Catalysis

catalysis
2014
ptq
cover and spine copy 8.indd 1 01/03/2014 07:23
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2014. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic,
mechanical, photocopying, recording or otherwise without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
3 A hydrotreat for Russian reners
Chris Cunningham

5 ptq&a

17 HCN and NOx control strategies in the FCC
Xunhua Mo, Bart De Graaf, Charles Radcliffe and Paul Diddams
Johnson Matthey, Process Technologies, Intercat
JM
Additives
27 Capturing maximum value with tight oil feeds in the FCC
Alexis Shackleford
BASF Catalysts

37 Maximising distillate while minimising bottoms
Allen Hansen, Adrian Humphries, Stephen McGovern
and Barry Speronello
Rive Technology, Inc

43 Dewaxing challenging parafnic feeds
Renata Szynkarczuk
Criterion Catalysts & Technologies
Michelle Robinson and Laurent Huve
Shell Global Solutions International

53 Maximising distillate and alkylation feed from the FCC
Alan Kramer and George Yaluris
Albemarle Corporation

59 Optimising hydroprocessing catalyst systems
Woody Shiett, Charles Olsen and Dan Torchia
Advanced Rening Technologies
David Brossard
Chevron Lummus Global

Catalytic Reformer No 3 at BPs Kwinana renery, Western Australia. Photo: BP
2014
www.eptq.com
Editor
Ren G Gonzalez
editor@petroleumtechnology.com
Production Editor
Rachel Zamorski
production@petroleumtechnology.com
Graphics Editor
Mohammed Samiuddin
graphics@petroleumtechnology.com
Editorial
PO Box 11283
Spring TX 77391, USA
tel +1 281 374 8240
fax +1 281 257 0582
Advertising Sales Manager
Paul Mason
sales@petroleumtechnology.com

Advertising Sales
Bob Aldridge
Advertising Sales Of ce
tel +44 870 90 303 90
fax +44 870 90 246 90
Publisher
Nic Allen
publisher@petroleumtechnology.com
Circulation
Jacki Watts
circulation@petroleumtechnology.com
Crambeth Allen Publishing Ltd
Hopesay, Craven Arms SY7 8HD, UK
tel +44 870 90 600 20
fax +44 870 90 600 40
ISSN 1362-363X

Petroleum Technology Quarterly (USPS
0014-781) is published quarterly plus
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to
Petroleum Technology Quarterly c/ o PO
Box 437, Emigsville, PA 17318-0437
Back numbers available from the Publisher
at $ 30 per copy inc postage.
espite signs in 2007 of a slowdown in various sectors of the economy,
reners remain a big play for prospective investors. It used to be
conventional wisdom that higher fuel prices and a slowing economy
would curb demand and increase supply, but for the past seven years
that has not proved to be the case. While the rate of increase in world oil demand
has declined since the surprising 4% surge in 2004, it nevertheless appears that
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
increasing oil consumption by China, India and even the Middle East producers
themselves will continue. It is also safe to assume that renery and petrochemical
conversion unit capacity will need to expand.
No massive new sources of energy are expected to come on stream for the
foreseeable future. The world will remain dependent on oil and gas for decades to
come even though the upstream industry faces increasing challenges in the
discovery and production of new sources. In fact, some well-placed industry
analysts think 2008 may be the year where there is no increase in crude supply at
all from regions outside of OPEC. For this reason, we will continue to see signicant
investment in renery upgrades despite surging costs security of feedstock
supply, albeit unconventional low-quality feedstock, takes precedence over the
quality of feedstock supply.
Feedstock options such as biomass (for biofuels production), Canadian tar sands
(for distillate production) and other types of unconventional crude sources require
reactor technology that allows for the integration of these operations into existing
process congurations. The quality of these types of feedstock are one important
reason why a wider array of catalysts has been introduced into the market. For
example, as reners cut deeper into the vacuum tower, the concentration of
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
(eg, <10), high metals, nitrogen and other undesirable components is one of the
main reasons why hydrotreaters and hydrocrackers are becoming larger to
accommodate not only higher volumes of catalyst, but also a wider variety of
catalyst with specic formulations.
Non-catalytic processes are also playing a signicant role in the reners ability
to process whatever unconventional crude sources become available. For example,
some reners processing higher volumes of resid and atmospheric tower bottoms
have considered adding certain types of solvent-extraction processes in addition
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
coker operations. Improvements in furnace technology, such as with olen steam
cracker operations, have resulted in signicant increases in worldwide ethylene
capacity.
However, any expansion of the value chain (eg, ethylene-to-propylene via
dehydrogenation) requires investment in catalytic-based processes, as discussed in
the following articles authored by experts in the eld of downstream process
technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded to the Q&A published in this issue of PTQ Catalysis, as
well as to those respondents who addressed the online questions (www.eptq.com)
that addressed the specics of certain reactor and catalytic issues of importance to
the industry.
Security of
feedstock supply
Ren G Gonzalez
Vol 13 No 2
2008
PTQ CATALYSIS 2008 5
D
catalysis
ptq
ed cont copy.indd 1 03/03/2014 10:57
As hydrocracking team lead at CRITERION, Herman Jongkind is responsible for generating ideas for
new catalysts, as well as preparing, characterizing and testing them, making sure this information
is transferred to the catalyst plants in a joined R&D/manufacturing effort. Among Hermans most
recent and proudest achievements are Z-FX10 and Z-FX20, new generation catalysts that raise
the yield of middle distillates above the traditional bar for hydrocrackers. Herman says success at
CRITERION comes when nding that one little thing that makes a catalyst work better, thereby
leading to a whole new generation of catalysts.
The beauty of catalysis is in the details
one small discovery can lead to a whole
new platform of catalysts.
Meet Herman Jongkind:
Hydrocracking Catalyst Developer and Discoverer.
Leading minds. Advanced technologies.
www.CRITERIONCatalysts.com
criterion.indd 1 27/02/2014 14:16
Catalysis 2014 3
Editor
Chris Cunningham
Production Editor
Rachel Storry
Graphics Editor
Rob Fris
Editorial
tel +44 844 5888 773
fax +44 844 5888 667
Business Development Director
Paul Mason

Advertising Sales
Bob Aldridge
Advertising Sales Ofce
tel +44 844 5888 771
fax +44 844 5888 662
Publisher
Nic Allen
Circulation
Jacki Watts
tel +44 844 5888 776
fax +44 844 5888 667
ISSN 1362-363X

PTQ (Petroleum Technology Quarterly) (ISSN
No: 1632-363X, USPS No: 014-781) is published
quarterly plus annual Catalysis edition by Crambeth
Allen Publishing Ltd and is distributed in the US
by SP/Asendia, 17B South Middlesex Avenue,
Monroe NJ 08831. Periodicals postage paid at New
Brunswick, NJ. Postmaster: send address changes to
PTQ (Petroleum Technology Quarterly), 17B South
Middlesex Avenue, Monroe NJ 08831.
at $30 per copy inc postage.
Vol 19 No 2
2014
A hydrotreat for
Russian reners
O
f all the worlds leaders, none knows better how to make a headline than
Russias President Vladimir Putin. Back in 2011, for instance, the news
was of street demonstrations in Russia demanding higher availability
and lower prices for fuel, amongst other basics. Putins response was to impose
high duties on refnery product exports. You might say that this intervention
was counter-intuitive in the usual context of refning developments, designed
as it was to shore up production of heavy fuel oil, the staple of Russian winter
heating, at the expense of diesel production. All of this did not stop even bigger
street protests in Moscow later on, this time against election results, but at least
demonstrators had the means to keep warm at home.
While other matters led the headlines for President Putin in the frst quarter
of 2014, fuel prices were back to make the second-page lead. The Kremlin said
that it would raise the duty on fuel exports, not quite to the original promise
of parity with fuel oil duty, but to signifcantly higher levels by 2016. The rise
in duty is to be stepped to provide a reprieve for smaller, less-developed refn-
eries that specialise in fuel oil production, to preserve their profts in the
meantime. But the outlook for Russias refning majors is a boost for profts
from their diesel output, effectively a shift in emphasis for their product slate
from the bottom to the middle of the barrel.
Equally, more lucrative production of diesel gives the bigger refners greater
confdence in their capital expenditures on new plant. Russian refners are
among the biggest current spenders on new equipment and the rise in export
duty should inspire the construction of more units to meet Euro IV and V
specifcations. That means more ULSD production and, in the context of an
issue of Catalysis, major growth in an already important market for hydrotreat-
ing catalysts. Two new hydrocrackers, each with more than 50000 b/d
capacity, were due for commissioning in Russia early in the current year and
many more such refnery revamps are expected to follow, along with a supply
of catalyst to feed them.
Of course someone has to pay for a boost in Russias ULSD production.
Inevitably, the sector that will have to stump up is western Europes belea-
guered refning industry. An increased fow of high quality diesel from the east
will squeeze diesel price spreads and hence the already-limited margins of
European refners for whom diesel production is the mainstay of their vulnera-
ble proftability.
There may also be a boost for the Russian refning industry from potential
markets to the east. China has been talking of a signifcantly greater reliance
on natural gas for its power production, in response to deadly levels of air
pollution in the north east of the country, the outcome of an expansion in coal
burning to match growth in the nations economy in recent years, along with
growth in vehicle ownership. If pressure also mounts to burn cleaner automo-
tive fuels sooner, and Chinas refners cannot meet the new demand, no doubt
their counterparts in Russia will be on hand to help out.
CHRIS CUNNINGHAM
Editor
Ren G Gonzalez
Production Editor
Rachel Zamorski
Graphics Editor
Mohammed Samiuddin
Editorial
PO Box 11283
Spring TX 77391, USA
tel +1 281 374 8240
fax +1 281 257 0582
Advertising Sales Manager
Paul Mason

Advertising Sales
Bob Aldridge
Advertising Sales Of ce
tel +44 870 90 303 90
fax +44 870 90 246 90
Publisher
Nic Allen
Circulation
Jacki Watts
tel +44 870 90 600 20
fax +44 870 90 600 40
ISSN 1362-363X

Petroleum Technology Quarterly (USPS
0014-781) is published quarterly plus
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to
Petroleum Technology Quarterly c/ o PO
Box 437, Emigsville, PA 17318-0437
at $ 30 per copy inc postage.
espite signs in 2007 of a slowdown in various sectors of the economy,
reners remain a big play for prospective investors. It used to be
conventional wisdom that higher fuel prices and a slowing economy
would curb demand and increase supply, but for the past seven years
that has not proved to be the case. While the rate of increase in world oil demand
has declined since the surprising 4% surge in 2004, it nevertheless appears that
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
increasing oil consumption by China, India and even the Middle East producers
themselves will continue. It is also safe to assume that renery and petrochemical
conversion unit capacity will need to expand.
No massive new sources of energy are expected to come on stream for the
foreseeable future. The world will remain dependent on oil and gas for decades to
come even though the upstream industry faces increasing challenges in the
discovery and production of new sources. In fact, some well-placed industry
analysts think 2008 may be the year where there is no increase in crude supply at
all from regions outside of OPEC. For this reason, we will continue to see signicant
investment in renery upgrades despite surging costs security of feedstock
supply, albeit unconventional low-quality feedstock, takes precedence over the
quality of feedstock supply.
Feedstock options such as biomass (for biofuels production), Canadian tar sands
(for distillate production) and other types of unconventional crude sources require
reactor technology that allows for the integration of these operations into existing
process congurations. The quality of these types of feedstock are one important
reason why a wider array of catalysts has been introduced into the market. For
example, as reners cut deeper into the vacuum tower, the concentration of
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
(eg, <10), high metals, nitrogen and other undesirable components is one of the
main reasons why hydrotreaters and hydrocrackers are becoming larger to
accommodate not only higher volumes of catalyst, but also a wider variety of
catalyst with specic formulations.
Non-catalytic processes are also playing a signicant role in the reners ability
to process whatever unconventional crude sources become available. For example,
some reners processing higher volumes of resid and atmospheric tower bottoms
have considered adding certain types of solvent-extraction processes in addition
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
coker operations. Improvements in furnace technology, such as with olen steam
cracker operations, have resulted in signicant increases in worldwide ethylene
capacity.
However, any expansion of the value chain (eg, ethylene-to-propylene via
dehydrogenation) requires investment in catalytic-based processes, as discussed in
the following articles authored by experts in the eld of downstream process
technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded to the Q&A published in this issue of PTQ Catalysis, as
well as to those respondents who addressed the online questions (www.eptq.com)
that addressed the specics of certain reactor and catalytic issues of importance to
the industry.
Security of
feedstock supply
Ren G Gonzalez
Vol 13 No 2
2008
PTQ CATALYSIS 2008 5
D
catalysis
ptq
ed cont copy.indd 2 28/02/2014 10:41
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HYDROPROCESSING
ALKYLATION
HYDROGENATION
HYDROCRACKING
OLEFINS METATHESIS
FCC
cbi_ptq_catalysis_ad_mar_2014.indd 1 2/21/2014 1:56:35 PM
cbi.indd 1 28/02/2014 10:22
Q
What catalytic options are available for chloride removal
from liquid renery streams?
A
Olivier Ducreux, Adsorbents Business Line Manager, Axens,
olivier.ducreux@axens.net
Different solutions can be implemented for chloride
removal from gas or liquid phase refnery streams
depending on several factors including:
Chloride species present
Composition of the stream to be treated.
Axens developed some solutions to remove all trace of
chlorides species to avoid corrosion or catalyst poisoning
issues around the reformer, isomerisation, hydrockrack-
ers or HDT units. AxTrap 800 series are highly effcient
trapping adsorbents, designed for the removal of chlo-
ride from liquids and gas streams (H
2
net gas, stabiliser
off-gas) to levels lower less than 0.1 ppm.
If only HCl is present in the feed stream, which is
mostly the case in gas and light hydrocarbon streams
such as LPG, a simple guard bed set-up is suffcient for
chloride removal. Many adsorbent vendors propose
HCl removal adsorbents, either based on promoted
alumina or based on metal oxide technologies. Axens
promoted alumina based adsorbents, named AxTrap
858, have demonstrated much better cost effciency in
the liquid phase, due to their better cost/performance
ratio and much better mass transfer characteristics
(and thus higher pickup capacities). HCl removal
adsorbents can be implemented easily and effciently
regardless of the composition of the feed stream.
If organic chlorides are present in the feed stream
and need to be removed, simple adsorption technology
can be only partially effcient. Its effciency is strongly
dependent on the chloride species to be removed and
on the composition of the feed stream:
If the feed stream is only or mostly paraffnic an
adsorbent guard bed implementing a multilayer adsor-
bent mix (Axens Multibed technology), one for the
removal of HCl and one for the removal of organic
chlorides, can be implemented. This simple and
straightforward solution is suffcient in most cases,
especially but not limited to the gas phase. Axens has
several industrial references for this application
If the feed stream is highly olefnic or highly aromatic,
competition between organic chlorides and some of the
components of the feed stream can render simple
adsorption technologies less effcient. In such (rare)
cases catalytic technologies become necessary. A noble
metal catalyst used for transformation of organic chlo-
rides into HCl followed by a simple HCl guard bed
adsorbent will be effcient even in the most diffcult
cases. Axens has an adapted catalysts for this
application.
A
Axel Dueker, Product Manager Fuel Upgrading, Clariant
BU Catalyst, Axel.dueker@clariant.com
Chloride removal for HCl as well as organic chlorides
is typically achieved by so-called Cl-guards. The
removal mechanism of state-of-the-art Cl-guards is the
chemical conversion of the chlorides with the guard
material into chloride salts. Less sophisticated materi-
als utilise physical adsorption to bind the chlorides but
handling of such materials after use is diffcult as
uncontrolled emissions of adsorbed compounds may
occur. Some of the available less sophisticated materi-
als may also form increasing levels of organic chlorides
during operation. Materials containing alumina and
aluminosilicates should therefore be avoided. Due to
the highly competitive environment in todays refning
industry, many refneries across the globe have shifted
their focus and now aim for the combined removal of
HCl and organic chlorides.
Clariant offers a series of Cl-guards designed for the
removal of HCl and organic chlorides from liquid and
gaseous hydrocarbon streams at high pick-up capacities.
The ActiSorb Cl products are based on an engineered
combination of zinc oxide with a special binder to espe-
cially enhance the removal of organic chlorides. A large
number of refneries all over the world had identifed
the outstanding performance of Clariants Cl-guards.
A
Claus Brostrm Nielsen, Product Manager, Haldor Topse,
clbn@topsoe.dk
Chloride is typically found in refnery streams due to
continuous addition of chloride compounds in the
catalytic naphtha reformers or isomerisation units. The
chloride present as organic chloride in liquid refnery
streams can be converted into HCl by a hydrotreating
catalyst. HCl is then trapped downstream the hydro-
treating unit by a chloride guard, where HCl is
absorbed on alumina containing alkali metals. Chloride
present in refnery streams as HCl does not need any
catalytic treatment, but can directly be absorbed by the
chloride guard.
For chloride absorbing, Topse offers several products
like HTG-1 and HTG-2 which are specifcally developed
for maximum chloride uptake from refnery streams.
Q
Are there economic advantages in trading spent catalyst
for precious metals recovery over sending it for landll/
cement production?
www.eptq.com Catalysis 2014 5
catalysis q&a
Additional Q&A can be found at www.eptq.com/QandA
Q&A copy 12.indd 1 28/02/2014 11:11
A
Sam Bowles, PGM Rening Sales Executive, Rening and
Chemicals Europe Johnson Matthey Process Technologies,
Sam.Bowles@matthey.com
Platinum group metal (PGM) bearing catalysts are
typically employed on substrates (carriers) such as
soluble and insoluble alumina, silica alumina, zeolite,
or carbon support. They have many roles in many
different industries. In the petroleum industry they can
provide a signifcant role in reforming and isomerisa-
tion, however the costs of the PGM loadings on the
catalysts can be huge. Unfortunately the harsh envi-
ronments which contaminate the catalysts mean that
over time they lose their effciency and thus no longer
perform effectively and are considered spent. It is at
this stage where new PGM catalysts must be used and
you are left with the choice of what to do with the
spent catalyst.
As the precious metal used in catalysts is an expen-
sive and scarce resource, their recovery, recycling and
re-use is essential to maintain long term global sustain-
ability. In addition, the economics of any process that
utilises precious metals is key to proft and growth.
Precious metals such as platinum, palladium and
rhodium constitute a signifcant investment, so an
important factor in the economics of these processes is
the ability to recover the precious metal content from
the catalyst once it is spent. A quick and effcient
retrieval of the metals is of utmost importance. By
trading the spent catalyst for precious metals refning
you have the ability to recover the precious metal
content from the catalysts. If the PGM catalysts have a
greater value of precious metal contained, compared to
the costs of refning and recovering it, then there is a
clear economic advantage in refning the spent cata-
lysts. If you then consider the sheer magnitude of
PGM bearing catalysts used by businesses in the
process technology industry, it means that there can be
millions of dollar worth of precious metal available
that can be recovered.
Trading spent catalyst for precious metal recovery
also facilitates closed loop refning as the precious
metal content recovered in these spent catalysts can be
used to manufacture future orders allowing for better
metal management, which can be important especially
with fuctuating metal prices (see Figure 1).
Sending the spent catalyst for refning also elimi-
nates the costs of disposing in landfll and can help
mitigate the environmental issues associated with
disposing of spent catalyst in a landfll or disposal site,
especially for those that are considered as hazardous
waste. Any company that exports controlled waste has
a duty to take all reasonable steps to ensure that their
waste is handled lawfully and safely. By sending the
spent catalysts to a well-established, highly specialist
refner they have the expertise and licences to ensure
that wastes are treated correctly through responsible
operations and are in compliance with any applicable
international, environmental and legal regulations. All
of this is achieved without forfeiting the value of the
precious metal content.
Further information on the refning of spent catalyst
can be found by visiting www.jmrefning.com .
A
clbn@topsoe.dk
Spent catalysts containing precious metals can be
handled by specialist companies that can recover most
of the precious metals. The recovery of the metals is
typically so high that there is a large economic advan-
tage in sending the spent catalyst for metal recovery
rather than using the spent catalyst for landfll/cement
production. Due to the high prices of precious metals,
even catalysts containing small amount of metals are
worth sending for metal recovery.
A
Steve Metro, Senior Business Leader Naphtha Products,
UOP Catalysts, Adsorbents, and Specialties, steve.metro@
honeywell.com
Spent catalysts that contain precious metals such as
UOP Platforming catalysts are never sent to direct land
fll due to the Pt content and monetary value. They are
sent to reputable precious metals recovery frms such
as Gemini Industries, Sabin Metal Corporation or
Heraeus Precious Metals, where they can effciently
recover Pt, Re, Ir, and Pd from solid alumina
substrates.
Q
We are not getting the cycle life we were expecting from
our hydrotreating catalyst after presulphiding. How should
we be adjusting process conditions after presulphiding?
A
Ken Koziol, Hydrotreating Global Sales Support Manager
Catalyst, Adsorbents, & Specialties, UOP, ken.koziol@
honeywell.com
This question is complicated based on the use of the
term presulphiding as it is either referring to prob-
lems with a hydrotreating catalyst that has been
presulphided prior to being loaded into the reactor or
it is referring to performance issues with the hydro-
treating catalyst after it has been in-situ sulphided
with a sulphiding agent such as DMDS during the unit
start-up. With regards to any hydrotreating catalyst
and its performance after start-up, one key item that is
critical to maintain the optimum catalyst activity is to
maintain the feed free of cracked stocks for 72 hours
6 Catalysis 2014 www.eptq.com
1 6 0 0
1 9 0 0
1 8 8 7
1 5 2 6
1 0 3 9
1 8 0 0
1 7 0 0
1 5 0 0
1 4 0 0
1 3 0 0
1 2 0 0
1 1 0 0
1 0 0 0
2 0 1 0 2 0 1 1 2 0 1 2 2 0 1 3 2 0 1 4
Figure 1 PM Pt x in US dollars over the last ve years
Source: LPPM.com
Q&A copy 12.indd 2 28/02/2014 11:11
www.jmprotech.com
UK Tel +44 (0)1642 553601 Fax +44 (0)1642 522542
Johnson Matthey is a global supplier of market
leading hydrogen plant catalysts, FCC additives,
technologies and services for the oil rening industry.
At Johnson Matthey we are committed to helping
our customers nd solutions to their toughest
challenges and offer a full spectrum of value
added products and services to improve the
performance and protability of their processes.
proven process
performance
j matthey.indd 1 28/02/2014 10:26
after sulphiding unless the catalyst has been pre-acti-
vated with cracked feed protection. During these frst
three days after catalyst activation, the hydrotreating
catalyst is in a state of hyperactivity and thus the
introduction of cracked stocks can create aggressive
coking on the catalyst, thus diminishing the activity of
the catalyst for the rest of the cycle. After sulphiding, it
is important to bring the respective catalyst operating
temperatures up or down from the fnal sulphiding
hold temperature as necessary to meet the target prod-
uct specs and no higher. It is also important to make
sure the recycle gas scrubber is immediately put in
service after sulphiding to remove the excess hydrogen
sulphide as increased levels of hydrogen sulphide will
require a higher temperature to meet the same product
specifcations.
With regards to other issues that could occur during
sulphiding that can impact the catalyst performance, it
is critical to make sure that the temperatures of the
sulphiding steps and the necessary hydrogen sulphide
breakthroughs are reached and maintained as detailed
by the catalyst manufacturer as these steps are critical
to reach the optimum catalyst activity for the cycle. It
is also imperative to understand the hydrotreating
reactor temperature limitations during start-up as
there have been cases where units have been designed
with integrated heat exchange based on normal opera-
tion but during start-up this heat is not available to
fully activate the catalyst, such as in a diolefns reactor,
where it may be of value to have this catalyst pre-acti-
vated to maintain the necessary activity. Another key
item during the sulphiding process is to make sure
that the feed rate used during the sulphiding is greater
than 70% of design to make sure that the full catalyst
is being fully contacted and sulphided.
If this question is referring to issues with presul-
phided catalyst performance then the key items to
review with your catalyst supplier and the presulphid-
ing service supplier are the sulphur level of the
presulphided catalyst, the metals content of the cata-
lyst provided, and fnally verifying that the method of
presulphiding is appropriate for the respective Type I
or Type II catalyst that had been chosen. Issues in any
of these areas can impact hydrotreating performance.
A
clbn@topsoe.dk
The cycle life of a hydrotreating catalyst depends on
many factors, such as feed properties, product require-
ments and operating conditions. If the cycle life is not
reached with the design parameters, one of these
factors must be relaxed. This could be processing an
easier feedstock, like lower sulphur and nitrogen
content, lower end boiling point or density or less
metal content. If the feedstock properties cannot be
changed, the product requirements could be relaxed,
like higher product sulphur and nitrogen. The last
option is to change the operating conditions to more
favourable conditions, like reduced feed rate, higher
hydrogen partial pressure, higher hydrogen oil ratio or
increased treat gas purity. Any change in these factors
will have a positive effect on the cycle life of the
hydrotreating catalyst.
A
Brian Watkins, Brian Slemp, Greg Rosinski, Carrie
Constantine, Meredith Lansdown, Advanced Rening
Technologies Technical Service
There are several likely reasons for not achieving the
expected cycle life from a catalyst loading. First, it is
important to understand the difference between the
types of ex-situ catalyst sulphiding in order to ensure
that you are gaining the most activity from the ex-situ
sulphided catalyst. Once optimum catalyst activity is
ensured, you can then examine the process conditions
after the completion of the activation to help to main-
tain the proper cycle life.
Presulphided catalyst
This type of catalyst has had the stoichiometric
amount of sulphur, plus some excess, added to the
catalyst surface so that it is ready to be activated once
in the reactor under the proper conditions. This type of
start-up requires that the H
2
S that is generated by the
decomposition of the sulphur compound present on
the catalyst is recirculated and allowed to activate the
catalyst once the catalyst bed temperatures are high
enough. Use of liquid during this start-up can help
with controlling the heat of reaction produced when
the sulphur chemical begins to react. This type of acti-
vation can create a very high delta temperature in the
reactor if not monitored closely. If this type of activa-
tion is used, and there is an upset during start-up, it is
possible to lose some of the required H
2
S and can end
up with a catalyst system that may be signifcantly less
than 100% activated. Use of virgin feedstock during
this start-up process will help to mitigate this issue
due to availability of extra sulphur in the feed as well
as provide additional heat control from the extra mass
in the reactor.
Presulphided/activated catalyst
This type of ex-situ sulphiding has actually had the
metal sites on the catalyst converted from the oxide
state to the sulphided state. This process, where the
sites are already converted to the active phase is easier
to start up since there is less heat generated which
results in a lower chance of a thermal runaway. The
conversion of the oxide metal sites to sulphide sites in
the ex-situ process also helps to ensure that as much of
the catalyst activity as possible is maintained for the
process. This type of ex-situ sulphiding can also be
passivated for ease of handling during loading, or it
may require special handling during loading in order
to avoid contact with oxygen.
Once the system is sulphided the initial catalyst
activity is extremely high. The extremely high activity
will generate higher than average temperatures on the
catalyst surface. The increased surface temperature can
cause incremental coking and excessive deactivation of
the catalyst active sites. The hydrotreating system will
not achieve its ultimate run life potential from the
excessive initial coking deactivation if feedstocks
Q&A copy 12.indd 3 28/02/2014 11:11
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containing large amounts of coke precursors are
processed immediately after start-up. To minimise this,
ART recommends using virgin feedstock (low olefn
and low aromatic content) with a lower end point that
has lower coking potential for the frst 72 hours after
catalyst activation. The use of the lower reactivity
virgin feed helps moderate the catalyst surface
temperature and control coke distribution to minimise
the negative impact on activity to allow a longer over-
all operating cycle.
Another issue to address that can affect any catalyst
cycle is poisons. It is recommended to monitor the
spent catalyst for poisons. If the catalyst that is
removed contains a higher than expected quantity of
poisons, then it is time to explore the use of specialty
guard catalysts in order to protect the main bed hydro-
treating catalyst.
Q
Is there a catalyst option for upgrading LCO to ULSD
without an additional process step?
A
Antoine Fournier, Business Line Group Manager, Catalyst
Technology Department, Axens and Jacinthe Frcon,
Technology Group Manager, Middle Distillates & Conversion
Business Line, Axens, jacinthe.frecon@axens.net
Axens already has experience with pure LCO feed-
stock hydroprocessing. When, most of the time,
producing ultra low sulphur diesel can be achieved
with a conventional catalyst in a single stage process,
the main constraint with LCO hydroprocessing is to
meet other characteristics associated to Euro V produc-
tion, and in particular the cetane and/or the density
specifcations.
In that case, several approaches could be envisioned:
Using a two-stage approach with the implementation
of a noble metal catalyst section in order to complete
the aromatic saturation required for cetane improve-
ment and density reduction while maximising the
diesel yield (minimum cracking)
Using a combination of pretreatment and cracking
catalysts in a single stage process in order to reduce
the density and improve the cetane thanks to naph-
thenic ring opening. This solution can bring a higher
density and cetane boost compared to the two-stage
approach (pure hydrogenation option) but results in a
lower diesel yield.
A
clbn@topsoe.dk
Upgrading of LCO feedstock to ULSD is possible with
a catalytic treatment in a typical hydrotreating unit.
Depending on the properties of the LCO, a hydrotreat-
ing catalyst can make the upgrade to ULSD; however,
in some cases, a hydrocracking catalyst is needed. If
the LCO is high in density, maximum aromatics satu-
ration is needed in order to reach the density and
cetane number specifcations for ULSD. This is
obtained by using a NiMo hydrotreating catalyst at
high pressure. However, if the LCO is high in density,
and the density specifcations cannot be reached by
sulphur removal and aromatics saturation, it is recom-
mended to use a hydrocracking catalyst in the lower
beds to reach the density specifcations for ULSD.
Topse has several references on the use of hydroc-
racking catalyst for this application and has recently
also introduced the NiMo catalyst TK-609 HyBRIM
which has an exceptionally high hydrogenation activ-
ity, making it the optimum choice for LCO upgrading.
A
Anubhav Kapil, Lead Technical Sales Specialist CA&S
Rening Hydroprocessing, UOP, Anubhav.Kapil@honeywell.
com
Light cycle oil (LCO) is a by-product of catalytic crack-
ing and is normally high in sulphur, nitrogen and
aromatic content. LCO material typically is in the same
boiling range as diesel, but as it is rich in multi-ring
aromatics, it produces fuel with very low cetane
number (typically 1525). Because of the high sulphur
and low cetane number, LCO makes a poor diesel fuel
blending stock.
Ultra low sulphur diesel (ULSD) specifcation can
vary slightly from country to country, but generally it
means diesel fuel with substantially lowered sulphur
(less than 10 or 15 wtppm). If sulphur speciation of a
LCO feedstock is conducted, we will fnd that a signif-
cant portion of the sulphur is found in
alkyldibenzothiophenes (DBT). In order to achieve the
ultra low sulphur, most of these diffcult refractory
compounds in the feed have to be converted; this
makes the upgrade of LCO to ULSD complex.
Depending on whether one is trying to make just
ULSD or also trying to produce high quality diesel
product with low aromatics, careful consideration has
to be given not only to feed quality but also to the
product objectives.
UOP has made signifcant advancement in the feld
of upgrading LCO to ULSD by developing state-of-the
art catalysts as well as processes optimised for LCO
upgrading. The main technologies available for LCO
upgrading are the Unionfning process and the
Unicracking process. UOP offers the Unionfning
process with both base metal as well as noble metal
catalysts. The choice of which process and catalyst to
use depends on the desired improvement in cetane
index and on existing limitation at the refnery. The
one limitation of base metal Unionfning is that it
requires a high severity operation and provides only a
modest improvement in cetane number. A partial
conversion Unicracking unit with moderate distillate
selectivity catalyst is generally the best option when
trying to achieve ULSD with good cetane number
improvement. The hydrocracking catalyst helps
convert the complex DBT and signifcantly benefts
cetane by cracking the most diffcult to hydrogenate
aromatic compounds to naphtha.
A
There are several basic impacts that need to be under-
stood when considering upgrading any particular
Q&A copy 12.indd 4 28/02/2014 11:11
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arounds. This may mean that processing additional
LCO, or processing it completely in a single hydro-
treater, may require the use of a system with higher
pressure and additional hydrogen in order to utilise a
more powerful NiMo catalyst designed for aromatic
saturation and removal of the additional hard sulphur
compounds.
In general, cracked stocks (cokers and LCOs) are
more challenging to hydrotreat and require a higher
weighted average bed temperature (WABT) compared
to a straight run (SR) material at the same product
targets. Feeds from the fuid catalytic cracker (FCC) are
much higher in aromatics than their SR counter parts
and are especially concentrated in poly aromatics. This
also gives these feeds a much lower API gravity rela-
tive to SR or coker stocks. The concentration of
sulphur and nitrogen in these feeds are dependent on
the presence of a pretreater upstream of the FCC
which can help in lowering the total sulphur or nitro-
gen content. However, the sulphur and nitrogen
compounds in FCC are usually the more diffcult
refractory species requiring a much higher required
WABT to achieve the same product specifcation (see
Figure 2).
If your distillate hydrotreater has incremental hydro-
gen available and operates at high enough pressure,
LCO can be processed, but will likely require the
switch to an all NiMo catalyst system. LCO normally
contains the highest amount of aromatics and therefore
will provide the maximum volumetric expansion from
hydrotreating. LCO will also undergo the largest
increase in cetane across the hydrotreater as shown in
Figure 3.
As always, ART is prepared to discuss these options
and assist in making the best choice with the catalyst
system already in use, and also to help prepare for the
next catalyst load in order to take advantage of this
process change.
Q
We are experiencing excessive pressure drop during
hydrotreating as a result of iron scale build-up in the catalyst
bed. Is the problem best addressed in the desalter or is this
more likely to be carry-through of plant corrosion problems?
A
Iron works its way into hydrotreater feed as rust and
iron scale from corrosion of upstream equipment and
piping as well as unfltered particulates present in the
feed. Iron naphthenates can form from piping corro-
sion due to naphthenic acid in the feed, and the iron
readily precipitates out in the presence of heat and
H
2
S. Characterisation of the iron to help identify the
source is important to understand and develop the
best methodology to mitigate its effects on the hydro-
treater. Iron scale materials are due primarily from
corrosion of piping and equipment en route to the
hydrotreater. This is a solid type of iron that, if allowed
to bypass the feed flters or there are no flters present,
stream in a refnery, especially LCO. With increases in
the fnal boiling point of the feed, the total sulphur and
nitrogen, the concentration of hard sulphur, and
aromatics content all increase. This is independent of
the source of feedstock (see Figure 1). In order to main-
tain the same product specifcations, this will need to
be compensated for by increasing the reactor tempera-
ture. Examining your available hydrotreaters and their
processing capabilities as well as the availability for an
increased demand for hydrogen in one area or another
in the refnery is important to avoid unexpected turn-
0 . 6
1 0
0 . 9
0 . 8
0 . 7
0 . 5
0 . 4
0 . 3
0 . 2
0 . 1
F
r
a
c
t
i
o
n

