Journal of Natural Gas Chemistry 11(2002)99108

Recent Technological Developments in Cobalt Catalysts for Fischer-Tropsch Synthesis

Junling Zhang, Jiangang Chen, Yongwang Li, Yuhan Sun
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China [Manuscript received October 5, 2002; revised November 8, 2002]

Abstract: Co-based catalysts are often utilized due to their high Fischer-Tropsch synthesis (FT) activity, C+ hydrocarbon selectivity, low water-gas shift reaction (WGS) activity and relatively low cost. Selec5 tive control of C+ hydrocarbons and the catalyst longevity are critical in the design of cobalt catalysts. 5 Thus, various methods to improve the performance of Co catalysts have been suggested. The progress in cobalt catalysts reviewed in the last few decades, mainly involved the support, promoter, preparation and deactivation of Co-based catalysts. Key words: FT synthesis, cobalt catalyst, support, promoter, preparation, deactivation

1. Introduction Because of the environmental demands for cleaner and cleaner fuels, there is an obvious trend in energy consumption from oil and coal to clean resources. Natural gas, the cleanest fossil fuel, has attracted a great deal of attention over the last decades and is projected to play an even more important role in coming years. When FT synthesis was discovered in Germany during the last century, it is the promising ones to convert coal and natural gas to clean, environmentallysound fuels and chemicals via syngas[1,2]. Cobalt, iron and nickel catalysts for FTS were rst developed in the early 1900s. These metals are typical transition elements, the outermost electron congurations of which are 3dx 4s2 (x<10). Usually CO can be activated when adsorbing onto exposed metal with an empty d-orbital due to the formation of - ligands[3,4]. Generally, nickel catalysts are considered to be a type of methanation catalyst. Iron and cobalt catalysts are good for higher hydrocarbon production,

and it is now accepted that supported cobalt catalysts are preferred for FTS, because of their high FT activity, high selectivity for linear hydrocarbons and low activity for the water-gas shift reaction[3]. Usually, the FTS reaction is regarded as a surfacecatalyzed polymerization process in which the adsorbed CHx monomers, formed by hydrogenation of adsorbed CO, react with the surface H atoms and hydrocarbon fragments to produce hydrocarbons with a broad range of chain lengths due to the limitation of the typical ASF (Anderson-Schulz-Flory) distribution[5]. For instance, the standardprecipitated Co catalyst (100Co : 5ThO2 : 7.5MgO : 200Kieselguhr) gives a hydrocarbon distribution (mass) with C1 C2 11%; C3 C4 9.0%; C5 C11 31.0%; C12 C19 27.3%; C+ 21.4%[1]. Earlier researchers illustrated the in20 uence of the electron state of metallic cobalt on the process of hydrocarbon synthesis and roughly judged its inuence on the activity and product selectivity throughout hydrogenation and chain growth of Co catalysts. The high activity and low-carbon hydro-

Corresponding author. Tel: +86-351-4041627; Fax: +86-351-4041153; E-mail address: yhsun@sxicc.ac.cn; The authors acknowledge nancial support from the State Key Foundation Program for Development and Research of China (Contact: G1999022402).

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carbons are favored when Co catalysts have a strong ability in CO hydrogenation. However, the strong chain growth ability of Co catalysts leads to greater heavy hydrocarbons and olens production and thus lower activity[1,3]. Ishihara et al.[6] found that the surface concentration of H and CO species is closely related to the electron density of the alloy, which depends on the type of mixed oxide and its composition. On a catalyst with a high H/CO surface ratio, the surface CHx fragments are easily hydrogenated to terminate chain growth; oppositely, the chain growth was promoted on the low H/CO ratio[7]. The active sites of iron catalysts are extremely complicated that these FeO, FeO, FeCx , and FeS2
Table 1. Company Shell[11] Exxon[11] Gulf Oil[11] Sasol[12,13] IFP[12] Statoil[14]

species are the reaction centers during the CO hydrogenation process and the active sites change with reaction atmosphere[1,810]. Dierent from iron catalysts, the active sites of Co catalysts are easier to be studied, i.e. metal cobalt, CoO and Co3 O4 are relatively inactive for FTS[5]. Industrial FTS catalysts are a multi-component system, and the typical catalyst formulations of the major petroleum corporations are presented in Table 1. Formulations of potential industrial catalysts typically contain a noble metal, oxide promoters and supports. In this paper, we will summarize recent progress in Co catalysts.

