沸石分子筛上四甲苯异构化反应的研究
|
摘要
C10重芳烃中含有大量的混合四甲苯组分,所以采用四甲苯异构化法合成均四甲苯的工艺路线可行。由于Hβ分子筛独特的拓扑结构,使其具有适度的酸性和催化择形性。在催化反应中,表现出不易结焦,催化活性高等优点广泛应用到石油化工领域中。
本文研究了以混合四甲苯为原料生产均四甲苯的工艺流程,异构化反应试验采用Hβ分子筛催化剂,在固定床微型反应实验装置上进行。考察了反应温度、反应压力、体积空速等实验条件对四甲苯异构化反应的影响。得到了最佳工艺条件：反应温度250℃～260℃,反应压力2.0MPa～2.5MPa,体积空速1.4h-1～2.0h-1。
分别采用离子交换、化学液相沉积对Hβ分子筛进行了改性研究,采用XRD、Py-IR、N2物理吸附和NH3-TPD等分析手段对Hβ分子筛改性前后的结构和酸性质进行了表征,评价了改性前后Hβ分子筛对四甲苯异构化合成均四甲苯的催化反应性能,研究了不同改性方法对Hβ分子筛的孔道结构特性、酸性和催化性能的影响规律。
分别用Cu2+、Mo6+和Mg2+对Hβ分子筛进行离子交换改性。研究结果表明,Cu2+、Mo6+、Mg2+交换改性可以调变Hβ分子筛的孔结构特性、酸量及酸强度,在一定程度上均提高了四甲苯异构化反应的催化活性和均四甲苯的选择性及收率。
分别用NiO、P2O5以及二者共同对Hβ分子筛进行化学液相沉积改性。研究结果表明,负载氧化物的Hp分子筛骨架结构未被破坏,氧化物覆盖了分子筛的强酸中心,重新优化了分子筛上B酸与L酸中心的分布。适量的NiO、P2O5以及二者共同沉积改性后Hβ分子筛催化剂显示出较好的催化性能,偏连四甲苯的转化率,均四甲苯的选择性和收率都有不同程度的提高。
C10 aromatic hydrocarbons contains a lot of mixed tetramethylbenzene.So it is feasible to synthesis of durene by mixed tetramethylbenzene isomerization.Hβzeolite has moderate acidity, good thermal stability and shape selectivity because of unique structure. HP is showed hard coking, high catalytic actibity in the catalytic reaction which is used petrochemical industry.
This paper presented a new process for production of durene from mixed tetramethylbenzene. The catalyzed isomerization with the presence of hydrogen occured over Hβzeolite in the fixed-bed microreactor experimental device, which used mixed tetramethylbenzene as raw materials. The effects of reaction temperature, reaction pressure and volume space velocity on the catalytic were investigated.The experimental results show that at the reaction conditions of 250℃～260℃,2.0MPa～2.5MPa, 1.4h-1～2.0h-1.
In this paper, ion exchange and the chemical liquid deposition method were used to modify Hβzeolite. Analytical technique including XRD, Py-IR, N2 physisorption and NH3-TPD were used to characterize the structure and acidity of HP zeolite before and after modification. Catalytic performance of zeolite were evaluated by the isomerization of mixed tetramethylbenzene for synthesis of durene in the fixed-bed microreactor experimental device. The rule of different modified methods to the influence of structure, acidity and catalytic performance for Hβzeolite were studied.
Cu2+、Mo6+ and Mg2+ were used to modify Hβzeolite by ion-exchange method. The results show that pore structure, acid and acid strength of HP zeolite can be modulated and catalytic performance improved by modification of Cu2+、Mo6+ and Mg2+. Largely, modified Hβzeolite echanced conversion of 1,2,3,5-TEMB and 1,2,3,4-TEMEB、selectivity to durene and the yield of durene.
Aqueous solution of NiO、P2O5 and mixed both were used to modify HP zeolite by the chemical liquid deposition method. The results show that the framework structure of loaded oxide to HP zeolite was not destroyed. Modified Hβzeolite covered the acid sites of zeolite and optimized distribution to B and L acid. Hβzeollites modified by proper nickel oxide、phosphorus pentoxide and mixed both exhibited excellent catalytic performance.It was improved the conversion of 1,2,3,5-TEMB and 1,2,3,4-TEMB、the selectivity to durene and the yield of durene.
