催化学报 ›› 2011, Vol. 32 ›› Issue (12): 1790-1802.DOI: 10.1016/S1872-2067(10)60285-9

• 研究论文 • 上一篇    下一篇

极性溶剂相费托合成的产物分布特征

高军虎 1,2,3, 吴宝山 1,3, 周利平 1,2,3, 杨勇 1,3, 郝栩 1,3, 徐元源 3, 李永旺 1,3,*   

  1. 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, 山西太原 030001; 2中国科学院研究生院, 北京 100049; 3中国科学院山西煤炭化学研究所煤间接液化国家工程实验室, 山西太原 030001
  • 收稿日期:2011-07-22 修回日期:2011-08-12 出版日期:2011-12-21 发布日期:2015-04-23

Product Distribution of Fischer-Tropsch Synthesis in Polar Liquids

GAO Junhu1,2,3, WU Baoshan1,3, ZHOU Liping1,2,3, YANG Yong1,3, HAO Xu1,3, XU Yuanyuan3, LI Yongwang1,3,*   

  1. 1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China; 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 3National Engineering Laboratory for Coal Indirect Liquefaction, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
  • Received:2011-07-22 Revised:2011-08-12 Online:2011-12-21 Published:2015-04-23

摘要: 在间歇反应釜中研究了极性溶剂中工业铁基催化剂上费托合成的产物分布特点, 考察了不同极性溶剂 (聚乙二醇 400 和 600, 1,4-丁二醇, 乙二醇) 和非极性溶剂正辛烷, 反应条件 (温度, 进料 H2/CO 比, 反应时间) 和操作模式 (间歇, 半连续) 对产物选择性和链增长因子 α 的影响. 结果表明, 在所考察的条件下, 产物中 α-烯烃 (除了乙烯) 的选择性几乎不随碳数变化, 这完全不同于采用非极性介质的传统费托合成, 对于高选择性地生产线性 α-烯烃具有重要的意义. 通过优化操作条件, 产物中 α-烯烃的平均含量可超过 70%. 产物分布大多偏离理想的 ASF 分布, 无法用烯烃再吸附理论来解释. 链增长因子 α 均大于 0.85, 表明极性介质有利于长链烃的生成.

关键词: 费托合成, α-烯烃选择性, 极性溶剂, 聚乙二醇, 反应介质, 二次反应, 产物分布

Abstract: The effect of using polar liquid as the reaction medium for Fischer-Tropsch synthesis on the product distribution was studied. The experiments were performed with an industrial iron-based catalyst in a batch autoclave reactor with different liquid phases (polyethylene glycol 400, polyethylene glycol 600, 1,4-butanediol, and glycol). The reaction conditions were temperature of 200–240 °C, initial H2/CO molar ratios of 1.00–2.03, catalyst particle sizes of 20–40 mesh and > 150 mesh, and reaction time of 24–144 h. The α-olefin selectivity was significantly increased to more than 70% and was almost independent of carbon number with all the polar liquids. Most of the hydrocarbon distribution were not of the ideal Anderson-Schulz-Flory pattern and could not be explained by the mechanism of olefin readsorption and secondary reactions. The chain growth probability α was larger than 0.85 for all conditions, and it was slightly influenced by changes of reaction conditions, liquid, and reaction time. There was product separation during reaction in this catalytic system, which meant that it did not have the problem of separating the catalyst from the wax product that traditional slurry reactors have. The result suggested new opportunities for the selective production of linear α-olefins and for mechanistic investigations of Fischer-Tropsch synthesis.

Key words: Fischer-Tropsch synthesis, α-olefin selectivity, reaction medium, polar liquid, polyethylene glycol, product distribution, secondary reaction