5066 Ind. Eng. Chem. Res.

2003, 42, 5066-5090

Detailed Kinetics of Fischer-Tropsch Synthesis on an Industrial

Fe-Mn Catalyst
Jun Yang,†,‡ Ying Liu,†,‡ Jie Chang,† Yi-Ning Wang,† Liang Bai,† Yuan-Yuan Xu,†
Hong-Wei Xiang,† Yong-Wang Li,*,† and Bing Zhong†

Group of Catalytic Kinetics & Theoretical Modeling, State Key Laboratory of Coal Conversion,
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, People’s Republic of China, and
Department of Chemistry, Jinan University, Guangzhou 510632, People’s Republic of China

The detailed kinetics of the Fischer-Tropsch synthesis over an industrial Fe-Mn catalyst was
studied in a continuous integral fixed-bed reactor under the conditions relevant to industrial
operations [temperature, 540-600 K; pressure, 1.0-3.0 MPa; H2/CO feed ratio, 1.0-3.0; space
velocity, (1.6-4.2) × 10-3 Nm3 kg of catalyst-1 s-1]. Reaction rate equations were derived on the
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basis of the Langmuir-Hinshelwood-Hougen-Watson type models for the Fischer-Tropsch

reactions and the water-gas-shift reaction. Kinetic model candidates were evaluated by the global
optimization of kinetic parameters, which were realized by first minimization of multiresponse
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objective functions with a genetic algorithm approach and second optimization with the
conventional Levenberg-Marquardt method. It was found that an alkylidene mechanism based
model could produce a good fit of the experimental data. This model shows that the desorption
of the products and the insertion of methylene into the metal-alkylidene bond are the rate-
determining steps. The activation energy for olefins formation is 97.37 kJ mol-1 and smaller
than that for the paraffin formation (111.48 kJ mol-1). In this model, the readsorption and
secondary reactions of olefins are taken into account, and deviations of hydrocarbon distribution
from the conventional ASF distribution can therefore be quantitatively described. However, the
deeper information for the olefin-to-paraffin ratio has not intrinsically been described in the
present stage, leaving for the further improvements in models to consider the transportation-
enhanced readsorption and secondary reaction of olefins more practically in the reactor modeling
stage.

1. Introduction The quality of a detailed kinetic model is closely

Fischer-Tropsch synthesis (FTS) is an industrially
important process for the conversion of syngas (H2/CO)
derived from carbon sources such as coal, peat, biomass,
and natural gas into hydrocarbons and oxygenates.
Today, it continuously attracts interest as an option for
the production of clean transportation fuels and chemi-
cal feedstocks.1-3 The FTS product is composed of a
complex multicomponent mixture of linear and branched
hydrocarbons and oxygenated products, the majority of
which are linear hydrocarbons.3,4
The FTS kinetics has extensively been studied, and
many attempts have been made for the rate equations
describing the FTS reactions.4-13 In most cases, the
hydrocarbon products were lumped according to the
carbon number of hydrocarbon molecules with an ideal
Anderson-Schulz-Flory (ASF) distribution. Although
a few of the available kinetic models were developed
based on the detailed mechanism of the Langmuir-
Hinshelwood-Hougen-Watson (LHHW) type,4,10-13 only
two of them simultaneously considered both the syn-
gas conversion rates and the hydrocarbon formation
rates.11-13 We have pointed out the deficiencies existing
in the conventional lumped models and those tailing
syngas conversion rates with a carbon number distribu-
tion formula when a comprehensive simulation is
required.13
†
Chinese Academy of Sciences.
‡
Jinan University.
10.1021/ie030135o CCC: $25.00 © 2003 American Chemical Society
Published on Web 09/11/2003
related to the understanding of the mechanism in the
FTS catalytic reaction system, in which a polymeriza-
tion process has been recognized to be dominant;
however, sufficient details on the FTS mechanistic
aspect are not yet fully understood.10,14,15 In 1946,
Herington first treated the molar distribution of hydro-
carbons from FTS in terms of a polymerization mech-
anism.15,16 The same formulation was rediscovered by
Anderson et al. in 1951 and named the ASF distribu-
tion.7,16 In the ASF model, the formation of hydrocarbon
chains was assumed as a stepwise polymerization pro-
cedure and the chain growth probability was assumed
to be independent of the carbon number. However,
significant deviations from the ideal ASF distribution
have been observed in many studies.17-20 Pichler et al.21
for the first time reported the deviations of experimental
results from the ASF distribution. The usual deviations
of the distribution of the linear hydrocarbons are a
relatively higher selectivity to methane, a relatively
lower selectivity to ethane, and an increase in the
chain growth probability with increasing molecular size
in comparison to the ideal ASF distribution. Several
different explanations about the cause of these devia-
tions have been proposed.22-24 Some authors25,26 inter-
preted the deviations from the standard ASF distribu-
tion by the superposition of two ASF distributions. They
suspected the existence of two sorts of sites for the chain
growth on the catalyst surface and, therefore, proposed
that each site might individually yield the ideal ASF

distribution with different chain growth probabilities.
However, this explanation cannot interpret the increase
of the paraffin/olefin ratio with the chain length. On the
basis of the experiments with cofed olefins, it was noted
that the readsorption and secondary reaction of olefins
had a great influence on the products distribution of
FTS.27 Some researchers28-30 proposed a more plausible
explanation for these deviations and suggested that the
occurrence of secondary reactions of the olefins caused
the deviations from the ASF distribution. Iglesia et al.30
developed a model describing the olefin readsorption
effect enhanced by intraparticle and interparticle trans-
port processes. They suggested that the diffusion limita-
tion within liquid-filled pores slowed the removal of
1-olefins, which caused an increase of their residence
time within the catalyst pores. In their model, the CO
hydrogenation model and the olefin readsorption model
were treated separately. In 1992, Zimmerman and
Bukur31 developed a model for both the formation of
linear hydrocarbons and the water-gas-shift (WGS)
reaction over iron catalysts. In their model, the read-
sorption and secondary reaction of olefins were taken
into account and the increase of the paraffin/olefin ratio
with the carbon number can be predicted. However, the
results displayed significant deviations between model
predicted and experimental mole fractions, especially
for methane and ethene. Kuipers et al.32 proposed a
chain-length-dependent olefin readsorption mechanism
to explain the fact that the paraffin/olefin ratio increases
with the carbon number. On the basis of the olefin
cofeeding kinetic experiments over cobalt catalyst in a
continuously operated and well-mixed slurry reactor,
Schulz and Claeys33 developed a kinetic model for the
Fischer-Tropsch reaction system.
It is well accepted that the FTS reaction is a surface
polymerization reaction, but its detailed mechanism is
still not fully understood. Recent mechanistic studies
show new evidence in favor of a mechanism start with
CO dissociation. It is generally agreed that the FTS
proceeds via the dissociation of CO, further forming
carbide on the surface in sequence of the hydrogenation
of this carbide.10,34,35 Despite considerable research
efforts, uncertainties still remain about the mechanism
of chain growth in the FTS reaction. Brady and Pettit36
proposed an alkyl mechanism and suggested that the
chain growth is initiated by the insertion of methylene
into the adsorbed alkyl. Martinez et al.37 proposed a
chain growth mechanism, in which the chain growth is
initiated by an R-vinyl and the polymerization process
proceeds through the reaction between methylene and
an alkenyl. Joyner38 developed an alkylidene mecha-
nism and assumed the chain growth process propagated
via the successive insertion of methylene into the
metal-alkylidene bond. With this model, one can easily
explain the formation of R-olefins as the primary
products in FTS. These proposed models have provided
a basis for a workable kinetic model derived from
experimental data. However, models are still far from
meeting the demands for both better mechanism un-
derstanding and applications in engineering scale-up,
leaving a great deal of work under the expectation for
a better treatment in considering both the fundamental
mechanism and self-consistency in rate expressions.10,13
Lox and Froment11,12 studied the FTS kinetics over
an iron catalyst. On the basis of the LHHW scheme,
they developed several sets of “elementary steps”, from
which detailed kinetic models were derived by assuming
Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5067
the carbide mechanism for the FTS and the formate
intermediate scheme for the WGS reaction. The rates
of CO or H2 consumption and product formation were
unified in these models. Experimental data were re-
gressed with large-scale nonlinear optimization ap-
proaches for determining the “best” kinetic parameters,
and statistical analysis was applied to validate the
feasibility of both models and parameters in them. The
final model could describe the distribution of linear
paraffins and olefins of FTS obeying the ideal ASF
distribution at the level of surface reaction. However,
the deviations, observed in many experiments, from the
ideal ASF distribution were totally neglected in their
model. Very recently, we have proposed a systematic
approach for considering more complicated olefin read-
sorption phenomena in kinetic modeling on the basis
of ideas similar to those of Froment.13 Although pri-
mary, namely, a limited number of mechanism sets,
from which only about 10 kinetic models were scanned,
were considered, our optimal model for an industrial
iron catalyst showed a better description for the non-
ideal ASF distribution than that from Lox and Froment.
However, the models based on the detailed mechanism
scan for FTS processes need to first describe the most
intrinsic factors involved, namely, those defined at the
surface mechanism level, and the solubility/diffusivity-
enhanced paraffin/olefin ratio dependence on the carbon
number should be described through modification of the
models with intrinsic significances. This modification
needs to be carefully arranged at both the surface
mechanism and the reactor simulation levels because
the transportation-enhanced phenomena may not fun-
damentally be reflected solely either in an “intrinsic”
kinetic model or in reactor models using the intrinsic
kinetics correctly. This is because reactor models can
fundamentally account for transportation phenomena,
and at the same time long-chain olefins staying in the
catalyst pores filled with wax are difficult to remove
instantly as “defined” even in the case of kinetic
experimental conditions. In fact, this is a dilemma for
the kinetics modeling of FTS. The difficulties arise,
making kinetic modeling impossible, if one wants to
fundamentally take the transportation phenomena into
account for the modeling of a kinetic reactor. On the
basis of this understanding, we first make an attempt
to grasp the most significant intrinsic information at
the mechanism kinetic level, and later efforts will be
devoted to solving the modification problem for consid-
ering the transportation-enhanced phenomena with the
combination of kinetics and reactor simulations.
The goal of this paper is, therefore, to establish and
test detailed mechanistic kinetic models for the Fis-
cher-Tropsch system over an industrial Mn-Fe cata-
lyst while considering many more possibilities in mech-
anism combinations than before. The new mechanistic
model, in which the olefin readsorption and secondary
reactions are taken into account, combines all of the FTS
reactions with WGS reaction in a self-consistent way,
leaving the transportation-enhanced olefin readsorption
factor for further work in the combination of kinetics
and reactor simulations.
2. Experimental Section
The experimental setup used in this study is shown
in Figure 1. A micro-fixed-bed reactor (a 1.0 m long
stainless steel tube of 0.012 m in internal diameter with
5068 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003
Figure 1. Experimental setup: (1) gas cylinders; (2) pressure
meters; (3) pressure regulators; (4) pressure regulators before the
reactor; (5) mass flow controllers; (6) the reactor; (7) wet flowmeter;
(8) needle valves; (9) backpressure regulator; (10) purification
columns; (11) wax condenser; (12) oil/water condenser; (13) wax
trap (hot trap); (14) cold trap; (15) high-temperature ball valves;
(16) ball valves; (17) salt bath.
a temperature-controlled molten salt bath to achieve a
uniform temperature profile in the catalyst bed) was
used for all kinetic experiments. The catalyst used in
the kinetic study is an industrial manganese-promoted
iron catalyst prepared by Institute of Coal Chemistry
(ICC), Chinese Academy of Sciences. The preparation
method has been patented, and some open information
can be found in the literature.39,41 The fresh catalyst
was crushed and sieved to particles with diameters of
0.25-0.36 mm (40-60 ASTM mesh), which has been
proved to be a compromising particle size safe for
neglectable intraparticle transfer limitations and prom-
isingly easy operations to the reactor during the
experiment.10-13 A 3.58 g (3 cm3) catalyst was used for
the kinetic experiments. The catalyst was diluted by 24
cm3 inert silica sand [(catalyst:sand ) 1:8 (v/v)] with
the same mesh size range. Before the reaction, the
catalyst was reduced in situ with syngas (H2/CO ) 2.0)
in the reactor.
In a typical reduction procedure, operation conditions
were adjusted to 0.25-0.30 MPa and 1000 h-1 at 513
K, and then the temperature was raised to 548 K at
the rate of 1 K h-1 and retained at that temperature
for the whole reduction stage. After reduction for 36 h,
the temperature was lowered to 513 K and then the
operation conditions were adjusted to the desired value
for the FTS. For intrinsic kinetic studies, a high space
velocity is needed to exclude the external diffusion
limitation. In our work, the space velocity of (1.6-4.2)
× 10-3 Nm3 kg of catalyst-1 s-1 is much higher than
those reported by others,5,13 ensuring the kinetic experi-
ments with the neglected external diffusion effect.
The syngas was prepared by blending of pure CO and
H2 (>99.99% purity). The CO and H2 passed through a
series of an oxygen-removal trap, a heated silica gel
molecular sieve trap, and an activated charcoal trap to
remove tiny amounts of oxygen, water, and other
impurities. The flow rates of CO and H2 were controlled
by two Brooks 5850E mass flow controllers. The outlet
of the reactor is connected with a hot trap (420 K) and
then an ice trap (273 K) at the system pressure. After
these product collectors, the pressure was released
through a backpressure regulator. The flow rate of the
tail gas was monitored by a wet test gas meter. Gas
samples for the gas chromatograph were collected after
removal of the water.
For kinetic studies, a stabilization period of more than
1000 h was used to ensure that the stable catalytic
phases were established. This could avoid the sharp
change in crystalline structures observed in previous
experimental studies by other researchers.40,41-45 Ki-
netic samples were cumulatively collected during a
typical period of 10-16 h. For each operation condition,
it took at least 10 h to ensure the steady-state behavior
of the catalyst after a change of the reaction conditions.
The products of the synthesis were separated into
three portions: gas phase, liquid phase (from the ice
trap), and wax phase (from the hot trap). Both the
purified syngas and the tail gas were analyzed on a gas
chromatograph. H2, O2, N2, CH4, and CO were separated
on a 13× molecular sieve packed column (1.5 m × 3 mm
i.d., Ar carrier flow) and detected with a thermal
conductivity detector (TCD). C1-C5 hydrocarbons in the
gas phase were analyzed on a C220/C-22 (170-250 µm)
packed column (7.2 m × 3.2 mm i.d.) flame ionization
detector (FID) with N2 as the carrier. CO2 was measured
on a silica gel packed column (1 m × 3 mm i.d, H2
carrier) with TCD and quantified by an external stan-
dard method. The oil product from the cold trap was
separated on a 60 m × 0.25 mm (i.d.) OV-101 capillary
column (N2 carrier, FID) with the temperature pro-
grammed from 333 K (maintained for 20 min) to 563 K
at the rate of 3 K min-1. The wax product from the hot
trap was first dissolved in CS2 (0.5-1.0 mass %) and
then analyzed on a OV-101 capillary column, FID, and
N2 carrier with the temperature programmed (1 K
min-1) from 343 to 563 K. The water phase was
separated by using a BD-wax (GW, US) capillary
column (N2 carrier, FID). All of the data in steady-state
reactions showed promising material balances with
carbon, hydrogen, and oxygen material balances be-
tween 95 and 104%.
The experiences from our intensive experimental
investigations of the catalytic performances of various
FTS catalysts showed that better material balances are
difficult to reach in practice. This is partially due to the
fact that small fluctuations during a sampling time
brought about certain experimental errors for the final
results and partially due to the fact that the complexity
of the FTS products caused difficulties in analyses. In
addition, detailed kinetic modeling requires the infor-
mation of the compositions of the reactants and almost
all FTS products (hydrocarbons relevant) in each stream.
It is estimated that about 5% error in the total material
balances could produce very large errors (sometimes
several times) for the contents of components with very
small mole fractions in a stream. This error amplifica-
tion phenomenon in FTS makes it even more difficult
to achieve high modeling accuracy in detailed kinetics.
3. Kinetic Models
3.1. Active Site Assumption. The overall FTS
reactions can be simplified as the combination of FTS
reactions and the WGS reaction.11,12
paraffin formation: nCO + (2n + 1)H2 )
CnH2n+2 + nH2O (1)
olefin formation: nCO + 2nH2 ) CnH2n + nH2O (2)
WGS reaction: CO + H2O ) CO2 + H2 (3)