h
a
r
d

s
u
l
p
h
u
r
0
4 5 0 5 0 0 5 5 0 6 0 0 6 5 0 7 0 0 7 5 0 8 0 0
Feed 90% poi nt (D86), F
S R
L C G O
F C C L C O
6 0
1 0 0
9 0
1 2 0
1 1 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
R
e
q
u
i
r
e
d

i
n
c
r
e
a
s
e

i
n

W
A
B
T
,

F
0
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0
FCC LCO, %
8 . 0
1 0 . 0
9 . 5
9 . 0
8 . 5
7 . 5
7 . 0
6 . 5
6 . 0
5 . 5
C
e
t
a
n
e

i
n
d
e
x

i
n
c
r
e
a
s
e
5 . 0
1 9 2 1 2 3 2 5 2 7 2 9 3 1 3 3 3 5 2 0 2 2 2 4 2 6 2 8 3 0 3 2 3 4
Feed API gravi t y
1 0 0 % L C O 1 0 0 % S R
Figure 1 Fraction of hard sulphur depends on endpoint
Figure 2 Impact of FCC LCO on ULSD hydrotreater
Figure 3 Impact of FCC LCO on ULSD cetane index
Q&A copy 12.indd 5 28/02/2014 11:11
form the crust layer in the hydrotreater and require
special grading materials to help minimise this prob-
lem. Efcient and effective use of the desalter is always
recommended to avoid bringing in additional iron
sources that can overwhelm the catalyst grading
system.
These iron particulates ll 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
network is also valuable (see Figure 1).
If iron is known to be the cause of the pressure drop
issues, then 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.
Other options are to utilise materials that are
specially designed to increase the void fraction in the
top bed of the reactor and are efcient at trapping iron,
other particulates and scale. These measures are help-
ful for delaying pressure drop build-up, but they do
not prevent eventual pressure drop build-up. Effective
feed ltration to remove particulates (at least 25
microns) provides a longer lasting solution in helping
mitigate pressure drop build-up from these sources, as
well as a way to identify the sources of iron that are
present in the process.
If the amount of iron that is making it into the
hydrotreater requires too large a volume of grading
materials at the top of the hydrotreater, such that it is
impacting the desired cycle length, then the remaining
option is to remove it from the feed altogether. As
feed rates and qualities vary signicantly day after
day, upstream prevention combined with guard bed
technology can extend the cycle length of the
hydrotreater.
It has also been found that some of the synthetic
crudes may also contain very ne particulates of clay
or sand that are associated with asphaltenes or other
heavy polycyclic molecules. These particulates can be
removed through proper use of the desalter to avoid
crude tower fouling. However, these small particulates,
typically <5 microns, when not properly removed, can
pass through feed lters into the catalyst beds result-
ing in pressure drop issues.
A
clbn@topsoe.dk
Pressure drop problems due to iron scale in hydro-
treating units is a common problem seen at reneries.
Iron can be found both as very small particles or even
at larger scales, both typically originating from corro-
sion. Corrosion can take place upstream the
hydrotreating unit in pipes and equipment. The corro-
sion products are transferred to the hydrotreating unit
with the oil and gas streams during normal operation
and will plug the top of the catalytic bed causing
excessive pressure drop build-up. In worst case, the
hydrotreating unit is forced to shut down for catalyst
replacement. The pressure problem due to iron scale
can be minimised with an optimal graded bed in the
top of the catalyst bed. The grading should have
enough void to accumulate the iron scale without
causing increased pressure drop. Furthermore, the
grading should have an optimum shape and porosity
to be able to catch even the very ne iron particles
which would otherwise reach the bulk catalyst. For
this specic purpose, Topse has developed the grad-
ing product TK-25 which has a unique shape and a
porosity specically designed to trap small iron
particles.
A
Ken Koziol, Hydrotreating Global Sales Support Manager
Catalyst, Adsorbents, & Specialties, UOP, ken.koziol@
honeywell.com
From our experience, the issue of iron reaching the
hydrotreater and creating pressure drop problems is
primarily caused by upstream corrosion problems. In
many cases, the root cause is the crude choice and its
respective acidity which is causing corrosion problems
throughout the downstream towers and process units.
Another area where corrosion issues propagate is in
intermediate storage tanks due to issues with inade-
quate dewatering, oxygen incursion, and/or too low
feed draws out of the tank. The only way to extend
your cycle life on your hydrotreater is through the use
of an enhanced grading system to focus on the ne
iron particulates beyond the classical high void wagon
wheel/honeycomb topping material and rings. This is
done through the use of strategically designed grading
beds at the top of the hydrotreater reactor instead of
support media that incorporate such 21st century tech-
nology as Crystaphases patented CatTrap Reticulation
Technology disks or other macrotrap highly porous
material which have the capacity to hold the ne iron
particulates. Remember that grading systems are
extending your cycle performance but only the correc-
tion of the root cause of the iron levels will remove the
issue.
Porous ceramic
material
Iron sulphide
gums adsorbed
Particulates are trapped
in the macro pores
Figure 1 Internal and external void space in macroporus ring
structure
Q&A copy 12.indd 6 28/02/2014 11:11
A
clbn@topsoe.dk
The choice of catalyst for a hydrotreating unit depends
on the feedstock, product requirements and operating
conditions. Generally, at low pressure, a CoMo type
catalyst is the optimal choice for HDS, and at high
pressure, a NiMo type catalyst is the optimal choice for
both HDS and HDN. When a NiMo catalyst is applied
at low pressure in order to increase HDN then the
HDS conversion would be lower, and this would often
be the case also if a stacked bed CoMo/NiMo catalyst
was applied. Therefore, in most cases, a single type
catalyst system is the optimal solution. Topse offers
catalyst products for all ranges of pressure and all
types of feeds such as the high activity CoMo catalyst
TK-578 BRIM and the high activity NiMo catalyst
TK-609 HyBRIM.
A
One of the keys to successful ULSD production is a
detailed understanding of the chemistry involved. It
has been known for some time that there are two reac-
tion pathways to remove sulphur from
dibenzothiophene and substituted dibenzothiophenes.
The frst pathway is the direct abstraction route, which
involves adsorption of the molecule on the catalyst
surface via the S atom followed by C-S bond scission.
C-H bonds using chemisorbed hydrogen then replace
the C-S bonds. This is the primary pathway over
cobalt-molybdenum (CoMo) based hydrotreating cata-
lysts. The rate determining step is the C-S bond
scission and not C-H bond formation, which explains
the low H
2
partial pressure dependency of desulphuri-
sation over CoMo catalysts. The second pathway, the
hydrogenation route, involves saturation of one
aromatic ring followed by the extraction of the S atom.
Nickel-molybdenum (NiMo) catalysts, which exhibit a
higher hydrogenation activity than CoMo catalysts,
have a higher selectivity for desulphurisation via this
route.
To reduce sulphur to <50 ppm, alkyl substituted
dibenzothiophenes must be desulphurised. A number
of these compounds will have alkyl groups attached to
the carbon atoms adjacent to the sulphur atom (the 4
and 6 positions) and this leads to a shielding effect or
steric hindrance for adsorption via the sulphur atom.
Consequently the reaction rate for the direct abstrac-
tion route is considerably reduced. On the other hand,
if one of the aromatic rings is saturated, it is no longer
planar and can fex, allowing easier interaction of the
sulphur atom with an active site. The hydrogenation
route that is preferred over NiMo catalysts is not inhib-
ited by alkyl substitution and, depending on the
catalyst properties and operating conditions, will have
a higher HDS rate than CoMo catalysts. The SmART
system is based on high activity, specifcally designed
catalysts which take advantage of the different reaction
mechanisms for sulphur removal. Dibenzothiophenes
(DBT) and lighter sulphur containing molecules, the
Q
What developments are there in catalysts for producing
high quality middle distillates from streams derived from non-
petroleum sources such as natural gas, biomass or coal?
A
Anders Bo Jensen, General Manager Hydrocracking
Technology, Haldor Topse, abj@topsoe.dk
The gas-to-liquids (GTL) process used to convert natu-
ral gas into high quality middle distillates consists of
three steps:
1. Reforming of natural gas into a mixture of carbon
monoxide (CO) and hydrogen (H
`
), known as synthesis
gas or syngas, preferably by auto-thermal reforming
(ATR)
2. Catalytic conversion of syngas to high quality
paraffnic hydrocarbons by the Fischer-Tropsch (FT)
process
3. Hydroprocessing of the paraffnic FT products to
high quality diesel and jet fuel products. The biomass-
to-liquid (BTL) and coal-to-liquid (CTL) processes
share the same process steps except for the frst step of
syngas generation which is based on gasifcation.
Recent FT process developments include the intro-
duction of multi-channel FT reactor technology, which
provides for enhanced heat and mass transfer and
allows the use of more active FT catalysts, which
together with the multi-channel reactor intensifes the
highly exothermic chemical reaction. This enables a
small scale modular approach and engineering designs
that are signifcantly more compact than conventional
FT process units.
The hydroprocessing step involves saturation of
light olefns, hydrodeoxygenation of light oxygenates,
as well as hydrocracking and isomerisation of
long chain paraffns to produce middle distillates that
are inherently low in sulphur and aromatics. The
required degree of isomerisation depends on the prod-
uct cold fow specifcations. Recent catalyst
developments provide increased selectivity towards
middle distillates with minimum over-cracking to
light ends. For small scale upgraders, only simple
process confgurations can be justifed with co-process-
ing of light and heavy FT products applying
multi-function catalysts or optimised stacked-bed cata-
lyst loadings.
Q
Is HDS and HDN best addressed by staged catalysis or is
there an effective one-step catalytic option for the task?
A
Antoine Fournier, Business Line Group Manager, Catalyst
Technology Department, Axens and Jacinthe Frcon,
Technology Group Manager, Middle Distillates & Conversion
Business Line, Axens, jacinthe.frecon@axens.net
While direct hydrodesulphurisation is the preferred
pathway with CoMo catalysts, the use of a NiMo cata-
lyst helps increase the aromatic saturation and the
HDN activity of a reaction system.
Depending upon the unit constraints and objectives,
the combination of both NiMo and CoMo catalysts in
the same section is in some cases economically
justifed.
Q&A copy 12.indd 7 28/02/2014 11:12
so-called easy sulphurs, are more effectively desulphu-
rised via a direct sulphur abstraction route, and these
reactions are best catalysed by a CoMo containing cata-
lyst. Substituted DBTs, or hard sulphur, are more
effectively removed by hydrogenation of an aromatic
ring followed by C-S bond scission. This type of reac-
tion is more effcient over a NiMo containing catalyst.
The SmART system can therefore give better perfor-
mance than either CoMo or NiMo alone. The
signifcant advantage of the system is not only due to
the staged catalyst confguration but also to unique
catalyst formulations. The systems NiMo catalyst was
developed to promote the hydrogenation route for
HDS with partially desulphurised feed at a moderate
H
2
partial pressure.
An additional beneft of the NiMo component is the
enhanced HDN activity over an all CoMo system will
help to improve both product colour and colour
stability.
Detailed work in ART laboratories has elucidated the
mechanism of the staged system. Figure 1 shows that
the system removes easy sulphur as well as a CoMo
catalyst, removes hard sulphur as well as a NiMo cata-
lyst, and removes the transition species better than
either a CoMo or NiMo catalyst.
Another important advantage of the SmART system
concept is the effcient use of H
2
. Figure 2 illustrates
how the SmART system can be tailored to provide the
best balance of maximum HDS activity while minimis-
ing H
2
consumption.
The SmART system design is the culmination of an
extensive effort put towards understanding the chem-
istry and process conditions required for ultra low
sulphur fuels. ART has devoted signifcant resources to
designing the best ULSD catalysts for use in the
system. This effort has lead to the recent commerciali-
sation of ARTs new CoMo catalyst 425DX, and the
new NiMo catalyst, 545DX. These new technologies
capitalise on the extensive material science and catalyst
knowledge encompassed in the ART joint venture.
1 2 0
1 6 0
1 4 0
1 0 0
8 0
6 0
4 0
2 0
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r
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E a sy su lp h u r
1 3 1 7 6
M ix e d
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C o M o
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S m A R T
1 0 0
P
r
o
d
u
c
t

