catalysis

2016

ptq
 We create
chemistry
that makes
individual
refiners love
fueling the
world.

As the global leader in catalysis, BASF helps fuel the world

by providing innovative technologies, products and services
to enhance performance and sustainability in the petroleum
refining industry. We create value for refineries through a
flexible offering of FCC catalysts and additive solutions, and
advanced technical service. When individual solutions solve
global problems, it‘s because at BASF, we create chemistry.

www.catalysts.basf.com/refining

311568_CL_AZ_Raffineriekatalysatoren_210x297_RZ.indd 1 04.02.16 13:36

 catalysis Security of
ptq
feedstock supply
2016 Vol 13 No 2 3 Revisiting the rare
2008
www.eptq.com Chris Cunningham

D
Editor 5 espite
catalysis
signs q&a
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
19 conventional
Guarding against wisdomcontaminants
that higher fuel prices and a slowing economy
would curb demand and increase supply, but for the past seven years
Production Editor that has notMichael
proved to Schmidt
be the case.Haldor While Topsoethe rateA/Sof increase in world oil demand
Rachel Zamorski has declinedHenrik since theRasmussen Haldor Topsoe2004,
surprising 4% surge in Inc 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
27 will
themselves Increasing
continue. FCCIt ispropylene
also safe toyield assume that refinery and petrochemical
Graphics Editor conversion unit capacity will need to expand.
Mohammed Samiuddin Rudolf Látka, Vladimír Oleríny and Norbert Kováč Slovnaft
No massive new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com Tom Ventham
foreseeable future. The world Johnson
will remainMatthey ProcessonTechnologies
dependent oil and gas for decades to
come even though the upstream industry faces increasing challenges in the
Editorial discovery and production of new sources. In fact, some well-placed industry
35 Kinetic engine drives catalyst development
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 regionsAndreaoutsideBattiston
of OPEC. For this reason, we will continue to see significant
tel +1 281 374 8240 investment Albemarle
in refineryCorporation
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quality of feedstock supply.
43 Revamping
Feedstock options suchfor ULSD production
as biomass (for biofuels production), Canadian tar sands
Advertising Sales Manager (for distillateMike
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Paul Mason Rogers Criterion Catalysts & Technologiescrude sources require
reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com
process confi Kirit Sanghavi
gurations. TheAlonqualityUSAofRefining
these types of feedstock are one important
Advertising Sales reason why a wider array of catalysts has been introduced into the market. For
Bob Aldridge example, as refiners cut deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com
51 Look beyond the catalyst
metals in the VGO requires a properly designed guard bed system to protect active
catalysts in theAustin SchneiderThe characteristics of feedstock with low API gravity
hydrocracker.
Advertising Sales Office (eg, <10), high metals, nitrogen and other undesirable components is one of the
tel +44 870 90 303 90
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main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 accommodate not only higher volumes of catalyst, but also a wider variety of
catalyst57 withCalcium containing feedstock processing
specific formulations.
Publisher
Non-catalytic processes are also playing a significant role in the refiner’s ability
Nic Allen Chinthala Praveen Kumar, Sukumar Mandal, Gopal Ravichandran,
to process whatever unconventional crude sources become available. For example,
publisher@petroleumtechnology.com
some refiners Srikanta
processing Dinda,higherAmit V Gohel,
volumes of Ashwani
resid and Yadav atmospheric and Asit Kumar
tower Das
bottoms
Circulation have considered adding certain
Reliance Industries Limited types of solvent-extraction processes in addition
Jacki Watts to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
circulation@petroleumtechnology.com coker operations. Improvements in furnace technology, such as with olefin steam
cracker operations, have resulted in significant increases in worldwide ethylene
Crambeth Allen Publishing Ltd capacity.
Hopesay, Craven Arms SY7 8HD, UK However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax +44 870 90 600 40
the following articles authored by experts in the field of downstream process
ISSN 1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
Cover
editorial
OMV’s and responded
Schwechat toback-to-back
refinery, Vienna: the Q&A published
trials at the refinery in this
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the full questions
story, see PTQ’s (www.eptq.com)
Q2 2016 issue.

Petroleum Technology Quarterly (USPS

0014-781) is published quarterly plus
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437
Back numbers available from the Publisher
at $30 per copy inc postage.
that addressed the specifics of certain reactor and catalytic issues of importance to
Photo: OMV
the industry.
©2016. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
René G Gonzalez
NO REST FOR THE
LEADER
While you’ve been getting to know the scientists behind our advanced research and
technology the past few years, we’ve been increasing the performance and quality
of our catalysts. We’ve continued to surge ahead with industry leading results; the
next generation of SENTRYTM, CENTERATM and ASCENTTM catalysts are here.
Our advanced array of products protect refining operations and provide solutions for
hydroprocessing needs.

Criterion brings all the technology together into practical, customized solutions for
your refinery:

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Hydrotreating: Meeting strict fuel standards and maximizing advantaged feeds
Residue Upgrading: Both Fixed Bed and Ebullated Bed methods to turn the
bottom end of the barrel into valuable fuels
Hydrocracking: Increasing the Distillate yields and processing heavier feeds
Tail Gas: Ensuring that you meet strict air quality standards at the lowest temperatures

With technical customer service second to none, Criterion continues to lead the
industry for catalyst performance and value. We look forward to working with you.

Leading minds. Advanced technologies.

www.CRITERIONCatalysts.com
 catalysis Security
Revisiting of
the rare
ptq
feedstock supply
Vol213 No 2
Vol 21 No
2016 2008

DD
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
Editor René G Gonzalez o you recall the Great Rare Earth Crisis of 2010? Elements such as
refiners remain a big play for prospective investors. It used to be
Chris Cunningham
editor@petroleumtechnology.com lanthanum and cerium, which had been shown back in the 1960s to
editor@petroleumtechnology.com conventional wisdom that higher fuel prices and a slowing economy
transform the activity of zeolites, suddenly appeared to be very rare
would curb demand and increase supply, but for the past seven years
indeed. All of a sudden, price rises for compounds of these esoteric materials
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 achieved
declined since percentages in the tens
the surprising of thousands.
4% surge in 2004, Would refining appears
it nevertheless becomethat an
production@petroleumtechnology.com
production@petroleumtechnology.com
unmanageably expensive business?
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
In fact
increasing oilthe technology by
consumption supply
China, side of refining
India and even already had its
the Middle Eastsolutions
producers to
Graphics Editor the problem and the catchphrase of 2011 became
themselves will continue. It is also safe to assume that refinery and petrochemical ‘rare earth free’. Since the
Rob Fris Graphics Editor 1990s, catalyst
conversion suppliers
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to expand.
Mohammed Samiuddin
graphics@petroleumtechnology.com
Nozeolites
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the development of rare earth free catalysts in the US at the time). tower, the concentration of
sales@petroleumtechnology.com metalsAs in athe VGO requires a properly designed guard bed
result of one of those territorial disputes that arise between neigh- system to protect active
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bouring states, China cut its supply of rare earths to Japan and the market
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Shaw went into panic mode. While China did indeed restrict exports of rare earths
main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90
circulation@petroleumtechnology.com through imposed quotas, fear of curtailed supply is chiefly what drove prices
accommodate not only higher volumes of catalyst, but also a wider variety of
through the roof. Rare earths are used in key components for technologies
catalyst with specific formulations.
Publisher with a profileprocesses higher than refining’s
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Crambeth Allen Publishing Ltd
NicArms
Allen Non-catalytic are also significant role ner’s ability
Hopesay, Craven SY7 8HD, UK instance – so the perceived prospect of a slow-down in key sectors of the
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tel +44 844 5888 776 to process whatever unconventional crude sources become available. For example,
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in addition
Jacki Watts
ISSN 1362-363X tives to rare earths. It quickly became clear
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed that the crisis was not quite as
circulation@petroleumtechnology.com cokerdire as the markets
operations. imagined.in furnace technology, such as with olefin steam
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Crambeth Allen Publishing
PTQ (Petroleum Technology Quarterly) (ISSN Ltd
thing in the commodities business. China is reported as the major user of
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No: 1632-363X, USPS No: 014-781) is published
Hopesay, Craven Arms SY7by8HD,
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by SP/Asendia, 17B 870 90 600Avenue,
South Middlesex 40
Monroe NJ 08831. Periodicals postage paid at New the that or set articles
following up businessauthored in China to avoid
by experts anyfield
in the issues of with export quotas,
downstream process
Brunswick, NJ. Postmaster: send address changes to
ISSN
PTQ (Petroleum 1362-363X
Technology Quarterly), 17B South while China’s
technology. own technology
PTQ wishes to extend sector is thriving
its gratitude to the on authors
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Middlesex Avenue, Monroe NJ 08831. supplies
editorial and of rare earths.
responded to theBut Q&A thatpublished
internal in supply
this issue mayofone PTQday become
Catalysis, as
Back numbers available from the Publisher
at $30 per copy inc postage.
wellrestricted,
as to those respondents
which after all whois what addressed
monopolies the online
can do questions (www.eptq.com)
to raise prices.
Petroleum Technology Quarterly (USPS
that addressed the specifics of certain reactor and catalytic issues of importance to
0014-781) is published quarterly plus the industry.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. CHRIS CUNNINGHAM
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez
Catalysis 2016 3
maximize
propylene
Refiners can tap into the huge potential of the FCC
to maximize petrochemical yields by modifications
to process conditions and the use of Johnson
Matthey’s INTERCAT JM ZSM-5 additives.

ZSM-5 chemistry is more than just cracking gasoline.

When optimizing LPG olefins the ZSM-5 shape
selective zeolite creates new gasoline olefins through
light olefin oligomerization that can be cracked
back down into LPG olefins. Johnson Matthey has
applied these insights to our high activity ZSM-5
additives for enhanced propylene production.

UK Tel +44 (0)1642 553601 Fax +44 (0)1642 522542

www.jmprotech.com
 catalysis q&a
Q We are experiencing sudden drops in pressure differential
across the regenerated catalyst slide valve. What is the likely
cause and is this a sign of bigger problems to come?
A David Banks, Account Manager, Refinery Catalyst, David
Banks@basf.com, Jason Goodson, Account Manager, Refining
Catalysts, Jason.Goodson@basf.com and Yorklin Yang, Global
Process Technology Advisor - Refining Catalysts, Yorklin.Yang@
basf.com, BASF Catalysts
While it is not uncommon to encounter catalyst circu-
lation challenges from time to time on any given FCC
unit, the potential sources of the issue are quite varied,
and can be as challenging to diagnose as they are to
manage operationally. However, these problems can
generally be dealt with effectively by using a system-
atic approach in combination with patience,
persistence, and a sound understanding of the FCC
pressure profile.
Aeration
One of the most prevalent causes of slide valve differ-
ential loss is standpipe over- or under-aeration.
Aeration involves injection of a gaseous medium
(generally air or steam) at regular intervals along the
length of a standpipe to replace volume lost due to
compression. Proper aeration is essential to ensure a
consistent standpipe density and reliable pressure gain.
Too much or too little aeration can be equally problem-
atic for catalyst circulation and slide valve dP, as either
can dramatically impact standpipe density and in turn
destabilise the pressure build.
Over-aeration is much more commonly observed
than under-aeration and can be attributed to a number
of likely sources. More often than not, over-aeration is
simply the result of having opened several aeration
points much wider than necessary. The prevailing
mentality here is ‘if a little is good, a lot is better’,
which in the case of aeration is not at all true. In other
cases, a transient/temporary circulation problem may
have required more aeration than normal, but once
recovered, the aeration flow does not get reset back to
normal rates.
Given the high frequency of circulation problems
brought about by non-ideal aeration rate, one of the
first checks the refiner is encouraged to make is to
verify standpipe aeration rates and, if necessary, adjust
downward or upward accordingly, always starting
from the top of the standpipe. The success of adjusting
aeration can be assessed by monitoring the pressure
profile in the standpipe. An ideal standpipe density is
around 40 lb/ft3.
Additional Q&A can be found at www.eptq.com/QandA
www.eptq.com
Aeration rates can be calculated based on compres-
sion of entrained gas, however a simple rule of thumb
is to apply aeration of 0.8 x catalyst circulation rate
(tons/min), where the aeration rate is in scfm per 6 ft
of standpipe elevation. So, for example, a unit with a
circulation rate of 35 tons/min with aeration points 8 ft
apart would require 0.8 x 35 x 8 / 6 = 37 scfm per
aeration point.
Just as important as the aeration flow is the quality
of aeration media itself. The flow to each tap is
governed by a restriction orifice (RO), which relies on
a consistent quality to ensure stable flow. Wet air or
steam can be profoundly problematic as it interferes
with the consistency required at the RO and can addi-
tionally cause plugging at the nozzle tip where it
comes into contact with the catalyst.
Regenerator operation
Often, the source of problems at the regenerated cata-
lyst slide valve lies in the operation of the regenerator
itself, ranging anywhere from air distributor integrity
to cyclone performance to instrumentation. For
instance, a combustion air distributor can become
partially plugged and lead to poorly fluidised or stag-
nant catalyst at the standpipe entrance. In some cases,
partial mechanical failure of an air grid distributor in
the region of the standpipe entrance has resulted in
excessive standpipe over-aeration (as described above)
as catalyst entrains combustion air downward.
Typically, problems in the regenerator itself will be
apparent elsewhere, as increased afterburn, higher
losses or changes in the radial temperature profile.
Circulation problems can arise simply due to an
increase in the catalyst circulation rate due to low
regenerator temperature, which in turn can be caused
by a drop in Ecat activity or processing light feed. The
easiest ways to increase regenerator temperature
quickly if the bed temperature is low are to increase
catalyst additions and, if possible, recycle slurry oil.
Poor cyclone function can result in changes in the
particle size of circulating catalyst, in particular a loss of
0-45 micron fines. Catalyst fines are critical for good
fluidisation. In case of a loss of fines, troubleshooting is
needed to find the root cause. Possible corrective actions
include increasing the fresh catalyst fines content, recy-
cling fines from a third stage separator or using a high
fines content fluidisation enhancing additive.
Other potential issues from the regenerator include
faulty bed level readings, or refractory spalling (typical
in excessive thermal cycles, repeated shutdowns) and
plugging the slide valve.
Catalysis 2016 5
Topsoe’s new HyBRIM™ catalysts for FCC pretreatment

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Q What regular checks for nickel and vanadium contamination
should we make on our FCC equilibrium catalyst and how
should we respond to rising levels of contamination?
A Melissa Clough, Technology Specialist, Refining Catalysts,
Melissa.Clough@basf.com, Rebecca Kuo, Technical Service
Engineer, Refining Catalysts, Rebecca.Kuo@basf.com and
Vasilis Komvokis, Technology Manager, Europe, M. East &
Africa - Refining Catalysts, Vasilis.Komvokis@basf.com, BASF
Catalysts
Nickel (Ni) and vanadium (V) contaminants that come
with resid FCC feeds decrease activity of the FCC cata-
lyst and promote unwanted dehydrogenation reactions
in the unit. The dehydrogenation activity of typical
contaminant metals can be expressed in terms of
equivalent Ni as: Ni + V/4 + Fe/10 + 5Cu - 4/3Sb.
While V only has one quarter of the dehydrogenation
effect as Ni, it interacts with sodium (Na) to destroy
the zeolite under regenerator conditions. Because resid
feeds typically contain higher levels of Ni and V
compared to other metals, it is important to continu-
ously monitor the Ni and V levels on the equilibrium
catalyst (Ecat) through the periodic analytical results
that catalyst manufacturers provide. As a rule of
thumb, Ecat Ni tends to be a concern above 500 ppm
and Ecat V above 1000 ppm – of course, this number
depends on the individual FCC unit. Adding fresh
catalyst can mitigate effects of Ni and V, but there are
also alternative methods.
There are numerous ways to respond to rising levels
of Ni:
1) Catalyst manufacturers use a specialty alumina that
is incorporated into the catalyst particle. A portion of
the Ni that interacts with the specialty alumina is
passivated. However, because both Ni and alumina are
immobile, there is no guarantee that all of the Ni will
contact the alumina for passivation.
2) When Ecat Ni goes above 1000 ppm, refiners can
inject antimony (Sb) into the feed. Sb forms an alloy
with Ni, which effectively passivates the Ni.
3) BBT, discussed later.
There are also numerous ways to respond to rising
levels of V:
1) All fresh catalysts have residual Na from manufac-
turing that can contribute to zeolite deactivation in
conjunction with V. In BASF FCC catalysts, this resid-
ual Na is at an industry low, typically 0.15-0.2 wt%
due to the high accessibility of the zeolitic active sites
and a unique series of ion-exchange/calcination steps
2) Vtraps, which can be utilised to mitigate V from
migrating to the catalyst particle and permanently
destroying the Y-zeolite. These should be used when
seeing sharp drops in activity, higher coke and H2, and
limitations on the wet gas compressor. The amount of
Vtrap should be tailored to the specific refinery, and
takes into account V levels, sulphur levels, as well as
base catalyst technology. The economic value of imple-
menting Vtrap technologies includes increased unit
conversion, and the possibility of processing more
resid feeds in the FCC.
To deal with the high Ni challenge, BASF has devel-
www.eptq.com
oped the new Boron Based Technology (BBT) platform.
In BBT the enhanced Ni tolerance is achieved by a
boron compound that is loaded on a special inorganic
support introduced into the catalyst. Under FCC unit
conditions this boron compound is mobile and will
seek out and passivate Ni. Combining the novel use of
boron with a pore architecture that minimises diffu-
sional limitations of heavy feed molecules, this new
technology allows the lowest H2 and coke yields
coupled with higher liquid hydrocarbon yields. The
performance of BoroCat, the first catalyst from the BBT
platform, in commercial FCC unit trials resulted in
significantly lower H2 and coke yields, improved
liquid product yields and improved unit profitability.
In summary, active Ecat metals management is key
to a successful FCC operation. Depending on the FCC
objectives and constraints, numerous avenues are
available at dealing with contaminant Ni and V from
feed.
Q Is there an alternative to inert entry procedures for
catalyst unloading?
A Romain Vial, Eurecat France, Reactor Management Services
Product Manager, r.vial@eurecat.fr
In most of cases, severe catalyst agglomeration contrib-
utes to long lasting inert entry.
Wetting the catalyst prior to unloading is an alterna-
tive with several downsides:
• Channelling could occur, which would lead to a
non-wetted section inside the reactor and thus associ-
ated self-heating risks and safety issues during
subsequent unloading
• Down the road, extra processing costs such as liquid
effluent destruction, lower metal reclaim value of
spent catalyst, or unexpected pre-processing of catalyst
prior to regeneration might occur
• Depending of the wetting agent (for instance, soda
ash water) the catalyst might not be suitable for
regeneration
• Wet unloading is typically slower than dry
unloading.
Catalyst agglomeration usually has three immediate
severe consequences:
• A potentially risky situation with the presence of a
pillar of catalyst or cavern that creates unsafe working
conditions
• Severe planning deviation and associated increase in
time spent under inert for jack hammering or
vacuuming
• Use of destructive techniques which means that cata-
lyst will no longer be suitable for regeneration.
Eurecat has developed CarboDump, an innovative
technology to address these catalyst agglomeration
issues during unloading.
The principle is based on the rapid expansion of
gaseous CO2 into the catalyst bed initiated from
outside of the reactor. The expansion removes the
weak links due to dust, coke, scales or polymers creat-
ing agglomeration of the particles. With free flowing
Catalysis 2016 7
 properties retrieved, efficient and fast dry gravity
dumping can be resumed.
CarboDump can be used to start gravity dumping
instead of rodding, to break mountains or stalagmites
of agglomerated catalyst, or to collapse caverns, as
well as to lower the angle of repose and consequently
reduce the volume of catalyst to be dug out. In very
severe agglomeration situations, CarboDump can be
used to replace jack hammering inside the reactor as
an assistance to vacuuming.
CarboDump will bring three main advantages to the
end user: minimise the amount of time spent in an
inert; a secure working area; and maximise catalyst
recovery for further reuse. In that regard, it could be
considered as a good alternative to time-consuming
inert entry procedures.
Q Is there a single-bed catalyst solution for hydrotreating a
blend of straight run gas oil and light cycle oil? If not, what’s
the alternative?
A Andrea Battiston, Global FCC & Coker Additives Specialist,
Albemarle, Andrea.Battiston@albemarle.com
Blending straight run gas oil (SRGO) with light cycle
oil (LCO) introduces a technical penalty for hydrotreat-
ing operations that typically results in higher operating
temperature and reduced hydrogen outlet pressure.
This is due to the higher inhibition effect by nitrogen,
the higher content of aromatics to saturate, in particu-
lar of polynuclear aromatics (PNA), and the larger
presence of refractory sulphur species in the LCO
stream. As a consequence, catalyst selection requires
particular care.
While in principle it is possible to apply a single-bed
catalyst solution (defined here as a single-catalyst
system, neglecting the guard bed section) for treating a
SRGO/LCO blend, that is most often not the best solu-
tion. In fact, applying a combination of catalysts allows
positioning of the most suited catalyst type in each
zone of the hydrotreater, for example to boost (hydro-
genation) activity locally or/and to improve overall
stability. This approach leads in general to a more effi-
cient operation, which can be translated into a higher
LCO intake, higher LCO final boiling point (FBP) and/
or better product properties and higher volume swell,
which all provide improved economics for refiners.
For designing the optimal reactor catalyst loadings
for, among others, applications that include treating
SRGO/LCO blends, Albemarle has developed and is
continuing to optimise Stax, its proprietary kinetic
engine and loading optimisation technology. Through
the application of Stax, Albemarle engineers can design
the right loading scheme for each situation by captur-
ing synergistic effects at work in the reactor.
All considered, from an operation’s perspective there
is a case where applying a single catalyst system for
SRGO/LCO blends can be the preferred solution,
namely for low or low-to-medium pressure hydrotreat-
ers with high operating temperature, where fully
exploiting hydrogenation activity is not possible. This
8 Catalysis 2016
applies in particular to hydrotreaters that operate at a
high space velocity and/or with challenging SRGO/
LCO blends. For this kind of unit, stability in operation
can become particularly critical and the best choice can
be a single CoMo catalyst solution with moderate HYD
selectivity in the whole reactor. Albemarle catalyst
solutions for such applications are KF 757, KF 758 or
KF 780.
In the other cases, using an optimised combination
and positioning of catalysts is by far the best solution.
In all instances, Stax can provide the answer with
respect to the optimal catalyst loading to maximise
operating profit over the whole cycle.
A Rainer Rakoczy, Global Product Manager Fuel Upgrading
Catalysts, Clariant, rainer.rakoczy@clariant.com
There is a narrow range of operation where a single
bed catalyst solution can work for hydrotreating a
blend of straight run gas oil and LCO. LCO as a blend-
ing component for hydrotreater feeds can offer volume
advantages and some benefit for cold flow improve-
ment (CFI). But there are considerations to keep in
mind and these can have effects on the hydrotreater
operation.
LCO as a blending component
for hydrotreater feeds can
offer volume advantages and
some benefit for cold flow
improvement
Due to high olefins and aromatics concentrations in
LCOs, exotherms can pose problems, especially in
single bed hydrotreating reactors. As the FCC process
allows for a lot of flexibility in the feed, the composi-
tion of LCO can fluctuate. This can push the design
limits of the process, which, as is the case with any
hydroprocessing, is already stressed. Additional
concerns about the heat limitations of the process and
the availability of hydrogen restrict LCO as a blending
component. This is true even in multi-bed hydrotreat-
ers with the best options for quench.
In order to achieve the desired results, an intelli-
gently designed, mixed catalyst loading of the single
bed reactor combined with a recycle of light product
fractions in small amounts, such as wild naphtha, may
help. A detailed evaluation of equipment capabilities
and blended feedstock properties by application,
process engineering and catalyst supplying partners
can help to identify an appropriate solution.
A Allan K Uldam, Product Manager, Refinery Business Unit,
Haldor Topsoe A/S
Hydroprocessing of blends of straight run gas oil and
light cycle oil for the production of ultra-low sulphur
diesel is sometimes feasible in single-bed reactor
design.
www.eptq.com
 Flexibility

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The ISOSLURRY catalyst development program at Chevron Lummus Global has benefited from decades of LC-FINING
technology and residuum hydroprocessing catalyst development experience and expertise. This superior slurry catalyst
used with LC-SLURRY technology can handle even the most challenging of feedstocks, including SDA-tar, while consistently
maintaining stable conversion of nearly 97%. Not only is this unique slurry catalyst promoted
and preactivated for superior hydroprocessing performance, it is formulated for easy handling
and injection. Use ISOSLURRY catalyst if you want the highest yields of superior quality liquid
products from the bottom of your barrel.