Active sites for the above reactions in FTS are still
not clear especially in the cases of iron catalysts. This
is because of the fact that the iron-based catalysts
starting from their oxide precursors have experimen-
tally proved to have complex phase transfer during the
reduction as well as synthesis operation.40,41-45 The
controversy in the active sites (or phases) in the FTS
system appeals the need for much attention to be paid
to the understanding of the FTS mechanism at a deep
level; for example, the work for Co or Ru catalysts, for
which metal phases are believed to be active phases for
FTS, has been considered at even a molecular level with
many interesting results achieved, casting an encourag-
ing light on the detailed mechanism understanding.46
For iron catalysts, however, we expect many more
challenges in this direction.41-49 Here, we will not go
into these controversies and instead will use experi-
mental data to fit many possible mechanism-derived
kinetic models, which are anyhow expected to reflect
the most important points of FTS catalysis and chem-
istry. Beyond the complexities in the FTS catalysis with
iron catalysts, it is generally accepted that reactions in
eqs 1-3 can be assumed to take place on two kinds of
active sites. The active sites for the hydrocarbon forma-
tion and the WGS reaction are iron carbides and
magnetite (Fe3O4), respectively.4,11-13,47-49
3.2. Kinetic Models for the Formation of Linear
Hydrocarbons. 3.2.1. Elementary Reactions of the
FTS. The FTS is a complex network of parallel and
series reactions involving different extents and deter-
mining altogether the overall catalyst performance. The
whole synthesis reaction can be simplified as the
combination of FTS reactions and the WGS reaction.
The FTS reactions considered here consist of surface
steps in five categories:50 (1) adsorption of reactants (H2
and CO); (2) chain initiation; (3) chain propagation; (4)
chain termination and desorption of products; (5) read-
sorption and secondary reaction of olefins.
The CO adsorbed on the catalyst surface either in the
molecule state or in the dissociated state18,51-53
CO + s1 ) COs1 (4)
COs1 + s1 ) Cs1 + Os1 (5)
where s1 is an empty catalytic site, on which hydro-
carbon can be formed. The dissociative adsorption of
hydrogen takes place on two adjacent free active
sites.51-53
H2 + 2s1 ) 2Hs1 (6)
For the further formation of hydrogenated carbon
species, mechanism studies for FTS often assumed the
formation of CH2 and CH3 species,4,10-13,55 while recent
characterization and theoretical studies in energetics
debate for the increased possible formation of CH
species on several transition-metal surfaces.46,57 For iron
catalysts, the situation considered in theoretical models
(or the model catalysts and operation conditions in
characterization) describing the catalyst surfaces is
definitely too far from a real working catalyst, which
continuously changes in both the bulk phase and
surfaces due to the carbonization of the iron and the
hydrogenation of carbon species on the surface during
reduction and reactions.40-45,47,52 The carbides on the
catalyst surface may exchange carbon and hydrogen
sources with reactants and surface intermediates during
Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5069
Fischer-Tropsch catalysis cycling. The precise defini-
tion of the catalysis cycle during FTS on iron catalysts
is, therefore, impossible with the current understanding
of the FTS catalysis. Nevertheless, some conventional
ideas/treatments may serve for the development of
kinetic models. We here take advantage of the conven-
tional idea that the building block “CH2” is formed by
the reaction of a surface carbon with dissociated
hydrogen4,10-13,50,54,56 to build the kinetic models. It is
thus assumed that surface carbon species undergoes a
reaction with surface hydrogen:
Cs1 + Hs1 ) CHs1 (7)
CHs1 + Hs1 ) CH2s1 (8)
or with molecular hydrogen according to an Eley-Rideal
(ER) mechanism:
Cs1 + H2 ) CH2s1 (9)
Another possible pathway of the formation of “CH2”
starts with molecularly adsorbed carbon monoxide and
successive hydrogen-assisted dissociation,4,18,55
COs1 + Hs1 ) HCOs1 + s1 (10)
HCOs1 + Hs1 ) Cs1 + H2Os1 (11)
Cs1 + Hs1 ) CHs1 (12)
CHs1 + Hs1 ) CH2s1 (13)
or assisted by molecular hydrogen via the ER mecha-
nism:
COs1 + H2 ) H2COs1 (14)
H2COs1 + H2 ) CH2s1 + H2O (15)
There is still a controversy about the mechanism of
chain growth in the FTS. The alkyl mechanism proposes
that the reaction is initiated by the formation of a
methyl species and that chain growth takes place by
the successive insertion of methylene into the metal-
alkyl bond:36
CH2s1 + CnH2n+1s1 ) Cn+1H2n+3s1 + s1 (16)
The alkylidene mechanism proposes that the forma-
tion of the adsorbed ethylidene initiates the chain
formation and that chain growth is facilitated by meth-
ylene insertion into the metal-alkylidene bond:38
CH2s1 + CnH2ns1 ) Cn+1H2n+2s1 + s1 (17)
Another mechanism assumes that chain growth is
initiated by the adsorption of CO on the active sites
already containing a hydrocarbon intermediate and then
by a sequence of hydrogenation:56,58
CO + CnH2n+1s1 ) CnH2n+1s1CO (18)
CnH2n+1s1CO + H2 ) CnH2n+1s1C + H2O (19)
CnH2n+1s1C + H2 ) CnH2n+1s1CH2 (20)
5070 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003
Table 1. Elementary Reaction Sets for FTS
FT I 1 CO + s1 ) COs1
2 COs1 + H2 ) H2COs1
3 H2COs1 + H2 ) CH2s1 + H2O
4 H2 + 2s1 ) 2Hs1
5(n) CH2s1 + Hs1 ) CH3s1 + s1
CH2s1 + CH3s1 ) CH3CH2s1 + s1
CH2s1 + CnH2n+1s1 ) CnH2n+1CH2s1 + s1
6(n) CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
7(n) CnH2n+1s1 ) CnH2n + Hs1
FT II 1 CO + s1 ) COs1
2 COs1 + H2 ) H2COs1
3 H2COs1 + H2 ) CH2s1 + H2O
4 H2 + 2s1 ) 2Hs1
5(n) CH2s1 + Hs1 ) CH3s1 + s1
CH2s1 + CH3s1 ) CH3CH2s1 + s1
CH2s1 + CnH2n+1s1 ) CnH2n+1CH2s1 + s1
6 (n) CnH2n+1s1 + H2 ) CnH2n+2 + Hs1
7 (n) CnH2n+1s1 ) CnH2n + Hs1
FT III 1 CO + s1 ) COs1
2 COs1 + H2 ) H2COs1
3 H2COs1 + H2 ) CH2s1 + H2O
4 H2 + 2s1 ) 2Hs1
5(n) CH2s1 + CH2s1 ) CH2CH2s1 + s1
CH2s1 + CnH2ns1 ) CnH2nCH2s1 + s1
6(n) CnH2ns1 + Hs1 ) CnH2n+1s1 + s1
7(n) CH3s1 + Hs1 ) CH4 + 2s1
CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
8(n) CnH2ns1 ) CnH2n + s1
FT IV 0 H2 + 2s1 ) 2Hs1
1 CO + s1 ) COs1
2 COs1 + Hs1 ) HCO s1 + s1
3 HCOs1 + Hs1 ) Cs1 + H2Os1
4 H2Os1 ) H2O + s1
5 Cs1 + Hs1 ) CHs1 + s1
6 CHs1 + Hs1 ) CH2s1 + s1
7(n) CH2s1 + Hs1 ) CH3s1 + s1
CH2s1 + CH3s1 ) CH3CH2s1 + s1
CH2s1 + CnH2n+1s1 ) CnH2n+1CH2s1 + s1
8(n) CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
9(n) CnH2n+1s1 ) CnH2n + Hs1
FT V 0 H2 + 2s1 ) 2Hs1
1(n) CO + Hs1 ) Hs1CO
CO + CH3s1 ) CH3s1CO
CO + CnH2n+1s1 ) CnH2n+1s1CO
2(n) Hs1CO + H2 ) Hs1C + H2O
CH3s1CO + H2 ) CH3s1C + H2O
CnH2n+1s1CO + H2 ) CnH2n+1s1C + H2O
3(n) Hs1C + H2 ) Hs1CH2
CH3s1C + H2 ) CH3s1CH2
CnH2n+1s1C + H2 ) CnH2n+1s1CH2
4(n) CnH2n+1s1CH2 ) CnH2n+1CH2s1
5(n) CnH2n+1s1 + H2 ) CnH2n+2 + Hs1
6(n) CnH2n+1s1 ) CnH2n + Hs1
Termination of the chain growth can occur via
several routes. For the desorption of an olefin, a
single-site mechanism was assumed that R-olefins (1-
alkenes) may be formed by a β-hydride elimination
reaction
CnH2n+1s1 ) CnH2n + Hs1
or by the desorption of adsorbed alkylidene
CnH2ns1 ) CnH2n + s1
For the desorption of a paraffin, both a single-site
reaction with molecular hydrogen
CnH2n+1s1 + H2 ) CnH2n+2 + Hs1
FT VI 1 CO + s1 ) COs1
2 COs1 + s1 ) Cs1 + Os1
3 Cs1 + H2 ) CH2s1
4 Os1 + H2 ) H2O + s1
5 H2 + 2s1 ) 2Hs1
6(n) CH2s1 + Hs1 ) CH3s1 + s1
CH2s1 + CH3s1 ) CH3 CH2s1 + s1
CH2s1 + CnH2n+1s1 ) CnH2n+1CH2s1 + s1
7(n) CnH2n+1s1 + H2 ) CnH2n+2 + Hs1
8(n) CnH2n+1s1 ) CnH2n + Hs1
FT VII 0 H2 + 2s1 ) 2Hs1
1(n) CO + Hs1 ) Hs1CO
CO + CH3s1 ) CH3s1CO
CO + CnH2n+1s1 ) CnH2n+1s1CO
2(n) Hs1CO + Hs1 ) Hs1C + HOs1
CH3s1CO + Hs1 ) CH3s1C + HOs1
CnH2n+1s1CO + Hs1 ) CnH2n+1s1C + HOs1
3(n) CnH2n+1s1C + Hs1 ) CnH2n+1s1CH + s1
4(n) CnH2n+1s1CH + Hs1 ) CnH2n+1s1CH2 + s1
5(n) CnH2n+1s1CH2 ) CnH2n+1CH2s1
6 HOs1 + Hs1 ) H2O + 2s1
7(n) CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
8(n) CnH2n+1s1 ) CnH2n + Hs1
FT VIII 1 CO + s1 ) COs1
2 COs1 + s1 ) Cs1 + Os1
3 Cs1 + Hs1 ) CHs1 + s1
4 CHs1 + Hs1 ) CH2s1 + s1
5(n) CH2s1 + Hs1 ) CH3s1 + s1
CH2s1 + CH3s1 ) CH3CH2s1 + s1
CH2s1 + CnH2n+1s1 ) CnH2n+1CH2s1 + s1
6 H2 + 2s1 ) 2Hs1
7 Os1 + Hs1 ) HOs1 + s1
8 HOs1 + Hs1 ) H2O + 2s1
9(n) CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
10(n) CnH2n+1s1 ) CnH2n + Hs1
FT IX 1 CO + s1 ) COs1
2 COs1 + s1 ) Cs1 + Os1
3 Cs1 + Hs1 ) CHs1 + s1
4 CHs1 + Hs1 ) CH2s1 + s1
5(n) CH2s1 + CH2s1 ) C2H4s1 + s1
CH2s1 + CnH2ns1 ) CnH2nCH2s1 + s1
6 H2 + 2s1 ) 2Hs1
7 Os1 + Hs1 ) HOs1 + s1
8 HOs1 + Hs1 ) H2O + 2s1
9(n) CnH2ns1 + Hs1 ) CnH2n+1s1 + s1
10(n) CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1
11(n) CnH2ns1 ) CnH2n + s1
FT X 1 CO + s1 ) COs1
2 COs1 + s1 ) Cs1 + Os1
3 Cs1 + H2 ) CH2s1
4(n) CH2s1 + CH2s1 ) CH2CH2s1 + s1
CH2s1 + CnH2ns1 ) CnH2nCH2s1 + s1
5 H2 + 2s1 ) 2Hs1
6 Os1 + H2 ) H2O + s1
7(n) CnH2ns1 + Hs1 ) CnH2n+1s1 + s1
8(n) CnH2n+1s1 + H2 ) CnH2n+2 + Hs1
9(n) CnH2ns1 ) CnH2n + s1
and a dual-site reaction with an adsorbed hydrogen
atom
CnH2n+1s1 + Hs1 ) CnH2n+2 + 2s1 (24)
were considered.
(21) It is generally agreed that the R-olefins desorbed from
the catalyst surface can readsorb on the active sites and
take place as secondary reactions, which have signifi-
cant influences on the product distribution of the
FTS.29,59
(22)
On the basis of the above five categories of elementary
reactions, we can define 10 possible mechanisms for
FTS, as shown in Table 1.
3.2.2. Rate Expressions of the Hydrocarbon
Formation. On the basis of the detailed elementary
(23) reaction steps of FTS listed in Table 1, the formation
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5071

