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Petro Qui Mica 1 Articulo
Petro Qui Mica 1 Articulo
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.
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
Figure 7. Reaction rate for FTS (0, O) and WGS (2) versus space velocity the catalyst loading is 20 wt %, the productivity would be 0.3
(from ref 6). (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-
Figure 8. Productivity comparison between the iron catalyst (240 °C) and 0.47 (g of hydrocarbon)/cm3/h. If the catalyst density is 1 g/cm3,
the cobalt catalyst 220 °C) (from ref 7).
the maximum productivity is ∼0.5 (g of hydrocarbon)/(g of
The comparison in Figure 87 shows that the iron catalyst is more catalyst)/h; on the other hand, if the density is 2.7 g/cm3,10 the
productive at the more severe conditions (i.e., at higher space maximum productivity is ∼0.19 g/(g of catalyst)/h. Considering
velocities and at higher reactor pressures). these four examples, and realizing that they involve estimates
Common practice frequently is the factor that determines the that may not correspond to the actual situation, it appears that
expression used for catalytic activity. Today, the activity for these larger units are operated in a manner such that the ultimate
an iron catalyst is usually expressed on the basis of 1 g of iron, productivity of the catalyst is not realized. It therefore appears
while for the cobalt catalyst, this is usually reported on the basis that engineering advances for the operation of the slurry bubble
of 1 g of catalyst. For the use of the catalyst, the productivity column reactor and in the catalyst formulation provide op-
per reactor volume is the important consideration. The expres- portunities to realize significant advances in productivity.
sion of the activity as indicated above can be used once the
reactor type, the catalyst loading, and the operating conditions Selectivity
are defined. For mechanistic considerations, all of the methods
fall short of providing a preferred expression of catalytic activity. 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
Reactor Productivity
the data compiled by Kuo11 (Figure 9). However, prior to the
It is difficult to obtain productivity data for catalysts utilized Mobil data that was reported by Kuo, Kölbel’s data that was
in a slurry reactor that is operated under commercial conditions. generated in Germany in the 1950s was the standard for slurry-
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8941
Figure 13. Contact time-C1 and C2 selectivity correlation (from ref 16).
Figure 11. Effect of space velocity on product yield. The C10+ yield is (i.e., at the top of the reactor) being reincorporated into products,
greater at higher space velocities. Data at 240 °C, 0.79 MPa, and (H2/CO)in as claimed by Iglesia,15 thereby reducing the fraction of the
) 2 (from ref 13). products that are derived from the C1 surface species and
reducing the fraction of methane in the products. In a third
phase reactor considerations, e.g., ref 12. As can be seen by example,16 the fraction of methane that is produced remains
the data point in Figure 9 representing Kölbel and Ralek’s result, constant with increasing CO conversion (Figure 13). Thus, at
the methane and/or wax production is much lower than that the present time, it does not appear that one can make a valid
obtained by other workers. In agreement with the Mobil data, assessment for the selectivity for methane production at various
we find that the methane plus ethane selectivity increases as CO conversion levels for the cobalt catalyst.
the CO conversion increases above ∼75% for the low-alpha WGS activity in the catalyst may, or may not, be a desirable
iron catalyst (Figure 10). A major reason for the increase in the feature of the catalyst. If one is to operate with a synthesis gas
methane production at higher CO conversion is that the as is derived from coal (H2/CO ) 0.5-1.0), one needs to obtain
concentration of water has increased so that the WGS reaction water gas shift within the FT reactor or to operate in a hydrogen
occurs at about the same rate as the FTS; thus, there is an deficient mode that will limit CO conversion, or to conduct
increase in the H2/CO ratio (Figure 5 for H2/CO inlet ) 0.7). WGS in a unit located upstream of the reactor. On the other
While the general shape of the curve will be the same when hand, if the syngas is obtained from natural gas, the H2/CO
operating with a high-alpha iron catalyst, the fraction of methane ratio may be 2 or greater; in this case, one wants to limit the
produced is much lower (ca. 1-3% at low CO conversion). extent of water gas shift. In the case of a cobalt catalyst, the
The situation for methane is not as clear-cut when one CO2 production that results from WGS that is shown in Figure
considers the cobalt catalyst. Yates and Satterfield,13 using a 12 is typical. Thus, WGS only occurs to a measurable extent
cobalt catalyst that was intended to reproduce a Ruhrchemie with a cobalt catalyst as the CO conversion is ∼80% or greater.
catalyst in a continuous stirred tank reactor (CSTR), found that With the iron catalyst, WGS always occurs but becomes more
methane corresponded to an increasing fraction of the hydro- important as the CO conversion increases. Thus, the iron catalyst
carbons as the CO conversion increased (low space velocity, appears to be the choice when the synthesis gas is derived from
Figure 11). On the other hand, data obtained while operating coal. For syngas derived from natural gas, the cobalt catalyst is
with a cobalt-titania catalyst in a fixed-bed reactor show that usually preferred; iron would be considered in this case only
the methane fraction of hydrocarbons decreases with increasing when the CO2 that is produced could be recycled to the gasifier.
