catalysis

2013

ptq

cover and spine copy 7.indd 1 27/02/2013 14:10

 When you can’t predict
what’s in the pipeline
THINK ®
MIDAS FCC
CATALYST

TO CAPTURE THE VALUE OF

OPPORTUNITY CRUDES

grace.com

grace.indd 1 26/02/2013 16:20

 catalysis Security of
ptq
feedstock supply
2013 Vol 13 No 2 3 Follow that market
2008
www.eptq.com Chris Cunningham

D
Editor 5 espite
ptq&asigns in 2007 of a slowdown in various sectors of the economy,
René G Gonzalez refiners remain a big play for prospective investors. It used to be
editor@petroleumtechnology.com
15 conventional
Advances in wisdom that higher fuel
FCC pretreatment prices and a slowing economy
catalysis
would curb demand and increase supply, but for the past seven years
Production Editor that has not Bill Gillespie,
proved to beAlexei
the case. Gabrielov,
While the Thomas
rate of Weber
increaseand Larryoil
in world Kraus
demand
Rachel Zamorski has declined
since the surprising
Criterion Catalysts & Technologies 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 by China, India and even the Middle East producers
23 New
themselves catalyst Itincreases
will continue. is also safe FCC distillate
to assume thatyield
refinery and petrochemical
Graphics Editor conversion unit capacity will need to expand.
Mohammed Samiuddin Carl Keeley, Jeremy Mayol, Stefano Riva and Vasileios Komvokis
No massive new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com
foreseeable Basf
future. Corporation,
The world will Refining
remainCatalysts
dependent on oil and gas for decades to
come evenStephen
though Challisthe upstream industry faces increasing challenges in the
Editorial discovery and production of new sources. In fact, some well-placed industry
Chalcat Consulting
PO Box 11283 analysts think 2008 may be the year where there is no increase in crude supply at
Spring TX 77391, USA all from regions outside of OPEC. For this reason, we will continue to see significant
tel +1 281 374 8240 investment
29 Bestin refi nery upgrades
practices for SOx despite
emissions surging costs — security of feedstock
control
fax +1 281 257 0582 supply, albeit unconventional low-quality feedstock, takes precedence over the
of feedstock
quality Ray Fletcher supply.

Feedstock Intercat
options such as biomass (for biofuels production), Canadian tar sands
Advertising Sales Manager (for distillate production) and other types of unconventional crude sources require
Paul Mason
reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com
process41
confiCatalysts
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quality ofmanagement
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Advertising Sales reason why a wider array of
Ross Brunson, Uwe Flessner catalysts has andbeen introduced
Paige Morse into the market. For
Bob Aldridge example, as refiners cut deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com
Clariant
metals in the VGO requires a properly designed guard bed system to protect active
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Advertising Sales Office (eg, <10),
tel +44 870 90 303 90
49 high metals, the
Extending nitrogen and other
lifecycle undesirable components
of hydroprocessing catalystis one of the
main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90
accommodate Roland not Hoffman
only higher and Bob Leliveld
volumes of catalyst, but also a wider variety of
Publisher
catalyst withAlbemarle Catalysts Company
specifi c formulations.
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,
55 ners
some refi Predicting
processing FCC unitvolumes
higher performance of residwith laboratory tower
and atmospheric testing bottoms
Circulation have considered adding
Kenneth Bryden 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.
Grace Improvements
Catalysts Technologies 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 61 Refining refiners’ spent catalysts
However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20 B J Stephan
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax +44 870 90 600 40
the following
articles
Gulf Chemical authored by experts inCorporation
and Metallurgical 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
well as to those respondents who addressed the online questions (www.eptq.com)
Petroleum Technology Quarterly (USPS
that NexBTL
addressed
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technology cs of Finland,
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0014-781) is published quarterly plus the industry.
Photo: Neste Oil
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. ©2013. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
Periodicals postage paid at Emigsville PA. reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
Postmaster: send address changes to mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
Petroleum Technology Quarterly c/o PO 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
Box 437, Emigsville, PA 17318-0437
statements, opinions or views or for any inaccuracies.
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez

ed cont.indd 1 26/02/2013 18:01

 “My hobbies? Fishing, downhill skiing, and
inventing breakthrough catalysts.”

Meet Alexei Gabrielov:

Outdoor Enthusiast, CRITERION Scientist.

Father of three sons and ten patents, Alexei Gabrielov would love nothing more than to ideate and invent
all day long. And after 16 years of active research in catalysis working with CRITERION and Shell, Alexei
has done his fair share of both. He helped bring to life a new generation of catalysts technologies including
CENTINEL GOLD and CENTERA®. Recently, Alexei and his colleagues invented and developed a new
state-of-the-art nickel-moly FCC pretreat catalyst, Criterion’s CENTERA® DN-3651.

Leading minds. Advanced technologies.

www.CRITERIONCatalysts.com

criterion.indd 1 26/02/2013 16:09

 catalysis Security ofmarket
Follow that
ptq
feedstock supply
Vol213 No 2
Vol 18 No
2013 2008

DD
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
Editor René G Gonzalez emand for refining catalysts in Europe and North America will not be the
refiners remain a big play for prospective investors. It used to be
Chris Cunningham
editor@petroleumtechnology.com main driving force for manufacturers in the coming years, certainly in terms
editor@petroleumtechnology.com conventional wisdom that higher fuel prices and a slowing economy
of volumes sold and perhaps in terms of technical development. Demand
would curb demand and increase supply, but for the past seven years
for petroleum-derived motor vehicle fuel in these long-established markets is
Production
Production Editor Editor that has not proved to be the case. While the rate of increase in world oil demand
Rachel Zamorski
Rachel Storry has stagnant,
declined more
since so theassurprising
biofuels take an increasing
4% surge in 2004,share of demand,appears
it nevertheless while road that
production@petroleumtechnology.com
production@petroleumtechnology.com
vehicles continue to drive more miles for every litre
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly at the pump. By contrast, in
the Asia-Pacific region, the Middle East and Brazil,
increasing oil consumption by China, India and even the Middle East producers greater car ownership and
Graphics Editor stricter limits
themselves for emissions
will continue. are the
It is also safereasons
to assume behind
that the overwhelming
refinery majority
and petrochemical
Rob Fris Graphics Editor of the world’s planned new refinery
conversion unit capacity will need to expand. projects. Catalyst manufacturers looking for
Mohammed Samiuddin
graphics@petroleumtechnology.com
Noas big a share
massive newof growth
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energyinare sales need to to
expected follow
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foreseeable future. remain dependent
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tel +44 844 5888 773 come In Maythough
even last year,theGrace signed industry
upstream a memorandum of understanding
faces increasing challenges to produce
in the
Editorial
fax +44 844 5888 667 FCC catalyst
discovery in Qingdao,
and production of China, as a wholly
new sources. In fact,foreign-owned
some well-placed enterprise. The
industry
PO Box 11283 opportunity
analysts think 2008 to manufacture
may be the year locally
wherefor there
China’sis noexpanding
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Spring
Business TX 77391,
Development USA
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— the rocketing price of rare earth metals as China
Advertising Sales Feedstock
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— hasbiofuels production),
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itself, as thetar sands
price
Advertising
Bob Aldridge Sales Manager (for of
distillate production) and other types of unconventional crude sources require
Paul Mason
sales@petroleumtechnology.com these materials has tumbled from its highs of 2010/11. According to
reactor technology
Qingdao’s that allows
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sales@petroleumtechnology.com
Advertising Sales Office process
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in the vicinity,Thein thequality
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tel +44 844 5888 771 Sales reason why a wider array of catalysts has been introduced
promote local expansion of refining and petrochemicals manufacturing. into the market. For
Bob
fax +44 844 Aldridge
5888 662 example, as refi
A couple ofners cut earlier,
months deeper Grace
into the had vacuum
agreed totower,set up thea jointconcentration
venture based of
sales@petroleumtechnology.com metals in the VGO requires a properly designed guard bed
on the production of FCC catalysts and additives in Abu Dhabi, United Arab system to protect active
Publisher catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Emirates. The deal would deliver the first plant in its region able to produce
Nic Advertising
Allen Sales Office (eg, <10), high metals, nitrogen and other undesirable components is one of the
tel +44 870 90 303 90
publisher@petroleumtechnology.com FCC catalysts. With an estimated 16 FCC plants expected to be built within the
main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 Gulf region during the next few years, the potential for catalyst suppliers is as
accommodate not only higher volumes of catalyst, but also a wider variety of
Circulation big as it gets. Prior to Grace’s manufacturing deal, Albemarle had signed up
catalyst with specific formulations.
Jacki Watts Publisher with Abu Dhabi’s leadarerefiner, Takreer,a signifi
to supply FCCincatalyst
Nic Allen Non-catalytic processes also playing cant role the refiforner’s a ability
major
circulation@petroleumtechnology.com expansion at Ruwais refinery. The expansion is expected to make Ruwais the
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. For example,
world’s biggest RFCC site by the early months of 2014.
some refiners processing higher volumes of resid and atmospheric tower bottoms
Crambeth Allen Publishing Ltd
Circulation By the end adding
have considered of nextcertain
year, Albemarle should have large-scale
types of solvent-extraction processes production
in addition of
Hopesay, Craven Arms SY7 8HD, UK
tel +44 844Jacki Watts
5888 776 hydroprocessing catalysts in operation in Brazil. The
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed new plant will extend an
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ISSN 1362-363X Allen Publishing Ltd processing catalyst, to meet the regulatory requirement for ultra-low-
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However, production of
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dehydrogenation) was investment
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quarterly plus annual Catalysis edition by Crambeth
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editorial feedstocks.
and responded to the Q&A published in this issue of PTQ Catalysis, as
Monroe NJ 08831. Periodicals postage paid at New
Brunswick, NJ. Postmaster: send address changes to
well asPetrobras
to those expects
respondentsto bewho addressed
operating a newthe refinery,
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0014-781)
Back numbersisavailable
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from the Publisher
the coming
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annual Catalysis
copy incedition
postage. by Crambeth Allen
at $30 per
Publishing Ltd and is distributed in the USA mates that its demand for refinery catalyst will expand five-fold through the
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. first half of the current decade.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437 chris cunningham
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez
Catalysis 2013 3

ed cont.indd 2 26/02/2013 17:57

cbi.indd 1 26/02/2013 16:13
 ptq&a
Q Is the quality of vapour/liquid distribution as big an issue
as catalyst choice in hydroprocessing, and what types of
internals provide optimum results?
A Aris Macris, Licensing Technology Manager, Shell Global
Solutions (US) Inc, Aristides.Macris@Shell.com
The performance of hydroprocessing reactors is deter-
mined not only by the choice of catalyst loaded, but
also by the design of the reactor internals used.  distribution could reduce catalyst system performance
The key incentive for installing internals technology
is to achieve a uniform liquid and temperature distri-
bution over the catalyst beds.
Key characteristics and advantages of sophisticated
reactor internals include:
• Full catalyst utilisation
• Better and safer performance by eliminating radial
maldistribution
• Lower catalyst deactivation rates and safer unit
operation
• Minimum pressure drop
• Improved product quality
• Operating over a wide window for liquid and gas
rates, and having a high tolerance to tray tilt
• Ease of installation and maintenance through use of
boltless design.
All hydroprocessing technology providers and cata-
lyst suppliers offer reactor internals technology. Our
state-of-the-art internals help to optimise catalyst utili-
sation, maximise catalyst cycle length and increase
process safety. In addition to typical reactor internals,
we provide top tray designs that reduce pressure drop
build-up and fouling, especially when processing diffi-
cult feeds.  These Shell proprietary top bed filters have
two main functions:
• Pre-distribution of gas and liquid to the high disper-
sion liquid/gas distributor tray (HD tray) located
directly below
• Protection of the bed from fines by filtration as sedi-
mentation both during normal operation and start-up
or upsets.
Upgrading to state-of-the-art internals can provide
performance gains similar to improvements achieved by
upgrading to the latest generation of catalyst technolo-
gies. By taking advantage of both available hardware
and catalyst designs, overall process capability increases
can deliver strong value to operating facilities.
A Andre Schaap, HPC Technical Specialist, Albemarle,
andre.schaap@albemarle.com
The performance of a catalyst system is determined by
its activity. A good vapour/liquid distribution is
Additional Q&A can be found at www.eptq.com/QandA
www.eptq.com
Q&A copy 11.indd 1
required to make full use of the activity potential of a
catalyst system. Until the mid-1990s, distributor design
received much less attention than catalyst activity
improvements. As hydrotreater operations became
more severe (lower sulphur specifications and feed-
stock containing more refractory sulphur species), the
performance of the distributor became increasingly
important — to the extent that poor vapour/liquid
far below what could be recaptured using the latest
catalyst technology. The need for improved vapour/
liquid distribution has prompted much development
in the past 10 years, and improved designs have been
introduced by most technology providers and catalyst
companies.
If your operation is high severity and your reactor
internals are relatively old, poorly designed and/or
badly maintained, replacing them with a new, state-of-
the-art distributor will result in a dramatic
improvement in catalyst system performance. The
improvement generated from optimally utilising the
catalyst is likely to outweigh the impact of catalyst
choice. If your distributor is relatively new and in
good repair, upgrading the design will potentially offer
some improvement in catalyst utilisation, but these
improvements will most likely be smaller than select-
ing the latest generation of catalyst.
Q Can you suggest a checklist for effective preparation
and loading of beds at a catalyst change-out? Why are these
factors important?
A Paul Temme, HPC Technical Services Team Leader,
Albemarle, paul.temme@albemarle.com
The importance of a good catalyst loading process
should not be underestimated. It is just as important
(or even more so) than catalyst sulphidation and
break-in. There are methods for recovering from less
than optimal sulphidation, but a poor loading has few
remedies other than a shutdown, dump and reload.
In the following catalyst loading checklist, each item
is meant to promote effective communication between
client, catalyst vendor and catalyst loading contractor.
Clearly defining expectations, responsibilities and
targets ahead of time will result in a smooth loading
process.
Finalise reactor loading diagram
1. Has a target loading diagram been prepared?
2. Has the type of catalyst (CoMo, NiMo or other) been
Catalysis 2013 5
27/02/2013 11:59
 clearly identified and loading method (sock or dense)
reviewed?
3. Is the loading diagram consistent with previous load-
ings in terms of void space and use of ceramic balls?
4. Is the target loading density in line with the catalyst
vendor’s latest information on the catalysts? Has there
been a change in density since the last loading that
may not have been communicated to the client, which
could cause problems during loading?
Contact loading contractor
5. Who is the catalyst handling company? Did it load
for the last turnaround?
6. What type of catalyst loader is to be used? Has the
catalyst vendor been consulted?
Hold expectations meeting with loading contractor
7. Was a consensus reached on the details of executing
the loading? For example, will a vacuum be available
to remove catalyst dust? How will catalyst be
“walked” on (snow shoes, wooden board, and so on)
during the loading?
8. Is everyone aware of their job responsibilities?
9. How will outages be tracked during loading? Is
video available to provide those outside the reactor
with the ability to inspect the progress?
Mild hydrocracking (MHC) can be
applied in ULSD units to process
heavier feeds and/or improve
diesel product qualities
Finalise procedures
10. Have shutdown, unloading, loading and start-up
procedures been reviewed with the technical service
representative? Has a spent catalyst sampling plan
been identified (number of samples, location of
sampling, method of sampling, and so on)?
Verify catalyst inventory
11. What are the catalyst quantities on site? In a typical DMHC unit, the incremental diesel yield
12. Was this directly verified?
13. Is the inert support material new or used?
14. How is the catalyst being stored?
15. Is the catalyst protected from weather?
Record any issues during catalyst loading
16. If dense loaded beds were not level, was the bed
manually levelled, corrected by machine adjustments,
or was the bed reloaded?
17. Were there any issues with the dense loading
machine? What were they? How were they rectified? improvement are illustrative. The actual values will be
18. Was any catalyst breakage observed during any
part of the loading? dewaxing, process conditions employed, and so on.
19. Were there any issues with transfer of catalyst?
What were they? the greater the difference between conventional
6 Catalysis 2013 www.eptq.com
Q&A copy 11.indd 2
20. Were final bed outages taken from the bottom of
the tray?
21. If there was rain during loading, how was the cata-
lyst protected?
Receive loading report
22. Does the report capture all issues from the loading,
resolved and unresolved?
23. Has the loading report been distributed to all the
personnel?
Q Do you recommend a catalytic dewaxing stage for mild
hydrocracking in my gas oil hydrotreater?  
A Lawrence (Larry) S Kraus, Hydroprocessing Product &
Development Manager, Criterion Catalysts & Technologies,
lawrence.kraus@cri-criterion.com
Mild hydrocracking (MHC) can be applied in ULSD
units to process heavier feeds and/or improve diesel
product qualities. MHC allows heavier feeds to be
processed while maintaining T-95 and density specifi-
cations. MHC, specifically selective ring opening
(SRO), is an effective means of upgrading diesel prod-
uct cetane while minimising the H2 consumption per
unit of CN improvement. Distillate MHC (DMHC)
involves passing distillate boiling range materials over
conversion catalysts. This results in molecules that are
in the low end of the distillate boiling range being
converted into the naphtha boiling range to some
degree. A key aspect of DMHC operation is minimis-
ing feed conversion to naphtha while meeting other
required specifications for the diesel fraction.
When insufficient cold flow property improvements
are achieved as the other process objectives (for exam-
ple, T-95 reduction, diesel cetane improvement) are
met, increasing the severity of DMHC operations to
further improve cold flow properties results in non-se-
lective conversion that leads to significant naphtha
production/diesel yield loss. In most instances, this
hurts refinery profitability. In these cases, utilising a
shape-selective dewaxing catalyst to selectively
convert the paraffinic species responsible for poor cold
flow properties achieves the desired cold flow proper-
ties while minimising additional diesel yield loss.
loss per °C of cloud point (CP) improvement using
conventional hydrocracking catalysts and a shape-
selective dewaxing catalyst is illustrated below:
Incremental conversion, wt%/°C
CP improvement
Shape-selective dewaxing catalyst 0.5
Conventional hydrocracking catalyst >1
These values of incremental conversion per °C of CP
specific for the feedstock properties, required depth of
The lower the additional dewaxing requirement,
27/02/2013 12:00
 ISOMIX -e ®

