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catalysis

2015

ptq

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

As the global leader in catalysis, BASFs drive is to


fuel the world by providing innovative technologies,
products, and services to enhance performance and
sustainability for the petroleum refining industry. We
create and deliver value to refineries through flexible
FCC catalysts and additive solutions, and advanced
technical service. When individual solutions solve global
problems, its because at BASF, we create chemistry.
www.catalysts.basf.com/refining

Security of
feedstock supply

catalysis
ptq

Vol 13 No 2
2015
2008
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
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tel +1 281 374 8240
fax +1 281 257 0582
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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
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Back numbers available from the Publisher
at $30 per copy inc postage.

3 Change for the better


Chris Cunningham

5 espite
ptq&a
signs in 2007 of a slowdown in various sectors of the economy,

refiners remain a big play for prospective investors. It used to be


wisdom and
that ZSM-5
higher fuel
prices and apropylene
slowing economy
17 conventional
Hydrogen transfer
in maximising
would curb demand and increase supply, but for the past seven years
De to
Graaf,
Mehdi
Charles
Radcliffe,
Martin
Evans
that has notBart
proved
be the
case. Allahverdi,
While the rate
of increase
in world
oil demand
has declinedand
since
the
surprising
4%
surge
in
2004,
it
nevertheless
appears
that
Paul Diddams
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
Johnson Matthey Process Technologies
increasing oil consumption by China, India and even the Middle East producers
themselves will continue. It is also safe to assume that refinery and petrochemical
conversion
capacity
will maximises
need to expand.
23 unit
ZSM-5
additive
propylene
No massive new sources of energy are expected to come on stream for the
Carl Keeley,
Vasileios
Komvokis,
Modesto
Miranda,
Harristo
foreseeable future.
The world
will remain
dependent
on oil
and gasDavid
for decades
come even and
though
the
upstream
industry
faces
increasing
challenges
in the
Jason Smith
discovery and production of new sources. In fact, some well-placed industry
BASF
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 significant
investment
in refineryactivity
upgradesindespite
surging costs security of feedstock
29 Increased
FCC pretreat
supply, albeit unconventional low-quality feedstock, takes precedence over the
Charles supply.
Olsen and Brian Watkins
quality of feedstock
FeedstockAdvanced
options such
as biomass
(for biofuels production), Canadian tar sands
Refining
Technologies
(for distillate production) and other types of unconventional crude sources require
reactor technology that allows for the integration of these operations into existing
Recovering
andquality
refining
precious
process35
confi
gurations. The
of these
typesmetals
of feedstock are one important
reason whyBradford
a wider array
of
catalysts
has
been
introduced
into the market. For
Cook and Robert Jacobsen
example, as refiners cut deeper into the vacuum tower, the concentration of
Sabin Metal Corp
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),
metals, nitrogen
and
other
undesirable
components is one of the
39high
Structured
catalysts
for
steam
reformers
main reasons why hydrotreaters and hydrocrackers are becoming larger to
William
Whittenberger
Johnson
Matthey
accommodate
not only
higher volumes
of catalyst,
butProcess
also a Technologies
wider variety of
catalyst withPeter
specifi
c
formulations.
Farnell Johnson Matthey plc
Non-catalytic processes are also playing a significant role in the refiners ability
to process whatever unconventional crude sources become available. For example,
45ners
Four-stage
some refi
processinghydrocracking
higher volumes pretreatment
of resid and atmospheric tower bottoms
have considered
adding
certain
types
of
solvent-extraction
processes in addition
Stefano Melis
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
Albemarle
coker operations.
Improvements in furnace technology, such as with olefin steam
cracker operations, have resulted in significant increases in worldwide ethylene
capacity.47 Catalysis Industry Updates
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 field 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
therefinery,
specifi
cs of certain reactor and catalytic issues of importance
to
OMVs Schwechat
Austria.
Photo: OMV
the industry.
2015. 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.

Ren G Gonzalez

Maximum
PROTECTION

for

Maximum
PERFORMANCE

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portfolio to protect your catalyst investment.
With exceptional stability in severe environments, SENTRY MaxTrap catalysts maximize removal
of specific feed poisons.
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Trust Criterions SENTRY Guard Catalysts and Support portfolio to keep your catalyst bed running
at peak performance throughout its life. Our scientists stand behind it.

Leading minds. Advanced technologies.

www.CRITERIONCatalysts.com

Security
Change forof
feedstock
the better supply

catalysis
ptq

Vol213 No 2
Vol 20 No
2008
2015
Editor

Editor Ren G Gonzalez


Chris
Cunningham
editor@petroleumtechnology.com
editor@petroleumtechnology.com
Production
Editor
Production
Editor
Rachel Storry
Rachel Zamorski
production@petroleumtechnology.com
production@petroleumtechnology.com
Graphics Editor
Rob Fris Graphics Editor
graphics@petroleumtechnology.com
Mohammed Samiuddin
graphics@petroleumtechnology.com

Editorial
tel +44 844 5888 773
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667
Editorial

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USA
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telAdvertising
+44 844 5888Sales
771 Manager
fax +44 844Paul
5888Mason
662
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Publisher
Nic Allen
Advertising Sales
publisher@petroleumtechnology.com
Bob Aldridge
sales@petroleumtechnology.com

Circulation
Sales Office
JackiAdvertising
Watts
tel
+44 870 90 303 90
Louise
Shaw
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circulation@petroleumtechnology.com

Publisher
Crambeth Allen
Publishing Ltd
NicArms
Allen
Hopesay, Craven
SY7 8HD, UK
publisher@petroleumtechnology.com
tel
+44 844 5888 776
fax +44 844 5888 667
Circulation

Jacki Watts
ISSN 1362-363X

circulation@petroleumtechnology.com
PTQ (Petroleum Technology
Quarterly) (ISSN Ltd
Crambeth
Allen Publishing
No: 1632-363X, USPS No: 014-781) is published
Hopesay,
Craven
Arms
SY7by8HD,
UK
quarterly plus annual Catalysis edition
Crambeth
tel +44Ltd870
600 20
Allen Publishing
and is90
distributed
in the US
by SP/Asendia,
17B 870
South Middlesex
fax +44
90 600Avenue,
40
Monroe NJ 08831. Periodicals postage paid at New
Brunswick, NJ. Postmaster: send address changes to
PTQ (Petroleum
Technology
Quarterly), 17B South
ISSN
1362-363X
Middlesex Avenue, Monroe NJ 08831.
Back numbers available from the Publisher
at $30 per copy inc postage.

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.

DT

espite signs in 2007 of a slowdown in various sectors of the economy,


here has been an unusual incidence of comings and goings and shuffling
refiners remain a big play for prospective investors. It used to be
around in the catalyst industry since the last issue of Catalysis. Often
conventional wisdom that higher fuel prices and a slowing economy
enough, this is an ominous sign of business in crisis. But in the case of
would curb demand and increase supply, but for the past seven years
refining catalysts, and no doubt to the relief of refiners keen to ensure reliable
that has not proved to be the case. While the rate of increase in world oil demand
the material,
the message
frominall2004,
of thisitactivity
is that appears
the industry
has supplies
declinedofsince
the surprising
4% surge
nevertheless
that
seems
to
be
doing
just
fine.
demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
This issue
of Catalysis sees
CatacelIndia
take and
a bow
(see
p39)
as theEast
latest
recruit
increasing
oil consumption
by China,
even
the
Middle
producers
of
Johnson
Matthey
Process
Technologies.
The
group
already
included,
themselves will continue. It is also safe to assume that refinery and petrochemical
among its
brands
with
theneed
JM subscript,
conversion
unit
capacity
will
to expand.catalyst additives specialist Intercat,
as massive
well as Katalco
with its
for expected
methanol,tohydrogen,
natuNo
new sources
of catalysts
energy are
come onsubstitute
stream for
the
ral gas and
gas-to-liquids.
Theremain
Cataceldependent
acquisitionon
extends
Mattheys
foreseeable
future.
The world will
oil andJohnson
gas for decades
to
reach
intothough
steam reforming;
the product
interest features
catalysts
on
come
even
the upstream
industryrange
facesofincreasing
challenges
in the
a metaland
foil production
base, ratherofthan
more conventional
ceramic
pellet arrangediscovery
newthesources.
In fact, some
well-placed
industry
ment.think
This,2008
says
thebedeveloper,
delivers
activity,in improved
heat
analysts
may
the year where
therehigher
is no increase
crude supply
at
all from
regions
outside
of OPEC.
thisimproved
reason, wecarbon
will continue
to see
signifi
transfer,
lower
pressure
dropFor
and
resistance
all
at cant
the
investment
in refinery upgrades despite surging costs security of feedstock
same time.
supply,
albeit
unconventional
low-quality feedstock,
takes
precedence
over for
the
Prior
to the
takeover, the independent
Catacel was
perhaps
best known
quality
of feedstock
supply.
its work
on catalysis
and heat exchange for fuel cells, an area of interest the
Feedstock
such the
as biomass
(for biofuels production), Canadian tar sands
companyoptions
shares with
new owner.
(for distillate
production)
and
other
types
of unconventional
sources
Shortly after the Catacel deal, Johnson
Matthey soldcrude
its gold
andrequire
silver
reactor
technology
that
allows
for
the
integration
of
these
operations
into
existing
refining business to Asahi Holdings, saying at the time and in line with
the
process
confi
The
quality of these
types
of feedstock
are one
important
growth
ingurations.
its process
technologies
line-up
that
its long term
strategy
is to
reason
a wider array
of catalysts
been introduced
into the
market.
For
turnwhy
its chemical
expertise
to highhas
technology
applications
for sale,
rather
example,
as
refi
ners
cut
deeper
into
the
vacuum
tower,
the
concentration
of
than be embroiled in industrial processing activity on its own account.
metalsFor
in the
VGO
requires
a
properly
designed
guard
bed
system
to
protect
active
its part, W.R. Grace took the opposite line to acquisition with a decicatalysts in the hydrocracker. The characteristics of feedstock with low API gravity
sion to split down the middle into two new and separate companies. The
(eg, <10), high metals, nitrogen and other undesirable components is one of the
resulting half of interest here is based on the Grace Catalysts Technologies
main reasons why hydrotreaters and hydrocrackers are becoming larger to
business and also includes the former groups Materials Technologies diviaccommodate not only higher volumes of catalyst, but also a wider variety of
sion. For the time being at least, we shall have to grow accustomed to calling
catalyst with specific formulations.
this new entity
New Grace.
The company
emerging
the
other
of
Non-catalytic
processes
are also playing
a signifi
cant rolefrom
in the
refi
nershalf
ability
the
group
majors
on
construction
materials.
to process whatever unconventional crude sources become available. For example,
immediate
effect
of all
this was
leapand
in the
value of tower
the combined
some The
refiners
processing
higher
volumes
of aresid
atmospheric
bottoms
companys
shares;
projected
earnings
per
share
well
above
previous
estihave considered adding certain types of solvent-extraction processes in addition
mates;
and
a
slew
of
buy
advice
from
Wall
Streets
tipsters.
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
appeared toinview
the technology,
Chinese Newsuch
Yearasaswith
an opportunity
coker Albemarle
operations.also
Improvements
furnace
olefin steam
for renewal
withhave
an announced
of its divisions
following
its
cracker
operations,
resulted in reorganisation
significant increases
in worldwide
ethylene
takeover of lithium battery specialist Rockwood. The aim appears to be for
capacity.
more independent
activity
the corporations
business groups,
However,
any expansion
of for
the each
valueofchain
(eg, ethylene-to-propylene
via
including Refining
Solutions.
Alongside
other activities
in the world
of cataldehydrogenation)
requires
investment
in catalytic-based
processes,
as discussed
in
it seems
like just
anotherby
day
in the in
office.
the ysis,
following
articles
authored
experts
the field 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 specifics of certain reactor and catalytic issues of importance to
CHRIS CUNNINGHAM
the industry.

Ren G Gonzalez
Catalysis 2015

pcs myth.indd 1

8/3/12 09:55:39

catalysis q&a
Q

Do we need to regenerate spent catalyst to remove any


remaining carbon and therefore avoid processing surcharges
before we send it for metals reclamation?

Brad Cook, Vice President Sales and Marketing, Sabin


Metal Corp., bcook@sabinmetal.com

Spent precious metal bearing catalysts typically contain


high amounts of carbon and moisture (sometimes even
large chunks of carbon are present). This carbon and
moisture content must be minimised in order to
achieve accurate samples for value determination. It is
wise therefore to work with a full service precious
metals refiner that offers in-house thermal reduction (in
other words, kilning). This eliminates the need for the
refiner to trans-ship spent catalysts to off-site facilities
before the materials are delivered to a second location
for final recovery. This saves significant time and cost,
returning metals values more quickly and cost-effectively through one-stop shopping.

Jay Jaffe, Gulf Chemical and Metallurgical Corp.,


jay.jaffe@eramet-gulf.com

Gulf Chemical and Metallurgical Corps (Freeport,


Texas) process makes it unnecessary to remove carbon
before reclaiming NiMo or CoMo catalyst. The first part
of the GCMC process is a high temperature roaster, and
spent catalyst, which has had prior carbon removal, still
has to go through the same steps. In light of the double
handling, extended bin rentals and possibly double
freight involved with a hazardous waste, adding a first
step to the reclamation process would only add costs to
existing proven solutions. Through our recovery process
we are able to recycle 99% by weight of each dry ton of
spent catalyst we receive. Every pound of molybdenum
we recover as molybdenum oxide goes back into the
fresh catalyst market as a raw material. Our vanadium
goes to steel mills to provide strengthening properties to
their metal and/or super-alloy manufacturers for aerospace applications. The nickel/cobalt goes through a
smelting process before going to a nickel refiner where
it is refined and separated into high purity products.
Fused alumina is converted to a product that is used as
a fluxing agent in steel mills.

Is there a catalytic route for optimising the RVP of


gasoline from the FCC?

Kenneth Bryden, Manager Catalyst Evaluations Research


and Services, Grace Catalysts Technologies, Kenneth.Bryden@
grace.com

The Reid vapour pressure (RVP) of gasoline is primarily determined by the amount of light hydrocarbons
(C4s and C5s) present in the gasoline. RVP declines as
molecular weight increases. For example, the pure
component RVP of n-butane is 52 psi, the pure component RVP of n-pentane is 15 psi, and the pure
component RVP of n-hexane is 5 psi. The quantity of
C4s in gasoline has a greater effect on RVP than the
quantity of C5s. Modifying the FCC catalyst by changing equilibrium unit cell size and other properties can
shift the relative proportions of the hydrocarbon
species present in the FCC gasoline and thus shift the
RVP.
Any consideration of gasoline RVP must take into
account the entire gasoline pool of the refinery and the
unit operations that are used to produce the gasoline.
When a low RVP gasoline is desired to meet government RVP requirements, it is preferable to take C4s out
of the FCC gasoline pool and use alkylation to transform isobutane and butenes into high octane, low
vapour pressure alkylate. To reduce RVP, refineries
should optimise debutaniser operation to minimise the
C4s present in the FCC gasoline and thus maximise C4s
sent to the alkylation unit. Complexes with sufficient
alkylation capacity should also examine opportunities
to maximise butylene production from the FCC. This
can be done via proper choice of FCC catalyst and
additives.
Catalysts with lower hydrogen transfer will produce
more butylene. ZSM-5 additives and specialised dual
zeolite catalyst technologies can also increase the
amount of butylene produced. Multiple objectives
must be met in FCC operation and careful consideration of operating objectives and unit constraints is
needed when selecting a catalyst to meet a desired
goal such as optimising RVP.
Working closely with the technical service team of an
experienced FCC catalyst supplier is essential in identifying the best catalyst choice to meet refinery
objectives. An example of the application of optimised
catalyst technology to improve the properties of the
overall gasoline pool can be found in the article Role of
FCC catalyst in refinery profitability, PTQ, Q1 2014 by I
Chavdarov, D Stratiev, I Shishkova, R. Dinkov, V
Jegorov and P Petkov.

Paul Diddams, Global FCC Additives Market Manager,


Paul.Diddams@matthey.com

Gasoline RVP is usually lower than limits until light


volatiles are added to boost octane. Traditionally, C4s
are/were added to the gasoline up to the RVP limit.