CO conversion (Figure 12).14 This result is consistent with a The product distribution of the total hydrocarbons is usually
mechanism with the alkenes produced at lower conversion levels considered to follow an Anderson-Schulz-Flory distribution.
8942 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007
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 increased with increasing particle size of the catalyst (Figures
does not contain potassium to approach 0.9 for a catalyst 20 and 21). They also reported results that indicate the reaction
containing 0.04 K/Co (Figure 17).18 At the same time, there is was diffusion controlled. This type of selectivity that depends
a linear decline in activity with increasing K/Co ratio so that as upon both the physical and chemical characteristics of the
little as 0.04 wt % potassium will result in about a 5-fold sample has been quantified, and it is observed that the catalyst
decrease in catalyst activity (Figure 18). The impact of the can be modified so that a minimum of methane and a maximum
promoter on the activity of an iron catalyst appears to depend of C5+ products can be produced (Figure 22). Thus, in Figure
upon operating temperature. Potassium appears to be an activity 22a, the C5+ product selectivity increases, which is claimed to
promoter when operating at high temperatures using a low-alpha be because of olefin reincorporation, reaches a maximum, and
iron catalyst (Figure 19).5 However, when operating at a lower then decreases as diffusion limitations become dominant. The
(200 °C) temperature, the alkali appears to be acting as a catalyst opposite is observed for methane production (Figure 22b), where
poison. Unfortunately, these data for the iron catalyst only olefin reincorporation causes a decrease in the amount of
provide the alkali content in relative concentrations. methane formed, attains a minimum, and then increases as the
more rapid diffusion of hydrogen effectively increases the H2/
Impact of Diffusion CO ratio in the interior of the catalyst pellet and, hence, the
Workers at Exxon have produced a significant amount of rate of formation of methane.
literature relating product selectivity to the physical properties In a slurry reactor, the size of the catalyst pellet is so small
of the catalyst and to the number and distribution of the that one would not anticipate diffusion to provide an impact
catalytically active cobalt sites.15,19-24 The workers at the former upon conversion or selectivity. However, as more active
Gulf Oil obtained results for cobalt supported on three sizes of catalysts become available, this may not be the case. The data
support particles25 and found that the amount of methane 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).
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 Figure 25. Deactivation of an iron catalyst (unpublished CAER data).
accumulation within the catalyst pellet, pressure drop across
the bed, etc.; these properties limit catalyst life because of the plant. Obviously, higher catalyst activity is always desirable
operating conditions and physical properties of the catalyst. The from a productivity viewpoint, and as more active catalysts are
other factor is the loss of catalyst sites through poisoning and/ developed, deactivation of the catalyst may become an issue.
or fouling. It has been shown in experiments lasting 3500 h or
more that both cobalt and iron catalysts decline in laboratory Conclusions
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 In summary, it is concluded that iron catalyst may be as active
catalysts in commercial operations are difficult to obtain. Sasol and, at more severe conditions of pressure and space velocity,
workers have indicated that they replace their iron catalysts even have a higher activity than a cobalt catalyst. The selectivity
because of physical changes in the catalyst or to attrition and properties of an iron catalyst may be varied over a wide range
not due to the loss of catalyst sites due to poisoning and/or by the use of promoters. In contrast, the use of promoters with
fouling. Shell has indicated that they expect their supported a cobalt catalyst to control selectivity has, to date, been limited,
cobalt catalyst to have a lifetime of five or more years in their and the elements that may alter selectivity appear to have a
fixed-bed reactor operations. Thus, it appears that catalyst very detrimental impact on the catalytic activity. Cobalt catalysts
lifetime is not a major issue for operation in today’s commercial exhibit two distinct advantages for some applications. The lack
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8945
of water gas shift activity allows one to reject the oxygen in (10) Behrmann, W. C., et al. U. S. Patent 5,545,674, Aug 13, 1996.
CO as water rather than CO2 so that the carbon efficiency of (11) Kuo, J. C. W. Two-stage process for conversion of synthesis gas
to high quality transportation fuels; Final Report DOE/PC/60019-9; DOE:
the cobalt catalyst is almost twice that of the iron catalyst, Washington, DC, Oct 1985.
especially when operating at high conversion levels. If the (12) Kölbel, H.; Ralek, M. The Fischer-Tropsch synthesis in the liquid
process is operated at ∼30% conversion, the iron catalyst rejects phase. Catal. ReV.sSci. Eng. 1980, 21, 225.
a significant fraction of the oxygen as water so that the (13) Yates, I. C.; Satterfield, C. N. Hydrocarbon selectivity from cobalt
advantage of cobalt, while still present, is not as great. The Fischer-Tropsch catalysts. Energy Fuels 1992, 6, 308.
