液相晶化法合成SAPO系列分子筛的研究
|
摘要
本文介绍了SAPO-34分子筛的开发意义和国内外研究现状,并对SAPO-34分子筛的合成方法、原料的影响进行了深入的研究。
本文采用一种新的方法——液相晶化法合成了SAPO-34分子筛和SAPO-20分子筛;采用自动吸附仪、XRD、SEM和FT-IR等手段对合成的SAPO-34和SAPO-20分子筛样品进行了表征;采用液相晶化法合成SAPO-34分子筛时,晶化温度、晶化时间和原料的纯度对分子筛有重大影响;140～180℃和96～120h是适宜的晶化温度和晶化时间;硅源的纯度对合成的SAPO-34分子筛的结晶影响最大。
对于SAPO-20分子筛,研究了干胶颗粒的大小、干胶中模板剂的加入、模板剂加入的顺序和HF的加入对分子筛的影响。其中,干胶的颗粒越小,越容易合成出结晶度高的SAPO-20分子筛;在干胶中加入吗啉模板剂对分子筛的结晶影响不是很大;加入HF能提高分子筛的结晶度。
硅源、铝源、磷源和水的比例相同,模板剂的种类不同将会合成出完全不同的分子筛,以吗啉为模板剂合成出的是SAPO-20分子筛,以吗啉和四乙基氢氧化铵为模板剂合成的是SAPO-34分子筛。
对不同的原料合成的SAPO-34分子筛进行MTO催化性能的测试,结果表明,在320℃时,部分分子筛样品的甲醇转化率达到95%以上,乙烯丙烯的总选择性达到78%以上。
The research meaning of SAPO-34 molecular sieve and methanol-to-Olefins at home and abroad were reviewed.The synthetic method and the effect to SAPO-34 molecular sieve of the purity of raw materials were studied in this article.
A series of SAPO-34 molecular sieve samples and SAPO-20 molecular sieve samples were synthesized with a new method that named liquid-phase crystallization method.SAPO-34 and SAPO-20 molecular sieve samples have been characterized by specific surface area,XRD,SEM and FT-IR techniques.Crystallization temperature,crystallization time and the purity of alumina,silica sol and template have important effect to the crystallization of SAPO-34 molecular sieve.140-180℃and 96-120h were suitable crystallization temperature and crystallization time of SAPO-34 molecular sieve synthesized with liquid-phase crystallization method.The purity of silica sol was the seriousest effect to the crystallization of SAPO-34 molecular sieve.
The effect to SAPO-20 molecular sieve of the size of dry gel granule,the time of adding template and HF were studied.The result showed the small size dry gel granule was advantageous to the crystallization of SAPO-20 molecular sieve.Add some template to dry gel when making it,have little effect to SAPO-20 molecular sieve.HF would improved the crystallization of SAPO-20 molecular sieve.
The raw materials composition were same,only the quantity of template was changed,different molecular sieve were synthesized.SAPO-20 molecular sieve samples have been synthesized by using Morpholine as template,while SAPO-34 molecular sieve samples have been synthesized by using Morpholine and tetraethylammonium hydroxide (TEAOH) as template.
The SAPO-34 molecular samples synthesized with different purity sources with liquid-phase crystallization method were investigated by MTO process.The resulte showed at 320℃,the conversion of CH_3OH exceeded 95%,the overall selection of ethylene and propylene is more than 78%.
本文采用一种新的方法——液相晶化法合成了SAPO-34分子筛和SAPO-20分子筛;采用自动吸附仪、XRD、SEM和FT-IR等手段对合成的SAPO-34和SAPO-20分子筛样品进行了表征;采用液相晶化法合成SAPO-34分子筛时,晶化温度、晶化时间和原料的纯度对分子筛有重大影响;140～180℃和96～120h是适宜的晶化温度和晶化时间;硅源的纯度对合成的SAPO-34分子筛的结晶影响最大。
对于SAPO-20分子筛,研究了干胶颗粒的大小、干胶中模板剂的加入、模板剂加入的顺序和HF的加入对分子筛的影响。其中,干胶的颗粒越小,越容易合成出结晶度高的SAPO-20分子筛;在干胶中加入吗啉模板剂对分子筛的结晶影响不是很大;加入HF能提高分子筛的结晶度。
硅源、铝源、磷源和水的比例相同,模板剂的种类不同将会合成出完全不同的分子筛,以吗啉为模板剂合成出的是SAPO-20分子筛,以吗啉和四乙基氢氧化铵为模板剂合成的是SAPO-34分子筛。
对不同的原料合成的SAPO-34分子筛进行MTO催化性能的测试,结果表明,在320℃时,部分分子筛样品的甲醇转化率达到95%以上,乙烯丙烯的总选择性达到78%以上。
The research meaning of SAPO-34 molecular sieve and methanol-to-Olefins at home and abroad were reviewed.The synthetic method and the effect to SAPO-34 molecular sieve of the purity of raw materials were studied in this article.
