Production of Synthetic Fuel Using the Fischer-Tropsch Method

Current Status & Future Prospects

T.A.Arshad*
*Trinity College & Department of Chemical Engineering & Biotechnology,
University of Cambridge
Abstract
This paper seres as an oerie! of the prospects of the Fischer Tropsch process for the
production of alternatie fuels. The arious unit operations in use today are introduced and
co"pared. The selectiity and conersion achieed #y different catalysts is discussed. Possi#le
future i"proe"ents in the Fischer Tropsch process are reie!ed$ and its future econo"ic and
eniron"ental outloo% is analysed.
1. Introduction
Currently$ the ast "a&ority of the !orld's
fuel and che"ical production is #ased on
crude oil. The %no!n reseres of "ethane are
a#out (.) ti"es that of crude oil$ and those of
coal al"ost *) ti"es. Moreoer$ the pro#le"
of +stranded' natural gas has #een
longstanding$ and any "oderately si,ed
facility !hich could conert this gas to li-uid
products for easy transportation to point of
use !ould go a long !ay to!ards soling it. .t
is for these "a&or reasons that the Fischer
Tropsch /FT0 process$ starting in 1er"any in
the (2*3s and gaining strength oer the ne4t
53 years$ is once again starting to figure
pro"inently in glo#al energy discourse.
6inear hydrocar#ons #eing the na&or
product of FT synthesis$ FT diesel fuel has an
e4cellent cetane nu"#er of around 7). Using
the lo!-te"perature FT /6TFT0 under
appropriate conditions to produce paraffins
heaier than diesel$ high -uality diesel fuel
can #e produced !hen co"#ined !ith
hydrocrac%ing.
2. Reactors for Fischer Tropsch Synthesis
Adances in reactor design for the Fischer
Tropsch synthesis "irror the ariation in
interest in the process itself. 8eactors suited to
the Fischer Tropsch synthesis !ere first
deeloped #efore and during the second !orld
!ar$ "ost of the" in 1er"any. These !ere
adia#atic or internally cooled fi4ed #ed
reactors$ "ultitu#ular reactors or slurry
reactors !ith entrained catalysts /9ais$
*33*0. Their production capacity !as ery
s"all #y current standards /a#out () ##l:day0$
and thus had little co""ercial scope /Sie and
;rishna$ (2220. A second phase of reactor
deelop"ent !as spurred #y the Ara# oil
e"#argo of the (273s$ and significant
i"pore"ents in reactor design !ere
achieed. Seeral plants e"ploying different
technologies !ere erected$ including the
"ultitu#ular fi4ed #ed South African Coal$
<il and 1as Corporation /Sasol0 syste" in
Sasol#urg$ South Africa$ and the circulating
fluidised #ed syste" !ith a first plant in
Sassol#urg in (2)) follo!ed #y t!o others in
Secunda and =it!atersrand in (2>3 and
(2>*. These increased the capacity to ?)33
##l:day /@enson$ (2)(A ;eith$ (2B?A 1arrett$
(2?30.
The core issue facing design of Fischer
Tropsch reactors is that the #asic reaction
underpinning the synthesis is highly
e4other"ic$ and thus high rates of heat
transfer are re-uired to achiee isother"icity$
!ith the ai" of "ini"ising the te"perature
rise across the catalyst #ed. The Fischer
Tropsch synthesis is %inetically controlled.
=ith increasing te"perature /Schult,$ (2220
selectiity of the undesired "ethane rises
gro!ing car#on deposits deactiate the
catalyst /this effect is "ost pronounced
!ith Fe #ased catalysts0
the aerage chain length of the product
"olecules is reduced$ an undesira#le affect
in a process ai"ed at diesel for"ation
There are t!o "odes of operation for the
Fischer Tropsch processC a high te"perature
"ode /533-5)3 DC0 usually e"ploying Fe
#ased catalysts ai"ed at the for"ation of
gasoline and olefins /6ei#old et al.$ *33>A
Steyn#erg et al.$ (2220$ and a lo! te"perature
"ode /*33-*B3 DC0 !ith Fe or Co catalysts
targeted at the for"ation of linear !a4es or
high -uality diesel /!hen co"#ined !ith
hydrocrac%ing0 /Eager and Fspino,a$ (22)A
Fspino,a et al.$ (2220. The lo! te"perature
Fischer Tropsch /6TFT0 is thus of interest
here.
