Anaerobic Digestion of Agro-Industrial

ANAEROBIC DIGESTION OF AGRO-INDUSTRIAL
WASTES: INFORMATION NETWORKS

Technical Summary on Gas Treatment
AD-NETT
Project FAIR-CT96-2083 (DG12-SSMI)
FINAL VERSION
August 2000
Barbarossastraat 35
P.O. Box 151
6500 AD NIJMEGEN
00 31 24 328 42 84
00 31 24 323 93 46
Our reference: H0489.A0/R002/TS/GR 25 January 2000
ANAEROBIC DIGESTION OF AGRO-INDUSTRIAL
WASTES: INFORMATION NETWORKS
AD-NETT
Project FAIR-CT96-2083 (DG12-SSMI)
FINAL VERSION
Prepared by : ir. A.H.H.M. Schomaker, ing. A.A.M. Boerboom, Dr. ir. A. Visser,
ing. A.E. Pfeifer (Novem)
Approved by : ir. A.H.H.M. Schomaker Initials:
AD-NETT Project FAIR-CT96-2083 (DG12-SSMI)
H0489.A0/R002/TS/GR - i - 25 January 2000
DISCLAIMER
Contract number: 355299/4010
This project is cofunded by the Dutch energy from waste biomass program
(EWAB).
Control and co-ordination of the EWAB program are at:
Novem
Catharijnesingel 59
PO Box 8424
3503 RE Utrecht
The Netherlands
telephone : +31-30-239.36.31
telefax : +31-30-231.64.91
The project has been executed by:
HASKONING Consulting Engineers and Architects
PO Box 151
6500 AD Nijmegen
Date of report: August 1999
H0489.A0/R002/TS/GR - ii - 25 January 2000
CONTENTS
Page
ABSTRACT 1
1. INTRODUCTION 3
1.1 AD-NETT 3
1.2 Anaerobic digestion 3
1.3 Gas treatment 5
2. BIOGAS COMPOSITION 7
2.1 Biogas components 7
2.2 Biogas composition 8
3. STANDARDS ON GAS QUALITY AND EMISSIONS 9
3.1 Standards applicable gas quality for biogas utilisation. 9
3.2 Standards applicable on flaring of biogas 10
3.3 Standard emission for biogas fuelled internal
combustion engines 11
4. TREATMENT OF RAW BIOGAS 13
4.1 Introduction 13
4.2 Removal of water 14
4.3 Removal of H
2
S 15
4.4 Special gas engine lubricants 18
4.5 Removal of dust 18
4.6 Removal of CO
2
18
5. TREATMENT OF FLUE GAS 19
5.1 Lean burn engines 19
5.2 DeNO
x
systems 19
6. UPGRADING OF BIOGAS 21
6.1 Pressure Swing Adsorption (PSA) 21
6.2 Membrane separation 22
6.3 Physical (water, methanol) or chemical CO
2
-absorption
techniques 22
6.4 Evaluation of CO
2
removal techniques 23
7. CONCLUSIONS 24
REFERENCES 25
SUPPLIERS OF GAS TREATMENT EQUIPMENT 27
H0489.A0/R002/TS/GR - 1 - 25 January 2000
ABSTRACT
This technical summary on gas treatment in relation to anaerobic digestion (AD)
deals with the treatment processes for biogas in all stages of AD. Three major
topics are discussed:
the treatment of raw biogas in order to produce a biogas quality which is ac-
cording to the required standards for driving gas engines or gas fired boilers;
the treatment of flue gasses produced by gas engines or gas fired boilers in
order to meet the emissions standards in a certain country;
the upgrading of biogas to natural gas quality or a required synthesis gas
quality by the removing of macro components like CO
2
.

The context for the discussion of these three topics is presented in the first
three chapters of this technical summary.

Chapter 1 presents a short introduction of the
AD-NETT context;
the basic technology of anaerobic digestion;
the topic of gas treatment with the identification of the three main concepts
i.e. treatment of raw biogas, treatment of flue gas and the upgrading of bio-
gas;
the principles of gas treatment i.e. removal or conversion, application of ad-
ditives, catalysts, bacteria or based on a physical principle;
identification of specific elements in AD and gas treatment i.e. scale (small,
big) and budget (low, high), ease of operation, ease of monitoring, ease of
maintenance, fail safety, production of hazardous or toxic pollutants.

Chapter 2 gives a review on the composition of biogas. The description of the
composition concerns:
available components in the biogas;
treatment objectives for specific components i.e. reduction of toxicity, acidifi-
cation, harmfulness for equipment or compliance with emission standards;
effect of the digester feed and the AD-process itself on the composition of
the biogas;
variation of the biogas composition under normal operating conditions.

In chapter 3 the emission standards dealing with AD in the countries participat-
ing in the AD-NETT are discussed. First of all the policy and intentions of the
European Community and the available standards are presented. Furthermore
attention is paid to:
emission of components which have high priority in reduction;
standards in relation to biogas flaring;
standards in relation to biogas utilisation in gas engines, gas boilers or in re-
lation to the delivery of upgraded biogas to the natural gas grid.

Chapter 4 focuses on the treatment of the raw biogas in the form as the digester
produces it. Attention will be given to:
the removal of water;
the reduction of H
2
S by aerobic bacteria;
H0489.A0/R002/TS/GR - 2 - 25 January 2000
wet gas treatment systems;
gas treatment by utilising special gas engine lubricants;
removal of dust particles.

In chapter 5 the possibilities for treatment of the flue gasses that are formed by
the gas engine or gas boilerare reviewed. In this respect flue gasses are those
specifically generated from:
lean burn gas engines;
catalytic and non-catalytic DeNO
x
systems.

Chapter 6 deals with the possibilities to upgrade biogas to a quality required by
the natural gas grid. Upgrading techniques discussed are:
membrane separation;
wet treatment;
active carbon;
pressure swing adsorption.
In chapter 7 conclusions on the maturity of gas treatment for AD are presented
based on the present state of the art.
Chapter 8 presents a list of the main literature references with short descriptions
of the scope of each reference and relevant ordering information. In this chapter
an overview is given of the main suppliers of gas treatment equipment.
H0489.A0/R002/TS/GR - 3 - 25 January 2000
1. INTRODUCTION
1.1 AD-NETT
AD-NETT is a network of professionals working in anaerobic digestion (AD) of
agro-industrial wastes in Europe and Canada. AD-NETT is sponsored by the EC
FAIR programme in the EU and by national programmes in Switzerland and
Canada. The network began in January 1997 and will continue to December
1999.