A series of SAPO-34 molecular sieve samples and SAPO-20 molecular sieve samples were synthesized with a new method that named liquid-phase crystallization method.SAPO-34 and SAPO-20 molecular sieve samples have been characterized by specific surface area,XRD,SEM and FT-IR techniques.Crystallization temperature,crystallization time and the purity of alumina,silica sol and template have important effect to the crystallization of SAPO-34 molecular sieve.140-180℃and 96-120h were suitable crystallization temperature and crystallization time of SAPO-34 molecular sieve synthesized with liquid-phase crystallization method.The purity of silica sol was the seriousest effect to the crystallization of SAPO-34 molecular sieve.
The effect to SAPO-20 molecular sieve of the size of dry gel granule,the time of adding template and HF were studied.The result showed the small size dry gel granule was advantageous to the crystallization of SAPO-20 molecular sieve.Add some template to dry gel when making it,have little effect to SAPO-20 molecular sieve.HF would improved the crystallization of SAPO-20 molecular sieve.
The raw materials composition were same,only the quantity of template was changed,different molecular sieve were synthesized.SAPO-20 molecular sieve samples have been synthesized by using Morpholine as template,while SAPO-34 molecular sieve samples have been synthesized by using Morpholine and tetraethylammonium hydroxide (TEAOH) as template.
The SAPO-34 molecular samples synthesized with different purity sources with liquid-phase crystallization method were investigated by MTO process.The resulte showed at 320℃,the conversion of CH_3OH exceeded 95%,the overall selection of ethylene and propylene is more than 78%.
引文
[1]洪定一.对碳一化学研究开发工作的思考.见:天然气化工利用研讨会论文集.重庆,2003.
[2]Vora Bipin V.Natrual Gas to High Value olefin[J].Proc.World Pet.Congr.1999,15(3):38-39.
[3]UOP LLL.Process for Producing Producing Polymer Grade Olefin[P].US,US 5914433,1997-07-22.
[4]UOP LLC.Process for Producing Ethylene[P].US,US644 4869,2001-07-19.
[5]John Q.Chen,Andrea Boxxano.Recent Advancements in Ethylene and Propylene Production Using the UOP/Hydro MTO Process[J].Catalysis Today,106(2005):103-107.
[6]Kupelkova L,Novakova J,etal.Reactivity of surface species on zeolites in methanol conversion[J].J Catal,1990,124(2):441-450.
[7]Hutchings G J,et al.The conversion of methanol and other o-compounds to hydrocarbons over zeolite beta[J].J Catal,1994,147(1):177-185.
[8]Bibby D M,Chang C D,etal.Methane conversion[M].ElsevierAmsterdam,1988,127.
[9]Salehirad F,Anderson M W.Solid-state NMR studies of adsorption complexed and surface methoxy groups on methanol-sorbed microporous materials[J].J Catal,1998,177(2):189-207.
[10]Stocker M.Methanol-to-hydrocarbons:catalytic materials and their behavior[J].Micro.Meso.Mater.,1999,29(1-2):3-48.
[11]Hutching G J,Gottschalk F.Hydrocarbon Formation from Methylating Agents over Zeolite Catalyst ZSM-5.Comments on the Mechanism of Carbon-Carbon Bond and Methane Formation[J].J Chem.Faraday Trans 2,1987,83:571-583.
[12]Mole T.Isotopic and Mechanistic Studies of Methanol Conversion[J].Stud Surf Sci Catal,1988,36:145-146.
[13]Kazansky V B,Senchenya I N.Quantum Chemical Study of the Electronic Structure and Geometry of Surface Alkoxy Groups as Probable Active Intermediates of Heterogeneous Acidic Catalysts:What Are the Adsorbed Carbenium Ions[J].J Catal,1989,119(1):108-120.
[14] Hutchings G J, Hunter R. Methanol Conversion to Hydrocarbons over Zeolite H-ZSM-5: Investigation of the Role of CO and Ketene in the Formation of the Initial C-C bond [J]. J Catal, 1993,142(2): 602-616.
