A defect-free SAPO-44 zeolite membrane firmly anchored the porous α-Al2O3 plate substrate was successfully synthesized. The separating results showed that the H2/N2 and H2/CO permselectivities were higher than those ...A defect-free SAPO-44 zeolite membrane firmly anchored the porous α-Al2O3 plate substrate was successfully synthesized. The separating results showed that the H2/N2 and H2/CO permselectivities were higher than those of the corresponding Knudsen diffusion and the substrate, attaining 5.78 and 7.15 respectively.展开更多
In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation pro...In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.展开更多
SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere.In this work,n-dodecyltrimethoxysilane(DTMS)was used to mo...SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere.In this work,n-dodecyltrimethoxysilane(DTMS)was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment.The modified membranes were fully characterized.Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones.The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO2 permeance of 1.18×10-6 mol·m-2·s-1·Pa-1 for separation of dry CO2/CH4 at 298 K.However,its separation selectivity declined to 0.9 and the CO2 permeance was only about 1.7×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 at same temperature.High temperature(e.g.353 K)could reduce the effect of moisture to improve SAPO-34 separation selectivity,but further increasing temperature(e.g.373 K)led to decrease in CO2/CH4 separation selectivity.A significant decrease of selectivity was observed at higher pressure drop.The modified SAPO-34 membrane showed decreased CO2 permeance but increased separation selectivity for dry CO2/CH4 gas mixture,and super performance for wet CO2/CH4 gas mixture due to the improved hydrophobicity of membrane surface.A separation selectivity of 65 and CO2 permeance of 4.73×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 mixture can be observed at 353 K with a pressure drop of 0.4 MPa.Furthermore,the modified membrane exhibited stable separation performance during the 120-hour test for wet CO2/CH4 mixture at 353 K.The hydrophobic modification paves a way for SAPO-34 membranes in real applications.展开更多
Methanol-to-olefins(MTO)is industrially applied to produce ethylene and propylene using methanol converted from coal,synthetic gas,and biomass.SAPO-34 zeolites,as the most efficient catalyst in MTO process,are subject...Methanol-to-olefins(MTO)is industrially applied to produce ethylene and propylene using methanol converted from coal,synthetic gas,and biomass.SAPO-34 zeolites,as the most efficient catalyst in MTO process,are subject to the rapid deactivation due to coke deposition.Recent work shows that steam regeneration can provide advantages such as low carbon dioxide emission and enhanced light olefins yield in MTO process,compared to that by air regeneration.A kinetic study on the steam regeneration of spent SAPO-34 catalyst has been carried out in this work.In doing so,we first investigated the effect of temperature on the regeneration performance by monitoring the crystal structure,acidity,residual coke properties and other structural parameters.The results show that with the increase of regeneration temperature,the compositions of residual coke on the catalyst change from pyrene and phenanthrene to naphthalene,which are normally considered as active hydrocarbon pool species in MTO reaction.However,when the regeneration temperature is too high,nitrogen oxides can be found in the residual coke.Meanwhile,as the regeneration temperature increases,the quantity of residual coke reduces and the acidity,BET surface area and pore structure of the regenerated samples can be better recovered,resulting in prolonging catalyst lifetime.We have further derived the kinetics of steam regeneration,and obtained an activation energy of about 177.8 kJ·mol^(-1).Compared that with air regeneration,the activation energy of steam regeneration is higher,indicating that the steam regeneration process is more difficult to occur.展开更多
As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin(MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosph...As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin(MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite(CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this minireview to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.展开更多
Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weigh...Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weights （MWs） and concentrations in the synthesis precursor, several samples were synthesized and characterized. Applying a PEG capping agent to the precursors led to the formation of tuned mesopores within the microporous matrix of the SAPO. The effects of the PEG molecular weight and PEG/Al molar ratio were investigated to maximize the efficiency of the catalyst in the methanol-to-olefin （MTO） process. Using PEG with a MW of 6000 resulted in the formation of both Zeolite Rho and chabazite structural frameworks （i.e., DNL-6 and SAPO-34）. Pure SAPO-34 samples were successfully prepared using PEG with a MW of 4000. Our results showed that the PEG concentrations affect the porosity and acidity of the synthesized materials. Furthermore, the SAPO-34 sample synthesized with PEG （MW of 4000） and a PEG/Al molar ratio of 0.0125 showed a superior catalytic stability in the MTO reaction owing to the tuned bi-modal porosity and tailored acidity pattern. Finally, through reactivation experiments, it was found that the catalyst is stable even after several regeneration cycles.展开更多
文摘A defect-free SAPO-44 zeolite membrane firmly anchored the porous α-Al2O3 plate substrate was successfully synthesized. The separating results showed that the H2/N2 and H2/CO permselectivities were higher than those of the corresponding Knudsen diffusion and the substrate, attaining 5.78 and 7.15 respectively.