There are seeral techni-ues of ensuring
the high rates of heat transfer re-uired$ and
these for" the #asis of t!o "a&or classes of
FT reactorsC fi4ed #ead and fluidised #ed.
2.. !"lti#t"b"lar $i%ed Bed &eactors
These are the only type of fi4ed #ed
reactors in operation today. They consist of
narro! tu#es pac%ed !ith catalyst particles
and surrounded on the outside #y !ater. A
large flo! of syngas is then passed through
the tu#es.
Fig. (C Multitu#ular Fi4ed @ed 8eactor /9ry$ *33*0
The high flo!rate of syngas is necessary to
ensure tur#ulent flo!$ thus "ini"ising the
#uild-up of reactants$ inter"ediates and
products on the catalysts and inner tu#e
surfaces. The tu#es are "ade narro! to
"ini"ise heat loss #et!een catalyst and tu#e
!all$ and to "a4i"ise the the heat tranfer area
per unit "ass of catalyst. .nspite of these
precautions$ readial te"perature gradients of *
to B DC$ and those of () to *3 DC$ are typical
/9ry$ (22?0.
Adantages of "ultitu#ular reactors
includeC
They are easy to operate
They can #e used oer a !ide te"perature
range$ irresespectie of !hether gaseous or
li-uid products are desired
6i-uid products /such as diesel0 tric%le
do!n the #ed$ and can #e easily separated
fro" the e4it gas using a decanter placed
do!nstrea"
Any G
*
S /usually present in syngas as an
i"purity0 entering the reactor during a
process upset is a#sor#ed #y the catalyst
particles at the top /9ry$ (2230$ thus
shielding the #ul% of the catalyst and
preenting a large decrease in actiity.
The disadantages of "ulti-tu#ular
reactors are pri"arily econo"ic.
They are e4pensie to fa#ricate$ costing four
ti"es as "uch as slurry #ed reactors
The high flo!rate of syngas through the
narro! tu#es results in a differential
pressur across the tu#e$ thus re-uiring
e4pensie gas co"pression if the e4haust
gas is to #e recycled /usually done for Fe
catalysts$ !hich !ould other!ise hae a
lo! conersion0
They i"pose a li"it on the "a4i"u"
catalyst surface area$ since s"all catalyst
particles increase the pressure drop across
the tu#es
8eplace"ent of deactiated catalyst in large
narro!-tu#ed fi4ed #ed reactors is ti"e
consu"ing and effort intensie$ leading to
losses #oth in ter"s of do!nti"e and "an-
effort.
Fig. *C Fluidised @ed 8eactors /A0 Circulating Fluidised @ed /CF@0 /@0 Fi4ed Fluidised @ed
/FF@0 /C0 Slurry @ed 8eactor /9ry$ *33*0
2.2. $l"idised Bed &eactors
Fluidised #ed reactors acco"plish rapid
rates of heat transfer #y tur#ulent fluidisation
of the catalyst particles. They can either #e
t!o phase$ such as the fi4ed fluidised #ed
/FF@0 and the circulating fluidised #ed
/CF@0$ or three phase$ of !hich the slurry
reactor is the only type. The t!o phase types
are generally used for the high te"perature
"ode /GTFT0$ such as the Sasol plants in
Sasul#urg /9ry$ (2>(0 and the shell plant in
@intuli$ Malaysia /9ais$ *33*0
For lo! te"perature operation$ !ith li-uid
products /thus giing a three phase reaction0$
the slurry reactor is co""on. The application
of these reactors to FT synthesis !as studies
in the (2)3s$ ;ol#el's (.)" i.d unit #eing the
"ost pro"inent. .n the (273s$ Sasol used their
pilot plants to co"pare the perfor"ance of
fi4ed and slurry #ed reactors$ and found the"
to #e si"ilar in ter"s of e4tent of conersion
and selectiity /9ry$ (2>(0. The pro#le" of
separation of the fine iron-#ased catalyst
Sasol !ere using fro" the !a4 product
signiicantly delayed their co""ercial
applications$ and it !as only four decades ater
;ol#el's discoery that F44on /no! F44on
Mo#il0 successfully e"ployed a (.* " i.d. $
>.) %ilotonne:year slurry #ed reactor for"
!a4 production /Fidt et al.$ (22B0.
