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catalysis

ptq catalysis 2009

2009

ptq

cat cov.indd 1 4/2/09 10:56:41


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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

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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
It is also safe fleettowill lead to
assume thatsome growth
refinery andinpetrochemical
new refinery
Graphics
GraphicsEditor construction and expanded refined
Mohammed
Editor conversion unit capacity will needproduct
to expand. output.
MohammedSamiuddin
Samiuddin Despite
No massive an industry
new sources slowdown that has
of energy are forced
expected cancellation
to come of onprojects
stream in for the
the
graphics@petroleumtechnology.com
graphics@petroleumtechnology.com refining
foreseeableandfuture.
petrochemical
The worldsectors will remainof the energy industry,
dependent on oil and somegas forrefiners
decades will
to
continue
come even withthough
expansion theplans based on
upstream long-term
industry facestrends to matchchallenges
increasing refinery productin the
Editorial profiles
discoverywithand a global market that
production of newis demanding
sources. cleaner
In fact,fuels some andwell-placed
more diesel,industry
which
Editorial isanalysts
expected to be2008in higher demand than gasoline
PO
POBox
Box11283
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
tel+1
+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
fax+1+1281
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
bed system bedprotect
technology
active
installed in hydrotreaters and mild hydrocrackers, the
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity level of metals contaminants
Advertising
AdvertisingSales
SalesOffice is(eg,
high enough
Office <10), highin crude feeds
metals, nitrogen to justify
and other financing delayedcomponents
undesirable coking unit upgrades.
is one of the In
tel
tel+44
+44870
87090
90303
30390 addition, many why of those refiners expanding their dieselare production
fax
90 main reasons hydrotreaters and hydrocrackers becomingwill improve
larger — to
fax+44
+44870
87090
90246
2469090 their crude unit/vacuum
accommodate not onlydistillation
higher volumes units atof the front end
catalyst, butofalso
the refinery
a widertovarietyexpandof
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
VGO hydrotreater to process the resulting coker naphthas,
further increasing feed contaminants while decreasing reactor
hydrogen partial pressures. The ongoing challenge to the
feedstocks, such as Swedish city diesel)? With current budget refiner is to maintain stable long-term operations while
constraints, what factors should justify the implementation operating with both high metals deposition from the feed
of counter-current reactor technology over conventional co- contaminants and high reactor bed outlet temperatures due
current reactor technology?
❞ to the reaction exotherms, both of which can result in higher
deactivation rates.
Criterion has been mitigating these impacts by developing
Sal Torrisi, Business Manager, Distillate Catalysts, unit-specific catalyst systems. Typical catalyst systems employ
Criterion Catalysts & Technologies, sal.torrisi@cri- activity and size graded top-bed products from the proprietary
criterion.com: Recent significant performance advances in Sentry OptiTrap family to control pressure drop from
conventional NiMo catalyst technology (eg, Centinel Gold particulates and foulants, a demetalisation section using
DN-3330) have proven in commercial operations that a products from the proprietary Sentry MaxTrap portfolio, to
higher degree of aromatic saturation can be achieved protect from a number of possible feed poisons, and high-
compared with prior generation catalysts. In the diesel activity main-bed products from the Ascent product line with
boiling range, virtually all polynuclear aromatics (PNAs) and a commercially proven ability to provide high levels of
a substantial quantity (20–50%) of monoaromatics can be performance and low deactivation rates in these challenging
removed in an appropriately designed and operated single- VGO operations.
stage reactor hydrotreater. When deep aromatic saturation is In addition to protection from feed contaminants, the
required (>50%), the two-stage reactor approach using a technology produces catalysts with improved tolerance to
noble metal catalyst in the second reactor is still preferred. thermal-based deactivation. This tolerance allows for reduced
This approach is favoured in regions where there are deactivation rates at higher temperatures and lower hydrogen
stringent aromatics specifications or where refiners are partial pressures, leading to a longer cycle life in FCC pretreat
looking to selectively fix hydrogen into liquids (ie, where and VGO units. This improved stability at high temperatures
volume gain delivers extra margin). is particularly useful in operations with high reactor outlet
temperatures due to feed quality or system constraints.
Rasmus Breivik, Manager, Refinery Group, Haldor Topsøe,
rao@topsoe.dk: Industrial experience of producing ultra-low Woodrow K Shiflett, Director of Marketing, Advanced
aromatic diesel such as Swedish city diesel since the early 1990s Refining Technologies (ART), wosh@chevron.com: High-
has resulted in an improved HDS/HDA technology that is a sulphur, high-nitrogen streams, such as heavy coker gas oils
cost-effective solution for upgrading heavy diesel fractions to and coker gas oils and DAOs, have been processing in VGO
high-quality ultra-low sulphur diesel. Developments hydrotreaters without notable problems for years. ART has
in dearomatisation catalysts have led to the commercialisation extensive experience in this area from the long-term and
of catalysts with four times higher activity for the saturation of widespread application of its ApART Catalyst Systems in
aromatics. Required catalyst volumes have been reduced to a numerous VGO hydrotreaters. Such catalyst systems are
level that makes counter-current reactors no longer justifiable tailored to maximise HDS removal to produce low-sulphur
from an economical perspective. 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

❝ 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?
FCC associates.
Heat release and exotherm control rarely pose challenges
unless coker naphthas, excessive light coker gas oil content or
How were any of the expected problems handled, such as a other highly olefinic components are present in the VGO
higher exothermic heat release?
❞ hydrotreater feed. Such feedstocks typically find homes in
other hydroprocessing units such as NHTs and light distillate
hydrotreaters, which are designed to accommodate the high
Kevin D Carlson, Global Business Manager, FCC Pretreat olefin contents.
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
❝ With more TGU capacity likely to be added
downstream from Claus units to achieve 99.9% sulphur
recovery, what important parameters should refiners
upon to process the resulting difficult feed streams. In consider in catalyst selection? How does end-of-cycle
addition to the high aromatic and contaminant levels of these catalyst reuse/regeneration factor into tail gas catalyst
heavy coker gas oils, a number of refiners are utilising the selection?

