Petroleum Technology Quaterly

special features
Heat management
carbon capture
refining
gas processing
petrocHemicals
PETROLEUM TECHNOLOGY QUARTERLY
ptq
Q2 2010
cover and spine copy 3.indd 1 11/3/10 22:42:10
C h e c k o u t To p s e c a ta lysts a n d te c h n o lo g ie s
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2010. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic,
mechanical, photocopying, recording or otherwise without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held responsible for any
statements, opinions or views or for any inaccuracies.
5 Geographical trade-offs
ChrisCunningham
7 Processing Trends
11 ptq&a
15 Anode-grade coke from traditional crudes

MitraMotaghi,KanuShreeandSujathaKrishnamurthyKBR Technology
21 Catalytic reforming options and practices

TomZhou Fluor Enterprises
FrederikBaars Fluor BV
27 Planning for carbon capture
SuzanneFergusonFoster Wheeler
35 Online cleaning and decontamination of a butadiene unit
DinoPolveriniandCosimoCucinelli Polimeri Europa
MarcelloFerrara ITW
41 Optimisation of product yield and coke formation in a RFCC unit
SepehrSadighi,SeyyedRezaSeifMohaddecy,OmidGhabouli
andMehdiRashidzadeh Research Institute of Petroleum Industry
47 Optimising steam systems: part I
IanFlemingSpirax Sarco
55 Calculating column relief loads
HaribabuChittibabu,AmudhaValliandVineetKhanna Bechtel india PVE Ltd
DipanjanBhattacharya Bechtel Corporation
67 Crude oil selection: optimisation by weight or by volume?
MDPawdeandSachinSinghHindustan Petroleum Corporation Ltd (HPCL)
75 Designing for sulphur removal and storage: part 1
ShamimGandhi,WayneChungandKrishNangia Fluor Corporation
87 When MTBE outscores ETBE for bioenergy content
EelcoDekker BioMCN
95 Microchannel reactors in fuel production
DerekAtkinson Oxford Catalysts
JeffMcDaniel Velocys
101 Hydrotreating in the production of green diesel
RasmusEgeberg,NielsMichaelsen,LarsSkyumandPerZeuthenHaldor Topse
115 Selecting technologies for onshore LNG production
SaeidMokhatabTehran Raymand Consulting Engineers
121 Estimation of heat losses from process piping and equipment
AlirezaBahadoriandHariBVuthaluruCurtin University of Technology
124 Industry News
127 New Products
KBRsROSEsolventdeasphaltingprocessatNavajoRefningCompanys75,000bpdrefneryinArtesia,NewMexico.On
p15,KBRauthorsdiscussacombinationofsolventdeasphaltinganddelayedcokingtominimisefueloilproductionand
produceanodegradecoke. Photo: KBR
Q2 (Apr, May, Jun) 2010
www.eptq.com
p
t
q
Y L R E T R A U Q Y G O L O N H C E T M U E L O R T E P
p
t
q
contents/ed com copy 5.indt 1 29/3/10 12:18:28
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the process more secure with our innovative valves and controls, which is why
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T
he European Union has arguably
been the global leader in biodiesel
production and use, with overall
biodiesel production increasing from 1.9
million tonnes in 2004 to nearly 10.3 million
tonnes in 2007. Biodiesel production in the
US has also increased dramatically in the
past few years from 2 million gallons in 2000
to approximately 450 million gallons in 2007.
According to the National Biodiesel Board,
171 companies own biodiesel manufacturing
plants and are actively marketing biodiesel.1.
The global biodiesel market is estimated
to reach 37 billion gallons by 2016, with an
average annual growth rate of 42%. Europe
will continue to be the major biodiesel
market for the next decade, followed closely
by the US market.
Although high energy prices,
increasing global demand, drought and
other factors are the primary drivers
for higher food prices, food competitive
feedstocks have long been and will
continue to be a major concern for the
development of biofuels. To compete,
the industry has responded by
developing methods to increase process
effciency, utilise or upgrade by-
products and operate with lower
quality lipids as feedstocks.
Feedstocks
Biodiesel refers to a diesel-equivalent
fuel consisting of short-chain alkyl
(methyl or ethyl) esters, made by the
transesterifcation of triglycerides,
commonly known as vegetable oils or
animal fats. The most common form
uses methanol, the cheapest alcohol
available, to produce methyl esters.
The molecules in biodiesel are primarily
fatty acid methyl esters (FAME),
usually created by transesterifcation
between fats and methanol. Currently,
biodiesel is produced from various
vegetable and plant oils. First-
generation food-based feedstocks are
straight vegetable oils such as soybean
oil and animal fats such as tallow, lard,
yellow grease, chicken fat and the by-
products of the production of Omega-3
fatty acids from fsh oil. Soybean oil
and rapeseeds oil are the common
source for biodiesel production in the
US and Europe in quantities that can
produce enough biodiesel to be used in
a commercial market with currently
applicable technologies.
First-generation feedstocks for
PTQ Q2 2010 5
Editor
Chris Cunningham
editor@petroleumtechnology.com
Production Editor
Rachel Zamorski
production@petroleumtechnology.com
Graphics Editor
Mohammed Samiuddin
graphics@petroleumtechnology.com
Editorial
tel +44 844 5888 773
fax +44 844 5888 667
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Paul Mason
sales@petroleumtechnology.com

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Bob Aldridge
sales@petroleumtechnology.com
Advertising Sales Offce
tel +44 844 5888 771
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Publisher
Nic Allen
publisher@petroleumtechnology.com
Circulation
Jacki Watts
circulation@petroleumtechnology.com
Crambeth Allen Publishing Ltd
Hopesay, Craven Arms SY7 8HD, UK
tel +44 844 5888 776
fax +44 844 5888 667
ISSN 1362-363X

Petroleum Technology Quarterly (USPS 0014-781)
is published quarterly plus annual Catalysis edition
by Crambeth Allen Publishing Ltd and is distributed
in the USA by SPP, 75 Aberdeen Rd, Emigsville, PA
17318. Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to Petroleum
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Back numbers available from the Publisher
at $25 per copy inc postage.
Vol 15 No 3
Q2 (Apr, May, J un) 2010
Geographical
trade-offs
I
f the contents of this editors email inbox and quite possible yours since
the turn of the year are anything to judge by, the industry debate on emissions
trading and carbon control is generating enough heat for its own signifcant
contribution to global warming. Depending on where you are in the world, the
naysayers hold a signifcant lead over the doomsayers if number of paragraphs
published is the measure of the argument.
Whatever the level of political combat, and as this issue of PTQ demonstrates,
refners can always be relied upon to take the pragmatic approach and are
pressing ahead with practical plans to deal with cap-and-trade, carbon offsets or
whatever else government bodies care to unleash on them. On p27, Suzanne
Ferguson of Foster Wheeler Energy outlines the practical and economic issues
that must underlie a decision if any is to be taken to capture produced
refnery carbon emissions. Meanwhile, in our Processing Trends pages, beginning
on p7, Tom Yeung of Hydrocarbon Publishing outlines his organisations new
survey of refners actual plans for dealing with greenhouse gas emissions.
Sources of the information are a direct survey of refning companies and a
review of refners intentions that are already in the public domain.
The table accompanying the Processing Trends article is particularly telling for
the concerted support, or preference, it reveals for a carbon cap-and-trade
approach over a carbon tax system among Western European refners. Compare
this with the position in North America, where proposals remain in Congressional
limbo. The industry lobbying system in Brussels does not have the clout
of its counterpart in Washington, and there was never any doubt that
companies would have to march to the tune of the legislators in matters of
emissions regulation.
Established in 2005, the European Unions Emissions Trading System (ETS)
immediately became the worlds largest multi-state emissions trading scheme.
According to the system, large emitters of carbon dioxide within the EU must
monitor and annually report their CO
2
emissions, and they are obliged every
year to return an amount of emission allowances to the government that is
equivalent to their CO
2
emissions in that year.
A signifcant provision of the original ETS was the inclusion of allowances, or
carbon offsets. These are effectively credits granted to projects that claim money
has been spent to reduce carbon emissions. By potentially easing the burden
imposed by central government, carbon offsets made the ETS more attractive to
major producers of CO
2
, including refners. Since it is diffcult to demonstrate
any saving in emissions, unless CO
2
is either not produced or is permanently
stored, selecting projects and handing out permits to those whose work justifes
the credits is a major challenge for the Brussels bureaucrats. The estimated value
of carbon offsets by 2012, at current levels of growth, has been reckoned to
exceed the EUs total spending on renewable energy projects.
Nonetheless, there are approaches to a system of credit where it is due that
might work in a more appropriate fashion. For instance, at the European Refnery
Technology Conference held late last year in Berlin, a speaker called for rewards
for refners within the rules of the ETS. If refners took steps to produce cleaner
fuels, albeit producing more CO
2
in the process, emissions trading would refect
the improvement in fuel quality rather than the extra greenhouse gas produced.
However, since its latest review of the ETS, the EU seems determined to replace
the system of carbon offsets with a more auction-based trading system.
CHRIS CUNNINGHAM
p
t
q
contents/ed com copy 6.indt 2 12/3/10 13:25:27
2008 Criterion Catalysts & Technologies L.P. (cri815_0508)
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criterion 1 9/3/09 10:13:45
Refnery CO
2
management strategies
Tom Yeung, Hydrocarbon Publishing Company
tyeung@hydrocarbonpublishing.com
The recent global climate summit in Copenhagen,
Denmark, has not produced any clear guidance on when
and how defnitive climate legislation will be carried out
by many countries, including the worlds two largest
GHG emitters: China and the US. Meanwhile, on 23
February 2010, the US Environmental Protection Agency
(EPA) announced that it will slow down its earlier ruling
regarding CO
2
emissions from refneries, while also
possibly raising the threshold on these limits. These
happenings are indicative of diffculties in passing land-
mark legislation, which will affect national
environmental policies that tie in to the well-being of
heavy industry and other businesses. Oil companies
have anticipated uncertainties in upcoming climate
change rules that could ultimately impact company
sustainability. Therefore, many frms have already initi-
ated or implemented programmes throughout their
operations to address carbon emissions.
Taking these developments into account, Hydrocarbon
Publishing Company, in its latest strategic report, set out
to identify the specifc steps and strategies oil companies
are taking to help curb their GHG emissions. The data
were gathered through two methods: a direct survey
sent to oil companies (excluding any E&P concerns)
around the globe; and a comprehensive search of
company websites and press releases. Both the survey
and information search focused on four key areas:
energy effciency improvements, cogeneration, renew-
able power sources, carbon capture and sequestration
(CCS), and future legislative preferences.
Results of direct survey
The survey, titled Refnery CO
2
Management Survey,
contained roughly 20 questions and was conducted via
email across the global refning community in the
summer of 2009. A copy can be viewed at www.hydro-
carbonpublishing.com/survey.php.
Surveys were sent out to process engineers, mainte-
nance engineers, operations managers, unit managers,
and others in an attempt to establish what steps refners
are actively taking to reduce their carbon footprints. Chi
Square statistical tests were performed on the data to
determine statistical signifcance.
The survey focused on the four main topics mentioned
above, along with preferences in carbon legislation for
refners. In terms of preferred carbon legislation in pric-
ing CO
2
emissions, 47% stated that they would prefer a
carbon cap-and-trade (CCT) system, while 26% felt that
a carbon tax (CT) would be the best approach. These
preferences may have something to do with how a
particular refnery defnes carbon management. Carbon
management defnitions varied among survey
Reduce gasoline cutpoint
respondents: 34% stated that they defne carbon
management as internal emissions and product
consumption plus external power/utility generation;
32% agreed with defning carbon management as inter-
nal emissions and production consumption, but not
external power/utility generation; and 28% felt that the
entire life cycle needed to be taken into account to
derive an accurate defnition of carbon management.
With regard to energy management, 64% of refners
who responded are using or have used some type of
energy management programme at their refneries.
Energy effciency benchmarking was almost universally
used (94% of respondents). The use of energy manage-
ment programmes and energy effciency benchmarking
appears to be popular, as 70% of respondents stated that
they are seeing both economic and environmental bene-
fts from the use of these programmes.
On-site or exclusively associated power generation
systems was another focus area of the survey, with 68%
of refnery respondents currently utilising on-site or
exclusively associated power generation systems. Out of
the 68%, 42% are using a steam generator with a steam
turbine as the systems prime mover, while 44% are util-
ising natural gas as the primary combustion fuel.
Natural gas may be a popular fuel choice as it is a
cleaner-burning alternative to other fuels and could help
reduce GHG emissions in a refnery.
CCS is seen as a future technology that can help curb
GHG emissions from industrial plants, including refner-
ies. Of the refners surveyed, 51% are currently involved
or are considering involvement in CCS projects at their
facilities. Within a refnery, the main areas of focus for
these projects appear to be the H
2
plant (39%) and the
FCCU (24%). Post-combustion amine absorption (27%),
oxycombustion (23%) and pre-combustion steam reform-
ing (23%) are viewed as the best future carbon-capture
technologies, while injecting CO
2
into depleted oil or gas
felds and enhanced oil recovery (30%) are the preferred
storage methods for refners.
In a fnal summary question, refners were asked to
select purchase carbon credits, implement energy
management, utilise lower carbon fuels for utility gener-
ation, supplement fossil-based energy with renewable
energy or implement CCS as the best way to comply
with impending CO
2
caps. A majority (70%) feel that the
use of energy management programmes is the best route
for refners with regard to meeting GHG caps, followed
by purchasing carbon credits (15%).
Further statistical breakdowns of the survey were
performed by region (North America vs Europe) and
type of oil company (integrated vs independent vs
national). While North American and European
responses were almost identical and matched the global
responses presented above, major differences were seen
in the answers to certain questions when comparing
www.eptq.com PTQ Q2 2010 7
Processing Trends
proc trends copy 3.indd 1 8/3/10 14:41:35
An area in which many oil companies appear to differ
is the use of renewable energy for curbing GHG emis-
sions. The direct survey received insignicant responses
to the question of renewable energy use in a renery. On
the other hand, a majority of West European oil compa-
nies report involvement in renewable energy on their
websites and in press releases, which could be due to
large government subsidies; for instance, $0.133/kWh
for wind electricity in Germany and $0.6053/kWh for
photovoltaic solar electricity in Italy.
In contrast to the position taken by US and Canadian
rms, most European and Asian oil companies favour
CCT over CT. As expected, many small, independent
reners and oil concerns, particularly in Africa, provided
no climate change position or carbon strategies in any
public announcements, and their inputs are not included
in Table 1.
What does it mean?
Major oil companies are very proactive in formulating
strategies and taking steps to comply with future CO
2
cap legislation. In the name of business sustainability,
the impact on the bottom line must rst be considered
when investing in any sort of project to cut carbon emis-
sions. This fact may explain why the use of energy
management and/or energy efciency programmes is
such a popular method for reners looking to curb GHG
emissions. The direct survey and search of company
climate change policy announcements led to the same
conclusion. Reners prefer energy efciency improve-
ment programmes (often referred to as the low-hanging
fruit of GHG emissions mitigation options), which they
can obtain easily and recoup investment from quickly
while waiting for clarity on legislation.
On the other hand, short- and medium-term concerns,
such as depressed demand, poor margins, market
erosion by biofuels and decreasing consumption in
developed nations due to higher vehicle fuel efciency,
have not distracted companies from impending regula-
tory requirements for GHG emissions, which is why
they are also pursuing other carbon footprint reduction
options, such as renewable energy (solar and wind) and
CCS projects. The next decade could be a very challeng-
ing time for reners, but it could also provide
opportunities for well-prepared concerns to expand
market shares at the expense of many companies, partic-
ularly small ones, which lack resources and have no
strategy for tackling and adapting to the not-so-distant,
costly climate change legislation as revealed in the
survey and search. Despite uncertainties, many devel-
oped countries and China are expected to slash GHG
emissions by 2020, just ten years away.
For further discussions and analyses of the direct
survey and publicly announced company policies, plus
the latest technology advances for improving energy
efciency, cogeneration, renewable energy use and
carbon capture, refer to Hydrocarbon Publishings multi-
client strategic report, Renery CO
2
Management
Strategies: Technology Solutions to Reduce Carbon Footprint
and Meet Business Sustainability Goals (www.hydrocar-
bonpublishing.com/ReportP/CO
2
Cap.php), March 2010.
integrated and national oil companies to independent
reners. Both integrated (59%) and national (83%) oil
companies prefer CCT, while independent reners
prefer a CT (55%) to regulate GHG emissions. Also,
current or future involvement in CCS projects generated
varied responses. Again, a majority of integrated (70%)
and national (83%) oil companies mentioned participa-
tion in current and/or future CCS projects, while 80% of
independent reners indicated no current interest or
plan in CCS projects in the future. This distinct differ-
ence among these three groups could be due to the
currently exorbitant costs of CCS projects. Independent
reners would face sustainability problems if CCS was
required by legislation. As to the best way to comply
with impending CO
2
cap legislation, integrated (66%),
independent (67%) and national oil companies (50%) all
prefer energy management programmes.
Company policies from other sources
While the results of the survey presented above were
sent in by individual reneries, a search of oil company
websites and press releases was undertaken to deter-
mine corporate policies in regard to curbing renery
GHG emissions. Oil companies around the globe seem
to be actively engaged in utilising energy efciency
programmes and combined heat and power plants at
their operations. A number of rms are also involved in
consortiums researching the possibilities of using CCS to
help curb GHG emissions.
8 PTQ Q2 2010 www.eptq.com
www.ptqenquiry.com
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L o w w a te r
a b s o rp ti o n
C a ta ly s t
to x i n fre e
Company Country Energy Combinedheat Renewableenergy Carboncapture Positionincarbonpricing
effciency andpower (excludingbiofuels) andstorage(CCS) (CTorCCT)
UnitedStates
Chevron
CT
ConocoPhillips
a
CCT
b
ExxonMobil CT
FlintHillsResources
LyondellBasell
MarathonPetroleum CT
ValeroEnergy
Canada
HuskyEnergy
a
ImperialOil
a
a
CT
Irvingoil
a
SuncorEnergy
a
CCT
b
LatinAmericaandCaribbean
Ecopetrol Colombia
Petrobras Brazil
a
Pemex Mexico CCT
Petroperu Peru
WesternEurope
BP UK CCT
CEPSA Spain
a
Eni Italy
a
CCT
ERG Italy
a
CCT
GalpEnergia Portugal
a
HellenicPetroleum Greece
MotorOilHellas Greece
OMV Austria
a
CCT
RepsolYPF Spain
a
CCT
RoyalDutchShell UK/Netherlands CCT
Saras Italy
a
CCT
Statoil Norway CCT
Total France
EasternEurope,CIS
CzechRefning CzechRepublic
MOL Hungary
a
Rosneft Russia
MiddleEast
ADNOC(Takreer) UAE
a
SaudiAramco SaudiArabia
a
Tupras Turkey
Asia-Pacifc
AttockRefnery Pakistan
CaltexAustralia Australia CCT
CosmoOil Japan
a
CCT
CPC Taiwan
a
HindustanPetroleum India
IdemitsuKosan Japan
IndianOil India
JapanEnergy Japan
NewZealandRefning NewZealand
NipponOil Japan
Pertamina Indonesia
PetroChina China
a
Petronas Malaysia
Sinopec China
SKEnergy SouthKorea
a
aNotacommercialcarbon-captureproject,butpartofconsortiumresearchingCCSpossibilities
bNotfnalcompanydecision,butleaningtoward
Refnersfavouredstrategiesforcarbonreduction
Table1
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
info@revamps.com
www.revamps.com
PROCESS
CONSULTING
SERVICES,INC.
vacuum ejectors- and above all,
mate these interdependent com-
ponents into a fully integrated
system that reliably and consis-
tently maximizes VGO yields low
in microcarbon and vanadium.
Difficult? Not a job, certainly, for
anyone who only sits in the
office doing nothing but running
simulations. This isnt to say
that models are not important.
They are. But to produce any-
thing of real value these process
and equipment models need to
have been tested and checked
against actual measured pres-
sures, temperatures, flows and
stream compositions. And the
person who runs the simulations
must always keep in mind the
dictum of one of the grand old
men of refining: "Fluids obey the
laws of physics and not the
whims of the process designer."
In these times when every barrel
of crude needs to be converted
to highest value products, one
must look to the expertise not
just of the engineers who run the
models, but of those who also
wear Nomex and get dirty
measuring real unit performance.
Designing
Deepcut
Vacuum Units
That Really
Work
Every barrel of vacuum gas oil
(VGO) you can save from being
reduced to coke in the delayed
coker unit is a barrel more that
can go to the FCCU. Thats a
good reason to raise HVGO cut-
point. But how to do it? Some
people think the job can be done
just by running computer models
in the engineering office, relying
on vendors and their data sheets
for a clue to true equipment per-
formance. Experience, however,
shows it just aint so. For either a
grass roots project or a revamp,
designing a deepcut vacuum unit
to handle heavy sour crudes that
are becoming more common
today demands a lot more.
It takes personal experience in
doing tube-by-tube design of
the fired heaters and knowing
where and how to inject coil
steam, managing the hydraulics
of the heater including critical
two-phase flow in the tubes and
transfer line, how to deal with
corrosion and fouling in heat
exchangers, balance the intricate
details of tower internals and
To learn more about designing and
operating deepcut vacuum units,
ask for Technical Papers 185, 199,
and 205.
www.ptqenquiry.com
pcs.indd 1 11/3/10 22:28:04
Q
How do I achieve the maximum yield of LCO from the FCC
unit with the least possible increase in bottoms yield?
A
Yen Yung yen.yung@albemarle.com; Alan Kramer alan.
kramer@albemarle.com, Albemarle Catalysts
The frst thing the refner should do to maximise
distillate-range product in the refnery is to remove all
distillate from the FCCU feed. That means optimising
the separation in the upstream fractionators to remove
all components having an atmospheric boiling range
lower than 370C (700F) from the FCC feedstock.
Traditionally, light cycle oil (LCO) production is
enhanced by lowering reaction temperature and/or
reducing FCC catalyst activity. As a consequence,
conversion and bottoms cracking deteriorate. This can
be circumvented by applying bottoms recycle at the
expense of fresh feed intake.
The major challenge when maximising LCO yield is
hence the reduction of conversion without sacrifcing
bottoms conversion. Therefore, an FCC catalyst is
required with a high bottoms cracking power and high
selectivity to LCO production. Albemarles Upgrader
MD, Coral MD and Amber MD are designed to achieve
a maximum LCO yield. They feature:
High accessibility to maximise the diffusion of oil
feed molecules to the active sites for maximum bottoms
conversion
The high accessibility enhances the diffusion of
primary products from the reaction zone and conse-
quently minimises the conversion of LCO molecules to
secondary products
High matrix-to-zeolite ratio to minimise cracking of
LCO molecules
Tailored zeolite activity and selectivity for optimum
bottoms cracking potential
Maximum resistance to the deleterious effect of feed
contaminants like nitrogen, carbon residue and metals.
Furthermore, Albemarles BCMT-500 additive lever-
ages our catalyst technology and provides extreme
bottoms conversion power in an additive form. This is
the solution for refners faced with challenging situa-
tions caused by sudden or short-term yield degradation
due to opportunity feedstocks being sent to the FCCU.
Q
What catalyst type, or types, do you recommend for
minimum octane loss in FCC gasoline hydrotreaters?
A
George Anderson george.anderson@albemarle.com; Steve
Mayo steve.mayo@albemarle.com, Albemarle Corporation
Octane loss incurred across FCC gasoline hydrotreaters
is primarily a result of olefns saturation. The goal of
this operation is to achieve suffcient removal of
P
sulphur (and nitrogen) from the FCC naphtha stream
while minimising the saturation of olefnic molecules.
If the refnery is planning to hydrotreat full-range
FCC naphtha, it is generally preferable to utilise a
licensed selective naphtha HDS process. These
processes use operating conditions and catalysts
designed to minimise olefn saturation reactions while
maximising desulphurisation reactions. Gasoline prod-
uct specs with total ((R+M)/2) road octane loss of 3
octane numbers can typically be achieved. The cata-
lysts used in these processes are proprietary.
If the refnery is planning to post-treat the FCC
naphtha using conventional naphtha hydrotreating
technology, it is going to face some tough business and
technical choices. Conventional hydrotreating of full-
range FCC naphtha is generally uneconomic in terms
of octane loss and hydrogen consumption, regardless
of the type of catalyst used. Typical loss of road octane
will be on the order of 57 octane numbers, at best. In
this case, the refnery is best served by taking advan-
tage of the fact that olefns are most predominant in
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the light naphtha fractions, while sulphur, nitrogen
and aromatics are most predominant in the heavier
naphtha fractions.
Caustic treating processes can be used to remove
sulphur from the light naphtha fraction while main-
taining most of the olefns. The heavy fraction can be
fully hydrotreated to remove sulphur, nitrogen and
olefns, accepting the resultant octane loss. The octane
loss may be limited to 35 road octane numbers using
this strategy. CoMo catalyst is recommended for fully
hydrotreating the heavy naphtha fraction.
A further optimisation of this strategy may be
achieved by separating an additional, mid-range cut
with naphtha hydrotreating followed by naphtha
reforming. CoMo or NiMo catalyst can be used to
hydrotreat the mid-range naphtha fraction, depending
on the nitrogen content. All of these conventional
hydrotreating options require sweet FCC naphtha (ie,
pretreated FCCU feed) to successfully control octane
loss. These strategies also require that the refner have
the fexibility to continually optimise the light/heavy/
mid splits to meet the product specs and minimise
octane loss.
Q
Can you recommend a strategy for the best possible
production of transportation fuels from heavy vacuum residue
in a new-build refnery?
A
Hiroshi Toshima hiroshi.toshima@albemarle.com; Steve
Mayo, Albemarle Catalysts
The strategy for achieving clean distillate production
from vacuum residue is a crucial issue for a new refn-
ery. The strategy is even more important in light of the
trend toward heavier and more sour feeds, increasing
environmental legislation in many countries and future
bunker fuel regulations. The representative VR conver-
sion processes commercially applied are coking and
ebullated-bed hydrocracking. There are many coking
projects ongoing globally; however, coking produces a
low-value coke and provides a limited increase in
distillate production. Secondary hydrotreating of the
coker products requires more intensity due to the high
sulphur, nitrogen and aromatics content. E-bed
processes, with improved sediment reduction catalyst
technology, offer the opportunity to increase the distil-
late yield much more than earlier generation catalyst
technology. In many cases, this enables E-bed process
economics to be even more attractive than coking
economics.
Another technology for VR-to-distillate processing is
a solvent deasphalting (SDA) unit, replacing the
vacuum tower. The asphaltenes in VR are the mole-
cules that accelerate catalyst deactivation and
create instability in the products. Deasphalted oil
(DAO) can be used as the feed for a hydrocracking
process thatmaximises distillate production. Using SDA
to replace the vacuum tower and either DAO hydro-
cracking, DAO fxed-bed hydrotreating or DAO E-bed
hydrocracking processes may be one of the best solu-
tions for a new refnery to increase distillate
production.
Finally, slurry-bed hydrocracking (SHC) is an emerg-
ing technology. Several technology providers are
developing commercial slurry bed conversion
processes. Secondary upgrading of the SHC products
can be integrated in a high-pressure loop for improved
performance and economics. Depending on the time-
frame for design of the new refnery, SHC may be a
viable conversion technology for maximum distillate
production.
A
Yen Yung, Albemarle Catalysts
The FCC process is the premier conversion process to
convert residual feedstocks such as vacuum gas oil and
residues to transportation fuels. Modern design can
handle heavily contaminated feedstocks, thanks to
improvements in equipment design, such as feed
nozzles and catalysts coolers, and advancement in FCC
catalysts. Modern FCC catalysts are resistant to
metal contamination, which is encountered when
processing heavy vacuum residue. The process is very
selective for the production of gasoline and has the
fexibility to produce high amounts of propylene or
LCO, a diesel blending component. All major process
licensors offer a FCC design capable of cracking resid-
ual feedstocks for maximum gasoline, maximum LCO
or maximum propylene. Albemarle catalysts are
renowned for maximising the intake of residual
feedstocks to the FCCU, and the company champions
the continuous development of resid fuid
cracking catalysts, the latest being our Upgrader
catalyst family.
www.ptqenquiry.com
upgrading process for the oil refining industry, producing vast
quantities of transportation fuels. It is also expected that it
will gain importance as supplier of propylene worldwide
and occasionally ethylene. The FCC process and the
products it produces will have to meet strict emission
standards.
With respect to the processing of residual feedstock in
FCC, perhaps the most important change in modern
FCC catalyst design is the quantification and subsequent
optimisation of catalyst accessibility. Data from about 20
commercial experiences show that when contaminants
like iron, vanadium, calcium and sodium increase, cata-
lyst accessibility decreases rapidly. When catalysts with
high accessibility (as measured by the AAI Akzo Acces-
sibility Index) are used, very marked improvements in
activity and selectivity are achieved.
High accessibility and accessibility retention are
required the make the processing of even more contam-
inated residual feedstock possible. Akzo Nobel has intro-
duced the Opal, Sapphire and Coral catalysts line
featuring enhanced accessibility.
To enhance the production of light olefins, especially
propylene, in the FCCU stable narrow pore zeolites, eg
ZSM-5, are required. This has to be combined with a host
FCC catalyst featuring high propensity to produce
olefinic precursors, which are subsequently cracked to
light olefins.
Increased ability of the FCC catalysts system to make
lower sulphur-containing products is necessary for an
overall more profitable refining operation. Reduced
NO
x
and SO
x
emissions from the FCC stack are also
required.
The introduction of new FCC catalyst additives as
capital free solutions to cleaner air and cleaner fuels is
one of the most important developments in refining cat-
alysts during recent years. Specific examples from Akzo
Nobel are Resolve additives for full-range gasoline sul-
phur reduction, KDSO
x
and KDNO
x
for SO
x
and NO
x
abatement, respectively and KNO
x
-Down, a unique non-
platinum CO promoter with significant NO
x
reduction
capabilities
H ow are process licensors and plant operators

working together in adapting new information
technology systems that are becoming critical to the
molecular management of molecules in the process-
ing facility?
Goelzer: Traditionally, there has been a dis-connect
between process technology suppliers and refiners with
respect to on-line yield and molecular management as
opposed to yield expectations (often simplistically pre-
sented) for a base H&M balance scenario and perhaps a
few alternatives.
From the perspective of the process technology sup-
plier or catalyst supplier, extensive disclosure of molecu-
lar and heteroatom spectrums in base H&M balance
feeds and co-products could present serious commercial
problems with respect to marketing and competition
and guaranteed performance.
Refiners might under-recognise limitations of test
methods available for such detailed profiling and might
under-accept the importance of changes in crude slates
or in oilfield operations; and also squeeze the technolo-
gy/catalyst suppliers unduly with respect to
tolerance/flexibility.
Some refiners have begun to recognise the potential
for advanced on-line management of organic hydrogen
and molecular changes either via heuristic approaches
or via more sophisticated on-line and refinery laborato-
ry analysis along with actual use of this more sophisti-
cated analytical information.
For example, BP promoted a heuristic method for
FCC/RFCC units recognising that an upgraded or mod-
ern fluid catalytic cracker operating with equivalent
reactor outlet temperatures over 975F creates its own
pilot plant.
A number of refiners are beginning to routinely (daily
or weekly) employ low temperature simulated distilla-
tion analysers (nominally under ASTM D-2887) and
high temperature simulation distillation analysers for
sophisticated monitoring of distillation and fractiona-
tion and lift/vaporisation potentials. ASTM D-86 along
with RVP and flash point testing remain optimal choice
for distillation quality control on finished white prod-
ucts and ASTM D-1160 still constitutes reference stan-
dard for sales vacuum gas oils. But ASTM D-86 and ASTM
D-1160 can be misleading or very misleading when
employed for other than these product quality purposes.
Berthold Technologies developed an online analyser
for directly measuring organic hydrogen in feeds and to
key marker products from conversion units
(FCC/RFCC/VGO hydrocrackers/delayed cokers/ULS
diesel hydrotreaters), ie Berthold LB-340-B
hydrogen/sulphur/gravity analyser. But acceptance has
been slow regarding day-to-day optimisation of opera-
tions and processing severities based on organic hydro-
gen as key fundamental parameter of refining.
QUES TI ONS & ANS WERS
PTQ AUTUMN 2002
18
Kidextractor
Quarter page
Do you have any questions you would like to put to our
panellists? Send them to editor@petroleumtechnology.com
ENQUIRY NO 314
www.ptqenquiry.com
After you have used
it the first time, the
Kid Extractor will
become your trusty
hydraulic-tube-
bundle-extractor
KI DExtr actor Ltd.
P.O. Box 11, Zebbug
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Fax. 00356- 21- 462755
MOBILE:00356-94-20596
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Website:www.kidextractor.com
Document1 21/9/2002 12:09 Page 1
Q&A copy 3.indd 2 10/3/10 09:39:10
www.mprservices.com
There is a company that can help you monitor and optimize the operation of your amine/
glycol treating units! MPR Services has been doing this successfully since 1989 for their
customers around the world!
What Does MPR Technology Do?
Remove contaminants
Reduce solvent losses
Eliminate foaming
Prevent corrosion
Stop forced shut-downs
Since 1989, MPR Services, Inc. has used their technologies to
clean amine and glycol solvents. Utilizing special ion exchange
resins with unique control and regeneration methods, the HSSX
Process continues to be used successfully to remove Heat Stable

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chlorides, sodium and other contaminants.
The HSSX Process removes HSS from; MEA, DEA, MDEA, DIPA, Sul nol M, Sul nol D, Flexorb
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and many other proprietary and generic amine and glycol solvents.
Upon completion of the HSSX Process, your amine or glycol system will exhibit improved performance with:
Less foaming,
Less lter plugging,
Lower amine losses,
Lower corrosion rates,
Reduced solvent circulation,
Reduced stripping steam requirements,
Lower NH
3
levels at the waste water treatment plant.
The HSSX Process can take a slipstream from your system and clean the solution on-line, or it can clean the
solution off-line while the system is down. The HSSX Process may also be used to clean spent amine or glycol
from storage tanks.
MPR Services has cleaned over 4 million gallons of amine and glycols for many of the major oil companies,
gas plants, ammonia plants, and coal gasi cation plants. MPR provides all necessary personnel and specialized
equipment to perform their services at the plant.
MPR also offers full analytical laboratory services to support job planning, as well as support on-site to jobs in
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MPR Services can help you monitor and optimize the operation of your amine/glycol treating units!
Contact us today!
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mpr.indd 1 9/3/10 14:06:53
ConocoPhillips is committed to offering environmentally
friendly delayed coking technology all over the world. We
design and implement industry- leading systems that meet
stringent environmental emissions standards globally.
Our advanced closed blowdown system, an essential
part of the ConocoPhillips delayed coking process, safely
condenses the steam and hydrocarbon vapors during the
coke drum steaming and water quench operations. This
system safely recovers heavy hydrocarbons and inerts
released from the coke drums during upset conditions.
The coke storage area is comprised of high walls to reduce
wind- borne dust, and the coke is handled by overhead
crane. The ThruPlus
design meets rigorous environmental

guidelines for venting the coke drum after quenching the
coke. The processing of oil bearing solid waste recovers
solids and oily solids from the ref nery. The oil is contained
within the coker process and converted to valuable
ref ned products.
ConocoPhillips Billings ref nery was awarded the
Clean Air Act Excellence Award in 2006 and the EPA
Energy Star
Award in 2006 and 2007.