The "ain adantages of a slurry #ed
reactor oer a "ultitu#ular reactor are
The cost of the reactor is only a#out B3H of
a si"ilar capacity "ultitu#ular syste"
/9ry$ *33*0
The pressure drop across the #ed is lo!er$
gi#ing lo!er co"pression costs
8eplace"ent of catalyst can #e si"ply done$
so longer runs can #e carried out
The slurry #ed reactor has a higher degree of
isother"icity$ since the li-uid !a4 acts as a
heat sin%$ eli"ination hot spots typical in a
"ulti-tu#ular reactor.
A "a&or disadantage is that any catalyst
poison$ such as G
*
S$ entering the reactor
deactiates all the catalyst
3. FT Catalysts
Catalysts !hich display sufficient actiity
for co""ercial application of FT processes
are Ii$ 8u$ Co and Fe. The pri"ary source
for the Fe catalyst is scrap iron. .f the price of
scrap is ta%en to #e (.3$ the prices of Ii$ Co
and 8u are *)3$ (333 and )3$333 respectiely.
Iic%el is ery hydrogenating$ giing "ethane
yields that are too high$ !hile the scarcity and
cost of 8u e4cludes it. This leaes only Fe
and Co as ia#le FT catalysts.
Fe catalysts hae a high iron content /)g
;
*
<$ )g Cu and *)g Si<
*
per (33g F #eing a
typical co"position0$ and are prepared #y
precipotation. @efore use$ the catalyst is
reduced !ith either G
*

or a "i4ture of G
*
and
C<. /9ry et al.,(2>(0
Co catalysts are e4clusie to 6TFT /high
te"peratures lead to e4cess "ethane0. 1ien
the high cost of Co relate to Fe$ "ini"ising
the a"ount of Co needed !hile "a4i"ising
the surface area is o#iously desira#le. This is
achieed #y using Al
*
<
5
$ Ti<
*
or Si<
*
as a
#ase or the catalyst. .n order to pro"ote the
reduction process and aoid #uildup of
reaction "aterial on the catalyst surface$ a
s"all a"ount of a no#le "etal /usually Pr$ 8u
or 8e0 is used as a pro"oter /.glesia et al.$
(2250. .t has also #een fond that the
correlation #et!een actiity and catalyst area
is independent of the nature of the support
used /.glesia$ (2270.
4. FT Selectivity
.rrespectie of conditions$ the FT process
results in seeral products$ including olefins$
paraffins and o4ygenated products. The
aria#les /i.e. the degrees of freedo" the
designer can "anipulate0 !hich affect this are
the te"perature$ feed gas co"position and
pressure$ and types of catalyst and pro"oters
used. 9ue to the step!ise gro!th process on
the catalyst surface$ the relationship #et!een
the arious products is fi4ed$ regardless of
conditions /9ry$ (22?A 9ry$ (2230.
Fig. 5C Gydrocar#on Selectiity /9ry$ (22?0
For #oth Fe and Co catalysts$ increase in
te"perature shifts the selectiity to lighter
/lo!er car#on nu"#er0 and "ore
hydrogenated products. There is a greater
degree of #ranching$ and "ore secondary
products /such as aro"atics0 are for"ed. Co is
"ore hydrogenatig than Fe$ the products in
general are "ore hydrogenised$ and the
increase in "ethane selectiity !ith
te"perature is "ore pronounced.
