catalysis

2017

ptq

cover and spine copy 10.indd 1 27/02/2017 12:51

 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

basf.indd 1
311995_CL_AZ_Raffineriecatalysatoren_Hydrocarbon_Anzeige_210x297.indd 1 24/02/2017
05.08.16 12:47
15:19
 catalysis Security of
ptq
feedstock supply
2017 Vol 13 No 2 3 Catalysing economic recovery
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
23 conventional
Increased steam wisdom that higher
methane fuel prices
reformer and a slowing economy
throughput
would curb demand and increase supply, but for the past seven years
Production Editor that has notMarie proved Basin
to beandthe Daniel
case. While Garythe rate of increase in world oil demand
Rachel Zamorski has declinedAir since
Liquidethe surprising 4% surge in 2004, it nevertheless appears that
production@petroleumtechnology.com demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
William Whittenberger and Jumal Shah
increasing oil consumption by China, India and even the Middle East producers
themselves will Johnson
continue.Matthey It is Process
also safeTechnologies
to assume that refinery and petrochemical
Graphics Editor conversion unit capacity will need to expand.
Mohammed Samiuddin No massive new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com 29 future.
foreseeable Optimising The world middle will distillate
remain dependent production on oil inand
a hydrocracker
gas for decades to
come even Jens though A Hansen and Asbjørn S Andersson
the upstream industry faces increasing challenges in the
Editorial discovery and production of new sources. In fact, some well-placed industry
Haldor Topsoe
PO Box 11283 analysts think 2008 may be the year where there is no increase in crude supply at
Spring TX 77391, USA all from regions outside of OPEC. For this reason, we will continue to see significant
tel +1 281 374 8240 investment
37 Lessonsin refinery from upgrades
FCC historydespite surging costs — security of feedstock
fax +1 281 257 0582 supply, albeit unconventional low-quality feedstock, takes precedence over the
Jacqueline
quality of feedstock Pope, Melissa Clough and Alexis Shackleford
supply.
FeedstockBASF optionsCatalysts
such as biomass (for biofuels production), Canadian tar sands
Advertising Sales Manager (for distillate production) and other types of unconventional crude sources require
Paul Mason
reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com
process47 confi Designing
gurations. and engineering
The quality of these catalysts
types of for hydrotreating
feedstock are one important
Advertising Sales reason whyKarl a widerKrueger, Max Ovchinnikov and Thomas Weberthe market. For
array of catalysts has been introduced into
Bob Aldridge example, as refiners cut deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com
Criterion Catalysts & Technologies
metals in the VGO requires a properly designed guard bed system to protect active
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Advertising Sales Office (eg, <10),
tel +44 870 90 303 90
53 high metals, for
Catalysts nitrogen
higher and other distillate
middle undesirableyields components is one of the
main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 accommodate Alex notYoononly higher volumes of catalyst, but also a wider variety of
catalyst withChevronspecific Technology
formulations.Marketing and Advanced Refining Technologies
Publisher
Non-catalytic processes are also playing a significant role in the refiner’s ability
Nic Allen Meredith Lansdown
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. For example,
some refiners Chevron
processing higher volumes of resid and atmospheric tower bottoms
Circulation have considered Brianadding
Watkins certain types of solvent-extraction processes in addition
Jacki Watts to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
circulation@petroleumtechnology.com coker operations.Advanced Refining Technologies
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 61 Catalyst filling in a fixed bed tubular reactor
However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20 Subrata Das and Naresh Kumar Singh
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax +44 870 90 600 40
the following articles
Fluor Daniel authored by experts in the fi eld of downstream process
ISSN 1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded to the Q&A published in this issue of PTQ Catalysis, as
well Cover
as to those respondents who addressed the online questions (www.eptq.com)
Petroleum Technology Quarterly (USPS
that High pressure section of the hydrocracking unit at Galp Energia’s Sines refinery, Portugal.
addressed the specifics of certain reactor and catalytic issues of importance to
Photo: Galp Energia
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. ©2017. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
Periodicals postage paid at Emigsville PA. reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
Postmaster: send address changes to mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
Petroleum Technology Quarterly c/o PO The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
Box 437, Emigsville, PA 17318-0437
responsible for any statements, opinions or views or for any inaccuracies.
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez

ed cont copy 3.indd 1 01/03/2017 11:06

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 catalysis Security
Catalysingof
ptq
feedstock supply
economic recovery
Vol213 No 2
Vol 22 No
2017 2008

DC
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
Editor René G Gonzalez atalysis makes the world of refining revolve that much faster. But can
refiners remain a big play for prospective investors. It used to be
Chris Cunningham
editor@petroleumtechnology.com it help to ease the pain of international sanctions for one of the world’s
editor@petroleumtechnology.com conventional wisdom that higher fuel prices and a slowing economy
biggest oil drillers? Russia vies with Saudi Arabia as the world’s largest
would curb demand and increase supply, but for the past seven years
producer. However, the federation’s refining industry is a long way from the
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 lead with regard
declined since the to technical
surprising performance.
4% surge inOil refiners
2004, in Russia need
it nevertheless to import
appears that
production@petroleumtechnology.com
production@petroleumtechnology.com
close to three quarters of the catalysts they need.
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidlyThere is no domestic production
of hydrocracking
increasing oil consumption catalystsbyand the hydrotreating
China, India and even catalysts
the Middleproduced East internally
producers
Graphics Editor to clean up diesel do not deliver a product that meets
themselves will continue. It is also safe to assume that refinery and petrochemical Euro 5 standards. Russian
Rob Fris Graphics Editor production of FCC catalysts
conversion unit capacity will need to expand. is well under half the amount that domestic
Mohammed Samiuddin
graphics@petroleumtechnology.com
Norefiners
massive need.new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com However, clean
foreseeable future. Thefuels
world standards
will remain in Russia
dependentare set onto oilcatch
and gas up for
with Western
decades to
Editorial
come standards,
even though and refiners are desperate
the upstream industry to improve their under-achieving
faces increasing challenges incon- the
tel +44 844 5888 773
Editorial
fax +44 844 5888 667 versionand
discovery rates, which of course
production of newmeans sources. accelerated
In fact, demand from those industry
some well-placed refiners
PO Box 11283 for high
analysts think performance
2008 may be catalysts.
the year where there is no increase in crude supply at
Spring
Business TX 77391,
Development USA
Director all fromThe internal
regions solution
outside of OPEC.to meetFor thisdemands
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catalyst
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investment to berefithe
nery responsibility
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ysis of feedstock
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be the company’s Omsk refinery in southern Siberia, which is
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confi gurations. The quality of these types of feedstock are one 6000 t/y
Advertising Sales
Nic Allen reason why a wider catalysts
of hydrotreating array of and catalysts
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of cracking into the
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Bob Aldridge
publisher@petroleumtechnology.com example,
will account for around one third of national demand, according to Gazprom. of
as refi ners cut deeper into the vacuum tower, the concentration
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Louisetel +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
circulation@petroleumtechnology.com study centres for catalysis. One of these, based in Novosibirsk, a mere stone’s
accommodate not only higher volumes of catalyst, but also a wider variety of
throw (on a Russian scale) from Omsk, is the Boreskov Institute which will
catalyst with specific formulations.
Publisher lead on the development
processes areof hydrogenation catalysts. Theinrefinery
the refihas
ner’salready
Crambeth Allen Publishing Ltd
NicArms
Allen Non-catalytic also playing a signifi cant role ability
Hopesay, Craven SY7 8HD, UK tested the first domestically produced hydrotreating catalyst. Even closer to
publisher@petroleumtechnology.com
tel +44 844 5888 776 to process whatever unconventional crude sources become available. For example,
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processing the Institute
higher volumes for Problems
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have considered adding certain types of solvent-extraction processes in addition and production of catalytic
Jacki Watts
ISSN 1362-363X cracking
to overall material.
improvements to crude unit (eg, vacuum tower revamps) and delayed
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operations. the turn of this year,inGazprom
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PTQ (Petroleum Technology Quarterly) (ISSN Ltd
pilot plant for catalytic cracking tests has started up at the centre; the catalysts
capacity.
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Hopesay, Craven Arms SY7by8HD,
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online questions
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industry.
burden of lost income, albeit it is an unexpected return to the days of
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA Russian privatisation.
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 CHRIS CUNNINGHAM
Box 437, Emigsville, PA 17318-0437
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez
Catalysis 2017 3

ed cont copy 3.indd 2 28/02/2017 09:49

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 catalysis q&a
Q What is the best route to prevent catalyst damage through
overheating in the regenerator in maximum propylene mode?
A Rick Fisher, Senior Technical Service Engineer, Johnson
Matthey Process Technologies, USA, rick.fisher@matthey.com
The first thing to come to mind to prevent overheating
in the regenerator is of course a catalyst cooler but as
this requires a major revamp and a large capital expen-
diture we will explore other more palatable options.
In maximum propylene mode, the riser tempera-
ture will most likely be maximised. To achieve this
increase in riser temperature, catalyst circulation has to
increase to provide the additional heat required for the
increased riser temperature and this results in increased
coke make and regenerator temperatures. To reduce
the regenerator temperature, we must find a way to
decrease the delta coke which will increase the catalyst
circulation rate.
One issue some FCC operators experience when cat-
alyst circulation increases is that residence time in the
stripper section becomes insufficient to fully purge
all strippable hydrocarbons from the FCC catalyst. In
more extreme cases, steam flows can be ‘dragged down’
by the high catalyst flow rate. In both these cases, the
rate of coke entering the regenerator increases (the rate
of coke divided by the catalyst circulation rate being
defined as ‘delta coke’), a fact that is made worse by
the unstripped hydrocarbons being of a relatively high
hydrogen content, further boosting regenerator tem-
peratures (due to the high energy of combustion of
hydrogen) and leading to accelerations in the hydro-
thermal deactivation of the FCC main catalyst (accel-
erated by the presence of elevated levels of hydrogen,
further exacerbated if quantities of steam from the
stripper are also pulled under). Therefore, the over-
all net effect is an increase in the temperature of the
regenerator.
Improvements can be made in stripper efficiency
either by increasing the stripping steam rate when cat-
alyst circulation increases (stripping steam rate should
be set above the point at which reductions in steam rate
result in increases in regenerator temperature) or by
redesigning the stripper, perhaps moving to structured
packing, to increase the throughput of the stripper but
again this mechanical solution requires a revamp and
capital.
Another approach can be to employ other methods
of decreasing delta coke to offset any regenerator tem-
perature escalations caused by the increased coke make
and possible stripper inefficiencies at the higher sever-
ity required for maximum propylene production. FCC
Additional Q&A can be found at www.eptq.com/QandA
www.eptq.com
Q&A copy 22.indd 1
delta coke is made up of four different components:
occluded coke (strippable coke), contaminant coke
(metals coke), feed coke (Concarbon) and conversion
coke (catalytic coke). When stripper operation becomes
de-optimised due to high severity/high catalyst circula-
tion rates, the occluded coke component increases.
Johnson Matthey’s Intercat Cat-Aid is effective in
reducing delta coke. Cat-Aid enables enhanced matrix
pre-cracking of Concarbon type molecules and passiv-
ates the effects of metals that promote dehydrogenation
reactions. This will have the effect of reducing feed coke
and contaminant coke to generate an overall delta coke
reduction of approximately 10% based on commercial
trials.
The purpose of Cat-Aid is to lift a constrained FCC
unit away from the normal limitations (be it high
regenerator temperature, maximum air blower rate,
maximum catalyst cooler duty or wet gas compressor
throughput) and take advantage of this shift by making
operational adjustments that are most economically
attractive for the refiner (for example, increasing resi-
due processing, increasing equilibrium catalyst activity,
increasing riser temperature, and so on). In this case,
use of Cat-Aid would allow the refiner to increase the
riser temperature to achieve maximum propylene pro-
duction without compromising other aspects of the FCC
operation.
A Jayden Yin, Oversea Marketing Director, Rezel Catalysts
Corporation, jayden.yin@rezel.com.cn
To prevent catalyst damage through overheating in
the regenerator in maximum propylene mode, the best
route is:
1. Introducing rare earth metal ions into the zeolite(s)
and intensifying calcination to effectively improve the
thermal and hydrothermal stability of zeolites during
the preparation of the major active components of zeo-
lite Y and other shape selective molecular sieves in the
catalyst
2. Employing a specific dispersion technology (devel-
oped by us) to make better contact between matrix
particles and zeolite crystals during the catalyst prepa-
ration. The superior thermal conductivity of the matrix
particles prevents the zeolite crystals from overheating,
so catalyst activity could still be reserved when the
overheating took place in the regenerator.
A Martin-Modesto Miranda, Regional Subject Matter Expert,
BASF Catalysts, martin-modesto.miranda@basf.com
Maximum propylene production is based on three
pillars:
Catalysis 2017 5
27/02/2017 10:44
 • Catalyst design
• Reactor severity
• Feed quality.
Of course, these three pillars are interconnected in the
maximum propylene FCC unit:
1. FCC catalysts are designed based on feed quality and
unit constraints
2. Units run at very high severity by increasing the riser
outlet temperature (ROT) to the maximum allowed or
the optimum for the unit constraints
3. Propylene producers try to use light feeds (VGO,
UCO, HT VGO) to increase propylene production, but
these desirable feeds may not be available. In those
cases, other heavier feeds like residue can be used in
propylene production FCC units.
Maximum propylene units using lighter feeds need a
less coke selective catalyst to produce the coke needed
to keep the units in heat balance. This allows the unit
to take advantage of the catalyst propylene selectivity
with the highest ROT possible to reach the unit con-
straints. Despite very high ROT (555°C), it is unusual to
have high regenerator (regen) temperatures (>750°C).
If you are at high regen temperatures, the recommen-
dation here is to explore with your catalyst supplier
to swap the propylene produced by thermal cracking
(high ROT) with propylene produced by catalytic
cracking (catalyst selectivity). Some ideas, like increas-
ing the ZSM-5 content or modifying the zeolite content,
can help to produce the same or more propylene with
lower ROT. Operating at a lower ROT will by heat
balance lower the regen temperature, and it will also
reduce thermal cracking and thus the coke yield, fur-
ther reducing the regen temperature. The overall effect
will be lower regen temperature.
In units that process resid feeds, high regen tempera-
tures are common. Normally, these residue units have
high coke yields due to feed properties and metals con-
tamination. In this case, a highly coke selective catalyst
will reduce the catalytic coke produced. In addition, a
metals resistant catalyst will reduce the coke produced
by metal catalysed dehydrogenation reactions. All these
actions will reduce coke yield and the regen tempera-
ture. As recommended with lighter feeds, increasing
ZSM-5 and reducing ROT to maintain LPG product will
also reduce coke yield. In resid FCC units, this option
has to be optimised because reducing ROT may result
in higher slurry yield.
Briefly to summarise the ways to reduce regen
temperature:
• Reduce coke make due to non-selective thermal
cracking by reducing ROT. Compensate the lower
propylene yield using ZSM-5 additive and/or an opti-
mised zeolite content catalyst.
• Reduce catalytic coke through improving catalyst
coke selectivity. Using a highly coke selective catalyst
which can reduce delta coke and maintain bottoms
upgrading.
• Reduce the contaminant coke make due to feed met-
als. A metals resistant catalyst will reduce significantly
the coke produced by those metals effects in the FCC
catalyst. Vanadium traps and nickel passivation tech-
6 Catalysis 2017
Q&A copy 22.indd 2
nologies are available in the BASF FCC catalyst portfo-
lio to reduce these metals effects.
A Dennis Kowalczyk, Vice President, Global Customer
Technology, FCC, W. R. Grace & Co., Dennis.Kowalczyk@Grace.
com
The best route to prevent catalyst damage via hydro-
thermal and metals-catalysed deactivation is to mini-
mise delta coke for an FCC unit operating in maximum
propylene mode. Delta coke is determined via FCC
heat balance calculation and represents the wt% coke
burned from the catalyst particles during each pass
through the regenerator. Minimising delta coke results
in minimisation of the differential between the regen-
erator dense bed temperature and the reactor outlet
temperature. For max propylene units, reactor outlet
temperature is typically higher by 20-30°C relative to
conventional gas oil cracking units. With a low delta
coke operation, the rate of catalyst deactivation is
reduced because the bulk temperature of the regenera-
tor fluidised bed is lower and the internal temperature
rise of the catalyst is also lower during the initial stage
of coke combustion. The most efficient way to achieve
the lowest delta coke operation is to select a catalyst
that provides the desired yield structure at the lowest
coke yield per unit of conversion. There are many arti-
cles written regarding the subject of low delta coke
catalyst, but key features of this type of catalyst design
would include excellent zeolite stability, optimised
equilibrated zeolite unit cell size (proper rare earth
level) and high levels of resistance to nickel-catalysed
dehydrogenation reactions and vanadium-catalysed
destabilisation of the zeolite.
In addition to utilising a low delta coke catalyst, it
is important to minimise hydrocarbon carry to the
FCC regenerator. A well-designed and optimised reac-
tor disengaging system will provide high efficiency
separation of product from catalyst. Also, the catalyst
stripping section is designed to sweep hydrocarbon
vapour from the interstitial space between the cat-
alyst particles and to allow residence time for hydro-
carbons to diffuse out of the catalyst pores. Units
operating in maximum propylene mode typically
require a relatively high rate of catalyst circulation, so
it is important to have good stripper section contact-
ing between steam and catalyst at the higher catalyst
flows. Preventing hydrocarbon carry to the regenerator
protects the catalyst by minimising the temperature
rise (thermal deactivation) and incremental steam for-
mation (hydrothermal deactivation) that result from
combustion of FCC product. In order to assess the
performance of the catalyst stripper, it is important to
monitor the hydrogen-in-coke content of combusti-
ble material on the spent FCC catalyst flowing to the
regeneration section. Therefore, for accurate estimation
of hydrogen-in-coke, it is critical to have accurate anal-
ysis of the FCC flue gas. And finally, some FCC units
are equipped with catalyst coolers, and this provides
an extra degree of freedom in controlling regenerator
temperature.
www.eptq.com
27/02/2017 10:44
 Flexibility

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clg.indd 1 24/02/2017 12:57

 condenser design was 26 240 ft2
(2438 m2). For two to three times 120
Q What
the hydrocarbon vapour load, the
are the principal causes of yield degradation in the regenerator, the catalyst will deactivate more quickly

Operating pressure, Torr

required 110
FCC unit? surface area is 31 500ft
2
and higher catalyst make-up rates are required to main-
(2926 m2) to 34 850 ft2 (3238 m2). Put tain the Ecat activity.
A Rick Fisher, 100
differently, area Senior
cannotTechnical
be added to
Service If the Ecat analysis is looking healthy and does not
MDP of preceding
Engineer, Johnson
an installed ejector is 83 Torr
Matthey Processcondenser
Technologies,that USA,wasrick.fisher@matthey.com
90 appear to be the source of the problem, another reason
18 Torr
designed for 26 240onft2the
Yield degradation . Therefore,
FCC unit is usually attrib- why there could be 11 Torr degradation is problems
yield higherwith
higher
for 30 000
utable to a lb/h
change or in 45feed
000 quality
lb/h ofof some sort, 80 be it a the catalyst circulation. The catalyst circulation may be
hydrocarbon
higher aromatic vapour
contentloading
or a spike thein metals for exam- lower than normal and this is obviously a function of
condenser is 20% or 33% under-sur-
ple. However, if the feed qualities have not 70 changed, the unit heat balance. High feed preheat temperatures,
faced.
and this As has
a result, because through
been verified surface laboratory testing low reactor temperature or low riser steam flows can
area
of theis combined
now fixed,FCC LMTD feed,must
thenrisethere are a few 60 other all lower the catalyst circulation rate and impact the
to
potential root causes that can equa-
balance the fundamental be reviewed. The100 150
quality conversion. 200
Additionally, if250
the FCC unit 300has a catalyst
Design point Hydrocarbon vapour loading, %
tion Q = U*A*LMTD. To effect an
of the circulating Ecat inventory can paint a very good cooler, a low catalyst cooler duty will result in a higher
increase
picture ofinthe LMTD, condenser
condition of theoper-
unit. Regular Ecat anal- regenerator temperature and a lower catalyst circula-
ating pressure, in
ysis can show if the catalyst this example,
is being Figure
deactivated at a tion response
9 First intercondenser rate. Cat-Aid or Lo-Coker
to hydrocarbon loading additives can be used
must rise 18 torr for the 45 000 lb/h
greater magnitude than normal or if there has been to decrease delta coke and regenerator temperature,
case. At this from
contamination required metals.operating why the firstand
If the microactivity stagethereby
ejectorincreasing
is not thevacuum
catalyst column pressure
circulation rate. abruptly
pressure, the fi rst stage ejector simply
total surface area (TSA) are lower than normal, it is pos- tracking its performance rises higher.
Occasionally it is the case that the fluidisation of the
MDP is surpassed
sible that the catalyst bymake-up
18 torr and,rate is curve.
too low, Theor there root catalyst
cause inisthethe standpipes is not sufficient and the flow
therefore,
is a higher the amountfirst ofstage suppression
ejector losses.
fresh catalyst There may of heatcan transfer
become in uneven
the Predicting
and sluggish.and specifying
This too design
will have
breaks performance. Consequently, fi rst inter-condenser due to the
be a mechanical problem with the fresh catalyst addi- an impact on yields and can be detectable through a cracked gas load
the
tion vacuum
system and column rises excessive
pressuremake-up
the targeted rate is nothydrocarbon
being low loading differential Specifying
that pressure across theconservatively
regenerated cata-the
appreciably and potentially is leads to a rise in its operating pres- design
achieved. This can be verified by reviewing a complete lyst slide valve. The main cause of uneven catalyst cir- cracked gas load is wise.
catalyst mass balance, accounting for sure.
unstable. Oncewith-
additions, first culation, assuming Cracked
inter-condenser the ABDgases are inerts
and Fprop of thewithin an
Ecat are
The process team wonders why operating pressure surpasses the ejector
drawals, reactor side losses, regenerator side losses typical, is insufficient standpipe aeration. Nevertheless, system and will not
the
and added hydrocarbon
the regenerator loading
bed level. is MDP
If torch of the used
oil is being ejector problems
that precedes condense.
haveit also been seen At on
a given temperature
the spent catalyst
affecting the system this way and – in this example, MDP is 83 torr
to supplement the heat balance, if the direct fired air standpipe, whereby slugs of condensate were – and pressure within a condenser,
being
heater is running, or if there is excessive afterburn in the entrained with the stripping steam and causing pres-

