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BIOMASS PYROLYSIS LIQUIDS

UPGRADING AND UTILISATION


An assessment study executed for the Commission of the European
Communities, Directorate-General Science, Research and Development,
Biomass Unit.
BIOMASS PYROLYSIS LIQUIDS
UPGRADING AND UTILISATION
Edited by
A. V. BRIDGWATER
Department of Chemical Engineering and Applied Chemistry,
Aston University, Birmingham, UK
and
G. GRASSI
Commission of the European Communities,
Brussels, Belgium
ELSEVIER APPLIED SCIENCE
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WITH 87 TABLES AND 90 ILLUSTRATIONS
1991 ECSC, EEC, EAEC, BRUSSELS AND LUXEMBOURG
British Library CataloguiDg in Publication Data
Biomass pyrolysis liquids upgrading and utilisation.
1. Biomass fuels
I. Bridgwater, A. V. (Anthony V.) II. Grassi, G. 1929-
662.88
ISBN 1-85166-565-X
Library of Congress Cataloging-in-Publication Data
Biomass pyrolysis liquids upgrading and utilisation/edited by
A. V. Bridgwater and G. Grassi.
p. cm.
Includes bibliographical references and index.
ISBN 1-85166-565-X
1. Biomass chemicals. 2. Pyrolysis. I. Bridgwater, A. V.
II. Grassi, G.
TP248.B55B563 1991
662' ,88---<1c20 90-45279
Publication arrangements by Commission of the European Communities, Directorate-
General Telecommunications, Information Industries and Innovation, Scientific and
Technical Communication Unit, Luxembourg
EUR 12642 EN
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Preface
Biomass pyrolysis has been practised for centuries in the manufacture
of charcoal for industry and leisure. Only in the last two decades,
however, has attention focussed on a better understanding of the
science and technology, with the resultant benefits of better designed
and controlled processes that give high yields of liquid products. These
liquids, or 'bio-oil' as it is referred to, can be used in a variety of ways:
-combustion to replace conventional fuel oil in boilers, process
equipment such as kilns and in gas turbines for power generation;
-upgrading by hydrotreating or with zeolites to gasoline, diesel and
other hydrocarbon fuels, of chemicals;
--extraction and upgrading to fuel additives and chemical
specialities.
Any charcoal produced can also be utilised to form char- water
slurries, analogous to coal-water slurries, or bioi-oil slurries which
may be used as liquid fuels in many combustion applications.
A group of experts was set up in the EC Energy from Biomass
programme to evaluate the status and opportunities for deriving useful
liquid products from biomass pyrolysis. This book is a report of their
findings and conclusions. It forms an authoritative guide to the wide
range of technologies employed in biomass pyrolysis, and product
upgrading, utilisation and characterisation. Recommendations and
conclusions are included to identify promising areas of research and
development that will be of value to researchers, planners and
companies throughout the world.
v
A. V. BRIDGWATER
G. GRASSI
Contents
Preface v
1. The European Energy from Biomass Programme 1
G. GRASSI (Commission of the European Communities,
Brussels, Belgium)
2. A Review of Biomass Pyrolysis and Pyrolysis Technologies . 11
A. V. BRIDGWATER and S. A. BRIDGE (Aston University,
Birmingham, UK)
3. Direct Catalytic Liquefaction Technology of Biomass: Status
and Review 93
D. MEIER (Federal Research Centre for Forestry and
Forest Products, Hamburg, Federal Republic of
Germany) and M. Rupp (VEBA OEL Entwicklungs
GmbH, Gelsenkirchen, Federal Republic of Germany)
4. Upgrading of Pyrolysis Oils by Hydrotreatment 103
E. CHURIN (Universite Catholique de Louvain, Belgium)
5. Charcoal-Water Slurries: State of the Art and Future
Prospects
C. ESNOUF (CEMAGREF, Antony, France)
vii
119
viii Contents
6. Contribution to the Analytical Study of Biomass Pyrolysis
Oils . 155
P.-L. DESBENE, M. ESSAYEGH, B. DESMAZIERES and J.-J.
BASSELIER (Universite de Paris VI, Paris, France)
7. Product Standards for Pyrolysis Products for Use as Fuel in
Industrial Firing Plants . 177
F. RICK and U. VIX (Technischer Uberwachungs-Verein
Rheinland eV, KOln, Federal Republic of Germany)
8. Utilisation of Pyrolysis Liquids in Refineries . 219
M. Rupp (VEBA OEL Entwicklungs GmbH,
Gelsenkirchen, Federal Republic of Germany)
9. Upgrading of Biomass Pyrolysis Liquids to High-Value
Chemicals and Fuel Additives 227
T. STOIKOS (Chemical Process Engineering Research
Institute, Thessaloniki, Greece)
10. Integrated Liquid Fuel Processes 243
A. V. BRIDGWATER (Aston University, Birmingham,
UK)
11. Environmental Aspects of Gaseous Emissions from Wood
Carbonisation and Pyrolysis Processes 263
C. MEZERETTE and P. GIRARD (Centre Technique Fores-
tier Tropical, Nogent sur Marne, France)
12. Pilot Plant Requirements 289
M. Rupp (VEBA OEL Entwicklungs GmbH,
Gelsenkirchen, Federal Republic of Germany)
13. Biomass Pyrolysis in Brazil: Status Report 299
C. A. LUENGO and M. O. CENCIG (University of
Campinas, Brazil)
14. Overview of Thermochemical Conversion of Biomass in
Canada 311
the late R. D. HAYES (Energy, Mines and Resources
Canada, Ottawa, Canada)
Contents ix
15. Pyrolysis in Finland 327
Y. SOLANTAUSTA and K. SIPILA (Technical Research
Centre of Finland, Espoo, Finland)
16. Development of Pyrolysis Reactor Concepts in the USA 341
J. DIEBOLD (SoLar Energy Research Institute, GoLden,
CoLorado, USA)
17. Conclusions and Recommendations 351
A. V. BRIDGWATER (Aston University, Birmingham,
UK)
Index . 363
1
The European Energy from Biomass Programme
G. GRASSI
Head of the Biomass R&D Programme (DG XII), Commission of the
European Communities, 200 rue de la Loi, B-1049 Brussels, Belgium
INTRODUCTION
Renewable energy sources are capable of providing a significant
fraction of Europe's needs in the 21st century. In particular, bio-energy
has the potential to provide the EC with as much energy as the current
exploitation of North Sea oil fields (the equivalent of two million
barrels of oil per day) or currently installed nuclear power, but without
the hazards or without any contribution to the CO
2
build-up, and with
the advantage of being infinitely renewable.
At present, biomass contributes over 2% of the EC's primary
energy needs, mainly as firewood and charcoal, and about 60% of its
industrial needs as timber. Beyond the year 2000, agro-forestry
biomass will have potential production of around 600 million tonnes of
dry material per year. This could provide up to 10% of the European
Community's needs of 100 MTOE/y with a cost-effective, sustainable,
environmentally acceptable, although limited, alternative energy
source, as well as providing 100% of its industrial requirements of
120-230 million m
3
/y of timber.
Over the IS-year life of the European Community's Research,
Development and Demonstration activities on energy from biomass,
many positive effects have been identified, including:
-a significant potential energy contribution of 10%;
-a significant potential industrial contribution for timber and fibre
of up to 100%;
2 G. Grassi
-socio-economic benefits through creation of new jobs;
-environmental benefits through CO
2
absorption, lower sulphur
emissions, forest fire control, erosion control, etc.
The fourth R&D Energy from Biomass programme, now being
implemented, covers six main sectors of activity:
(1) Production of biomass (short-rotation forestry, sweet sorghum).
(2) Harvesting, transportation, storage of biomass.
(3) Biological conversion (acid and enzymatic hydrolysis).
(4) Thermochemical conversion (pyrolysis, catalytic processes).
(5) Integrated pilot projects.
(6) Assistance to large integrated biomass schemes-LEBEN
projects.
The main for EC support in selecting the projects
were:
-industrial involvement;
-international collaboration;
-R&D pre-competitive projects;
-wide industrial impact;
-research activity of interest for all the Community.
The main results of the call for proposals were the following:
Total number of proposals received:
Total cost of the activities proposed:
Contribution requested from the EC:
203
153MECU
89MECU
which shows a substantial increase compared to the previous R&D
Programme. In particular the following observations were made in this
latest programme:
-It appears that many proposals are now approaching the pre-
competitive stage of full or integrated biomass system
development.
-More and larger projects are being proposed with correspondingly
higher funding levels requested. This shows the growth in
collaboration and interaction between research centres in Europe.
-Expert networks have been constituted on specific scientific topics
such as short-rotation forestry, annual crops, enzymatic hydroly-
sis, pyrolysis liquids upgrading and utilisation to provide a
European resource of expertise to aid implementation of the
emerging technologies.
The European Energy from Biomass Programme 3
-There is an increase in industrial participation, in particular from
larger industrial organisations.
FUEL PRODUCTS
The basic strategic objective of the present and future R&D program-
mes is the production of liquid 'bio-fuels':
(1) Bio-ethanol produced from sugar or starch for the transporta-
tion market employing advanced technologies and using new
crops. This is at present given low emphasis by the Commission,
but should develop at a significant rate after the year 2000.
(2) Liquid fuel or bio-crude-oil bio-oil from thermochemical pro-
cessing by pyrolysis of lignocellulosic materials. The application
is for general thermal applications such as boilers, process heat
and turbines and as a substitute for the extensive fossil fuel
imports. Possibilities of upgrading this crude liquid fuel to
synthetic hydrocarbons are also being considered.
(3) Oxygenated fuels such as methanol and fuel alcohol are
produced through gasification processes and, while perceived to
have a long-term future, are only included in the current
programme at a modest level.
CONVERSION TECHNOLOGIES
For biomass conversion technologies, the most promising route
currently seems to be the thermochemical one for the production of
pyrolytic oils or bio-oil. The economic viability of this process is
promising in the medium term, and its integration into conventional
energy systems presents no major problems. This liquid is of moderate
heating value; is easily transported; can be burnt directly in thermal
power stations; can possibly be injected into the flow of a conventional
petroleum refinery, burnt in a gas turbine, or upgraded by hydrotreat-
ing or zeolite-based processes to obtain light hydrocarbons for
transport fuel. The technologies for producing bio-oil are evolving
rapidly with improving process performance, higher yields and better
quality products. There is, therefore, considerable justification for a
substantial and robust R&D programme in this area.
4 G. Grassi
After a thorough analysis of the state of the art, perspectives,
opportunities and constraints of the range of available thermochemical
conversion technologies, the European Commission has decided to
concentrate most of its efforts on pyrolysis, up-grading of the derived
liquid products and product utilisation. This decision was motivated by
the following reasons:
(1) The European Commission began the modern development of
this oil technology about seven years ago. At that time there was
almost no R&D and no industrial activity in the EC, except for
some very limited university-based research.
(2) Since then, some significant results have been obtained which
indicate that pyrolytic conversion processes are very promising
for the production of useful, valuable, economical liquid fuels,
with potential for premium liquid fuel substitution. Pyrolysis is
attractive because converting solid biomass and wastes into
liquid products presents many advantages in transport (the
energy density is increased about four-fold), storage, handling,
retrofitting, combustion and flexibility in production and market-
ing. A relatively unsophisticated technology is employed in
which biomass is converted in a very fast and efficient way into
liquid fuels at high efficiency (up to 80%) which can be directly
utilised.
(3) In 1988, the European Commission expanded this activity by
constituting a European Expert Network known as Pyrolysis
Liquids Upgrading and Utilisation Group (PLUUG) covering
most of the subjects considered of greatest potential interest:
pyrolysis and liquefaction processes, liquids upgrading, utilisa-
tion, and definition of standards concerning bio-oil, char slurries
and waste disposals. At that time, this multi-sectoral activity
constituted the only R&D in the EC.
(4) The five largest markets envisaged for pyrolysis products are:
-synthetic oil for boilers and power stations;
-synthetic oil as refinery feedstock;
-synthetic oil for gas turbines and modified diesel engines;
---<:har slurry for boilers and power stations;
---<:harcoal for the steel and non-ferrous metal industry.
This multi-sectoral and comprehensive R&D work on biomass
pyrolysis and related activities will have the characteristics of a real
European Community programme with the active participation of over
The European Energy from Biomass Programme 5
30 organisations from universities, research centres and industries
in ten member states.
The activity will focus on three main topics:
-advanced pyrolysis technologies and improvement of existing
ones;
-upgrading of pyrolysis liquids or bio-oil by catalytic hydrotreating,
zeolite conversion and development of charcoal-based slurries;
-utilisation of the pyrolysis liquids or bio-oil in boilers, power
stations, refineries, gas turbines and modified diesel engines.
Thermochemical conversion technologies can also be applied to the
treatment of urban waste, using analogous technologies with minor
modifications, and producing very similar products.
ORGANISATION
The thermochemical sector will be managed by the Commission with
the assistance of coordinators as indicated in Fig. 1. The coordination
activity has the following objectives:
-to follow up and transfer information and activate interactions
between various sectors;
-to evaluate and define eventual re-orientation of activities;
-to carry out techno-economic evaluations and construct models;
-to provide assistance in the definition of norms and standards;
-to provide assistance in the transfer of technologies and to
stimulate international cooperation;
-to organise special workshops.
The coordination structure is shown on Fig. 1 with the Programme
Manager, Overall Coordinator and five Sector Coordinators with their
allocation of individual projects. Figure 2 shows the relationship with
the other activities in the overall Energy from Biomass programme.
The required interactions between all the projects will be reinforced
by a common Technical Annex to all the contracts which sets out the
interactive requirements between each group. This is reproduced in
Table 1. In addition, in order to reduce the overall number of
contracts, projects have been grouped into common areas wherever
possible as either associated contracts or subcontracts. This will also
have the effect of encouraging collaboration as well as streamlining the
contract negotiation and implementation process.
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G. Grassi
Table 1
General technical annex for all energy from biomass contracts in thermo-
chemical conversion
These projects are part of a co-ordinated CEC activity in the field of
thermochemical conversion of biomass. The contractors will, therefore,
participate in a coordinated network dealing with relevant R&D topics to
facilitate interaction and effect collaboration as follows:
(1) Pyrolysis plants will be built and operated by the following organisa-
tions: CRES, Egemin, Aston University, Twente University and LNETI.
Samples of bio-oils from each process will be made available for analysis
by P&M Curie University in collaboration with UCL and CTFT, for
upgrading by UCL and CPERI, and for testing on a variety of
applications by UEF and Noel Penny as detailed in the relevant sections
below. Data will be made available to the University of Aston for
technical and economic assessment and to the University of Naples for
modelling pyrolysis processes.
(2) The liquid products from each of the pyrolysis plants detailed above in
section 1 will be characterised by physical and chemical properties and
by detailed analysis by P&M Curie University in collaboration with UCL
and CTFT. The products will be compared with samples from other
processes from Canada and the USA.
(3) Samples of the liquid products from some or all of the pyrolysis
processes detailed above in section 1 will be upgraded to hydrocarbons
through hydro heating by UCL in collaboration with VEBA. The
products from hydrotreating will be characterised as detailed in section 2
by P&M Curie University in collaboration with UCL and CTFT.
(4) Zeolite upgrading will be coordinated by Aston University on bio-oils
from Egemin, LNETI, CRES and/or Bio-Alternative in the context of
the LEBEN project and/or from other sources. Tests will be commis-
sioned and small units designed for installation on one or more of the
above pyrolysis units. The products will be characterised as detailed in
section 2 by P&M Curie University in collaboration with UCL and
CTFT.
(5) High pressure liquefaction of biomass will be carried out by the
University of Compiegne, University of L'Aquila and Institute of Wood
Chemistry in collaboration with VTT. The liquid products will be
characterised as detailed in section 2 by P&M Curie University in
collaboration with UCL and CTFT.
(6) Char-water and char-oil slurries will be manufactured by ENEL and
KTI and CADET and tested by them and UEF for combustion and
power generation.
(7) The opportunities for incorporation of pyrolysis oil into a conventional
refinery for upgrading and blending will be assessed by VEBA. Relevant
data on product characteristics will be supplied by P&M Curie
University in collaboration with UCL and CTFT. Relevant data on
pyrolysis and liquefaction processes will be supplied by Egemin, Aston
The European Energy from Biomass Programme 9
Table l-contd.
University, Twente University, LNETI, CRES, University of
Compiegne, University of L'Aquila and Institute of Wood Chemistry in
collaboration with VTT. Relevant data on process performance and
economics will be shared with Aston University in the context of
technoeconomic evaluation.
(8) High added value chemicals will be manufactured by CPERI from
bio-oils supplied by one or more of: Egemin, Aston University, Twente
University, LNETI, CRES, University of Compiegne, Institute of Wood
Chemistry, and University of L'Aquila as they become available.
Comparisons will be made with oils from other sources such as from
Canada and the USA in the context of the agreed collaboration.
(9) Combustion trials of bio-oil and char slurries will be carried by UEF,
and by Noel Penny on a gas turbine. Oils from one or more of: Egemin,
Aston University, Twente University, LNETI, CRES, University of
Compiegne, Institute of Wood Chemistry, and University of L'Aquila
will be used as they become available. Comparisons will be made with
bio-oils from other sources such as Bio-Alternative, KTI/Italenergie,
and from Canada and the USA in the context of the agreed
collaboration.
(10) IRIN will apply their experience of integrated waste-water treatment
from the olive oil and similar industries to pyrolysis waste"waters from
one or more of the processes referred to in section 1 and/or other
relevant processes as material is available. This will assess the feasibility
of different techniques and produce outline treatment plant designs and
costs. Relevant data will be supplied to Aston University for evaluation.
(11) TUv will develop suitable standards for assessment and utilisation of
bio-oils in a variety of applications using relevant information on
characteristics from P&M Curie University, UCL and CTFT; perfor-
mance data from CADET, UEF, and Noel Penny; and upgraded
product data from UCL, VEBA and CPERI. Data will be utilised as
soon as it becomes available.
(12) Aerimpianti will monitor emissions and other environmental aspects
resulting from the operation of their refuse-derived fuel gasification
plant. The consequences for environmental control measures will be
assessed.
(13) On gasification, ASCAB will derive results from the pressurized fluid
bed oxygen gasifier at Clamecy on eucalyptus feeds to establish
performance criteria and viability assessment.
(14) Other projects that are initiated during the course of this programme
will contribute to this coordination in a similar way as the projects listed
above.
(15) Other activities in any of the above areas may also be carried out in the
context of agreed collaboration with other countries and organisations
including Canada, Brazil and the International Energy Agency Bio-
energy Agreement, and these activities will also form part of this
coordinated programme.
10
G. Grassi
Table l-contd.
(16) All contractors will provide confidential information to the Commission,
and performance and cost data in Aston University for techno-economic
assessment.
Coordination
All the above contractors will fully cooperate in the coordination activity to
effect interaction and collaboration between all activities, which will be
managed by the Commission with the assistance of the coordinators.
2
A Review of Biomass Pyrolysis and Pyrolysis
Technologies
A. V. BRIDGWATER & S. A. BRIDGE
Energy Research Group, Chemical Engineering Department, Aston
University, Birmingham B47ET, UK
ABSTRACT
Biomass, as the only renewable source of fixed carbon, has attracted
considerable attention as a renewable energy resource after the oil crises
of the last 15 years. Of the variety of technologies available for
converting biomass into more useful and valuable energy products,
thermochemical processing and particularly pyrolysis have been
investigated for the economic production of liquid fuels. The charac-
teristics of pyrolysis processes, upgrading technologies and products are
summarised in this overview paper in order to focus on the
opportunities, constraints and requirements for successful implementa-
tion of these technologies in Europe.
1 INTRODUCTION
The potential offered by biomass and solid wastes for solving some of
the world's energy problems is widely recognised. The energy in
biomass may be realised either by direct use as in combustion, or by
upgrading into a more valuable and usable fuel such as fuel gas or fuel
oil or higher-value products for the chemical industry. This upgrading
may be by physical, biological, chemical or thermal methods to give a
solid, liquid or gaseous fuel.
This chapter presents an overview of the technologies of thermo-
chemical conversion by pyrolysis and liquefaction, and in particular
considers the production and properties of liquid fuels. All the aspects
11
12 A. V. Bridgwater & S. A. Bridge
outlined are described in more depth in the rest of this book, and this
introductory chapter serves to explain the opportunities and con-
straints in which liquid fuel production by biomass pyrolysis has to
operate, and the complex interactions that affect implementation.
The range of thermochemical technologies is first characterised in
terms of process parameters and products in order to provide a
comparison between the various thermochemical conversion tech-
nologies. Pyrolysis processes are then described in more detail,
concentrating on process principles, state of development, unresolved
problems, and opportunities and potential from which an R&D
strategy is proposed. The most advanced examples of each mode of
pyrolysis are described in detail.
All aspects of pyrolysis liquids upgrading and utilisation are covered
in the succeeding chapters of this book, and reference will be made to
these further details when relevant.
2 THERMOCHEMICAL TECHNOLOGIES
There are four main thermochemical methods of converting biomass:
pyrolysis, liquefaction, gasification and combustion. Each gives a
different range of products and employs different equipment con-
figurations operating in different modes. These are summarised in
Table 1, and depicted in Fig. 1.
The main characteristics of these processes are summarised in Table
2 to give some indication of the processing constraints and limitations
of each technology. Whilst combustion is a thermochemical process, it
is not considered further as it is well established and has limited
development opportunities for satisfying longer-term energy require-
Table 1
Thermochemical conversion technologies and products
Technology
Pyrolysis
Liquefaction
Gasification
Combustion
Primary product
Gas
Liquid
Solid char
Liquid
Gas
Heat
Example of application
Fuel gas
Liquid fuel substitution
Solid fuel or slurry fuel
Liquid fuel substitution
Fuel gas
Heating
Review of Biomass Pyrolysis Technologies 13
ments. It is worth noting in Table 2 the different feed requirements for
the various technologies, the scale to which each has been developed,
and the variation in types and proportions of products that are
produced by the different processes.
3 PRODUCTS
Some materials directly produced from a thermochemical conversion
process can be used more readily than raw biomass and may be
considerably more valuable. These primary products can be used as
such, or further converted into even more useful and/or valuable
secondary fuel or chemical products. The main products are outlined
below and characterised later in this chapter, and in more detail in
individual chapters of this book.
3.1 Primary products
The primary products from thermochemical conversion can be gas,
liquid and/or solid char, depending on the conversion technology
CONVERSION
TECHNOLOGY
PYROLYSIS
UOUEFACTION
GASIFICA TION
.:.:.:.:.:.:.:.:.:.:.:-:.:.:.:.:.:.:.:.;

<1;[-':10J
LIQUID
:
::,'.r, ............................. ::::
;;;: LHV FUEL GAS ..
FIG. 1. Primary products from biomass conversion.
14 A. V. Bridgwater & S. A. Bridge
Table 2
Characteristics of thermochemical conversion technologies
Figures quoted are typical, and can vary considerably according to technology
and operating conditions.
Pyrolysis Liquefaction Gasification
Slow Flash
Feedstock
Feed size Any Small Very small Mixed, large
Moisture content Low Very low Very low 50% max.
Parameters
Temperature,OC 400-600 450-900 250-400 1000-1500
Pressure, bar 001-1 1 100-200 Up to 20
Maximum throughput 5 005 01 40
achieved to date, dry/th
Products
(dry basis on dry feed)
Gas Yield, %wt Up to 40 Up to 70 20 100-250
HHV, MJ/Nm
3
5-10 10-20 2-6 5-15
Liquid Yield, %wt Up to 30 Up to 70 Up to 50 Up to 3
HHV,MJ/kg 23 23 30 23
Solid Yield, %wt 30 Up to 15 Up to 25 nil (ash)
HHV, MJ/kg 30 30 30
HHV, High heating value.
employed. These primary products can be used directly, or they may
be subjected to further chemical processing, which is described below,
to give a higher quality and value fuel or chemical products. The
possible primary products and their processing origins are summarised
in Table 3. The technologies for upgrading, and likely viable size
ranges are summarized in the relevant sections below.
Much of the present interest in thermochemical conversion centres
on liquid products due to their high energy density which reduces the
cost of storage and transport as shown in Table 4, and potential for
premium liquid fuel substitution which is discussed later. Oil and
slurry mixtures have a clear advantage over woodchips and straw in
energy density, and for transporting over longer distances this
difference may be a decisive factor.
The gas is a low to medium heating value fuel gas that may be used
as such for process heat (e.g. for feed drying) or power generation
Review of Biomass Pyrolysis Technologies 15
Table 3
Thermochemical conversion primary products and technologies
Product Form Components Source
Fuel gas LHV CO, H
2
, CO
2
, Pyrolysis,
CH4 , N2 air gasification
MHV CO, H
2
, CO
2
, Pyrolysis,
CH
4
and higher O
2
gasification
hydrocarbons
Liquid Oil, primary Water-insoluble Pyrolysis, flash
oxygenates
Oil, secondary Water-insoluble Pyrolysis, slow
oxygenates
Oil, liquefaction Water insoluble Liquefaction
oxygenates
Char-oil slurry Charcoal, oil Pyrolysis, flash
Char-water slurry Charcoal, water, Pyrolysis
stabiliser
Aqueous Waste water Water-soluble Pyrolysis,
oxygenates, liquefaction,
e.g. acetic acid gasification
Solid Charcoal Pyrolysis
Heat Hot gas Combustion
LHV, low heating value; MHV, medium heating value.
Table 4
Some characteristics of biomass and fuel derivatives
bulk density Heating value Energy
(kglm
3
) dry basis density
(GIlt) (Gllm
3
)
Straw -100 20 2
Woodchips -400 20 8
Pyrolysis liquid -1200 23 27
Char -300 30 9
Char-water slurry (50/50) -1000 15 15
Char-oil slurry (20/80) -1150 24 28
16 A. V. Bridgwater & S. A. Bridge
either on the plant or for export. It contains CO, CO
2
, H
2
, CH
4
and
significant quantities of both saturated and unsaturated hydrocarbons.
Whilst it could be physically and chemically upgraded to higher-value
products such as methanol or gasoline, conversion by gasification is
more efficient.
The liquid approximates to biomass in elemental composition, and is
composed of a very complex mixture of oxygenated hydrocarbons.
The complexity arises from the degradation of lignin, and the broad
spectrum of phenolic compounds that result from uncontrolled de-
gradation. The liquid, particularly from flash pyrolysis processes, is
often referred to as 'oil' or 'bio-oil', but can resemble tar, particularly
from slow pyrolysis processes. This liquid can also be upgraded to
liquid hydrocarbon fuels. Utilisation of this material is discussed later.
The pyrolysis liquid from flash pyrolysis processes is a low viscosity
dark-brown mobile fluid with up to 15 or 20% water, but usually no
phase separation unless a very wet feed has been used. From slow
pyrolysis processes the liquid is a thick black tarry fluid with up to 20%
wt water and with viscosity ranging from gas oil to heavy fuel oil.
More details of characteristics and uses are included later in this
chapter and in many of the contributions to this book.
The solid product from pyrolysis processes is char, which has limited
current applications in developed countries for metallurgical and
leisure industries. An alternative approach to a liquid product lies in
grinding the char and slurrying it with water with a stabiliser, as in
coal-water mixtures. A slurry can also be made from the bio-oil and
char, although less is known about this type of material. Stable and
mobile slurries with concentrations of up to 60% wt charcoal have
been reported. Slurries can also be made from the oil and char with
reported maximum charcoal concentrations of 25%. Slurries from oil,
char and water pose still-unresolved problems of stability.
Water is also produced from any moisture in the biomass feed and as
a reaction product from pyrolysis. This often contains very high levels
of organic matter which makes disposal an important consideration in
process design.
3.2 Secondary products
A wide range of secondary products can be produced from the primary
products summarised above, including hydrocarbon transport fuels,
oxygenate transport fuels, power, bulk chemicals including hydrogen
and ammonia, and chemical specialities. Examples of the more
Review of Biomass Pyrolysis Technologies 17
significant possibilities are shown in Fig. 2 and summarised in Table 5.
Some of the processes for effecting these transformations are commer-
cially available and proven, whilst others are still at the exploratory
research and development stage, and the status of these upgrading and
refining technologies is summarised in Table 6, with an indication of
what development work is still required and a possible timescale
showing the time likely to elapse before they could become commer-
cially available. This latter point does, however, significantly depend
on how fossil fuel prices change, and represents a situation where
there is considerable market pull.
3.3 Utilisation
Relatively unconventional fuels such as bio-oil and fuel alcohol will
require their own marketing infrastructure to be developed, whereas
synthesised conventional fuels such as gasoline and diesel can, in
principle, be readily accommodated in the established fossil fuel
infrastructure. There are some overlaps (for example, bio-oil might be
incorporated into a refinery feed stream), but the distribution, storage
and handling aspects of product utilisation must not be ignored.
CONVERSION
Tf.CHNOLOG r
PROCESSIHO
Tf.CHHOI.OG r
FIG. 2. Primary and secondary products from thermochemical conversion.
18 A. V. Bridgwater & S. A. Bridge
Table 5
Secondary products and sources
Secondary product
Hydrocarbon fuels
Gasoline
Diesel
Fuel oil
Oxygenate fuels
Methanol
Fuel alcohol
Power
Chemicals
Hydrogen
Ammonia
Speciality chemicals
Source
Pyrolysis
Pyrolysis
Liquefaction
Gasification
via methanol
Pyrolysis
Pyrolysis
Liquefaction
Gasification
via methanol
Pyrolysis
Liquefaction
Gasification
Gasification
Pyrolysis
Gasification
Combustion
Gasification
Gasification
Pyrolysis
Liquefaction
Process
Q
Hydrotreating + refining
Zeolites + refining
Hydrotreating + refining
MTG
Hydrotreating + refining
Zeolites + MOGD
Hydrotreating + refining
MOGD
Stabilisation
Stabilisation
Synthesis
Synthesis
Turbine
Engine, turbine or
Rankine cycle
Rankine cycle
Conversion
Synthesis
Extraction and/or
conversion
Extraction and/or
conversion
Q Abbreviations; MTG, Mobil's methanol-to-gasoline process; MOGD,
Mobil olefins to gasoline and distillate.
Of the primary pyrolysis products, char is very stable and will not
deteriorate, and liquids are relatively stable if stored correctly.
Liquids, however, have significant advantages over solids in handling
and transport, but potential disadvantages could arise from the
chemical and physical instability of pyrolytic liquids, slurries and
mixtures, although there are mixed reports on such problems. These
are discussed later, but unless the properties of these liquids can be
completely controlled, their advantages cannot be fully realised.
Generally, liquid or gaseous products are easier to handle in the
combustion process and this is important in retrofitting existing
equipment. Existing oil-fired burners cannot be fuelled directly with
Review of Biomass Pyrolysis Technologies
Table 6
Transformation technologies and timescales
Technology Product Current status
Combustion and steam turbine Power and heat Commercial
Engines, spark Power Commercial
ignition and diesel
Ammonia synthesis Ammonia, etc. Commercial
Methanol synthesis Methanol Commercial
Methanol to gasoline Gasoline Commercial
Refining hydrocarbons Gasoline, etc. Commercial
Hydrogen production Hydrogen Commercial
Gas turbines Power and heat Demonstration
Fuel alcohol synthesis Fuel alcohol Pilot
Methanol to gasoline Gasoline, etc. Demonstration
and diesel
Hydrotreating Hydrocarbons Laboratory
Zeolite upgrading Gasoline Laboratory
and BTX
Approximate time before being commercially available.
b Approximate time before commercially implemented.
19
Time Time
b
(y) (y)
0 0
0 0
0 15
0 15
0 15
0 15
0 25
5 10
5 15
5 15
10 20
15 25
solid biomass without major reconstruction or replacement of the unit,
which may not be attractive in uncertain fuel markets. However
pyrolytic oils, char-oil slurries and char-water slurries are likely to
require only relatively minor modifications of the equipment, or even
none is some cases. Powdered-coal-fired furnaces can relatively easily
accept charcoal as a partial fuel replacement, as long as the volatile
content is compatible with the furnace design.
It may be possible to fire turbines and modified diesel engines with
pyrolytic oils or upgraded pyrolytic oils, and perhaps even char-water
slurries, but there is little recent practical experience.
Several of the accompanying chapters to this book describe primary
and secondary products and possibilities for their utilisation.
4 THE PROCESS OF PYROLYSIS
4.1 Principles
Pyrolysis is thermal degradation either in the complete absence of
oxidising agent, or with such a limited supply that gasification does not
occur to an appreciable extent, the latter may be described as partial
20 A. V. Bridgwater & S. A. Bridge
gasification. Relatively low temperatures of 500-800C are employed,
compared with 800-1100C in gasification. Three products are usually
obtained: gas, liquid and char, the relative proportions of which
depend very much on the pyrolysis method and reaction parameters.
Fast or flash pyrolysis, for example, is used to maximise either gas or
liquid products according to the temperature employed, while slow
pyrolysis is known as carbonisation and is used to maximise solid
charcoal production. The range of primary products that are derived
from pyrolysis were described above and are summarised with typical
applications in Fig. 3. The variations in processing technologies and
their effect on the product mix are summarised in Section 4.2 below.
Pyrolysis is attractive because solid biomass and wastes, which are
difficult and costly to manage, can be readily converted to liquid
IIi
Slurry with water
L 50tlas fuet
Gasify Bum for drying or heating
Generate power
5011 as fuel
50nd to refinery
Slurry with charccal
Upgrade by hydrotreating
upgrade by
5011 as fuel
Bum for drying
Bum for heating
Generate power
Incinerate
Degrade biologicatly
Incorporate in product
FIG. 3. Primary products from pyrolysis and applications.
Review of Biomass Pyrolysis Technologies 21
products. These liquids, as liquid or slurry, have advantages in
transport, storage, combustion, retrofitting, and flexibility in produc-
tion and marketing. The energy density advantages were summarised
in Table 4.
4.2 Pyrolysis technologies
Pyrolysis has been practised for centuries for production of charcoal.
This requires relatively slow reaction at low temperatures to maximise
solid char yield. More recently, studies into the mechanisms of
pyrolysis has suggested ways of substantially changing the proportions
of the gas, liquid and solid products. This is achieved by changing the
rate of heating, and the reaction temperature.
Flash or fast pyrolysis can give high yields of liquids or 'bio-oil' of up
to 70% wt on a dry feed basis on a laboratory scale. This process
involves very high heating rates combined with moderate temperatures
of less than 650C, short residence times and rapid quenching of liquid
pyrolysis products. These high heating rates, of up to a claimed
lOOOC/s or even 10 OOOC/s, at temperatures below about 650C and
with rapid quenching, cause the liquid intermediate products of
pyrolysis to condense before further reaction breaks down higher-
molecular-weight species into gaseous products. The high reaction
rates also minimise char formation, and under some conditions no char
is apparently formed. At higher maximum temperatures the major
product is gas. Pyrolysis at these high heating rates is known as fast,
flash, or ultra-pyrolysis according to the heating rate and residence
time, although the distinctions are blurred. Other work has attempted
to exploit the complex degradation mechanisms by carrying out
pyrolysis in unusual environments. The characteristics of the main
modes of pyrolysis are summarised in Table 7, and variants are
summarised in Tables 8 and 10 and described in Section 5 of this
chapter.
Most flash pyrolysis processes are based on indirect heating of
biomass by gas-phase heat transfer from a hot surface such as the
reactor wall in the case of a rotary kiln, or hot solids such as sand in a
twin fluid-bed system. Heat transfer in such processes is mainly by
convection, although radiative heat transfer can also be significant.
The relatively low heat transfer rates between gas and solid that result
from this method of heating can necessitate longer contact times as
well as larger reactor volumes for the heat transfer gas.
22 A. V. Bridgwater & S. A. Bridge
Table 7
Pyrolysis technology variants
Residence Heating Maximum Major
time rate temperature product
eC)
Carbonisation Hours-days Very low 400 Charcoal
Conventional 5-30 min Low 600 Bio-oil, charcoal
and gas
Fast 0.5-5s Fairly high 650 Bio-oil
Flash
Liquid <Is High <650 Bio-oil
Gas <Is High <650 Chemicals
and fuel gas
Ultra <05s Very high 1000 Chemicals
and fuel gas
Vacuum 2-30s Medium 4llIl Bio-oil
Hydropyrolysis <lOs High <500 Bio-oil
and chemicals
Methanopyrolysis <lOs High >700 Chemicals
Table 8
Characteristics of pyrolysis processes
Figures quoted are typical, and can vary considerably according to process,
feedstock and operating conditions
Carbon- Slow Flash
isation
Low temp. High temp.
Parameters
Temperature,oC 300-500 400-600 450-600 700-900
Pressure, bar 1 01-1 1 1
Maximum throughput achieved to 5 1 005 010
date, dry t/h
Products
(dry basis on dry feed)
Gas Yield, %wt Up to 150 Up to 60 Up to 30 Up to 80
HHV, MJ/Nm
J
3-6 5-10 10-20 15-20
Liquid Yield, %wt, Up to 25 Up to 30 Up to 70 Up to 20
dry basis
HHV, MJ/kg 20 20 24 22
Solid Yield, %wt Up to 40 Up to 30 Up to 15 Up to 15
HHV, MJ/kg 30 30 30 30
Review of Biomass Pyrolysis Technologies 23
A more recent approach is ablative pyrolysis, which relies on heat
transfer from a hot surface through a liquid film to the pyrolysing
particle of biomass. This approach is claimed to be capable of
producing similar high liquid product yields, as well as offering
potential advantages of higher reactor-specific capacities and smaller
equipment sizes.
The heat required for pyrolysis can also be added indirectly in a
variety of ways such as indirect firing, hot gas, or hot liquid such as
metal or molten salt, or directly by partial gasification with limited
addition of oxidising agent such as air to give direct heating.
4.3 Liquid product
The process of pyrolysis is complex, but the most accepted theory is
that primary vapours are first produced, the characteristics of which
are most influenced by heating rate. These primary vapours then
further degrade to secondary tars and gases if held at a high
temperature for long enough for secondary reactions to occur. The
proportions and characteristics of these secondary materials are a
function of temperature and time. Yields of liquids from pyrolysis can
thus be influenced by the rate of reaction, with fast or flash pyrolysis at
lower temperatures of typically 450-650C giving the highest liquid
yields, and progressively high temperatures giving progressively higher
gas yields and lower liquid yields. Examples are described and
illustrated later.
The liquid product, known as bio-oil, may be readily burned and has
been employed for this purpose, for example by Bio-Alternative and
Ensyn (see later in this chapter). Some problems have, however, been
reported in use, particularly in storage, where phase separation,
polymerisation, and corrosion of containers can occur. In addition the
high oxygen and water contents make it incompatible with conven-
tional fuels although it may be utilised in a similar way. Some
conversion or upgrading for oxygen and water removal and stabilisa-
tion is necessary to give a product that is fully compatible with
conventional fuels.
It is important to differentiate between primary products or oils, and
secondary products or tars, and to appreciate the difference in
properties between flash pyrolysis liquids or primary oils and slow
pyrolysis products or secondary oils or tars. Primary oils tend to have a
lower viscosity, be more stable under ambient conditions, less sensitive
24 A. V. Bridgwater & S. A. Bridge
to water contamination due to great miscibility with water, and more
homogeneous.
Upgrading technology is not well developed; most attention has
been paid to hydrotreating and more recently some attention has been
afforded to zeolite synthesis to give synthetic gasoline, other hydrocar-
bons and olefins. The main characteristics are outlined below to
demonstrate the complexity of pyrolysis technology and product
utilisation. Details are given in the relevant chapters of the book.
4. 3. 1 Characteristics and utilisation
The liquid product is a highly oxygenated hydrocarbon with an
appreciable proportion of water from both the original feed moisture
and reaction product. Solid char may also be present. These properties
make it relatively unstable in both chemical and physical terms and
may cause problems in utilisation and upgrading. It is readily
combustible, but care has to be taken in storage, handling and
atomisation. Some of the characteristics are discussed below.
The water content is important as it has several effects: it lowers
heating value, affects pH (acidity), reduces viscosity, influences both
chemical and physical stability, reduces potential pollution problems
from waste-water disposal and could affect subsequent upgrading
processes. The interactions are poorly understood. The water is
difficult to measure and remove, since evaporation or distillation at
normal temperatures of around 100C or higher can cause significant
and potentially deleterious physical and chemical changes in the liquid.
Lower-temperature drying is not successful due to the nature of the
relationship between water and the organic component in which the
water seems to be chemically combined, such as water of hydration.
This phenomenon also makes early claims of water content and
consequently oxygen content of liquids on a dry basis subject to
uncertainty, although recent analytical advances have overcome such
problems. Utilisation and consideration of oil on a 'wet' or 'as-
produced' basis therefore seem to be more sensible.
Particulate levels may be high from char and ash carry-over.
Separation of solids from liquids is poorly researched, and reliance is
usually placed on primary separation in the vapour phase downstream
of the reactor before condensation of liquids. Char levels of up to 15%
by weight in the liquid have been reported (see Section 5.1).
The oxygen content of the pyrolysis liquid is very high, at up to
40% wt (see Table 9). When produced from dry or low-moisture-
Review of Biomass Pyrolysis Technologies 25
content feeds it typically has a heating value a little above that of the
biomass feed, in the range 20-25 MJ/kg.
A low pH arises from the organic acid content (e.g. acetic and
formic acids), and is therefore corrosive. Mild steel is not suitable for
handling or storage. Polypropylene piping, for example, has been used
to overcome this problem.
Polymerisation or deterioration of the liquid can be caused by
temperatures above around 100C and/or exposure to air (through
oxidation) which adversely affect physical properties such as viscosity,
and phase separation with deposition of a bitumen-like substance.
Heating the liquid to reduce viscosity for pumping or atomisation
needs to be considered carefully and thoroughly tested. Exposure to
air alone also causes deterioration, but at a slower rate than
temperature increase. Maintenance in a sealed enclosure has been
claimed to cause substantial pressure increases, so some minimal
venting is necessary to avoid pressure build-up but minimise exposure
to oxygen. Pyrolysis liquid has been reported as having been stored in
this way in a useable form for up to two years without problems.
Health hazards associated with pyrolysis liquids are also poorly
understood. Some toxicity and health tests on primary bio-oils have
been reported as comparatively less hazardous than equivalent fossil
fuel liquids.
Compatibility with conventional fuels is variously reported: pyrolysis
liquids have been described as immiscible but compatible. They cannot
be expected to be assimilated into a conventional fuel-marketing
infrastructure without some conversion or upgrading to give a product
that is wholly compatible with conventional fuels. The alternative is to
create a discrete pyrolysis liquids storage, distribution and utilisation
system, that is managed by experts who understand the special
problems of this fuel. It is likely that, in the short term, dedicated
applications will be developed, possibly in multi-fuel applications.
Some properties that have been reported are summarised in
Table 9.
4.3.2 Upgrading
Upgrading technology is based either on orthodox hydrotreating
technology to produce successively lower-oxygen-content hydrocar-
bons, or on the evolving zeolite technology to produce high quality
hydrocarbon fuels or aromatic chemicals directly. Both topics are
26 A. V. Bridgwater & S. A. Bridge
Table 9
Bio-oil properties
Alten GTRf
Laval SERf Tubingen Waterloo BASA
Elemental analysis,
% wt (wet basis)
C 6190 395 499 486 7262 5470 5812
H 600 75 70 72 1075 690 655
0 3102" 526 430 442 1506" 384" 3481
N 105 <01 <01 127 052
S 003 024
a 006
H/C ratio 1-16 228 168 178 151 135
O/C ratio 018 100 065 068 053 045
Moisture, % wt 1460 290 184 1870 45
pH 20 2-40 27
Ash, %wt 150 02 <005
Char content, % wt 920 92
Viscosity, cp 55 at 10 at 1300 at 40 at 250 at
70C 6O"C 30"C 4O"C 6O"C
HHV, MJ/kg
(wet) 263 243 21-1 223 232 222
Specific gravity 1195 123
(15/4C)
Density, g/cm
3
123 123 1-20 1216
at 55C
Pour point, C 27 -23
" By difference.
described more comprehensively in separate chapters, but the chemi-
cal principles are summarised in Fig. 4.
Hydrotreating is based on technology that is established in the
petroleum industry and is in principle readily adaptable. Preliminary
results indicate that conventional hydrotreating processes may be
readily adapted to pyrolysis liquids. The product is a low-grade
Hydrotreating (laboratory scale)
CzH30 + 15H
2
2(CH2)n + H20
bio-oil hydrogen gasoline, etc. water
Zeolites (fundamental research)
3(CH2)n + CO2
gasoline, etc. carbon dioxide
FIG. 4. Conceptual chemistry of bio-oil upgrading processes.
Review of Biomass Pyrolysis Technologies 27
gasoline that would require orthodox refining and blending to give a
marketable product. There are two approaches to hydrotreating:
(1) A dedicated purpose-designed and built hydrotreating
operation.
(2) Assimilation of bio-oil into a conventional oil refinery to utilise
the existing hydro treating operation.
Both processing options are described in later chapters.
Zeolite-based synthesis has been extensively demonstrated for
alcohol feeds, and a commercial plant is currently operating in New
Zealand. A little experience has been gained on upgrading products of
biomass pyrolysis, but there are insufficient data to draw any robust
conclusions. A significant feature is the high yield of aromatics which
give a premium-value gasoline product, and from which benzene,
xylene and/or toluene could be recovered. There are three basic
approaches to synthesising hydrocarbons from pyrolysis liquids. In all
cases the crude hydrocarbons would need to be subjected to orthodox
refining.
(1) Convert primary pyrolysis vapours to hydrocarbons in a close-
coupled operation. The primary product is aromatic-rich gaso-
line with a significant olefin by-product that could be alkylated
to yield more hydrocarbons.
(2) Condense the liquids, then process them with zeolites in the
liquid phase, which could be a remote operation to take
advantage of the economies of scale.
(3) Condense the liquids, then revaporise them for zeolite upgrad-
ing in the gas phase, which again could be a remote operation to
take advantage of the economies of scale.
Neither of these upgrading technologies is yet available commer-
cially, nor have robust mass balance and performance data been
produced. Hydrotreating is, however, more developed and could use
conventional hydrotreating practice for earlier implementation.
An alternative approach is to reduce the oxygen content to a
sufficiently low level that it may be satisfactorily blended with
conventional fuels. This might be achieved by less complete hydro-
genation. Simple distillation over activated clay such as bentonite has
been claimed to give a stable and storable product in one low-cost
step. No work on blending requirements of partially upgraded
products is known to have been carried out.
28 A. V. Bridgwater & S. A. Bridge
4.3.3 Blending
It has been suggested that limited quantities of crude bio-oil could be
assimilated into a conventional refinery operation to use existing
standard refinery operations for upgrading and refining. This is
currently being investigated in the EEC JOULE programme. Bio-oil
has a relatively high oxygen content and oxygen is not easy to remove,
being placed in this respect between nitrogen and sulphur con-
taminants in oil.
4.4 Solid product
4.4.1. Charcoal
When pyrolysis is optimised for charcoal production, yields of up to
30% wt on dry feed (volatile-free basis) are obtained. This occurs in
slow pyrolysis with reaction times of hours or days. Partial car-
bonisation gives higher yields, when the product contains a high level
of volatiles, and this is also referred to as torrified wood. At the very
high heating rates encountered in fast and flash pyrolysis, very low
char yields result, and have been reported as approaching zero under
some process conditions. Char yields can be optimised for production
of material for char-water slurries, although an integrated approach is
necessary for maximum energy recovery. The low char yields from
flash pyrolysis could be incorporated into the bio-oil to give a higher
yield of liquid fuel at a higher overall energy efficiency that could
exceed 80%.
4.4.2 Slurries
A possible outlet for the char is slurrying with the bio-oil, or with
water, or with both oil and water. Only a limited amount of char can
be introduced into oil as unacceptably high viscosities result from a
char concentration higher than about 25% wt. The maximum con-
centration of char in water that can be handled is about 60% to retain
mobility. The costs of the additives are significant at up to one-third of
the slurry preparation cost. A recent development is the production of
a ternary mixture of char, water and mineral oil which is claimed to
have several advantages.
Coal-water slurries are increasingly used in large boilers and these
slurries can be simply and/or partially replaced by char-water slurries.
The char-water slurry cannot, however, be an outlet for pyrolytic
waste-water as unstable sludge formation results. The ash content of
Review of Biomass Pyrolysis Technologies 29
the char is an important consideration in developing liquid fuels, and
de-ashing is necessary. Although in principle it seems to be atttractive
to remix all products of pyrolysis processing into one single liquid
biomass-derived fuel, this does not currently seem possible.
4.5 Chemicals
Many hundreds of chemical constituents have been identified to date
in pyrolysis liquids, and increasing attention is being paid to the
possibility of recovering individual compounds or families of chemi-
cals. The potentiallly much higher value of speciality chemicals
compared with fuels could make recovery of even small concentrations
viable. An integrated approach to chemicals and fuels production
offers interesting possibilities.
High temperature flash pyrolysis gives non-equilibrium chemicals
such as ethylene and propylene, but the concentrations are not
currently considered sufficiently high to make utilisation viable.
4.6 Water
A key feature of the pyrolysis process is that water is produced in
significant quantities of typically between 20 and 40% wt on the feed,
depending on feed moisture content. The water phase is highly
contaminated with dissolved and suspended organics, with a COD of
typically 150000. This therefore represents a major problem of
disposal or utilisation. This waste-water must be considered in the
specification, evaluation and selection of pyrolysis technologies. If
biological treatment is not appropriate or too expensive, part of the
heat of combustion of the products will be required for incineration of
this heavily contaminated water fraction. The pyrolysis gas could be
used for this purpose, but this may not be enough in cases where the
primary feedstock has a high water content and the gas is required for
feed drying.
Design specifications of future liquid fuel production processes are
likely to require oil condensation above 100C to avoid production of a
discrete water phase. The water and lower-boiling-point organics
would thus report to the gas stream to be burnt, i.e. incinerated.
The water content can be considered an advantage because it
reduces the viscosity of the liquid. In this respect, therefore, the raw
oil can be considered an outlet or disposal route for some of the
pyrolysis water. Phase separation is likely to occur at water concentra-
tions greater than 20%; it could only be counteracted by costly
30 A. V. Bridgwater & S. A. Bridge
emulsifiers. Moreover the water could render the oil more unstable
and more corrosive. Methanol has been suggested as a possible
additive but not evaluated.
Flash pyrolysis processes fed with a dried material with a moisture
content below about 10% wt will usually give a single homogeneous
product with no phase separation.
4.7 Gas fuel product
The gaseous product from pyrolysis is usually an MHV fuel gas of
about 15-22 MJ/Nm\ or an LHV fuel gas of around 4-8 MJ/Nm
3
from partial gasification depending on feed and processing parameters.
It has a high level of hydrocarbons, particularly methane, and
saturated and unsaturated hydrocarbons from the complex thermal
degradation processes. The heating value is enhanced if the gas is used
hot, from the sensible heat and the relatively high tar content. The gas
may be used for feed drying, process heating, power generation, or
exported for sale.
4.8 Pyrolysis status
A demonstration plant of 500 kg/h is currently operating in Italy for
liquid production, with plans for a series of small commercial units
there, in Spain, and in Greece. A number of demonstration plants
for flash pyrolysis are operating in North America at a scale of up to
25 kg/h with plans for several commercial developments ranging up to
20 t/h, including a commercial installation planned for California
based on the SERI ablative pyrolyser. Examples of current activities
are described below in Section 5.
5 PYROLYSIS TECHNOLOGIES
Pyrolysis produces a solid char, liquid products (tar and pyroligneous
acid) and a fuel gas, the proportions of which are dependent on the
process conditions and the nature of the feedstock. It has been found
that heating rate and temperature play an important role in the
distribution of the pyrolysis products. At low heating rates between
001 and 2C/s and at relatively low temperatures of less than 500C,
char, gas and liquid products are produced in approximately equal
amounts. Flash and fast pyrolysis are claimed to involve extremely
high heating rates from 1000C/s up to 1 X 10
6o
C/s. This high heating
Review of Biomass Pyrolysis Technologies 31
rate and the very low residence times maximise the production of
liquid products (at temperatures up to 600C) or gaseous products (at
temperatures above 700C) while minimising char formation.
Examples of recent and/or well developed pyrolysis activities are
summarised below to show how different groups of researchers have
tackled the problems of high heating rate, low temperature and rapid
quenching of products to maximise yields of preferred products. The
examples are listed in Table 10 with cross-reference to the section
where they are described, and the key features of each process are
summarised in Table 11. The rest of this chapter is devoted to a
description of each of the processes referred to in Tables 10 and 11.
5.1 Conventional pyrolysis for liquids
Example: Alten-Alternative Energy Technologies (a consortium of
KTI and I talenergie, but no longer in partnership)
The aim of this activity was to develop a small-scale pyrolysis process
to convert wood and agricultural wastes into marketable fuel products
such as fuel oil, charcoal and char-water slurries. The application
envisaged was a network of small-scale pyrolysis plants to produce
bio-oil to fire a 27 MW power station in the context of the A vezzano
LEBEN project.
5.1.1 Introduction
The pyrolysis plant, developed by Alten (KTI and Italenergie), has
been in operation since 1985, and is the largest biomass pyrolysis unit
dedicated to bio-oil production in Europe. The design capacity of the
plant was 1 t/h dry biomass, but only 300-500 kg/h has been achieved
on a continuous basis.
5.1. 2 Description and operation
Figure 5 shows the arrangement of equipment, and Fig. 6 is a
flowsheet of the process.
The feed is screened, rechipped and dried in a rotary drier before
entering the fluid-bed reactor. Drying fuel is currently propane, but
the product fuel gas would be used in a commercial venture. Air is
added to the reactor to give a partial gasification reaction to provide
reaction heat. This results in a poor-quality, low-heating-value fuel
gas. The reaction temperature and pressure are about 500C and 1 atm
Table 10
Examples of pyrolysis technologies
Pyrolysis technology Organisation Section
Liquids
Conventional for liquids Alten (KTI + Italenergie) 5.1
Transport for liquids and Ensyn Engineering 5.2
gases
Fast entrained flow for Georgia Tech Research Inst. 5.3
liquids
Vacuum for liquids and Laval University 5.4
chemicals
Ablative for liquids and Solar Energy Research Inst. 5.5
chemicals
Low temperature for Tiibingen University 5.6
liquids and charcoal
Flash fluid bed for liquids Waterloo University 5.7
and chemicals
Solids
Conventional for charcoal Bio-Alternative SA 5.8
and liquids
Gases
Molten salt pyrolysis for Aston University 5.9
gases
Methanopyrolysis for Brookhaven National Lab. 5.10
gases and chemicals
Hydropyrolysis for gases Toronto University 5.11
and hydrocarbons
Twin fluid-bed fast TNEE 5.12
pyrolysis for gases
Free-fall radiation for University of Zaragoza 5.13
gases
Chemicals
Transport for liquids and Ensyn Engineering 5.2
gases
Vacuum for liquids and Laval University 5.4
chemicals
Ablative for liquids and Solar Energy Research Inst. 5.5
chemicals
Flash fluid-bed for Waterloo University 5.7
liquids, chemicals,
sugars; also
hydropyrolysis for
hydrocarbons
Molten salt for gases and Aston University 5.9
chemicals
Methanopyrolysis for Brookhaven National Lab. 5.10
gases and chemicals
Hydropyrolysis for gases Toronto University 5.11
and hydrocarbons
Review of Biomass Pyrolysis Technologies
Air
Quencher
Char
receiver
nS.ltI,m .
T tank
BIO-OIL
FIG. 5. Flow diagram-Alten.
Recycled
water
33
Flare
Filter
respectively. The char formed is separated from the vapour stream in a
hot gas cyclone. The char is cooled in a sequence of water-cooled
screw conveyors and stored in a silo.
The vapour and gas streams pass through a quench vessel where
they are cooled and condensed by direct contact with recycled product
water. The mixture of oil and water is separated in a settlement tank
before sending the oil to storage and recycling the water through an air
cooler. Excess water is removed to maintain a constant-height
interface. The resulting water condensate has a very high COD at
around 150000 and requires treatment prior to disposal. Further liquid
is removed from the product gas in a cyclone and filter, before burning
the gas in a flare.
The gas from the drier is also sent to the flare to eliminate
pollutants. If the gas is required for electric power generation, the gas
would have to be first cooled and dried to about 30C before used in a
gas engine. The gas may also be used internally as a fuel source for
drying the feed, or for other process heat applications.
Feedstocks tested include wood chips, olive husks, straw and vine
trimmings.
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Review of Biomass Pyrolysis Technologies
Table 12
Typical mass balance
Inputs (kg) Outputs (kg) HHV
(Mf/kg)
Dry biomass 1O()0 Charcoal 205 297
Moisture 20 Bio-oil 205 263
Pyrolysis air 39() Fuel gas 1000 41
Losses
Total 141() Total 141()
Basis: 100 kg dry ash free (d.aJ.) biomass feed.
5. 1.3 Results
Energy (%)
32
28
32

100
A typical mass balance and energy output is shown in Table 12.
5.1. 4 Properties of products
37
The bio-oil is black and fairly viscous and contains a significant
proportion of charcoal of up to 15% by weight of the oil. This caused a
'lumpy' texture in early samples. A typical bio-oil analysis is shown in
Table 13, and a gas analysis in Table 14.
The char is a coarse powder with particle sizes ranging from 40 to
50,um to several millimetres, the particles are mainly needle-shaped
and similar to the size and shape characteristics of the feed. It has a
high porosity and a large surface area, about 15-20% volatiles, a very
Table 13
Typical bio-oil analysis
Elemental analysis % wt (wet basis)
C
H
N
S
a (by difference)
H/C ratio
OIC ratio
Moisture, % wt
Ash, %wt
Char content, % wt
Viscosity, cp at 70C
HHV, MJ/kg
Specific gravity (15/4C)
6190
600
105
()03
3102
116
018
1460
150
920
55
263
1195
38 A. V. Bridgwater & S. A. Bridge
Table 14
Gas analysis % vol., (dry basis)
CO 276
CO2 218
H2 47
O2
N2 382
CH
4
47
CzH4 04
CzH6 03
Others (by difference) 16
Higher heating value 5 MJ/Nm
3
low sulphur content and a low oxygen content. The char has an
empirical formula CHo.2500.07 and a higher heating value of
295 MJ/kg. Experiments are being carried out to obtain a pumpable
charcoal-water slurry that can be burnt in industrial installations. Up
to 60% weight solid slurries have been successfully produced. Char-
bio-oil slurries have also been produced, but the maximum solids
content is 30%.
5.1. 5 Special features and problems
This was the first substantial plant for bio-oil production to be
designed and built in Europe, and remains the only large-scale plant.
Its performance has not yet been optimised.
Particular problems reported include:
-reactor control of temperature and solids flow rate;
--<har separation from the pyrolysis vapours;
--<har in the bio-oil product;
-waste-water disposal;
-gas cleaning prior to flaring;
-drying energy requirement;
-scale-up.
5.1. 6 Bibliography
1. Antonelli, L., Agricultural and forestry wastes pyrolytic conversion. In
Energy from Biomass 4, Proceedings of the Third Contractors ' Meeting,
Paestum, 25-27 May 1988, ed. G. Grassi, D. Pirrwitz & H. Zibetta.
Elsevier Applied Science, London, 1989, p. 485.
Review of Biomass Pyrolysis Technologies 39
2. Antonelli, L., Improvement of pyrolysis products: bio-oil and
biocarbon/emulsion and slurries. In Energy from Biomass 4, Proceedings of
the Third Contractors' Meeting, Paestum, 25-27 May 1988, ed. G. Grassi,
D. Pirrwitz & H. Zibetta. Elsevier Applied Science, London, 1989, p. 53l.
3. Antonelli, L., Improvement of Pyrolysis Conversion Technology Utilising
Agricultural and Forestry Wastes. EEC Contract No. EN3B-0121-1,
Interim and Final Reports, 1988, 1989.
4. Manufacturers' literature: ALTEN Consortium, Via Monte Carmelo 5,
0166 Roma, Italy.
5.2 Transport reactor for liquids and gases
Example: Ensyn Engineering Associates Inc., Canada
This project was initiated around 1986 with the main objective of
employing fast pyrolysis to produce non-equilibrium chemicals such as
ethylene and propylene on a continuous commercial scale. The process
can also be used to produce pyrolytic liquids for fuel oil and chemicals
production.
5.2.1 Introduction
Around 1981, a fast pyrolysis experimental programme (Ultrapyroly-
sis) was started at the University of Western Ontario in collaboration
with the Forintek Canada Corporation with support from the ENFOR
programme of the Canadian Forestry Service (Environment Canada
and Energy Mines and Resources, Canada). The aim was to develop a
new reactor design in order to exploit and optimise fast pyrolysis
product yields. An Ultra-Rapid Fluidised reactor (URF), with a
maximum feed rate of 1 kg/h, was designed and constructed.
The URF system utilises either a solid heat carrier, such as sand, or
a gas heat carrier, like nitrogen, to carry heat into a turbulent vertical
contactor (a cyclonic mixer termed a 'thermovortactor') where rapid
mixing between the feed particles and heat carrier occurs within 30 ms.
This rapid heating causes fast pyrolysis which leads to the production
of non-equilibrium chemical intermediates such as ethylene. This
reaction continues in the plug-flow entrained reactor. The reactor is a
1-m length of Inconel pipe heated by an electric oven. The products
are initially quenched in the 'cryovortactor' (also a cyclonic mixer with
cryogenic nitrogen as the coolant) while additional cooling is carried
out in a water-cooled coil heat exchanger. This cooling helps to freeze
the intermediates before subsequent decomposition and/or re-
polymerisation occurs.
40 A. V. Bridgwater & S. A. Bridge
Feed rates of up to 03 kg/h have been achieved along with reactor
temperatures in the range 650-1000C and gas residence times of
50-900 ms. Over 500 runs have been carried out using the above
system with feedstocks such as Avicel cellulose (100 mm powder), lEA
poplar, red maple and lignin. For cellulose, it was found that the
asymptotic total gas yield increased from 28% (by mass) to 88% as the
temperature is increased from 650 to 900C. Kinetic data have also
been obtained from this system.
The success of this process led to the design, construction and
testing of a Rapid Thermal Processing (RTP) reactor system, rated
nominally at 10 kg/h, which is about 20 times the capacity of the URF
system. Two additional upflow (transport) reactors have been designed
and tested at wood feedrates of 30 and 100 kg/h. Results were
Carrier gas
Char
drop-out
vessel
BIOMASS
Char
Sand
Liquid
FIG. 7. Flow diagram-Ensyn.
Liquid
Gas
Filter
cyclone
system
Review of Biomass Pyrolysis Technologies 41
consistent with the 10 kg/h downflow unit. Three more RTP units are
scheduled.
5.2.2 Description and operation
Figure 7 shows the arrangement of equipment, and Fig. 8 is a
flowsheet of the RTP downflow process. Upflow reactor patents have
been filed and are not disclosed at present.
Hot sand flows from two heat-carrier feeders to the jet reactor
system where they are injected towards the centre of the RTP reactor.
The feedstock is delivered from a feeder to the top of the reactor and
then injected into the cloud of turbulent hot solids. Heat is transferred
to the feedstock as the feed and hot sand are mixed together. After
mixing, the feed and sand pass through a tubular reactor, the length of
which can be adjusted to control the residence time. Furnaces are used
to heat the sand feeders, mixer and the reactor lengths, and these are
activated about 8 h before an experiment. The sand feeder ovens are
set at a temperature about 150C higher than the desired reaction
temperature to make up for the heat losses due to the
SAND BIOMASS

Heat carrier
Feeder
Electrostatic
feeder preCipitator
i
Filter
cyclone
i
Pyrolyser
f----
Quencher

Condenser

nd recycle
Char & sand
............................................
collector

FIG. 8. Flowsheet-Ensyn.

