A series of Cu-SSZ-13 catalysts with the same Cu loading were prepared by different methods of incipient wetness impregnation [Cu-SSZ-13(IWI)], ion exchange[Cu-SSZ-13(IE)] and hydro-thermal synthesis [Cu-SSZ-13(HTS)]....A series of Cu-SSZ-13 catalysts with the same Cu loading were prepared by different methods of incipient wetness impregnation [Cu-SSZ-13(IWI)], ion exchange[Cu-SSZ-13(IE)] and hydro-thermal synthesis [Cu-SSZ-13(HTS)]. Their activity for selective catalytic reduction of nitrogen oxides(NO_x) with NH3 was determined. The results show that the Cu-SSZ-13(HTS) catalyst exhibits a better ammonia selective catalytic reduction(NH3-SCR)activity compared with the other two catalysts, over which more than 90% NO conversion is obtained at 215-600℃under the space velocity of 180,000 h^(-1). The characterization results reveal that the Cu-SSZ-13(HTS) catalyst possesses more amount of stable Cu^(2+) in the six-membered ring and high ability for NH3 and NO adsorption, leading to its high NH3-SCR activity, although this catalyst has low surface area. On the other hand, the activity of Cu-SSZ-13(IE) catalyst is almost the same as that of Cu-SSZ-13(IWI) catalyst at the temperature lower than 400 ℃, but the activity of the former is much higher than that of the latter at > 400 ℃ due to the high activity of Cu-SSZ-13(IWI) catalyst for NH3 oxidation.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
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
Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown ...Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.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
The main disadvantage of microporous SSZ-13 catalyst used in the methanol to olefins(MTO) process is its rapid deactivation due to its relatively low coke resistance. Meanwhile, the hierarchical zeolites usually exhib...The main disadvantage of microporous SSZ-13 catalyst used in the methanol to olefins(MTO) process is its rapid deactivation due to its relatively low coke resistance. Meanwhile, the hierarchical zeolites usually exhibit improved catalytic stability thanks to their better mass transfer ability. Herein, the hierarchically nanoporous SSZ-13 zeolites were one-pot synthesized by using N,N,N-trimethyl-1-adamantanammonium hydroxide as a microporous structure directing agent and C_(18)H_(37) N^+(CH_3)_2 C_6H_(12) N^+(CH_3)_2 C_6 H_(13)(Br^-)_2(hereinafter abbreviated as C_(18-6-6) Br_2) as a mesoporogen. The hierarchically nanoporous SSZ-13 catalyst was characterized by XRD, N_2 physisorption, SEM, TEM, TG-DTG, ^(27) Al and ^(29) SiNMR spectroscopy and NH_3-TPD techniques. The results showed that the hierarchical SSZ-13 zeolite synthesized in the presence of the C_(18-6-6) Br_2 surfactant exhibits aggregates of primary nanocrystals and contains the well-developed mesopores and excellent acidity. Compared to its conventional counterpart, the hierarchical SSZ-13 zeolite has longer catalytic lifetime and higher selectivity for ethylene and propylene in the MTO reaction, which can be attributed to the synergistic effect of their good acidity and improved diffusion properties resulted from the hierarchical pore structure.展开更多
To study the infl uence of the preparation method on Cu active sites and the reaction pathway in NO reduction by NH 3 over Cu-SSZ-13, three kinds of catalysts (Cu ion-exchanged SSZ-13 1 , one-pot synthesis Cu-SSZ-13 2...To study the infl uence of the preparation method on Cu active sites and the reaction pathway in NO reduction by NH 3 over Cu-SSZ-13, three kinds of catalysts (Cu ion-exchanged SSZ-13 1 , one-pot synthesis Cu-SSZ-13 2 , and Ce 0.017 -Fe 0.017 /Cu- SSZ-13 [Ce and Fe ion exchange on the basis of Cu-SSZ-13 2 ]) were prepared. In situ diff use refl ectance infrared Fourier transform spectroscopy and H 2 temperature program reduction were used to study the diff erences in the reaction pathways and Cu active sites over the three kinds of catalysts. Density functional theory was employed to study the eff ect of active sites on the reaction pathway. In situ DRIFTS showed that the reaction pathway on Cu-SSZ-13 1 during NO oxidation was diff erent from that on Cu-SSZ-13 2 and Ce 0.017 -Fe 0.017 /Cu-SSZ-13. The diff erence was that intermediate NO 2 was involved in the selective catalytic reduction reaction on Cu-SSZ-13 1 , whereas NO 2 was not found during the reaction process on Cu-SSZ-13 2 and Ce 0.017 -Fe 0.017 /Cu-SSZ-13. H 2 -TPR studies revealed that the three catalysts had diff erent Cu active sites, which were located in the six-membered ring, eight-membered ring, and CHA cage. On the basis of DFT studies, NO and O 2 were more conducive to form nitrate when the Cu species was on the six- and eight-membered rings;by contrast, NO and O 2 were more conducive to form NO 2 in the cage. These results showed that diff erent preparation methods led to various Cu active sites, and varying Cu active sites could lead to diff erent NO oxidation processes.展开更多