Email techma@chevron.com to get the strength, flexibility, and performance you need to
meet the challenges of vacuum residuum hydroprocessing and increase your bottom line.
 One deciding factor for splitting the catalyst into
multi-bed reactor designs is the exotherm, which often
needs to be limited to around 40°C/70°F or sometimes
lower. Another factor is the maximum bed height
which often is limited to around 10 m/33 ft.
Modern high performance reactor internals will
secure optimal inter-bed mixing, quenching, and redis-
tribution in multi-bed designs. For single bed solutions,
optimal distribution of liquid and gas is also important
in order to maximise catalyst and unit performance.
Q We are planning to process an imported crude and
understand that we need to be aware of arsenic and
phosphorus contamination of catalyst. At what level of arsenic
and phosphorous should we take action – and what action?
A Michael T Schmidt, Product Manager, Refinery Business
Unit, Haldor Topsoe A/S
Both arsenic and phosphorus are in the category of the
most harmful catalyst contaminants – actually signifi-
cantly more harmful than silicon, nickel, vanadium,
and iron. The problem with arsenic is that it very effec-
tively titrates the active catalytic sites by forming CoAs
and NiAs, thereby permanently damaging the catalyst.
Phosphorus, on the other hand, will deposit on the
catalyst’s alumina carrier, blocking access to the active
sites. In some cases, it is seen that phosphorous can
coat the entire catalyst particle’s exterior, which will
destroy all transportation of reactants into the cata-
lyst’s pore system.
To mitigate the severe effect of arsenic and phospho-
rus, it is important to install guard catalysts on top of
the high-active main catalyst. Topsoe commands very
effective guard catalysts for trapping particularly arse-
nic and phosphorus. These guard catalysts are
recognised to have an open alumina pore structure,
enabling diffusion of large molecules into the catalyst
pellet. The arsenic guard is also designed with a high
load of nickel, which will secure a high capacity for
trapping arsenic from the feed.
As a rule of thumb, it is advisable to consider these
guard products, if the feed content of arsenic exceeds
50 wt ppb, and the feed content of phosphorous
exceeds 1 wt ppm. The unit throughput (or space
velocity in the reactor) is of course equally important
for the amount of contaminants being introduced.
A Umakant Joshi, Process and Development Engineer,
Crystaphase, umakant.joshi@crystaphase.com
The arsenic target should be zero. If arsenic reaches the
main bed, it can bind with nickel in the catalyst to
form nickel arsenide, poisoning the catalyst. Raising
the bed temperature to compensate for loss of activity
can make things worse by actually accelerating deacti-
vation. Even at concentrations as small as 5 parts per
billion by weight (ppbw), these effects can be
significant.
To protect the catalyst from arsenic poisoning, make
sure the feedstock purification system above your
main bed collects arsenic. The best approach will
10 Catalysis 2016
depend on an analysis of your feedstock and your
reactor. With the right system design, you can catch
arsenic before it hits your catalyst, without limiting
throughput or contributing to pressure drop. In our
experience with poison control systems at Crystaphase,
we find an ActiPhase based system picks up arsenic
particularly well, removing it from the feedstock and
preventing arsenic problems before they jeopardise
reactor stability.
Phosphorus problems take more than one form and
have a variety of origins. Above a concentration of 0.5
ppmw, how much you can tolerate and how you
should handle it depends on how it gets there.
Phosphorus occurs naturally as phosphates in many
oil deposits, Western Canada being one example.
Phosphates are also introduced to improve viscosity in
fracturing fluids, to limit oxidation and wear in lube
oils, and to inhibit corrosion when handling high TAN
crude. As a soluble foulant, phosphorus often makes it
from these sources all the way to the main bed, the
most expensive place to cause damage.
Like arsenic, phosphorus poisons the active sites of
the catalyst, shortening catalyst life, cutting cycle
lengths, and limiting reactor performance. If phospho-
rus is simply poisoning the catalyst, active poison
control in the feedstock purification system above your
main bed is a straightforward preventative.
But phosphorus is not only a poison; it has the
added dimension of becoming a particle. Soluble phos-
phorus compounds, like diphosphate ester, can
precipitate out of the feedstock in the main bed, then
accumulate as particles, contributing to pressure drop.
The way to handle this is to trigger precipitation above
the main bed, within a filtration system designed to
collect the resulting particles while maintaining opti-
mal throughput.
As with arsenic, the best solution will depend on the
results of feedstock and reactor analysis. But with
phosphorus, the lab work is doubly important, as you
must determine whether the problem is poisoning,
precipitation, or some combination. Our tech service
team has recommended feed purification systems
based on ActiPhase in such scenarios, for its properties
as both precipitant and collector.
So the analysis will tell, but it sounds like your feed-
stock purification solution will require active control
for both arsenic and phosphorus to protect the value of
your catalyst and maintain optimal performance in
your reactor.
A Melissa Clough, Technology Specialist, Refining Catalysts,
Melissa.Clough@basf.com, Rebecca Kuo, Technical Service
Engineer, Refining Catalysts, Rebecca.Kuo@basf.com and
Vasilis Komvokis, Technology Manager, Europe, M. East &
Africa - Refining Catalysts, Vasilis.Komvokis@basf.com, BASF
Catalysts
Phosphorus on fresh FCC catalyst is about 0.05-0.08
wt%. Phosphorous is not inherently poisonous to the
FCC catalyst. It is, however, a contaminant for catalysts
in hydroprocessing. Metal phosphates in feed are
possible, so the presence of phosphates could indicate
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 Global leader in
hydroprocessing offering
a complete range of
catalysts and services

Advanced Refining Technologies

7500 Grace Drive
Columbia, MD 21044 USA
+1.410.531.4000
www.artcatalysts.com

More than 70 years of

FCC application expertise
• 100+ FCC experts stationed • Flexible manufacturing enables
around the globe rapid commercialization of
• Customized technical support, innovations
including unit optimization and • Grace’s process minimizes
onsite troubleshooting risk, maximizes refiner
• Industry’s broadest portfolio profitability
supported by global R&D team

www.grace.com
Grace® 7500 Grace Drive, Columbia, MD 21044 USA | +1 410.531.4000 | www.grace.com | Grace®, ART® and
TALENT TECHNOLOGY TRUST™ are trademarks, registered in the United States and/or other countries, of
W. R. Grace & Co.-Conn. Copyright © 2016 W. R. Grace & Co.-Conn. All rights reserved.
 higher metals, such as Ni and V, which are detrimental
to FCC catalyst performance.
Arsenic is a notable catalyst contaminant in the
hydroprocessing step, but not for FCC catalysts. For
FCC operations, arsenic on fresh catalyst (from REO
and the kaolin clay) is very low, typically between 0.5
and 7 ppm, well below any environmental regulations
for handling. Arsenic levels on FCC Ecat can range
from 50-600 ppm. However, pure arsenic is volatile at
FCC conditions and does not stay on the catalyst.
Arsenic hydride (AsH3), or arsine, does end up in the
C3= stream, on which there is usually an arsenic limit/
specification. Some FCCs use arsine traps to achieve
chemical grade propylene. Additionally, BASF makes
several purification media that will remove arsine and
other contaminants from a propylene stream. The pres-
ence of rare earths can lead to errors in the
measurement of arsenic, resulting in much higher
levels (10x) than correct amounts. Measurements
should be done by a certified environmental lab.
A Rainer Rakoczy, Global Product Manager Fuel Upgrading
Catalysts, Clariant, rainer.rakoczy@clariant.com
It goes without saying that for any refinery or petro-
chemical plant there is a general operating limit for
impurities. Contaminant limits differ by catalyst type
and manufacturer, which should be discussed with
each catalyst supplier for any process change.
We have found many cases where operators did not
recognise that they were running with phosphorus
contamination downstream in their heavier hydrocar-
bons. Some anti-corrosion chemicals contain
phosphorus as an active ingredient that can find their
way into the bottom fractions. This is especially true in
the CDU section, but also in other downstream
equipment.
Even in trace amounts, arsenic will manipulate metal
function (hydrogen transfer) and acidity (cracking or
other conversion properties) on the catalyst. There are
three ways to mitigate this issue:
• Dedicated chemicals during desalting at the very
beginning of the refinery
• Having the right metal traps installed at the turn-
around or catalyst change-out
• Installing the appropriate active grading of catalyst
in the hydrotreaters.
Having a catalyst supplier that can offer assistance in
all of these areas is ideal, such as Clariant, which offers
desalting chemicals through its Oil and Mining
Services and catalyst active grading and metal traps
through its Catalyst division. In the end, the most effi-
cient solution comes from working together with the
crude section and operations to identify the appropri-
ate mitigation strategy for your operation.
A Robert Bliss, Global Hydroprocessing Specialist, Albemarle,
Robert.Bliss@Alemarle.com
Arsenic concentrations in crude oils vary significantly
across the globe from nil to as high as 1 ppm (1000
ppb) and crudes containing high levels (>300 ppb) are
typically associated with specific geographical produc-
12 Catalysis 2016
tion regions. Some of the regions known to have the
highest concentrations of arsenic include the Canadian
Alberta Oil Sands bitumen deposits, the Venezuelan
Orinoco Belt extra heavy crude deposits and Russian
crudes from the Western Urals.
Arsenic compounds found in petroleum are primar-
ily derived from aryl and alkyl substituted arsine.
These organoarsenic compounds can vary greatly in
structure and molecular weight; as a result they
distribute evenly across all petroleum distillate frac-
tions (naphtha, diesel, VGO) and negatively impact
hydroprocessing units across all application segments
(NHTs, KHTs, DHTs, CFHTs, HCUs).
Depending on the hydroprocessing unit’s operating
conditions, arsenic concentrations as low as 10 ppb
may require specialty guard catalysts to protect the
activity of the main bed catalyst. This is because arse-
nic is one of the most severe poisons for base metal
(for example, NiMo, CoMo) hydroprocessing catalysts
(HPC). Studies have shown activity losses exceeding
50% at arsenic loadings as low as 0.8 wt% on catalyst.
This is very severe compared to a moderate poison
such as silicon where catalyst activity losses do not
exceed 50% until loadings in excess of 8 wt% on cata-
lyst are realised. Arsenic is a permanent poison; once it
is on the catalyst it cannot be removed and it will
Arsenic is a permanent poison;
once it is on the catalyst it cannot
be removed and it will prevent
catalyst regeneration at loadings
as low as 0.3 wt% on catalyst
prevent catalyst regeneration at loadings as low as 0.3
wt% on catalyst.
Arsenic bonds directly with nickel and cobalt
promoter atoms on molybdenum disulphide (MoS2)
HPC active sites, forming nickel arsenides (NiAsy) and
cobalt arsenides (CoAsy). Once formed, these arsenide
compounds do not destroy the MoS2 structure however
they do alter its electronic state, resulting in substantial
catalyst deactivation. Further, it has been shown that
arsenic has a higher affinity towards nickel than cobalt.
Thus catalysts designed with larger amounts of nickel
will ‘trap’ larger amounts of arsenic.
Because catalyst deactivation from arsenic poisoning
is so severe, it is critical in hydroprocessing applica-
tions known to have arsenic contaminated feedstocks
to employ an arsenic specific trapping catalyst layer in
the top bed guard system to protect the main bed HPC
below. Albemarle has extensive experience in the
design and application of arsenic traps; our latest two
arsenic traps include KG 8, commercialised in 2011,
and KG 16-MAC (Maximum Arsenic Capture),
commercialised in 2014.
Phosphorus in crude oil and in petroleum distillate
fractions originates from many sources. For example,
www.eptq.com
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trademark of W. R. Grace & Co.-Conn. © 2016 W. R. Grace & Co.-Conn.
 Gas Gas + feed
Introduce
spiking agent
Temperature
1. 2. 3.
Begin catalyst Introduce Begin first stage
drying oil and soak sulphiding
Time, hours
Figure 1 In-situ spiked sulphiding scheme (with a spiking agent)
sources can include innate organic phosphorus
compounds such as phosphatides (also an issue with
‘renewable’ feedstocks), dialkyl phosphate esters in
well stimulation gelling agents, phosphorus based drill-
ing fluids and phosphorus based corrosion inhibitors
(for instance, tributly phosphate, metal phosphates or
dithiophosphates). Like arsenic, concentration of phos-
phorus in crude oil and in petroleum fractions varies
significantly, from nil to as high as 1 ppm (1000 ppb).
Phosphorus compounds found in refinery feedstocks
are primarily derived from organophosphates or phos-
phate esters. These phosphates can vary greatly in
structure and molecular weight; as a result they too
can distribute evenly across all petroleum distillate
fractions (naphtha, diesel, VGO) and negatively impact
hydroprocessing units across all application segments
(NHTs, KHTs, DHTs, CFHTs, HCUs).
Depending on the hydroprocessing unit’s operating
conditions, phosphorus concentrations as low as 10 ppb
may require specialty guard catalysts to protect the activ-
ity of the main bed catalyst. This is because phosphorus
is a severe poison for hydroprocessing catalysts (HPC).
Studies have shown activity losses exceeding 50% at
phosphorus loadings as low as 2 wt% on catalyst.
Phosphorus is a permanent poison; once it is on the cata-
lyst it cannot be removed and it will prevent catalyst
regeneration at loadings as low as 1 wt% on catalyst.
Phosphorous compounds will decompose in the
hydroprocessing reactor environment and the resulting
phosphates will deactivate catalyst by adsorbing onto
the catalyst’s alumina support. After appreciable accu-
mulation of the adsorbing phosphates mass transfer
will become limited and eventually complete blocking
of pores will occur (pore mouth plugging). This mech-
anism is more pronounced with high temperature/
high pressure operations and it will have a greater
impact on small mean pore diameter sized main bed
catalysts.
14 Catalysis 2016
Gas + feed + spiking agent Gas + feed
Stop spiking agent
injection
H2S
breakthrough
4. 5.
Begin second stage Introduce design feed
sulphiding and begin ramp to
SOR conditions
Because catalyst deactivation from phosphorus
poisoning is so severe, it is critical in hydroprocessing
applications known to have phosphorus contaminated
feedstocks to employ phosphorus specific trapping
catalyst(s) in the guard bed system to protect the main
bed HPC below. Albemarle has extensive experience in
the design of catalyst guard systems to mitigate the
impact of phosphorus.
The best way to determine which arsenic and/or
phosphorus traps and the quantity required to address
the loss of activity in your unit is to utilise the applica-
tion knowledge of your Albemarle technical service
team to design a guard catalyst system solution that
will exceed your objectives. Albemarle also offers
analytical services to quantify the level of arsenic/
phosphorus contamination in your feedstock.
Q What steps should I pay particular attention to in the
pre-sulphiding process to obtain best performance from
hydroprocessing catalyst?
A Barbara Slettenhaar, Technical Consultant, Hydroprocessing
Catalysts, Albemarle, Barbara.Slettenhaar@Albemarle.com
Catalyst sulphiding is the conversion of inactive
metal-oxides on the catalyst into active metal-sulphide
slabs. An example of a reaction taking place is:
MoO3 + H2 + 2H2S MoS2 + 3H2O + heat
The sulphiding reaction requires the presence of H2
and H2S. The most common procedure is to apply a so
called liquid sulphiding procedure where H2S is
formed either by thermal decomposition of a spiking
agent such as DMDS or TBPS, or by hydrodesulphuri-
sation of the feedstock itself. The latter, which is
referred to as ‘feed-only sulphiding’, reduces safety/
health issues and omits the handling costs of a spiking
www.eptq.com
 Catalyst innovation. Commercial
experience. Committed to results.

ExxonMobil leverages its

research and development
efforts to support a program
of continuous improvement
in catalyst performance.

Innovation process ExxonMobil* catalyst portfolio

Value chain Technology area Process Catalyst offerings

Styrenics Alkylation EBMaxSM EM-3300, EM-3700
Phenolics Alkylation Cumene EM-5100, EM-5510
XyMaxSM, XyMaxSM-2,
Xylene isomerization EM-4600, EM-4410
EMHAI, AMHAISM
Polyesters & fiber Transalkylation TransPlus NG
SM
EM-1100
Disproportionation PxMaxSM EM-2300
Olefin removal OlgoneSM EM-1850
FCC naphtha desulfur-
SCANfining™ RT-225
ization
Fuels Benzene reduction BenzOut™ EM-8650
Octane enhancing OCTGAIN™ EM-8000
Diesel dewaxing MIDW ™ EM-6320
Fuels/lubes Hydroprocessing RHC, MPHC, LHDC EM-7400 Series
Lubes dewaxing MLDW ™ EM-7100
™
Hydro isomerization MSDW EM-7320
Lubes
MWI™ EM-7820
Hydrofining MAXSAT™ EM-7520
Synfuels Methanol to gasoline MTG EM-9000

* ExxonMobil catalysts are manufactured by ExxonMobil Catalysts Technologies, LLC, an affiliate of ExxonMobil.

Contact us for more information: www.catalysts-licensing.com

ExxonMobil, the ExxonMobil logo, the interlocking “X” device and all product names herein are trademarks of Exxon Mobil Corporation.

L1015-060E49

5088 - Updates to Catalyst AD_v4.indd 1 19/10/15 15:53

 Risk of potential deviations during an in-situ sulphiding using DMDS
Step Deviation
Drying Temperature ramp too fast
Soaking dP too high after first feed introduction
Cracked material in startup feed
Feed with high FBP (>380°C)
Feed containing free water
Product containing sediments on recycle
Feed rate too low
First stage Inject DMDS below decomposition T
sulphiding
dT >15°C or peak temperature >245°C
Premature breakthrough
Prolonged failure of DMDS pump
% H2 <60%
Second stage T ramp too fast
sulphiding
H2S <5000 ppm Risk of running out of reactant
Not enough spiking agent
Table 1
agent. Albemarle Stars catalysts, as an example, can be
started up applying either of the above sulphiding
procedures.
Although each catalyst vendor will have their own
start up procedure, typically five steps can be distin-
guished (see Figure 1): drying, wetting with oil, low
temperature sulphiding, high-temperature sulphiding,
and start of normal operation.
When the sulphiding is completed, the start-up feed
will slowly be replaced by the design operation feed.
Since freshly sulphided catalyst is particularly sensitive
to coking, we recommend avoiding cracked material
during the first three days on stream. Operating at
lower severity in the beginning is beneficial for catalyst
life, e.g. by using relatively easy feeds to reduce oper-
ating temperatures, by avoiding the presence of coke
precursors and by maximising H2/oil ratios.
A Rainer Rakoczy, Global Product Manager Fuel Upgrading
Catalysts, Clariant, rainer.rakoczy@clariant.com
Performing pre-sulphiding properly is the key for opti-
mum performance and lifetime of any non-precious
metal hydrotreating catalyst. Using the right feed for
the recommended amount of time during start-up can
save months in cycle lifetime. It is recommended to
work with the catalyst supplier to have pre-start-up
meetings and, ideally, be present during start-up.
16 Catalysis 2016
Risk Action
Re-condensation of water on cold catalyst Reduce temperature ramp
further downstream ->risk of metal leaching
Compressor trip Begin with reduced feed rate and
increase as temperature increases
Coke formation and hence activity loss Avoid using cracked feedstock. Check
quality of feed before startup
Risk of coke formation and hence activity loss Adjust cutpoint or use alternative feed
Risk of metal leaching and hence activity loss Change to dry feed
Sediment deposition resulting in pressure drop Keep in once through mode and send
product to slops
Non-optimal wetting and risk of Increase feed rate (fresh or sediment
channeling/maldistribution free recycle)
DMDS remains in reactor and undecomposed Increase T, stop DMDS injection
DMDS may lead to high dT when T is increased
Reaction might go too fast Reduce DMDS rate
Low-temperature sulphidation not completed Hold temperature and reduce DMDS rate
High T and no H2S, risk of reduction Reduce T
Insufficient ppH2, potential coke formation Purge and increase MUG rate or purity,
or reduce spiking agent rate
Sulphiding reaction too fast, decreasing Monitor H2S and T ramp
H2S<5000 ppm results in incomplete sulphiding
Stop T ramp until H2S outlet >5000 ppm
Incomplete sulphidation Adjust spiking rate or finish the
sulphiding using feed in a once
through mode
It is advised not to apply cracked feed stocks and to
limit the recycling of liquid products, even during the
heat-up sequence. Also, it is important to ensure suffi-
cient sulphur availability for the entire time and that
H2S formation is monitored properly. There are
contractors that specialise in supplying specialised
equipment, beyond test tubes, that can help with this
process.
A Reinder van Bruggen, Area Sales & Totsucat Product
Manager, Eurecat, r.vanbruggen@eurecat.fr
To obtain best performance from hydroprocessing cata-
lyst, you should make sure that all risks of catalyst
malperformance are eliminated. This can be achieved
by loading catalyst that is already activated (Totsucat),
so no in situ sulphiding is required when starting up
the unit.
This eliminates the risk of catalyst reduction (due to
exposure to hydrogen at high temperature), loss of H2S
(leading to insufficient activation) in case of interrup-
tion of the in situ sulphiding, and catalyst damage in
case of temperature runaway from the activation
exotherm.
Using already activated catalyst also eliminates the
need to manipulate DMDS or similar chemicals, gener-
ation of H2S, the need to monitor it and the risk of
poisoning downstream units with H2S.
www.eptq.com
Q What types of catalyst, in what sort of condition are worth
sending for precious metals recovery rather than landfill? Or
should everything go for recovery operations?

A Uwe Duerr, Head of Sales EMEA/CIS Ethylene/Derivatives,

Clariant, uwe.duerr@clariant.com
The recovery of precious metals is important in order
to use these scarce resources in a sustainable way. In For
technology
general, recovery can pay out already with catalysts
that have a relatively low precious metal content.
Typically, the catalysts with the lowest content hold
about 200-300 ppm of precious metals. Whether, in solutions
your specific case, it is economically worthwhile to
send these to recovery depends on a number of factors:
• Precious metal content of the spent catalyst (as
mentioned above)
• Overall cost of the recovery service
• Condition of the catalyst. Contamination with toxic
agents or organic solvents can make the recycling
process more expensive.
• Precious metal recovery rate achieved by the
reclaimer
• Market price fluctuations of precious metals. These
have been very volatile in the recent years.
As these factors may vary greatly, we recommend to
talk to a specialised precious metal reclaimer, such as
Heraeus Precious Metals, who can provide you with a ...certified -
independent -
detailed cost-revenue calculation.

Q Is there a catalytic alternative to thermal incineration worldwide...

that involves no sulphur emissions at the last stage of the

think
sulphur plant?

EDELHOFF.
A Niklas Bengt Jakobsson, General Manager, New
Environmental Solutions, Haldor Topsoe A/S
There is a catalytic alternative to thermal oxidation as
the last step in a Claus plant. The solution that would
minimise the sulphur emissions would be to apply a
catalytic oxidation stage that selectively converts all Life Support Systems
sulphur components to SO2 which then can be Vacuuming Technologies
removed very efficiently using a caustic scrubber or a Dense Loading Units
hydrogen peroxide scrubber. The hydrogen peroxide Tu b u l a r E q u i p m e n t
scrubber produces dilute (50%) sulphuric acid and can
be attractive when there is a local offtake of sulphuric
acid. Topsoe supplies this technology, named SMC,
which will also convert residual hydrogen and carbon
monoxide in the gas.