The prime motive of AD-NETT is to enable exchange of information and experi-
ence and to disseminate this information to relevant organisations, such as po-
tential users and developers. In this respect AD-NETT publishes amongst oth-
ers on its Internet site http://www.ad-nett.org - news on developments in the
network, information about technical developments on AD and reports from da-
tabases of plant and contacts.
AD-NETT aims to examine and compare successes and failures of the world
wide application of AD technology in order to gain from past experience and to
pass this information on to potential users of the technology.
The information presented in this report is restricted to the application of AD for
treatment of agro-industrial wastes, although many of the gas treatment tech-
niques described are also suited for anaerobic wastewater treatment, treatment
of landfill gas, and digestion of VGF and other organic waste streams.
The technical summary on gastreatment is the Dutch contribution to the AD-
Nett, and was prepared by HASKONING, a Dutch engineering and consultancy
firm, in close co-operation with Novem, the Dutch Agency for Energy and the
Environment.
1.2 Anaerobic digestion
AD is applied in particular in the agricultural sector all over the world in the form
of small on-farm digesters producing biogas to heat farmhouses, dairies and
other farm buildings. Larger scale centralised anaerobic digesters (Centralised
AD) have also been developed, using feedstock imported from a number of
sources, specifically residues from livestock farming (such as dairy, beef and pig
slurry, or poultry litter) and the food processing industries (including vegetable
preparation and dairy food processing). Figure 1 presents a basic layout of an
AD-plant.
Anaerobic digesters produce conditions that encourage the natural breakdown
of organic matter by bacteria in the absence of air-oxygen. Figure 2 shows the
degradation routes in the AD-process, during which organic material is con-
verted by various types of micro-organisms into methane (CH
4
) and carbon di-
oxide (CO
2
), the main components of the biogas |ref 1|.
H0489.A0/R002/TS/GR - 4 - 25 January 2000
Feedstock
Storage and
pre-treatment
(mixing, screening)
Digester
Biogas
storage
Digestate
Biogas cleaning
Upgrading
(natural gas)
Engine
turbine
Gas burner
boiler
Flue gascleaning Fluegas cleaning
Gas treatment techniques reviewed
Flue gas Natural gas Flue gas
Figure 1: Basic Layout of an AD-plant
PROCESS MATERIAL BACTERIA
PARTICULATE ORGANIC MATERIAL
Hydrolysis
Fermentation
(acidogenesis)
Fermentation
(acetogenesis)
Methanogenesis
AMINO ACIDS / SUGARS
FATTY ACIDS
ACETATE / HYDROGEN
METHANE / CARBONDIOXIDE
Lipolytic, proteolytic
and cellulytic bacteria
Fermentative bateria
Hydrogen producing
bacteria
Methanogenic bacteria
PROTEINS CARBOHYDRATES LIPIDS
H0489.A0/R002/TS/GR - 5 - 25 January 2000
Figure 2: Anaerobic conversion of organic material into biogas.
In addition to CH
4
and CO
2
other volatile components like hydrogen sulphide
(H
2
S) and ammonia (NH
3
) are also formed by the mineralisation of organic ma-
terial during the AD-process and will finally end up in the biogas in small
amounts.
1.3 Gas treatment
At the site of the AD plant two gas streams are produced that need treatment:
biogas and flue gas.
Biogas is produced as an end product in anaerobic digesters and is normally
stored and utilised on site. Storage can be done in different types of storage
facilities like:
a water sealed, floating gas holder;
a gas bag;
the digester head space with a foil membrane;
a separate gas tank for high-pressure storage.
Gas engines or gas boilers produce flue gas. In order to meet emission stan-
dards applicable in a certain country flue gas treatment is needed.
In this report the following concepts of gas treatment are reviewed:
The treatment of the raw biogas as it is produced in anaerobic digesters in
order to protect storage facilities or to make the gas suitable for gas engines
or gas fired boilers.
The treatment of the biogas focussed on upgrading the biogas to a natural
gas quality or a required synthesis gas quality.
The treatment of the flue gasses that are produced by gas engines or gas
fired boilers in order to meet emission standards in a certain country.
The various treatment techniques that are considered in this report are based
on one of the following principles:
removal of certain constituents of the biogas;
conversion of certain constituents of the biogas into other, non or less harm-
ful components.
Table 1 lists the techniques that can be used for the treatment of biogas in rela-
tion to the compound to be removed.
If relevant, specific elements in AD and gas treatment like scale and budget
(high, low) of the plant, ease of operation, ease of monitoring, ease of mainte-
nance, fail safes and the production of hazardous or toxic pollutants are in-
cluded. Table 2 lists the importance of such parameters in relation to the size of
the AD-plant. From table 2 it is clear that for small scale AD-plants the treatment
technique to be considered should be a low-budget reliable technique that is
easy to operate, monitor and maintain. These demands have implications on the
type of treatment that can be applied and the possible end-use of the biogas.
Table 3 shows these possibilities for using biogas in AD-plants.
H0489.A0/R002/TS/GR - 6 - 25 January 2000
Table 1: Overview of techniques used for biogas treatment
COMPOUND REMOVED TECHNIQUE PRINCIPLE
Water Demister
Cyclone separator
Moisture trap
Water tap
Adsorption to silica
Glycol drying unit
physical
physical
physical
physical
physical
physical
H2S Air oxygen dosing
FeCl3 dosing to digester slurry
Adsorption to Fe2O3 pellets
Absorption with caustic solution
Absorption with iron solution
Absorption closed loop systems
Membrane separation
Biological filters
Activated carbon
Molecular sieves
biological
chemical
physical-chemical
physical-chemical
physical-chemical
physical-chemical
physical
biological
physical-chemical
physical
CO2 Pressure swing adsorption
Membrane separation
Absorption techniques
physical-chemical
physical
physical-chemical
Table 2: Importance of gas treatment aspects in relation to the size
of the AD-plant (+ = important, - = less important)
PARAMETER SMALL SCALE AD-PLANT
1)
LARGE SCALE AD-PLANT
2)
Low budget + +/-
Ease of operation + +/-
Unattended operation + -
Ease of monitoring + -
Ease of maintenance + +/-
Safety standards + +
Health standards + +
1) AD-plant with capacity lower than 5.000 tons feedstock per year (arbitrarily set)
2) AD-plant with capacity higher than 5.000 tons feedstock per year (arbitrarily set)
Table 3: Possible application of biogas in relation to the size of the AD-
plant (+ = yes, - = no)
END-USE SMALL SCALE PLANTS
1)
LARGE SCALE PLANTS
2)
Direct gas use (e.g. heating) + +
Production electricity +/- +
Combined heat power generation - +
Upgrading to natural gas - +
1) AD-plant with capacity lower than 5.000 tons feedstock per year (arbitrarily set)
2) AD-plant with capacity higher than 5.000 tons feedstock per year (arbitrarily set)
H0489.A0/R002/TS/GR - 7 - 25 January 2000
2. BIOGAS COMPOSITION
2.1 Biogas components
Biogas produced in AD plants is primarily composed of methane (CH
4
) and car-
bon dioxide (CO
2
), with smaller amounts of hydrogen sulphide (H
2
S) and am-
monia (NH
3
). Slight concentrations of hydrogen (H
2
), nitrogen (N
2
), carbon mon-
oxide (CO) and oxygen (O
2
) are occasionally present in the biogas. Finally the
biogas is usually saturated with water and might contain dust particles.