s
u
l
p
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p
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1 . 1 5
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e
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c
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A ll C o M o
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SmART Syst ems
A ll N iM o
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Figure 1 SmART gives highest conversion Figure 2 Optimising HDS and H
2
consumption
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clg.indd 1 26/02/2013 17:02
HCN and NOx control strategies
in the FCC
I
ncreasing environmental aware-
ness at a global level is driving
enforcement of more stringent
regulations to limit emissions of
sulphur and nitrogen containing
gases to the atmosphere.
NOx (mixed nitrogen oxides) and
SOx (mixed sulphur oxides) emis-
sions have been under scrutiny for
some time now, especially in North
America and Europe. More recently,
however, hydrogen cyanide (HCN)
emissions (present in FCC fue gas
at levels up to about 150ppm) have
come under scrutiny in the US and
some parts of Europe. Controlling
fue gas emissions of this new
species is an emerging challenge for
refners operating FCC units.
The origin of HCN in FCC fue
gas has been poorly understood and
public domain information very
limited. In this article we explain
our recent research on nitrogen
chemistry as it relates to the FCC
regenerator, covering the origin of
HCN and its relationship with other
nitrogen containing gases. We also
explain how modern FCC unit
designs geared for low NOx emis-
sions may unintentionally have been
trading these off against HCN and
ammonia emissions. Continuing
development of catalytic additives
for FCC regenerator fue gas emis-
sions control will help refners to
meet the emerging regulatory emis-
sion limits. We explain how to use a
combination of operating variables,
additives and regenerator design to
reduce emissions.
FCC NOx and SOx emissions
The FCC unit is a major conversion
unit present in many refneries
throughout the world. FCC units are
Results of research into emissions from the FCC, plus guidance on how to
obtain the minimum level of NOx
XUNHUA MO, BART DE GRAAF, CHARLES RADCLIFFE and PAUL DIDDAMS
Johnson Matthey, Process Technologies, Intercat
JM
Additives
highly fexible and able to upgrade
feeds comprising many components
ranging from light-sweet hydro-
treated VGO to heavy-sour residues,
and may include additional heavy
streams from other refnery units,
such as coker gas oils. Because of
the resilience of the process and
catalyst system, the majority of FCC
feedstocks contain many contami-
nants including metals (Ni, V, Cu,
Fe, Ca, Na, K) and heteroatoms
(sulphur, S and nitrogen, N).
The FCC converts low value, high
molecular weight (high boiling
point) hydrocarbon feeds to lighter,
more valuable products via cleavage
of C-C bonds (cracking). Typically,
5-6wt% of the feed is converted to
coke as a byproduct
of cracking. This is burned in
the FCC regenerator where the
heat of combustion is used to
provide the energy required to
vaporise and crack the feed (hence,
the FCC unit is said to be in heat
balance).
Metals accumulate on the catalyst
where they deactivate/poison the
catalyst or cause undesired side
reactions such as dehydrogenation
and additional coke and gas forma-
tion. Some contaminants in the feed
are transferred to the regenerator in
the coke. In this way, a portion of
the sulphur and nitrogen in the feed
is combusted in the regenerator.
The products of combustion of
sulphur and nitrogen in the FCC
regenerator include the gases SO
2
,
SO
3
, COS, H
2
S, N
2
, NO, N
2
O, NO
2
,
NH
3
and HCN, all which may
contribute to stack emissions at vari-
ous concentrations in the FCC fue
gas. The exact composition of these
gases in the fue gas depends upon
the detailed reaction conditions. A
simplifed reaction pathway for
nitrogen compounds is shown in
Figure 1.
In full burn FCC units (where
coke is combusted in an excess of
oxygen) the main species formed are
the most highly oxidised species:
SO
2
, SO
3
, N
2
and NO. However, in
partial burn FCC units (where the
coke is combusted under sub-stoi-
chiometric oxygen conditions) much
higher levels of the reduced S and
N species (COS, H
2
S, NH
3
, HCN)
are present in the fue gas as it
leaves the regenerator. In partial
burn units a controlled amount of
the carbon in the coke burned is
N O , N
2
O , N O
2
A ro m a tic N (c o k e )
A m in e s
(u n strip p e d p ro d u c ts)
N H
3
N
2
O
2
O
2
O
2
O
2
C H
H
2
O
N O x
HCN
2 C O +2 N O 2 C O
2
+N
2
is ve ry slo w u n d e r F C C c o n d itio n s
Figure 1 Regenerator nitrogen reactions
cat intercat.indd 1 28/02/2014 11:23
Investigation of coke combustion
Intercat
JM
used temperature
programmed oxidation (TPO) to
study coke combustion, to better
understand FCC regenerator chem-
istry. The TPO protocol involves
pre-heating a sample of coked cata-
lyst (spent catalyst) in an inert
atmosphere up to a chosen initial
temperature (for example, 150C),
then switching to the combustion
gas containing oxygen. (In more
detailed studies, additional selected
gases may also be included, for
instance CO
2
, CO, SO
2
, steam.). The
temperature is then ramped (for
instance at 10C/min) to 730C then
held there isothermally. The result-
ing combustion fue gases are
continuously analysed by an on-line
infrared detector and mass spec-
trometer. It is worth noting that the
nature of the coked catalysts has
signifcant effect on the emission
profles during TPO. The emission
profles are dependent on the types
of nitrogen species formed. These
depend on the nature of the nitro-
gen species in the feed, CCR,
contaminant metals, conversion and
stripping of the catalyst. The lab
TPO data shown in this article were
obtained using a spent catalyst
taken from a commercial FCC unit
(containing 1 wt% carbon, 0.1 wt%
sulphur and 395 ppm nitrogen), and
from a synthetic spent catalyst
prepared using a metals-free FCC
catalyst.
The frst nitrogen containing
species evolved (at the lowest
temperature in the TPO) is HCN
(see Figure 2). HCN production is
observed at low temperatures,
beginning at about 450C (780F). At
this low temperature the rate of
conversion of HCN to the thermo-
dynamically more stable NO or N
2
forms is slow, so the HCN survives
to be observed. NO does not begin
to be formed until the temperature
exceeds about 570C (1060F). After
this point, as the temperature is
increased the HCN concentration
declines while NO increases; HCN
conversion is fast enough that
further HCN formed is readily
converted into NO or nitrogen.
Despite being thermodynamically
unstable at this temperature N
2
O is
also observed at temperatures
combusted to CO rather than CO
2
in
order to decrease the heat produced
in the regenerator via coke combus-
tion. This allows the processing of
heavier, higher coke making feeds
within regenerator temperature
constraints. Most partial burn units
have a CO boiler downstream of the
regenerator in which CO is
converted to CO
2
to control CO
emissions and recover additional
heat of combustion for steam
production. The CO boiler also
converts reduced S and N species to
more highly oxidised forms, so the
result in both full burn and partial
burn with a CO boiler is that the
fue gas contaminants reaching the
stack are predominantly SOx (SO
2
,
SO
3
) and NOx (NO, N
2
O, NO
2
).
Other species are generally only
present at much lower concentra-
tions. Note that a partial burn unit
without a CO boiler will emit
substantial levels of the CO and
reduced S and N gaseous species
and there are actually still a number
of such FCC units being operated in
this way.
Nitrogen chemistry in the
FCC regenerator
FCC feedstocks contain many differ-
ent nitrogen compounds, generally
measured as total and basic nitro-
gen. Normally, 30-50% of the feed
nitrogen compounds are basic nitro-
gen species that strongly adsorb on
acid sites on the catalyst. This tightly
bound nitrogen is not removed in
the stripper and therefore carried
with the catalyst into the regenera-
tor where it is combusted as part of
the coke together with the carbon,
hydrogen and sulphur. As a rule of
thumb, about half of the feed total
nitrogen is combusted in the FCC
regenerator. See Table 1 for a typical
FCC nitrogen balance.
Coke composition primarily
depends on feed properties and
stripper effciency. Coke is
comprised of carbon-rich polycyclic
aromatic structures containing
heteroatoms and contaminant
metals as well as unstripped hydro-
carbon products (10-30% of coke can
be gasoline, diesel and fuel oil range
products that are not stripped from
the pores of the catalyst). Typically,
coke has a hydrogen content of 5-8
wt%, largely present in the
unstripped products. The concentra-
tion of nitrogen in coke is an order
of magnitude higher than in the
feed (about 50% of feed nitrogen
goes to coke compared to about 5%
of feed carbon).
Combustion of carbonaceous coke
and unstripped hydrocarbons in the
regenerator forms CO
2
, CO and
H
2
O. Sulphur in coke forms SO
2
,
SO
3
, COS and H
2
S, but nitrogen in
coke behaves very differently. When
oxygen reacts with carbon-rich coke,
much of the nitrogen is initially
converted to HCN; the same chem-
istry is observed in coal combustion.
At typical steady-state FCC regener-
ator bed temperatures (680-755C,
1255-1390F), HCN is thermody-
namically unstable and, given
suffcient time, all of the HCN
would be converted. Nitrogen
followed by NO are the most ther-
modynamically stable nitrogen
species under FCC regenerator
conditions, with the thermodynamic
equilibrium concentration of NO
being about 10 ppm in nitrogen.
However, the much higher levels of
HCN found in commercial FCC unit
fue gases clearly illustrates that
nitrogen reactions are kinetically
controlled and do not reach thermo-
dynamic equilibrium. HCN present
as a reactive intermediate can be
hydrolysed by steam in the regener-
ator to form NH
3
. Both HCN and
NH
3
can be readily oxidised to form
N
2
or NO, depending on regenera-
tor conditions and the presence of
combustion promoters which
catalyse these reactions. Previously,
the reaction of CO + NO was
thought to be one of the main driv-
ing forces for reducing NO. Our
work shows this reaction to play a
very minor role under FCC
conditions.
Product Nitrogen, wt%FF
Fuel gas NH
3
/HCN 5-15
Gasoline 1-5
LCO/diesel 10-20
HCO/bottoms 25-35
Coke 35-60
Typical nitrogen balance: wt% feed
nitrogen to FCC products
Table 1
around 650C, indicating that N
2
O
may also either be a reactive inter-
mediate in the formation of NO or a
byproduct of the reduction of NO.
When higher oxygen levels are
used in the combustion gas (for
example, 4 vol%) both the rate of
HCN formation and its subsequent
conversion is increased notably: the
frst traces of NO in fue gas appear
at a lower temperature, ~550C
(1020F).
These experiments show that
HCN is most readily formed at low
temperatures, especially where
oxygen concentrations are high,
while at higher temperatures HCN
becomes unstable and is readily
converted to NOx and nitrogen.
HCN formation and survival is
favoured at low temperatures. The
zones within the FCC regenerator
where these conditions occur are the
entry point for the cooler spent cata-
lyst (at about 500-550C, close to the
HCN maxima in the TPO experi-
ments) and the cold air at about
190C. As spent catalyst and air mix
with the hot catalyst in the bed their
temperatures increase and HCN
formation declines and is replaced
by combustion of nitrogen in coke
to NOx or N
2
. Some of the HCN
that was initially formed in the
cooler zones heats up in the regen-
erator (especially when passing up
through the bubbling catalyst bed)
and is converted to NOx or N
2
. Any
HCN surviving at the fue gas exit
did not have suffcient contact time
at elevated temperatures to be
converted.
This explains why HCN emissions
are highly dependent on regenerator
spent catalyst and air distributor
design (see Figure 3).
If spent catalyst is deposited on
the top of a poorly mixed catalyst
bed, where it takes more time to
heat up, it spends longer under
conditions ideal for HCN formation
and survival, resulting in higher
HCN levels in the fue gas.
If the spent catalyst enters the
lower part of a well mixed regenera-
tor catalyst bed, but far enough
above the air injection for it to have
already been heated to above
~650C, it will more rapidly heat up.
The time available for HCN forma-
tion is therefore minimised, and any
HCN formed has better contact with
the hot catalyst bed where it is more
likely to be converted. Large bubbles
can offer HCN an escape route; air
distribution should be optimised to
avoid large bubbles that spout gas
and catalyst into the dilute phase.
Note that conditions exist where
HCN in fue gas can be also reduced
by hydrolysis (reaction with steam).
Hydrolysis is an alternative, low
temperature destruction path where
HCN is converted to ammonia
(NH
3
), which may go on to be
oxidised to NO. The relative
amounts of HCN and NH
3
breaking
through will depend on many varia-
bles, such as metals on catalyst, type
of nitrogen in feed, and regenerator
design.
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
T
P
O

N
O
x

e
m
i
s
s
i
o
n
,

p
p
m
0
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 7 3 0
Temperature, C
N
2
O (8 % )
N O
2
N H
3
H C N (2 5 % )
N O (6 7 % )
Figure 2 TPO of spent catalyst regeneration without CO promoter (IR detector, 3% O
2
,
2.5% H
2
O in N
2
)
Scenario 1
Spent catalyst return on top
of the regenerator fluid bed
High amounts of non-oxidised
N-species (HCN, NH
3
) can be emitted
H ig h te m p e ra tu re
L o w o x yg e n c o n c e n tra tio n
M in im u m b a c k m ix in g o f g a s p h a se
L o w re sid e n c e tim e o f c o m b u stio n g a se s
Scenario 2
Spent catalyst return just above the air grid
Rapid coke combustion at low temperature
L o we st p o ssib le re g e n e ra to r te m p e ra tu re
S p e n t c a ta lyst 5 3 0 C 9 8 0 F )
A ir 2 0 0 C 4 0 0 F )
H ig h e st o x yg e n c o n c e n tra tio n
H ig h e st a m o u n ts o f H C N fo rm e d
Wh e re b u b b le s will b re a k th ro u g h th e b e d
su b sta n tia l H C N e m issio n is p o ssib le
Scenario 3
Spent catalyst return in the middle of the bed
Moderate coke combustion limits the
emission of non-oxidised N-species
M o d e ra te /h ig h te m p e ra tu re
L o w/m o d e ra te o x yg e n c o n c e n tra tio n
H ig h a m o u n t o f b a c k -m ix in g h e lp s
c o n ve rsio n o f H C N a n d N H
3
in to N
2
a n d N O
L o we st H C N e m issio n e x p e c te d
Figure 3 Effects of regenerator layout
Another important item to
consider is that mixing effects play a
major role in combustion kinetics.
Introduction of spent catalyst
into the centre of the bed without
proper radial mixing can be
much worse for emitting reduced
nitrogen species in ue gas
compared with spreading spent cata-
lyst onto the top of a bubbling bed.
4
The effect of CO promoters on HCN
Appropriate catalytic additives can
increase the rate of conversion of
HCN in the FCC regenerator. Both
platinum (Pt), and non-Pt promoters
efciently increase the rate of HCN
conversion, leading to lower concen-
tration in the ue gas.
The results of TPO experiments
shown in Figure 4 and Figure 5
compare spent catalyst combustion
with and without the addition of
various CO promoters.
The highest levels of HCN are
formed in the absence of CO
promoter. Adding either Pt or
non-Pt CO promoters decreases the
amount of HCN and NH
3
observed
by catalysing their conversion to
more oxidised forms. However, Pt
based promoters increase the NO
signicantly, while non-Pt CO
promoters increase NOx to a lesser
extent very much in line with
commercial experience using these
additives (see Table 2).
The use of non-Pt promoters is
now widely practised and has led to
signicant NOx reduction (typically
~70%) by eliminating this undesired
side effect of Pt promoters. In the
US, non-Pt promoters have almost
entirely replaced Pt based CO
promoters.
CO promoters help conversion of
CO to CO
2
within the regenerator
bed, reducing afterburning (combus-
tion of CO to CO
2
in the dilute
phase above the regenerator catalyst
bed leading to increased tempera-
tures). Figure 6 shows that this
activity is short-lived with a half life
measured in hours, meaning that
where afterburn is a problem CO
promoter has to be added semi-
continuously. Fresh and equilibrated
CO promoters have different effects
on FCC nitrogen chemistry.
Fresh Pt based and non-Pt CO
promoters both initially increase
3 0 0
4 0 0
3 5 0
2 5 0
2 0 0
1 5 0
1 0 0
5 0
T
P
O

N
O
x

e
m
i
s
s
i
o
n
,

p
p
m
0
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 7 3 0
Temperature, C
B
N
2
O (5 )
Wit h COP
H ig h e st N O
N O
2
N H
3
H C N (5 )
N O
3 0 0
4 0 0
3 5 0
2 5 0
2 0 0
1 5 0
1 0 0
5 0
T
P
O

N
O
x

e
m
i
s
s
i
o
n
,

p
p
m
0
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 7 3 0
Temperature, C
A
N
2
O (5 )
Wit hout addit ive
L o we st N O
H ig h e st H C N
N O
2
N H
3
H C N (5 )
N O
3 0 0
4 0 0
3 5 0
2 5 0
2 0 0
1 5 0
1 0 0
5 0
T
P
O

N
O
x

e
m
i
s
s
i
o
n
,

p
p
m
0
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 7 3 0
Temperature, C
C
N
2
O (5 )
Wit h COP-NP
L o we st H C N
N O
2
N H
3
H C N (5 )
N O
Figure 4 Impact of CO promoter on N-species selectivity in the TPO of spent catalyst
(IR detector, 2% O
2
in N
2
)
e
-1 2
2 e
-1 2
3 e
-1 2
4 e
-1 2
5 e
-1 2
H
C
N
,

M
S

r
e
s
p
o
n
s
e
0
1 5 0 2 5 0 3 5 0 4 5 0 5 5 0 6 5 0 7 5 0
Temperat ure, C
P t a d d itive d e a c t
C O P N P d e a c t
S p e n t c a t
Figure 5 Impact of CO promoter on N-species selectivity in TPO of spent catalyst
(mass spec.)
HCN emissions from their FCC
units. This is an update of the
process described by the author in
Reducing FCC unit NOx emissions,
which explains steps 1-5 in more
detail.
Step 1: determine unit operating
variable effects on NOx and HCN
The rst step to NOx/HCN
reduction is to thoroughly under-
FCCs, residual HCN is combusted
and the vast majority of the NOx is
produced in the CO boiler, so this
approach is not relevant to these
units.)
Steps to reduce FCC NOx and
HCN formation
There are a series of steps which can
be followed by reners faced with
requirements to reduce NOx and
NOx (Pt > non-Pt). However, NOx
production markedly differs after
aging.
As Pt and non-Pt CO promoters
age, the active metal sinters to form
large clusters hundreds of atoms in
diameter (see Figure 7). In Pt based
CO promoters, the Pt clusters
continue to drive conversion of
intermediates (HCN, NH
3
) to NOx
with selectivity towards making
NOx increasing with increasing age
(Pt particle size, see Figure 8). Aged
non-Pt promoters however exhibit a
very different effect: the activity for
NOx formation is short-lived, while
its activity for HCN conversion (to
nitrogen) remains for a long time
(see Table 3 and Table 4).
Metals and feed affect the selectiv-
ity of the ue gas nitrogen species.
With a synthetic spent catalyst
(steam deactivated, no metals
applied and using a standard VGO,
selectivities towards NH
3
and HCN
change compared with the commer-
cially obtained spent catalyst (see
Table 5). Where the commercially
obtained spent catalyst did not
show NH
3
in ue gas, the synthetic
spent catalyst shows NH
3
upon coke
oxidation. The pattern in ue gas
products that appears is very similar
to the commercially obtained spent
catalyst as both the Pt combustion
promoter as well as the non-Pt
combustion promoter effectively
destruct HCN. Again, the selectivity
towards NO is high over the Pt, low
over the non-Pt combustion
promoter. Note that the non-Pt
combustion promoter also exhibits a
higher efciency in NH
3
destruction
compared to the Pt combustion
promoter. This shows that both Pt
and non-Pt combustion promoters
can effectively oxidise reduced
nitrogen species, but the non-Pt
combustion promoter is more effec-
tive in these reactions than the Pt
combustion promoter and exhibits a
higher selectivity to nitrogen over
NO.
Reduction of renery NOx and
HCN emissions
With this improved understanding
of the chemistry, we will explain
some practical steps for reners to
minimise FCC regenerator NOx and
HCN emissions. (In partial burn
1 6 0
2 0 0
1 8 0
1 4 0
1 2 0
N
O
x
,

p
p
m
1 0 0
6 5
7 5
7 0
6 0
5 5
A
f
t
e
r
b
u
r
n
,

F
5 0
0 6 0 1 2 0 1 8 0 2 4 0 3 0 0
Ti me, mi nut es
C O o x id a tio n a c tivity d e a c tiva te s ra p id ly
I m m e d ia te sta b le N O x fo rm a tio n
Figure 6 CO promotion activity of Pt CO promoter has a shorter half life than NOx
production
Atom pairs
Single atoms
1nm
Fresh COP
COP in Ecat
150 nm
P t sin te rs a s th e a d d itive a g e s
I n fre sh C O P th e P t is h ig h ly
d isp e rse d m o stly a s sin g le
a to m s < < 1 n m
P t a to m s m ig ra te a n d c lu ste r
in to la rg e r p a rtic le s o n a g e in g
3 0
2 5
2 0
1 5
1 0
5
F
r
e
q
u
e
n
c
y
,

%
0
4 6 8 1 0 1 2 1 4 1 6 1 8 2 0 M o re
Si ze, nm
A P S 1 3 -1 4 n m
Figure 7 TEM study of CO promoters (fresh and e-cat)
w/o COP Pt-COP Non-Pt COP
N in coke, wt% 1.16 1.17 1.17
NOx in FG, ppmw 112 388 145
N in coke to NOx, % 24 79 29
Balance N in coke to N
2
, % 76 21 71
Impact of CO promoter type on FCC NOx formation: commercial FCC data
Table 2
therefore critical to minimise
additions (or better, to replace the Pt
CO promoter with a non-Pt
promoter).
Pre-blending CO promoter results
in a large excess of Pt usage for
most of the time. Any CO promoter
additions should be independent
from fresh catalyst to avoid exces-
sive use which will drive up NOx
formation.
Step 3: establish the minimum level
of platinum promoter additions
Shot dosing promoter causes only
small, short-term spikes in NOx
emissions. A strategy of either
manual application, or using an
additive loader, to dose promoter
only when required to suppress
spikes in afterburn will minimise Pt
in the inventory.
Having minimised the usage of
platinum promoter, the NOx and
HCN emissions can be reassessed. If
further reductions in NOx are
required proceed to Step 4.
Step 4: replace platinum promoter
with a non-platinum promoter such
as COP-NP
Numerous commercial trials of
COP-NP have demonstrated signif-
cant reductions in NOx emissions
when substituting platinum based
combustion promoters, while main-
taining equal afterburn control and
low CO emissions. Furthermore,
COP-NP reduces HCN emissions.
Step 5: try a NOx reduction additive
If NOx and HCN emissions are still
above the required level, then a
NOx reduction additive like
Intercat
JM
s NOxGetter can be used.
Step 6: regenerator modication
If after carrying out all of the above
steps NOx or HCN emissions are
still above target, then hardware
solutions are required to improve
the spent catalyst and air distribu-
tion within the regenerator.
This process to minimise NOx
emissions can be illustrated as a
fow chart (see Figure 9).

