Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production...Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.展开更多
In this work, a dual-phase material consisting Gd0.1Ce0.9O2-δ （GDC, 60 wt%） was synthesized. of La0.7Ca0.3Cr0.95Zn0.05O3-δ （LCCZ, 40 wt%） and Properties including phase structure, sintering behavior, electrical ...In this work, a dual-phase material consisting Gd0.1Ce0.9O2-δ （GDC, 60 wt%） was synthesized. of La0.7Ca0.3Cr0.95Zn0.05O3-δ （LCCZ, 40 wt%） and Properties including phase structure, sintering behavior, electrical conductivity and oxygen permeability for LCCZ-GDC were evaluated. The results show that dense LCCZ-GDC dual-phase disks were obtained at the sintering temperature of 1250, 1300, 1350 and 1400 ℃ by tape casting and high temperature sintering method. The grain sizes of both GDC and LCCZ grew up with the increasing of sintering temperature. The average grain size of GDC was about 0.5, 0.8, 1.4, 1.8 μm while the average grain size of LCCZ was about 0.8, 1.5, 1.8 and 2 pm after sintering at 1250, 1300, 1350 and 1400℃, respectively. Oxygen flux of LCCZ-GDC decreased with the increase of sintering temperature from 1250 to 1400 ℃. The oxygen flux of LCCZ-GDC sintered at 1250 ℃ reached 0.079 mL/min/cm2 at 975℃ with a membrane thickness of 800 μm. Dual-phase material of LCCZ-GDC will be a promising oxygen transport membrane material for its low sintering temperature and good microstructure.展开更多
A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray di...A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction （HTXRD）. The thermal expansion coefficient of BSFZ is 10.5×10^-6 K^-1, which is lower than that of cobalt-based perovskite materials. The BSFZ membrane was also used to construct reactors for the partial oxidation of methane （POM） to syngas. Results show that the BSFZ membrane can be operated for the POM reaction for more than 100 h without any fractures. The CO selectivity of 97% is obtained. The steady oxygen permeation flux reaches around 2.5 mL/min cm^2 during POM reaction.展开更多
A series of BaZr0.2Co0.8-χFeχO3-σ materials for oxygen separation were synthesized through a citric and EDTA acid combined complexing method, and their crystal structures, oxygen permeabilities, sintering and seali...A series of BaZr0.2Co0.8-χFeχO3-σ materials for oxygen separation were synthesized through a citric and EDTA acid combined complexing method, and their crystal structures, oxygen permeabilities, sintering and sealing abilities were investigated. The results showed that the cubic perovskite structure was formed for materials in the composition range investigated. Oxygen permeation flux and stability, as well as sintering and sealing abilities of the synthesized materials were increased or improved apparently due to the introduction of zirconium. For example, the oxygen permeation flux reached 0.8 mL/min · cm2 when χ = 0.2 or 0.3 at 950℃, and a stable time-related oxygen permeation flux was found for the BaZr0.2Co0.3Fe0.5O3-σ membrane at 800℃.展开更多
Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-δ (y≤0.4) and BaBixCo0.2Fe0.8-xO3-δ (x=0.1 -0.5). The mater...Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-δ (y≤0.4) and BaBixCo0.2Fe0.8-xO3-δ (x=0.1 -0.5). The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-δmembrane reached about0.77×106 mol/cm2 ·s under an air/helium oxygen partial pressure gradient at 900 ℃, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2Co0.展开更多
研究了具有氧离子导电性和电子导电性的钴系钙钛矿型复合氧化物混合导电体材料中氧的选择性透过能力,考察了该体系中 A 位低价金属离子置换量、置换金属离子的种类及 B 位置换金属离子的种类对氧的透过率的影响.结果表明:改变钙钛矿型...研究了具有氧离子导电性和电子导电性的钴系钙钛矿型复合氧化物混合导电体材料中氧的选择性透过能力,考察了该体系中 A 位低价金属离子置换量、置换金属离子的种类及 B 位置换金属离子的种类对氧的透过率的影响.结果表明:改变钙钛矿型复合氧化物的组成,提高材料中氧空位浓度和氧离子导电率,有利于提高氧离子的扩散速度,即提高氧的透过率和降低氧透过的起始温度.将钙钛矿型复合氧化物混合导电体氧透膜与固体电解质氧透膜进行了比较,前者具有结构简单的优点,有希望成为一种新型高温氧分离膜介质材料.展开更多
基金Financial support by the Spanish Ministry of Science(PID2022139663OB-I00 and CEX2021-001230-S grant funded by MCIN/AE I/10.13039/501100011033)with funding from Next Generation EU(PRTR-C17.I1)within the Planes Complementarios con CCAA(Area of Green Hydrogen and Energy)+2 种基金carried out in the CSIC Interdisciplinary Thematic Platform(PTI+)Transición Energética Sostenible+(PTI-TRANSENER+)the Universitat Politècnica de València(UPV)the support of the Servicio de Microscopía Elcectronica of the UPV。
文摘Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.