本文研究了以混合四甲苯为原料生产均四甲苯的工艺流程,异构化反应试验采用Hβ分子筛催化剂,在固定床微型反应实验装置上进行。考察了反应温度、反应压力、体积空速等实验条件对四甲苯异构化反应的影响。得到了最佳工艺条件：反应温度250℃～260℃,反应压力2.0MPa～2.5MPa,体积空速1.4h-1～2.0h-1。
分别采用离子交换、化学液相沉积对Hβ分子筛进行了改性研究,采用XRD、Py-IR、N2物理吸附和NH3-TPD等分析手段对Hβ分子筛改性前后的结构和酸性质进行了表征,评价了改性前后Hβ分子筛对四甲苯异构化合成均四甲苯的催化反应性能,研究了不同改性方法对Hβ分子筛的孔道结构特性、酸性和催化性能的影响规律。
分别用Cu2+、Mo6+和Mg2+对Hβ分子筛进行离子交换改性。研究结果表明,Cu2+、Mo6+、Mg2+交换改性可以调变Hβ分子筛的孔结构特性、酸量及酸强度,在一定程度上均提高了四甲苯异构化反应的催化活性和均四甲苯的选择性及收率。
分别用NiO、P2O5以及二者共同对Hβ分子筛进行化学液相沉积改性。研究结果表明,负载氧化物的Hp分子筛骨架结构未被破坏,氧化物覆盖了分子筛的强酸中心,重新优化了分子筛上B酸与L酸中心的分布。适量的NiO、P2O5以及二者共同沉积改性后Hβ分子筛催化剂显示出较好的催化性能,偏连四甲苯的转化率,均四甲苯的选择性和收率都有不同程度的提高。
C10 aromatic hydrocarbons contains a lot of mixed tetramethylbenzene.So it is feasible to synthesis of durene by mixed tetramethylbenzene isomerization.Hβzeolite has moderate acidity, good thermal stability and shape selectivity because of unique structure. HP is showed hard coking, high catalytic actibity in the catalytic reaction which is used petrochemical industry.
This paper presented a new process for production of durene from mixed tetramethylbenzene. The catalyzed isomerization with the presence of hydrogen occured over Hβzeolite in the fixed-bed microreactor experimental device, which used mixed tetramethylbenzene as raw materials. The effects of reaction temperature, reaction pressure and volume space velocity on the catalytic were investigated.The experimental results show that at the reaction conditions of 250℃～260℃,2.0MPa～2.5MPa, 1.4h-1～2.0h-1.
In this paper, ion exchange and the chemical liquid deposition method were used to modify Hβzeolite. Analytical technique including XRD, Py-IR, N2 physisorption and NH3-TPD were used to characterize the structure and acidity of HP zeolite before and after modification. Catalytic performance of zeolite were evaluated by the isomerization of mixed tetramethylbenzene for synthesis of durene in the fixed-bed microreactor experimental device. The rule of different modified methods to the influence of structure, acidity and catalytic performance for Hβzeolite were studied.
Cu2+、Mo6+ and Mg2+ were used to modify Hβzeolite by ion-exchange method. The results show that pore structure, acid and acid strength of HP zeolite can be modulated and catalytic performance improved by modification of Cu2+、Mo6+ and Mg2+. Largely, modified Hβzeolite echanced conversion of 1,2,3,5-TEMB and 1,2,3,4-TEMEB、selectivity to durene and the yield of durene.
Aqueous solution of NiO、P2O5 and mixed both were used to modify HP zeolite by the chemical liquid deposition method. The results show that the framework structure of loaded oxide to HP zeolite was not destroyed. Modified Hβzeolite covered the acid sites of zeolite and optimized distribution to B and L acid. Hβzeollites modified by proper nickel oxide、phosphorus pentoxide and mixed both exhibited excellent catalytic performance.It was improved the conversion of 1,2,3,5-TEMB and 1,2,3,4-TEMB、the selectivity to durene and the yield of durene.
引文
[1]Lloyd C, Fetterly, El Cerrito, Cakif, et al. Production of Polymethylbenzenes[P]. US2756261,1956-07-24.
[2]Rabo Jule A, et al. Future opportunities in zeolite science and technology[J]. Appl. Catal. A:General.2005,229(1-2):7-10.
[3]李生柱等.国外1,2,4,5-四甲基苯概况[J].化学世界.1996,8(6)：404-408.
[4]丁志平,房鼎业.100t／a均苯四甲酸二酐的技术开发[J].化学工业与工程技术.2003,24(1)：7-10.
[5]伍川,黄培,王晓东等.均四甲苯的制备及应用[J].化工技术与开发.2004,33(3)：24-28.
[6]谭袆生,郭志英等.均四甲苯及其衍生物的国内外现状和应用[J].太化科技.1991,3(3)：11-13.