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clg.indd 1 26/02/2013 17:02

 hydrocracking and shape-selective dewaxing catalysts.
Clearly, if additional CP improvement is needed in a
DMHC unit, a shape-selective dewaxing catalyst can
be used to achieve this at much higher diesel yields.
For example, an additional 10°C CP reduction can be
achieved with ~5 wt% higher diesel yield using the
shape-selective dewaxing catalyst.
Criterion and Shell currently offer SDD-800 shape-
selective dewaxing catalyst. Due to its specific formu-
lation and manufacturing process route, SDD-800 has
very high distillate selectivity. It is currently in use in
more than 30 distillate fuel hydroprocessing units
worldwide and 10 more are currently under design
or revamp.
Q What are recent and current developments in
catalyst technology for hydrodenitrogenation and hydro-
desulphurisation, and what level of performance should I be
looking for?
A Steve Mayo, Global HPC Applications Technology Manager,
Albemarle, steven.mayo@albemarle.com
Catalyst development is a continuous process. All cata-
lyst suppliers devote substantial resources to
continuously improving and bringing improved cata-
lysts to the market. Albemarle has been a leader in
hydroprocessing catalyst development and was first to
Do not neglect the importance
of guard bed catalysts and
regenerated/rejuvenated
catalysts in the selection process
market with Type II catalysts (Stars technology) and
bulk metal catalysts (Nebula). More recently, we have
introduced Stax technology to optimise catalyst system
design, to simultaneously meet multiple unit objectives.
The level of catalyst performance required varies
greatly by unit operation. Low-severity units can
usually enjoy long cycles without using the latest
generation of catalyst improvements, while high-
severity units can easily justify use of the latest catalyst
developments to capture maximum economic gain.
Catalyst cost in a hydroprocessing unit is a small part
of the overall operating cost. Improved performance
can be leveraged in numerous ways to justify the
slightly higher up-front cost for the latest technology.
Many catalyst decisions focus on longer cycle length,
but the real economic gains come from changes in unit
operation to exploit volume swell and upgrade
margins.
Finally, do not neglect the importance of guard bed
catalysts and regenerated/rejuvenated catalysts in the
selection process. Improvements have also been made
in top layer catalysts to resist shortened cycles due to
pressure drop build-up and catalyst poisoning. Make
8 Catalysis 2013 www.eptq.com
Q&A copy 11.indd 3
sure your catalyst supplier has a complete portfolio of
solutions to address any issues that caused your
hydrotreater to shut down prematurely. Regenerated
and rejuvenated catalysts are often wise choices when
maximum catalyst activity is not a requirement.
There are numerous strategies to cascade regenerated
catalysts to lower severity units. Rejuvenation
can restore near 100% of fresh catalyst activity, making
it a good choice for return into the same or similar
service.
A Lawrence (Larry) S Kraus, Hydroprocessing Product &
Development Manager, Criterion Catalysts & Technologies,
lawrence.kraus@cri-criterion.com
Criterion Catalysts & Technologies is continuously
improving the performance of its hydrotreating catalyst
product line in order to provide optimal solutions for
refiners. Two of the most recent additions to the compa-
ny’s catalyst portfolio are DN-3651 and DC-2635.
DN-3651 is a new-generation Centera catalyst that
overcomes the challenging process environment and
difficult feeds encountered in FCC feed pre-treatment
(FCC-PT). It shows up to 140% relative volumetric
activity (RVA) improvement in hydrodenitrogenation
(HDN) and hydrodesulphurisation (HDS) over the
current-generation FCC PT catalyst, Ascent DN-3551,
over a broad application range. Test data have been
obtained with DN-3651 processing a variety of feeds (S
= 1.3-4.2 wt%, N = 1870-4720 wppm) over a wide
range of operating conditions (P = 1000-1800 psig
[70-124 barg], LHSV = 0.50-1.14 hr-1). DN-3651
combines the commercially demonstrated stability and
contaminant tolerance features of Ascent DN-3551, an
industry-proven NiMo FCC-PT catalyst, with the
unique Centera active site architecture, allowing for
step-out HDS, HDN and aromatics saturation (ASAT)
performance, plus high catalyst stability in FCC PT
applications. DN-3651 provides strong performance
gains that can provide a wide range of value-added
operating improvements. Since its introduction in 2011,
it has been used in 11 FCC-PT units to enable
improved levels of FCC conversion, increased upgrad-
ing of challenging low-value feeds, extended
operational cycle lives, and improved FCC-PT/FCC
complex profitability. More than 5 million pounds of
DN-3651 have been sold so far.
DC-2635 is a new CoMo Centera designed for broad
application in distillate hydrotreating. It has shown
115-130% higher ULSD RVA than DC-2618 over a
broad range of processing conditions (P = 175-870 psig
[12-60 barg], LHSV = 0.65-1.2 hr-1) when processing a
wide variety of feed types (SRGO, SRGO/cracked
stock blends, T-95 = 665-795°F [352-424°C], S = 1.1-3.0
wt%, N = 50-410 wppm). The activity advantage of
DC-2635 over previous generations of CoMo DHT
catalysts provides operators with maximum unit flexi-
bility in terms of feed difficulty, throughput, cycle
length, and so on to increase unit profitability. It does
not show significantly higher H2 consumption than
previous generations of Centera and Centinel CoMo
catalysts.
27/02/2013 12:00
 The maximum achievable performance level of
hydrotreating catalyst systems is specific for individual
units. The activity level of the catalyst system designed
for a particular unit is a function of the unit process
objectives, including product specifications, through-
put targets, cycle length targets, unit capabilities and
feed properties. Improved catalyst activity and stability
provide refiners opportunities to increase unit through-
put and/or feed difficulty without reducing cycle
length, to improve product properties and downstream
unit performance, or to increase catalyst cycle length.
Catalyst system performance can be specifically
tailored to meet exact refiner needs. New-generation
Criterion catalysts such as DN-3651 and DC-2635
provide refiners the ability to fully capture opportuni-
ties at their hydrotreating units.
A John Jeanneret, Sr Business Leader, Hydrotreating
Catalysts, UOP, john.jeanneret@honeywell.com
Hydrotreating has many different applications in a
modern refinery, and each application has different
feedstock and product considerations. One way to look
at hydrotreating is to divide the field into pre-treat and
post-treat applications. In most pre-treat applications,
we are generally trying to remove sulphur, nitrogen,
metals and other contaminants such as
silicon and arsenic down to very low levels (for exam-
ple, less than 0.5 ppm S and N in naphtha
hydrotreating), in order to protect expensive catalysts in
downstream process units such as reforming, isomerisa-
tion and hydrocracking units. In post-treat applications,
we focus on removing sulphur in order to meet increas-
ingly stringent low-sulphur fuel regulations (for
example, Euro V regulations of less than 10 ppm S in
both gasoline and diesel), while preserving or enhanc-
ing desirable fuel properties such as octane in gasoline
or cetane in diesel. The situation around an FCC unit is
more complicated since many refineries have both an
FCC feed pre-treater and an FCC gasoline post-treater,
and the processing objectives for the FCC unit may
differ from one refinery to another.  When you consider
the wide range of hydrotreating applications, feedstock
contaminants and processing objectives, you begin to
understand why hydrotreating catalyst vendors offer
such a wide array of catalysts and grading materials.
In recent years, the development of so-called Type II
hydrotreating catalysts has resulted in substantial
improvements in catalyst activity.  We use a measure
called Relative Volume Activity (RVA) to compare the
hydrodesulphurisation (HDS) and hydrodenitrogena-
tion (HDN) performance of different catalysts in the
same application. In general, the best Type II catalysts
offer 20-30% higher HDS and HDN RVA, when
compared to the best Type I catalysts. This additional
catalyst activity can be used to increase operating
severity (ie, accomplish deeper sulphur and nitrogen
removal in the same reactor volume), or it can be used
to extend the cycle length of the hydrotreater. The
trade-off is that these Type II catalysts are generally
more difficult and more expensive to regenerate than
conventional Type I catalysts.
www.eptq.com
Q&A copy 11.indd 4
The use of grading materials has also evolved
dramatically in the last few years.  Grading materials
are loaded directly on top of the catalyst bed and can
perform many functions such as improving flow
distribution, trapping particulates, absorbing catalyst
poisons like silicon and arsenic, and managing the
heat of reaction, as well as physically containing the
catalyst bed. In the recent past, the end of cycle for
most hydrotreaters was determined not by catalyst
deactivation but by a build-up of pressure drop at the
top of the bed.  New top-bed grading materials, such
as Crystaphase’s CatTrap products, do a very effec-
tive job of trapping particulates before they can form
the crust at the top of a catalyst bed that causes pres-
sure drop.  Skilled hydrotreating catalyst suppliers
have a great deal of experience in tailoring a grading
strategy to meet the objectives and challenges of
each unit.
A George Hoekstra, President, Hoekstra Trading,
george.hoekstra@hoekstratrading.com
You should expect 20% activity improvement from a
new catalyst. This will be noticeable in the form of a
4°C (7°F) lower start-of-run temperature on your unit.
Another way to realise this benefit is to process more
difficult feed. For example, in an ultra-low-sulphur
Improved catalyst activity
and stability provide refiners
opportunities to increase unit
throughput and/or feed difficulty
without reducing cycle length
diesel unit, a 20% activity increase should allow you to
increase light cycle oil (LCO) feed content to the extent
of adding 50 ppm more nitrogen to the blended feed.
Independent testing has shown that ART’s 420DX
CoMo catalyst achieved this level of improvement
above its previous catalyst, and above market-leading
competitive brands, for use in high-pressure diesel
hydrotreaters. For low-pressure diesel hydrotreaters,
Haldor Topsøe’s TK-578BRIM and TK-570BRIM
showed best performance, 20% better than any
competitive brand tested. These findings are from a
four-year independent pilot plant testing programme
that evaluated 36 diesel hydrotreating catalysts includ-
ing products from all major catalyst suppliers. The
multi-client programme was sponsored by a group of
independent refiners and Hoekstra Trading.
Recent improvements in catalyst performance stem
from finding better ways to attach promoter metals
(cobalt or nickel) to molybdenum disulphide slabs
during manufacture. A cobalt atom attached to a
molybdenum disulphide slab is 250 times more active
than one attached to the alumina surface; and this
difference is multiplied further when the cobalt atom is
Catalysis 2013 9
27/02/2013 16:24
 attached at the right location on the slab. This provides
lots of leverage for catalyst improvement.
Claims of better catalyst performance have often
been exaggerated by suppliers trying to differentiate
their products. For this reason, competitive side-by-
side independent testing, using a standardised
protocol, provides great insight for refiners who really
want to improve unit performance and profit.
Q We have begun feeding coker naphtha, with unwelcome
levels of arsenic and silicon, into our ULSD unit. Should we
boost the guard bed catalyst section of the reactor? What
resulting loss of main bed capacity should be acceptable?
A Zdenek Sedlacek, HPC Technical Service, Albemarle,
zdenek.sedlacek@albemarle.com
Co-processing coker naphtha in ULSD units brings
several challenges, including higher levels of impuri-
ties, polymerisation issues and a reduction in
hydrogen partial pressure. Additional guard bed
catalysts with higher capacity and tolerance to silicon
and arsenic poisoning should be installed to minimise
deactivation of the main catalyst. Furthermore, a close
examination of the grading system along with the
specific activity levels of the guard/grading catalysts
will be important to minimise undesired polymerisa-
tion reactions that could result in pressure drop issues.
Lastly, the reduction in hydrogen partial pressure from
the vaporised naphtha should be factored in to ensure
that the ULSD unit still provides reasonable perfor-
mance. An optimal balance between the guard bed and
main bed catalysts will depend on the specific feed
properties, process conditions and objectives of the
ULSD unit.
A Paul Ceccato, Regional Manager, Technical Services
Americas, Criterion Catalysts & Technologies, Paul.ceccato@
cri-criterion.com
One of the primary impacts of including coker naphtha
in the ULSD feed blend is a potential increase in
contaminant levels of silicon (Si) and arsenic (As), which
deactivate the catalyst and decrease cycle life. Si bonds
with the alumina base of the catalyst to block access to
active sites, while As directly attacks the active metals.
In both cases, cumulative exposure deteriorates the
overall system activity and unit performance.
When designing a ULSD catalyst loading scheme,
the impact of Si and As introduced by the coker naph-
tha must be addressed with specialised Si and As trap
catalysts. For Si, the average Si content of the coker
naphtha should be determined through frequent
sampling of the delayed coker naphtha at various coke
drum levels. Similarly, an average As content should
be determined to assess its potential contribution.
Completing mass balances on the Si and As in the
combined ULSD feed, evaluating the activity impact
on the main catalyst with time, and balancing unit
objectives such as feed severity and cycle life will set
the required Si and As trap protection requirements.
Si trap catalyst is designed with high surface area for
10 Catalysis 2013 www.eptq.com
Q&A copy 11.indd 5
increased Si capacity and protection of the main cata-
lyst. To balance the protection and activity requirements
of the ULSD catalyst system and meet unit objectives, Si
trap catalysts can be either low activity with very high
Si capacity such as Criterion’s MaxTrap[Si] or active
with high Si capacity such as Criterion’s DN-140.
Optimising these two Si trap products minimises the
overall ULSD activity impact when replacing some
main catalyst volume. Si trap catalyst is positioned at
the top of the reactor, below the top bed grading.
As trap catalyst is designed with high metals to
increase As capacity and protection of the main cata-
lyst. With a high metals content, the inclusion of As
trap catalyst such as Criterion’s MaxTrap[As] below
the Si trap catalyst at the top of the reactor protects the
main catalyst without sacrificing activity.
The introduction of Si and As by co-processing coker
naphtha in a ULSD unit is addressed by loading Si and
As trap catalysts. Depending on the relative quantities
of each contaminant, minimal impacts to the overall
system activity are possible; however, in extreme cases,
some cycle life is jeopardised. For this reason, the risk/
benefit of including coker naphtha in the ULSD feed
blend must be evaluated along with the other impacts
on hydrogen partial pressure, increased space velocity
and fractionation requirements.
AJohn Jeanneret, Sr Business Leader, Hydrotreating
Catalysts, UOP, john.jeanneret@honeywell.com
Many silicon and arsenic trap materials available today
also have considerable hydrodesulphurisation (HDS)
activity. You should look for guard bed materials with
a good balance between silicon or arsenic capacity and
high HDS activity. We recommend that you consider
increasing the volume of silicon and arsenic guard bed
materials used in your ULSD unit. This results in
reducing the amount of hydrotreating catalyst avail-
able to meet your ULSD specifications, and it may be
necessary to increase the operating temperature of the
unit reactor and accept a shorter cycle length. If you
are processing a large volume of coker naphtha with
high levels of silicon and arsenic, you might consider
adding an additional reactor vessel to hold the larger
volumes of guard bed materials that may be required.
Q Is there some means to monitor coke formation in fixed
bed reforming catalyst and how do I best avoid coke formation
in the first place?
A
Tony Poparad, Sr Manager, Naphtha Catalyst Sales, UOP,
tony.poparad@honeywell.com
As coke levels increase on fixed-bed reforming cata-
lyst over the course of a cycle, the catalyst
deactivates. This means the reactor temperatures need
to be increased in order to achieve the desired sever-
ity (product octane, aromatics production, and so on)
at constant operating conditions. One way to monitor
the deactivation of the catalyst is to track the actual
temperature requirement to achieve the desired sever-
ity of operation versus the theoretical temperature
27/02/2013 12:00
 relentless

UOP has been serving catalyst customers for

decades, and constant innovation ensures we’ll
be there for decades to come.

Pilot plants. A true commitment to fast, thorough research and

development. A vast team of experienced, dedicated engineers
and scientists. The reasons to choose UOP catalysts are many,
but perhaps the biggest of all is that UOP never quits innovating. When you use UOP
catalysts, you’ll know you’re using products specifically designed to help optimize
your operation. UOP invented the refining and petrochemical technology used in most
operations today, and that knowledge and expertise comes through in every catalyst we
develop. You’ll always get the high stability and global support your business needs, and
you’ll be working with a company that will keep you on the leading edge year after year.

For more information about UOP catalysts, visit www.uop.com/catalysts.

© 2013 Honeywell International, Inc. All rights reserved

uop.indd 1 Adsorbents Ad_v6.indd 1

SPM-UOP-35 28/02/2013 10:17
2/27/13 2:11 PM
 that was required when the catalyst was freshly
regenerated (at start-of-run conditions). Reactor
temperature is normally expressed as the weighted
average inlet temperature (WAIT) of all the reactors.
Since the feed quality/quantity and other operating
conditions change over time, the theoretical WAIT
requirement needs to be normalised to account for
these changes. UOP can assist the users of its catalyst
to predict the theoretical WAIT requirement over time
so that catalyst deactivation can be monitored over
the course of a cycle. This can allow for more efficient
regeneration planning and the optimisation of
operating severity in the unit. The condition
(age, contaminant level, and so on) of the catalyst
loaded into the reactors can also drastically affect
the rate of coke formation and the ability of the
catalyst to perform well as it becomes increasingly
coked.
UOP has found that it is normally economical to
regenerate the catalyst when the spent catalyst coke
level in the last reactor has reached approximately 20
wt%. This corresponds to a WAIT deactivation of
30-40°F (17-22°C) from start of run to end of run. In
actuality, many customers extend their cycles beyond
this point in order to minimise the number of regen-
erations they need to perform.
Catalyst coking, or deactivation, can be altered in
several different ways. Monitoring the D86 distillation
end point (EP) of the feed is very important, since the
coking rate will increase with increasing feed EP. UOP
has determined that feed EP levels above 400°F (204°C)
will generally cause the catalyst deactivation rate to
increase very rapidly. The feed EP should be controlled
to even lower levels if possible for non-straight-run
naphtha feed components such as coker naph-
tha.  Changes to the paraffinicity of the feed will also
impact the catalyst deactivation rate. More paraffinic
feed will deactivate catalyst faster than less paraffinic
(more naphthenic) feed. Higher octane products and
higher throughputs will also cause more rapid catalyst
deactivation, so some operators reduce severity or feed
rate over time in order to help extend their cycles. The
relative amount of recycle gas to feed (normally
expressed as the hydrogen-to-hydrocarbon ratio) and
operating pressure of the unit also play a large role in
determining the overall coking rate. Lower hydrogen-to-
hydrocarbon ratios and operating pressures lead to
faster deactivation rates. While there may be some flex-
ibility to manipulate the hydrogen-to-hydrocarbon
ratio, it is normally maximised to increase cycle
lengths.
Most operators cannot readily change the operating
pressure of the unit by a significant amount to affect
the catalyst deactivation rate. Changing the catalyst to
a more coke-tolerant variety can also help operators
to increase cycle lengths or to operate at higher sever-
ity during a constant cycle. UOP’s R-500 Fixed-Bed
Platforming catalyst can normally increase cycle
lengths by more than 25% over existing catalysts, and
allow for significantly increased severity or through-
put when the cycle length is kept constant.
12 Catalysis 2013 www.eptq.com
Q&A copy 11.indd 6
Q Introduction of low rare earth FCC catalysts was originally
driven largely by raw material pricing issues. With experience
and hindsight, what are the technical issues justifying their
selection?
A Mark Schnaith, Sr Business Leader, FCC/Alkylation/
Treating, UOP, mark.schnaith@honeywell.com
The movement to lower rare earth (RE) FCC catalyst
had been under way long before the recent issue with
raw material price. The RE price spike added emphasis
to the investigation of RE-free catalysts and effective
alternatives. Some key technical reasons to consider
low rare earth catalysts in the FCC process are
improved coke selectivity and reduced hydrogen trans-
fer to preserve light olefins for petrochemical use.
Conversely, low RE can reduce the activity stability of
the catalyst, leading to higher make-up rates and cost.
Thus, there will always be a balance between desired
results and the cost of achieving those results when it
comes to the use of RE.
A George Hoekstra, President, Hoekstra Trading,
george.hoekstra@hoekstratrading.com
The 2010 price spike in rare earth metals caused
many refiners to compromise unit performance for
the sake of catalyst cost. It was one of several
episodes, such as the ULSD catalyst supply scare in
2003, the molybdenum price spike in 2004 and the
molybdenum price crash in 2007, all of which took
their toll on unit performance and profitability.
An important lesson from experience and hindsight
is that refiners should maintain flexibility in
their catalyst supply. Those who choose to stay
captive to a single supplier are inevitably hurt worst
when these external changes cause mini-panics in the
industry.   
Q When catalyst is removed from an HDS unit, the reactor
must be blanketed with nitrogen to keep the catalyst from
heating and possibly igniting. Are there safer alternatives for
catalyst removal?
A J Gary Welch, Technical Consultant, Cat Tech International,
gwelch@cat-tech.com
Since the introduction of hydrotreating and hydroc-
racking in the mid-20th century, refiners have
struggled with the task of safely removing catalysts
from reactors. Cobalt, nickel and molybdenum oxides
on the fresh catalyst are converted to sulphides when
the catalyst is activated in the reactor. These
sulphides are very reactive towards oxygen and can
spontaneously ignite when exposed to air. In the early
days, refiners often passivated catalysts by a
controlled burn in the reactor. This was very time
consuming and led to the release of large quantities
of toxic gases (SO2, NOx, CO, among others). This is
not allowed with today’s regulations for environment
and safety. The industry then went to inert unloading.
This created an oxygen-depleted work environment.
There were many fatalities related to these operations,
27/02/2013 12:00
 and the catalysts could still self-ig-
nite after removal. Through the
years, safety improvements have
dramatically reduced the incidents
of fatalities, but catalyst ignition
still creates serious environmental
and safety problems.
In today’s world, the CATnap
Catalyst Passivation Technology
from CatTech International is
available to reduce the reactivity
of the catalyst so that it can be
safely removed in an air environ-
normally required for an inert
entry can be minimised or elimi-
nated. A significant side benefit is
the elimination of catalyst dusting.
The dust adheres to the catalyst
pellets so that the environment is
not exposed to the toxic and pyro-
phoric catalyst dust particles. This
technology is applicable to all
liquid (trickle) flow hydrotreating
and hydrocracking units from
naphtha to residuum. Catalyst
treated with the passivation chemi-
cal can still be sent for reclamation
or regeneration as with non-
treated catalyst.