基金supported by the National Science and Technology Planning Project(No.2011BAC08B00)the National High Technology Research and Development Program of China(863 Program)(No.2012AA03A611)
文摘In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.
基金Supported by the National Natural Science Foundation of China(21490585,21776128)the“Six Top Talents”and“333 Talent Project”of Jiangsu Province,State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201602,ZK201719)Priority Academy Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere.In this work,n-dodecyltrimethoxysilane(DTMS)was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment.The modified membranes were fully characterized.Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones.The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO2 permeance of 1.18×10-6 mol·m-2·s-1·Pa-1 for separation of dry CO2/CH4 at 298 K.However,its separation selectivity declined to 0.9 and the CO2 permeance was only about 1.7×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 at same temperature.High temperature(e.g.353 K)could reduce the effect of moisture to improve SAPO-34 separation selectivity,but further increasing temperature(e.g.373 K)led to decrease in CO2/CH4 separation selectivity.A significant decrease of selectivity was observed at higher pressure drop.The modified SAPO-34 membrane showed decreased CO2 permeance but increased separation selectivity for dry CO2/CH4 gas mixture,and super performance for wet CO2/CH4 gas mixture due to the improved hydrophobicity of membrane surface.A separation selectivity of 65 and CO2 permeance of 4.73×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 mixture can be observed at 353 K with a pressure drop of 0.4 MPa.Furthermore,the modified membrane exhibited stable separation performance during the 120-hour test for wet CO2/CH4 mixture at 353 K.The hydrophobic modification paves a way for SAPO-34 membranes in real applications.
基金the National Natural Science Foundation of China(91834302)。
文摘Methanol-to-olefins(MTO)is industrially applied to produce ethylene and propylene using methanol converted from coal,synthetic gas,and biomass.SAPO-34 zeolites,as the most efficient catalyst in MTO process,are subject to the rapid deactivation due to coke deposition.Recent work shows that steam regeneration can provide advantages such as low carbon dioxide emission and enhanced light olefins yield in MTO process,compared to that by air regeneration.A kinetic study on the steam regeneration of spent SAPO-34 catalyst has been carried out in this work.In doing so,we first investigated the effect of temperature on the regeneration performance by monitoring the crystal structure,acidity,residual coke properties and other structural parameters.The results show that with the increase of regeneration temperature,the compositions of residual coke on the catalyst change from pyrene and phenanthrene to naphthalene,which are normally considered as active hydrocarbon pool species in MTO reaction.However,when the regeneration temperature is too high,nitrogen oxides can be found in the residual coke.Meanwhile,as the regeneration temperature increases,the quantity of residual coke reduces and the acidity,BET surface area and pore structure of the regenerated samples can be better recovered,resulting in prolonging catalyst lifetime.We have further derived the kinetics of steam regeneration,and obtained an activation energy of about 177.8 kJ·mol^(-1).Compared that with air regeneration,the activation energy of steam regeneration is higher,indicating that the steam regeneration process is more difficult to occur.
基金supported by the National Natural Science Foundation of China(21971082)the Jilin Province Science and Technology Development Plan(20190201229JC and 20200201096JC)+1 种基金the China Postdoctoral Science Foundation(2018M640280 and 2019T120235)for supporting this workthe National 111 Project(B17020)。
文摘As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin(MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite(CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this minireview to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.
文摘Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weights （MWs） and concentrations in the synthesis precursor, several samples were synthesized and characterized. Applying a PEG capping agent to the precursors led to the formation of tuned mesopores within the microporous matrix of the SAPO. The effects of the PEG molecular weight and PEG/Al molar ratio were investigated to maximize the efficiency of the catalyst in the methanol-to-olefin （MTO） process. Using PEG with a MW of 6000 resulted in the formation of both Zeolite Rho and chabazite structural frameworks （i.e., DNL-6 and SAPO-34）. Pure SAPO-34 samples were successfully prepared using PEG with a MW of 4000. Our results showed that the PEG concentrations affect the porosity and acidity of the synthesized materials. Furthermore, the SAPO-34 sample synthesized with PEG （MW of 4000） and a PEG/Al molar ratio of 0.0125 showed a superior catalytic stability in the MTO reaction owing to the tuned bi-modal porosity and tailored acidity pattern. Finally, through reactivation experiments, it was found that the catalyst is stable even after several regeneration cycles.
