SO_4～（2-）/TiO_2-SiO_2固体超强酸及其催化酯化反应的研究
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摘要
随着绿色化学的倡导,“绿色催化”这一全新的概念摆在了我们的面前。固体超强酸具有高活性、高选择性、低腐蚀、低污染以及容易与反应物分离、可重复利用、热稳定性好等特点,符合绿色催化的要求,因而对固体超强酸的研究成为当前的热点之一。
本文论述了固体超强酸催化剂的研究进展及其在酯化反应中的应用。采用溶胶一凝胶法制备SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂,考察它在乙酸甲酯酯化反应中的催化活性。用正交试验法对催化剂的制备条件进行优化,并对催化剂的酸强度、酸结构进行了系统的研究。具体工作分为三部分进行:
1)催化剂制备及催化活性考察。用正交试验分析得出制备SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂的最佳条件为:钛酸丁酯(TBT)含量为A_1(0.5g),硫酸含量为B_3(1.5m1),焙烧温度为C_1(400℃),钛酸丁酯加入温度为D_2(20℃)。其中焙烧温度对催化剂的催化活性影响最大。
2)采用Hammett指示剂法、TG和IR分析手段对催化剂物性进行表征。结果表明:SO_4~(2-)/ZiO_2-SiO_2催化剂的酸强度最大达-12.70。SO_4~(2-)/TiO_2-SiO_2固体超强酸的酸中心模型是螫合式双配位。
3)对催化剂的失活机理进行讨论,结果表明用于乙酸甲酯酯化反应的SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂失活的主要原因是催化剂表面积碳和SO_4~(2-)流失。
With Green Chemistry being advocated, the brand-new concept of green catalyst has been brought forward recently. Solid superacid has many advantages such as high activity, well selectivity, and no corrosiveness, no pollution, and liability to be separated from the reaction material. It is a green industrial catalyst that is helpful to recycling and possesses wide prospect of application. Thus, research on solid superacid has drawn more and more attention in industrial catalyst field.In this paper, we recounted the recent development of solid supeeracids and their appliance in esterification. The SO_4~(2-)/TiO_2-SiO_2 solid superacid catalyst was prepared by sol-gel method;its catalytic activity was investigated to synthesis of methyl acetate. The reactive condition of catalyst was optimized by orthogonal method. The acid strength and structures of solid superacid catalyst was research. The whole process is divided into three parts which are as follow:1) The examination of catalytic preparation and property. By orthogonal experiments, we have educed SO_4~(2-)/TiO_2-SiO_2 catalytic best preparative conditions: the amount of tetrabutyl titanate is A_1 (0.5g), the amount of vitriol is B_3 (1.5ml), the temperature of calcine is C_1 (400 ℃), the temperature of dripping tetrabutyl titanate is D_2 (20℃) . The temperature of calcine is the maximal influencing factor for catalytic activity of catalysts.2) We have investigated catalytic physical properties by song analytical methods, such as IR, TG and Hammett indicator. Then we have drawn a conclusion: the maximal acid strength of SO_4~(2-)/TiO_2-SiO_2 solid superacid catalyst is -12.70. The acid centre mode of SO_4~(2-)/TiO_2-SiO_2 is chelate structure.3) By discussing the mechanism of catalytic losing activity. We have concluded that the main losing activity reason of SO_4~(2-)/TiO_2-SiO_2 solid superacid catalysts used in synthesis of methyl acetate is the accumulated carbon of catalytic surface and the loss of SO_4~(2-).
