The oxidative dehydrogenation （ODH） reactions of ethane and propane were investigated in a catalytic membrane reactor, incorporating oxygen-permeable membranes based upon La2Ni0.9V0.1O4＋δor Ba0.5Sr0.5Co0.8Fe0.2O3-...The oxidative dehydrogenation （ODH） reactions of ethane and propane were investigated in a catalytic membrane reactor, incorporating oxygen-permeable membranes based upon La2Ni0.9V0.1O4＋δor Ba0.5Sr0.5Co0.8Fe0.2O3-δ. As a compromise between the occurrence of a measureable oxygen flux and excessive homogenous gas phase reactions, the measurements were conducted at an intermediate temperature, either at 550 or 650 oC. The results show the dominating role of the oxygen flux across the membrane and available sites at the membrane surface in primary activation of the alkane and, hence, in achieving high alkane conversions. The experimental data of ODH of propane and ethane on both membrane materials can be reconciled on the basis of Mars-van Krevelen mechanism, in which the alkane reacts with lattice oxygen on the membrane surface to produce the corresponding olefin. It is further demonstrated that the oxygen concentration in the gas phase and on the membrane surface is crucial for determining the olefin selectivity.展开更多
Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of metha...Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.展开更多
A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ（BCFNO） tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to...A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ（BCFNO） tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas.At 875 ℃,95% of methane conversion,91% of H 2 and as high as 10 ml cm-2·min-1 of oxygen permeation flux were obtained.There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials.The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas（COG） atmosphere.展开更多
Recently the CAS Qingdao Institute of Bioenergy and Processes in collaboration with the Leibniz Universit?t Hannover,Forschungszentrum Jülich and Bayer AG has made attempts to carry out methane aromatization reac...Recently the CAS Qingdao Institute of Bioenergy and Processes in collaboration with the Leibniz Universit?t Hannover,Forschungszentrum Jülich and Bayer AG has made attempts to carry out methane aromatization reaction in an oxygen-permeable membrane reactor to展开更多
The influence of surface pre-treatments, shot-peening (SP) and laser remelting (LR), on oxygen permeation behaviors of titanium alloy TC11 was investigated. Optical microscope, SEM with EDAX, XRD, and microhardness te...The influence of surface pre-treatments, shot-peening (SP) and laser remelting (LR), on oxygen permeation behaviors of titanium alloy TC11 was investigated. Optical microscope, SEM with EDAX, XRD, and microhardness tester were employed to characterize the microstructure, composition and hardness of this alloy. The results show that the surface roughness is increased by shot-peening, and the microstructure with fine-grain can be obtained by LR pre-treatment. The pre-treated samples were oxygen-permeated at (810± 10) ℃ for 10 h in atmospheric air. The outer layer consists essentially of TiO2, trace Ti2 N, Ti3Al and Ti3AlN for the SP pre-treatment and thin oxygen solution layer is found in the subsurface layer. As for LR pre-treatment, the outer layer consists mainly of TiO2 and small amounts of TiO, and the inner layer consists of alpha crystals, rich in interstitial atoms. Samples by LR pre-treatment has thicker hardened layer with higher hardness values in comparison with SP pre-treated ones.The boost diffusion of oxygen and hardening mechanisms were discussed based on the experimental results.展开更多
Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon...Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.展开更多
Solar thermochemical conversion technologies are promising for effectively utilizing solar energy by capturing the full spectrum of solar radiation.To overcome the challenges of low energy conversion efficiency and in...Solar thermochemical conversion technologies are promising for effectively utilizing solar energy by capturing the full spectrum of solar radiation.To overcome the challenges of low energy conversion efficiency and intermittency faced by solar thermochemical conversion,these technologies can be effectively integrated with membrane reactor technology.Although the performance of solar thermochemical membrane reactors has been experimentally tested,the chemical reactions and oxygen transport mechanisms during the energy conversion process remain poorly understood.This study introduces a resistance network model to elucidate the interactions between interfacial reactions and bulk diffusion during simultaneous oxidationreduction reactions on both sides of the membrane.We analyzed the oxygen flux of the membrane reactor under various operating conditions using this model to identify the reaction/transport-limiting side of the overall process.The most effective solar membrane reactor configuration utilizes natural gas and CO_(2),facilitating clean conversion of fossil fuels with significant advantages in fuel production and energy efficiency.Introducing CH_4 lowers the overall reaction temperature,maintains low oxygen partial pressure on the sweep side,and produces a synthesis gas with a 2:1 H_2/CO molar ratio.Finally,a sensitivity analysis was used to explore the relationship between overall fuel production performance and operational parameters,highlighting the critical role of this research in enhancing the reaction and transport performance of membrane reactors and advancing the development of solar-driven thermochemical fuel production technologies.展开更多
文摘The oxidative dehydrogenation （ODH） reactions of ethane and propane were investigated in a catalytic membrane reactor, incorporating oxygen-permeable membranes based upon La2Ni0.9V0.1O4＋δor Ba0.5Sr0.5Co0.8Fe0.2O3-δ. As a compromise between the occurrence of a measureable oxygen flux and excessive homogenous gas phase reactions, the measurements were conducted at an intermediate temperature, either at 550 or 650 oC. The results show the dominating role of the oxygen flux across the membrane and available sites at the membrane surface in primary activation of the alkane and, hence, in achieving high alkane conversions. The experimental data of ODH of propane and ethane on both membrane materials can be reconciled on the basis of Mars-van Krevelen mechanism, in which the alkane reacts with lattice oxygen on the membrane surface to produce the corresponding olefin. It is further demonstrated that the oxygen concentration in the gas phase and on the membrane surface is crucial for determining the olefin selectivity.
