苯选择加氢制环己烯新型Ru-Zn催化剂的研究
|
摘要
苯选择加氢制环己烯具有原子经济性和环境友好等特点，开展苯选择加氢制环己烯催化剂的研究具有重要的应用价值和一定的学术意义。本论文主要工作是：研究了新型Ru-Zn催化剂的制备方法，并对催化剂进行了表征。主要结论如下：
一、催化剂的制备和操作条件研究：研究了各种因素对沉淀法制备的Ru-Zn催化剂活性选择性的影响，和Fe／Ru比对Ru-Fe催化剂的影响。确定了Ru-Zn和Ru-Fe催化剂的最佳制备条件为：Zn／Ru或Fe／Ru质量比8:92，RuCl_3·xH_2O的浓度为0.18mol·L~(-1)，在70～80℃温度下，将RuCl_3和ZnSO_4·7H_2O或FeSO_4·6H_2O的混合溶液，采用反加法缓慢滴加到过量25％的NaOH溶液中，得到黑色胶状沉淀，继续搅拌10分钟，陈化24h，将沉淀及上清液一并转移至高压釜中。在150℃，5.0MPa，1000r／min还原2h。冷却后取出放置24h，将沉淀洗涤至pH=8±0.5。
催化剂的加氢条件：反应浆液由水、苯、ZnSO_4、催化剂和ZrO_2组成。50mL H_2O，29mL C_6H_6，0.25g Ru-Zn或Ru-Fe催化剂，8.79g ZnSO_4·7H_2O、1.25g ZrO_2。预处理1h。反应条件：150℃，5.0MPa氢气压力，搅拌速率1000r／min。
在上述条件下，在Ru-Zn催化剂上，15min时，苯转化率77.3％，环己烯选择性63.5％，收率49.1％，优于文献报道结果。
二、催化剂的表征。对催化剂进行了活性选择性测定，利用X射线衍射、物理吸附仪，激光粒度分析仪，化学吸附仪等对催化剂进行了表征。XRD给出了Ru-Zn催化剂的晶体和固溶体特征。当Zn／Ru比小于12％时，Ru和Zn以固溶体形式存在；当Zn／Ru比大于15％时，Ru-Zn催化剂体相中观察到零价锌。并从溢流现象和化学反应耦合的观点解释了这一实验事实。XRD半高宽法给出，随着Zn含量的增加，Ru微晶粒径由5.6nm变为4.6nm。BET比表面数据表明，纯Ru催化剂的比表面积(222m~2·g~(-1))比含Zn催化剂(～72m~2·g~(-1))大得多。催化剂上述物性参数的变化是助剂对催化剂活性选择性的影响的原因之一。
The preparation and characterization of a novel Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene have been carried out in this paper. The selective hydrogenation of benzene is of great synthetic and industrial line owing to its atomic economy and clean production; therefore it is very significant to study on these catalysts no matter in industrial application or in theory field.
1 .The preparation conditions of Ru-Zn and Ru-Fe catalyst are as following: The suitable mass ratio of Zn/Ru is 8:92, and the concentration of RuCl_3· xH_2O is about 0.18 mol·L~(-1). At 70~80℃, the mixture of RuCl_3· xH_2O and ZnSO_4 was added drop by drop to a solution of sodium hydroxide (20 wt.% NaOH), leading to a black ruthenium-zinc hydroxide precipitate. Then the precipitate together with the mother liquid was reduced in an autoclave under the conditions of 140℃, hydrogen pressure keeps 5.0 MPa and stirring rate of 1000 r/min for 2h. After reduction, the precipitate was washed thoroughly to pH=8±0.5 .
The optimal operation conditions of the Ru-Zn catalyst are that the reaction temperature is about 140℃, the hydrogen pressure is 5.0 MPa and the stirring rate is 1000 r/min, pretreatment time is 1 h. The suitable composition of the slurry is 50mL H_2O, 29mL C_6H_6, 0.25 g Ru-Zn or Ru-Fe catalyst, 8.79g ZnSO_4-7H_2O and 1.25g ZrO_2.
The Ru-Zn catalyst was used for hydrogenation of benzene under above conditions, at 15 min, the yield of cyclohexene achieve 49.1% at benzene conversion of 77.3%.
