Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用

王志苗; 张洪起; 周立超; 李芳; 薛伟; 王延吉

doi:10.11949/0438-1157.20190395

您当前的位置：

首页 >

文章列表页 >

Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用

催化、动力学与反应器 | 更新时间：2026-07-24

- Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用
- Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate
- 化工学报 2019年70卷第12期页码：4625-4634
- 作者机构：
  
  1. 河北工业大学化工学院，河北省绿色化工与高效节能重点实验室，天津 300130
  2. 天津市本质安全化工技术重点实验室，天津 300130
- 作者简介：
  
  王志苗（1985—），女，硕士，实验师，wangzhimiao@hebut.edu.cn
  薛伟（1975—），男，博士，教授，weixue@hebut.edu.cn
  王延吉（1962—），男，博士，教授，yiwang@hebut.cdu.cn
- 基金信息：
  
  国家自然科学基金项目(21776057);天津市自然科学基金项目(17JCYBJC20100;18JCYBJC21500);河北省留学人员科技活动择优资助项目(CL201605)
- DOI：10.11949/0438-1157.20190395
  中图分类号： O 643;X 511
- 收稿：2019-04-16，
  
  修回：2019-08-23，
  
  网络首发：2020-06-09，
  
  纸质出版：2019-12-05
- 稿件说明：
移动端阅览
王志苗, 张洪起, 周立超, 李芳, 薛伟, 王延吉. Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用[J]. 化工学报, 2019, 70(12): 4625-4634

WANG Zhimiao, ZHANG Hongqi, ZHOU Lichao, LI Fang, XUE Wei, WANG Yanji. Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate[J]. CIESC Journal, 2019, 70(12): 4625-4634
王志苗, 张洪起, 周立超, 李芳, 薛伟, 王延吉. Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用[J]. 化工学报, 2019, 70(12): 4625-4634 DOI： 10.11949/0438-1157.20190395.

WANG Zhimiao, ZHANG Hongqi, ZHOU Lichao, LI Fang, XUE Wei, WANG Yanji. Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate[J]. CIESC Journal, 2019, 70(12): 4625-4634 DOI： 10.11949/0438-1157.20190395.

摘要

采用微乳液法制备了Ce为助剂的Pd-Ce-O/SiO

催化剂，用于苯酚氧化羰基化合成碳酸二苯酯（DPC）反应。活性评价结果显示，催化剂性能随着Ce用量的增加而提高，当Ce/Pd摩尔比为10/1时，苯酚转化率为64.4%，碳酸二苯酯选择性为83.4%。利用XRD表征发现，部分Ce

进入到PdO晶格中，使得失活Pd原子中的电子更容易向Ce转移，从而易于再生，表现出更好的催化性能。根据上述结果，设计制备了Pd-O/CeO

催化剂用于本反应，苯酚转化率和碳酸二苯酯选择性分别仅为24.0%和23.3%。表征发现，在Pd-Ce-O/SiO

催化剂表面，Pd物种主要是PdO，而Pd-O/CeO

表面的Pd物种则以PdO

为主。由于苯酚氧化羰基化反应的活性中心为Pd(Ⅱ)，所以Pd-O/CeO

催化性能较差。并且，由于Pd与CeO

之间存在强相互作用，催化剂表面Pd含量较低，这也是Pd-O/CeO

催化活性较差的原因之一。

Abstract

A Pd-Ce-O/SiO

catalyst with Ce as auxiliary was prepared by microemulsion method for oxidative carbonylation of phenol to synthesize diphenyl carbonate (DPC). The activity evaluation results showed that the catalyst performance increased with the increase of the amount of Ce. When the Ce/Pd molar ratio was 10/1

the phenol conversion rate was 64.4%

and the diphenyl carbonate selectivity was 83.4%. The XRD results showed that part of Ce

entered into PdO crystal lattice

erefore the electrons of deactivated Pd could easily be transferred to Ce. So the Pd-Ce-O/SiO

catalyst could be easily regenerated and showed better performance. According to the above mentioned results