www.eptq.com PTQ Q4 2016 41

8 Catalysis 2017 www.eptq.com

Q&A copy 22.indd 3 27/02/2017 10:45

 sure surges in the base of the stripper and entrance to
the standpipe. Use of specially designed low APS addi-
tives, such as FlowCat, can help to improve catalyst
fluidisation.
Other causes of yield degradation on an FCC unit
could be linked with mechanical damage. Damage
to the stripper can result in insufficient stripping effi-
ciency and can be identified by looking at the hydro-
gen-in-coke, calculated from the flue gas analysis.
Furthermore, damage to the spent catalyst distributor
or the main air grid can cause maldistribution and after-
burn in the regenerator. It has been seen in some cases
of yield degradation that damage to the feed-slurry
exchanger has resulted in feed leaking directly into
bottoms, and also reactor bypass isolation valves pass-
ing, which results in the same condition. Mechanical
damage to the feed distributors can impact the feed
vaporisation through affecting droplet formation and
dispersion in the riser cross section, and damage to the
lift steam distributor can cause maldistribution of the
catalyst up-flow through the riser. Aside from mechan-
ical damage, a low acceleration zone velocity or insuf-
ficient feed steam rates can also have a negative impact
on unit yields.
Riser residence time additionally plays a role in the
conversion chemistry and insufficient residence times
will have a negative impact. A reduced riser residence
time can be caused by coke accumulation in the riser,
thus reducing the cross sectional area and increasing
the velocity. Another cause is an excessive use of lift
steam, which is something that should be optimised for
each individual unit through step testing.
Many potential causes for yield degradation have
been summarised here, however, as previously men-
tioned, yield degradation is most typically caused by a
change in the feed properties. There are some catalyst
poisons that are more difficult to detect than others
and may not be frequently tested. Basic nitrogen for
example will temporarily poison the acid sites but is
not retained on the catalyst so will not show up on the
routine Ecat analysis. It is very important to carry out
full unit check runs regularly on an FCC unit, which
provides the individual typical operation and will help
to identify the source of a problem when trying to trou-
bleshoot unusual operations.
A Dennis Kowalczyk, Vice President, Global Customer
Technology, FCC, W. R. Grace & Co., Dennis.Kowalczyk@Grace.
com
FCC operating yields are a function of the interaction
between feedstock, catalyst, unit operating conditions
and mechanical performance. When there is degradation
in FCC yields, there is typically some combination of
factors but feedstock often plays a significant role. Key
attributes of the feed that will result in yield degradation
include higher boiling range and carbon residue content,
higher levels of basic nitrogen and an increase in the
level of contaminant metals such as nickel, vanadium,
sodium, calcium and iron. Heavier feed often results in
a hotter regenerator, which in turn lowers the ratio of
catalyst to oil in the reaction zone and increases the level
www.eptq.com
Q&A copy 22.indd 4
of thermal cracking relative to catalytic cracking. Basic
nitrogen acts as a temporary poison for the zeolite and
reduces conversion levels. Metals contamination can
produce more coke and heat the regenerator (NI/V),
can deactivate the zeolite in the catalyst (Na/V), and can
block the catalyst pores (Fe/Ca). Each of these metals
effects will result in degradation in the yield of the most
valuable FCC products.
Over time, the condition of the FCC mechanical
equipment can be affected by high temperature and
by the erosive forces of catalyst flow. As equipment
efficiency deteriorates, yield degradation can result.
Maintaining good performance of the FCC feed nozzles
is critical in order to have effective feed droplet disper-
sion and rapid vaporisation of the hydrocarbon mole-
cules. If feed nozzle performance is compromised, poor
distribution of oil with the catalyst can degrade FCC
yields via incomplete feed vaporisation and increased
thermal cracking. Once the FCC products are formed,
it is important to rapidly separate product from catalyst
and to quench the reaction mixture in order to mini-
mise any thermal cracking of valuable FCC product.
Therefore, maintaining performance of the catalyst dis-
engaging and stripping sections is important for hold-
ing good yields. And any operating shifts that result in
a hotter regenerator will lower the ratio of catalyst per
unit of oil at constant reactor conditions, which gener-
ally results in some loss of total liquid volume yield.
Catalyst is obviously a key factor in maintaining
good FCC yield performance. Since the condition of
the equilibrium catalyst is monitored closely, clues as to
the cause of any observed degradation in yield patterns
can be detected. Catalyst activity level is a major con-
tributor to FCC yield pattern and has to be maintained
at constant levels. There are many factors that can
cause a loss of activity including improperly operating
catalyst addition systems, higher level of feed contam-
inants (both carbon and metals), and deterioration in
performance of the catalyst stripping and regeneration
sections, resulting in higher catalyst deactivation rates.
When FCC additives are used in combination with a
base catalyst to drive certain yields such as propylene
and butylenes, improper control of the addition ratio
can result in loss of desired yields.
In summary, there is a complex interaction between
catalyst, feedstock and unit operations that can result in
yield degradation. When yield degradation is observed,
it is important to conduct a thorough investigation of
all potential causes. Keys to effective troubleshooting
include frequent analysis of the feedstock properties
and the condition of the equilibrium catalyst. This infor-
mation then serves as a benchmark that can be used to
more quickly and accurately identify and address the
cause of an undesirable shift in FCC product yields.
A Jayden Yin, Oversea Marketing Director, Rezel Catalysts
Corporation, jayden.yin@rezel.com.cn
There are many causes for the decrease of the yield of
FCC products in the operation of FCC units. The most
commonly encountered is the change in quality of the
feedstock. Metals such as Ni, V, Fe, and others have
Catalysis 2017 9
27/02/2017 10:45
 the most significant impact on the yield of the crack-
ing products. Among the metals, nickel has the highest
dehydrogenation activity which easily generates H2
and coke. Its effect is generally evaluated using the H2/
CH4 ratio in the dry gas and the H2 volume generated
per barrel feed oil. In general, if the nickel content is
over 1000 ppm in the Ecat, measures need to be taken.
V can migrate into the catalyst microsphere and destroy
the zeolite crystal structures, which could lead to a per-
manent loss of catalyst surface area and activity. The
degree of V poisoning is associated with the V concen-
tration, temperature of regenerator, way of regener-
ation, sodium content, % steam, and zeolite types. In
general, if the V content in the Ecat is over 2000 ppm,
measures need to be taken. For Fe, with its deposition
on the catalyst, nodules can form if sulphur exists,
which could lead to a significant decrease of catalyst
surface area, pore volume and catalytic activity. In addi-
tion, the content of N and S in the feed oil, particularly
an increase in basic nitrogen, could lead to a significant
decrease in the yield of cracking products. S and basic
N could neutralise the acid sites in the catalyst, leading
to temporary catalyst deactivation and a decrease in
products yield.
Q Can you suggest a scheme for desulphurising naphtha
from the FCC unit to meet Tier 3 requirements?
A Brian Watkins, Technical Service Manager, Advanced
Refining Technologies, Brian.Watkins@Grace.com and Chuck
Olsen, Global Technology Manager, Advanced Refining
Technologies, Chuck.Olsen@Grace.com
Tier 3 gasoline regulations are requiring that all gaso-
line is to contain ≤10 wppm sulphur. This is a decrease
from the current Tier 2 regulations of ≤30 wppm sul-
phur. This change in product sulphur can have a dra-
matic impact on refiners that have a significant portion
of their gasoline pool generated from the FCC unit. In
order to meet this regulation there are only a few meth-
odologies to reduce the gasoline sulphur pool. These
involve some level of hydrotreating, either before or
after the FCC unit, or removal of naphtha sulphur
species directly in the FCC process. The process of
hydrotreating after the FCC unit however can have a
dramatic effect on the gasoline octane levels due to the
additional olefin saturation that occurs when reducing
the product sulphur.
For refiners that utilise a hydrotreater in front of their
FCC unit, changes to that operation need to be consid-
ered in order to meet the desired product targets. To
address these needs, Advanced Refining Technologies
LLC (ART) utilises the ApART Catalyst System for
FCC pretreatment. This technology is designed to pro-
vide significant increases in HDS conversion while at
the same time providing significant upgrading of FCC
feedstock quality and increasing yields. In essence, an
ApART Catalyst System is a staged bed of high activity
NiMo and CoMo catalysts where the relative quantities
of each catalyst can be optimised to meet individual
refiner’s goals and constraints. ART has continued to
10 Catalysis 2017
Q&A copy 22.indd 5
10 000
FCC gasoline sulphur, ppm
1000
100
10
1
10 100 1000 10 000 100 000
FCC feed sulphur, ppm
Figure 1 Relationship between FCC gasoline sulphur and FCC feed
sulphur
develop a better understanding of the reactions and
kinetics involved in FCC pretreating, and, through
its relationship with Grace Refining Technologies, a
detailed understanding of the effects of hydrotreating
on FCC unit performance.
It is clear that FCC pretreating plays an important
part in reducing the sulphur content of FCC products.
ART has completed many studies looking into the
effects of hydrotreating on FCC performance and the
quality of the FCC products. The work demonstrates
that reducing the sulphur in FCC gasoline and LCO
simply requires a reduction in the sulphur of the FCC
feed by increasing the severity of the pretreater. Figure 1
shows the relationship between FCC feed sulphur and
the resulting sulphur of the FCC gasoline.
These data are generated using a variety of FCC feeds
that had been hydrotreated over several types of cata-
lysts and catalyst systems. As can be seen in the chart,
there is a good correlation between FCC feed sulphur
and the corresponding FCC gasoline sulphur. In this
case, the sulphur content in the FCC gasoline is roughly
100 times less than the sulphur in the feed to the FCC
unit. Increasing the severity of the pretreater operation
to reduce the product sulphur will tend to move the cat-
alyst towards more of a PNA mode of operation. This
mode of operation, while beneficial to the FCC unit
in many ways, can impact the cycle length due to the
increased temperatures.
Both the hydrotreating catalyst system and the oper-
ating strategy for the pretreater are critical to providing
the highest quality feed for the FCC unit. Optimising the
hydrotreater to remove nitrogen and PNAs improves
FCC product value when targeting gasoline produc-
tion, but this needs to be balanced against the costs of
higher hydrogen consumption and shorter cycle length
that result from this mode of operation. Use of tailored
ApART catalyst systems with 586 DX and 486 DX cata-
lysts can optimise the FCC unit in order to produce not
only high quality feeds to the FCC unit but also lower
sulphur products, resulting in less impact on down-
stream hydrotreating. This tailoring can also be benefi-
cial if the FCC products are able to be blended directly
without hydrotreating, as they can be driven towards
lower sulphur and higher gravity products, allowing the
refiner to be able to blend these fuels directly without
sacrificing the FCC gasoline octane level.
www.eptq.com
27/02/2017 10:45
 Bringing Unity To
Honeywell UOP’s vast hydroprocessing
catalysts lineup is called Unity™ because
Hydroprocessing we bring a unified approach, delivering
complete catalyst, equipment, licensing
and technical support solutions for
hydrotreating, pretreat and hydrocracking.

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honeywell.indd 1 14/12/2016 11:11

SPM-UOP-138 UnityAd_A4.indd 1 12/7/16 4:19 PM
 A Colin Baillie, Segment Manager, Environmental Additives,
W. R. Grace & Co., Colin Baillie@Grace.com
To comply with 2017 Tier 3 regulations, refiners in
North America will be required to produce gasoline
with a 10 ppm sulphur limit. One of the consequences
of achieving lower sulphur gasoline is the octane loss
associated with the additional hydrotreatment required.
As every refinery is different in terms of feedstocks pro-
cessed, configuration of product streams contributing to
the final gasoline pool, as well as the processing units
available for desulphurisation, there is no ‘one size fits
all’ approach for utilising a lower FCC naphtha sulphur
to achieve Tier 3 compliance. Nevertheless, it can cer-
tainly be an important part of a refiner’s strategy,
Of all the product streams going to the gasoline pool,
FCC naphtha is the largest contributor of sulphur.
Therefore a reduction of FCC naphtha sulphur can have
a significant impact refinery wide. There are various
ways in which reducing naphtha sulphur can be a part
of a refiner’s overall strategy for Tier 3 compliance. FCC
naphtha is typically split into lighter and heavier cuts.
The lighter cuts can often be sent directly to the refinery
gasoline pool, so decreasing the sulphur content of these
cuts will directly decrease the gasoline pool sulphur.
Reducing the sulphur of the heavy naphtha from the
FCC does not directly result in lower gasoline pool sul-
phur, because the heavy naphtha sulphur is typically
controlled irrespectively by post-treatment downstream
from the FCC unit. This hydrotreatment is very effec-
tive in providing low sulphur levels, but has the draw-
back of decreasing octane levels. Therefore, reducing
the sulphur content of the heavy naphtha cut from the
FCC unit can allow a lower severity on downstream
post-treatment units while providing the additional
benefit of reduced octane loss.
Many other countries have either implemented 10
ppm gasoline sulphur limits, or are in the process of
doing so. This has required significant investment in
increased hydrotreating and hydrocracking capacity.
To complement these investments and minimise octane
loss in the hydrotreaters, Grace’s gasoline sulphur
reduction (GSR) technologies have played an important
role in the overall strategy of many refineries to com-
ply with tighter gasoline sulphur specifications. GSR
technologies have been used by more than 70 refineries
worldwide, representing more than 15 countries. For
example in Japan, which was the first country to adopt
10 ppm gasoline sulphur, over 50% of refiners continue
to use the technology.
A Melissa Clough, Technology Specialist, Refining Catalysts,
BASF Catalysts, melissa.clough@basf.com
For refiners, multiple strategies exist for meeting Tier 3
requirements (10 ppm gasoline sulphur, see Figure 1)).
First, hydrotreating is an option. Feed hydrotreating can
remove up to 90% of the feed sulphur and will improve
overall FCC operations. On the back-end, naphtha
hydrotreating is also an option and can remove up to
99% of the remaining sulphur. Refiners must watch out
for octane loss, which can be significant. In a refinery
case, a loss of 2-3 octane numbers has been observed
12 Catalysis 2017
Q&A copy 22.indd 6
Gases
Hydrotreating
Cut point adjustment
Catalyst technology Gasoline Gasoline
post-treat
Sulphur credits
LCO
Feed Feed
pre-treat sulphur
HCO
Coke SOx
Sulphur credits
Figure 1 Options for gasoline sulphur reduction
in gasoline post-treating. Octane loss will increase with
increasing post-hydotreating severity. Another strategy
to employ is cut point adjustment, which pushes some
of the heavy naphtha (and thus some of the benzothio-
phene and heavier sulphur species) into light cycle oil
(LCO). Another method exists on paper whereby refin-
eries can utilise sulphur credits that are either accumu-
lated, traded between refining companies, or purchased
on the sulphur credit market. Finally, FCC catalyst solu-
tions exist to reduce naphtha sulphur in the form of a
catalyst solution, called NaphthaClean, or in the form
of an additive, called Low Sulphur Additive (LSA).
NaphthaClean is amenable for refineries who need a
more permanent solution. For refiners who require FCC
naphtha sulphur reduction on a spot basis, LSA is more
applicable. Spot basis treatment is employed during a
hydrotreater turnaround, during a hydrogen outage,
or while processing high sulphur feeds. In both cases,
NaphthaClean and LSA, a reduction of 20-40% is seen.
The range depends on a number of variables including
whether or not the feed is hydrotreated. A gasoline sul-
phur speciation study is often employed prior to using
an FCC catalyst technology to ensure the best fit and an
accurate sulphur reduction target. BASF has developed
a specialised sulphur speciation tool in order to best
make this recommendation to refiners.
A Claus B Nielsen, Product Manager, Haldor Topsoe A/S,
clbn@topsoe.com
The production of low sulphur gasoline is often done
by blending straight-run gasoline, alkylates, and isom-
erates (containing zero sulphur) with FCC gasoline
(containing say 100 wtppm sulphur). This enables
the refiner to maintain a gasoline pool of less than 30
wtppm sulphur (Tier 2).
However, when switching to ultra low sulphur gaso-
line, containing less than 10 wtppm sulphur for meeting
the Tier 3 requirements, this blending becomes much
more challenging. It will require further desulphu-
rising of the naphtha from the FCC unit, lowering the
sulphur content in the FCC gasoline to typically below
20 wtppm sulphur.
Removal of sulphur from the FCC naphtha is most
often done in an FCC post-treatment unit using spe-
cially developed hydroprocessing catalysts. In these
units, the sulphur is removed while octane is to a large
degree preserved by using selective hydroprocessing
www.eptq.com
27/02/2017 10:45
 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
™
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Lubes
MWI™ EM-7820
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L1015-060E49

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

 catalysts. Going from Tier 2 to Tier 3 will increase the
degree of sulphur conversion, and therefore refiners can
experience constraints in their current units, like cycle
length, temperature, product quality. In particular, the
loss of octane will increase rather significantly, which
will influence the octane value in the gasoline pool.
In order to overcome these constraints, a possible
solution is installing new catalysts with higher catalytic
activity for sulphur removal and high selectivity in
order to limit octane losses. Haldor Topsoe’s HyOctane
catalysts fulfill these criteria and are already used by
refiners making ultra low sulphur gasoline.
Q What are the principal causes of excessive pressure drop
in our hydrotreater and what solutions are available?
A Brian Watkins, Technical Service Manager, Advanced
Refining Technologies, Brian.Watkins@Grace.com and Chuck
Olsen, Global Technology Manager, Advanced Refining
Technologies, Chuck.Olsen@Grace.com
There are several causes for pressure drop related to
a poor turnaround or poor catalyst loading. A dam-
aged or dirty outlet collector, dirty support screens or
improper size grading at the bottom of a catalyst bed
can all lead to high pressure drop in a lower bed. It is
important that the reactor and screens be cleaned before
loading any catalyst. Proper size grading of catalyst at
the bottom of each bed is also important. If the catalyst
size difference between layers is too large, smaller diam-
eter catalyst can migrate through subsequent layers and
ultimately plug the support screens or outlet collector. It
is also critical to make sure nothing (tools, hardhats and
so on) gets left in the reactor during a loading.
Pressure drop in a lower bed can also be caused by
the gradual accumulation of iron sulphide or other
fines. Iron (Fe) can work its way into hydrotreater feed
as rust and iron scale from corrosion of upstream equip-
ment and piping as well as unfiltered particulates pres-
ent in the feed. Iron naphthenates can form from piping
corrosion due to naphthenic acid in the feed, and the
iron readily precipitates out in the presence of heat and
H2S. These iron particulates fill the interstitial spaces
in the catalyst bed which will result in a higher than
expected pressure drop. To help mitigate the pressure
drop associated with iron, ART uses a series of grading
materials which have high void space to accumulate
and ‘store’ these particulates. Use of a specialised iron
trapping material (GSK-10) which has high internal
void space for trapping iron inside its large pore net-
work is also valuable.
If iron is known to be the cause of the pressure drop
issues, then changes to larger diameter catalysts can
also be used in an effort to allow for additional void
space in the reactor. Sock loading a large portion of the
top of the reactor will also greatly increase the effective
void space, allowing the smaller iron particles to move
through the reactor.

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GASOLFIN_HP.indd 1 2/2/17 8:57 PM

14 Catalysis 2017 www.eptq.com

Q&A copy 22.indd 7 27/02/2017 10:45

 Another option is materials that Medallion to the hydrotreater and avoid tank-
are specially designed to dramat- 16 mm age, oxygen scavengers, and so on).
ically increase the void fraction in Hardware solutions like Shell
the top bed of the reactor and are MacroRing Global Solutions’ scale catching
very good at trapping iron as well 8 mm trays for gas phase reactors like
as other particulates and scale. NHTs or filter trays for reactors
These measures are helpful for Ring which operate in mixed phase
delaying pressure drop build-up, 6.4, 4.8, provide additional capacity for
3.2 mm
but they do not prevent eventual particulates to be captured prior to
pressure drop build-up. Effective entering the catalyst bed. These fil-
feed filtration to remove particulates Filter lobe ter tray elements sit in the top head
5.6, 3.2,
(at least 25 microns) provides a lon- 2.5 mm of the reactor, above the distribution
ger lasting solution in helping mit- tray, and do not reduce active cata-
igate pressure drop build-up from lyst volume.
these sources, as well as a way to Figure 1 Top bed grading options Particulates and polymerisation
identify the sources of iron that are products typically result in a dP
present in the process. increase at or near the top bed of a reactor. Coke for-
Excessive coke formation can also result from hydro- mation can lead to dP issues at the top of the reactor but
gen starvation from poor gas distribution, or low H2/ also in lower beds due to asphaltene precipitation or
oil ratio combined with higher temperatures has also accelerated coking in areas of low H2/oil ratio or high
been identified as a cause of lower bed pressure drop. temperature.
It is important to keep the H2/oil ratio above a specified It is impossible to prevent all pressure drop causing
minimum, and if reduced H2 availability is anticipated precursors from entering the reactor and a good cat-
the charge rate should be reduce or cracked stocks alyst load is critical as it will evenly distribute these
removed for the period to ensure the minimum H2/oil particles or compounds over the entire catalyst volume.
ratio is maintained. It is imperative to use a catalyst grading system which
Another cause for lower bed pressure drop which we includes size grading to provide void fraction control
have seen involves debris or water introduced though down the reactor and enable full utilisation of the grad-
the quench line. ing system to minimise dP build-up. Activity grading
Quench rates should be adjusted to measure reac- is also crucial to allow polymerisation precursors to
tor internals performance. If the response to quench is react in a controlled manner. Top bed grading products
unusual and the reactor dP fluctuates with fluctuating offered by Criterion Catalysts & Technologies are shown
quench rate, the cause may be due to solids in the reac- in Figure 1. Depending on the fouling potential of the
tor internals. feed and fouling history of the reactor, the grading sys-
tem can be optimised to minimise dP build-up. Catalyst
A Pat Gripka, Americas Technical Manager, Criterion size and shape are also important and main bed catalyst
Catalysts and Technologies, Pat.Gripka@CRI-Criterion.com of larger diameter (say, 2.5 mm) may also be part of the
Pressure drop increase in hydrotreating reactors is typ- solution.
ically caused by deposition of particulates, polymer- Start-up and emergency response procedures are
isation byproducts, or coke. Each of these reduces the important to ensure dust and fines are removed during
catalyst void fraction, thus resulting in delta P increase. start-up and that contaminants from exchangers, heat-
Sources of feed particulates are corrosion byproducts ers, and so on are not dislodged during shutdown and
like iron sulphide (FeS) from upstream units often due end up at the top of the reactor. Routine monitoring of
to processing high total acid number (TAN) crudes, the unit and normalisation of the pressure drop to a
coke fines from delayed cokers, catalyst fines in streams standard base set of conditions is critical.
derived from the FCC unit or sodium salts from poor In operation, hydrotreaters that are struggling from
desalting or NaOH carryover. Polymerisation byprod- pressure drop issues have few options to alleviate this
ucts are formed by polymerisation of diolefins and ole- challenge immediately. Additional feed filtration, if pos-
fins in the feed stream in the presence of oxygen. Even sible, can stabilise the system and chemical injections
with a blanketed feed tank or hot routing of cracked can provide short-term relief but the key parameters
stocks to the hydrotreater, oxygen contamination can which drastically affect pressure drop immediately are
occur from another feed from tankage. Coking potential feed and gas rates. In some cases, options to reduce feed
is related to feed aromaticity, asphaltene content, carbon and gas rates or change to less contaminated feeds can
residue (CCR) and contaminant metals. extend reactor cycle life, but these will likely come with
Key elements to preventing pressure drop build-up an economic penalty.
are filtration, upstream corrosion protection, proper Pressure drop can also build up downstream of the
desalting and feedstock management. Filtration sys- reactor due to deposition of salts in the cooling train.
tems should be properly designed to remove particu- High chlorine contamination often leads to increased
lates from upstream units. Typical filter size is 10-100 deposition of NH4Cl upstream of the continuous water
microns. Steps must be taken to minimise exposure of wash. Intermittent water washing should be used to
cracked stocks to oxygen (inert blanketed tanks, run hot dissolve the salt and reduce dP.

