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D
5 ptq Catalysis Roundtable
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
René G Gonzalez refiners remain a big play for prospective investors. It used to be
editor@petroleumtechnology.com
11 conventional
Maximising wisdom fuels from thatthe higherFCCfuel unitprices and a slowing economy
would
Bruce Adkins and Ken Bruno Albemarlebut for the past seven years
curb demand and increase supply,
Production Editor that has not proved to be the case. While the rate of increase in world oil demand
Rachel Zamorski
has declined Yen Yung
since theAlbemarle
surprising Catalysts
4% surge in 2004, it nevertheless appears that
production@petroleumtechnology.com demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
increasing oil consumption by China, India and even the Middle East producers
21 Active site developments for improved productivity
themselves will continue. It is also safe to assume that refinery and petrochemical
Graphics Editor
conversion Kevin Carlsonwill
unit capacity Criterion
need toCatalysts
expand. & Technologies
Mohammed Samiuddin No massive new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com
foreseeable future. The world will remain dependent on oil and gas for decades to
come 25 evenRing-shaped
though the upstream catalystsindustrymake the faces gradeincreasing challenges in the
Editorial
discovery Brianproduction
and Moyse Haldor of new Topsøe
sources. In fact, some well-placed industry
PO Box 11283 analysts think 2008 may be the year where there is no increase in crude supply at
Spring TX 77391, USA all from regions outside of OPEC. For this reason, we will continue to see significant
tel +1 281 374 8240 31 Reducing
investment in refinery sulphur
upgrades oxide emissions
despite surgingfrom costs the FCC unitof feedstock
— security
fax +1 281 257 0582 supply,
albeit Colin unconventional
Baillie, Renaud low-quality
Kieffer and feedstock,
Maria Luisa takesSargenti
precedence over the
quality of feedstock supply.
Grace Davison Refining Technologies Europe
Feedstock options such as biomass (for biofuels production), Canadian tar sands
Advertising Sales Manager (for distillate production) and other types of unconventional crude sources require
Paul Mason
reactor37 technology
Maximising that allows for the integration
FCC distillate production of these operations into existing
sales@petroleumtechnology.com
process configurations. The quality of these types of feedstock are one important
Advertising Sales reason whyJoe McLean
a wider array BASF Catalysts
of catalysts has been introduced into the market. For
Bob Aldridge example, as refiners cut deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com metals in the VGO requires a properly designed guard bed system to protect active
47 Advances in methanol synthesis
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Advertising Sales Office
(eg, <10), Terry
high Fitzpatrick
metals, nitrogen andand Tom otherHicks Johnson components
undesirable Matthey Catalysts is one of the
tel +44 870 90 303 90 main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 accommodate not only higher volumes of catalyst, but also a wider variety of
catalyst54 withCatalytic steam generation
specific formulations.
Publisher
Nic Allen
Non-catalyticFranck Letellier
processes areand alsoDave
playing Wardlea signifi Oxford
cant roleCatalyst
in theGroup refiner’s ability
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. For example,
some refiners processing higher volumes of resid and atmospheric tower bottoms
Circulation have considered adding certain types of solvent-extraction processes in addition
Jacki Watts to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
circulation@petroleumtechnology.com coker operations. Improvements in furnace technology, such as with olefin steam
cracker operations, have resulted in significant increases in worldwide ethylene
Crambeth Allen Publishing Ltd capacity.
Hopesay, Craven Arms SY7 8HD, UK However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20
dehydrogenation) requires investment in catalytic-based processes, as discussed in
fax +44 870 90 600 40
the following articles authored by experts in the field of downstream process
ISSN 1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded
Cover caption: to Western
BP Kwinana refinery, the Q&A published
Australia: a filter suppliedin this
by Pall issue of
Corporation PTQ Catalysis,
cut emissions of catalyst dust as
from the FCC unit.
well as to those respondents who addressed the online questions Photo: BP
(www.eptq.com)
Petroleum Technology Quarterly (USPS
that addressed the specifics of certain reactor and catalytic issues of importance to
0014-781) is published quarterly plus the industry.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA ©2010. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
Periodicals postage paid at Emigsville PA. mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
Postmaster: send address changes to The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
Petroleum Technology Quarterly c/o PO has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held responsible for any
Box 437, Emigsville, PA 17318-0437 statements, opinions or views or for any inaccuracies.
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez
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grace.indd 1 29/1/10 12:11:04
catalysis Security of may
Metals supply
T
he European Union has arguably
been the global leader in biodiesel
production ptq and use, with overall
biodiesel production increasing from 1.9
million tonnes in 2004 to nearly 10.3 million
feedstock supply
impede catalysis
tonnes in 2007. Biodiesel production in the
Vol 15 No
2010
past
Vol213 No 2
US has also increased dramatically in the
2008
few years from 2 million gallons in 2000
growth
to approximately 450 million gallons in 2007.
DR
According to the National Biodiesel Board,
171 companies own
Editor Editor
biodiesel manufacturing ecently
espite published
signs in 2007 estimates for the future
of a slowdown of catalyst
in various markets
sectors of thesuggest that
economy,
René G Gonzalez
plants and are actively marketing biodiesel.1.
Chris Cunningham therefivalue
ners of industrial
remain a big chemical
play for catalysis
prospectiveby the mid-point
investors. of It this
useddecade
to be
editor@petroleumtechnology.com
editor@petroleumtechnology.com
The global biodiesel market is estimated conventional
will be $7.5 billion,wisdom
of which thatthe higher
market fuelforprices
refinery and a slowing
catalysts will economy
account
to reach 37 billion gallons by 2016, with an would curb demand and increase supply,
for some $4.3 billion. For the refinery sector alone that represents annual but for the past seven years
growth
Production Editor thatupwards
has notof proved to be the case. While the rate of increase in world oil demand
average Production
annual growthEditor
rate of 42%. Europe 5% — a more cheerful view of the future than most businesses can at
Rachel Zamorski
will Rachel
continue to Zamorski
be the major biodiesel hasleast
declined
currentlysince thefor.
hope surprising 4% surge in 2004, it nevertheless appears that
production@petroleumtechnology.com
production@petroleumtechnology.com
market for the next decade, followed closely demand beyond 2008
This level of rising market will grow, along
value with
is no prices.Catalyst
surprise. It is a safe bet that rapidly
developments have
by the USEditor
Graphics market. increasing oil consumption by China, India and
enabled a fast and effective response, time and again, to whatever even the Middle East producers
form of
AlthoughSamiuddin
Mohammed high energy prices, themselves will continue. legislation
environment-mending It is also safe to assume
is thrown in the that refineryofand
direction petrochemical
fuels producers.
Graphics Editor
graphics@petroleumtechnology.com conversion unit capacity will need to expand.
increasing global demand, drought
Mohammed Samiuddin Catalyst developments are key to the preservation of margins when the crude
and other factors are the primary driv- No massive
supply newtakes
situation sources
one of of energy
its moreare expected to
disconcerting come
turns. And onthey
streamhelpfor the
refin-
graphics@petroleumtechnology.com
Editorial foreseeable future. The world will remain dependent on oil and gas for decades to
ers for higher food prices, food ers to derive greater flexibility from their line-ups of processing units when
tel +44 844 5888 773 come even though the upstream industry faces increasing challenges in the
competitive feedstocks
fax +44 844 5888 667 have long been variation in demand for products and quality of raw material inputs present
Editorial to be a major discovery and production of new sources. In fact, some well-placed industry
and will continue different types of challenges. The catalyst producers’ continuing high spend on
POtheBox 11283 analysts think 2008 may be the year where there is no increase in crude supply at
concern for
Advertising development
Sales Manager of biofu- research and development indicates more of the same in the future, by way of
Spring TX 77391, USA all from regions outside of OPEC. For this reason, we will continue to see significant
els. Totel compete,
Paul Mason the
+1 281 374 8240 industry has response to
investment in challenges faced by the
refinery upgrades refining
despite industry.
surging costs — security of feedstock
sales@petroleumtechnology.com
responded by281
developing
fax +1 257 0582methods to However, the technological consensus
supply, albeit unconventional low-quality feedstock, between producers and consumers
takes precedence of
over the
increase process efficiency, utilise or catalysts is obviously
quality of feedstock supply. not the only significant factor in the marketplace. Variables
Advertising Sales
upgrade by-products and operate with as unpredictable
Feedstock optionsassuch priceasvariations
biomass (for in the crudeproduction),
biofuels slate are lurking on thetar
Canadian supply
sands
Bob Aldridge
Advertising
lower SalesasManager
quality lipids feedstocks. (forside, and production)
distillate current thinking is that
and other theofnext
types five years may
unconventional crude put unwelcome
sources require
sales@petroleumtechnology.com
Paul Mason pressure on the thatpriceallows
ratherfor than
reactor technology the the size of the
integration market
of these for catalysts,
operations as the
into existing
sales@petroleumtechnology.com
Feedstocks
Advertising Sales Office cost of
process commodity
confi gurations. raw
The materials
quality inflates
of theseand typessources become tighter.
