Applied Catalysis A: General 396 (2011) 116122

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

FischerTropsch synthesis over one eggshell-type Co/SiO2 catalyst in a slurry phase reactor
Chun Chen, Hisashi Yuuda, Xiaohong Li
Department of Chemical Processes and Enviroments, Faculty of Environmental Engineering, The University of Kitakyushu, 1-1, Hibikino, Wakamatsu, Kitakyushu, Fukuoka, Japan

a r t i c l e

i n f o

a b s t r a c t
The eggshell type cobalt catalyst (Co/SiO2 ) was prepared via a spray method. Characterization of surface information between cobalt and the support of silica gel was obtained by SEM and EPMA techniques. The discrete cobalt particle sizes were calculated based on XRD analysis. The prepared eggshell Co/SiO2 catalysts were investigated for FischerTropsch (FT) synthesis in a slurry-phase reactor and compared with conventional impregnated catalyst under the conditions of P = 1.0 MPa, T = 503 K, W/F = 5.0 g-cat h/mol and H2 /CO = 2. Results indicated that eggshell Co/SiO2 catalyst was inclined to generate long chain hydrocarbons and had relatively low CH4 selectivity. The parameters that respond to the performance of FT synthesis had been upgraded when compared with those of a conventional impregnated catalyst. In generated hydrocarbons for 1800 m supported catalyst, CH4 selectivity decreased from 22.98% to 9.68%, and C5+ selectivity increased from 61.66% to 79.45%. Meanwhile, the chain growth probabilities () also increased from 0.84 to 0.90. According to H2 -chemisorption and space-time yield (STY), the turnover frequency (TOF) of each catalyst was calculated. The higher TOF value of eggshell catalyst means better FT synthesis performance than is available using conventional impregnated catalyst. 2011 Elsevier B.V. All rights reserved.

Article history: Received 18 August 2010 Received in revised form 31 January 2011 Accepted 2 February 2011 Available online 26 February 2011 Keywords: Eggshell Cobalt Spray method FischerTropsch synthesis

1. Introduction In the near future, increasing dependence on natural gas reserves for fuel production is expected due to the sharp shrinking of crude oil stocks, as well as more and more concern about environmentally friendly fuels. In our meeting this challenge, the efcient utilizing of natural gas via FischerTropsch (FT) synthesis has become a highlight of research work, as part of gas to liquid (GTL) techniques [13]. The fuels produced by FT processes are environmentally superior to conventional crude oil derived fuels because of virtually zero sulphur content. It is well accepted that FT synthesis is a surface catalyzed stepwise growth process using CHx monomers formed by the hydrogenation of CO in the presence of a transition metal catalyst [4,5]. Among the metal catalysts used, cobalt is the preferred FT active metal for conversion of natural gas derived synthesis gases (syngas of H2 /CO = 2) because of its high activity, high selectivity for long chain hydrocarbons and low water-gas shift (WGS) activity [69]. Previous studies showed that FT synthesis rates were proportional to cobalt metal dispersion. To expose as many metal cobalt atoms as possible to gaseous reactants, one normally deposits cobalt on a high surface carrier, such as silica [8,1013],

Corresponding author. Tel.: +81 93 695 3286; fax: +81 93 695 3378. E-mail address: lixiaohong@env.kitakyu-u.ac.jp (X. Li). 0926-860X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2011.02.002

alumina [1316], titania [7,13,17,18], or even carbon nanotubes [19]. On these supports, silica has been widely used since it has a higher surface area, more porosity, better stability and weaker metalsupport interactions. Conventionally supported cobalt catalysts are prepared via aqueous impregnation of porous oxide supports with solutions of various cobalt salts [6,8,10,20,21]. The supported cobalt salts are decomposed via calcinations in an oxidizing atmosphere. The prepared impregnated cobalt catalyst should be reduced in hydrogen to obtain high FT synthesis activity metallic cobalt. For impregnated prepared catalyst, cobalt is deposited on the support surface and its internal pores. The cobalt catalysts prepared from these methods demonstrate good metal dispersion and reducibility. However, due to the metallic cobalt deposited on the pore sites of the support, CO transfer limitation is unavoidable, thus leading to high H2 /CO ratios in these sites; such high H2 concentration is benecial to produce methane. To overcome such shortcomings, researchers have proposed eggshell-type catalysts [6,2224]. Eggshell-type catalysts, in which a thin layer of catalytic material is placed in the external surface of a spherical supported particle, exhibit excellent metal-utilizing efciency and overcome many limits, such as cobalt-support strong interaction, cobalt-support macrodistribution and restricted diffusion of CO into catalyst particles. Moreover, heat transfer is also one of the main issues in FT synthesis, since it is a highly exothermic process. If the evolved heat is not removed, catalytic sintering, decay and attrition are the net result.