[15]Salehirad F, Anderson M W. Solid-state 13C MAS NMR Study of Methanol-to-Hydrocarbon Chemistry over H-SAPO-34 [J]. J Catal, 1996,164(2): 301-314.
[16] Dahl IM, Kolboe S. On the Reaction Mechanism for Propene Formation in the MTO Reaction over SAPO-34 [J]. Catal Lett, 1993,20: 329-336.
[17] Kolboe S, Dahl I M. Methanol Conversion to Hydrocarbons. Use of Isotopes for Mechanism [J]. Stud Surf Sci Catal, 94: 427-434.
[18] Benito P L, Gayubo A G, Aguayo A T. Effect of Si/Al Ratio and Acidity of HZSM-5 Zeolites on the Primary Products of Methanol to Gasoline Conversion [J]. J Chem Tech Biotechnol, 1996,66: 183-191.
[19] Campo A E S, Gayubo A G, Aguayo A T. Acidity, Surface Species, and Mechanism of Methanol Transformation into Olefins on SAPO-34 [J]. Ind Eng Chem Res, 1998, 37: 2336-2340.
[20] Clarence C D,S ilvestri A J. The Conversion of Methanol and Other O-Compounds to Hydrocarbons over Zeolite Catalysts[J]. J Catal,1977,47: 249-259.
[21]Clarence C D, Cynthia C T W, Richard F S. Methanol Conversion to Olef ins over ZSM -5.[J] J Catal, 1984, 86: 289-296.
[22] Schneider M, Schmidt.F. Process for Preparing Lower Olef ins. Eur Pat Appl, EP 0448000. 1991.
[23] Vora B V, Marker T. Process for Producing Light Olef ins from Crude Methnaol. US Pat Appl, US 5714662.1998.
[24] Mu vaney R C, Marker T. Process for Producing Light Olef ins. US Pat Appl, US 5744680. 1998.
[25] Sun Hsiang Ninc. Catalytic Conversion of Oxygenates to Olef ins.U S Pat Appl, US 6046373. 2000.
[26]Latter J R,Sun Hsiang Ninc.Process for Converting Oxygenates to Olef ins Using Molecular Sieves Catalysts Comprising Des irab le Carbonaceous Deposits.US Pat Appl,U S 6023005.2000.
[27]Machteld M,Strohmaier K G.Process for Manufacture of Molecular Sieves.中国,CN 1596222.2005.
[28]Guth F,Kessler H.Process for the Synthcs is of Precu rsors of Molecular Sieves of the Silicoaluninophophate.US Pat.Appl,U S 5096684.1992.
[29]Cao Guang,Shah M J.Synthes is of Aluminophosphates and Silicoa uminophosphates.Eur Pat Appl,EP 2525160.2005.
[30]Cao Guang,Mertens M M.Chabaz ite-Containing Molecular Sieve,Its Synthesis and Its Use in the Conversion of Oxygenates to Olef ins.PCT Int Appl,WO 200506623.2005.
[31]Mertens M M,Cao Guang.Chabaz ite-Type Molecular Sieve,Its Synthesis and Its Use in the Conversion of Oxygenates to Olef ins.PCT Int Appl,WO 200506622.2005.
[32]Chen Chusheng,Feng Shaojie,Ran Shen,et al.Conversion of Methane to Syngas by a Membrane-Based Oxidation-Reforming Process.Angew Chem Int Ed,.2003,42:5 196-5198.
[33]Liu Zhong min,Sun Cheng lin,Wang Gong wei,et al.New Progress in R &D of Lower Olefin Synthesis.Fuel Process Technol,2000,63(2-3):161-172.
[34]赵毓璋,景振华.甲醇制烯烃催化剂及工艺的新进展.石油炼制与化工,1999,30(2):23-28
[35]刘中民.合成气经由二甲醚制取低碳烯烃新工艺.中国科学院院刊,1997,6:433-434.
[36]Chang Yunfeng,Waughn S N.Spray Drying Molecular Sieve Catalyst.PCT Int Appl,WO 2005056184.2005.
[37]William A W,Jeffrey T E.Method for Making Catalysis.Ger Offen,DE 69828199.2005
[38]Chang Yunfeng,Stephen N V.Molecular Sieve Catalyst Composition,Its Making and Use in Conversion Processes.US Pat Appl,U S 2005075525.2005.
[39]李宏愿,梁娟,汪荣慧等.硅磷酸铝分子筛SAPO-34的合成.石油化工,1987,16(5):340-346
[40]何长青,刘中民,杨立新等.三乙胺法合成磷硅铝分子筛SAPO-34的研究.天然气化工,1993,18(5):14-18.