[7]李敏,张佐光,仲伟虹等.聚酰亚胺树脂研究与应用进展[J].复合材料学报.2000,17(4)：48-53.
[8]崔小明等.均苯四甲酸二酐的生产及应用[J].化工中间体.2002,3(4)：14-15.
[9]仓理,杨晓东等.均苯四甲酸二酐的生产及其在涂料工业中的应用[J].涂料工业.2007,37(12)：33-36.
[10]赵帆,张刚等.均苯四甲酸二酐的性质及应用[J].精细石油化工.1998(4)：53-55.
[11]Scott J W, Ross Jr, Luthy R V. Production of Durene from Fractions containing Polyalkyl Benzenes Having 9 to 10 Carbon atoms per Molecule[P]. US2910514, 1959-10-27.
[12]张春雷,巢花庆,肖致亮等.芳烃化学与芳烃生产[M].长春：吉林大学出版社.2000,289-321.
[13]庞金铭,张绍军,许长春等.重整碳十重芳烃综合利用工艺及装置.CN1094388A,1994-11-02.
[14]Sanford R A, Forest P, et al. Process for Producing Durene[P]. US2874200, 1959-02-17.
[15]李慧民,叶照坚,张国华等.偏四甲苯液相异构化制均四甲苯[J].化学与粘合.1992(2)：72-76.
[16]Becker, Karl, Dr.Dipl.Chem, Berrouschot, Hans-Dieter, et al. Verfahren zur Isomerisierung von Tetramethylbenzolen. DL(east),137703.1979-09-19.
[17]Becker, Karl, Jauch, Ruth, Karl-Klaus, Ramhold, Dr.Dipl-Chem. Verfahren zur Isomerisierung von Tetramethylbenzolen. DL(east),137704.1979-09-19.
[18]张岱山等.偏四甲苯连四甲苯异构化制备均四甲苯概述[J].精细石油化工.1988,12(2)：22-24.
[19]赵敏杰等.C10芳烃中四甲苯异构化制备均四甲苯[J].精细石油化工.2006,23(6)：4-6.
[20]赵开鹏,韩松等.重整C10芳烃的综合利用[J].石油化工.2000,4(3)：298-302.
[21]Tatsuaki Y, Namba S, Inaka A. Selectivity alkylation of 1,2,4-trimethybenzene with methanol on modified HZSM-5 type zeolite catalysts[J].Stud Surf Sci Catal. 1985,28(6):498-502.
[22]Kaoru O, Akio F, Yashima Y. Selective Synthesis of Acetylene from Methane by Microwave Plasma Reation[J]. Fuel.1997,76(3):281-282.
[23]Peng W, Takayukik K, Tatsuaki Y, et al. Ammoxi mation of ketones over titanium Mordenite[J]. Journal of Catalysis.1997,168(1):400-411.
[24]Lugstein A, Jentys A, Vinek H. Hydroconversion of n-heptane over bifunctional HZSM-5 zeolites Influence of the metal concentration and distribution on the activity and selectivity[J]. Applied Catalysis General.1998,166(5):29-38.
[25]陶克毅,王玲,藏雅茹等.无机氟改性的HZSM-5分子筛催化1,2,4—三甲苯与甲醇烷基化合成1,2,4,5-四甲苯的研究[J].化学工业与工程.1995,12(2)：9-13.
[26]金宏等.偏三甲苯—甲醇烷基化制均四甲苯的研究[J].金陵石油化工.1992,8(4)：1-4.
[27]丁瑛,孙滔,赵开鹏等.混合三甲苯制均三甲苯联产均四甲苯[J].石油炼制与化工.1990,6(5)：25-29.
[28]李栋潘,贾定先,张盈珍等.含锆层柱蒙脱石对1,2,4-三甲苯歧化反应的催化作用[J].催化学报.1998,19(1)：58-62.
[29]Jone W, Tennakoon D, Tilak B, Thomas J M. Structural aspects of metal-oxide-pillared sheet silicates. An investigation by magic-angle-spinning nuclear magnetic resonance, fourier-transform infrared spectroscopy and powder X-ray diffractometry[J]. J Chem Soc, Faraday Trans 1,1986(10):3081-3095.
[30]Schezer J, et al. Catakytuc Materials:Relation between structure and reactivity [C]. In:ACS Symp Ser 248. Am Chem Soc, Washington D C,1984,57:26-33.
[31]Wadlinger R L, Kerr G T, Risubski E J. Catalytic composition of a crystalline zeolite[P]. US3308069,1967-03-07.