rates of the linear paraffins and olefins were derived. atoms. Here we introduce a readsorption factor βn,
For each model, the possible rate-determining steps which is defined as follows:
(RDSs) were identified, while all other steps were
assumed to be at quasi-equilibrium. k8- PCnH2n[s1]
βn ) (n g 2) (30)
Before we derive the rate expression of hydrocarbon k8+ [CnH2ns1]
formation, first, it is assumed that the steady-state
conditions are reached for both the surface composition The chain growth probability for the carbon chain
of catalyst and the concentration of all of the intermedi- with n carbon atoms is
ates involved. Second, it is assumed that the rate
constant of the elementary steps for the formation of k5[CH2s1]
hydrocarbons is independent of the carbon number of Rn )
the intermediates involved in the elementary reactions k5[CH2s1] + k7K6[Hs1]2/[s1] + k8+(1 - βn)
except for methane. Third, there are two types of (n g 2) (31)
uniformly distributed active sites respectively for FTS
and WGS reactions on the catalyst surface.4 The concentration of surface intermediates can be
For the derivation of the rate expressions, FT III expressed as a function of the partial pressure of CO,
H2, and H2O by applying the pseudo-equilibrium rela-
in Table 1 will be demonstrated. It is assumed
tion
that the RDSs are steps 5, 7, and 8 (model FT III).
The remaining steps can be considered to be rapid
and at equilibrium. The rates of formation of paraffins
PH22PCO PH22PCO
[CH2s1] ) K1K2K3 [s1] ) K′3 [s1] (32)
and olefins with n carbon atoms can thus be written PH2O PH2O
as
[Hs1] ) xK4PH2[s1] (33)
RCH4 ) k7M[CH3s1][Hs1] )
k7MK6[CH2s1][Hs1]2/[s1] (25) Substitution of eqs 32 and 33 in eq 31 yields

[CnH2ns1]
RCnH2n+2 ) k7[CnH2n+1s1][Hs1] ) Rn ) )
[Cn-1H2n-2s1]
k7K6[CnH2ns1][Hs1]2/[s1] (n g 2) (26) PH22PCO
k5K′3 [s1]
PH2O
RCnH2n ) k8+[CnH2ns1] - k8-PCnH2n[s1] (n g 2) (27)
PH22PCO
k5K′3 [s1] + k7K6K4PH2[s1] + k8+(1 - βn)
The pseudo-steady-state conditions are applied to the PH2O
concentration of surface intermediates [CnH2ns1]: (n g 2) (34)

d[CnH2nS1] Equation 28 can be rearranged as

- ) k5[CnH2ns1][CH2s1] -
dt k5[CH2s1][Cn-1H2n-2s1]
k5[Cn-1H2n-2s1][CH2s1] + k7[CnH2n+1s1][Hs1] + [CnH2ns1] ) +
k5[CH2s1] + k7K6[Hs1]2/[s1] + k8+
k8+[CnH2nS1] - k8-PCnH2n[s1] ) k5[CnH2ns1][CH2s1] -
k5[Cn-1H2n-2s1][CH2s1] + k7K6[CnH2ns1][Hs1]2/[s1] + k8-PCnH2n[s1]
(n g 2) (35)
k8+[CnH2ns1] - k8-PCnH2n[s1] ) 0 (n g 2) (28) k5[CH2s1] + k7K6[Hs1]2/[s1] + k8+

Equation 35 can be rewritten in the following form:13

After rearrangement, eq 28 yields
Xn ) RAXn-1 + BYn (36)
[CnH2ns1]
) where Xn, RA, Yn, and B are defined as follows:
[Cn-1H2n-2s1]
k5[CH2s1] Xn ) [CnH2ns1]

( )
) (n g 2) (37)
k8-PCnH2n[s1]
k5[CH2s1] + k7K6[Hs1]2/[s1] + k8+ 1 - k5[CH2s1]
k8+[CnH2ns1] RA ) )
k5[CH2s1]
k5[CH2s1] + k7K6K4PH2[s1] + k8+
(n g 2) (29)
k5[CH2s1] + k7K6[Hs1]2/[s1] + k8+(1 - βn) PH22PCO
k5K′3 [s1]
PH2O
where k5[CH2s1] is related to the chain growth of (38)
hydrocarbon and k8+(1 - k8-PCnH2n[s1]/k8+[CnH2ns1]) is PH22PCO
the rate of olefin formation, which is the net effect of k5K′3 [s1] + k7K6K4PH2[s1] + k8+
desorption and readsorption of olefins with n carbon PH2O
5072 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

k8- Thus, the expression of the concentration of [CnH2n+1s1]

B) +
) is
k5[CH2s1] + k7K6K4PH2[s1] + k8
[CnH2n+1s1] ) K6[CnH2ns1][Hs1]/[s1] )
k8-
(39) PH22.5PCO n
PH22PCO
k5K′3 [s1] + k7K6K4PH2[s1] + k8+
K6K4 0.5
K′3
PH2O
[s1] ∏
i)2
Ri (n g 2) (50)
PH2O

Yn ) PCnH2n[s1] (n g 2) (40) The concentrations of the surface intermediates [CH3s1],

[COs1], and [H2COs1] can be derived on the basis of the
elementary steps 1-4 and 7 in FT III.
From eq 36, we get

X2 ) RAX1 + BY2 (41) PH22.5PCO

[CH3s1] ) K6K1K2K3K40.5 [s1] )
PH2O
X3 ) RA2X1 + RABY2 + BY3 (42)
PH22.5PCO
0.5
K6K′3K4 [s1] (51)
X4 ) RA3X1 + RA2BY2 + RABY3 + BY4 (43) PH2O

............ [COs1] ) K1PCO[s1] (52)

n [H2COs1] )
Xn ) RAn-1X1 + B ∑
i)2
RAi-2Y(n-i+2) (n g 2) (44) K2PH2[COs1] ) K1K2PCOPH2[s1] ) K′2PCOPH2[s1] (53)

where X1 and Yn-i+2 are defined as follows: Normalization of the concentration of the sites on the
catalyst surface leads to
X1 ) [CH2s1] ) K3′PH22PCO/PH2O[s1] (45)
1 ) [s1] + [Hs1] + [COs1] + [CH2s1] + [H2COs1] +
n n
Yn-i+2 ) PC(n-i+2)H2(n-i+2)[s1] (n g 2) (46)
[CH3s1] + ∑
i)2
[CnH2ns1] + ∑[CnH2n+1s1]
i)2
(54)
Thus, the concentration of [CnH2ns1] can be rewritten
as Combining eqs 32, 33, and 49-53 with eq 54 gives
[CnH2ns1] )
n
1 ) [s1] + xK P
4 H2 + K1PCO[s1] +
RA n-1
[CH2s1] + B[s1] ∑ RA i-2
PC(n-i+2)H2(n-i+2) ) 2
PH2 PCO
i)2
K′3 [s1] + K1K2PCOPH2[s1] +
n
PH2O
RAn-1K′3PH22PCO/PH2O[s1] + B[s1] ∑
i)2
RAi-2PC (n-i+2)H2(n-i+2)
PH22.5PCO PH22PCO n i
(47) K6K40.5K′3
PH2O
[s1] + K′3
PH2O i)2
∑∏
j)2
(Rj)[s1] +
Substituting eqs 32 and 47 into eq 30 yields

