Applied Catalysis A: General 186 (1999) 91–107

Kinetic modelling of Fischer–Tropsch product distributions

Hans Schulz ∗ , Michael Claeys
Engler-Bunte-Institut, Universität Karlsruhe, Kaiserstraße 12, 76128 Karlsruhe, Germany

Abstract
Starting from the idea of Fischer–Tropsch (FT) synthesis as an ideal polymerisation reaction it is easily realised, that
product olefins undergo secondary reactions and thereby modify the product distribution. This generally leads to chain length
dependencies of certain olefin reaction possibilities, which are again suited to serve as a characteristic feature for the kind
of olefin conversion. By extending an existing model and accounting for olefin readsorption, incorporation, hydrogenation
and isomerisation via double bond shift and the chain length dependence of product solubilities, typical deviations from ideal
distributions can be simulated and experimentally observed data with cobalt and iron catalysts can be satisfactorily described,
suggesting the correctness of the assumptions made. Furthermore, other existing models dealing with the same issue are
briefly discussed in this paper. ©1999 Elsevier Science B.V. All rights reserved.
Keywords: Fischer–Tropsch synthesis; Kinetic modelling; Secondary olefin reactions; Incorporation; Hydrogenation; Isomerisation; Chain
length dependence; Solubility; Cobalt; Iron

1. Introduction those by Herington [11] and Friedel and Anderson

The variety of composition of Fischer–Tropsch (FT)
products with e.g. hundreds of individual compounds
shows a remarkable degree of order with regard to
class and size of the molecules, that suggests a strict
kinetic basis, which is undoubtedly complex, however,
as not accidental it is well suited for kinetic modelling,
provided the main surface reactions and their interre-
lations, are well understood as based on thoroughly
measured experimental data.
The first attempts to describe the molar FT carbon
number product distribution mathematically as a poly-
merisation reaction, generally believed to proceed via
addition of a single carbon monomer [1–10], were
∗ Corresponding author. Tel.: +49-721-608-2961; fax:
+49-721-693019
E-mail address: hans.schulz@ciw.unikarlsruhe.de (H. Schulz)
[12], and may be presented as:
MN = M1 · α N −1 (1)
where N indicates the carbon number, α the chain
growth probability and MN the molar fraction of linear
products with carbon number N. This equation, which
is equivalent to the Schulz–Flory equation derived for
condensation polymers, predicts a linear relationship
between lg(MN ) and N, where α, can be obtained from
the slope of these so called Anderson–Schulz–Flory
(ASF) plots. It implies independence of chain growth
probability α from the carbon number of the growing
species.
In addition Anderson et al. [5,12,13] introduced
chain branching via addition of a C1 -monomer at the
penultimate carbon atom of a growing chain into the
model. The rate constants of chain branching were as-
sumed to be carbon number independent.

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92 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
Novak et al. [14,15] studied modifications of the
ASF model, like by additional chain growth or desorp-
tion by combination of growing chains or additional
cracking and chain growth via C1 and C2 monomers.
Referring to olefin cofeeding studies during FT syn-
thesis [16], which revealed, that olefins can readsorb
and initiate new hydrocarbon chains during FT syn-
thesis, Novak et al. [14] also modelled these effects on
FT distributions, which had in the first place been sus-
pected by Herington [11]. Their analysis for FT con-
version in a CSTR showed, that such reactions should
lead to higher chain growth probabilities, the prod-
uct composition, however, still would follow an ideal
ASF distribution (except for C1 ), assuming a chain
length independent readsorption of olefins. For a plug
flow reactor an insignificant deviation (with increasing
carbon number decreasing chain growth probabilities)
from an ideal distribution was predicted. Chain length
dependent effects as solubility or diffusivity likewise
were not considered by these authors.
A further development of Anderson’s model and
comparison with experimental data was published
by Wojciechowski et al. [17–23]. This model defines
a number of abstract kinetic parameters, which al-
low calculations of product distributions, including
methyl-branched isomers. It further predicts a straight
line for linear products in the ASF plot, and carbon
number independent molar ratios of methyl-branched
to linear compounds of the same carbon number,
2-methyl-branched compounds being the major frac-
tion among the branched compounds. Furthermore,
the authors suggested that experimentally observed
breaks of the distributions of the linear paraffins were
due to different ways of chain termination and could
be described by a superposition of two ‘ideal’ dis-
tributions. After having made sure that experimental
artifacts could be excluded, other authors [24,25]
suspected the existence of two sorts of growth sites,
each yielding ideal distributions with different chain
growth probabilities, to explain the break in the ASF
diagram of the total product in the range C8 –C12 ,
which has been also observed by many other re-
searchers [22,23,26–32].
Also starting with an ideal system (chain length in-
dependent chain growth probability, one sort of prod-
ucts) Schulz et al. [33–35] developed a kinetic model
of FT synthesis which they termed a ‘non trivial sur-
face polymerisation’, relating to the fact that its C1
monomer is formed ‘in situ’ on the catalyst surface.
By stepwise adopting assumptions like
• formation of different kinds of primary products
(olefins, paraffins, oxygenates),
• formation of methyl-branched species during chain
growth, and
• consideration of carbon number dependent rate con-
stants,
the ideal model was extended and essential features
of observed product distributions could be moni-
tored/described.
In particular, Anderson’s postulate of carbon num-
ber independent chain branching probabilities was
questioned. By implying exponentially with increas-
ing carbon number decreasing chain branching rate
constants, a complete description of the chain length
dependent distributions of all mono-methyl-branched
compounds, which satisfactorily agreed with exper-
imental data, was reached. The model can likewise
be used to determine chain length dependent prob-
abilities of chain growth and chain branching from
experimentally obtained FT product composition
data. The model can also allow for the formation of
different sorts of compounds as paraffins, olefins and
oxygenates, which desorb in distinct ratios indepen-
dent of carbon number. Furthermore, secondary olefin
reactions, hydrogenation and double bond shift, were
qualitatively linked to the FT reaction scheme. Devi-
ations from ideal ASF kinetics, displaying decreasing
slopes in the ASF diagram or increasing chain growth
probabilities respectively, with increasing carbon
number were suspected to be caused by incorporation
of ␣-olefins and their chain length dependent solubili-
ties (increasing with increasing carbon number) in the
liquid FT product or reactor residence times likewise.
However, a quantification of this suggestion, which
had earlier been provided by Pichler [36] and Bell
[30], had not been implied into the model.
Introduction of secondary olefin reactions (incor-
poration and hydrogenation) into modelling of FT
product distributions (to explain experimental distri-
butions obtained from FT synthesis experiments with
Co, Ru catalysts in fixed bed reactors) was performed
by Iglesia et al. [37–40], who allowed for ␣-olefin
readsorption. Again, with carbon number increasing
residence times were assumed to be the reason for ex-
perimentally observed chain length dependencies of
␣-olefin-paraffin ratios and chain growth probabilities,
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107 93

