Chemical Industry and Engineering Progress ›› 2018, Vol. 37 ›› Issue (05): 1795-1803.DOI: 10.16085/j.issn.1000-6613.2017-1325
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CHEN Huanzhang1,2, ZHANG Yue1, FENG Xue1, SUN Zhaoli1
Received:
2017-06-30
Revised:
2017-12-04
Online:
2018-05-05
Published:
2018-05-05
陈焕章1,2, 张悦1, 冯雪1, 孙朝利1
通讯作者:
陈焕章(1962-),男,教授,研究方向为固体酸催化剂及精细化学品开发。
作者简介:
陈焕章(1962-),男,教授,研究方向为固体酸催化剂及精细化学品开发。E-mail:chenhuanzhang@yeah.net。
CLC Number:
CHEN Huanzhang, ZHANG Yue, FENG Xue, SUN Zhaoli. Research progress of SO42-/MxOy solid superacid catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(05): 1795-1803.
陈焕章, 张悦, 冯雪, 孙朝利. SO42-/MxOy型固体超强酸催化剂的研究进展[J]. 化工进展, 2018, 37(05): 1795-1803.
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[1] HINO M,ARATA K.Solid catalysts treated with anions.Ⅲ.Reaction of butane to isobutane catalyzed by ironoxide treated with sulfate ion.Solid superacid catalyst[J].Chemistry Letters,1979(10):1259-1260. [2] 刘焘,李利军,黄文艺,等.固体超强酸催化剂SO42-/高岭土制备乙酰丙酸[J].化工进展,2013,32(6):1300-1306. LIU D,LI L J,HUANG W Y,et al.Solid superacid catalyst SO42-/kaolin for preparation of levulinic acid[J].Chemical Industry and Engineering Progress,2013,32(6):1300-1306. [3] ECORMIER M A,WILSON K,LEE A F.Structure-reactivity correlations in sulphated-zirconia catalysts for the isomerisation of α-pinene[J].Journal of Catalysis,2003,215(1):57-65. [4] SOHN J R,SEO D H.Preparation of new solid superacid catalyst,zirconium sulfate supported on γ-alumina and activity for acid catalysis[J].Catalysis Today,2003,87(1/2/3/4):219-226. [5] 付新.固体酸催化剂的研究进展[J].广东化工,2012,39(5):286-287. FU X.Research progress on solid acid catalysts[J].Guangdong Chemical Industry,2012,39(5):286-287. [6] 李佩莹.固体酸催化剂研究近况综述[J].广州化工,2010,38(12):42-44. LI P Y.A review of the current research on solid acid catalysts[J].Guangzhou Chemical Industry,2010,38(12):42-44. [7] 熊森,吴洪特,于兵川.复合固体超强酸催化酯化反应研究进展[J].化学与生物工程,2013(3):10-13. XIONG S,WU H T,YU B C.Research advance on composite solid superacid catalysts applied to esterification reaction[J].Chemistry & Bioengineering,2013(3):10-13. [8] SATOSHI F,HIROMI M,KAZUSHI A,et al.Catalytic action of sulfated tin oxide for etherification and esterification in comparison with sulfated zirconia[J].Applied Catalysis A:General,2004,269:187-191. [9] 陈颖,孙雪,李金莲,等.固体超强酸催化制备生物柴油研究进展[J].化工进展,2009,28(3):383-389. CHEN Y,SUN X,LI J L,et al.Research progress of biodiesel preparation with solid superacid catalysts[J].Chemical Industry and Engineering Progress,2009,28(3):383-389. [10] 颜康,贺新,李树白.固体超强酸SO42-/Fe2O3的制备及其对甲缩醛合成反应的催化性能[J].化学试剂,2017,39(1):75-77. YAN K,HE X,LI S B.Preparation of solid superacid SO42-/Fe2O3 and catalytic performance for synthesis of methylal[J].Chemical Reagents,2017,39(1):75-77. [11] 苏孟兴,刘宏儒,杨儒,等.