The composition of the patented Co catalysts of several petroleum companies Component of main catalyst Oxide promoter IIIB, IVB, VB Th, Zr, Hf, Ce, U, Al, Si La, Mn, Th, Mg, IIIB, IVB Zr, Ti, Cr Cu, Sc, Mo, K, Ti La Noble metal promoter Pt, Ir, Rh, Re, Ru Re, Ru Ru Pt Re Support SiO2 TiO2 , -Al2 O3 -Al2 O3 SiO2 -Al2 O3 Reactor Fixed-bed Fixed-bed Slurry-bed

Active component of the catalyst: Co.

2. Catalyst support 2.1. Traditional support The most popular supports for FT synthesis include SiO2 , Al2 O3 , TiO2 , MgO, active carbon, kieselguhr and zeolites. Reuel et al.[15] reported that the specic activity increased in the sequence: Co/MgO<Co/C<Co/SiO2<Co/Al2 O3 <Co/TiO2 for 10% Co catalysts loaded on the supports at 0.1 MPa, 498 K and H2 /CO=2. Iglesia et al.[2] believed that the intrinsic rate of supported Co catalysts had nothing to do with metal dispersion or supports at typical FT conditions (high temperature, pressure and CO conversion). Li et al.[16] also observed that the FT reaction is structurally insensitive for Co/TiO2 between 0.5% and 10% dispersion. These opposite viewpoints of the inuence of the support on the reaction activity and selectivity show that the functionality of the support is multi-sided. Bessel[17] investigated the relationship between catalytic properties and support acidity, surface area, reducibility and adsorptive properties for FT synthe-

sis. Supports with a high surface area produced high Co dispersions and highly active FT catalysts. The nature of the higher hydrocarbons strongly depended upon the support acidity, with the non-zeolite and low acidity supports producing the classic straightchained FT products. Of the zeolite supported catalysts, the most strongly acidic ZSM-5 supported catalyst produced the most highly-branched products. Lipidus et al.[18] reported on the inuence of calcination temperature on the reaction properties of 10%Co/Al2O3 and Co/SiO2 . The total hydrocarbon yield decreased on Co/SiO2 catalysts but increased on Co/Al2 O3 catalysts while increasing the calcination temperature. The nature of the oxide phases are thought to be responsible for the variation in catalytic properties. On the surface of the Co/SiO2 catalyst, Co3 O4 supposedly reduces the total hydrocarbon yield. The cobalt-support surface compounds cause an increase in the total hydrocarbon yield and the C+ 5 fraction selectivity on Co/Al2 O3 catalysts. The interaction between the metal and the support for supported Co catalysts has a distinct inuence on the reducibility and dispersion of the catalysts and their

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properties. For example, Bechara et al.[19,20] found that the cobalt reducibility was inuenced by cobalt loading and the porosity of the supports because of the heterogeneity of the cobalt distribution. An increase in the size of the reduction improves the activity and selectivity for high molecular hydrocarbon weight. Lapszewicz et al. examined the inuence of

silica pore size (between 420 nm) on FT reaction properties. These authors attributed the catalytic properties to changes in the surface H/CO ratio (See Figure 1)[7,21]. Figure 1 shows that CO conversion and CH4 selectivity increased but turnover frequency (TON) was constant with the increase of the H/CO ratio adsorbed on the catalyst surface.

Figure 1. Turnover numbers for CO conversion (1) and CH4 formation (2) as a function of the ratio of hydrogen and carbon monoxide adsorbed on the catalyst surface.

However, Saib et al.[22] observed a dierent phenomena over 20%Co/SiO2 catalysts. Between 2 and 15 nm, the reducibility and dispersion of metallic cobalt were found to increase with the pore size of the supports with an average pore diameter larger than or equal to 4 nm, hence decreasing the dispersion. In FT synthesis, supported catalysts with a 10 nm pore size of supports proved to be the most active and selective for hydrocarbon formation.
Table 2. Co (wt%) 10.1 9.2

A large number of patents indicate that, for Co/TiO2 catalysts, the crystallite phases of TiO2 and SMSI between cobalt and the support play important roles in the FT reaction[23,24]. Payne and Mauldin prepared titanium supports with dierent rutile phase contents by calcination of commercial Degussa-25. When Co2 (CO)8 impregnates TiO2 , the cobalt catalysts exhibit dierent catalytic properties, as shown in Table 2.

