Catal Lett DOI 10.

1007/s10562-009-0021-0

Slurry-Phase FischerTropsch Synthesis Using Co/c-Al2O3, Co/SiO2 and Co/TiO2: Effect of Support on Catalyst Aggregation
Jong-Hyeok Oh Jong Wook Bae Seon-Ju Park P. K. Khanna Ki-Won Jun

Received: 15 February 2009 / Accepted: 5 May 2009 Springer Science+Business Media, LLC 2009

Abstract The catalytic performance of Co/c-Al2O3, Co/ SiO2 and Co/TiO2 catalysts has been investigated in a slurry-phase FischerTropsch Synthesis (FTS). Although Co/SiO2 catalyst shows higher CO conversion than the other catalysts, the intrinsic activity is much higher on Co/ TiO2 due to large pore size and low deactivation of large cobalt particles by reoxidation mechanism. Co/c-Al2O3 catalyst conrms low formation rate of oxygenates and C5? selectivity because of deactivation of catalyst due to catalyst aggregation and reoxidation by the in situ generated water during the FTS reaction. Long-chain hydrocarbons such as wax formed during FTS reaction generally contains water and trace amount of oxygenate which are conducive to the formation of a macro-emulsion of wax products. Formation of such macro-emulsion on the catalyst suggests that the presence of proper amount of alcohol content derived FTS reaction on large pore of catalyst inhibits the catalyst aggregation. The intrinsic activity (turn-over frequency; TOF) of cobalt-based catalysts, in a slurry-phase FTS reaction, is affected by the average pore size of catalyst, cobalt particle size, degree of reduction of cobalt species and possible reoxidation by in situ generated water.

Keywords FischerTropsch synthesis Turn-over frequency Pore size of catalyst Slurry-phase reaction Product distribution

1 Introduction Conversion of synthesis gas to heavy hydrocarbon using FischerTropsch Synthesis (FTS) is a well known process. Synthesis gas is normally derived from coal gasication or natural gas reforming. Of late FTS has attracted a great deal of attention mainly due to the increased demand for environmentally benign liquid fuels. Supported cobalt catalyst has been widely studied due to its high activity, high selectivity to long-chain parafns, and low activity for water-gas shift (WGS) reaction [1, 2]. The physical and morphological properties of supports play an important role in altering FTS activity, e.g., the pore size and the surface structure of support inuences the cobalt dispersion, particle size, reducibility and diffusion coefcient of reactants and products [38]. Alumina is one of the most promising supports due to its strong mechanical strength and high surface area, especially for the slurry-phase FTS reaction. In case of Al2O3 support, it has been reported that cobalt particle size and reducibility decreases due to the strong metal-support interaction which leads to formation of inactive cobalt species such as cobalt aluminate [3, 6, 9]. However, the interaction between SiO2 and cobalt species has been described as relatively weak which is considered better for cobalt reducibility and large cobalt particle size formation. Due to large particle size, cobalt dispersion is usually much lower in silica-supported cobalt catalyst than that of alumina-supported catalyst [9]. Amongst metal oxides, TiO2 is also widely adopted for FTS reaction and, in spite of its

J.-H. Oh J. W. Bae S.-J. Park P. K. Khanna K.-W. Jun (&) Petroleum Displacement Technology Research Center, Korea Research Institute of Chemical Technology (KRICT), P.O. Box 107, Yuseong, Daejeon 305-600, Korea e-mail: kwjun@krict.re.kr Present Address: P. K. Khanna Nanoscience Laboratory, Center for Materials for Electronics Technology (C-MET), Panchwati, off Pashan Road, Pune 411 008, India