Additional Q&A can be found at www.eptq.com/QandA

www.eptq.com

Catalysis 2015 5

However, these days where ethanol is present at high


levels there is little or no room for adding C4s indeed
in many cases C5s become a problem. Methanol is a
poor blending oxygenate for this reason. (It is more
volatile than ethanol and pushes up the RVP.) So what
can be done catalytically? The objective is in principle
to decrease the amount of C5 in the gasoline cut, which
ideally means increasing C6+ iso-paraffins since olefins
and aromatics are also limited and naphthenes and
n-paraffins have lower octane. In the FCC, the best
way to achieve this is with a high silica-alumina ratio
ZSM-5 additive (low unit cell size/volume) that
encourages isomerisation reactions without excessive
cracking of heavy naphtha to light naphtha plus LPG.
Rare earth on the base catalyst may also be increased
to encourage saturation of iso-olefins to iso-paraffins
via hydrogen transfer, which increases the overcracking point and avoids excessive light naphtha
formation.

What are the advantages of in situ sulphiding over


presulphiding (or vice versa)?

Robert Bliss, Mid-Distillates HPC Specialist, Robert.Bliss@


Albemarle.com, and Jignesh Fifadara, Marketing Specialist
Applications Technology, Jignesh.Fifadara@Albemarle.com,
Albemarle

There are several advantages of both in situ sulphiding


and presulphiding (ex situ sulphiding), but it is first
important to understand the chemistry behind the
process. Most hydrotreating catalysts utilise oxidic
forms of molybdenum, cobalt, and nickel (MoO3, NiO,
and CoO) which need to be activated to sulphides
(MoS2, Ni3S2 and Co9S8) to perform the necessary
hydrotreating objectives. Sulphiding reactions are
exothermic, consume hydrogen, and release water.
High temperature and high hydrogen pressure in the
absence of sulphur compounds favour reduction of the
metals and should be avoided prior to catalyst activation. Lower valence oxides and metals are catalytically
inactive and are only very slowly converted into
sulphides. Therefore, proper sulphiding is critical to
the reactor performance.
In situ sulphiding occurs when the oxidic catalyst is
activated after the catalyst loaded into the reactor,
whereas ex situ activation occurs before catalyst loading. For this reason, one of the key benefits of in situ
sulphiding is the ease of catalyst handling and loading
into the reactor. When the catalyst has been ex situ
presulphided, the general recommendation is that the
catalyst should be loaded in an inert atmosphere. The
presulphided catalyst has the potential to be self-heating, if exposed to air for extended periods of time. This
is especially true for air flow through the catalyst. The
exception can be small reactors that can be loaded in
just a couple of hours, where there is no air flow
through the catalyst bed. In multibed reactors, loading
under inert conditions is mandatory due to the duration of the loading process and to properly install the
reactor internals. In situ sulphiding via a spiking agent

6 Catalysis 2015

(such as DMDS) is still the most common industrially


practised sulphiding procedure and also perceived to
be the cheapest option. However, there are certain
risks associated with in situ sulphiding. Due to the
toxic nature of sulphiding agents, extra precautions
need to be taken to mitigate leaks within the system.
Another drawback is the potential for incomplete
sulphiding of the active metals, which can be caused
by either low mass flux or equipment failures during
the start-up process. The downtime associated with in
situ sulphiding is longer, but different catalyst vendors
require different temperatures and hold periods to
fully activate their catalysts.
It is important to note the difference between presulphurised and presulphided catalysts. The active metals
on presulphurised catalysts are still in the oxide (inactive) form where the catalyst pore structure contains
sulphur compounds designed to decompose during
the first stage sulphiding temperatures. While presulphided catalyst eliminates the need to handle the
sulphiding agents at the refinery, it has some of the
same risks associated with in situ sulphiding.
Presulphided catalysts contain active metals that are
fully sulphided and will result in low to no exotherm
during start-up. With presulphiding, the catalyst is
treated off-site in a high temperature processing facility at controlled conditions. Loading and handling of
the catalyst becomes a concern (and can extend the
loading process), but no additional activation steps are
required during start-up. In general, this allows the
refinery to reduce the overall start-up time of the unit.
While presulphiding allows the refiner to mitigate
some of the risks mentioned with in situ sulphiding,
the option can be more expensive and have longer
lead times for catalyst delivery.
Both options are currently utilised by refiners and
each method provides some benefit. In addition to
cost, downtime and safety, refiners need to consider
unit application and the type of catalyst being utilised,
to optimise catalyst performance of their operation.

Charles Radcliffe, Senior Tech Service Engineer Europe,


Johnson Matthey, Charles.Radcliffe@matthey.com

The main advantages of presulphiding are that the


unit can be brought back on line quicker and there is
no need to handle toxic and extremely odorous presulphiding agents.

What is the best catalyst arrangement in the FCC for


maximising propylene output?

Carel Pouwels, Global FCC Specialist Resid, Albemarle,


carel.pouwels@albemarle.com

Maximising propylene from an FCC unit is no sinecure


as it requires a complete understanding of the profitability from the FCC unit and the chemistry involved in
maximising propylene. The optimisation of propylene is
never a standalone goal as refiners need to take into
account other (yield) objectives and unit limitations.
While optimal process conditions (such as high reac-

www.eptq.com

residue (MCR)? Refiners who cut


deep should not be surprised when
the HVGO product MCR is over 2
wt % and the vanadium content is
in excess of 10 ppmw. Any one of
such difficulties can result in lower
revenue, unstable operation or
even unit shutdown. It is critical to
understand that the inherent
properties of these low API gravity
crudes dictate that exact process
design is of paramount importance.
The point of this litany of possible
problems is to remind you not to
skimp in the early phases of
engineering. From the start of the
LP work through the completion of
front-end process engineering,
actual product yield and qualities
depend on the process design.

Nasty Stuff

This exchanger has seen better crude slates

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.

be questioned. Whichever the case,


however, an inescapable fact is
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ene catalyst outperformed other technologies in terms


of:
Improved coke selectivity
Reduced slurry yield
Reduced dry gas
Improved metals tolerance.

Figure 1 Performance of Albemarles maximum propylene catalyst

tor temperature) should be applied, even more


important is the catalyst technology to be used. Key to
a successful catalyst technology is low hydrogen transfer activity, while at the same time an optimum MAT
activity is required. Often the activity should be high
in order to generate the maximum precursors in the
gasoline fraction which in turn can be converted into
propylene. But when the refiners goal is to maximise
propylene and LCO, the MAT activity needs to be
tempered. For resid applications, typically one needs a
catalyst with low coke selectivity to control the regenerator temperature and allow processing of a
maximum amount of resid. The opposite can be
required when processing very clean and light feeds,
and when high coke selectivity is required to master
the heat balance and avoid the addition of torch oil or
other extra heat supplies.
As said, hydrogen transfer needs to be minimised in
order to maximise propylene. One of the crucial catalyst parameters is high matrix activity as matrix has
lower hydrogen transfer activity than zeolite. The
zeolite technology in turn needs to be optimised for
the generation of olefins in the gasoline range, and
catalyst manufacturers typically apply Y-zeolite or REY
(the latter being higher in hydrogen transfer. Next, a
shape selective zeolite is used to convert the light
gasoline olefins into propylene; ZSM-5 is the mostly
applied zeolite for this purpose.
Albemarle has been very successful in all feed applications (ranging from very light hydrotreated VGO
applications up to the heaviest resid units), delivering
record propylene yields with its maximum propylene
catalyst AFX. This unique catalyst features high matrix
activity in combination with its proprietary ADZT-150
zeolite technology which catalyses reactions all the
way to light olefins. The AFX catalyst applies a unique
assembly technology with the highest accessibility
index. This catalyst property has proven to be a key
parameter to reducing hydrogen transfer and thus
contributing to record propylene yields.
While record propylene yields are often considered
the highest priority, what ultimately counts is the profitability of the FCC unit and that goes beyond
propylene alone. Several refiners have trialled other
maximum propylene catalysts than AFX, but each of
them decided to turn back to Albemarles catalyst as it
proved to add more value. Figure 1 illustrates the
number of cases where Albemarles maximum propyl-

8 Catalysis 2015

Ron Butterfield, Senior Technical Service Engineer,


Johnson Matthey, Ron.Butterfield@matthey.com

For existing FCC units, the most common method


utilised to increase propylene output is to use ZSM-5
additives at up to about 15% of total catalyst additions.
ZSM-5 is a shape selective additive that promotes the
cracking of olefin intermediates from FCC gasoline.
High quality ZSM-5 additives can provide increases in
propylene of 2-5 wt% with no increase in propane,
n-butane, dry gas or coke. This approach will provide
a yield shift from gasoline into LPG olefins and
improve gasoline octanes while all other product selectivities remain unaffected.
For maximum propylene FCC units, high concentrations of ZSM-5 additives in inventory (up to 30%) are
needed. At these concentrations, ZSM-5 additives work
together with the base catalyst. The base catalyst alone
cracks feed and slurry into LCO and gasoline. However,
all reactions involving gasoline and smaller molecules
take place on both the base catalyst and the ZSM-5
additive. The base catalyst needs to be optimised to
minimise hydrogen transfer and maximise conversion.
These two objectives are not always perfectly aligned.
Minimising hydrogen transfer can be achieved by
reducing Y-zeolite unit cell size by lowering rare earth
on zeolite. Balancing the zeolite to matrix ration is also
important, as the matrix part of the catalyst exhibits
lower hydrogen transfer than the zeolite. The optimal
base catalyst composition and additive concentration is
always feed and unit dependent. In practice, most high
propylene FCC units tend to use low rare earth zeolite,
and those units which also process residue feeds tend to
have a lower zeolite to matrix ratio.

Clint Cooper, Technical Account Manager,


Technology, clint.cooper@rivetechnology.com

Rive

For conventional FCC units trying to maximise propylene output, most refiners will use a catalyst having
relatively low levels of rare earth exchange. This lower
unit cell size E-cat will inhibit hydrogen transfer reactions, which will increase yields of LPG olefins.
Additionally, many refiners will implement a ZSM-5
additive in order to further raise propylene yield.
ZSM-5 preferentially cracks the lower octane olefin
components in the C7C10 gasoline range into lighter
olefins in the C2C5 range, primarily propylene.
Rive Technology (Rive) has developed and commercialised Molecular Highway technology whereby a
precise series of mesopores are engineered into Y
zeolite, the primary active component of all FCC catalysts. These mesopores promote improved diffusion of
FCC feed molecules into and out of the zeolite crystals
of the FCC catalyst.
In addition to decreasing formation of coke,

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bottoms and dry gas, Rive has commercially demonstrated its ability to increase propylene production for
a given set of operating conditions. These valuable,
reactive molecules are quickly and efficiently channelled through the mesopores of the zeolite instead of
succumbing to secondary and tertiary cracking reactions, which would turn them into LPG paraffins and
dry gas.
Even larger propylene gains can be achieved for
refiners utilising the ZSM-5 additive, alongside a Rive
FCC catalyst. Because Rive also preserves the olefinicity of the gasoline range molecules, the combined
system of Rive catalyst with the ZSM-5 additive has
shown dramatic increases in propylene yield.
When the ZSM-5 additive is not used, switching to a
Rive catalyst typically increases the absolute propylene
yield by nearly 1 wt%. When the ZSM-5 additive is
used, switching to a Rive catalyst typically increases
the absolute propylene yield by nearly 2 wt% (all
values derived from ACE testing at constant 75 wt%
conversion).

We are finding high levels of catalyst fines in our marine


diesel product. Is there a processing cause/remedy that will
avoid heavy duty filtration of the product?

Charles Radcliffe, Senior Tech Service Engineer Europe,


Charles.Radcliffe@matthey.com

Assuming that this is FCC catalyst fines, and there is


no slurry being blended into the product, it sounds as
if either there is flooding occurring in the bottom of
the main fractionator, or a slurry exchanger leak,
although an exchange between LCO/HCO and slurry
would be unusual other than in a reboiled side stream
stripper.

Processing tight oil will increase the sodium, calcium and


iron content of our FCC feed. Can you outline some problems
and solutions we should expect?

Ann Benoit, Technical Service Representative, Ann.


Benoit@grace.com, and Kenneth Bryden, Manager Catalyst
Evaluations Research and Services, Kenneth.Bryden@grace.
com, Grace Catalysts Technologies

Tight oil feeds generally have high levels of iron,


calcium and sodium present in them.1 These contaminants deposit on the FCC catalyst and act as poisons
that have a negative impact on unit operation.
Sodium reduces the activity of catalyst and can result
in the destruction of zeolite. Maximising sodium tolerance within an FCC catalyst system requires the
highest quality zeolite. Grace catalysts have consistently demonstrated excellent zeolite stability and
activity retention in the face of high contaminant
metals. Sodium and vanadium work synergistically to
destroy zeolite crystallinity and increasing levels of
sodium can amplify the destructive effects of vanadium. Incorporating a vanadium trap in the catalyst
system can provide widely dispersed trapping capabil-

10 Catalysis 2015

ity to more effectively reduce the negative impacts of


the contaminant. Graces IVT-4 is an integral rare earth
based vanadium trap that converts contaminant vanadium into an inert rare earth vanadate, greatly
reducing zeolite deactivation and coke and gas production. Grace is currently using IVT-4 in 60%+ of its
worldwide catalyst formulations.
Iron can have a negative effect on catalyst performance. While particulate tramp iron from rusting
refinery equipment does not have a significant detrimental effect on catalyst, finely dispersed iron
particles in feed (either as organic compounds or as
colloidal inorganic particles) can deposit on the catalyst surface, reducing its effectiveness. The iron
deposits combine with silica, calcium, sodium, and
other contaminants to form low melting phases,
which collapse the pore structure of the exterior
surface, blocking molecules from entering the catalyst
particle and reducing conversion. Like iron, calcium
deposits on the exterior surface of the catalyst. As
calcium builds up on the surface, the particle
becomes compromised and this can result in unit
conversion loss. Iron, in combination with calcium
and/or sodium, has a greater negative effect on catalyst performance than does iron alone.2
The symptoms of iron and calcium poisoning
include a loss of bottoms cracking and conversion as
feed particles are blocked from entering the catalyst
particle. In addition to a drop in conversion and a
decline in bottoms cracking, poor catalyst circulation
could be a symptom of poisoning. A potential indication of iron poisoning is a drop in E-cat ABD. Nodule
formation on the catalyst, due to the build-up of iron
on the surface, prevents the E-cat from packing as
densely.
In evaluating the potential for iron poisoning, it is
important to calculate the incremental iron from the
feed, and not only assess the total iron level on E-cat.
This is because different catalysts have different starting iron contents. A general rule of thumb is that
performance could suffer with as little as 0.2 wt%
incremental iron, particularly for low alumina catalysts
that are more prone to iron poisoning. The level, of
course, is dependent upon factors such as the catalyst
resistance to iron poisoning and the concentration of
alkali metals contaminants such as calcium and
sodium.
To manage iron poisoning, refiners should reformulate to more iron-resistant catalysts and consider
higher fresh catalyst additions. Catalyst design can be
optimised to resist the effect of contaminant iron and
calcium. High alumina catalyst, especially catalyst with
alumina based binders and high diffusivity matrices,
such as Graces Midas and Achieve catalyst platforms,
are best suited to process iron and calcium containing
feeds because they are more resistant to the formation
of low melting point phases that permanently destroy
the surface pore structure. Optimum distribution of
mesoporosity (pores in the 100-600 size range) also
plays a role in maintaining performance because diffusion to active sites remains unhindered, even with high

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levels of contaminant metals. The resistance of Midas


to iron and calcium poisoning has been demonstrated
in multiple commercial applications.1,3 Catalyst reformulation (to more resistant catalyst formulas
containing Graces high diffusivity matrices) and
higher fresh catalyst additions to purge the contaminants from the inventory are effective strategies to
recover from iron and calcium contamination in the
FCC unit.
References
1 Bryden K, Habib E T, Topete O, Schiller R, Catalytic solutions for
processing shale oil in the FCC, PTQ Processing Shale Feedstocks, 2014.
2 Yaluris G, Cheng W-C, Boock L T, Peters M, Hunt L J, The Effects of
Fe Poisoning on FCC Catalysts, AM-01-59, 2001 NPRA Meeting, New
Orleans, LA.
3 Cher Y-Y , Koebel J, Schiller R, Enhanced bottoms cracking and process
flexibility with MIDAS FCC catalyst, Catalagram 112, W R Grace & Co.,
2012.

Todd Hochheiser, Senior Technical Service Engineer,Todd.


