Effects of support morphologies on stability of Cu/SiO<sub>2</sub> for catalytic hydrogenation of dimethyl oxalate to ethylene glycol

XIE Dongmin; FANG Song; CHEN Liuyun; XU Chao; XIAO Benduan; SU Tongming; QIN Zuzeng

doi:10.12434/j.issn.2097-2547.20250276

您当前的位置：

首页 >

文章列表页 >

Effects of support morphologies on stability of Cu/SiO₂ for catalytic hydrogenation of dimethyl oxalate to ethylene glycol

更新时间：2026-06-25

- Effects of support morphologies on stability of Cu/SiO₂ for catalytic hydrogenation of dimethyl oxalate to ethylene glycol
- Vol. 51, Issue 6, Pages: 52-64(2026)
- 作者机构：
  
  1.广西大学化学化工学院，广西南宁 530004
  2.广西华谊能源化工有限公司，广西钦州 535008
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250276
  CLC： TQ225.24;TQ426
- Received：17 June 2025，
  
  Revised：2025-07-16，
  
  Published：25 June 2026
- 稿件说明：
移动端阅览
谢冬民,方松,陈柳云等.载体形貌对Cu/SiO₂催化草酸二甲酯加氢制乙二醇反应稳定性的影响[J].低碳化学与化工,2026,51(6):52-64. DOI: 10.12434/j.issn.2097-2547.20250276.

XIE Dongmin,FANG Song,CHEN Liuyun,et al.Effects of support morphologies on stability of Cu/SiO₂ for catalytic hydrogenation of dimethyl oxalate to ethylene glycol[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(6):52-64. DOI: 10.12434/j.issn.2097-2547.20250276.
谢冬民,方松,陈柳云等.载体形貌对Cu/SiO₂催化草酸二甲酯加氢制乙二醇反应稳定性的影响[J].低碳化学与化工,2026,51(6):52-64. DOI: 10.12434/j.issn.2097-2547.20250276. DOI：

XIE Dongmin,FANG Song,CHEN Liuyun,et al.Effects of support morphologies on stability of Cu/SiO₂ for catalytic hydrogenation of dimethyl oxalate to ethylene glycol[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(6):52-64. DOI: 10.12434/j.issn.2097-2547.20250276. DOI：

摘要

草酸二甲酯（DMO）加氢反应是制备乙二醇（EG）的一条兼具经济性与技术性的绿色路线。采用水热法制备了纳米颗粒状、块状以及球状SiO

载体并以此为载体制备了Cu基催化剂，探究了载体形貌对Cu/SiO

催化DMO加氢反应稳定性的影响。采用XRD、SEM、XPS和H

-TPR等对催化剂物化性质进行了分析。结果表明，Cu/SiO

的稳定性受SiO

载体形貌影响。反应70 h后，Cu/SiO

-N（N代表纳米颗粒状）的DMO转化率和EG选择性分别达到98.4%和89.5%，没有出现明显的失活。与块状和球状SiO

负载的催化剂以及商用催化剂相比，Cu/SiO

-N具有更高的稳定性。稳定性提高主要归因于Cu/SiO

-N的Cu

与Cu

相对含量之比较大，抗积碳性能较好。

Abstract

The hydrogenation of dimethyl oxalate (DMO) to produce ethylene glycol (EG) is a green route that combines economic viability with technical feasibility. Nanoparticle-

bulk- and sphere-shaped SiO

supports were prepared by hydrothermal method for supporting Cu-based catalysts

aiming to investigate the effect of support morphologies on the stability of Cu/SiO

in DMO hydrogenation. The physicochemical properties of the catalysts were characterized by XRD

SEM

XPS

-TPR and so on. The results show that the stability of the Cu/SiO

catalyst is affected by the morphologies of the SiO

support. After 70 h of hydrogenation of DMO to EG

the DMO conversion rate and EG selectivity of the Cu/SiO

-N (N represents nanoparticle-shaped) catalyst still reaches 98.4% and 89.5%

respectively

without significant deactivation. Compared with the bulk- and sphere-shaped SiO

-supported catalysts

as well as commercial catalysts

the Cu/SiO

-N catalyst exhibits higher stability. The improvement in stability is mainly due to the higher relative content ratio of Cu

to Cu

and bet

ter anti-carbon deposition performance.

