改性Fe-Cu催化剂上由合成气合成酮和醇

第25卷第9期催化学报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中国煤化工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催化学报第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催化剂上由合成气合成酮和醇苏运来12*,刘博,裴素朋,王向宇1,刘中民2Ⅰ郑州大学工业催化研究所,河南郑州450052;2中国科学院大连化学物理研究所,辽宁大连116023)要:采用熔融法制备了三类改性催化剂 FeCuVKMn FeCuVKCe和山中国煤化工低级酮和低碳醇在一定的温度范围内O转化率、C2+OH选择性及酮和醇的收率随反应温度CNMHG表现出比其他催化剂更宽的活性温度区间;适量加入助剂可使Fe(u催化剂的催化性能显著改書.催化剂沽性及选择性的高低顺序是 FeCuVKMn>FeCuvKco> FeCuVKce> FeCuVK;最高活性温度的高低顺序是 FeCuVK=F∈ CuVKCe> FeCuVKM> FecuvKco.关键词:低碳醇,酮,合成气,铁铜基催化剂(Ed wGBh