www.eptq.com Catalysis 2017 15

Q&A copy 22.indd 8 27/02/2017 10:46

 Working with expert technical advisors from your
catalyst and technology provider to identify the source
of the issue results in a solution which yields maximum
economic benefit for the refiner. For units with recur-
ring dP problems, hardware solutions like scale catch-
ing trays and filter trays, additional filtration, addition
of guard reactors, and improved feedstock manage-
ment have helped mitigate dP problems. Whenever a
dP problem occurs, it is important to understand the
underlying causes. In some instances specialised Sentry
catalyst baskets can be installed to allow a detailed
understanding of the fouling profile when the reactor is
skimmed or catalyst is changed. Therefore, it is import-
ant to draw on catalyst and technology experts like
Criterion, whose insights and industry experience pro-
vide a vast array of pressure drop solutions for hydro-
treating units both immediately and in planning for the
future.
A Christina Borch, Product Manager, Haldor Topsoe A/S,
cb@topsoe.com
Pressure drop due to iron scale in hydrotreating units is
a common problem seen at refineries. Iron can be found
both as very small particles or even at larger sizes, both
typically originating from corrosion. Corrosion can
take place upstream the hydrotreating unit in pipes
and equipment. The corrosion products are transferred
to the hydrotreating unit with the oil and gas streams
during normal operation and will plug the top of the
catalyst bed, causing excessive pressure drop build-up.
In the worst case, the hydrotreating unit is forced to
shut down for catalyst replacement. The pressure prob-
lem due to iron scales can be minimised with an optimal
graded bed in the top of the catalyst bed. The grading
should have enough void to accumulate iron scale with-
out causing increased pressure drop. Furthermore, the
grading should have an optimum shape and porosity
to be able to catch even very fine iron particles which
would otherwise reach the bulk catalyst. For this
specific purpose, Topsoe has developed the grading
product TK-26 TopTrap which has a unique shape and
a porosity specifically designed to trap small iron par-
ticles. Inorganic iron, frequently seen to increase from
running acidic crudes, is effectively stored in the inert
TK-26 TopTrap product. Faced with the challenges
of spot market crudes makes it very important for the
refiner to consult with the hydroprocessing catalyst
supplier because almost all catalyst solutions are unique
and have to be designed to match the specific situation.
Another solution could be installing a scale catcher.
The scale catcher collects particles before they reach
the top bed. This reduces plugging of the catalyst bed,
which otherwise leads to maldistribution and increased
pressure drop.
A Guillaume Vincent, HPC Global Business Manager, Porocel,
gvincent@porocel.com
Any hydrotreating unit can encounter an operational
problem during its cycle which can force an unsched-
uled shutdown and costly catalyst replacement. One
of these operational issues is the build-up of pressure
16 Catalysis 2017
Q&A copy 22.indd 9
across the catalyst bed which can be an especially rapid
phenomenon. There are many possible reasons for rapid
pressure drop build-up, namely: type of feedstocks
hydrotreated (cracked molecules); plugging of outlet
collector; deposition of particulates at catalyst inter-
faces; short catalyst; and breakage of catalyst during the
loading and/or the cycle. Porocel is now able to provide
very effective hydroprocessing products and services, to
mitigate pressure drop build-up during the entire cycle
of your unit. For particulate issues, Porocel recommends
applying CatGuard PMT-60 which features a high void
fraction, to trap particulates which tend to deposit at
catalyst interfaces at the top of your reactor. For hydro-
treating cracked feedstocks containing reactive mole-
cules, Porocel recommends applying CatGuard PMT-20
in order to provide mild hydrogenation to gradually
saturate olefins while limiting fouling at the top of your
reactor. The full Porocel CatGuard grading portfolio is
available in different sizes and shapes and we recom-
mend gradually decreasing the void fraction to mitigate
delta P build-up (19 mm Medallion → 9 mm Hollow
Cylinder → 5 mm Hollow Cylinder, 5 mm trilobe,
2.5mm trilobe). Porocel is also able to length grade the
main bed of your catalyst to meet a specific length tar-
get, while providing quality control during the produc-
tion, to decrease start of cycle pressure drop. Applying a
larger diameter main bed catalyst (2.5 mm vs 1.3 mm) is
another option to decrease start of cycle pressure drop
for your unit. Porocel has extensive resale inventory
worldwide of large and small diameter catalysts which
can be used as an alternative to fresh catalysts in many
refining applications with 30-70% the cost of fresh cat-
alyst. Porocel also provides technical support to assist
the refinery in choosing the proper loading method for
your unit (sock loading or dense) according to the unit
constraints.
Q What level of performance (compared with fresh catalyst)
should I allow for regenerated hydroprocessing catalyst before
its only value is in metals recovery?
A Allan K Uldam, Product Manager, Haldor Topsoe A/S,
aku@topsoe.com
Evaluation of catalyst regenerability highly depends
on type and amount of contaminants, especially metal
deposition on the catalyst. Catalyst suppliers, as well
as regeneration companies, offer analysis of spent cat-
alyst. Such analysis may be used to evaluate the suit-
ability of having the catalyst ex situ regenerated. If the
catalyst is deemed suitable for ex situ regeneration, it is
expected to regain 80-85% of the activity of fresh cata-
lyst. Typically, the top grading material is not suitable
for regeneration and should thus be replaced after each
cycle.
The analysis of spent catalyst can also be used to
evaluate the integrity, such as strength and the length
distribution, of the catalyst in question. Broken catalyst
will result in higher pressure drop in operation, and
typically batches showing an average particle length of
less than 3 mm should not be reused. However, this cri-
www.eptq.com
27/02/2017 10:46
 New 2nd generation HyBRIM™ NiMo catalyst

For significantly
better performance,
The answer is HyBRIM ™

The new 2nd generation TK-611 HyBRIM™ catalyst for high pressure
ultra-low sulfur diesel and hydrocracker pretreatment service.
• 25% higher HDS and HDN activity
• Unmatched stability throughout the cycle
• Superior volume swell for increased profitability

Now that’s performance that pays.

Scan the code or go to

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haldor.indd 1 14/12/2016 09:54

 terion should be evaluated on a case-by-case basis.
Based on the specified feedstock properties, it is
expected that the bulk catalyst can be regenerated twice.
Often this provides an overall catalyst lifetime of at least
two and a half times the expected first cycle length.
Typical catalyst loss during regeneration will be less
than 10% for each cycle. The losses will have to be com-
pensated by fresh (or equivalent regenerated) catalyst.
In many cases, especially for demanding services, it is
beneficial to boost the activity recovery following regen-
eration by specialised reactivation methods, such as the
Topsoe ReFRESH process.
Often ReFRESH catalyst will show an activity recov-
ery of 95% compared to fresh catalyst. This high recov-
ery of activity is particularly useful in ultra low sulphur
diesel operation.
A Amit Kelkar, Global Application Specialist, Criterion
Catalysts and Technologies, Amit.Kelkar@CRI-Criterion.com
The level of activity required will depend on the per-
formance requirements of the unit. A simple measure is
looking at minimum cycle required for the performance
need. Once this is established you can evaluate the cost
of fresh solution with the added cycle life to see if the
cost benefit still applies favourably for a regenerated
catalyst solution. Obviously, if the performance require-
ments of the hydrotreating unit in question require
the maximum activity to provide the required product
properties or cycle life, regenerated catalyst alone is
probably not a viable option for that unit. If the unit
has the horsepower needed for the current feedstock or
product requirements, a regenerated catalyst for a part
or full load may be a viable option. In cases like this
where performance is elastic, consideration of a combi-
nation of regenerated material with fresh catalyst can
produce the desired activity for performance and cycle
length.
There are some other key characteristics to consider
besides just activity when deciding to use a regen solu-
tion. The catalyst must meet the minimum contamina-
tion metals guidelines and must be of sufficient length
and strength to avoid causing delta P problems. For
these reasons, a catalyst is usually regenerated and
reused one time only. Consult with your catalyst sup-
plier to understand the options available.
A Brian Watkins, Technical Service Manager, Advanced
Refining Technologies, Brian.Watkins@Grace.com and Chuck
Olsen, Global Technology Manager, Advanced Refining
Technologies, Chuck.Olsen@Grace.com
The level of performance remaining on a catalyst that is
simply regenerated is dependent on the type of catalyst
that is being regenerated. There are significant differ-
ences between regenerating traditional oxide catalysts
vs chelated Type II catalysts. The high activity of Type II
catalysts is due in part to the unique chelate technology
employed in their manufacture. One of the issues with
these types of catalysts is a high loss of activity after a
conventional regeneration. Type II catalysts typically
recover only 70-80% of fresh catalyst activity following
18 Catalysis 2017
Q&A copy 22.indd 10
a conventional regeneration whereas traditional oxide
catalyst is 90-95% of fresh catalyst activity. At that activ-
ity level the catalysts are suitable for cascading to less
demanding applications, but are not active enough to
reuse in ULSD or hydrocracking pretreat units and it is
recommended that the Type II catalyst undergo a sec-
ond step processing to regain activity.
To address the issue of catalyst reuse, ART developed
Phoenix catalyst, a process to restore DX catalysts and
other catalysts to near-fresh activity. It involves a con-
trolled regeneration followed by a proprietary reacti-
vation which results in 90-95% of fresh catalyst activity
recovery. Once regenerated, the catalyst goes through
the reactivation process which involves the application
of nanoscale redispersants and a carefully controlled
drying step. It is critical that the correct amount of
redispersing agent is used for optimum activity, and
further it is important that the catalyst is dried properly.
The activity of the Phoenix catalyst again exceeds 95%
of fresh activity, providing a viable option for catalyst
restoration.
It is highly recommended to work with your supplier
in order to determine the level of acceptable contami-
nants on the catalyst as well, since most poisons are per-
manent and, depending on the specific poison, can have
a serious impact at very low levels.
Phoenix is a mark of Advanced Refining Technologies LLC.
A Michael Martinez, HPC Technical Service Manager, Porocel,
mmartinez@porocel.com
The aim of regeneration is to remove coke deposited
on the catalyst surface to restore as much original
activity as possible. To be suitable for regeneration, the
content of contaminant metals on spent catalysts, such
as nickel, vanadium, arsenic, silicon and iron, needs to
be low. To be reused in the hydrotreating unit, at least
80% of catalytic activity in terms of HDS and HDN
versus fresh is recommended in order to keep good
hydrotreated product properties. Such an activity level
can be easily achieved for atmospheric distillates and
lighter feeds. It becomes more complicated to regener-
ate spent hydrotreating catalysts used in more severe
conditions such as vacuum gas oil (VGO) due to more
severe contamination and sintering. Industrial regen-
eration using oxidative atmosphere (air) uses different
types of technologies. Porocel uses the moving belt
regenerator (MBR) which provides several advantages
such as good control of local temperature to avoid exo-
therm and low abrasion due to its gentle handling of the
catalyst. If more activity is required (higher than 80%),
Porocel Excel rejuvenation can be applied to both Type
I or Type II catalysts. After regeneration, Excel rejuve-
nation can achieve at least 90% of catalytic activity, and
often higher than 95% compared with fresh catalysts
for more challenging units such as KHT, DHT or ULSD.
Anyway, if the regenerated activity is a real concern for
the refinery, some cascading can be considered in less
severe operations, in high metal service or as make-up
after top catalytic bed skimming prior to considering
its metal reclaim. Porocel has 12 pilot units to perform
www.eptq.com
27/02/2017 10:46
 breakthrough
catalyst
technology
Johnson Matthey’s new breakthrough technology, CATACELJM SSR, a high
performance structured catalyst for steam reforming, delivers more activity and
better heat transfer at a lower pressure drop than traditional pelleted catalysts.

Our CATACELJM SSR technology is proven to ease operating limits on the reformer
and can allow higher throughputs because of reduced tube wall temperatures, lower
pressure drop and impressive resistance to carbon deposition.

Our technical support team will work with you to assess your
needs and determine if CATACELJM SSR technology is
a good fit for your operation.

USA Tel +1 330 298 7005 x115

j matthey.indd 1 24/02/2017 12:48

 activity testing and operating conditions can be cus-
tomised to simulate a particular application in order to
make the right decision. Prior to any industrial regen-
eration, Porocel will provide the refinery a full detailed
pre-job to assess the regenerability of your catalyst
including chemical/physical characterisation of the
catalysts.
Q What options are available to maximise butanes
production for the alkylation unit?
A Alexis Shackleford, Technical Marketing Specialist, BASF
Catalysts, alexis.shackleford@basf.com
Maximising butanes from the FCC unit can be accom-
plished through operating moves and catalyst changes.
The best route for your refinery depends on your
unique unit limitations. Operating changes to increase
C4s are to increase cat/oil, increase ROT, and increase
catalyst addition rates. Catalytic options for increased
C4s are to decrease hydrogen transfer (usually through
decreasing rare earth content), increase matrix activity,
and use a ZSM-5 light olefins additive. However, each
of these has drawbacks for achieving the same increase
in butylenes. Increasing the ROT and thus the cat/oil
will increase C4s and gasoline octane but will also sig-
nificantly increase dry gas. If your unit is at a dry gas
limitation, this would not be feasible. Increasing catalyst
activity through increased catalyst addition rates comes
Full Reactor Solutions For Your Refinery
We offer our Hydroprocessing Catalyst (“HPC”) Solutions and Technical Support
CatGuard PMT
®
Excel Catalyst
®
Durocel-222
Contact us to discuss Porocel’s Solutions for your refinery:
North America, +1 832-688-9696, americas@porocel.com
Europe, +352 50 24 54-1, europe@porocel.com • Asia, +65 68 63 83 82, asia@porocel.com
20 Catalysis 2017
Q&A copy 22.indd 11
with an increase in operational expenses and a higher
increase in total LPG vs increasing ROT. Catalytic
changes such as reducing rare earth are the most selec-
tive towards C4s and boost octane. Decreasing rare earth
results in the lowest increase in total LPG (good if unit
is limited on LPG processing) but comes at the expense
of lower gasoline yield. And lastly, using a ZSM-5 addi-
tive increases C4s along with octane, but will give the
largest increase in total LPG and the largest decrease in
gasoline yield.
A Tom Ventham, Account Manager Oil & Gas Business
– Europe & Africa, Johnson Matthey Process Technologies,
Europe, Tom.Ventham@Matthey.com
Many refineries find they are in an imbalance in terms
of alkylation feedstock from the FCC unit. Unless a C4
isomerisation unit is available it is likely isobutane will
be short. The steps required to increase isobutane yield
in the FCC unit will also typically increase butylene
yield. Secondary optimisation can then be performed
to achieve close to the desired stoichiometric ratio of
i C4 and C4= for alkylation. An effective way to increase
alkylation feedstock in a conversion refinery is to add
ZSM-5 to the FCC unit. ZSM-5 cracks low octane value
straight-chain hydrocarbons in the gasoline boiling
range to propylene and butylene, in the ratio of 55-60%
C3= to 45-40% C4=. ZSM-5 also promotes isomerisation
reactions, meaning significant amounts of isobutylene
are produced. Although ZSM-5 chemistry only allows
Porocel designs Full Reactor Solutions
from Naphtha through VGO hydroprocessing:
• CatGuard ® PMT (metal traps and grading)
• Excel ® rejuvenated catalysts
• Durocel-222 (Ceramic bed support)
Worldwide technical support including:
• Reactor Loading Design
• SOR/EOR predictions
• Start-up support
• HPC unit monitoring and troubleshooting
• Catalyst performance warranty
Porocel’s HPC solutions deliver
50-70% the cost of fresh catalyst, 90% of the activity
www.eptq.com
28/02/2017 09:49
 for production of olefinic materials under normal FCC
conditions, secondary hydrogen transfer reactions
that occur on the RE-USY component of the main FCC
catalyst saturate some C4=, and to a lesser extent C3=, ARKEMA’S
CARELFLEX
to paraffins. The most susceptible molecule to satura- ®
tion through hydrogen transfer in the standard LPG
range is isobutylene, which is converted to isobutane.
This means the use of ZSM-5 additives in the FCC will SULFIDING
increase the production of both butylenes and isobutane
(via this secondary saturation on the main FCC catalyst).
SERVICE
What can be done to further optimise for maximise
feedstock to the alkylation unit? One step is to con- Manufacturing dimethyl disulfide
sider a C4 selective type of ZSM-5 additive. Such addi- (DMDS) at three Arkema sites,
tives flip the C3= : C4= ratio to favour C4 in the range of activating hydroprocessing catalysts
45-40% C3= and 55-60% C4=. This can be of benefit in worldwide.
situations where propylene production is not econom-
ically favoured or limitations such as the volumetric
throughput of the wet gas compressor or other hydrau- Carelflex® sulfiding service offers:
lic constraints in the FCC gas con section, and allows • Sulfiding procedures, technical
for a larger production of C4 components if C3 make guidance, training, and 24/7
could be reduced or maintained when compared to a
coverage during activation
standard ZSM-5 additive. Johnson Matthey C4 selective
additive Intercat ZMX can be formulated to focus reac- • Patented, low-odor DMDS Evolution®2
tant cracking in either the heavy gasoline or LCO range • High pressure pumping
depending on which is more economic or desirable for • H2S analysis with remote data access
the refinery.
during activation
Once total butylene yield has been maximised
through the use of ZSM-5/ZMX additives, optimisa- • Arkema amines available for
tion of the i C4= : i C4 ratio can be performed by altering passivation of hydrocracking catalysts
the hydrogen transfer index of the main FCC catalyst.
Preference towards isobutane will be achieved with the Our global logistics network and
use of fresh catalyst with high rare earth on zeolite and experienced Carelflex® sulfiding
high zeolite-to-matrix ratio. However, although such a
catalyst may be more active, requiring a lower addition service team stand ready for
rate for constant conversion, the high hydrogen transfer your next activation.
of such a catalyst will reduce ZSM-5 effectiveness for C3
and C4 olefins. This conflict means an economic opti- For Customer Service,
mum can be found by balancing the different factors
and interactions. call 800.628.4453
This brings in the final part of this strategy, which is to
realise the advantages of dynamic optimisation of FCC
light end yields. The operation of many refinery alkyla-
tion units is variable, either through operational distur-
bances or changes in planning demands. Injecting your
chosen ZSM-5/ZMX additive separately through an
accurate and reliable addition device allows for almost
online optimisation of alkylation feed as produced in the
FCC, as well as being able to compensate and correct for
fluctuations in FCC operation caused by feed changes as
well as variations in operation and Ecat properties.
There is great advantage in optimisation of this sepa-
rate, almost independent, light end section of the FCC
unit with ZSM-5/ZMX additives to maximise isobutane
and butylene feed to alkylation. And by using a com-
pany specialised in this area of ZSM-5 and C4 selective
ZMX technology, industry-leading additive addition
systems, and a dedicated global technical service team
dmds-evolution.com
experienced in ZSM-5/ZMX use, achieving the max-
imum benefit can be turned into a relatively simple
process.

Carelflex and Evolution are registered trademarks of Arkema.

© 2017 Arkema Inc. All rights reserved.

www.eptq.com

Q&A copy 22.indd 12 27/02/2017 10:46

 crystaphase ptq revamps supplement-stability.pdf 1 2016-09-07 10:55 AM

What’s eluding your reactor?

Stability.