At ConocoPhillips, we believe we are
def ned by what we pass on to the next
generation. Our ThruPlus
Delayed Coking
Technology offers safe, clean, proven
and prof table coking units for several
generations in the future. Safe. Clean.
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ConocoPhillips. Energy for tomorrow.
Tur ni ng heavy cr ude i nt o hi gh val ue
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For help solving your delayed
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us via our Web site at
www.ThruPlus.com.
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conoco.indd 1 9/3/10 14:08:24
Anode-grade coke from traditional crudes
I
n an era of economic and politi-
cal uncertainties, refnery
margins will continue to be
dictated by processing heavier,
sourer crudes. The dramatic
increase in residuum content from
10% in light sweet crudes to 50% in
extra-heavy crudes poses interest-
ing challenges, while presenting
some unique opportunities. This is
especially true when it comes to
producing high-value products
from low-value, bottom-of-the-
barrel streams.
According to conventional
wisdom, the residuum is either
removed as fuel oil or asphalt, or
subjected to thermal conversion
processes for upgrading. Traditional
resid upgrading methods include
resid fuidised catalytic cracking
(RFCC), visbreaking (VB) and
delayed coking (DC).
RFCC is a widely used carbon
rejection technology to convert
high-boiling, high-molecular-weight
hydrocarbon fractions to more valu-
able gasoline, olefnic gases and
other products. However, due to
the nature of the process, it is
limited to processing lighter, low-
metals, low-sulphur residues.
Visbreakers are essentially a
means of improving the viscosity of
the residuum so as to minimise the
addition of valuable distillate
boiling-range cutter stock to meet
fuel oil specifcations. As world
economics seems to be infuenced
by the use of natural gas, the
production of fuel oil has a nega-
tive effect on refnery product slate
and economics. This situation is
expected only to worsen as refners
face regulatory pressures ranging
from new maritime bunker fuel
A combination of solvent deasphalting and delayed coking is an option to
minimise fuel oil production and produce anode-grade coke
MItrA MotAghI, KAnu Shree and SujAthA KrIShnAMurthy
KBR Technology
specifcations to carbon dioxide cap
and trade and carbon footprint
limitations. This leaves refneries
with the challenge to minimise fuel
oil production.
Carbon rejection choice
Residues from heavy crude oils
contain high concentrations of
sulphur, complex hydrocarbons and
heavy metals such as nickel and
vanadium. Due to the nature of
these residues, delayed coking tech-
nology is the most commonly used
carbon rejection technology. In
addition, it enables the refner to
signifcantly reduce production of
low-value fuel oil. Coking is a ther-
mal cracking process in which,
typically, a low-value residual oil,
such as atmospheric or vacuum
residue (VR), is converted into valu-
able distillate products and off-gas,
leaving behind low-value fuel-grade
coke. High-sulphur petroleum coke
prices are distressed and, as is
evident in Canada, coke is just
being piled up in large quantities
with no real economic outlet.
On the other hand, anode-grade
coke is in high demand in the elec-
trode industry. The world market
for anode-grade coke is projected to
be approximately 1720 million tpa.
The high price differential between
the two grades, coupled with
increasing demand for anode-grade
coke, creates an unprecedented
need to fnd an alternate path to
improve the economics of coke
production while maintaining
higher refnery margins.
Production of anode-grade coke
is greatly infuenced by the sulphur
and metal content of the feed or, for
all practical purposes, the VR. The
volume and quality of the residue
is essentially determined by the
quality of the vacuum gas oil frac-
tion and the ability to process this
fraction through conventional
hydroprocessing or catalytic crack-
ing conversion units. In most cases,
the limiting factor is the metals
content or the Conradson carbon
residue (CCR) in the gas oil.
The residue volume and quality
is by balance a reject defned by gas
oil quality. Furthermore, not much
attention has been paid to improv-
ing the quality of the residue prior
to coking, primarily because of
issues associated with the methods
used to improve the residue
quality.
One approach to reduce the
metals and sulphur content of the
residuum is hydrotreating. While
hydrotreating addresses the sulphur
and metals content of the feed, it is
an expensive proposition incurring
high capital investment due to high
operating pressures and high
hydrogen consumption with poor
catalyst cycle length. In addition,
hydrotreating increases the level of
saturates in the residuum, which
may make it unsuitable for anode
coke production because other
physical requirements, such as
the world market for
anode-grade coke
is projected to be
approximately
1720 million tpa
kbr.indd 1 8/3/10 14:45:32
volatile carbonaceous material
content, bulk density and grindabil-
ity, may no longer be met. So, in
reality, hydrotreating is not an
economic option for residuum
upgrading for anode coke produc-
tion, and is therefore not widely
practised.
Three-product ROSE
The solution to obtaining anode-
grade coke from traditional crudes,
therefore, lies in alternative low-
sulphur, low-metals content feed
options to the coker unit. The
options become obvious when
analysing the residuum at the
molecular level, where it is clear
that the undesirable impurities in
the coke are essentially asphaltenic
in nature and can be separated by
solubility-driven processes.
The solution involves the use of a
proven solubility-based physical
separation process solvent deas-
phalting in which a paraffnic
solvent preferentially extracts
paraffnic and resinic molecules,
leaving behind asphaltenic prod-
ucts. While solvent deasphalting is
primarily an aromatics rejection
process, it is also a metals and CCR
rejection process. The aromatic
molecules that are rejected contain
the majority of the metals and CCR,
thereby producing a deasphalted
oil (DAO) that can be processed in
downstream units directly or after
the removal of resins.
While DAO has been traditionally
hydrotreated and/or catalytically
cracked owing to its higher value
molecules, the resin that is
produced has so far been used only
for production of fuel oil or road
asphalt. The resin product is a rela-
tively low-metal, low-sulphur
residuum that is high in asphaltene-
free CCR. Due to these
characteristics, resin is very good
for producing higher quality coke,
and an excellent feedstock for the
production of anode-grade coke.
Inherent in the solvent deasphalt-
ing process is the ability to draw
out the resinic molecules and to
adjust the volume and quality of
the resin. The operating conditions
of the asphaltene separator can be
adjusted to lift the resinic molecules
in the DAO. The resinic molecules
are then recovered from the DAO
by partially expanding the solvent
under supercritical conditions. This
arrangement provides the fexibility
to balance the streams to down-
stream processing needs, while
consistently meeting the required
DAO quality and exercising other
disposition options for the interme-
diate resin streams.
While this addresses the issue of
providing low-sulphur, low-metals
feed to the coker, the issue of deal-
ing with streams used to make fuel
oil remains. While the higher value
distillate products used for cutter
stock can be used as saleable prod-
ucts, streams of much poorer
quality, such as the clarifed slurry
oil (CSO) from the FCCU, now
require an alternative outlet. The
slurry oil is a highly aromatic reject
from the FCCU. Being denser than
water, transporting the CSO by sea
is not easy either. However, the
CSO, despite being a reject from the
FCCU, has low sulphur primarily
because of the hydrotreated feed to
the FCCU.
So while the CSO may not have
the superior quality required for
producing high-value distillate
products, it can still be blended
with the resin from the three-
product ROSE (residuum oil
supercritical extraction) process to
be used as feedstock for production
of anode-grade coke. In fact, an
optimum feed to the delayed coker
to produce anode-grade coke would
be a blend of the resin from the
ROSE process, the CSO from the
FCCU and the required amount of
VR to compensate for any quality
giveaway. In effect, what this gives
the refner is the ability to insulate
the coke grade from fuctuations in
the quality of the crude and hence
always produce anode coke, irre-
spective of the quality of the crude.
Furthermore, the use of ROSE resin
R
e
s
i
n
s
e
p
a
r
a
t
o
r
A
s
p
h
a
l
t
e
n
e
s
e
p
a
r
a
t
o
r
D
A
O
s
e
p
a
r
a
t
o
r
Resin
stripper
Asphaltene
stripper
DAO
stripper
R O SE
exch an g er
Start
resid u u m
R esin
h eater
H o t o il
H o t
o il
So lven t
circu latio n
Asp h alten e
h eater
Static
m ixer
D AO
h eater
So lven t
sto rag e
C o n d en so r
Asp h alten e D AO
Steam
Steam
R esin
C o o ler
Steam
H o t o il
R O SE
exch an g er
So lven t
recycle
Figure 1 Three-product ROSE
kbr.indd 2 8/3/10 14:45:57
along with the available CSO will
substantially moderate the varia-
tions in VR quality that the refnery
may see with changing crude slates,
thereby enhancing the fexibility
and reliability of the anode-grade
coker.
Although ROSE offers an excel-
lent feedstock for anode coke
production, it introduces the issue
of disposal of the asphaltenes
produced. While the resin cut can
be utilised for making anode-grade
coke, the asphaltenic molecules
remain. These asphaltenes can be
subjected to coking too but, owing
to their high impurity levels, will
only produce low-quality high-
sulphur fuel-grade cokes. However,
delayed coking can only tolerate a
CCR of 3438%. Therefore, the
amount of resin extracted depends
on the quality of the remaining
pitch or, in other words, only so
much resin is drawn out so that the
CCR of the pitch remains within
the limits of the delayed coking
unit. As a result, the refnery will
produce a fxed amount of anode-
grade coke and the balance will be
a lower amount of poorer quality
fuel-grade coke.
If the CCR of the asphaltenes is
too high for delayed coking, another
alternate would be to divert these
molecules away from the refnery
to industries or end users outside
the refning business who have an
incentive to process these streams.
The major challenge here is in the
handling and transportation of
these molecules. The asphaltene
product is a high-viscosity liquid
that solidifes at ambient tempera-
ture. A low-cost, high-capacity solid
pelletisation technology such as
KBRs Aquaform is an obvious
solution. This will help refners to
economically store and move these
rejects to a more desirable end use,
such as solid fuel for cement kilns,
the steel industry or the utility
industries.
Delayed coking
In its simplest form, delayed coking
is a semi-continuous process, irre-
spective of the type of coke
produced. Although the coking
process is continuous, coke removal,
handling and disposal are carried
out in a batch manner. The feed is
heated to the reaction temperature
in a direct-fred heater and subse-
quently transferred to the coke
drums. The coking reaction is
delayed until the heated feed is
transferred into the coke drums,
where the residence time is long
enough for the coking reactions to
go to completion. Coke is deposited
in the drum and the cracked vapour
product exits the drum from the
top, then enters the downstream
fractionator. Coke is removed from
the drum by taking the drum off-
line. In order to achieve near
steady-state unit operation, the coke
drums operate in pairs, so that one
drum is in flling mode, while the
other is off-line for decoking. The
chemistry of coking is similar to a
severe thermal cracking process,
wherein the larger molecules such
as paraffns and paraffnic side
chains are cracked into smaller
molecules, which then polymerise
and condense to form coke.
Depending on feed quality and
the operating conditions of the
coker, the quality of coke produced
may vary from fuel-grade and
anode-grade to needle-grade coke.
Fuel-grade coke is used primarily
in power and cement plants as fuel;
anode-grade coke is widely used in
the aluminium industry for the
manufacture of electrodes; and
high-grade needle coke is a
premium coke used to manufacture
electrodes for the steel industry.
Table 1 shows typical specifcations
for three grades of coke.
The operating conditions of the
coker unit are selected according to
the quality of the feedstock and the
process objectives. The three
primary operating variables that
affect product yield and coke qual-
ity are coke drum pressure, recycle
ratio and coke drum temperature.
Table 2 shows commercial data
published by a US refner to illus-
trate the typical range of coker
operating conditions for producing
different grades of coke.
Most modern coker units are
designed and operated at low pres-
sure, low temperature and low
recycle ratios to maximise the yield
of distillate products and hence
produce fuel-grade coke as a
byproduct. Cokers producing
anode-grade and needle-grade coke
need to be subjected to more severe
conditions of temperature and pres-
sure, along with a high recycle
ratio. Increasing the recycle ratio
means increasing the hydraulic
capacity of the coker. This means
that the fresh feed to the coker
needs to be reduced to stay within
the limitations of the hydraulic
Property Fuel coke Calcined anode coke Calcined needle coke
Bulk density, kg/m
3
880 720800 670720
Sulphur, wt% 3.57.5 1.03.5 0.20.5
Nitrogen, ppmw 6000 50
Nickel, ppmw 489 200 57
Vanadium, ppmw 141 350
Volatile combustible material, wt% 12 0.5 0.5
Ash content, wt% 0.35 0.4 0.1
Moisture content, wt% 812 0.3 0.1
HGI 3570+ 60100
Coeffcient of thermal expansion, x 10-7C 15
Specifcations for three grades of coke
Table 1
Fuel grade Anode coke Needle coke
Drum pressure, bar 1.01.5 1.53.0 4.07.0
Recycle ratio, vol% 510 2530 5080
Drum temperature, C 435440 440445 450455
Typical range of coker operating conditions for producing different grades of coke
Table 2
kbr.indd 3 11/3/10 14:10:23
solution economically unattractive.
In an attempt to improve the coke
quality, several combinations of VR
and CSO from the FCCU were
tested, confrming that the produc-
tion of anode-grade coke from the
existing crude slate was not viable.
Changing the crude slate was not
an option, and an economic analy-
sis indicated that the production of
anode-grade coke would have a
signifcant and positive impact on
refnery margins.
In an effort to reduce overall fuel
oil production, the refnery is also
considering the implementation of
a traditional two-product solvent
deasphalting unit as a low-capital
option to separate suffcient
volumes of high-quality DAO to be
sent to the FCCU, while rejecting
the pitch to fuel oil.
The option to use a three-product
solvent deasphalting unit to
produce a DAO stream for feed to
the FCCU, a pitch stream for fuel
and an intermediate resin stream
for use as a coker blend stock was
evaluated. The three potential feed
streams VR, ROSE resin and
CSO for testing in a delayed coker
are shown in Table 3.
Several combinations of VR, CSO
and ROSE resin were tested for
coke quality. The results (see Table
4) indicate that a combination of
resin and CSO will produce high-
grade anode coke. This is primarily
because of the ability of the ROSE
unit to suffciently improve the
sulphur, metals and C
7
insolubles
content in the resin stream to allow
for the production of anode-grade
coke.
The use of ROSE resin along with
the available CSO will also substan-
tially moderate the variations in VR
quality that a refnery may see with
changing crude slates, thereby
enhancing the fexibility and relia-
bility of the anode-grade coker.
Conclusion
Anode coke production can be real-
ised from traditional crudes by
adopting a technology solution that
involves the integration of a
commercially proven niche version
of the ROSE process and FCC slurry
oil to custom blend feed for anode
coke production.
The combination of solvent deas-
phalting and niche-delayed coking
represents an economic solution to
minimise fuel oil production and
produce anode-grade coke, which
can be implemented at a fraction of
the cost of other resid processing
options.
Mitra Motaghi is an Associate with the
KBR refning technology business unit in
Houston, with specifc focus on resid and
hydroprocessing technologies. She holds an
MS degree in chemical engineering from Texas
A&M, Kingsville, Texas.
Kanu Shree is an Associate with the KBR
refning technology business unit in New
Delhi, with specifc focus on resid and
hydroprocessing technologies. She holds a BS
degree in chemical engineering from the Indian
Institute of Technology.
Sujatha Krishnamurthy is an Associate with
the KBR refning technology business unit in
New Delhi, with specifc focus on resid and
hydroprocessing technologies. She holds a BS
degree in chemical engineering from Anna
University, Chennai, India.
capacity of the original coker unit.
Hence, three-product solvent deas-
phalting becomes the obvious
choice to cut down the amount of
original feed to the unit, wherein
the extracted resinic molecules,
along with the stranded streams
from the refnery such as CSO and
balance VR, become a reduced fresh
feed to the coker unit. The balance
capacity can be met by increasing
the recycle ratio, which, in fact,
favours anode coke production.
Refnery case study
In this example, an FCC-based
refnery is processing heavy crudes
and has no bottoms processing
capability. Under the current oper-
ating scenario, the VR is cut with
distillates and sold as high-sulphur
fuel oil.
The quality of VR is too high in
sulphur and metals content, such
that the addition of a delayed coker
processing the entire VR stream
would result in the production of
low-grade petroleum coke. When
processing the entire VR stream, the
large size of the coker and the lack
of an economic outlet for the high-
sulphur petroleum coke made this
Vacuum residue Slurry oil Resin
SG @60F 1.0279 1.0926 1.017
API gravity 6.2 -2.0 7.6
Sulphur, wt% 3.9 0.9 3.5
CCR, wt% 20.3 9.9 17.6
Nickel, wppm 47 1 20
Vanadium, wppm 163 1 65
Three potential feed streams
Table 3
Coke specs 20/80 CSO/VR 40/60 CSO/VR CSO+ resin
Dry gas, wt% 4.2 4.2 4.2
C
3
+ liquid, lv% 61.8 59.9 60.7
Coke, wt% 33.0 35.3 34.4
Coke quality
Capacity, bpsd 20 000 20 000 20 000
Coke, MT/D 1090 1177 1144
Sulphur, wt% <3.0 4.2 3.2 2.9
Nickel, ppmw <200 113 79 36
Vanadium <200 391 272 115
Coke type Fuel grade Fuel grade Anode coke
Combinations of VR, CSO and ROSE resin tested for coke quality
Table 4
kbr.indd 4 8/3/10 14:46:30
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Catalytic reforming options and practices
R
efners throughout the world
utilise catalytic reforming to
produce high-octane reformate
for gasoline blending and high-
value aromatics (benzene, toluene
and xylene, BTX) for petrochemical
use. Reforming is also a major
source of refnery-based hydrogen.
Reforming operations continue to
be challenged in the context of
lowering gasoline pool aromatic/
benzene content; however, the cata-
lytic reforming unit is still a
mainstay of refnery operations.
The recent upward trend in hydro-
treatment needs has put even more
emphasis on reformer hydrogen
production. The main differences in
technology among the various
reforming processes are discussed
in this article, and special attention
is given to chloride control and
corrosion management.
Feedstock
The standard feed to a catalytic
reforming unit (CRU) is hydro-
treated straight-run naphtha (SRN),
typically containing C
6
through C
11

paraffns, naphthenes and aromat-
ics. Naphtha from different sources
varies greatly in its ease of reform-
ing. Most naphthenes react rapidly
and effciently to form aromatics.
This is the basic reaction of reform-
ing. Paraffns are the most diffcult
compounds to convert. A rich
naphtha (lower paraffn, higher
naphthene content) makes the oper-
ation much easier and more
effcient. The types of naphtha used
as feed to the CRU can impact the
operation of the unit, activity of the
catalyst and product properties.
When catalytic reforming is used
mainly for BTX production, a C
6
-C
8

Design and practice in catalytic reforming is evolving to meet refnery challenges,
including lower gasoline pool benzene content and increased demand for hydrogen
Tom Zhou Fluor Enterprises
FReDeRik BaaRs Fluor BV
cut (initial and fnal boiling points
IBP-FBP 60140C), rich in C
6
, is
usually employed. For production
of a high-octane gasoline pool
component, a C
7
-C
9
cut (IBP-FBP
90160C) is the preferred choice.
1

Reformate benzene content can be
reduced by minimising the amount
of benzene and benzene precursors
(cyclohexane and methylcyclopen-
tane) in the reformer feed via
prefractionation. Alternatively, the
benzene can be reduced by post-
fractionation of the reformate and
further processing of the light
reformate.
In a refnery where maximisation
of middle distillate production is a
priority, the heavier portion of the
naphtha that is traditionally routed
to a catalytic reformer unit may
instead be sent to the kerosene or
diesel pool, within fash point spec-
ifcation limits. In most cases, a
lighter CRU feed will result in an
increased cycle length for a semi-
regenerative (SR) unit due to
decreased coke make.
Non-straight-run naphthas (for
instance, fuid catalytic cracking
(FCC) naphtha or visbreaker/coker
naphtha) can also be processed in a
CRU, but only after severe hydro-
treatment involving (di)-olefn
saturation, in addition to the basic
naphtha hydrotreater functionality
of removing heterogeneous atoms
(sulphur and nitrogen). Their higher
endpoint and/or higher paraffn
content results in a higher coke
laydown. Cyclic and continuous
catalyst regeneration (CCR) reform-
ers are generally able to process
FCC naphtha with a higher feed
endpoint as long as regenerator
capacity exists to burn the addi-
tional coke that is produced.
2
The
reprocessing of FCC naphtha is
Sp en t
catalyst
R
e
c
o
v
e
r
y
s
e
c
t
i
o
n
Stacked
reactor
Combined
feed
exchanger
Combined
feed exchanger
S
e
p
a
r
a
t
o
r
Stabiliser
R eg en erated
catalyst
CCR
regenerator
Aro m atics
rich refo rm ate
Lig h t
en d s
Fu el g as
N et H
2
rich g as N ap h th a feed
fro m treatin g
N et g as
co m p resso r
Fired h eaters
Figure 1 CCR with stacked reactors Courtesy: UOP
fluor 2.indd 1 8/3/10 14:51:23
ThyssenKrupp
Uhde
Solutions in Refining
Technologies
Uhde GmbH
Edeleanu Refining Technologies Division
Friedrich-Uhde-Str. 2
65812 Bad Soden
Germany
Phone +49 (61 96) 205 1715
Fax +49 (61 96) 205 1717
www.uhde.eu
Visit us at
Beijing, PRof China, 1-4 June 2010, Stand 27 J
As an internationally renowned engineering
partner and plant construction company,
Uhde offers complete service packages from
the initial concept to the turnkey plant.
Uhde provides these services to refineries
around the world. Two of our main specialities
are naphtha and middle distillate processing.
In line with the trend towards improving the
quality of gasoline and diesel, our Edeleanu
Refining Technologies Division has executed
numerous hydrodesulphurisation projects
during the last few years. Several plants, not
only based on world-class technologies
supplied by well-known licensors such as
Axens
Haldor Topsoe
Kellogg Brown & Root
UOP
but also proprietary Edeleanu technologies
designed in co-operation with catalyst
suppliers such as Albemarle or BASF, are
currently under construction.
The total capacity of all our naphtha and
diesel hydrotreating projects since 2001 now
exceeds 15 million tonnes per year. The
treated products meet the European Clean
Fuels Directive.
Isomerisation of light gasoline or gas conden-
sate yields another valuable blending compo-
nent for gasoline. Our Edeleanu Refining
Technologies Division executes projects for
grassroots plants or revamps of catalytic
reformers for that purpose.
In keeping with our slogan Engineering with
ideas, we provide a comprehensive range of
supplies and services which extends from the
initial feasibility study and financing right
through to operation of the turnkey plant.
Middle Distillate Desulphurisation Unit for
Shell Deutschland Oil GmbH in Wesseling, Germany
C5/C6 Isomerisation, PCK Schwedt, Germany
www.ptqenquiry.com
uhde.indd 1 9/3/10 14:12:52
directs them to the reactor outlet.
Low fow should be avoided, as it
will result in accelerated coke
laydown.
Reactor metallurgy
Reactor vessels in a SR CRU service
are standalone items and can be
either hot or cold shell, depending
on design preference. In cold-shell
designs, an internal refractory lining
protects the vessel wall from expo-
sure to the process temperature. In
CCR service, the reactors are invari-
ably of the hot-shell design and can
be either individually positioned or
stacked to form a compartmented
single vessel.
8
In a SR CRU, a cold
wall (carbon steel with refractory
typically restricted to the lower
octane middle cut. If desulphurisa-
tion only is required, processing the
FCC naphtha in a selective hydro-
treating unit is the more
straightforward solution.
Fixed-bed units vs CCR reformers
The conventional CRU type is the
SR fxed-bed reforming unit, which
is used for limited octane improve-
ment. The unit is operated at high
pressure to mitigate carbon forma-
tion. As carbon laydown increases,
reactor temperatures are raised to
achieve the target octane at the
expense of reformate yield. A cyclic
regenerative process with a swing
reactor system is used for higher
severity and octane operation. With
CCR reforming (see Figures 1 and
2)
3,4
, extremely high severities are
obtainable without frequent shut-
downs due to catalyst deactivation.
The units operate at a low pressure
with the associated yield benefts of
higher reformate and hydrogen
yields.
The decision to convert high-
pressure SR catalytic reformers to
CCR-type units hinges entirely on
economics.
5
Some reforming licen-
sors have developed a hybrid unit,
by adding a CCR reactor and regen-
erator to an original SR reforming
unit.
4,6,7,8
Typical examples are
shown in Figures 3 and 4. The
conversion could cost less than half
that of a new CCR and increases
throughput and/or cycle length.
4

To some refners, a complete
conversion to CCR remains
economically attractive relative to a
hybrid unit, due to the higher on-
stream factor, lower operating
pressure, and higher yields of
hydrogen and naphtha.
9
Virtually
all new reforming units are of the
CCR design.
Reactor design
There are three types of reactors
predominantly in use in the reform-
ing process. These are spherical,
downfow and radial. As catalyst
improved over the years, the reac-
tor pressure could be reduced to
take advantage of the increased C
5
+
and hydrogen yields at lower oper-
ating pressure. At lower pressure,
the pressure drop through the
reactor becomes an important
consideration; therefore, more
modern designs of reforming units
employ reactors that are radial fow
in design and combine good fow
distribution with low pressure
drop.
The combined feed is directed
from the reactor inlet nozzle into
so-called scallops, which are long,
vertical channels positioned along
the entire circumference of the reac-
tor. The scallops have holes or,
more commonly these days, profle
wire screens along the entire length,
through which gas passes radially
into the annular catalyst bed and
inwards to a centre pipe that
collects the reactor products and

Fig1:


R eco very
system
B o o ster
co m p resso r
R ecycle
co m p resso r
Feed
R
1
R
2
R
3
Regen C2
regenerator
Reactors and heaters
S
e
p
a
r
a
t
o
r
H yd ro g en
rich g as
R efo rm ate to
stab ilisatio n
Figure 2 CCRwithside-by-sidereactorsCourtesy: Axens
New feed/efuent
exchanger
Heater
H3
New heater
H4
Heater
H2
Heater
H1
Feed
R
1
R
2
R
3
Air
cooler
Recycle
compressor
Charge
pump
New reactor
R4
Regenerator
Reactors
S
e
p
a
r
a
t
o
r
Hydrogen
rich gas
Unstabilised
reformate
Figure 3 SRandCCRhybridprocess Courtesy: Axens
fluor 2.indd 2 8/3/10 14:51:40
lining) with an inner stainless steel
liner is the norm. However, hot-
shell design necessitates the use of
1.25Cr-0.5Mo, or in some cases
2.25Cr-1Mo, with stainless steel
internals suitable for service above
538C (1000F) to meet the require-
ments for both high-temperature
strength and resistance to hydrogen
attack.
Reforming catalyst and catalyst
regeneration
The reforming catalyst consists of
noble metals impregnated on an
alumina base, with a cylindrical (SR
applications) or spherical shape (SR
and CCR applications). A wide
variety of metals can be used, but
platinum is predominantly used.
Multi-metallic catalysts composed
of platinum (Pt) and rhenium (Re)
are the most common type found
in a fxed-bed CRU. Rhenium
helps to improve catalyst life by
retarding coke deposition to prevent
deactivation.
Pt-Sn catalysts are utilised in CCR
reforming units. The presence of tin
(Sn) prevents platinum agglomera-
tion or sintering during the
regeneration and provides better Pt
dispersion.
2
In the reactors, both the
metal(s) and the chloride base
help catalyse desirable reactions.
Optimum catalyst performance
requires a proper balance of these
two catalytic functions. Catalyst
deactivation usually occurs as a
result of coke formation covering
the active sites of the catalyst. To
regenerate the catalyst, the coke
must be burned off and the catalyst
oxidised (oxychlorinated to redis-
perse the platinum and restore the
chloride balance), dried and fnally
reduced. Each step of the regenera-
tion procedure is critical to return
the catalyst system to its usual high
performance and to ensure long
catalyst life.
SR and cyclic reformers utilise
fxed-bed reforming reactor(s) for
regeneration, while a CCR reformer
has a dedicated moving-bed regen-
erator with associated piping and
equipment. In SR operation, the
catalyst is allowed to coke up and
needs to be regenerated periodi-
S
e
p
a
r
a
t
o
r
Feed
H eaters
R eco n tact
system
Stab iliser
sectio n
Rx 3
Rx 4
Rx 2 Rx 1
Combined
feed
exchanger
New equipment
required
Catalyst
regenerator
Figure 4 SR and CCR hybrid process Courtesy: UOP
cally in-situ. A cyclic reformer has
a swing/spare reactor to allow unit
operating severity to be maintained
while one reactor is being regener-
ated. A cyclic or CCR reformer is
more robust to feed upsets, as it is
regenerated on-line. The reactor
operating pressure is lower than
with SR operation, which is benef-
cial to reformate/aromatics yield.
Although the lower operating pres-
sure accelerates coke laydown, this
is taken care of by on-line
regeneration.
The catalyst regeneration system
in a CCR reformer performs two
functions: catalyst regeneration and
catalyst circulation. These days, all
regeneration steps, except for reduc-
tion, occur in the regenerator. The
reduction takes place in the reduc-
tion zone above the frst reactor.
The catalyst exits the zone and
fows by gravity to the frst reactor.
Catalyst developments continue,
with manufacturers constantly
introducing catalysts that exhibit a
better yield pattern or a higher
activity.
Reforming catalyst can only be
regenerated if the cause of the deac-
tivation is sulphur and/or carbon
laydown. Other (permanent)
sources of deactivation will typi-
cally require catalyst replacement.
Chloride-related corrosion control
To assure the metallic and acidic
functions of a reforming catalyst,
chloride is continuously injected
into the process. Depending on the
levels of nitrogen in the feed to the
CRU, ammonium chloride could
form and deposit on process equip-
ment, with the risk of corrosion or
reduced effciency (for instance, in
compressors). Injections with refor-
mate, naphtha or water are an
option for cleaning out salts depos-
ited in the recycle gas compressor.
2
A good design should focus on
removing organic nitrogen from the
reformer feed and minimising
hydrochloric acid (HCl) in the reac-
tor loop. While the SR reformer
operation is dry during normal
operation, this changes during
regeneration, with water being
formed as a result of coke being
burnt off. While the low chrome
reactors are not at risk when hot
Each step of the
regeneration
procedure is critical
to return the catalyst
system to its usual
high performance
and ensure long life
fluor 2.indd 3 8/3/10 14:52:01
but can create problems when
mixed with other (wet) streams.
Chloride absorbers (on net gas, LPG
or stabiliser feed) are typically
installed to overcome this.
Depending on the CCR regenera-
tor design type, the regenerator
vent gas can also contain signifcant
amounts of HCl. Caustic scrubbers
are generally employed to remove
HCl from the vent gas. Recontacting
the vent gas and/or reduction step
purge gas with spent catalyst
(aimed at reabsorbing HCl back
into the process) has recently been
introduced
11
as a means of reducing
HCl losses and therefore chloride
consumption.
References
1 Prestvik P, Moljord K, Grande K, Holmen A,
Catalytic Naphtha Reforming, Antos G J, Aitani
A M, Marcel Dekker, New York, 2004, 1718.
2 Hydrocarbon Publishing Company, Third
Quarter 2009 Hydrocracking and Catalytic
Reforming, Worldwide Refnery Processing
Review, 225273.
3 UOP, CCR Platforming Process for Motor
Fuel Production, www.uop.com/objects/
CCR%20Platforming.pdf.
4 Domergue B, le Goff P-Y, Ross J, Octanizing
reformer options, PTQ, Q1 2006, 67 & 72.
5 1996 ERTC, London, Oct 1996, Global
Technology Forum, Surrey, England, 29.
6 Gendler J L, Domergue B, IFP Solutions for
Revamping Catalytic Reforming Units, 1996
NPRA Annual Meeting, San Antonio, Texas.
7 Stephens G, Travers Ph, Mank L, Revamping
Catalytic Reforming Units, Revue de lInstitut du
Ptrole, 1994, 49, 5.
8 Peters S T, Platforming

Technology Advances:
CycleX System for Increased Hydrogen
Production from a Fixed-bed Reforming Unit,
2003 NPRA Annual Meeting, San Antonio,
Texas.
9 1996 NPRA Q&A and Technology Forum:
Answer Book, 1996 NPRA Q&A Session, San
Antonio, Texas.
10 Brear J M, Williamson J, Integrity and Life
Assessment of Catalytic Reformer Units, www.
seseurope.com/htm/SESpapers_pdf, SES 2006.
11 2009 ERTC UOP pre-seminar.
Fred Baars is a Technical Director with Fluor
BV, Haarlem, the Netherlands, responsible for
refnery studies and basic engineering projects.
Email: frederik.baars@fuor.com
Jun (Tom) Zhou is a Principal Process Engineer
with Fluor Enterprises, Houston, Texas,
with experience in front-end and detailed
engineering design for catalytic reforming
units. Email: tom.zhou@fuor.com
during regeneration, the area
downstream at the effuent cooler
presents a great risk of corrosion.
To maintain corrosion control
during regeneration, separator
water pH is kept above 7 by adjust-
ing caustic injection during the coke
burning and oxidation steps.
For CCR reforming, the regenera-
tor and its internals are normally
made of stainless steel, which is
considered to be adequate for chlo-
ride corrosion resistance, since
temperatures inside the regenerator
are kept above the water dew point.
However, special attention needs to
be paid to instrument taps and
nozzles, where cooling and conden-
sation can occur. Heat tracing and
nitrogen purging are required
to limit chloride corrosion.
Alternatively, the metallurgy can be
upgraded from stainless steel to
materials such as Hastelloy.
Most HCl concentrates in the
reformer net gas and liquefed
petroleum gas (LPG). While these
streams are dry, they do not gener-
ally pose problems inside the CRU,
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fluor 2.indd 4 11/3/10 22:37:18
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RZ_AZ_Auge_210x297_1130_E.indd 1 06.05.2009 17:05:48 Uhr
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Planning for carbon capture
T
he management of carbon
and energy security can be
approached in much the same
way as any other new investment
project. By using an investment
planning approach and applying
this specifcally to focus on energy
security and greenhouse gas (GHG)
management, the selection of the
right project to meet objectives can
be achieved. This article explains
how an investment roadmap model
can be adapted to projects tailored
to energy security and carbon
reduction, including location and
process considerations.
The goal of investment planning
is to support companies in the
selection of the right project to
achieve their strategic goals. This
involves determining if the projects
are both economically and techni-
cally feasible, ensuring the optimum
use of capital and determining the
most appropriate timeframe for the
project.
There is a wide range of ques-
tions to be addressed when
embarking on a new project, such
as:
What products are required?
What feedstocks are available?
What are the possible process
routes?
Is the proposed location suitable?
The best way to meet the projects
requirements is to follow a simple
roadmap process (see Figure 1).
Investment planning roadmap
Agree objectives
It is fundamentally important to
defne what the project aims to
achieve. This can range from a
simple debottleneck of a plant to
achieving a carbon dioxide (CO
2
)
An investment planning roadmap for a project incorporating carbon capture
should address the schemes basic objectives and its viability in the market
SuzAnne FerguSon
Foster Wheeler
emissions target for a global corpo-
ration. There may also be a number
of stakeholders involved, so this
stage is key in ensuring alignment
between the parties involved.
Market analysis
This step is essential to drive the
confguration of feedstock, product
slate and plant towards the opti-
mum economic solution, thus
maximising the plants margin.
Market analysis will determine
product demand and price (includ-
ing CO
2
pricing, for example), as
well as the price and availability of
feedstocks.
Plant confguration studies
For most applications, linear
programming (LP) is used to
develop a model of the project,
incorporating product yield, capital
and operating cost data for each
potential unit operation. The results
of the market analysis are also
input into the model, which is then
run to determine the best perform-
ing confguration on a net present
value (NPV) basis. The LP model
generated can then also be used to
explore rapidly a number of what-if
scenarios, enabling the projects
economic sensitivity to variations in
key product or feedstock prices to
be understood.
Site selection
The suitability of the proposed loca-
tion (or locations) can be assessed
by considering four key factors:
Site: land availability, ground
conditions, structures and obstruc-
tions, severe weather protection,
earthquake zonal rating
Port: already existing, dredging
requirements, jetty location, existing
facilities, suitability of surrounding
waterways
Infrastructure: local and national
!GREEOBJECTIVES
-ARKETANALYSIS
0LANT
CONFIGURATIONSTUDY
-OREDETAILEDREVIEWS
%CONOMIC
FINANCIALANALYSIS
2ECOMMENDEDCONFIGURATION
DEVELOPMENTROADMAP
#ONSTRUCTABILITY
STUDIES
3ITE
SELECTION
$EVELOPOFFSITES
UTILITIESMARINE
FACILITIESCONCEPT
#OSTESTIMATES
Figure 1 The investment planning roadmap
fw.indd 1 10/3/10 13:25:11
road network, heavy haul routes,
rail network, regional and national
airports
Local area: towns and industry
nearby, construction resources,
schools and emergency services,
prevalent health hazards, landfll
materials, local labour.
This assessment looks at the suit-
ability of prospective sites and
enables the cost of infrastructure
development, ground remediation
and so on to be factored into the
cost estimate.
Offsites and utilities
Scope of the utilities and offsite
requirements will be based on data
from process unit technology
providers and from the contractors
own data. Major equipment lists for
all utilities, tankage and other
offsite requirements will be identi-
fed, including intermediate tankage
based on high-level shutdown
philosophy and marine facility
requirements.
Constructability studies
It is crucial to consider constructa-
bility during the investment
planning stage of a project in order
to determine issues that could
impact the design. Such issues
include access routes for large or
heavy equipment and the costs/
benefts of modular rather than
stick-built fabrication. At this stage,
a high-level schedule for the full
project through to start-up can be
developed and the contracting strat-
egy can be planned.
Cost estimates
Cost estimates, based on current
market data for the plants
location, are based on stages in the
investment planning process. High-
level operating costs, including
maintenance, insurance, labour,
feedstocks, catalyst and chemical
requirements are developed, along
with the capital cost estimate.
Economic and fnancial modelling
Capital and operating cost estimates
are fed into models to ensure that
the plant economics are suffciently
robust and achieve the objectives
specifed at the beginning of the
investment planning process.

Fig1:

Assumptions within the models

should refect the companys long-
term outlook and should consider a
number of scenarios. The projects
internal rate of return (IRR) should
be considered, along with the NPV,
in order to determine the magni-
tude of the reward for the estimated
costs of investment.
Investment planning process
conclusion
Investment planning can be an iter-
ative process and, while changes
are frequently made in later design
stages, the earlier they occur in the
projects development the lower the
cost of changes and iterations.
A well-conceived investment
plan, based on real data and tested
against real scenarios, gives a sound
basis upon which to progress the
project and meet the original objec-
tives of the company. The plan
should focus on all issues affecting
the projects cost and development
not just the confguration of the
process units.
The roadmap approach to invest-
ment planning can be tailored to
any type of project to ensure that
goals are achieved and that the
right project solution is developed
from the beginning.
The roadmap approach can be
applied to maximise energy secu-
rity and to manage GHG emissions.
Technology options that can be
applied in these areas must also be
considered.
Energy security and GHG
management options
A well-developed design, utilis-
ing optimal feedstocks, energy
integrated fow schemes and a
high-value product slate, is inher-
ently likely to be effcient,
minimising energy demand and
waste streams. However, there are
almost always some unavoidable
energy demands and carbon emis-
sions. This section introduces some
of the key options for mitigation of
energy security risks and abatement
of GHG emissions. This article deals
only with CO
2
, since it is the largest
single contributor to the greenhouse
effect.
Energy security
Energy security can mean different
things to different people, but is
generally related to a need to
ensure access to low-cost and relia-
ble energy supplies. Threats to
energy security can be from a
number of sources, such as:
Political instability
Attacks on energy infrastructure
High dependence on single
primary fuels through lack of diver-
sifcation of supply
Severe weather, accidents or
natural disasters
Unreliable electricity supply
and/or transmission systems
Limited supplies of primary fuels
Fluctuating primary fuel prices.
Energy consumption is well docu-
mented as rising directly in line
with population growth and GDP.
This has led to seriously overbur-
dened energy infrastructure in
many parts of the world, where
either population or industry, or
both, are increasing rapidly. This
can apply to both fuel and electric-
ity resources. Therefore, security of
energy supply is a key concern for
many operators.
In the process industries, there
are a number of ways to improve
the energy security of a plant or
plants. Reducing energy demand
and increasing energy effciency can
make the site less vulnerable, but
does not, in itself, deliver energy
security, unless there is also a relia-
ble power supply suffcient to meet
the plants reduced needs.
Options for delivering energy
security centre on using a diverse
range of sources of supply, such
that, should one source fail or
become too expensive, an alterna-
It is crucial to consider
constructability
during the investment
planning stage of a
project to determine
issues that could
impact the design
fw.indd 2 10/3/10 13:25:20
www.ptqenquiry.com
albemarle.indd 1 10/3/10 13:13:33
tive can be used. This can apply to
either on-site or over-the-fence elec-
tricity generation, as well as to
process heating; however, we will
refer here primarily to on-site
generation and process heating,
which provide the plant with
greater independence from external
threats to energy supply.
On-site power generation can be
signifcantly more effcient than
standalone power generation, since
it can be integrated with the proc-
ess. A number of options for
integration include:
Power generation from steam
raised in waste-heat boilers
Boiler feed water preheating
against process-generated low-
grade heat
Cooling water (for process cool-
ing) against a cold process stream
Use of on-site sources of fuel.
Optimisation of energy integra-
tion across the site can also reduce
the need for energy inputs to the
plant; for example, the addition of
new process units may provide a
source of waste heat that can elimi-
nate the need for a process heater
elsewhere. It is important to
consider that the plant must still be
able to start up and maintain avail-
ability, so the capital expense may
not be signifcantly reduced by
energy integration. However, if the
plant is able to run for a signifcant
proportion of its operating hours
with fewer process heaters in oper-
ation, then clearly the energy
demand of the plant will be
reduced.
If both power and steam are
needed by the process, co-
generation of electricity and steam
(or hot water) for process heating
in a combined heat and power
(CHP) plant should be considered.
If the CHP plant can accept a
number of different feedstocks,
such as coal, fuel oil or locally
produced biomass, its contribution
to the energy security of the site is
even greater.
The addition of renewables to
supplement the power generation
portfolio can also increase the
diversity of generation; however,
the likely load factor of each type
of generation should be taken into
account. Adding renewables also
helps to directly reduce the GHG
emissions of the plant.
Carbon abatement options
There is mounting worldwide
concern over the prospect of climate
change due to anthropogenic CO
2
emissions, to which the power
generation and processing indus-
tries are major contributors.
There are a number of drivers for
the process industry to manage and
reduce its CO
2
emissions, most of
which lead back to concern over
climate change. Whether the site
wishes to make the most of an
opportunity for additional income
from the sale of CO
2
credits or to
mitigate the risk of penalties
imposed by future legislation, the
management of CO
2
emissions is
growing in importance.
Greenfeld development projects
have the advantage of being able to
design their processes for reduced
CO
2
emissions through process
selection and choice of primary
energy supply. Both new and exist-
ing plants can consider the
following options:
Effciency improvements
Fuel substitution
Feedstock substitution
Confguration modifcations
Carbon capture and storage.
It is generally recognised that the
most cost-effective approach to
carbon abatement is improvement
in effciency, which can be poten-
tially applied to existing and
planned assets. Confguration modi-
fcations can mean swapping one or
several process units for more eff-
cient alternatives, or debottlenecking
part of the plant to minimise carbon
emissions to the atmosphere.
Most options will be specifc to
the location and type of plant;
however, carbon capture and stor-
age can be applied to almost all
processes in some form or another.
Carbon capture and storage
Carbon capture and storage (CCS)
is the process of removing or reduc-
ing the CO
2
content of streams
normally released to the atmos-
phere and transporting captured
CO
2
to a location for permanent
storage.
CCS can be applied to a wide
range of large, single-point sources,
such as process streams, heater and
boiler exhausts and vents. Three
principal groups of technologies are
employed:
Pre-combustion capture
Post-combustion capture
Oxyfuel combustion capture.
Once captured, CO
2
is compressed,
dried and transported to a suitable
storage location, such as saline
aquifers, depleted oil felds
where enhanced oil recovery could
be employed and depleted gas
felds.
Pre-combustion CO
2
capture
A solid or gaseous feedstock is fed
to an oxygen or air-blown pressu-
rised gasifer or reformer, where it
is converted to syngas. The syngas
is then passed through a shift reac-
tor, which increases the hydrogen
and CO
2
content of the syngas. This
high-pressure, high-temperature
syngas is then cooled, before being
washed with a solvent to absorb the
CO
2
, leaving an essentially pure
hydrogen stream and a CO
2
-rich
solvent stream. The solvent regen-
eration process then releases a CO
2

stream that can be dried and
compressed for export. This process
Air
Peedstock
Nitrogen
water/steam
CO
2
export
Sulphur
ASU
Gasifier/
reformer
Shift
reactor
Heat
recovery
HP
hydrogen
LP
steam
MP HP
AGP
process
SPU & tail gas
treating
Drying and
compressing
Lxcess
water
Oxygen
Figure 2 Pre-combustion fow scheme
fw.indd 3 10/3/10 13:25:30
tion chamber. The fue gases pass
through an electrostatic precipitator
to remove particles, limestone
scrubbing to remove sulphur, and
cooling and condensation to
abstract water. The remaining fue
gases contain a high proportion of
CO
2
, which can then be purifed,
dried and compressed for export.
Steam from the boiler is used to
generate power via a steam turbine
(see Figure 4).
Variations:
A range of fuels can be used in
an oxyfuel fow scheme
It may be possible to convert
existing boilers into oxyfuel boilers
if they can be suffciently sealed.
Other processes
There are a number of processes
that do not ft exactly into one of
the above categories by defnition,
although the technologies are the
same. For example, in the ammonia
process, a stream of CO
2
is
produced as part of the process;
this is removed by solvent washing
according to the scheme for pre-
combustion carbon capture.
However, the ammonia process
does not obviously fall into this
group, since the stream was never
intended to be combusted and,
therefore, cannot be called pre-
combustion. The removal of CO
2
from natural gas in natural gas
treating plants is a further example
of this type of process.
Investment planning for energy
security and GHG management
An energy security and/or CO
2
management project requires each
of the steps to be identifed in the
investment planning roadmap, just
as any other project does. Applying
the investment planning approach
ensures that objectives are well
defned, the project is appropriate
to the market, the confguration of
the solution is optimal, the costs are
well defned, and the economic and
fnancial case is robust.
Agree objectives
At this stage, the aims of the project
and the scope to which they apply
should be determined. For example,
a company may wish to reduce CO
2

emissions from all of its process
plants to meet an internal goal, or it
offers high potential for integration,
as it generates a pure, high-pressure
hydrogen stream, and the syngas
cooling train can be used to raise a
signifcant quantity of HP, MP and
LP steam (see Figure 2).
Variations:
A range of coals, petcoke, fuel
oils, municipal solid waste and
biomass can be used as gasifer
feedstock
Natural gas and light liquid feed-
stocks can be used with a reformer
A range of CO
2
solvent removal
systems are available, including
Selexol and methyl-diethanolamine
(MDEA), as well as alternative tech-
nologies such as membranes and
pressure swing absorption (PSA).
Post-combustion CO
2
capture
Flue gases from power generation
are cooled by direct water contact
before they enter a blower designed
to overcome the absorption system
pressure drop. The fue gases enter
the absorption column, where they
are washed with a solvent such as
monoethanolamine (MEA). The fue
gases are stripped of up to 90% of
their CO
2
content and released to
the atmosphere from the top of the
absorber. The CO
2
-rich solvent is
then heated against lean solvent
and regenerated in a stripping
column. The solvent then returns to
the absorption column, while the
released CO
2
is dried and
compressed for export. The high-
light of the post-combustion process
is that it is suitable not only for new
installations, but also may be retro-
ftted to existing plants (see
Figure 3).
Variations:
A range of processes use differ-
ent solvents: MEA, ammonia,
sterically hindered MEA and even
seawater
For high-sulphur feeds, the proc-
ess can be coupled with a fue gas
desulphurisation unit, enabling the
direct-contact cooler to be
eliminated.
Oxyfuel combustion CO
2
capture
In this process, fuel is combusted
with oxygen from an air separation
unit. The temperature in the boiler
is moderated by recycling a portion
of the fue gas back to the combus-
D irect
co n tact
co o ler
D ryin g an d
co m p ressio n
H EX
Excess
water
Lean
so lven t
Ven t
B lo wer
Flu e
g as
Absorber
Stripper
C O
2
exp o rt
Figure 3 Post-combustion fow scheme
!IR
&UEL
.ITROGEN
&LUEGASRECYCLE
#/
EXPORT
!35
/XYFUEL
BOILER
0ARTICLE
REMOVAL
3ULPHUR
REMOVAL
7ATER 'YPSUM
,IMESTONE
SLURRY
&LYASH
#OOLER
CONDENSER
$RYINGAND
COMPRESSING
!SH
/XYGEN
Figure 4 Oxyfuel fow scheme
fw.indd 4 10/3/10 13:25:38
may wish to focus on one location
in which there is a specic driver,
such as an emissions trading
scheme. Likewise, there may be a
plant with a need to improve
energy security in response to a
frequently interrupted electricity
supply from an overloaded, over-
the-fence grid connection.
With any investment project, a
number of stakeholders will be
involved and it is important to keep
them all positively engaged, partic-
ularly if a new technology such as
CCS is to be employed. Non-
governmental organisations (NGOs)
and local residents may be
concerned about new technology
and require reassurance that risks
to the environment and safety are
mitigated responsibly. They may
also wish to know what other
options were considered during the
project development.
Market analysis
A wide range of schemes offers
incentives for energy efciency and
reduced CO
2
emissions; these
augment the natural economic driv-
ers for the process industry, to
minimise waste and maximise qual-
ity and output.
Understanding what is available
in the region in which a project will
operate could enable the project to
be signicantly more economic.
Examples include regional emis-
sions trading and grants for new or
clean technology demonstrations.
The reverse can apply, particularly
with the currently uncertain future
of regulating GHG emissions, if
taxes or levies may be brought into
force in the near future. Being at a
transition point in legislation can
make it particularly difcult to
predict and select a rm basis for
investment.
Equally there may be the oppor-
tunity to use captured CO
2
for
enhanced oil recovery or enhanced
gas recovery, either by the project
company itself or sold over the
fence to an operator.
Understanding the market and
legislative context of the project will
help to mitigate the risk of being
locked into expensive carbon penal-
ties or high electricity or fuel prices,
while identifying any additional
revenue streams that may not
usually be encountered.
Plant conguration studies
Once the projects objectives are
dened and the applicable market
and legislative framework is under-
stood, potential process routes and
technologies can be identied. LP is
useful for determining the optimum
conguration for energy security
and for minimising CO
2
emissions.
The ability to run a number of
what-if scenarios, once the LP
model has been developed, enables
the projects sensitivity to volatile
fuel, electricity or carbon prices to
be understood. In addition, the
impact of low availability in proc-
ess units with a high energy
demand can be determined, and an
assessment can be made of how to
congure the plant for optimal
conversion of feedstocks into prod-
ucts carrying the highest margin.
The cost/benet of building redun-
dancy into the power supply can
also be quantitatively assessed.
Just as the product yield and
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fw.indd 5 10/3/10 13:25:52
energy demand of each process unit
is built into the LP model, so can it
include the amount of CO
2
emitted.
This enables the minimum CO
2
emissions case to be identifed. If
the minimum emissions case is not
economic without carbon capture,
as a result of a high anticipated
carbon emissions penalty, carbon
capture units can be added to the
model to determine whether this
will improve the projects margin,
despite the additional capital and
operating costs.
Case study
A hydrogen production unit (HPU)
in a refnery produces a signifcant
portion of the sites CO
2
emissions
and can be the ideal candidate for
reducing CO
2
emissions. A number
of capture techniques can be
applied. For example, Foster
Wheeler has previously compared
the following options:
A Pre-combustion capture on HPU
syngas between the shift reactor
and the PSA
B Post-combustion capture on the
HPU reformer itself, where the
reformer is fred on PSA tail-gas
C Post-combustion carbon capture
on other refnery fred heaters, fred
on natural gas.
In this study, both of the carbon
capture options (A and B) delivered
signifcant CO
2
emissions reduc-
tions at a lower project cost (capital
and operating) than applying post-
combustion capture to other
refnery fred heaters on the site.
Site selection
While market analysis will have
dealt with locally applicable drivers
and the price and availability of
primary fuels and/or reliable elec-
tricity supplies, there are several
additional points to be considered
with respect to site location. Most
critically, for a project to even
consider CCS as an option for CO
2
emissions management, a suitable
storage location, and a viable trans-
port route to that location, must be
identifed at the earliest stages of
the project.
While some projects may be
conveniently located close to a
depleted oil or gas feld, others may
be relatively stranded. Options such
as shipping can be considered in
such cases, although selection of
alternative technology, or retroft,
may be a more appropriate alterna-
tive. The site selection stage should
also consider whether renewables
would offer advantages.
For both new and existing sites,
the availability of extra plot space
should be considered. Currently,
many countries require power
generators to prove that their new
plant is carbon capture ready
(CCR), which usually translates to
ensuring that there is suffcient
additional space on site to locate
the capture plant, and identifying a
storage location.
For retroft projects, the available
space may be a key determinant in
the selection of technology. For
example, a site with a number of
dilute sources of CO
2
may wish to
optimise the layout of a CO
2