基金financially supported by the National Key Research and Development Program of China (No. 2016YFC0204300)the National Natural Science Foundation of China (Nos. 21577034 and 21333003)the Science and Technology Commission of Shanghai Municipality (No. 16ZR1407900)
文摘A series of Cu-SSZ-13 catalysts with the same Cu loading were prepared by different methods of incipient wetness impregnation [Cu-SSZ-13(IWI)], ion exchange[Cu-SSZ-13(IE)] and hydro-thermal synthesis [Cu-SSZ-13(HTS)]. Their activity for selective catalytic reduction of nitrogen oxides(NO_x) with NH3 was determined. The results show that the Cu-SSZ-13(HTS) catalyst exhibits a better ammonia selective catalytic reduction(NH3-SCR)activity compared with the other two catalysts, over which more than 90% NO conversion is obtained at 215-600℃under the space velocity of 180,000 h^(-1). The characterization results reveal that the Cu-SSZ-13(HTS) catalyst possesses more amount of stable Cu^(2+) in the six-membered ring and high ability for NH3 and NO adsorption, leading to its high NH3-SCR activity, although this catalyst has low surface area. On the other hand, the activity of Cu-SSZ-13(IE) catalyst is almost the same as that of Cu-SSZ-13(IWI) catalyst at the temperature lower than 400 ℃, but the activity of the former is much higher than that of the latter at > 400 ℃ due to the high activity of Cu-SSZ-13(IWI) catalyst for NH3 oxidation.
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supported by the INCOEmission project coordinated by BASF SE,Germanythe support from the Fundamental Research Funds for the Central Universities(DC201502080409)~~
文摘Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
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.
基金the National Natural Science Foundation of China(No.51371123)the Natural Science Foundation of Shanxi Province(No.201701D121024)the Research Project Supported by Shanxi Scholarship Council of China(No.2017-042)for providing financial support for this study
文摘The main disadvantage of microporous SSZ-13 catalyst used in the methanol to olefins(MTO) process is its rapid deactivation due to its relatively low coke resistance. Meanwhile, the hierarchical zeolites usually exhibit improved catalytic stability thanks to their better mass transfer ability. Herein, the hierarchically nanoporous SSZ-13 zeolites were one-pot synthesized by using N,N,N-trimethyl-1-adamantanammonium hydroxide as a microporous structure directing agent and C_(18)H_(37) N^+(CH_3)_2 C_6H_(12) N^+(CH_3)_2 C_6 H_(13)(Br^-)_2(hereinafter abbreviated as C_(18-6-6) Br_2) as a mesoporogen. The hierarchically nanoporous SSZ-13 catalyst was characterized by XRD, N_2 physisorption, SEM, TEM, TG-DTG, ^(27) Al and ^(29) SiNMR spectroscopy and NH_3-TPD techniques. The results showed that the hierarchical SSZ-13 zeolite synthesized in the presence of the C_(18-6-6) Br_2 surfactant exhibits aggregates of primary nanocrystals and contains the well-developed mesopores and excellent acidity. Compared to its conventional counterpart, the hierarchical SSZ-13 zeolite has longer catalytic lifetime and higher selectivity for ethylene and propylene in the MTO reaction, which can be attributed to the synergistic effect of their good acidity and improved diffusion properties resulted from the hierarchical pore structure.
文摘To study the infl uence of the preparation method on Cu active sites and the reaction pathway in NO reduction by NH 3 over Cu-SSZ-13, three kinds of catalysts (Cu ion-exchanged SSZ-13 1 , one-pot synthesis Cu-SSZ-13 2 , and Ce 0.017 -Fe 0.017 /Cu- SSZ-13 [Ce and Fe ion exchange on the basis of Cu-SSZ-13 2 ]) were prepared. In situ diff use refl ectance infrared Fourier transform spectroscopy and H 2 temperature program reduction were used to study the diff erences in the reaction pathways and Cu active sites over the three kinds of catalysts. Density functional theory was employed to study the eff ect of active sites on the reaction pathway. In situ DRIFTS showed that the reaction pathway on Cu-SSZ-13 1 during NO oxidation was diff erent from that on Cu-SSZ-13 2 and Ce 0.017 -Fe 0.017 /Cu-SSZ-13. The diff erence was that intermediate NO 2 was involved in the selective catalytic reduction reaction on Cu-SSZ-13 1 , whereas NO 2 was not found during the reaction process on Cu-SSZ-13 2 and Ce 0.017 -Fe 0.017 /Cu-SSZ-13. H 2 -TPR studies revealed that the three catalysts had diff erent Cu active sites, which were located in the six-membered ring, eight-membered ring, and CHA cage. On the basis of DFT studies, NO and O 2 were more conducive to form nitrate when the Cu species was on the six- and eight-membered rings;by contrast, NO and O 2 were more conducive to form NO 2 in the cage. These results showed that diff erent preparation methods led to various Cu active sites, and varying Cu active sites could lead to diff erent NO oxidation processes.