Independent Catalyst Test

ment and provide catalyst that
will not spontaneously ignite. This
technology is widely used in
the Far East, but has received
limited acceptance in the western
world.
Reports 2010, 2011 & 2012
CATnap technology involves the
application of a proprietary passiv- OUR REPORT WILL HELP YOU:
ation chemical to a recirculating oil
stream during the shutdown • Simplify catalyst selection
process. The chemical coats the
surfaces of the catalyst with an
• Choose the right
organic film, which retards oxygen catalyst with
penetration to the reactive metal confidence
sulphides. The catalyst is suffi-
ciently passivated that it can be
• Save hundreds of
safely removed from the reactor thousands on
under air and will not ignite once your next catalyst
outside the reactor. Elimination of purchase
the need for nitrogen during the
unloading is a significant cost
savings for many customers. The
CATnap shutdown procedure We have tested catalysts from all major suppliers. Our
eliminates a hot hydrogen strip-
ping operation. This and other
reports provide full test data, analysis, and activity rank-
time-saving features frequently ings. Our reports are available for immediate delivery.
save the refiner many hours, if not
days, during the turnaround. The Our team brings the industry’s leading independent
shutdown procedure is tailored to lab, innovative test methods, and sound, objective
each application based on criteria analysis. Our real-world experience includes 150
such as unit configuration, feed-
stock, operating history and other
catalyst testing runs and 100 catalyst decisions.
features. These procedures are
designed to minimise hydrocarbon
Contact us today for
vapour (LEL) or toxic gas issues independent test data,
inside the reactor.
There are many other safety and
reports, and catalyst
time-saving benefits as a result of rankings.
working in a breathable atmo-
sphere and with non-reactive
catalyst. Although the treated cata-
lyst is relatively benign, it is still Hoekstra Trading LLC
unloaded by technicians in breath-
ing apparatus since it is a confined
www.hoekstratrading.com
space operation. However, the george.hoekstra@hoekstratrading.com
areas around manways and dump
nozzles are free of nitrogen blan- +1 630 330-8159
keting, which means the hot zones

www.eptq.com Catalysis 2013 13

Q&A copy 11.indd 7 27/02/2013 12:01

cattec.indd 1 26/02/2013 16:59
 Advances in FCC pretreatment catalysis

Performance data for a new FCC pretreat catalyst show a substantial advance in
HDS and HDN activity

BILL GILLESPIE, ALEXEI GABRIELOV, THOMAS WEBER and LARRY KRAUS

Criterion Catalysts & Technologies

C
atalysts applied in FCC feed Process conditions: high throughput Feedstock properties: high throughput
pretreat (FCC PT) service experimentation experimentation
must operate robustly with
the wide range of feeds charged to
Hydrogen/oil ratio, SCFB 4060 Hydrogen, wt% 11.65
these units. These feeds’ origins (~675 Nm3/m3) Carbon, wt% 85.60
include crude atmospheric and Pressure, psig 1350 (93 barg) Nitrogen, wt% 0.44
vacuum towers, cokers, ROSE/ LHSV, hr-1 0.86 Sulphur, wt% 2.05
deasphalters, FCC units, lube units Target N, wppm 500 Basic nitrogen, wppm 1447
Target S, wppm 200 API gravity 19.29
and others. FCC PT units often HTSD 50% (°F) 774 (412°C)
process synthetic feeds. Catalysts HTSD 95% (°F) 980 (527°C)
that operate in FCC PT service Table 1
must obtain optimised sulphur, Table 2
nitrogen and aromatic saturation features of Ascent DN-3551, an
performance to drive the FCC industry-proven NiMo FCC PT high throughput experimentation.
process’s economic performance. catalyst,1 with Centera’s active site The high throughput reactor
They must also be able to operate architecture. This allows for step- system utilises multiple tubular
stably in an environment where out hydrodesulphurisation (HDS), flow reactors with automated
significant levels of contaminants hydrodenitrogenation (HDN) and process control and sampling. The
such as nickel, vanadium, silicon, aromatics saturation (ASAT) perfor- use of this multi-tube reactor
sodium, arsenic and asphaltenes mance, plus high catalyst stability system allows significant accelera-
are present. Often, several catalysts in FCC PT applications. tion of catalyst development
are utilised in a tailored package to relative to conventional testing
fulfill the demands placed on the Catalyst development and testing techniques. Leads generated with
FCC PT unit. The new-generation A significant aspect of the DN-3651 high throughput equipment were
Centera catalyst DN-3651 combines development programme is that the confirmed by conventional-scale
commercially demonstrated stabil- catalyst was developed specifically pilot plant testing. The reactor
ity and the contaminant tolerance for FCC PT applications utilising conditions and feedstock properties

30
Activity improvement relative

Activity improvement relative

25
13
20 DN-3651 11
9
to DN-3551, ºC

15
to DN-3551, ºF

7
10 5
5 3
1
0
–1
–5 –3
Approach 1 –10 –5
Approach 2 –7
–15
Approach 3 –9
Approach 4 –20 –11
0 50 100 150 200 250
Approach 5
DN-3651 development samples Catalyst sample number

Figure 1 DN-3651 HDN activity improvement: high throughput experimentation

www.eptq.com Catalysis 2013 15

criterion.indd 1 27/02/2013 12:08

 15 DN-3651

Activity improvement relative

Activity improvement relative

7
10
5

to DN-3551, ºC
3

to DN-3551, ºF
5
1
0
–1
–5 –3

–10 –5
Approach 1
–7
Approach 2 –15
–9
Approach 3
Approach 4 –20 –11
0 50 100 150 200 250
Approach 5
DN-3651 development samples Catalyst sample number

Figure 2 DN-3651 HDS activity improvement: high throughput experimentation

enclosed in the highlighted area in

Process conditions: pilot plant testing, Feedstock properties: pilot plant testing,
Figures 1 and 2, labelled DN-3651,
synthetic feed synthetic feed
represent samples tested as part of
scale-up and manufacturing opti-
Hydrogen/oil ratio, SCFB 6700 Sulphur, wt% 4.24 misation. Use of high throughput
(~1115 Nm3/m3) Nitrogen, wt% 0.422
Pressure, psig 1800 (124 barg) Basic nitrogen, wt% 0.136
experimentation allowed rapid
LHSV, hr-1 1.14 MCR, wt% 1.2 development of a reliable manufac-
Target N, wppm 260 Ni/V, wppm 1.0 turing process, yielding the highest
Target S, wppm 1000 API gravity 11.62 practical catalyst performance.
HTSD 50% (°F) 754 (401°C)
HTSD 95% (°F) 966 (519°C)
These data, coupled with pilot
Table 3 plant data and discussed below,
clearly demonstrate success in
used in high throughput experi- Table 4 exceeding the 10°F (5.5°C) HDN
mentation are listed in Tables 1 and activity improvement target, as
2, respectively. scale-up and commercialisation well as providing significantly
The target performance level for phase, while Figure 2 illustrates improved HDS activity.
DN-3651 was an improvement in HDS activity. The activity as Pilot plant testing was conducted
HDN activity of at least 10°F presented in these plots is the in trickle-flow, fixed-bed reactors
(5.5°C) relative to DN-3551 (~20 decrease in temperature required to using 50 cc catalyst loads. The cata-
RVA [relative volume activity]) achieve the target sulphur or nitro- lyst load consisted of whole pellets
with equivalent or better HDS gen level in the product relative to diluted with an equal volume of an
activity. Figure 1 illustrates the that required by DN-3551. 80-60 mesh fraction of silicon
high throughput experimentation Approach 4 shown in Figures 1 carbide. Plug flow and wetting
data for HDN activity obtained and 2 represents the approach that requirements were assured for each
during the prototype development ultimately led to the final formula- test. A variety of commercial FCC
phase, as well as during the tion of DN-3651. The points PT feedstocks were used to demon-
strate the advantage of DN-3651 in
various operations.
40 In the first example, the commer-
Temperature advantage,

Temperature advantage,

35 20 cial unit processes high-sulphur,

700ºF 720ºF 40ºF
30 371ºC 382ºC 393ºC high-nitrogen synthetic feedstocks
25
15 at high pressure. The process
conditions employed and the test
20
ºC
ºF

10 feed properties are given in Tables

15
3 and 4. Data were obtained at 700,
10 5 720 and 740°F (371, 382 and 393°C),
HDS
5
HDN
producing typical product nitrogen
0 0 levels in the ranges 200-900, 50-500
0 100 200 300 400 500 600 700 800 900 and 6-350 wppm, respectively,
Run length depending on the catalyst used and
the time on stream. Product
Figure 3 HDN and HDS activity improvement: pilot plant testing, synthetic feed sulphur levels were typically

16 Catalysis 2013 www.eptq.com

criterion.indd 2 27/02/2013 12:08

 Up to 40% activity increase with Topsoe.com /hyBRIm

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Improved durability and activity from

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Haldor Topsøe A/S is proud to announce HyBRIM™, its next

generation catalyst production technology that builds on the
proven BRIM™ technology.

The enhanced features of our new HyBRIM™ technology result in

an activity increase of up to 40% compared to our current BRIM™
generation catalysts. This higher activity can be used to:

≥ Achieve longer cycles at the same feed rate
≥ Process tougher feeds
≥ Increase conversion to achieve higher volume swell
In 2013, we will celebrate Haldor Topsøe’s 100th birthday.
He founded our company over 70 years ago with a passion
for science and innovation. These values continue to show
us the way forward as we create sustainable solutions that
make a difference to the world of today – and tomorrow.

≥ Increase throughput

haldor.indd 1 26/02/2013 16:11

10395_HT_Ad_210x297mm_PTQ.indd 1 15/02/13 11.40
 Process conditions: pilot plant testing,
25
Asia-Pacific VGO feed
680ºF 716ºF

Temperature advantage, º C
Temperature advantage, º F 360ºC 380ºC 12
20
Hydrogen/oil ratio, Nm3/m3 503
10 (3020 SCFB)
Pressure, barg 70 barg (1015 psig)
15 8
LHSV, hr-1 0.9
Target N, wppm 700
6 Target S, wppm 1000
10
4
5 Table 5
HDS 2
HDN
0 0 Feedstock properties: pilot plant testing,
0 100 200 300 400 500 600 700 800 Asia-Pacific VGO feed
Run hours

Figure 4 HDN and HDS activity improvement: pilot plant testing, Asia-Pacific VGO feed Sulphur, wt% 2.07
Nitrogen, wt% 0.1936
Basic nitrogen, wppm 0.062
API gravity 26.7
160 HTSD 50% (°C) 440 (824°F)
HTSD 95% (°C) 603 (1117°F)
US Midwest US West US West US Gulf
feed Coast feed 1 Coast feed 2 Coast feed
140 Table 6
DN-3551
DN-3651
Centera DN-3651 over Ascent
120
DN-3551 catalyst. The activity
advantage of DN-3651 was main-
100
tained throughout the duration of
the extended pilot plant test, which
included high-temperature opera-
80 tion, where catalyst deactivation is
HDN HDS HDN HDS HDN HDS HDN HDS typically accelerated. This indicates
Test 1 Test 2 Test 3 Test 4 that DN-3651 has stability equiva-
lent to that of DN-3551, which has
Figure 5 RVA comparison: DN-3651 Centera and DN-3551 Ascent, multiple feeds consistently demonstrated high
stability in commercial FCC PT
service.
Gas rate, Nm3/m3 Another example illustrates the
0 500 1000 significant activity advantage of
60 DN-3651 and stable operation at
380°C (716°F) in a moderate hydro-
gen pressure of 70 barg (1000 psig)
HDN RVA advantage vs

50 SRVGO
0.15% N using an Asia-Pacific VGO feed.
40 1.75% S
The process conditions employed
DN-3551

and the test feed properties are

30 82% HKGO
0.42% N given in Tables 5 and 6.
US West Coast
4.24% S Figure 4 demonstrates a tempera-
20
0.43% N ture advantage of 5-10°C (9-18°F) for
2.03% S Centera DN-3651 over the previ-
10
ous-generation Ascent DN-3551
0 catalyst under moderate pressure
0 2000 4000 6000 8000 conditions. These data also demon-
Gas rate, scf/bbl strate that DN-3651 has the same
high stability as DN-3551 at moder-
Figure 6 DN-3651 Performance (RVA) vs DN-3551: hydrogen availability impact ate pressure. This is attributable to
the use of the commercially proven
800-2300, 200-1200 and 30-70 HDN (temperature required to Ascent catalyst support technology
wppm, respectively, at the three achieve 260 wppm product nitro- for DN-3651.
temperatures. gen) and 12-20°F (7-11°C) in HDS Summary data for four more
Figure 3 illustrates temperature (temperature required to achieve examples, labelled as Tests 1-4 and
advantages of 20-25°F (11-14°C) in 1000 wppm product sulphur) for demonstrating the performance of

18 Catalysis 2013 www.eptq.com

criterion.indd 3 27/02/2013 12:09

 DN-3651 processing a variety of
feedstocks of different origins over
a wide range of operating pressures
(1250–1600 psig, 86-110 bar), are
presented in Table 7 and Figure 5.
The feeds processed and process
conditions employed in these tests
are shown in Table 7.
In Figure 5, DN-3651 shows
significant activity advantages over
DN-3551. DN-3651 has HDN RVA
of 120–135 and HDS RVA of
120–130 compared with DN-3551
(RVA = 100).
The advantages in performance of
DN-3651 over DN-3551 are
enhanced when operating at
high hydrogen availability (a
hydrogen-rich environment). Figure
6 illustrates the relationship between
DN-3651’s HDN RVA advantages
over DN-3551 and H2 availability.
While DN-3651 shows advantages
in performance in all process condi-
tions, these data show that it has an
even greater advantage in hydro-
gen-rich environments. This allows
the capabilities of units in this oper-
ating environment to be more fully
utilised.
Catalyst characterisation
Commercial DN-3651 catalyst was
characterised using transmission
electron microscopy (TEM) and
X-ray photoelectron spectroscopy
(XPS) and compared with DN-3551.
TEM images of sulphided DN-3651
and DN-3551 are shown in
Figure 7.
Evaluation of the Centera
DN-3651 TEM image shows that
the sample consists of supported
(90%) and unsupported bulk (10%)
domains, having particle sizes in
the range 2.5-6.0 nm, centred
around 3.5 nm. While the average
degree of stacking for the
supported particles is <1.5 due to
the presence of a substantial
amount of single layers, it is clearly
>2.0 for the unsupported particles.
Evaluation of sulphided DN-3551
TEM images yields an average
particle size of around 4.0 nm and
an average degree of stacking
around 1.5. The striking difference
between these two catalysts is the
dispersion of particle sizes, leading
to much less uniform active
domains for DN-3651, which
www.eptq.com
criterion.indd 4
Centera DN-3651 Ascent DN-3551
Lavg, nm = 3.5; navg = 1.3 to 2.0 Lavg, nm = 4.0; navg = 1.5
Figure 7 TEM images: Centera DN-3651 (left) and Ascent DN-3551 (right)
provides higher catalyst activity (DDS) selectivity ratio is HYD/DDS
from greater accessibility of active = 4.
site edges. In a previous publication,2 char-
XPS measurements show that the acterisation data for DN-3630 NiMo
active form of DN-3651 is fully Centera catalyst, an ultra-high-
sulphided with an approximate activity catalyst designed for ULSD
Mo:S stoichiometry slightly below operations, were reported. DN-3630
1:2. XPS spectra for DN-3651 are was characterised using TEM,
shown in Figure 8. This finding extended X-ray adsorption fine
suggests that the edge structure is structure (EXAFS) and Fourier
incompletely covered with sulphur, transform infrared (FTIR)/nitric
which should lead to a high oxide (NO) adsorption. The FTIR/
concentration of unco-ordinated NO adsorption data obtained were
metal sites, which are ideally suited consistent with the edge surface of
for hydrogenation reactions. This is sulphided DN-3630 containing only
confirmed in DBT HDS measure- co-ordinatively unsaturated nickel
ments, where the hydrogenation and no co-ordinatively unsaturated
(HYD) and direct desulphurisation molybdenum. The high activity of
Feed properties and testing conditions: Centera DN-3651 and Ascent DN-3551,
multiple feeds
Test 1 Test 2 Test 3 Test 4
US Midwest US West US West US Gulf
Canadian feed Coast feed 1 Coast feed 2 Coast feed
LHSV, hr-1 0.75 0.86 1.00 0.50
Gas rate, SCFB/Nm3/m3 3500/585 4060/675 3450/575 2000/335
Pressure, psig/barg 1400/97 1350/93 1600/110 1250/86
Density @ 60F, g/cc 0.9659 0.9384 0.9131 0.9682
Sulphur, wt% 3.32 2.05 1.29 3.45
Nitrogen, ppm 2640 4380 1870 2330
Aromatics by UV, wt% C
Mono 5.8 4.9 5.3 5.0
Di 4.7 4.2 4.4 3.8
Tri 6.5 5.0 3.9 5.5
Tetra 6.1 3.8 2.6 6.5
Total 23.0 17.9 16.3 20.7
Distillation, wt% off ?F/?C ?F/?C ?F/?C ?F/?C
0% 367/186 540/282 322/161 666/352
10% 560/293 599/315 549/287 717/381
30% 725/385 710/377 664/351 835/446
50% 809/432 774/412 734/390 930/499
70% 861/461 828/442 800/427 1036/558
90% 941/505 922/494 895/479 1177/636
95% 999/537 980/527 943/506 1232/667
100% 1095/591 1010/543 1058/570 1316/713
Table 7
Catalysis 2013 19
27/02/2013 12:09
 generations of FCC PT catalysts for
a a wide range of feed properties and
processing conditions. This was
achieved by a new process that
creates chemically unique active
sites with enhanced activity and
improved dispersion, while utilis-
Mo(IV)

ing the proven support properties

of Ascent catalysts.

Acknowledgement
The authors would like to acknowledge the
efforts of Theo Meuris and David Grisafe in the
240 236 232 228 224 220 development of DN-3651.
Binding energy, eV
References
1 Bavaro V, Gripka P, Gabrielov A, Zhang C,
b Value Driven Catalyst Developments in FCC
Pretreatment Service, AIChE Spring National
Meeting, Orlando, FL, 23-27 Apr 2006.
2 Smegal J A, Weber T, Kraus L S, Criterion
CENTERA hydroprocessing catalysts: improved
active site architecture provides improved
Ni(II)

ULSD HDS activity, Prepr. Pap.-Am. Chem. Soc.,

Div. Pet. Chem., 2010, 55, 2, 21.

Bill Gillespie is a Senior Staff Chemist and has

been with Criterion/Shell for 32 years, carrying
out various assignments in catalyst R&D. He
890 880 870 860 850 has conducted research in hydrotreating,
Binding energy, eV hydrocracking, catalytic reforming and a
number of exploratory programmes. He holds
a PhD from the University of California at
c Berkeley in chemistry.
Alexei Gabrielov is a Team Lead, Catalyst
Development, at Shell Projects and Technology
(Criterion). He has worked for Shell/Criterion
for 17 years, leading numerous R&D projects,
and has a strong record in heterogeneous
S2–

catalysis (PhD, 1990 from Moscow State) as

176
Binding energy, eV
Figure 8 Mo 3d (a), Ni 2p (b) and S 2p (c) XPS Spectra: sulphided DN-3651
DN-3630 was attributed to this
novel active site architecture and to
improved active metals dispersion.
FTIR/NO adsorption analyses and
other additional characterisation
data for DN-3651 will be reported
separately.
Conclusions
Centera DN-3651 provides gains in
performance that can provide a
168 160
wide range of operating improve-
ments. To date, 11 FCC pretreat
operations have selected DN-3651
as a component of their catalyst
system for increased levels of FCC
conversion, increased upgrading of
challenging low-value feeds and
extended operational cycle lives.
Centera DN-3651 represents a
substantial improvement in HDS
and HDN activity over previous
well as in chemical engineering.
Thomas Weber is Principal Scientist
Catalyst Development at Shell Projects and
Technology (Criterion) and Professor of Solid-
State Inorganic Chemistry at the Eindhoven
University of Technology. He has a strong
record in heterogeneous catalysis and is
currently the president of the Dutch Catalysis
Society. Before joining Shell in 2008, he was
associate Professor in Heterogeneous Catalysis
and Industrial Chemistry at the Swiss Federal
Institute of Technology in Zurich (ETH). He
holds a PhD in inorganic chemistry from the
University of Bielefeld, Germany.
Lawrence (Larry) Kraus is the Hydroprocessing
Product & Development Manager for Criterion
Catalysts & Technologies. Prior to that, he held
the Technical Service Manager/Team Lead for
the Clean Fuels, Projects & Strategic Accounts
Group. He holds a BS degree in chemical
engineering from Kansas State University, and
MS and PhD degrees in chemical engineering
from Northwestern University.

20 Catalysis 2013 www.eptq.com

criterion.indd 5 27/02/2013 12:09

 Crude unit

Gas / liquid Hydrotreating catalysts Hydrogen catalysts

purification Process
S, Hg, Cl removal Naphtha HDS Hydrogen plant diagnostics

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Vacuum tower VGO HDS SOx NOx removal
Light olefin production
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FCC unit Metals traps
Activity boosters
CO oxidation

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process technology for oil refining processes.

