ISSN 00231584, Kinetics and Catalysis, 2012, Vol. 53, No. 6, pp. 742–746. © Pleiades Publishing, Ltd., 2012.

Original Russian Text © A.Yu. Krylova, 2012, published in Kinetika i Kataliz, 2012, Vol. 53, No. 6, pp. 790–795.

RUSSIAN CONGRESS ON CATALYSIS—RUSCATALYSIS

(OCTOBER 3–7, 2011, MOSCOW)

Fischer–Tropsch Synthesis Catalysts as the Core of the Strategy

for Obtaining Synthetic Liquid Fuels
A. Yu. Krylova
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
email: krylova@ips.ac.ru
Received February 7, 2012

Abstract—The Fischer–Tropsch synthesis is a practically significant reaction catalyzed by Fe and Co, which
are active at different H2 : CO ratios of 0.5 and 2, respectively. For this reason, Fecontaining catalysts are
preferentially used in coaltoliquids (CTL) and biomasstoliquids (BTL) processes, while Cocontaining
catalysts are preferred for the gastoliquids (GTL) technology. With the Fe catalysts, which are remarkable
for their high CO2 formation selectivity, it is appropriate to carry out the carbon dioxide reforming of the feed
stock.
DOI: 10.1134/S0023158412060067

The Fischer–Tropsch synthesis is the second stage
in most processes used in obtaining synthetic fuel. It is
essential that it can be carried out with any organic
feedstock (natural gas, oil gas, coal, peat, biomass,
etc.), which is initially subjected to oxidative reform
ing into synthesis gas (carbon monoxide + hydrogen
mixture). The oxygen introduced into the oxidizer at
the first stage of the process is withdrawn at the second
stage as Н2О or СО2 simultaneously with hydrocarbon
formation.
The development of natural gas, coal, and biomass
conversion processes for energy generation stimulates
the development of technologies aimed at chemical
utilization of alternative raw materials. These are gas
toliquids (GTL), coaltoliquids (CTL), and biom
asstoliquids (BTL) processes. In turn, interest in
these processes attracts keen attention to the Fischer–
Tropsch synthesis and its development at the new level.
The Fischer–Tropsch synthesis is a catalytic poly
merization process taking place in the presence of a
Group VIII metal (mainly Co or Fe). The catalyst
used in this reaction determines the syngas synthesis
method and composition, the yield and composition
of the resulting hydrocarbons (desired product), the
necessity and way of upgrading the product, the oxy
gen withdrawal method, and even the way of utilizing
water and СО2.
Natural gas reforming can be carried out using oxy
gen (pure oxygen or air), water, or carbon dioxide as
the oxidizer. These reactions are described by the fol
lowing chemical equations [1]:
СН4 + 1/2О2 ↔ СО + 2Н2, (I)
СН4 + Н2О ↔ СО + 3Н2,
СН4 + СО2 ↔ 2СО + 2Н2.
In partial methane oxidation (reaction (I)), the
CO : H2 molar ratio in the synthesis gas is 1 : 2. Steam
methane reforming (reaction (II)) affords a synthesis
gas still richer in hydrogen (CO : H2 = 1 : 3). The car
bon dioxide reforming of methane (reaction (III))
yields a synthesis gas with an equimolar ratio of the
components.
The formation of hydrocarbons from CO and Н2 can
be described by the following chemical equation [2]:
СО + 2Н2 ↔ [–СН2–] + Н2О. (IV)
The stoichiometric molar CO : Н2 ratio in this
reaction is 1 : 2. The most appropriate process for
obtaining synthesis gas of this composition is partial
methane oxidation (reaction (I)). Simple calculations
demonstrate that, in the case of complete CO conver
sion, it is possible to derive 208.5 g of hydrocarbons (in
terms of СН2 groups) from 1 m3 of synthesis gas. The
synthesis gas obtained by steam methane reforming
(reaction (II)) contains more hydrogen than is dic
tated by the stoichiometry of the Fischer–Tropsch
reaction and, therefore, needs conditioning (correc
tion of its composition). Naturally, the theoretical
hydrocarbon yield calculated for “stoichiometric”
synthesis gas will then alter. In this case, oxygen is
withdrawn from the reaction zone as water.
A number of side reactions may occur under the
Fischer–Tropsch synthesis conditions, including the
water gas shift reaction [3]:
СО + Н2О ↔ СО2 + Н2. (V)
This reaction is catalyzed by transition metal oxides,
such as iron oxide, which is the main component of
the Fischer–Tropsch synthesis catalyst [3]. With the
(II) Fe catalysts, even “dry” Fischer–Tropsch synthesis
(yielding no water) is possible when the water gas sift
(III) reaction occurs at a high rate. The dry synthesis is