The inuence of rutile content on the reaction performance of Co/TiO2 CO conversion (mol%) 5 97 CH4 yield (mol%) 15.1 5.4 O2 chemsorption (mol/g) 53 205

Rutile in titania (wt%) 28 100

Pretreatment conditions: 1st stage 523 K/air/3 h; 2nd stage 723 K/H2 /1 h. Reaction conditions: P=1.93105 Pa, T=473 K, GHSV=1000 h1 , H2 /CO=2.15.

2.2. Supports prepared by new methods Recently, many researchers devoted themselves to the exploitation and application of new FT catalysts. Iwasaki et al.[25] rstly applied novel uniform mesoporous materials (silicate crystallite meso-

porous material, SCMM) to FT synthesis. For the 5% Co catalysts supported on SCMM, the catalytic activity was found decreased in the sequence: Co/SCMM-1>Co/SCMM-2>Co/SiO2 and the nature of the product hydrocarbons is vastly dierent at 2.1 MPa, 506 K, 2,000 h1 and H2 /CO/Ar=6/3/1. In

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the case of SCMM-1 with a negative charge near the surface, olens and branched hydrocarbons were eciently produced, whereas the SCMM-2 with a negative charge in the middle of the crystallite platelets produced mainly normal hydrocarbons with a high chain growth probability () for CO hydrogenation. Yin et al.[26] introduced a regular hexagonal mesopore HMS to the FT catalytic system, which led to improved catalytic activity and C+ selectivity. Bet5 ter catalytic properties seemed to be associated with shorter channels and larger textural mesoporosity. However, Co/SBA-15 was shown to be an undesirable FT catalyst due to its low reducibility[27]. Natural Pillared Clays (PILCS) are bi-dimensional porous materials[28]. Using these materials as supports, a limit in the growth of the products for the complex reaction, e.g. FTS, will be reached due to an adequate porous texture. Their application as the supports of Co catalysts indicates that the Co20Al catalyst has a conversion similar to a standard catalyst but with a high selectivity to liquid hydrocarbons[28] because of the texture of the support compared with the standard FT catalyst at 2 MPa, 473553 K, 6,120 h1 and H2 /CO=2. The new methods of support preparation and treatment are described as the following literatures. Tsubaki et al. developed a simple preparation method for bimodal silica that involves directly introducing SiO2 sol into the large pores of SiO2 gel pellets. 10% Co catalyst supported on bimodal silica exhibited remarkably high FT activity in the slurry reactor due to its bimodal structure, having not only a higher surface area but also a larger pore size[29]. Recently, our laboratory[30] prepared Co catalysts supported on ammonia nitrate-modied silica. These could improve the activity and C+ selectivity when tested at 2 5 MPa, 453503 K, 425 h1 and H2 /CO=2. Klabunde et al.[31] reported the rst examples of solvated metal atom dispersion (SMAD). They found that the SMAD Co-Mn/SiO2 catalyst leads to unusual CO activation mechanisms and hence aects the selectivity in the FT reaction products. Co UFP (ultrane particles) prepared by the chemical reduction method in the liquid phase was more active for the FT reaction than a precipitated Co catalyst due to their nonporous structure. Hence, Kikuchi et al. developed UFP Co catalysts and added Cr, Ti, Mn, Zr and Mo oxides. Among these catalysts, Co-Cr exhibited the highest activity because it had the smallest cobalt particles. In the experiment, methane selectivity decreased while C+ selectivity increased[32]. The 5

