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草酸二甲酯加氢制乙二醇Cu/SiO2基催化剂研究进展
Research progress in Cu/SiO2-based catalysts for dimethyl oxalate hydrogenation to ethylene glycol
- 低碳化学与化工 2025: 1-15.
- 作者机构：
西南化工研究设计院有限公司 多孔材料与分离转化全国重点实验室，四川 成都 610225
- 作者简介：
王佳杰（1991—），博士，工程师，研究方向为低碳分子转化催化剂，E-mail：drwang1991@foxmail.com。
李文龙（1989—），硕士，高级工程师，研究方向为铜系催化剂与催化工艺，E-mail：liwenlong@swchem.com。
- 基金信息：四川省科技创新人才项目(2024JDRC0016)
DOI：10.12434/j.issn.2097-2547.20250293
中图分类号： TQ426;TQ039;TQ032收稿：2025-07-08，
修回：2025-08-18，
网络出版：2025-12-23，
- 稿件说明：
移动端阅览
王佳杰,李文龙,赵安民等.草酸二甲酯加氢制乙二醇Cu/SiO2基催化剂研究进展[J].低碳化学与化工,
WANG Jiajie,LI Wenlong,ZHAO Anmin,et al.Research progress in Cu/SiO2-based catalysts for dimethyl oxalate hydrogenation to ethylene glycol[J].Low-Carbon Chemistry and Chemical Engineering,
王佳杰,李文龙,赵安民等.草酸二甲酯加氢制乙二醇Cu/SiO2基催化剂研究进展[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20250293.
WANG Jiajie,LI Wenlong,ZHAO Anmin,et al.Research progress in Cu/SiO2-based catalysts for dimethyl oxalate hydrogenation to ethylene glycol[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20250293.
摘要
煤制乙二醇（EG）路线是我国煤炭清洁高效利用战略的核心技术之一，草酸二甲酯（DMO）加氢制EG是煤制EG路线的关键步骤。Cu/SiO
2
基催化剂因其优秀的催化性能和可控的成本而实现了在DMO加氢制EG中的工业化应用。然而，现有技术还存在H
2
循环能耗大、催化剂寿命短等问题。首先，介绍了DMO加氢反应路径、催化剂活性位点与构效关系和失活机理。然后，从构效关系和工业应用角度出发，对复合制备工艺、助剂改性和催化剂微观-介观结构设计等活性中心调控策略进行了分析。最后，对用于DMO加氢制EG的Cu/SiO
2
基催化剂的未来发展进行了展望，如研究催化剂表面物种的动态演变及失活机理、寻找更有效的活性中心调控指标和研制适应低
n
(H
2
)/
n
(DMO)的Cu/SiO
2
基催化剂及其配套工艺。
Abstract
Coal-to-ethylene glycol (EG) route is a pivotal technology within the strategic framework of coal’s clean and efficient utilization in China
and dimethyl oxalate (DMO) hydrogenation to EG is the key step in the route. Due to its outstanding catalytic performance and controllable cost
Cu/SiO
2
-based catalysts have achieved industrial application in DMO hydrogenation to EG. However
present technologies are still limited by high energy cost of H
2
circulation and short catalyst lifespans. Firstly
the reaction pathway of DMO hydrogenation
the active sites of the catalyst and their structure-activity relationships
as well as the deactivation mechanism were introduced. Then
from the perspectives of structure-activity relationship and industrial application
the active center regulation strategies such as the composite preparation process
promoter modification and microscopic-mesoscopic structure design of the catalyst were analyzed. Finally
the future developments of Cu/SiO
2
-based catalysts for DMO hydrogenation to EG were prospected
such as studying the dynamic evolution and deactivation mechanism of surface species of catalysts
seeking more effective active center regulation indicators and developing Cu/SiO
2
-based catalysts suitable for low
n
(H
2
)/
n
(DMO) and their supporting processes.
