Applied Catalysis A: General 186 (1999) 27–40

Fischer–Tropsch technology — from active site to commercial process

J.J.C. Geerlings a,∗ , J.H. Wilson a , G.J. Kramer a , H.P.C.E. Kuipers a , A. Hoek a , H.M. Huisman b
a Shell International Oil Products B.V., Shell Research and Technology Centre, P.O. Box 38000, 1030 BN Amsterdam, The Netherlands
bShell International Chemicals B.V., Shell Research and Technology Centre, P.O. Box 38000, 1030 BN Amsterdam, The Netherlands

Abstract
An overview of current research at Shell in the area of Fischer–Tropsch technology is given covering the full range from a
detailed understanding at the atomic level right up to the commercial process. Studies of model catalysts under Fischer–Tropsch
reaction conditions are reviewed, which have yielded new information on the nature of the active site. A recently developed
kinetic network is described which couples these model catalyst studies to the macroscopic world of ‘real catalysts’. Finally,
the advantages and disadvantages of various suitable reactor types will be discussed, with the emphasis placed on a comparison
between multitubular fixed bed and slurry type reactors. ©1999 Elsevier Science B.V. All rights reserved.
Keywords: Fischer–Tropsch reaction; Synthesis gas

1. Introduction the Fischer–Tropsch step should aim to utilise synthe-

Fischer–Tropsch technology forms the heart of
many natural gas conversion processes which have
been developed by various companies in recent years
[1]. In these processes, natural gas is first of all par-
tially oxidised to yield a mixture of carbon monoxide
and hydrogen, generally referred to as synthesis gas.
The Fischer–Tropsch reaction forms the second step,
in which synthesis gas is converted into a mixture
of mainly long straight chain paraffins with water as
a by-product. In the final step these hydrocarbons
undergo further hydrogenation or hydrocracking to
yield clean middle distillates as products.
It is well known that the economic viability of gas
conversion is determined by capital costs and average
product price. In this respect it should be realised that
the manufacture of synthesis gas is by far the most
capital intensive part of a gas conversion plant. Hence,
∗ Corresponding author.
sis gas as efficiently as possible. Selectivity consider-
ations are thus extremely important in the design of
the Fischer–Tropsch section of a gas conversion plant.
For a plant producing only middle distillates, the C5+
selectivity (i.e. the fraction of pentanes and heavier
hydrocarbons in the total product) should be as high
as possible. If olefins or waxes are co-produced, then
their selectivities should be optimised simultaneously.
Most reviews of Fischer–Tropsch technology sep-
arate catalyst development and reactor technology.
However, one of the main messages of this paper is
that to achieve an optimum in performance for the
complete process, the catalyst and the reactor should
be optimised in a combined fashion. The first part
of this paper is devoted to reviewing our fundamen-
tal studies of model catalysts under Fischer–Tropsch
reaction conditions. State-of-the-art surface science
techniques have been employed to yield information
on the relationship between the surface atomic struc-
ture of model catalysts and their performance in the