742
 FISCHER–TROPSCH SYNTHESIS CATALYSTS AS THE CORE 743

described by the following overall equation, which Weight fraction

includes Eqs. (I) and (II):
2СО + Н2 ↔ [–СН2–] + СО2. (VI)
The “dry” synthesis needs a COrich synthesis gas
(CO : H2 = 2 : 1 mol/mol). In this case, the theoretical
yield of hydrocarbons is again 208.5 g/m3, but half the
CO contained in the synthesis gas is used to remove
oxygen as СО2. If the synthesis gas obtained by partial
methane oxidation is used in the “dry” synthesis, this
synthesis will yield a twice smaller amount of hydro
carbons (104 g/m3), because half the carbon of the
synthesis gas will again turn into СО2. Thus, the Fis
cher–Tropsch synthesis over the Fe catalysts needs a
COrich synthesis gas, and oxygen is withdrawn from
the reaction zone via СО2 formation. Obviously, in this
case it is appropriate to produce synthesis gas by car
bon dioxide or steam–oxygen reforming of methane.
This will exclude or reduce СО2 emissions to the
atmosphere and a waste of carbon from the feedstock.
The Fischer–Tropsch synthesis always yields a
wide variety of products, including gases (С1–С4
hydrocarbons and СО2), liquids (С5–С18 hydrocar
bons, water, and oxygencontaining byproducts:
alcohols, ketones, and aldehydes), and solids (С19+
hydrocarbons). During the synthesis, these com
pounds dissolve in one another and mix, yielding com
mon phases. Particular groups of products are then
separated out of these phases, including the following
hydrocarbon fractions: gasoline (С5–С10 hydrocar
bons), diesel oil (С11–С18 hydrocarbons), and wax
(С19+ hydrocarbons).
The Fischer–Tropsch synthesis kinetics is deter
mined by the growth of the hydrocarbon chain via the
successive addition of СН2 or CHOH groups on the
catalyst surface. Under the assumption that the prob
ability of chain propagation and termination is inde
pendent of the chain length, the proportions of partic
ular hydrocarbons can be calculated using the Ander
son–Schulz–Flory distribution equation [4, 5]:
Wn = n(1 – α)2αn – 1,
where Wn is the weight fraction of the hydrocarbon
containing n carbon atoms and α is the quantity char
acterizing the chain propagation probability.
Knowing α, it is possible to calculate the total
product distribution. By substituting the values of α
and n into the Anderson–Schulz–Flory equation, one
can determine the amounts of individual hydrocar
bons and product fractions forming from CO and Н2
(Fig. 1). The Anderson–Schulz–Flory equation is fre
quently used in calculating the total material balance
of the process.
The value of α characterizes the polymerizing
properties of the catalyst and depends on its composi
tion and operating conditions.
The Anderson–Schulz–Flory equation poses lim
itations on the molar mass distribution of the Fischer–
Tropsch synthesis products [6]: the proportion of the
gasoline fraction (С5–С10) cannot exceed 48%, and
1.0
C1–C4
0.8
C19+
0.6 CH4
0.4 C5–C10
C11–C18
0.2
0 0.2 0.4 0.6 0.8 1.0
α
Fig. 1. Distribution of Fischer–Tropsch synthesis products.
the proportion of the diesel fraction (С11–С18) cannot
be larger than 39%. Methane and wax (С19+) can be
obtained with 100% selectivity.
Thus, the target products of the Fischer–Tropsch
synthesis—gasoline or diesel fraction of liquid hydro
carbons—cannot be obtained by this method with a
selectivity higher than 50%. However, the possibility of
selectively synthesizing wax allows the yield of middle
distillates to be substantially raised. In this case, the
process is carried out in two stages (scheme). At the
first stage, such catalysts are used with which it is pos
sible to produce the maximum amount of wax (α >
0.9). At the second stage, this wax is subjected to
hydrocracking or hydroisomerization. The total yield
of the С11–С18 fraction from the Fischer–Tropsch
synthesis and hydrocracking can be over 70%. For the
first time, this method of synthesis of middle distillates
was suggested by Shell Co. and was commercialized in
Malaysia [7].
Routes for obtaining middle distillates from CO
and Н2:
Route I
Synthesis gas Fraction C11–C18 <39%
Route II
Fraction C11–C18 Fraction C +
19
>70%
Scheme.
The route involving hydrocracking or hydroi
somerization provides means to vary the composition
of the middle distillate. There are two variants of this
process. In the first variant, which is aimed at produc
ing diesel fuel, the following liquid fractions are
obtained (wt %): naphtha, 15; kerosene, 25; diesel
fuel, 60. The second variant of the process is designed
for obtaining kerosene as the main fraction. Its prod
uct has the following fractional makeup (wt %): naph
tha, 25; kerosene, 50; diesel fuel, 25.

