Page 118 - 《精细化工》2020年第5期

第 37 卷第 5 期 精 细 化 工 Vol.37, No.5
202 0 年 5 月 FINE CHEMICALS May 2020

催化与分离提纯技术
合成气直接制低碳烯烃用 Fe/K/Mg-O-Al 催化剂

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邢 宇，赵晨曦，贾高鹏，田红美，高玉集，刘振新
（郑州轻工业大学 材料与化学工程学院 河南省表界面科学重点实验室，河南 郑州 450002）

摘要：传统费托合成着眼于制取蜡/油等长碳链饱和烃，其催化剂的“金属/酸性氧化物”界面可以极化和稳定反
应中间体，从而促进加氢和 C—C 偶合，有助于较长链烷烃的生成。为了从合成气直接获取高附加值的低碳烯
烃，催化剂设计理念应该与以制取较长链烷烃为目的的传统费托催化剂取法相异。该文着眼于“弱加氢金属/固
体碱型载体”费托合成制低碳烯烃催化剂的基础研究，采用表面碱性的载体和碱性的钾助剂，逆转上述传统催
化剂中“金属/酸性氧化物”之间界面的状况，削弱对加氢和 C—C 偶合的促进，达到抑制加氢、抑制 C—C 偶
合的目的。所测 Fe/K/Mg-O-Al 系列催化剂的烯烷比取决于强碱性位的数量及其占总碱性位的比值。在 1200 ℃
钝化处理条件下，与简单 MgO 担载的弱碱性催化剂相比，复合氧化物 MgAl 2 O 4 担载的强碱性催化剂将低碳烯
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烃（C 2 ~C 4 ）产物分布值显著提高了 84%，将 C 2 ~C 4 烯烷比显著提高了 266%。
关键词：费托合成；CO 加氢；低碳烯烃；铁催化剂；尖晶石；催化技术
中图分类号：TQ426.64；TQ221.2 文献标识码：A 文章编号：1003-5214 (2020) 05-0968-08

Fe/K/Mg-O-Al catalysts for direct production of lower olefins from syngas

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XING Yu, ZHAO Chenxi, JIA Gaopeng, TIAN Hongmei, GAO Yuji, LIU Zhenxin
（Henan Provincial Key Laboratory of Surface and Interface Science, School of Materials and Chemical Engineering,
Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China）

Abstract: Traditional Fischer-Tropsch synthesis focuses on the production of long chain saturated
hydrocarbons such as wax/oil, whose catalyst's “metal/acidic oxide” interface can polarize and stabilize the
reaction intermediates, thus promoting hydrogenation and C—C coupling, and contributing to the formation of
longer chain alkanes. In order to obtain high value-added lower olefins directly from syngas, the concept of
catalyst design should be different from that of the traditional Fischer-Tropsch method to produce long-chain
alkanes. Therefore, the basic research of catalysts for Fischer Tropsch synthesis of low-carbon olefins with
"weak hydrogenation metal/solid base support" was carried out. Base support and potassium promoter were
adopted to reverse the status of above-mentioned interface between "metal/acid oxide" in the traditional
catalysts, weaken the promotion of hydrogenation and C—C coupling, and achieve the purpose of
inhibiting hydrogenation and C—C coupling. The ratio of olefin to paraffin (O/P) of Fe/K/Mg-O-Al series
catalysts depended on the number of strong basic sites and their ratio to the total basic sites. Under the same
passivation treatment at 1200 ℃, compared with those in the weak base catalyst supported by simple MgO,
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the hydrocarbon product distribution value of C 2 ~C 4 hydrocarbon was increased by 84% in the strong base
catalyst supported by composite oxide MgAl 2 O 4 , and the C 2 ~C 4 olefin/paraffin ratio was increased by 266%.
Key words: Fischer Tropsch synthesis; CO hydrogenation; lower olefins; iron catalyst; spinel; catalysis
technology

费托合成（Fischer-Tropsch）是指将煤、天然气 剂和反应条件下生成各种含碳氢有机物的过程。依
和生物质等制成的合成气（CO + H 2 ）在一定的催化 托不同的催化剂和工艺参数，费托产物类别可以有

收稿日期：2019-11-04; 定用日期：2020-02-12; DOI: 10.13550/j.jxhg.20191047
基金项目：国家自然科学基金（21571161）；河南省高等学校重点科研项目资助计划（20A150044）；省属高校基本科研业务费专项资
金项目（19KYYWF0402）；郑州轻工业大学博士科研基金（2016BSJJ034/CLY20170069/LZX2016）
作者简介：邢宇（1976—），男，副教授，E-mail：yuxing@zzuli.edu.cn。联系人：刘振新（1974—），女，副教授，E-mail：
zhenxinliu@zzuli.edu.cn。