Hochheiser@matthey.com, and Jeff Oberlin, Regional Sales
and Marketing Manager, Jeff.Oberlin@matthey.com, Johnson
Matthey

Processing tight oil may lead to increased sodium,


calcium, and iron in the FCC feed. Sodium leads to
destruction of Y-zeolite and neutralisation of matrix
sites. Calcium neutralises acid sites and exacerbates the
effects of iron poisoning. Iron contributes to a low
melting eutectic on the exterior of the catalyst particle
limiting hydrocarbon diffusion. Signs of iron poisoning
include nodule formation on the surface of E-cat particles, a decline in E-cat apparent bulk density (ABD),
and a conversion decline. Fresh iron deposited on E-cat
acts as a reverse SOx reduction additive by capturing
H2S in the reactor and releasing it as SOx in the regenerator. Fresh iron effects typically last two to three
days during which time there will be an increase in
flue gas SOx, a higher requirement for SOx additive,
and/or increased scrubber caustic usage. Metals
poisoning can be combatted by increasing fresh catalyst addition rate and/or introducing flushing E-cat.
Alternatively, an iron trapping additive such as
Johnson Matthey Intercats Cat-Aid can be used to
mitigate iron poisoning.

We want to improve the cold flow product properties


from our ULSD hydrotreater. What is the best approach for
catalytic dewaxing?

Robert Bliss, Mid-Distillates HPC Specialist, Robert.Bliss@


Albemarle.com, and Jignesh Fifadara, Marketing Specialist
Applications Technology, Jignesh.Fifadara@Albemarle.com,
Albemarle

Diesel fuel is a very complex mixture of paraffins,


isoparaffins, naphthenes and aromatics. Paraffins,
sometimes referred to as wax, typically have higher
melting points than their branched or cyclic counter-

12 Catalysis 2015

parts of equivalent carbon number due to larger


attractive intermolecular forces. These intermolecular
forces and, in turn, melting points increase with
increasing paraffin chain length. As the temperature of
diesel fuels drops, long chain normal paraffins agglomerate and begin to form crystals. The rate of crystal
formation as well as crystal size increases with
decreasing temperature. At low enough temperatures,
the crystals will become so large they will precipitate
out of the fuel as solids. These solids will adhere to the
surface of fuel filters and over time they will
completely plug the filters, causing engines to stall due
to lack of fuel.
The low temperature operability limit for a diesel
engine is the lowest temperature at which the engine
can be started and will continue running. There are
three prevailing test methods used to predict the low
temperature operability limit for diesel fuels. These
include cloud point (CP), cold filter plug point (CFPP)
and pour point (PP):
The cloud point of a fuel is the temperature at which
the concentration and size of crystals in a sample
become large enough to create a visually detectable
cloudy appearance. This temperature is typically 3-9C

The primary advantage of noble


metal dewaxing catalysts is the much
higher isomerisation selectivity,
leading to minimum loss of diesel
yield to light gases and naphtha
(5-15F) above the low temperature operability limit.
There are international standards organisations with
prescribed methods for measuring CFPP such as
ASTM D2500
The cold filter plug point of a fuel is the lowest
temperature at which a specific volume of fuel will
pass through a specific filter size in a predefined time
period. An example international standards organisations prescribed method for measuring CFPP is ASTM
D6371
The pour point of a fuel is the temperature at which
a sample of fuel will no longer pour from a container.
An example international standards organisations
prescribed method for measuring CFPP is ASTM
D5949.
Collectively, these tests are commonly referred to as
the cold flow properties of a fuel.
There are several strategies employed by fuel manufacturers to improve diesel cold flow properties. These
include the use of cold flow improvement additives,
undercutting diesel fractions to reduce long chain
paraffin content, dilution with kerosene to again
reduce long chain paraffin content, catalytic dewaxing
or additional processing using solvent dewaxing technologies. The use of additives, undercutting, kerosene

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dilution and solvent dewaxing processing all involve dewaxing catalyst; for existing units a revamp is
high capital costs and margin erosion due to significant required. The primary advantage of noble metal
diesel yield loss. Catalytic dewaxing provides a dewaxing catalysts is the much higher isomerisation
competitive economic alternative to reduce the impact selectivity, leading to minimum loss of diesel yield to
of these strategies.
light gases and naphtha.
The general principle behind catalytic dewaxing
Unfortunately the best approach to catalytic dewaxis to employ a catalyst with functionality to initiate ing is a very complex question whose answer depends
a combination of hydrogenation, hydrocracking upon the degree of desired cold flow improvement,
and/or isomerisation reactions to either reduce paraf- available unit hardware (reactors, beds, quenches,
fin chain lengths or to rearrange the chains to produce internals), unit revamp feasibility, hydroprocessing
lower melting point isoparaffins. There are objectives/constraints and the particular set of
two commonly employed solutions for catalytic economics for your unit. Fortunately, catalyst vendors
dewaxing, either a single stage flow scheme that and technology licensors have proprietary unit perforemploys a base metal dewaxing catalyst or a two stage mance and economic evaluation tools at their disposal
flow scheme that employs a noble metal dewaxing to assist you in evaluating your unit and its
catalyst.
specific circumstances.
The single stage solution is
the least capital intensive solution because it involves the use
of a base metal dewaxing catalyst layer at an optimal location
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PREMIERE INTEGRATED
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DOWNSTREAM EVENT
metal dewaxing catalysts have
historically been designed with
small pore diameters to selectively diffuse paraffins into the
catalyst pill while preventing
diffusion
of
isoparaffin,
napthenic and aromatic constituents. The diffused paraffins
are then exposed to zeolitic
based active sites where they
are cracked and/or isomerised
to form smaller chain paraffins
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Catalysis 2015 15

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19-02-15 19:08

Hydrogen transfer and ZSM-5 in


maximising propylene
Used at high concentrations to maximise propylene from the fluid catalytic
cracking unit, ZSM-5 strongly influences a complex matrix of reactions
BART DE GRAAF, MEHDI ALLAHVERDI, CHARLES RADCLIFFE, MARTIN EVANS and PAUL DIDDAMS
Johnson Matthey Process Technologies

he fluid catalytic cracking


(FCC) unit is a versatile tool
that can readily accommodate
the need for increasing propylene
demand. In the Middle East and
Asia, new petrochemical FCC units
are being built to add capacity, but
in the US the advent of cheap and
abundant natural gas liquids (from
shale gas) displacing heavier feeds
in steam crackers has reduced the
production
of
propylene.
Maximising propylene production
in the FCC can be achieved by
changes in operation and especially
the use of ZSM-5 containing
additives.
For maximum (or just increased)
propylene operations, the feedstocks can be as diverse as a light
hydrotreated VGO to blends
containing
atmospheric
and
vacuum residues. The optimal
cracking catalyst for each feed is
very different. Typically, it is
assumed that ZSM-5 effects are
additive to those of the base catalyst. The effects of hydrogen
transfer in the FCC, ZSM-5 and
combinations of both are reasonably
accurately described at low concentrations (up to about 10%) of ZSM-5
additive in the circulating inventory. However, for operations
where high concentrations of ZSM-5
additives are used to maximise
propylene the simple models of
these effects no longer hold true.
Both catalysts (ZSM-5 and base
catalyst) in the inventory guide an
elaborate but elegant interplaying
reaction matrix between all components from gasoline to LPG range.
This has a surprising influence on
ZSM-5 effects at high concentrations
and helps to explain apparent

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contradictions in the literature. In a


previous article1 we outlined mechanisms for ZSM-5 in FCC; here we
expand this picture to include the
effects of base catalysts with various
levels of hydrogen transfer on
ZSM-5.

Hydrogen transfer in the FCC

The role of hydrogen transfer in


FCC is a well-known phenomenon
and its effect on LPG olefins is
generally assumed to be well
understood. Hydrogen transfer
reactions in FCC are bimolecular
reactions.
Naphthenes
donate
hydrogen to olefins and become
aromatics while the olefins are
hydrogenated
into
paraffins.
Paraffins are more stable than
olefins which reduces the rate of
cracking reactions. Therefore hydrogen transfer increases gasoline yield
and
lowers
LPG
yield.
Simultaneously,
olefinicity
is
reduced in both fractions. This
simple model is sufficient to
describe the effects of oil cracking
over base catalyst, or over base
catalyst with low concentrations of
ZSM-5 blended in. However, this
model is insufficient to describe the
catalytic interactions in high propylene operations, where high amounts
of ZSM-5 containing additives are
present with the base catalyst in the
circulating inventory.
Hydrogen transfer is affected by
several factors:
Base catalyst: the higher the rare
earth stabilisation of the base catalyst, the higher the acid site
concentration in Y-sieve and the
higher the rate of the bimolecular
hydrogen transfer reactions
Feed: feeds that contain a lot of

hydrogen donors (naphthenes, typically hydrotreated feeds) have


higher rates of hydrogen transfer
Unit design/configuration: higher
contact times and more back mixing
increase hydrogen transfer in the
FCC unit
Unit operation: decreasing the
hydrocarbon partial pressure (for
instance, using steam in the riser)
reduces the rate of hydrogen transfer and is a common feature in
maximum propylene FCC unit
designs.
These effects combine to determine which of the various
pathways, such as cracking and
hydrogen transfer, are balanced
against each other.

The role of ZSM-5 on LPG yield and


gasoline composition

Hydrogen transfer reduces the


gasoline range olefins. As cracking
rates of olefins over ZSM-5 are
much higher than those of paraffins,
an increase in hydrogen transfer
reduces the effectiveness of ZSM-5
additives. Additionally, not all
gasoline range olefins are equally
crackable. Straight-chain normal
olefins (C7 and higher carbon
number) are very crackable. Their
branched isomers suffer from diffusion limitation and are therefore
much less crackable. Therefore,
once all the straight-chain olefins
have reacted, no further increases in
propylene can be expected.2
The acid sites of ZSM-5 can readily crack olefins or isomerise in
monomolecular reactions, but they
can also oligomerise small olefins.
The Mobil Olefin to Gasoline and
Distillate (MOGD) process3 utilises
coupling of light olefins. Lower

Catalysis 2015 17

14.5

1% REO
3% REO
5% REO

Aromatics, ff wt%

14.0
13.5
13.0
12.5
12.0
11.5

10

15

20

25

30

ZSM-5, wt%
Figure 1 Gasoline aromatics on feed basis at 71 wt% conversion for base catalysts
containing 1 , 3 and 5 wt% RE2O3. The base catalysts are tested with 5 and 25 wt%
ZSM-5 additive added and as-is

temperatures and higher pressures


favour oligomerisation of propylene
and butylene. Propylene can readily
form large molecules under the
right conditions as the existence of
polypropylene shows. At higher
temperatures and lower pressures,
thermodynamics heavily favour
small olefins, but with a distribution
tail for higher olefins. For example,
cracking of pentene over ZSM-5 is
feasible and occurs readily, but only
via a dimerisation step.4 At elevated
temperatures, adsorption of large
olefins is reduced and the likelihood
for a bimolecular reaction involving
two large olefins becomes small and
cracking becomes the dominant
mechanism to shape the olefins
distribution curve. Note that at both
low and high temperatures both
mechanisms occur, but relative reaction rates change with temperature.
The key question is whether LPG
range olefins and their distribution
in the FCC is in thermodynamic
equilibrium
or
is
kinetically
controlled? Kinetic control is
demonstrated by the fact that
adding ZSM-5 additive to an FCC
unit not only shifts LPG yields, but
also substantially changes the ratio
between propylene and butylenes.
If the olefin distribution were
controlled by thermodynamic equilibrium, this shift in composition
would not have been possible.

Pilot plant study

An ACE pilot plant study was

18

Catalysis 2015

conducted to establish the effects of


ZSM-5 additives on light olefin
yields and gasoline composition.
For this purpose, FCC catalysts with
rare earth levels of 1, 3 and 5 wt%
were selected. These catalysts were
then deactivated over 10-20 hours
in 100% steam to match catalyst
activity, and then blended with
various levels of equilibrated Super
Z Excel (a leading, commercially
available ZSM-5 additive). ZSM-5 is
more stable under laboratory deactivation conditions than the REUSY
containing FCC base catalyst.
Because ZSM-5 zeolite has a higher
silica alumina ratio (SAR) and
smaller micropores than REUSY, it
requires more severe deactivation.
Deactivation conditions recommended for ZSM-5 additives are
815C for 20 hours in 100% steam, a
protocol that would be overly
destructive for the zeolite-Y present
in regular FCC base catalysts.
The study was carried out at
1060F (570C) to mimic petrochemical FCC operating conditions
(equivalent to a riser outlet temperature of about 550C) using a VGO
feed.

Effects of ZSM-5 and base catalyst


on gasoline composition

Previous studies have shown that


adding small amounts of ZSM-5
additive to the base catalyst (around
5 wt%) results in a slight increase in
gasoline aromatics as calculated on
feed basis;5,6 and when adding high

amounts of ZSM-5 additive to an


FCC base catalyst, gasoline aromatics as calculated on feed basis
decrease slightly.1,7,8 However, this
study shows the effect is strongly
dependent on the hydrogen transfer
activity of the catalyst system. The
higher the hydrogen transfer activity of the base catalyst, the more
pronounced is the increase in gasoline aromatic cores on feed basis
when a small amount of ZSM-5 is
added (see Figure 1). However,
when higher concentrations of
ZSM-5 are blended with base catalyst, gasoline aromatic cores on feed
basis remain constant compared to
the base case without ZSM-5 for
intermediate and high levels of rare
earth on the base catalyst, and
decrease for the low rare earth on
base catalyst.
Why do gasoline aromatic cores
increase at low levels of ZSM-5
addition? At low levels (here,
5 wt%) of ZSM-5 additive, the
majority of the reactions involving
gasoline molecules take place on the
base catalyst, because 95% of the
particles are base catalyst. Therefore
the effect on gasoline composition
of ZSM-5 is really additive to that
of the base catalyst. This case
closely resembles the cracking of
pure gasoline feedstock.1 ZSM-5 can
add to the amount of gasoline
aromatic cores formed, but cannot
reduce them. An increase in hydrogen transfer means an increase in
gasoline aromatic cores, as the cases
without ZSM-5 show (see Figure 1).
At low levels of ZSM-5 gasoline,
intermediates that leave ZSM-5 via
oligomerisation and cyclisation can
be dropped back into (mainly) the
gasoline aromatics pool. The more
hydrogen transfer in the system the
more additional aromatics can be
formed. This increase in aromatics
is partially due to hydrogen transfer
of naphthenes into aromatics, but
this is only a part of the story. More
cyclic hydrocarbons are being
formed overall (see Figure 2) upon
the addition of a small amount of
ZSM-5, with the majority of them
being aromatic in nature. This effect
becomes more pronounced at
higher levels of hydrogen transfer
in the catalytic system.
At high concentrations of ZSM-5,

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Naphthenics + aromatics,
ff wt%

18.5

1% REO
3% REO
5% REO

18.0
17.5
17.0
16.5
16.0
15.5

10

15

20

25

30

ZSM-5 in inventory, additive wt%


Figure 2 Gasoline aromatics and naphtenes on feed basis at 71 wt% conversion for base
catalysts containing 1, 3 and 5 wt% RE2O3. The base catalysts are tested with 5 and 25
wt% ZSM-5 additive added and as-is

14

1% REO
3% REO
5% REO

13
12

C3=, wt%

11
10
9
8
7
6
5
4

10

15

20

25

30

ZSM-5 in inventory, additive wt%


Figure 3 Propylene yields at 71 wt% conversion for base catalysts containing 1, 3 and 5
wt% RE2O3. The base catalysts are tested with 5 and 25 wt% ZSM-5 additive added and
as-is

14

1% REO
3% REO
5% REO

13
12
11

C4=, wt%

gasoline aromatic cores remain


constant for intermediate and high
rare earth catalysts, or are reduced
for low level rare earth catalyst. The
effect is beyond dilution of the
hydrogen transfer of the base catalyst, because adding an inert does
not have the same effect on the
amount of aromatic cores formed.
Clearly, the ZSM-5 and base catalyst both contribute actively to the
composition of the gasoline and
LPG range (molecules). At higher
ZSM-5 addition levels, less cyclic
hydrocarbons are being formed (see
Figure 2). The amount of gasoline
aromatic cores stays the same (at
high and intermediate hydrogen
transfer levels) or reduces (at low
hydrogen transfer levels). A slight
reduction
in
naphthenes
is
observed. An increase in ZSM-5
additive in inventory results in
higher propylene and butylene
yields (see Figures 3 and 4). The
starting level of propylene differs
with the base catalyst rare earth,
and
the
propylene
response
towards increasing ZSM-5 additive
in inventory is somewhat reduced
for the higher rare earth levels.
However, the difference in propylene response for the higher rare
earth catalysts compared to the
lower rare earth levels remains
more or less constant. For the butylene responses to ZSM-5 addition,
the same observation holds true.
The role of ZSM-5 as catalyst in
the FCC unit is quite diverse (see
Figure 5). Pilot plant experiments
and commercial experience both
show that the role of ZSM-5
involves more than just cracking
olefins. For example, this is illustrated by the fact that the increased
propylene and butylene yields (at
constant conversion) outpace the
decrease in gasoline olefins (see
Figure 5). For the 1% rare earth catalyst, an increase in propylene from
4.7 wt% to 12.1 wt% (an increase of
7.4 wt%) goes hand in hand with a
decrease in gasoline olefins (on feed
basis) from 9.6 wt% to 7.0 wt% (a
decrease of 2.6 wt%). Obviously, the
increase in LPG and total decrease
in gasoline do match (with a small
deviation for ethylene, a test effect).
At high concentrations of ZSM-5,
the interplay between ZSM-5 and

10
9
8
7
6
5
4

10

15

20

25

30

ZSM-5 in inventory, additive wt%


Figure 4 Butylene yields at 71 wt% conversion for base catalysts containing 1, 3 and 5
wt% RE2O3. The base catalysts are tested with 5 and 25 wt% ZSM-5 additive added and
as-is

Catalysis 2015 19

$ WIN $

C6
C3

C8

C7

C4

C3
C3

C5

START

C4

C4

base catalyst (see Figure 6) determines the composition of gasoline


and LPG yields. Here ZSM-5 is not
a mere dilution of the base catalyst,
but an active catalyst in shaping the
whole boiling range from LPG to
heavy naphtha.

