硅烷修饰SBA-15固载聚醚离子液体催化剂的制备与性能
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摘要
将3种聚醚离子液体,即Cl[PECH-MIM]-OH、Cl[PECH-MIM]-COOH和Cl[PECH-MIM]-NH_2,分别与助催化剂ZnBr_2反应制得复合型聚醚离子液体,再用硅烷(CPTES)修饰分子筛SBA-15,并将其固载复合聚醚离子液体,制得固载化催化剂SCP-OH/[ZnBr_2]、SCP-COOH/[ZnBr_2]和SCP-NH_2/[ZnBr_2]。利用红外光谱仪、热重分析仪、电镜扫描仪对SBA-15及3种固载化催化剂进行化学结构、热性能和表观形貌的表征,并研究其催化环氧丙烷(PO)与CO_2合成碳酸丙烯酯(PC)反应的性能。结果表明,复合型聚醚离子液体成功固载于硅烷分子筛上,实现了离子液体的相态转变及其高效的非均相转化CO_2。对于3种固载化离子液体催化环氧丙烷与CO_2的羰基化反应,SCP-COOH/[ZnBr_2]的催化性能最佳,在CO_2压力3.0 MPa、反应温度130℃、液时空速为0.5 h~(-1)的反应条件下,PO转化率为83.8%、产物PC选择性为94.1%,并且连续使用80 h后仍保持良好的催化性能。
Three kinds of polyether ionic liquids, Cl[PECH-MIM]-OH, Cl[PECH-MIM]-COOH and Cl[PECH-MIM]-NH_2, were used to react with the ZnBr_2 promoter for preparing corresponding composite polyether ionic liquids. Then silane coupling was applied to bond molecular sieve SBA-15 with the immobilized SCP-OH/[ZnBr_2], SCP-COOH/[ZnBr_2] and SCP-NH_2/[ZnBr_2]. The chemical structure, thermal properties and morphology of SBA-15 and three immobilized catalysts were characterized by infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. Their catalytic properties in the conversion CO_2 with propylene oxide(PO) to propylene carbonate(PC) were studied. Results showed that the composite polyether ionic liquids were successfully immobilized on the silane molecular sieves, with the phase transition of the ionic liquids and efficient heterogeneous conversion of CO_2. SCP-COOH/[ZnBr_2] shows the best catalytic performance among three immobilized catalysts in the reaction of CO_2 with PO. When the CO_2 pressure of 3.0 MPa, reaction temperature of 130 ℃, and liquid hourly space velocity(LHSV) of 0.5 h~(-1),the PO conversion and PC selectivity are 83.8% and 94.1%, respectively. After continuous use for 80 h, SCP-COOH/[ZnBr_2] still maintains good catalytic performance.
Three kinds of polyether ionic liquids, Cl[PECH-MIM]-OH, Cl[PECH-MIM]-COOH and Cl[PECH-MIM]-NH_2, were used to react with the ZnBr_2 promoter for preparing corresponding composite polyether ionic liquids. Then silane coupling was applied to bond molecular sieve SBA-15 with the immobilized SCP-OH/[ZnBr_2], SCP-COOH/[ZnBr_2] and SCP-NH_2/[ZnBr_2]. The chemical structure, thermal properties and morphology of SBA-15 and three immobilized catalysts were characterized by infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. Their catalytic properties in the conversion CO_2 with propylene oxide(PO) to propylene carbonate(PC) were studied. Results showed that the composite polyether ionic liquids were successfully immobilized on the silane molecular sieves, with the phase transition of the ionic liquids and efficient heterogeneous conversion of CO_2. SCP-COOH/[ZnBr_2] shows the best catalytic performance among three immobilized catalysts in the reaction of CO_2 with PO. When the CO_2 pressure of 3.0 MPa, reaction temperature of 130 ℃, and liquid hourly space velocity(LHSV) of 0.5 h~(-1),the PO conversion and PC selectivity are 83.8% and 94.1%, respectively. After continuous use for 80 h, SCP-COOH/[ZnBr_2] still maintains good catalytic performance.
引文
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[17]郭立颖,马秀云,王立岩,等.氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能[J].化工进展,2017,36(2):581-587.(GUO Liying,MA Xiuyun,WANGLiyan,et al.Preparation and catalytic performance of1-aminopolyether-3-methylimidazolium ionic liquids[J].Chemical Industry and Engineering Progress,2017,36(2):581-587.)
[18]SAPTAL V B,BHANAGE B M.Bifunctional ionic liquids for the multitask fixation of carbon dioxide into valuable chemicals[J].Chem Cat Chem,2016,8(1):244-250.
[19]FUJITA S I,NISHIURA M,ARAI M.Synthesis of styrene carbonate from carbon dioxide and styrene oxide with various zinc halide-based ionic liquids[J].Catalysis Letters,2010,135(3/4):263-268.
[20]BAJ S,KRAWCZYK T,JASIAK K,et al.Catalytic coupling of epoxides and CO2 to cyclic carbonates by carbon nanotube-supported quaternary ammonium salts[J].Applied Catalysis A:General,2014,488(169):96-102.
[2]QIAN Q L,YANG Y F,SHAO H X.Solid electrolyte interphase formation by propylene carbonate reduction for lithium anode[J].Physical Chemistry Chemical Physics,2017,19(42):28772-28780.