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strong metal-support interaction, low surface area results in formation of large cobalt particles. Due to better mechanical properties of SiO2 and TiO2, these are widely used as supports in a xed-bed FTS reaction. Also, it has been reported [6] that metal-support interaction affects the reducibility of cobalt oxide species in the following order; Al2O3 [ TiO2 [ SiO2 [6]. Oukaci et al. [10] reported that the FTS activity of the cobalt-supported catalysts varied in the order of Al2O3 [ SiO2 [ TiO2 for a slurry bubble column reactor (SBCR). However, a different trend reported by Reuel and Bartholomew [4] on the catalytic activity of cobalt-based catalyst as a function of support, is also noteworthy. They described that the activity declines in the following order; Co/TiO2 [ Co/Al2O3 [ Co/SiO2 with respect to reducibility and cobalt particle size. In addition, support having a large pore size is generally responsible for the formation of large particle size with facile reducibility [11]. Although there are a large number of reports focusing on the inuence of support with different textural properties, systematic and comparative study on the support such as c-Al2O3, SiO2 and TiO2 with respect to intrinsic activity has not been established taking into consideration of the pore size of the support, aggregation phenomenon of the catalyst and particle size of cobalt species in a slurry-phase FTS reaction. In the present investigation, the cobalt-based FTS catalysts with three different supports were prepared by impregnation method and their catalytic activities were compared with respect to intrinsic activity (TOF), nature of catalyst aggregation and pore size of support in a slurryphase continuous stirred tank reactor (CSTR). The different FTS activity on c-Al2O3, TiO2 and SiO2 support is further substantiated by characterization techniques such as BET surface area measurement, powder X-ray diffraction (XRD) analysis, temperature-programmed reduction (TPR), H2 chemisorption and O2 titration.

nitrate (Co(NO3)2 6H2O) was used as a metal precursor and dissolved in ethanol so as to obtain 20 wt% cobalt on support. The prepared catalyst was dried at 393 K for 12 h and subsequently calcined at 773 K for 5 h. The nal catalysts i.e., Co/c-Al2O3, Co/SiO2 and Co/TiO2 are designated as CoA, CoS and CoT, respectively for ease of presentation. 2.2 Catalytic Activity Test The schematic reaction apparatus is shown in Fig. 1 that includes a reactor with capacity of 600 mL equipped with a magnetic stirrer and two traps (separation units such as hot and cold trap) operating at 473 and 323 K, respectively to remove the heavy hydrocarbons and water formed during FTS reaction. Prior to activity test, the FTS catalyst was activated at 673 K in a xed-bed reactor (I.D. = 50 mm) for 12 h with 5% H2/He. The activated (reduced) catalyst was transferred to the reactor without the exposure to air. The activity test was carried out in a slurry-phase continuous stirred tank reactor (CSTR, I.D. = 80 mm) under the following reaction conditions; liquid medium (squalane) = 300 g; catalyst = 5.0 g; T = 493 and 513 K; P = 2.0 MPa; space velocity (SV; L/kgcat/h) = 2,000 and 1,000; feed composition of H2/CO/CO2/Ar = 57.3/28.4/ 9.3/5.0 mol%, respectively. Efuent gas from the CSTR reactor was analyzed by an online gas chromatograph (YoungLin Acme 6000 GC) employing GS-GASPRO capillary column connected with ame ionization detector (FID) for the analysis of hydrocarbons and Porapak Q/ molecular sieve (5A) packed column connected with thermal conductivity detector (TCD) for the analysis of carbon oxides and internal standard gas i.e., Ar.

2 Experimental 2.1 Catalyst Preparation The cobalt based catalysts were prepared by impregnation method in the slurry of supports such as c-Al2O3, SiO2 and TiO2 with ethanol as a solvent. The i-Al2O3 (Catapal B precalcined at 623 K for 5 h, surface area (Sg)of 231 m2/g and average pore diameter of 7.2 nm), TiO2 (Degussa P25 with size range of 74 * 117 lm which is previously calcined at 723 K for 5 h, Sg of 49 m2/g and average pore diameter of 48.7 nm) and SiO2 (Davisil 645 with size range of 173 * 221 lm used without calcination, Sg of 324 m2/g and average pore diameter of 10.9 nm) were adopted as supporting materials for the preparation of catalysts. Cobalt