0926-860X/99/$ – see front matter ©1999 Elsevier Science B.V. All rights reserved.
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28 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
Fischer–Tropsch reaction. These studies represent
part of the scientific basis on which the development
of our Fischer–Tropsch catalysts is founded. Next, we
switch from this microscopic picture to a macroscopic
kinetic description of the Fischer–Tropsch reaction.
This kinetic network bridges the gap between the
world of model catalysts and the complex supported
catalysts used in practice. We briefly review exist-
ing kinetic models of the Fischer–Tropsch reaction,
which are compared to our own approach. In the last
part of this paper, we deal with reactor technology.
The advantages and disadvantages of various suitable
reactor types are discussed, with particular attention
paid to both slurry and fixed bed technologies.
2. Basic research on the Fischer–Tropsch synthesis
Heterogeneous catalysts for industrial applications
often consist of a porous inorganic material which is
used to support small metal particles. By dispersing
the metal in this way, a large total area of metal sur-
face is available at which catalytic reactions can oc-
cur. For high catalytic conversions, a high metal par-
ticle dispersion is desirable, particularly for reactions
showing a low ‘turnover number’ (defined as the num-
ber of reactant molecules converted per surface metal
site per second). It is also possible to influence the
state of the catalyst surface by the addition of separate
promoter species. There are a large number of dif-
ferent ‘recipes’ used for the preparation of heteroge-
neous catalysts. The inherent compositional and struc-
tural inhomogeneity of these supported systems makes
the problem of identifying the underlying reasons for
their catalytic performance extremely difficult. Such
knowledge is essential for placing the development
and optimisation of catalysts for industrial processes
on a scientific, as distinct from empirical, basis [2].
In order to reduce the level of complexity, a com-
mon approach is to study model catalysts such as
single-crystal metal surfaces [3,4]. With the contin-
uing improvement of modern surface science tech-
niques, the preparation and characterisation of clean
and well-defined metal surfaces under ultra-high vac-
uum (UHV) conditions has now become a routine task.
Much effort over the past two decades has been de-
voted to the effect of exposing metal surfaces to differ-
ent molecules. It is now known that the adsorption of
molecules from the gas phase can seriously influence
the atomic structure of metal surfaces, causing a range
of adsorbate-induced restructuring effects [5–7]. Most
catalytic reactions take place at elevated temperatures
and pressures. It is therefore, questionable whether the
results obtained in a UHV experiment can be usefully
related to phenomena occurring under catalytic reac-
tion conditions. This problem can be partially circum-
vented by combining a UHV system with a high pres-
sure reaction cell. In this approach, the model cata-
lyst is given a similar treatment to that encountered in
practice and can subsequently be transferred back to
UHV for detailed surface analysis, without the need
to expose the surface to ambient conditions. To make
the direct link between structure/composition and cat-
alytic performance, in-situ methods are obviously pre-
ferred. Unfortunately, there are only a few in-situ anal-
ysis techniques available which can be applied to char-
acterise catalyst surfaces under high pressure and high
temperature conditions. One of the few in-situ tech-
niques available, which is especially useful in model
catalyst studies, is polarisation modulation reflection
absorption infrared spectroscopy (PM-RAIRS) [8].
We will describe below how cobalt surfaces be-
have under Fischer–Tropsch reaction conditions. We
will give a summary of the main results, the details of
which can be found in the original publications [8–10].
The experiments were performed in two experimental
set-ups, both of which combine a high-pressure reac-
tion cell with a UHV system equipped with a num-
ber of techniques, including X-ray photoelectron spec-
troscopy (XPS) and facilities for sample preparation.
One of the UHV systems is additionally equipped with
a scanning tunneling microscope (STM).
A Co(0001) surface has been studied with in-situ
PM-RAIRS and ex-situ STM. The experiments clearly
show the dynamical structural nature of a model cat-
alyst surface under practical CO hydrogenation reac-
tion conditions. It appears that the number of surface
defects is linked to the activity in the Fischer–Tropsch
reaction.
2.1. The restructuring of Co(0001) under
Fischer–Tropsch reaction conditions
Fig. 1(a) shows a STM image of the atomically flat
terraces of a clean Co(0001) surface separated by steps
J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40 29
30 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40