C3 and C4 olefins
Beta scission
Gasoline range
molecules
Olefin
isomerisation

Conclusions

When ZSM-5 is used at moderate/


low concentrations it functions
largely in accord with the traditional
view: it primarily converts the products of the Y-zeolite based catalyst.
However, when ZSM-5 is used at
high concentrations it interacts with
the Y-zeolite based catalyst, feed
and intermediate product mixture
very differently to shape the overall
composition and yields in the gasoline and LPG fractions.
References
1 de Graaf B, Allahverdi M, Evans M, Diddams P,
Snakes and ladders for maximising propylene,
PTQ, Q4 2014, 87-95.
2 Donnelly S P, Mizrahi S, Sparrell P T, Huss A
Jr, Schipper P H, Herbst J A, How ZSM-5 works
in FCC, ACS New Orleans meeting, Sept 1987.
3 Tabak S A, Krambeck F J, Garwood W E,
Conversion of propylene and butylene over
ZSM-5 catalyst, AIChE Journal, 32, 1986, 15261531.
4 Abbot J, Wojciechowski B W, The mechanism
of catalytic cracking of n-alkenes on ZSM-5
zeolite, Can. J. Chem. Eng., 63, 1985, 462-469.
5 Biswas J, Maxwell I E, Octane enhancement
in fluid catalytic cracking. Role of ZSM-5
addition and reactor temperature, Applied
Catalysis, 58, 1990, 1-18.
6 Zhao X, Harding R, ZSM-5 additive in fluid
catalytic cracking. Effect of hydrogen transfer

Diesel range
molecules

Olefins
oligomerisation
Aromatic
transalkylation

Olefin
aromatisation

Figure 5 Reaction pathways over ZSM-5 in the FCC unit. ZSM-5 catalyses many more
reactions in the FCC than only cracking of olefins
characteristics of the base cracking catalysts
and feedstocks., Ind. Eng. Chem. Res., 1999,
3854-3859.
7 Adewuyi Y G, Klocke D J, Buchanan J S,
Effects of high-level additions of ZSM-5 to a
fluid catalytic cracking (FCC) RE-USY catalyst,
Appl. Catal. A: Gen., 131, 1995, 121-133.
8 Buchanan J S, Adewuyi Y G, Effects of high
temperature and high ZSM-5 additive level on
FCC olefins yields and gasoline composition,
Appl. Catal. A: Gen., 134, 1996, 247-262.
Bart de Graaf is FCC R&D Director with
Johnson Matthey Process Technologies, Inc. He
holds an MSc in chemical engineering and a
PhD in heterogeneous catalysis and chemical
processes. Email: Bart.deGraaf@matthey.com
Mehdi Allahverdi is FCC Applications Manager
with Johnson Matthey Process Technologies,
Inc., Savannah, Georgia, US. He holds a
PhD in materials science and engineering

Gasoline range
molecules

Crack on RE-USY
E-USY

from McGill University, Canada.


Email: Mehdi.Allahverdi@matthey.com
Charles Radcliffe is an Intercat Europe, BV
Senior Technical Consultant, FCC and Refining
for Europe. He holds a BSc in chemical
engineering from Birmingham University, UK,
and an MBA from The Open University, UK.
Email: Charles.Radcliffe@matthey.com
Martin Evans is Vice President of Engineering
Technical Services with Johnson Matthey
Process Technologies, Inc. He holds 22 patents
in FCC catalyst addition systems and a BSc in
chemical engineering from the University of
Wales. Email: m.evans@matthey.com
Paul Diddams is Vice President for FCC
Additives with Johnson Mattheys Refineries
Division. He holds a BSc in chemistry from the
University of Newcastle-upon-Tyne, UK, and a
PhD in physical chemistry from the University
of Cambridge, UK.
Email: Paul.Diddams@matthey.com

Aromatic
transalkylation

Olefin
aromatisation

nsfe
f r:
fe
r
Hydrogen Transfer:
olefin to paraffin
naphthene to aromatic

Ol fi
f / lil
Olefins/oligomers

Olefin
isomerisation

Figure 6 Y-sieve and ZSM-5 both catalyse many reactions of gasoline (and LPG, see Figure 5) range molecules. The relative ratio
between both zeolites will determine the composition and yields of gasoline and LPG

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Catalysis 2015 21

cattec.indd 1

26/02/2013 16:59

ZSM-5 additive maximises propylene


Multi-stage phosphorus treatment improves ZSM-5 zeolite stabilisation and
creates more propylene producing acid sites
CARL KEELEY, VASILEIOS KOMVOKIS, MODESTO MIRANDA, DAVID HARRIS and JASON SMITH
BASF

ZSM-5 chemistry

ZSM-5 is used to fine-tune the


production of gasoline and light
olefin products.1-4 Its usage rates in
FCC units vary across the industry
according to specific unit goals,
which depend on objectives, capacity and market. FCC units targeting
gasoline octane enhancement have
low usage requirements (for example, 1-4 wt% ZSM-5 additive
loading), while those targeting a
maximum light olefins yield have

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3.0

Nominal olefins yield,


wt% of feed

lobally, there is strong


demand for light olefins,
especially
propylene.
Propylene is an important feedstock for the petrochemicals
industry in producing polypropylene,
acrylonitrile,
propylene
glycols, cumene, butyraldehydes,
acrolein and other valuable products. Primarily produced by steam
crackers, the fluid catalytic cracking
(FCC) unit is the second largest
propylene producer. Due to the
shale gas revolution in the US,
propylene yields from steam crackers have declined, opening an
opportunity for FCC units around
the world to increase propylene
production. To meet this opportunity, FCC operators rely on ZSM-5
based additives to change the yield
distribution and quality of FCC
liquefied petroleum gas (LPG) and
gasoline.1-4 Since demand for
propylene can vary significantly,
ZSM-5 usage rates are different for
different FCC units.4 With the
growing demand to increase
propylene from FCC units, BASF
has invested in the understanding
of ZSM-5 chemistry to increase its
effectiveness.

Base
Base + 15% ZSM-5
Base + 30% ZSM-5
Base + 50% ZSM-5

2.5
2.0
1.5
1.0
0.5
0

10

11

Carbon number
Figure 1 The amount of light olefins in naphtha at different ZSM-5 loadings. The
challenge is how to convert the remaining C6 and C7 olefins to C3 and C4 olefins

relatively high usage requirements


(10-20
wt%
ZSM-5
additive
loading).
The ZSM-5 crystal is a shape
selective zeolite used in FCC units
to convert light gasoline range

Feed quality and FCC


catalyst properties
play a key role in
the amount of LPG
generated from the
ZSM-5 additive
olefins (C6-C9) to LPG (C3 and C4
olefins).1 Without ZSM-5 the light
gasoline olefins are converted to
low octane paraffins via a hydrogen transfer mechanism. Since rare
earth promotes hydrogen transfer,
low rare earth FCC catalysts are
preferred for maximum light olefin

production. Consequently, the use


of ZSM-5 increases both light olefin
production and gasoline octane. As
can be imagined, there are different
pathways in which C6-C9 olefins
may crack. For example, a C9 molecule may crack to a C6 molecule
and a C3 molecule, or a C5 molecule
and a C4 molecule. An accepted rule
of thumb states additives that only
use ZSM-5 zeolite should have an
LPG product selectivity of approximately 50-60 wt% C3=, 20-40 wt%
C4=, and 10-20 wt% iso-butane.
Small amounts of propane and
normal butane may also be generated. Small changes in LPG product
selectivity have also been observed
for ZSM-5 with different feeds.
Feed quality and FCC catalyst
properties play a key role in the
amount of LPG generated from the
ZSM-5 additive. These effects are
related to the hydrogen transfer
tendency of the feed and the catalyst. The higher the hydrogen
transfer, the lower the olefinicity of

Catalysis 2015 23

It is important to note the impact


of ZSM-5 on activity dilution of
FCC catalyst. As ZSM-5 additive is
inert in terms of conversion, higher
levels of ZSM-5 can dilute the activity of the FCC catalyst. By
fine-tuning the additive injection
rate, the refinery can optimise light
olefin production and gasoline
octane. However, as the ZSM-5
injection rate increases, FCC catalyst activity is diluted. The rule of
thumb is every 5 wt% of ZSM-5
additive reduces FCC catalyst activity by 1-2 wt%. Therefore, when
targeting a maximum light olefins
yield (that is, using 10-20 wt%
ZSM-5 loading), it is more profitable to integrate most of the ZSM-5
functionality within the FCC catalyst formulation to avoid activity
dilution, and have a small amount
of separate additive addition for
fine-tuning yields. When done
properly, the ZSM-5 loading can be
increased significantly without any
detrimental effect on the catalyst
physical and catalytic functions.2

16

ZSM-5 (with P)
ZSM-5 (no P)
FCC

Propylene yield,
wt% at 70% conversion

14
12

~8%

10
8

~4%

6
4
2
0

FCC

FCC + ZSM-5
(no P)

FCC + ZSM-5
(with P)

Figure 2 Effect of ZSM-5 and phosphorus on propylene yields

Propylene yield, wt%

16
14
12
10
8
6
4

1000F at 100% steam


1200F at 100% steam
1350F at 100% steam

2
0

10

20

30

40

Development of a ZSM-5 additive

50

60

70

80

90

100

Zeolite acidity, micromoles/g


Figure 3 Effect of steam deactivation on ZSM-5 framework acid sites and propylene yield

the C6-C9 hydrocarbons; therefore,


lower amounts of LPG olefins are
generated by ZSM-5.2-4
As the amount of ZSM-5 applied
to a unit increases, a refiner will
experience diminishing returns in
terms of additional LPG, mostly

due to lower quantities of readily


crackable C6-C9 olefins. The larger
olefins in this range are more easily
cracked, leaving behind C6 and
small amounts of C7. These represent targets to improve the total
LPG olefins yield (see Figure 1).

Effect of steam and phosphorus to boost ZSM-5 propylene yields*

Ethylene
Propylene
C3=/C2=
Butenes
Propane
Total C2Gasoline
Coke
Acty@ c/o=7.7

Fresh
without P
4.2
8.6
2.0
6.7
8.9
6.2
29.8
3.2
1.83

Steamed
without P
0.9
9.4
10.9
10.3
1.0
1.9
39.3
3.2
1.57

Fresh
with P
4.2
12.7
3.1
10.4
3.8
5.4
29.5
2.2
1.99

Steamed
with P
2.1
13.7
6.5
12.2
1.5
3.1
33.2
2.1
2.03

*ACE cracking data @ 70% conversion for a mixture of 76.5 wt% of 1 wt% REO FCC catalyst and 23.5 wt% of
MOA ZSM-5 additive. Steam deactivation conditions: 15h/1500F/100% steam.

Table 1

24 Catalysis 2015

To address the need to use less


ZSM-5 to maximise propylene
yield, BASF has developed a novel
ZSM-5 additive called ZIP Olefins
Additive. Many approaches were
explored from different zeolite
properties (for instance, silica to
alumina ratio, crystal size, and so
on), to exploring zeolite modifications
(such
as
phosphorus
alternatives), to synthesis process
improvements.
An
interesting
improvement came in the form of a
novel
multi-stage
phosphorus
treatment.
Phosphorus helps to slow down
the dealumination of the ZSM-5
framework.
This
stabilisation
means more active acid sites and
thus higher activity.1 In some additives, phosphorus also acts as a
binder. Depending on the composition of the rest of the additive,
phosphoruss effect on binding and
attrition resistance may be more or
less important.
Figure 2 shows the effect of
ZSM-5 additive, with and without
phosphorus, on propylene yield.
For these experimental conditions,
the base propylene yield is ~6 wt%

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Propylene yield, wt%

16
14
12
10
8
6
4

1000F at 100% steam


1200F at 100% steam
1350F at 100% steam

2
0

10

20

30

40

50

Phosphorous based acidity, micromoles/g


Figure 4 Role of ZSM-5 phosphorus based acidity on propylene yields

Propylene yield, wt% at 70%


conversion

15.0

12.5

10.0

7.5

5.0

ZIP olefins additive


MOA additive
0

10

15

20

25

ZSM-5 additive, wt%

Propylene yield, wt% at C/O 7.7

without any ZSM-5 additive.


Addition
of
ZSM-5
additive
without phosphorus increases the
propylene yield to nearly 10 wt%,
and treating the additive with
phosphorus further increased the
propylene yield to about 14 wt%.
Table 1 shows the impact of
steam and phosphorus on the
performance of BASFs Maximum
Olefins Additive (MOA) combined
with a low hydrogen transfer FCC
catalyst. MOA is an optimised,
ZSM-5 based additive produced
using conventional manufacturing
techniques. Based on these results,
un-steamed ZSM-5 additive is less
active for propylene generation,
with or without phosphorus. The
introduction of steam increases
propylene yield, and the combination of steam and phosphorus gives
the highest selectivity to propylene.
Based on these experiments,
active sites necessary for propylene
production involve phosphorus
and are enhanced by steaming.
BASF developed a new methodology
using
Fourier
transform
infrared (FT-infrared) spectroscopy
with pyridine adsorption to characterise the nature of the phosphorus
inside ZSM-5.7 This new technique
allows us to separate and quantify
phosphorus based acid sites from
zeolite framework and non-framework acid sites. A study using this
technique suggested maldistribution
of phosphorus within ZSM-5 additives produced via conventional
manufacturing techniques. Figure 3
shows the effect of steam deactivation on framework ZSM-5 acid sites
and propylene yield. As the steam
severity increases, the acidity
decreases; however, the propylene
yield increases. Thus, ZSM-5 zeolite
framework acidity does not generate
more propylene as steam severity
increases, so propylene yield must
be due to another acid site.
Figure 4 shows propylene yield
increases as the phosphorus based
acidity increases with more severe
steam deactivation. Phosphorus
based acid sites therefore play a
key role in propylene formation
after steam deactivation.
Based on the above, BASFs
research focused on maximising
the phosphorus based acidity

15.0

12.5

10.0

7.5

5.0

ZIP olefins additive


MOA additive
0

10

15

20

25

ZSM-5 additive, wt%


Figure 5 Propylene yields for a) varying additive at 70% conversion and b) varying
additive at C/O=7.7

contribution to improve ZSM-5


performance. The result was a
novel,
multi-stage
phosphorus
treatment to improve ZSM-5
zeolite stabilisation and create
more propylene producing acid
sites. By utilising this new technology, ZIP Olefins Additive produces
more propylene at iso-ZSM-5

loading and crystal content.