r---+

FUEL GAS.
CHEMICALS
LIQUID
PRODUCT
42 A. V. Bridgwater & S. A. Bridge
transport/reactor system and also to provide the heat required to raise
the feedstock from ambient to reaction temperature. The sand flow
rates are adjusted to maintain the desired reactor temperature and to
ensure isothermal conditions.
The products are rapidly quenched in a quench vessel and the solids
are removed in a drop-out vessel. A condenser and filter/cyclone
system are then used to separate the liquids from the gaseous
products. The fluid products are sampled and identified by standard
analytical procedures. An electrostatic precipitator is used when
aerosol yields are high.
Gas samples are collected in sampling bags and are analysed for
hydrogen, carbon dioxide, carbon monoxide and C
C
C
6
hydrocarbons.
5.2.3 Results
Table 15 shows typical results that were obtained using the RTP and
the URF unit. The results obtained are similar. The maximum total
liquid yield obtained from poplar to date is 80% at 500C and 250 ms.
The maximum total liquid yield from cellulose is 90% at 650C and
100 ms residence time, and for hardwood, maximum total liquid yield
is 77% at 550C and 250 ms residence time. Char yields ranged from
15% at 500C to approximately 3% at 800C. An analysis of the liquid
product has been carried out but results are not available. Over 900
experiments have been carried out with mass balance closures from 91
to 110%.
Table 15
Poplar pyrolysis-gas yields (dry wood basis)
RTP,20kg/h URF,
lkg/h
6500C 6500C 6500C 8000C 8000C 8000C
Residence time, ms 800 210 570 190 527 195
Gas composition,
% vol.
CO 165 135 433 380 419 400
CO2
99 69 68 84 108 100
Hz
01 01 05 05 09 08
CH
4
33 1-1 67 43 56 50
CzH4
16 14 40 33 43 39
Others 15 19 23 22 56 54
Total gas yield 329 249 636 567 691 651
Review of Biomass Pyrolysis Technologies 43
5.2.4 Special features and problems
Because sand is used to heat the feedstock instead of gas, the design is
more compact since the heat capacity of solids is higher per unit
volume than that of gas.
Solids are more easily separated from the product gas, allowing less
dilution and a corresponding higher energy density.
The size of a scaled-up reactor will depend to a large extent on the
heat flux.
Problems include:
-materials of construction at high temperature with abrasive solids,
which is overcome with the upflow design;
-residence time control in a scaled-up process.
5.2.5 Bibliography
1. Mok, L. K., Graham, R. G., Overend, R. P., Freel, B. A. & Bergougnou,
M. A., Ultra pyrolysis: the continuous fast pyrolysis of biomass. In
Bioenergy '84, GOteborg, Sweden, Vol. III, ed. H. Egneus & A. Ellegard.
Elsevier Applied Science London, 1984, p. 23.
2. Graham, R. G., Bergougnou, M. A., Mok, L. K., de Lasa, H. I. & Freel,
B. A., Ultrapyrolysis of cellulose and wood components. In 5th Canadian
Bioenergy R&D Seminar, ed. S. Hasnain. Elsevier Applied Science,
London, 1984, p. 386.
3. Graham, R. G., Bergougnou, M. A., Mok, L. K. S & de Lasa, H. I., Fast
pyrolysis (ultrapyrolysis) of biomass using solid heat carriers. In Funda-
mentals of Thermochemical Biomass Conversion, ed. R. P. Overend, T. A.
Milne & L. K. Mudge. Elsevier Applied Science, New York, 1985, p. 397.
4. Graham, R. G., Freel, B. A., Bergougnou, M. A., Overend, R. P. &
Mok, L. K., Fast pyrolysis of cellulose. In Energy From Biomass, 3rd EC
Conference, Venice, Italy, March 1985, ed. W. Palz, J. Coombs & D. O.
Hall. Elsevier Applied Science, London, 1985, p. 860.
5. Graham, R. G., Freel, B. A., Overend, R. P., Bergougnou, M. A. &
Mok, L. K., The kinetics of the fast pyrolysis of cellulose at 900C. In
Energy from Biomass and Wastes X, Washington DC, April 1986, ed.
D. L. Klass. Elsevier Applied Science and Institute of Gas Technology,
London, 1985, p. 593.
6. Graham, R. G., Freel, B. A. & Bergougnou, M. A., The production of
pyrolytic liquids, gas and char from wood and cellulose by fast pyrolysis. In
Research in Thermochemical Biomass Conversion, Phoenix, Arizona,
USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier Applied
Science, London and New York, 1988, p. 629.
5.3 Fast entrained-flow pyrolysis for liquids
Example: Georgia Tech. Research Institute, USA
This project was initiated in 1980 with the support from the US
Department of Energy (USDoE). Its aim is to determine the
44 A. V. Bridgwater & S. A. Bridge
conditions required to optimise oil yields from wood using an
entrained flow pyrolyser.
5.3.1 Introduction
Earlier research in the 1970s showed that higher oil yields could be
obtained by using a rotating-tube furnace (typically 28% wt) rather
than a stationary one (typically 17% wt). This increase was attributed
to the 'showering' of the wood particles through the gases in the
rotating-tube furnace as opposed to the 'packed-bed' mode of the
stationary type. Based on the above observation plus literature reports
on the pyrolysis of sawdust in fluidised beds, an entrained-flow bed
reactor was designed for the production of oil.
A process research unit was built and completed in 1983. In 1985,
modifications were made so that optimisation of the oil yield could be
further investigated, based on experience gained in the operation of
the pilot plant and the results of the commissioning runs. The major
changes were the replacement of the 8 in diameter (2032 cm) reactor
tube with a 6 in (1524 cm) tube, the addition of a quench vessel and a
BIOMASS
Pyrolyser
Loss in
weight Char
feeder
Mixer
section
Burner
Waste
water
-- Water
+--Air
io--"i....,....--.J+-- Propane
Air I propane
FIG. 9. Flow diagram-GTRI.
OIL
Gas to
flare
Review of Biomass Pyrolysis Technologies 45
second de mister. The nominal operating feed rate is 568 kg/h of dry
biomass.
5.3.2 Description and operation
Figure 9 shows the arrangement of equipment, and Fig. 10 is a
flowsheet of the process.
The feed is dried, hammer-milled to about 15 mm and fed from a
loss-in-weight feeder into the reactor via a rotary valve. The reactor
used is a 6 in inner diameter vertical tube made of stainless steel. The
initial feed point was the refractory-lined mixing section, located
below the reactor tube. However, by introducing the feed into feed
ports higher up the reactor, the effective length of the reactor could be
reduced, which in turn reduced the residence time.
The wood particles are entrained in a stream of hot combustion gas
(1700F, 927C) obtained by burning propane gas and air stoichi-
ometrically. Gas and wood flow concurrently upwards through the
reactor tube in which pyrolysis takes place; the resulting mixture
consists of non-condensable gases, water vapour (moisture plus
pyrolytic reaction water), pyrolysis oil vapours and char.
A cyclone separator is used to remove most of the char particles.
The exiting gas stream consists of non-condensable gases, water
vapour, pyrolysis oil vapours and some char fines. The hot effluent
enters a water-sprayed quench vessel where it is rapidly cooled. After
the quench vessel, the mixture enters an air-cooled condenser in
BIOMASS
Air
Propane
Loss in
weight
feeder
Pyrolyser
Inert gas
generator
Cyclone
Char
receiver
Quencher
Char
FIG. 10. Flowsheet-GTRI.
Gas to flare
BIO-OIL
46 A. V. Bridgwater & S. A. Bridge
which the pyrolysis vapours are condensed with some water vapour.
The condensed phases are removed via sumps and receivers and the
gaseous product is passed through two demisters connected in series.
Most of the aerosols present in the gaseous product are removed in the
demisters. The remaining effluent, consisting of non-condensable
gases, water vapour and remaining aerosols, enters a flare where it is
burnt and the combustion products are exhausted to the atmosphere.
5.3.3 Results
Table 16 shows some of the most recent results with liquid yields
approaching 60% wt on feed. Recent modelling and optimisation
studies have produced predictive models which indicate that yields of
70% wt are achievable with a well designed reactor and system.
5.3.4 Properties of products
The oils are highly oxygenated with no phase separation. They have an
initial boiling-point range from 70 to 90C. They are heat-sensitive and
will decompose when heated to temperatures greater than 185-195C.
The oils are acidic, have an acrid odour and also exhibit corrosive
properties with some metals. A typical bio-oil analysis is shown in
Table 17.
5.3.5 Special features and problems
A reactor model has been devised and tested that predicts that yields
of over 70% are achievable.
Recent design studies show that with current wood and biomass
prices in the USA, and current energy costs, a 2 tlh module can be
economically viable and give an acceptable payback time on the
investment.
In the scaled-up process waste-water production will be minimised
or eliminated by controlled cooling and condensation of oil.
Table 16
GTRI product yields (Modified Reactor)
Run no. 2-11/0 2-12/0 3-17 3-18 3-19
Temperature, C 501 524 499 504 500
Yields, % wt (dry ash-free feed)
Oil 481 538 521 600 549
Char 76 84 100 121 212
Total gas 443 378 379 279 239
By difference.
Review of Biomass Pyrolysis Technologies
Table 17
Typical bio-oil analysis from GTRI
Elemental analysis % wt (wet basis)
C
H
N
S
a
H/C ratio
OIC ratio
Moisture, % wt
Ash, %wt
Char content, % wt
Viscosity, cp at 60C
HHV,MJ/kg
Density, g/cm
3
Problems include:
395
75
<01
526
228
100
290
02
27-31
10
243
123
47
-accumulation of tarry material in the first stages of the air-cooled
condenser;
-design of high-temperature bio-oil cooler/condenser to avoid
water condensation;
-lack of operational experience on recycled product gas for reactor
heating.
5.3.6 Bibliography
1. Knight, J. A., Pyrolysis of pine sawdust. In Thermal Uses and Properties of
Carbohydrates and Lignins, ed. F. Shafizadeh et al. Academic Press, New
York, 1976, p. 159.
2. Knight, J. A., Gorton, C. W., Kovac, R. J., Elston, L. W. & Hurst, D. R.,
Oil production via entrained flow pyrolysis of biomass. In Proc. 13th
Biomass Thermochemical Conversion Contractors' Meeting, Arlington,
Virginia, 27-29 Oct. 1981, p. 475.
3. Knight, J. A., Gorton, C. W., Kovac, R. J. & Elston, L. W., Entrained
flow pyrolysis of biomass. In Proc. 14th Biomass Thermochemical
Conversion Contractors' Meeting, Arlington, Virginia, 23-24 June 1982,
p.250.
4. Knight, J. A., Gorton, C. W. & Kovac, R. J., Entrained flow pyrolysis of
biomass. In Proc. 15th Biomass Thermochemical Conversion Contractors'
Meeting, Atlanta, Georgia, 16-17 March 1983, p. 409.
5. Knight, J. A., Gorton, C. W. & Kovac, R. J., Entrained flow pyrolysis of
biomass. In Proc. 16th Biomass Thermochemical Conversion Contractors'
Meeting, Portland, Oregon, 8-9 May 1984, p. 287.
48 A. V. Bridgwater & S. A. Bridge
6. Knight, J. A., Gorton, C. W., Kovac, R. J. & Newman, C. W., Entrained
flow pyrolysis of biomass. In Proc. 1985 Biomass Thermochemical
Conversion Contractors' Meeting, Minneapolis, Minnesota, 15-16 Oct.,
1985, p. 99.
7. Kovac, R. J., Gorton, C. W., O'Neil, D. J. & Newman, C. J., Low
pressure entrained flow pyrolysis of biomass to produce liquid fuels. In
Proc. 1987 Biomass Thermochemical Conversion Contractors' Review
Meeting, Atlanta, Georgia, 20-21 May 1987, p. 23.
8. Elliott, D. c., Comparative analysis of gasification/pyrolysis condensates.
In Proc. 1985 Biomass Thermochemical Conversion Contractors' Meeting,
Minneapolis, Minnesota, 15-16 Oct. 1985, p. 361.
9. Baker, E. G. & Elliott, D. C., Catalytic upgrading of biomass pyrolysis
oils. In Research in Thermochemical Biomass Conversion, Phoenix,
Arizona, USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester.
Elsevier Applied Science, London and New York, 1988, p. 883.
5.4 Vacuum pyrolysis for fuels and chemicals
Example: University of Laval, Canada
The objective of this project is to investigate the potential of
low-pressure pyrolysis to produce high yields of condensable vapours
and to condense fractions selectively from different sections of the
reactor to examine the potential for fractionation and recovery of
chemicals.
5.4.1 Introduction
Early studies carried out by the University of Sherbrooke indicated
that pyrolysis under reduced pressure can be employed to convert
biomass into chemical and fuel products. This method is characterised
by low pressure and short residence time of the vapour products within
the reactor. A series of experiments were conducted batchwise by
using a retort operated at temperatures between 207 and 534C. The
optimum temperature range was found to be between 350 and 400C
and a yield of 60% wt (on a dry ash-free wood basis) of pyrolytic oil
was obtained at an average heating rate of lOoC/min and at a total
system pressure between 03 and 23 mm Hg (40-307 Pa). The feed-
stock used was aspen poplar. In view of the high yields of pyrolytic oil
obtained using low-pressure pyrolysis, a 30 kg/h vacuum pilot plant,
based on this technique, was designed, constructed and tested.
5. 4.2 Description and operation
Figure 11 shows the arrangement of equipment, and Fig. 12 is a
ftowsheet of the process.
Scraper
rachet
Multiple
hearth
reactor
BIOMASS
Review of Biomass Pyrolysis Technologies
Charcoal
receiver
Primary condensing
unit
Collection
vessel
LIQUID
PRODUCT
Secondary
condensing
unit
FIG. 11. Flow diagram-University of Laval.
FIG. 12. Flowsheet-University of Laval.
Gas to
analysis
Vacuum
pump
49
Gas to
flare
Gas to flare
50 A. V. Bridgwater & S. A. Bridge
The feed is woodchips with a particle size from to ! in Tyler mesh
(6 mm to 127 mm). They are fed via a hopper on the top of the
reactor, which is hermetically sealed. This is equipped with a
variable-rate feeding device that feeds the chips into the preheated
reactor at a constant feed rate of between 08 and 4 kg/h.
The reactor is a multiple-hearth furnace 2 m high and 07 m
diameter, with six hearths. Electric heating elements are used to heat
the reactor. The temperatures of the heating plates increase from top
to bottom of the reactor. A typical temperature profile is 200 to 400C.
At steady-state conditions, the absolute system pressure of the system
is less than 80 mm Hg (107 kPa). The organic vapours and gaseous
products are removed from the reactor by a mechanical vacuum pump
via six outlet manifolds which correspond to the six heating plates. The
char falls to the bottom of the reactor where it is collected in a metallic
jar on a load cell. The process unit is connected to a central
microprocessor which simultaneously gathers data and controls about
75 operating parameters.
The clean-up system is a series of shell and tube heat exchangers
(primary condensing unit) and a train of receivers (secondary con-
densing unit). Each outlet manifold is connected to a heat exchanger
where the vapours are condensed and recovered as organic liquid in
individual receivers. Cool-to-warm tap water is used as the cooling
medium on the shell side. The vapours from the heat exchangers are
then collected in the secondary condensing unit where the aqueous
phase is primarily recovered. The first receiver is immersed in a bath
of water-ethylene glycol mixture. The next two are immersed in baths
of dry ice-acetone while the final receiver is filled with glass wool at
room temperature. The non-condensable gases are pumped into a
SOO-litre vacuum vessel.
5.4.3 Results
Some results obtained using the multiple-hearth reactor are shown in
Table 18. The highest yields of 'bio-oil' are obtained at the lowest-
pressure and the higher-temperature conditions. The optimum tem-
perature range for maximum oil yield from wood was found to be
between 425 and 450C at the bottom of the reactor.
One potential advantage of using a multiple-hearth reactor con-
figuration is the capacity to fractionate the pyrolysis products by use of
multiple outlets at different levels (see Table 19). The separation of
the aqueous and the oil phases is important at the industrial level
Review of Biomass Pyrolysis Technologies 51
Table 18
Product yields for low-pressure pyrolysis at Laval University
Temperature, C 425 363 465 450
Pressure, mm Hg 12 18 80 12
Feedstock, kg 598 599 339 1543
Yields, % wt (wood organic basis)
Oil 464 416 397 509
Water 182 149 216 165
Char 242 330 247 213
Total gas 112 105 140 113
Gas composition, % vol. (dry basis)
CO 592 604 600 607
CO
2
336 349 314 316
CH4
24 09 33 27
H2
09 01 07
Others 39 37 46 50
because the recovery of chemicals during distillation of large amounts
of water is less economical.
5.4.4 Properties of products
A typical analysis of the oil is shown in Table 20. This oil is highly
oxygenated and consists of phenols, sugars and both aliphatic and
aromatic hydrocarbons. The gases are mainly CO and CO
2

Table 19
Separation of water and pyrolytic oil during condensation
Run no. Reactor Temperature, C Primary Secondary
Pressure condensing condensing
(mmHg) Hearth Cooling Unit" Unit"
VI water
Oil Water Oil Water
(%) (%) (%) (%)
C019 80 465 11-28 522 192 74 212
C023 12 450 50-55 322 15 367 296
C024 30 450 30-35 398 16 272 314
C025 10 450 15-20 478 34 272 216
"Percentages are based on total condensates.
52 A. V. Bridgwater & S. A. Bridge
Table 20
Elemental analysis of bio-oil from Laval
University
Elemental composition, % wt
Carbon 499
Hydrogen 70
Oxygen 430
Nitrogen
HIC ratio 168
OIC ratio 065
Ash
Moisture 184
Density, g/cm
3
at 55C 123
Viscosity, cp
Heating value, MJ/kg 211
5.4.5 Special features and problems
Low pressure removes the primary products quickly and avoids
secondary reactions.
Fractionation provides some separation of liquids evolved at
different temperatures in a continuously operating system.
Recent testing of this unit at throughputs of 30 kg/h showed that the
primary condensing unit composed of six shell and tube heat exchan-
gers was inefficient due to clogging problems. The six individual
exchangers were substituted by a single spray-type condensing unit,
similar to the secondary condensing unit. The new system proved to
work very satisfactorily.
Other problems include:
-heat transfer to the hearths in a scaled-up operation;
-high volume of reactor and other equipment from vacuum
operation;
--development of very large-capacity vacuum pumps;
-uncertain scale-up potential for wood feedstocks.
5. 4. 6 Bibliography
1. Roy, C., de Caumia, B., Brouillard, D. & Menard, H., The pyrolysis
under vacuum of aspen poplar. In Fundamentals of Thermochemical
Biomass Conversion, ed. R. P. Overend, T. A. Milne & L. K. Mudge.
Elsevier Applied Science, New York, 1985, p. 237.
Review of Biomass Pyrolysis Technologies 53
2. Lemieux, R., Roy, C., de Caumia, B. & Blanchette, D., Preliminary
engineering data for scale-up of a biomass vacuum pyrolysis reactor. In
ACS Symposium, Production Analysis and Upgrading of Oils from
Biomass, Denver, CO., April 1987, p. 12.
3. Roy, C., de Caumia, B. & Pakdel, H., Preliminary feasibility study of the
biomass vacuum pyrolysis process. In Research in Thermochemical Biomass
Conversion, Phoenix, Arizona, USA, April 1988, ed. A. V. Bridgwater &
J. L. Kuester. Elsevier Applied Science, London, 1988, p. 585.
4. Roy, C., de Caumia, B., Brouillard, D. & Lemieux, R., Development of a
biomass vacuum pyrolysis process for the production of liquid fuels and
chemicals. In Energy from Biomass and Wastes IX, Lake Buena Vista,
Florida, 28 Jan.-1 Feb., 1985, p. 1085.
5. Baker, E. G. & Elliott, D. c., Catalytic upgrading of biomass pyrolysis
oils. In Research in Thermochemical Biomass Conversion, Phoenix,
Arizona, USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier
Applied Science, London and New York, 1988, p. 883.
6. Pakdel, H., Roy, C. & Zeidan, K., Chemical characterization of hydrocar-
bons produced by vacuum pyrolysis of aspen poplar wood chips. In
Research in Thermochemical Biomass Conversion, Phoenix, Arizona,
USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier Applied
Science, London, 1988, p. 572.
7. Roy, c., De Caumia, B. and Plante, P., Performance study of a 30kg/h
vacuum pyrolysis process development unit. In 5th European Conference on
Biomass for Energy and Industry, ed. G. Grassi, G. Gosse & G. dos
Santos. Elsevier Applied Science, London, 1990, p. 2.595.
5.5 Ablative pyrolysis for liquids and chemicals
Example: Solar Energy Research Institute, USA
The original aim was to convert biomass into non-equilibrium gases in
a low-pressure process without the addition of a catalyst. This aim was
modified in 1984 to produce liquid fuels in high yield, and more
recently it has been modified again to consider production of hydro-
carbon fuels such as gasoline, aromatics such as benzene, xylene and
toluene, and chemical fractions such as polyphenols.
5.5.1 Introduction
In 1980 it was demonstrated that when biomass was moved relative to
a red-hot nichrome wire, rates of pyrolysis of up to 3 cm/s were
measured as a localised surface phenomenon. Extremely high heat
fluxes were attained by this technique and it was found to be two
orders of magnitude greater than black-body radiation at similar wall
temperatures.
54 A. V. Bridgwater & S. A. Bridge
Initially a smooth-walled vortex reactor without a recycle loop,
made from Inconel 800H in order to withstand temperatures of
1000C, was used. However, early experimentation demonstrated that
severe coke deposits were formed at wall temperatures much above
625C. Since a lower reactor temperature of 625C was needed, a
vortex reactor made from stainless steel was designed, constructed and
tested. Very high organic vapour yields resulted from this lower wall
temperature operation. The design capacity of the vortex reactor is
50 kg/h biomass but the maximum throughput achieved to date is
32 kg/h.
5.5.2 Description and operation
Figure 13 shows the current configuration of the reactor system and
Fig. 14 is a ftowsheet of the process. Biomass, with a particle size of
about 5 mm, is metered into the system, where it is entrained and
mixed with the recycled stream. The biomass particles, entrained in
the carrier gas, enter the vortex reactor tangentially at speeds of over
400 m/ s so that the particles are forced to the reactor wall by high
centrifugal forces.
The reactor is made from 316 stainless steel with a diameter of
134 cm and a length of 70 cm. The reactor is heated externally by
three electric cylindrical furnaces. To force the particles into tighter
helical paths than would naturally occur, a helical rib having a pitch of
25 mm and width and height of 3 mm was machined from the wall of
Feed
hopper
100C
ejector
FIG. 13. Flow diagram-Solar Energy Research Institute.
GAS
at 5C
LIQUID
product
BIOMASS
Carrier
gas
Review of Biomass Pyrolysis Technologies 55
FIG. 14. Flowsheet-Solar Energy Research Institute.
the reactor. An insulated recycle loop is also added tangentially at the
exit of the reactor to recycle partially pyrolysed feedstock and any
large char particles. The fine char, gases and vapours in the reactor
leave through the axial exit which extends part way into the reactor.
The wall temperature has to be limited to a maximum of about
625C to ensure production of a liquid film between the wall of the
reactor and the particle, which then vaporises and leaves the reactor.
Higher wall temperatures result in solid coke formation on the wall
which prevents rapid particle movement and quickly fouls the heat-
transfer surfaces of the reactor.
The product stream then passes through a char cyclone where the
char is removed. The diameter is 4 in (10 cm) and operates at
475-500C. The vapours pass to the first heat exchanger which is a
38 cm diameter cyclone. The condensed liquids and water are retained
in the receiver. The cooled gas stream at about 80C is then passed to
a series of heat exchangers before passing through an orifice meter,
and then to flare.
5.5.3 Results
Using this experimental layout, oil yields of 67% wt (including
moisture on a wet feed basis) or 55% (dry oil/on dry feed basis) have
been obtained with about 10% wt (on a dry feed basis) char.
56 A. V. Bridgwater & S. A. Bridge
5.5.4 Properties of products
The liquid obtained is highly oxygenated, dark brown in colour and
acidic with a pH between 2 and 3. Because of this acidity, the oil has
been stored in glass or stainless steel tanks. The aqueous and the
organic condensates are dissolved in each other. If nitrogen is used
rather than steam as the carrier gas, an organic phase and an aqueous
phase are both present at water contents above about 25%. Small
samples of the oil have appeared to be stable at room temperatures for
a prolonged time but exothermal reactions will occur if the tempera-
ture of the oil is raised to lOOC or more. The fresh oil vapours have
been found to irritate the eyes and the nose; however, when tested to
investigate whether they were carcinogenic with cancer-prone mice,
they were found not to promote cancer formation cells. Analytical
data are given in Table 21.
The phenol fraction has been successfully extracted and polymerised
with formaldehyde to form a plywood resin. This process is being
yommercially exploited.
While municipal solid waste (MSW) has been successfully pyrolysed,
problems arose from early deposition of an asphalt-like condensate
(having a melting point of around 80C) in the first heat exchanger,
which required modification of the condenser train.
The char from wood has a volatile content of 15-45%, a bulk
density between 018 and 024 g/ cm
3
and a higher heating value of
33 MJ/kg. The empirical formula is CHo.5300.12'
Table 21
Elemental analysis of bio-oil from the SERI process
Elemental composition, % wt (on feed)
Carbon
Hydrogen
Oxygen
Nitrogen
H/C ratio (atomic)
O/C ratio (atomic)
Ash
Moisture
Density, g/cm
3
at 55C
Viscosity, cp
Heating value, MJ Ikg
a Calculated.
486
72
442
<01
178
068
123
544
57
398
<01
126
055
005
15
90 at 30C
223
a
203
Review of Biomass Pyrolysis Technologies 57
5.5.5 Special features and problems
Very high heat transfer rates are achieved between the hot wall and
biomass particles centrifuging against the hot reactor wall . Unpyrolysed
material is easily recycled through the solids recycle loop. The reactor
has a very high specific capacity and can in principle be easily
scaled-up. Although the heat transfer is novel, it has been modelled on
the basis of first principles.
Zeolite synthesis of gasoline and aromatics has been demonstrated
on a slipstream. Recovery of phenolics for resin production is being
commercialised.
The concept is planned to be scaled-up for liquid fuel production by
Interchem-Pyrotech Inc. in Northern California.
Problems include:
-recovery of the oils has proved to be difficult because of their
volatility (due to aldehydes) and their tendency to form stable
aerosols;
-many of the condensables are water-soluble;
-MSW pyrolysis gives a heavier and more viscous product with a
high melting point that requires different handling and recovery.
5.5.6 Bibliography
1. Diebold, 1. P., Ablative pyrolysis of macroparticles of biomass. In
Proceedings of the Specialists' Workshop on the Fast Pyrolysis of Biomass,
Copper Mountain, Colorado, October 1980. Solar Energy Research Insti-
tute, Golden, Colorado 80401, SERI/CP-622-1096, p. 237.
2. Diebold, J. P. & Scahill, J. W., Ablative entrained-flow fast pyrolysis of
biomass. In Proc. 16th Biomass Thermochemical Conversion Contractors'
Meeting, Portland, Oregon, 1984, p. 319.
3. Diebold, J. & Scahill, 1., Production of primary pyrolysis oils in a vortex
reactor. In ACS Symposium, Production Analysis and Upgrading of Oils
from Biomass, Denver, CO, April 1987, p. 21.
4. Diebold, 1. P. & Power, A. 1., Engineering aspects of the vortex pyrolysis
reactor to produce primary pyrolysis oil vapours for use in resins and
adhesives. In Research in Thermochemical Biomass Conversion, Phoenix,
Arizona, USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier
Applied Science, London and New York, 1988, p. 609.
5. Baker, E. G. & Elliott, D. c., Catalytic upgrading of biomass pyrolysis
oils. In Research in Thermochemical Biomass Conversion, Phoenix,
Arizona, USA, April 1988, ed. A. V. Bridgwater & 1. L. Kuester. Elsevier
Applied Science, London and New York, 1988, p. 883.
6. Diebold, 1., Evans, R. & Scahill, 1., Fast pyrolysis of RDF to produce fuel
oils, char and a metal-rich by-product. In Energy from Biomass and Wastes
XIII, ed. D. Klass. IGT, 1989.
58 A. V. Bridgwater & S. A. Bridge
5.6 Low-temperature pyrolysis for liquids and charcoal
Example: Tubingen University, Germany
The objective of this research is to convert biomass such as sewage
sludge, agricultural wastes and refuse/MSW into fuels or raw materials
for the organic chemicals industry.
5. 6.1 Introduction
This process was developed as an alternative solution to landfill and
incineration of sewage sludge. Several batch and continuous
laboratory-scale plants up to 5 kg/h have been built and tested. The
principle is to use low temperatures of less than 350C and long
reaction times of up to an hour to achieve low oxygen content oils and
high yield of fine chemicals. The principle has been licensed to several
organisations in Europe, North America and Australia and several
plants of up to 2 t/h are operating or under construction based on
sewage sludge or MSW.
5.6.2 Description and operation
Figure 15 shows one configuration of the reactor system based on
dried sewage sludge, and Fig. 16 is a conceptual ftowsheet of the
process based on refuse/MSW.
BIOMASS
Feeder
hopper
Augur kiln
Char
receiver
Char and ash
FIG. 15. Flow diagram-University of Tiibingen.
Gas to
analysis
and meter
Review of Biomass Pyrolysis Technologies 59
BIOMASS
14-__ .--_R_a_w..::.
g
a_S_IO--,' p_,oc_e_SS_h_ea_! GAS surplus
BIO-OIL
FIG. 16. Flowsheet-University of Tiibingen.
At a laboratory scale, both batch and continuous-screw reactors
have been used. Sludge dewatered to about 20% wt solids, or other
biomass, is heated slowly to 300-350C in an oxygen-free environment
for about 20 min, and the liquid product collected in an ice-cooled
bath. The continuous-screw reaction system is shown in Fig. 15. No
additives are needed as the silica, silicates and heavy metals present in
the sludge are claimed to act as catalysts. The vapour is condensed and
collected. Feedstocks tested include sewage sludge, rape, lupine and
Euphorbia.
Four types of equipment have been used on a larger scale for
low-temperature conversion. These are a rotary furnace (up to
80 kg/h), a fluidised bed (up to 400 kg/h), a reactor with a transport
belt for MSW conversion (up to 200 kg/h) and a cone screw converter
for the conversion of agricultural wastes.
5. 6.3 Results
Oil yields ranging from 18 to 27% wt (feed basis) and char yields from
50 to 60% wt (feed basis) have been achieved.
5.6.4 Properties of products
Table 22 shows the elemental analysis of the products.
60 A. V. Bridgwater & S. A. Bridge
Table 22
Elemental analysis of products [5]
Oil Char Water vapour Product water
C 7262 3505 059 433
H 1075 292 1154 1053
N 127 124 009 035
CI 006 108 006
S 024 015 014
o (by difference) 1506 859 8763 8459
Others 5112
5.6.5 Special features and problems
Liquids with very low oxygen content (less 5% wt oxygen) have
been reported from a sewage sludge feed. The low oxygen level and
chemical intermediates are claimed to be due to low reaction
temperature, natural catalysts in the feed and slow reaction times. The
oils contain aliphatic hydrocarbons and fatty acids as the main
components.
The oil derived from sewage sludge has been reported as being used
as fuel for a diesel engine.
Problems include:
-lack of definitive reaction mechanisms and pathways to account
for low oxygen content liquids.
5.6. 6 Bibliography
1. Bayer, E., Niedertemperaturkonvertierung von Kliirschlamm zu 01, Baden-
Baden, 25-26 Oct., 1984, p. 141.
2. Bayer, E. & Kutubuddin, M., 01 aus Kllirschlamm. In lahrbuch Wasser
Versorgungs und Abwasser Technik, Ausgabe 85/86, p. 563.
3. Bridle, T. R., Campbell, H. W., Sachdev, A. & Marvan, I., Thermal
conversion of sewage sludge to liquid and solid fuels. Paper presented at
1983 CSChE Conference, Toronto, Oct. 1983.
4. Bridle, T. R., Sludge derived oil : wastewater treatment implications.
Environmental Technology Letters, 3 (1982) 151.
5. Bayer, E., Niedertemperaturkonvertierung, ein Konzept zur um-
weltschonenden Abfallbehandlung, Essen, 14-17 Sept. 1988 (leaflet).
6. Bayer, E. & Kutubuddin, M., Thermocatalytic conversion of lipid-rich
biomass to oleochemicals and fuel. In Research in Thermochemical Biomass
Conversion, Phoenix, Arizona, USA, April 1988, ed. A. V. Bridgwater &
J. L. Kuester. Elsevier Applied Science, London and New York, 1988,
p.518.
Review of Biomass Pyrolysis Technologies 61
5.7 Flash pyrolysis in a shallow fluid bed for liquids
Example: University of Waterloo, Canada
This programme was initiated in the early 1980s with the main
objective of establishing conditions for maximising liquid yields from
biomass, particularly from forest materials.
5.7.1 Introduction
Initially, a bench-scale continuous flash pyrolysis unit using a fluidised
bed at atmospheric pressure was employed. The reactor conditions
used were feed rates of up to 50 g/h with a particle size range between
140 and 60 mesh (between 105 and 250 f.lm) in a nitrogen atmosphere
over a temperature range of 400-650C. Results indicated that at an
apparent vapour residence time of 05 s, organic liquid yields of
60-70% (moisture-free) could be obtained from hardwoods such as
aspen poplar and maple whilst yields of 40-60% could be obtained
from agricultural wastes such as wheat, straw, corn stover and bagasse.
Using the results obtained from the bench-scale unit, a larger process
unit of 3 kg/h was designed, constructed and tested. This has been
extensively studied and a 200 kg/h pilot plant based on results from
this unit is being constructed in Spain.
5. 7. 2 Description and operation
A flow diagram of the 3 kg/h process unit at Waterloo is shown in Fig.
17, and a flowsheet in Fig. 18. The wood is air-dried (to 7% wt
moisture), hammer-milled and screened to a particle size of 595 f.lm
(30 mesh) . The wood is then conveyed from a hopper by a variable-
speed twin-screw feeder into a cavity where it is conveyed into the
reactor by recycled product gas. The feed injection point is within the
bed itself. The reactor bed material is sand and the fluidising agent is
recycled product gas (a CO-C0
2
-CH4 mixture) which is preheated in
the inlet line by controlled electric heaters. In addition, the reactor is
wrapped with heating coils allowing extra heat to be added either to
the bed of sand or to the freeboard space. The feed hopper and feeder
are mounted on a hinged platform resting on a load cell, and hopper
weight loss is continuously recorded.
The fluid bed was designed to entrain the char and blow it from the
bed while retaining the sand. This is done by careful selection of sand
size, biomass particle size, bed velocity and reactor configuration. This
is called the 'blow-through' mode of operation since there is a
62
BIOMAS
A. V. Bridgwater & S. A. Bridge
BIOMASS
Ballast .-----'_-,
tank
Hot
water
condenser
Ice
water
condenser
SIO-Oll
To gas analysis
Filter
--+- To vent
Compressor
FIG. 17. Flow diagram-University of Waterloo.
Recycled product gas
FIG. 18. Flowsheet-University of Waterloo.
Gas analyser
and flare
Review of Biomass Pyrolysis Technologies 63
negligible amount of char present in the sand and hence there is no
need for sand circulation or replacement.
The reaction temperature (from 425 to 625C) is controlled by a
thermocouple within the fluid bed which regulates the inlet gas heating
coils. The reactor pressure of about 125 bar (125 kPa) absolute is
monitored by differential and absolute bellows-type gauges.
Throughputs from 15 to 3 kg/h have been used.
The reaction products pass through a cyclone where char is
removed. The vapours and the gaseous product pass through two
condensers in series. These condensers are vertical and have pyrolysis
gas inside the tubes; each condenser has a clean-out plug at the top
and a condensate collection pot at the bottom. The first condenser is
held at about 60C while the second one uses chilled water at about
OC as the cooling medium. Tarry products are collected in the
condensers. The effluent gases then pass through a filter to remove tar
mist and then to a recycle compressor. A proportion of this gas stream
is taken from the compressor discharge and used to fluidise the reactor
bed and convey feed into the reactor, while the excess is vented
through a gas analyser and gas meter as product gas. The product gas
is analysed for CO and CO
2
in an on-line infrared gas analyser-
recorder. Samples of the product gas are also taken periodically and
analysed by gas chromatography.
5. 7.3. Results
High yields of liquid product were obtained at temperatures around
500C which is believed to be due to minimum secondary decomposi-
tion reactions occurring at such low temperatures (see Table 23).
5. Z 4 Properties of products
The liquid product is highly oxygenated with no phase separation. It
has a low viscosity and contains 10-20% wt water depending on the
moisture content of the feedstock and the reaction temperature
employed. It is dark in colour with an acrid smell. The liquid is quite
stable at room temperature over a 12-month period. Some properties
of the liquid product are outlined in Table 24.
The gas produced has a higher heating value of about 144 MJ/Nm
3
.
This value increases at higher reaction temperatures as the CH
4
content increases and the CO
2
content decreases.
64 A. V. Bridgwater & S. A. Bridge
Table 23
Reported pyrolysis yields from different woods at optimal conditions
Temperature, C
Moisture content, % wt
Particle top size, mm
Apparent residence
time, s
Feed rate, kg/h
Yields, % wt
(dry wood basis)
Water
(reaction product)
Char
Organic liquids (dry)
Gas composition
(% wt dry wood basis)
CO
CO
2
H2
CH
4
CzH4
Others
Total gas
Brockville
poplar
471
589
002
044
019
025
1150
504
520
1000
047
210
970
1650
6290
White
spruce
382
337
002
038
017
004
780
500
700
1000
065
191
1160
1220
6650
Red
maple
412
489
001
036
016
026
980
508
590
590
047
198
980
1375
6790
Table 24
Properties of pyrolytic liquids
Elemental analysis,
C
H
o (by difference)
H/C ratio
O/C ratio
Water content, % wt (wet)
pH
Density, gl cm
3
Higher heating value, MJ Ikg
Brockville
poplar
5470
690
3840
151
053
1870
240
120
2320
White Red
spruce maple
5400
680
3920
155
054
2240
210
122
2270
5470
640
3890
140
053
1800
240
1-19
2240
Review of Biomass Pyrolysis Technologies 65
5. 7.5 Special features and problems
Char and sand separation is avoided by entraining the char.
The shallow-bed reactor which may have scaling problems from bed
instability at high throughputs/large diameters.
Recycled gas is used for ftuidisation and blanketing, thus avoiding
dilution.
Problems include:
-stable tar aerosols are formed which pass readily through the
condensers and require special handling; electrostatic pre-
cipitators work well.
5. Z 6 Bibliography
1. Scott, D. S. & Piskorz, J., The flash pyrolysis of aspen-poplar wood. Can.
J. Chern. Eng., 60 (Oct. 1982) 666.
2. Scott, D. S. & Piskorz, J., The continuous flash pyrolysis of biomass. Can.
J. Chern. Eng., 62 (Jun. 1984) 404.
3. Scott, D. S., Piskorz, J. & Radlein, D., Liquid products from the
continuous flash pyrolysis of biomass. Ind. Eng. Chern. Process Des. Dev.,
24 (1985) 581.
4. Scott, D. S., Piskorz, J., Grinshpun, A. & Graham, R. G., The effect of
temperature on liquid product composition from the fast pyrolysis of
cellulose. In ACS Symposium on Production, Analysis and Upgrading of
Pyrolysis Oils from Biomass, Denver, Colorado, April 1987, p. 1.
5. Scott, D. S., Piskorz, J., Bergougnou, M., Graham, R. G. & Overend, R.
P., The role of temperature in the fast pyrolysis of cellulose and wood. Ind.
Eng. Chern. Process Des. Dev., 27 (1988) 8.
6. Scott, D. S. & Piskorz, J., The composition of oils obtained by the fast
pyrolysis of different woods. In ACS Symposium on Production, Analysis
and Upgrading of Pyrolysis Oils from Biomass, Denver, Colorado, April
1987, p. 215.
7. Piskorz, J., Radlein, D. , Scott, D. & Czernik, S., Pretreatment of wood
and cellulose for production of sugars by fast pyrolysis. J. Anal. Appl.
Pyrolysis, 16 (1989) 127,
5.8 Conventional fixed-bed pyrolysis for charcoal and bio-oil
Example: Bio-Altemative SA, Switzerland
The objective is the production from the pyrolysis of wood and solid
wastes of solid fuels and liquid fuel by-products which can be stored
and transported easily.
5.8.1 Introduction
The company was started in 1983 as Bio-Carbon Neuchatel SA, and
later changed its name to Bio-Alternative SA (BASA). A continuous,
66 A. V. Bridgwater & S. A. Bridge
integrated carbonisation demonstration plant process is situated at the
company's headquarters and several commercial sales have been made
of up to 2 t/h capacity. The charcoal can be used as fuel or converted
to char slurries, and the liquid product-bio-oil-has been successfully
used as a boiler fuel.
5.8.2 Description and operation
A flow diagram of the 50 kg/h pilot plant in Switzerland is shown in
Fig. 19, and a flowsheet in Fig. 20. Biomass with particle sizes ranging
BIOMASS


Twin
lock
hoppers
Feed
hopper
CHARCOAL
Hot raw gas:
either to boiler,
or to gas cleaning
and cooling train for
power generation
OIL
FIG. 19. Flow diagram-Bio-Alternative.
Review of Biomass Pyrolysis Technologies 67
Tars
BIOMASS
POWER
BIO-OIL
FIG. 20. Flowsheet-Bio-Alternative.
from 5 to 500 mm is first crushed and dried (optimal moisture content
10-15% wt) before being transported to the top of the reactor from a
feed hopper. The temperature at the top of the reactor is about 120C.
Feed rates of 40-100 kg/h have been used in the pilot plant.
The pyrolysis pilot unit is a vertical cylinder about 3 m high and 1 m
in diameter. It is fitted with an interlocked twin-feed hopper fed by
screw feeder. A horizontal stirrer and a vibrator are used to prevent
bridging of the feed in the reactor. The heat necessary for the reaction
is obtained through internal combustion, regulated by a system of air
injection into the reactor through tuyeres. Temperature probes are
used to measure the temperatures in the reactor. At the edge of the
reactor, temperatures of about 1000C have been measured. However,
the temperatures in the interior of the reactor are lower and this
results in a radial temperature gradient. The pressure of the system is
between 2 and 5 mbar (200-500 Pa) below atmospheric.
Char is removed through a rotary valve at the base of the reactor
and through a water-cooled system (an endless screw) which is at
4O-50C. The char product is stored in plastic bags or steel containers.
Product gas leaves the top of the reactor at 120C containing tar
vapours and moisture. This is contacted with hot pyrolysis oil at
l1O-120C which condenses the tar but leaves the water vapour in the
68 A. V. Bridgwater & S. A. Bridge
gas phase. A sight-glass is used to control the liquid level in the
contactor and the excess liquid is periodically removed by manual
discharge. The gas with about 10-20% water is then blown to a boiler
for co-firing with fuel oil. Alternatively, the gas may be used for power
generation. This requires further cooling by a heat exchanger to
remove the water and tars present followed by filtration through a
paper cartridge filter to remove tar traces. It is burnt in a l6-litre
modified Ford engine coupled to a generator.
Feedstocks tested include wood, MSW, bark, sawdust, grape
wastes, olive oil wastes and coconut shells.
5. 8. 3 Results
Two sets of data are presented in Table 25. The duration of each run
was 35 h.
5.8.4 Properties of products
The liquid product is viscous with no phase separation. It has been
successfully fired in a boiler without any problems. Properties of the
oil are summarised in Table 26.
The char formed is partially crushed, ranging in size from fine dust
(extracted from a hood) to lumps up to 30 mm x 10 mm x 10 mm. At
present, this material is briquetted for marketing in the leisure
industry for barbecues. The empirical formula for the char is
Table 25
Results from test runs over 35 h [2]
Input
Wood, kg
Water in wood, kg
Air, kg
Output
Charcoal, kg
Oil, kg
Gases and vapours below 100C, kg
Yields, % wt of wood
Charcoal
Oil (as recovered, reported at 20% water)
Gases and vapours below 100C, kg
Run 1: Run 2:
Fir wood Beech wood
255
7425
3840
n.a.
29
15
n.a.
1653
2470
6590
5028
2587
11294
304
157
n.a.
Review of Biomass Pyrolysis Technologies
Table 26
Elemental analysis of bio-oil [2]
Elemental composition, % wt
Carbon
Hydrogen
Oxygen
Nitrogen
Sulphur
HIC ratio
OIC ratio
Water content, % wt
Viscosity, cp
Net heating value, MJ/kg
Ash, %wt
pH
Density at 15C, g/cm
3
R!m 1:
Fir wood
5812
655
3481
052
135
045
45
250 at 60C
222
<005
Run 2:
Beech wood
5510
720
3510
200
06
156
047
140
10 at 70C
209
27
1216
69
CHOo020000b with a volatile content between 12 and 18%, and it has a
net heating value of 293-300 MJ/kg.
The fuel gas is usually burnt and a typical gas analysis is shown in
Table 27. It has a heating value on a dry tar-free basis of 38-
55 MJ/Nm
3
.
5.8.5 Special features and problems
The oil is condensed at around 110C, leaving most of the water in the
vapour phase for combustion with the fuel gas. This solves the
waste-water disposal problem associated with pyrolysis processes.
The process can accept a wide variety of biomass such as forestry
and agro-industrial wastes (wheat, maize or rice straw).
CO
CO
2
H2
N2
Table 27
Gas analysis of BASA process (% vol.)
Oxygen and hydrocarbons
163
132
79
484
142
70 A. V. Bridgwater & S. A. Bridge
Some bridging of the feedstock occurs even with the use of a stirrer
and a vibrator.
Problems include:
-as a carbonisation process, the upper limit on liquids production is
around 15-20% wt on feed, and cannot be improved.
5.8.6 Bibliography
1. Guiol, R., private communication, 1988.
2. Bridgwater, A. V. & Churin, E., Report to EC DG XII, 1988.
3. Bio-Alternative SA, Technique de carbonisation et de pyrolyse. In
Pyrolysis as a Basic Technology for Large Agro-Energy Projects, Proceed-
ings of a Workshop held in L'Aquila, Italy, 15-16 Oct. 1987, ed. E.
Mattucci, G. Grassi & W. Palz. Commission of the European Communities
(EUR 11382 EN), Belgium, 1989, p. 205.
5.9 Molten salt pyrolysis for gases, liquids and chemicals
Example: Aston University, UK
The aim of this project is to develop a molten-salt pyrolyser to
produce liquid and gaseous fuels from biomass. This work is a
continuation of research into thermal processing of biomass and
industrial wastes in molten salts which started in 1980.
5.9.1 Introduction
Over 20 different molten salts systems have been investigated on a
laboratory scale in order to determine their ability to dissolve and
react with biomass. It was observed that ammonia enhanced the
solubility of wood in molten salts and that wood dissolved completely
in sodium/potassium hydroxide and sodium/potassium ethanoate mix-
tures. It was found that wastes such as tyres and plastics were soluble
in melts of alkali metal carbonates, particularly the eutectic mixture
of lithium/sodium/potassium carbonates. Although the lithium/
sodium/potassium carbonate mixture has a high melting point, 393C,
which makes it unsuitable for biomass solubility testing because
pyrolysis starts below this temperature, it has a high stability and low
corrosion rate.
The effect of molten salts is to provide higher heat transfer rates, to
dissolve the biomass to give a homogeneous reaction mixture, and to
enhance and/or catalyse preferred reactions.
In 1987, a 2-litre capacity continuous molten-salt system was
designed, constructed and tested.
Review of Biomass Pyrolysis Technologies
BIOMASS
Vent
Nitrogen
Nitrogen -----+\
,....u.+L-,
FIG. 21. Flow diagram-Aston University.
5. 9.2 Description and operation
71
Product gas
collection
A flow diagram of the 3 kg/h pilot plant is shown in Fig. 21, and a
flowsheet in Fig. 22.
The reactor is a cylindrical, type 304 stainless steel vessel with an
inner liner of the same steel for the salt bath. It is fitted with an
agitator with a sealed carbon bearing assembly, a pocket for the
furnace temperature control thermocouple, a bursting disc assembly to
cope with possible violent gas evolution, an inert-gas feed line and a
vapour offtake, all mounted on the removable lid. The feeder consists
of a sealed hopper with agitated sides to prevent bridging, with a
variable-speed open helical spring screw feeding raw material into a
wide-mouthed reactor inlet. The reactor is heated by a purpose-built
Nitrogen
BIOMASS
GAS to analysis and flare
LIQUID product
FIG. 22. Flowsheet-Aston University.
72 A. V. Bridgwater & S. A. Bridge
3 kW electric resistance furnace with a three-term electronic tempera-
ture controller. Feed rates of up to 3 kg/h are used in the experiments.
Vapours leaving the reactor pass through first horizontal then
vertical copper concentric-tube coolers to reduce the vapour tempera-
ture. Next, two triple-helix water-cooled glass reflux condensers are
used to condense the liquid product oils which fall into a sealed vessel
from which samples are taken for analysis. Gaseous products are
metered with a standard dry gas meter and sampled for both on-line
analysis and (collected in plastic bags) for gas chromatography or mass
spectrometry before passing through a flame trap to an outside flare.
The product gas composition is continuously monitored for H
2
, CO,
CO
2
and CH
4
using dedicated gas analysers and recorded at 10 s
intervals by a microcomputer-based data-logger. Reactor pressure is
measured by a water manometer, the product gas flow rate by a
rotameter and the total volume of gas produced by a gas meter. These
variables, along with the temperature of the salt bath, are recorded
manually.
To prevent air entering the system and to provide a carrier gas for
the gas analysis system, the equipment is operated with a nitrogen
purge. This purge is introduced at three points, the stirrer, the feeder
and the reactor, each of which is metered separately.
Two eutectic mixtures have been tested, the Li/Na/K carbonate
eutectic (435 mol% Li
2
C0
3
: 315 mol% Na2C03: 250mol% K
2
C0
3
,
melting point 397C) and Na/K hydroxide eutectic (49 mol% NaOH:
51 mol% KOH, melting point 193C). The feedstock is in-house
manufactured pine 'chips' (no bark) sieved to the size range 0-
475 mm. For the triple alkaline carbonate eutectic, a salt temperature
of 500C was chosen, whilst 300C was picked for the Na/K
hydroxide eutectic. These temperatures were chosen as they were the
midpoints of the solubility range for wood in these salts.
5.9.3 Results
Three main areas of experimental work have been carried out to date.
It was found that the heating rate in the molten salt is more rapid than
in a gaseous environment. The heating rates measured in molten salt
were from four to ten times faster than those measured in air. It was
also observed that in the alkaline melt, the cellulose core of the wood
was dissolved leaving a honeycomb-like structure of lignin.
All runs using the Li/Na/K carbonate eutectic at 500C were
terminated after approximately 20 min of feeding. This was due to
Review of Biomass Pyrolysis Technologies 73
feed blocking up the feed tube. It was found that the wood was not
assimilated into the molten salt.
The runs using the Na/K hydroxide eutectic lasted up to 1 h. In this
case the wood dissolved in the melt to produce gaseous, liquid and
solid products.
5.9.4 Properties of the products
For runs with carbonate melt, a thick smoke of fine tar particles was
formed along with low yields of gas which consisted of primarily CO
and CO
2
(up to 95%), the balance being CH
4
and H
2
. For hydroxide
melts, the liquid product consists of 97-98% water, the balance being
an organic product which has yet to be analysed. This liquid is
alkaline, possibly because of entrained particles of hydroxide in the
product gas dissolving in the condensate. The gaseous product consists
of about 98% H
2
, the balance being mainly methane. The solid
product remains within the melt. This consists of an organic residue of
mainly formate and ethanoate ions, and carbonates; the carbonates
are produced by the reaction of the hydroxide with the carbon from
the biomass. The fouled melt may be partially regenerated by heating.
Fouled melt was heated to a temperature of 400C and yielded a gas
containing H2 and CH
4
.
5.9.5 Special features and problems
By dissolving biomass in molten salt, a homogeneous reaction mixture
is obtained. Molten salts provide much higher rates of heat transfer
and also offer opportunities for catalysis or participation in the
reactions.
High yields of high-purity hydrogen (up to 98%) can be obtained.
Problems include:
-if carbonate is formed, the melt has to be regenerated, and
processes for this have not yet been evaluated;
---carbonate and organic residue in the melt lowers its effectiveness,
also therefore necessitating melt regeneration;
-the reaction mechanisms and pathways have not been evaluated,
and the catalytic effect remains to be identified and quantified.
5. 9. 6 Bibliography
1. Iredale, P. J. & Hatt, B. W., The pyrolysis and gasification of wood in
molten hydroxide eutectics. In Fundamentals of Thermochemical Biomass
Conversion, ed. R. P. Overend, T. A. Milne & L. K. Mudge. Elsevier
Applied Science, New York, 1985, p. 143.
74 A. V. Bridgwater & S. A. Bridge
2. Venning, N. J., Fuels from tyres by pyrolysis in molten salts. PhD thesis,
Aston University, 1981.
3. Pitt, M. J., Pyrolysis of plastics in molten salts. MPhil thesis, Aston
University, 1979.
4. Maund, J. K. & Earp, D. M., Biomass pyrolysis in molten salts for fuel
production. Paper presented at International Conference on Pyrolysis and
Gasification, Luxembourg, May 1989.
5. Maund, J. K. & Earp, D. M., Thermal conversion of biomass in molten
salt media. Paper presented at Euroforum New Energies '88, Saarbriicken,
Germany, 24-28 Oct. 1988.
6. Maund, J. K. Bridgwater, A. V. & Smith, E. L., Thermal conversion of
biomass in molten salts. In Biomass for Energy and Industry, 4th EC
Conference, Orleans, France, May 1987, ed. G. Grassi, B. Delmon, J.-F.
Molle & H. Zibetta. Elsevier Applied Science, London, 1987, p. 1031.
7. Earp, D. M. & Maund, J. K., Thermal conversion of biomass in molten
salt media. Third EEC Progress Report-Jan to Sept. 1988.
8. Earp, D. M. & Maund, J. K., Thermal conversion of biomass in molten
salt media. In Energy from Biomass 4, Proc. Third Contractors' Meeting,
Paestrum, 25-27 May 1988, ed. G. Grassi, D. Pirrwitz & H. Zibetta.
Elsevier Applied Science, London, 1989, p. 557.
9. Maund, J. K. & Earp, D. M., Fuels from biomass by conversion in molten
salts. In Research in Thermochemical Biomass Conversion, Phoenix,
Arizona, USA, April 1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier
Applied Science, London and New York, 1988, p. '42.
5.10 Methanopyrolysis
Example: Brookhaven National Laboratory, USA
The project was initiated in October 1980 for the purpose of creating a
database of the process chemistry for the rapid pyrolysis of biomass
(which includes wood and agricultural products) with both reactive
and non-reactive gases for the production of liquid and gaseous
hydrocarbon fuels and feedstocks.
5.10.1 Introduction
This research arose out of work carried out on the flash pyrolysis of
coal in a bench-scale, entrained-flow tubular reactor of 25 mm
diameter. It was found that the yields of liquid and gaseous hydrocar-
bons were up to 50% higher than those obtained by using slow
pyrolysis. This bench-scale reactor was later modified so that wood
could be used as the feedstock. Preliminary experiments with wood
indicated similar results and because there were no data available at
that time, a database was created.
Review of Biomass Pyrolysis Technologies 75
5.10.2 Description and operation
A flow diagram of the experimental equipment is shown in Fig. 23,
and a flowsheet in Fig. 24. The oven-dried wood particles, in the size
range 300-1000 mm, drop through the reactor from a wood feeder
enclosed in a high-pressure vessel. To prevent agglomeration and to
provide a good free-fall in the reactor, approximately 15-30% of a fine
silica flour (Cab-O-Sil) is mixed with the wood feed [3-6]. The gaseous
feed is preheated in an electrical resistance tube and entrains the wood
particles which then flow concurrently down the reactor. Feed rates of
up to 2lb/h (1 kg/h) are used.
The pyrolyser is a tubular reactor 203 cm long and made of Inconel
617. This reactor can be operated at pressures of up to 4000 psi
(276 MPa) and gas temperatures of up to 1000C. Below the reactor is
a 76 cm forced-air cooling section in which the product gases are
cooled to approximately 250-300C. The char is removed from the
effluent gas in a pressure vessel which is also maintained at 250-300C
BIOMASS
Gas preheater
Sample points
Pressure
regulator
Methane Helium
Reactor
heaters
(x4)
Char
receiver
.QQ.Q.lm.
Refrig-
Water erant
Condensates
Gas to vent
Gas
meter
FIG. 23. Flow diagram-Brookhaven National Laboratory.
76
Drier
Feeder
A. V. Bridgwater & S. A. Bridge
Gas
meter GAS product
Methane
Pyrolyser
Char
receiver
Freon
cooled
condenser
Water
cooled
condenser
L..--.... Char
LIGHT
ORGANICS
TAR
PRODUCT
FIG. 24. Flowsheet-Brookhaven National Laboratory.
to prevent liquid product condensation. The heavier liquids are
collected in a water-cooled condenser (-15C) and the lighter liquids
in a Freon-cooled condenser (--40C). The remaining gases are
reduced to atmospheric pressure, measured by a positive displacement
meter, and vented to the atmosphere.
On-line product analysis was accomplished by a programmable gas
chromatograph which determines CO, CO
2
, CH
4
, CzH6 and BTX
(benzene, toluene, xylene) concentrations on an 8-minute cycle.
Sample ports are provided every 5 cm along the length of the reactor.
Products heavier than BTX are not measured on-line due to
condensation in the sample lines and the temperature limit (230C) of
the gas chromatograph. These products are collected in the condensers
and measured at the end of each experiment. Typically, a steady
reactor temperature is achieved within 3-4 min after feeding wood
particles into the reactor and a run lasts approximately 60-75 min.
Feedstocks tested included pine, Douglas fir and lignin. The gaseous
feeds included helium, argon, nitrogen and methane.
Review of Biomass Pyrolysis Technologies 77
5. 10.3 Results
The product gas consists of ethylene, ethane, BTX (mainly benzene)
and carbon monoxide (see Table 28). For pine wood at lOOOC and
50 psi (340 kPa) , the yields of ethylene was found to be about eight
times higher with methane than with helium. As the methane-to-wood
mass flow rate increases, the ethylene and benzene yield also increases
and reaches a saturation point. Ethylene and benzene yields over 50%
based on wood carbon conversion are attained and the CO yields
reached over 40% at high methane-to-wood ratios. The enhancement
of hydrocarbons is attributed to the formation of free radicals from the
biomass decomposition which subsequently react with methane.
Methane balances were performed by mass flow rate into and out of
the reactor. Within experimental error, no appreciable net consump-
tion or production of methane was observed.
5. 10.4 Special features and problems
Significant yields of valuable fuels and chemical feedstocks such as
benzene and ethylene are produced.
Table 28
Flash pyrolysis of pine wood at 50 psi (340 kPa)
Wood feed rate, Ib/h
a
Gas feed rate, Ib/h
Particle residence time, s
Gaseous feed/wood ratio,
lb/lb
Carbon conversion to
product, %
CH
4
CzH4
BTX
CO
CO
2
Total conversion
C
2
H
4
concentration
(% vol)
a Fed with 30% Cab-O-Sil.
Methane gas feed
9O(Je 1 (}()Oe
055 055
384 384
110 130
698 698
1570 2740
1190 2460
3560 3870
240 270
6560 9340
075 1-31
Helium gas feed
9O(Je 1 (}()Oe
049 049
095 095
120 150
194 194
1210 1190
1470 370
820 800
4460 5300
320 350
8280 8010
065 018
78 A. V. Bridgwater & S. A. Bridge
Valuable data on pyrolysis fundamentals have been derived.
Problems include:
-a process design optimisation and scale-up for chemicals or fuels
production is required using the experimental bench-scale data
obtained;
-yields of non-equilibrium chemicals may not be high enough to
justify further interest based on the established design;
-an economic assessment of the process based on the data is
required to justify further interest for development.
5.10.5 Bibliography
1. Steinberg, M. & Fallon, P. T., Flash pyrolysis and hydropyrolysis of
biomass Progress Report No.2. In Proc. 13th Biomass Thermochemical
Conversion Contractors' Meeting, Arlington, Virginia, Oct. 1981, p. 445.
2. Steinberg, M. & Fallon, P. T., Flash pyrolysis of biomass with reactive and
non-reactive gases. In Proc. 14th Biomass Thermochemical Conversion
Contractors'Meeting, Arlington, Virginia, June 1982, p. 452.
3. Steinberg, M., Fallon, P. T. & Sundaram, M. S., Flash pyrolysis of biomass
with reactive and non-reactive gases. In Proc. 15th Biomass Thermochemi-
cal Conversion Contractors' Meeting, Atlanta, Georgia, March 1983, p. 42l.
4. Steinberg, M., Fallon, P. T. & Sundaram, M. S., Flash pyrolysis of biomass
with reactive and non-reactive gases. In Proc. 14th Biomass Thermochemi-
cal Conversion Contractors' Meeting, Portland, Oregon, May 1984, p. 299.
5. Sundaram, M. S., Steinberg, M. & Fallon, P. T., Flash pyrolysis of biomass
with reactive and non-reactive gases. In Fundamentals of Thermochemical
Biomass Conversion, ed. R. P. Overend, T. A. Milne & L. K. Mudge.
Elsevier Applied Science, New York, 1985, p. 167.
6. Steinberg, M., Fallon, P. T. & Sundaram, M. S., Flash methanolysis--the
flash pyrolysis of biomass with methane gas. In Proc. 1985 Biomass
Thermochemical Conversion Contractors' Meeting, Minneapolis,
Minnesota, Oct. 1985, p. 15.
5.11 Hydropyrolysis-gases and hydrocarbons
Example: University of Toronto, Canada
The overall objective of this project is the production of a liquid
product from woodchips which can be handled in typical chemical
engineering processes.
5.11.1 Introduction
This project was one of those initiated as a response to the oil crises in
the 1970s. The initial studies on liquefaction of powdered wood-water
slurry were carried out in I-litre and 2-litre batch autoclaves using
Review of Biomass Pyrolysis Technologies 79
nickel metal as catalyst with hydrogen as the reducing gas. Water-to-
wood mass ratios of 5 : 1, wood-to-nickel ratios around lO: 1 and cold
hydrogen pressures from atmospheric up to lO7 MPa were used. At
350C, oil yields were in the range 30-40% and contained lO% water.
The oxygen content of the oils was between lO and 15%. The oils had
a viscosity from 1 Pas to 10 Pas, and an aromatic carbon content of
approximately 33%. Carbon dioxide yields as high as 25% were
obtained. In subsequent experiments, wood slurries were processed in
a semi-continuous 2-litre reactor using nickel carbonate as catalyst
with hydrogen. Oil yields of up to 25% were obtained.
Studies investigating the conversion of single chip particles were
then carried out using single wood rods of about 1 g with water at a
water-to-wood mass ratio of 3. This was pyrolysed between 330 and
350C inside a lO-ml reactor at about 2400 psi (166 MPa) resulting in
products such as acetone-soluble oil, water-soluble organics and gases.
Oil yields of up to 50% were obtained. It was inferred that steam was
primarily responsible for liquefaction (swelling and physical disin-
tegration of the wood particle) but liquid water was required for
stabilisation of the oil.
On the basis of these results, a laboratory-scale, high-pressure,
2-litre autoclave, cascade system was designed, constructed and tested.
In the single-chip studies steam was generated from the water within
the reactor, but with the cascade system steam was used as the primary
liquefaction agent.
The process is different from orthodox liquefaction in a liquid
medium in that initially there is no liquid-phase carrier to provide heat
transfer or transport the reagents and products, although the process-
ing conditions are not dissimilar.
It has been shown that the steam causes an initial high mass
conversion rate which is proportional to the initial surface area of the
wood. As the wood collapses, a second, slower, mass conversion
occurs which is controlled by heat transfer through the reactor walls
and the condensed aqueous phase. For woodchips the former rate
dominates in the liquefaction.
5.11. 2 Description and operation
A flow diagram of the experimental equipment is shown in Fig. 25,
and a flowsheet of the process in Fig. 26. Woodchips with a moisture
content of 5-8% are loaded into a stainless steel basket g)
which is then placed into the nitrogen-purged, preheated reactor. The
80
BIOMASS
A. V. Bridgwater & S. A. Bridge
Nitrogen
Water
BIOMASS
Reactor +
Alternative
steam entry
points
Gas
Oil and water
Heaters
FIG. 25. Flow diagram-University of Toronto.
Gas
FIG. 26. Flowsheet-University of Toronto.
OIL
and water
Review of Biomass Pyrolysis Technologies 81
reactor was machined from a single ingot of TP316 stainless steel, with
an inner diameter of 38 cm, an internal volume of 600 ml and length
4S72 cm. It has three steam inlet ports located 76, 229 and 381 cm
from the base. Steam is obtained from a 2-litre autoclave usually
maintained at 3S0C by upper and lower temperature control; it is
passed through a two-way valve to the steam injection lines. Three
thermocouples and a pressure gauge are used to control the internal
conditions of the reactor. Two 183 m electrical heaters joined in
parallel are wrapped helically around the outside of the reactor. The
temperature at the top and middle of the reactor are typically
400-420C. However, because of conduction, the base temperature
falls as low as 300C. Although a brass block heater partially
overcomes this problem, temperature limitations on the outlet valve
preclude further heating, A new valve should solve the problem. The
reactor is insulated with lightweight ceramic brick and layers of glass
wool. The design pressure is 3S00 psi (2413 MPa) at 3S0C.
After the inlet valve is closed, steam is admitted for about 7 sand
the temperature is maintained at the desired level for lS-180 s, after
which the products are discharged into the cooling lock and then
passed to the product receiver. The volume of the gas is determined by
using a water-displacement system.
Feedstocks tested include lEA poplar woodchips with particle sizes
ranging from OS to lS cm, and wood dowels of diameters 17S, 2S
and 31 cm.
5.11. 3 Results
Results obtained so far are preliminary since the reactor unit was
commissioned only in early 1987. The chips disintegrate fairly rapidly,
initially yielding considerable amounts of aqueous-phase solids as an
oil precursor. Product oil yields of up to SO% with no solids
contamination have been obtained and the oil is easily separated from
the aqueous phase. There is a continuous production and reaction of
the aqueous-phase solids for poplar dowels 1 3 cm diameter and
greater [S]. It was found that dowels of 31 cm diameter reacted faster
than 2S cm dowels and in addition, oil yields were higher (SO% versus
43%). This observation is attributed to the smaller annular void space
in the reactor which forces initially condensed water to the upper,
hotter walls. Table 29 shows results for the 31 cm dowels.
82 A. V. Bridgwater & S. A. Bridge
Table 29
Detailed results for 3.1-cm diameter dowels
Run 1 Run 2
Input and reaction conditions
Wood dowel (765% moisture), g
Steam temperature, C
Steam injection time, s
Reaction time, s
Output
Acetone-soluble (dry), g
Acetone-insoluble (dry), g
Gas volume, litre
Aqueous phase, ml
Unconverted wood, g
Wood-to-aqueous ratio
Yield (dry), % wt
a
Total carbon in acetone-soluble oil, %b
a As acetone-soluble oil.
1618
355
5
120
709
137
90
3400
100
1 :21
474
688
b Estimated from runs made under similar conditions.
5.11. 4 Properties of products
1677
355
5
150
790
61
100
2900
00
1: 17
510
739
The oil typically softens just over 100C and has an oxygen content
between 20 and 25% wt. It is thermally stable up to approximately
200C. A full characterisation of the oil is, however, not available.
Molecular weight determinations were performed by HPSEC (High
Performance Size Exclusion Chromatography). The typical number-
average molecular weight of the oil is between 500 and 550.
The aqueous-phase solids are finely divided material which remains
suspended in the aqueous phase. It is believed that this material
represents the final precursor of the oil. The product gas contains
mainly CO
2
(93%), CO (7%), and traces of methane.
5.11. 5 Special features and problems
Woodchips are used instead of the usual wood slurries used for
liquefaction. Catalysts are not needed for this conversion process.
Problems include:
-solids handling in scale-up.
Review of Biomass Pyrolysis Technologies 83
5.11. 6 Bibliography
1. Boocock, D. G. B., Agblevor, F., Chowdhury, A., Holysh, M. & Porretta,
F., The liquefaction of poplar by rapid aqueous pyrolysis: results from
semi-continuous and batch units. In 5th Canadian Bioenergy R&D Seminar,
ed. S. Hasnain. Elsevier Applied Science, London, 1984, p. 450.
2. Beckman, D. & Boocock, D. G. B., Can. J. Chern. Eng., 61 (1983) 80.
3. Boocock, D. G. B., Agblevor, F., Holysh, M., Porretta, F. & Sherman,
K., Liquefaction of poplar chips by aqueous thermolysis. In Energy from
Biomass and Wastes X, Lake Buena Vista, Florida, 28 Jan.-1 Feb. 1985,
ed. D. L. Klass. Elsevier Applied Science & Institute of Gas Technology,
London, 1985, p. 1107.
4. Boocock, D. G. B., Agblevor, F., Chowdhury, A., Kosiak, L., Porretta, F.
& Vasquez, E., Ultrastructure changes in poplar chips during steam
liquefaction. In Energy from Biomass and Wastes IX, ed. D. L. Klass.
Elsevier Applied Science & Institute of Gas Technology, London, 1985, p.
749.
5. Boocock, D. G. B., Chowdhury, A. & Allen, S. G., The production and
evaluation of oils from the steam pyrolysis of poplar chips. In ACS
Symposium, Production Analysis and Upgrading of Oils from Biomass,
Denver, CO, April 1987, p. 90.
6. Boocock, D. G. B., Chowdhury, A. & Kosiak, L., Aspects of the steam
liquefaction of poplar wood chips in a gravity fed reactor. In Research in
Thermochemical Biomass Conversion, Phoenix, Arizona, USA, April
1988, ed. A. V. Bridgwater & J. L. Kuester. Elsevier Applied Science,
London and New York, 1988, p. 843.
5.12 Twin fluid-bed fast pyrolysis for gases
Example: TNEE, France
The objective of this research is to produce medium heating value gas
which can be used in an industrial application such as direct firing of a
lime kiln in the pulp and paper industry.
5.12.1 Introduction
This project arose out of work carried out at TNEE in collaboration
with the University of Nancy. The University of Nancy carried out
fundamental research on fast pyrolysis using a vertical quartz tube
heated by an electric furnace from 500C up to 1000C. Heating rates
of 1000C/s and residence times of less than 1 s were estimated. Feed
weights of 100-300 mg with a particle size ranging from 25 to 400 mm
were used with moisture contents from 0 to 100%. Results indicated
that gas yields increased with temperature and moisture content. For
dry softwoods the increase was from 139% at 500C to 613% at
1000C, and for hardwoods the increase was from 167% (500C) to
84 A. V. Bridgwater & S. A. Bridge
676% (lOOOC). The main components were CO, CO
2
and CH
4
The
heating value of the pyrolytic gas was a maximum of 20 MJ/Nm
3
at
750C but this decreased to 18 MJ /Nm3 at lOOOC.
A 20 kg/h pilot unit was then constructed to pyrolyse pine bark on a
continuous basis using a fluid bed, a combustor, and raining packed-
bed heat exchangers (RPBE). The RPBE is a novel, high-efficiency,
high-temperature, heat transfer system. Two such units are used to
recover heat from the combustion of char and transfer it to the
incoming combustion air. The results obtained confirmed data col-
lected using the bench-scale equipment, particularly in that the
pyrolysis gas composition and the heating value could be higher than
17 MJ/m
3
depending on the conditions used. A unit with a nominal
throughput of 500 kg/h of dry fir bark was next constructed.
5.12.2 Description and operation
The 500 kg/h process is depicted schematically in Fig. 27, and a
flowsheet of the process in Fig. 28. The feed is milled, sieved to less
than 5 mm and dried (optimum moisture content 40%, dry basis)
before entering a fluid bed reactor of hot sand. The sand has a mean
particle size of 200 Jlm. The bed is fluidised by recycled product gas,
and as fast pyrolysis occurs, a medium heating value fuel gas
containing hydrocarbons is produced. The resultant gas leaves the
reactor through a special packed contacting zone (RPBE) where it
encounters sand raining down at a temperature of 980C. This
contacting zone acts as an efficient countercurrent heat exchanger and
the heated tars entrained by the gas are gasified.
The gas is passed through a cyclone to remove the carrier fines, ash
and char, which are combined with the overflow stream from the
reactor. The gas is cooled by two air-cooled exchangers and then
passed through a cold-water scrubber to condense the moisture. A side
stream of the gas is recycled to fluidise the reactor. Steam is sometimes
used instead of recycled product gas for fluidisation.
The overflow of sand carries char and ash out of the fluid bed. These
are fed into the combustion chamber where the combustion of the char
heats up the sand; preheating of the air allows the sand to be raised to
about 980C. The combustion takes place in a circulating bed so that
the sand is carried to the top of the pyrolyser by the exhaust gas; the
sand is separated from the exhaust gas in a cyclone, and drops into a
distributor mounted over the RPBE which in turn surmounts the
fluidised bed.
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Review of Biomass Pyrolysis Technologies 87
By using a double RPBE, heat is recovered from the combustion
exhaust gas and used to preheat the combustion air. The exhaust gas is
cooled countercurrently by sand in the first RPBE. The heated sand
then enters the second RPBE where they flow in countercurrent to the
combustion air, which is heated to about 650C in the process. The
preheated combustion air then passes directly to the combustor.
5.12.3 Results
Table 30 shows typical yields.
5.12.4 Properties of products
The fate of the tar and waste-water products is unclear. The lower
heating value of the gas can be as high as 17 MJ /Nm
3
and its density is
about 095 kg/m3. This gaseous product can be used to fire a lime kiln
in the paper industry or provide heat for an industrial process.
5.12.5 Special features and problems
The RPBE permits the pyrolysis process to be energetically self-
sufficient through the combustion of char, thereby maximising the gas
yield.
Table 30
Product yields from the TNEE fast pyrolysis process
Feed
Moisture content, % wt (dry basis)
Fluid bed temperature, C
Sand temperature at the RPBE entry, C
Sand/bark flow rate ratio
Char, kg/kg dry bark
Tar, kg/kg dry bark
Gas water content, kg/kg dry bark
Gas, kg/kg dry bark
Composition, % vol. (dry basis)
CO
CO
z
Hz
CH
4
CzH4
CzHz
Cz
H
6
Lower heating value, MJ/Nm
3
Energy efficiency (based on LHV dry gas), %
Bark
38
760
980
20
0210
0038
0345
0800
4300
1570
2270
1700
120
040
Traces
1486
67
88 A. V. Bridgwater & S. A. Bridge
The process is self-stabilising. For example, when the pyrolysis
temperature is too low, more char is produced, the combustion of
which increases the temperature of the sand and therefore that of the
pyrolysis bed. Conversely, if the temperature increases, the quantity of
char decreases; this causes a reduction in temperature, thereby
restoring steady-state conditions.
Problems include:
-process complexity, which results in the capital cost being too high
for current energy costs;
---control of solids between the pyrolysis bed and the combustion
chamber.
5.12.6 Bibliography
1. Deglise, X., Richard, C., Rolin, A. & Francois, H., Fast
pyrolysis/gasification of lignocellulosic materials at short residence time. In
Energy from Biomass, 1st EC Conference, Brighton, England, Nov. 1980,
ed. W. Palz, P. Chartier & D. O. Hall. Applied Science Publishers,
London, 1981, p. 548.
2. LeLan, A., Fast pyrolysis of wood wastes to medium energy gas. In
Thermochemical Processing of Biomass, ed. A. V. Bridgwater. Butter-
worths, London, 1984, p. 159.
3. Gourtay, F., Nogues, J. C. & LeLan, A., The TNEE fast pyrolysis process.
Its application in the paper industry. In Biomass for Energy and Industry,
4th EC Conference, Orleans, France, May 1987, ed. G. Grassi, B. Delmon,
J.-F. Molle & H. Zibetta. Elsevier Applied Science, London, 1987, p.
1057.
4. LeLan, A., Le procede TNEE de pyrolyse rapide-son application dans
l'industrie de la pate a papier. Paper presented at Joumees Techniques
MEl 87, Paris, April 1987.
5.13 High-temperature free-fall radiation pyrolysis for gases
Example: University of Zaragoza and Hunosa, Spain
The aim is to use a very high-temperature, tubular reactor, with
biomass free fall (formerly named high-temperature fluid-wall-
HTFW) to flash-pyrolyse biomass in order to maximise gas yields.
5.13.1 Introduction
Based on a design patented by Matovich in 1976, the (HTFW) reactor
was designed and constructed to withstand temperatures of up to
2200C by Hunosa under the technical direction of the University of
Zaragoza. The maximum feed rate used to date is 110 kg/h. The main
Review of Biomass Pyrolysis Technologies 89
component of the tubular reactor is a core of a porous refractory
material (for example, graphite) capable of emitting sufficient radiant
energy to activate the reactants fed into the tubular space. It is this
predominantly radiative heat-transfer mechanism which distinguishes
the HTFW reactor from the more conventional pyrolysers that employ
convective or conductive heat transfer techniques to transfer heat to
the reactants.
5.13.2 Description and operation
A schematic of the experimental equipment is shown in Fig. 29, and a
flowsheet of the process in Fig. 30. Biomass is fed to the top of the
reactor at a rate of 60-110 kg/h from a screw feeder. The feed is
BIOMASS
Nitrogen,
6 electrode
heaters
Nitrogen
for
quenching