{ [
PH22.5PCO n i
K6K4 K′30.5
∑ ∏(Rj)[s1] (55)
βn ) (k8-/k8+) PCnH2n/ RAn-1K′3PCOPH22/PH2O + PH2O i)2 j)2

The concentration of free active site [s1] can thus be

k8- expressed as follows:

[
×
k5K′3PCOPH22/PH2O[s1] + k7K6K4PH2[s1] + k8+

]} xK P
n [s1] ) 1/ 1 + 4 H2 + K1PCO +
∑ (RAi-2PC(n-i+2)H2(n-i+2)) (n g 2) (48)
i)2
PH22PCO
According to the definition of chain growth probability K′3 + K1K2PCOPH2 +
Rn in eq 34, we have PH2O

n
PH22.5PCO PH22PCO n i

[CnH2ns1] ) [CH2s1] ∏ Ri )
0.5
K6K4 K′3
PH2O
+ K′3
PH2O
∑ ∏(Rj) +

]
i)2 j)2
i)2
PH22PCO n PH22.5PCO n i
K′3
PH2O
[s1] Ri
i)2
∏ (n g 2) (49) K6K4 K′30.5

PH2O
∑ ∏(Rj)
i)2 j)2
(56)
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5073

Substituting eq 56 into eqs 49 and 50 yields n

RCnH2n ) k8+(1 - βn)K′3PH22PCO/PH2O ∏ Rj /

[
[CnH2ns1] ) j)2

[
PH22PCO
xK P
2
PH2 PCO n 1+ + K1PCO + K′3 +
∏
4 H2
K′3 Ri/ 1 + xK4PH 2
+ K1PCO + PH2O
PH2O i)2
PH22.5PCO
PH22PCO PH22.5PCO K1K2PCOPH2 + K6K40.5K′3 +
PH2O

]
0.5
K′3 + K1K2PCOPH2 + K6K4 K′3 +
PH2O PH2O PH22PCO n i

]
PH22PCO PH22.5PCO
K′3
P H 2O x
(1 + K6 K4PH2)
i)2
∑∏
j)2
(Rj) (61)
n i n i
K′3
PH2O
∑ ∏
i)2 j)2
(Rj) + K6K40.5K′3
PH2O
∑ ∏(Rj)
i)2 j)2 3.3. Kinetic Models for the WGS Reaction. The
kinetics of the WGS reaction has been intensively
(n g 2) (57) studied by many researchers, and several mechanisms
were proposed.60-64 It is generally accepted that the
[CnH2n+1s1] ) WGS reaction over supported iron catalysts proceeds via

[
a mechanism of formate species due to a limited change
PH22.5PCO n of oxidation states of the iron cations.4,60-64 Rethwisch
0.5
K6K4 K′3
PH2O
∏
i)2
Ri/ 1 + xK4PH 2
+ K1PCO + and Dumesic61 suggested that the WGS reaction pro-
ceeds on active sites different from those for FTS, and
for supported iron catalysts, the magnetite is the most
PH22PCO PH22.5PCO active phase for the WGS. On the basis of the formate
0.5 intermediate mechanism, the elementary steps of the
K′3 + K1K2PCOPH2 + K6K4 K′3 + WGS, and corresponding expressions of rates, equilib-
PH2O PH2O
rium constants are summarized in Table 2.

]
If we assumed that the slowest step in the WGS is
PH22PCO n i PH22.5PCO n i step IV (WGS 3), the rate of CO2 formation can be
K′3
PH2O
∑ ∏
i)2 j)2
(Rj) + K6K4 K′3 0.5

PΗ2Ο
∑ ∏(Rj)
i)2 j)2
written as follows:

RCO2 ) r4 ) kWGS4[COOH-s2] -
(n g 2) (58)
k-WGS4PCO2[H-s2] (62)
Substituting eqs 57 and 58 into eqs 25-27, we have
From the elementary step listed in Table 3, we have
RCH4 ) [CO-s2] ) KWGS1PCO[s2] (63)

[
3
PH2 PCO
KWGS2PH2O[s2]2 ) [OH-s2][H-s2] (64)
k7MK4K6K′3
PH2O
/ 1+ x K4PH2 + K1PCO +
KWGS3[OH-s2][CO-s2] ) [COOH-s2][s2] (65)
2 2.5
PH2 PCO PH2 PCO
K′3 + K1K2PCOPH2 + K6K40.5K′3 + [H-s2] ) xKWGS5PH2[s2] (66)
PH2O PH2O

]
On the basis of eqs 63-66, the concentrations of the
PH22PCO n i
2 surface intermediates [CO-s2], [OH-s2], and [COOH-
K′3
PH2O
(1 + K6 K4PH2)
i)2
x ∑∏
j)2
(Rj) (59) s2] can be derived as follows:

[CO-s2] ) KWGS1PCO[s2] (67)

RCnH2n+2 )
[OH-s2] ) KWGS2KWGS5-0.5PH2OPH2-0.5[s2] (68)

k7K4K6K′3
PH23PCO

PH2O
∏
n

j)2
Rj /
[
1+ xK P
4 H2 + K1PCO + [COOH-s2] )
KWGS1KWGS2KWGS3KWGS5-0.5PH2OPCOPH2-0.5[s2] (69)
PH22PCO PH22.5PCO
0.5 If Kp is used to represent the equilibrium constant of
K′3 + K1K2PCOPH2 + K6K4 K′3 + the WGS reaction, it can be expressed by the equilib-
PH2O PH2O rium partial pressures of CO, CO2, H2, and H2O.

PH22PCO

]
2 /
n i PCO P/
x ∑∏
2 H2
K′3 (1 + K6 K4PH2) (Rj) (60) Kp ) (70)
PH2O i)2 j)2 P/COPH
/
2O
5074 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

Table 2. Elementary Steps and Corresponding Expressions of Rates and Equilibrium Constants for the WGS Reaction
step elementary reaction expressions of rates and equilibrium constants
I CO + s2 ) COs2 KWGS1 ) [COs2]/PCO[s2]
II H2O + 2s2 ) OHs2 + Hs2 KWGS2 ) [OHs2][Hs2]/PH2O[s2]2
III COs2 + OHs2 ) COOHs2 + s2 KWGS3 ) [COOHs2][s2]/[COs2][OHs2]
IV COOHs2 ) CO2 + Hs2 r4 ) kWGS4[COOHs2] - k-WGS4PCO2[Hs2]
KWGS4 ) kWGS4/k-WGS4
V 2Hs2 ) H2 + 2s2 1/KWGS5 ) PH2[s2]2/[Hs2]2

Table 3. Rate Expressions for the WGS Reaction

model RDS rate expression
WGS1 step I RCO2 ) kv(PCO - PCO2PH2PH2O-1/Kp)/(1 + KvPCOPH2/PH2O)
WGS2 step III RCO2 ) kv(PCOPH2O/PH20.5 - PCO2PH20.5/Kp)/(1 + KvPH2O/PH20.5)2
WGS3 step IV RCO2 ) kv(PCOPH2O/PH20.5 - PCO2PH20.5/Kp)/(1 + KvPCOPH2O/PH20.5)

According to eqs 63, 64, and 66, the partial pressures Thus, the expressions of [H-s2] and [COOH-s2] can be
of CO, H2O, and H2 can be written as follows: obtained by substituting eq 80 into eqs 66 and 78.

P/CO ) [CO-s2]/(KWGS1[s2]) (71)

[H-s2] )
xKWGS5PH 2
(81)
/ 2 1 + KpKWGS4KWGS5 PCOPH2O/PH20.5
0.5
PH 2O
) [OH-s2][H-s2]/(KWGS2[s2] ) (72)

/
[COOH-s2] )
PH ) [H-s2]2/(KWGS5[s2]2) (73)
2
KpKWGS4KWGS50.5PCOPH2O/PH20.5
(82)
If we assumed that step IV reached the equilibrium 1 + KpKWGS4KWGS50.5PCOPH2O/PH20.5
state, the expression of partial pressure of CO2 at the
/
equilibrium state (PCO 2
) can be obtained: Finally, the rate expression of CO2 formation can be
/ expressed as
PCO 2
) [COOH-s2]*/(KWGS4[H-s2]*) (74)
kv(PCOPH2O/PH20.5 - PCO2PH20.5/Kp)
Substituting eq 71-74 into eq 70 gives RCO2 ) (83)
1 + KvPCOPH2O/PH20.5
KWGS1KWGS2[COOH-s2]*[s2]*
Kp ) (75) where Kv ) KpKWGS4KWGS50.5 and kv ) kWGS4Kv.
KWGS4KWGS5[CO-s2]*[OH-s2]*
By different assumptions of the RDS in WGS, other
When eq 65 is substituted into eq 75, Kp can be rate expressions of CO2 of the WGS reaction can be
expressed as derived, and the results are tabulated in Table 3. The
equilibrium constant Kp of the WGS reaction can be
KWGS1KWGS2KWGS3 calculated by the following relation:11-13
Kp ) (76)
KWGS4KWGS5 5078.0045
Kp ) - 5.8972089 + 13.958689 ×
T
Equation 76 can rewritten as follows:
10-4T - 27.592844 × 10-8T 2 (84)
KWGS4KWGS5KP A total of 39 kinetic models of FTS can be obtained by
KWGS3 ) (77)
KWGS1KWGS2 the combination of 13 FTS models with 3 WGS models.

Substituting eq 77 into eq 69 yields

[COOH-s2] )
KpKWGS4KWGS50.5PCOPH2OPH2-0.5[s2] (78)
As a result of the assumption that the RDS is step
IV, it can be considered that the concentration of the
adsorbed species [COOH-s2] is much larger than those
of the other adsorbed species.
[COOH-s2] + [s2] ) 1 (79)
The concentration of the empty active site, [s2], can be
obtained by substituting eq 78 into eq 79
1 1000 h, aiming at the complete establishment of the
[s2] ) (80)
1 + KpKWGS4KWGS50.5PCOPH2O/PH20.5
4. Results and Discussion
4.1. Experimental Results. Iron-based Fischer-
Tropsch catalysts, once exposed in the synthesis gas
under typical reduction or initial reaction conditions,
are normally reduced by H2 and CO, transforming from
their oxide phases to metallic and carbide phases.40,41-45
During this transformation stage, the phases of cata-
lysts greatly change with time on stream as well as
changes in operation conditions, leading to irreproduc-
ible experimental data. To minimize (it can never be
completely eliminated in FTS over iron catalysts) the
effect of a “sharp” phase change on the quality of kinetic
data, the catalyst used for kinetic tests was reduced and
then stabilized at a fixed operation condition for about
catalyst phase for FTS. After this stabilization stage,
operation conditions were switched according to kinetic
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5075

Figure 2. Catalyst stability with time on stream (H2/CO ) 2.0; P ) 23 bar; GHSV ) 5.1 × 10-4 Nm3 kg of catalyst-1 s-1).