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jm.indd
Untitled-11 1 26/02/2013
31/07/2012 17:04
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exxon.indd 1 26/02/2013 16:34

 New catalyst increases FCC distillate yield
A FCC trial with a new residue maximum distillate catalyst provided an improved
yield structure at a similar fresh catalyst addition rate and rare earth level
CARL KEELEY, JEREMY MAYOL, STEFANO RIVA and VASILEIOS KOMVOKIS BASF Corporation, Refining Catalysts
STEPHEN CHALLIS Chalcat Consulting
T
he FCC unit at a refinery in
western Europe is a Shell
design adapted to process
some residue. The base catalyst was
a VGO processing catalyst with a
high Z/M ratio and 2.3 wt% rare
earth level.
In 2009, the FCC unit’s operating
objective changed from maximum
conversion to maximum distillate
production. Aligned with this
change in operating objective, the
unit began to process 15-20 wt% of
residue comprising of vacuum resi-
due and wash oil from the vacuum
distillation unit. Wash oil from the
vacuum distillation unit (VDU) is
the material from the heaviest
pumparound between the bottom
and the heavy distillate. This
pumparound is set to limit coking
in the flash zone of the VDU tower.
Part of this material was drawn as
a product and sent to the FCC unit.
This resulted in Conradson carbon
residue (CCR) of up to 2 wt% and a
moderate contaminant metal level,
with nickel and vanadium up to
6000 ppmw on equilibrium catalyst
(e-cat).
A trial with another supplier’s
maximum distillate catalyst (with a
low Z/M ratio) was abandoned as it
was judged that, at a higher coke
yield, the total gain in LCO from
both a reduced gasoline yield and
improved bottoms upgrading was
below expectation. Since the driver
for a catalyst change was still valid,
BASF was invited to help improve
the unit’s performance. This resulted
in the selection of BASF’s Stamina
catalyst for selectively maximising
distillate with a residue feed.
This article presents the details of
a Stamina catalyst trial conducted
www.eptq.com
basf.indd 1
Matrix
Zeolite
Zeolite Matrix
Figure 1 BASF’s Proximal Stable Matrix & Zeolite (Prox-SMZ) Platform
at the refinery in 2010. Operating
data and results for a 65% change-
over to Stamina catalyst are
discussed; these were the basis of
the refinery’s decision to engage in
a long-term supply contract.
Stamina catalyst
was selected to best
fit the objectives,
constraints and
operation of the unit
and to deliver the
highest value
Catalyst selection
BASF provides technical service to
understand unit operation and all
the constraints. The company has a
large range of tools that are selec-
tively used, based on specific needs,
to ensure a flawless catalyst change
and optimised unit operations with
Matrix
Zeolite
the new catalyst. The tools selected
in this case were:
• Cold Eyes Review: to develop a
detailed understanding of the unit’s
objectives, constraints and operation
• Operating Data Analysis: to
review the base operation, and to
help monitor and optimise unit
performance during the trial
• Real-time Circulating Catalyst
Activity Estimator: to manage cata-
lyst additions during the trial.
Stamina catalyst was selected to
best fit the objectives, constraints
and operation of the unit, and to
deliver the highest value. This FCC
unit was one of the first to trial
Stamina catalyst. Since then, the
catalyst has been used in many
units.
Stamina is based on BASF’s
Proximal Stable Matrix & Zeolite
(Prox-SMZ) platform (see Figure 1).1,2
This platform is built on two main
features, one being the presence of
an ultra-stable and coke-selective
matrix and the other being the close
proximity of an ultra-low sodium
zeolite and the matrix, which are
Catalysis 2013 23
28/02/2013 12:25
 Figures 2a-c Stamina catalyst customisation for FCC unit in a western European refinery
Figures 3a-c Stamina trial feed quality and unit throughput
formed in a single manufacturing
step. Stamina shows superior zeolite
and matrix surface area retention
compared to other technologies,2
which reflects the advantages of the
novel Prox-SMZ matrix and the
ultra-low sodium zeolite technology.
It is the synergy between the zeolite
and matrix that leads to rapid trans-
fer of reactants from the matrix acid
sites to the zeolitic acid sites. This
Figures 4a-d Stamina trial contaminant metal levels
24 Catalysis 2013
basf.indd 2
enhanced transfer helps to stabilise
coke precursors produced by the
matrix cracking, leading to higher
LCO production without producing
excessive amounts of dry gas and
coke.
BASF has made strides in devel-
oping catalyst technologies with the
lowest sodium levels, as it is well
known that sodium cations have
a negative impact on zeolite
stability.3 Sodium cations in the
unit feed stream and at operating
conditions are converted to sodium
hydroxide, which catalyses the
hydrolysis of the zeolite silica-
hydroxide (---Si-OH) bonds, lead-
ing to zeolite collapse.
Thus, BASF FCC catalysts suffer
less sodium acid site neutralisation
and zeolite deactivation, and have
inherent vanadium resistance.
Furthermore, because of the low
sodium content of these catalysts,
hydrogen transfer reactions are
minimised, which improves the
LCO quality — particularly the
cetane — at a similar rare earth
oxide/zeolite level. Note that the
added sodium was similar, but the
resulting total sodium on e-cat was
much lower due to the lower
sodium on the fresh catalyst (see
Figure 4c), and BASF FCC catalysts
also use a separate particle vana-
dium trapping technology.
To meet the refinery’s objective of
distillate maximisation, the Stamina
catalyst was customised. The rare
earth content was similar to that of
another supplier’s catalysts (see
Figure 2a). To improve bottoms
upgrading, the matrix surface area
was significantly increased (see
www.eptq.com
27/02/2013 12:31
 Figures 5a-c Stamina trial improved LPG yield

Figures 6a-c Stamina trial improved gasoline yield

Figures 7a-f Improved LCO yield and reduced slurry yield

Figure 2b) and the zeolite surface
area was similar; thus, the total
surface area increased (see Figure
2c).
Catalyst performance
Comparing operating conditions
during the Stamina catalyst trial
with another supplier’s distillate
catalyst trial:
• Feed CCR, density and unit feed
rate were similar (see Figure 3)
• Vanadium and nickel were simi-
lar (see Figures 4a and b)
• The added sodium was similar,
but the resulting total sodium on
e-cat was much lower due to the
lower sodium on the fresh catalyst
(see Figure 4c)
• The fresh Stamina catalyst had
similar iron on catalyst content.
However, the added feed iron was
significantly higher during the
Stamina trial, resulting in a higher
e-cat iron measurement (see Figure
4d). Despite the relatively high
level of iron in the unit feed, flush-
ing e-cat was not required, as there
were no signs of catalyst surface
sintering, dry gas selectivity

www.eptq.com Catalysis 2013 25

basf.indd 3 27/02/2013 12:31

 Figures 8a-c Stamina trial dry gas yield
Figures 9a-c Stamina trial coke yield
deterioration and/or activity loss.
Note that BASF FCC catalysts are
highly engineered particles with a
designed pore structure and high
overall porosity, and therefore are
resistant to iron pore-plugging
deactivation
• The Stamina catalyst at a similar
fresh catalyst addition rate provided
a significantly improved yield struc-
ture towards maximising LCO
• A desired reduction in the LPG
yield of about 3 wt% (see Figure 5).
However, if a refinery needed to
maintain the same LPG yield, a
lower rare earth oxide/zeolite cata-
lyst formulation, either on its own
or in combination with the ZSM-5
additive, could be used to convert
gasoline to LPG. If this is achieved
through combining the benefits of
the BASF FCC catalyst and
Maximum Olefin Additive (a opti-
mised ZSM-5-based additive), the
remaining gasoline will also have a
higher octane
• A desired reduction in gasoline
yield of about 4 wt% (see Figure 6)
• Outstanding increase in the LCO
yield with Stamina (see Figures
7a-c): about 8 wt% compared to
another supplier’s base maximum
conversion catalyst, and about
26 Catalysis 2013
basf.indd 4
5 wt% compared to another
supplier’s maximum distillate cata-
lyst (see Figure 7c)
• Slurry yield data are shown in
Figure 7. Considering the time
series for the unit feed rate (see
Figure 3c) and unit slurry yield
(see Figure 7d), the change to
The change to the
Stamina catalyst was
considered successful
in achieving the
refinery’s objectives
another supplier’s maximum distil-
late catalyst was accompanied by
an operating period with a low
unit feed rate. Thus, to compare
the catalysts on a similar basis, we
consider the operating period with
the competitor’s maximum distil-
late catalyst in January, where the
unit feed rate was on average
higher/more typical. The data for
this period show that the slurry
yield for the Stamina catalyst is
similar to that of the other suppli-
er’s maximum distillate catalyst;
however, the Stamina LCO yield is
much greater at similar operating
conditions, due to the improved
LCO selectivity of the Stamina
catalyst
• The dry gas and coke yields
(Figures 8 and 9) at improved
bottoms cracking of Stamina
(Figure 7) are remarkable, given
that the matrix surface area of the
Stamina catalyst was significantly
higher compared to the other
supplier’s catalyst (Figure 2b).
Overall, the change to the
Stamina catalyst was considered
successful in achieving the refin-
ery’s objectives of maximising
distillate production with increased
residue processing. Providing
value-added technical service
during the trial’s preparation phase
and throughout the trial ensured
that the unit was fully optimised
with the new catalyst.
Conclusion
Close co-operation with the refin-
ery enabled BASF to demonstrate
its catalyst technology and techni-
cal service. During the 2010
commercial trial, the performance
of BASF’s residue maximum distil-
late catalyst exceeded the refiner’s
www.eptq.com
27/02/2013 12:31
 expectations. The Stamina catalyst
provided an improved yield struc-
ture at a similar fresh catalyst
addition rate, at a similar rare earth
level, with higher added active
matrix level and improved zeolite
surface area stability:
• Net LPG and gasoline yield
decreased by about 7 wt%
• LCO yield increased by 5 wt%
and was even higher at about
+8 wt% when compared to the base
competitor maximum conversion
catalyst
• Dry gas and coke yield were
similar, despite the significant
increase in matrix surface area from
50 to 70 m2/g (the base competitor
maximum conversion catalyst had
a matrix surface area of 35 m2/g)
• Using standard feed and product
prices, typical for an FCC unit in
Europe, Middle East and Africa,
the estimated profit improvement
was almost 1 $/bbl of fresh feed
delivered by the improved yield
structure towards maximising LCO.
Stamina is a trademark of BASF.
25 years excellence
in VaPOr PressUre TesTinG
MINIVAP ON-LINE
• Vapor Pressure of Gasoline, Crude Oil and LPG
• According to the Latest ASTM & ISO Standards
• Unparalleled Measuring Accuracy
• Up to 2 Sample Streams
• Automatic Calibration
• Fast and Easy Maintenance
Phone +43-1-282 16 27-0 | Fax +43-1-280 73 34 | info.grabner-instruments@ametek.at
ON-LINE half page kette.indd 1
www.eptq.com
basf.indd 5
References
1 McLean J B, The role of FCC catalyst
technology in maximising diesel production,
NPRA AM-09-34.
2 Kraus M, Kiser N, Fu Q, Yang J, Thornton
O, Finch J, Stamina – new FCC catalyst for
maximum distilate yield demonstrated in Big
West’s Salt Lake City refinery, NPRA AM-10-
171.
3 Xu M, Liu X, Madon R J, Pathways to Y zeolite
destruction: the role of sodium and vanadium,
Journal of Catalysis, 207, 2002, 237-246.
Carl Keeley is Marketing Manager for Europe,
Middle East & Africa with BASF Corporation,
Refining Catalysts. He has over 12 years’
experience in the chemical and hydrocarbon
industries, specialising in providing technical
support for operations and licensing for FCC,
and feed and product treating. He holds a MEng
in chemical engineering and applied chemistry
from Aston University, UK, and is a professional
engineer (CEng) and a member of the Institute
of Chemical Engineers in the UK.
Jeremy Mayol is Technical Account
Manager with BASF Corporation, Refining
Catalysts. With over 15 years’ experience in
hydrocarbon processing, he is a recognised
technical specialist in FCC unit operations,
troubleshooting and process simulation. He has
worked for BASF for four years and previously
worked for INEOS and BP Refining & Marketing
at the Lavera Refinery.
Stefano Riva is Technical Service Manager
for Europe, Middle East & Africa with BASF
Corporation, Refining Catalysts. He has over
20 years’ FCC experience, with Engelhard and
BASF in technical sales and technical service,
with Tamoil, and at ExxonMobil’s Trecate
refinery, Italy.
Vasileios Komvokis is Technology Manager
for Europe, Middle East & Africa with BASF
Corporation, Refining Catalysts. Prior to
joining BASF, he was a Research Professor at
the Chemical Engineering Department of the
University of South Carolina. He holds a BS
and MS in chemistry and a PhD in chemical
engineering from Aristotle University of
Thessaloniki, Greece. Parallel to his studies, he
worked for six years as a Researcher at CPERI
Institute of Thessaloniki.
Stephen D Challis is a Senior FCC Consultant.
With over 32 years’ experience, he has been
a consultant to BASF for about three years
and previously worked for ExxonMobil for 29
years, with 22 years spent as a FCC process
specialist providing operations and technical
support to EMEA FCC units on optimisation,
troubleshooting, project development, design
and startups.
05.06.2012 14:52:27
Catalysis 2013 27
27/02/2013 12:31
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in guard bed media. norpro.steinefrenz@saint-gobain.com

norpro.indd
Norpro 1 XPore 80 Ad_newpub.indd 1
MacroTrap 26/02/2013 16:19
2/12/13 3:46 PM
 Best practices for SOx emissions control
Applying the key elements of experience gained since the introduction of
SOx-reducing additives for FCC operations
Ray Fletcher
Intercat
S
Ox-reducing additives were
first introduced into the FCC
world in 1984 by Arco
Refining. Clean air legislation
enforced by the Environmental
Protection Agency required FCC
units operating with the US to
begin introducing SOx-reducing
additives as one of the best availa-
ble control technologies. The use of
these additives quickly spread
throughout the refineries in North
America.
A substantial body of experience
has been accumulated within the
industry since SOx additives were
first injected into FCC units. This
experience spans a very wide range
of operations, including “mild
reductions”, in which modest levels
of SOx reductions were required,
up to and including ultra-deep
reductions to 5 ppm or less. These
operations span full-, partial- and
two-stage combustion regenerators.
Refineries operating in strict
compliance zones have been
required to reduce SOx emissions
for decades. Some refiners have
chosen the path of large capital
investment via the installation of
catalytic feed hydrotreaters or flue
gas scrubbers to control SOx emis-
sions. Many refiners have chosen to
use additives as a capital-free route
to control emissions.
As regulations spread more
widely, many refiners are now
being required to reduce SOx emis-
sions. This article is intended to
enable these refiners to take advan-
tage of the experience accumulated
within the industry and crystallises
the most useful lessons learned
since the mid-1980s.
The term SOx is used throughout
www.eptq.com
intercat.indd 1
this article to represent total
oxidised sulphur in the form of SO2
plus SO3, which is emitted from the
FCC flue gas stack.
SOx emissions chemistry
The reactions related to sulphur
combustion are well understood. A
simplified overview of these reac-
tions is helpful in understanding
how to control SOx emissions
within the FCC regenerator.
In full-combustion operations,
100% of the sulphur contained
within the coke will be oxidised.
Approximately 90% of this oxidised
sulphur will be in the form of SO2,
with the remainder being oxidised
to SO3. SOx-reducing additives
absorb SO3. Most SOx-reducing
additives contain cerium, which
functions as an “oxygen sponge”
and catalyses SO2 to SO3. The SO3 is
then reacted with magnesium-
forming magnesium sulphate. The
magnesium sulphate is transported
into the reducing atmosphere of the
reactor vessel, where sulphur is
released as H2S. The magnesium is
then regenerated to MgO and is
available for additional absorption
reactions within the regenerator.
These reactions are:
S + O2 → SO2 (1)
SO2 + ½ O2 → SO3 (2)
SO3 + MgO → MgSO4 (3)
MgSO4 + 8[H] → MgO + H2S + 3H2O (4)
Sulphur combustion within the
partial-combustion regenerator is
very similar to combustion within
the full-burn regenerator. The
notable exception is insufficient
oxygen to fully oxidise the sulphur
to SO2. A portion of the sulphur
will be partially oxidised to COS, as
shown below:
S + CO → COS (5)

COS + H2O → CO2 + H2S (6)
Two-stage regenerators are
unique in that the first stage oper-
ates in partial combustion, while
the second stage normally operates
in full combustion. The first-stage
regenerator’s sulphur combustion
reactions are dominated by reac-
tions 1 and 5, while in the
second-stage regenerator reactions
1 and 2 predominate.
Predicting SOx emissions
Development of an accurate uncon-
trolled SOx emissions model is the
first step when initiating a SOx
additive trial. Baseline data are
used to develop a correlation that
accurately predicts SOx emissions.
The additive of choice is then
injected into the unit. SOx emis-
sions will drop rapidly as the
additive begins to circulate within
the unit. The correlation is used to
calculate the uncontrolled SOx
emissions for comparison with
observed emissions. This enables
the process engineer to calculate
the efficiency of the SOx reduction
and additive.
SOx emissions will correlate with
feed sulphur in some but not all
units (see Figure 1). The sulphur
present within the FCC feedstock
partitions differently between coke
and liquid products, depending on
the type of sulphur molecules
Catalysis 2013 29
27/02/2013 12:42

This exchanger has seen better crude slates
Nasty Stuff
Heavy crudes are here to stay.
As long as oil prices remain high,
Canadian, Venezuelan, Deep Water
Gulf of Mexico, Mexican and
other low API gravity crude oils
will play an ever more important
role in supplying world refineries.
And prices promise to remain high
because gainsayers notwithstanding,
Hubbert was right.
A big question is how to best handle
these nasty crudes? Do you
revamp existing units or invest in
new capacity? With refineries now
running flat out, the balance might
seem to favor grass roots expansion,
but given the substantial cost
multiplier over revamps, this could
pcs nasty.indd 1
be questioned. Whichever the case,
however, an inescapable fact is
that the process design of the project
will prove crucial. Between the
charge pump, the desalter and the
units' distillation columns there are
many places where miscalcula-
tions in the process design could
wreck the entire project.
Can you really be sure of attaining
desired crude rates? Desalting
viscous crude is extremely difficult.
Minimizing coking or asphaltene
precipitation in the heaters demands
extreme care. Can you reasonably
expect high diesel and HVGO
recoveries, acceptable levels of
nickel, vanadium, and microcarbon
3400 Bissonnet Ph: [1] (713) 665-7046
Suite 130 Fx: [1] (713) 665-7246
Houston, Texas 77005 info@revamps.com
USA www.revamps.com
residue (MCR)? Refiners who cut
deep should not be surprised when
the HVGO product MCR is over 2
wt % and the vanadium content is
in excess of 10 ppmw. Any one of
such difficulties can result in lower
revenue, unstable operation or
even unit shutdown. It is critical to
understand that the inherent
properties of these low API gravity
crudes dictate that exact process
design is of paramount importance.
The point of this litany of possible
problems is to remind you not to
skimp in the early phases of
engineering. From the start of the
LP work through the completion of
front-end process engineering,
actual product yield and qualities
depend on the process design.
The message is clear. Nasty crudes
will continue to make up an
increasing proportion of refineries'
crude slates. But time is precious.
The sooner we face this fact,
unwelcome as it may be, the more
expeditiously we can adapt.
For a more in depth review of
heavy crude challenges, ask us for
Technical Papers 173, 185 and
197.
1/6/12 11:58:35
 present within each feedstock.
Those refiners experiencing 900
frequent feed slate variation will
800
generally have difficulty using the

SOx emissions, ppm

feed sulphur correlation. 700
A better correlation developed by
the engineers of Gulf Oil correlates 600
coke sulphur to slurry sulphur
500
within a power function, as shown
below: 400

Coke S = UF * (slurry S) 1.265 (6) 300

200
The unit factor (UF) and the 0.0 0.5 1.0 1.5 2.0 2.5
exponential term are typically Feed sulphur, wt%
modified to match the operating
data. The Gulf correlation is often
the most accurate tool for predict- Figure 1 SOx vs feed sulphur
ing coke sulphur. Unfortunately,
though, the Gulf correlation does
not fit the data from every unit. In 40
A
these instances, the process engi-
SOx emissions, ppm