of feedstock are one important
Biodiesel
tel +44 844refers to aSales
5888 771
Advertising diesel-equivalent reason Fewwhy producing
a wider industries can relyhas
array of catalysts more been than petroleuminto
introduced refining on suchFor
the market. a
fax +44 844 5888 662
fuel consisting of short-chain alkyl broad range
example, as refinersof commodity
cut deepermetals into theto catalyse
vacuumitstower, processes, from relativelyof
the concentration
Bob Aldridge
(methyl or ethyl) esters, made by the
sales@petroleumtechnology.com minor
metals transition
in the elements
VGO requires such as designed
a properly cobalt and guardmanganese
bed system to rare earths active
to protect and
Publisher
transesterification of triglycerides, precious
catalysts metals.
in the During theThe
hydrocracker. pastcharacteristics
decade, the price of such with
of feedstock metals low hasAPIrisen by
gravity
Nic Allen
commonlyAdvertising knownSales Office oils or
as vegetable (eg,around
<10), high 300%.metals,
The chief reasonand
nitrogen for other
this fluctuation
undesirable is components
much the same as itofwas
is one the
publisher@petroleumtechnology.com
tel +44 870
animal fats. The most common 90 303 90 form mainfor reasons
shifts in why the prices of a wider
hydrotreaters and base of commodity
hydrocrackers arematerials:
becoming demand
larger from
— to
fax +44 870 90 246 90 accommodate not only of higher
uses methanol, the cheapest alcohol
Circulation the “hot” economies Asia, volumes
China in of catalyst,The
particular. but vagaries
also a wider variety of
of commodity
available,
Jacki Watts to produce methyl esters. catalyst with specifi c formulations.
pricing aside, there are also growing fears about the future availability of the
Publisher
circulation@petroleumtechnology.com
The molecules NicinAllenbiodiesel are primar- Non-catalytic
types of metals processes
found inare also playing
refinery a signifi
catalysts. The cant role in the
US National refiner’s
Research ability
Council
ily fatty acid methyl esters (FAME),
publisher@petroleumtechnology.com to process whatever unconventional crude sources become
has compiled a list that includes a number of these metals, whose supply, it available. For example,
Crambeth Allen Publishing Ltd some refiisners
usually created by transesterification says, at aprocessing higher
highly critical volumes
level. of resid
Difficulties in and
sourcingatmospheric towersaid
metals could, bottoms
the
Hopesay, Craven Arms SY7 8HD, UK have considered adding certain types of solvent-extraction processes in addition
between Circulation
fats and
tel +44 844 5888 776methanol. Currently, council, expose a range of US industries to political, economic and other risk.
biodiesel Jacki Watts from various to overall improvements
in Europetofollows crude unit (eg, vacuum tower revamps)
2010, theand delayed
fax +44 844is5888 produced
667 Thinking similar lines. During European
circulation@petroleumtechnology.com
vegetable and plant oils. First-genera- coker operations. Improvements in furnace technology,
Commission is thought likely to produce its own list of at-risk, economically such as with olefi n steam
cracker operations, have resulted in significant increases in worldwide ethylene
tion
ISSN food-based
Crambeth 1362-363X feedstocks are straight
Allen Publishing Ltd important metals and to propose measures such as stockpiling. Meanwhile,
capacity.
vegetable
Hopesay, oils such
Craven Arms as SY7
soybean8HD,oilUK and Japan is known to be actively stockpiling uncommon metals as a safeguard for
However, any expansion of the value chain (eg, ethylene-to-propylene via
animal fats
tel +44 such
870 as90 tallow,
600 20lard, yellow its technologically intensive industries.
Petroleum Technology Quarterly (USPS 0014-781) dehydrogenation) requires investment in catalytic-based processes, as discussed in
grease, fax
is published +44 870
chicken
quarterly 90
and600
fatannual
plus the40 by-products
Catalysis edition There have been alarms over the supply of so-called strategic metals in the
by Crambeth Allen Publishing Ltd and is distributed the following articles authored by experts in the field of downstream process
of the production
SPP, 75 Aberdeenof Omega-3 fatty past and instances of stockpiling that have backfired on eventually over-
in the USA by
ISSNfish 1362-363X
Rd, Emigsville, PA technology. PTQ wishes to extend its gratitude to the authors who provided
acids from
17318. Periodicals postageoil. Soybean
paid at Emigsville PA.oil and supplied
editorial andhoarders.
responded However,
to the Q&A there published
are fairly tight in thisgeographical
issue of PTQ andCatalysis,
geologicalas
Postmaster: send address changes to Petroleum
rapeseeds oil are
Technology Quarterly c/o POthe common source limits to the supply side of many of the metals in
well as to those respondents who addressed the online questions (www.eptq.com) question. It would be as well
for biodiesel
Box 437, Emigsville,production
PA 17318-0437 in the US and
thatfor some reassurance
addressed the specifiabout their future
cs of certain availability.
reactor and catalytic issues of importance to
Back numbers available
Petroleum from theQuarterly
Publisher
Europe inisTechnology
at $25 per copy
0014-781)
quantities
inc postage.
published
that can (USPS
quarterly plus
produce Among the advances in catalyst technology that refiners have to look
the industry.
enough
annual biodiesel
Catalysis edition byto Crambeth
be used Allenin a forward to in the next five years and beyond, it may be that none will draw as
Publishing Ltd and is distributed in the USA
commercial market with currently
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
much favourable attention as advances in recycling metals from spent catalyst.
applicable
Periodicals technologies.
postage paid at Emigsville PA.
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CATALYSIS 2010 3
www.criterioncatalysts.com
© 2008 Criterion Catalysts & Technologies L.P. (cri815_0508)
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for further information
Q I understand that high levels of sodium or potassium in Q We are at the initial stages of planning a revamp of our
the feed to the FCCU can have a seriously deleterious effect HF-based alkylation unit. What’s the current federal view of
on the acid sites of the catalyst. Are there any pre-treatment the technology and should we be looking for alternatives?
steps I should apply?
A Edwin van Rooijen, Business Manager, Albemarle
A Yen Yung, Global Technical Specialist, Fluid Cracking Catalysts
Catalysts, Albemarle Catalysts Solid acid alkylation by AlkyClean is one alternative.
FCC catalyst contamination by potassium is rare. The The technology and proprietary solid acid catalyst
measures to avoid the deleterious effect of potassium AlkyStar are developed and demonstrated by Lummus
contamination are similar to the more commonly found Technology, Albemarle Catalysts Corporation and
phenomenon of contamination by sodium. Neste Oil. The process significantly improves the safety
Sodium salts enter the refinery with the crude oil. of refinery alkylation over conventional liquid acid-
Desalting is generally applied to remove the sodium based processes, reducing the potential hazards
from the crude. Any remaining sodium ends up in the associated with the transportation and handling of
heaviest distillates and the residue, and can find its liquid acids. The process gives refiners a competitive,
way into the FCC or thermal conversion units. The cleaner and inherently safer alkylation technology. No AlkyC
operation of the crude desalter must therefore be moni- acid-soluble oils or spent acids are produced, and there Award
tored and optimised cautiously. In several refining is no need for product post-treatment to remove traces from
steps of refineries processing sour crudes, caustic is of acid. The process has also proven to be economic which
applied for corrosion control by acids. Proper monitor- and robust, requiring minimal maintenance. as the
ing of the separation of sodium from the oil stream is nolog
required too.
Some FCCUs processing vast amounts of long resi- Q What sort of run length should I reasonably expect from
dues are equipped with an FCC feed desalter to limit the guard bed in my hydrotreater?
not only sodium contamination of the FCC catalyst,
but also to prevent the formation of salts in the frac- A Steve Mayo, Global HPC Applications Technology
tionator overhead vessel. We recommend routine Manager, Albemarle Catalysts
measurement of the sodium content of FCC feed, espe- There are three uses for guard beds in hydrotreaters:
cially import feed. If large quantities of sodium are collection of solids to prevent pressure drop build-up,
found in the import feed, leave it to settle in a tank to controlled removal of reactive species, and adsorption
remove the sodium with the water, if possible, or adapt of inorganic poisons to protect downstream catalysts.
the catalyst addition policy to avoid excessive catalyst Failure of any of these functionalities can result in
contamination. premature shutdown. In general, guard beds should be
Modern resid FCC catalysts such as Upgrader and sized so that the capacity of the bed for solids collec-
Coral SMR have excellent resistance to the deleterious tion and/or poison adsorption is similar in cycle length
effect of metals poisons such as sodium, nickel, vana- to that of the main bed catalyst. Data from spent cata-
dium, calcium and, when present, potassium. lyst analysis and canisters can be used to optimise
subsequent guard bed configurations for maximum
A Kevin Carlson, Global Business Manager, FCC Pretreat cycle life.