2. XRD results show crystal and solid solution character of the catalysts. Zinc exists in its metal state in the catalyst with lower content of zinc, while the content of zinc increasing further, a new phase of zinc is found. Meanwhile it was found that Ru crystallite size decreases from 5.6 nm to 4.6 nm with increase of the content of zinc in the catalyst.
BET results show that activities of the catalysts are relative to their specific surface areas. The larger the specific surface area is, the higher the activity and
一、催化剂的制备和操作条件研究：研究了各种因素对沉淀法制备的Ru-Zn催化剂活性选择性的影响，和Fe／Ru比对Ru-Fe催化剂的影响。确定了Ru-Zn和Ru-Fe催化剂的最佳制备条件为：Zn／Ru或Fe／Ru质量比8:92，RuCl_3·xH_2O的浓度为0.18mol·L~(-1)，在70～80℃温度下，将RuCl_3和ZnSO_4·7H_2O或FeSO_4·6H_2O的混合溶液，采用反加法缓慢滴加到过量25％的NaOH溶液中，得到黑色胶状沉淀，继续搅拌10分钟，陈化24h，将沉淀及上清液一并转移至高压釜中。在150℃，5.0MPa，1000r／min还原2h。冷却后取出放置24h，将沉淀洗涤至pH=8±0.5。
催化剂的加氢条件：反应浆液由水、苯、ZnSO_4、催化剂和ZrO_2组成。50mL H_2O，29mL C_6H_6，0.25g Ru-Zn或Ru-Fe催化剂，8.79g ZnSO_4·7H_2O、1.25g ZrO_2。预处理1h。反应条件：150℃，5.0MPa氢气压力，搅拌速率1000r／min。
在上述条件下，在Ru-Zn催化剂上，15min时，苯转化率77.3％，环己烯选择性63.5％，收率49.1％，优于文献报道结果。
二、催化剂的表征。对催化剂进行了活性选择性测定，利用X射线衍射、物理吸附仪，激光粒度分析仪，化学吸附仪等对催化剂进行了表征。XRD给出了Ru-Zn催化剂的晶体和固溶体特征。当Zn／Ru比小于12％时，Ru和Zn以固溶体形式存在；当Zn／Ru比大于15％时，Ru-Zn催化剂体相中观察到零价锌。并从溢流现象和化学反应耦合的观点解释了这一实验事实。XRD半高宽法给出，随着Zn含量的增加，Ru微晶粒径由5.6nm变为4.6nm。BET比表面数据表明，纯Ru催化剂的比表面积(222m~2·g~(-1))比含Zn催化剂(～72m~2·g~(-1))大得多。催化剂上述物性参数的变化是助剂对催化剂活性选择性的影响的原因之一。
The preparation and characterization of a novel Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene have been carried out in this paper. The selective hydrogenation of benzene is of great synthetic and industrial line owing to its atomic economy and clean production; therefore it is very significant to study on these catalysts no matter in industrial application or in theory field.
1 .The preparation conditions of Ru-Zn and Ru-Fe catalyst are as following: The suitable mass ratio of Zn/Ru is 8:92, and the concentration of RuCl_3· xH_2O is about 0.18 mol·L~(-1). At 70~80℃, the mixture of RuCl_3· xH_2O and ZnSO_4 was added drop by drop to a solution of sodium hydroxide (20 wt.% NaOH), leading to a black ruthenium-zinc hydroxide precipitate. Then the precipitate together with the mother liquid was reduced in an autoclave under the conditions of 140℃, hydrogen pressure keeps 5.0 MPa and stirring rate of 1000 r/min for 2h. After reduction, the precipitate was washed thoroughly to pH=8±0.5 .
The optimal operation conditions of the Ru-Zn catalyst are that the reaction temperature is about 140℃, the hydrogen pressure is 5.0 MPa and the stirring rate is 1000 r/min, pretreatment time is 1 h. The suitable composition of the slurry is 50mL H_2O, 29mL C_6H_6, 0.25 g Ru-Zn or Ru-Fe catalyst, 8.79g ZnSO_4-7H_2O and 1.25g ZrO_2.
The Ru-Zn catalyst was used for hydrogenation of benzene under above conditions, at 15 min, the yield of cyclohexene achieve 49.1% at benzene conversion of 77.3%.