which reached asymptotic values as ␣-olefin : paraffin

ratios decreased to zero as carbon number increased.
In contrast however, diffusional limitations within
liquid filled catalyst pores (and to a smaller extent
interparticle diffusional effects) were considered to Fig. 1. Balance around a chemisorbed surface species SpN .
enhance readsorption and chain initiation, and thereby
lead to the formation of heavier and more paraffinic applied reaction conditions [44,45], we have extended
products. Hydrogenation of olefins to paraffins on our existing kinetic model taking into account olefin
non FT alike hydrogenation sites was believed to be hydrogenation, isomerisation (double bond shift) and
suppressed at typical FT conditions, i.e. high water incorporation and in particular chain length dependent
partial pressure (high conversion), and/or high CO product solubilities. The validity of this model has
partial pressure. Their model was also linked to cat- been checked with experimental data obtained from
alyst properties and reaction conditions and, as an FT synthesis runs in a slurry reactor with cobalt and
implication, is supposed to predict high C5+ selectiv- iron catalysts, as described in the following.
ity with Co and Ru catalysts as a result of ␣-olefin
readsorption. 2. Description of the original model and model
Furthermore, in cases of severe transport restriction extensions
(e.g. large catalyst particles) high local H2 : CO ra- 2.1. Basic model
tios were expected to cause methane formation by hy-
drogenolytic C–C bond cleavage of olefins. Secondary The basic model starts with the assumptions, that
olefin isomerisation via double bond shift was not in- only one sort of product PrN can desorb and no chain
cluded in their model and even not considered. branching occurs (see Fig. 1 and [33]).
In further attempts to describe the impact of sec- A mass balance around a surface species SpN at
ondary olefin reactions (incorporation and hydrogena- steady state results in:
tion) on deviations from ideal ASF distributions, chain rg,N −1 = rg,N + rd,N (2)
length dependent solubilities of the primarily formed
and assuming first order kinetics with regard to the
olefins were taken into account by Zimmerman et al.
concentration of a certain surface species:
[41] and Kuipers et al. [42]. Zimmerman et al. ob-
tained a rather poor agreement of model simulations kg,N −1 · cs,Sp,N −1 = kg,N · cs,Sp,N + kd,N · cs,Sp,N (3)
for a product distribution including olefin contents in and rearranged:
hydrocarbon fractions obtained by experiments with a
kg,N −1
stirred tank reactor using the commercial iron based cs,Sp,N = · cs,Sp,N −1 (4)
Ruhrchemie catalyst. Kuipers et al., who argued that kg,N + kd,N
chain length dependent solubility would usually dom- The formation rate of a product compound with N
inate diffusional effects [43], found a fair agreement carbon atoms rN (i. e. its desorption rate) is given by:
of experimentally observed product distributions and
paraffin to ␣-olefin ratios obtained with a model cata- rN = rd,N = kd,N · cs,Sp,N
lyst (Co–SiO2 ) at low conversion by applying a model, kd,N
= · kg,N −1 · cs,Sp,N −1 (5)
which involves additional olefin cracking (hydrogenol- kg,N + kd,N
ysis) and the assumption, that preferential physisorp- and with the definition of the desorption probability
tion of long hydrocarbon chains (olefins) possibly con- pd,N
tributes to deviations from ideal ASF kinetics by cre- 
ating an ‘umbilical cord’ between the ␣-olefin and the kd,N
pd,N = analogously : chain growth
growth site. kg,N + kd,N

Based on recent extensive studies with cofeeding of kg,N
olefins of different chain length during FT synthesis probability pg,N = (6)
kg,N + kd,N
in a gradientless slurry reactor with cobalt and iron
catalysts, which strongly suggest diffusional effects on follows:
secondary olefin reactions to be very unlikely at the rN = pd,N · kg,N −1 · cs,Sp,N −1 (7)
94 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
An analogous balance can be made for the surface
species SpN−1 , SpN−2 , etc. to Sp1 , which leads to:
rN = pd,N · pg,N −1 · pg,N −2 · pg,N −3 . . . pg,2 · kg,1
·cs,Sp,1 (8)
Since all product compounds are formed starting
from a C1 species, the sum of the formation rates of
all products must equal the consumption rate of the
species Sp1 , the chain starter:
X
rN = (kd,1 + kg,1 ) · cs,Sp,1 (9)
N N →∞ MN
It should be noted, that the sum of formation rates
of all organic compounds on a carbon basis equals the
rate of CO consumption, which links the model to the
actual conversion of synthesis gas.
The molar content of a product compound MN with
N carbon atoms in the total organic product spectrum
is:
rN
MN = P = pd,N · pg,N −1 · pg,N −2 · pg,N −3 . . .
N rN
N−1
Y
pg,2 · pg,1 = pd,N · pg,N (10)
N=1
i.e. the product of the reaction probabilities of all reac-
tion steps required to form the specific compound. In
case of carbon number independent probabilities the
model turns into the equation for ideal ASF kinetics
Eq. (1).
In a similar manner the formation of methyl-branched
compounds as opposed to linear compounds can be
expressed [35,46,47].
The model can in turn be used to determine the
chain length dependent probabilities of a surface
species from experimentally derived product distri-
butions. Since these calculations are started at (high)
carbon numbers, where no further changes of the
slope in the A–S–F plot are expected (asymptotic end
value of the chain growth probability (see Eq. (11))
and is proceeded towards lower carbon numbers, the
knowledge of the whole product spectrum including
very high carbon number fractions (N > 20) is nor-
mally not required; in contrast to the determination of
chain growth probabilities based on e.g. Heringtons
model [11,37–40].
Fig. 2. Kinetic scheme of secondary olefin reactions taking into
account the solubility of olefins in liquid F–T product.
MN +1 ṅN +1 pg,N · pd,N+1
lim = lim = lim
N →∞ ṅN N →∞ pd,N
= pg,N (11)
(ṅN = experimentally obeserved molar formation rate
of compounds with carbon number N)
Reaction probabilities can then be calculated using
[46]:
1
pg,N −1 =
1 + pd,N · (ṅN −1 /ṅN )
and pg,N + pd,N = 1 (12)
2.2. Extension of the model taking into account
olefin readsorption
In the following the impact of the carbon number
dependent solubility of olefins, that can readsorb and
undergo secondary reactions, on the product distri-
bution, the chain growth probabilities and the molar
olefin content in the respective hydrocarbon fractions
will be incorporated in the model.
The following additional assumptions are made (as
visualised in Fig. 2):
Assumptions:
1. Primarily only ␣-olefins and paraffins are formed
at a carbon number independent molar ratio
(‘primary olefin selectivity’). This assumption is
mainly based on experimentally observed chain
length independent olefin contents in hydrocarbon
fractions from F–T runs with catalysts/reaction
conditions, that hardly allow for olefin readsorp-
tion (i.e. Fe–Mn catalysts and high space velocity
[48]). Results from experiments with cofeeding
of olefins of different chain lengths in a slurry
reactor with cobalt and iron catalysts also indi-
cate carbon number independent primary olefin
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107 95