Table 4. Catalyst Performance with Time on Stream during the Stability Test
time on stream (h)
34 83 180 273 404 516 641 845 960
temperature (K) 543 543 556 556 556 556 556 556 556
pressure (MPa) 2.30 2.30 2.30 2.30 2.30 2.30 2.30 2.30 2.30
GHSV (10-4 Nm3 kg of catalyst-1 s-1) 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1
CO conversion % 94.8 94.6 96.1 96.9 95.9 96.4 96.0 96.1 96.0
H2 conversion % 43.7 40.1 44.3 47.6 41.7 44.6 47.4 45.8 44.8
H2/CO (in feed gas) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
H2/CO (in tail gas) 21.55 22.13 28.33 34.35 28.61 30.43 25.95 27.25 28.21
selectivity CO2 (%) 36.09 40.88 38.71 39.13 36.73 39.27 40.37 38.70 38.80
selectivity (wt %)
C1 7.51 9.39 13.35 14.44 15.62 16.80 16.76 16.84 16.90
C20 3.00 4.26 6.17 7.04 7.41 8.20 8.20 8.24 8.30
C2) 5.31 5.18 5.35 4.81 4.87 4.91 4.85 4.39 4.41
C30 1.76 2.18 2.77 2.94 3.32 3.55 3.63 3.59 3.63
C3) 7.63 8.15 8.82 8.91 8.61 9.08 9.28 8.47 8.50
C40 1.51 1.83 2.07 2.11 2.31 2.51 2.51 2.49 2.48
C4) 6.04 6.19 6.58 6.46 6.68 6.63 7.05 6.37 6.40
C2-4)/tol‚HC (wt %) 18.99 19.51 20.75 20.18 20.16 20.62 21.18 19.23 19.21
C2-4)/C2-40 2.89 2.19 1.70 1.48 1.38 1.28 1.30 1.18 1.17
C5+ 67.24 62.82 54.89 53.29 51.19 48.33 47.72 49.61 49.40

sampling arrangements. The reaction results during the
stabilization stage are summarized in Table 4 and
Figure 2. From these results, it can be found that the
catalyst reached a stable stage after about 500 h on
stream under the conditions used. The selectivity to CO2
was maintained at the level of 40 ( 2%, that to CH4 at
16 ( 1%, that to C5+ at 50 ( 2%. For the activity, CO
conversion reached to a level of 95 ( 1%. This confirmed
that kinetic data sampling may be based on a rather
stable stage of the catalyst in the following kinetic
experimental stage.
Kinetic sampling conditions were arranged according
to orthogonal arrangement of sampling points, enabling
efficient and optimal distribution of experimental points.13
The reaction condition variables that need to be con-
sidered are temperature, pressure, and H2/CO ratio. For
each variable, four values were planned, bringing about
16 experimental points (corresponding to an orthogonal
table of L16(43)). The experimental results obtained in
this investigation for different reaction temperatures,
total reaction pressures, space velocities, and H2/CO
ratios are given in Table 5. Five more points were added
to consider more reaction conditions, among which one
point (no. 16 in Table 5) was the reference point (no. 12
in Table 5). The order of kinetic experiments was from
no. 1 to no. 21 listed in Table 5. From the results listed,
it can be found that the CO and H2 conversions at no.
16 well reproduced those at no. 12, indicating that the
catalytic phase reached a stable state.
4.2. Estimation of the Kinetic Parameters. 4.2.1.
Reactor Model of the Fixed Bed. The reactor model
for describing the kinetic experimental conditions is
assumed to be a plug-flow homogeneous state. At this
stage, the transportation in catalyst pores and the
solubilities of different hydrocarbons are not considered
in order to avoid the unsolvable difficulties in the
5076 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

Table 5. Operation Conditions and Resulting Product Quantities

T P H2/CO Fin reaction CO convn H2 convn Vexit oil wax water
no. (°C) (MPa) ratio (mL/min) time (h) (%) (%) (mL/min) (g) (g) (g)
1 283.0 1.98 2.05 342.0 10.60 40.9 28.2 308.9 2.46 2.14 7.20
2 283.2 2.51 2.62 348.6 10.67 57.0 28.9 292.5 3.62 2.83 8.04
3 283.3 3.05 3.08 435.6 7.01 57.6 26.8 375.8 2.16 1.85 8.40
4 283.1 1.50 1.03 343.6 12.86 21.8 21.0 341.6 1.92 3.36 5.10
5 283.2 3.05 3.06 349.3 11.33 70.1 28.9 287.8 3.52 3.24 14.30
6 297.0 2.02 1.03 449.7 6.02 35.8 27.6 404.3 2.28 3.06 4.50
7 297.2 2.51 3.13 462.9 10.83 69.0 25.8 408.7 4.21 3.41 15.52
8 297.1 3.01 2.58 456.1 7.51 74.9 36.6 346.7 3.89 2.64 10.02
9 297.2 3.02 2.59 606.9 10.22 59.2 33.7 482.6 5.83 4.27 15.77
10 297.1 1.50 2.07 454.7 10.51 35.2 26.8 411.5 2.71 2.02 8.20
11 297.0 2.05 2.05 342.0 6.02 66.1 34.5 270.2 2.46 1.62 4.60
12 312.2 2.02 3.05 684.6 7.03 63.3 27.7 575.0 3.02 0.78 12.70
13 312.3 3.02 2.04 686.9 13.25 70.9 38.0 492.5 12.56 4.55 27.59
14 312.1 2.50 1.02 678.6 11.04 42.6 31.1 599.4 9.18 7.49 12.60
15 312.0 1.50 2.55 686.9 9.01 38.9 17.1 672.4 3.23 0.58 11.50
16 312.2 2.02 3.05 684.8 7.02 63.8 27.1 569.2 3.53 0.68 13.23
17 328.5 2.50 2.04 892.6 5.51 67.4 35.0 713.7 5.75 1.96 14.00
18 328.4 2.02 2.55 894.1 7.01 59.3 25.5 788.7 4.60 1.20 15.40
19 328.3 1.51 3.05 896.1 8.05 45.0 17.3 866.4 2.82 0.83 13.30
20 328.4 3.02 1.02 908.4 8.04 63.9 47.2 665.2 13.33 6.72 15.10
21 328.1 2.50 2.55 1378.9 4.50 66.1 32.4 1123.5 5.25 1.20 16.50

Table 6. Stoichiometric Coefficients of the Matrix for FTS Reactions

reaction path
component
reactants CO + H2O CO + 3H2 2CO + 4H2 2CO + 5H2 nO + 2nH2 nO + (2n + 1)H2
products CO2 + H2 CH4 + H2O C2H4 + 2H2O C2H6 + 2H2O CnH2n + nH2O CnH2n+2 + nH2O
CO -1 -1 -2 -2 -n -n
H2 1 -3 -4 -5 -2n -(2n + 1)
CO2 1 0 0 0 0 0
H2O -1 1 2 2 n n
CH4 0 1 0 0 0 0
C2H4 0 0 1 0 0 0
C2H6 0 0 0 1 0 0
...
CnH2n 0 0 0 0 1 0
CnH2n+2 0 0 0 0 0 1

integration of the reactor model embedded in a param- (RCnH2n+2, RCnH2n, RCO2, ...). The partial pressure of the
eter optimization procedure. This simplification may ith component can be calculated by using the following
lose the transportation-enhanced readsorption phenom- formula:
ena, and further modification to the kinetic models
obtained is needed. This will be discussed elsewhere. mi
From the group of equations (1)-(3), the total number Pi ) PT (i ) 1, 2, 3, ..., Nc) (87)
Nc
of the components, Nc, and of the reactions, NR, are 2N
+ 3 and 2N, respectively, where N is the maximum ∑ mi
carbon number of hydrocarbons considered. The matrix i)1
of the stoichiometric coefficients between the products
and reactions according to the FTS and the WGS where PT is the total pressure in the reactor.
reaction is listed in Table 6.11-13 Numerical integration of the continuity equation (85)
The model of the fixed-bed reactor used in our kinetic is performed by using Gear’s method.65
study can be described as follows:11-13 4.2.2. Optimization Method. In the estimation of
parameters of the kinetic model, the Levenberg-Mar-
dmi NR quardt (LM) algorithm still plays an important role.

dW
) ∑
j)1
RijRj (i ) 1, 2, ..., Nc; j ) 1, 2, ..., NR) (85)
with the initial condition
W ) 0; mi ) mi,0
where W is the weight of the catalyst used, mi and mi,0
are the mole flow rates of component i along the reactor
axis and at the inlet of the reactor, NR is the number of
reactions involved, Nc is the total number of compo-
nents, Rij is the stoichiometric coefficient for the ith
component in reaction j, and Rj is the rate of reaction j
However, in most cases, the objective function based
upon the nonlinear and experimental data frequently
contains more than one minimum.66 As a general
algorithm, LM-type continuum methods often fail in
locating global minima. In our paper, to avoid getting
trapped in local minima, the parameters of the various
(86) rival models in this paper were estimated in a first step
using the genetic algorithm (GA) approach that was
developed in this group67 and then using the LM
algorithm to make refined optimization, after which
the statistical tests and the physiochemical constraints
are used to evaluate the significance of models and
parameters. The GA algorithm encoded in this group
using a real-number code chromosome representation to
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5077

Table 7. Values of the Parameters for the Mechanism FT III WGS3a

parameter value unit parameter value unit
k5,0 7.88 × 103 mol g-1 s-1 bar-1 Ev 58.43 kJ mol-1
E5 75.52 kJ mol-1 k-8 2.77 × 10-5 mol g-1 s-1 bar-1
k7M,0 2.01 × 106 mol g-1 s-1 bar-1 Kv 2.76 × 10-2 bar-0.5
E7M 97.39 kJ mol-1 K1 2.59 bar-1
k7,0 1.10 × 106 mol g-1 s-1 bar-1 K2 1.67 × 10-3 bar-1
E7 111.48 kJ mol-1 K3 8.34 × 10-2
k8,0 8.79 × 103 mol g-1 s-1 K4 1.21 bar-1
E8 97.37 kJ mol-1 K6 0.10
kv,0 3.42 mol g-1 s-1 bar-1.5
a All of the energetic values are estimated to be in the 95% confidence level, and frequencies may be lowered to 90%.

ensure a wide searching space for optimal kinetic
parameters. The GA procedure consists mainly of four
parts: randomly producing an initial population, ran-
domly selecting two individuals from the population
space to crossover (using certain operator), producing the
next generation of population, nonuniform mutation, and
repeating these steps to scan the whole searching space.
For estimation of the models, 20 model responses
in the regression procedure were the outlet concen-
trations of 15 paraffins and olefins (such as CH4, C2H4,
C2H6, C3H6, C3H8, C4H8, C4H10, etc.) selected as the
most significant Fischer-Tropsch products, along with
the concentrations of CO2, the conversions of CO and
H2, and the overall concentrations of C5+ and C11+
hydrocarbons. The objective function is defined as
follows:
The relative residual (RR) between experimental and
calculated values of responses will be used to show the
deviations between the model and experiment
mi,exp - mi,cal
RR ) × 100 (91)
mi,exp
The dependence of the reaction rate parameters on
temperature can be described by the Arrhenius law.
ki(T) ) ki,0 exp(-Ei/RT) (92)
4.2.3. Parameter Estimation. For scanning the
models by parameter optimization, several basic physi-
cal criteria are applied: the rate constants and equi-
librium constants should be positive, and the activation

(mi,exp - mi,cal
) energies for the paraffins and olefin formation and for
2
fi,obj ) (i ) 1, 2, ..., Nexp) (88) the WGS reaction should be in the range of values
mi,exp reported by other researchers. The optimization proce-
dure by the GA and LM methods has been set to find
where mi,exp and mi,cal are the experimental and calcu- the minimum, which provided (1) a reasonable fit to the
lated values of conversions of reactants or the selectivi- experimental data, (2) physically meaningful values of
ties of products, respectively, and Nexp is the total the model parameters, and (3) acceptable values of
number of experimental runs. Because of the com- statistical parameters, such as F values for the models
plexity of the models, a multiresponse objective function and t values for the parameters.
should be introduced, which is expressed in the follow- A total of 25 kinetic models are rejected because of
ing form: unreasonable values of the parameters. The discrimina-

( )
Nresp Nexp mij,exp - mij,cal 2 comparing first their MARR and second statistical tests
FTol,obj ) ∑ ∑ Wi
mij,exp
i)1 j)1
(i ) 1, 2, ..., Nresp; j ) 1, 2, ..., Nexp) (89)
where Wi represents the weighting factor of the ith
objective function (it expresses the relative importance
of the ith response). Those responses with the most
accurate measurement and/or with special significance
in the regression are provided with greater weights):
Nresp is the number of responses in the system, mij,exp is
the experimental value of the ith response for the jth
kinetic experiment, and mij,cal is the calculated value of
the ith response for the jth kinetic experiment.
The adjustable model parameters for the several
kinetic models were calculated by minimizing FTol,obj
with the GA and LM methods.
The accuracy of the fitted model relative to the
experimental data was obtained from the MARR (mean
absolute relative residuals) function:
tion of the remaining 14 rival models is performed by
on models (F test) and parameters (t test). The result
shows that only two kinetic models’ MARR are within
the 20%. The two models are FT III WGS3 (MARR
18.6%) and FT VI WGS3 (MARR 19.2%).
4.3. Results and Discussion. The parameters of
the remained best model are listed in Table 7, and
all of them are statistically significant. The estimated
activation energy for chain growth, E5, is 75.52 kJ
mol-1, indicating that the methylene insertion into
the metal-alkylidene bond has a moderate height of
energy barrier that it needs to overcome. The activation
energy for methane formation, E7M, is 97.39 kJ mol-1,
which is in good agreement with that reported by
Vannice58 (89 kJ mol-1) and smaller than that for other
paraffin formation, E7, with a value of 111.48 kJ mol-1,
which can explain the higher selectivity of methane than
those of other paraffins. The activation energy of olefin
formation is 97.37 kJ mol-1, much smaller than that of
paraffins, which can interpret the general fact that the
selectivity is much higher to alkenes on the Fe-Mn

( )
catalysts than on other iron-based catalysts.67 This is
Nresp Nexp mi,exp - mi,cal 1 different from Dictor and Bell69 (80-90 kJ mol-1 for
MARR ) ∑ ∑ mi,exp NrespNexp
× 100 (90) paraffins and 100-110 kJ mol-1 for olefins) as well as
j)1 i)1 Lox and Froment11,12 (94.5 kJ mol-1 for paraffins and
5078 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

Figure 5. Comparison of the calculated and experimental product

distribution (FT III WGS3 reaction conditions: T ) 556 K, P )
Figure 3. Comparison of calculated and experimental CO conver- 2.51 MPa, H2/CO ) 2.62, GHSV ) 1.6 × 10-3 Nm3 kg of catalyst-1
sions (FT III WGS3). s-1).

