甲醇制烯烃(MTO)用SAPO-34分子筛催化剂研究新进展
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摘要
由于孔径较小、酸性适中、水热稳定性较强,SAPO-34分子筛被认为是甲醇制烯烃(MTO)工艺的最佳催化剂而受到广泛关注。合成SAPO-34分子筛的影响因素有模板剂、原料、硅铝比,反应条件等。本文综述了SAPO-34分子筛改性方面的研究进展,并对未来高性能SAPO-34分子筛的发展进行了展望。
Due to the moderate acid strength, relatively small pores and hydrothermal stability, SAPO-34 melecular sieve is supposed to be one of the most excellent catalysts, many research works have been reported relating to its synthesis and crystallization mechanism and catalytic properties for methanol to olefin(MTO) reaction. In this paper, the influence factors of SAPO-34 molecular sieves synthesis such as templates, raw materials, ratios of SiO_2/Al_2O_3 and reaction conditions were discussed, and advances in modification of SAPO-34 molecular sieve were reviewed. Then, the development trends of synthesis of SAPO-34 molecular sieve with excellent MTO performance in future are also prospected.
Due to the moderate acid strength, relatively small pores and hydrothermal stability, SAPO-34 melecular sieve is supposed to be one of the most excellent catalysts, many research works have been reported relating to its synthesis and crystallization mechanism and catalytic properties for methanol to olefin(MTO) reaction. In this paper, the influence factors of SAPO-34 molecular sieves synthesis such as templates, raw materials, ratios of SiO_2/Al_2O_3 and reaction conditions were discussed, and advances in modification of SAPO-34 molecular sieve were reviewed. Then, the development trends of synthesis of SAPO-34 molecular sieve with excellent MTO performance in future are also prospected.
引文
[1]Schwartz A B.A new process to improve octane and quality of gasoline[J].Advanced Catalysis,1968,18:259-261.
[2]Salvador P,Kladnig W.Surface reactivity of zeolites type H-Y and Na-Ywith methanol[J].Chem Soc Faraday Trans,1977,73:1153.
[3]Meisel S L,Mc Cullough J P,Lechthaler C H,et al.Gasoline from methanol in one step[J].Chem Tech,1976,6:86-89.
[4]Inui T,Matsuda H,Yamase O,et al.Highly selective synthesis of light olefins from methanol on a novel Fe-silicate[J].J Cata1,1986,98(2):491-501.
[5]张大治.分子筛催化转化氯甲烷制取低碳烯烃及其反应机理的研究[D].大连:中国科学院大连化学物理研究所,2007.
[6]Barger P T.Methanol conversion process using SAPO catalysts:US Patent,5095163[P].Mar,10,1992.
[7]Barger P T,et al.Metal aluminophosphate catalyst for converting methanol to light olefins:US Patent,5126308[P].Jun,30,1992.
[8]Lewis J M O,et al.Chemical conversion process:US Patent,49737929[P].Nov,27,1990.
[9]Obrzut D L,Adelkanattu P M,Thundimadathil J,et al.Reducing methane formation in methanol to olefins reaction on metal impregnated SAPO-34molecular[J].React Kinet Catal Lett,2003,80(1):113-121.
[10]Dubois D R,Obrzut D L,Liu J,et al.Conversion of methanol to olefins over cobalt-,manganese-and nickel-incorporated SAPO-34 molecular sieves[J].Fuel Proc Technol,2003,83:203-218.
[11]Inui T,Kang M.Reliable procedure for the synthesis of Ni-SAPO-34 as a highly selective catalyst for methanol to ethylene conversion[J].App Catal A:General,1997,164:211-223.
[12]Kang M.Methanol conversion on metal-incorporated SAPO-34s[J].JMole Catal A:Chemical,2000,160:437-444.
[13]Fung S C,et al.Conversion of oxygenates to olefins:US Patent,20060025644A1[P].Feb,2,2006.
[14]Janssen M J G,et al.Silicoaluminophosphate molecular sieve:US Patent,6953767B2[P].Oct,11,2005.
[15]Mertens M M,et al.Catalyst and process for the conversion of oxygenates to olefins:US Patent,20060074266A1[P].Apr,6,2006.
[16]Wendelbo R,et al.Microporous crystalline silicoaluminophosphate composition,catalytic material comprising said composition and use of these for production of olefins from methanol:US Patent,6334994 B1[P].Jan,1,2002.
[17]Chen J S,Wright P A,Thomas J M.SAPO-18 catalysts and their bronsted acid sites[J].J Phys Chem,1994,98:10216-10224.