[41]付晔,王乐夫,谭宇新等.晶化条件对SAPO-34结晶度及催化活性的影响.华南理工大学学报(自然科学版),2001,4:30-32.
[42]郑燕英,杨廷录,周小虹等.制备条件对SAPO-34分子筛结构及MTO活性的影响.燃料化学学报,1999.4,27(2):140-142.
[43]何长青,刘中民,杨立新等.双模板剂控制SAPO-34分子筛的品粒尺寸[P].分子催化,1994,8(3):207-212.
[44]何长青,刘中民,杨立新等.模板剂对SAPO-34分子筛晶粒尺寸和性能的影响[J].催化学报,1995,16(1):33-37.
[45]徐如人,庞文琴,屠昆岗等.沸石分子筛的结构与合成,吉林大学出版社,1987.
[46]Inui T,Matsuda H,et al.Preparation of silico-alumino-phosphatcs by the rapid crystallization method and their catalytic performances in the conversion of methanol to light olcfins.Appl Catal,1990,58(1):155-163.
[47]Liang J,Li H Y.etal.Characteristics and performance of SAPO-34 catalyst for methanol-to-olefin conversion[J].Appl Catal,1990,64:31-40.
[48]Barger P T,Lesch D A,et al.[J].Arab J Sci Eng Chem Res,1998,37:2336.
[49]Watanabe Y,Koiwai A,et al.[J].Multinuclear NMR Studies on the Thermal Stability of SAPO-34.J Catal,1993,143(2):430-436.
[50]刘红星,谢在库,张成芳等.不同模板剂合成SAPO-34分子筛的表征与热分解过程研究[J].化学物理学报,2003.12,16(6):521-527.
[51]Briend M,Vomschied R,Peltre MJ,et al.[J].J Phy Chem,1995,99:8270.
[52]McNicol B D,Pott G T,Loss K R et al.Spectroscopic Studies of Zeolite synthesis,Evidence for a Solid-state Mechanism.Adv.Chem.Series 121 "Molecular Series",Meier W.N.Uytterhoeven J.B.,(Eds)1973.152-161.
[53]Xu W,Li J,Li Wetal.Nonaqueous Synthesis of ZSM-35 and ZSM-5,Zeolite.1989,9:468-473
[54]Tsapatsis M,Lorallo M,Davis M E.High-resolution Electron microscopy Study on the Growth of Zeolite L Nanocusters,Microp.Mater.1996,5:381-388.
[55]Serrano D P,Uguina U A,Ovejerog et al.Evidence of Solid-solid Transformations during the TS-1 Crystallization from amorphous Wetness impregnated SiO_2-TiO_2Xerogels.Microp.Mesop.Mate.1996,7:309-321.
[56]Uguina M A,Serrano D P,Overjeor G et al.Zeolites.1997,18:368.
[57]Serrano D P,Van Griekan R Sanchez P,Sanz,R et al.Crystallizetion Mechanizam of all-silica Zeolite beta in Fluoride Medium,Microporous Mesoporous Mater.201,46:35-46.
[58]Rao P,Prasad R H,Leon Y,Matsukata M.Synthesis of BEA by Dry Gel Conversion and Its Characterization.Microp.Hesop.Mater.1998,21:305-313.
[59]Matsukata M,Osaki T,Ogura M et al.Crystallization Behavior of Zeolite Beta during Steam-assited Crystallization of Dry Gel,Microporous Mesoporous Mater.2002,56:1-10.
[60]Djieugoue M A,Prakash A M,Kevan L.Catalytic study of methanol-to-olefins conversion in four small-pore silicoaluminophosphate molecular sieves:influence of the structural type.nickel incorporation,nickel location,and nickel concentration[J].J Phys Chem B.2000,104,6452-6461.
[61]Prakash A M,Unnlkrishnan S.Synthesis of SAPO-34:high silicon incorporation in the presence of morpholine as template[J].J Chem Soc Faraday Trans,1994,90(15),2291-2296.
[62]Anderson M W,Sulikowski B,Barrier P J,etal.In situ solid-state NMR studies of the catalytic conversion of methanol on the molecular sieve SAPO-34[J].J Phys Chem,1990,94,2730-2734.
[63]Zibrowius B,Loffler E,Hunger M.Multinuclear MAS NMR and IR spectroscopic study of silicon incorporation into SAPO-5,SAPO-31 and SAPO-34 molecular sieves[J].Zeolites,1992,12,167-174.