基金the financial support from the National Basic Research Program of China("973 Program",No. 2012CB215404)the National Natural Science Foundation of China(No.51261120378)the State Key Laboratory of Coal Resources and Safe Mining(No.2013CRSMZZ01)
文摘In this work, a dual-phase material consisting Gd0.1Ce0.9O2-δ （GDC, 60 wt%） was synthesized. of La0.7Ca0.3Cr0.95Zn0.05O3-δ （LCCZ, 40 wt%） and Properties including phase structure, sintering behavior, electrical conductivity and oxygen permeability for LCCZ-GDC were evaluated. The results show that dense LCCZ-GDC dual-phase disks were obtained at the sintering temperature of 1250, 1300, 1350 and 1400 ℃ by tape casting and high temperature sintering method. The grain sizes of both GDC and LCCZ grew up with the increasing of sintering temperature. The average grain size of GDC was about 0.5, 0.8, 1.4, 1.8 μm while the average grain size of LCCZ was about 0.8, 1.5, 1.8 and 2 pm after sintering at 1250, 1300, 1350 and 1400℃, respectively. Oxygen flux of LCCZ-GDC decreased with the increase of sintering temperature from 1250 to 1400 ℃. The oxygen flux of LCCZ-GDC sintered at 1250 ℃ reached 0.079 mL/min/cm2 at 975℃ with a membrane thickness of 800 μm. Dual-phase material of LCCZ-GDC will be a promising oxygen transport membrane material for its low sintering temperature and good microstructure.
基金supported by Program for New Century Excellent Talents in Chinese Ministry of Education(No.NECT-07-0307)Natural Science Foundation of Guangdong province(No.7300769)+1 种基金Fok Ying Tung Education Foundation(No.114019)New Teacher Fund of Ministry of Education of China(No.20070561032).
文摘A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction （HTXRD）. The thermal expansion coefficient of BSFZ is 10.5×10^-6 K^-1, which is lower than that of cobalt-based perovskite materials. The BSFZ membrane was also used to construct reactors for the partial oxidation of methane （POM） to syngas. Results show that the BSFZ membrane can be operated for the POM reaction for more than 100 h without any fractures. The CO selectivity of 97% is obtained. The steady oxygen permeation flux reaches around 2.5 mL/min cm^2 during POM reaction.
基金the National Advanced Materials Committee (Grant No.715-006-0122), the Ministry of Science and Technology of China (Grant No. 1999022401) and the National Natural Science Foundation of China (Grant No. 59789201).
文摘A series of BaZr0.2Co0.8-χFeχO3-σ materials for oxygen separation were synthesized through a citric and EDTA acid combined complexing method, and their crystal structures, oxygen permeabilities, sintering and sealing abilities were investigated. The results showed that the cubic perovskite structure was formed for materials in the composition range investigated. Oxygen permeation flux and stability, as well as sintering and sealing abilities of the synthesized materials were increased or improved apparently due to the introduction of zirconium. For example, the oxygen permeation flux reached 0.8 mL/min · cm2 when χ = 0.2 or 0.3 at 950℃, and a stable time-related oxygen permeation flux was found for the BaZr0.2Co0.3Fe0.5O3-σ membrane at 800℃.
文摘Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-δ (y≤0.4) and BaBixCo0.2Fe0.8-xO3-δ (x=0.1 -0.5). The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-δmembrane reached about0.77×106 mol/cm2 ·s under an air/helium oxygen partial pressure gradient at 900 ℃, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2Co0.
文摘研究了具有氧离子导电性和电子导电性的钴系钙钛矿型复合氧化物混合导电体材料中氧的选择性透过能力,考察了该体系中 A 位低价金属离子置换量、置换金属离子的种类及 B 位置换金属离子的种类对氧的透过率的影响.结果表明:改变钙钛矿型复合氧化物的组成,提高材料中氧空位浓度和氧离子导电率,有利于提高氧离子的扩散速度,即提高氧的透过率和降低氧透过的起始温度.将钙钛矿型复合氧化物混合导电体氧透膜与固体电解质氧透膜进行了比较,前者具有结构简单的优点,有希望成为一种新型高温氧分离膜介质材料.