capture unit by locating the capture
units CO
2
absorption step close to
the source of emissions and pump-
ing CO
2
-loaded solvent to central
solvent regeneration and CO
2
compression units, thus minimising
the space required close to the
source and reducing the amount of
ducting required.
Offsites and utilities
The requirements for utilities and
offsites are specifc to the process
confguration. More attention than
usual may be paid to sparing and
redundant capacity, but otherwise
this step is largely unchanged from
the general roadmap.
Constructability studies
For a CCS project, the physical size
of the equipment, particularly for a
post-combustion scheme, presents
challenges in terms of ensuring
constructability. In some cases, the
factor determining the number of
CO
2
absorption trains required is
fxed by the capacity of the largest
possible size of vessel that can be
shipped to the site.
Cost estimates, economic and
fnancial modelling
Economic modelling when design-
ing for maximum energy security
may be made slightly more complex
by considering a greater number of
options, or by performing sensitiv-
ity analysis on key variables such
as plant availability. A revenue
stream with an uncertain value,
such as CO
2
, should be explored to
determine the levels at which differ-
ent options become economic.
Conclusion
The investment planning roadmap
ensures that project objectives are
well defned, the project is appro-
priate for the market, the
confguration of the solution is opti-
mal, the costs are well defned and
the economic case is robust. This
rigorous and staged process is
particularly important for projects
in which there is a wide range of
unknowns, such as future CO
2
price
or penalty and volatile fuel prices,
coupled with an array of potential
options for mitigation.
Breaking the investment planning
process into manageable stages
enables a clearer picture to be
drawn and recorded with respect to
which options have and have not
been considered and how they
compare against each other and
against the overall objectives.
This article is based on a paper presented
by Mike Green, Process Consultant, Foster
Wheeler, at the Lovraj Kumar Memorial Trust
Annual Workshop, Managing Carbon Footprints
in the Process Industry, New Delhi, Nov 2009.
Selexol is a trade mark; the process is licensed
by UOP LLC.
Suzanne Ferguson is a Senior Process
Engineer with Foster Wheeler, Reading, UK,
where she is a member of the CCS and
gasifcation team in the Business Solutions
Group. She has a masters degree in chemical
engineering from the University of Surrey, UK.
Email: suzanne_ferguson@fwuk.fwc.com
The investment
planning roadmap
ensures that project
objectives are well
defned and the
economic case is
robust
fw.indd 6 10/3/10 13:26:10
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amistco.indd 1 10/12/09 12:30:59
Online cleaning and decontamination of
a butadiene unit
E
xtractive distillation of butadi-
ene is accompanied by a
characteristic fouling issue.
The material laid down in trays is
hard and polymeric, typically
formed in vapour spaces, and is
commonly identifed as popcorn
polymer. It is diffcult to remove
from equipment surfaces, infam-
mable and can cause serious
damage to internals, so its removal
is a priority during unit turnarounds.
Most butadiene is a by-product of
ethylene production from steam
crackers. The C
4
stream isolated
from the steam cracking process is
fed to butadiene extraction units,
where butadiene is separated from
the other C
4
s by extractive distilla-
tion. The amount of C
4
s produced
in steam cracking depends on the
composition of the feed to the
cracking unit. Heavier feeds yield
higher amounts of C
4
s and butadi-
ene than lighter feeds. Crackers
using light feeds typically produce
low quantities of C
4
s and do not
feature butadiene extraction units.
Butadiene capacity is determined
by ethylene cracker operating rates,
the type of feed being cracked and
the availability of butadiene extrac-
tion capacity. Butadiene is typically
isolated from other C
4
s produced in
steam cracking by extraction into a
polar aprotic solvent such as
acetonitrile, from which it is then
stripped by distillation.
Polimeri Europa, part of the Eni
Group, has 18 production sites in
Europe, along with four research
facilities. The companys Brindisi,
Italy, site includes a 147 000 tonne/
year butadiene unit, which uses
acetonitrile as the extractant solvent.
The extractive distillation section of
Chemical treatment by closed-loop recirculation reduced cleaning time for a
butadiene unit turnaround from a typical 20 days to 24 hours
Dino PolvErini and Cosimo CuCinElli Polimeri Europa
marCEllo FErrara ITW
this unit comprises four columns: a
frst and a second extractor (contain-
ing 90 trays each), a stripper (also
containing 90 trays) for stripping
butadiene and acetylenic com-
pounds from the solvent, and a
solvent regenerator. The unit under-
goes turnaround every fve years.
During the latest turnaround, to
improve operations, the company
wanted to fnd ways of reducing
the time it takes to achieve safe
entry conditions and of modifying
the polymer to make it easier to
remove. During previous turna-
rounds, operators encountered a
bottleneck during the removal of
the polymer inside the extractive
distillation section. This problem is
inherent to the butadiene unit and
is encountered, to a greater or lesser
extent, worldwide.
So-called popcorn polymer is a
well-recognised operational prob-
lem inside butadiene units in
particular and more generally
throughout the petrochemical
industry. This polymer is sticky and
hard to remove, to such an extent
at Polimeri Europa that the trays
could not be cleaned on-site and
instead had to be dismounted and
mechanically cleaned off-site.
This operation was particularly
diffcult and time consuming
because the frst and second extrac-
tor, as well as the stripper, are each
93m high. The dismounted trays
had to be cleaned at ground level
by mechanical scraping, as hydro-
blasting would have had little
effect. This was made more diffcult
by the adhesive nature of the poly-
mer. After cleaning, the trays were
remounted and restored to opera-
tion. Together, these diffculties
added up to a lengthy cleaning
operation that had a huge impact
on plant downtime. Based on
historical cleaning data from the
site, 20 days of mechanical cleaning
was scheduled for a typical
turnaround.
Ensuring safe entry conditions for
operators was also problematic.
Conventional gas-freeing methods
were not suffcient. Extra precau-
tions had to be taken and operators
needed to wear breathing apparatus
when they were working inside the
columns. Once the polymer was
eventually removed by mechanical
means, its noxious odour added to
the problems. To try and solve
some or all of these problems,
Polimeri Europa decided to
feld trial two novel technologies
for modifying polymers and
degassing/decontamination.
ITW has developed and patented
a technology for online cleaning
productions units, which has a
number of advantages over conven-
tional manual cleaning or
hydroblasting, including:
A closed-loop operation, with no
need to open units during cleaning
A safe and environmentally
friendly operation
Popcorn polymer is
diffcult to remove
from equipment
surfaces, infammable
and can cause serious
damage to internals
itw.indd 1 8/3/10 14:56:45
units, particularly popcorn-type
polymer, ITW successfully set up a
fve-year research programme to
develop a chemical that could
modify the polymeric deposits to
make them much easier to remove.
Industrial test
The novel polymer modifer is
completely safe for use inside a unit
as it does not contain any:
Metals
Compounds of P, B, S, As, Bi, Si
or Pb
Halogens
Compounds that might be harm-
ful to plant metallurgy
Carcinogenic compounds
Compounds that, at operational
dosages, might interfere with
biological waste treatment processes.
According to laboratory tests, this
chemical treatment is able to modify
butadiene polymers from a hard-to-
remove, sticky substance into a
sand-like material that is much
easier to remove.
The original work scope specifed
that, while the polymer should be
modifed for easier removal, it
should be left in place for
subsequent mechanical cleaning on-
site, thereby reducing the need to
dismount the trays and perform
mechanical cleaning off-site, thus
reducing associated downtime and
additional mechanical operations.
In fact, the fnal outcome of the
polymer modifcation and cleaning
operations went beyond the origi-
nal plan. For Online Cleaning, the
chemical would have to be circu-
lated inside the unit by means of a
closed-loop circulation system.
Before the technologies were put
into operation at Brindisi, ITW and
Polimeri Europa agreed upon a
circulation scheme whereby no
additional external piping would be
needed to implement a circulation
loop; instead, the units own equip-
ment would be used exclusively.
Before turnaround, operations
personnel carried out conventional
shutdown procedures, which
included fushing out entrained
hydrocarbons, according to the
normal schedule. Once the unit was
fushed out, the circulation loop
could be established. After the
circulation loop was closed, the
No waste generation
No emissions.
The technology has already been
applied successfully to many refn-
ery units to remove heavy
asphaltenes/paraffns and coke-like
deposits. A production unit can be
Online Cleaned in 24 hours on an
oil-to-oil basis, and a crude distilla-
tion unit can be Online Cleaned,
spec-to-spec, in about 30 hours. If
cleaning is performed just prior to
turnaround, a subsequent ITW
Improved Degassing/Decontamin-
ation step can be applied to
improve turnaround operations and
reduce downtime.
One characteristic of ITWs Online
Cleaning process is that no waste is
generated and washing fuids can
be fully reused and/or reprocessed.
Moreover, because it is a closed-
loop operation, no airborne
emissions are generated.
To address the removal of poly-
meric compounds from petrochemical

Fig1:

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MOVING AHEAD
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itw.indd 2 10/3/10 13:31:57
extractive distillation section would
be partially flled with a carrier that
is available from the site. Thereafter,
patented chemical would be
injected into the loop and circula-
tion started up by means of the
extractive distillation sections
bottom pumps.
Immediately after circulation
started, the chemical began to take
effect, in that the polymer inside
the loop became disengaged and
entrapped in the bottom pumps
flters. These flters very quickly
flled up with polymer and subse-
quently required cleaning. As a
flters delta P reached the opera-
tional target level, the pump was
bypassed and a spare pump was
brought into service.
Since the disengaged, modifed
polymer was in a sand-like state,
and not at all sticky, it was very
easy to remove from the flter
baskets. Simply extracting a flter
basket from its housing and turning
it over enabled the polymer to be
transferred directly into drums for
subsequent disposal.
The circulation process lasted 24
hours. During that time, polymer
was continually removed from the
system and entrapped in the bottom
pump flters, which were cleaned
about 30 times. Once the circulation
process was complete, the washing
fuids (the carrier and the polymer
modifer) were pumped out for
subsequent reuse. In this instance,
the fuids were transferred to a
tank and thereafter fed to the
ethylene unit. No problems were
recorded during the reprocessing of
the washing fuids together with
the feed in the ethylene unit.
Once the butadiene unit had been
drained according to normal proce-
dures, the Improved Degassing/
Decontamination step could be
implemented. This adds a patented
chemical treatment by water circu-
lation or injection into steam. The
chemical temporarily solublises
hydrocarbons in water, thereby
quickly removing them from metal
surfaces. It simultaneously elimi-
nates any H
2
S/ mercaptan
emissions, reduces benzene inside
the equipment to levels below 1
ppm and eliminates any problems
with pyrophoric solids. The chemi-
cal does not form emulsions and
has a low chemical oxygen demand
(COD).
Results
The application of Online Cleaning
and Improved Degassing/Decon-
tamination achieved a range of
positive results. At the manway
opening, the extractive distillation
columns were almost metal clean,
unlike conditions at the start of
cleaning operations, when a thick,
sticky polymer was frmly attached
to the equipment. Only a small
amount of polymer was left inside
the columns, and this was located
almost exclusively in the dead legs.
This unexpected result far
Figure 1 Extractive distillation bottom
Figure 2 Extractive distillation trays
outperformed the original scope of
work, whereby the polymer was
expected to remain in the columns,
although in a modifed state that
would be relatively easy to remove.
Figures 1 to 4 show the column
internals immediately after the
manway was opened and before
any maintenance activity had taken
place. Images of the chimney trays
(see Figures 5 and 6) clearly show
the amount of polymer originally
present in the trays and the amount
left after cleaning.
Once the manway was opened,
the equipment was safe for opera-
tor access and the following
conditions were recorded:
LEL =0 %
itw.indd 3 10/3/10 13:32:12
H
2
S=0ppm
Benzene=0ppm
No problems with pyrophoric
solids
Noparticularodourwasdetected
insidetheequipment.
In view of these conditions, oper-
ators did not need to wear any
breathing apparatus. Similarly, the
modifed polymer that had been
entrained in the bottom pumps
flters, as well as minor amounts
left in the columns (see Figures 7
and 8), had no odour. This was an
additional unexpected result, as
butadienepolymersarewellknown
in industry for their characteristi-
cally strong odour that remains
detectableforyears.
Finally, because Online Cleaning
operates in a closed loop, it is
applied to all equipment in the
loop. This is particularly signifcant
for lines, as it is a huge and expen-
sivejobtomechanicallycleanthem.
As a result, they are cleaned only
under specifc and strict conditions,
such as when the fouling deposits
might impair the units operations.
Eventually, fouling build-up can
become a problem during the run,
and lead to serious operational
problemsandincreaseddowntime.
Acknowledgments
Special thanks to all operating personnel
of Polimeri Europa Brindisis butadiene
unit, who co-operated in the application of
these technologies, and to Polimeri Europas
management, who agreed to the testing of
novel technologies.
Dino Polverini is the Production Manager of
Polimeri Europas Brindisi site. He graduated in
chemical engineering from Bologna University,
Italy, and has 12 years experience in the feld.
Email: dino.polverini@polimerieuropa.com
Cosimo Cucinelli is Manager of the butadiene
unit at Polimeri Europas Brindisi site. He
graduated in chemical engineering from Turin
University, Italy, and has eight years experience
in the feld.
Email: cosimo.cucinelli@polimerieuropa.com
Marcello Ferrara is Chairman of ITW Srl. He
holds a doctorate in industrial chemistry from
Messina University, Italy. He has 23 years
experience in the refning/petrochemical
industry and holds patents for new processes
and additive compositions for environmental
control and improving petroleum/
petrochemical processes.
Email: mferrara@itw.it
Figure 5 Chimney trays
Figure 4 Downcomer
Figure 3 Extractive distillation distributor and trays
itw.indd 4 10/3/10 13:32:27
Figure 6 Chimney tray particular
Figure 7 Minor polymer left (easy to remove)
Figure 8 Minor polymer left (easy to remove)
temperature spread in the cross-
section of the catalyst bed without
any risk of hotspot formation. Due
to this improved temperature
control, it is possible to increase the
cycle length of the catalyst by
driving the end-of-run temperature
closer to the design temperature of
the reactor. Therefore, when
considering a catalyst cycle, it is safe
to say that modern VLT internals
raise the incremental production of
diesel.
The required height for installed
VLT reactor internals is, in general,
lower than for the old design. The
difference in free reactor volume
between the old and compressed
VLT reactor internals allows for
additional catalyst to be loaded in
the reactor, creating an additional
possibility to increase the throughput
of the hydrotreating unit.
J
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Effective reuse of hydrotreating
catalysts is a practical way for
refners to save money and reduce
their environmental footprint.
Improvements in recovery of spent
catalyst activity have made several
technological leaps from in-situ
regeneration to ex-situ regeneration
to active site rejuvenation. Each of
these technological developments
expanded the range of catalysts
and the range of applications for
which catalyst reuse is viable.
Albemarle believes the next gain in
the reuse of hydrotreating catalyst
will come from proper positioning
of the catalyst to take advantage of
an understanding of reaction
chemistry in the reactor. Albemarle
has pioneered this understanding
of reaction chemistry and simul-
ation with the development of STAX
technology. This allows for catalyst
system simulation, optimisation and
design with multiple constraints.
STAX catalyst systems designed to
maximise the reuse of hydrotreating
catalyst, while still meeting cycle
length and product property
requirements, can be a very
economical solution in these times
of constrained operating budgets.
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Most hydroprocessing catalyst
suppliers have commercialised
various processes for returning
activity to high-performance, Type
II catalysts after usage. Unlike
earlier generations of hydro-
processing catalysts, nano-scale
reorientation of the active metal
components is required in addition
to carefully conducted oxidative
regeneration processes. ARTs most
recent effort in this arena has been
the commercialisation of the Phoenix
reactivation process, which has
proven to be particularly resilient
and robust in treating an apprec-
iable variety of hydrotreating
catalysts and returning them to
high-performance states.
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For the future supply of biofuels,
there is no silver bullet solution.
Several pathways are being
developed, starting from a range of
raw materials, and different types of
biomass and algae are among these
options. Key to the successful
production of biofuels is low cost
and the availability of the starting
materials in large quantities. The
technology based on algae is still in
its early phase of development and
actually, to some extent, a hype.
Major technical hurdles are to be
overcome at the production side,
such as how and where to grow
algae in bulk quantities in a
sustainable way, and how to extract
and convert the raw materials. So,
in Albemarles view, algae are, in
theory, extremely interesting, but, in
practice, still far away. Other biofuels
technologies are much closer to
realisation and will precede algae
oils by many years.
*1IMJJ*+)*) ppp'îmj'\hf
Our knockout drum needs
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Can we add one without
overhauling the vessel?
Read more on this topic at
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ITS A MORE COMMON problem than
you might think. A vertical knockout
drum removes free liquid from a
certain gas stream. But at the time the
plant was built, a mist eliminator was
not considered necessary. Now mist
is carrying over and causing trouble
downstream. There is no manway, so
adding a conventional mist eliminator
would require cutting the vessel open.
nstead, if the fanged exit nozzle
is at least six inches in diameter, you
can simply hang a patented MistFix
mist eliminator inside, securing it
between the fanges.
Even when there is a manway,
MistFix avoids entry, welding, and
recertifcation in retrofts. For new
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installation cost and downtime.
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V|slF|x |rserl|or r|sl e||r|ralor
ppp'imj^gjnbkr'\hf
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Q&A copy 2.indd 2 10/12/09 11:46:27
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itw.indd 5 11/3/10 11:13:24
In a single process step, BASF
combines a new, advanced FCC
catalyst matrix with our proven
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Suitable for all FCC feedstocks
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HDXtra, the rst catalyst derived from
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Optimisation of product yield and coke
formation in a RFCC unit
R
esidue fuid catalytic cracking
(RFCC) is used for upgrading
heavy feedstocks to light
products such as gasoline. In this
study, simulation of a commercial
RFCC unit was calibrated against
actual plant data, acquired in test
runs, and its performance predicted
by simulation studies. The effects of
key operating variables, such as
temperature, input, steam fow rate
to the riser, recycle rate of light
cycle oil (LCO) on the yield of
products and rate of coke deposi-
tion on the catalyst, were studied.
The simulation results demonstrate
that during the study period, and
while all other operating parame-
ters are held constant, the rate of
injected steam to the riser, and the
recycle rate of LCO, can reduce
coke formation in the RFCC
process.
Fluid catalytic cracking
Fluid catalytic cracking (FCC) is an
effective refnery process for the
conversion of heavy gas oils to
gasoline. It is carried out at high
temperature by contacting residue
feed with an appropriate catalyst
without hydrogen. After separation
from the catalyst, the hydrocarbons
are separated into desired products,
such as LPG, gasoline, distillate and
fuel oil. In this process, coke is
deposited on the catalyst during the
reaction and is burned off in the
regenerator. When applied to the
upgrading of heavy oil, the catalytic
cracking process has been used to
maximise the gasoline yield of
refneries.
The processing of heavier crude
oil sources has resulted in an
increase in the boiling point and
Simulation studies of a commercial residue fuid catalytic cracking unit indicate
the conditions for an optimum balance of product yield with low coke deposition
SepehR Sadighi, Seyyed Reza SeiF Mohaddecy, oMid ghabouli and Mehdi RaShidzadeh
Research Institute of Petroleum Industry
Conradson carbon residue (CCR) of
the feedstock used in FCC plants.
This process, using heavy residual
oil, is RFCC, which requires differ-
ent catalysts to those used in the
FCC process.
1
RFCC catalysts are
designed to be more stable than
FCC catalysts because of the higher
cracking temperature required for
heavier feedstocks. Moreover, they
should tolerate high levels of cata-
lyst poisons, compared to FCC
catalysts, because of the RFCC
feeds higher content of heavy
metals, such as nickel, iron and
vanadium.
2
To maintain acceptable yields,
licensors and catalyst suppliers
have modifed traditional FCC tech-
nology in such key areas as catalyst,
feed injection, riser design, separa-
tion section and reactor/regenerator
design. These improvements have
enabled FCC operators to apprecia-
bly increase their level of residue
processing, so that their conversion
rate is 75% of the fresh feedstock.
This new generation of catalysts
substantially reduces riser residence
time, providing greater selectivity
and control over distillate products.
Licensors are now looking to
shorten this to remove the riser
altogether. Effcient and rapid sepa-
ration of products from the catalyst
is essential; otherwise, cracking will
continue to lead to unwanted gas
and coke production.
process description
RFCC is an extension of conven-
tional FCC technology, offering
better selectivity to produce higher
amounts of gasoline and less
gas than hydro and thermal proc-
esses. In order to control the
Gas (C
4
+ lighter)
Gasoline
Light gas oil
Heavy gas oil
Steam
Combustion air
Raw oil charge
Flue gas to particulates
Removal & energy recovery
Regenerated
catalyst
Spent
catalyst
Crude oil
Catalyst
stripper
Clarifed slurry
Fractionator
Slurry
settler
Regenerator
Reactor or
separation vessel
Figure 1 Block fow diagram of the target refnerys RFCC unit
nioc.indd 1 8/3/10 15:00:49
heat balance and recover part of
the heat for steam production,
the design of an RFCC unit
includes two-stage regeneration,
mix temperature control and cata-
lyst cooling.
3,4
The catalyst used for RFCC is an
acidic matrix such as crystalline
aluminosilicate zeolite (USY or rare
earth exchanged HY) in an inor-
ganic matrix, which meets the
required physico-chemical proper-
ties. The major limitation of the
RFCC process is the requirement of
high-quality feedstock (high H/C
ratio and low metal content) to
avoid the deposition of coke, high
catalyst consumption and unit oper-
ability. Therefore, this process can
only treat atmospheric residue,
which contains relatively low
amounts of metals, sulphur and
carbon. However, the availability of
such feeds is limited in refneries.
Moreover, the crude from which
they are derived is relatively high
in price.
5-8
As Figure 1 shows, RFCC utilises
a riser-reactor, catalyst stripper,
frst-stage regeneration vessel,
second-stage regeneration vessel,
catalyst withdrawal well and cata-
lyst transfer lines.
Fresh feed is fnely atomised with
dispersion steam and injected into
the riser through the feed nozzles
over a dense catalyst phase. The
small droplets of feed make contact
with the freshly regenerated cata-
lyst and vapourise immediately.
The oil molecules mix intimately
with the catalyst particles and crack
to form lighter, more valuable
products. Steam is injected through
nozzles into the mixture of catalyst
and vapourised feed. The operation
is carried out at a temperature
that is consistent with targeted
yields.
Products exit the riser-reactor

Fig1:

Unstabilised
LPG
Inerts
Regen.
steam
RFCC coke
Raw FCC
feed
Inject steam
Strip steam
FCC ofgas
FRCG
LCO
CSO
FCC
mixer
Blended FCC
feed
RFCC
product
RFCC
fractionator
T
RFCC
Figure 2SimulationofRFCCunit
Temperature, C
Gasoline
LCO
25
30
35
40
45
20
5l5 520 525 530 535 540
%

,
d
l
e
i
Figure 3EffectofrisertemperatureonyieldsofgasolineandLCO
Specifcation Value
Infuenceriserlength,m 38
Riserdiameter,m 0.5
Riserinlettemperature,C 525
Riserinletsteamfow,kg/hr 3500
Specifcations and operating
conditions of riser
Table 1
True boiling point range, C Sp.Gr. Feed rate, bpd
Lightvacuumgasoil 241-421 0.878 10400
Heavygasoil 224-453 0.896 5370
Heavyvacuumslabs 355-534 0.957 9570
Treatedresidue 361-562 0.952 60860
Fresh feed analysis
Table 2
Product name Volume % in product
Simulation Actual data
Lightgas&LPG 7.58 9.69
Gasoline(FRCG) 49.66 50.76
Lightcycleoil 31.88 29.05
Clarifedoil 10.88 10.5
Comparison of product yields: simulation results and actual data
Table 3
nioc.indd 2 8/3/10 15:01:00
through a high-effciency, close-
coupled, proprietary riser
termination device. Spent catalyst is
pre-stripped by a high-effciency
packed stripper prior to regenera-
tion. The product vapour is
quenched to give the lowest dry
gas and maximum gasoline yields
attainable. Final recovery of catalyst
particles is performed in cyclones
before the product vapour is trans-
ferred to the fractionation section.
Catalyst regeneration is carried
out in two independent stages
equipped with proprietary air and
catalyst distribution systems, which
create fully regenerated catalyst
with minimum hydrothermal
deactivation.
These benefts are achieved by
applying the frst-stage regenerator
in a partial-burn mode, the second-
stage regenerator in full combustion
mode, and both regenerators in
parallel with respect to air and fue
gas fows.
The process is capable of upgrad-
ing feeds to about 6 wt% Conradson
carbon content without additional
catalyst cooling, with less air, lower
catalyst deactivation and smaller
regenerators than a single-stage
regenerator design. Gas oil extrac-
tion can be easily retroftted.
Process simulation
This article reports on the effects of
recycling LCO on the yield of prod-
ucts and coke deposition on the
catalyst in an Iranian RFCC unit.
9

The specifcations and operating
conditions for the riser, as well as a
fresh feed analysis, are shown in
Tables 1 and 2, respectively.
In addition, unstable LPG is
injected with the fresh feed at a
fow rate of 2200 bpd. In this study,
Hysys Refnery was used for simu-
lation and sensitivity analysis of the
RFCC unit.
10
In this simulator, kinetics corre-
spond to operating conditions by
the tuning of kinetic coeffcients.
Simulation of the RFCC unit is
shown in Figure 2, and a compari-
son between the predicted product
yields and actual data taken from
the target refnery is shown in Table
3. This confrmed the ability of the
simulator to predict the desired
outputs.
Temperature, C
CSO
Coke
5
7
9
ll
l3
3
5l5 520 525 530 535 540
%

,
d
l
e
i
Figure 4 Effect of riser temperature on yields of coke and CSO

Gasoline
LCO
Piser inlet steam, kg/hr
32
34
36
40
38
42
30
3000 3200 3400 3600 3800 4000
%

,
d
l
e
i
Figure 5 Effects of riser inlet steam on product yields

Figure 6 Effects of riser inlet steam on yields of gasoline and coke
Coke
Gasoline
Piser inlet steam, kg/hr
40.5
40.6
40.7
40.9
40.8
40.4
5.2l
5.22
5.23
5.25
5.24
5.20
3000 3200 3400 3600 3700 3900
%

,
d
l
e
i
y

e
n
i
l
o
s
a
G
%

,
d
l
e
i
y

g
n
i
k
o
C
nioc.indd 3 8/3/10 15:01:14
Effects of injected steam
The effects on gasoline and LCO
yields of injecting steam to the riser
are shown in Figure 5. The fgure
indicates that increasing the rate of
injected steam has a positive effect
on the yield of gasoline, but it
decreases LCO production. In view
of the importance of gasoline
production and coke formation, a
sensitivity analysis of these varia-
bles is shown in Figure 6. This
demonstrates that a rate of 3200
kg/hr of injected steam is the opti-
mum for production of gasoline
with the least amount of coke
formation.
LCO recycle stream
Since recycling LCO dilutes the
feed entering the riser, it decreases
coke formation in the RFFC proc-
ess.
11
Figure 7 shows a new scenario
in which LCO product is recycled
and combined with fresh feed. To
fx the rate of combined feed, the
rate of fresh feed is decreased
accordingly.
The effects of LCO recycle on the
yields of gasoline and LCO, as well
as the rate of coke deposition on
the catalyst, are shown in Figures 8
and 9. Figure 8 indicates that
increasing the recycle stream
increases the LCO yield and
decreases the yield of gasoline.
Regarding Figure 9, it is obvious
that increasing the recycle stream
decreases coke formation and that a
LCO recycle fow rate of more than
3000 bpd represents optimum
conditions. Since it decreases coke
formation, increasing the rate of
LCO recycle can be benefcial to the
life of the catalyst.
Conclusion
In this study, the RFCC process was
frst of all simulated using Hysys
Refnery software. The simulation
was validated by comparing
predicted yields with measured
data taken from a commercial
RFCC unit. The effects on the yields
of gasoline and LCO, and on coke
formation, of temperature, inlet
steam fow rate to the riser and
LCO recycle rate were investigated.
The results confrmed that
temperature had a positive effect
on gasoline yield, but it had the
reverse effect on LCO production.
Moreover, the inlet steam fow rate
to the riser had a direct effect on
gasoline production, but because of
increasing coke formation it must
be introduced at an optimum rate.
Although LCO recycle leads to a
decrease in gasoline production, it
has a notable effect on coke
formation.
Hysys Refnery is a mark of Hyprotech and KBC
Advanced Technologies.
References
1 Corma A, Martinez-Trirguero J, The use of
MCM-22 as a cracking zeolitic additive for
FCC, J. Catal, 165, 1997, 102.
Results and discussion
Effects of feed temperature
The effects of the temperature of
the feed entering the riser on
the yield of products and coke
formation are shown in Figures 3
and 4.
Figure 3 shows that raising the
feed temperature increases both the
cracking rate and the yield of gaso-
line; as a result, the yields of LCO
and CSO decrease. Since it also
promotes coke formation, which
accelerates catalyst deactivation,
raising the temperature is an impor-
tant variable that should be handled
with caution.
LvGO
HGO
HvS
T PCC
feed
OCT LPG
LCO product
Cutter Cutter back
CDU LPG
PCC offgas
PPCG
LCO
CSO
PPCC coke
TLL-l00
TP feed
P
Unstabilised
LPG
TP excess
Paw PCC feed
PCC
mixer l
PCC
mixer 2
Pecycle
RFCC
T
FCC
yield
(mass)
FCC
yield
(vol)
Figure 7 Recycling part of LCO product as inlet feed
LCO
Gasoline
LCO recycle, bbl/d
40.3
40.6
40.5
40.4
40.7
40.9
40.8
40.2
3l.4
3l.2
3l.8
3l.6
32.2
32.0
32.6
32.4
3l.0
0 l000 2000 3000 6000 5000 7000
%

,
d
l
e
i
y

e
n
i
l
o
s
a
G
%

,
d
l
e
i
y

O
C
L
Figure 8 Effect of LCO recycling on gasoline and LCO yields
nioc.indd 4 8/3/10 15:01:24
2 ChoSI,JungKS,WooSI,Regenerationof
spent RFCC catalyst irreversibly deactivated
by Ni, Fe andV contained in heavy oil, Appl.
Catal.,33,2001,249.
3 OConnor P, Verlaan J P J, Yanik S J,
Challenges, catalyst technology and catalytic
solutions in resid FCC, Catal Today, 1998, 43,
30513.
4 Andersson S I, Myrstad T, Evaluation of
residue FCC catalysts, Appl Catal A: General,
1998,170,59.
5 ParkSK,JeonHJ,JungKS,Regenerationof
spentcatalystbyremovingmetalpoisonssuch
asV,Ni,andFe,Ind. Eng. Chem. Res.,42,2003,
736.
6 Lars S, Andersson T, Lundin T, Jras S,
OttersedtJ,Appl. Catal., 2,1982,207.
7 Pompe R, Jras S, Vanderberg N G, Appl.
Catal.,13,1984,171.
8 Lappas A A, Nalbandian L, Iatridis D K,
Voutetakis S S, Vasalos I A, Effect of metals
poisoningonFCCproductsyields:studiesinan
FCCshortcontacttimepilotplantunit,Catal
Today,65,2001,233.
9 MeyersRA,Handbook of Petroleum Refning
Processes,McGraw-Hill,1997.
10 Hysys Refnery User Guide, KBC Advanced
Technologies,KBCProfmatic.
11 AncheytaJ,RodriguesS,Resultsofprocess-
ingVGO-LCOblendsinaFCCcommercialunit,
Energy and Fuels,2002,16,718723.
Sepehr Sadighi is a Project Manager at the
Research Institute of Petroleum Industry,
Tehran,specialisinginmodellingandsimulation
studies of refnery processes. He has a
bachelors degree in chemical engineering
from Iran University of Science and
Technology and a masters in separation
technology from the Technology University
ofSharif.Email Sadighi_sepehr@yahoo.com
Seyyed Reza Seif Mohaddecy is a Senior
Researcher at the Research Institute of
Petroleum Industry, Tehran, and a Lecturer in
Chemical Engineering at Arak Islamic Azad
University. He has a bachelors degree in
chemical engineering from Tehran University
and a masters from Sharif University of
Technology.Email Seifsr@ripi.ir
OmidGhabouliisaResearcherattheResearch
Institute of Petroleum Industry, National
IranianOilCompany,Tehran.
Mehdi Rashidzadeh is Head of the Catalyst
Research Center at the Research Institute of
Petroleum Industry, Tehran, He has a Phd in
chemistry.
LCO
Gasoline
LCO recycle, bbl/d
40.3
40.6
40.5
40.4
40.7
40.9
40.8
40.2
5.l5
5.20
5.25
5.l0
0 l000 2000 3000 6000 5000 7000
%

,
d
l
e
i
y

e
n
i
l
o
s
a
G
%

,
d
l
e
i
y

e
k
o
C
Figure9EffectofLCOrecyclingongasolineandcokeyields
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Optimising steam systems: part I
S
o far 2010 is proving to be
another challenging year for
the refning industry. Not only
is it currently experiencing spare oil
production capacity of over 6
million barrels/day, leading to a
fall in refning margins, but the US
Environmental Protection Agency
(EPA) has confrmed its stance, that
greenhouse gases (GHGs) are a
threat to health and welfare. This
has led to the Mandatory Reporting
of Greenhouse Gases Rule, requir-
ing all US oil and petrochemical
companies, as with all sectors of the
economy, to monitor and report
their GHG emissions. In Europe,
the EU has committed to cutting its
CO
2
emissions by 20% by 2020 from
1990 levels.
This article, and part II to be
published at a later date, looks at
ways of optimising the steam
system, to reduce energy costs
(lowering GHG emissions), water
consumption and boiler chemicals.
In addition, ensuring the steam is
of the correct quality, quantity and
pressure when it arrives at its point
of use can improve process
performance.
It is estimated that steam genera-
tion accounts for approximately
50% of the total energy consump-
tion in a typical refnery, with
energy costs accounting for more
than 50% of the total operating
expenditure.
The US Department of Energy
estimates that steam generation,
distribution and cogeneration offer
the most cost-effective energy eff-
ciencies in the short term, with
potential energy savings of more
than 12%. Table 1 estimates the
typical savings that can be achieved
Simple techniques to reduce the cost of ownership of a refnerys steam
distribution system and condensate return using steam traps and separators
Ian FlemIng
Spirax Sarco
for the steam distribution system
and condensate return of a US
refnery.
Further savings can be achieved
in the powerhouse where steam is
generated. However, this article
measure Fuel saved, % Payback period, yr Other benefts
Improved insulation 313 1.1
Steam trap maintenance 1015 0.5
Automatic steam trap monitoring 5 1
Leak repair 35 0.4 Reduced requirement
for major repairs
Flash steam recovery/ Dependent on existing Variable dependent Reduced water
condensate return use for fash steam on application consumption and
water treatment costs
Condensate return alone 10 1.1 Reduced water consumption
and water treatment costs
Potential savings in a refnerys steam distribution system and condensate return
S
t
e
a
m

d
i
s
t
r
i
b
u
t
i
o
n
Table 1
Saturated
water line
Evaporation
lines
Critical
point
Lines of
constant
pressure
Dry saturated
steam line
Superheated
steam region
E
D C
B
Dryness fraction lines
Lnthalpy h, k1/kg
l00
200
300
400
0
500
h
f
h
fg
l500 2000 2500 3000 3500
C

,
t

e
r
u
t
a
r
e
p
m
e
T
l000 0
A
Figure 1 Temperature enthalpy diagram
spirax.indd 1 11/3/10 14:11:59
will examine only steam distribu-
tion and condensate return.
Before looking at potential
improvements and ways of optimis-
ing the steam system, it is worth
understanding the basic properties
and characteristics of steam. These
can be outlined in a temperature
enthalpy diagram (see Figure 1).
When energy is added to water,
the temperature rises until it
reaches the point of evaporation
(point B in Figure 1), which varies
with pressure. The energy required
to reach point B is sensible heat (h
f
).
Any additional energy will convert
the water to steam at a constant
temperature. At point D, all water
has been completely converted to
steam, which is known as dry satu-
rated steam with a steam quality
(dryness fraction) of 100%.
The energy added between points
B and D is the enthalpy of evapora-
tion (h
fg
) and is the energy steam
gives out as it condenses back to
water. It is the enthalpy of evapora-
tion that is used in refning.
If further energy is added, the
steams temperature will increase,
creating superheated steam (E).
Superheated steam is used in a
typical powerhouse (at approxi-
mately 100 barg and 450C) as part

Fig1:

of the cogeneration or combined

heat and power (CHP) system.
For heating purposes, super-
heated steam offers very little extra
energy and, in fact, the steam has
to cool to saturated temperature
before the enthalpy of evaporation
can be released. Therefore, using
superheated steam instead of satu-
rated steam at the point of use
actually slows down the heating
process.
For the process to achieve maxi-
mum effciency, steam needs to
arrive at the correct:
Quality: target dryness fraction of
100%
Quantity to allow the process to
meet demand
Pressure, which determines satu-
rated steam temperature and
specifc volume, so affecting ther-
mal transfer.
Steam quality is a measure of
dryness fraction. If the dryness frac-
tion is lower than 100% (say, point
C in Figure 1), the available energy/
kg of steam is less. Steam quality
can be improved by ensuring the
mains are well insulated and
condensate is removed effectively
using steam traps and separators.
The quantity of steam required
will depend on the process energy
requirements. Effective deliver
relies on correct sizing of the steam
distribution lines and control valves
serving the application. This can
become an issue when processes
are upgraded or additional assets
are added, as it increases the steam
load beyond the steam mains origi-
nal specifcation. This results in
increasing velocities within the
steam system, causing higher pres-
sure losses through the distribution
system. If the steam pressure is
lower than the acceptable design
pressure, the process is de-rated, as
the steam is at a lower saturation
temperature, reducing the energy
transfer rate.
Several key areas have the great-
est effect on reducing energy costs
and improving effciency: steam
system insulation, water hammer
and steam trapping.
Steam system insulation
Steam mains and ancillary equip-
ment must be effectively insulated,
in particular valves, strainers and
separators, which have large surface
areas. After any maintenance work
on the steam system, the insulation
must be replaced properly; good
insulation reduces heat losses by up
to 90%.
To put this into context, 1m of an
uninsulated 100mm steam main
operating at 10 barg emits approxi-
mately 1.0 kW, which is equivalent
to wasting nearly 16 tonnes of
steam a year. This assumes that the
pipe is dry and there is no wind
chill. Good insulation reduces these
loses to approximately 1.6 tonnes of
steam a year.
But even when insulation stand-
ards are good, a certain amount of
steam condenses out during distri-
bution. This needs to be removed
to maintain steam quality and
prevent the possibility of water
hammer.
Water hammer
As steam begins to condense,
condensate forms droplets on the
inside of the walls. These are swept
along in the steam fow, merging
into a flm. The condensate then
gravitates towards the bottom of
the pipe, where the flm begins to
increase in thickness.
Steam
Steam
C o n d en sate
Steam
Slu g
Figure 2 Developmentofconditionsforwaterhammer
Flash steam b u b b le
im p lo d es as steam
co n d en ses
C o o l
co n d en sate
Flash steam
Figure 3 Developmentofconditionsforthermalshock
spirax.indd 2 10/3/10 09:56:02
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The build-up of droplets of
condensate along a length of steam
pipework can eventually form a
slug of water, which will be carried
at steam velocity (2530 m/s) along
the pipework (see Figure 2). This
slug of water will eventually slam
into bends in the pipework, valves
or separators in its path.
There is a second cause of water
hammer known as thermal shock.
This occurs in two-phase systems,
where water occurs in two states
(water and steam) in the same pipe.
It can also occur in steam mains,
condensate return lines and heat
exchange equipment. Steam bubbles
become trapped within pools of
condensate, which have cooled
suffciently below saturated temper-
ature and immediately collapse.
Since a kilogram of steam occu-
pies several hundred times the
volume of one kilogram of water,
when the steam collapses conden-
sate is accelerated into the resulting
vacuum. As the void is flled, water
impacts the centre, sending shock
waves in all directions.
Thermal shock can, therefore,
occur where higher temperature
return systems containing fash
steam are discharged into sub-
cooled condensate return lines. The
forces resulting from water hammer
can be immense, causing steam
mains to physically move or, in
worst-case scenarios, rupture.
At best, water hammer increases
maintenance costs and at worst a
ruptured steam main will bring the
plant to a halt, possibly causing
injury to personnel. Water hammer
can be prevented easily through
good engineering practice and by
using steam traps at regular inter-
vals to prevent the build-up of
condensate.
Steam trapping
Some of the most common prob-
lems found in a steam system can
be traced back to either the steam
trap application or poor condensate
removal. These issues can normally
be resolved through good engineer-
ing practice, selection of the correct
steam trap and a steam trap
management programme.
Types of steam trap
When selecting steam traps, it is
worth remembering that most use
three principles of operation,
summarised in Table 2. Each princi-
ple has its strengths and weaknesses,
dependent on the application being
served. Table 3 gives examples of
applications and the preferred type
of trap for the application.
There are some general rules and
guidelines on where to position
steam traps:
Mechanical Thermodynamic Thermostatic
Principle of operation: Principle of operation: Principle of operation:
Distinguishes between steam and Distinguishes between steam and Uses difference in temperature between
condensate using difference in density condensate through variation of fow steam and condensate
between steam and condensate dynamics between the two fuids
Condensate has to cool below the steam saturation
Removes condensate as it forms Removes condensate as it forms temperature before the trap will open, which leads
to backing up of condensate
Three main types of steam trap
Table 2
Application Trap types Comments
Process applications Mechanical Mechanical steam traps will remove the condensate as it forms, regardless of fuctuating loads,
eg, heat exchangers: ensuring maximum steam space and heating surface area within the heat exchanger
Reboilers
Preheaters Mechanical steam traps also have the greatest capacity, making them ideal for process applications
Water heaters