Fig. 1 Schematic diagram of reaction apparatus for slurry-phase FTS reaction

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2.3 Catalyst Characterization The BET surface area, pore volume and pore size distribution was estimated from nitrogen adsorption and desorption isotherm data at 77 K using a constant-volume adsorption apparatus (Micromeritics, ASAP-2400). The pore volume of the samples was determined at a relative pressure (P/Po) of 0.99. The calcined sample was degassed at 573 K with a He ow for 4 h before measurement. The pore size distribution of the samples was determined by the BJH (Barett-Joyner-Halenda) model from the data of desorption branch of the nitrogen isotherms. The powder X-ray diffraction (XRD) patterns of the samples were obtained with a Rigaku diffractometer using Cu-Ka radiation. The reduced samples at 673 K for 12 h with 5% H2/N2 ow, followed by passivation with 0.1% O2/He for 0.5 h at room temperature (RT), were used to identify the crystalline phases of Co3O4, CoO and Co metal species. The cobalt content (wt%) was further determined by using the X-ray uorescence (XRF) analysis with SEA5120 equipment. The temperature programmed reduction (TPR) experiments were performed to determine the reducibility of Co3O4. Prior to the TPR experiment, the sample was pretreated in a He ow up to 623 K and kept for 2 h to remove the adsorbed water and other contaminants followed by cooling to 323 K. The reducing gas containing 5% H2/Ar mixture was passed over the sample at a ow rate of 30 mL/min with the heating rate of 10 K/min up to 1,000 K. The efuent gas was passed over a molecular sieve trap to remove the generated water and analyzed by a GC equipped with TCD. H2 chemisorption measurement was carried out using a Micromeritics ASAP 2020C. Before measurement, the sample was dried in vacuum for 40 min at 673 K and subsequently reduced at 673 K in owing H2 for 12 h. After reduction, the sample was evacuated for 2 h at the same temperature and the H2 adsorption isotherm was obtained at 373 K. The H/Co ratio at zero pressure was found by extrapolation of the linear part of the isotherm. Particle size estimation was rst made based on hemispherical geometry, assuming complete reduction and an H/Co adsorption stoichiometry of 1 [12, 13] and reconsidered with the degree of reduction. The extent of cobalt reduction was determined by O2 titration of reduced sample at 673 K, using the same instrument mentioned above assuming that all the metallic Co was converted to Co3O4. The crystallite size of cobalt was recalculated by taking the extent of reduction into consideration. The calculation of metallic cobalt particle size (d(Co0); nm) out by using the following equation; was carried d Co0 ; nm 96=dispersion% degree of reduction [12, 13].

3 Results and Discussion 3.1 Physicochemical Properties of Catalysts The summarized results of surface area and pore volume for CoA, CoT and CoS catalysts are shown in Table 1 and BJH pore size distribution is shown in Fig. 2. The surface area increased in the order of CoS [ CoA [ CoT, however, the average pore size is found to be smallest on CoA catalyst. Upon impregnation of cobalt on the support, the surface area decreased, especially on CoA catalyst. The mono-modal pore size distribution of all catalysts revealed a uniform distribution of cobalt species on each support. The larger pore size of 25.1 nm and small surface area of 40 m2/g was observed on CoT catalyst. Support having a large pore size such as TiO2 and SiO2 is generally responsible for the formation of large cobalt particles facilitating the reduction [11]. The small pore size of 6.9 nm and small pore volume on CoA is not benecial for diffusion of FTS products generated. Due to uniform pore size distribution of cobalt impregnated on Al2O3 support, the catalyst shows reduced pore volume and average pore

Table 1 Physical properties of FTS catalysts Notation Surface area (m2/g) CoA CoT CoS 139 40 247 Pore Average volume pore (cm3/g) diameter (nm) 0.326 0.263 0.992 6.9 25.1 12.9 Support Surface area 231 49 336 Pore Pore volume diameter 0.474 0.204 1.113 7.2 16.1 11.0

CoA = 20 wt% Co/c-Al2O3; CoT = 20 wt% Co/TiO2; CoS = 20 wt% Co/SiO2

dV/dlog(D) pore volume (cm /g)

CoA CoT CoS Al2O3 TiO2 SiO2

0 1 10 100

Pore diameter (nm)