Figure 6. Comparison of the calculated and experimental product

Figure 4. RRs of calculated and experimental CO2 selectivity (FT distribution (Lox and Froment’s model reaction conditions: T )
III WGS3). 556 K, P ) 2.51 MPa, H2/CO ) 2.62, GHSV ) 1.6 × 10-3 Nm3 kg
of catalyst-1 s-1).

132.3 kJ mol-1 for olefins) over a Fe-Cu-K catalyst. It

is evident that all of the estimated activation energies
of the hydrocarbon formation are mostly within those
reported in the literature (all between 70 and 105 kJ
mol-1).11,12,17,69 The activation energy of 58.43 kJ mol-1
for the WGS reaction in this work is comparable with
the values reported in the literature.6,8,11,12,70
A comparison between the experimental and calcu-
lated values of conversion of CO and selectivities of CO2
are presented in Figures 3 and 4. The figures show that
the RRs between the model and experiment are mostly
within 20%.
Figures 5-10 show the comparison of experimental
and calculated product distributions. Figure 5, 7, and 9
are predicted by model FT III WGS3 and Figure 6, 8,
Figure 7. Comparison of the calculated and experimental product
and 10 by Lox and Froment’s ASF model. The ASF distribution (FT III WGS3 reaction conditions: T ) 585 K, P )
model appears to give a strong deviation for the selec- 3.02 MPa, H2/CO ) 2.04, GHSV ) 3.2 × 10-3 Nm3 kg of catalyst-1
tivity to hydrocarbons, lower to methane and higher to s-1).
other hydrocarbons. As shown in these figures, the
selectivities to olefins predicted with the ASF type model
are lower than those to paraffins, in contrast with the orientations of kinetic and reactor models in considering
experimental results. The modeled product distributions the intrinsic mechanism information and the transpor-
using FT III WGS3 are in good agreement with the tation effects. The kinetic model developed is significant
experimental selectivities, and the deviation for meth- only for the cases excluding the diffusivity and solubility
ane is described fairly accurately. factors, which are believed to be significant in enhancing
It should be noted that the current kinetic model has the olefin readsorption and secondary reaction and,
not considered the effect of diffusivity and solubility of therefore, in changing the olefin and paraffin selectivi-
olefins with different chain sizes on the paraffin/olefin ties. However, kinetic experiments can never exclude
ratio on the basis of the understanding of different the diffusivity and solubility (mobility) especially of

Figure 8. Comparison of the calculated and experimental product
distribution (Lox and Froment’s model reaction conditions: T )
585 K, P ) 3.02 MPa, H2/CO ) 2.04, GHSV ) 3.2 × 10-3 Nm3 kg
of catalyst-1 s-1).
Figure 9. Comparison of the calculated and experimental product
distribution (FT III WGS3 reaction conditions: T ) 601 K,
P ) 1.51 MPa, H2/CO ) 3.05, GHSV ) 4.2 × 10-3 Nm3 kg of
catalyst-1 s-1).
Figure 10. Comparison of the calculated and experimental
product distribution (Lox and Froment’s model reaction condi-
tions: T ) 601 K, P ) 1.51 MPa, H2/CO ) 3.05, GHSV )
4.2 × 10-3 Nm3 kg of catalyst-1 s-1).
heavy olefins. Figure 11 shows the dependence of the
olefin-to-paraffin ratio on the carbon number. It can be
seen that the kinetic model without considering the
transportation effect (diffusivities and solubilities) has
not predicted the correct dependence compared with
experimental results. This again proved the understand-
ing in FTS that pure olefin readsorption and secondary
reaction have little consequence to the observed olefin/
Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5079
Figure 11. Comparison of the calculated and experimental olefin/
paraffin ratios for different carbon numbers (FT III WGS3 reaction
conditions: T ) 585 K, P ) 3.02 MPa, H2/CO ) 2.04, GHSV )
3.2 × 10-3 Nm3 kg of catalyst-1 s-1).
paraffin ratio dependence on the carbon number if the
transportation enhancement is not considered.19 We
have recently tested the kinetic models developed in this
group in a reactor simulation task, in which all of the
transportation effects are comprehensively considered
thanks to the nonintrinsic factor excluded kinetic
models, and the primary results recovered the experi-
mentally observed olefin/paraffin ratio dependence cor-
rectly. This later work is too extensive to present here
and will be discussed elsewhere.
5. Conclusions
Kinetic experiments of the Fischer-Tropsch reaction
over an industrial Fe-Mn ultrafine particle catalyst are
carried out for a wide range of industrially relevant
conditions. Different reaction equation combinations
were evaluated by global parameter optimization, which
involved the minimization of the multiresponse objective
function by a GA approach and a LM method. It was
found that a kinetic model for the FTS based on the
alkylidene mechanism gives the best fit of the experi-
mental data. The best model shows that two elementary
steps, the insertion of methylene into the metal-
alkylidene bond and the desorption of hydrocarbon
products, are intrinsically slower than the others in FTS
and the RDS of the WGS reaction is the desorption of
CO2 via formate intermediate species. The activation
energy for alkene formation is 97.37 kJ mol-1 and is
much smaller than that for paraffins formation, 111.48
kJ mol-1, which can interpret the higher alkene selec-
tivity on Fe-Mn catalysts than on other iron-based
catalysts.
Acknowledgment
Financial support from the Chinese Academy of
Sciences (Project No. KGCX1-SW-02), Committee of
Science and Technology of China via 863 plan (Project
No. 2001AA523010), Shanxi Natural Science Founda-
tion (20031032), and the National Natural Sciences
Foundation of China (Project No. 29673054) is gratefully
acknowledged.
5080 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

Appendix: Rate Expressions of the Different Models of FTS

Model FT I: RDS, steps 5-7.
n i
RCH4 ) k6MK4PH2R1/(1 + x K4PH2 + K1PCO + K′3PH22PCO/PH2O + K1K2PH2PCO + x K4PH2 ∑ ∏
i)1 j)1
Rj))2
( (A1)

n n i
RCnH2n+2 ) k6K4PH2 ∏
j)1
Rj /(1 + x K4PH2 + K1PCO + K′3PH22PCO/PH2O + K1K2PH2PCO + x K4PH2 ∑ ∏
i)1 j)1
Rj))2
( (n g 2)
(A2)
n
RCnH2n ) k7+(1 - βn) K4PH2x ∏
j)1
Rj /[1 + xK4PH 2
+ K1PCO + K′3PH22PCO/PH2O + K1K2PH2PCO +
n i

xK P ∑(∏R )] (n g 2) (A3)

{[ ]}
4 H2 j
i)1 j)1

k7- n
- +
βn ) (k7 /k7 ) PCnH2n/ R1RA n-1
+
2
∑ (RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2) (A4)
PCOPH2 i)2

k5K′3
PH2O x
[s1] + k6 K4PH2[s1] + k7+

k5K′3PH22PCO/PH2O
Rn ) (n g 2) (A5)
k5K′3PH22PCO/PH2O + k6xK4PH2 + k7+(1 - βn)/[s1]

k5K′3PH21.5PCO/PH2O
R1 ) (A6)
k5K′3PH21.5PCO/PH2O + k6xK4

PH22PCO
k5K′3 [s1]
PH2O
RA ) (A7)
PH22PCO
k5K′3 [s1] + k6xK4PH2[s1] + k7+
PH2O

Model FT II: RDS, steps 5-7.

0.5
RCH4 ) k6MK4 PH2 R1/ 1 + 1.5
[ x K4PH2 + K1PCO + K′3
PH22PCO

PH2O
+ K1K2PH2PCO + x K4PH2 ∑
n

∏Rj)
i)1 j)1
(
i

] (A8)

RCnH2n+2 )

0.5
k6K4 PH2 1.5
∏
n

j)1 [
Rj / 1 + x K4PH2 + K1PCO + K′3
PH22PCO

PH2O
+ K1K2PH2PCO + x K4PH2 ∑
n

∏Rj)
(
i)1 j)1
i

] (n g 2) (A9)

RCnH2n )

+
x
k7 (1 - βn) K4PH2 ∏
j)1
n

[
Rj / 1 + x K4PH2 + K1PCO + K′3
PH22PCO

PH2O
+ K1K2PH2PCO + x K4PH2 ∑
n

∏Rj)
i)1 j)1
(
i

] (n g 2)

(A10)

PH22PCO
k5K′3 [s1]
PH2O
Rn ) (n g 2) (A11)
PH22PCO
k5K′3 [s1] + k6PH2 + k7+(1 - βn)
PH2O
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5081

PH22PCO
k5K′3 [s1]
PH2O
R1 ) (A12)
PH22PCO
k5K′3 [s1] + k6
PH2O

PH22PCO
k5K′3 [s1]
PH2O
RA ) (A13)
PH22PCO
k5K′3 [s1] + k6PH2 + k7+

{ [ ]}
PH2O

k7- n
- +
βn ) (k7 /k7 ) PCnH2n/ R1RA n-1
+
2
∑ (RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2) (A14)
PCOPH2 i)2

k5K′3 [s1] + k6PH2 + k7+

PH2O

Model FT III: RDS, steps 5, 7, and 8.

RCH4 ) k7MK4K6K′3
PH23PCO

PH2O
/ 1+
[ xK P 4 H2 + K1PCO + K′3
PH22PCO

PH2O
+ K1K2PCOPH2 + K6K40.5K′3
PH22.5PCO

PH2O
+

PH22PCO

]
2
n i
K′3
PH2O
(1 + K6 K4PH2) x
i)2
∑∏
j)2
(Rj) (A15)

RCnH2n+2 ) k7K4K6K′3
PH23PCO

PH2O
∏
n
Rj /
[ 1+ xK P 4 H2 + K1PCO + K′3
PH22PCO

PH2O
+ K1K2PCOPH2 + K6K40.5K′3
PH22.5PCO

PH2O
+

]
j)2

PH22PCO n i
2

K′3
PH2O
(1 + K6 K4PH2)xi)2
∑∏
j)2
(Rj) (n g 2) (A16)

+ 2
RCnH2n ) [k8 (1 - βn)K′3PH2 PCO/PH2O ∏
n

[
Rj]/ 1 + xK4PH 2
+ K1PCO + K′3
PH22PCO

PH2O
+ K1K2PCOPH2 +

]
j)2

PH22.5PCO PH22PCO n i
K6K4 K′3 0.5

PH2O
+ K′3
PH2O x
(1 + K6 K4PH2)
i)2
∑∏
j)2
(Rj) (n g 2) (A17)

PH22PCO
k5K′3
PH2O
Rn ) (n g 2) (A18)
PH22PCO
k5K′3 + k7K6K4PH2 + k8+(1 - βn)/[s1]
PH2O

- +

{ [
βn ) (k8 /k8 ) PCnH2n/ RA n-1
K′3PCOPH2 /PH2O + 2
k8-

k5K′3PCOPH22/PH2O[s1] + k7K6K4PH2[s1] + k8+

×

∑
i)2
n
(RAi-2PC (n-i+2)H2(n-i+2)
)
]} (n g 2) (A19)

k5K′3PH22PCO/PH2O[s1]
RA ) (A20)
k5K′3PH22PCO/PH2O[s1] + k7K6K4PH2[s1] + k8+
5082 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

Model FT IV: RDS, steps 7-9.

