醇添加对钴基催化剂费托合成反应的影响

doi:10.3866/PKU.WHXB201303072

物理化学学报 >> 2013, Vol. 29 >> Issue (05): 1063-1072.doi: 10.3866/PKU.WHXB201303072

醇添加对钴基催化剂费托合成反应的影响

姚芳芳^1,2,3, 吴宝山^1,3,4, 周利平^3,4, 高军虎^3,4, 李莹^3,4, 李永旺^1,3,4

1 中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原 030001;
2 中国科学院大学, 北京 100049;
3 中国科学院山西煤炭化学研究所, 煤炭间接液化国家工程实验室, 太原 030001;
4 中科合成油技术有限公司, 太原 030001

收稿日期:2013-01-21 修回日期:2013-03-06 发布日期:2013-04-24
通讯作者: 吴宝山 E-mail:wbs@sxicc.ac.cn
基金资助:
国家重点基础研究发展计划(973) (2011CB201401)和中国科学院知识创新工程项目(KJCX2-YW-N41)资助

Effect of Alcohol Addition on Fischer-Tropsch Synthesis over Cobalt-Based Catalysts

YAO Fang-Fang^1,2,3, WU Bao-Shan^1,3,4, ZHOU Li-Ping^3,4, GAO Jun-Hu^3,4, LI Ying^3,4, LI Yong-Wang^1,3,4

1 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, P. R. China;
2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China;
3 National Engineering Laboratory for Coal Indirect Liquefaction, Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, P. R. China;
4 Synfuels China Co. Ltd., Taiyuan 030001, P. R. China

Received:2013-01-21 Revised:2013-03-06 Published:2013-04-24
Supported by:
The project was supported by the National Key Basic Research Program of China (973) (2011CB201401) and Intellectual Innovation Project of Chinese Academy of Sciences (KJCX2-YW-N41).

摘要/Abstract

摘要：

在固定床微反应器上利用全产物在线分析方法, 研究了钴基催化剂上伯醇C_nH_2n+1OH (n=2, 3, 5, 6)在惰性气氛(Ar)和氢气气氛下的反应行为以及添加C_nH_2n+1OH对费托(FT)合成反应的影响, 并结合原位漫反射傅里叶变换红外光谱(DRIFTS)表征. 结果表明: 碳数为n的醇在Ar 气氛和H₂气氛下反应主要有脱羰和脱水两条反应路径, 分别生成碳数为n-1的烃和相同碳数的烃. 低碳数醇(乙醇和正丙醇)的添加对费托合成产物分布无明显影响; 而较高碳数的醇(正戊醇, 正己醇)的加入使碳数为n-1以上烃的选择性显著增加, 这是由于C_nH_2n+1OH加入后生成的碳数为n-1和n的中间体可进一步发生链引发反应, 生成更多的长链烃.

关键词: 钴基催化剂, 费托合成, 全产物在线分析, C₂-C₆伯醇, 添加实验, 反应机理

Abstract:

C_nH_2n+1OH (n=2, 3, 5, 6) primary alcohol activation, hydrogenation and its additional effects on the performance of the Fischer-Tropsch (FT) synthesis over a cobalt catalyst were investigated in a fixed bed micro-reactor. All products were analyzed using an on-line gas chromatography. The diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to investigate intermediates on the catalyst surface. In the presence of argon or hydrogen, C_nH_2n+1OH underwent two main reactions: direct de-carbonylation to produce (CH₂)_n_-1 hydrocarbons, and dehydration to produce (CH₂)_n hydrocarbons. The addition of lower carbon number alcohol (ethanol or 1-propanol) into the FT synthesis reaction had no significant effect on the hydrocarbon product distribution. While co-feeding higher carbon number alcohol (1-pentanol or 1-hexanol) into the FT synthesis reaction, the selectivity to hydrocarbons with carbon numbers greater than or equal to n-1 increased markedly because of the additive?s chain initiation on the catalyst surface.

Key words: Cobalt-based catalyst, Fischer-Tropsch synthesis, On-line analysis of all products, C₂-C₆ primary alcohols, Co-feeding experiment, Reaction mechanism

MSC2000:

O643

姚芳芳, 吴宝山, 周利平, 高军虎, 李莹, 李永旺. 醇添加对钴基催化剂费托合成反应的影响[J]. 物理化学学报, 2013, 29(05): 1063-1072.

