catalysis

ptq catalysis 2009

2009

ptq

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 catalysis Security of
ptq

feedstock supply
5 Editorial Comment: Refining and catalyst industry profitability
René G Gonzalez
Vol 14 No 2
Vol 13 No 2
2009
2008 7 PTQ Catalysis roundtable
www.eptq.com

D
15 Hydrocracking and hydrotreating developments
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
René G Gonzalez René G Gonzalez
refiners remain a big play for prospective investors. It used to be
editor@petroleumtechnology.com
conventional wisdom that higher fuel prices and a slowing economy
19 Increasing
would curbolefinsdemandyield and increase supply, but for the past seven years
hasJose
that notMaria
provedAguilar
to beandthe Jcase.
M Leon Gil CEPSA
While the rateGibraltar-San
of increase Roque refinery
in world oil demand
Production Editor
Rachel Zamorski has Fernando
declined Sanchez
since Arandilla Grace
the surprising Davison
4% surge in 2004, it nevertheless appears that
production@petroleumtechnology.com demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
increasing oil consumption
23 Reducing by China,from
NOx emissions India FCC
and even the Middle East producers
regenerators
themselves
Ye-Mon Chen and David Brosten Shell Global Solutionsnery
will continue. It is also safe to assume that refi (US)and petrochemical
Graphics Editor conversion unit capacity will need to expand.
Mohammed Samiuddin No massive new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com 27 Impact
foreseeable future.ofThelow-sulphur
world will remainbunkers on refineries
dependent on oil and gas for decades to

come Mike Stockle
even thoughand theTina Knight Foster
upstream Wheeler
industry Energy
faces Limited challenges in the
increasing
Editorial discovery and production of new sources. In fact, some well-placed industry
PO Box 11283 33 Continued
analysts think 2008 may gains in FCC
be the pretreating:
year where there is nopart 1 in crude supply at
increase
Spring TX 77391, USA all fromDesiree
regionsJ outside
De Haan, ofAndy
OPEC. For this and
Shivaram reason, weDwill
Kevin continue to see significant
Carlson
tel +1 281 374 8240 investment
in Catalysts
Criterion refinery & upgrades despite surging costs — security of feedstock
Technologies
fax +1 281 257 0582 supply, albeit unconventional low-quality feedstock, takes precedence over the
quality of feedstock supply.
39 Mercury
Feedstock options removal in hydrocarbon
such as biomass streams Canadian tar sands
(for biofuels production),
Advertising Sales Manager distillate
(for Steve Catchpole
production) Johnson Matthey
and other Catalysts
types of unconventional crude sources require
Paul Mason

reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com
47 Producing
process configurations. propylene
The quality glycol
of theseform
typesbiomass
of feedstock are one important
Advertising Sales reason
why Pavone
Tony a widerSRI array of catalysts has been introduced into the market. For
Consulting
Bob Aldridge example, as refiners cut deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com metals in the VGO requires a properly designed guard bed system to protect active
51 Increasing ULSD production with current assets
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Advertising Sales Office <10),
(eg, Bobhigh
Leliveld Albemarle
metals, nitrogenCatalyst
and Company BV
other undesirable components is one of the
tel +44 870 90 303 90
main Steven Mayo
reasons why Albemarle
hydrotreatersCorporation
and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 accommodate not only higher volumes of catalyst, but also a wider variety of
catalyst with specific formulations.
Publisher
Nic Allen Non-catalytic processes are also playing a significant role in the refiner’s ability
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. For example,
some refiners processing higher volumes of resid and atmospheric tower bottoms
Circulation have considered adding certain types of solvent-extraction processes in addition
Jacki Watts to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
circulation@petroleumtechnology.com coker operations. Improvements in furnace technology, such as with olefin steam
cracker operations, have resulted in significant increases in worldwide ethylene
Crambeth Allen Publishing Ltd capacity.
Hopesay, Craven Arms SY7 8HD, UK However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax +44 870 90 600 40
the following articles authored by experts in the field of downstream process
ISSN 1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded to the Q&A published in this issue of PTQ Catalysis, as
wellFoster Wheeler-built
as to first-of-a-kind
those respondents who methyl methcrylate
addressed the online(MMA) plant for
questions Lucite
(www.eptq.com)
thatInternational
addressedinthe Singapore
specificsstarts production
of certain ahead
reactor andofcatalytic
schedule.issues
The new 120 000
of importance to
Petroleum Technology Quarterly (USPS
0014-781) is published quarterly plus the tonnes per year plant, which uses Lucite’s state-of-the-art Alpha technology to produce
industry.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
MMA, is located on Jurong Island and will supply customers in Asia, where the demand
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. for MMA has grown most rapidly.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to Photo courtesy of Foster Wheeler/Lucite International
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437

Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez

©2009. 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.

PTQ CATALYSIS 2008 5

contents copy 2.indd 1 4/2/09 21:13:31

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 Refining
Security and
of
catalysis catalyst industry
ptq
feedstock supply
Vol
Vol14
13No
No22
2009
2008
profitability

C
D
Editor atalyst
René
Editor espitedemand
signs in in 2007 theofpetroleum
a slowdown refining
in various industry
sectors will
of theprimarily
economy, be
RenéGGGonzalez
Gonzalez dictated
refinersbyremain volumea growth big play in forhydroprocessing
prospective investors. catalysts and increased
It used to be
editor@petroleumtechnology.com
editor@petroleumtechnology.com refined product wisdomoutput in the Africa-Mideast
conventional that higher fuel pricesand andAsia-Pacific
a slowing economy regions.
Global
would efforts
curb to reduce and
demand air pollution
increase supply,by lowering but for thethesulphur content
past seven in
years
Production motor vehicle fuels will tocontinue to boost
Whilecatalyst loadings, as will
in the ongoing shift
ProductionEditor
Editor that has not proved be the case. the rate of increase world oil demand
Rachel toward heaviersince grades theofsurprising
crude oil4% (which
surgehave higher sulphur levels) and the
RachelZamorski
Zamorski has declined in 2004, it nevertheless appears that
production@petroleumtechnology.com
production@petroleumtechnology.com
development
demand beyond of unconventional
2008 will grow, petroleum
along with resources
prices. such as a
It is Canadian
safe bet tar sands.
that In
rapidly
the Africa-Mideast and Asia-Pacific regions, growing
increasing oil consumption by China, India and even the Middle East producers motor fuel demand due to the
rapid expansion
themselves will of the motor
continue. vehicle
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assume thatsome growth
refinery andinpetrochemical
new refinery
Graphics
GraphicsEditor construction and expanded refined
Mohammed
Editor conversion unit capacity will needproduct
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MohammedSamiuddin
Samiuddin Despite
No massive an industry
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of energy are forced
expected cancellation
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stream in for the
the
graphics@petroleumtechnology.com
graphics@petroleumtechnology.com refining
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decades will
to
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come even withthough
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Editorial profiles
discoverywithand a global market that
production of newis demanding
sources. cleaner
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more diesel,industry
which
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expected to be2008in higher demand than gasoline
PO
POBox
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11283 think may be the year where thereinisthe nofuture.
increase Forinexample,
crude supply Total’sat
Spring CEO, Michel Benezit, noted in mid-January that the company is moving forward
SpringTXTX77391,
77391,USA
USA all from regions outside of OPEC. For this reason, we will continue to see signifi cant
tel
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+1281
281374
3748240
8240 with a $2.2 billion upgrade to its Port Arthur, Texas,
investment in refinery upgrades despite surging costs — security of feedstock refinery even though other
fax
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281257
2570582 refiners
0582 supply,on the US
albeit Gulf Coast are low-quality
unconventional cancelling projects.feedstock, takes precedence over the
Currently, the refinery
quality of feedstock supply. expansions moving forward are focused on upgrading a
facility’s capability
Feedstock options to process heavy and
such as biomass (forsour crudes
biofuels and meet ULSD
production), Canadianrequirements
tar sands
Advertising
AdvertisingSales
SalesManager
Manager beyond 2012. For example,and newotherunitstypesat the
Paul (for distillate production) ofTotal Port Arthur crude
unconventional refinery expected
sources to
require
PaulMason
Mason come on-line in late 2011 will increase the refinery’s ability to process cheaper heavy
sales@petroleumtechnology.com reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com and sour confi
crudegurations.
and enable it to produce 60 000 bpd of of feedstock
ULSD. While
process The quality of these types are large amounts
one important
Advertising ofreason
hydrotreating catalyst will be required to supply the hydrotreater’s reactors,
AdvertisingSales
Sales why a wider array of catalysts has been introduced into the market. For
Bob delayed coking capacity will be increased significantly to demetallise coker gas oilof
BobAldridge
Aldridge example, as refiners cut deeper into the vacuum tower, the concentration
sales@petroleumtechnology.com
sales@petroleumtechnology.com
feeds
metalsto hydroprocessing
in the VGO requires units. Of course,
a properly even with
designed the latest
guard guard to
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technology
active
installed in hydrotreaters and mild hydrocrackers, the
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Advertising
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SalesOffice is(eg,
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and other financing delayedcomponents
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is one of the In
tel
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30390 addition, many why of those refiners expanding their dieselare production
fax
90 main reasons hydrotreaters and hydrocrackers becomingwill improve
larger — to
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2469090 their crude unit/vacuum
accommodate not onlydistillation
higher volumes units atof the front end
catalyst, butofalso
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the potential
catalyst withcapacity
specific of downstream FCC and hydroprocessing units.
formulations.
Publisher
Publisher
Nic Similarly,
Non-catalytic ExxonMobil
processesplans are alsoon spending
playing a signifi$1 billioncant to roleboost
in the thereficlean
ner’s diesel
ability
NicAllen
Allen output
publisher@petroleumtechnology.com
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. ForAntwerp,
at its refineries in Baytown, Texas, Baton Rogue, Louisiana, and example,
Belgium.
some refiOther oil companies
ners processing higher have also announced
volumes of resid and projects to boost
atmospheric towertheirbottoms
diesel
Circulation production, while several continue to be affected by
have considered adding certain types of solvent-extraction processes in addition variations in crude prices and
Circulation
Jacki
JackiWatts
Watts declining
to overalldemand
improvements in gasoline-focused
to crude unitmarkets. (eg, vacuumFor example,
tower revamps)Valero Energy’s
and delayed Q4
circulation@petroleumtechnology.com
circulation@petroleumtechnology.com 2008
cokerearnings
operations.report shows a loss of
Improvements inover
furnace$3 billion and thesuch
technology, companyas with is temporarily
olefin steam
shutting down a significant
cracker operations, amountinofsignifi
have resulted its refining capacity in
cant increases on worldwide
the US GulfethyleneCoast,
Crambeth
CrambethAllen
AllenPublishing
PublishingLtd including
Hopesay,
Ltd capacity. its Texas City refinery and a portion of its Corpus Christi, Texas, refinery.
Hopesay,Craven
CravenArms
ArmsSY7
SY78HD,
8HD,UKUK Marathon
However, Oilany andexpansion
ConocoPhillips of the are value alsochain
postponing or cancelling refinery
(eg, ethylene-to-propylene via
tel +44 870 90 600 20
tel +44 870 90 600 20 expansions or upgrades.
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax
fax+44
+44870
87090
90600
60040
40 Surprisingly,
the following all of these
articles refiningbycompanies’
authored experts infacilities
the field areofconsidered
downstream to beprocess
high
ISSN on the Nelson complexity index and capable of processing a wide variety of crude
ISSN1362-363X
1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
feedstocks relative to theirtocompetitors. Regardless,
editorial and responded the Q&A published in worldwide
this issue of demand for dieselas
PTQ Catalysis,
continues
well as toto increase
those annually.who
respondents For addressed
example, there is an estimated
the online questions50 million tonne
(www.eptq.com)
Petroleum Technology Quarterly (USPS
per
thatannum
addressed shortage
the specifi of diesel forecasted
cs of certain reactor forandEurope
catalyticby 2015.
issues of Related to this
importance to
Petroleum Technology Quarterly (USPS projection, Sonhoe Development Company announced in late 2007 plans to build
0014-781) is published quarterly plus the industry.
0014-781) is published quarterly plus
annual Catalysis edition by Crambeth Allen a refinery in Teesside, UK, which will become one of the largest of its kind in Europe.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. Despite the apparent lack of progress since the project was announced, the
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
Periodicals postage paid at Emigsville PA.
Periodicals postage paid at Emigsville PA. developers claim the project remains on schedule as due diligence has been carried
Postmaster: send address changes to
Postmaster: send address changes to
Petroleum Technology Quarterly c/o PO out, and the facility is expected to be operating by 2014. The facility will make up
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437
Box 437, Emigsville, PA 17318-0437 7–10% of the previously noted European diesel deficit.
Back numbers available from the Publisher
Back numbers available from the Publisher
at $25 per copy inc postage. Despite the global economic downturn, the fundamentalsRené of certain G planned
Gonzalez and
at $30 per copy inc postage.
borderline projects still stack up. If and when the credit markets improve and
financing becomes available, more projects will go forward simply because there are
millions of barrels of heavy crude that still need to be extracted and processed.

René G Gonzalez

PTQ CATALYSIS 2009 5

PTQ CATALYSIS 2008 5

ed comment copy 2.indd 1 2/2/09 14:01:45

 Travel with us,
and you’re always
on the road
to innovation.

THE CLEAN FUELS TEAM

www.criterioncatalysts.com
© 2008 Criterion Catalysts & Technologies L.P. (cri815_0508)
www.ptqenquiry.com
for further information

cri815_A_roadInnovation_ptq.indd 1 5/29/08 12:07:17 PM

criterion 1 30/1/09 14:07:12
 PTQ Catalysis roundtable
The industry’s expectations for higher margins in specific areas, such as distillate, have
resulted in formulations that provide higher yields and longer cycle lengths. In many
cases, a catalyst’s ability to help meet impending emissions limitations is becoming the
main thrust for catalyst selection. The following responses are supplemented by more
focused responses at www.eptq.com/QandA
❝ At what point does a two-stage reactor design
significantly enhance HDS/HDA catalyst effectiveness
(considering recent efforts to process solvent or distillate
feedstocks, such as Swedish city diesel)? With current budget
constraints, what factors should justify the implementation
of counter-current reactor technology over conventional co-
current reactor technology?
❞ to the reaction exotherms, both of which can result in higher
Sal Torrisi, Business Manager, Distillate Catalysts,
Criterion Catalysts & Technologies, sal.torrisi@cri-
criterion.com: Recent significant performance advances in
conventional NiMo catalyst technology (eg, Centinel Gold
DN-3330) have proven in commercial operations that a
higher degree of aromatic saturation can be achieved
compared with prior generation catalysts. In the diesel
boiling range, virtually all polynuclear aromatics (PNAs) and
a substantial quantity (20–50%) of monoaromatics can be
removed in an appropriately designed and operated single-
stage reactor hydrotreater. When deep aromatic saturation is
required (>50%), the two-stage reactor approach using a
noble metal catalyst in the second reactor is still preferred.
This approach is favoured in regions where there are
stringent aromatics specifications or where refiners are
looking to selectively fix hydrogen into liquids (ie, where
volume gain delivers extra margin).
Rasmus Breivik, Manager, Refinery Group, Haldor Topsøe,
rao@topsoe.dk: Industrial experience of producing ultra-low
aromatic diesel such as Swedish city diesel since the early 1990s
has resulted in an improved HDS/HDA technology that is a
cost-effective solution for upgrading heavy diesel fractions to
high-quality ultra-low sulphur diesel. Developments
in dearomatisation catalysts have led to the commercialisation
of catalysts with four times higher activity for the saturation of
aromatics. Required catalyst volumes have been reduced to a
level that makes counter-current reactors no longer justifiable
from an economical perspective.
❝ Can you point out any interesting results where coker
gas oils and other relatively high-sulphur, nitrogenous
streams have been treated in a single-stage VGO hydrotreater?
How were any of the expected problems handled, such as a
higher exothermic heat release?
❞ hydrotreater feed. Such feedstocks typically find homes in
Kevin D Carlson, Global Business Manager, FCC Pretreat
and Sentry Products, Kevin.carlson@cri-criterion.com: In
recent years, a number of new cokers have come on-line to
take advantage of widening margins between medium and
heavy crudes. This trend continues, resulting in existing VGO
hydrotreaters, many with single-bed reactors, being called
upon to process the resulting difficult feed streams. In
addition to the high aromatic and contaminant levels of these
heavy coker gas oils, a number of refiners are utilising the
www.eptq.com
Q_A copy 2.indd 1
VGO hydrotreater to process the resulting coker naphthas,
further increasing feed contaminants while decreasing reactor
hydrogen partial pressures. The ongoing challenge to the
refiner is to maintain stable long-term operations while
operating with both high metals deposition from the feed
contaminants and high reactor bed outlet temperatures due
deactivation rates.
Criterion has been mitigating these impacts by developing
unit-specific catalyst systems. Typical catalyst systems employ
activity and size graded top-bed products from the proprietary
Sentry OptiTrap family to control pressure drop from
particulates and foulants, a demetalisation section using
products from the proprietary Sentry MaxTrap portfolio, to
protect from a number of possible feed poisons, and high-
activity main-bed products from the Ascent product line with
a commercially proven ability to provide high levels of
performance and low deactivation rates in these challenging
VGO operations.
In addition to protection from feed contaminants, the
technology produces catalysts with improved tolerance to
thermal-based deactivation. This tolerance allows for reduced
deactivation rates at higher temperatures and lower hydrogen
partial pressures, leading to a longer cycle life in FCC pretreat
and VGO units. This improved stability at high temperatures
is particularly useful in operations with high reactor outlet
temperatures due to feed quality or system constraints.
Woodrow K Shiflett, Director of Marketing, Advanced
Refining Technologies (ART), wosh@chevron.com: High-
sulphur, high-nitrogen streams, such as heavy coker gas oils
and coker gas oils and DAOs, have been processing in VGO
hydrotreaters without notable problems for years. ART has
extensive experience in this area from the long-term and
widespread application of its ApART Catalyst Systems in
numerous VGO hydrotreaters. Such catalyst systems are
tailored to maximise HDS removal to produce low-sulphur
FCC gasoline as well as optimise FCC performance through
HDN and PNA removal functions. A number of publications
describe this technology, in collaboration with ART’s Grace
FCC associates.
Heat release and exotherm control rarely pose challenges
unless coker naphthas, excessive light coker gas oil content or
other highly olefinic components are present in the VGO
other hydroprocessing units such as NHTs and light distillate
hydrotreaters, which are designed to accommodate the high
olefin contents.
❝ With more TGU capacity likely to be added
downstream from Claus units to achieve 99.9% sulphur
recovery, what important parameters should refiners
consider in catalyst selection? How does end-of-cycle
catalyst reuse/regeneration factor into tail gas catalyst
selection?
❞
PTQ CATALYSIS 2009 7
2/2/09 10:05:15
 Nilanjan Brahma, Business Manager, Eurecat, nilanjan.
brahma@eurecat.com: Tail gas catalysts are typically in
service for many years and regeneration is rarely considered.
One factor that should be evaluated when considering a fresh
charge of tail gas catalyst is preactivation of the catalyst load.
Preactivation of tail gas unit (TGU) catalysts installed in
proprietary Shell Claus Off-gas Treatment (SCOT) units offers
significant advantages over a traditional start-up, where the
oxidic catalyst is sulphided after loading. The preactivation
benefits include:
— No additional sulphur chemicals (spiking agents) need to
be introduced in cases where sufficient amounts of sour gas
are not available.
— Temperature limits in the SCOT unit will not adversely
affect the activity of the TGU catalyst, since the catalyst is
activated prior to loading. In many units, the temperatures in
SCOT units are not optimal for obtaining maximum catalyst
activity
— There will be no water make from sulphiding upon
start-up
— Exotherm phenomena during start-up are eliminated
— The catalyst is immediately ready to perform after loading.
One preactivation technology that has been used in
dozens of TGUs is Eurecat’s Totsucat process. With Totsucat,
a totally sulphided and activated catalyst can be loaded in
the TGU, eliminating start-up hassles and unnecessary
delays associated with sulphiding.
Breivik: Tail gas treating is a special subset of hydrotreating
due to the fact that TGUs operate just above ambient pressure
and the feed gas contains large amounts of water. TGU
catalysts are thus designed with a pore size distribution and
porosity to minimise diffusion limitations, resulting in better
utilisation of the catalyst activity for converting the organic
sulphurs to H2S.
It is also important that TGU catalysts are capable of
handling temperature excursions without significant loss of
surface area and catalyst strength. Due to fluctuations in the
oxygen-to-fuel ratio, the catalyst may be exposed to elevated
temperatures during a typical cycle.
Soot formation is the other frequently occurring issue in a
TGU, due to operation with a too low oxygen-to-fuel ratio in
the Claus unit. The soot formation results in an elevated
pressure drop over the TGU catalyst bed. It should be noted
that even a very small pressure drop increase is typically
unacceptable, as the blower does not have additional capacity
to compensate for the increase in pressure drop and
consequently the throughput of the TGU is decreased.
Therefore, even the smallest pressure drop increase will often
require a catalyst replacement to keep the refinery operating
at full capacity.
www.ptqenquiry.com
for further information
8 PTQ CATALYSIS 2009 www.eptq.com
Q_A copy 2.indd 2
Since pressure drop is so critical for the cycle length of a
TGU, all TGU catalysts are produced in large sizes such as
1/8in, 1/10in and 1/6in in various shapes.
Haldor Topsøe recently introduced a new TGU catalyst
designated TK-222 in a 1/8in ring shape, which will reduce
the start-of-run (SOR) pressure drop by 85% compared to any
other commercial available TGU catalyst. Using TK-222 will
allow the refiner to handle much more soot formation before
the end-of-run (EOR) pressure drop is reached. Alternatively,
a TGU using TK-222 will be able to process much more tail
gas with the same blower capacity, thus effectively
debottlenecking the TGU, which means the refiner can
process higher sulphur crudes without building additional
tail gas capacity.
Due to the criticality of the SOR pressure drop in a TGU,
regeneration of the TGU catalyst for reuse in the TGU is not an
option many refiners would consider. Regenerated catalyst will
result in a higher SOR pressure drop compared with new
catalyst due to some catalyst breakage during the handling and
regeneration process.
Steve Massie, Business Manager, Gas Treating Catalysts,
Criterion Catalysts & Technologies, steve.massie@cri-
criterion.com: The most important factor in tail gas treatment
is reliably meeting the stringent emission requirements. If
these requirements are not met, then, depending on the
location and requirements, the refinery or gas plant must shut
down, cut back on production and/or pay fines. Therefore, the
TGU catalyst must be robust and stable, able to withstand
upsets and continue to operate to meet the environmental
requirements. Once these first parameters are met, the site may
then consider the lower purchase cost associated with low-
density catalysts, and the lower operating cost associated with
low-temperature catalysts. Criterion’s 234 TGU catalyst exhibits
both of these features. It is a low-density catalyst and can be
operated at lower reactor inlet temperatures.
Once the catalyst reaches its end-of-cycle (EOC) without
unusual incidents such as sooting, it has no other value except
reclamation of the transition metal components. If the catalyst
is sooted, regeneration can be considered. However, due to the
critical nature of this processing unit, regeneration economics
are not considered worth the risk.
Elise Mophett, BASF Catalysts, Global Product Technology
Manager, Adsorbents, elise.mophett@basf.com: As
environmental regulations push sulphur recovery efficiencies
to ever-increasing levels, even to the extent of upstream plant
shutdowns, should the sulphur recovery unit (SRU) not meet
emissions expectations, the need for catalyst optimisation
through the SRU is crucial. Minor contaminants like carbonyl
sulphide (COS) and carbon disulphide (CS2) can escape even
2/2/09 10:05:28
 www.ptqenquiry.com
for further information