A Rainer Rakoczy, Global Product Manager Fuel Upgrading

Catalysts, Clariant, rainer.rakoczy@clariant.com
It is possible to remove almost all sulphur components
using a catalytic solution. Drop-in solutions compatible
with most commercially available sulphur removal tech-
nologies exist that have been tested and proven for
Edelhoff Technologies USA LLC
decades. These operate upstream of the sulphur unit and Houston, Texas · USA
independent of Claus catalysts. The catalysts are capable
Edelhoff Technologies GmbH
of nearly complete conversion of sulphur compounds at Iserlohn, NRW · Germany
nearly ambient pressure and above 200°C, offer low www.edelhoff-technologies.com
initial pressure drop, are suitable for cold start-up, and
are a carefree solution to sulphur emissions control.

www.eptq.com Catalysis 2016 17

Process Notes
Maximize Reliability in
Grassroots Crude Units
Crude unit operators are far too familiar with a long list
of crude unit reliability problems including fouling in
heat exchangers and fired heaters, poor desalting, cor-
rosion of piping and equipment, and coking in the vac-
uum column wash zone. Many millions of dollars have
been spent fighting these problems, yet they continue
to force unplanned shutdowns with depressing regu-
larity.
Revamps must address reliability issues, but project
scope is hindered by the limitations of existing equip-
ment. Grassroots design of crude and vacuum units
presents an opportunity to get everything right the first
time. Here are a few tips for designing a reliable and
profitable crude/vacuum unit.
HEAT EXCHANGER AND HEATER FOULING
High velocities in heat exchanger tubes produce high
shear at the walls, preventing foulants from accu-
mulating. High shell-side velocities, coupled with ex-
changer designs that minimize dead zones in the flow,
eliminate shell-side fouling. In fired heaters, high mass
fluxes maximize wall shear, shorten residence time,
and lower wall film temperatures, all of which reduce
coking. Furthermore, reliable heaters must have cor-
rectly sized burners with proper burner-to-burner and
burner-to-tube spacing.
3400 Bissonnet St.
Suite 130
Houston, TX 77005, USA
Crude units can be designed for reliability.
DESALTING
Desalter size is highly dependent on crude blend due
to dramatic variation in required centerline velocity.
A unit must be designed with the flexibility to care-
fully control desalter temperature, which can range
from 110°C to 150°C, by shifting heat from upstream to
downstream of the desalters. Vendors are often judged
on cost alone, which results in minimum sizing for the
design crudes and rates. Carefully consider whether
long-term crude trends will soon render these desalt-
ers inadequate.
CORROSION
In grassroots design, be realistic about metallurgy. Be-
cause modern refineries do not run a steady diet of the
same crude, consider the sulfur and TAN numbers of
potential crudes outside the unit’s design blend. Chron-
ic corrosion issues, or the inability to process high-mar-
gin opportunity crudes, will quickly overshadow the ini-
tial savings from choosing too low of a metallurgy.
VACUUM COLUMN WASH ZONE COKING
Wash zones are not for fractionation, they are for
de-entrainment! Pursuing fractionation efficiency by
specifying a deep bed with small crimp packing is a
recipe for rapid coking. The correct choice of packing
combined with the right wash rate and good distribu-
tion will properly de-entrain while preventing coke for-
mation.
+1 (713) 665-7046
info@revamps.com
www.revamps.com
 Guarding against contaminants
Analysing spent hydroprocessing catalyst underpins the development of guard
bed catalysts to counter contaminants
MICHAEL SCHMIDT Haldor Topsoe A/S
HENRIK RASMUSSEN Haldor Topsoe Inc
A
very important parameter for
the cycle length of a hydro-
processing unit is the
deactivation rate of the installed
catalyst. The deactivation of a
hydrotreating catalyst can be coke
induced and contaminant induced.
Coke deposition is to a large extent
controlled, but also dictated, by the
unit operating regime (temperature,
hydrogen availability, residence
time and partial pressure of hydro-
gen). This will normally cover most
middle distillate units making
ULSD or lighter products.
However, in units processing heav-
ier feedstocks like vacuum gas oil
(VGO), heavy coker gas oil
(HCGO), deasphalted oil (DAO), or
even heavier cuts, the refinery
normally faces a dual type deacti-
vation. The coking reactions here
are even more significant because
the feedstock is heavy and contains
lots of aromatic coke precursors in
the high boiling fraction. But heavy
feedstocks will often also contain a
significant amount of heavy metals
and other contaminants. In particu-
lar, this includes nickel, vanadium,
iron, silicon, arsenic, phosphorus,
calcium and sodium. These contam-
inants are present in processed
feedstocks at ppm or even ppb
levels, but the effect is significant.
Following a non-reversible path-
way, heavy metals will be
deposited on active catalyst follow-
ing different mechanisms. The
outcome is that activity is lost
permanently and will thus not even
be regained during catalyst
regeneration.
Topsoe researchers have within
the past few years analysed and
characterised a huge number of
www.eptq.com
S Sulphur
Vanadium
Nickel
Aromatic rings S
Naphthenic rings
S S
S
S
S
S
S S
S S
S S S
S
S
S
S
Figure 1 Large porphyrin-like asphaltene molecule
spent catalysts retrieved from (see Figure 1). Generally, the metal-
industrial hydrotreater units oper- lic species of the crude are
ating on heavy feedstocks like VGO concentrated in the resid portion,
and HCGO. This characterisation but some organometallic species
work tries to understand how these are present in the lower boiling
contaminants are deposited to help ranges with a boiling point above
us develop more effective guard 660°F (350°C).
bed catalysts. Introduction of feeds containing
vanadium, nickel or iron (such as
Contaminants to deal with atmospheric tower bottoms) into
In general, the heavier the hydro- VGO hydrotreating could have
carbon cut the higher the content of severe consequences in terms of
contaminants. In a feed stream such cycle length. The relatively high
as VGO, DAO and HCGO, metals space velocity of these units
contamination is therefore mainly (compared to resid hydrotreating)
an issue for FCC pretreaters, hydro- could result in metal migration into
cracker pretreaters and lube units. the active, main bed catalyst. To
Vanadium and nickel are mainly overcome this problem, a highly
found in large, porphyrin-like active demetallation catalyst with a
structures (asphaltenes) in crude oil high metal pick-up capacity must
Catalysis 2016 19
 be installed on top of the main
catalyst bed. Topsoe has commer-
cialised specially designed VGO
demet catalysts designated TK-453
and TK-455 MultiTrap.
The large molecules containing
these metals require catalyst shapes
with a high surface to volume ratio
to remove these metals efficiently.
Iron will mainly deposit on the
catalyst surface, whereas nickel and
vanadium will deposit inside the
catalyst pore structure due to the
very large average pore sizes of
TK-453 and TK-455.
Arsenic is a true catalyst poison
as it will chemically react with
active catalytic sites, for instance
transforming the catalyst’s nickel
and cobalt into NiAs or CoAs.
Poisoned sites will not be reacti-
vated during regeneration, and
even small amounts on the catalyst
will affect catalyst activity in a criti-
cal way. Fortunately, the
concentration of arsenic is in the
ppb range and can be effectively
dealt with by utilising Topsoe’s
high capacity arsenic traps TK-49 as
an extrudate, and TK-45 and TK-41
in a ring shape.
Silicon found in oil fractions orig-
inates from Si-containing anti-foam
additives used in coker units, as
well as from the use of chemicals
introduced during oil transport and
tertiary oil recovery. Silicon reacts
with the surface of the catalyst and
forms a silica gel, hindering access
to the active catalytic sites and
thereby deactivating the catalyst.
Silicon penetrates into the pore
system of the catalysts, and deacti-
vation is proportional to the
concentration of silicon on the
catalyst.
Contaminants overview
Contaminant Ni/V Fe
Origin Crude Crude
Typical VGO feed 1-5 1-3
concentration wtppm wtppm
Contamination Precipitation Precipitation Titrating Reducing Absorbed Coating
mechanism on as sulphides. as sulphides. active
main bed Pore mouth Pore mouth
catalyst plugging plugging
arsenides.
Real poisoning
Severity + +
Table 1
20 Catalysis 2016
to FCC pretreaters or hydrocracker
pretreaters is a major challenge in
some refineries. The phosphorus
quickly deactivates the conven-
tional catalyst and reduces cycle
length dramatically. Topsoe has
developed specific guard bed cata-
lysts, TK-31 and TK-455 MultiTrap,
to effectively protect the main cata-
lyst. These guard catalysts, with
proprietary properties and compo-
Figure 2 Macroporous particulate trap sition, will be able to prolong the
TK-26 TopTrap cycle length of the unit.
The main source of sodium in a
Haldor Topsoe’s TK-400 series FCC or hydrocracker pretreat feed
catalysts for naphtha and TK-453 is normally poorly desalted crudes.
for heavier fractions provide the This type of inorganic sodium will
highest silicon pick-up on a volume not easily enter the catalyst’s pore
basis. system. Sodium will therefore tend
Phosphorus species are rarely to deposit around the exterior of
found in typical crudes; however, the catalyst, forming a solid crust
some opportunity crudes (and, in between catalyst pellets, which will
particular, renewable feeds) often harm activity and cause pressure
contain significant amounts of drop issues.
phosphorus. Furthermore, phos- We should not forget to mention
phorus-containing anti-corrosion inorganic iron, which is a very
additives can be found in diesel common contaminant. Iron rust
and VGO fractions. Phosphorus originates from corrosion of
compounds are decomposed in the upstream equipment and may
hydrotreater, and the phosphates consist of everything from large
react with the alumina support flakes to the smallest particle tank
(much like silicon), forming very rust. Large particle rust is known to
stable aluminium phosphates. be easily trapped in filters, scale
Accumulated amounts of phos- catchers and high void catalytic
phates will reduce accessibility materials. However, 5-10 micron
to the active sites of hydrotreating inorganic iron particles are very
catalysts and lower the hard to handle as they will pass
activity accordingly. Phosphorus feed filters and, without a proper
compounds are often found to orig- graded bed system, enter the cata-
inate from injection of corrosion lyst bed. Inorganic iron will also
inhibitors in the form of preferentially deposit in the outer
thiophosphorus compounds like surface of the catalyst, unless a
thiophosphate esters, thiophos- very large pore demet catalyst is
phites and tributyl phosphate. utilised as a guard catalyst, and
Handling of organic phosphorus will eventually lead to increasing
compounds in the VGO being fed pressure drop.
To handle inorganic iron, Haldor
Topsoe introduced themacroporous
particulate trap TK-25 TopTrap a
number of years ago and it has
As Fe Si P Na proven to be a leading trap material.
Crude Corrosion Additives Additives Salt The company recently launched
50-250 0-3 0-3 0-2 0-2
an improved particulate trap,
wtppb wtppm wtppm wtppm wtppm
designated TK-26 TopTrap, with an
void to catalyst of optimised daisy shape with three
sites resulting surface area. catalyst axial holes to provide about 20x
forming in pressure Co-reaction exterior
higher pick-up capacity as
drop with P
compared to TK-25 TopTrap. TK-26
+++ + +(+) +++ ++ TopTrap is designed with a 61%
particle void fraction as well as a
large internal pore volume and
www.eptq.com
macro pores Larger sized inorganic
contaminants deposit in the spaces Products
between traps; fines or smaller 11/2in TK-15
sized materials enter the pore
system and are trapped within the
5 /8in TK-10

structure of the particle itself (see

/2in
1 TK-26
Figure 2). The internal particle void TopTrap

Size
of TK-25 TopTrap is 25%, so that 3/16in TK-30 TK-709 TK-710 TK-45
the total void in this product is
greater than 85%. /8in
1
TK-30 TK-335 TK-437 TK-337 TK-41 TK-831

More exotic metals like calcium, 1/10in QL

TK-455
TK-31 TK-339 Multi- TK-341 TK-743 TK-453
zinc and magnesium are also Trap

observed in some units. These can 1/15in QL TK-340 TK-49

all originate from different addi-
tives but are also occasionally
found in porphyrin structures in
crude. These contaminants are
quite common in units upgrading
spent lube oils to new base lubes
stocks and can be a challenge. They
are harmful to the main bed cata-
lyst because they tend to stick to
the surface of the catalyst, thereby
preventing access to the pore
system. Table 1 summarises the
mechanisms of contamination.
The importance of utilising
specialised graded bed catalysts and
guard catalysts designed to handle
these many poisons with different
Activity
Figure 3 Haldor Topsoe’s graded bed products
deposition mechanism cannot be
overstated. The ‘one size fits all‘
approach will simply not provide
the refiner with an optimised cata-
lyst loading for proper protection of
the main bed catalyst and the cycle
length will be reduced. Haldor
Topsoe has fine-tuned its catalyst
portfolio to provide proper main
bed protection by constantly adding
new and improved graded bed
products. This is illustrated in Figure
3, which expresses 23 graded bed
products as a function of size vs
catalytic activity.
Demetallisation functionality
(HDM) in a gas oil hydrotreater is a
function of pressure, temperature,
residence time (LHSV), catalyst and
feed. The catalyst system selected is
a key factor in determining the
cycle length. It is not only impor-
tant to install the proper HDM
catalysts but also a main bed cata-

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www.eptq.com Catalysis 2016 21

 is difficult to simulate in a realistic
Largest pore size Large pore size manner in lab-scale pilot units,
Si

Pick-up (fresh catalyst basis)

Highest pore volume High pore volume almost all development work for
P Low activity Medium activity
making new, improved guard cata-
lysts relies on retrieving industrially
aged spent catalysts. One option is
Medium pore size to sample catalyst while the indus-
Medium pore volume
High activity trial reactor is being unloaded. This
obviously gives valuable informa-
tion about the contamination profile
and illuminates how well certain
contaminants migrate through the
different catalyst layers. The best
TK-562 Brim TK-455 MultiTrap TK-743 way to get good samples is to
unload the catalyst by vacuuming.
Figure 4 Bulk analyses for phosphorus and silicon: canister test (ICP-MS) However, if the catalyst is being
dumped through a bottom dump
chute it is not possible to identify
Unit B reactor results: spent lube HDT the exact position of the catalyst
Gradient from top to bottom that is being sampled. The catalyst
Reactor top Reactor bottom unloaded by gravity through a
dump tube will funnel out like
Pick-up (fresh catalyst basis)

Si
P
2 cycles grains emptying from a silo.
Alternatively, we recommend using
1 cycle Petroval’s sampling method called
Probacat, which will drill down
1 cycle through the bed and a set of perfect
core samples of the bed is collected.
The other option is to have cata-
lyst test baskets or canisters installed
in a known location within the reac-
tor during the entire cycle. The
canister will hold several catalysts in
TK-831,1/8in R TK-743,1/10in QL TK-562,1/16in TL
different compartments, and each
catalyst within the canister is
Figure 5 Bulk analyses for Si and P: samples from the catalyst bed (ICP-MS) exposed to practically the same type
and amount of contaminants. In
lyst that has both a high capacity rus. This high level of capacity of collaboration with clients, Topsoe
and tolerance for metals. demet catalyst will protect the main installs 10-20 test canisters in vari-
The metal capacity of a hydro- bed catalyst and allow for longer ous hydrotreating units every year,
treating catalyst is mainly run lengths. and we analyse the contents after
determined by the catalyst’s poros- Our main bed catalysts, BRIM the cycle to continuously optimise
ity. However, the rate of metal and HyBRIM, show a high level of the catalyst formulation for maxi-
removal is a catalytic reaction and both capacity and tolerance for mum pick-up of the contaminants
is therefore very much dependent metals. In FCC pre-treat services, mentioned here.
on catalyst activity and reactor these catalysts have shown as much Our research laboratories are
operating temperature. Based on as 25 wt% of nickel, vanadium and equipped with a wide range of
experience, it is advisable to have iron. Designed with an optimum analytical tools for characterising
reactor temperatures above 600°F combination of pore diameter, pore spent catalysts. ICP-MS, X-ray fluo-
(315°C) to ensure that enough volume and surface area, the cata- rescence, X-ray diffraction and
demetallisation takes place. The lysts have also shown pick-ups as state-of-the-art microscopy are
severity of the feed is also an high as 20 wt% of silicon and within the range of possibilities.
important factor. The actual metal phosphorus. The first thing in the toolbox is
pick-up for a catalyst is dependent always to characterise the spent
on all of the above factors. Retrieving spent catalyst samples catalyst using a precise bulk analy-
Haldor Topsoe’s demet catalysts It is essential to have access to rele- sis method. An exact quantification
show very high metals pick-ups, vant and representative spent of what is present in the sample is
with as much as 40 wt% of nickel catalyst samples if a detailed under- required. The most efficient method
plus vanadium pick-up in FCC standing of contamination type, to apply for this purpose is
pre-treat service and over 20 wt% degree and profile is to be obtained. inductive coupled plasma mass
each of both silicon and phospho- Because the contamination process spectrometry (ICP-MS).

22 Catalysis 2016 www.eptq.com

 Scanning electron microscope (SEM) and electron
micro probe analyser (EMPA) are tools used to deter-
mine the chemical composition in localised areas of
solid materials. The method is ideal for a combination ARKEMA’S
of structural and chemical information. An electron
CARELFLEX
®
beam interacts with the sample and produces electrons
both for imaging and characteristic X-rays. Both the
energy and the wave length of the X-rays can be SULFIDING
detected. SERVICE
The strength of canisters and spent catalyst analyses Manufacturing dimethyl disulfide
Topsoe installed canisters in a hydrotreater designed to
process and upgrade spent lube oils to base oils and (DMDS) at three Arkema sites,
group 2+ lubes. Spent lube oil contains large amounts of activating hydroprocessing catalysts
contaminants and additives, such as zinc, magnesium, worldwide.
calcium and, in particular, phosphorus and silicon. All
of these contaminants deposit on catalysts, causing Carelflex® sulfiding service offers:
significant loss of activity. Two canisters were installed
in the top of the reactor with catalysts having different
Sulfiding procedures, technical
properties (pore volume, pore size, surface area and guidance, training, and 24/7
active metal content). Besides the canisters, catalyst coverage during activation
samples were also obtained from the unloading of the Patented, low-odor DMDS Evolution®2
three reactors. Some of the unloaded catalyst samples
High pressure pumping
had been in operation for one cycle and other samples
had been in the reactor for two cycles. In-line H2S monitoring during the
activation
Analysis by ICP-MS Arkema amines available for
The spent catalysts unloaded from the reactors were passivation of hydrocracking catalysts
analysed using ICP-MS in order to quantify the bulk
amounts of phosphorus and silicon in particular. This
Our global logistics network and
analysis confirmed that the catalysts indeed were heav-
ily contaminated. The numbers also confirmed the experienced Carelflex® sulfiding
theory that catalysts with a high pore volume and service team stand ready for
large open pores could trap most phosphorus and sili- your next activation.
con. Figures 4 and 5 illustrate how three different
catalysts from the canister picked up different amounts
For Customer Service,
of phosphorus and silicon, reflecting the difference in
porosity and activity. call 800.628.4453

Analysis by SEM and EDS

Now it was time to apply the SEM technique to map
and quantify exactly where the contaminants were pres-
ent. Figures 6 to 8 show the quantitative cross-section
analyses of TK-562 BRIM, TK-831 and TK-743 using the
SEM/EDS technique. These catalysts were all grabbed
from different locations in the reactor and represent a
bulk catalyst, a graded bed catalyst and an effective
HDM catalyst. Hence, the last two mentioned have the
biggest pore systems and the largest pores.
A firm crust of phosphorus is seen on the surface of
the main bed catalyst pellet. The phosphorus content in
the crust exceeds 15 wt% and silicon is around 10 wt%.
In fact, the crust appears to be a complex matrix of the
impurities of the spent lube oil as it also contains high
amounts of calcium, magnesium and zinc. The two
measurements made within the catalyst pellet show a dmds-evolution.com
steep drop in the phosphorus content, whereas silicon is
fairly constant at all points.
Looking at the TK-831 and TK-743 samples, there is a
significant difference. While they also have a crust
Carelflex and Evolution are registered trademarks of Arkema.
layer surrounding them, the crust is thinner and, more © 2016 Arkema Inc. All rights reserved.

www.eptq.com Catalysis 2016 23

 OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 41.6 3.6 1.4 0.9 <0.5 6.0 15.7 <0.5 6.2 14.9 0.0 1.4 <0.5 0.0 7.0
2 39.9 3.7 1.3 1.0 <0.5 1.3 24.5 <0.5 2.3 17.1 0.0 1.2 <0.5 0.0 6.1
3 44.2 2.7 1.1 0.6 <0.5 10.2 16.9 <0.5 4.9 11.7 0.0 0.9 0.5 0.0 5.5
Catalyst
4 44.2 2.2 1.5 <0.5 <0.5 9.7 16.5 <0.5 4.6 12.4 0.0 1.2 0.6 0.0 6.0
5 51.2 2.9 1.0 <0.5 <0.5 10.2 15.5 <0.5 2.4 12.6 0.0 1.0 <0.5 0.0 1.8
6 46.6 1.3 <0.5 <0.5 14.7 8.9 9.8 4.3 5.0 5.0 0.0 0.6 1.3 0.0 1.0
Crust
7 44.6 <0.5 <0.5 <0.5 24.0 10.5 5.0 5.9 6.7 <0.5 0.0 0.2 2.0 0.0 0.6

Catalyst 8 42.6 <0.5 <0.5 <0.5 26.7 10.0 2.5 6.3 7.7 <0.5 0.0 0.2 2.4 0.0 0.6
wt%

Figure 6 EDS analysis of a cross-section of TK-562 BRIM

OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 33.0 2.8 1.0 0.9 0.7 10.9 23.4 3.7 0.7 25.7 0.0 2.3 0.0 0.5 5.9
Catalyst 2 51.7 5.2 1.0 <0.5 <0.5 3.5 18.0 <0.5 2.2 8.9 0.0 0.7 0.0 0.6 2.4

3 30.5 0.8 <0.5 <0.5 23.5 4.1 14.4 0.7 3.0 <0.5 0.0 <0.5 0.0 1.4 <0.5

Crust 4 42.2 <0.5 <0.5 <0.5 26.1 4.7 18.3 2.7 2.5 <0.5 0.0 <0.5 0.0 1.3 0.7

5 44.4 <0.5 <0.5 <0.5 27.4 5.2 14.9 2.1 2.4 <0.5 0.0 <0.5 0.0 1.5 0.6

6 52.9 <0.5 <0.5 <0.5 24.0 5.8 11.5 1.6 1.8 <0.5 0.0 <0.5 0.0 1.1 <0.5
Catalyst
wt%

Figure 7 EDS analysis of a cross-section of TK-831 (ring shape)

OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 33.7 3,7 1.0 0.0 0.7 5.2 14.9 0.0 8.6 14.5 0.5 1.2 0.0 0.5 14.2
Catalyst 2 48.0 4.4 0.9 0.5 2.3 4.9 12.8 0.0 6.6 10.8 <0.5 0.7 0.0 <0.5 7.3

3 47.7 1.5 <0.5 <0.5 21.4 4.3 10.5 2.7 5.0 2.7 <0.5 0.6 0.0 1.7 0.8

Crust 4 51.2 <0.5 <0.5 <0.5 25.3 4.0 8.4 3.6 4.3 <0.5 <0.5 <0.5 0.0 1.8 <0.5

5 48.7 <0.5 <0.5 <0.5 29.3 4.5 7.3 2.7 4.2 <0.5 <0.5 <0.5 0.0 1.8 0.6

6 46.0 <0.5 <0.5 <0.5 32.9 5.1 6.4 3.2 4.0 <0.5 <0.5 <0.5 0.0 1.5 <0.5

Catalyst wt%

Figure 8 EDS analysis of a cross-section of TK-743 (HDM catalyst)

importantly, the phosphorus
species are found in much higher
concentrations within the catalyst
pellet than was the case for TK-562
BRIM. The crust itself is again very
rich in phosphorus, silicon and the
other contaminants.
The data shows a good correla-
tion between the catalyst’s porosity
and pore size and its ability to
allow phosphorus and silicon
compounds to enter the catalyst
pore system. This data as well as
dozens of other similar canister
studies has enabled Haldor Topsoe
to generate optimised catalysts
designed to pick up the specific
poisons causing issues in each indi-
vidual hydrotreating unit, resulting
in a better performance and cycle
length. The graded bed system
needs to be designed for each unit
to effectively eliminate unit
constraints.
Michael T Schmidt is Product Manager with
Haldor Topsoe, responsible for the development
and quality of Topsoe’s FCC pretreat and
hydrocracking pretreat catalysts. He holds
a degree in chemical engineering from the
Technical University of Denmark (DTU).
Henrik Rasmussen is Vice President of
Catalyst and Technology with Haldor Topsoe,
responsible for the catalyst and license
technology business for the US, Canada,
and the Caribbean. He holds a degree in
chemical engineering from the University of
Copenhagen.

24 Catalysis 2016 www.eptq.com

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Process Notes

This exchanger is a victim of its design.