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For all the engineering that goes into
stabilizing your reactor’s performance, the
CMY

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to control: your feedstock.
With Crystaphase reactor optimization, you
can take control of the particles, poisons,
and maldistribution that otherwise wreck
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The result: predictable performance, year
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Put your reactor back on schedule. Email
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crystaphase.indd 1 14/12/2016 10:33

 Increased steam methane reformer
throughput
Switching to a foil based catalyst technology raised throughput substantially for
a hydrogen producer
MARIE BASIN and DANIEL GARY Air Liquide
WILLIAM WHITTENBERGER and JUMAL SHAH Johnson Matthey Process Technologies
A
ir Liquide delivers hydrogen
and carbon monoxide to a
wide range of companies in
the refining and chemicals industry
by operating more than 50 steam
methane reformer (SMR) units
worldwide. Each unit is designed
to respond to demand which can
vary over time. Amongst its fleet,
Air Liquide has a 12-tube SMR in
Roussillon, France. The plant’s nom-
inal hydrogen capacity was reached
with conventional reforming cat-
alyst and could not be increased
any further due to the limitation of
the reformer flue gas temperature.
However, in 2015 the customer
foresaw an increase in its hydro-
gen consumption. Accordingly, Air
Liquide was required to investigate
solutions to debottleneck the plant.
Air Liquide approached Johnson
Matthey which has been involved
in the development of steam
reforming catalysts for many dec-
ades. Johnson Matthey identified
its recently commercialised Catacel
SSR as a possible solution. This
next generation reforming catalyst
is a coated, foil based alternative to
metal impregnated ceramic pellets.
Simulations suggested the enhanced
heat transfer, activity and pressure
drop properties would allow the
reformer throughput to be increased
by the desired rate. In August 2015,
the conventional pelleted catalyst
was entirely replaced by Catacel
SSR, with the objective of increasing
the production rate by 5%.
Roussillon SMR unit
The Air Liquide SMR plant in
Roussillon was started up in 2010
(see Figure 1). It includes the follow-
ing units: a hydrodesulphurisation
www.eptq.com
catalysis JM.indd 1
Figure 1 Air Liquide steam methane
reformer unit in Roussillon, France
unit, a reformer that comprises 12
reformer tubes with a diameter of
5in and one burner, a CO shift reac-
tor, and a PSA unit for final product
purification. The plant operates with
a natural gas feed and has a nominal
capacity of 2450 Nm3/h of hydrogen
with conventional catalyst.
The production rate was con-
strained by a high flue gas exit
temperature which was close to its
maximum value of 1000°C. This
Figure 2 Catacel SSR fan (left) and stack (right)
high flue gas temperature pre-
vented increasing the process gas
exit temperature.
Catacel SSR
For many years, catalyst impreg-
nated ceramic pellet media has
driven steam methane reforming
reactions in hydrogen, methanol,
and ammonia plants. Steam reform-
ing catalyst design is a balance
between many competing require-
ments and catalyst features such
as strength, heat transfer, activity,
pressure drop and avoidance of
unwanted side reactions such as
carbon formation. By adopting a
foil based structure, Catacel SSR
breaks away from many of the
limitations imposed by the use of
ceramic pellets. It is a catalyst sys-
tem that exhibits a higher activity,
improved heat transfer, lower pres-
sure drop and improved resistance
to carbon formation all at the same
time. Performance of this technol-
ogy has been proven in the hydro-
gen market since May 2012.1
Catacel SSR uses a special high
temperature alloy as a substrate
material. Alloy strip is formed into
Catalysis 2017 23
27/02/2017 10:52
 space of the fans. This aids in the
speed and accuracy of the catalyst
installation.
As previously described, the outer
edges of each fan must be located
close to but not touching the inside
tube surface and each stack must
rest directly over the stack below
without any gaps that could create
hot spots. However, the internal sur-
faces of reformer tubes can be quite
irregular, especially on plants that
have been in service for some time.
Hence the installation of Catacel
SSR is managed using patent pro-
Figure 3 Gas forced out of duct and back into the underside vents tected deployment technology that
forms part of the support structure
engineered foil structures called back into the triangular duct on the along with patent protected installa-
fans (see Figure 2). The fans are underside of the fan (see Figure 3). tion tools and methodologies.
coated with a nickel based steam The washers that separate the fans During the installation at
reforming catalyst using a propri- from one another facilitate this flow Roussillon, each stack of fans was
etary process that ensures the cata- back into the fan. Once inside the inserted in a compressed configura-
lyst remains attached to the surface fan, the gas is free to move to the tion and engaged with the stack (or
of the foil during the catalyst life- next fan in the stack and repeat the support) below. Using compressed
time. The fans are stacked one upon process. air, it was then expanded to bring
another in the reforming tube, sep- The features of Catacel SSR result the fan edges into the correct posi-
arated by thin metal washers. The in approximately 20-30% more heat tion versus the tube wall. Deposition
outer edges of the fans are located transfer for the same (or lower) was observed on the wall of some
close to, but not touching, the inter- pressure drop when compared to tubes but it was scraped off and did
nal surface of the tube. traditional catalyst pellets. In addi- not inhibit the loading. The instal-
The stacked fans deliver superior tion, the fans offer 1.5 to 2.0 times lation was completed according to
heat transfer by impinging gas on more geometric surface area than schedule. Outage and pressure drop
the internal surface of the reform- conventional pellets. Thus it pro- measurements during and on com-
ing tube rather than relying on con- vides a step change in the achieva- pletion of the loading confirmed
vective heat transfer mechanisms. ble performance from conventional each stack had successfully inter-
During operation, gas flows down pelleted steam reforming catalyst. locked with the stack below.
the tube and encounters the first fan Figure 4 shows a comparison of the
structure. It cannot move through different generations of pelleted Increasing hydrogen throughput by
the fan and therefore it is forced ceramic catalyst against Catacel SSR. increasing reforming temperature
out of the triangular ducts. The The enhanced heat transfer provided
process gas thus jets directly onto Installation at Roussillon by Catacel SSR allows additional
the internal surface of the reformer Catacel SSR is supplied as preas-
tube, where it gathers heat. Having sembled stacks up to a metre long.
nowhere else to go, the gas flows The fans are mounted on a support
around the edges of the fan and structure that sits within the central
Relative performance indicator

Activity
Heat transfer
Pressure drop

Rings 4-hole Quadralobe Catacel SSR

Figure 4 Relative performances of various steam reforming catalysts Figure 5 Installation of Catacel SSR

24 Catalysis 2017 www.eptq.com

catalysis JM.indd 2 27/02/2017 10:52

 burner firing to take place before
Increasing hydrogen throughput by increasing reforming temperature
the maximum flue gas exit temper-
ature is reached. Thus it is possible
to achieve a higher reformer exit Conventional catalyst Catacel SSR
temperature for the same flue gas Flue gas temperature, °C 1000.1 997.5
Reformer exit temperature, °C 816 828.5
temperature. Consequently, follow- S/C 3.24 3.1
ing the installation at Roussillon the Pressure drop, bar 0.68 0.51
methane conversion is higher and Dry syngas flow rate, Nm3/h 4043 4178
the hydrogen production from the Methane slip, mol% 6.7 6.2
Hydrogen production before PSA, Nm3/h 2965 3078
reformer is improved. Table 1 com- Hydrogen throughput, Nm3/h 2450 2490
pares the conventional catalyst per- Performances in capacity increase
formances with that of Catacel SSR Increase in syngas flow rate, % - 3.3
for the maximum flue gas tempera- Increase in hydrogen before PSA, % - 3.8
Tflue gas - Tsyngas, °C 184 169
ture allowed.
The increased capacities in syn-
gas and hydrogen production Table 1
before purification (by pressure
swing adsorption, PSA) are 3.3% Increasing hydrogen throughput by increasing plant load
and 3.8%, respectively, compared
to former operation. The increase in Conventional catalyst Catacel SSR
dry syngas flow rate is in line with Flue gas temperature, °C 1000 1000
predictions. Besides, this capac- Reformer exit temperature, °C 816 819
S/C 3.2 3.1
ity enhancement is achieved at a
Pressure drop, bar 0.68 0.57
lower reformer pressure drop than Dry syngas flow rate, Nm3/h 4043 4299
with conventional catalyst: 0.51 bar Methane slip, mol% 6.7 7.0
instead of 0.68 bar. Hydrogen production before PSA, Nm3/h 2965 3135
Hydrogen throughput, Nm3/h 2450 2553
The heat transfer enhancement
Performances in capacity increase
by Catacel SSR is also highlighted Increase in syngas flow rate, % 6.3
by the lower difference between Increase in hydrogen before PSA, % 5.7
syngas and flue gas temperatures Tflue gas - Tsyngas, °C 184 181
compared to conventional catalyst:
initially 184°C, reduced to 169°C. Table 2

Increasing hydrogen throughput by Plant load

increasing plant load
The previous case clearly indicates
that additional burner firing is pos-
sible thanks to Catacel SSR. The
increased hydrogen production is
achieved through a higher reformer
exit temperature and thus a higher
methane conversion. However, the
hydrogen production of the unit
can be increased more substantially
by also increasing the plant load
in addition to increasing burner
firing. Table 2 summarises the per-
formances of Catacel SSR in this
operating mode and compares it
to operation with previous con-
ventional catalyst under the lim-
itation of the maximum flue gas
temperature.
In this operating mode, the syn-
gas flow rate is increased by 6.3%.
The hydrogen throughput from
the reformer is 5.7% higher. This
capacity increase is achieved at a
lower reformer pressure drop than
with pellets: 0.57 bar instead of 0.68
bar.
Plant load range
(dry syngas production)
Below 50%
51-70%
71-80%
81-90%
91-100%
101-105%
>105%
Table 3
Performance over a year in operation
A year of operation with Catacel
SSR was achieved without any
incident. Data was collected from
September 2015 until September
2016 to compare with the perfor-
mance of pellets over the year
2014. Plant loads for both time
periods are shown in Table 3. As
can be seen, the plant was oper-
ated at more than 100% load (with
respect to dry syngas production)
with the catalyst for an extended
period of time. Obviously, the plant
load is dependent on the opera-
Pellets Catacel SSR
(% of operating time) (% of operating time)
4.2 2.0
6.3 2.3
13.4 38.2
19.0 18.1
57.1 14.9
0.0 19.8
0.0 4.7
tor’s demand but the results clearly
show that a maximum increase of
hydrogen throughput by over 5%
was successfully sustained.
Such an increase in production
was possible because the flue gas
temperature at the reformer exit
remained below the threshold of
1000°C, even at 106% load. Figure
6 shows the decrease of flue gas
temperature when the plant is oper-
ated with Catacel SSR compared to
operation with conventional pel-
lets. For a load range between 91%
and 100%, the flue gas temperature

www.eptq.com Catalysis 2017 25

catalysis JM.indd 3 27/02/2017 10:52

 performance that can then allow the
Catacel SSR unit limits to be overcome.
1000 Conventional catalyst Collaboration between Air
Liquide and Johnson Matthey facil-
Flue gas exit temperature, ºC
990 itated an understanding of the end
user requirements, identifying the
980
existing bottlenecks and possible
970
solutions. Although the SMR at Air
Liquide’s Roussillon plant is tailored
960 for conventional pelleted reforming
catalyst, the benefits of the coated
950 foil based structure to overcome the
previously observed limit on flue
940 gas exit temperature were demon-
81-90 91-100 101-105 106+
Plant load, %
strated. Catacel SSR catalyst has
and continues to demonstrate that
Figure 6 Comparison of flue gas exit temperature for various plant loads it is mechanically and chemically
robust over a range of operating
conditions. Assessing the reduction
108 Catacel SSR in total natural gas usage at differ-
Conventional catalyst ent plant rates, Air Liquide has been
106
also able to validate the increased
104
plant efficiency and highlight the
Plant efficiency

102 long term value. By employing

100 the novel catalyst, the required 5%
increase in throughput was achieved
98
successfully and without incurring
96 any capital cost to modify the plant
94 equipment as otherwise may have
been necessary.
92
81-90 91-100 101-105 106+ CATACEL SSR is a trademark of Johnson
Plant load, % Matthey Process Technologies.
References
Figure 7 Plant efficiency (syngas flow/total natural gas flow) at various loads 1 Farnell P, Whittenberger W, Foil supported
catalysts deliver high performance in
is decreased by up to 7°C, giving a flexibly, robustly and efficiently to steam reformers, Nitrogen + Syngas 2015
margin to increase the plant hydro- meet the user’s needs. As a world International Conference, Istanbul, Feb 2015.
gen throughput. leader in gases, technology and ser- 2 Whittenberger W, Catacel SSR novel
The overall efficiency of the vices for industry and health, Air structured catalysts for high performance in
reformer and water gas shift section Liquide is always striving to explore steam reformers, PTQ Catalysis, 31-33, 2015.
can be assessed by considering the process improvements and thereby
total natural gas flow rate required exceed customer expectations. Marie Basin is a Research Engineer with Air
Liquide Research and Development. She is
to produce syngas. Figure 7 pre- Steam reforming remains the
a chemical engineer and graduated from
sents this data for different plant dominant process for the production
École Nationale Supérieure des Industries
loads. The savings on natural gas of hydrogen. Despite being a mature Chimiques (ENSIC Nancy, France) and
with Catacel SSR are high thanks process there is still an opportunity Imperial College London.
to better conversion in the reformer to employ innovative technologies Daniel Gary is Senior International Expert in
due to higher reforming tempera- to drive improvement. Structured gas production and gas purification with Air
tures, and lower fuel consumption Catacel SSR technology represents Liquide. He graduated from University Paul
due to increased heat transfer in the the next generation of steam reform- Sabatier Toulouse in chemical engineering.
reformer. Savings are in the range ing catalysts offered by Johnson Jumal Shah is a Hydrogen Technologist with
of 3-4% for loads between 80% and Matthey, delivering a significant Johnson Matthey in Billingham, UK. He holds
105%, even reaching 5% at a load of improvement in performance com- a MEng in chemical engineering from the
University of Bradford.
106%. pared to traditional pelleted cata-
William A Whittenberger is Site and
lysts. Adoption of the catalyst has
Technology Director with Johnson Matthey
Conclusions shown the benefits of cooler tubes Process Technologies, which acquired the
Hydrogen is used in oil refineries, with lower methane slip and lower assets of Catacel Corp in 2014. He co-founded
chemical plants and in clean trans- pressure drop. Whilst greater bene- Catacel in 2001. He holds a bachelor’s degree
portation solutions. Due to chang- fits may be achieved with a reformer in mechanical engineering from Ohio State
ing market conditions there is a designed round the catalyst,2 even University, and a MBA from Pepperdine
greater need to be able to operate for existing plants it can improve University.

26 Catalysis 2017 www.eptq.com

catalysis JM.indd 4 27/02/2017 10:52

rezel.indd 1 14/12/2016 11:08
 5th
REFINING
INDIA
PTQ's international conference for India
held in partnership with Industrial Development Services

Lalit Hotel, New Delhi

3-4
18-19 September 2017

ptq
PETROLEUM TECHNOLOGY QUARTERLY

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 Optimising middle distillate production in
a hydrocracker
How to maximise middle distillate production and assure product quality from a
range of hydrocracking catalysts and processing schemes
JENS A HANSEN and ASBJØRN S ANDERSSON
Haldor Topsoe
H
ydrocracking is one of the
key processes of a modern
refinery, and a hydrocracking
unit is one of the most profitable
units in a refinery. Hydrocracking
will continue to be a very impor-
tant process to meet the increased
demand for clean transportation
fuels. In view of this, new devel-
opments in hydrocracking catalysis
and process technologies are contin-
uously taking place.
The processing requirements will
determine the optimum design of
a hydrocracking process and the
optimum catalyst selection. This
will include the feed rate and feed
quality as well as the make-up gas
quality and availability. Typical
hydrocracker feedstocks are
straight-run gas oils, vacuum gas
oils (VGO), coker gas oils, fluid
catalytic cracking oils, and decant
oils as well as mixtures of those.
The desired product(s), which may
range from liquefied petroleum
gas (LPG), naphtha, kerosene, and
diesel to unconverted oil (UCO) as
well as the required product prop-
erties and yield, determine the con-
version requirements.
Nowadays, practically all hydro-
crackers operate with a pretreat-
ment catalyst for removal of
nitrogen compounds in front of
the hydrocracking catalyst. Recent
developments within NiMo hydro-
treating catalyst technologies like
the HyBRIM technology invented
by Topsoe resulted in a new hydro-
cracking pretreatment catalyst
named TK-611 HyBRIM.1 This cata-
lyst lifted the activity by 25% com-
pared to the previous generation
of commercially available state-of-
the-art pretreatment catalysts like
www.eptq.com
catlayis haldor.indd 1
the Topsoe TK-609 HyBRIM cata-
lyst. The use of such a catalyst in
hydrocracking service adds addi-
tional flexibility to the operation of
a hydrocracker like longer catalyst
cycles, more throughput, better
product qualities, or even the abil-
ity to process more severe feed-
stocks. It also allows the refiner to
cut back on pretreatment catalyst
volume and to install less active
hydrocracking catalysts, resulting
in an improved middle distillate
selectivity and/or product quality,
if this is economically feasible.
Last but not least, optimum oper-
ation of a hydrocracker not only
requires high performance state-
of-the-art pretreatment and hydro-
cracking catalysts but also well
functioning reactor internals and cat-
alyst grading systems. Furthermore,
an optimal process scheme should
be used. The company developed
a full range of proprietary high
performance reactor internals. For
full conversion hydrocrackers, the
build-up of heavy polynuclear aro-
matic compounds (HPNA) has to
be controlled to ensure seamless
operation. For hydrocrackers, where
HPNA management is needed,
Topsoe developed a new technology
named HPNA Trim.
Selection of hydrocracking catalysts
When it comes to the selection of
the best hydrocracking catalyst sys-
tem for a given application, many
different factors have to be taken
into consideration. This is far more
complicated than selecting a hydro-
cracking pretreatment catalyst,
where the use of a high activity
hydrocracking pretreatment cata-
lyst would be the preferred choice,
as this gives additional flexibility
in hydrocracking catalyst selection
and operation as mentioned above.
In the selection of a hydrocracking
catalyst system, a very important
factor would be the optimisation
of the catalyst loading to maxim-
ise the profitability of the unit. The
profitability of the unit is related to
the values of the different products
from the hydrocracker. For each
product, the value is related to the
quality of the product. Some hydro-
crackers produce mainly naphtha,
whereas other units produce mainly
middle distillates. For a number of
hydrocrackers, the production of
UCO for either lube production or
for steam cracker feedstock is very
valuable. Other hydrocrackers bene-
fit from their ability to shift between
the production of mainly naph-
tha and the production of mainly
middle distillates dependent on a
change in seasonal demands and/
or in the value of products. In some
areas, the cold flow properties of
the diesel product are very impor-
tant. For hydrocrackers aiming at
production of high quality UCO for
use as feedstock for lube dewaxing,
the viscosity index of the UCO is a
crucial factor. In essence, this means
that hydrocrackers have very dif-
ferent processing objectives, and
that all hydrocrackers are unique in
typical feedstock composition and
main objectives.
To meet different processing
objectives, a broad portfolio of
hydrocracking catalysts for dif-
ferent applications is a must. The
portfolio of base metal hydrocrack-
ing catalysts offered by Topsoe is
shown in Figure 1. It is well known
that low activity hydrocracking
Catalysis 2017 29
27/02/2017 10:48

Middle distillate selectivity
TK-921
Figure 1 The portfolio of Topsoe base metal hydrocracking catalysts
catalysts have a high selectivity
towards middle distillate produc-
tion, whereas high activity hydro-
cracking catalysts exhibit a lower
middle distillate selectivity. Topsoe
offers three series of hydrocracking
catalysts, which cover a wide activ-
ity range. The red series is for appli-
cations where maximum product
hydrogenation is required. The blue
series is for applications where the
improvement of cold flow proper-
ties of diesel is important. The cat-
alyst belonging to the D-sel series is
used to maximise the middle distil-
late yield. In many cases, the use of
more than one hydrocracking cat-
alyst in a given unit is the optimal
choice. It is possible to combine, for
example, a hydrocracking catalyst
from the red series with a hydroc-
racking catalyst from the blue series
Feed
Single stage
hydrocracking
Fractionator
Recycle oil
(optional)
HPNA trim
(optional)
Figure 2a Single stage hydrocracking unit; 2b Two stage hydrocracking unit
30 Catalysis 2017
catlayis haldor.indd 2
once-through hydrocracking, two
stage hydrocracking, and sepa-
rate hydrotreat hydrocracking. The
TK-939 D-sel
most common design is the single
TK-926
stage system.
TK-949 D-sel
A simplified process scheme for
TK-925
TK-943
single stage and two stage hydroc-
TK-931
racking is shown in Figure 2. In sin-
TK-947
TK-941 gle stage hydrocracking, the fresh
TK-951 feedstock and UCO are treated with
TK-961 surplus hydrogen over a hydroc-
TK-971
racking pretreatment catalyst fol-
lowed directly by a hydrocracking
Activity catalyst system. In many cases,
two reactors are used, one for the
hydrocracking pretreatment cata-
lyst including catalyst grading and
to tune the properties of the pro- one for the hydrocracking catalyst
duced diesel, so that good cold flow system. The product is fractionated
properties and an excellent cetane into light ends, naphtha, kerosene,
number are obtained at the same diesel, and UCO. The UCO can be
time. This loading solution was suc- recycled back to the reactor. It is an
cessfully used by a handful of com- option to let the UCO recycle pass
mercial units. a HPNA Trim unit for removal and
In the following, three cases will management of HPNA compounds
be discussed, which illustrate how before it is recycled back to the
the selection of catalysts and the reactor. Once-through hydrocrack-
use of different process schemes ing is without liquid recycling. For
can result in a maximisation of mid- simplicity’s sake, the high pressure
dle distillate production and of the separator as well as the recycle
product quality of diesel. compressor were omitted from the
process scheme shown in Figure 2.
Catalysts for maximising middle In the two stage process, the hydro-
distillate production in single stage cracking pretreatment of the feed-
and two stage units stock and part of the hydrocracking
Traditionally, hydrocracking pro- are carried out in the same way as
cess configurations are classified by during the single stage process.
four basic process schemes: single The product from the first cracking
stage hydrocracking with recycle, stage is fractionated in the same
fractionation system as mentioned
H2 Feed H2 above, and the UCO is passed to
an additional reactor loaded with
a hydrocracking catalyst system.
As mentioned before, it is in this
Two stage case also an option to let the UCO
hydrocracking
recycle pass a HPNA Trim unit. In
the two stage process, the hydroc-
Fractionator
racking in the second stage can take
place in the absence of ammonia
and in a sulphur-free atmosphere
Products (sweet operation), or in a sulphur
Products
containing atmosphere (sour oper-
ation). In case a sweet operation is
desired in the second stage, this can
Unconverted be carried out with two separate
Recycle oil Unconverted
oil (optional)
oil (optional) gas recycle loops or with a common
HPNA trim
(optional)
recycle gas that has been amine
Pretreatment catalyst treated. In the single stage process,
Hydrocracking catalyst hydrocracking is carried out in the
presence of ammonia and hydro-
gen sulphide (sour operation). The
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27/02/2017 10:48
 activity and selectivity of a hydroc-
racking catalyst are very dependent
on the amount of ammonia present
in the treat gas. The presence of
ammonia passivates the acidic sites
typically provided by the silica alu-
mina and/or zeolite compounds
present in the hydrocracking cat-
alyst support. A small bleed of the
recycle oil is normally taken out for
HPNA management. The HPNA
Trim technology is a versatile tool
for minimising the bleed rate.
For many hydrocrackers, the main
objective is maximisation of middle
distillate production. In this case, a
hydrocracking catalyst system with
a high middle distillate selectivity
should be selected. As can be seen
in Figure 1, the natural choice would
be to use the Topsoe catalyst TK-939
D-sel. Due to the lower activity of
TK-921, TK-925, and TK-926, these
catalysts would be less attractive to
use in existing single stage hydroc-
rackers. In the absence of ammonia
it was demonstrated in dedicated
pilot testing that TK-921 can have
a better middle distillate selectiv-
ity than TK-939 D-sel in two stage
hydrocracking. From a process
point of view, the lower activity of
TK-921 is not an issue in this sweet
environment, as the required reac-
tor temperature will be significantly
lower than 400°C. When the ammo-
nia concentration in the treat gas of
the second stage becomes higher, it
becomes attractive to use the more
active TK-939 D-sel catalyst.
Based on these findings, the opti-
mal catalyst loading for a single
stage unit and a two stage unit aim-
ing at maximising the middle dis-
tillate yield from a VGO feedstock
was studied in pilot plant testing. A
single stage catalyst loading using
the TK-609 HyBRIM pretreatment
catalyst in front of the TK-939 D-sel
hydrocracking catalyst was com-
pared with a two stage loading con-
sisting of the pretreatment catalyst
TK-609 HyBRIM and the TK-939
D-sel hydrocracking catalyst in the
first stage and the TK-921 hydro-
cracking catalyst in the second
stage. The yields of kerosene (160-
285°C), heavy diesel (285-370°C),
and a wide boiling middle distil-
late cut (>160°C) for the two pro-
cess schemes are shown in Figure
www.eptq.com
catlayis haldor.indd 3
Product quality from single and two stage processing at a CFR of 2.25
Two stage Single stage
Kerosene/160-285°C Mono-aromatics, wt% 10.6 14.2
Smoke point, mm 27 25
Heavy diesel/285-370°C Mono-aromatics, wt% 8.4 10.5
CCI (ASTM D 4737) >70 >70
Cloud point,°C -12 -8
Table 1
3. The combined feed ratio (CFR) is racking catalysts in the same unit
the amount of combined feed (fresh can be beneficial. When it comes to
and recycle oil) relative to the fresh product quality, the kerosene and
feed rate. For the single stage pro- heavy diesel cuts produced from
cess, the results obtained for two a two stage process are of a better
different CFR cases are given. The quality than those obtained from
middle distillate yield obtained in processing in a single stage process
the two stage process was higher as shown in Table 1. The aromatic
than that found for the single stage content in the kerosene and die-
process. The middle distillate yield sel cut is found to be lower in the
decreases in the single stage pro- two stage process. The best kero-
cess, when the CFR is decreased. sene smoke point is obtained in two
For a typical single stage operation, stage processing. The heavy diesel
the operating CFR is in the range cloud point is lower in two stage
1.3-1.6, so the middle distillate yield processing than in single stage pro-
from a typical commercial single cessing. The properties of the naph-
stage operation is in fact lower than tha cuts are similar. The improved
that shown in Figure 3. The CFR product qualities obtained in two
used in the two stage test, how- stage processing do not result in an
ever, is quite typical of industrial overall higher hydrogen consump-
applications. This example clearly tion as compared with that of sin-
illustrates that a two stage process gle stage processing due to the fact
gives a higher middle distillate that a lower amount of light ends
yield than a single stage process for and naphtha cuts are formed. The
hydrocracking of VGO. It also illus- hydrogen is consumed in a more
trates that the use of two hydroc- intelligent way.
Two stage processing with TK-609 HyBRIM,
TK-939 D-sel and TK-921 at a CFR of 2.25
Single stage processing with TK-609 HyBRIM
and TK-939 D-sel at a CFR of 2.25
Base case: single stage processing at a CFR of 1.75
(CFR = Combined Feed Ratio)
VGO feed
12 SG 0.92
Sulphur 1.9 wt%
10
Nitrogen 1400 wt ppm
8 Simdist (10/50/90) 356/441/528ºC
∆Yields, vol% FF
6
4
2
0
−2
−4
160-285 ººC 285-370 ºC 160-370 ºC
Figure 3 Middle distillate yields for single and two stage processing
Catalysis 2017 31
27/02/2017 10:49

