Catalysis Communications 8 (2007) 18201824 www.elsevier.

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Preparation of a new precipitated iron catalyst for FischerTropsch synthesis

Hiroshi Hayakawa
a

a,b,*

, Hisanori Tanaka c, Kaoru Fujimoto

Department of Chemical Processes and Environment, The University of Kitakyushu, 1-1 Hibikino Wakamatsu-ku Kitakyushu-shi Fukuoka 808-0135, Japan b Technology Development Center, Electric Power Development Co. Ltd., 6-15-1, Ginza, Chuo-ku, Tokyo 104-8165, Japan c Wakamatsu Research Institute, Electric Power Development Co. Ltd., 1 Yanagisakimachi Wakamatsu-ku Kitakyushu-shi Fukuoka 808-0111, Japan Received 2 September 2006; received in revised form 4 January 2007; accepted 13 February 2007 Available online 20 February 2007

Abstract It is well known that a typical precipitated iron catalyst was prepared by iron(III) nitrate (Fe(NO3)3). The modied iron catalyst was prepared by iron(II) sulfate in our laboratory. The results from catalytic performance tests showed that the iron catalyst prepared from iron sulfate (cat-S) has the higher activity for FischerTropsch synthesis (FTS) than the catalyst prepared from iron nitrate (cat-N). The results from XRD of catalyst before use showed the dierence denitely. The XRD patterns of these catalysts indicate that the main phase of cat-N is Fe2O3, whereas the phases of cat-S are a mixture of Fe2O3 and Fe3O4. It is considered that magnetite was directly formed during precipitation and contained in the catalyst before use enhances the activity for FTS. 2007 Elsevier B.V. All rights reserved.
Keywords: FischerTropsch synthesis; Iron catalyst; Iron(II) sulfate; Magnetite

1. Introduction Iron catalysts have been used for the commercial FischerTropsch Synthesis (FTS) process, especially for synthesis of the coal-derived syngas. Many kinds of precipitated iron catalysts which contain various promoters and supports have been investigated to improve the activity, selectivity, and attrition strength. Also, many studies on iron catalysts have been reported in which eorts were focused on the change in phase of a precipitated catalyst during activation and reaction. Bukur studied that the commercial promoted precipitated iron catalyst was characterized before and after use for FTS. It was found that a hematite (Fe2O3) existed in the catalyst before pretreatment, and that after pretreatment by syngas, hematite was transformed to magnetite
* Corresponding author. Address: Technology Development Center, Electric Power Development Co. Ltd., 6-15-1, Ginza, Chuo-ku, Tokyo 104-8165, Japan. Tel.: +81 3 3546 2211; fax: +81 3 3546 1685. E-mail address: hiroshi_hayakawa@jpower.co.jp (H. Hayakawa).

and iron carbide [1]. Bian et al. studied the reduction behavior with precipitated iron catalysts. the catalyst which showed Fe2O3 from XRD analysis before use, transformed to metallic iron and iron carbide after reduction by CO [2]. Sirimanothan et al. studied the changes in phase and activity during reaction in a stirred tank reactor. Potassium and/or silicon promoted catalyst were prepared and used as samples for tests. All samples were indicated to Fe2O3 before use and transformed to Fe3O4 and iron carbides during FT reaction [3]. All catalysts studied so far were prepared from iron nitrate. On the other hand, several groups reported that iron catalysts prepared from iron sulfate showed the positive eects on FT reactions. Bromeld and Coville have proposed that low-level sulded iron catalyst exhibited enhanced FTS activity and WGS activity [4]. Wu et al. studied on the iron catalyst which was prepared by spray-drying using iron sulfate. It was found that this catalyst contained the sulfate and had the higher activity than a sulfate-free catalyst. However, its structure was not claimed particularly [5].