Fig. 2 Pore size distribution of CoA, CoT and CoS catalysts with each support of Al2O3, TiO2 and SiO2

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J. Oh et al. Table 2 Cobalt particle size and surface area measured by H2 chemisorption and reduction degree by O2 titration Notation H2 chemisorption H2 uptakes (mmol/g) CoA CoT CoS
a b

Co particle size (nm)a 15.3 61.4 26.0

Co surface area (m2/g-metal) 44.1 11.0 25.9

Co dispersion (%)a 6.5 1.6 3.8

Reduction degree (%)b

Particle size of Co3O4 from XRD 9.6 26.8 13.9

Co content (wt%) from XRF

0.06015 0.01678 0.04685

65.1 73.0 86.4

19.8 19.9 19.8

Cobalt particle size and dispersion was corrected by considering the reduction degree and Co content which is veried by XRF analysis

The degree of reduction of cobalt oxide is measured by O2 titration by considering theoretical O2 uptake with the following equation; 3Co + 2O2 ! Co3 O4

size which means efcient deposition of cobalt species in the inner pore of Al2O3 support. Although the surface area after cobalt impregnation decreased, the average pore size of CoT and CoS catalysts slightly increased. This may be considered mainly due to deposition of large cobalt particles on the outer surface of SiO2 and TiO2. Thus, the interparticular large pores induced from deposited cobalt oxides contribute to the increased average pore size on CoT and CoS catalysts. The initial average pore size of SiO2 and TiO2 support is around 11.0 and 16.1 nm, respectively which increases to 12.9 and 25.1 nm catalyst after cobalt loading. Normally, cobalt-support interaction depends on the type of support and cobalt particle size, and its interaction is generally stronger on TiO2 and weaker on SiO2 [46, 9]. In the case of CoS catalyst, the interaction of the metal salt with support is small thus leading to high degree of reduction of cobalt species. But, since CoA and CoT catalysts show a strong metal-support interaction and are difcult to reduce completely, the estimated particle size assuming complete reduction may not always be accurate. The summary of cobalt particle size, surface area of metallic cobalt and its dispersion which is recalculated by considering the reduction degree by O2 titration and cobalt content by XRF analysis is shown in Table 2. It is observed that the Co particle size in CoA (15.3 nm) is smaller and therefore it gives high surface area and larger Co dispersion in comparison to CoS and CoT catalysts. Due to the weak metal-support interaction and medium pore size of CoS catalyst, reducibility of cobalt species is slightly easier thus yielding medium cobalt particle size. From XRD analysis, the crystalline phases of cobalt species in the reduced and successively passivated FTS catalysts are shown in Fig. 3. It is found that the presence of Co3O4 in CoA catalyst is more prominent than in CoT and CoS catalysts suggesting relatively homogeneous distribution of cobalt particles on Al2O3 support. To verify the above result, the particle size of Co3O4 is further estimated from X-ray line broadening using the Scherrers equation. The particle size of Co3O4 at 2h = 36.8 and CoO at 62.0

CoA

Intensity (a.u.)

Co3O4 CoO Co TiO

CoT

CoS

10

20

30

40

50

60

70

80

2 Theta (degree)
Fig. 3 X-ray diffraction (XRD) patterns of reduced and subsequently passivated FTS catalysts

have similar dimensions and its size is around 9.6, 26.8 and 13.9 nm on CoA, CoT and CoS, respectively. Thus, the particle size of cobalt was bigger in case of CoT and smalller in CoA catalyst. Temperature-programmed reduction proles of FTS catalyst prepared with different supports are shown in Fig. 4. The TPR data reveal that the different supports inuence the reduction behavior of the catalysts in a different way. The reducibility reects the extent of metalsupport interaction. As shown in Fig. 4, CoA and CoT show two major peaks with different relative intensity and CoS had an additional small third peak at around 970 K. At *620 K, CoT and CoS show the rst reduction peak which is attributed to the reduction of Co3O4 to CoO. However, in case of CoA, reduction of Co3O4 was much difcult and needed higher temperature (*750 K). Similarly, second peak is due to metallic cobalt arising out of reduction of CoO. A third peak in case of CoS catalyst at around 950 K is considered from the reduction of cobalt silicate based on the literature [14]. From Fig. 4, one can see that CoS catalyst is the easiest to reduce to Co metal but CoA is relatively difcult. The O2 titration method was

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1100
766 982

1000 900

CoA Intensity (a.u.)