Feed H2 Feed
Separate hydrotreat
Fractionator
Products
Stripper
gas
Recycle oil Unconverted
oil (optional)
Pretreatment catalyst
Hydrocracking catalyst
HDA catalyst
Figure 4a Separate hydrotreat; 4b Separate hydrotreat with stripper
For new hydrocrackers aiming at
maximising middle distillate pro-
duction, it is highly relevant to con-
sider a two stage design rather than
a single stage design. A revamp of
once-through hydrocrackers and
single stage hydrocrackers to two
stage hydrocrackers can be a very
attractive way to boost production
of middle distillates.
How to produce ultra low aromatics
diesel from a feedstock rich in LCO
Cracked products such as light
cycle oil (LCO) have a considerably
lower cetane value than straight-
run distillates. LCO is a poor diesel
fuel blending component due to its
poor engine ignition performance
and its high sulphur content. In a
clean fuels refinery, LCO can be an
issue. Many North American refin-
ers have historically routed their
LCO to a hydrocracker in order to
crack it into naphtha and lighter
products. The produced naphtha
product quite often requires cata-
lytic reforming before it is blended
into the gasoline pool. With the
increased demand for diesel that
has to meet, for example, demand-
ing sulphur, cetane, and aro-
matic specifications, new ways to
upgrade LCO to high quality diesel
are of profound interest. Up to now
it has been a challenge to produce
diesel meeting the low diesel aro-
32 Catalysis 2017
catlayis haldor.indd 4
H2
Separate hydrotreat
with stripper
Gas
Fractionator
Products
Recycle oil Unconverted
Stripper oil (optional)
matic content as specified by some
countries and regions (for exam-
ple, 10% in California and 5% in
Sweden) when processing LCO in
a hydrocracking unit. In fact, the
dream scenario was to find a way
to produce a diesel product with
less than 5% aromatics. By per-
forming process modifications and
by using existing catalysts in new
ways, it is now possible to produce
It is now possible to
produce high quality,
low aromatic diesel
from LCO that by
far meets the diesel
aromatic target
high quality, low aromatic diesel
from LCO that by far meets the die-
sel aromatic target.
Industrial processing of LCO
alone or in combination with a gas
oil is practised in various hydro-
cracking process layouts. These
include single stage and two stage
process designs as shown in Figure
2. With a LCO feedstock, the recy-
cle oil is a diesel boiling material.
Since there is now also an interest
in co-production of middle dis-
tillates, it is desirable if the mid-
dle distillates can be routed to the
diesel pool without any further
upgrading. It is not a challenge to
meet the diesel sulphur specifica-
tion. However, in both single stage
and two stage processing mode it
is difficult to produce high cetane
or low aromatic diesel from LCO.
In a typical two stage design, the
diesel product is a blend of die-
sel produced in the first stage and
in the second stage. In general, the
diesel product from the first stage
has a high aromatic content, which
cannot meet a 10% diesel aromatic
target.
In the early days of hydrocrack-
ing, one of the first process lay-
outs used in the industry was the
so-called separate hydrotreat pro-
cess (see Figure 4a). In essence, this
process is a two stage operation,
where no hydrocracking catalyst is
used in the first step. Only a hydro-
cracking pretreatment catalyst is
used in the first stage. In this pro-
cess, part of the hydrotreated feed
from the first stage ends up in the
diesel product.
Another variation of the sepa-
rate hydrotreat process includes a
stripper after the first stage reac-
tor, which removes the hydrogen
sulphide and ammonia from the
liquid product (see Figure 4b). The
stripped, deeply hydrotreated liq-
uid product from the first stage can
then be routed to the second stage
reactor and processed essentially in
the absence of ammonia. As men-
tioned in the previous example, this
allows for the use of low activity
and high selectivity hydrocracking
catalysts. In this case, where hydro-
genation of the LCO aromatics was
needed, a natural catalyst choice
would be a hydrocracking cata-
lyst from the red series (see Figure
1) to get as much hydrogenation
and ring opening as possible. Since
co-production of diesel was also
required, a hydrocracking cata-
lyst of moderate activity with good
middle distillate selectivity like
the Topsoe hydrocracking catalyst
TK-931 would seem to be a suitable
choice. However, it turned out that
the aromatic saturation activity of
TK-931 was not sufficient to give a
diesel aromatic content below 10%.
www.eptq.com
27/02/2017 10:49
 In order to produce lower diesel
Properties of the feedstock, first stage product, and final jet and diesel product
aromatics, it was decided to intro-
duce a noble metal hydro dearo-
Feedstock First stage product Jet product Diesel product
matisation (HDA) catalyst after the
SG (D 4052) 0.929 0.893-0.897 0.83-0.84 0.850-0.865
hydrocracking catalyst. S, wt ppm (D 4294) 4200 25-35 <0.2 <0.3
Topsoe developed a range of N, wt ppm (D 4629) 1018 1-2 <0.2 <0.2
noble metal HDA catalysts and a Aromatics (D 6591)
Mono, wt% 21.6 50.4-53.0 <0.5 <0.7
two stage process for diesel dea-
Di, wt% 30.0 2.0-2.3 <0.1 <0.1
romatisation to be able to meet Tri+, wt% 5.9 0.2-0.3 <0.05 <0.05
the Swedish diesel specification of Sim. Dist. (D 7213C)
maximum 5% aromatics and the 10 wt% 218 206-208 178-180 231-242
50, wt% 281 269-270 207-208 271-274
Californian specification of max-
90, wt% 348 336-338 222-230 337-341
imum 10% aromatics. This tech- Cetane Index (D 4737) 26 32-33 - 45-52
nology is already being used by Smoke point, mm (D 1322) - - 22-24 -
several operators in stand-alone
aromatics saturation units. The Table 2
present Topsoe HDA catalyst port-
folio includes TK-907, TK-911, and dimension of the GC×GC chromato- ity occurs as the di- and tri+-aro-
TK-915. TK-915 is the most active of gram is similar to that of a normal matics are saturated into mainly
these catalysts and has the best tol- GC chromatogram, where increas- mono-aromatics but also to a lesser
erance towards hydrogen sulphide ing retention time is proportional extent into naphthenes. To further
and ammonia. TK-915 was tested in to increasing boiling point. Adding illustrate this reaction, the fate of a
combination with TK-931 for LCO a second dimension with separa- dimethyl-substituted naphthalene
upgrading, as illustrated by the fol- tion according to polarity makes was tracked. The C2-diaromatic (C2-
lowing example. a much more detailed composi- Na) was very abundant in the feed
The hydrocracking pretreat- tional analysis of the complex oil but was not found in the product.
ment catalyst TK-609 HyBRIM was samples possible. In this case, the The C2-Na can be partly saturated
loaded in the first stage reactor. least polar compounds (paraffins) into a C2-tetralin (C2-Te) or be fully
In the second stage, the red series appear in the top of the chroma- saturated into a naphthene (C2-De).
hydrocracking catalyst TK-931 was togram, and the more polar com- Neither of these saturation products
loaded on top of the noble metal pounds (aromatics) are found near were abundant in the feed, but they
HDA catalyst TK-915. Each stage the bottom of the chromatogram. could easily be identified in the
was operated at a pressure of 105 Figure 5 shows the chromatogram first stage product. This finding is
barg. The testing took place in a of the feed (top) and the first stage in agreement with the HPLC based
modified two stage pilot unit able product (bottom). The most impor- aromatic analysis results shown in
to simulate the process shown in tant trend is a shift along the ordi- Table 2.
Figure 4b. The feedstock was a nate, which represents a decrease The first stage product was com-
mixture of gas oil and LCO with in polarity. This decrease in polar- bined with the recycle oil before
the properties given in Table 2.
The testing lasted more than 2000 Paraffins Feed
hours. The first stage reactor was
operated at a temperature of about
350°C, whereas the second stage Naphthenes
CH3
reactor was operated in the range
C2-De
307-335°C. C2-Na
Mono CH3
The properties of the hydro- aromatics
C2-Te
treated product from the first stage
Di+
is shown in Table 2. The product aromatics CH3
C2-Na
sulphur level was below 35 wtppm,
and most of the di- and tri+-aro- Paraffins First stage product C2-Te
CH3
matics were converted into mono-
aromatics. The feedstock and first
stage products were also analysed Naphthenes CH3
by the so-called GC×GC gas chro-
C2-De
matography technique, which in a CH3
Mono
three dimensional plot gives a clas- aromatics
sification of the hydrocarbon spe-
cies present (see Figure 5). Access to Di+ aromatics
such information is crucial to under-
stand the fundamental chemistry Figure 5a GCxGC chromatogram of feed for dearomatisation; 5b GCxGC chromatogram
of the different catalysts. The first of first stage product

www.eptq.com Catalysis 2017 33

catlayis haldor.indd 5 27/02/2017 10:49


Paraffins
Second stage feed
C2-De
C2-Te
Paraffins
C6-BZ
Paraffins
HDA bed effluent
C6-cHex
Figure 6a Second stage feed; Figure 6b HC bed effluent; Figure 6c HDA bed effluent
it was routed to the second stage
reactor. The combined feed had a
content of about 32% mono-aro-
matics. The aromatics content was
about 15% mono-aromatics after
treatment with TK-931. Further
treatment with the HDA cata-
lyst TK-915 resulted in a dramatic
reduction in the diesel aromatics
(see Table 2). The diesel product
contained less than 1 wt% aromat-
ics, which is outstanding, and less
than 1 wtppm sulphur. The cetane
index was higher than 45. The pro-
duced diesel will be excellent as a
diesel blendstock. The jet fuel was
also extremely low in aromatics,
resulting in a high smoke point.
The density of the jet was rela-
tively high, but by adjusting the
kerosene/diesel cut point it was
possible to produce a jet product
meeting the Jet-A1 specifications.
The chemistry occurring in the
second stage reactor was also
studied by GC×GC (see Figure 6).
TK-931 has a dual purpose in this
configuration. The high hydro-
34 Catalysis 2017
catlayis haldor.indd 6
Naphthenes
Mono
aromatics
CH3
Di+ aromatics C2-Te
CH3
HC bed effluent
Naphthenes CH3
C6-BZ
CH3
Mono
aromatics
Di+ aromatics
CH3
C6-cHex
CH3
Naphthenes
genation capacity enables further
conversion of mono-aromatics into
naphthenes, but the cracking func-
tion also plays a very important role
in this process. Instead of undergo-
ing the saturation reaction described
above, the C2-Te can also undergo
a ring opening reaction into a one
ring aromatic compound C6-Bz
(see Figure 6b). The benefit of this
type of reaction is the fact that the
density is lowered without remov-
ing the compound from the diesel
boiling range, which results in a
significant cetane boost. In order
to saturate the remaining aromat-
ics, TK-915 HDA catalyst is used.
As can be seen from Figure 6c, it is
not possible to detect any aromatic
compounds in the reactor effluent
by GC×GC chromatography.
This example clearly illustrates
that it is possible to upgrade LCO to
a high yield of low aromatic, high
cetane diesel by combining process
technologies with innovative cat-
alyst loading schemes involving a
HDA catalyst in combination with a
hydrocracking catalyst in a separate
hydrotreat two stage process with a
stripping of the first stage effluent
between the two stages.
A more active hydrocracking cat-
alyst than TK-931 can be used in
case a higher naphtha production
is desired. In fact, it is also possible
to exclude the hydrocracking cata-
lyst and only use a HDA catalyst in
the second stage reactor. This will
result in less ring opening, and the
produced jet and diesel will end up
having a higher density than that
found when a hydrocracking cat-
alyst is used in front of the HDA
catalyst.
Is full conversion in a once-through
unit possible?
Normally, a recycle unit (single
stage or two stage process layout)
will be the route to take to achieve
full conversion. In some cases, how-
ever, it is possible to achieve full
conversion in a once-through hydro-
cracker by adjusting the properties
of the feedstock, so that no UCO is
produced. As no UCO is produced,
a dedicated costly distillation col-
umn separating the UCO from the
other products is no longer needed.
Two Topsoe hydrocracking cata-
lysts, TK-925 and TK-926, were com-
pared in once-through pilot testing
using a light vacuum gas oil. The
objective of the test was to maximise
the production of a full range die-
sel (>180°) and to identify operating
conditions eliminating the produc-
tion of UCO. The results of the test-
ing are summarised in Figure 7.
The yield of the full range diesel
(>180°C) is shown in Figure 7a for
both catalysts as a function of the
ASTM D86 95% boiling point of
the full range diesel. The D86 95%
boiling point will decrease with
increasing reactor temperature,
and a specified D86 95% temper-
ature for the full range diesel can
be obtained by adjusting the reac-
tor temperature. The obtained D86
95% temperatures were within the
accepted range. TK-926 gave a bet-
ter diesel yield than TK-925. With
regard to diesel properties, the
cloud point obtained with TK-926
was much lower than that obtained
with TK-925 (see Figure 7b). The
highest cetane index (+4 to 5) was
www.eptq.com
27/02/2017 10:49
 as seen in Figure 7c obtained with
TK-925 due to its high hydrogena- A Light VGO feed
tion activity. The cetane index SG 0.8816
obtained with TK-926 was very sat- Sulphur 0.55 wt%
isfactory. This case clearly illustrates 78 Nitrogen 601 wt ppm
that high amounts of diesel with Simdist (10/50/90) 308/399/451 ºC
77
good properties can be produced

>180ºC yield, wt% FF

without co-production of UCO. 76
Commercially, this approach was
used successfully. 75
Other tests showed that the die- 74
sel yield can be further improved
by the use of TK-939 D-sel. In a 73
particular case with a slightly heav-
72 TK-925
ier feedstock (SG: 0.8937, S: 0.32
TK-926
wt%, N: 1138 wt ppm, SimDist
71
10/50/90%: 382/421/471°C), the
20
yield of a full range diesel (>145°C) B
Cloud point, ºC
TK-925
with a requested D86 95% diesel 10
TK-926
boiling point of 360°C was 12 wt% 0
FF higher with TK-939 D-sel than −10
with TK-926. The cloud point of the −20
diesel was found to be -30°C with
−30
the TK-939 D-sel catalyst and -48°C
with the TK-926 catalyst. C 70
Cetane index

For a given application, the opti-
mum catalyst system including a
high activity pretreatment cata-
lyst can be tailor-made to give the
desired diesel quality (D86 95% T,
cloud point, and cetane index). The
requested front end temperature of
the full range diesel will also vary
depending on the flash point spec-
ification. The obtainable yield of
the full range diesel depends on the
quality and nature of the feedstock,
on the specified front end and back
end diesel temperatures, as well
as on the diesel cold flow require-
ments. If boosting the cetane index
is required, a catalyst from the red
series can be part of the loading.
Some refiners may have a light vac-
uum gas oil or a heavy gas oil that
can be upgraded to high quality
diesel by installing a simple once-
through hydrocracker without a
UCO distillation unit.
For a traditional once-through
hydrocracker, a catalyst system
can also be tailor-made to give the
requested yield structure and die-
sel quality. In many cases, this will
require that more than one hydroc-
racking catalyst is loaded.
Conclusion
A major factor in maximising the
profitability of a hydrocracker is to
choose a catalyst system that can
TK-925
68
TK-926
66
64
62
365
Figure 7 Once-through pilot testing: middle distillate yield (>180°C product), cloud point
and cetane index vs ASTM D86 95% temperature
give the highest possible combined
value of products. In all cases, this
will call for the use of a high activ-
ity hydrocracking pretreatment cat-
alyst like Topsoe TK-611 HyBRIM.
When it comes to selection of the
hydrocracking catalyst system, it is
far more challenging to select the
best system as many factors have to
be considered. What is the optimal
product yield structure? What are
the optimal properties of each of
the produced products? What is the
value of each product related to the
product quality? All of these fac-
tors are refinery specific, and it is a
complicated analysis to determine
the best product structure with the
optimal product quality.
This article demonstrates how to
maximise middle distillate produc-
tion and how to impact product
quality, for instance cold flow prop-
erties, by the use of hydrocrack-
ing catalysts from different catalyst
series and by the use of different
370 375 380 385 390
Diesel 95% T, ºC
processing schemes. A new way to
produce very low aromatic, high
cetane diesel from LCO feedstock
with a high selectivity to diesel is
presented. This process includes the
innovative use of a hydrocracking
pretreatment catalyst, a hydrocrack-
ing catalyst, and a hydro dearomati-
sation catalyst.
HyBRIM, D-sel and HPNA Trim are trademarks
of Haldor Topsoe.
Reference
Schmidt M T, Developments in hydrotreating
catalyst, PTQ Q3 2016.
Jens Anders Hansen is a Senior Principal
Research Scientist with Haldor Topsoe
working primarily in hydrocracking catalyst
development, in the design of hydrocracking
test units, and in the evaluation of
hydrocracking catalysts.
Asbjørn Sune Andersson is a Principal Research
Scientist in Refinery R&D with Haldor Topsoe.
He holds a MS and a PhD in organic chemistry
from the University of Copenhagen.

www.eptq.com Catalysis 2017 35

catlayis haldor.indd 7 27/02/2017 10:49

 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
 Lessons from FCC history

Detailed catalyst data collected over 15 years reveal shifts in FCC yields in response
to changing market conditions, and provide a marker for future unit operations

JACQUELINE POPE, MELISSA CLOUGH and ALEXIS SHACKLEFORD

BASF Catalysts

U
nderstanding the evidence
of past activity is vital to the
Gasoil Resid
future of refining operations.
100
Aggregated data paint the macroe-
90
conomic trends that have driven the
industry. BASF regularly analyses 80
Proportion of total, %

41 38 40 38 38 37 39 38 43 48 45 51 52 50 49
equilibrium catalyst (Ecat) samples 70
from over 200 fluidised catalytic 60
cracking (FCC) units in refineries 50
globally to monitor key parameters
40
including surface area, contaminant 59 62 60 62 62 63 61 62 57 52 55 49 48 50 51
metals, and activity. In addition, 30
the company has operating data 20
snapshots from over 250 FCC units. 10
From these two sets of data, global 0
and regional trends can be extracted
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
and evaluated in order to under-
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
stand market drivers and indus-
try needs. This article will cover 15 Figure 1 Percentage of FCC units processing resid and gasoil feeds based on Ecat data
years of Ecat trends in the indus- suggests more resid processing today
try, while focusing on both Ecat
properties and ACE testing data.
Operating data are also explored 3.0
Gasoil
and juxtaposed against Ecat trends
2.5 Resid
for clarification. The data analysed Average
Concarbon, wt%

in this article represent the historical

turbulence that has rocked the FCC
industry, from changing econom-
ics to varying feedstocks and global
raw material pricing shocks. The
data also highlight the need for ever
changing technology in both cata-
lysts and hardware design.
Over the years, technology
advances, crude slates, and econom-
ics have changed how refineries
operate their FCC units. First, hard-
ware changes such as advanced feed
nozzles, riser termination devices,
and stripper efficiency improve-
ments represent significant changes
to operations. Major innovations
have also impacted the FCC cat-
alyst, such as using zeolite-based
catalysts, which show improved per-
formance compared to the original
2.0
1.5
1.0
0.5
0
2002 2004 2006 2008 2010 2012 2014 2016
Figure 2 Operating benchmarking data for feed Concarbon content separated by resid and
gasoil units suggest a clear differentiation when using metals to segment units
amorphous FCC catalysts. Also, new oline demand in Western Europe,
matrix materials are now being uti- which has impacted how refiners in
lised by refiners for improved coke this region operate their FCC units.
selectivity, bottoms cracking, and Increasing demand for petrochemi-
metals passivation. Economic driv- cal feedstocks from heavy oil sources
ers are also affecting refineries. One has also led to a change in operating
example of this is the declining gas- strategies. This article examines Ecat

www.eptq.com Catalysis 2017 37

basf.indd 1 28/02/2017 10:39

 trends and operating data trends
Global
over the past 15 years. Ecat trends
4.0 North America are explored and segregated based
Europe, Middle East, Africa on global region, while operating
3.5 Asia trends are segregated based on type
Latin America of operation (for instance, residual
3.0 feed and gasoil feed).
REO, wt%

Feed changes have impacted refin-

2.5 eries globally, for example tight oil
crudes in North America and heav-
2.0 ier crudes in Asia. In this article,
nickel (Ni) and vanadium (V) con-
1.5
tent is used as a marker for residual
feed (resid) and gasoil feed pro-
1.0
2002 2004 2006 2008 2010 2012 2014 2016 cessing. Resid units are defined as
having greater than 3000 ppm Ni +
V content on Ecat. Conversely, gas-
Figure 3 Ecat benchmarking data for REO (rare earth oxide) content - increased until the oil units are defined as having less
price of REO peaked in 2010; since, values have levelled off to a lower value than 3000 ppm Ni + V. As Figure 1
shows, in recent years, especially
2013 and after, the percentage of
units processing resid feed is greater
170 Global
than gasoil feed according to Ecat
North America
data benchmarking. This trend is in
160 Europe, Middle East, Africa
Asia
stark contrast to 2002 when units
Latin America processing resid feed represented
150
less than 40%. This is a significant
TSA, m2/gm

increase in the number of refineries

140
that have shifted to resid feeds in
130 the past 15 years, which impacts cat-
alyst selection, hardware, and unit
120 operations of the refinery.
Feed Concarbon is the measure of
110 the coke forming tendencies of the
hydrocarbon feed. To confirm the
100 division of resid versus gasoil units
2002 2004 2006 2008 2010 2012 2014 2016 based on metals, feed Concarbon
data, provided by the refineries,
Figure 4 Ecat benchmarking data for total surface area (TSA) were examined. The data in Figure 2
suggest a good divide between gas-
oil and resid units using the above
definitions. Resid units have higher
75 Concarbon (average ~2 wt%), as
expected due to higher contami-
74 nation, while gasoil units’ average
Concarbon is ~0.5 wt%. There has
73 been a slight increase in resid feed
Concarbon in recent years from a
72 global perspective, which is a result
FACT, wt%

of heavier crudes being processed.