2. XRD results show crystal and solid solution character of the catalysts. Zinc exists in its metal state in the catalyst with lower content of zinc, while the content of zinc increasing further, a new phase of zinc is found. Meanwhile it was found that Ru crystallite size decreases from 5.6 nm to 4.6 nm with increase of the content of zinc in the catalyst.
BET results show that activities of the catalysts are relative to their specific surface areas. The larger the specific surface area is, the higher the activity and
引文
[1] 梁红玉，张连红，姜恒．苯部分加氢制环己烯研究的进展[J]．抚顺石油学院学报．2000，20(2)：34～39
[2] 叶代放，庞先粲，黄仲涛．聚酰胺生产新技术——苯不完全加氢制环己烯的开发研究[J]．高分子通报．1993，(3)：170～177
[3] 张乐，刘振宇，刘寿长．钉催化苯选择加氢制环己烯的研究进展[J]．煤炭转化．2001，24(2)：40～45
[4] 刘寿长．苯部分加氢制环己烯催化技术研究进展[J]．精细与专用化学品．2004，12(24)：4～6
[5] 王东升．苯部分加氢制环己烯[J]．石油化工．1991，20(11)：785～791
[6] R Truffault. Catalytic hydrogenation of aromatic hydrocarbons in liquid media in the presence of nickel black and phosphoric anhydride[J]. Bull.Soc.Chem. 1934, 5(1): 391～406
[7] J R Anderson, C Kemball. Catalytic exchange and deuteration of benzene over evaporated metallic films in a static system[J]. Australian J.Chem. 1957, 10: 409～412
[8] W C Drinkard. Selective catalytic hydrogenation of aromatics to cycloolefins. Germany patent for invention[J]. Germany.often.2,221,139. 7, 1972,11
[9] H Nagahara, M Konishi, U.S.Patent 4,734,536 to Asahi chem. Co. (1988).
[10] 贾继飞，张涛，徐竹生，等．苯选择加氢制环己烯的研究进展[J]．精细石油化工．1997，3(1)：46～50
[11] A M Zhang, J L Dong, Q H Xu. Palladium cluster filled in inner of carbon nanotubes and their catalytic properties in liquid phase benzene hydrogenation [J]. Catal Today. 2004, 93～95:347～352
[12] P J Van der Steen.J.J.F.Scholten. The influence of modified on the Selectivity to cyclohexene in the gas-phase hydrogenation of benzene over ruthenium [A]. In: Int.Congr.Catal.[C],1984.Vering chernie weinheim, Fed Rep Ger: 1985, 659～670
[13] J Q Wang, P J Guo, SRYan, MHQiao, H X Li, K N Fan. Colloidal??RuB/Al_2O_3·xH2O catalyst for liquid phase hydrogenation of benzene to cyclohexene.Journal of Molecular Catalysis A: Chemical 2004, 222:229～234
[14] S H Xie, M H Qiao, et al. A Novel Ru-B/SiO_2 Amorphous Catalyst Used in Benzene-Selective Hydrogenation[J] .Appl.Catal.A, 1999, 176(1):129～134
[15] L Ronchin, L Toniolo. Selective hydrogenation of benzene to cyclohexene catalyzed by Ru supported catalysts Influence of the alkali promoters on kinetics, selectivity and yield[J] .Catalysis Today.2001, 66(2):363～369
[16] Z Liu, W L Dai, B Liu, J F Deng. The Effect of Boron on Selective Benzene Hydrogenation to Cyclohexene over Ruthenium Boride Powders [J] .Journal of Catalysis. 1999, 187(2):253～256
[17] J Q Wang, Y Z Wang, S H Xie, M.H. Qiao, H. X. Li, KN Fan. Partial hydrogenation of benzene to cyclohexene on a Ru-Zn/m-ZrO_2 nanocomposite catalyst[J].Appl.Catal. A 2004, 272(1):29～36