[32]Martens J A, Tielen M, Jacobas P A, Weitkamp J. Estimation of the void structure and pore dimensions of molecular sieve zeolites using the hydroconversion of n-decane[J]. Zeolites,1984,4(2):98-107.
[33]Martens J A, Jacbs P A, et al. The potential and limitations of the n-decane hydroconversion as a test reaction for characterization of the void space of molecular sieve zeolites[J]. Zeolites,1986,6(5):334-338.
[34]Newsan J M, Treacy M M J, Koetsier W T, De Gruyter C B, et al. Structural characterization of zeolite beta[J]. Proc.R.Soc.Lond.1988,A420,375-405.
[35]孟宪平,王颖霞,林炳雄,韦承谦,张婉静.p沸石堆垛层错结构的研究[J].物理化学学报.1996,12(8)：727-734.
[36]Higgins J B, Lapierre R B,Schlenker J L,Rohrman AC, Wood J D, et al. The framework topology of Zeolite Beta-A Correction[J]. Zeolites,1989,9,358-363.
[37]周峰,李广站等.p沸石的合成研究[J].山东冶金,2007,29(6)：55-57.
[38]王桂茹,王安杰,刘靖,郭新闻等.催化剂与催化作用[M].大连：大连理工大学出版社.2004,67.
[39]Emiis C A, et al. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. J Catal. 1993,141:347-354.
[40]Takeshi Sugii, Ryuichiro Ohnishi, Jin Zhang, Toshio Okuhara. Acidity-attenuated heteropolyacid catalysts:Acidity measurement using benzonitrile-TPD and catalytic performance in the skeletal isomerization of n-heptane[J]. Catalysis Today.2006,116(2):179-183.
[41]Kumar N, Masloboischikova O V, Kustov L M, Heikkila T, et al. Synthesis of Pt modified ZSM-5 and Beta zeolite catalysts:Influence of ultrasonic irradiation and preparation methods on physico-chemical and catalytic properties in pentane isomerization[J]. Ultrasonics Sonochemistry.2007,14:122-130.
[42]Tingfang Hu, Jingpeng Chen, Haiyan Wang. Influence of shaped and modified Hβ zeolite on etherification of FCC light gasoline[J]. Micr. Mes. Mater.2006, 94:283-287.
[43]Zekai Zhang, Shenglin Liu, Xiangxue Zhu, Qingxia Wang, Longya Xu. Modification of Hβ zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline[J].Fuel.2008,89:103-110.
[44]梁必超,杨德琴,孔德金,施力等.Hβ和SiO2负载磷钨酸催化剂用于甲苯和均三甲苯反应制备二甲苯的催化性能[J].华东理工大学学报.2008,34(3)：315-318.
[45]王华,黄韬,杜鹃,刘中民等.通过Hβ分子筛上的烯烃水合反应提高FCC汽油品质[J].催化学报.2005,26(6)：451-452.
[46]Alexandre F, Costa, Henrique S. Cerqueira. BEA and MOR as additivies for light olefins production[J]. Applied Catalysis A:General,2007,319:137-413.
[47]Sharath R K, Nagaraju N, Komandur V R Chary. Esterification of alcohols with acetic acid over zeolites Hβ, HY and HZSM-5[J]. Appl Catal A:Gen,2006,299: 185-192.
[48]Halgeri A B, Das J, Bhat Y S, Bhardwaj A I. Zeolite beta catalyzed C7 and C9 aromatics transformation[J]. Appl Catal A:General. 1994,116,71-79.
[49]Pokhriyal S K, Ratnasamy P, Bhat R N, Hegde S G, et al. Reactions of Aromatic Hydrocarbons over Zeolite β[J]. J Catal.1989,119,65-70.
[50]陈庆龄,张成芳,谢在库,刘红星等.Hβ沸石上甲苯歧化和C9芳烃烷基转移反应[J].华东理工大学学报.2005,26(3)：260-264.
[51]Tsai T C, Wang I, Huang S T, et al. Disproportionation of Toluene and of Trimethylbenzene and Their Transalkylation over Zeolite Beta[J]. Ind.Eng. Chem.Res.1990,29,2005-2012.
[52]Komatsu T, Wang Z B, Kamo A, et al. Isomerization of n-heptane over Pt-loaded zeolite β catalysts[J]. Appl.Catal.A:General.1997,159,119-132.
[53]庞新梅,高晓慧,张莉,石晓庆,周至远,曹庚振.β沸石的催化裂化反应性能[J].石油学报,2009,16(3)：77-79.