selectivities [45]); the products desorb into the rg,Sp,N −1 · mMe = (rg,Sp,N + rd,P,N + rd,Ol-(1),N
liquid product phase, from the catalyst surface. −ra,Ol-(1),N ) · mMe
2. ␣-Olefins can either readsorb to form a surface
species, which is indistinguishable from ‘indig- ⇔ kg · cs,Sp,N −1 · mMe = (kg · cs,Sp,N + kd,P · cs,Sp,N
ineous’, via chain growth formed surface alkyl +kd,Ol-(1) · cs,Sp,N − ka · cl,Ol-(1),N ) · mMe (13)
species SpN , or readsorb to form a species Sp0N ,
which does not participate in chain growth and can Balance around Ol-(1)N :
either reversibly desorb as an n-olefin-(1) or as an 0
end-product EPN . EPN represents either paraffins (rd,Ol-(1),N + rd,Ol -(1),N ) · mMe = (ra,Ol-(1),N
0
or olefins with internal double bonds. The path- +ra,Ol -(1),N ) · mMe + ṅl,Ol-(1),N,out
way of readsorption of EPN and further formation +ṅg,Ol-(1),N,out
of ␣-olefins is not accounted for in the scheme, 0 0
since the addition of olefins with internal double ⇔ (kd,Ol-(1) · cs,Sp,N + kd,Ol -(1) · cs,Sp,N ) · mMe
bonds during F–T synthesis over cobalt and iron = (ka + ka0 ) · cl,Ol-(1),N · mMe + V̇l · cl,Ol-(1),N
catalysts was found not to affect secondary chain
V̇g
growth, which can occur via n-olefin-(1) readsorp- + · cl,Ol-(1),N (14)
tion [44,45]. KN
3. By implying the surface species Sp0N , the model Balance around EPN :
accounts for secondary hydrogenation and sec-
0
ondary isomerisation (double bond shift), without (rd,P,N + rd,EP,N ) · mMe = ṅl,EP,N,out + ṅg,EP,N,out
stating or excluding that these reactions are to take 0 0
⇔ (kd,P · cs,Sp,N + kd,EP · cs,Sp,N ) · mMe
place at different kind of sites.
4. Effects of diffusional limitations (intra and inter V̇g
= V̇l · cl,EP,N + · cl,EP,N (15)
particle) of reactants and products are excluded. KN
The reactor is regarded to perform gradientless
with regard to concentrations and temperature (remark: the solubilities of EPN are assumed to be
(e.g. CSTR and usage of very small catalyst equal to the solubilities of Ol-(1)N )
particles), the reaction is at steady state and Balance around Sp0N :
the products leave the reactor continuously via 0 0 0
ra,Ol -(1),N · mMe = (rd,EP,N + rd,Ol-(1),N ) · mMe
gas and liquid phase, the two phases being at
thermodynamic equilibrium, which can be ex- ⇔ ka0 · cl,Ol
0 0 0
-(1),N · mMe = (kd,EP · cs,Sp,N
pressed by the so called partition coefficient 0 0
+kd,Ol -(1) · cs,Sp,N ) · mMe (16)
KN (= cl,N /cg,N ) [49]. KN is strongly carbon
number dependent; solubilities of alkenes in a C30 (Note: Product condensation, which would affect
alkane can be described with the following equa- concentrations in gas and liquid phases at high carbon
tion: KN = K2 ·b(N -2) (typical values: K2 = 1.91, numbers, is not taken into account explicitely. This
b = 1.53 at 190◦ C; K2 = 1.09, b = 1.46 at 250◦ C is, however, of no importance for the considerations
[44,45]). made, since experimentally observed molar contents
5. All rate constants are assumed to be carbon num- of ␣-olefins, which could readsorb and thereby mod-
ber independent; except for N = 2: according to ify product distributions, have usually reached neg-
studies with cofeeding of olefins of different chain ligibly small values at carbon number ranges, where
length, the reactivity of ethene is 10–40 times quantitative product condensation typically takes place
higher than for C3+ olefins [44,45]. For that rea- (N ≈ 20).V̇g and V̇l (the total gaseous and liquid vol-
son the rate of adsorption of ethene is consid- umetric flow rates), which are determined by process
ered to be 10–25 (40) times higher than for other conditions and the catalyst performance, are also not
0 /k 0 = 10).
␣-olefins (e.g. ka,2 /ka = 10; ka,2 a explicitly formulated, could however be incorporated
At steady state the following mass balances can be in the model.)
expressed: The combination of Eqs. (13), (14) and (16) leads
Balance around SpN : to the following expression, Eq. (17):
96 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107

(17)
which, in analogy to Eq. (3) expresses the formation
rate of a surface species SpN via chain growth from a The total carbon number distribution can again be
surface species SpN-1 (left hand side) and the effective derived by multiplication of the single (effective) re-
rate of consumption of the surface species SpN via des- action probabilities, that lead to the formation of a
orption (including olefin readsorption) and chain pro- regarded product (see Eq. (10)). In addition separate
longation. A direct comparison with Eq. (3), derived calculations of olefin and paraffin distributions, based
in the model without olefin readsorption allows for the on their desorption probabilities, are possible:
assignment of effective rate constants for olefin des- kd,P
orption and total product desorption (kd,Ol-(1),eff,N and pd,P,eff,N =
kg + kd,total,eff,N
kd,total,eff,N ), which include the carbon number depen-
dent ratio KN and thereby links the extended model kd,Ol-(1),eff,N
and pd,Ol-(1),eff,N = (20)
to physico-chemical effects. kg + kd,total,eff,N
By replacing the rate constants in Eq. (6), which
The formula of the molar olefin-(1) content in the
defines the reaction probabilities, the following chain
fraction of the respective hydrocarbons of the same
length dependent effective probabilities can be ex-
carbon number (‘olefin-(1) selectivity’)
pressed as in Eq. (18):
kg 1 cl,Ol-(1),N 1
pg,eff,N = = = (21)
kg + kd,total,eff,N 1 + (kd,total,eff,N /kg ) cl,Ol-(1),N + cl,EP,N 1 + (cl,EP,N /cl,Ol-(1),N )
and pd,eff,N = 1 − pg,eff,N
(18)
which, after regrouping and simplifying results in:
1
pg,eff,N =  
kd 
1+ kg
1
kd,Ol (1)
-  +  k
1
−1  · A
1+ kd,P 1+ -
d,Ol (1)
kd,P
 
 ka mV̇Me 
 
A= ! 
g
with 1 −    −1  (19)
 0
kd,Ol 0
kd,EP kd,Ol-(1) −1 V̇l 
ka mV̇Me + ka0 mV̇Me 1− -(1)
kd,Ol-(1) + kd,P · kd,P + V̇g
+ 1
KN
g g
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
or the ratio cl,EP,N /cl,Ol-(1),N respectively can be ob-
tained by combining Eqs. (14)–(16):
c1,EP,N
= (kd,Ol-(1) /kd,P )−1 (ka · mMe /V̇g )
c1,O1-(1),N
+(ka0 · mMe /V̇g )(1 − (1 − (kd,Ol
0
-(1) /kd,Ol-(1) )
0
×(kd,Ol-(1) /kd,P )(kd,EP /kd,P )−1 )/(1 + (kd,Ol
0 2.3. Theoretical model calculations
-(1)
0
/kd,Ol-(1) )(kd,Ol-(1) /kd,P )(kd,EP /kd,P )−1 )



+(V̇l /V̇g ) + (1/KN ) (V̇l /V̇g ) + (1/KN ) (22)
Eqs. (19) and (22) are arranged in a way, that they
only contain dimensionless terms or parameters of the
extended model, KN being the only carbon number
dependent term. Intensive parameters of the model are:
kd /kg fixes the ‘primary chain growth probabil-
ity’ (pg = kg /(kg + kd )) without olefin read-
sorption
kd,Ol-(1) expresses the ‘primary selectivity
/kd,EP of ␣-olefins in hydrocarbon frac-
tions’ kd,Ol-(1) /kd,Ol-(1) + kd,EP 0 = 1/1+
0 −1
(kd,Ol-(1) /kd,EP ) which is believed to be
carbon number independent and typically
lies in the range 70–90 mol% [48].
ka · mMe determines the rate of olefin-(1) readsorp-
/V̇g tion to form surface species SpN
ka0 · mMe determines the rate of olefin-(1) readsorp-
/V̇g tion to form surface species Sp0N , that do
not participate in chain growth
0
The ratios kd,Ol 0
-(1) | kd,Ol-(1) and kd,EP | kd,P reflect
the comparative desorption behaviour of olefins and
‘inert’ products (paraffins and olefins with internal
double bonds) from surface species SpN and Sp0N , and
are set at unity for the model calculations.
The ratio of the actual volumetric flow rates (at re-
action conditions) of the liquid and the gaseous phase
leaving the reactor (V̇l /V̇g ) is generally very low (e.g.
0.0001–0.0006 for the experimental results examined
in this paper) and can normally be neglected in the
model calculations.
The dimensionless parameters ka ·mMe /V̇g and ka0 ·
mMe /V̇g are coupled with V̇l /V̇g and contain terms,
which determine the rates of olefin readsorption to
yield surface species SpN and Sp0N , respectively. A
variation of these has particularly to be understood as
a variation of ka or ka0 .
97
0 |k 0 are be-
Furthermore, the ratios ka,2 | ka and ka,2 a
lieved to be equal and to lie between 10 and 25 (40)
(see above).
In the following it is demonstrated how olefin-(1)
readsorption can affect the product carbon number dis-
tribution and the corresponding chain growth proba-
bilities and molar olefin-(1) contents in the respective
hydrocarbon fractions as a function of carbon num-
ber. The formation of species Sp0N , which do not par-
ticipate in chain growth is not taken into account for
the time being (i.e. ka0 · mMe /V̇g = 0). Fig. 3 shows
the results of model calculations, where the value of
ka · mMe /V̇g = 0 has been varied over the wide range
from 0 to 10 (ka,2 /ka = 10). The ‘primary chain growth
probability’ was chosen to be 0.7 (i.e. kd /kg = 0.43),
and a ‘primary olefin-(1) content’ of 80 mol% was
assumed (i.e. kd,Ol-(1) /kg = 4). The ‘primary’ product
distribution, as not affected by secondary olefin reac-
tions is presented as dashed lines.
In accordance with typical values obtained at
our FT experiments in a slurry reactor a ratio of
V̇l /V̇g = 0.0001 was assumed, the values for solubility
(KN ) refer to the reaction temperature of 250◦ C (see
above; KN = 1.09·1.46N -2 ).
These calculations show how extremely the product
distribution could be affected by olefin-(1) readsorp-
tion. Experimentally often observed deviations from
ideal A–S–F plots with high values at C1 , low values
at C2 and a curvature, which approaches a straight line
at high carbon numbers are described properly by the
model; correspondingly the deviations in chain growth
probabilities (middle of Fig. 3) can be depicted. These
curves reach assymptotic high values as olefin con-
tents (right of Fig. 3) have decreased towards negli-
gibly small values (or constant values at high carbon
numbers). Likewise, the so calculated olefin-(1) con-
tents as a function of carbon number display a typical
curvature, with a relatively low value at C2 , a maxi-
mum value at C3 and a decline with increasing carbon
number.
At high carbon numbers a constant chain growth
probability is reached; this limiting pg,eff,N value can
be calculated as follows:
98 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107