B
neer is required to investigate other 30
correlations (multivariable linear
regressions, and so on) for more 20
accurate matching of the baseline
data.
Figure 2 demonstrates graphically 10
how two separate units were able
to correlate flue gas SOx emissions 0
extremely well using the Gulf 0.05 0.15 0.25 0.35
correlation. In Figure 1, the feed Slurry sulphur, wt%
sulphur correlation has a variation
of up to 200 ppm, while the Gulf Figure 2 Gulf correlation
correlation in Figure 2 has a varia-
tion of approximately 10 ppm. removed per mass additive.) Minor the greatest return on investment in
reductions may be effectively terms of cost per kilogram of
Common operating modes for SOx achieved via “cerium-free” additive sulphur removal.
reduction technologies. Typical additive effi-
Refiners typically operate in one of ciencies for these technologies are Deep reductions
three general modes of operation, approximately 5 kg/kg. The latest Deep SOx reductions are typically
including mild, deep or ultra-deep high-activity additives will also be in the range of 60-90%. PUFs are
SOx reductions. Guidelines for effective in this service, with the generally in the range of 20-40 kg/
additive choice are provided below PUFs averaging 40-50 kg/kg. kg. The observed PUF is the func-
for each of these modes of SO2 Refiners selecting additives for their tion of several factors, including
control. first application are advised to initial and final SOx levels
select the technology that provides plus regenerator hydrothermal
Mild reductions
Minor reductions are typical in the Minor SOx reductions
initial stages of SO2 emissions
standards. These standards typi-
Additive SG SG SG SG SG
cally require reductions of 50% or
Charge rate, tpd 2750 2590 10 170 9480 2790
less. Table 1 provides examples of Sulphur, wt% 0.62 0.62 0.36 0.31 0.78
refiners who were required to meet Slurry sulphur, wt% 1.5 1.44 0.86 0.79 2.2
the early EPA standards in North Flue gas O2 1.4 1.6 1.0 1.0 0.8
SO2 uncontrolled, ppm 780 800 386 331 559
America. Additive efficiencies were
SO2 controlled, ppm 398 336 158 126 235
in the 15-18 range while utilising SO2 reduction, % 51 42 41 38 0.42
earlier generation technology. Additive addition, kg/day 125 117 153 115 168
(Additive efficiency is referred to as Additive efficiency, kg/kg 17 15 15 15 15
the pick-up factor (PUF) and is
defined as the mass sulphur Table 1

www.eptq.com Catalysis 2013 31

intercat.indd 2 27/02/2013 12:42


Oil Sands Crude
– Profits and
Problems?
Canadian bitumen production
currently runs about 1 MMbpd,
with some being sold as Synbit
and Dilbit. Over the next 10-12
years output is expected to
increase to 3.5 MMbpd and more
refiners will begin investing to
process it and come to depend
on the Synbit and Dilbit for a
significant part of their supply.
Few today, however, have ever
processed these feeds at high
blend ratios, and are unaware
that conventional process and
equipment designs are not up
to the job. Canadian oil sands
PROCESS
CONSULTING
SERVICES,INC.
pcs 2.indd 1
feedstocks are extremely hard
to desalt, difficult to vaporize,
thermally unstable, corrosive, and
produce high di-olefin product
from the coker. If you intend to
lock into a long-term supply,
therefore, it is imperative that you
consider reliability and run length
from a particular design.
Too low tube velocity in the
vacuum heater tubes will lead to
precipitation of asphaltenes. Too
fast a flow rate will erode the
tube bends. If coil layout, burner
configuration and steam rate are
not correct, run length will be
measured in months, not years.
Diluent recovery unit designs
must take into account possible
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on today’s experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
with know-how who have real
experience wearing Nomex® suits
and measuring true unit per-
formance in Northern Alberta.
Shouldn’t this be kept in mind
by those considering long term
supply agreements?
For a discussion of factors
involved in designing refinery units
to process difficult oil sands feed-
stocks, ask for Technical Papers
#234 and 238.
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
info@revamps.com
www.revamps.com
1/6/12 21:05:28
 conditions. High-activity additives Deep SOx reductions
are recommended to avoid dilution
effects. Table 2 provides examples
Additive SSG SSG SSG SSG SSG
of refiners currently achieving Charge rate, tpd 2319 15 194 2210 2120 5114
moderate reduction levels. Sulphur, wt% 0.8 1.08 0.75 0.8 0.72
Slurry sulphur, wt% 2 1.99 2.1 1.89 1.6
Ultra-deep reductions Flue gas O2 1.9 1.4 2.1 2.6 2.5
SO2 uncontrolled, ppm 1189 689 1255 1061 744
California currently has one of the SO2 controlled, ppm 489 241 137 238 288
most stringent SO2 emissions SO2 reduction, % 58 65 89 78 59
standards in effect today. Refiners Additive addition, kg/day 92 276 170 147 125
in the Los Angeles basin are Additive efficiency, kg/kg 36 33 29 28 35
required to meet a 0-5 ppm SO2
emissions standard. High-activity Table 2
SOx-reducing additives are
required to meet these standards. negatively impacted. Intercat has operations, unlike full-combustion
The additive addition rate is a developed a proprietary set of base operations, there is a practical upper
strong function of the efficiency of loading guidelines for partial-burn limit to additive injection rates. It is
combustion air and spent catalyst operations to eliminate the negative recommended that the process engi-
mixing. Several refiners have impact on coke burning. neer monitors the concentration of
successfully achieved these oxidised sulphur being emitted from
ultra-low emission standards. Guidelines for establishing daily the regenerator. Increases in the
Optimisation of regenerator injection rates additive injection rate should be
performance is highly recom- Additive injection rates are typi- curtailed once the oxidised sulphur
mended for the lowest possible cally increased to meet flue gas has been fully eliminated from the
additive addition rates. targets as the uncontrolled SO2 regenerator off-gas.
Computational particle fluid levels increase. There is no theoreti- Two-stage regenerators present a
dynamics (CPFD) is an invaluable cal limitation to SO2 removal by special case for SO2 removal. The
tool to assist refiners in establish- SOx additives in full-combustion first stage typically operates in
ing the best available mixing operations. Commercial experience partial combustion, while the second
performance within the combus- sets a practical upper limit for SOx stage operates in full combustion.
tion zone of the regenerator. additive additions of approximately The resulting configuration operates
Multiple refiners have proven that, 20% of fresh catalyst, although as a hybrid operation having neither
even at ultra-low emission levels, fresh catalyst additions may have complete full nor partial combustion
SOx-reducing additives are more to be increased slightly to counter characteristics. Industry experience
cost effective than installing and any dilution effects at concentra- indicates that SOx additives opti-
operating flue gas scrubbers. tions over approximately 10%. This mised for partial burn operations
implies that units with higher cata- tend to perform better in such units.
Guidelines for base loading lyst injection rates will be able to
SOx-reducing additives do not achieve lower emission standards Maximising SOx additive efficiency
affect delta coke in full-combustion via the use of additives (see The following process variables
operations. This enables base load- Table 3). have a positive effect on SOx addi-
ing of the additive for the swiftest As stated previously, the limiting tive efficiency. Manipulation of
possible control. Intercat first reagent in partial-burn operations is these variables, when possible, will
recommends the determination of oxygen. In partial-combustion result in increased additive effi-
the equilibrium additive injection mode, a portion of the sulphur is ciency and reduced operating costs:
rate followed by injections at three oxidised to COS. The higher the • Increase flue gas oxygen concen-
times the daily equilibrium level CO-to-CO2 ratio, the higher the tration An increase in oxygen
for a period of seven days. This concentration of these reduced concentration within the regenera-
base loading period will result in species will be. In partial-burn tor will tend to shift the SO2 ↔ SO3
the swiftest possible compliance to
SO2 emissions.
Base loading in partial-combus- Example additive injection rates
tion operations is more complex.
Oxygen is the limiting reagent for Case 1 Case 2
these operations. Therefore, the 2 TPD catalyst additions 5 TPD catalyst additions
most efficient effective SOx addi- Additive SOx emissions, Additive SOx emissions, Additive
usage, kg/day ppm concentration, % ppm concentration, %
tives for partial-burn operations 0 1519 1519
include an enhanced oxidation 500 425 20 425 9.1
package. Care must be exercised 1000 53 >20 53 16.6
during base loading to ensure that
the CO-to-CO2 ratio is not Table 3

www.eptq.com Catalysis 2013 33

intercat.indd 3 27/02/2013 12:42


70
60
SOx emissions, ppm
50
40
30
20
10
0.8
Figure 3 SOx vs excess oxygen
equilibrium in the direction of SO3.
Additive efficiency has been
observed to increase in most units
up to approximately 2% excess
oxygen in the flue gas
• Increase catalyst circulation rate
An increase in catalyst circulation
will directionally result in a more
rapid regeneration of the SOx addi-
tive. The concentration of
regenerated additive will be higher,
resulting in increased SOx
adsorption
• Increased regenerator pressure
The SO2 ↔ SO3 equilibrium favours
SO3 at higher pressures. Operating
at higher pressure will shift the
equilibrium towards SO3, thereby
improving additive efficiency
• Use of CO promoters CO promot-
ers may assist the shift of SO2 ↔
SO3 equilibrium in favour of SO3.
Use of CO promoters will enhance
additive performance
• Lower regenerator temperature
The SO2 ↔ SO3 equilibrium favours
SO3 at lower temperatures. Where
possible, operating at a lower regen-
erator temperature will shift this
equilibrium towards SO3, thereby
improving additive efficiency.
Low conversion operations
SOx-reducing additives are tri-
functional catalysts possessing an
oxidation reaction, an adsorption
reaction and a release mechanism.
The release of sulphur as H2S occurs
in the reducing atmosphere of the
riser and the reactor stripper. A
reduction in the riser outlet temper-
ature, implemented to achieve
maximum LCO yield, will reduce
34 Catalysis 2013
intercat.indd 4
1.2 1.6 2.0 2.4 2.8
Excess oxygen, %
overall reactor temperatures. This
lower temperature can negatively
impact H2S release. This effect has
been observed at approximately
510°C (950°F) in some operating
units. Intercat has developed a
SOx-reducing additive, Super
SOxGetter-DM, with enhanced
release functionality for those refin-
ers desiring to operate with lower
riser outlet temperatures.
Low cerium SOx-reducing additives
Recent substantial price escalations
in the cerium market have had a
significant impact on SOx additive
price. As a result, Intercat devel-
oped a low cerium additive
possessing approximately 50% less
cerium. This additive, Super
SOxGetter-II, is now being injected
into over 40 operating units, with
efficiencies equal to or greater than
the original Super SOxGetter.
Troubleshooting SOx performance
SOx emissions reduction achieved
in full-combustion regenerators is
directly related to the amount of
additive injected into the unit. The
higher the rate of additive injection,
the greater the SOx reduction will
be. The only practical limitation to
the additive addition rate is the
possibility of base catalyst dilution.
It is helpful to consider the varia-
bles that impact the SOx-
reducing additive’s efficiency.
Understanding the impact of these
variables will enable the process
engineer to effectively troubleshoot
periods in which the additive
response does not meet expecta-
tions. The first four factors being
observed are most frequently
followed by six factors that are
occasionally observed. The last two
factors refer to specific regenerator
designs that may impact additive
efficiencies.
Flue gas analyser reliability
One of the most common reasons
for an apparent loss in additive effi-
ciency is the accuracy of the flue
gas stack analyser. These analysers
are operating in challenging envi-
ronments containing both moisture
and particulate matter. It is strongly
recommended that the instrumenta-
tion groups within the refinery
place a high priority on routine
maintenance of the flue gas
analyser. In particular, extra care is
required to ensure that the flue gas
conditioning system is properly
removing water and catalyst fines.
The process engineer is recom-
mended to first verify flue gas
analyser accuracy when confronted
with an unexplained increase in
SOx emissions.
Flue gas composition
Oxygen concentration in the
combustion zone plays a significant
role in determining additive effi-
ciency (see Equations 1 and 2). It
has been observed in full-
combustion regenerators that the
concentration of excess oxygen has
a measurable impact on additive
efficiency up to approximately 2%.
Those units operating lower than
2% excess oxygen will typically
observe an improvement in addi-
tive efficiency by increasing the
excess oxygen concentration in the
flue gas (see Figure 3). Operating at
oxygen levels greater than 2% will
likely have little impact on additive
efficiency.
SOx additive efficiency is
strongly impacted by CO concen-
tration in units operating in partial
combustion. There is an inverse
response between additive effi-
ciency and CO concentration. As
CO concentration increases, the
additive efficiency decreases. This
is directly related to the concentra-
tion of oxidised sulphur exiting
the regenerator. A useful rule of
thumb relating additive efficiency
www.eptq.com
27/02/2013 12:42
 to CO concentration is that addi-
tive efficiency drops by 300 1.30
approximately 10% for every 1%
1.25
increase in flue gas CO 250

SOx emissions, ppm

concentration. 1.20

Ecat Fe, wt%

200 1.15
Step changes in equilibrium iron
Organic iron entering the unit with 1.10
the feedstock is a catalyst that 150 1.05
oxidises sulphur to SO2. Several
units operating stably with 1.00
100
SOx-reducing additives have Sox 0.95
observed “unexplained” step change Ecat Fe
increases in SOx emissions immedi- 50 0.90
0 20 40 60 80 100
ately following a spike in
Days
equilibrium catalyst iron levels (see
Figure 4). Fortunately, the half-life
of this organic iron is very short at Figure 4 SOx and equilibrium iron
approximately two to three days.
SOx emissions will rapidly return to
baseline levels after the organic iron 1000 1005
has been removed from the feed SOx

Riser outlet temperature, ºF

900 1000
slate. The extra SO2 responds well to Riser
800 995
SOx emissions, ppm

increased additive injections.

Catalyst losses
Catalyst losses within the reactor/
regenerator system will result in a
perceived reduction in additive effi-
ciency. The additive efficiency
actually remains constant. However,
the amount of additive necessary to
achieve targeted emissions levels
will need to be increased, as a
portion of the additive is lost
together with the base catalyst.
Refiners increasing the fresh catalyst
injection rate to compensate for
losses must also increase the addi-
tive injection rate proportionally.
Regenerator mechanical damage
Mechanical damage to the distribu-
tors or cyclones within the
regenerator will result in maldistri-
bution and increased catalyst and
additive losses. Both effects will
reduce the apparent efficiency of the
SOx additive. Increased additive
additions will likely be required
until the damage has been repaired.
CO promoter
CO promoters are extremely effi-
cient at oxidising CO to CO2. Such
materials are also very efficient at
oxidising SO2 to SO3. The use of a
CO combustion promoter will
result in enhanced SOx additive
efficiency in some units. Units
utilising CO combustion promoters
700
600
500
400
300
200
100
0 955
29/9/2008
Figure 5 SOx and riser outlet temperature
while injecting SOx additives may
observe an increase in SOx emis-
sions if the CO promoter use is
stopped. The SOx additive effi-
ciency has not changed. However,
the oxidation impact of the CO
promoter has been eliminated,
thereby reducing apparent effi-
ciency. This incremental increase in
SOx emissions will be recovered by
an additional additive injection.
Maximum LCO operations
SOx-reducing additives are highly
advanced tri-functional catalysts.
One of these functionalities is the
release of sulphur as H2S in the
reducing atmosphere of the reactor
vessel. This release function is
temperature sensitive. The reduc-
tion in riser outlet temperatures is a
standard operating response to
maximise LCO. This lower operat-
ing temperature may negatively
990
985
980
975
970
965
960
28/11/2008 27/1/2009 28/3/2009
affect the H2S release mechanism in
some units (see Figure 5). Intercat
has developed a SOx-reducing
technology, Super SOxGetter-DM,
for use in low-temperature maxi-
mum LCO operations. This
technology enables low-tempera-
ture operations to control SOx
emissions, with efficiencies equiva-
lent to standard operations.
Poor stripper efficiency
FCC operations with poor stripper
efficiencies tend to see higher hydro-
gen on coke levels. The low stripper
efficiency often results in heavy oil
carry-under into the regenerator
vessel. Sulphur concentrates in the
heavier oil fractions. Therefore, low
stripper efficiencies tend to lead to
higher sulphur loadings into the
regenerator. Additional additive
injections will likely be required in
these operations.

www.eptq.com Catalysis 2013 35

intercat.indd 5 27/02/2013 12:42

dupont.indd 1 23/2/12 15:04:26
 Catalyst-to-oil effects
SO3 absorption occurs within the
combustion zone of the regenerator
as long as active magnesium sites
are available for reaction. H2S
release occurs within the reducing
atmosphere of the reactor vessel.
An increased catalyst-to-oil ratio
has the effect of increasing the
additive regeneration rate. Additive
efficiency is therefore enhanced at
higher catalyst-to-oil ratios (see
Figure 6). Alternatively, processing
a higher concarbon-containing
feedstock may result in an incre-
mental loss in additive efficiency
due to a reduction in the catalyst-
to-oil ratio. This incremental loss in
SOx reduction will be recovered by
additional additive injection.
Additive loader failure
In order to ensure compliance at
the lowest possible operating cost,
refiners have almost universally
chosen to employ additive loading
systems rather than pre-blending
into the host catalyst system. The
precision and reliability of this
loader therefore has a direct impact
on environmental compliance. It is
strongly recommended that the
refiner selects the loader technology
exhibiting the highest precision and
best reliability possible. Non-
compliance of SOx emission
standards should never be the
result of poor loader reliability.
Large regenerator inventories
Large FCC regenerators tend to
experience lower spent catalyst
and combustion air distribution
efficiencies than do smaller regen-
erators. Poor catalyst distribution
will result in regions of the regener-
ator cross-sectional area not
receiving equivalent SOx additive
concentration. This may result in
reduced additive efficiency.
Regenerator maldistribution
FCC regenerator maldistribution
may limit the depth of SOx reduc-
tion. One particular refiner was
required to drop its SOx emissions
from >100 ppm to 25 ppm. This
operator found that reductions of
less than 60 ppm were not possible.
The root cause of this inability to
reach targeted levels was found to
www.eptq.com
intercat.indd 6
370
320
SOx emissions, ppm
270
220
170
120
70
6.2
Figure 6 SOx vs cat-to-oil ratio
be maldistribution within the
regenerator. The new 25 ppm target
was easily met at a lower addition
rate after the unit was shut down
for distributor modification. Data
analysis after startup confirmed
that the maldistribution had been
eliminated.
Maldistribution may be identified
via multiple methodologies. The
most common method is to review
radial and vertical temperature
profiles within the regenerator.
Large radial variations present at
similar elevations are indicative of
maldistribution. A second indica-
tion of maldistribution is often
observed via afterburn profiles.
Maldistribution is present when
afterburning occurs primarily in
one quadrant or hemisphere of the
regenerator. Severe maldistribution
is indicated by localised afterburn-
ing, which is unstable and shifting
from quadrant to quadrant.
An additional method to verify
maldistribution is to use a reaction
mix sampling device in conjunction
with a portable gas analyser. This
method involves identifying fittings
on the regenerator at similar levels,
which permit the insertion of the
RMS device through a packing
gland. The end of the probe inserted
into the regenerator vessel is fitted
with a Mott filter to prevent fines
entering the gas analyser. The porta-
ble gas analyser is then connected to
the RMS device outlet and used to
measure gas concentrations. Gas
measurements are taken at multiple
points at a constant elevation along
the circumference of the regenerator.
6.4 6.6 6.8 7.0 7.2 7.4
Cat-to-oil, wt/wt
Comparison of the oxygen, carbon
monoxide, carbon dioxide and nitro-
gen oxide will provide a direct
indication of maldistribution within
the regenerator.
An example of this technique is
provided in Figure 7 and Table 4.
The spent catalyst distributor in the
regenerator of this particular refiner
was located on the north side of the
regenerator. The regenerated cata-
lyst standpipe is located on the
south side of the regenerator. The
combustion gas analysis within the
vessel clearly confirmed severe
maldistribution within the regener-
ator. It is interesting to note that
while this regenerator operates in
full combustion, the northern hemi-
sphere of the vessel was operating
in partial combustion.
Maldistribution within the regen-
erator vessel may result in less than
optimal distribution of SOx addi-
tive over the cross-sectional area of
the regenerator vessel. As Table 4
shows, the combustion gases after
mixing in the plenum averaged 250
ppm SOx even though the SOx
level in the southwest quadrant
was 85 ppm. SOx additive will
readily reduce the SOx in the
southern hemisphere to near zero
values, while the northern hemi-
sphere will remain at 200 ppm or
greater. The flue gas concentration
would then average 100 ppm. This
refiner would be forced to over-
inject to achieve SOx emissions of
less than 100 ppm. The refiner was
an excellent candidate for a spent
catalyst distributor modification.
This modification was made with a
Catalysis 2013 37
27/02/2013 12:42
 North Regenerator
C/L

CM II
CM I

CB 0º CP I
No. 1 5º CD
352º 20º
CL 22º
330º

9 1 /8 ”
322º

62º
CR

5ft 51/16”

Modified dipleg
Modified dipleg with offset
with offset Detail A1
Detail A1

90º

CO II CF
4ft 117/16”

CE
CC

Hopper
125º
CP II
87/8”

135º
222º
CO
CN 140º
CO I
150º Catalyst
P1 withdrawal
180º 172º No. 2
180º
CJI CA
No. 3
Plan view

Figure 7 Regenerator configuration

measurable improvement in mixing
efficiency, resulting in lower SOx
emissions at constant conditions.
Computational particle fluid
dynamics (CPFD) is a technique
enabling refiners to determine the
root cause and the degree of mald- The net result is generally the abil-
istribution present within the ity to easily achieve emission
regenerators. Modifications to the targets at reduced additive
spent catalyst and/or combustion consumption. Intercat offers CPFD
air distributors can then be imple- analysis as a service to analyse
mented to achieve optimal mixing. distribution efficiency.