Pd-O/CeO

was designed and prepared for oxidative carbonylation of phenol. However

unlike Pd-Ce-O/SiO

Pd-O/CeO

showed poor catalytic performance. The phenol conversion and DPC selectivity was only 24.0% and 23.3% respectively. The characterization results showed that PdO was the main species of Pd on the surface of Pd-Ce-O/SiO

but there was more PdO

on Pd-O/CeO

. Because Pd(Ⅱ) is the active site for oxidative carbonyation

Pd-O/CeO

exhibited inferior activity to Pd-Ce-O/SiO

. In addition

in Pd-O/CeO

catalyst

the surface Pd content was lower than that of other catalyst because of the strong interaction between Pd species and CeO

. That s one of the reasons for the poor activity of Pd-O/CeO

关键词

Keywords

references

崔小明 . 国内外聚碳酸酯的供需现状及发展前景分析 [J ] . 石油化工技术与经济 , 2017 , 33 ( 1 ): 18 - 23 .

Cui X M . Supply and demand status of polycarbonate at home and abroad and its development prospect analysis [J ] . Technology ＆ Economics in Petrochemicals , 2017 , 33 ( 1 ): 18 - 23 .

Gong J L , Ma X B , Wang S P . Phosgene-free approaches to catalytic synthesis of diphenyl carbonate and its intermediates [J ] . Applied Catalysis A: General , 2007 , 316 : 1 .

Figueiredo M C , Trieu V , Eiden S , et al . Spectroscopic investigation of the electrosynthesis of diphenyl carbonate from CO and phenol on gold electrodes [J ] . ACS Catalysis , 2018 , 8 ( 4 ): 3087 - 3090 .

王延吉 , 赵新强 . 绿色催化过程与工艺 [M ] . 2 版 . 北京 : 化学工业出版社 , 2015 .

Wang Y J , Zhao X Q . Green Catalytic Process and Technology [M ] . 2nd ed . Beijing: Chemical Industry Press , 2015 .

付嫱 , 欧阳春 , 曾毅 , 等 . 甲基苯基碳酸酯歧化反应研究进展 [J ] . 化工进展 , 2017 , 36 ( 8 ): 2748 - 2755 .

Fu Q , Ouyang C , Zeng Y , et al . Progresses in the research on disproportionation of methyl phenyl carbonate [J ] . Chemical Industry and Engineering Progress , 2017 , 36 ( 8 ): 2748 - 2755 .

Tang R Z , Chen T , Chen Y , et al . Core-shell TiO 2 @SiO 2 catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate [J ] . Chinese Journal of Catalysis , 2014 , 35 ( 4 ): 457 - 461 .

Yang X , Ma X B , Wang S P , et al . Transesterification of dimethyl oxalate with phenol over TiO 2 /SiO 2 : catalyst screening and reaction optimization [J ] . AIChE Journal , 2008 , 54 ( 12 ): 3260 - 3272 .

Yin X , Zeng Y , Yao J , et al . Kinetic modeling of the transesterification reaction of dimethyl carbonate and phenol in the reactive distillation reactor [J ] . Industrial & Engineering Chemistry Research , 2014 , 53 ( 49 ): 19087 - 19093 .

薛伟 , 张敬畅 , 王延吉 , 等 . 新型超细包覆型催化剂的制备及催化苯酚氧化羰基化合成碳酸二苯酯 [J ] . 化工学报 , 2004 , 55 ( 12 ): 2076 - 2081 .

Xue W , Zhang J C , Wang Y J , et al . Preparation of novel ultrafine embedded catalyst for oxidative carbonylation of phenol to diphenyl carbonate [J ] . Journal of Chemical Industry and Engineering (China) , 2004 , 55 ( 12 ): 2076 - 2081 .

Lu W , Du Z P , Yuan H , et al . Synthesis of diphenyl carbonate over the magnetic catalysts Pd/La 1- x Pb x MnO 3 ( x = 0.2—0.7) [J ] . Chinese Journal of Chemical Engineering , 2013 , 21 : 8 - 13 .