[64]Ashtekar S,Chilukuri S V V,Chakrabarty D K.Small-pore molecular sieve SAPO-34 and SAPO-44 with chabazite structure:A study of silicon incorporation[J].J Phys Chem,1994,98,4878-4883.
[65]Zubkov S A,Kustov L M,et al.Investigation of hydroxyl groups in crystalline silicoaluminophosphate SAPO-34 by diffuse reflectance infared spectroscopy[J].J Chem Sco Faraday Trans,1991,87(6),897-900.
[66]Blackwell C S,Patton R L.Solid state NMR of silicoaluminophosphate molecular sieves and aluminophosphate materials[J].J Phy Chem,1984,88,6135-6139.
[67]Blackwell C S,Patton R L.Aluminum-27 and phosphorus-31 nuclear magnetic resonance studies of aluminophosphate molecular sieves[J].J Phy Chem,1988,92,3965-3970.
[68]李军,张凤美,李黎声等.SAPO-34分子筛研究进展.化工进展,2005,24(4):434
[69]刘红星,谢在库,张成芳等用氟化氢-三乙胺复合模板剂合成SAPO-34分子筛[J].催化学报,2003.4,24(4):279-283.
[70]刘红星,谢在库,张成芳等.用TEAOH-C4H9NO复合模板剂合成SAPO-34分子筛的研究Ⅱ.SAPO-34分子筛的表面酸性和催化性能[J].催化学报,2004.9,25(9):710.
[71]徐如人,庞文琴,于吉红等.分子筛与多孔材料化学,科学出版社,2004.
[72]Tan J,Liu Z M,Bao X H.et al.Crystallization and Si incorporation mechanisms of SAPO-34.Micro.Meso.Mater.,2002,53(1-3):97-108.
[73]Lok B M,Messina C A,Lyle P R,etal.Crystallina Silicoaluminophosphate[P].US 4440871,1984.
[74]李宏愿,梁娟,刘子名,赵素琴,汪荣慧.硅磷酸铝分子筛SAPO-11,SAPO-34和SAPO-20的合成[J].催化学报,1988,1(9):87.
[75]徐文肠,窦涛,吴峰.AIPO4-20及其杂原子分子筛的合成研究[J].太原工业大学学报,1989,3(20):21.
[76]Lok,B.M,Messina,C.A.,Patton,R.L.et al.,J.Amer.Chem.Soc.,1066092(1984).
[77]Sunil Ashtekar,Satyanarayana V.V.Chilukuri,Dipak K.Chakrabarty.Small-Pore Molecular.Sieves SAPO-34 and SAPO-44 with Chabazite Structure:A Study of Silicon Incorporation[J].J.Phys.Chem.1994,98:4878-4883.
[78]Emil Dumitriu,Doina Lutic,Vasile Hulea,Dana Dorohoi,Abdelkrim Azzouz,Elisabeth Colnay and Charles Kappenstein.Synthesis optimization of chabasite-like SAPO-47 in the presence of sec-butylamine[J].Microporous and Mesoporous Materials.1999,31:187-193.
[79]杜爱萍,许磊,张大治,刘中民,王公慰.SAPO-34和SAPO-44分子筛上吸附甲醇的TPSR-MS研究[J].催化学报,2004,8(25):619-623.
[2]Vora Bipin V.Natrual Gas to High Value olefin[J].Proc.World Pet.Congr.1999,15(3):38-39.
[3]UOP LLL.Process for Producing Producing Polymer Grade Olefin[P].US,US 5914433,1997-07-22.
[4]UOP LLC.Process for Producing Ethylene[P].US,US644 4869,2001-07-19.
[5]John Q.Chen,Andrea Boxxano.Recent Advancements in Ethylene and Propylene Production Using the UOP/Hydro MTO Process[J].Catalysis Today,106(2005):103-107.
[6]Kupelkova L,Novakova J,etal.Reactivity of surface species on zeolites in methanol conversion[J].J Catal,1990,124(2):441-450.
[7]Hutchings G J,et al.The conversion of methanol and other o-compounds to hydrocarbons over zeolite beta[J].J Catal,1994,147(1):177-185.
[8]Bibby D M,Chang C D,etal.Methane conversion[M].ElsevierAmsterdam,1988,127.
[9]Salehirad F,Anderson M W.Solid-state NMR studies of adsorption complexed and surface methoxy groups on methanol-sorbed microporous materials[J].J Catal,1998,177(2):189-207.