& Sentry Products, Criterion Catalysts & Technologies
Feed contaminants such as sodium or potassium can,
indeed, adversely affect FCC operations. Pre- Q Is Fischer-Tropsch becoming a significant and efficient
treatment of the feed in a hydrotreater results in option for the economic conversion of flare gas? Are there any
improvements in FCC performance, but can also result catalyst developments I should be keeping an eye on?
in catalyst deactivation and pressure drop build-up in
the pre-treated unit. Proper application of top-bed A Frans Plantenga, Technical Director, Albemarle AFT
grading and demetallisation products, such as those The key challenge when converting flare gas to liquid
found in Criterion’s Sentry portfolio, can mitigate these is the scale of the operation. So far, to be economical,
issues, but often improved crude handling and installations have been built on a large scale. So, the
desalting can provide an effective long-term solution. solution to this problem lies in the successful scaling
At crucial moments, the right reaction matters. When you are looking
for the right reaction from your process catalyst, turn to BASF. Our
technical experts will recommend the right catalyst from our innovative
product line that will achieve the desired reaction. The end results
may also include greater yield and better end product properties.
When the catalyst is right, the reaction will be right. Trust BASF.
� Adsorbents � Chemical catalysts � Polyolefin catalysts
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For more information, please visit www.catalysts.basf.com/process
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SÜD-CHEMIE www.ptqenquiry.com
www.sud-chemie.com for further information
T
o grasp the true complexity
of the FCC process, it is
important to recall the inter- $RY GAS
( (3 #(
play between chemical reactions, #( #(
thermodynamics and fluid mechan-
ics occurring simultaneously in an
FCCU, and the roles they play in #OKE
influencing yields.
The role of catalyst can best be &EED ,0'
visualised with the aid of a lumped # #
kinetic model. A great many
lumped kinetic models for oil refin-
ing processes can be found in the
literature. The most elaborate are
structure oriented lumping (SOL) "OTTOMS
,#/
models, wherein the lumps are SLURRY
²# ²n²# 'ASOLINE
based more on chemical similarity #n²#
than boiling point and can number
in the hundreds or even thousands.1
However, for our purpose, a much ²#
CONVERSION
simpler network, such as the one
shown in Figure 1, will suffice. The
lumps shown in Figure 1 are the Figure 1 FCC reaction network
traditional ones used in petroleum
refining, defined primarily on the pathway, or even group of selectivi- Interfacial transport phenomena
basis of boiling point: coke, bottoms, ties, without considering the entire introduce additional transfer
LCO, gasoline, LPG and dry gas. reaction network. Contributing resistances
While cracking is the main reac- additional complexity to the overall • Isothermal vs adiabatic operation
tion implied by the arrows in Figure reaction network is the interplay of: Most laboratory tests are operated
1, many other solid-catalysed reac- • Diffusion Reaction rates in FCC isothermally or, at best, semi-
tions take place in the FCC process: catalyst particles are strongly influ- adiabatically. Commercial units
isomerisation, dehydrogenation, enced by diffusion. Classical operate adiabatically. Translation of
condensation, transalkylation and diffusion-reaction theory2 maintains results from laboratory to commer-
hydrogen transfer. that local reaction rates are depend- cial scale can be challenging.
Consider gasoline selectivity. ent on the flux of reactants as well
According to Figure 1, increasing as diffusivity, which can differ Producing middle distillates in
the rates of the dot-dash arrow greatly for various compounds the FCCU
reactions relative to the rates of the • Mechanistic similarity For reac- Based on the reaction network
dash arrow reactions will cause the tions with mechanistic similarities, postulated in Figure 1, Figure 2
gasoline yield to increase. However, it can be extremely difficult to influ- shows the yields of bottoms
higher gasoline selectivity (gasoline ence one without influencing the (slurry), LCO and gasoline as a
yield per unit conversion) also other. This is a prime reason for the function of 221°C+ conversion. The
requires that the dotted arrow reac- prevalence of auto-correlations in corresponding TBP (true boiling
tion rates be reduced. FCC test data point) cutpoints are: gasoline,
In practice, it is difficult to alter • Multiphase phenomena FCC is a C5-221°C; LCO, 221–343°C; and
the selectivity of any single reaction complex multiphase process. bottoms, >343°C. These cutpoints
Bottoms
zeolite provides for higher LPG and
gasoline selectivity.3,4 Therefore,
middle distillate production is
generally favoured by higher matrix
Gasoline
cracking (as evidenced by higher
meso surface area) and reduced
zeolite cracking. In other words,
#ONVERSION WT middle distillate production
increases as the zeolite-to-matrix
ratio (Z/M) decreases. The benefits
Figure 2 Overcracking of LCO of this approach with respect to
increasing LCO at a constant
are typical for a gasoline mode of to overcracking. In all three regions, conversion of 70 wt% are shown in
operation, which is characterised by the gasoline yield increases with Table 1.5
a gasoline endpoint as high as conversion. Not shown in the graph For greatest bottoms conversion,
possible, at the expense of the LCO is zone 4, the gasoline overcracking the feed molecules need to reach
initial boiling point. zone, where the net production of the active sites quickly. Conversion
Most FCCUs have been designed gasoline drops. Clearly, when the of the desirable products in the
for operation in the LCO overcrack- LCO yield is the main objective, the diesel boiling range and other
ing mode for the sake of high gasoline yield suffers. The greatest secondary reactions, such as
gasoline yields. Nonetheless, a benefits are obtained with a catalyst hydrogen transfer, aromatisation
substantial increase of LCO in the having a high bottoms cracking and condensation, have to be
30–40 wt% range can be obtained. selectivity and a somewhat lower avoided. This is achieved by
A challenge to overcome is to limit gasoline selectivity. increasing the accessibility of the
the potential loss in bottoms conver- catalyst. Accessibility is the prop-
sion. The actual yield of gasoline Maximising catalytic conversion of erty that allows primary products
and LCO will depend on operating bottoms to middle distillates to escape promptly from the reac-
severity, feed type, and quality and The catalytic approach for produc- tion sites.
catalyst. Figure 2 illustrates what is ing the greatest yield of middle Outstanding performance of
achievable with a conventional distillates in FCC is easy to visual- highly accessible catalysts, as meas-
catalyst at low 221°C+ conversion ise using Figure 1. The challenge is ured by our internally developed
(= 100 - LCO - bottoms) levels. to selectively crack the large slurry Albemarle Accessibility Index (AAI)
In zone 1, the LCO yield is low molecules to LCO, while keeping method, has been confirmed in
due to insufficient bottoms conver- down the coke yield and avoiding several applications.6-8 A typical
sion. In zone 2, the LCO yield overcracking of LCO molecules into example of the benefits of high
increases with conversion, as the lighter products. In terms of Figure accessibility is shown in Figure 3.
cracking of bottoms to LCO exceeds 1, this means increasing the reac- This is data from an FCCU process-
the cracking of LCO to lighter prod- tion rates of the LCO-producing ing resid and operating in
ucts. In zone 3, the net production reactions (solid arrows) while low-severity LCO mode.
of LCO drops with conversion due decreasing the rates of the LCO-
Hydrotreated VGO operation
Reduced Z/M ratio and higher meso surface area results in a greater
with high middle distillate and
LCO yield and better bottoms conversion propylene yields
The second maximum LCO exam-
ple is an FCCU processing large
Yields at 70 wt% conversion, wt% High Z/M Low Z/M
Dry gas 2.7 3.1
amounts of hydrotreated vacuum
C3s 5.4 5.3 gas oil in a market favouring high
C4s 9.3 9.1 propylene yields. The refiner has
Gasoline 45.4 45.3 switched from a competitive cata-
LCO 16.9 18.7
Bottoms 13.2 11.3
lyst to an Amber MD catalyst
Coke 7.1 7.2 featuring higher mesoporosity,
(Lab SCT-RT data; resid feed) lower Z/M ratio and higher AAI
than the previous catalyst. At
Table 1 constant operating conditions in
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and 0.6 wt% less bottoms than the Highly accessible Albemarle
competitive catalyst. Despite a catalyst with high matrix activity
2.5 wt% drop in conversion, the
bottoms yield stayed virtually
,#/ ,6
increased by 2.4 wt% (see Table 2).
9IELD IMPROVEMENT WT
depend on the adsorption of dark-
,0'
coloured bodies, which are usually #OKE
# #
asphaltene molecules. In the case of
9IELD WT
ary reactions (long
dash arrows) is
reduced, preventing
gasoline from convert-
ing into LPG and coke.