固体酸SO42-/SnO2的表征及其催化水解反应性能[J].中国油脂,2013,38(8):67-72. SU M X,LIU H R,YANG R,et al.Characterization of solid acid SO42-/SnO2 Sn and its catalytic hydrolysis performance[J].China Oils and Fats,2013,38(8):67-72. [12] 孙群宁,白浩,刘学军.固体酸催化剂的研究进展[J].广东化工,2013,40(23):110-112. SUN Q N,BAI H,LIU X J.The applied and research development of solid acid catalyst[J].Guangdong Chemical Industry,2013,40(23):110-112. [13] 钱祺,王丹雅,王磊,等.硫酸促进型固体超强酸在水预处理条件下的稳定性对比[J].化工学报,2016,67(4):1610-1617. QIAN Q,WANG D Y,WANG L,et al.Comparison on stability of sulfated solid superacid with water pretreatment[J].CIESC Journal,2016,67(4):1610-1617. [14] 汤晓君.介孔SO42-/TiO2固体酸催化合成丙酸丁酯[J].高师理科学刊,2014,34(1):69-72. TANG X J.Synthesis of n-butyl propionate on mesoporous SO42-/TiO2 solid acid[J].Journal of Science of Teachers' College and University,2014,34(1):69-72. [15] 董成,王刚,侯鑫,等.Sol-gel法制备SO42-/ZrO2-SiO2及催化合成对硝基苯甲酸甲酯的研究[J].化学研究与应用,2014,26(4):514-520. DONG C,WANG G,HOU X,et al. Study on SO42-/ZrO2-SiO2 prepared by sol-gel method and its activity on catalytic synthesis of methyl p-nitrobenzoate[J].Chemical Research and Application,2014,26(4):514-520. [16] 陈同云,赵静霞,林宇霖,等.固体酸SO42-/TiO2-La2O3催化合成乙酸正丁酯[J].安徽工业大学学报(自然科学版),2012,29(4):349-352. CHEN T Y,ZHAO J X,LIN Y L,et al.Catalytic synthesis of n-butyl acetate with SO42-/TiO2-La2O3 solid acid[J].Journal of Anhui University of Technology(Natural Science Edition),2012,29(4):349-352. [17] 赵培瑞,李娜,陈茜文,等.改性固体酸SO42-/ZrO2催化合成没食子酸甲酯的研究[J].中南林业科技大学学报,2017,37(6):114-118. ZHAO P R,LI N,CHEN X W,et al.Study on synthesis of methyl gallate catalyzed by modified solid superacid SO42-/ZrO2[J].Journal of Central South University of Forestry & Technology,2017,37(6):114-118. [18] 张学富,赵先锐,陈同云.固体超强酸SO42-/ZrO2-TiO2的声化学制备及表征[J].工业催化,2012,20(2):24-28. ZHANG X F,ZHAO X R,CHEN T Y. Sonochemical preparation and characterization of SO42-/ZrO2-TiO2 solid superacid[J].Industrial Catalysis,2012,20(2):24-28. [19] 陈同云.超声波共沉淀法制备SO42-/Fe2O3-ZrO2固体超强酸及其性能研究[J].合成化学,2007,15(4):494-497. CHEN T Y. Preparation of SO42-/Fe2O3-ZrO2 solid superacid by ultrasonic co-deposition and its performance study[J].Chinese Journal of Synthetic Chemistry,2007,15(4):494-497. [20] 熊森,吴洪特,程玄,等.复合固体超强酸SO42-/TiO2-ZrO2催化合成肉桂酸苄酯[J].山东化工,2016,45(19):23-26. XIONG S,WU H T,CHENG X,et al.Composite solid superacids SO42-/TiO2-ZrO2 catalytic synthesis of benzyl cinnamate esters[J].Shandong Chemical Industry,2016,45(19):23-26. [21] 郑晓凤,于洋,刘海舰.SO42-/TiO2-SnO2固体超强酸无溶剂催化合成季戊四醇硬脂酸酯[J].当代化工研究,2016(7):50-51. ZHENG X F,YU Y,LIU H J.Synthesize pentaerythritol stearate catalyzed by SO42-/TiO2-SnO2 solid superacid without solvent[J]. Contemporary Chemical Industry,2016(7):50-51. [22] 訾俊峰.固体超强酸SO42-/ZrO2-Al2O3的制备及催化酯化反应性能研究[J].