Fig. 2. STM images of the restructured Co(0001) surface after 1 h exposure to high-pressure CO hydrogenation conditions showing (a)
two distinct levels separated by monoatomic steps, and covered with small island features which exhibit a remarkably narrow lateral size
distribution with a mean diameter of 1.75 nm, and (b) straight step edges with parallel island-free zones clearly visible on the upper step
edge. The image in (a) is a plan view representation of the data shown in Fig. 1(b). Taken from Ref. [9].
 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
of varying height. After exposoure to synthesis gas
(H2 /CO = 2) at a reaction temperature of 523 K and
a pressure of 4 bar the surface structure has changed
considerably. Fig. 1(b) shows the surface at a higher
magnification after 1 h of reaction. The surface now
appears covered with a high density of similarly sized
particles. The average particle diameter is 1.75 nm.
The same image is shown in plan view in Fig. 2(a).
The upper level is just one atomic step higher than
the lower level while, for a given layer, the particles
are of almost identical height. We have interpreted the
particles observed in STM as small islands of cobalt
atoms occupying the threefold hollow sites of the un-
derlying close packed terrace. From the mean island
diameter and the nearest neighbour distance for bulk
cobalt (0.25 nm), the fraction of all cobalt atoms in the
uppermost atomic layer occupying edge sites is calcu-
lated to be around 50%.
The STM images show that a surface restructuring
process has taken place as a result of the high pressure
and high temperature treatment. Similar island struc-
tures have not been seen on the clean surface follow-
ing annealing. A close examination of the structure
near steps gives an indication of the mechanism of
surface restructuring. First, we observe straight steps
with a low kink density compared to the clean surface.
Second, parallel to the upper edges of these straight
steps, we find a clear empty zone where cobalt islands
do not occur. This can be clearly seen in Fig. 2(b),
for example. Both observations are consistent with an
etch-regrowth restructuring mechanism, which does
not necessarily require a net loss of cobalt atoms via
the gas phase. In summary, the STM results provide
direct evidence that the surface of Co(0001) under-
goes a massive restructuring under Fischer–Tropsch
reaction conditions. As a result of this restructuring
process, a large fraction of the surface cobalt atoms is
occupying edge sites.
To get a better insight into the surface restructur-
ing process as observed by STM, the adsorption be-
haviour of CO on Co(0001) was further studied with
PM-RAIRS. Fig. 3 shows a number of PM-RAIR spec-
tra as obtained after adsorption of CO on an annealed
Co(0001) surface and a defective Co(0001) surface,
respectively. The defective surface has been created
via argon bombardment without subsequent anneal-
ing. The annealed surface shows only a one symmet-
ric signal after 10 Langmuir CO, which is associated
31
Fig. 3. Sequence of PM-RAIR spectra taken under pure CO on
an annealed (solid line) and a defective Co(0001) surface (broken
line).
with CO adsorbed at well-ordered terrace sites. In ad-
dition to this peak the defective surface shows a pro-
nounced shoulder at higher frequencies, which has
been attributed to CO adsorbed on defect sites [8,10].
This qualitative picture remains the same when the
CO pressure is increased to 100 mbar at room temper-
ature. For the defective surface most of the intensity
now appears in the highest frequency peak, which has
shifted to 2080 cm−1 . The main observation of this
series of measurements is that this defect peak also
starts to develop in the spectrum taken from the an-
nealed surface, after the temperature is increased at
constant CO pressure to 493 K. This observation is
in qualitative agreement with the STM results, which
revealed extensive roughening of the surface after a
similar treatment in synthesis gas.
Fig. 4 shows another sequence of PM-RAIR spec-
tra taken from a sputtered Co(0001) surface. At
298 K under 100 mbar of pure CO, the defect peak
at 2080 cm−1 dominates the spectrum. No significant
change in the PM-RAIR spectrum is observed when
an additional 200 mbar of hydrogen is added at 298 K.
The rest of the sequence in Fig. 4 shows the effect
of raising the temperature stepwise to 490 K under
synthesis gas (H2 /CO = 2). The sharp defect peak at
2080 cm−1 shows a large decrease in intensity with in-
creasing temperature, accompanied by a small shift to
lower frequencies. At 490 K, the peak has totally dis-
32 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
Fig. 4. Sequence of PM-RAIR spectra taken on a sputtered
Co(0001) surface. The starting conditions were 100 mbar of CO
at 298 K; 200 mbar of H2 was then added and the temperature in-
creased stepwise to 490 K. It can be seen that the absorption signal
due to CO attached to defect sites is removed in an irreversible
process.
appeared. The peak at about 2020–2060 cm−1 shows
an increase in intensity with increasing temperature
and is similarly accompanied by a shift to lower fre-
quencies. Upon lowering the temperature to 298 K the
2080 cm−1 absorption signal does not appear again, a
clear indication of the irreversibility of the process.
The behaviour of the defect peak at 2080 cm−1 is a
central result of the PM-RAIRS studies. The results of
Figs. 3 and 4 clearly show that defects can be created
by annealing a Co(0001) surface in a high-pressure
CO environment or, in higher concentrations, by di-
rectly roughening the surface through argon sputter-
ing. As can be seen in Fig. 4, heating in synthesis gas
instead of pure CO, does not lead to the creation of
a corresponding defect CO signal in RAIRS. Given
the STM observation that surface defects are created
during annealing of Co(0001) in synthesis gas, one
is led to the conclusion that these defects sites are
apparently unable to adsorb CO to a measurable ex-
tent under synthesis gas at 490 K. The interpretation
of these results is that these defect sites are occupied
by hydrocarbons under Fischer–Tropsch reaction con-
ditions and obviously not in a pure CO atmosphere.
In agreement with this interpretation ex-situ XPS re-
veals the presence of hydrocarbons on the surface. In
addition to these analytical results, kinetic measure-
ments under similar conditions showed that a sputtered
Co(0001) surface is approximately a factor 5–10 more
active than the annealed surface. Taken in combina-
tion with the STM, PM-RAIRS and XPS results, the
kinetic measurements constitute clear evidence that
defects are active sites for hydrocarbon synthesis in
the Fischer–Tropsch reaction, an observation that is of
obvious importance in the process of developing im-
proved Fischer–Tropsch catalysts.
3. A quantitative kinetic model for FT catalysis
on pure cobalt
The experimental results described above, which
clearly show that cobalt surfaces are dynamic under
Fischer–Tropsch reaction conditions, do not preclude
a macroscopic kinetic description of their steady-state
catalytic behaviour. Over the past 5 years, we have
actively sought to find an unambiguous description of
Fischer–Tropsch kinetics, based on well defined model
experiments [11,12]. To this end, we have developed
a differential reactor in which flat model catalysts can
be tested. We are now in a position to measure product
distributions up to C20 from a 20 cm2 catalyst surface
at CO conversion levels less than 1% and at pressures
between 1 and 20 bar [13]. Such measurements, some
of which will be presented in this section, are ideal
for the development and testing of kinetic hypothe-
ses and conceptual models. Only by using experimen-
tal data from such dedicated model experiments, one
can overcome the intrinsic difficulty that complicates
any description of the FT process, namely the sub-
tle interplay between chemical kinetics and the phys-
ical (transport) properties of product molecules rang-
ing from methane to ‘polyethylene’.
In this section, we present the outline of a kinetic
model for the FT synthesis which has been fully quan-
tified based on kinetic measurements of cobalt foils.
3.1. Elements of the kinetic model
The general consensus is that the Fischer–Tropsch
reaction is a combination of the following elemen-
tary chemical processes. To begin with, chemisorbed
 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40 33