关键词

Keywords

references

YANG J X , LIN L , ZHANG P , et al . Facile and optimized ion-exchange method for synthesizing low-cost and stable Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Industrial & Engineering Chemistry Research , 2023 , 62 ( 37 ): 14866 - 14878 .

赵丽娜 , 张慧丹 , 赵金仙 , 等 . Zr助剂含量对Cu/SiO 2 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 ( 2 ): 61 - 68 .

ZHAO L N , ZHANG H D , ZHAO J X , et al . Effects of Zr additive contents on catalytic performances of Cu/SiO 2 nanotube catalysts for dimethyl oxalate hydrogenation to ethylene glycol [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 2 ): 61 - 68 .

刘应杰 , 成春喜 , 胡燕 , 等 . 合成气乙二醇产品质量提升技术综述 [J ] . 工业催化 , 2024 , 32 ( 7 ): 14 - 18 .

LIU Y J , CHENG C X , HU Y , et al . A review on product quality improvement methods for synthesis gas to ethylene glycol [J ] . Industrial Catalysis , 2024 , 32 ( 7 ): 14 - 18 .

靳珲青 , 石晓丹 , 靳刘艳 , 等 . DMO经两种反应路径加氢制乙醇催化剂研究进展 [J ] . 低碳化学与化工 , 2024 , 49 ( 1 ): 42 - 51 .

JIN H Q , SHI X D , JIN L Y , et al . Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 1 ): 42 - 51 .

XU Y X , KONG L X , HUANG H J , et al . Promotional effect of indium on Cu/SiO 2 catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Catalysis Science & Technology , 2021 , 11 ( 20 ): 6854 - 6865 .

YE R P , LIN L , LI Q H , et al . Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon-oxygen bonds [J ] . Catalysis Science & Technology , 2018 , 8 ( 14 ): 3428 - 3449 .

石晓丹 , 赵江涛 , 张雨 , 等 . Ti 3 C 2 MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能 [J ] . 低碳化学与化工 , 2025 , 50 ( 3 ): 47 - 57 .

SHI X D , ZHAN J T , ZHANG Y , et al . Catalytic performance of Cu-based catalyst supported on Ti 3 C 2 MXene for hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 3 ): 47 - 57 .

GONG J L , YUE H R , ZHAO Y J , et al . Synthesis of ethanol via syngas on Cu/SiO 2 catalysts with balanced Cu 0 -Cu + sites [J ] . Journal of the American Chemical Society , 2012 , 134 ( 34 ): 13922 - 13925 .

ZHAO Y J , ZHANG Y Q , WANG Y , et al . Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation [J ] . Applied Catalysis A: General , 2017 , 539 : 59 - 69 .

LIANG B L , MA J G , SU X , et al . Investigation on deactivation of Cu/ZnO/Al 2 O 3 catalyst for CO 2 hydrogenation to methanol [J ] . Industrial & Engineering Chemistry Research , 2019 , 58 ( 21 ): 9030 - 9037 .

ZHU Y Y , WANG S R , ZHU L J , et al . The influence of copper particle dispersion in Cu/SiO 2 catalysts on the hydrogenation synthesis of ethylene glycol [J ] . Catalysis Letters , 2010 , 135 ( 3/4 ): 275 - 281 .

ZHENG J , HUANG L , CUI C H , et al . Ambient-pressure synthesis of ethylene glycol catalyzed by C 60 -buffered Cu/SiO 2 [J ] . Science , 2022 , 376 ( 6590 ): 288 - 292 .

TIAN H Y , EN H F , LI B W , et al . Cu@C/SiO 2 catalyst with tunable Cu + species by sorbitol for the selective hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Surfaces and Interfaces , 2025 , 56 : 105494 .

WANG X P , CHEN M , CHEN X K , et al . Constructing copper-zinc interface for selective hydrogenation of dimethyl oxalate [J ] . Journal of Catalysis , 2020 , 383 : 254 - 263 .

LI Z , LI Y H , WANG X P , et al . Hydrogenation of dimethyl oxalate to ethanol over Mo-doped Cu/SiO 2 catalyst [J ] . Chemical Engineering Journal , 2023 , 454 : 140001 .

AI P P , JIN H Q , LI J , et al . Ultra-stable Cu-based catalyst for dimethyl oxalate hydrogenation to ethylene glycol [J ] . Chinese Journal of Chemical Engineering , 2023 , 60 : 186 - 193 .