albemarle4.indd 1 4/2/09 21:09:25

 the most efficient amine-based tail TGU if levels are high. In
some cases, 50% of the sulphur leaving the SRU comes from
COS and/or CS2 contamination. The use of a titanium dioxide
catalyst, BASF SRC 99ti or BASF DD-931, in the first Claus
catalyst bed with high activity activated alumina, BASF DD-
431, will assure maximum destruction of COS and CS2 before
the TGU. In addition, should TGU bypass be required, the
Claus unit will have the best available catalyst configuration,
allowing for the maximum achievable recovery until the TGU
is back on-line.
❝ With over 60% of the world’s 260 announced
downstream projects postponed or cancelled, how will this
affect timing and scope of projects focused on reducing CO2
emissions and meeting future CCS requirements?
❞ making reactor volume available to do some additional
Alan Del Paggio, Vice President, Upstream and Renewables,
CRI/Criterion, Alan.DelPaggio@cri-criterion.com: CRI/
Criterion’s products, which support CCS, are in fact
multifunctional and can be used in a broader range of
applications. For example, hydrogen permeable palladium
and/or palladium alloy membranes can also be used in
distributed hydrogen production to augment hydrogen
production and/or recovery, as well as to enhance hydrogen
purity. Within this context, the postponement of CCS
projects represents a fractional loss of opportunity and is not
catastrophic. We are hopeful, however, that CCS activities
will resume when global economic conditions allow.
❝ Many refiners expect favourable distillate margins in
the first half of 2009, even with the slowdown in worldwide
economic activity. Beyond taking some of the obvious
measures to increase distillate production, what cost-effective
3rd
refining
China
★
2009 ★
★
★ ★
17–18 March 2009
Beijing
The networking event of the year for everyone
with an interest in refining technology in China.
Combine it with a visit to CIPPE, 19-21 March
www.refiningchina.com
10 PTQ CATALYSIS 2009 www.eptq.com
Q_A copy 2.indd 3
strategies are available to increase ULSD or Euro V diesel
production? Considering that 20–30% straight-run (50
cetane) diesel is typically downgraded to LCO in the catalytic
cracker, how can this practice be reduced to 10%?
❞
Larry Kraus, Team Leader, Clean Fuels, Projects and
Strategic Accounts, Criterion Catalysts & Technologies,
lawrence.kraus@cri-criterion.com: Some of this high cetane,
heavy diesel (or LVGO) is sent to the FCC because it contains
the most difficult to treat sulphur species and can cause cold
flow property issues. We have been very successful in the past
few years in developing and commercialising higher activity
HDS catalysts that can handle this heavy diesel in the ULSD
unit, easily managing the HDS requirements while also
catalytic dewaxing to improve diesel cold flow properties.
More than a dozen of these applications are operating
worldwide.
For the heavy diesel that goes to an FCC pretreat unit, we
have been successful in turning this material into ULSD,
either directly at the FCC pretreat unit or by recovering the
FCC pretreat LSD product and reprocessing it in the ULSD
unit using modified catalyst systems. Hydrotreated diesel
streams are difficult to process because the sulphur and
nitrogen species remaining in them are very refractory.
Criterion has commercial experience processing hydrotreated
diesel streams in a variety of low- and high-pressure units.
For the heavy diesel that is processed in the FCCU, much of
this will convert to lower cetane, higher density, more
aromatic LCO. This volume of LCO can be processed to ULSD
and even meet Euro V diesel specifications given the right
catalyst system. A range of catalytic solutions is available to
increase the LCO processing by enhanced single-stage aromatic
saturation, selective ring opening or two-stage aromatic
saturation. All of these solutions are practised commercially
throughout the world.
❝ Is there a noticeable increase in requests by operators
★
for assistance in coordinating the catalyst change-out and
turnaround service cycle? If so, is this because
proper turnaround management of new catalyst technology
and catalyst enhancement systems has become more
complicated or is it due to more stringent reliability and
safety standards?
❞
Shiflett: In a broad sense, at ART we do not detect an
increase across the board, but note that refiners who have
suffered from reliability issues are more prone to requesting
additional help in executing catalyst loadings. With respect
to reliability assurance, it is difficult to separate concerns
about proper catalyst loading and concerns about rigorous
installation of the latest technology in reactor internals and
gas-liquid distribution systems. Both procedures must be
done correctly to ensure maximum performance is obtained
from the reactor/catalyst system. ULSD regulatory activity in
recent years has driven the demand for the latest in reactor
internals and distribution technologies, such as the
proprietary IsoMix internals offered by Chevron Lummus
Global (CLG). Performance guarantees for such internals in
new designs as well as in revamps to existing units have
naturally resulted in technology provider coordination of
their installation in the 2006-2008 period. Subsequent
reinstallations, properly facilitated, are managed by the
effective collaboration of the skilled loading contractor and
the refiner’s start-up team.
Large units, such as residual oil RDS and VRDS units, and
many ULSD units typically will involve catalyst loads of
500–1500 tonnes. Such sheer catalyst quantity dictates that
adequate resources be on-site to coordinate the proper
2/2/09 10:05:42
 www.ptqenquiry.com
for further information

albemarle 2.indd 1 4/2/09 09:43:20

 loading of the several types of grading components and
catalysts employed. Indeed, for decades ART has offered its
RDS/VRDS customers skilled technical support for catalyst
loadings. Owing to the close working relationship between
ART as catalyst provider and CLG as licensor of VRDS, RDS
and proprietary Isotreating units, seamless support to both
internals installation and catalyst loading for these units is
readily provided.
Dan Torchia, Catalyst Sales and Services Manager, Chevron
Lummus Global, dan.torchia@chevron.com: CLG has
noticed an across the board increase in requests for assistance
with managing and executing catalyst change-outs, reactor
inspections and start-ups. The scope of these requests ranges
from a simple review of turnaround procedures to hands-on
execution and management of the entire process. This increase
is believed to be driven by:
— Need for increased operating safety as unit severity
continues to increase
— Longer operating cycles (less frequent turnarounds and
“loss of memory”)
— Reduced refinery staff levels
— Shift from longstanding local habits to industry best
practices
— Demand for higher operating factors.
Typically, this activity should begin immediately following
a catalyst change-out decision and address schedule, activities
and contractors, as well as identify and assign responsible
individuals in the various organisations and departments. The
turnaround plan should be finalised several months in
advance of the actual event to allow for methodical ordering
of supplies, scheduling of resources and the all too common
early shutdown.
CLG believes that this planning and working together is
essential to get the most from your operating unit, from your
Catalyst handling
and mechanical work
With more than 25 years
of experience
Mourik International
is a world leading supplier
for catalyst handling,
vessel and reactor services.
We think globally, but act
locally, as we operate
through a world-wide
network of subsidiary
organizations.
Offices: Europe, Middle East, Asia,
North America, South America
mourik.com
www.ptqenquiry.com
for further information
12 PTQ CATALYSIS 2009 www.eptq.com
Q_A copy 2.indd 4
new load of catalyst and to assure the safest possible operation
of the unit throughout the cycle.
❝ How are catalysts performing with the limited amount
of biofuel feedstocks currently processed through select diesel
hydrotreaters? What performance capabilities can refiners
expect to see in a biodiesel catalyst beyond 2010?
❞
Shiflett: Some time ago, ART embarked on a pilot plant
study using ULSD proprietary SmART catalyst systems to
define the landscape for the co-processing of bio-derived
and petroleum-derived diesel stocks, with a subsequent
publication on the work. Owing to uncertainties in US
tax credits for biomass-containing alternative diesel and
national EU biofuels targets overlaid with no EU-wide tax
policy on biodiesel, there is yet limited feedback from the
field. Should co-processing take an appreciable role in
diesel production employing biocomponents, concerns about
pour point and cloud point can be addressed by the
appropriate tailoring of catalyst systems in modest biofuel co-
processing. The accommodation of higher and higher oxygen
content with greater biofuel utilisation will have design and
revamp implications for facilities that must handle the
resultant exotherms within current infrastructures.
Torrisi: Criterion catalysts for the co-processing of biofeeds
in diesel production have performed as anticipated in
commercial application. We expect co-processing to remain
a viable, attractive strategy for refiners and will therefore
continue our research to produce new catalyst options for
this renewable feed blend. New products and technologies
will produce catalysts that will help refiners to leverage their
existing processing assets with drop-in catalytic solutions.
Mourik International B.V.
Nieuwesluisweg 110
3197 KV Botlek-Rotterdam
The Netherlands
Tel. +31-10-296 56 00
Fax +31-10 296 56 09
E-mail: mint@mourik.com
2/2/09 10:06:12
 www.ptqenquiry.com
for further information

albermarle 1.indd 1 4/2/09 09:42:10

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basf.indd 1 30/1/09 12:14:47

