8938 Ind. Eng. Chem. Res.

2007, 46, 8938-8945

Fischer-Tropsch Synthesis: Comparison of Performances of Iron and Cobalt

Catalysts
Burtron H. Davis*
Center for Applied Energy Research, UniVersity of Kentucky, 2540 Research Park DriVe,
Lexington, Kentucky 40511

Biomass represents a source of syngas that can be further processed to hydrocarbon fuels. This paper examines
the Fischer-Tropsch technology for the biomass-to-clean fuels scenario. A comparison of the activities,
selectivities, and lifetimes of iron and cobalt catalysts for Fischer-Tropsch synthesis is made. For the more
severe conditions, iron is the more active catalyst, whereas a cobalt catalyst may be more active at low-
severity conditions. In spite of many reports, there are still considerable differences in defining catalyst activity.
The selectivity for methane likewise shows a wide range of reported results. Under the proper conditions,
both catalysts are capable of operating for 6 months or more.

Introduction for commercial operation. At first glance, this should be an easy

Synthesis of hydrocarbon fuels from synthesis gas derived
from coal or natural gas by the Fischer-Tropsch option is a
well-established commercial process. As the “biorefinery”
concept, i.e., biomass to fuels, gains momentum, the Fischer-
Tropsch synthesis (FTS) needs to be considered from the
biomass feedstock point of view. Many catalysts have been
utilized for studies of the Fischer-Tropsch synthesis. For
example, supported ruthenium catalysts have been widely
utilized for mechanism studies, and while these results have
academic interest, the commercial Fischer-Tropsch synthesis
plants have utilized either iron or cobalt catalysts. Thus, this
paper will review the iron and cobalt systems.
The H2/CO ratio of the syngas generated from a specific
feedstock, say, a particular coal, may vary widely depending
upon the gasifier used. For example, a H2/CO ratio of nearly
2.0 may be obtained from coal using a Sasol-Lurgi gasifier,
but the ratio may be ∼0.7 using a GE (formerly Texaco) gasifier.
While the ratio obtained may be varied somewhat by the amount
of CO2 or steam added with the carbonaceous feed, the C/H
ratio of the feedstock will also impact the H2/CO ratio of the
syngas. The high oxygen content of most biomass materials
leads to the conversion of a large fraction of the carbon to CO2
and a syngas with a low (1 or less) H2/CO ratio.
Once the syngas is generated and the H2/CO ratio is defined,
the same amount of hydrogen must be generated to produce
the hydrocarbon fuel with a general formula of CH2+n, where
n is usually in the 0.1-0.2 range. The difference in the C/H
ratio in the syngas and in the product defines the amount of
carbon that must be converted to CO2 to generate the required
amount of hydrogen by the water gas shift (WGS) reaction. If
the cobalt catalyst is selected for the FTS, then a WGS unit
must be installed after the gasifier and before the FT reactor.
On the other hand, because the iron catalyst has WGS activity,
the two reactions, WGS and FTS, may be carried out in the
same reactor. Thus, either catalyst system can be used with the
syngas derived from biomass, and a similar amount of carbon
must be converted to CO2 to generate the hydrogen that is
needed to produce the hydrocarbons.
In general, one is interested in the comparison of activity,
selectivity, and lifetime of a catalyst under conditions appropriate
* Phone: (859) 257-0253. Fax: (859) 257-0302. E-mail: davis@
caer.uky.edu.
10.1021/ie0712434 CCC: $37.00 © 2007 American Chemical Society
Published on Web 11/28/2007
task. However, in practice, it is a very demanding task to make
a useful comparison. Three reactor types have been utilized for
FTS in many laboratory studies and at the commercial scale:
fixed-bed, fluidized circulating and fixed-bed, and liquid slurry-
phase reactors. In general, these reactors utilize different
temperatures and different catalyst sizes. The optimum selectiv-
ity of two catalysts usually will not occur for the same reaction
conditions. In addition, the catalytic activity and selectivity may
not be constant with CO conversion levels, and this is not always
taken into account. In the following, we make an attempt to
make a valid comparison of some of the synthesis properties
of iron and cobalt FTS catalysts.
Comparison of Catalytic Activity
There are a number of ways to compare the activity of a
catalyst: measure of the activity per site (turnover number
(TON)), conversion/(g of catalyst), conversion/(volume of cata-
lyst), conversion/(unit of active catalytic component), and con-
version/(surface area). For the cobalt catalyst, the situation is
clear. A measure of the number of surface cobalt atoms can be
obtained directly from the amount of hydrogen or carbon mon-
oxide that is adsorbed on the reduced catalyst. Thus, a measure
of the number of cobalt surface atoms and the CO converted
by these catalysts allows one to obtain the CO conversion/
(surface cobalt). When such a plot is made, almost all cobalt
catalysts exhibit a constant activity per surface cobalt; that is,
a plot of the CO conversion versus the cobalt dispersion is linear
(Figure 1).1 The only exception reported to date for this is the
Ru promoted cobalt catalyst in some limited situations. Since
Ru is a FT catalyst, it may contribute to the synthesis as well
as the cobalt, even though its intended function is as a promoter.
There appears, contrary to the conclusion one may reach from
the data in Figure 1, to be room for debate when selecting the
best cobalt catalyst. On the basis of turnover data, cobalt
supported on titania appears to be the superior catalyst (Figure
2).2 However, if we make a comparison from another study,
we conclude that silica supported cobalt is the more active
catalyst (Figure 3).3 Comparing results from a third study
indicates that the alumina supported cobalt catalyst has the
superior activity (Figure 4).4 The conclusion one reaches in
comparing the data in Figures 1-4 is that, while it may be easy
to measure the number of active sites in cobalt catalysts, there
is a considerable variation in the effects introduced by the