The properties of the main gas components mentioned above are outlined be-
low:
CH
4
gas is considered as a valuable fuel. The gas is non-toxic, non-smelling,
and is lighter than air. When burned CH
4
is converted into a molar equivalent
amount of CO
2
and water.
CO
2
is an inert colourless, odourless gas and is heavier than air. CO
2
is
mildly toxic, is an asphyxiant and has an occupational exposure standard
(OES) of 5.000 ppm. A higher CO
2
concentration in the biogas results in a
lower calorific value of the biogas.
H
2
S is a colourless gas. Since H
2
S is heavier than air, it might cause extra
danger at low levels. At low concentrations this gas has the typical smell of
rotten eggs. At higher, more dangerous concentrations is has no smell. Due
to its toxic properties hydrogen sulphide has an OES of 10 ppm. In addition
to its toxicity H
2
S is corrosive which can cause problems during combustion
of the biogas. When burned the H
2
S in the gas is converted into SO
2
, also a
toxic product, which can cause acidification.
NH
3
is a pungent and lachrymatory gas that is lighter than air. The OES is 10
ppm. When burned in a flare or a gas engine, NO
x
-products are formed.
Normally, NH
3
concentrations in the biogas are rather low.
Water vapour, although a harmless product, becomes corrosive in combina-
tion with the NH
3
, CO
2
and especially the H
2
S of the biogas. The maximum
water content of the biogas is governed by the gas temperature. When wa-
ter saturated biogas leaves the digester, cooling of the gas will result in con-
densation of water.
In view of the properties of the main biogas components listed above, treatment
of biogas will often be required. The treatment is commonly focussed on:
Removal of water, which is needed because of potential accumulation of
moisture in equipment in the gasline, the formation of a corrosive acidic so-
lution when water is combined with H
2
S and in order to create optimal condi-
tions for the end-use of the biogas.
Removal of H
2
S, which is required because it is toxic, corrosive and since it
can damage gas-equipment. The H
2
S concentration in the gas should be
kept below the recommendations of the manufacturer of the equipment
used. Furthermore, burning of biogas results in the oxidation of H
2
S to SO
2
.
In order to comply with environmental regulations for SO
2
emissions the H
2
S
level in the biogas should be kept sufficiently low.
Removal of CO
2
will be required if the biogas needs to be upgraded to the
quality of natural gas (in terms of Wobbe-index, corrosion, etc).
H0489.A0/R002/TS/GR - 8 - 25 January 2000
2.2 Biogas composition
The biogas production and composition in AD-plants is dependent on the type
of feedstock and the operational parameters used in the digestion process.
The feedstocks used for anaerobic digestion vary considerably in composition,
homogeneity and biodegradability. Table 4 shows some characteristics and op-
erational parameters for different agricultural feedstocks.
Table 4: Characteristics and operational parameters for different agricul-
tural feedstocks |ref. 2|.
FEEDSTOCK TOTAL
SOLIDS (TS),
%
VOLATILE
SOLIDS (VS),
% of TS
BIOGAS YIELD,
m
3
/Kg VS added
METHANE
CONTENT,
VOL. %
RETENTION
TIME,
days
Pig slurry 3-8 70-80 0.25-0.50 70-80 20-40
Cow slurry 5-12 75-85 0.20-0.30 55-75 20-30
Chicken slurry 10-30 70-80 0.35-0.60 60-80 > 30
Garden waste 60-70 90 0.20-0.50 n.a. 8-30
Fruit waste 15-20 75 0.25-0.50 n.a. 8-20
Food remains 10 80 0.50-0.60 70-80 10-20
Tables 5 show a comparison between biogas from an average AD plant and
natural gas.
Table 5: Composition of biogas from an AD-plant and natural gas in the
Netherlands |ref. 3, 4|.
COMPONENT DIMENSION NATURAL GAS BIOGAS
CH4 vol-% 85 55-70
CO2 vol-% 0,89 30-45
C2H6 vol-% 2,85 ---
C3H8 vol-% 0,37 ---
C4H10 vol-% 0,14 ---
N2 vol-% 14,35 ---
O2 vol-% < 0,5 ---
H2S mg/m
3
< 5 0-15.000
NH3 mg/m
3
--- 0-450
Humidity -- dew point at 10C saturated
Caloric value, lower-upper MJ/m
3
32-35 20-28
Wobbe index, lower-upper MJ/m
3
40-44 20-30
H0489.A0/R002/TS/GR - 9 - 25 January 2000
3. STANDARDS ON GAS QUALITY AND EMISSIONS
3.1 Standards applicable gas quality for biogas utilisation.
The biogas as produced in AD plants can be used for several purposes:
direct-gas use;
fuel for an engine connected to a generator to produce electricity;
combined heat and power generation;
upgrade of biogas to natural gas quality to run motor vehicle engines or to
supply to the local gas net (pipeline or substitute natural gas quality).
In the case of direct-gas use water and H
2
S removal will be the appropriate
treatment steps. If the gas is to be used by gas engines, or if it is upgraded to a
natural gas quality, the biogas composition should comply with the appropriate
requirements. Table 6 list typical requirements for gas engines.