[18]李天文,周国成,林朝阳,等.模板剂在分子筛合成中的作用[J].化工中间体,2006(11):16-19.
[19]王鹏飞.SAPO-34催化剂的制备及在甲醇制烯烃反应中的应用[D].上海:华东理工大学,2011.
[20]郑燕英,杨廷录,等.制备条件对SAPO-34分子筛结构及MTO活性的影响[J].燃料化学学报,1999,2:140-144.
[21]Lok B M,Messina C A,Patton R.L.Silicoaluminophosphate molecular sieves:another new class of microporous crystalline inorganic solids[J].Journal of the American Chemical Society,1984,106(20):6092-6609.
[22]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.
[23]何长青,刘中民,杨立新,等.双模板剂法控制SAPO-34分子筛的晶粒尺寸[J].分子催化,1994,8(3):207-212.
[24]梁光华,狄春雨,王龙,等.不同铝源合成SAPO-34分子筛及其MTO催化性能[J].石油学报,2014,30(5):885-890.
[25]张媛,张伟,刘志玲,等.SAPO-34分子筛催化剂制备及发展现状[J].工业催化,2016,24(2):14-20.
[26]刘光宇,田鹏,刘中民.二乙胺导向合成SAPO-34及与其它模板剂的对比[J].催化学报,2012,33(1):174-182.
[27]梁光华.SAPO-34分子筛表面酸性及其催化性能研究[D].太原:太原理工大学,2014.
[28]李俊汾,樊卫斌,董梅,等.SAPO-34分子筛的合成及甲醇制烯烃催化性能[J].高等学校化学学报,2011,32(3):765-771.
[29]孔令涛,沈本贤,蒋章.硅含量对氯甲烷制取低碳烯烃的SAPO-34分子筛酸性的影响[J].化工进展,2015,34(2):413-418.
[30]Tian Peng,Wei Yingxu,Ye Mao,et al.Methanol to olefins(MTO):From fundamentals to commercialization[J].ACS Catalysis,2015,5(3):1922-19388.
[31]崔宇,王垚,魏飞.SAPO-34分子筛硅铝比对甲醇制烯烃反应性能及积碳组成的影响[J].2015,66(8):2982-2989.
[32]李宏愿,梁娟,刘子名,等.硅磷酸铝分子筛SAPO-11、SAPO-34和SAPO-20的合成[J].催化学报,1988,(9):87-91.
[33]何长春,刘中民,杨立新,等.三乙胺法合成磷硅铝分子筛SAPO-34的研究[J].天然气化工,1993,18(6):14-18.
[34]刘旗,李奕怀,燕溪溪,等.晶化时间对SAPO-34分子筛合成及性能的影响[J].上海第二工业大学学报,2015,32(2):114-119.
[35]Barger P T,Heght S A.Methanol conversion process using SAPOcatalysts[P].US5095163,1991.
[36]Li Z,Martinez-triguero J,Yu J,et al.Conversion of methanol to olefins:stabilization of nanosized SAPO-34 by hydrothermal treatment[J].Journal of Catalysis,2015,329:379-388.
[37]关新新,刘克成,武光军,等.SAPO-34分子筛的氮化及在甲醇制烯烃(MTO)中的应用[J].分子催化,2006,20(3):270-273.
[38]关新新,刘克成,武光军,等.含N微孔SAPO-34分子筛的制备、表征及催化性能[J].石油学报:石油加工,2007,23(1):15-19.
[39]Kang M.Methanol conversion on metal-incorporated SAPO-34s(Me APSO-34s)[J].J Mol Catal A-Chem,2000,160(2):437-444.
[40]王兴旺,李世洪,孙岩,等.Mn改性SAPO-34分子筛及其MTO催化性能研究[J].现代化工,2015,35(5):85-87.
[41]Sun H,Vaughn S N.Conversion of oxygenate(s)to hydrocarbon(s)using small pore non-zeolitic molecular sieve catalysts-comprises using silico-alumino-phosphate molecular sieve catalysts containing alkaline earth metals:US6040264[P].2000.
[42]Stanko Hotevar,Janea Levec,et al.Acidity and catalytic activity of Me APSO-34(Me=Co,Mn,Cr),SAPO-34,and H-ZSM-5molecular sieves in methanol dethydration[J].Journal of Catalysis,1992,135(2):518-532.
[43]吕金钊.稀土(La,Y)改性SAPO-34分子筛催化转化甲醇制烯烃研究[D].大连:大连理工大学,2009.
[44]Tian S X,Ji S F,Lu D D.Preparation of modified Ce-SAPO-34 catalysts and their catalytic performances of methanol to olefins[J].J Energ Chem,2013,22(4):605-609.