www.eptq.com PTQ CATALYSIS 2009 7

Q_A copy 2.indd 1 2/2/09 10:05:15


Nilanjan Brahma, Business Manager, Eurecat, nilanjan. Since pressure drop is so critical for the cycle length of a
brahma@eurecat.com: Tail gas catalysts are typically in TGU, all TGU catalysts are produced in large sizes such as
service for many years and regeneration is rarely considered. 1/8in, 1/10in and 1/6in in various shapes.
One factor that should be evaluated when considering a fresh Haldor Topsøe recently introduced a new TGU catalyst
charge of tail gas catalyst is preactivation of the catalyst load. designated TK-222 in a 1/8in ring shape, which will reduce
Preactivation of tail gas unit (TGU) catalysts installed in the start-of-run (SOR) pressure drop by 85% compared to any
proprietary Shell Claus Off-gas Treatment (SCOT) units offers other commercial available TGU catalyst. Using TK-222 will
significant advantages over a traditional start-up, where the allow the refiner to handle much more soot formation before
oxidic catalyst is sulphided after loading. The preactivation the end-of-run (EOR) pressure drop is reached. Alternatively,
benefits include: a TGU using TK-222 will be able to process much more tail
— No additional sulphur chemicals (spiking agents) need to gas with the same blower capacity, thus effectively
be introduced in cases where sufficient amounts of sour gas debottlenecking the TGU, which means the refiner can
are not available. process higher sulphur crudes without building additional
— Temperature limits in the SCOT unit will not adversely tail gas capacity.
affect the activity of the TGU catalyst, since the catalyst is Due to the criticality of the SOR pressure drop in a TGU,
activated prior to loading. In many units, the temperatures in regeneration of the TGU catalyst for reuse in the TGU is not an
SCOT units are not optimal for obtaining maximum catalyst option many refiners would consider. Regenerated catalyst will
activity result in a higher SOR pressure drop compared with new
— There will be no water make from sulphiding upon catalyst due to some catalyst breakage during the handling and
start-up regeneration process.
— Exotherm phenomena during start-up are eliminated
— The catalyst is immediately ready to perform after loading. Steve Massie, Business Manager, Gas Treating Catalysts,
One preactivation technology that has been used in Criterion Catalysts & Technologies, steve.massie@cri-
dozens of TGUs is Eurecat’s Totsucat process. With Totsucat, criterion.com: The most important factor in tail gas treatment
a totally sulphided and activated catalyst can be loaded in is reliably meeting the stringent emission requirements. If
the TGU, eliminating start-up hassles and unnecessary these requirements are not met, then, depending on the
delays associated with sulphiding. location and requirements, the refinery or gas plant must shut
down, cut back on production and/or pay fines. Therefore, the
Breivik: Tail gas treating is a special subset of hydrotreating TGU catalyst must be robust and stable, able to withstand
due to the fact that TGUs operate just above ambient pressure upsets and continue to operate to meet the environmental
and the feed gas contains large amounts of water. TGU requirements. Once these first parameters are met, the site may
catalysts are thus designed with a pore size distribution and then consider the lower purchase cost associated with low-
porosity to minimise diffusion limitations, resulting in better density catalysts, and the lower operating cost associated with
utilisation of the catalyst activity for converting the organic low-temperature catalysts. Criterion’s 234 TGU catalyst exhibits
sulphurs to H2S. both of these features. It is a low-density catalyst and can be
It is also important that TGU catalysts are capable of operated at lower reactor inlet temperatures.
handling temperature excursions without significant loss of Once the catalyst reaches its end-of-cycle (EOC) without
surface area and catalyst strength. Due to fluctuations in the unusual incidents such as sooting, it has no other value except
oxygen-to-fuel ratio, the catalyst may be exposed to elevated reclamation of the transition metal components. If the catalyst
temperatures during a typical cycle. is sooted, regeneration can be considered. However, due to the
Soot formation is the other frequently occurring issue in a critical nature of this processing unit, regeneration economics
TGU, due to operation with a too low oxygen-to-fuel ratio in are not considered worth the risk.
the Claus unit. The soot formation results in an elevated
pressure drop over the TGU catalyst bed. It should be noted Elise Mophett, BASF Catalysts, Global Product Technology
that even a very small pressure drop increase is typically Manager, Adsorbents, elise.mophett@basf.com: As
unacceptable, as the blower does not have additional capacity environmental regulations push sulphur recovery efficiencies
to compensate for the increase in pressure drop and to ever-increasing levels, even to the extent of upstream plant
consequently the throughput of the TGU is decreased. shutdowns, should the sulphur recovery unit (SRU) not meet
Therefore, even the smallest pressure drop increase will often emissions expectations, the need for catalyst optimisation
require a catalyst replacement to keep the refinery operating through the SRU is crucial. Minor contaminants like carbonyl
at full capacity. sulphide (COS) and carbon disulphide (CS2) can escape even

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the most efficient amine-based tail TGU if levels are high. In strategies are available to increase ULSD or Euro V diesel
some cases, 50% of the sulphur leaving the SRU comes from production? Considering that 20–30% straight-run (50
COS and/or CS2 contamination. The use of a titanium dioxide cetane) diesel is typically downgraded to LCO in the catalytic
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
cracker, how can this practice be reduced to 10%?

the TGU. In addition, should TGU bypass be required, the Larry Kraus, Team Leader, Clean Fuels, Projects and
Claus unit will have the best available catalyst configuration, Strategic Accounts, Criterion Catalysts & Technologies,
allowing for the maximum achievable recovery until the TGU lawrence.kraus@cri-criterion.com: Some of this high cetane,
is back on-line. 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

❝ 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
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
emissions and meeting future CCS requirements?
❞ making reactor volume available to do some additional
catalytic dewaxing to improve diesel cold flow properties.
More than a dozen of these applications are operating
Alan Del Paggio, Vice President, Upstream and Renewables, worldwide.
CRI/Criterion, Alan.DelPaggio@cri-criterion.com: CRI/ For the heavy diesel that goes to an FCC pretreat unit, we
Criterion’s products, which support CCS, are in fact have been successful in turning this material into ULSD,
multifunctional and can be used in a broader range of either directly at the FCC pretreat unit or by recovering the
applications. For example, hydrogen permeable palladium FCC pretreat LSD product and reprocessing it in the ULSD
and/or palladium alloy membranes can also be used in unit using modified catalyst systems. Hydrotreated diesel
distributed hydrogen production to augment hydrogen streams are difficult to process because the sulphur and
production and/or recovery, as well as to enhance hydrogen nitrogen species remaining in them are very refractory.
purity. Within this context, the postponement of CCS Criterion has commercial experience processing hydrotreated
projects represents a fractional loss of opportunity and is not diesel streams in a variety of low- and high-pressure units.
catastrophic. We are hopeful, however, that CCS activities For the heavy diesel that is processed in the FCCU, much of
will resume when global economic conditions allow. 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

❝ 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
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
measures to increase distillate production, what cost-effective 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


3rd turnaround service cycle? If so, is this because
proper turnaround management of new catalyst technology

refining and catalyst enhancement systems has become more


complicated or is it due to more stringent reliability and

China

safety standards?

2009 ★

★ ★ 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
17–18 March 2009 done correctly to ensure maximum performance is obtained
from the reactor/catalyst system. ULSD regulatory activity in
Beijing 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
The networking event of the year for everyone naturally resulted in technology provider coordination of
with an interest in refining technology in China. their installation in the 2006-2008 period. Subsequent
Combine it with a visit to CIPPE, 19-21 March 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
www.refiningchina.com 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

10 PTQ CATALYSIS 2009 www.eptq.com

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loading of the several types of grading components and new load of catalyst and to assure the safest possible operation
catalysts employed. Indeed, for decades ART has offered its of the unit throughout the cycle.
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
❝ How are catalysts performing with the limited amount
of biofuel feedstocks currently processed through select diesel
hydrotreaters? What performance capabilities can refiners
readily provided.

Dan Torchia, Catalyst Sales and Services Manager, Chevron


expect to see in a biodiesel catalyst beyond 2010?

Lummus Global, dan.torchia@chevron.com: CLG has Shiflett: Some time ago, ART embarked on a pilot plant
noticed an across the board increase in requests for assistance study using ULSD proprietary SmART catalyst systems to
with managing and executing catalyst change-outs, reactor define the landscape for the co-processing of bio-derived
inspections and start-ups. The scope of these requests ranges and petroleum-derived diesel stocks, with a subsequent
from a simple review of turnaround procedures to hands-on publication on the work. Owing to uncertainties in US
execution and management of the entire process. This increase tax credits for biomass-containing alternative diesel and
is believed to be driven by: national EU biofuels targets overlaid with no EU-wide tax
— Need for increased operating safety as unit severity policy on biodiesel, there is yet limited feedback from the
continues to increase field. Should co-processing take an appreciable role in
— Longer operating cycles (less frequent turnarounds and diesel production employing biocomponents, concerns about
“loss of memory”) pour point and cloud point can be addressed by the
— Reduced refinery staff levels appropriate tailoring of catalyst systems in modest biofuel co-
— Shift from longstanding local habits to industry best processing. The accommodation of higher and higher oxygen
practices content with greater biofuel utilisation will have design and
— Demand for higher operating factors. revamp implications for facilities that must handle the
Typically, this activity should begin immediately following resultant exotherms within current infrastructures.
a catalyst change-out decision and address schedule, activities
and contractors, as well as identify and assign responsible Torrisi: Criterion catalysts for the co-processing of biofeeds
individuals in the various organisations and departments. The in diesel production have performed as anticipated in
turnaround plan should be finalised several months in commercial application. We expect co-processing to remain
advance of the actual event to allow for methodical ordering a viable, attractive strategy for refiners and will therefore
of supplies, scheduling of resources and the all too common continue our research to produce new catalyst options for
early shutdown. this renewable feed blend. New products and technologies
CLG believes that this planning and working together is will produce catalysts that will help refiners to leverage their
essential to get the most from your operating unit, from your existing processing assets with drop-in catalytic solutions.

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 Mourik International B.V.
locally, as we operate Nieuwesluisweg 110
through a world-wide 3197 KV Botlek-Rotterdam
network of subsidiary The Netherlands
organizations. Tel. +31-10-296 56 00
Fax +31-10 296 56 09
Offices: Europe, Middle East, Asia, E-mail: mint@mourik.com
North America, South America

mourik.com
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reaction matters...