Regenerator maldistribution Additive loader guidelines

There are many fresh catalyst load-
ers being utilised in the industry,
O2 vol% CO, ppm SO2, ppm NOx, ppm
which have poor precision and reli-
Position 1 0.1 2828 440 152
Position 2 2.6 1429 191 133 ability. Refiners using these systems
Position 3 4.3 1068 83 218 are typically required to gauge
Flue gas 2.6 83 248 109 their fresh hoppers multiple times
per week to estimate fresh catalyst
Table 4 injections. Fresh catalyst injection

38 Catalysis 2013 www.eptq.com

intercat.indd 7 27/02/2013 12:43

 rate precision is typically +/-0.5 Intercat loader precision
t/d at best. This same technology
cannot be economically used for
adding SOx additives. Product Target, kg/day Actual, kg/day Delta, kg/day Precision, %
Example 1 Catalyst 10 323 10 302 -21 99.8
Intercat loaders are now present Example 2 Catalyst 3025 3002 -23 99.2
in nearly 300 refiners worldwide. Example 3 Catalyst 2557 2525 -32 98.7
These systems are being used for Example 4 Catalyst 1622 1616 -6 99.6
both fresh catalyst and additive Example 5 Catalyst 1447 1441 -6 99.6
Example 6 Catalyst 1400 1401 1 100.1
injection. As Table 5 shows, preci- Example 7 Additive 427 429 2 100.5
sion levels greater than 99% are Example 8 Additive 418 415 -3 99.3
common with Intercat loading Example 9 Additive 230 229 -1 99.6
systems. Additionally, the loaders Example 10 Additive 191 191 0 100.0
Example 11 Additive 85 85 0 100.0
typically operate for over 15 years, Example 12 Additive 81 81 0 100.0
requiring nothing more than occa- Example 13 Additive 42 42 0 100.0
sional maintenance checks. Example 14 Additive 16 16 0 100.0

Conclusion
The refining industry has accumu-
lated substantial experience in a
wide range of operations since SOx
additives were first used in the
1980s. This experience has been
crystallised into a set of guidelines
that are applicable to most FCC
operations. SOx-reducing additives
regularly achieve reductions of over
95% in full-combustion operations
and up to 70% reductions in partial-
combustion operations. Finally, the
importance of using high-precision,
Table 5
high-reliability loaders for the
economic use of such additives
cannot be over-emphasised.
Further reading
1 Huling, McKinney, Readal, Sulphur
distribution in high conversion riser catalyst
cracking, Gulf Oil Company, Pittsburgh PA.
2 Fletcher R P, Evans M E, Optimizing &
troubleshooting the FCC regenerator for
reduced emissions, 2010 AFPM Annual
Meeting, AM-10-173.
3 Fletcher R P, Evans M E, Preventing the most
common environmental excursions on the
FCC, 2011 AFPM Annual Meeting, AM-11-38.
Ray Fletcher is a Senior Technologist with
Intercat Inc, Sea Girt, New Jersey. He has worked
as a process engineer on FCC, hydrotreating,
catalytic reforming, alkylation and catalytic
polymersation and has a chemical engineering
degree from the University of Washington.
Email: RFletcher@intercatinc.com

◗ www.digitalrefining.com is an
easy-to-use website for the
refining, gas and petrochemical
processing industries.

◗ A simple search facility enables

you to find and display relevant
information across the whole
spectrum of articles, literature,
news, events and companies.

◗ Readers can download technical

articles and other information
from over 40 categories.

◗ Find relevant industry events

worldwide.

◗ Read news items focusing on

contracts, company news and new
products.

www.eptq.com Catalysis 2013 39

intercat.indd 8 28/02/2013 11:41

sabin.indd 1 27/02/2013 15:01
 Catalysts for hydrogen management

Use and optimisation of high-performance catalysts are an important tool to

increase hydrogen supply in a refinery

ROSS BRUNSON, UWE FLESSNER and PAIGE MORSE

Clariant

H
ydrogen management is a
critical requirement for refin- Steam
eries these days. This simple
molecule provides the means to
HC feed HTS
meet environmental regulations
and process more challenging feed-
stocks, both of which are keys to
sustainable and profitable opera-
tions. The Catalysts business unit of
Clariant (formerly the Catalyst
Division of Süd-Chemie) is a lead-
ing supplier of catalysts and
technical service to the refining
industry, and a specialist in hydro- Purification Pre-reformer Primary
gen operations. Our high- reformer
performance catalysts and technical Reforming
service experts enable optimal
performance for operations PSA purge gas
to reformer
throughout the hydrogen plant.
The demand for hydrogen at
modern refineries is an increasingly
Hydrogen
challenging topic for operators.
Available crudes are often lower in
quality – heavier and more sour –
than in recent years, thus requiring
more hydrogen to process. HTS CO shift CO2 removal
Additionally, sulphur and aromat-
ics specifications for transportation Figure 1 Simplified diagram of hydrogen plant operations
fuels continue to be lowered world-
wide, which again demands more
hydrogen to reach these new Catalysts and adsorbents often used in hydrogen plants
targets. For refiners, these demands
often require an increase in hydro- Application Catalyst type Clariant catalyst
treating capacity and a boost to Hydrodesulphurisation CoMo/NiMo HDMax 200/300 series
hydrogen purity levels in Sulphur removal ZnO ActiSorb S2
operations. Deep desulphurisation CuZn ActiSorb S6
Chloride guard Activated Al2O3 ActiSorb Cl2
There are four basic operations Pre-reforming Ni ReforMax 100
for hydrogen plants: feedstock Steam reforming Ni
treatment; steam reforming; water Naphtha ReforMax 250
gas shift; and raw hydrogen purifi- LPG, butane ReforMax 210 LDP
Methane ReforMax 330 LDP
cation, typically with the use of a High-temp. shift FeCr ShiftMax 120
pressure swing adsorption (PSA) Medium-temp. shift CuZn ShiftMax 300/500
unit. This article discusses the Low-temp. shift CuZn ShiftMax 200 series
high-performance catalysts for each Methanation Ni Meth 134
of these operations that enable the
best overall performance, and can Table 1

www.eptq.com Catalysis 2013 41

clariant.indd 1 27/02/2013 13:47

 action loves reaction
Chemical reactions require chemical catalysts. As the
global leader in chemical catalysts, BASF acts through
continuous product and process innovations in collaborative
partnerships with our customers. The result is a broad
chemical catalyst portfolio backed by dedicated customer
and technical service and enabled through the strength of
BASF - The Chemical Company.
At BASF, we create chemistry for a sustainable future.
www.catalysts.basf.com/process

n Adsorbents
n Fine Chemical Catalysts
n Environmental Catalysts

n Catalysts for Fuel Cells

n Catalysts for Oleochemicals & Other Biorenewables

n Oxidation & Dehydrogenation Catalysts

n Petrochemical Catalysts

n Polyolefin Catalysts

n Refining Catalysts

n Syngas Catalysts

n Custom Catalysts

basf.indd 1 26/02/2013 16:12

 boost production levels and purity
of existing units. Optimal operation
of hydrogen plants is best achieved
by a thorough understanding of
catalyst-related topics, including
reaction chemistry, design informa-
tion, operations optimisation,
equilibrium considerations,
startup/shutdown procedures and
troubleshooting.
A simplified schematic of hydro-
gen operations is shown in Figure 1.
Catalysts commonly used in these
processes are shown in Table 1.
Feedstock treatment
Feedstock purification is a funda-
mental first step in hydrogen
operations. It removes sulphur,
chlorides, olefins and other impuri-
ties that can poison downstream
catalyst systems and foul or
corrode equipment. Hydrogenation
is the first step, with three key
processes to consider: saturation of
olefins to paraffins, hydrodesul-
phurisation of sulphur-containing
materials to hydrogen sulphide,
and hydrodechlorination of
alkylchlorides to hydrogen chloride.
Products used in these applica-
tions include HDMax 200 and 300
series for hydrogenation, ActiSorb
LDP shape increases crush strength and surface area, and shows low pressure drop
compared to standard rings and enhanced wheel (EW) shape
Relative Avg. radial
Relative geometric crush, lb
Catalyst: ∆P surface area DWL
16 x 16 x 6 mm Raschig ring 1.00 1.00 117
16 x 6 mm EW spoked wheel 1.09 1.53 131
19 x 19 x 7 mm Raschig ring 0.70 0.84 220
19 x 16 mm x 10-hole LDP 0.66 1.48 190
19 x 12 mm x 10-hole LDP 0.68 1.55 170
Table 2
species; that is, greater than 32 steam. The simplified reaction
wt% pick-up. For deep desulphuri- scheme is as follows:
sation, ActiSorb S6 is a
copper-zinc-based product that is CxHy + H2O → x CO + (x + ½ y) H2
typically applied to protect a
pre-reforming catalyst from The preferred configuration for
premature poisoning by sulphur. reforming depends on the quality of
ActiSorb Cl2 is used to remove the feedstock available and the
hydrogen chloride. amount of heavy hydrocarbons that
a plant will process into hydrogen.
Pre-reforming and reforming The most common process uses
Steam reforming is the conversion methane and is referred to as steam
of hydrocarbon feeds to synthesis methane reforming (SMR).
gas (a mixture of CO and H2) using Hydrogen production utilising SMR
1.00
Relative activity, %

0.75
Cl2 for chloride removal, ActiSorb
S2 for desulphurisation, and
ActiSorb S6 for deep desulphurisa- 0.50
tion. The HDMax series will
hydrogenate olefins and alkylchlo- Benchmark A
rides, and will convert most 0.25 Benchmark B
Benchmark C
sulphur-containing species. HDMax
ReforMax 100
catalysts are typically used with a
0
downstream zinc oxide-based 0 5 10 15 20 25
sulphur trap and are resistant to Time on-stream, hr
heavy hydrocarbons. The HDMax Test conditions: DGSV = 20.000 1/h; S/C = 2.5; T = 480ºC; P = 30 bar
200 series are cobalt-molybdenum 1.00
catalysts, and the HDMax 300 Benchmark A
series are nickel-molybdenum cata- Benchmark B
lysts with the advantage of Benchmark C
Relative activity, %

0.75
remaining in the sulphided state ReforMax 100
more easily than the CoMo option.
The ActiSorb series products are 0.50
absorbents used to purify the
hydrogenated feedstocks. ActiSorb
S2 and S6 are particularly effective 0.25
for sulphur removal in hydrogen
operations, and are typically
0
installed in beds following HDMax 0 5 10 15 20 25
series catalysts. The ActiSorb S2 is Time on-stream, hr
a zinc oxide material with a very Test conditions: DGSV = 20.000 1/h; S/C = 2.5; T = 480ºC; P = 30 bar; S = 25 ppmv S
high surface area that enables high
pick-up of sulphur-containing Figure 2 ReforMax 100 activity and poison resistance compared to benchmark

www.eptq.com Catalysis 2013 43

clariant.indd 2 27/02/2013 13:47


140
Crush, lb DWL (5/8" × 1/4" EW)
120
100
80
60
40
20
0 enhanced by the use of hibonite
0.10
Figure 3 Advantages of calcium aluminate carrier vs alpha alumina
is increasingly being considered a
utility gas within the refining and
petrochemical industry.
For units with heavier feeds,
including naphtha, a pre-reforming
unit can be installed upstream of
the SMR and offers several advan-
tages. A pre-reformer will allow the
processing of heavy feed including
naphtha at low steam-to-carbon
ratios (S/C) without issues from
coking of the catalysts used in the
production of hydrogen. The
pre-reformer also allows the SMR
to operate at 8-10% higher rates (at
the same heat load) by reducing the
required reforming duty. It can
contribute to a longer operating
lifetime for the SMR equipment at
increased hydrogen production
capacity by reducing the heat loads
and avoiding problems due to
carbon formation and the associ-
ated pressure drop increase. The
overall S/C can be reduced by utili-
sation of a pre-reformer, and it will
lower energy consumption.
ReforMax 100 is a catalyst for
pre-reforming, with higher activity
and better poison resistance when
compared to benchmark catalysts
(see Figure 2).
The reforming reaction is endo-
thermic and the equilibrium is
favoured by a high exit tempera-
ture, high steam-to-gas ratio and
low exit pressure. Catalysts used
for SMR need to combine the high-
est performance under extreme
operating conditions with high
structural integrity and minimum
pressure drop.
Nickel-based reforming catalysts
44 Catalysis 2013
clariant.indd 3
Calcium aluminate
Alpha alumina
0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
P.V., cc/gm
have been produced by Clariant
(and predecessor company
Süd-Chemie) for more than 50
years. The ReforMax series are the
preferred choices for this reaction.
Each of these catalysts has several
decades of commercial application
and more than 100 users. ReforMax
330 is preferably used in meth-
ane-rich feeds, while ReforMax 210
is potassium promoted for use with
heavier feeds such as heavy natural
Refinery operators
have several options
to increase hydrogen
supply, and the use
and optimisation of
high-performance
catalysts are an
important tool
gas or LPG, and ReforMax 250 is
the best choice for naphtha feeds.
These catalysts are often used in
layers in a reformer tube, geared to
the quality of the feedstock.
The low differential pressure
(LDP) shape of these catalysts
combines high activity, high
geometric surface area, increased
side crush strength and decreased
pressure drop, which is critical to
performance in this application (see
Figure 3). The high surface area
compared with a standard Raschig
ring means ReforMax 330 LDP
achieves 50% higher activity and
more than 35% lower pressure
drop. The LDP shape provides the
highest crush strength, which is
needed to withstand the extreme
physical stress due to the expansion
and compression of the reformer
tubes during startup, shutdown
and upset conditions (see Table 2).
The performance of ReforMax
210 and ReforMax 330 is further
(calcium aluminate) carrier to
inhibit coke formation. In addition,
ReforMax 210 has the optimal
balance of potassium promotion to
tailor its acidity to avoid coking of
heavier feedstocks. Figure 3 shows
the comparison of the higher crush
strength and high activity due to
greater pore volume versus an
alpha alumina carrier. This is all
accomplished without any concern
for the fouling of downstream
equipment or catalyst from the
presence of an alkaline promoter.
Catalyst loading is a particularly
important procedure for reformer
operations. Uniform loading across
and between each tube is critical to
ensure long-term stable operations.
Variation in the loaded density can
cause pressure drop variations
across the tubes and can lead to
uneven flow and localised hot spots
that may damage the tubes and
reduce tube life. Catalyst settling
within the tube can also cause hot
banding of the tubes and decreased
tube life. Employing one of the
currently available dense loading
methods will avoid these types of
catalyst loading problems.
Shift reaction
The shift reaction is the reaction of
carbon monoxide with steam to
produce hydrogen and carbon
dioxide:
CO + H2O ↔ H2 + CO2
This is an exothermic equilibrium
reaction, which means it is favoured
by a lower outlet temperature, as
well as a higher steam-to-gas ratio.
However, due to the exothermic
nature of this reaction and the
considerably high CO concentration
in this particular feed, significant
heat of reaction is produced.
www.eptq.com
27/02/2013 13:47
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Relative activity, %
Figure 4 ShiftMax 120 activity vs benchmarks
ShiftMax 120 is a copper-
promoted iron-chromium catalyst
that shows high performance for
such high-temperature shift (HTS)
reactions. The performance of
ShiftMax 120 is based on hundreds
of commercial charges (see Figure
4). Most users see a 20-30%
improvement in activity compared
to other available HTS catalysts,
and thus can operate at lower inlet
temperatures compared to other
HTS catalysts, reducing the exit CO
leakage, which then increases
hydrogen production and produces
more high-pressure steam in the
waste heat boiler. ShiftMax 120 also
delivers high mechanical strength
compared to other available HTS
catalysts, which enables it to
survive the high temperature
generated across the catalyst and
the common waste heat boiler leaks
that can cause catalyst breakage
1.3
1.2
Relative catalyst volume
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0 0.05
Figure 5 Volume of methanation catalyst required for CO and CO2 removal
46 Catalysis 2013
clariant.indd 4
ShiftMax 120
Benchmark A
Benchmark B
Months on-stream
and pressure drop increase without
replacement.
Some hydrogen units operate at
more moderate temperatures and
require catalysts optimised for these
conditions. Medium-temperature
shift typically operates between
204°C (400°F) and 316°C (600°F) and
with higher inlet CO concentrations
in the feed. The copper-zinc catalyst
ShiftMax 300 or 500 catalysts are
optimised for these conditions.
ShiftMax 200 series catalysts are
optimised for low-temperature shift
reactions, typically run between
204°C (400°F) and 260°C (500°F).
Low-temperature shifts are
installed downstream of a HTS
reactor and are used to reduce CO
concentration and increase H2
concentration further.
A methanation step may be
required in the older-designed,
non-PSA plants to remove residual
CO = 0.1
CO = 0.2
CO = 0.3
T = 600ºF (316ºC)
0.10 0.15 0.20 0.25 0.30
CO2, mol%
CO and CO2 to levels below
5 ppmv, if downstream operations
are sensitive to these contaminants.
Meth 134 is a spherical nickel cata-
lyst for this application, and is
available in a reduced and stabi-
lised version to enable faster
startup. The operation and sizing of
this unit are highly dependent on
the CO concentrations of the feed
(see Figure 5).
Conclusion
Refinery operators have several
options to increase hydrogen
supply, and the use and optimisa-
tion of high-performance catalysts
are an important tool. A pre-
reformer can be helpful for the
utilisation of heavy and/or other
refinery off-gasses as a replacement
for natural gas to produce
hydrogen.
Clariant’s catalyst technology
enables full plant capabilities and
maximises the energy efficiency of
hydrogen production. The high-
activity catalysts — such as
HDMax, ReforMax, ShiftMax and
Meth series — help operators main-
tain and optimise the designed
plant performance in energy effi-
ciency and hydrogen output,
keeping operating costs down.
Overall understanding of the basic
principles of catalytic reactor opera-
tions can help operators avoid
costly performance and operating
problems.
ActiSorb, HDMax, Meth, ReforMax and
ShiftMax are marks of Clariant.
Ross Brunson is Clariant’s Technical Sales
Manager for Western Canada and West
Coast of the US. He also serves as Clariant’s
Global Topic Expert for hydrogen production
catalysts and holds a BS degree in chemical
engineering from The University of California
at Berkeley.
Uwe Flessner is the Sales Director for
Methanol and Hydrogen Catalysts in
Clariant’s Business Sector Syngas. He has 20
years of experience in catalytic processing
techniques for the oil industry and holds a PhD
in chemistry from the Technical University of
Munich, Germany.
Paige Marie Morse is Global Marketing
Manager for the Catalysts Business of Clariant.
She is based in Munich, Germany, previously
worked at Dow and Shell in the US, and holds
a PhD in chemistry from the University of
Illinois.
www.eptq.com
27/02/2013 13:48
bete.indd 1 26/02/2013 11:17
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 Extending the lifecycle of hydroprocessing
catalyst
The economic downturn has put pressure on refiners to look for opportunities to
reduce expenses and maintain margins, particularly with their catalysts
ROLAND HOFFMAN and BOB LELIVELD
Albemarle Catalysts Company BV
O
ver the past few years,
many parts of the world
have been hit with a
mandated reduction in the sulphur
content of on-road diesel to a
maximum concentration of 10-15
ppm. Since then, refiners have
struggled to find low-cost strate-
gies to meet these stringent
specifications. In addition, most
refiners no longer have the excess
capacity to rerun or blend off-
specification products. Ultra-low-
sulphur diesel (ULSD) has to be
produced correctly the first time or
the refinery’s economics will
suffer. The performance delivered
by the ULSD catalyst is thus criti-
cal to the refinery’s profitability.
Re-usage of spent catalyst has
always been an economically attrac-
tive alternative to landfilling or
selling to metal reclaim companies.
In the current era of ULSD, such
reuse is only justified when the
performance of the recycled cata-
lyst is similar or equal to that of the
fresh catalyst.
React technology was introduced
in 2003 by Albemarle and Nippon-
Ketjen to restore the performance
of spent Stars catalysts close to its
original level. This proprietary
patented technology has become
strategically important for many
refiners worldwide. To date, more
than 150 customers are using it in
over 750 units. By the end of 2013,
it is expected to be used to reacti-
vate more than 50 000 tonnes of
Stars.
In this article, we describe how
this technology contributes to effec-
tively lowering catalyst costs for
ULSD operations without compro-
mising performance.
www.eptq.com
albemarle.indd 1
organic coating. The treatment
boosts performance, giving Stars
catalysts typically 95% of their
initial activity.
The improvements in dispersion
were studied with scanning trans-
mission electron microscopy.
These analyses revealed considera-
ble improvements in dispersion
after applying “Reactivation”.
Figure 1 shows that spent and
regenerated Ketjenfine KF 757 (a
Stars catalyst) contains agglomer-
ated metals and metals crystals,
Figure 1 Spent and regenerated KF 757 whereas the Reactivated catalyst
catalyst contains agglomerated metals has a dispersion similar to fresh
and metals crystals, whereas the catalyst.
Reactivated catalyst has a dispersion Figure 2 shows the distribution
similar to fresh catalyst
of cobalt and molybdenum over
the surface of a regenerated cata-
React technology lyst. It can be seen that a much
This technology restores the perfor- better dispersion is achieved on
mance of used Stars catalysts using the Reactivated catalyst. The
a proprietary regeneration process performance of the regenerated
followed by redispersion of the catalyst is thus restored close to
active metals. As with fresh Stars the activity level of fresh Stars
catalysts, the Type II active sites are catalyst. Besides KF 757, the React
recreated and protected by an technology can be used with the
complete Stars catalyst
portfolio.
Stars catalysts can
undergo multiple reacti-
vations with little to no
activity loss and no
appreciable yield losses
due to mechanical
handling. For example,
Albemarle partner
Eurecat has demon-
strated that KF 757 can
be successfully reacti-
vated up to four times
while retaining more
than 90% of the fresh
Figure 2 Spot analyses performed by scanning catalyst’s activity (see
transmission electron microscopy Figure 3).
Catalysis 2013 49
28/02/2013 10:27
 reaction rate. Zone 2 ends when
1× React organic nitrogen has been almost
completely removed. At this point,
Fresh the feedstock enters Zone 3 and the
hydrogenation route HDS picks up
speed. Even though the partial
pressure of H2 is at its lowest in
2003 2005 2007 2009 Zone 3, the catalyst is operating in
BCS: >1MPa BCS: >1MPa BCS: >1MPa BCS: >1MPa a nitrogen-free environment.
L: 3.3mm L: 3.0mm L: 2.8mm L: 2.6mm
<1.5mm: 1% <1.5mm: 5% <1.5mm: 7% <1.5mm: 5%
Without nitrogen, the rate of hydro-
<2mm: 6% <2mm: 16% <2mm: 20% <2mm: 23% genation of aromatics, including the
RVA: 97% RVA: 93% RVA: 93% RVA: 92% aromatic rings of sterically
VF: 0.35 VF: 0.32 VF: 0.33 VF: 0.32
hindered dibenzothiophene mole-
cules, increases. Finally, the
2× React 3× React 4× React feedstock exits the reactor with a
sulphur content below 10 ppm.
Figure 3 KF 757 has been successfully reactivated up to four times while retaining more The reaction zones vary in both
than 90% of the fresh catalyst’s activity size and position as a function of
feedstock properties, operating
Stax technology consumed, so the partial pressure conditions and process objectives.
In 2009, Albemarle introduced Stax of H2 is reduced and the partial Understanding where reaction
technology as a methodology for pressure of H2S increases, the latter conditions change presents an
designing catalyst systems to opti- creating some inhibition. As the opportunity to improve system
mise for particular reactions taking rate of direct-route HDS slows, the performance. Rather than settling
place within a hydrotreater. Key to feedstock moves into Zone 2. In for an average level of performance
this technology is the ability to from a single catalyst across all
“see” inside a reactor and develop Understanding where zones, an optimised catalyst system
a simulation model to predict can be designed using catalysts that
performance at every point. A reaction conditions perform well in a particular regime.
simplified, conceptual reactor zone Figure 5 shows some of the
model can be used to illustrate the change presents options for optimising catalyst
principles embodied in Stax selection “trans reactor”; that is, as
technology. an opportunity to the feedstock moves through the
In ULSD operations, three reac- various reaction zones. In Zone 1,
tion zones can be identified as
improve system reaction rates are generally limited
having markedly different condi-
tions, impacting reaction kinetics
performance by the direct desulphurisation rate
due to the shear abundance of reac-
(see Figure 4). In Zone 1, the tions taking place. Desulphurisation
primary reaction occurring is Zone 2, the focus of reaction chem- of mercaptans, sulphides and thio-
(direct-route) HDS. The rate of istry shifts from the removal of phenes and hydrogenation of
desulphurisation is fast and sulphur to the removal of nitrogen, olefins occur rapidly and effectively
sulphur content drops rapidly. At organic nitrogen being the main with relatively modest catalyst
the same time, hydrogen is inhibitor to increasing the HDS activity. That is not to say that