Table 6: Typical requirements for gas engines |ref. 3|.
COMPONENT DIMENSION RANGE
Energy content MJ/m
3
13-21
Variation in energy content MJ/m
3
0-2
Maximum temperature feed C 40-60
Minimum delivery pressure mbar 25-80
Humidity biogas % < 70-80
H2S mg/m
3
< 1000-2000
Chloride and Fluor (total) mg/m
3
< 60-80
For upgrading biogas to natural gas quality removal of CO
2
, H
2
S, NH
3
, water
and dust is essential in order to achieve the required quality. Table 7 lists the
required gas quality in order to be used as natural gas substitute in the Nether-
lands. At the moment no European standard has been defined, but it can be
assumed that differences in the European countries will be small.
Table 7: Typical requirements for biogas to be injected in natural gas
line applicable the Netherlands |ref. 3|.
PARAMETER DIMENSION VALUE
Caloric value MJ/m
3
34,7-34,9
Wobbe-index MJ/m
3
43,5-44,4
H2S mg/m
3
< 5
H2O (dew point at 1 bar) C - 35
For utilisation of biogas as vehicle fuels the same upgrade technique is used as
for natural gas. In practice the upgrading of biogas up to vehicle fuel quality in-
volves removal of CO
2
, H
2
S, NH
3
, particles and water. The methane contents
should be at least 95 % |ref. 5|. Quality requirements for vehicle fuel of biogas
are different in different countries.
H0489.A0/R002/TS/GR - 10 - 25 January 2000
3.2 Standards applicable on flaring of biogas
If biogas utilisation is not possible, biogas combustion with flares is required,
since direct emission of the biogas into open air is prohibited for safety and
health reasons.
Guidelines in the Netherlands
In the Dutch emission guidance (NER 3.5/90.1) the following restrictions for
permanent flares are mentioned:
the outlet temperature of the flue gas has to be at least 900 C;
the residence time in the flare has to be at least 0.3 seconds;
the flare has to be of the closed type (no visible flame). However, if flares
are only being used during periods of maintenance (of utilisation equipment),
the use of a simple open or half-open flare is allowed.
The maximum limit of H
2
S and other organosulphur compounds in the biogas to
be flared is 50 ppm. If this limit is exceeded, sulphur has to be removed from the
biogas with a sulphur removal to this limit of 50 ppm or a removal efficiency of at
least 98 %. To prevent the formation of dioxins, the halogenated hydrocarbons
content has to be lower than approximately 150 mg/m
3
.
Guidelines in other countries
At present there is no European guideline regarding standards for the flaring of
biogas. Based on the information available at this stage it seems that in many
European countries specific rules for the flaring of biogas do not exist. For ex-
ample: Denmark, Spain, Austria, the United-Kingdom and Italy do not have any
regulating rules for flaring of biogas. In countries that do have emission stan-
dard, there can be considerable differences. Table 8 shows the standards on
emission control on landfill gas flares in Germany and Switzerland. In addition
the recommended values for the United Kingdom are shown.
Table 8 Emission controls on landfill gas flares based on the German TA-
luft regulations, the Swiss regulations and the recommendations
used in the United Kingdom |ref 6|.
GUIDELINES UK TA LUFT GERMANY SWISS DIMENSIONS
Carbon monoxide
Nitrogen oxides
Unburned hydrocarbons
Dust
SO2
HCl
Cd
Hg
Dioxins and furans (TEQ)
50
150
10
---
---
---
---
---
---
50
200
10
10
50
30
0.05
0.05
0.18
60
80
20
20
50
20
0.1
0.1
---
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
ng/m
3
Furthermore it is expected that in the near future the use of open flares will be
limited and that flaring of biogas will be restricted to enclosed flares in the UK.
H0489.A0/R002/TS/GR - 11 - 25 January 2000
3.3 Standard emission for biogas fuelled internal combustion engines
Guidelines in the Netherlands
In the Netherlands, the emission of NO
x
in exhaust gasses of biogas fuelled in-
ternal combustion engines is restricted |ref. 7|:
new engines < 50 kW: 800 g NO
x
/GJ * 1/30 of the engine efficiency;
new engines > 50 kW and < 50 MW: 140 g NO
x
/GJ * 1/30 of the engine effi-
ciency.
This means that if the engine efficiency increases, higher emissions are ac-
cepted. The engine efficiency is the percentage of power (energy) output that
can be obtained from the energy input.
Guidelines in other countries
There can be considerable differences in the regulations between the different
European countries. In addition to the restrictions for emission during biogas-
combustion used in the Netherlands, the standards as applied in Spain, Den-
mark, Italy and Austria are given as examples for the various regulations and
standards which are applied within Europe.
Austria
Table 9 gives the data regarding emission restriction during the combustion of
biogas as applied in Austria. The emission restriction are based on:
- Lufteinhaltverordnug fr Kesselanlagen BGBI Nr. 19/1989 idgf (LVR-K);
- Deutsche Technische Anleitung zur Reinhaltung der Luft (TA-Luft 1986)
|ref 8 |;
- Richtlinienvorschlages Entgasung von Deponiekrpern der WAV
(WAV, 1997) |ref 9 |.
Table 9: Maximal emission values as applied in Austria based on the LVR-
K, TA-Luft 1986, and WAV 1997.
WAV 1997 PARAMETER LVR-K
1)
TA-LUFT
1986
2)
< 2.000 m
3
/h > 2.000 m
3
/h
DIMENSION
Dust
NOx
SO2
CO
50
-
-
100
5
200
500
100
5
-
100
100
5
200
100
100
mg/m
3
mg/m
3
mg/m
3
mg/m
3
HCl
HF
Pb, Zn, Cr
As, Co, Ni
Cd
Hg
Total organic carbon
PCDD/PCDF
CO:CO2
H2S
O2 content
30
0,7
5
1
0,1
0,1
20
0,1
0,002
-
11
20
5
5
1
0,2
0,2
-
-
-
5
3
20
5
5
1
0,1
0,1
20
0,1
0,002
5
3
20
5
5
1
0,1
0,1
20
0,1
0,002
5
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
ng/m
3
-
mg/m
3
%
1)
small plants,
2)
landfill gas
Denmark
H0489.A0/R002/TS/GR - 12 - 25 January 2000
Danish regulations are focussed on natural gas and natural gas fuelled engines.