623 769

CoT
612

700
678

600
981

CoS

500 400 300 100

10

20

30

40

50

60

70

80

90

Time (min)

Fig. 4 Temperature-programmed reduction (TPR) proles of the FTS catalysts

used to measure the degree of reduction of the catalysts and the results are summarized in Table 2. Overall, it is observed that smaller cobalt particle size is difcult to reduce due to strong interaction of cobalt species with support especially when c-Al2O3 is used. 3.2 FTS Activity Correlated with Cobalt Particle Size and Pore Size of Support The proper selection of supporting material is important to obtain high catalytic activity with respect to the dispersion of active metals and diffusion (mass transfer) in the pores of support. Especially, in the slurry-phase reaction, attrition resistance and pore size distribution are important properties. The high attrition resistance of c-Al2O3 is major

Table 3 CO conversion and product distribution at different temperature and space velocity on different FTS catalysts Notation Conv. of CO (C-mol %) TOF (910-3/s)a Product distribution (C-mol %)b C1 T = 493 K; SV = 2,000 L/kgcat/h CoA CoT CoS CoA CoT CoS CoA CoT CoS
a b

Temp (K)

800

reason for adopting it for the slurry-phase reaction, however, its small pore size and strong interaction between cobalt and support is not benecial for obtaining high catalytic activity. It has been reported that the variation of pore size of c-Al2O3 affects the FTS activity and large pore size is good for obtaining high FTS activity [11, 15]. The bimodal pore size distribution also helps to solve poreblocking by heavy hydrocarbons formed during the FT reaction [16]. The activity and selectivity for FTS reaction are summarized in Table 3 and the variation of CO conversion with time on stream (TOS) is shown in Fig. 5. From the start of reaction to around 20 h at 493 K and SV = 2,000 L/kgcat/h, CO conversion on CoA is similar to that of CoT, but CO conversion on CoA only gradually increased to 31.9% at *80 h on stream. The low selectivity to methane in the slurry-phase FischerTropsch reaction is observed at low CO conversion, especially on CoT and CoS catalysts. It suggests that the cobalt metal on the c-Al2O3 was rearranged to a proper state during FTS either due to the surface reconstruction mechanism or due to redispersion of cobalt species [17, 18]. CoS showed the highest CO conversion of 34.8% and the lowest conversion of 18.2% was observed on CoT. The difference in CO conversion at 493 K is related with degree of reduction of cobalt oxide. The activity of CoS is highest among the selected catalysts due to the presence of large number of metallic cobalt particles. CoA catalyst is found to have relatively poor reduction degree, but it has superior metal dispersion and metallic surface area than that of CoT catalyst therefore it shows better catalytic activity when compared with CoT catalyst. From the literature, it is understood that for better selectivity to higher C5? products

C24

C5?

Olens in C24

31.9 18.2 34.8 61.3 54.3 69.2 68.8 73.2 95.8

12.2 27.9 20.6 23.4 83.1 40.9 13.1 56.0 28.3

4.3 1.7 2.1 7.5 5.5 6.9 5.8 9.6 31.0

5.8 3.1 4.5 10.2 6.1 10.0 7.8 8.6 29.3

89.9 95.2 93.4 82.3 88.4 83.1 86.4 81.8 39.7

55.6 58.6 56.1 42.7 37.0 41.9 44.8 29.5 13.2

T = 513 K; SV = 2,000 L/kgcat/h

T = 513 K; SV = 1,000 L/kgcat/h

The values of CO conversion and selectivity are the averaged values for around 10 h after stabilizing catalytic activity at each reaction conditions TOF = moles of CO converted per total mole of surface Co atom per second The content of alcohol (C7C12) in heavy hydrocarbons is around 2.08, 3.17 and 4.04 wt% for CoA, CoT and CoS, respectively