methyl species are formed by means of CO dissocia-

tion and stepwise addition of hydrogen atoms. These
methyl species can either undergo methanation or al-
ternatively act as initiators for chain growth. Chain
growth occurs via sequential addition of CH2 groups
while the growing alkyl chain remains chemisorbed
to the metal by means of a terminal methylene group.
At any point during this chain growth process ter-
mination may occur to give either an ␣-olefin (via
␤-hydrogen elimination) or an n-paraffin (via primary
␣-hydrogenation). The resulting paraffins are assumed
to be inert: the known occurrence of hydrogenolysis Fig. 5. Graphical illustration of the kinetic network.
reactions can be neglected under normal process con-
ditions. In contrast, ␣-olefins are able to re-enter the thickness δ, mass balance in the liquid phase requires
FT chain growth process by reversing the chain ter- that:
mination step (so-called ‘reinsertion’). Alternatively,
␣-olefins may undergo secondary hydrogenation. The d =

ξ = = ξ
relevance of making a distinction between primary and δCn,l = −(kd + kd + h2 )Cn,l + kd Cn,g + kd ξn
dt
secondary hydrogenation will become clear shortly. (2)
For completeness we mention that a variety of initiat-
ing species has been proposed for the Fischer–Tropsch d  0  =
δCn.l = −kd Cn,l
0
+ ka Cn,g
0
+ h1 ξn + h2 Cn,l (3)
reaction; see for instance a recent example proposing dt
vinyl species [14]. In this paper we do not describe
experiments, yielding information on the initiation of where C0 denotes paraffin concentrations. Note that
the reaction. This subject will therefore, not be dis- wax can build up in the reactor (with a rate˙␦) since the
cussed any further. only outlet is via the gas phase. During steady state
A complete kinetic model should ultimately be operation, however, the liquid phase concentrations
based on a Langmuir–Hinshelwood description of the will remain constant. This implies that
elementary reaction steps, which includes a descrip-
tion of the overall rate dependence on reactant/product d