For engines > 120 kW the following restrictions exist |ref 10 |:
- NO
x
550 mg/Nm
3
- CO 500 mg/Nm
3
- unburned carbonhydrogens 1500 mg/Nm
3
with 30 % electric efficiency
Biogas is not specifically mentioned in the regulations in Denmark.
Spain
In Spain there are no strict regulations regarding NO
x
emission standards during
combustion with gas engines using natural gas or biogas. Other more general
regulations regarding diverse industrial activities give some tentative guidelines
regarding emission standards. These guidelines are |ref 11 |:
- SO
2
4300 mg/m
3
- NO
x
615 mg/m
3
(measured as NO
2
)
- CO 625 mg/m
3
Italy
In Italy a number of regulations exist regarding anaerobic digestions systems
and biogas utilisation. Table lists 10 emission standards as defined in Italy.
Table 10: Conditions for biogas-utilisation and maximal emission standards
for the combustion of biogas as applied in Italy |ref 12|.
PAREMETER AVERAGE DAILY AVERAGE 30 Minutes AVERAGE 1 hour UNIT
Dust
NOx
SO2
CO
10
200
-
50
10-30
-
-
100
-
-
-
-
mg/m
3
mg/m
3
mg/m
3
mg/m
3
HCl
HF
Cd, Ti
Hg
Total organic carbon
10
1
-
-
10
10-60
2-4
-
-
-
-
-
0.05
0.5
-
mg/m
3
mg/m
3
mg/m
3
mg/m
3
mg/m
3
When evaluating the regulations in the different countries it is seen that there is
a considerable variation. To our knowledge, at present there is not yet a stan-
dard European guideline or European regulation. When applying anaerobic di-
gestion one should check local and national regulations and legislation.
H0489.A0/R002/TS/GR - 13 - 25 January 2000
4. TREATMENT OF RAW BIOGAS
4.1 Introduction
The raw biogas produced in a digester is normally treated in order to remove
water, H
2
S, dust and/or CO
2
. The choice of the cleaning method employed and
the compound to be removed depends on the type of end use of the gas.
Table 10 shows the compound(s) of the biogas that needs to be removed in re-
lation to the end-use of the gas.
Table 11: Removal of specific compounds present in biogas, in relation to the
gas utilisation (+ = yes, - = no).
BIOGAS UTILISATION WATER H2S DUST CO2
Direct heating (gas boilers/burners) + +
1)
+ -
Electricity (gas engine) + +
1)
+ +/-
2)
Upgrade for natural gas + + + +
1)
removal required if input limits are exceeded
2)
dependent of CO2 content biogas and manufacturers specification.
The treatment methods for the removal of water, H
2
S and dust are reviewed
below. The more sophisticated removal methods for CO
2
are discussed in detail
in chapter 6 that deals with biogas upgrading techniques to natural gas quality.
Figure 3 show the different removal techniques which will be discussed in more
detail in the chapter.
DIGESTER
Removal of water, f oam
and dust
Removal
of H
2
S
Specific
removal of dust
Removal
of CO
2
Figure 3 Treatment techniques for biogas.
Removal of water and foam is always needed for the prevention of corrosion in
the biogas line. At present very simple and cheap methods exist that will remove
water in sufficient quantities. Water removal is normally accomplished with the
removal of foam and dust. If the biogas is to be used removal of H
2
S is needed
in most cases. CO
2
removal and specific methods for the removal of dust is only
need when a high quality gas is required. This can be the case when the biogas
is to be used as a substitute for natural gas or when sensitive equipment is
used.
H0489.A0/R002/TS/GR - 14 - 25 January 2000
4.2 Removal of water
In AD plant technology the removal methods for water are commonly based on
separation of condensed water or gas drying. In addition to water also other
impurities in the biogas such as foam and dust are removed.
Condensation methods
Methods employed using separation of condensed water are based on the prin-
cipal that water droplets are caught or entrapped and subsequently removed.
The removal can be either manually or automatic. Techniques using separation
of condensed water include the application of:
demisters, in which liquid particles are separated with a wired mesh (micro
pores);
cyclone separators, in which water drop(let)s are separated using centrifugal
forces equal to several hundred gravities;
moisture traps, in which condensation of water by expansion of the biogas
takes place;
water taps in the gaspipe, from which condensed water from the biogas can
be removed from the gas.
Of the methods mentioned above the simplest method is based on using water
taps in the gas-pipe. Normally this will give a sufficient removal of water for the
gas to be used in gasengines.
Drying methods
Methods based on gas drying include:
Cooling of the gas and leading it through a demister with micro pores (cool
dryer)
When the gas is cooled the gas becomes over-saturated with water. Dew
points of 20 tot 2 C can be reached. As a result, condensation of the water
in the gas occurs. The condensed water is entrapped in a demister. In order
to have a high efficiency the demister is equipped with micro pores.
Adsorption of the gas to silica (adsorption dryer)
Using adsorption dryers a high removal of water can be achieved. The gas is
led through a column filled with silica in which dew points of -10 tot -20 C
can be reached. Usually two columns are used simultaneously: one column
for adsorption of water, while the other is regenerated in that stage. Regen-
eration can be done by evaporation of the water by heating. As alternatives
for silica also activated carbon or molecular sieves can be used for this dry-
ing process.
H0489.A0/R002/TS/GR - 15 - 25 January 2000
Glycol drying unit (glycol dryer)
Drying takes place using tri-ethylene-glycol (a water binding component).
Dew points of -5 tot -15 C can be reached. Used glycol is pumped into a re-
generation unit, where regeneration takes place with a temperature of 200
C.
Removal of water is essential in preventing potential accumulation of moisture in
equipment installed and the formation of a corrosive acidic solution. However,
as indicated in paragraph 1.3 and tables 2 and 3 the appropriate technique is
strongly dependent on the size of the AD-plant and the end-use of the gas. For
small scale AD-plants water removal techniques are limited to the application of
moisture traps or water taps in the gas line. These methods are commonly used
and are sufficient for using of gas in gas-engines. The other techniques men-
tioned are not justified economically or do not fulfil the criteria mentioned in ta-
bles 2 and 3. Only if the objective of the biogas treatment is upgrading to a
natural gas or vehicle fuel quality, water removal based on drying methods can
be considered.
4.3 Removal of H
2
S
A number of techniques have been developed over the years for the removal of
H
2
S from the biogas. These techniques are outlined in this section.
