还原介质和还原温度对Ru-Zn催化苯选择加氢制环己烯性能的影响

doi:10.16085/j.issn.1000-6613.2016-2247

化工进展 ›› 2017, Vol. 36 ›› Issue (08): 2962-2970.DOI: 10.16085/j.issn.1000-6613.2016-2247

还原介质和还原温度对Ru-Zn催化苯选择加氢制环己烯性能的影响

孙海杰¹, 陈凌霞¹, 黄振旭¹, 孙良玲¹, 李永宇¹, 刘寿长², 刘仲毅²

1. 郑州师范学院化学化工学院, 环境与催化工程研究所, 河南郑州 450044;
2. 郑州大学化学与分子工程学院, 河南郑州 450001

收稿日期:2016-12-05 修回日期:2017-02-28 出版日期:2017-08-05 发布日期:2017-08-05
通讯作者: 李永宇,博士,副教授,主要研究方向为无机纳米材料。
作者简介:孙海杰(1982-),男,博士,讲师。E-mail:sunhaijie406@zznu.edu.cn。
基金资助:
国家自然科学基金（21273205，21543011，U1304204）、河南省科技攻关项目（162102210333）、河南省高等学校重点科研项目（16A150025）及河南省高校科技创新团队支持计划（16IRTSTHN001）项目。

Effect of reduction medium and reduction temperature on the performance of Ru-Zn catalysts for selective hydrogenation of benzene to cyclohexene

SUN Haijie¹, CHEN Lingxia¹, HUANG Zhengxu¹, SUN Liangling¹, LI Yongyu¹, LIU Shouchang², LIU Zhongyi²

1. Institute of Environmental and Catalytic Engineering, Department of Chemistry, Zhengzhou Normal University, Zhengzhou 450044, Henan, China;
2. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2016-12-05 Revised:2017-02-28 Online:2017-08-05 Published:2017-08-05

摘要/Abstract

摘要： 用共沉淀法分别在5% NaOH溶液、蒸馏水、0.035mol/L ZnSO₄溶液和0.145mol/L ZnSO₄溶液中用H₂还原制备了Ru-Zn（5% NaOH）催化剂、Ru-Zn（H₂O）催化剂、Ru-Zn（0.035mol/L ZnSO₄）催化剂和Ru-Zn（0.145mol/L ZnSO₄）催化剂。结果表明，它们催化苯选择加氢制环己烯的活性高低顺序为Ru-Zn（5% NaOH）催化剂 > Ru-Zn（H₂O）催化剂 > Ru-Zn（0.035mol/L ZnSO₄）催化剂≈Ru-Zn（0.145mol/L ZnSO₄）催化剂，环己烯选择性高低顺序与活性顺序正好相反。因为还原介质可以影响Ru-Zn催化剂的组成和织构性质，进而影响它的催化性能。Ru-Zn（H₂O）催化剂的环己烯收率最高，说明蒸馏水作还原介质最好。随还原温度升高，Ru-Zn（H₂O）催化剂比表面积逐渐减小，催化剂活性逐渐降低。同时粒径逐渐增大，Ru粒子上有利于环己烯加氢生成环己烷的楞位和顶点位减少，环己烯选择性升高。在100℃还原温度下制备的Ru-Zn（H₂O）催化剂的环己烯收率可达58.1%。

关键词: 苯, 加氢, 环己烯, 催化剂, 钌, 锌

Abstract: The catalysts of Ru-Zn(5%NaOH),Ru-Zn(H₂O),Ru-Zn(0.035mol/L ZnSO₄) and Ru-Zn(0.145mol/L ZnSO₄) were prepared by H₂ reduction in 5% NaOH,distilled water,0.035mol/L ZnSO₄ and 0.145mol/L ZnSO₄ using a co-precipitation method. The activities of the catalysts for selective hydrogenation of benzene to cyclohexene were in the order of:Ru-Zn(5%NaOH) > Ru-Zn(H₂O) > Ru-Zn(0.035mol/L ZnSO₄)≈Ru-Zn(0.145mol/L ZnSO₄),but their selectivities to cyclohexene were in the inverse order. The reason is that the reduction media could influence the composition and texture properties of the Ru-Zn catalysts,and further affects their catalytic performance. The Ru-Zn(H₂O) catalyst gave the highest cyclohexene yield among these catalysts,suggesting that the distilled water was the best reduction medium. The specific surface of Ru-Zn(H₂O) catalysts decreased with the increase of the reduction temperature,and the activity of the catalysts was lowered. Meanwhile,the particle sizes of the Ru-Zn catalysts increased resulting in the decrease of numbers of the corner sites and the edge sites on the catalysts suitable for hydrogenation of cyclohexene to cyclohexane. Thus the selectivity to cyclohexene increased with the increase of the reduction temperature. The Ru-Zn(H₂O) catalyst reduced at 100℃ gave a cyclohexene yield of 58.1%.