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Fig. 1. Schematic ow diagram of slurry-phase FT synthesis apparatus.

An eggshell-type catalyst could effectively remove the redundant heat especially with combined with use of a slurry phase reactor, since the reactions were conducted on catalyst external surfaces. The released heat could easily transfer and enter into the solvent, whose temperature could be adjusted by a temperature control programme. Besides use in a slurry phase reactor, eggshell-type catalysts could also be applied to xed bed reactors because of the heat-removing effect of the catalyst itself. This work is aimed at producing a high performance Co/SiO2 eggshell catalyst to conduct FT synthesis. The prepared catalyst was characterized by SEM, EPMA, XRD and H2 chemisorption. The characterization results were discussed, together with the results of catalytic performance in FT synthesis conducted in a slurry phase reactor. The reaction activities of eggshell catalysts were studied and compared with those of the conventional impregnated cobalt catalysts. The effects of support size and W/F had also been intensively investigated.

2.2. Characterization of catalyst After calcination, the microstructure of the cobalt particles deposited on silica gels was measured using scanning electron microscopy (SEM, model S-3000N, HITACHI, Japan) and the elemental concentration map was constructed by using an electron probe microanalyzer (EPMA, model JXA-8100, JEOL Ltd., Japan). Before measuring, the catalyst pellet was embedded into resin and cut by the microtome method. The EPMA sample plates were analyzed at a 15 kV acceleration voltage of 1.87 107 A and a backscatter electronic beam diameter of 10 m. The X-ray diffraction (XRD) patterns of impregnated and eggshell Co/SiO2 catalysts were obtained at room temperature using a diffractometer (Rigaku Electronic, D/Max-VC) that employs Ni-ltered Cu(K ) radiation ( = 1.5404 A). Diffraction patterns were obtained with an X-ray gun operated at 40 kV and 20 mA, using a scan rate of 2 min1 (2) from 10 to 80 . The crystal size of the Co3 O4 over the calcined catalyst was estimated from the Scherrer formula and the diffraction (2 = 44.5 ). The crystal size of the metallic cobalt in the reduced catalysts was proportionate to the crystal size of Co3 O4 , as illustrated in the reference [25]. H2 -chemisorption was adopted to analyze cobalt reduction extent and to judge FT synthesis performance of a series of prepared catalysts using an Autosorb-1-C (Quantachrome, Yuasa Ionics) analyzer. Each sample catalyst weight of 0.5 g was loaded in the analyzer. Before measuring, the sample catalysts were evacuated at 473 K for 30 min and 323 K for 30 min to remove water and air, respectively. In order for us to ensure consistency of the study, the H2 chemisorption analysis was strictly conducted at the same condition as reduction treatment before FT synthesis. The sample catalysts were reduced in owing hydrogen with temperature programming from ambient to 673 K at the rate of 3 K/min and then the temperature was maintained at 673 K for 3 h, next they were evacuated for 1 h at 673 K to remove the gas phase and they were cooled in vacuum to 593 K. After this temperature was reached, H2 adsorption isotherms were measured between 10 mmHg to 850 mmHg. The amount of H2 chemisorbed was determined by extrapolating the linear part of the isotherm to zero pressure. 2.3. FT synthesis FT synthesis was carried out in a 100 cm3 slurry-phase reactor. A schematic diagram of the apparatus used in the present study is shown in Fig. 1. Prior to the conduct of the FT synthesis, the