[18] J Q Wang, H.X.Li, et al .Study on the deactivation of amorphous NiB/ZrO_2 catalyst during the selective hydrogenation of cyclopentadiene to cyclopentene[J]. J.Appl.Catal.A:General. 1998, 168(1): 151～157
[19] S Niwa, F Mizukami, S Isoyama , et al . Partial Hydrogenation of Benzene with Ruthenium Catalysts Prepared and Properties of the Catalysts. J Chem Tech Biotechnol, 1986,36:236～246
[20] J Q Wang, H X Li, S H Song, Y J Li, J F Deng. Regeneration at room temperature for amorphous NiB/SiO_2 catalyst deactivated in cyclopentadiene hydrogenation[J].Appl.Catal.A. 1999, 184(1): 33～39
[21] C Milone, G Neri, A Donato, et al. Selective Hydrogenation of Benzene to Cyclohexene on Ru/γ,- Al_2O_3. J Catal, 1996,159 (2) 253～262
[22] 唐雷，石秋杰．钌催化剂上苯加氢制环己烯的影响因素[J]．工业催化．2005，13(7)：7～12
[23] 吴敏，孙作霖，陈志祥等．液相法苯选择加氢制环己烯反应条件的探讨[J]．合成纤维工业．2005，28(3)：5～9
[24] 杨新丽，郭益群，刘寿长．苯选择加氢制环己烯Ru-Co-B／ZrO_2催化剂的研究[J]．化学研究与应用．2003，15(5)：664～666[25] 刘寿长，王海荣，韩民乐，等．高活性高选择性苯部分加氢制环己烯催化的研究[J]．燃料化学学报．2001，29(增刊)：126～129
[26] 王辉，刘仲毅，张洪权，等．苯选择加氢制环己烯非晶合金催化剂Ru-M-B／ZrO_2的失活与再生[J]．催化学报．2005，26(5)：407～411
[27] Milone C, Neri G., Donato A, et al. Selective Hydrogenation of Benzene to cyclohexene on Ru/γ-Al_20_3[J].J.Catal. 1996, 159(2):253～258
[28] CharlesN Satterfield．庞礼等译．实用多相催化，北京大学出版社，1985：86
[29] 李远志，周瑞．负载型非晶态催化剂Ru-B／TiO_2的制备及应用[J]．化学研究与应用．2002，12(6)：614～616
[30] Z Liu, S H Xie,, B Liu, J F Deng. Benzene-Selective Hydrogenation to Cyclohexene over Supported Ruthenium Boride Catalysts Prepared by a Novel Method. New J Chem.,1999, 23:1057～1058
[31] 师瑞娟．间歇法苯选择加氢催化剂中试研究：[硕士学位论文]，2005．
[32] 王建强，郭平均，乔明华，等．Ru／AlOOH催化剂的制备表征及其苯选择加氢反应的研究[J]．化学学报．2004，62(18)：1765～1770
[33] V Spinace Estevam, M Vaz Jorge. Liquid-phase hydrogenation of benzene to cyclohexene catalyzed by Ru/SiO2 in the presence of water-organic mixtures[J]. Catalysis Communications. 2003, (4): 91～96
[34] 王建强，谢颂海，陈海鹰，等．Ru／ZrO_2·xH_2O催化剂的制备及苯选择性加氢反应研究[J]．复旦学报(自然科学版)．2002，41(4)：429～438
[35] 路芳，刘菁，徐杰．负载型钌基催化剂催化苯选择加氢合成环己烯[J]．化学进展．2003，13(4)：338～343
[36] L Ronchin, L Tonilo. Selective hydrogenation of cyclohexene catalyzed by Ru supported catalysts. Influence of the alkali promoters on kinetics, selectivity and yield [J]. Catalysis today. 2001, (66): 363～369
[37] V Mazzieri, F Coloma-Pascual, A Arcoya, P C L'Argentiere, N S Figoli. XPS, FTIR and TPR characterization of Ru/Al_2O_3 catalysts.[J] .Applied Surface Science. 2003, (210): 222～230
[38] S C Liu, Y M Wu, Z Wang. Study of a Ru-La/ ZrO_2 Catalyst Prepared by Precipitation Method for Selective Hydrogenation of Benzene to Cyclohexene??Precipitation Method for Selective Hydrogenation of Benzene to Cyclohexene [J]. Journal of Natural Gas Chemistry. 2005,14(4):226～232