sol-gel synthesis of inorganic metal oxides is an effective technique developed to control the texture of the support. During the process of sol-gel synthesis, organic compounds of TEOS and Al(OPr-i)3 are hydrolyzed to Si(OH)4 and Al(OH)3 and are simultaneously reduced in size. In an acid medium, a high surface area and low branched network structure can be obtained, while a low surface area and branched structure supports are more favorable. Ernst et al. prepared Co/SiO2 catalysts using the sol-gel technique[33]. At pH1, the Co/SiO2 -A catalyst prepared by a cobalt precursor and oxalic acid using hydrolysis and condensation of tetraethoxysilane exhibited microporous features of microporous, while the Co/SiO2 -B catalyst represented the mesoporous feature at pH7. Bianchi et al. examined the inuence of cobalt loading on Co/SiO2 sol-gel catalysts for FT synthesis at dierent temperatures and pressures[34]. As a result, high CO conversions were observed with a particular sensitivity to the reaction pressure and a limitation of the produced hydrocarbon fraction to C6 or C9 at low or high pressure, respectively. Some groups used other metal oxides as the support for FT synthesis. Frydman prepared niobium pentoxide (Nb2 O5 ) by calcination of niobic acid at 873 K, which was used to prepare Co-Rh/Nb2 O5 catalysts[35]. In these catalysts, an unusual elevation of the selectivity to long chain hydrocarbons was observed, especially for the bimetallic catalysts after the HTR reached 56% in the diesel fraction. Bruce et al. reported on Ru-Co/CeO2 catalyst with the well-stability and low water gas shift[36]. Colley et al. tested Cr-modied Co/MnO (1:1) at 493 K, 5 MPa, 250 h1 and H2 /CO=2[37]. They found that the addition of 2%Cr promoter could improve the chain hydrocarbon selectivity, especially for C+ hydrocar16 bons, but the catalytic activity and selectivity of the Co catalysts remained unchanged when the Cr loading increased from 2% to 25%. Their characterizations by XPS and XRD demonstrated that the Cr promoter might exist on the surface of the Co catalysts and exhibit weak electron eects. The in situ DRIFTS of Co/MnO catalysts showed that the incorporation of MnO into cobalt catalysts could stabilize the metal cobalt particles[38]. Bruce et al. found that Co/ZrO2 and Co/Ni-ZrO2 catalysts displayed excellent catalytic activity and C+ selectivity[39]. For ex5 ample, cobalt supported on 3wt%Ni-ZrO2 led to the formation of 60% C+ hydrocarbons. Xiang et al. pre5 pared high surface area ZrO2 gel with mesoporous features by using the supercritical uid drying technique

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(SCFD)[40], and they found that ZrO2 gel produced excellent reaction results. Zhang et al.[41] tested the Co/ZrO2 catalyst at 493 K, 2 MPa, 500 h1 and H2 /CO=2 and found that CO conversion reached 96% and C+ selectivity was 79%. 5 2.3. Complex metal oxides as support Rathousky et al.[42] found that the catalytic properties of 10%Co/SiO2-Al2 O3 was more similar to Co/SiO2 than to Co/Al2 O3 , but not dierent from Co/Al2 O3 and Co/SiO2 . They thought that the SiO2 -Al2 O3 multiplex could lead to the formation of more acid sites, which increased the product of the isomerization reaction. For example, the fraction of i-alkanes in liquid formed over 10%Co/SiO2 Al2 O3 reached 50%, while its polymerization ability decreased and resulted in the formation of 70%C4 -C10 hydrocarbons. In order to acquire more C4 hydrocarbons, Sethuraman applied both Co-Ni-ZrO2 and H2 SO4 -ZrO2 , giving 24%C4 hydrocarbons[43]. When gasoline with a high octane number is required for FT synthesis, the bifunctional catalysts are designed to possess polymerization and hydropolysis[20,44]. The -Al2 O3 crystal structure is that of a spinel with a decit of cations. The migration of cobalt ions into the alumina lattice sites with octahedral or tetrahedral symmetry under calcination conditions form the irreducible spinel compound[45]. The reduction of Co/Al2 O3 catalysts is suppressed by the formation of these irreducible spinel compounds. Khassin et al. and Chernavskii et al. suggested a method to hinder the CoAl2 O4 compound in which MgAl2 O4 or ZnAl2 O4 was used in place of pure -alumina as the support of the Co FT catalysts[46,47]. 2.4. Interaction between metal and support It is well known that these supports, such as TiO2 , MnO, Al2 O3 and SiO2 , easily react with metal cobalt to form the irreducible compounds, which are inactive for FT synthesis. So it is essential to investigate the metal-support interactions by various surface techniques. For example, Riva et al. investigated the metal-support interaction in Co/SiO2 and Co/TiO2 by XPS, TPR, XRD and TEM[24]. A significant Co- Titanium interaction was found while none was discovered for Co/SiO2 , and cobalt spread on titania during the reduction and tended to sinter on silica. The reduction of 25%Co/SiO2 was examined by in-situ EXAFS, XPS and XRD[48]. These studies