Distribution lines Thermodynamic Thermodynamic traps are robust and relatively low cost. TDs remove the condensate as it forms,
eg, steam mains so eliminating the risk of condensate backing up into the steam line
Thermostatic Thermostatic traps, by their nature, will back up with condensate, but they are robust and relatively low cost.
Thermostatic traps can be used on distribution mains, providing there is a cooling leg between
the trap and the steam mains
Critical tracing Thermodynamic Thermodynamic traps are the frst choice, as they are compact, robust and low cost. They remove
eg, sulphur lines condensate as it forms, ensuring the traced product does not solidify
Mechanical Mechanical traps are also used, but tend to be less compact
Non-critical tracing Thermostatic Thermostatic traps allow the condensate to sub-cool within the tracer before being discharged. This makes
eg, instrumentation use of the sensible heat in the condensate and reduces the release of fash steam, particularly important
if the trap is discharging to grade
Preferred type of trap for various applications
Table 3
spirax.indd 3 10/3/10 09:56:17
sate line. This is because the
differential pressure across the
steam trap has been reduced, so
less condensate will pass through a
given sized orifce.
Table 4 shows typical steam
losses from a single 1/2 inch TD
steam trap used on high-pressure
(HP), medium-pressure (MP) and
low-pressure (LP) steam mains
when failed open. Although the
fgures are conservative, this clearly
shows the need to ensure steam
traps are checked regularly and
failed traps replaced as soon as
possible. HP traps should be
checked at least every six months,
while MP and LP traps annually.
During a steam trap audit, it is
not unusual to fnd more than 10%
of the steam trap population failed
open, where a customer has not
implemented a steam trap manage-
ment scheme. In value terms, this
normally shows potential annual
savings of $100 000s, with a payback
of less than six months. Figure 5
shows examples taken from actual
steam trap audits.
Along the steam main at approxi-
mately every 3050m intervals,
using a pocket that is the same
diameter as the steam main up to
100mm. This will ensure all conden-
sate running along the bottom of
the pipe is captured and removed
(see Figure 4)
At all low points on the steam
main and wherever the steam main
rises; at a gantry, for example
Before control valves, in particu-
lar valves serving a process. A
separator ensures steam entering
the process is dry, saturated steam,
improving the effciency of heat
exchange. It also minimises the risk
of erosion of the control valve,
reducing maintenance costs, and
ensures condensate is drained when
the control valve is in the closed
position, preventing the risk of
water hammer. A typical separator
and trap installation protecting a
pressure control valve station is
shown in Figure 5
Before steam isolation valves, to
remove the potential build-up of
condensate when the valve is closed
At the end of each steam main;
this should be ftted with either a
steam trap with good air venting
properties or a separate air vent.
Modern steam trap stations
normally consist of quick-ft connec-
tors, which allow traps to be
isolated and changed in minutes.
This has signifcantly reduced main-
tenance costs and the total cost of
ownership of steam traps.
Testing and maintaining steam traps
Modern steam traps are gener-
ally reliable and robust, assuming
they have been correctly sized and
selected for the given application.
However, they can fail. A steam
trap has two modes of failure: it can
fail either open or closed/blocked.
If a steam trap fails open, there
are two major consequences:
Steam wastage, resulting in
higher energy costs/greater emis-
sions, increased consumption of
water and boiler feed chemicals
If the condensate is being
returned, the condensate line
becomes pressurised, which can
have the effect of de-rating the
capacity of any other steam trap
discharging into the same conden-
Line pressure Approx steam loss, t/yr* Approx steam loss, t/yr*
(discharging into condensate line) (discharging to grade)
100 barg 460 920
20 barg 95 190
5 barg 25 50

* Based on 8700 hours/year
Steam losses from a 1/2 inch TD steam trap
Table 4
Flow
Steam trap set
C o n d en sate
Steam
TD trap with
in b u ilt strain er
Figure 4 Steam trap arrangement
3TOPVALVE
3EPARATOR
3TRAINER 0NEUMATIC
CONTROLVALVE
#ONTROLLER
3AFETY
VALVE
4RAPSET
h,OWv
PRESSURESTEAM
h(IGHv
PRESSURESTEAM
Figure 5 Typical separator and trap installation
During a steam trap
audit, it is not unusual
to fnd more than
10% of the steam
trap population
failed open
spirax.indd 4 10/3/10 09:56:33
Cold steam traps
Cold steam traps are either failed
closed, blocked or have been
isolated (having failed open).
Although it is harder to achieve a
return on investment by repairing
these traps, the consequences of
ignoring this situation can be much
more costly. Failing to replace or
maintain cold traps can result in:
Corrosion leading to system
degradation and increased mainte-
nance costs
Water hammer, with the poten-
tial for catastrophic failure of the
steam system a major safety
issue
Freezing, leading to pipe
ruptures
Valve erosion, wire drawing,
vibration and failed valve packing,
where traps have failed upstream
of control valves
Corrosion and loss of heat
transfer on tracing lines, leading
to higher pumping costs or
solidifcation of the product being
traced
Blade erosion, vibration and
drive shaft wear on turbines.
Separators on a steam system
Separators are used to remove
entrained water in the steam
system, to bring the steam quality
to nearly 100%. They consist of
baffe plates, which separate the
water droplets from the steam fow
(see Figure 6).
Separators should be installed in
the following applications:
Upstream of control valves,
particularly just before a process
where they: protect steam
equipment from erosion caused by
wet steam; ensure the process
receives dry saturated steam, so
improving performance; and drain
the build-up of condensate
upstream of the control valve when
in the closed position
At boiler off-take, to knock out
any carry-over prior to distribution
Downstream of desuperheater
stations, to remove any remaining
Unit Steam loss, $
Aromatics 51111
Firewater 6975
Flareskid 28087
Lightolefns 323847
OSBLPR 58667
Piperack 45054
Pyronaphtha 21932
Cyclohexane 28811
Airsystems 20454
Annualloss 584938
Failed open
15%
Not in use
5%
Failed closed
or blocked
20%
Working correctly
60%
Cost of steam wasted from failed
open traps from a US chemical plant
Table 5 SteamtrapauditsofUKandUSrefneries
Steam trap audit results from a UK refnery
Flow Measurement up
to 400 C. Non-Intrusive.
No clogging, no risk of leaks,
no pressure loss.
refinery-solutions.com
www.ptqenquiry.com
spirax.indd 5 10/3/10 09:56:49
water that was not absorbed by the
superheated steam
Upstream of steam turbines,
preventing the risk of damage
through water droplets or water
hammer.
Desuperheater stations
Superheated steam is generated in
most plant powerhouses as part of
the cogeneration or CHP process.
The pressures and temperatures
generated are far too high to be
used in most refning and petro-
chemical processes. Therefore, this
HP superheated steam is let down
to the MP and LP distribution lines,
using turbines or pressure-reducing
stations.
All steam desuperheaters work
on the same principle: injecting
water into the superheated steam,
where it evaporates, absorbing
excess energy and resulting in
steam with approximately 5C of
superheat. This remaining super-
heat is soon lost as the steam is
distributed to the point of use.
Figure 7 shows a typical desuper-
heater application on a letdown
station.
The quantity of water required
to desuperheat the steam is control-
led by maintaining the steam
temperature downstream of the
desuperheater to between 5C and
10C above the steam saturation
temperature.
If the temperature is too close to
the saturation curve, there is a risk
that too much water will be injected
into the system, leading to poor
steam quality and all the problems
associated with this. If the tempera-
ture is too high, excessive superheat
will remain, affecting the perform-
ance of the downstream process.
Although not much can go wrong
with the average desuperheater, it
is worth checking the required set
points for temperature and pres-
sure, and whether the desuperheater
is still correctly sized, particularly if
operating conditions or parameters
have changed.
Conclusion
This article has discussed the
importance of ensuring steam
reaches its point of use at the
correct quality, quantity and
pressure, and has looked at some of
the key areas to consider in reduc-
ing maintenance costs and energy
losses; namely the impact poor
steam quality can have on the steam
system and how this can be
improved through:
Ensuring the steam system is
properly insulated
That condensate is promptly
removed from the distribution
system
Using the correct steam trap for a
given application
Putting in place a steam trap
management programme
The use of separators
Checking the installation and
performance of desuperheater
stations.
The second part of this review of
steam system optimisation will
consider steam at the point of use
and the importance of returning
condensate back to the powerhouse.
It will also look at examples of why
heat exchangers stall and how this
has been overcome, together with
ways of utilising fash steam within
the plant.
Ian Fleming is Market Development Manager
for Oil and Petrochemicals at Spirax Sarco,
Cheltenham, UK. He has 20 years experience
in steam systems.
Email: ian.feming@uk.spiraxsarco.com
7.5 M
TE
P E
P G
P C V
1 .5 M
Air
3 M
P G P G
C o o lin g
water
T VC
Air
C h eck
valve
P C V
co n tro ller
TC V
co n tro ller
D esu p erh eater
D esu p erh eated
M P /LP steam
Su p erh eated
H P steam
Figure 7 Desuperheater application on a letdown station
Figure 6 Steam system separator
Air and
incondensable
gases vented
spirax.indd 6 11/3/10 21:55:16
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Calculating column relief loads
E
mergency relief in the process
industries aims to protect
equipment, the environment
and operating personnel from
abnormal conditions. Appropriate
estimation of relief loads under
extreme conditions is important for
the correct sizing of relief valves
and fare headers, and for the selec-
tion of disposal media. In addition,
during debottlenecking or revamp-
ing of process units, adding a new
relief valve and modifying the relief
system can be very costly and, in
terms of construction, diffcult to
implement.
Estimating accurate relief loads
for distillation columns under vari-
ous conditions is more complex
Conventional, steady-state and dynamic simulation techniques are compared in
a study of relief loads for failure modes applied to a distillation column
Haribabu CHittibabu, amudHa Valli and VinEEt KHanna Bechtel india PVE Ltd
dipanjan bHattaCHarya Bechtel Corporation
because of compositional changes
along the column height. The
conventional method of estimating
relief load (unbalanced heat
method) is normally conservative
and leads to bigger relief valves
and fare headers, but it is the
approach most widely practised.
With increasing computing speed
and software reliability, process
simulation is increasingly used as
an important tool for estimating
relief load and properties. Steady-
state simulation can also be used to
estimate the relief load within limi-
tations and can overcome some of
the assumptions envisaged in the
conventional method. Dynamic
simulation provides an alternative
method for determining relief load
under abnormal conditions.
This article considers different
methods for estimating relief load
for a distillation column a debu-
taniser in this case and discusses
the strengths and weaknesses of
each method. There are many emer-
gency cases that apply to a
distillation column, and estimation
of the maximum possible relief load
requires an understanding of plant
behaviour and identifcation of the
worst case.
Case study: a debutaniser
The debutaniser column separates
liquifed petroleum gas (LPG)
components from light naphtha.
Refux
pump
Product
pump
Feed
pump
Reboiler
Steam
Condensate
CWS CWR
CWS CWR
To fare, R 135F
174 psia
391F
178 psia
391F
412F
P
set
= 214 psia
Of gas
Sour water
Bottom, naphtha product, B
615600 lb/hr, 391F
Distillate, sour LPG, D
58120 lb/hr, 104F
Feed, F
673700 lb/hr, 301F
196000 lb/hr
Debutaniser
Reflux
drum
LC
PC
FC
FC TC
LC
LC
FC
FC
PDC
Figure 1 Distillation column (debutaniser)
betchel.indd 1 10/3/10 10:16:44
The overhead includes a
cooling water total
condenser, refux drum
and off-gas valve, which
is normally closed. The
debutaniser operates at
174 psia and relief is set
at 214 psia. The debutan-
iser bottom is heated by
a thermosyphon reboiler
utilising medium-pressure
steam. Figure 1 shows a
fow diagram of the debu-
taniser under evaluation.
Major relief conditions or
plant situations identifed
for the debutaniser are
loss of refux, loss of feed
and site-wide power
failure.
Conventional method
The conventional approach
is also known as the
unbalanced heat method,
where a mass and energy balance is
developed under relief conditions,
based on the scenario under consid-
eration, to determine if there is any
unbalanced or excess heat. The
unbalanced heat is divided by the
latent heat of vapourisation of the
top tray liquid to give the relief
load:
Relief load = Q
unbalanced (excess)
/
The conventional method for
determining the relief load of a
column is available in various liter-
ature
1
and hence is not covered in
detail here.
There are several assumptions in
determining relief loads:
Feed, products, refux and top
tray liquid compositions are unal-
tered during the relief condition
Feed, product, refux and strip-
ping medium will continue at the
normal rate unless the hydraulics at
the relieving condition determine
otherwise
Enthalpy is balanced on the top
tray and all unbalanced heat will
reach and act upon the top tray
liquid
There is enough top tray liquid
available to generate vapour during
upset conditions.
To determine Q
unbalanced
, the frst
step is to develop a sketch around
the affected system (see Figure 2)
and perform a mass and energy
balance in line with the upset
condition:
R = Q
unbalanced (excess)
/
where
F = Debutaniser or column feed
rate at relief
h
F
= Specifc enthalpy of feed at
relief
B = Debutaniser or column
bottom rate at relief
h
B
= Specifc enthalpy of bottom at
relief
D = Debutaniser distillate rate at
relief
h
D
= Specifc enthalpy of distillate
at relief
Q
R
= Reboiler heat input at relief
Q
C
= Condenser duty at relief
(generally, the design duty can be
considered)
h
L
= Specifc enthalpy of top tray
liquid
= Latent heat of vapourisation
of top tray liquid
R = Relief load
Credit may be taken for reboiler
pinch. At relieving pressure, the
column temperature rises and the
reboiler temperature difference may
fall, leading to lower heat input to
the column. This is reboiler pinch.
2
Assume that the volume of the
sump is suffcient to maintain a
constant reboiler circulation rate
and to re-rate the reboiler to obtain
duty at relief condition. If there was
a signifcant reduction in the
reboiler duty at relief, the lighter
components would begin travelling
towards the bottom, causing the
duty to rise again. Many designers
re-rate the reboiler with feed
composition instead of bottoms
composition in these circumstances,
to maintain a more conservative/
realistic reboiler duty at relief.
Loss of refux
Refux stops immediately
The refux drum and the
To p tray
Excess h eat
R
F, h
F
D , h
D
B , h
B
Q
R
Q
C
Debutaniser
Reflux
drum
Figure 2 Distillation column: unbalanced heat envelope
Relief valve
opens
Reflux stops
Time, min
l00
200
300
400
500
600
700
800
900
0
0 5 l0 l5 20 25 30 35 40 45 50 55 60
r
h
/
b
l

0
0
0
,
l

,
e
t
a
r

w
o
l
P
Peed
8ottoms
Pelief
Peflux
Overhead
from column
Distillate
Reflux drum fills
Figure 3 Loss of refux: fow vs time
Q
unbalanced
= F h
F
- B h
B
- D h
D
+ Q
R
- Q
C
- (F - B - D) h
L
betchel.indd 2 11/3/10 21:57:38
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column sump level, and fnally
reaches zero
The column overhead vapour
rate decreases, the refux drum level
drops, and the distillate rate
decreases to maintain the condenser
level and fnally becomes zero.
Therefore:
Site-wide power failure (SWPF)
All electrical equipment fails,
therefore the feed pump, the debu-
taniser bottom pumps and the
refux pumps stop
Assuming all cooling water
pumps are electrically driven, the
condensing duty is also immedi-
ately lost
Steam is assumed to fow contin-
uously to the reboiler. Therefore:
Dynamic simulation of relief
conditions
Chemical plants and refneries are
never truly at a steady state and
this is the case during relief. The
transient behaviour of a column is
best studied by means of dynamic
simulation, which has gained in
importance since the 1990s and has
been used increasingly successfully
as the reliability of simulation soft-
ware has increased. The equations
for material, energy and composi-
tion balances include an additional
accumulation term, which is
differentiated with respect to time.
The inclusion of an accumulation
term enables the dynamic model to
rigorously calculate compositional
changes at each stage and to modify
vapour/liquid equilibrium over
time.
Unlike steady-state simulation,
dynamic simulation works within a
Pressure-Flow (P-F) network with
two basic equations: resistance and
volume balance. The resistance
equation defnes fow between pres-
sure hold-ups, and the volume
balance equation defnes material
balance at pressure hold-ups.
For the case under consideration,
the accuracy of dynamic simulation
Time, min
l60
l70
l80
l90
200
2l0
220
230
240
250
l50
0 l0 l5 20 25 30 35 40 45 50 55 60 5
a
i
s
p

,
e
r
u
s
s
e
r
p

f
e
i
l
e
P
Pelief pressure
Pelief valve set pressure
Pelief valve accumulated
pressure
Peak pressure
Figure 4 Loss of refux: relief pressure vs time
Time, min
20
40
60
80
l00
l20
0
0 l0 l5 20 25 30 35 40 45 50 55 60 5
%

,
l
e
v
e
l

p
u
d
l
o
H
Peboiler sump
Peflux drum
Column sump
Reflux drum fills
Figure 5 Loss of refux: holdup level vs time
Upset condition Relief load, lb/hr Temperature, F Molecular weight
Loss of refux 124 980 164 49.28
Loss of feed 43 650 164 49.28
Site-wide power failure 342 796 164 49.28
Relief load calculated by conventional method
Loss of feed
Feed stops immediately
After some time, when the
column level drops, the bottom
product decreases to maintain the
Table 1
O O
Q
unbalanced
= F h
F
- B h
B
- D h
D
+ Q
R
- Q
C
- (F - B - D) h
L
O
Q
unbalanced
= F h
F
- B h
B
- D h
D
+ Q
R
- Q
C
- (F - B - D) h
L
O O O
O O O
O O O
O O
Q
unbalanced
= F h
F
- B h
B
- D h
D
+ Q
R
- Q
C
- (F - B - D) h
L
O
condenser food, restricting the
overhead vapour path and pressu-
rising the column
The feed is pumped and suff-
cient head is available to maintain
the feed fow rate at relief
condition
Bottom product continues at the
same rate. Therefore:
betchel.indd 3 10/3/10 10:17:09
provides extra inputs compared
with steady-state simulation:
Dimensions, especially volumes,
for all static equipment; column
bottom and refux drum levels are
set to normal to simulate hold-ups
A vendor curve for pressure fow
relationships for rotating equipment
Specifc conductance for control
valves (Cv value) for pressure fow
relationships, and an actuator mode
and rate for valve actuator
dynamics
Detailed exchanger thermal
design for calculation of pressure
drop and heat transfer coeffcient. If
detailed design is not available, a
resistance term for the pressure
fow relationship and overall UA
can be specifed
Actual tray information such as
diameter, fow path, distributor
details, weir length and height are
required for column hydraulic
performance
Controller for determining
control actions during transitions.
Credit is not taken for the control
action, which reduces the relief
load; for example, the column
bottom temperature controller
reduces the steam fow rate when
the column bottom temperature
rises at the relief condition.
Loss of refux condition
The refux pump is stopped in fve
minutes (see Figure 3). The level in
the refux drum starts to increase
(see Figure 5). The overhead vapour
from the column continues to fow
through the condenser and fll the
refux drum. After 17 minutes, the
refux drum foods and the fow to
the condenser is blocked; the
column pressure starts to increase
(see Figure 4). When the column
reaches the set pressure, after
about 21 minutes, the relief valve
starts to open. Note that the
pressure did not reach the maxi-
mum accumulated pressure for
the given orifce area of the relief
valve.
Initially, the level in the column
bottom sump decreases as the
refux is stopped, and the bottoms
product level control valve closes to
maintain the column sump level.
The feed continues at a constant
rate, since its pressure upstream of
Peed
8ottoms
Pelief
Peflux
Overhead
from column
Distillate
Relief valve
open
Relief valve
close
Relief flow
Feed stops
Time, min
l00
0
200
300
400
500
600
700
800
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
r
h
/
b
l

0
0
0
l

,
e
t
a
r

w
o
l
P
Bottom & distillate
flow zero
Figure 7 Loss of feed: fow vs time
Time, min
l60
l70
l80
l90
200
2l0
220
230
240
250
l50
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
a
i
s
p

,
e
r
u
s
s
e
r
p

f
e
i
l
e
P
Pelief pressure
Peak pressure
Pelif valve
accumulated pressure
Figure 8 Loss of feed: relief pressure vs time
Time, min
20
l0
30
40
50
60
70 l20
ll8
ll6
ll4
ll2
ll0
l08
l06
l04
l02
l00
0
0 l0 l5 20 25 30 35 40 45 50 55 60 5
t
h
g
i
e
w

r
a
l
u
c
e
l
o
M
Peboiler duty
Column sump
molecular weight
Pinched reboiler duty
D
u
t
y
,

8
T
U
/
h
r
Figure 6 Loss of refux: reboiler duty and molecular weight vs time
betchel.indd 4 10/3/10 10:17:19
the control valve is higher than the
relief pressure.
Figure 6 shows the reboiler duty
and column sump molecular weight
during this relief condition. As soon
as the refux is stopped, the molecu-
lar weight in the column sump
increases, leading to an increase in
the boiling temperature of the
column bottoms, fnally resulting
in reduced reboiler duty.
After 17 minutes, when the path
for the overhead vapour was
blocked (condenser fooded), lighter
components started to fll the
column sump and reboiler duty
again started to increase. After 21
minutes, when the relief valve
started to open, reboiler duty
settled, based on the column sump
composition at relief condition.
Loss of feed condition
The feed pump stops after fve
minutes (see Figure 7). After 10
minutes, the column sump level
drops (see Figure 9) and the bottom
fow is reduced to maintain the
column sump level. As the column
overhead vapour starts to decrease
(see Figure 7), the refux drum level
decreases and the distillate fow
reduces to maintain the refux drum
level. After 20 minutes, when distil-
late and bottoms stop completely,
only the vapour generated by the
reboiler is condensed by the
condenser. Figure 10 shows the
pinched reboiler duty, condenser
duty and column sump molecular
weight.
During loss of feed, the column
sump molecular weight increases,
resulting in reduced reboiler duty.
Since the top refux is maintained
at normal fow, the lighter compo-
nents start migrating towards the
bottom. The column profle starts
becoming lighter and the tempera-
ture profle starts lowering. This
also results in the lower molecular
weight of the column overhead
vapour. After about 11 minutes, the
condenser is not able to fully
condense the overhead vapour due
to its lower molecular weight,
resulting in a rise in column pres-
sure (see Figure 8). When the
column reaches the set pressure,
after about 23 minutes, the relief
valve starts to open. Note that the
Time, min
20
40
60
80
l00
l20
0
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
%

,
l
e
v
e
l

p
u
d
l
o
H
Peflux drum
Column sump
Reboiler sump level drops
Column sump level drops
Peboiler sump
Figure 9 Loss of feed: holdup level vs time
Pinched reboiler duty
Condenser
duty
Time, min
l0
l05
l06
l07
l08
l09
ll0
lll
ll2
ll3
ll4
l04
20
30
40
50
60
70
0
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 40.0 35.0
r
h
/
8
T
U

,
y
t
u
D
Condenser duty
Column sump
molecular weight
Peboiler duty
Figure 10 Loss of feed: reboiler duty and molecular weight vs time
Peed
8ottoms
Pelief
Peflux
Overhead
from column
Distillate
Relief valve open
Site-wide power failure
Time, min
50
l00
l50
200
250
300
0
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
r
h
/
b
l

0
0
0
l

,
e
t
a
r

w
o
l
P
Figure 11 Site-wide power failure: fow vs time
betchel.indd 5 10/3/10 10:17:30
pinched reboiler duty at this time is
higher because of the lower molec-
ular weight in the column sump.
After about 35 minutes, all non-
condensable or lighter components
exit the column, reboiler duty
reduces again to about 42% of
normal, and the column stabilises
at total refux mode.
Site-wide power failure condition
Assume that site-wide power fail-
ure occurs after fve minutes (see
Figure 11). During the power fail-
ure, the feed pump, column bottom
pump, refux pump and cooling
water pump stop, and their respec-
tive fows become zero immediately.
The column sump level increases
immediately as the tray inventories
are dumped to the bottom (see
Figure 13).
As the fows of feed, distillate,
bottoms and cooling water are cut,
the vapours generated by the
reboiler cause the column pressure
to increase (see Figure 12). After 11
minutes, the relief valve opens.
Initially, there is mass transfer
between the vapours from the
reboiler and the residual liquid on
the trays; progressively, as the trays
dry up, the temperature and molec-
ular weight of the overhead
(relieving) vapour increase. The
bottoms progressively become
heavier, resulting in a continuous
decrease in the reboiler duty (see
Figure 14). As the pinched reboiler
duty carries on decreasing, the
relief valve will eventually close.
During power failure, the relief
load is relatively low compared
with the loss of feed condition
because the pinched reboiler duty
is much less due to the high molec-
ular weight in the column. During
loss of feed, continuing refux
makes the column relatively lighter.
The time taken to pressure up the
column is much higher in the loss
of feed scenario because the
condenser is available, compared to
the loss of power condition,
where condensing duty was lost
immediately.
Summary
Loss of refux condition
Figure 15 shows a comparison of
relief load values obtained for loss
Time, min
20
40
60
80
l00
l20
0
5.0 0.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
%

,
l
e
v
e
l

p
u
d
l
o
H
Peflux drum
Column sump
Column sump
level increases
Peboiler sump
Figure 13 Site-wide power failure: hold-up level vs time
Time, min
l0
l02
l04
l06
l08
ll0
ll2
ll4
ll6
ll8
l20
l00
20
30
40
50
60
70
0
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
r
h
/
8
T
U

,
y
t
u
D
t
h
g
i
e
w

r
a
l
u
c
e
l
o
M
Peboiler duty
Condenser duty
Increasing column
sump molecular weight
Reboiler duty
decreases
Molecular weight
Figure 14 Site-wide power failure: reboiler duty and molecular weight vs time
Time, min
l60
l70
l80
l90
200
2l0
220
230
240
250
l50
0.0 5.0 l0.0 l5.0 20.0 25.0 30.0 35.0 40.0
a
i
s
p

,
e
r
u
s
s
e
r
p

f
e
i
l
e
P
Pelief pressure
Peak pressure
Pelif valve
accumulated pressure
Figure 12 Site-wide power failure: relief pressure vs time
betchel.indd 6 10/3/10 10:17:42
of refux. According to the conven-
tional method, the predicted relief
load is higher than the value
obtained by dynamic simulation. In
the conventional method, the
assumption is that all of the unbal-
anced heat will vapourise the top
tray liquid, which has a lower
specifc enthalpy. The molecular
weight and temperature are lower
for the top tray at bubble point and
relief pressure when compared to
dynamic simulation, which simu-
lates refux failure, resulting in a
higher temperature and molecular
weight.
In a dynamic simulation of loss of
refux, the column almost reaches a
new steady-state condition after 25
minutes. The rectifying section of
the column goes dry and only the
stripping section is involved in
mass transfer. This new steady state
can also be reasonably simulated
using a steady-state simulator (see
Steady-state simulation to obtain
relief load and properties).
There is a marginal difference in
the relief load obtained by steady-
state simulation and dynamic
simulation because, in steady-state
simulation, the column pressure has
been raised to an accumulation
pressure (set pressure +10% or
+16% based on the scenario),
whereas in dynamic simulation the
pressure safety valve starts opening
at its set pressure and the pressure
does not reach the maximum accu-
mulated pressure for the selected
orifce area. Note that the conven-
tional method and steady-state
simulation are not time dependent,
so the relief load appears constant
in comparison with the dynamic
simulation relief load.
Loss of feed
relief load obtained for loss of feed.
The relief load calculated by the
conventional method is lower than
by dynamic simulation. In the
conventional method, the condenser
duty equals the design duty and
the cooling effect is predominant.
In dynamic simulation, the
condenser duty is not fxed and the
hold-up of the individual compo-
nents in the column determines the
behaviour of the condenser.
Initially, during loss of feed, the
reboiler duty decreases due to
pinch and the lighter components
subsequently travel to the bottoms
and the whole column profle
becomes lighter. Eventually, the
reboiler duty again starts to raise
due to the decrease in molecular
weight. This phenomenon cannot
be evaluated with the conventional
Time, min
20
40
60
80
l00
l20
l40
0
0 5 l0 l5 20 25 30 35 45 40
r
h
/
b
l

0
0
0
l

,
d
a
o
l

f
e
i
l
e
P
Steady-state simulation
Dynamic simulation
Conventional method
Figure 15 Loss of refux: relief load vs time
Time, min
20
l0
30
40
50
60
80
70
90
l00
0
0 5 l0 l5 20 25 30 35 40
r
h
/
b
l

0
0
0
l

,
d
a
o
l

f
e
i
l
e
P
Dynamic
simulation
Conventional method
Figure 16 Loss of feed: relief load vs time
Upset condition Relief load, lb/hr Temperature, F Molecular weight
Loss of refux 90 800 310 62.5
Loss of feed 93 500 117 44.2
Site-wide power failure 29 250 290 76
Relief load calculated by dynamic simulation
Table 2
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method, but validates the hypothe-
sis that, if the pinched duty is too
low, the designer should re-evalu-
ate the reboiler duty, assuming
lighter composition in the column
bottoms.
Site-wide power failure
relief load obtained for site-wide
power failure. In dynamic simula-
tion, the relief load obtained is
much lower than by the conven-
tional method. In reality, during
this condition, after the trays dry
up the column simply acts as a boil-
ing pot without mass transfer.
The reboiler duty continuously
decreases as the contents become
heavier with time. According to the
conventional approach, reboiler
duty and relief rate are calculated
at one instant, which is at the start
of the emergency (not at the start of
relief). This results in a conservative
estimate. The effect of hold-up
volumes and time taken to pressu-
rise is normally ignored.
The conventional method is the
most conservative and requires less
effort during design. Steady-state
simulation to determine the relief
load has limited applicability. For
grassroots designs, the conventional
method may be the most appropri-
ate, as detailed design and/or
complete vendor information may
not be available at the time of the
relief systems design. It also helps
to build in inherent design margins
for any possible future expansion/
debottlenecking operation, and to
minimise changes during the late
stages of the project due to any
unforeseen design development.
Dynamic simulation models the
system rigorously and tends to
provide more accurate results,
taking into account actual system
dynamics and confguration. It tries
to emulate plant behaviour, which
usually results in lower relief loads.
Dynamic simulation also provides
relief loads based on time, which
can be further analysed for optimis-
ing the relief systems design.
Dynamic simulation can be particu-
larly useful in unit revamps, to
limit the capital cost involved in
relief system modifcations.
Steady-state simulation to obtain
relief load and properties
Simulate the distillation column
into three sections: column, column
overhead system and reboiler
system
The column can also be simulated
as a reboiled column (column with
a reboiler) with theoretical stages
and normal operating pressure
Defne a refux stream and
feed it to the top tray
Defne the feed stream and
assign an appropriate feed location.
Give a normal pressure drop across
the column
Fix the normal reboiler duty to
the energy stream and normal boil-
up ratio (as a specifcation)
Converge the column
The column overhead system
includes a pressure safety valve
(PSV), cooling water condenser and
refux drum
Time, min
50
l00
l50
200
300
250
350
400
0
0 5 l0 l5 20 25 30 35 40
r
h
/
b
l

0
0
0
l

,
d
a
o
l

f
e
i
l
e
P
Dynamic simulation
Conventional method
Figure 17 Site-wide power failure: relief load vs time
Refux
pump
CWS
Refux
Recycle
Internal energy duty = external reboiler duty
Set
To condenser
To relief
CWR
Steam
To external
reboiler
Total liquid from
column bottom stage
(internal stream)
Condensate
Of gas
Sour water
Distillate
Bottom
Twinned
column bottom
Feed
Internal
energy
stream
Debutaniser
Reflux
drum
External
reboiler
Figure 18 Distillation column steady-state simulation relief condition
betchel.indd 8 11/3/10 22:02:46
Split the overhead vapour
from the column to relief and to
condenser, and set the relief
fow rate to zero
Simulate the condenser as a
shell and tube exchanger with cool-
ing water on the tube side and
overheadvapourtotallycondensed.
Simulate the refux drum, refux
pump, distillate product and refux
The refux from the refux
pump should be same as the
defned refux stream to the top
tray, so connect them through a
recycleblock
The reboiler system should be
simulated as a separate shell and
tube heat exchanger (external
reboiler) in order to study reboiler
pinchatrelievingconditions
Create an internal stream of
the total liquid from the bottom
stage in the column. The internal
stream minus the column bottoms
is the feed to the external reboiler,
so split the internal stream to the
external reboiler and twinned
column bottoms. Set the column
bottoms fow rate to the twinned
columnbottomsstream
Specify the normal UA to the
externalreboiler
Specify the hot side of the
externalreboiler.Forthecaseunder
consideration, the hot-side inlet is
steam at its saturation condition
and the hot-side outlet is total
condensate
Increase the column pressure to
relief pressure (PSV set pressure +
allowable accumulation). Since the
bottom pressure is higher (relief
pressure + normal P), the bubble
point of the column bottom
increases. The temperature differ-
ence across the external reboiler
reduces, leading to lower external
reboiler duty (pinch). The calcu-
lated duty of the external reboiler
should be equal to the energy
stream attached to the column
(internal energy stream). Iterate the
column internal energy stream so
that it matches the external reboiler
duty.EventhoughtheLMTDtends
to increase in the condenser, many
designers tend to restrict the maxi-
mum condenser duty to design
duty due to uncertainties in the
calculation. For this exercise, the
condenser duty is limited to the
designdutyonly.
Now the column is at relieving
pressure, giving an idea of the
reduced reboiler duty and the
amount of overhead vapour. The
next step is to simulate the cause of
overpressure to the maximum
convergenceofthecolumn.Forloss
of refux, increase the fow to
relief, so that fow to the condenser
is reduced and, ultimately, the fow
to the refux is reduced.
Simultaneously reduce the distillate
fow step-wise as the refux pump
is stopped. At the same time, keep
iteratingthecolumninternalenergy
stream so that it matches the exter-
nal reboiler duty. Ultimately, when
the refux and distillate are zero, all
the overhead vapour from the
column is the relieving fow.
The above methodology can also
be extended to other emergencies,
where it is expected that the reliev-
ing scenario could approach the
steady-statecondition.
References
1 Sengupta M, Staats FY, A new approach to
relief valve load calculations,May1978.
2 Rahimi Mofrad S, Tower pressure relief
calculation,Hydrocarbon Processing,Sep2008.
Haribabu Chittibabu is an Engineering
Specialist in the Advanced Simulation and
Analysis group at Bechtel India. He has a
bachelors degree in chemical engineering
from University of Madras and a masters in
petroleum refning and petrochemicals from
AnnaUniversity,India.
Email: hchittib@bechtel.com
Amudha Valli is an Engineering Specialist in
the Advanced Simulation and Analysis group
at Bechtel, India. She has a bachelors degree
in chemical engineering from Coimbatore
Institute of Technology, India, and a masters
inchemicalengineeringfromAnnaUniversity,
India.Email: an@bechtel.com
Vineet KhannaisProjectEngineeringManager
withBechtelIndia.Hehasabachelorsdegreein
chemicalengineeringfromtheIndianInstitute
ofTechnology,Delhi,India.
Email: vkhanna@bechtel.com
Dipanjan Bhattacharya is an Engineering
Specialist in the Advanced Simulation and
Analysis group at Bechtel, Houston. He has
a bachelors degree in chemical engineering
from Jadavpur University, India, and masters
in chemical engineering from University of
Oklahoma.Email: dbhatta1@bechtel.com
PTQ1-4-4c_X3.pdf 1 23.02.2009 10:42:13 Uhr
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Crude oil selection: optimisation by
weight or by volume?
L
inear programming (LP) is a
technique used widely for
optimisation in petroleum
refneries. LP models of refneries
are used for capital investment
decisions, the evaluation of term
contracts for crude oil, spot crude
oil purchases, production planning
and scheduling, and supply chain
optimisation. Robustness and preci-
sion in the LP model are critical to
the proftability of the refnery. A
good refnery LP model accurately
captures unit operation yields and
properties, stream blending, the
extent of constraints on product
specifcations, fexibility on cargo
sizes of crudes and fnished prod-
ucts, and other relevant data.
The methodology of crude oil
evaluation using an LP model is as
critical as a good LP model itself.
Each refner has its unique require-
ments of LP that depend upon the
environment in which the refnery
operates and the market to which it
caters. The methodology of evalua-
tion should address, among other
concerns, the time horizon of opti-
misation, unit of measurement of
crude and product quantities and
prices, the option to import fnished
products, and inventory pricing
and accumulation/depletion. Deve-
loping an accurate assessment
methodology, which closely refects
the realities faced by a particular
refnery, is an interesting process.
This article is based on the
authors experiences in setting up a
LP-based crude oil evaluation
system for Hindustan Petroleum
Corporation (HPCL). It discusses
how units of measurement of crude
and product quantities and prices
(the choice between weight-based
The LP model should optimise crude and products in their trading units for accurate
assessment of crude oil worth and maximisation of gains from product blending
M D PawDe and Sachin Singh
Hindustan Petroleum Corporation Ltd (HPCL)
and volume-based optimisation)
can give conficting recommenda-
tions. The paper also describes
options available in Aspen Process
Industry Modelling System (PIMS)
to specify correctly the desired
methodology of optimisation.
Optimisation of crude oil trades
The world over, crude oil is traded
by volume; it is priced in dollars
per barrel. Volume-based LP
models, which capture crude oil
yields in volume per cent (vol%)
and buy/sell crudes by volume,
assess them accurately. However,
weight-based models need to incor-
porate proper conversion and
comparison methods for the correct
evaluation of crude oils.
Let us consider two hypothetical
crude oils, A and B, one heavy (API
35) and the other light (API 45), but
with the same weight per cent
(wt%) and vol% yields. Yields in
weight and volume will be the
same if the individual ratios of
stream density to crude density are
identical for both the crudes (see
Table 1).
Table 1
crude oil a crude oil B
Whole crude API 35.0 45.0
Whole crude density 0.8494 0.8013
Expansion, vol% 0.2 0.2
Stream densities
1

LPG 0.5738 (0.6755) 0.5413 (0.6755)
Naphtha 0.7455 (0.8777) 0.7033 (0.8777)
Kerosene 0.8048 (0.9474) 0.7592 (0.9474)
Gas oil 0.8624 (1.0153) 0.8135 (1.0153)
VGO 0.9234 (1.0871) 0.8711 (1.0871)
Vacuum resid 0.9907 (1.1663) 0.9346 (1.1663)
Product blend 0.8476 (0.9978) 0.7996 (0.9978)
Product yield, wt%
2

LPG 0.6 0.6
Naphtha 18.4 18.4
Kerosene 13.1 13.1
Gas oil 40.3 40.3
VGO 19.6 19.6
Vacuum resid 8.1 8.1
Total 100.0 100.0
Product yield, vol%
2

LPG 0.8 0.8
Naphtha 20.9 20.9
Kerosene 13.8 13.8
Gas oil 39.6 39.6
VGO 18.0 18.0
Vacuum resid 6.9 6.9
Total 100.0 100.0
1. Figures in brackets are the ratios of stream density to the respective crude oil density.
2. Yields are hydroskimming; fuel and loss has been assumed to be zero for simplicity of demonstration.
Yields and densities of crude oils a and B
hpcl.indd 1 10/3/10 11:29:29
Product prices and standard
densities used for sample calcula-
tions are shown in Table 2.
Conversion factors used for naph-
tha, kerosene, gas oil and resid are
from Platts. For liquifed petroleum
gas (LPG) and vacuum gas oil
(VGO), typically produced densities
have been used.
Using $/MT prices from Table 2,
and wt% yields, product value in
$/MT is determined and divided
by a bbl/MT conversion factor for
the respective crudes to arrive at
their $/bbl value. It can be
concluded from Table 3a that both
crudes have the same value in $/
MT; the conclusion is also apparent
from the fact that both crudes have
the same wt% yields. One hundred
tonnes of either of the crudes will
provide the same revenue to the
refnery; their break-even prices per
barrel are respectively $62.3 and
$58.7. In other words, the refner
can pay 3.6 $/bbl more for crude
oil A than for crude oil B to make
the same proft. Let us call this
Conclusion 1.
Product values are now recalcu-
lated using vol% yields and $/bbl
prices from Table 2. Both crudes
have the same vol% yields and,
hence, are expected to have the
same value per barrel.
The calculation in Table 3b shows
that the refner cannot pay any
more per barrel for crude oil A than
they are paying for crude oil B. Let
us call this Conclusion 2.
Which of these conclusions is
correct? Conclusion 1 is the recom-
mendation of optimisation by
weight, whereas Conclusion 2 is the
result of volume optimisation.
Optimisation by weight ascribes
higher values to heavier barrels
than to lighter barrels of crude oils
(A and B respectively). On the other
hand, optimisation by volume
values heavier and lighter crudes at
par.
A mixed weight-volume optimi-
sation model buys, sells, transfers
and stores crudes and products in
their actual trading units. Such a
model gives due credit to heavier
and lighter products, and is an
accurate way of evaluating crude
oils.
Let us rework the gross product
value for mixed yields, starting frst
from weight and then from volume
yields. Let us assume that the
refner sells gas oil, kerosene and
VGO by volume and the rest of the
products by weight. Starting with
weight yields, mixed yields are
calculated using actual product
densities of products sold by
volume. Starting from volume
yields, the mixed yields are calcu-
lated using actual densities of
products sold by weight. $/bbl
prices for gas oil, kerosene and
VGO, and $/MT for LPG, naphtha
and vacuum resid are derived from
Table 2.
It is evident from Tables 4a and
Table 3a
Product $/bbl $/MT bbl/MT Standard density
LPG 35.40 396.45 11.2 0.5616
Naphtha 53.31 479.76 9.0 0.6989
Kerosene 66.71 527.02 7.9 0.7962
Gasoil 66.01 491.77 7.45 0.8443
VGO 57.27 400.89 7.0 0.8985
Vacuumresid 47.51 308.80 6.5 0.9677
Product prices and standard densities
Table 2
Crude oil A Crude oil B A-B
$/MT 461.0 461.0 0.0
bbl/MT 7.405 7.850 -
$/bbl=($/MT)/(bbl/MT) 62.3 58.7 3.6
Calculation of gross product using wt% yields
$/bbl 60.3 60.3 0.0
bbl/MT 7.405 7.850 -
$/MT=($/bbl)*(bbl/MT) 446.8 473.7 (26.9)
Calculation of gross product using vol% yields
Table 3b
$/MT 453.9 474.3 (20.3)
bbl/MT 7.405 7.850 -
$/bbl=($/MT)/(bbl/MT) 61.3 60.4 0.9
Mixed yields starting from wt% yields
$/bbl 61.2 60.3 0.9
bbl/MT 7.405 7.850 -
$/MT=($/bbl)*(bbl/MT) 452.9 473.2 (20.3)
Mixed yields starting from vol% yields
Table 4a
Table 4b
hpcl.indd 2 10/3/10 11:29:37
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o
k