关键词
Keywords
references
YE R P , LIN L , WANG L C , et al . Perspectives on the active sites and catalyst design for the hydrogenation of dimethyl oxalate [J ] . ACS Catalysis , 2020 , 10 ( 8 ): 4465 - 4490 .
汤之强 ， 李金兵 ， 代武军 . 环氧乙烷/乙二醇生产技术与国产银催化剂研发应用进展 [J ] . 工业催化 , 2021 , 29 ( 5 ): 20 - 22 .
TANG Z Q , LI J B , DAI W J . Production technologies of EO/EG and advance of silver catalyst research and applications [J ] . Industrial Catalysis , 2021 , ( 29 ): 20 - 22 .
陈冲冲 , 委娇娇 , 杨红兵 , 等 . 草酸二甲酯高效低温加氢催化剂研究进展 [J ] . 石油学报（石油加工） , 2024 , 40 ( 5 ): 1224 - 1234 .
CHEN C C , WEI J J , YANG H B , et al . Advances in research of high-efficiency catalysts for low temperature hydrogenation of dimethyl oxalate [J ] . ACTA Petrolei Sinica (Petroleum Processing Section) , 2024 , 40 ( 5 ): 1224 - 1234 .
胡一博 , 韩强 , 赵娜 , 等 . 用于草酸二甲酯选择性加氢催化剂的研究进展 [J ] . 山东化工 , 2023 , 53 ( 7 ): 101 - 103 .
HU Y B , HAN Q , ZHAO N , et al . Recent progress in catalysts for selective hydrogenation of dimethyl oxalate [J ] . Shandong Chemical Industry , 2023 , 53 ( 7 ): 101 - 103 .
HERMAN T T , CORNELIS J E . Ruthenium catalysed hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Chemical Communications , 1997 , 7 : 667 - 668 .
YIN A Y , GUO X Y , DAI W L , et al . High activity and selectivity of Ag/SiO 2 catalyst for hydrogenation of dimethyl oxalate [J ] . Chemical Communications (Camb) , 2010 , 46 ( 24 ): 4348 - 4350 .
ZHU J , ZHAO G F , MENG C , et al . Superb Ni-foam-structured nano-intermetallic InNi 3 C 0.5 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Chemical Engineering Journal , 2021 , 426 : 130857 .
HUANG H J , SHANG X , LI X , et al . epsilon-iron carbide for the hydrogenation of carbonyl groups in esters [J ] . ACS Catalysis , 2024 , 14 ( 15 ): 11294 - 11301 .
GONG J , ZHENG F L , ZHANG H Q , et al . The interfacial effect of SiO 2 -Ni 3 Mo 3 N efficiently catalyzes the low-temperature hydrogenation of dimethyl oxalate to ethanol [J ] . Chinese Chemical Letters , 2025 , 36 ( 8 ): 111122 .
温晓楠 , 张后进 , 胡艳飞 . 煤制乙二醇工艺技术及其生产装置运行分析 [J ] . 广州化工 , 2025 , 53 ( 4 ): 148 - 149 .
WEN X N , ZHANG H J , HU Y F . Analysis of coal-to-ethylene glycol process technology and its production unit operation [J ] . Guangzhou Chemical Industry , 2025 , 53 ( 4 ): 148 - 149 .
CHEN K X , WANG H S , LUO X T , et al . Recent advances in high-performance Cu/SiO 2 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Chemical Engineering Science , 2025 , 313 : 121761 .
YAN W Q , ZHANG J B , ZHOU R J , et al . Identification of synergistic actions between Cu 0 and Cu + sites in hydrogenation of dimethyl oxalate from microkinetic analysis [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 52 ): 22451 - 22459 .
LUN G D , AN W Q , ZHOU J H , et al . A DFT study on the formation mechanism of side product 1,2-propanediol in the hydrogenation of dimethyl oxalate over copper catalyst [J ] . Journal of Fuel Chemistry and Technology , 2024 , 52 ( 4 ): 553 - 564 .