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100 90
CoA CoT CoS

CO conversion (C-mol%)

80 70 60 50 40 30 20 10 0 0 20 40 60 80 100 120 140 160 180 200 220 240

T=493 K SV=2000 T=513 K SV=1000

T=513 K SV=2000

Time on stream (h)

Fig. 5 CO conversion with time on stream (h) on different FTS catalysts T = 493513 K; P = 2 MPa; space velocity (SV) = 1,000 2,000 L/kgcat/h; feed compositions of H2/CO/CO2/Ar (mol %) = 57.3/28.4/9.3/5.0

in wide pore catalysts are preferred [19]. In the present case, CoA has the smallest pore diameter which inuences the diffusion of FTS products, thus showing relatively poor C5? selectivity at the reaction conditions of 493 and 513 K and SV = 2,000 L/kgcat/h. However, due to the presence of large pore and large cobalt particles, CoT shows high C5? selectivity. FTS activity of all catalysts at 513 K and space velocity (SV) = 2,000 L/kgcat/h showed similar trend as observed at 493 K and same SV with exception of CoS catalyst. The observed initial conversion on CoS at the beginning of reaction at 513 K and there after steady decline to 69.2% could be attributed to the presence of highly active cobalt metal particles. The different behavior of CoA catalyst at 513 K and 1,000 L/kgcat/h could be attributed to the partial deactivation of small cobalt particles due to the high H2O concentration at high CO conversion [20]. Furthermore, the higher olen selectivity in C2C4 hydrocarbons on the catalysts may be related to high C5? selectivity in our reaction conditions due to the possible secondary reaction of olens to heavy hydrocarbons [16]. During present study, we observed that after a certain period of reaction time, SV changed from 2,000 to 1,000 L/ kgcat/h at 513 K. This led to dramatic increase in conversion of CO on CoT and CoS at steady-state in comparison to CoA and therefore, the conversion of CO on CoT and CoS was quite stable at around 73.2 and 95.8%, but a rapid decrease from 95.0 to 68.8% is observed on CoA at TOS of 240 h. The reasons for such differences could be the pore blocking due to formation of wax on the surface of CoA. Careful examination revealed formation of lump inside the reactor wall due to the aggregation of catalyst particles. Since, the mass of the aggregated CoA catalyst was

*2.53 g and the mass of catalyst without heavy hydrocarbons was *1.23 g as calculated from TG analysis, we conclude that 26 wt% of CoA catalyst had not participated in the FT reaction. Reduced participation of CoA catalyst thus obviously leads to suppression of CO conversion from the maximum value to around 68.8% at 513 K with SV value of 1,000 L/kgcat/h. No such observation was made in the case of other catalysts used because of the fact that no aggregation was noticeable on the CoT and CoS catalysts. Chakrabarty et al. [21] have reported that the hydrocarbonwater emulsion can be used as hydrocarbon transport through a pipeline. The hydrocarbons include conventional petroleum, FT hydrocarbons, tar sand and even coal liquids. In the present studies, FTS wax contains water and trace amount of oxygenates, including higher alcohols which can make it easier to form a macro-emulsion of FTS products. Therefore, alcohol content in the FTS derived heavy hydrocarbons were analyzed by GC-MS. Alcohol content in the heavy hydrocarbons on CoA, CoT and CoS was found to be about 2.08, 3.17 and 4.04 wt% with the composition of C7C12 alcohols, respectively. It suggests that relatively less amount of alcohol content on CoA having small pore size causes catalyst aggregation. To elucidate the point that the intrinsic activity varies with cobalt particle size and pore size of catalysts used in the present study, the correlation between turn-over frequency (TOF) and cobalt particle size was made (Fig. 6) and was compared with the value of reference TOF data reported by Iglesia [3] for supports such as Al2O3, SiO2 and TiO2. In general, the cobalt particles above 68 nm in size have trivial effects in enhancing the intrinsic activity [22], and cobalt with smaller particles size of below 5 nm is easily re-oxidized by water and eventually results in