High temperature
fluid wall
reactor
Quenching zone
Post reaction
zone
Solids

Bag
filter
Gas to flare
FIG. 29. Flow diagram-University of Zaragoza and Hunosa.
90
Nitrogen
A. V. Bridgwater & S. A. Bridge
Gas to
analyser
FIG. 30. Flowsheet-University of Zaragoza and Hunosa.
GAS
tollare
entrained by nitrogen into the reactor. The residence time of the
particles in the reaction zone is estimated to be between 04 and 12 s,
depending on operating conditions. As the feed falls, it is rapidly
heated by radiation to the reaction temperature. The heating rate is
estimated to be 10
6
C/s.
The reactor has an internal diameter of 30 cm, and an effective
length of 18 m. The total plant height is 12 m. The reactor core is
made from uniformly porous graphite that allows the permeation of a
radiation-transparent gas, namely nitrogen, through the reactor wall
into the reactor. This nitrogen input creates a protective envelope of
gas or a 'fluid wall' which blankets the inner side of the reactor wall,
thus reducing the contact of reactants and products with the radiating
surface. The reactor core is heated by a set of six electrodes located
symmetrically around it.
At the reactor exit, the product stream can be quenched by a
supplementary nitrogen stream. Further cooling is achieved by heat
exchange with a water-ethylene glycol solution.
The solids (mainly char, ash plus unconverted biomass) are collected
in a vessel at the bottom of the reactor, in a cyclone downstream and
also in a bag-filter system. It is claimed that absolutely no liquid
product is formed during the experiments. The flow rate of the exit gas
is measured by a Venturi meter.
A gas chromatograph is used to determine the composition of the
gas stream exiting from the reactor. In addition, the evolution of CO,
Review of Biomass Pyrolysis Technologies 91
CO
2
and H2 is continuously monitored by on-line analysers. The water
content of the gas is determined by measuring the weight increase in a
desiccant.
The feedstock tested is pine sawdust (20% moisture and 400 mm
average particle diameter).
5. 13.3 Results
Table 31 shows GC analysis results for two different reactor wall
temperatures, 1600C and 1800C. High gas yields are obtained at
these high temperatures with 80% of the biomass gasified at 1800C.
At 2000C and 250 mm particle size, gas yields of 98% (as kg N2 free
gas/kg biomass d.a.f.) have been achieved.
It was found that as the feed rate is increased the gasification
efficiency decreases, i.e. although the overall gas production increases
when increasing the biomass throughput, the mass of gas produced per
unit mass of feed decreases. For example, at a temperature of 1600C
and nitrogen flow rate of 42 Nm
3
/min, increasing the feed rate beyond
14 kg/min caused a decrease in the gas yield. If the nitrogen flow is
increased, both the residence time and the conversion rate of the
feedstock decreases, the LHV of the exit gas decreases and the cost
increases. Then the nitrogen flow must be minimised, or preferably
changed to offgas.
Biomass feed rate, kg/h
Nitrogen flow rate, Nm
3
/h
Particle diameter, mm
Table 31
Gas analysis
Gas analysis, % vol. (dry basis),
CO
CO
2
H2
CH4
N2 (by difference)
Gas yield, kg product gas/kg biomass
(nitrogen-free basis)
Lower heating value, MJ/Nm
3
Temperature cae)
1600 1 BOO
1080
2580
400
1130
180
1420
100
7170
075
324
1080
2580
400
1320
1-10
1690
030
6850
078
352
92 A. V. Bridgwater & S. A. Bridge
5.13.4 Properties of the products
The gas has a lower heating value of between 25 and 45 MJ/Nm
3

This low heating value is due to the dilution effect of nitrogen in the
product gas. Contaminants such as tars have not been detected in the
product gas.
5.13. 5 Special features and problems
By employing this type of reactor, very high temperatures and high
heating rates can be achieved to pyrolyse biomass. Radiative heat
transfer is uniquely the main mode of heat transfer. No tars or liquids
are formed. Very high gas yields of up to 98% have been achieved.
Problems include:
-nitrogen used for creating the envelope causes dilution of the gas
product-ways of overcoming this problem are currently under
study;
-high pyrolysis temperatures increase heat losses and can reduce
energy efficiency;
---costs are too high to make this reactor viable.
5.13.6 Bibliography
1. Matovich, E., Thagard Technology Company, US Patent 3933434, 20 Jan.
1976.
2. Corella, J., Santamaria, J., Monzon, A. & Gonzalez-Canibano, J.,
Influence of operating conditions of gas production during high-
temperature pyrolysis of biomass. In Biomass for Energy and Industry, 4th
EC Conference, Orleans, France, May 1987, ed. G. Grassi, B. Delmon,
J.-F. Molle & H. Zibetta. Elsevier Applied Science, London, 1987, p.
1036.
3. Corella, J., Monzon, A., Santamaria, J. & Gonzalez-Canibano, J.,
Ultra-fast biomass pyrolysis in a high-temperature (2200C), fluid-wall
reactor. Trans. ASME, 110 (Feb. 1988) 10-13.
3
Direct Catalytic Liquefaction Technology of
Biomass: Status and Review
D. MEIER
Federal Research Centre for Forestry and Forest Products,
Institute of Wood Chemistry and Chemical Technology of Wood,
Leuschnerstrasse 91, D-2050 Hamburg 90,
Federal Republic of Germany
&
M. Rupp
VEBA OEL Entwicklungs GmbH, Uhlenbrockstrasse 10,
D-4650 Gelsenkirchen, Federal Republic of Germany
ABSTRACT
Direct catalytic liquefaction of biomass is one approach to produce
liquid fuels and chemicals from biomass. In contrast to pyrolysis, in
which thermal treatment only leads to depolymerization of the macro-
molecules of biomass (carbohydrates and lignin), further reactions are
introduced in direct liquefaction by addition of pressurized reducing gas
(hydrogen or carbon monoxide) and a catalyst to the reactor. High
biomass conversion rates of up to 95% are obtained because char
formation is suppressed as recondensation and recombination of
thermal cracking products are reduced. Generally, the oils are more stable
than pyrolysis oils due to the lower content of unsaturated compounds
and lower oxygen content, which is in the range of 8-12%. As direct
catalytic liquefaction of biomass is a high-technology method depending
on many parameters, development has not been as rapid as in pyrolysis.
However, yields and qualities of liquid products are promising and it is
possible that some of the experience gained with existing coal liquefac-
tion technologies can be adopted to the new feedstock biomass.
93
94 D. Meier & M. Rupp
DEFINITION
Direct catalytic liquefaction of biomass means the direct reductive
thermal conversion of lignocellulosic material (or one of its com-
ponents, cellulose or lignin) into a liquid (oil) or at least soluble
material in a reducing atmosphere, in the presence of a catalyst and in
a liquid-phase system.
PRINCIPLE AND OBJECTIVE OF THE REACTION
The conceptually ideal reaction mechanism of the thermal treatment
of biomass, is as follows: the macromolecular constituents, cellulose,
hemicelluloses and lignin, are cleaved into radicals which are saturated
and stabilized by catalytically activated hydrogen to give low-
molecular-weight products. The oxygen of the biomass is removed as
carbon monoxide and carbon dioxide. The remaining products are
pure hydrocarbons with a high calorific value and ready to use as a
motor fuel or chemical feedstocks.
However, due to the many different types of bonds of the
biomolecules (carbon-carbon, hydroxyl, ether, carbonyl, carboxyl),
many concurrent reactions occur, i.e. further degradation, reconden-
sation and recombination. This leads not only to the formation of pure
hydrocarbons (oils) but also to the formation of oxygenated hydrocar-
bons (such as phenols, catechols, furans), gases, high-molecular-
weight compounds (tar) and solid residue (char). Furthermore, water
is produced because of the high oxygen content (about 45%) of
biomass. Hence, R&D activities in the field of direct liquefaction are
concentrated on minimizing these unavoidable secondary reactions by
selection of appropriate process conditions and suitable catalysts.
HISTORICAL DEVELOPMENT
The first attempts to convert biomass into an oil of commercial
importance were conducted by Lindblad between 1927 and 1932 [1].
He was able to liquefy wood, cellulose and isolated lignins by
hydrogenolysis in a batch process at about 450C and 22 MPa using a
variety of catalysts. In 1929 Ipatiew & Petrow [2] published results on
the production of gasoline and aromatic hydrocarbons by heating
Direct Catalytic Liquefaction of Biomass 95
wood tar at 440-480C under hydrogen pressure. Berl [3] reported in
the period 1934-1944 the production of a 'proto oil' by heating wood
in an aqueous phase to temperatures greater than 230C in the
presence of catalysts, such as limestone, magnesite, dolomite and
zeolite.
In the 1940s and later, the method of hydrogenolysis was used by
other lignin chemists to study both the composition of the complex
natural polymer and the production of phenols from isolated lignins or
lignin-containing spent liquors from the pulp industry. A group at the
Noguchi Institute in Japan [4] converted lignin sulphonate with a
pasting oil, generally phenol, and a catalyst at 370-430C and at least
10 MPa hydrogen into a liquid product mixture and reported a yield of
44% monophenols. However, despite expending considerable effort,
the Crown Zellerbach Corporation in the USA could not repeat the
Japanese results. Instead of 44%, only 21% monophenols were
obtained [5].
In general, biomass has only played a very small role in the
development of liquefaction technology on an industrial scale. Most
work has been carried out with fossil raw materials, especially coal.
Between World War I and World War II the hydrogenation of coal
was industrially developed in Germany and in 1943/1944 12 plants
converted 4 million tons of coal, coal tars and lignite into motor fuels.
After World War II the hydrogenation activities of fossil materials
were substantially reduced due to the low cost of mineral oil.
ACTIVITIES IN THE USA AND CANADA
At the beginning of the first oil crisis, research activities started again
on the conversion of renewable lignocellulosics or cellulosic wastes
into liquid fuels. The US Bureau of Mines coordinated studies at the
Pittsburgh Energy Research Center (PERC) into the possibility of
producing oil by treating wood in an aqueous phase with carbon
monoxide up to 135 MPa with and without alkaline catalysts [6].
Based on the results of these studies, a pilot plant in Albany, Oregon,
was built. With that plant two process concepts were studied [7].
1 The PERC mode
The PERC process was based on the recycling oil technique. Wood
flour was mixed with a pasting oil (solid concentration 7%). A typical
96 D. Meier & M. Rupp
loading of the reactor consisted of 7% wood, 25% water which
contained 5% sodium carbonate as catalyst (based on dry wood) and
68% recycle oil. The reducing atmosphere consisted of a mixture of
CO and H
2
The conversion reaction took place at 300-340C and
about 20 MPa. At about 20 min residence time the oil yield was
between 40 and 55%, with an oxygen content of the oils ranging from
about 17% at the lowest temperature (294C) to 12% at the highest
temperature (340C).
2 The LBL mode
The LBL process, developed by Lawrence Berkeley Laboratories
worked with an aqueous phase as carrier. Prior to conversion, the
wood flour was treated with 005% sulphuric acid at 180C for 45 min
to improve the slurry formation. Reaction was carried out at 330-
360C and 17-24 MPa synthesis gas. Residence time was varied
between 5 and 60 min. Oil yields were found to be dependent on
residence time (363% at 22 min compared with 154% at 40 min).
Further investigations on direct liquefaction were conducted at the
University of Sherbrooke, Canada. Research focused on an integrated
concept, i.e. solvolysis of wood in recycled process oils or in
high-boiling alcohols (glycols), followed by hydrogenation of the
dissolved and suspended material [8]. A specially designed defibrillat-
ing valve is used for the disintegration of the biomass and mixing with
the carrier liquid under pressure. With this valve, feed slurry contain-
ing 285% suspended wood plus 125% of new solid wood presented
no problems. In a cascade reactor maximum oil yields of 60% were
obtained from wood at 320C and about 14 MPa with a 10-minute total
residence time.
At the University of Toronto, Canada, a 'Cascade Autoclave
System' has been used for the solubilization (liquefaction) of poplar
wood [9]. Woodchips (100 g) were treated for 2 min with steam which
was injected at 340C for 7 s into the preheated (c. 400C) reactor.
Only small amounts of acetone-insolubles were obtained. The result-
ing liquid was soluble in acetone. It solidified on cooling and could
easily be separated from the condensed water. The oils had oxygen
contents in the low 20%s and softened just over 100C.
A second water-based liquefaction technology has been studied at
the University of Arizona in Tucson, Arizona, USA [10]. The process
was based on an extruder-feeder reactor system. As the wood flour
Direct Catalytic Liquefaction of Biomass 97
slurry entered the reactor, it was mixed with superheated steam and
carbon monoxide. The steam was used to heat the wood flour slurry
up to the reaction temperature of 350C. Steam and carbon monoxide
reacted via the water-gas shift reaction to provide hydrogen for
liquefaction. Slurry concentrations of up to 60% could be pumped
with the extruder system. The yield of crude distillate oils was in the
range 24-30% having an oxygen content of about 8%.
ACTIVITIES IN EUROPE
At the Royal Institute of Technology, Stockholm, Sweden, the
liquefaction of peat was investigated. The technology was based on the
recycle oil principle [11]. In a first dewatering step the peat was heated
and compressed followed by dissolution in the heated recycle oil. The
slurry. then entered the high-pressure reactor, where liquefaction took
place in a hydrogen atmosphere.
The conversion of peat into liquid products was also investigated at
the Technical Research Centre of Finland (VTT) in Espoo. The aim of
the research work was to identify the most promising process concept
for liquefaction by high-pressure liquid-phase treatment. The work
concentrated on pretreatment, slurry and pumping, and primary
liquefaction [12]. Experiments were carried out in a batch reactor
system with a facility for charging the feed slurry into the preheated
reactor. Different carrier oils were tested: anthracene oil, tetralin, and
I-methylnaphthalene. Yields of 70-80% pentane-soluble products
were obtained with a hydrogen consumption of less than 1 %. The
following operating parameters were used: temperature in the range
380-420C; pressure of reducing gas (hydrogen or carbon monoxide)
about 20 MPa and residence time 10 min.
The latest developments at the VTT are the thermal treatment of
spent Kraft black liquor from the pulp industry [13]. Experiments were
carried out in a I-litre batch autoclave at 300-350C, 20 MPa pressure,
in an atmosphere of carbon monoxide, hydrogen or nitrogen, and a
residence time of 45 min. The dissolved organics in the black liquor
were converted to an organic phase (tar) which was separated from the
water. It is planned to hydrotreat the organic residue in order to
obtain a clean fuel for the operation of a gas turbine. A major
drawback of the process is the remaining sodium salts in the organic
phase.
98 D. Meier & M. Rupp
Direct catalytic liquefaction is being investigated at the University of
Manchester, Institute of Science and Technology, UK. Earlier
studies were done by reacting cellulose and organic constituents of
municipal refuse as well as dried sewage sludge in the presence of a
ruthenium catalyst supported on aluminium silicate in an aqueous
medium. The temperature ranged from 200 to 350C in the presence
and absence of a reducing gas such as hydrogen and carbon monoxide.
Oil yields were about 35%. From the results of the basic research, the
so-called Manoil process was developed in conjunction with Salford
University Industrial Centre, Sim-Chem Ltd and Greater Manchester
County Council. The conversion of cellulosic refuse and other
biomass-derived cellulosic material is performed in a continuously
working reactor. The feedstock material is mixed with a metal catalyst
such as nickel, and a process liquid. It is reported that no addition of
hydrogen is necessary by careful choice of the catalyst, the slurrying
fluid and the reaction conditions [14].
Currently, liquefaction is under investigation in France at the
Technical University of Compiegne [15]. The liquefaction of wood is
carried out in two steps. In the first step the wood is converted into a
liquid in the presence of phenol as a solvent at temperatures up to
250C with the addition of 1% sulphuric acid. After removing the
solvolysis oil, an aqueous and a light organic fraction are obtained.
The second step involves a catalytic hydrotreatment of the heavy
residue.
At the Technical University of Berlin, FRG, the conversion of
biomass is studied in a two-step process which is similar to the French
concept [16]. In the first stage, the biomass is extracted with tetralin at
300-400C at about 4 MPa pressure. The extract, which yields about
55%, is mixed again with tetralin and catalytically hydrotreated with
sulphided NiMo catalyst at 35 MPa and temperatures between 300 and
450C. According to the reports available, the oil from biomass has an
oxygen content below 1 %.
A single-step process is being investigated at the Federal Research
Centre for Forestry and Forest Products, Hamburg, FRG [17].
Catalytic hydro liquefaction in the liquid phase has been conducted
using a 3 x l-litre-capacity autoclave system-consisting of a reactor,
hot separator and cooler-for the simulation of a continuous process.
Small biomass particles are mixed with recycled oil (starting oil is a
mixture of pyrolysis oil with pitch tar from tall-oil distillation) and
catalysts. The most favourable results were obtained with palladium
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100 D. Meier & M. Rupp
on active charcoal (Pd/C) or iron as catalysts. The conversion reaction
is carried out at about 20 MPa hydrogen at 380C for 15 min. Liquid
products in the gas phase are flash-distilled in the hot separator. The
bottom residue is used as carrier oil, and the remaining products are
cooled down to room temperature to yield a light and middle distillate
net product oil (NPO) with a boiling range between 80 and 360C. The
material balance reveals that 36 parts of the NPO can be obtained
from 100 parts of dry wood and 4 parts of hydrogen in the presence of
50 parts of carrier oil. The yield of gases is 38 parts, 17 parts of them
are hydrocarbons which can be steam-reformed to give the necessary
hydrogen. In addition, 25 parts of an aqueous phase and 5 parts of
solids are produced. The oil is 99% miscible with n-hexane and has an
oxygen content of about 12%. With respect to the energy balance 59%
of the input energy (biomass and hydrogen) is contained in the net
product oil. A schematic concept of necessary modules of a continuous
liquefaction plant is depicted in Fig. 1.
SUMMARY
According to this review, there are generally four basic liquefaction
concepts:
(1) high-pressure reaction in an aqueous medium with carbon
monoxide and carbonate as catalyst;
(2) high-pressure reaction in recycle oil with hydrogen and
hydrocracking/hydrotreating metal catalysts;
(3) high-pressure steam treatment followed by high-pressure
hydrotreatment of the tar extract;
(4) medium-pressure solvolysis in an organic medium, and distilla-
tion of the solvent followed by high-pressure hydrotreatment of
the tar residue.
The extent of process development of all concepts is fairly low in
comparison with pyrolysis techniques. There are various reasons for
this, including:
-high pressure (up to 30 MPa) equipment is necessary which is
expensive and requires considerable resources;
-many process parameters must be studied. Even in coal liquefac-
tion, which has been investigated for decades, there is still much
to learn in order to optimise the process.
Direct Catalytic Liquefaction of Biomass 101
The economics of direct catalytic liquefaction technologies are difficult
to determine due to the small database available. Results of a
techno-economic assessment of direct biomass liquefaction (made by
members of the lEA Group) indicate that atmospheric flash pyrolysis
appears to be more economic than catalytic liquefaction of biomass
[18]. With respect to process energy efficiency, both processes attain
50-60%. Production costs for direct liquefaction were calculated to be
US$815/t compared with US$673.8/t for pyrolysis. It was predicted
that these could be reduced by advanced technology to US$584.7 It
compared with US$514.5/t for pyrolysis.
Although thermochemical conversion processes are generally
viewed as capital-intensive, the cost of feedstock was found to be the
largest operating cost, and hence the final product cost was found to
be most sensitive to feedstock costs.
REFERENCES
1. Lindblad, A. R., Preparation of oils from wood by hydrogenation. Ing.
Vetenskap Akad. Handl., 107 (1931) 7-59.
2. Ipatiew, W. & Petrow, D., Uber die pyrogene Zersetzung von Holzteer in
Gegenwart von Wasserstoff und unter Druck. Angew. Chern., 1 (1928)
172-6.
3. Berl, E., The production of oil from plant materials. Science, 99 (1944)
309-12.
4. Oshima, M., Maeda, Y. & Kashima, K., Process for liquefaction of lignin.
Canadian Patent 700209, 1964.
5. Goheen, D. W., Low molecular weight chemicals. In Lignin-
Occurrence, Formation, Structure, and Reactions, ed. K. V. Sarkanen &
C. H. Ludwig. Wiley-Interscience, New York, 1971, pp. 797-832.
6. Appell, H. R., Friedmann, S., Yavorsky, P. M. & Wender, I., Converting
organic wastes to oil, a replenishable energy source. Report of Investiga-
tion 7560, Bureau of Mines, Washington, DC, 1971.
7. Thigpen, P. L. & Berry, W. L., Liquid fuels from wood by continuous
operation of the Albany, Oregon biomass liquefaction facility. Paper
presented at Energy from Biomass and Wastes VI, Lake Buena Vista, FL,
USA,1982.
8. Chornet, E., Eugene, D. & Arsenault, R., Conversion of lignocellulose
materials via hydrogenolysis and solvolysis at low severity conditions. In
Specialists' Meeting on Biomass Liquefaction at the University of
Saskatchewan, 16-17 Feb. 1982, pp. 31-2.
9. Boocock, D. G. B. & Poretta, F., Physical aspects of the liquefaction of
poplar chips by rapid aqueous thermolysis. 1. Wood Chern. Technol., 6
(1986) 127-44.
102 D. Meier & M. Rupp
10. White, D. H., Wolf, D. & Zhao, Y., Biomass liquefaction utilizing
extruder-feeder systems. In Pre prints of ACS Symp. on Production,
Analysis and Upgrading of Oils from Biomass, 32(2) (1987) 1Q6-16.
11. McKeough, P., Nissilii, M., Solantausta, Y., Beckman, D. & Ostman, A.,
Techno-economic assessment of direct biomass liquefaction processes.
Research Report No. 337, Technical Research Centre of Finland (VTT),
Espoo, 1985.
12. Solantausta, Y., Technical Research of Finland, pers. comm., 1989.
13. McKeough, P., Alen, R., Oasmaa, A. & Johansson, A., Improved
utilization of black liquor through liquid-phase thermal processing. Paper
presented at the VTT Symp. on Non-Waste Technology, Espoo, Finland,
20-23 June 1988.
14. Bult, J. M. E., The Manoil project. Paper presented at the 89th annual
conference of the Institute of Wastes Management, Torbay, UK, June
16-19 1987.
15. Bouvier, J. M., Gelus, M. & Maugendre, S., Direct liquefaction of wood
by solvolysis. In: Pyrolysis Oils from Biomass: Producing, Analyzing, and
Upgrading, ed. E. J. Soltes & T. A. Milne, ACS Symposium Series,
Washington, DC, 1988.
16. Nelte, A. & Meier zu K6cker, H., Direct liquefaction of wood and
agricultural wastes (biomass). In Euroforum New Energies, Proc. Int.
Congress, Saarbrikken, FRG, 24-28 Oct. 1988, pp. 673-75.
17. Meier, D. & Faix, 0., Production of synfuels and chemical feedstocks by
direct hydro liquefaction of lignocellulosic biomass. In Euroforum New
Energies, Proc. Int. Congress, Saarbrucken, FRG, 24-28 Oct. 1988, pp.
670-2.
18. Elliott, D. C. et al. A technical and economic analysis of direct biomass
liquefaction. In Energy from Biomass and Wastes XIII, ed. D. Klass.
IGT, Chicago, 1989.
4
Upgrading of Pyrolysis Oils by Hydrotreatment
E. CHURIN
Unite de Catalyse et Chimie des Materiaux Divises, Universite Catho-
lique de Louvain, Place Croix du Sud 1, 1348 Louvain-la-Neuve,
Belgium
ABSTRACT
Bio-oil can be produced by high-pressure, low-temperature liquefaction
in a liquid-solid phase system or by moderate-temperature pyrolysis in
a gas-solid phase system at ambient pressure. Both processes give an
oxygenated product. While this liquid can be utilised directly in some
applications, stabilisation or upgrading is needed to produce material
that is compatible with conventional hydrocarbon fuels and can be used
in applications based on these fuels. This chapter describes the
technology and status of hydrotreating-one of the technologies being
developed for upgrading.
INTRODUCTION
Liquids can easily be produced from biomass by pyrolysis or high-
pressure liquefaction but the quality of the product is relatively low
compared with conventional hydrocarbon fuels and it has so far only
been used directly to substitute for heavy fuel oil in direct firing
applications. The low quality is mainly due to the high proportion of
oxygen, which for pyrolysis liquids is typically 30-40% wt, and for
high-pressure liquefaction liquids is typically 15-20% wt, making this
latter product of significantly higher quality than pyrolysis liquids (see
Chapter 3). Distillation or extraction only yields very low quantities of
usable fuel products, so upgrading has to employ chemical processing.
103
104 E. Churin
Oxygen must be eliminated and heavy molecules cracked in order to
improve the quality of the oil. These transformations need a catalyst.
One possibility is to treat the oil under high pressure with hydrogen in
the presence of a catalyst typically used in petroleum hydrotreating.
Another is to treat the pyrolysis vapours, before condensation, with
a zeolite-based catalyst at atmospheric pressure.
The first possibility, which is based on the well established
hydrotreatment technology for processing of different petroleum cuts,
is considered in this chapter.
WHAT IS HYDROTREATMENT?
The effect of the hydrogen on the transformation of petroleum
products can be roughly divided into two processes:
-hydrotreating;
-hydrocracking.
In the first case only the carbon-heteroatom bonds are broken and
some hydrogenation occurs. In the second case carbon-carbon bonds
are broken.
Hydrotreating
The application of hydrotreating to different petroleum cuts is
principally motivated by the fact that the marketing specifications for
fuels have become stricter, largely owing to environmental considera-
tions and because naphthas used as feedstocks for catalytic reformers
must meet very stringent sulphur specifications of less than 1 ppm to
protect platinum catalysts. At the same time catalytic reforming
provides relatively cheap hydrogen as a by-product which can be used
for sulphur removal by hydrogen treatment.
In recent years the production of conversion or cracked products has
increased relative to straight-run products. These products contain
high quantities of olefins, aromatics and nitrogen compounds with
some sulphur, so hydrodesulphurization has evolved to become a more
general hydrotreating process. The following variations are found:
-hydrotreating of distillates;
-hydrotreating of pyrolysis gasoline;
-smoke point improvement of kerosene;
-hydrodesulphurisation and demetallisation of heavy fractions.
Upgrading of Pyrolysis Oils by Hydrotreatment 105
In a classical hydrotreating process the feed is mixed with a
hydrogen-rich stream and heated by heat exchange with reactor
effluents and by a furnace before contacting the catalyst in the reactor.
The reaction conditions depend on the nature of the charge and the
conversion desired but temperatures are typically around 300-3S0C
and pressures typically 4-6 MPa. Under these conditions sulphur and
nitrogen are removed and olefins and some aromatics will be hydro-
genated. The hydrogen sulphide produced can be easily removed from
the gas stream and can be converted into elemental sulphur by the
Claus process.
Pyrolysis gasoline is the C
s
-200C cut of the by-product from steam
cracking (e.g. ethylene production). The cut presents unacceptable
odour, colour and gum-forming tendencies. These properties can be
improved by hydrotreatment. One objective can be the recovery of
benzene, toluene and xylene to be used as chemicals and in this case
two stages may be needed. In the first, di-olefins are selectively
hydrogenated to mono-olefins at high pressure and low temperatures
(SO-130C) in a trickle-flow mode. In the second stage the product is
completely desulphurised and ole fins saturated. In this stage the
reactor operates at 45-65 MPa and 230-2S0C. The catalyst can be a
supported nickel-molybdenum.
Another simple example of hydrotreatment is smoke point improve-
ment, where the aromatic fraction of kerosene is hydrogenated to
naphthenes, improving the burning characteristics.
The petroleum fractions exploited are becoming heavier and contain
much more sulphur and heavy metals which accumulate after distilla-
tion at the 'bottom of the barrel'. The desulphurisation of residual
fractions containing metals and asphaltenes differs from conventional
desulphurisation. The hydrogen partial pressure can be as high as
15 MPa while the lower reactivity of the sulphided species calls for
substantially longer contact times.
Hydrocracking
Hydrocracking is one of the ways of converting the heavy fractions
into middle and light distillates. Other processes are coking,
visbreaking/thermal cracking and catalytic cracking. An important
aspect of these processes is that they operate at very low pressure, and
investments are lower than for hydrocracking. A very important
feature of hydrocracking is the flexibility with respect to the range of
products obtained and their high quality.
106 E. Churin
During hydrocracking, heavy oil fractions are catalytically converted
under high hydrogen pressure to products of lower molecular weight.
The severity of the process depends on the degree of conversion
required. When a limited reduction in the molecular weight is
required, a single-stage process can be used, but when high conversion
is required, a mUlti-stage process is needed. In the first stage
hydrotreating is aimed principally at removing or reducing nitrogen-
containing compounds which have an adverse effect on catalytic
activity. Most of the hydrocracking reaction take place in the last
stage. Typical reaction conditions are a temperature of 400C and
pressure between 10 and 15 MPa. In mild hydrocracking a pressure of
5 MPa is used.
HYDROTREATMENT OF BIOMASS-DERIVED OILS
The quantity of oxygen contained in pyrolysis oils is considerably
greater than the oxygen content of any other material which could be
used as fuel or raw material to produce it (Table 1). This affects the
energy content, and the heating value is rather low. Stability is also
adversely affected.
In the case of bio-oils, hydrotreatment should produce organic
compounds free of oxygen, nitrogen and sulphur as a result of the
following reactions.
Oxygen-containing compounds- Hydrocarbons + H
2
0
Nitrogen-containing compounds- Hydrocarbons + NH3
Sulphur-containing compounds- Hydrocarbons + H
2
S
In addition to these reactions, a reduction in the molecular weight of
the compounds and an increase in the HI C ratio will normally be obtained.
Table 1
Composition of fuels and raw materials
Fuel or raw material
Fuel oil no. 2
Petroleum
Fuel oil no. 6
Shale oil
Oil from coal
Pyrolysis oil (Waterloo, Canada)
Pyrolysis oil (Georgia Tech., USA)
Pyrolysis oil (Raiano, Italy)
Atomic Oxygen (% wt)
ratio, Hie
172
171 0-05
152 1
148 04
126 35
141 40
131 38
131 26
Upgrading of Pyrolysis Oils by Hydrotreatment 107
Studies on upgrading deal with different catalysts, bio-oils and
processes. The hydroprocessing of high-pressure liquefaction oils and
pyrolysis oils in a flow reactor was studied by Elliott & Baker at the
Pacific Northwest Laboratory, Oregon, USA [1,2]. The high-pressure
liquefaction oils were produced at Albany, Oregon, USA, in the
biomass liquefaction facility of the US Department of Energy. This
was an alkali-catalysed process with reducing gas (CO and H
2
) at a
pressure of 14 MPa and temperature around 320C. TR7 oil represents
the aqueous slurry process with an acid treatment and TR12 represents
the recycle oil slurry process. Because of the severity of the reaction
conditions the oxygen content of the oils is about 15%, which is much
lower than the oxygen content of pyrolysis oils. The hydrotreated
pyrolysis oils were produced at Georgia Tech Research Institute
(entrained bed pyrolysis) [3], University of Waterloo (flash pyrolysis)
[4], SERI (vortex reactor) [5], Laval University (vacuum pyrolysis)
[6]. The elemental composition of the oils is presented in Table 2.
The reaction conditions for the hydroprocessing of the high-pressure
liquefaction oils were: temperature 400C; pressure 14 MPa; space
velocity between 01 and 06h-
1
; the catalyst was sulphided cobalt-
molybdenum supported on alumina.
Figure 1 shows the effect of the space velocity on the oxygen content
of the products. At very low space velocities the oil is almost
completely deoxygenated. Under the same reaction conditions TR7 oil
gives a higher yield than TR12 oil with lower oxygen content. The
difference in the reactivity may be due to the higher multi-ring
phenolics content of TR12 oil.
The figure shows that a very low space velocity must be used if a
product is required with a low oxygen content. In the case of pyrolysis
Table 2
Elemental composition of biomass-derived oils
Percentage by wt (wet basis)
Element Georgia Waterloo SERf
Laval TR7 TR12
Carbon 395 453 486 499 748 726
Hydrogen 75 75 72 70 80 80
Oxygen 526 469 442 430 166 163
Nitrogen <01 <01 < 01 <01 <01
Ash 02 003 05 30
Moisture 290 245 184 35 50
108
%0 8
6
4
2
0
0.0 0.1 0.2
E. Churin
0.3
LHSV
0.4
EI TR7
TR12
Pyrel. Oils
0.5 0.6
FIG. 1. Effect of space velocity on the oxygen content of hydrotreated bio-oils
(from [5]).
oils the oxygen rejection is much more sensitive to the space velocity
than for high-pressure liquefaction oils.
Elliott showed that the pyrolysis oils needed initial hydrotreatment
at temperatures between 250C and 280C in order to stabilise the oil
before upgrading under conditions similar to those for high-pressure
liquefaction oils. Table 3 shows the results obtained in each stage with
the pyrolysis oils produced at Georgia Tech.
Non-isothermal conversion with temperatures of about 250-280C at
the bottom of the bed and 370-400C at the top of the bed has also
been proposed [2].
Table 3
Two-stage upgrading of Georgia Tech pyrolysis oil
Catalyst
Temperature, C
Pressure, MPa
LHSV, (vol. oil/vol. cat. h)
Yield
Total oil, 1/1 feed oil
C5-225C, 1/1 feed oil
Hydrogen consumption, l/l feed oil
Stage 1
CoMo
247
13-5
062
069
007
60
Stage 2
CoMo
353
13-5
011
062
045
576
Upgrading of Pyrolysis Oils by Hydrotreatment 109
Two different pyrolysis oils produced at the pyrolysis unit located in
Raiano, Italy, and operated by the Alten Consortium were
hydrotreated in a batch reactor by Churin at the Universite Catholique
de Louvain [7]. The catalysts tested in typical hydrotreating conditions
were CoMo, NiMo and phosphorus-modified NiMo supported on
alumina. One of the oils was produced from wood and contained 30%
oxygen and the other was produced from olive husks, a lignin-rich
material, and contained around 15% oxygen and 3% nitrogen.
The hydrotreatment was effected in two stages (at 250C and 380C)
but the wood-derived oil showed only a very limited upgrading
because the batch reactor does not allow for optimum contact time.
Under the same conditions the olive husk-derived oil showed 70% of
hydrodeoxygenation (HDO) but only 58% of hydrodenitrogenation
(HDN). With this oil the hydrogen consumption rate was very high
from 230C. Wood-derived oil showed good conversion only in the
presence of a hydrogen donor solvent (tetralin). The difference in the
reactivity of the oils may be due to the oxygen content and to the
nature of the oxygenated functions; in fact, the olive husk-derived oil
presented most of the hydroxyls in the phenolic form and had very low
acid content. These experiments show that the nature of the oils to be
treated is very important and probably bio-oils derived from lignin
constitute the best feed for hydrotreatment.
Gevert and Otterstedt at Chalmers University of Technology in
Gothenburg, Sweden, have extracted TR12 oil with decalin and
recovered about 30% of the oil [8]. The extracted oil in decalin was
hydro treated in . a batch reactor at temperatures between 300C and
390C and a pressure of about 15 MPa, with a CoMo catalyst. The
results showed that the heavier fraction of the feed can be converted
hydrothermally but the production of naphtha needed a catalyst. They
found that the higher the temperature, the higher the conversion to
the gasoline fraction, which represented around 20% at 400C. Gas oil
and naphtha fractions constituted about 60% at 400C and 10 or
15 MPa.
Nelte & Meier zu Kocker [9] studied the hydro treatment of an oil
obtained by liquefaction of wood in a carrier oil (tetralin or a recycle
oil) at 5 MPa and 400C. The upgrading stage was effected at 35 MPa
and 300-400C, with a carrier oil/biomass-derived oil ratio of 2. The
oxygen content of the product obtained was about 1 %.
Soltes and coworkers at the Department of Forest Science at Texas
A&M University [10,11] have conducted studies on the hydro process-
110 E. Churin
ing of tars produced by pyrolysis of biomass. The tests were carried
out in batch and trickle-bed reactors with decalin and methylcyclo-
hexane as hydrogen donors. The results obtained in the batch reactor
tests (standard conditions were temperature 400C, pressure, 7 MPa
at room temperature, reaction time 60 min, oil charged 60 g, catalyst
20 g, solvent 100 g) showed that the highest yields were obtained with
the catalysts made up of 5% or 2% of noble metals (Pt, Pd, Rh, Ru)
on alumina or charcoal. For these catalysts the yields were the same
for both hydrogen donor solvents at between 30% and 50%. The yield
obtained with a CoMo catalyst and methylcyclohexane or decalin was
very low. The results obtained with the trickle-bed reactor with decalin
as hydrogen donor showed that the higher the pressure and tempera-
ture, the higher the conversion (for temperature between 350C and
400C and pressure between 5 and 10 MPa). A curious result was that
the oxygen removal was not affected by changes in space velocity
(when varied between 05 and 3 hr-
l
). The best result for the flow
reactor tests was obtained with a platinum-on-alumina catalyst.
PYROLYSIS OILS CO-PROCESSING WITH HYDROGEN
DONOR SOLVENTS
The utilisation of hydrogen donor solvents is very interesting in
upgrading bio-oils. It is well known that some compounds, when
subjected to an external source of energy (from only light for the most
reactive to high temperatures for the less reactive) can generate free
radicals. For example, free radicals are intermediates in the disin-
tegration of organic coal. They are very important because the value
and the nature of the product obtained depend on the manner in
which they are stabilised. The most important possibilities are reaction
of the highly reactive free radicals:
-with each other to give higher-molecular-weight materials, includ-
ing coke;
-abstracting hydrogen from neighbouring hydrogen-rich groups or
molecules in the mixture.
In the reaction mixture these two possibilities are in competition.
The higher the temperature, the higher the rate of formation of
radicals, and if sufficient hydrogen is not available, the first possibility
will be favoured. The second possibility can be exploited to stabilise
Upgrading of Pyrolysis Oils by Hydrotreatment 111
the radicals and facilitate the conversion. This can be done if the
concentration of hydrogen-rich compounds which are able to donate
hydrogen is increased. This is the choice of some coal liquefaction
processes such as EDS (Exxon Donor Solvent) and SRC (Solvent
Refined Coal). Deno et al. [12] reviewed the use of hydrocarbons and
other compounds as hydrogen donors. A large number of reactions of
this type are known and hydrogen transfer can occur at temperatures
as low as 25C. Hydroaromatic compounds are very active for this
transfer. Tetralin is one of the most widely used and the most studied.
Tetralin has also been used in wood liquefaction [13].
The influence of the presence of tetralin and the minimum quantity
needed to allow for a good conversion were studied by Churin et al.
[14]. A bio-oil was treated with 2, 1 and 05 parts of tetralin, which did
not dissolve the oil at room temperature. Reaction without tetralin
was also carried out. The total quantity of liquid phase always
amounted to 400 g with an oil/catalyst ratio of 5.
Table 4 shows that the conversion obtained without solvent is quite
good, as shown by a hydrodeoxygenation (HDO) of 70%; nitrogen is
also eliminated to the extent of 58%; 50% had a boiling point lower
than 370C. When tetralin was added (at a ratio of O 5) HDO
increased to 80% and HDN to 75% and the distillable products
represented 75%. For equal parts of tetralin and oil, the oxygen
content of the product was 22% but interestingly, almost all the
product was distillable and the residuum represented only 5%.
The results confirm the beneficial influence of hydrogen donor
solvents. It is difficult here to distinguish between the contribution of
Table 4
Characteristics of hydrotreated oils
Percentage
Without Tetralin/oil ratio
tetralin
05 1
Oxygen 47 3 22
HDO 70 80 85
HDN 58 75 85
Volatile fraction 50 75 95
112 E. Churin
the catalyst and that of the co-processed solvent. Tetralin yields
naphthalene after donating hydrogen. Naphthalene is rapidly trans-
ported to the catalyst surface where it is hydrogenated, replenishing
the hydrogen donor which thus plays the role of hydrogen carrier. It
gives up hydrogen to the free radicals, returns to the catalyst surface
where it reacts with dissociatively adsorbed hydrogen, and then
shuttles back to the oil. At the same time, the other compounds
constituting the oil are also adsorbed on the catalyst surface and
C-O, C-N and some C-C bonds are broken. It must not be
forgotten that hydrodeoxygenation and hydrodenitrogenation occur on
the surface of the catalyst and not through the hydrogen donor. Table
4 shows that in the presence of a hydrogen donor the percentages of
HDO and HDN are higher. This can be explained by the higher level
of activity of the catalyst. By saturating the free radicals the hydrogen
donor prevents this recombination which can lead to high-molecular-
weight compounds. They can adsorb irreversibly on the catalyst
surface and produce coke, thus blocking active sites and pores.
CATALYSTS USED IN HYDROTREATMENT OF
PYROLYSIS OILS
The most common catalysts used in hydrotreatment are mixtures of:
---cobalt and molybdenum (CoMo);
-nickel and molybdenum (NiMo);
-nickel and tungsten (NiW).
They are always used in their sulphided form and supported on
alumina or silica-alumina. Metals such as platinum or palladium are
much more active hydrogenation catalysts than metal sulphides, but
they are strongly poisoned by sulphur and cannot be used in the
processing of heavy petroleum fractions or coal-derived liquids. The
CoMo catalysts provide good selectivity for the HDS reaction and a
rather low hydrogen consumption because of the low hydrogenating
activity. The hydrogenating activity of NiMo and NiW is much higher.
They provide good selectivity for the HDN reaction because it needs
hydrogenation of the molecule before breaking the C-N bond.
It is very difficult to obtain information regarding the selectivity of
these catalysts for the HDO reaction of complex feeds, and that
obtained for model compounds presents many discrepancies.
Upgrading of Pyrolysis Oils by Hydrotreatment
Table 5
Specific rate constants for HDO and HYD
NiMoP
NiMo
CoMo
16 X 10-
9
09 X 10-
9
05 X 10-
9
48 X 10-
9
35 X 10-
9
10 X 10-
9
113
Ratcliff et al. [15] studied the HDO activity of NiMo catalysts on
aluminophosphate supports having a P / Al atomic ratio of 0-1 in the
transformation of a lignin model compound, 4-propylguaiacol. They
found that by incorporation of phosphorus the production of dealky-
lated phenols and hydrocarbons was increased.
In a study of HDO of o-cresol and HYD of naphthalene with
phosphorus-modified alumina-supported NiMo catalysts, Callant [16]
found a maximum activity at around 1 % of phosphorus. Table 5 shows
the specific rate constants obtained for CoMo, NiMo and phosphorus-
modified NiMo catalysts.
NiMo-based catalysts provide a much higher hydrogenating activity
and a higher deoxygenating activity than CoMo-based catalyst. This
result is not in accord with Elliott [1], who reported that aNiMo
catalyst was less effective than CoMo in removing oxygen. The higher
hydrogenation activity of NiMo catalysts leads to high hydrogen
consumption: 440 litre kg-
1
for NiMo and 380 litre kg-
1
for CoMo.
Some of the light products such as benzene and methyl-substituted
benzenes are also hydrogenated and this constitutes hydrogen wastage,
because the value of these compounds as gasoline components is lower
than that of the non-hydrogenated compounds because of the lower
octane number.
CATALYST AGEING
During the conversion, catalysts lose their activity at a rate that
depends on the reaction conditions and on the nature of the feed to be
transformed. The deactivation appears as a consequence of the
deposition of coke and metals, blocking pores, sintering of the active
phase, poisoning of active sites, etc. Coke formation is a consequence
of the polymerisation of some compounds to give high-molecular-
weight structures which are irreversibly adsorbed on the surface of the
114 E. Churin
catalyst. Coking rate increases with increasing temperature, decreasing
hydrogen partial pressure and increasing feed boiling range. High
levels of some compounds (such as mono- and di-olefins) also
contribute to increased coking rates. The blocking of pores is due
mainly to the accumulation of metals contained in the feed; in the case
of petroleum, nickel and vanadium contained in porphyrin-type
compounds are the main contaminants. When the metal content is
very high, especially tailored catalysts are used for demetallisation.
Sintering of the active phase can take place if the reaction is conducted
in extremely severe conditions or during regeneration of the deactiv-
ated catalyst. The consequence will be, as in the other cases, a
diminution of the number of active sites, which leads to lower reaction
rates.
No studies have been found dealing with the deactivation of
catalysts during the upgrading of pyrolysis oils. Baker [17] reported
that during a 48-hour test run with a high-pressure liquefaction oil,
hydrogen consumption fell rapidly. The author measured carbon
contents higher than 10% on catalysts used in a batch reactor. Such
values are extremely high for short-duration tests and may indicate
severe deactivation of the catalyst.
The very low space velocity needed to obtain good deoxygenation of
pyrolysis oils as shown in Fig. 1 may be a consequence of severe
deactivation of the catalyst and not of the difficulty of breaking the
C-O bond. In fact, studies with model compounds show that
deoxygenation is quite a rapid reaction.
A possible way to contribute to diminished catalyst deactivation is to
pretreat the oil with cheap disposable catalyst. This can provide
further stabilisation by condensation of the most reactive fractions
before contacting the supported catalyst. The results obtained in the
first experiments in the author's laboratory with molybdenum and iron
catalysts seem to be promising.
The extension of the deactivation of the catalyst should be precisely
determined because if it loses activity very rapidly this has to be
considered in the design of the conversion process and especially in the
choice of the reactor. The majority of hydrotreating reactors in
commercial use contain fixed beds of catalysts of either downflow,
upflow or radial flow design; when the feed is mixed vapour and
liquid, the reactor is commonly called a trickle-bed reactor. Reactors
can contain multiple beds of catalyst and trays in order to redistribute
flows to achieve better catalyst effectiveness. This kind of reactor is
Upgrading of Pyrolysis Oils by Hydrotreatment 115
not expensive but it needs to be taken out of service for catalyst
regeneration. This operation cannot be effected very frequently
because of the perturbations on the whole process and other pos-
sibilities must be considered . .
An alternative can be the ebull-ating or expanded-bed reactor used
in the H-oil process (licensed by Hydrocarbon Research, Inc., and
Texaco) and the LC-Fining process (licensed by the Lummus Com-
pany and Cities Service Research and Development Company) to
hydrotreat and hydrocrack residual feedstocks. Some of the ad-
vantages of this reactor, which is more expensive than a fixed-bed
reactor, are a longer on-stream factor because the catalyst is added
and withdrawn without shutting the reactor down, constant catalyst
activity, constant product yield and product quality, and elimination of
catalyst bed plugging due to feed particulate contamination.
CONCLUSION AND RECOMMENDATIONS FOR FUTURE
RESEARCH
The results obtained by a number of researchers clearly show that
hydrotreatment constitutes an interesting way to improve the quality
of biomass-derived oils. The upgrading takes place through a hydro-
deoxygenation and hydrocracking of heavy fractions and products
obtained are in the range of gasoline and gas oil fractions. The
hydroprocessing technology used in the petroleum refining industry
can be successfully adapted to bio-oils because similar catalysts and
reaction conditions are needed. However, some peculiarities of
biomass-derived oils such as reactivity and instability must be taken
into account and the introduction of a pretreatment step appears to be
very helpful. The preferred catalysts are CoMo and NiMo supported
on alumina or phosphorus-modified alumina in the sulphided form;
sulphided compounds must be added to the feed because the sulphur
content of the bio-oils is not high enough to maintain the active phase
in the sulphided state. Noble-metal-based catalysts are also active but
they are much more expensive and are claimed to deactivate more
rapidly.
At the present state of the research a number of points need
further investigation in order to clarify the potential and drawbacks of
this upgrading process.
116 E. Churin
-The IQng-term stability Qf the catalysts. This includes nQt Qnly
deactivatiQn by cQke fQrmatiQn but alsO' stability Qf the sulphided
phase which can becQme reduced if nO' precautiQns are taken
cQncerning the sulphur cQncentratiQn in the feed.
-MQdel cQmpQund studies. The literature shQWS discrepancies in
the mechanism by which hydrQdeQxygenatiQn take place. A clear
understanding will facilitate the design Qf new, mQre active
catalysts.
-DevelQping new catalysts. New catalysts can be Qbtained by
mQdifying thQse which have shQwn gQQd activity to' take intO'
aCCQunt the peculiarities Qf biQ-Qils. Cheap, disPQsable catalysts
need to' be develQped fQr a pretreatment stage.
-DevelQping data in flQW reactQrs. With a few exceptiQns mQst Qf
the research Qn biQ-Qil upgrading has been carried Qut in batch
reactQrs.
-CQ-processing Qf biQ-Qils and petrQleum-derived fractiQns. This
eQuId be the first step fQr the intrQductiQn Qf biQmass-derived Qil
intO' the market Qf high-quality fuel.
ACKNOWLEDGEMENTS
The authQr acknQwledges the financial SUPPQrt Qf the CQmmissiQn Qf
the EurQpean CQmmunities fQr the biQmass upgrading studies and
thanks Dr Grassi and Dr Pirrwitz Qf the BiQmass divisiQn Qf the DG
XII fQr many useful discussiQns.
REFERENCES
1. Elliott, D. C. & Baker, E. G. In Energy from Biomass and Wastes X, ed.
D. L. Klass. IGT, Chicago, 1987, p. 765.
2. Baker, E. G. & Elliott, D. C. In Research in Thermochemical Biomass
Conversion, ed. A. V. Bridgwater & I. L. Kuester. Elsevier Applied
Science, London and New York, 1988, p. 883.
3. Knight, I. Pyrolysis as a Basic Technology for Large Agro-Energy
Projects, 15-17 October 1987, L'Aquila, Italy.
4. Scott, D. & Piskorz, I., Can. J. Chem. Eng., 62 (1982) 404.
5. Diebold, I. In Specialists' Workshop on Fast Pyrolysis of Biomass, 19-22
October 1980, Copper Mountain, Colorado, USA, p. 237.
Upgrading of Pyrolysis Oils by Hydrotreatment 117
6. Roy, c., de Caumia, D., Blanchette, D., Lemieux, R. & Kaliaguine, S.
In Energy from Biomass and Wastes IX, ed. D. L. Klass. IGT, Chicago,
1985, p. 1085.
7. Churin, E., Grange, P. & Delmon, B., EEC Contract EN3B-0097-B, Fuel
Report.
8. Gevert, B., PhD thesis, Chalmers University of Technology, Gothenburg,
Sweden, 1987.
9. Nelte, A. & Meier zu K6cker, H. In Proc. Int. Congress, Euroforum
New Energies, Saarbrucken, FRG, Vol. 3, Stephens and Associates, UK,
1988, p. 673.
10. Soltes, E. J., Lin, S.-c. K., Sheu, Y.-H. E., Amer. Chem. Soc., Div. Fuel
Chem., Prepts, 37(2) (1987), 229.
11. Soltes, E. J. & Lin, S.-c. K., Biotech. and Bioeng. Symp., 13 (1983) 53.
12. Deno, N., Petersen, H. & Sainer, G. S., Chem. Rev., 60(1) (1960) 7.
13. Burton, A., De Zutter, D., Poncelet, G., Grange, P. & Delmon, B., EEC
Contract ESE-R-033-B (1986), Final Report.
14. Churin, E., Grange, P. & Delmon, B. Paper presented at EEC Biomass
Contractors' Meeting, 25-27 May 1988, Paestum, Italy.
15. Ratcliff, M. A., Johnson, D. K., Posey, F. L., Maholland, M. A.,
Cowley, S. W. & Chum, H. L. In Research in Thermochemical Biomass
Conversion, ed. A. V. Bridgwater & J. L. Kuester. Elsevier Applied
Science, London and New York, 1988, p. 941.
16. Callant, M., MSc thesis, Universite Catholique de Louvain, 1988.
17. Baker, E. & Elliott, D., Amer Chem. Soc., Div. Fuel Chem., Prepts,
32(2) (1987) 257.
5
Charco al-Water Slurries: State of the Art and
Future Prospects
CATHERINE ESNOUF
Centre National du Machinisme Agricole, du Genie Rural, des Eaux et
des Forets (CEMAGREF), BP121, 92164 Antony Cedex, France
ABSTRACT
Charcoal-based slurries with water or oil provide an alternative liquid
fuel that has some advantages over bio-oil. The characteristics of
slurries are described and recent research and development activities on
production and testing of slurries are reviewed. Several char-water
slurry and ternary slurry manufacturing processes are described and
techno-economically evaluated, concluding that there are currently
limited opportunities for implementation, but research and development
in well defined areas could improve the economic viability of these
products.
1 INTRODUCTION: WHY SOLID-LIQUID MIXES?
1.1 Why liquids?
The considerable advantages that can be gained from the use of liquid
fuels provide justification for attempting to transform solid fuels into
liquid fuels. The main advantages are:
-great ease and reduced cost of transport, due to greater energy
density;
-easier storage and handling, which is essential in the case of small
(10-20 kW) and medium (500 kW-5 MW, for district heating) size
ranges;
119
120 Catherine Esnouf
-a simple combustion technology, giving good performance with
low emissions of pollutants.
Dry pulverized mineral coal, handled pneumatically, has met great
success in reconversion of fuel technologies, but can only be con-
sidered for large installations of around 30 MW upwards.
1.2 Why not 'liquefaction'?
Liquefaction refers to treatment leading to a modification of the
structure at a molecular level. Results obtained to date in the
liquefaction of mineral coal lead to very high capital and high
operating costs which, in view of the yield from conversion, do not
give a profitable process.
In the case of biomass, liquefaction would be effected directly from
wood, and research is under way in this direction, as reported in
Chapters 2 and 3.
1.3 Definition of a charcoal slurry
This term includes all formulations of pulverized coal slurries (mineral
coal or vegetable charcoal) in one or more liquids, fuel or not (fuel-oil,
'water, alcohol, etc.), which give a stable liquid.
1.4 Target markets
Initial evaluation suggests that larger sizes in the combustion market,
by replacement of heavy fuel-oil, is possible, but strong competition is
likely from pulverized mineral coal. In the combustion market for
small and medium power ranges (from 20 kW to 5 MW), substitution
of domestic fuel will require the limitation of capital cost for boilers'
retrofitting. If slurries can be used in this way, the marketing of
slow diesel engines for generator sets is possible. (The boat engine
market will be limited by the extra space needed to store the fuel).
2 HISTORY OF MINERAL COAL SLURRIES
Projects concerning vegetable charcoal slurries are derived from those
involving mineral coal. It is therefore relevant to review how these
developed. The coal slurry concept dates back to the start of the
petroleum industry in the form of slurries in fuel-oil. Whenever there
was a shortage of petroleum supplies, interest revived and the most
recent work started in 1973.
Charcoal-Water Slurries 121
2.1 Mineral coal/fuel mixtures
These projects were orientated to finding a substitute for heavy
fuel-oil. Using the conventional technology of industrial crushing, the
size characteristics of the coal were typical of pulverized dry coal, i.e.
a diameter of 1-200 Ilm, with an average of 551lm.
Thus maximum concentrations of 50% coal in oil were obtained,
reduced in practice to 45% to minimize the risk of obstructing the
pipelines. Some demonstration operations were realized, including:
-in 1981, on a 400-MW boiler, by Florida Power and Light, USA;
-in 1982-1984, on an electric 121-MW boiler, by Florida Power,
Bartow, USA;
-in 1984, on 2 x 265-MW boilers, by Tokyo Electric Power, Japan.
The mixes were produced and marketed by the companies, as
'Coalliquid' (USA), 'Comco' (USA), and 'Japan COM Company' .
The technical results were satisfactory but economic profitability was
not achieved, for it took 10 to 15 years to realize a return on the
investment. The substitution of fuel-oil was only 30%, and transfor-
mation of the boiler was costly due to the need for a smoke dust
removal system, an ash removal device, new devices for injection into
the burners, special pumps, etc.
These projects led to the conclusion that a less costly suspension
fluid was needed so attention turned to water.
2.2 MineraI coal-water mixtures
These processes developed very rapidly from 1980 to 1985. Three
precursors used a virtually similar technology which enabled them to
obtain concentrations of 70-75% coal (by weight): Atlantic Research
Corporation (USA); Carbogel-Fluidcarbon in Sweden; and Slurry-
tech (USA).
The technology is characterized by the addition of chemical addi-
tives as surface-active agents which increase wettability of the solid by
the water, and by multi modal size distribution to optimize the space
density of the solid, which is obtained by wet grinding in a ball-type
mill.
Starting in 1982, this technology led to demonstration operations in
the USA, Japan and Sweden involving power capacities up to
75MW.
122 Catherine Esnouf
In 1983-1984, large-scale marketing of these products stumbled over
the following two obstacles:
-the 70% coal concentration could only be obtained by a process
(nature of surface-active agent and granulometry) that was
specific to each type of coal;
---<:onversion of the boilers for these mixtures required very costly
capital investment in dust removers and ash pits which are only
profitable for high-power boilers (above 20 MW). However, thus
equipped, these boilers can burn dry pulverized coal for less cost,
including the capital cost necessary to protect against risks of
explosion.
In these conditions, industrially produced coal-water mixtures only
penetrated the market slowly.
These mixtures continue, however, to be developed in Japan, due to
a determined policy to reduce energy dependency; in China; and in
the USSR (where transfer of Siberian coal to the West by pipeline is
anticipated in early 1990). The processes are also used to transform
very wet raw materials such as slimes (the by-product of coal-washing
plants), for example using the Cerchar process (Charbonnages de
France) or by the Fluocarbelf process (Elf-France Company).
2.3 Purified mixtures
It can be concluded from this brief analysis that in order to penetrate
the market significantly, the slurries must require as little modification
as possible to the user's technical environment, i.e. they must be real
substitutes for fuel. A primary objective is, therefore, to remove ash
from the coal before slurrying.
Current standards relating to dust emission into the atmosphere limit
the discharge for medium-sized power plants 3 MW) to 024 g/MJ.
This corresponds to a coal with 08% ash (if all the ash leaves in the
smoke). Ash removal must therefore be highly efficient since washed
coal contains 8-12% of ash on average.
Ash removal to this extent requires ultra-fine grinding to an average
diameter of 10 f.tm to extract the mineral matter. The problem is then
that there is no longer a multimodal size distribution and the surface
area of the solid is very extensive. This limits the coal content to 55%
by weight which, including losses due to water vaporization on
combustion (1000 kJ/kg), gives mixtures with a lower heating value of
approximately 15 MJ /kg.
Charcoal- Water Slurries 123
More recent research incorporates a small percentage of fuel-oil
(6-20%) to increase the LHV of the mixture and as an agent to aid
ash removal. Mixtures that meet ash removal standards and with a
lower heating value (LHV) of 24 MJ /kg have been produced. It
seems, however, that the combustion characteristics of the mixture
lead to high burner derating which may affect the viability of the
processes [1].
3 THE PLACE OF VEGETABLE CHARCOAL COMPARED
WITH MINERAL COAL
It has been shown that mineral coal slurries have not yet been able to
penetrate the market significantly. What may be the advantage of
biomass?
Production of mixtures from biomass excludes the direct use of
wood as swelling limits the content of solid matter so wood charcoal
must be used. How does this material compare with mineral coal?
3.1 Disadvantages
A major problem is dispersion of biomass over large areas and hence
high cost of the biomass resource. Also, charcoal represents only 50%
of the energy contained in biomass. In addition, charcoal is highly
hygroscopic.
3.2 Advantages
Vegetable charcoal has characteristics such as friability and low ash
content which will reduce the cost of conversion into a mixture.
Because it is highly friable, grinding can be less costly, and the energy
cost of crushing is also reduced. Charcoal contains little ash. Poplar
wood, from a short-rotation coppice for example, contains 08-11 %
ash, i.e. the charcoal obtained has 24-33% ash. Mineral coal usually
contains more than 10% ash.
In addition, wood varieties can be chosen with a low ash content,
e.g. pine will give a charcoal with 07% ash. In the ash, sulphur which
is always present in coals and heavy fuel-oils, is not significant.
However, the melting temperature of the ash must be monitored to
avoid clinker formation in the burners.
The burning characteristics of the mixture can be improved if the
charcoal contains a high percentage of volatile matter, i.e. resulting
from carbonization at a relatively low temperature of 350-400C.
124 Catherine Esnouf
3.3 What are the favourable market opportunities?
For high power outputs of more than 50 MW, the market is occupied
by pulverized coal. The rest of the market is possible, i.e. power
outputs below 50 MW such as diesel engines for generator sets.
3.4 Co-products
The role of pyrolysis liquids (bio-oil), co-product of charcoal produc-
tion, should be considered by using it in the mixture to increase the
energy yield of the conversion process.
To conclude, biomass-based slurries would appear to be favourably
placed for certain gaps in the market.
4 FUNDAMENTAL ASPECTS OF SLURRY MANUFACTURE
Slurries must satisfy several objectives of a somewhat contradictory
nature.
4.1 Charcoal concentration
The minimum lower heating value required for the liquid to be usable
in boilers currently retrofitted is 167 MJ/kg. However, the LHV
of wood charcoal is from 27 to 31 MJ/kg. Therefore the minimum
charcoal concentration has to be 53-61 % by weight of the total.
A theoretical maximum volume concentration of solid is known,
which corresponds to the case when the liquid is no longer of sufficient
volume to wet the whole of the surface area of the divided solid. For a
given mass, this concentration depends on the size range
characteristics.
The liquid has a dual role when applying stress to the solid/liquid
mixture. Firstly it wets all of the particles and thus provides lubrica-
tion, and secondly it withstands shear resulting from the stress applied
to the mixture, thus giving it the macroscopic properties of a liquid.
There is a further complexity in that the charcoal particles are not
produced in the form of regular spheres of the same size.
In order to obtain the maximum concentration of solid, a number
of physical and chemical modifications are necessary:
-Physically, a suitable size distribution is used to enable small
particles to fill the spaces left by larger ones. To do this, a
multimodal distribution is required, i.e. several populations of
particles of distinctly different diameters.
Charcoal- Water Slurries 125
-Chemically, the wettability of the solid can be increased by adding
a surface-active agent (dispersing agent) such as naphthalene
sulphonates.
4.2 Stability
The slurry mixture must be stable with no solids deposit for long-term
storage, for example three months, although periodic stirring may be
required.
The viscosity must be low enough to permit pumping through pipes
and spraying in fine droplets into the burner to give good combustion.
In nozzle-type burners, this operation corresponds to a high shear rate
applied to liquids and the fluids which exhibit dilatancy have very high
viscosities, as opposed to pseudo-plastic fluids. It is considered that a
viscosity of 15 Pa s (1500 cP) should not be exceeded for a shear rate
of 100 S-I.
To satisfy these two objectives, 'stabilizing' chemical additives are
included, such as CMC (carboxymethylcellulose).
In the case of certain mixtures, there is a risk of ageing, with
viscosity increasing over time due to the effect of shearing with
agitation. Flow tests over a long period must, therefore, be carried out
to reduce this risk.
4.3 PoUution
When modifying boilers in respect of dust and ash removal or
removing ash from charcoal, less than 024 g/MJ must be discharged
from plants under 3 MW. This standard corresponds to solid-fuel
boilers.
The standard for liquid-fuel boilers is stricter since it imposes a
requirement of less than 005 g/MJ in plants under 9 MW.
In addition, the tendency is towards increasing the severity of these
standards in the future, and it is possible that, by 1995, the next limit
will be set at 0024 g/MJ.
5 STATUS OF CHARCOAL SLURRY TECHNOLOGY
Most of the bibliography concerns wood charcoal-fuel slurries. The
most extensive work was carried out in Brazil, and is briefly described
below.
126 Catherine Esnouf
5.1 Charcoal-heavy fuel-oil mixtures
5.1.1 Brazilian work [2-5]
Two groups have carried out most of the work: the national petroleum
company Petrobras, and Copene (Petroquimica do Nordest SA) in
association with the Japanese IHI (Harima Heavy Industries Co Ltd,
Japan). This work was extensively developed in the years 1980-1983.
The mixtures were the first-generation type mentioned in Section 2:
low-concentration slurries in heavy fuel-oil using crushing technologies
developed from pulverized coal.
Copene's objective was to use heavy fuels with high sulphur and
nitrogen contents without exceeding S02 and NO
x
emission standards,
by mixing with a product free of these elements, i.e. vegetable
charcoal.
For Petrobas, the aim was to limit petroleum imports. Wood
charcoal was chosen in preference to mineral coal, for Brazilian coals
have an average of 50% ash content (bituminous and sub-bituminous
coal). In addition, wood charcoal is produced at a rate of
1210 000 t/year in Brazil, at a cost of US$1O million/million kcal (1982
price), i.e. half the price of fuel oil. This vegetable charcoal comes
from wood cut in the native forests (forest clearance) and is carb-
onized using conventional techniques (mills, pits, etc.). Its characteris-
tics are as follows:
Ash content
Volatile matter content
Moisture
Gross heating value
Average diameter
4-10%
20-30%
5-15%
6000-8000 kcal/kg
3mm
The ease of crushing wood charcoal was confirmed. It was crushed to
pass through a 200-mesh sieve (74 J.tm). The mixtures in general
contained 30% charcoal and 05% additives and were stable over a
7-day period. The Brazilian heavy fuel used is more viscous than US
heavy fuel no. 6. The maximum concentration of vegetable charcoal
was 40% compared with 50% for mineral coal.
The difference between these wood charcoal slurries compared with
mineral coal is interesting:
-Without additives, vegetable charcoal separates more quickly.
-The best additives are not the same in both cases.
Charcoal-Water Slurries 127
-For the same particle sizes, the viscosities of the charcoal mixtures
were higher, e.g.
At 80C, 3000 cP compared with 2000 cP for coal slurry;
At 120C, 300 cP compared with 200 cP for coal slurry.
These observations are believed to be due to too high a particle size
of the charcoal, preserving the porous structure of the solid.
Combustion tests in a small heavy-fuel oven (200 kg/h) equipped
with a vaporizing burner specially designed for slurries, were very
encouraging.
The conclusion is identical to that drawn from the same types of
mineral coal mixes, namely that ash removal devices must be installed
on the boilers and that the burners undergo a power reduction of
30-50%.
The many planned pilot projects were abandoned in 1983 due to the
drop in petroleum prices. Currently, work has ceased.
5.1. 2 Use of Georgia Tech., USA, pilot charcoal
The Pittsburgh Energy Technology Center tested the combustion
characteristics of mixtures obtained from the products of pyrolysis in
the entrained bed of the Georgia Tech. Research Institute (Atlanta,
USA) [6]. Nowhere is there any mention of the stability characteristics
of the tested mixture: 30% wood charcoal, 20% pyrolysis oil, 50% of
heavy fuel oil. However, it is reported elsewhere [7] that the pyrolysis
oils used are fluid only if they contain at least 25% water, that they
are degraded with decomposition and formation of coke if they are
heated for a prolonged period, and that they are acid and highly
corrosive.
The fuel charcoal slurry contains 13% ash, has a higher heating
value of 9550 kcal/kg and a viscosity of 225 cP at 60C. The particle
size of the charcoal is relatively coarse with 92% less than 75 !lm.
In a heavy-fuel burner, combustion is good and satisfies the
objective of reducing the S02 and NO
x
content in the flue gas. It is
specified that ash collection devices would be necessary.
The conclusion is the same as in the preceding case.
5.2 Charcoal-domestic fuel-oil mixtures
Combustion tests in a diesel engine were carried out by the Southwest
Research Institute, San Antonio, Texas, on 10% and 20%
128 Catherine Esnouf
charcoal/fuel mixtures. No details are given concerning the charac-
teristics of the mix; the charcoal particle size is very fine with mean
diameter 14 !.lm. The mixture behaves essentially like the fuel-oil and
90% or more of the charcoal is burned. Engines with a pre-combustion
chamber are preferable to direct injection engines [8].
This brief study is a starting point for tests of more sophisticated
mixtures, and especially the design of appropriate injectors and
long-term tests giving special attention to wear and corrosion.
S.3 Charcoal-water mixes
With the exception of the Italian and French work described later in
detail, only one bibliographical reference mentions such work. It is a
Japanese patent explicitly concerning vegetable charcoal, its mixing
with water and a type of crusher and mixer to enable laboratory-scale
operations [9].
Brazilian work under the leadership of Petro bas [unpublished]
should have given rise to the construction of two charcoal/water pilot
plants in refineries. These projects were cancelled in 1983 due to the
drop in petroleum prices. The work today concerns emulsions of
distillation residues (asphaltenes) in water with three pilot plants of
10 t/h supplying refinery boilers.
6 WORK BY COGIS AND KTI
Laboratory tests have been conducted using two different types of char
produced in the Raiano pyrolysis plant from wood and olive husks
[10,11].
6.1 Charcoal-oil slurries
The first objective was utilization of all the products of pyrolysis, by
slurrying of charcoal in the pyrolysis oil (bio-oil). The composition and
flow characteristics of the pyrolysis oil (containing water and fine
charcoal) were:
Pyrolysis oil
Charcoal
Water
Viscosity at 70C
Viscosity at 100C
70%wt
15%wt
15%wt
13000cP
1900cP
Charcoal-Water Slurries 129
By using pyrolysis oil and charcoal as base products it was intended
to formulate an optimized mixture, characterized by a viscosity of
400-600 cP at 50C, to give comparable pump ability to that of no. 6
fuel oil. The charcoal, therefore, was ground to 100% < 200 !!m,
50% < 30!!m and 10% < 2/3 !!m. The particle size distribution was
similar to that generally adopted for pneumatic transportation and
combustion of pulverized coal. The charcoal particles surface was
examined microscopically and found to be highly discontinuous, with a
pronounced porosity.
At the beginning of the work, attempts were made at producing a
mixture by preparing first a charcoal-water slurry, then adding the oil
under heating (80-85C) and subjecting the sludge to strong mechani-
cal stirring, sometimes followed by ultrasonic stabilization by means of
piezoelectric or magnetostrictive devices. When an excess of oil was
reached, this was not dispersed and it collected as a floating layer.
After removing the excess oil, the remaining very thick charcoal-
pyrolysis oil-water mixture kept stable and the water-in-oil emulsion
constituted a stable film around the char particles. Therefore this
product could be stored for some time without any further separation
of the three components.
Tests have been carried out on various combinations of pyrolysis oil,
charcoal, surface-active additives of the non-ionic type (ethoxylated
nonylphenols, with 4 or 15 ethoxyl groups), water and methanol. Due
to the alcohol in some formulations, an average temperature of 50C
for mixture preparation was chosen (at this temperature the oil
viscosity drops substantially and the alcohol does not have too high a
vapour pressure).
The preparation procedure included oil preheating to 50C, mixing
of surfactants with alcohol (when this was to be used) and, finally,
addition of the mixture to the oil under heavy agitation (stirrer
working at 750 rpm). After thorough mixing, water (when necessary,
and in addition to that already contained in the oil) was added slowly.
If the mixture preparation procedure did not require any alcohol
addition, the surfactants were dissolved or dispersed into water and
the resulting mixture was added to the oil.
Processing pyrolysis oil in this way proved to be very difficult, due to
the similarity of its behaviour to that of asphalts (up to a given
temperature the oil flows on a glass wall without wetting it; further, it
tends to form a lump around the stirrer).
From all the tests conducted it was clear that pyrolysis oil behaved
130 Catherine Esnouf
in a different way from petroleum-derived oils, showing a much lower
propensity to mixing, due to incompatibility with any solvent except
alcohols or tetrahydrofuran.
A preliminary set of tests showed that pyrolysis oil does not mix, or
mixes only under heating, with several mineral oil fractions, solvents
and glycols. After that, a series of mixture preparation tests were
performed using various types of surface-active materials (including
triethanolamine). Emulsified products could be obtained although they
were very thick, and not pumpable, even without charcoal addition to
the emulsions. Further, methanol had been adopted as diluent, in
order to obtain products in the viscosity range of 200-600 cP, typical
of pumpable products (viscosity measured by Brookfield viscometer at
20 rpm). It was found that adding water to the mixture of oil and
alcohol and surfactants (15%) would generally enhance viscosity as a
sign of the formation of water-in-oil emulsions.
Slurries have been prepared without any water addition. It is worth
mentioning again that the pyrolysis oil produced in Raiano at that time
consisted of 70% pyrolysis oil, 15% water in the form of emulsion or
dispersion in droplets and 15% charcoal consisting of very fine
particles not separable by decantation. Therefore some water and
charcoal were always present, even in those tests where neither water
nor charcoal had actually been added to the products.
As the slurries produced were very thick with a low charcoal
concentration, the work was then oriented to the preparation of
charcoal-water slurries, and the oil was used alone or upgraded.
6.2 Charcoal-water slurries
The tests were oriented to investigate the following points: grinding
techniques, size distribution influence on viscosity and stability,
dispersion and stabilization agent selection and dosing, influence of the
oxygen during char milling and influence of char pretreatment at high
temperature.
The results of this first phase were:
(a) The maximum solid content of the char-based mixture was 52%
by weight, with a slurry viscosity below 1000 cPo
(b) The bimodal size distribution curve of the pulverized char
produced an unstable slurry.
(c) By using a very finely ground char powder with a monomodal
size distribution, the same solid content and the same viscosity
Charcoal- Water Slurries 131
as for the bimodal distribution was obtained, but with the
advantage of a very good slurry stability. Another advantage is
the simplicity of the process to obtain the monomodal slurry.
Those conclusions are perfectly consistent with the size of
pores in the charcoal structure: the particle size must be as low
as the pore size to optimize the wettability of charcoal.
(d) None of the surface modifications of the char by heating
treatment, wetting, or ash leaching resulted in an increase in the
solid content of the slurry.
At this stage of the programme the experimental work was
transferred from laboratory to pilot plant. The main results are as
follows.
Solid content
Values higher than those on the laboratory scale were obtained, and
concentrations around 55-56% could be produced with micronized
charcoal.
Slurry viscosity
The samples produced had a viscosity in the range 600-2000 cP at
30C, which is compatible with pumpability requirements. Further-
more the behaviour is pseudoplastic which means significant ad-
vantages in industrial application.
Slurry stability
A series of slurries produced during the tests have been stored in
drums and the tendency for solid separation and water separation
checked every two to three days.
The analysis of the results shows that all the products can be used in
an industrial plant if mildly mixed daily, as is normally done in
installations using coal-water mixtures.
6.3 Charcoal-mineral coal-water slurries
Since the maximum content of solid obtained using only char was
55-56%, even using micronized powder, another line of investigation
was started to produce slurries with char and mineral coal.
The basic concepts of this approach are:
-The mineral-coal can be used for coal-water mixtures with a solid
content up to 65-70%.
132 Catherine Esnouf
-The combination of the two solids makes it possible to reconsider
use of a bimodal distribution using the mineral coal for the coarse
fraction.
-The dilution of sulphur makes utilization of large quantities of
coal possible while remaining within the limits imposed by
environmental regulations.
The new system consists in incorporating coal with an average
particle size of about 45!lm in a micronized pyrolysis charcoal slurry
with a mean particle size of 12-16 !lm.
Experimental work
A first phase of work resulted in slurries with char and coal, in a ratio
of 60: 40. The coarse coal is added to the char slurry (50%). The
behaviour is Newtonian. The resulting slurries have a LHV of
4000 kcal/kg and are usable as fuel in a burner.
A second phase attempted to increase the solid content up to 65%,
with ratios of char-coal of 40/60, 50/50 and 54/46. Analysis of the
samples shows increasing viscosities. With small adjustments to the
quantity of additive which is increased to almost 1%, the slurries
obtained were good and usable in a burner. The LHV is greater than
4500 kcal/kg.
In conclusion, this second group of samples confirms the possibility
of producing mixed slurries with 65% solid and good viscosity stability
and comparable with coal-water slurries.
The final experiments tried to increase further the solid content
above 65%. The result was that it was possible to reach 69 or 70% but
the viscosity was high and at the limits of acceptability for industrial
applications.
6.4 Conclusion
Satisfactory slurries of charcoal in pyrolysis oil could not be obtained
as the viscosity was too high.
Charcoal-water slurries of up to 55% charcoal could be obtained,
using very finely ground charcoal. These results were considered as not
sufficiently interesting and the work has been recently oriented to
ternary mixtures of charcoal-coal-water slurries to increase the solid
content.
Apart from the consideration of sulphur content reduction in water
mixtures, the mixing of charcoal and coal is questionable. It increases
Charcoal- Water Slurries 133
the process complexity, and it increases the constraints on plant
location, in order to allow biomass and coal supply at reasonable costs.
No economic evaluation of the process is presently available.
7 WORK BY CEMAGREF, UNIVERSITE DE
TECHNOLOGIE DE COMPIEGNE AND CENTRE
TECHNIQUE FORESTIER TROPICAL (CTFT)
The work presented here is the most recent activity in this area and
was carried out in the context of the Energy from Biomass pro-
gramme, CEE-DG XII, 1986-1989.
7.1 Objective
The aim was to obtain a purified charcoal-water mixture able to
supply small- and medium-power boilers without ash removal equip-
ment, whilst respecting current environmental standards. The entire
wood-to-slurry energy line has been studied and its economic cost-
effectiveness estimated. It should be noted that, as use in medium-
power boilers corresponds to discontinuous operation, the mixture
must also be easy to ignite.
7.2 Presentation of the energy line
The energy line, as envisaged at the very beginning, is as follows. The
raw material is short-rotation coppice (SRC) , poplar or eucalyptus,
including the bark although it is rich in ash. The woodchips are
pyrolysed in a Cemagref-Framatome pyrolyser with recycling of
volatile matter, which gives maximum charcoal yield. Removal of ash
by treating with acid or by selective agglomeration is followed by
multimodal ultrafine wet grinding and formulation of the slurry (see
the flowsheet in Fig. 1).
r--- ---- --------------,------------- ------------j
, , I I
A
: (PTdl f \: /F5T votafile. .. ____ Burned--!... __ Electr i cify
. , t. /' production
_Drying __ , OOT wood --.. Pyrolysis ............
1 oor wood ) (15% water .........
(50% wafer content) 0
33
T chaf [ oa f
content ) water
/water
1=-::.-===3 +--ctTI---- Deashin.g
0.61 Charcoal waler Wet ball'
slurry 57% d.m. mill ""
18400 kJlkg Additives
,'h j 1.<':-1..;"
mill
100-200)1
FIG. 1. Overall fiowsheet of charcoal-water slurry production from wood.
134 Catherine Esnouf
The final heating value must take into account the heat of
evaporation of the water, which represents a loss of approximately
1000 kJ per kJ of mix, which gives an effective HHV of 17400 kJ/kg.
For the work described here, carbonization was carried out in a
retort by CTFT.
7.3 Crushing
The objective of the study was to determine the type of crusher best
suited to charcoal, i.e. the one which minimizes the transformation
cost. It was also hoped to reduce energy consumption compared with
crushing of mineral coal.
Hammer and nozzle mills require a very high energy consumption
and were abandoned in favour of crushers acting essentially by
compression, which profit from the fragility of the charcoal structure.
A thorough study was made, therefore, of ball and vertical-type mills
(Five-Cail-Babcock).
The tests determined the crushability index (Wi, work index)
representing the suitability for crushing of a material in a given
crusher. Wi relates the specific crushing energy, E., to the initial and
final size range. Dgo is the size prior to crushing, corresponding to 80%
by weight of fines. The same applies for d
so
after crushing.
Wi is calculated using Bond's formula:
For dgo > 70 /lm: Es = 10 Wi ( k -k) in wet crushing
Es = 13 Wi ( k -k) in dry crushing
For d
so
< 70 /lm, a correction factor has to be applied equal to:
d
so
+ 103
1 145dgo
Wi and Es are expressed in kW hit, and d
so
and Dso are in /lm.
On the variable-speed output, the two test crushers were equipped
with a torque meter placed on the drive shaft. Mechanical torque (and
therefore power) is recorded via a remote measuring device. It is an
essential measurement which, cumulatively, gives the specific mechan-
ical power (Es) of crushing, by ignoring the poor transmission
efficiency of small control sets.
Charcoal-Water Slurries 135
A wet ball gives a crush ability index equal to 26 kW hit from 550 f.1m
to 13 f.1m. This index is fairly high compared with mineral coal, which
is generally between 15 and 20 kW hit. Taking a transmission
efficiency of 092, the specific industrial electrical energy to reduce size
from Dgo = 10 mm to d
so
= 13 f.1m will be equal to 110 kWh/t. At this
value, 5 kW hit should be added for the various auxiliaries.
The results on a vertical mill from 1500 f.1m to 14 f.1m show a
crush ability index Wi equal to 52 kW hit. Generally, for mineral coal,
the crush ability index Wi is found to be about 8 kW hit; thus an
appreciable increase is observed. The slope of the Rosin-Rammler
curve is approximately 130. Size dispersion is therefore lower than for
the ball mill, which is a conventional result for vertical mills.
Taking a transmission efficiency of 092, the specific industrial
electrical energy to reduce size from Dso = 10 mm to d
so
= 14 f.1m is
equal to 28 kW hit. To this value should be added the energy
consumed by the various auxiliaries, in particular the turbine. This
consumption is estimated at 10 kW hit. The total electrical energy
consumed will therefore be 38 kW hit.
Economic optimization leads to the choice of a wet ball mill as the
capital cost is much lower (35% less) and the additional energy cost is
not sufficient to reverse the effect. The cost is reduced further if an
initial grinding step is introduced with a centrifugal crusher leading to
80 f.1m, and the wet ball mill thus providing only the final milling from
80 !lm to 15-20 !lm.
7.4 Ash removal
If it is assumed that all the ash produced in the boiler leaves in the flue
gas, which is a very pessimistic hypothesis, charcoal with 07% ash
content must be produced to respect the standard of 1 g/thermie. This
will be the objective initially.
7.4.1 Chemical treatment
Tests giving an initial selection of process parameters were carried out
using birch and chestnut wood. Chemical treatment with acid may
affect the mineral salts contained in the ash (CaO, MgO, K
2
0, etc.),
the proportions of which vary according to species; therefore the tests
had to be confirmed by tests on poplar and eucalyptus. The different
treatment parameters studied were reaction time, temperature, acid
type (HCI, H
2
S0
4
), concentration, treatment with one or more acids
136 Catherine Esnouf
combined, initial ash content (1-4%) and charcoal/acid ratio (40-
200 gil). Each test was carried out on 20 g of charcoal, and the ash
content was determined after combustion at 815C for 2 h.
Results show that it would be advantageous to use 05 M HCl (i.e.
pH = 03) for at least 1 h, at ambient temperature with an average size
of 200 !Lm. The ash removal rate, of 20-70%, depends very much on
the initial ash content (see Fig. 2).
An important result is that all the mineral elements are affected in
the same way, except for silica, which is responsible for the differences
between the tests.
A charcoal/acid ratio of 10% and a reaction time of 10 min can be
used without significant loss in performance. The results obtained on
two types of poplar were a reduction of 34% to 1'2%, and a reduction
of 13% to 08%. It should be noted that ash removal is insufficient to
satisfy the objective. An attempt must be made to replace it or
combine it with ash removal by selective agglomeration (see below).
t
.c
111
<
\
\
\
\
\
:e----- --e----- - - - ----..
0-2M 0-5M M
FIG. 2. Influence of nature of acid and of concentration.
Charcoal- Water Slurries 137
As the aqueous phase obtained from pyrolysis is acid, it may be
possible to use it for ash removal. A spot test with liquid at pH 27
showed a reduction of 34% to 15%, a very interesting result. The
flowsheet in Fig. 3 can then be proposed.
Other systems should be compared economically with the above,
taking into account the necessity for condensation of the aqueous
phase and a more costly capital investment for treatment of discharge
water with a phenol and ketone content.
7. 4.2 Treatment by selective agglomeration
The principle is as follows: very finely milled charcoal (a few Ilm) is
dispersed in a large quantity of water and a hydrophobic liquid while
stirring very vigorously; the hydrophobic particles of charcoal remain
bonded together whereas the hydrophilic mineral matter, liberated by
crushing, accumulates in the aqueous phase [12]. Screening allows
recovery of agglomerated charcoal with ash removed. The product is
known as ultracarbofluid (UCF) or, if biomass is used as the source of
charcoal, bio-UCF. The flowsheet is shown in Fig. 4.
The hydrophobic liquid used is domestic fuel-oil, which has the
advantage of enhancing the final energy content of the slurry. Light
fractions of crude oil not currently marketed can also be used
(presently used mixed with heavy fuels), or light crude oils.
10t acetic acid
for start-up,pH 27
It Pce-oMh;", 11 Sp;"-dCy;", Ql
charcoal 200 -- - --- // 1
- - /
- - -- /
---- /
/
t 1/
Acid
recycling
Acid equivalent to _____ /
at least o,s t of :
pyrolysis aqueous I
phase Extra I HCL or
acetic acid
Washing and
neutral ization
/ \
Water + Clean
minerals
disposal
charcoal
FIG. 3. Conceptual ftowsheet for de-ashing charcoal with acidic pyrolysis
liquor.
138 Catherine Esnouf
Charcoal Water I l
p . Purified and
.. __ hydrophobic liqUid
.. ':' ... ,. ....... .
Hydrophobic liquid Water and ash I

