高丙烯选择性FMTP催化剂的合成及研究
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摘要
为提高甲醇制丙烯催化剂的丙烯单程收率,降低催化剂结焦,发展易于工业化应用的多级孔结构SAPO-34制备方法,提出利用合成晶化液自身的磷酸-三乙胺缓冲体系对晶体原位自刻蚀,通过XRD、SEM、氮吸附等方法对合成样品表征并催化评价。结果表明:晶化初期以晶粒生长为主,后期在磷酸-三乙胺缓冲体系下被刻蚀出现介孔和大孔,介孔孔容占微介总孔容的53.7%;随晶化/刻蚀时间的延长,晶体4个侧表面形成沿对角线分布的刻蚀区和非刻蚀区,进而形成金字塔形结构的SAPO-34。自刻蚀分子筛丙烯单程收率达45.5%,焦炭选择性<2%,催化剂寿命提高>2倍。该方法在2 m~3搅拌釜成功工业化放大,制备的催化剂寿命达250 min。
In order to improve the propene yield and inhibit coking,a synthetic method of hierarchical porous SAPO-34 using in-situ self-etching in phosphoric acid-triethylamine buffer solution was proposed. The synthetic products were characterized through X-ray diffraction,scanning electron microscope and nitrogen adsorption and catalytic testing.Results show that the crystal grows preliminary and it is etched in the H_3PO_4-TEA buffer in a later period resulting in mesopores and macropores,the mesoporous volume of which is as high as 53.7% of micro-mesoporous volume.With the increase of crystallization/etching time,the four side surfaces of the crystal are etched diagonally to etching and non-etching zones,parallelepiped SAPO-34 crystal even becomes pyramid. The in-situ self-etching SAPO-34 achieves 45.5% selectivity of propene,together with the coke selectivity less than 2%,and triple lifetime.This method has been successfully applied in a 2 m~3 stirred tank for industrial scaling-up,and the catalyst is active during 250 min with WHSV of 1.5 h~(-1).
In order to improve the propene yield and inhibit coking,a synthetic method of hierarchical porous SAPO-34 using in-situ self-etching in phosphoric acid-triethylamine buffer solution was proposed. The synthetic products were characterized through X-ray diffraction,scanning electron microscope and nitrogen adsorption and catalytic testing.Results show that the crystal grows preliminary and it is etched in the H_3PO_4-TEA buffer in a later period resulting in mesopores and macropores,the mesoporous volume of which is as high as 53.7% of micro-mesoporous volume.With the increase of crystallization/etching time,the four side surfaces of the crystal are etched diagonally to etching and non-etching zones,parallelepiped SAPO-34 crystal even becomes pyramid. The in-situ self-etching SAPO-34 achieves 45.5% selectivity of propene,together with the coke selectivity less than 2%,and triple lifetime.This method has been successfully applied in a 2 m~3 stirred tank for industrial scaling-up,and the catalyst is active during 250 min with WHSV of 1.5 h~(-1).
引文
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[19]朱彭龄.磷酸三乙胺-乙腈流动相体系反相分离2,4-二硝基氟苯-氨基酸衍生物[J].分析测试技术与仪器,2012,18(1):1-13.ZHU Pengling.Anti-phase separation of 2,4-dinitrofluorobenzyamino acid derivatives in TEA-acetonitrile flow phase system[J].Analytical Test Techniques and Instruments,2012,18(1):1-13.
[20]朱杰.流化床甲醇制丙烯催化剂的研究[D].北京:清华大学,2010.
[21]吴金雄,李牛,项寿鹤.低硅体系下SAPO-34分子筛的合成[J].石油化工,2012,41(5):510-514.WU Jinxiong,LI Niu,XIANG Shouhe.Synthesis of SAPO-34 under low silicon system[J].Journal of Petrochemical Industry,2012,41(5):510-514.
[2]袁学民,孙世谦,张蒙,等.国内甲醇制烯烃技术最新进展[J].现代化工,2012,32(12):29-31.YUAN Xuemin,SUN Shiqian,ZHANG Meng,et al.The latest progress of methanol to olefins technology in China[J].Journal of Modern Chemical Industry,2012,32(12):29-31.
[3]赵以辉,苏传好,吕杨.清华大学流化床甲醇制丙烯(FMTP)试验装置核心——反应再生系统技术特点[J].山东化工,2011,40(5):98-99.ZHAO Yihui,SU Chuanhao,LYU Yang.Core test device of fluidized bed methanol to propylene(FMTP)from Tsinghua university-reaction regeneration system[J].Journal of Shandong Chemical Industry,2011,40(5):98-99.
[4]赵以辉,苏传好.流化床甲醇制丙烯(FMTP)技术催化剂损耗问题探讨[J].河南化工,2011,28(11):34-36.ZHAO Yihui,SU Chuanhao.Discussion on catalyst loss of methanol to propylene in fluidized bed(FMTP)[J].Journal of Henan Chemical Industry,2011,28(11):34-36.