This is consistent with
the reduced diffusion
#OKE CONV "OTTOMS COKE
'ASOLINE CONV 'ASOLINE COKE
resistance associated
with the improved
2UBY 'O
5LTRA #OMPETITOR #OMPETITOR #OMPETITOR PoSD. A more robust
interpretation is that
the combination of
Figure 8 Comparison of commercially available “maximum gasoline” catalysts PoSD and more selec-
tive active sites is
used in this section are based on At constant conversion (Figure 6), responsible for these yields.
the deactivation and feed condi- Go-Ultra increases the gasoline Figure 7 shows yield improve-
tions shown in Table 5. yield by as much as 3%, at the ments at constant coke. Here, the
Figures 6 and 7 are based on expense of coke and LPG. The trend is also clear: 4% more gaso-
four testing comparisons between magnitude varies between the four line and 2% more LPG, at the
four Ruby formulations and the comparisons, but the pattern is the expense of bottoms (slurry).
same formulations in Go-Ultra same: reduced coke and an equal- (Differences in dry gas are very
form. Results are plotted as yield to-smaller reduction in LPG. At small and are neglected here.) Also
differences between the catalysts. constant conversion, the scheme shown in Figure 6 is the simplified
reaction network for the case of
constant coke. In this case, the
Feed and e-cat properties and base case FCCU conditions improved yields must come from
the dot-dash reaction arrows. (Note:
Feed properties E-cat properties FCCU base conditions bottoms, that is material boiling
API 25.0 MAT activity 70.0 Feed rate, bpd 70 000 above 343°C, exist in both feed and
S, wt% 0.5 Ni, ppm 500 CTO 5.2 slurry.) This demonstrates the
Total N, wt% 1000 V, ppm 1000 CAR, tpd 7
coke-selective bottoms cracking
D1160 T5, °C 303 Cat inv, ton 400
T50, °C 398 RxT, °C 540 advantage of ADM-25 as well as
T95, °C 527 Max RgT, °C 735 the improved PoSD.
CCR 0.7 221°C + conv, wt% 72.3
Economic case study
Table 6 An economic case study was
performed for a 70 000 bpd gas oil
Economic case study
FCCU running against a maximum
regenerator temperature constraint
of 735°C. Table 6 gives the feed and
Base Case 1 Case 2 Case 3 e-cat properties and base case
Go-Ultra Go-Ultra Go-Ultra
conditions for this FCCU.
base cond. higher RxT higher feed
Feed rate, bpd 70 000 70 000 70 000 82 000 Table 7 shows the results of the
CTO 5.2 5.5 5.8 5.1 case study. In Case 1, the liquid
Coke, wt% 5.58 5.54 5.87 5.52 yield improvements alone of Go-
Delta coke, wt% 1.08 1.01 1.01 1.07
Ultra translate to a $28 000/day
RxT, °C 521 521 535 521
RgT, °C 735 724 735 735 improved margin. Note that this
221°C + conv, wt% 72.3 72.7 75.6 71.0 case does not take full advantage of
Margin, $/bbl Base +$0.40 +$0.68 +$0.10 the catalyst’s coke benefits; the
Gross margin, $/day Base +$28M/day +$48M/day +$68M/day
regenerator is loafing at 724°C, fully
11°C below maximum.
Table 7 In Case 2, the riser temperature is
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Catalysts for hydrogen Services to improve plant Hydroprocessing catalysts in Specialist measurement and
production, the market leaders. performance and profitability. conjuction with SINOPEC. diagnostic services; from
column scans to FCC studies.
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www.jmcatalysts.com/refineries for further information
UK USA
Tel +44 (0)1642 553601 Tel +1 630 268 6300
Fax +44 (0)1642 522542 Fax +1 630 268 979
Kevin Carlson
Criterion Catalysts & Technologies
W
hile global economies
begin to show signs of Centera
recovery, refinery margins
2ELATIVE ($3 VOLUMETRIC ACTIVITY
Main Products
Regeneration
of spent catalysts
XpresS ex-situ activation (sulphiding) of fresh and regenerated catalysts
Rejuvenation of catalysts
Resale of once regenerated catalysts
Sale of GUARDIAN material (guard bed catalysts)
Additional Services
Laboratory
expertise of spent catalysts
Pilot plant ex-situ activation
Technical support
Storage of catalysts
Brian Moyse
Haldor Topsøe
O
il refineries in the US,
Canada and other regions
of the world are showing
their age. Within the worldwide
oil refining system, there are refin-
eries in operation that are more
than 100 years old. These are,
indeed, the senior citizens of our
industry. So, it comes as no
surprise, then, that corrosion is a
large and expensive issue for refin-
ers to address on a daily basis. A
refinery can end up spending
millions of dollars every year deal-
ing with corrosion issues.
Obviously, fouling affects many
different aspects of refinery opera-
tions.1 However, this article will
deal with only one aspect of foul- Figure 1 Debris from distributor tray
ing, which inevitably results from
corrosion. We will deal exclusively fouling sources besides iron corro- fairly large-sized flakes and deposit
with the subject of fouling of fixed- sion products: on top of the catalyst bed.
bed catalytic reactors used for • Catalyst fines and dust (FCC- Even if feeds containing cracked
hydroprocessing of the whole range derived streams) stocks are fed directly to the unit
of refinery streams. • Coke fines (coker-derived and not via a tank, there are still
streams) issues to be faced. In these cases,
The problem • Sediment (tar sands, inefficient the olefins and diolefins react read-
As regards catalytic hydroprocess desalter operation) ily in the reactor inlet to form
ing units, it is desirable to maximise • Salts (Na, K, P, etc) polymeric materials. These gummy
on-stream time and achieve the • Carbonaceous material spalled reaction products provide the
desired cycle length without from heater (polymeric) “glue” to cement together any
outages or interruption. It is not • Metal sulphides (Ni, V, etc). foreign matter entrained in the feed
unusual to see some operations It should also be pointed out that and can ultimately form a crust on
halted due to unfavourable pres- treating cracked feedstocks or top of the bed. Of course, this
sure drop across all or part of the blends containing cracked material results in high delta P, flow maldis-
catalytic reactor. Most often, this is presents an additional complication. tribution and possibly hot spots in
caused by feedstock contaminants, This is because cracked stocks the catalyst bed.
which usually include a very well- contain olefins and, in particular, As everyone is no doubt aware, a
known corrosion product — iron. diolefins. If such feeds are exposed catalyst bed makes for a great filter.
This is shown in Figure 1, a photo- to oxygen, as for example when Unfortunately, this undesirable
graph of debris recovered from the using non-blanketed feed tanks, facet brings with it an increase in
top of a gas/liquid distributor tray. gums will form. The gums can pressure drop as the catalyst bed
Note the variation in the size cause fouling of the heater itself fouls. Feed filtration is a good idea
of particles. and the heat exchange train. in such cases, because whatever
It should also be mentioned that, Deposits can build up in the heater material can be removed in this
in hydroprocessing, there are other and will eventually slough off as step means that much less is passed
maximum void space available to
deposit debris in the top catalyst
layers of the bed.
Spheres are the worst possible
choice in cases where pressure drop
is an issue. It is permissible to use
spherical support media at the
bottom of the bed or reactor, but
they should definitely not be used
-ONTHS ON
LINE
as bed topping in any units experi-
encing pressure drop issues.
Figure 2 Unit pressure drop in a naphtha hydrotreating unit We might also mention that even
units that do not have pressure
to the reactor. The average size of hydroprocessing units worldwide. drop issues could actually benefit
the filter element employed is 25 The only difference is the actual from replacing spherical topping
micron. This means that even units values of psi and on-stream time. with a high-void type product. This
currently employing feed filtration The shape of these curves is exactly would protect the unit from unfa-
are not necessarily “out of the the same. vourable pressure drop excursions
woods”, since particles smaller than Figure 2 also shows that, after a in cases of plant trips, refinery
the nominal filter element size are little more than a year on-line, the upsets and power outages.
going to pass through to the reac- reactor pressure drop rises expo- Normally, if a refinery experiences
tor. Also, it appears that for any nentially and requires that the cycle an emergency trip due to a power
given industrial application, the be terminated and the unit shut outage, for instance, the pressure
micron size of the filter is selected down for corrective action. This drop across the hydrotreater reactor
not for its efficacy but rather on situation can and will occur when will be higher on restart than it was
what the refiner considers to be an the bed void fraction, either overall prior to the event.
acceptable replacement or back- or in a particular layer, is reduced
wash frequency. from its start-of-run (clean bed) Early solutions
Figure 2 shows an example from value down to 22%. The range is One of the early approaches to miti-
an actual naphtha hydrotreating actually between 20% and 25%, so gate this kind of problem was the
unit, depicting the development of we selected 22% as representative. use of scale traps or “trash baskets”
the reactor pressure drop as a func- When this occurs, pressure drop in the top of the reactor. It is obvi-
tion of months on stream. It can be takes off exponentially, resulting in ous that these baskets could only
seen that normally the reactor pres- channelling, catalyst bypassing, hot hold back particles larger than the
sure drop is predictable and follows spots and so on. mesh size used in their construc-
the variations typically encountered Table 1 shows start-of-run, clean tion.2 Anything of a smaller size
as a result of the usual fluctuations bed void fraction of materials that would naturally pass through into
in feed rate. This is normal and to are typically loaded into a reactor, the catalyst bed.
be expected. This plot is also typical be they catalytic or inert topping/ Also, some primitive grading
of hundreds that we have seen from support media. The right-hand systems were initially used on the
top of the lead catalyst bed. These
Clean bed void fraction and pressure drop all involved the use of layers of
inert spheres on top of the catalyst
bed, larger on top and smaller
Catalyst shape SOR void, % SOR - 22 = useful void, %
Spheres 33 11
below, actually the opposite of
Cylinders 40 18 what was used on the bottom of
Threelobes 42 20 the bed.