 Hydrocracking and
hydrotreating developments
Current emphasis on middle distillate production requires the expansion of hydroprocessing
capabilities affecting reactor and catalyst design. Increased diesel yields depend on the ability
to effectively upgrade cracked feedstocks and LCO, while eliminating fuel oil production
A
gainst a backdrop of global
recession, most refinery
investment up to 2012 involves
improvements to existing assets.
Improvements to catalytic processes will
focus primarily on hydrotreating and
hydrocracking. This includes expansion
of necessary hydrogen sources and tail
gas treating/sulphur recovery capacity.
These expanded hydroprocessing
networks, coupled with efficiency
improvements to crude units and
select thermal conversion processes
(eg, delayed coking and visbreaking),
increase the facility’s Nelson complexity
index. The higher the refinery’s
complexity index, the more capable it
is of processing and converting heavier
feedstocks into lighter components.
Over the next two to three years, the
light components expected to yield the
highest margins are typically in the
middle distillate range. However, the
high concentration of metals
contaminants and inorganics found in
many of today’s crudes can decrease a
hydroprocessing catalyst’s activity level
and ability to upgrade feedstocks into
ULSD and other high-margin products.
Regardless of how much additional
reactor capacity is added to compensate
for the negative effects of these metals
contaminants, the most cost-effective
strategy may be to consider employing
several types of catalyst in each reactor.
In almost every case, an increase in
catalyst inventories at many refineries is
a reflection of the flexibility needed to
deal with the changes in feedstock
properties that typically require higher
severity hydrotreating/hydrocracking
conditions (eg, higher temperature, and
hydrogen partial pressure). More
importantly, it is the cost of maintaining
a diversity of catalyst types inventoried
at refineries that complicates refinery
operations, particularly in the current
downturn.
Economic considerations
The downturn in the global economy
comes just as several world-scale facilities
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rene.indd 1
René Gonzalez
are due to come on-line in 2009 and
2010. For example, the United Arab
Emirates (UAE) is set to double its
refining capacity as it and other Middle
Eastern countries make efforts to
diversify their oil and gas industry away
from simple crude oil exports. A glut of
spare refining capacity may actually
accelerate efforts to remain competitive
by increasing refinery complexity. It
therefore stands to reason that the level
of catalyst capabilities will also increase.
While cyclicality is built into refining
outlooks, the current negative outlook
stems from demand changes that appear
to be structural and enduring, according
to Andrew Oram, Senior Credit Officer
for Moody’s. The downturn marks the
end of a long boom period for refiners
that began in 2003 as world demand for
diesel and other products took off.
By the end of 2009, another 2.5
million bpd of refining capacity will be
added around the world, according to
Goldman Sachs. But those projects that
have taken years to move from the
conceptual phase to construction are
now threatening to flood the market
with a glut of extra capacity just as
growth in demand for many
hydrocarbon-based products has slowed
in line with a weakening global
economy. It is impossible to predict
how long this downward cycle will last,
just as it was difficult to predict when it
would begin. But more complex refinery
networks, as well as those with rapidly
expanding populations such as in the
Middle East, may be somewhat insulated
from the downturn because domestic
demand for refined products is booming
and refining units are part of larger
state oil firms. For example, Saudi
Arabia, the world’s top oil exporter,
became the fastest growing oil consumer
in 2008 and will see oil product demand
increase by 7.0% in 2009 to 1.8 million
bpd. Large facilities under construction
in the region include two export-
orientated refineries in Saudi Arabia, a
refinery in Kuwait and the Abu Dhabi
National Oil Company’s (Adnoc)
refinery expansion at Ruwais, which is
scheduled to be completed by 2014 and
will add 417 000 bpd to Adnoc’s refining
capacity.
The major slowdown in China’s
economy is, of course, another aspect
to consider with regard to refinery
profitability. China has seen a drop in
its economic growth as The Organisation
for Economic Co-operation and
Development (OECD) economies
curtails its demand for Chinese goods.
For example, Chinese exports in
November 2008 fell 2.2% from the
same period in 2007, the first decline in
seven years. China’s economic growth
slowed to 9.0% in Q3 2008, down from
11.9% in 2007. The World Bank has cut
China’s 2009 growth forecast from 9.2–
7.5%, the lowest since 1990. China’s
economic annual growth has averaged
9.9% for the past 30 years. A recent
International Energy Agency (IEA)
forecast noted oil demand in China
grew 5.3% to 7.9 million bpd in 2008,
but expects it to weaken to 3.5% growth
in 2009, approximately 180 000 bpd
less than previously expected. According
to the IEA, if the country’s economy
were to expand by only 7.0% in 2009,
oil demand growth would be just 70
000 bpd, a level not seen since the
late 1990s.
However, many other factors must be
taken into account when considering
the viability of today’s refinery
operations, including:
— The previously noted flexibility in
the refinery’s configuration for crude
processing
— The superior product slate of the
refinery
— The strategic location of the facility
— Freight advantages
— Ability to maximise jet fuel and
diesel and minimise furnace oil
— Captive cogeneration power plants
to meet the facility’s steam and power
requirements
— Hydrogen production efficiency.
The most complex refiners can choose
the types of crude they want to process.
PTQ CATALYSIS 2009 15
2/2/09 10:11:06
 This advantage may become even more
important in the future as refiners strive
to reduce their overall emissions by
differentiating crudes according to their
potential to generate CO2. Being able to
choose the types of crude to be processed
depends to a large extent on a facility’s
catalyst-based processes, including
hydrotreating, hydrocracking, fluid
catalytic cracking (FCC) and others.
Global distillate demand
Since the new millennium, diesel
hydrotreating has primarily involved
sulphur removal to low (<500 ppm) or
ultra-low (<10 ppm) levels. In addition,
cetane uplift and poly-aromatic
hydrocarbon (PAH) removal are possible
with new catalysts. Hydrotreating diesel
can require severe processing, especially
when ultra-low sulphur is needed and
the feedstock contains cracked
components. The highest activity
catalysts are usually required for ULSD
production to reach acceptable cycle
lengths. CoMo catalysts are most often
specified for diesel and ULSD
hydrotreating operations, but NiMo
catalysts may be preferred in some
cases.
Hydrocracking catalysts usually
incorporate zeolites to selectively crack
heavier feed components into lighter
products. Nitrogen in the feed causes
substantial inhibition of the acid sites
in the zeolite responsible for cracking.
Pretreatment of hydrocracker feedstock
to reduce nitrogen content to a low
level substantially increases the
conversion activity of the zeolitic
hydrocracking catalyst. In today’s
refinery environment, a high pressure
hydrocracking unit may be too costly
for many oil companies. A more
affordable solution that generally costs
about a third of a full hydrocracking
unit is a mild hydrocracking (MHC)
unit. For example, more than 20 Axens
MHCs have already been licensed for a
combined capacity of 700 000 bpsd.
Should favourable economics compel
refiners to achieve near-complete
elimination of heavy fuel oil, the first
step would be to process FCC cycle oils
in the MHC unit, along with VGO.
More than likely, this would require the
addition of a second stage to the MHC
unit to process VGO, LCO and heavy
crude oil (HCO), essentially converting
the unit into a full hydrocracker. The
second step would be to consider the
construction of a vacuum resid
hydroprocessing unit, which would
treat FCC feed. Another alternative is to
install an atmospheric resid pretreater,
shut down the vacuum tower and feed
that product to a resid FCCU. Eighty per
cent of the world’s crude could be
processed in this manner.
However, some relatively high
operating costs are to be expected for an
16 PTQ CATALYSIS 2009 www.eptq.com
rene.indd 2
FCC pretreater, considering that it is
to be tasked with saturating
dibenzothiophenic compounds in the
heavy tail of resid-based feedstock. In
addition to at least one guard bed to
mitigate metals and nitrogen
contamination of reactor catalyst, the
pretreater reactors will require a well-
planned combination of the latest
NiMo/CoMo catalyst formulations,
probably operating at H2 partial
pressures in excess of 1900–2200 psi
and even higher pressures at end of run
(EOR). The elimination of SOx and NOx
precursors via pretreatment will
certainly go a long way towards meeting
future NOx and SOx emissions from the
FCC regenerator.
This seems to be the case with
numerous refiners currently in operation
throughout the world, including the
NPRC refinery in Japan processing Arab
Light crude. The facility employs a
vacuum resid desulphurisation unit for
FCC pretreatment.
For distillate-focused refiners
currently thinking of phasing out FCC
operations, it should be mentioned
that complete dependence on
hydrocracking may leave them with a
significant vacuum residue problem,
which the FCCU can address. The latest
developments in resid FCC processing
technology and catalysts, including the
processing of feeds with higher CCR
and metals content while increasing
LCO yields, have rendered the FCCU a
viable option over the construction of
a visbreaker, particularly if the FCCU
already exists and can be upgraded.
Resid cracking over modern catalysts in
a resid FCCU produces valuable
products in addition to fuel oil
cutter stocks.
Catalyst efficiency
In the process of hydrocracking
paraffinic hydrocarbon, it is important
to produce useful middle distillates at
higher yields to improve the economical
efficiency of the process. In addition,
the resulting gas oil is necessarily low in
pour point. That is, development of a
highly efficient hydrocracking catalyst,
which can enhance the cracking activity
and middle distillate yield of the
hydrocracking process, while also
making it possible to produce a gas oil
with low pour point, holds the key to
an improvement in economical
efficiency at low-to-moderate hydrogen
partial pressures.
Of course, VGO hydrocracking has
been an established process for decades.
However, since the difference between
the reactivity of a paraffinic hydrocarbon
and that of a VGO is so significant that
it is difficult to use the catalyst for the
latter as it is for hydrocracking a
paraffinic hydrocarbon, R&D aims at
the development of a highly efficient
catalyst for paraffinic hydrocarbons.
Briefly, these developments, as noted in
research by Aoki et al, generally include
catalyst comprising platinum loaded
into a support containing silica
alumina.1
Other research has demonstrated the
hydrocracking of paraffinic hydro-
carbons using a catalyst comprising
platinum loaded into a crystalline
aluminosilicate (zeolite). The crystalline
aluminosilicate catalyst is at a
satisfactorily higher level of cracking
activity, but the middle distillate yield
is low and the resulting gas oil fails to
obtain a sufficient pour point. On the
other hand, amorphous solid acid
catalysts, such as silica alumina, are at a
satisfactorily higher level in achieving
middle distillate yield along with the
low pour point of the resulting gas oil,
but are low in cracking activity. Ideally,
catalyst suppliers strive to formulate
hydrocracking catalysts that satisfy
high cracking activity and middle
distillate yield as well as low
pour point.
Inorganic contaminants in refinery
feedstocks are often poisons for
hydroprocessing catalysts. The source of
these contaminants is frequently the
crude itself, with different contaminants
associated with various crude sources.
Some contaminants are introduced
during normal refining processes or
from upset conditions. To control this
growing problem, increasing volumes
of catalysts with a high capacity to
adsorb contaminants at the top of the
reactor’s catalyst bed are being employed.
These sacrificial catalyst layers protect
downstream catalysts from the
poisoning, allowing them to retain their
high activity for a longer time and
increase cycle length.
Reactor investment
vs catalyst cost
The total on-site capital cost estimate
for a new hydrotreater plant varies,
depending on the licensed and
proprietary technology. It consists of
three parts: a two-reactor system (in
series) with interstage H2S stripping,
hydrogen make-up compressors and
remaining on-site capital equipment.
The cost of the reactor system and
make-up compressors is a function of
the percentage of cracked stocks present
in the hydrotreater feed pool, whereas
the cost of the remaining on-site
equipment is a function of capacity.
The combined flow rates, space
velocities calculated from kinetic
models and pressure are used to size
each reactor, with the restrictions that
the reactor length-to-diameter ratio
must be greater than or equal to five,
and the diameter must be less than or
equal to 15 ft. The cost of each reactor
is a function of the wall thickness and
2/2/09 10:11:30
 reactor weight. Next, the hydrogen
make-up compressor costs are calculated
based on the hydrogen consumption.
Differences in capital costs at a given
capacity level are the result of variations
in the fractions of the different types of
feed (eg, straight run vs cracked stocks)
and the sulphur level of the feed to the
hydrotreater. For example, an estimate
of $1600 bpsd is believed to be a more
representative ISBL investment cost to
produce ULSD.
The revamped hydrotreater on-site
capital portion of the model utilises
only the space velocity calculated for
the second reactor, used to lower the
diesel pool sulphur content from 500
ppm (manually specified) to 7 ppm. The
revamped hydrotreater capital cost
includes only an additional reactor,
heater and separator, and assumes the
existing inside battery limit equipment
will remain unchanged.
Until recently, on-site capital costs
for new and revamped hydrotreater
plants have included the initial catalyst
charge. The off-site capital cost for a
new plant has been assumed by many
in the industry to be 45% of the on-site
capital cost, and the off-site capital cost
for a revamped plant is assumed to be
30% of the on-site capital cost.
Hydrotreater catalyst cost (in dollars
per barrel) is a function of space
velocities and has been calculated
assuming a two-year life, with CoMo
catalyst typically in the first reactor and
NiMo in the second reactor. CoMo is
more reactive in removing sulphur
from the less challenging sulphur-
containing molecules. Below 500 ppm,
however, the sulphur present is more
likely to be contained in sterically
hindered molecules and more difficult
to remove using a CoMo catalyst. In
contrast, NiMo has higher activity on
more challenging sulphur-containing
molecules. Published data have shown
that the costs of both catalysts are $10
per pound, including royalty.
Yields
The volume and weight percentage
yields of ULSD produced by the typical
distillate hydrotreater can vary
considerably, depending on the fraction
of cracked stocks in the feed and the
level of aromatics saturation. An average
yield and energy content were estimated
for this article, based on the Criterion
data in a June 2000 study by the
National Petroleum Council. The yield
of hydrotreater product in the distillate
boiling range was assumed to be 98% by
weight, and the API gravity was assumed
to increase by two numbers, which
means the volume yield was 99.2%.
There was also a small increase in the
Btu content of the product on a weight
basis (98.2% of the feed energy content
in 98.0 wt% of the feed). The energy
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rene.indd 3
content declines on a volume basis,
because the heat content of the product
is 0.989 times the heat content of the
feed on a volume basis.The same
hydrogen consumption and hydrogen
plant cost estimation methodologies are
used by many for both the new and
revamp cases.
In the US, oil refiners must produce
100% ULSD by 2011. Refiners are
projected to invest $6.3–9.3 billion to
meet full compliance with the ULSD
Rule through 2011. Most refiners are
close to completing upgrades necessary
for full compliance. After 2011, the first
full year of 100% ULSD, the projected
differential of marginal prices is expected
to decline, because of lower distribution
and capital investment costs.
In Europe and the Middle East, where
hydrocracking capacity is significantly
higher than in the US, uncertainties
over the pace of engine, refinery and
pipeline testing technology
development; the availability of
personnel, thick-walled reactors and
reciprocating compressors; the
behaviour of ULSD in the oil pipeline
system; and cost recovery by oil pipelines
further cloud the outlook for the
transition to very low levels of sulphur
in diesel fuel.
LCO to distillate
LCO, containing 50–85% aromatics, is
a distressed refinery stream with limited
future disposition options, which is
why refiners are considering additional
upgrading options such as
hydrocracking. Hydrotreating and
hydrocracking licensors have proposed
various process configurations and new
catalyst capabilities so refiners can
avoid the costly option of severely
hydrotreating multi-ring thiophenic
LCO. It should be noted that higher
costs come with new catalyst
capabilities. However, despite recently
announced price increases in FCC
catalyst (including LCO upgrading
catalysts) by major catalyst suppliers
such as Albemarle, BASF and Grace
Davison, catalyst costs remain a small
part of the overall refinery operation
relative to feedstock costs.
Severe hydrotreating improves LCO,
with an increase of one cetane number
for every 75–80 ft3 of hydrogen
consumed. These conditions are
required to desulphurise the sulphur
found in the alkyldibenzothiophenes
(DBT). If LCO is to be upgraded to
ULSD, it is evident that LCO
hydrotreating would have to be
relatively severe (high pressure) to
achieve a limited improvement in
cetane number, aromatics reduction
and density.
Running relatively high percentages
of cracked stocks such as LCO and light
coker gas oil (eg, in the 30–50% range)
begs the question as to how fast does
this affect hydrotreating catalysts
currently available for ULSD production?
Other problems encountered with LCO
processing such as fouling and corrosion
also need to be considered as some
refiners try to process higher percentages
of cracked stocks through their ULSD
hydrotreaters. How often refiners go off-
spec or increase rerun in an effort to
process higher LCO fractions is difficult
to ascertain. It seems to depend on
multiple factors, including:
— Production of only one grade of
diesel (eg, less than 10 ppm S)
— Availability of tankage for rerun
material
— Deactivation rates for
hydrodesulphurisation (HDS) catalyst at
severe hydrotreating operations
— LCO end point limits (ie, how much
undercutting is required?).
Again, depending on the volume of
LCO being hydrotreated in ULSD
operations with FCC post-treaters, one
of the unanticipated problems reported
by a number of refiners deals with EOR
conditions, where there may be a close
relationship to LCO content and
product colour. The higher EOR
temperatures produce olefins that
react with nitrogen and sulphur
compounds.
Whenever an FCC pretreater is
employed to achieve ULSD and low-
sulphur gasoline specifications and
LCO quality is an issue (eg, increased
levels of dibenzothiophenes),
adjustments to the FCCU itself may be
necessary. A detailed discussion on
what adjustments are necessary to the
FCCU is beyond the scope of this article
and can be obtained in the recently
released FCC study authored by myself
and FCC expert Warren Letzsch, The
FCCU in Transition, available from www.
eptq.com/studies.
New desulphurisation
technologies
Beyond traditional hydrotreating to
remove sulphur from diesel streams,
new technologies are under develop-
ment that could reduce the cost of
desulphurisation. They include sulphur
adsorption, sulphur oxidation, gas-to-
liquids and biodiesel. Each of these
technologies is in the first stages of
commercialisation. It is uncertain
whether any of them will make a
significant contribution to meeting the
requirements of future refined product
specifications, although they may have
some impact later in the next decade.
References
1 Nobuo Aoki, et al, USPTO Patent Application
20080306321, Process for producing liquid
hydrocarbon with hydrocracking catalyst.
PTQ CATALYSIS 2009 17
2/2/09 10:12:07
 o r ld wid e u s e ou r hy
rs w d ro p
i ne
f no lo g i e s and c at aly st s
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r p u ho al i t y r
e a ne s show y o w. (O 0 fe e
c et
l
L
u ww w. cl g-
1) 5 1 0
cl e . 4 2. 2ds .
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cleaner
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Heavy R low sulfur fuel oil

D (0.1% - 0.5% S)
Feeds S RFCC feed
(3-6 MCR)
(5-15 ppm V & Ni)
coker feed

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clg.indd 1 30/1/09 12:19:04

 Increasing olefins yield

Plant data show how an FCCU’s propylene yield is maximised while minimising
its dry gas and slurry yield at a CEPSA refinery. An integrated catalyst system was
used to process high nickel-containing feedstock to avoid fuel gas system limits

Jose Maria Aguilar and J M Leon Gil CEPSA Gibraltar-San Roque refinery
Fernando Sanchez Arandilla Grace Davison

T
he Spanish oil group CEPSA
operates three refineries in Spain 
— Gibraltar-San Roque, La Rábida
and Tenerife — which in total can distil
430 000 bpd (or 21.5 million tpy) of 
crude oil, representing more than one-
third of Spain’s distillation capacity. Two
of these refineries, including the 240 000 
$RYGASWT

bpd (or 12 million tpy) Gibraltar-San

Roque facility, operate FCCUs that are
currently utilising FCC catalysts from 
Grace Davison’s ProtAgon family of
catalysts. The main FCCU objective at
the Gibraltar-San Roque refinery is to

maximise its propylene production, as
well as to minimise its dry gas yield while ProtAgon–17C
using high nickel-containing feedstocks,

minimise its slurry yield and increase *AN *AN *AN
LPG olefinicity.
The Gibraltar-San Roque FCCU is a
UOP side-by-side (SBS) design operating Figure 1 Evolution of dry gas production in the Gibraltar-San Roque FCCU
at 538°C and typically processing
feedstock with a UOP K-factor (K) of
12.0 and specific gravity (SG) of 0.915.
The facility is distinguished by its 
petrochemicals-producing capabilities as
well as its lubricant manufacturing units.
Consequently, its range of products is 
more diverse than those produced by a 100% ProtAgon–17C
typical refinery.

FCC operating data
In December 2003, the Gibraltar-San
Roque FCCU was modified to maximise
propylene production, and by the
summer of 2005 was operating
successfully. However, when the unit
began processing a feedstock that
contained twice as much nickel, there
was a huge increase in its dry gas yield,
which started to limit the light ends
area. This resulted in the need to operate
at a lower reactor temperature, leading
to a lower propylene and butylenes yield
and an increase in slurry; in other words,
a reduction in total throughput.
CEPSA’s R&D facilities in Madrid
carried out an extensive catalyst
evaluation in 2007 to look at the options
for maximising propylene, while taking
into consideration the constraints of the
commercial FCCU. The base catalyst
www.eptq.com
grace.indd 1
0ROPYLENEYIELDWT




*AN
Figure 2 Propylene production in the Gibraltar-San Roque FCCU
Brilliant (preblended with 8–9%
OlefinsUltra) was compared to ProtAgon-
17C, a catalyst already used in another
CEPSA refinery. Grace Davison developed
this first-generation ProtAgon catalyst to
maintain or increase the propylene
make and allow CEPSA to operate a
*AN *AN
different optimisation scenario. The data
obtained in the Davison circulating riser
(DCR) pilot plant established that
ProtAgon-17C offered all the benefits
required to meet the FCCU’s objectives,
so CEPSA chose to use it at its Gibraltar-
San Roque refinery.
PTQ CATALYSIS 2009 19
2/2/09 10:14:06
 During the first six months, a blend
of 50% ProtAgon-17C and 50% Brilliant
 (with 8–9% OlefinsUltra), the previous
catalyst, was used. ProtAgon-17C had a
"RILLIANT/LEFINS5LTRA
quick impact on the FCCU
0ROPYLENEPRODUCTIONn-T DOVER

0ROT!GONn# Peri
and continued to perform well. As a
Cata
 result, CEPSA decided to use 100% Add
ProtAgon-17C. Feed
As well as maximising its propylene Fresh
yield, an important objective for the SG f
 refinery was to reduce its dry gas UOP
production. Figure 1 shows this objective Con
was clearly achieved using ProtAgon- Ope
17C. Also, Figure 2 shows that propylene Reac

production started to increase as soon as Rege
ProtAgon-17C was added to the FCCU, Rege
despite the fact that the unit was very Preh
close to its hydraulic limit. In addition, Cat-

     when propylene production is compared E-ca
&RESHFEEDn-TD at constant fresh throughput, it is clear MAT
that ProtAgon-17C has a beneficial effect Vana
compared to the Brilliant catalyst, as Nick
Nick
Figure 3 Propylene production at constant fresh throughput shown in Figure 3. ProtAgon-17C offered
Yield
CEPSA the opportunity to open its
Tota
operating window, allowing an increase
Tota
in LPG yield at constant feed quality,
Tota
 maintaining LPG yield while using a Nap
"RILLIANT/LEFINS5LTRA more aromatic feed (Figure 4) or reducing LCO
0ROT!GONn# unit severity. Figure 5 shows the HCO
 evolution of the slurry yield, which has MCB
decreased steadily over time following Coke
the switch to ProtAgon-17C. Prop
Buta
,0'YIELDWT


Conclusion
The CEPSA Gibraltar-San Roque refinery Table
switched from a technology that utilised

an additive for propylene maximisation
to an integral catalyst system. The new
technology uses ProtAgon-17C, a
 propylene maximisation catalyst from
Grace Davison. This catalyst led to a
clear increase in propylene yield, while
 providing a lower hydrogen and dry gas
        make. It also allows CEPSA to process a
2EFRACTIVEINDEX
higher throughput or higher nickel-
containing feeds while avoiding
Figure 4 Comparison of LPG yield with feed aromaticity limitations in the fuel gas system.
Further benefits include a higher
conversion and a clear improvement in
bottoms cracking, which has resulted in
 historically low slurry yield values,
achieved at slightly lower catalyst

additions.

ProtAgon, Brilliant and OlefinsUltra are marks
4OTALSLURRY²# YIELDWT

of Grace Davison.


 Jose Maria Aguilar is FCC Plant Manager,

CEPSA Gibraltar-San Roque refinery, Spain.
 Maria Aguilar has a BS in chemistry from
Cádiz University.

J M Leon Gil is FCC Process Engineer,
CEPSA Gibraltar-San Roque refinery, Spain.

ProtAgon–17C Leon Gil has a BS in industrial engineering
 from Seville University.
Fernando Sanchez Arandilla is Regional
 Technical Sales Manager at Iberian
*AN *AN *AN
Peninsula, Grace Davison Europe. Sanchez
Arandilla has a BS in Chemical Engineering
from Granada University.
Figure 5 Evolution of slurry yield Email: fernando.sanchez@grace.com

20 PTQ CATALYSIS 2009 www.eptq.com

grace.indd 2 2/2/09 10:14:35

 E T H Y L E N E O X I D E C ATA LY S T S | H Y D R O G E N & S P E C I A L T I E S | S T Y R E N E C ATA LY S T S |
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ccc711_PTQ_sep07.indd 1 11/26/07 1:41:41 PM

cri 1 2/2/09 13:50:50
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Together with Eni, UOP has developed a feedstock-flexible

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uop.indd 1 2/2/09 13:52:29

 Reducing NOx emissions
from FCC regenerators
Case study demonstrates the performance of new technology for reducing NOx
emissions in regenerator flue gas. The new developments reduce NOx emissions
whether the FCCU is operating in full- or partial-burn mode
Ye-Mon Chen and David Brosten
T
he FCC regenerator is a major
NOx emission source in refineries.
Several existing technologies are
available to reduce NOx emissions from a
FCC regenerator, which include De-NOx
catalyst additives, selective catalytic
reduction (SCR) and selective non-
catalytic reduction (SNCR). Technology
recently developed by Shell Global
Solutions can be used as a standalone
strategy, to reduce NOx emissions to as
low as 40 ppm or less, or in conjunction
with one of the previously noted existing
technologies.
NOx formation
Most NOx emissions from FCC flue gas
come from nitrogen in the feed. The
contribution of direct oxidation of N2 to
NOx is negligible, particularly for full-
combustion FCC regenerators. For
partial-combustion regenerators, the
contribution of direct oxidation of N2 to
NOx is relatively small if low-NOx burner
technology is applied in the CO boiler/
incinerator.
A recent study shows1 that about 50%
of nitrogen in the feed exits the FCCU
on the reactor side, and the remaining
50% exits as coke on spent catalyst sent
to the regenerator. Of the 50% feed
nitrogen exiting from the reactor, about
10% ends up as ammonia, which is
collected in sour water, and the other
40% ends up in various streams of the
reactor liquid products.
This article focuses on the remaining
50% feed nitrogen, which enters the
regenerator in the form of coke on spent
catalyst. As the spent catalyst is
regenerated and coke is burned off in
the regenerator, the nitrogen species on
coke are released into the flue gas.
Recent studies1,2 further show that less
than 5% of feed nitrogen on coke is
released in the form of NOx emissions in
the flue gas. More than 45% of feed
nitrogen on coke is initially released in
the form of NOx or other intermediates,
but is converted in situ to N2 in the
regenerator.
A recent study2 of batch regeneration
www.eptq.com
shell.indd 1
Shell Global Solutions (US)
2.0
1.5
O2, CO, CO2 in flue gas, %
1.0
0.5
0.0
0 5
Figure 1 CO, CO2 and O2 in the flue gas as a function of time2
of spent FCC catalyst with oxygen and
helium reveals a close interaction between
the combustion of carbon and the release
of nitrogen in the coke. Figure 1 shows
the concentrations of CO, CO2 and O2 in
the flue gas as a function of time as coke
on catalyst is burned off in the batch
regeneration experiment. The amount of
coke on catalyst was not directly
measured, but Figure 1 implies that coke
on catalyst was removed continuously,
converted to CO/CO2 and became
negligible after 26 minutes, as both CO
and CO2 concentrations fell to negligible
levels. For the first nine minutes, the O2
concentration remained low and the CO
concentration was higher than CO2,
indicating a reduction environment in
this period of the batch regeneration. As
O2 broke through the unit at ten minutes
and its concentration continued to rise,
coinciding with a sharp drop in CO
concentration and a rise in CO2, the
batch regeneration shifted gradually from
a reduction environment to an oxidation
environment.
Figure 2 shows the concentrations of
NO, HCN and N2 in the flue gas as a
function of time as coke nitrogen is
released in the same batch regeneration
Measured O2
Measured CO
Measured CO2
10 15 20 25 30 35 40
Time, minutes
experiment. Most of the coke nitrogen
was released as N2, which peaked at 13.5
minutes at 200 ppm, under a reduction
or a slightly oxidation environment. A
fraction of coke nitrogen was released as
HCN, which peaked at 10.5 minutes at
35 ppm under the same environment.
The NO concentration was below 20
ppm for the first 14 minutes under a
reduction or slightly oxidation
environment when both coke on catalyst
and CO were present. NOx levels
increased sharply afterwards, and peaked
at 18 minutes at 190 ppm, when the CO
concentration fell to negligible levels
and the O2 concentration increased
beyond 1%, as shown in Figure 1.
The proposed reaction kinetics2 for the
release of coke nitrogen in the CC catalyst
regeneration process involves the initial
volatilisation of coke nitrogen as HCN,
which could be hydrolysed to another
intermediate, NH3. Both intermediates,
HCN and NH3, can be oxidised to NO,
which can be reduced to N2 by the
presence of CO or/and coke on catalyst.
Low-NOx regenerator
The FCC regenerator design has a direct
impact on the effectiveness of in situ
PTQ CATALYSIS 2009 23
2/2/09 10:18:46