[5]ZHOU Huaqun,WANG Yao,WEI Fei,et al.Kinetics of the reactions of the light alkenes over SAPO-34[J].Applied Catalysis A:General,2008,348(1):135-141.
[6]田树勋.甲醇制烃反应催化剂积炭研究进展[J].石油学报(石油加工),2016,32(2):427-436.TIAN Shuxun.Progress of coke study on methanol to hydrocarbon catalysts[J].Journal of Petroleum Processing(Petroleum processing),2016,32(2):427-436.
[7]YANG Heqin,LIU Zhicheng,GAO Huanxin,et al.Synthesis and catalytic performances of hierarchical SAPO-34 monolith[J].Journal of Materials Chemistry,2010,20(16):3227-3231.
[8]LIU Yuanlin,WANG Lingzhi,ZHANG Jinlong,et al.A layered mesoporous SAPO-34 prepared by using as-synthesized SBA-15 as silica source[J].Microporous and Mesoporous Materials,2011,145(1/2/3):150-156.
[9]KANG Eun A,KIM Tae Wan,CHAE Ho Jeong,et al.Synthesis of mesoporous SAPO-34 zeolite from mesoporous silica materials for methanol to light olefins[J].Journal of Nanoscience and Nanotechnology,2013,13(11):7498-7503.
[10]刘蓉,王晓龙,肖天存,等.多级孔结构SAPO分子筛的制备及其催化甲醇制烯烃的性能[J].石油化工,2016,45(12):1434-1440.LIU Rong,WANG Xiaolong,XIAO Tiancun,et al.Preparation of hierarchical SAPO molecular sieve and its catalytic performance in methanol to olefins[J].Journal of Petrochemical Industry,2016,45(12):1434-1440.
[11]KONG L,JIANG Z,ZHAO J,et al.The synthesis of hierarchical SAPO-34 and its enhanced catalytic performance in chloromethane conversion to light olefins[J].Catalysis Letters,2014,144(9):1609-1616.
[12]SUN Q,WANG N,XI D,et al.Organosilane surfactant-directed synthesis of hierarchical porous SAPO-34 catalysts with excellent MTO performance[J].Chemical Communications,2014,50(49):6502-6505.
[13]刘蓉,肖天存,王晓龙,等.介孔导向剂制备多级孔结构SAPO-34分子筛催化剂及其在甲醇制烯烃反应中的应用[J].工业催化,2016,24(12):23-30.LIU Rong,XIAO Tiancun,WANG Xiaolong,et al.Preparation of hierarchical SAPO molecular sieve and its catalytic performance in methanol to olefins[J].Journal of Petrochemical Industry,2016,24(12):23-30.
[14]丁佳佳,刘红星,管洪波,等.SAPO-34分子筛的介孔化制备及其在甲醇制烯烃中的应用[C]//2015年中国化工学会年会论文集.北京:[s.n.],2015.
[15]XI D,SUN Q,CHEN X,et al.The recyclable synthesis of hierarchical zeolite SAPO-34 with excellent MTO catalytic performance[J].Chemical Communications,2015,51(60):11987-11989.
[16]任淑,刘国娟,吴晛,等.酸处理可控制备多级孔SAPO-34及其甲醇制烯烃性能[J].催化学报,2017,38(1):123-130.REN Shu,LIU Guojuan,WU Xian,et al.Enhanced MTO performance over acid treated hierarchical SAPO-34[J].Chinese Journal of Catalysis,2017,38(1):123-130.
[17]刘休,任淑,杨承广,等.碱处理法制备多级孔SAPO-34及其MTO催化性能[C]//第18届全国分子筛学术大会论文集(上).上海:[s.n.],2015.
[18]OGURA M,SHINOMIYA S Y,TATENA J,et al.Alkali treatment technique-new method for modification of structural and acidcatalytic properties of ZSM-5 zeolites[J].Applied Catalysis A:General,2001,219(1):33-43.
[19]朱彭龄.磷酸三乙胺-乙腈流动相体系反相分离2,4-二硝基氟苯-氨基酸衍生物[J].分析测试技术与仪器,2012,18(1):1-13.ZHU Pengling.Anti-phase separation of 2,4-dinitrofluorobenzyamino acid derivatives in TEA-acetonitrile flow phase system[J].Analytical Test Techniques and Instruments,2012,18(1):1-13.
[20]朱杰.流化床甲醇制丙烯催化剂的研究[D].北京:清华大学,2010.
[21]吴金雄,李牛,项寿鹤.低硅体系下SAPO-34分子筛的合成[J].石油化工,2012,41(5):510-514.WU Jinxiong,LI Niu,XIANG Shouhe.Synthesis of SAPO-34 under low silicon system[J].Journal of Petrochemical Industry,2012,41(5):510-514.