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Platinum Metals Rev., 2011, 55, (4), 263267

263 2011 Johnson Matthey

http://dx.doi.org/10.1595/147106711X593717 http://www.platinummetalsreview.com/

By Arno de Klerk (University of Alberta, Edmonton, Alberta, Canada) and Edward Furimsky(IMAF Group, Ontario, Ottawa, Canada), RSC Catalysis Series, No. 4, Royal Society ofChemistry, Cambridge, UK, 2010, 294 pages, ISBN: 978-1-84973-080-8, 121.99,US$205.00, 139.95 (Print version); e-ISBN: 978-1-84973-201-7 (Online version)

Reviewed by Stewart Brown

Johnson Matthey Precious Metals Marketing, Orchard Road,Royston, Hertfordshire SG8 5HE, UK

Email: [email protected]

Introduction

Catalysis in the Refning o Fischer-Tropsch Syncrude

is the ourth book in the Royal Society o Chemistrys

Catalysis Series. Written by Arno de Klerk and Edward

Furimsky rom the University o Alberta and the IMAF

group in Ontario, Canada, respectively, this book pro-

vides a review o the somewhat neglected area o refn-

ing and upgrading catalysts, rather than the more widely

published area o Fischer-Tropsch synthesis itsel (1).

This book provides an excellent and comprehensive

evaluation o the catalytic processes or syncrude con-

version to useul products such as uel and oils.

The book consists o eleven chapters, which are

well presented and divided into easily manageable

segments. The writing style is very clear and explains

the processes concisely and simply. The frst two

short chapters put syncrude refning into contextwithin the Fischer-Tropsch process as a whole and

allow non-specialists to quickly grasp the technology.

The remaining chapters take the reader on a logi-

cal and well thought out journey through the

Fischer-Tropsch production o syncrude; the upgrad-

ing o waxes, oxygenates and crude; the catalysis

o the refning process; the commercial products

obtained during the process; and fnally a review o

the current patent literature and uture perspectives.

Fischer-Tropsch Processes

Fischer-Tropsch is the process whereby synthesis gas(hydrogen and carbon monoxide) is converted into a

mixture o hydrocarbons, oxygenates, water and car-

bon dioxide. The hydrocarbons thus produced can be

refned and used in place o more conventional liquid

uels derived rom crude oil. Synthetic uel can be pro-

duced by a variety o methods, with gas-to-liquid (GTL),

coal-to-liquid (CTL) and biomass-to-liquid (BTL) being

the most widespread. An outline o a Fischer-Tropsch

acility is summarised in Figure 1.

Fischer-Tropsch synthesis has been carried out

predominantly using iron- and cobalt-based catalysts

Catalysis in the Refining ofFischerTropsch Syncrude

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http://dx.doi.org/10.1595/147106711X593717 Platinum Metals Rev., 2011, 55, (4)

since the 1930s, having been commercialised in Ger-

many in 1936 to provide transport uel or the coal

rich, oil poor nation. South Arica has since become

the largest user o Fischer-Tropsch technology, devel-oped in response to international sanctions that pre-

vented the import o crude oil, and nearly the entire

countrys diesel is currently produced rom coal by

this method (2).

In the present book, Chapters 3 and 4 provide a good

technical overview o and background to the chemistry

o Fischer-Tropsch reactions. These chapters concen-

trate on how dierent reaction and catalyst conditions

aect the composition o the syncrude (Figure 2).

Chapter 3 concludes with an examination o current

industrial Fischer-Tropsch processes. The message

is that this area o chemistry is not just an academicpursuit, but rather a key technology or uture energy

security and uel production. The table o production

acilities provides a timeline rom the frst acilities

employed by Germany during the Second World War

right up to the gigantic Shell Pearl GTL plant in Qatar.

This plant began shipments o its GTL Gasoil product

in 2011 with ull production scheduled or 2012. In

Chapter 4, the reader is taken in more detail through

the initial processing steps o Fischer-Tropsch synthe-

sis and how the syncrude produced diers rom that

obtained rom conventional crude oil. The dierences

in chemical composition are vital in understanding

which downstream refning and upgrading processes

are required to produce useul commercial products.

Platinum Group Metals in the Upgrading of

Fischer-Tropsch Syncrude

Chapter 5 is where the main topic o the book really

gets going, it is by ar the largest chapter in the whole

book with over 120 pages devoted to it. Here the

reader is provided with a review o the technical detail

behind the catalysis o upgrading Fischer-Tropsch

syncrude. The chapter is split into our main sections

corresponding to the most widely utilised conversion

technologies. These are:

(a) oligomerisation,

(b) isomerisation and hydroisomerisation,(c) cracking and hydrocracking,

(d) hydrotreating.

Although this chapter contains the most signif-

cant amount o inormation, it only concerns the

upgrading o syncrude rather than the refning.

Catalytic reorming, which is an important platinum

group metal (pgm) utilising process in refneries, is

mentioned in a later chapter.