KINETICS AND CATALYSIS Vol. 53 No. 6 2012

744 KRYLOVA

Basic characteristics of diesel fuel and jet kerosene obtained by middle distillate synthesis [8]
Characteristic
Middle dis
tillate boling range, density (15°C), aromatics, sulfur, isoparaffins, smoke point, cloud cetane
°С kg/m3 ppm ppm wt % mm point, °C number’
Kerosene 150–180 750 0 0 >70 125 –30 –
Diesel fuel 180–360 800 0 0 – – –20 75

Note that the synthetic middle distillates obtained
via the Fischer–Tropsch synthesis are similar in prop
erties to the corresponding petroleum products
(table), but they are superior to the latter in that they
are almost free of sulfur, nitrogen, and aromatic com
pounds.
Shell Co. has carried out extensive tests of synthetic
middle distillates as motor fuels [9]. Furthermore, a
Boeing cargo aircraft of the US armed forces, fueled
by synthetic kerosene, has accomplished a Transamer
ica flight. These tests confirmed that kerosene and die
sel fuel obtained by the synthesis of middle distillates
can be used as motor fuels.
There are two variants of the Fischer–Tropsch syn
thesis, namely, low and hightemperature ones [10].
The lowtemperature synthesis is conducted at
<250°С in the presence of a Co or Fe catalyst. The
comparatively low temperature is favorable for the for
mation of heavier hydrocarbons [11], so liquid hydro
carbons and wax are mainly obtained under these con
ditions. This variant is usually carried out with cata
lysts yielding products with large α values of >0.9. The
lowtemperature Fischer–Tropsch synthesis is most
often used as the first stage of middle distillate synthe
sis. It is generally recommended for natural gas
reforming yielding the smallest possible proportion of
gaseous products. The hightemperature synthesis is
performed at 320–350°С in the presence of a Fe cata
lyst. Under these conditions, the synthesis affords ole
finrich hydrocarbon mixtures that are usable as a
feedstock in a wide variety of petrochemical processes
(alkylation, hydrogenation, oligomerization, sulfo
chlorination, etc.). The hightemperature variant is
commonly recommended for use as a step of industrial
coal and biomass processing, because COrich syn
thesis gas is used to carry out the Fischer–Tropsch
synthesis over Fe catalysts.
The Fischer–Tropsch synthesis is a very exother
mic process (ΔН227°С = –165 kJ/mol) [2]. The neces
sity of efficient heat removal causes difficulties in its
practical implementation. For this reason, the reac
tion is conducted in reactors that most completely sat
isfy the heat removal requirement [12]. These include
fixedbed, fluidizedbed, and slurry reactors (Fig. 2).
Shellandtube fixedbed catalytic reactors (Fig. 2a)
were the first to be used in the Fischer–Tropsch syn
thesis. They are presently employed by Shell Co.
(Malaysia) and Sasol Co. (Sasol1, South Africa) in
the lowtemperature synthesis in the presence of Co
and Fe catalysts. The size of the porous catalyst gran
ules placed inside the tubes of the apparatus is typically
2–4 mm, and this leads to a strong effect of internal
diffusion on the Fischer–Tropsch synthesis [13].
Obvious advantages of this type of reactor are that the
flowthrough process is comparatively easy to carry
out, the reaction products are easy to separate from the

Synthesis gas in

Products out Gaseous

products out

Liquid products
+ catalyst out

Synthesis gas in
Products out Synthesis gas in
(а) (b) (c)

Fig. 2. Fischer–Tropsch synthesis reactors [12]: (a) shellandtube reactor, (b) fluidizedbed catalytic reactor, and (c) slurry reactor.