[10]Stocker M.Methanol-to-hydrocarbons:catalytic materials and their behavior[J].Micro.Meso.Mater.,1999,29(1-2):3-48.
[11]Hutching G J,Gottschalk F.Hydrocarbon Formation from Methylating Agents over Zeolite Catalyst ZSM-5.Comments on the Mechanism of Carbon-Carbon Bond and Methane Formation[J].J Chem.Faraday Trans 2,1987,83:571-583.
[12]Mole T.Isotopic and Mechanistic Studies of Methanol Conversion[J].Stud Surf Sci Catal,1988,36:145-146.
[13]Kazansky V B,Senchenya I N.Quantum Chemical Study of the Electronic Structure and Geometry of Surface Alkoxy Groups as Probable Active Intermediates of Heterogeneous Acidic Catalysts:What Are the Adsorbed Carbenium Ions[J].J Catal,1989,119(1):108-120.
[14] Hutchings G J, Hunter R. Methanol Conversion to Hydrocarbons over Zeolite H-ZSM-5: Investigation of the Role of CO and Ketene in the Formation of the Initial C-C bond [J]. J Catal, 1993,142(2): 602-616.
[15]Salehirad F, Anderson M W. Solid-state 13C MAS NMR Study of Methanol-to-Hydrocarbon Chemistry over H-SAPO-34 [J]. J Catal, 1996,164(2): 301-314.
[16] Dahl IM, Kolboe S. On the Reaction Mechanism for Propene Formation in the MTO Reaction over SAPO-34 [J]. Catal Lett, 1993,20: 329-336.
[17] Kolboe S, Dahl I M. Methanol Conversion to Hydrocarbons. Use of Isotopes for Mechanism [J]. Stud Surf Sci Catal, 94: 427-434.
[18] Benito P L, Gayubo A G, Aguayo A T. Effect of Si/Al Ratio and Acidity of HZSM-5 Zeolites on the Primary Products of Methanol to Gasoline Conversion [J]. J Chem Tech Biotechnol, 1996,66: 183-191.
[19] Campo A E S, Gayubo A G, Aguayo A T. Acidity, Surface Species, and Mechanism of Methanol Transformation into Olefins on SAPO-34 [J]. Ind Eng Chem Res, 1998, 37: 2336-2340.
[20] Clarence C D,S ilvestri A J. The Conversion of Methanol and Other O-Compounds to Hydrocarbons over Zeolite Catalysts[J]. J Catal,1977,47: 249-259.
[21]Clarence C D, Cynthia C T W, Richard F S. Methanol Conversion to Olef ins over ZSM -5.[J] J Catal, 1984, 86: 289-296.
[22] Schneider M, Schmidt.F. Process for Preparing Lower Olef ins. Eur Pat Appl, EP 0448000. 1991.
[23] Vora B V, Marker T. Process for Producing Light Olef ins from Crude Methnaol. US Pat Appl, US 5714662.1998.
[24] Mu vaney R C, Marker T. Process for Producing Light Olef ins. US Pat Appl, US 5744680. 1998.
[25] Sun Hsiang Ninc. Catalytic Conversion of Oxygenates to Olef ins.U S Pat Appl, US 6046373. 2000.
[26]Latter J R,Sun Hsiang Ninc.Process for Converting Oxygenates to Olef ins Using Molecular Sieves Catalysts Comprising Des irab le Carbonaceous Deposits.US Pat Appl,U S 6023005.2000.
[27]Machteld M,Strohmaier K G.Process for Manufacture of Molecular Sieves.中国,CN 1596222.2005.
[28]Guth F,Kessler H.Process for the Synthcs is of Precu rsors of Molecular Sieves of the Silicoaluninophophate.US Pat.Appl,U S 5096684.1992.
[29]Cao Guang,Shah M J.Synthes is of Aluminophosphates and Silicoa uminophosphates.Eur Pat Appl,EP 2525160.2005.
[30]Cao Guang,Mertens M M.Chabaz ite-Containing Molecular Sieve,Its Synthesis and Its Use in the Conversion of Oxygenates to Olef ins.PCT Int Appl,WO 200506623.2005.
[31]Mertens M M,Cao Guang.Chabaz ite-Type Molecular Sieve,Its Synthesis and Its Use in the Conversion of Oxygenates to Olef ins.PCT Int Appl,WO 200506622.2005.
[32]Chen Chusheng,Feng Shaojie,Ran Shen,et al.Conversion of Methane to Syngas by a Membrane-Based Oxidation-Reforming Process.Angew Chem Int Ed,.2003,42:5 196-5198.
