第25卷第9期催化學報2004年9月Vol. 25 No. 9Chinese Journal of CatalystSeptember 2004Article ll:0253-983x2004)90683Communication : 683-684Synthesis of Ketones and Alcohols via Syngas on Fe-Cu Based CatalystsSU Yunlai'2, LIU Bo, PEI Supeng, WANG Xiangyu', LIU Zhongmin1 Institute of Industrial Catalysis Zhengzhou University Zhengzhou 450052, Henan, china2 Dalian Institute of Chemical Physics The Chinese Academy of Science, Dalian 116023, Liaoning, ChinaKey words: higher alcohol, ketone, syngas iron-copper based catalystCLC number 0643Document code: AThe synthesis of higher alcohols from coalwere prepared by modifying Fe-Cu based catalystsural gas via syngas has theThe synthetic reactions were performed in a stainless-tion of gasoline octane enhancers and alcohols 1 21, steel fixed-bed reactor(p 6 mm)surrounded byand a number of catalysts and some processesand bath. The experimental installation was thebeen developed 3-5. CuMnFeZrO,L 6] and Mn-modi- same as that in Ref[ 8fied Ni//MoS 7] catalysts for the synthesis of highFrom Table 1, it can be seen that, with theer alcohols were also studied. The higher alcohols crease of promoter contents, there was a significantcould be synthesized from syngas on Fe-Cu, Fe-Cu- increase in X( CO), SC2+ OH )and Y, and reachedCo and Fe-Cu-Mn based catalyst 891. In this paper, maximum on FeCuVKMn(7.5%MnO2 )and FeCuthe effects of promoters and temperature on the VKCe(6.4%CeO2), respectively. The maximum ofcatalytic performance of Fe-Cu based catalysts are re- Y was obtained on FeCuvKCo( 12. 1%Co3O4), butportedthe maxima of X( co)and S( C+ OH)on FeCuvKcoThe purified magnetite copper oxide, potassium (8.9%CO3O4 ) Higher promoter contents led tohydrate and different amounts of manganese dioxide poorer catalytic performace. The order of activity andor cerium oxide or cobalt oxide were thoroughly selectivity of the four catalysts were FeCuVKMn>mixed and fused in an electric furnace at about 1 800 FeCuVKCo> FeCuVKCe> FeCuVK. However theK then cooled, crushed and screened. Three serieorder of the most active temperature was FeCuvKof samples FeCuVKMn, FeCu VKCe and FeCuVKCo FeCuVKCe> FecuvKMn> FeCuvKCoTable 1 Catalytic performance of Fe-Cu based catalysts for synthesis of ketones and alcoholsn( Fe)X( CO)Y/gM mt h))AlcoholKetoneFeCuvK2.16480.012FeCuVKMn2.3FeCuVKMn3403FeCuvKMn1.462337.867.00.365FeCuvKMnFeCuvKceFeCuvKce1.4635FeCuvKce2.110.30.299FeCuvKce13.FeCuVKCoFeCuVKco2.11.40.3060.017FeCuvKco中國煤化工0.313CNMHG 0.3160.024Reaction conditions: n(H, yn(Co)=2. 3, v( cat )=0.5 ml, SV=5000 h, p=6.0 MPa; the same below. MO.- MnO, CeO or Co OReceived date: 2004-03-08. First author Su Yunlai male born in 1963, doctor associate professouthor: SU Yunlai. Tel: (0371 )7766076:E-1Foundation item Supported by the Foundation of State Key l aboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS.684催化學報第25卷From table 2, it can be seen thTable 2 Effect of temperature on catalytic performanceture had remarkable influence on the Co conversionof Fe- Cu based catalyststhe C2+ oh selectivity and the yield of ketones and alu( Mo,) T X( oO) SC2+OH) Y/g/ml h))cohols which increased with the temperature increaseAlcoho KetoneFeCuVK59820.4within 598-648 K. Most X( CO), S(C2+ OH)and Y62323.640.20.2320.011reached a maximum at 648 K on Fecuvk and fecu64825.146.70.2880.012VKCe, at 623 K on FeCuvKMn and at 598 K onFeCuvKMn 7.5 598 30.9FeCuvKCo respectively. On comparing the activit62337.867.00.3650.050and selectivity the FeCuvKCo exhibited a broader64836.062.30.3040.032range of active temperature than othersFecuvKce 6 4 598 27.30.20.2140.020From Table 3, it can be seen that C-C linear62329.5530.2700.01864835,056.50,3100.021alcohols were the main products. The alcohol distri- FeCuvKco 12.1 598 35.0 60.880.3160.024catalyst, where branched alcohols prevailed/t'abution was similar to that on MoS.-based catalyst 10but remarkably different from that on Cu-Zn based64832.861.20.3050.019Table 3 product distribution on Fe-Cu based catalysts(MO2)u alcohol%(ketone y%T/KFecuvK45.522.212,840.6511.0FeCuVKMnFecuvKceFeCuVKCo31.816.22.012.8rue Xuebao( Acta Phys-Chim Sin ) 2003, 195):42References7 Qi HJ, Li DB, Ma Y g, Li wh, Sun Y H, Zhong bI Majocchi L, Lietti L, Beretta A, Forzatti P, MicheliRanliao Huarue Xuebao( Fuel Chem Technol ) 2003Tagliabue L. Appl Catal A, 1998, 16(2): 3933K2):1192 Hindermann J P, Hutchings G J, Kiennemann A. 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Wuli hucSurf sci Catal, 1983, 16:709改性Fe-Cu催化劑上由合成氣合成酮和醇蘇運來12*,劉博,裴素朋,王向宇1,劉中民2Ⅰ鄭州大學工業(yè)催化研究所,河南鄭州450052;2中國科學院大連化學物理研究所,遼寧大連116023)要:采用熔融法制備了三類改性催化劑 FeCuVKMn FeCuVKCe和山中國煤化工低級酮和低碳醇在一定的溫度范圍內(nèi)O轉(zhuǎn)化率、C2+OH選擇性及酮和醇的收率隨反應(yīng)溫度CNMHG表現(xiàn)出比其他催化劑更寬的活性溫度區(qū)間;適量加入助劑可使Fe(u催化劑的催化性能顯著改書.催化劑沽性及選擇性的高低順序是 FeCuVKMn>FeCuvKco> FeCuVKce> FeCuVK;最高活性溫度的高低順序是 FeCuVK=F∈ CuVKCe> FeCuVKM> FecuvKco.關(guān)鍵詞:低碳醇,酮,合成氣,鐵銅基催化劑(Ed wGBh