Key words: benzene, hydrogenation, cyclohexene, catalyst, ruthenium, zinc

中图分类号:

O643.38

孙海杰, 陈凌霞, 黄振旭, 孙良玲, 李永宇, 刘寿长, 刘仲毅. 还原介质和还原温度对Ru-Zn催化苯选择加氢制环己烯性能的影响[J]. 化工进展, 2017, 36(08): 2962-2970.

SUN Haijie, CHEN Lingxia, HUANG Zhengxu, SUN Liangling, LI Yongyu, LIU Shouchang, LIU Zhongyi. Effect of reduction medium and reduction temperature on the performance of Ru-Zn catalysts for selective hydrogenation of benzene to cyclohexene[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2962-2970.

参考文献

[1] ZHOU G B,DOU R F,BI H Z,et al. Ru nanoparticles on rutile/anatase junction of P25 TiO₂:controlled deposition and synergy in partial hydrogenation of benzene to cyclohexene[J]. Journal of Catalysis,2015,332:119-126.
[2] SUN H J,DONG Y Y,LI S H,et al. The role of La in improving the selectivity to cyclohexene of Ru catalyst for hydrogenation of benzene[J]. Journal of Molecular Catalysis A:Chemical,2013,368/369:119-124.
[3] 张晔,付海燕,李瑞祥,等. 聚乙二醇稳定的Ru-B纳米粒子催化苯选择加氢为环己烯的性能研究[J]. 无机化学学报,2013,29(3):577-582. ZHANG Y,FU H Y,LI R X,et al. Polyethylene glycol stabilized RuB nanoparticles:an effective catalyst for selective hydrogenation of benzene to cyclohexene[J]. Chinese Journal of Inorganic Chemistry,2013,29(3):577-582.
[4] SUN H J,PAN Y J,LI S H,et al. Selective hydrogenation of benzene to cyclohexene over Ce-promoted Ru catalysts[J]. Journal of Energy Chemistry,2013,22(5):710-716.
[5] 孙海杰,李永宇,李帅辉,等. ZnSO₄和La₂O₃作共修饰剂单金属Ru催化剂上苯选择加氢制环己烯[J]. 物理化学学报,2014,30(7):1332-1340. SUN H J,LI Y Y,LI S H,et al. ZnSO₄ and La₂O₃ as co-modifier of the monoclinic Ru catalysts for selective hydrogenation of benzene to cyclohexene[J]. Acta Physico-Chimica Sinica,2014,30(7):1332-1340.
[6] 孙海杰,周小莉,赵爱娟,等. Zn₄Si₂O₇(OH)₂H₂O盐修饰的纳米Ru催化剂催化苯选择加氢制环己烯[J]. 无机化学学报,2015,31(7):1287-1295. SUN H J,ZHOU X L,ZHAO A J,et al. Selective hydrogenation of benzene to cyclohexene over nano-sized Ru catalyst modified by Zn₄Si₂O₇(OH)₂H₂O[J]. Chinese Journal of Inorganic Chemistry,2015,31(7):1287-1295.
[7] FAN G Y,LI R X,LI X J,et al. Effect of organic additives on partial hydrogenation of benzene[J]. Catalysis Communications,2008,9:1394-1397.
[8] 孙海杰,郭伟,周小莉,等. 非晶态合金Ru基催化剂在苯选择加氢中的应用进展[J]. 催化学报,2011,32(1):1-16. SUN H J,GUO W,ZHOU X L,et al. Progress in Ru-Based amorphous alloy catalysts for selective hydrogenation of benzene to cyclohexene[J]. Chinese Journal of Catalysis,2011,32(1):1-16.
[9] 孙海杰,陈建军,黄振旭,等. 阿拉伯树胶修饰的纳米Ru-Zn催化剂上苯选择加氢制环己烯[J]. 无机化学学报,2016,32(4):202-210. SUN H J,CHEN J J,HUANG Z X,et al. Selective hydrogenation of benzene to cyclohexene over the nano-sized Ru-Zn catalyst modified by Arabic gum[J]. Chinese Journal of Inorganic Chemistry,2016,32(4):202-210.
[10] YAN X H,ZHANG Q,ZHU M Q,et al. Selective hydrogenation of benzene to cyclohexene over Ru-Zn/ZrO₂ catalysts prepared by a two-step impregnation method[J]. Journal of Molecular Catalysis A:Chemical,2016,413:85-93.
[11] ZHANG P,WU T B,JIANG T,et al. Ru-Zn supported on hydroxyapatite as an effective catalyst for partial hydrogenation of benzene[J]. Green Chemistry,2013,15:152-159.
[12] SUN H J,JIANG H B,LI S H,et al. Effect of alcohols as additives on the performance of a nano-sized Ru-Zn(2.8%) catalyst for selective hydrogenation of benzene to cyclohexene[J]. Chemical Engineering Journal,2013,218:415-424.
[13] 孙海杰,陈秀丽,黄振旭,等. NaOH浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响[J]. 化工学报,2016,67(4):1324-1332. SUN H J,CHEN X L,HUANG Z X,et al. Effect of NaOH concentration on performance of Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene[J]. CIESC Jouranl,2016,67(4):1324-1332.