71
Data presented in this article are
representative of refineries across
70
the globe. The trends are com-
Global
69
piled from 2002-2016 and repre-
North America
sent global averages. Importantly,
Europe, Middle East, Africa
68 Asia
shifts in averages require large
Latin America moves globally and are indicative
67 of market pressures and opportu-
2002 2004 2006 2008 2010 2012 2014 2016 nities. Further, a shift in the data
requires a change across a region
Figure 5 Ecat benchmarking data for fluidised activity (FACT) as opposed to minor regional (or

38 Catalysis 2017 www.eptq.com

basf.indd 2 27/02/2017 10:56

 refinery specific) changes. In order
to differentiate between regional 995 535
Gasoil
market differences, the Ecat trends

Riser outlet temperature, ºC

Riser outlet temperature, ºF
Resid
presented here are broken into the 990
Average
global regions of North America,
Latin America, Europe Middle East 530
985
and Africa (EMEA), and Asia. The
first half of this article focuses on
Ecat properties, while the second 980
half looks at ACE testing at con- 525
stant conditions. 975

Equilibrium catalyst benchmarking

970 520
analyses 2002 2007 2012
Equilibrium catalyst properties
Rare earth, designated REO for rare 80
earth oxide, is a key component of 79
an FCC catalyst. REO improves 78
zeolite stability, imparts higher 77
Conversion, vol%

activity, and changes the selectiv-

76
ity of the catalyst toward higher
gasoline at the expense of liquefied 75
petroleum gas (LPG). REO is also 74
incorporated into some FCC addi- 73
tives. In 2010, the rare earth crisis 72
started after China limited its REO 71
exports, which affected REO prices
70
globally. During this time, the REO
content of Ecats around the world 69
2002 2007 2012
dropped significantly due to the
high cost of the raw material. Even
when REO prices stabilised in 2012, Figure 6 Operating benchmarking data for riser outlet temperature (top) and conversion
levels did not reach historical lev- (bottom)
els. Specifically, the data in Figure
3 show that the average REO con- occurred as a response to make up remove contaminants from the feed
tent in 2015 was 2.2 wt%, while the for the lower REO content previ- such as sulphur (S) and nitrogen
historical maximum was 2.6 wt% ously discussed. The jump in TSA (N). Due to lower contaminants
(black dotted line). This suggests was an attempt to boost catalyst in the FCC feed, catalyst activity
that there was, and to some extent activity. can remain high. Coupled with
still is, an economic incentive to Activity (see Figure 5) relates the highest TSA and REO, North
operate with lower REO. to both REO and TSA. In North America shows the highest Ecat
Looking at regional trends, North America, a large number of refin- activity during the time frame stud-
America operates at the highest ers utilise feed hydrotreaters, which ied. This is due to, in part, the pro-
REO content. This is due to a num-
ber of reasons, the most important
being that North America is a gas-
8.0
oline driven market, serving both Gasoil
the domestic and Latin American Resid
demands via exports. Asia has one Average
7.5
Catalyst/oil ratio

of the lowest REO content globally,

partially driven by the incentive for
petrochemicals. 7.0
The total surface area (TSA)
trend, shown in Figure 4, also sug-
gests significant differences region- 6.5
ally. Activity directly correlates to
TSA, with a higher TSA leading
to a higher activity catalyst. North 6.0
2002 2004 2006 2008 2010 2012 2014 2016
America has the highest TSA glob-
ally, with Asia in direct contrast.
In 2011, a significant jump in TSA Figure 7 Operating benchmarking data for catalyst to oil ratio

www.eptq.com Catalysis 2017 39

basf.indd 3 27/02/2017 10:56

 lyst activity or catalyst to oil (cat/
oil) ratio. The global trend shows
Global
that refiners have lowered the ROT
North America
in recent years; however conversion
Europe, Middle East, Africa
3500 Asia
has remained relatively steady, or
Latin America even increased. This suggests that
3000 the activity of the catalyst is stead-
2500 ily increasing as well as the cat/oil
Nickel, ppm

ratio. Another reason refiners might

2000
reduce ROT is to avoid downstream
1500 constraints, such as wet gas com-
pressor limitations.
1000
Another important trend is the
500 cat/oil ratio. The cat/oil ratio shown
0 in Figure 7 exhibits an increase in
2002 2004 2006 2008 2010 2012 2014 2016 recent years. This increase takes
place due to a significant global
3000
drop in regenerator temperature
2500 of 73°F (23°C) from 2009 to 2012,
Vanadium, ppm

2000 while the feed rate and feed preheat

1500
1000
500
0 in cat/oil ratio also coincides with
2002
Figure 8 Ecat benchmarking data for nickel (top) and vanadium (bottom)
cessing of tight oils, which require
higher activity for heat balance pur-
poses. On the contrary, Asia has the
lowest TSA and REO, thus the low-
est Ecat activity.
Operating data can also give a
good indication of how refiners
are responding to market drivers.
0.35
0.30
Phosphorus, wt%
temperature have remained fairly
constant. As Figure 6 shows, even
with ROT decreasing, conversion
remained the same, resulting from
the increase in cat/oil. This increase
2004 2006 2008 2010 2012 2014 2016
the drop in catalyst activity after the
REO crisis began in 2010.
Ni and V content on Ecat are
shown in Figure 8. There has been
Refiners can change the riser out- a steady increase globally in both.
let temperature (ROT) to achieve This is indicative of the economic
a change in conversion. A lower drivers that have been present over
ROT leads to lower conversion, all the past 15 years; heavier and more
else being equal. If a refiner wants difficult to process crudes repre-
to maintain the same conversion sent an opportunity for refineries
while lowering ROT (see Figure 6), that can process them. Refineries
there is more dependence on cata- planning to process heavier crudes
face an implication of increased
hydrogen and coke yields. Asia
Global processes very heavy feed, result-
North America ing in higher metals contamina-
Europe, Middle East, Africa tion. While the global average is
Asia increasing, North America is steady
Latin America or decreasing compared to the rest
of the world. This can be a result
of hydrotreating feeds or process-
ing tight oils, another opportunity

0.25
crude available to oil refiners. Both
0.20 hydrotreated and tight oil feeds
have less metals compared to resid
0.15 feed. Due to higher metal contam-
ination trends globally, catalyst
0.10 manufacturers are developing new
concepts for enhanced metals pas-
0.05 sivation to combat these issues. To
handle higher feed contaminants,
0
2002 2004 2006 2008 2010 2012 2014 2016 coke selectivity and metals passi-
vation technologies are essential
for increased flexibility for a refin-
Figure 9 Ecat benchmarking data for phosphorus (P) ery. For example, BASF has cre-

40 Catalysis 2017 www.eptq.com

basf.indd 4 27/02/2017 10:56

 ated a new technology to passivate
Ni called Boron Based Technology. Global
This technology uses the chemistry 0.5 North America
of boron to passivate Ni, leading to Europe, Middle East, Africa
less coke and dry gas.5 Asia
Figure 9 demonstrates an increase 0.4
Latin America

Hydrogen, wt%
in the phosphorus (P) content in
Ecat since 2009, with a 40% increase 0.3
between 2009 and 2013. This is
indicative of higher ZSM-5 usage, 0.2
with a negligible amount of higher
P content from the fresh catalyst.
ZSM-5 cracks low octane gaso- 0.1
line into LPG. Driving this is the
increased demand for propylene/ 0
petrochemicals over the last 15 2002 2004 2006 2008 2010 2012 2014 2016
years, leading to an economic incen- 4
tive for higher C3 and C4 olefins. In
Asia, for example, it is not uncom-
3
mon for refineries to run over 20%
ZSM-5.
H2/C1

The Ecat P trend suggests that 2

demand for propylene and buty-
lene from FCCs will remain high.
For this, catalyst technology must
be tuned for improved control of
hydride transfer while maintaining
activity. Furthermore, improved
or tailored additive solutions will
become more commonplace to meet
this industry need.
Equilibrium catalyst ACE testing
The data shown in this section were
obtained from ACE testing, which is
run at constant operating conditions
with a constant feed. Therefore, any
changes in the data are a result of
Ecat activity and selectivity. This
method allows for a direct look at
the catalyst selectivities outside of
any operational changes affecting
the unit.
Over the last two years, hydro-
gen (see Figure 10) has increased
globally due to increased metals
contamination, specifically Ni. Ni
is a well-known dehydrogenation
catalyst, leading to an increase
in hydrogen production. As we
have seen, Asia has the highest
Ni content, with the hydrogen
1
0
2002 2004 2006 2008 2010 2012 2014 2016
Figure 10 Ecat benchmarking for hydrogen (top) and hydrogen selectivity (bottom)
Asia (see Figure 11). The trend in REO content and increasing ZSM-5
Asia can be attributed to two fac- usage globally. The C4 olefins (C4=)
tors: higher ZSM-5 usage and lower trend follows the same suit. Figure
REO content in Ecat, both of which 12 (bottom) shows a jump in C4 ole-
are in response to strong LPG pric- fins starting in 2008. The economic
ing in the region. driver is the valuable feed to alkyla-
An economic incentive for higher tion units, to produce a high octane
olefins leads to a steady increase gasoline blend component. Higher
in propylene (C3=) over the past C4 selectivity also indicates higher
15 years (see Figure 12 top). This gasoline octane potential from the
increase was accomplished by catalyst.
implementing various catalyst The operating data follow the
changes, including lowering the same trends as the Ecat data. An
Global
North America
23
Europe, Middle East, Africa
Asia
21 Latin America
LPG, wt%

trend following suit. Prior to these

last couple of years when metals 19
increased, hydrogen selectivity was
decreasing. This suggests that refin- 17
ers are turning to more resid cat-
alyst technologies such as Borocat
15
and Flex-Tec. 2002 2004 2006 2008 2010 2012 2014 2016
Globally, liquefied petroleum gas
(LPG) has increased, especially in Figure 11 Ecat benchmarking data for LPG

www.eptq.com Catalysis 2017 41

basf.indd 5 27/02/2017 10:56

 increase in both total LPG and LPG
7.0 olefins in recent years is evident in
the data (see Figure 13). This trend
6.5 is in line with strong butylene and
Propylene, wt%
propylene demand globally.
6.0 All regions saw a drop in gas-
oline and gasoline selectivity (see
5.5
Figure 14). Europe, Middle East and
Global Africa has one of the lowest gaso-
5.0 North America
line yields globally, resulting from
Europe, Middle East, Africa
Europe’s economic drivers towards
4.5 Asia
diesel. Also, Asia is a more LPG
Latin America
4.0 driven market, further lowering the
2002 2004 2006 2008 2010 2012 2014 2016 gasoline selectivity. Finally, North
America, being a more gasoline
7.5
Total C4 olefins, wt%

driven market, shows higher gas-

7.0 oline and gasoline selectivity than
the global average.
6.5

6.0
Continual monitoring
5.5
of key Ecat parameters
2002 2004 2006 2008 2010 2012 2014 2016
allows refiners to
troubleshoot
Figure 12 Ecat benchmarking data for C3 olefins (top) and total C4 olefins (bottom)
their FCC units
32 appropriately
30 Light cycle oil (LCO) trends are
shown in Figure 15. The trend here
is less clear, potentially suggesting
28 that the demands for LCO have
Total LPG, vol%

shifted over the years. Before the

26 recession in 2008, LCO demand
was high, but since, LCO yields
24
have decreased. Asia’s LCO trend
is in line with the lowest level of
gasoline production. To determine
22 Gasoil
whether or not the LCO yield trend
Resid
Average
is purely an activity effect, the
20 LCO/bottoms (BOT) ratio is shown.
2002 2007 2012 The LCO trend recently is the oppo-
20 site of the LCO/BOT trend, which
is steady/slightly increasing, indi-
cating that this is an activity effect
19
LPG olefins, vol%

of the catalyst. Examining operat-

ing data suggests a similar trend
18 (see Figure 16, bottom). LCO yields
are slowly decreasing, yet bottoms
17 yield is declining rapidly. This indi-
cates two changes: a) an improve-
ment in bottoms cracking ability of
16 the FCC catalyst employed; and b) a
catalyst activity effect.
15 Finally, operating data trends can
2002 2004 2006 2008 2010 2012 2014 2016 be examined for gasoline RON (see
Figure 16). The trend indicates that
Figure 13 Operating data benchmarking LPG (top) and LPG olefins (bottom) FCC gasoline has been produced

42 Catalysis 2017 www.eptq.com

basf.indd 6 01/03/2017 11:55

 with lower octane than in the past,
on average almost a whole number 50
drop in RON. RON can be increased
by undercutting gasoline, higher

Gasoline yield, wt%

ROT or ZSM-5 additions, or lower- 48
ing REO on zeolite. The decrease in
RON is in line with lower ROT (see
above) despite higher ZSM-5 usage. 46
Juxtaposing this with the trend for
higher butylenes, this is indicative
44
of a refinery trend of exploring
alternative options for high octane
blending components. Refineries
42
are depending more on butylenes 2002 2004 2006 2008 2010 2012 2014 2016
to feed their alkylation units to
0.70 Global
produce high octane blending com-
North America
ponents and are willing to let gaso-
Gasoline selectivity, wt/wt Europe, Middle East, Africa
line RON off the FCC decline. The 0.68
Asia
trends together, and the knowledge Latin America
of alkylation unit growth in the US, 0.66
indicate this is a long term trend.

Conclusions 0.64
Continual monitoring of key Ecat
parameters, including surface area, 0.62
metals content, and activity, allows
refiners to troubleshoot their FCC
0.60
units appropriately. When aggre- 2002 2004 2006 2008 2010 2012 2014 2016
gated, these data tell a deeper story.
61
Ecat trends are indicative of histor-
Gasoline benchmarking, vol%

ical market drivers and industry 60

needs. First, REO content in the
catalyst responded quickly to the
REO crisis in 2010, with the levels
not rebounding since the recession
subsided. In response, surface area
increased to make up for activity.
Phosphorus has steadily increased,
indicating higher ZSM-5 usage,
especially in Asia, where market
incentives for light olefins are very
strong. The higher ZSM-5 usage
and REO not increasing back up
to historical levels indicate that
very strong incentives are pres-
ent for light olefins and are likely
to remain. Historical trends can
help elucidate the future of FCC
– the need for light olefins will
be a driver for catalyst and addi-
tive technology. When juxtaposed
against operating data, the data
suggest that the drivers for light
olefins will remain in the future.
More refiners are processing
resid feeds, leading to an increase
in metal contaminants on Ecat and
an increase in hydrogen produc-
tion. In response, catalyst suppliers
innovate to provide new catalyst
technologies that can better com-
59
58
57
56
55
54
53
52
51
2002
Figure 14 Ecat benchmarking data for gasoline yield and selectivity (top) and operating
benchmarking data gasoline yield (bottom)
bat metal contamination. Although
there is an increase in metal con-
tamination globally, the trend in
North America is flat or declining.
The decline is attributable to the
processing of lighter feeds such
as tight oil and the usage of feed
hydrotreaters. Globally, the ROT
steadily decreased over the past
decade, resulting in lower gasoline
RON. Due to a significant drop in
regenerator temperatures (perhaps
due to improved catalyst technol-
ogy and hardware), catalyst cir-
Gasoil
Resid.
Average
2004 2006 2008 2010 2012 2014 2016
culation increased over the past
few years and, despite lower ROT,
conversion remains fairly constant.
Lower bottoms yields have been
visible despite increased resid pro-
cessing, indicating implementation
of both bottoms cracking technolo-
gies and techniques. The historical
trends regarding metals contami-
nation also paint a picture for the
future – opportunity crudes will
continue to be processed. Novel
concepts for enhanced metals pas-
sivation will be a driver for future

www.eptq.com Catalysis 2017 43

basf.indd 7 27/02/2017 10:57

Process Notes
On Budget, On Time, Offline
Flawless project execution will not prevent a unit shut-
down due to selecting the wrong metallurgy for a chal-
lenging crude slate.
No matter how well it is fabricated and installed, a shell
and tube exchanger with cold, high viscosity vacuum
resid on the tube side will have poor heat transfer per-
formance.
On-time shipping and installation of a too-small de-
salter will not prevent crude column overhead corro-
sion if the centerline velocity is overly optimistic for the
design crude.
A high labor efficiency factor for installation of tower
internals will not increase vacuum resid cut point, but
properly designed stripping trays will.
Managing major projects such as grassroots crude,
coker, and FCC unit construction is hard work. Large
revamps are even harder. In projects costing tens of
millions to billions of dollars, detailed engineering and
construction are monumental tasks that consume
most of the overall project budget and schedule. As a
project advances from a design on paper to steel on the
ground, success requires relentless focus on meeting
cost and schedule expectations, leading project man-
3400 Bissonnet St.
Suite 130
Houston, TX 77005, USA
Projects must ultimately meet process goals.
agement to seem an end in itself. However, the suc-
cess of a project rests upon the foundation that is built
during conceptual design and front-end engineering.
With surprising regularity, a unit’s failure to meet per-
formance expectations does not stem from the de-
tailed engineering and construction phases or faulty
equipment manufacturing. Instead, project failure is
often the result of poor front-end flow scheme design
and initial process equipment specification.
A well-defined, early phase activity that consumes
only a few percent of the overall project budget may
seem trivial. In reality, solid front-end flow scheme de-
velopment and equipment design are prerequisites for
successful project execution. Rework and late stage
process modifications usually reside at the top of the
list of post-audit culprits in late and over budget proj-
ects.
Unit startup can quickly re-designate a project from
shining success to haunting failure. Selecting a part-
ner with an extensive experience list and a specialized
understanding of the unit at hand can ensure startup
goals are met while minimally impacting the overall
project budget.
+1 (713) 665-7046
info@revamps.com
www.revamps.com
 catalyst technology. Coke selectivity
Global
will be necessitated by this increase A
19 North America
in metal contaminants globally in Europe, Middle East, Africa
order to provide the necessary flexi- Asia
bility to refiners. 18 Latin America
Transportation fuels remain the

LCO, wt%
heart of the FCC unit’s product
17
yield slate. Low value bottoms
products continue to decrease while
catalyst activity stays constant, 16
indicating the implementation of
improved bottoms cracking tech-
15
nologies across the regions versus 2002 2004 2006 2008 2010 2012 2014 2016
using higher activity to crack bot- B
1.8
toms. New rules around marine
bunker fuel specification will fur-
1.6

LCO/BOT, wt/wt
ther drive lower bottoms produc-
tion. Refiners will continue to seek
1.4
out transportation fuel maximis-
ing technologies while pushing for
more light olefins yields. The shifts 1.2
2002 2007 2012
in FCC yields in the last decade and
C
a half are indicative of an industry 20
that is pushing itself to get more 19
out of each and every barrel of oil
18
LCO, vol%

that is processed. These changes are

driven in part by the implementa- 17

tion of novel FCC catalyst technol- 16

ogies that enable higher profitability 15
in the refinery complex.
14
Borocat and Flex-Tec are trademarks of BASF 2002 2007 2012
Catalysts. D Gasoil
10
Resid
References Average
1 Kayser J C, Versatile fluidized bed reactor, US 9
Pat. 6,069,012, 1998.
2 Vogt E T C, Weckhuysen B M, Fluid catalytic
BOT, vol%

8
cracking: recent developments on the grand
old lady of zeolite catalysis, Chem. Soc. Rev.,
7
44, 2015, 7342-7370.
3 Komvokis V, Tan L X L, Clough M, Pan S,
Yilmaz B, Ch 8: Zeolite in Fluid Catalytic 6
Cracking (FCC) in Zeolites in sustainable
Chemistry, Springer, 2015, 271-298. 5
4 Gschneidner K A Jr, The rare earth crisis – 2002 2007 2012
the supply/demand situation for 2010-2015,
Material Matters, 6, 2011, 32-41.
Figure 15 Ecat benchmarking data for LCO and LCO/BOT (top) and operating data
Jacqueline Pope is a Product Manager in benchmarking for LCO and bottoms (bottom)
BASF’s Chemical Intermediates division. She
holds a PhD in chemistry from Texas A&M
University and a BS in biochemistry from St. 93.5
Gasoil
Edward’s University.
93.0 Resid
Melissa Clough is a technology specialist with
Average
Gasoline RON

BASF’s refining catalyst business. She holds a

92.5
PhD in chemistry from Texas A&M Univ, a BS in
chemistry from the University of Florida, and
92.0
an MBA from the University of N. Carolina.
Alexis Shackleford is the Technical Marketing 91.5
Specialist for BASF. She is involved in FCC
catalyst publications, presentations, and 91.0
new product introduction. She holds a BS in 2002 2004 2006 2008 2010 2012 2014 2016
chemical engineering from Michigan State
University. Figure 16 Operating data benchmarking for gasoline RON

www.eptq.com Catalysis 2017 45

basf.indd 8 27/02/2017 10:57

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
 Designing and engineering catalysts for
hydrotreating
Advanced analytical and experimental techniques combine in the development
of a new hydrotreating catalyst