XIAO T T , YANG Z B , ZHEN Z H , et al . Efficient descriptor for designing high-performance Cu-based catalysts for the hydrogenation of dimethyl oxalate to methyl glycolate [J ] . The Journal of Physical Chemistry C , 2024 , 128 ( 19 ): 7926 - 7935 .
YANG Q C , ZHOU J L , BAO R J , et al . Optimization and prediction of catalysts for precise synthesis of methyl glycolate from dimethyl oxalate using machine learning coupled with particle swarm optimization algorithm [J ] . Chemical Engineering Science , 2024 , 297 : 120295 .
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 .
SUN J , YU J F , MA Q X , et al . Freezing copper as a noble metal-like catalyst for preliminary hydrogenation [J ] . Science Advance , 2018 , 4 : e3275 .
YIN A Y , GUO X Y , DAI W L , et al . The nature of active copper species in Cu-HMS catalyst for hydrogenation of dimethyl oxalate to ethylene glycol: New insights on the synergetic effect between Cu 0 and Cu + [J ] . The Journal of Physical Chemistry C , 2009 , 113 : 11003 - 11013 .
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 .
WANG Y , SHEN Y L , ZHAO Y J , et al . Insight into the balancing effect of active Cu species for hydrogenation of carbon-oxygen bonds [J ] . ACS Catalysis , 2015 , 5 ( 10 ): 6200 - 6208 .
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 .
ZHANG P , HUANG L , YANG J X , et al . The regulation of surface copper species coupled with ammonia-evaporation and hydrothermal aging process to enhance catalytic hydrogenation properties of Cu-SiO 2 Catalysts [J ] . Catalysis Letters , 2023 , 154 ( 3 ): 1007 - 1017 .
XU C F , CHEN G X , ZHAO Y , et al . Interfacing with silica boosts the catalysis of copper [J ] . Nature Communication , 2018 , 9 ( 1 ): 3367 .
张博 , 张素华 , 惠胜国 , 等 . 草酸二甲酯加氢制乙二醇Cu/SiO 2 催化剂失活机理的研究: 硫中毒 [J ] . 天然气化工—C1化学与化工 , 2012 , 37 ( 3 ): 39 - 43 .
ZHANG B , ZHANG S H , HUI S G , et al . Study on deactivation mechanism of Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Natural Gas Chemical Industry , 2012 , 37 ( 3 ): 39 - 43 .
高超 , 李速延 , 左满宏 , 等 . 草酸二级制加氢制乙二醇Cu/SiO 2 催化剂失活研究 [J ] . 工业催化 , 2016 , 24 ( 2 ): 58 - 60 .
GAO C , LI S Y , ZUO M H , et al . Deactivation reason analysis of Cu/SiO 2 catalyst for dimethyl oxalate hydrogenation to ethylene glycol [J ] . Industrial Catalysis , 2016 , 24 ( 2 ): 58 - 60 .
ZHENG J W , ZHOU J F , LIN H Q , et al . CO-mediated deactivation mechanism of SiO 2 -supported copper catalysts during dimethyl oxalate hydrogenation to ethylene glycol [J ] . The Journal of Physical Chemistry C , 2015 , 119 ( 24 ): 13758 - 13766 .
LIU L J , LU J Y , YANG Y H , et al . Dealuminated beta zeolite reverses Ostwald ripening for durable copper nanoparticle catalysts [J ] . Science , 2024 , 383 ( 6678 ): 94 - 101 .
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 hydrogenation [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 27 ): 12381 - 12388 .
LUN G D , JIA W T , LUO Z W , et al . Mechanistic insights into deactivation of Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Applied Surface Science , 2025 , 701 : 163248 .
成春喜 , 江甜 , 刘应杰 , 等 . 煤制乙二醇加氢催化剂结焦物的分析 [J ] . 化学与生物工程 , 2023 , 40 ( 11 ): 56 - 59 .
CHEN C X , JIANG T , LIU Y J , et al . Analysis of coke on coal-to-ethylene glycol hydrogenation catalysts [J ] . Chemistry & Bioengineering , 2023 , 40 ( 11 ): 56 - 59 .