For Fe #ased catalysts$ the degree of
#asicity of the surface is of critical
i"portance. Chain gro!th in the products
#eo"es "ore pro#a#le !ith #asic pro"oters
in the order 6i$ Ia$ ; and 8#. Although it has
#een o#sered that pro"oters increase the
actiity of Co catalysts$ it re"ains unclear
!hether selectiities are influenced /<u%aci
et al.$ (2220.
The lo!er the partial pressure of C< and
the higher the partial pressyre of G
*
$ the lo!er
the pro#a#ility of chain gro!th and the "ore
li%ely ter"ination to paraffin.

Fig. BC Conersion as a Function of @ed 6ength for 6TFT !ith C< and Fe Catalysts /9ry$
*33*0
. !ossible Future I"prove"ents in the FT
!rocess
There are seeral possi#le future
#rea%throughs$ decreasing the capital cost
associated !ith generating the syngas or
i"proing the ther"al efficiency of the plant
as a !hole$ !hich could i"proe the
econo"ic ia#lity of FT fuels.
Since an FT plant produces significant
-uantities of lo! pressure stea"$ co"#ining it
!ith a po!er generation plant !ould result in
a step rise of the efficiency of the process.
Sales of the energy assocaited !ith the stea"
!ould add to the profit earned per #arrel of
FT fuel produced.
'.. (eat E%changer &eforming
?3H of the cost associated !ith an FT plan
co"es fro" syngas generation. The
co"#ination of a heat e4changer refor"er
!ith an autother"al refor"er$ a process
si"ilar to the co""on used co"#ined
refor"ing !ith the only difference that the
e4it gas fro" the autother"al refor"er
supplies energy to the stea" refor"er instead
of a fired heater$ could significantly reduce
this #urden.
Potential #enefits are /Joosloo$ *33(0C
53H less o4ygen consu"ption
An appro4i"ate increase of BH in
the ther"al efficiency of the plant
@efore the full potential of this techni-ue
can #e realised$ the pro#le" of "etal dusting
in the heat e4changer refor"er "ust #e
addressed.
'.2. )%ygen Transfer !embranes
@y using cera"ic "e"#ranes to separate
the o4ygen fro" the air$ and co"#ining the
o4ygen re"oal and refor"ing stations into a
single unit$ large saings can #e "ade through
reduced capital costs due to the eli"ination of
the o4ygen plant and increased ther"al
efficiency. The econo"ic ia#ility of the
critically i"portant syngas generation stage
!ould thus #e i"proed. Current research in
this area focuses on the re-uired "echanical
strength of the cera"ic tu#es and
"a4i"isation of o4ygen flo!.
#. Critical Analysis of the Future !rospects
of FT Synfuels fro" $cono"ic%
$nviron"ental and &e"and
!erspectives
Fischer Tropsch fuels hae seeral inherent
adantages a#oe traditional fuels and other
synfuels ali%e. They are adapta#le$ #eing a#le
to produce li-uid products of arying car#on-
nu"#er fro" al"ost any car#onaceous
feedstoc%$ !ith coal$ natural gas and #ioass
#eing the "ost co""on. Secondly$ #ecause of
the si"ilarity of the final refined FT products
to traditional fuels$ they are co"pati#le !ith
#oth the e4isting transportation and storage
infrastructure$ and the appliances these fuels
are used in$ such as ehicles and aeroplanes.
Moreoer$ they can also #e #lended !ith
conentional fuels o!ing to this si"ilarity.
/Morita$ *33(A Su,u%i$ *33(A Ti&"ensen et al.$
*33*0.Thirdly$ FT fuels$ especially diesel
!hich is of interest here$ is of ery high
-uality$ haing a large cetane nu"#er and
#eing free fro" nitrogen and non-linear
conta"inants such as aro"atics. Ma&or
disadantages of FT fuels re"ain the large
capital cost of the plant$ and their co"paratie
energy inefficiency relatie to conentional
#iofuels and other non-conentional fuels
such as "ethanol and hydrogen.
