氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

宋宇淙; 丁晓墅; 闫亚辉; 王淑芳; 王延吉

doi:10.11949/j.issn.0438-1157.20181455

您当前的位置：

首页 >

文章列表页 >

氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

催化、动力学与反应器 | 更新时间：2026-07-24

- 氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能
- Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis
- 化工学报 2019年70卷第4期页码：1401-1408
- 作者机构：
  
  1.河北工业大学化工学院，绿色化工和高效节能河北省重点实验室，天津 300130
  2.中国船舶重工集团公司第七一八研究所，河北邯郸 056027
- 作者简介：
  
  宋宇淙（1993—），女，博士研究生，yucong0508@163.com
  丁晓墅（1985—），女，博士，副教授，dxshu@hebut.edu.cn
  王延吉（1962—），男，博士，教授，yjwang@hebut.edu.cn
- 基金信息：
  
  国家青年自然科学基金项目(21606070);河北省青年科学基金项目(B2016202256);国家自然科学基金重点项目(21236001);国家自然科学基金项目(21576069)
- DOI：10.11949/j.issn.0438-1157.20181455
  中图分类号： O 643.32;TQ 225.5
- 收稿：2018-12-05，
  
  修回：2019-01-24，
  
  网络首发：2020-06-15，
  
  纸质出版：2019-04-12
- 稿件说明：
移动端阅览
宋宇淙, 丁晓墅, 闫亚辉, 王淑芳, 王延吉. 氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能[J]. 化工学报, 2019, 70(4): 1401-1408

SONG Yucong, DING Xiaoshu, YAN Yahui, WANG Shufang, WANG Yanji. Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis[J]. CIESC Journal, 2019, 70(4): 1401-1408
宋宇淙, 丁晓墅, 闫亚辉, 王淑芳, 王延吉. 氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能[J]. 化工学报, 2019, 70(4): 1401-1408 DOI： 10.11949/j.issn.0438-1157.20181455.

SONG Yucong, DING Xiaoshu, YAN Yahui, WANG Shufang, WANG Yanji. Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis[J]. CIESC Journal, 2019, 70(4): 1401-1408 DOI： 10.11949/j.issn.0438-1157.20181455.

摘要

针对甲醇气相氧化羰基化直接合成碳酸二甲酯（DMC）反应中催化剂活性低和稳定性差的

问题，制备了一系列氧化石墨烯复合金属催化剂，并对其进行活性评价。结果表明：催化剂PdCl

-CuCl

-KOAc/AC@GO-HCl表现出最佳的催化活性和稳定性：DMC的空时收率（STY）为800~900 g·(L cat)

-1

·h

-1

，且反应16 h内活性无明显下降；甲醇选择性保持在95%以上，CO选择性为35%~40%。结合XRD和XPS表征发现，活性物种Cu

Cl(OH)

的生成，提高了催化剂催化活性，而CuO和KCl均可导致催化剂的失活。

Abstract

A series of graphene oxide composite metal catalysts were prepared and evaluated for their activity in the direct synthesis of dimethyl carbonate (DMC) by methanol vapor phase oxidative carbonylation. The results show that the catalyst PdCl

-CuCl

-KOAc/AC@GO-HCl has the best catalytic activity and stability. The space time yield (STY) of DMC was between 800－900 g·(L cat)

-1

·h

-1

and the catalytic activity was stable in 16 h without significant decrease. Methanol selectivity was maintained above 95%

and CO selectivity was between 35%－40%. Combined with results of XRD and XPS analyses

it was found that the formation of the active species Cu

Cl(OH)

improved the catalytic activity of the catalyst

while both CuO and KCl could cause the deactivation of the catalyst.

关键词

Keywords

references

王延吉 , 赵新强 . 绿色催化过程与工艺 [M ] . 北京 : 化学工业出版社 , 2014 . 6 .

Wang Y J , Zhao X Q . Green Catalytic Process and Technology [M ] . Beijing : Chemical Industry Press , 2014 .

Ono Y . Dimethyl carbonate for environmentally benign reactions [J ] . Pure & Applied Chemistry , 1997 , 35 ( 1/2 ): 15 - 25 .

Pacheco M A , Marshall C L . Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive [J ] . Energy & Fuels , 1997 , 11 ( 1 ): 2 - 29 .

Tomishige K , Sakaihori T , Sakai S I , et al . Dimethyl carbonate synthesis by oxidative carbonylation on activated carbon supported CuCl 2 catalysts: catalytic properties and structural change [J ] . Applied Catalysis A General , 1999 , 181 ( 1 ): 95 - 102 .

