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.

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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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