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At crucial moments, the right reaction matters. When you are looking
for the right reaction from your process catalyst, turn to BASF. Our
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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

René Gonzalez

A
gainst a backdrop of global are due to come on-line in 2009 and refinery expansion at Ruwais, which is
recession, most refinery 2010. For example, the United Arab scheduled to be completed by 2014 and
investment up to 2012 involves Emirates (UAE) is set to double its will add 417 000 bpd to Adnoc’s refining
improvements to existing assets. refining capacity as it and other Middle capacity.
Improvements to catalytic processes will Eastern countries make efforts to The major slowdown in China’s
focus primarily on hydrotreating and diversify their oil and gas industry away economy is, of course, another aspect
hydrocracking. This includes expansion from simple crude oil exports. A glut of to consider with regard to refinery
of necessary hydrogen sources and tail spare refining capacity may actually profitability. China has seen a drop in
gas treating/sulphur recovery capacity. accelerate efforts to remain competitive its economic growth as The Organisation
These expanded hydroprocessing by increasing refinery complexity. It for Economic Co-operation and
networks, coupled with efficiency therefore stands to reason that the level Development (OECD) economies
improvements to crude units and of catalyst capabilities will also increase. curtails its demand for Chinese goods.
select thermal conversion processes While cyclicality is built into refining For example, Chinese exports in
(eg, delayed coking and visbreaking), outlooks, the current negative outlook November 2008 fell 2.2% from the
increase the facility’s Nelson complexity stems from demand changes that appear same period in 2007, the first decline in
index. The higher the refinery’s to be structural and enduring, according seven years. China’s economic growth
complexity index, the more capable it to Andrew Oram, Senior Credit Officer slowed to 9.0% in Q3 2008, down from
is of processing and converting heavier for Moody’s. The downturn marks the 11.9% in 2007. The World Bank has cut
feedstocks into lighter components. end of a long boom period for refiners China’s 2009 growth forecast from 9.2–
Over the next two to three years, the that began in 2003 as world demand for 7.5%, the lowest since 1990. China’s
light components expected to yield the diesel and other products took off. economic annual growth has averaged
highest margins are typically in the By the end of 2009, another 2.5 9.9% for the past 30 years. A recent
middle distillate range. However, the million bpd of refining capacity will be International Energy Agency (IEA)
high concentration of metals added around the world, according to forecast noted oil demand in China
contaminants and inorganics found in Goldman Sachs. But those projects that grew 5.3% to 7.9 million bpd in 2008,
many of today’s crudes can decrease a have taken years to move from the but expects it to weaken to 3.5% growth
hydroprocessing catalyst’s activity level conceptual phase to construction are in 2009, approximately 180 000 bpd
and ability to upgrade feedstocks into now threatening to flood the market less than previously expected. According
ULSD and other high-margin products. with a glut of extra capacity just as to the IEA, if the country’s economy
Regardless of how much additional growth in demand for many were to expand by only 7.0% in 2009,
reactor capacity is added to compensate hydrocarbon-based products has slowed oil demand growth would be just 70
for the negative effects of these metals in line with a weakening global 000 bpd, a level not seen since the
contaminants, the most cost-effective economy. It is impossible to predict late 1990s.
strategy may be to consider employing how long this downward cycle will last, However, many other factors must be
several types of catalyst in each reactor. just as it was difficult to predict when it taken into account when considering
In almost every case, an increase in would begin. But more complex refinery the viability of today’s refinery
catalyst inventories at many refineries is networks, as well as those with rapidly operations, including:
a reflection of the flexibility needed to expanding populations such as in the — The previously noted flexibility in
deal with the changes in feedstock Middle East, may be somewhat insulated the refinery’s configuration for crude
properties that typically require higher from the downturn because domestic processing
severity hydrotreating/hydrocracking demand for refined products is booming — The superior product slate of the
conditions (eg, higher temperature, and and refining units are part of larger refinery
hydrogen partial pressure). More state oil firms. For example, Saudi — The strategic location of the facility
importantly, it is the cost of maintaining Arabia, the world’s top oil exporter, — Freight advantages
a diversity of catalyst types inventoried became the fastest growing oil consumer — Ability to maximise jet fuel and
at refineries that complicates refinery in 2008 and will see oil product demand diesel and minimise furnace oil
operations, particularly in the current increase by 7.0% in 2009 to 1.8 million — Captive cogeneration power plants
downturn. bpd. Large facilities under construction to meet the facility’s steam and power
in the region include two export- requirements
Economic considerations orientated refineries in Saudi Arabia, a — Hydrogen production efficiency.
The downturn in the global economy refinery in Kuwait and the Abu Dhabi The most complex refiners can choose
comes just as several world-scale facilities National Oil Company’s (Adnoc) the types of crude they want to process.

www.eptq.com PTQ CATALYSIS 2009 15

rene.indd 1 2/2/09 10:11:06


This advantage may become even more FCC pretreater, considering that it is catalyst for paraffinic hydrocarbons.
important in the future as refiners strive to be tasked with saturating Briefly, these developments, as noted in
to reduce their overall emissions by dibenzothiophenic compounds in the research by Aoki et al, generally include
differentiating crudes according to their heavy tail of resid-based feedstock. In catalyst comprising platinum loaded
potential to generate CO2. Being able to addition to at least one guard bed to into a support containing silica
choose the types of crude to be processed mitigate metals and nitrogen alumina.1
depends to a large extent on a facility’s contamination of reactor catalyst, the Other research has demonstrated the
catalyst-based processes, including pretreater reactors will require a well- hydrocracking of paraffinic hydro-
hydrotreating, hydrocracking, fluid planned combination of the latest carbons using a catalyst comprising
catalytic cracking (FCC) and others. NiMo/CoMo catalyst formulations, platinum loaded into a crystalline
probably operating at H2 partial aluminosilicate (zeolite). The crystalline
Global distillate demand pressures in excess of 1900–2200 psi aluminosilicate catalyst is at a
Since the new millennium, diesel and even higher pressures at end of run satisfactorily higher level of cracking
hydrotreating has primarily involved (EOR). The elimination of SOx and NOx activity, but the middle distillate yield
sulphur removal to low (<500 ppm) or precursors via pretreatment will is low and the resulting gas oil fails to
ultra-low (<10 ppm) levels. In addition, certainly go a long way towards meeting obtain a sufficient pour point. On the
cetane uplift and poly-aromatic future NOx and SOx emissions from the other hand, amorphous solid acid
hydrocarbon (PAH) removal are possible FCC regenerator. catalysts, such as silica alumina, are at a
with new catalysts. Hydrotreating diesel This seems to be the case with satisfactorily higher level in achieving
can require severe processing, especially numerous refiners currently in operation middle distillate yield along with the
when ultra-low sulphur is needed and throughout the world, including the low pour point of the resulting gas oil,
the feedstock contains cracked NPRC refinery in Japan processing Arab but are low in cracking activity. Ideally,
components. The highest activity Light crude. The facility employs a catalyst suppliers strive to formulate
catalysts are usually required for ULSD vacuum resid desulphurisation unit for hydrocracking catalysts that satisfy
production to reach acceptable cycle FCC pretreatment. high cracking activity and middle
lengths. CoMo catalysts are most often For distillate-focused refiners distillate yield as well as low
specified for diesel and ULSD currently thinking of phasing out FCC pour point.
hydrotreating operations, but NiMo operations, it should be mentioned Inorganic contaminants in refinery
catalysts may be preferred in some that complete dependence on feedstocks are often poisons for
cases. hydrocracking may leave them with a hydroprocessing catalysts. The source of
Hydrocracking catalysts usually significant vacuum residue problem, these contaminants is frequently the
incorporate zeolites to selectively crack which the FCCU can address. The latest crude itself, with different contaminants
heavier feed components into lighter developments in resid FCC processing associated with various crude sources.
products. Nitrogen in the feed causes technology and catalysts, including the Some contaminants are introduced
substantial inhibition of the acid sites processing of feeds with higher CCR during normal refining processes or
in the zeolite responsible for cracking. and metals content while increasing from upset conditions. To control this
Pretreatment of hydrocracker feedstock LCO yields, have rendered the FCCU a growing problem, increasing volumes
to reduce nitrogen content to a low viable option over the construction of of catalysts with a high capacity to
level substantially increases the a visbreaker, particularly if the FCCU adsorb contaminants at the top of the
conversion activity of the zeolitic already exists and can be upgraded. reactor’s catalyst bed are being employed.
hydrocracking catalyst. In today’s Resid cracking over modern catalysts in These sacrificial catalyst layers protect
refinery environment, a high pressure a resid FCCU produces valuable downstream catalysts from the
hydrocracking unit may be too costly products in addition to fuel oil poisoning, allowing them to retain their
for many oil companies. A more cutter stocks. high activity for a longer time and
affordable solution that generally costs increase cycle length.
about a third of a full hydrocracking Catalyst efficiency
unit is a mild hydrocracking (MHC) In the process of hydrocracking Reactor investment
unit. For example, more than 20 Axens paraffinic hydrocarbon, it is important vs catalyst cost
MHCs have already been licensed for a to produce useful middle distillates at The total on-site capital cost estimate
combined capacity of 700 000 bpsd. higher yields to improve the economical for a new hydrotreater plant varies,
Should favourable economics compel efficiency of the process. In addition, depending on the licensed and
refiners to achieve near-complete the resulting gas oil is necessarily low in proprietary technology. It consists of
elimination of heavy fuel oil, the first pour point. That is, development of a three parts: a two-reactor system (in
step would be to process FCC cycle oils highly efficient hydrocracking catalyst, series) with interstage H2S stripping,
in the MHC unit, along with VGO. which can enhance the cracking activity hydrogen make-up compressors and
More than likely, this would require the and middle distillate yield of the remaining on-site capital equipment.
addition of a second stage to the MHC hydrocracking process, while also The cost of the reactor system and
unit to process VGO, LCO and heavy making it possible to produce a gas oil make-up compressors is a function of
crude oil (HCO), essentially converting with low pour point, holds the key to the percentage of cracked stocks present
the unit into a full hydrocracker. The an improvement in economical in the hydrotreater feed pool, whereas
second step would be to consider the efficiency at low-to-moderate hydrogen the cost of the remaining on-site
construction of a vacuum resid partial pressures. equipment is a function of capacity.
hydroprocessing unit, which would Of course, VGO hydrocracking has The combined flow rates, space
treat FCC feed. Another alternative is to been an established process for decades. velocities calculated from kinetic
install an atmospheric resid pretreater, However, since the difference between models and pressure are used to size
shut down the vacuum tower and feed the reactivity of a paraffinic hydrocarbon each reactor, with the restrictions that
that product to a resid FCCU. Eighty per and that of a VGO is so significant that the reactor length-to-diameter ratio
cent of the world’s crude could be it is difficult to use the catalyst for the must be greater than or equal to five,
processed in this manner. latter as it is for hydrocracking a and the diameter must be less than or
However, some relatively high paraffinic hydrocarbon, R&D aims at equal to 15 ft. The cost of each reactor
operating costs are to be expected for an the development of a highly efficient is a function of the wall thickness and

