Symposium on Advances in Fischer-Tropsch Chemistry Presented Before the Division of Petroleum Chemistry, Inc. 219th National Meeting, American Chemical Society San Francisco, CA, March 26-31, 2000 <= Study of the Activation of Supported Cobalt Catalyst for Fischer-Tropsch Synthesis ‘M-C. Marion IEP CEDI ~ Solaize ~ BP 3 69390 Vernaison, France 0. Ducreus, J. Lynch and M. Roy Institut Francais du Pétrole Let 4, Avenue de Bois-Préau~ BP 311 92506 Rueil Malmaison Cedex, France INTRODUCTION Interest in the Fischer-Tropsch synthesis forliquid hydrocarbon produc- tion is increasing in the context of clean fuel production. Cobalt containing catalysts are known to be good candidates for Fischer-Trospch synthesis, particularly for the production of long chain paraffinic hydrocarbons. ‘The activity of cobalt catalysts is usually attributed to the active sites located on the surface of supported cobalt metallic particles formed after reduction (1). Thus, the activation step (reduction procedure) is very important and must be optimized for each catalyst in terms of: + the reduction temperature of cobalt species (2), «the effect of promoters on the cobalt reduction temperature a3) + the reactions which can occur between the active phase and the support (2). ‘Usually, for Fischer-Tropsch syn- thesis, cobalt catalysts are reduced between 200 and 400°C (4, 5). How- ever, according to TPR charac- terizations of supported cobalt cata~ lyst, some cobalt species require hhigher temperatures to be reduced @):Inourstudy, which concems pure cobalt alumina supported catalyst, ‘we studied the impact of an increase of the reduction temperature (from 350°C to 500°C) on both its metallic state and its activity. EXPERIMENTAL ‘The cobalt catalystis prepared by ‘wet impregnation of aqueous cobalt nitrate onacommercial alumina from (GBET = 180 m?/g, porous volume = 0.5 ce/g), representing @ total cobalt loading of 13 wt%. Then, thesampleis dried and calcinediin air at 400°C. ‘The cobalt catalyst, beforeand af- ter reduction from 350 to 500°C, is characterized by TPR (Figure 1). O2 chemisorption is also performed on two reduced samples. TPR experi- ments are performed using 1g of powdered catalyst loaded in a U- shaped reactor tube. Temperature is, increased from ambient to900°C,5°C per minute, under a Fi2/ Ar mixture (Hz =5%). Hydrogen consumption is measured on a TCD detector. In situ XRD measurements were carried out using Cu K(@) radiation —coraz0s before redveton Reduced shat 400°C +++ Reduced shat 450°C —Reduoed sh at S00"‘on a Siemens D501 0-28 powder dif- fractometer equiped with an Anton Paar XRK reaction chamber. The powdered sample (0.2 g) is placed on a ceramic holder and pressed lightly. ‘The inlet gas flow passes through the sample. XRD patterns are recorded after 2h30 at the chosen temperature. ‘The catalyst activity is evaluated ina fixed bed apparatus, using 20g of catalyst in pellet form, diluted in SiC. ‘The reaction tests are performed at 20 bar under a301/h flow rate of syngas witha Fi2/CO molar ratioof 2.0 at 200 to 220°C. Prior to reaction, the cata- lystis reduced in situ, under a Hi/No mixture (1/3) either at 350°C during 24 hours or at 500°C for 10hours. CO conversion rates are calculated based ‘on the CPG analysis performed in line on the gas effluent. The liquid products are collected and analyzed by chromatography in order todeter- mine the selectivities. The chain growth probability (alpha coeffi- cient) is calculated from plots of the Table 1. Effect of the Reduction Temperature on the Catalytic Performance {for Fischer Tropsch Synthesis, Cupar remnced a 35PC | Caer edaced a SOFC [CO conversion |. a2oorc ” 15 - 210°C as 3 a 215-200°0 ease) 53.20% Seleciviy at ISOC ny - cus 2 15 cae 9 B [Alpha coefficient 058 a7 Anderson-Schultz-Flory distribu- tions using the C10-C40 data. RESULTS AND DISCUSSION ‘TPR curves recorded before and after reduction at different tempera~ tures are presented in Figure 1. The calcined catalyst sample presents two reduction maxima: lower temperature region (around 200- 400°C) and a higher temperature region located between 400 and 800°C. The lower temperature region can be attrib- uted to the reduction of easily reduced bulk cobalt oxide (and perhaps to residual cobalt ni- trate or the first small reduction peak at 205°C), whereas the higher tem- perature peak may be due to cobalt oxide in strong interaction with the alumina support (2,3). TPR data after prior reduction show a decrease of the higher reduction peak (400- 800°C) when increasing the tempera- ture (the signal visible at around 250° Cis due to reoxydation of surface ‘metallic cobalt, due toa slight air leak during transfer between reduction and the TPR measurement). The per- centage of unreduced cobalt (ie. re- maining after the first reduction step) decreases with an increase of the re- duction temperature. Moreover, chemisorption of oxygen performed on the reduced samples also show an increase of the accessible reduced co- z= Cohe fog Cone > 3 Lh 52 3 “| = ; Core wmanamarnae | | 3 i cone i = ool cone oe str roution 48010 =} “© 2 & & &@ © @ 6 eS bo oe we 20 (CuK) 20Cu(e) Figure 2. XRO Cos0« pattems under Ha atmosphere at ferent emperatres. Figure. 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