本文论述了固体超强酸催化剂的研究进展及其在酯化反应中的应用。采用溶胶一凝胶法制备SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂,考察它在乙酸甲酯酯化反应中的催化活性。用正交试验法对催化剂的制备条件进行优化,并对催化剂的酸强度、酸结构进行了系统的研究。具体工作分为三部分进行:
1)催化剂制备及催化活性考察。用正交试验分析得出制备SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂的最佳条件为:钛酸丁酯(TBT)含量为A_1(0.5g),硫酸含量为B_3(1.5m1),焙烧温度为C_1(400℃),钛酸丁酯加入温度为D_2(20℃)。其中焙烧温度对催化剂的催化活性影响最大。
2)采用Hammett指示剂法、TG和IR分析手段对催化剂物性进行表征。结果表明:SO_4~(2-)/ZiO_2-SiO_2催化剂的酸强度最大达-12.70。SO_4~(2-)/TiO_2-SiO_2固体超强酸的酸中心模型是螫合式双配位。
3)对催化剂的失活机理进行讨论,结果表明用于乙酸甲酯酯化反应的SO_4~(2-)/TiO_2-SiO_2固体超强酸催化剂失活的主要原因是催化剂表面积碳和SO_4~(2-)流失。
With Green Chemistry being advocated, the brand-new concept of green catalyst has been brought forward recently. Solid superacid has many advantages such as high activity, well selectivity, and no corrosiveness, no pollution, and liability to be separated from the reaction material. It is a green industrial catalyst that is helpful to recycling and possesses wide prospect of application. Thus, research on solid superacid has drawn more and more attention in industrial catalyst field.In this paper, we recounted the recent development of solid supeeracids and their appliance in esterification. The SO_4~(2-)/TiO_2-SiO_2 solid superacid catalyst was prepared by sol-gel method;its catalytic activity was investigated to synthesis of methyl acetate. The reactive condition of catalyst was optimized by orthogonal method. The acid strength and structures of solid superacid catalyst was research. The whole process is divided into three parts which are as follow:1) The examination of catalytic preparation and property. By orthogonal experiments, we have educed SO_4~(2-)/TiO_2-SiO_2 catalytic best preparative conditions: the amount of tetrabutyl titanate is A_1 (0.5g), the amount of vitriol is B_3 (1.5ml), the temperature of calcine is C_1 (400 ℃), the temperature of dripping tetrabutyl titanate is D_2 (20℃) . The temperature of calcine is the maximal influencing factor for catalytic activity of catalysts.2) We have investigated catalytic physical properties by song analytical methods, such as IR, TG and Hammett indicator. Then we have drawn a conclusion: the maximal acid strength of SO_4~(2-)/TiO_2-SiO_2 solid superacid catalyst