[54]Ramaswamy A V, Venkatesan C, Jaimol T, Moreau P, Finiels A. Liquid phase selective benzoylation of chlorobenzene to 4,4'-dichlorobenzophenone over Zeolite H-Beta[J]. Catalysis Letters.2007,75(1-2):119-123.
[55]石晓庆,李萍,张莉,庞新梅,王宝杰.几种β分子筛在催化裂化催化剂中的应用研究[J].石化技术.2008,15(3)：6-9.
[56]Tomonobu T, Fujimoto K, Ge Q, et al. Influence of Pd ion-exchange temperature on the catalyticperformance of Cu-ZnO/Pd-β zeolite hybrid catalyst for CO hydrogenation to light hydrocarbons[J]. Catal.Commun,2008,9:1775-1778.
[57]Ping Liu, Xinggung Zhang, Yue Yao, Jun Wang. Pt catalysts supported on β zeolite ion-exchanged with Cr(Ⅲ) for hydroisomerization of n-heptane[J]. Applied Catalysis A:General,2009,371:142-147.
[58]刘金龙,王国良,秦如意,李树本等.改性对β沸石表面酸性及丙烯水合醚化反应性能的影响[J].燃料化学学报.2002,30(4)：353-357.
[59]杨伯伦,路士庆,吴江,王华军等.镧改性β分子筛上的异丁烯水合醚化复 合反应[J].催化学报.2007,28(1)：73-79.
[60]Jim Schwarz, Adriana Contescu, Cristian Contescu. Methods for Preparation of Catalytic Materials[J]. Chem Rev.1995,95:477-510.
[61]申群兵,朱学栋,董娇娇,吴勇强,朱子彬.载钼分子筛催化剂上C9+重芳烃的轻质化[J].石油学报.2009,25(3)：351-357.
[62]Huifeng Li, Mingfeng Li, Yang Chu, Hong Nie. Influence of different modified β zeolite on skeletal isomerization of n-hexene in the presence of hydrogen[J]. Microporous and Mesoporous Materials.2009,117:635-639.
[63]Kenichi Komura, Qiu Jun, Yoshihiro Kubota, Yoshihiro Sugi, et al. Synthesis of Cyclohexylbenzene by Hydroalkylation of Benzene over Pd/Hβ Binary Catalyst [J].Chin J Catal,2007,28(3):246-250.
[64]谷峰,孟禹,王海彦,魏民等.改性p沸石负载碳化钼催化剂上正己烷的异构化[J].石油与天然气化工.2009,38(2)：96-99.
[65]李承烈等.烃类异构化[M].北京：中国石化出版社.1992,123-130.
[66]Guisnet M, Gnep N S, Morin S, et al. Mechanisms of xylene isomerization over acidic solid catalysts[J]. Microporous and Mesopruus Materials,2006,35:47-49.
[67]曹声春,胡艾希等.催化原理及其工业应用技术.长沙：湖南大学出版社.2001.151-152.
[68]Zhang W.M., P.G Smirniotis, M.Gangoda, et al. Brφnsted and Lewis Acid Sites in Dealuminated Zeolites Characterized by NH3-TPD,FT-IR,and MAS NMR Spectroscopy[J]. J.Phys.Chem.2000,104:4122-4129.
[69]Motoyuki Masahiro, Yamamoto Koji. Process for preparing dialkynaphthalene[P]. US5844064(A)-1998-12-01.
[70]Romero M D, Calles J A, Rodriguez A, et al. Influence of the preparation method and mental precursor compound on the bifunctional Ni/HZSM-5 Catalysts[J]. Ind.Eng.Chem.Res.1997,36:3533-3540.
[71]Minchev C, Zubkov C, Valtcher V, et al. Nature of actuve sites and catalytic activity of SAPO-5 synthesized in the presence of nickel cations[J]. Appl.Catal. 1994,119:195-201.
[72]张铭金.沸石分子筛催化剂上萘择形烷基化基础研究：[博士学位论文],中国科学院山西煤炭化学研究所,山西：2000.
[73]Pekka Tynjala, Tuula T, Pakkanen, et al. Modification of ZSM-5 zeolite with Trimethyl phosphate Part 1. structure and acidity[J]. Microporous and Mesoporous Materials,1998,20:363-369.
[2]Rabo Jule A, et al. Future opportunities in zeolite science and technology[J]. Appl. Catal. A:General.2005,229(1-2):7-10.
[3]李生柱等.国外1,2,4,5-四甲基苯概况[J].化学世界.1996,8(6)：404-408.