Ronchin L , Vavasori A , Amadio E , et al . Oxidative carbonylation of phenols catalyzed by homogeneous and heterogeneous Pd precursors [J ] . Journal of Molecular Catalysis A: Chemical , 2009 , 298 : 23 - 30 .

Yang X J , Han J Y , Du Z P , et al . Effects of Pb dopant on structure and activity of Pd/K-OMS-2 catalysts for heterogeneous oxidative carbonylation of phenol [J ] . Catalysis Communications , 2010 , 11 : 643 - 646 .

Zhang Y L , Xiang S L , Wang G Q , et al . Preparation and application of coconut shell activated carbon immobilized palladium complexes [J ] . Catalysis Science & Technology , 2014 , 4 : 1055 - 1063 .

Yin C F , Zhou J , Chen Q M , et al . Deactivation causes of supported palladium catalysts for the oxidative carbonylation of phenol [J ] . Journal of Molecular Catalysis A: Chemical , 2016 , 424 : 377 - 383 .

Vavasori A , Toniolo L . Multistep electron-transfer catalytic system for the oxidative carbonylation of phenol to diphenyl carbonate [J ] . Journal of Molecular Catalysis A: Chem ., 1998 , 139 ( 2 / 3 ): 109 - 119 .

Xue W , Zhang J C , Wang Y J , et al . Effect of promoter copper on the oxidative carbonylation of phenol over the ultrafine embedded catalyst Pd-Cu-O/SiO 2 [J ] . Journal of Molecular Catalysis A: Chemical , 2005 , 232 ( 1 / 2 ): 77 - 81 .

Liang Y H , Guo H X , Chen H P , et al . Effect of doping cerium in the support of catalyst Pd-Co/Cu-Co-Mn mixed oxides on the oxidative carbonylation of phenol [J ] . Chinese Journal of Chemical Engineering , 2009 , 17 ( 3 ): 401 - 406 .

张光旭 , 吴元欣 , 马沛生 , 等 . 非均相催化一步合成碳酸二苯酯（Ⅸ）: Ce的添加方法对Pd-Sn催化剂性能的影响 [J ] . 化工学报 , 2005 , 56 ( 1 ): 82 - 87 .

Zhang G X , Wu Y X , Ma P S , et al . Direct synthesis of diphenyl carbonate with heterogeneous catalysis reaction(Ⅸ): Effect of Ce loading methods on catalytic activity of catalyst [J ] . Journal of Chemical Industry and Engineering (China) , 2005 , 56 ( 1 ): 82 - 87 .

Yang X J , Yin C F , Han J Y , et al . Effect of oxygen species on the liquid product distribution in the oxidative carbonylation of phenol over Pd/M-OMS-2 catalysts [J ] . Reac. Kinet. Mech. Cat ., 2016 , 117 : 269 - 281 .

Spezzati G , Su Y Q , Hofmann J P , et al . Atomically dispersed Pd-O species on CeO 2 (111) as highly active sites for low-temperature CO oxidation [J ] . ACS Catalysis , 2017 , 7 : 6887 - 6891 .

刘逸锋 , 沈本贤 , 皮志鹏 , 等 . CeO 2 表面氧化转移FCC烟气中SO 2 的反应过程 [J ] . 化工学报 , 2016 , 67 ( 12 ): 5015 - 5023 .

Liu Y F , Shen B X , Pi Z P , et al . Oxidation transferring mechanism of SO 2 in FCC flue gas over CeO 2 surface [J ] . CIESC Journal , 2016 , 67 ( 12 ): 5015 - 5023 .

袁烨 , 王志苗 , 安华良 , 等 . Pd-O/CeO 2 纳米管催化苯酚氧化羰基化反应 [J ] . 催化学报 , 2015 , 36 ( 7 ): 1142 - 1152 .

Yuan Y , Wang Z M , An H L , et al . Oxidative carbonylation of phenol with a Pd-O/CeO 2 -nanotube catalyst [J ] . Chinese Journal of Catalysis , 2015 , 36 ( 7 ): 1142 - 1152 .