THIERRY T , MAGGY K , CATHERINE L . Metal particle size in silica-supported copper catalysts. Influence of the conditions of preparation and of thermal pretreatments [J ] . Journal of Physical Chemistry B , 2000 , 104 ( 5 ): 965 - 972 .
THIERRY T , MAGGY K , CATHERINE L , et al . Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption [J ] . Journal of Physical Chemistry B , 2002 , 106 ( 9 ): 2277 - 2286 .
WANG Y H , WEI J Y , SUN M L , et al . Dual-tuning SiO 2 nanosphere size and hydrothermal reaction temperature toward urchin-like copper phyllosilicate hollow nanospheres catalyst in dimethyl oxalate hydrogenation [J ] . Fuel , 2025 , 401 : 135907 .
周焕文 , 邓少亮 , 乔川 , 等 . 一种草酸酯气相加氢制乙二醇的纳米催化剂及制备方法 : 111715226A [P ] . 2020-07-20 .
ZHOU H W , DENG S L , QIAO C , et al . A nanocatalyst for dimethyl oxalate gasous hydrogenation to ethylene glycol and its preparation method : 111715226A [P ] . 2020-07-20 .
姚元根 , 杨锦霞 , 林凌 , 等 . 一种草酸酯加氢制乙二醇用铜基催化剂及其制备方法 : 112588290A90 [P ] . 2020-12-14 .
YAO Y G , YANG J X , LIN L , et al . A copper-based catalyst for dimethyl oxalate hydrogenation to ethylene glycol and its preparation method : 112588290A90 [P ] . 2020-12-14 .
YIN A Y , GUO X Y , FAN K N , et al . Ion-exchange temperature effect on Cu/HMS catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . ChemCatChem , 2010 , 2 ( 2 ): 206 - 213 .
CUI K , JING Y L , LI X H . Organic compound modified Cu-based catalysts for the hydrogenation of esters [J ] . ChemCatChem , 2024 , 17 ( 3 ): e202401597 .
HUANG L , LIN L , CHEN C C , et al . β -cyclodextrin promoted the formation of copper phyllosilicate on Cu-SiO 2 microspheres catalysts to enhance the low-temperature hydrogenation of dimethyl oxalate [J ] . Journal of Catalysis , 2022 , 413 : 943 - 955 .
YE R P , ZHANG C , ZHANG P , et al . Facile preparation of efficient Cu-SiO 2 catalysts using a polyhydroxy molecular template to regulate surface copper species for dimethyl oxalate hydrogenation [J ] . Catalysis Communications , 2023 , 174 : 106586 .
LI T Y , LIN L , CHEN C C , et al . Insights into a new formation mechanism of robust Cu/SiO 2 Catalysts for low-temperature dimethyl oxalate hydrogenation induced by a chelating ligand of EDTA [J ] . Catalysts , 2022 , 12 ( 3 ): 320 .
YE R P , LIN L , YANG J X , et al . A new low-cost and effective method for enhancing the catalytic performance of Cu-SiO 2 catalysts for the synthesis of ethylene glycol via the vapor-phase hydrogenation of dimethyl oxalate by coating the catalysts with dextrin [J ] . Journal of Catalysis , 2017 , 350 : 122 - 132 .
WANG M L , YAO D W , LI A T , et al . Enhanced selectivity and stability of Cu/SiO 2 catalysts for dimethyl oxalate hydrogenation to ethylene glycol by using silane coupling agents for surface modification [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 20 ): 9414 - 9422 .
WANG M L , HOU S X , YANG Y W , et al . Surface amine species promoted Cu/SiO 2 catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Industrial & Engineering Chemistry Research , 2023 , 62 ( 27 ): 10399 - 10408 .
LI H B , ZHANG Y F , JI D Y , et al . Carbon nanotube and copper phyllosilicate hierarchically integrated catalyst for the efficient hydrogenation of ethylene carbonate to methanol and ethylene glycol [J ] . Fuel , 2024 , 375 : 132555 .