C
o
m
p
a
n
y
swa4778-04_PTQ_AR_20100226.indd 1 2/26/10 11:12 AM
www.ptqenquiry.com
swagelok.indd 1 9/3/10 14:28:56
4b that both methods draw the
same conclusion: crude oil A -
crude oil B = 0.9 $/bbl. That is, the
refner can shell out 0.9 $/bbl more
for crude oil A than they can for
crude oil B to make the same
margin. Table 5 summarises the
results.
The value of crude oil A decreases
when it is priced by volume
compared with when it is priced by
weight. On the other hand, the
value of crude oil B increases when
it is priced by volume compared
with when it is priced by weight.
Value in mixed units lies between
weight and volume values for crude
oil A, but is higher than either of
the two for crude oil B. These
observations are explained below.
Notations used for crude proper-
ties are:
b: bbl per MT of the crude
d
crude
: Crude oil density, kg/l
d
product
: Product blend density, kg/l
: Volume expansion factor, %
The following notations are used
for product i:
w
i
: wt% yield
d
i
: density, kg/l
s
i
: standard density, kg/l
p
i
: price in $/MT
q
i
: price in $/kL
Product blend density is the
density if all of the product streams
were to be blended together:
d
product
= w
i
/ (w
i
/ d
i
)
Mathematically, product blend
density d
product
should have been
equal to the whole crude density;
however, almost all of the crude
oils expand when split into individ-
ual streams, and the fnal blend is
lighter than the original crude oil.
The expansion is characterised by a
parameter called the volume expan-
sion factor , which is expressed in
vol%:
Finishedproducts Finishedproducts Finishedproducts
pricedbyweight pricedinmixedunits pricedbyvolume
Crude oil A (35 API) 62.3 61.3 60.3
Crude oil B (45 API) 58.7 60.4 60.3
Crude oil A - crude oil B 3.6 0.9 0.0
Grossproductvaluesanddifferentials,$/bbl
Table5
Cabinda
(AP| 32.6)
Qua |boe
(AP| 34.8)
Nemba
(AP| 38.9)
Saharan blend
(AP| 44.6)
26.2
28.1
21.8
10.7
11.9
6.5
25.4
32.9
17.4
17.2
12.2
23.9
26.3
15.5
19.8
9.9
20.4
24.2
18
25.2
l0
20
30
40
50
60
70
80
90
l00
0
t
n
e
c
r
e
P
vac resid
vGO
Gas oil
Kerosene
Naphtha
LPG
Figure1wt% cut yields
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15852-az-GJP4.3e-59x270.indd 1 02.03.2010 16:43:44 Uhr
hpcl.indd 3 10/3/10 11:29:45
Qua Iboe and Nemba. This has a
signifcant bearing on decisions
based on the absolute refning
margins of the crudes. Second, the
relative values of crudes differ
according to evaluation methodolo-
gies (for instance, Qua Iboe Saharan
Blend delta is 3.0 $/bbl by weight,
but only 0.5 $/bbl by volume).
Pecking orders are different for the
two cases.
Optimisation of product blending
Different markets trade fnished
= 100 * (1/ d
product
- 1/ d
crude
)
Gross product values are calcu-
lated from weight and vol% yields
(GPW
w
and GPW
v
respectively):
GPW
w
= w
i
p
i
/ b
where b=6.2898 / d
crude
GPW
v
= (w
i
/d
i
) * q
i
/ b
Since q
i
= p
i
* s
i

GPW
v
= (w
i
/d
i
) * p
i
s
i
/ b
Product worth in volume will be
greater than product worth in
weight if:
(w
i
/d
i
) * p
i
s
i
/ b > w
i
p
i
/ b or
w
i
p
i
* (s
i
/d
i
) / w
i
p
i
>1
For calculating product value in
mixed units (GPW
m
), s
i
is kept equal
to d
i
for the products that are priced
in weight. The term s
i
/d
i
= 1 for
these products and does not
contribute to change in gross prod-
uct value from weight to mixed
units.
Calculations for crude oils A and
B are shown in Table 6. For crude
oil A, GPW
v
is 0.967 * GPW
w
; GPW
m

= 0.985 * GPW
w
: value by volume is
the least and by weight it is the
greatest. For crude oil B, GPW
v
is
1.028 * GPW
w
; GPW
m
= 1.029 *
GPW
w
: value in mixed units is
higher than by either weight or
volume.
Figures 1 and 2 illustrate the
weight and volume cut yields of
the following crude oils: Cabinda
(API 32.6), Qua Iboe (API 34.8),
Nemba (API 38.9) and Saharan
Blend (API 44.6). Cabinda is the
heaviest and Saharan Blend is the
lightest crude oil in the set. For all
of the crudes, the wt% yield of naph-
tha is lower and of vacuum resid is
higher than their respective vol%
yields. Also, the relative changes are
different for different crudes.
Pecking order is calculated based
on the values of crude oil by weight
and by volume and is shown in
Figure 3.
Two points need to be noted from
the above. First, the absolute value
of product values has changed it
has increased for Saharan Blend
and Cabinda, but has reduced for
Crude oil A Crude oil B
Whole crude density, d
crude
, kg/l 0.8494 0.8013
Volume expansion factor , % 0.2 0.2
Product blend density, d
product
, kg/l 0.8476 0.7996
w
i
p
i
*(s
i
/d
i
) / w
i
p
i
, all products 0.967 1.028
w
i
p
i
*(s
i
/d
i
) / w
i
p
i
, for ker, gas & VGO 0.985 1.029
Gross product values
Table 6
Table 7
Blending streams Quantity, TMT Stream density, kg/l
Light naphtha 100 0.7316
Heavy naphtha 25 0.7600
Gas oil stream 200 0.8600
Available quantities and densities of three refnery streams
Cabinda
(AP| 32.6)
Qua |boe
(AP| 34.8)
Nemba
(AP| 38.9)
Saharan blend
(AP| 44.6)
23
26.9
22.3
11.6
14.2
5.5
23.4
32.4
18.2
19.6
10.3
21.9
25.6
16.2
22.7
8.2
18.4
23.3
18.5
28.4
l0
20
30
40
50
60
70
80
90
l00
0
t
n
e
c
r
e
P
vac resid
vGO
Gas oil
Kerosene
Naphtha
LPG
19.6
22.7
Figure 2 Vol% cut yields
Weight, %
Qua |boe (79.6 $/bbl)
Nemba (78.l $/bbl)
Saharan 8lend (76.6 $/bbl)
Cabinda (72.8 $/bbl)
Volume, %
Qua |boe (77.6 $/bbl)
Nemba (77.l $/bbl)
Saharan 8lend (76.7 $/bbl)
Cabinda (75.l $/bbl)
Figure 3 Pecking order according to wt% and vol% yields
hpcl.indd 4 10/3/10 11:29:54
petroleum products either by
volume or by weight, or by a
mixture of both. For example,
Arabian Gulf markets trade naph-
tha in $/tonne, whereas Singapore
markets have naphtha traded in $/
bbl. US markets have naphtha in
cents/gallon, another volume unit.
Gasoline and gas oil are traded in
$/bbl and fuel oil in $/tonne both
in Singapore and in the Arabian
Gulf. Prices of fnished products in
Indian markets are indexed to
Arabian Gulf prices, but their units
of measurement are not all the
same. For instance, fuel oil is traded
by weight in the Arabian Gulf, but
by volume in local Indian markets.
Exports of fuel oil by Indian refn-
eries are again in weight units.
This section illustrates a refners
decision to maximise gas oil vs
naphtha. The refnery sells naphtha
by weight and gas oil by volume.
The refner has three streams avail-
able to blend: light naphtha to
produce fnished naphtha product,
a gas oil stream to produce fnished
gas oil, and a heavy naphtha
stream, which can be blended either
to gas oil or to naphtha. It is
assumed that other specifcations
such as sulphur or fash point are
not constraining this blending.
Refer to Table 7 for the available
quantities and densities of these
streams. Prices of fnished naphtha
and gas oil are listed in Table 8.
They correspond to 55 and 65 $/bbl
with Platts specifed bbl/MT
conversion factors of 9.00 and 7.45,
respectively.
Table 9 summarises the two
options, production quantities and
sales realisation, in each of the two
cases. Sales realisation is calculated
both in weight units and in trading
units (naphtha by weight and gas
oil by volume).
By blending heavy naphtha to
naphtha, the realisation in weight
units is $158.7 million, which is
greater than by blending it in gas
oil ($158.5 million). An LP model
that optimises according to weight
recommends blending to naphtha.
On the other hand, a mixed-unit
optimisation recommends blending
to gas oil. An opportunity is lost
because of a wrong optimisation of
about $1 million (158.0157.0).
These typical production fgures are
from about 6 million bbl of crude
oil processed. Thus, accurate opti-
misation can save up to $0.17 /bbl.
Modelling in Aspen PIMS
Aspen PIMS is widely used LP soft-
ware for modelling refnery
operations in production planning
and crude oil purchasing. Two of
its features related to mixed-unit
optimisation are discussed below.
Mixed-unit buying and selling:
VOL and VPRICE
PIMS provides the option for using
VOL/VPRICE and WGT in Buy
and Sell tables for incorporating
mixed-unit optimisation in weight-
and volume-based LP models,
respectively.
However, there is a technical
difference between using VOL and
VPRICE in a weight-based model.
Specifying VOL in Buy and Sell
tables means that the product is
bought and sold in volume units.
Its price is also specifed in volume
units. Optimisation of the product
is by volume.
On the other hand, VPRICE is the
price of the product in volume
units; the product is still optimised
by weight, and minimum and maxi-
mum constraints are by weight,
although fnal selling is by volume.
We recommend using VOL in
weight-based models and WGT in
volume-based models for mixed-
unit optimisation.
The following is an example
of using VOL in a Sell table in
a weight-based PIMS LP model
(see Table 10). The refner sells LPG
and naphtha by weight, but gaso-
line in volume units. Specifying
VOL for gasoline ensures mixed-
unit optimisation. The constraints
and price of gasoline are in
TkL and $/kL, while for LPG and
naphtha they are in TMT and
$/MT.
Product prices Unit of trade $/kL $/MT
Finished naphtha $/MT 345.9 495.0
Finished gas oil $/kL 408.8 484.3
Prices of refnery naphtha and gas oil
Table 8
Heavy naphtha naphtha Heavy naphtha gas oil
Quantity Quantity, Product density, Quantity, Quantity, Product density,
TMT TkL kg/l TMT TkL kg/l
Finished naphtha 125 169.58 0.7371 100 136.69 0.7316
Finished gas oil 200 232.56 0.8600 225 265.45 0.8476
Sales realisation, m$
Weight units 158.7 158.5
Mixed units 157.0 158.0
Production and sales options for refnery naphtha and gas oil streams
Table 9
TABLE RATIO
TEXT RT1
PURCCR1 Crude 1 (Upper Zakum) 100.0
PURCCR2 Crude 2 (Arab Light) 125.0
PURCCR3 Crude 3 (Qua Iboe) 135.0
PURCCR4 Crude 4 (Azeri Light) 140.0
PURCCR5 Crude 5 (Arab Heavy) 80.0
PURCCR6 Crude 6 (Spot Cargo) 135.0
Refnery term cargoes
Table 11
hpcl.indd 5 10/3/10 11:30:03
Ratio constraints of crude oil and fnished products
Ratio tables are used for incorporating the constraints of
processing crude oils in certain ratios to each other, or
selling certain products in predefned ratios only.
Specifying weight ratio in a weight-based LP model is
equivalent to applying volume ratios in a volume-based
model. Since crude oil is traded by volume, a ratio table
can be used in a weight-based model to incorporate
volume ratio. The following example illustrates the use
of this table.
A refnery is planning for quarterly crude oil
purchases. It has already scheduled crude cargoes from
its term suppliers. Management has instructed that a
part of the inventory crude oil also needs to be depleted.
To meet the planned processing rate, the refnery still
needs to purchase a spot cargo. For preparation of the
pecking order, it needs to evaluate each spot grade along
with the scheduled quantity of term crude oil.
Total crude oil (inventory + term + spot) for the quar-
ter is roughly three times the monthly crude distillation
units capacity specifed in the LP model. The refnery
needs to prorate the quarterly crude quantity to the
monthly throughput. It has a weight-based LP model;
exact optimisation requires that the ratio of crude oils
(term grades with each other and term to spot) be in
volume units.
Table 11 lists the term cargoes of the refnery. Upper
Zakum (100 000 tonnes) and Arab Light (125 000 tonnes)
were part of the opening inventory; parcels of Qua Iboe
(135 000 tonnes), Azeri Light (140 000 tonnes) and Arab
Heavy (80 000 tonnes) are scheduled to arrive during
the month. One parcel of 135 tonnes of spot cargo is to
be purchased for processing during the month. The ratio
table ensures that the crude oils are prorated to the
crude distillation units capacity. This proration is by
weight, which is exactly equivalent to the crudes
volume proration.
Conclusion
Optimisation purely by weight and optimisation purely
by volume can give signifcantly different recommenda-
tions for crude oil purchases and product blending. A
realistic value for crude oil is assessed when both crudes
and fnished products are priced in their trading units.
Also, the LP analysis should optimise in trading units
and not merely use standard conversions for presenting
the fnal output in trading units. Also, if crude and prod-
uct densities are correctly captured in the LP analysis,
both weight- and volume-based models give the same
results and either of them can be used for mixed-unit
optimisation.
M D Pawde is Deputy General Manager, International Trade and Supplies,
at Hindustan Petroleum Corporation Ltd (HPCL), India. He holds a bachelors
degree in chemical engineering from Nagpur University.
Email: mdpawde@hpcl.co.in
Sachin Singh is Deputy Manager, International Trade and Supplies, at
Hindustan Petroleum Corporation Ltd (HPCL), India. He holds a bachelors
degree in chemical engineering from Indian Institute of Technology, Kanpur.
Email: sachinks@hpcl.co.in
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cbi.indd 1 9/3/10 14:27:19
Designing for sulphur removal and
storage: part 1
T
he sulphur block is an essen-
tial part of any new or revamp
refnery project and its cost
contributes signifcantly to the over-
all cost of a project. A typical
sulphur block includes facilities for
hydrogen sulphide removal, amine
regeneration, sour water treating,
sulphur recovery, tail gas treating,
sulphur degassing, sulphur granu-
lation and sulphur storage. The
major criteria in selecting the
sulphur blocks design include the
projects environmental regulatory
constraints, process design require-
ments, operating philosophy, plant
reliability, and the associated capi-
tal and operating costs.
This two-part article discusses
some key issues in process design
confguration, which should be
addressed during the early phases
of any sulphur block project. These
include selection of unit capacity
and number of processing trains,
the sparing philosophy, amine
system design considerations, such
as solvent selection. It also
addresses issues such as licensor
selection for the sulphur recovery
and tail gas treating units. Design
considerations for revamping exist-
ing sulphur block units or installing
new facilities, and integration of a
new sulphur block with upstream
process units are also discussed in
this article.
Many projects aim to increase
bottom-of-the-barrel processing and
produce clean fuels mandated by
regulatory agencies. Most of these
projects are based on processing
heavy crude with greater amounts
of sulphur and nitrogen. Regardless
of the confguration of the upstream
process units, sulphur and nitrogen
Selection of technologies for the sulphur block must serve legislative demands
and the effcient operation of upstream processes
Shamim Gandhi, Wayne ChunG and KriSh nanGia
Fluor Corporation
compounds are converted to hydro-
gen sulphide (H
2
S) and ammonia
(NH
3
) and must be removed from
the hydrocarbon product streams.
H
2
S and NH
3
are processed in a
series of downstream sulphur block
units, including the hydrogen
sulphide removal unit (HSRU), the
amine regeneration unit (ARU), the
sour water treating unit (SWTU),
the sulphur recovery unit (SRU)
and the tail gas treating unit
(TGTU). To handle the additional
H
2
S and NH
3
load from new and
modifed upstream process units,
either the existing sulphur block
units are revamped or new units
are added.
The SRU and TGTU sections
contribute signifcantly to the capi-
tal cost of the sulphur block;
however, the HSRU, ARU and
SWTU also play an important role
in integrating sulphur block units
with upstream process units.
The following issues should be
considered during the early phases
of a sulphur block project; they are
based on recent experience with
new and revamp refnery projects:
Project-specifc environmental
requirements
Sulphur block unit capacity and
train confguration selection
Process licensor selection for
SRU/TGTU
Design basis for SRU/TGTU
Amine system design issues,
including solvent selection
Sour water treating options
Sulphur degassing and sulphur
storage design considerations.
environmental requirements
Sulphur block units are primarily
environmental control process
units. They allow upstream process
units to generate revenue, while
keeping the refnery in compliance
with health, safety and environ-
mental (HSE) requirements. The
purpose of the sulphur block is to
meet or exceed these requirements
and to maintain a high degree of
reliability so as not to interrupt the
operations of the upstream process
units.
One of the frst activities is to
identify clearly the environmental
regulatory requirements that are
specifc to the project and could
affect the design of the sulphur
block.
refnery fuel gas specifcation
Process units generate refnery fuel
gas, which is treated for H
2
S
removal prior to reuse as fuel in the
refnerys fred heaters and boilers.
Typical specifcations can vary
between 50 and 160 ppmv H
2
S. In
addition, for US refneries, the latest
regulations under consideration
by the Environmental Protection
Agency (EPA) limit annual
Sulphur block units
allow upstream
process units to
generate revenue,
while keeping
the refnery in
compliance with hSe
requirements
fluor1.indd 1 10/3/10 11:41:16
allowable H
2
S emissions. Other
components such as carbonyl
sulphide (COS) and mercaptans
should also be addressed to meet
total sulphur limits in the fuel gas.
It is important to fnalise the H
2
S
specifcation early in the design
cycle; it affects solvent selection for
the upstream process units and the
fuel gas contactors.
Tail gas emissions specifcation
The specifcation for sulphur diox-
ide (SO
2)
emissions leaving the
TGTU incinerator stack can vary
between 10 and 250 ppmv, depend-
ing on local environmental
regulations. The type of TGTU
selected is based on the required
level of sulphur recovery and the
specifcation for SO
2
emissions from
the thermal oxidiser. The vent from
the sulphur degassing section is
normally routed to the thermal
oxidiser for incineration. The degas-
sing vent, however, can be recycled
to the SRU reaction furnace if the
requirement for thermal oxidiser
stack gas emissions is very tight;
say, less than 100 ppmv. The recy-
cle affects the design of the SRU,
especially its burner control
systems.
Sulphur recovery requirement
Depending on local regulations, the
sulphur recovery requirement can
vary from 98.599.9%. A three-stage
Claus process can achieve about
97%; however, recovery in excess of
99.5+% is typically required for new
projects, which require a TGTU.
Table 1 shows typical sulphur
recovery levels for various SRU/
TGTU technologies.
Regulatory requirements for
sparing SRU capacity
Some agencies require the refnery
to install spare SRU/TGTU capacity
as a condition for permitting. This
should be considered in establish-
ing the capacity and train
confguration. For example, some
states have a requirement for 75%
SRU/TGTU remaining capacity.
This requires the refnery to main-
tain at least 75% capacity of the
project requirement, even during a
shutdown of one SRU or TGTU.
This requires the refnery to install
additional capacity over actual
sulphur loads. It also essentially
eliminates the possibility of the two
SRUs with a common TGTU confg-
uration, as a shutdown of one
TGTU will cause the shutdown of
both SRU trains.
Fugitive emissions from liquid
sulphur storage tanks
Sulphur product is stored in liquid
sulphur storage tanks or sulphur
pits. These are a source of fugitive
emissions of H
2
S and SO
2
. The tanks
are typically vented to atmosphere
or, in some cases, to the thermal
oxidiser. Alternative destinations
may be required, such as recycle of
the tank vent to the SRU reaction
furnace. The vent recycle has to be
accounted for in the design of the
SRU and TGTU.
H
2
S emissions from sour water
storage tanks
Sour water streams from the
upstream process units are normally
routed to the sour water degassing
drum, so that H
2
and H
2
S gas can
be fashed off to a closed loop sour
gas system. Degassed sour water is
stored in the sour water tanks
before being stripped in the SWTU.
Sour water tanks are typically a
source of H
2
S emissions. A layer of
SRU/TGTU technology Sulphur recovery, %
Two-stage Claus 9495
Three-stage Claus 9698
Direct oxidation 98.599.0
Sub-dew point 98.599.5
Direct oxidation/reduction 99.5
Hydrogenation + amine treatment 99.8+
Sulphur recovery
Table 1
Operating scenario Normal operation Planned turnaround
#1 #2 #3 #4 #5
One SRU train down for maintenance No No Yes Yes Yes for Option C No
Process unit Design feed rate, Maximum sulphur, Estimated sulphur load,
MBPSD load MT/D MT/D
Resid desulphurisation unit 1 50.0 350 350 350 350 350 350
Resid desulphurisation unit 2 50.0 349 349 349 0* 349 349
Resid desulphurisation unit 3 50.0 349 349 0* 349 0* 349
Hydrocracker 73.0 61 0* 61 61 61 61
Kerosene hydrotreater 39.0 16 16 16 16 16 16
Distillate hydrotreater 65.5 139 139 0* 139 139 139
Naphtha hydrotreater 21.0 3 3 3 3 3 0*
Imported fuel gas treater 12 12 12 12 12 12
Total sulphur, MT/D 1279 1218 791 930 930 1276
Sulphur plant confguration Capital cost, MM$ Operating load, % of design capacity
Option A - 2 @720 MT/D *** 176 88.8 84.6 109.9** 129.2** 64.5 88.6
Option B - 2 @750 MT/D *** 182 85.3 81.2 105.5** 124.0** 62.0 85.1
Option C - 3 @450 MT/D (Selected) 200 94.7 90.2 87.9** 103.3** 103.3** 94.5
* Zero sulphur load, as unit is down for planned turnaround. ** SRU operating rate with one train down for maintenance.
*** The 2@720 MT/D and 2@750 MT/D options will not meet the sulphur load during planned turnaround, whereas the selected 3@450 MT/D option will essentially
meet the requirements for all turnaround cases.
SRU capacity selection: an example
Table 2
fluor1.indd 2 10/3/10 11:41:30
oil on the top of sour water will
absorb any H
2
S. Otherwise, the vent
from sour water tanks can be
collected, compressed and delivered
to the closed-loop sour gas system
in the renery.

Capacity selection
An important activity associated
with sulphur block design is the
selection of unit capacity and
number of processing trains.
Historically, a process conguration
with two SRUs coupled to a
common TGTU was widely used to
minimise installed cost. With
greater emphasis on HSE, and the
renerys need to minimise
economic loss resulting from an
unplanned TGTU shutdown, it is
becoming popular to have a dedi-
cated TGTU with each SRU.
Capacity and number of
processing trains
If new sulphur block units are
required, the next step is the selec-
tion of unit capacity and number of
processing trains. Different capacity
options should be considered, such
as 1100%, 250% and 335%. The
capacities of new units and the
number of processing trains are
fundamentally based on detailed
H
2
S, amine and sour water balances;
in addition, a detailed evaluation of
various operating scenarios is
required to ensure that the units are
adequately sized and spared, if
required.
Consideration should be given to
the renery turnaround schedule,
including planned maintenance of
the SRU. Enough capacity should
be provided so that the SRU does
not become a bottleneck during a
planned shutdown.
Capital and operating costs
should be developed for the vari-
ous options to ensure a cost-effective
basis for selecting the train congu-
ration. For SWTU, HSRU and ARU
train selection, it is common to have
a different number of trains than
for the SRU/TGTU. See Table 2 for
an example calculation.
Sparing philosophy
The main objective of sparing is to
prevent a sulphur block unit from
curtailing upstream operations as
well as meeting regulatory require-
ments. In order to deal with sparing
capacity, the renery may consider
the following options:
Oxygen enrichment mode of oper-
ation If the renery is located in an
area where oxygen supply is avail-
able at a reasonable cost, the
renery can consider designing
SRUs with oxygen enrichment tech-
nology. The additional capacity
associated with oxygen enrichment
An important activity
associated with
sulphur block design
is the selection of
unit capacity and
number of processing
trains
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fluor1.indd 3 12/3/10 14:17:42
Selection of process licensor
The SRU and TGTU are typically
licensed units, and therefore require
a process design package from an
experienced process licensor. The
HSRU, ARU and SWTU are typi-
cally open-art units, and the process
design for these units can be devel-
oped without the use of any
licensed technology.
Selection of a licensor involves
preparing an invitation-to-bid (ITB)
to various pre-qualifed licensors.
On receipt of the proposal pack-
ages, a detailed evaluation is
conducted using industry-accepted
methods, such as a K-T analysis.
This method is based on a compara-
tive analysis of licensor experience,
technical designs, economic consid-
erations, and commercial terms and
conditions.
Some of the major criteria associ-
ated with the SRU/TGTU licensor
selection are:
Licensor qualifcations This cate-
gory includes the total number of
sulphur recovery and tail gas treat-
ing units awarded over the previous
510 years, along with the number
of repeat licences. The licensors
experience with the size of SRU
being considered should be closely
evaluated. It is also important that
the evaluation of a licensors quali-
fcation be focused on the actual
experience and qualifcation of the
proposed team
Technical considerations As part
of technical considerations, the
process confguration, operating
conditions and overall sulphur
recovery are compared for each
proposed technology. Items such as
process simplicity, catalyst require-
ments, operating fexibility, unit
turndown capability, utility and
off-sites impacts, reliability and
maintenance, safety impacts and
emissions are evaluated
Economic considerations An
economic evaluation using the net
present value (NPV) method is
performed over a 25-year operating
period. There are minimal revenues
associated with the product streams
from the SRU/TGTU. The NPV
calculations are primarily based on
total capital cost and annual operat-
ing costs, such as utilities, licence
is used only for peak shaving or for
spare capacity, such as when one
train is shut down for maintenance.
In oxygen enrichment mode of
operation, the capacity of the SRU
can be increased up to 25% with
almost no initial capital cost, or up
to 150% of its original design capac-
ity with minimum pre-investment
costs. Any capacity increase above
25% would require pre-investment
on the metallurgical selection of the
burner and additional design capac-
ity of other components within the
sulphur recovery system
Optimising sulphur recovery train
size If the oxygen supply is not
available or cost prohibitive, the
size of the sulphur recovery train
can be optimised to include some
spare capacity. Planned mainte-
nance of an SRU is typically
conducted during a shutdown of a
group of upstream process units.
Detailed sulphur balances are
required for each group to ensure
that the on-line SRU train has
enough capacity when the other
SRU train is down. If necessary, a
spare train could be considered.
Figure 1 Amine regeneration unit
Slop oil
Vent to vapour
recovery
Rich
amine
Rich amine
pump
Lean amine
Amine
fltration
Lean amine
pump
Cond.
LP steam
Sour water
Acid gas
to SRU
Acid gas
to fare
Refux
pump
Flash drum
Regenerator
FC
TC
LC
LC
FC
FC
LC
FC
PC
CW
FC
fluor1.indd 4 10/3/10 11:41:48
www.ptqenquiry.com
merichem gtp.indd 1 8/9/09 10:51:32
fees and catalyst costs. To perform
accurate NPV calculations, detailed
in-house capital cost estimates are
prepared for each technology on a
project-specifc, normalised basis.
Estimated total installed cost
(TIC) from a licensors proposal
should never be used to facilitate
this economic evaluation, as
such estimated fgures are often
low and exclude a lot of cost items,
such as foundation preparations,
contingencies, escalations and
owners cost.
Commercial considerations Licensor
guarantees, licence fees, engineer-
ing fees and catalyst costs are
evaluated. Compliance with terms
and conditions, project execution
schedule and other requirements
are evaluated. Performance guaran-
tees on sulphur recovery effciency,
SO
2
emissions, sulphur product
purity and catalyst run length are
compared.
Amine system design
In the process of refning crude oil
to produce low-sulphur refned
products, sour gas is produced. The
H
2
S it contains is usually removed
in the gas contactors of the HSRU
using a circulating amine solution,
such as diethanol amine (DEA) or
methyl diethanol amine (MDEA).
Lean amine is also used in liquid-
liquid contactors to remove H
2
S
from liquefed petroleum gas (LPG)
products. The rich amine, loaded
with H
2
S, is then regenerated in an
ARU.
Figure 1 shows a simplifed fow
diagram for a typical ARU. H
2
S is
stripped from the rich amine solu-
tion in a regenerator to produce a
lean amine. The lean amine is recir-
culated back to the contactors in the
HSRU or to other upstream process
units to complete the amine circuit.
Stripped acid gas is sent to a SRU
for further processing.
Solvent selection
Aqueous alkanol-amines are typi-
cally used to remove H
2
S, CO
2
and
some COS from sour gas and sour
liquid streams by a reactive absorp-
tion process. The process involves a
chemical reaction between a weak
base (amine) and a weak acid
(gases), producing a water-soluble
salt that can be regenerated using
steam stripping to release the acid
gases from the rich amine solution.
There are several types of amine
contactor in the refnery. High-
pressure absorbers process
hydrogen recycle gas streams in the
reactor loops of hydroprocessing
units. The H
2
S specifcation is based
on requirements for the technology
used in the hydroprocessing unit.
These high-pressure units are typi-
cally the major source of H
2
S
pick-up.
Low-pressure absorbers treat
refnery sour gas. The sulphur spec-
ifcation for treated fuel gas is
typically 50160 ppmv H
2
S, depend-
ing on the environmental regulatory
requirement. In addition, there are
liquid-liquid contactors in the refn-
ery to remove H
2
S from liquid
hydrocarbon streams, such as LPG.
The sulphur specifcation for treated
LPG is about 20 ppm wt H
2
S.
When appropriate amine contac-
tors are identifed, an evaluation is
required to select the optimum type
of amine. For existing facilities, an
evaluation of the current system
may be required, with the objective
of maintaining a single solvent at
the refnery. For example, if the
solvent used is MEA, the conver-
sion of the existing MEA solvent
system to MDEA could be consid-
ered. This would increase existing
capacity by about 15%, with a posi-
tive impact on utilities.
For new applications, the tertiary
amine MDEA is preferred over
monoethanol amine (MEA) and
DEA. MDEA selectively removes
dilute H
2
S from sour gas and liquid
streams. It is chemically less corro-
sive than MEA, thus allowing
circulation of solution strength to
50%, which equates to a lower
circulation rate and consequently
relatively smaller equipment. The
maximum acid gas loading for 45
wt% aqueous MDEA solution
ranges from 0.450.50 mole acid
gas/mole MDEA (see Table 3).
MDEA has a lower heat of reaction
with H
2
S, hence requires less energy
for regeneration. It does not react
with and is not degraded by COS
and CS
2
.
In general, MDEA has lower capi-
tal and operating costs when
compared to MEA and DEA. The
capital cost would be lower since
lower circulation is required. The
operating cost would be lower due
to less steam usage. This makes
MDEA the recommended solvent
for new applications. MEA,
however, may still be preferred for
low-pressure contactor applications
with stringent sour gas specifca-
tions. Similarly, DEA may be
preferred if a portion of CO
2
must
be absorbed from the sour gas.
Centralised or standalone amine
system
A refnery can be designed with a
centralised amine system that
would supply amine to all or most
users. Some situations may require
a standalone ARU dedicated to a
single user. One such standalone
case is the amine system for the
TGTU. A separate solvent system is
typically required for stringent H
2
S
removal levels for the absorber in
the TGTU, which operates at very
Amine Solution concentration limit, % Gas loading limit
(mole acid gas/mole amine)
MEA 20 0.40
DEA 2535 0.400.50
MDEA 4045 0.400.45
Amine concentrations and maximum loadings
Table 3
When appropriate
amine contactors
are identifed, an
evaluation is
required to select
the optimum type
of amine
fluor1.indd 5 16/3/10 14:59:19
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merichem process.indd 1 11/6/09 12:25:11
low pressures of approximately
0.5 psig. In some cases, the TGTU
licensor may also select a proprie-
tary type of amine solvent, with
special additives.
Another case where a dedicated
amine system may be required is
for hydroprocessing units that
cannot accept lean amine with any
residual CO
2
. They utilise a nickel-
based catalyst system, which can be
deactivated by CO
2
present in the
lean amine solvent. Residual CO
2
may be present in the lean amine if
the centralised system is treating
process gas from a coker or FCC
units, or treating imported gas
streams with high CO
2
content.
Amine integrated model
Once all the amine users have been
identifed, an integrated simulation
model should be developed. This
should include all amine contactors
and the ARU, modelled as one
system. The objective is to validate
contactor performance in meeting
H
2
S and CO
2
specifcations and to
develop a preliminary sizing basis
for the ARU and the associated
steam requirements.
Different simulation software
packages are commercially availa-
ble to prepare the integrated model.
Signifcant variations in residential
H
2
S prediction have been noted
between different simulation pack-
ages. Comparison to plant data is
recommended to validate the simu-
lation results.
Rich amine system
The ARU receives rich amine from
numerous upstream process units,
many of which are operating at high
pressure. As the ARU is designed for
low design pressures, our preferred
design practice is that the upstream
unit be provided with a rich amine
fash drum with a design pressure
equivalent to the amine fash drum
in the ARU, typically about 150 psig.
This approach avoids the potential
for one unit to cause an over
pressure condition in the ARU or
in any other refnery unit connected
to the rich amine header. This
greatly simplifes the relief systems
design and eliminates any cases of
vapour breakthrough relief. Plant
safety is increased, as the need for
complicated procedures to lock
open block valves on the amine
distribution header is eliminated,
particularly during planned and
unplanned shutdowns.
A separate rich amine fash drum
is also preferred for liquid treating
units, such as LPG treating units.
Amine regenerator design
Figure 1 shows a typical open-art
design for the ARU. It consists of a
stripping column with approxi-
mately 20 valve trays, equipped
with an overhead condenser system.
Some systems utilise a pumparound
system with a liquid cooler instead
of the overhead condenser system.
The pressure drop is somewhat
lower, but it raises the height of the
column.
Careful consideration should be
given to the pressure profle across
the ARU and SRU/TGTU in the
early phase of the design, consider-
ing plot location and impact to
equipment sizing.
The critical parameter for the
ARU is the stripper bottoms pres-
sure. For a system using 45 wt%
MDEA solvent, the maximum pres-
sure is about 18 psig. Selecting a
higher pressure would raise the
temperature in the column bottom
and lead to amine degradation.
Selecting a much lower pressure
would result in insuffcient acid gas
pressure to the SRU. The SRU
needs about 12 psig acid gas pres-
sure at the inlet to the unit. This is
required to account for the pressure
drop across the SRU and TGTU
sections with reasonably sized
equipment.
Metallurgical considerations
Corrosion of carbon steel compo-
nents in amine services is not
caused by the amines themselves,
but by dissolved acid gases, such as
H
2
S and CO
2
, or by amine degrada-
tion products, such as heat-stable
salts. Variables affecting the corro-
sion rates are acid gas composition,
type of amine, solvent concentra-
tion, operating temperature,
solution purity, amine velocity and
type of metallurgy selected.
The type of amine primarily
affects allowable concentration and
loading. In general, MEA is more
corrosive than DEA, MDEA or
other amines, so lower concentra-
tions and loadings are required.
Typical limits for carbon steel corro-
sion concerns are shown in Table 3.
Two key preventive measures are
the use of upgraded alloys in criti-
cal areas and meeting the velocity
limits for rich amine piping. For
example, the lean amine piping
from the regenerator to the rich/
lean exchanger, and the lines to and
from the regenerator reboiler, are
specifed as 316L to avoid corrosion
due to high temperature (260F).
Stress corrosion cracking (SCC)
has occurred because of MEA, DEA,
MDEA, diisopropanol amine
(DIPA) and other amines. It is
signifcantly more prevalent in
MEA systems than in other amines.
There are no indications that inhibi-
tors, caustic soda, flters or
reclaimers contribute to or inhibit
cracking tendencies. Thermal stress
relief is considered the most effec-
tive means of preventing amine
SCC. In the past, some refners and
gas plant operators stress relieved
only above certain operating
temperatures, but most of the
industry now stress relieves all
amine services, except ambient
temperature storage tanks.
Sour water system design
Sour water containing appreciable
concentrations of H
2
S and NH
3
is
produced in refnery process units.
The sour water is routed to a
SWTU. See Figure 2 for a simplifed
process fow diagram of a typical
SWTU. It includes a sour water
stripping column, where water
from the upstream units is steam
stripped to suitable levels of H
2
S
and NH
3
for further processing in
Sour water tanks are
sources of fugitive
H
2
S emissions.
Various methods
are available to
contain them
fluor1.indd 6 10/3/10 11:42:08
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the downstream wastewater treat-
ing unit. The SWTU is also designed
to separate gas, light hydrocarbons
and oil emulsions from the sour
water.
A signifcant volume of stripped
sour water is reused in upstream
process units, as wash water in
hydroprocessing units or desalting
water from crude units. The remain-
ing stripped sour water is routed
for additional treatment to the
wastewater-treating unit to meet
environmental regulations as a
plant effuent. Acid gas rich in H
2
S
and NH
3
from the SWTU is sent to
the SRU for further processing.
Phenolic SWT
In addition to H
2
S and NH
3
, sour
water may also contain phenols,
cyanides, chlorides and carbon
dioxide from upstream units where
oxidisation is involved. The level of
these contaminants in the sour
water streams depends on the refn-
ing processes and the origin of the
process feedstock. For example,
FCC and coker units produce sour
water with high levels of phenols.
The phenols are not removed in the
SWTU but stay in the stripped sour
water.
Since upstream hydroprocessing
units cannot use stripped sour
water with signifcant levels of
phenols, a standalone phenolic
SWTU is required for processing
sour water from the units that
produce phenols. Stripped sour
water from the phenolic SWTU is
not reused in the hydroprocessing
units; instead, it is routed to the
crude unit desalter for recycling the
benzenes and phenols. Any excess
stripped sour water is routed
directly to the wastewater-treating
unit.
Sour water storage tank
Sour water storage is required
upstream of the SWTU. For the
phenolic SWTU, a dedicated storage
tank is necessary so that sour water
can be processed separately. The
sour water storage tank provides the
hold-up time needed for weathering
the sour water and the surge time
required in the event of a SWTU
shutdown. In some cases, the sizing
basis for the storage tanks is dictated
by local agencies.
Sour water tanks are sources of
fugitive H
2
S emissions. Different
methods are available to contain
them. Some systems are based on a
foating-roof tank with a diesel oil
layer above the water phase to
absorb H
2
S. The spent oil is with-
drawn and replaced when it is
almost saturated with H
2
S. Other
systems are based on a cone roof
tank with a push-pull system, with
a vent to the fare system. To avoid
H
2
S release to fare, systems can be
specifed to compress the vent to
the refnery sour gas system using
a liquid ring pump.
SWTU metallurgy
The sour water feed to the SWTU
contains NH
3
in addition to H
2
S.
Ammonia is released from sour
water in the sour water stripper
Slop oil
Vent to vapour
recovery
Sour
water
Sour water
pump
Sour water
charge pump
Stripped sour water
pump
Vent to vapor
recovery
Stripped
sour water
Cond.
LP steam
Acid gas
to SRU
Acid gas
to fare
Refux
pump
Sour water
surge drum
Stripper
FC
TC
LC
LC
FC
FC
LC
PC
CW
Figure 2 Sour water stripping
fluor1.indd 7 10/3/10 11:42:19
and ows out with the overhead
acid gas, where bisulphide (NH
4
HS)
can be formed. As the overhead gas
stream cools down and condensa-
tion occurs, ammonium bisulphide
salt can precipitate and corrode
carbon steel materials.
Corrosion rates increase as a
function of aqueous NH
4
HS concen-
tration. NH
4
HS corrosion is also
sensitive to ow regime and wall
shear stress. Severe corrosion and
erosion can occur on carbon steel
tubes in heat exchangers if the uid
velocity exceeds acceptable limits.
Another concern is ammonium
salt corrosion in the steam reboiler.
Some units have experienced
ammonium chloride corrosion due
to the amount of chlorides in the
sour water feed. This can cause
corrosion on carbon steel or SCC on
austenitic stainless steel.
Each section of the SWTU needs
to be evaluated carefully for mate-
rial selection. The typical alloy
upgrades for a SWTU include 304L,
2205 duplex, Alloy 825 and tita-
nium. For example, on one unit,
304L was used for cladding the
overhead accumulator and the top
of the stripper column; titanium
was used for the overhead
condenser header and tubes; and
304L was used for the overhead
piping between the column,
condenser and accumulator.
Conclusion
The trend in rening is to increase
bottom-of-the-barrel processing and
produce clean fuels. The sulphur
block is an essential part of these
aims and contributes signicantly
to project costs. Substantial
improvements in project execution
can be achieved by addressing key
design issues early.
Sulphur block units are primarily
for environmental control. They
enable upstream process units to
generate revenue, while keeping
the renery in compliance with
HSE requirements, which should be
clearly identied during the early
phases of a project to design or
upgrade a sulphur block. Other key
activities include selection of unit
capacity, number of processing
trains, amine system design and
sour water treating options.
The second part of this article will
address design and selection issues
regarding the SRU, TGTU, and
product sulphur degassing and
storage.
Shamim A Gandhi is a Principle Process
Engineer with Fluor Corporation in Aliso Viejo,
California, with over 25 years of petroleum
rening and gas treating experience. He has a
MS in chemical engineering from the University
of California at Berkeley.
Email: Shamim.gandhi@uor.com
Wayne C Chung is a Manager of Process
Engineering with Fluor Corporation in Aliso
Viejo, California, with over 30 years of gas
processing and renery experience. He has a
MS in chemical engineering from Arizona State
University.
Email: Wayne.chung@uor.com
Krish K Nangia is a Director of Process
Engineering with Fluor Corporation in Aliso
Viejo, California, with more than 35 years of
renery and gas processing experience. He has
a PhD in chemical engineering from McGill
University, Montreal, Canada.
Email: Krish.nangia@uor.com
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When MTBE outscores ETBE for
bioenergy content
D
espite improvements in
engine technology and fuel
effciency, total CO
2
emis-
sions from road transport fuels
continue to grow every year. We
must reduce our global dependency
on the use of fossil energy.
Over the past decade, we have
seen an increase in the use of
biodiesel as an alternative to
diesel, with ethanol being used as
a biocomponent in gasoline, either
in ethyl tert-butyl ether (ETBE) or
through splash blending. Although
these biofuels are made from
renewable resources, the past few
years have seen increasing concern
over sustainability issues, such as
deforestation, indirect land use
change and competition with food.
These issues are driving legisla-
tors to insist on the use of better
biofuels made from more sustain-
able feedstocks. For biodiesel,
alternative oil feedstocks include
algae, jatropha and used cooking
oils. Much effort is similarly going
into the research and development
of cellulosic ethanol. But there are
other solutions. One such alterna-
tive sustainable fuel, biomethanol,
is already commercially available in
large volumes.
Biofuel generations
The development towards more
sustainable biofuels has been
described by some as second-
generation biofuels to distinguish
between traditional biofuels and
those with more environmentally
friendly attributes. In the EUs
Renewable Energy Directive (RED),
however, there is no mention of
the term. And to make matters
more confusing, some of the latest
If MTBE is produced from biomethanol, its bioenergy content as a fuel additive
will be counted twice, according to EU biofuels regulations
EElco DEkkEr
BioMCN
developments are now described as
third- or fourth-generation biofuels.
Even though there is no clear def-
nition of these different generations,
a number of specifc characteristics
are typically mentioned in refer-
ence to second-generation biofuels:
feedstock sustainability; innovative
technology; similar fuel properties;
and reduction in GHG emissions.
These help to distinguish between
different biofuels and demonstrate
that biomethanol does, indeed,
qualify as a better biofuel.
What makes a second-generation
biofuel?
Feedstock sustainability
Biofuels were introduced as an
important part of the solution to
reducing the use of fossil energy
sources and limiting the effects of
global warming. But with growing
volumes of ethanol and biodiesel
being blended in the fuel pool,
there also came concern over the
potential negative effects some
biofuels themselves might have on
the environment.
Although many factors have
an impact on the agricultural
sector, when food prices shot up
in 2008 many analysts were quick
to blame biofuels as the main
cause. Deforestation, change in
land use and child labour are but
a few of the other negative trends
blamed on biofuels. As a result of
these concerns, there is increas-
ing pressure on biofuel producers
to start using more sustainable
feedstocks.
Article 17 of the RED lists sustain-
ability criteria that biofuels need to
fulfll to be taken into account for:
Measuring compliance with the
requirements of the RED concern-
ing national targets
Measuring compliance with
renewable energy obligations
Eligibility for fnancial support
for the consumption of biofuels and
bioliquids.
An exception is made for biofuels
made from waste and residues.
These only need to comply with the
sustainability criteria described in
paragraph 2 of the same article,
which deals with GHG emissions.
One such feedstock is crude
glycerine, the raw material for
producing biomethanol. Crude
glycerine is a processing residue
from biodiesel production and
the oleochemical industry, and is
recognised as such in Annex V.C.18
of the RED:
Wastes, agricultural crop resi-
dues...and residues from processing,
including crude glycerine (glyc-
erine that is not refned), shall be
considered to have zero life-cycle
greenhouse gas emissions up to
the process of collection of those
materials.
Innovative technology
Another common denominator in
discussions about better biofuels
is the use of innovative production
technologies to convert sustainable
feedstocks into biofuels. Typical
examples include Fischer-Tropsch,
hydrogenation processes and
biomass gasifcation.
Biomethanol production is based
on the original methanol produc-
tion process, which converts natural
gas (CH
4
, methane) into methanol.
Here, three stages steam reform-
ing, synthesis and distillation
produce 99.85% pure methanol.
biomcn.indd 1 10/3/10 12:12:35
and fed to an evaporator, which is
optimised to prevent early glycerine
degradation. Glycerine vapour is
fed to the existing steam reformer,
just like natural gas in the original
process.
In the reformer, as with natu-
ral gas, the glycerine is split into
syngas (the reformer can also be
fed with a mixture of biogas and
natural gas). When converting a
signifcant amount of glycerine,
the CO/CO
2
ratio in the syngas is
slightly different to that of syngas
produced from natural gas only,
but this is of no consequence for
the feed to the methanol synthe-
sis. Steam reforming of glycerine
produces no components other than
those expected in a conventional
syngas mixture. Hence, methanol
synthesised from natural gas and
biomethanol produced from glyc-
erine are chemically identical. So
(apart from expensive C
14
analysis)
it is not possible to identify whether
a methanol molecule has a natu-
ral gas or glycerine origin. As for
performance and applications, there
is no difference whatsoever.
1
BioMCN has a total methanol
capacity of 1 million tonnes, of
which currently 200 000 tonnes have
been converted to biomethanol.
Similar fuel properties
Even though biodiesel and ethanol
are used in blend formulations, or
even to fully replace fossil diesel
and gasoline respectively, they do
not have exactly the same proper-
ties as their fossil counterparts.
They can differ in terms of cloud
point, acidity or energy content.
Ideally, a better biofuel should
have properties very similar to
those of its fossil counterpart.
Biomethanol is chemically iden-
tical to regular methanol made
from natural gas (Figure 1). As
such, it can be used to convert
any existing methanol applica-
tion into a bioalternative. Like
ethanol, biomethanol has a lower
energy content and is more acidic
than gasoline. However, this does
not have to be an issue, because
the relevant question should be:
What makes an ideal fuel? The
answer may surprise some (see
Table 1).
After purifcation, natural gas is
cracked in a steam reformer. Steam
reforming mixes the methane
with large amounts of steam. The
methane/steam mixture fows
through pipes over a catalyst and is
heated to 500850C. After the steam
reformer, the methane is split into
syngas: a mixture of carbon monox-
ide (CO), carbon dioxide (CO
2
)
and hydrogen (H
2
). The syngas is
cooled to an ambient temperature
and compressed to close to 100
bar before it is fed to the synthesis
reactor. In this reactor, the syngas
components react to form methanol.
This methanol contains about 17%
water, which is removed by distil-
lation. In the distillation process,
water, light alkanes and the heavy
ends (denser fractions) are removed
from the main stream. The outcome
is 99.85% pure methanol.
The production process for
biomethanol is no different to the
production of regular methanol.
What is different is the origin of the
gas stream going into the methanol
reformer. Instead of natural gas,
the feedstock is glycerine. It is not
possible to feed liquid glycerine to
the reformer directly. It frst has to
be converted to the gas phase. The
glycerine is purifed and evaporated
in a process patented by BioMCN.
The crude glycerine contains
several impurities, mainly water,
sodium and potassium salts, and
a certain amount of undefned
organic components. These have
to be removed, since the glycerine
feedstock to the evaporation unit
has to have a high purity level with
a low chloride and sulphur content.
The glycerine is purifed in a
vacuum distillation process, where
it can be evaporated below its
degradation temperature to remove
unwanted components. The organic
matter (heavy fractions) that has
been removed from crude glycerine
can be used in fermentation units to
produce biogas for generating green
electricity (so also contributing to
the reduction of CO
2
emissions).
The purifed glycerine is heated