--- --
--- ---
Charcoal-water - hydrophobic liquid
mix - bio-ultracarbofluid (bio-UCF)
FIG. 4. Flowsheet of bio-UCF production.
Only spot tests have been carried out to date on the preparation of
such bio-UCFs. With a mass of fuel-oil corresponding to 20% of the
weight of the charcoal, a crushed charcoal with an average diameter of
8 J.1m and a treatment time of 30 s, the optimum is a reduction of 41 %
to 12% ash.
This reduction alone is not sufficient, but combined with the acid
treatment described previously, it is possible to get down to 08% ash.
However, in the final ternary slurry obtained, respect for the smoke
pollution standard imposes less than a 095% ash content for a
medium charcoal at 7500 kcal/kg as the domestic fuel contributes to
the energy value without any ash incorporation. The two associated
ash-removal operations, therefore, enable the result sought to be
obtained.
The two actions are complementary, since selective agglomeration
preferentially eliminates the silica and the alumina. Neutralization is
not necessary since separation of the agglomerates liberates the acid
aqueous phase. The agglomerates are rinsed until a neutral pH is
obtained. The diagram of combined ash removal and slurry prepara-
tion would then be as shown in Fig. 5. This ftowsheet is used for the
economic assessment.
To conclude, according to the initial ash rate and in particular the
respective percentages of silica, calcium oxide and potassium oxide, a
choice has to be made to remove ash by either acid or selective
agglomeration, or a combination of the two.
A detailed study of coppice-grown poplar and eucalyptus is neces-
sary to choose the optimum process. The choice of ash-removal
method affects the nature of the mixture, binary or ternary bio-UCF.
Charcoal- Water Slurries
1 t charcoal Crushing . 800f0<80(,1m-. Wet mill 7 13
and grinding C ( ) - Mean11ll - I-lm
Addition 3t HCI 01 M
I Ash removal by acid
'- Start with =-__ --,
f . 15W1MHCI I I
Recycling
12t HCI
I
I
10 min
retention
I
I
I
I
I
I
I
Ash removal by selective
agglomeration
250 kg fuel -----:>..
L!J 30 , ",teo'ioo
+
I
I
I
I
I
I
I
I
I
I
L ____ _
Acidic
water

R
----Separation of
agglomerates
(yield 98,.)
Charcoal and fuel
1225 kg
20 kg additives Washing
630 kg wa'e, r I
cb Formulation
..... -----
2075 t slurry
charcoal I fuel I waterl additive
47 12 40 1
FIG. 5. Flowsheet of bio-UCF production with acid washing.
139
The characteristics and possible applications of these mixes are
different. Use of the aqueous phase of pyrolysis needs to be studied in
greater depth.
7.S Characteristics of the charcoal-water slurries
7.5.1 Binary charcoal-water slurry
The mixture is manufactured in a single stage: multimodal ultrafine
crushing is carried out in a ball crusher in a wet process, water and
140 Catherine Esnouf
additives being added in the same crusher. The characteristics of the
mixture depend on the parameters: size range used, type and quantity
of additives; 60-65% charcoal mixes have been obtained with vis-
cosities below 2 Pa s.
As a typical slurry, obtained from any wood charcoal, the following
was chosen:
52 % charcoal
42% water
1 % dispersing agent
20-50 ppm stabilizer
Viscosity
Bimodal size
{
70% of mean diam. 4 JLm
30% of mean diam. 25 JLm
Tamol (naphthalene
sulphonate)
Carboxymethylcellulose
('Hercules')
1900 cP at 100 S-1
For a charcoal of LHV 7500 kcal/kg, the mixture has a theoretical
LHV of 4275 kcal/kg, i.e. an effective LHV of 4035 kcal/kg
(16900 kJ/kg). The mixture obtained, therefore, has a heating value
compatible with the objectives. The rheological behaviour of the mix
is dilatant (apparent viscosity increases with the shearing rate).
Combustion tests are under way on this mixture using a pilot burner of
15 kg/h (100 kW).
It is probable that the major disadvantage of these slurries will be a
difficulty in ignition for intermittent cycles. If a refractory hearth is
necessary for re-ignition, the capital cost of boiler conversion will be
considerably increased. However, the production process is very
simple.
Z5.2 Ternary charcoal-water-fuel mixtures
The production process was described earlier for such slurries. The
composition depends essentially on the particle sizes: the ultrafine
crushing necessitated by ash removal does not permit a multi modal
mixture so the maximum charcoal concentration is lower than with
binary mixtures. The corresponding loss of heating value is largely
compensated by the addition of fuel. In addition, ash removal is better
with smaller sizes but the formation of agglomerates then requires a
larger amount of fuel to maintain a separation yield close to 100%.
Charcoal- Water Slurries 141
From the results obtained, a satisfactory composition with regard to
these different criteria is the following:
charcoal
47
water
40
fuel-oil
12
additives
1
-The size range is average: 0-7 !Lm (100% < 38 !Lm).
-The dispersing agent is a non-ionic wetting agent of Cemulsol
type, sapogenates, Arcopal N, at an average concentration of
08%.
-Stabilizers, 20 ppm.
The viscosity is 1900 cP at 100 S-l. The slurry exhibits pseudo-plastic
behaviour (apparent viscosity decreases with the shearing rate) which
is a positive effect of considerable importance in boiler use.
For a charcoal of LHV 7500 kcal/kg, the mixture has a theoretical
LHV of 4725 kcal/kg, and an effective LHV (water vaporization) of
4480 kcal/kg (18700 kJ /kg); 75% of the energy content is due to the
charcoal and the calorific value is largely compatible with the
objectives. Combustion tests on these mixtures will start in 1990. It is
probable that this type of slurry will be more compatible with
intermittent operation of boilers.
7. 5. 3 Conclusion
Two types of slurry, binary or ternary, can be obtained which seem to
satisfy viscosity and heating value specifications imposed for conver-
sion of domestic fuel boilers. Much work, however, remains to be
done.
The combustion characteristics in a boiler and in an engine remain
to be specified, as do the necessary modifications to the equipment,
and the derating for boiler retrofitting.
Other products also remain to be tested as the ternary phase in
replacement of domestic fuel, namely distillation fractions of non-
marketed petroleum, crude oils, pyrolysis tars, etc.
The manufacturing criteria thus chosen must then be tested on
selected coppice woods and used on a continuous pilot model (the
tests described here are batch).
7.6 Economic assessment of binary slurries production
This estimate concerns the binary charcoal-water mixture with the
exception of the ash-removal stage, according to the ftowsheet
142 Catherine Esnouf
1 OOT wood
(50'. moisture) (18390 MJ)
3340 MJ. i .e. 930 kWh 21 kWh ----..
t r-----r----'
Electricity production
or sale of heat
100T wood
062t water
(15'. moisture) (16610 MJ)
115t pyroligneous liquor
(7524 MJ)
9 kWh
38 kWh
03 t air
O33t charcoal (10345 MJ)
0577t charcoal-water slurry (9730 MJ)
FIG. 6. Mass/energy balance of a charcoal-water slurry production. ODT,
oven-dried ton, i.e. 0% moisture basis; the heating values take into account
the energy that must be expended to vaporize water in the slurry.
presented in Fig. 1 and the mass and energy balances presented in
Fig. 6.
An evaluation was first made of a plant transforming 10 t of dry
matter per hour, operating continuously 8000 h per annum and
treating short-rotation coppice poplar wood. The basic cost of the
woodchips was estimated, including all expenses, at 290 FF/ODT
excluding transport (414 ECU/ODT). Excess pyrolysis volatiles are
burned to supply steam to a turboalternator providing the electricity
necessary for the process.
Z 6.1 Capital cost
This is made up as shown in Table 1.
Z 6.2 Cost of transformation
Calculation of the cost of transformation, per item or across the entire
output, uses the following conventions (I = capital cost).
Charcoal-Water Slurries 143
Table 1
Capital cost of 10 tlh (dry matter) charcoal-water slurry production, 1989
Capital Wood Dry- Pyro- Crushing Gas burner Total
costs recep- ing lysis and slurry and turbo
tion and prepara- alternator
storage tion
Equipment, million FF 13-70 406 664 545 557 35-42
Installed plant,
million FF' 1877 556 91 747 7-63 4853
Installed plant,
million ECU 268 079 13 107 109 693
Percentage of total 386 115 188 154 157 100
a Capital cost including engineering fees and start-up costs = equipment cost x 137.
The fixed costs are composed of:
-The amortization of the installation, which is set at a rate of 8%
over 10 years, i.e. an annual charge of 149% I.
-The equipment servicing and maintenance, i.e. 4% I.
-The taxes and duties: 2% I.
The total annual cost represents 219% of the capital cost. This cost is
independent of plant operating time.
The staff costs include labour remunerated at an average
140000 FF/year/person (including overheads) and management costs
which work out at 50% of the cost of labour. The total labour cost for
n employees is 1 5 x 140 000 x n FF I year.
The variable costs depend on the plant operating time and consist
essentially of the cost of the additive (017 ECU IMJ produced).
The cost of wood supplies is not included in the calculation of trans-
formation cost. According to these assumptions, the transformation
cost is broken down as shown in Table 2.
The high cost of wood reception, storage and slurry preparation,
should be noted-particularly the cost of crushing (high capital
cost).
The total cost of transformation is 300 FF per tonne of slurry, 74
centimes per thermie, 254 ECU /GJ.
Z 6. 3 Optimization of transport and transformation costs together
The optimization consists of determining which size of plant offers the
best compromise between achievable economies of scale and increas-
144 Catherine Esnouf
Table 2
Cost of transformation of the different stages in charcoal-water slurry
production
Fixed Number of Staff Energy Additive
expenses staff costs balance (WOOFF/year)
(1000FF/ (WOOFF (kW)
year) /year)
Reception 4110 1 210 20 0
Drying 1218 250 525 210 0
Pyrolysis 1993 250 525 90 0
Crushing/
suspension 1635 5 1050 390 923
Turbo alternator 1671 0 0 -710 0
Total 10627 11 2310 0 923
Total Total Total Total Percentage
(lOOOFF (FF/T) (c/thermie) (ECU/GJ) per
/year) item
4320 9359 232 079 31
1743 3776 094 032 13
2518 5455 135 046 18
3608 7816 194 066 26
1671 3620 090 031 12
13860 30026 744 254 100
Table 3
Total cost of slurry excluding wood cost
Basis: current average yield of wood = 13 ODT/hectare/year
1/ concentration of SRca
001 005 01 02
Size of plant, t of slurry/day 410 1130 1750 2680
Collection radius, km 76 56 49 43
Transport cost, FF /t of slurry 149 117 107 97
Fixed transformation
cost, FF /t of slurry 152 112 99 87
Variable cost, FF/t of slurry 20 20 20 20
Total cost of slurry excluding
wood cost FF/t of slurry 321 250 225 204
c/therrnie 8 62 56 51
ECU/GJ 273 212 191 174
a 1/ = ratio of plantation surface to total surface.
Charcoal-Water Slurries 145
ing cost of transport as the plantation size increases. This is carried out
in relation to the value of the exogenous parameter of short-rotation
coppice (SRC) concentration within the plant collection radius. The
scaling coefficient for capital cost versus size is taken as 07. The
results are shown in Table 3.
The foreseeable improvement in productivity of SRC up to
17 ODT/hectare-year on average, does not give a significant reduction
in transformation cost (only 02-04c/thermie).
The biomass concentration coefficient will be fixed at 01 for the
following estimation.
7.6.4 Estimate for production cost charcoal-water slurry
The cost of production is obtained by summing.
--cost of woodchip production;
-transporting woodchips;
-transformation into charcoal-water slurry.
The last two items were examined in the previous paragraph.
The base case examined is thus a plant size of 1750 t of slurry/day, a
SRC concentration of 01, a discount rate of 003 for wood planta-
tions, and an agricultural labour cost at the minimum French legal
level. The final results are indicated in Table 4.
In conclusion, the total cost of slurry is 665 FF/t (future case) or
745 FF/t (present case), that is to say 56 ECU/GJ or 63 ECU/GJ.
Table 4
Total production cost of 1750 tf d charcoal-water binary slurry
Hypothetical SRC productivity
Item Unit Current Percentage Future Percentage
of total of total
Wood cost FF/ODT
290 }
67
250 }
64
c/thermie 1243 1072
Transport of c/thermie 265 15 255 16
wood
Transfor- c/thermie 295 16 283 18
mation
Storage c/thermie 04 2 04 2
Total c/thermie 1843 100 1650 100
FF/t 745 665
ECU/GJ 63 56
146 Catherine Esnouf
7.7 Economic assessment of ternary slurries (UCF)
The estimate is made according to the production ftowsheet already
presented in Section 7.4, i.e. a combined de-ashing step, including
Hel acid treatment, and selective agglomeration; the hydrophobic
liquid phase is light fuel-oil (domestic fuel).
The overall mass and energy balance of the production is very
similar to that of binary slurries, as is the pyrolysis step.
The main points are as follows: 1 t of oven-dried wood and 80 kg of
fuel-oil give 068 t of a slurry having a real lower heating value (taking
into account the water vaporization heat) of 18700 MJ It: and contain-
ing 47% solid charcoal.
The economic evaluation is carried out in the same way as for the
binary slurry with the same hypothetical values.
The capital cost is different for the milling and slurry preparation
step, as the particle size required is much lower, and the preparation
now includes all the ultra-cleaning equipment. As the energy require-
ments are more important for charcoal milling, the turboalternator
cost is also increased.
The size of the production unit is determined, as before, by the
forest density, to optimize the transportation/scale economics ratio.
At 01 density, a unit producing 2700 t/ day of slurry is an optimum
size.
For such a capacity, the capital costs are broken down as in Table 5.
Table 5
Capital cost of a 2700 tid ternary slurry production unit
Capital
costs
Currency
Equipment
million FF
Plant cost
including
engineering
and start-up
fees
Million FF
Million ECU
Percentage of
total
Wood
reception
and
storage
98
134
19
32
Dry-
ing
29
40
57
9
Pyro-
lysis
47
64
91
15
Milling
and
slurry
preparation
95
130
185
31
Gas burner
and turbo-
alternator
41
56
8
13
Total
310
424
603
100
Charcoal- Water Slurries 147
The production cost is broken down as follows (per ton of slurry):
-The standing charges of transformation cost are 219% of the
capital cost; added to the staff costs, they represent 95 FF/t slurry
(135 ECU/T), that is to say 117% of total cost.
-The operating costs include the additive (08% at 10 FF /kg)
80FF/t, the acid (145 kg 10MN HCI) l160FF/t, and the light
fuel-oil (12% at lOOOFF/t) 120FF/t. The total operating cost
excluding staff is thus 21160FF/t (30 ECU/t), that is to say
249% of total cost.
-The wood transport (optimized) and storage cost represents
118 FF/t (167 ECU/t), that is 134% of total cost.
-The wood itself represents 427 FF/t, (605 ECU/t), that is 50%
of total cost.
In conclusion, the production cost of bio-UCF is estimated at
850FF/t (120 ECU/t), that is to say 19 centimes/thermie
(65 ECU/GJ).
Considering the present official OPEC price for crude oil ($18/bbl),
the domestic fuel is 10 centimes/thermie, so bio-UCF is nearly twice
the price. Compared with binary slurry, the cost is not significantly
higher (19 c/thermie compared with 184 c/thermie). The main items
making up that price are the wood, representing half of the cost, and
the fuel and additive representing 23% of the cost. So, finding
alternative additives and hydrophobic phases is of considerable impor-
tance for cost reduction.
Considering other possible improvements, an increase in short-
rotation coppice from 13 t/ha to 17 t/ha would save a significant
15 centimes/thermie (8%) for bio-UCF and 2 centimes/thermie
(11 %) for binary mixtures.
Utilization of the pyrolysis liquids could also mean a significant cost
decrease. The simplest way is to sell their energy content on-site,
through steam generation for instance. This would represent a
2 c/thermie (10%) reduction for bio-UCF and 25 c/thermie (235%)
for binary mixtures. Any other more valuable strategy for use of
pyrolysis liquids (upgrading to motor-fuel, for instance) will have to be
taken into account in the future and will represent an increase in
competitivity for slurries.
7.8 Preliminary appraisal of final energy cost
The comparison with other fuels must be made in terms of final energy
cost, that is to say including the boiler's capital cost and efficiency and
148 Catherine Esnouf
the boiler operating time per year (the hypothetical value here is
4000 h/year).
The bio-UCF slurry and binary slurry are compared with light
fuel-oil and woodchips. This assessment is very preliminary as specific
data on boiler modifications for such slurries are not yet available.
In the case of bio-UCF, the boiler is not equipped with ash and dust
removal whereas, for binary slurries the boiler capital cost includes
those items.
The comparison of bio-UCF with light fuel-oil is shown in Fig. 7, the
final energy cost being computed as a function of oil price and boiler
rating. For each fuel, five power levels have been considered: 500 kW,
1 MW, 15 MW, 25 MW and 4 MW, the increase in power meaning a
decrease in energy cost. This graph shows that the bio-UCF would be
competitive against a light fuel-oil cost of around 23 c/thermie
,
1075
(!)
-
=>
u
w
....
III
0
U
>.
850
OJ
L
(IJ
c:
(IJ
iii
x- 4MW
c:

625
(<> 500kW
- 1MW
Light
t:
fuel-oil
E)-
3 4 5 6 7 8 9
Light fuel-oil cost (ECU IGJ)
FIG. 7. Slurries and light fuel-oil costs as a function of oil price and boiler size.
Charcoal-Water Slurries 149
(78 ECU/GJ), i.e. around 40$/bbl crude oil. For binary slurries, the
equivalent figure would be 65-74 ECU/GJ.
The comparison with woodchips is shown in Figs 8 and 9 for 500 kW
and IMW.
It is seen that the bio-UCF and binary slurries are more interesting
than woodchips for 500-kW boilers but again the comparison with light
fuel is not attractive. If crude oil prices increase, the binary slurry and
woodchips become competitive more rapidly, but the difference is not
very significant. At 1 MW, woodchips show a significantly lower cost
compared with slurries, and this scale effect increases with boiler
power.
This apparent advantage of woodchips is considerably hindered by
transportation cost. Figure 10 shows the distance that makes slurries
...,
(!)
-
::l
U
W
+'
<1\
13
11
3 9

OJ
L
cv
c
IV
I1J
c
u. 7
5
-+- Chips
*. Char:water
-EJ- Fuel-oil
3 4 5 7 8 9
Light fuel-oil cost (ECU/GJ)
FIG. 8. Comparison of energy costs for a 500-kW boiler unit.
150 Catherine Esnouf
::; 11
(!)
- ::)
U
W
....
III
0
U
>.
9
CI
L.
41
c
41
iii
c
iJ:
7
Light fuel-oil cost (ECU/GJ)
FIG. 9. Comparison of energy costs for a I-MW boiler unit, operating
4000 h/year.
competitive with chips. It can be seen that for a I-MW boiler, slurries
can be fairly competitive, but not above this size.
These very preliminary results show that the probable market for
slurries is small boiler units, where, apart from their economics,
woodchips are difficult to cope with. In the future, more attention has
to be paid to such units, as well as very small units (20 kW) for
household heating. In any case, the cost has to be reduced to improve
the comparison with light fuel-oil.
Nevertheless, these pessimistic results can be tempered in terms of
the commom agricultural policy in Europe.
Short rotation coppice growing can be considered as a solution for
diversification of European agriculture and its cost must be compared
with that of other possible policies. In these conditions, Table 6
QI
u
Charcoal-Water Slurries
.... ........... ...... ............................ L ......... .
Slurries cheaper
500
4001--: ... :.......... ,.< ............... , ..... .
...
. !!!
u
c
o
WoodChips cheaper
300
...
L
o
a.
II)
c
."
t=. 200
100
o
o
Char:water
-+- UCF
2 3
Boiler power (MW)
FIG. 10. Distance for competitivity of slurries and woodchips.
151
4
demonstrates its full advantage: the grant is calculated to ensure a final
energy cost for the mix equal to that of domestic fuel.
For each slurry, two estimates are presented, one for the state-of-
the-art and one for a probable environment and technology improve-
ment: higher SRC efficiency 170DT/ha, sale of pyrolysis liquids,
domestic fuel at 41 ECU/GJ.
In addition, export of the technology to developing countries is
possible since the cost of the raw material is lower there (see Table 7)
and this cost represents 50-70% of the final cost price of the slurry.
Low-speed diesel engines could be run on bio-UCF rather than on
domestic fuel for local electricity generation.
This market has to be thoroughly investigated in the future, with
comparisons made with the gasifier-engine route.
152 Catherine Esnouf
Table 6
Cost of different agricultural policies (Grant Required in FF /hectare )
Wheat Rape Ethanol Binary slurry
export production production a (Present)
3000-4800 7000-8000 5000-12000 2800-3500
Binary slurry Ternary Ternary
(Advanced) slurry slurry
(Present) (Advanced)
1100-2000 3700-4000 2300-3400
a Large-scale production, so the product is sold for its energy content .
To conclude, although the present price of slurries is 19 times that
of domestic fuel for a crude barrel at $18, this energy route is among
tqe most advantageous for the diversification of European agriculture
and would appear promising for developing countries.
The cost estimates must be worked out precisely in the future,
particularly when technical progress enables the estimation of the cost
of boiler retrofitting and the exact rating of boilers and diesel engines.
Eucalyptus short-rotation coppices in the South of Europe must also
be considered.
In the case of developing countries, an estimate must be made of the
possible market for diesel engines running on this fuel.
Table 7
Cost of wood in developing countries (FF/t of dry matter, 1987)
Raw material Cost (FFlt) Region
Wood waste 0-50
Collected wood 120-220 Philippines
Natural forest or
{230-300
West Africa
agro-industrial 100-120 Hevea, West Africa
plantation
Wood
{ 150-200
Brazil
from energy 150-280 Philippines
plantations 150-250 Congo
(
Source: Brazil Carbonization and paper mill units)
Philippines Dendrothermal Programme
Africa CfFf
Charcoal-Water Slurries 153
8 CONCLUSION
What are the prospects for development of charcoal slurries and what
work has to be carried out in the future?
Charcoal suspensions in water will not find a significant outlet unless
they enable retrofitting of conventional oil boilers (heavy fuel or better
domestic fuel) without the installation of ash removal devices.
Charcoal must therefore have only a low ash content.
In comparison with mineral coal, vegetable charcoal presents the
advantage of great friability and a low ash content which is adjustable
with careful choice of wood variety.
The work of the CEMAGREF-CTFT-UTC group has enabled ash
levels to be obtained on charcoal compatible with atmospheric
pollution standards. The choice of ash removal technique will depend
on the nature of the charcoal ash (silica and calcium oxide) and
therefore of the wood varieties chosen. A detailed study of eucalyptus
and poplar cultivated in coppices will be necessary to choose the best
energy route.
In terms of slurry formulation, two types of slurries, binary and
ternary, can be obtained, which satisfy viscosity and heating value
specifications imposed for conversion of boilers to domestic fuel.
8.1 Future work
Combustion characteristics in boilers and diesel engines remain to be
specified, as do the necessary modifications to equipment and the
de-rating to be anticipated.
In bio-UCF preparation, other products still remain to be tested as
additives and as the hydrophobic phase in replacement of domestic
fuel-namely un-marketed distillation fractions of petroleum, crude
oils, pyrolysis tars-to reduce the cost. The manufacturing criteria thus
chosen must be tested on coppice woods on a continuous pilot plant.
It must not be forgotten that in the preliminary estimates presented
above, no credit is considered from the use of pyrolysis liquids. Any
utilization, e.g. as on-site energy usage as well as complex upgrading
to motor fuels, will imply a significant improvement in the economics
of the process.
The cost estimate shows that the slurry obtained is 19 times more
expensive than domestic fuel at the current price ($18/bbl) but it also
shows that this energy route is among the most advantageous for diversi-
fication of European agriculture. The cost effectiveness must be dealt
154 Catherine Esnouf
with in detail in the future as the technique of the energy route is
gradually optimized.
In addition, and after a study of the possible outlets, export of a
technology such as this to developing countries must be studied, the
advantage being the lower cost of the energy plantations and the
importance of foreign currency saving.
REFERENCES
1. Fran'<Ois, O. & Antonini, G., Le charbon liquide. La Recherche, 19
(1989) 1038-48.'
2. Kunert, R. et al., Characterization of charcoal-oil mixtures: evaluation of
stability and rheology properties. Paper presented at 4th Int. Symp. on
Coal Slurry Combustion, 10-12 May 1982, Orlando, USA.
3. Moro, J. P., Overview of Brazilian coal and charcoal-oil mixtures
program. Paper presented at 4th Int. Symp. on Coal Slurry Combustion,
10-12 May 1982, Orlando, USA.
4. The characteristics of slurry fuels. IHI Eng. Res., 15(2) (1982) 51-8.
5. Lopez & Murata, Physical properties and combustibility of mixtures of oil
and charcoal. Third Int. Symp. on Coal Oil Mixture Combustion, 1981.
DOE Technical Information Center, pp. 1055-80.
6. Demeter, J. J., Combustion of low sulfur-low nitrogen char produced by
pyrolysis of wood wastes. In Energy from Biomass Symp., 14-18 Aug.
1978. IGT, Chicago, 1978, pp. 275-92.
7. Pyrolytic oils characterization and data development for continuous
processing. Knight, J. A. et aI., report for EPA No. 600/2-80-120, August
1980.
8. Ryan, T. W., Diesel engine injection and combustion of slurries of coal,
charcoal and coke in diesel fuel. SAE Trans., 93(1) (1984) 1703-19.
9. Tsuneo, M., Japanese Patent Appln 8514805, 7 October 1985.
10. Salvi, G., Study on the production of charcoal slurry based on biomass
pyrolysis products. In Energy from Biomass 1, ed. G. Grassi & H.
Zibetta. Elsevier Applied Science, London, 1986, pp. 339-43.
11. Antonelli, L., KTI activities in the field of biomass pyrolysis. In Pyrolysis
and Gasification, ed. G. L. Ferrero, K. Maniatis, A. Buekens & A. V.
Bridgwater. Elsevier Applied Science, London, 1989, pp. 85-92.
12. Cadet International, European Patent 87-40106603, 1987.
6
Contribution to the Analytical Study of Biomass
Pyrolysis Oils
P.-L. DEsBENE, M. ESSAYEGH, B. DESMAZIERES & 1.-1. BASSELlER
Laboratoire de Chimie Organique et Structurale, Universite de Paris
VI, 4 place Jussieu, 75230 Paris Cedex OS, France
ABSTRACT
Biomass pyrolysis oils contain a very wide range of complex organic
chemicals. Analytical techniques are steadily developing and permit
increasingly accurate and detailed characterization of the constituents of
pyrolysis products. Previously identified chemicals are listed and recent
advances in analytical techniques are reviewed.
1 INTRODUCTION
The use of biomass pyrolysis to produce char, tars, etc. [1], has been
known since antiquity, but the composition of these products remained
unknown for a long time. The first attempts to analyse wood
condensates date from the early part of this century [2], and now, from
extensive studies [3-10], pyroligneous acid is well known by chemists
and industrialists (see Table 1). Unfortunately, few data are available
in the case of tars. Until recently, studies concerning these complex
organic mixtures were mainly oriented towards the identification of
particular families of compounds:
-polycyclic hydrocarbons [11-13];
-phenols [13-18];
-light fatty acids [19-22];
-carbonyl compounds [23-24].
155
156 P.-L. Desbene et al.
Table 1
Compounds identified in pyroligneous acid
Organic acids Aldehydes and ketones Pyridines
Formic acid Acetaldehyde Pyridine
Acetic acid Acetone Methylpyridine
Propanoic acid 2-Butanone
Butanoic acid 2-Pentanone Lactones
2-Butenoic acid 2-Hexanone Valerolactone
2-Methyl-2-butenoic acid Cyclopentanone
Pentanoic acid 2-Methylcyclopentanone Esters
Hexanoic acid Furfural Methyl formate
Alcohols
Methylfurfural Methyl acetate
Methanol
Phenols Ethers
2-Propanol
Catechol Dimethoxymethane
3-Methylpropanol
1,1-Dimethoxyethane
4-Methylbutanol
Amines
Methylamine
No attempts were made to characterize pyrolysis oils as a function of
temperature until 1980 [25]. Now, it is known that the production of
organic tars depends on temperature, with a maximum at 500C
[25-30], but the variations of composition versus this parameter were
relatively little studied [31] until the researches of Elliott in 1986 [32].
In fact, before this fundamental study, which is the first global
approach of wood tars analysis, the only compounds identified were
polyaromatic hydrocarbons [33,34].
2 STUDY OF THE COMPOSITION OF PYROLYSIS OILS
AS A FUNCTION OF PROCESSING CONDITIONS
Elliott [32] used the coupling of capillary gas chromatography and
mass spectrometry to characterize tars obtained from the carb-
onization of various species of softwood and hardwood (maple, oak,
walnut-tree, hornbeam, birch) in processes at different temperatures.
This analysis is qualitative (identification of the products) and quan-
titative (estimation of the main product yields). Elliott gave an
interesting comparison between the composition of oxygenated tars
(i.e. obtained at low temperature) and deoxygenated tars (obtained at
high temperature).
The compounds identified in these two types of pyrolysis oils are
reported in Tables 2 and 3. Some of these compounds have been
mentioned previously in various studies.
Analysis of Biomass Pyrolysis Oils 157
Table 2
Products identified and quantified in oxygenated tars obtained at low
temperature (Elliott [32])
Organic acids
Benzoic acid
4-Hydroxy-3-methoxybenzoic acid
Abietic acids
Phenols
Phenol
2-Methylphenol
3-Methylphenol
4-Methylphenol
Methylhydroxyphenol
4-Methyl-2-methoxyphenol
4-Ethyl-2-methoxyphenol
4-Propyl-2-methoxyphenol
4-Propenyl-2-methoxyphenol
4-Hydroxy-3-methoxybenzaldehyde
4-Hydroxy-3,5-dimethoxybenzaldehyde
2,6-dimethoxyphenol
4-Methyl-2,6-dimethoxyphenol
4-Ethyl-2,6-dimethoxyphenol
4-Propyl-2,6-dimethoxyphenol
4-Propenyl-2,6-dimethoxyphenol
4-Acetyl-2,6-dimethoxyphenol
1-(3,5-dimethoxy-4-hydroxyphenol)
Alcohols
Furfuryl alcohol
2-Hydroxy-3-methyl-2-cyc1opentenone
1-( 4-Hydroxy-3-methoxyphenyl)-2-propanone
Table 3
Aldehydes and ketones
2-Methyl-2-butenal
Furfural
3-Methyl-2-cyc1opentenone
2-Propanone
Aromatic hydrocarbons
Indene
Naphthalene
I-Methylnaphthalene
1-Phenylnaphthalene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Cyc1openta[ d,e ,f]phenanthrene
Fluoranthrene
Aceanthrylene
Acephenanthrylene
Pyrene
Benzo[ a ]pyrene
Products identified and quantified in deoxygenated tars obtained at high
temperature (Elliott [32])
Phenols
Phenol
Aromatic hydrocarbons
Dibenzofuran
Indene
Biphenyl
Naphthalene
I-Methylnaphthalene
2-Methylnaphthalene
1-Phenylnaphthalene
2-Phenylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Cyc1openta[d,e,f]
phenanthrene
Fluoranthrene
Aceanthrylene
Pyrene
Acephenanthrylene
Benz[ a ]anthracene
Chrysene
Benzo[ a ]pyrene
158 P.-L. Desbene et al.
The main conclusions of Elliott's work are the following.
(i) The composition of tars is strongly dependent on the process.
However, a common characteristic is the low level of sulphur
and nitrogen compounds.
(ii) Although they are condensates, pyrolysis oils are only partially
volatile. Consequently, only a part of pyrolysis oils is analysed
by GC/MS coupling. This low volatility is explained by rela-
tively high molecular weight and by strong polarity.
(iii) The four oxygenated tars are very similar. IR spectra present
ketone, alcohol and ether bands; NMR spectra are charac-
terized by methyl aryl ethers and aromatic aldehydes. Some
differences appear between tars coming from different lignins.
(iv) The Georgia Tech and Rome processes are the least severe, as
proved by:
-the presence of furanic compounds, levoglucosan and
abietic acids;
-the near-total absence of polyaromatic hydrocarbons.
The BCL and SERI processes are more severe, and the tars
obtained are highly aromatic (100% and 82% respectively).
(v) There are important differences in the composition of pyrolysis
oils according to the treatment applied. These differences are
summarized in Table 4, which gives the main classes of
compounds identified.
(vi) Differences also appear from the nature of the wood. Tars
resulting from the carbonization of softwood contain significant
amounts of monomethoxyphenols and those obtained from
hardwood have a greater proportion of dimethoxyphenols.
The method of analysis is, however, somewhat biased. The tech-
nique used to simplify the organic matrix, i.e. extraction by CH
2
Cl
2
prior to GC/MS analysis, is of limited use to recover highly polar
components and the results are biased towards low-polarity products.
In order to avoid these difficulties, it is proposed to use a set of
high-performance chromatographic techniques to simplify the complex
organic mixture of pyrolysis oils in the current work.
Analysis of Biomass Pyrolysis Oils 159
Table 4
Classes of compounds encountered in tars from different wood carbonization
processes
Conventional High-temperature Conventional High-tempera-
flash flash pyrolysis at gasification at ture
pyrolysis at 600-650"C 700-800"C gasification at
450-500"C 900-1 OOO"C
Acids Phenols Phenols HAPs:
Phenols Catechols Benzaldehydes Naphthalene
Gaiacols Benzaldehydes Naphthofurans Acenaphthylene
Syringols Benzofurans HAPs: Phenanthrene
Alcohols Aromatics and HAPs: Naphthalenes Fluoranthrene
Aldehydes Benzenes Phenanthrenes Pyrene
Ketones Biphenyls Fluorenes Acephenan-
Furans Naphthalenes Acenaphthylenes thrylene
Benzanthracenes
Benzopyrenes
3 APPROACH TO MAPPING COMPONENTS OF
PYROLYSIS OILS
The procedure adopted before performing the final capillary gas
chromatography is based on two chromatographic separation tech-
niques using quite different principles:
-The improved API 60 method is an acid-base separation.
-Steric exclusion allows separation as a function of the
component's molecular sizes.
3.1 Acid-base separation of pyrolysis oils
This method uses the differences of interaction in organic media
between a solute and ion-exchange resins (styrene-divinylbenzene
copolymers, bonded to sulphonates and ammonium, respectively, in
cation and anion exchangers). As the mobile phase is organic, the
system is non-aqueous and there is no ion exchange. An association
between the functional groups of the sample and resins is observed.
The strength of this association is a function of the acid-base
characteristics of components analysed.
The sample is deposited on the resin surface by means of a solvent
(the least polar possible) compatible with its solubility. Bonds of
different strengths are formed and are then progressively destroyed as
160 P.-L. Desbene et al.
prim e
concentration of.
'-----------...1 eluate and recycling
of mobile phase
FIG. 1. Device used for acid-base separation of the components of pyrolysis
oil. V. and Vb are three-way values allowing the use of columns 1 and/or 2;
column 1 filled with IRA 904 resin and column 2 with A 15 resin.
a function of their nature by thorough elution using mobile phases of
increasing polarities. The components are eluted according to their
increasing acid-base characteristics.
Originally, this chromatographic technique was long and tedious.
Some years ago, an improvement was made [35], by means of the
device described in Fig. 1. A complete acid-base separation can be
completed in 7 h compared with more than eight days in the case of
the original method.
After developing the improved API 60 method for analysis of heavy
oil fractions, an adaptation was necessary for pyrolysis oils analysis.
Some of the solvents used in the separation of heavy oil fractions, such
Table 5
Elution sequence and acid-base characteristics of the fractions collected in the
case of pyrolysis oils analysis using the improved API 60 method
Ion exchanger
A15 + IRA 904
(coupled)
IRA 904
A15
ELuent
Benzene-cyclohexane,
75:25
Benzene
Benzene-acetonitrile
Acetonitrile
Methanol
Benzene
Benzene-THF
THF
Methanol
Acid-base characteristic
of the fraction collected
Neutral
Weak acids
Medium acids
Strong acids
Very strong acids
Weak bases
Medium bases
Strong bases
Very strong bases
Analysis of Biomass Pyrolysis Oils 161
as acetic acid and diethylamine [36], are not suitable for the analysis of
wood pyrolysis oil. These solvents gave solvates which were difficult to
destroy. The elution sequence used to analyse pyrolysis oils as well as
acid-base characteristics of the fractions collected are reported in
Table 5. Regardless of the wood species considered, pyrolysis oils are
dehydrated by azeotropic distillation before injection, so the chromat-
ographic separation is performed in entirely organic medium.
The acid-base balance obtained after analysis of hornbeam wood is
shown in Fig. 2. In order to allow comparison, the results obtained
with various species are reported in Table 6.
The main features of these results are the following.
(i) The separation of acid-base fractions depends on both the
nature of the wood species and the process (fast or slow
pyrolysis). In the case of hornbeam and poplar a similar
Neutral
A C ids -t------3 4 % r------J
Medium aCids
Weak 11
0
/0
aCids
51 %
Very strong aCids
strong
ac I ds
Medium bases
FIG. 2. Acid-base separation of hornbeam pyrolysis oil. (a) global separation;
(b) separation of acidic fractions; (c) separation of basic fractions.
162 P.-L. Desbene et al.
Table 6
Acid-base separation of pyrolysis oils as a function of wood
species (mass balance)
Acid-base characteristic
of fractions collected

Hornbeam"
Pine"
Poplar"
Hornbeam
b
" Slow pyrolysis.
b Fast pyrolysis.
Neutral
(%)
37
65
35
54
Acidic
(%)
335
165
29
22
Basic
(%)
28
135
27
185
acid-base balance is obtained, but the results are quite
different for pine pyrolysis (softwood).
(ii) Totally different balances are obtained with the same species
(here hornbeam) as a function of pyrolysis conditions (slow or
fast).
(iii) However, if the proportions by weight for poplar and horn-
beam are quite similar, qualitative compositions are different,
as shown by the capillary gas chromatograms of the various
acid-base fractions of their pyrolysis oils (see Fig. 3).
(iv) Finally, apart from the neutral fraction, which is the most
abundant regardless of wood species, the medium-acid fraction
and the medium-base fraction are predominant in acids and
bases.
After this first separation, the organic matrix is fairly simplified but the
complexity of the fractions collected remains too great and impedes
identification of the components by GC/MS coupling. So, according to
the procedure previously described [36], a second preparative chroma-
tography of the collected acid-base fractions was used. This second
preparative chromatography uses steric exclusion as the separation
principle.
3.2 Preparative sterlc exclusion chromatography of the diJferent
acid-base fractions
Steric exclusion has been used occasionally in the field of wood
liquefaction [37-40], but its application to the analysis of pyrolysis oils
ne u tral hornbeam
L
0
50
neutral poplar
o 50
pine
0
50
Analysis of Biomass Pyrolysis Oils
1<)0 0
mrn ,
100 0
min.
II.
100 0
mtn.
acidic hornbeam
50
acidic poplar
50
acidic pine
III lJ
50
10,0 0
mIn.
10P 0
min.
10,0 0
m,n,
basi c horn be am
50
basic poplar
50
basic piM
50
163
100
min.
100
min.
10.0
min.
FIG. 3. Capillary gas chromatograms of various acid-base fractions of
pyrolysis oils obtained by slow pyrolysis.
is almost an innovation. Only Shen et al. [41] had performed such a
separation before this work was undertaken at the P. et M. Curie
University. They had separated four classes of components from a
pyrolysis oil:
-heavy hydrocarbons,
-light hydrocarbons and esters,
-phenolic derivatives,
-aromatic compounds.
164 P.-L. Desbene et al.
This technique of sorting as a function of molecular size was applied
to each of the fractions obtained from the API 60 separation. Each of
the acid-base fractions was resolved into three subfractions having
different molecular weights. As an example, Fig. 4 shows the
separations of the predominant acid-base fractions.
Regardless of the acid-base fraction separated, the preparative
sterlc exclusion chromatographies were performed under the same
conditions (mobile phase THF, chromatographic gel Styragel 10 fJ.m,
one 1(f A column and two 50 A columns, flow rate 06 ml/min).
After this second preparative separation, 27 fractions were obtained
RI
a
V (ml)
10 20 30
b
10 20 30
c
o 10 20 30
FIG. 4. Preparative high-performance steric exclusion chromatography of
acid-base fractions from pyrolysis oils of hornbeam wood (obtained by slow
pyrolysis): (a) neutral fraction; (b) medium acid fraction; (c) medium basic
fraction.
Analysis of Biomass Pyrolysis Oils 165
for each of the pyrolysis oils analysed and an attempt was made to
identify the components by capillary gas chromatography-mass
spectrometry coupling.
3.3 Approach for 'mapping' pyrolysis oil components
3.3.1 Conditions of structure determinations
Every fraction was studied using two ionization modes:
-electronic impact at 70 e V;
-<:hemical ionization by ammonia and methane.
These two ionization modes are complementary. The first allows the
fragmentation of molecules and gives precious structural information.
The second is used to obtain the molecular weights. For each fraction,
a comparison is established between the total ionic current in
electronic impact and in chemical ionization. The molecular weight is
then obtained for each peak of the GC chromatogram.
After determination of molecular weights, a search was made for
the ten best correlations between the electronic impact spectra and
the mass spectrometer library. Thus, the structures of a number of
fragments were obtained and hypothetical structures were established.
Among these hypothetical structures, the most likely were retained,
according to the physico-chemical properties of the compound (acid-
base characteristics, polarity, chromatographic behaviour).
3.3.2 Determination of a 'map' of samples
The organic mixtures obtained in the case of the subfractions from
steric exclusion chromatography of neutral and acidic fractions are so
simple that the simplified procedure described above allowed an
attempt to identify their likely structures. The structures identified in
neutral fractions are reported in Table 7 (classification by formulae).
A similar classification of weak, medium, strong and very strong acidic
fractions is reported in Tables 8, 9 and 10.
Some conclusions can be drawn from the results given in these four
tables.
(i) Microdistillation of each of the fractions was performed at the
temperature of gas chromatographic analysis. The proportion of
compounds characterized in these conditions is estimated at
more than 60%.
Table 7
Constituents of the neutral fraction of a hornbeam pyrolysis oil (obtained by
slow pyrolysis)
Alcohols
Furfuryl alcohol
Methoxytetrahydrofuryl alcohol
Esters, ketones and aldehydes
Methyl furan carboxylate
Butyl-2-one acetate
Tetrahydrofuryl acetate
Propyl acetate
Acetyl cyc10pentene
Acetyl cyc10hexene
Methyl benzoate
Ethyl methylbenzoate
Methyl dimethoxybenwate
Methyl hexadecanoate
2-Pentanone
S-Methyltetrahydrofuranone
Methylcyc1opentanone
Ethylmethylcyc1opentanone
(2-Methylfuryl)ethanone
Indanone
(3-Ethylnaphthalene)-
propan-2-one
Furfural
Methyltetrahydrofurfural
Ethers
Methyltetrahydrofuran
Propyldioxolane
Methoxytoluene
2-Propylfuran
Ethoxybenzene
Dimethoxybenzene
Ethylmethoxybenzene
Dimethoxytoluene
Methylethyldihydropyran
Ethylbutyldihydropyran
Dimethoxydimethylbenzene
Dimethoxystyrene
Diethoxybenzene
Dimethoxyethylbenzene
Dimethoxyethoxybenzene
Trimethoxybenzene
Di-t-butylmethoxybenzene
Trimethoxybenzene
Trimethoxyallylbenzene
Dimethoxymethyldihydro-
benzofuran
(Methoxybenzofuryl)styrene
Aromatics
j-Propylbenzene
Indene
Propyltoluene
Butylbenzene
j-Propyltoluene
t-Butylbenzene
Dimethylethylbenzene
Diethylbenzene
Tetramethylbenzene
Ethylpropylbenzene
3-Phenyl-l-butene
Methylindene
Ethylstyrene
Propyl styrene
Pentylbenzene
Methylbenzofuran
Naphthalene
Methyldibenwfuran
Dimethylbenwfuran
Dibenzofuran
Dimethylindane
Methylnaphthalene
Methyltetrahydronaphthalene
Ethyltetrahydronaphthalene
Dimethylnaphthalene
Propylnaphthalene
Propylallylnaphthalene
j-Propylnaphthalene
j-Propylbiphenyl
Dimethylbiphenyl
Diethylbiphenyl
Fluorene
Methylfluorene
Anthracene
Pyrene
Methylpyrene
Acephenanthrylene
Butylvinylnaphthalene
Methylphenyl-2,3-dihydrobenzofuran
Benzofluorene
Xanthene
Hydrocarbons
Ethylcyc10pentene
Propylcyc1opentene
j-Propylcyc1opentene
j-Propylcyc1opentane
2-Butylcyc1opentane
3-Methyl-4-octene
Dimethylethylcyc1o-
hexadiene
Tetramethylcyclo-
hexadiene
Dimethylundecane
Tridecane
Tetradecane
Bicyc10hexyl
Dimethylbicyc10hexyl
Pentadecane
Hexadecane
Dipropyldodecane
Methylheptadecane
Analysis of Biomass Pyrolysis Oils 167
Table 8
Constituents of the weak acid fraction of hornbeam oil pyrolysis obtained by
slow pyrolysis
Phenols
Phenol
Methylphenol
Dimethylphenol
Ethylphenol
Methylethylphenol
Dimethoxyphenol
Propylphenol
i-Propylphenol
Trimethylphenol
Dimethylmethoxyphenol
Methylpropylphenol
Diethylphenol
Butenylphenol
Propenylmethoxyphenol
Propenyldimethoxyphenol
Trimethoxyphenol
Propylmethoxyphenol
Methyl methoxyhydroxybenzoate
Dimethoxyhydroxybenzaldehyde
Acetyldimethoxyphenol
Propionyldimethoxymethylphenol
Butyryldimethoxyphenol
Lactone
Butyrolactone
Esters, aldehydes and ketones
Acetylfuran
Acetoxymethylbenzofuran
Acetoxyethylbenzofuran
Methylfurfural
Trimethylbenzaldehyde
Dimethylcyclohexanone
Methylheptanone
Ethers
Methoxypentane
Dimethylmethoxybenzofuran
Ethylmethoxybenzofuran
Aromatic
Toluene
(ii) The improved API 60 method seems to be an efficient
technique for acid-base separation. The components identified
in each of the fractions are more polar when the acid-base
characteristics are more extreme.
(iii) Pyrolysis oils obtained after slow pyrolysis of wood contain
mainly:
-saturated hydrocarbons and aromatics (neutral fraction);
-ethers (particularly abundant in neutral fractions);
-esters (in neutral and weak acid fractions);
-aldehydes and ketones (neutral fractions, weak, medium
and strong acids);
-phenols, containing:
(a) monophenols (essentially in weak and medium acid
fractions) .
168 P.-L. Desbene et al.
Table 9
Constituents of the medium acid fraction of hornbeam pyrolysis oil obtained
by slow pyrolysis
Organic acid
Ethylbenzoic acid
Aldehydes and ketones
Dimethylformylbenzaldehyde
Vinylmethoxybenzaldehyde
Trimethylformylbenzaldehyde
Trimethoxybenzaldehyde
2-Propylacetophenone
Dimethylbenzofuranone
Dimethyldihydrobenzo-
pyranone
Ethers
Dimethoxyallylbenzene
Methyldibenzofuran
Bifuran
Naphthols and phenols
Ethylnaphthol
Trimethylnaphthol
Ethylhydroxyphenol
Dimethylhydroxyphenol
Dihydroxyindane
Methylhydroxy-l,2-
dihydronaphthol
Methoxyphenol
Allylethoxyphenol '
Trimethylmethoxyphenol
Allylethylphenol
Propylmethoxyphenol
Vinylmethoxyphenol
Allylformylphenol
Methyl methylhydroxybenzoate
Trimethylhydroxyindane
Methylhydroxyindane
Hexenylphenol
Ethyl dimethyl benzophenone
Methyl dimethoxyhydroxy-
benzoate
(b) naphthols and diphenols, only in the most polar fractions
(medium, strong and very strong acids);
-and some organic acids in strong and very strong acids.
(iv) Finally, in addition to the large groups of compounds of which
many members can be isolated from slow pyrolysis oils (in the
tables), some groups are present but are only represented by
some of their members. These compounds are:
-alcohols,
-lactones.
In the case of subfractions from basic fractions, the organic mixtures
are still too complex and the method of identification described above
is not sufficient.
Because of the importance of nitrogenous bases in oil derivatives or
from coal liquefaction fractions [42-47], efforts have so far been
limited to identification of these compounds in pyrolysis oils.
Analysis of Biomass Pyrolysis Oils 169
Table 10
Constituents of strong and very strong acid fractions of hornbeam oil pyrolysis
(obtained by slow pyrolysis)
Organic acids
2-Methylbutyric acid
Methoxyhydroxybenzoic acid
Alcohol
2-Benzofurylethanol
3.3.3 Nitrogenous bases
Naphthols and phenols
(di and mono)
Dimethylnaphthol
Diethylnaphthol
Methoxyacetylnaphthol
Dihydroxybenzene
Methyldihydroxybenzene
Acetyldihydroxybenzene
Methylmethoxydihydroxybenzene
Methylpropyldihydroxybenzene
i-Propyldihydroxybenzene
Propyldihydroxybenzene
i-Butyldihydroxybenzene
Methylethyldihydroxybenzene
Methoxypropyldihydroxybenzene
Methylpropionyldihydroxy-
benzene
Methyl dimethyldihydroxy-
benzoate
Methoxydihydroxybenzene
Methoxyphenol
Methylhydroxybenzoate
H ydroxybiphenyl
Dimethoxyacetylphenol
Dimethylpropionylphenol
Hydroxystilbene
Because of the low level of nitrogenous compounds in pyrolysis oils, a
concentration technique is required. The two best methods have been
tested from those described in the literature [48-53] for the concentra-
tion of these products from complex organic mixtures.
-The first method is a classical extraction [49] with dilute sulphuric
acid, followed by neutralization of the aqueous phase at pH 12
and extraction of nitrogenous bases using dichloromethane.
-The second method uses chromatographic concentration [50] on a
silica bed impregnated with hydrochloric acid. Nitrogenous bases
are concentrated in the column head and undergo total elution
with methanol.
170 P.-L. Desbene et al.
Yields of extracts from slow pyrolysis oil from hornbeam by these
two techniques are reported in Table 11. These results show that:
(i) the two techniques are relatively reproducible, with small mean
deviations;
(ii) the so-called 'extractive' method is slightly more accurate than
the 'chromatographic' method, with a smaller standard
deviation;
(iii) the 'chromatographic' method, however, gives better quantita-
tive measures than the 'extractive' technique and leads to
systematically greater extraction yields;
(iv) finally, the 'extractive' method is more tedious and sensitive
than the 'chromatographic' technique, due to emulsion
formation.
The chromatographic method was selected to concentrate nitroge-
nous bases. Although it has lower reproducibility, this method is easier
and its quantitative results are better. Optimization of the stationary
phase was necessary to perform the analysis of the constituents of
nitrogenous bases by capillary Gc.
Stationary phases (similar to CP SIL 5) are unsuitable for analysis of
these mixtures because of some of their physico-chemical properties,
such as:
-high polarity;
-the presence of several isomers of some compounds;
Table 11
Comparative study of the efficiency and reproducibility of
nitrogenous bases extraction from slow pyrolysis oils from
hornbeam
Experiment
1
2
3
Extractive
method [49]
(%)
185
160
166
170Ol
b
Chromatographic
method [50]
(%)
274
200
260
245 O3W
a Expressed as g per 100 g of pyrolysis oil.
b The precision reported here corresponds to the mean
deviation.
Analysis of Biomass Pyrolysis Oils 171
-low volatility of some compounds of this family, for instance benz
[a ]acridine (bp760 = 438C).
Stationary phases have been examined for a high level of chemical
inertness and good thermal stability. Among the phases commercially
available, the series CP SIL CB seemed the most suitable. After a
comparative study of a standard mixture containing 13 nitrogenous
bases, the less polar stationary phase of this series, i.e. CP SIL 5 CB,
was selected. This phase is a polydimethylsiloxane support chemically
bonded. It can be used up to 325C. The chromatograms obtained
using this stationary phase with the standard mixture of nitrogenous
bases (Fig. 5) and with the nitrogenous base fractions extracted from
pyrolysis oil (Fig. 6) demonstrate its efficiency. This stationary phase
had not been used previously to separate such compounds.
v
III
C
o
a.
III

