Nanosized SSZ-13 zeolite was synthesized by traditional hydrothermal method using N,N,N-trimethyl-1-adamantanaminium hydroxide as the structure-directing agent (SDA). The influence of different preparative conditions ...Nanosized SSZ-13 zeolite was synthesized by traditional hydrothermal method using N,N,N-trimethyl-1-adamantanaminium hydroxide as the structure-directing agent (SDA). The influence of different preparative conditions of nanosized SSZ-13 was investigated systematically. The synthetic zeolites were characterized by X-ray powder diffraction (XRD), nitrogen physisorption, and scanning electron microscopy (SEM). By means of the self-assembled method, the thin SSZ-13/polyvinyl alcohol nanocomposite membranes were obtained by incorporating the nanosized SSZ-13 zeolite into the polymeric precursor (polyvinyl alcohol (PVA)). The permeation properties of pure CO2 and CH4 through the mixed matrix membranes (MMMs) were measured. The results showed that the highly crystalline SSZ-13 zeolite in a dispersed nanocrystal form with a controllable particle size of 100 nm could be hydrothermally synthesized by optimizing the synthetic parameters and the selectivity of CO2/CH4 of the MMMs could reach a value of 40 by changing the amount of nanosized SSZ-13 zeolite.展开更多
High-quality standard oil synthetic zeolite-13(SSZ-13) membranes with thickness only ~ 1.0 μm were prepared on tubular supports by the new seeded-gel approach. Seeded-gel approach is simpler than the normal secondary...High-quality standard oil synthetic zeolite-13(SSZ-13) membranes with thickness only ~ 1.0 μm were prepared on tubular supports by the new seeded-gel approach. Seeded-gel approach is simpler than the normal secondary-growth one since adding seeds in the gel is simpler than seeding on the support surface. The synthesis time was greatly reduced from 3.0 to 1.0 d after synthesis modification of gel aging and seed sizes. Low temperature ozone calcination was used for the removal of the organic structural directing agent. The best SSZ-13 membrane displayed CO_(2)permeances of 1.3 × 10^(-6) and 1.5 × 10^(-6) mol·m^(-2)·s^(-1)·Pa^(-1) and CO_(2)/CH_(4) and CO_(2)/N_(2) selectivities of 125 and 27 for equimolar CO_(2)/CH_(4) and CO_(2)/N2mixtures at 0.2 MPa pressure drop and 298 K, respectively. Separation performance of the membrane in the two binary mixtures is higher than that of most zeolite membranes. Three SSZ-13 membranes were reproducibly prepared on tubular supports by seeded-gel approach and the standard deviation ratios of CO_(2) permeance and CO_(2)/CH_(4) selectivity are 12.5% and 7%, respectively. It suggests that this new synthesis approach is creditable. The effects of temperature and pressure on separation performance of the thin SSZ-13 membranes were studied in the two binary mixtures. The tubular SSZ-13 membranes displayed great potentials for CO_(2) capture from natural gas, biogas and flue gas.展开更多
SSZ-13和SAPO-34是性能优异的甲醇制烯烃(methanol to olefins,MTO)催化剂。本文从酸性、积炭、烃池物种及其反应途径等方面介绍了SSZ-13和SAPO-34的酸强度和酸中心密度的差异及其对MTO反应催化性能的影响,综述了SSZ-13和SAPO-34在MTO...SSZ-13和SAPO-34是性能优异的甲醇制烯烃(methanol to olefins,MTO)催化剂。本文从酸性、积炭、烃池物种及其反应途径等方面介绍了SSZ-13和SAPO-34的酸强度和酸中心密度的差异及其对MTO反应催化性能的影响,综述了SSZ-13和SAPO-34在MTO中的催化反应机理和失活机理的研究进展。总结显示,尽管SSZ-13和SAPO-34都是CHA型拓扑结构,但SSZ-13的酸性强于SAPO-34,更有利于碳正离子的生成;与修边机理相比,侧链烷基化机理是更主要的反应途径,且SSZ-13的甲基化速率比SAPO-34高3个数量级;SSZ-13和SAPO-34的积炭速率和积炭物种存在差异,积炭行为受温度影响较大。从催化剂的角度,指出合理调控酸强度和酸中心密度、研制出能够抑制反应失活的催化剂结构、发展高产乙烯或者丙烯的特色MTO催化剂是以后的研究方向;从反应机理的角度,认为SSZ-13和SAPO-34在MTO反应中活性中间体的形成以及转化途径、活性物种到积炭物种的演变有待进一步研究。此外,如何在MTO反应过程中观察到高活性的反应中间体是今后研究的难点。展开更多
文摘Nanosized SSZ-13 zeolite was synthesized by traditional hydrothermal method using N,N,N-trimethyl-1-adamantanaminium hydroxide as the structure-directing agent (SDA). The influence of different preparative conditions of nanosized SSZ-13 was investigated systematically. The synthetic zeolites were characterized by X-ray powder diffraction (XRD), nitrogen physisorption, and scanning electron microscopy (SEM). By means of the self-assembled method, the thin SSZ-13/polyvinyl alcohol nanocomposite membranes were obtained by incorporating the nanosized SSZ-13 zeolite into the polymeric precursor (polyvinyl alcohol (PVA)). The permeation properties of pure CO2 and CH4 through the mixed matrix membranes (MMMs) were measured. The results showed that the highly crystalline SSZ-13 zeolite in a dispersed nanocrystal form with a controllable particle size of 100 nm could be hydrothermally synthesized by optimizing the synthetic parameters and the selectivity of CO2/CH4 of the MMMs could reach a value of 40 by changing the amount of nanosized SSZ-13 zeolite.