16 PTQ CATALYSIS 2009 www.eptq.com

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


reactor weight. Next, the hydrogen content declines on a volume basis, begs the question as to how fast does
make-up compressor costs are calculated because the heat content of the product this affect hydrotreating catalysts
based on the hydrogen consumption. is 0.989 times the heat content of the currently available for ULSD production?
Differences in capital costs at a given feed on a volume basis.The same Other problems encountered with LCO
capacity level are the result of variations hydrogen consumption and hydrogen processing such as fouling and corrosion
in the fractions of the different types of plant cost estimation methodologies are also need to be considered as some
feed (eg, straight run vs cracked stocks) used by many for both the new and refiners try to process higher percentages
and the sulphur level of the feed to the revamp cases. of cracked stocks through their ULSD
hydrotreater. For example, an estimate In the US, oil refiners must produce hydrotreaters. How often refiners go off-
of $1600 bpsd is believed to be a more 100% ULSD by 2011. Refiners are spec or increase rerun in an effort to
representative ISBL investment cost to projected to invest $6.3–9.3 billion to process higher LCO fractions is difficult
produce ULSD. meet full compliance with the ULSD to ascertain. It seems to depend on
The revamped hydrotreater on-site Rule through 2011. Most refiners are multiple factors, including:
capital portion of the model utilises close to completing upgrades necessary — Production of only one grade of
only the space velocity calculated for for full compliance. After 2011, the first diesel (eg, less than 10 ppm S)
the second reactor, used to lower the full year of 100% ULSD, the projected — Availability of tankage for rerun
diesel pool sulphur content from 500 differential of marginal prices is expected material
ppm (manually specified) to 7 ppm. The to decline, because of lower distribution — Deactivation rates for
revamped hydrotreater capital cost and capital investment costs. hydrodesulphurisation (HDS) catalyst at
includes only an additional reactor, In Europe and the Middle East, where severe hydrotreating operations
heater and separator, and assumes the hydrocracking capacity is significantly — LCO end point limits (ie, how much
existing inside battery limit equipment higher than in the US, uncertainties undercutting is required?).
will remain unchanged. over the pace of engine, refinery and Again, depending on the volume of
Until recently, on-site capital costs pipeline testing technology LCO being hydrotreated in ULSD
for new and revamped hydrotreater development; the availability of operations with FCC post-treaters, one
plants have included the initial catalyst personnel, thick-walled reactors and of the unanticipated problems reported
charge. The off-site capital cost for a reciprocating compressors; the by a number of refiners deals with EOR
new plant has been assumed by many behaviour of ULSD in the oil pipeline conditions, where there may be a close
in the industry to be 45% of the on-site system; and cost recovery by oil pipelines relationship to LCO content and
capital cost, and the off-site capital cost further cloud the outlook for the product colour. The higher EOR
for a revamped plant is assumed to be transition to very low levels of sulphur temperatures produce olefins that
30% of the on-site capital cost. in diesel fuel. react with nitrogen and sulphur
Hydrotreater catalyst cost (in dollars compounds.
per barrel) is a function of space LCO to distillate Whenever an FCC pretreater is
velocities and has been calculated LCO, containing 50–85% aromatics, is employed to achieve ULSD and low-
assuming a two-year life, with CoMo a distressed refinery stream with limited sulphur gasoline specifications and
catalyst typically in the first reactor and future disposition options, which is LCO quality is an issue (eg, increased
NiMo in the second reactor. CoMo is why refiners are considering additional levels of dibenzothiophenes),
more reactive in removing sulphur upgrading options such as adjustments to the FCCU itself may be
from the less challenging sulphur- hydrocracking. Hydrotreating and necessary. A detailed discussion on
containing molecules. Below 500 ppm, hydrocracking licensors have proposed what adjustments are necessary to the
however, the sulphur present is more various process configurations and new FCCU is beyond the scope of this article
likely to be contained in sterically catalyst capabilities so refiners can and can be obtained in the recently
hindered molecules and more difficult avoid the costly option of severely released FCC study authored by myself
to remove using a CoMo catalyst. In hydrotreating multi-ring thiophenic and FCC expert Warren Letzsch, The
contrast, NiMo has higher activity on LCO. It should be noted that higher FCCU in Transition, available from www.
more challenging sulphur-containing costs come with new catalyst eptq.com/studies.
molecules. Published data have shown capabilities. However, despite recently
that the costs of both catalysts are $10 announced price increases in FCC New desulphurisation
per pound, including royalty. catalyst (including LCO upgrading technologies
catalysts) by major catalyst suppliers Beyond traditional hydrotreating to
Yields such as Albemarle, BASF and Grace remove sulphur from diesel streams,
The volume and weight percentage Davison, catalyst costs remain a small new technologies are under develop-
yields of ULSD produced by the typical part of the overall refinery operation ment that could reduce the cost of
distillate hydrotreater can vary relative to feedstock costs. desulphurisation. They include sulphur
considerably, depending on the fraction Severe hydrotreating improves LCO, adsorption, sulphur oxidation, gas-to-
of cracked stocks in the feed and the with an increase of one cetane number liquids and biodiesel. Each of these
level of aromatics saturation. An average for every 75–80 ft3 of hydrogen technologies is in the first stages of
yield and energy content were estimated consumed. These conditions are commercialisation. It is uncertain
for this article, based on the Criterion required to desulphurise the sulphur whether any of them will make a
data in a June 2000 study by the found in the alkyldibenzothiophenes significant contribution to meeting the
National Petroleum Council. The yield (DBT). If LCO is to be upgraded to requirements of future refined product
of hydrotreater product in the distillate ULSD, it is evident that LCO specifications, although they may have
boiling range was assumed to be 98% by hydrotreating would have to be some impact later in the next decade.
weight, and the API gravity was assumed relatively severe (high pressure) to
to increase by two numbers, which achieve a limited improvement in
means the volume yield was 99.2%. cetane number, aromatics reduction
There was also a small increase in the and density.
Btu content of the product on a weight Running relatively high percentages References
1 Nobuo Aoki, et al, USPTO Patent Application
basis (98.2% of the feed energy content of cracked stocks such as LCO and light 20080306321, Process for producing liquid
in 98.0 wt% of the feed). The energy coker gas oil (eg, in the 30–50% range) hydrocarbon with hydrocracking catalyst.

www.eptq.com PTQ CATALYSIS 2009 17

rene.indd 3 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
t
ro c
e
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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
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l
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u ww w. cl g-
1) 5 1 0
cl e . 4 2. 2ds .
an . c 3 17 7
om

cleaner
transportation fuels

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

www.ptqenquiry.com
for further information

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.