Fig. 3. Calculation results with the extended kinetic model taking into account carbon number dependent product solubilities; effect of
olefin-(1) readsorption as surface species SpN . (Dashed lines: without readsorption, solid lines: with readsorption). (Model parameters:
0
kd /kg = 0.43, kd,Ol-(1) /kd,P = 4, kd,Ol 0
/kd,Ol-(1) = 1, kd,EP /kd,P = 1, ka ·mMe /V̇g = varied, ka0 · mMe /V̇g = 0, ka,2 /ka = 10, V̇l /V̇g = 0.0001). left:
P30 -(1)
A–S–F plot (normalised for N =1 MN ); middle: chain growth probability pg,N in dependence of carbon number; right: molar olefin-(1)
content in carbon number fractions.

1 the ASF distribution and the chain growth probabili-

lim pg,eff,N =
N→∞ 1 + (kd,P /kg )
1 From the above kinetic modelling it turns out, that
=

1 + (kd /kg ) · (1/ 1 + (kd,Ol-(1) /kd,P )
1
= = 0.92
1 + (0.43 · 0.02)
Olefin-(1) contents in the product decrease as ka
increases (i.e. an increase of ka · mMe /V̇g ). The pro-
nounced change of the slope of the ASF curve appears
in the same carbon number range, where the olefin
content decreases strongly.
Fig. 4 clarifies the effect of additional olefin hy-
drogenation and isomerisation of primary ␣-olefins by
taking into account the parameter ka0 · mMe /V̇g in the
model.
This additional route causes a further decrease of
the olefin-(1) contents in the respective carbon num-
ber fractions (see solid black line (ka · mMe /V̇g = ka0 ·
mMe /V̇g = 1), Fig. 4 right). Simultaneously the effect
of olefin readsorption on the total product distribution
in the ASF diagram (left) is less pronounced and lower
chain growth probabilities (middle) are obtained. The
grey lines show the case, discussed above, without in-
cluding this route (ka0 · mMe /V̇g = 0); the dashed lines
count for the case without any olefin readsorption.
An exclusive olefin readsorption via Sp0N species,
which don’t participate in chain growth, would also
lead to the characteristic shapes of the curves of
olefin-(1) contents, however, would have no effect on
ties (not shown).
desired product distributions (e.g. wax yield or high
olefinicity) could be achieved by controlling extent and
(23) selectivity of secondary olefin reactions. Both reaction
conditions and catalyst properties are of influence (see
also below).
3. Experimental work and fitting of experimental
data with the extended model
3.1. Experimental
The experiments were performed in a continuously
operated stirred slurry reactor with powdered catalyst
particles (dp < 100 ␮m) suspended in the liquid reac-
tion product/wax (for details see e.g. [44–46]). Prod-
ucts left the reactor continuously via gas and liquid
phase. Effects of diffusional restriction of reactants
and products were found to be negligible at the reac-
tion conditions applied in the reactor system [44,45],
which fulfils assumptions made in the model described
above.
One cobalt and two iron catalysts were used. They
were prepared via discontinuous co-precipitation,
starting from nitrate solutions of the respective salts
(except ZrOCl2 ), with a NH3 solution and, after a
washing and drying procedure, subsequent impreg-
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107 99

Fig. 4. Calculation results with the extended kinetic model taking into account carbon number dependent product solubilities; additional
effect of olefin-(1) readsorption as surface species Sp0N . (Dashed lines: without readsorption, grey solid lines: with readsorption as species
SpN , black solid lines: with readsorption as species SpN and Sp0N ). (Model parameters: kd /kg = 0.43, kd,Ol-(1) /kd,P = 4, kd,Ol 0
-(1) /kd,Ol-(1) = 1,
0
kd,EP 0 /k 0 = 10, V̇ /V̇ = 0.0001) left: A–S–F plot (normalised for
/kd,P = 1, ka ·mMe /V̇g = 0 or 1, respectively, ka0 · mMe /V̇g = 1, ka,2 /ka = 10, ka,2 a l g
P30
N =1 MN ); middle: chain growth probability pg,N ; right: molar olefin-(1) content in hydrocarbon fractions.

nation with RuCl3 or K2 CO3 solutions, respectively
(‘incipient wetness method’). In case of the cobalt
catalyst, Aerosil® (Degussa) was present/suspended
in the salt solution and included in the precipitate. The
compositions of the catalysts (in mass ratios) were:
100Co–15ZrO2 –100Aerosil® –0.66Ru (33.5 wt.%
Co∗ )
100Fe–13Al2 O3 –10Cu (52.7 wt.% Fe∗ )
100Fe–13Al2 O3 –10Cu–5K (50.7 wt.% Fe∗ )
(* refering to the catalyst at its oxidic state)
Before the synthesis experiments, all catalysts were
pretreated in a separate fixed bed reactor by tempera-
ture programmed (2◦ C/min) calcination in Argon and
reduction in a H2 –Ar mixture (1/3 mol/mol) (final tem-
perature 550◦ C with the cobalt catalyst, 400◦ C with
the iron catalysts), and then (under inert atmosphere)
transferred to the slurry reactor (for further details see
[44]).
In Table 1 the reaction conditions are listed.
The below discussed product distributions refer to
one single reaction condition, which had been main-
tained for ca. 60 days. The duration of this period of
steady state conversion is sufficiently long to assure
for a representative composition even of the liquid
product phase; noticeable catalyst deactivation did not
occur during this period.
At reaction temperature volatile organic compounds
were collected in glass ampoules [50] from the reactor
effluent and analysed gas-chromatographically (100 m
capillary column, RTx-1 (Restek), flame ionisation
detector, gas chromatograph: HP 5880 A (Hewlett
Packard), temperature program: −80–280◦ C). The
liquid product (‘wax’) was analysed using the so
called flushing injection technique (wax dissolved
in e.g. n-octane, method described by Poulson
and Jensen [51], see also [44,46]), a wide bore
capillary column and a flame ionisation detector
(gas-chromatograph: F22 (Perkin-Elmer), temperature
program: 50–350◦ C); with this method paraffins up to
carbon numbers of N = 60 could reliably be analysed.
Fig. 5 shows the three obtained product distribu-
tions (open circles: volatile hydrocarbons; solid cir-
cles: liquid products) visualised as ASF-plots
P of the
total hydrocarbon product (normalised for 45 N =2 MN ,
see Fig. 5 left), the total chain growth probability (as
calculated from the molar distribution of the product
gaseous phase with the method described above, see
Fig. 5 middle) and the molar olefin-(1) content in the
respective hydrocarbon fractions (see Fig. 5 right) as
functions of carbon number.
All distributions show deviations from ideal
Schulz–Flory kinetics displaying a characteristic cur-
vature in the ASF plots with relatively high values at
C1 , low values at C2 and from C3 onwards decreas-
ing olefin-(1) contents. At high carbon numbers the
curves in the ASF diagrams turn into straight lines,
and the slopes of these (or the chain growth probabil-
ities respectively) remain unchanged at high carbon
numbers. The changes in the ASF plots indeed co-
incide with the strong declines of the corresponding
100 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107