ascertained that cobalt was in the metallic state. FT-IR coupled with probe molecular adsorption is a sensitive technique for investigation of solid surfaces. Ishihara et al. studied the electronic state of metals using NO as the probe molecule on Co-Ni alloy catalysts[6]. IR bands around 1,800 cm1 were found and assigned to bend-type and linear-type NO. The bent-type (NO ) is formed by electron donation from the metal to the anti-bonding orbital of the NO molecule, but the linear-type (NO+ ) is formed by electron withdrawal from NO. Both bent and linear type NO bands appeared at high wave numbers on CoNi/SiO2 -ZrO2 and Co-Ni/SiO2 -Nb2 O5 , but at a lower wave number on Co-Ni/SiO2 -MgO. Originally, it was thought that the band shift of adsorbed NO resulted from the dierent electron density of the Co-Ni alloy supported on dierent mixed oxides. The extent of electron acceptance and donation of metal oxides depended on the components of the mixed oxides. As a result, the remarkable support eect of mixed oxides arises from the creation of electronic, unsaturated sites. This leads to a change in the electron density of the Co-Ni alloy, which determines the surface coverage of CO and H2 . Kadinov et al. and Fredriken et al. studied 4.7%Co/SiO2 and 5%Co/Al2 O3 catalysts using CO/CO+H2 as the probe molecule[49,50]. Several surface species were detected and identied as CO adsorbed on cobalt ions (Co+ ) in dierent oxidation states (CO =2,1602,180 cm1 ), CO on metallic cobalt (the linear-mode CO CO =2,020-2,060 cm1 and the bridged-type CO CO =2,0001,800 cm1 ). 3. Promoters The functions of the modiers for Co catalysts are summed up as follows: (1) to structurally modify the metal surfaces induced by the promoter; (2) to interact with metal cobalt because the active sites are blocked/covered due to the migration of the modiers; (3) to improve the reducibility and dispersion of metal cobalt; (4) to transfer charge between the modier and the metal; (5) to aect of the electrostatic elds of modier ions; (6) to play important roles in the activation of CO and H2 ; (7) to improve the longevity of Co catalysts. 3.1. Tradition metal oxides as promoter The earlier promoters, such as ThO2 and MgO, were successfully exploited in the standard industrial Co catalysts[51]. The degree of reduction for

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the supported cobalt catalyst was only 39% in the presence of kieselguhr due to its migration to the surface of cobalt oxide, but the addition of ThO2 increased the reducibility to 75%. Further investigation revealed that preferential segregation of ThO2 on the surface could prevent the encapsulation of cobalt oxide by kieselguhr. Recently, the practical applications of cobalt catalysts have been gradually replaced by other modiers because of the radiation of ThO2 . Russian scientists utilized TiO2 and ZrO2 in place of ThO2 and obtained a catalyst similar to ThO2 promoted Co catalysts[52], and the US Department of Energy also supports similar research. Withers et al. prepared a 3.5%Co/6.6%Zr/SiO2 catalyst using gas-phase deposition with the CO2 (CO)8 cobalt precursor[53]. Results demonstrated that this catalyst produced the best liquid fuel selectivity, and product distributions correlated to the ASF prediction. Ali et al. found that a high loading of ZrO2 could improve the catalytic rate and the yield of heavy hydrocarbonsThese authors thought that the active interface created in ZrO2 -Co could facilitate CO dissociation[54]. Rhor et al. examined the inuence of ZrO2 on the properties of Co/Al2 O3 catalysts and found that ZrO2 could improve the concentrations of reactive intermediates but hardly aect the reducibility, dispersion and intrinsic rate[55]. However, Feller et al. observed that, for ZrO2 -promoted Co/SiO2 , enhancing ZrO2 loading could decrease the dispersion and interaction between metal cobalt and SiO2 while increasing the reducibility of the catalysts[56]. Chen et al. characterized ZrO2 -modied Co/SiO2 catalysts using in-situ FT-IR, H2 -TPD and CO-TPD methods[57]. A Co-ZrO2 interface formed on the Co/Zr/SiO2 catalysts that increased hydrogen and CO uptake adsorbed at low temperatures and aected the adsorption-mode of CO. A strong interaction between metal cobalt and the support in TiO2 -modied Co catalysts could also be observed. For example, 3%Co/Al2 O3 -TiO2 (014wt%) catalysts were designed to examine the inuence of TiO2 on the properties and catalytic performance of cobalt catalysts[58]. A study by ESCA (electron spectroscopy for chem. Anal) showed that the dispersion of metal cobalt increased with the TiO2 loading, and there was an interaction between cobalt and TiO2 . The CoTiO3 phase was observed by LRS and XRD. Furthermore, the addition of TiO2 improved the product selectivity of the FT catalysts. Other transition metal oxides (e.g. MoOx , CrOx and MnOx ) were also used in FT catalysts[59,60]. For instance, Zhang et al. discovered