基金supported by the National High-Tech Research and Development Program of China (No. 2006AA11A189)the Research on Novel Technology of Hydrogen Production from Oven Gas from Metallurgy Process (No. 07DZ12036)the National Key Technolo-gies Research and Development Program of China (No. 2006BA103A05)
文摘Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.
基金supported by the National High Technology Research and Development Program of China (Project No. 2006AA11A189)
文摘A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ（BCFNO） tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas.At 875 ℃,95% of methane conversion,91% of H 2 and as high as 10 ml cm-2·min-1 of oxygen permeation flux were obtained.There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials.The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas（COG） atmosphere.
文摘Recently the CAS Qingdao Institute of Bioenergy and Processes in collaboration with the Leibniz Universit?t Hannover,Forschungszentrum Jülich and Bayer AG has made attempts to carry out methane aromatization reaction in an oxygen-permeable membrane reactor to
基金Project (50171073) supported by the National Natural Science Foundation of China
文摘The influence of surface pre-treatments, shot-peening (SP) and laser remelting (LR), on oxygen permeation behaviors of titanium alloy TC11 was investigated. Optical microscope, SEM with EDAX, XRD, and microhardness tester were employed to characterize the microstructure, composition and hardness of this alloy. The results show that the surface roughness is increased by shot-peening, and the microstructure with fine-grain can be obtained by LR pre-treatment. The pre-treated samples were oxygen-permeated at (810± 10) ℃ for 10 h in atmospheric air. The outer layer consists essentially of TiO2, trace Ti2 N, Ti3Al and Ti3AlN for the SP pre-treatment and thin oxygen solution layer is found in the subsurface layer. As for LR pre-treatment, the outer layer consists mainly of TiO2 and small amounts of TiO, and the inner layer consists of alpha crystals, rich in interstitial atoms. Samples by LR pre-treatment has thicker hardened layer with higher hardness values in comparison with SP pre-treated ones.The boost diffusion of oxygen and hardening mechanisms were discussed based on the experimental results.
基金supported by the National High Technology Research and Development Program of China (Grant No. 2006AA11A189)Science and Technology Commission of Shanghai Municipality (Grant Nos. 0952NM01400 and 07DZ12036)
文摘Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.
基金supported by the National Natural Science Foundation of China(Grant Nos.52090062,52306242)。
文摘Solar thermochemical conversion technologies are promising for effectively utilizing solar energy by capturing the full spectrum of solar radiation.To overcome the challenges of low energy conversion efficiency and intermittency faced by solar thermochemical conversion,these technologies can be effectively integrated with membrane reactor technology.Although the performance of solar thermochemical membrane reactors has been experimentally tested,the chemical reactions and oxygen transport mechanisms during the energy conversion process remain poorly understood.This study introduces a resistance network model to elucidate the interactions between interfacial reactions and bulk diffusion during simultaneous oxidationreduction reactions on both sides of the membrane.We analyzed the oxygen flux of the membrane reactor under various operating conditions using this model to identify the reaction/transport-limiting side of the overall process.The most effective solar membrane reactor configuration utilizes natural gas and CO_(2),facilitating clean conversion of fossil fuels with significant advantages in fuel production and energy efficiency.Introducing CH_4 lowers the overall reaction temperature,maintains low oxygen partial pressure on the sweep side,and produces a synthesis gas with a 2:1 H_2/CO molar ratio.Finally,a sensitivity analysis was used to explore the relationship between overall fuel production performance and operational parameters,highlighting the critical role of this research in enhancing the reaction and transport performance of membrane reactors and advancing the development of solar-driven thermochemical fuel production technologies.