ZIPs improvement in propylene
is visible in Advanced Cracking
Evaluation (ACE) pilot unit tests.
The deactivation conditions for the
ZSM-5 additive were: 1500F
(~816C) for 15 hours in 100% steam.
The deactivated ZIP was combined
with a low hydrogen transfer FCC

Catalysis 2015 25

Propylene, wt%

Commercial results

Actual propylene
Estimated propylene
Beginning of ZIP trial

29 Jan

26 Feb

26 Mar

23 Apr

21 May

Propylene yield, wt%

Figure 6 Actual propylene yields vs statistical model predictions

Actual propylene
Estimated propylene
Beginning of ZIP trial

19 Apr

17 May

14 Jan

12 Jul

Figure 7 ZIP produces a similar propylene yield using less ZSM-5 additive

Propylene, wt%

BASF ZIP
BASF MOA

0.89

0.90

0.91

0.92

0.93

0.94

0.95

Feed specific gravity


Figure 8 Propylene yield vs feed quality

catalyst to evaluate ZIPs performance. Figure 5 shows ZIP produces


more propylene than BASFs
Maximum Olens Additive (MOA).
Since product selectivity for
ZSM-5 additives is related primarily to the shape of the zeolite itself1,

26

Catalysis 2015

there is no change in selectivity for


ZIP Olens Additive compared to
other ZSM-5 additives. However,
due to ZIPs higher activity,
improved octane enhancement and
light olen yields can be achieved
using less ZSM-5 additive.

A successful trial at CEPSAs La


Rbida Renery in Huelva, Spain,
in 2013, using BASFs Maximum
Propylene Solution (MPS) catalyst5,
set the stage for a ZIP Olens
Additive
trial.
MPS
catalyst
combines the superior selectivities
of an FCC catalyst based on the
Distributed
Matrix
Structures
(DMS) platform, with ZSM-5 functionality based on BASFs MOA
ZSM-5 additive.2,6 This FCCs operating objective is to maximise
propylene.
Conventional
fuels
based FCC units produce 4-6 wt%
propylene, whereas this unit can
produce >11 wt% propylene.
Using operating data, a statistical
model was built to predict propylene yield for a range of operating
conditions. The estimated propylene based on this model is shown
in Figure 6 for the MOA ZSM-5
additive, and is in good agreement
with the actual propylene yield.
To evaluate the performance of
ZIP, MOA was replaced with ZIP
in the catalyst formulation. Using
3% less ZSM-5, ZIP achieved similar propylene yields for the units
typical feed quality and operating
conditions (see Figure 7). The estimated propylene yield in Figure 7 is
still based on the expected performance from MOA, whereas the
actual propylene yield is generated
using 3% less ZSM-5 in the form of
ZIP. As mentioned earlier, the ability to add less ZSM-5 additive for
the same effect reduces the activity
dilution of the base catalyst to
maintain high catalyst activity.
Figure 8 shows the new operating
window achieved using ZIP. Because
ZIP has more propylene producing
acid sites, it performed well even
when feed quality deteriorated.
After the trial period, and based
on the FCC unit protability assessment, CEPSA La Rbida chose to
continue
using
ZIP
Olens
Additive. To fully evaluate the
potential of this additive, additional
trials are planned.

Conclusion

Increasing global demand for


propylene provides a signicant
economic incentive for reners to
maximise propylene production

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from FCC units. To respond to this


need, BASF has developed a new
ZSM-5 additive called ZIP Olens
Additive, based on a novel, multistage
phosphorus
treatment
technology. ZIP is a solution for
FCC units seeking a more efcient
route to enhance octane, and those
seeking to maximise propylene
production beyond what is possible
with traditional ZSM-5 additives.
The ability to use less additive
lowers the activity dilution impact
of the additive, allowing higher
conversion from the base catalyst.
Results from CEPSAs La Rbida
Renery show that ZIP produces
similar propylene using less additive in a unit targeting maximum
propylene yield.
References
1 Degnan T F, Chitnis G K, Schipper P H, History
of ZSM-5 fluid catalytic cracking additive
development at Mobil, Microporous and
Mesoporous Materials, Vol 35-36, Apr 2000,
245-252.
2 McLean J, Smith G M, Maximizing Propylene
Production in the FCC Unit: Beyond Conventional
ZSM-5 Additives, NPRA AM-05-61.

3 Rahimi N, Karimzadeh R, Catalytic cracking


of hydrocarbons over modified ZSM-5 zeolites
to produce light olefins: A review, Applied
Catalysis A: General, 398, 2011, 117.
4 Zhao X Harding R H, ZSM-5 Additive in Fluid
Catalytic Cracking. Ch 2. Effect of Hydrogen
Transfer Characteristics of the Base Cracking
Catalysts and Feedstocks, Industrial &
Engineering Chemistry Research, 1999, 38 (10),
38543859.
5 Llanes J M, Aramburu B, Arjona M, Serrano
E, CEPSA and Miranda M, Keeley C, Komvokis
V, Riva S, BASF, New catalyst increases olefin
yields, Hydrocarbon Processing, Apr 2014, 63-66.
6 McLean J, Weber W A, Harris D H, Distributed
Matrix Structures a Technology Platform for
Advanced FCC Catalyst Solutions, NPRA AM03-38.
7 Dr Xinsheng Liu developed this methodology.
He works in BASFs Refining Catalysts R&D
facility in Iselin NJ, USA.

Carl Keeley is Marketing Manager, Refining


Catalysts for EMEA, BASF plc (UK). Prior to
joining BASF in 2012, he worked with UOP,
BP and Dow. He holds a MEng in chemical
engineering and applied chemistry from Aston
University, UK. He is a professional engineer
and member of the Institute of Chemical
Engineers (CEng MIChemE).
Email: carl.keeley@basf.com

Vasileios Komvokis is Technology Manager,


Refining Catalysts for EMEA, BASF plc (UK).
Prior to joining BASF in 2012, he was a
researcher at CPERI Institute of Thessaloniki,
Greece, and a research Professor at the
Chemical Engineering Department of the
University of South Carolina, USA. He holds
BS and MS degrees in chemistry and a PhD in
chemical engineering from Aristotle University,
Greece. Email: vasileios.komvokis@basf.com
Modesto Miranda is Technical Sales Manager,
Refining Catalysts EMEA with BASF Espanola
Sl. He has more than 20 years of experience in
unit modelling, optimisation, troubleshooting
and FCC and refinery operations.
Email: martin-modesto.miranda@basf.com
David Harris is a Research Associate in Refining
Catalysis Research based at the BASF Global
Catalyst R&D centre in Iselin NJ. He has 30
years of experience in FCC catalyst R&D with
BASF, Engelhard, Akzo and Filtrol, and holds
BSc, MSc and PhD degrees in chemistry from
the Universities of Bristol and Sussex, UK.
Email: david.h.harris@basf.com
Jason Smith is Marketing and Product
Manager for FCC Additives with BASF Iselin NJ,
USA, responsible for marketing and product
management of BASFs line of FCC additives.
He holds a BSChE from the Georgia Institute
of Technology and an MBA from Lehigh
University.
Email: jason.k.smith@basf.com

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Catalysis 2015 27

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Increased activity in FCC pretreat


Advances in metal chelation techniques deliver higher performance catalysts for
FCC pretreat
CHARLES OLSEN and BRIAN WATKINS
Advanced Refining Technologies

he process of optimising a
catalyst is no easy task. A few
of the keys to success are
designing the proper pore size
distribution into the catalyst, optimising the metals composition and
maximising utilisation of the
metals. Extensive work has been
completed to define the optimum
pore architecture of catalysts for
processing heavy feeds.
Figure 1 compares the relative
activity of different catalyst preparations as a function of increasing
catalyst pore size. The pore size
and surface area of a catalyst are
dependent variables, meaning that
as the pore size increases, the
surface area decreases, and thus the
number of active sites decreases.
On the left side of Figure 1, the
catalysts have a high surface area,
but the pores are too small to allow
large VGO molecules access to the
active sites. On the right side of the
figure, the pores are very large and
allow easy access, but the surface
area (and thus the number of active

sites) is quite low. In both cases, the


activity is low. The optimum
support has a pore size distribution
which
minimises
diffusion
constraints and maximises the
number of accessible active sites.
Another important parameter for
catalyst performance is the composition of active metals. Figure 2
shows the relationship between the
relative activity of a catalyst and
the active metals loading. As
expected, activity increases with
increasing level of metals, but there
is a limit. The figure indicates that
there is an optimum metals loading
beyond which adding more metals
actually hurts catalyst performance.
Catalyst activity decreases when
excess metals are added because
they begin to block the pores.
Yet another critical aspect is the
utilisation of metals, or maximising
the number of active sites. Current
generation catalysts typically rely
on the formation of Type II active
sites during catalyst activation.
Type II sites are known to provide

significantly higher activity at the


same metals loading as catalysts
containing Type I active sites. An
effective way to maximise the
concentration of Type II active sites
is through the use of chelate technology
during
the
metals
impregnation step. ART has been
steadily improving the application
of chelates with its DX technology.
The latest catalysts developed via
this optimisation process are
Advanced Refining Technologies
(ART) 586DX and 486DX catalysts
which are new catalysts designed
for maximum performance in FCC
pretreat applications. 586DX is a
NiMo catalyst with significantly
improved HDS and HDN activity.
In FCC pretreat applications, this
catalyst can provide superior nitrogen removal as well as aromatic
and polynuclear aromatic (PNA)
saturation in order to provide
significant FCC feed upgrading for
increased FCC yields. Figure 3
compares the activity of 586DX and
AT575. The figure shows that
120

115

Decreasing
pore size

Increasing
pore size

Optimum region for


best performance

Relative activity

120

100
90
80

115
100
90
80
70

Relative activity

130

60

70

50

60
Decreasing access to active sites

Increasing access to active sites

Figure 1 Optimised pore structure is key to performance

www.eptq.com

Catalysis 2015 29

170

Relative activity

160
150
140
130
120
110
100
90

Metals surface coverage

Figure 2 Proper metals surface coverage is critical

Relative volume activity

130
125

586DX
AT575

120
115
110
105
100
95
90

HDS

HDN

Relative volume activity

Figure 3 586DX out-performs AT575 in FCC pretreat

190
180
170
160
150
140
130
120
110
100
90
80
70

HDS
HDN

AT775

AT792

AT795

486DX

Figure 4 486DX has superior performance in high pressure FCC pretreating

586DX has nearly 20% higher HDN


activity and 15% higher HDS activity compared to AT575. 586DX has
a large pore size distribution, similar to AT575, which gives the
catalyst exceptional stability on
heavy feeds.
It benefits from the latest
advancement in DX technology. It
has lower loss on ignition than

30

Catalysis 2015

conventional chelated catalysts and


requires no special handling or
start-up procedures. In just a short
time since its commercialisation,
586DX has been installed in four
FCC pretreat units. The performance has been excellent with as
much as 10F improvement in HDS
activity over the previous catalyst.
586DX has already been selected

for another cycle in some of these


units.
Another recent advancement to
ARTs FCC pretreat catalyst technology is 486DX. This is a CoMo
catalyst that has outstanding HDS
activity coupled with high HDN
activity. Figure 4 shows a comparison of the activity of several
generations of ART HDS catalysts
for FCC pretreat along with 486DX.
The results from side-by-side testing clearly show that 486DX
exhibits a significant improvement
in performance over the prior
generation. There has been continuous improvement in activity with
each generation since the introduction of ApART in 2004. Most
recently, 486DX has been shown to
have a 20% HDS advantage as well
as a 10% improvement for HDN
over AT795.
In lower pressure applications,
486DX continues to maintain its
advantage over previous generations, including AT795 (see Figure
5). Figures 4 and 5 demonstrate the
robustness of 486DX performance
and indicate that it is an effective
catalyst over a wide range of
conditions.
Both the hydrotreating catalyst
system and the operating strategy
for the pretreater are critical to
providing the highest quality feed
for the FCC. Driving the hydrotreater to remove nitrogen and
PNAs improves FCC product value
when targeting gasoline production, but this needs to be balanced
against the increased costs of
higher hydrogen consumption and
shorter cycle length that result from
this mode of operation. To address
this need, ART utilises the ApART
catalyst system for FCC pretreatment. This technology is designed
to provide increases in HDS
conversion while at the same time
providing significant upgrading of
FCC feedstock quality and increasing yields. In essence, an ApART
catalyst system is a staged bed of
high activity NiMo and CoMo catalysts where the relative quantities
of each catalyst can be optimised to
meet each refiners goals and
constraints. ART has continued to
develop a better understanding of
the reactions and kinetics involved

www.eptq.com

Global leader in
hydroprocessing
catalysts offering
the complete
range of catalysts
and services

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www.eptq.com

Relative volume activity

190
180
170
160
150
140
130
120
110
100
90
80
70

HDS
HDN

AT775

AT792

AT795

486DX

Figure 5 486DX performance in low pressure FCC pretreat

25

Activity advantage, F

in FCC pretreating and, through its


relationship with Grace Refining
Technologies, a detailed understanding
of
the
effects
of
hydrotreating
on
FCC
unit
performance.
The appropriate choice of an FCC
pretreat catalyst system must, in
addition to other potentially important considerations such as feed
metals removal, represent an optimisation of sulphur removal
capability as well as HDN and
saturation activity. The flexibility of
the ApART system offers the
potential to provide maximum
HDS activity, and thus lowest FCC
gasoline sulphur content, while also
providing a maximum in FCC unit
conversion
at
constant
coke
operation.
The addition of 586DX and
486DX to the ApART system portfolio enhances the flexibility and
performance of these systems for
FCC pretreat. They expand the
capability to significantly reduce
required SOR temperatures for
both HDS and HDN. The optimised
system of 586DX/486DX offers
refiners an enhanced ability to
generate lower sulphur FCC products as well as still delivering the
benefits of nitrogen removal and
polyaromatic saturation. Figure 6
shows a comparison of an AT575/
AT795 system with the new
586DX/486DX system. There is a
clear and significant improvement
in both HDS and HDN activity
with the ApART system.
The additional HDS activity
combined with maximum nitrogen
removal and aromatic saturation
allows refiners to utilise 586DX as a
standalone catalyst for maximum
upgrade in refinery markets
demanding
increased
yields.
Refiners can also choose to utilise
486DX as a standalone catalyst in
order to minimise hydrogen
consumption while still achieving
excellent sulphur removal for meeting Tier III sulphur regulations.
Combining these two catalysts in
an ApART catalyst system is ideal
for hydrotreaters that need to operate with controlled or minimised
hydrogen consumption yet still
require low sulphur while maintaining yield gains in their FCC.

20

HDS
HDN

15
10
5
0

AT575 / AT795

586DX / 486DX

Figure 6 Comparison of AT575/AT795 and 586DX/486DX ApART catalyst systems

These units are able to benefit from


a lower start of run temperature as
well as being able to gain some
additional improvements that are
not often achieved in a system of
100% NiMo or CoMo.

Extensive pilot testing


and experience enable
the right catalyst
system to be tailored
for maximum refinery
profit

This technology has been applied


in over 70 units in commercial
service since its inception.
Extensive pilot testing and experience enable the right catalyst
system to be tailored for maximum
refinery profit. 586DX and 486DX
will enable refiners to enhance their
operation with either increased
cycle length or additional feedstock
processing in order to maximise
margin. The ability of these catalysts to perform in different
configurations provides a high level
of versatility and makes it a catalyst
capable of exceeding refiners needs
in
demanding
FCC
pretreat
applications.

Conclusion

Advanced Refining Technologies


(ART) first introduced the catalyst
system for FCC feed pretreating in
2002. The ApART technology was
designed to provide maximum
HDS activity while also providing
significant upgrading of FCC feeds.

Charles Olsen is Director, Distillate R&D and


Technical Services with Advanced Refining
Technologies (ART).
Brian Watkins is Manager of ARTs Distillate
Pilot Plants and Technical Service, providing
customer support and monitoring globally.
Email: brian.watkins@grace.com

Catalysis 2015 33

relentless

UOP has been serving catalyst customers for


decades, and constant innovation ensures well
be there for decades to come.
Pilot plants. A true commitment to fast, thorough research and
development. A vast team of experienced, dedicated engineers
and scientists. The reasons to choose UOP catalysts are many,
but perhaps the biggest of all is that UOP never quits innovating. When you use UOP
catalysts, youll know youre using products specifically designed to help optimize
your operation. UOP invented the refining and petrochemical technology used in most
operations today, and that knowledge and expertise comes through in every catalyst we
develop. Youll always get the high stability and global support your business needs, and
youll be working with a company that will keep you on the leading edge year after year.