(14) U.S. Patent, 4,568,663, Feb. 4, 1986.
second advantage of the cobalt catalyst is that it can be added (15) Iglesia, E. Design, synthesis and use of cobalt-based Fischer-
to a support that can provide robustness that the iron catalyst Tropsch synthesis catalysts. Appl. Catal., A 1997, 161, 59.
does not have in the unsupported state. Catalyst robustness (16) Hurlbut, R. S.; Puskas, I.; Schumacher, D. J. Fine details on the
becomes an important, and perhaps a deciding, factor for slurry selectivity and kinetics of the Fischer-Tropsch synthesis over cobalt
bubble column reactors where the ability to remove wax from catalysts by combination of quantitative gas chromatography and modeling.
Energy Fuels 1996, 10, 537.
the reactor will determine the success of the operation. (17) Van Berge, P. J.; Everson, R. C. Cobalt as an alternative Fischer-
Tropsch catalyst to iron for the production of middle distillates. Stud. Surf.
Acknowledgment Sci. Catal. 1997, 107 (Natural Gas Conversion IV), 207-212.
(18) U.S. Patent 4,880,763, Nov 14, 1989.
This work was supported by U.S. DOE contract number (19) Iglesia, E.; Soled, S. L.; Fiato, R. A.; Via, G. H. Bimetallic synergy
DE-FC26-98FT40308 and the Commonwealth of Kentucky. in cobalt-ruthenium Fischer-Tropsch synthesis catalysts. J. Catal. 1993,
143, 345.
(20) Madon, R. J.; Iglesia, E.; Reyes, S. C. Non-Flory product
Literature Cited
distributions in Fischer-Tropsch synthesis catalyzed by ruthenium, cobalt
(1) Iglesia, E.; Reyes, S. C.; Madon, R. J.; Soled, S. L. Selectivity control and iron. ACS Symp. Ser. 1993, 517, 383.
and catalyst design in the Fischer-Tropsch synthesis: Sites, pellets, and (21) Iglesia, E.; Soled, S. L.; Fiato, R. A. Fischer-Tropsch synthesis
reactors. AdV. Catal. 1993, 39, 221. on cobalt and ruthenium. Metal dispersion and support effects on reaction
(2) Bartholomew, C. H.; Pannell, R. B.; Butler, J. L. Support and rate and selectivity. J. Catal. 1992, 137, 212.
crystallite size effects in carbon monoxide hydrogenation on nickel. J. Catal. (22) Iglesia, E.; Reyes, S. C.; Soled, S. L. In Computer-Aided Design
1980, 65, 335. of Catalysts and Reactors; Becker, E. R., Pereira, C. J., Eds.; Marcel Dekker,
(3) Withers, H.P., Jr.; Eliezer, K. F.; Mitchell, J. W. Slurry-phase Fischer- Inc.: New York, 1992.
Tropsch and kinetic studies over supported cobalt carbonyl derived catalysts. (23) Iglesia, E.; Soled, S. L.; Baumgartner, J. E.; Reyes, S. C. Synthesis
Ind. Eng. Chem. Res. 1990, 29, 1807. and catalytic properties of eggshell cobalt catalysts for the Fischer-Tropsch
(4) Singleton, A. E. Advances make gas-to-liquids process competitive synthesis. Top. Catal. 1995, 2, 17.
for remote locations. Oil Gas J. 1997, 95, 68. (24) Iglesia, E.; Reyes, S. C.; Madon, R. J.; Soled, S. L. Selectivity
(5) Dry, M. E. The Fischer-Tropsch synthesis; Catalysis: Science and control and catalyst design in the Fischer-Tropsch synthesis: sites, pellets
Technology; Anderson, J. R., Boudart, M., Eds.; Springer-Verlag: Berlin, and reactors. AdV. Catal. 1993, 39, 221.
1981; Vol. 1, p 159. (25) Beuther, H.; Kobylinski, T. P.; Kibby, C. E.; Pannell, R. B. South
(6) Xu, L.; Bao, S.; O’Brien, R. J.; Raje, A.; Davis, B. H. Don’t rule Africa Patent 855317, July 15, 1985.
out iron catalysts for Fischer-Tropsch synthesis. CHEMTECH 1998, 28, (26) Withers, H. P., Jr.; Eliezer, K. F.; Mitchell, J. W. Slurry-phase
47. Fischer-Tropsch synthesis and kinetic studies over supported cobalt
(7) van Berge, P. J.; Everson, R. C. Natural Gas Conversion IV. In carbonyl derived catalysts. Ind. Eng. Chem. Res. 1990, 29, 1807.
Studies in Surface Science and Catalysis; de Pontes, M., Espinoza, R. L.,
Nicolaides, C. P., Scholz, J. H., Currell, M. S., Eds.; Elsevier: Amsterdam, ReceiVed for reView September 13, 2007
1997; Vol. 107, p 207. ReVised manuscript receiVed October 26, 2007
(8) Kölbel, H. Chemische Technologie. Band 3: Organische Technologie Accepted October 26, 2007
I; Carl Hansen Verlag: München, Germany, 1959; p 439.
(9) Koros, R. M. U.S. Patent 5,384,336, Jan 24, 1995. IE0712434