8ecent studies /Ta%eshita and Ka"a&i$
*33>A Jallentin$ *33>0 indicate that regardless
of glo#al C<
*
policy /"ore specifically
!hether glo#al C<
*
e"issions are capped at a
certain *(33 target$ or allo!ed to continue
unchec%ed0 has a Lnoticea#leM share in the
energy future of the !orld. This conclusion is
understanda#le since inspite of the
afore"entioned econo"ic disadantages of
FT fuels$ #oth supply push and de"and pull
factors faour their use. <n the supply side$
the co"pati#ility !ith e4isting syste"s as
"entioned a#oe$ and the need for "iddle
distillates especially in the aiation industry
of interest to us$ contri#te to this effect.
FT fuels are also set to play a crucial role
in "eeting the gro!ing energy de"and of the
transportation sector oer the course of this
century. 1ro!th in the aiation industry oer
the ne4t fe! decades is li%ely to #e restricted
#y a !orld!ide crude oil shortfall. This can
#e oerco"e #y synthetic fuels$ including
those "ade through the FT process /Allen$
(2220. The FT process$ !hile "ore costly
than traditional fuels$ is econo"ical enough to
partially fill the oid created #y the crude oil
shortfall.
=hen oil is produced fro" "ethane ia the
FT process$ only a#out three -uarters of the
car#on content of the "ethane ends up in the
products$ the re"ainder #eing conerted to
car#on dio4ide. This "eans that the C<
*
e"issions of FT fuel fro" "ethane after
co"#ustion are 55H "ore than hydrocar#ons.
As for coal #ased FT plants$ a#out a third of
the coal is #urnt to fuel the highly
endother"ic gasification reaction. <erall$ FT
fuels deried fro" coal e"it t!ice as "uch
C<
*
than conentional fuels /9ry$ (2220.
Go!eer$ !hether the glo#al te"perature rise
is caused #y increased C<
*
leels or cyclic
long ter" changes /such as the +little ice age
three centuries ago0$ and !hether glo#al
!ar"ing !ill lead to eniron"ental disasters
are issues still de#ated a"ongst scientists
/8o#inson et al.$ (22>0. Moreoer$ tests
indicate that FT diesel is #iodegrada#le
/Sch!a#erg et al.$ (22>0. Thus$ the erdict on
the ia#ility of FT synfuels fro" an
eniron"ental perspectie is far fro" a
certain negatie$ inspite of the high C<
*
e"issions.
'. Conclusions
<!ing to the a#undance of natural gas and
coal reseres$ the search for a practical use of
stranded natural gas reseres and the
ersatility of the process in #eing a#le to
produce a range of products under different
conditions$ the Fischer Tropsch process is
e4periencing a rene!ed interest. 9ifferent
types of unit operations$ especially reactors$
are in e4istence and in use for different target
products.
The lo! te"perature FT process$ "ost
suited to diesel production$ is usually run !ith
the aid of a slurry #ed reactor. Co#alt #ased
catalysts$ inspite of their higher cost$ are "ore
suita#le than iron #ased ones #ecause of the
su#stantially larger conersion they achiee.
.n future$ o4ygen consu"ption and the
ther"al efficiency of the FT synthesis could
#e i"proed #y process i"proe"ents.
The oerall outloo% for a ne! FT plant$
especially one ai"ed at diesel production$ is
positie. FT diesel is not only of a ery high
-uality /large cetane nu"#er and lo!
percentage of i"purities0$ #ut also easily
adapta#le to the e4isting infrastructure$ #oth n
ter"s of transportation and end use.
Moreoer$ the ersatility of the FT process in
#eing a#le to produce a range of products #y
"erely altering process conditions !ithout
large ariations in the flo!sheet or unit
operations further i"proes the prospects of
recoering inest"ent ad "a%ing profit.
Go!eer$ the large capital cost of the plant$
and its co"paratie energy inefficiency$ are
notes of caution that "ust #e ta%en account
of.
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