δCn,l = δ̇Cn,l (4)
pressures and temperature 1 . Here, we restrict our- dt
selves to an ‘effective rate’ model. The ingredients of
this model are shown graphically in Fig. 5. Using the Finally, mass balance in the gas phase (for olefins and
notation as shown, mass balances for Cn species in the paraffins alike) gives:
different phases can be set up as follows. They read:  
V d 8
d Cn,g = − ka + Cn,g + kd Cn,l (5)
ξ ξ =
ξn = −(kd + h1 + g)ξn + gξn−1 + ka Cn,l (1) A dt A
dt
where V, A and 8 are the reactor volume, the catalyst
for the chemisorbed phase, where the surface concen-
(or liquid) surface area and the gas flow rate, respec-
tration of a chemisorbed species is denoted by ␰ and
tively. Details of the model and its analysis will be
the liquid (olefin) concentration by C= . For flat model
published elsewhere [16]. It suffices to say at this point
catalysts covered with a homogeneous liquid layer of
that the model can be solved analytically in the form
of recursive relations between the Cn and the Cn + 1
1 In the literature one finds two type of kinetic descriptions. The
species.
first one is of the type discussed here and most references in As described in Ref. [16] the gas–liquid equilibrium
this paper. The second type does contain Langmuir–Hinshelwood
adsorption terms but is in its predictions typically limited to the
can be quantified by a gas–liquid collision rate with
CO conversion. See e.g. the review by Wojciechowski [15]. sticking coefficient, S, given by:
34 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
r Table 1
kB T
ka = S which @ 220◦ C equals :
2π M
216
ka = √ (m/s) (6)
nc
6◦ in combination with an Arrhenius-type desorption
term. By fitting the data to the gas–liquid equilibrium
of pure C5 –C25 one finds:
kd = kd0 exp(−Ed /kB T ) with
 0
kd = 290 (m/s)
@ 220◦ C : (7)
Ed /kB = 230nc (K)
Note that the desorption energy is proportional to
the number of carbon atoms (nc ); note also that no
distinction is made between paraffins and olefins. The
simple description of Eqs. (6) and (7) predicts the
exponential decrease in hydrocarbon vapour pressure
with carbon number and is accurate within 10%.
It has been pointed out in the literature [17] that
this exponential dependence of the vapour pressure
leads to a critical chain growth parameter, α c , of 0.7
(≈ exp(−230/T)) below which the FT reaction is a
dry process and above which heavy wax is inevitably
present. Under certain experimental conditions (no-
tably low pressure operation) the FT process on a Co
foil too will run under dry conditions. During dry op-
eration, hydrocarbon product molecules evaporate di-
rectly from the cobalt metal surface rather than from
the surface of a hydrocarbon liquid. This leads to an
enhancement in the effective desorption energy Ed /KB .
On the basis of experimental work by Brand et al. [18],
we estimate Ed /KB for evaporation from a metal sur-
face to be 680 K per CH2 -group, i.e. more than twice
as strong. It can be shown [16] that under conditions
of dry operation, the effective desorption energy per
CH2 -group can be anywhere between 230 and 680 K,
depending on the hydrocarbon coverage of what can
then be best described as the hydrocarbon physisorp-
tion layer.
The significance of an explicit quantification of the
gas–liquid equilibrium lies in the fact that, in doing
so, unnecessary freedom in the remaining parameters
is eliminated. In the language of surface science: the
hydrocarbon residence times at the catalyst surface
(or in the liquid) have been fixed in accordance with
experiment (pure-component vapour pressures) so that
they can be unambiguously compared with the various
Reactor and process parameters
Reactor volume V 10 ml
Cobalt surface area A 40 cm2
Reaction temperature 493 K
Gas flow rate @ 1 bar 8 1 Nml/min
@ 18 bar 8 18 Nml/min
Gas residence time 10 min
H2 : CO (syngas) ratio 2
CO conversion @ 1 bar 0.8%
@ 18 bar 0.5%
reaction time scales. These reaction time scales are
quantified in the next section.
3.2. Quantification of Fischer–Tropsch kinetics at 1
and 18 bar syngas pressure
We consider two experiments done sequentially: the
first at 1 bar and the second at 18 bar synthesis gas
pressure. Apart from the difference in total pressure,
all other conditions were kept the same and are sum-
marised in Table 1.
The product spectra at both pressures are shown
in Fig. 6 and show the total yield (i.e. ␣-olefins and
n-paraffins) as a function of carbon number, together
with the n-paraffin to ␣-olefin (P/O) ratio. At 18 bar
this is a complete description; at 1 bar a large num-
ber of isomers is also formed. These are neglected
in the present discussion since they do not affect
its outcome. The drawn lines in Fig. 6 are fits to
the model, presented above, with fixed rate con-
stants for C3+ products (see Fig. 5). Note that for
C1 and C2 we have introduced additional parameters
to describe their respective deviations from ’ideal’
Anderson–Schulz–Flory behaviour for completeness
purposes only. In the present discussion, we are only
interested in the fixed rate constants used to predict
the C3+ product spectrum. The rate constants giving
the best description of the data as shown in Fig. 6 are
summarised in Table 2.
A total of four kinetic parameters only had to be
fitted. These are:
• The effective desorption energy per CH2 unit
(Ed /kB ): This is used to obtain a correct slope for
the P/O ratio, which depends on the surface resi-
dence time of 1-olefin products and hence on the
desorption energy. For the 1 bar experiments, we
obtain a value markedly higher than that of a hy-
 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40 35

Fig. 6. Cn -yield of n-paraffins and a-olefins and the paraffin to olefin (P/O) ratio for a 40 cm2 cobalt foil, at 1 bar and 18 bar total pressures.
Process conditions are given in Table 1.

