Pore Size Effect of Ru-Zn/ZrO2 Catalyst on Partial Hydrogenation of Benzene to Cyclohexene

doi:10.6023/A16100569

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (3): 321-328.DOI: 10.6023/A16100569 Previous Articles

Article

Ru-Zn/ZrO₂催化剂在苯部分加氢反应中的孔径效应

周功兵^a, 王浩^b, 裴燕^b, 乔明华^b, 孙斌^c, 宗保宁^c

a 重庆师范大学化学学院绿色合成与应用重点实验室重庆 401331;
b 复旦大学化学系上海市分子催化和功能材料重点实验室上海 200433;
c 中国石化石油化工科学研究院催化材料与反应工程国家重点实验室北京 100083

投稿日期:2016-10-28 修回日期:2017-01-20 发布日期:2017-02-13
通讯作者: 乔明华,E-mail:mhqiao@fudan.edu.cn;宗保宁,E-mail:zongbn.ripp@sinopec.com E-mail:mhqiao@fudan.edu.cn;zongbn.ripp@sinopec.com
基金资助:
项目受国家重点基础研究发展规划项目（No.2012CB224804），国家重点研发专项项目（No.2016YFB0301602），国家自然科学基金（No.21373055），上海市科委科技基金（No.08DZ2270500），北京高能所同步辐射实验室开放课题，重庆市教委科学技术研究项目（No.KJ1500305）及重庆市科委基础与前沿研究计划项目（No.cstc2016jcyjA0392）资助.

Pore Size Effect of Ru-Zn/ZrO₂ Catalyst on Partial Hydrogenation of Benzene to Cyclohexene

Zhou Gongbing^a, Wang Hao^b, Pei Yan^b, Qiao Minghua^b, Sun Bin^c, Zong Baoning^c

a Key Laboratory of Green Synthesis and Applications, College of Chemistry, Chongqing Normal University, Chongqing 401331;
b Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433;
c State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083

Received:2016-10-28 Revised:2017-01-20 Published:2017-02-13
Supported by:
Project supported by the National Key Research Program of China (No. 2012CB224804), the National Key Research and Development Project of China (No. 2016YFB0301602), the National Natural Science Foundation of China (No. 21373055), Science and Technology Commission of Shanghai Municipality (No. 08DZ2270500), Beijing Synchrotron Radiation Facility, the Scientific and Technological Research Program of Chongqing Municipal Education Commission (No. KJ1500305), and the Science & Technology Commission of Chongqing Municipality (No. cstc2016jcyjA0392).

1. Pore Size Effect of Ru-Zn/ZrO₂ Catalyst on Partial Hydrogenation of Benzene to Cyclohexene.PDF(458KB)

Abstract

Partial hydrogenation of benzene to cyclohexene is an important industrial process and features exceptional superiority to processes such as dehydration of cyclohexanol, dehydrogenation of cyclohexane, and the Birch reduction in terms of inexpensive feedstock, succinct reaction route and consequently, improved operational simplicity. In this work, the pore size effect on the partial hydrogenation of benzene to cyclohexene over the Ru-Zn/ZrO₂ catalysts was studied for the first time. Three ZrO₂ supports with the same tetragonal crystallographic form (t-ZrO₂) but different pore sizes were synthesized by the precipitation and the solvothermal methods. Using these ZrO₂ samples, the Ru-Zn/ZrO₂ catalysts were prepared by the deposition-precipitation method followed by reduction in ZnSO₄·7H₂O aqueous solution. The supports and catalysts were characterized by powder X-ray diffraction (XRD), N₂ physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), CO chemisorption, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), temperature-programmed reduction of H₂ (H₂-TPR), and transmission electron microscopy (TEM). It is identified that the Ru nanoparticles (NPs) on these catalysts had similar size and chemical state. In the partial hydrogenation of benzene to cyclohexene, a pronounced pore size effect of the catalyst was identified. With the increase in the pore size, while the turnover frequency (TOF) of benzene was essentially unchanged, the initial selectivity (S₀) to cyclohexene increased steadily. The Ru-Zn/ZrO₂(11.7) catalyst with the ZrO₂ support having the pore size of 11.7 nm exhibited the highest S₀ (88%) and yield (54%) of cyclohexene. On the basis of the characterization results, the similarity in the TOFs of benzene on the Ru-Zn/ZrO₂ catalysts with different pore sizes is associated with the identical sizes of the Ru NPs. On the other hand, we tentatively propose that the ZrO₂ support with large pore size is beneficial for the out-diffusion of the cyclohexene nano-droplets formed in the pore channels, thus avoiding consecutive hydrogenation to cyclohexane and improving the S₀.