Table 1
Reaction conditions of F–T experiments in a stirred slurry reactor (steady state conversion)
Catalysts

Co–Zr–SiO2 –Ru Fe–Al–Cu–K Fe–Al–Cu

Mass of active metal (mMe ) g 4.18 4.06 4.06

Reaction temperature (T) ◦C 190 250 250
Total volumetric inlet flow (V̇SG,∈ ) ml(NTP)/min 37 65 58
Molar H2 /CO inlet ratio, (H2 /CO)in mol/mol 2.53 1.91 1.84
Total pressure (ptot ) bar 8.9 10.0 10.1
H2 -partial pressure (pH2 ) bar 5.5 6.5 5.7
CO-partial pressure (pCO ) bar 2.2 0.6 2.8
H2 O-partial pressure (pH2 O ) bar 1.1 1.2 0.5
CO2 -partial pressure (pCO2 ) bar – 1.5 0.4
Mean reactor residence time in gas phase (τ ) min 37 28 26
Total CO-consumption rate (rCO ) ␮mol/(minl gMe ) 43 194 78

Table 2
adjusted to obtain the best possible fit with the exper-
Model parameters used to fit the experimental F–T product distribu-
tions shown in Fig. 5. (In all three cases: ka,2 /ka = 10, ka,2 0 /k 0 = 10, imental data. In accordance with cofeeding studies
a
0
kd,Ol /k = 1 and k 0 /k = 1; K according to the re- [44,45] the higher reactivity of ethene as compared to
-(1) d,Ol -(1) d,EP d,P N
spective reaction temperatures (see above)) higher olefins-(1), was taken into account by setting
0 /k 0 as being 10.
ka,2 /ka and ka,2
Parameters Catalysts a
With these parameters and the carbon number de-
Co–Zr–SiO2 –Ru Fe–Al–Cu–K Fe–Al–Cu
pendent partition ratio KN a good quantitative descrip-
kd /kg 0.6 (0.625)a 0.49 (0.671)a 0.9 (0.526)a tion of the experimental data could be obtained with
kd,Ol-(1) /kd,P 4 (80)b 4 (80)b 4 (80)b the kinetic model. Some uncertainties are discussed in
ka · mMe /V̇g 0.85 0.12 1.0
the following.
ka0 · mMe /V̇g 0.60 0.07 1.9
V̇l /V̇g 0.0004 0.0004 0.0001
a“Primary chain growth probability”.
3.2. Co–Zr–SiO2 –Ru
b‘Primary’ molar olefin-(1) content in fraction of linear hydrocar-
bons (in mol%). Generally with this Cobalt catalyst the best fit was
obtained. Only the high methane selectivity (as re-
olefin-(1) contents (from C3 onwards to negligible flected in the low chain growth probability at N = 1)
values at higher carbon numbers), which underlines was not satisfactorily to be described by the model.
the impact of olefin-(1) readsorption on chain growth. Additional methane formation from hydrogenolytic
The results of model calculations to fit the experi- C–C bond rupture reactions of higher hydrocarbons
mental data are also shown in Fig. 5 as the solid lines; (as proposed by several authors [37–40,42]) could be
the used parameter sets are compiled in Table 2. excluded in the present case, since olefin cofeeding
The dashed lines represent theoretical (ideal) prod- studies with this catalyst [44,45] showed no indication
uct distributions without olefin-(1) readsorption, for this reaction pathway. It is therefore suggested, that
which are characterised by the ‘primary’ chain growth the additional methane formation originates from C1
probability (expressed as kd /kg ) and the ‘primary’ species which do not participate in chain growth and
olefin-(1) selectivity (expressed as kd,Ol-(1) /kd,P ). may be formed on different kinds of catalytic sites, as
The values of kd /kg were estimated from the initial suggested earlier [47,52].
slope in the ASF diagram at low carbon numbers,
kd,Ol-(1) /kd,P was chosen to equal 4 in all three cases, 3.3. Fe–Al–Cu–K
which corresponds to a primary olefin-(1) selectivity
of 80 mol% (see also discussion below). The param- The deviation of calculated chain growth probabil-
eters ka · mMe /V̇g , ka0 · mMe /V̇g were then iteratively ity as a function of carbon number, from the experi-
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107 101

Fig. 5. Calculations with the extended kinetic model taking into account carbon number dependent product solubilities; fitting of experimental
data with the catalysts: Co–Zr–SiO2 –Ru (top), Fe–Al–Cu–K (middle) and Fe–Al–Cu (bottom). (Dashed lines: without readsorption, solid
P
lines: with readsorption as species SpN and Sp0N ). (Model parameters: see Table 2) left: ASF plot (normalised for 45 N =2 MN ); middle:
chain growth probability pg,N ; right: molar olefin-(1) content in hydrocarbon fractions.