ci
LL
o
t
10
I
20
Time (min)
I
50
FIG. 5. Capillary gas chromatogram of a standard mixture of nitrogenous
bases on a CP SilS CB column, length 25m, de 022 mm, d
film
=012mm.
Injection: 1/30 split; V; = 1 Ill; flow rate 2 ml/min, detection by FID; tempera-
ture programming between 50C and 2500C).
172
FID
response
D 1D 20
P.-L. Desbene et al.
time (min)
so 1DO
FIG. 6. Capillary gas chromatogram of nitrogenous bases extracted by the
so-called chromatographic method (analysis conditions are the same as in the
case of the standard mixture of nitrogenous bases.
After optimizing the capillary gas chromatography analysis, the
components of the nitrogenous base fraction were identified by
GC/MS coupling. The bases identified are reported in Table 12.
This study shows that nitrogenous bases belong to very different
classes (pyridines, naphthyridines, quinolines, indoles, etc.). Some of
these families (indoles, quinolines and naphthyridines) have only a few
members identified (or present).
Other families of compounds present in oil and coal liquefaction
fractions (such as carbazoles and to a lesser extent acridines), are
completely absent in the components identified. According to this
preliminary study, the components of nitrogenous base fractions of
pyrolysis oils are principally pyridines, pyrazines, piperazines and
purines.
4 CONCLUSION
The complex organic mixtures of pyrolysis oils have become better
known over the last few years, but only some of their constituents
have been identified. Elliott reports rightly that some of the studies
give a distorted image of the composition of pyrolysis oils, because of
the concentration techniques used. The results are biased towards the
high-volatility compounds.
Analysis of Biomass Pyrolysis Oils 173
Table 12
Nitrogenous bases identified after chromatographic extraction of slow pyrolysis
oils from hornbeam
Pyridines
Methylmethoxypyridine
Methoxypyridine
Methoxyethoxypyridine
N, N -Dimethyl-4-aminopyridine
2-Pyridyl ethanol
Isopropylmethylpyridine
Propylpyridine
Butylpyridine
Quinolines
Tetrahydroquinoline
Methyltetrahydroquinoline
Indole
Methylethoxyindole
Piperazines
DI (N-methyl) methyl-
dimethoxypiperazine
Dimethoxyethylpiperazine
(N, N' -Dimethyl)-
dimethoxypiperazine
Pyrazines
Methylethylpyrazine
Butylhydroxypyrazine
Methoxybutylpyrazine
Dimethoxytetramethyl-
tetrahydropyrazine
Naphthyridines
Methylnaphthyridine
Methoxydihydronaphthyridine
Methylethyloctahydro-
naphthyridine
Methylethyltetrahydro-
naphthyridine
Methylmethoxynaphthyridine
Dimethylocta-
hydronaphthyridine
Purines
Methylpurine
Dimethylpurine
Propylpurine
Methylpropylpurine
Methylhydroxydihydro-
purine
The analysis strategy described above partly corrects this bias by
using chromatographic techniques. The compounds are separated
regardless of their volatility and of their polarity. This method allows
an appreciable improvement: 60% of the original material can be
analysed by capillary gas chromatography after fractionating pyrolysis
oils into 27 subfractions.
Some of the constituents of the pyrolysis oils described in this paper
have, of course, been identified previously and described in the
literature. However, the approach of mapping as a function of polarity
(acid-base characteristic) as reported here is an innovation in this field
of applied organic analysis.
For the future, it is necessary to consider analysis of these
subfractions by means of techniques that are complementary to
capillary GC and better adapted to low-volatility compounds. There-
174 P.-L. Desbene et al.
fore it is intended to study all of the subfractions in capillary
supercritical fluid chromatography. This recently developed technique
has a higher performance than liquid chromatography and is relatively
well adapted to medium-polarity compounds.
Finally, the study will be completed by more precise structural
identification, which will require:
-the study of model compounds, followed by their co-injection in
the subfractions tollected;
-the use of more sophisticated techniques than GC/MS coupling
[coupling of supercritical fluid chromatography and tandem mass
spectrometry (MS-MS), high-resolution mass spectrometry],
when standards are available.
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E. I., Kun, V. N., Dikun, P. P. & Kostenko, L. D., Izv. Vyssh. Licheb.
Zaved. Les Zh., 15 (1972) 99.
13. Rachinskii, A. V., Dorzet, N. M., Lavina, L. M., Chuprova, N. A.,
Belikova, Z. P., Repyakh, S. M., Nikolaeva, G. V., Tikhomirova, G. V.
& Levin, E. D., Kromatogr. Anal. Khim. Drev., (1975) 249.
Analysis of Biomass Pyrolysis Oils 175
14. (a) Levin, E. D., Chuprova, N. A., Belikova, Z. P. & Kondalintseva, T.
F., Materialy Nauch. Konf., (1965) 98; (b) Levin, E. D. & Chuprova, N.
A., Materialy Nauch. Konf., (1965) 54; (c) Levin, E. D. & Chuprova, N.
A., Gidroliz. Lesokhim. Prom. St., 19 (1966) 14.
15. Shposhnikov, Y. K. & Kosyukova, L. V., Gidroliz. Lesokhim. Prom. St.,
19 (1966) 19.
16. Wellburn, A. B. & Hamming, F. W., Nature (London), 212 (1966) 1364.
17. Matweka, Z. 0., Tr. Leningrad. Lisoteck. Akad., 100 (1967) 343.
18. Luten, J. B., Ritskes, J. M. & Wesseman, M. J., Z. Lebensm. Unters.
Forsh., 168 (1979) 289.
19. Brulin, H. H. & Pensar, G., Acta. Chem. Scand., 19 (1965) 531.
20. Bardyshev, I. I., Bulgakov, A. N. & Pertovskii, A. L., Khim. Priv.
Soedin., 6 (1970) 539.
21. Ekman, R. & Pensar, G., Snom. Kemistisevram. Tiedonantoja, 80 (1971)
40.
22. Holmbom, B., J. Am. Oil Chem. Soc., 54 (1977) 289.
23. Tischenko, D., Zh. Prikl. Khim., 39 (1966) 438.
24. Love, S. & Bratzler, L. J., J. Food. Sci., 31 (1966) 218.
25. Diebold, J. P., Proc. Specialists' Workshop on Fast Pyrolysis of Biomass.
1980, NTIS No. SERI-CP 622-1096.
26. Diebold, J. P. & Scahill, J. W., Entrained-flow, fast ablative pyrolysis of
biomass. In Annual Report, 1984. NTIS No. SERI/PR-234-2655.
27. RensfeJt, E., Blomkvist, G., Ekstrom, C., Engstrom, S., Espenag, B. G.
& Liinanki, L. In Energy from Biomass and Wastes III, ed. D. L. Klass.
IGT, Chicago, 1978, p. 465.
28. Flanigan, V. J., Punya Kumleard, A. & Sitton, O. C., Biotech. Bioeng.
Symp., 14 (1985) 3.
29. Nunn, T. R., Howard, J. B., Longwell, J. P. & Peters, W. A. In
Fundamentals of Thermochemical Biomass Conversion, ed. R. P. Over-
end, T. A. Milne and L. K. Mudge. Elsevier Applied Science, London,
1985, p. 293.
30. Epstein, E., Kosstrin, H. & Alpert, J. In Energy from Biomass and
Wastes VIII, ed. D. L. Klass. IGT, Chicago, 1978, p. 769.
31. Milne, T. A., Evans, R. J. & Soltys, M. N. In Energy from Biomass and
Wastes VIII, ed. D. L. Klass. IGT, Chicago, 1984.
32. (a) Elliott, D. c., Analysis and Comparison of Biomass
Pyrolysis/Gasification Condensates. Final Report, PNL 5943 UC-61 D,
1986. (b) Elliott, D. c., Pyrolysis Oils from Biomass, ed. E. J. Soltes and
T. A. Milne. In ACS Symposium Series, No. 376. American Chemical
Society, Washington DC, 1988, p. 55.
33. Rose, G. R., Singh, S. P., Onischak, M. & Babu, S. P. In Energy
from Biomass and Wastes V, ed. D. L. Klass. IGT, Chicago, 1981,
p.613.
34. Beck, S. R., Mann, U. & Bartsch, R. A., Application of SG FM
Technology to Alternate Feedstocks, Phase III. Final Report, Texas Tech.
University, Lubbock, Tx.
35. Desbene, P. L., Lambert, D. c., Richardin, P., Basselier, J. J., Huc, A.
Y. & Boulet, R., Anal. Chem., 56 (1984) 313.
176 P.-L. Desbene et at.
36. Desbene, P. L., Essayegh, M. & Basselier, J. J., J. Chromatogr.,
submitted for publication.
37. Collins, C. J., Triolo, R and Lietzke, M. H., Fuel, 63 (1984) 1202.
38. Meier, D., Doring, R. & Faix, 0., 3rd EC Conference, Elsevier Applied
Science, London, 1985, p. 732.
39. Schwald, W., Concin, R, Bonn, G. & Bobletev, 0., Chromatographia,
20 (1985) 35.
40. Schaleger, L. L. & Davis, H. G., Special Meeting on Biomass
Liquefaction, ed. R. L. Eager, J. F. Mathews & J. M. Pepper, University
of Saskatchewan, Saskatoon, Saskatchewan, Canada, 1982, p. 191.
41. Shen, Y. E., Philip, C. V., Anthony, R. G. & Soltes, E. J., J.
Chromatogr. Sci., 22 (1984) 497.
42. Guerin, M. R., Rubin, I. B., Rao, T. K., Clark, B. R. & Epler, J. c.,
Fuel, 60 (1981) 282.
43. Hirao, K., Shinohara, V., Tsuda, H., Fukushima, S., Takahashi, M. &
Ito, N., Cancer Res., 36 (1976) 329.
44. Dong, M., Schmeltz, I., Lavoie, E. & Hoffmann, D., Carcinogenesis: a
comprehensive survey. In Polynuclear Aromatic Hydrocarbons, Vol. 3,
ed. P. W. Jones & R. I. Freundenthal. Raven Press, New York, 1978, p.
97.
45. Lee, M. L., Novotny, M. W. & Bartle, K. D., Analytical Chemistry of
Polycyclic Aromatic Compounds. Academic Press, London, 1981, p. 441.
46. Petroy, R. A. & Petersen, M. R., Mutation Res., 90 (1981) 309.
47. Mahlum, D. D., Frazier, M. E., Petroy, R A. & Renne, R. A.,
Comparison of in vitro and in vivo Studies with Coal Liquids from SRC-ll
Prouss. NIlS No. PNL-4836, 1983.
48. Jewel, D. M., Weber, J. H. & Lancher, H. P., Anal. Chem., 44 (1972)
1391.
49. Later, D. W., Lee, H. L., Bartle, K. D., Kong, R C. & Ivassilavos, L.,
Anal. Chem., S3 (1981) 1391.
50. Shmitter, J. M., Ignatiadis, I., Arpino, P. & Guiochon, G., Anal. Chem.,
SS (1983) 1685.
51. Hangen, D. A., Peal, M. J., Suhvbler, K. M. & Stamards, V. L., Anal.
Chem., 54 (1982) 32.
52. Novotny, M., Kump, R., Merli, F. & Todd, L. J., Anal. Chem. S2 (1980)
401.
53. Ignatiadis, I., Shmitter, J. M. & Guiochon, G., J. Chromatogr., 246
(1982) 23; Ignatiadis, I., Shmitter, J. M. & Guiochon, G., J.
Chromatogr., 248 (1982) 203.
7
Product Standards for Pyrolysis Products for Use
as Fuel in Industrial Firing Plants
F. RICK & U. VIX
Institute for Energy Technology and Environmental Protection, Energy
Utilisation Department, Technischer Uberwachungs-Verein Rheinland
eV, Postfach 101750, D-5000 K6ln 1, Federal Republic of Germany
ABSTRACT
The relevant properties and characteristics of fuels used in oil-firing
applications are listed and described in terms of their significance. The
properties of some pyrolysis oils are compared with the properties of
conventional mineral oils in order to assess the consequences for the
process plant required and the behaviour of these fuels in combustion
technology.
The process plant technology available for heavy fuel-oil is, to a large
extent, applicable to pyrolysis oils. However, some important properties
such as lubricating ability, corrosion and chemical behaviour with
respect to sealing materials have not yet been adequately researched.
The anticipated flue gas emissions have been derived from the
material specifications available, suggesting that there will be a tendency
to form coke dust and nitrogen oxides (NO
x
)' On the other hand,
there are no emissions of sulphur or heavy metals. The oils
contain toxic substances with potentially carcinogenic and mutagenic
properties.
The most important properties of pyrolysis-derived charcoals are
described. The factors that influence the material characteristics of
charcoal-liquid mixtures are explained, making use in part of research
findings from the slurrying of mineral coals. On the basis of these
material characteristics, the requirements for process plant for combus-
tion of charcoal slurries are derived.
177
178 F. Rick & U. Vix
1 PRODUCT STANDARDS FOR PYROL YTIC OILS
1.1 Introduction
For oils produced from pyrolysis of biomass, recourse can be made to
the process technology used in conventional combustion with mineral
oils, or even, because of their similar properties, to experience with
coal-based fuel oils. The design of a combustion plant is determined by
a number of fuel properties which are mostly familiar to the
combustion engineer from mineral oil technology, or which may be
established on the basis of statistical studies from a few key values.
First, a list of the important properties and characteristic values with
their significance for plant and combustion technology must be
compiled. A study can then be made, with the help of the available
literature, of the properties displayed by pyrolysis oils, and how they
differ from conventional fuel oils and to what extent. Conclusions can
be drawn from this comparison with regard to the process to be used
which provide important answers for both the operator and the
planner.
It must not be forgotten that pyrolysis oils are not standardised
products, but can exhibit a wide range of properties and compositions
according to the source material and pyrolysis technique employed.
Furthermore, it is not at present possible to judge whether all the
testing techniques developed for mineral oils can also be applied to
pyrolysis oils without modification.
For this study, reports on the Tech Air Process (Cordele, Georgia)
and on the EC's Raiano Project (Italy) have been evaluated.
1.2 Material properties and characteristic values
1. 2.1 Density
The density of a fuel-oil gives a first indication of its composition; it is
specific for one batch. The C/H ratio, and thus the molecular
structure, influence the density. With an increase in the proportion of
hydrogen, the density falls and the heating value rises. These
correlations have been studied statistically in the case of mineral oils
so that, within certain limits of accuracy, the composition and the
heating value can be deduced from the density. The heating value is
also influenced by the sulphur content.
Product Standards for Pyrolysis Products 179
A further relationship exists between density and viscosity; heavier
oils generally also exhibit higher viscosity.
The density is temperature-dependent, normally being specified at
15C. Determination of density is carried out in accordance with DIN
51757.
The temperature dependence of density for mineral oils in given by
[1]:
where
d
t
= density at tOC in kg/m
3
;
d
15
= density at 15C in kg/m3.
The cubic coefficient of expansion, a, is given by:
a = 068 kg/m
3
c for light fuel-oil; d
15
= 840-860 kg/m
3
a = 062 kg/m3 C for heavy fuel-oil; d
15
= 920-960 kg/m
3
The determination of heating value is derived from density accord-
ing to Zerbe [2]:
Hu = 52921 - 1l932d
15
- 293 S [kJ /kg]
where d is in kg/m3 S = sulphur content in % wt.
The C/H ratio is approximately given by:
C/H = 001l(d
15
- 8(0) + 6 [kg C/kg H]
When only C, Hand S are considered as constituents of the oil, an
elementary yield analysis dependent upon the sulphur content can be
derived:
H = (100 - S)/(C/H + 1)
C= 100- S - H
The density of pyrolysis oils, according to information in the
literature, is always in excess of 1000 kg/m
3
; they are therefore heavier
than water. Conversely, the heating value only reaches about 50-60%
of the heating value of heavy fuel-oil, so that the above relationships
no longer apply for the heating value. Available data show that the
density of pyrolysis oils is dependent upon the process temperature,
the gas outlet temperature from the pyrolysis reactor and also the
180 F. Rick & U. Vix
sample position. The density of the condensed oil rises as the gas
outlet temperature increases.
The density of pyrolysis oils also changes with temperature, al-
though no comparative measurements are available for the cubic
coefficients of expansion. However, it may safely be assumed that
these are similar to the values for fuel oils.
The high density of the wood oils can be regarded as advantageous,
as it increases the heating value per unit volume and thus reduces the
difference from conventional oils in storage and transport. For a
similar volume flow, approximately 18-20% more mass is delivered
than in the case of heavy fuel-oil.
1.2.2 Lower and higher heating values
The lower and higher heating values are a measure of the quantities of
heat released in total combustion. An exact definition of these terms
may be found in DIN 5499 and the measurement technique is
described in DIN 51900. The lower and higher heating values refer to
a temperature of 25C of the reaction reactants before combustion,
and of the reaction products after combustion. The higher heating
value (HHV) also includes the vaporisation enthalpy of the water
resulting from the combustion process. The conventional measurement
technique from DIN 51900 establishes the higher heating value from
which the conventional lower heating value (LHV) for combustion
without flue gas condensation can be calculated:
LHV=HHV-rw
where r = specific vaporisation enthalpy of water at 25C = 2442 kJ /kg;
w = water formed in combustion in kg H
2
0/fuel.
From the elementary yield analysis, the proportion of water formed
by oxidation of hydrogen can be calculated:
w = h[kg hydrogen/kg fuel] x 8924 [kg H
2
0/kg hydrogen]
If the fuel contains free water, as is normal for pyrolysis oils, this must
also be taken into account.
Thus, for LHV, it follows that:
LHV = HHV - 2179 H - 2442 W
where H = proportion of H in the fuel [% mass];
W = proportion of water in the fuel [% mass].
Product Standards for Pyrolysis Products 181
The water content of pyrolysis oils is between 10 and 14%, i.e.
about 100-140 g water has to be vaporised per kg oil. If the water
dispersed in the pyrolysis oil were removed, the LHV would rise by
about 340 kJ /kg or only by about 16%. Therefore, from an energy
point of view, extraction of the water is not worthwhile.
1.2.3 Viscosity
Viscosity is a measure of the internal friction in a fluid. It is the most
important criterion for the differentiation of oil types. The design of
oil storage tanks, supply facilities and atomisation is determined by the
viscosity.
Viscosity does not describe the lubricating properties of the oils
which are crucial for selection of supply pumps.
Dynamic (11, eta) and kinematic (v, nu) viscosities, which are
dependent upon the density, are used:
v=!!.
d
The units of viscosity are described in Table 1. The equation for
conversion is given by:
11 [cP]
v [cSt] = d [kg/d
m
3]
Besides these SI units, various empirical units such as degrees
Engler (OE), Redwood or Saybold, which can be converted to the
kinematic viscosity, are employed. According to Ubbelohde, the
following approximate relationship exists between E and cSt:
[cSt] = 713E - 631/
o
E
In combustion technology it is usual to specify the kinematic
viscosity, which is exponentially dependent upon temperature. In a
Kinematic viscosity
m
2
/s
1 stokes = 10-
4
m
2
/s
1 cSt = 1 mm
2
/s
Table 1
Units of viscosity
Dynamic viscosity
Pa s; pascal second
1 Pa s = 1 N s/m2
= 1 kg/sm
1 poise = 01 Pa s
182 F. Rick & U. Vix
A Wood Oil, initial Quality
B Wood Oil after storage, 8 month, 0 C
C Wood Oil after storage, 8 month, ambient temperature
D Wood Oil, vacuum stripped, (water free)
(c St)
1100000
50000
30000
10000
1-=
3000
I!:
2000 1.0
1IlO/l
Roo
300
?oo
1\,\
150 '\
,,\
100 \

AO
"-
AO \. \. '-...
.,
Ino
40
"''''
'0
\ \

25
20 \ \
I\. f'.-
12

)iI
10 '\
'"
1\
9
='D.
B
7
'\ '1:1
A 1,\
,,...
5
4.5
"
4
,.
"
3
07 '\
2.2
flight
2
1.7
'"
-20 -10 10 20 30 40 50 60 70 80 90 100 110 120 130 1400C 160
Temperature
FIG, 1. VT dependency of wood oils (Georgia Tech-Air), according to
Ubbelohde [23]. Delivery point: condenser.
Product Standards for Pyrolysis Products
183
corresponding coordinate system, these viscosity/temperature curves
are given as straight lines (VT straight lines), so that the whole VT
relationship can be described by specification of two value pairs (see
Fig. 1-the Ubbelohde illustration). This property is maintained until
the cloud point or setting point is approached. Here, the straight line
changes to an asymptotic curve to infinity at the setting point.
Determination of viscosity is carried out according to DIN 51550,
the VT relationship being dealt with in DIN 51563.
While the upper limit for pumpability is about 600 cSt, a much lower
viscosity and thus a higher temperature is required for atomisation.
Figure 1 shows the viscosity curve of normally available fuel-oils
according to Ubbelohde [23], with Fig. 2 as a linear graph. It is
important for the plant constructor that the VT gradient reduces
substantially with increase of temperature, i.e. an excessive increase in
temperature causes only a small change in viscosity. In order to limit
the energy and investment necessary for preheating, an exact know-
ledge of the viscosities required for optimum atomisation is necessary,
as excess heating brings no advantage. For heavy fuel-oil, heating to
over lOOoe is necessary.
200
180
160
140
1\
\
\
\
iii
120
<..>
>-
'iii
100
0
<..>
en
80
:>
I\HeaVY ( il
\
60
r"\
'\
40
20


r-.
Light Oil
-----
t---l----
o
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Temperature C
FIG. 2. VT dependency of mineral oils, linear graph.
184 F. Rick & U. Vir
Typical viscosity values for various atomisation systems, in accord-
ance with [1] and [3], are given as:
Pressure atomiser (heavy oil)
Pressure atomiser (light oil)
Steam pressure atomiser (heavy oil)
Rotary atomiser
10-20 cSt
25-5 cSt
10-30 cSt
30-60 cSt
Various investigations of viscosities for wood oils are known from the
literature. These values have been entered on a graph according to
Ubbelohde (Figs 1 and 3). First it is seen that the linear gradient is
also maintained for wood oils in this method of representation. The
viscosities are lower than that of heavy fuel-oil. The wood oil obtained
from the condenser from Cordele (Tech-Air) differs only slightly from
the Raiano (Alten) sample. The oil tapped at the ventilator is
somewhat thinner, apparently containing lighter components. The
lower density supports this theory.
Investigations of the ageing behaviour at various storage tempera-
tures were carried out in Cordele. Viscosity tends to be reduced for
both oil samples when stored cold, while storage at ambient tempera-
tures shows no significant influence. When storage is at higher
temperatures (HOC), the viscosity rises with increase of the storage
period (Figs 3 and 4).
Measurements are also available for the influence of water content
on viscosity. The VT curves of the water-free oils show a tendency to
somewhat increased viscosity. Thus the water content here has a
favourable effect (Figs 3 and 4).
Thus, similar temperatures are required for supply and atomisation
to those needed for heavy fuel-oil. Storage temperatures should not be
too high, ranging from 35 to 45C.
1.2.4 Setting point, cloud point
The setting point indicates at which temperature the oil ceases to flow
as a result of the increase in viscosity. Determination of the setting
point is carried out in accordance with DIN 51583. The equivalent
pour point according to ASTM indicates at which temperature the oil
still just flows. Depending upon the technique used, it is about 2-4 K
above the setting point. The setting point may rise as a result of
storage and temperature effects. In practice, the setting point is less
significant than the cloud point according to DIN 51583. Precipitation
of solid paraffins in conventional oils commences at the cloud point.
Product Standards for Pyrolysis Products 185
Ge ...... -r.clrAtr
rnril2/S (c St)
I I I I I I I I I I I I I I I I I

A Wood Oil, 'initial QUa.lit'y -
r;ru;ru;n
-
<nnM
S Wood Oil after storage, 8 month, 0 C
-
"""""
----
C Wood Oil after storage, 8 month, ambient temperature =
1nt1OO
D Wood Oil, vacuum stripped, (water free)
-

'>Mt\
""""
w",'
"""
>00 \
1\" --;;;;;-
\ \
W\ 1\
An fP '\ '\ '\
"
.n '\ \
-;;n
.n \. \ \ \
.n
\
25
"
""
\ \ I'\.
leavy Oil
,..
-;;;-
\
,n
"-
\ \ 1\
-.;;:
,
\
tc '[

I'\.
f'S'
,
'\
1\
--..
"

I'\.

? 7
"-
? ?
f\ Light Oil
2
"
1.5
-20 - 10 10 20 30 40 50 60 70 80 90 100 110 120 130 140 .c 160
Temperature
FIG. 3. VT dependency of wood oil derived from pyrolysis (Georgia Tech-
Air, according to Ubbelohde [23]. Delivery point: draught fan.
186 F. Rick & U. Vix
mm
2
/s (c SO
r!
50000

10000
3000

2000 '5M
1000
",,, "
600
Q
300_
"-
200
"1\
" 150
,
."
100 "'-.\
"1:'\
60
60
-"'-
50
40
1,\,
30

''\
25
.,
20
\
\r-. 1\
1.
'"
12
I'
16 \
9
6
. Heavy Oil
I
6
5
.5
3.5
3
2.7
<,2
2
1.7
1.5
-20 -10 10 20 30 40 50 60 70 80 90 100 110 120 130 140 .c 180
Temperature
FIG. 4. VT dependency of wood oil derived from pyrolysis (Georgia Tech-
Air), according to Ubbelohde [23]. Influence of storage time. Storage
temperature 110C.
Product Standards for Pyrolysis Products 187
The cloud point can only be established for transparent light oils. The
cloud point, defined according to ASTM, is about 2 K lower than the
setting point. The paraffin precipitates can clog filters and pipes,
leading to plant failure.
In the case of light fuel-oil, the cloud point is between approx. 0 and
-5C and the setting point of heavy fuel oil is between 20 and 40C.
In the same context, for tar oils the term 'freedom from sediment' is
used, as defined in DIN 51603 Part 2. Freedom from sediment means
freedom from crystalline precipitations at a specified storage
temperature.
Measurements of the pour point exist for wood oils with values
around 26C, i.e. in the lower range of the typical values for heavy
fuel-oil. A study on freedom of sediment would be of value, as a
similar behaviour to that of tar oils has to be taken into account
because of the molecular composition.
1. 2. 5 Specific heat and thermal conductivity
The specific heat of fuel-oils is of significance in the calculation of the
preheating requirement. It is determined by the molecular composi-
tion of the fuel-oils and is also temperature-dependent.
As already explained, the molecular composition can be correlated
with density, so an approximation of the specific heat may be obtained
via the density and temperature. The specification for mineral oils,
according to [1], is as follows:
I
, 1
Cm 0 = (1687 + 0OO1696t) [kJ /kg K]
where C
m
= specific heat [kJ /kg K].
According to Kraussold, the following equations apply.
For oils with d
I5
> 09:
c
m
I: = 41868(09210 - 0560d
I5
+ 0OOO55t) [kJ/kg K]
For oils with d
l5
< 09:
C
m
I: = 41868(06920 - 0308d
15
+ 0OOO55t) [kJ/kg K]
In practice, for an approximate calculation, the value C
m
= 2 kJ/kg K
may be assumed.
188 F. Rick & U. V,x
Thermal conductivity is required for the calculation and design of
the heating surfaces or the heating surface temperatures in preheaters
and containers. It is also dependent on density and temperature. In
the case of mineral fuel-oils, the following relationship can be used:
0422
;. = - (1- 000054t) [kJ/m h K]
dIs
where dIs = density at 15C [kg/dm3];
t = oil temperature [0C].
The value for heavy fuel-oils around 100C is 042 compared with a
value for water of 24 kJ/m h K. This relatively poor thermal con-
ductivity limits the surface temperature in preheaters and heating coils
of storage tanks.
Comparable values for pyrolysis oils are not available at present.
1. 2.6 Significant properties for safety
The significant properties for safety considerations are not the material
constants, but the characteristic values describing material properties
which are strongly influenced by the testing conditions. Therefore, an
exact definition of these testing conditions is very important for the
determination and evaluation of the corresponding characteristic
values. Thus, the numerical values for the same terms can differ if they
have been determined by different test techniques.
1. 2. 6.1 Flash point. The flash point is defined as the lowest
temperature at which so much fuel vapour forms over the fluid surface
at atmospheric pressure that external ignition leads to combustion.
The combustion takes place instantly in the form of an explosion.
Determination of the flash point is carried out for flash points between
5 and 65C (light fuel-oils) by the Abel-Pensky method, DIN 51755,
and for flash points from 65 to 200C by the Pensky-Martens method,
DIN 51758. Both tests are carried out in an enclosed crucible.
For flash point determination in a closed crucible, the flash point can
be related to the ignition limit (lower explosion limit) in air at
atmospheric pressure, as a fixed relationship of temperature and
partial pressure exists over the vapour pressure curve. Also the
proportion by volume of the gas mixture to the total volume has the
same relationship as its partial pressure to the total pressure.
Product Standards for Pyrolysis Products 189
When determining the flash point in an open crucible, this relation-
ship no longer exists and the flash points determined in this way are
often considerably (about 30C) higher.
When determining the flash point in the case of material mixtures
such as fuel-oils, the lower ignition limit of the lightest partial fraction
is measured-in other words, blends with lighter fractions have
considerable influence on the flash point.
For normal commercial fuel oils, minimum values for the flash point
are specified according to type (Table 2). These also determine the
classification into hazard classes [24]. Thus, the flash points for wood
oils lie within the range for heavy oils, so the same hazard class can
also be assigned.
Hazard classes for inflammable liquids which cannot be mixed with
water or which cannot be mixed with water in all ratios are as listed in
Table 3.
1.2.6.2 Ignition limits. Ignition limits or explosion limits describe
the limiting concentrations of fuel vapour in air within which combus-
tion can take place without further addition of air when ignition is
caused by a suitable ignition source. Ignition limits are generally
specified as the proportion by mass or by volume of fuel vapour per
unit volume at 25C. As the proportion by volume corresponds with a
definite partial pressure, it is also possible, as shown above, to specify
a temperature in combination with the vapour pressure curve as shown
in Fig. 5.
As fuel-oils are material mixtures of many different hydrocarbons,
no uniformly exact values can be specified. As an alternative, a
relationship discovered by Zabetakis [4] can be used. According to
this, in the case of most hydrocarbons (C > 4), the lower ignition limit
Table 2
Minimum and typical values for the flash point
Light fuel-oil
Heavy fuel-oil
Wood oil
Flash point cae)
Minimum value,
DIN 51603
55
80
Typical value
60-90
90-180
110-120
190 F. Rick & U. Vix
Table 3
Hazard classes for inflammable liquids with
limited miscibility with water
Hazard class
AI
All
AlII
Flash point (0C)
Below 21
21-55
55-100
is about 45-50 mg/m
3
relative to room temperature. If the stoichio-
metric concentration is known, an approximate value for the lower
ignition limit can also be determined from this.
Estimates of the lower ignition limit for hydrocarbon C
4
+ are:
C
L25
= 45 mg/m
3
[mg/m
3
]
C
L25
=055C
st
[vol. %]
where C
L25
= lower ignition limit in [mg/m
3
or % vol. at
atmospheric pressure and 25C;
Cst = stoichiometric concentration in vol. %.
The ignition limits widen with increasing temperature so that, on
reaching the spontaneous ignition temperature, the upper limit is
100% and the lower limit 0%. The temperature dependency can be
estimated with sufficient accuracy according to [5] with a relationship
100% r-------------"O"""'!I...----
delayed -+ undelayed


l flammable
mixture
autoignition
!
- ..J
o
:t!.,9Ui"1l1
0%
flash point autoignition temperature
temperature ---+
FIG. 5. Ignition limits. Cst = stoichiometric concentration.
Product Standards for Pyrolysis Products 191
determined for paraffins:
e
L25
eLt = eL25 - 1275 (t - 25)
where e
Lt
= lower ignition limit at temperature tOe.
Further information is provided in the following section.
1.2.6.3 Spontaneous ignition temperature. The ignition tempera-
ture or spontaneous ignition temperature refers to the lowest tempera-
ture at which a fuel-air mixture ignites itself without an external
ignition source. The ignition temperature is dependent on the design
and surface of the test vessel. The lowest ignition temperature is
reached mostly not with a stoichiometric, but with a slightly over-rich,
mixture. The measurement technique is standardised according to
DIN 57194. The values established with this technique are very low
but, in practice, spontaneous ignition only occurs at higher
temperatures.
Ignition temperature is influenced by molecular composition. In the
case of paraffins and their isomers, the ignition temperature falls with
increasing chain length; in the case of paraffin-based fuel oils, the
ignition temperature is about 220-300e. The ring compounds (aro-
matics) are more stable, so that the ignition temperatures for
aromatic-rich oils, particularly tar oils, rise to 380-440C.
According to Nabert & Schon [6], the safety-related characteristic
values for fuel-oils shown in Table 4 are specified.
At present, it is not possible to give a value for the lower ignition
limit or the ignition temperature of pyrolysis oils. In view of their
Table 4
Safety-related ignition limits and ignition temperatures for fuel-
oils
Light fuel-oil
Heavy fuel-oil
Ignition limits
in air (vol. %)
Lower
06
06
Upper
65
65
Ignition
temperature
roC)
220
220-300
192 F. Rick & U. Vix
aromatic-rich composition, however, a relatively high ignition tem-
perature would be expected.
1. 2. 7 Composition
In addition to viscosity, the elementary yield analysis is a further
important criterion for the design of combustion plants. With the help
of elementary yield analysis, the combustion calculation can be carried
out from which the quantities of combustion air and flue gas and also
the composition of the flue gas can be determined. Table 5 shows the
elementary yield analysis of some pyrolysis oils in comparison with
normal commercial fuel-oil.
The high proportion of process-related water is noticeable as well as
the high oxygen content which, however, was only analysed in sample
3. This may be assumed to be of a similar order of magnitude for the
other samples, as the sum of the analyses falls well short of 100%.
According to [7], the oxygen exists in molecular bonding, with organic
acids, alcohols, aldehydes, ketones and phenols as the possible oxygen
carriers. According to [8], the oil should contain about 20% phenolic
compounds. The organic acids react acidically and the phenols even
more strongly. The pH value of wood oils is about 3.
Table 5
Elementary yield analyses (% wt)
Sample
a
Analysis 1 2 3 4 5
Water content 140 104 140 Traces 01
Solids 03 04 01
Ash 008 003 10 01
C 512 656 620 863 852
H 76 78 70 135 11-1
N 08 09 10 200mg/kg 03
S <001 <001 Traces 02 23
0 ? ? 150 10
Total 739 851 990 100 999
C/H ratio 674 841 886 639 768
Conradson <01 8-10
a Key: 1, wood oil condenser-Tech Air [5]; 2, wood oil ventilator-
Tech Air [5]; 3, wood oil-Raiano (Alten pyrolysis project, Raiano); 4,
light fuel-oil typical values; 5, heavy fuel-oil typical values.
Product Standards for Pyrolysis Products 193
The C/H ratio, at 67-89, is in the same range as that of heavy
fuel-oil.
The sulphur content is very small, whereas the nitrogen content is
about three times as high as in heavy oil. Practically no S02 is
generated in combustion, whereas a higher emission of nitrogen oxides
is to be expected, as explained in more detail below. The nitrogen is
bonded, according to [9], in ammonia, various amines and pyridines.
When there is no filtering, the oils can contain a high proportion of
solid carbon particles [10].
Data on ash content vary widely but, in contrast to mineral oils, no
toxic nickel or vanadium oxides are contained in the ash. As may be
expected from the feed materials, the most important ash constituents
are probably sodium, potassium, calcium and, in smaller quantities,
manganese. A further inorganic component from the feed material is
phosphorus. In addition, various metallic oxides from process plant
abrasion, and silicon from impurities in the feed (such as sand), may
occur [11].
The molecular composition was investigated by Kaupp & Goss [9].
According to these workers, wood oils consist of over 100 different
organic compounds, the proportions of which vary widely according to
initial material and processing. The evaluation and application in
combustion technology is less affected by this variability, although
important criteria relating to occupational health and safety in
handling these materials may well be important.
1. 2.8 Analysis by fractional distillation
By means of fractional distillation, it can be established what
proportions by volume of the oil are vaporised at which temperatures.
Being a mixture of many different hydrocarbons, oils do not have one
boiling point but rather a boiling curve. Boiling first takes place at
atmospheric pressure. However, for heavy fuel-oils containing propor-
tions of compounds which do not boil easily, boiling must be
continued from 360C under vacuum in order to avoid thermal
cracking. The results are converted to atmospheric pressure. The
boiling behaviour of mineral fuel-oils is specified in key points by DIN
51603.
It is important for combustion technology purposes to know how
easily and how completely an oil can be vaporised. Thus, boiling
behaviour is crucial for the combustion time of the fuel droplets after
194 F. Rick & U. Vix
expulsion from the atomiser. Boiling residues can indicate a tendency
for coking.
Figure 6 shows the boiling curves of mineral oils [12] and wood oil
[5]. In contrast to mineral oils, commencement of boiling in wood oils
takes place at about 100C as a result of the free water content. Then
the readily boiling constituents vaporise rapidly, expressed in a steep
rise in the boiling curve which levels off at higher temperatures. The
end of boiling is quickly reached. A large unboilable residue of about
50% is left as low as approximately 270C.
The early end of distillation with a large distillation residue indicates
an easy thermal breakdown of pyrolysis oils. The maximum heating
surface temperature of preheaters and heating pipes should therefore
not be set too high, as deposits of cracked oil can otherwise form on
them.
1.2.9 Coke residue according to Conradson
A helpful guide for assessment of the tendency to form coke is the
measurement of coke residue by Conradson's method as described in
DIN 51551. Here, oil is distilled at low temperature in the absence of
air. The percentage by weight of the residue so produced is specified in
"0
())
....
.!!1
:;::;
.!!!
"0

.
())
E
::J
g
100
%
80
60
40
20
o
50
/
V
l7
/
Light Fuel Oil
V

'I
J
Wood Oil
....
. '
{
".,." ""'V
.............
.......
.....................
Heavy Fuel Oil
100 150 200 250 300 350 C 400
FIG. 6. Boiling ranges of fuel-oils.
Product Standards for Pyrolysis Products 195
relation to the weight of the original sample. Ash is also contained in
the coke residue. For heavy fuel-oil, the residual value lies between 6
and 10%, i.e. 6-10% of the oil is converted to coke when the oil is
heated in the absence of air.
In practice, however, there should always be sufficient air to burn up
the coke particles. Coke particles are formed as a carbon residue from
the oil droplets created by atomisation. In the course of combustion,
heat acts upon the oil droplets by first evaporating the volatile
constituents, then breaking down or cracking the rest until finally a
carbon skeleton remains which is difficult to break down any further.
Difficulties can arise if, owing to inadequate atomisation, the coke
particles are so large that the time spent in the flame is insufficient for
complete combustion or if the burning process is prematurely discon-
tinued owing to lack of air or cold surfaces. When flow conditions are
unfavourable, this can lead to coke deposits being formed on jets and
baffle plates.
No values are at present to be found in the literature for the coke
residue from pyrolysis oils but it can be inferred from the early end of
distillation that the coke residue will be relatively high. According to
Churin [13], the coke residue in the case of the Raiano pyrolysis oil is
about 20-25%. When designing burners or combustion chambers,
therefore, coke formation should be expected and the fineness of
atomisation and the residence time should be so selected that any
droplet reduced to coke particles can still be burnt up.
1. 2.10 Miscibility
In order to stabilise the characteristics of pyrolysis oils, a mixture with
heavy fuel-oil might be tried. A study of its miscibility would be
worthwhile from this point of view. However, under certain cir-
cumstances, difficulties could arise due to precipitation of high-
molecular-weight hydrocarbons.
1. 2.11 Synopsis
A list of material values studied to date is contained in Table 6. As a
guide, the values for heavy fuel-oil are also included.
1.3 Combustion calculations
All relevant values for the design of air and flue gas channels and for
the flue gas composition can be determined from the elemental
analysis by means of combustion calculations. Table 7 shows the
196
F. Rick & U. Vix
Table 6
Technical characteristics of liquid fuels
Property Important for: Typical values
Pyrolysis
Heavy.rel-
oil 01
Physical/chemical properties
Density, kg/dm
3
Transport, storage, 12 094
energy density
Lower heating value, Combustion, 21100- 40200
kJ/kg energy utilisation 24700
Viscosity, cSt Storage, supply 9O/50C 2OO/50C
Atomisation 17/1000C 25/1000C
Setting point, C Storage 26 25-30
Heat c:racity, kJ /kg K
Preheating ? 2
Therm conductivity, Preheating, heating ? 042
kJ/mhK surface loading
Combustion technology, plant technology
Boiling curve Thermal stability Spa 98-
5%/290C
1000C
Combustion 1O%/105C 10%/340C
Emissions (dust) 50% Epa/
280"C
Coke residue, % wt Emissions (dust) 20-25 8-10
Miscibility Quality, Limited Good with
stabilisation other
mineral oils
Lubricity Supply (pumps)
Slifht
Good
Corrosion Material selection Slight
Chemical Material selection High? High
aggressiveness (seals)
Safety technology
Flash point, C Hazard class, storage 110-120 90-180
temperature,
ignition quality
Ignition limit, Safety technology, ? 45
mg/m
3
ignition quality
Ignition temperature, C Safety technology, ? 220
ignition quality
Composition
Water, % wt Corrosion 10-14 01
Solids, % wt Emission 04-10 01
Ash, %wt Emission 01-1 01
C, %wt Heating value 50-67 85-86
H, %wt Heating value 7-8 11-115
N, g/kg Emission 8-10 3-5
S, %wt Emission, corrosion <001 1-26
0 , %wt Heating value 15-25
C/H
Heating value, 65-9 76-7-8
flame radiation
metals
Corrosion 3
Nickel, mg/kg Emissions 0 Approx.2oo
Vanadium, mg/kg Emissions, corrosion 0 100-1200
a SP, starting point of boiling; EP, end point of boiling.
Product Standards for Pyrolysis Products 197
Table 7
Characteristic combustion values
Tech-Air Raiano Heavy Light
condensor fuel-oil fuel-oil
oil
Heating value, LHV, MJ/kg 21164 24923 42700 40200
Theoretical air requirement,
m
3
/kg
5690 6857 11250 10550
(Vair,th) m
3
/MJ
0269 0275 0263 0262
Minimum flue gas
Quantity dry, m
3
/kg 5449 6572 10486 9928
(VFmin.dry) m
3
/MJ
0257 0264 0246 0247
VFmin.dry
0958 0958 0932 0941
Vair,th.
Minimum flue gas
Quantity wet, m
3
/kg 6466 7523 11985 11-16
(VFmin.wet) m
3
/MJ
0306 0302 0281 0278
Flue gas moisture, % vol. 157 126 125 110
Maximum CO
2
1738 1745 1523 1587
content, % vol.
results of the combustion calculation for some pyrolysis oils compared
with conventional fuel-oils.
The stoichiometric quantity of air in relation to heating value differs
only slightly from comparable values for mineral oils. The specific flue
gas volume rises by about 7%. The flue gas moisture is somewhat
higher than that from heavy fuel-oil, i.e. the water condensation point
of the flue gas is also higher. However, owing to the low sulphur
content, the flue gas temperature can nevertheless be kept lower, as
there is no risk of condensing sulphuric acid and the important acid
condensation point for heavy fuel-oil need not be considered.
1.4 Emissions
For anticipated emissions, only speculation based on the material
properties can be made.
Firstly, there is a probable susceptibility to form coke. Conclusions
cannot be drawn from the product characteristics as to the formation
of other products of partial combustion such as carbon monoxide, soot
and unburned hydrocarbons.
NO
x
is another air pollutant which can be formed in two different
198 F. Rick & u. Vix
Table 8
Calculated NO
x
emissions from pyrolysis oil
a
Emission of N0
2
By stoichiometric By air excess, Rei. on
combustion, 02 = 0% 02 =3%02 fuel
Conversion (mg N0
2
/m
3
(mg N0
2
/m
3
(mgN0
2
/
rate (%) flue gas) (vpm) flue gas) (vpm) kWh)
100 4824
35 1688 824 1447 706 1565
a Computed with density N0
2
= 205 kg/m\ V
P
min dry = 5449 m
3
/kg. LHV =
5879 kW h/kg.
ways: from nitrogen in air at high temperatures and from nitrogen
compounds in the fuel. This latter formation mechanism also operates
at low temperatures.
Theoretically, 1 mg nitrogen per kg oil produces 2143 mg NO or
3286 mg N0
2
in the flue gas. In the case of a higher nitrogen content
in the fuel, a conversion rate of 35-40% can be expected. Table 8
shows the expected emissions from a pyrolysis oil containing 08%
nitrogen (8000 mg/kg). These emissions would exceed the heavy
fuel-oil NO
x
limit of 450 mg/m
3
at 3% O
2
according to the German
Technische Anleitung Lult [25].
Heavy fuel-oil contains approximately 3000 mg N /kg oil. At a
slightly higher conversion rate of approximately 45 %, fuel nitrogen
would produce 380 mg N0
2
/m
3
of flue gas at 3% O
2
equalling
374 mg N0
2
/kW h.
1.5 Plant technology
Pyrolysis oils are unlikely to achieve the product stability of the
'tailor-made' mineral oils as the production processes and the possible
supplementary materials added are too varied. Therefore, separate
studies and tests are necessary for each oil. Nevertheless, studies to
date of the material characteristics of pyrolysis oil clearly show that the
normal plant technology for heavy fuel-oil can be applied. However, a
few peculiarities must be taken into account.
1. 5.1 Storage
Pyrolysis oils are less resistant to ageing than mineral oils. Long
Product Standards for Pyrolysis Products 199
storage should be avoided. If storage is necessary, then the storage
temperature should be kept as low as possible, at about 10K above the
setting point. When they are stored at higher temperatures the
viscosity changes, as well as some other characteristics.
1. 5. 2 Preheating
Preheating is necessary for supply and atomisation. The oil may have
to be heated to 100-130C for atomisation. The heating surface
temperatures must be restricted as, at higher temperatures, cracking
would be expected.
1. 5. 3 Supply
Owing to the aromatic character of pyrolysis oils, reduced lubricating
power is expected. In addition, according to the processing of the oils,
solid carbon particles could cause increased abrasion. Conventional
supply units such as gear pumps or spindle pumps, however, make use
of the lubricating properties of the mineral oils. Other pump types
may be needed with external lubrication. Attention must be paid to
ensuring that the supply is as free of fluctuation as possible, and if
reciprocal pumps are employed, appropriate precautionary measures
should be taken.
1.5.4 Materials
Water content and acid reactions caused by organic acids and phenols
are pyrolysis oil characteristics. Although corrosion tests (copper strip
test, DIN 51759) have not shown noticeable reaction, corrosion of the
commonly used ferrous materials must be expected. Additional
investigations are necessary. The durability of plastic materials used
for sealing needs to be examined as well. Many plastic materials have
only a low durability when exposed to aromatic compounds.
1. 5. 5 Atomisation
Since pyrolysis oil probably tends to form coke, good atomisation must
be ensured. Steam or compressed-air jet atomisers are recommended.
After shut-down of the burner, the oil ducts of the atomiser can easily
be purged by steam or compressed air. Thus coking of the atomiser
torch caused by heat reflection from the furnace can be prevented.
The preheating temperature has to be reduced when employing a
rotary cup atomiser, as cracking due to the lower thermal stability of
pyrolysis oils could commence on the rotary cup.
200 F. Rick & U. Vix
1. 5. 6 Combustion chamber
In order to prevent the formation of coke and unburned hydrocar-
bons, intensive high-temperature combustion is preferred. High tem-
perature, however, favours the formation of thermal NO
x
A solution
is perhaps offered by staged combustion or the injection of NH
3