[33]Liu Zhong min,Sun Cheng lin,Wang Gong wei,et al.New Progress in R &D of Lower Olefin Synthesis.Fuel Process Technol,2000,63(2-3):161-172.
[34]赵毓璋,景振华.甲醇制烯烃催化剂及工艺的新进展.石油炼制与化工,1999,30(2):23-28
[35]刘中民.合成气经由二甲醚制取低碳烯烃新工艺.中国科学院院刊,1997,6:433-434.
[36]Chang Yunfeng,Waughn S N.Spray Drying Molecular Sieve Catalyst.PCT Int Appl,WO 2005056184.2005.
[37]William A W,Jeffrey T E.Method for Making Catalysis.Ger Offen,DE 69828199.2005
[38]Chang Yunfeng,Stephen N V.Molecular Sieve Catalyst Composition,Its Making and Use in Conversion Processes.US Pat Appl,U S 2005075525.2005.
[39]李宏愿,梁娟,汪荣慧等.硅磷酸铝分子筛SAPO-34的合成.石油化工,1987,16(5):340-346
[40]何长青,刘中民,杨立新等.三乙胺法合成磷硅铝分子筛SAPO-34的研究.天然气化工,1993,18(5):14-18.
[41]付晔,王乐夫,谭宇新等.晶化条件对SAPO-34结晶度及催化活性的影响.华南理工大学学报(自然科学版),2001,4:30-32.
[42]郑燕英,杨廷录,周小虹等.制备条件对SAPO-34分子筛结构及MTO活性的影响.燃料化学学报,1999.4,27(2):140-142.
[43]何长青,刘中民,杨立新等.双模板剂控制SAPO-34分子筛的品粒尺寸[P].分子催化,1994,8(3):207-212.
[44]何长青,刘中民,杨立新等.模板剂对SAPO-34分子筛晶粒尺寸和性能的影响[J].催化学报,1995,16(1):33-37.
[45]徐如人,庞文琴,屠昆岗等.沸石分子筛的结构与合成,吉林大学出版社,1987.
[46]Inui T,Matsuda H,et al.Preparation of silico-alumino-phosphatcs by the rapid crystallization method and their catalytic performances in the conversion of methanol to light olcfins.Appl Catal,1990,58(1):155-163.
[47]Liang J,Li H Y.etal.Characteristics and performance of SAPO-34 catalyst for methanol-to-olefin conversion[J].Appl Catal,1990,64:31-40.
[48]Barger P T,Lesch D A,et al.[J].Arab J Sci Eng Chem Res,1998,37:2336.
[49]Watanabe Y,Koiwai A,et al.[J].Multinuclear NMR Studies on the Thermal Stability of SAPO-34.J Catal,1993,143(2):430-436.
[50]刘红星,谢在库,张成芳等.不同模板剂合成SAPO-34分子筛的表征与热分解过程研究[J].化学物理学报,2003.12,16(6):521-527.
[51]Briend M,Vomschied R,Peltre MJ,et al.[J].J Phy Chem,1995,99:8270.
[52]McNicol B D,Pott G T,Loss K R et al.Spectroscopic Studies of Zeolite synthesis,Evidence for a Solid-state Mechanism.Adv.Chem.Series 121 "Molecular Series",Meier W.N.Uytterhoeven J.B.,(Eds)1973.152-161.
[53]Xu W,Li J,Li Wetal.Nonaqueous Synthesis of ZSM-35 and ZSM-5,Zeolite.1989,9:468-473
[54]Tsapatsis M,Lorallo M,Davis M E.High-resolution Electron microscopy Study on the Growth of Zeolite L Nanocusters,Microp.Mater.1996,5:381-388.
[55]Serrano D P,Uguina U A,Ovejerog et al.Evidence of Solid-solid Transformations during the TS-1 Crystallization from amorphous Wetness impregnated SiO_2-TiO_2Xerogels.Microp.Mesop.Mate.1996,7:309-321.
[56]Uguina M A,Serrano D P,Overjeor G et al.Zeolites.1997,18:368.
[57]Serrano D P,Van Griekan R Sanchez P,Sanz,R et al.Crystallizetion Mechanizam of all-silica Zeolite beta in Fluoride Medium,Microporous Mesoporous Mater.201,46:35-46.
[58]Rao P,Prasad R H,Leon Y,Matsukata M.Synthesis of BEA by Dry Gel Conversion and Its Characterization.Microp.Hesop.Mater.1998,21:305-313.