Air/oxygen dosing to the biogas system
This technique is based on the biological aerobic oxidation of H
2
S to elemental
sulphur by a group a specialised micro-organisms. In order to have the bacteria
developed in the biogas system, liquid-manure-wetted surface is required. The
following reaction occurs in the biogas:
2 H
2
S + O
2
2 S + 2 H
2
O
The small amount of oxygen (approximately 5 %) required in this method is in-
troduced in the biogas system e.g. by using an air pump. As a result the sul-
phide in the biogas is oxidised into sulphur and the H
2
S concentration of the
biogas is lowered. The results obtained with this method to date are very prom-
ising. A reduction of H
2
Slevels down to 20-100 ppm H
2
S which equals 30- 150
mg/m
3
H
2
S, and removal efficiencies of H
2
S between 80-99 % have been
achieved |ref. 13|. The H
2
S removal obtained with this method is sufficient for a
direct use of biogas in gas-engines. On the other hand, the H
2
S concentration
remains too high for the use of biogas as a substitute of natural gas. The major
advantages of this removal method are:
Investment and exploitation costs are very low compared with other H
2
S re-
moval methods.
Operation, monitoring, maintenance and unattended operation are very easy
to realise.
No special chemicals or equipment are required.
H0489.A0/R002/TS/GR - 16 - 25 January 2000
Addition of iron chloride to the digester slurry
This technique is based on the formation of insoluble iron sulphide salts in the
digester slurry. The precipitation reaction of the iron salt can be written as:
2 Fe
3+
+ 3 S
2-
2 FeS + S
Due to the precipitate formed stripping of H
2
S to the biogas is prevented. The
method is very effective in reducing high H
2
S levels. A reduction of H
2
S concen-
trations in the biogas down to 100 ppm has been achieved. The major advan-
tages of this method are:
Operation and exploitation costs are low.
Operation, monitoring, maintenance and unattended operation is easy to
realise.
H
2
S is prevented from being transferred to the biogas, so no part of the gas
line, including the part prior to a biogas treatment, is brought in contact with
the H
2
S.
Adsorption using iron oxide pellets
In this technique, in which the gas is led through a box of pellets, the iron oxide
pellets reacts with the H
2
S in the biogas according to the following reaction:
Fe
2
O
3
+ 3 H
2
S Fe
2
S
3
+ 3 H
2
O
Regeneration of the iron pellets is done with oxygen:
2 Fe
2
S
3
+ 3 O
2
2 Fe
2
O
3
+ 6 S
Normally two boxes of pellets are installed in the gasline. One box is loaded
whereas the other is regenerated. When the iron pellets are completely covered
with sulphur the pellets are replaced. Adsorption using iron boxes is a simple,
cheap and easy to operate and maintain method in which high removal efficien-
cies can be obtained. The disadvantages of the method are: the great amount
of heat released during the regeneration, dust of the packing can be toxic and
the method is sensitive for a high water content of the biogas.
Absorption with liquids
In this method we can distinguish physical and chemical absorption processes.
In physical absorption H
2
S is removed by absorption of H
2
S in water or organic
solvents. Due to high consumption of water or high cost associated with regen-
eration of the liquid this method is not suitable for use in AD plants. By adding
chemicals to the water the absorption process can be greatly enhanced result-
ing in a chemical absorption process. We can distinguish the following options
of chemical absorption of H
2
S:
Chemical absorption with a diluted sodium hydroxide (NaOH) solution. The
NaOH reacts with hydrogen sulphide to form sodium sulphide or sodium hy-
drogen sulphide. The sodium salts, which are formed, have to be disposed
of and the method is not regenerative.
H0489.A0/R002/TS/GR - 17 - 25 January 2000
Chemical absorption with iron salts solution. In this process an iron chloride
solution is used. The process is based on the formation of insoluble precipi-
tates that needs to be removed.
Chemical absorption using closed systems. In closed systems the absorp-
tion phase is followed by regeneration. An example is the Gluud-process. In
this process, H
2
S is removed using iron(III)hydroxide resulting in the forma-
tion of Fe
2
S
3
. Regeneration is done with oxygen-air. Another example is the
direct formation of elemental sulphur using an iron(III)chloride solution. By
adding complexing chemicals the formation of FeS or Fe(OH)
3
is prevented.
Regeneration again is done with oxygen-air.
The physical and chemical absorption processes mentioned above in general
have the disadvantage of a relative high consumption of water and/or chemi-
cals, which makes the method less attractive for small-scale AD-plants. For
large-scale AD-plants the method may become economically more feasible.
Other methods
Other methods that can be used include:
Membrane separation. H
2
S can be separated from the gas using a semi-
permeable membrane. In this process the biogas is led through a mem-
brane. H
2
S can pass the membrane whereas CH
4
and CO
2
cannot pass the
membrane.
Biological treatment. Biological treatment methods are based on using spe-
cific bacteria that are able to oxidise the H
2
S. In this method the biogas is led
through a special biological filter. In this filter H
2
S is in a first step absorbed
to a liquid phase and subsequently oxidised by the bacteria present in the
filter.
Activated carbon processes.
Application of molecular sieves.
Evaluation of H
2
S removal techniques
Table 12 shows a comparison between the different techniques for H
2
S removal.
Table 12 illustrates clearly that air dosing or FeCl
3
dosing are the best solutions
to remove H
2
S, especially for small-scale low budget AD plants.
However, when a natural gas quality is needed, techniques like chemical ab-
sorption have to be applied, In this case H
2
S removal is normally combined with
CO
2
removal.
H0489.A0/R002/TS/GR - 18 - 25 January 2000
Table 12: Comparison of different available H
2
S removal techniques
REMOVAL TECHNIQUE 1 2 3 4 5 6 7
Air dosing + + + + + + ++
FeCl3 dosing + + + + + + +
Fe2O3 pellets + + + +-/ + +/- +/-
Chemical absorption using caustic +/- + +/- +/- + +/- +/-
Chemical absorption using iron solution +/- + +/- +/- + +/- +/-
Chemical absorption based on closed loop system +/- + +/- +/- + +/- +/-
Membrane separation - - - - + + -
Biological treatment - +/- +/- +/- + + +/-
Activated carbon - +/- +/- +/- + +/- +/-
Molecular sieve - +/- +-/ +/- + +/- +/-
1. Application on small scale (+ = yes) 5. H2S treated gas < 250 ppm (+ = yes)
2. Application on large scale (+ = yes) 6. environmental impact (+ = low)
3. Simplicity (+ = simple) 7. costs (+ = low)
4. operation and maintenance (+ = little)
4.4 Special gas engine lubricants
Special gas engine lubricants are available that can deal with a relatively large
amount of contaminants, and research is on going. Engine suppliers are well
known with the different types of lubricants. The choice of the type of lubricant
depends mainly on the biogas quality and combustion conditions, which are
both specific for feedstock and location. If this information is known, a choice
can be made. Other factors to be considered include the frequency of lubricant
analyses and maintenance.