Conclusions
FCC regenerator nitrogen chemistry
is complex with a subtle interplay
between regenerator design and
FCC operation. It will also provide
a base line method to evaluate
improvements and demonstrate
progress to the regulators. Typical
variables are: excess oxygen, opti-
mise the use of Sb, optimise
regenerator bed levels.
Step 2: discontinue any pre-blended
promoter usage
While platinum promoter does
effectively control afterburn and
assists in HCN conversion, it is a
major factor in increasing NOx. It is
stand the existing regenerator
operation. Reducing FCC unit NOx
emissions explains the usefulness of
regression analysis for determining
the effect of major FCC operating
variables on regenerator NOx
emissions, and a similar approach
is needed to evaluate HCN
emissions.
The resulting analysis allows the
refner to assess how operating
variables can be adjusted to mini-
mise NOx and HCN emissions
while minimising the impact on
1 5 0
2 5 0
3 0 0
2 0 0
1 0 0
5 0
N
O
x
,

p
p
m
0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0
Days
P t C O P
C o m m e rc ia l F C C U
Tra n sitio n fro m P t C O P
to C O P -N P
N O x d ro p s b y 7 0 %
C O P -N P a d d itio n s b e g in
Figure 8 NOx emissions remain for a long time following discontinued use of Pt CO promoter

CO/CO
2
, NO, HCN, NH
3
, N
2
O, Total N
Vol/Vol Vol% Vol% Vol% Vol% rel. to w/o COP
w/o COP 0.52 39 12 - 0.3 1.0
Pt-COP 0.24 89 8 - 0.3 1.9
Non-Pt COP 0.23 84 6 - - 1.7
Impact of fresh CO promoter on N-species selectivity in the TPO of spent
catalyst (IR detector)
Table 3

CO/CO
2
, NO, HCN, NH
3
, N
2
O, Total N
w/o COP 0.52 39 12 - 0.3 1.0
Pt-COP 0.30 92 8 - - 2.0
Non-Pt COP 0.31 67 6 - - 1.4
Impact of deactivated CO promoter on N-species selectivity in TPO of spent

CO/CO
2
, NO, HCN, NH
3
, N
2
O, Total N
w/o COP 0.70 15 2.9 11 0.3 1.0
Pt-COP 0.15 93 0.1 7 - 3.4
Non-Pt COP 0.15 64 - 3 - 2.5
Impact of deactivated CO promoter on N-species selectivity in TPO of spent
Table 4
Table 5
cattec.indd 1 26/02/2013 16:59
Johnson Matthey. He holds a MSc in chemical
engineering from Twente University and a
PhD in heterogeneous catalysis and chemical
processes from University of Amsterdam.
Charles Radcliffe is a Technical Consultant,
FCC and Rening. He has more than 30 years
technical and managerial experience in the
rening, petrochemical and plastics industries,
and holds a BSc in chemical engineering from
Birmingham University and an MBA from The
Open University.
Paul Diddams is Vice President for FCC Additives
within Johnson Mattheys Reneries Division.
He has over 25 years experience in rening and
catalysis, and holds a BSc in chemistry from
Newcastle University and a PhD in physical
chemistry from Cambridge University.
NOXGETTER and COP-NP are trademarks of
Intercat
JM
.
References
1 Radcliffe C, Reducing FCC unit SOx
emissions, PTQ, Catalysis, 2008.
2 Mo X, de Graaf B, Diddams P, HCN emissions
in uid catalytic cracking, PTQ, Q2 2013.
3 Diddams P A, AFPM Annual Meeting, San
Antonio, 2013 AM-13-19.
4 Wilson J W, AFPM Annual Meeting, San
Antonio, 2003, AM-03-44.
Xunhua Mo is a Catalyst Development
Scientist with Johnson Matthey Technology
Center in Savannah, USA. She holds a PhD in
chemistry from Clemson University.
Bart de Graaf is FCC R&D Director with
coked catalyst. A substantial part of
the nitrogen from the feed is left in
the coke and during its combustion
HCN is readily formed at low
temperatures in the presence of
oxygen, as well as nitrogen and
NOx. FCC regenerator conditions
generally favour conversion of HCN
to nitrogen or NO.
Combustion promoters help
reduce HCN by catalysing its
conversion to nitrogen or NO. Pt
combustion promoters prefer to do
this by creating mainly NO, whereas
non-Pt promoters prefer to convert
HCN to nitrogen.
Move to full burn or
hardware changes
Remove promoter and
add separately
Minimise promoter
additions to reduce
NOx/HCN
Determine what operating variables
affect NOx/HCN in your unit data
with Intercat
JM
s help
Operate to minimise NOx/HCN
within unit operating constraints
Start here...
Using Pt
Full burn regen?
NOx/HCN
emissions under
target?
Using
pre-promoted
catalyst?
Use non-Pt promoter
NOx/HCN
emissions under
target?
NOx/HCN
emissions under
target?
Trial NOXGetter
Improve catalyst/air
distribution
SUCCESS
NOx/HCN
emissions under
target?
NOx/HCN
emissions under
target?
No No Yes
Yes
Yes
Yes
Yes
No
No
No
No
Yes
No
Yes
Yes
No
Figure 9 Process to minimise NOx emissions
Ai m for More Di esel , Better Di esel
ExxonMobils MIDW
TM
*

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Increased sulfur removal and reduced naphtha yields
Proprietary catalyst** isomerizes waxy n-paraffns in
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2
S, ammonia, and organic S and N
Stand-alone or integrate with others
* MIDW is a trademark of ExxonMobil Research and Engineering Company
** Available from ExxonMobil Catalyst Technologies LLC
ExxonMobil Research and Engineering
Companys MIDW* Technology
Improves Product Yield and Quality
3225 Gallows Road, Fairfax, Virginia 22037-0001, USA
www.exxonmobil.com/refningtechnologies +1-703-846-2568 fax +1-703-846-3872 tsl.email@exxonmobil.com
exxon.indd 1 28/02/2014 10:25
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Capturing maximum value with tight oil
feeds in the FCC
T
ight oil production has
changed the refning land-
scape for major portions of
the US and market forecasts show
dramatic changes in the interna-
tional refning community as tight
oil production rates continue to
ramp up. According to Hart Energy
estimates, tight oil production will
represent 46% of domestic crude oil
production in 2020.
1
While tight oil
is of higher quality, many US refn-
eries have been confgured to
process the increasingly heavy sour
crudes previously projected to be
available. Fluidised catalytic crack-
ers (FCC) at refneries processing
tight oil have seen serious operat-
ing changes; choice of catalyst and
overall catalyst management strat-
egy is a critical factor in achieving
successful optimisation. BASF is the
market leader in supplying FCC
catalysts to refneries processing
tight oil. In general, tight oil FCC
feeds are light, paraffnic, have
different contaminants, and are low
in vacuum gasoil (VGO) and resid-
uum content. Typical challenges for
FCCs processing these crudes
include high amounts of liquefed
petroleum gas (LPG), maintaining
stable heat balance, higher alkali
metals, increased iron loadings and
reduced feed rates. This article will
illustrate how BASF is helping
refners to capture maximum value
with tight oil feeds through operat-
ing strategies, innovative catalysts
and technical service. BASF has a
diverse catalyst portfolio providing
the fexibility required to help solve
these problems including high
activity, optimum delta coke and
high iron tolerance.
Tight oil quality varies between
FCCs processing tight oil feeds require catalyst choices to deal with higher
conversion, heat balance concerns, and higher sodium, calcium and iron
ALEXIS SHACKLEFORD
BASF Catalysts
oil felds and has been shown to be
highly variable even from the same
feld. Batch shipping these crudes
by truck and rail increases this vari-
ability. Given this, there are many
general properties which tight oil
crudes exhibit. Tight oil formations
are relatively young, light, low boil-
ing point, low in Concarbon, have
high naphtha and distillate yields,
lower vacuum gasoil cuts, contain
almost no vacuum resid, have low
contaminants of sulphur, nitrogen,
nickel and vanadium but have
higher sodium, calcium, potassium
and iron. The high naphtha and
distillate yields can choke the crude
column, limiting crude rates. Low
sulphur will reduce the sulphur
load across the refnery, thus lower-
ing the sulphur plant loads. Due to
the high naphtha yield, which is
more paraffnic, maintaining the
octane balance can become diffcult,
requiring the need to maximise
alkylation and reforming, and plac-
ing higher emphasis on FCC
gasoline octane. With the low resid
content of the crude, refners may
consider shutting down the resid
processing unit and feeding the
resid directly to the FCC. Crude
compatibility also needs to be
addressed when blending the
light/sweet tight oil crudes with
heavy/sour crudes, creating a
dumbbell feed that does not act as
a homogeneous mixture, resulting
in asphaltene precipitation.
Processing tight oil in the FCC
brings benefts and challenges to
refners. The VGO cut of tight oil is
typically light, low carbon produc-
ing, and low in contaminant
sulphur, nitrogen, nickel and vana-
dium. Table 1 shows the VGO cut of
two tight oils compared to West
Texas Intermediate (WTI) and Maya.
The resid cut of tight oils shows the
same trend in properties as the VGO
cut, including being light and low
carbon producing. The light, low
boiling point feed is easily converted
to lighter products. The lower
sulphur and nitrogen in the feed
reduces gasoline sulphur and fue
gas NOx and SOx, making it easier
to meet regulations. With less nickel
and vanadium, hydrogen and coke
are lower. However, high conver-
sion and high LPG yield may limit
the gas plants throughput and thus
the FCC rate. The lower coke
making tendency of the feed can
constrain the unit on heat balance
and catalyst circulation.
VGO cut properties TX Shale Bakken Core WTI Maya Blend
API gravity 31.9 24.5 26.3 21
Sulphur, wt% 0.18 0.27 0.46 2.05
Acidity, mg KOH/g 0.049 0.053 0.095 0.085
Nitrogen, wt% 0.01 0.11 0.13 0.18
Refractive index, 67C 1.4588 1.4824 1.4759 1.498
Nickel, ppm 0.09 0.47 0 0.64
Vanadium, ppm 0.08 0.14 0 4.48
Concarbon, wt% 0.03 0.68 0.01 0.47
Properties of VGO cut from different crude sources by KBC
Table 1
basf cat.indd 1 28/02/2014 11:52
sabin.indd 1 27/02/2013 15:01
include higher e-cat activity
through higher additions, higher
rare earth (REO) content, or chang-
ing to a less coke selective catalyst.
If the unit cannot maintain heat
balance, some less desirable options
to investigate are turning on the air
pre-heater, adding torch oil and
reducing dispersion or stripping
steam. The air pre-heater and air
grid designs need to be reviewed to
avoid damage when operating
outside of start-up. Adding torch
oil and reducing dispersion or
stripping steam cause the negative
impacts of higher catalyst deactiva-
tion rates and burning higher value
products over coke. Another
concern with low regenerator bed
temperatures is the unit may
become circulation limited due to
slide valve pressure drop. To
reduce catalyst circulation, increase
the feed pre-heat temperature
While traditional contaminants
are low, tight oil crudes can contain
high iron, sodium and calcium,
requiring higher catalyst addition
rates. Iron in FCC feed in particular
is a concern to many refners.
2
Iron
deposits on the outside of the cata-
lyst forming iron nodules which
are spike-like protrusions on the
surface of the catalyst. Figure 1
shows a BASF equilibrium catalyst
(e-cat) having 1.5 wt% iron from
processing tight oil. Iron acts as a
mild dehydrogenation catalyst,
increasing hydrogen and coke, and
can act as a CO promoter (which
can be a problem in partial burn
units). The iron nodules reduce the
e-cats apparent bulk density and,
at very high levels, can cause pore
mouth plugging. BASF catalysts
such as the DMS and Prox-SMZ
platforms
3,4
have high porosity,
giving excellent tolerance to pore
mouth plugging due to iron. Figure
2 shows a histogram of all e-cats
BASF analyses across the globe.
The BASF units are highlighted in
red, showing how BASF supplies
the majority of high iron (over 0.9
wt% iron on e-cat) FCC units.
Sodium is an alkali metal which
neutralises the catalysts acid crack-
ing sites. BASF has some of the
lowest fresh sodium catalyst in the
industry, giving them excellent
sodium tolerance. Figure 3 is a
histogram showing how BASF has
the majority of the low sodium
e-cats. Abnormal contaminants seen
in tight oil feeds include phospho-
rus, lead and barium but these are
at low levels and have no discerni-
ble effects on FCC yields or catalyst
selectivity.
Heat balance is normally the
main challenge for refneries
processing tight oil. Low coke
producing feeds cause low regener-
ator temperatures and result in
catalyst circulation constraints.
With lower coke yield, ensure the
air blower is rated for the lower air
requirement and the pressure drop
across the air grid is maintained.
Minimum regenerator temperature
is set by maintaining effcient coke
burn, typically 1250-1260F (677-
682C). Operating moves to
increase bed temperature include
using a CO promoter to reduce
afterburn and heat up the bed,
reducing partial burn or going into
full burn, increasing feed pre-heat
and using oxygen injection.
Increasing delta coke through
increasing HCO/slurry recycle
(nozzle erosion may be a concern),
lowering the FCC feed hydrotreater
severity (if an option), and feeding
more resid to the FCC will increase
bed temperatures as well. Catalyst
solutions to increase delta coke

Figure 1 SEM micrograph of an e-cat taken
from a unit processing tight oil showing
iron nodules
3 0
4 0
3 5
2 5
2 0
1 5
1 0
5
P
r
o
p
o
r
t
i
o
n

o
f

a
l
l

u
n
i
t
s
,

%
0
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
0
0 -0 . 4 0 . 4 -0 . 5 0 . 5 -0 . 6 0 . 6 -0 . 7 0 . 7 -0 . 8 0 . 8 -0 . 9 0 . 9 +
Iron, wt %
B A S F
A ll d a ta
Figure 2 Histogram of e-cat iron ranges for all e-cat analysed in Q2 2013 by BASF
3 0
4 0
4 5
3 5
2 5
2 0
1 5
1 0
5 P
r
o
p
o
r
t
i
o
n

o
f

a
l
l

u
n
i
t
s
,

%
0
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
0
< 0 . 1 0 . 1 -0 . 2 0 . 2 -0 . 3 0 . 3 -0 . 4 0 . 4 -0 . 5 0 . 5 -0 . 6 0 . 6 +
Sodi um, wt %
B A S F
A ll d a ta
Figure 3 Histogram of e-cat sodium ranges for all e-cat analysed in Q2 2013 by BASF
basf cat.indd 2 03/03/2014 15:47
across the air grid is maintained.
Minimum regenerator temperature
is set by maintaining effcient coke
burn, typically 1250-1260F (677-
682C). Operating moves to
increase bed temperature include
using a CO promoter to reduce
afterburn and heat up the bed,
reducing partial burn or going into
full burn, increasing feed pre-heat
and using oxygen injection.
Increasing delta coke through
increasing HCO/slurry recycle
(nozzle erosion may be a concern),
lowering the FCC feed hydrotreater
severity (if an option), and feeding
more resid to the FCC will increase
bed temperatures as well. Catalyst
solutions to increase delta coke
include higher e-cat activity
through higher additions, higher
rare earth (REO) content, or chang-
ing to a less coke selective catalyst.
If the unit cannot maintain heat
balance, some less desirable options
to investigate are turning on the air
pre-heater, adding torch oil and
reducing dispersion or stripping
steam. The air pre-heater and air
grid designs need to be reviewed to
avoid damage when operating
outside of start-up. Adding torch
oil and reducing dispersion or
stripping steam cause the negative
impacts of higher catalyst deactiva-
tion rates and burning higher value
products over coke. Another
concern with low regenerator bed
temperatures is the unit may
become circulation limited due to
slide valve pressure drop. To
reduce catalyst circulation, increase
the feed pre-heat temperature
While traditional contaminants
are low, tight oil crudes can contain
high iron, sodium and calcium,
requiring higher catalyst addition
rates. Iron in FCC feed in particular
is a concern to many refners.
2
Iron
deposits on the outside of the cata-
lyst forming iron nodules which
are spike-like protrusions on the
surface of the catalyst. Figure 1
shows a BASF equilibrium catalyst
(e-cat) having 1.5 wt% iron from
processing tight oil. Iron acts as a
mild dehydrogenation catalyst,
increasing hydrogen and coke, and
can act as a CO promoter (which
can be a problem in partial burn
units). The iron nodules reduce the
e-cats apparent bulk density and,
at very high levels, can cause pore
mouth plugging. BASF catalysts
such as the DMS and Prox-SMZ
platforms
3,4
have high porosity,
giving excellent tolerance to pore
mouth plugging due to iron. Figure
2 shows a histogram of all e-cats
BASF analyses across the globe.
The BASF units are highlighted in
red, showing how BASF supplies
the majority of high iron (over 0.9
wt% iron on e-cat) FCC units.
Sodium is an alkali metal which
neutralises the catalysts acid crack-
ing sites. BASF has some of the
lowest fresh sodium catalyst in the
industry, giving them excellent
sodium tolerance. Figure 3 is a
histogram showing how BASF has
the majority of the low sodium
e-cats. Abnormal contaminants seen
in tight oil feeds include phospho-
rus, lead and barium but these are
at low levels and have no discerni-
ble effects on FCC yields or catalyst
selectivity.
Heat balance is normally the
main challenge for refneries
processing tight oil. Low coke
producing feeds cause low regener-
ator temperatures and result in
catalyst circulation constraints.
With lower coke yield, ensure the
air blower is rated for the lower air
requirement and the pressure drop

Figure 1 SEM micrograph of an e-cat taken
from a unit processing tight oil showing
iron nodules
3 0
4 0
3 5
2 5
2 0
1 5
1 0
5
P
r
o
p
o
r
t
i
o
n

o
f

a
l
l

u
n
i
t
s
,

%
0
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
0
0 -0 . 4 0 . 4 -0 . 5 0 . 5 -0 . 6 0 . 6 -0 . 7 0 . 7 -0 . 8 0 . 8 -0 . 9 0 . 9 +
Iron, wt %
B A S F
A ll d a ta
Figure 2 Histogram of e-cat iron ranges for all e-cat analysed in Q2 2013 by BASF
3 0
4 0
4 5
3 5
2 5
2 0
1 5
1 0
5 P
r
o
p
o
r
t
i
o
n

o
f

a
l
l

u
n
i
t
s
,

%
0
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
0
< 0 . 1 0 . 1 -0 . 2 0 . 2 -0 . 3 0 . 3 -0 . 4 0 . 4 -0 . 5 0 . 5 -0 . 6 0 . 6 +
Sodi um, wt %
B A S F
A ll d a ta
Figure 3 Histogram of e-cat sodium ranges for all e-cat analysed in Q2 2013 by BASF
basf cat.indd 2 28/02/2014 11:52
which has the added beneft of
increasing the liquid yield due to
less coke production. If the unit has
a fuel gas fred heater, operating at
higher pre-heat temperatures also
has the economic beneft of burning
lower cost natural gas over burning
coke. Changes in catalyst bed
heights may also provide small
benefts. A long term option is to
change out the slide valve port size
to remove the slide valve pressure
drop constraint.
Due to the paraffnic nature of
tight oils, they produce low octane
straight run naphtha and low
octane naphtha from the FCC.
Catalysis options include reformu-
lating to a lower REO catalyst
which increases the gasoline octane
but offsets the heat balance. Also,
consider using ZSM-5 to increase
the gasoline octane up to the wet
gas compressor limit.
The slurry system may be another
challenge for refners. Processing
incompatible crudes can result in
slurry exchanger fouling due to
asphaltene precipitation. Low
slurry make due to high conversion
results in higher ash content, very
high residence time in the bottom
of the main fractionator, and low
slurry velocity; all of which can
result in fouling and line settling.
The infuence of tight oil on the
FCC will be different, depending
on the operating strategy of the
refner. Three industry examples
follow the different ways in which
tight oil feeds impacted operation
and how BASF catalyst technolo-
gies were applied.
The frst example is a unit
processing unhydrotreated VGO
and going to 100% Eagle Ford with
BASF NaphthaMax catalyst. The
feed gravity shows a large increase
from 22 to 28 API (see Figure 4).
Feed Concarbon and nitrogen
decreased, while sulphur increased.
Both nickel and vanadium
decreased by half. Sodium
increased from essentially no addi-
tive sodium to 0.1 wt% additive
sodium on the e-cat (see Figure 5).
The e-cat iron also increased from
0.7 wt% to 0.8 wt% (see Figure 6).
With the higher sodium and iron,
the BASF NaphthaMax catalyst
continued to provide high activity
2 6
3 0
2 9
2 8
2 7
2 5
2 4
2 3
2 2
2 1
F
e
e
d

A
P
I
2 0
Figure 4 Tight oil resulting in increased feed API for a VGO unit
0 . 3 5
0 . 3 0
0 . 2 5
0 . 2 0
E
-
c
a
t

s
o
d
i
u
m
,

w
t
%
0
Figure 5 Tight oil resulting in increased e-cat sodium for a VGO unit
0 . 8 0
0 . 9 0
0 . 8 5
0 . 7 0
0 . 6 5
E
-
c
a
t

i
r
o
n
,

w
t
%
0 . 6 0
Figure 6 Tight oil resulting in increased e-cat iron for a VGO unit
1 5
2 5
2 0
1 0
5
S
l
u
r
r
y

r
e
c
y
c
l
e
,

%
0
Figure 7 Tight oil resulting in increased slurry recycle to maintain heat balance for a
VGO unit
basf cat.indd 3 28/02/2014 11:52
and high iron tolerance. The lower
coke making properties of the feed
decreased regenerator temperature,
and slurry recycle was increased to
maintain the bed temperature (see
Figure 7). Conversion on the unit
increased an impressive 11 vol%
with the tight oil feed (see Figure 8).
The LPG increased signifcantly
from 24 vol% to 30 vol%. With the
more paraffnic feed, the gasoline
RON decreased 1.5 numbers.
The second example concerns a
refnery processing 70% hydro-
treated VGO which transitioned
80% of the feed to Eagle Ford. The
refnery uses BASFs NaphthaMax
II catalyst. The impact of tight oil is
less on the hydrotreated feed unit
as the hydrotreater conditions are
also adjusted, thus modulating the
impact (see Table 2). Feed gravity
increased 0.7 numbers, and feed
contaminants stayed relatively
constant. Conversion increased
2 vol% with 1 vol% increase in
liquid yield. To maintain regenera-
tor dense bed temperature, pre-heat
was increased, lowering the coke
yield and contributing to the liquid
yield increase. The refnery stopped
ZSM-5 addition and yet LPG
increased by 0.9 vol%. Throughout
the change, the catalyst continued
to give high performance and
deliver value to the refnery.
The last example concerns a unit
processing Bakken crude. Prior to
Bakken, the FCC processed only
VGO. However, the Bakken crudes
VGO yield is relatively low, leaving
extra FCC capacity. To take advan-
tage of the extra capacity, the
refner decided to send resid to the
FCC, which improved the plants
economics. Observed changes
include concarbon increasing from
zero to 1 wt%, nickel and vana-
dium doubling, and iron on the
Operation Base Change
Feed gravity, API 26.6 +0.7
Feed sulphur, wt% 0.5 +0.1
Feed nitrogen, ppmw 960 -90
Feed Concarbon, wt% 0.16 -
Pre-heat temperature, F 625 +43
Reactor temperature, F 965 +3
Cat to oil ratio, wt/wt 5.8 -0.2
Dense temperature, F 1270 +3
Catalyst addition, tons/day Base -
ZSM-5 additions Yes (5%) No
Equilibrium catalyst Base Change
E-cat FACT, wt% 77 -
Ni + V, ppm 1500 +50
Fe, wt% 0.62 -
Na, wt% 0.19 -0.01
Normalised yields Base Change
Conversion, vol% 80 +2.0
Dry gas, wt% 1.8 -0.1
C
3
=, vol% 8.4 +0.4
LPG, vol% 27.7 +0.9
Gasoline, vol% 63.6 +1.9
LCO, vol% 15.3 -1.7
Slurry, vol% 4.8 -0.3
Coke, wt% 4.10 -0.05
Total liquid yield, vol% 111.3 +0.9
Yield shifts of a unit processing hydrotreated VGO tight oil
Table 2
8 5
9 0
8 0
7 5
C
o
n
v
e
r
s
i
o
n
,

w
t
%
7 0
Figure 8 Tight oil resulting in higher conversion for a VGO unit
1 . 5
2 . 0
1 . 0
0 . 5
F
e
e
d