mental values with the catalyst Fe–Al–Cu–K, are due
to the fact, that the calculated chain growth probabil-
ities (see above) are solely based on the distribution
the volatile hydrocarbons which is representative up
to about C15 . In this case, however, even at carbon
numbers above C14,15 ␣-olefins are present in consid-
erable amounts and can participate in secondary chain
growth. Respectively, the asymptotic carbon number
independent value of the chain growth probability is
not yet reached. However, the description of the ASF
curve is still satisfactorily.
3.4. Fe–Al–Cu
With this catalyst double bond isomerisation was
very pronounced. Olefin-(1) contents in olefin frac-
tions of the same carbon number were below 20 mol%.
These values are close to the partial equilibria of the
linear mono olefins (i.e. 12 mol% butene-(1) content
among the linear C4 olefins and 4.8 mol% hexene-(1)
among the linear C6 olefins [53]). Double bond iso-
merisation equilibria are only weakly dependent on
temperature [54]).The assumption earlier made in the
102 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
model, that olefins with internal double bonds do not
readsorb and form a surface species SpN or (after des-
orption via Sp0N ) an olefin-(1), which could partici-
pate in secondary chain growth, might therefore not
hold in this system, where double bond isomerisation
is very pronounced. However, carbon number depen-
dent trends are even in this case described adequately.
The absolute values of the parameters ka · mMe /V̇g
and ka0 ·mMe /V̇g give an idea about the extend to which
secondary olefin reactions have taken place. For ex-
ample, with the alkalised iron catalyst these values
are much smaller than with the non-alkalised (remark:
reactor residence times and the mass of active metal
or the ratio mMe /V̇g respectively were similar in both
cases). This is in qualitative accordance with olefin
cofeeding studies at the same reaction conditions with
these catalysts [44,45], and confirms the wellknown
effect of potassium promotion of iron FT catalysts to
inhibit secondary olefin reactions.
Assuming the reaction steps of adsorption to be rate
determining, the selectivities of secondary olefin re-
actions (incorporation or alternatively hydrogenation
plus isomerisation via double bond shift) can be esti-
mated: with the cobalt catalyst a selectivity of olefin
hydrogenation plus isomerisation of ca. 48%, with the
catalyst Fe–Al–Cu–K ca. 42% and with the catalyst
Fe–Al–Cu ca. 71% can be determined (see also be-
low).
4. Further considerations and discussion
The model can further be used to study the ef-
fect of reaction parameters individually (e.g. partial
pressures of H2 , CO or H2 O) on secondary olefin
reactions. Fig. 6 shows the model fit with data ob-
tained from FT experiments in the same slurry reactor
with varied water partial pressure over the cobalt cat-
alyst Co–Zr–SiO2 –Ru (details see [44,55]). Again a
very good description of the total product distributions
in the ASF diagrams (only representative samples of
the gaseous product phases are available), the chain
growth probabilities and the molar olefin-(1) contents
can be given, the adjusted parameters are listed in
Table 3.
The increase of water partial pressure obtained by
addition of water to the syngas leads to a strong in-
Table 3
Model parameters used to fit the experimental FT product distri-
0 /k 0 = 5,
butions shown in Fig. 6. (In both cases: ka,2 /ka = 5, ka,2
a
0
kd,Ol /k = 1 and k 0 /k = 1; K according to the re-
-(1) d,Ol-(1) d,EP d,P N
spective reaction temperatures (see above))
Parameters Water partial pressures
pH2 O =0.9 bar pH2 O =8.5 bar
kd /kg 0.55 (0.645)a 0.20 (0.833)a
kd,Ol-(1) /kd,P 4 (80)b 4 (80)b
ka · mMe /V̇g
0.75 0.07
ka0 · mMe /V̇g 0.5 0.25
V̇l /V̇g 0.0004 0.0006
SHydr. + Isom. c 46% 79%
a Primary chain growth probability.
b ‘Primary’ molar olefin-(1) content in fraction of linear hydrocar-
bons (in mol%).
c Selectivity of hydrogenation plus isomerisation via double bond
shift of primarily formed n-olefins-(1).
crease of the ‘primary chain growth probability’ (from
ca. 65 to ca. 85%) or a strong inhibition of prod-
uct desorption, the characteristic feature of FT syn-
thesis [33–35]. Secondary olefin reactions are gener-
ally suppressed by water, as indicated by lower values
of the parameters ka · mMe /V̇g and ka0 · mMe /V̇g (re-
mark: the quotient mMe /V̇g is also identical in the two
cases). The selectivity of olefin hydrogenation plus
isomerisation can be estimated: it equals ca. 46% at
pH2 O = 0.9 bar and ca. 79% at the high water partial
pressure (pH2 O = 8.5 bar). This is, so far, in contradic-
tion to experimental findings by Iglesia et al. [38],
who cofed ethene during FT synthesis over cobalt and
ruthenium catalysts in fixed bed reactors at different
water concentrations and reported the preferred selec-
tive ethene incorporation in water enriched systems.
However, in all the above shown model calcula-
tions a ‘primary olefin-(1) selectivity’ of 80 mol%, or
kd,Ol-(1) /kd,P = 4, was assumed. The following analy-
sis shows, that secondary olefin reactions are strongly
dependent on this input parameter. Table 4 presents
the respective model parameters, ka · mMe /V̇g and
ka0 · mMe /V̇g , which were adjusted to obtain an optimal
fit of experimental data for the run with the cobalt cat-
alyst (conditions, see Table 1), and the corresponding
selectivities of secondary olefin reactions as a function
of varied ratios of kd,Ol-(1) /kd,P .
With increasing primary olefin-(1) selectivities
(range: 70–99 mol%) strongly increasing values of
ka0 · mMe /V̇g are required, indicating the preferred
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107 103

Fig. 6. Calculations with the extended kinetic model taking into account carbon number dependent product solubilities; fitting of experimental
data with the catalyst Co–Zr–SiO2 –Ru at two different water partial pressures (reaction conditions: T = 190◦ C, pH2 ≈ 5.8 bar, pCO ≈ 2.9 bar,
τ ≈ 27 min [45,55]). (Dashed lines: without readsorption, solid lines: with readsorption as species SpN and Sp0N ). (Model parameters: see
P
Table 3) left: ASF plot (normalised for 15 N =2 MN ); middle: chain growth probability pg,N ; right: molar olefin-(1) content in hydrocarbon
fractions.