Quadralobes 45 23 In those cases where feed filtra-
Ring catalysts 53 31
High-void inerts 55–65 33–43
tion was employed, the size of the
filter openings chosen would affect
Spheres provide lowest void fraction its efficacy, on-stream time and how
often it had to be replaced. The
Table 1 average size of feed filters used in
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for further information
3225 Gallows Road, Fairfax, Virginia 22037-001, USA
www.exxonmobil.com/refiningtechnologies • +1-703-846-2568 • fax +1-703-846-3872 • technology.licensing@exxonmobil.com
Conclusion
Graded catalyst beds have come of
age. They have clearly demon-
strated that the combined use of
shape-optimised topping materials Figure 4 TK-25 TopTrap topping material
and ring-shaped hydroprocessing
catalyst provides the optimal solu- ing unit monitoring and analyses of hydrotreating unit, AM-00-33, NPRA Annual
tion for units that are pressure drop samples taken from the reactor at Meeting 26–28 Mar 2000, San Antonio, Texas.
limited. end-of-run. This offers the refiner
Ideally, the graded bed should be the most viable approach to under- Brian Moyse is Technical Manager for
Hydroprocessing Catalysts and Technology in
composed jointly between the standing and thus the opportunity
the Refinery Sales Group at Haldor Topsøe. He
refiner and catalyst supplier, and to solve any delta P issues.
is an international expert in the application of
grading should be selected based grading technology and hydrotreating. He has
References
upon feedstock analyses, actual 1 Wright B, No room for foul play, published and presented numerous papers in
contaminants and poisons encoun- Hydrocarbon Engineering, Sept 2009. the field of hydroprocessing. He was awarded
tered and optimised over time. This 2 Johnson B, Basket case: graded catalyst beds the NPRA Lifetime Service Award in 2006.
requires a planned approach includ- solve pressure drop problems in a naphtha Email: bmm@topsoe.com
Catalyst handling
and mechanical work
With more than 25 years
of experience
Mourik International
is a world leading supplier
for catalyst handling,
vessel and reactor services.
We think globally, but act Mourik International B.V.
locally, as we operate Nieuwesluisweg 110
through a world-wide 3197 KV Botlek-Rotterdam
network of subsidiary The Netherlands
organizations. Tel. +31-10-296 56 00
Fax +31-10 296 56 09
Offices: Europe, Middle East, Asia, E-mail: mint@mourik.com
North America, South America
mourik.com
www.ptqenquiry.com
for further information
www.eptq.com CATALYSIS 2010 29
www.ptqenquiry.com
for further information
A
lthough the amount of
sulphur oxide (SOx) emitted
SOx removed Treated with H2S
from FCC units (FCCUs) is from flue gas in the sour gas
relatively small, it still accounts for
Products (with H2S)
most of the SOx released from oil
refineries. The major options for
reducing SOx emissions from the
Stripper:
FCCU include flue gas scrubbing Hydrolysis of Mg sulphide
Flue gas
(FGS), hydrodesulphurisation (with SOx) MgS (s) + H2O (g) = MgO (s) + H2S (g)
(HDS) and the use of a SOx-
reduction additive. FGS requires a Regenerator: Stripping steam sulphate
significant capital investment and Formation of SOx
the operating costs are high. In S (coke) + O2 (g) = SO2 (g)
addition, discarding the spent treat- SO2 (g) + 1/2 O2 (g) = SO3 (g)
SOx.raw
Our knockout drum needs 3% O2
a mist eliminator!
S.charge (%)
RSV (t/h)
O2 (%)
Can we add one without Figure 2 Linear dependency of SOx emissions with feed sulphur content, vacuum residue
overhauling the vessel? throughput and flue gas oxygen content
IT’S A MORE COMMON problem than
you might think. A vertical knockout formation and a stable sulphate feed sulphur content and SOx
drum removes free liquid from a is formed under regenerator concentration.
certain gas stream. But at the time the conditions. Various scientific studies have
plant was built, a mist eliminator was In the reactor, the magnesium shown that the fraction of
not considered necessary. Now mist sulphate is reduced by hydrogen to thiophenic sulphur in the feed has
is carrying over and causing trouble
downstream. There is no manway, so
form magnesium sulphide. Super a direct impact on the coke sulphur
adding a conventional mist eliminator Desox plays an important role here content deposited on spent catalyst
would require cutting the vessel open. too because the magnesium in the and thus on SOx emissions.
alumina spinel is less basic than Therefore, changes in uncontrolled
free magnesium oxide, thereby SOx emissions can be accurately
making the sulphate easier to estimated by measuring thiophenes
reduce. In addition, vanadium on in the feed. However, it is uncom
the spinel structure further mon for refiners to be able to
decreases the stability of the magne measure thiophenic feed content on
sium sulphate, especially under a regular basis. It is therefore
reducing conditions and in the recommended to estimate uncon
presence of steam. The magnesium trolled SOx emissions by measuring
sulphide is then hydrolysed to a feed sulphur or even better with
magnesium oxide in the stripper, slurry sulphur (the slurry being the
which returns to the regenerator to most aromatic product of the
complete the catalytic cycle. FCCU).
0LVW)L[LQVHUWLRQPLVWHOLPLQDWRU
Due to the operating variables
,QVWHDGLIWKHÀDQJHGH[LWQR]]OH Establishing a baseline for that can affect SOx additive
LVDWOHDVWVL[LQFKHVLQGLDPHWHU\RX uncontrolled SOx emissions performance, it is necessary to
FDQVLPSO\KDQJDSDWHQWHG0LVW)L[ Several operating variables have establish a baseline of uncontrolled
mist eliminator inside, securing it been identified as having significant SOx emissions to be able to calculate
EHWZHHQWKHÀDQJHV effects on the performance of SOx- the true SOx reduction caused by
Even when there is a manway,
reduction additives.1-3 Some of these the additive. Such a baseline is
0LVW)L[DYRLGVHQWU\ZHOGLQJDQG
UHFHUWL¿FDWLRQLQUHWUR¿WV)RUQHZ include the presence of combustion calculated by performing correl
and old vessels, it drastically cuts promoters, the ratio of catalyst ations for every relevant parameter
installation cost and downtime. circulation rate to unit catalyst based on pre-trial unit data. To
inventory, unit temperatures, avail establish a baseline for Refinery A,
Read more on this topic at ability of oxygen in the regenerator, three months’ unit data were used.
www.amistco.com
SO2* = 291 + 1729 S.feed (%) + 5.04 RSV (t/h) - 64.5 O2 (%)
www.ptqenquiry.com
32 CATALYSIS 2010 for further information www.eptq.com
3/ MG.M
use feed properties instead. In this
respect, the main parameters turned
out to be feed sulphur content (S.
charge), vacuum residue through- 0.8 wt% Super Desox
put (RSV) and flue gas oxygen 24% SOx reduction
content, as shown in Figure 2. 1.5 wt% Super Desox
Using the data from the refinery, 52% SOx reduction
the correlation shown in Figure 3
was established using the raw SO2
values from the pre-trial period
(from 21 October 2008 to 12 January
.ORMALISED 3/ / #ALCULATED 3/
2009). The high value of R2 (84.2)
signifies the good correlation
obtained.