a maximum in the catalytic activity and that a small amount of Mn could improve the C+ hydrocarbons 5 selectivity on 12%Co/Mn/Al2 O3 [60]. 3.2. Rare earth metal oxides promoters Rare earth oxides (e.g. La, Ce, Gd) improve the performance of Co FT catalysts. An investigation of La-modied 10%Co/Al2 O3 catalysts by Vada et al. demonstrated that the addition of La favored the formation of heavy hydrocarbons and increased the selectivity of olens and chain growth probability at low La loadings (La/Co=0.05). However, the catalytic activity, heavy hydrocarbon and olen selectivities all decreased at high La loading (La/Co=0.10)[61]. SSITKA showed that the TOF increased with improving the La loading. Haddad et al.[62] discussed the inuence of La promotion on the reaction performance of 20%Co/SiO2 catalysts in a La/Co range between 0 and 0.75. They drew similar conclusions to those for the La-promoted Co/Al2 O3 catalysts. Adachi et al. found that the highest activity and C+ selectivity ex5 isted for 3%La-promoted Co/SiO2 catalysts in the range of 010wt% of La. These authors[63] thought that La could weaken the interaction between metal cobalt and the support, and induce more CO to become the active state. Ernst et al.[64] compared the inuence of Ce and La on the reaction performance of 25%Co/SiO2. Both the promoters acted as hydrogen storage agents and thus inuenced the selectivity of these catalysts (methane formation), but the catalyst promoted with Ce and La had a low catalytic activity. 3.3. Noble metal promoters Supported Ru catalysts are excellent FT catalysts, with high activity and chain growth ability. Indeed, supported Ru catalysts produce a C+ selectiv5 ity of over 90% at lower temperatures and initiate the FT reaction at 373 K. The application of metal ruthenium to FT synthesis is restricted because of its high cost. Usually metal ruthenium is used as a promoter of supported Co catalysts. Iglesia reported on Ru-modied Co/TiO2 and Co/SiO2 catalysts, in which the addition of Ru tripled the activity and increased the C+ selectivity from 84.5% to 5 91.1%[4]. Belambe and Kogelbauer et al. discussed the inuence of the Ru promoter on the catalytic performance of Co/Al2 O3 catalysts[65,66]. The calcination temperature of Ru-modied Co catalysts had a distinct inuence on the overall rate, but the reduction temperature of these catalysts had no aect on