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


2015 Honeywell International, Inc. All rights reserved

SPM-UOP-87 Adsorbents Ad_297x210mm.indd 1

2/18/15 9:47 AM

Recovering and refining precious metals


Some factors to consider when choosing a route for recovering precious metals
from catalyst
BRADFORD COOK and ROBERT JACOBSEN
Sabin Metal Corp

recious metals are perhaps


among the most recycled
commodities on Earth, mainly
because their value usually makes
it worthwhile to spend time and
effort to recover them. The process
of recovering and refining precious
metals has been around for a long
time, but even today it remains
somewhat of a hidden industry.
This article aims to clear up some
of the most common myths
surrounding what is considered
both a science and an art for recovering maximum value from spent
precious metal-bearing catalysts.
When spent precious metal-bearing materials are reclaimed, there
are really only two essentials to
consider: accurate sampling and
precise analysis of the entire catalyst lot. That is because there are
still organisations (or even individuals) who will offer to pay you for
the remaining precious metals in
your spent process catalysts based
upon some unknown (mythical?)
and unproved premise instead of
actual precious metal content and
an accurate assay during the recovery and refining process. A catalyst
owner must be aware of this kind
of transaction; do your homework,
and check your quotes and
contracts carefully.
Another area that feeds this myth
concerns the recovery and refining
process itself: the methods and
procedures that ultimately extract
the remaining precious metals from
spent catalyst lots.

Two methods for PGM recovery

Precious metals refiners typically


use one of two methods to recover
and refine platinum group metals

www.eptq.com

(PGMs) from spent catalysts. PGMs


include platinum (Pt), palladium
(Pd), ruthenium (Ru), and rhodium
(Rh). Rhenium (Re), which is not
considered a PGM, is also present
in many spent catalysts and is a
valuable precious metal too. These
refining methods are pyrometallurgical
and
hydrometallurgical
technologies. There is a clear
distinction between these technologies that affects the outcome with
regard to capturing the highest
possible amount of remaining
precious metals in the spent catalyst lot, including Re, now worth
about $3000/kg.

Sampling is a series
of processes used
by precious metals
refiners to create a
homogeneous mass
from spent catalyst
lots
After a batch of spent precious
metal-bearing catalysts is homogenised and a representative sample
drawn, a series of laboratory instrument
analysis
procedures
is
conducted, commonly known as
assaying. Sampling is a series of
processes used by precious metals
refiners to create a homogeneous
mass from spent catalyst lots which
are randomly sampled in order to
determine the type and percentage
of precious metals remaining in the
entire lot. However, in cases where
the lot size is large (as it usually is

in the petroleum and petrochemical


industries), sampling is accomplished from a moving stream
(auto sampling).
Assaying ultimately enables the
precious metals refiner and the
catalyst owner to agree on the
value of the recoverable precious
metals contained in the spent catalyst. Once this is done, the actual
refining the processes that extract
the precious metals by one of the
two previously mentioned techniques can begin.

Pyrometallurgical vs
hydrometallurgical processing

What happens when spent catalysts


contain a significant quantity of Re?
Re is usually present in about a
third of PGM-bearing hydrocarbon
processing catalysts; for example, in
combination with Pt for reforming
naphthas into other desirable products. While all precious metals
refiners are capable of recovering
most of the Re content from spent
process
catalysts
on
soluble
alumina carriers, until recently
none has been able to recover virtually all of the Re content. There are
many reasons for this, but the main
reason concerns the inability to
separate the remaining Re with a
practical process for its recovery
and subsequent refining. This is
because refiners recover Re by
dissolving their carriers (typically
gamma-aluminum
oxide)
with
strong caustic or acidic chemicals
(the hydrometallurgical or digesting process). While this process is
capable of recovering the soluble
PGMs and Re content in spent catalysts, an unknown portion of the
desirable pay metals, sometimes as

Catalysis 2015 35

much as 20%, may remain behind


due to the insolubility of their
substrates or carriers. Insolubility
occurs because the substrate may
change phase as a result of overheating during years of operation,
preventing dissolution, even with
strong solvents.
A refiner who uses pyrometallurgical technology (for example,
Sabins Pyro-Re process) can
recover virtually all the Re content
from spent catalyst lots (semiregenerative and cyclic fixed bed),
particularly from catalysts on
substrates that cannot be dissolved
with caustic chemicals. The Pyro-Re
process also offers advantages with
regard to maximising the return
value of all precious metals in the
catalyst lot, including PGMs.

Cheaper is not better

Cheapness usually proves to be


false economy. Take, for example, a
precious metals refiners recovery/
refining reclamation contract that is
five cents lower per kilo than the
next lowest quote. The myth here
lies in the fact that many refiners
are middle men who simply broker
materials out to third party
vendors. In the precious metals
refining industry, there are essentially three categories of refining
organisations: full service refiners
(those organisations that provide
full in-house recovery and refining
capabilities, including transport
logistics to eliminate transshipping
charges and delays for settlement
returns);
samplers/processors
(those organisations which partially
process materials, perhaps upgrading them somewhat and combining
smaller lots into larger lots); and
brokers (companies or individuals
who simply buy and sell refining
services and use off-site, third party
refiners). We have seen some of
these organisations promise returns
as high as 99.99% of remaining
precious metals. The question arising here is: 99.99% of what? We
have seen this happen many times
over the years, where major refineries
award
recovery/refining
contracts on the basis of a few
pennies per pound difference in
processing fees. In fact, there are
organisations that require the

36

Catalysis 2015

lowest bidder to get the business,


no matter what the cost. While they
are understandably trying to cut
costs, this strategy has little to do
with the real money involved; the
actual returned value of precious
metals in the spent catalysts.
This is another good reason why
catalyst owners should consider
working with a refiner who
provides full in-house processing
capabilities, beginning with storage
and shipping arrangements and
continuing
through
in-house
sampling and assaying, with an
open line for the catalyst owner or
its representative to be present at
any of stage of the process. Middle
men simply add margin but no
value. Many times, large lots of
spent catalysts are sent to two or
three different processing facilities,
obviously adding costs and delays
along the way. When this happens,

Quality precious
metals recovery and
refining requires
skilled people,
sophisticated
equipment and many
years experience
settlements are delayed, and the
catalyst owner may have to finance
replacement metals for new catalyst
to ensure a seamless process flow.
Quality precious metals recovery and refining requires skilled
people, sophisticated equipment
and many years experience to
complete the full cycle and arrive at
accurate
(and
agreed
upon)
samples that are used to determine
actual precious metals content in a
spent catalyst lot.

Precious metals in spent catalysts

Documentation is supplied regarding the type and quantity of


precious metals incorporated into
process catalysts when they are
purchased. You may even have had
some of this material sampled and
tested. However, there are many

circumstances that can affect the


bottom line with regard to acquiring the highest possible amounts of
remaining precious metals. Here
are a few to consider.
First, consider the variability
(contents) of precious metals loading when the catalyst was
manufactured; we know that each
catalyst bead is slightly different, so
it stands to reason that each drum
of catalyst is also slightly different.
Anyone who manufactures a product composed of at least one
extremely valuable ingredient is
going to try very hard to keep the
level of that ingredient at the bare
minimum. In other words, it is not
impossible that a drum filled with
precious metal-bearing catalyst
contains slightly less precious
metals content than was contracted
for. On the other hand, sometimes
half the drums contain less than the
average, and half contain more
than the average. An average is an
average.
The second key issue is the
amount of water the catalyst
contains prior to a processing
campaign which typically lasts for
a number of years. The average
water content may be listed on the
certificate when the catalyst was
purchased, but there is no way for
the catalyst owner to accurately
determine the average water
content after the catalysts life cycle.
The difference here can be significant with regard to total precious
metals recovered.
Adding to the myth of actual
precious metal-bearing catalyst
composition are the other elements
that accrue during processing such
as coke, carbon, sulphur, and
perhaps additives that may have
been used to extend their life
cycles. All these elements have an
effect with regard to final recovery
at the precious metals refiner.
However, when the spent catalyst
lot is processed by hydrometallurgical techniques, these factors
become more critical since they can
interfere with the digesting
method and its ability to capture all
of the lots remaining precious
metals and its Re content as well.
This should be clearly understood
by the catalyst owner with regard

www.eptq.com

to which technique pyrometallurgical or hydrometallurgical is


used for recovery and refining.
Also, when conventional pyrometallurgical processes are used,
everything in an electric arc furnace
melts but the Re may be lost by
vaporisation of its oxide. Sabins
Pyro-Re process eliminates this
loss.

Are you getting your original


precious metals back?

Precious metals refiners of any


significant size receive thousands of
customers spent catalyst lots every
year. It is obviously not cost-effective to refine each lot separately;
that is, after the sampling stages are
completed and remaining values
are agreed upon with the catalyst
owner. Instead, think of the entire
recovery/refining process as you
would think about how a bank
works. You deposit your money,
but when you withdraw it you do
not get the same cash back.
Obviously, it is irrelevant that you
get the same cash back because that
is not what matters. What matters
is that your money was counted
properly when you made the
deposit, and that is why proper
sampling and analysis is critical to
help assure maximum returns of
remaining precious metals.

Accurate sampling for maximising


returns

In order to determine commercial


value, the materials must first be
treated or processed to allow them
to be homogenised. Once the materials are rendered homogeneous,
samples are drawn that represent
the actual precious metals content
of the entire bulk materials lot.
There are a number of ways of
doing this: melting, dissolving into
solution, and blending are a few
examples. Suffice to say that the
method chosen to achieve this
uniform state must be fit for
purpose. The goal is to eliminate
anything that can get in the way of
obtaining
that
representative
sample, because without that even
the best analytical lab in the world
will be of no use.
Once a precious metals refiner
and the catalyst owner have agreed

www.eptq.com

on a value, or settled the lot as it


is known in the industry, the
money can change hands. Usually
this money is in the form of
high-purity metals returned to a
pool account with a catalyst manufacturer so the customer can order
another parcel of fresh catalyst, but
other options are typically available
for the final commercial transactions including replacement metals
and/or payment.
In other words, the catalyst
owner does not receive the same
metal back, only its equivalent in
new metal or cash. In the end,
mathematical calculations determine
the
values,
and
the
cost-effectiveness is achieved by the
precious metals refiner by refining
large batches of like materials in a
single run.

Finding and
working with the
right refiner can
make a significant
difference in returns,
thus enhancing
overall corporate
profitability
Enhancing corporate profitability

Most hydrocarbon and petrochemical processors operate precious


metals asset recovery departments
in one form or another. These are
typically managed as independent
profit centres which, because of
global economic uncertainties, have
assumed more important roles in
the past few years. Finding and
working with the right refiner can
make a significant difference in
returns, thus enhancing overall
corporate profitability.
There are more than a few unfortunate stories about organisations
selection of, and relationship with,
its precious metals refiner. There
may be serious legal implications if
the refiner violates environmental
regulations when processing spent
catalysts.

With the dynamics of cost, profits


and possible legal issues, it is
clearly in your best interest to work
with a precious metals refining
organisation
that
does
the
following:
Provides the highest possible
returns
Provides rapid processing turnaround time
Complies with applicable environmental standards concerning
process effluent disposal or atmospheric discharges at its facilities.
There are many criteria to
consider when selecting a precious
metals refiner. Mainly the rules
come down to specific areas that
can be controlled and that apply to
virtually all refiners who process
spent catalysts containing PGMs,
Re or other precious metals. These
include the policies and procedures
associated
with
the
refiners
sampling, assaying, processing and
logistics arrangements. Each of
these areas is briefly covered as a
way of examining how to select
and work with the right refiner to
meet the catalyst owners specific
requirements.

Conclusion

The key to selecting and working


with a precious metals refining
organisation hinges upon due diligence on the owners part with
regard to determining all of its
policies and procedures, including
point-to-point transport logistics
which will also reduce costs and
speed processing and thus return
materials values quickly. Key
emphasis must be placed on the
refiners environmental policies and
procedures.
Pyro-Re is a trademark of Sabin Metal
Corporation.

Bradford M Cook is Vice President Sales and


Marketing with Sabin Metal Corporation,
with an extensive background in the precious
metals industry.
Robert T Jacobsen is a Vice President of Sabin
Metal Corp, with a background in the precious
metals industry, starting in the mid-1960s. He
holds a BA in chemistry from the University of
Rochester, a masters degree in education from
Columbia University, and a PhD in chemistry

Catalysis 2015 37

breakthrough
catalyst
technology
Johnson Mattheys new breakthrough catalyst technology, CATACELJM SSR, a
high performance catalyst coated stackable structured reactor for steam
reforming, delivers greater capacity and longer catalyst life than traditional
pelleted catalysts.
Our CATACELJM SSR technology is proven to ease operating limits on the reformer
and increase throughput through reduced tube wall temperature, lower pressure
drop, decreased energy consumption, and improved carbon resistance.
Our technical support team will work with you to
assess your needs and determine if
CATACELJM SSR technology is a good
fit for your operation.

Tel +44 (0)1642 553601

Fax +44 (0)1642 522542

USA Tel +1 330 298 7005

www.jmprotech.com
www.catacel.com

Structured catalysts for steam reformers


A foil based catalyst aims to avoid the limitations of ceramic pellet substrates in
steam reforming
WILLIAM WHITTENBERGER Johnson Matthey Process Technologies
PETER FARNELL Johnson Matthey plc

team reforming catalyst design


is a balance between many
competing requirements such
as strength, heat transfer, activity,
pressure drop and the avoidance of
carbon formation. Catacel SSR is a
coated foil based alternative to
metal-impregnated ceramic pellet
media. A foil based structure
enables SSR to avoid many of the
limitations imposed by the use of
ceramic pellets. It exhibits higher
activity, improved heat transfer,
lower pressure drop and improved
carbon resistance all at the same
time.
Depending on the plant design,
SSR can be used to decrease tube
temperatures, reduce natural gas
fuel consumption or increase
throughput of the reformer. New
reformers can typically be designed
with lower capital cost of the radiant box. This technology has been
demonstrated in two commercial
hydrogen plants since May 2012.

Catalyst coated foil

The principle of the technology is


the ability to coat catalyst materials
onto the surface of thin metal foils.
The coating process ensures that
the catalyst remains attached to the
surface of the foil during the catalysts lifetime.
Alloy strip is formed into engineered foil supports called fans (see
Figure 1). The fans are coated with a
nickel based steam reforming catalyst. The fans are quite springy and
can easily be pulled or pushed into
different diameters or shapes.
They are stacked one upon
another, separated by thin metal
washers (see Figure 2) in groups up
to one metre long over a support

www.eptq.com

Figure1 Catacel SSR fan

structure that sits within the central


space of the fans. This central structure aids in the speed and accuracy
of catalyst installation by avoiding
the need to install the fans individually. The stacked fans deliver
superior heat transfer by impinging
gas on the internal surface of the
reforming tube, rather than relying
on convective heat transfer mechanisms. This results in about 20-30%
more heat transfer for the same (or

Figure 3 Gas forced out of triangular ducts

Figure 2 Catacel SSR stack

lower)
pressure
drop
when
compared to traditional catalyst
pellets. In addition, the fans offer
1.5 to 2.0 times more geometric
surface area than conventional
pellets.