[4]丁志平,房鼎业.100t／a均苯四甲酸二酐的技术开发[J].化学工业与工程技术.2003,24(1)：7-10.
[5]伍川,黄培,王晓东等.均四甲苯的制备及应用[J].化工技术与开发.2004,33(3)：24-28.
[6]谭袆生,郭志英等.均四甲苯及其衍生物的国内外现状和应用[J].太化科技.1991,3(3)：11-13.
[7]李敏,张佐光,仲伟虹等.聚酰亚胺树脂研究与应用进展[J].复合材料学报.2000,17(4)：48-53.
[8]崔小明等.均苯四甲酸二酐的生产及应用[J].化工中间体.2002,3(4)：14-15.
[9]仓理,杨晓东等.均苯四甲酸二酐的生产及其在涂料工业中的应用[J].涂料工业.2007,37(12)：33-36.
[10]赵帆,张刚等.均苯四甲酸二酐的性质及应用[J].精细石油化工.1998(4)：53-55.
[11]Scott J W, Ross Jr, Luthy R V. Production of Durene from Fractions containing Polyalkyl Benzenes Having 9 to 10 Carbon atoms per Molecule[P]. US2910514, 1959-10-27.
[12]张春雷,巢花庆,肖致亮等.芳烃化学与芳烃生产[M].长春：吉林大学出版社.2000,289-321.
[13]庞金铭,张绍军,许长春等.重整碳十重芳烃综合利用工艺及装置.CN1094388A,1994-11-02.
[14]Sanford R A, Forest P, et al. Process for Producing Durene[P]. US2874200, 1959-02-17.
[15]李慧民,叶照坚,张国华等.偏四甲苯液相异构化制均四甲苯[J].化学与粘合.1992(2)：72-76.
[16]Becker, Karl, Dr.Dipl.Chem, Berrouschot, Hans-Dieter, et al. Verfahren zur Isomerisierung von Tetramethylbenzolen. DL(east),137703.1979-09-19.
[17]Becker, Karl, Jauch, Ruth, Karl-Klaus, Ramhold, Dr.Dipl-Chem. Verfahren zur Isomerisierung von Tetramethylbenzolen. DL(east),137704.1979-09-19.
[18]张岱山等.偏四甲苯连四甲苯异构化制备均四甲苯概述[J].精细石油化工.1988,12(2)：22-24.
[19]赵敏杰等.C10芳烃中四甲苯异构化制备均四甲苯[J].精细石油化工.2006,23(6)：4-6.
[20]赵开鹏,韩松等.重整C10芳烃的综合利用[J].石油化工.2000,4(3)：298-302.
[21]Tatsuaki Y, Namba S, Inaka A. Selectivity alkylation of 1,2,4-trimethybenzene with methanol on modified HZSM-5 type zeolite catalysts[J].Stud Surf Sci Catal. 1985,28(6):498-502.
[22]Kaoru O, Akio F, Yashima Y. Selective Synthesis of Acetylene from Methane by Microwave Plasma Reation[J]. Fuel.1997,76(3):281-282.
[23]Peng W, Takayukik K, Tatsuaki Y, et al. Ammoxi mation of ketones over titanium Mordenite[J]. Journal of Catalysis.1997,168(1):400-411.
[24]Lugstein A, Jentys A, Vinek H. Hydroconversion of n-heptane over bifunctional HZSM-5 zeolites Influence of the metal concentration and distribution on the activity and selectivity[J]. Applied Catalysis General.1998,166(5):29-38.
[25]陶克毅,王玲,藏雅茹等.无机氟改性的HZSM-5分子筛催化1,2,4—三甲苯与甲醇烷基化合成1,2,4,5-四甲苯的研究[J].化学工业与工程.1995,12(2)：9-13.
[26]金宏等.偏三甲苯—甲醇烷基化制均四甲苯的研究[J].金陵石油化工.1992,8(4)：1-4.
[27]丁瑛,孙滔,赵开鹏等.混合三甲苯制均三甲苯联产均四甲苯[J].石油炼制与化工.1990,6(5)：25-29.
[28]李栋潘,贾定先,张盈珍等.含锆层柱蒙脱石对1,2,4-三甲苯歧化反应的催化作用[J].催化学报.1998,19(1)：58-62.
[29]Jone W, Tennakoon D, Tilak B, Thomas J M. Structural aspects of metal-oxide-pillared sheet silicates. An investigation by magic-angle-spinning nuclear magnetic resonance, fourier-transform infrared spectroscopy and powder X-ray diffractometry[J]. J Chem Soc, Faraday Trans 1,1986(10):3081-3095.