Fig1:

Pu rity
Formula
Methanol Bio-methanol
Feed sto ck
Well to wh eel C O
2
> 99.85%
N atu ral g as
> 99, 85%

C ru d e g lycerin e
/ 70%
Figure 1 Methanolandbiomethanolareidentical
Ideal property Low carbon number alcohols vs gasoline
1. Highoctaneindex MuchbetterRONandMON
2. Highheatofvapourisation(latentheat) Signifcantlyhigher
3. Lowstochiometricair-fuelratio(AFR) Muchlower
2 & 3 combined: reduces cycle temperature
4. Highspecifcenergyratio Higher
5. Highfamespeed 3050%higher
Improves EGR tolerance
6. Highmolarratioofreactantstoproducts Higher
More work, less heat rejection
7. Lowcombustiontemperature Lower
Reduces heat rejection
8. Lowcarbonnumber Yes
9. GoodgCO
2
/MJ Betterthangasoline
10.LiquidatSTP Yes
Minimises oxygen displacement
Ideal fuel properties
Table 1 Courtesy: James Turner, Lotus Engineering
Biomethanol
biomcn.indd 2 10/3/10 12:12:46
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Reduction in GHG emissions
Another objective of the RED is
the reduction of GHG emissions.
Depending on the type of feed-
stock used and the energy input to
produce a biofuel, the average well
to wheel reduction of GHG emis-
sions is very different. The RED
has set clear targets for reducing
GHG emissions, and in future those
biofuels that do not meet the lower
limits will no longer be included in
the bioenergy targets.
According to paragraph 2 of arti-
cle 17, biofuels can only be taken
into account for compliance with
the requirements of the directive
if GHG savings are at least 35%.
From January 2017, the savings
will have to be at least 50%, and for
new installations that start produc-
tion after 1 January 2017, emissions
savings will have to be at least 60%
from January 2018.
For biomethanol made from crude
glycerine, the current GHG savings
are already around 57%, and after
some further process optimisations
the emissions savings are expected
to even exceed 70% later this year.
Biomethanol in fuel applications
Biomethanol meets all the require-
ments of a second-generation
biofuel. So how can it be used most
effciently to contribute to renew-
able energy targets?
Option 1: Biodiesel To produce
biodiesel, 10% methanol is added to
90% vegetable oil in an esterifca-
tion process, resulting in 90%
biodiesel and 10% crude glycerine.
This allows for a perfect closed-loop
system (see Figure 2). But, because
the RED considers biodiesel to be
of 100% bio-origin, there is no
immediate beneft to replacing the
existing methanol unless it helps to
improve CO
2
emissions reduction
potential or when required by
specifc national legislation
Option 2: Bio-DME Di-methyl
ether (DME) can be used in diesel
engines, as liquifed petroleum gas
(LPG) is used in gasoline engines.
In Europe, DME is still primarily
used as a propellant in spray cans,
while China is advancing its use as
an energy product
Option 3: Biohydrogen Even
though the use of hydrogen as
engine fuel has been investigated
for many years, so far it can hardly
be called a commercial break-
through. Despite attractive low
tailpipe emissions, most hydrogen
produced today is still made from
natural gas. An alternative and
sustainable way of producing
(bio)hydrogen is by converting
biomethanol into biohydrogen.
Since the use of hydrogen as a
transportation fuel is currently
limited to demonstration projects, a
more immediate short-term oppor-
tunity is to use biomethanol in
direct methanol to hydrogen fuel
cells (DMFCs) as battery replace-
ments in laptop computers and
mobile phones
Option 4: Biogasoline In 1979, the
New Zealand government decided
to build a commercial 14 500 bpd
plant in Montunui, owned 75% by
the New Zealand government and
25% by Mobil. The resulting gaso-
line has properties very similar to
those of regular gasoline made from
BioMCN
plant
vegetable oil Lsterification plant 90% biodiesel
l0% glycerine 8iomethanol
Figure 2 Biomethanol can be produced in a perfect closed loop
crude oil. The plant started up in
1985 and operated successfully for
around ten years until its conver-
sion to chemical-grade methanol
production
2

Option 5: Direct blending (M85)
Just as they consume E85 (85%
ethanol, 15% gasoline), fexifuel
vehicles can run on M85 (85%
biomethanol, 15% gasoline). This is
a very effcient way of using the
bioenergy content of biomethanol
while maintaining as much of the
CO
2
reduction potential as possible.
However, the use of high alcohol
blends in Europe is currently still
limited
Option 6: Bio-MTBE When the frst
biofuels mandates were imple-
mented, one solution chosen by
several refneries was to switch
existing methyl tert-butyl ether
(MTBE) facilities to produce ETBE.
A drawback of this switch is that
output is limited to either a fossil
oxygenate (MTBE) or a bio-
oxygenate (ETBE).
With biomethanol, the same
plant can produce both a regular
(fossil) oxygenate as well as a bio-
oxygenate without having to make
changes. This enhances fexibility
and enables refneries to choose the
option with the highest return.
In Europe, about 4 million tonnes
of oxygenates are blended every
year. In todays market, bio-MTBE
is therefore the best option for
adding biomethanol to existing fuel
formulations while still meeting the
requirements of the Fuel Quality
Directive (EN228).
MTBE
Despite the clear beneft of MTBE
in reducing emissions and thus
contributing to better air quality,
it was the centre of much negative
attention in the 1990s when high
levels of MTBE were found to be
contaminating Californian ground-
water. This was caused by leaking
underground storage tanks and
spills due to overflling.
Groundwater contamination
involving gasoline is not new.
MTBE has attracted attention to
this problem because it has become
a widely used gasoline component,
with several specifc properties that
distinguish it from other gasoline
biomcn.indd 3 10/3/10 12:12:53
ingredients such as benzene and
toluene:
3
MTBE is more soluble in water
than other gasoline components, so
in certain conditions it tends to
spread faster and further through
the soil, creating a halo effect
around the spill
MTBE has a very low taste and
odour threshold that is noticeable
at low concentrations
MTBE biodegrades more slowly
and therefore may appear to persist
in the environment for longer.
These properties highlighted the
fact that there were problems with
underground storage releasing
gasoline into the groundwater, but
also made MTBE stand out from
the other contaminants. Its strong
smell and taste are easy to detect,
and resulted in it becoming the
scapegoat of a much more serious
problem, which has led some states
to ban MTBE.
Several reports have demon-
strated that the incidence of
serious groundwater contamina-
tion by MTBE, both in the US and
Europe, is in fact low. Nevertheless,
it has led to many misconceptions
and prejudices against MTBE.
These are largely unfounded
because it has been demonstrated
that the environmental and health
impact of MTBE is comparable,
with the exception of certain minor
variations, with that of ETBE and
tert-amyl methyl ether (TAME).
MTBE has undergone a full EU
risk assessment study for both
health and environmental effects.
The results were published in the
Offcial Journal of the European Union
on 4 December 2001. Both health
and environmental effects are eval-
uated, together with the potential
for exposure, to assess the overall
risk that a substance may present.
This process led to a formal deci-
sion by the EU that MTBE is not
classifed as carcinogen, mutagen or
reproductive toxin.
4
The presence of MTBE in ground-
water is certainly not inherent to
the product itself, but can clearly
be attributed to careless handling.
Banning MTBE does not solve the
underlying problem of gasoline
leakage and may create a false
sense of security, as contamination
860 kilo
Bio-MTBE
1000 kilo
ETBE
Figure 3 Adminstratively, only 860kg of bio-MTBE are needed to replace a tonne of ETBE
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could go undetected much longer.
MTBE has delivered signifcant air
quality benefts by reducing harm-
ful exhaust emissions. As long as
the issue of groundwater contami-
nation is avoided through proper
handling and storage, the public
need not be denied the proven
benefts of MTBE, which can now
be further extended when MTBE is
made from biomethanol.
Bio-MTBE and bottom line results
To encourage the development and
use of more sustainable biofuels,
RED Article 21.2 specifes that the
energy content of biofuels made
from a sustainable feedstock be
counted twice towards operators
targets:
For the purposes of demon-
strating compliance with national
renewable energy obligations
placed on operators and the
target for the use of energy from
renewable sources in all forms of
transport referred to in Article 3(4),
the contribution made by biofuels
produced from...residues...shall be
considered to be twice that made
by other biofuels.
According to Annex V.C.18 of the
RED, crude glycerine is labelled as a
residue from processing. This means
the bioenergy content of biometha-
nol, which is made from crude
glycerine, will be counted twice no
later than the implementation of
the Directive in December 2010.
In December 2009, well in
advance of this RED implementa-
tion deadline, the Dutch parliament
accepted an amendment to national
legislation to implement the so-
called double counting measure
with immediate effect. An impor-
tant element of the legislation is
the verifcation protocol, which
describes how producers and
consumers of these better biofu-
els have to demonstrate compliance
with the rules and regulations of
the amendment to be allowed to
count the bioenergy content twice.
One tonne of biomethanol
contains 20 GJ of bioenergy. When
counted twice, the same volume
is then reported to have 40 GJ of
bioenergy. In comparison, bioetha-
nol contains 27 GJ of bioenergy. In
other words, 1 tonne of biometha-
nol can (administratively) replace
1.5 tonnes of bioethanol (see
Table 2).
To fully appreciate the impact
of the higher bioenergy content of
biomethanol, the production proc-
ess of bio-MTBE has to be compared
to that of ETBE, an alternative bio-
oxygenate. (Bio-)MTBE is produced
through the chemical reaction of
(bio)methanol with isobutylene,
whereas for ETBE ethanol is used
as an alternative to methanol. The
addition ratios are very different,
though. Whereas MTBE contains
~36% methanol, ETBE contains
~45% ethanol.
To confuse matters further, the
energy contribution of these alco-
hols relative to their total energy
content is also lower than their
volumetric share. The RED contrib-
utes 37% of the energy content
of ETBE (36 GJ/tonne) to etha-
nol (versus 45% in volume), and
only 22% of the energy content of
MTBE (35 GJ/tonne) to biometha-
nol (versus 36% in volume). From
these fgures, the real and admin-
istrative bioenergy content of both
oxygenates can be calculated and
compared (see Table 3).
In other words, despite the fact
that biomethanol has a lower
bioenergy content than ethanol, and
bio-MTBE contains less biometha-
nol than ETBE contains ethanol, the
double counting rule results in a
16% higher (administrative) bioen-
ergy content for bio-MTBE.
For every tonne of ETBE blended
today, only 860kg of bio-MTBE is
needed to achieve the same amount
of bioenergy (see Figure 4). This is
what makes bio-MTBE an interest-
ing product for refneries to comply
with the biofuel mandates in their
respective countries.
To meet their biofuel obligations,
refneries have various options.
Replacing fossil fuels with E85 and
B100 (100% biodiesel) would be the
easiest from an operational point of
view, but so far demand for these
products is too low to meet the
necessary targets. Solutions will
therefore have to be found within
the existing fuel specifcations
Actual energy content Administrative energy content
Energy content Energy content Energy content Energy content
by weight by weight by weight by weight
(lower calorifc (lower calorifc (lower calorifc (lower calorifc
value, MJ/kg) value, MJ/l) value, MJ/kg) value, MJ/l)
Bioethanol 27 21 27 21
Biomethanol 20 16 40 32
Bioethanol vs biomethanol energy contents
Table 2
Table 3
Alcohol, Isobutylene, Energy per Bioenergy, Bioenergy per
% % tonne, GJ % tonne, GJ
ETBE 45.1 54.9 36 37 13.3
MTBE(fossil) 36.4 63.6 35 0 0
Bio-MTBE(2ndgen) 36.4 63.6 35 22 7.7x2=15.4
Administrative bioenergy for ETBE, MTBE and bio-MTBE
Scenario Refnery Biocontent (per tonne oxygenate) Blend impact
Current X%ETBE 13.32GJ
Maintain X%bio-MTBE 15.44GJ +16%
Reduce 0.86X%bio-MTBE 13.32GJ =
Increase 1.03X%bio-MTBE 15.90GJ +19%
The higher energy content of bio-MTBE makes for versatile production at refneries
Table 4
biomcn.indd 5 10/3/10 12:13:15
laid down in the Fuel Quality Directive (EN228). This
currently allows for a maximum of 15% oxygenates
and 5% ethanol, provided the fnished gasoline prod-
uct stays within specifc limits (eg, oxygen content and
vapour pressure, RVP).
This has resulted in a more or less common approach
in Western Europe, where ~5% oxygenate (ETBE or
MTBE) is frst blended at the refnery. This blend
is better known as Blending Oxygenate Basestock
(EuroBOB). Even though the exact composition can
differ between refneries or as a result of blend cost
formulations, all EuroBOBs have in common that up
to 5% ethanol can be added afterwards at the rack or
depot to formulate the fnished gasoline product that is
sold at the petrol station (EN228, Euro 95).
Depending on the current strategy to meet biofuel
objectives, refneries can beneft in different ways from
the higher energy content of bio-MTBE:
Option 1: Maintain By replacing current ETBE
volumes with bio-MTBE, the bioenergy content of the
EuroBOB goes up. This gives a refnery the choice of
blending less ethanol at the depot to replace it with
less expensive gasoline components, or continuing to
blend the same amount of ethanol to sell gasoline with
a higher biocontent while staying within the limits of
the EN228 specifcations
Option 2: Reduce If the objective is to sell EuroBOB
gasoline with the same bioenergy content as its ETBE
counterpart, bio-MTBE allows the amount of bio-
oxygenate to be reduced, thus creating room to blend
other less expensive gasoline components
Option 3: Increase Even though bio-MTBE has a
higher bioenergy content than ETBE, the overall energy
content of ETBE is slightly higher. If a refnery requires
the same amount of energy contribution from the
oxygenate component, about 3% more bio-MTBE needs
to be added. This results in an even higher bioenergy
content contribution than option 1, with the same alter-
native options at the depot. Table 4 summarises these
options.
Conclusion
MTBE is known to make an important contribu-
tion to reducing GHG emissions. Now that it can be
made from biomethanol, the overall emissions during
its lifecycle are reduced even further. And, because
biomethanol is made from crude glycerine, the bioen-
ergy content counts twice. This enables refneries and
gasoline blenders to reformulate their gasoline compo-
sition to give the best balance between bioenergy on
the one hand and cost on the other.
References
1 www.greencarcongress.com/2007/12/dkrw-selects-ex.html
2 www.efoa.org/EFOA_Pages/04_Environ/04c_Water.asp
3 www.efoa.org/EFOA_Pages/04_Environ/04a_Risk.asp
4 DekkerE,LantingK,Biomethanolasasecond-generationbiofuelfor
transportation,Biofuels Technology,Issue12009.
Eelco Dekker is Chief Marketing Offcer of BioMCN, Delfzijl, The
Netherlands, where he is responsible for biomethanol marketing and
newbusinessdevelopment.Email: info@BioMCN.EU
www.eptq.com
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Microchannel reactors in fuel production
B
iofuels produced entirely
from waste such as agricul-
tural by-products and
municipal solid waste have
attracted attention as a substitute
for petroleum-based transport fuels.
Since they do not contain aromatics
or sulphur-containing contami-
nants, the liquid fuels produced via
biomass to liquids (BTL) are typi-
cally of a higher quality, and they
burn more cleanly than petroleum-
based diesel and jet fuels. They
could also prove to be valuable in
the effort to reduce carbon emis-
sions. A study carried out by the
Southern Research Institute Carbon
to Liquids Development Center
in the US used the GREET
(Greenhouse gases, Regulated
Emissions & Energy use in
Transportation) model to show that
biomass-based FT diesel (biodiesel)
production and use results in net
greenhouse gas (GHG) emissions
savings of 135% compared to petro-
leum-based diesel, and GHG
savings of 129% compared to
petroleum-based gasoline. This is
largely because bio-derived synthetic
diesel production relies on biomass,
rather than fossil fuels, as a
feedstock.
Despite their potential advan-
tages, economic, environmental and
technical obstacles remain to be
overcome before biofuels produced
from waste can achieve wider
application. A major problem is
that it takes roughly one tonne of
biomass to produce one barrel of
liquid fuel. As a result, to avoid the
economic and environmental costs
of transporting feedstock to central
processing plants, BTL production
facilities need to be relatively small
A demonstration plant aims to confrm the potential for microchannel and other
technologies in the distributed production of biofuels
Derek Atkinson Oxford Catalysts
Jeff McDAniel Velocys
and located near the source of the
feedstock. Establishing small-scale
distributed production of biofuels
as a practical and economically
feasible option requires, in turn, the
development of relatively small
facilities that can produce typically
5002000 bpd of liquid fuels, eff-
ciently and cost-effectively.
The Fischer-Tropsch (FT) process,
in which synthesis gas (syngas), a
mixture of carbon monoxide (CO)
and hydrogen (H
2
), is converted
into various liquid hydrocarbons
using a catalyst at elevated temper-
atures, is a key process in BTL.
However, fxed-bed or slurry-bed
reactors, the two conventional reac-
tor types currently used for FT
processes, are designed to work at
minimum capacities of 5000 bpd.
They only function well and
economically at capacities of 30 000
bpd or higher, and the technology
does not scale down effciently.
However, new reactor designs,
such as microchannel reactors,
combined with more effcient FT
catalysts optimised for use in them,
offer a practical way forward.
Microchannel reactors are compact
reactors that have channels with
diameters in the millimetre range.
They are well suited to the job
because they greatly intensify
chemical reactions, enabling them
to occur at rates 10 to 1000 times
faster than in conventional systems.
For example, microchannel FT reac-
tors developed by Velocys and
using a new highly active FT cata-
lyst developed by Oxford Catalysts
accelerate FT reactions by 1015-
fold compared to conventional
reactors, and exhibit conversion
effciencies in the range of 70% per
pass. This is a signifcant improve-
ment over the 50% conversion (or
less) per pass achieved in conven-
tional FT plants. Their effcient
conversion rates, combined with
their modular construction, makes
microchannel FT reactors, in theory,
an excellent tool for small-scale
distributed production of biofuels
from a wide variety of sources.
Demonstration plant
Developing the technology is one
thing. Establishing it as a practical
and commercially viable solution is
another. A demonstration plant
now being commissioned in the
town of Gssing, Austria, by a
coalition that includes project
developer and lead engineering
integrator SGC Energia (SGCE), the
Oxford Catalysts Group, developers
of the microchannel FT technology,
along with the engineering frm,
Repotec, the Technical University of
Vienna (TUW), and gasifcation
facility owners Biomass CHP
Gssing aims to operate an FT
microchannel reactor and effectively
integrate it with other key steps in
Microchannel
reactors intensify
chemical reactions,
enabling them to
occur 10 to 1000
times faster than in
conventional systems
oxford catalyst.indd 1 10/3/10 12:14:42
the BTL process, including biomass
gasifcation and syngas cleaning.
In the late 1980s, the town of
Gssing, located in southern
Austria near the borders of
Hungary and Slovenia, was the
administrative centre of the poorest
region in Austria. Then, in the
1990s, the city developed a model
to replace energy dependence on
fossil fuels with renewable sources.
By 2001, Gssing had achieved
energy self-suffciency through the
installation of a biomass plant that
takes advantage of steam gasifca-

Fig1:

tion technology. The developments

in Gssing led to the establishment
of the Renewable Energy Network
Austria (RENET). As a result,
Gssing has become a magnet for
companies and researchers keen
to develop renewable energy
technologies.
Other factors determined the
choice of Gssing as the site for a
demonstration of FT microchannel
biofuels production technology.
These included the enthusiasm
expressed by the local technology
community as well as the availabil-
ity of a new test facility and R&D
building with the utilities in place
for SGCE to install the FT and gas
conditioning skids necessary for its
trial. Gssing is also home to a
gasifcation plant that has been
operating in a stable manner for
seven years (Figure 1). The syngas
resulting from this gasifcation
process has the necessary character-
istics and high H
2
/CO ratio
required for FT.
Reduced dimensions
Microchannel process technology is
a developing feld of chemical
processing that enables rapid reac-
tion rates by minimising heat and
mass transport limitations, particu-
larly in highly exothermic or
endothermic reactions. This is
achieved by reducing the dimen-
sions of the reactor systems. In
microchannel reactors, the key
process steps are carried out in
parallel arrays of microchannels,
each with typical dimensions in the
range 0.15mm (see Figure 2). This
modular structure enables reduc-
tion in the size and cost of the
chemical processing hardware.
When microchannel technology is
employed, plant size is small.
Conventional FT reactors are up to
60m tall. In contrast, microchannel
reactor assemblies are roughly 1.5m
in diameter, have a low profle and
sit horizontally. Their modularity
and productivity make them
convenient for use in small-scale
biofuels production plants, and also
opens up the possibility for their
use on offshore platforms to
produce liquid fuel via gas to
liquids (GTL) processes.
Microchannel FT reactor design is
also fexible. For example, where
increasing the size of conventional
reactors normally requires plant
designers to increase the size of
each reactor unit, which alters fow
and reaction dynamics in the reac-
tor, the modular structure of
microchannel reactors means that
increasing plant size to build
demonstration or even commercial-
sized plants can be done by
numbering up. This involves
simply adding more reactors with
the same dimensions. In conven-
tional FT plants, scaling up typically
Figure 1 TheGssinggasifcationplantCourtesy: SGCE
Boiling heat transfer
High heat flux
FT
Microchannel process
technology module
10 times higher heat fux
than conventional reactors
0.01 0.20
0.01 0.20
Figure 2 Inamicrochannelreactor,asinglereactormoduleconsistsofhundredsof
rowsofmicrochannelseachcontaininglargenumbersofparallelmicrochannels.The
orientationandsizeofthechannelswithineachrowisdeterminedbytheapplication,
adjacentrowsofchannelspotentiallyhavingdifferentdutiesCourtesy: Velocys
involves a lot of fabrication in the
feld, as well as respecifcation of
reaction conditions and plant
components. This can be both
expensive and time-consuming. In
contrast, microchannel reactors can
be shop-fabricated, so microchannel-
based plants can be constructed
more quickly and easily, thus
reducing setup costs and the risks
associated with scaling up in
conventional reactors.
Modular construction also makes
the plants more durable and easier
to service because maintenance and
catalyst replacement can be carried
out by replacing individual
modules, rather than requiring a
prolonged shutdown of the entire
system. Finally, the overall capital
costs associated with FT microchan-
nel reactors are relatively low
compared to conventional reactor
systems such as slurry beds.
Process intensifcation
The performance of microchannel
reactors is attributable to their
process-intensifed design, which
results in enhanced heat and mass
transfer capabilities (see Table 1).
Conventional reactor systems rely
on the use of bulky hardware to
manage the heat in FT reactions,
and they have relatively small heat
transfer areas per volume of cata-
lyst. In contrast, in microchannel
reactors, each reactor block has
thousands of thin process channels
flled with FT catalyst, which are
interleaved with water-flled cool-
ant channels. As a result, they are
able to dissipate the heat produced
from the exothermic FT reaction
much more quickly than conven-
tional systems.
This makes them suitable for
carrying out both highly exothermic
catalytic reactions, such as FT
synthesis, and highly endothermic
reactions, such as steam methane
reforming (SMR), in which heat
must be effciently transferred
across reactor walls in order to
maintain an optimal and uniform
temperature, to maximise the cata-
lyst activity and prolong catalyst
life. This allows microchannel reac-
tors to operate at much higher
throughput and productivity.
As a result, microchannel process
technology is looking like a break-
through not only for small-scale FT,
but also for a large number of
chemical and process systems that
involve thermal processing. They
include, for example, ethane crack-
ing, hydrocracking, SMR, ethylene
oxidation, separations, mixing and
emulsifcation, catalytic processes,
gas processing for operations such
as hydrogen production, and inte-
grated and multiphase systems.
Catalysts improved and optimised
Another reason for the increased
throughput per unit volume in
microchannel reactors is that they
enable the use of more active cata-
lysts. Catalysts play a key role in
the FT process. Taking advantage
of the high productivity of these
reactors in BTL processes requires
the right FT catalyst for the job. In
order to boost conversion rates to
an economic level, microchannel
reactors require an FT catalyst with
an exceptional level of activity.
An FT catalyst developed by
Oxford Catalysts enables operators
of microchannel reactors to achieve
productivities (defned as kg/m
3
/h)
that are orders of magnitude higher
than for more conventional systems
(see Figure 3). A demonstration
carried out by Velocys in 2008 in a
nominal two-gallon per day micro-
channel reactor that operated for
more than 4000 hours using the
new catalyst achieved productivi-
ties of more than 1500 kg/m
3
/h. In
contrast, fxed-bed reactors typi-
cally operate at 100 kg/m
3
/h,
while slurry-bed reactors operate at
200 kg/m
3
/h.
The key to the improved perform-
ance of the new FT catalyst is in a
patented catalyst preparation
method, known as organic matrix
Pixed bed Slurry bed Microchannel
200
400
600
800
l000
l200
l400
l600
l800
0
m
/
g
k

,
y
t
i
v
i
t
c
u
d
o
r
p

t
s
y
l
a
t
a
C
3
r
h
/
Figure 3 Productivity of conventional FT catalysts in fxed-bed and slurry reactors,
compared to productivity of the Oxford Catalyst FT catalyst in a microchannel reactor
Microchannel Conventional
Heat transfer, W/cm
2

Convective 120 <1
Boiling 120 <1
Mass transfer (contact time in seconds 0.001-0.3 110
Selectivity, %C
5
+ 7882 8194
Selectivity, %CH
4
<10 No information available
Alpha ratio 0.890.92 >0.9
Contact time, ms <250 No information available
Catalyst life, years Not yet determined 2
Sources: Velocys test data and estimates from Nexant
Microchannel technology offers enhanced heat and mass transfer
Table 1
also produces fewer very small
crystallites that could sinter at an
early stage of operation. This results
in greater catalyst stability. Less
stable crystallites tend to deactivate
quickly, reducing the activity of the
catalysts.
The method can be used to
produce supported base metal cata-
lysts for applications other than
those produced for FT. Evaluations
indicate that catalysts prepared via
OMX perform better than catalysts
containing the same metals but
prepared using standard methods,
such as mechanical milling, wet or
dry impregnation, or via sol-gel or
co-precipitation in a range of base
metal catalysed reactions. Aside
from their higher activity, the cata-
lysts have a longer life and the need
for precious metal promoters on the
catalysts can be reduced, or in some
cases eliminated, while still retain-
ing or even exceeding the benefts
of more conventional catalysts.
Work is currently in hand to scale
up the process to make it possible
to supply formed catalysts in
commercial quantities.
Scaling down
An essential characteristic required
for distributed biofuels production
is the ability to operate effciently
on a small scale. Microchannel
technology shrinks processing hard-
ware, while at the same time
improving its performance. As well
as improved heat transfer proper-
ties and higher energy effciency,
microchannel design enables opti-
mal temperature control across the
catalyst bed, which maximises cata-
lyst activity and life by preventing
the formation of hotspots. It also
results in higher reactor productiv-
ity as well as increased economies
of scale and increased yields of
target products. The reduction in
the reactant residence time achieved
using microchannel reactor technol-
ogy also means inherently safer
operation.
Another advantage of microchan-
nel reactors is their capability to
handle large volumes of feedstock
and their ability to produce quality
fuels from a variety of resources,
including waste wood and munici-
pal solid waste. In terms of
productivity, they far outstrip more
conventional designs and could
help enable the distributed produc-
tion of next-generation biofuels to
become a viable economic reality
and a practical way to reduce
carbon emissions in the near future.
Derek Atkinson is the Business Development
Director responsible for the petroleum and
petrochemical markets at Oxford Catalysts Ltd,
part of the Oxford Catalysts Group, Oxford.
Email: Derek.Atkinson@oxfordcatalysts.com
Jeff McDaniel is the Business Development
Director for Velocys Inc, Columbus, Ohio, part
of the Oxford Catalysts Group.
Email: mcdaniel@velocys.com
combustion (OMX). The OMX
method combines the metal salt and
an organic component to make a
complex that effectively stabilises
the metal. On calcination, combus-
tion occurs to fx the crystallites at
a very small size and in a very
narrow range. Since the calcination
step is quick, metal crystallites do
not have time to grow and hence
remain at an appropriate size for
these types of catalytic reactions.
This is important, because the level
of catalyst activity, selectivity and
stability is related to the surface
area of the catalyst. This, in turn, is
related to crystal size, so producing
catalysts with the optimal crystal
size for a given application is a key
goal for catalyst developers. The
big challenge lies in achieving the
right balance between catalyst activ-
ity and stability. If the crystal size
is too large, the catalyst activity
and, hence, conversion rates are
reduced. If too small, the catalyst
becomes unstable.
The OMX method produces crys-
tallites that exhibit a terraced
surface (see Figure 4), which
enhances catalyst activity. OMX
Figure 4 Transmission electron microscope picture of the FT catalyst produced using the
OMX method
Microchannel
technology shrinks
processing hardware,
while at the same
time improving its
performance
Moving science forward
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Hydrotreating in the production of
green diesel
B
efore feedstocks derived from
renewable organic material
can be used in conventional
car engines and distributed using
existing fuel infrastructure, it is
desirable to convert the material
into hydrocarbons similar to those
present in petroleum-derived trans-
portation fuels. One well-established
method for this purpose is the
conversion of vegetable oils into
normal paraffns in the gasoline or
diesel boiling range by employing a
hydrotreating process. In this proc-
ess, the renewable organic material
is reacted with hydrogen at elevated
temperature and pressure in a cata-
lytic reactor. The clear advantage of
hydrotreating seed oils (or fatty
acid methyl ester, FAME) relative
to the use of FAME biodiesel is the
fact that the fnal products from this
simple hydroprocessing process
(simple paraffns) are the same
components as those present in
normal fossil diesel.
The same types of catalysts are
used in the hydrotreating of renew-
able feeds as are presently used for
the desulphurisation of fossil diesel
streams to meet environmental
specifcations. Thus, a co-processing
scheme where fossil diesel and
renewable feedstocks are mixed
and co-processed is possible,
producing a clean and green diesel
meeting all EN 590 specifcations.
The hydrotreating may also take
place in a dedicated standalone unit
that processes 100% renewable
diesel. In either case, the new feed
components mean that completely
new reactions occur and new prod-
ucts are formed. This gives rise to a
series of challenges relating to cata-
lyst and process design.
A novel scheme enables co-processing of light gas oil and tall diesel to produce a
renewable diesel meeting EN 590 specifcations
RAsmus EgEBERg, NiEls michAElsEN, lARs skyum and PER ZEuthEN
Haldor Topse
challenges of hydrotreating
renewable feeds
Hydrotreating is a vital part of fuel
production, and the economy of the
refnery depends on the on-stream
factor of these units. Thus, before
introducing even minor amounts of
new feedstocks into a diesel hydro-
treater, it is important to know the
implications and how to mitigate
any potential risks.
When considering the conversion
of most naturally occurring, oxygen-
containing species, it is evident that
these are much more reactive than
refractory sulphur compounds,
which must be removed to produce
diesel with less than 10 ppm
sulphur. This means that the prob-
lem of industrial operation will
typically not be to achieve full
conversion, but rather to be able to
control exothermic reactions when
using an adiabatic reactor. As the
reactions also consume large
amounts of hydrogen (for a 100%
renewable feed, a hydrogen
consumption of 300400 Nm
3
/m
3
is
not unusual), higher make-up
hydrogen and quench gas fows are
needed even when co-processing
quite small amounts. Thus, the
refnery hydrogen balance must be
checked, and the unit capacity may
be lower than when processing
fossil diesel only.
The depletion of hydrogen
combined with high temperatures
may lead to accelerated catalyst
deactivation and pressure drop
build-up. Control of these factors
would require the use of tailor-
made catalysts and a careful
selection of unit layout and reaction
conditions. In this way, it is possi-
ble to achieve a gradual conversion
without affecting the cycle length
and still meeting product
specifcations.
In contrast to conventional
hydrotreating, high amounts of
propane, water, carbon monoxide
(CO), carbon dioxide (CO
2
) and
methane (CH
4
) are formed. These
gases must be removed from the
loop either through chemical trans-
formation by a gas cleaning step
such as an amine wash or, more
simply, by increasing the purge gas
rate. If not handled properly, the
gases formed will give a decreased
hydrogen partial pressure, which
will reduce the catalyst activity.
Further problems with CO and CO
2

may occur due to competitive
adsorption of sulphur and nitrogen-
containing molecules on the
hydrotreating catalyst. The CO,
which cannot be removed by an
amine wash unit, will build up in
the treat gas, requiring a high purge
rate or another means of treat gas
purifcation. In the reactor effuent
train, liquid water and CO
2
may
form carbonic acid, which must be
handled properly to avoid increased
corrosion rates.
Before introducing
even minor amounts
of new feedstocks
into a diesel
hydrotreater, it is
important to know
the implications
topsoe.indd 1 10/3/10 12:22:42
When processing other feed
types, such as tall oil or vegetable
oils with a high content of free fatty
acids, severe corrosion of pipes and
other equipment upstream of the
reactor will take place, which is also
the case when processing high-TAN
fossil crudes.
Finally, the main products from
this process are normal paraffns
with high cloud and pour points,
and they may be problematic in
harsh climates. However, in contrast
to the FAMEs, the n-alkanes
produced can be transformed into
iso-alkanes with excellent cold fow
properties in dewaxing refnery
processes without compromising
other improved properties of the
diesel product. Such iso-dewaxing
may take place over a base-metal
sulphidic catalyst with high diesel
yields and be controlled separately
to provide different grades of prod-
uct quality, such as summer and
winter diesel fuels.
These challenges impose restric-
tions on current industrial practice
involving the hydrotreatment of a
feed comprising oil and renewable
organic material with respect to
how much of the organic material
can be used in the process, normally
below 5 vol%. In order to achieve
better economy in the co-processing
scheme, it would be desirable to
increase the proportion of renewa-
ble organic material in the feed up
to 25 vol% or more.
In this article, the fundamental
reactions taking place when
processing renewable feeds are
investigated and resolved in detail.
Based on this information, special
catalyst formulations have been
developed and are currently
running in industrial operation.
These are designed to have a high
activity and stability under the
harsh conditions prevailing in this
operation. Finally, we will describe
how process innovations have led
to a new technology that mitigates
the challenges mentioned above
and enables Preem to co-process up
to 30% tall oil-derived material in a
revamped hydrotreating unit.
Reaction pathways in renewable
diesel hydroprocessing
The industrial goal of hydrogenat-
ing biologically derived (renewable)
feedstocks is to produce hydrocar-
bon molecules with boiling points
in the diesel range, which are
directly compatible with existing
fossil-based diesel and meet all
current legislative specifcations.
With the introduction of feedstocks
stemming from renewable sources,
new types of molecules with a
signifcant content of oxygen are
present and must be treated prop-
erly by both the hydrotreating
process and catalysts. In order to
ensure trouble-free operation, it is
imperative to understand and
control the new types of reactions
that occur when higher levels of
oxygenates are processed. Overall,
the reactions can be characterised
as a (hydro-)deoxygenation, which
is to say production of a liquid
product with no oxygen. However,
several reaction pathways exist, and
other reactions such as the satura-
tion of double bonds and reactions
involving CO and CO
2
complicate
the picture. Thus, a fundamental
knowledge of the detailed reaction
chemistry is needed for catalyst
design and evaluation of process
design.
Although many different types of
renewable feeds exist, the chemistry
of hydrotreating vegetable oil or
animal fat to produce diesel-type
molecules is somewhat simplifed
by the fact that most such feed-
stocks, almost independent of seed
type, are supplied as so-called
triglycerides (triacylglycerols), an
example of which is shown in
Figure 1. Triglycerides can be seen
as the condensation of glycerol
(which may be seen as the C
3
back-
bone of the molecule) and three
carboxylic acids (also termed fatty
acids). Although the triglyceride
form is common to almost all oils
and fats, the chain lengths and
degree of unsaturation vary signif-
cantly. This affects product
properties and hydrogen consump-
tion. Vegetable oils and animal fats
may also contain signifcant
amounts of impurities, such as
alkalis and phosphorus, that need
to be removed either in a separate
process or through carefully
designed guard beds. Notably, the
content of sulphur and nitrogen
species is very low in these feed-
stocks, and therefore the required
hydrosulphurisation (HDS) conver-
sion is lower when co-processing
renewable feeds.
Acids and bases may catalyse the
transesterifcation of triglycerides,
where the three fatty acids are
converted into the corresponding
esters. This is the basis for the
production of FAME-type biodiesel,
which is a process in competition
with hydrotreating triglycerides to
form paraffns.
To investigate how the trig-
lycerides react under typical
hydroprocessing conditions, a pilot
plant test with a NiMo catalyst
O
O
16:0 Palmitic acid
O
O
9c18:1 Oleic acid
O
O
9c12c18:2 Linoleic acid
Figure 1 Example of triglyceride structure
A fundamental
knowledge of the
detailed reaction
chemistry is needed
for catalyst design
and evaluation of
process design
topsoe.indd 2 10/3/10 12:22:59
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was conducted using a blend of 75
vol% Middle East SR LGO and 25%
rapeseed oil. Rapeseed oil is a trig-
lyceride of fatty acids, mainly C
18

acids and varying amounts of the
monounsaturated C
22
erucic acid. In
this case, the C
22
constituted about
22 wt%, and the average degree
of unsaturation was four double
bonds/mole.
At conditions of 350C, 45 barg,
LHSV = 1.5 h
-1
and a hydrogen-to-
oil ratio of 500 Nl/l, the gaseous
and liquid products were analysed,
and yields and hydrogen consump-
tion were calculated. The conversion
of triglycerides was confrmed to be
100% by monitoring the yield of
propane, since one mole of propane
is produced for each mole of trig-
lyceride. (The C
3
backbone of the
triglyceride will be hydrogenated to
propane.) Furthermore, yields of
CO (0.6 wt%), CO
2
(1.2 wt%) and
CH
4
(0.1 wt%) were observed. The
total liquid product was analysed
by gas chromatography, and the
results are shown in Figure 2.
The chromatographs in Figure 2
show that the high-boiling rapeseed
oil feed is not present in the prod-
uct, and instead four normal
paraffns are formed with chain
lengths of 17, 18, 21 and 22, respec-
tively. No other liquid products are
formed in any appreciable amounts.
This product distribution can be
explained by the different mecha-
nisms by which the triglycerides
may react.
Once the fast double-bond hydro-
genation reactions have saturated
the fatty acids, the connection
between fatty acids and the C
3
back-
bone may be broken by one of at
least two distinct reaction pathways
(see Figure 3). The frst pathway
involves a complete hydrogenation
to form six moles of water, one
mole of propane and three moles of
normal paraffns with the same
chain length as the fatty acid chains
(n-C
18
and n-C
22
in the case of rape-
seed oil) per mole of reacted
triglyceride. This pathway is usually
termed hydrodeoxygenation, or
simply the HDO pathway. The
other pathway involves a decarbox-
ylation step, where three moles of
CO
2
, one mole of propane and three
moles of normal paraffns with a
chain length that is one carbon-
atom shorter than the fatty acid
chains (n-C
17
and n-C
21
in the case
of rapeseed oil) are produced. Since
the paraffns produced are in the
diesel boiling range, this is the
reason why the diesel hydrotreater
is the unit of choice for processing
such feeds.
As both CO
2
and CO are
produced, two additional reactions
need to be taken into consideration,
which are also shown in Figure 3.
Hydrotreating catalysts are known
to be active for both reverse water
gas shift (CO
2
+ H
2
CO + H
2
O)
and methanation (CO + 3H
2
CH
4