KARL KRUEGER, MAX OVCHINNIKOV and THOMAS WEBER

Criterion Catalysts & Technologies

T
here are few areas of research
that are more mature than
hydroprocessing catalyst
development. This has been an area
of active research for over seven
decades, involving academic, busi-
ness and government institutions,
with thousands of patents granted
and many major breakthroughs in
activity and stability along the way.
The reason for this persistent inter-
est is driven by the enormous value
that a better catalyst solution can
offer. As an example, an improved
hydrocracker pretreat catalyst with
higher aromatic saturation (HDA)
and hydrodenitrogenation (HDN)
activity will produce millions of
dollars in extra revenue over the
course of a commercial run. The
benefit of higher activity catalysts
is not unique to first stage hydroc-
racking. Indeed, similar opportuni-
ties exist across the whole spectrum
of hydrotreaters in a refinery com-
plex, making the case for advanced
catalyst technology clear.
Oil refiners worldwide are being
challenged to provide clean trans-
portation fuels in order to meet
stricter environmental regulations
while moving to more difficult
crudes. In particular, removal of
sulphur in diesel fuels to ultra low
levels continues to be implemented
throughout the world following an
early adoption of ultra low sulphur
diesel (ULSD) standards in Europe,
Japan, and the US in the early
2000s. The implementation of Tier
3 gasoline sulphur regulations in
the US, starting in 2017, has refin-
ers focused on changes in both pre-
treat and post-treat catalyst systems.
Finally, the new lower marine fuels
specifications dropping to 0.5% sul-
units in combination with sophis-
In the past...
ticated hydrotreating and hydroc-
racking will be further ahead, with
Design catalyst all refiners looking for hydropro-
formulations cessing catalyst solutions to handle
heavier and more difficult feeds as
2020 approaches.
The task of developing these
advanced catalyst technologies
Test catalyst falls to catalyst suppliers and there
formulations are various strategies that can be
employed to accomplish this task.
Criterion Catalysts & Technologies
(Criterion) has over 29 years of cat-
alyst research and development,
Analyse results
applying customised catalyst sys-
Draw conclusions
tems and operating strategies to
improve days on stream, generate
higher yields and facilitate the pro-
cessing of more challenging feeds.
Figure 1 Traditional linear workflow of The traditional workflow that
catalyst development has been utilised in the industry
for decades is best characterised as
phur in 2020 represents yet another highly linear (see Figure 1). It entails
upcoming challenge. Refiners that a sequential movement through the
are investing in residue conversion design of catalyst formulations, the
Current method...
Figure 2 Parallel workflows of advanced development techniques

www.eptq.com Catalysis 2017 47

cat criterion.indd 1 01/03/2017 11:07


Figure 3 Density functional theory
calculations optimise aluminium and
oxygen distribution on γ alumina surfaces
testing of those formulations, the
analysis of those test results, and the
application of those learnings to the
next batch of catalyst formulations.
The linear nature of this process
misses opportunities for parallel
work which ultimately slows inno-
vation and invention. This tradi-
tional workflow is also one that is
filled with barriers. Barriers such as
limited testing capability, poor data
management tools, and classical
methods of catalyst characterisation
are major roadblocks to discovery.
Over the past 10 years, Criterion
has moved away from this old fash-
ioned process to one that embraces
parallel workflows and one that
destroys barriers. In this new work-
flow, ideation, screening, and anal-
ysis all take place simultaneously,
resulting in a more efficient work-
flow where no process is beholden
to another. This parallel workflow is
enabled by several key technologies:
computational modelling, advanced
characterisation, high throughput
experimentation, and advanced
data analytics (see Figure 2). In the
past decade, these techniques have
proven their ability to produce step-
out innovations compared to other
methodologies. For this reason, they
are widely employed in industries
such as pharmaceuticals, electron-
48 Catalysis 2017
cat criterion.indd 2
ics, and aerospace where innova-
tion is the driver of success. When
applied together, these technologies
affect a paradigm shift in the R&D
pipeline where innovation becomes
easier and scientists can focus on
new technology development.
Computational modelling is
where it all starts. It is hardly pos-
sible to engineer technology plat-
forms exceeding today’s activity by
trial and error methodologies alone.
New synthetic strategies must be
based on a precise understanding of
which structural aspects of the com-
plex catalyst system should be opti-
mised. This starts with the carrier
by adjusting it to the right surface
area and pore size distribution, both
of which influence surface prop-
erties that enable the formation of
highly active Type II catalysts.
Among the surface properties that
are crucial in generating Type II
particles is the right distribution of
aluminium and oxygen at the car-
rier surface. In order to fundamen-
tally understand this property, its Figure 4 Scanning transmission electron
influence in the active phase gen- microscopy shows the positions of
eration, as well as how to engineer molybdenum atoms in a NiMo catalyst
this surface, Criterion is increas-
ingly performing quantum chemical physical feature for all hydropro-
calculations in a high performance cessing catalysts is the catalytically
computing facility. These ab initio active MoS2 edge responsible for
or ‘first principles’ methods allow sulphur, nitrogen, and aromat-
calculation of structural proper- ics removal. Achieving the right
ties, simulation of their functioning active site architecture is crucial for
during catalyst preparation, and high performance so we have put
elucidation of their catalytic action. a major effort towards the chal-
Figure 3 shows the results of den- lenging task of characterising this
sity functional theory (DFT) calcu- feature in alumina supported, non-
lations, targeted at optimising the model catalyst systems operating on
aluminium and oxygen distribution real feedstocks.
on two prominent surfaces of γ alu- Aberration corrected scanning
mina (111 and 100 surfaces). This transmission electron microscopy
structural setting enables a balanced (STEM) has been applied to reveal
deposition of metal components the exact position of individual
during catalyst synthesis, ensuring molybdenum atoms in real cata-
formation of particles with the right lysts. Figure 4 shows data from a
morphology and structure. commercial NiMo Centera catalyst
Another technology that goes pulled from ULSD service on a
hand in hand with computational straight-run gas oil. The top image
modelling is advanced catalyst shows the edge region of a particle
characterisation. By applying the in top view (white arrow) where
most cutting edge surface science the catalytic reaction takes place;
techniques, we are able to gain every yellow spot represents one
new insights into the structure and metal atom. The structure of the
function of catalysts. This insight is metal atoms in the particle is largely
fundamental in driving the devel- determined by the regular arrange-
opment of the next generation of ment of the bulk MoS2 structure
catalyst platforms. One critical shown in the inset. In this perfect
www.eptq.com
01/03/2017 11:08
 regularity, however, catalytic activ-
ity would be relatively low; alter-
ation is required to switch active
sites on. The image shows this
clearly – distortions engineered into
the arrangement of metal atoms
close to the edge enable the high
performance of Centera catalysts.
An edge-on view of the MoS2 slab
can be seen in the bottom image
(white arrow); again, each spot rep-
resents a metal atom in the edge.
This concept of engineering the
active edge sites has the advantage
that activity remains high regard-
less of the particle size. We are
thus able to move away from the
traditional credo in catalysis which
requires generation of very small
particles for high activity. Through
this we were able to accommodate
structural functions for both direct
desulphurisation and hydrogena-
tion into one larger particle.
Equally important to idea gener-
ation is catalyst screening. Perhaps
the most important improvement in
catalyst testing has been the utilisa-
tion of high throughput experimen-
High throughput funnel
High throughput
catalyst preparation
(tens of thousands)
Primary screening
(Thousands)
Secondary
screening
(Hundreds)
Scale up
(One)
Figure 5 The high throughput funnel
tation. This technique, with roots
in combinatorial chemistry, utilises
miniaturisation, robotics, and auto-
mation to activity test a huge num-
ber of catalyst formulations in a
short period of time. Historically,
catalysts were tested in micro-flow
units that contained only one cata-
lyst. Operation of these units was
largely manual, requiring signifi-
cant human intervention for most
tasks. This was improved somewhat
with the invention of multi-barrel
units that combined two to four
reactor tubes in a common heating
bath. While some process parame-
ters such as temperature and treat
gas rate were computer controlled,
these systems were only minimally
programmable. These old systems
have now been completely sur-
passed by high throughput exper-
imentation. These units typically
test a minimum of 16 reactors at a
time utilising one-hudredth the vol-
ume of catalyst used traditionally.
These systems are fully automatic
and utilise robotics for tasks such
as product collection. They are also
infinitely programmable and can
run unmanned for days at a time.
The result is a laboratory that tests
catalysts five times faster than pre-
viously possible with the same man-
power requirements.
Criterion’s high throughput work-
flow is a funnel that is used to rap-
idly sieve through approaches and
arrive at a prototype formulation
(see Figure 5). This workflow is the
key to rapidly screening a large

Reforming
Hydrotreating
ULSD
FCC Pretreat
Hydrocracking
Isomerization
Dewaxing

SELECT THE BEST CATALYST

Refinery Catalyst DISCRIMINATIVE YOUR FEED COST-EFFECTIVE

Testing POWER YOUR CONDITIONS COMPARISON
Take advantage of Parallel testing enables We test catalyst Independent
our technology to data replication - systems with real comparative testing
accurately select the best Accurately evaluate feed stocks and enables the unbiased
catalyst and help boost catalyst vendor options relevant process performance
your refinery margins and compare against conditions and evaluation of
the incumbent catalyst production strategy commercial catalysts

www.avantium.com/rct

www.eptq.com Catalysis 2017 49

cat criterion.indd 3 01/03/2017 11:08


Centinel Gold
ULSD DC-2318
DN-3330
FCCPT DN-3310
HCPT DN-3300
Figure 6 Catalyst developments leading to Centera GT
number of ideas and quickly com-
mercialising products with step-out
performance. Catalyst preparation
and various stages of testing all
play a role in this process. Custom
designed robots handle the task of
synthesising thousands of different
formulations. The choreographed
motions of these individual
machines complete all the stages
of catalyst preparation from metals
impregnation to calcination with
no human intervention. Requests
for catalysts are submitted in the
afternoon and finished catalysts are
waiting in the morning. This enor-
mous catalyst preparation capacity
allows any and all routes of inves-
tigation to be explored. To increase
the speed at which promising
approaches are identified, a rapid
primary screening test is employed.
US
Gulf Coast
feed
DC-2635
DC-2638
130
Relative volumetric
alyst development process, includ-
Centera Centera GT ing catalyst preparation, physical
property measurement, and activ-
ity testing. Through this design,
DC-2618/2635 DC-2638 the database houses in a structured
form every piece of data known
DN-3630/3636 DN-3638
about every sample ever prepared.
These data are then processed in
DN-3651 DN-3655
the background to identify statis-
DN-3620/3621 DN-3622
tically significant descriptors for
catalyst activity. This system goes
far beyond the traditional design of
experiments that must be carefully
set up and executed to gain useful
This fast test provides a first look at results. Instead, it allows statistical
activity and can be used to quickly models to be built on the fly using
narrow the field of study to only the entirety of information collected
the most promising areas. More in the database. This data science
detailed secondary screening is then approach to examining results has
employed to tease out the finer syn- greatly improved the speed of data
thetic details and maximise catalyst analysis as well as the accuracy of
activity, leading to a final prototype conclusions drawn.
formulation. This highly efficient The Centera catalyst technology
workflow has allowed Criterion platform was originally launched in
scientists to make decisions faster 2009, and it showcased innovations
and explore entire areas of research developed for Criterion’s Ascent
that would normally be neglected, and Centinel Gold catalyst technol-
meaning that now almost no stone ogies. The advances in the catalyst
remains unturned. support implemented in the Ascent
High throughput experimentation catalysts have been successfully
creates such a wealth of data that merged with the advancements in
it is essentially a requirement to Type II active phases implemented
pair it with advanced data analyt- in Centinel Gold technology to pro-
ics. Embracing ‘big data’, Criterion vide the foundation for the Centera
has built a custom database and platform. Further advances in the
front-end that houses the entire cat- manufacture of Centera catalysts
have resulted in activity enhance-
ments that were attributed to the
Middle East US Canadian better dispersion of MoS2 crystal-
feed West Coast synthetic lites in the active catalyst, realised
feed feed through improved support technol-
ogy, enhanced decoration of edges
DN-3636 DN-3621 DN-3651 of MoS2 particles with promoter
DN-3638 DN-3622 DN-3655 metals leading to increased catalytic
activity, and maximised degree of

120 sulphidation resulting in forma-

tion of ideal Type II active sites.
activity

110
These catalysts have been applied
100 in hydrotreating units across the
90 world for ULSD, hydrocracker and
FCC pretreat services.
80
HDS HDS HDN HDS HDN HDS The accelerated development of
Conditions 1.0 LHSV
Criterion’s newest catalyst tech-
1.15 LHSV 1.5 LHSV 0.75 LHSV
600 psig 870 psig 1300 psig 1400 psig nology, Centera GT, was a direct
1200 scf/bbl 2000 scf/bbl 3400 scf/bbl 3500 scf/bbl
result of investing in computational
Feed properties Sulphur 1.73 wt% Sulphur 1.24 wt% Sulphur 0.69 wt% Sulphur 3.67 wt% modelling capabilities, deploying
Nitrogen 249 ppm Nitrogen 242 ppm Nitrogen 1750 ppm Nitrogen 3020 ppm
34.3º API 31.8º API 19.2º API 13.2º API massively parallel high throughput
T95% 676ºF T95% 764ºF T95% 704ºF T95% 1075ºF
catalyst testing, and leveraging state
of the art catalyst characterisation
Figure 7 Comparison of relative volumetric activities: Centera and Centera GT catalyst methods and data analytics tools.
families Launching in 2017, Centera GT

50 Catalysis 2017 www.eptq.com

cat criterion.indd 4 01/03/2017 11:08

 builds upon the fundamentals of
the original Centera platform while
incorporating enhancements to the
catalyst carrier as well as the struc-
ture of the active metal sites.
Atomically specific modifications
to the alumina carrier have resulted
in the creation of novel nanoscale
surface features as well as a more
desirable set of bulk chemical and
physical properties. The modified
catalyst carrier enabled Criterion
scientists to engineer and construct
highly dispersed MoS2 particles
with step-out intrinsic activity for
HDS, HDN, and HDA. The effect
was so pronounced that it provided
the highest active metal utilisation
observed for alumina supported
catalysts or unsupported bulk metal
oxide formulations. Advanced
catalyst characterisation meth-
ods including aberration corrected
STEM were key to the development
of Centera GT.
An extensive pilot plant evalua-
tion of new catalyst technology was
carried out to assess fully the appli-
cability of this catalyst technology
across hydrotreating applications,
REFCOMM
Coking, Cat Cracking, Sulfur Recovery, and Instrumentation & Electrical
REFININGCOMMUNITY.COM
www.eptq.com
cat criterion.indd 5
quantifying the expected activity
and stability benefits. The result
is the introduction of a new cata-
lyst family, Centera GT for ULSD,
hydrocracker and FCC pretreat ser-
vices (see Figure 6).
Figure 7 shows HDS activity data
for two catalysts, DC-2638 and
DN-3638, tested in ULSD applica-
tion at 40 bar and 60 bar respec-
tively. Both Centera GT catalysts
exhibited >10ºF improvement in
HDS activity compared to their
Centera predecessors.
Conclusion
Applied together, computational
modelling, advanced characterisa-
tion, high throughput experimen-
tation and advanced data analytics
form a powerful combination for
developing advanced catalyst tech-
nologies. The playground has
changed from one where work
progresses slowly in many sepa-
rate silos into one where routine
tasks are completed automatically
and data flows seamlessly across
a global team. This has led to
many discoveries towards the lat-
GALVESTON
MAY 8-12, 2017
est generation of high performance
catalysts.
CENTINEL GOLD, CENTERA and CENTERA GT
catalysts are marks of Criterion Catalysts and
Technologies.
Karl Krueger is a Senior Research Chemist with
Criterion Catalysts and Technologies. He works
on the development of new hydrotreating
catalyst technologies and is the team lead for
distillate and tail gas catalyst development. He
holds a PhD in chemistry with a specialisation
in nanotechnology from Rice University and a
bachelor of science degree in chemistry and
mathematics from Texas Lutheran University.
Max Ovchinnikov is a Senior Research Chemist
with Criterion Catalysts and Technologies
based in Houston TX. He is primarily engaged
in research and development of heterogeneous
catalysts for hydroprocessing applications. He
holds a PhD in organic chemistry from Iowa
State University.
Thomas Weber is a Principal Scientist
performing catalyst development for
Shell P&T at the Shell Technology Centre
Amsterdam and holds the chair in Solid State
Inorganic Chemistry at Eindhoven University
of Technology, The Netherlands. He is leading
the global innovation programme at Criterion
Catalysts and is contributing to catalyst
development in several areas, among them
distillate applications.
- TRAINING
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- EXHIBITION
BUDAPEST
OCT 2-5, 2017
Catalysis 2017 51
01/03/2017 11:09
 Let’s do
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grace.indd 1 24/02/2017 12:53

 Catalysts for higher middle
distillate yields
The appropriate hydroprocessing catalyst system can deliver higher yields of
middle distillates at minimal cost
ALEX YOON Chevron Technology Marketing and Advanced Refining Technologies
MEREDITH LANSDOWN Chevron
BRIAN WATKINS Advanced Refining Technologies
W
ith the continued interest
in processing domestic
crude sources, as well as
utilising opportunity feed sources,
refiners in the US have been explor-
ing ways to maximise their mid-
dle distillate production. Several
domestic feed sources have reduced
demand on the ULSD hydrotreater,
making it significantly easier to
treat ULSD; however, other feed
sources, with the low cost of crude,
have begun to be an issue that was
not previously considered. A crit-
ical element in all the approaches
to increasing diesel yield is the
proper design and selection of a
catalyst system for the hydropro-
cessing unit. Improvements in
catalytic solutions have made sig-
nificant advances in allowing the
hydrotreater or hydrocracker to
increase middle distillate yield.
This approach to increasing diesel
yields requires a detailed under-
standing of feed and operating con-
ditions such that the hydrotreater
or hydrocracker can be operated
at optimum conditions for the unit
cycle, and all of these have lim-
its depending on the various feed
properties. Challenges in terms of
hydrogen consumption, yield shifts,
changes in cycle life, and the chem-
istry involved will be discussed in
order to provide some guidance
and understanding, to maintain
product quality with existing assets
and minimal investment. This arti-
cle summarises the requirements
to understand the various cata-
lytic options and unit operation, to
demonstrate that higher yields of
middle distillate can be achieved
with existing assets and minimal
investment.
www.eptq.com
q2 clg.indd 1
Hydroprocessing at
Chevron/ART/CLG
The optimisation of new hydropro-
cessing catalysts plays a critical role
in achieving optimum performance
in refinery hydroprocessing units,
especially after the unit has been
in operation. Hence, Chevron as
a refinery operator has paid close
attention to hydroprocessing cata-
lyst developments over the years
both as a catalyst designer and a
catalyst manufacturer. Since the
year 2000, with the launch of the
joint venture Advanced Refining
Technologies Ltd. (ART) with Grace,
this focus has increased even more.
The catalyst focus has roots
in the 1960s when Standard Oil
of California (as Chevron was
called then) first developed mod-
ern hydrocracking and installed a
demonstration unit. Standard Oil
of California then went on to build
many hydrocrackers at its own
refineries and for other Standard
Oil companies, some of which later
became parts of Exxon, Mobil and
BP. At that time, Chevron designed
and manufactured hydrocracking
catalysts, or more widely consid-
ered hydroprocessing catalysts since
these were designed to perform
both hydrotreating and hydroc-
racking. The catalyst manufactur-
ing technology was unique in that
a liquid solution of components
was gelled in order to make the
catalysts, hence the name cogel.1
Dual function catalysts have been
the cornerstone of Chevron tech-
nology and continue to be utilised
in the company’s refinery hydroc-
rackers as well as around the world
in licensed hydrocrackers from the
Chevron joint venture with CBI
Lummus, called Chevron Lummus
Global (CLG), and supplied with
catalysts from ART.
Various technology providers
have designed hydrocrackers with a
separate hydrotreating reactor and
hydrocracking reactor. However,
CLG designed hydrocrackers and
Chevron refinery hydrocrackers
do not have such distinction and
require that both hydrotreating and
hydrocracking take place inside a
single reactor. Even ART’s highly
zeolitic catalysts are employed in
this manner. This is especially the
case with Chevron refinery units
that have been revamped over the
years. In various severe services, a
conventional alumina based hydro-
treating catalyst alone is not robust
enough to meet the dual objectives
required. In fact, both hydrotreat-
ing and hydrocracking objectives
needed to be met within a limited
catalyst volume where other typical
hydrocrackers are able to employ
conventional alumina based hydro-
treating catalysts.
To meet such severe performance
requirements, Chevron led a joint
research and development effort
to produce its most recent cata-
lyst series, ICR 1000, which builds
on cogellation technology. Typical
alumina based hydroprocessing
catalysts have faced limits on the
amount of metals that can be depos-
ited on the base, which then limits
their performance. Cogellation tech-
nology enabled the development
of the ICR 1000 series of catalysts
to overcome this limitation and
improve catalytic hydroprocessing
capabilities by doubling and some-
times tripling catalyst activity com-
pared to alumina based catalysts,
Catalysis 2017 53
27/02/2017 15:05
 In addition, ICR 1000 was tested
Multiple train Multiple train
first stage second stage in ULSD hydrotreating to deter-
mine whether its hydroprocess-
Separator
ing capabilities could be utilised
Combined train
effluent streams Products in this operation. As the results in
Isocracking Isocracking the second part of the article will
show, the catalysts demonstrated
marked improvements in hydrodes-
ulurisation coupled with significant
aromatics saturation, leading to
Second stage product volume enhancement with-
feed out any detrimental effect on liquid
Sample point
yield. ICR 1000 is in its second cycle
of operation in a commercial ULSD
unit within Chevron. Application
in other types of hydroprocessing
units is being actively explored.
Figure 1 Multi-train, multi-stage Isocracking unit
ICR 1000 application in a commercial
hydrocracker
The refinery and the hydroc-
+200
racker in this case study are both
Chevron’s own. The hydrocracker
Temperature, ºF

Reactor effluent 70% is a relatively complex unit in that

Boiling point (Train B)
there are two stages, which is a
preferred configuration for max-
imum conversion, highest liquid
yield, and lowest catalyst volume
Reactor effluent 50%
Boiling point (Train B) (see Figure 1). A two stage configu-
ration is where there are two reac-
tion zones with separation of light
Base
and heavy molecules in the reactor
effluent stream between tzhe two
Figure 2 Reactor effluent distillation reaction zones. Separation can uti-
lise high pressure equipment or
while at the same time meeting as well as outside, demonstrating low pressure equipment, includ-
dual function objectives. higher conversion and distillate ing the option of a vacuum tower.
The ICR 1000 series catalysts yield improvement. An example of Intermediate separation recovers
have now been deployed in multi- one such successful hydrocracker products and prevents recracking
ple hydrocrackers within Chevron deployment is shared here. of the lighter oil as conversion is