is -12.70. The acid centre mode of SO_4~(2-)/TiO_2-SiO_2 is chelate structure.3) By discussing the mechanism of catalytic losing activity. We have concluded that the main losing activity reason of SO_4~(2-)/TiO_2-SiO_2 solid superacid catalysts used in synthesis of methyl acetate is the accumulated carbon of catalytic surface and the loss of SO_4~(2-).
引文
[1] 姚蒙正,程侣柏,王家儒.精细化工产品合成原理(第二版).北京:中国石化出版社.2000:575-578
[2] 赵立芳,何柱生,王峰期,固体超强酸在酸催化反应中的应用.宝鸡文理学院学报(自然科学版),1999,19(3):68-71
[3] 荒田一志.石油化工译从,1992,(1):9
[4] Barrualt. et al. J Chem Soc Com M. 1988, 21: 1403
[5] 卢文奎,陈庆龄,卢冠忠,毛东森.固体酸代替液体酸催化剂的环境友好新工艺.石油化工,2001,30(2):152-156
[6] 焦肇林,潘慧方,罗明润.稀土氧化物作为邻苯二酸酐和辛醇酯化催化剂的研究.催化学报,1987,8(6):14-16
[7] 李晓莉,杨跃杰,任智英.稀土氧化物(Nd_2O_3)催化合成乙酸乙酯.长春师范学院学报,2000,19(5):1-3
[8] 王恩波,胡长文,许林,等.多酸化学导论.北京:化学工业出版,1997
[9] 段颖波,张绍华,李殿纯,等.固载型杂多酸催化法连续制乙酸乙酯.辽宁化工,1992,(5):3-5
[10] 杨水金,余协卿.固载杂多酸盐TiSiW_(12)O_(40)/TiO_2催化剂合成氯乙酸异丙酯.精细石油化工进展,2000,(1):1-3
[11] 王新平.用杂多酸固载化催化剂催化酯化反应.精细石油化工,1994,(2):15-17
[12] 刘新河.硫酸铁水合物催化合成苯甲酸异戊酯.吉林化工学院学报,2000,17(2):15-16
[13] 邵作范,李明阳.硫酸铁水合物催化合成乙酸酯.辽宁化工,1997,26(5):286-287
[14] 夏泽斌,闰建中,付旭峰等.水合硫酸铁在丙烯酸酯化反应中的催化作用.中南工业大学学报,1996,27(5):620-622
[15] 刘勇,成本诚.酯化反应中的固体酸催化剂.湖南化工,1991,21(3):13-16
[16] Zhang huai-bin. Catalytic property of HZSM-5 in esterification reactions. HuaXueXueBao, 1998, 16(2): 156-161
[17] 李红,杨辉荣,黄承亚.固体超强酸TiO_2/SO_4~(2-)-沸石分子筛催化合成邻苯二甲酸二辛酯.石油化工.1998,27(9):399-401
[18] 赵瑞兰,赵振华,侯雁.用β沸石作催化剂合成丙酸戊酯的研究.湖南师范大学自然科学 学报,2002,25(4):50-54
[19] 鲁波.沈庆扬,等.大孔磺酸型阳离子交换树脂催化合成甲基丙烯酸甲酯.化学反应工程与工艺,1995,11(4):332-335
[20] 赵银,李俊梅.磺酸型阳离子交换树脂催化合成肉挂酸甲酯,离子交换与吸附,1995,11(5):445-448
[21] 丁亮中,罗新湘,俞善信.强酸性阳离子交换树脂催化合成马米酸二异戊酯.合成化学.2002,10(2):156-157,160
[22] [日]田部浩三,御园生诚。等著.郑禄彬,等译.新固体酸和碱及其催化作用.北京:化学工业出版社,1992:2
[23] Hino M.,Reactions of Butane and Isobutane Catalysed by Titanium Oxide Treated with Sulphate Ion. Solid Superacid Catalyst, J. Chem. Soc. Chem. Comm., 1979: 1148
[24] Hino M., Arata K., Synthesis of.Solid Superacid Catalyst with Acid Strength of Ho≤-16.04, J. Chem. Soc. Chem. Comm., 1980, 18: 851
[25] 蒋文伟.超强酸催化剂的研究进展.精细化工.1997,14(1):46-49
[26] 曾健青,罗庆云,王琴,等.SO_4~(2-)/M_mO_n型固体超强酸催化剂的研究进展.石油化工,1994,23(3):191-197
[27] Arata K., Hino M. Synthesis of the Solid Superacid Catalysit of Tinoxide Treated with Sulfate Ion. Appl. Catal, 1990, 59: 205-212
