煤制化学品：合成气直接制低碳烯烃催化剂研究进展

doi:10.16085/j.issn.1000-6613.22020-1402

摘要/Abstract

摘要：

低碳烯烃是重要的化工原料，直接法合成气制低碳烯烃是非石油路线生产烯烃的新途径。本文首先介绍了直接法合成气催化转化制烯烃的两种工艺路线，即双功能催化剂反应偶联和费-托合成路线制低碳烯烃；接着对CO加氢反应的热力学进行了分析。重点从催化剂活性相、尺寸效应、助剂、金属载体相互作用等方面对合成气直接法制低碳烯烃催化剂的研究进展以及CO加氢反应机理进行了综述。文章指出：在基础研究方面，反应机理仍待进一步明晰，催化剂的开发应聚焦于对O/P及产物链长的精准调控；工业化方面，要考虑到真实的工业化反应环境与实验室反应之间的差异，同时要注意与上下游的产业联合。

关键词: 合成气, 低碳烯烃, 催化剂, 反应机理, 工业应用

Abstract:

Lower olefins are important chemical raw materials and the direct synthesis of lower olefins from syngas is a new non-petroleum route. This article first introduces two routes of synthesis gas catalytic conversion to olefins: the coupling route and the Fischer-Tropsch route. Then the thermodynamics of the CO hydrogenation reaction was analyzed. The research progress of the catalysts for direct synthesis of low-carbon olefins from syngas and the reaction mechanism of CO hydrogenation are reviewed mainly from the aspects of active phase, size effect, promoters, and metal support interactions. As an outlook, we believe that the reaction mechanism still needs to be further clarified through basic researches, and the catalyst development should focus on the precise control of O/P and product’s chain length. In terms of the industrialization, it is necessary to take into account the difference between the real reaction environment in plant and laboratory reactions, and to pay attention to the compatibility with both upstream and downstream.

Key words: syngas, lower olefins, catalyst, reaction mechanism, industrial application

中图分类号:

刘义涛, 朱明辉, 杨子旭, 孟博, 涂维峰, 韩一帆. 煤制化学品：合成气直接制低碳烯烃催化剂研究进展[J]. 化工进展, 2021, 40(2): 594-604.

Yitao LIU, Minghui ZHU, Zixu YANG, Bo MENG, Weifeng TU, Yifan HAN. Advances of catalysts for direct synthesis of lower olefins from syngas[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 594-604.

图/表 8

图1 反应偶联直接法制低碳烯烃示意图[4-5]

图2 1927—2017年“费-托合成制低碳烯烃”学术论文和专利（柱状图）与油价的关系（实线）

表1 CO加氢反应[7]

产物	主反应
甲烷	$C O + 3 H_{2} \overset{}{\to} C H_{4} + H_{2} O$
烷烃	$(2 n + 1) H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} + n H_{2} O$
烯烃	$2 n H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} + n H_{2} O$
水气变换	$C O + H_{2} O \overset{}{\to} C O_{2} + H_{2}$
产物及类型	副反应
醇类	$2 n H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} O + (n - 1) H_{2} O$
Boudouard反应	$2 C O \overset{}{\to} C + C O_{2}$
催化剂变化	反应式
催化剂氧化/还原	$M_{x} O_{y} + y H_{2} \overset{}{\to} y H_{2} O + x M$
体相碳化物生成	$M_{x} O_{y} + y C O \overset{}{\to} y C O_{2} + x M$

表1 CO加氢反应[7]

产物	主反应
甲烷	$C O + 3 H_{2} \overset{}{\to} C H_{4} + H_{2} O$
烷烃	$(2 n + 1) H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} + n H_{2} O$
烯烃	$2 n H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} + n H_{2} O$
水气变换	$C O + H_{2} O \overset{}{\to} C O_{2} + H_{2}$
产物及类型	副反应
醇类	$2 n H_{2} + n C O \overset{}{\to} C_{n} H_{2 n + 2} O + (n - 1) H_{2} O$
Boudouard反应	$2 C O \overset{}{\to} C + C O_{2}$
催化剂变化	反应式
催化剂氧化/还原	$M_{x} O_{y} + y H_{2} \overset{}{\to} y H_{2} O + x M$
体相碳化物生成	$M_{x} O_{y} + y C O \overset{}{\to} y C O_{2} + x M$

