Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响

葛浩; 孙燕; 孙启文

doi:10.12434/j.issn.2097-2547.20240465

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Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响

更新时间：2025-04-25

- Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响
- 暂无标题
- 低碳化学与化工 2025: 1-11.
- 作者机构：
  
  上海兖矿能源科技研发有限公司煤液化气化及高效低碳利用全国重点实验室，上海 201203
- 作者简介：
  
  葛浩（1991—），博士，工程师，研究方向为C1化学，E-mail：haoge_1122@163.com。
  孙启文（1958—），博士，研究员，研究方向为煤液化及新型煤化工，E-mail：yetech@ye-tech.com。
- 基金信息：
  
  国家重点研发计划(2023YFB4103200)
- DOI：10.12434/j.issn.2097-2547.20240465
  中图分类号： TQ016.1
- 收稿日期：2024-11-22，
  
  修回日期：2025-02-25，
  
  网络出版日期：2025-04-25，
- 稿件说明：
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葛浩,孙燕,孙启文.Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响[J].低碳化学与化工,

GE Hao,SUN Yan,SUN Qiwen.Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas[J].Low-Carbon Chemistry and Chemical Engineering,
葛浩,孙燕,孙启文.Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20240465.

GE Hao,SUN Yan,SUN Qiwen.Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20240465.

摘要

通过设计高效的无机金属催化剂提升合成气制醇效率及高碳醇（C

醇）选择性对可持续化学和能源开发具有重要意义。为研究Al助剂对CoMn催化剂结构和合成气制高碳醇催化性能的影响，采用共沉淀法制备了不同 Al掺杂量的CoMnAl催化剂，利用XRD、SEM、EDX、N

吸/脱附、ICP、XPS和CO/H

/NH

-TPD等表征技术对比了Al助剂掺杂后对CoMn催化剂的结构、组成、形貌、化合价态以及表面化学性质等的影响，并在260 °C、3 MPa、

(CO):

(Ar) = 80:40:30及反应空速3000 h

-1

条件下对CoMnAl催化剂的催化性能进行了测试。结果表明，作为结构助剂时，适量的Al掺杂会与其他金属产生不同程度的金属间相互作用，从而影响催化剂的比表面积和颗粒尺寸；作为电子助剂时，Al与Co发生电子转移并形成Co-Al-O 活性相，进而影响催化剂的还原性能和氧缺陷形成，有效提高了催化剂的催化性能。原位FT-IR表征揭示了Al助剂掺杂后CoMnAl(0.3)催化剂的反应路径为醛基插入过程，有效抑制了反应中甲烷的生成，提高了总醇选择性，其总醇选择性达到42%，高碳醇在总醇中占比（物质的量分数）高达48.8%。通过精确调控Al助剂的掺杂量，可以有效调控催化剂的结构和表面氧缺陷，从而提高合成气制醇过程的高碳醇选择性。

Abstract

Designing effective inorganic metal catalysts to improve the efficiency of syngas-to-alcohol conversion and the selectivity of higher alcohols (C

alcohols) is critical for the development of sustainable chemistry and energy. To investigate the effect of Al additions on the structure and catalytic performance of CoMn catalysts in synthesis of high-carbon alcohols from syngas

CoMnAl catalysts with varying Al addition quantities were produced by co-precipitation. The effects of Al doped on the structure

composition

morphology

valence state and surface chemical properties of CoMn catalysts were compared using characterization techniques such as XRD

SEM

adsorption/desorption

ICP

XPS and CO/H

/NH

-TPD. The catalytic performance of CoMnAl catalysts was tested under conditions of 260 ℃

3 MPa

(CO):

(Ar) = 80:40:30 and space velocity of 3000 h

-1

. The results show that when Al is doped in appropriate amounts as a structural promoter

it interacts with other metals to variable degrees

influencing the specific surface area and particle size of catalyst. As an electronic promoter

Al facilitates electron transfer with Co to form a Co-Al-O active phase

which in turn affects the reducibility and formation of oxygen defects of the catalyst

significantly enhancing its catalytic performance. In situ FT-IR characterization reveals that the reaction pathway of the CoMnAl(0.3) catalyst doped with Al additives is an aldehyde insertion process

which effectively inhibites the formation of methane in the reaction and improves the total alcohol selectivity to 42%. The percentage of higher alcohols in the total alcohols reaches 48.8% (mole fraction). By precisely controlling the amount of Al doped

it is possible to effectively regulate the structure and surface oxygen defects of the catalyst

thereby enhancing the selectivity for higher alcohols in the syngas-to-alcohol process.

关键词

Keywords

references

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