Log S, N

• Reaction rate limited by direct desulphurisation

Zone 1 Zone 1 • Moderate activity catalyst acceptable
• CoMo or NiMo acceptable
N
• Reaction rate limited by inhibition
• Catalyst performance critical
Zone 2 Zone 2 • High HDN activity needed
• Medium to high pressure: NiMo preferred
• Low to medium pressure: CoMo preferred
S
• Reaction rate unconstrained
Zone 3 Zone 3 • Selectivity most important
• Balance hydrogen consumption and stability

S <10 ppm

Figure 4 Reaction zones in a ULSD unit Figure 5 Trans reactor catalyst selection: Stax

50 Catalysis 2013 www.eptq.com

albemarle.indd 2 28/02/2013 12:26

 Reactor Turnkey Services
HPA offers all reactor turnkey services from
blinds to blinds using state of the art equipment.
We specialize in inert-entry using the latest life
support units. All our catalyst technicians are
trained in vessel rescue, first aid, and CPR.

Hydropac Catalyst Dense Loading

The Hydropac allows the sprinkling of catalyst
in a continually uniform pattern at a rate slow
enough to let each particle settle, but fast
enough for acceptable loading time. The
Hydropac sits just six inches below the trays,
is able to rotate both directions, and can
load around transfer tubes and other internal
obstructions.

Catalyst Unloading Services

Our catalyst unloading services make use of
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Vessel Repairs and Retro-Fits

We have our U and R stamp allowing us to do
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Hydroprocessing Associates is ISO 9001 and

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Hydroprocessing Associates is located in the

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country.
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E-mail: peter@hpa-usa.com

www.hpa.sg www.hpa-usa.com

BDGBK\GURFDUERQZRUOGBLQGG 
hpa.indd 1 23/2/12 12:28:06
 catalyst selection is irrelevant. As
the feedstock moves towards the
bottom of Zone 1 and into Zone 2,
catalyst activity becomes increas-
ingly important to promote the
direct desulphurisation of
slower-to-react thiophenes and
benzothiophenes.
Zone 2 is the region where cata-
lyst selection is most critical, both
for unit performance and for oper-
ating stability. Catalyst activity is
important and, in particular, deni-
trogenation (HDN) activity is
crucial to reach the highest perfor-
mance. Organic nitrogen slows all
hydrogenation reactions in Zone 2,
thus limiting the hydrogenation
route desulphurisation and
aromatic saturation. The primary
function of Zone 2 is elimination of
this organic nitrogen inhibition.
When organic nitrogen is near zero,
the feedstock enters Zone 3 and the
character of favoured reactions
changes significantly from Zone 2.
In this conceptual model for
ULSD units, Zone 3 is the finishing
section, where hydrogenation is
enhanced and the remaining, diffi-
cult (hydrogenation route) sulphur
is removed. With no organics pres-
ent, any catalyst will operate at its
highest performance potential. That
is, of course, favourable for desul-
phurisation, but may not be
desirable from a hydrogen
consumption and stability point of
view. Proper catalyst selection must
balance the objectives of the unit
(desulphurisation, cetane uplift,
aromatic saturation) with the capa-
bilities of the unit (hydrogen partial
pressure, hydrogen availability) to
400
390
380
370
nWABT, ºC
360
350
340
330
320
310
300
0 5
Time on stream, months
Figure 6 Normalised ULSD performance of KF 848 fresh and Stax React on a feed diet of
80% heavy gas oil (HGO) and 20% light cycle oil (LCO)
52 Catalysis 2013
albemarle.indd 3
Rejuvenated catalysts can be very
cost effective
Product RVA HDS
KF 757 100
KF 757 React 95
KF 772 130
Stax (50% React/50% KF 757) 100
Stax (30% React/70% KF 772) 128
Table 1
maintain stable performance
throughout the cycle.
The conceptual model just
described serves as an insightful
abstraction, but to be of practical
significance a model is needed to
select the catalyst, position in the
reactor and depth. Stax technology
is Albemarle’s extension of the
reactor zone concept to a tool that
allows optimisation in many
dimensions; most importantly, in
the current environment, along an
economic one in the case of the
application of React catalysts. The
proper selection of the fraction and
positioning of these catalysts
provides optimal performance at
reduced fill costs.
Application of React through Stax
technology
A primary way of benefiting from
the typically greater than 95%
activity recovery obtained after
rejuvenation is a reload of the
ULSD unit with 100% of React cata-
lyst. This way of applying the
technology is attractive as it offers
significant cost savings compared
with the acquisition of fresh cata-
lysts. The performance of this
100% fresh
30% React + 70% fresh
50% React + 50% fresh
10 15 20 25
catalyst supplemented with fresh
top layers is usually capable of
meeting the requirements for full
cycle length and unit operation.
For refiners who are interested in
maintaining maximum flexibility
with respect to unit performance,
there is an alternative method of
deploying React. Many refiners
load the Reactivated catalyst in
combination with fresh catalyst in
ratios ranging from 30-70%. The
fresh catalyst can either be of the
same generation or of a later gener-
ation having higher activity. Table
1 shows the RVA-HDS for various
catalyst loadings using KF 757
React in combination with KF 757
and KF 772. Compared to the
systems with 100% fresh KF 757
and fresh KF 772, the activity level
is not significantly affected by the
introduction of KF 757 React in the
loading scheme.
Stax with KF 848
The application of React in combi-
nation with Stax technology is
illustrated by the following exam-
ple, where a European refiner
successfully implemented the Stax
technology in the ULSD unit. After
the first cycle of fresh KF 848 cata-
lyst, the refiner applied a loading
scheme containing 30% React KF
848 in combination with 70% fresh.
In an additional cycle, the amount
of React catalyst was increased to
50%. For the three consecutive
cycles, the operating temperatures
for a 10 ppm ULSD production
were nearly identical (see Figure
6). This commercial example illus-
trates that there is no penalty on
performance by applying combina-
tions of React catalyst together
with fresh.
Figure 7 illustrates the cost
reduction achieved when loading
React catalysts. Obviously, the
amount of savings is determined
by the market price for molybde-
num, as molybdenum costs
constitute a significant part of the
price of fresh catalyst. The cost
savings provided through the use
of these catalysts are evident, in
particular at higher levels of
molybdenum prices. The figure
provides the approximate annual
savings by applying Stax React
www.eptq.com
28/02/2013 10:27
 compared to a full fresh system.
The savings take into account the
credit that refiners can get by
sending the spent catalyst for
reclaim instead of applying for
reuse. Even in the most conserva-
tive scenario (for instance, 30%
React and a molybdenum price of
$8/lb), the savings per year
amount to $75 000, which trans-
lates into a 10% saving on fill costs
for a 22-month cycle. When 50% is
used and the price of molybdenum
is $30/lb, the savings increase to
$400 000 per year, representing a
30% savings over a full fresh load.
Licensees
Albemarle and Nippon Ketjen have
responded to market demands for
React catalyst products and services
by certifying Eurecat and Porocel
as technology providers. Already,
10 plants worldwide are in service
and capable of providing these
services to our customers. This
year, we will also see a new React
plant in India, operated by Eurecat.
Albemarle works closely with its
www.eptq.com
albemarle.indd 4
new catalyst at the licensee’s plant,
500 and samples may be requested for
30% React
400 detailed analyses.
50% React
350 In addition, Albemarle works
k euro per year
300 with its licensees to optimise the
React treatment on mixed beds and
250
to perform laboratory treatments
200
on difficult samples with, for exam-
150 ple, excessive carbon or other
100 contaminants. X-ray diffraction is
50 used to analyse the quality of
0
Reactivated products. Albemarle
8.00 19.00 30.00 also works collaboratively with
Molybdenum price, licensees to solve specific chal-
dollars per lb lenges and to provide additional
activity testing when necessary.
Figure 7 Cost savings per year for a 175 m3 This close cooperation ensures that
ULSD unit applying 30% and 50% React in the REACT licensee is providing
loading scheme (22-month cycle) exceptional value to the refiner.
licensees to ensure customers get STAX, REACT and STARS are all trademarks of
appropriate catalyst activity and Albemarle Catalysts Company BV.
service. Each Stars grade has its own
Roland Hoffmann is Manager, Total Catalyst
optimum React treatment. Licensees Management, Albemarle Catalysts Company
are asked to demonstrate their capa- BV. Email: roland.hoffmann@albemarle.com
bility each time they apply the Bob Leliveld is Marketing Manager,
technology to a new catalyst type. A Hydroprocessing Catalysts, Albemarle
trial, usually attended by Albemarle Catalysts Company BV.
personnel, is performed for each Email: bob.leliveld@albemarle.com
◗ www.digitalrefining.com is an
easy-to-use website for the
refining, gas and petrochemical
processing industries.
◗ A simple search facility enables
you to find and display relevant
information across the whole
spectrum of articles, literature,
news, events and companies.
◗ Readers can download technical
articles and other information
from over 40 categories.
◗ Find relevant industry events
worldwide.
◗ Read news items focusing on
contracts, company news and new
products.
Catalysis 2013 53
28/02/2013 14:06
 EXTEND
YOUR REACH
ATTEND 2013 AFPM MEETINGS
Be a part of these important
industry events.
Security Conference
San Antonio, TX
April 15 - 17
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May 21 - 24
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May 22 - 23
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September 8 - 10
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Dallas, TX
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Houston, TX
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27/02/2013 11:03
 Predicting FCC unit performance with
laboratory testing
Proper simulation of e-cat and reaction conditions is critical for modelling future
FCC unit operations
KENNETH BRYDEN
Grace Catalysts Technologies
W
hy do we do testing? We
do testing because we
want to predict in the lab
what is going to happen in the
field. Leo Baekeland, an entrepre-
neur and pioneer in the plastics
industry, famously spoke of the
importance of lab and pilot plant
testing when he stated in his
1916 Perkin Medal acceptance
speech, “The principle: ‘Commit
your blunders on a small scale and
make your profits on a large
scale,’ should guide everybody
who enters into a new chemical
enterprise.” Conducting testing
before commercial implementation
reduces risk for a refiner. Examples
of questions that pilot testing can
answer include:
• What will be the effect of a poten-
tial feedstock change on yields?
• How will a new catalyst technol-
ogy perform?
• Which catalyst technology is best
for my operating goals?
• What effect will an additive have
on my yield structure?
Figure 1 outlines what pilot test-
ing intends to accomplish. On a lab
scale, the goal is to match the
complex processes occurring in a
commercial FCC unit. In the unit,
catalyst deactivates over a period of
many weeks due to temperature,
steam and contaminant metals.
Commercial deactivation conditions
are too slow to be practically
copied in the lab, so an accelerated
lab deactivation is done to generate
a simulated e-cat to match the
chemical and physical properties of
the commercial e-cat. Bench-scale
(ACE or MAT) or pilot-scale (DCR)
test equipment is then used to
simulate the reaction conditions in
www.eptq.com
grace.indd 1
Commercial unit
Laboratory
deactivation
Fresh catalyst
Fresh catalyst
Metal deposition make-up
50-100% steam
2-50 hours
1400-1500°F Regenerator
~50 days/1300°F
~20% steam
Simulated ECAT
Equilibrium
catalyst
Key properties
ZSA, MSA, UCS
Ni, V, Fe, Sb, metals distribution
Oxidation state, age distribution
Figure 1 Laboratory testing strategies
the FCC unit and react catalyst and
feed to produce products.
Laboratory deactivation approaches
When studies are being done for
feedstock selection or process
development, commercial e-cat is
usually used and no lab deactiva-
tion is needed. However, catalyst
selection studies and catalyst R&D
start with fresh catalyst. Fresh FCC
catalysts need to be deactivated
before testing because fresh cata-
lysts are too active and the
selectivities seen in fresh catalysts
do not represent e-cats in the FCC
unit. Temperature, metals and
steam are therefore used to turn
fresh catalyst into simulated e-cat.
Commercial e-cat properties that
we want to match with simulated
e-cat include: surface area, unit cell
size (UCS), metals concentration,
metals oxidation state and metals
distribution.
Key yields
Coke, dry gas, LPG, gasoline,
Yields gasoline composition, bottoms,
conversion C/O
Flue Yields
gas
Riser reactor
~980°F, 2-5s
Pilot plant
DCR E-cat or
ACE simulated
e-cat
MAT
Feedstock
Air
Feedstock
Ni, V, Fe, Na
Accelerated conditions to simu-
late hydrothermal deactivation of
zeolite typically involve times of
two to 50 hours, temperatures
between 1400°F and 1525°F (760°C
and 830°C), and steam concentra-
tions between 50% and 100%.1 At
temperatures below 1400°F, it may
be impossible to match the equilib-
rium UCS, and at temperatures
above 1525°F unrealistic zeolite
sintering can be encountered.
Contaminant metals such as
nickel and vanadium accelerate
catalyst deactivation and have
dehydrogenation activity that
increases coke and hydrogen. It is
important to test catalysts with
contaminant metals in order to real-
istically assess the performance of
catalysts with metals trapping and
passivation technologies. The best
way to simulate the contaminant
metals is to apply the same metals
level to the fresh catalyst that is
Catalysis 2013 55
27/02/2013 13:52
 (MM), cyclic metals impregnation
CPS provides a good match to CPS matches yield selectivities in
e-cat properties (CMI) and cyclic propylene steam- DCR evaluation
ing (CPS).2 The Mitchell method
involves impregnation of fresh
E-cat CPS Conversion = 74
AI2O3, wt% 44.8 44.3 catalyst with organic nickel and E-cat CPS
RE2O3, wt% 1.3 1.4 vanadium naphthenates followed Cat to oil 8.2 7.7
Na2O, wt% 0.5 0.4 by steam deactivation for four to 20 H2 yield, wt% 0.10 0.13
Ni, ppm 2240 2550 hours. The CMI method involves C1 + C2, wt% 1.9 1.8
V, ppm 4170 4020 Total C3, wt% 5.3 4.9
Surface area, m2/g 137 145 multiple cycles of cracking with C3=, wt% 4.6 4.3
Zeolite, m2/g 104 111 metals spiked feedstock and regen- Total C4, wt% 9.5 9.3
Matrix, m2/g 33 34 eration, resulting in a deactivation C4=, wt% 6.6 6.7
Zeolite, m2/g 24.26 24.24 time of more than 50 hours. The Gasoline, wt% 51.6 52.5
G-Con RON EST 92.9 93.2
CPS method involves impregnation G-Con MON EST 80.7 80.7
Table 1 of fresh catalyst with organic nickel LCO, wt% 17.8 17.9
and vanadium compounds, Bottoms, wt% 8.2 8.1
present on the e-cat, and then deac- followed by ageing in a cyclic Coke, wt% 5.5 5.4
tivate all the fresh catalyst samples redox environment for ~20 hours.
in a study under the same The reducing atmosphere (which Table 2
conditions. simulates the riser) is a blend of
Deactivation methods that simu- steam, nitrogen and propylene, and blend of steam, air and SO2. Grace
late poisoning by contaminant the oxidising atmosphere (which developed the CPS deactivation
metals include the Mitchell method simulates the regenerator) is a method, and additional details can
be found in reference 3. The CPS
method provides a good match to
Comparison of deactivation procedures
e-cat properties and yields, as seen
in Tables 1 and 2, where the prop-
Method erties and pilot plant yields of fresh
Mitchell CMI CPS Commercial
Deactivation environment Inert/oxidising Cyclic redox Cyclic redox Cyclic redox
catalyst deactivated via CPS are
Effect on vanadium compared to commercial e-cat. The
Vanadium valence +5 +3 to +5 +3 to +5 +3 to +5 CPS method has been adopted by
Vanadium mobility High Low Low Low many labs around the world and
Zeolite destruction High Low Low Low
Effect on nickel
can be easily fine-tuned to match
Nickel valence +2 +2 to 0 +2 to 0 +2 to 0 the severity and specific deactiva-
Reaction with Sb No Yes Yes Yes tion conditions of different
Sulphur effects Minimal S/V competition S/V competition S/V competition commercial units by adjusting the
Metals distribution Uniform Shell concentrated Uniform/shell* Shell concentrated
Metals age distribution Uniform Non-uniform Uniform Non-uniform
temperature, the number of redox
Implementation Easy Tedious Easy - cycles and the amount of oxygen in
the regeneration atmosphere.
*Grace is developing a shell impregnation method.
Table 3 is a comparison of the
Table 3 different lab deactivation methods
to the conditions in a commercial
unit. In deactivating catalyst with
20% no metals 20% low metals 60% high metals
contaminant metals, it is important
Mild steam (10% of total metals) (90% of total metals) to include the effect of sulphur
Standard steam Severe steam competition by using SO2 as part of
100
the simulated regenerator
Cumulative activity and nickel,

90 Youngest 20% has conditions.

~2% of the Ni but
80 contributes ~50% Under commercial regenerator
of the activity Oldest 60% has
70 ~90% of the Ni but conditions, calcium oxide and
60
contributes ~20% barium based metals traps are
of the activity
rapidly poisoned by sulphur and
50
%

Middle 20% has

lose their vanadium trapping abil-
40
~8% of the Ni but ity. This sulphur poisoning does
30 contributes ~30% not happen with rare earth based
of the activity
20 vanadium traps. Testing of vana-
Cumulative nickel
10 dium traps in the laboratory
Cumulative activity
0 without simulating the SO2 present
0 10 20 30 40 50 60 70 80 90 100 in a commercial regenerator can
Cumulative weight, % give a false prediction of catalyst
metals trapping ability.
Figure 2 Lab deactivation to simulate age distribution (AD-1) Commercial FCC units differ in

56 Catalysis 2013 www.eptq.com

grace.indd 2 27/02/2013 16:25

 CPS with age distribution

Deactivation procedure
Presteaming 5 hrs at 1500°F,
50 wt% steam
5 hrs at 1500°F,
50 wt% steam
5 hrs at 1500°F,
50 wt% steam
AMACS
Metals deactivation None 2150 ppm Ni, 2500 ppm V 4300 ppm Ni, 5000 ppm V

Analysis
20hr 1450°F CPS 40hr 1450°F CPS Compressor suction drums:
Zeolite SA, m2/g 183 141 83
Matrix SA, m2/g 52 44 34
Unit cell size, A 24.32 24.29 24.27
Ni, ppm 31 2130 4370
V, ppm 40 2770 5430
MAT 78 68 49
Kinetic conversion 3.56 2.15 0.97
Activity contribution, % 41 25 34
Metals contribution, % 0.2 14.0 85.8
Fraction in blend, % 20 20 60