许昌学院学报,2011,30(5):87-89. ZI J F.Preparation of magnetic solid superacids SO42-/ZrO2-Al2O3 and research of its catalysis for esterification[J].Journal of Xuchang University,2011,30(5):87-89. [23] 张首才.固体超强酸Al2O3/SO42-催化合成乙酸丙酯[J].松辽学刊(自然科学版),2001(1):63-64. ZHANG S C.Synthesis of propylaectate using Al2O3/SO42- as catalysis[J].Songliao Journal(Natural Science Edition),2001(1):63-64. [24] 赵强,孟双明,郭永,等.复合固体超强酸SO42-/Fe2O3/Al2O3/ZnO/ZrO2催化剂的制备及其催化性能[J].应用化工,2014,43(3):507-509. ZHAO Q,MENG S M,GUO Y,et al.Preparation of solid superacid SO42-/Fe2O3/Al2O3/ZnO/ZrO2 and its catalytic activity property[J].Applied Chemical Industry,2014,43(3):507-509. [25] 刘焘,李利军,刘柳,等.固体超强酸催化剂S2O82-/ZrO2-TiO2-Al2O3制备乙酰丙酸[J].化工进展,2012,31(9):1975-1979. LIU D,LI L J,LIU L,et al.Solid superacid catalyst S2O82-/ZrO2-TiO2-Al2O3 for preparation of levulinic acid[J]. Chemical Industry and Engineering Progress,2012,31(9):1975-1979. [26] 黄凯,鹿可强,倪嵩波.复合固体超强酸催化剂SO42-/ZrO2-Al2O3-WO3的制备及表征[J].武汉科技大学学报,2010,33(6):603-608. HUANG K,LU K Q,NI S B.Preparation and characterization of composite solid superacid catalyst SO42-/ZrO2-Al2O3-WO3[J].Journal of Wuhan University of Science and Technology,2010,33(6):603-608. [27] 范乐明,吕萌,刘凯鸿,等.纳米磁性固体超强酸SO42-/ZrO2-TiO2-Fe3O4催化葡萄糖的甲苷化反应[J].应用化工,2014,43(4):621-624. FAN Y M,LÜ M,LIU K H,et al.Characterization of glucose reaction in methanol by nano-magnetic solid acid SO42-/ZrO2-TiO2-Fe3O4[J]. Applied Chemical Industry,2014,43(4):621-624. [28] 杨阳,李裕.磁性固体超强酸制备及催化合成乙酸正丁酯研究[J].无机盐工业,2015,47(3):68-72. YANG Y,LI Y.Study on the preparation of magnetic solid super acid and catalytic synthesis of n-butyl acetate[J].Inorganic Chemicals Industry,2015,47(3):68-72. [29] 王义刚,聂小安.磁性固体酸催化剂S2O82-/ZrO2-TiO2-Fe3O4的制备及其催化合成乙酰丙酸[J].中南大学学报(自然科学版),2016,47(1):26-32. WANG Y G,NIE X A.Preparation of magnetic solid acid catalyst S2O82-/ZrO2-TiO2-Fe3O4 and its application to synthesis of levulinic acid[J].Journal of Central South University(Natural Science Edition),2016,47(1):26-32. [30] JING H W,WANG X M,LIU Y,et al.Preparation of magnetic nanocomposites of solid acid catalysts and their applicability in esterification[J].Chinese Journal of Catalysis,2015,36(2):244-251. [31] 薛俊礼,程振玉,吉惠杰,等.三元稀土固体超强酸催化剂SO42-/Nd2O3-ZrO2-Fe2O3的制备工艺研究[J].吉林化工学院学报,2015,11:25-29. XUE J L,CHENG Z Y,JI H J,et al.Study on preparation technology of ternary rare earth solid superacid catalyst SO42-/Nd2O3-ZrO2- Fe2O3[J].Journal of Jilin Institute of Chemical Technology,2015,11:25-29. [32] 王来娟,古莉娜.La掺杂对SO42-/ZrO2固体酸催化剂催化性能的影响[J].安徽化工,2015,41(3):20-23. WANG L J,GU L N.Study on catalytic efficiency of La-doped SO42-/ZrO2 solid acid catalyst[J].Anhui Chemical Industry,2015,41(3):20-23. [33] 马惠琴,王卫,马媛媛.La添加对S2O82-/ZrO2-Al2O3固体超强酸催化剂性能的影响[J].