Table 4
Model parameters used to fit the experimental FT product distri-
bution obtained with the cobalt catalyst, see Fig. 5. Effect of the
parameter kd,Ol-(1) /kd,P on selectivity of secondary olefin reac-
0 /k 0 = 10, k 0
tions. (In all cases: ka,2 /ka = 10, ka,2 a d,Ol-(1) /kd,Ol-(1) = 1,
0
kd,EP /kd,P = 1; kd /kg = 0.6 and V̇l /V̇g = 0.0004, KN according to
the respective reaction temperatures (see above))
Parameter kd,Ol-(1) /kd,P
2.3 (70)a 4 (80)a 9 (90)a 19 (95)a 100 (99)a
ka · mMe /V̇g 0.95 0.85 0.75 0.70 0.65
ka0 · mMe /V̇g 0.05 0.60 2.2 5.0 26.0
SHydr. + Isom. b 21% 48% 76% 88% 98%
a ‘Primary’ molar olefin-(1) content in fraction of linear hydrocar-
bons (in mol%).
b Selectivity of hydrogenation plus isomerisation via double bond
shift of primarily formed n-olefins-(1).
olefin consumption via Sp0N species, that are not
involved in chain growth. This results in strongly (lin-
early) increasing selectivities of olefin hydrogenation
and isomerisation.
Primary olefin-(1) selectivities, which can be es-
timated by back calculations from results of olefin
cofeeding experiments [44,45] lie in the range of up
to 80% with the cobalt catalyst, ca. 80% with the cat-
alyst Fe–Al–Cu and ca. 85% with the alkalised iron
catalyst Fe–Al–Cu–K. With all catalysts the selectiv-
ities of hydrogenation plus isomerisation of the con-
verted added olefins amount to almost carbon number
independent values of ca. 75–90%. The fitting of the
experimental product distributions with the model re-
sulted in selectivities of olefin hydrogenation plus iso-
merisation of around 40–70% (see above). This may
indicate, that incorporation of olefins is overpredicted
by the model, however, the results of the backcalcula-
tion of primary olefin-(1) selectivities from the result
of cofeeding studies is not very accurate and can only
give a rough idea of the respective real primary olefin
selectivites, which, as a parameter of the model, has a
strong effect on the observed selectivities, but almost
no effect on the quality of the data fit. (Remark: In
other models much higher values of primary olefin se-
lectivities have been used (as calculated by us): Iglesia
et al. [37–40] adjusted chain termination probabilities
of olefins and paraffins at β O = 0.4 and β H = 0.058,
which corresponds to a primary olefin selectivity of
ca. 87% to fit their experimental results for a Co–TiO2
catalyst with their model; Kuipers at al. [42] chose pri-
mary selectivities between 92 and 96% or T par = 0.02
or 0.018, T ol = 0.49 or 0.2, respectively to fit their ex-
perimental data (catalysts: Co-foil and Co–SiO2 ). The
impact of the primary olefin selectivity was not dis-
cussed by the mentioned authors.). The discrepance
of the model interpretations (ref.: effect of water on
SHydr. + Isom. ) and the results of ethene cofeeding of
Iglesia et al. [38] may be due to the choice of the
primary olefin-(1) selectivity, which itself (like the
primary chain growth probability) might be affected
by water.
It should further be noted, that the chain length de-
pendences of the olefin-(1) selectivities can in any case
be well described as an effect of the chain length de-
pendence of the product solubility in the model, even
104 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
without taking into account readsorption of olefins to
form ‘growing’ species SpN (ka ·mMe /V̇g = 0). However,
olefin cofeeding studies proove, that deviations from
ideal chain growth polymerisation kinetics are, at least
to some extent, due to olefin incorporation [44,45 and
references therein].
A carbon number dependence of rate constants of
chain growth or primary chain termination (account-
ing for effects of holdup of products/olefins due to
physisorption), which would also lead to chain length
dependent chain growth probabilities, could be ex-
cluded by Komaya and Bell [56] from interpretations
of transient response, isotopic tracer studies with a
Ru–TiO2 catalyst.
Physisorption, besides solubility and diffusional ef-
fects has been suggested by Kuipers et al. [43] to
contribute to chain length dependences observed in
FT distributions. Due to these authors, the strength of
physisorption, as solubility likewise, increases expo-
nentially with increasing carbon number, and should
therefore as well affect chain length dependent resi-
dence times of reaction products in a reaction system
(for effects of solubility on product residence times see
also [45]). They further proposed physisorption or a
physisorbed layer likewise to act as an ‘umbilical cord’
between an olefin and the growth site, from which
it desorbed. This scenario would suggest a transport
limitation, which would lead to a preferred reinser-
tion of indigenous olefins as opposed to insertion of
added/cofed olefins. Recent studies, with cofeeding of
olefins-(1) of different chain length in a slurry reactor
[44,45], however, show no evidence for the presence
of severe transport limitations (‘umbilical cord’ or dif-
fusion). In fact, longer chain olefins were preferen-
tially converted by hydrogenation plus isomerisation
and incorporation, and, moreover, very high apparent
activation energies of these reactions (ca. 150 kJ/mol)
argue against the existence of such limitations at the
specific reaction conditions applied.
Kuipers et al. [43] also discussed and compared the
strength of carbon number dependencies of the dif-
ferent effects (solubility, physisorption and diffusion),
which had been incorporated in published FT models.
Using Raoult’s law and the Clausius–Clapeyron equa-
tion they calculated a chain length dependence of solu-
bility as being fitted with e(0.55 ± 0.1)N (the correspond-
ing temperature was not mentioned by the authors),
in which N is the carbon number; for physisorption
they report a much weaker chain length dependence
(∝e(0.2 ± 0.1)N ), which, however, was just estimated by
fitting of experimental results (reaction temperature:
220◦ C) and lacks of substantial literature data. The
chain length dependence of diffusivity of DN ∝ e-0.3N
used by Iglesia et al. [37–40] for fitting their data with
their model accounting for diffusion enhanced olefin
readsorption solely, was noted by Kuipers et al. [43] to
disagree with literature, that predicts a much weaker
dependence proportional to N-0.6 . They therefore con-
cluded, dissolution and physisorption to usually dom-
inate among the three effects, that could cause chain
length dependent olefin reactions during FT synthesis.
On the other hand: systematic studies by Iglesia et al.
[37–40] provide some evidence that catalyst proper-
ties like particle diameter, average pore size and metal
dispersion can affect secondary olefin reactions and
that the effect of chain length dependent product dif-
fusivity cannot generally be ignored.
In a recent publication by van der Laan et al. [57]
dealing with chain length dependencies in FT prod-
uct distributions effects of solubility and physisorption
were regarded to cause the observed deviations from
ideal kinetics and incorporated into a model, which
accounts for olefin readsorption (no olefin hydrogena-
tion and isomerisation were considered) by lumping
the two effects together as matching a dependence pro-
portional to e(0.29 ± 0.07)N (observed by fitting of ex-
perimental results; reaction temperature: 250◦ C). An-
other paper (by Zimmerman et al. [41]) contains no
explicit information about the used chain length de-
pendence of solubility of FT products.
The solubilities used in our model are based on
Henry’s law (pN = γ N ·xN ·pN sat ), which in contrast to
Raoult’s law (pN = xN ·pN ), is valid for highly di-
sat
luted solutions [49] or small concentrations of a cer-
tain compound in the liquid phase, as present in a FT
system. The partition coefficient KN = (cl,N /cg,N )
can be expressed as (details see [44,45]):
ρwax (T ) · RT
KN = (24)
γN (T ) · pN
sat (T )
and also predicts an exponential and temperature de-
pendent increase with increasing carbon number. The
so derived dependencies of solubilities were deter-
mined as being proportional to e.g. e0.43N at 190◦ C
and e0.38N at 250◦ C, and differ significantly from the
dependencies used by other authors (see above).
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
Another distinguishing feature of our model as op-
posed to others is the incorporation of secondary olefin
hydrogenation and isomerisation via readsorption as
non-growing species Sp0N . Although taken into ac-
count in their kinetic scheme, Iglesia et al. [37–40]
have not made use of an additional olefin hydrogena-
tion route, whereas Kuipers et al. [42] have used a
second hydrogenation site for their model simulation.
Other models [41,57] only allow for readsorption on
growth sites.
None of the mentioned models, however, considers
the formation of olefins with internal double bonds
in any way; generally only linear ␣-olefins and linear
paraffins have been taken into account. (Remark: Zim-
merman et al. [41] used the experimentally observed
sums of all olefins in the fractions of the respective hy-
drocarbons for their model fitting, which may be one
reason for a rather poor agreement of model simula-
tions and experimental data). In our view olefin iso-
merisation via double bond shift plays a role in most
FT systems or at most reaction conditions respectively.
Our attempt to account for olefin isomerisation by
considering olefins with internal double bonds to be
‘inert’ with respect to readsorption, however, should
only count in systems, which are far away from partial
equilibria of olefin isomerisation and could be a mat-
ter of improvement of the presented, extended model.
As a further improvement the formation of oxy-
genates and their secondary reactions [58–63], which
show similarities to secondary olefin reactions could
be regarded. Finally, the additional effect of primary
and secondary chain branching [35,47] on total prod-
uct distributions could be examined in more detail.
(Remark: the incorporation of chain branching in the
existing basic model predicts slight deviations of the
product distributions of linear compounds in the ASF
diagram and chain length dependent probabilities of
linear chain growth [46]). However, all extensions of
the model coincide with an increase of model param-
eters.
5. Conclusions
Deviations from ideal Schulz–Flory kinetics and
with increasing carbon number decreasing molar
olefin-(1) contents in the respective hydrocarbon frac-
tions, which are observed in FT synthesis with differ-
105
ent kinds of catalysts, can be well described with a
kinetic model by accounting for olefin-(1) readsorp-
tion, incorporation, hydrogenation and isomerisation
of olefins-(1) and their chain length dependent solu-
bility in the liquid FT product as the only chain length
dependent parameter. Particularly, considering the in-
corporation and the olefin isomerisation and a sound
knowledge of the temperature dependent solubility
is believed to have led to the good agreement with
different sets of experimental data obtained in a gra-
dientless slurry reactor, where effects of diffusional
limitations can be neglected.
The so derived model, which is the extension of
an existing basic model, thereby leads to an improved
understanding of the kinetic occurrences in the com-
plex FT regime. It should, however, not be ignored,
that even the extended model still is based on simpli-
fications, which may explain discrepancies between
predictions and experimental data. This may be an in-
centive for further modifications of the flexible basic
model.
6. List of symbols and abbreviations used
6.1. Symbols
␣ chain growth probability (Eq. (1))
a adsorption
ASF Anderson–Schulz–Flory
c concentration (mol/m3 )
d diameter (␮m)
EP end product
FT Fischer–Tropsch
γ activity coefficient-
k rate constant (m3 /(min gMe ))
K partition coefficient (KN = cl,N /cg,N )
m mass (g)
M molar content in total organic products (mol%)
ṅ molar flow rate (mol/min)
Ol-(1) olefin-(1)
p reaction probability
p pressure (bar)
P paraffin
Pr organic product
ρ density (kg/m3 )
106 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107