2. Experimental 2.1. Catalyst preparation The 15 wt% Co/SiO2 eggshell catalysts were prepared by a spray method. Cobalt nitrate was used as a precursor of cobalt and dissolved with ethanol and distilling water to form spray solutions. Silica gels (Fuji-silica Q-15, average size: 300 m, 1300 m and 1800 m) were used as eggshell supports. The amount of cobalt nitrate was calculated based on the amount of support silica gels and needed to obtain a cobalt weight ratio of 15 wt% in Co/SiO2 catalysts. Cobalt solutions were atomized as ne sprays using a spraying apparatus. The spray solutions were sprayed on the support surfaces in batches. Until the current ne spray was dried on support surfaces, the spray process could continue to proceed. To make sure that the cobalt particles could be well-deposited on support surfaces, one should stir the silica particles during the spray process. After being sprayed, the eggshell catalysts were dried overnight at 393 K and then calcined at 473 K for 2 h. The 15 wt% Co/SiO2 impregnated catalysts were prepared by an incipient-wetness impregnation method. The cobalt nitrate was used as a precursor of cobalt, and silica gels (the same as eggshell catalyst supports) were used as the supports. After being dried overnight at 393 K, the catalysts were calcined at 473 K for 2 h.

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catalysts were reduced in pure H2 (100 ml/min) at 673 K for 3 h. The reduced catalyst was then transferred to a mortar lled with 50 ml of n-hexadecane solvent. After transferring the slurry mixture into the autoclave followed by xing it to a cover equipped with a motor-driven at blade impeller, we purged the reaction system with syngas. The operating conditions were H2 /CO = 2, T = 503 K, P = 1.0 MPa, W/F = 5.0 g-cat h/mol; stirring speed was maintained at 1050 rpm. Efuent gas passed through two consecutive traps to condense the remaining liquid products. The efuent gas ow rate was measured with a wet gas ow meter. Products in the efuent gas were analyzed via three consecutive online gas chromatographs (GC). CO, CO2 and CH4 were analyzed with a GC equipped with a packed column and a thermal conductivity detector (TCD), while the amounts of other gaseous hydrocarbon products, C1 C5 and C6 C10 , were determined with two different GC equipped with a packed column and a ame ionization detector (FID). After the course of reaction, liquid products in the traps were mixed into the reaction mixture, where an internal standard was added. Subsequently, the product distribution was analyzed with a FID GC equipped with a capillary column (DB-2881). The catalyst activities were evaluated in terms of CO conversion and product distribution (space-time yield, STY: mol/kg-cat/h). The yield of the hydrocarbons was calculated on a carbon basis.

3. Results and discussion 3.1. Catalyst microstructure and XRD analysis To directly view the prole structure of the prepared catalysts, we used the SEM and EPMA characteristic analyses to identify the microstructure information of cobalt deposited on the surface of support (silica gel average size 300 m); the resulting gures are shown in Figs. 2 and 3. In SEM gures, circle regions represent the support silica gel particles. The relatively dark circles in impregnated Co/SiO2 catalyst mean that cobalt particles and supports were overlapped, as shown in Fig. 2(a). In Fig. 2(b), the dark colour at the outside of support illustrates that cobalt was deposited on the external surface of support in eggshell Co/SiO2 catalyst. These results could also be more clearly certied from EPMA gures. In EPMA gures, the distribution of the cobalt on the surface of silica gel is tested using the area scan method, where the concentration is represented by the colours. The dark colour ring (cobalt) and white ring (silica gel) in the Fig. 3(a) of impregnated Co/SiO2 catalyst mean that the cobalt was deposited uniformly on silica gel from its surface to inside. Unlike the procedure used with the impregnation method, the cobalt was sprayed on the surface of silica gel when preparing the eggshell cobalt catalyst. Almost all of the cobalt atoms were deposited on the external surfaces of silica gel. In Fig. 3(b) of eggshell Co/SiO2 catalyst, only a narrow cobalt ring, representing cobalt dispersion on silica gel external surface, is illustrated. The samples of Co/SiO2 catalyst (impregnated and eggshell type, support size: 1800 m) were examined by XRD to determine catalyst chemical form and crystallite size. In all calcined catalysts prepared from cobalt nitrate, XRD reveals the presence of a Co3 O4 crystalline phase, as shown in Fig. 4. To more accurately detect the Full-Width Half-Maximum (FWHM), we slowly scanned around the diffraction (2 = 44.5 ) area at the rate of 0.2 min1 from 43.0 to 46.0 . After smoothing and multi-peak separation, the crystal sizes of Co3 O4 over the calcined catalysts were calculated (impregnated Co/SiO2 : d (Co3 O4 ) = 30.14 nm and eggshell Co/SiO2 : d (Co3 O4 ) = 34.54 nm), based on Scherrer formula and the XRD diffractions at 44.5 . Thus, there was a clear result for the crystal size of the metallic cobalt in the reduced catalysts, since the crystal size of metallic cobalt is proportional to the size of Co3 O4 .