1566-7367/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2007.02.017

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In our previous studies, the precipitated iron catalysts were prepared by iron nitrate, and were tested in a stirred tank reactor of laboratory scale. From the results of characterization study, the silica-free catalyst (Fe/Cu/K) and the silica-containing catalyst (Fe/Cu/K/SiO2) showed different reduction behavior [6]. The purpose of the present study is to investigate the catalytic performance and the changes in phase of the silica-free precipitated iron catalysts which was prepared iron sulfate, instead of iron nitrate to be clear its eect. 2. Experimental 2.1. Catalyst preparation Two silica-free catalyst were prepared, and one (cat-N) was prepared by precipitation from an aqueous nitrate solution by adding an aqueous solution of (NH4)2CO3 which was similar to that of Kunugi et al. [7]. And second was prepared by precipitation from an aqueous sulfate solution by adding an aqueous solution of Na2CO3. The precipitates were ltered and washed with distilled water several times. The washed lter cakes were dried in air at the range of 373393 K and subsequently calcined in air at the range of 653693 K. Both catalysts were promoted by copper and potassium. Cat-N was prepared by mixing aqueous solutions of
Table 1 Physical properties of precipitated iron catalysts Catalyst Component (on mass basis) analyzed Fe Cat-N Cat-S 100 100 Cu 0.7 0.9 K 2.2 1.9 S 0.09 BET results Surface area (m2/g) 55 33 Pore volume (cm3/g) 0.330 0.326

Cu(NO3)2 3H2O and Fe(NO3)3 9H2O, prior to precipitation, whereas cat-S was prepared by CuSO4 5H2O and FeSO4 7H2O, instead of copper nitrate and iron nitrate. The concentrations of aqueous solutions were 0.5 1.0 mol/L, and the volumes of solutions corresponded to 2030 g of the obtained catalysts. Both cat-N and cat-S were impregnated heated samples with an aqueous solution of K2CO3. 2.2. Activation and reaction procedure Activation on the iron catalysts in the slurry phase was performed in a 100 cc continuous stirred tank reactor (CSTR). Three grams of the catalyst precursor were suspended in 50 ml of n-C16H34 in the 100 cc reactor. The system was purged with 150 cc/min in the 100 cc reactor of N2, then the pressure and temperature were raised to 0.5 Mpa and 523 K respectively, and these conditions were retained for 0.5 h, after which time the temperature was raised to 573 K. Subsequently, catalyst activation was conducted by switching the feed gas from N2 to syngas. Activation was carried out at 0.5 MPa, 573 K, H2/CO ratio of 1.0, and space velocity (W/F) was 7.5 (g-cat h/mol) for a certain period. The stirring speed in the reactor was 1800 rpm. Following the activation, the reactor was subjected to the reaction conditions. Reaction was carried out at 2.0 MPa, 533 K, H2/CO ratio of 1.0, and apace velocity (W/F) was 7.5 (g-cat h/mol) for a certain period. Light hydrocarbons and water were collected in a separator (cold trap) connected to the down stream of the reactor, and heavy hydrocarbons were collected in the reactor with the initial solvent. These were analyzed by an o-line FID gas chromatograph (GC) (column packing: Silicone SE30). Euent gas from the separator was analyzed with an on-line TCD GC (column packing: Molecular Sieve 5A

Fig. 1. XRD patterns of the fresh cat-N and cat-S.

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and Porapak N) and FID (column packing: PLOT Fused Silica). 2.3. Characterization of the catalysts The surface area of the catalysts were measured by the BET method with QUANTA CHROME AUTOSORB1MP. XRD patterns of catalyst samples were measured by a RIGAKU X-ray diractometer. The samples after reduction and reaction for XRD measurements were obtained from the reactor. The reduced and reacted samples were
Table 2 Catalytic performance of precipitated iron catalysts Catalyst CO conversion (%) CO2 selectivity (%) Kp STY (mg/g-cat/h) Hydrocarbon selectivity CH4 (%) C2-4 (%) C5+ (%) STY: C5+ hydrocarbon productivity. Kp: PCO2PH2/PCOPH2O. Cat-N 85.9 43.9 5.9 297 4.9 27.5 67.6 Cat-S 90.3 45.9 16.7 349 4.4 0.3 16.8 3.6 78.5 3.2

