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Zr助剂含量对Cu/SiO2纳米管催化草酸二甲酯加氢制乙二醇反应性能的影响
Effects of Zr additive contents on catalytic performances of Cu/SiO2 nanotube catalysts for dimethyl oxalate hydrogenation to ethylene glycol
- 低碳化学与化工 2025, 50(2): 61-68.
- 作者机构：
太原理工大学 化学与化工学院 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：
赵丽娜（1997—），硕士研究生，研究方向为一碳化学与化工，E-mail：609655492@qq.com。
赵金仙（1987—），博士，副教授，研究方向为一碳化学与化工，E-mail：zhaojinxian@tyut.edu.cn。
- 基金信息：国家自然科学基金(22179091;21808154)
DOI：10.12434/j.issn.2097-2547.20240164
中图分类号： TQ225.24;TQ426收稿日期：2024-04-17，
修回日期：2024-05-28，
纸质出版日期：2025-02-25
- 稿件说明：
移动端阅览
赵丽娜,张慧丹,赵金仙等.Zr助剂含量对Cu/SiO2纳米管催化草酸二甲酯加氢制乙二醇反应性能的影响[J].低碳化学与化工,2025,50(02):61-68.
ZHAO Lina,ZHANG Huidan,ZHAO Jinxian,et al.Effects of Zr additive contents on catalytic performances of Cu/SiO2 nanotube catalysts for dimethyl oxalate hydrogenation to ethylene glycol[J].Low-carbon Chemistry and Chemical Engineering,2025,50(02):61-68.
赵丽娜,张慧丹,赵金仙等.Zr助剂含量对Cu/SiO2纳米管催化草酸二甲酯加氢制乙二醇反应性能的影响[J].低碳化学与化工,2025,50(02):61-68. DOI： 10.12434/j.issn.2097-2547.20240164.
ZHAO Lina,ZHANG Huidan,ZHAO Jinxian,et al.Effects of Zr additive contents on catalytic performances of Cu/SiO2 nanotube catalysts for dimethyl oxalate hydrogenation to ethylene glycol[J].Low-carbon Chemistry and Chemical Engineering,2025,50(02):61-68. DOI： 10.12434/j.issn.2097-2547.20240164.
摘要
随着我国聚酯工业的迅猛发展，乙二醇（EG）需求量持续增大，使用助剂对Cu基催化剂进行改性已成为提高乙二醇产率的有效策略之一。采用一锅法制备了Zr助剂掺杂的Cu/SiO
2
纳米管催化剂用于草酸二甲酯（DMO）加氢合成乙二醇，采用XRD、N
2
吸/脱附、FT-IR、TEM、H
2
-TPR和XPS等对催化剂进行了表征，并重点考察了Zr助剂含量（
n
(Zr)/
n
(Cu)）对催化性能的影响。结果表明，适量Zr助剂（
n
(Zr)/
n
(Cu) = 0.05）的引入有利于活性组分Cu均匀分布在纳米管上，提高了Cu物种的分散度。此外，Cu与Zr之间的电子转移增强了金属之间的相互作用，有利于催化剂表面Cu
+
物种的稳定，进而提高催化剂的活性和稳定性。在反应温度为210 ℃、反应压力为2.4 MPa、原料
n
(H
2
)/
n
(DMO)为110、质量空速为0.405 h
-1
和反应时间为40 h条件下，Cu-Zr
0.05
/SiO
2
催化性能最佳，其DMO转化率和EG选择性分别达到99.1%和91.9%。
Abstract
With the rapid development of polyester industry in China
the demand for ethylene glycol（EG） continues to increase
and the use of additives to modify copper-based catalysts has become one of the effective strategies to improve the yield of ethylene glycol. Zr additive-doped Cu/SiO
2
nanotube catalysts were prepared by one-pot method for dimethyl oxalate hydrogenation to ethylene glycol. The catalysts
were characterized by XRD
N
2
adsorption/desorption
FT-IR
TEM
H
2
-TPR and XPS. The effects of Zr contents (
n
(Zr)/
n
(Cu)) on catalytic performances was investigated. The results show that introduction of appropriate amount of Zr (
n
(Zr)/
n
(Cu) = 0.05) is conducive to the copper species uniform distribution on the nanotubes
which improves the dispersion of copper species. In addition
the electron transfer between Cu and Zr enhances the interaction between metals
which is conducive to the stability of Cu
+
species on catalyst surface
thereby improving the activity and stability of catalyst. Under the conditions of reaction temperature of 210 ℃
reaction pressure of 2.4 MPa
n
(H
2
)/
n
(DMO) of 100
weight hourly space velocity of 0.405 h
-1
and reaction time of 40 h
Cu-Zr
0.05
/SiO
2
shows the best catalytic performance. The DMO conversion and EG selectivity of Cu-Zr
0.05
/SiO
2
reach 99.1% and 91.9%
respectively.
关键词
Keywords
references
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