2 PRODUCT STANDARDS FOR SLURRIES FROM
PYROLYSIS CHARCOAL AND WATER OR OIL
2.1 Introduction
As a result of the chemical reaction in the pyrolysis of biomass,
various products with differing degrees of usefulness are formed. The
proportions of these products are dependent upon the type of process
and how it is operated. The possible products are:
Gas Heating value 2000-18000 kJ 1m
3
Oil Heating value 20000-27000 kJ Ikg
Charcoal Heating value 25000-31000 kJ/kg
Water Heating value approx. 4000 kJ/kg
The gas formed in pyrolysis can be used directly at the plant to help
provide the process heat requirement, as the expense of transport and
purification this would need is not worthwhile for the low heating
value. The pyrolysis oil is storable, with some reservations. It can be
employed directly as a fuel with a moderate heating value at relatively
low expense using conventional combustion technology. In addition,
employment as a chemical raw material is possible, as pyrolysis oils
contain a large number of potentially commercially interesting organic
compounds.
Employment of the two residual materials charcoal and water poses
more of a problem. As the charcoal is produced in the form of a dry
dust with a broad grain size spectrum, considerable problems can arise
through dust nuisance or through measures to prevent dust nuisance in
the cooling and removal of the charcoal from the pyrolysis plant.
Nevertheless, because of its high heating value, use of the charcoal as
fuel is very interesting. Basically, the firing of powdered coal is a
well-known technology, but has only been used up to now in large-
and medium-scale plants, as the cost of equipment and operation is
relatively high.
Product Standards for Pyrolysis Products 201
For this reason, owing to the greater ease of handling and thus
greater economy, there have also been continual attempts in con-
ventional combustion technology to slurry solid fuels, i.e. to deliver
the ground coal as a pumpable medium with a high energy density.
This does not refer to chemical conversion into liquid components but
to mixing the coal with liquids such as water, fuel oil, pyrolysis oil or
methanol, possibly with the addition of surface-active substances to
improve flow behaviour and stability.
A basic distinction must be made between those mixtures in which
the liquid possesses no heating value of its own and those in which a
part of the heating value of the slurry mixture is provided by the
liquid. Both binary mixtures and mixtures of several constituents are
possible. Mixing pyrolysis charcoal with the aqueous liquid produced
by pyrolysis is an obvious possibility as, in this way, at least some of
the environmentally harmful liquid would be used up.
As a mixture of charcoal and liquid, in any case, necessitates
grinding the charcoal and, in some circumstances, sifting to produce
the desired grain size distribution, many attempts have been made to
carry out a further preparation process in order to improve the
combustion characteristics and environmental impact. In the case of
mineral coal, part of the sulphur (pyritic sulphur) and the ash can be
removed. For this purpose, however, very fine grinding is necessary to
separate the macerates from the minerals.
In the past, however, many projects on mineral coal have shown
that the production and use of coal slurries is not easy, the difficulties
being in details of the plant technology. Therefore, in order to benefit
from the advantages offered by a liquid medium, considerable
expenditure on development, planning and technical equipment is
necessary which is only economically viable in the case of very
high-cost pressure on the fuel side. The enviJ;onmental attraction of
the reduction of ash and sulphur in the case of mineral coal would not
playa major role in the case of charcoal from biomass, as biomass is
naturally low in ash and sulphur. There are even larger obstacles to be
overcome in the process technology than in the separation of the ash
and sulphur-containing constituents from mineral coal.
Therefore, studies should be made from an economic point of view
of whether conventional dust firing is not more advisable, even for
smaller plants. This, however, is not the subject of this work. Another
alternative would be the combustion of a moistened charcoal (to bind
the dust) in a fluidised bed.
202 F. Rick & U. Vix
If, when all the economic marginal conditions are taken into
account, slurrying of the charcoal appears to be worthwhile, the
following compilation of product characteristics and requirements
from the plant technology derived from them, may be of assistance in
finding a technically feasible solution.
2.2 Characteristics of pyrolysis charcoal
Some examples of the characteristics of charcoals from various
pyrolysis processes are listed below.
Reference [8]: Tech-Air Vertical-Bed Reactor (Georgia Tech)
Heating value, kJ/kg
Bulk Density, kg/m3
Volatiles, %
Quality
27900-31400
160-208 kg/m
3
3-25
Particulate, suitable as replacement
material in coal dust firing plants
Alten Pyrolysis Project: Raiano Fluid Bed Reactor (Alten)
Heating value, kJ/kg 29511
Composition % wt
C
H
N
o
S
Ash
Water
81
2
1
8
Traces
7
1
Immediateanalysis, % wt
Fixed C 76
Volatiles 16
Ash 7
Water 1
According to [14], charcoal from poplar and birch has an ash
content of 24-33%.
2.3 Characterisation of charcoal slurries
2.3.1 Heating value, LHV
The heating value of the charcoal-liquid mixture is calculated propor-
tionally from the heating values of the constituents less the vaporisa-
tion enthalpy of the water portion.
LHV (slurry) = E LHVici - rc
w
Product Standards for Pyrolysis Products
where r = heat of vaporisation of water 2442 kJ/kg;
C
w
= proportion by mass of water;
LHV
i
= lower heating value of material i;
Ci = proportion by mass of material i.
203
If a minimum heating value of approximately 18 ()()() kJ /kg is
required for liquid fuels, the proportion of charcoal necessary can be
simply derived from this relationship. Thus, for a binary mixture, a
minimum charcoal proportion of approximately 65-70% must be
achieved (Figure 7).
Ternary mixtures of charcoal-water-light fuel-oil permit more
flexibility. With 10% mineral oil, the proportion of charcoal can be
reduced to approximately 50-55% (Fig. 8).
The high proportion of charcoal required is the major problem in
production of the mixture. The proportion of charcoal influences both
the stability and the viscosity of the mixture.
2.3.2 Density
In the case of solid porous materials such as charcoal, a distinction
must be made between various reference quantities for the density.
The bulk density (p) is calculated as the quotient of the mass of
charcoal tipped into a container and the volume of the filled container.
The bulk density is influenced by the size distribution and shape of the
grains.
The grain density (Pk) is the quotient of mass and volume of the
individual grains. The solid density (Ps) is the quotient of mass and
volume of the charcoal substance free of pores.
The porosity can be calculated from this expression:
p = Ps - Pk x 100%
Ps
The density of a mixture of solids with liquids cannot simply be
calculated from the weighted densities of the individual components.
Changes of volume occur even in a mixture of different liquids. The
volume of the mixture is not the sum of the volumes of the
constituents, and when solids are added, this is even less so. The liquid
partially penetrates the pores of the charcoal grains and the solid
structure is also partly changed. This apparent contraction of volume is
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206 F. Rick & U. Vix
represented by the contraction value c:
Volume balance: V
M
= c(Vs + V
F
)
Mass balance: mM = ms + mF
Density definition: P = m/V
The indices Sand F denote solid and fluid (liquid) respectively.
The density of the mixture is given by:
mM 1
PM=-=
VM c(Cs/Ps + CFlpF)
where C
i
= mJmM = proportion by mass of component i in the mixture.
The extent of the volume difference is also influenced by the effect
of any surface-active substances added. In addition, the density of the
slurry will continue to change for a while after the mixing procedure,
as the penetration of the liquid into the pores takes time and the air
forced out of the pores only escapes slowly.
The density of a 70% charcoal mixture should be approximately
1200 kg/m3. Thus, for a bulk density of about 200 kg/m
3
, the contrac-
tion value is in the range 02-03. If the charcoal is ground, the
porosity drops and the volume difference is reduced.
2.3.3 Viscosity
The viscosity of a charcoal-liquid mixture cannot be described by the
simple Newtonian laws of fluids. Therefore, the main principles used
to describe the rheological characteristics of a fluid substance will be
briefly explained.
In general, the law of flow is
T = F(v)
Here, T is the shear stress, v the shear rate and F(v) the characteristic
material function, i.e. the way in which the shear stress is dependent
upon the shear rate.
For Newtonian fluids such as oil or water, the relationship of shear
rate and shear stress is linear and can be expressed by a fixed factor,
the shear viscosity 1/.
Product Standards for Pyrolysis Products 207
For many viscous materials, however, the shear viscosity is depend-
ent upon the shear rate.
'l'=.,,(v) x V
Fluids whose viscosity reduces with increasing shear rate are
described as structurally viscose or pseudoplastic.
Fluids whose viscosity rises with increasing shear rate are described
as dilatant.
Expressed mathematically,
Structurally viscose or pseudoplastic: m < 1
Dilatant: m > 1
The shear rate is the quotient of the flow velocity and the
characteristic dimension perpendicular to the direction of flow.
For single-aperture pipe nozzles, the representative shear rate is
determined in accordance with the Hagen-Poiseuille pipe flow law
[15]:
2.nw
Yrep=D
where w = mean flow velocity;
D = nozzle diameter.
It is known from various studies on slurries of mineral coal with
water that slurries exhibit very complex rheological behaviour. When
the coal concentration is low, i.e. less than 50%, an almost Newtonian
behaviour is achieved. As the coal concentration rises, this behaviour
deviates. Starting from the static viscosity, the viscosity first reduces
with increasing shear rate (pseudoplastic behaviour) but, at a certain
shear rate, begins to rise again (dilatant behaviour) [15]. The rise
varies significantly according to the composition of the mixture. In
some formulations no rise is seen over wide ranges, with the slurry
again acting like a Newtonian fluid [16].
The viscosity is strongly dependent upon the type of additive.
Higher standards of stability are gained, in some circumstances, at the
expense of a higher viscosity.
Little is known to date about the temperature dependence of the
viscosity of slurries. In the case of charcoal-water mixtures the
208 F. Rick & U. Vix
influence is probably not very great. In the case of mixtures with oil,
their temperature-dependent viscosity is more important.
Viscosity requirements are derived from the requirements for
pumpability and ability to be atomised. In general, approximately
600 cP is regarded as the upper limit for pumpability. Atomisation is
possible from about 30 cP.
Some data and specifications from the literature are listed for an
assessment of the order of magnitude of the characteristics and for
comparison with the viscosities of conventional oils.
Reference {14]: CEMAGREF
Charcoal, wt %
Grain
Water, wt %
Additives, wt %
Viscosity, cP
Rheology
Heating value, kJ/kg
57
70% mean diameter 4 11m
30% mean diameter 25 11m
42
1 (dispersant + stabiliser)
1900 at shear rate v = 100 S-1
Dilatant
16900
Reference [14]: CEMAGREF
Charcoal, wt %
Grain
Water, wt %
Oil, wt %
Additives wt %
Viscosity, cP
Rheology
Heating value, kJ /kg
47
Mean diameter 7 11m
finer grain for ash removal
100% <38 11m
40
12
1 (dispersant + stabiliser)
1900 at shear rate v = 100 S-1
Pseudoplastic
18700
Product Standards for Pyrolysis Products 209
Reference [15]
Viscosity at shear rate v = 100 S-l of a mixture with mineral
coal:
Proportion
of coal (wt %)
70
66
60
50
Viscosity
(cP)
435
215
100
50
Transition
point
(s -1)
60
100
150
From 200 S-l Newtonian
Rheology: Pseudoplastic to transition point, then dilatant
Reference [16]
Viscosity at shear rate v = 100 S-l of a mixture with mineral coal:
Proportion Viscosity Transition
of coal (wt %) (cP) point
(s -1)
715 1200 120
705 700 120
Rheology: Pseudoplastic to transition, then dilatant
Additive
HD 2038 ICI
HD990ICI
These data clearly show that the viscosity of mixtures with a higher
proportion of coal will cause difficulties in transport and atomisation.
2.4 Plant technology
2.4.1 Combustion
Charcoal-water mixtures are not easily combusted. First, the water
portion must be vaporised. At a water content of 30%, between 3 and
4% of the slurry heating value is used for this purpose. This amount,
while in itself small, is missing in the ignition zone where it is most
needed. The time taken for vaporisation is largely dependent on
droplet size and thus on the quality of the atomisation.
Further heat input vaporises the volatile constituents of the char-
coal. When the ignition temperature is exceeded, combustion of the
emerging gases commences. The charcoal grains are further heated
until the ignition temperature of the charcoal is reached. The duration
of combustion of the charcoal grains is proportional to the square of
210 F. Rick & U. Vix
the particle diameter. It is thus primarily determined by the grain size
distribution. As a whole, the flame is longer than with oil or even coal
dust with the same heat output. The higher water content simplifies
gasification reactions through the dissociation of the water vapour into
OH and H radicals. Non-dissociated H
2
0 contributes to improved gas
radiation.
This short description of the combustion process shows the demands
made on the fuel, on the conduct of the process and on the burner.
To improve ignition, the charcoal should contain a high proportion
of volatile constituents, if possible between 20 and 30%. To this end,
correspondingly low process temperatures should be chosen in the
pyrolysis process. The addition of mineral oil can have a similar effect.
The charcoal should have a small grain size with a relatively narrow
grain size spectrum to ensure rapid and even combustion.
Before entry into the combustion chamber, the fuel should be
heated as high as possible. Temperatures of more than 100C at a
corresponding feed pressure would be advantageous as vaporisation of
the water content would commence on emergence of the fuel from the
nozzle.
The combustion air should also be heated as much as possible
(300-400C) to support the ignition.
The flow conditions at the burner should be so arranged that heat
transport from the combustion zone into the ignition zone is ensured
by intensive contraftow. This is best effected by high-speed rotation of
the combustion air entering. Flame plates must be regarded as less
desirable, as deposits of unburnt charcoal and ash can easily form on
them.
The fuel flow must also be controlled in the combustion chamber.
The flame should be kept compact in order to permit full combustion
of all the charcoal grains. Heat loss in the vaporisation and ignition
zone should be avoided in all cases by appropriate lining. Employment
of a separately lined combustion chamber, known as cyclone firing,
may be of advantage.
The ignition of a charcoal-water mixture can only take place in a
warm plant. Therefore, the boiler must be heated with an auxiliary
fuel until the required values for the surface temperature of the
combustion chamber walls (approx. lOOOC) , the combustion air
(250-300C) and the fuel preheating (1l0-120C) are reached. To be
on the safe side, when the slurry is switched on, this support fuel must
also continue to be supplied until a steady flame formation from the
Product Standards for Pyrolysis Products 211
slurry is observed. In some circumstances, e.g. high water content or
low volatile content, the support fuel must remain switched on
permanently.
When uncooled combustion chambers are employed (cyclone fir-
ing), the ash fusibility should be watched. If necessary, fluid ash
removal should be provided [17,18].
2.4.2 Storage and transport
A precondition for the economic production of slurries in continuous
processes and for their employment in industrial firing plants is
adequate stability. During storage, neither separation of the liquid
phases (in ternary mixtures) nor precipitation of the charcoal particles
must occur. Even separation of grain sizes through differing rates of
settling must be regarded as a serious fault. If such stability as
described cannot be achieved through the mixture formulation, special
measures must be taken.
In tank units, stirring devices, bottom scrapers and circulation
devices must be provided. Level container floors with an outlet pipe at
the side have proved troublesome [16]. Conically inclined floors with
the outlet below are preferred.
In the pipes, a minimum speed (approx. 07 mls [18]) must be
exceeded to prevent sedimentation. A lower speed is common,
especially in suction pipes.
In the case of slurries with mineral coal, the erosion effect of the
coal particles is regarded as the determining factor for the working life
of the plant and for the cost of maintenance. Charcoal, however, is
much softer than coal, so this problem is of less significance.
The limitation of erosion, the prevention of sedimentation and also
the rheological behaviour are all decisive factors for the optimum
transport velocity. The optimum viscosity is in the range of the
transition point from pseudoplastic to dilatant behaviour.
Special problems can arise in filling hot pipe sections. As a result of
heating the combustion chamber during the start-up operation, the
empty atomiser torch reaches a high temperature. When the slurry is
introduced, the liquid phase can dry out in the hot pipe sections
causing the charcoal dust adhering to the walls to form a blockage. To
avoid this problem, the charcoal concentration can be reduced during
the start-up. However, this solution is not practicable in the case of
slurries delivered ready for use. As an alternative, oil could be fed in
212 F. Rick & U. Vix
first, immediately followed by the slurry. This, however, leads to
various problems in the regulation of the fuel/air ratio.
2.4.3 Atomisation
The prospect of making use of this fuel is only feasible if the problem
of the atomisation of the charcoal slurries can be satisfactorily
resolved. It is the atomisation which produces the large surface area
necessary for rapid transport of material and heat for ignition of the
fuel. However, energy is required for the enlargement of the surface
area and, in the case of conventional oil atomisers, this is provided by
the fuel pressure and/or by an auxiliary medium applied under
pressure such as steam or compressed air. Put simply, the higher the
discharge velocity, the smaller the droplets generated. The pressure
which has to be applied here increases in proportion to the square of
the discharge velocity.
The discharge volume Q is calculated as follows:
Q =cAV(2p/p)
where A = discharge cross-section = ;rd
2
/4;
p = nozzle pressure;
p = density;
c = discharge coefficient;
d = nozzle diameter.
The discharge coefficient c is dependent upon the Reynolds number,
Re, as follows:
where Re = wdp / fJ;
w=V(2p/p).
Hence
Re = V(2p/p) dp/fJ
Re = V(2pp) d/fJ
When this is substituted in the flow equation:
Q = coA[(2pp )112 d/fJ]fJ(2p/ P )112
Q = coA(2pp )fJ
12
(d/fJ)fJ(2p/ P )112
Product Standards for Pyrolysis Products 213
which resolved gives:
Q = K(p)(fl+
1
)/2(p)(fl-
1
)12(T/)-fl
and
K = coA2(fl+l)/2dfl
In Newtonian fluids the shear viscosity T/ is independent of the shear
rate, but not in the fluids concerned here. At the high discharge
velocities required, the dilatant leg of the viscosity curve is normally
reached, so that the viscosity increases and a higher pressure has to be
applied for the same throughput.
Thus, an atomiser is required which operates at relatively low shear
rates, if possible at the viscosity optimum. A possibility here is the
rotary cup atomiser which also tolerates higher viscosities. The fluid is
fed at low pressure into a rotating conical cup. As a result of
centrifugal force, the fluid spreads inside the cup as a thin film which
flows towards the larger cross-section of the cone. At the rim of the
cup the fluid film fragments into fine droplets, aided by the tangential
air flow.
Experiments have also been carried out with so-called Y -nozzles and
T-nozzles [18] in which an auxiliary medium, steam or compressed air,
provides the atomisation energy. Y -nozzles exhibited an uneven
distribution of the fluid/steam mixture. T-nozzles produced better
results.
Information on the quantity of atomisation steam required, the
nozzle pressure and the shear rate, however, was not found in the
literature.
To put this into perspective, the normal operational viscosities of
various atomisation systems must be compared with the known
viscosities of charcoal slurries. For steam jet atomisers (Y or T types),
a viscosity of up to approximately 40 cP is acceptable and for rotary
cup atomisers up to approximately 80 cP. This is still much lower than
the viscosity range of known slurries with a high charcoal content.
Coal slurries are only capable of atomisation up to a coal content of
approximately 45% [18]. Thus, the requirement for the highest
possible charcoal loading is contrary to the requirement for good
atomisation capability.
For obvious reasons, the droplet size distribution must be larger
than the charcoal grain distribution. Larger droplets exhibit a higher
concentration of charcoal than small droplets, as only the smallest
214 F. Rick & U. Vix
charcoal particles are distributed uniformly throughout all droplets.
Very small droplets are practically free of charcoal [15]. A higher
proportion of fine droplets is therefore undesirable. At a lower
charcoal loading, up to about 45%, i.e. as long as the charcoal slurry
still behaves like a Newtonian fluid, the direct relationship between
nozzle pressure and droplet size remains in force. At higher charcoal
concentrations, the viscosity is increasingly influenced by the as-yet-
unknown shear rate, so that the curve of the droplet size spectrum
against nozzle pressure becomes erratic.
The complete set of values which influence the atomisation of
coal-water slurries have been described with general validity by the
creation of eight undimensioned coefficients [15]: The list of para-
meters is:
f(d
32
, D, L, p, Po, TI, Tlo, 6
p
, a, 6
p
, d
K
, C
K
) = 0
where d
32
= Sauter diameter;
D = nozzle diameter;
L = characteristic nozzle length;
p = density;
Po = density of ambient gas;
TI = dynamic viscosity;
Tlo = viscosity of ambient gas;
6
p
= nozzle pressure;
a = surface tension;
6
p
= density difference, charcoal/carrier medium;
d
K
= particle diameter;
C
K
= charcoal concentration.
Even in conventional oil atomisers, the nozzles are parts which are
particularly subject to wear. This applies even more so for nozzles
through which coal slurries are to be atomised. The choice of material
and the design therefore merit particular attention. Designs in which
the coal slurry is subject to acute changes of direction have proved
unsatisfactory, as have nozzles with tangential inflow and turbulence
chamber. The nozzle material must withstand both high thermal and
high mechanical abrasive stresses.
The atomisation of charcoal slurries cannot yet be regarded as
having been satisfactorily solved.
Product Standards for Pyrolysis Products 215
2.4.4 Emissions
In addition to economic and technical conditions, the potential
environmental effect plays an increasing role in the selection of a fuel.
At present, hardly any reliable values for charcoal slurries can be
found in the literature. However, some information on mineral coal
slurries is available which, despite the difference in product origins,
provides a point of reference:
Burn out 97% at air factors from 125 to 13 (25-30%
Particle emission
Sulphur
Nitrogen oxides
2.4.5 Operation
excess air).
Filters are necessary to comply with legal
requirements.
Wood charcoal contains practically no sulphur.
The formation of nitrogen oxides in a coal slurry
firing plant is claimed to be lower than in a
comparable dust firing plant. This is because
the flame temperature of slurry combustion is
about 200C lower. The high water content in
the flame probably also has some reaction
kinetics significance. It is also known that
NO
x
production in oil flames is reduced by
moist combustion air. The conversion rate of
the fuel nitrogen into NO is claimed to be
only about 10-20%.
To counter the many difficulties which accompany the operation of a
charcoal slurry firing plant, there are also some advantages. Charcoal-
water slurries are not explosive and hardly need to be regarded as
materials which affect water purity. This also applies to charcoal-
water-mineral oil mixtures as long as heavy fuel-oil is used. In the
case of light fuel-oil being used, the hazard classes applicable to this
must be borne in mind.
2.5 Synopsis
The viability of pyrolysis for the exploitation of biomass is largely
dependent upon the value of the pyrolysis products. After the thermal
process, the heating value originally existing in the raw product is
mostly contained in the oil and charcoal products.
There are several possible ways of utilising the pyrolysis oil. In
addition to its use as a chemical raw material, its direct use as a fuel
216 F. Rick & U. Vix
can be realised with the technology familiar in heavy fuel-oil com-
bustion plants. However, information on fuel characteristics is still
needed for the design of plant and equipment. The oil quality should
be further improved through optimisation of process control pro-
cedures and of pretreatment measures such as filtration.
Larger obstacles stand in the way of the utilisation of charcoal. The
subsequent processing of part into active charcoal is possible but the
greater part, if pyrolysis is widely applied, must be used as fuel. In
larger plants, the ground charcoal can be used as a replacement fuel in
dust firing units.
In a powdered condition, however, the charcoal possesses a low
bulk density and thus a small energy content relative to volume. This
renders storage and transport considerably more expensive.
By mixing the charcoal with a liquid medium, water and/or oil, it is
possible to create a pumpable, easily transported fuel with a relatively
high energy density. Counter to these advantages, there are major
problems in the application technology, particularly in atomisation and
combustion. If economic conditions in the future open up a wider
market for pyrolysis, much research and development work still
remains to be carried out.
In further research and development work for the formulation of
product requirements in industrial plants for energy generation, the
overall system with all its interrelationships must be examined more
closely, starting with the pyrolysis process and including exploitation
of the commodities produced and disposal of noxious substances, in a
pertinent techno-economic context.
The future exploitation of biomass as a renewable material will be
essentially determined not only by economic developments but by the
environmental impact and operational reliability of the processes
developed and implemented.
REFERENCES
1. Hansen, W., Olfeuerungen. Springer-Verlag, Berlin, Heidelberg and New
York,1970.
2. Zerbe, C., MineraLOle und verwandte Produkte, 2. Auftage. Springer-
Verlag, Berlin, Heidelberg and New
3. Niepenberg, H. P., Babcock Handbuch 01. Verlag G. Kopf, Stuttgart,
1973.
Product Standards for Pyrolysis Products 217
4. Zabetakis, M. G., Flammability Characteristics of Combustible Gases and
Vapors. Bureau of Mines, Bulletin 627, US Dept of the Interior, 1965.
5. Knight, J. A., et az', Wood oil from pyrolysis of pine bark-sawduSt
mixture. In Fuels and Energy from Renewable Resources, ed. D. A.
Tillman, K. V. Sarkanen & L. L. Anderson. Chicago, 1977.
6. Nabert, K. & Schon, G., Sicherheitstechnische Kennzahlen brennbarer
Gase und Dampfe, 2. Auftage. Eich-Verlag, Braunschweig, 1970.
7. Niepenberg, H. P., Oppenberg, R. & Rick, F., Zusammenstellung
sicherheitstechnischer Daten zur Vermeidung von Explosionen in
Feuerraumen. Die Industriefeuerung, Nr 11 (1978) 17-31.
8. Knight, J. A., Pyrolysis of wood residues with a vertical bed reactor. In
Progress in Biomass Conversion, Vol. I, ed. K. V. Sarkanen & D. A.
Tillman. Georgia Institute of Technology, Atlanta, GA, 1979.
9. Kaupp, A. & Goss, J. R., State of the Art for Small Scale (to 50kW) Gas
Producer-Engine Systems. Final Report to USDA Forest Service, Univer-
sity of California, Davis, CA.
10. Bridgwater, A. V., Economic Aspects of the Raiano Pyrolysis Plant.
Report to EEC DGXII Biomass Energy Programme.
11. Elliott, D. c., Comparative analysis of biomass pyrolysis condensates. In
Health and Environmental Research on Complex Organic Mixtures, Proc.
DOE 62 Symposium Series, Richland, WA, USA., 1987.
12. Gumz, W., Kurzes Handbuch der Brennstoff- und Feuerungstechnik.
Springer-Verlag, Berlin, Gottingen and Heidelberg, 1962.
13. Churin, E. & Delmon, B., What can we do with pyrolytic oils? In
Pyrolysis and Gasification, ed. G. L. Ferrero, K. Maniatis, A. Buekens &
A. V. Bridgwater. Elsevier Applied Science, London, 1989, pp. 326-33.
14. Esnouf, c., Charcoal-water slurries: state of the art and future prospects.
(this volume, pp. 119-154).
15. Glaser, H. W., Zerstauben von Kohle/Wasser-Suspension mit Einstoff-
Druckdusen. Die Industriefeuerung, Nr 41 (1987) 50-57.
16. Krischke, H. G. & Langhoff, J., Herstellen einer Kohle-Wasser-
Suspension und Einsatz als Brennstoff an der 6 MW Wirbelschichtanlage
Konig Ludwig. VDI-Bericht, Nr. 645, Dusseldorf, 1987.
17. Beer, J. M., et az', Das Verhalten von konzentrierten Kohleschlammen
hinsichtlich Verbrennung, Warmetibertragung, Schadstoffemission und
Ascheablagerung. VGB Kraftwerkstechnik 65, Heft 10, Essen, 1985.
18. Burkhard, T. & Thylander, L., Der Einsatz von Kohle/Wasser-
Gemischen in technischen Feuerungen. VDI-Bericht, Nr 574, Dtisseldorf,
1985.
19. Deutsche BP AG, Das Buch vom ErdOl, 4. Auftage. Reuter und Klockner
Verlag, Hamburg, 1978.
20. Kramer, K., Erdol Lexikon. Springer-Verlag, Heidelberg, 1972.
21. Francis, W. & Peters, M. C., Fuels and Fuel Technology. Pergamon Press,
Oxford, 1980.
22. Lohoff, K., Brennstoffversuche mit einter Staub-Heizol-Suspension. Die
Industriefeuerung, Nr. 46 (1989) 31-37.
23. Ubbelohde, L., Zur Viskosimetrie, 7. Auft. Hirzel-Verlag, Stuttgart, 1965.
24. Verordnung tiber Anlagen zur Lagerung, Abfiillung und BefOrderung
218 F. Rick & U. Vix
brennbarer Fliissigkeiten zu Lande (Verordnung iiber brennbare
Fliissigkeiten---VbF) vom 27.02. 1980, Bundes Gesetz Blatt (BGBI), I, pp.
173-229, BGBI. III, pp. 7102-43. Erste A.nderungsverordnung vom
03.05. 1982, BGBI I, p. 569.
25. Erste Allgemeine Verwaltungsvorschrift zum Bundes Immis-
sionsschutzgesetz (Technische Anleitung zur Reinhaltung der Luft-T A-
Luft) vom 27.02. 1986, Gemeins. Ministerial-Blatt (GMBl) pp. 95 ff.,
berichtigt am 04. April 1986, GMBI. pp. 202 ff.
8
Utilisation of Pyrolysis Liquids in Refineries
MARTIN Rupp
VEBA OEL Entwicklungs GmbH, Uhlenbrockstrasse 10, D-4650
Gelsenkirchen, Federal Republic of Germany
ABSTRACT
Pyrolysis liquids have a number of characteristics that limit their fuel
use to combustion applications such as boilers, furnaces and turbines.
These liquids can be catalytically upgraded in dedicated plants to
hydrocarbons. An alternative approach is to introduce them into a
conventional refinery to utilise orthodox oil-refining technologies for
upgrading. This chapter describes the opportunities and limitations for
upgrading pyrolysis liquids in an oil refinery.
1 DESCRIPTION OF PROBLEM
The pyrolysis of biomass for maximum production of a liquid product,
the pyrolysis oil, is a biomass conversion route which is being
considered seriously by the EEC research authorities. This route has
the advantage over direct biomass utilization through combustion in
that a liquid energy carrier is produced which can be stored, handled
and distributed much more easily than the biomass itself. Therefore,
production of pyrolysis oils is preferable for biomass utilization in
terms of flexibility and acceptability and consequently in developing
future market potential.
Unfortunately, the primary pyrolysis oil from a pyrolysis unit, does
not meet the requirements of a storable liquid fuel which fits into the
219
220 Martin Rupp
existing distribution and utilization structures based on petroleum-
derived products.
Table 1 compares a pyrolysis oil from the Raiano plant with Arabian
light crude oil and a Bunker C heavy fuel oil. It can be seen that the
pyrolysis oil has a much poorer .quality than even the heavy fuel oil,
which itself has a rapidly shrinking share of the market because of its
negative environmental impact. Apart from the water and ash content,
the critical quality targets are the high oxygen and nitrogen and the
low hydrogen content. The high oxygen and nitrogen accounts for the
instability of the pyrolysis oil. The low hydrogen content reflects
the high amount of aromatic compounds, which are regarded as cancer
suspect agents. Strict regulations are in preparation, especially for the
middle distillates (diesel fuel), according to EPA rules.
In comparison with petroleum-derived products, positive attributes
of the pyrolysis oil derived from biomass are the low sulphur content
and the absence of vanadium and nickel.
Nevertheless, both from the technical and from the environmental
requirements, substantial upgrading of pyrolysis oils from biomass is
Table 1
Comparison of properties of mineral oils and pyrolysis oils from biomass
Density, g/ cm
3
Carbon, % wt
Hydrogen, % wt
Sulphur, % wt
Nitrogen, % wt
Oxygen, % wt
H/C ratio
Light oil <185C, % wt
Middle distillate 185-325C,
%wt
Vacuum gas-oil 325-500C, % wt
Residue, % wt
Viscosity at 88C, cP
Lower heating value, MJ/kg
a Water, 146%; ash, 15%.
Arabian Bunker C
light
crude
oil
0856
855
126
17
02
177
20
27
28
25
2
0980
857
105
07-35
}2.0
147
64
423
Pyrolysis
oil
(Raiano,
waf basis)"
1-195
738
72
004
126
178
1-17
230
251
Utilisation of Pyrolysis Liquids in Refineries 221
necessary to achieve a general acceptance and a significant contribu-
tion to a future energy scenario.
2 UPGRADING OF PYROLYSIS OILS FROM BIOMASS
Upgrading can be performed by two different ways: by hydrogen
addition processes, or by carbon rejection processes. Both types of
processes are widely used in the petroleum industry. Typical hydrogen
addition processes are hydrotreating and hydrocracking. The most
frequently used carbon rejection process is delayed coking which, from
the chemical point of view, is a pyrolysis process. A modern carbon
rejection technique is the use of ZSM-5 catalysts which minimize coke
yield. However, processes using ZSM-5 catalysts have only been
investigated at laboratory scale.
The advantage of hydrogen addition processes is the high quality of
the products at maximum liquid yield. The disadvantage is the high
hydrogen consumption which leads to high processing costs, but this is
only a short-term economic consideration. The market value of the
by-products, especially coke, is rapidly going downwards, because of
their unfavourable environmental impact. Thus, the economic re-
lationship between these two types of processes will change in the near
future.
As mentioned above, both types of upgrading processes are widely
used in the petroleum industry. Therefore, instead of erecting new
upgrading units for pyrolysis oils, co-processing of pyrolysis oils with
conventional crude oils in existing refineries appears to be a preferred
route for upgrading pyrolysis oils derived from biomass. The
advantage of this approach is that small-scale pyrolysis plants can be
built on a modular and decentralized basis, transferring the product
for upgrading in existing plants with only limited additional investment
required.
Refineries have very large processing capacities. Table 2 gives
typical figures for throughputs of a refinery and upgrading units within
a refinery. In addition, processing capacities for pyrolysis oils derived
from biomass are given when the mixing rate related to crude oil is
limited to 5 or 10%. Assuming a production capactiy of 10 000 t/ a for
a pyrolysis plant the production output from 50 pyrolysis plants can be
accommodated in such a refinery, substituting only 5% of the crude oil
feed of the refinery.
222 Martin Rupp
Table 2
Typical refinery throughput
Throughput Possible capacity for
(tla) pyrolysis oil at different
mixing rates (tla)
5% 10%
Refinery 10000000 500000 1000000
Atmospheric distillation 3000000 150000 300000
Vacuum distillation 1800000 90000 180000
Olefin plant 1600000 80000 160000
Reformer 500000 25000 50000
Middle distillate 1300000 65000 130000
desulphurization
Hydrocracker 1600000 80000 160000
Visbreaker 700000 35000 70000
Coker 1600000 80000 160000
3 COPROCESSING OF MINERAL OILS IN EXISTING
REFINERIES
3.1 Entry points for pyrolysis oils
A simplified processing scheme of a modern refinery with substantial
conversion characteristics is shown in Fig. l.
Crude oil first passes through a desalting unit, in which salts are
dissolved in water and the water-salt mixture is then separated from
the oil. Desalted, water-free oil is distilled in an atmospheric distilla-
tion tower into naphtha, middle distillates and residue. The residue is
further processed in a vacuum distillation unit. Products are vacuum
gas oil and vacuum residue.
Distillation products are either used as marketable products (pool)
or further converted in a catalytic reformer unit (naphtha) or an olefin
plant (naphtha) or a middle distillate desulphurization plant or a
hydrocracker plant (vacuum gas oil) or a visbreaker (residue).
Possible entry points for pyrolysis oils are the desalting unit
(water-containing oils) or the distillation units (water-free oils), as
shown in Fig. l.
3.2 R&D needs
The expected problems from feeding biomass pyrolysis oils into a
crude mineral oil refinery are based on the very different qualities of
both oils.
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224 Martin Rupp
The high water content and the high water-solubility of pyrolysis oils
may seriously influence the behaviour of the desalting unit. Distillation
units are influenced by the different boiling range of pyrolysis oils. In
addition, the qualities of the distillation products may change, which
could adversely influence the qualities of the final marketable products
or the behaviour of the upgrading units. Another problem may be the
acidity of pyrolysis oils which would increase the corrosiveness of the
feed oil.
The main requirements for R&D in this area are as follows:
Characterization of pyrolysis oils
The knowledge of refinery-relevant analytical data of biomass-derived
oils is a fundamental need. The applicability of conventional charac-
terization methods to biomass liquids has to be investigated.
of pyrolysis oils and mineral crude oils
The miscibility of pyrolysis oils and mineral crude oils at different
mixing ratios has to be investigated with respect to:
-liquid-phase separation;
-influence on chemical mixture properties compared with pure
mineral crude oil;
-influence on physical mixture properties such as viscosity.
Desalting/draining
The behaviour of the desalting unit has to be simulated. The effect of
different mixing ratios of pyrolysis oil and mineral oil on operation and
on efficiency of desalting and draining has to be evaluated. The high
water solubility of pyrolysis oil may seriously reduce these efficiencies.
Alternatively the possibility of reducing water solubility of pyrolysis
oils or the separate pretreatment of pyrolysis oils by, for example,
distillation has to be considered.
Distillation
The influence of different mlxmg ratios on operating behaviour,
product distribution and product qualities has to be studied in a
laboratory plant. The thermal instability of pyrolysis oils may cause
serious problems in distillation units. To obtain relevant information
distillation studies have to be performed in a continuous distillation
unit.
Utilisation of Pyrolysis Liquids in Refineries 225
Corrosion
The low pH/high acid content of pyrolysis oils may cause corrosion
problems. Investigations on this problem may lead to the possibility of
pretreating the oil in order to remove carboxylic groups or oxygen. In
this case downstream feed points for introducing pyrolysis oils may be
possible.
Upgrading
Upgrading studies are necessary on bio-oil and mixtures of bio-oil and
conventional products where changes of quantity and quality of feed
streams occur, depending on the results of distillation tests.
The most important questions to be answered are how the qualities
of upgrading unit products are influenced, and how the operating
behaviour of upgrading units changes. The catalytic processes, in
particular, have to be studied experimentally, because the presence of
oxygen-containing components may reduce the activity and lifetime of
catalysts. The required increase in severity of processing conditions
and hydrogen consumption are important data for establishing the
processing costs.
4 GOALS
An R&D programme on the co-processing of biomass-derived pyroly-
sis oils with mineral crude oils is needed to demonstrate the technical
feasibility of this approach. The required changes of the process steps
have to be determined and expressed in terms of performance and
investment. In addition the influence of process severity gives infor-
mation on additional energy, feedstock and material consumption
(hydrogen, catalyst, etc.). With the background of the petroleum
refining industry together with modern scale-up techniques this infor-
mation can be generated from relatively small-scale experiments.
A possible change in product qualities influences the value of the
products. This can be calculated by existing price formulae with
respect to the required product pool qualities.
Combining the information on investment, processing costs and
product values, the value of the pyrolytic oil at the refinery gate can be
evaluated relative to the market values of the refinery products.
Last but not least, a serious R&D programme with sound results is
essential to reach general acceptance of pyrolysis oils derived from
biomass by the refining community.
9
Upgrading of Biomass Pyrolysis Liquids to High-
Value Chemicals and Fuel Additives
THOMAS STOIKOS
Chemical Process Engineering Research Institute, PO Box 19517,
54006 University City, Thessaloniki, Greece
ABSTRACT
Upgrading of lignocellulosic by-products to high-value-added chemi-
cals is a very promising R&D activity, but it is at an early stage of
development.
Phenols constitute a large fraction of the liquids derived from
thermochemically treated biomass and have attracted considerable
interest because of their diverse applications. They can be utilized as
pure components, blended with other materials, or serve as precursors
for the production of many other chemicals.
This paper reviews current activities in the production of high-value-
added chemicals through pyrolysis of biomass, concluding that there are
many possibilities and considerable R&D is necessary to develop
conversion and extraction techniques.
INTRODUCfION
Liquid products obtained from pyrolysis of wood and other forms of
biomass are very complex mixtures of components consisting of
roughly one-third each of neutral and phenolic compounds and the
balance of organic acids, higher aldehydes, ketones, esters and water.
Due to significant amounts of oxygenated compounds, these liquids
have relatively low heating values, are relatively unstable, have high
viscosity, have low volatility and are corrosive and incompatible with
227
228 Thomas Stoikos
the less polar petroleum feedstocks. There are several potential
upgrading procedures for improving the properties of such phenol-
containing streams and mitigating the aforementioned problems.
These processes aim to convert the biomass oils to products that can
be used as light fuel components or feedstocks for producing com-
modity and speciality chemicals.
One method for alleviating the problems associated with the
pyrolytic liquids is catalytic hydrodeoxygenation [1-4]. This upgrading
procedure involves extensive hydrotreatment with hydrogen or hydro-
gen and carbon monoxide under high pressure and/or in the presence
of hydrogen-donor solvents (tetralin, decalin, etc.). The active in-
gredients of typical catalysts used in this approach are sulphided forms
of transition metals such as nickel, molybdenum and cobalt (see
Chapter 4). In a hydrorefining operation phenols are converted into
hydrocarbons and the oxygen present in the hydroxyl group is
removed as water.
A second route for ralslOg the energy density and producing
hydrocarbons from such liquids is dehydration and decarboxylation
over acidic zeolites without the need for any reducing gas; this
is conducted at atmospheric pressure [5-12]. The shape and size
selectivity of these catalysts limit the terminal size of the aromatic
products, resulting in a mixture consisting of up to 17% wt C
7
-C
lO
hydrocarbons [8], which are high-grade gasoline components.
Another upgrading technique involves fractionation of the pyrolysis
oils and recovery of selected components. Due to the chemical
complexity of these mixtures and the low concentration of any single
constituent, it has not been commercially feasible to extract anyone
isolated component. Therefore, utilization of the liquids for this type
of upgrading has depended on grouping and recovering fractions of
similar functionalities and general chemical properties.
The thermochemical process conditions can be suitably adjusted to
cause or increase the production of specific chemicals in the liquid
products. This may be achieved either by a pretreatment of the
biomass material or use of catalysts.
A novel concept of upgrading with potential commercial significance
involves oxygen-alkylation of the phenolics in the biomass pyrolysis
liquids and formation of methyl aryl ethers. This scheme was first
successfully applied to coal liquids which also contain large quantities
of phenols. Specifically, it was demonstrated that these ethers are fully
compatible with gasoline and are excellent non-metallic blending
Upgrading of Biomass Pyrolysis Liquids 229
agents and octane improvers [13-15]. In view of the abundance of
lignocellulosic materials and the increasingly stringent antipollution
regulations placed on automobile emissions concerning lead from
motor gasoline, the conversion of phenols to aromatic ethers may offer
an attractive solution to the problem of octane shortage. The most
favorable phenolics for this purpose are phenol, cresols and xylenols
because the resultant ethers have high octane numbers and their
boiling points are within the range of gasoline [14].
This chapter presents an overview of the efforts to develop processes
for adding value to the biomass pyrolysis liquids through separation
and recovery of selected components or chemical conversion to
products of higher value for various industrial applications or as
transportation fuel additives.
UPGRADING TO HIGH-VALUE-ADDED PRODUCTS BY
FRACTIONATION
Laval University
Researchers from the Laval University (Canada) have reported on the
separation of valuable chemicals from wood-derived oils [16,17]. The
products from a vacuum pyrolysis unit can be separated into an
organic and an aqueous phase in two condensing systems. The
separation is achieved at the outlet of the reactor by a sophisticated
recovery method which involves the pressure of the pyrolysis unit and
the temperature of the cooling water of the condensers. The oil
samples are subsequently subjected to sequential elutions by solvent
chromatography. Phenols and low-molecular-weight carboxylic acids
are two classes of compounds that can be recovered in distinct
fractions.
Selected components can be used for diverse purposes in industry.
For example, phenols, eugenol and guaiacol which are present in
significant amounts, have pharmaceutical applications; hydroxy-
methylpyrone, vanillin and isoeugenol can be used in the food industry
as flavoring agents; oxygenated heterocyclic compounds such as
furfural have application in the paint industries. Table 1 lists a number
of high-value chemicals that are found in pyrolysis oils with their
corresponding market values in 1986 US dollars.
230 Thomas Stoikos
Table 1
Market values of high-value chemicals derived
from biomass pyrolysis oils [17]
Product
Pyrolysis oil
Camphor
m-Cresol
o-,p-Cresol
Eugenol
Furfural
Guaiacol
Isoeugenol
Price (1986 US$/kg)
011
396-770
376
191
859-1289
159
595
1169-1233
SRI International
SRI International has proposed an interesting upgrading procedure
that does not need the separation and isolation of single components.
This scheme pertains to the manufacture of phenol-formaldehyde
adhesives for use in plywood manufacturing [18]. Plywood residues are
pyrolyzed to produce about 25% char and 25% oil, the latter
supplying the phenolics requirement of the plant. The balance of the
oil and char have sufficient energy to supply the whole plant. Another
potential application of the phenolic adhesive approach would be in
the manufacture of reconstituted composition products from wood
fiber, flakes or chips.
Solar Energy Research Institute
Work related to the SRI approach has been reported by the Solar
Energy Research Institute (SERI) with very promising results [19).
Biomass pyrolysis oil is fractionated on the basis of solubility and
differences in reactivity to give a product suitable for use in phenol-
formaldehyde-type resins. The pyrolysis condensates are washed with
water to separate a water-soluble fraction. The water-insoluble mater-
ial is dissolved in ethyl acetate and then washed with aqueous sodium
bicarbonate to remove the strong organic acids as water-soluble
sodium salts. The organic material remaining in the ethyl acetate
solution consists of phenolic and neutral compounds which can be
recovered by evaporating the solvent. If needed, the phenolics can be
isolated from the neutrals by using sodium hydroxide to form the
soluble sodium phenolates in the aqueous phase, neutralizing with
Upgrading of Biomass Pyrolysis Liquids 231
acids to reform the phenols, then extracting with ethyl acetate and
evaporating the solvent.
Preliminary phenol-formaldehyde adhesive formulation work con-
firmed the need to remove the organic and acid fractions from the
phenols/neutral fraction, but the latter can be used without further
purification. This result eliminates an additional process cost and
increases the yield of adhesive material. In the formulation, it was
found that the phenols/neutrals material can be used to replace not
only phenol, but also part of the formaldehyde. An economic
evaluation of the process showed that the cost of producing the
phenols/neutrals fraction is very competitive with that for phenol,
even if no credit is allowed for the organics rejected from the process.
Market and technical aspects
For any separation and recovery process to be viable, the components
of interest should be marketable, be produced in sufficient quantities,
and be recoverable at reasonable cost. In most cases further processing
is required for concentration and purification of the desired products.
CATALYTIC UPGRADING TO HIGH-VALUE CHEMICALS
Wood and other forms of biomass have been the subject of technical
investigations as alternative feedstocks to petroleum and coal for a
number of specific chemicals by judiciously selecting the necessary
experimental conditions and using appropriate catalysts.
University of A1icante
At the University of Alicante (Spain) pyrolysis experiments were
carried out using almond shells as feed, with the purpose of studying
the chemical products which can be formed in the presence or absence
of catalytic compounds [20]. The highest amounts of liquid were
produced at temperatures between 420 and 610C and contained
water, acetic acid, hydroxyacetone, 1-hydroxy-2-butanone, 2-
furaldehyde, methanol, formaldehyde, acetone, 2-propanol, 3-methyl-
1-butanol, propionic acid and acetaldehyde. Table 2 shows the results
obtained in a series of experiments carried out at 500C in a fluidized
bed reactor using CoCh as a catalyst, compared with the results
without any catalyst.
232 Thomas Stoikos
Table 2
Effect of CoCl
2
on the products of pyrolysis of moisture-free
almond shells at 500C (% wt)
Product Catalyst
Solids
Liquids
Acetic acid
2-Furaldehyde
Water
Methanol + formaldehyde
Acetone
2-Propanol
Hydroxyacetone
1-Hydroxy-2-butanone
3-Methyl-1-butanol
Propionic acid
Acetaldehyde
Gases
None 141% CoCl
2
264
583
98
057
17-0
095
007
005
18
13
069
014
018
148
413
461
72
75
232
14
019
017
042
124
Many inorganic chemicals were tested as catalysts, but CoCh was
selected for the study because it allowed better control of the
homogeneity in the impregnation step. It is noteworthy that in the
presence of the catalyst the yield of 2-furaldehyde increases sig-
nificantly, while other compounds are completely absent. Separation
or fractionation of the liquid products is not reported.
University of Waterloo
The Waterloo Fast Pyrolysis Process (Canada) has been developed to
maximize the yields of liquids and their anhydrosugar (mainly levoglu-
cosan) content [21). The research was carried out using wheat chaff, a
typical agricultural waste material. The results of the pyrolysis tests at
500C for untreated material and material treated with 5% H
2
S0
4
are
given in Table 3.
The pretreatment of wheat chaff with sulfuric acid leads to a
conversion of over 70% of the cellulose to fermentable sugars; this is
demonstrated by the significant increase in the yield of levoglucosan.
A substantial drop in the yield of monomer fragmentation products
such as hydroxyacetaldehyde is also observed, as well as a lower char
yield. It is claimed that the acid has two critical effects on the pro-
Upgrading of Biomass Pyrolysis Liquids 233
Table 3
Pyrolysis of wheat chaff at 500C
Feed Yield, rna! (% wt)
Wheat chaff Wheat chaff
untreated acid-washed
Product at room temp.
Gas 141 122
Char 276 164
Water 111 84
Organics 479 596
Total 1007 966
Levoglucosan 12 147
Other sugars 08 88
Hydroxyacetaldehyde 32 tr
Cellulose converted into sugars 73 708
(glucose equivalent), %
cess. First, it removes alkali and alkaline-earth metal cations which
apparently catalyze fragmentation and charring rather than
depolymerization reactions and suppress the levoglucosan yields.
Secondly, it has a positive catalytic effect in releasing anhydrosugars.
The experimental results reported are preliminary and have not been
optimized. Further processing and utilization of the chemicals pro-
duced have not been reported.
University of Tiibingen
A thermocatalytic process has been reported by the University of
Tiibingen (FRG) for the conversion of biomass to oleochemicals and
oil [22]. This process has been designed to produce fatty-acid mixtures
directly from plants, seeds or agricultural waste materials. In the
presence of silicaeceous catalysts the lipids and phospholipids of these
substances are converted to C
12
-C
18
fatty acids at temperatures
between 280 and 320C. Under these conditions, the cellulose and
lignin components of the biomass are converted to char which may be
used as activated charcoal. Both fatty acids and activated charcoal are
valued five times more than fuel. Apart from the fatty acids, a fuel is
obtained which is equivalent to diesel oil. From 100 kg of rape seeds
the process gives 20 kg of fatty acids, 15 kg of diesel oil and 30 kg of
234 Thomas Stoikos
activated charcoal. Other plants tested with the process include
euphorbia, soybeans, lupins and olive waste.
CPERI
At the Chemical Process Engineering Research Institute (CPERI)
considerable work has been carried out on the upgrading of pyrolysis
oils to produce methyl aryl ethers (MAE) by catalytically converting
the phenolic fraction.
Previous work on phenols from coal liquids was carried out for the
US Department of Energy [15]. The phenols were extracted with
aqueous sodium hydroxide, then reacted with dimethyl sulfate to give
the MAE product. In a variety of extensive laboratory and automotive
tests, it was demonstrated that, when the MAE mixture is blended
with commercial gasoline, it produces an equivalent or superior fuel in
terms of octane rating, economy, oil consumption, engine wear,
exhaust emissions and drive ability performance. A comparison of the
research octane number . (RON) for a base gasoline and this base
gasoline containing 5, 10 and 15% by volume of MAE is given in
Table 4, from which it is evident that the latter are promising octane
improvers.
The work at CPERI includes three parallel research activities.
(1) Investigation of the experimental parameters which influence
the yield of biomass pyrolysis liquids and their phenolic content.
(2) Qualitative and quantitative characterization of the liquids and
separation of the phenol components.
(3) Upgrading of the phenolic fraction by studying the catalytic
conversion of the model compound phenol to anisole.
Table 4
Research octane numbers for base
gasoline and base gasoline containing
methyl aryl ethers
Gasoline RON
Base 932
Base + 5% vol. MAE 938
Base + 10% vol. MAE 954
Base + 15% vol. MAE 963
Upgrading of Biomass Pyrolysis Liquids 235
A method has been developed for analysis of the biomass pyrolysis
liquid products and separation of the phenolic fraction [23,24]. The
technique was first tested with model mixtures and then applied to real
samples. The analytical method indicates that a typical liquid resulting
from fir wood pyrolysis contains by weight 35% neutrals, 34%
phenols, 5% organic acids and 10% water, and the balance is
non-extractable compounds. The recovery of phenols using silica gel
chromatography reached over 95%.
The objective of the catalytic upgrading activities has been to
determine the conditions for obtaining high yields of aromatic ethers
while minimizing other side reactions. For this purpose, the reaction of
phenol with methanol was studied, since it is essentially the simplest
and most basic case for the alkylation of the phenolic fraction.
A theoretical study was conducted on the thermodynamic equi-
librium of the system resulting from the methylation of phenol. The
constituents which were assumed to be present in the mixture were
phenol, methanol, anisole, o-,p- and m-cresols, 2,4- and 2,6-xylenols,
o-,p- and m-methylanisoles, 2,3-methylanisole and water. The
composition of the system was evaluated as a function of the
temperature and the methanol/phenol molar ratio. The calculation
was performed by minimization of the free energy of the system. The
study covered temperatures between 250 and 500C and
methanol/phenol molar ratios between 1: 1 and 8: 1. It was found that
the yield of ethers is highest at 250C and decreases with increasing
temperature. In addition, the yield of ethers increases with increasing
methanol/phenol molar ratio. The results indicate that the formation
of ethers is equilibrium-limited, while ring alkylation depends on
reaction temperature. These observations were also reported in an
experimental study of similar systems [25].
Alkylation of phenolic compounds with methanol is promoted on
appropriate catalytic surfaces and has been a subject of considerable
interest [26-33]. Research efforts have focused on understanding and
resolving the problem of nonspecific methylation, namely the competi-
tion between the reactions of the alcohol with the o-,p- and
m-positions of the aromatic ring and the reaction with the phenolic
oxygen. A good catalyst should provide high conversion of phenols,
show high selectivity for aromatic ether production and be easily
formulated from readily available materials.
A summary of the experimental work of CPERI is compared with
236 Thomas Stoikos
Table 5
Summary of the results for the catalytic methylation of phenol to anisole
Catalyst Temp. Methanol/ Phenol Anisole Reference
("C) phenol conversion selectivity
molar (%) (%)
ratio
H-ZSM5 297 1:1 113 642 [32]
Mn/Alz03-1 250 4:1 160 822 [34]
Mn/AI20r-2 275 4: 1 183 729 [34]
La2(HP04)3 300 5:1 126 943 [32]
BaS0
4
300 5:1 74 909 [32]
13X 310 8:1 727 546 [30]
the results of other investigators on the catalytic methylation of phenol
in Table 5.
Discussion
An overview of the numerous studies gives an indication of appropri-
ate conditions and catalysts which need to be employed for conversion
and upgrading of the phenolic compounds present in biomass pyrolysis
liquids, to methyl aryl ethers. These are:
(1) The catalysts should include in their structure appropriate metal
ions which function as active acidic centers.
(2) Infrared studies have shown that the molecules of both phenol
and methanol are adsorbed on the active sites, forming pheno-
late and methoxyl structures. Anisole (the simplest ether
produced from phenol and methanol) can be formed from the
interaction of the reactants adsorbed on adjacent sites or can be
obtained as the product of the reaction of one of the com-
ponents present in the gaseous phase with the corresponding
surface-active complex. A favorable condition for obtaining the
aromatic ether is the formation of a strongly polarized bond
between the metal ion and the phenolic oxygen. This makes the
phenolic oxygen more prone to an attack by a methyl cation.
Catalysts with such properties include La2(HP04h, BaS04,
BP0
4
and certain types of zeolites.
(3) The selectivity to anisole is higher at relatively low temperatures
(200-300C) and short residence times.
Upgrading of Biomass Pyrolysis Liquids 237
(4) Since the phenolic fraction of the pyrolysis oils is a complex
mixture of light and heavy components, a two-step process may
be proposed for the most efficient conversion to aromatic ethers.
In the first step, the feed would be passed over a catalyst which
promotes the cracking of side chains from the heavy alkylated
and alkoxylated phenols, and the formation of lighter phenols.
An experimental study on model compounds has shown that a
hydrotreatment catalyst with MoS
2
/NiS as active ingredients on
phosphated y-A1203 serves this purpose well [35]. Keeping the
temperature at 350C and using H2 at 35 MPa, maintains the
selectivity to phenols and minimizes conversion to hydrocar-
bons. In the second step, the stream of light phenol products
would be passed over another catalyst which favors anisole
formation.
COMPARISON OF THE UPGRADING TECHNIQUES
The primary oils resulting from the thermochemical treatment of
lignocellulosic biomass vary in quality according to the severity of the
conversion procedure. Low-pressure pyrolysis products have high
oxygen and water contents and therefore a low energy density. They
contain low-molecular-weight organic acids, ketones, aldehydes and
furans which are thermally unstable even at relatively low tempera-
tures. Thermal decomposition of these mixtures is observed below
200C. High-pressure liquefaction products have less oxygen and water
and consequently a higher energy density than pyrolysis products.
They have higher viscosity due to the lower water content and exhibit
better thermal stability.
There are three major upgrading techniques for the biomass-derived
oils. Catalytic hydrotreatment at high pressures and upgrading with
zeolites at ambient pressure are refining processes that primarily
produce fuels. Production and recovery of higher value chemicals by
appropriate physicochemical methods is the third upgrading option.
The selection of an upgrading route depends on the desired final
product, as well as the characteristics and the value of the primary oil.
Furthermore, the upgrading strategy should be carefully selected so
that the more highly valued products obtained more than justify the
cost of conversion.
Catalytic hydrotreatment of high-pressure liquefaction products
shows favorable results in terms of yields of high-quality gasoline
238 Thomas Stoikos
(Cs--225C boiling range), but requires long residence times [4].
Pyrolytic products, on the other hand, are not amenable to such
processing directly because they are too thermally unstable and an
undesirable solid residue is formed at the prevailing conditions.
However, through less severe hydrotreatment, pyrolysis oils can be
stabilized and made amenable to catalytic hydrotreatment to hydro-
carbons [4]. Furthermore, a factor that has to be taken into account
in evaluating the economics of hydrotreatment is that the process
is carried out under high pressures (13-17 MPa) and requires the
consumption of large amounts of hydrogen.
Catalytic processing is an emerging technique for the conversion of
biomass pyrolysis oils to upgraded products. The concept was first
tested by using zeolites for the chemical modification of the oils to
light hydrocarbon fuels. The components which decompose under
hydrotreatment conditions are very reactive in the presence of these
types of catalyst and thus the problem of thermal instability is
alleviated. In addition, the need for hydrogen consumption in the
upgrading process is eliminated. A yield of 17% of CS-C
lO
hydrocar-
bons has been reported in a study of hydrocracking of pyrolytic oil
from poplar wood [8].
Numerous processes have been reported on the production of
high-value-added chemicals from biomass pyrolysis liquids. These
processes are based on careful selection of the experimental condi-
tions, applications of various physicochemical methods and use of
suitable catalysts. However, there has been limited utilization of the
products, primarily because of the complexity of the mixtures of
chemicals in the pyrolysis oils. The most promising results have been
obtained at SERI. It has been demonstrated that a phenolic-rich
fraction can be extracted from pyrolysis oil which can replace a major
portion of synthetic phenol-formaldehyde-type resins and adhesives.
CONCLUSIONS AND RECOMMENDATIONS
Several opportunities with significant economic potential have been
identified for the production of high-value-added chemicals and fuel
additives from liquids obtained by thermochemical conversion of
lignocellulosic biomass. The production and utilization of high-value-
added chemicals will enhance the competitiveness, market penetration
and acceptance of biomass raw materials without having to wait for oil
Upgrading of Biomass Pyrolysis Liquids 239
prices to increase. Future research in this field should have the
following characteristics:
(1) Production of speciality chemicals instead of high volume
industrial chemicals. The biomass routes are not currently recog-
nized as being competitive with petrochemicals or coal for the
production of basic industrial chemicals. Therefore, the direc-
tion should be to develop commercial processes for the produc-
tion of speciality chemicals that take advantage of the specific
chemical structures of lignocellulosic biomass and its derivatives
arising from thermochemical reactions.
(2) Application and development of effective and energy-saving
separation techniques for the recovery of useful chemicals.
When the recovery of individual products is not technically or
economically feasible, processes should be developed for the
separation of groups of chemicals with similar functionalities.
An example of such a category is the phenolic fraction. Phenols
can be utilized in the formulation of resins and adhesives or
upgraded to methyl aryl ethers as octane improvers.
(3) Development of novel catalytic processes with high selectivity
and yield of the desired product. Research activities in this
direction should include development of suitable catalysts.
(4) For any developed process it is essential to study the potential
markets for the high-value chemicals produced and clarify all
technical and economic aspects.
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land, WA, 1988.
2. Stevens, D. J., An overview of biomass thermochemical liquefaction
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Upgrading of Pyrolysis Oils from Biomass, ACS Div. Fuel Chemistry,
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3. Soltes, E. J. et al., Catalyst specificities in high pressure hydroprocessing
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of Pyrolysis Oils from Biomass, ACS Div. Fuel Chemistry, Denver, CO,
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4. Baker, E. & Elliott, D. c., Catalytic hydrotreating of biomass-derived
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240 Thomas Stoikos
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(2) 2S7.
S. Prasad, Y. S., et al., Catalytic conversion of Canola oil to fuels and
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6. Prasad, Y. S. et al., Catalytic conversion of Canola oil to fuels and
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7. Chantal, P. D. et al., Reactions of phenolic compounds over HZSM-S.
Appl. Catal., 18 (198S) 133-4S.
8. Chantal, P. D. et al., Production of hydrocarbons from aspen poplar
pyrolytic oils over HZSM-S. Appl. Catal., 10 (1984) 317-32.
9. Chen, N. Y. et at., Fluidized bed upgrading of wood pyrolysis liquids and
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1987,32(2) 264.
10. Renaud, M. et al., Conversion of vacuum pyrolytic oils from Populus
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Pyrolysis Oils from Biomass, ACS Div. Fuel Chemistry, Denver, CO,
5-10 April 1987, 32(2) 276.
11. Diebold, J. & Scahill, J., Biomass to gasoline (BTG): Upgrading pyrolysis
to aromatic gasoline with zeolite catalysis at atmospheric pressure.
In Production, Analysis, and Upgrading of Pyrolysis Oils from Biomass,
ACS Div. Fuel Chemistry, Denver, CO, 5-10 April 1987, 32(2) 297.
12. Dao, L. H. et at., Reactions of biomass pyrolysis oils over ZSM-S zeolite
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Biomass, ACS Div. Fuel Chemistry, Denver, CO, 5-10 April 1987, 32
(2) 308.
13. Singerman, G. M., Methyl aryl ethers from coal liquids as gasoline
extenders and octane improvers. SAE Paper No. 810443, in SAE SP-480,
1981.
14. Fleming, R. D. & Talbot, A. F., Aryl ethers from coal liquids as fuels.
Paper presented at Symposium on Chemistry of Oxygenates in Fluids,
ACS, Kansas City, USA, 12-17 Sept. 1982.
15. Fleming, R. D., Methyl Aryl Ethers from Coal Liquids as Gasoline
Extenders and Octane Improvers. DOE/CE/50022-1 Report, Nov. 1980.
16. Pakdel, H. & Roy, c., Chemical characterization of wood oils obtained in
vacuum pyrolysis process development unit. In Production, Analysis, and
Upgrading of Pyrolysis Oils from Biomass, ACS Div. Fuel Chemistry,
Denver, CO, 5-10 April 1987, 32(2) 203.
17. Roy, C. et al., Preliminary feasibility study of the biomass vacuum
pyrolysis process. In Research in Thermochemical Biomass Conversion,
ed. A. V. Bridgwater & J. L. Kuester. Elsevier Applied Science, London,
1988, pp. 585-96.
18. Wasselle, L. A., Chemicals from wood wastes and pulping residues. In
SRI International Report, Melno Park, CA, USA, June 1982.
19. Diebold, J. & Power, J., Engineering aspects of the vortex pyrolysis
reactor to produce primary pyrolysis oil vapors for use in resins and
adhesives. In Research in Thermochemical Conversion, ed. A. V. Bridg-
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water & J. L. Kuester. Elsevier Applied Science, London, 1988, pp.
609-28.
20. Font, R. et al., Chemicals from almond shells by pyrolysis in fluidized bed.
In Proc. Internat. Conference, Pyrolysis and Gasification, Luxembourg,
23-25 May 1989.
21. Scott, D. S. et al., Sugars from cellulosics by the Waterloo fast pyrolysis
process. In Proc. Internat. Conference, Pyrolysis and Gasification,
Luxembourg, 23-25 May 1989.
22. Bayer, E. & Kutubuddin, M., Thermocatalytic conversion of biomass to
oleochemicals and oil. In Proc. 5th European Conference, Biomass for
Energy and Industries, Lisbon, 9-13 October 1989.
23. Vasalos, I. A., Production and utilisation of synthetic liquid fuels. In
Energy from Biomass 1, ed. G. Grassi & H. Zibetta. Elsevier Applied
Science, London, 1987, pp. 357-61.
24. Vasalos, I. A. et al., Production and utilization of synthetic liquid fuels. In
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dos Santos. Elsevier Applied Science, London, 1990, pp. 681-5.
25. Gould, K. A. & Long, R. B., a-Alkylation of phenols for upgrading of
coal derived liquids. I. Reaction of phenols with branched olefins. Ind.
Eng. Chem. Fundam., 22 (1983) 321-9.
26. Renaud, M. et aI., Anisole production by alkylation of phenol over
ZSM-5. Can. l. Chem. Eng., 64 (1986) 787-91.
27. Marczewski, M. et aI., Alkylation of aromatics II. Alkylation of phenol
with methanol on various zeolites. Heterogeneous Catalysis and Fine
Chemicals, (1988) 273-82.
28. Marczewski, M. et al., Alkylation of aromatics. I. Reaction network of the
alkylation of phenol by methanol on USHY zeolite. l. Mol. Catal., SO
(1989) 211-18.
29. Nozaki, F. & Kimura, I., A study of catalysis by metal phosphates. IV.
The alkylation of phenol with methanol over metal phosphate catalysts.
Bull. Chem. Soc. lap., 50(3) (1977) 614-19.
30. Janaradanarao, M. et al., Catalytic alkylation of phenol with methanol.
National Symposium on Catalysis, Institute of Technology, India, 1978,
pp.51-7.
31. Balsama, S. et al., Alkylation of phenol with methanol over zeolites.
Appl. Catal., 13 (1984) 161-70.
32. Pierantozzi, R. & Nordquist, A. F., Selective a-alkylation of phenol with
methanol. Appl. Catal., 21 (1986) 263-71.
33. Shabalin, I. I. et aI., An infrared spectroscopic study of the adsorption of
phenol on y-A1203 during alkylation by methanol. Kinetica i Kataliz, 15
(6) (1974) 1540-5.
34. Vasalos, I. A. et aI., Production and Utilization of Synthetic Liquid Fuels.
Final Report, EN3B-0052-GR, July 1989.
35. Ratcliff, M. et al., Catalytic hydrodeoxygenation and dealkylation of a
lignin model compound. Production, Analysis, and Upgrading of Pyrolysis
Oils from Biomass, ACS Div. Fuel Chemistry, Denver, CO, 5-10 April
1987, 32(2) 249.
10
Integrated Liquid Fuel Processes
A. V. BRIDGWATER
Energy Research Group, Chemical Engineering Department, Aston
University, Aston Triangle, Birmingham B4 JET, UK
ABSTRACT
Considerable work has been carried out on pyrolysis technologies,
product upgrading technologies and biomass production technologies,
but little attention has been paid to the interaction of these areas or their
integration into a viable and efficient liquid fuel production process.
This paper describes some of the interactions and optimisation exercises
necessary for successful implementation.
1 INTRODUCTION
An integrated process starts with biomass in the field or in the forest
and considers all stages in the processing or conversion up to the point
of producing a product that can be assimilated into the market place
and that has a value. The total process can be summarised in Fig. 1,
which shows the traditional view of the two separate areas of
production and conversion. These need to be integrated into a
complete system for minimum cost and maximum performance.
Within both areas there are opportunities for optimisation and some of
these are explored later.
2 FEEDSTOCK
2.1 Materials
A variety of feedstocks have been considered for pyrolysis, including
energy crops such as wood and annual crops, wood wastes and many
243
244
WOODY
BIOMASS
CONVERSION
A. V. Bridgwater
PRODUCTION
FUEL
PRODUCT
FIG. 1. Overall process for producing and converting biomass.
agricultural wastes, and all forms of municipal waste [1]. The
characteristics and costs vary considerably and most processes have
been dedicated to one particular feedstock. The handling problems of
biomass generally have led to the view that a process has to be
designed for a particular feedstock for successful operation. Charac-
teristics and costs offeedstocks are generally available (e.g. [1]).
One of the potential feedstocks for thermochemical conversion is
wood. This will be available from a number of sources: processing
residues, forest residues, whole trees from thinnings and the produce
from short-rotation energy forestry plantations [1].
-Processing residues are produced primarily in sawmills; these
consist of slabs and blocks of wood as well as chips.
-Forest residues represent a relatively large resource although
usually produced in areas far removed from centres of habitation.
They are the tops and branches which, in normal harvesting
operations, are left in the forest and account for up to 50% of the
total biomass. Harvesting systems for residues involve the use of
Integrated Liquid Fuel Processes 245
terrain or landing chippers which produce a heterogeneous
mixture of wood, bark and foliage with no uniformity of particle
size.
-Whole trees can be harvested from early thinnings, predominantly
from conifers, and chipped or chunked at a landing. Again, the
processed material is not uniform in composition or size.
-Short-rotation energy forestry (SRF) is primarily hardwood cop-
pice harvested on cutting cycles of 3-5 years or single-stem trees
grown on rotations of 15-20 years. These are harvested in the
winter when the leaves have fallen and are usually collected in
bunches prior to chipping which gives a relatively uniformly sized
product. This is due to the better control of feeding to the
chipper.
Annual energy crops, straw and agricultural wastes, and social
wastes are also potential feedstocks, all of which will necessarily have
received some pre-processing prior to conversion as part of a handling
system.
Typical properties are summarised in Table 1.
2.2 Production
2.2.1 Size and shape controls in the forest
There are various processes for comminuting biomass in the forest
including disc, drum and screw chippers, chunkers, shredders, hoggers
and crushers. Of these disc and screw chippers are the most commonly
used.
-Disc chippers are often relatively small and the range of particle
size is quite large, ranging from fines through to long 'stringy'
pieces. There are machines which provide a screen for removing
Table 1
Typical properties of biomass [1]
Forest Processing Whole SRF MSW Straw
residues residues trees (flUff)
Moisture (wet basis), % 30-60 20-60 40-60 40-60 15-40 10-20
Mean particle size, mm 5 x 20 5 x 20 5 x20 5 x20 20 5 x 200
Size range, mm 2-150 2-75 2-100 2-50 Up to 500 5-1000
Bulk density (wet, kg/m') 300 350 300 350 100 200
246 A. V. Bridgwater
the fines but these are rarely viable in many European
applications.
-Screw chippers produce a relatively uniform particle size in terms
of length, the thickness being determined by the diameter of the
material being fed. Particle size can be varied from the traditional
pulp chip to a chunk by changing the size of screw, a fairly simple
operation. Such machines can be powered by an agricultural
tractor in the 150 hp class and have the advantage that the power
requirement and hence cost of production is some 30% cheaper
than for disc chippers.
-Drum chippers allow the greatest control of particle size but their
relative size and power requirements preclude their use in the
forest. Hoggers, shredders and crushers are also more usually
found at the plant although they do not give the same control of
particle size as do drum chippers.
In terms of supplying feedstock to the conversion facility there
appear to be two options:
(1) use of a screw chipper/chunker to produce relatively large
material which can be comminuted further and more accurately
at the plant, or
(2) development of drum chipper technology suitable for applica-
tion in the field.
Although the first option requires double handling of the material, it
does offer the advantage that forest biomass stored as chunks dries
more quickly than chips, thus giving lower transport costs and possibly
providing a more desirable feedstock.
It is important not to forget that there is a relationship between the
characteristics of the material produced in the forest, the requirements
of the conversion process in terms of particle size and shape, and the
effect of particle characteristics on the end product( s ), as illustrated
later in Fig. 3 [1,2]. Some conversion processes require well-defined
feed material which may need extensive pretreatment, and other
processes are more flexible with respect to feed characteristics.
2.2.2 Size and shape controls in the plant-pretreatment
Three main operations can take place in the pretreatment section of a
system: size reduction (by chipping or re-chipping), screening, and size
increase (by, for example agglomeration or pelletisation). The last can
Integrated Liquid Fuel Processes 247
be justified only in extreme circumstances. Pretreatment is the
interface between feed provision and conversion and, simply, the more
pretreatment, the higher the cost and the lower the overall process
efficiency. If screening is required, important consideration must be
given to the undersize fraction since, if this cannot be used, the system
efficiency will be impaired.
2.2.3 Storage, handling and feeding requirements
A high length-to-diameter ratio (of more than about 25) generally
causes problems of bridging in free-flowing systems unless forced
feeding is practised. This is generally unacceptable for anything other
than feeding the reactor itself.
3 PRODUCTS
3.1 Rio-oil
The crude liquid product may be readily burned and has been
employed for this purpose. Some problems have been reported in its
use, and special precautions may have to be taken in handling, storage
and combustion. The crude bio-oil has a high miscible water content
and a high oxygen content, and compatibility with conventional fuels is
variously reported as immiscible but compatible. For these reasons,
pyrolysis liquids cannot be assimilated into a conventional fuel
marketing infrastructure. Some conversion or upgrading is necessary
to give a product that is compatible with conventional fuels-the
alternatives were summarised in Chapter 1 and discussed in detail in
other chapters. The alternative is to create a discrete pyrolysis liquids
storage, distribution and utilisation system, that is managed by experts
who understand the special problems of this fuel. This is only likely to
be viable either in exceptional conditions or in a dedicated application.
The water content is important as it has several effects; it reduces
the heating value, affects the pH, reduces the viscosity, influences both
chemical and physical stability, reduces potential pollution problems
from waste water disposal by absorbing the water in the product and
could affect subsequent upgrading processes.
3.2 Secondary products
The full range of primary pyrolysis products and their applications was
described in Chapter 1. Figure 2 shows the overall range of secondary
248
CONVERSION
TECHNOLOGY
A. V. Bridgwater
PROCESSING
TECHNOLOGY
""""", ,
""""", ,
: . SECONDARY ' .:.
. : PRODUCTS :-:
FIG. 2. Overall pyrolysis conversion to primary and secondary products.
products that can be derived from pyrolysis, with emphasis on the
production and utilisation of liquid fuels such as bio-oil and derivatives
and slurries. Gaseous fuels are also produced under appropriate
conditions, either as a byproduct or as the major product. While in all
cases these can be transformed into secondary products, byproduct
gases will tend to be used in-plant, such as for power generation, and
major products such as alcohol fuels and other synthesised products
will only be produced from large gas production systems. Char is also
produced to a varying extent which can either be utilised in-plant or
converted into a char-oil or char water slurry as described below.
3.3 Slurries
A possible outlet for the char is slurrying with the oil, or with water,
or with both oil and water. Only a limited amount of char can be
introduced into oil as unacceptably high viscosities result from a char
concentration higher than about 30% wt. The maximum concentration
of char in water that can be handled is about 60% wt to retain
mobility. Costs of the additive are reported to be significant at about
one-third of the slurry preparation cost.
Integrated Liquid Fuel Processes 249
4 INTERACTIONS WITH REACTOR
The critical step in an overall thermochemical conversion process to
produce a valuable product from biomass, is the reactor. This has both
absolute and preferred requirements in respect of feedstock charac-
teristics. It also significantly influences the characteristics of the
product(s); and conversely the product required will affect the mode of
reaction and type of reactor. This inter-relationship is further compli-
cated by the effects of feedstock characteristics on product characteris-
tics as depicted in Fig. 3. Examples of reactors are included to
illustrate some of the effects.
-Liquids production by fast or flash pyrolysis require small particle
sizes (Iilelow about 3 mm) to achieve the very high rates of
reaction that cause liquid oils and tars to be formed in preference
to char and gases. Consistency in size and shape is important for
high conversion efficiencies.
-Liquids production by pressure liquefaction requires pumping a
slurry or paste of particles to pressures of up to 500 bar. The
ability to pump this mixture places a size and shape constraint on
the particle sizes, but this cannot be readily defined.
-Orthodox pyrolysis or carbonisation in fixed-bed, moving-bed or
rotary-kiln type reactors probably has the least specific feed
requirements of any system, as long as the reactor is adequately
sized.
-Fixed-bed systems have a minimum size and shape requirement to
avoid plugging the reactor, to support the bed, and avoid blowing
particles out of the reactor; and a maximum size range require-
ment to keep voids free for gas flow. Lean-phase reactors such as
fluid beds and rotary kilns are more tolerant, but there is still a
minimum size and shape to avoid eluting partially reacted or
high-surface-area particles from the reactor which reduces
p
;
c
T
FIG. 3. Interaction of feed, reactor and product.
250 A. V. Bridgwater
efficiency and increases gas clean-up problems. Conversely,
entrained-bed and cyclonic reactors have more critical constraints
in terms of both size and shape consistency to ensure that the
residence time is correct for complete reaction [2].
Any mismatch between feed characteristics and reactor requirements
is met by adding pretreatment stages before the reactor, as shown in
Fig. 4. A similar problem attends matching conversion to product
application, which may require provision of product clean-up or
upgrading downstream of the reactor, which is also included in Fig. 4
for completeness. A basic objective of system design or specification is
minimisation of cost, which is aided, for example, by minimising the
number of steps in the process, and/or by maximising overall process
efficiency.
In practice, the biomass producer has little control over most of the
characteristics listed above. There may be a choice of feedstocks
available such as wood, MSW or straw. In the case of wood, for
example, there is a choice of species, mode of growth and harvesting
such as coppice, short-rotation forestry or conventional forestry, all of
which will be largely determined by economics, markets and local
conditions.
For a given biomass resource of wood or straw, there is only the
particle size and shape over which the producer can exercise any real
control. MSW can be considered in the same way as wood in that it
cannot be converted raw or untreated, and would have to be subjected
to some form of processing. The relationships and interactions for
MSW are much more complex. The requirements and influences of
size and shape in production and conversion of wood have been
explored to identify critical interactions and recommend strategies for
optimisation as well as recommendations for R&D [2).
F
E
E
D
P
_____ .R
o
D
U
-----c
T
FIG. 4. Interaction of feed, reactor and product with pretreatment and
post-treatment steps.
Integrated Liquid Fuel Processes 251
5 UPGRADING
5.1 Principles
The crude pyrolysis liquid has a high oxygen content which has to be
eliminated to produce a hydrocarbon fuel that is entirely compatible
with conventional fuels. This oxygen can, in principle, be rejected as
water or carbon dioxide using hydrotreating or zeolite synthesis
respectively.
Hydrotreating is based on technology that is established in the
petroleum industry and is in principle readily adaptable to pyrolysis
liquids although a more complex multistage process is required. The
product is a low-octane gasoline suitable for blending.
Zeolite-based synthesis has been extensively demonstrated for
alcohol feeds. Some experience has been gained on upgrading
products of cellulose pyrolysis, but there is concern over the problems
of coking and few results are yet available. The main product is a
high-octane gasoline.
Neither technology is yet available commercially; robust mass
balance and performance data have not been produced.
The main overall processing routes from biomass at the factory gate
to liquid fuel are shown in Fig. 5.
5.2 Hydrotreating
Hydrotreating may be carried out in a plant that is close-coupled to
the pyrolysis plant, either on a satellite pyrolyser or central pyrolysis
plant. The alternative is to carry out the hydrotreating within a
conventional oil refinery using conventional and existing technology.
This approach is justified by the claim that up to 20% of the feed to a
refinery could be crude pyrolysis liquids, although there is not yet any
evidence that this would be acceptable. It is, however, worth noting
that hydrotreating of pyrolysis liquids employs similar technology to
conventional refinery hydrotreating, although the oxygen content of
crude oil is zero, and the hydrogen is utilised for different reactions.
There are several ways of approaching the question of where to
perform the hydrotreating upgrading of biomass. These are illustrated
in Fig. 6.
Case 1 Satellite pyrolysis plants feeding a dedicated central
hydrotreater, with crude hydrocarbons going to a conven-
tional refinery.
252 A. V. Bridgwater
BIOMASS
HYDROCARBONS
FIG. 5. Alternative processing routes for pyrolysis liquids within the factory
gate.
Case 2 Satellite pyrolysis plants each with its own dedicated
hydrotreater, with crude hydrocarbons going to a conven-
tional refinery.
Case 3 Satellite pyrolysis plants feeding crude pyrolysis liquids to a
conventional refinery with associated hydrotreater.
Case 4 Satellite pyrolysis plants feeding a dedicated central
hydrotreater with associated dedicated refinery.
Case 5 Biomass feeding a central large pyrolysis plant with as-
sociated dedicated hydrotreater, with crude hydrocarbons
going to a conventional refinery.
Case 6 Biomass feeding a central large pyrolysis plant, feeding crude
pyrolysis liquids to a conventional refinery with associated
hydrotreater.
Case 7 Biomass feeding a central large pyrolysis plant with associated
dedicated hydrotreater and associated dedicated refinery.
Biomass
Biomass
Bi omass
Integrated Liquid Fuel Processes
PYROL YSIS HYDRO-
REFINING
PLANTS TREA TING
Hydrocarbon
Producta
Hydrocarbon
ProdUCIB
Biomass
______ .. Hydrocarbon
ProdUCIB
Biomass

Hydrocarbon
Producta

Biomass
-
-----ltt[J---.. Hydrocarbon
Producta
Biomass

Small satelli te
<IIID
Dedicated hydro
pyrolysis p l ant treating plant
8]
<IIIllIID
Integral hydrotreatlng ...
I
plant with refinery

Central
Stand-alone
pyrolysis plant hydrotreating
plant
..... ...... . .
FIG. 6. Alternative hydrotreating scenarios.
Hydrocarbon
Products
Micro
refinery
ConvenUonal
reflnery
253
254 A. V. Bridgwater
Some of these options, such as the construction of a dedicated mini- or
micro-refinery or dedicated micro-hydrotreating plants, are clearly not
viable, but the full range of alternatives is shown to illustrate the
diversity of solutions available. The optimum route depends on
productivity of biomass feed, cost of each operation, yield of each
operation, and value of product. This requires optimisation, but there
are too many site-specific variables and a dearth of information to
enable generalised solutions to be presented. This is, however, an area
of considerable importance and potential, which requires addressing in
the future.
5.3 Zeolite upgrading
Upgrading of pyrolysis products to hydrocarbons by zeolites is
analogous, except that far fewer data are available. There are three
basic approaches:
(1) Convert primary pyrolysis vapours to hydrocarbons, then feed
the products to a refinery. This has to be a close-coupled
operation.
(2) Condense the liquids, then process them with zeolites in the
liquid phase, which would be a remote operation to take
advantage of the economies of scale.
(3) Condense the liquids, then revaporise them for zeolite upgrad-
ing in the gas phase, which would also be a remote operation to
take advantage of the economies of scale.
The major products are aromatics--benzene, xylene and toluene-
which make this fraction a high-octane gasoline material. These
aromatics are also potentially more valuable in their own right as
chemicals. A major by-product has been reported to be olefins. These
can command a good price as a chemical feedstock, subject to
quantities and locations, or can be considered for alkylation to
increase the hydrocarbon fuel yield. The range of alternatives for fuel
production is shown in Fig. 7, and again some of these options are not
economically viable.
While the technology appears to be very attractive in giving high
yields of valuable hydrocarbons in a conceptually simple process, there
are several problems to be overcome arising from the coking be-
haviour of the catalyst. This will require continuous regeneration as in
a fluid catalytic cracker on a conventional refinery.
Biomass
Biomass
Biomass
Biomass
Biomass
Biomass
Biomass


Integrated Liquid Fuel Processes
PYROL YSIS ZEOUTE
REFINING
& ALKYLA TION


Hydrocarbon
Products
Hydrocarbon
Products
Hydrocarbon
Products
Hydrocarbon
Products

::: .. -l---- Hydrocarbon
Small satelllle
pyrolysis plant
Central
pyrolysis plant
I
Integral zeolile and
alkylation
plant with refinery

Stand-alone
zeolite and
alkylation plant
fD
LJ


.......... -
Products
Hydrocarbon
Products
Micro
rennery
Conventional
refinery
FIG. 7. Alternative zeolite upgrading scenarios.
255
256 A. V. Bridgwater
6 SYSTEM PERFORMANCE AND COST
6.1 Mass and energy balances-liquid fuels
In order to show how different systems compare in terms of mass
balance and energy efficiency, an overall conceptual process is
summarised in Table 2. This starts from wet biomass in the forest, and
produces increasingly refined and hence valuable products through
pyrolysis oil, to crude hydrocarbons, to refined hydrocarbons. The
table gives typical but fairly conservative mass conversions for each
step, and constructs a conceptual mass balance, and overall mass and
energy efficiencies based on typical data reported in the literature
including relevant chapters in this book. Supportive notes are included
to explain the data used.
The four balances are identical, but have different bases to show
overall conversions both from the feedstock and to different products.
The overall yields are comparable with other reported data. Small
changes in efficiency at any stage could have a significant effect on the
overall conversion figures. The four balances provided are:
(1) starting with 100 weight units of daf (dry ash free basis) wood or
200 weight units of wet wood at 50% moisture;
(2) producing 100 weight units of crude pyrolysis oil;
(3) producing 100 weight units of crude hydrocarbons;
(4) producing 100 weight units of refined hydrocarbons.
6.2 Yield model
In general terms the yield of bio-oil from wet biomass is given by the
following expression:
Yield = Mass wet wood x E
bp
X Est x Esr x Ed X Ep
where E
bp
= fractional mass conversion efficiency or yield
of biomass production;
Est = fractional mass conversion efficiency or yield of
solid transport;
Esr = fractional mass conversion efficiency or yield of
size reduction;
Ed = fractional mass conversion efficiency or yield of drying
(including moisture content changes);
Ep = fractional mass conversion efficiency or yield of pyrolysis.
Integrated Liquid Fuel Processes
257
Table 2
Overall typical mass and energy balances to liquid products
Process step performances
Process step Yield Notes
(%daf)
t Biomass production 50-tOO Some biomass has to be left in the forest or
field . Production is assumed to be export
from site at 100% yield.
2 Transport 100 Minimal loss in transport would be expected.
3 Size reduction 80-100 The proportion of reject material depends on
feed characteristics and reactor requirements
(see above). Minimal material will be lost.
4 Drying 90-100 Some fines will be lost, but these are ignored.
Drying to 0% water is assumed, although
unrealistic.
5 Pyrolysis 20-70 Yields of up to 70% wt have been achieved in
pilot plant operation, so 50% yield is
conservative.
6 Transport 100 Only applies if separate/remote upgrading is
used. Losses in transport should be minimal.
7 Upgrading 30-50 Yield depends on the extent of upgrading and
oxygen removal.
8 Transport tOO Only applies if separate/remote refining is
used. Losses in transport should be minimal.
9 Refining 75-100 Yield depends on the extent of upgrading
carried out previously and losses in refining.
Mass balances
Process step Water Yield (massdaf) Mass balances on yield and water
content
(typical Range Typical Wood Pyro- Crude Refined
% wt) assumed lysis HIC HIC
oil
1 Biomass SO 50-100 100 200" 400 1000 1112
production
2 Transport SO 100 100 200 400 1000 1112
3 Size SO 80-100 100 200 400 1000 1112
reduction
4 Drying 0 90-100 100 100 200 500 556
5 Pyrolysis 20-70 SO SO 100 250 278
6 Transport 100 100 SO 100 250 278
7 Upgrading 30-50 40 20 40 100 111
8 Transport 100 100 20 40 100 111
9 Refining 75-100 90 18 36 90 100
(continued)
258 A. V. Bridgwater
Table 2-( continued)
Overall yields
Fraction Overall yield (%)
Pyrolysis oil
Crude hydrocarbons
Refined hydrocarbons
a 100 on dry basis.
Mass basis
50
20
18
Energy basis
56
45
41
(In all cases moisture content changes are also included, as for
example during storage.)
Other process steps may be readily added, analogously.
For refined hydrocarbons the analogous expression is:
Yield = Mass wet wood x Ebp X Est x Esr x Ed X Ep x Eu x E
lt
x Er
where
Eu = fractional mass conversion efficiency or yield of upgrading;
Elt = fractional mass conversion efficiency or yield of liquid transport;
Er = fractional mass conversion efficiency or yield of refining.
E
bp
, Est> Em Ed and Ep are defined as before, and moisture content
changes are included, as above.
Again, other process steps may be readily added in an analogous
way.
6.3 Charcoal and slurry products
A similar exercise is carried out for charcoal, char-water slurries and
char-oil slurries in Table 3, and analogous yield models can be
derived:
Yield = Mass wet wood X Ebp X Est X Esr X Ed X Ec x Eu X Elt X Esl
where
Ec = fractional mass conversion efficiency or yield of carbonisation;
Esl = fractional mass conversion efficiency or yield of water slurrying.
E
bP
' Est, Esn Ed, Ep and E
lt
are defined as before, and moisture
content changes are included, as above.
Again, other process steps may be readily added, and char-oil
slurry yield models derived in an analogous way.
Table 3
Overall typical mass balances to slurry products
Process step performances
Process step
1 Biomass production
2 Transport
3 Size reduction
4 Drying
5 Carbonisation
6 Slurrying, char-water
7 Flash pyrolysis
8 Slurrying, char-oil
Mass balances
Yield (% daf) Notes
50-100
100
80-100
90-100
30
167
20-70
90-110
Water
content
Some biomass has to be left in the forest or field.
Production is assumed to be export from site at 100%
yield.
Minimal loss in transport would be expected.
The proportion of reject material depends on feed
characteristics and reactor requirements (see above).
Minimal material wiD be lost.
Some fines will be lost, but these are ignored. Drying to
0% water is assumed, although unrealistic.
Volatile free char is assumed, at typical yields of 30% wt
on dry biomass feed.
60% wt char is assumed-the maximum found to be
possible for stable and mobile slurry [3]. This gives a
167% wt yield of slurry on char feed.
Yields of up to 70% wt have been achieved in pilot plant
operation, so 50% yield is conservative. Some char is
also produced at yields of up to 15 or 20% wt on feed.
Assumes 50% oil and 125% char yield from flash
pyrolysis of biomass, giving a 20% wt char slurry in
bio-oil. The maximum found to be possible for a stable
and mobile slurry is 25% [3]. The yield for flash
pyrolysis is conservative as shown above. This gives a
100% wt yield of slurry on bio-oil + char feed.
Additives, if necessary, will increase this yield.
Yield (mass, daf) Mass balances on yield and water
for process step
(typical % wt) Wood Charcoal Char
Range Assumed water slurry
slurry
1 Biomass 50 50-100 100 200" 666 400 320
production
2 Transport 50 100 100 200 666 400 320
3 Size 50 80-100 100 200 666 400 320
reduction
4 Drying 0 90-100 100 100 333 200 160
5 Carbonisation 30 30 30 100 60
6 Slurrying, 40 167 167' 50 167 100
char-water
7 Flash pyrolysis
Liquid 50-70 50
Char 5-20 125
8 Slurrying, 625 100
char-oil
e
(continued)
260
Overall yields
A. V. Bridgwater
Table 3 -(continued)
Fraction Overall yield (%)
Mass basis
Charcoal
Char-water slurry
Char-oil slurry
100 on dry basis.
b Yield on char or char + bio-oil.
30
50
625
Energy basis
50
50
72
c assumes 50% oil and 125% char yield from flash pyrolysis.
6.4 Cost models
The conceptual mass balances in Table 2 are used to derive production
costs for each of the three liquid products using the step efficiencies
quoted in the table, and taking total costs for each process step from
biomass in the forest or field to individual product. Table 4 lists the
individual step costs used in the cost model and shows the results for
the specific cases listed and for the general cases where the efficiency
of each step in the process can vary. The models can be further
developed for other process steps and/or other products in an
analogous way. Optimisation can be carried out, for example, on
process steps or transport costs.
The results show the significance of upstream conversion and
handling steps with, for example, the cost of production, transport and
size reduction of wet biomass having an ll-fold greater significance
than the cost of upgrading and liquid transport on the final product
cost.
7 CONCLUSIONS
Little attention has been given to the design or specification of
integrated systems for efficiently converting biomass to useful and
marketable fuel products. There are two major areas requiring further
study-integration of biomass production with conversion, and op-
timisation of biomass conversion systems.
Integrated Liquid Fuel Processes 261
Table 4
Process step production costs and cost models
Process step Cost (Total production cost)
Biomass production B /wet tonne
Transport (solid) 1; /tonne (wet)
Size reduction S /wet tonne
Drying D /dry tonne
Pyrolysis P /tonne pyrolysis liquid
Transport (liquid) 7; /tonne liquid
Upgrading V /tonne crude hydrocarbons
Transport (liquid) 7; /tonne liquid
Refining R /tonne refined hydrocarbons
From mass balances in Table 3
Cost of pyrolysis liquid, Cp = P + 2D + 4S + 41; + 4B
Cost of crude hydrocarbons, C
c
= V + 257; + 25P + 5D + lOS + 101;
+ lOB = V + 257; + 25C
p
Cost of refined hydrocarbons, CR = R + 1117; + l11V + 2787; + 278P
+ 556D + 11-12S + 11121; + 1112B
= R + 3897; + 1-11 V + 278C
p
=R+117;+1-11C
c
Generally
If E is the efficiency of conversion of each step, with subscripts referring to
each operation as above, then:
D S 1; B
Cp = P + - + + + ---::---::--
Ep Ep * [H20] Ep * [H20] * Es Ep * [H20] * Es
7; V 7; P D
CR=R+-+-+ + +-----