RCH4 ) k8MK0PH2R1/(1 + xK P 0 H2 x
+ K1PCO(1 + K2 K0PH2) + PH2O/K4 +
n i
K4K3K2K1K0PCOPH2/PH2O(1 + K5 K0PH2 + K6K5K0PH2) + x xK P ∑(∏R ))
0 H2
i)1 j)1
j
2
(A21)

n
RCnH2n+2 ) k8K0PH2 ∏
j)1
Rj /(1 + xK0PH 2 x
+ K1PCO(1 + K2 K0PH2) + PH2O/K4 +
n i
K4K3K2K1K0PCOPH2/PH2O(1 + K5 K0PH2 + K6K5K0PH2) + x x K0PH2 ∑ ∏(
i)1 j)1
Rj))2 (n g 2) (A22)

x
RCnH2n ) k9+(1 - βn) K0PH2 ∏
j)1
Rj /[1 + xK0PH 2 x
+ K1PCO(1 + K2 K0PH2) + PH2O/K4 +
n i
K4K3K2K1K0PCOPH2/PH2O(1 + K5 K0PH2 + K6K5K0PH2) + x x K0PH2 ∑ (∏Rj)]
i)1 j)1
(n g 2) (A23)

k7K′3PH22PCO/PH2O
Rn ) (n g 2) (A24)
k7K′3PH22PCO/PH2O + k8xK0PH2 + k9+(1 - βn)/[s1]

k7K′3PH22PCO/PH2O
R1 ) (n ) 1) (A25)
k7K′3PH22PCO/PH2O + k8xK1PH2

{ [ k9-

]}
n
- +
βn ) (k9 /k9 ) PCnH2n/ R1RA n-1
+ ∑(RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2)
2
k7K′3PH2 PCO/PH2O[s1] + k8 K0PH2[s1] + k9 x + i)2

(A26)

k7K′3PH22PCO/PH2O[s1]
RA ) (A27)
k7K′3PH22PCO/PH2O[s1] + k8xK0PH2[s1] + k9+

Model FT V(I): RDS, steps 1, 5, and 6.

[ ( )x ]
1 PH2O 1 1 1 n i

x
RCH4 ) k5MPH2 K0PH2R1/ 1 + x K0PH2 + 1 +
K2K3K4 P 2
+
K3K4 PH2
+
K4
K0PH2 ∑ ∏Rj)
i)1 j)1
( (A28)
H2

[ ( )x ]
n
1 PH2O 1 1 1 n i

x
RCnH2n+2 ) k5PH2 K0PH2 ∏
j)1
Rj / 1 + x K0PH2 + 1 +
K2K3K4 P 2
+
K3K4 PH2
+
K4
K0PH2 ∑ ∏R ) (
i)1 j)1
j (n g 2) (A29)
H2

[ ( )x ]
n
1 PH2O 1 1 1 n i

x
RCnH2n ) k6+(1 - βn) K4PH2 ∏
j)1
Rj / 1 + xK0PH2 + 1 +
K2K3K4 P 2
+
K3K4 PH2
+
K4
K0PH2 ∑ ∏Rj)
i)1 j)1
( (n g 2)
H2
(A30)
k1PCO
Rn ) (n g 2) (A31)
k1PCO + k5PH2 + k6+(1 - βn)

k1PCO
R1 ) (n ) 1) (A32)
k1PCO + k5PH2

k1PCO
RA ) (A33)
k1PCO + k5PH2 + k6+
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5083

- +

{ [
βn ) (k6 /k6 ) PCnH2n / R1RA n-1
+
k6-

k1PCO + k5PH2 + k6 +
n

∑
i)2
(RAi-2PC (n-i+2)H2(n-i+2)
]}
) (n g 2) (A34)

Model FT V(II): RDS, steps 2, 5, and 6.

[ ( )x
n i
1 1
x
RCH4 ) k5MPH2 K0PH2R1 / 1 + xK0PH2 + 1 +
K3K4PH2
+
K4
K0PH2 ∑ ∏Rj) +
(

]
i)1 j)1
n i

x
K1PCO K0PH2(1 + ∑ ∏Rj))
(
i)1 j)1
(A35)

[ ( )x
n n i
1 1
x
RCnH2n+2 ) k5PH2 K0PH2 ∏ Rj / 1 + x
K0PH2 + 1 +
K3K4PH2
+
K4
K0PH2 ∑ ∏Rj) +
(

]
j)1 i)1 j)1
n i
K1PCO K0PH2(1 + x ∑ ∏ Rj))
(
i)1 j)1
(n g 2) (A36)

[ ( )x
n n i
1 1
x
RCnH2n ) k6+(1 - βn) K0PH2 ∏ Rj / 1 + x K0PH2 + 1 +
K3K4PH2
+
K4
K0PH2 ∑ ∏Rj) +
(

]
j)1 i)1 j)1
n i
K1PCO K0PH2(1 + x ∑ ∏Rj))
(
i)1 j)1
(n g 2) (A37)

k2PCOPH2
Rn ) (n g 2) (A38)
k2PCOPH2 + k5PH2 + k6+(1 - βn)

k2PCO
R1 ) (n ) 1) (A39)
k2PCO + k5

k2PCOPH2
RA ) (A40)
k2PCOPH2 + k5PH2 + k6+

- +

{ [
βn ) (k6 /k6 ) PCnH2n/ R1RA n-1
+
k6-

k2PCOPH2 + k5PH2 + k6 +
∑
i)2
n
(RAi-2PC (n-i+2)H2(n-i+2)
)
]} (n g 2) (A41)

Model FT V(III): RDS, steps 3, 5, and 6.

x
RCH4 ) k5MPH2 K0PH2R1/ 1 +
[ x K0PH2 + 1 +
( )x 1
K4
K0PH2
n

∑ (
i

∏Rj) +

( ) ]
i)1 j)1

K1K2PCOPH2 n i

x K0PH2 K1PCO +
PH2O
(1 + ∑ (∏Rj))
i)1 j)1
(A42)

x
RCnH2n+2 ) k5PH2 K0PH2 ∏
n

[
Rj / 1 + x
K0PH2 + 1 +
( )x 1
K4
K0PH2
n

∑ ∏Rj) +
(
i

( ) ]
j)1 i)1 j)1

K1K2PCOPH2 n i

x K0PH2 K1PCO +
PH2O
(1 + ∑ ∏Rj))
(
i)1 j)1
(n g 2) (A43)

+
x
RCnH2n ) k6 (1 - βn) K0PH2 ∏
n
Rj /
[
1+ xK P 0 H2
( )x
+ 1+
K4
1
K0PH2 ∑
n
(∏Rj) +
i

( ) ]
j)1 i)1 j)1

K1K2PCOPH2 n i

x K0PH2 K1PCO +
PH2O
(1 + ∑ (∏Rj))
i)1 j)1
(n g 2) (A44)
5084 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

k3PCOPH22/PH2O
Rn ) (n g 2) (A45)
k3PCOPH22/PH2O + k5PH2 + k6+(1 - βn)

k3PCOPH22/PH2O
R1 ) (n ) 1) (A46)
k3PCOPH22/PH2O + k5M

k3PCOPH22/PH2O
RA ) (A47)
k3PCOPH22/PH2O + k5PH2 + k6+

{ [
βn ) (k6-/k6+) PCnH2n/ R1RAn-1 +
2
k6-

k3PCOPH2 /PH2O + k5PH2 + k6 +

∑
i)2
n
(RAi-2PC (n-i+2)H2(n-i+2)
)
]} (n g 2) (A48)

Model FT VI: RDS, steps 6-8.

RCH4 ) k7MK50.5PH21.5R1/ 1 +
[ xK P 5 H2 + K1PCO + K4-1
PH2O

PH2
+ K1K2K4
PH2PCO

PH2O
+ K′3
PH22PCO

PH2O
+

x K5PH2 ∑
n
(∏Rj)
i)1 j)1
i

] (A49)

0.5
RCnH2n+2 ) k7K5 PH2 1.5
∏
n
Rj /
[
1+ xK P 5 H2 + K1PCO + K4 -1
PH2O

PH2
+ K1K2K4
PH2PCO

PH2O
+ K′3
PH22PCO

PH2O
+

]
j)1

n i

x K5PH2 ∑ ∏Rj)
(
i)1 j)1
(n g 2) (A50)

+
x
RCnH2n ) k8 (1 - βn) K5PH2 ∏
n

[
Rj / 1 + xK5PH 2
+ K1PCO + K4 -1
PH2O

PH2
+ K1K2K4
PH2PCO

PH2O
+ K′3
PH22PCO

PH2O
+

]
j)1

n i

xK5PH2 ∑ ∏Rj)
(
i)1 j)1
(n g 2) (A51)

PH22PCO
k6K′3 [s1]
PH2O
Rn ) (n g 2) (A52)
PH22PCO
k6K′3 [s1] + k7PH2 + k8+(1 - βn)
PH2O

PH2PCO
k6K′3 [s ]
PH2O 1
R1 ) (n ) 1) (A53)
PH2PCO
k6K′3 [s ] + k7
PH2O 1

k6K′3PH22PCO/PH2O[s1]
RA ) (A54)
k6K′3PH22PCO/PH2O[s1] + k7PH2 + k8+

- +

{ [
βn ) (k8 /k8 ) PCnH2n/ R1RA n-1
+
2
k8-

k6K′3PCOPH2 /PH2O[s1] + k7PH2 + k8 +

∑
i)2
n
(RAi-2PC (n-i+2)H2(n-i+2)
)
]} (n g 2) (A55)
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5085

Model FT VII(I): RDS, steps 1, 7, and 8.

(
PH2O
RCH4 ) k7MK0PH2R1/ 1 + x K0PH2 + +
K6 K0PH2x

( ) )
PH2O 1 1 1 n i 2

+ + + +1 xK P ∑(∏R )0 H2 j (A56)
x
K2K3K4K5K02PH22 K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2

(
n PH 2 O
RCnH2n+2 ) k7K0PH2 ∏ Rj / 1 + xK0PH 2
+ +
j)1
x
K6 K0PH2

( ) )
PH2O 1 1 1 n i 2

+ + + +1 xK P ∑(∏R )
0 H2 j (n g 2) (A57)
x
K2K3K4K5K02PH22 K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2

[
n PH 2 O
x
RCnH2n ) k8+(1 - βn) K0PH2 ∏ Rj / 1 + xK0PH2 + +
j)1
x
K6 K0PH2

( ) ]
PH2O 1 1 1 n i
+ + + +1 xK0PH2 ∑ (∏Rj) (n g 2) (A58)
x
K2K3K4K5K02PH22 K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2

k1PCO
Rn ) (n g 2) (A59)
k1PCO + k7xK0PH2[s1] + k8+(1 - βn)

k1PCO
R1 ) (A60)
k1PCO + k7xK0PH2[s1]

k1PCO
RA ) (A61)
k1PCO + k7xK0PH2[s1] + k8+

{ [ k8-

]}
n
- +
βn ) (k8 /k8 ) PCnH2n/ R1RA n-1
+ ∑ (RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2) (A62)
x
k1PCO + k7 K0PH2[s1] + k8 + i)2

Model FT VII(II): RDS, steps 2, 7, and 8.