Table 2
that a de-chemisorbed olefin will re-enter the chain
Kinetic parameters required to fit the experimental data of Fig. 6a
growth process. This produces the characteristic
Quantity Unitb 1 bar 18 bar ‘change in slope’ in the Anderson–Schulz–Flory
Desorption energy Ed /kB K 410 230 (ASF) product distribution, usually referred to as
Liquid layer growth δ̇ d0 /s 0 0.096 ’non-ASF behaviour’. At 1 bar, the yield spectrum
Chain growth probability α∞ – 0.575 0.926 is essentially ASF-like so that only an upper limit
P
TOFCO g · ξn 1/s 0.0146 0.168 ξ
ξ for ka can be given.
De-chemisorption kd /g – 0.76 0.55 ξ
Primary hydrogenation h1 /g – <0.05 0.025 The other parameters, kd and δ̇, are not variables but
ξ
Chemisorption ka d0 /s <100 10 000 fixed by boundary conditions. In the former case, this
Secondary hydrogenation h2 d0 /s 400 1100 is the chain growth probability at high carbon num-
a Only the parameters in bold have to be varied to obtain the fits. bers:
This is the limiting value of the chain growth probability for large ξn g
carbon numbers. α∞ lim = ξ
(8)
b The unit of the liquid-to-surface parameters and of the liquid n→∞ ξn−1 g + h1 + kd (1 − Γ )
layer growth is (m/s). For convenience they have been expressed
in units d0 = 3.25 Å, corresponding to the linear dimensions of a where the -insertion probability, Γ , is given by:
CH2 unit or ‘monolayer’ thickness.
ξ
ka
drocarbon liquid, reflecting ‘dry’ operation under Γ = ξ
(9)
ka + h2 + kd (1 + (ka A/8)) + δ̇
these conditions. Indeed, the model does not pre-
dict any wax build-up in this case. At 18 bar, wax A and 8 are given in Table 1. In the limit of large car-
build-up does occur and the desorption energy is bon numbers, evaporation becomes negligibly small
correspondingly reduced to the liquid value. and 0 reaches a constant value determined by δ̇, which
• The primary hydrogenation rate (h1 ): This deter- itself has a fixed value determined by the condition
mines the P/O level at small carbon numbers. Since that the total liquid density must be identical to that
at 1 bar the P/O line is virtually straight, only an of a F–T liquid (675 kg/m3 ).
upper limit can be given.
• The secondary hydrogenation rate (h2 ): This deter- 3.3. Critical discussion of the kinetic parameters
mines the level of the P/O ratios. Basically, it is ad-
justed so that is equals the effective desorption rate While at first glance the above quantification appar-
for the carbon number at which P/O is unity. ently yields a satisfactory description of the FT pro-
ξ
• The olefin chemisorption rate (ka ). This deter- cess, some severe problems show up on a closer in-
mines the re-insertion probability, i.e. the chance spection of the high pressure data. In particular, the
36 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
Fig. 7. The effective desorption rate kd for the desorption energies
(per CH2 unit) as appropriate for 1 bar (410 K) and 18 bar (230 K),
respectively.
‘change in slope’ around C8 can only be explained
ξ
by assuming unphysically high values for ka . This
can be understood as follows: a change in slope in
an ASF plot must, within the context of the kinetic
model outlined above, necessarily reflect a change in
the re-insertion probability of the primarily produced
olefins. As seen from its expression (Eq. (9)), 0 is
chain-length dependent by dint of the chain-length de-
pendence of the desorption rate, kd . This in turn de-
pends – for given process conditions – solely on the
effective desorption energy, which is determined by
fitting the (experimental) P/O values. Fig. 7 shows the
actual values of kd as a function of carbon number for
the 1 and 18 bar cases. Clearly, in order for 0 to be
appreciably different from zero, thereby giving rise to
the observed non-ASF behaviour of the 18 bar exper-
ξ
iments, ka must be in excess of 103 d0 /s (c.f. Eq. (9))
ξ
Thus, the 18 bar value for ka required by our model
is more than 100 times larger than its upper limit at
1 bar. This is unexpected, indeed we believe it is un-
ξ
physical: quite generally, ka is given by
ξ
ka ∝ (1 − θall )a × θHb (10)
where (1 − θ all ) is the fraction of all chain growth
sites which are occupied, and θ H is the chemisorbed
hydrogen coverage. The exponents a and b are con-
stants whose precise values will depend on the molec-
ular pathway of the chemisorption process. Since of
the two constituent factors – free adsorption sites and
chemisorbed hydrogen – the first decreases with pres-
sure and the second increases, the anticipated overall
pressure dependence is very weak.
We therefore, conclude that the observation of
non-ASF behaviour in the Fischer–Tropsch product
distribution does not necessarily imply that secondary
growth reactions of ␣-olefins are occurring to a sig-
nificant extent. This is an important conclusion to
reach, as these secondary growth reactions play a
central role in current models of C5+ selectivity in the
Fischer–Tropsch reaction. These models are reviewed
in the next section. In our view, the current analysis
shows that the simple kinetic model outlined above
does not yet contain all the essential elements required
to yield a proper description of the Fischer–Tropsch
reaction over cobalt catalysts.
4. Strategies for optimal C5+ selectivity
In Section 1 of this paper, we emphasised the
need for operating at high C5+ selectivities in the
Fischer–Tropsch step for the overall economics of gas
conversion processes. To optimise the C5+ selectivity,