Han M S , Lee B G , Ahn B S , et al . Surface properties of CuCl 2 /AC catalysts with various Cu contents: XRD, SEM, TG/DSC and CO-TPD analyses [J ] . Applied Surface Science , 2003 , 211 ( 1 ): 76 - 81 .

Han M S , Lee B G , Suh I , et al . Synthesis of dimethyl carbonate by vapor phase oxidative carbonylation of methanol over Cu-based catalysts [J ] . Journal of Molecular Catalysis A Chemical , 2001 , 170 ( 1 ): 225 - 234 .

Wang R , Zhong L I , Zheng H . Catalytic performance of Cu 2 (OH) 3 Cl catalysts supported on various supports for methanol oxidative carbonylation [J ] . Chinese Journal of Catalysis , 2009 , 30 ( 10 ): 1068 - 1072 .

王延吉 , 赵新强 , 苑保国 , 等 . 甲醇气相氧化羰基化合成碳酸二甲酯的研究(Ⅰ): 催化剂制备及反应性能 [J ] . 燃料化学学报 , 1997 , ( 4 ): 323 - 327 .

Wang Y J , Zhao X Q , Yuan B G , et al . Study on gas phase oxidative carbonylation of methanol to dimethyl carbonate (Ⅰ): Catalyst preparation and reaction performance [J ] . Journal of Fuel Chemistry and Technology , 1997 , ( 4 ): 323 - 327 .

姜瑞霞 , 王延吉 , 赵新强 , 等 . 甲醇气相氧化羰基化合成碳酸二甲酯的研究(Ⅱ): 助剂对催化性能的影响 [J ] . 燃料化学学报 , 1999 , ( 4 ): 319 - 322 .

Jiang R X , Wang Y J , Zhao X Q , et al . Study on gas phase oxidative carbonylation of methanol to dimethyl carbonate (Ⅱ): Effect of additives on catalytic performance [J ] . Journal of Fuel Chemistry and Technology , 1999 , ( 4 ): 319 - 322 .

姜瑞霞 , 王延吉 , 赵新强 , 等 . 甲醇气相氧化羰基化合成碳酸二甲酯的研究(Ⅲ): 催化剂的失活再生 [J ] . 燃料化学学报 , 2000 , 28 ( 5 ): 478 - 480 .

Jiang R X , Wang Y J , Zhao X Q , et al . Study on gas phase oxidative carbonylation of methanol to dimethyl carbonate (Ⅲ): Deactivated regeneration of catalyst [J ] . Journal of Fuel Chemistry and Technology , 2000 , 28 ( 5 ): 478 - 480 .

王延吉 , 姜瑞霞 , 赵新强 , 等 . 甲醇气相氧化羰基化合成碳酸二甲酯的催化剂结构表征 [J ] . 河北工业大学学报 , 2000 , 29 ( 1 ): 97 - 101 .

Wang Y J , Jiang R X , Zhao X Q , et al . Structural characterization of catalysts for gas phase oxidative carbonylation of methanol to dimethyl carbonate [J ] . Journal of Hebei University of Technology , 2000 , 29 ( 1 ): 97 - 101 .

Yang P , Cao Y , Dai W L , et al . Effect of chemical treatment of activated carbon as a support for promoted dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol over Wacker-type catalysts [J ] . Applied Catalysis A General , 2003 , 243 ( 2 ): 323 - 331 .

王淑芳 , 崔咏梅 , 赵新强 , 等 . 合成碳酸二甲酯PdCl 2 -CuCl 2 -KOAc/AC催化剂失活过程分析 [J ] . 化工学报 , 2004 , 55 ( 12 ): 2008 - 2014 .

Wang S F , Cui Y M , Zhao X Q , et al . Analysis of deactivation of PdCl 2 -CuCl 2 -KOAc/AC catalyst for synthesis of dimethyl carbonate [J ] . Journal of Chemical Industry and Engineering (China) , 2004 , 55 ( 12 ): 2008 - 2014 .

李致伯 . 甲醇气相氧化羰基化制备碳酸二甲酯 [D ] . 汕头 : 汕头大学 , 2010 .

Li Z B . Synthesis of dimethyl carbonate by gas-phase oxidative carbonylation of methanol [D ] . Shantou : Shantou University , 2010 .

King S T . Oxidative carbonylation of methanol to dimethyl carbonate by solid-state ion-exchanged CuY catalysts [J ] . Catalysis Today , 1997 , 33 ( 1 ): 173 - 182 .