4.5 Removal of dust
As mentioned in paragraph 4.1 removal of water is accomplished with dust re-
moval. Normally the dust removed in this way is sufficient. Only if the gas is
used in sensitive equipment additional specific dust removal is required.
If specific dust removal is needed, dust filters have to be used. For this purpose
air filter type filters are needed and are often placed before regulator valves or
gas utilisation equipment. To prevent dust filters from clogging, the gas must be
free of any oil or water droplets. Dust filters must therefore be placed behind the
condensation traps and oil separators. The use of dust filters has consequences
for the choice of extraction machines, due to pressure losses. As mentioned in
paragraph 1.3 and tables 2 and 3 the appropriate technique is strongly depend-
ent on the size of the AD-plant and the end-use of the gas. This means that
dust removal will only be considered for large-scale AD plants.
4.6 Removal of CO
2
As indicated in the introduction of this chapter ( 4.1) treatment techniques for
the removal of CO
2
are reviewed in chapter 6.
H0489.A0/R002/TS/GR - 19 - 25 January 2000
5. TREATMENT OF FLUE GAS
5.1 Lean burn engines
The emission of flue gas from internal combustion (IC) engines can be con-
trolled using lean burn engines. Lean burn engines use a lambda sonde, which
measures the oxygen contents of the exhaust gas. With this information the
oxygen inlet, and in this way the oxygen-fuel mixture, is regulated. The lambda
control regulation results in optimal combustion conditions and low NO
x
emis-
sion.
The lambda sonde occasionally causes problems. Due to contaminants in the
biogas, the lambda sonde gets contaminated after a while, and gives inaccurate
results. Minimising the lambda (richer fuel mixture) causes a low NO
x
emission,
but results in an undesired increase of CO and hydrocarbons emission, and re-
sults in lower engine efficiency. A high lambda (lean mixture) leads generally to
a low NO
x
emission too.
Frequent maintenance is therefore necessary to keep the lambda sonde and
engine in optimal condition and to fulfil the required emission standards. Re-
placement of the oxygen measurement device is required at least every year.
5.2 DeNO
x
systems
DeNO
x
can take place by the use of non-catalytic and catalytic systems. The
systems described in this paragraph are usually applied at waste incineration
plants |ref. 14| and might be used at large scale utilisation of biogas from AD-
plants.
Non-catalytic systems
Non-catalytic DeNO
x
-systems are referred to as SNCR-systems. SNCR stands
for Selective Non Catalytic Reduction. SNCR-systems use ammonia or urea as
a reactant to reduce NO
x
.
The reactant is injected with steam into the fluegas just above the fire zone at
temperatures of 800 to 1000 C.
Catalytic systems
Two types of catalytic DeNO
x
are being discussed |ref. 15|:
non-selective catalyst, which reduces the emission of NO
x
, but also reduces
the emission of CO and hydrocarbons;
selective catalyst, which reduces NO
x
by using ammonia or urea, also re-
ferred to as the SCR, Selective Catalytic Reduction-system.
H0489.A0/R002/TS/GR - 20 - 25 January 2000
Non-selective catalyst
With the non-selective catalyst system NO
x
is reduced using CO as reactant:
NO + CO N
2
+ CO
2
The amount of CO is essential for optimisation of the DeNO
x
. The lambda of the
engine therefore has to be regulated. With this method also hydrocarbons (ex-
cluded CH
4
) are oxidised to water and carbon dioxide.
Selective catalyst (SCR)
NO
x
is changed into N
2
by using ammonia or urea as a reactant. Large scale
plants use ammonia (gaseous or in solution):
4 NO + 4 NH
3
+ O
2
4 N
2
+ 6 H
2
O
8 NO
2
+ 8 NH
3
7 N
2
and 12 H
2
O
Small scale DeNO
x
plants use urea for safety reasons.
The catalyst material in SCR-systems generally consists of a carrier of titanium
oxide (TiO
2
) with added active substances like vanadium oxide (V
2
O
5
) and tung-
sten oxide (WO
3
).
For the catalytic reaction, the lambda has to be higher than with the non-
catalytic system, and an exhaust gas temperature of at least 300 C is needed.
In the case of biogas fuelled engines, this type of catalysts is being used if a
very high DeNO
x
removal efficiency (> 90%) is required. For example if the ex-
haust gas is used as CO
2
source for greenhouses. The costs of a selective
catalyst DeNO
x
system are relatively high compared to the non-selective DeNO
x
system.
H0489.A0/R002/TS/GR - 21 - 25 January 2000
6. UPGRADING OF BIOGAS
Upgrading of biogas to substitute natural gas (SNG) involves a number of steps
|ref. 16, 17,18, 19, 20, 21|.
At first, water (vapour) and H
2
S have to be removed. Subsequently CH
4
/CO
2
separation must be carried out, using one of the following techniques for the
removal of CO
2
:
Pressure swing adsorption (PSA);
Membrane separation;
Physical or chemical CO
2
-absorption.
If the gas is meant for input in a natural gas piping system, the gas has to be
cooled and has to be compressed. Dust and (halogenated) hydrocarbons have
to be removed, and the gas needs to be odorised for safety reasons.
The three techniques focussed on the removal of CO
2
are reviewed below. The
techniques for the removal of water, H
2
S, dust and hydrocarbons are discussed
in chapter 4.
6.1 Pressure Swing Adsorption (PSA)
The PSA unit is schematically shown in figure 4. The unit exists of at least three
active carbon beds. The process in each bed (successively) is as follows:
The bed is fed with biogas under pressure. In this step the bed will be loaded
with carbon dioxide upon saturation, while methane is released. If the break
through point is reached, the process will be switched to the next bed. After
saturation the bed is depressurised to ambient pressure. In this step a CH
4
/CO
2
mixture is released with a high content of CH
4
and will be recycled into the feed.