Figure 1. Effect of cobalt dispersion, support, and alloying on FTS Co-
time yields ((mol of CO converted)/((total g)(atom of Co)(s))) (from ref
1).
Figure 2. Turnover number (TON) for unsupported and supported cobalt
catalysts (plotted from data in ref 2).
support. Presumably a factor in the differences in the data in
Figures 2-4 is the variation in the conversion levels and in the
conditions utilized in the studies.
The situation for the iron catalyst cannot be defined in the
simple manner as was done above for the cobalt catalyst. First,
the active iron catalyst is a mixture that may contain iron
carbides, iron oxides, and even metallic iron.5 For this catalyst
mixture, the active species has not been defined. For example,
there are claims that Fe3O4 is active, while there are other claims
that it is the carbide phases, and not Fe3O4, that have catalytic
activity. No direct measure of catalytic sites is available for iron
catalysts. Thus, a reliable measure of the TON for iron catalysts
is not possible today.
The rate of conversion of CO with an iron catalyst depends
upon the total CO conversion level; that is, the CO conversion
is not linear over the total conversion range (Figure 5).6
Furthermore, the H2/CO ratio in the reactor depends upon the
CO conversion level (Figure 5). This causes the productivity
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8939
Figure 3. Effect of support on activity of Co/Zr catalysts in a fixed-bed
reactor (from ref 3).
Figure 4. Comparison of relative activity of Co supported on titania, silica,
and alumina (from ref 4).
Figure 5. Variation of hydrogen (0) and CO (O) conversion and the H2/
CO ratio (]) in the exit gas with flow rate (from ref 6).
of an iron catalyst to be strongly dependent upon the CO
conversion level (Figure 6). The reason for this is that the water
gas shift (WGS) reaction that competes with the Fischer-
Tropsch synthesis (FTS) becomes more important at higher CO
conversion levels (Figure 7).
It is difficult to obtain literature data for the rate of CO
conversion with a cobalt catalyst as the space velocity is varied.
One comparison of iron and cobalt catalysts has been provided
by van Berge and Everson.7 At the higher space velocities, the
iron catalyst is more active, but at the lower space velocities
(higher conversion), the cobalt catalyst becomes more active.
8940 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007
Figure 6. Productivity of precipitated iron catalyst operated at 270 °C for
different Cu contents (ref 6).
Figure 7. Reaction rate for FTS (0, O) and WGS (2) versus space velocity
(from ref 6).
Figure 8. Productivity comparison between the iron catalyst (240 °C) and
the cobalt catalyst 220 °C) (from ref 7).
The comparison in Figure 87 shows that the iron catalyst is more
productive at the more severe conditions (i.e., at higher space
velocities and at higher reactor pressures).
Common practice frequently is the factor that determines the
expression used for catalytic activity. Today, the activity for
an iron catalyst is usually expressed on the basis of 1 g of iron,
while for the cobalt catalyst, this is usually reported on the basis
of 1 g of catalyst. For the use of the catalyst, the productivity