C
C
R
,

w
t
%
0
Figure 9 Feed CCR increase due to inclusion of resid when processing tight oil
There are several
operating moves which
reners processing
tight oil feeds can
make to maximise
value from the FCC
basf cat.indd 4 03/03/2014 11:25
choose
wisely.
cricatalyst.com
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.
cri.indd 1 28/02/2014 10:24
close to 200 FCCs around the
world, with the three cases high-
lighted. Case 1 shows a large
improvement in both gravity
(increasing from 22 to 28API) and
conversion (increasing from 75 to
86 vol%). Case 2 shows a milder
response of higher gravity and
conversion due to the feed hydro-
treater dampening the response.
Case 3 goes in the opposite direc-
tion with poorer feed quality and
lower conversion due to the deci-
sion to process resid, which
improved the overall economics of
the refnery. These three cases show
three very different impacts of how
tight oil can be processed.
Depending on how the refnery
chooses to operate with tight oil
feed, there is a unique catalyst solu-
tion for each situation.
Based on typical Gulf Coast
economics, there are several operat-
ing moves which refners
processing tight oil feeds can make
to maximise value from the FCC.
First, run in maximum conversion
over maximum LCO mode. Tight
oils in general have more straight
run diesel that further reduces the
need to maximise LCO from the
FCC. Maximise the LPG olefnicity
as propylene and butylenes
continue to be valuable, while LPG
saturates are low value. Increase
LPG olefnicity by balancing cata-
lyst activity, REO level and riser
outlet temperature. Also consider
using ZSM-5 up to the gas plant
capacity limit. If short on gasoline
octane, lowering the REO on cata-
lyst and using ZSM-5 will improve
economics despite the gasoline loss,
but the increase in LPG may not be
feasible. Maximising feed pre-heat
will help with heat balance and
circulation limits. If the unit has a
furnace, burning natural gas is
more economical than making coke
to keep the FCC in heat balance.
Proactive catalyst management
continues to be important due to
the variability of the feed.
Conclusion
In summary, tight oil production
will continue providing economic
feedstocks to US refneries; market
forecasts show dramatic changes in
the international refning commu-
for enhanced metals tolerance and
resid upgrading.
5
The trial is still
ongoing, with the Fortress catalyst
providing the refnery excellent
metals tolerance and activity reten-
tion with this challenging feed.
The changes each refnery experi-
enced due to processing tight oil
are summarised in Figure 13. The
fgure shows BASF benchmarking
of conversion vs feed gravity for
e-cat increasing from 0.6 wt% to
over 1 wt% (see Figures 9, 10 and
11). The unit also saw extremely
high levels of sodium in the feed
(see Figure 12). The average sodium
level of 0.7 wt% on e-cat is in the
top 1% of all units BASF analyses.
To give the refner improved opera-
tion, the unit changed catalyst from
BASFs VGO NaphthaMax catalyst
to the BASF resid catalyst Fortress
3 0 0 0
4 0 0 0
2 0 0 0
1 0 0 0
E
-
c
a
t
,

p
p
m
0
N I
V
Figure 10 E-cat nickel and vanadium increase due to inclusion of resid when processing
tight oil
0 . 8 5
1 . 0 5
1 . 1 5
0 . 9 5
0 . 7 5
0 . 6 5
E
-
c
a
t

i
r
o
n
,

w
t
%
0 . 5 5
Figure 11 E-cat iron increase due to inclusion of resid when processing tight oil
0 . 6
1 . 0
0 . 9
0 . 8
0 . 7
0 . 5
0 . 4
0 . 3
0 . 2
0 . 1
E
-
c
a
t

s
o
d
i
u
m
,

w
t
%
0
Figure 12 E-cat sodium increase due to inclusion of resid when processing tight oil
basf cat.indd 5 28/02/2014 11:52
technology, NPRA AM-11-01.
Alexis Shackleford is a Technology Specialist
with BASF Rening Catalysts division in
Houston, Texas where she is involved with
new product development, new product
introductions and catalyst testing. She was
previously a process engineer working with
renery process units and holds a BSChE from
Michigan State University.
2 Wieland W S, Chung D, Simulation of iron
contamination, Hydrocarbon Engineering, Mar
2002.
3 McLean J, et al, Distributed matrix structures
a technology platform for advance FCC
catalyst solutions, NPRA AM-03-38.
4 Kraus M, et al, The stamina test, Hydrocarbon
Engineering, Sept 2010.
5 McLean J, et al, Multi-stage reaction
catalysts: a breakthrough innovation in FCC
nity. FCCs transitioning to tight oil
feed are generally experiencing
higher conversion, heat balance
concerns, higher sodium, higher
calcium and higher iron. Increased
LPG yields may limit the refnerys
gas plant, and gasoline octane can
be short. FCC catalyst technology
and service must be fexible to meet
the challenging feed quality and
operating conditions associated
with the crude. A variety of BASF
catalysts are being used in tight
oil applications; they include
NaphthaMax, NaphthaMax II,
NaphthaMax III, HDXtra, Stamina,
PetroMax, Endurance, Flex-Tec,
and Fortress, showing that there is
no one size fts all catalyst
solution.
NaphthaMax, NaphthaMax II, NaphthaMax
III, HDXtra, Stamina, PetroMax, Endurance,
Flex-Tec, and Fortress are trademarks of BASF
Catalysts.
References
1 P Jain, Higgins T, Naphthas future, Fuel, Dec
2013.
1 7 1 9 2 1 2 3 2 5 2 7 2 9 3 1 3 3 3 5
Feed gravi t y, API
8 0
9 0
9 5
8 5
7 5
7 0
6 5
6 0
5 5
C
o
n
v
e
r
s
i
o
n
,

v
o
l
%
5 0
C a se 3 : M ild re sid .
C a se 1 : VG O
C a se 2 : H I VG O
Figure 13 BASF benchmarking of FCCs from around the world: conversion vs feed gravity
showing the operational changes due to tight oil for three cases
Readers can download technical articles and other
information from over 40 categories.
Find relevant industry events worldwide.
Read news items focusing on contracts, company
news and new products.
For more articles relating to catalysts and additives, go to www.DigitalRening.com
dig ref half page ad copy.indd 1 01/03/2014 08:20
basf cat.indd 6 01/03/2014 08:21
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Maximising distillate while
minimising bottoms
T
he refning industry, espe-
cially in the US, has
undergone signifcant changes
during the last 5-10 years. Crude oil
prices have gone from about $30/
bbl to over $140/bbl, back down to
$35/bbl, and have recently hovered
around $100/bbl.
The primary transportation fuels,
gasoline, diesel and jet fuel,
currently account for over 80% of
US refnery output. Achieving these
high yields requires converting
heavy fuel oil into lighter products.
For the last 50 years, the refning
industry has relied on the fuid
catalytic cracking (FCC) process as
the primary conversion unit in the
refnery. Over 90% of refneries in
the US include an FCC unit. The
FCC unit converts heavy fuel oils
into more desirable lighter products
such as distillate and gasoline
blend stocks, alkylation feed, LPG
and the less desirable light gases
and coke. Until recently, most FCC
units were operated to maximise
gasoline production; however, that
is changing because of shifting
demand for transportation fuels.
Gasoline consumption peaked in
2007 and has continued to decline
since then (see Figure 1).
Continuing improvements in
vehicle fuel effciency and the
imposition of greenhouse gas
(GHG) emission limits from light
duty vehicles will continue to
reduce gasoline demand. Average
fuel economy requirements for US
light duty vehicles are expected to
increase from 30.1 miles per gallon
in 2012 to an equivalent of 35.5
mpg in 2016 and 54.5 mpg in 2025,
based on required reductions in
vehicle GHG emissions.
1
A recent
An FCC catalyst with reduced resistance to diffusion raises diesel output without
the traditional bottoms penalty
ALLEN HANSEN, ADRIAN HUMPHRIES, STEPHEN MCGOVERN and BARRY SPERONELLO
Rive Technology, Inc
National Research Council report
2
concluded that it is feasible to
reduce light duty vehicle fuel
consumption to 20% of 2005 levels
by 2050. Distillate consumption
dipped with the 2008 recession, but
has been slightly increasing since
then.
In addition to the changing
demand structure, the relative
prices of gasoline and diesel fuel in
the US have also changed in recent
years (see Figure 2). Until August
2004, monthly average wholesale
prices for refner gasoline had been
higher than diesel prices 95% of the
6 0 0 0
1 0 0 0 0
9 0 0 0
1 2 0 0 0
1 1 0 0 0
8 0 0 0
7 0 0 0
5 0 0 0
4 0 0 0
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1 0 0 0 U
.
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.

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2
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D istilla te fu e l o il
F in ish e d m o to r g a so lin e
Figure 1 US product consumption data
Source: Energy Information Administration, www.eia.gov
J
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1
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Figure 2 Relative gasoline and distillate wholesale prices (Energy Information Administration)
cat rive.indd 1 28/02/2014 11:57
reduction in total transportation
fuel yield. Increasing the matrix
activity and reducing the zeolite
content of the catalyst will also
improve overall distillate selectiv-
ity, but generally is accompanied
by an increase in coke selectivity.
Beyond the catalytic opportunities
described above, overcoming the
diffusion limitations of todays cata-
lysts can open the door to enhanced
LCO selectivity while minimising
any trade-offs. The conversion of
large VGO and resid molecules to
LCO, gasoline and gases is usually
modelled as a series of parallel and
series reactions, such as the network
shown in Figure 3, as proposed by
numerous researchers such as
Heydari et al.
3
All light products
can be formed directly from the
larger, heavy molecules through the
parallel reactions, but the series
pathways are also signicant. The
cracking reactions are usually
considered as rst order in the reac-
tant. Series, rst order reactions
usually result in a maximum of the
yield of the reaction intermediates
as feed conversion increases. This is
true of the FCC process. As conver-
sion is increased, LCO, then
gasoline, then LPG, all reach a
maximum yield and then decline as
conversion is increased.
Although the reactions are
modelled as simple rst order reac-
tions, the rate constants are actually
lumped parameters that include
other physical processes such as the
diffusion of the feed and product
molecules into and out of the cata-
lyst. In rapid conversion processes
like FCC, these inter- and intra-par-
ticle diffusion transport rates can be
the controlling steps in determining
the overall rate of reaction and
overall product selectivity in a
series reaction network. Catalyst
technologies that improve inter-
and intra-particle diffusion
transport rates can therefore be a
key component of an LCO maximi-
sation strategy.
Advantage of Molecular Highway
technology
For the last 40 years, essentially all
modern FCC catalysts have used
faujasite (Y zeolite) as the primary,
active cracking component in the
time. Since then, monthly average
wholesale prices for rener diesel
have been higher than gasoline
almost 75% of the time. Diesel
prices have been higher than gaso-
line in all but two of the last 36
months. This is a dramatic reversal
in the relative historical prices of
gasoline and diesel.

Reners reaction
Reners have been gradually shift-
ing their operations to meet this
changing demand and price struc-
ture, increasing distillate production
at the expense of gasoline. The FCC
unit is a major gasoline producer in
the renery. Many reners have
shifted their FCC operations to
distillate mode, at least during
part of the year, to help meet this
changing demand structure.
There are several operational
changes that reners can make to
their FCC operations in order to
increase distillate production at the
expense of gasoline. These include:
Minimising diesel fractions in the
FCC feed
Changing the cut point between
gasoline and light cycle oil (LCO)
products
Reducing cracking severity by
increasing feed temperature, lower-
ing riser outlet temperature, or
lowering catalyst activity
Changing the FCC catalyst to a
more distillate selective catalyst
(lower zeolite/matrix ratio).
The rst three items are opera-
tional changes that any rener can
implement. Removing diesel frac-
tions from the feed eliminates the
cracking of good quality distillate to
lighter products. Changing the cut
point between FCC product gaso-
line and LCO directly shifts gasoline
to distillate without changing any
other product yields or the overall
FCC volume swell. Reducing crack-
ing severity increases LCO yield by
reducing upgrading of heavy prod-
ucts into transportation fuels. The
lower cracking severity impacts all
other yields in addition to LCO and
gasoline. Lower value heavy fuel oil
yield increases while alkylation feed
decreases. Decreasing riser outlet
temperature can also decrease gaso-
line octane, which may impact other
renery operations to maintain
gasoline pool octane. Many reners
have implemented these operational
changes; however, catalyst changes
provide yet another powerful lever
to improve LCO yields.
Catalytic opportunities
Catalyst changes can increase LCO
yield while minimising the negative
aspects of distillate mode FCC
operation. ZSM-5 additives can be
used to increase gasoline octane
and light olen production at
reduced severity to maintain alkyl-
ation feed and gasoline octane.
However, the net result is still a
Butenes
Butanes
Propenes
Propanes
LPG (4)
Gasoline (3)
Gasoil (1)
LCO (2)
Coke (6)
Dry gas (5)
k
1 2
k
1 3
k
2 5
k
3 6
k
1 4
k
1 5
k
1 6
k
2 3
k
4 6
k
2 4
k
2 6
k
3 5
k
3 4
Figure 3 Typical FCC reaction network
In addition to the
changing demand
structure, the
relative prices of
gasoline and diesel
fuel have changed in
recent years
cat rive.indd 2 28/02/2014 11:57
catalyst. The catalyst particles are a
physic-chemical mixture of the
zeolite crystals, an active or inert
binder and other components that
can assist in the cracking reactions
or provide another function such as
metals trapping. The faujasite parti-
cles are introduced into the catalyst
formulation as individual particles
that are 1-5 microns in diameter,
while the fnal catalyst particles
have an average particle size of
about 70-80 microns. The zeolite is
a molecular sieve with most of its
active sites inside the small pores of
the individual crystallites. The size
of these pores is similar to (or often
smaller than) that of the molecules
that are being converted, so molec-
ular access to all of the interior
active, catalytic sites is limited by
diffusion.
These diffusional resistances can
impact selectivity as well as activ-
ity. If the primary cracked
fragments are delayed in leaving
the zeolite crystal, then they have a
higher probability of re-cracking to
lighter products. This re-cracking
will reduce the yield of intermedi-
ate products such as LCO and
gasoline and increase the yield of
less valuable, lighter gases, together
with coke.
Rive Technology has developed
methods to reduce these diffusional
resistances and increase the yield of
the more valuable products by
introducing a uniform series of
larger diameter holes into the
zeolite crystals themselves, prior to
or after incorporation into the
fnished catalyst. This creates a
network of intermediate-sized
mesopores or molecular high-
ways within zeolite crystals,
including type Y zeolite used in
FCC catalyst (see Figure 4). These
40 diameter mesopores are larger
than the 7.5 diameter micropores
which exist naturally in Y zeolite, so
they provide both improved access
for large feed molecules to the inte-
rior of the zeolite crystals (where
the active sites are located), and
improved escape of distillate mole-
cules from the zeolite before they
re-crack to light gases and coke.
The Molecular Highway technol-
ogy process begins with standard Y
zeolite and then further processes it
Figure 4 Modied zeolite pore structure
Figure 5 Photomicrographs of modied zeolite
cat rive.indd 3 28/02/2014 11:57
Improved pore structure and
reduced diffusional resistances
allow larger molecules to access the
zeolite and cracked products to exit
before over-cracking to produce
coke. This improved balance
between cracking and coke can be
seen in Figure 6. Bottoms (CSO)
yield is plotted versus coke yield in
this fgure for two refneries where
the incumbent catalyst was tested
against a commercial catalyst with
Molecular Highway technology,
produced and jointly developed by
W.R. Grace. These results were
generated in an ACE unit, but these
yield differences have been
confrmed with controlled trials at
each refnery.
5,6
In commercial oper-
ations, the refner can effectively
control the unit severity and coke
yield by adjusting operating condi-
tions, including riser temperature,
feed temperature and possibly cata-
lyst cooler duty. Accordingly, the
modifed catalyst has been shown
to produce less low value bottoms
at a given coke yield.
This provides an opportunity to
maintain or reduce bottoms yield
while lowering unit severity, which
translates into higher yields
of more valuable products.
Additionally, many refners use the
ratio of LCO to bottoms yields
(LCO/CSO) as a measure of desira-
ble catalyst selectivity since it is an
indicator of the catalysts ability to
produce good yields in a reduced
severity environment. Figure 7
compares the ratio of LCO/CSO
yields for commercial Rive catalysts
versus the incumbents at the two
refneries. In each case, LCO selec-
tivity is improved over CSO at all
levels of severity (coke yield).
Similarly, gasoline and LPG
yields increase with Rive catalyst at
a given severity (see Figure 8). The
yield of gasoline plus LPG consist-
ently increases relative to the yield
of low value bottoms. In these
examples, we have combined gaso-
line and LPG since some refners
prefer to maximise LPG and olefns,
while others need to minimise LPG.
Both gasoline and LPG olefns are
valuable, and the split between
them can be controlled through fne
tuning of the catalyst formulation
(for instance rare earth content and
tallinity. They also contain millions
of micropore openings that are too
small to resolve at this magnifca-
tion. In addition, though, the
crystals now also show an extensive
network of mesopore openings that
were created during the processing.
These unique molecular highways
are hydrothermally stable in the
FCC unit and result in a materially
improved product yield structure
and increased middle distillate yield
in catalytic cracking.
Catalyst performance: impact of
enhanced diffusion
With conventional catalysts, the
yield of low value bottoms
increases when FCC severity is
lowered to increase LCO yield.
Rive catalysts mitigate this problem
by increasing the yield of transpor-
tation fuels, while reducing bottoms
yield, allowing refners to better
optimise their distillate operations.
to chemically burrow a network of
surface-accessible mesopores
throughout the crystal without
materially affecting its crystal struc-
ture. The high resolution feld
emission scanning electron photo-
micrographs in Figure 5 illustrate
the transformation.
4
The top photo
is of a high quality Y zeolite repre-
sentative of the type used in
modern FCC catalysts. It has angu-
lar prismatic crystals and fat, sharp
crystal faces characteristic of highly
crystalline material. Each crystal
face also contains millions of 7.5
diameter micropore windows that
are too small to see at even the
85 000X100 000X magnifcation of
these images.
The lower photo shows a sample
of the same type zeolite after it has
been processed to create the addi-
tional mesopore network. The
particles retain the prismatic, sharp
angular faces characteristic of crys-
9
1 3
1 2
1 5
1 4
1 1
1 0
8
7
6
5
4
C
S
O

y
i
e
l
d
,

w
t
%
3
2 3 4 5 6 7
Coke yi el d, wt %
R e fin e ry B I n c u m b e n t
R e fin e ry B R ive
R e fin e ry A R ive
R e fin e ry A I n c u m b e n t
Figure 6 Bottoms yield for Rive catalysts versus coke
2 . 5
3 . 5
4
3
2
1 . 5
L
C
O
/
C
S
O
,

w
t
/
w
t
1
2 3 4 5 6 7
Coke yield, wt%
Figure 7 LCO/CSO Selectivity for Rive catalysts versus coke
cat rive.indd 4 28/02/2014 11:57
industrial experience including extensive work
in FCC spanning hardware design, modelling,
technical service, and hands-on operations.
Previously, he worked for Aspen Technology,
and Mobil Research and Engineering. He holds a
bachelors degree in chemical engineering from
the University of Delaware, and a masters and
PhD in the same eld from the University of
Illinois Urbana-Champaign.
Adrian Humphries is Director of Technical
Services at Rive Technology. He has over 30
years of experience in the catalyst industry,
serving in a variety of senior leadership roles
at Albemarle Corporation, Akzo Nobel, Filtrol,
Hermes Catalysts, and Quanta Technologies in
various product development and marketing
roles, many of which focused on uid catalytic
cracking and additives. He holds a PhD in
chemistry and catalysis from the University of
Bristol, England.
Stephen McGovern is the FCC Technology
Advisor to Rive Technology. He has been active
in the rening and petrochemical industries
for over 40 years, and is currently a principal
of Petrotech Consultants, an independent
consulting rm specialising in rening
technologies and economics. Previously,
he was with Mobil Technology Company in
process development and renery technical
support in the areas of catalytic cracking and
hydroprocessing. He holds BS and MS degrees
in chemical engineering from Drexel University
and a PhD in chemical engineering from
Princeton University.
Barry Speronello is a Research Fellow at
Rive Technology. He has over 30 years of
service at Engelhard Corporation and then
BASF Catalysts LLC after its acquisition of
Engelhard. He retired from BASF in 2009 as a
Research Fellow and joined Rive Technology
where he has worked since. He is an inventor
on 53 US Patents, primarily in the areas of
catalytic cracking, emission control catalysis,
and oxidation chemistry, and holds a PhD in
ceramic engineering from Rutgers University.
with no increase in bottoms yield,
leading to:
Better optimised yield structure
The ability to run more feed
The opportunity to process
heavier, cheaper feedstocks
Higher recycle rates in order to
minimise bottoms yield.
Molecular Highway is a mark of Rive
Technology.
References
1 EPA and NHTSA Set Standards to Reduce
Greenhouse Gases and Improve Fuel Economy
for Model Years 2017-2025 Cars and Light
Trucks, Ofce of Transportation & Air Quality,
EPA-420-F-12-051, Aug 2012 .
2 Transition to Alternative Vehicles and Fuels,
National Research Council of the National
Academies, 2013.
3 Heydari M, AleEbrahim H, Dabir B, Study of
seven-lump kinetic model in the uid catalytic
cracking unit, American Journal of Applied
Sciences, 7 (1), 71-76, 2010.
4 Li K, Valla J, Garcia-Martinez J, Realizing the
commercial potential of hierarchical zeolites:
new opportunities in catalytic cracking,
ChemCatChem, 6 (1), 46-66, Jan 2014.
5 Krishnaiah G, Speronello B, Duncan H,
Molecular Highway
TM
technology for FCC
catalysts in a commercial renery, AFPM
Annual Meeting, AM-12-25, 2012.
6 Dight L, Krishnaiah G, Speronello B, Hansen
A, Crosby J, Rive Molecular Highway
TM
catalyst
delivers over $2/50/bbl uplift at Alons Big
Spring, Texas Renery, AFPM Annual Meeting,
AM-13-03, 2013.
Allen Hansen is a Consultant to Rive
Technology and founder and Vice President
of ClinChain Inc., providing modelling and
advanced optimisation consulting services
to the process industries. He has 24 years of
activity), and through operational
changes (such as riser temperature
and cat-to-oil ratio). Therefore, the
total is most important and trans-
portation fuels overall are increased
relative to bottoms with Rive cata-
lysts, at any level of severity.
Economics
The impact of modifed pore struc-
ture and increased diffusion has
been shown to produce improved
yields. In addition to the two sets
of catalyst comparisons described
above, which have been vetted
through controlled refnery trials,
numerous additional studies have
produced the same trends on a
variety of feed types comparing
incumbent catalyst formulations
against catalysts with Molecular
Highway technology. This provides
substantial fexibility to refners to
re-optimise their operations within
their specifc economics and
constraints, with uplifts generally
estimated to be worth between
$1.00/bbl and $2.50/bbl of FCC
feed.
Summary
In contrast to the traditional
approach of lower operating sever-
ity and lowering the zeolite activity
of conventional FCC catalyst, Rive
Technology has introduced
Molecular Highway technology to
maximise distillate production.
While the traditional approach
drops LPG into gasoline, gasoline
into LCO and LCO into bottoms,
Molecular Highway technology
enables refners to crack more
bottoms into valuable transporta-
tion fuel at lower riser temperatures.
FCC catalysts formulated with this
novel technology have been
commercially proven to achieve
uplifts much greater than were
previously achieved in FCC units.
Benefts of catalysts with
Molecular Highway technology
include:
Less bottoms yield at fxed oper-
ating conditions
Optimised LCO yield at lower
severity, with no increase in
bottoms yield
Alleviation of constraints such as
air rate, wet gas rate and regenera-
tor temperature at lower severity,
2 3 4 5 6 7
Coke yi el d, wt %
1 5
G
a
s
o
l
i
n
e
+
L
P
G
/
C
S
O
,