0ROPYLENEYIELD WT

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 *AN *AN *AN
area. This resulted in the need to operate
at a lower reactor temperature, leading
to a lower propylene and butylenes yield Figure 2 Propylene production in the Gibraltar-San Roque FCCU
and an increase in slurry; in other words,
a reduction in total throughput. Brilliant (preblended with 8–9% different optimisation scenario. The data
CEPSA’s R&D facilities in Madrid OlefinsUltra) was compared to ProtAgon- obtained in the Davison circulating riser
carried out an extensive catalyst 17C, a catalyst already used in another (DCR) pilot plant established that
evaluation in 2007 to look at the options CEPSA refinery. Grace Davison developed ProtAgon-17C offered all the benefits
for maximising propylene, while taking this first-generation ProtAgon catalyst to required to meet the FCCU’s objectives,
into consideration the constraints of the maintain or increase the propylene so CEPSA chose to use it at its Gibraltar-
commercial FCCU. The base catalyst make and allow CEPSA to operate a San Roque refinery.

www.eptq.com PTQ CATALYSIS 2009 19

grace.indd 1 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


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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


Shell Global Solutions (US)

T
he FCC regenerator is a major
NOx emission source in refineries. 2.0
Several existing technologies are
available to reduce NOx emissions from a
FCC regenerator, which include De-NOx
catalyst additives, selective catalytic 1.5
O2, CO, CO2 in flue gas, %

reduction (SCR) and selective non-


catalytic reduction (SNCR). Technology
recently developed by Shell Global
Solutions can be used as a standalone 1.0
strategy, to reduce NOx emissions to as
low as 40 ppm or less, or in conjunction Measured O2
with one of the previously noted existing Measured CO
0.5
technologies. Measured CO2

NOx formation
Most NOx emissions from FCC flue gas 0.0
0 5 10 15 20 25 30 35 40
come from nitrogen in the feed. The
Time, minutes
contribution of direct oxidation of N2 to
NOx is negligible, particularly for full-
combustion FCC regenerators. For Figure 1 CO, CO2 and O2 in the flue gas as a function of time2
partial-combustion regenerators, the
contribution of direct oxidation of N2 to of spent FCC catalyst with oxygen and experiment. Most of the coke nitrogen
NOx is relatively small if low-NOx burner helium reveals a close interaction between was released as N2, which peaked at 13.5
technology is applied in the CO boiler/ the combustion of carbon and the release minutes at 200 ppm, under a reduction
incinerator. of nitrogen in the coke. Figure 1 shows or a slightly oxidation environment. A
A recent study shows1 that about 50% the concentrations of CO, CO2 and O2 in fraction of coke nitrogen was released as
of nitrogen in the feed exits the FCCU the flue gas as a function of time as coke HCN, which peaked at 10.5 minutes at
on the reactor side, and the remaining on catalyst is burned off in the batch 35 ppm under the same environment.
50% exits as coke on spent catalyst sent regeneration experiment. The amount of The NO concentration was below 20
to the regenerator. Of the 50% feed coke on catalyst was not directly ppm for the first 14 minutes under a
nitrogen exiting from the reactor, about measured, but Figure 1 implies that coke reduction or slightly oxidation
10% ends up as ammonia, which is on catalyst was removed continuously, environment when both coke on catalyst
collected in sour water, and the other converted to CO/CO2 and became and CO were present. NOx levels
40% ends up in various streams of the negligible after 26 minutes, as both CO increased sharply afterwards, and peaked
reactor liquid products. and CO2 concentrations fell to negligible at 18 minutes at 190 ppm, when the CO
This article focuses on the remaining levels. For the first nine minutes, the O2 concentration fell to negligible levels
50% feed nitrogen, which enters the concentration remained low and the CO and the O2 concentration increased
regenerator in the form of coke on spent concentration was higher than CO2, beyond 1%, as shown in Figure 1.
catalyst. As the spent catalyst is indicating a reduction environment in The proposed reaction kinetics2 for the
regenerated and coke is burned off in this period of the batch regeneration. As release of coke nitrogen in the CC catalyst
the regenerator, the nitrogen species on O2 broke through the unit at ten minutes regeneration process involves the initial
coke are released into the flue gas. and its concentration continued to rise, volatilisation of coke nitrogen as HCN,
Recent studies1,2 further show that less coinciding with a sharp drop in CO which could be hydrolysed to another
than 5% of feed nitrogen on coke is concentration and a rise in CO2, the intermediate, NH3. Both intermediates,
released in the form of NOx emissions in batch regeneration shifted gradually from HCN and NH3, can be oxidised to NO,
the flue gas. More than 45% of feed a reduction environment to an oxidation which can be reduced to N2 by the
nitrogen on coke is initially released in environment. presence of CO or/and coke on catalyst.
the form of NOx or other intermediates, Figure 2 shows the concentrations of
but is converted in situ to N2 in the NO, HCN and N2 in the flue gas as a Low-NOx regenerator
regenerator. function of time as coke nitrogen is The FCC regenerator design has a direct
A recent study2 of batch regeneration released in the same batch regeneration impact on the effectiveness of in situ

www.eptq.com PTQ CATALYSIS 2009 23

shell.indd 1 2/2/09 10:18:46


zone by the introduction into the dense-
phase catalyst zone of more than one
250
fluidisation gas stream, each of which is
directed and controlled in such a manner
as to cause the formation of multiple
200
fluidisation regions. Thus, introduced
HCN, NO, N2 in flue gas, ppm

into the central portion of the dense-


phase catalyst zone is a high superficial
150
velocity fluidisation gas stream that
passes by way of conduit (30) to
fluidisation gas distribution ring or rings
100
Measured N2 (32) near the bottom of the regenerator
Measured HCN vessel. Introduced into the annular
50 Measured NO portion of the dense-phase catalyst zone
is a low superficial velocity fluidisation
gas stream that passes by way of conduit
0 (36) to fluidisation gas distribution ring
0 5 10 15 20 25 30 35 40 or rings (38) located within the annular
Time, minutes portion near the bottom of the
regenerator vessel.
Figure 2 NO, HCN and N2 in the flue gas as a function of time2 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
2 24 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
46 36
38 includes the introduction of spent
32 32 catalytic cracking catalyst into the high-
48 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
Figure 3 Schematic diagram of the low-NOx regenerator system high-velocity central region in a
horizontal direction and mixes with
reduction of NOx to N2, and hence the catalyst zone further includes a high- catalyst circulating from the bottom end
reduction of the final NOx emissions in velocity central region (22), located in of the low-velocity annular region. The
the flue gas. The Shell low-NOx the central portion (26) of the dense- regenerated catalyst is removed from the
regenerator technology shown in Figure phase catalyst zone, and a low-velocity low-velocity annular region by way of
3 enables the unit to operate in both full- annular region (24), located in the conduit (54), which removes regenerated
and partial-combustion modes with low annular portion (28) of the dense-phase catalyst from the annular portion of the
NOx emissions. catalyst zone. It is a significant aspect of dense-phase catalyst zone.
As shown in Figure 3, the regenerator the new regenerator technology that One advantage of the new regenerator
system (1) includes a single regenerator the high-velocity central region and the system is that the induced catalyst
vessel (10) with an upper end (12) and low-velocity annular region are formed circulation pattern distributes partially
lower end (14). The regenerator vessel within the dense-phase catalyst zone regenerated spent catalyst to the
(10) includes a dilute-phase catalyst zone without the use of a structural element proximity of the surface (20), which
(16) above and a dense-phase catalyst such as a vertical baffle or a partition. results in reducing NOx emissions from
zone (18) below, with a transition surface The two fluidisation regions are instead the regenerator. Another advantage of
(20) between the two. The dense-phase formed within the dense-phase catalyst the new regenerator system is that the