+ H
2
O). The relative extent of these
two reactions accounts for the
observed distribution between CO,
CO
2
and CH
4
. The water gas shift
activity of the catalyst makes it
diffcult to ascertain whether the
observed CO and CO
2
are produced
by a decarboxylation reaction as
described above or by a similar
decarbonylation route as proposed
in the open literature.
The relative usage of the decar-
boxylation and HDO reaction routes
is of major importance for the
hydrotreating process, as this infu-
ences hydrogen consumption,
product yields, catalyst inhibition,
treat gas composition and heat
balance. If all triglycerides react by
the decarboxylation route, seven
moles of hydrogen will be
consumed as opposed to the 16
moles of hydrogen consumed when
all triglycerides are converted via
the HDO route; in other words,
63% lower hydrogen consumption.
However, if all the CO
2
produced is
shifted to CO, and all the CO
formed is subsequently converted
into CH
4
, a total of 19 moles of
hydrogen will be consumed by the
R eten tio n tim e, m in
5 1 0 1 5 20 25 30 35 40 45
G
C

F
I
D

s
i
g
n
a
l
,

a
.
u
.
Figure 2 Simulated distillation chromatogram of feed (top) and product (bottom) from
pilot plant testing of 25% rapeseed oil co-processing. All rapeseed oil is converted into
normal paraffns with chain lengths of 17, 18, 21 and 22, respectively
R eten tio n tim e, m in
n C
1 7
n C
1 7
n C
1 8
n C
21
n C
22
n C
1 7
+n C
1 8
5 1 0 1 5 20 25 30 35 40 45
G
C

F
I
D

s
i
g
n
a
l
,

a
.
u
.
= 64%
n C
21
n C
21
+n C
22
= 63%
topsoe.indd 3 10/3/10 12:23:16
even and odd normal paraffns (see
Figure 2), it was found that the
molar conversion of CO
2
by water-
gas-shift was 5060%, and that
around 30% CO was converted to
methane. This means hydrogen
consumption by the decarboxyla-
tion route is roughly 11 mole/mole,
and thus hydrogen consumption is
closer to that of the HDO route.
Since the yield of high-value liquid
diesel molecules will be roughly
17/18 (94%) of that obtained by the
HDO route, and the occurrence of
CO and CO
2
in the recycle gas
poses a series of processing chal-
lenges, it is not straightforward to
determine which route is optimum,
as this will depend on the operating
conditions, the fow sheet and the
catalyst employed in the hydrot-
reater. Furthermore, the overall
refnery confguration as well as the
local prices of hydrogen and diesel
product will infuence the preferred
reaction route.
The characteristics of the renewa-
ble diesel directly refect the high
amounts of n-paraffns in the prod-
uct. This has the benefcial effect of
a lower specifc gravity and higher
cetane index, which are both prop-
erties that add to the value to the
product. On the other hand, normal
paraffns have quite high melting
points (n-C
18
: 28C), and therefore
the product is observed to have a
higher cloud point than a corre-
sponding product from the pure
LGO when co-processing rapeseed
oil. The NiMo catalyst used in the
test is virtually non-acidic, and
therefore no or very little isomerisa-
tion to iso-paraffns was expected.
Depending on the amount of co-
processed rapeseed oil, the high
cloud point may require a dewax-
ing step to meet specifcations.
Fundamental study of reaction
mechanisms
Understanding and controlling
selectivity by using the described
reaction routes is a key to the
decarboxylation route, meaning
19% higher hydrogen consumption.
In this pilot plant test, the split
between decarboxylation and HDO
was about 65/35. This can be found,
for instance, by analysing the rela-
tive rates of n-C
17
and n-C
18
, as
shown in Figure 2. This ratio varies
with type of catalyst, operating
conditions and type of renewable
feed. From the present experiment,
the hydrogen consumption related
to pure rapeseed oil conversion was
calculated to be about 280 Nm
3
/m
3
.
This is very high compared with
conventional diesel hydrotreating,
but typical of renewable diesel
hydrotreating, and one of the
reasons why only small amounts of
these feeds are usually co-processed.
For 5% rapeseed oil co-processing,
the additional hydrogen consump-
tion will be about 14 Nm
3
/m
3
.
When combining the measured
hydrogen consumption with the
relative rate of decarboxylation
inferred from the distribution of
O
O
13c Erucic acid
Octadecane
Octadecane
Docosane
9c Oleic acid
Rapeseed oil
HDO pathway products
Heptadecane
Heptadecane
Henicosane
Decarboxylation pathway products
Reverse WGS
Methanation
Decarboxylation
HDO
+ 7H
2
CH
4
+ l6H
2
O
O
O
Propane
water
O
H H
water
O
H H
water
O
H H
water
O
H H
water
O
H H
water
Hydrogen water
water Methane
Carbon
monoxide
Carbon
monoxide
Carbon
monoxide
O
O O O
O
H H H H
O
+
Hydrogen
H H
Hydrogen
H H
Hydrogen
H H
+
H H
Carbon dioxide
Propane
O C O
Carbon dioxide
O C O
Carbon dioxide
O C O
+
+ -
+ -
+
H H
O
9c12c Linoleic acid
O
C
O C
Figure 3 Reaction pathways in hydrotreating of rapeseed oil
topsoe.indd 4 10/3/10 12:23:39
design of optimum catalysts for this
very demanding service. To eluci-
date the elemental steps of the
conversion process, a fundamental
study of the reaction mechanisms
was undertaken. Methyl laurate (n-
dodecanoate) was chosen in order
to model hydrotreating of normal
seed oils and animal fats, as this
molecule shares the main character-
istics (an ester bonded fatty acid) of
the naturally occurring triglycer-
ides. The tests were carried out in a
micro-reactor setup at conditions of
300C, 50 barg, a hydrogen-to-oil
ratio of 1250 Nl/l and varying
WHSV (in the range 10100 hr-1).
It was observed that all liquid
hydrocarbon products had 11 or 12
carbon atoms, and that the most
abundant ones were 1-dodecanol,
n-C
11
and n-C
12
and the correspond-
ing alkenes, but also smaller
amounts of 1-dodecanal and
dodecanoic acid were observed.
This product distribution verifes
the existence of the two routes
described above, in this case lead-
ing to n-C
11
and n-C
12
. The only
products associated with the decar-
boxylation route were C
11
alkenes
and alkanes, and no oxygenate
intermediates were detected.
However, the HDO route leading
to C
12
products appeared to proceed
by a more complicated mechanism,
as several intermediates were
detected. The frst step of a simple
reaction scheme would be a step-
wise hydrogenation of the
connecting oxygen in the ester,
forming an aldehyde, which is
hydrogenated to the alcohol and
then to the alkane, or possibly
water is split from the alcohol,
forming an alkene prior to the
alkane. This reaction route is indi-
cated by the dashed arrows in
Figure 4. This explanation is in
qualitative accordance with the
observed intermediates, but the
proportions in which they are
formed called for further investiga-
tions of this hypothesis.
As a very high alkene/alkane
ratio was observed far above equi-
librium, the hydrogenation of
alkene to alkane appears to be a
rate-limiting step, and thus the
preceding reactions must be in
quasi-equilibrium. However, the
only alcohol observed was
1-dodecanol and not 2-dodecanol or
any other alcohols as would have
been expected in this case.
Therefore, another reactive interme-
diate must be involved, and since
ketones are known to exist in equi-
librium with their enol form, a
simple conjecture would be that
such an enol (possibly in an
adsorbed state) is formed and reacts
further to form either the alkene or
the 1-alcohol. This new intermedi-
ate is shown in the shaded box in
Figure 4.
To corroborate that the enol inter-
mediate is a vital part of the
reaction scheme, further studies
with other model compounds were
carried out showing that simple
ketones react much faster than alco-
hols. The alcohol would only yield
the corresponding alkane and small
amounts of the alkene, whereas the
observed products from ketones
were large amounts of the corre-
sponding alcohols as well as alkenes
and alkanes. This shows that
ketones must react through a differ-
ent intermediate and not only
through the alcohol.
Another test was designed to
examine whether the possibility of
forming an enol intermediate has
implications for the reactivity. Thus,
the reactivities of a ketone with and
without hydrogen in the -position
was investigated (see Figure 5).
Without -hydrogen, the ketone
cannot isomerise into an enol, and
it was also observed that this
compound reacted much slower (by
as much as a factor of 10) and
formed quite different products.
For the compound shown to the left
in Figure 5, the corresponding alco-
hol, two 2,4-dimethylpentenes and
2,4-dimethylpentane were formed.
For the compound shown to the
right in Figure 5, only a trace
1 Dodecene
1 Dodecanol
Product from
HDO pathway
C H
4
+C O
2
C H
3
O H +
C H
3
+H
2
+H
2
+H
2
+H
2
+H
2
H
2
O
+H
2
H
2
O
H
2
O
C H
1 0
H
20
C
1 0
H
21
n C
1 1
H
24
H
H
O H
H O
C
1 0
H
21
C
1 0
H
21
O H
H H
H O H
H
C
1 0
H
21
C
1 0
H
21
n C
1 2
H
26
H H
H H
H
H O
H
H
+H
2
Product from
decarboxylation pathway
Dodecanal
+
Figure 4 Overall reaction scheme for methyl laurate deduced from a model compound study. The dashed arrows mark the reactions
found not to play a dominant role. Instead, a new enol intermediate (shaded box) is proposed
topsoe.indd 5 10/3/10 12:23:49
amount of the alcohol and at least
fve different isomers of C
9
alkanes
and alkenes resulting from methyl
shifting as well as small amounts of
cracked products were detected.
Several experiments thus gave a
clear indication of the fact that
direct catalytic hydrogenation of a
carbonyl group does not occur
during a reaction with hydrogen at
modest temperatures over a hydro-
treating catalyst. Furthermore, all
our results point towards the enol
form (when formation is possible)
being the reactive intermediate for
the carbonylic reactants.
The detailed mapping of the reac-
tion intermediates not only enables
rationalisation of the selectivities
observed in industrial operation,
but also gives clues as to how
the catalyst should be designed
to favour certain reactions. Further-
more, understanding how process
conditions affect the reactivity of
feed and intermediate compounds
makes it possible to design revamps
and new units at optimum condi-
tions tailored to the economy and
confguration of the refnery.
Catalyst technology
In the rational design of catalyst
systems for the processing of
renewable material, several factors
have to be taken into account. The
catalysts must be able to handle
rough conditions inside the reactor
caused by the formation of CO,
which inhibits desulphurisation,
and to handle increased hydrogen
consumption and fast reactions,
leading to a large temperature
increase in the top of the catalyst
bed. Furthermore, the problem of a
high content of n-paraffns in the
products, with resulting poor cold
fow properties, has to be
addressed.
Depending on the amount and
quality of the organic material
blended into the diesel feed pool, a
choice of catalyst that is not
designed or tailor-made to handle
co-processing may result in poor
desulphurisation, hydrogen starva-
tion and pressure drop build-up,
and the hydrotreated product may
not meet the required targets for
cold fow properties. The challenges
thus have to be evaluated carefully
when designing a catalyst solution
for a hydrotreater treating biofuel.
To overcome the problems
associated with processing of
biocomponents, Topse introduced
three new catalysts: TK-339 and
TK-341, which are both HDO cata-
lysts, and an iso-dewaxing catalyst
designated TK-928. Together with
our graded bed catalysts and our
conventional ultra-low sulphur
diesel (ULSD) catalysts, these prod-
ucts will extend the cycle length
and ensure that on-spec diesel fuel
is produced without operational
problems. These catalysts may be
employed in both co-processing
and standalone units
Pilot plant testing showed that
the use of existing hydrotreating
catalysts will only give a very
limited reaction control in the top
part of the hydroprocessing reactor.
As the reaction of vegetable and/or
animal oils with hydrogen is a
highly exothermic process that
consumes high amounts of hydro-
gen, the temperature may rise very
rapidly in the top of the reactor,
and the hydrogen partial pressure
may be very low at the active reac-
tion sites on the catalyst. These
conditions will lead to coke forma-
tion and catalyst plugging, and will
cause a high pressure drop as well
as increased deactivation rates of
the catalyst. Thus, there was an
urgent need for an improved cata-
lyst formulation that would enable
refners to convert the components
derived from renewable organic
material in the feedstock at the
same time as maintaining a low
pressure drop and a low catalyst
deactivation rate.
A programme began to develop
specialised catalysts that enable a
more gradual conversion of the
renewable feed, thereby extending
the effective reaction zone and at
Fast
O O
2, 4-dimethyl-3-pentanone
(with A-hydrogen can
be isomerised to enol form)
Slow
2, 2, 4, 4-tetramethyl-3-pentanone
(without A-hydrogen cannot
be isomerised to enol form)
Figure 5 A ketone without hydrogen in the -position is not able to isomerise into the
proposed enol intermediate. We observed a much lower reactivity of this ketone (shown
to the right) and a very different product distribution pattern
Co-processing of
bio feed begins
Start-up with
Topsoe bio-fuel
catalysts
R u n d ay
0.5
1 .0
1 .5
2.0
2.5
3.0
3.5
4.0
0.0
0 200 400 600 800 1 ,000 1 ,200 1 ,400 1 ,600 1 ,800
R
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a
c
t
o
r

p
r
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s
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u
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e

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Topse biofuel catalyst
topsoe.indd 6 10/3/10 12:23:58
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the same time incorporating func-
tions that suppress the formation of
carbonaceous deposits on the cata-
lyst. This cannot be done by simply
lowering the activity of the cata-
lysts, since this will cause the HDS
activity to drop in a co-processing
scheme, which will in turn reduce
unit capacity. Thus, a proper
balance between high stability and
high activity was needed, which
was obtained with the new HDO
catalysts TK-339 and TK-341. These
catalysts will, in combination with
a good grading design, ensure full
conversion of the biofeed without
compromising the cycle length.
To illustrate the importance of a
proper catalyst system, Figure 6
shows the pressure drop in an
industrial ULSD hydrotreater,
which after two years of operation
started to co-process a few per cent
of vegetable oil. The catalyst solu-
tion was originally designed for the
hydrotreating of a conventional
feed, and when the refner intro-
duced organic feed the pressure
drop began to increase. As a result
of this, the refner was limited as to
how much biofeed could be proc-
essed, and it was impossible to
continue the operation with the
biofeed. The refnery contacted
Topse and, after studing the feed
and the operating conditions, it
recommended replacing the upper
30% of the catalyst layer with an
alternative mixture of graded bed
products balanced with the HDO
catalyst TK-339. In this specifc case,
it was estimated that the existing
bulk catalyst would have suffcient
activity to meet the targeted cycle
length, but for other applications a
complete catalyst replacement
might be required.
When the next opportunity for a
shutdown of the hydrotreater arose,
the new catalyst system was
installed. As can be seen from
Figure 6, the pressure drop has
been quite stable since this date and
at the same very low level as before
the introduction of biofeed.
Carbon monoxide inhibition
In the co-processing test with rape-
seed oil, the observed HDS activity
was the same as in a corresponding
test with 100% light gas oil (LGO).
This is somewhat surprising, since
substantial amounts of CO and CO
2

were detected, which are known to
inhibit many catalytic reactions. In
particular, CO is known to be selec-
tively adsorbed on catalytic sites
and to block reactants from adsorb-
ing and reacting. As the product
gases are recycled in industrial
hydrotreating units, and CO is not
removed to any signifcant extent
by amine scrubbing, it is of great
interest to investigate how different
types of hydrotreating catalysts are
affected by CO in the treat gas.
Pilot plant tests were carried out
to investigate how the HDS and
hydrodenitrogenation (HDN) activi-
ties of CoMo-type and NiMo-type
catalysts respond to co-processing
with rapeseed oil (see Figure 7).
The relative volume activities were
calculated, taking the lower amount
of sulphur and nitrogen in the feed
into account. It is evident that
CoMo catalysts were severely
infuenced by the introduction of
rapeseed oil to the feed. Both HDS
and HDN activities were very low
compared with the case where pure
LGO was processed. In contrast to
this, the NiMo catalyst activity
was almost unchanged when co-
processing rapeseed oil. In order to
explain these results, a new set of
tests was conducted, using the pure
LGO as feed, but using a treat gas
consisting of 1% CO in 99% H
2

instead of 100% H
2
. As shown in
Figure 7, the effect of CO is very
similar to that of co-processing
rapeseed oil. For CoMo, the HDS/
HDN activity dropped signifcantly.
No or little effect was seen for
NiMo. It is important to stress that
the lower activities observed are
inhibition effects and not a perma-
nent deactivation. When the CO is
removed from the treat gas or the
rapeseed oil is removed from the
liquid feed, initial activity will be
restored.
These results showed that the
inhibition of catalyst activity when
20
40
60
80
l00
0
Pure LGO,
l00% H
2
Papeseed oil/LGO,
l5/85%, l00% H
2
Pure LGO,
l/99% CO/H
2
A
,

%
v
P
HDS
HDN
20
40
60
80
l00
0
Pure LGO,
l00% H
2
Papeseed oil/LGO,
l5/85%, l00% H
2
Pure LGO,
l/99% CO/H
2
A
,

%
v
P
HDS HDN
Figure 7 Inhibition effects of co-processing are mainly the result of CO formation. CoMo
catalysts are much more severely inhibited than NiMo catalysts
CO inhibition for CoMo-type catalyst
CO inhibition for NiMo-type catalyst
topsoe.indd 7 10/3/10 12:24:07
processing renewable feeds can be
explained by the formation of CO
in the hydrotreating reactor. It was
also shown that, in almost all cases,
NiMo catalysts are the preferred
choice for this type of operation.
Dewaxing catalysts
ULSD specifcations and cold fow
properties are more frequently seen
by refners as limiting parameters.
This is especially the case when
hydroprocessed renewable products
are blended into the diesel pool.
Generally, ULSD cold fow proper-
ties are adversely affected by the
concentration of waxy molecules,
which are the normal and slightly
branched paraffns in the gas oil.
The high melting point of the paraf-
fns in the upper ULSD boiling
range mainly dictates the cold fow
properties.
The common routes taken to
improve the cold fow properties of
diesel-range products are fraction-
ating/blending, the use of additives
and catalytic dewaxing.
The concentration of long-chain
paraffns may be reduced by lower-
ing the end boiling point of the
ULSD product. This may also be
done by removing the heavy end of
the feed (however, thereby reduc-
ing the potential diesel pool) or by
blending into low boiling gas oil;
i.e., high-value kerosene (however,
thereby adversely affecting other
properties such as cetane number).
Cold fow properties may be
improved by the addition of
tailored chemicals such as cloud
point depressants. This method is
effective in many cases; however,
for biofuels, it is necessary to add
these expensive chemicals in
relatively high concentrations.
Additionally, many chemicals only
have a signifcant effect on one of
the cold fow properties and do not
improve others, thus requiring the
addition of several different
chemicals.
Finally, a more attractive way of
effectively improving the cold fow
properties of diesel fuels is catalytic
hydrodewaxing. This improves cold
fow properties by selective isomer-
isation and hydrocracking of the
normal and slightly branched paraf-
fns. The hydrodewaxing catalyst is
highly zeolitic and either selectively
isomerises or cracks mainly the
normal paraffns, which have poor
cold fow properties. The dewaxing
catalyst only slightly affects other
compounds of the gas oil:
isoparaffns, naphthenes, aromatic
compounds, and so on. An inherent
property of all dewaxing-type cata-
lysts is the formation of some
lighter products from the heavier
feed components; mainly the forma-
tion of naphtha and some C
1
-C
4
gas.
Depending on the refnery layout,
these lighter products may,
however, make an appreciable
contribution to improved refnery
margins.
Different types of dewaxing cata-
lysts exist on the market. Catalysts
based on zeolite ZSM-5, possibly in
combination with a base metal, may
effectively lower the cloud point
with no or even negative hydrogen
consumption, but have the draw-
back of giving an olefnic product
with low stability. Furthermore, the
deactivation rates are often very
high for this type of catalyst, thus
requiring frequent regeneration,
and the catalyst does not have any
HDS activity.
Other types of catalysts are based
on noble metals. These types of
catalysts are very expensive and
very sensitive to organic nitrogen
and sulphur compounds, and thus
call for a separate stage in the high-
pressure loop and a separate
reactor.
Topse has developed TK-928 to
effectively solve the issues
connected with other types of
dewaxing catalysts. TK-928 is a
sulphidic catalyst supported on an
acidic carrier able to operate in a
sour environment. It has medium-
high HDS and HDN activity, so
reactor volume is not lost in terms
of desulphurisation capacity. The
hydrogenating activity of the cata-
lyst gives a slightly higher hydrogen
consumption, but this will translate
into improved product properties,
such as lower density and higher
cetane number.
One option is to load the dewax-
ing catalyst close to the outlet of the
C H
4
Decarboxylation
HDO
+2H
2
+5H
2
Methyl oleate
O
O
Octadecane
Heptadecane
HDO pathway products
Decarboxylation pathway products
Water
O
O C O
H H
Water
O
H H
M eth an e
C H
4
M eth an e
C arb o n d io xid e
Figure 8 Reaction pathways in hydrotreating RTD
A more attractive
way of effectively
improving the cold
fow properties
of diesel fuels
is catalytic
hydrodewaxing
topsoe.indd 8 10/3/10 12:24:15
reactor, thereby permitting the
dewaxing function to be switched
on/off by temperature control in
the last bed by use of quench gas
and reactor inlet temperature
control. To make use of the dewax-
ing catalyst during winter time
operation, the reactor temperatures
are increased. During summer time
operation, the amount of quench
gas injected before the last bed is
adjusted to operate the dewaxing
catalyst at lower temperatures, to
limit the activity of TK-928 and
the associated higher hydrogen
consumption and yield loss.
Revamp of mild hydrocracking unit
at Preem AB Gothenburg
Preem has formed a partnership
with Sunpine, a company produc-
ing raw tall diesel (RTD) based on
tall oil from Kraft paper mills in the
northern part of Sweden. Tall oil
mainly consists of resin acids and
free fatty acids as well as a number
of contaminants in smaller
concentrations. Through a transes-
terifcation process, the majority of
free fatty acids are converted to
FAMEs, while the resin acids are
left almost unconverted. In order to
transform this RTD into a renewa-
ble diesel, Preem contacted Topse,
which had previously revamped
some of the companys refnery
units in Gothenburg and Lysekil,
and supplied catalysts for these
units. The RTD differs from other
feedstocks used for renewable
diesel production in that it is non-
edible and thus does not negatively
affect the global food shortage or
food prices.
Preem was interested in revamp-
ing an existing mild hydrocracking
unit into a green hydrotreating unit,
where large quantities of RTD could
be co-processed together with LGO.
In brief, Preem requested that up to
30% RTD be co-processed with
LGO to produce a renewable diesel
meeting EN 590 specifcations. This
high fraction of tall oil-derived
material posed a serious challenge
regarding hydrogen consumption,
exotherm, catalyst selection and
corrosion both up- and downstream
of the reactor. Preem entered into a
development agreement with
Topse in order to revamp the mild
hydrocracking unit (MHC), with
the aim of producing green diesel
based on RTD. The basic engineer-
ing was recently concluded by
Topse, and the revamped unit was
expected to start up in 2010.
The chemistry for this feed type
is slightly different from that of the
triglycerides described earlier,
because the main constituents are
FAMEs. However, the two reaction
pathways are still the same (see
Figure 8), and the reverse water-
gas-shift and methanation reactions
also occur. The main difference
from processing triglycerides lies in
the fact that a high yield of meth-
ane is obtained instead of propane.
Handling high-TAN feed
Since the feed contained many
unconverted free fatty acids, as well
as resin acids, a major concern was
the feed handling and the mineral/
renewable feed blending system.
The high level of acids has the
negative effect of increasing corro-
sion in pipes, heat exchangers and
fred heaters upstream of the
hydrotreating reactor. So far, this
has imposed a limitation on the
industrial applicability of the attrac-
tive concept of hydrotreating
mixtures of conventional mineral
oil with signifcant proportions of
tall oil or tall oil-derived material.
To address this problem, a new
RTD feed system was invented by
Preem and Topse, such that
mixing with the mineral feed is
carried out in several stages. Part of
the RTD is introduced at an injec-
tion point after the fred heater and
prior to entering the reactor. In this
way, all existing process equipment
upstream of this injection point is
not affected. Another part of the
RTD feed is introduced between the
frst two beds of the reactor to
control the temperature profle, but
also to control the TAN and thereby
minimise corrosion. The fow
scheme is shown schematically in
Figure 9.
With the new injection system,
where RTD is only injected after the
fred heater and as a liquid quench
to the second reactor bed, exposure
of hardware to highly corrosive
RTD is very limited, and only
minor changes to material selection
are necessary. These changes have,
in fact, prepared the unit for future
operation with an even higher frac-
tion of RTD feed.
Another concern is the large
amount of heat released due to the
hydrogenation of the RTD. In order
to control the heat release, the effu-
ent from the frst catalytic bed in
the hydrotreating reactor is mixed
with fresh RTD feed, as described
above. In this way, quenching is
provided by the RTD. This means
H eat
exch an g er
Fired
h eater
LG O feed
R TD
Hot
separator
Hydrotreating
reactor with
4 catalyst beds
M ake -u p +
recycle H
2
To am in e u n it
Pro d u ct
Figure 9 Process fow diagram for the revamped unit at Preem Gothenburg
topsoe.indd 9 10/3/10 12:24:28
that more hydrogen can be used to
prevent coke formation and fouling,
thereby ultimately giving a higher
unit reliability and lower invest-
ment cost. Furthermore, injecting a
part of the RTD as liquid quench
provides a relatively higher hydro-
gen partial pressure upstream of
the reactor, preventing gum forma-
tion and corrosion.
The splitting of RTD into several
streams and delaying the mixing of
the mineral feed with renewable
organic material prior to hydrot-
reating thus serve several purposes.
One purpose is to eliminate the risk
of corrosion, particularly in
upstream equipment, and another
is to provide a liquid quench, which
makes it possible to control heat
release from the exothermic reac-
tions, thereby lengthening the
lifetime of the hydrotreating cata-
lysts to a signifcant degree.
Selection of catalyst
The selection of catalysts must be
carried out in accordance with proc-
ess modifcations and reaction
conditions. It is highly desirable to
control the temperature gradient in
each catalyst bed. However, as the
conversion of high amounts of RTD
constitutes a very fast reaction
consuming substantially higher
amounts of hydrogen than in the
case of conventional hydrotreating,
it is necessary to have specialised
catalysts for conversion of renewa-
ble material. The Topse TK-339
and TK-341 catalysts are especially
designed to cope with these reac-
tions and to resist the formation of
coke/gum. In addition to this, high-
activity Topse BRIM catalysts are
needed to ensure high HDS activity.
In the present case, Preem chose
a catalyst loading consisting of an
extended grading system, Topses
biofuel catalysts and a BRIM NiMo
catalyst. As the RTD is split
between the frst two beds, the risk
of catalyst fouling in the frst bed is
smaller, but in the second bed a
higher amount of grading and
biofuel catalyst is required. Pilot
plant tests in a semi-adiabatical
reactor using the same loading
used in the industrial unit showed
this confguration to be very stable
and able to operate for extended
periods without pressure drop
problems.
Handling of CH
4
, CO and CO
2
in
the recycle gas
We also designed modifcations to
the recycle gas loop to handle the
gases formed, in particular CO and
CO
2
. The CO
2
can, to a large extent,
be removed in a downstream amine
wash, but, to avoid build-up of CO
and CH
4
in the loop, a purge can be
established and a methanator
applied to remove CO from the
purge gas. If the purge gas is
simply burnt off, the methanator is
obviously not required, but if the
purge gas is recovered CO may
be an undesirable component.
Inhibition by CO is not a concern
when the right catalyst type is
selected. However, the Preem refn-
ery considered it necessary to
remove CO, since the purge gas is
used in another refnery unit where
CO would be a catalyst poison. The
existing purge gas recovery unit is
a cryogenic unit that cannot remove
CO.
In the methanator, CO reacts with
hydrogen to form methane:
CO + 3H
2
CH
4
+ H
2
O
This elimination of CO and CO
2