HOSAKA S , KURNIAWAN E , YAMADA Y , et al . Vapor-phase dehydrogenation of 1-decanol to decanal over Cu/SiO 2 catalyst prepared by organic additives-assisted impregnation [J ] . Applied Catalysis A: General , 2023 , 653 : 119079 .

DING J , ZHANG J , ZHANG C , et al . Hydrogenation of diethyl oxalate over Cu/SiO 2 catalyst with enhanced activity and stability: Contribution of the spatial restriction by varied pores of support [J ] . Applied Catalysis A: General , 2015 , 508 : 68 - 79 .

YU J , CHEN G Q , GUO Q S , et al . Ultrasmall bimetallic Cu/ZnO x nanoparticles encapsulated in UiO-66 by deposition-precipitation method for CO 2 hydrogenation to methanol [J ] . Fuel , 2022 , 324 : 124694 .

HOANG T T N , TSAI D-H . Low-temperature methanol synthesis via (CO 2 + CO) combined hydrogenation using Cu-ZnO/Al 2 O 3 hybrid nanoparticle cluster [J ] . Applied Catalysis A: General , 2022 , 645 : 118844 .

HAN C Y , ZHANG H T , LI C M , et al . The regulation of Cu-ZnO interface by Cu-Zn bimetallic metal organic framework-templated strategy for enhanced CO 2 hydrogenation to methanol [J ] . Applied Catalysis A: General , 2022 , 643 : 118805 .

SONG Y B , ZHANG J , LV J , et al . Hydrogenation of dimethyl oxalate over copper-based catalysts: Acid-base properties and reaction paths [J ] . Industrial & Engineering Chemistry Research , 2015 , 54 ( 40 ): 9699 - 9707 .

WU P , MA C L , WU J H , et al . Study on the deactivation and regeneration mechanism of Cu-Al catalyst in the hydrogenation of diethyl oxalate [J ] . Fuel , 2024 , 365 : 131153 .

ZHAO Y J , KONG L X , XU Y X , et al . Deactivation mechanism of Cu/SiO 2 catalysts in the synthesis of ethylene glycol via methyl glycolate hydrogenatio n [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 27 ): 12381 - 12388 .

VASILIADOU E S , EGGENHUISEN T M , MUNNIK P , et al . Synthesis and performance of highly dispersed Cu/SiO 2 catalysts for the hydrogenolysis of glycerol [J ] . Applied Catalysis B: Environmental , 2014 , 145 : 108 - 119 .

AI P P , ZHANG L , NIU J C , et al . Boron-doped lamellar porous carbon supported copper catalyst for dimethyl oxalate hydrogenation [J ] . Chinese Journal of Chemical Engineering , 2023 , 55 : 222 - 229 .

ZHANG M H , TAN X C , ZHANG T , et al . The deactivation of a ZnO doped ZrO 2 -SiO 2 catalyst in the conversion of ethanol/acetaldehyde to 1,3-butadiene [J ] . RSC Advances , 2018 , 8 ( 59 ): 34069 - 34077 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Study on deactivation mechanism of Cu/SiO2 catalyst in hydrogenation of dimethyl oxalate

Study on deactivation mechanism of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Effects of CO and methyl glycolate on hydrogenation of dimethyl oxalate to ethyl glycol over Cu/SiO2 catalysts

Effect of amount of ammonia on preparation of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Experimental study on formation promotion and stabilization mechanisms of CO2 hydrate in nano-SiO2 dispersion

Related Author

DU Jiaqi

LI Wenlong

WANG Jiajie

SONG Yuanjiang

WANG Xiaoli

ZHAO Anmin

LI Yang

HU Zhibiao

Related Institution

C1 Chemistry, Southwest Institute of Chemical Co., Ltd.

华东理工大学化学工程国家重点实验室

上海浦景化工技术有限公司

沈阳化工大学化学工程学院

College of Chemical Engineering, Shenyang University of Chemical Technology

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：465839 Visits Today：286

⁰

Effects of support morphologies on stability of Cu/SiO2 for catalytic hydrogenation of dimethyl oxalate to ethylene glycol

DOI：10.12434/j.issn.2097-2547.20250276

摘要

Abstract

关键词

Keywords

references

Effects of support morphologies on stability of Cu/SiO₂ for catalytic hydrogenation of dimethyl oxalate to ethylene glycol