Opportunity or Annoyance?
Price differentials between conventional and opportu-
nity crudes compel refiners to process increasing per-
centages of lower valued opportunity crude. However,
as many refiners have learned the hard way, opportu-
nity crudes are tied to unique processing challenges.
Furthermore, existing crude unit configurations may
limit high-profit opportunity crude to a disappointingly
small proportion of the total unit blend.
Over the course of 20 years, Process Consulting Ser-
vices has completed more than 130 revamp and grass-
roots designs supported by over 75 detailed test runs.
An extensive collection of test run equipment perfor-
mance data and feed/product analyses enables confi-
dent prediction of real-world opportunity crude perfor-
mance. PCS has enabled refiners worldwide to extend
crude unit run lengths from months to years while im-
proving yields and operability.

Processing a changing slate of opportunity crudes of

varying compositions requires a CDU/VDU design that
is flexible, reliable, and commercially proven. A good
design must control chronic problems associated with
many of these crudes including corrosion, exchanger
fouling, tray plugging, vacuum heater and wash bed
coking, and unreliable product quality prediction. CDU/
VDU designs for challenging crudes should be based
on proven best-practices rather than simply on a low-
CAPEX strategy. For example, a poorly designed heat
exchanger may operate well initially, but high foul-
ing will quickly lower efficiency and eventually limit
throughput. Up front investment in engineering expe-
rience and know-how pays dividends when units meet
Test run feed and product samples
capacity and run-length targets.

3400 Bissonnet St. +1 (713) 665-7046

Suite 130 info@revamps.com
Houston, TX 77005, USA www.revamps.com
 Increasing FCC propylene yield

A test run with ZSM-5 additive demonstrated to a refinery that it could

significantly raise production of propylene in the FCC

RUDOLF LÁTKA, VLADIMÍR OLERÍNY and NORBERT KOVÁČ Slovnaft

TOM VENTHAM Johnson Matthey Process Technologies

A
new 22 000 bpd FCC unit
was constructed by Slovnaft
in 1999. Slovnaft is Slovakia’s
only modern, fully integrated refin-
ery. The FCC processes mainly
hydrotreated VGO feed with typi-
cal unit objectives of LPG and
gasoline production. High value
LPG components are sought for
downstream processes such
as polypropylene, ETBE and
alkylation. The FCC limitation is
typically found in the gas concen-
tration section (LPG Merox, C3
splitter).
FCC propylene study
In 2014 Slovnaft investigated modi-
fications to increase propylene
production. The typical propylene
yield from the Bratislava refinery
FCC unit is approximately 6 wt%
on a fresh feed basis. Industry
experience has shown standard
FCC units with VGO feed are typi-
cally capable of producing up to
10-12 wt% propylene by imple-
menting relatively simple
techniques that maximise gasoline
overcracking to LPG and retain
olefinicity.
Slovnaft performed a significant
Refinery processes
Others
(97% from FCC)
Acrylonitrile 35%
production
On-demand processes
Propylene 8%
oxide
Polypropylene
production Steam crackers
57%
Figure 1 Industrial uses of propylene1
Propylene market demands
Slovnaft was pursuing methods to Figure 3 Propylene supply to petrochemicals
elevate propylene production
because of the worldwide market million t/y, 35% is produced by
trend of increased propylene refinery processes (of which the
demand and value. The drive for FCC process itself accounts for 97%),
propylene is mainly to satisfy petro- 57% is produced by steam crackers
chemical industry demands, and 8% by ‘on-purpose’ propylene
especially growth in polypropylene processes (see Figure 3).3 Propylene
demand (see Figures 1 and 2).1,2 demand is expected to continue to
Based on 2011 data, approximately increase by almost 5% a year, with
68% of refinery produced propylene new propylene production capacity
is supplied to the chemicals indus- not expected to keep up with this
try.3 Of the chemical industry’s total demand growth, resulting in the
propylene requirement of 109 appearance of a ‘propylene gap’.3
100
Others
Market volume, million tons

90
amount of research in this area and Films
80 Textiles
identified several options that could
increase propylene output from the 70 Injection moulding
FCC unit. The company decided to 60 55.83
take a stepwise approach by 50
performing tests to determine the 40
capabilities and sensitivities of 30
methods to define the optimum
20
strategy to be implemented. This
research concluded that the most 10
effective way for Slovnaft to 0
increase FCC propylene yield 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022
would be the use of a high activity
ZSM-5 additive. Figure 2 Projected polypropylene market growth 2012-20222

www.eptq.com Catalysis 2016 27

 hydrogen transfer on the main
Projections of Super Z Excel performance at Slovnaft
catalyst.
It was predicted that, following
Super-Z Excel in FCC unit, wt% 2.5% 5.0% 7.5% the increase in LPG, the net yield
FCC gasoline octane boost reduction would be from gasoline.
RON gain 1.3 1.9 2.2
MON gain 0.5 0.8 0.9 Although the estimate shows a
Yield shifts, % small reduction in LCO yield this is
C2 or lighter, wt%/vol% No change No change No change due to the reported low gasoline/
C3=, wt%/vol% 1.7/3.0 2.9/5.2 3.8/6.6 LCO cutpoint at Slovnaft being
C3, wt%/vol% No change No change No change
Total C4=s, wt%/vol% 1.0/1.5 1.7/2.6 2.2/3.3 below the standard 221°C cutpoint
iC4=, wt%/vol% 0.3/0.4 0.5/0.8 0.6/1.0 (gasoline 90% boiling point being
nC4=, wt%/vol% 0.7/1.0 1.2/1.8 1. /2.3 170°C). An unchanged bottoms
nC4, wt%/vol% No change No change No change yield was predicted as ZSM-5 only
iC4, wt%/vol% 0.5/0.8 0.8/1.3 1.0/1.7
Gasoline, wt%/vol% -3.0/-3.7 -5.2/-6.4 -6.7/-8.2 cracks molecules found in lighter
LCO, wt%/vol% -0.1/-0.1 -0.3/-0.2 -0.3/-0.3 intermediate product ranges. There
Bottoms, wt%/vol% No change No change No change is also no change expected in the
Coke, wt%/vol% No change No change No change coke yield, as ZSM-5 is heat balance
neutral, so will not typically alter
Table 1 the coke requirements of the
system.
Supply-side effects are also ZSM-5 test run plans As part of this estimate an addi-
impacting this situation. In China, The additive chosen by Slovnaft for tion plan was developed (see Table
demand is outstripping investment this test run was Intercat Super Z 2) for loading the additive over the
in traditional sources of propylene Excel supplied by Johnson Matthey. course of the test run. This started
production, and in North America, Designed for high propylene FCC with a base load phase during the
the shift to shale gas based ethane operations, Super Z Excel has high first seven days to quickly boost the
feedstocks for steam crackers has activity and stability, resulting additive concentration to the work-
reduced propylene generation from in the efficient generation of ing level. Following the base load, a
this traditional source of the propylene. maintenance dose regime was
commodity. This trend is expected In cooperation with Intercat, planned to preserve the correct
to be observed in Europe too as Slovnaft developed an estimate to level of ZSM-5 activity for the
imports of American shale gas to anticipate the yield and octane remainder of the test run period.
European steam crackers will add to improvements that would be Due to unrelated disturbances in
the propylene imbalance.4 Although observed when adding Super Z upstream units during the initial
various propylene on-demand Excel (see Table 1). stages of the test run Slovnaft were
projects will look to fill this propyl- The main yield shift expected not able to precisely follow the
ene gap, there will be a lag before was an increase in the propylene planned loading protocol.
this extra supply is realised. In addi- yield followed by a boost in buty- However, sufficient amounts of
tion, many of these projects will be lenes yield. The yield of isobutane Super Z Excel were added to attain
sensitive to commodity and crude was also expected to increase. the concentrations needed to
oil prices as well as political and Although ZSM-5 only produces observe yield responses.
environmental pressures that are olefins, because isobutene is the ZSM-5 is a fast acting additive,
apparent in the regions where many most readily saturated LPG mole- meaning yield changes can typi-
of these projects are located, such as cule via hydrogen transfer, cally be seen after the first week of
China. The FCC unit remains a flexi- isobutane yield also increases addition. The octane improvement
ble and cost-effective method for with ZSM-5 due to the secondary with ZSM-5 requires the full
increasing propylene production to effect of converting some of concentration of the additive to be
fill the demand gap. the produced isobutylene via present at steady state to determine
the entire benefit.
Super Z Excel addition protocol for Slovnaft test run
LPG yield effects
Super-Z Excel in FCC unit, wt% 2.5% 5.0% 7.5% When Super Z Excel additions to
Super-Z Excel Additions the FCC unit began, the propylene
Steady state, kg/day 30 61 94 yield responded almost immedi-
Accelerated policy
Day 1, kg/day 310 630 950
ately. Figure 4 shows the change in
Days 2 and 3, kg/day 190 370 570 propylene yield as ZSM-5 was
Days 4 and 5, kg/day 170 330 510 introduced.
Days 6 and 7, kg/day 130 260 400 Slovnaft estimated that the typi-
Days 8+, kg/day 30 61 94
cal FCC propylene yield without
ZSM-5 was averaging 6 wt% prior
Table 2 to the start of the test run. As

28 Catalysis 2016 www.eptq.com

ZSM-5 was added in base load, Super Z Excel
with over 2.5 tonnes of additive Start Stop
10 10

SZE concentration,
added in the first four days of the

Propylene yield,
9 8
test run, the propylene response
was major, with propylene yield 8 6

wt%

exceeding 9 wt% in the first week.
This represents a 50% increase.
A constant ZSM-5 addition rate
followed the base load, leading to a
gradual increase in the inventory
wt%
7 4
6 Propylene 2
SZE concentration
5 0

14

14

14

5
concentration. The addition rate

01

01

01

01
20

20

20
/2

/2

/2

//2
0/

1/

2/
was increased again towards the

12

/1

/4

/2
/1

/1

/1

16

15
7/

25
28

17

27
end of the test run, leading to a
second propylene yield peak above Figure 4 Propylene yield on a mass feed basis
9 wt%. When the test run ended,
the ZSM-5 concentration decayed
along with the propylene yield, Start-up Super Z Excel
with the propylene half-life of 29
Shutdown Start Stop
Super Z Excel measured to be in LPG yield, wt%
27
the range of 23 days. The propylene
yield remained above the base line 25
for six weeks, falling to only 7 wt% 23
at the end of the data set compared 21
to the base line of 6 wt%. This
19
shows that residual ZSM-5 activity
14

14

14

14

5
was still present six weeks after the
01

01

01

01
20

20

20

20
/2

/2

/2

/2
1/

3/

0/

2/
final addition. Based on the period
5/

/6

/8

/2
1/

2/

/1

/1
1/

30

29

25
28

when ZSM-5 concentration
exceeded 5 wt% in the inventory to
the final day of additions, the aver-
age propylene yield reached 8.9
wt%, or a 47% increase on the base
line.
It was also observed that the total
LPG yield (see Figure 5) increased
when ZSM-5 was introduced to the
FCC unit and continued to climb
for the rest of the test run as ZSM-5
concentration increased. By the end
of the test run, the total LPG yield
increased 7 wt% compared to the
pre-test run base line. It was
expected that the total LPG increase
would be made up of 55-60%
propylene and 45-40% butylene
with some saturation of produced
isobutylene via hydrogen transfer
on the main catalyst.
Unfortunately, due to the short
duration of this test run, steady
27
Figure 5 Total LPG (all C3 and C4 components) yield on a mass feed basis
stages. The first decay is of the ity mainly produces butylenes and
component in ZSM-5 chiefly deactivates more slowly, meaning
responsible for producing high the total LPG yield remained well
quantities of propylene. This is the above the base line level due to this
most active or highest acidity part residual activity still being present
of ZSM-5, which deactivates most in the weeks after additive addi-
rapidly, resulting in the LPG tions were stopped.
decrease observed immediately
following the end of Super Z Excel Testing unit response to sudden
additions. The second component ZSM-5 additive additions
of ZSM-5 activity is of lower inter- Part of the plan was to test the
stitial acidity and is hence more response of the FCC unit to large,
stable. This secondary ZSM-5 activ- sudden additions of ZSM-5 addi-
LPG yield
Super Z Excel SZE additions
29
Start Stop
1200
LPG yield, kg/day
LPG yield, wt%

27 1000
state was not reached. After addi-
800
tive additions were stopped, LPG 25
yield declined as the activity of the 600
23
ZSM-5 present in the inventory 400
decayed. Although the abruptness 21 200
of the decay appears dramatic this 19 0
only represents a partial decay of
14

14

14

15

15
01

01
20

20

20

20

the most active part of the ZSM-5

/2

/2

/2
0/

1/

2/

2/
12

/1

/2
/1

/1

/1

5/

cracking functionality. When

16

25
7/
28

17

27

analysing the decay, it was noticed

that the ZSM-5 deactivates in two Figure 6 Total LPG yield on a mass feed basis and ZSM-5 addition rate

www.eptq.com Catalysis 2016 29

 LPG olefinicity effects
Start-up Super Z Excel By increasing propylene yield with-
1.9
Shutdown Start Stop out a major change in propane
1.8 yield, an increase in C3 olefinicity
Propane yield, 1.7 was clearly observed (see Figure 8)
1.6
as the test run progressed. This
wt%
1.5
1.4 olefinicity increase was another
1.3
1.2 way Slovnaft measured ZSM-5
1.1 effectiveness and was another proof
0 that the propylene yield increase
14

14

14

14

5
was due to the addition of Super Z
01

01

01

01
20

20

20

20
/2

/2

/2

/2
1/

3/

0/

2/
Excel and not the result of an
5/

/6

/8

/2
1/

2/

/1

/1
1/

30

29

25
28

27
increase in conversion or a shift to
a more crackable feed.
Figure 7 Propane yield on a mass feed basis Slovnaft also observed changes in
the C4 yield structure (see Figure 9),
with a higher yield of butylenes
Start-up Super Z Excel
Shutdown Start Stop
with ZSM-5.
7.0 Although ZSM-5 produces signif-
6.5 icant amounts of unsaturated C4
C3 olefinicity

6.0
material, less saturated material is
5.5
5.0
directly produced (see Figure 10). A
4.5 common observation when using
4.0 ZSM-5 is that a portion of the
3.5 iso-butylene produced becomes
saturated to iso-butane via hydro-
14

14

14

14

5
01

01

01

01
20

20

20

20

gen transfer on the main catalyst. A

/2

/2

/2

/2
1/

3/

0/

2/
5/

/6

/8

/2
1/

2/

/1

/1
1/

30

29

25

noteworthy increase in iso-butane

28

27

was not observed during this test

run due to low rare earth on fresh
Figure 8 C3 olefinicity defined at propylene yield/propane yield catalyst (~1 wt% rare earth oxide),
resulting in weak hydrogen transfer
tive. Three tests were run where propane yield did not increase capabilities.
spikes of high ZSM-5 additions of significantly with Super Z Excel Slovnaft also noticed that conver-
more than 500 kg/day were made (see Figure 7). ZSM-5 does not sion in the ETBE unit improved as
(see Figure 6). The initial spike was directly increase propane yield as a result of an increase in the
part of the base load of Super Z the chemistry only allows for the amount of isobutylene fed to the
Excel. The second two spikes were generation of olefins. However, a unit originating from the FCC unit.
used by Slovnaft to test the unit small fraction of the propylene These secondary indicators of
response to high ZSM-5 additions produced by ZSM-5 can be satu- increased LPG olefins production
as the test run neared its conclu- rated to propane via hydrogen from the FCC unit when using
sion. In each of these three cases, transfer on the FCC main catalyst. Super Z Excel gave Slovnaft further
the response of increasing LPG This reaction is very slow, so only a confidence in the benefits using
yield was clearly visible. small increase in propane was such an additive can give.
It was noted that, as expected, observed.
ZSM-5 additive effect on FCC
conversion
Start-up Super Z Excel A concern often expressed by refin-
2.4
Shutdown i-C4 Start Stop ers who are unfamiliar with the use
7.5
n-C4 of ZSM-5 additives is whether the
Normal-butylene
Iso-butylene

2.2 7.0 addition of large amounts of ZSM-5

yield, vol%

yield, vol%

2.0 6.5 will cause dilution of the main FCC

1.8 6.0 catalyst, and cause a loss in FCC
1.6
conversion. This was monitored
5.5
very closely by Slovnaft, and it was
1.4 5.0 observed that conversion did not
14

14

14

14

vary significantly (see Figure 11)

01

01

01

01
20

20

20

20
/2

/2

/2

/2

during the test run period, demon-

1/

3/

0/

2/
5/

/6

/8

/2
1/

2/

/1

/1
1/

30

29

25
28

27

strating no negative effects on unit

conversion through use of the
Figure 9 Iso-butylene and n-butylene yields on a mass feed basis additive.

30 Catalysis 2016 www.eptq.com

 Feed quality is a very strong
driver of conversion at Slovnaft. As Start-up Super Z Excel
Shutdown i-C4 Start Stop
conversion was at the low end 7.0 1.8

Iso-butane yield,
n-C4
(~75 wt%) of the normal conversion

Normal-butane
6.5
1.6

yield, vol%
range (75-85 wt%), this indicates 6.0
5.5 1.4

vol%
the feed quality during the test run
period was poor. Poor feed quality 5.0 1.2
4.5
and low unit conversion would 1.0
4.0
normally result in low LPG yields
3.5 0.8
without the presence of active

14

14

14

14

5
01

01

01

01
ZSM-5. Poor feed quality may also

20

20

20

20
/2

/2

/2

/2
1/

3/

0/

2/
5/

/6

/8

/2
result in a reduction in the presence

1/

2/

/1

/1
1/

30

29

25
28

27
of crackable material in the gasoline
range for ZSM-5 to convert to LPG. Figure 10 Iso-butane and n-butane yields on a mass feed basis
This suggests a more challenging
environment for ZSM-5 to be oper-
ating in.
Start-up Super Z Excel
Shutdown Start Stop
88
Gasoline selectivity effects Unit conversion,
86
The ZSM-5 effect was also seen by 84
looking at gasoline selectivity (see 82
wt%

Figure 12). Gasoline selectivity was 80

78
relatively constant through the base 76
line period. (Operational changes 74
that increase conversion will also 72
tend to generate gasoline yield
14

14

14

14

5
01

01

01

01
20

20

20

20
increases of a similar order.)
/2

/2

/2

/2
1/

3/

0/

2/
5/

/6

/8

/2
1/

2/

/1

/1
1/

30

29

25
However, when Super Z Excel was

28

27
introduced, the gasoline was
cracked to LPG with no change in Figure 11 Unit conversion (100-LCO-DCO)
conversion. This resulted in a step
drop in gasoline selectivity due to
ZSM-5. The shape of this trend also Start-up Super Z Excel
Shutdown Start Stop
proved to Slovnaft that Super Z 0.72
Gasoline conv.,

Excel was still actively cracking 0.70

0.68
wt%/wt%

gasoline to LPG by the end of the 0.66

data set, with gasoline selectivity 0.64
0.62
still below the typical level 0.60
observed before the start of the test 0.58
0.56
run. 0.54
4

14

14

5
1

01

01

01

01

Gasoline octane effects

20

20

20

20
/2

/2

/2

/2
1/

3/

0/

2/
5/

/6

/8

/2

As well as generating LPG olefins,

1/

2/

/1

/1
1/

30

29

25
28

27

Super Z Excel was also effective in

increasing gasoline octane number Figure 12 Gasoline selectivity (gasoline yield/conversion)
(see Figure 13).
It was thought that some of the
increase in octane was due to the Start-up Super Z Excel
slip of LPG components into the Shutdown RON Start Stop
96.0 83.0
gasoline product. However, when MON
82.8
95.5
Slovnaft looked at this data on a 82.6
94.0
cross-plot (see Figure 14), the RON 82.4
MON
RON

93.5 82.2
octane values measured during the
93.0 82.0
test run were above expectation at 81.8
92.5
the gasoline Reid vapour pressure 81.6
values observed at that time. 92.0 81.4
14

14

14

14

5
01

01

01

01
20

20

20

20
/2

/2

/2

/2
1/

3/

0/

2/

Comparing test run results to

5/

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/8

/2
1/

2/

/1

/1
1/

30

29

25
28

27

industry averages
It has already been shown that
Slovnaft successfully increased Figure 13 RON and MON values of FCC gasoline

www.eptq.com Catalysis 2016 31

 the FCC feed processed at Slovnaft
94.8 is of generally good quality, being
94.6 Super Z Excel
Base
hydrotreated VGO, and so is easily
94.4
cracked. Moreover, the FCC unit is
94.2
operated in a high severity mode
94.0
conducive to high propylene yields,
93.8
with an average riser temperature
RON

93.6
93.4 of 536°C.
93.2 This high base line propylene
93.0 may suggest further large increases
92.8 may be challenging if the paradigm
92.6 of a maximum propylene yield ceil-
92.4 ing is to be believed.
47 48 49 50 51 52 53 54 55 56 Despite the high base line propyl-
Reid Vapour Pressure, kPa ene yield, the 3 wt% propylene
increase seen at Slovnaft was far
Figure 14 Cross-plot of gasoline RON octane versus gasoline RVP above average (see Figure 16),
confirming that the ZSM-5 test run
at Slovnaft had been successful.
50
Some FCC units operating in a
45 deep maximum propylene mode
40 are able to achieve propylene yield
Observations, %

35 increases of 5 wt% or greater when

30
using large amounts of ZSM-5
(10-30% of total catalyst additions),
25
showing that there is further scope
20 for Slovnaft if large propylene
15 yields are desired.
10 It was found that the concentra-
5 Slovnaft tion of ZSM-5 used during the
Mean = 5.7 SZE trial = 6.0 Slovnaft Super Z Excel test run was
0
0 1 2 3 4 5 6 7 8 9 10 above the average compared to
Base propylene yield, wt% Intercat’s ZSM-5 trial database (see
Figure 17). However, it should be
Figure 15 Histogram of base propylene yield in a number of commercial FCC units remembered that this was a
condensed test run conducted over
a short time period to test the
30
advances in propylene yield that
could be achieved. Therefore, the
25
Super Z Excel concentration did not
Observations, %

20
reach a steady state that would
generate a stable propylene yield
15 response at a constant ZSM-5
concentration.
10 Despite not reaching a steady
state ZSM-5 concentration during
5 this brief test run, the propylene
Slovnaft
Mean = 1.1 SZE trial = 3.0 yield increase per mass amount of
0 ZSM-5 concentration in the FCC
0 0.5 1.0 1.5 2.0 2.5 3.0 More
inventory was above the observed
∆Propylene yield, wt% test run average (see Figure 18).
Although this measure is only
Figure 16 Histogram of delta propylene yield with ZSM-5 in a number of commercial judged fairly once the FCC inven-
FCC units tory composition and FCC
operation have reached a steady
propylene yield from the FCC Firstly, it was seen that the base state of the combination, the sensi-
unit. But how did these results line propylene yield at Slovnaft tivity of the Slovnaft FCC unit to
compare to industry trends? Using was already higher than the aver- ZSM-5 use and the high cracking
Johnson Matthey’s database of age over all the cases studied (see activity of Super Z Excel mean the
ZSM-5 tests, Slovnaft compared Figure 15). results observed exceeded normal
their results to general trends. This is not overly surprising as expectations.