24 PTQ CATALYSIS 2009 www.eptq.com

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

www.eptq.com PTQ CATALYSIS 2009 25

shell.indd 3 2/2/09 10:19:46


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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


— Pre-upgrading sulphur removal
For example, installing VGO
 hydrotreating to reduce the sulphur
 content of FCC, LCO and DCO

 — Residue upgrading Direct
n

hydrotreatment of the hardest to treat
n
residue streams
 n
n
— Whole crude hydrotreatment To

n
convert high-sulphur crudes to low-

3ULPHURCONTENT

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,

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

28 PTQ CATALYSIS 2009 www.eptq.com

foster wheeler.indd 2 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 2ESID(#+ !2$3

Figure 6 Impact of desulphurisation options on carbon emissions

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

www.ptqenquiry.com
www.eptq.com for further information PTQ CATALYSIS 2009 31

foster wheeler.indd 5 2/2/09 14:12:36


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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  -AYACOKING 53'#
feeds, Criterion’s proprietary Ascent -ARSCOKING 53'#
 -ARSCRACKING 53'#
catalysts are being increasingly used for
5RALSCRACKING %UROPE
their ability to: 
"RENTCRACKING %UROPE
— Show greater stability in more severe 
BBL

operations at higher temperatures and



lower pressures
— Be employed flexibly to select the 
optimum fluid catalytic cracking (FCC) 
pretreat operating strategy to maximise n
FCC margins
— Process heavier feeds with more n
contaminants n
           
— Desulphurise, denitrify and saturate
to a high degree using lower amounts of
hydrogen Figure 1 Past and current cracking and conversion margins. Source: IEA
— Produce ultra-low sulphur diesel
(ULSD) and low-sulphur gasoline to the capability to process more heavier crudes have resulted in the
— Work effectively and in conjunction difficult feeds. higher production of lower value,
with mild hydrocracking catalysts in the difficult VGOs more suited to the FCC
more severe operating regimes employed FCC in a growing middle pretreat/FCC complex than a
for mild hydrocracking. distillate market hydrocracking unit due to the high level
FCC continues to serve an important of feed contamination.
Clean fuels success role in the refining industry, with an In addition to reviewing how to best
In complex and integrated refineries, estimated 350–400 FCCUs in operation optimise FCC operations, Criterion is
meeting stringent gasoline and ULSD today. Improvements in technology and working with various refiners to increase
specifications has greatly increased the catalysis have increased the conversion their middle distillate yield from the
impact of process unit interactions. This level of VGO feedstocks into more FCC pretreat/FCC complex by increasing
move to clean fuels, continued increases valuable middle distillates, gasoline and VGO conversion in the FCC pretreat
in crude pricing as well as shifts in olefin products. Ongoing market changes (PT) unit through modified operating
demand between motor gasoline and in pricing and product demands have strategies or catalyst systems.
diesel have required competitive refiners raised questions over how best FCC
to re-evaluate how to best utilise both assets can be utilised. Need for higher activity and
available refining assets and limited While FCC yields vary based on feed stability in pretreatment
capital budgets. quality and process conditions, typical Success in the pretreatment of FCC feed
In vacuum gas oil (VGO) processing, operations yield 50–60 vol% gasoline is a function of both catalytic performance
increases in hydroprocessing and 15–20 vol% light cycle oil (LCO) and catalyst stability. Since being
performance have been achieved with from a VGO feed. Prior to widespread introduced to the market in 2006, Ascent
the Ascent family of catalysts. In today’s clean fuels introduction, similar pricing catalysts have been selected globally in
refining environment of increasing feed for both gasoline and distillate products over 50 applications involving VGO
difficulty and contracting profit provided strong incentives for FCC treatment. Commercial success has been
margins, these improvements in conversion, producing both gasoline measured by improved FCC operations,
catalytic performance have allowed and distillate from the low-value fuel oil longer catalyst cycle lives and the ability
refiners to review how to best utilise pool. Continued demand growth for to process more difficult feeds. Ascent
their refining assets. Refiners who low-sulphur diesel, however, has catalysts are manufactured by a process
are using the Ascent technology to increased the low sulphur diesel margins, providing enhanced promoter metals
pretreat the feed for FCC operations are thereby making gasoline production less utilisation through an optimised catalyst
realising significant benefits, from desirable in some markets. physical structure designed to better
extended periods between unit Globally, both increased coker tolerate the contaminant metals present
shutdowns, increases in refinery yields capacity and increased processing of in heavy gas oil feeds.

www.eptq.com PTQ CATALYSIS 2009 33

criterion.indd 1 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
2UN HR directly from the FCC PT unit.
Figure 2 shows the improved metal
uptake capacity of Ascent catalyst when
Figure 3 Accelerated ageing test comparing Ascent stability to Type II catalyst compared to demetallisation catalysts
and the previous generation of FCCU PT
Ascent DN-3551 is the most active high desulphurisation performance catalyst DN-200.
FCC PT nickel molybdenum (NiMo) while reducing the operational hydrogen Figure 3 shows the comparative
catalyst. It is well suited to high-severity requirement (to be discussed in more performance in a medium-pressure,
FCC PT operations, providing high detail in part II). Its design promotes accelerated ageing catalyst test of Ascent
contaminant metals tolerance while increased HDN and aromatics saturation catalyst vs a Type II catalyst. In this test,
performing a high degree of denitrifi- the feed and conditions were chosen to
cation (HDN), desulphurisation (HDS) accelerate the ageing of the catalyst so
and aromatic saturation (HDA) — Feed and operating conditions that comparative results could be seen
reactions critical in FCC feed quality in a shorter time.
upgrading (to be discussed in more detail Catalyst system DN-3551 NiMo
in part II of this two-part article). Ascent’s LHSV 0.9 hr-1 Case study 1
Capacity 411 m3/hr
DN-3551 NiMo catalyst is designed to Extend cycle life in FCC PT unit
Pressure 82 bar
achieve very high FCC feed PT to help Low deactivation rates have been
H2/oil 550 m3/m3
meet tighter specifications on achieved at a refinery that has been
Feed type SR GO, SR VGO & 20% HCGO
downstream FCCU operation and Feed
operating with Ascent DN-3551 for over
product slate (see Case study 2). It can be S.G. 0.924 one year, following successful runs with
supplied in an oxide (non-presulphurised) Sulphur, wt% 2.2 previous generations of Criterion
form and provides the advantage of Nitrogen, wppm 2400 catalysts. Processing a challenging mix
being able to employ conventional Concarbon, wt% 0.6 of crudes and coker feeds, this unit is
handling and start-up procedures and Feed metals, pwwm <3 currently achieving excellent
conventional ex-situ regeneration for D2887 10% - C 332 performance with less than half of its
reuse in the same or lower severity D2887 95% - C 543 previous cycle deactivation rates. The
service. The Ascent manufacturing Product GO observed superior catalyst activity and
technology produces inherently stronger S.G. 0.866 stability allow for an extended unit run
catalysts that improve recovery during Sulphur, wt% 0.20 length, reduce days off stream due to
regeneration. Nitrogen, wppm 1200 catalyst change-outs and process
Ascent DC-2551 features similar Concarbon, wt% <0.3 economically attractive opportunity
performance, stability and regenerability Feed metals, pwwm <0.3 feeds. Table 1 and Figure 4 give the
to Ascent DN-3551. It is well suited to details of feed operating conditions and
severe FCC PT operations that value a Table 1 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
Desiree J de Haan is Technical Consultant,
FCC Pretreat/Mild Hydrocracking, with
Figure 6 Stability and activity increase observed in unit 636 Criterion Catalysts & Technologies covering
units in the EMEAR region. de Haan is
produce improved FCC feed quality each of the four operating mode options a graduate from Uterecht University in
while providing longer cycle lengths. were considered in an economic analysis. inorganic chemistry and catalysis.
HRLP worked together with Criterion The economic evaluation included Email: D.DeHaan@cri-criterion.com
to determine how to take full advantage amortised catalyst replacement cost and Andy Shivaram is Technical Manager, FCC
of the facility’s capabilities. Several turnaround cost for each mode, as well Pretreat/Mild Hydrocracking, with Criterion
potential operating modes were as FCC conversion shifts for the predicted Catalysts & Technologies in Fareham
examined, including HDS mode, HDN FCC feed quality in each mode. Given Hampshire, UK. Shivaram is a graduate
mode, PNA saturation mode and a constantly changing market economics of chemical engineering from Cambridge
combination PNA-HDN mode. The cycle and refinery conditions, the economic University.
length and turnaround cost impact for advantage of one mode over another Email: Andy.Shivaram@cri-criterion.com
each mode were considered along with fluctuates, but HRLP’s economic analysis Kevin D Carlson is Global Business
the downstream effects of each mode. indicated a consistent and significant Manager, FCC Pretreat & Sentry Products,
Table 3 shows the four operating advantage to run in PNA mode over with Criterion Catalysts & Technologies
strategies that were considered along HDS mode or HDN mode. While PNA- in Houston, Texas. He has worked in the
with the characteristics, advantages and HDN mode is less economically attractive industry for over 18 years and has been
disadvantages of each. than PNA mode, PNA-HDN mode an author of a number of technical papers.
The advantages and disadvantages of provides a reasonable compromise 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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sudchemie.indd
Prozessfarbe 1
CyanProzessfarbe MagentaProzessfarbe GelbProzessfarbe Schwarz 30/1/09 12:26:21
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