[39] 师瑞娟，刘寿长，王辉，等．沉淀法制备苯选择加氢制环己烯双助剂Ru系催化剂研究[J]．分子催化．2005，19(2)：141～145
[40] H Nagahara, M Ono, Y Fukuoka, et al. Partial hydrogenation of benzene to cyclohexene [J]. Stud.Surf.Sci.Catal., 1995, 92:375～378
[41] M Konishi , H Nagahara. Partial hydrogenation of monocyclic aromanc hydrocarbons[P]. JP 62108826, 1987
[42] H Nagahara, M Konishi. Microcrystalline ruthenium and solid basic zinc sulfatca for manufacture of cyclohexene from benzene [P]. JP 62205037, 1987
[43] R Deguchi, Y Fukuoka. Preparation of cycloolefins by ruthenium-catalysed reduction of monocylic aromanc hydrocarbons[P]. JP 63243039, 1988
[44] H Nagahara, M Konishi. Preparation of cycloolefins from monocylic aromanc hydrocarbons with ruthenium-containing reduction catalysts [P]. JP 6363627, 1988
[45] 刘寿长，罗鸽，谢云龙．沉淀法制备苯选择加氢制环己烯Ru-Zn催化剂的研究[J]．分子催化．2002，16(5)：349～354
[46] 李玉敏．工业催化原理．天津大学出版社，1992．132～133
[47] 韩民乐．苯选择加氢制环己烯Ru催化剂的研究．：[硕士学位论文]，2004．
[48] J Struijk, R Moene, T Vander Kamp, 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]. Appl.Catal. 1992,89:77～102
[49] Y Fukuoka, M Kono, H Nagahara, et al. Reaction Scheme for Partial Hydrogenatian of Benzene with Ruthenium Catalyst—Water System.Nippon Kagaku Kaishi, 1991,227(11 ): 1223～1229(Japan)
[50] M Kono, Y Fukuoka, Mitsui O, et al. Liquid-Phase Hydrogenation of Cyclohexene with Highly Siliceous Zeolites.Nippon Kagaku Kaishi, 1989, 207(3):521～527(Japan)
[51] J Struijk, J J F Scholten. Selectivity Hydrogenation to Cyclohexene in the??Liquid Phase Hydrogenation of Benzene and Toluene over Ruthenium Catalysts, and Infuenced by Reaction Modifiers[J]. Appl. Catal.. 1992, 82:277～287
[52] P J Vander Steen, Scholten J J F. Selectivity to cyclohexene in the gas phase hydrogenation of benzene over ruthenium, as influenced by reaction modifiers[J]. Appl.Catal. 1990, 58(1):291～299
[53] H Nagahara, M Ono, M Konishi, et al. Partial hydrogenation of benzene to cyclohexene [J]. Appl. Surf. Sci. 1997, 121:448～451
[54] C U I Odenbrand, S T Lundin. Hydrogenation of Benzene to cyclohexene on a unsupported Ru catalyst-effect of poisions[J]. J.Chem. 1981, 31 (11):660～669
[55] S Niwa, F Mizukami, Tohe Makoto, et al. Partial hydrogenation of benzene witn ruthenium [J]. Nippon Kagaku Kaishi {Japan}, 1990, (3): 284～290
[56] C U I Odenbrand, S T Lundin. Hydrogenation of benzene to cyclohexene on a ruthenium catalyst: Influence of some reaction parameters [J]. J.Chem. Technol. Biotechnol.,1980, 30(12): 677～687
[57] J Paul, J E David, G David. Arene hydrogenation in a room temperature ionic liquid using a ruthenium claster catalyst [J].Chem. Commun.,1999, 25(2):327～336
[58] 韩民乐，刘寿长，杨笑迪，等．助剂对Ru-B／ZrO_2非晶合金催化剂性能及表面性质的影响[J]．分子催化．2004，1(18)：47～52
[59] 刘寿长，朱伯仲，罗鸽．苯部分加氢制环己烯的非晶态Ru-M-B／ZrO_2催化剂的表征[J]．分子催化．2002，16(3)：217～222
[60] 庞先燊，叶代放，陈凤楼．液相法苯部分加氢制环己烯[J]．石油化工，1994，23(9)：566～571