The next step is to regenerate the active carbon bed by putting it under vacuum,
in which the carbon dioxide is released.
The PSA technique gives high efficiency rates (to 98%), but it is a relatively ex-
pensive process due to capital costs (control system).
Methane rich recycle
Biogas
Molecular sieves Mixing vessel
Submitted
natural gas
CO
2
H
2
S CFC
1
2 3
Figure 4: Pressure Swing Adsorption process
H0489.A0/R002/TS/GR - 22 - 25 January 2000
6.2 Membrane separation
Membrane separation is based on selective permeability of membranes for dif-
ferent components. Figure 5 shows the process scheme of this separation pro-
cess. The membrane efficiency varies between 73 % and 83%. Advantages are
the simple techniques and operation. Disadvantages are the efficiency and the
energy input for high pressures that are needed (20-35 bar) and high tempera-
ture.
Biogas
H
2
S CFC
CO
2
Substitute
Natural gas
Membranes
Figure 5: Upgrading biogas using gas separation membranes
A pilot study has been carried out |ref. 16| with a low-pressure (8 bar) mem-
brane separation system. An active carbon filter is needed in the feed line to
remove trace components. Relatively to high-pressure membrane separation
techniques, a reduction of costs could be achieved of 10 % per m
3
natural gas
equivalents. The major lack of knowledge during the pilot study was the long-
term behaviour of the membranes. Research on this has been initiated.
6.3 Physical (water, methanol) or chemical CO
2
-absorption techniques
These absorption techniques are based on the principle of separation of CO
2
and CH
4
by using an absorbent. Figure 6 shows the technique schematically.
One of the methods is the use of water as absorbent liquid. Biogas is fed into a
vessel. In this vessel the water is sprayed. During the flushing the concentration
of carbon dioxide decreases with distance and the gas becomes more concen-
trated with methane. The washing liquid is generated in two depressurisation
steps. At a pressure drop from 10 bar down to 4 bar, methane and part of the
carbon dioxide is released and is recycled. After the next pressure drop CO
2
is
released. The efficiency is about 95 %.
H0489.A0/R002/TS/GR - 23 - 25 January 2000
6.4 Evaluation of CO
2
removal techniques
In Table 13 the three reviewed CO
2
removal processes are compared.
Biogas
H
2
S
Substitute
Natural gas
CFC
CO
2
Drying Absorber
Washing liquid
regeneration
Figure 6: Upgrading biogas using physical absorption techniques
Table 13: Comparison of different available CO
2
removal techniques
UPGRADING BY PSA
Application Large scale plants (CDA)
Stage in the development Proven technique
Experience (in years) 12 years
Emission to the air Chlorinated and fluor hydrocarbons (can be flared)
CO2 reduction and CH4 reduction
Energy efficiency Energy input : energy output rate: 1:15
Gas pretreatment Gas drying, H2S removal
UPGRADING BY MEMBRANE SEPARATION
Stage in the development Proven technique (high pressure separation)
Pilot stage (low pressure separation)
Experience (in years) Appr. 10 years (high pressure separation)
Energy efficiency Energy input : energy output rate: 1:10
(high pressure)
UPGRADING BY PYSICAL/CHEMICAL ABSORPTION
Stage in the development Proven technique
Experience (in years) Appr. 10 years
Energy efficiency Information not available
H0489.A0/R002/TS/GR - 24 - 25 January 2000
7. CONCLUSIONS
This technical summary has dealt with different aspects of gas in AD plants. The
topics have been:
production and composition of biogas,
treatment of biogas,
treatment of flue gas.
On an average base the biogas formed in AD plants consist of:
55-80 vol.-% CH
4
20-45 vol.-% CO
2
0-1,5 vol.-% H
2
S
0-0,05 vol.-% NH
3
saturated with water.
Prior to utilisation the biogas needs to be treated in order to:
prevent corrosion of equipment installed.
fulfil demands on gas quality either for gas equipment or in case of gas up-
grading to natural gas quality.
Biogas treatment can involve the removal of water, H
2
S and/or CO
2
.
For the removal of water several methods based on separation of condensed
water or on gas drying are available. For small scale AD plants water removal is
limited to moisture traps and water taps in the gas line. If upgrading of biogas is
the treatment objective gas drying techniques become necessary.
In order to remove H
2
S several methods have been developed. Based on the
economics and simplicity in terms of (unattended) operation and maintenance,
air-oxygen dosing in the biogas and iron chloride dosing to the digester slurry
are the most suitable, especially for small-scale farms. For large-scale farms or
when upgrading of biogas to natural gas is the objective, chemical absorption of
H
2
S might become more feasible.
When biogas is upgraded to natural gas quality, in addition to water and H
2
S
removal, CO
2
removal is one of the gas treatment objectives. CO
2
removal
techniques that can be applied are a pressure swing adsorption unit, a high or
low-pressure membrane separation unit, and physical or chemical absorption
techniques.
Flue gases as produced at the site of AD plants by gas engines or boilers need
to be treated. Emission control can be done using lean burn engines or catalytic
or non-catalytic DeNO
x
systems.
H0489.A0/R002/TS/GR - 25 - 25 January 2000
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x
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H0489.A0/R002/TS/GR - 26 - 25 January 2000
|15| DeNO
x
-installation gas engines oil production site at Berkel, NAM/BUO,
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|19| Evaluation of Landfill Gas Upgrading Project Carbiogas B.V. at Nuenen,
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Netherlands, 1997.
H0489.A0/R002/TS/GR - 27 - 25 January 2000
SUPPLIERS OF GAS TREATMENT EQUIPMENT
Carbiogas B.V.
PO Box 90
8500 AB Joure
The Netherlands
Carbotech Anlagenbau GmbH
PO Box 130140
D-45291 Essen
Germany
Cirmac B.V.
PO Box 995
7301 BE Apeldoorn
The Netherlands
Dynaf Energietechniek B.V.
PO Box 54
800 AB Alkmaar
The Netherlands
Eltacom
PO Box 276
2700 AG Zoetermeer
The Netherlands
Petrogas Gas systems B.V.
PO Box 20
2800 AA Gouda
The Netherlands
Spruyt Energiesystemen B.V.
PO Box 8349
3503 Utrecht
The Netherlands
Zanthingh Energie systemen B.V.
PO Box 255
1430 AG Aalsmeer
The Netherlands

Anaerobic Digestion of Agro-Industrial

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