King S T . Reaction mechanism of oxidative carbonylation of methanol to dimethyl carbonate in Cu-Y zeolite [J ] . Journal of Catalysis , 1996 , 161 ( 2 ): 530 - 538 .

Li Z , Xie K , Slade R C T . Studies of the interaction between CuCl and HY zeolite for preparing heterogeneous CuI catalyst [J ] . Applied Catalysis A General , 2001 , 209 ( 1 ): 107 - 115 .

黄丽明 . 无氯铜配合物催化甲醇氧化羰基化合成碳酸二甲酯 [D ] . 武汉 : 武汉工程大学 , 2013 .

Huang L M . Synthesis of dimethyl carbonate from oxidative carbonylation of methanol catalyzed by copper complex without chloride [D ] . Wuhan : Wuhan Institute of Technology , 2013 .

王瑞玉 . 完全无氯铜基催化剂制备与催化甲醇氧化羰基化的研究 [D ] . 太原 : 太原理工大学 , 2010 .

Wang R Y . Preparation and catalytic performance of chloring-free copper oxidative carbonylation of methanol [D ] . Taiyuan : Taiyuan University of Technology , 2010 .

王瑞玉 , 李忠 , 郑华艳 , 等 . 无氯Cu/AC催化剂的制备及其催化气相甲醇氧化羰基化反应性能 [J ] . 催化学报 , 2010 , 31 ( 7 ): 851 - 856 .

Wang R Y , Li Z , Zheng H Y , et al . Preparation of chlorine-free Cu/AC catalyst and its catalytic properties for vapor phase oxidative carbonylation of methanol [J ] . Chinese Journal of Catalysis , 2010 , 31 ( 7 ): 851 - 856 .

毕朝刚 . 氧化石墨烯及其复合物的制备与表征 [D ] . 大连 : 大连理工大学 , 2014 .

Bi C G . Synthesis and characterization of graphene oxides and their composites [D ] . Dalian : Dalian University of Technology , 2014 .

袁定重 , 陈碧波 . 氧化石墨烯负载席夫碱钯催化剂的合成、表征及对Suzuki反应催化性能的研究 [J ] . 有机化学 , 2014 , 34 ( 8 ): 1630 - 1638 .

Yuan D Z , Chen B B . Synthesis and characterization of graphene oxide supported Schiff base palladium catalyst and its catalytic performance to Suzuki reaction [J ] . Chinese Journal of Organic Chemistry , 2014 , 34 ( 8 ): 1630 - 1638 .

丁晓墅 . 高选择性气相合成碳酸二甲酯催化过程及集成工艺研究 [D ] . 天津 : 河北工业大学 , 2013 .

Ding X S . Highty selective gas-phase synthesis of dimethyl carbonate and integrated process optimization [D ] . Tianjin : Hebei University of Technology , 2013 .

Ma X , Zhao R , Xu G , et al . Physico-chemical properties of supported Cu catalysts for production of dimethyl carbonate [J ] . Catalysis Today , 1996 , 30 ( 1 ): 201 - 206 .

张震 , 张婧 , 王胜平 , 等 . 碱式氯化铜对氧化羰基合成碳酸二乙酯催化活性的影响 [J ] . 化工学报 , 2006 , 57 ( 4 ): 805 - 809 .

Zhang Z , Zhang J , Wang S P , et al . Effect of copper chloride hydroxide on catalytic synthesis of diethyl carbonate by oxidative carbonylation of ethanol [J ] . Journal of Chemical Industry and Engineering (China) , 2006 , 57 ( 4 ): 805 - 809 .

王淑芳 . 气相直接合成碳酸二甲酯PdCl 2 -CuCl 2 -KOAc/AC催化剂的研究 [D ] . 天津 : 河北工业大学 , 2002 .

Wang S F . Study of PdCl 2 -CuCl 2 -KOAc/AC catalyst for gas-phase direct synthesis of dimethyl carbonate [D ] . Tianjin : Hebei University of Technology , 2002 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

氮掺杂多孔碳催化剂位点调控方法及作用机制研究

聚丙烯定向转化制芳烃：金属-分子筛协同催化机制

甲醇和乙酸甲酯一步法制丙酸甲酯催化剂的可控制备与性能调控

Co-Pt/HAP的制备及其催化1，2-丙二醇氨化反应

TS-1/In-TS-1催化果糖一步法醇解制备乳酸甲酯连续化试验