separated from the wax product and solvent by ltration in a glove box before being transferred to the XRD instrument. The sulfur composition of the catalyst was determined by the high temperature oxidized method of JIS M 8813. 3. Results and discussion Cat-N and cat-S were subjected to the activity tests and the characterization studies. Their physical properties and the structures of the catalysts before use are shown in Table 1 and Fig. 1. It can be seen from Table 1 that the two catalysts have similar compositions and surface area. The surface area of cat-S was smaller than that of silica-containing iron catalyst which was prepared from iron nitrate in our previous studies [6]. It is considered that pore structure of cat-S was similar to cat-N. The XRD patterns of cat-N indicate that the main phases are all hematite (Fe2O3), while the XRD patterns of cat-S indicate that the phases are a mixture of hematite and magnetite (Fe3O4). Both catalysts present sharp and strong intensity. Fe3+ from iron nitrate formed to hematite (Fe2O3), whereas Fe2+ from iron sulfate formed to hematite (Fe2O3) and magnetite (Fe3O4) whose structure consist

Fig. 2. Carbon number product hydrocarbon distribution and ASF plots of cat-N.Catalyst activity at 260 C, 2 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/ mol). Catalyst activation at 300 C, 0.5 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/mol).

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of a mixture of FeO and Fe2O3. It seems that some of Fe2+ from iron sulfate might be oxidized to Fe3+, which formed to Fe2O3 during the air calcination. The reason why the above phenomenon occurs is not clear. The for-

mation of magnetite must have strong relations to the fact that the raw material of iron is ferrous ions (Fe2+). The results of reaction tests are shown in Table 2.

Fig. 3. Carbon number product hydrocarbon distribution and ASF plots of cat-S Catalyst activity at 260 C, 2 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/ mol) Catalyst activation at 300 C, 0.5 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/mol).

Fig. 4. XRD patterns of fresh cat-N and cat-N reduced in the slurry phase for 3 h: reduction at 300 C, 0.5 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/mol).

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Fig. 5. XRD patterns of fresh cat-S and cat-S after reaction in the slurry phase: reduction at 300 C, 0.5 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/mol). Reaction at 260 C, 2.0 MPa, H2/CO = 1 and W/F = 7.5 (g-cat h/mol).

The results of the reaction tests showed that the activity of the cat-S was higher than that of the cat-N. Cat-S was prepared three times and each sample was tested. The CO conversion data were 90.3%, 92.3% and 87.0%. The reproducibility was dened. The methane and C2-4 selectivity of cat-S was smaller than that of cat-N. So, the C5+ hydrocarbon productivity of cat-S was higher than that of cat-N. It has been reported that the activity of the catalyst which was prepared by iron sulfate, was higher than that of the catalyst iron nitrate. And, the sulfate species enhances the activity of FT catalyst from the literature [4]. In the case of our catalyst, sulfur content was only 0.06 wt%. The structures of cat-N and cat-S catalysts after reduction/reaction are shown in Figs. 2 and 3. The XRD results of the reduced catalysts showed that iron carbide (Fe2.5C) was present in both cat-N after reduction and cat-S after reaction for 3 h, as shown in Figs. 4 and 5. As both catalysts have high activity after reduction, the activated phase can be observed as iron carbide (Fe2.5C). All of the hematite (Fe2O3) in cat-N was reduced and rapidly transformed into active sites. As the reduction by syngas (hydrogen and carbon monoxide) proceeded, iron oxide was transformed from Fe2O3 ) Fe3O4 ) a-Fe or iron carbide. a-Fe could not be observed in our reduced catalyst, because the metallic iron was fairly reactive to carbon dissociated from carbon monoxide. On the other hand, the behavior of hematite in cat-S was similar to cat-N above. The magnetite in cat-S was trans-

formed to the active sites without the transformation from hematite to magnetite. It suggests that the existence of magnetite in cat-S prevents the coagulation of iron oxide and keep the pore structure during reduction. 4. Conclusions The catalyst prepared from iron(II) sulfate has higher activity and C5+ hydrocarbon productivity than that of the catalyst prepared from iron nitrate. The XRD results of catalysts before use indicate that hematite and magnetite existed in the catalyst prepared from iron sulfate, dierent from the catalyst prepared from iron nitrate. The reason why the activity of the catalyst prepared from iron sulfate was higher was considered to prevent iron oxide from coagulation during reduction from Fe2O3 to Fe3O4 by the existence of magnetite. References
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