[61] S C Hu, Y W Chen. Partial Hydrogenation of Benzene on Ru-Zn/SiO_2 catalysts[J]. Ind. Eng. Chem. Res.2001, 40:6099～6104
[62] S C Hu, Y W Chen. Effect of Preparation on Ru-Zn catalysts in Partial Hydrogenation of Benzene[J]. Ind. Eng. Chem. Res.2001, 40:3127～3132
[2] 叶代放，庞先粲，黄仲涛．聚酰胺生产新技术——苯不完全加氢制环己烯的开发研究[J]．高分子通报．1993，(3)：170～177
[3] 张乐，刘振宇，刘寿长．钉催化苯选择加氢制环己烯的研究进展[J]．煤炭转化．2001，24(2)：40～45
[4] 刘寿长．苯部分加氢制环己烯催化技术研究进展[J]．精细与专用化学品．2004，12(24)：4～6
[5] 王东升．苯部分加氢制环己烯[J]．石油化工．1991，20(11)：785～791
[6] R Truffault. Catalytic hydrogenation of aromatic hydrocarbons in liquid media in the presence of nickel black and phosphoric anhydride[J]. Bull.Soc.Chem. 1934, 5(1): 391～406
[7] J R Anderson, C Kemball. Catalytic exchange and deuteration of benzene over evaporated metallic films in a static system[J]. Australian J.Chem. 1957, 10: 409～412
[8] W C Drinkard. Selective catalytic hydrogenation of aromatics to cycloolefins. Germany patent for invention[J]. Germany.often.2,221,139. 7, 1972,11
[9] H Nagahara, M Konishi, U.S.Patent 4,734,536 to Asahi chem. Co. (1988).
[10] 贾继飞，张涛，徐竹生，等．苯选择加氢制环己烯的研究进展[J]．精细石油化工．1997，3(1)：46～50
[11] A M Zhang, J L Dong, Q H Xu. Palladium cluster filled in inner of carbon nanotubes and their catalytic properties in liquid phase benzene hydrogenation [J]. Catal Today. 2004, 93～95:347～352
[12] P J Van der Steen.J.J.F.Scholten. The influence of modified on the Selectivity to cyclohexene in the gas-phase hydrogenation of benzene over ruthenium [A]. In: Int.Congr.Catal.[C],1984.Vering chernie weinheim, Fed Rep Ger: 1985, 659～670
[13] J Q Wang, P J Guo, SRYan, MHQiao, H X Li, K N Fan. Colloidal??RuB/Al_2O_3·xH2O catalyst for liquid phase hydrogenation of benzene to cyclohexene.Journal of Molecular Catalysis A: Chemical 2004, 222:229～234
[14] S H Xie, M H Qiao, et al. A Novel Ru-B/SiO_2 Amorphous Catalyst Used in Benzene-Selective Hydrogenation[J] .Appl.Catal.A, 1999, 176(1):129～134
[15] L Ronchin, L Toniolo. Selective hydrogenation of benzene to cyclohexene catalyzed by Ru supported catalysts Influence of the alkali promoters on kinetics, selectivity and yield[J] .Catalysis Today.2001, 66(2):363～369
[16] Z Liu, W L Dai, B Liu, J F Deng. The Effect of Boron on Selective Benzene Hydrogenation to Cyclohexene over Ruthenium Boride Powders [J] .Journal of Catalysis. 1999, 187(2):253～256
[17] J Q Wang, Y Z Wang, S H Xie, M.H. Qiao, H. X. Li, KN Fan. Partial hydrogenation of benzene to cyclohexene on a Ru-Zn/m-ZrO_2 nanocomposite catalyst[J].Appl.Catal. A 2004, 272(1):29～36
[18] J Q Wang, H.X.Li, et al .Study on the deactivation of amorphous NiB/ZrO_2 catalyst during the selective hydrogenation of cyclopentadiene to cyclopentene[J]. J.Appl.Catal.A:General. 1998, 168(1): 151～157