Key words: Ru-Zn/ZrO₂, pore size effect, benzene, cyclohexene, hydrogenation

Cite this article

Zhou Gongbing, Wang Hao, Pei Yan, Qiao Minghua, Sun Bin, Zong Baoning. Pore Size Effect of Ru-Zn/ZrO₂ Catalyst on Partial Hydrogenation of Benzene to Cyclohexene[J]. Acta Chim. Sinica, 2017, 75(3): 321-328.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Dou, R. F.; Tan, X. H.; Fan, Y. Q.; Pei, Y.; Qiao, M. H.; Fan, K. N.; Sun, B.; Zong, B. N. Acta Chim. Sinica 2016, 74, 503. (窦镕飞, 谭晓荷, 范义秋, 裴燕, 乔明华, 范康年, 孙斌, 宗保宁, 化学学报, 2016, 74, 503.)
[2] Sun, H. J.; Jiang, H. B.; Li, S. H.; Dong, Y. Y.; Wang, H. X.; Pan, Y. J.; Liu, S. C.; Tang, M. S.; Liu, Z. Y. Chem. Eng. J. 2013, 218, 415.
[3] Sun, H. J.; Wang, H. X.; Jiang, H. B.; Li, S. H.; Liu, S. C.; Liu, Z. Y.; Yuan, X. M.; Yang, K. J. Appl. Catal. A 2013, 450, 160.
[4] Zhang, P.; Wu, T. B.; Jiang, T.; Wang, W. T.; Liu, H. Z.; Fan, H. L.; Zhang, Z. F.; Han, B. X. Green Chem. 2013, 15, 152.
[5] Xu, H. L.; Huang, J. J.; Yang, X. Y.; Du, J. M.; Shen, J.; Shen, W. Acta Chim. Sinica 2006, 64, 1615. (徐华龙, 黄静静, 杨新艳, 杜俊明, 沈江, 沈伟, 化学学报, 2006, 64, 1615.)
[6] Kang, J. C.; Cheng, K.; Zhang, L.; Zhang, Q. H.; Ding, J. S.; Hua, W. Q.; Lou, Y. C.; Zhai, Q. G.; Wang, Y. Angew. Chem. Int. Ed. 2011, 50, 5200.
[7] Liu, Y. C.; Fang, K. G.; Chen, J. G.; Sun, Y. H. Green Chem. 2007, 9, 611.
[8] Zuo, S. F.; Huang, Q. Q.; Zhou, R. X. Catal. Today 2008, 139, 88.
[9] Gelesky, M. A.; Chiaro, S. S. X.; Pavan, F. A.; dos Santos, J. H. Z.; Dupont, J. Dalton Trans. 2007, 5549.
[10] Xia, Q. H.; Hidajat, K.; Kawi, S. Catal. Today 2001, 68, 255.
[11] Wang, J. Q.; Guo, P. J.; Qiao, M. H.; Yan, S. R.; Fan, K. N. Acta Chim. Sinica 2004, 62, 1765. (王建强, 郭平均, 乔明华, 闫世润, 范康年, 化学学报, 2004, 62, 1765.)
[12] Job, N.; Pereira, M. F. R.; Lambert, S.; Cabiac, A.; Delahay, G.; Colomer, J. F.; Marien, J.; Figueiredo, J. L.; Pirard, J. P. J. Catal. 2006, 240, 160.
[13] Preising, H.; Enke, D. Colloids Surf. A 2007, 300, 21.
[14] Zhou, G. B.; Liu, J. L.; Tan, X. H.; Pei, Y.; Qiao, M. H.; Fan, K. N.; Zong, B. N. Ind. Eng. Chem. Res. 2012, 51, 12205.
[15] Zhao, Y. J.; Zhou, J.; Zhang, J. G.; Wang, S. D. J. Mol. Catal. A 2009, 309, 35.
