焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响

靳刘艳; 赵江涛; 张雨; 艾培培; 黄伟

doi:10.12434/j.issn.2097-2547.20240206

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焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响

低碳分子转化合成 | 更新时间：2025-03-27

- 焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响
- Effects of calcination temperatures on performances of MOF-derived Cu@C catalysts for catalytic hydrogenation of dimethyl oxalate to ethylene glycol
- 低碳化学与化工 2025, 50(3): 30-38.
- 作者机构：
  
  太原理工大学化学工程与技术学院省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
- 作者简介：
  
  靳刘艳（1998—），硕士研究生，研究方向为碳一化学与多相催化，E-mail：jinliuyan0423@163.com。
  艾培培（1987—），博士，副教授，研究方向为碳一化学与多相催化，E-mail：aipeipei@tyut.edu.cn；
  黄伟（1962—），博士，教授，研究方向为碳一化学与多相催化，E-mail：huangwei@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金青年科学基金(22008166);山西省面上青年基金(201901D211047);山西省高等学校科技创新项目(2019L0185)
- DOI：10.12434/j.issn.2097-2547.20240206
  中图分类号： TQ530.2
- 收稿日期：2024-05-10，
  
  修回日期：2024-06-06，
  
  纸质出版日期：2025-03-25
- 稿件说明：
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靳刘艳,赵江涛,张雨等.焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响[J].低碳化学与化工,2025,50(03):30-38.

JIN Liuyan,ZHAO Jiangtao,ZHANG Yu,et al.Effects of calcination temperatures on performances of MOF-derived Cu@C catalysts for catalytic hydrogenation of dimethyl oxalate to ethylene glycol[J].Low-carbon Chemistry and Chemical Engineering,2025,50(03):30-38.
靳刘艳,赵江涛,张雨等.焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响[J].低碳化学与化工,2025,50(03):30-38. DOI： 10.12434/j.issn.2097-2547.20240206.

JIN Liuyan,ZHAO Jiangtao,ZHANG Yu,et al.Effects of calcination temperatures on performances of MOF-derived Cu@C catalysts for catalytic hydrogenation of dimethyl oxalate to ethylene glycol[J].Low-carbon Chemistry and Chemical Engineering,2025,50(03):30-38. DOI： 10.12434/j.issn.2097-2547.20240206.

摘要

草酸二甲酯（DMO）加氢制乙二醇（EG）是煤基合成气制EG的关键步骤，该步骤对于替代传统石油衍生路线生产EG并实现煤炭高附加值转化具有重要意义，而高效、稳定的催化DMO加氢制EG催化剂是推动煤基合成气制EG进一步发展的关键。以Cu-1

5-苯三羧酸金属有机骨架（Cu-BTC MOF）为前驱体，将其在N

气氛、不同温度下焙烧得到了Cu@C-

（

为焙烧温度）催化剂，并将Cu@C-

催化剂用于催化DMO加氢制EG反应。通过XRD、SEM、H

-TPR、XPS和N

物理吸/脱附对催化剂进行了表征，研究了焙烧温度对其物相组成、形貌、还原性能、表面元素组成和织构性质的影响。结果表明，焙烧温度改变了Cu物种与碳载体（Cu—O—C）的相互作用，进而显著影响了Cu颗粒尺寸和

(Cu

+ Cu

)。得益于适中的Cu物种与碳载体的相互作用，Cu@C-500催化剂具有最小的Cu颗粒尺寸和最大的

(Cu

+ Cu

)。在240 ℃、2.5 MPa、反应空速为0.2 h

-1

和

(DMO)为200反应条件下，Cu@C-500催化剂的DMO转化率达100%，EG选择性达94.13%，且在250 h内未出现失活现象。

Abstract

Hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG) represents a pivotal step in EG production from coal-based syngas. This process is of great significance for replacing traditional petroleum-derived route to produce EG and achieving high value-added conversion of coal. Efficient and stable catalysts for catalytic hydrogenation of DMO to EG are crucial for promoting the further development of coal-based syngas for EG production. Cu-1

5-phenyltricarboxylic acid metal organic framework (Cu-BTC MOF) was used as a precursor and calcined under N

atmosphere at different temperatures to obtain Cu@C-

(

is the calcination temperature) catalysts

and Cu@C-

catalysts were used to catalyze the hydrogenation of DMO to EG. The catalysts were characterized by XRD

SEM

-TPR

XPS and N

physical adsorption/desorption. The effects of calcination temperatures on phase compositions

morphologies

reduction performances surface element compositions and texture properties were also investigated. The results show that calcination temperatures change the interaction between Cu species and the carbon support (Cu—O—C)

thereby significantly affecting the Cu particles sizes and

(Cu

+ Cu

). Thanks to the moderate interaction between Cu species and the carbon support

Cu@C-500 catalyst has the smallest Cu particle size and largest

(Cu

+ Cu

). Under the reaction conditions of 240 ℃

2.5 MPa

weight hourly space velocity

of 0.2 h

-1

and

(DMO) of 200

Cu@C-500 catalyst achieves

the DMO conversion rate of 100% and EG selectivity of 94.13%

and no deactivation occurs within 250 h.

关键词

Keywords

references

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