[19] S Niwa, F Mizukami, S Isoyama , et al . Partial Hydrogenation of Benzene with Ruthenium Catalysts Prepared and Properties of the Catalysts. J Chem Tech Biotechnol, 1986,36:236～246
[20] J Q Wang, H X Li, S H Song, Y J Li, J F Deng. Regeneration at room temperature for amorphous NiB/SiO_2 catalyst deactivated in cyclopentadiene hydrogenation[J].Appl.Catal.A. 1999, 184(1): 33～39
[21] C Milone, G Neri, A Donato, et al. Selective Hydrogenation of Benzene to Cyclohexene on Ru/γ,- Al_2O_3. J Catal, 1996,159 (2) 253～262
[22] 唐雷，石秋杰．钌催化剂上苯加氢制环己烯的影响因素[J]．工业催化．2005，13(7)：7～12
[23] 吴敏，孙作霖，陈志祥等．液相法苯选择加氢制环己烯反应条件的探讨[J]．合成纤维工业．2005，28(3)：5～9
[24] 杨新丽，郭益群，刘寿长．苯选择加氢制环己烯Ru-Co-B／ZrO_2催化剂的研究[J]．化学研究与应用．2003，15(5)：664～666[25] 刘寿长，王海荣，韩民乐，等．高活性高选择性苯部分加氢制环己烯催化的研究[J]．燃料化学学报．2001，29(增刊)：126～129
[26] 王辉，刘仲毅，张洪权，等．苯选择加氢制环己烯非晶合金催化剂Ru-M-B／ZrO_2的失活与再生[J]．催化学报．2005，26(5)：407～411
[27] Milone C, Neri G., Donato A, et al. Selective Hydrogenation of Benzene to cyclohexene on Ru/γ-Al_20_3[J].J.Catal. 1996, 159(2):253～258
[28] CharlesN Satterfield．庞礼等译．实用多相催化，北京大学出版社，1985：86
[29] 李远志，周瑞．负载型非晶态催化剂Ru-B／TiO_2的制备及应用[J]．化学研究与应用．2002，12(6)：614～616
[30] Z Liu, S H Xie,, B Liu, J F Deng. Benzene-Selective Hydrogenation to Cyclohexene over Supported Ruthenium Boride Catalysts Prepared by a Novel Method. New J Chem.,1999, 23:1057～1058
[31] 师瑞娟．间歇法苯选择加氢催化剂中试研究：[硕士学位论文]，2005．
[32] 王建强，郭平均，乔明华，等．Ru／AlOOH催化剂的制备表征及其苯选择加氢反应的研究[J]．化学学报．2004，62(18)：1765～1770
[33] V Spinace Estevam, M Vaz Jorge. Liquid-phase hydrogenation of benzene to cyclohexene catalyzed by Ru/SiO2 in the presence of water-organic mixtures[J]. Catalysis Communications. 2003, (4): 91～96
[34] 王建强，谢颂海，陈海鹰，等．Ru／ZrO_2·xH_2O催化剂的制备及苯选择性加氢反应研究[J]．复旦学报(自然科学版)．2002，41(4)：429～438
[35] 路芳，刘菁，徐杰．负载型钌基催化剂催化苯选择加氢合成环己烯[J]．化学进展．2003，13(4)：338～343
[36] L Ronchin, L Tonilo. Selective hydrogenation of cyclohexene catalyzed by Ru supported catalysts. Influence of the alkali promoters on kinetics, selectivity and yield [J]. Catalysis today. 2001, (66): 363～369
[37] V Mazzieri, F Coloma-Pascual, A Arcoya, P C L'Argentiere, N S Figoli. XPS, FTIR and TPR characterization of Ru/Al_2O_3 catalysts.[J] .Applied Surface Science. 2003, (210): 222～230
[38] S C Liu, Y M Wu, Z Wang. Study of a Ru-La/ ZrO_2 Catalyst Prepared by Precipitation Method for Selective Hydrogenation of Benzene to Cyclohexene??Precipitation Method for Selective Hydrogenation of Benzene to Cyclohexene [J]. Journal of Natural Gas Chemistry. 2005,14(4):226～232
[39] 师瑞娟，刘寿长，王辉，等．沉淀法制备苯选择加氢制环己烯双助剂Ru系催化剂研究[J]．分子催化．2005，19(2)：141～145
[40] H Nagahara, M Ono, Y Fukuoka, et al. Partial hydrogenation of benzene to cyclohexene [J]. Stud.Surf.Sci.Catal., 1995, 92:375～378
[41] M Konishi , H Nagahara. Partial hydrogenation of monocyclic aromanc hydrocarbons[P]. JP 62108826, 1987