32 Catalysis 2016 www.eptq.com

Conclusions
50
The FCC team at Slovnaft success-
fully executed a short but 45
instructive study to determine the 40
additional propylene yield that

Observations, %
35
could be attained from the 30
Bratislava refinery FCC unit. The
25
ZSM-5 test run was carried out
over a period of 49 days using 20
Intercat Super Z Excel from 15
Slovnaft
Johnson Matthey. The results from 10 SZE trial = 5.9
this test run show a rapid and 5
significant increase in LPG olefins, Mean = 3.1
0
with the average propylene yield 0 1 2 3 4 5 6 7 8 9 More
increasing from 6.1 to 8.9 wt% on a ZSM-5 concentration in FCC inventory, wt%
fresh feed basis. The high propyl-
ene yield results recorded elevated Figure 17 Histogram of ZSM-5 concentration in a number of commercial FCC units
the Slovnaft FCC unit to a similar
percentage of propylene production 50
as with dedicated maximum
45
propylene FCC units designed
40
specifically for high propylene
Observations, %

yields. In addition, increases in 35

butylenes, total LPG and gasoline
octane value were observed, which
is consistent with high activity
ZSM-5 use.
In the view of Slovnaft, this test
run delivered numerous benefits
that would assist future projects
and strategies. The most important
benefit was the proof that propyl-
ene yield could be successfully
increased from the FCC unit and
could be exploited to fill the addi-
tional propylene demand that exists
in the Slovnaft refinery if bottle-
necks were removed. The second
discovery was that the test run
revealed previously unknown
bottlenecks or operational pinch
points when the FCC unit is oper-
ated in maximum propylene mode,
such as the loss of LPG components
to dry gas and gasoline either due
to equipment capacity or a shift in
operational protocols when operat-
ing in this novel mode. These
findings will be used as inputs in
future FCC debottlenecking studies.
Finally, the test run gave Slovnaft
experience in ZSM-5 operation
including the LPG response when
adding large spikes of additive to
the FCC unit, how downstream
equipment is impacted as the
composition of the LPG cut changes
with ZSM-5, and the decay period
after additions have ceased.
Overall, this brief test run of Super
Z Excel gave Slovnaft a wealth of
30
25
20
15
10
5 Slovnaft
Mean = 0.35
0
0 0.1 0.2
Propylene yield per wt% additive, wt%/wt%
Figure 18 Histogram of propylene yield increase over ZSM-5 concentration in a number
of commercial FCC units
useful information that can now be
used when planning future
strategies to increase refinery
profitability.
References
1 Propylene: 2015 World Market Outlook and
Forecast up to 2019, Jun 2015.
2 Synthetic & Bio-Based Polypropylene
Market Analysis by Application and Segment
Forecasts to 2022, Jun 2015.
3 Refinery sources will fill the future propylene
gap, Oil & Gas Journal, Vol 101, No 4, 27 Jan
2013.
4 WoodMac: China, North America face
propylene oversupply, Oil & Gas Journal, Vol
112, No 9d, 29 Sept 2014.
Rudolf Látka is a Chemical Engineer with
Slovnaft, a member of the MOL Group. With
more than 30 years of experience in the
oil and gas industry, he has participated in
the preparation, realisation, operation and
optimisation of the FCC complex, a part of the
refinery Residuum Processing Project for resid
SZE trial = 0.51
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
conversion to gasoline. He retired at the end
of 2015.
Vladimir Oleríny is an Operative Maintenance
Coordinator for the FCC and hydrocracking
complex at Slovnaft refinery. From the initial
FCC start-up in 1999 until 2012, he worked
as a FCC Panel Operator. He holds a master’s
degree in chemical engineering from Slovak
University of Technology in Bratislava.
Norbert Ková is a Process Engineer with
Slovnaft. He previously worked at both
the Danube refinery and TVK (now MOL
Petrochemicals), holding various positions
including Energy Efficiency Engineer. He holds
a master’s degree in chemical engineering from
the University of Pannonia, Veszprém.
Tom Ventham is a Senior Technical Service
Engineer for Johnson Matthey. He has held
this position since 2010, supporting refineries
in Europe, and he previously worked for MW
Kellogg Ltd as a Process Engineer and Murco
Milford Haven refinery in the position of
FCC Engineer. He holds a master’s degree in
chemical engineering from Imperial College,
London, and is a Chartered member of the
Institute of Chemical Engineers (IChemE).

www.eptq.com Catalysis 2016 33

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 Kinetic engine drives catalyst
development
Development of a NiMo catalyst for medium-to-high and high pressure middle
distillates hydrotreating
ANDREA BATTISTON
Albemarle Corporation
H
ydroprocessing is an impor-
tant refinery process for
upgrading low value feed
streams to higher value intermedi-
ates and on-specification fuels,
including ultra-low sulphur diesel
(ULSD). Albemarle’s Stax kinetic
model continues creating commer-
cial value by helping refiners
optimise hydrotreater loadings, and
has become a fundamental tool
with Albemarle’s research and
development for the design of new
hydrotreating catalysts.
Ketjenfine (KF) 880 Stars for
medium-to-high and high pressure
middle distillates hydrotreating is
the first catalyst designed using the
Stax kinetic engine. This NiMo
catalyst offers superior hydrogena-
tion activity for demanding
operations. The benefits include
higher feedstock upgrading,
increased throughput and/or cycle
length, improved product proper-
ties and higher volume swell.
Together with the STAX technol-
ogy, KF 880 brings significant
advantages for the most demand-
ing middle distillates hydrotreating
operations.
ULSD middle distillates
hydrotreating: reactor zones and
catalyst selection
The chemical reactions and related
kinetics in a hydrotreater change
with the nature of the feedstock, the
operating conditions, the degree of
conversion and the time on-stream.
This means that applying a single
catalyst load is rarely the optimal
solution. Stax technology enables
the refiner and catalyst manufac-
turer to design the right loading
scheme for each situation by taking
www.eptq.com
• HDS of easy sulphur via DDS.
Medium-to-high and high pressure
Low & medium pressure
Zone • PNA conversion and HDN via HYD.
1
Catalyst with low affinity for the adsorption of coke precursors.
• Hydrogenation limited by nitrogen inhibition.
Zone • HDS shifts to HYD route.
2 • HDN can become critical.
Catalyst with high HDN/HYD activity if ppH2 allows.
• Nitrogen-inhibition-free zone.
Zone
3 Catalyst with high HYD activity.
Tune HYD activity based on operation’s targets and constraints.
Figure 1 Stax technology applied to a generic ULSD hydrotreater
into account process objectives, of non-sterically hindered (di-)
economics and constraints. benzothiophenes proceeds well into
In its Stax engine, Albemarle iden- zone 2, but sulphur removal by
tifies three main reactor zones for hydrogenation becomes increas-
middle distillates hydrotreating ingly important. Hydrogenation
operations (see Figure 1). In zone 1, (HYD) becomes the main HDS
the primary reactions are hydro- reaction route for refractory
genation of olefins and the sulphur at higher pressure and, in
conversion of easy sulphur via the general, when hydrogenation reac-
direct hydrodesulphurisation (HDS) tions are not thermodynamically
route, also called direct desulphuri- limited.
sation (DDS). At the same time, Residual organic nitrogen inhibits
polynuclear aromatics (PNA) and the HYD route. The faster the
nitrogen species start being organic nitrogen removal, the more
converted via hydrogenation. effective is the removal of refractory
In zone 1, the main risks to oper- sulphur. At the same time di- and
ation are condensation reactions of di+-aromatics are further saturated
PNA species and coke deposition. to monoaromatics. Most of the HDS
Consequently, the preferred choice and polyaromatics saturation to
is a catalyst that does not have too monoaromatics takes place in zones
high an affinity for the adsorption 1 and 2. Conversely, the saturation
of coke precursors. of monoaromatics to naphthenes in
As the feedstock moves down the zones 1 and 2 typically does not
reactor, the sulphur removal rate occur as the inhibition effect by
decreases because more refractory nitrogen and PNAs is still too high.
species need to be converted. DDS In low and most medium
Catalysis 2016 35

10000
Concentration, wtppm
1000
100
10
Zone 1
1 and consumption are not limita-
0 0.1
Figure 2 Stax test study comparing NiMo (high HYD) and CoMo (high DDS) Type II
catalysts’ operation in the reactor: P=30 bar, T=350°C
pressure ULSD hydrotreaters, Zone
2 extends to the reactor bottom. At
higher pressure or when easier
feedstock is processed, on the other
hand, the hydrodenitrogenation
(HDN) reaction rate can be high
enough to remove the organic
nitrogen fully, thus creating zone 3.
At that point, all hydrogenation
reactions are boosted, including
that of sterically hindered sulphur.
The hydrogenation of residual di-
and monoaromatics is also boosted,
which can be used for additional
volume swell.
Catalyst selection for zone 2 is
the most critical for both the opera-
tion’s activity and stability. If the
pressure is low or if thermody-
namic limitation occurs for
hydrogenation reactions, a catalyst
with a high DDS activity is prefera-
10000
Concentration, wtppm
1000
100
10
Zone 1
1 treater. The reference reactor
0 0.1
Figure 3 Stax test study comparing NiMo (high HYD) and CoMo (high DDS) Type II
catalysts’ operation in the reactor: P=60 bar, T=350°C
36 Catalysis 2016
strongly depends on operating
targets and constraints. The absence
NiMo sulphur
CoMo sulphur
of organic nitrogen boosts the activ-
NiMo nitrogen ity of all types of catalyst, but
CoMo nitrogen mostly of highly hydrogenating
ones. An additional consideration is
that zone 3 may be replaced by zone
2 during the cycle as hydrogenation
activity decreases with catalyst
aging. This must be taken into
account when designing the catalyst
Zone 2 Zone 3 (NiMo only) load. Where hydrogen availability
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 tions, a catalyst with high HYD
Reactor length, (dimensionless) activity would be the preferred solu-
tion. Conversely, where hydrogen
consumption is a constraint, or for
stability considerations, a catalyst
with a lower HYD activity would be
ble. Conversely, where conditions the best choice.
are suitable for hydrogenation, The right catalyst system is
catalysts with a high HYD activity always the one that best balances
are preferred, as they enable much the operation’s objectives (desul-
phurisation, cetane uplift, volume
The right catalyst swell, and so on) with its limita-
tions (ppH2/hydrogen availability,
system is always operating temperature and cycle
length) over the entire cycle.
the one that best
Stax reactor zones:
balances the learning from testing
Tests run by Albemarle highlight
operation’s objectives the effects of specific catalyst func-
tionalities on performance in the
with its limitations various reactor zones as a function
over the entire cycle of ppH2. The HDS and HDN results
for KF 848 (Type II Stars NiMo
catalyst) and KF 757 (Type II Stars
faster removal of organic nitrogen CoMo catalyst) are shown in
and, with it, of refractory sulphur. Figures 2 and 3. KF 848 and KF 757
For zone 3, catalyst selection catalysts are used as references to
illustrate the behaviour of Type II
NiMo catalysts (high HYD activity)
and Type II CoMo catalysts (high
DDS activity), respectively.
NiMo sulphur
CoMo sulphur
The figures depict the evolution
NiMo nitrogen of sulphur and nitrogen as SRGO
CoMo nitrogen (total sulphur = 1.2 wt%; refractory
sulphur ∼1200 ppmwt) is being
converted along the reactor at 30
and 60 bar inlet ppH2. The catalyst
systems were run in parallel in the
same conditions and in varying
amounts to simulate conversion at
Zone 2 Zone 3 (NiMo only) Zone 3 the different heights in a hydro-
0.2 0.3 0.4 0.5 length of 1.0 (dimensionless)
Reactor length, (dimensionless) considered here is the length
needed by the KF 757 system to
reach 8 wtppm sulphur product at
30 bar.
www.eptq.com
 By comparing the results, it is
possible to understand the main
differences in behaviour between a
NiMo and a CoMo Type II
catalyst.
When operating at moderate
pressure (30 bar, see Figure 2), the
main route for sulphur removal for
most of the reactor is DDS. Because
of this, a CoMo catalyst provides a
higher sulphur conversion than a
NiMo catalyst, despite the higher
nitrogen slip. In this case, this holds
well into zone 2, down more than
half of the reactor.
A NiMo catalyst can remove
nitrogen faster than a CoMo cata-
lyst, which can boost sulphur
removal via the HYD route when
approaching the reactor’s bottom.
In this case, the NiMo catalyst even
reaches a nitrogen-free zone (zone
3) in view of the easy feedstock
utilised. However, the advantage of
the overall process remains limited
mainly because the ppH2 is low, so
that at the end the CoMo and the
NiMo catalysts reach basically the
same HDS performance for ULSD
production.
The case illustrated is boundary
for the use of either a CoMo or a
NiMo catalyst. With more difficult
feedstocks, at low pressure the
nitrogen level remains higher down
to the bottom of the reactor. Also,
for a NiMo catalyst, zone 3 cannot
be reached. As a result, the HYD
reaction route is significantly less
effective and a CoMo catalyst typi-
cally delivers an overall better
performance for ULSD. Also, in
terms of stability a CoMo catalyst is
preferable at low pressure.
When operating at higher pres-
sure (60 bar, see Figure 3), it is
advantageous to apply a catalyst
with a higher HYD activity.
Although a CoMo catalyst is still
more effective at removing easy
sulphur via DDS at the reactor’s
top, its higher capacity for remov-
ing nitrogen in zone 2 enables a
NiMo catalyst to reach zone 3 much
faster, with an overall advantage in
removing hard sulphur. Thus, at a
higher pressure, applying a NiMo
catalyst is the best choice as HDS
and HYD of aromatics are the main
targets. If hydrogen consumption is
a specific constraint, a CoMo cata-
www.eptq.com
Commercial case A - comparison between operations in cycles 1 and 2
Case A
Feed composition and properties
LCO + VBGO, vol%
Sulphur, wt%
Nitrogen, ppmwt
Density, g/ml
Operating parameters
ppH2 inlet, bar
H2/oil ratio, NL/L
Avg. total feed rate, %, normalised
Table 1
lyst can still be applied at the
reactor bottom under the NiMo
catalyst to limit the saturation of di-
and monoaromatics.
As mentioned previously, being
able to reach zone 3 has a signifi-
cant impact on HDS and on the
saturation of residual di- and
monoaromatics. Monoaromatic
saturation, in particular, is very
difficult and is significantly inhib-
ited by the nitrogen still present in
zone 2, so incremental monoaro-
matic saturation occurs primarily in
zone 3. Hence, when hydrogen
consumption is not a constraint and
cetane uplift and volume swell are
the operating targets, applying a
catalyst system capable of creating
and maintaining a larger zone 3 at
the reactor bottom will bring a
significant advantage by generating
additional high value diesel
through cetane uplift and volume
swell.
KF 767
KF 860
KF 757
KF 848
KF767
Cycle 1 Cycle 2
Figure 4 Commercial case A - comparison between catalysts loading in cycles 1 (CoMo)
and 2 (Stax CoMo/NiMo/CoMo)
Cycle 1 Cycle 2
5 + 1 (6) 5 + 1 (6)
0.94 0.95
202 213
0.860 0.858
54 58
170 177
100 102.5
Stax technology at work:
commercial experience
Two case studies illustrate how
refiners have successfully applied
Albemarle’s Stax technology to
increase their operating margins.
Case A is a medium-to-high pres-
sure ULSD operation treating a
blend of straight run gasoil and
cracked feedstock. The refinery
used to operate with KF 757 Stars,
a CoMo catalyst with high DDS
activity. The main reason for select-
ing KF 757 was to guarantee
stability in view of the moderate
ppH2 at reactor bottom.
The optimisation strategy for the
new cycle (see Figure 4, Cycle 2) has
been to increase the overall hydro-
genation activity within the
operation’s constraints while still
guaranteeing sufficient stability over
the cycle. A high performance Stax
CoMo/NiMo/CoMo configuration
was used, operating with similar
KF 767 Stars (high HYD CoMo) to
lower nitrogen from the top.
KF 860 and KF 848 Stars (NiMo) to
maximise HDN and HDS.
KF 767 Stars for HDS, stability and
to limit H2 consumption.
Catalysis 2016 37
 refractory sulphur most effectively.
410 KF 767 catalyst was preferred over
400 a NiMo in the lower section to limit
390 H2 consumption and to preserve
380 the operation’s stability throughout
WABT, ºC

the cycle.
370
The new system lowered the
360 start-of-run temperature (WABT)
350 by approximately 20°C, which also
340 allowed an increase in the overall
Cycle 1
330 stability of the operation. The cycle
Cycle 2
length was more than doubled as a
320
0 2 4 6 8 10 12 14 16 18 20 22 24 result (see Figure 5).
Time on stream, months Case B is a medium-to-high pres-
sure hydrotreater that was
Figure 5 Case A - comparison of the start-of-run WABT and the cycle length between revamped by Albemarle and its
cycles 1 and 2 Alliance partner UOP to meet the
refinery’s growing diesel demand.
The revamp lead to an increase of
over 30% in the unit’s capacity. The
operating hydrogen pressure was
also slightly increased.
KF 860 KF 860 Stars (NiMo) to boost HDN and
KF 757 guarantee stability at the top. To capture maximum advantage
from the revamp, Stax technology
was used to design the new catalyst
system. A KF 757/KF 868/KF 767
KF 868 Stax (CoMo/NiMo/CoMo) load,
KF 868 Stars (high HYD NiMo) to
KF 868 enlarge zone 3 and boost volume which had provided good perfor-
swell. mance before the revamp, was
changed out for a KF 860/KF 868
KF 767
Stax (NiMo) system designed to
upgrade more heavy cracked
components to diesel. The strategy
in this case was to remove nitrogen
as fast as possible in zone 2 to
Cycle 1 Cycle 2
enable a substantial zone 3 opera-
tion for the unconstrained
Figure 6 Commercial case B - comparison between catalysts loading in cycles 1 hydrogenation of refractory
(Stax CoMo/NiMo/CoMo, before revamp) and 2 (Stax NiMo, after revamp) sulphur and of di- and monoaro-
matics. A comparison between the
Commercial case B - comparison between operations in cycles 1 and 2 loaded systems and operating
parameters in cycles 1 (CoMo/
NiMo/CoMo, before revamp) and
Case B Cycle 1 Cycle 2
Feed composition and properties
2 (NiMo, after revamp) is shown in
LCO, vol% 2 8 Figure 6 and Table 2, respectively.
LCGO, vol% 18 19 The main result of the revamp
Nitrogen, ppmwt 240 332 and of the application of the new
Density, g/ml 0.854 0.860
Operating parameters
Stax design was an increase in the
ppH2 inlet, bar 46 52 total feed rate of over 25% and an
H2/oil ratio, NL/L 460 360 even higher intake of distressed
Avg. total feed rate, %, normalised 100 125 feedstocks. In particular, over 30%
more high density and poor cetane
Table 2 LCGO and over 350% more LCO
components were fully upgraded
conditions and feed properties as in an early stage. A combination of KF to valuable Euro V diesel (see
the previous cycle (see Table 1, 848 and KF 860 high hydrogenation Figure 7).
Cycle 1). activity NiMo catalysts was used in
KF 767 CoMo catalyst was used the middle section, where the ppH2 KF 880 Stars catalyst
for the upper section, as inhibition was still high and the additional In addition to optimising reactor
by nitrogen was not too high, to hydrogenation activity would accel- loading using existing catalysts,
start lowering the nitrogen slip at erate nitrogen removal and tackle Stax technology is currently used

38 Catalysis 2016 www.eptq.com

 choose
wisely.
At CRI, we provide catalyst and process solutions tailored for the
petrochemical and refining industry. Our technology is an integral part in
helping achieve success in a customer's application. Our strengths in R&D,
catalyst manufacturing and technical service allow CRI to progress quickly
from lab scale to production to customer results. We pride ourselves on
developing lasting relationships with our customers through collaboration
and successful implementation of catalytic solutions.

It is all part of our commitment to delivering innovation.

cricatalyst.com
 60 30
Cycle 1

Light cycle oil (LCO)

(LCGO) intake, t/h
Light coker gasoil 50 25 Cycle 2

intake, t/h
40 20
30 15
20 10
10 5
0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time on stream, days Time on stream, days

Figure 7 Case B - comparison of the cracked stock intake during cycles 1 and 2 (first 180 days; cycle 2 is still running). Albemarle’s
incumbency has already been reconfirmed for the next cycle

by Albemarle R&D to support new increased by decreasing space

“RVA +20 to 25%
catalyst design. HDS
+15%
KF 880 Stars, Albemarle’s new
“RVA +30 to 35%
supported NiMo grade for medi- HDN
+20%
um-to-high and high pressure
“Density +3.0 to 3.5 g/l
middle distillates hydrotreating, is reduction
+2.0 to 2.5 g/l
the first catalyst created using the
Stax catalyst engine. KF 880 is Figure 8 Average performance advantage
Albemarle’s highest performance of KF 880 Stars catalyst compared with KF
NiMo catalyst with increased 868 and KF 848 Stars catalysts
hydrogenation activity to boost
removal of nitrogen and refractory KF 880 Stars catalyst compared
sulphur, and aromatics saturation. with KF 868 and KF 848 Stars,
The sweet spot application for KF Albemarle’s NiMo reference cata-
880 Stars catalyst is in zones 2 and lysts, is summarised in Figure 8, as
3 in medium-to-high and high pres- derived from pilot plant test results
sure operations, where sufficient with various feedstocks in the
ppH2 is available and superior 70–80 bar ppH2 inlet range.
hydrogenation activity is required. A test comparing KF 880 with
KF 880 Stars catalyst can be applied KF 848, both as full loads on HGO
to a wide range of value proposi- at 80 bar ppH2 inlet, hydrogen/oil
tions, including upgrading ratio = 500 NL/L and 341°C,
distressed feedstock to ULSD, shows KF 880’s significantly higher
volume swell and increased feed HDS, HDN and HDA activity in
throughput and cycle length. zones 2 and 3 (see Figure 9).
The performance advantage of Sulphur conversion in the test was
Zone 2 Zone 3
1000
KF848
KF880
Product sulphur, ppm
vs KF 848
velocity.
vs KF 868
The advantage in density reduc-
vs KF 848
tion of KF 880 starts developing in
vs KF 868
zone 2 (+2.0 g/L) as a result of its
vs KF 848
superior hydrogenation activity
vs KF 868
and peaks in zone 3 (+3.9 g/L)
where the nitrogen inhibition on
aromatics saturation has been fully
removed.
In zone 1, KF 861 NiMo catalyst
would be the preferred choice, as it
offers the same performance at the
reactor’s top but at reduced cost for
refiners. Note that loading up to 30
vol% KF 861 catalyst at the top of
the reactor has a negligible impact
on the activity of the overall cata-
lyst system.
Superior hydrogenation activity in
middle distillates hydrotreating
Stax solutions for medium-to-high
and high pressure middle distillates
applications where high hydro-
genation activity is required are
summarised in Figure 10.
KF 861 catalyst is Albemarle’s
choice for zone 1, as it delivers high
activity and stability at the reactor
top at a reduced cost. The main
NiMo catalysts to be applied in

zones 2 and 3 are KF 868, as a base

100
case, and KF 880, Albemarle’s new
supported NiMo option. As shown,
KF 880 catalyst delivers boosted
10
HYD activity that can be used by
refineries seeking higher feedstock
KF 880 vs KF 848
upgrading, improved product
Product nitrogen: 25 vs 40 4 vs 12 <0.3
properties and additional volume
∆Density, g/l: +0.3 +2.0 +3.9 swell to improve operating margin.
1
0 5 10 15 20 25 30 In addition, Nebula catalyst can
Time on stream, days be applied in Stax combinations
starting from deep zone 2 and zone
Figure 9 Pilot plant test results of KF 880 compared with KF 848 Stars catalyst 3. Because of its unique active site

40 Catalysis 2016 www.eptq.com

density, Nebula provides extremely
high HYD activity. When Nebula is
placed higher in the reactor, its
additional activity can be exploited
to maximise HDN and HDS perfor-
mance. Alternatively, when the
catalyst is placed at the reactor’s
bottom, it yields increased monoar-
omatics saturation, cetane uplift
and volume swell. The benefit for
HDS remains.
Albemarle has developed and is
continuously refining Stax, its
proprietary kinetic model and reac-
tor load optimisation technology,
which is routinely used for the
development of new catalysts.
KF 880 Stars, Albemarle’s
top-performing NiMo grade for
medium-to-high and high pressure
middle distillates hydrotreating, is
the first catalyst designed with the
direct support of the Stax kinetic
platform. It offers increased hydro-
genation activity for refiners
seeking higher feedstock upgrad-
ing, improved product properties
and volume swell.
www.eptq.com
Zone 1 Apply catalyst with low affinity for PNA adsorption. KF 861
Balance
KF 868
Zone 2 Apply catalyst with high HDN/HYD activity.
Boost KF 880
Nebula
KF 868
Zone 3 Apply catalyst with high HYD activity.
KF 880
Boost Exploit cetane uplift and volume swell.
Nebula
Figure 10 Stax solutions for medium-to-high and high pressure middle distillate
applications to deliver high hydrogenation activity
Andrea Battiston is a Senior Technical responsibilities in catalyst research and
Specialist Hydroprocessing with Albemarle development, laboratory testing and
Corporation, providing support to the application technology. He holds a MSc degree
company’s global Clean Fuels Technology in chemical engineering from Politecnico di
business and technical groups in a variety Milano, Italy, and a PhD in heterogeneous
of distillates hydroprocessing applications. catalysis and spectroscopy from Utrecht
He has held positions with various University, The Netherlands.
Catalysis 2016 41
cattec.indd 1 26/02/2013 16:59
 Revamping for ULSD production