石河子大学学报(自然科学版),2014,32(3):360-365. MA H Q,WANG W,MA Y Y.Effect of La content on the catalytic activity of the solid superacid S2O82-/ZrO2-Al2O3[J].Journal of Shihezi University(Natural Science Edition),2014,32(3):360-365. [34] 李三喜,徐妍如,王松.SO42-/TiO2-HZSM-5固体超强酸催化剂的制备及酯化性能[J].化工进展,2015,34(3):745-750. LI S X,XU Y R,WANG S.Preparation of solid superacid SO42-/TiO2-HZSM-5 catalyst and its catalytic performance in esterification[J].Chemical Industry and Engineering Progress,2015,34(3):745-750. [35] 金昌磊.分子筛超强酸SO42-/TiO2/USY催化合成胡萝卜酸乙酯的研究[J].化学研究与应用,2015,27(4):462-465. JIN C L.Study of the synthesis of diethyl malonate with SO42-/TiO2/USY[J].Chemical Research and Application,2015,27(4):462-465. [36] 曾飞虎,林玉香,陈锦辉,等.S2O82-/ZrO2-SiO2固体超强酸的合成及其催化合成硬脂酸正丁酯[J].石油化工,2013,42(2):198-203. ZENG F H,LIN Y X,CHEN J H,et al.Preparation of S2O82-/ZrO2-SiO2 solid super acid catalyst and its activity in synthesis of butyl stearate[J].Petrochemical Technology,2013,42(2):198-203. [37] 吴思展,舒华,陈良为,等.S2O82-/V2O5-CeO2型固体超强酸催化剂的制备研究[J].铜仁学院学报,2011,13(5):136-139. WU S Z,SHU H,CHEN L W,et al.Study on preparation of solid superacid catalyst S2O82-/V2O5-CeO2[J].Journal of Tongren University,2011,13(5):136-139. [38] ZHANG C,LIU T,WANG H J,et al.Synthesis of acetyl salicylic acid over WO3/ZrO2 solid superacid catalyst[J].Chemical Engineering Journal,2011,174(1):236-241. [39] 曹永军.固体酸WO3/TiO2的制备及其催化合成正丁酸己酯[J].应用化工,2011,40(6):978-980. CAO Y J.Preparation of WO3/TiO2 solid acid and synthesis of hexyl butyrate[J].Applied Chemical Industry,2011,40(6):978-980. [40] 孟瑶,李锋,宋华.SO42-/MxOy型固体超强酸酸中心结构及其在轻质烷烃异构化反应中的机理研究进展[J].化工进展,2015,34(11):3906-3914. MENG Y,LI F,SONG H.Advance in surface characteristics of SO42-/MxOy solid superacid and its isomerization mechanisms for light alkane[J].Chemical Industry and Engineering Progress,2015,34(11):3906-3914. [41] MANTILLA A,FERRAT G,LOPEZ-ORTEGA A.et al.Catalytic behavior of sulfated TiO2 in light olefins oligomerization[J].Journal of Molecular Catalysis A:Chemical,2005,228(1/2):333-338. [42] LI X,HUANG W.Synthesis of biodiesel from rap oil over sulfated titania-based solid superacid catalysts[J].Energy Sources,Part A:Recovery,Utilization,and Environmental Effects,2009,31(18):1666-1672. [43] KHDER A S,EL-SHARKAWY E A,EL-HAKAM S A,et al.Surface characterization and catalytic activity of sulfated tin oxide catalyst[J].Catalysis Communications,2008,9(5):769-777. [44] MARCAEWSKI M,KAMINSKA E,MARCZEWSKA H.Decomposition of styrene dimers:the influence of the acid strength of the catalyst[J].Reaction Kinetics,Mechanisms and Catalysis,2013,108(1):59-68. [45] YANG F,LI Y,ZHANG Q,et al.Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO42-/MxOy solid superacid catalyst[J].Carbohydrate Polymers,2015,131:9-14. [46] LEE J S,PARK D S.Interaction of pyridine and ammonia with a sulfate-promoted iron oxide catalyst[J].Journal of Catalyst,1898,120(1):46-54. [47] GARDY J,HASSANPOUR A,LAI X J,et al.Synthesis of Ti(SO4)O solid acid nano-catalyst and its application for biodiesel production from used cooking oil[J].Applied Catalysis A:General,2016,527:81-95. [48] SONG H,ZHAO L L,WANG N,et al.Isomerization of n-pentane over La-Ni-S2O82-/ZrO2-Al2O3 solid superacid catalysts:deactivation and regeneration[J].Applied Catalysis A:General,2016,526:37-44. [49] CHEN H W,WANG B,MA H Z,et al.Oxidation and isomerization of cyclohexane catalyzed by SO42-/Fe2O3-CoO under mild condition[J].Journal of Hazardous Materials,2008,150(2):300-307. [50] 赵彩云,郭燕,刘霞,等.固体超强酸的制备、表征及应用[J].石油化工应用,2014,33(2):8-12. ZAHO C Y,GUO Y,LIU X,et al.The preparation,characterization and application of super solid acid[J].Petrochemical Industry Application,2014,33(2):8-12. [51] LI Y F,SU J J,LI R F.Preparation and characterization of super-microporous alumina with crystalline structure[J].Microporous and Mesoporous Materials,2017,243:9-15. [52] 马允.SO42-/MxOy型固体超强酸催化剂的研究进展[J].应用化工,2014,43(10):1879-1883. MA Y.Advances in SO42-/MxOy solid superacid catalysts[J].Applied Chemical Industry,2014,43(10):1879-1883. [53] 汪颖军,邱学,所艳华,等.复合型SO42-/MxOy型固体超强酸催化剂研究进展[J].工业催化,2011,19(12):7-14. WANG Y J,QIU X,SUO Y H,et al.Research advance on compound SO42-/MxOy solid superacid catalysts[J]. Industrial Catalysis,2011,19(12):7-14. [54] 刘建平,吴丽丽,张俊俊,等.稀土固体超强酸S2O82-/ZrO2-La2O3催化合成柠檬酸三丁酯[J].华东交通大学学报,2015,32(3):108-113. LIU J P,WU L L,ZAHNG J J,et al.Synthesis of tributyl citrate catalyzed by rare earth solid superacid S2O82-/ZrO2-La2O3[J].Journal of East China Jiaotong University,2015,32(3):108-113. [55] 徐培飞,葛利伟,王慧敏.稀土超强酸S2O82-/ZrO2-La2O3催化合成癸二酸二丁酯[J].江西化工,2017(2):44-49. XU P F,GE L W,WANG H M.Synthesis of dibutyl sebacate by S2O82-/ZrO2-La2O3[J].Jiangxi Chemical Industry,2017(2):44-49. [56] 吴兰艳,梁还,满玉,等.固体超强酸催化合成PESA及其阻垢性能研究[J].环境科学与技术,2016,39(11):113-117. WU L Y,LIANG H,MAN Y,et al.Synthesis of polyepoxysuccinic acid with solid superacid catalysts and its scale inhibition[J]. Environmental Science & Technology,2016,39(11):113-117. [57] 赵永庚.改性SO42-/MxOy型固体超强酸在模拟油品深度脱硫中应用研究[D].扬州:扬州大学,2016. ZHAO Y G.Study on the application of modified SO42-/MxOy solid superacid in simulating oil depth desulfurization[D]. Yangzhou:Yangzhou University,2016. [58] XU G,WANG L,CHEN Y J,et al.Highly efficient dynamic kinetic resolution of secondary aromatic alcohols using a low-cost solid superacid as a racemization catalyst[J].Tetrahedron Letters,2013,54(37):2013,5026-5030. [59] SHAH A K,KUMAR M,ABDI S H R,et al.Solvent-free aminolysis of aliphatic and aryloxy epoxides with sulfated zirconia as solid acid catalyst[J].Applied Catalysis A:General,2014,486:105-114. |
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