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the overall rate or intrinsic activity. Tsubaki et al. evaluated the Ru, Pd and Pt-modied 10%Co/SiO2 catalysts at T =513 K, p=1.0 MPa, H2 /CO=2 and W/F =5(gh)/mol[67]. The catalytic activity decreased in the order: RuCo>PdCo>PtCo>Co, in which Ru could promote the reduction of Co catalysts, but Pt and Pd increased the dispersion and hardly aected the reducibility of the catalysts. This shows that these noble metals played dierent roles in the properties of Co catalysts. Ru could enrich the surface metal cobalt particles, while Pt and Pd were highly dispersed in the lattice of metallic cobalt and formed Pt-Co and Pd-Co alloys. Rhenium is also a popular promoter for supported FT Co catalysts. Vada et al. investigated 1%Pt and Re-modied 8.7%Co/Al2 O3 catalysts at 473 K, 5 bar, H2 /CO=2, and 473 K, 1 bar, H2 /CO=7[68]. The apparent rates of these catalysts increased while the product selectivity remained unchanged, which is in agreement with the number of active sites due to the high reducibility of the modied catalysts[10]. Rygh et al.[69] inspected the inuence of 1%Re promoter on the properties of 12%Co/Al2 O3 using the DRIFTS technique. They found that Re could promote the reduction of metal cobalt, increase the adsorption amounts of bridged-type CO, lower the reduction temperature of cobalt catalysts and suppress the migration of formate species. Li et al.[70]carefully investigated the inuence of B, Ru and Re on the performance of Co/TiO2 catalysts and discovered that Ru and Re improved the catalytic activity and C+ hydrocarbon selectivity. 5 For example, syngas conversion increased from 50% 54% to 68%71% and methane selectivity dropped from 9.5% to 5.5% at 0.5 (hg)/NL. Ru and Remodied Co/Nb2 O5 catalysts were characterized by TPR, XRD and chemisorption[71]. Re could suppress the aggregation of metal cobalt and favor the formation of diesel fractions, but Ru increased the number of active sites and simultaneously promoted the selectivities of gasoline and diesel fractions. Schanke et al. investigated 0.4% Pt-modied 9%Co/Al2 O3 and 9%Co/SiO2 catalysts at T =483 K, p=1 bar and H2 /CO=7[72]. The activities of Pt-modied catalysts were approximately 3 to 5 times greater than those of the unmodied catalysts, but the product selectivities were hardly inuenced. A further study revealed that Pt could lower the reduction temperature of Co catalysts, improve the dispersion and reducibility of Co catalysts, increase the reaction intermediates but not aect the intrinsic rate.

4. Preparation

The activity and selectivity of Co catalysts are closely associated with their preparations. The product selectivity strongly depends on a complex interplay between diusion, reaction and convection processes occurring between catalyst pellets and reactors at typical FTS conditions. For example, Iglesia et al.[73] prepared eggshell Co catalysts intending to suppress CO diusion and found that catalysts with intermediate shell thicknesses exhibited the maximum C+ hydrocarbon selectivity due to the 5 decrease in syngas and product transport restrictions. Peluso et al.[74] prepared eggshell Co/Zr/SiO2 catalysts in order to favor the production of the C10 C20 hydrocarbons. Sun et al. prepared FT 10%Co/SiO2 catalysts from mixed cobalt salts[75]. The co-impregnation of cobalt acetate and cobalt nitrate could improve the catalytic activity but hardly aected the product selectivity and chain growth probability (). It was assumed that metal cobalt readily reduced from cobalt nitrate could promote the reduction of Co2+ to the metallic state in cobalt acetate by the H2 spillover mechanism during the reduction process. Kraum et al.[76] examined the inuence of cobalt precursors (e.g. Co(COO)2 , Co(CH3 COO)2 , Co(acac)2 and Co(NO3 )2 ) on the properties of Co/TiO2 catalysts. The dispersion of Co catalysts from organic cobalt salts was higher than that of Co/TiO2 catalysts from Co(NO3 )2 . Van de Loosdrecht et al.[77] prepared 2.5% and 5%Co/Al2 O3 catalysts using cobalt nitrate, cobalt citrate and CoEDTA as cobalt precursors and also drew similar conclusions. During CO hydrogenation, Ho[78] observed that the signicant eects of adding Th when ethanol was employed as the impregnation solvent instead of water were attributed to a more extensive Co-ThO2 interface formed because of a better dispersed Th phase. Ming investigated the eect of the impregnation solution pH value on the dispersion, reducibility and reaction performance of Co/SiO2 catalysts[79]. The pH value of impregnation solution rst inuenced the surface charge and solubility of the silica gel and then the physical and chemical properties of the cobalt species on the surface of the silica gel. For instance, at pH<5, cobalt deposits as a cation. At pH<2 the silica surface is positively charged making the dispersion of cobalt and consequently the catalytic activity both poor. At pH5, cobalt reacts to form silicates or irreducible hydrosilicates.