A sandwich catalyst system has given the additional activity needed to process
difficult feed in a hydrotreater

MIKE ROGERS Criterion Catalysts & Technologies

KIRIT SANGHAVI Alon USA Refining

A
lon Big Springs refinery and
Criterion Catalysts have
worked for over 10 years to Gasoline
5
achieve an impressive track record Diesel and ULSD
Price diff.: gasoline − diesel/ULSD
of successes in their distillate 4
Price / US gallon, $

hydrotreater, boosting diesel capac-

ity and production by up to 20%, 3
and greatly improving unit flexibil-
ity. With the current strong market 2
for diesel, this gain has allowed
1
them not only to track their prod-
uct demands, but it has
0
dramatically boosted profitability Prices before 1984: Prices after 2006:
for their shareholders. The gasoline >> diesel ULSD > gasoline
−1
sustained collaboration between
20 1

20 5

20 9

20 3
19 1

19 5

19 9

19 3

19 7
99

03

20 7

11

15
19 9

19 3

87

91

19 5

1
8

9
9

0
7

Alon and Criterion has been a

19

19

20

20

20
19

crucial factor in the success of the

refinery.
In the early 2000s, Criterion
worked with Shell Global Solutions
to find a cost-effective way to bring
Alon’s distillate hydrotreater unit
to ULSD production. Low operat-
ing pressure, difficult feed and
limited hydrogen availability were
serious challenges. The refinery
chose to install new reactor vessels
with reactor internals from Shell
Global Solutions. The catalyst was
Criterion’s first-generation Cobalt-
Molybdenum ULSD product.
In the years following its success-
ful transition to ULSD production,
Alon continued to work closely
with Criterion. The challenge was
to extend the catalyst life cycle and
increase straight run diesel (SRD)
and light cycle oil (LCO) cut points
for improved refinery economics.
The refiner needed to push the
cycle from about nine months to at
least 12 months in order to synchro-
nise with the semi-regen reformer
regenerations. Increasing demand
for diesel was putting pressure on
the refinery to raise the cut points
Figure 1 Gasoline and diesel price trends in the US
of their straight run and LCO to
maximise diesel yields. In 2010,
Alon loaded a first-generation
Centera sandwich system, which
gave a large boost in activity and
enabled significant gains towards
increasing the unit’s flexibility and
profitability.
In 2014 Alon implemented a
revamp in the crude distillation
unit. One of the main objectives of
that revamp was to boost the
straight run diesel yield, which
would increase available feed to the
ULSD unit for higher diesel produc-
tion. Again, the success of this
project was crucial for the refinery
to increase profitability in the face of
shifting market demand. Criterion’s
second-generation Centera sand-
wich system with DC-2635 CoMo
and DN-3636 NiMo has given the
additional activity needed to process
the additional difficult feed and at
the same time maintain catalyst
cycle flexibility and once again
contributing to Alon’s success.
US refiners shift towards increased
diesel production
Most refineries in North America
and other regions in the world were
designed and built 40 or more years
ago, and in order for them to
survive they have had to adapt
continually to shifting fuels
markets. The major recurring
themes in these shifts have been
tighter environmental requirements
(lower sulphur and so on) and a
push towards higher energy effi-
ciency, particularly in transportation
fuels. In the Americas, the recent
arrival of shale oil with higher
yields of naphtha has also had an
impact on the fuels market by
contributing to gasoline oversupply.
Figure 1 shows average gasoline
and diesel prices in the US since
1979. The diesel-gasoline price gap
has been relatively stable over most
of the period, with some notable
exceptions. In the late 1970s/early
1980s, major improvements in auto-
mobile fuel efficiency pushed

www.eptq.com Catalysis 2016 43


Straight-run distillates
from Crude Unit CDU
and VDU towers
FCC distillates −
light cycle oils (LCO)
Coker light gas oil
hydrotreater
(CLGO)
Hydrocracker products
− HC diesel and HC kero.
Figure 2 Blending of diesel, kerosene and jet in a typical refinery
gasoline demand downwards,
which had the effect of closing the
long-standing gap between the two
transportation fuels prior to that
time. In 2006, the introduction of
ULSD specifications for on-road
vehicles marked the beginning of
an upward trend in diesel pricing,
but the major shift in the price gap
which occurred in the 2000-2010
period was driven largely by
European and other countries that
recognised the higher energy effi-
ciency of diesel over gasoline as a
transportation fuel. European
governments implemented various
forms of vehicle taxation and fuel
incentives that favoured diesel
powered vehicles. The effect was
dramatic. In 1990, diesel powered
cars in Europe represented about
13.8% of demand, while by 2009
that proportion had increased to
46%. European refiners have been
unable to keep up with the demand
shift ever since, and as a result,
exports of diesel to Europe as well
1600
1400
1200
1000
TBP, ºF
Kero.
hydrotreater
Diesel
Distillate Diesel
blending
splitter
pool
as imports of gasoline from Europe
have grown, thus further driving
the price gap in the US. In recent
years, the arrival of domestic shale
oil production has pushed the price
gap even further apart, due to the
higher proportion of condensates
and naphtha that are produced
from those operations. Today, prac-
tically all North American refiners
are pushing to maximise their
diesel and kerosene production.
The resulting increase in yields of
diesel range material in the refinery
has increased feed rates and feed
difficulty in many ULSD units.
Maximising distillate production
Over the past 20 years or more,
refiners have been making large
efforts to maximise diesel produc-
tion by optimising cut points,
improving fractionation efficiencies
and driving their conversion units
to maximise diesel range material.
In 2010, the US Energy Information
Administration (EIA) released a
Distillate boiling
point expansions
paper1 on this subject which
outlines a range of measures that
Jet / refineries have implemented to
kero.
follow this trend.
No. 1 In a typical refinery, diesel and
diesel distillate products are made from
No. 2 blends of a range of refinery
diesel streams (see Figure 2). The distillate
hydrotreater (ULSD unit) is an
Furnace
oil essential and critical element to
diesel production since it has the
Off-road
diesel role of transforming the lower qual-
ity diesel range material from the
crude unit, the FCC and the coker
into finished diesel components. As
the production of diesel range
material in those upstream units is
increased, the DHT unit must have
the ability to handle that additional
load in terms of higher throughput
and higher catalyst activity.
Fractionation improvements in the
crude unit for higher diesel yield
The yield of diesel and kero range
material from a crude distillation
column is adjusted by changing the
boiling range (cut points) of the
draw stream. Increasing the cut
point range affects properties of the
stream such as the heaviness and
the cold flow properties.
Lowering the ‘front end’ of the
boiling range brings naphtha range
material into the kero jet. This light
material lowers the flash point of
the kerosene, which is limited by
the final product specifications.
Raising the ‘back end’ of the distil-
lation will bring vacuum gas oil
range material into the diesel,
affecting the cold flow properties
and gravity as well as bringing in
heavier sulphur and nitrogen
species that are more difficult to
treat.
In the FCC fractionation column,
lowering the front end cut point of
LCO will shift heavy gasoline into
the LCO. This affects not only the

800 flash point, but it also lowers the

diesel cetane index. The heavy end
600 of the LCO contains not only diffi-
400 Vacuum cult sulphur and nitrogen, but also
tower polyaromatic species, which have a
200 Kero Vacuum gas oil bottoms
Naphtha Jet Diesel (FCC feed) (Coker feed) large impact on the performance of
0 the ULSD catalyst.
0 10 20 30 40 50 60 70 80 90 100 Poor or inefficient fractionation
Volume, % causes overlap of the distillation
cuts and will negatively affect
Figure 3 Increasing diesel/kero yield by expanding the distillation range important properties such as flash

44 Catalysis 2016 www.eptq.com

point and cloud point. It limits the
ability to expand the cut point range
because the property constraints Overhead gas
(flash, cold flow and so on) are Light naphtha
reached sooner. Improving product Heavy naphtha
Vac. diesel
separation is therefore an important (to DHT)
Crude Kero. LVGO
aspect of maximising diesel yield. charge
Diesel HVGO
Diesel/ VGO separation AGO
Poor separation between the diesel Slop wax
and VGO cut will reduce diesel
yield in two ways: Atmospheric
distillation (CDU) Asphalt/resid.
1. Diesel left in the VGO by ineffi- Vacuum distillation
cient separation will result in those (VDU)
molecules going with the VGO to
FCC feed. They are subsequently Figure 4 Typical crude oil distillation unit with atmospheric and vacuum fractionation
cracked to light naphtha in the FCC towers
reactor.
2. When VGO molecules flash and
are recovered in the diesel cut (as
Diesel section
‘over-flash’) the cold flow proper- Atmospheric
ties are affected, and it is often distillation (CDU)
necessary to reduce the cut point
(by reducing the diesel draw rate) AGO section
to correct for this effect.
Improving the separation
between diesel and VGO allows Wash section Diesel (to DHT)
more diesel to be recovered by
reversing both of these mecha-
Crude
nisms. The following section charge Stripping AGO (to FCC)
describes ways of implementing section
those improvements in the crude Stripping steam
distillation unit.
Bottoms to VDU
Atmospheric distillation
modifications to improve diesel yield
Figure 4 depicts a typical crude oil Figure 5a Typical flash zone arrangement of the atmospheric distillation tower
distillation unit with an atmospheric
and vacuum tower where diesel and
kero are produced in the atmos-
pheric towers from side draws. The Diesel section
Atmospheric
quality of diesel/VGO separation in distillation (CDU)
the atmospheric tower is affected by
the number of theoretical stages Structured AGO section Diesel spillback
between the AGO and diesel draws. packing
Diesel range material that remains
unflashed in the bottoms of the Wash section AGO wash Diesel (to DHT)
atmospheric tower is recovered in
the LVGO top product of the
vacuum tower, which most often is Crude
AGO (to FCC)
charge Stripping
sent to the FCC or hydrocracker. In section
US refineries (where gasoline yields Stripping steam
were historically favoured) there
may be as few as only 2-5 trays in
the AGO and wash sections between Bottoms to VDU
the atmospheric tower flash zone
and the diesel draw tray. Outside Figure 5b Flash zone arrangement with improvements to diesel/VGO separation
the US, refiners may often have as
many as 10-15 trays in this section A recent article2 describes a project vacuum distillation towers. Figure 5a
for better control of diesel end point to improve diesel yield by modifica- shows a typical atmospheric column
and cold flow properties. tions to the atmospheric and flash zone with the AGO and diesel

www.eptq.com Catalysis 2016 45

 Figure 6a shows a typical vacuum
column arrangement with spray
To vacuum
ejectors sections. Figure 6b shows an exam-
ple of a revamped vacuum column
with low pressure drop structured
LVGO packing and an additional product
LVGO section Spray section to FCC or HCU
draw for vacuum diesel.
HVGO section Spray section LVGO
to FCC or HCU Maximising LCO at the FCC
Maximising LCO yield at the FCC
Wash oil section LVGO
Spray section
to FCC or HCU is an important lever to increase
overall diesel production in the
ADU refinery, and a range of effective
bottoms tactics have been reported to that
end in recent literature.3
Resid. to asphalt,
Shifting the cut point in the frac-
coker or bunker fuel tionator is the most direct way to
adjust the LCO yield; however the
high aromatic content of the FCC
Figure 6a Typical vacuum tower arrangement product makes it increasingly diffi-
cult to process at the distillate
hydrotreater as the end point is
increased. Lowering the FCC reac-
To vacuum
ejectors Low dP tor temperature can have the effect
structured packing (x4) of increasing LCO, but the associ-
Vacuum diesel Vacuum diesel ated reduction in conversion
section to DHT
increases slurry oil yield, and
LVGO section LVGO reduces gasoline and lighter prod-
to FCC ucts. For most refiners this is not an
HVGO section
economically attractive option.
HVGO
to FCC
Recycling heavy cycle oil from the
Wash oil section fractionator back to the FCC reactor
Wash oil feed can improve LCO yield. Often
to coker or FCC
ADU
this practice is combined with the
bottoms use of more zeolytic FCC catalysts,
which are designed to promote
conversion of the heavier cycle oils.
Resid. to asphalt,
coker or bunker fuel Minimising diesel range in the
FCC feed by recovering it in the
crude fractionation towers is
Figure 6b Vacuum tower with improved internals for additional vacuum diesel draw perhaps the most direct and effec-
tive strategy for maximising overall
draws. Figure 5b shows the changes flash zone. Resid is the bottom diesel yield in a refinery.
to the CDU, which include imple- product. The draw trays are sepa- The Alon refinery reported FCC
menting an AGO wash system and rated by spray sections, which offer feed containing up to 20% diesel
installing structured packing heat recovery with low pressure range material prior to their unit
sections above the flash zone. Diesel drop but have poor separation effi- revamp. That percentage dropped
and AGO ‘spillbacks’ are installed to ciency. This arrangement gives the to the 4-6% range following the
ensure effective liquid wetting of the lowest possible resid yield for revamp.
separation sections. asphalt or bunker fuel operation,
but because of the low efficiency of Catalyst choice
Vacuum tower modifications for the spray sections the separation In a hydrogen constrained environ-
recovering diesel between the products (wash oil, ment such as the Alon Big Spring
The Alon refinery implemented a LVGO and HVGO) is poor. ULSD unit, processing capacity is
complete revamp of the VDU The Alon refinery redesigned the maximised by choosing a catalyst
which added a new top product column in a revamp to include system that provides maximum
draw to allow the diesel range structured packing for improved activity while it minimises chemical
material from the CDU bottoms separation in the upper sections, hydrogen consumption. Figure 7
stream to be recovered. and an additional draw for recover- shows the chart that Criterion uses
Typical vacuum towers have ing the cleaned-up diesel range for making catalyst selections for a
three distillate draws above the material at the top of the column. ULSD unit.

46 Catalysis 2016 www.eptq.com

 Cobalt-molybdenum catalysts
tend to use less hydrogen than
nickel-molybdenum catalysts
because they have a lower hydro-
genation power, and CoMo catalysts
will favour direct HDS reaction
mechanisms (which use less hydro-
gen) over indirect. Their weakness is
that they are more prone to nitrogen
inhibition and thus less robust for
processing more difficult feeds. To
overcome the CoMo catalyst‘s limi-
tations while at the same time
minimising hydrogen consumption,
Criterion pioneered the develop-
ment of combined CoMo/NiMo/
CoMo stacked catalyst systems in
the early-mid 2000s.
The three-zone CoMo/NiMo/
CoMo stacked system functions by
removing easy sulphurs in the
upper part of the reactor using
cobalt-molybdenum catalyst; then
nitrogen species are reduced in a
layer of NiMo catalyst placed in the
upper-mid section of the reactor.
The NiMo layer is sized to provide
maximum nitrogen removal while
minimising aromatic saturation and
hence hydrogen consumption as
well. High activity cobalt-molybde-
num catalyst is loaded in the lower
sections of the reactor to complete
the desulphurisation reactions by
direct desulphurisation, again mini-
mising hydrogen consumption. The
CoMo/NiMo/CoMo sandwich
catalyst system enables the refiner
to process much more difficult
feeds than pure CoMo catalysts,
and has been proven in many
applications in the refining world
(see Figure 8).5,6,7
Collaboration yields success
The Alon Big Springs refinery in
West Texas has operated for over
75 years, and currently processes
about 73 000 b/d of crude from
Texas and other areas. It is config-
ured with an FCC and a propane
deasphalting unit (PDA) to extract
heavy PDA gas oil, and it has four
hydrotreaters – a NHT, a jet hydro-
treater, a DHT and a gas oil
hydrotreater. Hydrogen for all of
the hydrotreaters is supplied by a
semi-regen naphtha reformer.
Prior to early 2005, the Alon
refinery had only a single diesel
hydrotreater, which operated at 700
www.eptq.com
Feed difficulty / severity
CoMo
P = 400 psig
pH2 = 250 psia
Hydrogenation environment / H2 consumption
Figure 7 Criterion catalyst selection map for ULSD
psi. The unit had been revamped in
1992 for 500 ppm diesel production.
With ULSD requirements on the
horizon, they realised that their
unit was not capable of desul-
phurising their tough feeds
containing 25% LCO to the 8-10
ppm ULSD product at the required
rates. Capital was very tight, and
the refinery could not afford to
build a new high pressure ULSD
unit like many other refiners were
doing. Hydrogen supply was also
very limited, and so a key require-
ment for the ULSD unit was low
hydrogen consumption.
The refinery canvassed five cata-
lyst vendors for a solution; they
found that processing their feed
was too challenging with the exist-
ing unit, considering the low
pressure, the single reactor volume
and the difficulty of the feedstock.
At the time, Criterion and Shell
Global Solutions proposed a low
cost unit revamp which would
have two reactors in series, lower-
ing the LHSV to 0.83 hr-1. The
reactors would be loaded with
• Easy S removal
CoMo
• Exotherm control
NiMo • Slow HDS regime
• Remove inhibiting N
CoMo • Fast indirect HDS
• Minimise PNA saturation
Figure 8 Catalyst placement in the CoMo/
NiMo/CoMo sandwich design
CoMo
NiMo
NiMo
CoMo
Stack
P = 600 psig P = 800 psig P = 1300 psig
pH2 = 430 psia pH2 = 650 psia pH2 = 1150 psia
Criterion’s highest activity cobalt-
molybdenum catalyst. The high
activity cobalt-molybdenum cata-
lyst would achieve maximum
desulphurisation while minimising
hydrogen consumption from
aromatic saturation. With these
modifications, Alon successfully
migrated to ULSD production.
However, over the first years of
operation the unit struggled to
process difficult feeds. The initial
catalyst cycles with all-CoMo cata-
lyst did not have enough activity to
process the available LCO and to
synchronise with the reformer
regeneration cycles. The refinery
was forced to reduce endpoint by
as much as 35-40°F on the LCO and
straight run diesel cuts to restore
enough flexibility in the operation.
Since that time, the Alon refinery
has worked closely with Criterion
to improve the unit performance
and to respond to large incentives
to upgrade more LCO for diesel
production. Over years, the unit
saw a steady increase in both feed
rate and the cut points of the feed
components, which resulted from
collaborative efforts by Alon and
Criterion to optimise the unit oper-
ation. In 2009, Criterion tested the
Centera sandwich catalyst system.
The robustness and improved
activity of the Centera sandwich
over the CoMo catalyst allowed an
increase in the D-86 T90 of the LCO
of about 25°F – from 630-635°F to
the 655-665°F range. Straight run
diesel D-86 T90 increased from
Catalysis 2016 47
 generation Centera sandwich system
+200 in 2014 yielded substantial gains in
this progress. These major steps
contributed in a large way to overall
consumption, SCF/B
Chemical hydrogen
+150
refinery profitability. The success
Selected catalyst Alon has had with the distillate
system hydrotreater unit over the past
+100
almost 10 years is a demonstration
of beneficial results from a contin-
+50 ued collaboration with Criterion
Catalysts & Technologies and unit
improvements to take advantages of
Base the opportunities provided.
1st generation 100% Centera 2nd generation
Centera sandwich CoMo Centera sandwich
CENTERA is a trademark of Criterion Catalysts
& Technologies
Figure 9 Comparison of hydrogen consumption – 2012 catalyst testing programme
References
1 Publication of the U.S. Energy Information
627°F to the 650-655°F range, with Conclusion
Administration, Office of Petroleum, Gas, and
cold flow constraints applied in Refiners in North America and
Biofuels Analysis, Department of Energy, Office
the winter months. The sandwich around the world are adapting to of Policy and International Affairs – Increasing
system enabled these improve- shifting fuels markets. In recent Distillate Production at U.S. Refineries – Past
ments with only a very nominal 5% years, demand and prices for diesel Changes and Future Potential, Oct 2010.
increase in hydrogen consumption. have outpaced gasoline quite 2 Singh D, Meeting diesel specifications at
In 2012, the most recent sandwich substantially. Refiners have sustained production, Hydrocarbon Processing,
design with second-generation increased their efforts to maximise Apr 2011.
Centera catalysts was tested against production of diesel range material 3 Niccum P K, KBR, Houston, Texas, Maximize
the original system and a 100% in all the units of the refinery. The diesel production in an FCC-centered refinery,
Centera CoMo catalyst for this unit. distillate hydrotreater in many refin- Part 2, Hydrocarbon Processing, Jan 2012.
4 Torrisi S, New Generation Flexibility –
Figures 9 and 10 show the results of eries has seen increases in feed rate
Customized CENTERA Catalyst solution
those tests. The new generation and feed difficulty, thus increasing
extends cycle life and feed processing
Centera sandwich system demon- demands on the catalysts. capabilities of ALON USA’s challenging ULSD
strated even higher levels of Maintaining consistent, long term Unit, Catalyst & Technology News, publication
activity, and again with only very collaboration with Criterion, the of Criterion Catalysts and Technologies Ltd.,
small increases in hydrogen Alon refinery in West Texas has Feb/Mar 2011.
consumption. Coupled with Alon’s implemented a series of improve- 5 Kraus L S, Gripka P J, Combined CoMo/
improvements to the crude unit ments to a low pressure, tightly NiMo Catalyst System Advantages in ULSD
towers implemented in the 2014 constrained ULSD unit to allow it Production: Part I – Pilot Plant Studies, ACS
revamp, loading this new catalyst to process more difficult feeds and 2010 Annual Meeting.
system has allowed a dramatic to increase operational flexibility. 6 Kraus L S, Gripka P J, Combined CoMo/
NiMo Catalyst System Advantages in ULSD
increase in unit throughput and The implementation of Criterion’s
Production: Part II – Commercial Experience,
further increases in the LCO and first generation Centera sandwich
ACS 2010 Annual Meeting.
straight run cut points. system in 2010 and the second- 7 Gripka P J, Kraus L S, Increase ULSD
Production with Customized ULSD Catalyst
+200 System Design, AIChE 2010 Spring Symposium,
Temperature at start of run, ºF

San Antonio TX.

+150 Mike Rogers is a Senior Engineer with Criterion

Catalysts & Technologies, Edmonton. He has
over 25 years of experience in oil refining with
Selected catalyst
+100 system Shell in Canada. He provides technical support
in the areas of hydroprocessing and catalysis
in Canada and the US, and holds a Master’s
in chemical engineering from the University
+50
of Alberta, and a BSc in chemical engineering
from the University of Waterloo.
Kirit Sanghavi is General Manager, Process
Base
1st generation 100% Centera 2nd generation Design & Engineering for Alon USA. He has
Centera sandwich CoMo Centera sandwich 23 years of experience working for EPCs and
refiners, and has published several technical
Figure 10 Comparison of temperature requirement for 8 ppm product sulphur – 2012 papers. He holds a BSc in chemical engineering
catalyst testing programme from the University of London.

48 Catalysis 2016 www.eptq.com

 UOP has been serving catalyst customers for decades, and constant
innovation ensures we’ll be there for decades to come.

Relentless 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. 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, please visit

www.uop.com/catalysts

© 2016 Honeywell International. All rights reserved.