Three fractions with varying metals levels and activity

I think I’ve got liquid carryover.
Table 4 what can I do about it?
It happens in petrochemical
Age distribution deactivation provides Good agreement between e-cat and plants, refineries, and anywhere
a good match to commercial e-cat AD-1 in DCR evaluation else that the gas approaching
a compressor is wet. Traces of
E-cat AD-1 Conversion = 77 aqueous or organic liquid escape
Al2O3, wt% 39.2 40.2 E-cat AD-1 the inlet knockout drum, often
RE2O3, wt% 2.8 2.6 Cat to oil 11.8 10.9
Na2O, wt% 0.4 0.3
intermittently, and silently damag-
H2 yield, wt% 0.11 0.22
Fe, wt% 0.8 0.5 C1 + C2, wt% 3.2 3.0 ing the compressor. Telltale signs
P2O5, wt% 0.2 0.1 C2=, wt% 1.0 0.9 include pitting corrosion, salt
CaO, wt% 0.3 0.1 Total C3, wt% 6.5 6.5 deposits, and diluted lubricants.
Ni, wt% 3320 3050 C3=, wt% 5.6 5.7
V, wt% 3090 3870 Total C4, wt% 11.3 11.4 Typical 1980’s mist eliminator technology
Sb, wt% 689 <50 C4=, wt% 8.2 8.2 Cooler
Surface area, m2/g 129 159 Gasoline, wt% 50.1 50.4
Zeolite, m2/g 95 123 G-Con P, wt% 3.0 3.0
Matrix, m2/g 34 36 G-Con I, wt% 19.8 19.4 Stage 1 Stage 2
Zeolite, m2/g 24.29 24.29 G-Con A, wt% 34.7 34.7
G-Con N, wt% 10.4 10.2 Knockout
drums
Table 5 G-Con O, wt% 32.2 32.8
G-Con RON EST 93.9 94.0
G-Con MON EST 80.3 80.5 Instead of trying to repair
their catalyst turnover rates. When LCO, wt% 16.8 16.9 symptoms, look for the root cause,
it is desired to very closely match Bottoms, wt% 6.2 6.2 which usually involves the mist
lab-simulated e-cat to e-cat from a Coke, wt% 5.0 5.3
eliminator in the knockout drum.
specific refinery, age distribution Problems may include improper
deactivation can be used. Table 6 mist eliminator specifications,
Commercial e-cat consists of cata- overloading, uneven velocity, waxy
lyst particles with varying age, and activity distribution for e-cat deposits, liquid slugs, foaming,
surface area, UCS, metals level, from a refiner on the US east coast incorrect installation, and several
activity and selectivity. Sink/float and how this age distribution can other possibilities. New, high-
experiments that separated refinery be simulated by deactivating three capacity, high-efficiency mist
e-cat into age fractions have deter- separate catalyst fractions: one eliminator technologies pay off the
mined that activity and selectivity representing the youngest 20%, one first time you avoid shutdown.
are dominated by the youngest representing the middle 20% and
fraction of the catalyst. Typically, one representing the oldest 60%. A Read more on this topic at
the youngest 20% of the inventory greater number of fractions could www.amacs.com
contains less than 10% of the be used in the simulation, but
contaminant metals and contributes Grace has found that three age frac-
about 50% of the overall activity. tions results in the least complexity
For a specific unit, the metals and while still giving a good match to
activity distribution will depend on commercial yields. Table 4 shows
Phone:+1-713-434-0934 • Fax: +1-713-433-6201
catalyst addition rate, deactivation the chemical and physical proper-
amacs@amacs.com
rate and catalyst activity. Figure 2 ties of the three fractions that were
presents the contaminant nickel deactivated, Table 5 shows how the

www.eptq.com Catalysis 2013 57

grace.indd 3 27/02/2013 16:30

 properties of a blend of the three
Control Control fractions match those of commer-
Meter valve valve Meter cial e-cat, and Table 6 provides
yields from the DCR evaluation of
Regenerator Stripper
commercial e-cat and the simulated
e-cat produced by the AD-1 proto-
col. As the DCR results show, there
Feed Feed
storage storage is excellent agreement between the
tank No. 1 tank No. 2 Condenser
yields of the e-cat and the AD-1
Heat Stabiliser deactivated catalyst. The discrep-
exchanger column
ancy in hydrogen yield is likely
Feed Feed due to the presence of passivating
tank tank antimony on the e-cat, but not on
Riser
reactor the AD-1 deactivated catalyst.
Scale Scale In summary, fresh FCC catalysts
need to be deactivated before test-
ing. CPS is a rapid method to
Stripping
Feed steam match e-cat properties and yields.
Feed
preheater
Dispersant To better match a specific refinery’s
pump steam e-cat, CPS with age distribution can
be used, but it is more time
consuming.
Liquid product receivers
FCC catalyst testing
Figure 3 DCR pilot plant schematic Performance testing of FCC catalysts
can be done by either bench-scale
testing or pilot plant-scale testing.
Comparison of test unit conditions to commercial FCC unit conditions
Examples of bench-scale testing
equipment include fixed-bed micro-
MAT/ACE Circulating riser Commercial activity testing (MAT) and fixed
Nature of operation Unsteady state Steady state Steady state
fluidised bed testing, one example
Catalyst contact time 12-150 secs 2-5 secs 2-8 secs
Temp. range 930-1100°F 930-<1100°F 980-1030°F of which is the Advanced Cracking
Hydrocarbon partial pressure ~12 psia 20-45 psia 20-50 psia Evaluation (ACE) instrument
Catalyst inventory 5-10g 2-3kg 100 tons marketed by Kayser Technology.
Advantage Easy to set up Mimics commercial operation
Several pilot plant designs are in
operation throughout the world and
Table 7 include both once-through and
circulating designs. The most
common is the Grace-developed
Comparison of DCR to commercial FCC unit run at same operating conditions Davison Circulating Riser (DCR).
Table 7 provides a comparison of
the conditions in these test units to
DCR Run 1 DCR Run 2 Refiner A
Rx exit temp., °F 1000 1000 1000 commercial operation.
Regen catalyst temp., °F 1366 1366 1366 MAT and ACE testing have the
Feed temp., °F 486 486 486.4 advantages that they are easy to set
Rx exit pressure, psig 40.0 40.1 28.9
up and require small amounts of
Rx exit HC pressure, psia 35.3 35.5 19.1
Riser bot HC pressure, psia 14.2 14.2 24.3 material. The DCR pilot plant has
Cat/oil ratio 7.7 7.7 6.5 the advantage that it mimics all the
Conversion, wt% 76.9 77.5 77.5 processes present in commercial
Kinetic conversion 3.34 3.44 3.44
operation and it can operate at the
H2 yield, wt% 0.17 0.17 0.15
C1 + C2, wt% 4.1 4.1 3.9 same hydrocarbon partial pressure
Total C3, wt% 6.8 6.8 6.1 as a commercial unit. Figure 3 is a
C3=, wt% 5.5 5.5 4.7 schematic drawing of the DCR. The
Total C4 , wt% 11.2 11.5 10.2
system consists of three main units:
Gasoline, wt% 50.0 50.1 51.6
RON (DCR - est from Gcon) (92.5) (92.6) 91.1 a riser, a stripper and a regenerator.
MON (DCR - est from Gcon) (80.0) (80.1) 81.6 Both the regenerator and the strip-
LCO, wt% 14.3 13.9 14.9 per are equipped with slide valves
Bottoms, wt% 8.8 8.7 7.6
for control of catalyst circulation
Coke, wt% 4.7 4.8 5.4
rate. The DCR is typically operated
in adiabatic mode, where changing
Table 8 feed preheat or regenerator

58 Catalysis 2013 www.eptq.com

grace.indd 4 27/02/2013 13:52

 Summary of laboratory testing strategies
unit performance. Table 9 describes
the typical strategies for different
testing objectives. Grace Catalysts
Testing activity Catalyst deactivation Testing reactor Technologies has extensive catalyst
Feedstock evaluation E-cat ACE/DCR
Process development E-cat DCR
deactivation and testing capabilities
Catalyst selection Lab deactivation ACE/DCR to support the development of new
Catalyst monitoring E-cat ACE products, the customisation of
Catalyst R&D Lab deactivation ACE/DCR existing products, and to provide
Emission control additives E-cat/additive DCR
Other additive selection E-cat/additive ACE/DCR
technical support.

Table 9
temperature will result in a change
in catalyst circulation to maintain
the reactor outlet temperature, the
same process control strategy used
in many commercial FCC units.
Due to the similarity between the
DCR riser and the commercial FCC
unit riser, yields obtained from the
DCR simulate commercial FCC unit
yields closely. Table 8 compares
DCR yields to commercial yields
when the DCR was run at the same
conditions as a commercial FCC
unit with e-cat and feed from the
unit.
The DCR is a highly flexible pilot
plant and has been used to success-
fully evaluate many different
feedstocks, including resids, naph-
thas, gases and feeds from
non-petroleum sources such as
vegetable oils and pyrolysis oils.
Due to its simplicity of operation
and ability to match commercial
yields, the DCR has become the
leading commercially available tech-
nology for small-scale FCC pilot
units. There are currently 26 DCR
technology licences worldwide.
Summary
In order to minimise risk, proper
catalyst deactivation and testing are
important in predicting commercial
References
1 Young G in Fluid catalytic cracking: science
and technology, Magee J S, Mitchell M M Jr, Eds,
Studies in Surface Science and Catalysis, Vol 76,
Elsevier, Amsterdam, 1993, 257.
2 Cheng W-C, Habib E T Jr, Rajagopalan
K, Roberie T G, Wormsbecher R F, Ziebarth
M S, Fluid catalytic cracking, Handbook of
Heterogeneous Catalysis, 2nd ed, Ertl G,
Knözinger H, Schüth F, Weitkamp J, Eds, Wiley-
VCH, Weinheim, 2008, Vol 6, 2741-2778.
3 Wallenstein D, Roberie T, Bruhin T, Catalysis
Today, 127, 2007, 54-69.
Ken Bryden is Manager of the FCC
Evaluations Research Group in Grace Catalysts
Technologies. He holds a BS degree in chemical
engineering from the University of California
Davis and a PhD in chemical engineering from
the Massachusetts Institute of Technology. He
is co-inventor on one issued patent and co-
author of nine peer-reviewed journal articles.

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unique solutions for at-line and
laboratory elemental analysis
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Determination of Sulfur and other

elements at-line and in the laboratory
Visit us at
Discover more exciting details at Pittcon 2013,
17-21 March,
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 Refining refiners’ spent catalysts
Spent catalyst is the raw material for a recycling operation that delivers fresh
catalyst and specialist metals
B J STEPHAN
Gulf Chemical and Metallurgical Corporation
G
ulf Chemical and Metal-
lurgical Corporation (GCMC)
provides environmental
services to petrochemical refineries
through a business designed to
treat spent catalysts generated by
the refineries in their hydrotreating,
hydrodesulphurisation and residual
desulphurisation processes. Fully
permitted by federal, state and
local agencies for receiving, storing
and processing both hazardous and
non-hazardous spent catalyst at its
Freeport, Texas, location, GCMC
operates a service for safely
and environmentally responsible
handling of spent catalysts. The
company converts 99% of catalyst
and fouling compounds into
commodity forms of molybdenum,
vanadium, nickel, cobalt and
alumina.
Recycling and secondary mining
forms the basis of GCMC’s busi-
ness. Through complete recycling,
the company adds value to catalyst
consumers by enabling them to use
materials with the highest initial
activity to increase yields and
extend an operating cycle to
maximise profitability while mini-
mising the carbon footprint of their
production units. This will become
more important as the next stage of
the shale development relies not
only on natural gas, but also on
shale oil. These feedstocks will
present additional challenges, as
the deactivation of catalysts and
fouling as a function of time will
become non-linear at different
points along the operating cycle.
Due to these factors, partial treat-
ment or landfilling of refinery
wastes is not an environmentally or
financially sustainable practice.
www.eptq.com
eramet.indd 1
Process
There are three distinct plants and
several support facilities that oper-
ate as one integrated process at
GCMC (see Figure 1). They can be
operated independently, in
sequence, or as batch processes,
depending on the types of material
being recycled. The logistics, stor-
age, classification and analytical
functions tie all of the processes
together in order to track, control
and optimise the value chain.
Logistics
Materials arrive by truck or rail and
are contained in different vessels
including bulk railcars and trucks,
roll-off boxes, collapsible sacks and
a variety of totes. The choice of
container depends on the character-
istics of the spent catalyst and the
method of loading at the customer’s
location.
Storage and classification
The entire process begins with spent
catalyst being classified and stored
Typical composition of hydrotreating
catalyst
Characteristics Weight %
Moisture 7.73
Oil 12.5
C (fixed) 12.0
S 6.21
Mo 4.03
V 4.72
P 0.25
Fe 0.38
Ni 2.38
Co 0.57
Si02 0.85
Others 15.0
AL2O3 33.39
Table 1
according to the characteristics of
the material. Table 1 shows a typical
composition for hydrotreating cata-
lyst. These characteristics may be
inherent to the original catalyst
itself, including molybdenum, nickel
and cobalt.
Other properties are imparted to
the spent material due to additives
and materials that are naturally
occurring in the crude oil, including
volatile organic compounds, phos-
phorus, nickel, arsenic, vanadium,
iron and silicon. GCMC has a
specialised Resource Conservation
and Recovery Act (RCRA) permitted
storage management system, includ-
ing facilities with primary and
secondary containment.
Oil recovery
Some spent catalysts, particularly
those containing vanadium, also
contain residual oil, which is
collected and managed using an
oil-water separator. Catalyst fines
are removed from the oil and recy-
cled in a process described below.
The oil is segregated and sent
off-site for fuel recovery.
Roasting plant
The roasting plant is used to
produce calcine, which provides
feedstock for the remaining plants.
Spent catalysts are mixed with
reagent chemicals and thermally
treated using controlled amounts of
heat and oxygen to burn residual oil
present in the catalysts and to
oxidise molybdenum and vanadium
to their highest valence states to
make them react with the reagents.
These reactions produce soluble
and insoluble metal compounds,
depending on the types of catalyst
Catalysis 2013 61
27/02/2013 13:54
 Spent catalysts
Roasting Grinding
Soda ash & leaching
roasting
Grinding
PCC Leaching
ESP
Dust
recycled
to process
Figure 1 Plants and support facilities at GCMC
and their associated contaminants.
GCMC uses proprietary multiple
hearth furnaces with pyrolysis and
oxidation, which provide excellent
thermal properties while remaining
efficient for the high volumes of
material that are processed yearly.
SO2 and particulate removal
The roasting process also liberates
particulate matter, hydrocarbons
and sulphur from the spent catalyst.
The roasters operate in conjunction
with a post-combustion chamber
(PCC) and two electrostatic precipi-
tators (ESP). During roasting,
hydrocarbons are burned off. Part of
the sulphur is oxidised to sulphur
dioxide and part of it is converted to
sodium sulphate. GCMC uses a
series of ESPs, high-temperature bag
houses and a circulating dry scrub-
ber to capture the particulates and
sulphur. In this step, the ESPs are
62 Catalysis 2013
eramet.indd 2
Alumina concentrate smelting
Lime Coke
Dryer
Filtration
Solids
Ni/Co
alloy
Liquid
Recovery
V205 Mo03
Recovery of Recovery of
vanadium molybdenum
Water treatment
Solvent Recovery of
extraction ammonia
used to collect particulates and recy-
cle them back into the process for
valorisation. The off-gases are
humidified with water sprays and
contacted with hydrated lime in a
counter-current entrained bed reac-
tor, where the reaction consumes
the water and generates a dry
byproduct
Hydrometallurgical plant
The calcine that has been produced
during the roasting process is
ground and leached to produce a
slurry containing all of the remain-
ing metals and contaminants.
Grinding is necessary to ensure all
of the solids have a uniform particle
size distribution to increase the
dissolution rate of soluble metals
and to improve the efficiencies of
mechanical decantation and filtra-
tion. Using decantation circuits and
filtration, a solid concentrate
Gas
DC electric cleaning
arc furnace
Fused
calcium
aluminate
NPDES
outfall
containing alumina along with
oxides of nickel and cobalt is
produced. This material provides
the base feedstock for the pyromet-
allurgical plant. The soluble fraction
of the slurry is treated to remove
phosphorus, aluminium and arsenic
waste. The purity of V2O5 and MoO3
is reduced when these contaminants
are present, ultimately reducing
yield. This comprises the 1% of
material that is not currently recy-
cled and is disposed of as hazardous
waste (99/100%).
Vanadium and molybdenum are
contained in the purified solution
and mixed with reagents to precipi-
tate ammonium metavanadate
(AMV), which is further calcined at
high temperatures to decompose
into ammonia and vanadium
pentoxide (V2O5). Vanadium is a
contaminant found in crude oil and
ultimately one of the contributors to
www.eptq.com
27/02/2013 13:54
 fouling of catalysts. It is primarily
used for master alloys of steel and
chemical production. In higher
concentration, it gives steel the
toughness necessary to be formed
into drill bits and steak knives.
The granular V2O5 is fused and
quenched on a rotating wheel to
produce flakes typically containing
over 99% V2O5. Particulate matter
and ammonia are further recovered
in a series of bag houses and scrub-
bers. Ammonia in the process gas is
also recycled and used to make
reagents consumed in the hydrome-
tallurgical process.
Molybdenum is the primary
component of the filtrate from the
AMV precipitation. This filtrate is
treated with a reducing agent,
heated and acidified to precipitate
molybdic acid. After filtration and
washing, the molybdic acid is
calcined to produce molybdenum
trioxide (MoO3) that is over 98%
pure.
GCMC’s molybdenum can be
found in industrial and consumer
products including stainless steel.
This is used for everything from
chemical processing equipment to
kitchen sinks. Molybdenum chemi-
cals are used in many industrial
catalysts and water treatments. The
company produces chemical-grade
molybdenum trioxide for
complete, 360-degree sustainable
loop back into the fresh catalyst
industry, as well as technical grades
for speciality alloys (see Figure 2).
Molybdenum and vanadium left
in the filtrate from the molybdenum
recovery process are recovered
through solvent extraction. The strip
liquor is recycled and the raffinate is
sent to the ammonia recovery
circuit. The ammonia gas is recov-
ered by scrubbing with dilute acid
to regenerate ammonium chloride
and sulphate.
Pyrometallurgical plant
As discussed above, a base feed-
stock for the pyrometallurgical plant
is a solid concentrate containing
alumina, along with oxides of nickel
and cobalt, which are produced in
the hydrometallurgical plant. The
concentrate is dried and reduced in
the presence of carbon using a
proprietary electric arc furnace to
www.eptq.com
eramet.indd 3
Shipped to GCMC
Spent catalyst waste Stored and classified
Sulphur and metals removal Roasting process
Gulf
360º
Oil refining Leaching process
Molybdenum recovery Leach residue
Mo03 Alumina concentrate
Fresh catalyst manufacturers EAF process
Technical-grade oxide Nickel/cobalt alloy
Stainless steel Calcium aluminate
Oil refinery Product
Vanadium recovery
V205
Bear Metallurgical
Ferrovanadium
High-performance steel
Forgings
Aerospace
Military
Construction
Automotive
Figure 2 A 360-degree sustainable loop back into the fresh catalyst industry
produce a high-grade alloy of nickel, In addition to GCMC in the US, it
cobalt and fused alumina. Nickel is owns Valdi in France, which recy-
added to alloys to increase their cles metals from batteries, spent
corrosion resistance. Cobalt is added catalysts, and stainless steel scales
a to alloys to increase their high- and grindings along with metal
temperature strength. Nickel and hydroxide sludges. The recovery of
cobalt are sold as an alloy directly to this waste from the metal treatment
major commodity consumers, while industry involves reducing its chem-
alumina is recycled and used for ical components into a metal form
applications in the abrasive and directly reuseable by foundries and
steel industries. steel producers.
The decision to convert spent oil
Sustainable development refining catalyst into base materials,
Over the past 50 years, GCMC has which are used to make fresh cata-
recycled approximately 1 300 000 lyst or used as direct replacements
tons of spent catalyst. In one year, for virgin ores, is a matter of
the company will recycle around commitment to conservation and
2500 tons of ceramics and 30 000 recovery.
gallons of oil. It owns Bear
Metallurgical Corporation, which
converts molybdenum and vana-
B J Stephan is Senior Executive Vice
dium oxides into ferromolybdenum
President of Gulf Chemical and Metallurgical
and ferrovanadium alloys. GCMC is
Corporation. Also Chairman of the Brazosport
part of the Eramet Group, which Petrochemical Council, he holds a BS in geology
has mining and metallurgical opera- from The University of Pittsburgh, an MS in
tions including recycling and hydrology from Ohio University, and a MBA
chemical businesses. Eramet is the from Bay Path College, maintains a SPHR from
world’s largest producer of nickel The Society for Human Resource Management
carbonate and manganese chemicals and is a licensed Professional Geologist in
as well as refined manganese alloys. Pennsylvania.
Catalysis 2013 63
27/02/2013 13:54
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