Luo J Y , Meng M , Xian H , et al . The nanomorphology-controlled palladium-support interaction and the catalytic performance of Pd/CeO 2 catalysts [J ] . Catalysis Letters , 2009 , 133 : 328 - 333 .

Brun M , Berthet A , Bertolini J C . XPS, AES and Auger parameter of Pd and PdO [J ] . Journal of Electron Spectroscopy and Related Phenomena , 1999 , 104 : 55 - 60 .

Wu G W , Wu Y X , Ma P S , et al . Direct synthesis of diphenyl carbonate over heterogeneous catalyst: effects of structure of substituted perovskite carrier on the catalyst activities [J ] . Frontiers of Chemical Science and Engineering in China , 2007 , 1 ( 1 ): 59 - 64 .

张珍容 , 张世英 , 万隆 , 等 . Pd/Ce-HMS介孔材料的结构和表面化学态 [J ] . 化工学报 , 2007 , 58 ( 3 ): 776 - 780 .

Zhang Z R , Zhang S Y , Wan L , et al . Structure and surface chemical state of Pd/Ce containing hexagonal mesoporous silicas [J ] . Journal of Chemical Industry and Engineering (China) , 2007 , 58 ( 3 ): 776 - 780 .

Guimaraes A L , Dieguez D C , Schmal M . The effect of precursors salts on surface state of Pd/Al 2 O 3 and Pd/CeO 2 /Al 2 O 3 catalysts [J ] . Annals of the Brazilian Academy of Sciences , 2004 , 76 ( 4 ): 825 - 832 .

Luo M F , Hou Z Y , Yuan X X , et al . Characterization study of CeO 2 supported Pd catalyst for low temperature carbon monoxide oxidation [J ] . Catalysis Letters , 1998 , 50 ( 3 / 4 ): 205 - 209 .

Sanchez M G , Gazquez J L . Oxygen vacancy model in strong metal-support interaction [J ] . Journal of Catalysis , 1987 , 104 ( 1 ): 120 - 135 .

杨成 , 任杰 , 孙予罕 . CeO 2 和La 2 O 3 改性Pd/r-Al 2 O 3 甲醇低温分解催化剂的研究(Ⅰ): CeO 2 改性Pd/γ-Al 2 O 3 催化剂的结构和性能 [J ] . 催化学报 , 2001 , 22 ( 3 ): 283 - 286 .

Yang C , Ren J , Sun Y H . Study of CeO 2 - and La 2 O 3 -Modified Pd/γ-Al 2 O 3 catalyst for methanol decomposition at low temperature(Ⅰ): Structure and properties of CeO 2 -modified Pd/γ-Al 2 O 3 catalyst [J ] . Chinese Journal of Catalysis , 2001 , 22 ( 3 ): 283 - 286 .

Zhu H Q , Qin Z F , Shan W J , et al . Pd/CeO 2 -TiO 2 catalyst for CO oxidation at low temperature: a TPR study with H 2 and CO as reducing agents [J ] . Journal of Catalysis , 2004 , 225 ( 2 ): 267 - 277 .

Cargnello M , Doan-Nguyen V V T , Gordon T R , et al . Control of metal nanocrystal size reveal metal-support interface role for ceria catalysts [J ] . Science , 2013 , 341 ( 6147 ): 771 - 773 .

Boronin A I , Slavinskaya E M , Danilova I G , et al . Investigation of palladium interaction with cerium oxide and its state in catalysts for low-temperature CO oxidation [J ] . Catalysis Today , 2009 , 144 : 201 - 211 .

Wang Z , Qu Z P , Quan X , et al . Selective catalytic oxidation of ammonia to nitrogen over CuO-CeO 2 mixedoxides prepared by surfactant-templated method [J ] . Applied Catalysis B: Environmental , 2013 , 134 : 153 - 166 .

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

木质素热解油加氢脱氧催化剂耐水性调控的研究进展

载体对单原子电催化剂合成氨性能的影响与调控策略

疏水改性羰基铁负载TiO2光催化降解石油烃污染物

介孔碳负载Ni催化剂催化顺酐加氢反应研究

Pt-Ga/CeO2-ZrO2-Al2O3脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究