250
200
HCN, NO, N2 in flue gas, ppm
150
100
50
0 (36) to fluidisation gas distribution ring
0 5
Figure 2 NO, HCN and N2 in the flue gas as a function of time2
2 24
46
48
Figure 3 Schematic diagram of the low-NOx regenerator system
reduction of NOx to N2, and hence the
reduction of the final NOx emissions in
the flue gas. The Shell low-NOx
regenerator technology shown in Figure
3 enables the unit to operate in both full-
and partial-combustion modes with low
NOx emissions.
As shown in Figure 3, the regenerator
system (1) includes a single regenerator
vessel (10) with an upper end (12) and
lower end (14). The regenerator vessel
(10) includes a dilute-phase catalyst zone
(16) above and a dense-phase catalyst
zone (18) below, with a transition surface
(20) between the two. The dense-phase
24 PTQ CATALYSIS 2009 www.eptq.com
shell.indd 2
zone by the introduction into the dense-
phase catalyst zone of more than one
fluidisation gas stream, each of which is
directed and controlled in such a manner
as to cause the formation of multiple
fluidisation regions. Thus, introduced
into the central portion of the dense-
phase catalyst zone is a high superficial
velocity fluidisation gas stream that
passes by way of conduit (30) to
fluidisation gas distribution ring or rings
Measured N2 (32) near the bottom of the regenerator
Measured HCN vessel. Introduced into the annular
Measured NO portion of the dense-phase catalyst zone
is a low superficial velocity fluidisation
gas stream that passes by way of conduit
10 15 20 25 30 35 40 or rings (38) located within the annular
Time, minutes portion near the bottom of the
regenerator vessel.
The controlled introduction of the
various fluidisation gas streams at the
different fluidisation gas flow rates along
1/2 with the directed introduction of the
56 fluidisation gas streams to desired
1
locations induces a desired circulation of
the FCC catalyst within the dense-phase
catalyst zone, as depicted in Figure 3 by
the bold arrows (40) that show the
general direction and circulation of the
58 12 FCC catalyst within the dense-phase
catalyst zone. As shown by the bold
arrows, catalyst particles in the high-
velocity central region move in a
60 generally upward direction, and catalyst
10
particles in the low-velocity annular
16 region move in a generally downward
direction. Catalyst from the bottom end
20
(42) of the low-velocity annular region
18 flows into the high-velocity central
region, and most of the catalyst from
24 2 the top end (44) of the high-velocity
44
40 40 22
28 26 28 central region flows into the low-velocity
39 40 40 39 annular region, thereby forming the
14
52 catalyst circulation within the dense-
42 phase catalyst zone.
38 The regenerator system further
36
38 includes the introduction of spent
32 32 catalytic cracking catalyst into the high-
30 54 velocity central region through conduit
(50), which can be a riser or a standpipe.
50 Connected to the end of the conduit is a
spent catalyst distributor (52) that
introduces spent FCC catalyst into the
high-velocity central region in a
horizontal direction and mixes with
catalyst zone further includes a high- catalyst circulating from the bottom end
velocity central region (22), located in of the low-velocity annular region. The
the central portion (26) of the dense- regenerated catalyst is removed from the
phase catalyst zone, and a low-velocity low-velocity annular region by way of
annular region (24), located in the conduit (54), which removes regenerated
annular portion (28) of the dense-phase catalyst from the annular portion of the
catalyst zone. It is a significant aspect of dense-phase catalyst zone.
the new regenerator technology that One advantage of the new regenerator
the high-velocity central region and the system is that the induced catalyst
low-velocity annular region are formed circulation pattern distributes partially
within the dense-phase catalyst zone regenerated spent catalyst to the
without the use of a structural element proximity of the surface (20), which
such as a vertical baffle or a partition. results in reducing NOx emissions from
The two fluidisation regions are instead the regenerator. Another advantage of
formed within the dense-phase catalyst the new regenerator system is that the
2/2/09 10:18:59
 location and the spent catalyst distributor
design induce intimate mixing between 
catalyst and transport air, thus preventing

transport air or entrained hydrocarbon
from breaking through the dense bed, 
which results in reduced afterburn. 

./X /PPM


Case study 
The new low-NOx regenerator technology

was implemented as an integrated part #ASE!
of a recent major FCC revamp. The  #ASE"
original FCCU was a large side-by-side  #ASE#
unit with a regenerator diameter greater  #ASE$
than 50 ft. The scope of the revamp 
included:       
— A new Shell PentaFlow stripper3 #/PCT
— Proprietary catalyst circulation
enhancement technology (CCET)4 at Figure 4 NOx emission in partial combustion under four cases of air distribution
the stripper outlet
— A new, larger air blower
— Additional pairs of regenerator
cyclones for handling higher air flow 
— The low-NOx regenerator technology
#ASE!
consisting of a new spent catalyst  #ASE"
distributor, new regenerator outlets with #ASE#
CCET, new air distributors and the  #ASE$
control system.
#/

Unit performance was measured 

before and after the revamp. Several key
performance improvements (Table 1) 
were observed:
— The unit feed rate was increased by 
9200 B/D compared to before the
revamp. Two most significant 
contributing factors are a higher coke       
burning capability, due to the new air
blower and the new regenerator
modifications, and a higher catalyst
circulation capability, up to 40% higher,
due to CCET
— The unit conversion was 4.2 vol%
higher than before the revamp at a
lower feed rate. When adjusted to the
same feed rate via model simulation, the
conversion was 6.4 vol% higher than
before the revamp. Two most significant
contributing factors are the new stripper
and CCET
— The unit was able to operate in both
full- and partial-combustion modes with
low NOx emissions after the revamp.
Figure 4 shows the NOx level in partial-
combustion mode under four different
air distribution conditions. As shown in
the figure, NOx emissions are the lowest
with Case D, with 40 ppm @ CO
concentration of 2.4%. The unit can
reach NOx levels lower than 40 ppm
under either lower CO concentration or
full-combustion mode with O2
concentration (<1%), not shown in the
figure. However, partial combustion
with CO concentration in the range of
2.0–3.5% is the preferred mode of
operation because of its capability to
increase unit feed rate
— The unit was also able to operate in
both full- and partial-combustion modes
with low afterburn and without the use
of CO promoter. Figure 5 shows the
afterburn, in the range of 45–65ºF, in
www.eptq.com
shell.indd 3
!FTERBURN²&
Figure 5 Regenerator afterburn in partial combustion under four cases of air distribution
Unit conversion comparison at base case prior to revamp
After revamp (measured) After revamp (simulated)*
Feed property Base case Base case
Catalyst Base case Base case
Feed rate, BBL +9200 Base case
Dry gas/H2S, vol% +0.12 +0.26
C3-gasoline, vol% +5.95 +8.4
LCO, vol% -3.51 -3.73
HCO/slurry, vol% -0.54 -2.38
Coke, vol% +0.41 +0.46
Conversion, vol% +4.2 +6.4
Volume gain, vol% +2.4 +3.0
* Unit performance adjusted, via model simulation, to the same feed rate as before the revamp
Table 1
partial-combustion mode under four air 3 Chen Y, et al, Stripper technology — how to
distribution conditions. The afterburn is get more profits from FCC units, AM-05-25,
2005 NPRA annual meeting.
insensitive to CO concentration, but 4 Chen Y, et al, Catalyst circulation
more sensitive to air distribution, with enhancement technology provides new
Case A having the lowest afterburn. opportunity for de-bottlenecking FCC unit,
2004 NPRA annual meeting.
This article is based on a presentation (AM-08-
16) from the 2008 NPRA Annual Meeting.
Ye Mon Chen is Global FCC Licensing
Technology Manager, Westhollow Research
References Center, with Shell Global Solutions (US) in
1 Rosser F S, et al, Integrated view to
understanding the FCC NOx puzzle, 2004 Houston, Texas.
AIChE Annual meeting. David Brosten is Senior Advisor, FCC
2 Stevenson S A, et al, Model of NOx emission Technology, Westhollow Research Center,
from laboratory regeneration of spent fluid
catalytic cracking catalyst, Ind. Eng. Chem. with Shell Global Solutions (US) in
Research, 2005, 44, 2966–2974. Houston, Texas.
PTQ CATALYSIS 2009 25
2/2/09 10:19:46
 We keep the world
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for further information

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 Impact of low-sulphur
bunkers on refineries
Proposed IMO global sulphur specifications on bunker fuels market and options
available to reduce fuel oil sulphur are reviewed. The impact of these options on
refinery operations are examined with case studies of a typical European refinery

Mike Stockle and Tina Knight

Foster Wheeler Energy Limited

T
he International Maritime
Organisation (IMO) recently
announced that it is supporting 
a move to a global sulphur specification

on bunkers of 0.5 wt%, with certain
environmentally sensitive areas moving 
Main Main delayed
to even lower sulphur levels. Foster 
3ULPHURWT

Wheeler has examined the impact this 

could have on a typical European refinery 
configuration and operation, with a

series of worked examples that focus
on various refinery configurations, and 
SECAs
shows how these configurations could be 
adapted to meet the new specifications. 
Changes to refinery operation in terms 
of blending and crude selection are            
considered, as are options for residue 9EAR
upgrading to meet a 0.5 wt% fuel oil
specification, or to move out of the fuel
market altogether. A view is taken of Figure 1 Proposed IMO bunker fuel specifications
what exactly should be considered with
the increased upgrading required to meet
0.5 wt% bunkers in terms of refinery
investment, price of bunkers and impact 
on other key refinery considerations "UNKERS
such as CO2 emissions.  )NLAND
This specification would present a
significant bunker fuels sulphur content 
reduction over the coming years, which
is why the potential impacts these 
changes could have on fuel oil markets
and on the operation and configuration
-4!


of refineries are discussed.

IMO targets
Proposed changes to the standard and

SOx emission control areas (SECAs)
bunker fuel specifications are shown in 
Figure 1. As can be seen, the proposed           
changes would see significant changes 9EAR Source: Wood Mackenzie
in fuel oil sulphur content, with the
allowable sulphur content in bunkers
reducing from 4.5–0.5 wt% (almost a Figure 2 World fuel oil markets
90% reduction) and the allowable level
in SECAs reducing from 1.5–0.1 wt% (an SECAs, as the two current SECA regions be seen that bunkers currently make
almost 95% reduction). These changes are the Baltic Sea and the North Sea and up about 30% of the world fuel oil
will give refiners a number of significant English Channel. market and that over the coming years
challenges, which will vary for each growth in bunker fuels is expected to
region and refinery. If adopted, they Fuel oil markets make up for declining inland fuel oil
could be particularly challenging for The world fuel oil markets for the sales to keep global demand fairly
European refiners, since much of coming years are shown in Figure 2, as constant.
Europe’s bunker fuel market will be into predicted by Wood Mackenzie. It can The changes in bunkers’ specifications

www.eptq.com PTQ CATALYSIS 2009 27

foster wheeler.indd 1 2/2/09 10:27:44






n

n
 n
n

n

3ULPHURCONTENT








BA PIS OS FISK GHT NT ITO VA ENT NIA AN PE NTE RALS AJA GHT AVY ND UM GHT ATA AYA AIT AVY
$O 4A RCAD %KO Y,I AS) +U A.O "R SCO URB 3LO RIE 5 INSK N,I (E S"LE :AK N, :U - +UW (E
O NN 4E X
&
"O 7
Figure 3 Typical fuel oil sulphur content for various crude oils
have the potential to seriously impact
the world fuel oil markets and may also
impact the markets for other transport
fuels as the changes to the fuel oil
markets impact them.
The biggest impact outside of the fuel
oil market is likely to be on the distillate
and diesel markets. At 0.1 or 0.5 wt%
sulphur in fuel oil it seems possible that
there will be a switch to distillate use, as
it will become increasingly difficult and/
or expensive to achieve the required
level of desulphurisation in fuel oil.
According to information from Wood
Mackenzie, current global demand for
bunkers is focused on Asia Pacific (38%)
and Greater Europe (33%). A proportion
of the demand will be in SECAs and this
low sulphur bunker demand will increase
if the number of SECAs increases.
Discussion of options
A number of potential options exist to
reduce either fuel oil sulphur content or
the amount of high-sulphur fuel oil
produced. Options considered are:
— Crude substitution
— Blendstock hydrotreatment
— Residue desulphurisation
— Residue hydrocracking
— Crude desulphurisation
— Fuel oil destruction.
Crude substitution
For most refineries, the sulphur content
of the fuel oil they produce is largely
controlled by the crude oil processed in
the refinery. Figure 3 shows the impact
of crude selection by considering a range
of 24 crudes and looking at the sulphur
content of a blend of vacuum residue
and 15% straight-run kerosene.
From this chart, it can be seen that the
reduction from 4.5–3.5 wt% will have
little impact on refiners, as most crudes
will be able to produce fuel oil below 3.5
wt%, and where crudes do show levels
28 PTQ CATALYSIS 2009 www.eptq.com
foster wheeler.indd 2
L so treating these streams has less impact
RR 6A - A. / H A N R R IA
4E K AC NI IA A PE AB
L AS " UZ )RA )RAN - 5P !R !RA
!
above 3.5 wt% they will either be
blended with lower sulphur crudes or
processed in full upgrading refineries.
This is further confirmed when you
consider that the IMO’s figures for
2004–2006 show an average sulphur
content for bunkers of around 2.7 wt%.
The change to a 0.5 wt% sulphur
specification will be harder to achieve,
with very few crudes being able to
produce a fuel oil meeting this
specification without some sort of
residue upgrading/desulphurisation.
For SECA bunker fuels, the
requirements are even tougher: the
current 1.5 wt% can be met by low-
sulphur crudes and the 1 wt% limit
should be achievable from some
refineries, but a 0.1 wt% specification
will be extremely difficult to achieve.
None of the crudes considered can meet
this specification from blending vacuum
residue (VR) and kerosene, and for many
crudes 0.1 wt% would not be obtainable
even with residue desulphurisation.
Realistically, to achieve 0.1 wt% sulphur
would require a move from using fuel
oils to using distillate.
Desulphurisation options
The obvious solution to reducing
sulphur in bunkers is to look at
desulphurisation options, including:
— Blendstock desulphurisation
Removing sulphur from the easiest to
treat blend components of the fuel oil
“Realistically, to achieve
0.1 wt% sulphur would
require a move from
using fuel oils to using
distillate”
— Pre-upgrading sulphur removal
For example, installing VGO
hydrotreating to reduce the sulphur
content of FCC, LCO and DCO
— Residue upgrading Direct
hydrotreatment of the hardest to treat
residue streams
— Whole crude hydrotreatment To
convert high-sulphur crudes to low-
sulphur crudes.
Blendstock desulphurisation
Blendstock treatment is the easiest to
achieve, as the sulphur species are the
easiest to remove and there are fewer
other contaminants. However, the
blendstocks are lower in sulphur anyway,
on the overall sulphur content of the
AN
BI pool. To illustrate this, we can consider
the impact on some of the typical fuel
oil blends mentioned earlier. For
example, if we look at a blend of 85%
VR and 15% kerosene for Urals crude,
the fuel oil has a sulphur content of 2.55
wt%. If the kerosene is desulphurised to
10 ppm, this drops to just 2.52 wt% — a
reduction of just over 1%. This means
blendstock desulphurisation is only
really practical where a refinery fuel oil
product is marginally higher than the
fuel oil specification.
VGO hydrotreatment
Pretreatment of feeds to upgrading units,
such as VGO hydrotreatment before an
FCC, offers more scope for reducing the
sulphur content of the fuel oil. FCC
products are often relatively high in
sulphur and make up a significant part
of the fuel oil pool. By removing the
sulphur from these fractions, the overall
pool content can be significantly
reduced. While VGO is more difficult to
treat than diesel or kerosene, it is still
much easier to treat than a full residue
stream.
Residue upgrading
The next option to be considered is full
residue hydrotreating, either in a fixed-
bed, ebullating-bed or slurry-bed reactor.
Residue hydrotreatment is the most
difficult of the processes considered for
sulphur removal, as the higher levels of
impurities present additional challenges
in terms of removing those impurities
and maintaining run lengths for
the units.
Whole crude hydrotreatment
The final option to consider is whole
crude hydrotreating. This is an area that
is being investigated by a number of
companies and offers the potential to be
able to process high-sulphur crudes as if
they were low sulphur. However, it is
not yet commercially proven and so is
not considered further within the scope
of this article.
For all of the options considered so
2/2/09 10:27:56
 far, additional hydrogen will be required
for the higher level of catalytic reactions ,0'
,0'-EROX
(such as desulphurisation, ,0'
demetallisation), and for many refiners
this will present its own challenges, as .APHTHA
their hydrogen balance is already

,0'
,T (
constrained. This problem becomes even ( 3&' NAPH
)3/-
more significant because residue
.APHTHA ( &' #S
upgrading or treating processes have .AP
.APHTHA 'ASOLINE

#$5
3PLITTER
much higher hydrogen demands than ($4 2EFORMATE
2EF 3PLITTER
distillate treating processes (even non- #RUDE ##2
(VY
catalytic processes such as coking require ( 3&'
NAPH
hydrogen to treat the coker products).
+ERO +EROSENE
As refiners begin to look at reducing the ($4 *ET
sulphur content of fuel oil, the options (

,0'
3&'
for producing and optimising hydrogen $IESEL
systems will be equally as important as $IESEL($4 $IESEL
the changes in configuration to upgrade ( 3&'
the fuel oil. ( 3&'