[28] 蒋平平.SO_4~(2-)/ZrO_2超强酸催化活性的研究.化学世界.1994,35(8):411-413
[29] 于世涛,高根之.复合固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化合成DOP的研究.精细化工.1996,13(6):46-49
[30] 王存德.固体超强酸对合成丁乳酸正丁酯的催化活性.化学世界.1993,(7):311-314
[31] 梁世鼓,成本诚.高等有机化学.北京:高等教育出版社.1993.100
[32] 王恩波,胡长文,许林.多酸化学导论.北京:化学工业出版社.1998
[33] 李德庆,米镇涛.固体超强酸催化剂的发展与应用.化工进展.1996,(4):5-10
[34] Matsuhashi H., Hotori H., Arata K. Determination of Acid Strength of Solid Superacid by Temperature Programmed Desorption Using Pyridine. Catal. Lett.1994, 26: 325-328
[35] 高滋,华伟明,陈建民.正戊烷异构化反应表征固体超强酸.物理化学学报.1994,10(10):897-902
[36] Trung Tran M., Gnep N. S., Szabo G., et al. Influence of the Calcination Temperature on the Acidic and Catalytic Properties of Sulfated Zirconia. Appl. Catal. 1998, 27(171): 207-217
[37] Yamaguchi T., et al. Recent Progress in Solid Superacid.Appl. catal. 1990, 61: 1-25
[38] 卢冠忠.固体超强酸的结构及在酯化反应中的应用.工业催化.1993,(1):3-10
[39] 姚胜.M_xO_y/SO_4~(2-)型固体超强酸催化剂,化学通报,1990,2:23-28
[40] Yamaguchi T., Jin T., Ishida L., Tanale K., mater. Chem. phys. 1986, 16: 67
[41] 王新平,唐新硕.沉淀剂对SO_4~(2-)/ZrO_2-NiO催化性能的影响.石油化工,1996,25(1):20-27
[42] Lee J S, Park D S. J.Catal. 1989, 120(1): 53
[43] 高滋,陈建民.用常温正丁烷异构化反应表征固体超强酸性.物理化学学,1994,10(8):698-703
[44] Jin T., Machida M., Yamaguchi T.,et al.Infrared Study of Sulfur Containing Iron Oxide Behaviore of Sulfur during Reduction and Oxidation. Inorg. Chem. 1984, 23: 4396-4398
[45] Yamaguchi T., Jin T., Tanabe K. Structure of Acid sites on Sulfur Promoted iron Oxide. J. Phys.Chem., 1986, 90: 3148-3152
[46] Babou E, Bigot B., Sautet P the Super acidity of Sulfated Zirconia: An ab-initio Guantum Mechanical Study. J. Phys. Chem., 1993, 97: 11501-11509
[47] 刑其毅,徐瑞秋,周政,等.基础有机化学(上册).北京:高等教育出版社.1993,545-547
[48] 胡百华,王琪.乙酸酯化反应催化剂有效酸强度的研究.石油化工,1990,19(3):610
[49] 田部浩三著,催圣范译.超强酸与强碱.北京:化学工业出版社,1986
[50] 裘小宁.SO_4~(2-)/TiO_2-SiO_2固体超强酸的制备及应用.安徽工业大学学报,2005,22(3):246-248,252
[51] T.Lopez, P.Bosch, F.Tzompantzi, R.Gomez, J.Navarrete, E.Lopez-Salinas, M.E.Llanos.Effect of sulfation methods on TiO_2-SiO_2 sol-gel catalyst acidity. App.Catal.A.Gen197(2000)107-117
[52] 陈同云,古绪鹏,胡祥余.低温陈化法制备SO_4~(2-)/ZrO_2-TiO_2超强酸及其催化性能和稳定性研究.无机化学学报.2002,18(4):378-382