it is necessary to be in possession of an accurate pro-
cess model which relates selectivity to all the relevant
catalyst and process parameters. In the literature, such
a model has been published by Iglesia et al. [19–22].
The model of Iglesia et al. not only has direct impli-
cations for the design of F–T catalysts, but also for
the choice of the F–T reactor. While this model is in
many ways similar to the kinetic network outlined in
Section 3, it differs in its explanation for the observed
chain length dependence of secondary reactions. We
briefly discuss its main elements here, the details of
which can be found elsewhere [19–22].
The model of Iglesia et al. provides a complete de-
scription of the Fischer–Tropsch reaction, in which
secondary reactions such as the secondary growth of
␣-olefins discussed previously play a central role. One
implication of this model is that, to obtain optimal
values for the C5+ selectivity, the rate of secondary
hydrogenation reactions should be minimised whilst
the rate of re-adsorption of ␣-olefins should be max-
imised. With the latter idea in mind, it is natural to
suppose that the C5+ selectivity can be increased by
restricting the removal of ␣-olefins from the pores of
the catalyst particles as far as is practically possible.
It is argued that the presence of diffusional restric-
 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40
tions on the transport of ␣-olefins out of the catalyst
particles, can result in an increase in the ␣-olefin con-
centration inside the catalyst pores which leads to a
corresponding increase in the number of secondary
chain growth events. A detailed analysis reveals that
one structural parameter only (χ) actually suffices to
describe the C5+ selectivity of Fischer–Tropsch cata-
lysts. This parameter is given by
R02 εθ
χ= (11)
rp
where R0 and  are the radius and porosity of the cata-
lyst particle, respectively, rp is the average pore radius
of the catalyst support and θ is the density of active
metal atoms per unit area. It is assumed that the active
phase is distributed homogeneously over the support.
The authors show that the C5+ selectivity exhibits a
maximum as a function of χ. This maximum is quali-
tatively explained as follows. For smaller values of χ
the residence times of ␣-olefins in the catalyst particles
are lower which results in a corresponding loss in C5+
selectivity. For larger values of χ, differences in the
diffusion barriers for the reactants (rather than prod-
ucts) lead to a significant depletion of CO inside the
catalyst particles. This results in additional methane
production with an associated reduction in the C5+
selectivity.
The above model gives a satisfactory expla-
nation for many of the experimental observa-
tions in the literature such as the occurrence of
non-Anderson–Schulz–Flory product distributions
[19–22]. Nevertheless, we believe this description to
be incomplete. In the previous section we showed that
a kinetic model similar to that of Iglesia et al. could in-
deed be used to fit non-ASF product distributions, but
we argued that the parameters required are unphysi-
cal. This conclusion is strictly speaking only valid for
experiments with flat model catalysts, which are far
removed from a practical Fischer–Tropsch process.
However, it is also possible to provide a different
interpretation of some of the original data published
by Iglesia et al.. Fig. 8 [19–22] shows the olefin and
paraffin selectivity within the C4 fraction as a function
of bed residence time for a Co/TiO2 catalyst. The bed
residence time has been changed by varying the space
velocity at otherwise constant process conditions. The
figure suggests that 1-butene is selectively consumed
37
Fig. 8. Bed residence time effects on olefin and paraffin selectivity
within C4 products for a Co/TiO2 catalyst. Experiments were
performed in a tubular packed bed reactor, catalyst pellet size
0.17 mm. Reaction conditions: p = 20 bar, H2 /CO = 2.05, 9.5–72%
CO conversion. The selectivity is reported on a carbon basis as
the percentage of the converted CO appearing as a given product.
After E. Iglesia, Applied Catalysis A: General 161(1997) p.69.
with increasing bed residence time, without a corre-
sponding increase in the n-butane selectivity. The in-
terpretation given by Iglesia et al. is that 1-butene se-
lectively disappears as a result of its re-attachment to
the catalyst surface and subsequent secondary growth.
Closer inspection of the data, however, reveals that
the activity of the catalyst is not constant as the bed
residence time is varied. In Fig. 9 a measure of the
number of C4 molecules actually produced (the yield)
is plotted for two bed residence times. The interpre-
tation of Fig. 9 is completely opposite to that of Fig.
8. 1-Butene is apparently hydrogenated without any
evidence for re-adsorption and further growth.
In the next section, we show that our own pilot
plant experiments, which are fully representative for
the commercial scale, also cannot be described by Eq.
(11).
5. Fischer–Tropsch reactor technology
The Fischer–Tropsch reaction is a very exothermic
process and can only be operated in a relatively narrow
temperature range. This imposes stringent demands
on both heat removal and temperature control. Nowa-
days, three different reactor types have been applied
commercially or are considered suitable for commer-
38 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40