Fuel oil destruction options 6'/ ,#/ &## 4REATEDGASOIL

!TM &## GASOLINE
It is important to note, although not 2ES .APHTHA ($4
examined in this article, that should
6$5 ,#/$#/
proposed changes to the bunkers’ fuel !TMVACRESTOFUELOIL
specification happen, some refiners may 7. 3&'
find it preferable to stop producing fuel 62ES
'ASOIL
oil altogether. This means looking at 6ISBREAKER 2ESDUE (3&/
options that destroy fuel oil, either +EROSENETOFUELOIL
upgrading to other liquid products or $IESELTOFUELOIL
using it to produce power, steam or (3
3&' !MINETREATMENT 325 3ULPHUR
hydrogen.
&'
&UELGASSYSTEM ,0' (YDROGENPLANT (
Case study
As a base case, consider an FCC-based
refinery and the products and Figure 4 Base case refinery configuration
configuration of that refinery when
processing three different crudes:
Ekofisk, Urals and Arab Heavy. Consider Base case results for Ekofisk and Urals
how the configuration (Figure 4) and Crude Ekofisk Urals
product slate changes as the fuel oil Product slate BPSD BPSD
sulphur content is reduced, given LPG 17 824 17 036
configuration changes that include a Propylene 4587 4977
range of desulphurisation options. Gasoline 86 373 77 703
The potential price changes in bunkers Jet 8175
to make these schemes attractive will be Diesel 64 613 64 478
considered, and the impact the changes Fuel oil 20 413 38 459
could have on the carbon dioxide Coke
emissions from the refinery will also be Sulphur TPD 88 185
reviewed. Table 1 shows the key results CO2 emissions TPD 3822 4255
from the base case runs. Sulphur wt% of fuel oil 0.78 2.96
It can be seen from the results that Hydrogen plant TPD 0 0
the base case refinery running light
crude such as Ekofisk has no problems Table 1
meeting a 3.5 wt% sulphur specification
on export fuel oil. Urals crude also easily
achieves the 3.5 wt% limit. Arab Heavy, Results with VGO HDT added to configuration (FCC feed pretreatment)
on the other hand, cannot be blended to Crude Ekofisk Urals Arab Heavy
a 3.5 wt% fuel oil with this refinery Product slate BPSD BPSD BPSD
configuration and requires further LPG N/A 14 085 14 105
upgrading to meet the specification. Propylene N/A 4848 4028
This is not really a surprise, as Arab Gasoline N/A 77 757 69 238
Heavy is generally not processed as a Jet N/A 0 0
100% feed in the base case refinery Diesel N/A 64 165 21 323
configuration. Fuel oil 1.5 wt% N/A 773 0
Fuel oil 3.5 wt% N/A 37 781 90 036
VGO hydrotreater (HDT) Sulphur TPD N/A 262 342
The changes shown in Table 2 can be CO2 emissions N/A 5132 4791
seen when considering the addition of a Sulphur wt% of fuel oil N/A 2.52% 3.5 wt%/4 wt%
VGO HDT to the scheme for treating Hydrogen plant TPD N/A 93 64
FCC feed. A VGO HDT was added to the
refinery configuration and the fuel oil Table 2

www.eptq.com PTQ CATALYSIS 2009 29

foster wheeler.indd 3 2/2/09 10:28:06

 specification constrained to 1.5 wt%, as
per the current SECA requirements.
Ekofisk does not require further
%
upgrading to meet this reduced
specification, so the VGO HDT was not
required in this case. Adding a VGO
HDT to the Urals refinery allows it to
%
meet the 1.5 wt% specification in part.
Despite all of the VGO from the crude
unit being routed via the hydrotreater,
% only a small amount of 1.5 wt% fuel oil
can be produced. In order to meet this
"03$

specification, the 1.5 wt% fuel oil

% comprises around 62% distillate
components. The addition of the
hydrotreater to the Arab Heavy refinery
still does not allow the fuel oil pool (or
%
even part of it) to meet the 1.5 wt%
specification. Diesel components make
up 46% of the fuel oil pool to achieve
% 3.5 wt%, with a further grade at 4.0 wt%
"ASE 6'/($4 2ESID(#+ !2$3
needed to balance the pool.
,0' 0ROPYLENE 'ASOLINE *ET This demonstrates that removing
$IESEL WT&/ WT&/
sulphur from the FCC feed has only a
WT&/
small impact on the fuel oil sulphur
content and that, to make a step change
in fuel oil sulphur content, the sulphur
from the vacuum residue needs to be
Figure 5 Variation of product slate with desulphurisation options when processing removed.
Urals crude
Residue hydrocracking + VGO HDT
It is clear from the previous results that
the addition of further residue upgrading
Results with vacuum residue hydrocracking added to the configuration
would be required to meet a fuel oil
Crude Ekofisk Urals Arab Heavy specification of 0.5 wt%. The results of a
Product slate BPSD BPSD BPSD residue hydrocracker added to the
LPG 14 059 10 916 5515 refinery are shown in Table 3. From these
Propylene 4804 5860 5559 results, it can be seen that it is possible to
Gasoline 91 645 90 293 84 430 meet the 0.5 wt% sulphur specification
Jet 10 583 10 308 14 364 in fuel oil, but only by adding significant
Diesel 46 484 55 190 0 (and probably impractical) levels of
Fuel oil 0.5 wt% 34 251 10 778 75 392 distillates to the blend.
56% HDT distillates 75% HDT distillates 86% distillates
Fuel oil 1.5 wt% _ – – Residue desulphurisation
Fuel oil 3.5 wt% 18 801 13 849 The results of an atmospheric residue
48% distillates desulphurisation unit (ARDS) being
Sulphur TPD 89 274 637
added to the refinery to meet the 0.5
CO2 emissions 4088 5245 5999
wt% specification are shown in Table 4.
Sulphur wt% of 1.48 wt% 1.98 wt% 1.5 wt%
Ekofisk was excluded from the analysis,
refinery fuel oil 37% distillates 37% distillates
as from the previous example it has
Hydrogen plant TPD 0 314 676
been shown that residue upgrading is
not required to blend 0.5 wt% fuel oil in
Table 3 this case. In order to blend 0.1 wt% fuel
oil when processing Ekofisk, the LP
model selects an ARDS unit. It can be
Results with ARDS added to the configuration seen that the ARDS unit greatly reduces
Crude Urals Arab Heavy the amount of distillate blendstock
Product slate – – required to make the low-sulphur fuel
LPG 7813 2153 oil. Figure 5 shows how the product
Propylene 4977 4074 slate from a refinery processing Urals
Gasoline 81 380 72 801 crude varies with the different
Jet 1296 0 desulphurisation options.
Diesel 70 466 60 324
Fuel oil 0.5 wt% 30 886 57 445 Impact on carbon emissions
Fuel oil 1.5 wt% 0 0 Figure 6 summarises CO2 emissions from
Fuel oil 3.5 wt% 3550 0 the various refinery configurations.
Sulphur TPD 421 696 From this, it can be seen that the options
CO2 emissions 5146 6102 available to reduce sulphur in fuel oil
Hydrogen plant TPD 328 739 will result in higher CO2 emissions from
the refinery. This will present European
Table 4 refiners with further challenges as

30 PTQ CATALYSIS 2009 www.eptq.com

foster wheeler.indd 4 2/2/09 10:28:14

 

 %KOFISK
5RALS
!RAB(EAVY

#/TONNESDAY






"ASE 6'/($4
Figure 6 Impact of desulphurisation options on carbon emissions
emissions trading schemes come into
force and the level of allowable emissions
reduces. The proposed timing of the
changes in fuel oil specifications coincide
with the proposed timings for European
refiners moving from receiving free
emissions credits to having to buy credits
by auction, which this will only add to
the cost of reducing sulphur in fuel oil.
Summary and conclusions
The cases examined in this article
demonstrate that the proposed
reductions in sulphur specification are
achievable. However, for most refiners
to achieve the target specifications by
processing anything but the lowest
sulphur and most expensive crudes will
require significant investment in
desulphurisation technologies, or will
require significant levels of distillate to
be blended into the fuel oil pool.
If the specification changes take place,
they will have a number of impacts on
refineries and on the fuel oil markets.
One result of the changes in specification
could be to see a move away from fuel
oil to distillates, especially where SECA
regulations are in force. This will present
its own problems, as it will further
increase the pressure on distillate
production from European refineries
already under pressure to deal with a
shortfall in diesel production, and
increasing European diesel demand from
the dieselisation of the European
car fleet.
The changes to the fuel oil pool will
require significant investment by many
refiners if they wish to stay in the
bunkers market. The processes considered
are relatively capital intensive and a
typical European refinery of 200 000
BPSD (with VGO upgrading but no VR
conversion) could have to spend in
excess of $1 billion in order to upgrade
all of the fuel oil the refinery produces.
www.eptq.com
foster wheeler.indd 5
2ESID(#+ !2$3
To justify this level of investment and to
achieve an acceptable return on
investment, a significant increase in the
price of bunkers will be required, and
the work undertaken by Foster Wheeler
suggests the price of fuel oil would need
to be very close to that of diesel to
justify the investments required.
If it is assumed that all bunkers will
require desulphurisation, this would
require around 200 million tonnes per
annum of desulphurised or upgraded
residue. This equates to around 50–100
major upgrading projects around the
globe in the next 12 years.
The IMO’s plans for fuel oil are only a
proposal at the moment and the full
implications of the suggested changes
are still to be understood. However, it
does appear that they will present
refiners with some real challenges if they
are implemented as proposed. The
impacts on each refinery will depend
not only on where the specifications are
set, but also on the individual
opportunities open to that refinery. To
be ready to deal with potential reductions
in fuel oil sulphur, refiners need to start
investigating their options well ahead of
any changes.
This article is based on a presentation from
the November 2008 ERTC Annual Meeting in
Vienna, Austria.
Mike Stockle is Chief Engineer, Refinery
Technology, with Foster Wheeler Energy
Limited in the UK.
Email: michael_stockle@fwuk.fwc.com
Tina Knight is Process Engineer,
Downstream Business Solutions, with
Foster Wheeler Energy Limited in the UK.
Email: tina_knight@fwuk.fwc.com
www.ptqenquiry.com
for further information PTQ CATALYSIS 2009 31
2/2/09 14:12:36
ExperienceDifference-CE.qxd 3/2/06 4:52 PM Page 1

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sabin 1 2/2/09 13:53:39

 Continued gains in FCC
pretreating: part I
Case studies show where users are achieving significant gains in system capability,
flexibility and economics. Also discussed are catalyst system loadings that reduce the need
for low-activity demetallisation catalysts traditionally required to process heavier feeds
Desiree J De Haan, Andy Shivaram and Kevin D Carlson
Criterion Catalysts & Technologies
W
ithin the context of the
drive for clean fuels, shifting
product patterns and heavier
feeds, Criterion’s proprietary Ascent
catalysts are being increasingly used for
their ability to:
— Show greater stability in more severe
operations at higher temperatures and
lower pressures
— Be employed flexibly to select the
optimum fluid catalytic cracking (FCC)
pretreat operating strategy to maximise
FCC margins
— Process heavier feeds with more
contaminants
— Desulphurise, denitrify and saturate
to a high degree using lower amounts of
hydrogen
— Produce ultra-low sulphur diesel
(ULSD) and low-sulphur gasoline
— Work effectively and in conjunction
with mild hydrocracking catalysts in the
more severe operating regimes employed
for mild hydrocracking.
Clean fuels success
In complex and integrated refineries,
meeting stringent gasoline and ULSD
specifications has greatly increased the
impact of process unit interactions. This
move to clean fuels, continued increases
in crude pricing as well as shifts in
demand between motor gasoline and
diesel have required competitive refiners
to re-evaluate how to best utilise both
available refining assets and limited
capital budgets.
In vacuum gas oil (VGO) processing,
increases in hydroprocessing
performance have been achieved with
the Ascent family of catalysts. In today’s
refining environment of increasing feed
difficulty and contracting profit
margins, these improvements in
catalytic performance have allowed
refiners to review how to best utilise
their refining assets. Refiners who
are using the Ascent technology to
pretreat the feed for FCC operations are
realising significant benefits, from
extended periods between unit
shutdowns, increases in refinery yields
www.eptq.com
criterion.indd 1

 -AYACOKING 53'#
-ARSCOKING 53'#
 -ARSCRACKING 53'#
5RALSCRACKING %UROPE

"RENTCRACKING %UROPE

BBL



n
n
n
   
Figure 1 Past and current cracking and conversion margins. Source: IEA
to the capability to process more
difficult feeds.
FCC in a growing middle
distillate market
FCC continues to serve an important
role in the refining industry, with an
estimated 350–400 FCCUs in operation
today. Improvements in technology and
catalysis have increased the conversion
level of VGO feedstocks into more
valuable middle distillates, gasoline and
olefin products. Ongoing market changes
in pricing and product demands have
raised questions over how best FCC
assets can be utilised.
While FCC yields vary based on feed
quality and process conditions, typical
operations yield 50–60 vol% gasoline
and 15–20 vol% light cycle oil (LCO)
from a VGO feed. Prior to widespread
clean fuels introduction, similar pricing
for both gasoline and distillate products
provided strong incentives for FCC
conversion, producing both gasoline
and distillate from the low-value fuel oil
pool. Continued demand growth for
low-sulphur diesel, however, has
increased the low sulphur diesel margins,
thereby making gasoline production less
desirable in some markets.
Globally, both increased coker
capacity and increased processing of
       
heavier crudes have resulted in the
higher production of lower value,
difficult VGOs more suited to the FCC
pretreat/FCC complex than a
hydrocracking unit due to the high level
of feed contamination.
In addition to reviewing how to best
optimise FCC operations, Criterion is
working with various refiners to increase
their middle distillate yield from the
FCC pretreat/FCC complex by increasing
VGO conversion in the FCC pretreat
(PT) unit through modified operating
strategies or catalyst systems.
Need for higher activity and
stability in pretreatment
Success in the pretreatment of FCC feed
is a function of both catalytic performance
and catalyst stability. Since being
introduced to the market in 2006, Ascent
catalysts have been selected globally in
over 50 applications involving VGO
treatment. Commercial success has been
measured by improved FCC operations,
longer catalyst cycle lives and the ability
to process more difficult feeds. Ascent
catalysts are manufactured by a process
providing enhanced promoter metals
utilisation through an optimised catalyst
physical structure designed to better
tolerate the contaminant metals present
in heavy gas oil feeds.
PTQ CATALYSIS 2009 33
2/2/09 10:30:00
 compared to other cobalt molybdenum
(CoMo) catalysts and provides high
 contaminant metals (nickel, vanadium,
/THERMETALS silicon) tolerance. Due to its high HDN
-ETALSONSPENTCATALYSTFROMBASIS WT

 3ILICON and aromatic saturation capability, it is

.ICKEL able to overcome the FCC conversion

6ANADIUM loss typically associated with CoMo
catalyst application.
The use of either of these two catalysts,

separately or in a combined system, can
be tailored to the FCCU objectives of
 margin improvement. The FCC PT unit
can be operated for targeted
 desulphurisation, denitrification,
maximum polynuclear aromatics (PNA)

saturation or to effect some mild
$.n 6'/$EMET $.n 2ESID$EMET $.n hydrocracking.
Commercial unit 1 Commercial unit 2 In addition to high feed contaminant
metals tolerance, the Ascent technology
produces catalyst with improved
tolerance to thermal-based deactivation.
Figure 2 Improved metals uptake capacity of Ascent DN-3551 This allows for reduced deactivation
rates at higher temperatures (see Case
studies 1 and 2) and lower hydrogen
partial pressures, leading to longer cycle
 lives in FCC PT units. This improved
380°C 395°C 410°C
 stability of Ascent catalysts at high
N7!"4²#FOR($3

Type II catalyst temperatures is particularly useful in


operations that wish to increase middle
 distillate production through mild
hydrocracking by operating at elevated

temperatures (to be discussed in more
Ascent DN–3551
 detail in part II).
 Also to be discussed in part II are
examples of Ascent catalyst being used

        to make ULSD and low-sulphur gasoline
Figure 3 Accelerated ageing test comparing Ascent stability to Type II catalyst
Ascent DN-3551 is the most active
FCC PT nickel molybdenum (NiMo)
catalyst. It is well suited to high-severity
FCC PT operations, providing high
contaminant metals tolerance while
performing a high degree of denitrifi-
cation (HDN), desulphurisation (HDS)
and aromatic saturation (HDA) —
reactions critical in FCC feed quality
upgrading (to be discussed in more detail
in part II of this two-part article). Ascent’s
DN-3551 NiMo catalyst is designed to
achieve very high FCC feed PT to help
meet tighter specifications
downstream FCCU operation and
product slate (see Case study 2). It can be
supplied in an oxide (non-presulphurised)
form and provides the advantage of
being able to employ conventional
handling and start-up procedures and
conventional ex-situ regeneration for
reuse in the same or lower severity
service. The Ascent manufacturing
technology produces inherently stronger
catalysts that improve recovery during
regeneration.
Ascent DC-2551 features similar
performance, stability and regenerability
to Ascent DN-3551. It is well suited to
severe FCC PT operations that value a
2UNHR
high desulphurisation performance
while reducing the operational hydrogen
requirement (to be discussed in more
detail in part II). Its design promotes
increased HDN and aromatics saturation
Feed and operating conditions
Catalyst system DN-3551 NiMo
LHSV 0.9 hr-1
Capacity 411 m3/hr
Pressure 82 bar
H2/oil 550 m3/m3
on
Feed type SR GO, SR VGO & 20% HCGO
Feed
S.G. 0.924
Sulphur, wt% 2.2
Nitrogen, wppm 2400
Concarbon, wt% 0.6
Feed metals, pwwm <3
D2887 10% - C 332
D2887 95% - C 543
Product GO
S.G. 0.866
Sulphur, wt% 0.20
Nitrogen, wppm 1200
Concarbon, wt% <0.3
Feed metals, pwwm <0.3
Table 1
directly from the FCC PT unit.
Figure 2 shows the improved metal
uptake capacity of Ascent catalyst when
compared to demetallisation catalysts
and the previous generation of FCCU PT
catalyst DN-200.
Figure 3 shows the comparative
performance in a medium-pressure,
accelerated ageing catalyst test of Ascent
catalyst vs a Type II catalyst. In this test,
the feed and conditions were chosen to
accelerate the ageing of the catalyst so
that comparative results could be seen
in a shorter time.
Case study 1
Extend cycle life in FCC PT unit
Low deactivation rates have been
achieved at a refinery that has been
operating with Ascent DN-3551 for over
one year, following successful runs with
previous generations of Criterion
catalysts. Processing a challenging mix
of crudes and coker feeds, this unit is
currently achieving excellent
performance with less than half of its
previous cycle deactivation rates. The
observed superior catalyst activity and
stability allow for an extended unit run
length, reduce days off stream due to
catalyst change-outs and process
economically attractive opportunity
feeds. Table 1 and Figure 4 give the
details of feed operating conditions and
performance.