[53] 高根之,李慎举.SO_4~(2-)/TiO_2-Al_2O_3-SnO_2催化合成邻苯二甲酸二辛酯(DOP)的研究.山东化工.1997,(1):12-13
[54] 郭锡坤,林绮纯,林维明.固体超强酸催化剂ZrO_2-Dy_2O_3/SO_4~(2-)HZSM-5的制备及结构性能关系的研究.分子催化.2000,14(4):275-279
[55] 金华峰,李文戈.纳米复合固体超强酸SO_4~(2-)/ZnFe_2O_4的制备与催化合成癸二酸二乙酯的研究。无机化学学报.2002,18(3):265-268
[56] 廖世军,杨兆蓓,张小玲,等.SO_4~(2-)/ZrO_2-SiO_2催化剂的制备及其对乙酸/丁醇酯化反应的催化作用,分子催化.1998,12(1):53—58
[57] 尹喜林,陈焕梅.SO_4~(2-)/ZrO_2-TiO_2-SnO_2催化剂的制备及催化性能的研究.石油化工.1994,23(1):22-27
[58] 古绪鹏,陈同云,等.SO_4~(2-)/ZrO_2-TiO_2-La固体酸催化合成乙酸正丁酯.石油化工.2002,31(5):353-356
[59] 卢冠忠,江娴,王筠松.SO_4~(2-)/Ti-Al-O固体超强酸的酸强度及催化性能.催化学报.1995,16(1):21-25
[60] 卢冠忠,江娴,王筠松.多组元SO_4~(2-)/M_xO_y型超强酸催化酯反应的研究.工业催化.1994,2(2):14-18
[61] 夏勇德,华伟明,高滋.S_2O_8~(2-)处理的ZrO_2固体超强酸上的正丁烷异构化反应.化学学报.1999,57(12):1325-1331
[62] 徐景士,周国斌,陈慧宗,等.TiO_2/S_2O_8~(2-)固体超强酸催化长叶烯异构化反应.化学通报.2001,(10):647-650
[63] 张黎,王琳.S_2O_8~(2-)/ZrO_2固体超强酸的研究.高等学校化学学报.2000,21(1):116-119
[64] 张萍,刘鹏.玻璃球负载纳米级SO_4~(2-)/TiO_2固体超强酸的研究.河北工业科技.2003,20(3):46-49
[65] 姜波,张利新,赵立方.陶土负载TiO_2/SO_4~(2-)催化合成丁酸异戊酯.辽宁化工.2003,32(10):426-427,452
[66] 陈建民,缪长喜,等.SO_4~(2-)/ZrO_2固体超强酸储存稳定性研究.高等学校化学学报.1995,17(5):797-799
[67] 高根之,于世涛,杨锦宗.SO_4~(2-)/TiO_2-Al_2O_3-SnO_2催化剂的研制及其催化合成己二酸二辛酯.催化学报.1996,17(1):83-86
[68] 胡正水,王德宝,等.SO_4~(2-)/TiO_2固体超强酸的制备及用于催化酯化反应的研究.青岛化工学院学报.1997,18(4):326-331
[69] 方开泰,马长兴,著.正交与均匀试验设计.科学出版社.2001年出版
[70] 东北工学院数学师资班 编.正交试验法在冶金工业中的应用.冶金工业出版社.1977年10第一版
[2] 赵立芳,何柱生,王峰期,固体超强酸在酸催化反应中的应用.宝鸡文理学院学报(自然科学版),1999,19(3):68-71
[3] 荒田一志.石油化工译从,1992,(1):9
[4] Barrualt. et al. J Chem Soc Com M. 1988, 21: 1403
[5] 卢文奎,陈庆龄,卢冠忠,毛东森.固体酸代替液体酸催化剂的环境友好新工艺.石油化工,2001,30(2):152-156
[6] 焦肇林,潘慧方,罗明润.稀土氧化物作为邻苯二酸酐和辛醇酯化催化剂的研究.催化学报,1987,8(6):14-16
[7] 李晓莉,杨跃杰,任智英.稀土氧化物(Nd_2O_3)催化合成乙酸乙酯.长春师范学院学报,2000,19(5):1-3
[8] 王恩波,胡长文,许林,等.多酸化学导论.北京:化学工业出版,1997
[9] 段颖波,张绍华,李殿纯,等.固载型杂多酸催化法连续制乙酸乙酯.辽宁化工,1992,(5):3-5
[10] 杨水金,余协卿.固载杂多酸盐TiSiW_(12)O_(40)/TiO_2催化剂合成氯乙酸异丙酯.精细石油化工进展,2000,(1):1-3
[11] 王新平.用杂多酸固载化催化剂催化酯化反应.精细石油化工,1994,(2):15-17
[12] 刘新河.硫酸铁水合物催化合成苯甲酸异戊酯.吉林化工学院学报,2000,17(2):15-16
[13] 邵作范,李明阳.硫酸铁水合物催化合成乙酸酯.辽宁化工,1997,26(5):286-287
[14] 夏泽斌,闰建中,付旭峰等.水合硫酸铁在丙烯酸酯化反应中的催化作用.中南工业大学学报,1996,27(5):620-622
[15] 刘勇,成本诚.酯化反应中的固体酸催化剂.湖南化工,1991,21(3):13-16
[16] Zhang huai-bin. Catalytic property of HZSM-5 in esterification reactions. HuaXueXueBao, 1998, 16(2): 156-161
