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Effects of calcination temperatures on performances of MOF-derived Cu@C catalysts for catalytic hydrogenation of dimethyl oxalate to ethylene glycol
- Low-carbon Chemistry and Chemical Engineering Vol. 50, Issue 3, Pages: 30-38(2025)
- 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：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240206
CLC： TQ530.2Received：10 May 2024，
Revised：06 June 2024，
Published：25 March 2025
- 稿件说明：
移动端阅览
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
3
5-苯三羧酸金属有机骨架（Cu-BTC MOF）为前驱体，将其在N
2
气氛、不同温度下焙烧得到了Cu@C-
x
（
x
为焙烧温度）催化剂，并将Cu@C-
x
催化剂用于催化DMO加氢制EG反应。通过XRD、SEM、H
2
-TPR、XPS和N
2
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
n
(Cu
+
)/
n
(Cu
0
+ 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
n
(Cu
+
)/
n
(Cu
0
+ Cu
+
)。在240 ℃、2.5 MPa、反应空速为0.2 h
-1
和
n
(H
2
)/
n
(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
3
5-phenyltricarboxylic acid metal organic framework (Cu-BTC MOF) was used as a precursor and calcined under N
2
atmosphere at different temperatures to obtain Cu@C-
x
(
x
is the calcination temperature) catalysts
and Cu@C-
x
catalysts were used to catalyze the hydrogenation of DMO to EG. The catalysts were characterized by XRD
SEM
H
2
-TPR
XPS and N
2
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
n
(Cu
+
)/
n
(Cu
0
+ 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
n
(Cu
+
)/
n
(Cu
0
+ Cu
+
). Under the reaction conditions of 240 ℃
2.5 MPa
weight hourly space velocity
of 0.2 h
-1
and
n
(H
2
)/
n
(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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