per reactor volume is the important consideration. The expres-
sion of the activity as indicated above can be used once the
reactor type, the catalyst loading, and the operating conditions
are defined. For mechanistic considerations, all of the methods
fall short of providing a preferred expression of catalytic activity.
Reactor Productivity
It is difficult to obtain productivity data for catalysts utilized
in a slurry reactor that is operated under commercial conditions.
Figure 9. Reactor wax yield versus methane yield (modified figure from
ref 11).
Kölbel8 reported that a large pilot plant (60 m3) could produce
0.47-0.94 (g of hydrocarbon)/(g of catalyst)/h; however, the
maximum productivity during the operation of the pilot plant
was 0.44 (g of hydrocarbon)/(g of catalyst)/h. The slurry reactor
utilized by Sasol is 5 m diameter and 22 m tall. Assuming that
only 2/3 of the total volume is filled with slurry and, thus,
available for synthesis, the reactor volume containing catalyst
is ∼290 m3. The output from the plant is 2 500 bbl/day; if one
assumes a density of the product of 1 g/cm3, the output is
∼16 600 kg/h. This corresponds to a productivity of ∼58 kg/
h/m3. If the reactor contains 2 wt % catalyst in the slurry, the
productivity would be ∼2.9 g/(g of Fe)/h; on the other hand, if
the catalyst loading is 20 wt %, the productivity would be 0.3
(g of hydrocarbon)/(g of Fe)/h. While the productivity from the
operation of the U.S. DOE La Porte plant is not currently
available to the public, the run conditions are available. The
slurry concentration was to be in the range of 24-25 wt %
catalyst, and when operating at 250-260 °C and 710 psig (48.3
atm), the reactor productivity goal was 150 (g of hydrocarbon)/
L/h. If one assumes a density for the slurry of 1.25 kg/L, one
calculates a productivity of 0.5 (g of hydrocarbon)/(g of
catalyst)/h. Koros9 reports productivities in the range of 450-
750 (volume of CO converted)/(volume of catalyst)/h when
operating with a cobalt-titania catalyst in a 6 in. diameter slurry
bubble column reactor at space velocities of 2800-3600 h-1.
This should correspond to a productivity in the range of 0.28-
0.47 (g of hydrocarbon)/cm3/h. If the catalyst density is 1 g/cm3,
the maximum productivity is ∼0.5 (g of hydrocarbon)/(g of
catalyst)/h; on the other hand, if the density is 2.7 g/cm3,10 the
maximum productivity is ∼0.19 g/(g of catalyst)/h. Considering
these four examples, and realizing that they involve estimates
that may not correspond to the actual situation, it appears that
these larger units are operated in a manner such that the ultimate
productivity of the catalyst is not realized. It therefore appears
that engineering advances for the operation of the slurry bubble
column reactor and in the catalyst formulation provide op-
portunities to realize significant advances in productivity.
Selectivity
The production of methane should be related to the distribu-
tion of other carbon-number products if the Anderson-Schulz-
Flory distribution is followed. This is the case with much of
the data compiled by Kuo11 (Figure 9). However, prior to the
Mobil data that was reported by Kuo, Kölbel’s data that was
generated in Germany in the 1950s was the standard for slurry-