[59]Matsukata M,Osaki T,Ogura M et al.Crystallization Behavior of Zeolite Beta during Steam-assited Crystallization of Dry Gel,Microporous Mesoporous Mater.2002,56:1-10.
[60]Djieugoue M A,Prakash A M,Kevan L.Catalytic study of methanol-to-olefins conversion in four small-pore silicoaluminophosphate molecular sieves:influence of the structural type.nickel incorporation,nickel location,and nickel concentration[J].J Phys Chem B.2000,104,6452-6461.
[61]Prakash A M,Unnlkrishnan S.Synthesis of SAPO-34:high silicon incorporation in the presence of morpholine as template[J].J Chem Soc Faraday Trans,1994,90(15),2291-2296.
[62]Anderson M W,Sulikowski B,Barrier P J,etal.In situ solid-state NMR studies of the catalytic conversion of methanol on the molecular sieve SAPO-34[J].J Phys Chem,1990,94,2730-2734.
[63]Zibrowius B,Loffler E,Hunger M.Multinuclear MAS NMR and IR spectroscopic study of silicon incorporation into SAPO-5,SAPO-31 and SAPO-34 molecular sieves[J].Zeolites,1992,12,167-174.
[64]Ashtekar S,Chilukuri S V V,Chakrabarty D K.Small-pore molecular sieve SAPO-34 and SAPO-44 with chabazite structure:A study of silicon incorporation[J].J Phys Chem,1994,98,4878-4883.
[65]Zubkov S A,Kustov L M,et al.Investigation of hydroxyl groups in crystalline silicoaluminophosphate SAPO-34 by diffuse reflectance infared spectroscopy[J].J Chem Sco Faraday Trans,1991,87(6),897-900.
[66]Blackwell C S,Patton R L.Solid state NMR of silicoaluminophosphate molecular sieves and aluminophosphate materials[J].J Phy Chem,1984,88,6135-6139.
[67]Blackwell C S,Patton R L.Aluminum-27 and phosphorus-31 nuclear magnetic resonance studies of aluminophosphate molecular sieves[J].J Phy Chem,1988,92,3965-3970.
[68]李军,张凤美,李黎声等.SAPO-34分子筛研究进展.化工进展,2005,24(4):434
[69]刘红星,谢在库,张成芳等用氟化氢-三乙胺复合模板剂合成SAPO-34分子筛[J].催化学报,2003.4,24(4):279-283.
[70]刘红星,谢在库,张成芳等.用TEAOH-C4H9NO复合模板剂合成SAPO-34分子筛的研究Ⅱ.SAPO-34分子筛的表面酸性和催化性能[J].催化学报,2004.9,25(9):710.
[71]徐如人,庞文琴,于吉红等.分子筛与多孔材料化学,科学出版社,2004.
[72]Tan J,Liu Z M,Bao X H.et al.Crystallization and Si incorporation mechanisms of SAPO-34.Micro.Meso.Mater.,2002,53(1-3):97-108.
[73]Lok B M,Messina C A,Lyle P R,etal.Crystallina Silicoaluminophosphate[P].US 4440871,1984.
[74]李宏愿,梁娟,刘子名,赵素琴,汪荣慧.硅磷酸铝分子筛SAPO-11,SAPO-34和SAPO-20的合成[J].催化学报,1988,1(9):87.
[75]徐文肠,窦涛,吴峰.AIPO4-20及其杂原子分子筛的合成研究[J].太原工业大学学报,1989,3(20):21.
[76]Lok,B.M,Messina,C.A.,Patton,R.L.et al.,J.Amer.Chem.Soc.,1066092(1984).
[77]Sunil Ashtekar,Satyanarayana V.V.Chilukuri,Dipak K.Chakrabarty.Small-Pore Molecular.Sieves SAPO-34 and SAPO-44 with Chabazite Structure:A Study of Silicon Incorporation[J].J.Phys.Chem.1994,98:4878-4883.
[78]Emil Dumitriu,Doina Lutic,Vasile Hulea,Dana Dorohoi,Abdelkrim Azzouz,Elisabeth Colnay and Charles Kappenstein.Synthesis optimization of chabasite-like SAPO-47 in the presence of sec-butylamine[J].Microporous and Mesoporous Materials.1999,31:187-193.
[79]杜爱萍,许磊,张大治,刘中民,王公慰.SAPO-34和SAPO-44分子筛上吸附甲醇的TPSR-MS研究[J].催化学报,2004,8(25):619-623.