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54 Catalysis 2017 www.eptq.com

q2 clg.indd 2 28/02/2017 12:10

 Total reactor temperature rise
Base HDT HDT

Per bed temperature rise, ºF

Total ∆T (Train B)
HDT HDT

HCR

HCR
HDT

HDT
Bed
Bed X+1 (Train B) No. 1
HDT ~10% of
+30 Bed ICR 1000 reactor
No. X+1

HCR

HCR
HDT

HDT
Bed X (Train B) HDT HDT
HCR HCR
HDT HDT

Train A Train B
Base with ICR 1000
Days on stream Days on stream +365

Figure 3 Reactor temperature profile Figure 4 Catalyst loading diagrams

increased. Second stage reactors for performance comparison as the showcase difficulties faced by refin-
crack only the unconverted oil and, trends indicate product changes as ery unit engineers when extracting Table
in the absence of inhibitors, are well as other process data that are comparative performance.
capable of utilising smaller quanti- available to validate the conclusions. The catalyst loading schemat-
ties of catalysts compared to a sin- Figure 3 shows a reactor tempera- ics for two comparison trains are
gle stage configuration. A single ture profile graph for the same train shown in Figure 4.
stage configuration has one con- B. Again, about 365 days of data The loading on the right is for
tiguous reaction zone without any are shown here. Bed X tempera- train B whose effluent stream and
intermediate product separation. ture rise, which represents per bed temperature data were shown in
In addition to two stages, this reaction amount, is plotted with Figures 3 and 4. This train B was
hydrocracker has multiple trains in red X marks. The temperature rise loaded with ICR 1000 along with
each stage which enables on-stream of downstream bed X+1 is plotted layers of conventional hydrotreating
catalyst change-outs and restart to with blue diamond marks. Again, (HDT) catalysts and hydroprocess-
allow the maximum unit utilisation the absolute numbers are not critical ing (HCR) catalysts. This includes
rate and hence improve the refinery to determine the performance. Train reverse layering where HDT cat-
utilisation rate. The key unit perfor- B containing ICR 1000 performance alysts are loaded below HCR cat-
mance metrics that the deployment will be compared on the same basis alysts in a bed in order to provide
of ICR 1000 improved are conver- with another train. At the top of the correct catalyst type in the opti-
sion and yield. Since there is not Figure 3 in brown circles are total mum location and condition. This
an individual train fractionation, temperature rise for train B with allows the specific catalyst capa-
conversion is measured/estimated ICR 1000, representing total reaction bilities to match up with reaction
using effluent sampling and tem- amount for the train. The scale for requirements in the different zones
perature profile. The yield effect total temperature rise data is differ- of the hydroprocessing reactor. ICR
is measured from the incremental ent and is on the secondary Y axis. 1000 was loaded in bed X+1 in train
change in the combined fractiona- The raw plant data are shared to B and amounted to less than 10%
tion data. Figure 2 shows an effluent
sample distillation monitoring graph
for one train. Approximately 365 +200
Reactor effluent 70%
days of operation are shown. The Boiling point (Train A)

start of operation for this train B, or

Temperature, ºF

zero days on stream (DOS), is actu- Reactor effluent 50% Reactor effluent 70%
ally the Y axis intersect and not the Boiling point (Train A) Boiling point (Train B)
first black mark on the X axis. The
bottom smaller light blue X marks
represent the 50% boiling points of
train B effluent stream sample and Reactor effluent 50%
Boiling point (Train B)
the top larger darker blue marks
represent the 70% boiling points.
As expected of typical refinery data, Base
there is some fluctuation in the abso-
lute numbers. This is not so critical Figure 5 Reactor effluent distillation comparison

www.eptq.com Catalysis 2017 55

q2 clg.indd 3 27/02/2017 15:05

 In single train units, many changes
can happen to the feed as well as

Total reactor
temperature rise
to operational targets between cata-
lyst cycles lasting many years. This
Base makes comparison from one cycle
Total ∆T (Train B)
to another very difficult with a sin-
gle train unit. The unique design of
this multiple train unit and its oper-
ation allow easier comparison and
temperature rise, ºF

Bed X+1 (Train B)

+30 Bed X+1 (Train A) step-by-step introduction of new
Bed X (Train A) technologies.
After the unit lined out, the first
Bed X (Train B)
sign of performance difference
Per bed

showed up in the effluent sampling

data. Figure 5 is on the same basis as
Base Figure 2 with non-ICR 1000 train A
Days on stream Days on stream effluent stream 50% and 70% boiling
Days on stream +365 point data added. The red diamond
marks above the blue X marks for
Figure 6 Reactor temperature profile comparison train B are the data plots for train A.
Comparing the two trains’ effluent
sampling data shows a quantitative
change in the distillation, indicating
Base shifting conversion in the reactor
Total ∆T (Train B)
with ICR 1000 loaded. As meas-
ured by 50% boiling point, the ICR
1000 loaded reactor’s effluent stream
−30
exhibited 10-30°F lower tempera-
temperature rise, ºF

Bed X+1 (Train B)

+30 tures. The 70% boiling points for
Total ∆T (Train A) two trains show smaller differences.
This performance is also validated
Bed X (Train B) by temperature profile monitor-
ing. Figure 6 is on the same basis
Per bed

as Figure 3 with non-ICR 1000 train

Base
A, bed X and bed X+1 temperature
Days on stream Days on stream rises plotted to the right of the ICR
Days on stream +365 1000 containing train B data.
Comparing the temperature pro-
Figure 7 Reactor total temperature rise comparison files, bed X+1 on train B where ICR
1000 is loaded and shown as blue
diamond marks on the left hand
Comparative chart shows a much higher temper-
+200 operation period ature rise, or more reaction amount,
Selectivity, BPD

than the same location in bed X+1

Days on stream
Days on stream +365
Figure 8 Product selectivity improvement
of the total reactor load. All other reactor sequentially and often sev-
trains were loaded with catalysts as eral months apart, performance
shown in the schematic on the left comparison between trains without
without any ICR 1000. normalisation can be made easily,
Since the unit changes out each unlike with other hydrocrackers.
on non-ICR 1000 train A. Train A
bed X+1 exhibits a 10-15°F lower
temperature rise throughout the
similar calendar days of operation.
The total reaction amount for
each train can also be compared
(see Figure 7).
The brown circles at the top of
Figure 7 are the total temperature
rises for ICR 1000 system train B.
The orange squares on the right
chart in Figure 7 are the total tem-
perature rises for train A without
ICR 1000. The differences in total
train temperature rise range from
15-20°F. The amount of extra reac-
tion achieved with ICR 1000 in train

56 Catalysis 2017 www.eptq.com

q2 clg.indd 4 28/02/2017 10:40

 Sabin_One_Stop_PTQ.pdf 1 12/2/15 4:33 PM

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+20
Base
Temperature, ºF
−20
0 5
Figure 9 Performance sulphur curve
B is estimated to be around 20-30%.
Although not shown here, the dif-
ferences between total reaction
amounts in train B with ICR 1000
and train A are larger than the dif-
ferences between reaction amounts
in bed X+1 in the two trains. This
indicates that ICR 1000 affects not
just its bed performance but also
the performance of downstream
catalysts.
Often, added activity, especially
in hydrocrackers, comes at a cost of
reduced liquid selectivity. That was
a concern, and the unit performance
was carefully monitored. This was a
very difficult task since the unit has
multiple stages and multiple trains
with catalyst change-outs at differ-
ent times in each reactor and fre-
quent product slate changes. Crude
slate and feed changes were rela-
tively minor. But, as Figure 8 shows,
the refinery and ART’s technical
+1
Base
∆API
−1
Figure 10 API upgrade performance
58 Catalysis 2017
q2 clg.indd 5
Without ICR 1000
With ICR 1000
10 15 20 25 30 35 40 45 50 55 60
Product sulphur wt ppm
service team identified a compara-
tive operation period, filtering out
extraneous changes, and demon-
strated an almost 1000 b/d increase
in jet product selectivity.
Satisfied with the safety and per-
formance of ICR 1000, the refinery
has loaded a second charge. The
refinery is using the activity advan-
tage in many different ways to
achieve its profit objectives.
ICR 1000 in a ULSD application
ICR 1000 can be considered a hydro-
processing catalyst, combining both
treating and cracking functionality,
rather than a pure hydrotreating cat-
alyst. The old cogellation technology
was used to make hydrocracking
catalysts combining liquid solutions
of alumina and silica and metals
until the mixture gelled. ICR 1000
is produced in a similar manner
at the same plant and hence con-
Without ICR 1000
With ICR 1000
Base +50
Temperature, ºF
Test feedstock
API 28.8
Sulphur, wt% 2.0159
Total aromatics, wt% 23.7
D86 distillation, °F
IBP 281
10 370
30 475
50 538
70 586
90 641
FBP 681
Table 1
tains active sites necessary for both
carbon-carbon bond breaking and
carbon-heteroatom breaking and
removal. Depending on the feed
and processing conditions, the cat-
alyst can exhibit both hydrotreating
and cracking capabilities. In the first
example, enhanced hydrocracking
capability was prominent.
Given its other attributes, ICR
1000 was also successfully tested for
use in a ULSD application, where
meeting the difficult aromatics tar-
get in a severe operation was crit-
ical. It was successfully deployed
in a ULSD unit and is now in its
second cycle of operation. Some of
the data developed for ULSD appli-
cations is presented in this section.
ART studied two catalyst systems,
one with the latest Type II Ni/Mo
only, and the other with same Ni/
Mo catalyst and a layer of ICR 1000.
The test feedstock properties are
shown in Table 1.
Figure 9 shows how the product
sulphur varies with temperatures
applied to the catalyst systems. The
catalyst system with ICR 1000 out-
performed the catalyst system with-
out ICR 1000 by over 15°F under
typical ULSD conditions and by up
to 40°F in higher sulphur operation.
Figure 10 shows an API change
between feed and product for two
catalyst systems. Near the base tem-
perature where typical ULSD units
operate, the API upgrade difference
approaches almost 1. However, as
the temperature is raised, the dif-
ferences disappear. This is due to a
thermodynamic equilibrium effect
on aromatics saturation. Comparing
the hydrogen consumption of
both systems shows this more
clearly. Figure 11 shows hydrogen
www.eptq.com
27/02/2017 15:05
 consumption differences for two
systems at little more than 50 scf/
bbl around the base temperature. +100
The bottom set of data is included
for 100% Co/Mo catalyst system
results tested on the same feed-
Base
stock. Again, as the temperature is

raised the reverse reaction domi-
nates, resulting in lower hydrogen
consumption.
Tying the information in Figures 9,
10, and 11, the catalyst system con-
taining ICR 1000 can both meet the
ULSD sulphur targets and achieve
higher API improvement (higher
volume swell) at lower start of run
temperature than conventional cata-
lysts can achieve. These advantages
led to the application of ICR 1000 in
a Chevron refinery ULSD unit.
Conclusion
Every refiner faces different con-
straints, processes different feeds
but also has many different hydro-
processing units at its disposal.
Optimisation to improve profita-
bility requires in-depth discussion
between refinery operation and
technical staff and technology pro-
SCFB
−100
Co/Mo
NiMo
NiMo with ICR 1000
Base +50
Temperature, ºF
Figure 11 API upgrade performance
viders such as ART/CLG/Chevron. Marketing and Advanced Refining Technologies.
ICR 1000 and similar development He holds a PhD in chemical engineering from
in catalyst technology is just one MIT and a BS degree in chemical and petroleum
tool in the toolbox that can lead to refining from the Colorado School of Mines.
improved, profitable operation. Meredith Lansdown is a Process Engineer
with Chevron working on hydroprocessing
units in the Richmond, CA refinery. He holds
Reference
a BS degree in chemical engineering from the
1 Bridge A, Cash D, Mayer J, COGELS – Unique
University of Tulsa.
Family of ISOCRACKING Catalysts,1993 NPRA
Brian Watkins is Technical Services Manager
Annual Meeting.
with ART Distillate located in Chicago, IL. He
Alex Yoon is Director of Hydrocracking and holds a BS degree in chemistry from Western
Hydrotreating with Chevron Technology Illinois University in Macomb, Illinois.

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cattec.indd 1 26/02/2013 16:59
 Catalyst filling in a fixed bed
tubular reactor
A reactor filling methodology ensures even reactant distribution
and pressure drop
SUBRATA DAS and NARESH KUMAR SINGH
Fluor Daniel
T
his article discusses a cata-
lyst filling methodology for a
multi-tubular fixed bed reac-
tor system for a gas phase reaction
process to ensure uniform distribu-
tion of the reacting fluid in all of the
reactor tubes. It provides a suitable
procedure for filling the catalyst in
the reactor as per the catalyst dilu-
tion pattern required for a reactor
system. A reaction used to model
the filling methodology is the pro-
duction of 3-cyanopyridine (3-CP)
from 3-methylpyridine (3-MP).
It is good practice to maintain
overall pressure drop across each
reactor tube within +/-5% devia-
tion of the reference pressure drop.
The reference pressure drop can be
derived by passing an equivalent
gas flow rate (corresponding to the
actual reactant flow rate in the tube)
through the reference tube. The typ-
ical value of the reference pressure
drop measured for this reactor sys-
tem is 85 mmHg. All the tubes need
to be identified and marked follow-
ing an agreed and suitable marking
pattern. The tubes with thermocou-
ple elements are also to be marked
a priority and these are filled with
catalyst separately to ensure proper
catalyst distribution and a steady
reaction temperature profile.
Each of the reactor tubes is filled
with diluted catalyst (with different
ranges of dilution across the reac-
tor height). The reactor is provided
with suitable nozzles and baffles in
the shell side for circulating ther-
mal fluid for the removal of reaction
heat. The reactor feed in this case
consists of 3-MP, ammonia, air and
demineralised water in a vapour
state at a temperature of 325-345°C.
This is an exothermic reaction
www.eptq.com
catalysis fluor.indd 1
carried out in the presence of solid
catalyst in the form of cylindrical
pellets with a silica-alumina base. To
ensure homogeneous distribution of
reactant gas and a similar temper-
ature profile in all of the tubes it is
necessary to follow a suitable cata-
lyst filling strategy.
Process outline
The reactor feed enters the top dome
of the reactor from a side nozzle. The
material is allowed to pass through
a bed of inert material placed on a
supporting screen above the reactor
tube sheet to ensure uniform flow of
the feed to all of the tubes. Each tube
is filled in a uniform manner, with
catalyst material having different
dilution patterns at different reactor
heights. Heat of reaction is removed
by thermal fluid circulating in the
shell side. Temperature is measured
at different points in the tubes’ radii
and at different axial heights of the
tubes. Some of the temperature sens-
ing elements are linked to a temper-
ature controller which adjusts the
circulation of thermal fluid on the
shell side. The reactor is provided
with a safety relief system, feed cut-
off and purging facility.
Catalyst filling activity
In view of the six stages of cata-
lyst dilution for each tube, different
aspects of the catalyst filling exer-
cise are covered in the following
sections. The inert/catalyst mixture
zones in a reactor tube are the top
and bottom inert zones and four dif-
ferent catalyst inert mixture zones.
Safety measures and precautions
The top as well as the bottom dome
of the reactor need to be opened
and placed at the side of the reac-
tor to provide an empty work space
for a smooth and safe catalyst fill-
ing operation. Appropriate lifting
arrangements are required for rais-
ing and relocating the catalyst/inert
container from the ground floor to a
platform at the level of the reactor
top tube sheet. The reactor top tube
sheet working height needs to be
checked for any additional platform
requirement, if needed.
During sieving and blending of
the catalyst/inert mixture, some
emission of fine particles is unavoid-
able. This release of fine carbona-
ceous material is due to attrition of
the coated catalyst during handling.
As catalyst dust is harmful to the
respiratory tract, screening, blending
or sieving operations need to be per-
formed in a ventilated dry atmos-
phere on the platform adjacent to
the reactor top.
Preparation of the reactor tubes
In this reactor, there are 1678 reac-
tor tubes each 5m in length with
an internal diameter of 1.5in and
12 gauge thickness. The reactor has
a 1850 mm internal diameter and a
total length of 7500 mm at the tan-
gent line. Each of the reactor tubes
is provided with a 120 mm spring to
support the catalyst load.
On studying the tube sheet ori-
entation it was noted that only two
identical rows with eight tubes each
at the edge are placed side by side
in a straight line. So it was deemed
logical to number the tubes, keep-
ing one of these as the base row
and to mark all the other tubes by
row and number of tubes per row
accordingly. The tube sheet layout is
shown in Figure 1.
Catalysis 2017 61
27/02/2017 11:35
 Marking of tubes containing
thermocouples
There are a total of 25 reactor tubes
with thermocouple elements for the
measurement and control of reactor
temperature. Each of these tubes is
identified and marked clearly on the
reactor top tube sheet.
The thermocouples used in the
reactor system are of two categories.
The first category of thermocouples
(20 in number) has four temperature
sensors located 1.25m from each
other along the thermocouple pocket
(reactor tube length). The other vari-
ety has only one fixed sensing point
(totalling five in number). Hence a
total of 85 sensing points along the
reactor length is available to meas-
ure temperature variation. The ori-
entation of the thermocouple tubes
is made in such a way that each
sensing point of a particular thermo-
couple is at the same height (either
from the top or bottom of the tube
sheet) with respect to the sensing
point of another thermocouple. Such
an arrangement is helpful in provid-
ing radial variation of temperature
profile across the reactor cross sec-
tion and also to identify possible hot
spot locations in the event of a mal-
functioning reactor.
Pressure drop measurement
In order to ensure uniform flow of
reactant feed through all the tubes
it is essential to achieve very close
values of pressure drop across each
of the reactor tubes. For this pur-
pose, a pressure drop measurement
system across the reactor tube is
suggested and shown in Figure 2. A
specific quantity of gas is allowed
to flow through the reactor tube
and pressure drop is measured in
the manometer. The quantity of gas
flow is based on equivalent volu-
metric flow of gas as in actual reac-
tor operation. A blank experiment
was carried out to find the pressure
drop when there is no catalyst pack-
ing inside the tube. A few reference
tubes are chosen and the pressure
drop across these tubes was meas-
ured after filling these with differ-
ent quantities of diluted catalyst and
inert material.
Pressure drop across all of the
other tubes is measured for the same
gas flow rate and some quantity of
62 Catalysis 2017
catalysis fluor.indd 2
Figure 1 Reactor tube sheet layout
inert material and catalyst is added
or removed to ensure acceptable
pressure drop. As good practice, the
measured pressure drop across all
of the other tubes should be within
+/-5% of the reference value.
Preparation of catalyst
It is generally observed that, for an
exothermic gas-solid reaction with
a uniform concentration of catalyst,
the heat release rate varies with
reactor length and gives rise to the
Figure 2 Reactor with nozzle orientation
creation of a hot spot. The hot spot
is initially located at the reactor top
and with time it gradually moves in
a downward direction, mainly due
to loss of catalyst activity with time.
In order to achieve a moderately
uniform bed temperature, it is com-
mon practice to use a dilution pat-
tern across the reactor length. This is
due to controlled reactor heat liber-
ation in the upper zones because of
higher dilution with inert material
in the upper zones. Although the
reactant concentration in the reac-
tor inlet zones is higher compared
to those in the lower zones, cata-
lyst activity is moderated by using
larger quantities of inert material.
The main advantage of this cata-
lyst dilution technology is to achieve
a uniform heat release/distribution
throughout the reactor. Based on
this logic, a specific catalyst dilu-
tion pattern needs to be followed for
the reactor system. The reactor tube
length was divided into four zones,
namely Zone-I, Zone-II, Zone-III
and Zone-IV, respectively, from the
bottom of the reactor, in addition to
two small zones of inert material at
the top and bottom.
It was decided to keep a small
inert bed at the inlet and some inert
material at the reactor tube bottom.
A typical catalyst dilution pattern to
maintain uniformity of the exother-
mic reaction is summarised below.
The loading of Zones I, II, III and
IV, along with marked volumet-
ric percentages of C (catalyst) and I
(Inert) for each of them, is:
Top: 100% I
Zone IV: 25% C and 75% I
Zone III: 50% C and 50% I
Zone II: 75% C and 25% I
Zone I: 100 % C
Bottom: 100% I
It was considered essential that
the catalyst should be prevented
from absorbing humidity, especially
when it is being exposed at night.
All of the catalyst material is there-
fore premixed with inert material
and stored properly to avoid mois-
ture absorption.
For each of the zones in a reac-
tor tube, a measured quantity of
catalyst is mixed with inert mate-
rial according to the given dilution
pattern and a specific quantity of
the mixture is allotted at each level.
www.eptq.com
27/02/2017 11:35
 These allotted categories were duly
isolated and kept safely for filling.
Filling of catalyst
While filling, it should be kept in
mind that pressure drop across each
tube needs to be identical and hence
the top inert layer thickness is var-
ied to achieve this objective. Catalyst
filling in the reactor tubes can be
done with the help of different
measuring cylinders dedicated for
different zones and these are used
exclusively for filling each zone.
Particular care was taken while
carrying out the catalyst filling
operation to prevent the active film
of the support from coming loose
because of undue jolts.
It is necessary to charge the cata-
lyst as uniformly as possible into the
tubes. Therefore, feeding the tubes
is accomplished carefully whenever
possible, and always in the same
manner. The catalyst is allowed to
fall gently from the graduated cyl-
inder into a funnel with a large
discharge tube that is placed over
the mouth of the reactor tube. The
funnel is provided with a large dis-
charge tube to prevent clogging and
the same measuring cylinder and
funnel are used for the entire cata-
lyst filling operation.
After charging of a specific quan-
tity of catalyst, the depth of charge
is measured by means of a cali-
brated measuring rod to ensure that
the filling process is as prescribed.
After complete filling of each
tube, pressure drop across the tube
is measured using the manometer
system.
In order to ensure uniform distri-
bution of reactant gas through all
the tubes, pressure drop across each
of the tubes should be made as simi-
lar as possible. Passing a quantity of
air equivalent to the reactant gas in
commercial operation through each
tube will ensure even pressure drop.
Throughput of air is calculated
on the basis of actual volumetric
throughput of reacting gas during
actual plant operation after making
the necessary molecular weight cor-
rection at an operating temperature
of 350°C and a pressure of 8500 mm.
For the purposes of pressure drop
measurement, an air flow rate corre-
sponding to the volumetric flow rate
www.eptq.com
catalysis fluor.indd 3
of the reactant is maintained so that
the space velocity will be similar to
commercial operation.
The pressure drop is observed
in a single-leg U-tube pressure
gauge with a mercury manometer.
A few tubes were used for refer-
ence purpose and these tubes were
filled with catalyst very precisely For...
as per the prescribed filling pattern.
Pressure drop is measured in these technology solutions
tubes and, on average, pressure
drop was found to be 85 mm Hg.
for refineries and
This is considered to be the refer- chemical plants
ence pressure drop.
It is established that deviation
from the measured maximum and
minimum pressure drops in the
tubes does not exceed +/- 5% of the
mean value. Therefore an acceptable
pressure drop of 80-90 mm Hg was
maintained throughout the process.
If the pressure drop is too small
in any tube, a certain quantity of
fine white inert support is added
until the pressure drop increases
to the necessary level. This is only
intended for minor adjustments.
If air pockets are suspected while
filling (as observed from the meas-
urement of filled length for a spe- ... certified –
cific volume), the bed is emptied
and refilled again. If the pressure independent
drop is seen to be higher than the
worldwide
worldwide...
maximum, it is necessary to remove
part of the catalyst or, in extreme
cases, to empty the whole tube for
refilling. Such cases of erroneous think EDELHOFF.
packing involve loss of catalyst so
are carefully kept to a minimum. Life Support Systems
After each tube is filled, the differen-
Vacuuming Technologies
tial pressure drop should be noted.
Dense Loading Units
Tubular Equipment
Conclusion
A catalyst filling methodology is Services & Rentals
proposed for a multi-tubular fixed
bed reactor system for a gas phase
reaction process to ensure uniform
distribution of the reacting fluid in
all the reactor tubes. Attention must
be paid to preparation and filling
of the reactor tubes to ensure even
flow, particularly to consistent pres-
sure drop across the system.
Subrata Das is a Process Engineer with Fluor
Edelhoff Technologies USA LLC
Daniel India Pvt. He holds a MTech in chemical Houston, Texas · USA
engineering from Indian Institute of Technology
(IIT Delhi), India. Edelhoff Technologies GmbH
Iserlohn, NRW · Germany
Naresh Kumar Singh is a Sr. process specialist
with Fluor Daniel India Pvt. Ltd. He holds B.Tech. www.edelhoff-technologies.com
in chemical engineering from IIT-Roorkee.
Catalysis 2017 63
27/02/2017 11:35
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