Steve Catchpole
Johnson Matthey Catalysts

M
ercury is found in an ever- Reported levels of total mercury Level of mercury in refinery products
increasing number of hydro- in crude oil
carbons worldwide. The Product Amount, ppb w/w
level of mercury can vary significantly, Source Amount, ppb w/w LPG <10
depending on location. The situation is California (Cymric) 30 000 Gasoline 0.22–3.2
complex in refineries, as liquid feedstocks Alberta 2–400 Diesel 0.4–3
can contain elemental, organic and North Sea 2.5–9.3 Naphtha 3–60
inorganic species. Complete removal of Libya 0.1–12.2 Petroleum coke Up to 250
mercury is advisable to avoid catastrophic West Africa 1.5–3.5
failures in cryogenic equipment, to Angola 1.5–2.7 Table 2a
prevent poisoning of process catalysts,
and for health and safety reasons. Table 1 distribution of mercury. These data are
Additionally, hydrocarbon products summarised in Table 2b.
that can be labelled as mercury free are surprisingly mobile. Organo-mercury Due to its ability to manifest itself in
able to command an enhanced product compounds are easily broken down practically all of the crude column
value. For example, mercury-distressed when heated in a reducing atmosphere, products, mercury will be found in a
naphtha may be sold at $5–10 less than and elemental mercury is released number of downstream unit operations.
open-spec naphtha. during the hydrotreating and catalytic Figure 2 shows the measured distribution
There are now over 250 proprietary reforming stages of the refinery. in a FCC/resid cracker, and Figure 3
Puraspec mercury removal units (MRUs) As a result, whatever the original form shows the measured distribution in a
in service on a range of hydrocarbons, of mercury in the crude oil feed to hydrocracker of a typical world-scale
with more than 100 units in commercial the refinery, much of it ends up as refinery.
operation on liquid applications. The elemental mercury in the C3 to C6 Although the levels of mercury
new generation of Puraspec absorbents product streams; namely, LPG, gasoline recorded are low, the tonnages of liquid
have been shown to give effective and naphtha.2,4 hydrocarbons handled are enormous, so
removal and long life without impacting Published levels of mercury found in downstream processing equipment is
negatively on product quality. 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,
Mercury in hydrocarbons distribution of mercury in the crude feed poisoning of catalysts, and health and
Almost all hydrocarbons contain and product streams of the crude column safety. These can involve serious
mercury. In the case of natural gas and of a major world-scale refinery. It is also financial losses.
natural gas liquids, it is likely to be worthwhile to note the prevalence of
present as elemental mercury. In the mercury in the water effluent of the Corrosion
case of crude oil, it may also be present desalting operation. Mercury readily wets most surfaces and
as organo-metallic and ionic mercury. Data derived from world-scale forms amalgams with a number of
The concentration of mercury in natural refineries shed additional light on the metals. A particular concern is
gas varies widely from 450–5000 µg/Nm3
in some fields in North Germany to less
Measured mercury distribution in world-scale refineries
than 0.01 µg/Nm3 in some parts of the
US and Africa.1 Much higher levels of Refinery Mercury level in the Mercury level in the Mercury level in the
mercury can be found in crude oil.2 crude, ppb w/w naphtha, ppb w/w lpg, ppb w/w
Levels found in some crude oils are 1 – 100–200 >10
shown in Table 1. 2 – 50–100 750
Elemental mercury is only sparingly 3 – 5–10 –
soluble in liquid hydrocarbons3 (the 4 – 1 –
solubility in n-octane at 25°C is 2 ppm), 5 1200 30 –
so the high levels recorded show that 6 >5000 <1000 –
mercury compounds must also be 7 – 100 –
present. 8 – 1000 500–1000
Mercury has a high boiling point 9 – 150 –
(356.7°C), but has a high vapour
pressure at ambient temperature and is Table 2b

www.eptq.com PTQ CATALYSIS 2009 39

j mathey.indd 1 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


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tricat.indd 1 30/1/09 14:33:48


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

Tony Pavone
SRI Consulting

P
ropylene glycol (PG) is a basic conventional glycerin markets. Glycerin converting glycerin into PG or PDO
petrochemical used primarily prices, once $1000/mt, have dropped by simply requires substituting a hydrogen
in polyurethane polyols and 50% for refined grades, while raw by- ion for one of glycerin’s OH radicals. This
unsaturated polyester resins, and as product glycerin is often used as can be accomplished with conventional
an anti-freeze agent in aircraft de-icing boiler fuel. industrial chemistry (high-pressure,
applications, as well as an automotive Two organisations have patented moderate-temperature hydrogenation at
coolant. Total annual global consumption their processes for converting glycerin to a low residence time over a base metal
is 1.5 million metric tonnes. Historically, PG: Davy Process Technology in the UK catalyst), or biologically using an enzyme
PG has been made commercially by and the University of Missouri (the catalyst (moderate temperature and
simply hydrating propylene oxide (PO). Suppes process) using R&D funds from ambient pressure and long residence
PO, in turn, has been made historically the US government. time). If the substitution occurs on a
by the peroxidation of propylene using terminal carbon atom, the product is PG.
co-feeds of either ethylbenzene (EB) or Chemical structure of the If the termination occurs on the internal
isobutene (iC4). relevant molecules carbon atom, the product is PDO.
When EB is used, PO is produced with PG is a three-carbon molecule in which
styrene monomer co-product. When iC4 two of the carbon atoms are attached to Value proposition
is used, PO is produced with tertiary hydroxyl (-OH) radicals. The third The patent literature has taught for at
butyl alcohol (or sometimes methyl carbon atom is saturated with hydrogen. least the past 50 years methods for
tertiary butyl ether [MTBE]) co-product. The carbon atoms attached to OH converting glycerin to PG (albeit at low
An older technology produces PO from radicals are adjacent to each other. As a conversion rates). So why does the world
propylene via chlorohydrin chemistry. result, PG has its OH ions on one of the have renewed interest in the chemistry?
Recently, a new plant has been terminal carbon atoms and on its The basic reason is economics. As long
commissioned by SK Chemicals to avoid adjacent internal carbon atom. as glycerin market prices are significantly
co-product formation by using hydrogen higher than propylene monomer market
peroxide as the oxidising agent. prices, there is no compelling economic
Whichever historic route is taken, PG reason for making PG or PDO from
production economics are dominated by glycerin. In this economic world, it costs
the cost of the basic feedstock propylene. A similarly structured, but more more to make PG from glycerin than it
Produced from either natural gas liquids expensive molecule to make and buy, is costs to make PG from propylene.
or refinery naphtha, propylene prices 1,3-propane diol (PDO). Like PG, PDO is Biodiesel has changed this economic
have averaged $1000/mt over the past a three-carbon molecule with two of its world. Since 10% of the production of
three years, and PG market prices have carbon atoms connected to OH radicals. conventional biodiesel (methanol
been $1500/mt during the same period. However, with PDO, the OH groups are esterification of fatty acid) represents
During the mid-2008 crude oil price run- both on the terminal carbon atoms, glycerin by-product, the conventional
up, with naphtha prices exceeding with the centre carbon atom saturated markets for glycerin are well satisfied by
$1000/mt, market prices for both ethylene with hydrogen. Due to its structure, the conventional sources of glycerin
and propylene averaged approximately PDO can easily be polymerised with (from soap and surfactant manufactur-
$1500/mt, driving PG market prices to purified terephthalic acid to produce a ing). When there is an excess supply of
$2000/mt. polyester (poly tri methyl terephthalate) any commodity to a market, the market
that performs much like nylon when price of the commodity usually drops
Production of PG fabricated as a fibre, but costs only half precipitously.
from glycerin as much as nylon to manufacture. If the market price of glycerin changes
Most recently, several companies (Dow, The molecular structure of glycerin from initially being much more
Huntsman, ADM, Ashland/Cargill) have (mol wt: 92.1) is remarkably similar to expensive than propylene to finally
announced new commercial technology PG and PDO. Glycerin is also a three- being much less expensive than
projects for producing PG directly from carbon atom molecule, but each of the propylene, it makes sense that industrial
the glycerin that is a by-product of carbon atoms is attached to an OH routes to PG from glycerin might be
biodiesel production. Since biodiesel radical. As a result, glycerin is a solid at economically attractive.
production has increased dramatically room temperature (both PG and PDO
over the past five years, a glut of excess are liquids), and has a much higher Markets for glycerin
by-product glycerin has been produced boiling point than either PG or PDO. As shown in Table 1, the global demand
that cannot be absorbed into From a chemical structure perspective, for glycerin is approximately 600 kty.