Figure 10. Methane plus ethane selectivity versus CO conversion
(unpublished CAER data).
Figure 11. Effect of space velocity on product yield. The C10+ yield is
greater at higher space velocities. Data at 240 °C, 0.79 MPa, and (H2/CO)in
) 2 (from ref 13).
phase reactor considerations, e.g., ref 12. As can be seen by
the data point in Figure 9 representing Kölbel and Ralek’s result,
the methane and/or wax production is much lower than that
obtained by other workers. In agreement with the Mobil data,
we find that the methane plus ethane selectivity increases as
the CO conversion increases above ∼75% for the low-alpha
iron catalyst (Figure 10). A major reason for the increase in the
methane production at higher CO conversion is that the
concentration of water has increased so that the WGS reaction
occurs at about the same rate as the FTS; thus, there is an
increase in the H2/CO ratio (Figure 5 for H2/CO inlet ) 0.7).
While the general shape of the curve will be the same when
operating with a high-alpha iron catalyst, the fraction of methane
produced is much lower (ca. 1-3% at low CO conversion).
The situation for methane is not as clear-cut when one
considers the cobalt catalyst. Yates and Satterfield,13 using a
cobalt catalyst that was intended to reproduce a Ruhrchemie
catalyst in a continuous stirred tank reactor (CSTR), found that
methane corresponded to an increasing fraction of the hydro-
carbons as the CO conversion increased (low space velocity,
Figure 11). On the other hand, data obtained while operating
with a cobalt-titania catalyst in a fixed-bed reactor show that
the methane fraction of hydrocarbons decreases with increasing
CO conversion (Figure 12).14 This result is consistent with a
mechanism with the alkenes produced at lower conversion levels
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8941
Figure 12. Co-Re versus Ru selectivity (from ref 14).
Figure 13. Contact time-C1 and C2 selectivity correlation (from ref 16).
(i.e., at the top of the reactor) being reincorporated into products,
as claimed by Iglesia,15 thereby reducing the fraction of the
products that are derived from the C1 surface species and
reducing the fraction of methane in the products. In a third
example,16 the fraction of methane that is produced remains
constant with increasing CO conversion (Figure 13). Thus, at
the present time, it does not appear that one can make a valid
assessment for the selectivity for methane production at various
CO conversion levels for the cobalt catalyst.
WGS activity in the catalyst may, or may not, be a desirable
feature of the catalyst. If one is to operate with a synthesis gas
as is derived from coal (H2/CO ) 0.5-1.0), one needs to obtain
water gas shift within the FT reactor or to operate in a hydrogen
deficient mode that will limit CO conversion, or to conduct
WGS in a unit located upstream of the reactor. On the other
hand, if the syngas is obtained from natural gas, the H2/CO
ratio may be 2 or greater; in this case, one wants to limit the
extent of water gas shift. In the case of a cobalt catalyst, the
CO2 production that results from WGS that is shown in Figure
12 is typical. Thus, WGS only occurs to a measurable extent
with a cobalt catalyst as the CO conversion is ∼80% or greater.
With the iron catalyst, WGS always occurs but becomes more
important as the CO conversion increases. Thus, the iron catalyst
appears to be the choice when the synthesis gas is derived from
coal. For syngas derived from natural gas, the cobalt catalyst is
usually preferred; iron would be considered in this case only
when the CO2 that is produced could be recycled to the gasifier.
The product distribution of the total hydrocarbons is usually
considered to follow an Anderson-Schulz-Flory distribution.
8942 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