UOP-Catalysts-Ad-Relentless-7261-A4.indd 1 2/22/16 10:26 AM

UOP7261
 Look beyond the catalyst
Purification and dispersion strategies applied to hydroprocessing catalyst can
improve reactor performance
AUSTIN SCHNEIDER
Crystaphase
R
efiners are feeling the pres-
sure, and not just the kind of
pressure found inside hydro-
processing reactors. Lacklustre
catalyst performance and frequent
shutdowns are eroding profits. Less
product is refined, and what is
refined is of a lesser quality, further
cutting into margins. Additional
changeouts and higher tempera-
tures resulting from distribution
and pressure drop issues mean
greater risk exposure for equip-
ment, personnel, and the
environment. Certainly, companies
are feeling the pressure to turn
things around.
It is natural for refiners to look to
the catalyst – the reactor’s heart and
purpose – to solve the problem.
Unfortunately, ‘new and improved’
catalyst based solutions can be
expensive and may not really be
solutions at all. Ultimately, this
leaves refiners scratching their
heads, wondering what sort of black
magic is required to solve the
performance problem.
Optimising catalysis has very little
to do with the catalyst. And no
magic is required.
Purification and dispersion
strategies
Those seeking to improve catalyst
performance should set their sights
further upstream to the purification
and dispersion of the feedstock.
Purification and dispersion repre-
sent two distinct phases of catalysis
optimisation. Purification is the
process of removing foulants (parti-
cles and poisons) from the feedstock
that can interfere with catalyst
performance. Dispersion is the
process of maximising contact
www.eptq.com
between the feed and the catalyst,
resulting in stronger reactions
sustained for longer periods.
In traditional systems, the process
of purifying progressively impedes
dispersion, creating a Catch-22
dilemma. Crusting occurs in the
bed, blocking flow, creating hot
spots, and dramatically diminishing
catalyst contact, productivity, and
profitability. However, there is
an alternative to traditional systems.
Since 1989, Crystaphase has
provided purification and disper-
sion strategies to hundreds of
refining, petrochemical and chemi-
cal plants worldwide. Through a
disciplined understanding of the
quantifiable variables that impede
performance, we have developed a
systematic and replicable approach
for removing those obstacles.
Crystaphase reticulation technol-
ogy uses a proprietary internal
filtration design that eliminates
crusting in the purification phase,
thus maintaining uniform distribu-
tion in the dispersion phase,
allowing for longer production
cycles while mitigating pressure
drop problems.
Do you know your foulant?
Soluble and insoluble particles in
refinery feedstocks are increasingly
becoming a problem, due to the
processing of high acid and high
sulphur opportunity crude. Tight oil
and high TAN stocks are also more
commonplace, creating a challenge
for, and wreaking havoc with,
equipment. Cracked stocks come
with diolefins that can polymerise in
the reactor, forming carbonaceous
foulants. Other particles, like silica
fines, iron compounds and corro-
sion, can plug catalyst and
equipment.
Effective solutions require not
only knowing what is in your feed,
but how and where it accumulates,
and the chemistry behind it. This
insight can mean the difference
between developing a filtration
solution and creating a bigger
problem.
When examining elements in
refinery feedstock, it pays to be
thorough. Insoluble compounds
found in deposits are often incor-
rectly identified as catalyst poisons.
It is highly recommended that
numerous procedures are
conducted, so that the engineer or
scientist can correctly diagnose the
source and the chemistry behind the
problematic compounds. At
Crystaphase, a laboratory is dedi-
cated to foulant analysis and can
run a wide range of tests in order to
provide this crucial insight:
• Particle size analysis Using laser
diffraction, this can determine parti-
cle size distribution in a range of 0.1
to 3500 microns (µm), making it
possible to match a custom filtration
solution specifically to the particles
plaguing a reactor.
• Loss on ignition (LOI) Samples are
heated to approximately 500°C,
burning off any residual sulphur or
carbon, so that we can measure how
corrosion and carbon/polymer
deposition accelerate deposit
formation.
• Inductively coupled plasma (ICP)
We can test for a large array of
elements, reporting values as low as
a few ppm, identifying particles
contributing to pressure drop and
poisons shortening catalyst life.
• Scanning electron microscopy
Catalysis 2016 51
 (SEM) At up to 1200x magnification,
we can visually examine the shape
of accumulated foulant particles for
a clear picture of their role in dimin-
ished reactor performance. This
allows for the resolution of particles
and particle features as small as 1
µm. Understanding particle
morphology helps identify filtration
efficiencies and particle generation
sources.
• Energy dispersive X-ray spectros-
copy (EDS) EDS identifies the
chemical elements that make up
foulant particles. Together with SEM
imaging, it helps determine their
origin, trace their morphology under
process conditions, and determine
how they interfere with reactor
performance.
• Digital microscopy This cutting
edge tool can resolve samples down
to 1 µm with full depth of field, for
a lifelike, high acuity perspective on
the formation of foulant deposits.
• X-ray microtomography This tech-
nology lets us see inside a sample
and create a digital model of its
structure, allowing us to evaluate
the real world performance of its
filtration ability.
• Pressure drop analysis Combining
engineering and scientific program-
ming, this technology lets us
accurately predict the performance
of Crystaphase solutions at different
sizes and volumes.
• Reactor filtration and pressure drop
simulation A suite of software
allows us to anticipate pressure
drop issues and model proposed or
current solutions before the next
cycle, instead of after it.
The difference between particles
and poisons
Purification constitutes a science in
itself. While feed filters installed
upstream of hydroprocessing reac-
tors can remove particles larger than
10-50 µm (depending on the screen-
ing specifications), poisons or
soluble foulants such as iron naph-
thenate and asphaltenes can bypass
the filter system and precipitate out
in the catalyst bed. Additionally,
any particles below the micron
rating of the filter remain in the feed
post filtration, then agglomerate to
create larger problems downstream.
Crystaphase has developed an
52 Catalysis 2016
understanding of these foulants,
along with the means to eliminate
them. Specifically, we can effectively
capture and store particles in their
reactor beds, using a system that is
integrated directly into fixed bed
process applications.
Marketed as Crystaphase CatTrap
Technology, this solution features a
bypass design that eliminates cake-
layer formation. Here, particle
filtration actually occurs within inert
silica-alumina discs. With a high
porosity matrix, the product lets you
maintain flow much longer than
conventional solutions. Better yet, it
accomplishes this occupying far less
volume in the reactor, allowing you
to maximise catalyst load utilisation.
With high crush strength, increased
resistance to attrition and higher
density, CatTrap discs vary in size
and chemical composition, allowing
the solution to be customised to
specific applications.
ActiPhase Technology builds
upon CatTrap with catalytically
enhanced filtration designed for
problematic feeds, effective in elimi-
nating diolefin and coke deposition
and high TAN vacuum gas oil. This
helps to eliminate particle precipita-
tion that would otherwise occur in
the catalyst bed. One particle type in
particular, iron, has of late become
an especially prevalent problem in
hydroprocessing.
The age of iron
Generally, the presence of iron in
refinery feedstock and processes can
be attributed to a couple of sources.
The first, inherent iron, flows in
concentrations from 0.04-120 ppm.
For heavy crudes or bitumens, these
concentrations can range from
120-500 ppm, both soluble and
insoluble. The second source is a
result of corrosion from upstream
piping and process equipment
during upgrading processes. In turn,
this is caused by acidic compounds
in the feed, improperly matched
with process metallurgy.
As an example of the purification
challenges faced by refiners, one US
Gulf Coast unit had experienced
pressure drop issues for years. A
filtration system installed above the
main catalyst bed had little effect,
and the reactor was unable to go
beyond its 12-month production
cycle. After installing specialised
internals, catalyst was added atop
the distribution tray. Suddenly and
unexpectedly, the fouling rate
doubled, reducing cycle time to six
months.
At this point, late in the skim, the
refiner reached out to Crystaphase.
We identified the offending foulant
as iron sulphide, which had entered
the reactor as iron naphthenate,
completely bypassing the filtration
system. We hypothesised that
the iron was migrating in this solu-
ble form before precipitating in the
catalyst bed. We took samples back
to our lab for an overnight analysis.
Scanning electron microscopy
(SEM) confirmed the precipitation
problem. As the actual image shows
(see Figure 1), precipitated iron
results in a type of crystalline struc-
ture known as pyrrhotite – beautiful
and distinctly different in appear-
ance from particulate iron.
Since the skim was already in
process, a partial solution based
upon limited space availability was
implemented using an active filtra-
tion system. This would induce a
chemical reaction prior to inert
filtration, removing the precipitated
iron sulphide before it reached the
catalyst.
At the next changeout, we were
able to completely reconfigure
a solution built around the
precipitation issue, comparing
comprehensive data from both
shutdowns. This optimised configu-
ration, which included an ActiPhase
filtration system above the inert
filtration system, enabled the unit to
achieve a 16-month production
cycle.
This was the longest cycle the
reactor had achieved in 10 years,
and the first time in 16 years that
the shutdown was for activity, not
pressure drop. During the
changeout, Crystaphase was able to
make additional adjustments for
optimisation in dealing with precipi-
tated particles, which then resulted
in a 20-month cycle, nearly four
times longer than its shortest
production cycle of six months.
After more than a decade of strug-
gling with performance, this unit
was finally clear of pressure drop
www.eptq.com
issues, able to make better use of the
catalyst and operate at full potential.
How iron poisons profitability
As you can see in another example
of iron fouling, pressure drop is not
always an issue or an indicator. In
this case, the refiner was experienc-
ing catalyst deactivation within six
weeks of startup. Since the catalyst
in question was made from plati-
num, it was a particularly expensive
problem.
The refiner’s original plan was to
perform a hot hydrogen strip, a
process in which the accumulated
carbon is burned off, reactivating
the catalyst to run for several
additional 13-month cycles.
Unfortunately, when it came time
for the strip, the refiner discovered
iron deposits were binding with and
killing the catalyst. Instead of reacti-
vating, the refiner was forced to
vacuum out the reactor, haul the
material to a metal reclaimer to
separate the iron from the poisoned
catalyst, then put in a brand new
load.
Again, there was no pressure
drop, just activity loss due to iron
poisoning the catalyst. The refiner
was taking a financial hit not only
for the numerous shutdowns, but
for having to constantly replace
some of the most expensive catalyst
on the market. Crystaphase recom-
mended adding active filtration to
the load. This removed the iron
from the feed, mitigating the loss of
activity and enabling regeneration
of the catalyst.
At the next scheduled changeout
– and for the first time since the unit
had been in operation – the refiner
found no iron deposits, and was
able to regenerate the catalyst (see
Figure 2).
Figure 1 Scanning electron microscope images of iron sulphide: (left) a result of precipitation,
requiring active filtration to remove; (right) a result of natural corrosion processes
radial delta-T issues, and, ulti-
mately, an artificial cap on the inlet
temperature. All are particularly
problematic in reactor beds of 20 ft
or more.
At Crystaphase, dispersion solu-
tions are thorough, incorporating
unique geometry to enhance
uniform flow distribution and
performance while utilising the least
amount of reactor volume.
For refiners, that translates to
longer life cycles and greater yield.
By inhibiting rivulets, local hot spots
are eliminated, letting refiners opti-
mise reaction through greater
distribution, without having to
adjust temperature for problem
zones.
Turning down the heat
In heating trains, extremely high
skin temperatures can result in
dangerous side reactions and unex-
pected particle generation in the oil.
Higher temperatures near the piping
surface cause the oil in contact with
it to undergo reactions that would
not normally occur, resulting in
particle agglomeration. As we have
seen, feed filters are not always
sufficient in removing particles from
the feed.
Another refiner was running three
reactors in parallel trains on the
hydrocracker unit, processing 60 000
b/d fresh naphtha feed, with an
additional 20 000 b/d recycled. Even
though the refiner had installed 5
µm feed filters, it was seeing
100-1000 µm particles in the bed,
causing pressure drop and tempera-
ture excursion issues.
In this case, the refiner wanted to
run a comparison between our
recommendation and the existing
configuration. The first reactor was
skimmed and reloaded with the
original material. The second and
third reactor were skimmed and
loaded with 6 in of inert filtration,
which took up only half the volume.
Figure 3 shows a comparison of all
three reactors. In the two utilising

Dispersion: the science of going

against the flow
In order to truly maximise reactor
performance – and contact between
catalyst and feedstock – uniformity
of fluid distribution is a must.
Unfortunately, it can be a challenge
to maintain. Natural flow dynamics
invariably bring about the degrada-
tion of the reactor fluid stream, a
process known commonly as rivulet
formation or feed coalescence. This Figure 2 Iron fouling of catalyst: (left) a top grab sample from the original load showing
causes catalyst coking, widening iron deposits; (right) after Crystaphase treatment, showing no iron

www.eptq.com Catalysis 2016 53

 90
Reactor 1
80 Reactor 2

Normalised pressure drop, psi

Reactor 3
70

60

50

40

30

20

10

0
0 50 100 150 200 250 300 350 400 450 500 550 600
Days on oil

Figure 3 Pressure drop comparisons on three parallel reactors. At 300 days, the two reactors using Crystaphase treatments show
mitigated pressure drop, while the remaining reactor shows a steep increase

Crystaphase solutions, the refiner
saw a longer cycle length and
increased activity and throughput.
The risk of temperature excursion
was also reduced. All three reactors
are currently running on
Crystaphase configured filtration.
Performance is everything
Without question, the overriding
goal is to improve and extend the
performance of your catalyst.
Changing out your catalyst merely
addresses the symptoms of the
problem. Raising the temperature
on the incoming feedstock will let
you squeeze a little more activity
out of your catalyst, but it
also moves you that much closer
90
80
Normalised pressure drop, psi
to your next shutdown. As
foulants accumulate in your reactor
through agglomeration, precipita-
tion, and polymerisation,
maintaining flow will require
greater and greater pressure differ-
ential. The dreaded curve begins its
precipitous rise.
A more assured, and safer, path to
greater performance is to remove
any obstacle that lies in the way,
whether it is iron, nickel, vanadium,
silicon, or arsenic. Channelling and
coking can also limit oil-catalyst
interaction. Purification and disper-
sion strategies, based on accurate
insight of the unique conditions
occurring inside a reactor, allow you
to systematically remove those
Cycle 1
Cycle 2
obstacles, keeping temperatures in
optimal range and extending the
reactor’s life cycle.
Space is everything else
The reticulated solution developed
by Crystaphase, in which filtration
occurs within the product, has a
matrix of up to 85% internal poros-
ity. This maintains flow much
longer than conventional solutions,
while using reactor volume far
more efficiently. When randomly
loaded into a unit, the sum of the
effective porosity and external void
space exceeds 90%, which lets you
maximise your catalyst load
utilisation.
Another refiner was running a
coker naphtha feed into a naphtha
hydrotreater. Engineers were
encountering pressure drop issues
at 225 days, forcing a shutdown

Cycle 3 before the catalyst was spent. For

70 this reason, they had downgraded
Cycle 4 − Crystaphase
60 to recycled catalyst. Since they
could not achieve the longer cycle,
50 there was no point in using the
40 high activity catalyst for which the
reactor was designed.
30 Activity shutdowns are what
20 refiners seek to achieve. This means
the catalyst has gone through its
10 natural cycle prior to expiring. It is
0
what systems are designed for. It is
0 50 100 150 200 250 300 350 what catalyst companies base their
Days on oil models on. Basically, it is how
refiners get their money’s worth
Figure 4 With Crystaphase active filtration, this hydrotreater extended its cycle length to from their catalyst. In this case, we
300 days, still without encountering pressure drop problems provided a solution – reticulated

54 Catalysis 2016 www.eptq.com

technology – that allowed the
refiner to avoid these pressure drop
problems and extend production
through the natural life of the cata-
lyst. It now made economic sense
for the refiner to go back to using
the high activity catalyst.
Even better, the refiner was able
to replace 88 in of graded material
with 42 in of our active filtration
solution, which significantly
increased the catalyst volume. The
cycle length increased to 300 days,
at which point a shutdown was
implemented – in this case due to
activity, not pressure drop (see
Figure 4). That is a 33% longer
production cycle on higher activity
catalyst, resulting in a 25% increase
in daily throughput.
Throughput: an economic
eye-opener
Refiners understand that downtime
costs money. It is simple mathemat-
ics. When a reactor is offline for a
turnaround, it is not producing
product, which means no profit is
being generated. In addition to lost
productivity, there are costs for
material and labour. Turnarounds
are also risky. If something goes
Industrial catalyst service –
from start to finish
ICS_ad_PTQ_125x178mm.indd 1
www.eptq.com
wrong, there are costs associated
with that as well.
But consider what diminished
throughput can cost over the course
of an entire production cycle. If you
have a foulant problem that chokes
throughput by 10%, that represents
profits lost over months, even years.
The accrued loss can easily dwarf
the one-time cost of a turnaround,
and typically does. This is where
purification and dispersion solutions
can make a dramatic impact.
Another refiner was processing
straight run naphtha, which is
usually an easy feed to process.
Engineers like it because no addi-
tives are required, no poisons are
added, and no free radicals are pres-
ent that can turn into foulants. In
this case, however, the refiner was
facing increasingly shorter produc-
tion cycles, running 331 days on oil,
then 257 days, then 197 days before
a pressure drop shutdown was
required.
At this point, we recommended
replacing 180 cu ft of conventional
wagon wheels and rings with
159 cu ft of active filtration. This
strategy more than tripled the unit’s
production cycle to 716 days, which
had a dramatic impact on the refin-
er’s bottom line. Maintenance costs
associated with turnarounds –
labour, equipment, materials, and
downtime – were reduced, while
the additional production volume
generated more revenue. All
combined, the annual profitability of
the unit increased by nearly $3.9
million.
Conclusion
The examples detailed here are typi-
cal and continue to justify this
approach. Purification and disper-
sion strategies have extended
production cycles by as much as
10-fold and improved throughput
by up to 50%.
With its internal filtration design,
Crystaphase technology can purify
feedstocks without sacrificing
dispersion capabilities, and can do
so occupying far less space, letting
hydroprocessors maximise catalyst
load capacity.
Austin Schneider is Director of Technology
with Crystaphase and has worked in the
refining industry since 2004, focusing on
fixed bed reactor hydraulics, feed purification,
and particle generation. He holds a MS in
mechanical engineering and a BS in physics.
BUCHEN-ICS is your service specialist
for all work on catalyst-relevant process-
ing plants such as hydrocrackers, FCC-
reactors or UOP-CCR reformers and
extends from plant preparation through
to catalyst handling in normal and inert
atmosphere, all the way to regeneration,
passivation or the recycling of catalyst
material – at all times taking into account
safety and quality as well as on-time and
on-budget delivery
BUCHEN-ICS, Industrial-Catalyst Service GmbH
Emdener Str. 278 // 50735 Cologne // Germany
T +49 221 7177 0 // F +49 221 7177 218
info.ics@buchen.net // buchen-ics.com
A company of the REMONDIS Group
14.09.2015 07:37:31
Catalysis 2016 55
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Big changes
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Trust our long experience

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CATALYST SOLUTIONS THAT DELIVER VALUE:

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3088_Catalysts_A4_en.indd 1 03.06.14 14:37