(
PH2O
RCH4 ) k7MK0PH2R1/ 1 + x K0PH2 + +
K6 K0PH2x

( )x )
n i 2
1 1 1
K1PCO + + + +1 K0PH2 ∑ (∏Rj) (A63)
x
K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2

(
i PH 2 O
RCnH2n+2 ) k7K0PH2 ∏ Rj / 1 + x K0PH2 + +
j)1
x
K6 K0PH2

( )x )
n i 2
1 1 1
K1PCO + + + +1 K0PH2 ∑ (∏Rj) (n g 2) (A64)
x
K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2
5086 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

[
i PH2O
x
RCnH2n ) k8+(1 - βn) K0PH2 ∏ Rj / 1 + x K0PH2 + +
j)1
x

]
K6 K0PH2

( )x
n i
1 1 1
K1PCO + + + +1 K0PH2 ∑ ∏Rj)
( (n g 2) (A65)
x
K3K4K5K0PH2 K5 i)1 j)1
K4K5 K0PH2

k2K1xK0PH2PCO[s1]
Rn ) (n g 2) (A66)
k2K1xK0PH2PCO[s1] + k7xK0PH2[s1] + k8+(1 - βn)

k2K1xK0PH2PCO
R1 ) (n ) 1) (A67)
k2K1xK0PH2PCO + k7xK0PH2

k2K1xK0PH2PCO[s1]
RA ) (A68)
k2K1xK0PH2PCO[s1] + k7xK0PH2[s1] + k8+

{ [ k8-

]}
n
- +
βn ) (k8 /k8 ) PCnH2n / R1RA n-1
+ ∑(RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2)
x
k2K1 K0PH2PCO[s1] + k7 K0PH2[s1] + k8 x + i)2

(A69)

(
Model FT VIII: RDS, steps 5, 9, and 10.

PH2PCO 1 PH2O PH 2 O PH21.5PCO

RCH4 ) k9MK6PH2R1/ 1 + xK P 6 H2 + K1PCO + K2 1
+ + + K′3 +
x
PH2O K6K7K8 PH2 PH2O

)
K8 K6PH2
2
PH22PCO n i
K′4
PH2O
+ xK P ∑(∏R ) 6 H2
i)1 j)1
j (A70)

RCnH2n+2 ) k9K6PH2 ∏
i

(
Rj / 1 + xK6PH 2
+ K1PCO + K2 1
PH2PCO

PH2O
+
1
K6K7K8 PH2
PH2O
+
PH 2 O

x
+ K′3
PH21.5PCO

PH2O
+

)
j)1
K8 K6PH2
2 2
PH2 PCO n i
K′4
PH2O
+ xK P ∑(∏R )
6 H2
i)1 j)1
j (n g 2) (A71)

x
RCnH2n ) k10+(1 - βn) K6PH2 ∏
i

j)1 [
Rj / 1 + x K6PH2 + K1PCO + K21
PH2PCO

PH2O
+
1
K6K7K8 PH2
PH2O
+
PH 2 O

x
+

]
K8 K6PH2
1.5 2
PH2 PCO PH2 PCO n i
K′3
PH2O
+ K′4
PH2O
+ x K6PH2 ∑ ∏Rj)
i)1 j)1
( (n g 2) (A72)

k5K′4PH22PCO/PH2O
Rn ) (n g 2) (A73)
k5K′4PH22PCO/PH2O + k9xK6PH2 + k10+(1 - βn)/[s1]

k5K′4PH21.5PCO/PH2O
R1 ) (n ) 1) (A74)
k5K′4PH21.5PCO/PH2O + k9xK6
 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003 5087

k5K′4PH22PCO/PH2O[s1]
RA ) (A75)
k5K′4PH22PCO/PH2O[s1] + k9xK6PH2[s1] + k10+

{ [ k10-

]}
n
- +
βn ) (k10 /k10 ) PCnH2n/ R1RA n-1
+ ∑(RAi-2PC (n-i+2)H2(n-i+2)
) (n g 2)
2
k5K′4PH2 PCO/PH2O[s1] + k9 K6PH2[s1] + k10 x + i)2

(A76)

Model FT IX: RDS, steps 5, 10, and 11.

RCH4 ) k10K9K6 K′4 0.5

PH22.5PCO

PH2O
/ 1+
( xK P 6 H2 + K1PCO + K2 1
PH2PCO

PH2O
+ K2 2
PH2O

PH2
+
x
PH 2 O
+ K′3
PH21.5PCO

PH2O
+

)
K8 K6PH2
2 2
PH2 PCO PH22PCO n i
K′4
PH2O x
+ (1 + K9 K6PH2)K′4
PH2O
∑ ∏ Rj
i)2 j)2
(A77)

RCnH2n+2 ) k10K9K6K′4PH23PCO/PH2O ∏
i)2
n

(
Ri / 1 + x K6PH2 + K1PCO + K21
PH2PCO

PH2O
+ K22
PH2O

P H2
+
x
PH 2 O
+

)
K8 K6PH2
1.5 2 2 2
PH2 PCO PH2 PCO PH2 PCO n i
K′3
PH2O
+ K′4
PH2O
+ (1 + K9 K6PH2)K′4x PH2O
∑ ∏ Rj
i)2 j)2
(n g 2) (A78)

+ 2
RCnH2n ) k11 (1 - βn)K′4PH2 PCO/PH2O ∏
n

i)2
Ri /
[ 1+ xK P 6 H2 + K1PCO + K2 1
PH2PCO

PH2O
+ K2 2
PH2O

PH2
+
x
PH 2 O

K8 K6PH2
+

]
1.5 2 2
PH2 PCO PH2 PCO PH2 PCO n i
K′3
PH2O
+ K′4
PH2O
+ (1 + K9 K6PH2)K′4x PH2O
∑ ∏ Rj
i)2 j)2
(n g 2) (A79)

βn )

- +

{ [ 2
(k11 /k11 ) PCnH2n/ K′4PH2 PCO/PH2ORA n-1
+
2
k11-

k5K′4PH2 PCO/PH2O[s1] + k10K9K6PH2[s1] + k11 +

∑
i)2
n
RAi-2PC (n-i+2)H2(n-i+2)

(n g 2) (A80)
]}
k5K′4PH22PCO/PH2O
Rn ) (n g 2) (A81)
k5K′4PH22PCO/PH2O + k10K9K6PH2 + k11+(1 - βn)/[s1]

k5K′4PH22PCO/PH2O[s1]
RA ) (A82)
k5K′4PH22PCO/PH2O[s1] + k10K9K6PH2[s1] + k11+

where K′4 ) K1K2K3K4K62K7K8.

Model FT X: RDS, steps 4, 8, and 9.

0.5 2.5
RCH4 ) k8MK7K5 K′3PH2 PCO/PH2O/ 1 +
[ xK P 5 H2 + K1PCO + K2 1
PH2PCO

PH2O
+ K2 2
PH2O

P H2
+ K7K′3K5 0.5
PH22.5PCO

PH2O
+

K′3
PH22PCO

PH2O x
+ (1 + K7 K5PH2)K′3PH22PCO/PH2O ∑
n

∏Rj
i)2 j)2
i

] (A83)
5088 Ind. Eng. Chem. Res., Vol. 42, No. 21, 2003

RCnH2n+2 ) k8K7K50.5K′3PH23.5PCO/PH2O ∏
n

[
Ri/ 1 + xK5PH2 + K1PCO + K21
PH2PCO

PH2O
+ K22
PH2O

PH2
+

]
i)2

PH22.5PCO PH22PCO n i
K7K′3K5 0.5

PH2O
+ K′3
PH2O x
+ (1 + K7 K5PH2)K′3PH22PCO/PH2O ∑ ∏ Rj
i)2 j)2
(n g 2) (A84)

RCnH2n ) k9+(1 - βn)K′3PH22PCO/PH2O

n

∏ [
Ri/ 1 + xK5PH 2
+ K1PCO + K21
PH2PCO

PH2O
+ K22
PH2O

PH2
+

]
i)2

PH22.5PCO PH22PCO n i
K7K′3K50.5
PH2O
+ K′3
PH2O x
+ (1 + K7 K5PH2)K′3PH22PCO/PH2O ∑ ∏ Rj
i)2 j)2
(n g 2) (A85)

k4K′3PH22PCO/PH2O
Rn ) (n g 2) (A86)
k4K′3PH22PCO/PH2O + k8K7K5PH2 + k9+(1 - βn)/[s1]

PH22PCO
k4K′3 [s1]
PH2O
RA ) (A87)
PH22PCO
k4K′3 [s1] + k8K7K5PH2[s1] + k9+
PH2O

{[ ]}
βn ) (k9-/k9+) ×
PH22PCO k9- n
PCnH2n/ K′3
PH2O
RAn-1
[s1] + [s1] ∑ RAi-2PC (n-i+2)H2(n-i+2)
(n g 2)
PH22PCO i)2

k4K′3 [s1] + k8K7K5PH2[s1] + k9+

PH2O
(A88)

Nomenclature K1 ) equilibrium constant of the elementary reaction 1 for

FTS (bar-1)
E5 ) activation energy for chain growth (kJ mol-1) K2 ) equilibrium constant of the elementary reaction 2 for
E7M ) activation energy for methane formation (kJ mol-1) FTS (bar-1)
E7 ) activation energy for paraffin formation (kJ mol-1) K3 ) equilibrium constant the elementary reaction 3 for
E8 ) activation energy for olefin formation (kJ mol-1) FTS
Ev ) activation energy for the WGS reaction (kJ mol-1) K4 ) equilibrium constant the elementary reaction 4 for
fi,obj ) objective function for the ith response FTS (bar-1)
FTot,obj ) multiresponse objective function K6 ) equilibrium constant the elementary reaction 6 for
kWGS4 ) rate constant of the forward reaction in step IV FTS
(mol g-1 s-1) Kp ) equilibrium constant of the WGS reaction
k-WGS4 ) rate constant of the reversible reaction in step Kv ) group of constants of the WGS reaction (bar-0.5)
IV (mol g-1 s-1) KWGS1 ) equilibrium constant of CO adsorption elementary
k5 ) rate constant of chain growth (mol g-1 s-1 bar-1) step
k5,0 ) preexponential factor of chain growth (mol g-1 s-1 KWGS2 ) equilibrium constant of H2O adsorption elemen-
bar-1) tary step
k7M ) rate constant of methane formation (mol g-1 s-1 KWGS3 ) equilibrium constant of surface reaction elemen-
bar-1) tary step
k7M,0 ) preexponential factor of methane formation (n g KWGS4 ) equilibrium constant of CO2 desorption elementary
2) (mol g-1 s-1 bar-1) step
k7 ) rate constant of paraffin formation (mol g-1 s-1 bar-1) KWGS5 ) equilibrium constant of H2 desorption elementary
k7,0 ) preexponential factor of paraffin formation (n g 2) reaction
(mol g-1 s-1 bar-1) mi ) mole flow rate of component i (mol s-1)
k8 ) rate constant of olefin formation (mol g-1 s-1) MARR ) mean absolute relative residuals
k8,0 ) preexponential factor of olefin formation (n g 2) (mol N ) maximum carbon number of the hydrocarbons in-
g-1 s-1) volved
kv ) rate constant of CO2 formation (mol g-1 s-1 bar-1.5) Nc ) total number of components involved
kv,0 ) preexponential factor of CO2 formation (mol g-1 s-1 NR ) total number of reactions involved
bar-1.5) Nexp ) total number of experiments
k-8 ) rate constant of olefin readsorption reaction (mol g-1 Nresp ) total number of responses for parameter estimiza-
s-1 bar-1) tion

Pi ) partial pressure of component i (bar)
PT ) total pressure of the reaction system (bar)
R ) gas constant (J mol-1 K-1)
Rj ) overall reaction rate of reaction path j (mol g-1 s-1)
Ri ) rate of formation of component i (mol g-1 s-1)
RR ) relative residual between the experimental and
calculated values of the response
s1 ) active site for hydrocarbon formation
s2 ) active site for the WGS reaction
T ) temperature of the reaction system (K)
Wi ) weight of the ith response
W ) weight of the catalyst used (g)
Greek Symbols
R1 ) chain growth factor for carbon number 1
Rn ) chain growth factor for carbon number n (n g 2)
RA ) chain growth factor without olefin readsorption
Ri,j ) stoichiometric coefficient for the ith component in the
jth reaction
βn ) readsorption factor of 1-olefin with carbon number n
(n g 2)
Superscripts and Subscripts
cal ) calculated value
exp ) experimental value
i ) index indicating reactions
j ) index indicating components
M ) methane
n ) number of carbon atoms
* ) equilibrium state
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Received for review February 14, 2003
Revised manuscript received June 12, 2003
Accepted June 13, 2003
IE030135O