Figure 4 Gas flowing over the edges

Catalysis 2015 39

Pressure drop

Katalco GQ series
Catacel SSR

Mass flow

Heat transfer coefficient

Figure 5 Pressure drop vs flow

Katalco GQ series
Catacel SSR

Mass flow
Figure 6 Heat transfer vs flow

How SSR works

Relative performance
indicator

The stacked fans and impingement


mechanism work as follows. Gas
flowing down the tube encounters
the first fan structure. It cannot
move through the fan as the bottom
of the fan is closed and the central

hole is blocked by the support


structure. The gas is therefore
forced out of the triangular ducts,
impinging directly on the internal
surface of the reformer tube, where
it gathers heat (see Figure 3).
Having nowhere else to go, the gas

Activity
Heat transfer
Pressure drop

Rings

4-Hole

Quadralobe

Catacel SSR

Catalyst type
Figure 7 Relative performance of various steam reforming catalysts

40

Catalysis 2015

flows around the edges of the fan


and back into the triangular duct
on the underside side of the fan
(see Figure 4). The washers that
separate the fans from one another
facilitate this flow back into the fan.
Once inside the fan, the gas is free
to move to the next fan in the stack
and repeat the process.
The gas moving in and out of the
fans continuously flows over all of
the catalyst-coated surfaces of the
fans, where the reforming reaction
takes place.
The impingement heat transfer
mechanism results in a significant
performance benefit when compared
to pellets. Results from tests are
shown in Figures 5 and 6. A SSR
design was selected that gave a
pressure drop very similar to that of
Katalco GQ size Quadralobe reforming catalyst pellets (see Figure 5).
The improved heat transfer achieved
by the SSR design is shown in Figure
6, which illustrates an improvement
of approximately 30%.
The key performance indicators
for the SSR catalyst set on a timeline of the various Johnson Matthey
steam reforming catalysts is shown
in Figure 7. This shows how the
activity, heat transfer and pressure
drop of steam reforming catalysts
have developed over the past three
decades.
Set against this, the performance
improvements of the SSR catalyst
are substantially larger than those
that can be obtained by further
development of ceramic based
pellets and are larger than any
previous improvements seen.
Any of the improvements in
performance taken on their own
would generate substantial benefits
for operators of steam reformers.
However, as the activity and heat
transfer can both be markedly
improved whilst at the same time
reducing the pressure drop, it
generates the potential for noticeable
improvements
in
steam
reformer operation. The SSR catalyst will generate reductions in tube
wall temperature, increasing the
heat transfer efficiency of the
furnace. It will reduce the approach
to equilibrium and methane slip,
decrease operating pressure and
the risk of carbon formation,

www.eptq.com

In August 2008, an early version of


SSR was installed in a small can
reformer in a hydrogen plant in
Turkey. The plant ran well for four
years in spite of numerous upsets
unrelated to the catalyst. Even
though it was still performing well,
that catalyst was removed in
January 2013 at a scheduled turnaround and replaced with the
current version of SSR. The removal
and reinstallation process was
accomplished without major incident. The coated foils removed
maintained their original integrity
in spite of the process upsets and
significant contamination from
boiler feed water, indicating that
coated foil materials can survive
and thrive in a reforming environment. The new charge started up
well and has operated without
issue since installation.

Second installation: Mexico

In May 2012, SSR was installed in a


small can reformer in a hydrogen
plant in Mexico. This user sought
to obtain natural gas savings by
reducing fuel consumption, while
having the option to increase
throughput beyond the name plate
capacity, and attain a longer operational lifetime for both the catalysts
and reforming tubes. The reformer
configuration in the plant consisted
of reformer tubes of varying ages,
several of which had been
recharged with ceramic pellet catalyst as recently as January 2012.
After thorough study and analysis,
the plants managers decided to
replace the ceramic catalyst media
in all reformer tubes with SSR catalysts.
The
change-out
was
completed with minimal downtime
in May 2012 by plant staff under
supervision.
After installation, the hydrogen
plant restarted without incident,
and immediately demonstrated a
13.5% reduction in burner make-up
fuel consumption. Over the follow-

www.eptq.com

Furnace temperature, C

Initial installation: Turkey

940
920
900
880
860
840
820
800
300

Pellets
SSR
400

500

600

700

H2 production, Nm3/hr

Furnace temperature reduced 40-60C.


Lifetime of tubes and furnaces improved.

Figure 8 Furnace temperature reduction with SSR

ing weeks, the plants operating


conditions were optimised to take
advantage of SSR. Figures 8 and 9
show furnace temperature reduction (40-60C) and fuel savings
(25-30%) realised at various plant
rates with the optimised plant.
The plant continues to perform at
optimum levels and the estimated
payback time for the entire charge
is two years based only on fuel
savings alone. This does not
account for savings to be realised
over years to come by eliminating
catalyst and tube changes.

Case studies

The development path for SSR catalyst


has
demonstrated
its
performance in two small can
reformers. However, the majority
of operators in the syngas industry

Fuel to burner, Nm3/hr

increasing both catalyst and tube


lives. In a new reformer, considerable capital can be saved. These
benefits will be described in more
detail in the case studies presented
below.

120
110
100
90
80
70
60
50
40
30
20
10
0
300

use either top fired or side fired


reformers. A series of case studies
based on plant performance modelling follows, demonstrating several
scenarios in which the technology
can improve steam reforming operations for typical top fired and side
fired reformers.

Hydrogen plant uprate

In the first case study, a small


hydrogen plant was initially
designed to operate on naphtha
feedstock which was later changed
to natural gas. The heat exchange
duty in much of the plant was
reduced because the steam ratio
was reduced, which also decreased
the combustion air flow requirement, resulting in excess capacity
in the combustion air fans.
However, the reformer is now

Pellets
SSR
400

500

600

700

H2 production, Nm3/hr
20-30% savings in burner fuel.

Figure 9 Fuel savings with SSR

Catalysis 2015 41

Impact of SSR catalyst on a hydrogen plant reformer


Case
Base
Catalyst
QuadralobeJM
Description
Base
Relative feed flow, %
100.0
Relative fuel flow, %
100.0
Relative combustion air flow, %
100.0
Excess air, %
15.0
Exit temperature, C
860
Methane slip, mol%dry
2.80
Max tube wall temperature, C
890
Approach to equilibrium, C
2.8
Pressure drop, bar
1.29
Flue gas exit temperature, C
997
Relative hydrogen make, %
100.0

1
CatacelJM SSR
Same throughput
100.0
99.5
99.4
15.0
860
2.75
885
1.8
1.01
991
100.2

2
CatacelJM SSR
Additional throughput
115.0
112.5
105.0
7.5
861
2.80
891
2.1
1.28
1012
115.0

drop. The fuel required rises by


12.5% and the combustion air rises
by 5%. This reduces excess air
making the furnace more efficient,
with the result that the flue gas
temperature increases by just 15C.
Installing SSR catalyst in this
plant can provide a simpler and
more cost effective way of achieving the increased throughput
required. The operator in this case
is installing SSR catalyst during
2015 to support the plant uprate.

Hydrogen plant reduced steam ratio


Table 1

operating close to the tube wall


temperature limit. In an attempt to
moderate the peak tube wall
temperature at the top of the tubes,
excess fan capacity is currently
being used to provide high excess
combustion air.
Whilst the rest of the plant is
capable of operating at this higher
capacity, the tube wall temperatures are the limiting factor. The
option chosen to release the available capacity in the rest of the plant
is to change to SSR catalyst in the
steam reformer. The higher heat
transfer and higher activity of the
catalyst can reduce the tube wall
temperature significantly, allowing
higher throughput and firing for
the same reformer pressure drop.
Table 1 shows the reforming
parameters for the hydrogen plant
based on the Katalco, Quadralobe
and SSR catalysts.
The base case defines the maximum operating point of the plant
based on the current limit of tube

wall temperature and pressure drop.


Case 1 shows the impact of
installing SSR catalyst in the
reformer at the current throughput.
There is a significant improvement
in both the pressure drop and the
maximum tube wall temperature,

Installing SSR
catalyst can provide
a simpler and more
cost effective way
of achieving the
increased throughput
required
so that these conditions no longer
limit the reformer.
Case 2 shows that a 15% increase
in throughput can be achieved
within the existing constraints of
tube wall temperature and pressure

Cumulative
Expenditure,
Reduced
steam ratio
with SSR catalyst on a hydrogen plant reformer

expressed as
a % of total Installed Cost (TIC)
Factored off
Case
Base
Catalyst Equipment
QuadralobeJM
DescriptionFactored off
Base
Equipment
Relative gas
feed flow, %
100.0
Relative gas fuel flow, %
100.0
Relative total natural gas flow, %
100.0
Steam ratio
2.9
Pressure drop, bar
2.65
Exit temperature, C
827
Max tube temperature, C
867
Min carbon margin, C
39
Relative flue gas heat duty, %
100.0
Relative process gas heat duty, %
100.0
Relative hydrogen make, %
100.0

Table 2

42 Catalysis 2015

1
CatacelJM SSR
Same steam ratio
99.9
98.9
99.6
2.9
2.65
827
861
59
98.7
99.8
100.0

2
CataceljM SSR
Lower steam ratio
102.4
91.5
99.4
2.7
2.55
827
861
52
98.2
96.2
100.0

There is a trend in hydrogen plant


designs to seek operation at a lower
steam to carbon ratio to improve the
economics of the overall hydrogen
process. SSR catalyst, with its significant increase in activity, reforms the
hydrocarbons more quickly. This
increases the hydrogen content, thus
reducing the rate of carbon formation and increasing the rate of
carbon removal. Additionally, the
improved heat transfer of the catalyst results in a lower tube wall
temperature at all points along the
tube and, as carbon typically forms
at the tube wall, this will also reduce
the propensity for carbon formation.
Therefore, the benefits of the catalyst can be taken as a reduced steam
ratio to bring the plant to the same
margin from carbon formation as
with the pelleted catalyst at a higher
steam ratio.
An assessment of the benefits of a
reduction in steam ratio from 2.9 to
2.7 with SSR catalyst for a hydrogen plant is shown in Table 2.
The base case gives the key
parameters for the reformer with
Katalco Quadralobe pelleted catalysts, indicating that the tube wall
temperatures are 39C from the
carbon formation temperature.
Case 1 shows the predictions for
operation with the SSR catalyst at
the same hydrogen production rate
as the base case at the original
steam ratio. There is a 50% increase
in the margin between carbon
formation and the inside tube wall
temperature.
Case 2 shows the predictions for
operation with the SSR catalyst at
the lower steam ratio. The hydrogen production rate remains the
same by increasing the feed rate to

www.eptq.com

compensate for the increased methane slip. Overall, the reformers


efficiency is increased as the total
natural gas feed plus fuel flow is
lower than Case 1 and there is less
heat transferred into the flue gas or
process gas.

New reformers designed for SSR


technology

In recent years, there has been a


trend towards reformer designs
with larger diameter, longer tubes
to take advantage of the improved
catalysts and reformer tube materials available. Such designs result in
a smaller number of tubes, which
reduces the costs of the reformer.
The adoption of SSR catalyst can
have a significant impact on the
design of new reformers due to its
higher heat transfer, higher activity
and lower pressure drop. The
reduced tube wall temperature
allows the use of thinner wall tubes,
reducing the tube cost. The reduced
pressure drop allows the use of a
smaller number of longer tubes for
the same overall pressure drop,
creating additional cost savings.
Several reformer designs have
been investigated, with a redesign
based on SSR catalyst. Cost
comparisons have been made
between the reformer designs to
show the savings that are available.
The reformer designs have been
made on identical process duties
and the same design tube wall
temperature design margin.
Tables 3 and 4 show the results
for two different reformer configurations and duties where the design
based on Katalco Quadralobe has
been modified for SSR catalyst. The
key dimensions of the furnace are
given along with the key process
parameters. The final row in each
table gives an estimate of the relative cost of the radiant box for both
pelleted catalyst and SSR catalyst.
The data show a capital cost
saving of the order of 8-10% for
each of the designs listed.
Additional studies over a wider
range of reformer duties have
shown that this is repeatable for
most reformers, with the smallest
savings no less than 5% and some
redesigns showing a cost saving of
15%.

www.eptq.com

Impact of SSR catalyst on a new terrace wall reformer

Catalyst
Number tubes
Number tube rows
Number tubes/row
Tube ID, mm
Tube OD, mm
Tube wall thickness, mm
Tube heated length, m
Furnace length, m
Furnace width, m
Heat load, MW
Catalyst pressure drop, bar
Minimum tube wall margin, C
Relative cost, %

QuadralobeJM
352
2
176
108.0
132.0
12.0
13.72
36.03
2.00
134
3.31
34
100.0

CatacelJM SSR
322
2
161
111.4
132.0
10.3
14.00
32.95
2.00
134
3.31
34
90.2

Table 3
Impact of SSR catalyst on a new top fired reformer
Catalyst
Number tubes
Number tube rows
Number tubes/row
Tube ID, mm
Tube OD, mm
Tube wall thickness, mm
Tube heated length, m
Furnace length, m
Furnace width, m
Heat load, MW
Catalyst pressure drop, bar
Minimum tube wall margin, C
Relative cost, %

QuadralobeJM
728
14
52
115.0
134.4
9.70
13.18
14.96
32.52
263
2.83
79
100.0

CatacelJM SSR
636
12
53
115.6
134.4
9.40
14.25
15.22
27.94
263
2.78
79
92.0

Table 4

Conclusions

Structured SSR technology delivers


a significant improvement in performance compared to traditional
pelleted catalysts. The catalysts have
been demonstrated to be mechanically and chemically robust during

Structured SSR
technology delivers
a significant
improvement
in performance
operation over typical reforming
catalyst lives in commercial steam
reformers. Their adoption in a steam
reformer results in significantly
cooler tubes with lower methane
slip and lower pressure drop. This
can result in the easing of these
operating limits on the reformer,

which can allow significant increases


in throughput to be achieved.
Substantial savings can also be
made in the size and capital cost of
new reformers designed on the basis
of the technology.
KATALCO, QUADRALOBE, CATACEL and SSR
are marks of the Johnson Matthey Group of
Companies.
William A Whittenberger is Site and
Technology Director with Johnson Matthey
Process Technologies, Inc, which acquired the
assets of Catacel Corp, Ohio, in September
2014. He co-founded Catacel in 2001 to
develop and commercialise catalyst materials
and systems using metal foil substrates.
He holds a bachelors degree in mechanical
engineering from Ohio State University, a MBA
from Pepperdine University and 50 patents
covering foil based catalyst design.
Peter Farnell is Reforming Technology Manager
with Johnson Matthey Process Technologies.
He holds a masters degree in chemical
engineering from Loughborough University of
Technology, UK.

Catalysis 2015 43

15MAKT033-Cap-ad-update-fnl.pdf

CM

MY

CY

CMY

2/27/15

2:01 PM

Four-stage hydrocracking pretreatment


A four-zone approach to hydrocracking pretreatment catalysis aims for greater
flexibility in activity, stability, hydrogen consumption and pressure drop
STEFANO MELIS
Albemarle

n the current market that rewards


distillate production, many refiners are looking closely at the
performance of their hydrocrackers.
To improve hydrocracking margins,
refineries explore solutions ranging
from increasing feed severity to
improving yield structure and product quality. Multiple operational
constraints, in particular cycle length
and hydrogen availability, often
determine the feasibility of each
approach. In most cases, significant
improvements require highly reliable and tailored catalytic solutions.
Albemarles portfolio for hydrocracking pretreatment has eight
different catalysts (each available in
two different sizes) meeting refiners
needs in terms of activity, stability,
hydrogen consumption and pressure drop (see Table 1). These
catalysts can be sequenced in many
ways according to Albemarles Stax
technology (optimal catalyst system
design technology) to generate solutions for specific requirements.

Stax in hydrocracking pretreatment

In a traditional approach to catalyst


system design, pretreatment has two
parts (see Figure 1): the top of the
reactor is filled with grading/
demetallisation catalyst and the rest
of the reactor is filled with a single
active catalyst.
With such an approach during the
design phase, once the catalyst is
selected and the operational target is
set (typically, nitrogen slip) there is
relatively little flexibility left, apart
for some minor adjustments that can
be achieved with quenching strategy. This two-part approach to
pretreatment has consequences:
a) The top part of the active catalyst

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Albemarles hydrocracking pretreatment catalyst portfolio


Catalyst
Sizes
Ketjenfine R (KFR) 22 1.3Q, 3Q
KF 851
KF 861 Stars
KF 905
KF 848 Stars
KF 860 Stars
KF 868 Stars
Nebula 20

Properties
Maximum stability for heaviest feedstocks; demetallisation;
removal of asphaltenes and Conradson carbon residue
1.5Q, 3Q Excellent stability; lowest hydrogen consumption
1.3Q, 2Q Good stability; good hydrodenitrification (HDN) activity
1.3Q, 3Q Excellent stability; maximum direct desulphurisation (DDS)
activity; lowest hydrogen consumption
1.3Q, 2Q Good stability; high HDN activity
1.3Q, 2Q Excellent stability for VGO feeds; high HDN activity
1.3Q, 2Q Good stability; excellent HDN activity; denitrogenation
and dearomatisation
1.5Q. 2.3Q Extreme HDN and aromatic saturation activity

Table 1

will be exposed to much heavier


feed than the bottom part and could
be susceptible to fast deactivation.
To prevent this deactivation, the
low-activity grading zone could be
expanded but this sacrifices activity.
b) Product sulphur and aromatics
cannot be independently controlled
but are determined by the given
nitrogen slip. For example, if the
hydrogen consumption becomes too
high, the operating temperature of
the pretreatment at that point must
be reduced, so the product nitrogen
slip increases, thereby causing an
imbalance in the conversion section.
Alternatively, an active catalyst with

Grading + demetalisation

Active catalyst

Figure 1 Traditional two-step pretreatment

lower activity can be selected but


this will result in worse yields and a
shorter cycle length. When the product sulphur specification is not met,
this imbalance becomes even more
problematic. In such a case, the
nitrogen slip has to be reduced. This
has positive effects on the conversion section but is detrimental to
hydrogen consumption and cycle
length.
Albemarles approach is markedly
different. The basic principle is that
each reactor zone is exposed to an
oil product of a different quality, so
the reactions taking place in each
zone are very different. Hydrocracking pretreatment generally has
four zones that, depending on the
situation, could vary in length and
location (see Figure 2) or disappear.