[17] 李红,杨辉荣,黄承亚.固体超强酸TiO_2/SO_4~(2-)-沸石分子筛催化合成邻苯二甲酸二辛酯.石油化工.1998,27(9):399-401
[18] 赵瑞兰,赵振华,侯雁.用β沸石作催化剂合成丙酸戊酯的研究.湖南师范大学自然科学 学报,2002,25(4):50-54
[19] 鲁波.沈庆扬,等.大孔磺酸型阳离子交换树脂催化合成甲基丙烯酸甲酯.化学反应工程与工艺,1995,11(4):332-335
[20] 赵银,李俊梅.磺酸型阳离子交换树脂催化合成肉挂酸甲酯,离子交换与吸附,1995,11(5):445-448
[21] 丁亮中,罗新湘,俞善信.强酸性阳离子交换树脂催化合成马米酸二异戊酯.合成化学.2002,10(2):156-157,160
[22] [日]田部浩三,御园生诚。等著.郑禄彬,等译.新固体酸和碱及其催化作用.北京:化学工业出版社,1992:2
[23] Hino M.,Reactions of Butane and Isobutane Catalysed by Titanium Oxide Treated with Sulphate Ion. Solid Superacid Catalyst, J. Chem. Soc. Chem. Comm., 1979: 1148
[24] Hino M., Arata K., Synthesis of.Solid Superacid Catalyst with Acid Strength of Ho≤-16.04, J. Chem. Soc. Chem. Comm., 1980, 18: 851
[25] 蒋文伟.超强酸催化剂的研究进展.精细化工.1997,14(1):46-49
[26] 曾健青,罗庆云,王琴,等.SO_4~(2-)/M_mO_n型固体超强酸催化剂的研究进展.石油化工,1994,23(3):191-197
[27] Arata K., Hino M. Synthesis of the Solid Superacid Catalysit of Tinoxide Treated with Sulfate Ion. Appl. Catal, 1990, 59: 205-212
[28] 蒋平平.SO_4~(2-)/ZrO_2超强酸催化活性的研究.化学世界.1994,35(8):411-413
[29] 于世涛,高根之.复合固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化合成DOP的研究.精细化工.1996,13(6):46-49
[30] 王存德.固体超强酸对合成丁乳酸正丁酯的催化活性.化学世界.1993,(7):311-314
[31] 梁世鼓,成本诚.高等有机化学.北京:高等教育出版社.1993.100
[32] 王恩波,胡长文,许林.多酸化学导论.北京:化学工业出版社.1998
[33] 李德庆,米镇涛.固体超强酸催化剂的发展与应用.化工进展.1996,(4):5-10
[34] Matsuhashi H., Hotori H., Arata K. Determination of Acid Strength of Solid Superacid by Temperature Programmed Desorption Using Pyridine. Catal. Lett.1994, 26: 325-328
[35] 高滋,华伟明,陈建民.正戊烷异构化反应表征固体超强酸.物理化学学报.1994,10(10):897-902
[36] Trung Tran M., Gnep N. S., Szabo G., et al. Influence of the Calcination Temperature on the Acidic and Catalytic Properties of Sulfated Zirconia. Appl. Catal. 1998, 27(171): 207-217
[37] Yamaguchi T., et al. Recent Progress in Solid Superacid.Appl. catal. 1990, 61: 1-25
[38] 卢冠忠.固体超强酸的结构及在酯化反应中的应用.工业催化.1993,(1):3-10
[39] 姚胜.M_xO_y/SO_4~(2-)型固体超强酸催化剂,化学通报,1990,2:23-28
[40] Yamaguchi T., Jin T., Ishida L., Tanale K., mater. Chem. phys. 1986, 16: 67
[41] 王新平,唐新硕.沉淀剂对SO_4~(2-)/ZrO_2-NiO催化性能的影响.石油化工,1996,25(1):20-27
[42] Lee J S, Park D S. J.Catal. 1989, 120(1): 53
[43] 高滋,陈建民.用常温正丁烷异构化反应表征固体超强酸性.物理化学学,1994,10(8):698-703