[16] Wang, Z. Q.; Ma, Y. C.; Lin, J. X. J. Mol. Catal. A 2013, 378, 307.
[17] Campbell, P. S.; Santini, C. C.; Bayard, F.; Chauvin, Y.; Collière, V.; Podgoršek, A.; Costa Gomes, M. F.; Sá, J. J. Catal. 2010, 275, 99.
[18] Moulder, J. F.; Stickle, W. F.; Sobol, P. E.; Bomben, K. D. In Handbook of X-ray Photoelectron Spectroscopy, Ed.:Chastain, J., Perkin-Elmer, Minnesota, 1992, p. 89.
[19] Deroubaix, G.; Marcus, P. Surf. Interface Anal. 1992, 18, 39.
[20] Silvestre-Albero, J.; Serrano-Ruiz, J. C.; Sepúlveda-Escribano, A.; Rodríguez-Reinoso, F. Appl. Catal. A 2005, 292, 244.
[21] Lorenzut, B.; Montini, T.; Pavel, C. C.; Comotti, M.; Vizza, F.; Bianchini, C.; Fornasiero, P. ChemCatChem 2010, 2, 1096.
[22] Wang, J. Q.; Wang, Y. Z.; Xie, S. H.; Qiao, M. H.; Li, H. X.; Fan, K. N. Appl. Catal. A 2004, 272, 29.
[23] Yuan, P. Q.; Wang, B. Q.; Ma, Y. M.; He, H. M.; Cheng, Z. M.; Yuan, W. K. J. Mol. Catal. A 2009, 309, 124.
[24] Schwab, F.; Lucas, M.; Claus, P. Angew. Chem. Int. Ed. 2011, 50, 10453.
[25] Schwab, F.; Lucas, M.; Claus, P. Green Chem. 2013, 15, 646.
[26] Zhao, Y. J.; Zhou, J.; Zhang, J. G.; Wang, S. D. Catal. Lett. 2009, 131, 597.
[27] Zhou, X. L.; Sun, H. J.; Guo, W.; Liu, Z. Y.; Liu, S. C. J. Nat. Gas Chem. 2011, 20, 53.
[28] Foppa, L.; Dupont, J. Chem. Soc. Rev. 2015, 44, 1886.
[29] Li, W. Z.; Huang, H.; Li, H. J.; Zhang, W.; Liu, H. C. Langmuir 2008, 24, 8358.
[30] Jung, K. T.; Bell, A. T. J. Mol. Catal. A 2000, 163, 27.
[31] Warren, B. E. J. Appl. Phys. 1941, 12, 375.
[32] Robertson, S. D.; Anderson, R. B. J. Catal. 1971, 23, 286.
[33] Elmasides, C.; Kondarides, D. I.; Grünert, W.; Verykios, X. E. J. Phys. Chem. B 1999, 103, 5227.
[34] Ravel, B.; Newville, M. J. Synchrotron Rad. 2005, 12, 537.
[35] Sun, H. J.; Li, Y. Y.; Li, S. H.; Zhang, Y. X.; Liu, S. C.; Liu, Z. Y.; Ren, B. Z. Acta Phys.-Chim. Sin. 2014, 30, 1332. (孙海杰, 李永宇, 李帅辉, 张元馨, 刘寿长, 刘仲毅, 任保增, 物理化学学报, 2014, 30, 1332.)
[36] Bu, J.; Wang, J. Q.; Qiao, M. H.; Yan, S. R.; Li, H. X.; Fan, K. N. Acta Chim. Sinica 2007, 65, 1338. (卜娟, 王建强, 乔明华, 闫世润, 李和兴, 范康年, 化学学报, 2007, 65, 1338.)
[37] Wang, L. J.; Zhang, A. Q.; Li, L.; Liu, H. F.; Liu, S. Z. Acta Chim. Sinica 2012, 70, 1021. (王丽娟, 张爱清, 李琳, 刘汉范, 刘书正, 化学学报, 2012, 70, 1021.)