w
t
/
w
t
2 5
2 0
1 0
5
0
Figure 8 Gasoline + LPG selectivity for Rive catalysts versus coke
cat rive.indd 5 03/03/2014 11:00
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42_amacs.indd 1 27/02/2014 14:58
Dewaxing challenging parafnic feeds
I
mproving the cold fow proper-
ties of paraffnic feedstocks in a
selective way has become a hot
topic during the last decade as
refners search for more effective
and cost-effcient ways to achieve
improvements in cold fow proper-
ties. The growing trend is to use
catalytic dewaxing to limit the use
of cold fow additives, reduce kero-
sene blending requirements,
upgrade heavier feedstocks with
higher cloud and/or pour points
and, consequently, to create more
room in the blending pool for heav-
ier feeds.
Increasingly stringent specifca-
tions, the rise in new types of crude
from different origins or process
routes, and the desire to sell prod-
ucts that meet cold fow property
specifcations result in the need to
process more challenging types of
feedstocks some of them being
heavier, some lighter but of differ-
ent compositions, and some being
signifcantly more paraffnic.
This article gives an overview of
the possible catalytic dewaxing
solutions that can be offered to
solve different challenges in
improving cold fow properties.
Advances in catalyst and process
development by Shell Global
Solutions and Criterion enable not
only a better understanding of
what is achievable in a prescribed
set of conditions and constraints
but are also leading to the develop-
ment of innovative solutions in
association with customers.
Examples of research and
development carried out in under-
standing and processing paraffnic
feedstocks, as well as an illustration
of commercial applications of Shell
Catalytic dewaxing using recent developments in dewaxing catalysts provides an
alternative method for cold ow improvement in diesel and lube oil
RENATA SZYNKARCZUK Criterion Catalysts & Technologies
MICHELLE ROBINSON and LAURENT HUVE Shell Global Solutions International
Global Solutions and Criterions
catalytic dewaxing for some chal-
lenging feedstocks, are highlighted
here.
Cold ow improvement via catalytic
dewaxing
At low temperatures, products
with waxy components start to
crystallise and affect the fow char-
acteristics of the fnal product. To
avoid problems and to ensure that
products meet low temperature
fow properties, different techniques
have been and are being used in the
industry, from the use of additives
and/or kerosene blending to
advanced catalytic dewaxing.
0
1 0 0
1 5 0
5 0
50
100
M
e
l
t
i
n
g

p
o
i
n
t
,

C
150
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0
Carbon number
S e le c tive c ra c k in g
I so m e risa tio n
0
1 0 0
1 5 0
5 0
50
100
M
e
l
t
i
n
g

p
o
i
n
t
,

C
150
0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0
Boiling point, C
S e le c tive c ra c k in g
I so m e risa tio n
Figure 1 Possible reaction routes to decrease the melting point of a linear alkane of a
given carbon number (that is, a given boiling point). Note the difference between the two
routes: selective cracking decreases both the melting point and the boiling point (carbon
number), while isomerisation mostly affects the melting point leaving the boiling point
slightly impacted
1
and the carbon number unchanged
cat criterion.indd 1 28/02/2014 12:31
Inuence of molecular structure on
cold ow properties
A signifcant amount of research,
including the use of modern and
recently developed analytical tools,
has been carried out in the last fve
to 15 years, resulting in a large
database for investigating and
capturing the infuence of molecu-
lar structure on cold fow
properties.
These studies focused on under-
standing what type of isomerisation
and/or selective cracking of linear
alkanes had the greatest effect on
cold fow improvement, what were
the governing parameters, and how
this knowledge can be used to
design catalysts and catalytic
systems of superior performance.
This enables the development of
solutions to a number of key issues
such as achieving deep dewaxing
(by several tens of degrees) of
diesels or base oils with limited
yield loss and limited gas forma-
tion while keeping other properties
within agreed specifcations or
better.
Branching of linear alkanes by a
single methyl group already has a
signifcant impact on cold fow
properties (represented here by
melting point, as found in the liter-
ature,
2
or measured on a pure
sample).
For example, while nonadecane,
the linear alkane with 19 carbon
atoms, boiling at 329.7C (625.5F)
within the diesel boiling range, has
a melting point of +32.1C (89.8F),
any of its single methyl-branched
isomers has a signifcantly lower
melting point, the highest being for
2-methyl-octadecane with a melting
point of +13C (55.4F), the lowest
for the isomer with a methyl group
located in the middle of the chain,
9-methyl-octadecane, with a melting
point of -16.5C (2.3F, see Table 1).
While positioning a methyl group
in the middle of the chain shows
the largest fall in melting point, it is
also known that a single methyl
group is not suffcient when chain
length increases; this is illustrated
by a comparison of the melting
points of 9-methyl octadecane,
10-methyl eicosane and 13-methyl
hexacosane (see Table 2, left).
Therefore, more branching is
Three main cold fow properties
are typically used to characterise a
diesel fuel: cloud point, the most
stringent property; pour point; and
cold flter plugging point. Standard
industrial analytical methods are
prescribed for each of these
properties.
Flow improvers modify the wax
crystallisation process, by reducing
the crystal size and/or the lattice
formation of the solid phases, and
reduce both the cold flter plugging
point and the pour point. However
the cloud point, a property related
to individual component character-
istics and driven by the heaviest
molecules within the feedstock
boiling range, is also the most ther-
modynamically driven property.
Consequently it is also the most
diffcult to effectively reduce by
additives or by cost-effective dilu-
tion with kerosene. This becomes a
greater challenge when feeds are
becoming more paraffnic in nature,
with the presence of longer and
consequently higher cloud, linear
alkanes.
Cold fow improvers can signif-
cantly reduce cold flter plugging
point and pour point. Cloud point
improvement using additives is
typically within a couple of degrees,
up to a maximum of
3-4C (5-7F). With hydrotreated
kerosene blending, a cloud point
reduction of ~1C (1.8F) is typically
achieved for every 10% of kerosene
added. If a cloud point improve-
ment of more than 6-8C (11-14F)
is desired, then catalytic dewaxing
is usually a more economical long-
term solution than any alternative
method (additives and/or kerosene
blending and/or feedstock boiling
range adjustment).
Improving the cold fow proper-
ties of any feedstock requires
mainly modifying or removing
linear alkanes (usually referred to
as paraffns). This can be achieved
either by a physical separation
method (extraction) or by different
selective chemical reactions (cata-
lytic dewaxing). This article focuses
on the latter.
1
Conversion of linear and/or
slightly branched alkanes during
catalytic dewaxing is typically
carried out by a combination
of selective cracking and isomerisa-
tion reactions (see Figure 1),
the objective being to reduce cold
fow properties (represented
here by melting point), either by
selective cracking to lighter alkanes
and iso-alkanes with lower cold
fow properties or by isomerisation
of alkanes to iso-alkanes with simi-
lar molecular weights but lower
cold fow properties.

Methyl position in the chain (C
19
H
40
) Melting point C (F)
2-methyl-octadecane +13.0 (+55.4)
3-methyl-octadecane +0.5 (+32.9)
4-methyl-octadecane - 1.0 (+30.2)
5-methyl-octadecane -13.5 (+7.7)
6-methyl-octadecane - 4.0 (+24.8)
Melting points of single methyl branched isomers of nonadecane
Table 1
Main chain length Melting point Formula Melting point Viscosity
(carbon number) C (F) (C
30
H
62
) C (F) index
Methyl group position
18/9 methyl octadecane -16.5 (+2.3) n- triacontane(n-C
30
H
62
) +66 (+151) 190
20/10 methyl eicosane - 3.8 (+25.2) 2,6,10,15,19,23-
26/13 methyl hexacosane +28.9 (+84.0) hexamethyltetracosane -38 (-36) 116
Particle size distribution of fresh catalysts and additives (ASTM D4513)
Table 2
required to further decrease the
melting point, as illustrated by
n-triacontane and 2, 6, 10, 15, 19, 23
- hexamethyl tetracosane (see Table
2, right).
Of course, the more the molecules
are isomerised, the greater the boil-
ing point shift observed; this is
illustrated by high resolution,
two-dimensional gas chromatogra-
phy (2xGC) applied to carbon (see
Figure 2). The isomers of docosane,
n-C
22
H
46
, are located between the
elution of n-C
21
and n-C
22
.
Some other key properties may
also be affected, for instance a small
decrease in cetane index upon isom-
erisation for deeply dewaxed diesel
fuels, or a decrease in viscosity
index for base oil (see Table 2, right).
This was of particular interest to
Shell as the company was looking
to invest signicantly in gas-to-liq-
uids (GTL) applications where
dewaxing of essentially heavy
parafnic feedstock was targeted.
Since then, Pearl Qatar has started
up smoothly with two trains
including catalytic dewaxing of
light and medium-heavy, highly
parafnic base oils, showing the
excellent performance of the highly
selective isomerisation-dewaxing
reactors where cloud/pour point
improvements as high as 60-80C
(108-144F) are achieved on Shell/
Criterion dewaxing catalyst
SLD-821, leading to ultra-high qual-
ity base oils (see Table 3).
Inuence of boiling range
distribution of n-alkanes on cold
ow properties and dewaxing
On top of molecular structure and
molecule re-arrangement (via isom-
erisation) playing a signicant role
in cold ow properties improve-
ments, the distribution of linear
alkanes and their relative amounts
also signicantly inuences the
dewaxing process and its outcome.
This is illustrated by comparing
two feedstocks very similar in over-
all bulk properties but differing in
a subtle way in their distribution
and relative amounts of linear
alkanes (see Figure 3). The two
feedstocks contain 19.4 and 20 wt%
n-alkanes respectively, quantita-
tively measured by 2xGC carbon.
But the rst feedstock (in red)
contains almost 15% of C
17
+
n-al-
kanes and less C
16
-
n-alkanes, while
the second feed (in yellow) contains
only 12.5 wt% of C
17
+
n-alkanes and
more C
16
-
. Such differences inu-
ence the outcome of the dewaxing
process when a given improvement
is targeted.
1 5 0
2 5 0
2 0 0
1 0 0
5 0
S
e
c
o
n
d
-
d
i
m
e
n
s
i
o
n

r
e
l
a
t
i
v
e

r
e
t
e
n
t
i
o
n

t
i
m
e
s
,

s
e
c
o
n
d
s
0
0 1 2 5 2 5 0 3 7 5 5 0 0 6 2 5 7 5 0
Fi rst -di mensi on rel at i ve ret ent i on t i mes,
mi nut es
8 7 5
Figure 2 2xGC carbon - n-alkanes and isomerised alkanes in the diesel boiling range (and
extract)
Shell GtL base oils 4 cSt 5 cSt 8cSt
Vk100C (cSt) 3.8-4.2 4.8-5.4 7.5-8.5
Vk40C (cSt)
Viscosity Index 135 145 150
VdCCS, -30C 1000 1860 5300
Pour point, C <-30 <-24 <-15
Noack Volatility, %m 12 9 2
Flash point, C (D-93) 215 232 240
Shell GTL base oils quality and main characteristics
Table 3
1 . 5
2 . 5
2 . 0
1 . 0
0 . 5
0
6 9 1 2 1 5 1 8 2 1 2 4 2 7 3 0 7 1 0 1 3 1 6 1 9 2 2 2 5 2 8 8 1 1 1 4 1 7 2 0 2 3 2 6 2 9
Carbon number
Figure 3 Comparing two feedstocks of very similar bulk properties but somewhat
different distributions of n-alkanes
have developed state-of-the-art
selective cracking (SDD-800) and
isomerisation (SDD-821) dewaxing
catalysts for distillate applications.
A number of the fndings previ-
ously discussed were incorporated
into these developments.
Both catalysts have extensive
commercial application in units
worldwide. SLD-821, a base oil
counterpart dewaxing catalyst, was
developed using the same princi-
ples and is currently applied in
units processing highly paraffnic
feedstocks.
Typically, a selective dewaxing
catalyst converts exclusively linear
alkanes (waxes), which typically
represent a maximum of 10-15% of
standard feedstock molecules. In
the absence of linear and/or
slightly branched alkanes that can
be converted within the catalyst
pore structure, no reaction will take
place with these types of catalysts
(see Figure 6). On the contrary, the
larger the amount of linear alkanes
present, the deeper the conversion
will be, resulting in both molecular
rearrangement and boiling point
shift due to isomerisation and some
cracking, albeit selective, into
lighter molecules.
For well-balanced dewaxing solu-
tions, a speciality dewaxing catalyst
is typically installed at the back end
of the process line-up, where all
other required properties of the
targeted product have already been
met. To prevent yield loss, medium
pore zeolites, an active acidic cata-
lyst component, are used in
combination with a binder to selec-
tively crack or isomerise linear and
slightly branched alkanes present
in the feed and thus limit the cold
fow properties.
For catalytic dewaxing, reactant
shape-selective conversion of linear
paraffnic molecules theoretically
describes the required catalyst selec-
tivity. The reactant shape selectivity
concentration of linear alkanes is
maximised in the acidic zeolite, and
conversion (isomerisation or crack-
ing) is carried out at acidic catalytic
centres. In commercial applications,
the effectiveness of catalyst selectiv-
ity can be inhibited by adsorbing
poisons on the acidic site, leading to
blocking of catalyst active sites.
paraffnic crudes to be dewaxed in
their pool.
Dewaxing catalysts selectivity
Shell Global Solutions and Criterion
Examining the details of what
typically happens in selective crack-
ing-dewaxing with a highly
selective catalyst from the Shell/
Criterion dewaxing catalyst portfo-
lio is revealing (see Figure 4).
To be effcient in improving cold
fow, catalytic dewaxing must
target the heaviest linear alkanes;
this can be seen in a detailed char-
acterisation of feed and products
(see Figure 5).
The higher the proportion of
linear alkanes above C
16
, the more
conversion is needed and, as a
consequence, the higher the possi-
ble yield loss (as naphtha make).
These observations are key factors
in developing optimal technical
solutions with customers that have
one or more of these challenging
1 . 5
2 . 5
2 . 0
1 . 0
0 . 5
0
6 9 1 2 1 5 1 8 2 1 2 4 2 7 3 0 7 1 0 1 3 1 6 1 9 2 2 2 5 2 8 8 1 1 1 4 1 7 2 0 2 3 2 6 2 9
Carbon number
D e w a x e d p ro d u c t n a lk a n e s
F e e d sto c k n a lk a n e s
Figure 4 Comparing feedstock and dewaxed product for linear alkanes content and
distribution
2 0
6 0
8 0
4 0
0
2 0
4 0
6 0
8 0 C
o
m
p
o
s
i
t
i
o
n

c
h
a
n
g
e
,

%
1 0 0
6 9 1 2 1 5 1 8 2 1 2 4 2 7 3 0 7 1 0 1 3 1 6 1 9 2 2 2 5 2 8 8 1 1 1 4 1 7 2 0 2 3 2 6 2 9
Carbon number
Figure 5 Change in n-alkanes composition between feedstock and dewaxed product for a
given day of operation
Figure 6 Illustration of reactant shape
selectivity in zeolite containing dewaxing
catalyst
as well as Shells proprietary surface
passivation treatment, use reactant
shape selectivity and passivation
agents with a size that limits their
effects on the outer surface, while
they cannot easily enter and/or
diffuse within the smaller pore
structure (see Figure 7).
A carefully selected zeolite type
and controlled acidity during
synthesis before embedding the
crystals in a carrier, as well as
surface passivation that eliminates
catalytic activity on the outer
surface of the embedded zeolite
crystals, delivers superior perfor-
mance in term of yields and
resistance to deactivation by coke
formation when compared to
conventional dewaxing catalysts
used in diesel or base oil dewaxing
applications (see Figure 8).
Exceptional diesel yields are
achieved with SDD-800 as a func-
tion of pour or cloud point
reduction when compared to the
lesser results found when using a
conventional dewaxing catalyst.
Passivation of the external surface
clearly improves diesel yields and is
a key part of the successful applica-
Poisoned adsorption is usually
reversible when properly controlled.
The level and type of inhibitors
or catalyst poisons will have an
impact on the choice of a dewaxing
solution and its related catalyst
selection. Highly selective dewax-
ing is possible if no acidic function
is present on the outside of the
zeolite pores and channels. The
reactivity of feedstock molecules is
based upon their shape such that
linear and branched molecules can
react within the pore structure of
the zeolite while the other, more
bulky molecules are untouched.
Therefore, dewaxing catalysts
presenting a well-controlled outer
surface composition are used for
dewaxing by selective cracking
and/or isomerisation.
To make the outer surface of a
catalyst inactive, it is necessary to
chemically passivate the surface. A
number of outer surface passivation
methods are described in the litera-
ture, such as impregnation by inert
organic oxides, sublimation, or by
inorganic or organic agents binding
with the acidic centres on the outer
surface of a zeolite. All approaches,
Figure 7 Reactivity (cracking) on the outer surface of untreated dewaxing catalyst com-
pared to no activity after Shells passivation treatment
8 5
9 5
1 0 0
9 0
8 0
7 5
D
i
e
s
e
l

y
i
e
l
d

a
t

1
5
0
C
+
,

%
w
o
f
f
7 0
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0
Pour poi nt reduct i on, C
S D D -8 0 0
C o n ve n tio n a l d e w a x in g c a ta lyst
Figure 8 Performance comparison of Shell SDD-800 and a conventional dewaxing catalyst
I think Ive got liquid carryover.
what can I do about it?
Read more on this topic at
www.amacs.com
It happens in petrochemical
plants, refineries, and anywhere
else that the gas approaching
a compressor is wet. Traces of
aqueous or organic liquid escape
the inlet knockout drum, often
intermittently, and silently damag-
ing the compressor. Telltale signs
include pitting corrosion, salt
deposits, and diluted lubricants.
Phone:+1-713-434-0934 Fax: +1-713-433-6201
amacs@amacs.com
AMACS
Compressor suction drums:
Knockout
drums
Stage 2 Stage 1
Cooler
Typical 1980s mist eliminator technology
Instead of trying to repair
symptoms, look for the root cause,
which usually involves the mist
eliminator in the knockout drum.
Problems may include improper
mist eliminator specifications,
overloading, uneven velocity, waxy
deposits, liquid slugs, foaming,
incorrect installation, and several
other possibilities. New, high-
capacity, high-efficiency mist
eliminator technologies pay off the
first time you avoid shutdown.
First versus second stage dewaxing
Depending on unit capability,
targets and choice of dewaxing
catalyst, Shell/Criterion dewaxing
technology can be applied in a rst
or second stage dewaxing congu-
ration (see Figure 9).
In a rst stage conguration, the
dewaxing bed is part of the hydro-
treating section in the so-called
drop in solution. As a result, the
nickel-based dewaxing catalyst is
exposed to organic nitrogen slip
and ammonia that could adsorb
onto the dewaxing catalysts acidic
sites and inhibit catalyst perfor-
mance. Organic sulphur slip and/
or hydrogen sulphide have no
effect on rst stage dewaxing cata-
lyst activity or selectivity.
First stage dewaxing can provide
a reasonably low cost drop in
solution in existing hydrotreaters.
In a second stage conguration, a
minimum of two reactors with
stripper in between is required.
Feedstock is hydrotreated in the
rst reactor and hydrogen sulphide
and ammonia are stripped from the
liquid before it is dewaxed in a
dedicated, clean environment
second reactor, allowing the use of
highly selective, noble metal-based
isomerisation-dewaxing catalysts.
As a result, the cost of implemen-
tation is expected to be higher than
for a rst stage dewaxing solution;
however, compared to rst stage
dewaxing, noble metal isomerisa-
tion-dewaxing delivers superior
distillate yields and products.
To avoid formation of mercap-
tans, the dewaxing catalyst is
followed by a small post-treating
bed to ensure that product colour
properties are met.
The following section illustrates
the development of Shell/Criterion
dewaxing solutions from pilot plant
conrmation testing to commercial
implementation.
Developing solutions for deep
dewaxing of highly parafnic
feedstocks
The deep dewaxing of highly
parafnic feedstocks can be
developed in several steps, depend-
ing on requirements, market drivers,
level of equipment available and/or
re-usability, and the amount of
the temperature of the dewaxing
catalyst bed.
tion of Shell/Criterions dewaxing
catalyst technology solutions to
challenging parafnic cases. In
addition, surface treatment of these
dewaxing catalysts acts as a protec-
tion against coke and results in
extended life; commercial operation
of up to seven years without reacti-
vation or regeneration has been
reported.
1
Surface treatment also helps the
catalyst to resist poisoning. For
Shell/Criterion dewaxing catalysts,
most of the poisoning effects are
fully reversible. Nitrogen slip to the
dewaxing catalyst can cause a
temporary decline in activity, but
the catalyst can fully recover after
nitrogen levels are reduced to allow-
able levels. Tempering dewaxing
catalyst activity is used in commer-
cial units that operate in winter
(dewaxing) and summer (ULSD)
modes, allowing the exibility to
switch the dewaxing catalyst on or
off on demand. During summer
mode, when dewaxing is not
needed, the dewaxing catalyst is
dormant in the reactor and has
negligible dewaxing activity and
consequently delivers marginal
yield losses. During winter mode,
the dewaxing catalyst is turned on
by desorbing the nitrogen adsorbed
onto the catalyst during the summer
mode months. In winter mode, the
activity of the dewaxing catalyst can
be tuned to the desired levels of
cold ow improvement by adjusting
H
2
S /N H
3
H T
H T
P T
Hydrotreating
Post treating
Dewaxing
Dewaxing
Figure 9 First and second stage dewaxing
catalyst conguration
Catalysts and technology
provide immediate and
long-term benefits
H e a lth , sa fe ty a n d e n viro n m e n ta l
issu e s a re o f g re a t im p o rta n c e to
S h e ll G S , a n d th u s c e n tra l to a ll
th e se o p tio n s
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Short-term catalyst and
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investments
Longer-term solutions
requiring investment
Immediate catalyst solutions
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Sweating
the assets
Figure 10 The pentagons: from sweating
the asset to short-term catalyst and
process solutions, to longer-term solutions
requiring investment
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Merichem Company-FY14-MID.pdf 1 2/24/2014 8:19:32 AM
merichem.indd 1 28/02/2014 10:28
conditions applied, it was possible
to obtain deep to very deep dewax-
ing (20-45C, 36-81F improvement)
while maintaining dewaxed diesel
yields between 90 wt% and 86 wt%
on feed, by combining selective
cracking and isomerisation on
SDD-800 (see Figure 11).
The challenge becomes signif-
cantly greater when even more
paraffnic feedstocks have to be
considered. The frst approach is to
study whether or not a frst stage
dewaxing option is possible and, if
it is not applicable in a straightfor-
ward way, how to adjust it to make
it possible, at least temporarily, to
achieve very deep dewaxing for a
still-acceptable yield loss.
This was extensively studied by
Shell Global Solutions and Criterion
on highly paraffnic feedstocks of
different origins by comparing an
adapted frst stage dewaxing solu-
tion and a second stage option in
the presence of limited amounts of
poison (sulphur).
Case study 2
The frst option considered was an
adapted frst stage dewaxing solu-
tion with bed-to-bed temperature
control on the dewaxing catalyst to
ensure stable operation throughout
the cycle, avoiding uncontrolled,
deeper dewaxing than required and
consequently more yield loss than
desired at any point of the cycle.
This resulted in a rather
controlled operation with very
deep dewaxing achievable, albeit at
the expense of yield loss (see Figure
12). It proved possible, within unit
constraints, to achieve a depth of
dewaxing as high as 60C (108F)
while maintaining stable unit oper-
ation and a suffciently high yield
of good quality, deeply dewaxed
diesel and gasoline.
Case study 3
The next step in developing an
adequate solution for such a chal-
lenging, highly paraffnic feedstock
(containing up to 90-95 wt% of
paraffnic components) is to
consider a complete revamp of an
existing unit into a two-stage
dewaxing application. Shell Global
Solutions International has exten-
sively studied such an option,

Case study 1
A customer wanted a deep catalytic
dewaxing solution in an existing
unit with minimum investment and
the same depth of hydrodesulphur-
isation. With targeted pour and
cloud point improvements of
10-45C (18-81F) and starting from
a feedstock containing 20-30% of
heavy paraffnic components, only
a frst-stage dewaxing solution was
possible. By adjusting the location
of the dewaxing catalyst bed, using
SDD-800 and the right combination
of HDS/HDN hydrotreating cata-
lysts, it was possible to develop a
solution that was compatible with
the capability of the existing unit
and for cycles as long as fve years,
without having to rejuvenate,
regenerate or change the dewaxing
catalyst. With the new catalytic
system in place and with the right
catalyst confguration and process
investment that can be justifed for
the economic viability of the project.
Three typical steps are considered
(see Figure 10): sweating the asset,
where a catalytic solution is imple-
mented with minimum modifcation
to, or impact on, the existing unit;
revamp where a number of key
modifcations are required to adapt
a better solution; and fnally, the
development of a new solution
aimed at breakthrough performance
but with a signifcant investment
required. These three steps have
been developed for catalytic solu-
tions and are implemented
successfully in a number of commer-
cial operations or in the fnal phase
of development when targeting
specifcally deep catalytic dewaxing
of highly paraffnic feedstocks. The
three main steps will be illustrated
with examples and on-going
developments.
9 6
1 0 0
9 8
9 4
9 2
9 0
8 8
8 6
D
e
w
a
x
e
d

y
i
e
l
d
,

%
8 4
0 1 0 2 0 3 0 4 0 5 0
pour point, C
Figure 11 Dewaxed diesel yield as a function of delta pour point in commercial operation
8 0
1 0 0
9 0
7 0
6 0
W
a
x
i
n
g
,

%
5 0
0 1 0 2 0 3 0 4 0 5 0 6 0
c lo u d p o in t, C
Figure 12 Very deep dewaxing of highly parafnic feedstock (selective cracking)
way to an increase in applications
of dedicated catalytic dewaxing
solutions in refneries.
References
1 Domokos L, Huve L G, Kraus L S, Shell
Dewaxing Technologies for Distillate
Applications, Prep. Pap. Am. Chem. Soc., Div.
Pet. Chem. 2011, 56(2), 87.
2 Handbook of Chemistry and Physics, 65th
Edition 1984-1985, Weast R C, Editor CRC
Press, Inc. Boca Raton, Florida.
3 Huve LG, State of the art 2nd stage catalytic
dewaxing for distillates & lubes, presentation
at the 12th Russia & CIS Rening Technology
Conference (RRTC), Hotel Lotte, Moscow, 20 &
21 Sept 2012.
Renata Szynkarczuk is Technical Services
Engineer with Criterion Catalysts and
Technologies in Edmonton, Alberta. She holds
a M.Sc. in chemical engineering from the
Technical University of Wroclaw.
Michelle L.Robinson is Team Lead Distillate
Dewaxing with Shell Global Solutions
International B.V. in Amsterdam. She holds
a Masters in chemical engineering from
Loughborough University, UK
Laurent G Huve is Licensing Technology
Manager Dewaxing & Base Oils for Shell Global
Solutions International B.V. in Amsterdam. He
holds a degree in chemical engineering from
Ecole Nationale Suprieure de Chimie de
Mulhouse, France, and a PhD in chemistry from
the University of Haute Alsace, France.
high quality product, albeit at
higher temperature (see Figure 13).
It was shown that a dewaxed yield
as high as 80-87 wt% of feed can be
achieved, even at the deepest
dewaxing depth achieved.