[45]Schmidt F,Paasch S,Brunner E,et al.Carbon template SAPO-34 with improved adsorption kinetics and catalytic performance in the MTO-Reaction[J].Microporous and Mesoporous Materials,2012,164:214-221.
[46]Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chemical Communications,2009,(22):3282-3284.
[47]崔杏雨,王晶晶,等.多级SAPO-34的合成及其在甲醇制烯烃反应中的催化性能[J].无机化学学报,2018,34(2):300-308.
[48]Sun Qinming,Wang Ning,Bai Risheng,et al.Seeding induced nano-sized hierarchical SAPO-34 zeolites:cost-effective synthesis and superior MTOperformance[J].Journal of Materials Chemistry A,2016,4(39):14978-14982.
[49]孙启明.高性能SAPO-34分子筛的合成及MTO催化反应性能研究[D].吉林:吉林大学,2016.
[2]Salvador P,Kladnig W.Surface reactivity of zeolites type H-Y and Na-Ywith methanol[J].Chem Soc Faraday Trans,1977,73:1153.
[3]Meisel S L,Mc Cullough J P,Lechthaler C H,et al.Gasoline from methanol in one step[J].Chem Tech,1976,6:86-89.
[4]Inui T,Matsuda H,Yamase O,et al.Highly selective synthesis of light olefins from methanol on a novel Fe-silicate[J].J Cata1,1986,98(2):491-501.
[5]张大治.分子筛催化转化氯甲烷制取低碳烯烃及其反应机理的研究[D].大连:中国科学院大连化学物理研究所,2007.
[6]Barger P T.Methanol conversion process using SAPO catalysts:US Patent,5095163[P].Mar,10,1992.
[7]Barger P T,et al.Metal aluminophosphate catalyst for converting methanol to light olefins:US Patent,5126308[P].Jun,30,1992.
[8]Lewis J M O,et al.Chemical conversion process:US Patent,49737929[P].Nov,27,1990.
[9]Obrzut D L,Adelkanattu P M,Thundimadathil J,et al.Reducing methane formation in methanol to olefins reaction on metal impregnated SAPO-34molecular[J].React Kinet Catal Lett,2003,80(1):113-121.
[10]Dubois D R,Obrzut D L,Liu J,et al.Conversion of methanol to olefins over cobalt-,manganese-and nickel-incorporated SAPO-34 molecular sieves[J].Fuel Proc Technol,2003,83:203-218.
[11]Inui T,Kang M.Reliable procedure for the synthesis of Ni-SAPO-34 as a highly selective catalyst for methanol to ethylene conversion[J].App Catal A:General,1997,164:211-223.
[12]Kang M.Methanol conversion on metal-incorporated SAPO-34s[J].JMole Catal A:Chemical,2000,160:437-444.
[13]Fung S C,et al.Conversion of oxygenates to olefins:US Patent,20060025644A1[P].Feb,2,2006.
[14]Janssen M J G,et al.Silicoaluminophosphate molecular sieve:US Patent,6953767B2[P].Oct,11,2005.
[15]Mertens M M,et al.Catalyst and process for the conversion of oxygenates to olefins:US Patent,20060074266A1[P].Apr,6,2006.
[16]Wendelbo R,et al.Microporous crystalline silicoaluminophosphate composition,catalytic material comprising said composition and use of these for production of olefins from methanol:US Patent,6334994 B1[P].Jan,1,2002.
[17]Chen J S,Wright P A,Thomas J M.SAPO-18 catalysts and their bronsted acid sites[J].J Phys Chem,1994,98:10216-10224.
[18]李天文,周国成,林朝阳,等.模板剂在分子筛合成中的作用[J].化工中间体,2006(11):16-19.
[19]王鹏飞.SAPO-34催化剂的制备及在甲醇制烯烃反应中的应用[D].上海:华东理工大学,2011.
[20]郑燕英,杨廷录,等.制备条件对SAPO-34分子筛结构及MTO活性的影响[J].燃料化学学报,1999,2:140-144.
[21]Lok B M,Messina C A,Patton R.L.Silicoaluminophosphate molecular sieves:another new class of microporous crystalline inorganic solids[J].Journal of the American Chemical Society,1984,106(20):6092-6609.
[22]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.
[23]何长青,刘中民,杨立新,等.双模板剂法控制SAPO-34分子筛的晶粒尺寸[J].分子催化,1994,8(3):207-212.
[24]梁光华,狄春雨,王龙,等.不同铝源合成SAPO-34分子筛及其MTO催化性能[J].石油学报,2014,30(5):885-890.