Ru-Zn/ZrO₂催化剂在苯部分加氢反应中的孔径效应

Pore Size Effect of Ru-Zn/ZrO₂ Catalyst on Partial Hydrogenation of Benzene to Cyclohexene

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Guoqing Cui, Yiyang Hu, Yingjie Lou, Mingxia Zhou, Yuming Li, Yajun Wang, Guiyuan Jiang, Chunming Xu. Research Progress on the Design, Preparation and Properties of Catalysts for CO₂ Hydrogenation to Alcohols [J]. Acta Chimica Sinica, 2023, 81(8): 1081-1100.
[2]	Xinhong Cai, Jianzhong Chen, Wanbin Zhang. Development of Construction of Chiral C—X Bonds through Nickel Catalyzed Asymmetric Hydrogenation^★ [J]. Acta Chimica Sinica, 2023, 81(6): 646-656.
[3]	Huang Jiapian, Liu Fei, Wu Jie. Recent Advances in the Transformation of Difluorocyclopropenes^★ [J]. Acta Chimica Sinica, 2023, 81(5): 520-532.
[4]	Bin Xu, Xiuzhi Wei, Jiangmin Sun, Jianguo Liu, Longlong Ma. In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin [J]. Acta Chimica Sinica, 2023, 81(3): 239-245.
[5]	Jian Liu, Jinhua Ou, Zeping Li, jingyi Jiang, Rongtao Liang, Wenjie Zhang, kaijian Liu, Yu Han. Efficient Catalytic Hydrogenation of Nitroaromatic Using Cobalt Single-atom Derived from Metal-organic Framework [J]. Acta Chimica Sinica, 2023, 81(12): 1701-1707.
[6]	Luocong Wang, Zhewei Li, Caiwei Yue, Peihuan Zhang, Ming Lei, Min Pu. Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field [J]. Acta Chimica Sinica, 2022, 80(6): 781-787.
[7]	Junmin Chen, Chengqian Cui, Hanlin Liu, Guodong Li. Study on the Selective Hydrogenation of Quinoline Catalyzed by Composites of Metal-Organic Framework and Pt Nanoparticles^※ [J]. Acta Chimica Sinica, 2022, 80(4): 467-475.
[8]	Jun Luo, Lichao Jia, Dong Yan, Jian Li. Performance and Improvement of Ni-based Catalysts for Ethane Dehydrogenation [J]. Acta Chimica Sinica, 2022, 80(3): 317-326.
[9]	Bo Wu, Chong Wang, Baolin Li, Chunru Wang. Light-driven Molecular Magnetic Switch for a Metallofullerene^※ [J]. Acta Chimica Sinica, 2022, 80(2): 101-104.
[10]	Lingling Li, Yu Liu, Shuyan Song, Hongjie Zhang. Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance^※ [J]. Acta Chimica Sinica, 2022, 80(1): 16-21.
[11]	Yeming Wang, Hongwei Wang, Zhaohong Liu. Research Progress on EWG-Substituted N-Arylsulfonylhydrazones as the Diazo Compound Precursor [J]. Acta Chimica Sinica, 2021, 79(9): 1085-1096.
[12]	Yinghui Wang, Simin Wei, Jinwei Duan, Kang Wang. Mechanism of Silyl Enol Ethers Hydrogenation Catalysed by Frustrated Lewis Pairs: A Theoretical Study [J]. Acta Chimica Sinica, 2021, 79(9): 1164-1172.
[13]	Xiaomeng Zhang, Xiya Li, Wanfeng Xiong, Hongfang Li, Rong Cao. Ultrafine Platinum Nanoparticles Derived from Supramolecular Crystal for Catalytic Hydrogenation of Nitroarenes [J]. Acta Chimica Sinica, 2021, 79(2): 180-185.
[14]	Min Zhao, Xue Wang, Yanan Liu, Yufei He, Dianqing Li. Preparation of Efficient Pd/MgAl-LDO@Al₂O₃ Catalyst for Phenol Hydrogenation to Cyclohexanone [J]. Acta Chimica Sinica, 2021, 79(12): 1518-1525.
[15]	Ni Liao, Xia Zhong, Wen-Bin Liang, Ruo Yuan, Ying Zhuo. Metal-organic Frameworks (MOF)-based Novel Electrochemiluminescence Biosensing Platform for Quantification of H₂O₂ Releasing from Tumor Cells [J]. Acta Chimica Sinica, 2021, 79(10): 1257-1264.

Ru-Zn/ZrO2催化剂在苯部分加氢反应中的孔径效应