In terms o pgm usage, all but the oligomerisation

section contain numerous reerences to pgm-catalysed

processes. The subsections proceed in a logical ash-

Feed preparation

Feed-to-syngasconversion

Gas cleaning andH2:CO adjustment

Fischer-Tropschsynthesis

Refinery

Syncrudecooling/separation

Fischer-Tropsch gas loop

Offgas:CO2H2S

Water

Products:

FuelsChemicals

Syncrude

Raw material:CoalNatural gasBiomassWaste

Fig. 1. A simplifiedflow diagram of a Fischer-Tropsch-based facility (some liquid pyrolysisproducts may be produced, represented by the dashed line) (Reproduced by permissionof The Royal Society of Chemistry)

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ion, describing frst the background and mechanism o

each process, then the various catalysts used. The useo platinum and palladium as promoters in various

zeolite, silica-alumina, phosphate and sulonated zir-

conia catalysts is given considerable coverage, well

illustrated by graphs and tables detailing conversion,

yield and selectivity relationships with various eed-

stocks. The catalytic mechanisms detailed throughout

this book are very clear, giving the reader an under-

standing o the chemistry behind the refning and

upgrading processes. The vast range o dierent tem-

peratures, pressures, eeds, catalysts and other actors

are emphasised, giving a good eel or the complexity

o syncrude upgrading. The authors compare and con-trast these dierent actors and clearly show the eect

o each on the fnal products.

Each section gives a solid introduction and mecha-

nistic outline to each process, ollowed by an examina-

tion o the commercial aspects and a comprehensive

review o the current literature regarding catalyst devel-

opments. They conclude with a comparison o the vari-

ous modes o deactivation or dierent catalysts and

conditions. This is an area oten neglected when con-

centrating on activity, yields and selectivity.

Refining Catalysts

Chapter 8, despite being somewhat shorter thanChapter 5, nevertheless contains an excellent review

o refning catalysts, such as those employed in reorm-

ing, a signifcant area o pgm demand. The frst part

o the chapter demonstrates the dierences between

conventional oil refneries and those employing

Fischer-Tropsch technology. The generic plant designs

illustrated at the beginning o the chapter highlight the

major dierences in how the various refned ractions

are produced and again drives home the message that

to produce high quality uels and oils using Fischer-

Tropsch synthesis requires specialised equipment,

processes and catalysts to deal with the dierent chem-istries o syncrude and conventional crude oil. The frst

table in Chapter 8 highlights this urther by examining

the current conventional conversion processes and

their compatibility with Fischer-Tropsch refneries.

There are two subsections dedicated to the use o

platinum on acidic alumina and on non-acidic zeolite

respectively, highlighting the importance o platinum or

the production o synthetic uels. The higher amounts o

oxygenates in Fischer-Tropsch eed have been shown to

deactivate the acidic support, although it is very compat-

ible with the non-acidic L-zeolite catalyst (Figure 3). The

Syngas

Steam

Gaseousproducts

Wax

Gaseous products

Syngas

Steam

Wax Steam

Gaseous products Gaseous products

Steam

Syngas

Cyclones

Syngas

Fixed bed Slurry bubble column Circulating fluidised bed Fixed fluidised bed

Fig. 2. Fischer-Tropsch reactor technologies in industrial applications (Reproduced by permission of The RoyalSociety of Chemistry)

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much lower sulur content o the eed is a distinct advan-

tage over conventional crude eedstocks.

The fnal chapters examine the commercial prod-

ucts obtained rom Fischer-Tropsch syncrude, the cur-

rent patent literature and uture perspectives in this

technology. The authors do a very good job o putting

the catalysis reviewed in the preceding chapters into

a commercial context, whilst showing what the uture

may hold or this exciting area. The fnal chapter makes

the interesting point that Fischer-Tropsch plants havehistorically been built to deal with issues o energy

security. Going orward it appears that investment will

be driven by both the requirement to produce uels

rom alternative carbon sources and the price dieren-

tial between conventional crude and that produced by

Fischer-Tropsch technology.

Conclusions

The authors state that a review o catalysis in the refn-

ing o Fischer-Tropsch syncrude is the main objective

o the book. This objective has been achieved admi-

rably, providing an accessible and comprehensivereview o Fischer-Tropsch refning catalysis rom the

undamental chemistry to the commercial aspects

and applications. The reader is required to have a

general understanding o chemistry and catalysis, and

the book will appeal both to those looking to gain ini-

tial exposure to this topic, and to readers with greater

knowledge o the subject. The use o the pgms eatures

strongly throughout the book, dominating the chapters

on upgrading and refning syncrude.

Overall, this book will be o interest to a wide audi-

ence, rom those involved in the academic pursuit

o improving the catalysis to those involved with the

commercial development o Fischer-Tropsch refning.

It is clearly an exciting area to be involved with and

the potential to provide an alternative to conventional

uel sources is something that the authors convey par-

ticularly well.

References1 Advances in Fischer-Tropsch Synthesis, Catalysts, and

Catalysis, eds. B. H. Davis and M. L. Occelli, CRC Press,Boca Raton, Florida, USA, 2010

2 M. E. Dry, Catal. Today, 2002, 71, (34), 227

Pt PtPtPt Pt PtPtPt

H

Pt PtPtPt

H H

Pt PtPtPt

+ 4H2

End-on adsorption 1,6 Adsorption

Fig. 3. End-on adsorption of n-alkanes on platinum/L-zeolite which results in 1,6-ring closure andaromatisation (Reproduced by permission of The Royal Society of Chemistry)

Catalysis in the Refining of Fischer-Tropsch Syncrude

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The Reviewer

Dr Stewart Brown graduated withan MChem (Hons) and a PhD in

Chemistry from the University ofLiverpool, UK. He joined JohnsonMatthey in 2004 and spent 5

years as a Process DevelopmentChemist, involved in the scale-upof new catalysts and processes forthe Emission Control Technologiesbusiness unit. In 2009 he transferredto Precious Metals Marketing and iscurrently a Market Analyst within theMarket Research team, focusing on

platinum group metal demand fromthe chemical, electronics, automotiveand petroleum refining sectors.

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263-267-pmr-oct11