 Calcium containing feedstock processing
Development of a FCC catalyst/additive combination with high tolerance to
calcium contamination from lower cost feedstock
CHINTHALA PRAVEEN KUMAR, SUKUMAR MANDAL, GOPAL RAVICHANDRAN, SRIKANTA DINDA, AMIT V GOHEL,
ASHWANI YADAV and ASIT KUMAR DAS
Reliance Industries Limited
R
efiners continually find ways
to improve refining margin by
processing cheaper feedstocks,
such as heavy oil, resid and oppor-
tunity crudes in their FCC units.
Whenever processing of resid or
some cheaper feedstock is increased
in the FCC unit, plant operating
severity is adjusted. Both metals
and basic nitrogen compounds,
which are known to poison FCC
catalysts, are concentrated in the
heavier end of gas oils and resids.
These poisons, mostly present in
the heavier hydrocarbon molecules,
deposit on the catalyst during
cracking reactions.
Each type of poison affects the
FCC catalyst differently. Refiners
are conversant with the detrimental
effects of vanadium, basic nitrogen,
nickel and their treatments.
Vanadium deactivates Y-zeolite by
the formation of vanadic acid in the
presence of steam at high tempera-
ture and sodium facilitates the
dealumination reaction by forming
a low eutectic with the rare earth
metals present in Y zeolite. Nickel
promotes dehydrogenation reac-
tions leading to high fuel gas make
and coke formation and hence
reduces the selectivity of desired
products. Iron and calcium metals
deposit on the catalyst surface and
cause a loss of diffusivity, which
leads to a loss in conversion and an
increase in coke and bottoms.
Deposition of iron on FCC catalyst
reduces accessibility to the catalyst
pore and consequently reduces the
catalyst’s activity. Researchers have
studied the effect of calcium and
iron on coke formation over
ultra-stable Y-zeolite catalyst in the
absence and presence of nickel and
www.eptq.com
vanadium metal.1 Different zeolite
samples are prepared by impreg-
nating nickel and vanadium on
ultra-stable Y-zeolite, previously
exchanged with calcium. The cata-
lyst samples are used for cracking
n-hexane at 500°C. The study
showed that catalyst containing
calcium in combination with nickel
and vanadium reduces coke forma-
tion significantly and increases the
olefin to paraffin ratio.
There is plenty of reported infor-
mation on the effects of
contaminant nickel, vanadium,
sodium and other metals in the
FCC.2 Guthrie et al described passi-
vating the reactivity of contaminant
metals, such as nickel and vana-
dium, which deposited on a
catalytic cracking catalyst, by
adding to a cracking catalyst a
mixture of a calcium containing
material and a magnesium contain-
ing material in a separate reactor in
the presence of steam.2 The
preferred calcium containing mate-
rial was dolomite and the preferred
magnesium containing material
was sepiolite. The cheaper feed-
stock contains metal contaminants,
which contribute to lower conver-
sion and the production of more
fuel gas and coke. The higher fuel
gas yield often touches the reactor
cyclone velocity limits, which
results in lower severity operation
in the FCC unit, such as lower riser
temperature. Similarly, higher coke
yield leads to a higher regenerator
temperature that lowers unit
conversion.
However, there have not been
many studies focused specifically
on calcium contaminants and their
effect on the performance of FCC
catalysts/additives. Some crude
samples have a higher concentra-
tion of calcium, alone or with other
conventional contaminant metals
(Na, Ni and V). Hence, a study was
undertaken on the effects of
calcium on FCC catalyst/additive
on their performance in a fixed
fluidised bed reactor. The catalyst
and additive were optimised with
high zeolite and matrix components
to resist the effects of contaminants
like calcium in the feed. The perfor-
mance results are correlated with
physico-chemical characterisations
to gain a better understandings of
the effect of calcium on catalyst and
additive.
Experimental
Catalyst preparation
FCC catalyst and additive were
prepared according to procedu res
mentioned in earlier patent disclo-
sures.3 ZSM-5 additive was
prepared by mixing the required
quantities of kaolin clay, boehmite
alumina, phosphate salt, ZSM-5
zeolite and colloidal silica with a
suitable dispersant to obtain a free
flowing slurry, which was then
subjected to spray drying to form
catalyst microspheres. Two kinds of
phosphorus source, H3PO4 and
monoammonium hydrogen phos-
phate were used to introduce
phosphorus to the ZSM-5 additive
formulation. The composition
details of the catalyst and additive
are shown in Table 1. The obtained
spray dried microsphere particles
were calcined at 500°C for one hour
prior to hydrothermal deactivation.
The FCC catalyst was prepared
by mixing the required quantities
of kaolin clay, peptised boehmite
Catalysis 2016 57
 Typical compositions of catalyst and ZSM-5 additive formulations
Additive/catalyst composition
USY, wt%
ZSM-5, wt%
P2O5, wt%
Alumina, wt%
Silica sol, wt%
REO, wt%
Balance clay
Table 1
alumina, USY-zeolite and colloidal
silica with a suitable dispersant to
obtain a free flowing slurry, which
was then subjected to spray drying
to form catalyst microspheres. The
spray dried catalyst was exchanged
with lanthanum nitrate (a rare
earth salt) and then the sample was
calcined at 500°C for one hour prior
to hydrothermal deactivation.
A modified Mitchell method4 was
followed for the impregnation of
calcium on catalyst and additive
separately, followed by calcination
at 590°C for three hours. The
calcium content varied from 0 ppm
to 10 000 ppm using calcium naph-
thenate as the source of calcium
precursor since calcium is present
in crude mostly in the form of
calcium naphthenate.
All calcium doped catalyst and
additive samples were then hydro-
thermally deactivated at 800°C for
20 hours using 100% steam at
atmospheric pressure before the
cracking reaction took place.
BET surface area and pore volume
measurements
Nitrogen gas adsorption/desorp-
tion isotherms were obtained using
a Micromeritics ASAP 2020 unit.
The catalysts were degassed for
two hours at 300°C prior to adsorp-
tion. Nitrogen gas was dosed very
precisely for both adsorption and
desorption processes to generate
highly accurate isotherm data. The
BET surface area was determined
by considering relative pressure
(P/P0) between 0.05 to 0.20 and
pore volume at 0.98 relative pres-
sure. The t-plot was used to
calculate the external surface area
of the catalyst particles (calculated
as the surface area of pores larger
than micropores).
58 Catalysis 2016
Catalyst Additive
33 0 Feed injection time
0 45
0 11
12 5 Rx temp., °C
23 23
0.5 0 operation
Balance clay
NH3-TPD measurements
Ammonia temperature programmed
desorption (TPD) experiments were
carried out on a Micrometrics
Autochem 2920 unit equipped with
a thermal conductivity detector
(TCD). The sample was pre-treated
at 600°C under a flow of helium gas
for an hour. The sample was satu-
rated with ammonia at 120°C for 30
minutes and ammonia was flushed
out subsequently at the same
temperature in a helium flow for an
hour to remove weakly adsorbed
ammonia. TPD analysis was carried
out from 100°C to 600°C at a heating
rate of 10°C/min. The desorbed
ammonia was quantified with TCD
and the signal was plotted against
time/ temperature.
Cracking reaction
The advanced cracking evaluation
(ACE) unit is a fixed fluid bed reac-
tor for the evaluation of catalysts
and additives, feedstocks and
process development. It is down-
Physico-chemical properties of
prepared FCC catalyst (without
calcium impregnation)
Surface area and pore volume
Total surface area
Zeolite surface area
Matrix surface area
Total pore volume 0.203 cc/g
Zeolite pore volume 0.049 cc/g
Chemical analysis and acidity
Al2O3, wt%
Na2O, wt%
RE2O3, wt%
Total acidity, mmol/g
Average particle size distribution
and attrition index
APS, µ
Fines (<40 µ), %
Attrition Index (ASTM D5757)
(wt% loss in 5 hrs)
Table 3
ACE operating conditions
Parameter ACE protocol
Fixed at 30 seconds
C/O range 4 to 10
Feed rate, gm/min 2.0
545
Rx. pressure, kg/cm2(g) Atmospheric
Table 2
flow with respect to feed injection,
an isothermal tubular reactor
equipped with a central thermowell
to measure temperature in the cata-
lyst bed. The reactor is heated by
an electric furnace with a minimum
of three separate heating sections,
which allow fine control for isother-
mal operation. It includes control
system hardware and software that
enables accurate multiple runs
without operator intervention.5
Cracking reactions in the ACE reac-
tor take place in conditions that
simulate a commercial FCC riser
(see Table 2). The conversion is
varied by changing the catalyst
loading at constant feed rate.
The calcium impregnated catalyst
and additive were hydrothermally
deactivated at 800ºC for 20 hours
prior to performance evaluation.
The catalyst and additive are used
as a mixture of 75% catalyst and
25% additive for evaluation.
Reaction was carried out at four
different catalyst to oil ratios (from
4 to 10) to generate a wide range of
conversion data. The reaction
temperature was maintained at
545°C. Product gas and liquid were
analysed in an Agilent 3000A micro
GC and a Varian 450 GC SIMDIST
336 m2/g respectively.
226 m2/g
110 m2/g
Results and discussion
Physico-chemical properties of the
FCC catalyst
29.4 The spray dried catalyst after rare
0.28
earth exchange and calcination is
0.54
706 analysed by various physico-chemi-
cal techniques and the results are
summarised in Table 3.
71
The total surface area of prepared
4
FCC catalyst is 336 m2/g, which
3 decreases to 165 m2/g after hydro-
thermal deactivation at 800ºC for 20
hours (see Tables 3 and 4). The
www.eptq.com
decrease in surface area of steamed
FCC catalyst is mainly due to
dealumination of the zeolite, result-
ing in a loss of Al-OH-Si groups
responsible for Bronsted acidity;
hydrothermal treatment leads to
partial destruction of the Y-zeolite
structure and thereby a significant
decrease in surface area, pore
volume and acidity is anticipated.
The decrease further depends on
the severity of the hydrothermal
deactivation conditions and stabil-
ity of zeolite, which is formulation
specific. Exchange of rare earth
retards destruction of the Y-zeolite
during hydrothermal treatment,
which also results in an increase in
the strength of the acid sites. The
average particle size (APS) and
attrition index (AI) results (see
Table 3) are within the range of
required specifications of commer-
cial catalyst.
Acidity measurements were
carried out by the ammonia TPD
method. The ammonia TPD profile
of prepared FCC catalyst before
and after hydrothermal deactiva-
tion is shown in Figure 1. It can be
seen from Figure 1 that the acidic
sites are distributed in two regions:
one is due to weak acidic sites
(Tmax1: ~230ºC) and the other is due
to strong acidic sites (Tmax1: ~350ºC).
The total acidity of catalyst prior to
hydrothermal deactivation is about
0.706 mmol/g, decreasing to 0.044
mmol/g after steaming. The
decrease in acidity (both weak and
strong acidic sites) is very rapid in
FCC catalyst and the amount of
acid sites present in the catalyst are
minimal (0.044 mmol/g) after
hydrothermal deactivation.
The calcium impregnated (0, 5000
and 10 000 ppm) FCC catalyst
samples are hydrothermally deacti-
vated and their physical properties
are shown in Table 4. The total
surface area of calcium impreg-
nated catalyst samples reduces to
137 m2/gm from 165 m2/gm with
an increase in calcium level from 0
to 10 000 ppm. The decrease in total
pore volumes are also similar. The
question is whether the decrease in
these properties is due to zeolite
pore blockage or blockage of matrix
pores (mesopores) by calcium. To
understand further, a t-plot was
www.eptq.com
Surface area, pore volume and acidity of hydrothermally deactivated FCC catalyst
samples having calcium contents from 0 to 1 wt%
Parameters FCC catalyst (hydrothermally deactivated)
Calcium concentration on catalyst, ppm 0 5000 10 000
Total surface area, m2/g 165 149 137
Zeolite surface area, m2/g 107 107 92
Matrix surface area, m2/g 58 42 45
Total pore volume, cc/g 0.203 0.187 0.180
Zeolite pore volume, cc/g 0.049 0.049 0.042
Total pore volume reduction, % Base 7.9 11.3
Total acidity, mmol/g 0.044 0.044 0.036
Acidity reduction, mmol/g Base Nil 18
Table 4
used to calculate the matrix surface shows the NH3-TPD profiles of
area (pores larger than micropores) hydrothermally deactivated cata-
and acidity (ammonia TPD) of the lysts with calcium contents from 0
catalyst particles. to 10 000 ppm. Similar to the surface
It is interesting to note that the area results, the total acidity (weak
zeolite surface area (107 m2/g), acid sites) is also comparable, or not
zeolite pore volume (0.049 cc/g) much changed, when the calcium
and total acidity (0.044 mmol/g) are content is 0 ppm to 5000 ppm; acid-
the same and did not change when ity drops thereafter as zeolite
calcium is present in the catalyst up surface area is affected by an
to 5000 ppm (see Table 4). The increasing calcium level at 10 000
decrease in matrix surface area from ppm.
58 m2/g to 42 m2/g with no change
in zeolite surface area suggests that Physico-chemical properties of
impregnated calcium is mostly ZSM-5 additive
deposited in the catalyst matrix and The spray dried catalyst additive
possibly has not blocked the zeolite after calcination is analysed and
pores. However, when the calcium various physico-chemical proper-
content is increased to 10 000 ppm, ties are summarised in Table 5.
then the calcium partially filled The total surface area of prepared
both zeolite and matrix pores, ZSM-5 additive is 140 m2/g which
revealed in the decrease in zeolite increases to 170 m2/g after hydro-
surface area, zeolite pore volume thermal deactivation at 800ºC for 20
and acidity. Hence the prepared hours (see Tables 5 and 6). The
FCC catalyst is capable of capturing behaviour of steamed ZSM-5 addi-
calcium up to 5000 ppm. Figure 2 tive is different to that of FCC
Tmax1 Before steaming
After steaming
Tmax2
TCD signal, a.u.
100 200 300 400 500 600
Temperature, ºC
Figure 1 Ammonia TPD profile of FCC catalyst before and after hydrothermal deactivation
Catalysis 2016 59
 Physico-chemical properties of
prepared ZSM-5 additive (without 0 ppm
calcium impregnation) 5000 ppm
10 000 ppm
Surface area and pore volume

TCD signal, a.u.

Total surface area 140 m2/g
Zeolite surface area 110 m2/g
Matrix surface area 30 m2/g
Total pore volume (cc/g) 0.134
Zeolite pore volume (cc/g) 0.053
Chemical analysis and acidity
Al2O3, wt% 18.7
Na2O, wt% 0.11
P2O5, wt% 11.9
Total acidity, mmol/g 0.240
Average particle size distribution and
attrition index
100 200 300 400 500 600
APS, µ 77
Fines (<40 µ), % 6 Temperature, ºC
Attrition Index (ASTM D5757)
(wt% loss in 5 hrs) 4
Figure 2 Ammonia TPD profile of hydrothermally deactivated catalyst with calcium
Table 5 contents from 0 to 10 000 ppm

catalyst containing Y-zeolite. In Surface area, pore volume and acidity of hydrothermally deactivated ZSM-5
contrast to FCC catalyst, steaming additive samples with calcium content of 0-1 wt%
of ZSM-5 additive results in either
an increase in total surface area or Parameters ZSM-5 additive (hydrothermally deactivated)
the same total surface area, depend- Calcium concentration on additive, ppm 0 5000 10 000
Total surface area, m2/g 170 166 148
ing on the relocation of aluminum/ Zeolite surface area, m2/g 93 88 77
phosphate sites in the zeolite Matrix surface area, m2/g 77 78 61
framework and matrix. The surface Total pore volume, cc/g 0.153 0.151 0.136
area also depends on the severity of Zeolite pore volume, cc/g 0.042 0.040 0.035
Total pore volume reduction, % Base 1.3 11.1
hydrothermal deactivation condi- Total acidity, mmol/g 0.100 0.090 0.062
tions and the stability of the zeolite. Acidity reduction, mmol/g Base 10 38
It is well known in prior art that
the hydrothermal stability of ZSM-5 Table 6
zeolites in FCC additive is stabi-
lised by phosphates. Although tallinity and surface area loss is due to relocation of aluminum and
dealumination occurs in ZSM-5 observed. In fact, the surface area phosphorous sites outside the
zeolite, its crystal structure is increases, particularly that of the framework. The zeolite surface area
quite stable under hydrothermal matrix in ZSM-5 additives after also decreases if the sample under-
deactivations, hence not much crys- hydrothermal deactivation. This is goes severe hydrothermal
deactivations, leading to dealumi-
nation. The zeolite structure too
Tmax1 Fresh
collapses and this can be seen in a
Tmax2
Steamed
lower zeolite surface area and crys-
tallinity. The surface area further
depends on the phosphate contents
and binders used in the formula-
TCD signal, a.u.

tion. In the prepared ZSM-5

additive, the zeolite surface area
decreased to 93 m2/g from 110
m2/g and the matrix surface area
increased to 77 m2/g from 30 m2/g.
The average particle size and attri-
tion index results are within the
range of desired specifications.
Figure 3 shows the ammonia TPD
100 200 300 400 500 600 profile of prepared ZSM-5 additive
Temperature, ºC before and after hydrothermal
deactivation. The total acidity of
ZSM-5 additive is observed to be
Figure 3 Ammonia TPD profile of ZSM-5 additive before and after hydrothermal deactivation 0.240 mmol/g, which decreases to

60 Catalysis 2016 www.eptq.com

0.100 mmol/g. Unlike FCC catalyst,
the decrease in acidity of ZSM-5
0 ppm
additive is not significant. The total 5000 ppm
acid sites present in steamed addi- 10 000 ppm
tive are higher (0.100 mmol/g) in
comparison to steamed catalyst

TCD signal, a.u.

(0.044 mmol/g). The acid sites pres-
ent in fresh additive are mostly
weak acids with some strong acid
sites. However, only weak acid
sites are present in both catalyst
and additive after steaming.
The calcium impregnated (0, 5000
and 10 000 ppm) ZSM-5 additive
samples are hydrothermally deacti-
vated and their physical properties
are shown in Table 6. The results
show that the physical properties of
the FCC additive are not changed
appreciably when the calcium
concentration is between 0.0 ppm
and 5000 ppm. A marginal decrease
in zeolite surface area and acidity
are observed in 5000 ppm calcium
containing additive. This indicates
calcium is partially filling zeolite
pores at lower concentration levels
(<5000 ppm). However, at higher
concentrations (>5000 ppm),
calcium fills in both the zeolite and
matrix pores of the ZSM-5 additive.
The total surface area reduced from
166 m2/g to 148 m2/g due to a
decrease in zeolite surface area, as
well as matrix surface area in a
10000 ppm calcium containing
additive. Similarly, pore volumes
and acidities decrease significantly
when the calcium level is 10 000
ppm. Figure 4 shows the NH3-TPD
profiles of hydrothermally deacti-
vated ZSM-5 additives with
calcium contents from 0 ppm to
10 000 ppm. Similar to the surface
area results, the acidity is also
marginal decrease in 5000 ppm Ca
and the fall in acidity is much
higher when the calcium content is
100
Figure 4 Ammonia TPD profile of hydrothermally deactivated ZSM-5 additive with
calcium content from 0 to 10 000 ppm
vs calcium concentration is plotted
in Figure 5, which shows that the
catalyst has lost its activity by
1 wt% and 1.7 wt% when the
calcium level was increased to 5000
ppm and 10 000 ppm, respectively.
Escobar et al reported monometallic
catalysts containing iron or calcium
were less active than a USY-zeolite
sample.1 Both iron and calcium
favour the olefin to paraffin ratio
compared to the metal free sample.
These metals increase olefin forma-
tion and poison acid sites. The effect
of calcium concentration on fuel
gas, coke and CSO yields are shown
in Figure 6. The results show the
decrease in fuel gas yield with
increase in calcium level. It is inter-
esting to note that fuel gas make
reduces to 2.9 wt% from a base
level of 4.75 wt% when the calcium
76.5
76.0
Conversion, wt%
200 300 400 500 600
Temperature, ºC
level on catalyst/additive increases
to 10 000 ppm. The coke selectivity
plot shows that coke yield increases
with an increase in calcium level
and the increment is significant at
10 000 ppm. These findings contrast
with the nickel effect. Nickel makes
more coke and more fuel gas,
whereas calcium also shows more
coke but reduces fuel gas considera-
bly. In the current study, the
decrease in fuel gas yield can be
attributed to lower monomolecular
and bimolecular reactions, which is
also related to a decrease in acid
sites. Propylene and LPG yields
were also lower in 10 000 ppm
calcium containing samples.
The effect of calcium on propylene
yield is shown in Figure 7. The plot
shows that up to 5000 ppm calcium
level, there was not much change in

10 000 ppm.
75.5
Fluid catalytic cracking of
hydrotreated VGO on calcium 75.0
impregnated catalyst/additive
Calcium impregnated, steam deacti-
74.5
vated catalyst and additive were
evaluated in the ACE at 545°C
using hydrotreated VGO feed. 74.0
0 2000 4000 6000 8000 10 000 12 000
Conversion at a C/O ratio of 8.2
and product selectivities at a Calcium concentration, ppm
conversion level of 76 wt% are
shown in Figures 5 to 8. Conversion Figure 5 Conversion vs calcium loading from 0 to 10 000 ppm in FCC catalyst and additive

www.eptq.com Catalysis 2016 61

 ppm calcium level could be attrib-
5.0 8.0 uted to reduced catalyst activity of
Selectivity: dry gas and coke, the additive.

Selectivity: CSO, wt%

4.5 7.8
Estimated heat balanced yields
For prediction of heat balanced
4.0 7.6
plant yield based on ACE data,
wt%

conversion and coke factors are fed

3.5 7.4 to the FCC models to obtain heat
balanced conversion for the calcium
3.0 Dry gas 7.2 doped catalyst/additive. Selectivity
Coke deltas, thereafter, are imposed at
CSO the new conversion to predict final
2.5 7.0
0 2000 4000 6000 8000 10 000 12 000 yield shifts with the calcium
Calcium concentration, ppm impregnated catalyst/additive. The
estimated heat balanced yields are
shown in Table 7. It can be
Figure 6 Effect of calcium concentration on dry gas, coke and CSO yields in the FCC concluded that the catalyst loses its
conversion by 1.2 wt% and 2.1 wt%
when the calcium level on the cata-
76.0 lyst was increased to 5000 ppm and
10 000 ppm respectively.
Propylene selectivity, wt%

K Bryden et al studied the detailed

75.5 characterisation of tight oils and
cracking of these feedstocks under
different operating conditions.6
75.0 Tight oils are generally light, sweet
and easy to crack and contain sedi-
ments with high levels of iron and
74.5 alkali metals. Iron in combination
with calcium and/or sodium has a
stronger negative effect on catalyst
74.0 performance than iron alone. It is
0 2000 4000 6000 8000 10 000 12 000
reported that iron and calcium
Calcium concentration, ppm
poisoning results in a loss of bottom
cracking due to pore blockage, lead-
Figure 7 Effect of calcium concentration on propylene yield in the FCC ing to a drop in conversion.
However, the calcium tolerance of
these catalysts for FCC feedstocks in
40.5 17.0 general are not reported.
Yield: LPG and gasoline, wt%

The fuel gas make reduces to half

37.5 16.8 of the base level as the calcium level
on catalyst increases to 10 000 ppm.
Yield: LCO, wt%

LPG as well as propylene selectivity

34.5 16.6 for the base case and the 5000 ppm
calcium case is almost the same.
31.5 16.4 However, when the calcium level
increases to 10 000 ppm, the drop in
28.5 LPG 16.2
LPG and propylene is significant. As
LCO per the heat balance yield, LPG and
Gasoline propylene make drop by 3.2% and
25.5 16.0 1.18% at the 10 000 ppm calcium
0 2000 4000 6000 8000 10 000 12 000
level. Gasoline make increases to
Calcium concentration, ppm
43.7% from a base value of 39.9
wt%. The secondary cracking of
Figure 8 Effect of calcium concentration on yields of LPG, gasoline and LCO in the FCC gasoline to lighter products includ-
ing LPG and propylene is
propylene yield, but an appreciable Figure 8 shows the effect of calcium significantly reduced at the 10 000
decrease in propylene yield was on the yield of LPG, gasoline and ppm calcium level. The change in
observed when the calcium concen- LCO. The decrease in LPG and LCO and CSO make is not much at
tration was increased to 10 000 ppm. increase in gasoline yields at 10 000 5000 ppm calcium. However, LCO

62 Catalysis 2016 www.eptq.com

yield with 10 000 ppm calcium,
increases to 14.2% from a base value
of 13.4%. Similarly, CSO make
increases to 8.12 wt% from 7.38% in
the presence of 10 000 ppm calcium.
Conclusions
The catalyst and additive in this
study are tolerant to calcium metal
contamination up to 5000 ppm
without affecting the product yields
of propylene and LPG. The cata-
lysts lower the additional fuel gas
by 12% and 50% when the calcium
concentration is 5000 ppm and
10 000 ppm respectively. Coke
yields are observed to increase with
calcium level and the increment is
significant at 10 000 ppm calcium.
The calcium effect is similar to the
nickel effect with respect to coke
make; however, it contrasts with
nickel with respect to fuel gas.
Therefore the catalyst and additive
provide the feasibility for process-
ing inferior quality hydrocarbon
feedstock of higher boiling point.
The catalyst was found to lose
activity by 1.2% and 2.1 wt% when
the calcium level on the catalyst
increases to 5000 ppm and 10 000
ppm respectively. Further, LPG and
propylene yields were found to
decrease considerably at the 10 000
ppm calcium level and gasoline
make increased to 43.7% from a
base value of 39.9 wt%.
Surface area and pore volume
results show that initial pore block-
age is not much in the catalyst and
additive up to the 5000 ppm
calcium level. At higher calcium
loading (10 000 ppm), both zeolite
and matrix pores are affected in the
catalyst and additive, with a
decrease in surface area and pore
volume. This is due to calcium fill-
ing zeolite as well as matrix pores
in the catalyst and additive at
higher concentrations (>5000 ppm).
Acidity measurements further
confirm the observations of surface
area and pore volume. The decrease
in acidity of catalyst and additive
was marginal or the same up to the
5000 ppm calcium level and acidity
decreased when calcium was >5000
ppm. Therefore, it can be concluded
that up to 5000 ppm calcium on
catalyst/additive, there was negligi-
ble effect on desirable yields. The
www.eptq.com
Estimated heat balanced yields at constant ROT of 545°C
Parameters Base case
Calcium , ppm 0 5000
Yield pattern, wt%
Fuel gas 4.09
Total LPG 29.84
LPG (excluding C3=) 20.12
Propylene 9.72
Gasoline 39.89
LCO 13.37
CSO 7.38
Coke 5.44
Conversion 79.8
Process conditions
Riser outlet temp, °C 545
Reactor pressure, kg/cm2(g) 2.82
Cat/oil 10.28
Table 7
reduction in activity and product
selectivities could be explained due
to an appreciable amount of reduced
acid sites in the ZSM-5 additive and
catalyst when calcium concentration
was >5000 ppm. Hence, the catalyst
and additive of the current study
has a potential to process calcium
containing feedstock in the FCC.
These catalysts may also be
employed in FCC units where fuel
gas is the major constraint.
References
1 Escobar A S, Pereira M M, Cerqueira H S, Appl.
Cat. A: Gen. 339, 2008, 61.
2 Guthrie C F, Jossens L W, Kennedy J V,
Paraskos J A, US patent no. 5260240, 1993.
3 S Dinda, Kumar Ch. P, Gohel A V, Yadav A,
Mandal S, Ravichandran G, Das A K, Application
nos. WO2013005225A1, US2014/0116923 A1,
EP2729553A1.
4 Mitchell B R, Ind. Eng. Chem. Prod. Res. Dev.,
19, 1980, 209.
5 Kayser J C, US patent No. 6069012, 2000.
6 Bryden K, Federspiel M, Habib E T, Jr., Schiller
R, Catalagram 114, W R Grace & Co., 2014.
Chinthala Praveen Kumar is a General
Manager in the Refining R&D Division of
Reliance Industries Limited (RIL). He has 16
years of experience in FCC and heterogeneous
catalysis with several patents and publications
to his credit. He holds degrees in chemistry
(MSc and PhD) from Osmania University and
IICT, Hyderabad, respectively.
Email: praveen.chinthala@ril.com
Sukumar Mandal is Assistant Vice President,
Lead FCC and coker process groups in the
Refining R&D Division of RIL. He has 25 years
of experience in refining processes with several
patents and publications to his credit. He holds
Ca doped case
10 000
3.59 2.0
29.88 26.60
20.09 18.06
9.79 8.54
39.70 43.74
13.74 14.20
7.69 8.12
5.41 5.32
78.6 77.7
545 545
2.82 2.82
10.25 9.96
degrees in chemical engineering (MTech) from
IIT, Kanpur. Email: sukumar.k.mandal@ril.com
Gopal Ravichandran is Assistant Vice President,
Lead FCC catalyst group in the Refining R&D
Division of RIL. He has 20 years of experience
in refining catalysis with several patents and
publications to his credit. He holds degrees
in chemistry (MSc and PhD) from IIT Mumbai
and engineering (MTech) from IIT, Kharagpur,
respectively.
Email: ravichandran.gopal@ril.com
Srikanta Dinda is an Associate Professor with
BITS Pilani, Hyderabad. He has four years of
experience in FCC processes at the Refining
R&D division of RIL. He holds degrees in
chemical engineering and chemistry (MTech,
PhD) from Calcutta University and IIT
Kharagpur, respectively.
Email: srikanta.dinda@gmail.com
Amit V Gohel is a Manager in the Refining R&D
Division of RIL. He has nine years of experience
in FCC processes and holds a degree in
chemical engineering (BTech) from V.V.P. Engg.
College, Rajkot, Gujarat University.
Email: av_gohel@yahoo.co.in
Ashwani Yadav is a Manager in the Refining
R&D Division of RIL. He has 10 years of
experience in R&D in fluid bed and coking
process development and holds a chemical
engineering degree (Diploma and B.tech)
from Government Polytechnic Sonepat and
Rajasthan Vedyapeeth University, respectively.
Email: Ashwani.h.Yadav@ril.com
Asit Kumar Das heads the Refining R&D
division at RIL, Jamnagar. He has 30 years of
experience in refining research with several
publications and patents to his credit. He holds
degrees in chemical engineering (BTech, MTech
and PhD from Jadhapur University, IIT Kanpur,
and University of Gent, Belgium, respectively.
Email: asit.das@ril.com
Catalysis 2016 63
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