by means of a nickel-based metha-
nation catalyst is an innovative
solution based on experience in the
design of ammonia plants, where
methanation can be regarded as a
proven technology. Alternatively,
these components can be removed
by pressure swing absorption (PSA)
if the refner has spare capacity in
the PSA unit.
Another area of concern is the
CO
2
formed by the decarboxylation
reaction route, which in the pres-
ence of liquid water may form
carbonic acid downstream of the
reactor, where the risk of carbonic
corrosion in the air cooler and the
cold separator is high. Topse has
developed a simple solution to this
problem, which can be used in all
types of units processing feeds with
a high oxygen content.
Revamp overview
The new unit will produce diesel
with specifcations in accordance
with EN 590 based on 30 vol%
renewable organic material and
70 vol% mineral oil. The paraffn
content formed by the hydrogena-
tion of the RTD improves the cetane
index and lowers the density, but it
also worsens the cold fow proper-
ties of the product. Thus, the
blending of RTD is initially limited
to 30 vol% to ensure a suffciently
low cloud point. Presently, Preem
does not require a dewaxing proc-
ess, since the LGO has good cold
fow properties. Thus, a large quan-
tity of the RTD can be processed,
while still meeting cloud point
specifcations.
Compared with the current oper-
ating conditions of the MHC, the
unit will operate at a lower temper-
ature when revamped to green
diesel production, and the hydro-
gen consumption will be
signifcantly higher. As a result of
the exothermic HDO reactions, the
heater duty and fuel consumption
of the unit will be lower compared
with what is seen for normal HDS
mode. Thus, while co-processing
RTD and fossil LGO, an added
bonus will be desulphurisation of
the gas oil, which is accomplished
with less fuel consumption.
The process solutions make it
possible to increase the amount of
renewable feed to be processed. The
new feed injection system ensures
operation without any risk of corro-
sion, particularly of the upstream
equipment. At the same time, it is
possible to control heat release from
the exothermic reactions and extend
the lifetime of the hydrotreating
catalysts signifcantly. Catalysts are
tailored for the revamped unit
The selection of
catalysts must
be carried out
in accordance
with process
modifcations and
reaction conditions
topsoe.indd 10 10/3/10 12:24:37
design and ensure a high stability
while maintaining the required
HDS activity. The problems with
the formation of high amounts of
CO, CO
2
and CH
4
are mitigated
through a proper purging strategy,
methanation of the purge gas and
by solving the carbonic acid corro-
sion issue. The revamp solution
ensures that the unit is very fexible
in terms of feed type. The new
process design also allows for the
processing of animal fat, oil from
algae, jatropha oils, used oils or
other triglyceride feedstocks that
may be available in the future.
Conclusions
Hydrotreating renewable diesel
offers a unique opportunity to
produce a sustainable diesel fuel
completely compatible with existing
fuel infrastructure and engine tech-
nology. The process is very versatile
in terms of feed type and thus
offers great potential for future
operation on algae oils or other
high-yield feedstocks that cannot be
used for human nutrition.
There are, however, numerous
challenges when hydrotreating
organically derived material,
including high hydrogen consump-
tion and large exotherms across the
catalyst beds, which must be faced
to avoid catalyst deactivation and
fouling. Topse has developed
speciality catalysts for biofuel oper-
ation, which ensure low deactivation
rates and high stability towards
fouling. These catalysts may be
combined with BRIM catalyst to
ensure that ULSD is produced, and
with TK-928, which gives an isode-
waxing activity to obtain suffciently
low cloud points.
Hydrotreating of biofuels also
requires novel technology solutions
that take the new reactions and new
products into account. The process
design developed by Topse makes
it possible to run with high amounts
of renewable feed and ensures a
high unit reliability and low invest-
ment cost. In addition to the new
feed inlet and liquid quench system,
solutions were developed to miti-
gate all issues related to large
quantities of gases, including CO
2
and CO, that might inhibit the cata-
lyst activity and be built up in the
loop unless removed. Furthermore,
potential corrosion problems caused
by high-TAN components in the
feed and carbonic acid downstream
of the reactor were addressed to
ensure successful operation of the
hydroprocessing unit.
Rasmus Egeberg is R&D Project Manager for
Distillate Hydrotreating with Haldor Topse,
Lyngby, Denmark. He has a masters degree
from the University of Copenhagen and a
doctorate from the Technical University of
Denmark. Email: rce@topsoe.dk
Niels Hygaard Michaelsen is Sales Manager
in the Refnery Technology sales group at
Haldor Topse, Lyngby, Denmark. He has a
masters degree in chemical engineering.
Email: nhm@topsoe.dk
Lars Skyum is Marketing Manager for Distillate
Hydrotreating Catalysts at Haldor Topse,
Lyngby, Denmark. He has a masters degree
in chemical engineering from the Technical
University in Copenhagen, Denmark.
Email: lks@topsoe.dk
Per Zeuthen is Marketing Manager for
Hydrocracking and FCC Pretreatment
Catalysts at Haldor Topse, Lyngby, Denmark.
He has a masters degree in chemistry from the
University of Odense, Denmark.
Email: pz@topsoe.dk
www.ptqenquiry.com
topsoe.indd 11 10/3/10 12:24:48
8
th
Asia Petrochemicals Strategy
& Technology Conference
Euro PetroleumConsultants
20 & 21 May, Parkroyal Hotel, Kuala Lumpur
APTC 2010
Euro PetroleumConsultants
BBTC 2010
4
th
Asia Bottom of the Barrel
Technology Conference
18 & 19 May, Parkroyal Hotel, Kuala Lumpur
Now entering its fourth successful year, Asia BBTC is established as the
only event capable of bringing you up to date with the latest economic
and technology developments for upgrading crude oil residues including
the modernisation of existing facilities, new equipment and catalyst
innovations.
With its expert speaker panel and unrivalled networking opportunities
with key regional refinery management, Asia BBTC has become the
industry standard for excellence and is the must-attend resid upgrading
event for your calendar.
SPeCiAl rATeS for All refinery & PeTroChemiCAl PlAnT PerSonnel!
regiSTer at www.euroPetro.com, Tel: +44(0)20 7357 83964, email: conferences@europetro.com
Key SPeAKerS inClude:
M Radzif A Kadir,
Lube Base Oil Specialist,
MELAKA REFINERY
PETRONAS
Dr Maizar Rahman,
Commissioner,
PERTAMINA
Marcos Benicio Pompa Antunes,
Executive Director,
NANSEI SEKIYU K.K. /
PETROBRAS
Key highlighTS:
New Decade - New Challenges? Outlook for the Asian Refning
Industry
How to Select the Most Benefcial Technology for Residue Upgrading
Latest Catalysts and Technologies for Resid Upgrading
Cost-Saving Hydroprocessing Technologies & Equipment Innovations
Operator Presentations by Petronas Melaka Refnery, Pertamina,
BP Kwinana and Petrobras
Refinery-Petrochemical integration will be high on the agenda at APTC:
benefits and opportunities will be discussed and case studies from recent
projects in Korea, Middle East and Europe will be presented.
Leading solution providers and technology companies will present on their
latest cost-effective strategies and products, and we will hear positive
updates on new and ongoing petrochemical projects.
Join us in Kuala Lumpur to meet with the leading players in the Asian
petrochemical industry, be updated on the latest market issues and gain
an insight into how to maintain and improve the future of your business.
Key SPeAKerS inClude:
Byeong-Jae Park,
General Manager,
SK ENERGY
Ahmed Al-Emadi,
General Manager,
QATAR CHEMICAL
COMPANY
Thevarak Rochanapruk,
Vice President & Project Director,
PTT PHENOL
Key highlighTS:
Competitiveness in Petrochemicals in Uncertain Economic Times
Focus on Refnery-Petrochemical Integration - Practical Examples
Case Studies from SK Energy, RAFO, PTT Phenol, Shell MEG Plant at
SEPC, Q-Chem
Outlook and Technologies for Aromatics, Olefns and Polyolefns
Maximising Petrochemical Assets. Optimisation Strategies
epc.indd 1 9/3/10 14:46:44
Selecting technologies for onshore
LNG production
T
his article discusses the avail-
able process technology
options for onshore liquefed
natural gas (LNG) production
plants, including their limitations
and opportunities for integration in
order to achieve the right fow
scheme that takes advantage of
each technologys strength while
maximising integration to minimise
capital and operating costs.
A typical scheme for most gas
processing plants designed to
produce LNG from a sour gas feed
is shown in Figure 1. Field produc-
tion, upon arrival at the processing
plant, is processed in a slug catcher,
which captures liquid and then
allows it to fow into downstream
equipment and facilities at a rate at
which the liquid can be handled
properly. Gas from the outlet of the
slug catcher is directed to a high-
pressure (HP) separator, where fnal
separation of liquid from the gas
takes place. These liquids are stabi-
lised and then stored before sale on
the condensates market. The light
components stripped in the stabili-
sation column are recompressed
and mixed with the gas from the
slug catcher. The aim is to liquefy
the resulting raw gas in the down-
stream process.
The HP raw gas fows through to
the gas sweetening unit (GSU), in
which acidic components including
H
2
S and CO
2
are removed by means
of chemical solvents. Simultaneous
carbonyl sulphide (COS) removal in
the GSU is also desired, as it facili-
tates the downstream processing
and purifcation steps, and contrib-
utes to the reduction of the total
sulphur content of the treated gas.
The enriched acid gas from the GSU
For optimal design of LNG production plants, selection of the individual units
must be made on the basis of an integrated approach
Saeid MokhaTab
Tehran Raymand Consulting Engineers
is processed to produce elemental
sulphur in a sulphur recovery unit
(SRU), consisting of a Claus unit
and an associated tail gas treating
unit (TGTU) if higher recovery rates
are specifed for the SRU itself. The
fnal residual gas from the TGTU is
incinerated.
The treated sweet gas is then
dehydrated on molecular sieves to
achieve 1 ppmv water, to ensure
safe processing and transmission,
and then purifed on a mercury
guard bed to limit the mercury
content to nanogram levels (10 ng/
Nm
3
) and prevent any corrosion
problems in the cryogenic section.
Mercury is conventionally removed
using non-regenerable activated
carbon or a regenerative mercury
removal sieve, like UOPs Hg Sieve.
The dry and mercury-free gas is
then cooled to about -35C, where
heavy components are liquefed.
The cooling temperature is set such
that the quantity of these heavy
ends, extracted as natural gas liquid
(NGL), is adjusted so that the
remaining gas composition complies
with the LNG specifcation. Ethane,
propane and butane are extracted
by fractionation for the refrigerant
make-up and for the LPG market.
The lean gas is condensed and sub-
cooled down to about -160C to
produce LNG.
Gas
sweetening
unit
Gas
dehydration
& mercaptans
removal unit
Sulphur recovery
unit + tail gas
treating unit
Mercury
removal
unit
Nitrogen
removal
unit
Fractionation
unit
Sour water
stripping unit
Water treating
unit
LPG Sulphur
Of gas to
atmosphere
Of gas
Raw gas
HP
separator
Feed pre-treatment
Condensate
stabilisation
unit
Slug
catcher
Pre-
cooling
Refrigeration
system
Liquefaction
LNG
N
2
-rich gas to
fuel gas system
Condensate
Figure 1 LNG production plant: sequence and requirements
mokhatab.indd 1 10/3/10 12:32:06
Generally, the LNG sales specif-
cation allows a maximum nitrogen
content of about 1% to control the
Wobbe Index of import LNG. The
nitrogen content of some existing
gas felds is above 1%; conse-
quently, the excess nitrogen has to
be removed and a dedicated nitro-
gen removal unit installed. The
resulting nitrogen-rich vapour is
compressed and fed into the fuel
gas system, while the remaining
liquid, at about -160C, is pumped
into LNG storage tanks before
export by dedicated LNG carriers.
Flashed vapours and boil-off gas
are recycled within the process.
Technologies for designing an
LNG plant
For a given gas composition, differ-
ent process confgurations are
available and the choice of technol-
ogies can be vast. The number of
technology units and how they are
integrated signifcantly impacts
overall project economics and
success. Therefore, for optimal
design of the LNG plant, process
selection of the individual units
must be made on the basis of an
integrated approach that considers
interactions between units. The best
practice to establish the optimum
treating line-up for an LNG produc-
tion plant should be critically
examined, taking all the process
and environmental limitations into
account within a fexible, operable
and economically justifed window.
Feed pretreatment section
In a typical scheme for an LNG
production plant (see Figure 1),
there are several pretreatment units
to meet the required specifcation of
the LNG product. The frst specif-
cations to be met are H
2
S removal
to <4 ppmv, CO
2
to 50 ppmv, total
sulphur <30 ppmv as S, water to
0.1 ppmv and mercury to levels of
10 ng/Nm
3
.
CO
2
and H
2
S in the feed gas
signifcantly impacts the thermal
effciency of any LNG liquefaction
process because of the energy
required to reduce these contami-
nants in the context of the energy
put into the entire process. In fact,
a feed stream with a high concen-
tration of CO
2
results in a lower
thermal effciency than one without.
The impact of H
2
S on thermal eff-
ciency is indirectly linked to the
CO
2
composition (Yates, 2002).
Therefore, key elements in selecting
the optimum process for the GSU
are the requirements for full or
selective removal of CO
2
and the
co-adsorption of hydrocarbons.
Such a unit could be operated
with an aqueous amine solvent or
mixed physical/chemical solvent.
From a sustained development
point of view, co-adsorption of
hydrocarbons has two unwanted
effects. First, it reduces the effec-
tiveness with which the feed gas is
used in the downstream process;
second, the combustion of hydro-
carbons in the SRU results in an
increase in CO
2
emissions. In the
amine treating option, the co-
adsorption effect is very low
because the solubility of aromatics
and heavy hydrocarbons in the
aqueous solvent is low. In the
mixed-solvent treating option, the
co-adsorption effect is much
stronger because of the physical
solvent element in the GSU solvent.
The second step in the treating
process is a MSU, which brings the
gas to the fnal specifcation for
water and mercaptans (RSH)
content. Removal of RSH in a MSU
necessitates treating the regenera-
tion gas containing RSH in a
separate treating unit. There is an
optimum between the amine-based
GSU and the MSU for mercaptan
removal. There are two options:
frst, mixed physical/chemical proc-
esses can be used to remove part or
all of the mercaptans from the feed
stream, and the MSU can be used
as a polishing step. The second
option is to use an aqueous amine
solvent, which removes some
mercaptans (say, 1015%), leaving
most of the mercaptan removal to
the MSU.
Importantly, the mechanism for
removal of mercaptans in the amine
solvents is similar for the hydrocar-
bons and mercaptans; thus, some
degree of co-adsorption of these
components cannot be avoided.
This optimisation should take into
account three main factors: operat-
ing fexibility over the feed gas
range, environmental performance
and cost effectiveness. The choice of
which process option is most suita-
ble depends on the feed gas
composition. If the mercaptan
content of the feed gas is high, use
of an aqueous solvent for the GSU
requires construction of a very large
MSU, which makes this option
uneconomic. However, if the
mercaptan content is less than
approximately 400500 ppm, both
processes offer advantages and
disadvantages.
Given the magnitude of the
investment in an LNG production
plant, it is appropriate to carry out
a rigorous treating process selection
study to identify the most cost-
effective and ft-for-purpose
treatment package that removes
contaminants in an environmentally
friendly way.
Mokhatab and Meyer
1
discuss
several integration aspects of the
main gas treating processes
involved. Among the alternatives,
fully integrated solutions have the
following advantages:
One licence contract, one overall
guarantee and liability, and one
licence fee
Tailor-made solution to avoid
multiplying internal design
margins, which can result in signif-
cant savings in capital and
operating costs
These integrated concepts use
proprietary know-how from lead-
ing technology licensors and
engineering contractors who take
the feed stream and deliver the
required end product in the best
possible way
The scope of engineering services
continues to detailed engineering,
as well as to assistance at commis-
sioning and start-up, and after-sales
services (technical assistance, train-
ing and revamp studies).
However, the results of an
economic analysis clearly indicate
which alternative is economically
the preferred choice.
Determining the best treating
package depends very much on the
initial feed gas conditions, the
treated gas specifcations and envi-
ronmental requirements. Before the
treating package is selected, it is
strongly recommended that an opti-
misation study is carried out to
mokhatab.indd 2 10/3/10 12:32:19
obtain the lowest capex/opex and
largest operating window with
respect to feed gas composition.
2
In
fact, the right technology, which
results in a cleaner environment,
improved reliability and higher
margins, has to be chosen on the
basis of the environment of each
individual project on a case-by-case
basis, addressing the drawbacks
and advantages of each option.
Selecting the correct technology and
tailoring the right process for a
given application also requires
extensive industrial experience and
the opportunity to choose among
various technologies and process
options.
The most important milestone in
the chain of an LNG project is the
go-no go, which entails fnancial
analysis. If the owner is a major
independent and the fnances are
not a barrier, selection of a process
will go ahead. When the project
needs external fnancing, the owner
takes the advice of a LNG consult-
ant, who recommends robust and
well-known process options to
diminish the operating risks of the
facility.
NGL recovery
Several decisions must be taken
fairly early in an LNG projects
development to defne the process.
First, should NGL be recovered in
the project? This is primarily a
function of feed gas composition
and the required product specifca-
tions in the destination LNG
market. Assuming that a project
supports NGL recovery, the next
question is: where should the NGL
be extracted? The choice is either at
the point of production or at the
receiving terminal. Removal of
NGLs during LNG vapourisation
takes advantage of the fact that the
NGL components are already in
liquid form and uses this condition
during the fractionation process.
Ross et al
3
discuss the advantages of
integrating the NGL recovery and
vapourisation functions into a
single integrated unit as compared
to installing segregated vapourisa-
tion and NGL recovery units.
The major NGL recovery options
involve cooling, absorption or
adsorption-based processes. How-
ever, cryogenic refrigeration is
generally the most technically
advanced type of NGL recovery
process used today. It combines
high recovery levels (typically full
recovery of all of the propane and
heavier NGLs and recovery of 50
90% of the ethane) with low capital
costs and easy operation.
4
This is
less attractive on very rich gas
streams or where the light NGL
product (C
2
and C
3
) is not marketa-
ble. For gases very rich in NGL,
simple refrigeration is probably the
best choice. The cryogenic NGL
recovery unit can also be adapted
to effciently co-produce LNG (often
as a batch process) with little or no
loss in NGL recovery. However, the
power consumption for producing
LNG is quite high compared to
traditional baseload LNG produc-
tion plants, and the processing
effciency of the NGL recovery unit
often drops signifcantly.
5
Within the liquids recovery
Adding value to the oil,
gas and petrochemical
industries?
Absolutely.
ABB Engineering Services as part of ABB G lobal C onsulting provides technical
services to improve performance in the areas of compliance, operations and
engineering. We offer expertise in the following areas: environmental services;
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reliability; pressure relief; process safety; project services and technical software.
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E-mail: contact@ gb. abb. com
PTQ Q2 2010 (125x178) Mar 10.indd 1 10/03/2010 09:45:45
www.ptqenquiry.com
mokhatab.indd 3 10/3/10 12:32:28
(DMR) process. While the PPMR
process dominates the industry,
there has been considerable diversi-
fcation of liquefaction processes in
the last fve to seven years.
Increased competition has led to
increased train capacity, improved
driver integration and decreased
capital costs. The PPMR process,
which is applied in all Shell-advised
LNG plants, was originally selected
as the basis for the liquefaction
design. This process is generally
accepted to be the most cost-
effective, reliable baseload LNG
process available. It covers nearly
90% of the total baseload LNG
capacity installed worldwide since
1972. OCLP utilises essentially pure
refrigerant components in an inte-
grated cascade arrangement and
offers high effciency and reliability.
The DMR process is selected on the
basis of highest plant effciency
and, accordingly, the highest
production capacity for given
mechanical driver power and the
lowest specifc cost.
9
Studies of the different liquefac-
tion processes suggest there is none
that is substantially more effcient
than the others. Rather, each tech-
nology can be competitive within a
certain range of train sizes. The
ultimate choice of process depends
on project-specifc variables and the
potential development state of
novel processes.
Note that technology selection
starts at an early stage in the life of
a baseload LNG project and is typi-
cally addressed at the feasibility
study and pre-FEED defnition
stages. Process routes must be
chosen for the process itself, utili-
ties and plant off-site units. These
include proprietary and non-
proprietary technologies. This also
applies to the upstream part of the
LNG chain, which supplies gas to
the plant. Potential options must be
identifed and evaluation criteria
established. Selection could be
decided between alternative
processing technologies for operat-
ing units, the type of major
equipment or utility schemes.
Integrating NGL recovery and LNG
liquefaction technology
It is common practice for NGL
extraction to stand alone from LNG
liquefaction facilities for various
commercial or geographical
reasons.
10
However, various confg-
urations of integrated NGL recovery
and LNG liquefaction units exist,
depending on the component
selected for recovery as well as the
desired recovery level. Successful
integration of NGL recovery into
the LNG value chain has a signif-
cant effect on both process design
and overall project proftability
11
,
where, through careful process
selection and heat integration, the
integrated technologies result in
lower specifc power consumption
and increased net present value
compared with separated
facilities.
12
Nitrogen removal
There are several methods available
to remove nitrogen before it enters
the LNG plant. There are also
numerous options within any given
LNG technology to remove nitro-
gen in the liquefaction process
itself. Rejection of nitrogen into the
fuel gas stream is a common way to
handle nitrogen.
13
When evaluating
the nitrogen rejection options for an
LNG technology, sensitivity cases
need to be performed for various
levels of nitrogen removal and the
overall LNG process impact. In fact,
selection of the nitrogen rejection
technology has implications for the
design of both upstream and down-
stream process facilities. Issues to
be considered are the impact on the
size of equipment and the piping
system.
For a high feed gas fow rate and
relatively high nitrogen content,
cryogenic processing is the only
real option for nitrogen rejection.
The alternatives of pressure swing
adsorption or membrane technolo-
gies, which are often used in
small-scale LNG production plants,
require excessive power to achieve
sales gas specifcation and therefore
have very high capital and operat-
ing costs.
14
The main cryogenic
cycle options for nitrogen rejection
are: single-column cycle, double-
column cycle and pre-separation
column cycle. However, the key
parameter for process selection
is essentially the nitrogen
section of the gas processing plant,
there are issues of operating cost
and operating fexibility that
directly affect the processing cost.
While the effciency of the selected
liquids recovery process is an
important factor in the processing
cost, the fexibility of operating the
process to either recover or reject
ethane without sacrifcing effciency
or propane recovery is often the
critical factor.
6
As the industry has
matured and demand for more eff-
cient ethane recovery has increased,
several designs have been
developed.
It should be noted that the type
of NGL process has a signifcant
effect on the level of pretreatment
required. It is therefore important
to consider all implications before
any process is selected. Choosing
the best NGL recovery process
requires consideration of a broad
range of factors. The main variables
that affect the choice of the best
process for a given application
include inlet conditions (gas pres-
sure, richness and contaminants),
downstream conditions (for
instance, residue gas pressure) and
overall conditions (such as utility
costs). In addition to the feed gas
composition and operation mode,
the most decisive technical charac-
teristics of any process are upstream
and downstream pressure, which
have a signifcant infuence on the
performance of the various technol-
ogies available.
7
Liquefaction section
A number of liquefaction processes
have been developed, their differ-
ences mainly arising in the types of
refrigeration cycles they employ.
Mokhatab and Economides
8
present
a critical overview of the LNG proc-
ess and an analysis of the main
methods available for the liquefac-
tion of natural gas in an onshore
LNG plant. They also discuss selec-
tion issues relating to the main
technologies that affect LNG plant
confguration. The most commonly
utilised LNG technologies for
onshore applications are: Phillips
Optimised Cascade LNG Process
(OCLP), APCI Propane Pre-cooled
Mixed Refrigerant (PPMR) process,
and Shell Dual Mixed Refrigerant
mokhatab.indd 4 10/3/10 12:32:51
content itself. Feed pressure, fow
rate, contaminant levels and
level of hydrocarbons available in
the nitrogen vent are also
important.
Conclusion
Optimisation of an LNG production
plant can only be achieved by
considering it as a single entity;
attempts to optimise individual
process units in isolation will result
in lost opportunities. For the opti-
mum fow scheme, the designer
must understand the available tech-
nology, opportunities for integration
and their limitations. Technical risk,
licensor experience, level of
commercialisation, safety, and
health and environmental aspects
all need to be weighed up along
with process and economic
performance. Other factors include
commercial arrangements, use of
proprietary technology and licens-
ing costs, technology availability in
certain countries or concerns about
intellectual property protection, and
client preferences.
References
1 Mokhatab S, Meyer P, Selecting Best
technologylineupfordesigninggasprocessing
units, GPA Europe Sour Gas Processing
Conference,Sitges,Spain,1315May2009.
2 KlinkenbijlJM,DillonML,HeymanEC,Gas
pre-treatmentandtheirimpactonliquefaction
processes, 78th Annual GPA Convention,
Nashville,TN,13Mar1999.
3 RossFP,WaltherST,CuellarKT,Advanced
technologies provide improved economics for
liquefed natural gas facilities, Hydrocarbon
Processing,87,1,6163,2008.
4 LeeRJ,YaoJ,ElliotD,Flexibility,effciency
to characterize gas-processing technologies,
Oil & Gas Journal,97,50,9094,1999.
5 CuellarKT,WilkinsonJD,HudsonHM,Pierce
M C, Co-producing LNG from cryogenic NGL
recovery plants, 81stAnnual GPA Convention,
Dallas,TX,12Mar2002.
6 Pitman R N, Hudson H M, Wilkinson J D,
CuellarKT,NextgenerationprocessesforNGL/
LPG recovery, 77th GPA Annual Convention,
Dallas,TX,16March1998.
7 MokhatabS,PoeWA,SpeightJG, Handbook
of Natural Gas Transmission & Processing, 1st
Ed,GulfProfessional,Burlington,MA,2006.
8 Mokhatab S, Economides M J, Onshore
LNGproductionprocessselection,SPEAnnual
Technical Conference and Exhibition, San
Antonio,TX,2427Sept2006.
9 Mokhatab S, Economides M J, Process
selectioniscriticaltoonshoreLNGeconomics,
World Oil,227,2,95-99,2006.
10 ElliotD,Qualls,WR,HuangSh,ChenJJ,Lee
RJ,YaoJ,ZhangY,BeneftsofintegratingNGL
extraction and LNG liquefaction technology,
AIChE Spring National Meeting, Atlanta, GA,
1014Apr2005.
11 BarclayM,YangCC,NGLRecoveryprocess
synergies with the LNG value chain, AIChE
Spring National Meeting, Orlando, FL, 2327
Apr2006.
12 Lee R J,Yao J, Chen J J, Elliot D, Enhanced
NGLrecoveryutilizingrefrigerationandrefux
fromLNGplants,USPatent6401486,11Jun
2002.
13 YatesD,Thermaleffciency-design,lifecycle,
and environmental considerations in LNG
plantdesign,GasTechConference,Doha,Qatar,
1316Oct2002.
14 GarcelJC,Liquefactionofnon-conventional
gases, GPAE Europe Conference, Ashford, UK,
1416May2008.
Saeid MokhatabisProcessTechnologyManager
forTehranRaymandConsultingEngineers,Iran.
Hehasbeeninvolvedasatechnicalconsultant
inseveralinternationalgasengineeringprojects
and has published more than 150 academic
andindustrypapersonrelatedtopics.
Email: saeid_mokhatab@hotmail.com
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Estimation of heat losses from process
piping and equipment
T
he most important part of the
energy management strategy
in any process industry is
energy saving. In this article, an
attempt has been made to formulate
a predictive tool that is easier to
apply than existing approaches, less
complicated with fewer computa-
tions, and suitable for refnery
process engineers, for the rapid
estimation of heat losses in terms of
wind velocity and the temperature
differences between process piping
and equipment surfaces and the
surrounding air.
The tool developed in this study
could be of immense practical value
for engineers and scientists to make
a quick check of heat losses to air in
contact with walls or surfaces with-
out the need for experimental
measurement. The results can be
used in follow-up calculations to
determine heat losses from process
piping and equipment surfaces
under various conditions. In partic-
ular, engineers should fnd the tool
to be user-friendly with transparent
calculations involving no complex
expressions.
Due to limited energy resources,
and environmental pollution arising
from the use of fuels, energy saving
has become mandatory.
1
In particu-
lar, industrial and chemical
processing plants contain intricate
and costly piping confgurations.
Piping systems are also employed
in many other situations, including
water supply, fre protection and
district cooling/heating applications.
2
Several rigorous studies have
been reported in the literature on
the combined effects of convection
and surface radiation. However,
there is no simple-to-use predictive
An accessible predictive tool calculates surface heat losses from refnery piping
and equipment
AlirezA BAhAdori and hAri B VuThAluru
Curtin University of Technology
tool for an accurate estimation of
combination convection and radia-
tion flm coeffcients for air in
contact with vertical walls or
surfaces to give the combined heat
transfer coeffcient in terms of
the wind velocity and the tempera-
ture difference between the process
piping and equipment surfaces and
the surrounding air for heat loss
calculations from various cases.
In view of this shortfall, our
efforts have been directed at formu-
lating a simple-to-use, predictive
tool that can serve practising engi-
neers and applied researchers. The
principal value of the proposed tool
lies in its accuracy and simplicity,
wherein the relevant coeffcients
can be retuned quickly if more data
are available in the future. The case
study presented here demonstrates
the usefulness of the proposed tool.
The present study discusses the
formulation of a simple correlation
that can be of signifcant impor-
tance for engineers.
development of a simple
predictive tool
Equation 1 calculates a coeffcient, ,
which is the difference in tempera-
ture between a surface and the
surrounding air, C:
T = T
s
-T
a
(1)
The data required to develop the
frst correlation include reliable
data
3
for various values of wind
velocity, and the temperature differ-
ence between the surface and the
surrounding air. The following
methodology has been applied to
develop the predictive tool.
1,2
First, combination convection and
radiation flm coeffcients for air in
surfaces (h
cr
) in W/(m.C) are corre-
lated as a function of the
temperature difference between the
surface and the surrounding air
values (T) in C for different wind
velocity values (v) in metres per
second. Then, the calculated coeff-
cients for these equations are
correlated as a function of wind
velocity values. The derived equa-
tions are applied to calculate new
coeffcients for equation 2 to predict
surfaces. Table 1 shows the tuned
coeffcients for Equations 3 to 6
according to the data.
3
In brief, the following steps are
repeated to tune the coeffcients of
Equations 1 and 2:
Correlate the combination
convection and radiation flm coef-
Coeffcient Value
A
1
2.18201771352
B
1
2.65054426648 x 10
-1
C
1
-1.895691067097 x 10
-2
D
1
4.641521705558 x 10
-4
A
2
6.616737105648 x 10
-3
B
2
-1.119534124965 x 10
-3
C
2
9.485846901915 x 10
-5
D
2
-2.43542487435 x 10
-6
A
3
-1.581032525858 x 10
-5
B
3
3.699760242622 x 10
-6
C
3
-3.222348926402 x 10
-7
D
3
8.774496064317 x 10
-9
A
4
2.1240407483723 x 10
-8
B
4
-5.7213183786357 x 10
-9
C
4
5.3052858118086 x 10
-10
D
4
-1.572916658647 x 10
-11
Tuned coeffcients used in
equations 3 to 6
Table 1
curtin.indd 1 10/3/10 13:53:48
fcients for air in contact with
vertical walls or surfaces as a func-
tion of the temperature difference
between the surface and the
surrounding air for a given wind
Repeat step 1 for other values of
wind velocity
Correlate corresponding polyno-
mial coeffcients, which are obtained
in the previous steps, against wind
velocity, so that we have: a = f(v),
b = f(v), c = f(v), d = f(v) (see
Equations 3 to 6).
Equation 2 presents a new corre-
lation in which four coeffcients are
used to correlate the combination
convection and radiation flm coef-
fcients for air in contact with
process piping and equipment
surfaces, and the temperature
difference between the surface and
the surrounding air values:
h
cr
= a + b(T) + c(T)
2
+ d(T)
3
(2)
Where:
a = A
1
+ B
1
v + C
1
v
2
+ D
1
v
3
(3)
b = A
2
+ B
2
v + C
2
v
2
+ D
2
v
3
(4)
c = A
3
+ B
3
v + C
3
v
2
+ D
3
v
3
(5)
d = A
4
+ B
4
v + C
4
v
2
+ D
4
v
3
(6)

The tuned coeffcients used in
Equations 3 to 6 are given in Table
1 and help to cover the reported
data with wind velocity variations
up to 20 m/s and temperature
gradients (the temperature of a
surface less the temperature of
surrounding air) up to 280C.
Equation 7 calculates heat losses
from equipment surfaces occur
primarily by radiation and
convection:
Q = h
cr
(A
o
) (T
s
- T
a
) (7)
Results
Figure 1 illustrates the results of a
proposed correlation for predicting
contact with walls or surfaces in
comparison with some typical data
obtained from the literature.
3
Figure
2 demonstrates the performance of
a proposed predictive tool for a
wide range of conditions. As can be
seen, the results of the new
proposed correlation are accurate
and acceptable. This graph also
demonstrates the performance of
the proposed correlation. A case
study is given below to demon-
strate the simplicity of the proposed
predictive tool for the estimation of
surfaces.
Case study
How much heat can be saved per
linear metre by covering a 200 mm
NPS Sch 40 steam header, carrying
100 kPa (ga) steam at 120C, with a
25 mm thick layer of block insula-
tion? Assume ambient conditions
are -1C with a 24 km/h wind. For
the insulated pipe, assume that the
outside surface of the insulation is
at 10C
Solution
Using Equations 2 to 6, the heat
loss from the bare pipe is:
a = 3.2440444304 (from equation 3)
b = 2.64750085877 x 10
-3
(from equation 4)
c = -2.8669570727 x 10
-6
(from equation 5)
d = 2.016839208 x 10
-9
(from equation 6)
h
cr
= 33.9874 W/(mC) (from equation 2)
D
o
= 0.219 m
T
w
= 120C
T
a
= -1C
L= 1m
Q = h
cr
(Ao) (T
w
- T
a
) = (33.2)(1)() (0.219) (120 -
(-1))= 2917 W/(per linear m) (from equation 7)
Temperature of surface less temperature of air, C
l0
l
l0
l
l0
2
d
n
a

n
o
i
t
c
e
v
n
o
c

d
e
n
i
b
m
o
c

r
o
f

t
n
e
i
c
f
f
i
e
o
C
)
C

,
r
e
t
e
m

e
r
a
u
q
s
(
/
w

,
n
o
i
t
a
i
d
a
r
wind velocity 5.555 m/s
wind velocity 0 m/s (still air)
wind velocity l3.888 m/s (still air)
wind velocity l9.444 m/s
Figure 1 Prediction of combination convection and radiation flm coeffcients for air in
contact with vertical walls or surfaces in comparison with some typical data
3
Temperature of surface less temperature of air, C
10
1
10
0
10
2
10
1
C
o
e
f
c
i
e
n
t

f
o
r

c
o
m
b
i
n
e
d

c
o
n
v
e
c
t
i
o
n

a
n
d
r
a
d
i
a
t
i
o
n
,

W
/
(
s
q
u
a
r
e

m
e
t
e
r
,

C
)
Wind velocity = 17 m/s
Wind velocity = 0 m/s (still air)
Figure 2 Performance of proposed predictive tool for estimation of combination
convection and radiation flm coeffcients for air in contact with vertical walls or surfaces
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curtin.indd 2 10/3/10 13:54:53
For the insulated pipe, assume
that the outside surface of the insu-
lation is at 10 C. Then:
a = 3.24404443 (from equation 3)
b = 2.647500858 x 10
-3
(from equation 4)
c = -2.86695707 x 10
-6
(from equation 5)
d = 2.016839208 x 10
-9
(from equation 6)
h
cr
= 26.3857 (from equation 2)
Q = 26.3857(1)() (0.219+2 x 0.025) [10 -(-
1)]= 245 W/(per linear m)
(from equation 7)
Heat saved = 2917 - 245 = 2672 W/m
Conclusions
An attempt has been made to
formulate a novel and simple-to-use
predictive tool for the prediction of
heat loss rate for air in contact with
the process piping and equipment
surfaces. This tool gives the
combined heat transfer coeffcient,
in terms of the wind velocity and
the temperature difference between
the surface and the surrounding air.
The results can be used in follow-
up design calculations to determine
heat losses from equipment surfaces
...and get access to over 1,500 technical articles on every aspect of
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under various conditions.
Mechanical and process engineers
should fnd the proposed tool to be
user-friendly, with transparent
calculations involving no complex
expressions.
Acknowledgement
The lead author acknowledges the Australian
Department of Education, Science and Training
for Endeavour International Postgraduate
Research Scholarship (EIPRS), the Offce of
Research & Development at Curtin University
of Technology, Perth, Western Australia, for
providing Curtin University Postgraduate
Research Scholarship and the State Government
of Western Australia for providing top-up
scholarship through Western Australian Energy
Research Alliance (WA:ERA).
Nomenclature
A, B, C and D: Coeffcients
A
o
: Outside area, m
2
D
o
: outside diameter, m
h
cr
: Combined convection and radiation heat
transfer coeffcient, (W/(mC))
Q: Heat loss, W/(linear metre)
T
s
: Surface temperature, C
T
a
: Surrounding air temperature, C
v: Wind velocity, m/s
T: Temperature difference between the
surface and the surrounding air, C.
References
1 Bahadori A, Vuthaluru H B, A simple method
for the estimation of thermal insulation
thickness, Applied Energy, 87, 2010, 613619.
2 Bahadori A, Vuthaluru H B, A simple
correlation for estimation of economic
thickness of thermal insulation for process
piping and equipment, Applied Thermal
Engineering, 30, 2010, 254259.
3 Gas Processors and Suppliers Association
Engineering Data book, GPSA, 2004, 12th
edition, Tulsa, OK.
Alireza Bahadori is a PhD Researcher in the
School of Chemical and Petroleum Engineering
at Curtin University of Technology, Perth,
Australia. Email: alireza.bahadori@postgrad.
curtin.edu.au
Hari B Vuthaluru is an Associate Professor
in the School of Chemical and Petroleum
Engineering at Curtin University of Technology,
Perth, Australia.
curtin.indd 3 10/3/10 13:55:07
Korean frms lead in Ruwais
Four Korean companies have been
awarded a combined $9.65 billion
to expand facilities at Ruwais refn-
ery in Abu Dhabi. ADNOC
subsidiary Takreer signed contracts
worth $3.6 billion with GS
Engineering and Construction on
two out of seven packages covering
proposed work at Ruwais.
GS will build a residue fuid cata-
lytic cracking plant. Worth $3.11
billion, it is the largest overseas
plant order ever won by a single
Korean builder. Another package,
worth $520 million, awarded to GS
involves constructing port facilities
for exporting and importing crude
oil and petroleum products from
the refnery complex.
Samsung Engineering has signed
a $2.73 billion deal, while Daewoo
Engineering and Construction has a
$1.17 billion contract to build a 76-
tank storage facility. SK Engineering
and Construction has a contract
worth $2.12 billion to build a crude
distillation unit and facilities nearby.
NPRA attacks low-carbon rules
The National Petrochemical and
Refners Association (NPRA) has
fled a legal challenge to low-carbon
legislation in California that could
prevent the use of crude oil
extracted from Canadian tar sands.
In a statement, the NPRA said that
the California Air Resources Boards
(CARB) Low Carbon Fuel Standard
(LCFS) was unlawful for several
reasons, including its effect on
interstate commerce.
In its statement the NPRA said
that Californias LCFS is unlawful
for a number of reasons, including
the fact that it violates the
Commerce Clause of the United
States Constitution by imposing
undue and unconstitutional
burdens on interstate commerce.
Californias LCFS also would have
little or no impact on GHG emis-
sions nationwide and would harm
the USs energy security by discour-
aging the use of Canadian crude oil
P
the nations largest source of
crude and ethanol produced in
the American Midwest. Discourag-
ing the use of North American
transportation fuel sources would
only create additional, unneeded
burdens for Californias consumers
and economy, increase reliance on
energy from less stable parts of the
world and weaken national
security.
The LCFS is an ineffective tool for
reducing GHG emissions, it contin-
ued. The fuel prohibited from use
in California will simply be used
elsewhere, which will result in
increasing overall GHG emissions
due to less stringent environmental
standards in places those fuels
would ultimately be consumed and
in increased GHG emissions due to
increased transportation distances.
The California LCFS is only one
element of a broader effort to
impose various low-carbon fuel
standards at the state, regional and
national levels, says the NPRA:
While each of these individual
proposals is beset with its own
unique complications and chal-
lenges, all of them share some of
the same fundamental shortcom-
ings. The widespread production,
distribution, and use of alternative
fuels that would be required under
any LCFS poses signifcant environ-
mental and technological challenges.
Further, any LCFS may either
simply be unachievable or bring
about signifcant negative impacts
on American consumers and on the
nations environment, food supply,
and energy security.
Revamps in Ukraine
Ukraines Ukrtatnafta has awarded
CRI/Criterion Catalyst Company
and Shell Global Solutions Eastern
Europe contracts to supply Shell
reactor internals and a Criterion
catalyst system for two production
units at its Kremenchug refnery.
The equipment and catalyst
system will be used in a revamp
of a diesel hydrotreater unit to
Industry News
enable hydrotreating of vacuum
gas oil. The revamped unit will
produce low-sulphur vacuum gas
oil. The aim of the project is to
increase output of product and to
achieve longer operation between
regenerations.
Criterion has also been contracted
by Ukrtatnafta to revamp a second
diesel hydrotreater. This will enable
Kremenchug refnery to produce
automotive diesel to Euro-3, as well
as batches of diesel to Euro-4
standard.
QP, Shell expand Asian alliance
Qatar Petroleum International (QPI)
and Shell will jointly invest in two
of the Anglo-Dutch companys
petrochemical joint ventures in
Singapore. A new joint venture
company called QPI & Shell
Petrochemicals (Singapore) will
hold 50% of Petrochemical
Corporation of Singapore and a
30% stake in The Polyolefns
Company. QPI and Shell will each
hold a 50% stake in QPI & Shell
Petrochemicals (Singapore).
The deal is the second collabora-
tion between Qatar and Shell in
Asias downstream sector. These
two organisations are also develop-
ing a refnery-petrochemical project
with PetroChina.
Petrochemical Corporation of
Singapore operates two steam
crackers that produce an annual
1.9 million tonnes of ethylene. A
Japanese consortium led by
Sumitomo Chemical holds a 50%
stake in PCS. The Polyolefn
Company produces an annual
260 000 tonnes of low-density
polyethylene and 600 000 tonnes of
polyproylene. Another Japanese
consortium also led by Sumitomo
Chemical holds 70% of TPC.
Shell Eastern Petroleum operates
a 500 000 bpd refnery on Pulau
Bukom. The company is building a
petrochemical complex comprising
an 800 000 tpy steam cracker and
two downstream units due to be
fully operational in Q1 2010. In
ind news copy 3.indd 1 10/3/10 13:00:18
its petrochemical plant in Yeosu,
South Korea. LG Chem will use the
SimulFlow technology to increase
throughput of feedstock, enabling it
to increase its current ethylene
production when the unit comes on
stream this year.
UOPs SimulFlow is a high-
capacity distillation device that
supports the fractionation of petro-
chemical and refnery process
streams. The device offers more
than 100% improvement in capacity
over conventional distillation trays,
says its developer, and can be used
to maximise the proftability and
operating effciency of existing
plants. SimulFlow can also be used
to reduce space requirements and
capital investments for onshore and
offshore applications.
Upgrade consultants
Refnera de Cartagena has
appointed a joint venture of Foster
Wheeler USA and Process
Consultants (also a Foster Wheeler
company) to serve as consultant for
the expansion of the Cartagena
refnery in Colombia. The project
will expand the refnerys capacity
from 80 000165 000 bpd. It will
also improve the fuel quality to
meet Colombian and international
environmental specifcations. The
upgraded facility will produce
ultra-low sulphur gasoline and
diesel from a heavy crude oil slate.
Overall investment for the upgrade
project is more than $3 billion.
Refning report: a high-
investment, low-return future
According to an analysis and
report* from Dublin-based Research
and Markets, national oil compa-
nies will provide the impetus for
global refning capacity growth in
the next fve years. Global refning
capacity is expected to grow from
4513 million t/y at the end of 2009
to 5395.1 million t/y in 2015 at an
annual growth rate of 2.98%,
compared to 1.56% growth between
2000 and 2009. However, the report
estimates the global refning capac-
ity cushion (spare refning capacity)
will remain low over the next fve
years. Spare capacity, as high as
25% in the early 1980s, declined to
1011% in 20072008. Amid delays
Qatar, Shell and Qatar Petroleum
are building the Pearl gas-to-liquids
plant scheduled for completion by
the end of 2010. The $18 billion
project, the worlds largest to turn
natural gas into transportation
fuels, is entirely funded by Shell,
which will share revenue from its
output with Qatar.
Meter testing in the loop
The worlds largest calibration facil-
ity for oil and gas meters has
opened in The Netherlands. NMis
EuroLoop is being touted as a major
step forward with respect to the
accuracy of measuring large liquid
and gas fows.
According to NMi, no other facil-
ity in the world can assess and
calibrate industrial oil and gas
meters with such a low level of
measurement uncertainty. The
meters concerned are up to 30 inch
in diameter and are built into the
international trunk network for oil
and gas. Meters from around the
world will be shipped to EuroLoop
to be calibrated.
The loops construction enables
very large volumes of gas to be
reused repeatedly, so the new facil-
ity does not depend on the
consumption of gas, which is the
case with the current facility. In
addition to the low level of
measurement uncertainty, this
allows NMi to offer its clients a
faster service.
The EuroLoop facility includes
two large gasholders, each with a
capacity of 3500 m
3
. When a meter
is being installed or removed from
the system, or during low-pressure
testing, the excess gas is stored
temporarily in the holders. As a
result, it is unnecessary to fare off
gas. The temperature is an impor-
tant variable when taking gas and
oil measurements. Therefore ultra-
sound is used in the oil circuits to
continually monitor the tempera-
ture. The results obtained by fuid
meters are likewise dependent on
viscosity, so EuroLoop enables three
different viscosities to be tested.

Stepping up ethylene production
LG Chem has selected UOP distilla-
tion and mass transfer equipment
to increase ethylene production at
and cancellations of planned proj-
ects, the global refning capacity
cushion is expected to be around
13% by 2015.
Although the global refning
industry had started witnessing
higher returns since 2004, the
economic downturn since mid-2008
has transformed it back to its tradi-
tional model of a high-investment,
low-return business. As the demand
for products such as gasoline and
naphtha are unlikely to recover in
the coming years, global refning
margins will remain in the range of
$57/barrel and be sustained
mainly by middle distillates, which
will have steady demand.
Worldwide, growing environmen-
tal concerns have resulted in the
enactment of strict regulatory
frameworks and emission norms.
Demand for petroleum products
across all major markets has also
shifted towards lighter and cleaner
products. Demand for cleaner prod-
ucts mandates a reduction in the
sulphur content of products, apart
from improving other quality
parameters. Such requirements call
for heavy investments in refneries
to install adequate conversion and
desulphurisation facilities.
*The Future Of The Global Refning Industry to 2015
Benefting From National Oil Companies Growth
Wheat refner starts production
Europes largest wheat-based biore-
fnery has sold its frst cargo of
bioethanol. Annual production from
the new 250 million Ensus biore-
fnery on Teesside, England, is
expected to meet about a third of
the UK requirement for bioethanol
under the UKs Renewable
Transport Fuel Obligation, which
requires 3.5% of all transport fuel to
be biofuels in 201011.
The saving in carbon emissions
will be equivalent to taking 300 000
cars off the road. The plant will also
produce 350 000 tonnes a year of
high-protein animal feed, replacing
imports. The refnery takes animal
feed wheat, of which the UK has a
large surplus, and refnes it into
bioethanol and high-protein animal
feed. At the same time, the refnery
is capturing all the CO
2
it produces
for use in the food and drinks
industries.
ind news copy 3.indd 2 10/3/10 13:00:34
Researched and Produced by:
17th - 19th May 2010
Beurs - WTC Congress Center, Rotterdam, The Netherlands
Specialist Planning Manager, KNPC
I waslucky to attend thiswell
organised and varied summit.
It certainly added to my
knowledge and broadened my
knowledge spectrum.
2010 SPeaKerS INClude:

Dariusz Jacek Krawiec, President and CEO,
PKN Orlen S.A.
Dariusz focuses upon recovery from t he economic
downt urn and t he fut ure out look of t he refnery
indust ry.
Jean Jacques Mosconi, Senior Vice
President of Strategy, Total.
Jean discovers t he lat est t rends in global refning
as well as comparing how compet it ive mat ure
market s such as Europe and Nort h America are
against emerging dynamic market s.
Steve Welch, Chief Operating Of cer, US
R&M and Global Petrochemicals, BP.
St eve ident ifes t he lat est development s in refning
operat ions and st rat egy.
Jarmo Honkamaa, Deputy CEO &
Executive Vice President of Renewable
Fuels, Neste Oil.
Jarmo invest igat es t he current and fut ure role of
biofuels.
Mutlaq Al Azmi, Operations Manager,
Shuaiba refnery, Kuwait National
Petroleum Company.
Mut laq reveals operat ional excellence at t he
Shuaiba Refnery.
Dr Frigyes Lestak, General Manager, CO2
E ciency Shell.
Dr Frigyes Lest ak examines carbon ef ciency and
management st rat egies.
2010 SPONSOrS INClude:
2010 PlaTINIuM MedIa
ParTNerS INClude:
TO regISTer, contact richard Jones:
Email: richard.jones@wtgevents.com
Call: +44 (0) 20 7202 7690 - Fax: +44 (0) 20 7202 7600
Visit: www. ref ningsummit.com - Quote booking code: PTQ
IMPROVING
OPERATIONAL
PERFORMANCE
TO SECURE
FUTURE
PROFITABILITY
www.ref ningsummit.com
In association
with:
global summit.indd 1 9/3/10 14:50:12
Video leak detector
Siemens Industry Solutions Division
has developed video-based software
that detects plant leaks. ViaCC
enables the recognition of smoke,
fumes, leaking liquids and colours.
It contains detection methods that
can be combined and that are suit-
able for detecting edges, colours,
movements and so on. Up to 12
cameras record and transmit about
200 images per second to each
server. ViaCC can be integrated into
a range of automation systems,
such as T2000/3000 and PCS 7, or
into third-party systems via a gate-
way. The automation state and the
live situation are directly coupled.
This enables process data to be
inserted directly into a video image
and saved. Images can also be
displayed and/or recorded as a
function of the process. The video
detection data, for example of an
edge deviation or a colour change,
are then fed back into the automa-
tion system.
contact@siemens.com
Level measurement
Brooks Instrument has introduced
four level measurement products.
The MC1000 Continuous Level
Transmitter can be used as a stand-
alone product or as an option on
the companys 810 MLG series. The
MC1000 has either fanged or
threaded tank connections, a two-
wire 420 mA interface and a HART
interface option.
ANV/ANH Point Level Switches
are vertical or horizontal level
switches for detecting level varia-
tions and activate alarms
accordingly. They can be used for
normal, corrosive or hazardous
liquids and are certifed explosion-
proof or intrinsically safe.
The MR783 Multi-Point Level
Switch is certifed explosion-proof
or intrinsically safe and is capable
of indicating more than one level
per tank and triggers alarms
accordingly.
The CCB311 Flow Switch is
designed to detect low fows in
horizontal or vertical pipes with an
upward fow direction. It is suitable
for liquids or gases.
Jim.Hollis@BrooksInstrument.com
Gas seal
EagleBurgmanns Cartex GSDN gas
seal is intended for applications in
chemical plants and refneries.
Users can install the bidirectional
gas-lubricated seals to standardise
new pumps or to recondition exist-
ing pumps that have conventional
stuffng box packings or liquid-
lubricated mechanical seals.
The seat and shaft sleeve rotate
along with the pump shaft, while
the springs remain stationary.
Internal pressurisation together
with centrifugal forces creates a
self-cleaning effect at the sliding
faces during operation. This
prevents contamination and
increases reliability, especially in
applications where the media
contains solids, says the developer.
The seals are designed to with-
stand critical situations during
startup and shutdown or if a fault
occurs in the buffer gas supply. The
double balanced seals remain closed
and balanced in these situations.
ellen.klier@de.eagleburgmann.com
Vibration tester
Fluke Corporations 810 vibration
tester is designed and programmed
to diagnose the most common
mechanical problems of unbalance,
looseness, misalignment and bear-
ing failures in mechanical
equipment, including motors, fans,
blowers, belts and chain drives,
gearboxes, couplings, pumps,
compressors, closed coupled
machines and spindles.
When it detects a fault, the Fluke
810 identifes the problem and rates
its severity on a four-level scale to
help maintenance teams prioritise
tasks. It also recommends repairs.
For mechanical diagnosis, the user
places the triaxial TEDS accelerom-
eter on the machine under test. The
New Products
accelerometer has a magnetic mount
and can also be installed by attach-
ing a mounting pad using adhesive.
A quick-disconnect cable connects
the accelerometer to the tester. As
the machine under test operates,
the accelerometer detects its vibra-
tion along three planes of movement
and transmits that information to
the Fluke 810. The vibration tester
then provides a plain-text diagnosis
of the machine with a recom-
mended solution.
precision.measurement@fuke.com
Corrosion inspection
Phasor CV/DM from GE Sensing &
Inspection Technologies is said to
be the frst phased array inspection
device for corrosion spot identifca-
tion in the marketplace. Part of
GEs feld-proven phased array
offering, the device is designed for
inspection coverage with every
scan, so that the smallest corrosion
pit can be identifed, measured and
evaluated. Concurrently, inspection
times are signifcantly reduced, says
the developer.
The Phasor CV/DMs software
displays inspection data, optimising
the potential of the specially devel-
oped multi-element phased array
probe. The probe has 28 adjacent
and discrete elements to enable
linear coverage, while the software
enables the user to select and
display thickness measurement in
each discrete beam, the minimum
thickness in a current view, and the
minimum thickness recorded
during a current scan since the last
time the instrument was reset.
There is also the ability to freeze a
top view inspection image, similar
to a conventional C-scan, and an A-
scan is provided to confrm the
readings in a traditional format. All
data captured by the instrument
can be downloaded by SD card in
JPEG format for subsequent analy-
sis and printing. The instruments
onboard memory is suffcient to
store the data of a metre scan.
geit-info@ge.com
new prods copy 3.indd 1 11/3/10 11:31:22
ABB Global Consulting 117
ABB Open Control Systems 103
AchemAsia 2010 120
Aerzener 91
Albemarle Catalysts Company 29
Amistco Separation Products 34, 39
Axens OBC
BASF Catalyst 40
BJ Process and Pipeline Services 86
Borsig 73
Bryan Research & Engineering 83
Buchen-ICS 65
Burckhardt Compression 57, 63
CB&I 74
ConocoPhillips Technology Solutions 14
Criterion Catalyst & Technologies 6
Curtiss-Wright Flow Control 2-3
Delta Valve 113
Euro Petroleum Consultants 114
ExxonMobil Research and Engineering Company 32
Flexim 52
Flexitallic 89
Foster Wheeler 94
GEA Wiegand 70
Global Refning Summit 2010 126
Hoerbiger 45
Idrojet 12
ITW 49
Johnson Screens 20
KBC Advanced Technologies 4
Chas S Lewis 100
Linde 54
Lurgi 26
Merichem - Gas Technology Division 79
Merichem - Process Technology Division 81
MPR Services 13, 85
Neuman & Esser 19
NPRA Reliability & Maintenance Conference 108
Paharpur Cooling Towers 66
Process Consulting Services 10
Prosim 25
Rentech Boiler Systems IBC
Resource Development Company 77
Spectro Analytical Instrument 119
Sulzer Chemtech 36
Swagelok Company 69
Thermo Scientifc 99
TPS-Technitube 11
Uhde 22
UOP 46
Vereinigte Fllkorper-Fabriken 8
Yokogawa Europe 93
Alphabetical list of advertisers
For more information on these advertisers, go to www.ptqenquiry.com
ad index copy 5.indd 1 11/3/10 22:04:27
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15 Anode-grade coke from traditional crudes

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