S Ts
+
ER * Eu * Ep * [H20] ER * Eu * Ep * [H20] * Es
B
+------:----
ER * Eu * [H20] * Es
7.1 Integration of production and conversion
It is recommended that R&D be instigated to consider matching and
optimising the various wood harvesting systems with the various
conversion systems. Some specific recommendations are:
-A survey of appropriate harvesting systems and their charac-
terisation by performance and cost.
262 A. V. Bridgwater
-An examination and evaluation of comminution technologies with
respect to the requirements of the conversion process.
-Collation and analysis of data on product size distribution from
different comminution systems.
-An examination of the effects of each product size distribution on
each current and proposed conversion system.
-Design of systems technically and economically to optimise
utilisation of the full range of particle sizes from a woody biomass
feedstock.
7.2 Optimisation of conversion systems
There is considerable potential for optimisation of the conversion
process as exemplified by the hydrotreating options and the system
cost models. Specific recommendations include:
-Collate robust performance data on conversion and upgrading
processes.
-Collate data on transport and handling costs of biomass and
derived products.
-Assess the costs and feasibilities of the range of alternative
systems for production of useful and valuable products.
-Identify areas of limited data where this is critical to the sensitivity
of the processes.
-The cost models show the significance of conversion efficiency or
yield, and cost in early stages in the conversion process on final
product yield and cost. This helps to identify areas where greater
attention should be focused to help reduce the cost of biomass-
derived fuels.
REFERENCES
1. Mitchell, C. P. & Bridgwater, A. V., Pretreatment and characterisation of
feedstocks. In Proceedings of EC Conference on Gasification and Pyrolysis,
Luxembourg, May 1989.
2. Bridgwater, A. V. & Mitchell, C. P., Interfacing production and thermo-
chemical conversion of woody biomass. In Biomass for Energy and
Industry, ed. G. Grassi, B. Delmon & F. Zibetta. Elsevier Applied
Science, London, 1987.
3. Antonelli, L., Alten Final Report to EEC, 1989.
11
Environmental Aspects of Gaseous Emissions
from Wood Carbonisation and Pyrolysis Processes
CORINNE MEZERETIE & PHILIPPE GIRARD
Centre Technique Forestier Tropical, Cirad Department, 45 Bis Avenue
de la Belle Gabrielle, 94736 Nogent sur Marne Cedex, France
ABSTRACT
Most industrial pyrolysis technologies currently operating in Europe,
and worldwide, produce charcoal. The charcoal-making equipment
essentially consists of partial combustion kilns that do not recover the
by-product gases and condensable organic compounds. This often
results in atmospheric pollution and poor energy conversion yields.
This chapter provides information on the composition and toxicity of
gaseous pyrolysis effluents. Experimental results from various studies
including concentration and emission factors of pollutants are given for
different pyrolysis processes. Legislative aspects are discussed and some
treatment and utilisation techniques of such effluents are presented
including condensation and incineration.
1 INTRODUCTION
The development of techniques for thermochemical biomass conver-
sion, including pyrolysis, is hampered by a number of limiting factors:
-a significant drop in crude oil prices;
-the high cost of delivered biomass/lignocellulosic raw materials,
including waste;
-pyrolysis technology is still only at the research or industrial pilot
stage for many applications.
263
264 Corinne Mezerette & Philippe Girard
There are, however, several opportunities that could change the rate
of development of pyrolysis technology:
(1) When oil prices rise once more (as is likely in the medium and
long term), the availability of a method of co-generating liquid,
gaseous and/or solid fuels from biomass could contribute to the
improvement of the balance of trade in Europe. Agricultural
land now abandoned or set aside (1 million hectares in 1988-
1989 in the latter case) could be allocated to the production of
wood and lignocellulosic raw materials for the energy sector.
(2) In developing countries, the energy situation is fundamentally
different and in many cases, biomass supplies a considerable
proportion of energy-up to 60% in the least developed
countries. In the tropical zones with their potential for cheap,
abundant and renewable sources of biomass and wastes, pyroly-
sis can create opportunities for the development of national
energy resources. Efficient techniques developed in Europe
could thus rapidly find initial application in these areas.
(3) The rational use of biomass for energy can be less polluting than
conventional fuels, particularly coal and fuel-oil [1]. A proper
understanding of thermochemical processes can promote the use
of materials other than wood or biomass such as household or
industrial waste. The development of efficient pyrolysis tech-
niques can also solve related environmental problems and also
add value to urban and industrial waste.
Almost all current industrial pyrolysis is orientated to charcoal
production, and sometimes includes recovery of co-generated products
such as bio-oil. In charcoal-making, mass and energy yields are very
low (a maximum of 30% and 50% respectively), especially where
by-products are not recovered for recycling (see also Chapter 2). The
carbonisation process causes the loss from charcoal of 52-54% of the
initial carbon, 77-82% of the initial hydrogen and 87-90% of the
initial oxygen in the by-products.
This loss of material is seen in the emission of gases and complex
organic compounds which can cause substantial air, ground, and water
pollution. These pollutants can be divided into three major categories:
-dust and particles;
gases;
organic compounds.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 265
Recent research on pyrolysis has improved the understanding of the
processes involved and enhance process efficiency. This chapter aims
to provide a survey of the environmental and pollution problems
related to pyrolysis and to give a brief account of the means developed
to reduce emissions and improve conversion efficiency.
2 WOOD PYROLYSIS: BASIC MECHANISMS
Pyrolysis of biomass proceeds by the successive degradation of its
principal constituents, i.e. hemicellulose, cellulose and lignin, which
vary in thermal stability. The degradation processes produce a large
number of different substances. The reaction mechanisms are complex
and are not yet fully understood [2,3].
Five stages can, however, be defined for the slow pyrolysis process
[4]:
(a) Up to 2()(JOC: Drying-stage. Wood loses moisture, together with
some volatile compounds (oily and oleoresinous matter).
(b) 200-280C: Breakdown of the less thermally stable hemicellu-
lose. Xylans give off water (adding to the moisture already
present in the wood), acetic acid, formic acid and furfural.
Carbon monoxide, carbon dioxide and methanol also appear at
this stage.
(c) 2BO-350C: A distinct exothermic reaction begins at 280C
during which the temperature rises rapidly to 350C with no
external energy supply. CO and CO
2
emission continues, and
emission of hydrocarbons of low molecular weight now begins
(methane, ethane, ethylene). Lighter tars now appear, in
addition to acetic acid, formic acid, methanol and acetone.
(d) 350-500C: An external source of energy is now required to
maintain the process. Cellulose breaks down, producing water,
CO
2
and charcoal, with rapid reaction processes giving an
unstable intermediate substance (levoglucosan), which in turn
breaks down into substances similar to those obtained from
hemicellulose. Lignin also degrades to phenol compounds (phe-
nol, cresols and gaiacol) and methanol. Heavier tars begin to
appear.
(e) 500C and over: More or less complete dissociation now occurs.
The less abundant gases become enriched in hydrogen.
266 Corinne Mezerette & Philippe Girard
In addition to the above, a number of thermochemical phenomena add
to the diversity of the substances obtained and increase the complexity
of pyrolysis, including reaction and recombination of intermediates
and products, polymerisation, dehydration and cracking.
The composition and relative proportions of the three main products
of pyrolysis (charcoal, liquids and gases) vary according to the process
parameters:
-nature of the raw material;
-final reaction temperature;
-reaction rate;
-pressure;
-particle size of raw material;
-moisture content of raw material;
-atmosphere in which the reaction takes place;
-effect of catalysts.
Figure 1 shows the influence of reaction temperature and rate of
reaction [5] (see also Chapter 2).
Flash Fast Medium Slow
o bJ i
500
I _ i
i
GaS Liquid
Charcoal
t(s)
FIG. 1. Variation in the proportions of gas, tar and charcoal according to
reaction time and temperature.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 267
3 CHARACTERISTICS OF PYROLYSIS-RELATED
POLLUTION
The following areas of interest have been covered in studies on the
nature of compounds given off during wood pyrolysis:
-Economic. Recovery of substances such as:
(a) acetic acid, formic acid, methanol, ethanol, phenols. There
is a market for these products, although there is strong
competition from synthetic substances;
(b) flavouring substances for use as food additives, and which
are difficult to obtain by synthetic means.
-Scientific. Furthering the understanding of pyrolysis mechanisms.
-Environmental. More recently, the polluting nature of these
compounds has been studied, since a thorough understanding of
the characteristics and concentration of effluent to be processed is
essential to develop appropriate effluent processing techniques
such as sizing of incinerators, filters and condensers.
3.1 Types of poUutants
Several hundred different compounds are produced during pyrolysis,
and some of these have not yet been identified. If discharged into the
environment they may all be regarded as polluting to a greater or
lesser degree.
These pollutants may be classified in three ways:
-dust and particles in suspension;
-non-condensable gases;
---<.:ondensable or pyroligneous organic compounds in vapour or
aerosol form.
3.1.1 Particles and dust
These generally consist of soot, charcoal dust, ash and refractory tar
particles, which are entrained in the gaseous emissions. They are often
incorporated into tar bubbles of different sizes, which means that they
cannot easily be measured with the standardised detection methods
normally used in monitoring combustion units.
268 Corinne MezereUe & Philippe Girard
3.1. 2 Non-condensable gases
These include:
-noxious gases such as carbon monoxide;
-carbon dioxide;
-hydrocarbons (methane, ethane, ethylene, acetylene, propane,
isobutane, butene);
-hydrogen.
As wood and biomass rarely contain sulphur, noxious gases such as
SOx should not normally be found in pyrolysis effluents. Measure-
ments made on an industrial charcoal-making site showed very small
amounts of NO
x
(close to the detection limits) which are not
necessarily related to charcoal-making.
3.1. 3 Condensable or pyroligneous organic matter
These substances are given off either in vapour or aerosol form,
depending on the temperature of emission and the vapour saturation
point for each emitted compound. When they condense, a heterogen-
eous liquid is formed which can usually be separated into two phases:
-An aqueous phase, containing mainly initial moisture and reaction
water in which considerable quantities of organic acids and
alcohols are dissolved as well as other volatile substances [6]. The
nature of these substances is now well known.
-A viscous organic or tar phase, a number of studies carried out
on pyrolysis tars have identified 'families' of particular compounds
[6-8]:
(a) linear saturated and unsaturated hydrocarbons;
(b) polycyclic organic matter (POM);
(c) ketones and cyclic lactones;
(d) phenol compounds;
(e) furfuryl compounds;
(f) nitrogeneous organic compounds.
More than 400 different compounds have been identified in pyrolysis
tars, including over 40 POMs and some 50 nitrogenous organic
compounds [8]. Table 1 shows the main organic compounds found in
the condensable fraction of pyrolysis effluent.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 269
Table 1
Principal organic compounds found in the condensable fraction of pyrolysis
effluent
Alcohols
Methanol
Ethanol
2-Propenol
3-Methylpropanol
Ketones
Acetone
2-Butanone
2-Pentanone
2-Hexanone
Heptenone
Organic acids
Formic acid
Acetic acid
Propanoic acid
Butanoic acid
2-Butenoic acid
Pentanoic acid
Hexanoic acid
Furfuryl compounds
Furfural
Methylfurfural
Furfuryl alcohol
Phenolic compounds
Phenol
Cresols
Gaiacol
Dimethoxyphenol
Methylpropylphenol
Butenylphenol
Saturated and unsaturated linear hydrocarbons
Hexatriene
Tridecane
Dipropyldodecane
Pentadecane
Hexadecane
Cyclic hydrocarbons
Propylcyclopentane
Propylcyclopentene
Ethylcyclopentene
Aromatic hydrocarbons
Indene
Naphthalene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Pyrene
Benzo[ a ]pyrene
Chrysene
Benzofluorene
Basic nitrogen compounds
Methoxypyridine, ethanolpyridine,
propylmethylethylpyrazine, methoxybutylpyrazine,
butylhydroxypyrazine, etc.
Dimethoxypiperimidine, dimethoxyethylpiperimidine
Tetrahydroquinoline, methyltetrahydroquinoline
Methylpurine, dimethylpurine, propylpurine,
methylpropylpurine
270 Corinne Mezerette &: Philippe Girard
3.2 Measurement of gaseous emissions from pyrolysis
As statistical data on effiuents from pyrolysis processes was so scarce,
a collaborative project was established to carry out the following tasks:
-to describe and quantify atmospheric effiuents related to pyrolysis
activities.
-to test different fume-reprocessing systems [9-11].
An appropriate sampling system was developed and tested on several
industrial sites. In this project, CTFT collaborated with CITEPA
(Centre Interprofessionnel Technique d'Etudes de la Pollution At-
mospherique), EDF (Electricite de France), and LNE (Laboratoire
National d'Essai).
3.2.1 Methodology
In order to describe such emiSSions, representative samples of the
effiuent to be characterised had to be taken. Such sampling must be
carried out isokinetically to provide an accurate measurement of
particle and pollutant concentration in the emissions.
Given the particular characteristics of pyrolysis effiuent, i.e. a high
content of water and condensable substances and a high tar concentra-
tion, standard techniques were not applicable. A specific sampling
system for pyrolysis effiuent was therefore developed by CTFT and
LNE [12] which is depicted in Fig. 2. This system ensures:
-Precise measurement of effiuent flow through the chimney stack
under constant isokinetic conditions.
-Monitoring of the cycle as a whole (in the case of a batch system)
with sampling lasting long enough to be representative of the
60-180 min pyrolysis cycle time with continuous sampling of
condensable substances and sequential sampling of gases.
-Separation of condensates from the gaseous phase and measure-
ment of the proportion in the effiuent.
-Trapping of all tars before the filter, for subsequent measurement.
-Monitoring of parameters such as pressure and temperature at
various points and with time.
Gases and condensates are subsequently analysed by chromatography
[6]. This sampling system, however, does not allow direct measure-
ment of particles and dust incorporated with the tar.
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272 Corinne Mezerette & Philippe Girard
Using this system, several series of measurements were carried out
on different sites, with the following objectives:
-Study of emissions from partial combustion kilns and other
pyrolysis systems.
-Assessment of effluent concentration and emission factors for
different types of wood.
-Estimation of the energy content of fumes with a view to
recycling.
-Performance tests on different effluent processing systems.
3.2.2 Results
Tests were carried out on the following pyrolysis processes:
-a non-industrial partial combustion batch carbonisation system;
-an industrial system using a hot gas recycling process;
-a torrefaction process (partial pyrolysis at low temperature).
(a) Rate of production of pollutants. Emissions from a partial
combustion batch carbonisation kiln vary during the cycle according to
the average temperature of pyrolysis [9]. A general rule for the
production of substances cannot be defined as emissions vary accord-
ing to the type of kiln used and to the management of the pyrolysis
process. However, maximum emission levels occur during the exo-
thermic stage when the wood undergoes most transformation.
Figures 3a and 3b show how the components of the condensable and
non-condensable fractions change with time from a partial combustion
batch carbonisation kiln of capacity 2m
3
Figures 4a and 4b show, for
comparison, the rate of production of gaseous and liquid substances
during pyrolysis in an indirectly heated retort.
(b) Influence of wood species. Table 2 shows the emission charac-
teristics from a partial combustion carbonisation kiln for two different
wood species. These results show clearly that the nature of effluent will
differ for different wood species. Spruce tends to produce more
hydrocarbons and tar, whereas oak will generate more acid
compounds.
(c) Comparison of efJiuents from different processes. Table 3 gives
the characteristics of effluents from different methods of pyrolysis. It
appears that partial combustion processes generate more CO, CO
2
and
Gaseous Emissions from Carbonisation and Pyrolysis Processes 273
v
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\l, carbon dioxide; *, hydrocarbons.
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FIG. 3b. Partial combustion: condensates. 0, Tars; x, phenolic compounds;
\l, furfuryl compounds; *, acids.
274 Corinne Mezerette & Philippe Girard
100
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TEMPERATURE
FIG. 4a. Slow pyrolysis in retort: gas content. D, Hydrogen; x, carbon
monoxide; \1, carbon dioxide; *, hydrocarbons.
III
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TEMPERATURE
FIG. 4b. Slow pyrolysis in retort: condensates. D, Phenolic compounds; x,
furfuryl compounds; \1, acids.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 275
Table 2
Mean characteristics of partial combustion batch carbonisation kiln effluent
according to wood species used
Oak Spruce
(g/Nm3)
(kg/t dry (kg/t
(g/Nm3)
(kg/t dry (kg/t
wood) charcoal) wood) charcoal)
Gaseous substances
CO 60 122 350 40 110 380
CO
2
190 383 1100 151 412 1425
H2
25 5-1 146 17 47 165
Hydrocarbons 113 232 663 87 240 83-3
Condensable substances
Total mass of organic
compounds 56 110 330 36 105 350
Tars 170 345 99 13 336 116
Phenolic compounds 10 19 55 08 20 68
Furfuryl compounds 07 14 40 05 13 43
Acids 140 286 815 53 204 70
Light compounds 50 102 29 2-4 63 22
hydrocarbons than retort systems, to the detriment of condensable
pollutants. However, with processes based on hot gas recycling,
emissions for gaseous pollutants are lower than those found for partial
combustion systems. The two systems appear to give fairly similar
results for emissions of condensable pollutants.
Whatever the process used, it is apparent that pyrolysis generates
large quantities of noxious compounds which can be classified by their
emission factors in descending order, as shown in Table 4.
Further details of compounds found in pyrolysis products and
condensates can be found in Chapter 6 and [6,26].
A preliminary POM (polycyclic organic matter) emission measure-
ment was carried out during a series of tests on a partial combustion
kiln. The concentration of this group of pollutants was estimated at
50 mg/Nm3, with an emission factor of 135 kg/t of charcoal obtained,
which is very high considering the toxicity of these substances.
Direct measurements of nitrogenous organic compounds in eftluents
have not yet been carried out. However, according to Essayegh [8],
this group accounts for 24% of tars. By extrapolation of the results
given in Table 3 for partial combustion, emission factors for nitrogen-
ous organic compounds can be estimated at 08 kg/t of dry wood
used, and 27 kg/t of charcoal obtained.
276 Corinne Mezerette & Philippe Girard
These figures for POM and nitrogenous organic compounds must be
considered with caution since neither group has yet been thoroughly
assessed. Further tests are necessary in order to provide a sound
description of these two groups of noxious compounds.
(d) Special case of torrefaction. Torrefaction processes are at pre-
sent being extensively developed in France and, although tempera-
tures do not exceed 270-280C, torrefaction is a source of considerable
pollution. The main pollutants are acid compounds (56 kg/t torrefied
wood obtained). Fairly high emissions of phenol compounds have also
been noted at 4 kg/t torrefied wood obtained.
4 ENVIRONMENTAL ASPECTS
Pyrolysis can be a source of soil and water pollution when emissions
are condensed, for example in a chimney stack, as well as atmospheric
pollution. As shown in Section 3.2.2, the nature and quantities of
pollutants found in pyrolysis fume vary according to the wood species
used and to reaction characteristics.
These studies are only concerned with atmospheric pollution, as this
gives the most cause for concern, due to the ease of inhalation,
widespread dispersion of pollutants and contact with particularly
sensitive membranes. The effects on and damage to human tissues
vary according to the concentration and toxicity of the pollutants.
4.1 Hazards
Various studies have established the toxicity of substances in pyrolysis
smoke and particularly in the heavy tar fraction [14,15]. The effects of
different pollutants on animal and vegetable organisms as well as on
inert materials have been described by Detrie [16].
4.1.1 Gases
Wood and biomass rarely contain sulphur, and these studies have
never established the presence of sulphur compounds in pyrolysis
gases. Some American studies, however, have noted the presence of
SOx in wood-smoke. As to NO
x
substances which are formed only at
high temperatures, tests carried out at temperatures below 600C
showed only traces just over the sensitivity threshold of the measuring
apparatus used.
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278 Corinne Mezerette & Philippe Girard
Table 4
Noxious emissions from pyrolysis
CO
2
CO
Tars
Compound
emitted
Acids
Hydrocarbons
Phenolic compounds
Furfuryl compounds
Hydrogen
Emission factor
(kg /t charcoal)
370-1100
140-320
100-260
60-180
50-70
6-13
4-25
4-15
Apart from CO
2
, the only gas which is found in large quantities in
pyrolysis etlluent is carbon monoxide, which is very insidious and very
toxic.
4.1. 2 Condensable substances
The condensable fraction contains water and a substantial acid
fraction, with acetic, formic and propionic acids predominating to-
gether with the non-biodegradable toxic phenolic group.
The most toxic pyrolysis by-products, however, are the POM group
(polycyclic organic matter) and the nitrogenous organic substances in
tar, all of which display considerable mutagenic and carcinogenic
activity. A high degree of mutagenic activity has been detected in
charcoal tar and attributed to the presence of primary aromatic
carbohydrates. Similarly, carcinogenic activity has been detected and
attributed to the polycyclic nitrogenous derivatives (aza-arenes) found
in these forms of tar [17-20].
The 671 organic pollutants shown to be present in the atmosphere
and listed in EMIC data (Environmental Mutagen Information
Centre) have been classified by Kalsey [14] into four main groups:
-known carcinogens;
-probable carcinogens;
-substances favourable to the appearance of tumours or co-
carcinogens;
-mutagens.
Of these 671 pollutants, 77 are biologically active, with the
distribution shown in Fig. 5, according to [14].
Gaseous Emissions from Carbonisation and Pyrolysis Processes 279
Known
carcinogens
2S
Biologically active substances
77
Probable
carcinogens
20
tumours I
co-carcrnogens
1S
FIG. 5. Active atmospheric pollutants.
The different compounds in tar identified by Essayegh [8] include
seven in group 1, two in group 2, nine (including the phenols) in group
3 and 12 in group 4.
This means that 30 out of the 77 polluting chemical compounds
found in the atmosphere and known to be biologically active have
been found in pyrolysis tars. Where smoke is not reprocessed (as in
non-industrial and semi-industrial charcoal-making), these substances
are all emitted to the atmosphere.
It is possible that some of the 379 chemical compounds identified by
Essayegh-which include 49 nitrogenous organic substances-should
also be included in the groups mentioned above. Although not listed
by Kalsey as their presence in the atmosphere was not noted, this does
not necessarily mean they are not toxic.
Furthermore, no studies are known to have been made on the
biodegradability of substances given off by charcoal-making, nor on
possible recombination phenomena induced by exposure to UV rays in
the atmosphere.
4. 1. 3 Dust and particles
Tests carried out in conformity with French standards on different
charcoal-making processes were not able to include specific measure-
ments of dust and particles, since these agglomerate with the tar.
280 Corinne Mezerette & Philippe Girard
However, several studies have been made in the USA [21-24] on dust
emissions from wood-burning. In the case of residential heating, it
appears that:
-Emissions increase in volume as heat yields decrease, as a result
of poor combustion. Such conditions come close to those in which
pyrolysis occurs.
-Particles emitted are very small in size (017 f.l.m in diameter on
average), which facilitates dispersion and respiratory intake, thus
potentially increasing pulmonary infections in areas where
wood is used extensively as a source of energy.
Although care should be taken in comparing these results as they
will vary with different heating systems and operating conditions,
pyrolysis activities could affect the environment in a similar way unless
preventative measures are taken. The potential effects could be
enhanced by the particle fraction in charcoal-making smoke being
made up of tar and dust agglomerates which are liable to increase their
toxicity. Research is, therefore, necessary in this field to establish toxic
levels and 'effective' preventative measures.
4.2 Regulations
There is only limited information on the nature of regulations
governing charcoal-making activities worldwide. It seems that, gener-
ally, charcoal-making is not subject to any national regulations,
although various local arrangements for particular or similar installa-
tions may exist.
In France, for example, charcoal-making is subject to regulations
covering activities classified under Heading 104: 'Carbonisation of
wood by means other than stacks on woodland sites':
-A permit must be obtained in cases where substances produced by
pyrolysis are given off into the atmosphere.
-Where this is not the case, registration with the relevant author-
ities is sufficient; where pyrolysis gases are incinerated, the
relevant sites are classified under Heading 153a: 'Combustion
plant'.
The following criteria listed in various Orders or Draft Orders of the
Prefect are given as examples in Table 5 [11]. A more specific set of
regulations is currently being drafted by the department at the French
Ministry of the Environment for the prevention of industrial pollution.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 281
Table 5
Typical emission criteria for pyrolysis plants in France
General rules
-Emissions of toxic smoke, vapours, dust, aromatic gases,
etc., are prohibited.
-Gaseous emissions must be recovered and piped.
-Diffuse emissions must be avoided.
-Measurements of pollutants may be required, at the expense
of the operator.
-Plant must be provided with equipment necessary for meas-
urement of pollutants with positioning and apertures permit-
ting standardised measurements.
Special rules
Plant with gas incineration
-Temperature >750C (2 seconds).
-In case of system failure, the use of a flare is permitted
(maximum 200 hours per year).
-0
2
content> 7%.
-CO content<01-02%.
-C0
2
content < 12%.
-Concentration of solid particles < 130-300 mg/Nm3 (in rela-
tion to 7% CO
2
),
-Ejection speed > 8 m/s.
Plant without gas incineration
-Concentration of solid particles < 150 mg/Nm
3

-CO content <005%.
-Total hydrocarbon content < 300 mg/Nm
3

-Phenol content < 20 mg/Nm
3

-Emission through a chimney stack.
4.3 Economic impact
High emission levels of incompletely reacted material also have an
adverse economic effect in reducing yields of the main product,
affecting reliability of equipment and requiring higher investments in
pollution control equipment. One approach to reducing pollution is
better design which not only reduces emissions but also increases
yields, and increases plant availability. The combined effects can have
a significant economic impact.
5 POLLUTION REDUCTION TECHNOLOGIES
Several recovery systems for processing pyrolysis gaseous effluents are
being practised or studied. The two main considerations are economics
282 Corinne Mezerette & Philippe Girard
and technology. There is a cost implication in meeting legislative
requirements which can be offset by recovering energy and/or
by-products, and the recovery processes have to be designed for a
wide range of substances including dust, toxic gas, POM, and
hydrocarbons.
5.1 Condensation
Condensation of the condensable part of gaseous emissions is only
appropriate where viable uses for condensates exist. Three different
techniques are known to have been developed, and other methods are
proposed.
(a) Lambiotte/SIFIC: Two kilns with an annual capacity of
10 000 tons of charcoal each are now operating in the Nievre (France).
Pyroligneous liquor is first condensed, then distilled. Because of
competition from the petrochemical industry, the profitability of this
operation relies partly on the production of charcoal (which was
originally a by-product) and substances with high market value such as
aromatic food additives, and partly on the fact that capital costs for
this installation have been written off. Gas emissions are burnt to
supply energy for the wood dryer and to provide heat for the pyrolysis
process.
(b) Alten (KTl & Italenergie): A 500kg/h pilot plant has been built
and operated at Raiano in the Abruzzi region of Italy (see Chapter 2).
There are three main aims:
-to produce charcoal from small sized woody biomass;
-to condense the pyrolysis liquid in order to retrieve the tar
content for use as heavy fuel for heat or energy production;
-to recycle the light fraction and non-condensable gases to supply
the energy to dry the raw materials and/or to produce electricity.
This last aim has not yet been tested.
(c) Bio-alternative: A 2 t/h commercial carbonisation plant is oper-
ating in Spain. Condensed tar is used as heavy fuel-oil. Tar is
condensed above the boiling of water to lower the water content of
the tar and increase its heating value. The gas and water vapour are
burned.
(d) The SLBE: Where pyrolysis effluent is processed through
partial or total condensation without recovery of condensates for
chemical uses or to supply energy, or of a fraction of these con dens-
Gaseous Emissions from Carbonisation and Pyrolysis Processes 283
ates (aqueous phase), certain companies have put forward methods for
refining effluent by organic means.
The SLBE, an organisation which produces torrefied wood, has
chosen to condense all the condensable material, then refine it by
organic means based on biological processes with balanced nutrition.
(e) The CTFT: Another method has been tested based on electro-
filtration. This technique uses a wet electrostatic precipitator which
works with a circular discharge applied to a film of water. A potential
difference of 12-13 kV is applied between the ionising electrode and
the aqueous film, which is recycled inside the filter and collects the
deposited pollutants. A prototype tested with carbonisation smoke
gave very encouraging results:
Tars
Light compounds
Acids
Phenols
Furfuryl compounds
Total efficiency
Efficiency of removal (%)
94
34
56
84
68
66
Further work is needed to optimise the system.
This seems to be a very promising technique for processing
pyrolysis effluent and also for cleaning gasifier gas before feeding to
an engine. The electrofilter should be tested for these potential
applications.
5.2 Incineration
The heating value of pyrolysis vapour (containing gas and tars) is
sufficient to justify an energy recovery system. This can considerably
improve energy conversion yields if the energy produced is recycled
into the process. Various pyrolysis processes operate in this way, such
as Framatome/Proser/Cemagref, Lambiotte/CISR, and Sonocarb.
In the case of discontinuous batch processes, several reactors can be
coupled together to operate in succession, in order to even out
variations in vapour quality. Sonocarb has adopted this method to
process and recycle smoke from charcoal-making in a metal partial-
combustion kiln (see Fig. 6). With this process, part of the heat is
recycled to dry wood prior to carbonisation. A substantial amount of
energy remains for use in other areas such as drying of timber. Some
results are given in Table 6 and a detailed energy balance has been
published [25].
284 Corinne Mezerette & Philippe Girard
o
t
FIG. 6. Schematic of the Sonocarb unit with gas incineration. 1, Charcoal kiln;
2, smoke collector; 3, incinerator; 4, burner (propane-fired); 5, dilution of
gases; 6, hot air inlet for drying; 7, exit of moist air; 8, smoke exit; 9,
connection between kilns and collector; 10, air inlet.
Table 6
Performance of carbonisation effluent incineration
Sampling point Before After
incineration incineration
Concentration of by
weight, mg/Nm
Average gas output, Nm
3
/h
Average temperature, C
CO content, % of gases
CO
2
content, % of gases
O
2
content, % of gases
NO .. content, ppm
Total hydrocarbon content, ppm
C
50000
550
90
3
5
15
12000
A
2
5700
430
6
15
40-55
20-30
Gaseous Emissions from Carbonisation and Pyrolysis Processes 285
The results show the high efficiency of incineration of pyrolysis
vapours. Moreover, as substantial amounts of usable energy are
produced, the investment costs for the incineration equipment can be
recovered very quickly.
6 CONCLUSIONS AND RECOMMENDATIONS
It has been shown how pyrolysis and carbonisation techniques create
environmental pollution problems unless preventative steps are taken.
As concern for the environment grows, increasing attention will have
to be paid to the pollution aspects, but it must not be forgotten that
enhanced efficiency accompanies reduced emissions. Implementation
of this objective can be achieved by the following measures:
-Continuing fundamental and applied research on pyrolysis with
particular attention to yield improvement and consequent reduc-
tion in by-products and emissions. This can be achieved through a
better understanding of the phenomena involved and improved
design of equipment.
-Continuing to study emissions from pyrolysis processes and their
environmental effects.
-Developing new and more efficient pollution control techniques
and equipment. In the case of charcoal production, this will
necessarily require the development of effective smoke-recovery
systems. The prospects for smoke-incineration systems appear to
be promising as these not only reduce pollution but can also
supply considerable quantities of heat which can be recycled into
the process.
ACKNOWLEDGEMENTS
The authors wish to express their thanks to the AFME for their
financial assistance with a large section of the studies which gave the
results described in this chapter. We also wish to thank the LNE for
their very useful help with several effluent measurements which are
included here.
286 Corinne Mezerette & Philippe Girard
REFERENCES
1. Girard, P., Environmental problems in the use of biomass fuels. Global
and local aspects. Paper presented at International Conference, Pyrolysis
and Gasification, 23-25 May 1989, Luxembourg.
2. Deglise, X., Les conversions thermochimiques du bois. Revue Forestiere
Franfaise, 34(4) (1982) 249.
3. Shafizadeh, F., Pyrolys and combustion of cellulosic materials. Adv.
Carbohyd. Chem., 23 (1968) 419-74.
4. Briane, D. & Doat, J., Guide Technique de la Carbonisation. Edisud,
Aix-en-Provence, 1985.
5. Deglise, X. & Magne, P., Mecanismes fondamentaux de la gazeification.
Biomasse Actualites (Numero special) No.5, 1983.
6. Villeneuve, F. & Vergnet, A. M., Techniques analytiques applicables aux
liquides et aux gaz de pyrolyse de la biomasse tropicale. Bois et Forets des
Tropiques. Cahier scientifique No.9, 1988.
7. Beaumont, 0., Pyrolyse extractive du bois. These de doctorat de 3eme
cycle, Ecole Normale Superieure des Mines de Paris, 1981.
8. Essayegh, M., Etude analytique des jus pyroligneux. These de doctorat de
3eme cycle, Universite Pierre et Marie Curie, Paris, 1988.
9. Meyer, c., Determination des rejets atmospheriques lors de la car-
bonisation par combustion partielle. Memoire de fin d'etudes, Centre
Technique Forestier Tropical, 1986.
10. Girard, P., Meyer, c., Fontelle, J. P. & Boillot, M., Caracterisation des
emissions de carbonisation en four 11 combustion partielle. Mise au point
de systemes de traitement des fumees de carbonisation. Paper presented
at 4eme Conference Europeene, Application de la Biomasse pour
I'Energie et l'Industrie, 11-15 May 1987, Orleans, France.
11. Anon., Carbonisation du Bois et Pollution Atmospherique. CITEPA,
1986.
12. Lachenal, J., Mezerette, C., Vergnet, A. M. & Toledo, J. M., Implemen-
tation of a technique for particle and gaseous sampling in effluents from
pyrolysis in a metallic kiln. Paper presented at International Conference,
Pyrolysis and Gasification, 23-25 May 1989, Luxembourg.
13. Delsey, M., La Pollution due aux Moyens de Transport. INRETS,
Laboratoire energie nuisances, Notes d'information No. 13, 1979.
14. Kelsey, M. I., Kraybill, H. F. & Tucker, c., A data base of organic
pollutants that have been evaluated for carcinogenicity and mutagenicity.
Paper presented at International Conference on Residential Solid Fuels,
Portland, Oregon, USA, 1981.
15. Knoef, H. A. M., Stassen, H. E. M., Hurstad, A. & Visser, R.,
Environmental aspect of condensates from down draft biomass gasifiers.
Paper presented at 4th EC Conference on biomass for energy and
industry, Orleans, France, 1987.
16. Detrie, J. P., La pollution atmospherique. Dunod, Paris, 1969.
17. Morris, G., Health effect of residential wood combustion. The implica-
tions of environmental stoichasticity. Paper presented at International
Conference on Residential Solid Fuels, Portland, Oregon, USA, 1981.
Gaseous Emissions from Carbonisation and Pyrolysis Processes 287
18. Hirao, K., Shinohara, V., Tsuda, H., Fukushima, S., Takamash, M. &
Ito, N., Cancer. Res., 36 (1976) 329-35.
19. Dong, M., Schmeltz, I., Lavoie, E. & Hoffman, D., Carcinogenesis. A
Comprehensive Survey, Vol. 3, Polynuclear Aromatic Hydrocarbons.
Raven Press, New York, 1978, pp. 97-108.
20. Lee, M. L., Novotny, M. W. & Bartle, K. D., Analytical Chemistry of
Polycyclic Aromatic Compounds. Academic Press, London, 1981, pp.
441-9.
21. Muhl Baier, J. L., A characterization of emissions from wood burning
fireplaces . Paper presented at International Conference on Residential
Solid Fuels, Portland, Oregon, USA, 1981.
22. Harpea, J. P. & Knight, L. V., Measurement of wood heater thermal and
emissions performance. Paper presented at International Conference on
Residential Solid Fuels, Portland, Oregon, USA, 1981, pp. 210-26.
23. Butcher, P. J. & Ellenbecker, M. J., Particulate emission factors for small
wood and coal stoves. Paper presented at International Conference on
Residential Solid Fuels, Portland, Oregon, USA, 1981, pp. 289-303.
24. Imhoff, R. E. & Manning, J. A., Preliminary report on a study of the
ambient impact of residential wood combustion in Peterville, Alabama.
Paper presented at International Conference on Residential Solid Fuels,
Portland, Oregon, USA, 1981, pp. 520-50.
25. Girard, P., Expertise de Materiel de Carbonisation. Rapport AFME-
CTFT, Dec. 1988.
26. Elliott, D. C., Analysis and Comparison of Biomass Pyrolysis/Gasification
Condensates. Final Report, June 1986, PNL-5943, Pacific Northwest
Laboratory, Richland, WA, USA.
12
Pilot Plant Requirements
MARTIN Rupp
VEBA OEL Entwicklungs GmbH, Uhlenbrockstrasse 10, D-4650
Gelsenkirchen, Federal Republic of Germany
ABSTRACT
Process development provides the essential link between laboratory
research and the eventual commerical exploitation of that research. A
key feature of this process development is the pilot plant in which
process concepts are proved and data are derived for design and
optimization of a demonstration plant or commercial plant. The
objectives and functions of pilot plants in process developments are
described with reference to biomass conversion processes.
1 PROCESS DEVELOPMENT FOR BIOENERGY SYSTEMS
For most of his history, man has used biomass as his primary energy
source. However, from the beginning of the industrial age, the
contribution of biomass to energy supplies has continuously decreased
and today biomass has more-or-Iess no importance within the energy
scenario of the industrialized world.
Two facts have led to a revival of the interest in biomass as an energy
source during the last few years: the so-called energy crises in the
1970s and the increasing environmental problems associated with the
use of fossil energy carriers, especially the CO
2
problem. In addition,
the serious accident at Chernobyl has generated enormous political
pressure against nuclear energy, so that it is doubtful whether nuclear
energy can fulfil its hopes as a clean and unlimited energy source. The
289
290 Martin Rupp
use of biomass cannot solve all the problems with respect to future
energy supplies, but it may provide a significant contribution. There-
fore the development of bioenergy systems seems to be essential.
Unfortunately the economic figures do not support this assessment.
The actual oil price of about US$18/bbl gives biomass no chance to
enter the energy market. Also, extrapolation of future oil price
scenarios does not improve the situation. The oil price necessary for
economic use of bioenergy systems is probably at least US$50/bbl.
Such an oil price is not seen in a time scale which usually motivates an
industrial company to invest in bioenergy systems.
On the other hand, the environmental costs have to be paid and the
idea of charging these costs to energy consumption directly has
become more and more attractive, and has found its first promoters
within the politicians of the industrialized countries. This gives
biomass a much better chance in the energy market of the near future.
Therefore development of bioenergy systems has to start now. The
typical time-frame for the development of a large-scale process such as
an energy conversion unit is 12-15 years. In the case of a bioenergy
system it might be even longer because it is not only the conversion
unit that has to be developed. The special problem of bioenergy
systems is to integrate the periodic production of biomass with the
continuous conversion unit which transforms biomass into an energy
carrier suitable for the market.
The only questions which remain are to which stage of development
reasonably you should go, and who has to pay for the development.
Answers to these questions can be found in classical process
development with particular attention to the special needs of bio-
energy systems.
2 STEPS IN CLASSICAL PROCESS DEVELOPMENT
Process ideas are either born in the laboratory or result from
laboratory work, and are focused on an eventual commercial plant or
system. The link between these two ends, the process development, is
called the scale-up procedure, because the process has to be realized at
different scales increasing step by step in terms of throughput and of
cost. Nowadays highly developed mathematical tools and high-
performance computers support this procedure but they cannot
substitute for the technical realization of the individual scale-up steps.
Pilot Plant Requirements 291
The number of steps within the scale-up procedure depends on the
complexity and the degree of innovation of the process under
consideration. Figure 1 shows different ways of transforming process
ideas from laboratory results to a commercial process.
Laboratory Commercial
plant
Laboratory --------) Pilot Commercial
plant plant
Laboratory Process ----+) Pilot Commercial
development plant plant
unit
Laboratory Process ----+) Pilot ----+ Demonstration Commercial
development plant plant plant
unit
FIG. 1.
The economically most attractive way is the direct commercializa-
tion of laboratory results, using physical-chemical models for scale-up.
This is only possible when the process is, in principle, already
commercialized and only improvements have to be carried out. A
typical example is the development of a new catalyst for an existing
process.
Normally the process ideas are realized first on an intermediate scale
in a so-called pilot plant. The aim of construction and operation of a
pilot plant is to minimize technical and economical risks in process
development.
In some cases an additional step is necessary before pilot plant
operation can be considered. This step is often called a process
development unit (POU). One common reason for this scale-up step is
that the process cannot be operated continuously in the laboratory
because of the lack of suitable equipment.
Beyond the pilot plant stage for very large process units or a new
process based on an unusual feedstock or processes producing new
products, a demonstration plant is erected. Such a demonstration plant
normally uses real industrial-sized equipment. It often represents a
single train of a multi-train commercial plant.
The size and the costs of the different scale-up steps depend on the
type and size of the process under consideration. Energy transforma-
292 Martin Rupp
Table 1
Main features of process development steps
Typical figures for size and duration of operation from development of oil
conversion or coal liquefaction units
Development step Through- Construct- Total Operating
put ion annual time
(kg/h) costs costs (years)
(DM) (DM/year)
Laboratory
10-
1
05 x 10
6
Process development 10 5 x 10
6
10
6
3
unit (PDU)
Pilot plant 10
3
5 x 10
7
10
7
6
Demonstration plant 10
4
10
8
(10
8
t 2
Commercial plant 10
5
10
9
a Only for the start-up phase; costs should rapidly reduce by selling products.
tion processes are normally of a very large scale. Typical figures
derived from process development of oil conversion or coal liquefac-
tion units are given in Table 1. It is clear that both the size of plant
and costs for the different scale-up steps increase rapidly. If all these
costs have to be charged to the commercial plant, they have a large
impact on the cash flow of the commercial operation.
Another important fact that can be extracted from Table 1 is that
the operation of the pilot plant has the heaviest burden in terms of
cost and time.
3 PILOT PLANT REQUIREMENTS
The erection and operation of a pilot plant is a very expensive step in
process development. Nevertheless, it is an essential step as, without
pilot plant results, engineering and design work for commercial
process cannot start and it is only on this basis that reliable economic
data can be generated.
From the technical point of view, the main objective of the pilot
plant step is to reduce the scale-up factor for critical components and
parameters. Among the most critical parameters in process develop-
ment are the hydrodynamic conditions in reactors, heat exchangers
and separators. The chemistry itself does not depend on the scale of
the process, but every chemical reaction is connected with heat and
Pilot Plant Requirements 293
mass transfer and these transportation steps are heavily influenced by
the hydrodynamic conditions within the corresponding equipment. In
laboratory investigations it is normally not possible to achieve simul-
taneously both adequate conditions for the chemical reaction and
technically reliable hydrodynamic conditions.
In a pyrolysis process, the typical phenomena influenced by hydro-
dynamics are dust formation, dust entrainment and sedimentation.
Dust formation and entrainment have a considerable impact on
product quality and plant availability. Entrained solids often lead to a
rapid blockage and subsequent shut-down of the whole plant. To study
these problems and to find reliable technical solutions is an important
task for pilot plant operation.
Another important task is the selection and testing of equipment
such as pumps, drivers and heat exchangers. If the equipment
suppliers can be included in the development work by using their
experience and special skills, this will improve the probability of
finding a solution to the problem.
The size of the pilot plant is also influenced by the hydrodynamic
conditions, which should be near the range of an industrial plant, and
also the equipment used should be of an industrial scale or at least it
should allow the supplier to extrapolate to the industrial scale.
Nowadays high standards for the safety and the environmental
impact of a plant are set by the government. The pilot plant allows
measurements of emissions and can demonstrate safety systems on a
reliable scale. Without such data it is nearly impossible to obtain an
authorization for commercial operation.
Another important task is the investigation of corrosion and erosion
problems and the selection of suitable materials of construction for the
equipment of the plant.
Last but not least, a pilot plant can supply relatively large amounts
of product for the investigation of subsequent processing or market
evaluation.
4 EXAMPLE FOR PROCESS DEVELOPMENT IN PILOT
PLANT STAGE: PYROLYSIS UNIT FOR HYDROGENATION
RESIDUES AND COAL PITCH
VEBA OEL has developed a pyrolysis unit for hydrogenation residues.
Based on earlier commercial experience from coal liquefaction units, it
was decided to choose a rotary kiln as the pyrolysis reactor.
294 Martin Rupp
Because the pyrolysis step was only part of a much larger complex-
the residual oil hydrogenation plant-the objective of the development
was to ensure a high availability of the pyrolysis unit. Similar units
operating on residues from coal liquefaction have had run times of
only a few months. The reason for this has to be seen in the feed
material which forms sticky deposits during the pyrolysis process which
have to be continuously removed. The mechanical stress caused by the
cleaning device limited the plant availability, causing high operating
costs and high investment costs due to the necessary equipment
redundancy. One of the goals of the development was thus the design
of a suitable cleaning device.
A second goal was to maximize oil yield to improve the overall
process economics. From laboratory results it was known that maxi-
mum oil yield was achieved in the region of 500C. Therefore, the
plant was designed for a maximum temperature of 600C.
To fulfil the requirements for environmental acceptability, it was
decided to operate the pyrolysis unit as a closed system with an
externally heated rotary kiln. Clean fuel gas was selected as the fuel.
The main steps of the development are listed in Table 2. The total
development time was six years, of which less than three years was
operating time of the pilot plant. The total cost of the development
was around DM50 million.
Three interesting results can be deduced from Table 2.
-Pilot plant development is a step-by-step procedure. Not all
problems can be seen at first glance. The solution of one problem
improves the plant performance, and this better performance or
longer operating times show the next bottleneck or problem.
-Conceptual changes have to be taken into account during the
development. In this case two conceptual changes were under-
taken. The flow of the recycle gas was changed from co-current
to countercurrent flow. This caused the vapours and solids to be
taken away at different ends of the rotary kiln, resulting in higher
qualities of coke and liquids. The major change was the increase
of operating temperature to 850C, resulting in lower liquid yields
but in a significant improvement in length of operating cycle.
Economic analysis at this point showed that plant availability has
greater importance than maximum liquid yield.
-The third point is the importance of the availability of the pilot
Pilot Plant Requirements
295
Table 2
Main steps in development of Veba Oel's pyrolysis unit
Development step Duration Major problems Major improvements
(months)
Engineering, 12
equipment
procurement
Construction 6
First operating phase 4 Feed pump, Training of operators
measuring devices,
cleaning device
First revamp 2 Cleaning device, feed
pump
Second operating 3 Let-down systems for
phase coke and vapours
Second revamp 6 Conceptual change:
countercurrent
recycle gas flow
Third operating phase 6 Let-down system for First reliable balances
vapours,
condensation
system, solids in
liquids
Third revamp 3 New design for vapour
let-down, two-stage
condensation of
vapours
Fourth operating 6 Let-down system for Run time more than
period coke, throughput 300 h with scheduled
too small shut-downs,
investigation of
process parameters
Fourth revamp 4 New kiln for higher
temperature (850C),
new let-down system
for coke
Fifth operating period 8 None Run time of 1000 h with
scheduled shut-down,
verification of
environmental
standards
Start of engineering 3 Final definition of plant
for commercial design
plant
Sixth operating period 6 Check of concepts and
ideas from
engineering of
commercial plant
Finalization of 3 Ready for
engineering commercialization
296
R""idue
Thermal __ __ "..., .....
Oil
fuel Gas
Air
Storege
Martin Rupp
RecyCIO Gas
2, Condenser
SlOP
1. Condens.r
Step
PyrolY:51!: Gas
Flue GA5
,
: Pyrolysis Cok.e
--------+
Pyrolvsis 0111
S2."nX\,',"'Cn .....
F-yrolysis
Drum
Pyrolysis Oil II
n4>
FIG. 2. Flow sheet and total view of VEBA DEL's pyrolysis unit.
Pilot Plant Requirements 297
plant during the engineering phase of the commercial plant. The
pilot plant allows an easy check of the final concept and ideas in
the design phase of the commercial plant.
The final concept of the Veba pyrolysis process is shown in Fig. 2,
together with a view of the pilot plant in its last stage. The process is
now commercialized for processing coal pitch.
5 SPECIAL REQUIREMENTS FOR BIOENERGY SYSTEMS
All the topics mentioned above with respect to pilot plant operation
are also valid for a bioenergy system, but there are additional
requirements.
At the front end of the conversion system, the feed supply is
unconventional. Biomass may only be harvested once per year, and
the amount of biomass is influenced by weather conditions for
example, and may show large fluctuations. On the other hand it is
essential for the most economic operation of the conversion unit that it
runs continuously throughout the year. To integrate these factors,
an effective and optimized storage and transportation system for the
feed material has to be developed. This requires a pilot system for
production, harvesting, storage and transportation, which would
provide technical solutions for any problems in these steps and also
provide a real feed material for the conversion pilot plant.
Therefore the construction and operation of a pilot plant only makes
sense within the framework of an integrated project which starts with
biomass production and ends with the conversion unit. Independent
implementation of a conversion pilot plant and a feed supply system
only provides locally optimized results and the data cannot be
extrapolated reliably.
If a pyrolysis unit is specified for the conversion of biomass, the
products cannot be marketed directly into the existing market, and
upgrading or transformation to marketable products has to be in-
vestigated. To obtain reliable results and convince possible consumers,
relatively large amounts of primary conversion products have to be
supplied. This places a further requirement on the operation of a pilot
plant.
The development of a fully integrated bioenergy system requires a
considerable investment. As mentioned above, the current and pro-
jected oil price for the near and medium future do not encourage
298
Martin Rupp
industrial companies to invest in such a development. On the other
hand, environmental problems and social pressures resulting from
agricultural overproduction require a new assessment of energy supply
that considers the social, environmental and other costs. New bound-
ary conditions have to be set up and the development of alternatives
such as bioenergy is a prerequisite of such political considerations.
13
Biomass Pyrolysis in Brazil: Status Report
CARLOS A. LUENGO & MARIO O. CENCIG
Applied Physics Department, University of Campinas (Unicamp), PO
Box 6165, 13081 Campinas, Sao Paulo, Brazil
ABSTRACT
Wood and sugar-cane usage in Brazil is outlined from the perspective of
the opportunities for conversion into liquid fuels using modern pyrolysis
techniques and conversion technologies.
Wood consumption in Brazil exceeded 130million tons in 1986, with
about 40% being converted to charcoal for steel production. Wood
carbonization is carried out in brick kilns, and major manufacturers
also have condensation units for tar recovery. Liquid by-products are
used as boiler fuels and also, after further processing, as a source of
chemicals such as methanol and acetic acid.
In 1986 also, cane consumption reached over 200 million tons for
production of ethanol and sugar. The by-products of these processes
include bagasse which is used for steam raising, to substitute for fuel oil
in agro-industry and as cattle feed after appropriate defibrelation
treatment. Sugar-cane bagasse may also be used as an interesting source
of fuels and chemicals, by ultrafast pyrolysis of biomass. A new project
has been established to exploit this technology.
1 WOOD AND SUGAR-CANE AS INDUSTRIAL
FEEDSTOCKS
It is the sun-belt countries which do not have fossil fuel resources or
hard currency to buy them, where processes for alternative fuels and
chemicals from biomass and wastes has potential. Currently in Brazil
299
300 Carlos A. Luengo & Mario O. Cencig
there are two main industrial biomass programmes: charcoal for
steel-making and ethanol for motor vehicles.
Each year, over 100 million tons of wood and 200 million tons of
sugar-cane are processed in Brazilian steel and fuel activities [1].
About 40% of the wood produced is converted to charcoal for steel
production. For example, steel making in Minas Gerais demands over
7 million tons of charcoal each year, 20% of which is obtained from
short-rotation eucalyptus plantations [2]. Wood and sugar-cane bag-
asses are also widely used for heat generation and steam for
agro-industry. Fixed-bed boilers are commercially available and sev-
eral R&D fluidized-bed burners are being developed [3,4]. Industrial
wood gasifiers of up to 3 MW are used in semi-rural areas, and over
100 have been installed throughout the country [5]. Charcoal gasifiers
for small-scale power generation are used in remote locations and also
to power motor vehicles [6]. A 10
6
-kcal unit was developed for an
industrial 275-kW electric generator [7]. However, the largest single
consumer of wood is the low-income sector population in rural areas.
An active, decentralized market has developed in which wood which
originates from both native forests and also from extensive reforesta-
tion projects is available at an average cost of US$15-25/ton [2].
The only transportation fuel produced from biomass is ethanol
derived from sugar-cane. In 1986, 11 x 10
6
m
3
were produced [1],
enough to power a fleet of about 4 million automobiles and light
machinery. An ethanol chemical industry is also being developed, for
example, in 1987 about 400 million litres of alcohol were consumed to
produce 11 different products, such as ethylene and ethyl acetate, by
an array of small but active industries. The ethanol programme also
generates by-products which are actively utilized. Sugar-cane bagasse
amounting to over 50 million tons per year is valued at about
US$20/ton and is used as a fuel-oil substitute for boilers and as
feedstock for a steam defibrelation process to produce cattle feed.
Widespread markets for both wood and sugar-cane bagasse provide
potential feedstocks for processing into chemicals and fuels via
pyrolysis techniques.
2 FUELS AND CHEMICALS IN RELATION TO BIO-COAL
UTILIZATION
2.1 Low-temperature pyrolysis of wood
Most of the R&D on charcoal properties and manufacturing in Minas
Gerais is centralized at CETEC. There, wood processing into charcoal
Biomass Pyrolysis in Brazil 301
and tar feedstocks for the steel industry is pursued both at laboratory
and demonstration scales. Acesita, Belgo-Mineira and Mannesmann
are the major Brazilian steel industries using charcoal for both iron ore
reduction and blast furnaces. The material is currently obtained by
carbonization of wood at temperatures around 400C in brick kilns of
standard design as shown in Fig. 1. These kilns are operated in groups
for optimum performance. Typically, a charcoal production unit
delivers about 6000 t/year [8] and also includes tar recovery equipment
which yields 720 t/year of condensates. This product is used as a
fuel-oil substitute at the steel plants. More recently, research at
Acesita Energetica [9] has produced a prototype retort with a monthly
capacity of about 450 t of charcoal, 120 t of tar and 23 t of methanol
per month. A process flowsheet is shown in Fig. 2.
2.2 R&D on pyrolysis products
The eight steel industries produce and consume 10 million tons of coke
from coal and over 7 million tons of charcoal from biomass each year.
The coking ovens produce a significant quantity of chemicals. In 1987,
for example, 20 products were derived from 317000tons of tar,
including ammonia, BTX, pitch, creosote, anthracene and naph-
thalene. Pitch production reached 97000 tons in 1987, most of it used
for electrode manufacturing. Chemicals from coal, however, are
dependent on fluctuations in the much larger petrochemicals market
[10]. The possibility of developing a complementary carbochemistry
industry from the liquid products of low-temperature wood pyrolysis is
being pursued by Acesita Energetica [9]. Results from research at the
pilot stage were used for studying the technical and economic
feasibility of processing pyroligneous liquor into chemicals such as fuel
oils, solvents and phenols. Figure 3 shows the production scheme
which is currently under development.
Charcoal fines are conventionally recycled into blast furnaces at
major plants, although other possibilities are being pursued by the oil
company Petrobnis. For example, charcoal-oil slurry production and
briquetting on 1 t/h demonstration plants have been carried out at
distilleries in Paulinia (1983) and Manaus (1988) respectively [11].
Both developments have been halted due to internal policies.
A number of other activites are being pursued to recover valuable
materials from biomass. Forestry residues are being considered as a
carbon source by the steel company Vale do Rio Doce.
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Biomass Pyrolysis in Brazil 305
Baba\u, a coconut plant exploited for vegetable oils in the north-
east states of Piaui and Maranhao, is being actively studied since the
nut shell, which has high lignin content of about 39%, is wasted.
CETEC has developed a carbonization unit, and carried out
characterization studies of baba\u wood and coconut with a view to
utilization in blast furnaces [12].
The IPT (Instituto de Pesquisas Tecnol6gicas, Sao Paulo) has
designed and commissioned a continuous carbonization unit with an
output of 03 t/hour of carbonized baba\u shells [de Nucci, 0., IPT,
priv. comm.].
Charcoal- and bagasse-derived carbon materials are being studied at
LCA (Lab. Combustlveis Alternativos) from both basic and applied
viewpoints, including a study of structures utilizing small- and large-
angle X-ray scattering techniques [13]. A microscopic model for
biomass carbons has been proposed [14].
At the research center of Sao Jose dos Campos, graphitic materials
from lignins are synthesized both for aerospace structures [15] and
medical applications. Also, coke was obtained from Eucalyptus lignin,
by briquetting and pyrolysis [16].
The possibility of finding better binding materials, by upgrading
pitch obtained from bagasse or wood, is being investigated in the
context of the development of electrode materials [17].
3 HIGH-VALUE CHEMICALS AND/OR FUELS FROM
SUGAR-CANE BAGASSE
Fast pyrolysis, as a viable route for energy and chemical products, has
been pursued for the last few years on a variety of feedstocks. Initially,
a coal flash hydropyrolysis (FHP) bench unit, shown in Fig. 4, was
built following the early work of Steinberg & Fallon [18]. Results
showed that FHP is a viable alternative for processing low-grade
Brazilian coals [19,20]. After the recent work by Diebold at SERI [21]
using the vortex reactor, Consorzio Alten in Italy [KTI, Via Monte
Carmelo, 5, 00166 Rome] and others [22] suggested that pyrolysis
techniques seem both technically and economically promising for
production of liquids. From these studies the project Oldibio was
conceived with the sponsorship of Finep and Copersucar, with the
objective of developing flash pyrolysis processes for biomass and
wastes.
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Biomass Pyrolysis in Brazil 307
The possibility of selectively obtaining high-value products from
wood or sugar-cane bagasse is attractive in Brazil because both have
established markets throughout the country. It is intended to use
ultra-flash pyrolysis techniques to obtain primary vapours which will
be treated on-line with appropriate catalysts to yield fuels [23] and/or
chemicals [24]. Research was focused initially on obtaining particulate
materials from both feedstocks (wood and bagasse) to establish
grinding and drying procedures in the laboratory. The second step was
bench-scale experiments at the FHP unit described earlier. Several
runs demonstrated the feasibility of the concept and liquid and gas
fractions were obtained and characterized. However, systematic
blocking of the equipment due to coke formation in the high-
temperature reaction zone prevented much progress. A new bench-
scale reactor needs to be designed to remove primary vapours before
free-radical recombination proceeds. In addition, vacuum distillation
of wood and bagasse tar is being pursued to identify valuable products.
4 CONCLUSIONS
The biomass programmes in Brazil need new R&D initiatives. Fuels
and/ or chemicals from upgrading techniques applied to low-
temperature pyrolysis tars available from current charcoat production
may be a viable alternative which will continue to be studied by
Acesita Energetica. Cooperative research with European Community
sponsored laboratories is being initiated to help develop suitable
technologies to exploit biomass feedstocks for production of chemicals
and/or fuels.
REFERENCES
1. Anon., Baianfo Energetico Nacional. Ministerio das Minas e Energia,
Brasilia, 1987.
2. Resende Penedo, W., Madeira e carviio vegetal. In Economia e Tec-
nologia da Energia, ed. M. Zero. Finep, Rio de Janeiro, 1985, pp.
274-301.
3. Nacif Mitre, M., Caldeiras para a queima de madeira e In
ProdUfiio e Utilizafiio de Carviio Vegetal. SPT-OD8, Cetec, Belo Horizonte,
1982, pp. 319-47.
308 Carlos A. Luengo & Mario O. Cencig
4. Greco, C., Combustao e gaseifical;ao em leito fluidizado. In Gaseificafiio
da Madeira e Caroiio Vegetal. SPT-004, Cetec, Belo Horizonte, 1981, pp.
53-72.
5. Makray, Z., Gaseifical;ao em leito fixo para industriais. Paper
presented at Seminario Brasil-Europa de Energia de Biomassas e
Residuos, Belo Horizonte, 1988.
6. Siquieroli, W., Uso de gasogenio em motores do cicIo Otto. In Produfiio
e Utilizafiio de Caroiio Vegetal. SPT-008, Cetec, Belo Horizonte, 1982,
pp.379-85.
7. Jardim de Moraes, P. L., Gaseifical;ao para produo de energia eletrica.
Paper presented at Seminano Brasil-Europa de Energia de Biomassas e
Residuos, Belo Horizonte, 1988.
8. Antunes de Rezende, M. E. et al., Desenvolvimento da tecnologia de
fabrical;ao do carvao vegetal. In Anais IV Congresso Brasileiro de
Energia, Rio de Janeiro, 1987, pp. 49-59.
9. Carazza, F. et aI., Carboquimica vegetal: aproveitamento do licor
pirolenhoso. In Anais IV, Congresso Brasileiro de Energia, Rio de
Janeiro, 1987, pp. 6O-7l.
10. Cencig, M. 0., Doctoral thesis, Institute of Chemistry, Unicamp, 1989.
11. Moro, J. P., Briquetagem de finos de carvao vegetal. Paper presented at
2as. Jornadas de Engenharia dos Paises de Lingua Oficial Portuguesa,
Rio de Janeiro, 1987.
12. De Oliveria, J. B., Gomes, P. A. & Mendes, M. G., Otimizal;ao do
processo de carbonizao da madeira e do coco babaI;U em fornos de
alvenaria. In Caroiio Vegetal, SPT-006, Cetec, Belo Horizonte, 1982, pp.
103-30.
13. Hernandez, J., Calderon, I. H., Luengo, C. A. & Tsu, R., Microscopic
structure and electrical transport properties of heat treated coals and
Eucalyptus charcoal. Carbon, 20 (1982) 20l.
14. Emmerich, F. G., Souza, J. C., Torriani, I. & Luengo, C. A., Applica-
tions of a granular model and percolation theory to the electrical
resistivity of heat treated endocarp of babassu nut. Carbon 25(3) (1987)
417-24.
15. Polidoro, H. A., et al. Obten,<ao de grafites sinteticos a partir de
materias-primas nacionais. Ceramica, 32(199) (1986) 181-4.
16. do Nascimento, E. A. & Schuchardt, U. F., Obten,<ao de coque
metalurgico a partir de lignina hidrolitica de Eucalipto. In Anais IV
Congresso Brasileiro de Energia, Rio de Janeiro, 1987, pp. 41-8.
17. Reis Coutinho, A., Doctoral thesis, Institute of Physics, Unicamp (in
progress).
18. Steinberg, M. & Fallon, P. T., Flash hydropyrolysis of coal. Paper
presented at 173rd National Meeting of the American Chemical Society,
20-25 March, 1977.
19. Cencig, M. 0., Ciampi, G. J. S. & Luengo, C. A., Flash hydropyrolysis of
a high ash Brazilian coal. In Rolduc Symposia Coal Characterisation for
Conversion Processes 1986, ed. J. A. Moulijn & F. Kapteijn. Elsevier,
Amsterdam, 1986, pp. 83-9.
Biomass Pyrolysis in Brazil 309
20. Cencig, M. 0., Ciampi, G. J. S. & Luengo, C. A., Aplicaes da
hidropir6lise nipida a conversao de carv6es e biomassas. In Anais IV
Congresso Brasileiro de Energia, Rio de Janeiro. 1987, pp. 29-40.
21. Diebold, J. P., Report SERI/TR-332-586, June 1980.
22. Bridgwater, A. V. & Kuester, J. L. (eds), Research in Thermochemical
Biomass Conversion. Elsevier Applied Science, London, 1989.
23. Diebold, J. P. & Scahill, J. W., Conversion of wood to aromatic gasoline
with zeolite catalysts. In SERf Report, 1987 Annual AfChE Meeting, 29
March-2 April. Houston, Texas.
24. Diebold, J. P. & Power, A., In Research in Thermochemical Biomass
Conversion. Elsevier Applied Science, London, 1989.
14
Overview of Thermochemical Conversion of
Biomass in Canada
the late R. D. HAYEs*
Bioenergy Research and Development, Technology Branch, Energy,
Mines and Resources Canada, Ottawa, Canada KlA OE4
ABSTRACT
Thermochemical conversion of biomass in Canada has undergone a
considerable transformation in approach and expectations over the last
ten years. A decade ago, the promise of early commercialization quickly
evaporated and was replaced by a more realistic assessment that the
potential would likely not materialize except over the longer term. More
recently this outlook has been modified slightly in the wake of
unanticipated research progress and the surfacing of some special
near-term market applications.
1 INTRODUCTION AND HISTORY
During the late 1970s and early 1980s there was a short-lived
perception of panic in energy security accompanied by exaggerated
claims of technical readiness of thermochemical conversion applica-
tions. Several premature commercial demonstrations in the USA of
pyrolysis and gasification failed technically and financially. Govern-
ments and investors therefore became understandably cautious when
further approached by technology vendors. American communities
that once considered gasification and pyrolysis of municipal solid
wastes as environmentally attractive alternatives to relieve pressure on
* Sadly, Doug Hayes passed away during the preparation of this book. He will
be greatly missed by both colleagues and friends.
311
312 R. D. Hayes
decreased availability of landfill sites for urban refuse, turned their
attention to mass incineration and refuse-derived fuel (RDF) combus-
tion applications. Though environmentally less attractive in terms of
emissions, combustion offered less technical and financial risk than did
the more exotic thermochemical conversion options.
Canada was somewhat behind the USA, having felt less apparent
impact from the energy supply disruptions of 1973 and 1979. In those
days also there was less pressure to find alternatives to landfilling of
wastes than there was in many US cities, or as there is in some
Canadian cities today. Canadian thermochemical conversion research,
then in its infancy, therefore focused its effort on the long term. It
assumed a lengthy timeframe to mature innovative process develop-
ments. In theory, this new breed of technologies would presumably
become technically ready for the 1990s or 21st century, in a world
eager to embrace bioenergy, particularly from wood, as a sustainable
and environmentally attractive energy resource.
The ultimate vision of some researchers was to refine biomass in a
manner analogous to petroleum that would eventually lead to altern-
ative transportation fuels, preferably high-quality gasoline, plus a host
of high-value by-product speciality chemicals. As the bubble burst on
high world oil prices, the sense of urgency to accelerate R&D
diminished. Admittedly, severe federal budget reductions for energy
R&D also had their predictable effect on the 'sense of urgency'.
Except for one major project, gasification research in Canada all but
disappeared by 1984. The pyrolysis/liquefaction research community
collectively agreed to back off from upgrading studies, and concen-
trated instead on perfecting their processes for primary oil production.
Over the past decade, the science has become better understood and
technical advances have actually surpassed earlier expectations. Some
laboratories have begun to re-activate their upgrading research.
Scientists and engineers have broadened the scope of experimental
conditions and gained a much deeper understanding of the chemical
transformations of complex feedstocks to multiple products.
A new vision of conversion and product opportunities has begun to
reshape our view of the timeframe for commercialization. The
long-term perspective remains paramount, and perhaps even more so
since the global call for environmentally sustainable economic de-
velopment by the Brundtland Commission report, Our Common
Future [1].
In addition to the long-term vision, technical progress in the
Thermochemical Conversion of Biomass in Canada 313
identificatiPn of several highly valued speciality chemicals in wood
pyrolysis oil may be the market hook (albeit a small market) required
to help finance the high costs of staged scale-up from laboratory, to
process development unit, pilot plant, small commercial demonstra-
tion and eventually to full-scale commercial reality.
Several other near-term opportunities have also surfaced. Environ-
mental pressures have influenced the trial experimentation of biomass
pyrolysis liquefaction technologies on non-woody feedstocks such as
used tires, petroleum sludges, sewage sludge, and, once again,
municipal solid wastes. Impending environmental regulatory controls
on waste incineration and increasing costs for landfilling may create a
climate more ideal for fully contained emission-free thermochemical
processes.
Researchers, industry and government have all become more
creative in building a diversified, yet comprehensive, portfolio of
thermochemical conversion opportunities for the commercial world.
Though nothing thoroughly new has emerged, the past ten years have
seen an evolution from a subject of technical curiosity to one of
concerted effort toward cost-effective products for the marketplace,
some sooner than others.
2 PROSPECfIVE APPLICATIONS OF TECHNOLOGY (PAT)
A broader diversified portfolio, as referred to above, presents a major
challenge to the R&D planner. Added to this challenge is the
ever-present restraints in government R&D funding. This challenge
has necessitated a major overhaul in organizing R&D priorities in the
context of assessing a balance in both near- and long-term commer-
cialization and environmental opportunities and needs:
The commercialization process for a new technology as defined
within the Energy Diversity Division of Energy, Mines and Resources,
Canada, includes everything germane including opportunity identifica-
tion, the actual research, development, technical evaluation and
demonstration as well as the determination of current and projected
economic feasibilities, current and future market, expected timeframes
for commercialization, standards development, and many other factors
affecting market introduction and penetration. Once these elements
have been assessed and analyzed for the various feedstock/conversion
technology pathways, priorities could be established with respect to
314 R. D. Hayes
activities that government can, should, or must, carry out and those
that government should not, or cannot afford, to support.
The first step in the process is to organize the four basic elements of
a technology by resource (e.g. biomass, wastes, peat, etc.),
process(es), product(s), and market application. The particular feed-
stock combined with specific conversion processes and a particular
market application of products results in what we define as a
Prospective Application of Technology, or PAT. The picture can
become rather complex, especially when considering combinations of
thermochemical, biochemical and fractionation technologies that
might be otherwise overlooked during conventional analysis. In order
to illustrate many of the various combinations pictorially, we have
constructed a 'PAT map'.
Figure 1 is a simplified version of a 'PAT map' for thermochemical
technologies. One can visualize perhaps 100 or more probable
combinations of resources, processes, products, and market applica-
tions. The product possibilities alone include a vast array of oils, gases,
chars, carbon black, sugars, fermentation products, high-value spe-
ciality chemicals, medium-value commodity chemicals, olefins, gasoline
Thennoc:hen*: ..
Proc_
pyrolyois
h r<1fCXTeaDng
c_ytx:
soIlI8r7t pressurized
partial oDdation
",ygen gasific'-ion
soIvolysr;
hydTothermolys<s
proruct sepanbJn
etc.
Biomass.
peat &
wastes
Various combinations 01 lhermochemk:",
bk>chemical, extrac:tlonllractlcnatlon and
derlvatlzatlon
FIG. 1. Prospective Application of Technology (PAT) for thermochemical
technologies.
Thermochemical Conversion of Biomass in Canada 315
THERMOCHEMICAL
COMBUSTION
CA$lFICA liON
PYROLYSIS
CATALYSIS
HVDROTHERMOl't'SIS
SOL VOL lSIS. ETC,
VARIOUS COMIINATIONS OF BIOCHEMICAL
THERMOCHEMICAL, FRACTIONATION. EXTRACTION
AND DERIVATIlATION PROCESSES
FUel OIL;CA$ CM. ACETIC ACID RESINS FIBERS SUGAR ENZYMES
OLEFINS BTl METHANE CARBON BLACK GASOLINE ADDITIVES OlIGOMEAS
FURFURAL DIESEL FUEL SYNTHESIS GAS HEAT ALCOHOLS ADHESIVES/BINDERS
PHENOLIC DERIVATIVES CHARCOAL GASOLINE FLAVOURS/AROM .. S LOW MOL WT. LlGNINS
MANY FERMENTATION PRODUCTS ETC.
FIG. 2. PAT for bioenergy technologies.
and gasoline components, diesel fuel, and other materials. Figure 2 is
a more general PAT map encompassing most bioenergy technologies.
Our view of the world of thermochemical conversion of biomass is
no longer limited merely to the pyrolysis or gasification of wood to
heating oil and gas. Thermochemical conversion is not treated in
isolation from biochemical, fractionation or derivatization processes.
Even considering a single process technology, the variation in process
conditions, catalysts, reactants, or feedstocks can impact the range and
output of possible product combinations.
The second step will be to select a handful of promising PATs, and
perform an analysis of expected technical progress, economic feas-
ibility, market penetration, and timeframe for commercialization. In
theory, this should provide government (and industry) with a rationale
for desirable government (and industry) activities in those PATs such
as research, development, demonstration, detailed engineering,
market studies, economic and financial analysis, information dissemina-
tion, standards formulation, etc.
Some of the so-called 'thermochemical PATs' that are not typically
316 R. D. Hayes
represented at Thermochemical Conversion of Biomass conferences,
but which are included or planned for in Energy, Mines and
Resources' Bioenergy R&D program planning, include the following:
-thermochemical treatment of plant oils (oilseed, tall oil) to
produce high-cetane diesel fuel;
-biochemically and thermochemically derived lignin that is ther-
mally or thermochemically treated with or without catalysts to
produce gasoline and other chemicals;
-product derivation of thermochemical and biochemical lignins
(e.g. resins, adhesives, cement dispersants);
-thermochemical treatment of the steam-fractionated cellulose
component of biomass;
steam (thermal) production of adhesives with a fibre
by-product suitable for molding, pelletizing, or thermochemical or
biochemical processing;
-calcium magnesium acetate (CMA) production as a road de-icer
from aqueous effluents (i.e. dilute acetic acid) from pyrolysis and
biochemical processes;
-investigation of wheat chaff as a thermo- or bio-chemical conver-
sion feedstock;
-methanation of pyrolysis aqueous effluents;
-separation of short and long fibers of hardwoods where pulp
would be processed from the long fibers and fuels processed
biochemically or thermochemically from the lower-value short
fibers;
-source-separated and/or prescreened, or raw, municipal wastes
that undergo thermochemical or biochemical conversion with or
without pretreatment/fractionation.
3 EMR's BIOENERGY DEVELOPMENT PROGRAM
Figure 3 shows the historical trend in Canadian federal government
spending on bioenergy R&D including biomass production and
conversion. Figure 4 is a breakdown of thermochemical R&D expen-
ditures relative to other conversion technology areas.
Thermochemical Conversion of Biomass in Canada 317
Sl MILlI ONS