[3]杨子浩,林梅钦,董朝霞,等.超临界CO2在有机液体中的分散[J].石油学报(石油加工),2015,31(2):596-602.(YANG Zihao,LIN Meiqin,DONG Zhaoxia,et al.Dispersion of supercritical CO2 in organic liquids[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(2):596-602.)
[4]NORTH M,PASQUALE R,YOUNG C.Synthesis of cyclic carbonates from oxides and CO2[J].Green Chemistry,2010,12(9):1514-1539.
[5]XIAO B N,SUN J,WANG J Q,et al.Triethanolamine/KI:A multifunctional catalyst for CO2activation and conversion with epoxides into cyclic carbonates[J].Synthetic Communications,2013,43(22):2985-2997.
[6]马昱博,石峰,邓友全,等.NaY分子筛超笼内离子液体和金属配合物自组装制备溶剂分子和金属配合物一体化催化剂[J].催化学报,2010,31(8):933-937.(MA Yubo,SHI Feng,DENG Youquan,et al.Selfassembly of metal complex and ionic liquid in NaYmolecular sieve super cage to prepare solvent molecule and metal complex integrated catalyst[J].Journal of Catalysis,2010,31(8):933-937.)
[7]GUO L Y,DENG L L,JIN X C,et al.Catalytic conversion of CO2 into propylene carbonate in a continuous fixed bed reactor by immobilized ionic liquids[J].RSC Advances,2018,8:26554-26562.
[8]VALKENBERG M H,DECASTRO C,HLDERICH W F.Immobilisation of ionic liquids on solid supports[J].Green Chemistry,2002,4(2):88-93.
[9]JADHAV A H,THORAT G M,LEE K,et al.Effect of anion type of imidazolium based polymer supported ionic liquids on the solvent free synthesis of cycloaddition of CO2into epoxide[J].Catalysis Today,2016,265:56-67.
[10]TAHERIMEHR M,VANDEVOORDEEB,WEE L H,et al.Strategies for enhancing the catalytic performance of metal-organic frameworks in the fixation of CO2into cyclic carbonates[J].Chemsuschem,2017,10(6):1283-1291.
[11]HAN L,LI H Q,CHOI S J,et al.Ionic liquids grafted on carbon nanotubes as highly efficient heterogeneous catalysts for the synthesis of cyclic carbonates[J].Appl Catal A:Gen,2012,429/430:67-72.
[12]ZALOMAEVA O V,MAKSIMCHUK N V,CHIBIRYAEV A M,et al.Synthesis of cyclic carbonates from epoxides or olefins and CO2,catalyzed by metal-organic frameworks and quaternary ammonium salts[J].Journal of Energy Chemistry,2013,22(1):130-135.
[13]王中学,王大喜,赵震,等.SBA-15分子筛羟基结构性质及其催化活性的理论研究[J].无机化学学报,2012,28(1):88-96.(WANG Zhongxue,WANGDaxi,ZHAO Zhen,et al.Theoretical study on hydroxy structure and catalytic activity of SBA-15molecular sieve[J].Journal of Inorganic Chemistry,2012,28(1):88-96.)
[14]DAI W L,CHEN L,YIN S F,et al.3-(2-hydroxylethyl)-1-Propylimidazolium bromide immobilized on SBA-15as efficient catalyst for the synthesis of cyclic carbonates via the coupling of carbon dioxide with epoxides[J].Catalysis Letters,2010,135(3/4):295-304.
[15]郭立颖,张彬,李承媛,等.聚醚离子液体的合成及其对酚醛树脂性能的影响[J].塑料,2015,44(4):57-59.(GUO Liying,ZHANG Bin,LI Chengyuan,et al.Synthesis of polyether ionic liquids and their effects on the properties of phenolic resins[J].Plastics,2015,44(4):57-59.)
[16]郭立颖,马秀云,邓莉莉,等.氯化1-羧基聚醚-3-甲基咪唑离子液体的制备及催化性能[J].石油学报(石油加工),2017,33(2):342-348.(GUO Liying,MAXiuyun,DENG Lili,et al.Preparation and catalytic performance of 1-carboxypolyether-3-methylimidazolium ionic liquids[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(2):342-348.)
[17]郭立颖,马秀云,王立岩,等.氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能[J].化工进展,2017,36(2):581-587.(GUO Liying,MA Xiuyun,WANGLiyan,et al.Preparation and catalytic performance of1-aminopolyether-3-methylimidazolium ionic liquids[J].Chemical Industry and Engineering Progress,2017,36(2):581-587.)
[18]SAPTAL V B,BHANAGE B M.Bifunctional ionic liquids for the multitask fixation of carbon dioxide into valuable chemicals[J].Chem Cat Chem,2016,8(1):244-250.
[19]FUJITA S I,NISHIURA M,ARAI M.Synthesis of styrene carbonate from carbon dioxide and styrene oxide with various zinc halide-based ionic liquids[J].Catalysis Letters,2010,135(3/4):263-268.
[20]BAJ S,KRAWCZYK T,JASIAK K,et al.Catalytic coupling of epoxides and CO2 to cyclic carbonates by carbon nanotube-supported quaternary ammonium salts[J].Applied Catalysis A:General,2014,488(169):96-102.
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