[30]Schezer J, et al. Catakytuc Materials:Relation between structure and reactivity [C]. In:ACS Symp Ser 248. Am Chem Soc, Washington D C,1984,57:26-33.
[31]Wadlinger R L, Kerr G T, Risubski E J. Catalytic composition of a crystalline zeolite[P]. US3308069,1967-03-07.
[32]Martens J A, Tielen M, Jacobas P A, Weitkamp J. Estimation of the void structure and pore dimensions of molecular sieve zeolites using the hydroconversion of n-decane[J]. Zeolites,1984,4(2):98-107.
[33]Martens J A, Jacbs P A, et al. The potential and limitations of the n-decane hydroconversion as a test reaction for characterization of the void space of molecular sieve zeolites[J]. Zeolites,1986,6(5):334-338.
[34]Newsan J M, Treacy M M J, Koetsier W T, De Gruyter C B, et al. Structural characterization of zeolite beta[J]. Proc.R.Soc.Lond.1988,A420,375-405.
[35]孟宪平,王颖霞,林炳雄,韦承谦,张婉静.p沸石堆垛层错结构的研究[J].物理化学学报.1996,12(8)：727-734.
[36]Higgins J B, Lapierre R B,Schlenker J L,Rohrman AC, Wood J D, et al. The framework topology of Zeolite Beta-A Correction[J]. Zeolites,1989,9,358-363.
[37]周峰,李广站等.p沸石的合成研究[J].山东冶金,2007,29(6)：55-57.
[38]王桂茹,王安杰,刘靖,郭新闻等.催化剂与催化作用[M].大连：大连理工大学出版社.2004,67.
[39]Emiis C A, et al. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. J Catal. 1993,141:347-354.
[40]Takeshi Sugii, Ryuichiro Ohnishi, Jin Zhang, Toshio Okuhara. Acidity-attenuated heteropolyacid catalysts:Acidity measurement using benzonitrile-TPD and catalytic performance in the skeletal isomerization of n-heptane[J]. Catalysis Today.2006,116(2):179-183.
[41]Kumar N, Masloboischikova O V, Kustov L M, Heikkila T, et al. Synthesis of Pt modified ZSM-5 and Beta zeolite catalysts:Influence of ultrasonic irradiation and preparation methods on physico-chemical and catalytic properties in pentane isomerization[J]. Ultrasonics Sonochemistry.2007,14:122-130.
[42]Tingfang Hu, Jingpeng Chen, Haiyan Wang. Influence of shaped and modified Hβ zeolite on etherification of FCC light gasoline[J]. Micr. Mes. Mater.2006, 94:283-287.
[43]Zekai Zhang, Shenglin Liu, Xiangxue Zhu, Qingxia Wang, Longya Xu. Modification of Hβ zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline[J].Fuel.2008,89:103-110.
[44]梁必超,杨德琴,孔德金,施力等.Hβ和SiO2负载磷钨酸催化剂用于甲苯和均三甲苯反应制备二甲苯的催化性能[J].华东理工大学学报.2008,34(3)：315-318.
[45]王华,黄韬,杜鹃,刘中民等.通过Hβ分子筛上的烯烃水合反应提高FCC汽油品质[J].催化学报.2005,26(6)：451-452.
[46]Alexandre F, Costa, Henrique S. Cerqueira. BEA and MOR as additivies for light olefins production[J]. Applied Catalysis A:General,2007,319:137-413.
[47]Sharath R K, Nagaraju N, Komandur V R Chary. Esterification of alcohols with acetic acid over zeolites Hβ, HY and HZSM-5[J]. Appl Catal A:Gen,2006,299: 185-192.
[48]Halgeri A B, Das J, Bhat Y S, Bhardwaj A I. Zeolite beta catalyzed C7 and C9 aromatics transformation[J]. Appl Catal A:General. 1994,116,71-79.
[49]Pokhriyal S K, Ratnasamy P, Bhat R N, Hegde S G, et al. Reactions of Aromatic Hydrocarbons over Zeolite β[J]. J Catal.1989,119,65-70.
[50]陈庆龄,张成芳,谢在库,刘红星等.Hβ沸石上甲苯歧化和C9芳烃烷基转移反应[J].华东理工大学学报.2005,26(3)：260-264.
[51]Tsai T C, Wang I, Huang S T, et al. Disproportionation of Toluene and of Trimethylbenzene and Their Transalkylation over Zeolite Beta[J]. Ind.Eng. Chem.Res.1990,29,2005-2012.