Conclusions
Catalytic dewaxing provides an
alternative method for cold fow
improvement in diesel and lube oil
that cannot be met to a signifcant
level by more conventional meth-
ods. The latest generation of
dewaxing catalysts is specifcally
tailored to application and feed-
stock type by utilising shape
selective zeolites to preserve maxi-
mum distillate yields. Superior
selectivity in Shell/Criterions
dewaxing catalysts is ensured by a
proprietary outer surface passiva-
tion method. With the current
increase in heavy paraffnic mate-
rial on the market, refners must
adapt their processing facilities to
meet these new challenges.
The development of light tight
oils in North America and the pres-
ence of highly paraffnic crudes in
the former Soviet Union, China and
North America are opening the
starting from paraffnic feedstocks
with pour point as high as 40-45C
(104-113F), with the aim of reach-
ing cloud point and/or pour point
improvement as high as 70-75C
(126-135F). One of the key chal-
lenges in such an operation is the
remaining presence of poisons,
mainly sulphur and nitrogen, that
may hamper the activity and selec-
tivity of isomerisation-dewaxing
with noble metal dewaxing
catalysts.
Very long duration tests (>15 000
hours) were carried out in a large
pilot plant to develop detailed
understanding of such a challenging
operation by looking at various
paraffnic feedstock poisoning levels
(from below the detection limit to as
high as 19 ppmw sulphur) and at
varying space velocities.
To make the exercise comparable,
the same product quality was
targeted: a product with a pour
point of -30C (-22F), starting from
a feedstock pour point of 40-45C
(104-113F). While it is more than
benefcial to process feedstock as
free of poisons as possible, the pres-
ence of a limited amount of sulphur
does not prevent reaching the same
3 3 5
3 4 0
3 4 5
3 3 0
3 2 5
C
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50
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t

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60
0 1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 6000 7 0 0 0 8 0 0 0 9 0 0 0 1 0 0 0 0 1 1 0 0 0 1 2 0 0 0 1 3 0 0 0 1 4 0 0 0 1 5 0 0 0
Time on stream, hours
F e e d sto c k s p o u r p o in t: +4 0 -4 5 C
Ye a r 1 p o u r p o in t
Ye a r 2 p o u r p o in t Ye a r 2 c a ta lyst te m p e ra tu re
Ye a r 1 c a ta lyst te m p e ra tu re
WH S V = 1 . 4 T /m

3
. h
1
1 . 4 -2 . 0 T /m

3
. h
1
WH S V = 2 . 0 5 T /m

3
. h
1
F
e
e
d

1
;

S

=

4
.
6

p
p
m
F
e
e
d

2
;

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=

7
.
5

p
p
m
F
e
e
d

3
;

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=

5
.
4

p
p
m
F
e
e
d

4
;

S

=

1
9

p
p
m
F
e
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d

5
;

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=

6
.
8

p
p
m
F
e
e
d

6
;

S

=

2
.
2

p
p
m
F
e
e
d

7
;

S

=

2
.
4

p
p
m
F
e
e
d

8
;

S

<
1
.
0

p
p
m
F
e
e
d
s

9

&

1
0
;

S

<
1
.
0

p
p
m
F
e
e
d

1
1
;

S

=

1
.
3

p
p
m
F
e
e
d

1
2
;

S

=

1
.
0

p
p
m
F
e
e
d
s

1
3
,

1
4
,

1
5
;

S

=

1
.
3

p
p
m
F
e
e
d
s

1
6

&

1
7
;

S

<
1
.
0

p
p
m
F
e
e
d

1
8
;

S

=

2
.
0

p
p
m
Figure 13 Extensive pilot plant testing of several highly parafnic feedstocks containing various amounts of sulphur and processed
under different process conditions (WHSV and temperature) for deep dewaxing
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
info@revamps.com
www.revamps.com
PROCESS
CONSULTING
SERVICES,INC.
upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on todays experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
with know-how who have real
experience wearing Nomex
suits
and measuring true unit per-
formance in Northern Alberta.
Shouldnt this be kept in mind
by those considering long term
supply agreements?
Oil Sands Crude
Profits and
Problems?
Canadian bitumen production
currently runs about 1 MMbpd,
with some being sold as Synbit
and Dilbit. Over the next 10-12
years output is expected to
increase to 3.5 MMbpd and more
refiners will begin investing to
process it and come to depend
on the Synbit and Dilbit for a
significant part of their supply.
Few today, however, have ever
processed these feeds at high
blend ratios, and are unaware
that conventional process and
equipment designs are not up
to the job. Canadian oil sands
feedstocks are extremely hard
to desalt, difficult to vaporize,
thermally unstable, corrosive, and
produce high di-olefin product
from the coker. If you intend to
lock into a long-term supply,
therefore, it is imperative that you
consider reliability and run length
from a particular design.
Too low tube velocity in the
vacuum heater tubes will lead to
precipitation of asphaltenes. Too
fast a flow rate will erode the
tube bends. If coil layout, burner
configuration and steam rate are
not correct, run length will be
measured in months, not years.
Diluent recovery unit designs
must take into account possible
For a discussion of factors
involved in designing refinery units
to process difficult oil sands feed-
stocks, ask for Technical Papers
#234 and 238.
10 PTQ 01:10 01 PC PTQ 0107 ADF 10/19/07 4:42 PM Page 1
pcs 2.indd 1 1/6/12 21:05:28
Maximising distillate and alkylation feed
from the FCC
T
he tight oil revolution, falling
gasoline demand, Renewable
Fuel Standards requirements
and the emergence of the US as an
exporter of refning products have
changed the economics and operat-
ing objectives for many refners.
Distillate and alkylation feed from
the FCC unit are often more profta-
ble than gasoline. Where available,
cheaper tight oil crudes have
reversed the trend towards heavy
and sour crudes, thereby creating
both opportunities and challenges.
These paraffnic sweet crudes make
FCC feeds that have lower distillate
production, gasoline octanes and C
4

olefnicity. Tight oil feeds are gener-
ally low in nickel and vanadium,
but high in iron, calcium and, often,
sodium, which creates signifcant
challenges for FCC catalysts.
Albemarle has developed tech-
nologies to meet these changing
needs and has introduced catalysts
that help FCC unit operators to
achieve their yield objectives for
distillate and alkylation feed.
The Action FCC catalyst uses a
combination of novel zeolite and
alumina-based matrix technologies
to deliver maximum bottoms crack-
ing upgrading and metals tolerance.
These technologies provide the
catalyst surface chemistry and pore
architecture necessary to selectively
process molecules ranging from the
paraffns of tight oils to the multi-
ring aromatics of heavy residue
feeds.
Improved accessibility
Given the short contact times expe-
rienced in most FCC unit risers,
highly accessible catalysts enable
more of the active ingredients and
The tight oil revolution has changed FCC priorities. Operators can maximise
protability by adopting new catalysts to target their yield prole
ALAN KRAMER and GEORGE YALURIS
Albemarle Corporation
activity to be utilised in the reactor
(see Figure 1). Higher accessibility
means faster diffusion of feed mole-
cules into the catalyst particle,
which results in better bottoms
cracking and higher intrinsic activ-
ity. Higher accessibility also
accelerates the diffusion of reac-
tants out of the catalyst particle,
which helps to reduce secondary
reactions such as overcracking and
hydrogen transfer.
The strong matrix activity and
corresponding bottoms upgrading
offered by Albemarles ADM-20
and ADM-60 matrices provide
greater fexibility to balance the
contributions of the matrix and
zeolite. This enables custom design
of catalysts to suit specifc unit
needs for distillate and alkylation
feed production.
The high accessibility of the
matrix technology in Action also
provides high resistance to iron,
calcium and sodium contaminants,
which are present in heavy residues
and many opportunity feeds and
light tight oil-derived feedstocks.
1
The use of alumina-based matrices
means that Action catalysts main-
tain maximum activity and bottoms
cracking at high levels of iron and
calcium contamination. These cata-
lysts are also formulated with
ADZT-100, a novel high silica to
aluminum ratio zeolite technology
that is more resistant to deactiva-
tion by sodium or vanadium.
Zeolite rare earth exchange is
employed by some catalyst manu-
facturers to increase zeolite activity
and stability in the severe hydro-
thermal conditions of the FCC unit
and to provide resistance to
sodium- and vanadium-induced
zeolite destruction. However, the
activity provided by the matrices in
Action catalysts, the inherent
metals tolerance and the stability of
the high silica to alumina ratio
zeolites used mean that Albemarle
does not depend on high levels of
rare earth to maintain catalyst
6 0
1 0 0
9 0
8 0
7 0
5 0
4 0
3 0
2 0
1 0
C
a
t
a
l
y
s
t

a
c
c
e
s
s
e
d
,

%
0
Z e ro S h o rt M e d iu m L o n g
Cat al yst + hydrocarbon cont act t i me
L o w a c c e ssib ility
H ig h a c c e ssib ility
Figure 1 How much of the catalyst active ingredients ever see any reactant?
catalysis albemarle.indd 1 28/02/2014 12:37
Nasty Stuff
Heavy crudes are here to stay.
As long as oil prices remain high,
Canadian, Venezuelan, Deep Water
Gulf of Mexico, Mexican and
other low API gravity crude oils
will play an ever more important
role in supplying world refineries.
And prices promise to remain high
because gainsayers notwithstanding,
Hubbert was right.
A big question is how to best handle
these nasty crudes? Do you
revamp existing units or invest in
new capacity? With refineries now
running flat out, the balance might
seem to favor grass roots expansion,
but given the substantial cost
multiplier over revamps, this could
be questioned. Whichever the case,
however, an inescapable fact is
that the process design of the project
will prove crucial. Between the
charge pump, the desalter and the
units' distillation columns there are
many places where miscalcula-
tions in the process design could
wreck the entire project.
Can you really be sure of attaining
desired crude rates? Desalting
viscous crude is extremely difficult.
Minimizing coking or asphaltene
precipitation in the heaters demands
extreme care. Can you reasonably
expect high diesel and HVGO
recoveries, acceptable levels of
nickel, vanadium, and microcarbon
residue (MCR)? Refiners who cut
deep should not be surprised when
the HVGO product MCR is over 2
wt % and the vanadium content is
in excess of 10 ppmw. Any one of
such difficulties can result in lower
revenue, unstable operation or
even unit shutdown. It is critical to
understand that the inherent
properties of these low API gravity
crudes dictate that exact process
design is of paramount importance.
The point of this litany of possible
problems is to remind you not to
skimp in the early phases of
engineering. From the start of the
LP work through the completion of
front-end process engineering,
actual product yield and qualities
depend on the process design.
The message is clear. Nasty crudes
will continue to make up an
increasing proportion of refineries'
crude slates. But time is precious.
The sooner we face this fact,
unwelcome as it may be, the more
expeditiously we can adapt.
For a more in depth review of
heavy crude challenges, ask us for
Technical Papers 173, 185 and
197.
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
info@revamps.com
www.revamps.com
This exchanger has seen better crude slates
pcs nasty.indd 1 1/6/12 11:58:35
oil ratios and improved yield selec-
tivities and activities.
2
LCO/ bottoms ratio and LPG yield
Action delivered a 22% increase in
the LCO/bottoms ratio compared
with the competitors high zeolite
catalyst. Model simulations indicated
that even if the refner had lowered
the catalyst addition rate with Action
to maintain constant conversion, it
would still have provided more
bottoms cracking and an improved
LCO/bottoms ratio.
Refners can take advantage of
superior bottoms upgrading to
increase distillate, gasoline or gaso-
line plus distillate production,
depending on their proftability
objectives. In this case, Action was
formulated to maximise total liquid
product (gasoline plus distillate)
and LPG yield and olefns. It
increased LPG plus gasoline plus
diesel from 101% to 104% of feed at
constant conditions.
The isomerisation activity of
ADZT-100 meant that the gasoline
octane increased without the need
to use ZSM-5: RON and MON
increased by 0.5 and 0.3 numbers
respectively. Action also resulted in
a higher LPG yield and a more
olefnic LPG. For this refner, the
greater quantity of alkylation feed
from the FCC unit improved proft-
ability signifcantly.
Increased LPG olenicity and
gasoline octane
Actions ADZT-100 zeolite technol-
ogy helped to increase LPG
stability. Catalysts with lower
rare earth content have lower
hydrogen transfer and make more
olefnic LPG and higher gasoline
octane.
In addition, ADZT-100 technology
enhances isomerisation reactions
rather than hydrogen transfer reac-
tions. As a result, C
4
olefns
hydrogenation is averted, which
enables Action to achieve higher
butylene yields. Furthermore,
increasing isomerisation reactions
raises octane, which is particularly
important when processing tight
oils.
Example 1: Vacuum gas oil (VGO)
feed application
The large FCC unit in this applica-
tion is a side-by-side design with
recent updates to the riser and
regenerator. The feedstock is
hydrotreated VGO with low metals
and Conradson carbon values well
below 1 wt% and often below 0.5
wt%. The daily catalyst replace-
ment rate for this FCC unit is below
1% per day.
The main economic drivers for
the refner are distillate plus gaso-
line maximisation and bottoms
minimisation. Increasing LPG
olefns is another major objective
and more gasoline octane improves
unit proftability, so the refner
often uses ZSM-5 additives. A test
comparison of catalyst systems was
conducted during extended periods
without ZSM-5 additives. The
results are shown in Table 1 and
discussed below.
Comparison of e-cat phosphorous
and Z/M ratio
Phosphorus analyses from the equi-
librium catalyst indicate that both
catalysts, Action and a competitors
commercial catalyst, were relatively
free of additive. The difference in
results refects the differences in the
phosphorous content of the crack-
ing catalyst and residual amounts
from earlier periods of ZSM-5 addi-
tive use.
The riser temperature averaged
975F (524C) for both periods and
varied from 960F to 985F (516-
530C). The comparison was
conducted at constant operating
conditions, catalyst additions and
feed properties using KBCs CatOp
FCC model. For the projections, the
cut points were fxed at 430F and
670F (221C, 354C) for gasoline
and LCO respectively.
Activity retention and coke
selectivity
The feed to this unit is considered
quite crackable, but the low catalyst
replacement rate and moderately
high regenerator temperatures
favour a catalyst with good stabil-
ity and activity retention. Since this
unit processes a hydrotreated VGO
feed, the competitors catalyst
relied on zeolite to provide most of
the activity. However, the conver-
sion and coke selectivity results
showed that Actions highly active
and stable matrix components,
combined with the ADZT-100
zeolite technology, proved a more
appropriate ft.
High matrix catalysts can offer
signifcant coke selectivity advan-
tages over high Z/M catalysts,
which results in higher catalyst
circulation rates, higher catalyst to
Table 1

Competitors system Action
Equilibrium catalyst P
2
O
5
, wt% 0.13 0.06
Equilibrium catalyst zeolite/matrix (Z/M) ratio 1.45 0.63

Delta (Action Competition)
Conversion, wt% + 3.7
Coke selectivity (coke/kinetic conversion) 16% improved
Light cycle oil/bottoms ratio 23% improved
LPG, wt% +1.4
LPG olenicities, wt%/wt%
C
3
+0.025
C
4
+0.035
Gasoline octanes
RON +0.56
MON +0.25
Results from a FCC unit processing hydrotreated VGO, shown at constant operating
conditions and product cutpoints
High matrix catalysts
can offer signicant
coke selectivity
advantages over
high zeolite/matrix
catalysts
olefnicity and gasoline octane
without loss of liquid product.
Using typical Gulf Coast region
product values from an informal
survey conducted by Albemarle
in 2013, an economic analysis of
the volume shifts observed between
the catalysts suggests that Action
delivered an increase of $0.70 per
barrel feed processed in this FCC
unit.
Example 2: Residue feed application
The FCC unit in this commercial
example is a large, side-by-side unit
that processes a light sweet atmos-
pheric residue feed. The combined
feed Conradson carbon is typically
about 1.3 but can rise to more than
2. Sulphur is generally about
0.5 wt%. Nickel and vanadium are
in the feed at roughly equal
amounts and combine to deposit
about 5000 ppm total metals on the
equilibrium catalyst. The catalyst
replacement rate is about 3.3% with
Action.
The economic drivers for the
refner are minimising slurry make
and increasing C
4
olefnicity to
utilise available alkylation capacity.
To help maximise LPG olefnicity, a
ZSM-5 additive was employed with
both Action and the competitors
catalyst. The results are shown in
Table 2 and discussed below.
Comparison of e-cat phosphorous
and Z/M ratio
The phosphorus concentrations,
measured using X-ray fuorescence
on the equilibrium catalyst samples,
indicated that the amount of ZSM-5
additive in the unit equilibrium
catalyst was slightly lower on aver-
age during the Action catalyst
period. The periods used for the
competitors catalyst and for Action
were 47 and 31 individual weekly
cases respectively. All of the data
points within the Action dataset are
at 70% or greater turnover into the
inventory. The Z/M ratios demon-
strate a dramatic change in catalyst
technology from a low to a high
matrix activity catalyst.
Riser temperature
Throughout the competitors cata-
lyst period, the riser temperature
was maximised to minimise
bottoms yield. The improvement in
bottoms cracking subsequently
achieved with Action enabled the
refner to lower the riser tempera-
ture by 15F (8C) and tune the unit
to optimal LCO and olefns yields.
KBCs CatOp FCC model was
used to correct for changes in opera-
tions, feed and product cut points
and to forecast each weekly
balanced case on a consistent basis.
This meant each weeks data could
be tied to a consistent set of unit
conditions, feed rate and properties,
and equilibrium properties, thereby
removing the effects of operational
and feed changes from the analysis.
Unit conversion and coke selectivity
Compared on a constant basis of
unit operating conditions and feed
properties, both catalysts delivered
the same unit conversion and coke
selectivity in this residue process-
ing unit.
Despite the refner switching to a
lower zeolite activity and higher
matrix activity catalyst, both cata-
lysts showed similar levels of
conversion. This was partly because
Action catalyst additions were
lowered to maintain near constant
equilibrium catalyst activity. These
results demonstrate that, in commer-
cial applications, high matrix
catalysts do not show poorer coke
selectivity than low matrix catalysts,
though this is often observed in
small-scale laboratory testing.
2
Bottoms conversion and
LPG olenicity
The high matrix activity of Action
provided much greater bottoms
cracking and a substantial increase
in the LCO/bottoms ratio at
constant conversion, thereby satis-
fying the refners primary
economic goal.
The new catalyst also helped to
maximise alkylation feed. Action
provided similar LPG make to the
competitors catalyst at equal
conditions, but the LPG produced
was considerably more olefnic,
especially in C
4
olefns. As the
ZSM-5 additive level was slightly
lower during the Action period, if
the olefnicity data were to be
corrected to an equal ZSM-5 basis,
the improvement would be even
greater.
Increased RON and MON
Action increases RON and MON at
lower riser temperature in the raw
data and about 1 number over the
competitors catalyst when
corrected to constant conditions. A
Competitors system Action
Equilibrium catalyst P
2
O
5
, wt % 0.55 0.46
Equilibrium catalyst zeolite/matrix (Z/M) ratio 2.38 0.53

Delta
(Action Competition)
Riser temperature -15F (-8C)
Conversion, wt% No change
Coke selectivity
(coke/kinetic conversion) No change
Light cycle oil/bottoms ratio 17% improved
LPG olenicities, wt%/wt%
C
3
+0.043
C
4
+0.055
Gasoline octanes
RON +0.30
MON +0.28
Results from a FCC unit processing residue feed, shown at constant operating
conditions and product cutpoints
Table 2

The improved LPG
olenicity, octane
boost and bottoms
to LCO performance
contributed towards
improved protability
This article is based on a AFPM paper entitled
Take ACTION
TM
to Maximize Distillate and Alky
Feed from your FCC Unit.
References
1 Arriaga R, Bruno K, Sink or swim? How to
thrive in the ood of tight oils, paper AM-14-
64 presented at the AFPM Annual Meeting,
Orlando, USA, 2014.
2 Pouwels C, Bruno K, Better catalyst
evaluation strategies for maximizing FCCU
margins, paper AM-13-05 presented at the
AFPM Annual Meeting; San Antonio, USA, 2013.
Alan Kramer is Global FCC Modeling Specialist
for Albemarle. He has 16 years experience in
FCC including technical service, manufacturing
quality assurance, bench and pilot scale testing,
business development, and technical sales. He
holds a BS degree in chemical engineering from
Johns Hopkins University and MBA from Loyola
University in Baltimore.
George Yaluris manages the North American
FCC Technical Services team for Albemarles
Heavy Oil Upgrading division. He has 20
years FCC experience providing technical
support for the application of FCC catalysts,
commercialising new catalysts, developing
novel FCC catalyst and additive technologies.
He holds a diploma in chemical engineering
from the Aristotelian University of Thessaloniki,
Greece, and a PhD in chemical engineering
from the University of Wisconsin, Madison.
cracking and improve LPG olefnic-
ity, with C
4
olefns increasing
preferentially to make more alkyla-
tion feed. Isomerisation reactions
are enhanced, thereby helping to
increase gasoline octane and miti-
gate the effects of processing tight
oils.
The commercial cases from units
processing gas oil and residue feeds
demonstrate that Action catalysts
enable refners to maximise slurry
upgrading and to increase distillate
production or overall liquid prod-
uct. The results also show increased
butylene yields, LPG olefnicity and
gasoline octane. Action catalysts
deliver these benefts without using
ZSM-5 additives, which increase
LPG but make much more propyl-
ene than butylene and decrease
liquid product yield.
Overall, Action catalysts provide
the ideal performance profle for
refners that want to maximise
bottoms cracking and distillate
production, and keep the alkylation
unit full by improving LPG quality,
primarily C
4
olefnicity.
rule of thumb suggests that ZSM-5
technology raises MON at only 50%
the rate of RON. However, the
ADZT-100 zeolite technology isom-
erisation activity in Action helped
to increase MON by 90% of the
improvement seen in RON.
The improved LPG olefnicity,
octane boost and bottoms to LCO
performance contributed towards
improved proftability. The total
beneft, estimated using the values
described above, was over $1 per
barrel feed to the FCC unit.
Conclusion
The availability of cheaper feed-
stocks in the market is changing
the mix of crudes being processed.
Gasoline is less proftable than
it used to be, but the importance
of alkylate is growing because
it is an excellent, high octane,
low sulphur blending component
that will help refners meet US
EPA Tier III and other local
regulations.
Albemarles novel FCC catalyst is
designed to maximise bottoms
9
th
EFRC CONFERENCE
CONFERENCE FOCUS:
The Reciprocating Compressor and the Environment:
Why Recips are the Better Answer to Compression Problems
SPECIAL FEATURE:
Compressor Training:
Foundation Design for Reciprocating Compressors
September 10, 2014
September 11-12, 2014 Hofburg, Vienna - Austria
For Programme and Online Registration: www.recip.org
9
t
h