YAO Fang-Fang, WU Bao-Shan, ZHOU Li-Ping, GAO Jun-Hu, LI Ying, LI Yong-Wang. Effect of Alcohol Addition on Fischer-Tropsch Synthesis over Cobalt-Based Catalysts[J]. Acta Phys. -Chim. Sin., 2013, 29(05): 1063-1072.

参考文献

(1) Hao, X.; Dong, G.; Yang, Y.; Xu, Y.; Li, Y. Chem. Eng. Technol.2007, 30 (9), 1157.
(2) Xiang, H.W.; Tang, H. Q.; Li, Y.W. J. Fuel. Chem. Technol.2001, 29, 289. [相宏伟, 唐宏青, 李永旺. 燃料化学学报,2001, 29, 289.]
(3) Van Der Laan, G. P.; Beenackers, A. A. C. M. Cat. Rev. 1999, 41 (3-4), 255. doi: 10.1081/CR-100101170
(4) Rofer-DePoorter, C. K. Chem. Rev. 1981, 81 (5), 447. doi: 10.1021/cr00045a002
(5) van Dijk, H. A. J. The Fischer-Tropsch Synthesis: A MechanisticStudy Using Transient Isotopic Tracing; Eindhoven: TechnischeUniversiteit Eindhoven, 2001.
(6) Gao, H. Y.; Chen, J. G.; Xiang, H.W.; Yang, J. L.; Li, Y.W.;Sun, Y. H. Chin. J. Catal. 2001, 22, 133. [高海燕, 陈建刚, 相宏伟, 杨继礼, 李永旺, 孙予罕. 催化学报, 2001, 22, 133.]
(7) Sage, V.; Burke, N. Catal. Today 2011, 178 (1), 137. doi: 10.1016/j.cattod.2011.09.013
(8) Turner, M. L.; Marsih, N.; Mann, B. E.; Quyoum, R.; Long, H.C.; Maitlis, P. M. J. Am. Chem. Soc. 2002, 124 (35), 10456. doi: 10.1021/ja026280v
(9) Hou, L. Fischer-Tropsch Studies with Acetylenic Compounds asProbes. Ph. D. Dissertation, University of Pittsburgh, Pittsburgh,2005.
(10) Kummer, J. T.; Emmett, P. H. J. Am. Chem. Soc. 1953, 75 (21),5177. doi: 10.1021/ja01117a008
(11) Hall,W. K.; Kokes, R. J.; Emmett, P. H. J. Am. Chem. Soc.1957, 79 (12), 2983. doi: 10.1021/ja01569a001
(12) Hall,W. K.; Kokes, R. J.; Emmett, P. H. J. Am. Chem. Soc.1960, 82 (5), 1027. doi: 10.1021/ja01490a005
(13) Blyholder, G.; Emmett, P. H. J. Phys. Chem. 1959, 63 (6), 962.doi: 10.1021/j150576a044
(14) Blyholder, G.; Emmett, P. H. J. Phys. Chem. 1960, 64 (4), 470.doi: 10.1021/j100833a023
(15) Tau, L. M.; Dabbagh, H. A.; Halasz, J.; Davis, B. H. J. Mol.Catal. 1992, 71 (1), 37. doi: 10.1016/0304-5102(92)80006-3
(16) Tau, L. M.; Dabbagh, H. A.; Davis, B. H. Energy Fuels 1991, 5 (1), 174. doi: 10.1021/ef00025a030
(17) Sarkar, A.; Keogh, R.; Bao, S.; Davis, B. Catal. Lett. 2008, 120 (1-2), 25. doi: 10.1007/s10562-007-9261-z
(18) Sarkar, A.; Keogh, R. A.; Bao, S.; Davis, B. H. Appl. Catal. A:Gen. 2008, 341 (1-2), 146.
(19) Fan, G. X. Analysis of Fischer-Tropsch Synthesis Cold TrapOils. MS Dissertation, Institute of Coal Chemistry, ChineseAcademy of Science, Shanxi, 2007. [樊改仙. F-T 合成油相产物的分析研究[D]. 山西: 中国科学院山西煤炭化学研究所,2007.]
(20) Gao, J.;Wu, B.; Zhou, L.; Yang, Y.; Hao, X.; Xu, J.; Xu, Y.; Li,Y. Ind. Eng. Chem. Res. 2012, 51 (36), 11618. doi: 10.1021/ie201671g