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 .
LIU Z Y , LI Z , MA Z , et al . Histidine-derivate modified Cu/SiO 2 catalyst for selective hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Fuel , 2025 , 381 : 133701 .
CHEN C C , LIN L , YE R P , et al . Mannitol as a novel dopant for Cu/SiO 2 : A low-cost, environmental and highly stable catalyst for dimethyl oxalate hydrogenation without hydrogen prereduction [J ] . Journal of Catalysis , 2020 , 389 : 421 - 431 .
ZHENG J W , HUANG L L , CUI C H , et al . Ambient-pressure synthesis of ethylene glycol catalyzed by C 60 -buffered Cu/SiO 2 [J ] . Science , 2022 , 376 : 288 - 292 .
XU J , LONG Z C , CHEN Z C , et al . Disentangling the catalytic mechanisms of C 60 -buffered Cu/SiO 2 catalyst for DMO-to-EG conversion [J ] . ACS Catalysis , 2024 , 14 ( 19 ): 14733 - 14743 .
ZHENG X L , LIN H Q , ZHENG J W , et al . Pt-promoted Cu/SBA-15 catalysts with excellent performance for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Topics in Catalysis , 2014 , 57 : 1015 - 1025 .
SHESTERKINA A A , ZHURAVLEVA V S , KARTAVOVA K E , et al . Enhanced performance of bimetallic catalysts based on copper phyllosilicate in the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Mendeleev Communications , 2024 , 34 ( 4 ): 569 - 571 .
YU X B , VEST T A , GLEASON B N , et al . Enhanced hydrogenation of dimethyl oxalate to ethylene glycol over indium promoted Cu/SiO 2 [J ] . Journal of Catalysis , 2019 , 380 : 289 - 296 .
ZHENG X , LIN H , ZHENG J , et al . Lanthanum oxide- modified Cu/SiO 2 as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol [J ] . ACS Catalysis , 2013 , 3 ( 12 ): 2738 - 2749 .
CHEN C C , LIN L , YE R P , et al . Construction of Cu-Ce composite oxides by simultaneous ammonia evaporation method to enhance catalytic performance of Ce-Cu/SiO 2 catalysts for dimethyl oxalate hydrogenation [J ] . Fuel , 2021 , 290 : 120083 .
CUI G Q , ZHANG X , WANG H , et al . ZrO 2 - x modified Cu nanocatalysts with synergistic catalysis towards carbon-oxygen bond hydrogenation [J ] . Applied Catalysis B: Environmental , 2021 , 280 : 119406 .
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 .
ZHANG L , AI P P , GAO Z H , et al . Enhanced catalytic stability of Cu-based catalyst for dimethyl oxalate hydrogenation [J ] . Fuel , 2022 , 324 : 124536 .
MA Z , LI Y H , LI Z , et al . Elevating dimethyl oxalate hydrogenation activity over core-shell Cu/SiO 2 @CeO 2 catalysts [J ] . Chemical Engineering Journal , 2024 , 497 : 154592 .
YUE H R , ZHAO Y J , ZHAO S , et al . A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions [J ] . Nature Communication , 2013 , 4 : 2339 .
YIN A Y , GUO X Y , DAI W L , et al . Effect of initial precipitation temperature on the structural evolution and catalytic behavior of Cu/SiO 2 catalyst in the hydrogenation of dimethyl oxalate [J ] . Catalysis Communications , 2011 , 12 ( 6 ): 412 - 416 .
ZHAO Y J , LI S M , WANG Y , et al . Efficient tuning of surface copper species of Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Chemical Engineering Journal , 2017 , 313 : 759 - 768 .
LI B W , LIU J W , LIU Y , et al . Copper nanoparticles confined in hollow silica spheres: Understanding the confinement effect and enhanced catalytic performance for the selective hydrogenation of dimethyl oxalate [J ] . Microporous and Mesoporous Materials , 2025 , 386 : 113490 .
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