82 83 84 85 86 87 88 89 90
FIG. 3. Federal bioenergy R&D funding.
3.1 Brief review of non-thermochemical R&D
The following is a cursory view of Canadian R&D activities in
technical areas other than thermochemical.
The combustion area's main focus of effort is the evaluation and
improvement of industrial and residential combustor performance and
emissions. Also included has been support to Environment Canada's
National Incinerator Test and Evaluation Program (NITEP) and the
development of standards for performance, safety and emissions of
residential wood-burning appliances.
The biomass handling/preparation area includes research in biomass
materials handling, storage, drying, beneficiation, and preparation.
This research is seen to provide necessary infrastructural support for
all biomass conversion processes, but more importantly, to improve
biomass fuel quality with objectives to improve biomass combustion
performance and to reduce emissions. Examples of developments
include a bin, silo and non-consolidating feeder system that regulates
the controlled and non-disrupted feeding of hog fuel and chips to
burners, a device to exclude frozen lumps of hog fuel and chips to
burners, a continuous moisture sensor to provide improved combus-
318
<II
C

3.0
2.5
2.0
1.5
1.0
0.5
0.0
R. D. Hayes
Total $5,955,000
Combustion Biomass
Handling!
Preparation
Thermo-
chemical
35.4%
Bio-
chemical
FIG. 4. 1988/1989 bioenergy R&D expenditure forecast.
Infor-
mation
Tech!
Transfer
tion control of biomass of varying water content, and a low-energy
grinder to powder wood suitable for suspension-fired boilers.
The biochemical area receives the largest allocation of funds, in part
due to increasing industrial leverage provided by cost-shared R&D.
Much of the impetus for this area comes from mid-term (1990s)
competitive potential to enter the transportation fuel market with
biomass-derived ethanol-based blends and oxygenates and the longer-
term potential of neat ethanol fuel along with value-added by-
products. The program is divided into a number of areas including
enzymic and acid hydrolysis of lignocellulosics, steam and extrusion pre-
treatment and biomass fractionation, novel fermentation engineering,
biotechnology of enzymes and microorganisms, anaerobic digestion,
characterization and derivatization of lignin, and the development of
non-ethanol by-product streams, among others. The rate of achieve-
Thermochemical Conversion of Biomass in Canada 319
ments in this area over the past four years rivals that in the
thermochemical area. The lure and promise of biotechnology and the
recent accelerated progress are likely the major factors in attracting
industrial participation in an area that was viewed by our program as
very long-term only five or six years ago.
3.2 Canada's mainstream biomass thermochemical conversion R&D
An approach has evolved in Canada whereby, unlike earlier efforts, a
whole range of products and reactants are now considered. Products
include gases and oils of varying quality, sugar solutions in high yield,
chemicals (olefins, phenolics, as well as high-value specialty chemi-
cals), gasoline or diesel fuel, and higher-value carbon products.
Diversification of reactants include whole biomass, fractionated bio-
mass components, peat, and municipal solid waste, including source-
separated wastes such as used tires. Another area of research is the
treatment, and especially the conversion, of waste aqueous effluents
from thermochemical conversions into value-added co-products. Left
unprocessed, these effluents would otherwise incur a cost for waste
treatment.
3.2.1 Gasification
Canadian developments in biomass gasification for the production of
low-, medium- and high-energy gases have enjoyed world technical
acclaim over the past decade, but there has been a disappointing
uptake by Canadian industry. The cautious attitude of our industry
appears to have been due largely to premature and unsuccessful
attempts in the USA to commercialize immature technologies during
the latter 70s and early 80s. A possible revival of interest in
gasification technology applications appears to be for replacing in-
dustrial boilers that use oil and for municipal energy from waste
projects. The work to complete ongoing projects will continue,
although at a reduced level, and any impetus for an expanded
government program will likely wait for stronger industry confidence,
interest, and cost share. Application of Canadian technology in
developing countries may hold some promise.
Large-scale (10 t/h) gasification technology, developed through the
Biosyn project, offers a world-leading technology in pressurized, air-
or oxygen-fed, fluidized-bed gasification that can be adapted to the
production of synthesis gas for methanol production or low-energy gas
320 R. D. Hayes
for other applications such as space heating, gas turbines or industrial
diesel engine operation.
Another portion of the gasification research funds is directed to the
development of a small-scale gasifier that is designed to use wet wood
and produce a clean gas. The Heuristic gasifier is a two-stage reactor
that, in principle, operates similarly to a downdraft design. The first
stage is an updraft gasifier where producer gas and condensable vapors
(tars) are routed through a hot char bed below. The tars are to be
cracked in the second stage. The project now underway is to modify
the gasifier, optimize the operating parameters, and enhance cracking
in the second stage.
3.2.2 Liquefaction/pyrolysis
In 1985, research in the direct liquefaction of biomass was expected to
wind down because the rapid commercialization that was expected to
occur in the early 1980s did not materialize. The plan was to conclude as
much of the work as possible, revert to lower-cost basic research, and
pursue a strategy of chemicals from liquefaction. Then in 1986 there
appeared to be a turnaround in commercial interest. Unprecedented
technical achievements started to renew aspirations and industry
interest in exploiting selected market niches for pyrolysis products.
The following is a brief review of current projects. t
McGill University. Over the past several years researchers W. J. M.
Douglas and D. G. Cooper at McGill University have been studying
an interesting thermochemical approach to wood liquefaction using
aqueous hydrogen iodide at fairly mild conditions of pressure and
temperature (125C). Still far from certain is the exact nature of the
liquid products and the techno-economic practicality of hydrogen
iodide recovery and recycle. On the positive side, in addition to the
low-severity conditions of reaction, the process removes about 80% of
the oxygen in the wood, and the char yield is low.
University of Toronto. D. G. B. Boocock and co-workers at the
University of Toronto have undertaken the investigation of steam
pyrolysis or hydrothermolysis of wood. Based on their earlier work,
they recently designed and constructed a laboratory-scale cascade
t Most of the work referred to below in described and referenced in Chapter
2.
Thermochemical Conversion of Biomass in Canada 321
autoclave which can accommodate up to 100 g of woodchips or 170 g
of a single larger piece (38 cm reactor i.d., 600 ml volume). It is rated
at 241 MPa (3500psi) at 350C allowing for 76MPa (llOOpsi) gas
overpressure above the vapour pressure of water at that temperature.
Replicated results indicate that oil yield increases with increased chip
size. Dry-product oil yields are high (up to 50%) with no solids
contamination, and the oil is easily separable from the aqueous phase.
Coupled with an upgrading process, this technology may someday lend
itself well to commercialization.
In addition to their process development work, Professor Boocock's
group has contributed greatly to the basic understanding of biomass
liquefaction, especially through their scanning electron microscopic
studies. The group at the University of Toronto is also performing
upgrading studies through the catalytic hydrotreatment of model
compounds. Of potential interest too is their discovery in 1984 that a
particular clone of hybrid poplar yielded 6% phenol. This discovery
raises the prospect of matching processes more closely with specific
feedstocks in the interest of optimizing a particular product slate.
Efforts are now beginning genetically to engineer trees that are
designed for specific process/product applications.
Universite de Sherbrooke. E. Chornet, R. P. Overend and co-
workers at the Universite de Sherbrooke have been working on a
liquefaction process in pressurized solvent for some years. Their
approach involves an overall integration of biomass pretreatment,
fractionation, acid processing, and thermochemical and biochemical
treatment.
Funding for research at Sherbrooke in the areas of peat and wood
conversion is provided by a number of sources, including Energy,
Mines and Resources. The program there involves a comprehensive
variety of fundamental studies, product engineering and technology
development at laboratory and pilot plant levels. Examples of ap-
proaches under investigation include a thermomechanical-chemical
treatment to fractionate and liquefy biomass including steam treat-
ment, thermocatalytic conversion of fractionated products such as
lignin to monomers, ethylene glycol solvolysis/liquefaction,
acid/thermal/shear treatment of biomass and cellulose, and a variety
of biochemical investigations in combination with thermochemical
techniques. In association with other laboratories, the chemical
engineering laboratory of Professor Chornet is especially well
322 R. D. Hayes
equipped for analytical characterization of products derived from their
varous reaction systems.
University of Waterloo. D. S. Scott, J. Piskorz, D. Radlein and
co-workers at the University of Waterloo are well known for their
fluidized-bed flash pyrolysis development, also known as the WFPP
(Waterloo Fast Pyrolysis Process). A number of companies and the
European Economic Community have indicated their interest in
collaborating with the Waterloo group. The WFPP actually includes
five process options as follows:
(1) Direct thermal processing at 450-550C, atmospheric pressure,
and about 500 ms vapour residence time. They report high liquid
yield (80% including water, based on input wood) that is a
suitable fuel for conventional boilers.
(2) By varying the process conditions and adopting a mild sulfuric
acid pretreatment of wood followed by fluidized bed thermo-
pyrolysis, the WFPP produces a high yield and concentration of
anhydro-sugars rather than oil products. Their reproducible
yields of sugars from pure cellulose are about 80% of theoretical
in a concentrated form. One can easily speculate whether this
development could challenge some of the equally exciting
biochemical conversion methods of converting lignocellulosics to
fermentable sugars.
(3) Waterloo's hydrogasification work has been technically highly
successful, resulting in 75% conversion of wood carbon to
methane via pyrolysis over a nickel-alumina catalyst with
hydrogen at about 550C and 440 ms vapour residence time.
(4) Under current investigation is a fourth process option of
producing polyolefins from wood in a catalyzed reaction. Apart
from the use of catalysts, the process equipment and operating
conditions are very similar for all of the above process options.
(5) The Waterloo group is also performing upgrading research by
catalytically hydrotreating pyrolysis oil fractions, especially lig-
nin, in a continuous pressurized reactor.
University of Western Ontario. Although not currently funded by
Energy, Mines and Resources, M. Bergougnou, R. Graham and
co-workers have developed an ultra-rapid pyrolysis or ultrapyrolysis
process at the University of Western Ontario. Although there are
Thermochemical Conversion of Biomass in Canada 323
similarities in this work and the research at the University of
Waterloo, there are important differences. Whereas the Waterloo
process utilizes fluidized-bed heat transfer, Professor Bergougnou
employees a very rapid (30 ms) mixing and heat transfer in a vortical
contactor or vortactor followed by a plug-flow entrained-bed downflow
reactor (50-900 ms) and quenching (30 ms) with cryogenic nitrogen in
a cryovortactor. Dissimilar to the Waterloo process are the process
conditions (650-1000C, 50-900 ms residence time), and the main
product at these temperatures is gas rather than liquid. Since pyrolytic
fuel gas production has not been of high priority in Canada's
bioenergy R&D strategy, the current objective, in collaboration with
Ensyn Engineering (see below), is the production of chemicals and, in
particular, olefins.
It is interesting to note here that the Universities of Waterloo and
Western Ontario conducted an extensive data comparison from each
of their reactor systems. Using selected data from both groups at
around 500 ms residence time, liquid and gas production data were
plotted versus temperature. The temperature ranges were as follows:
Waterloo at 400-750C, and Western Ontario at 650-900C. With
combined data for each of the gas yield versus temperature, and liquid
yield versus temperature, respectively, there was remarkable agree-
ment of data in overlapping regions. A simple first-order kinetic model
is able to describe the oil yield over the temperature range of both
experiments.
Ensyn Engineering. Ensyn Engineering is a recently formed com-
pany whose principal investigator, R. Graham, has scaled-up the
University of Western Ontario ultrapyrolysis reactor by a factor of 20
to a 5-10 kg/h capacity RTP (Rapid Thermal Processor). The reactor
is designed to accept any carbonaceous feed (solid, liquid, or gas) by
injecting it into a turbulent cloud of hot solids. The mixed feed plus
solids is carried through a tubular transport reactor to an inertial
separator where vapour products are removed. This project is co-
sponsored by the private sector.
Work planned for the next few years involves thermal cracking and
catalytic treatment of pyrolysis oils and various lignin preparations
including steam-exploded biomass-derived lignin.
Laval University. Multi-stage vacuum pyrolysis was developed by
C. Roy and co-workers, initially at the Universite de Sherbrooke and,
324 R. D. Hayes
currently, at the Universite Laval. The technology consists of a
40 kg/h multiple-hearth vacuum pyrolysis process development unit
located near the Universite Laval. There is also an industrial cost-
shared pilot demonstration of a single-stage process at St Amable,
Quebec. The unit has a capacity of 200 kg/h and is designed for used
tires.
Although the multiple-hearth concept suffers from low heat transfer
relative to other pyrolysis processes and, at first glance, is capital-cost
intensive, it has a number of redeeming features that show commercial
promise as follows:
(1) A high yield of pyrolysis oil (50% based on wood).
(2) The production of co-product carboxylic acids and high-value
chemicals.
(3) Reactive charcoal at 25% of input wood.
(4) The aqueous phase is recovered separately as vapour or liquid
as an integral part of the process leaving a low-water-content of
water-free pyrolysis oil ready for upgrading.
(5) The multiple-hearth performs a product fractionation function
that could reduce extraction costs of high-value chemicals.
Centralized analysis. One final work of interest in Canada is a
Centralized Analysis project at BC Research. In 1984, a trial project
was set up whereby different Canadian bio-oils could be compared in a
standard manner. The project embraced a three-pronged approach.
Under the guidance of J. Howard and J. McKinley, BC Research
performed and/or coordinated the centralized analyses of optimized
oils produced by each researcher. Individual researchers also did some
of their own analyses to obtain immediate experimental feedback.
The second prong of the approach was that all researchers were
provided with a standard wood sample, Populus deltoides, by Forintek
Canada Corp. The idea was that when each process development
became almost optimized, the researcher would submit oil from the
standard wood sample to the centralized analysis team.
The third prong was a computer communications network link
called CoSy, through the University of Guelph, to provide fast
communication of analytical data. It was also used to encourage
multilateral and bilateral collaboration and problem-solving.
The centralized analysis project has entered Phase II. Learning from
Thermochemical Conversion of Biomass in Canada 325
the successes and pitfalls of the first 2! years, the scope of this project
has changed somewhat. Phase II has two major tasks.
Task 1 is a set of analytical techniques along the same lines as the
initial project except the methods that were considered to be less
interesting to the entire group are not included. The basic analyses of
task 1 include the following:
-Elemental analysis.
-Water content.
-Density.
-Carboxylic acids.
-Gas-liquid chromatography.
-Carbon-13 NMR.
-Gel permeation chromatography.
Task 2 consists largely of special analytical projects to meet the
special needs of individual researchers, the Energy, Mines and
Resources Bioenergy Development Program or groups of thermo-
chemical conversion researchers, that may arise over the next two
years.
4 INTERNATIONAL VIEW-IEA
Under the International Energy Agency, 11 countries signed a
three-year Bioenergy Agreement on Cooperative R&D, effective 1
January 1986 to 31 December 1988. This Agreement has since been
extended by another three years. Canada, USA, Sweden and Finland
agreed to collaborate on a project entitled Direct Biomass Liquefac-
tion (DBL). A Working Group of engineers and other specialists are
preparing a detailed technical-economic assessment (TEA) at com-
mercial size scale-up and operation of the most promising high- and
low-pressure pyrolysis/liquefaction processes. Both primary oil pro-
duction and upgrading are considered in the TEA. The upgrading
work on Canadian atmospheric and vacuum pyrolysis oils has been
conducted by D. Elliot at Battelle Pacific Northwest Laboratories.
Yields of products in the gasoline boiling range have so far reached
35% of primary oil by hydrotreating. The Working Group is attempt-
ing two types of analyses, one based on current state-of-the-art and the
second based on projected improvements and developments in the
technologies.
326 R. D. Hayes
ACKNOWLEDGEMENTS
The author wishes to acknowledge the various researchers in North
America without whose ideas, open discussion, and dedication to
research in thermochemical conversion of biomass, this paper would
not have been possible. Each has contributed to this paper, either
directly or indirectly. The following list is not complete, but includes
the principal investigators in Canadian laboratories and other notable
international collaborators. In alphabetical order, many thanks to
Narendra Bakhshi, Dave Beckman, Maurice Bergougnou, Michel
Bertrand, Dave Boocock, Jean Bouchard, Maurice Charron, Esteban
Chornet, Helena Chum, Jim Diebold, Allan Doienko, Murray
Douglas, Guy Drouin, Dick Eager, Doug Elliott, Bob Graham, Guy
Gravel, Michele Heitz, Ed Hogan, John Howard, Serge Kaliaguine,
Bjorn Kjellstrom, Bill Lowe, Jim McKinley, Hugh Menard, Tom
Milne, Ralph Overend, Hooshang Pakdel, Jim Pepper, Jan Piskorz,
Desmond Radlein, Tom Reed, Joe Robert, Christian Roy, Don Scott,
Tom Tidwell and their many colleagues, staff, and students.
REFERENCES
This paper contains technical contributions including progress reports from all
the Canadian and other workers mentioned here. The reader is referred to
these individuals or their published papers as primary references.
1. Brundtland, Gro Harlem, Our Common Future. World Commission on
Environment and Development, 1987.
15
Pyrolysis in Finland
YRJO SOLANTAUSTA & KAI SIPILA
Technical Research Centre of Finland, Biologinkuja 5, 02150 Espoo,
Finland
ABSTRACT
The pyrolysis of biomass has been applied industrially in the production
of coke from peat in Finland. Other related industrial utilization
schemes include gasification of wood residues and peat.
Research has been focused during this decade on high-pressure
conversion of peat and black liquor, flash pyrolysis of bark, lignin, and
peat, and hydro treatment of peat pyrolysate. All experimental work is
on the laboratory scale in batch or continuous units. Strong emphasis
has been placed on international cooperation, and that is expected to
continue.
The paper discusses also the results of a techno-economic assessment
of direct biomass liquefaction processes converting wood and peat to
gasoline and diesel fuels. The study was carried out by the working
group of the International Energy Agency, Direct Biomass Liquefaction
Activity, in which Canada, Finland, Sweden and the USA participated.
The potential for future cost reduction through research and
development was clearly demonstrated for both flash pyrolysis and
high-pressure conversion. The atmospheric flash pyrolysis, however,
was considered as the preferable route for further research, since the
risks involved were assessed to be smaller than with other technologies.
The Energy Department of the Ministry of Trade and Industry has
launched 10 national energy research programmes. Their combined
estimated cost during 1988-1992 is about 600 million Finnish marks
327
328 Yrjo Solantausta & Kai Sipilii
(FIM) , corresponding to about 130 million ECU. Five programmes
deal with energy production, two of which include aspects related to
pyrolysis.
1 INDUSTRIAL APPLICA nONS OF PYROLYSIS
The two most important technologies applied commercially, where
pyrolysis plays an important role, are carbonization and gasification.
There are two commercial carbonization plants in Finland [1]. Vapo
Inc. has a plant using sod peat at Haukineva with a capacity of
30000 t/year. Wood may also be fed to the process. By-product gases
and tars are utilized in a boiler, and electricity (12 MW
e
) and district
heat are produced. Other by-products are peat briquettes (max.
40 000 t/year). Both the raw material dryer and the reactor are rotary
kilns. The plant was designed and constructed by Outokumpu Inc.
The charcoal is used in the production of silicon and ferrosilicon.
Minor amounts are used as barbecue charcoal and absorption mater-
ial. The production of activated carbon has also been studied [2].
Carbonization was studied experimentally at VTT before the construc-
tion of the Haukineva plant. The reactor was a shaft furnace, and its
capacity was around 30 kg/h of coke.
Rautaruukki Inc. is producing metallurgical coke from coal for its
own steel mill at Raahe. The plant went on-stream in 1987. The
reactor is a shaft furnace and was designed by a company from the
Soviet Union. The pyrolysis gases are combusted at the plant. The tar
is condensed, and transported to the Federal Republic of Germany for
further upgrading.
The gasification of wood and peat has developed rapidly during the
last decade in Finland. Kemira Inc. built a High Temperature Winkler
(HTW) gasifier at Oulu in their fertilizer plant. Synthesis gas is
produced from 25 t/h peat (about 130 MW th) yielding 80 000 t/year
ammonia. The plant was started up in 1988 [3].
A. Ahlstrom Corporation manufactures both circulating fluid-bed
and fixed-bed gasifiers for biomass. Four Pyroflow plants have been
built for the production of fuel gas from sawdust and bark for lime
kilns (in Finland, Sweden and Portugal) [4]. About 10 fixed-bed
Bioneer gasifiers using woodchips and sod peat have been installed for
district heating boilers or industrial dyers. One unit has been installed
in Italy, where MSW is gasified.
Pyrolysis in Finland 329
2 RESEARCH ON PYROLYSIS IN FINLAND DURING THIS
DECADE
Research on pyrolysis has been carried out in three principal areas:
-in the characterization and upgrading of primary oils from direct
liquefaction to high-value products;
-in fundamental studies of gasification; and
-in combustion process development.
Flash pyrolysis of wood, bark and peat has been studied in a small
continuous (100 g/h) fluid-bed unit [5,6]. This work has been a
cooperation between the University of Waterloo, Canada, and VTT.
A small, fast heat-up grid reactor has also been employed. Material
balances for process concepts have been produced, and products have
been characterized [7]. The organic liquid products were separated
and identified by GC-MS and characterized by IR and GPC.
High-pressure liquefaction of peat was studied earlier at VTT [8].
The work was aimed at production of transportation fuels. Although
peat is considered most suitable for conversion [9], the economics are
not favourable as for any synfuel concept. However, the work started
at the beginning of the last decade was concluded with an experimen-
tal study of the hydroprocessing of peat tar [10] in collaboration with
the University of Toronto. High yields of hydrocarbons were pro-
duced. The study confirmed one of the results of the lEA DBL project
(see below), which concluded that peat was the most economic
feedstock for biomass-based transportation fuel production. Peat has
chemical characteristics which make it particularly suitable for conver-
sion to liquid products.
At present the emphasis on direct liquefaction at VTT is focused on
the conversion of black liquor [11-13]. Production of fuel-oil substi-
tute at a pulp mill offers considerable promise in some cases [14].
Research on the further treatment of the product has been initiated
within the EEC JOULE-programme.
Gasification of black liquor and biomass currently has high priority
at VTT. A fluid-bed PDU (200 kW, 10 bar) for gasification of solid
fuels has been used since 1988, and a PDU for black liquor gasification
(300 kw, 50 bar) is under construction.
The effects of low-temperature pyrolysis during drying of biomass
have been studied. The emphasis is on the behaviour of the organic
compounds released and their treatment at the plant [15].
330 Yrjo Solantausta & Kai Sipilii
3 lEA COOPERATIVE PROJECT ON DIRECT BIOMASS
LIQUEFACfION
3.1 Background
Canada, Finland, Sweden and the USA have had two cooperative
projects on thermochemical conversion within the lEA Forestry
Energy Agreement (now the Biomass Energy Agreement) during the
last decade. Italy and UK joined the third phase of the work, which
will operate between 1989 to 1991.
The objectives of the cooperation have been:
-to promote information exchange between the participating
countries;
-to identify potential improvements to the process concepts under
development and propose topics for research; and
-to evaluate research carried out in participating countries con-
nected with direct thermal liquefaction. The evaluation is based
on both technical and economic considerations.
They will thereby provide
-a basis for coordination of related national research and develop-
ment programmes, and
-an improved basis for decisions regarding a biomass liquefaction
test facility.
The Biomass Liquefaction Test Facility, project BLTF (1982-1984)
[16], was a major effort to study technical alternatives for a joint
experimental facility. The main conclusion was that the two competing
technologies (flash pyrolysis and high-pressure liquefaction) were both
promising. Since no experimental data on upgrading of the primary
liquids were available at the time, both were regarded as having
potential for the production of transportation fuels. Flash pyrolysate
was preferred as a fuel-oil substitute [17]. Raw materials considered
were wood and peat.
The aim of the second project, Direct Biomass Liquefaction (DBL)
(1986-1989) [18], was to compare the two technologies under de-
velopment in the production of transportation fuels. The method
Pyrolysis in Finland 331
applied was a techno-economic assessment. Elements in the study
were:
-experimental data were analysed;
-process concepts were constructed on the basis of information and
ideas proposed by the researchers developing these technologies;
-material and energy balances were calculated;
-equipment was sized, and investment and operating costs were
determined;
-process concepts were compared on the basis of technical and
economic considerations.
Altogether eight concepts were assessed. Two raw materials for
each concept were considered- wood and peat; and both present and
potential technology cases were included. Two methods (flash pyroly-
sis and high-pressure hydrogenation) were compared, bringing the
number of process alternatives to eight.
All the concepts studied include essentially three distinct steps:
primary liquid production, hydrotreatment, and refining. The first step
was sized for 2000 t/day wet biomass feed, and the first two steps were
considered to be an integrated process. The refining was considered to
take place in a central conventional oil refinery.
3.2 Results
The process concepts assessed are listed in Table 1. For all the
concepts both present and potential technology cases were considered.
Some of the data used as bases for the balances are included in
Table 1.
Flow diagrams for one of the cases Atmospheric Flash Pyrolysis
(AFP) wood, present technology, are shown in Figs 1, 2 and 3.
Table 1
Process concepts evaluated
Process concept
Atmospheric Flash Pyrolysis (AFP)
AFP
Liquefaction in Pressurized Solvent (LIPS)
LIPS
Raw Data
material sources
Wood [19,20]
Peat [21,22]
Wood [23,24]
Peat [25-27]
332 Yrjo Solantausta & Kai Sipilii
F
I
G
.

2
.

A
t
m
o
s
p
h
e
r
i
c

f
l
a
s
h

p
y
r
o
l
y
s
i
s
,

w
o
o
d
-
-
u
p
g
r
a
d
i
n
g
-
p
r
e
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;
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S
-
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:
,

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.
.
.

I
.
;
.
l

I
.
;
.
l

I
.
;
.
l

334
Feed
---+
Yrjo Solantausta & Kai Sipilii
FIG. 3. Refining of upgraded product from atmospheric flash pyrolysis of
wood.
Wood is dried (from 50 to 10%) and milled to a particle size of less
than 1 mm. The powder is fed to a fluid-bed pyrolyser, where wood is
pyrolysed at 500C. Condensed vapours, which contain about 30% of
oxygen (dry basis) and about 20% water, are hydrotreated in a
two-stage catalytic process. The first stage operates at 270C as a
stabilizing step for the second stage, which operates at 370C. The
Table 2
Specifications and performance of the process concepts
Basis: Feed 83 tlh, corresponding to 725 GJ/h for wood, 570 GJ/h for peat.
Product gasoline and diesel fuel (share specified).
Concept
AFP present, wood
AFP potential, wood
AFP present, peat
AFP potential, peat
LIPS present, wood
LIPS potential, wood
Electricity
consumption
(MW)
94
69
87
56
187
211
Product
(t/h) (GJ/h)
100 413
101 400
77 320
99 411
96 401
112 467
Gasoline Efficiency
(%) LHV
(%)
80 52
90 53
70 54
90 70
70 48
90 51
Pyrolysis in Finland 335
product, containing about 18% of oxygen, is transported to an oil
refinergy for final treatment.
A summary of the mass and energy balances for the alternatives is
shown in Table 2.
Efficiencies of transportation fuel production employing wood
feedstock are compared in Fig. 4. The development potential of AFP
in this respect seems to be rather small (efficiency around 50%),

t!.
>50
:I:
-J

Z40
W
(3
u::
u..
W
-J30
c[
:::IE
II:
W
:I: 20
t-
-J
-J

W 10
>
o
PRESENT POTENTIAL
ATMOSPHERIC FLASH
PYROLYSIS
LIQUEFACTION IN
PRESSURIZED SOLVENT
FIG. 4. Direct biomass liquefaction, wood feedstock: comparison of thermal
efficiencies.
336
Plant capacity
Time
Location
Currency
Yrjo Solantausta & Kai Sipi/o
Table 3
Parameters used in cost bases
1000 t dry biomass feed/day
September 1987
US Gulf Coast
US dollars (US$)
Annual operating time
Feedstock price, 50% moisture
8000h/y
Wood US$30/t
Peat US$20/t
US$0065/kWh Electricity price
Fixed operating cost
Operating labour
Maintenance labour
Maintenance material
Overheads
US$20/h incl. pay-roll burden
1% of FCI
a
Taxes, insurance
Other
Interest rate
Plant lifetime
Start-up costs
Working capital
Interest during construction
5% interest rate
10% interest rate
15% interest rate
a FCI, Fixed Capital Investment.
3% of FCI
2% of FCI
2% of FCI
1% ofFCI
10%
20y
10% of FCI
5% of FCI
65% of FCI
130% of FCI
195% of FCI
Table 4
Summary of economic data for biomass liquefaction
Basis: Rate of interest 10%, service life 20 y, wood US$30/t, peat US$20/t,
Sept. 1987, 1000 t/dry biomass d.
Concept Total capital Production cost
requiremen(
(US$/t)
a b c
b
d
AFP present, wood 389 364 114 867 670
AFP potential, wood 206 268 05 479 510
AFP present, peat 404 272 75 751 670
AFP potential, peat 305 260 24 589 420
LIPS present, wood 658 209 119 986 810
LIPS potential, wood 364 220 06 590 630
a a, liquefaction; b, upgrading; c, refining; d, total.
b Marginal cost (US$ million)
Pyrolysis in Finland 337
whereas the study indicates greater development potential for
Liquefaction In Pressurized Solvent (UPS).
Table 3 shows the assumptions and bases of the various parameters
used to determine product cost. The investment costs were determined
according to standard engineering practice, employing a wide range of
published data. A summary of economic data for the processes is
depicted in Table 4.
Production costs of the final product are compared in Fig. 5 with
two feedstock prices, US$lO and 30ft. Relative production cost refers
3r-------------------------------,
2.5
t-
en
o
o
Z 2
o

:::l
g 1.5
IX:
l.
W
>
t= 1

W
IX:
0.5
o
AFP PRESENT AFP POTENTIAL
LIPS PRESENT LIPS POTENTIAL
r
[
J
FEEDSTOCK COST
3O$/t
10 $/t
FIG. 5. Direct biomass liquefaction, wood feedstock: comparison of present
and potential technologies.
338 Yrjo Solantausta & Kai Sipilii
to the ratio product cost/product value. Product value is defined as an
average spot price from 1977 to 1987 for equivalent oil products, in
this case gasoline and diesel. Primary biomass liquids can also be
evaluated as fuel-oils with the same method.
3.3 Conclusions
With direct liquefaction of biomass, synthetic gasoline can be pro-
duced with high efficiency (above 50%). This applies to both AFP and
LIPS processes. Fuel-oil substitutes can be produced with an efficiency
of 60% or higher. Peat-fed processes have higher thermal efficiencies
than the ones based on wood. Direct methods are estimated to yield
higher efficiencies than indirect methods, which employ gasification.
If fuel-oil substitutes are the preferred products, AFP is the most
economic method of those available in the near future. AFP is also the
most economic route to transportation fuels from biomass, with
production cost for gasoline at about double the average spot price of
1977-1987. Although development potential exists both for high-
pressure liquefaction and pyrolysis, the development of the latter was
assessed as involving less risk.
4 PUBLIC FUNDING FOR THE ENERGY RESEARCH IN
FINLAND
The growing consumption of electricity largely determines the present
energy policy in Finland. Therefore the main emphasis in pyrolysis
research is focused on producing clean fuels for gas turbines.
The role of biomass (wood, pulping liquors, peat) in the Finnish
energy scene is important. About 30% of the primary energy
consumption is derived from renewable sources. About 7% (equal to
21 Mtoe/year) of all the primary energy is produced from pulping
black liquor, which corresponds to one-quarter of all the fuels used in
industry. Fuel wood adds 08 Mtoe/year, and peat is consumed
equivalent to 15 Mtoe/year. The share of these fuels can only be
increased by developing more economic and efficient new processes,
for instance Integrated Gasification Combined Cycle processes.
The additional potential for biomass-based electricity production
within the chemical pulp industry has been assessed to be around
600 MW during the next few decades. This figure can be reached by
increasing the electricity-to-steam ratio of a mill from the present 02
to about 04-06 with gasification combined cycles.
Pyrolysis in Finland 339
The Energy Department of the Ministry of Trade and Industry has
launched ten national energy research programmes. Their combined
estimated cost during 1988-1992 is about 600 million FIM, cor-
responding to about 130 million ECU. Five programmes deal with
energy production, two of which include aspects related to pyrolysis.
The Fuel Conversion Programme JALO and Combustion Technol-
ogy Programme LIEKKI both include pyrolysis and its effects on fuel
utilization. The JALO and LIEKKI programmes included a total of 41
separate projects in 1989, and their respective funding for 1989 was
103 million FIM and 252 million FIM, a total of about 8 million
ECU.
ACKNOWLEDGEMENTS
The authors wish to thank the DBL working group (D. C. Elliott, D.
Beckman, A. Ostman, V. Tulenheimo, B. Gevert, K. Hornell, and B.
Kjellstrom) for the information provided for this paper.
REFERENCES
1. Brandt, J., Sipilii, K. & Thun, R., Production and Use of Peat Coke. VTI
Research Notes 542, Espoo, 1986.
2. Sipilii, K. et al., Production of activated carbon from Finnish peat coke.
Paper presented at Symp. New Technologies in Peat Utilization of IPS
Commission II, Bad Zwischenahn, Nov. 5-8, 1979. In Recent Tech-
nologies in the Use of Peat. E. Schweizerbart'sche Verlagsbuchhandlung,
Stuttgart, 1983, pp. 199-207.
3. Sipilii, K., et al., Peat ammonia plant in Oulu-a case study. Paper
presented at Int. Conference Pyrolysis and Gasification, CEC Luxem-
bourg, 23-25 May 1989.
4. McKeough, P., Kurkela, E. & Sipilii, K., Thermochemical conversion of
peat into gases and liquids; recent developments in Finland. In Energy
from Biomass and Wastes X, April 7-10, 1986, Washington DC. IGT,
Chicago, 1986.
5. Scott, D. S., Piskorz, J., Westerberg, I. & McKeough, P., Flash pyrolysis
of peat in a fluidized bed. Fuel Proc. Tech., 18 (1988) 81-95.
6. Arpiainen, V., Lappi, M. & Nissilii, M., Flash-Pyrolysis of Peat, Wood,
Bark and Lignin. Part 3. Tests with peat and pine bark. VTI Research
Reports, Espoo, 1989.
7. Arpiainen, V. & Lappi, M., Products from the flash pyrolysis of peat and
pine bark. 1. Anal. Appl. Pyrolysis, 16 (1989) 355-76.
340 Yrjo So/antausta & Kai Sipilii
8. McKeough, P. et al., Techno-economic Assessment of Direct Biomass
Liquefaction Processes. VIT Research Reports 337, Espoo, 1985.
9. Hornell, C. et aI., Dissolution of peat and wood in tetralin compared with
coal. In: Fundamentals of Thermochemical Biomass Conversion, ed. R. P.
Overend et al. Elsevier Applied Science, London, 1985, pp. 827-38.
10. Oasmaa, A., Upgrading of peat pyrolysis oil. Internal report, VIT,
Espoo, 1989.
11. Johansson, A., A new chemical recovery system for the kraft process.
Biomass, 4 (1984) 155-60.
12. McKeough, P. & Johansson, A., Oil production by high-pressure thermal
treatment of black liquors. ACS Symp., 376 (1988) 104-12.
13. McKeough, P., Alen, R., Oasmaa, A. & Johansson, A., Thermochemical
conversion of black liquor. In Proc. 4th E. C. Con! on Biomass, Orleans,
France, 11-15 May 1987, ed. G. Grassi et al., Elsevier Applied Science,
London, 1987, pp. 362-5.
14. Jaakko Poyry Ltd., Technical and economic prospects for a black liquor
conversion process. Study for VIT Helsinki, 1987.
15. Fagerniis, L. & Sipilii, K., The behaviour of wax components in the drying
system of a peat power plant. Fuel Processing Technology, 21 (1989)
189-200.
16. Kjellstrom, B. (ed.), lEA Forestry Energy Project, a study of a biomass
liquefaction test facility. National Energy Administration, Sweden,
Stockholm, 1985.
17. McKeough, P. et al., Techno-economic Assessment of Direct Biomass
Liquefaction Processes. VIT Research Reports 337, Technical Research
Centre of Finland, Espoo, 1985.
18. Beckman, D. et al., Final report stage 2, Technoeconomic assessment of
selected biomass liquefaction processes. Research Reports 697, Technical
Research Centre of Finland, Espoo, 1990.
19. Scott, D. & Piskorz, J., The continuous flash pyrolysis of biomass. Can. J.
Chem. Eng., 62 (1984) 404-12.
20. Elliott, D. & Baker, E., Hydrotreating biomass liquids to produce
hydrocarbon fuels. In: Energy from Biomass and Wastes X. IGT, Chicago,
1986, pp. 765-84.
21. Piskorz, J. & Scott, D., Pyrolysis of Carex peat-results of pilot plant
pyrolysis tests performed for the Technical Research Centre. 5 Feb. 1988.
22. Elliott, D. C. et aI., Production of liquid hydrocarbon fuels from peat. J.
Energy Fuels, 2 (1988) 234-5.
23. Thigpen, P. & Berry, W., Liquid fuels from wood by continuous
operation of the Albany, Oregon biomass liquefaction facility. In: Energy
from Biomass and Wastes VI. IGT, Chicago, 1982, pp. 1057-93.
24. Baker, E. & Elliott, D., Catalytic hydrotreating of biomass-derived oils.
Am. Chem. Soc., Viv. Fuel Chem. Preprints, 32 (1987) 257-63.
25. McKeough, P. & Tulenheimo, V., Techno-economic Assessment of High
Pressure Peat Liquefaction. VIT Research Reports 492, Espoo, 1987.
26. Bjornbom, E. & Bjornbom, P., Some criteria for the selection of peat as a
raw material for liquefaction. Fuel 67, 10 (1988) 1589-92.
27. Gevert, B. & Otterstedt, J., Upgrading of directly liquefied biomass to
transportation fuels: catalytic cracking. Biomass, 14 (1987) 173-84.
16
Development of Pyrolysis Reactor Concepts in the
USA
JAMES DIEBOLD
Solar Energy Research Institute, 1617 Cole Boulevard, Golden,
Colorado 80401, USA
ABSTRACT
A number of pyrolysis reactors have been built in the USA over the last
15-20 years. Most have been oriented to the production of medium
heating value gas, with interest in liquids only emerging in more recent
years. Due to the complexity of the physical processes occurring during
pyrolysis and the interactive effect of the various parameters, there is
still much development possible. This chapter reviews developments in
reactor concepts since about 1970.
1 INTRODUCTION
Pyrolysis of biomass in the United States of America, has developed
from a slow, batch process, which in the 1920s and 1930s produced
large yields of char, water, gas, and small yields of a variety of various
organic condensates. Although gasification of biomass was utilized in
Europe during World War II for transportation fuels, there were ample
supplies of gasoline in the USA at that time. Pyrolysis of biomass was
not widely studied in the USA until the 1970s, when petroleum fuel
shortages revived an interest in alternative sources of energy. During
the 1970s and 1980s many different approaches to pyrolysis were
researched and developed. This paper highlights selected examples of
341
342 James Diebold
pyrolysis R&D performed in the United States, primarily during the
last 15 years, but the inclusion or exclusion of any particular project
should not be interpreted as an endorsement or a lack thereof.
These efforts resulted in a large variance in the reported yields, due
to the process variables at work. These process variables were poorly
understood by most of the researchers in the field at the time. In 1980,
an international specialists' workshop on fast pyrolysis helped to
identify a large number of global chemical reactions, which, when
taken together helped to explain the very different pyrolysis products
reported by a wide variety of researchers [1].
A simplification of this complex global scheme is shown in Fig. 1. A
search in the literature several years ago identified that global reaction
rates were available for cellulose, as shown in Fig. 2 in an Arrhenius
plot. A mathematical model was developed in which the several
simultaneous differential equations were numerically integrated. An
example of the output is shown in Fig. 3, in which it is seen that the
oligomeric liquids ('active') are formed very early as the temperature
rises. These oligomers then decompose to form char and primary
vapors. If the primary vapors stay in the reaction zone, they in turn
decompose to secondary gases and liquids [2].
Although the relative reaction rates can be catalyzed, i.e. by alkali
metals, the general overview of pyrolysis seems to be qualitatively
useful to predict the types of products to be expected from a certain
combination of heating rates and temperature history. For example,
the slow retorting of biomass at low temperatures has long been
known to maximize the yields of char, as would be predicted from Fig.
2; at low temperatures, the char-forming reaction has the fastest rate.
SECONDARY
GF.;
k 7.. yk
ACTIVE PRIMAR --!!...SECONDARY
FE,D
k
- VAPORS TAR (y)
\d CHAR (a) + H
2
0 (a)
CHAR (d) + H
2
0 (d)
FIG. 1. Simplified biomass global pyrolysis reaction scheme.
Development of Pyrolysis Reactor Concepts in the USA
TEMPERATURE, C
5ee 3e0 250
3
.
W
2
0::
Z
o
H
I-
U
a:
W
0::
t...
o
C\l
w
Ul
a:
aI
CJ
o
.J
"
-1
-2
-3
-4
-5

8 10 12 14 1 S 18 20
INVERSE TEMPERATURE, 10000/K
FIG. 2. Arrhenius plot for cellulose decomposition.
2 RETORTING OF BIOMASS
343
Although the retorting of biomass has been widely practiced, one
example of such an operation will have to suffice in this short paper. In
the 1920s and early 1930s, automobiles were made with a considerable
amount of wood. The Ford Motor Company generated 360 tonnes of
hardwood scrap each day of operation. They dried the wood scrap to
!% moisture at 150C using flue gases entering at 315C. The wood
scrap was then placed in one of three retorts, which measured 3 m in
diameter by 12 m high. The pyrolysis process was started by lighting a
fire in the bottom of the retort, after which the air was shut off and the
exothermic reactions of the char-forming pyrolysis reactions supplied
the remainder of the heat required. The yields of products were
30% wt char (about 60% of the energy), 21 % medium-energy gases,
and 49% 'green liquor' (the green liquor was stored in copper tanks).
Within the green liquor were yields of 5% acetic acid, 1% wood
344 James Diebold
atm PRESSURE
lee
C/s HEATING RATE
I.e
-.-.---
Ieee
e.9
/rcttve
900
0.8 I \
Temp
800
e.7
I
\
700
Z
0
I \ .
0
H
....
0.6
\ I
see
0 I&J
a:
Gases
0:
0:
e.s
see
L..
a:
....
0:
::I:
e.4
'lee It
CI
J:
H
I&J

e.3
300 r-
0.2
2e0
0.1
100
e.ee
0
2
10
TIME, sec
FIG. 3. Simulated pyrolysis of cellulose.
alcohol (methanol), 03% ketones, 9% soluble tars, and 5% insoluble
tar with 29% water by difference. The acids and methanol were
recovered and converted to methyl and ethyl acetates for use as paint
solve.nts [3].
3 PARTIAL OXIDATION FOR DIRECfLY SUPPLYING
HEAT FOR PYROLYSIS
3.1 Updraft, fixed bed
In an effort to improve upon the retorting in batches, various
approaches to pyrolysis were employed in the 1970s. The updraft
fixed-bed approach was developed at Georgia Tech and commercial-
ized by Techair [4]. In the updraft reactor, feed entered at the top of a
'fixed bed'. As the feed particle slowly moved downward with other
similar particles, it sequentially underwent drying, pyrolysis, and
Development of Pyrolysis Reactor Concepts in the USA 345
oxidation in well-defined horizontal strata, as determined by research
at SERI [5]. There was usually an excess of char produced over the
energy demands of the pyrolysis process. The pyrolysis vapors and
gases were removed from the top of the unit and contained about 25%
water-insoluble tars. The yields of char were about 30% and the
organic-laden aqueous phase comprised about 35%. The pyrolysis
gases were used to dry the feed. This type of reactor was also
researched at the Pacific Northwest Laboratory with refuse-derived
fuel (RDF) [6]. The Techair technology is now being marketed by
American Carbons to produce char.
3.2 Downdraft, fixed bed
The concept of a downdraft, fixed-bed gasifier was developed and
demonstrated at SERI to produce a medium-energy synthesis gas at
1 MPa pressure. (This technology was a variation on the downdraft
gasifiers developed in Europe during World War II to fuel automobiles
and trucks.) In the SERI gasifier, oxygen entered at the top of the bed
along with the fresh feed. Flaming combustion occurred at the top of
the bed, with the resulting char bed acting to crack residual tars. When
operated as an air gasifier at atmospheric pressures, the top of the
gasifier could be completely open [7]. Based on this gasifier, Syngas
Inc. developed commercial-scale units, with low-energy gases for
boiler applications as the short-term goal and for fueling internal
combustion engines for power generation as the long-term goal.
3.3 Fluidized beds
The use of fluidized beds with partial combustion was also developed
in the late 1970s at atmospheric pressures to produce char and
condensates. One example of this was a unit developed by Erco to
convert agricultural wastes to pyrolysis oils and char, with the gases
used for process energy. This was a bubbling, fluidized bed having a
diameter of 05 m. The production of pyrolysis liquids was optimized
at about 500C at around 35% and dropped off significantly at higher
temperatures with a corresponding increase in gas production [8].
Fluidized beds were studied by the Institute of Gas Technology for
the production of synthesis gas at 2 MPa pressure using oxygen diluted
with steam to effect a partial combustion of the products. By
increasing the reactor temperature from 750 to 820C, the unwanted
organic liquid yields were reduced from 4 to 15% of the dry feed. The
organic liquid yields were reported to be negligible at 820C with the
346 James Diebold
use of wet feed, which required more oxygen to attain the operating
temperature. The effect of pressure was to lower slightly the yields of
organic liquids [9}.
3.4 Entrained beds
The heating of entrained-bed pyrolysis reactors by direct heating of
the carrier gas with combustion has been developed at Georgia Tech
with the goal of producing pyrolysis liquids. They found that the liquid
yields were maximized by the use of carrier gases which had not been
preheated above about 750C and at a carrier gas/feed weight ratio of
about 8. Although a lower amount of carrier gas could be used if it
were preheated to higher temperatures, this resulted in lower yields of
the pyrolysis oils. Yields of pyrolysis oils on a moisture-free basis were
58% wt, although the condensates as produced were about 50% water
due to the condensation of the water formed during the combustion
used to preheat the carrier gases and also to the water formed by
pyrolysis [10).
4 INDIRECT COMBUSTION TO SUPPLY THE HEAT OF
PYROLYSIS
4.1 Fixed beds
The use of partial combustion in the pyrolysis reactor to supply the
heat needed for pyrolysis has the disadvantage that the products of
combustion are present in the product gas. If air is used for that partial
combustion, the product gases are usually changed from medium- to
low-energy gases. The use of a separate chamber to combust a fuel,
along with some technique to transfer the energy from the hot flue
gases to the pyrolysis reactor, has the advantage of producing gases
which are higher in their fuel value or which will require less clean-up
for use as synthesis gases. A 24 tonne/day, countercurrent fixed-bed
reactor design was used by Enerco, in which feed entered the top of
the reactor and char exited the bottom. The heat was delivered to the
bottom of the 'fixed bed' pyrolysis unit by a recycle stream of pyrolysis
gas, which had been heated to 300-500C by passing through a heat
exchanger heated by combustion of the pyrolysis gases. This system
produced charcoal and a condensate, which had a heat of combustion
corresponding to an oxygenated pyrolysis oil [11).
Development of Pyrolysis Reactor Concepts in the USA 347
4.2 Dual-fluidized beds
The petroleum industry has long utilized a dual-fluidized-bed reactor
system to crack heavy petroleum fractions catalytically. In this
approach, the endothermic cracking of the heavy oil to gasoline in a
fluidized bed results in the formation of coke on the catalyst. The
coke-laden catalyst is continuously removed from the pyrolytic bed
and sent to the combustion bed. The oxidation of the coke with air
reheats the catalyst and the heated catalyst is returned to the pyrolysis
bed. The heat transfer is thus actually a physical transport of the
heated surface, i.e. the catalyst particle, from the combustion zone to
the pyrolysis zone. With this dual-fluidized-bed concept applied to
biomass, the char is typically transported with the fluidized bed
particles to the combustion zone.
A very ambitious demonstration plant which used the dual-bed
approach, was built by the Occidental Research Corporation in the late
1970s to process refuse-derived fuel (RDF). From a 64-tonne/day
pilot plant single fluidized bed, the dual-bed pyrolysis concept was
scaled-up to a nominal l00-tonne RDF/day reactor. The RDF was
comminuted to a fluff prior to feeding. The pyrolysis system had a
large number of developmental problems which included extremely
fast wear of the fluff-producing mill, removal of char fines from the
pyrolysis stream with cyclone separators, and the subsequent fouling
of the pyrolysis oil recovery system. In addition, the nature of the
condensates changed because, in part, of higher yields of water. The
unit was only operated a total of 140 h before it was shut down [12].
The failure to operate this demonstration system smoothly was very
detrimental to the image of fast pyrolysis in the early 1980s. At about
this time, research was proceeding at Occidental Research to use
zeolites to upgrade pyrolysis oils to gasoline, in a manner analogous to
the cracking of heavy petroleum fractions in a refinery [13].
This dual-bed approach to pyrolysis has also been studied at the
Arizona State University with a wide variety of feedstocks in a
nominal 5-kg/h unit, primarily to produce synthesis gases rich in
olefins for conversion to alcohols and diesel fuel [14]. In addition,
Battelle-Columbus has developed a dual-bed having a diameter of
25 cm and a throughput of about 22 tonnes/day. This gasifier, when
operated at around 825C, produced a medium-energy synthesis gas,
which contained only about 05% wt of residual organic condensates
[15].
348 James Diebold
4.3 Single Buidized beds
The simplicity of single fluidized beds makes them attractive for
pyrolysis of biomass. Although small-scale fluidized single beds are
often electrically heated, this becomes quite expensive in a large,
commercial-sized unit. The use of flue gases flowing within heat-
exchange tubes immersed in the fluidized bed to provide the heat for
pyrolysis can result in a very efficient system. The factor limiting the
heat transfer has been determined to be the transfer of heat from the
flue gases to the heat-exchange tube [16]. Traditionally, increases in
gaseous convective heat transfer have been attained through the use of
higher gas velocities (increased furnace blower work) or through the
use of expensive finned tubing. A very recent development has been
the use of a pulsed combustor, which increases the heat-transfer
coefficient by four- to five-fold, while at the same time eliminating the
need for a furnace blower [17].
4.4 Entrained-Bow reactors
The use of combustion to heat externally a tubular, entrained-flow
pyrolysis reactor was researched at the Naval Weapons Center to
pyrolyze finely ground RDF to produce gases rich in olefins. The heat
transfer to the pyrolysis tube was analogous to that used in a naphtha
cracking furnace to make ethylene. The pyrolysis gases were com-
pressed and the olefins concentrated. The olefins were then converted
to polymer gasoline in a non-catalytic process [18].
A different type of entrained flow reactor was developed at the
Solar Energy Research Institute, in which the biomass was entrained
into a modified vortex tube. Very high heat-transfer rates into the
biomass particles are thought to be attained which result in ablative
pyrolysis. A recycle loop was added to allow the reactor to be
relatively insensitive to the particle size of the feed. Yields of pyrolysis
oils of 54% have been demonstrated when using a coarse sawdust as
feed and with carrier gas/feed weight ratios of about 1-2 [19]. The
scale-up of the concepts used in the vortex reactor is being pursued by
Pyrotech, which has built and briefly operated prototypes in the
5-25 tonne/day range.
5 SUMMARY
Over the last 15 years or so, there have been several pyrolysis reactors
built and operated in the USA, which were based on different
Development of Pyrolysis Reactor Concepts in the USA 349
combinations of the basic design variables. Most have been oriented to
the production of fuel gas. Each of these reactors have certain
advantages for specific applications, with no one reactor design clearly
superior from all perspectives. Due to the very large number of
possible combinations of design variables, it is entirely probable that
new pyrolysis reactors having novel features will continue to appear in
the future.
REFERENCES
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of Biomass, Copper Mountain, CO, 19-22 October. Solar Energy
Research Institute, Golden, CO, 1980. 80401 SERI/CP-622-1096 (NTIS).
2. Diebold, J. P. & Scahill, J. W., Ablative, entrained-Bow fast pyrolysis of
biomass. In Proceedings of the 16th Biomass Thermochemical Contractors'
Meeting, Portland, OR, 8-9 May, Pacific Northwest Laboratory, Rich-
land, WA, 99352, 1984. PNL-SA-12403, CONF-8405157.
3. Nelson, W. G., Waste wood utilization by the Badger-Stafford process.
Ind. Eng. Chem., 22(4) (1930), 312.
4. Tatom, J. W., Colcord, A. R., Knight, J. A. & Elston, L. W., Clean Fuels
from Agricultural and Forestry Wastes, EPA-600/2-76-090. US EPA,
1976.
5. Desrosiers, R., Gasification engineering. Paper presented at 12th Biomass
Thermochemical Conversion Contractors' Review Meeting, Washington,
DC, 18-19 March, 1981.
6. Hammond, V. L., Mudge, L. K., Allen, C. H. & Schiefelbein, G. F.,
Energy from Solid Waste by Pyrolysis-Incineration. Pacific Northwest
Laboratories, Richland, WA, 99352, 1972. BNWL-SA-4471.
7. Reed, T. B. & Markson, M., Biomass gasification reaction velocities. In
Fundamentals of Thermochemical Biomass Conversion, ed. Overend, R.,
Milne, T. & Mudge, L. Elsevier Applied Science, London, 1985, pp.
951-65.
8. Kosstrin, H., Direct formation of pyrolysis oils from biomass. In [1], pp.
105-22.
9. Kososki, G. M., Onischak, M. & Babu, S. P., Development of biomass
gasification to produce substitute fuels. In Proceedings of the 16th Biomass
Thermochemical Conversion Contractors' Meeting, Portland, OR, 8-9
May. Pacific Northwest Laboratory, Richmond, WA, 1984. PNL-SA-
12403, CONF-8405157.
10. Kovac, R. & O'Neil, D., Liquid biofuels production by an entrained
pyrolysis process. In Proceedings of IGT's Symposium Energy from
Biomass and Wastes XIII, New Orleans, LA, 13-17 Feb. 1989. Institute of
Gas Technology, Chicago, 1989, pp. 829-50.
350 James Diebold
11. White, E. W. & Thomson, M. J., The ENERCO Pyrolysis System. In
Thermal Conversion of Solid Wastes and Biomass, ACS Symposium Series
130, American Chemical Society, Washington, DC, 1980, pp. 275-284.
12. Harrison, B. & Vesilind, P. A., Design and Management for Resource
Recovery, Vol. 2, High Technology-a Failure Analysis. Ann Arbor
Science, Michigan, 1980, pp. 61-85.
13. Frankiewicz, T., The conversion of biomass derived pyrolytic vapors to
hydrocarbons. In [1], pp. 123-36.
14. Kuester, J. L., Fernandez, C. M., Wang, T.-C. & Heath, G., Liquid
hydrocarbon fuel potential of agricultural materials. In Fundamentals of
Thermochemical Biomass Conversion, ed. Overend, R., Milne, T. &
Mudge, L. Elsevier Applied Science, London, 1985, pp. 875-96.
15. Feldman, H. F., Paisley, M. A. & Applebaum, H. R., Conversion of
forest residues to a methane-rich gas in a high throughput gasifier. In
Proceedings of the 16th Biomass Thermochemical Contractors' Meeting.
Pacific Northwest Laboratory, Richland, WA. 1984. PNL-SA-12403,
CONF-8405157, pp. 13-38.
16. Flanigan, V. J., Punyakumleard, A., Sineath, H. H. & Sitton, O. C.,
'20' fire tube gasification system. In Proceedings of the 16th Biomass
Thermochemical Contractors' Meeting, Pacific Northwest Laboratory,
Richland, WA. 1984. PNL-SA-12403, CONF 8405157, pp. 83-102.
17. Durai-Swamy, K., Warren, D. W., Aghamohammadi, B. & Mansour,
M. N., Pulse-assisted gasification of black liquor and organic wastes for
medium-BTU gas. In lGT's Symposium Energy from Biomass and Wastes
XIII, New Orleans, LA, 1989. Institute of Gas Technology, Chicago,
1989, pp. 689-713.
18. Diebold, J. P. & Smith, G. , Commercialization potential of the China
Lake trash-to-gasoline process. In Design and Management for Resource
Recovery, Vol. 1. Energy from Waste, ed. Frankiewicz, T. Ann Arbor
Science, Michigan, 1980, pp. 113-40.
19. Diebold, J. P. & Power, A. J., Engineering aspects of the vortex pyrolysis
reactor to produce primary pyrolysis oil vapors for use in resins and
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Bridgwater, A. & Kuester, J. Elsevier Applied Science, London, 1988,
pp.609-28.
17
Conclusions and Recommendations
A. V. BRIDGWATER
Energy Research Group, Chemical Engineering Department, Aston
University, Aston Triangle, Birmingham B4 7ET, UK
INTRODucnON
This book has described the status of a wide range of technologies
relating to the production, upgrading, refining and utilisation of liquid
fuels by direct thermochemical processing of biomass. This final
chapter attempts to summarise the main problem areas in each of the
topics covered and hence identify research and development needs for
the short, medium and long term.
Each area is considered separately, although some overlap occurs
and integration of relevant technologies is one of the major require-
ments of future R&D programmes. The list is not intended to be
exhaustive, but to indicate what are currently considered to be the
priority areas. Each recommendation is numbered for cross-
referencing.
PYROLYSIS TECHNOLOGIES
Flash or fast pyrolysis under carefully controlled reaction conditions
offers the greatest potential for production of high yields of liquid fuels
and possibly chemical specialities. Although this topic has already
been extensively researched, there are still many areas requiring
further R&D, such as:
1. Improve the selectivity of, and the yield of liquids from, pyrolysis
processes through basic and applied research.
351
352 A. V. Bridgwater
2. Improve liquid product quality in terms of chemical and physical
characteristics such as stability, consistency and viscosity.
3. Examine the possibilities for speciality chemicals production,
either alone or in combination with liquid fuel production.
4. The use of catalysts within a flash pyrolysis reactor deserves
attention for improving selectivity and/or yield.
5. As waste-water can be a major pollutant from pyrolysis pro-
cesses, design or operating techniques for minimizing or elimina-
ting its production (for example by maintaining it as a vapour
until incineration) need investigation as an alternative to de-
veloping effective treatment processes.
6. Although capital costs of pyrolysis plants are not always the
largest cost item, process and design development should aim to
reduce both initial capital costs and operational costs of
maintenance.
7. Poor reliability or low availability of plants increases product
costs and reduces market interest, so another target is the
improvement of process reliability.
LIQUEFACfION TECHNOLOGIES
There are four approaches to liquefaction, all of which result in a
bio-oil with a lower oxygen content than pyrolysis liquids and which,
therefore, may be more stable and require less extensive upgrading to
hydrocarbon fuels than pyrolysis oil:
-High-pressure reaction in an aqueous medium with carbon
monoxide and carbonate as catalyst.
-High pressure reaction in recycled oil with hydrogen and
hydrocracking/hydrotreating metal catalysts.
-High pressure steam treatment followed by high pressure
hydrotreatment of the tarry extract.
-Medium pressure solvolysis in an organic medium, distillation of
the solvent followed by high pressure hydrotreatment of the tarry
residue.
The recommendations for R&D are as follows:
8. Develop custom-designed catalysts to improve product yield and
quality in all modes of liquefaction.
Conclusions and Recommendations 353
9. Build a flexible continuous-process development unit to study
process kinetics and obtain design and performance data for
scale-up and techno-economic assessment.
10. Investigate biomass fractionation and separate liquefaction of
liquids for chemicals production.
11. Examine co-processing of biomass with other solid fuels such as
lignite.
HYDROTREATMENT OF PYROLYSIS OILS
Hydrotreatment is one route for production of hydrocarbons from
pyrolysis and liquefaction liquids.
12. Further R&D on upgrading processes should be conducted in
flow reactors in order to optimise reaction conditions and
determine catalyst deactivation rate; therefore a continuous
system should be built.
13. The viability of disposable catalysts should be determined.
14. The compatibility and the extent of the conversion should be
determined for co-processing pyrolysis oils with petroleum-
derived products.
ZEOLITES AND CATALYSTS
This is a more recent approach to production of hydrocarbons from
pyrolysis liquids, and little research has been carried out although
preliminary results are very encouraging. Problems to date include the
following.
-Only 'off the shelf' catalysts have been used in research so far.
-There is currently no activity on application of zeolites to
pyrolysis liquids in Europe.
-Rapid catalyst deactivation through deposition of coke is a major
problem that needs to be resolved.
-Catalyst selectivity needs modification and improvement, for
example by manufacturing a specific multi-function catalyst, with
up to three components:
(a) large- and medium-pore zeolite;
(b) water gas shift function;
(c) hydrogenation/deoxygenation.
354 A. V. Bridgwater
Recommendations for R&D are separated into short- and medium-
term objectives.
Short-term efforts:
15. Develop basic knowledge about catalyst effects on biomass
conversion products.
16. For zeolites, study pore architecture, acid spectrum,
morphology.
17. Assess viability of multifunctional catalysts.
18. Study effects of process variables such as temperature and
vapour concentration.
Medium-term efforts:
19. Investigate tuning of different functions.
20. Investigate integration of a variety of catalyst functions in one
catalyst pellet, and assess viability.
CHAR-WATER SUPPLIES
Work carried out to date has reached the following conclusions.
-Slurries must be clean if they are to replace domestic fuel.
-Ash removal techniques are necessary to maintain pollution
control standards.
-Whilst the slurryis currently twice the price of domestic fuel, the
consequences of the EEC common agricultural policy make it an
interesting alternative.
There is still further R&D that needs to be carried out to establish
the optimum formulation of slurries and assess its performance in use:
21. Examine other additives with respect to the hydrophobic phase,
such as crude oils, non-marketed mineral oil distillation cuts,
pyrolysis tars, and upgraded pyrolysis liquids.
22. Evaluate the best ash removal process.
23. Examine other feeds for production of the charcoal such as
refuse (MSW), eucalyptus and poplar, and agricultural wastes.
24. Study the combustion characteristics of char-water slurries in
boilers and engines, including any necessary equipment
modifications.
Conclusions and Recommendations 355
25. Study possible outlets for the technology and the product in
developing countries, and the role of slurries compared with
fuel gas.
26. Carry out a detailed economic and market study of the
opportunities for char-water slurries, char-oil slurries and
ternary slurries.
ANALYSIS AND CHARACTERISATION OF PYROLYSIS
OILS
Analysis of pyrolysis products is necessary to obtain a sound under-
standing of the pyrolysis process and reaction mechanisms and derive
robust models of pyrolysis for design, optimisation and scale-up. It is
also essential for comparison of bio-oils from different processes and
for product characterisation.
Other analytical and characterisation applications include research
into pollutants/carcinogens, etc., estimation of upgrading efficiency
(e.g. by hydrotreating and zeolites), and studies into the ageing
processes of pyrolysis and liquefaction products.
R&D requirements can be thus summarised as follows.
27. Improve existing analyses through:
(a) SFC/MS coupling for high-mass/strong-polarity solution
systems;
(b) better identification of components through standards, use
of MS/MS techniques and high-resolution MS;
(c) a more quantitative approach not only to identify com-
ponents but also to estimate weight fractions which, for
example, will aid chemicals recovery assessment.
28. Try to solve the problem of basic fractions analysis.
29. Develop better cooperation through exchange of MS data and
other standards, and participation in analytical techniques
comparisons.
PRODUCT STANDARDS
In order to develop applications for bio-oils and slurries, it is necessary
to provide measures of performance that are standard for the fuel and
356 A. V. Bridgwater
energy sector in order to compare these novel fuels with conventional
fuels. While many tests can be applied to both conventional and
biomass-derived fuels, there are some special properties of biomass-
derived fuels which may require special tests to be formulated to
convince industry and potential users of the value of these products.
The R&D recommendations are summarised below.
30. Collect further data concerning product properties of biomass-
derived liquid fuels. A key factor is the provision of sufficient
bio-oils for testing and comparison.
31. Assess the suitability of conventional fuel tests and standards for
biomass-derived liquid fuels, and, where necessary, recommend
new or revised procedures.
32. Establish new standards, where necessary, for production of
these new fuels, so that pyrolysis process developers can target
their optimisation and design studies, and potential users can
assess the quality of the product they are buying.
33. Construct a data book of relevant properties.
34. Examine simple methods of purification for removal of water,
separation of suspended solids such as charcoal, and
neutralisation.
35. Evaluate suitable materials of construction for handling and
storage equipment such as pumps, atomisers, gaskets, pipes and
storage tanks.
36. Assess protection requirements for workers handling bio-oils.
37. Assess potential environmental consequences of spillage or
leakage.
38. Assess likely emissions from utilisation of the bio-oil and
requirements for pollution control.
LIQUIDS UTILISATION IN REFINERIES
Processing pyrolysis oils in standard refineries will require the follow-
ing areas to be examined.
39. Study the mixing behaviour of pyrolysis and conventional crude
oils.
40. Measure the fluid dynamics and thermal properties of such
mixtures.
41. Assess the influence of bio-oils on desalting and draining
facilities.
Conclusions and Recommendations 357
42. Assess the influence of bio-oils on distillation units.
43. Assess the influence of bio-oils on yield structure and product
quality of upgrading units.
44. Compare the technical and economic effects of feeding pyrolysis
or liquefaction products at different points in the refinery.
45. Assess the economic value of pyrolysis or liquefaction products
to a refinery.
CHEMICALS AND FUEL ADDITIVES
Chemicals nearly always have a higher value than fuel products and
chemicals production is, therefore, of considerable interest, even if
only a small fraction of the liquids produced is recovered for this
application. Recovery must, however, be both technically feasible and
economically viable. Further R&D should examine the following
areas.
46. Identify and evaluate the chemicals or families of chemicals that
are recoverable from bio-oils, estimate the cost-effectiveness of
their recovery and assess opportunities for conversion or
upgrading of these chemicals into more valuable products.
47. Investigate the more interesting of these chemicals for their
separability, yields and conversion, and establish production
schemes.
48. Develop catalysts with good stability and selectivity to the
required product.
49. For recovery of the phenolic fraction from bio-oils, develop
effective and energy-saving separation techniques and further
isolation and purification of selected valuable components.
50. For fuel additives, by catalytic treatment of mixtures of phenols,
develop a suitable process for producing the most valuable
aromatic ethers in terms of octane rating and other established
standards.
51. A longer-term possibility is the development of integrated
processes of thermochemical conversion of biomass, with re-
covery of valuable chemicals such as phenols, separation and
upgrading to aromatic ethers. Ideally the recovery of chemicals
still would leave a fuel product that can be utilised
economically.
52. The markets for any recovered chemicals must be carefully
assessed to avoid saturation or severe market imbalance.
358 A. V. Bridgwater
INTEGRATED PROCESSES
There are two major areas requiring further study:
-integration of biomass production with conversion and utilisation.
of biomass conversion systems.
Improved integration of production, conversion and utilisation
requires the following R&D.
53. Characterise harvesting and comminution systems in terms of
performance and cost.
54. Evaluate comminution technologies in relation to the require-
ments of the thermochemical conversion process, and examine
the effects of each product size distribution on each current and
proposed conversion system.
55. Optimise the design of systems, both technically and economic-
ally, to use the full range of particle sizes produced.
56. Evaluate conversion technologies in relation to the require-
ments of the applications that utilise the bio-oil or slurry
product in order to characterise the preferred process and aid
optimisation studies.
57. Evaluate the integration of thermochemical conversion pro-
cesses into a comprehensive biomass-processing system that
may include products such as pulp, bio-ethanol, electricity
and/or compost, that maximises the overall contribution of
biomass in an environmentally acceptable way.
Optimisation of complete integrated conversion systems requires the
following R&D.
58. Collate data on conversion and upgrading processes.
59. Collate data on transport and handling costs of biomass and
derived and upgraded products.
60. Collate data on costs of all relevant processes and materials.
61. Assess and compare alternative systems for production of useful
and valuable products including fuels and chemicals, through
techno-economic evaluation.
62. Identify areas of limited data where this is critical to the
sensitivity of the processes, and initiate targeted R&D pro-
grammes to resolve the uncertainties.
Conclusions and Recommendations 359
ENVIRONMENTAL ASPECTS
In order to reduce pollution from pyrolysis activities (particularly for
charcoal-making technologies) and improve the energy conversion
yields, the following R&D is necessary.
63. Carry out fundamental research on pyrolysis products with
particular regard to carcinogenic and mutagenic compounds.
64. Carry out extensive equipment performance tests in respect of
emissions and emission controls for acquisition of data.
65. Develop new and more efficient pyrolysis technologies including
waste and pollution treatment systems, such as incineration.
66. Investigate ways of managing aqueous effluents in the most
environmentally effective way.
67. Evaluate the cost of pollution control in pyrolysis processes.
PILOT PLANT REQUIREMENTS
An important step in process development is often construction of a
pilot plant to prove critical steps in a process and derive data for
design and scale-up. It is important that the requirements of the pilot
plant are clearly specified and that the cost of this step is fully justified
in terms of cost and time.
PYROLYSIS IN BRAZIL
For the Brazilian situation, the following aspects are important.
68. Investigate catalytic upgrading of eucalyptus wood carbonisation
tars with hydrocracking catalysts to diesel-like fractions.
69. Develop small-scale (around 30 t/ d) flash pyrolysis processes for
sugar-cane bagasse, and add a refining step using zeolites to give
diesel fuels.
70. Develop flash pyrolysis of bagasse for production of high-value
chemicals such as resins or binders.
PYROLYSIS IN CANADA
A key element in the successful implementation of thermochemical
processes for production of fuels and chemicals from biomass is the
360 A. V. Bridgwater
exchange of information and ideas through collabo