Fig. 9. Reinterpretation of the data of Fig. 8 for two values of the Bed residence time: t = 2 s (9.5% CO conversion) and t = 12 s (72% CO
conversion). The quantity plotted is proportional to the number of C4 molecules actually produced (the yield). The difference in catalyst
activity for the two residence times has been taken into account (it can be deduced from Fig. 8 that the catalyst activity at t = 12 s is
roughly a factor 1.26 higher than at t = 2 s).

cial application. These reactors are the gas/solid flu-
idised bed reactor, the multitubular fixed bed reactor
and the three phase slurry reactor.
The (two phase) gas/solid fluidised bed reactor has
been applied extensively by Sasol [23,24]. Today, two
versions of this reactor type are in operation, namely
the well-known circulating beds and the more recently
developed fixed fluidised bed reactor. The latter reac-
tor represents a significant improvement compared to
the circulating fluidised bed type both in terms of cost
and operability [23,24]. Both reactors use iron-based
catalysts, which inevitably leads to a large side pro-
duction of CO2 as a consequence of the water gas
shift reaction. Such inefficient use of expensive syn-
thesis gas however, makes this reactor technology less
well-suited for natural gas conversion processes. Of
course, CO2 can always be separated from the product
stream and recycled back to the synthesis gas manu-
facturing plant, but only at very significant additional
costs.
The multitubular fixed bed and three phase slurry
reactors are both much better suited for application in
natural gas conversion processes. In the remainder of
this section, we will focus on a comparison between
these two reactor types. It is generally recognised
that the main advantages of the multitubular reactor
are:
• easy scale-up, hence no expensive demonstration
unit necessary
• no system needed for separation of catalyst and liq-
uid product
• no problems with catalyst attrition
• larger catalyst loading of the reactor possible
Similarly, often quoted advantages of the slurry reactor
are:
• no intra-particle diffusion limitations due to use of
sufficiently small catalyst particles
• good isothermal operation due to excellent heat
transfer, both within the slurry as well as to the
cooling system
• catalyst can be added and removed during operation,
leading to a larger availability of the reactor
While the advantages of either reactor type stand
as such, they do not provide sufficient background to
prefer one reactor over the other. In principle, one
should compare the performances of optimised reac-
tor/catalyst combinations. For example, if the lifetime
of the catalyst is longer than the time between routine
mechanical inspections of the reactor, as is in fact the
case for the Shell catalyst, one of the advantages of
the slurry reactor vanishes. Likewise, arguments such
as ‘higher catalyst loading’ or no ‘diffusion limita-
tion’ are only meaningful when they lead to an over-
all increase in productivity and an associated reduc-
 J.J.C. Geerlings et al. / Applied Catalysis A: General 186 (1999) 27–40 39

tion in the costs. A good measure for this, in the case

of the Fischer–Tropsch process, is the combination
of selectivity and volumetric productivity. The volu-
metric productivity determines the total reactor vol-
ume required, which directly relates to the costs of the
Fischer–Tropsch section.
Regarding this point some clear opinions can be
found in the literature. The model of Iglesia et al., for
example, reveals that for large particles, which are re-
quired in fixed bed operation, optimal values of the
parameter χ and thus of C5+ selectivity can only be
obtained for low values of the site density θ (see Eq.
(11)). As a consequence of the low site density, the
volumetric productivity will be low which makes the
multitubular reactor far more expensive than the slurry Fig. 10. Performance of the second generation fixed bed
reactor. A similar conclusion has been drawn recently Fischer–Tropsch catalyst as measured in a pilot plant under fully
representative conditions. Plotted is the liquid (C5+ ) selectivity as
by de Swart [25,26], in a modelling study of both re- a function of catalyst activity for two process conditions.
actor types. The outcome of this study was that the
production of 5000 t middle distillates per day would
require either 10 multitubular reactors (6 m diameter, 6. Summary
20 m high) or 4 slurry reactors (7.5 m diameter, 30 m
high). On this basis it was concluded that the capi- An overview of the research at Shell in the area
tal costs of the slurry reactors would be 60% lower of Fischer–Tropsch technology has been given, cover-
than the multitubular reactors option. The main reason ing the full range from the surface structure of model
identified for this difference between the two reactor catalysts up to the commercial process. Evidence has
types was that the heat transfer rate in the slurry reac- been presented that ’surface defects’ are active sites
tor was approximately a factor of 5 higher than in the for hydrocarbon synthesis. The work on model cata-
multitubular reactor. lysts has been used to quantify a kinetic model, which
At Shell we have a long standing experience in the can be subsequently applied to real catalyst systems.
application of multitubular fixed bed reactors for the Finally, the advantages and disadvantages of the mul-
Fischer–Tropsch synthesis. An illustration of the pos- titubular fixed bed and the slurry reactors have been
sibilities of this reactor type is given in Fig. 10, which discussed. It has been argued that only a comparison
shows the C5+ selectivity as a function of volumetric between optimised reactor/catalyst combinations is a
productivity as measured in a pilot plant under fully meaningful one.
representative conditions. These results show that the
catalyst limitations, which might limit the scale-up
potential of multitubular fixed bed technology for the Acknowledgements
reasons outlined above have been removed. It can for
instance be deduced from Fig. 10 that in the exam- We are grateful to M.M.G. Senden for his helpful
ple worked out by de Swart significantly less than 10 comments.
multitubulars suffice. We are therefore, confident that
our multitubular fixed bed technology is competitive
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