As would be expected, it can be Figure 4 Flue gas SO2 emissions before and during Super Desox additions. Flue gas SOx
seen that increased feed sulphur was measured as SO2 by an online analyser, and the SO2 values are normalised to 3%
plays a major role in the above excess oxygen in flue gas
correlation; SOx emissions increase
with increasing feed sulphur. In around 19 January, indicated by the 0.5 wt% during 16 February to 29
addition, increased residue through subsequent and obvious drop in March. The average SOx-reduction
put can be expected to increase SOx flue gas SOx emissions illustrated in performance during this period
emissions, which is indeed observed Figure 4. remained high at 29%. In the subse-
in the correlation. The incorporation The effect was immediate, with quent period, between 30 March
of more residue results in increased average SOx reductions of 24% and 30 June, it was decided to
SOx emissions due to the more observed within the period 19 increase pre-blending levels to
refractive nature of its sulphur- January to 15 February, during 1.5 wt% to gain an idea of just how
containing compounds, which will which the additive was pre-blended much SOx reduction could be
thus end up more readily in the at 0.8 wt%. This can be effectively achieved, and during this period
coke on catalyst. The other impor- considered as a base-loading period, the average reduction rate increased
tant variable in the correlation is during which a stationary concen- to 52%. From 28 September,
flue gas oxygen content. As oxygen tration of additive is reached in the the refinery started pre-blending
increases, the coke yield decreases inventory. Super Desox at 1.8 wt% due to
and, therefore, less sulphur reaches It was subsequently decided to increased feed and slurry sulphur
the regenerator with coke. reduce pre-blending levels to levels, resulting in impressive
sions; the latter are based on the
correlation in Figure 3. In order to
reach the target of reducing SOx
emissions by 30%, Grace Davison
recommended using Super Desox
at 0.8 wt%, with a prior period of
base loading to accelerate the intro-
duction of the additive in the
Experience
the Sabin difference
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Corporate Headquarters:
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East Hampton, NY 11937
Telephone 631-329-1717 • Fax: 631-329-1985
Main Plant/Sales Office:
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Telephone 585-538-2194 • Fax: 585-538-2593
Web: www.sabinmetal.com • Email: sales@sabinmetal.com
Additional Facilities: Williston, ND • Cobalt, Ontario, Canada
Latin America • Mexico • Europe
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6ANADIUM PPM
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china ad.indd 1
MacroTrap ®
that lasts.
protects your catalyst. Particulates
in the incoming feedstock and iron
sulfide gums are trapped in the
interconnecting pores of the ceramic
media, preventing them from
reaching the catalyst bed and causing
premature pressure drop rise.
reactor operation.
www.ptqenquiry.com
for further information
Joe McLean
BASF Catalysts
I
ncreased demand on refiners to
process heavier crudes and
maximise diesel yields (see
Figure 1)1 means FCC units (FCCUs)
are continually pushed to their /THER ,0' 2ESIDUAL FUEL $ISTILLATE *ET FUEL
.APHTHA 'ASOLINE KEROSENE
operating limits. Higher diesel
yields are often achieved through
the use of selective, bottoms
upgrading FCC catalysts that
0ER CENT
feature active matrices. However,
these conventional bottoms upgrad-
ing catalysts also increase the yield
of undesirable products such as dry
gas and coke. This often pushes the
FCCU up against the limits of
performance in terms of gas )NCREMENT n
compression and metallurgy,
preventing the refiner from taking
full advantage of the potential for
increased diesel yields.
Figure 1 Global refined product demand focused on middle distillates, 2007–2030
Maximising distillate: fundamentals
The refining industry would like to
convert feed/bottoms in an FCCU
to light cycle oil (LCO) without
further cracking to gasoline.
Adjustments to the operating condi-
tions that can be applied to an
FCCU include reducing riser
temperatures and/or catalyst activ- LCO
ity by lowering the catalyst
make-up rate (see Figures 2 and 3).
9IELDS WT
Table 1
Bottom to the FCCU, or combination of
adjustments, will alone result in
increased output of LCO without at
the same time increasing bottoms
production. Only an improvement
in catalytic performance offers a
%
CAT ACTIVITY WT pathway to increased LCO produc-
tion while maintaining bottoms
conversion.
Figure 3 LCO and bottom yields’ response to lowering the equilibrium catalytic (e-cat) With BASF’s Novel Matrix
activity shows that the bottom yield response is more pronounced than LCO Material, LCO yield can be
increased by controlling the depth
of cracking. The conventional cata-
lyst approach to increasing LCO
yield has been to lower the Z/M
ratio, typically by both increasing
the matrix surface area (MSA) and
Z/M = 0.4
Z/M = 0.4 lowering the zeolite surface area
(ZSA).
BASF has introduced a manufac-
#OKE WT
,#/ WT
turing process for an advanced
Z/M = 4 matrix material. This is based upon
a novel technology platform that
Z/M = 4 differs from more conventional
matrix materials available to the
industry. Figure 5 compares the
hydrothermal stability of the new
#ONVERSION WT #ONVERSION WT
matrix material with a variety of
commercially available matrix
Figure 4a LCO yield vs conversion Figure 4b Coke vs conversion materials. It shows that the novel
manufacturing process has resulted
in a matrix material that demon-
strates improved hydrothermal
stability.
"!3&nPROPRIETARY MATRIX
Most conventional matrix materi-
#OMPETITIVE &## MATRIX " als, such as alumina, predominantly
#OMPETITIVE &## MATRIX ! have Lewis acid sites, measured by
3UR FACE AREA RETENTION
#OKE WT
,#/ SELECTIVITY
higher coke production.
This demonstrates a need for a
fundamentally different catalytic
approach to increasing LCO yield.
The need is to have a selective
matrix that would increase the LCO
yield without the accompanying
coke yield.
#ONVERSION WT
#OKE WT
New technology platform
Development of the novel matrix
material was extended to include Figure 6a Coke vs conversion Figure 6b LCO selectivity vs coke
both the crystallisation of Y zeolite
and the formation of the matrix in a
single step. The manufacturing
process forms both the matrix mate-
rial and zeolite in a single step, and 30% low Z/M
it brings them into very intimate
catalyst + baseline
30% low Z/M
contact, with an ultra-low sodium catalyst + baseline
content. The hexagonal crystallites
of Y zeolite, smaller than 1 µm, are
,#/ SELECTIVITY
in the immediate vicinity of, if not
#OKE WT
Baseline
in intimate contact with, the amor-
phous matrix materials.
crystallisation of
R
Y
L
T
AR P A N U G P C OV E C N
! *U * U 3E / *A
Y zeolite and the
-
-
!
.
$
3AMPLE TAKEN DATE
formation of the
matrix in a single step Figure 8 Z/M ratio for HDXtra from the e-cat data at Refinery 1
The blend containing the new tech-
nology platform had lower coke
yield and higher LCO selectivity
than the blend containing commer-
cially available matrix material.
This new technology platform is
Y N L G G T V V N N B
A
*U *U U U /
C O O *A *A &E
-
!
!
.
.
called Promixal Stable Matrix and
3AMPLE TAKEN DATE Zeolite (Prox-SMZ), and all four of
those features play an integral role
in its catalytic performance. Prox-
Figure 9a Z/M ratio for HDXtra from the e-cat data at Refinery 2 SMZ is a flexible platform that can
be tailored to individual applica-
advanced cracking evaluation other FCC catalysts were compared tions, including use with different
(ACE) unit at 970°F (520°C), with to the new matrix material. feeds.
hydrotreated feed containing 3.88 Figure 6a shows the plot of coke Using the Prox-SMZ platform, we
wt% Conradson carbon residue. versus conversion for the four have developed and commercial-
LCO selectivity is defined as the matrix materials tested. The ised HDXtra, a catalyst specifically
ratio of LCO to the sum of LCO competitive matrix materials had targeted for vacuum gas oil (VGO)
and heavy cycle oil (HCO). Three very similar coke yields. In contrast, operations. Other Prox-SMZ cata-
different matrix materials used in the proprietary matrix stood out lysts, including Stamina for resid
Since 1818, it has always been the goal of Zeochem to develop and manufacture products
which do not additionally load our air and environment with impurities. ZEOcat® products are
the answer whenever it comes to remove volatile organic compounds (VOC) from waste air
and gas streams, the removal of odours and smell from thermoformed plastics in the car-
and food industry, as catalyst carrier in gasoline and diesel exhaust catalyst, as catalyst for
organic and process reactions in chemical, fine chemical- and petrochemical processes.
ZEOcat® is the answer and our commitment for a cleaner world, made in Switzerland by
experts and under very hard environment regulations. ZEOcat® products are available in forms,
such as Pentasil, ZSM-5, Mordenite, Beta and L-zeolite in powder form and a variety as
beads. For more information please go to www.zeochem.com
www.ptqenquiry.com
for further information
maximisation and is
targeted at VGO feed
AY
N
UL
G
G
C T
OV
OV
N
N
B
operations
*U * U U / * A * A &E
- ! ! . .
3AMPLE TAKEN DATE
feed operations, are currently in the
process of being commercialised.
Figure 9b Na content for HDXtra from the e-cat data at Refinery 2 HDXtra: the catalyst for LCO
maximisation in VGO operations
HDXtra is the first commercialised
catalyst developed using the Prox-
SMZ technology platform.2 This
FCC catalyst was specifically engi-
neered for distillate maximisation
and is targeted at VGO feed opera-
tions. Its features include high
:- RATIO
matrix activity with good coke
selectivity, moderate zeolite activity
to maximise LCO, and low H trans-
fer activity to preserve hydrogen in
the LCO for minimal cetane penalty.