r reaction rate (mol/(min gMe )) [15] S. Novak, R.J. Madon, Ind. Eng. Chem. Fundam. 23 (1985)
S selectivity (mol%) 114.
Sp surface species [16] H. Schulz, B.R. Rao, M. Elstner, Erdöl und Kohle 22 (1970)
Sp0 surface species, that do not participate in chain 651.
[17] R. Taylor, B.W. Wojciechowski, Can. J. Chem. Eng. 61 (1983)
growth 98.
τ mean reactor residence time in reactor gas [18] R. Taylor, B.W. Wojciechowski, Fuel Proc. Techn. 8 (1984)
phase (min) 135.
T temperature (◦ C) [19] B.W. Wojciechowski, Can. J. Chem. Eng. 64 (1986) 149.
[20] B.W. Wojciechowski, Catal. Rev.-Sci. Eng. 30 (1988) 629.
V̇ volumetric flow rate (m3 /min) [21] B. Sarup, B.W. Wojciechowski, Can. J. Chem. Eng. 62 (1984)
249.
6.2. Indices [22] B. Sarup, B.W. Wojciechowski, Can. J. Chem. Eng. 66 (1988)
831.
d desorption [23] N.O. Egiebor, W.C. Cooper, B.W. Wojciechowski, Can. J.
Chem. Eng. 63 (1985) 826.
eff effective [24] L. König, J. Gaube, Chem.-Ing. Tech. 55 (1983) 14.
EP end product [25] G. Huff jr., C.N. Satterfield, J. Catal. 85 (1984) 370.
g gaseous [26] R.B. Anderson, in: P. Emmet (Ed.), Catalysis, vol. IV,
g growth Reinhold, New York, 1956, p. 1.
Hydr. olefin hydrogenation [27] A. Rautavuoma, H. Baan van der, Appl. Catal. 1 (1981) 247.
[28] A. Takuchi, J. Katzer, G. Schuit, J. Catal. 82 (1984) 3271.
Isom. olefin isomerisation via double bond shift [29] J. Baker, A.T. Bell, J. Catal. 78 (1982) 165.
l liquid [30] R. Dictor, A.T. Bell, J. Catal. 97 (1986) 121.
Me active metal [31] T.J. Donelly, I.C. Yates, C.N. Satterfield, Energy and Fuels
N carbon number 2 (1989) 734.
[32] T.J. Donelly, C.N. Satterfield, Appl. Catal. 52 (1989) 93.
Ol-(1) olefin-(1) [33] H. Schulz, K. Beck, E. Erich, Stud. Surf. Sci. Catal. 36 (1988)
P particle 457.
P paraffin [34] H. Schulz, K. Beck, E. Erich, Fuel Proc. Technol. 18 (1988)
s catalyst surface 293.
sat saturation [35] H. Schulz, K. Beck, E. Erich, in: M. Phillips, M. Ternan
(Eds.), Proc. 9th Int. Congr. on Catal., Calgary, 1988, vol. 2,
The Chemical Institute of Canada, Ottawa, 1988, p. 829.
[36] H. Pichler, H. Schulz, M. Elstner, Brennstoff-Chemie 48
References (1967) 78.
[37] E. Iglesia, S.C. Reyes, R.J. Madon, J. Catal. 129 (1991) 238.
[1] S.R. Craxford, E. Rideal, Brennstoff-Chemie 20 (1939) 263. [38] E. Iglesia, S.C. Reyes, R.J. Madon, S.L. Soled, Adv. Catal.
[2] R. Brady, R. Pettit, J. Am. Chem. Soc. 102 (1980) 6181. 39 (1993) 239.
[3] R. Brady, R. Pettit, J. Am. Chem. Soc. 103 (1981) 1287. [39] E. Iglesia, S.C. Reyes, S.L. Soled, in: E. Becker, R. Pereira
[4] A.T. Bell, Catal. Rev.-Sci. Eng. 23 (1981) 203. (Eds.), Computer Aided Design of Catalysts and Reactors,
[5] H.H. Storch, N. Golumbic, R.B. Anderson, The Marcel Dekker, New York, 1993, p. 199.
Fischer–Tropsch and Related Synthesis, Wiley, New York, [40] E. Iglesia, Appl. Catal. 161 (1997) 59.
1951. [41] W. Zimmerman, D. Bukur, S. Ledakowicz, Chem. Eng. Sci.
[6] A. Sternberg, J. Wender, Proc. Int. Conf. Coordination Chem., 47(9-11) (1992) 2707.
London 1959, The Chem. Soc., London, 1959, p. 53. [42] E.W. Kuipers, C. Scheper, J.H. Wilson, I.H. Vinkenburg, H.
[7] S. Roginski, Proc. 3rd Congr. on Catal., Amsterdam, 1965, Oosterbeek, J. Catal. 158 (1996) 228.
p. 939. [43] E.W. Kuipers, I.H. Vinkenburg, H. Oosterbeek, J. Catal. 158
[8] H. Pichler, H. Schulz, Chem.-Ing. Tech. 42 (1970) 1162. (1996) 228.
[9] P. Biloen, W.M.H. Sachtler, Adv. Catal. 30 (1981) 165. [44] M. Claeys, Ph.D. thesis, University of Karlsruhe, 1997.
[10] M.E. Dry, Catal. Today 6 (1990) 183. [45] H. Schulz, M. Claeys, Appl. Catal. A 186 (1999) 71.
[11] E.F.G. Herington, Chem. Ind. 65 (1946) 346. [46] E. Steen van, Ph.D. thesis, University of Karlsruhe, 1993.
[12] R.A. Friedel, R.B. Anderson, J. Am. Chem. Soc. 72 (1950) [47] H. Schulz, E. Steen van, M. Claeys, Stud. Surf. Sci. Catal.
1212, 2307. 81 (1994) 455.
[13] R.B. Abderson, L. Hofer, H. Storch, Chem.-Ing. Tech. 30 [48] H. Schulz, H. Gökcebay, in: Prepr. 9th Conf. on Catal. of
(1958) 560. Org. Reactions, Charleston, SC, USA, 1982; in: J.R. Kosak
[14] S. Novak, R.J. Madon, H. Suhl, J. Chem. Phys. 74 (1981) (Ed.), Catalysis of Organic Reactions, Marcel Dekker, New
6083. York, 1984, p. 153.
 H. Schulz, M. Claeys / Applied Catalysis A: General 186 (1999) 91–107
[49] A.B. Littlewood, Gas Chromatography;
Principles, Techniques and Applications, 2nd ed., Academic
Press, New York, San Francisco, London, 1970.
[50] H. Schulz, W. Böhringer, C.P. Kohl, N.M. Rahman, A. Will,
DGMK-Forschungsbericht 320, DGMK Hamburg, 1984.
[51] M. Poulson, H. Jensen, J. Chrom. Sci. 9 (1971) 300.
[52] H. Schulz, E. Steen van, M. Claeys, Top. Catal. 2 (1995) 223.
[53] J.E. Germain, Catalytic Conversion of Hydrocarbons,
Academic Press, London, New York, 1969.
[54] D.R. Stull, E.F. Westrum, jr., G.C. Sinke, The Chemical
Thermodynamics of Organic Compounds, Wiley, New York,
1969.
[55] H. Schulz, M. Claeys, S. Harms, Stud. Surf. Sci. Catal. 107
(1997) 193.
[56] T. Komaya, A.T. Bell, J. Catal. 146 (1994) 237.
107
[57] G.P. Laan van der, A.A.C.M. Beenackers, Stud. Surf. Sci.
Catal. 119 (1998) 179.
[58] T. Eidus, Ya. Russ, Chem. Rev. 36(5) (1967) 338.
[59] A. Aksoy, Ph.D. thesis, University of Karlsruhe,
1975.
[60] J.T. Kummer, H. Podgurski, W. Spencer, P.H. Emmett, J. Am.
Chem. Soc. 73 (1951) 564.
[61] J.T. Kummer, P.H. Emmett, J. Am. Chem. Soc. 75 (1952)
5177.
[62] R.J. Kokes, W.K. Hall, P.H. Emmett, J. Am. Chem. Soc. 79
(1957) 2989.
[63] L.-M. Tau, H.A. Dabbagh, S. Bao, B. Chawla, B.H. Davis,
in: M.J. Phillips, M. Ternan (Eds.), Proc. 9th Int. Congr.
on Catal., vol. 2, Calgary, 1988, The Chemical Institute of
Canada, Ottawa, 1988, p. 861.