[14] SUN H J,WANG H X,JIANG H B,et al. Effect of (Zn(OH)2)3) (ZnSO₄)(H₂O)5 on the performance of Ru-Zn catalyst for benzene selective hydrogenation to cyclohexene[J]. Applied Catalysis A:General,2013,450:160-168.
[15] 王正宝,张琪,路晓飞,等. 低碱浓度共沉淀制备苯选择加氢Ru-Zn催化剂[J]. 催化学报,2015,36(3):400-407. WANG Z B,ZHANG Q,LU X F,et al. Ru-Zn catalysts for selective hydrogenation of benzene using coprecipitation in low alkalinity[J]. Chinese Journal of Catalysis,2015,36(3):400-407.
[16] 何惠民,袁佩青,马悦铭,等. 苯在Ru-Zn/ZrO₂表面部分加氢反应的理论和实验研究[J]. 催化学报,2009,30(4):312-318. HE H M,YUAN P Q,MA Y M,et al. Theoretical and experimental study on the partial hydrogenation of benzene over Ru-Zn/ZrO₂ catalyst[J]. Chinese Journal of Catalysis,2009,30(4):312-318.
[17] WANG J Q,WANG Y Z,XIE S H,et al. Partial hydrogenation of benzene to cyclohexene on a Ru-Zn/m-ZrO₂ nanocomposite catalyst[J]. Applied Catalysis A:General,2004,272:29-36.
[18] SHEN J Y,ADNOT A,KALIAGUINE S. An ESCA study of the interaction of oxygen with the surface of ruthenium[J]. Applied Surface Science,1991,51(1/2):47-60.
[19] DAKE L S,BAER D R,ZACHARA J M. Auger parameter measurements of zinc compounds relevant to zinc transport in the environment[J]. Surface and Interface Analysis,1989,14(1/2):71-75.
[20] MORETTI G,FIERRO G,LO JACONO M,et al. Characterization of CuO-ZnO catalysts by X-ray photoelectron spectroscopy:precursors,calcined and reduced samples[J]. Surface & Interface Analysis,1989,14(6/7):325-326.
[21] FOLKESSON B. ESCA studies on the charge distribution in some dinitrogen complexes of rhenium,iridium,ruthenium,and osmium[J]. Acta Chemica Scandinavica,1973,27(1):287-302.
[22] WEHWER P S,MERCER P N,APAI G. Interaction of H₂ and CO with Rh₄(CO)12 supported on ZnO[J]. Journal of Catalysis,1983,84(1):244-247.
[23] LANGER D W,VESELY C J. Electronic core levels of zinc chalcogenides[J]. Physical Review B,1970,2(12):4885-4892.
[24] STRUIJK J,D'ANGREMOND M,LUCAS-DE REGT W J M,et al. Partial liquid phase hydrogenation of benzene to cyclohexene over ruthenium catalysis in the presence of an aqueous salt solution[J]. Applied Catalysis A:Genernal,1992,83:263-295.
[25] STRUIJK J,MOENE R,VAN DER KAMP T,et al. Partial liquid-phase hydrogenation of benzene to cyclohexene over ruthenium catalysts in the presence of an aqueous salt solution Ⅱ. Influence of various salts on the performance of the catalyst[J]. Applied Catalysis A:General,1992,89:77-102.
[26] 刘寿长,罗鸽,韩民乐,等. 浸渍法制备的苯部分加氢制环己烯催化剂的表征[J]. 催化学报,2001,22(6):559-562. LIU S C,LUO G,HAN M L,et al. Characterization of the catalyst prepared by impregnation for selective hydrogenation of benzene to cyclohexene[J]. Chinese Journal of Catalysis,2001,22(6):559-562.
[27] LIU J L,ZHU Y,LIU J,et al. Discrimination of the roles of CdSO₄ and ZnSO₄ in liquid phase hydrogenation of benzene to cyclohexene[J]. Journal of Catalysis,2009,268:100-105.
[28] 周功兵,谭晓荷,窦镕飞,等. Ru/ZrO₂ 催化剂在苯部分加氢反应中的粒径效应[J]. 中国科学:化学,2014,44(1):121-130. ZHOU G B,TAN X H,DOU R F,et al. The size effect of the Ru/ZrO₂ catalyst on partial hydrogenation of benzene to cyclohexene[J]. Scientia Sinica Chimica,2014,44(1):121-130.

还原介质和还原温度对Ru-Zn催化苯选择加氢制环己烯性能的影响

Effect of reduction medium and reduction temperature on the performance of Ru-Zn catalysts for selective hydrogenation of benzene to cyclohexene

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