Fig. 2. SEM microstructure photo of impregnated and eggshell Co/SiO2 catalyst.

3.2. Reaction performance of FT synthesis 3.2.1. Reaction performance over eggshell and impregnated catalyst To judge the reaction performance of prepared catalyst, the rst run was arranged to compare the performance between the eggshell and conventional impregnated Co/SiO2 catalyst (silica gel average size: 1800 m) over FT synthesis in a slurry-phase reactor. The catalyst activity was evaluated at the condition of T = 503 K, P = 1.0 MPa, W/F = 5.0 g-cat h/mol, H2 /CO = 2 and the stirring speed was maintained at 1050 rpm. The results are shown in Fig. 5. The CO conversion was stable for impregnated catalyst and remained at around 37%. In impregnated catalyst, the metallic cobalt existed in the pore canals of silica gels. The porous structure of silica gels determined that there is an intrapellet diffusion limitation (difference in diffusion rates between H2 and CO in pore canal) when reactants diffused to the metallic cobalt, and the different diffusion rates between H2 and CO caused their concentration gradient distributions [26]. The concentration ratio of H2 and CO (H2 /CO) is far larger than 2 in the pore sites. It is known that high concentrations of H2 would induce the chain growth termination and would affect the selectivity of CH4 and heavy hydrocarbons. When an eggshell catalyst was used, CO conversion decreased a little during the rst 2 h, then became stable. Although there was a limited improvement for CO conversion, the CH4 selectivity was decreased obviously when using the eggshell catalyst, since the transfer limitation of CO could be effectively eliminated. Also, it

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Fig. 3. EPMA photos of impregnated and eggshell Co/SiO2 catalyst.

Fig. 5. Comparison of the FT reaction performance between impregnated and eggshell Co/SiO2 (condition: T = 503 K, P = 1.0 MPa, W/F = 5.0 g-cat h/mol, H2 /CO = 2 and stirring speed was 1050 rpm).

Fig. 4. XRD patterns for the impregnated and eggshell Co/SiO2 (support size: 1800 m, ( ) Co3 O4 ).

was easier to leave the inside of catalyst after CH4 was generated since its transfer rate was higher than those of other hydrocarbons. Thus, CH4 selectivity was decreased obviously on eggshell Co/SiO2 catalyst, since H2 and CO intrapellet diffusion effects were suppressed more effectively compared with the case for impregnated catalyst. This could also be found in the results of hydrocarbon distribution in Fig. 6. On the carbon basis, the hydrocarbon synthesis rate was dened as space-time yield (STY), which is the number of moles of a given hydrocarbon per kilogram catalyst per hour (mol/kg-cat/h). According to the ASF equation calculation, the chain growth probabilities () were calculated for eggshell (1 = 0.90) and impregnated (2 = 0.84) cobalt FT synthesis, respectively. 1 was larger than 2 , which means that eggshell catalyst was more inclined to produce long chain hydrocarbons than impregnated catalyst. In impregnated catalyst, chain growth was blocked since CO is a diffusion-limited reactant compared with H2 . The diffusion limitation effect of reactants was eliminated because FT syntheses were conducted on catalyst external surfaces when using eggshell catalyst. This was obvious from the STY of hydrocarbons of C9+ shown in Fig. 6.

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Fig. 6. Hydrocarbon distribution for impregnated and eggshell Co/SiO2 (Eggshell: 1 = 0.90; impregnated: 2 = 0.84).