[42] H Nagahara, M Konishi. Microcrystalline ruthenium and solid basic zinc sulfatca for manufacture of cyclohexene from benzene [P]. JP 62205037, 1987
[43] R Deguchi, Y Fukuoka. Preparation of cycloolefins by ruthenium-catalysed reduction of monocylic aromanc hydrocarbons[P]. JP 63243039, 1988
[44] H Nagahara, M Konishi. Preparation of cycloolefins from monocylic aromanc hydrocarbons with ruthenium-containing reduction catalysts [P]. JP 6363627, 1988
[45] 刘寿长，罗鸽，谢云龙．沉淀法制备苯选择加氢制环己烯Ru-Zn催化剂的研究[J]．分子催化．2002，16(5)：349～354
[46] 李玉敏．工业催化原理．天津大学出版社，1992．132～133
[47] 韩民乐．苯选择加氢制环己烯Ru催化剂的研究．：[硕士学位论文]，2004．
[48] J Struijk, R Moene, T Vander Kamp, 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]. Appl.Catal. 1992,89:77～102
[49] Y Fukuoka, M Kono, H Nagahara, et al. Reaction Scheme for Partial Hydrogenatian of Benzene with Ruthenium Catalyst—Water System.Nippon Kagaku Kaishi, 1991,227(11 ): 1223～1229(Japan)
[50] M Kono, Y Fukuoka, Mitsui O, et al. Liquid-Phase Hydrogenation of Cyclohexene with Highly Siliceous Zeolites.Nippon Kagaku Kaishi, 1989, 207(3):521～527(Japan)
[51] J Struijk, J J F Scholten. Selectivity Hydrogenation to Cyclohexene in the??Liquid Phase Hydrogenation of Benzene and Toluene over Ruthenium Catalysts, and Infuenced by Reaction Modifiers[J]. Appl. Catal.. 1992, 82:277～287
[52] P J Vander Steen, Scholten J J F. Selectivity to cyclohexene in the gas phase hydrogenation of benzene over ruthenium, as influenced by reaction modifiers[J]. Appl.Catal. 1990, 58(1):291～299
[53] H Nagahara, M Ono, M Konishi, et al. Partial hydrogenation of benzene to cyclohexene [J]. Appl. Surf. Sci. 1997, 121:448～451
[54] C U I Odenbrand, S T Lundin. Hydrogenation of Benzene to cyclohexene on a unsupported Ru catalyst-effect of poisions[J]. J.Chem. 1981, 31 (11):660～669
[55] S Niwa, F Mizukami, Tohe Makoto, et al. Partial hydrogenation of benzene witn ruthenium [J]. Nippon Kagaku Kaishi {Japan}, 1990, (3): 284～290
[56] C U I Odenbrand, S T Lundin. Hydrogenation of benzene to cyclohexene on a ruthenium catalyst: Influence of some reaction parameters [J]. J.Chem. Technol. Biotechnol.,1980, 30(12): 677～687
[57] J Paul, J E David, G David. Arene hydrogenation in a room temperature ionic liquid using a ruthenium claster catalyst [J].Chem. Commun.,1999, 25(2):327～336
[58] 韩民乐，刘寿长，杨笑迪，等．助剂对Ru-B／ZrO_2非晶合金催化剂性能及表面性质的影响[J]．分子催化．2004，1(18)：47～52
[59] 刘寿长，朱伯仲，罗鸽．苯部分加氢制环己烯的非晶态Ru-M-B／ZrO_2催化剂的表征[J]．分子催化．2002，16(3)：217～222
[60] 庞先燊，叶代放，陈凤楼．液相法苯部分加氢制环己烯[J]．石油化工，1994，23(9)：566～571
[61] S C Hu, Y W Chen. Partial Hydrogenation of Benzene on Ru-Zn/SiO_2 catalysts[J]. Ind. Eng. Chem. Res.2001, 40:6099～6104
[62] S C Hu, Y W Chen. Effect of Preparation on Ru-Zn catalysts in Partial Hydrogenation of Benzene[J]. Ind. Eng. Chem. Res.2001, 40:3127～3132