N L G G T V V N N B HDXtra has been successfully
AY U *U U U C O O *A *A E
- * ! ! / . . &
demonstrated in three commercial
3AMPLE TAKEN DATE trials over the past year.
Trial at Refinery 1
Figure 10a MSA for HDXtra at Refinery 3 The first trial of HDXtra was at
Frontier in El Dorado, Kansas,
which operates as a hydrotreated
VGO refinery. HDXtra replaced a
NaphthaMax-II catalyst. This switch
can be most effectively seen in
Figure 8, where the e-cat Z/M ratio
drops from approximately 2.2 to
less than 1.
Another noticeable shift was in
Na, which on e-cat Na dropped
#OKE WT
Trial at Refinery 2
Figure 10b ACE coke levels of HDXtra over time at Refinery 3 Refinery 2 produced similar results,
#OKE WT
Trial at Refinery 3
At Refinery 3, the objectives were
to maximise feed rate and maintain
gasoline motor octane number
(MON). The refinery was previ-
ously using a competitive catalyst
designed for high LCO yields. The
base catalyst already had a rela- U L G P P
C T V V C N N B
* !U 3E 3E / .O .O $E *A *A &E
tively high MSA. Switching from
the competitive catalyst to HDXtra
increased the MSA from approxi-
mately 85 m2/g to 100 m2/g (see Figure 10c FCCU coke levels of HDXtra compared with the competitor at Refinery 3
Figure 10a). As in previous trials, e-
cat Na dropped dramatically during
the trial from about 0.25 wt% Na to
less than 0.1 wt%. This decrease in
Na not only improves the stability
of zeolite and the matrix, but also
decreases the hydride transfer,
which positively affects cetane.
HDXtra trial
Although the MSA increased, it
did not detrimentally impact the
WT
coke yield (see Figure 10a). This
reinforces the experimental obser-
vation during product development
that not all matrices are equal in
their catalytic behaviour. In Refinery
3, the ACE and FCCU coke data
remained at the same levels (see
Figures 10b and 10c). Unlike tradi- P
CT
V EC
N
B
AR
3E / .O $ *A &E -
tional high-MSA catalysts, HDXtra
did not lead to coke penalties.
Further observations of e-cat
change-over at Refinery 3 show Figure 10d Na levels over time at Refinery 3
how HDXtra has the lowest
commercially available Na (see
Figure 10d). Refinery 3’s normalised
BASF’s e-cat
benchmarking
WT
BASF HDXtra
Competitor
using HDXtra over the base
catalyst.
Refinery trials: conclusion
BASF’s e-cat benchmarking data-
UL G
P P T V V C N N base has shown through trials that
* !U 3 E 3 E /C .O .O $E *A *A
HDXtra has some of the highest
MSA and matrix stability available
and the lowest Na content (see
Figure 10f Normalised slurry levels at Refinery 3 Figure 11). Both factors result in
higher gasoline octane and better
LCO cetane in the unit. All three
Customer operating data at Refinery 3 trials show a significant increase in
normalised LCO yield, while the
Cases corrected for cut point, feed rate, feed quality and operating conditions coke and slurry levels remain
Catalyst supplier Competitor BASF ∆ constant. ACE testing of e-cats
Case title Base case HDXtra
confirmed the results.
Case date Oct 08 Jan 09
Conversion
Corrected fresh feed conversion, wt% 76.10 74.47 -1.63 Further developments
Product yields BASF is designing a set of solutions
Weight per cent basis
based on the Prox-SMZ technology
H2+C1+C2+C2=, wt% 2.12 2.05 -0.07
Total C3 + C4, wt% 22.38 19.69 -2.69 platform to address the needs of
Corrected C5+ gasoline, wt% 46.50 47.73 1.23 the refining industry. Stamina, an
Corrected light cycle oil, wt % 21.78 23.60 1.82 FCC catalyst for distillate maximi-
Corrected slurry, wt% 2.12 1.93 -0.19
sation targeted at resid feed
Coke, wt% 5.09 5.00 -0.09
Product properties operations, is currently undergoing
Gasoline RON, RON 92.5 93.2 0.7 extensive internal manufacturing
Gasoline MON, MON 80.4 80.6 0.1 trials. This catalyst was designed
with more macroporosity for heavy
molecule access, together with
Table 5 proven metals tolerance features.
References
Cumulative, %
1 Hart’s World Refining and Fuels Service
(WRFS) 2009.
2 McLean J B, The role of FCC catalyst
technology in maximizing diesel production —
two North American refinery success stories,
&REQUENCY
0ER CENT
Frequency
2009 NPRA paper.
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turn in catalysts. We’ll help you innovate when you need to move in a
With our expert catalyst new direction, and we’ll be there with expert support down the road.
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Catalysts with higher and more stable activity enable cost savings and boost
output in methanol production
F
or many years, methanol has
been used primarily as a
Competitor
chemical intermediate in Com
pet A
itor B
manufacturing plastics and resins, JM
then more recently in the manufac-
Others
ture of methyl tertiary butyl ether
(MTBE) for use as a lead anti-knock
replacement and octane enhancer,
allowing a methanol derivative to
enter the transportation fuel chain
in a significant way for the first Figure 1 Methanol technology market shares
time. However, now methanol is
being seen as a product that can be methanol synthesis catalysts and series catalysts — an improvement
introduced directly into the gaso- discuss the various changes that that is a step change in methanol
line pool by blending, allowing have occurred in the Katalco range synthesis catalysis.
indigenous resources to be used of catalysts against the backdrop of
and providing a diversity of supply changing industry requirements. Methanol synthesis catalysts
that can help to reduce dependence Since the initial development of the
on crude oil and attempt to break Methanol production first copper-zinc low-pressure
the cycle of apparently ever- ICI initiated work on catalysts for methanol synthesis catalyst, Katalco
escalating oil prices. methanol synthesis in the 1920s, 51-1, continuing development
China has introduced a national when the only commercial process programmes have improved
M85 standard that sees gasoline operated at high pressure. Follow performance in terms of activity,
blended with 85% methanol, which ing early research on copper-zinc by-products production, strength,
has been manufactured using catalysts, ICI announced the Low shrinkage and overall life. The orig-
China’s cheap and abundant Pressure Methanol (LPM) process inal catalyst was designed for
supplies of coal, helping to reduce in 1963 and the first single-train application in the multi-bed ICI
its dependence on expensive production unit started operation in Quench lozenge converter, and an
imported oil. 1966. early variant, Katalco 51-2, quickly
In the US, there is considerable JM Catalysts has recently devel- became the industry standard. As
support for the Open Fuel Standard oped a new generation of copper additional technologies were devel-
Act, which, if passed, would call for zinc methanol synthesis catalysts oped, different types of converter
car manufacturers to introduce flex- called Katalco Apico. This extends were used, the most noteworthy
ible fuel vehicles that can the performance of the Katalco 51 being gas-cooled and steam-raising
run on methanol/ethanol/gasoline in both axial and radial flow config-
mixtures. Currently, there is little urations. These often impose
methanol production left in North Now methanol is different requirements on the cata-
America, but the development of lyst, so JM Catalysts has developed
shale gas is set to reduce natural being seen as a a range of synthesis catalysts.
gas prices significantly in North It is worth considering the vari-
America. And, like China, the US
product that can be ous changes that have occurred in
has abundant coal reserves, which, introduced directly Katalco catalysts against the back-
through methanol, could be drop of changing industry
used to displace oil imported from into the gasoline pool requirements. These changes do not
abroad. come from any one aspect of the
In this article, we will look at by blending catalyst. The enhancements have
Activity
tion thermodynamics and loop
!L/
Refining: Catalysts:
Petroleum Production of chemicals
& petrochemical catalysts Gas purification
Carbon catalysts Petrochemistry
Homogeneous catalysts Special catalysts
Precious metal alloys
Chemical compounds Chemical Products –
E-scrap Inorganics and Organometallics:
Precious metal chlorides, nitrates,
Platinum Group Metal hydroxides, carbonates, acetates
Alloys Manufacturing: "Ammonium Perrhenate" (APR) and
Nitric gauzes "Perrhenic Acid" (PRA)
Thermocouple wires Homogeneous catalysts for petrochemistry,
Crucibles & labware e.g. CARAC, ROPAC, [RhH(CO)(PPh3)3],
Other custom alloys Rhodium Acetate
Comprehensive range of homogeneous catalysts
Trading – Buy/Sell/Lease: for other applications, e.g. Pd(dba)2, "Wilkinson's",
Platinum, Palladium, Rhodium, [Pd(PPh3)4], [{Ir(cod)}2(µ-Cl)2], "Karstedt's"
Ruthenium, Iridium, Silver, Gold Tailor-made compounds on an NDA basis
www.ptqenquiry.com
for further information
of the catalysts’ operational life.