34 PTQ CATALYSIS 2009 www.eptq.com

criterion.indd 2 2/2/09 10:30:11

 Case study 2
Houston Refining
Employing Ascent systems in its FCC PT
helped Lyondell Houston Refining ($3ACTIVITYPREVIOUSSYSTEM
($3ACTIVITY!SCENTSYSTEM
(HRLP), in Houston Texas, to meet the

.ORMALISED($37!"4
clean fuels challenge successfully and
reliably producing Tier II gasoline and
ULSD since early 2006. The addition of
hydroprocessing capability in FCC
naphtha and the expanded capability of
the diesel and heavy gas oil hydrotreating
units have not only allowed Tier II
compliance, but also increased overall
facility performance through operational
flexibility and yield improvements. To           
achieve this, a catalyst system is required $AYSONSTREAM
that has both excellent stability and
good performance under varying
process conditions. ($3ACTIVITYPREVIOUSSYSTEM
One particular area of focus is ($3ACTIVITY!SCENTSYSTEM
optimisation of the FCC feed
.ORMALISED($.7!"4

hydrotreaters (ie, FCC feed PT) to best

manage clean fuels production while
maximising FCC performance. Industry-
wide, the emphasis of FCC feed
hydrotreating has been to provide a
constant product sulphur to meet
previous gasoline specifications or on
the removal of contaminants (nitrogen,
polynuclear aromatics (PNA), metals
and concarbon) that reduce FCC           
conversion. Prior to the requirement of $AYSONSTREAM
30 ppm sulphur gasoline, FCC feed
hydrotreater optimisation resulted in Figure 4 HDS and HDN stability performance of Ascent catalysts: lower deactivation
balancing the economics of catalyst rates are achieved with DN-3551 compared to previous cycle with an older
cycle life and FCC conversion. generation Criterion catalyst, allowing longer cycles
The recent change in gasoline sulphur
requirements resulted in many refiners,
including HRLP, installing post-FCC
gasoline hydrotreating technology to
($3ACTIVITY#ENTINEL'OLDSYSTEM
meet this mandate. Due to addition of
($3ACTIVITYCURRENT!SCENTSYSTEM
the new post-FCC gasoline hydrotreater,
0RODSULPHUR 0RODSULPHUR
HRLP has shifted away from FCC feed
.ORMALISED($.7!"4

sulphur targets, requiring the refinery to

revisit how to best operate the clean
fuels system as a whole. This evaluation
included accessing the effects of FCC
feed hydrotreating severity on FCC <1 C /mo deactivation
conversion and yields as well as its
impact on the ULSD hydrotreaters.
Awareness and understanding of the
interactions between the FCC feed
hydrotreaters, the FCCU and the ULSD           
unit were key to implementing a $AYSONSTREAM
successful clean fuels strategy.
An important element of hydro- Figure 5 Stability and activity increase observed in unit 634
treating improvements at HRLP was
significant increases in hydroprocessing Key unit parameters for the FCC feed hydrotreaters
performance of the Ascent family of
catalysts. Working together with Unit 634 Unit 636
Criterion, HRLP reviewed a number of LHSV 2.0 hr-1 1.2 hr-1
operational strategies and FCC feed Pressure 61 bar 95 bar
hydrotreater unit technology H2/oil 185 m3/m3 225 m3/m3
improvements to better position itself Feed type SR VGO SR VGO & 50% HCGO
for operation in the future. Currently, Feed
HRLP operates two FCC feed units: 634 S.G. 0.935 0.951
(Figure 5) and 636 (Figure 6). Key unit Sulphur, wt% 2.0 2.4
parameters are shown in Table 2. Figure D2887 EP% - C 602 593
5 illustrates how observed gains in Hydrogen consumption 76 Nm3/m3 110 Nm3/m3
Ascent catalyst activity and stability
have increased both units’ capability to Table 2

www.eptq.com PTQ CATALYSIS 2009 35

criterion.indd 3 2/2/09 10:30:28

 between increased FCC conversion and
increased FCC feed hydrotreater cycle
length. With a plan to operate in PNA
($3ACTIVITY#ENTINEL'OLDSYSTEM 3.6 C /mo deactivation
($3ACTIVITYCURRENT!SCENTSYSTEM
mode, PNA-HDN mode is a useful
0RODSULPHUR 0RODSULPHUR secondary option to allow for some
flexibility in turnaround timing. In the
.ORMALISED($.7!"4

second half of 2007, the refinery

implemented a plan to run both units
634 and 636 in PNA saturation mode.

<1.7 C /mo deactivation

This article is based on a presentation from the
2008 ERTC In Vienna. Ascent (ASCENT) is a
mark of Criterion Catalysts & Technologies.

          

$AYSONSTREAM
Figure 6 Stability and activity increase observed in unit 636
produce improved FCC feed quality
while providing longer cycle lengths.
HRLP worked together with Criterion
to determine how to take full advantage
of the facility’s capabilities. Several
potential operating modes were
examined, including HDS mode, HDN
mode, PNA saturation mode and a
combination PNA-HDN mode. The cycle
length and turnaround cost impact for
each mode were considered along with
the downstream effects of each mode.
Table 3 shows the four operating
strategies that were considered along
with the characteristics, advantages and
disadvantages of each.
The advantages and disadvantages of
each of the four operating mode options
were considered in an economic analysis.
The economic evaluation included
amortised catalyst replacement cost and
turnaround cost for each mode, as well
as FCC conversion shifts for the predicted
FCC feed quality in each mode. Given
constantly changing market economics
and refinery conditions, the economic
advantage of one mode over another
fluctuates, but HRLP’s economic analysis
indicated a consistent and significant
advantage to run in PNA mode over
HDS mode or HDN mode. While PNA-
HDN mode is less economically attractive
than PNA mode, PNA-HDN mode
provides a reasonable compromise
Desiree J de Haan is Technical Consultant,
FCC Pretreat/Mild Hydrocracking, with
Criterion Catalysts & Technologies covering
units in the EMEAR region. de Haan is
a graduate from Uterecht University in
inorganic chemistry and catalysis.
Email: D.DeHaan@cri-criterion.com
Andy Shivaram is Technical Manager, FCC
Pretreat/Mild Hydrocracking, with Criterion
Catalysts & Technologies in Fareham
Hampshire, UK. Shivaram is a graduate
of chemical engineering from Cambridge
University.
Email: Andy.Shivaram@cri-criterion.com
Kevin D Carlson is Global Business
Manager, FCC Pretreat & Sentry Products,
with Criterion Catalysts & Technologies
in Houston, Texas. He has worked in the
industry for over 18 years and has been
an author of a number of technical papers.
Email: Kevin.Carlson@cri-criterion.com

FCC feed hydrotreater operating strategies

Mode HDS HDN PNA PNA-HDN
Description Operates throughout Operates throughout Operates throughout Operates for most of
cycle to target cycle to target cycle to maximise cycle to maximise PNA
sulphur removal nitrogen removal PNA saturation saturation; near the end
of cycle, operates to a
Figure
6: Stability Increased Observed
in Unit 636 secondary (nitrogen) limit
with lower PNA saturation

Cycle life 18 months 15 months 10 months 14 months

(for unit 634)
WABT trend Gradual increase Gradual increase Rapid increase over first Rapid increase over first 1–2
over cycle over cycle over cycle 1–2 months, then slow months, slow increase
increase throughout throughout PNA mode, then
cycle rapid increase in HDN mode

Advantages Longest cycle life, Simple to implement, Best feed quality for FCC Longer cycle life than
simple to implement better FCC feed quality conversion, consistent FCC PNA mode, best overall for
than HDS mode feed quality, achieves high balancing cycle and FCC
sulphur and nitrogen removal, feed quality
resulting in improved
unit 633 cycle life and/or
increased LCO upgrade to ULSD

Disadvantages Suboptimal FCC feed quality Suboptimal FCC feed quality Shortest cycle life Declining FCC feed quality
throughout most of cycle, throughout most of cycle, at end of cycle
results in lowest FCC conversion, better FCC conversion
higher LCO yield and than HDS mode
higher LCO product (negative
impact on unit 633 cycle and/or
LCO recovery to ULSD)

Table 3

36 PTQ CATALYSIS 2009 www.eptq.com

criterion.indd 4 2/2/09 10:30:40

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 Mercury removal in
hydrocarbon streams
The presence of mercury in refinery hydrocarbon streams results in detrimental effects,
including catalyst poisoning, corriosion and safety issues. Absorbent technology for
effective mercury removal is described with case studies and actual operating experience
M
ercury is found in an ever-
increasing number of hydro-
carbons worldwide. The
level of mercury can vary significantly,
depending on location. The situation is
complex in refineries, as liquid feedstocks
can contain elemental, organic and
inorganic species. Complete removal of
mercury is advisable to avoid catastrophic
failures in cryogenic equipment, to
prevent poisoning of process catalysts,
and for health and safety reasons.
Additionally, hydrocarbon products
that can be labelled as mercury free are
able to command an enhanced product
value. For example, mercury-distressed
naphtha may be sold at $5–10 less than
open-spec naphtha.
There are now over 250 proprietary
Puraspec mercury removal units (MRUs)
in service on a range of hydrocarbons,
with more than 100 units in commercial
operation on liquid applications. The
new generation of Puraspec absorbents
have been shown to give effective
removal and long life without impacting
negatively on product quality.
Mercury in hydrocarbons
Almost all hydrocarbons contain
mercury. In the case of natural gas and
natural gas liquids, it is likely to be
present as elemental mercury. In the
case of crude oil, it may also be present
as organo-metallic and ionic mercury.
The concentration of mercury in natural
gas varies widely from 450–5000 µg/Nm3
in some fields in North Germany to less
than 0.01 µg/Nm3 in some parts of the
US and Africa.1 Much higher levels of
mercury can be found in crude oil.2
Levels found in some crude oils are
shown in Table 1.
Elemental mercury is only sparingly
soluble in liquid hydrocarbons3 (the
solubility in n-octane at 25°C is 2 ppm),
so the high levels recorded show that
mercury compounds must also be
present.
Mercury has a high boiling point
(356.7°C), but has a high vapour
pressure at ambient temperature and is
www.eptq.com
j mathey.indd 1
Steve Catchpole
Johnson Matthey Catalysts
Reported levels of total mercury Level of mercury in refinery products
in crude oil
Product Amount, ppb w/w
Source Amount, ppb w/w LPG <10
California (Cymric) 30 000 Gasoline 0.22–3.2
Alberta 2–400 Diesel 0.4–3
North Sea 2.5–9.3 Naphtha 3–60
Libya 0.1–12.2 Petroleum coke Up to 250
West Africa 1.5–3.5
Angola 1.5–2.7 Table 2a
Table 1 distribution of mercury. These data are
summarised in Table 2b.
surprisingly mobile. Organo-mercury Due to its ability to manifest itself in
compounds are easily broken down practically all of the crude column
when heated in a reducing atmosphere, products, mercury will be found in a
and elemental mercury is released number of downstream unit operations.
during the hydrotreating and catalytic Figure 2 shows the measured distribution
reforming stages of the refinery. in a FCC/resid cracker, and Figure 3
As a result, whatever the original form shows the measured distribution in a
of mercury in the crude oil feed to hydrocracker of a typical world-scale
the refinery, much of it ends up as refinery.
elemental mercury in the C3 to C6 Although the levels of mercury
product streams; namely, LPG, gasoline recorded are low, the tonnages of liquid
and naphtha.2,4 hydrocarbons handled are enormous, so
Published levels of mercury found in downstream processing equipment is
refinery product streams are shown in exposed to a substantial amount of
Table 2a. Figure 1 displays the measured mercury. The main worries are corrosion,
distribution of mercury in the crude feed poisoning of catalysts, and health and
and product streams of the crude column safety. These can involve serious
of a major world-scale refinery. It is also financial losses.
worthwhile to note the prevalence of
mercury in the water effluent of the Corrosion
desalting operation. Mercury readily wets most surfaces and
Data derived from world-scale forms amalgams with a number of
refineries shed additional light on the metals. A particular concern is
Measured mercury distribution in world-scale refineries
Refinery Mercury level in the Mercury level in the Mercury level in the
crude, ppb w/w naphtha, ppb w/w lpg, ppb w/w
1 – 100–200 >10
2 – 50–100 750
3 – 5–10 –
4 – 1 –
5 1200 30 –
6 >5000 <1000 –
7 – 100 –
8 – 1000 500–1000
9 – 150 –
Table 2b
PTQ CATALYSIS 2009 39
2/2/09 10:34:22
 aluminium, because it is widely used in
cryogenic heat exchangers. This is a
Pipeline
potentially reactive metal protected
Storage
from attack by air and water by an oxide
layer. If the protective oxide layer is
Overhead Overhead damaged (say, by a small scratch) and
drum drum
liquid mercury is present, an amalgam is
Water formed, which will allow rapid reaction
3-5 6-8 with air or water:
11-14
ng/nm3 Sour water stripper
440-500 Sour water Hg + Al → Hg(Al)
9-15
stripper ppb wt
45-65
ppb wt ppb wt Hg(Al) + 6H2O → Al2O3.3H2O + H2 + Hg
15-25 ng/nm3
ppb wt
Aluminium heat exchangers are
ppb wt 1
ppb wt particularly vulnerable during de-riming
1-2 Pumparound
3-4 and start-up and shutdown. Since the
catastrophic failure of an aluminium
Desalter
heat exchanger at Skikda in 19755 there
ppb wt 1-2 ppb wt have been many reported incidents.5,6
Naphtha
5-7 The most recent was the Santos onshore
Preflash gas facility in 2004, when there was a
15-16 ppb wt
Kerosene massive blast and fire in the liquids
recovery section, resulting in the
Crude 3-4 ppb wt
shutting down of gas supplies.
column Diesel Mercury can also cause liquid metal
embrittlement (LME). This can occur in
the absence of water and produces rapid
brittle fracture. Mercury can diffuse into
the grain boundaries to form a liquid
Liquid Hg content
ppb wt amalgam. The cracks produced propagate
Gas Hg content
4-5 Atmospheric along the grain boundary. This type of
residue corrosion affects a broad range of
materials such as aluminium alloys,
copper-based alloys and some types of
Figure 1 Measured mercury distribution — crude distillation column steel. LME is particularly worrying

'AS

7ETGAS
COMPRESSOR #S
/VERHEAD
DRUM WGC
suction
  PPBWT
drum
Regenerator #S
37
PPBWT
  !LKY
&EED FEED
DRUM 3OUR
WATER
  PPBWT
Reactor .APHTHA 
PPBWT
!LKY
'ASOLINE
  PPBWT ALKYLATE
,IGHTCYCLEOIL
Main PPBWT
fractionator   NGNM
 
  PPBWT .APHTHA
(EAVYCYCLEOIL

PPBWT
,IQUID(GCONTENT
 
'AS(GCONTENT 3LURRY

Figure 2 Measured mercury distribution — FCC/resid cracker

40 PTQ CATALYSIS 2009 www.eptq.com

j mathey.indd 2 2/2/09 10:34:33

 because it is difficult to detect prior to
failure under pressure. 'AS
Corrosion is a particular concern for
LNG plants, so a mercury limit of less
PPBWT
than 0.01 µg/Nm3 is set on the feed.
 3OUR
Similarly, ethylene cracker plant WATER
operators favour their hydrocarbon feed
to contain less than 5.0 ppb of mercury,
and the same limit is set for the low
temperature storage of LPG. Debutaniser
More recently, following the move to PPBWT
ultra-low sulphur fuels, there are Hydrocracker  ,IGHT
concerns about corrosion of auto fuel reactor NAPHTHA
PPBWT PPBWT
meters and pumps.   
&EED (EAVYNAPHTHA
Poisoning of catalysts
Precious metal catalysts such as platinum PPBWT
and palladium are particularly prone to Pretreat
 
+EROSENE
poisoning by mercury. They react to reactor
form a 1:1 amalgam (ie, PtHg or PdHg)
that is stable at the low temperatures PPBWT
used in hydrogenation. Levels as high as  
2000 ppm have been found on the top ,IGHTDIESEL
Main
of 0.05% palladium acetylene fractionator
hydrogenation catalyst. True, the PPBWT
mercury can be driven off by heating  
(EAVYDIESEL
above 150–200°C, but this accelerates
sintering and hence loss of active
surface area.
PPBWT
Just over half of the world’s 500 ,IQUID(GCONTENT
 
ethylene crackers use naphtha feedstock 5NCONVERTEDOIL
'AS(GCONTENT
and, to avoid damage to the precious
metal ethylene purification catalysts, a
mercury limit is set. This varies from
5.0–1.0 ppb and is set by the operators.8 Figure 3 Measured mercury distribution — hydrocracker
So-called distressed naphtha is traded
with difficulty and at a $5–10/tes lower
price than open-spec naphtha.
A study of the hydrogenation of 100
benzene with a platinum catalyst has
found that only 5% coverage of the
active sites results in an 80% loss in 90
activity (Figure 4).7
80
Health and safety
Mercury is a toxic metal with a relatively
high vapour pressure. Consequently, 70
upon opening mercury-contaminated
equipment, workers will be exposed to
60
Relative reactivity %

mercury vapour levels well in excess of

the threshold limiting value (TLV) or the
maximum allowable concentration 50
(MAC).9,10 Suitable protective personal
protective equipment is required during
40
maintenance work. Mercury-
contaminated pipe work and vessels
may be classified as hazardous waste and 30
cannot be treated as ordinary scrap
iron.
Concern is now being shown over the 20
health hazard of mercury released to the
atmosphere, as it can undergo bio- 10
methylation reactions to form highly
toxic organo-mercury compounds such
0
as dimethyl mercury (DMM) that cause 0 20 40 60 80 100
severe renal and nerve tissue damage.
Extent pt/Hg formation, %
This was the reason for the tragic events
in Mina Mata Bay in the 1950s. The EU
has set up a working party to draw up
guidelines on acceptable levels for Figure 4 Effect of mercury on the rate of hydrogenation of benzene with a
mercury emissions to the atmosphere. platinum catalyst

www.eptq.com PTQ CATALYSIS 2009 41

j mathey.indd 3 2/2/09 10:34:42

 The EU has already issued directives Modern thinking has moved towards
banning the disposal of wastes Solubility of sulphur in liquid the inorganic route used in Puraspec
containing mercury by landfill hydrocarbons reactors for the removal of mercury
(Directives 99/31/EC and 2002/95/EC). Hydrocarbon Solubility, ppm w/w from gaseous and liquid hydrocarbons.
Pentane 300 This relies on the high reactivity of
Analysis Heptane 500 mercury with the metal sulphides of
A number of analytical techniques are Toluene 2500 certain variable valency metal
capable of measuring mercury down to sulphides:15
ppb levels. However, strict procedures Table 3
have to be followed to obtain accurate Hg + MxSy → MxSa + HgS
and reproducible results. optical emission spectroscopy (ICP-
Mercury is easily lost to sample lines OES).12 The reactive metal is incorporated in
and, in the case of liquids, on container Neutron activation analysis (NAA) is a an inorganic support and the absorbent
walls. Sample lines should be lined and sensitive analytical technique that can is supplied with reactive sulphide
as short as possible, and should be well be applied to liquid and solid samples. A present, or this is formed in situ by
purged to allow equilibration. Liquid weighed amount of the material to be reaction with H2S in the hydrocarbon to
samples should only be taken in glass or analysed is irradiated with neutrons in a be treated. The inorganic approach has a
ceramic-lined containers, as mercury nuclear reactor. This creates a number of number of advantages over the sulphur-
will plate out on metal surfaces. radioactive isotopes. Each isotope has its impregnated carbon approach:
Atomic fluorescence spectrometry is own characteristic decay pattern that — The spent mercury absorbent can be
now the method of choice for mercury can be used for both detection and recycled through metal smelters. This is
measurements in gases. The PSA Sir measurement. made possible by the use of a
Gallahad II is a typical instrument used Unfortunately, mercury is not the combination of metals with an
for mercury measurements.11 For gases, a easiest element to measure using this inorganic support that is compatible
known volume is passed over a gold technique, but with care it is possible to with smelting processes
trapping tube to concentrate the carry out measurements down to 5.0 — The materials can be used on wet
mercury. Gas at high pressure may need ppb. A particular attraction of this and dry gases
to be let down through an electrical technique is that it is possible to collect — The reactive species and the support
heated regulator to avoid condensation a sample on a remote location and have mesoporous structures with little
of liquids during depressurisation. courier it to a laboratory without affinity for hydrocarbons. There is little
Mercury is desorbed from the collector concerns of loss of mercury on container risk of capillary condensation even
tube by heating to 800°C with a carrier walls during handling. when used with gases at very high
gas for passage into the analyser. The Speciation of organo-mercury pressures (120+ bar)14
technique can be modified to measure compounds is a very specialised science — There is no risk of sulphur migration
mercury in liquid streams by using an requiring sophisticated gas chroma- by sublimation or dissolution
attachment to vapourise a measured tographic equipment, and most of this — The absorbents can be used to
volume of liquid over a collector. type of work is carried out at universities process liquid hydrocarbons.
Solid and liquid samples may also be and research establishments. Fortunately,
measured using a pretreatment process organo-mercury compounds occur only Mercury removal
such as that employed by a Leco rarely on gas processing plants. They are units (MRUs)
AMA254. This uses direct analysis of a more likely to be encountered in heavy Johnson Matthey has supplied over 250
combusted sample in a stream of oxygen. crude oil, but are likely to be broken MRUs for a range of duties from natural
Oxides of nitrogen and sulphur are down during refining. gas through NGLs to relatively high
removed on a catalyst tube and the molecular weight hydrocarbons. These
mercury is collected on a gold Mercury removal processes use fixed-bed absorbents that may be
amalgamator. This is reheated to desorb Operators have long been aware of the pre-activated or self-activating to give
the mercury for measurement on an presence of mercury in liquid mercury loadings in excess of 15 %w/w.
atomic absorption cell. The instrument hydrocarbons, but until relatively The reactor design may use axial flow
needs to be calibrated with a standard recently lacked the means to remove it. or radial flow to minimise pressure
reference material, typically an organo- Carbons doped with sulphur or drop, and the long bed life coupled
mercury compound in cyclohexane. potassium iodide have been tried, but with minimal need for operator
This can handle liquid samples of 50 µl are not really suitable because of the loss attention provides the ideal fit-and-
and solids of 5–100 mg to measure of sulphur by dissolution in the liquid forget solution for mercury removal.
mercury levels down to 2 ppb. Levels of hydrocarbons and of iodide in water.13
mercury higher than 1000 ppm can be They are also difficult to dispose of in an Design and location of MRUs
measured by inductive coupled plasma- environmentally satisfactory way. Some thought needs to be given to the
location of the MRU. Due to the high
mobility of mercury, it is better to
Typical examples of mercury removal units on liquid hydrocarbons remove it as near to the source as
possible. Thus, on a gas processing plant
Location Hydrocarbon Rate, t/hr Start-up Mercury content, ppb w/w
or LNG plant, placing the MRU on the
UK LPG 75 1997 60
feed gas will avoid mercury in the
M. East Condensate 2 x 164 1999 10
Far East LPG 182 2000 292 product streams or mercury being
Far East Naphtha 14 2002 20 released from the acid gas removal and
Far East Naphtha 0.22 2002 385 drying units.
UK Naphtha 130 2003 100 Location of the MRU on the naphtha
UK Naphtha 120 2004 150 feed to a cracker will give protection to
Netherlands Condensate 80 2004 300 the cryogenic units and precious metal
UK Naphtha 156 2005 60 catalysts on the product streams. This
also removes any concern over the
Table 4 formation of metal acetylides.