KINETICS AND CATALYSIS Vol. 53 No. 6 2012

 FISCHER–TROPSCH SYNTHESIS CATALYSTS AS THE CORE
catalyst, and the product is not contaminated with
small catalyst particles. Another advantage of these
apparatuses is that they van readily be scaled up by
increasing the number of reactor tubes inside the com
mon shell. However, longterm operation of shell
andtube reactors revealed their drawbacks: the cata
lyst is difficult to load into, and unload from, the reac
tor (the reduced catalyst us pyrophoric); there are
large temperature and pressure gradients across the
catalyst bed; the heat transfer area is small. In addi
tion, the reactors of this type designed for high output
rates (>30000 bbl/day) are very large and are difficult
to transport.
Some of the drawbacks inherent in fixedbed cata
lytic reactors can be eliminated by using fluidizedbed
or slurry reactors (Figs. 2b, 2c). These apparatuses
ensure intensive heat removal and ease of catalyst
loading and unloading. In addition, with catalyst pow
ders with a particle size of 50–150 µm, there is no
internal diffusion effect on the Fischer–Tropsch syn
thesis.
Reactors with a fluidized bed of a circulating Fe
catalyst powder (Fig. 2b), which are analogues of
widespread industrial catalytic cracking apparatuses,
were commercialized by Sasol Co. (Sasol1 and Sasol3,
South Africa). Advantages of the fluidizedbed cata
lytic reactors include, in addition to intensive heat
transfer, the possibility of creating a highcapacity unit
processing line. These apparatuses are employed in the
hightemperature Fischer–Tropsch synthesis. The
main drawbacks of the fluidizedbed catalytic reactors
are the necessity of maintaining the catalyst bed in the
fluidized state, control difficulties, and the short ser
vice life of the catalyst (1.5 months) because of its
abrasion. Furthermore, the scalingup of these appa
ratuses causes certain problems associated with the
difficulties in producing a fluidized bed.
A promising method for obtaining solid paraffins is
hydrocarbon synthesis over a powdered catalyst sus
pended in a liquid. Here, the catalyst bed is suspended
by feeding synthesis gas and/or an inert gas from the
bottom of the reactor. This generates a gas–liquid–
solid threephase system. Reactors of this type (slurry
reactors) are hollow vessels filled with a catalyst sus
pended in the molten paraffins resulting from the syn
thesis. Synthesis gas is entered at the bottom as a
stream or bubbles. Forced agitation in the reactor is
ensured by stirrers, by introducing an extra amount of
a gas, or by the “boiling” of the bubbles. Slurry reac
tors are used to carry out the lowtemperature Fis
cher–Tropsch synthesis, mainly in the presence of Co
catalysts. It is this Fischer–Tropsch technology that
has been put forward by the designers of new GTL
processes (Sasol, ExxonMobil, Assens, etc.). This
technology offers the following advantages: its output
capacity is high compared to that of the fixedbed cat
alytic reactors and is comparable with that of the flu
idizedbed catalytic reactors; the heavy products
(wax) are removed from the catalyst through their dis
KINETICS AND CATALYSIS Vol. 53 No. 6 2012
745
solution in the liquid phase. The disadvantages of the
threephase process include the problems inherent in
fluidized beds (complicated apparatus and scalingup
difficulties), as well as the long time to equilibrium in
the system and the relatively rapid poisoning of the
catalyst by catalyst poisons (primarily with sulfur).
Experience in use of Fe and Co catalysts in the Fis
cher⎯Tropsch synthesis allows their properties to be
compared. Other conditions being equal, the hydro
carbon yield with the Fe catalysts is lower than with Co
catalysts. Because of the high rate of the water gas shift
reaction, oxygen is removed from the surface of the Fe
catalysts as СО2, so part of the carbon goes to waste.
On the other, a significant advantage of the iron cata
lysts is their relative cheapness. The price of cobalt in
the foreign market is now $70000 per ton [14]. At the
same time, the price of iron items (wire, nails, etc.)
does not exceed $1000 per ton [15].
The reaction over the Fe catalysts is carried out
with COrich synthesis gas and yields hydrocarbon
mixtures rich in light olefins. The Co catalysts are
more expensive, but they more efficiently convert the
carbon of the feedstock into carbon of the liquid prod
ucts. In addition, they show a higher paraffin, particu
larly wax, formation selectivity, with α reaching a