100 493 K, WHSV 2000 513 K, WHSV 2000 513 K, WHSV 1000 from Ref. [3]

80

TOF ( x 10 /s )

-3

60

40

20

0 0 10 20 30 40 50 60 70 80

Co particle size (nm)

Fig. 6 The correlation of cobalt particle size with intrinsic activity (TOF) s T = 493 K; h T = 513 K; hollow symbol for SV = 2,000 and lled one for SV = 1,000 L/kgcat/h; gray symbol is for the recalculated TOF values at 473 K and 2.0 MPa from ref. [3]

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deactivation of catalyst. The TOF values of *10 nm cobalt species without the support are reported in the range of 1.6 9 10-3 * 3.0 9 10-3/s [3, 9, 22]. Therefore, we expected almost similar TOF from our samples having particle size about *15 nm. In practice, however, we found that TOF value is signicantly altered. It is therefore appropriate to consider the difference in TOF values from our samples due to the difference in pore size of the catalysts. The larger the pore size of support e.g., CoT, the higher the TOF value at all reaction conditions, even though it may have large cobalt particle size and lower reducibility. In addition, the observed low TOF value at low space velocity of 1,000 L/kgcat/h could be attributed to the low concentration of reactants in reaction medium with high CO conversion. In general, water produced could alter the catalytic activity depending on its concentration, cobalt particle size and average pore size of catalysts [20]. It is reported that water shows a positive effect for SiO2 support (high CO conversion and selectivity to C5?) at high CO conversion. But it shows, a negative effect for Al2O3 support and only a little effect for TiO2 [20]. In addition, at a high partial pressure regime of water, the water was found to be irreversibly affecting the catalytic activity. In the present studies a higher CO conversion on CoS and CoA catalysts due to narrow pore size distribution and small cobalt particle size was observed but the abrupt catalyst deactivation could be attributed to the irreversible effect of water by oxidation of small cobalt particles. In summary, the present investigation reveals that cobalt particle size and average pore size of catalyst simultaneously affect the intrinsic activity in a slurry-phase FTS reaction and the contribution of pore size is more signicant than particle size of cobalt species. Furthermore, the catalyst aggregation during FTS reaction could be suppressed by the extent of macro-emulsion formation from water and trace amount of oxygenates including higher alcohols in the case of catalysts having a large pore size such as CoT and CoS.

oxygenates, including C7C12 alcohols, is responsible for the difcult formation of macro-emulsion and eventually increased the catalyst aggregation, especially on the catalyst having small pore size like CoA, and fast catalyst deactivation by the possible irreversible oxidation under the conditions of high water concentration with high CO conversion. Although the cobalt particle size above 15 nm has trivial effects on enhancing the intrinsic activity, average pore size of catalyst signicantly affects the intrinsic activity in a slurry-phase FTS reaction due to the facile diffusion of heavy hydrocarbons formed inside of catalyst pore.
Acknowledgments The authors would like to acknowledge the nancial support of KEMCO and GTL Technology Development Consortium (Korea National Oil Corp., Daelim Industrial Co., Ltd, Doosan Mecatec Co., Ltd, Hyundai Engineering Co. Ltd and SK Energy Co. Ltd) under Energy & Resources Technology Development Programs of the Ministry of Knowledge Economy, Republic of Korea. P. K. Khanna thanks KOSEF for a Brain Pool fellowship.

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4 Conclusions Various supports such as c-Al2O3, TiO2, and SiO2 inuence the physico-chemical and catalytic properties of cobaltbased catalysts in the slurry-phase FTS reaction. Co/c-Al2O3 catalyst shows the smallest cobalt particle size and the highest dispersion but a poor degree of reduction due to the strong metal-support interaction. Co/SiO2 catalyst demonstrated the best catalytic performance because of high degree of reduction of cobalt species. Co/TiO2 catalyst has relatively bigger pore size and it aids an easy diffusion of FTS products. After the FTS reaction with Co/c-Al2O3 catalyst, a lump of catalyst aggregation was induced by heavy hydrocarbons formed during FTS reaction. Low concentration of

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