[25]张媛,张伟,刘志玲,等.SAPO-34分子筛催化剂制备及发展现状[J].工业催化,2016,24(2):14-20.
[26]刘光宇,田鹏,刘中民.二乙胺导向合成SAPO-34及与其它模板剂的对比[J].催化学报,2012,33(1):174-182.
[27]梁光华.SAPO-34分子筛表面酸性及其催化性能研究[D].太原:太原理工大学,2014.
[28]李俊汾,樊卫斌,董梅,等.SAPO-34分子筛的合成及甲醇制烯烃催化性能[J].高等学校化学学报,2011,32(3):765-771.
[29]孔令涛,沈本贤,蒋章.硅含量对氯甲烷制取低碳烯烃的SAPO-34分子筛酸性的影响[J].化工进展,2015,34(2):413-418.
[30]Tian Peng,Wei Yingxu,Ye Mao,et al.Methanol to olefins(MTO):From fundamentals to commercialization[J].ACS Catalysis,2015,5(3):1922-19388.
[31]崔宇,王垚,魏飞.SAPO-34分子筛硅铝比对甲醇制烯烃反应性能及积碳组成的影响[J].2015,66(8):2982-2989.
[32]李宏愿,梁娟,刘子名,等.硅磷酸铝分子筛SAPO-11、SAPO-34和SAPO-20的合成[J].催化学报,1988,(9):87-91.
[33]何长春,刘中民,杨立新,等.三乙胺法合成磷硅铝分子筛SAPO-34的研究[J].天然气化工,1993,18(6):14-18.
[34]刘旗,李奕怀,燕溪溪,等.晶化时间对SAPO-34分子筛合成及性能的影响[J].上海第二工业大学学报,2015,32(2):114-119.
[35]Barger P T,Heght S A.Methanol conversion process using SAPOcatalysts[P].US5095163,1991.
[36]Li Z,Martinez-triguero J,Yu J,et al.Conversion of methanol to olefins:stabilization of nanosized SAPO-34 by hydrothermal treatment[J].Journal of Catalysis,2015,329:379-388.
[37]关新新,刘克成,武光军,等.SAPO-34分子筛的氮化及在甲醇制烯烃(MTO)中的应用[J].分子催化,2006,20(3):270-273.
[38]关新新,刘克成,武光军,等.含N微孔SAPO-34分子筛的制备、表征及催化性能[J].石油学报:石油加工,2007,23(1):15-19.
[39]Kang M.Methanol conversion on metal-incorporated SAPO-34s(Me APSO-34s)[J].J Mol Catal A-Chem,2000,160(2):437-444.
[40]王兴旺,李世洪,孙岩,等.Mn改性SAPO-34分子筛及其MTO催化性能研究[J].现代化工,2015,35(5):85-87.
[41]Sun H,Vaughn S N.Conversion of oxygenate(s)to hydrocarbon(s)using small pore non-zeolitic molecular sieve catalysts-comprises using silico-alumino-phosphate molecular sieve catalysts containing alkaline earth metals:US6040264[P].2000.
[42]Stanko Hotevar,Janea Levec,et al.Acidity and catalytic activity of Me APSO-34(Me=Co,Mn,Cr),SAPO-34,and H-ZSM-5molecular sieves in methanol dethydration[J].Journal of Catalysis,1992,135(2):518-532.
[43]吕金钊.稀土(La,Y)改性SAPO-34分子筛催化转化甲醇制烯烃研究[D].大连:大连理工大学,2009.
[44]Tian S X,Ji S F,Lu D D.Preparation of modified Ce-SAPO-34 catalysts and their catalytic performances of methanol to olefins[J].J Energ Chem,2013,22(4):605-609.
[45]Schmidt F,Paasch S,Brunner E,et al.Carbon template SAPO-34 with improved adsorption kinetics and catalytic performance in the MTO-Reaction[J].Microporous and Mesoporous Materials,2012,164:214-221.
[46]Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chemical Communications,2009,(22):3282-3284.
[47]崔杏雨,王晶晶,等.多级SAPO-34的合成及其在甲醇制烯烃反应中的催化性能[J].无机化学学报,2018,34(2):300-308.
[48]Sun Qinming,Wang Ning,Bai Risheng,et al.Seeding induced nano-sized hierarchical SAPO-34 zeolites:cost-effective synthesis and superior MTOperformance[J].Journal of Materials Chemistry A,2016,4(39):14978-14982.
[49]孙启明.高性能SAPO-34分子筛的合成及MTO催化反应性能研究[D].吉林:吉林大学,2016.