42 PTQ CATALYSIS 2009 www.eptq.com

j mathey.indd 4 2/2/09 10:34:52

 - TRICAT

Main Products
 Regeneration of spent catalysts
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tricat.indd 1 30/1/09 14:33:48

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www.ptqenquiry.com

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for further information

oilandgas.saint-gobain.com

norpro 2 copy 1 2/2/09 13:55:52

 All fixed-bed reactors risk being fouled
by solid matter, so they should only be
used on the cleanest of crude oil and
NGLs. For this reason, they are most
suited to being used on the refinery
product streams rather than crude oil as
supplied. Typical examples of MRUs
supplied by Johnson Matthey are given
in Table 4. It is worth considering some
of the more interesting applications in
more detail.

Mercury removal from LPG

Propane and butane are often stored and
shipped at low temperatures and hence
there is the risk of mercury attack on
cryogenic equipment. They are also used
as aerosol propellants and for this duty
have to be completely free of odorous
compounds such as sulphur compounds.
A Puraspec reactor has been used for
several years for just this duty, treating
75 tes/h of liquid propane at 45°C prior
to refrigeration. The unit is of interest in
that COS, H2S and mercury are removed
and an ultra-dry molecular sieve is
used as a desiccant to remove any co-
produced water.

Mercury removal
from naphtha
In this application, a refinery was
supplying 130 tes/hr naphtha feed to an
ethylene cracker. The feed contained
40–140 ppb mercury. Part of the mercury
was in solution and part attached to
suspended matter. The palladium
acetylene hydrogenation catalyst was
found to be poisoned by mercury and
there were concerns with possible
corrosion of cryogenic equipment. A
1 µm filter was installed upstream of
two Puraspec reactors in lead lag
arrangement. The unit, shown in Figure
5, now operates to produce naphtha
with a mercury content of less than
1 ppb.
Conclusion
It is possible to remove mercury from a
wide range of liquid hydrocarbons to
meet the sales specifications now being
set by the process industry. The process
uses fixed-bed absorbents and only
requires minimal attention from plant
operators. A safe and reliable disposal
route has been established that allows
recycling of the spent absorbent with no
release of mercury to the environment.
Puraspec (PURASPEC) is a mark of Johnson
Matthey
References
1 Zettlitzer M, Scholer H F, Eiden R, Falter
R, Distribution of elemental, inorganic
and organic mercury in North German gas
condensates and formation brines, Society
of Petroleum Engineers International
Figure 5 Twin-bed Puraspec MRUs for naphtha feed
Symposium on Oilfield Chemistry,
Houston, Texas, 18–21 February 1997.
2 Environmental Protection Agency (EPA),
Mercury in petroleum and natural
gas: estimation of emissions from
production, processing and combustion,
Technical Report prepared by National
Risk Management Research Laboratory,
Willhelm M S, EPA-600/R-01-066,
September 2001.
3 Smit C J, Meijer H, Hendriks E M, Mercury
the volatile surprise in gas processing, GPA
Conference, Dublin, 18–21 May 2004.
4 Edmonds B, Moorwood R A S, Szczepanski
R, Mercury partitioning in natural gases
and condensates, GPA European Chapter
Meeting, London, 21 March 1996.
5 Dolle J, Gilbourne, LNG startup of the
Skikda LNG plant, Chem. Eng. Progress, 72,
39, 1976.
6 Lund D L, Causes and remedies for mercury
exposure to aluminium coldboxes,
75th Annual GPA Convention, Denver,
Colorado, 11–13 March 1996.
7 Affrossman S, Erskine W G, Paton J,
Investigation of the poisoning of platinum
group catalysts by thermal desorption.
Part 1 — mercury poisoning of benzene
hydrogenation on platinum, transactions
of the Faraday Society, 64, 2856–63, 1968.
8 Menon R K, Mercury and its impact on
ethylene purification catalysts, 17th
Ethylene Producers Conference, Atlanta,
11 April 2005.
9 Boogard P J, Houtsma, A-T A, Journee H
L, Van Sitteret N J, Effect of exposure to
elemental mercury on the nervous system
and the kidneys of workers producing
natural gas, Archives of Environmental
Health, 1966, 64, 10, 2856–63.
10 Spiric Z, Srebocan E, Mercury
Concentrations in ambient air and hares
at GPT Molve Area in the Idrija region and
the Northern Adriatic, Portoroz, Slovenia,
13–16 May 2001.
11 Shafawi A, Ebdon L, Foulkes M, Stockwell
P B, Corns W T, Determination of total
mercury in hydrocarbons and natural
gas condensates by atomic fluorescence
spectroscopy, Analyst.124, 185–189,1999.
12 Private communication, J Franks, ICI
Measurement Services Group, Wilton
Centre, Wilton, Cleveland, UK.
13 Openshaw P J, Woodward C, New
developments in mercury removal, AIChE
Spring National Meeting, Houston, Texas,
22–26 April 2001.
14 Carnell P J H, Openshaw P J, Rhodes E F,
Fixed-bed technology purifies rich gas with
H2S, Hg, Oil & Gas Journal, May 1999.
Steve Catchpole is Global Refinery Technical
Manager, Johnson Matthey Catalysts
Process Technologies in Billingham, UK. He
has been working in the field of catalyst
and absorbent-based technologies for
over 22 years. Catchpole graduated from
Loughborough University in 1986 with a
BSc in chemical engineering.
Email: katalco.syngas@matthey.com

www.eptq.com PTQ CATALYSIS 2009 45

j mathey.indd 5 2/2/09 10:35:06

JM_725_concepts 15/1/09 17:01 Page 2

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jmatthey.indd 1 30/1/09 12:24:34

 Producing propylene
glycol from biomass
Process and catalytic considerations for producing propylene glycol from
glycerin-derived biomass sources are compared to current conventional
sources, while economic factors and potential markets are discussed
P
ropylene glycol (PG) is a basic
petrochemical used primarily
in polyurethane polyols and
unsaturated polyester resins, and as
an anti-freeze agent in aircraft de-icing
applications, as well as an automotive
coolant. Total annual global consumption
is 1.5 million metric tonnes. Historically,
PG has been made commercially by
simply hydrating propylene oxide (PO).
PO, in turn, has been made historically
by the peroxidation of propylene using
co-feeds of either ethylbenzene (EB) or
isobutene (iC4).
When EB is used, PO is produced with
styrene monomer co-product. When iC4
is used, PO is produced with tertiary
butyl alcohol (or sometimes methyl
tertiary butyl ether [MTBE]) co-product.
An older technology produces PO from
propylene via chlorohydrin chemistry.
Recently, a new plant has been
commissioned by SK Chemicals to avoid
co-product formation by using hydrogen
peroxide as the oxidising agent.
Whichever historic route is taken, PG
production economics are dominated by
the cost of the basic feedstock propylene.
Produced from either natural gas liquids
or refinery naphtha, propylene prices
have averaged $1000/mt over the past
three years, and PG market prices have
been $1500/mt during the same period.
During the mid-2008 crude oil price run-
up, with naphtha prices exceeding
$1000/mt, market prices for both ethylene
and propylene averaged approximately
$1500/mt, driving PG market prices to
$2000/mt.
Production of PG
from glycerin
Most recently, several companies (Dow,
Huntsman, ADM, Ashland/Cargill) have
announced new commercial technology
projects for producing PG directly from
the glycerin that is a by-product of
biodiesel production. Since biodiesel
production has increased dramatically
over the past five years, a glut of excess
by-product glycerin has been produced
that cannot be absorbed into
www.eptq.com
sri.indd 1
Tony Pavone
SRI Consulting
conventional glycerin markets. Glycerin
prices, once $1000/mt, have dropped by
50% for refined grades, while raw by-
product glycerin is often used as
boiler fuel.
Two organisations have patented
their processes for converting glycerin to
PG: Davy Process Technology in the UK
and the University of Missouri (the
Suppes process) using R&D funds from
the US government.
Chemical structure of the
relevant molecules
PG is a three-carbon molecule in which
two of the carbon atoms are attached to
hydroxyl (-OH) radicals. The third
carbon atom is saturated with hydrogen.
The carbon atoms attached to OH
radicals are adjacent to each other. As a
result, PG has its OH ions on one of the
terminal carbon atoms and on its
adjacent internal carbon atom.
A similarly structured, but more
expensive molecule to make and buy, is
1,3-propane diol (PDO). Like PG, PDO is
a three-carbon molecule with two of its
carbon atoms connected to OH radicals.
However, with PDO, the OH groups are
both on the terminal carbon atoms,
with the centre carbon atom saturated
with hydrogen. Due to its structure,
PDO can easily be polymerised with
purified terephthalic acid to produce a
polyester (poly tri methyl terephthalate)
that performs much like nylon when
fabricated as a fibre, but costs only half
as much as nylon to manufacture.
The molecular structure of glycerin
(mol wt: 92.1) is remarkably similar to
PG and PDO. Glycerin is also a three-
carbon atom molecule, but each of the
carbon atoms is attached to an OH
radical. As a result, glycerin is a solid at
room temperature (both PG and PDO
are liquids), and has a much higher
boiling point than either PG or PDO.
From a chemical structure perspective,
converting glycerin into PG or PDO
simply requires substituting a hydrogen
ion for one of glycerin’s OH radicals. This
can be accomplished with conventional
industrial chemistry (high-pressure,
moderate-temperature hydrogenation at
a low residence time over a base metal
catalyst), or biologically using an enzyme
catalyst (moderate temperature and
ambient pressure and long residence
time). If the substitution occurs on a
terminal carbon atom, the product is PG.
If the termination occurs on the internal
carbon atom, the product is PDO.
Value proposition
The patent literature has taught for at
least the past 50 years methods for
converting glycerin to PG (albeit at low
conversion rates). So why does the world
have renewed interest in the chemistry?
The basic reason is economics. As long
as glycerin market prices are significantly
higher than propylene monomer market
prices, there is no compelling economic
reason for making PG or PDO from
glycerin. In this economic world, it costs
more to make PG from glycerin than it
costs to make PG from propylene.
Biodiesel has changed this economic
world. Since 10% of the production of
conventional biodiesel (methanol
esterification of fatty acid) represents
glycerin by-product, the conventional
markets for glycerin are well satisfied by
the conventional sources of glycerin
(from soap and surfactant manufactur-
ing). When there is an excess supply of
any commodity to a market, the market
price of the commodity usually drops
precipitously.
If the market price of glycerin changes
from initially being much more
expensive than propylene to finally
being much less expensive than
propylene, it makes sense that industrial
routes to PG from glycerin might be
economically attractive.
Markets for glycerin
As shown in Table 1, the global demand
for glycerin is approximately 600 kty.
PTQ CATALYSIS 2009 47
2/2/09 10:36:19
 methanol, some soap, some emulsion
Consumption breakdown for glycerin by major region, 2004, and dissolved salts. The raw biodiesel is
thousands of metric tonnes easily converted to on-spec product by
washing several times with water to
US Western Europe Japan Total remove residual amounts of methanol,
Personal/oral care products 83.0 63.0 14.4 160.4 fatty acid, salts and solids. The raw
Foods and beverages 47.0 36.0 – 83.0 glycerin takes much more effort to clean
Drugs/pharmaceuticals 15.0 29.0 21.6 65.6 up to a commercial product specification.
Polyether polyols 18.0 38.0 5.8 61.8 As a result, the small biodiesel producers
Tobacco 23.0 17.0 4.8 44.8
either landfill the raw glycerin product
Alkyd resins 6.0 18.0 7.5 31.5
or burn it as boiler fuel.
Other 12.0 92.0 33.3 137.3
The key concept in comparing these
Total 204.0 293.0 87.4 584.4
biodiesel producers is that a few have
Average annual growth rate, % the capability to actually produce
commercially competitive glycerin,
2001–2004 -3.8% 6.7% 0.5% 1.7% while the balance of the biodiesel
2004–2009 2.2% 7.0% -0.2% 4.4% producers (small producers) do not have
this capability. Therefore, their glycerin
Table 1 by-product does not compete for
conventional glycerin markets.
markets that do not compete with each
Key properties of commercial other. The first kind of biodiesel producer Purifying raw glycerin from
glycerin is a large capacity, on-purpose operation biodiesel plants
(>50 kty production) that has the As previously mentioned, the raw glycerin
Parameter Value
resources and the will to attempt to sell layer from a biodiesel plant is a water-rich
Melting point, °C 18.17
by-product glycerin into conventional ionic liquid containing a multitude of
Boiling point, °C at 1 atm 290
Specific gravity, in air 1.262
glycerin markets. The amount of effort “bad actors” that must be removed to
Vapour pressure, Pa at 50 °C 0.33 required to purify raw glycerin (skimmed meet commercial glycerin specifications.
Viscosity ,cp at 20°C 1499 or washed from a biodiesel reactor) to The key properties of commercial-grade
Heat of vapourisation, commercial specification glycerin is glycerin are presented in Table 2.
j/mol at 55°C 88.12 large and costly and will be explained in Commercial specifications for glycerin
Thermal conductivity, W/mK 0.28 further detail. are provided in Table 3. The composition
Flash point, °C open cup 177 The other kind of biodiesel producer of a typical raw glycerin product stream
Ignition point, °C 204 is an entrepreneur with little access to from a biodiesel plant is presented in
capital or to technology. These producers Table 4. Converting raw glycerin to
Table 2 have production capacities below 5 kty. commercial specification glycerin is not
Biodiesel can be made in a bath tub, and trivial, and generally requires a complexity
Historical and projected demand growth these “mom and pop” producers of unit operations.
rates are modest (2–5%/year) and surely conduct the entire operation in a single
not high enough to absorb the enormous reactor at atmospheric pressure. This Capturing value
amount of new glycerin capacity approach requires the manufacturer to The concept of making money from
expected from biodiesel by-product. pour natural oil (rapeseed in Europe, converting glycerin to PG, based upon
Where is all the glycerin from biodiesel soybeans in the US) into a simple the previous analysis, should essentially
going to go? One globally large producer reactor, add 1/10 portion of methanol, be revised. Rather than making
of conventional glycerin, which produces and a pinch of catalyst (typically sodium money from converting commercial-
on-purpose biodiesel, has intentionally methoxide), hydrochloric acid and specification glycerin to PG, the concept
decided to burn by-product glycerin in activated carbon. The mixture is heated can only be monetised successfully if
its steam boilers to avoid degrading the up, well mixed and allowed to settle for the basic feedstock is raw glycerin rather
market price of glycerin. 8–24 hours. The result is a two-phase than purified glycerin. For the business
SRI’s assessment of the biodiesel product, with an upper oil phase proponent, it means taking the extra
market indicates that there are two containing mostly biodiesel and a lower steps of first collecting raw glycerin from
entirely different biodiesel producer aqueous phase containing mostly water, biodiesel producers who are unable or

Commerical specifications for glycerin product

Grade Technical 96% vegetable 99.5% USP 99.5% USP 99.5% USP Kosher 99.7% USP Kosher
grade based (USP) (tallow derived) (vegetable based) (vegetable based) (vegetable based)
Assay, % 99.5+ 96.00–96.99 99.5 99.5 99.5 99.7
Specific gravity 1.249 1.249 1.249 1.249 1.249
Colour, APHA 20 max 20 max 20 max 20 max 20 max
Residue on ignition, % 0.01 0.01 0.01 0.01 0.01
Chloride, % 0.001 0.001 0.001 0.001 10 ppm
Sulphate, % 0.002 0.002 0.002 0.002 20 ppm
Heavy metals, ppm 5 max 5 max 5 max 5 max 5 max
Chlorinated compounds, % 0.003 0.003 0.003 0.003 30 ppm
Organic volatile impurities Passes test Meets req Meets req Passes test Meets req
Fatty acids & esters, Mas 1.0 ml/50 g Gly 1.0 ml/50 g Gly 1.0 ml/50 g Gly 1.0 ml/50 g Gly 1.0 ml/50 g Gly
Water, % 5 0.5 0.5 5 5
Ident: parts A & B Passes test Passes test Passes test Passes test Passes test
Limits: DEG Passes test Passes test Passes test Passes test Passes test

Table 3

48 PTQ CATALYSIS 2009 www.eptq.com

sri.indd 2 2/2/09 10:36:33

 Biodiesel plant-derived glycerin properties
Components MOL. WT. Fuel-grade glycerin, wt%
Water 18 41.2
Methanol 32 0.9
Vegetable oil 793 2.0
Free fatty acids 282 4.1
Biodiesel 296 9.4
Sodium methylate 54 0.3
Sodium hydroxide 40 0.9
Glycerin 92 39.2
Sodium soaps 304 2.0
100.0