(21) Dictor, R. A.; Bell, A. T. Ind. Eng. Chem. Fundam. 1984, 23 (2),252. doi: 10.1021/i100014a019
(22) Snavely, K.; Subramaniam, B. Ind. Eng. Chem. Res. 1997, 36 (10), 4413. doi: 10.1021/ie9702791
(23) Zhou, L. P. Kinetic Study of the Fischer-Tropsch Synthesis overan Industrial Iron-based Catalyst. Ph. D. Dissertation, Instituteof Coal Chemistry, Chinese Academy of Science, Taiyuan,2011. [周利平. 工业铁基催化剂F-T 合成动力学研究[D]. 太原: 中国科学院山西煤炭化学研究所, 2011.]
(24) Zhang, Q. H.; Kang, J. C.;Wang, Y. ChemCatChem 2010, 2,1030.
(25) Khodakov, A. Y.; Chu,W.; Fongarland, P. Chem. Rev. 2007, 107 (5), 1692. doi: 10.1021/cr050972v
(26) Xin, Q. In situ Techniques in Catalysis Research, 1st ed.; PekingUniversity Press: Beijing, 1993. [辛勤. 催化研究中的原位技术. 第一版. 北京: 北京大学出版社, 1993.]
(27) Weng, S. F. Fourier Transform Infrared Spectroscopy Analysis,2nd ed.; Chemical Industry Press: Beijing, 2010. [翁诗甫. 傅里叶变换红外光谱分析. 第二版. 北京: 化学工业出版社,2010.]
(28) Yee, A.; Morrison, S. J.; Idriss, H. J. Catal. 2000, 191 (1), 30.doi: 10.1006/jcat.1999.2765
(29) Zhang, J. L.; Ren, J.; Chen, J. G.; Sun, Y. H. Acta Phys. -Chim.Sin. 2002, 18, 260. [张俊岭, 任杰, 陈建刚, 孙予罕. 物理化学学报, 2002, 18, 260.] doi: 10.3866/PKU.WHXB20020314
(30) Szegedi, Á.; Popova, M.; Mavrodinova, V.; Minchev, C. Appl.Catal. A: General 2008, 338 (1-2), 44.
(31) Prieto, G.; Martínez, A.; Concepción, P.; Moreno-Tost, R.J. Catal. 2009, 266 (1), 129. doi: 10.1016/j.jcat.2009.06.001
(32) Jalama, K.; Coville, N. J.; Hildebrandt, D.; Glasser, D.; Jewell,L. L. Fuel 2007, 86 (1-2), 73.
(33) Zhou,W. Deactivation Studies of Co-Based Catalysts forFischer-Tropsch Synthesis in Fixed-Bed Reactor. Ph. D.Dissertation, Institute of Coal Chemistry, Chinese Academy ofScience, Taiyuan, 2005. [周玮. 钴基催化剂在固定床Fischer-Tropsch 合成反应中的失活行为研究[D]. 太原: 中国科学院山西煤炭化学研究所, 2005.]
(34) Mavrikakis, M.; Barteau, M. A. J. Mol. Catal. A: Chem. 1998,131 (1-3), 135.
(35) Cheng, J.; Hu, P.; Ellis, P.; French, S.; Kelly, G.; Lok, C. M.J. Phys. Chem. C 2008, 112 (25), 9464. doi: 10.1021/jp802242t
(36) Chen, L.; Zhu, Y.; Zheng, H.; Zhang, C.; Zhang, B.; Li, Y.J. Mol. Catal. A: Chem. 2011, 351, 217. doi: 10.1016/j.molcata.2011.10.015
(37) Chen, L.; Zhu, Y.; Zheng, H.; Zhang, C.; Li, Y. Appl. Catal. A:General 2012, 411-412, 95.
(38) Liu, X.; Li, X.; Fujimoto, K. Catal. Commun. 2007, 8 (9), 1329.doi: 10.1016/j.catcom.2006.12.002

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醇添加对钴基催化剂费托合成反应的影响

Effect of Alcohol Addition on Fischer-Tropsch Synthesis over Cobalt-Based Catalysts

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