Zoning

The first zone (Zone a) only exists


for extremely heavy feeds, for example with an asphaltene content
exceeding 500 ppm or an end boiling point higher than 650C. For
Zone a, dedicated catalysts with
specific pore size distribution and

Catalysis 2015 45

and demetalisation

Grading
Zone A: removal of metals, asphaltenes, CCR; management of heavy aromatics
Zone B: polyaromatics saturation; bulk HDS and HDN (removal of easy S and N)

atalyst

Zone C: aromatics saturation; HDS and HDN of difficult species


Zone D: HDN of extremely refractory N; deep saturation of monoaromatics

Figure 2 Four-zone approach to hydrocracking pretreatment

texture composition are necessary.


Indeed, even demetallisation catalysts quickly coke when the
feedstock is so heavy, which results
in metals and coke precursors slipping to the main catalyst and
consequent rapid deactivation. For
such conditions, Albemarle recommends KFR 22, which combines
hydrodemetallisation activity and
efficient removal of asphaltenes and
Conradson carbon residue.
Although by Zone b the feed is
partially cleaned up, stability is still
the main problem, so a robust catalyst is required. In this zone,
multi-ring polyaromatics (four rings
or more) are strongly adsorbed onto
the active sites and converted to
coke during the cycle. Similarly to
Zone a, a catalyst with a specific
pore size distribution and texture
composition is required, but now it
needs good activity for HDS and
HDN.
For this zone, we propose four
different catalysts, depending on
duty and unit limiting factors. In
most cases, KF 860 Stars is applied,
which delivers excellent HDS, HDN
and robustness. Alternatively, KF
851 and KF 861 Stars are options if
the unit is unconstrained by product
nitrogen or product sulphur. Finally,
KF 905 Stars can be applied to units
where the nitrogen target is relatively easy while the product
sulphur is limiting, which happens
in some mid- to low-pressure mild
hydrocrackers.
Zone c is perhaps the zone that
reflects the most typical perception
of hydrocrackers. Here, the only
critical performance characteristic is
HDN activity, so catalysts are
selected on activity requirements
weighted to cost. For this zone, we
recommend, in order of increasing

46 Catalysis 2015

activity, KF 851, KF 861 Stars, KF


848 Stars and KF 868 Stars.
Zone d, the final zone, is where
product nitrogen is typically below
100 ppm. Here, conversion of the
most difficult nitrogen molecules
occurs. In addition, as the product
nitrogen content is low, extensive
hydrogenation of monoaromatics
may occur with a corresponding
increase in hydrogen consumption.
The catalyst selection for this zone
therefore depends on unit objectives
and hydrogen availability. Typically,
a high-activity HDN catalyst like KF
848 Stars or KF 868 Stars is selected.
When extreme performance is
desired, we recommend our highest
activity catalyst, Nebula 20, for Zone
d. This has twice the hydrogenation
activity of other conventional catalysts. Such activity can be exploited
in two ways: by reducing product
nitrogen to very low levels, thereby
facilitating the operation of the
cracking catalyst and improving the
yields; or by operating at the same
product nitrogen slip as conventional systems but at a lower
temperature (longer cycle length) or
with more difficult feedstock, for
example, larger intakes of distressed
feedstocks.
When the unit is heavily
constrained by hydrogen consumption, we recommend using a
declining activity profile. Very active
catalyst, such as KF 868 Stars, is then
placed in Zone c to provide most of
the required HDN activity without
penalties in hydrogen consumption,
as here product nitrogen is relatively
high and hydrogenation of monoaromatics is not extensive. Less active
catalyst, for example, KF 851 or KF
861 Stars, is then placed in Zone d to
provide the additional HDN activity
necessary to reach the product

nitrogen slip target with minimal


hydrogen consumption, as monoaromatics saturation is mitigated
because the hydrogenation activity
of these catalysts is insufficient to
facilitate this reaction.

In action

Stax technology has been already


applied in numerous hydrocracking
units worldwide. One example is a
hydrocracking unit operating at 150
bar and processing a feedstock with
extremely heavy tails. For this unit,
a loading with KFR 22 (Zone a), KF
860 Stars (Zone b) and KF 868 Stars
(Zones c and d) was selected to
replace a competitors catalyst. The
result was a 30% improvement in
cycle length despite operating at
lower product nitrogen slip, with
the latter factor guaranteeing an
appreciable improvement in distillates yield.
A second example is a hydrocracking unit running at 110 bar. In
this case, the feedstock characteristics were such that Zone a was
absent. The loading consisted of a
combination of KF 860 Stars (Zone
b), KF 868 Stars (Zone c) and Nebula
20 (Zone d). In comparison with the
previous cycle, it was possible to
process an additional 510% of a
low value, heavy distressed feedstock while maintaining the same
cycle length, which improved the
refiners margin.

Conclusion

Stax is a commercially proven technology that tailors the catalyst


system for optimised operation of a
hydrocracking unit. Applying this
technology is possible through a
portfolio of hydrocracking pretreatment catalysts. Possibilities for
helping refineries to enhance their
operations and increase profitability
through the application of Stax
include improved distillate yield,
increased cycle length, processing
more difficult feedstocks, improved
product quality, optimised hydrogen addition, or combinations of
these targets.
Stefano Melis is a Global VGO Application
Specialist at Albemarle, The Netherlands.
He holds a BS in chemical engineering from
University of Cagliari, and a PhD in chemical
engineering from University of Bologna, Italy.

www.eptq.com

Catalysis Industry Updates


Johnson Matthey buys Catacel

Johnson Matthey has expanded its refinery catalysis


business with the acquisition of Catacel Corporation.
The Ravenna, Ohio-based company develops and
supplies technology based on metal foil coated catalysts
and sorbents to process industries. Its products include
high heat transfer catalyst technology for hydrogen and
syngas production and fuel processing systems for
stationary fuel cells (see p37 of this issue of Catalysis).
Catacel shapes special metal foils into a variety of
geometries and then coats the foils with different catalysts designed to enable target reactions within specific
processes. The resulting shaped and coated foils are
used within components that enable combustion, catalytic partial oxidation, fuel reforming, tail gas
combustion, desulphurisation, hydrogen production via
steam methane reforming, and carbon capture
processes.
For instance, Catacels stackable structural reactor
(SSR) technology is a catalyst system for steam
methane reforming that targets fuel savings or increases
in throughput in tubular reformers. Johnson Matthey is
already a major supplier of catalyst technology to steam
reformers in the hydrogen, methanol and ammonia
markets. Hence, further development and optimisation
of SSR technology will enable the parent company to
widen its range of catalyst technologies for hydrogen or
syngas manufacture.
Catacel is also active in the development of coated
catalysts and reactor systems for fuel processing
for stationary fuel cells. Johnson Matthey says it
will look to identify technical and commercial synergies
within its current businesses for growth in that market.
The Catacel business will be integrated into Johnson
Mattheys Process Technologies Division, alongside the
Intercat and Katalco brands, and will have access to its
new parents network of research and technology
centres with their development and characterisation
facilities.
Commenting on the acquisition, Johnson Matthey
says that Catacel complements its existing portfolio of
catalysts and technologies for the process industry and
that Catacel has strong and differentiated technology
and good prospects for future growth.
Johnson Matthey company Tracerco has opened a
Measurement Technology Centre (MTC) in Billingham,
England. The 9 million investment, which houses 150
people, provides a custom built research, development
and engineering test centre for its teams of scientists
and engineers. It is intended to give the business a platform to expand its technology for the oil, gas and
petrochemical industries.
Tracerco provides measurement and tracing services
for performance issues in the refining and petrochemicals industry.

www.eptq.com

Split decision for Grace Catalysts Technologies

W. R. Grace & Co has split into two independent


companies. The two companies are initially named
New Grace, in charge of Graces Catalysts Technologies
and Materials Technologies businesses, and New GCP,
to handle the former combined companys construction
materials and packaging materials operations.
At the announcement of the split, the Grace board
said that the move will enhance the strategic focus of
the two operating companies with industry-leading
market and technology positions, strong free cash flow
and high returns on invested capital created through
this transaction.
New Grace is predicted to have sales of approximately $1.8 billion, approximately $2.2 billion including
sales from the unconsolidated joint venture with
Advanced Refining Technologies (ART). Grace said it
believes that New Grace will seek to make strategic
acquisitions in its core segments as well as acquisitions
to expand its specialty chemicals and performance
materials ranges.

Albemarle realigns refining operations

Chemicals group Albemarle is reorganising its global


business units including the Refining Solutions arm
that produces refinery catalysts. The move follows
Albemarles take-over of Rockwood Holdings, a
specialist in lithium battery technology. The move will
align the companys strategic assets and businesses to
be market focused and enable it to more effectively
leverage its resources on innovation and growth.
The new business structure was scheduled to take
effect by the end of the first quarter of 2015 and will
comprise three global business units: Refining
Solutions,
Chemetall
Surface
Treatment,
and
Performance Chemicals. Refining Solutions will include
the companys heavy oil upgrading and clean fuels
technology businesses, including a range of catalyst
products for refinery-wide applications.
Silvio Ghyoot, who has been with Albemarle for 25
years in a variety of roles, will become President of
Refining Solutions.
In a statement, Albemarle said that the reorganisation
will help us achieve our goal of growing faster and
performing at even higher levels and help accelerate
the identification and achievement of strategic synergies beyond the identified cost synergies.

BASF expands global research and production

BASFs Refining Catalysts division has opened a fluid


catalytic cracking (FCC) catalysts testing and research
laboratory at the hte GmbH site in Heidelberg,
Germany. hte is a wholly owned subsidiary of BASF SE
and a provider of high throughput technology and
services for enhancing productivity in the research and

Catalysis 2015 47

development of catalysts for the refining industry.


The new laboratory will provide physical and chemical analyses and characterisations of hydrocarbons and
FCC catalysts, fine particles and slurries. It will also
develop advanced refining catalysts test methods,
complementing BASFs existing FCC catalysts laboratory in Iselin, New Jersey.
BASF is also building a new, world-scale chemical
catalysts production facility at the companys existing
site in the Shanghai Chemical Industry Park, Shanghai,
China. The plant is BASFs first process catalysts manufacturing facility in the Asia-Pacific region and will
produce base metal catalysts, custom catalysts, and
adsorbents for Chinese and wider Asian markets.
Construction of the new plant is under way and
manufacturing is due to start in the fourth quarter of
2016. According to the company, by 2020 BASF
Catalysts aims for local production of approximately
75% of the products it sells in the Asia-Pacific region.

From forest floor to gas meter

A company producing fuel gas from forest residues


using Haldor Topses catalyst technology has begun
feeding its product into Swedens natural gas supply
grid. One of Swedens leading energy companies,
Gteborg Energi, said that the plant, GoBiGas, has
become the worlds first large-scale demonstration
plant for the production of biogas through the gasification of biofuels and residues from forestry.
Haldor Topse has provided licensing, catalyst and
engineering for gas cleaning at GoBiGas, as well as
for the methanation section, enabling the plant to
produce substitute natural gas (SNG) by thermal gasification of forest residues such as branches, roots and
tops. The biomass is converted to gas with a methane
content of over 95% and the plant has a capacity of 20
MW SNG.
The GoBiGas project consists of two primary phases.
Phase one has focused on establishing the demonstration plant that is now in operation while the second
phase is to expand to a full-scale commercial plant with
a capacity of 80 MW SNG.
Until now, all running industrial references related to
SNG in Topse have been based on coal gasification or
coke oven gas. With the start-up of GoBiGas, Topse
says that it has demonstrated and proven that its catalytic solutions and process technology make it possible
to efficiently carry out biomass to SNG conversion.

Expansion ahead for catalyst regen

The catalyst regeneration market will grow at a


compound annual growth rate of 5.54% between 2014
and 2019 to reach an annual value of over $5 billion by
the end of the period, according to a report from
MarketsandMarkets Business Research.1
Off-site regeneration of catalysts is a key market for
regenerated catalyst and is segmented into two regeneration technologies: off-site and on-site. These two
regeneration technologies have application specific
demands that are differentiated by cost and efficiency.
The off-site catalyst regeneration has the highest

48 Catalysis 20155

market share and is also the fastest growing market.


Off-site regeneration is a rapidly growing technology
opted by oil refining and chemical and petrochemical
industries due to stringent environmental regulations,
cost optimisation, and better quality and performance
of regenerated catalysts.
The catalyst regeneration market is set to be worth
$5002.47 million by 2019, says the report. In terms of
volume, Europe dominated the catalyst regeneration
market in 2013 and is expected to register a steady
growth rate by 2019. However, as a result of the closure
of refineries in Europe, the regenerated catalyst market
is projected to undergo a slow growth rate. The catalyst
regeneration market in North America is set to experience a period of boom through the rest of the decade
due to recent discovery of shale gas.
The catalyst regeneration market in Asia-Pacific is
expected to grow at the highest rate between 2014 and
2019 due to the regions rise in refinery capacity and
penetration of regeneration services for refinery catalyst. Asia-Pacific and the rest of the world outside
North America and Europe together are expected to
account for more than 40% of the regenerated catalyst
market, in terms of value, by 2019.
1 Catalyst Regeneration Market by Technology (Off-site regeneration
and On-site regeneration), by Application (Refinery, Chemicals &
Petrochemicals, and Others), by Region (North America, Europe, AsiaPacific, and Rest of the World) - Forecast till 2019.

More on-purpose propylene for China

Honeywell company UOP has commissioned a second


unit in China to produce on-purpose propylene using
its C3 Oleflex technology. The plant was delivered to
Zhejiang Shaoxing Sanjin Petrochemical Co. and brings
global production capacity from the technology to
approximately 3.8 million t/y.
Propylene as a refinery product is currently unable to
meet rising global demand, hence the progress of technologies such as C3 Oleflex to make up the shortfall
with on-purpose propylene.
Since 2011, UOP has licensed the C3 Oleflex process
to more than a dozen producers with the largest share
of licensed capacity in China. China is the worlds largest energy consumer and its propylene consumption
accounts for more than 15% of worldwide demand,
which is growing annually at about 5-6%. By 2020, 20%
of the worlds propylene production is expected to
come from on-purpose production technologies, according to UOP.
In addition to technology licensing, UOP provided
Zhejiang Shaoxing Sanjin Petrochemical Co. with engineering design, catalysts, adsorbents, equipment,
training and technical service for the project.
Equipment supply included Callidus Low NOx
(Callidus Stage Gas Ledge Stabilisation) burners, manufactured at UOP Callidus Shanghai.
Zhejiang Shaoxing Sanjin Petrochemical Co., Ltd. will
produce 450 000 t/y of propylene at its facility. It is a
fully owned subsidiary of Zhejiang Fuling Holding
Group, in Shaoxing City, China, which specialises in
polypropylene production and produces 600 000 t/y.

www.eptq.com

The
safe
mu
pro
fun

A diesel catalyst solution that really STAX up.

Albemarle leads the way in designing catalyst systems to maximize volume swell.
Our commercial experiences validate the benefits of using STAX technology to realize economic gain from ultra-lowsulfur-diesel (ULSD) hydrotreaters and hydrocrackers. Albemarles Nebula catalysts deliver the highest denitrogenation
and hydrogenation activity of any base metal hydrotreating catalyst. When combined with our STAX technology to balance
unit objectives with capabilities, hydrogen addition over the catalyst cycle can be optimized based on the limitations of
the unit. The result? Efficient production of cleaner fuel with lower emissions and that equates to increased profitability.

For more information on Albemarle catalysts for maximizing volume swell or our exceptional
portfolio of products and services, call (281) 480-4747 or visit www.albemarle.com.

REFINERY CATALYST SOLUTIONS

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