www.eptq.com PTQ CATALYSIS 2009 47

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

www.eptq.com PTQ CATALYSIS 2009 49

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


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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
KF 767
in ULSD operations. Increasing the
throughput in a ULSD unit or processing
low-quality feedstocks without additional KF 770
capital investment are both great ways of KF 757
increasing margins and financial returns. 10 20 35 50 100
Based on new detailed insight into the Outlet partial pressure H2
chemistry taking place in a ULSD unit,
new catalysts and catalyst technology
are being introduced that can help boost Figure 1 Albemarle’s portfolio for ULSD production
performance.
Recent developments are able to
improve hydrodesulphurisation (HDS)
unit performance by up to 35% over the
most active catalysts in the current HYD sites DDS sites KF 757 Stars
hydroprocessing marketplace. For
+20%
example, the new Ketjenfine (KF) 770
HYD sites HYD sites KF 770 Stars
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 Figure 2 Build-up of performance benefit of Ketjenfine 770 Stars
cheaper, lower quality feedstocks, all
without additional capital expenditure. high throughput experimentation, has catalyst was tailored to achieve maximum
The KF 770 HDS catalyst’s functionality precisely those sites gearing its stability under the conditions of low and
focuses on reaching breakthrough performance at low and medium medium partial pressure of hydrogen.
performance in low- and medium- pressures to a start-of-run (SOR)
pressure range ULSD. It takes the place of performance activity benefit of more 35% cycle length increase
KF 757 Stars in Albemarle’s ULSD catalysts than 20%, as shown in Figure 2. In addition to 20% extra SOR activity,
(Figure 1). KF 757 is still available for Figure 3 compares the activity of KF detailed forecasting for specific cases
refiners running less severe operations. 770 vs KF 757 in a 20 bar pilot plant test. demonstrates that KF 770 can increase
The catalytic removal of refractory Over a period of more than 40 days, KF cycle length by up to 35% when
sulphur species occurs through a 770 continuously showed an advantage compared to KF 757 (Figure 5).
complex reaction scheme comprising at in HDS, achieving an extra volume The lower SOR temperature favours
least two routes: through direct route activity of 20–25%. catalyst stability, as the deactivation rate
HDS or direct desulphurisation (DDS) Prolongation of the test at 45 bar is a function of reactor temperature. In
and hydrogenation (HYD) sites. (Figure 4) clearly demonstrates that the addition, the high HDN activity of KF
A complicating factor at low and throughput in a unit with KF 770 can be 770 provides an extra boost in HDS
medium partial pressures of hydrogen is increased to 20% over the same unit activity by releasing HYD sites from
the slow rate of organic nitrogen loaded with KF 757. These and other inhibition by nitrogen species. It further
removal. As the nitrogen species inhibit pilot plant results confirm that the suppresses the needed reactor
the HYD sites, the catalyst’s effectiveness stability of KF 770 is equal to or better temperature for reaching ULSD
is largely determined by the number of than KF 757. Throughout the develop- specifications and builds to an overall
DDS sites. KF 770, developed through ment of KF 770, the formulation of the 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 Figure 7 Conditions in a typical hydroprocessing unit’s reactor catalyst system
regime. This is the essence of proprietary
Stax catalyst systems. Of course, this is
easier said than done, as it requires a Typical three-zone reactor model: zone 1, top catalyst layer; zone 2, middle
detailed understanding of the conditions
catalyst layer; zone 3, lower catalyst layer
at each point in the reactor. Zone 1 Zone 2 Zone 3
Key to the application of Stax is a Sulphur content High Medium Low
model that can predict the reaction Nitrogen content High Medium-low Very low
conditions at each point in the Polynuclear aromatics High Medium-low Zero
hydrotreating unit. Using new analytical H2S in gas 0–medium High Highest
methods and small-scale testing NH3 in gas 0–medium Medium High
equipment, it is now possible to see into H2 in gas High Medium Medium-low
the reactor and develop models based Main HDS reaction Direct Mainly direct Hydrogenation
on those observations. Technology has Main HDS inhibitor H2S Organic nitrogen –
been developed to track changes in HDS reaction rate Fast Slow Fast
sulphur, nitrogen and aromatics “by
slice” along the vertical axis of a Table 1
laboratory reactor. This allows the
concentration of bulk sulphur and hetero-atoms by structure. Catalyst selection and system design are
nitrogen to be tracked through the Stax is the technology for applying an made according to the reaction chemistry
reactor, and permits the analysis of understanding of hydroprocessing and process conditions in each reactor
samples using GCxGC to segregate 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


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

20
1 2 3 4

15
Product $, ppm

10

5
KF 767
STAX
0
0 10 15 20 25 30 35 40
Days on stream

Figure 8 Stax in practice

www.ptqenquiry.com
54 PTQ CATALYSIS 2009 for further information www.eptq.com

albemarle.indd 4 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 l A survey and refinery wish list of selected FCC unit components
associated gas plants, particularly when linked to: including feed nozzle injectors, cyclones and steam strippers (See
° Mild hydrocracking unit (MHC) sections 12.4, 12.5 and 12.6)
° Butylene alkylation unit
° Two-stage desulphurisation unit l Survey of rotating equipment developments for improving reliability
° High purity propylene plant of new and refurbished WGCs and MABs (See section 11)
° Separate draws within main fractionators
° Integrated slurry oil filtration unit l Process flow diagrams showing FCC units configured for specific
° Third-stage separator with underflow filtration (See section 8.2) 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)
Plus
l Survey of future long-term trends affecting FCCU process design
l Assessment of FCC catalyst formulations for processing and operations, including market and regulatory trends such as
hydrotreated cat feeds and non-hydrotreated cat feeds (See higher fractions of heavier feeds, synthetic blends and biomass
sections 6.7 and 9) 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
www.salvoglobal.com/fccu.asp www.gracedavison.com

Albemarle Catalyst 9, 11, 13, IBC Haldor Topsøe IFC


www.albemarle.com www.topsoe.com

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
www.refiningchina.com
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
www.criterioncatalysts.com
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


www.ge.com/oilandgas www.zeochem.com

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

w w w. p t q e n q u i r y. c o m

5 6 P T Q CATA LY S I S 2 0 0 9 www.eptq.com

ad copy.indt 1 4/2/09 21:17:53


www.ptqenquiry.com
for further information

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


Our advanced
catalytic engineering
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Axens’ HR series ACE™ technology catalysts deliver sustained, on-spec ultra-
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HR_ptq.indd 1 28/11/08 12:44:39


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