[44] Jin T., Machida M., Yamaguchi T.,et al.Infrared Study of Sulfur Containing Iron Oxide Behaviore of Sulfur during Reduction and Oxidation. Inorg. Chem. 1984, 23: 4396-4398
[45] Yamaguchi T., Jin T., Tanabe K. Structure of Acid sites on Sulfur Promoted iron Oxide. J. Phys.Chem., 1986, 90: 3148-3152
[46] Babou E, Bigot B., Sautet P the Super acidity of Sulfated Zirconia: An ab-initio Guantum Mechanical Study. J. Phys. Chem., 1993, 97: 11501-11509
[47] 刑其毅,徐瑞秋,周政,等.基础有机化学(上册).北京:高等教育出版社.1993,545-547
[48] 胡百华,王琪.乙酸酯化反应催化剂有效酸强度的研究.石油化工,1990,19(3):610
[49] 田部浩三著,催圣范译.超强酸与强碱.北京:化学工业出版社,1986
[50] 裘小宁.SO_4~(2-)/TiO_2-SiO_2固体超强酸的制备及应用.安徽工业大学学报,2005,22(3):246-248,252
[51] T.Lopez, P.Bosch, F.Tzompantzi, R.Gomez, J.Navarrete, E.Lopez-Salinas, M.E.Llanos.Effect of sulfation methods on TiO_2-SiO_2 sol-gel catalyst acidity. App.Catal.A.Gen197(2000)107-117
[52] 陈同云,古绪鹏,胡祥余.低温陈化法制备SO_4~(2-)/ZrO_2-TiO_2超强酸及其催化性能和稳定性研究.无机化学学报.2002,18(4):378-382
[53] 高根之,李慎举.SO_4~(2-)/TiO_2-Al_2O_3-SnO_2催化合成邻苯二甲酸二辛酯(DOP)的研究.山东化工.1997,(1):12-13
[54] 郭锡坤,林绮纯,林维明.固体超强酸催化剂ZrO_2-Dy_2O_3/SO_4~(2-)HZSM-5的制备及结构性能关系的研究.分子催化.2000,14(4):275-279
[55] 金华峰,李文戈.纳米复合固体超强酸SO_4~(2-)/ZnFe_2O_4的制备与催化合成癸二酸二乙酯的研究。无机化学学报.2002,18(3):265-268
[56] 廖世军,杨兆蓓,张小玲,等.SO_4~(2-)/ZrO_2-SiO_2催化剂的制备及其对乙酸/丁醇酯化反应的催化作用,分子催化.1998,12(1):53—58
[57] 尹喜林,陈焕梅.SO_4~(2-)/ZrO_2-TiO_2-SnO_2催化剂的制备及催化性能的研究.石油化工.1994,23(1):22-27
[58] 古绪鹏,陈同云,等.SO_4~(2-)/ZrO_2-TiO_2-La固体酸催化合成乙酸正丁酯.石油化工.2002,31(5):353-356
[59] 卢冠忠,江娴,王筠松.SO_4~(2-)/Ti-Al-O固体超强酸的酸强度及催化性能.催化学报.1995,16(1):21-25
[60] 卢冠忠,江娴,王筠松.多组元SO_4~(2-)/M_xO_y型超强酸催化酯反应的研究.工业催化.1994,2(2):14-18
[61] 夏勇德,华伟明,高滋.S_2O_8~(2-)处理的ZrO_2固体超强酸上的正丁烷异构化反应.化学学报.1999,57(12):1325-1331
[62] 徐景士,周国斌,陈慧宗,等.TiO_2/S_2O_8~(2-)固体超强酸催化长叶烯异构化反应.化学通报.2001,(10):647-650
[63] 张黎,王琳.S_2O_8~(2-)/ZrO_2固体超强酸的研究.高等学校化学学报.2000,21(1):116-119
[64] 张萍,刘鹏.玻璃球负载纳米级SO_4~(2-)/TiO_2固体超强酸的研究.河北工业科技.2003,20(3):46-49
[65] 姜波,张利新,赵立方.陶土负载TiO_2/SO_4~(2-)催化合成丁酸异戊酯.辽宁化工.2003,32(10):426-427,452
[66] 陈建民,缪长喜,等.SO_4~(2-)/ZrO_2固体超强酸储存稳定性研究.高等学校化学学报.1995,17(5):797-799
[67] 高根之,于世涛,杨锦宗.SO_4~(2-)/TiO_2-Al_2O_3-SnO_2催化剂的研制及其催化合成己二酸二辛酯.催化学报.1996,17(1):83-86
[68] 胡正水,王德宝,等.SO_4~(2-)/TiO_2固体超强酸的制备及用于催化酯化反应的研究.青岛化工学院学报.1997,18(4):326-331
[69] 方开泰,马长兴,著.正交与均匀试验设计.科学出版社.2001年出版
[70] 东北工学院数学师资班 编.正交试验法在冶金工业中的应用.冶金工业出版社.1977年10第一版