value of 0.8 and above. For this reason, they are rec
ommended for the synthesis of middle distillates. Over
the long history of the development of the GTL pro
cess, the Co catalyst have been preferred in the Fis
cher–Tropsch synthesis.
The development of processing technologies for
coal, and particularly for biomass, which has drawn
great attention in recent years, brings the Fe catalysts
to the forefront. These systems can be used with CO
rich synthesis gas, arte more stable, and provide means
to carry out the “dry” Fischer–Tropsch synthesis. The
Fe catalysts have been used by Sasol Co, (South
Africa) for several decades. They are employed in the
low and hightemperature Fischer–Tropsch synthe
ses, making it possible to combine these processes in a
single processing cycle, to widen the product range,
and to reduce the product cost.
Today, the most promising Fischer–Tropsch tech
nology is the synthesis in the gas–liquid–solid three
phase system in the presence of a catalyst suspended in
highboiling liquid hydrocarbons. Maintaining the
stability of this slurry system involves some technical
difficulties because of the complicated hydrodynamics
of the process and the proneness of the slurry to sepa
ration. Powdered catalysts with a particle size below
0.1 µm (submicron or nanosized particles) provide
means to stabilize the system considerably and to reduce
the internal diffusion limitations for the reaction.
The Topchiev Institute of Petrochemical Synthesis
(Russian Academy of Sciences) has developed cata
lysts with a particle size of ~500 nm that are prepared
and activated in situ by decomposing their precursors
in a hydrocarbon medium at 300°С. Below, we list the
process characteristics attained under the optimal Fis
746 KRYLOVA
cher–Tropsch synthesis conditions in the presence of
a nanosized 100Fe : 8Al2O3 : 3K2O (w/w) catalyst [16]:
Conditions
pressure, atm 20
temperature, С° 315
CO : H2 molar ratio 1 compact apparatuses at modular plants for converting
gas flow rate, nL/(g Fe h) 4.2
amount of Fe in the liquid phase, wt % 6 ing with natural petroleum in a petroleum pipeline.
Process characteristics
CO conversion, % 87
TOF, s–1 0.1
C5+ yield, g/m3 117
C5+ selectivity, % C 50
C5+ selectivity (without CO2 taken into account), 81
%C
C5+ productivity, (g C5+)/(kg Fe h) 438
Fractional composition of C5+, wt %
С5–С10 76
С11–С18 18
С19+ 6 6. Bellussi, G. and Zennaro, R., Encyclopedia of Hydro
α 0.63
Olefin content, % 45
n/iso ratio 4 clopedia/inglese/inglese_vol_3/161182_ing.pdf
Oxygenate content of the aqueous layer, % 14
A comparison between the properties of the 100Fe :
8Al2O3 : 3K2O (w/w) catalyst and those of the catalysts
developed by, e.g., Mobil and Reinpreussen PL Cos.
For the Fischer–Tropsch synthesis in the threephase
system [17] demonstrates that the nanosized catalyst is
more selective in terms of the formation of liquid
products at the same CO conversion level. (The selec
tivity of the industrial catalysts without СО2 taken into
account did not exceed 70%.) In addition, the nano
sized catalyst allowed a higher gas flow rate and
afforded a higher liquid hydrocarbon productivity of
up to 438 (g С5+)/(kg Fe h), which is 90–190 (g С5+)/
(kg Fe h) higher than the productivity of the industrial
catalysts.
A specific feature of the synthesis over the catalysts
developed at the Topchiev Institute of Petrochemical
Synthesis is that it is possible to obtain hydrocarbon
mixtures free of solid products. In the slurry reactors,
the hydrocarbon products do not accumulate and the
composition of the liquid phase practically does not
vary. Thus, it is unnecessary to continuously remove
the liquid phase with the catalyst dispersed in it from
the reaction zone or to separate the catalyst from the
reaction products. This markedly facilitates the tech
nical implementation of the process. The catalysts
containing Fe nanoparticles are activated under mild
conditions (300°С), obviating the need for hightem
perature reduction.
Use of nanosized catalyst particles substantially
facilitates the process, since, in this case, it is unneces
sary to maintain the catalyst particles suspended uni
formly over the entire reactor height and it is easier to
perform hydrodynamic calculations in reactor model
ing. The above facts suggest that the Fischer–Tropsch
synthesis using iron nanoparticles can be carried out in
oil gas into light synthetic petroleum suitable for mix
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