[52]Komatsu T, Wang Z B, Kamo A, et al. Isomerization of n-heptane over Pt-loaded zeolite β catalysts[J]. Appl.Catal.A:General.1997,159,119-132.
[53]庞新梅,高晓慧,张莉,石晓庆,周至远,曹庚振.β沸石的催化裂化反应性能[J].石油学报,2009,16(3)：77-79.
[54]Ramaswamy A V, Venkatesan C, Jaimol T, Moreau P, Finiels A. Liquid phase selective benzoylation of chlorobenzene to 4,4'-dichlorobenzophenone over Zeolite H-Beta[J]. Catalysis Letters.2007,75(1-2):119-123.
[55]石晓庆,李萍,张莉,庞新梅,王宝杰.几种β分子筛在催化裂化催化剂中的应用研究[J].石化技术.2008,15(3)：6-9.
[56]Tomonobu T, Fujimoto K, Ge Q, et al. Influence of Pd ion-exchange temperature on the catalyticperformance of Cu-ZnO/Pd-β zeolite hybrid catalyst for CO hydrogenation to light hydrocarbons[J]. Catal.Commun,2008,9:1775-1778.
[57]Ping Liu, Xinggung Zhang, Yue Yao, Jun Wang. Pt catalysts supported on β zeolite ion-exchanged with Cr(Ⅲ) for hydroisomerization of n-heptane[J]. Applied Catalysis A:General,2009,371:142-147.
[58]刘金龙,王国良,秦如意,李树本等.改性对β沸石表面酸性及丙烯水合醚化反应性能的影响[J].燃料化学学报.2002,30(4)：353-357.
[59]杨伯伦,路士庆,吴江,王华军等.镧改性β分子筛上的异丁烯水合醚化复 合反应[J].催化学报.2007,28(1)：73-79.
[60]Jim Schwarz, Adriana Contescu, Cristian Contescu. Methods for Preparation of Catalytic Materials[J]. Chem Rev.1995,95:477-510.
[61]申群兵,朱学栋,董娇娇,吴勇强,朱子彬.载钼分子筛催化剂上C9+重芳烃的轻质化[J].石油学报.2009,25(3)：351-357.
[62]Huifeng Li, Mingfeng Li, Yang Chu, Hong Nie. Influence of different modified β zeolite on skeletal isomerization of n-hexene in the presence of hydrogen[J]. Microporous and Mesoporous Materials.2009,117:635-639.
[63]Kenichi Komura, Qiu Jun, Yoshihiro Kubota, Yoshihiro Sugi, et al. Synthesis of Cyclohexylbenzene by Hydroalkylation of Benzene over Pd/Hβ Binary Catalyst [J].Chin J Catal,2007,28(3):246-250.
[64]谷峰,孟禹,王海彦,魏民等.改性p沸石负载碳化钼催化剂上正己烷的异构化[J].石油与天然气化工.2009,38(2)：96-99.
[65]李承烈等.烃类异构化[M].北京：中国石化出版社.1992,123-130.
[66]Guisnet M, Gnep N S, Morin S, et al. Mechanisms of xylene isomerization over acidic solid catalysts[J]. Microporous and Mesopruus Materials,2006,35:47-49.
[67]曹声春,胡艾希等.催化原理及其工业应用技术.长沙：湖南大学出版社.2001.151-152.
[68]Zhang W.M., P.G Smirniotis, M.Gangoda, et al. Brφnsted and Lewis Acid Sites in Dealuminated Zeolites Characterized by NH3-TPD,FT-IR,and MAS NMR Spectroscopy[J]. J.Phys.Chem.2000,104:4122-4129.
[69]Motoyuki Masahiro, Yamamoto Koji. Process for preparing dialkynaphthalene[P]. US5844064(A)-1998-12-01.
[70]Romero M D, Calles J A, Rodriguez A, et al. Influence of the preparation method and mental precursor compound on the bifunctional Ni/HZSM-5 Catalysts[J]. Ind.Eng.Chem.Res.1997,36:3533-3540.
[71]Minchev C, Zubkov C, Valtcher V, et al. Nature of actuve sites and catalytic activity of SAPO-5 synthesized in the presence of nickel cations[J]. Appl.Catal. 1994,119:195-201.
[72]张铭金.沸石分子筛催化剂上萘择形烷基化基础研究：[博士学位论文],中国科学院山西煤炭化学研究所,山西：2000.
[73]Pekka Tynjala, Tuula T, Pakkanen, et al. Modification of ZSM-5 zeolite with Trimethyl phosphate Part 1. structure and acidity[J]. Microporous and Mesoporous Materials,1998,20:363-369.