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5. Deactivation of cobalt catalysts The longevity of Co catalysts is pursued for industrial applications. Bartholomew reviewed the mechanisms of catalyst deactivation, which were classied into six types: poisoning, fouling, sintering, vapor compound formation accompanied by transport, attrition/crushing and vapor-solid or solid-solid reaction[80]. The deactivation behaviors of Co catalysts were mainly due to the following reasons: oxidation of metal cobalt, metal migration into the support lattice resulting in the formation of the inactive FT compounds (e.g. slicate, aluminate and titanate), the aggregation and growth of metal cobalt on the surface of catalyst and the loss of metal cobalt because of attrition (especially for the three-phase slurry bed reactor). Water is the main FT by-product and accounts for ca. 50wt% of all products. It is not thermodynamically possible for oxidizing metal cobalt to CoO (Co3 O4 and CoAl2 O4 ) at normal conditions (See Figure 2), but it is likely to oxidize metal cobalt to CoO under hydrothermal treatment.

Figure 2. The relationship of the thermal constant to temperature. (1) Co+Al2 O3 +H2 O=CoAl2 O4 +H2 , (2) Typical FT conditions, (3) Co+H2 O=CoO+H2 .

For example, van Berge et al.[81] investigated the oxidation behaviors of cobalt using the Mssbauer o spectra and a steady-state reaction at 493 K, 20 bar and 50%70% conversion. Incrementing the water pressure sped up the deactivation of Co catalysts, and the particle size threshold of metallic cobalt was closely associated with the H2 O, CO and H2 pressure.

A study about the deactivation of Al2 O3 -supported cobalt catalysts resulting from the presence of water vapor found that the oxidation of supported cobalt was limited to the surface layers if H2 was present during hydrothermal treatment[82]. The noble metalpromoted Co/Al2 O3 catalysts also deactivated more rapidly than the unpromoted catalysts. Further studies revealed that the deactivation caused by the presence of water vapor did not alter the turnover frequency but decreased the number of active intermediates leading to products. Zhang et al. [83] investigated the eect of water vapor on the reduction of a calcined, Ru-promoted Co/Al2 O3 catalyst during the standard reduction procedure (H2 , 623 K, 10 h) and TPR. The addition of water vapor hindered the reduction of Co catalysts and strengthened the interaction between cobalt and the support, leading to the formation of irreducible Co-Al spinels. In addition, the velocity and water pressure of the feed gas were found to inuence the deactivation of 0.5%Ptpromoted 15%Co/Al2 O3 [84]. When high velocity and low water pressure were maintained, this catalyst exhibited better stability. Moreover, the inuence of a small amount water on the reaction activity was reversible, but the catalyst was permanently deactivated at PH2 O /PCO 1. Simultaneously, CO2 selectivity was improved by the formation of compounds such as CoO, Co3 O4 and CoAl2 O4 because they are active for the WGS reaction. FT synthesis involves a group of highly exothermic reactions. A great deal of research has been devoted to the use of slurry-phase reactors because of their high heat removal capabilities, but these reactors normally lead to deactivation of Co catalysts due to the existence of catalyst attrition in slurry-phase reactors[85]. Wei et al. found that the supports had attrition resistances as follows: Al2 O3 >TiO2 (rutile)>SiO2 . The attrition resistances of supported Co catalysts followed this sequence: Co/Al2 O3 >Co/SiO2>Co/TiO2 (rutile) Co/TiO2 (anatase). We recently ran a stability test on a FT active Co/ZrO2/SiO2 catalyst for 500 h on a laboratory scale. The activity of this catalyst decreased but the hydrocarbon distribution barely changed with time on stream (TOS). Regeneration of the deactivated catalyst with H2 at 673 K partially restored the activity. Our characterizations showed that a hydrated cobalt silicate species in the catalyst was formed near the reactor outlet, indicating that the cause of deactivation was mainly the formation of inactive hydrated silicate

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between metallic Co and silica in the presence of high water partial pressure[86]. 6. Summary In this paper, some investigations were reviewed that improve the limited selectivity for middle distillates and the catalyst deactivation in present FT catalysts. Key improvements in cobalt catalysts include: (1) cobalt catalysts, promoted by Zr, Ti, Mn oxides, etc, were designed for production of waxes and then cracking to diesel fuel and olens, (2) new materials were exploited and applied to supported Co catalysts, (3) research in bifunctional or mixed metal/zeolite catalysts continued to produce gasoline in yields higher than predicted by ASF theory, (4) Co catalysts were applied in slurry-bed processes, (5) deactivation of Co catalysts was controlled. References
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