基金Financial supports from the National Natural Science Foundation of China (21921006, 21938007 and 21576131)the open project of the State Key Laboratory of Materials-Oriented Chemical Engineering of China (KL21-04)。
文摘High-quality standard oil synthetic zeolite-13(SSZ-13) membranes with thickness only ~ 1.0 μm were prepared on tubular supports by the new seeded-gel approach. Seeded-gel approach is simpler than the normal secondary-growth one since adding seeds in the gel is simpler than seeding on the support surface. The synthesis time was greatly reduced from 3.0 to 1.0 d after synthesis modification of gel aging and seed sizes. Low temperature ozone calcination was used for the removal of the organic structural directing agent. The best SSZ-13 membrane displayed CO_(2)permeances of 1.3 × 10^(-6) and 1.5 × 10^(-6) mol·m^(-2)·s^(-1)·Pa^(-1) and CO_(2)/CH_(4) and CO_(2)/N_(2) selectivities of 125 and 27 for equimolar CO_(2)/CH_(4) and CO_(2)/N2mixtures at 0.2 MPa pressure drop and 298 K, respectively. Separation performance of the membrane in the two binary mixtures is higher than that of most zeolite membranes. Three SSZ-13 membranes were reproducibly prepared on tubular supports by seeded-gel approach and the standard deviation ratios of CO_(2) permeance and CO_(2)/CH_(4) selectivity are 12.5% and 7%, respectively. It suggests that this new synthesis approach is creditable. The effects of temperature and pressure on separation performance of the thin SSZ-13 membranes were studied in the two binary mixtures. The tubular SSZ-13 membranes displayed great potentials for CO_(2) capture from natural gas, biogas and flue gas.
文摘SSZ-13和SAPO-34是性能优异的甲醇制烯烃(methanol to olefins,MTO)催化剂。本文从酸性、积炭、烃池物种及其反应途径等方面介绍了SSZ-13和SAPO-34的酸强度和酸中心密度的差异及其对MTO反应催化性能的影响,综述了SSZ-13和SAPO-34在MTO中的催化反应机理和失活机理的研究进展。总结显示,尽管SSZ-13和SAPO-34都是CHA型拓扑结构,但SSZ-13的酸性强于SAPO-34,更有利于碳正离子的生成;与修边机理相比,侧链烷基化机理是更主要的反应途径,且SSZ-13的甲基化速率比SAPO-34高3个数量级;SSZ-13和SAPO-34的积炭速率和积炭物种存在差异,积炭行为受温度影响较大。从催化剂的角度,指出合理调控酸强度和酸中心密度、研制出能够抑制反应失活的催化剂结构、发展高产乙烯或者丙烯的特色MTO催化剂是以后的研究方向;从反应机理的角度,认为SSZ-13和SAPO-34在MTO反应中活性中间体的形成以及转化途径、活性物种到积炭物种的演变有待进一步研究。此外,如何在MTO反应过程中观察到高活性的反应中间体是今后研究的难点。
文摘以硅溶胶、硫酸铝、氢氧化钠、去离子水为原料,以N,N,N-三甲基金钢烷氢氧化铵为模板剂(R),用传统的水热法合成分子筛SSZ-13,对合成产物用XRD、SEM、FT-IR和BET进行表征,并通过改变原料的配比和反应条件确定它的最佳合成条件.实验结果表明:在反应温度为155℃、晶化时间为3 d时,其最佳合成氧化物的摩尔比范围:SiO2/A12O3为40,Na2O/A12O3为12～16,R2O/A12O3为3～5,H2O/A12O3为900～1 350.在最佳条件下合成的分子筛SSZ-13,大大缩短了反应时间,加晶种或促进剂时,晶化时间缩短为2 d.