E
F
R
C

C
O
N
F
E
R
E
N
C
E
EFRC_Advert_PTQ.indd 1 20.02.2014 16:32:47
Advanced Rening Technologies
7500 Grace Drive
Columbia, MD 21044 USA
+1.410.531.4000
www.artcatalysts.com
Global leader in
hydroprocessing
catalysts offering
the complete
range of catalysts
and services
Penthouse Suite Sunday and Monday after 5:30 p.m. | Lunch Monday
art.indd 1 28/02/2014 16:52
Optimising hydroprocessing
catalyst systems
G
rowth in the output of
refned products is driven
strongly by demand for clean
diesel and new regulations on
gasoils between now and 2020.
Notably, annualised global growth
in demand for diesel and gasoil is
predicted to be about 2%, outpac-
ing gasoline at 1.3%, with the
estimated gasoline/diesel gasoil
ratio dropping from 0.85 in 2012 to
0.81 in 2020.
1
In addition to contin-
ued growth in Asia and continuing
recovery elsewhere, standards
covering motor vehicle mileage as
well as ethanol mandates in North
America and emerging regulatory
restrictions on marine fuels add
further momentum to this trend.
Bunker fuel regulations that will be
effective from 2015 and require
0.1% sulphur limits in emission
control areas (ECA) in North
America and northern Europe will
underlie a shift in demand to
diesel/gasoil products with an
expected concurrent boost in diesel
prices, primarily due to quality
requirements. Meanwhile, refning
capacity additions will outstrip
global demand in the 2015-2020
period and will continue to pres-
sure refning margins. In short, it
will be a period of opportunity for
refners that have the fexibility in
their hydrocracking capabilities,
especially if a robust ULSD hydro-
treater is available that can marry
their catalyst system needs and
operational responses to changing
economic scenarios.
In early 2013, Advanced Refning
Technologies (ART) and Chevron
Lummus Global (CLG) announced
an agreement in which ART has
exclusive rights to sell CLGs
Flexibility in catalyst technology and processing tactics optimises hydrocracker
and ULSD operations to meet diesel and gasoil production targets
WOODY SHIFLETT, CHARLES OLSEN and DAN TORCHIA Advanced Rening Technologies
DAVID BROSSARD Chevron Lummus Global
hydrocracking and lubes hydropro-
cessing catalysts to petroleum
refners worldwide for unit reflls.
The outcome of this agreement
streamlines hydroprocessing cata-
lyst supply and improves technical
service for refning customers by
establishing ART as the single point
of contact for all their hydropro-
cessing catalyst needs. In this
context, this article addresses
approaches to catalyst technology
and processing tactics to optimise
hydrocracker and ULSD unit oper-
ation in order to meet the need for
diesel and gasoil production in the
future.
Molecular management and
hydroprocessing units
Of all diesel boiling range materi-
als, FCC light cycle oil (LCO)
stands out as one of the lowest
value feedstock materials. It is
usually the most diffcult to
manage operationally in a hydro-
processing unit, largely due to its
combination of olefns and the
refractory nature of the LCO. It has
the highest demand for hydrogen
to produce a clean diesel or even
0.1 wt% sulphur marine gasoil, and
offers heat release management
challenges when processed at
higher fractions in a hydroprocess-
ing unit feed. Provided there is
adequate hydrogen supply, LCO is
sometimes best processed in the
hydrocracker along with other
feeds such as atmospheric or
vacuum gasoils) (AGO or VGO). In
addition, LCOs have variable qual-
ity: depending on the refnery
confguration, the LCO may be
produced from an FCC with a
feed pre-treater and consequently
may contain fairly modest levels of
sulphur and nitrogen. Although
they appear to be easier feeds
due to their lower levels of
contaminants, the remaining impu-
rities are also among the toughest
to treat.
Coker gasoils can be processed
either in the hydrocracker or the
ULSD unit subject to individual
unit capacities and infrastructure
limitations such as hydrogen avail-
ability, pressure, endpoint, and
impurities. Heavy coker gasoils
(boiling well above the diesel
range, >975F, 525C) are best sent
to a hydrocracker although they
can present challenges to process-
ing in signifcant quantities even in
modern, robustly designed hydroc-
rackers. A hydrocracker originally
designed or revamped for VGO
service is a most suitable outlet.
This offers more potential to
maximise diesel yields, especially
in recycle fow confgurations and
at higher pressures. Light coker
gasoils, on the other hand, are read-
ily processed to ULSD in a diesel
hydrotreater provided there is
adequate hydrogen partial pressure
and the unit has an appropriately
tailored catalyst system to remove
contaminants and provide the
required sulphur conversion.
Straight run (SR) gasoils present
the least challenging processing
constraints and can be fed to either
the hydrocracker or ULSD unit,
although the ULSD unit is typically
the preferred outlet. Exceptions
include cases where the SR feeds
are needed as diluent components
to aid in managing limitations to
hydrogen consumption, and heat
release issues in hydrocrackers
cat art.indd 1 28/02/2014 12:40
Catalyst system optimisation for
the SSOT is often infuenced
strongly by the desired outlet for
the UCO it produces: lube plant
feed will favour higher viscosity
index (VI), aromatics saturation
and HDS, while FCC feed will
favour HDN, removal of polynu-
clear aromatics and HDS. Balancing
with needs are the light product
drivers: ULSD or the less demand-
ing 0.1 wt% sulphur marine fuel. If
ULSD production is a target, and
cannot be produced within the
SSOT units constraints, it is critical
to factor in and model the effect of
this pre-processed component as
feed to the ULSD unit. It will
clearly include more diffcult, steri-
cally hindered sulphur compounds
for HDS in the ULSD unit.
Catalyst system selection and
optimisation is controlled by a
number of constraints that must be
accommodated in a single stage:
Hydrodemetalisation (HDM)
needs, driven by HVGO and/or
deasphalted oil (DAO) components
as well as by crude source (arsenic
and other contaminants), and coker
products in the feed (silicon
contaminations)
HDN requirements for the hydro-
cracking function of the catalyst
systems that follow
Hydroconversion targets for
removal of heavy components
HDS needs for products such as
ULSD, marine gasoil, and UCO
Aromatics removal (lube or FCC
applications)
Isomerisation (for lube needs).
Optimisation of a SSOT catalyst
system is further challenged when
the application involves a unit
converted from former service such
as FCC pretreatment or, in less
common cases, diesel treating. In
such cases, heat release and hydro-
gen consumption come into play as
these units typically contain only a
few deep beds. Semantics can
sometimes obscure the proper
application of catalyst technology.
A mild hydrocracker is merely a
low-conversion SSOT (<40%) and is
most effectively evaluated as a part
of the SSOT catalyst system
continuum.
SSOT systems typically demand
the highest activity catalyst
designed for more paraffnic and
naphthenic feeds.
Processing tactics are balanced
between these considerations of
feedstock molecular management
and the designs, limitations and
strategic intent of the unit in the
refning scheme. Hydrocrackers
have traditionally been designed to
pump hydrogen into the feedstock
to convert heavier, higher-boiling
materials into more valuable prod-
ucts, while capitalising upon
aromatics saturation to increase
volume swell as well as product
value parameters (density, cetane,
smoke point, and so on). Until
recently, ULSD has been a second-
ary priority and generally not even
a consideration in the original
design of the majority of hydroc-
racking units operating today. With
a robust ULSD unit in the refnery,
this order of priorities need not
only be overridden but can be
augmented by the latest catalyst
systems for hydrocracking that
have been designed for maximum
desulphurisation (HDS) activity as
well as fundamental nitrogen
removal (HDN), hydrocracking and
saturation.
The versatile hydrocracker and
catalyst system exibility
While several hydrocracker confg-
urations are in current use, two
dominate the landscape, especially
when addressing clean fuels
production: single-stage, once-
through (SSOT) confgurations and
two-stage, recycle (TSREC) confgu-
rations.
2
A perspective over a
decade of application is shown in
Figure 1.
The SSOT confguration is both
simple and versatile, and represents
the simplest option when uncon-
verted oil (UCO) has high value as
either a lube plant feed or a FCC
feed. This confguration dominates
the low conversion market (>70%
of that market). The SSOT process
confguration is shown in Figure 2.
22.6%
75.2%
2.2%
TSREC
SSOT
Other
Figure 1 Hydrocracker licences
F re sh
fe e d
R1 R2
Fractionator
G a s
N a p h th a
J e t
D ie se l
U n c o n ve rte d
b o tto m s
Figure 2 SSOT process conguration
+2 0
+4 0
+5 0
+3 0
+1 0
B a se
H
D
N

a
c
t
i
v
i
t
y
,

F
1 9 7 2 1 9 8 8 1 9 9 6 2 0 0 3 2 0 0 6 2 0 0 9 2 0 1 1 2 0 1 3
F o r u se w ith se le c t
h yd ro c ra c k e rs
Figure 3 Commercial development timeline for high activity SSOT hydrocracking
cat art.indd 2 28/02/2014 12:40
components to meet HDN and
HDS needs. Chevron Lummus
Global, teaming with Advanced
Refning Technologies, has met this
challenge over time as illustrated
by the rapid commercialisation of
hydrocracking pretreatment cata-
lysts (see Figure 3).
Without the fexibility of recycle
and adjustment of the recycle cut
point (RCP), product selectivity in
the SSOT is controlled by choice of
the catalyst system, and largely the
choice of the hydrocracking catalyst
component(s), and the operating
temperature regime and span.
Hydrocracking catalyst product
families typically exhibit a trade-off
between selectivity to distillates and
activity (temperature required for a
target conversion level). Premier
catalyst performance is defned by
innovations that increase both selec-
tivity and activity. Figure 4 shows
the progression of such performance
for the hydrocracking catalysts
provided by ART.
Catalyst system design in an
SSOT can involve more than a
single solution. While a single
hydrocracking catalyst from the B
range might seem an obvious solu-
tion for a refner desiring A
selectivity, but lacking the infra-
structure to compensate for the
lesser activity, synergies in
multi-catalyst combinations might
instead point to a system of A and
C catalyst and can actually achieve
a better result than pure B alone.
TSREC confgurations offer a
high level of fexibility, in addition
to providing the more favourable
means to achieve conversion levels
of over 90%. TSREC confgurations
are also the preferred means to
achieve full naphtha/gasoline
selectivity. The confguration is
shown in Figure 5.
TSREC units offer the refner the
ability to operate the two stages
differently in order to simultane-
ously meet separate goals for each
stage. This confguration also offers
the fexibility to balance the stages
to optimise the desired product
selectivity and qualities. Note that
although this unit is shown with
two reactors, they are often built
with multiple reactors, generally as
part of the frst stage providing
even greater ability to process
poorer value stocks. As an exam-
ple, the frst stage could be targeted
to provide a diesel draw suitable
for marine fuel blending as well as
pretreatment for the second stage
which could be targeted to produce
ULSD. Contrasted with the SSOT,
the TSREC has added operational
fexibility provided by the ability to
adjust RCP and per-pass conver-
sion in each stage, plus a second
catalyst system that allows optimi-
sation of an additional catalytic
component. In addition, TSREC
will enable production of other
very high quality products such as
Jet-A which can be recovered as a
single product or recovered with
the ULSD, depending upon the
economics of the day. In addition,
feedstocks can be shifted with the
ULSD unit to further add operating
space. This integration and fexibil-
ity permits the refnery to take full
advantage of seasonal or frequently
changing economics.
Selection and optimisation of a
catalyst system in the frst stage is
often infuenced by feed quality
and contaminants nitrogen,
sulphur, metals, silicon, and arsenic
being the typical suspects. This is
especially challenging for older
units but can be equally challeng-
ing for new units.
Following the removal of feed
contaminants, the remaining cata-
lyst volume can be used to achieve
conversion and selectivity goals.
Often the frst stage is required to
achieve 50-60% conversion after
removing feed contaminants for
both stages. Depending upon unit
objectives, frst stage cracking cata-
lyst can be chosen from any of the
A, B, or C groups.
Second stage catalyst selection will
largely be driven by the perfor-
mance of the frst stage to achieve
the units desired overall goals.
Second stage catalyst will contribute
signifcantly to improvement in
product quality and to the ability to
achieve very high levels of conver-
sion to the desired product, typically
diesel or total distillate these days.
ULSD unit and catalyst system
optimisation
ULSD units also face challenges in
molecular management. A properly
designed catalyst system and
K e ro /je t M a x n a p h th a D ie se l/k e ro
P ro g re ssive
g e n e ra tio n s
B a se m e ta l
H yd ro c ra c k in g
C a ta lyst p o rtfo lio
M a x d ie se l
A
B
C
S
e
l
e
c
t
i
v
i
t
y
Activity
Figure 4 Selectivity and activity improvements for hydrocracking catalysts by a leading
hydroprocessing catalyst supplier
F re sh
fe e d
G a s
N a p h th a
J e t
D ie se l
U n c o n ve rte d
b o tto m s
R1
R2
Fractionator
Figure 5 TSREC process conguration
cat art.indd 3 28/02/2014 12:40
eventually, a minimum in the prod-
uct sulphur curve is reached
(maximum HDS activity). The posi-
tion and magnitude of this
minimum, shown in Figure 6, varies
with feed properties and operating
conditions.
The fgure also shows relative
hydrogen consumption and, again,
as the percentage of the NiMo
component increases, hydrogen
consumption relative to the base
CoMo system increases. In the
region where the system shows the
best activity, hydrogen consump-
tion is only slightly greater than
that of the all-CoMo system, and
well below that for the all-NiMo
catalyst. This is a direct result of
the different kinetics for sulphur
and aromatics removal and is a
critical consideration when custom-
ising the staged catalyst system.
For units that have a hydrogen
constraint, the key to designing the
proper catalyst system is increasing
hydrogenation selectivity to
provide the highest HDS activity
while at the same time minimising
hydrogen consumption (that is,
minimising excess aromatics satura-
tion). How this is accomplished is
shown in Figure 7 which compares
the concentration profles for poly-
and mono-ringed aromatics as a
function of residence time for a
CoMo and NiMo catalyst under
typical ULSD unit conditions.
Figure 7 shows a rapid decrease
in polyaromatics concentration and
a corresponding increase in mono-
ringed aromatics for both catalysts
as the residence time is increased.
Clearly, however, the NiMo cata-
lyst is much more effcient at
hydrogenating the fnal aromatic
ring as evidenced by the lower
mono-ringed aromatic concentra-
tion with increasing residence time
compared to the CoMo catalyst. At
the longest residence time (lowest
LHSV) on the chart, the NiMo cata-
lyst has about 15 numbers
(absolute) lower mono-ringed
aromatics concentration than the
CoMo catalyst, and that corre-
sponds to about 300 scf/bbl higher
hydrogen consumption for the
NiMo catalyst.
These data demonstrate that the
hydrogenation activity of the
better performance than either
CoMo or NiMo catalysts alone.
An important aspect of the staged
catalyst system is designing the
optimum proportions of the CoMo
and NiMo catalysts to deliver the
best performance. This depends
upon a number of factors, includ-
ing the unit objectives, feed and
operating constraints. A more
detailed discussion of these factors
and how they impact system design
can be found in references 3 and 4.
One of the key advantages of the
system is the effcient use of hydro-
gen. Figure 6 illustrates how the
system can be tailored to provide
the best balance of high HDS activ-
ity while minimising hydrogen
consumption. The fgure shows that
as NiMo catalyst is added to the
system, there is a signifcant
increase in HDS activity relative
to the all-CoMo reference and,
optimised processing scheme can
help the refner maximise his proft
goals. To help refners deal with the
severe demands of ULSD, ART
developed a staged catalyst system
in 2001. This commercially success-
ful system utilises state-of-the-art
catalyst technology which is staged
in the proper proportions to
provide the best performance while
at the same time meeting each
refners requirements. The catalyst
staging is designed to take advan-
tage of the different reaction
mechanisms for sulphur removal; a
high activity CoMo catalyst eff-
ciently removes the unhindered,
easy sulphur via the direct abstrac-
tion route, and a high activity
NiMo catalyst then attacks the
remaining sterically hindered, hard
sulphur. Experience has proven
that the properly confgured
SmART Catalyst System provides
H yd ro g e n c o n su m p tio n
S u lp h u r
P
r
o
d
u
c
t

s
u
l
p
h
u
r
,

p
p
m
R
e
l
a
t
i
v
e

h
y
d
r
o
g
e
n

c
o
n
s
u
m
p
t
i
o
n
1 0 0 % C o M o 1 0 0 % N iM o
SmART Syst ems
Figure 6 Balancing high HDS activity while minimising hydrogen consumption
3 0
4 0
3 5
2 5
2 0
1 5
1 0
5
C
o
n
c
e
n
t
r
a
t
i
o
n
,

%
0
0 0 . 1 0 . 2 0 . 3 0 . 4 0 . 5 0 . 6 0 . 7 0 . 8 0 . 9 1 . 0 1 . 1 1 . 2
1
/
LHSV
, hours
C o M o c a ta lysts
N iM o c a ta lysts
M o n o s
P N A s
Figure 7 Effect of increasing residence time on aromatics conversion
cat art.indd 4 28/02/2014 12:41
A major multinational, vertically
integrated energy company, work-
ing with the licensor and catalyst
supplier, can provide a powerful
depth of knowledge on how to
optimise catalyst and unit
operations.
References
1 IHS CERA, Rening and Product Markets
Annual Strategic Workbook, 2013.
2 Torchia D, Arora A, Vo L, Clean, green,
hydrocracking machine, Hydrocarbon
Engineering, June 2012.
3 Olsen C, Krenzke L D, Custom catalyst
systems for meeting ULSD regulations, 2005
NPRA Annual Meeting, Paper AM-05-17.
4 Olsen C, DAngelo G, No need to trade
ULSD catalyst performance for hydrogen
limits: SmART approaches, 2006 NPRA Annual
Meeting, Paper AM-60-06.
Woody Shiett is the Deputy Managing
Director of Advanced Rening Technologies.
Charles Olsen is the Director, Distillate R&D
and Technical Services with Advanced Rening
Technologies.
Dan Torchia is the Director, Hydrocracking
and Lubes Catalysts with Advanced Rening
Technologies.
David Brossard is Proposals and Service
Manager with Chevron Lummus Global.
cannot be tolerated, a SmART
system can be designed which will
deliver high HDS activity and mini-
mise hydrogen consumption. In
cases where the hydrogen pressure
is lower, the staged catalyst system
is often more active than either
component alone without increas-
ing the hydrogen consumption
signicantly over the all-CoMo
system.
Service
State-of-the-art technical support is
required to get the most from
todays advanced catalysts and
catalyst systems. Assessing and
recognising unit limits is key to
achieve the reners operating cycle
goals, especially before a hard limit
is reached that will result in a
shortened cycle, reduced through-
put, or both.
The journey begins with speci-
cation of the appropriately tailored
catalyst system for the processing
and economic needs, and continues
with how catalysts are loaded and
how the unit is started up to
achieve the most from the catalyst.
system can be tuned by adjusting
the relative volumes (residence
times) in the CoMo and NiMo beds
in the reactor. Of course, not all
units have a hydrogen constraint,
and in those cases the incremental
increase in aromatics saturation
and the correspondingly higher
hydrogen consumption obtained by
the NiMo catalyst offers benets
such as cetane improvement and
the ability to process more cracked
stocks. Commercial experience with
the SmART catalyst system has
demonstrated that a properly
designed ULSD unit, combined
with the right catalyst system, can
process up to 100% cracked stocks
to produce <10 ppm sulphur and
provide signicant cetane uplift
and volume swell.
In applications where there is
sufcient hydrogen availability and
partial pressure, a NiMo catalyst is
likely the most active system for
HDS. However, it will consume
signicantly more hydrogen due to
its efciency at catalysing hydro-
genation reactions. If the
incremental hydrogen consumption
MINIDIS ADXper t
G ra b n e r I n stru m e n ts M e sste ch n i k G m b H | A-1 2 2 0 Vi e n n a , Au stri a | D r. O tto -N e u ra th -G a sse 1
P h o n e +4 3 -1 -2 8 2 1 6 2 7 -0 | F a x +4 3 -1 -2 8 0 7 3 3 4 | i n fo . g ra b n e r-i n s tru m e n t s @ a m e te k . a t
QUICK, ACCURATE, PORTABLE
DISTILLATION
P o rta b le , Tru e Atm o sp h e ri c D 7 3 4 4 D i sti ll a ti o n
E xce lle n t D 8 6 , I S O 3 4 0 5 , I P 1 2 3 C o rre l a ti o n
F u lly Au to m a te d M e a su ri n g a n d C le a n i n g
6 m L o f S a m p le
N o G l a sswa re , n o O p e n F l a m e
D i sti ll a ti o n o f G a so li n e , J e t F u e l , D i e se l , S o lve n ts,
U n k n o wn S a m p le s, R a ffi n a te s a n d B i o d i e se l
S p e ci fi e d fo r U se b y U S P i p e li n e s
ADXpert half page1.indd 1 06.12.2013 11:46:37
cat art.indd 5 28/02/2014 12:41
Albemarle IBC
www.albemarle.com
Advanced Rening Technologies 58
www.grace.com/About/Businesses/ART.aspx
AMACS Process Tower Internals 42 & 47
www.amacs.com
Axens OBC
www.axens.net
BASF Corporation, Catalysts Division 11
www.catalysts.basf.com
Cat Tech 23
www.cat-tech.com
CB&I 4
www.CBI.com
Chevron Lummus Global 16
www.chevronlummus.com
CRI Catalyst 33
www.cricatalyst.com

Criterion Catalyst & Technologies 2
www.criterioncatalysts.com
DigitalRening 35
www.digitalrening.com
eptq.com 15
www.eptq.com
EFRC 57
www.recip.org
Everlasting Valve 29
www.everlastingvalveusa.com
ExxonMobil Research & Engineering 25
www.exxonmobil.com/Apps/ReningTechnologies/
default.aspx
Grabner Instruments 63
www.grabner-instruments.com

Grace Davison IFC
www.grace.com/About/Businesses/GCT.aspx
Haldor Topse 36
www.topsoe.com
Johnson Matthey Process Technologies 7
www.jmprotech.com
Merichem 49
www.merichem.com
Process Consulting Services 52 & 54
www.revamps.com
Sabin Metal Corporation 28
www.sabinmetal.com
Saint-Gobain NorPro 26
www.norpro.saint-gobain.com
UOP, A Honeywell Company 9
www.uop.com
Alphabetical list of advertisers
For more information on these advertisers, go to www.ptqenquiry.com
ad index copy 10.indd 1 03/03/2014 15:54
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axens.indd 1 6/12/12 13:17:48

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The butylene advantage

Contactor that offers a variety of

. With a continuing record of success, Albemarles ACTION

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