图3 过渡金属元素CO解离能力

图4 不同反应压力下Co颗粒尺寸大小与TOF的相互关系及Co粒径对活性和甲烷选择性的影响[15-16]

(1bar=0.1MPa)

图5 尺寸效应对Fe/CNF催化剂合成气制烯烃选择性的影响（0.1MPa，350℃，H2/CO=1，TOS=15h）及尺寸效应对Fe/CNF催化剂TOF和选择性的影响（2MPa，340℃，H2/CO=1，TOS=1h）[17]

表2 费-托合成反应机理[48-49]

$C O \overset{}{\to} C + O$

$O + 2 H \overset{}{\to} H_{2} O$

$C + x H \overset{}{\to} C H_{x}$

C O + H \overset{}{\to} C H O H

$C O \overset{}{\to} C + O$

$O + 3 H \overset{}{\to} H_{2} O H$

链增长

$R + C H_{x} \overset{}{\to} R - C H_{x}$

$R - C H_{x} + (2 - x) H \overset{}{\to} R - C H_{2}$

$R - C - O H + C H O H \overset{}{\to} R - C - C O H + H_{2} O$

$R - C - C O H + 2 H \overset{}{\to} R - C H_{2} - C O H$

$R - C H + C O \overset{}{\to} R - C H - C O$

$R - C H - C O + H \overset{}{\to} R - C H_{2} - C H + H_{2} O$

链终止

$R - C H_{2} + H \overset{}{\to} R - C H_{3}$

$R - C H_{2} - C H_{2} - H \overset{}{\to} R - C H \overset{????}{?} C H_{2}$

$R + C O \overset{}{\to} 醇类$

$R - C H_{2} - C O H + 4 H \overset{}{\to} R - C H_{2} - C H_{3} + H_{2} O$

$R - C H_{2} - C O H + n H \overset{}{\to} 醇类$

$R - C H + 2 H \overset{}{\to} R - C H_{3}$

$R - C H - C O + n H \overset{}{\to} 醇类$

表2 费-托合成反应机理[48-49]

阶段

碳化物机理

烯醇机理

CO插入机理

链引发

$C O \overset{}{\to} C + O$

$O + 2 H \overset{}{\to} H_{2} O$

$C + x H \overset{}{\to} C H_{x}$

C O + H \overset{}{\to} C H O H

$C O \overset{}{\to} C + O$

$O + 3 H \overset{}{\to} H_{2} O H$

链增长

$R + C H_{x} \overset{}{\to} R - C H_{x}$

$R - C H_{x} + (2 - x) H \overset{}{\to} R - C H_{2}$

$R - C - O H + C H O H \overset{}{\to} R - C - C O H + H_{2} O$

$R - C - C O H + 2 H \overset{}{\to} R - C H_{2} - C O H$

$R - C H + C O \overset{}{\to} R - C H - C O$

$R - C H - C O + H \overset{}{\to} R - C H_{2} - C H + H_{2} O$

链终止

$R - C H_{2} + H \overset{}{\to} R - C H_{3}$

$R - C H_{2} - C H_{2} - H \overset{}{\to} R - C H \overset{????}{?} C H_{2}$

$R + C O \overset{}{\to} 醇类$

$R - C H_{2} - C O H + 4 H \overset{}{\to} R - C H_{2} - C H_{3} + H_{2} O$

$R - C H_{2} - C O H + n H \overset{}{\to} 醇类$

$R - C H + 2 H \overset{}{\to} R - C H_{3}$

$R - C H - C O + n H \overset{}{\to} 醇类$

图6 费-托合成中CO活化的基元步骤[53]

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