Figure 14. Chain growth probability R2 as a function of reactor pressure

at constant superficial velocity ((b), CAER result on iron catalyst under
175 psig; (2), CAER result on cobalt catalyst under 175 psig) (modification
of figure from ref 17).

Figure 17. Alpha versus K/Co ratio (from ref 18).

Figure 15. Mass % product distribution as a function of reactor pressure

at constant superficial velocity for the iron slurry-phase catalyst (from ref
17).

Figure 18. % CO conversion versus K/Co ratio (from ref 18).

Figure 16. Mass % product distribution as a function of reactor pressure

at constant superficial velocity for the cobalt catalyst (from ref 17).

Thus, when the log(mole fraction) of each product is plotted

versus the carbon number, a straight line should be produced;
the slope of this line can be related to the probability of chain
termination (β) relative to the chain growth (R). In this instance,
when R ) 0, methane is the only product. As R increases, the
fraction of heavier products increases, and as R approaches a
value of 1.0, the product approaches a high-molecular polyeth-
ylene product. In many situations, the product distribution does
not follow this simple, ideal distribution.
The selectivity for the heavier products is an important
consideration. Data that are typical of earlier work are shown
in the figure reproduced from a recent study by Sasol workers
(Figure 14).17 While the general perception is that a cobalt
catalyst produces heavier products than an iron catalyst, the data Figure 19. Dependence of activity change for an iron catalyst with the
in Figure 14 show that this is not the case. Our data are in amount of alkali promoter (data from ref 5).
general agreement with the data generated by the Sasol workers
(Figure 14). For the iron-based catalyst, the pressure can be With the iron catalyst, the product distribution can be varied
varied over a wide range without having a significant impact over a wide range merely by varying the potassium content.
upon the product distribution (Figure 15). In agreement with Thus, alpha ranges from ∼0.72 for low potassium catalyst to
much previous work, the product distribution changes to heavier ∼0.95 for high potassium containing iron catalysts. While the
products over a wide range of pressures, approaching that of alkali content does impact the activity of the iron catalyst, there
the high-alpha iron catalyst at pressures greater than 40 atm is a much more dramatic effect for the cobalt catalyst. Data
(Figure 16). obtained at atmospheric pressure with a cobalt catalyst indicate

Figure 20. Methane selectivity versus catalyst particle size (data from ref 25).
Figure 21. C5+ product selectivity for three particle size catalysts in fixed-bed reactor ((b), 185 °C, H2/CO ) 2; (2), 195 °C, H2/CO ) 2; (0), 195 °C,
H2/CO ) 1.5) (data from ref 25).
that the alpha value increases from ∼0.75 for a catalyst that
does not contain potassium to approach 0.9 for a catalyst
containing 0.04 K/Co (Figure 17).18 At the same time, there is
a linear decline in activity with increasing K/Co ratio so that as
little as 0.04 wt % potassium will result in about a 5-fold
decrease in catalyst activity (Figure 18). The impact of the
promoter on the activity of an iron catalyst appears to depend
upon operating temperature. Potassium appears to be an activity
promoter when operating at high temperatures using a low-alpha
iron catalyst (Figure 19).5 However, when operating at a lower
(200 °C) temperature, the alkali appears to be acting as a catalyst
poison. Unfortunately, these data for the iron catalyst only
provide the alkali content in relative concentrations.
Impact of Diffusion
Workers at Exxon have produced a significant amount of
literature relating product selectivity to the physical properties
of the catalyst and to the number and distribution of the
catalytically active cobalt sites.15,19-24 The workers at the former
Gulf Oil obtained results for cobalt supported on three sizes of
support particles25 and found that the amount of methane
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8943
increased with increasing particle size of the catalyst (Figures
20 and 21). They also reported results that indicate the reaction
was diffusion controlled. This type of selectivity that depends
upon both the physical and chemical characteristics of the
sample has been quantified, and it is observed that the catalyst
can be modified so that a minimum of methane and a maximum
of C5+ products can be produced (Figure 22). Thus, in Figure
22a, the C5+ product selectivity increases, which is claimed to
be because of olefin reincorporation, reaches a maximum, and
then decreases as diffusion limitations become dominant. The
opposite is observed for methane production (Figure 22b), where
olefin reincorporation causes a decrease in the amount of
methane formed, attains a minimum, and then increases as the
more rapid diffusion of hydrogen effectively increases the H2/
CO ratio in the interior of the catalyst pellet and, hence, the
rate of formation of methane.
In a slurry reactor, the size of the catalyst pellet is so small
that one would not anticipate diffusion to provide an impact
upon conversion or selectivity. However, as more active
catalysts become available, this may not be the case. The data
for the fraction of 1-alkene in the alkene component of each
8944 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

Figure 22. (a, b) Effect of structural parameters (χ) on FTS selectivity. Diffusion-enhanced readsorption (---) and diffusion-inhibited chain growth (s)
simulations and experimental data ((b), dispersion/support effects; (2), pellet size variations; (O) eggshell thickness variations; (a) C5+ selectivity; (b) CH4
selectivity [473 K, 2000 kPa, H2/CO ) 2.1, 55-65% CO conversion] (χ values from eq 2 with rp and Ro in m and θCo in surface Co atoms m-2) (ref 22).