Due to the high copper content,
initial catalyst reduction and devel-
opment of the copper surface area
leads to major changes in the physi-
cal structure, which is manifested
#OPPER SUR FACE AREA MG
!CTIVITY
years, are commonplace, even in
the arduous catalyst-in-tube steam-
raising duty discussed in the case
study below.
Choice of catalysts
JM Catalysts currently offers four
methanol synthesis catalysts;
4IME ON
LINE MONTHS
namely, Katalco 51-8, Katalco 51-
8PPT and Katalco 51-9S and the
premium product Katalco Apico. Figure 7 Activity of Katalco 51-9S
Providing a range of catalysts, and
not relying on a single universal reaction heat removal systems. each charged with 60m3 of Katalco
product, caters for the different These include, but are not limited 51-9S. Experience has shown that
methanol synthesis technologies to, the direct quench-cooled adia- with this type of reactor careful
and enables a choice of product for batic converter design, the axial initial catalyst charging is essential
the specific duty. This is particu- steam-raising catalyst-in-tube to ensure minimum pressure drop
larly pertinent in a climate where design or the catalyst-in-shell-side, variation between tubes, to give an
feedstocks are changing. Natural gas-cooled design such as the tube- even flow distribution and maxi-
gas has been the principal feed for cooled converter. Furthermore, the mum use of the relatively small
synthesis gas generation (account- savings through economies of scale volume of catalyst. The catalyst has
ing for ~80% of world methanol that might be accrued from build- been producing record production
production); synthesis gas genera- ing world-scale methanol plants can levels of 2600 tpd since May 2005,
tion historically has largely been benefit from the use of radial flow giving significant financial benefit.
based on pure steam methane converters such as the Davy Process As a result of the enhanced
reforming, whereas more recently Technology radial steam-raising performance of the catalyst, an
there are circumstances when converter. extended run of four years is
combined reforming, which planned. JM Catalysts has provided
includes an oxygen-fired secondary Case study: Titan Methanol detailed technical support through
or ATR, has its merits. This Lurgi-designed plant has a out, carrying out frequent
Coal gasification is another nameplate capacity of 2500 tpd and performance optimisations. Figure
method of syngas generation seeing the synthesis loop comprises two 7 confirms the activity achieved,
rapid expansion in the number of parallel steam-raising converters, which is 20% greater than Katalco
medium- and large-scale methanol
projects in China based on a rela-
tively cheap and plentiful resource,
with many more plants likely to
appear in the future. The US,
Australia, India and Russia also
-EASURED PRESSURE DROP BAR
have abundant supplies of coal. In
relation to the actual converter type,
and without going in to too much
detail, the different syngas-
generating technologies yield
different syngas compositions (for
instance, CO content), each compo-
sition yielding different reaction
rates over the synthesis catalyst.
Consideration of the exothermic
synthesis reactions means that some
4IME ON
LINE MONTHS
converter designs are better suited
than others to the different
synthesis gases, by virtue of their Figure 8 Pressure drop stability of Katalco 51-9S with time
OR
by-products commercial catalyst, leading to
E M
fewer catalyst change-outs. On a
ETH
ANO
2500 tpd plant currently achieving
UP
L
ART
AND
four years between change-outs, the
T
&ASTEST S
IMPR
Pre-reduced Highest typical time saved by doubling the
catalyst activity catalyst life is about nine-and-a-half
OVED EFFICIENCY
Apico days, equivalent to at least 23 750
tonnes of product methanol. This is
derived from savings on oxidation
of the previous catalyst charge prior
Strongest to discharge, time to discharge and
slowest
ES
product refill and then reduce the new
NG
deactivation
,OW
HA
ES
T C
T R
LYS
AT
OF
TA
A
E
#ONCENTRATION IN CRUDE METHANOL PPM
Overall benefit
-ETHYL PROPAN
OL
As indicated in the previous
"UTANOL
sections, the enhanced performance
of Katalco Apico leads to benefits in
many aspects of plant operation.
These are summarised in Table 1.
The total value of these benefits is
over $25 million in additional meth-
anol sales (assumed methanol price
$200/t). Additional savings related
to manning and material costs of
shutdown may also be realised.
+ATALCO !PICO +ATALCO
3
Terry Fitzpatrick is Methanol Technology
Manager within the GTL group of Johnson
Matthey Catalysts. His work has a particular
emphasis on the development of technology Figure 12 In-situ radial pellet strength of Katalco Apico
and catalyst applications for methanol
chemistry. He joined the catalyst business
(then ICI) over 20 years ago and has a Operating benefits of Katalco Apico
bachelor’s degree in chemical engineering from
Cambridge University, UK.
Tom Hicks is a consultant with Johnson Feature Benefit to operator Extra MeOH, tonnes
Pre-reduced catalyst Faster start-up 3000
Matthey Catalysts. He has worked on steam
Higher, stable activity Additional MeOH made 55 000
reforming catalysts and technology, shift and Doubled catalyst life Eliminated change-out 23 750
methanol catalysts, acetylene hydrogenation 50% lower by-products Increased efficiency 45 000
catalysts and ammonia synthesis technology Total 126 750
for ICI and now Johnson Matthey, and has a
bachelor’s degree in chemistry from Durham
University, UK. Table 1
A
spin-off from the Department exhibit conversion efficiencies in the This catalyst has been optimised for
of Chemistry at the range of 70% per pass and are use in FT microchannel reactors, to
University of Oxford in 2004, designed for economical production enable the small-scale distributed
Oxford Catalysts works on the on a small scale. A single micro- production of next-generation
development of metal carbide cata- channel reactor block might biofuels from a wide range of waste
lysts for the generation of clean produce up to 40 barrels (bbls) of feedstocks. Demonstrations of FT
fuels from both conventional fossil liquid fuel per day. In contrast, microchannel reactor technology, to
fuels and sustainable, renewable conventional FT plants are designed produce liquid fuels from biomass,
sources such as biomass waste. to work at minimum capacities of are due to take place in 2010. The
These include improved hydrodes- 5000 bbl/day, and function well technology is also being adapted to
ulphurisation (HDS), chemisorption, and economically at capacities of create small-scale gas-to-liquid
steam methane reforming (SMR) 30 000 bbl/day or higher. They (GTL) facilities for use offshore to
and Fischer-Tropsch (FT) catalysts. typically exhibit conversion efficien- capture the energy from flare gas.
The group, as a whole, focuses on cies of 50% or less per pass.
developing new and improved Instant steam
catalysts and catalyst-based tech- Although the group’s main focus is
nologies to create cleaner fuels for Microchannel on technology for cleaner and
the future. Within the group, greener liquid fuels, it also has a
Velocys concentrates on the devel- processing enables novel catalyst and fuel combination
opment of microchannel reactor that produces instant steam. This
technology, while catalyst develop- chemical reactions development is based partly on
ment is carried out by Oxford work originally carried out by Dr
Catalysts.
to occur 10 to 1000 Tiancun Xiao, one of the founders
Microchannel reactors are com- and Senior Scientific Advisor at
pact reactors that have channels
times faster than in Oxford Catalysts, as part of his
with millimetre-sized diameters. conventional systems search for a catalyst-based reaction
Small-diameter channels dissipate to create a portable hydrogen
heat more quickly than conven- generator for powering fuel cells.
tional reactors with larger-diameter Xiao’s starting point was an uncon-
channels in the range of 2.5–10cm Oxford Catalysts has also devel- ventional fuel mixture of an organic
(1–4 inch), so more active catalysts oped and patented a catalyst compound (methanol), with hydro-
can be used. Mass and heat transfer preparation method, known as gen peroxide passed over a
limitations reduce the efficiency of organic matrix combustion (OMX), platinum catalyst to produce hydro-
large, conventional high-pressure which makes it possible to achieve gen at room temperature via an
reactors used for hydroprocessing. high metal loadings while reducing exothermic reaction:
Microchannel processing enables the need for precious metal promot-
chemical reactions to occur 10 to ers and enabling precise control of H2O2 (hydrogen peroxide) + CH3OH (methanol)
1000 times faster than in conven- crystallite sizes. OMX played a key ==> 2 H2 + CO2 + H2O
tional systems. role in the development of these
Microchannel FT reactors, devel- improved HDS catalysts, which are The large amounts of heat and
oped by Velocys and using a new, designed to enable refineries to steam produced during this reac-
highly active metal carbide FT cata- meet the requirements for cleaner tion also made it possible to
lyst developed by Oxford Catalysts, fuels from less than ideal feed- reformulate the fuel to produce
will soon be trialled for the small- stocks. OMX also lies behind the high-temperature steam at room
scale distributed production of development of the new, highly temperature and pressure via the
biofuels from waste. These reactors active metal carbide FT catalyst. reaction:
With its submicron-level control, ACE technology provides dual activity for
superior levels of sulfur and nitrogen removal in all applications. Easy to load
and activate, HR series catalysts also offer excellent regeneration properties.