3.2.2. Effect of support size For more thorough investigations on eggshell catalysts, a series of reactions were conducted over three kinds of eggshell Co/SiO2 catalysts in which the sizes of support were shaped as: 300 m, 1300 m and 1800 m (average size). Reaction conditions were the same as previous reactions and the results are shown in Fig. 7. It was not clear how the size of support had inuenced the CH4 selectivity, since almost all of the reactions took place on catalyst external surfaces. The CO conversion increased about 8% as the support size increased from 300 m to 1300 m. When we continued increasing support size to 1800 m, CO conversion declined to a certain degree and the material had an activity similar to that of the catalyst of 300 m. It means there is an optimum size for the silica gel which would demonstrate the best activity for FT synthesis. A series of runs were conducted using impregnated and eggshell Co/SiO2 catalysts which contained different sizes of silica gel and cobalt weight ratios. The detailed parameters that could reect on the performance of FT synthesis are classied in Table 1; these include CO conversion (catalysts activity), CH4 selectivity (byproduct), C5+ selectivity (desired product) and ASF alpha value (chain growth probability). From the data of CO conversion, one can nd that eggshell catalysts had higher activity than impregnated catalysts when the cobalt content was the same in the two kinds of catalyst (15 wt%). The impregnated catalysts had similar activity to 15 wt% eggshell catalysts until cobalt content increased to 20 wt% in impregnated catalysts. As the support size exceeded 1300 m, the performance of FT synthesis was obviously upgraded for eggshell catalysts, which gave higher CO conversion, C5+ selectivity, and alpha value and far lower CH4 selectivity than impregnated catalysts. The upgraded performance may be attributed to a weakening efciency of intrapellet diffusion limitation which obviously existed in the pore structure catalysts. Due to
Table 1 FT synthesis performance over impregnated and eggshell Co/SiO2 . Catalyst Support size ( m) Co weight in catalyst (wt%) CO con. (%) CO2 selectivity (%) % Selectivities (carbon basis) C1 C2 C4 C5+ ASF alpha () Impregnated 300 15 29.86 1.18 9.04 13.62 77.34 0.90 20 43.45 1.23 9.68 14.53 75.79 0.89 15 32.25 2.94 21.82 13.79 64.39 0.83 1300 20 43.47 2.57 20.21 14.74 65.05 0.85

Fig. 7. Effect of support size on FT synthesis over eggshell Co/SiO2 .

the intrapellet diffusion limitation, there is a different mass transfer rate between H2 and CO. Thus, the H2 concentration is higher than CO concentration in the pore sites in impregnated catalysts. Moreover, the proportion of H2 and CO (H2 /CO) continued to enlarge along with pore canals from catalysts surface to its inside for each impregnated catalyst particle. It is well known that higher H2 con-

Eggshell 1800 15 35.33 1.97 22.98 15.36 61.66 0.84 20 42.12 2.12 24.44 14.88 60.68 0.85 300 15 38.98 1.02 8.79 11.20 80.01 0.90 1300 15 44.67 0.54 9.51 10.56 79.93 0.90 1800 15 38.81 0.44 9.68 10.87 79.45 0.90