Figure 23. 1-Alkene/total alkene versus carbon number ((b), 100Fe/6.0Cu/

8.1K/250SiO2; ([), 100Fe/6.0Cu/8.1K/250Al2O3; (2), 100Fe/6.0Cu/8.0K/
260MgAl2O4; (1), precipitated 100Fe/3.1Cu/8.1K/5.0SiO2) (unpublished
CAER results).

carbon number decreases with increasing carbon number for a Figure 24. Bulk activity maintenance for extended slurry reactor test of
supported iron catalyst compared to that of an unsupported catalyst L at baseline conditions (260 °C, 2.07 MPa, CO/H2 ) 1.0, and SV
catalyst. In this instance, the unsupported catalyst (1) was ) 2.0 nL/h per g of catalyst) (from ref 26).
present in 1-3 µm particles, whereas in the supported catalyst,
the particle size ranged from 25 to 250 µm. Thus, it appears
that, even for these small particle sizes, diffusional limitations
may be encountered for the rapid reactions. For the fraction of
alkenes of each carbon number, a plot similar to that of Figure
23 was obtained, again providing evidence that diffusion
limitations may be encountered even in the particle sizes that
are common for slurry bubble column reactors.

Catalyst Life
Two factors, at least, impact the useful life of a catalyst. One
factor is the physical properties such as catalyst attrition, wax
accumulation within the catalyst pellet, pressure drop across
the bed, etc.; these properties limit catalyst life because of the
operating conditions and physical properties of the catalyst. The
other factor is the loss of catalyst sites through poisoning and/
or fouling. It has been shown in experiments lasting 3500 h or
more that both cobalt and iron catalysts decline in laboratory
settings at a rate of <1% of unit activity per week of operation
for cobalt (Figure 24)26 and for iron (Figure 25). Lifetimes for
catalysts in commercial operations are difficult to obtain. Sasol
workers have indicated that they replace their iron catalysts
because of physical changes in the catalyst or to attrition and
not due to the loss of catalyst sites due to poisoning and/or
fouling. Shell has indicated that they expect their supported
cobalt catalyst to have a lifetime of five or more years in their
fixed-bed reactor operations. Thus, it appears that catalyst
lifetime is not a major issue for operation in today’s commercial
Figure 25. Deactivation of an iron catalyst (unpublished CAER data).
plant. Obviously, higher catalyst activity is always desirable
from a productivity viewpoint, and as more active catalysts are
developed, deactivation of the catalyst may become an issue.
Conclusions
In summary, it is concluded that iron catalyst may be as active
and, at more severe conditions of pressure and space velocity,
even have a higher activity than a cobalt catalyst. The selectivity
properties of an iron catalyst may be varied over a wide range
by the use of promoters. In contrast, the use of promoters with
a cobalt catalyst to control selectivity has, to date, been limited,
and the elements that may alter selectivity appear to have a
very detrimental impact on the catalytic activity. Cobalt catalysts
exhibit two distinct advantages for some applications. The lack

of water gas shift activity allows one to reject the oxygen in
CO as water rather than CO2 so that the carbon efficiency of
the cobalt catalyst is almost twice that of the iron catalyst,
especially when operating at high conversion levels. If the
process is operated at ∼30% conversion, the iron catalyst rejects
a significant fraction of the oxygen as water so that the
advantage of cobalt, while still present, is not as great. The
second advantage of the cobalt catalyst is that it can be added
to a support that can provide robustness that the iron catalyst
does not have in the unsupported state. Catalyst robustness
becomes an important, and perhaps a deciding, factor for slurry
bubble column reactors where the ability to remove wax from
the reactor will determine the success of the operation.
Acknowledgment
This work was supported by U.S. DOE contract number
DE-FC26-98FT40308 and the Commonwealth of Kentucky.
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ReceiVed for reView September 13, 2007
ReVised manuscript receiVed October 26, 2007
Accepted October 26, 2007
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