Table 4

unwilling to perform the purification prices globally. The $400/mt commercial-

themselves, and then adding the
processing capability to upgrade raw
glycerin to commercial glycerin.
Incidentally, Lurgi offers a modularised
process plant to do the entire job.
Making PG from glycerin
Davy Process Technology and the
University of Missouri have received
much press attention for offering
licensable processes to convert glycerin
to PG. Both licensors require commercial-
grade glycerin to avoid destroying their
catalysts. The Davy process is a vapour-
phase hydrogenation in which the molar
ratios of H2 to glycerin are enormous
(600:1 on a molar basis). In practice, its
unit would closely resemble a
conventional gas oil hydrocracker
operating at modest (25 bar) pressure.
Davy’s patents indicate that most
conventional hydrogenation catalysts
work adequately in its process. The
Missouri process is liquid-phase
hydrogenation using conventional
copper chromite catalyst. The chemistry
sequence for the hydrogenations takes
place in a two-step process: dehydration
of glycerol to acetol (intermediate
product) followed by acetol
hydrogenation to PG.
When attacked by hydrogen atoms,
the first step is to strip one OH radical
plus one hydrogen atom from the
glycerin molecule (in the form of a
water molecule). This produces an acetol
intermediate. Some researchers believe
the acetol actually converts to an epoxide
instead. The second step is to hydrogenate
either acetol or epoxide to the
corresponding glycol; in this case, PG.
Dow is producing semi-commercial
quantities of PG from glycerin using its
in-house toll processing subsidiary,
Haltermann. Haltermann modified an
existing (and conventional) hydrotreater
for glycerin feed.
Beyond 2010
Given this discussion, you might think
that the world is desperate to make PG
from glycerin. The enthusiasm for this
approach has been dampened by the
doubling of some commodity food
grade glycerin of 2007 is now priced
closer to $800/mt, removing half the
commercial potential for the concept.
A less immediate threat to the value
proposition is the long-term forecast for
biodiesel production. At current market
prices, biodiesel production only makes
economic sense when highly subsidised
by government. Some of the biodiesel
subsidies (especially in Germany) have
recently been lowered. If the subsidies
are eliminated, perhaps the anticipated
biodiesel production capacity will not
be realised. In the US, some soybean-
driven biodiesel capacity has actually
been mothballed. Without biodiesel,
there is no discount-priced glycerin
feedstock for making PG.
Even if biodiesel production makes
economic sense on one level for some
reasons, it is not at all certain that the
current practised chemistry (methanol
esterification of natural fatty acids) will
endure. Biodiesel can also be produced
by the direct hydrogenation of natural
fatty acids. ConocoPhillips converted an
idle hydrotreater in one of its UK oil
refineries to biodiesel direct hydro-
genation and plans to take the technology
global. Statoil claims a similar technology,
while a joint venture between ENI and
IFP is piloting a similar chemistry. Direct
hydrogenation does not produce a
glycerin by-product. Instead, it produces
a propane by-product.
It is reasonable to assume that
greenhouse gas (global climate change)
concerns will not dampen society’s
enthusiasm for making transportation
fuels and perhaps industrial chemicals
using natural feedstocks rather than
petroleum. Converting biodiesel by-
product glycerin to PG makes technical
sense, and under some business scenarios
makes economic sense. The direction of
petroleum prices, agricultural prices and
government intervention in markets will
determine the fate of PG from glycerin.
Tony Pavone is Senior Project Manager,
SRI Consulting in Menlo Park, California.
Email: apavone@sriconsulting.com

www.eptq.com PTQ CATALYSIS 2009 49

sri.indd 3 2/2/09 10:39:02

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norpro copy 1 2/2/09 13:55:17

 Increasing ULSD production
with current assets
An understanding of the detailed kinetics in ultra-low sulphur diesel
hydrotreaters yields an optimal catalyst system for higher throughput,
increased cycle length and lower reactor temperature

Bob Leliveld Albemarle Catalyst Company BV

Steven Mayo Albemarle Corporation

A
wide variety of catalyst solutions
for ultra-low sulphur diesel
(ULSD) service are available to Sweet SRGO SRGO cracked SRGO – LVGO cracked
the refining industry. The introduction feed
of Albemarle’s patented Stars technology
more than a decade ago marked the Nebula-20
beginning of the Type II catalysts era,
HDS & Cetane lift

which includes the application of these KF 848

catalysts with super active catalytic sites
in ULSD operations. Increasing the
throughput in a ULSD unit or processing
low-quality feedstocks without additional
capital investment are both great ways of
increasing margins and financial returns.
Based on new detailed insight into the
chemistry taking place in a ULSD unit,
new catalysts and catalyst technology
are being introduced that can help boost
performance.
Recent developments are able to
improve hydrodesulphurisation (HDS)
unit performance by up to 35% over the
most active catalysts in the current
hydroprocessing marketplace. For
example, the new Ketjenfine (KF) 770
HDS catalyst, built on Stars technology,
will enable ULSD refiners to substantially
improve their operating margins by
extending catalyst cycle length,
increasing throughput or running
cheaper, lower quality feedstocks, all
without additional capital expenditure.
The KF 770 HDS catalyst’s functionality
focuses on reaching breakthrough
performance in low- and medium-
pressure range ULSD. It takes the place of
KF 757 Stars in Albemarle’s ULSD catalysts
(Figure 1). KF 757 is still available for
refiners running less severe operations.
The catalytic removal of refractory
sulphur species occurs through a
complex reaction scheme comprising at
least two routes: through direct route
HDS or direct desulphurisation (DDS)
and hydrogenation (HYD) sites.
A complicating factor at low and
medium partial pressures of hydrogen is
the slow rate of organic nitrogen
removal. As the nitrogen species inhibit
the HYD sites, the catalyst’s effectiveness
is largely determined by the number of
DDS sites. KF 770, developed through
KF 770
KF 757
10 20
Figure 1 Albemarle’s portfolio for ULSD production
HYD sites
HYD sites
Figure 2 Build-up of performance benefit of Ketjenfine 770 Stars
high throughput experimentation, has
precisely those sites gearing its
performance at low and medium
pressures to a start-of-run (SOR)
performance activity benefit of more
than 20%, as shown in Figure 2.
Figure 3 compares the activity of KF
770 vs KF 757 in a 20 bar pilot plant test.
Over a period of more than 40 days, KF
770 continuously showed an advantage
in HDS, achieving an extra volume
activity of 20–25%.
Prolongation of the test at 45 bar
(Figure 4) clearly demonstrates that the
throughput in a unit with KF 770 can be
increased to 20% over the same unit
loaded with KF 757. These and other
pilot plant results confirm that the
stability of KF 770 is equal to or better
than KF 757. Throughout the develop-
ment of KF 770, the formulation of the
KF 767
35 50 100
Outlet partial pressure H2
DDS sites KF 757 Stars
+20%
HYD sites KF 770 Stars
catalyst was tailored to achieve maximum
stability under the conditions of low and
medium partial pressure of hydrogen.
35% cycle length increase
In addition to 20% extra SOR activity,
detailed forecasting for specific cases
demonstrates that KF 770 can increase
cycle length by up to 35% when
compared to KF 757 (Figure 5).
The lower SOR temperature favours
catalyst stability, as the deactivation rate
is a function of reactor temperature. In
addition, the high HDN activity of KF
770 provides an extra boost in HDS
activity by releasing HYD sites from
inhibition by nitrogen species. It further
suppresses the needed reactor
temperature for reaching ULSD
specifications and builds to an overall
35% increase in cycle length.

www.eptq.com PTQ CATALYSIS 2009 51

albemarle.indd 1 2/2/09 13:58:03

 Economic benefits
In addition to a longer cycle length, KF
30 770 can add significant value by enabling
higher throughputs or intakes of sour
feeds. For a 30 000 bpd distillate
25
hydrotreater, running at a 20% higher
throughput, this can add an additional
20 margin per year of up to $22 million.
This figure is based on an upgrading
Sulphur, ppm

margin of $10/bbl.
15 This advantage is illustrated further in
Figure 6, showing the extra margin
obtained with KF 770 as function of the
10 additional throughput. Three levels of
upgrading margin have been chosen to
reflect the various qualities of feed.
5 KF 770
KF 757
Catalyst systems: single or
0 mixed loads
15 25 35 45 For most of the history of hydrotreating
Days on stream in refineries, a single catalyst loaded in
a unit was sufficient to provide the
Figure 3 KF 770 performance vs KF 757 at conditions of 20 bar, SRGO feed: 1.17 expected level of performance. There
wt% S, 94 ppm N, FBP 700°F (371°C); H2/oil = 300 nl/ltr were exceptions, of course, such as
fixed-bed resid, but the majority of
applications did not need a different
approach. As the demands placed on
hydrotreating units have increased and
15
the requirements for hydrotreated
Equal LHSV product have become more stringent,
the opportunities for a more skilful
12 approach to catalyst system design have
become apparent.
The traditional approach to
LHSV KF 770
9 understanding the chemistry of
Sulphur, ppm

120% of KF 770
hydroprocessing is to analyse feed and
product properties, measure average
6
reactor temperature (WABT) and use
basic kinetic expressions to analyse unit
performance. Obviously, this approach
only provides an average view of how
3 the unit is operating. In recent years,
KF 770
KF 757 more sophisticated sulphur- and
nitrogen-specific analysis as well as inter-
0 bed temperature measurements have
70 80 90 100
given more insight into unit
Days on stream
performance. However, the information
is still not detailed enough to fully
Figure 4 KF 770 vs KF 757 at 45 bar, SRGO feed: 1.17 wt% S, 94 ppm N, FBP 700°F understand the reactions taking place
(371°C); H2/oil = 300 nl/ltr inside the unit.
Fully understanding the chemistry of
hydroprocessing inside the reactor is key
towards designing a catalyst system for
maximum performance. The problem,
of course, as shown in Figure 7, is that
LONGER there are many independent variables
CYCLE changing at every point in the reactor.
The chemistry taking place at any point
7!"4FORPPM3

both affects and is affected by these

KF 757 Stars variables.
No two slices of the reactor along the
vertical axis have the same reaction
environment, which means the best
KF 770 Stars catalyst for optimising system
120% SOR activity performance could be different at each
point. This has radically changed the
way we think about the application and
#YCLELENGTH development of ULSD catalysts. While
in certain conditions a single catalyst fill
is still the best solution, in other cases a
Figure 5 Increased cycle length with loading KF 770 combination of catalysts is preferred.

52 PTQ CATALYSIS 2009 www.eptq.com

albemarle.indd 2 2/2/09 10:45:24

 Consider the case of ULSD and a
conceptual reaction zone model, with
three zones represented in tabular form 
in Table 1. Although the zones can be
perceived as being equal in volume and
are frequently shown as such in graphical
illustrations, the size and position of 
each zone will in fact vary as a function
of feedstock properties, operating

!DDITIONALANNUALMARGIN--
conditions and process objectives.
Each of the zones in this ULSD- 
focused example has dramatically
different reaction conditions that affect
catalyst performance. In zone 1, the top
catalyst layer, the primary reaction 
occurring is through the previously
mentioned direct-route HDS (or DDS).
The rate of desulphurisation is fast and
sulphur content drops rapidly. At the

same time, hydrogen is consumed, so
BBL
ppH2 is reduced and ppH2S increases, BBL
the latter creating some inhibition. As BBL
the rate of direct-route HDS slows, the

feedstock moves into zone 2. In zone 2,       
the focus shifts from the removal of !DDITIONALTHROUGHPUTBPD
sulphur to the removal of nitrogen, with
organic nitrogen the main inhibitor to
an increased HDS reaction rate. Zone 2 Figure 6 Additional upgrading margin per year with KF 770 for three levels of
ends when the organic nitrogen has upgrading margin
been almost completely removed. At
this point, the feedstock enters zone 3
and the hydrogenation route HDS (HYD)
picks up speed. Even though ppH2 is at
its lowest in zone 3, the catalyst is
operating in a nitrogen-free environ-
ment. Here, the rate of hydrogenation of Nitrogen
Sulphur

aromatics — including the aromatic

rings of sterically hindered

Temperature
dibenzothiophene molecules —
increases. Finally, the feedstock exits the Catalyst

ppH2
system
reactor as ULSD.
It should be clear from this three-zone
NH3
H2S

example that understanding where

reaction conditions change presents an
opportunity to improve system
performance. Rather than an average
level of performance from a single
catalyst across all zones, an optimised
catalyst system can be designed using
catalysts that perform well in a particular
regime. This is the essence of proprietary
Stax catalyst systems. Of course, this is
easier said than done, as it requires a
detailed understanding of the conditions
at each point in the reactor.
Key to the application of Stax is a
model that can predict the reaction
conditions at each point in the
hydrotreating unit. Using new analytical
methods and small-scale testing
equipment, it is now possible to see into
the reactor and develop models based
on those observations. Technology has
been developed to track changes in
sulphur, nitrogen and aromatics “by
slice” along the vertical axis of a
laboratory reactor. This allows the
concentration of bulk sulphur and
nitrogen to be tracked through the
reactor, and permits the analysis of
samples using GCxGC to segregate
Figure 7 Conditions in a typical hydroprocessing unit’s reactor catalyst system
Typical three-zone reactor model: zone 1, top catalyst layer; zone 2, middle
catalyst layer; zone 3, lower catalyst layer
Zone 1 Zone 2 Zone 3
Sulphur content High Medium Low
Nitrogen content High Medium-low Very low
Polynuclear aromatics High Medium-low Zero
H2S in gas 0–medium High Highest
NH3 in gas 0–medium Medium High
H2 in gas High Medium Medium-low
Main HDS reaction Direct Mainly direct Hydrogenation
Main HDS inhibitor H2S Organic nitrogen –
HDS reaction rate Fast Slow Fast
Table 1
hetero-atoms by structure. Catalyst selection and system design are
Stax is the technology for applying an made according to the reaction chemistry
understanding of hydroprocessing and process conditions in each reactor
chemistry to optimise unit performance. section. This allows the catalyst system to

www.eptq.com PTQ CATALYSIS 2009 53

albemarle.indd 3 2/2/09 10:45:34


54 PTQ CATALYSIS 2009
albemarle.indd 4
be tuned to meet performance and
process objectives. Some of the
opportunities for achieving refinery
targets are:
— Maximum HDS with constrained
hydrogen consumption
— Maximum cetane uplift up to unit
hydrogen limit
— Maximum cycle length at specific
sulphur target
— Simultaneous sulphur and volume
gain target.
The concept of stacked beds has been
practised for decades, so it is important to
discriminate between stacked beds and
Stax technology. The purpose of stacked
beds is to enhance HDS or HDN in a unit
by applying more or less CoMo or NiMo
catalyst. The performance of the stacked
system is an average of the individual
HDS and HDN activities of the catalysts
in the system. Contrast that with Stax
technology, where the performance of
the catalyst system will be better than the
performance of any of the catalysts in the
system, either individually or on average.
Confirmation of the performance of Stax
catalysts systems can be accomplished in
the laboratory. However, a model is
needed to develop an optimised catalyst
system. Performance can change with
time on-stream and variation in feed
type and rate. The deactivation rate also
varies with position in the reactor. The
ability to consider many cases in the
process of developing both an active and
a robust catalyst system necessitates the
use of a model.
Stax technology has already been
introduced to several commercial units
with the expected benefit in performance.
In addition, both Albemarle and refiners
using the technology have been able to
confirm the benefit of the technology in
the laboratory. For example, a Stax
system was compared to a system with
100% KF 767 in ULSD service. The
objective of the refiner was to double
the throughput of the unit while still
producing ULSD with a reasonable cycle
length. One option was to double the
reactor volume using the current catalyst,
20
1 2
15
Product $, ppm
10
5
0
0 10 15
Figure 8 Stax in practice
www.ptqenquiry.com
for further information
KF 767. Alternatively, we wanted to
determine if a Stax system could achieve
the same result in the existing unit.
Process conditions were moderate at 60
bar ppH2 and 1.28/hr LHSV for the
existing unit and 0.64/hr LHSV for the
modified unit. Temperature and H2/oil
were varied to judge system robustness.
As can be seen in Figure 8, it was
observed that the performance of the
Stax and KF 767 systems are similar.
Since the Stax system is operating at
double the space velocity of the KF 767
system, it is easy to deduct that RVA
HDS is near 200 for the Stax system.
Conclusion
Ketjenfine 770 Stars is the latest
development by Albemarle for low- to
medium-pressure ULSD operations,
offering up to 35% benefit over a full
cycle. The first commercial applications
are meeting performance targets.
As well as developing single catalyst
solutions, significant performance can
be gained by understanding the
chemistry and kinetics of hydro-
processing reactions at every point in
the reactor. Until recently, the tools to
develop such a detailed understanding
were either unavailable or too expensive.
With Stax technology and the models
that support it, there is a new opportunity
to maximise catalyst performance. This
is especially true for units that run in
zone 3 mode, as most ULSD units
operating at medium to high pressure
do.
Stars (STARS), Ketjenfine and Stax (STAX) are
marks of Albemarle Corporation.
Bob Leliveld is Marketing Manager,
Hydroprocessing, with Albemarle
Catalyst Company BV in Amersfoort, The
Netherlands.
Email: bob.leliveld@albemarle.com
Steven Mayo is Global Manager,
Application Technology, with Albemarle
Corporation in Houston, Texas.
Email: steven.mayo@albemarle.com
3 4
KF 767
STAX
20 25 30 35 40
Days on stream
www.eptq.com
2/2/09 14:14:55
 Attention all FCCU operators
The FCCU in transition
How refiners can benefit from an unprecedented opportunity

Pre-eminent FCC expert, Warren Letzsch, and PTQ’s editor, Rene Gonzalez, have
co-authored an important new study with the single objective of informing refiners how they
can make their FCC unit operations more profitable. Topics covered include:

l How recent projects have generated major financial advantages by

converting HVGO from the latest generation deep cut vacuum
distillation units (See section 6.1 of the Study)

l How to provide a balanced output of clean burning gasolines and

ULSD gas oils while optimising chemical hydrogen consumption
and minimising outputs of lower value (See section 6.1)

l How larger refineries can explore parallel conversion opportunities

for heavy distillate conversion (See section 6.1)

l How modifications to major refinery assets, such as the vacuum

unit, delayed coker and MHC will directly benefit FCC operations
(See section 6.6)

l How refiners who have successfully increased diesel and/or

propylene production from their FCC unit are succeeding in
obtaining better separations from their FCC main fractionators (See
section 8.1)

l How best to benefit from changes in heat and energy balances

resulting from an increase in the size and complexity of regenerator
units (See sections 2.3, 4.1, 6.3 and 6.5)

l How proposed legislation for carbon capture and sequestration

mandates will affect FCC design, including details of CO2 capture
from conventional SMR plants and polygeneration gasification
plants, allowing the regenerator to operate on ambient air w/o CO2
capture (See section 6.5)

l How full-burn units are performing at higher severities processing

opportunity feeds but still meeting current and future emissions
targets (See sections 2.3 and 7.3)

l How to get the greatest productivity out of FCC/RFCC and
associated gas plants, particularly when linked to:
° Mild hydrocracking unit (MHC)
° Butylene alkylation unit
° Two-stage desulphurisation unit
° High purity propylene plant
° Separate draws within main fractionators
° Integrated slurry oil filtration unit
° Third-stage separator with underflow filtration (See section 8.2)
Plus
l Assessment of FCC catalyst formulations for processing
hydrotreated cat feeds and non-hydrotreated cat feeds (See
sections 6.7 and 9)
l A survey and refinery wish list of selected FCC unit components
including feed nozzle injectors, cyclones and steam strippers (See
sections 12.4, 12.5 and 12.6)
l Survey of rotating equipment developments for improving reliability
of new and refurbished WGCs and MABs (See section 11)
l Process flow diagrams showing FCC units configured for specific
product objectives (export-based refineries, refineries targeting
WCS feedstocks, FCCUs with turboexpander/cogeneration
capacity) (See figures 1.1, 5.1, 7.1 and 7.2)
l Survey of future long-term trends affecting FCCU process design
and operations, including market and regulatory trends such as
higher fractions of heavier feeds, synthetic blends and biomass
processed through the FCC. (See sections 13, 14.1 and 15)

For further details of the contents of this study and

how to purchase it, go to www.eptq.com/studies
fccu filler copy.indd 1 2/2/09 10:49:41
Cat 09 Ad Index.qxd 4/2/09 21:17 Page 1

AL P HAB E TI CAL L IS T OF AD VER T ISE RS

COMPANY PAGE COMPANY PAGE
NA M E NUMBER NAME NUMBER
Advanced Fluid Catalytic Cracking Unit 31, 54 Grace Davison 4
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Albemarle Catalyst 9, 11, 13, IBC Haldor Topsøe IFC

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Amistco Separation Products 37 Johnson Matthey Catalysts 46

www.amistco.com
www.jmcatalysts.com
Axens OBC
Mourik International 12
www.axens.net
www.mourik.com
Basf Catalyst 14
www.basf-catalysts.com Refining China Conference 10
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Buchen-ICS 8
www.buchen-ics.com Sabin Metal Corporation 32
www.sabinmetal.com
Chevron Lummus Global 18
www.chevronlummus.com Saint-Gobain NorPro 44, 50
www.norpro.saint-gobain.com
CRI Catalyst 21
www.cricatalyst.com Süd Chemie 38
www.sud-chemie.com
Criterion Catalyst 6
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Tricat Catalyst Service 43
www.eptq.com 49 www.tricatgroup.de

FCC Forum IBC UOP 22

www.eptq.com/studies www.uop.com

Ge Oil & Gas 2, 3 Zeochem 26

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YOU C A N A C C E S S I N F O R M AT I O N A N D C O N TA C T A D V E R T I S E R S D I R E C T AT

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albemarle 3.indd 1 4/2/09 09:44:32

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axens.indd 1 30/1/09 12:27:47