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centration would lead to higher CH4 and short chain hydrocarbon selectivity. The cobalt that existed in pore canals was harder to be reduced and utilized than external surface cobalt. Thus, low CO concentration, as well as high CH4 selectivity, low C5+ selectivity and low alpha values were obtained when impregnated catalyst was used. In eggshell catalyst, the reaction sites mainly existed on the support external surfaces; the intrapellet diffusion limitation was effectively diminished. Therefore, the performance of FT synthesis had been upgraded effectively by using eggshell catalysts when the size of silica gels is relatively large. As described above, the existing H2 and CO concentration gradient distribution would obviously affect the parameters of CH4 selectivity, C5+ selectivity and alpha value. The concentration gradient distribution caused by intrapellet diffusion limitation was related to the pore structure of pellet (silica gel). Thus, it could be suppressed by decreasing the size of silica gel. With the size of silica gel decrease, the pore canal shortened and spherical surface area increased, which means that the difference between impregnated and eggshell catalyst was not as obvious as big size supported catalyst. As shown in Table 1, when using small size silica gel as support, the parameters of CH4 and C5+ selectivity and alpha value for impregnated catalyst were almost the same as those for eggshell catalyst during FT synthesis. 3.2.3. Effect of W/F To study the effect of the W/F (catalyst weight/feed ow rate) ratio on FT synthesis, we conducted experiments at different W/F ratios which were adjusted by changing the syngas ow rate. The other reaction conditions were the same as those in previous experiments. According to the results obtained from these experiments, the advantages of utilization of eggshell Co/SiO2 catalyst were obvious compared with using impregnated Co/SiO2 catalyst, as shown in Fig. 8. Impregnated Co/SiO2 catalyst showed the lower CO conversion, indicating that a diffusion-controlled regime due to metallic cobalt existed in pore sites. Furthermore, CH4 selectivity was also obviously affected for impregnated catalyst with W/F change. One main inuencing factor for CH4 selectivity was H2 concentration, which was controlled by porous structure and syngas ow rate in an indicated position, especially in internal pore sites. Thus, there is an obvious uctuation of CH4 selectivity with W/F change in impregnated catalyst. In eggshell catalyst, all reactions took place on catalyst external surfaces. There was no diffusion controlled regime between H2 and CO, as was indicated in impregnated catalyst. The deviation of CH4 selectivity between impregnated and eggshell catalyst increased with feed gas ow decrease. Therefore, the eggshell Co/SiO2 catalyst demonstrated higher FT synthesis performance in different W/F conditions than impregnated Co/SiO2 catalyst. 3.3. H2 -chemisorption Chemical adsorption (chemisorption) is an interaction between the surface where the adsorption takes place and the substance deposited in the presence of a catalyst. The typical result of a catalyst characterization measurement by chemisorptions consists of a graphical representation of the chemisorption isotherm and tabuTable 2 H2 -chemisorption over impregnated and eggshell Co/SiO2 . Catalyst Support size ( m) Co weight in catalyst (wt%) Surface cobalt amount ( mol/g) Cobalt particle size (nm) H.C.-STY ( mol/g/s) TOF (s) Impregnated 300 15 40.51 31.20 6.29 0.16 20 45.81 36.90 9.15 0.20 15 39.98 31.70 6.79 0.17 1300 20 52.52 32.18 9.15 0.17 15 43.70 29.00 7.41 0.17 1800 20 57.15 29.57 8.87 0.15 Eggshell 300 15 38.65 32.80 8.21 0.21 1300 15 40.98 30.93 10.06 0.25 1800 15 33.67 37.65 8.17 0.24

Fig. 8. Effect of W/F on FT synthesis over eggshell Co/SiO2 .

lar data providing information on the amount of catalyst deposited on support surface and catalyst reduction extent. H2 chemisorption was adopted in this work and used to characterize the prepared eggshell and impregnated Co/SiO2 catalysts. As described previously, the crystal size of eggshell metallic cobalt (the size of support: 1800 m) is a little larger than that of impregnated metallic cobalt, as judged from XRD analysis. The data of metallic cobalt crystal size calculated from H2 chemisorption (Table 2) are consistent with XRD data.

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For the actual quantity dening the activity of a catalyst, the turnover frequency (TOF) is used; it is dened as the number of molecules of a given product per catalytic site per unit time. Concretely, the amounts of given product are the STY of generated hydrocarbons and catalytic sites are the surface metallic cobalt particles. From the data of chemisorption and STY of FT synthesis, TOF values of the two methods of catalysts preparation were calculated. For the same weight ratio cobalt catalyst (15 wt%), even though our eggshell catalyst gave a little lower surface cobalt amount than the conventional impregnated catalyst, the TOF of eggshell catalyst was still larger than that of impregnated catalyst. The high surface cobalt amounts mainly originated from the high internal surface area of pore canals in impregnated catalyst. As previously interpreted, CO diffusion was limited in impregnated catalyst when CO diffused to the metallic cobalt atoms which were deposited in pore sites. Thus, there was low utilization for the cobalt deposited in pore canals. On the other hand, almost all of metallic cobalt particles were deposited on the external surface of silica gel in eggshell Co/SiO2 catalysts. Therefore, the CO diffusion limitation impact on FT synthesis was effectively eliminated. The reduced metallic cobalt was effectively utilized and high performance of FT synthesis was obtained. 4. Conclusions One eggshell-type Co/SiO2 catalyst was prepared by the spraying method. SEM and EPMA characterization indicated that almost all cobalt atoms were deposited on silica gel external surfaces in the prepared eggshell cobalt catalyst. The crystal size of metallic cobalt was measured by XRD analysis. FT synthesis experiments were conducted at certain conditions, and the results demonstrated that eggshell type cobalt catalyst was inclined to generate long chain hydrocarbons and had relatively low CH4 selectivity. Higher TOF values calculated from H2 -chemisorption and STY of hydrocarbon also indicated that eggshell Co/SiO2 catalysts had higher

FT synthesis performance than conventional impregnated Co/SiO2 catalysts. References

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