Due to the dissimilarity among different producing layers,the influences of inter-layer interference on the production performance of a multi-layer gas reservoir are possible.However,systematic studies of inter-layer ...Due to the dissimilarity among different producing layers,the influences of inter-layer interference on the production performance of a multi-layer gas reservoir are possible.However,systematic studies of inter-layer interference for tight gas reservoirs are really limited,especially for those reservoirs in the presence of water.In this work,five types of possible inter-layer interferences,including both absence and presence of water,are identified for commingled production of tight gas reservoirs.Subsequently,a series of reservoir-scale and pore-scale numerical simulations are conducted to quantify the degree of influence of each type of interference.Consistent field evidence from the Yan'an tight gas reservoir(Ordos Basin,China)is found to support the simulation results.Additionally,suggestions are proposed to mitigate the potential inter-layer interferences.The results indicate that,in the absence of water,commingled production is favorable in two situations:when there is a difference in physical properties and when there is a difference in the pressure system of each layer.For reservoirs with a multi-pressure system,the backflow phenomenon,which significantly influences the production performance,only occurs under extreme conditions(such as very low production rates or well shut-in periods).When water is introduced into the multi-layer system,inter-layer interference becomes nearly inevitable.Perforating both the gas-rich layer and water-rich layer for commingled production is not desirable,as it can trigger water invasion from the water-rich layer into the gas-rich layer.The gas-rich layer might also be interfered with by water from the neighboring unperforated water-rich layer,where the water might break the barrier(eg weak joint surface,cement in fractures)between the two layers and migrate into the gas-rich layer.Additionally,the gas-rich layer could possibly be interfered with by water that accumulates at the bottom of the wellbore due to gravitational differentiation during shut-in operations.展开更多
The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift (RWGS) reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activ...The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift (RWGS) reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2+ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.展开更多
Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo spe...Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO(x)-Al2O3 catalyst and the contents of Mo^5+, Mo^4+, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.展开更多
The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemical...The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.展开更多
In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were...In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H2-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez(MoO4)3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez(MoO4)3 phase has low reducibility, therefore the Fe2(MoO4)3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.展开更多
Three-dimensionally ordered macro-porous (3DOM) TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by sc...Three-dimensionally ordered macro-porous (3DOM) TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy(SEM), X-ray diffractometer(XRD), high-resolution transmission electron microscopy(HRTEM) and temperature programmed reducfion(TPR) techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift (WGS) reaction in a wide temperature range (180-360 ℃). The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.展开更多
The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promot...The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promotion effect of Re on the methanation coupling with water gas shift of biogas was investigated from the perspective of activation energy.It was found that CH4 and CO2 formation rates,which separately represented the reaction rate of methanation and water gas shift,were both enhanced after Re addition compared to non-added catalyst.Two kinetics models including empirical model and K-model were employed and from the results of calculation,it showed that Re selectively decreased the activation energy of methanation reaction and had little impact on the activation energy of water gas shift.The increased CO2 formation rate was owing to the assistance of accelerated H2O production from methanation rather than the activation energy change in water gas shift.展开更多
The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of ...The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.展开更多
The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to amm...The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.展开更多
Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic cataly...Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift (WGS) reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles homogeneously dispersed on the supports with the particle size in the range of 1-2 nm. The reducibility of the catalysts was characterized by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of WGS reactor.展开更多
A numerical model of hydraulic fracture propagation is introduced for a representative reservoir(Yuanba continental tight sandstone gas reservoir in Northeast Sichuan).Different parameters are considered,i.e.,the inte...A numerical model of hydraulic fracture propagation is introduced for a representative reservoir(Yuanba continental tight sandstone gas reservoir in Northeast Sichuan).Different parameters are considered,i.e.,the interlayer stress difference,the fracturing discharge rate and the fracturing fluid viscosity.The results show that these factors affect the gas and water production by influencing the fracture size.The interlayer stress difference can effectively control the fracture height.The greater the stress difference,the smaller the dimensionless reconstruction volume of the reservoir,while the flowback rate and gas production are lower.A large displacement fracturing construction increases the fracture-forming efficiency and expands the fracture size.The larger the displacement of fracturing construction,the larger the dimensionless reconstruction volume of the reservoir,and the higher the fracture-forming efficiency of fracturing fluid,the flowback rate,and the gas production.Low viscosity fracturing fluid is suitable for long fractures,while high viscosity fracturing fluid is suitable for wide fractures.With an increase in the fracturing fluid viscosity,the dimensionless reconstruction volume and flowback rate of the reservoir display a non-monotonic behavior,however,their changes are relatively small.展开更多
Heterogeneous gold nanocatalysts have both inspired researchers with their unique catalytic performance and frustrated them due to the contradictions observed in their activities and stabilities.A recent breakthrough ...Heterogeneous gold nanocatalysts have both inspired researchers with their unique catalytic performance and frustrated them due to the contradictions observed in their activities and stabilities.A recent breakthrough has shown that gold nanoparticles(NPs)can retain their catalytically active size over a MgGa2O4 spinel support upon sintering at high temperatures.Herein,we report the catalytic activity of anti-sintering AuGMgGa2O4 for use in water gas shift reaction(WGSR)and catalytic combustion reactions,and the promoting effect of ceria.Upon adding ceria to 800℃-aged AuGMgGa2O4,the CO conversion in the WGSR was increased from ~1.5% to ~34.0% at 450 ℃,and the “light-off” temperatures(T50)for methane combustion and CO oxidation were decreased by ~80 and ~100 ℃,respectively.Characterizations using XRD,HAADF-STEM,EDS mapping,H2-TPR,XPS,and DRIFTs confirmed the proximate contact of Au with ceria and their significant synergistic effect,which thereby combined the benefits of ceria toward the dissociation of H2O or O2 and the Au NPs toward activating CO or CH4.These results show that this stepwise stabilization-activation strategy is efficient for rationally constructing stable and active gold nanocatalysts,which may open up possibilities for the wide application of gold nanocatalysts at elevated temperatures.展开更多
Tight gas reservoirs with mobile water exhibit multi-phase flow and high stress sensitivity.Accurately analyzing the reservoir and well parameters using conventional single-phase rate transient analysis methods proves...Tight gas reservoirs with mobile water exhibit multi-phase flow and high stress sensitivity.Accurately analyzing the reservoir and well parameters using conventional single-phase rate transient analysis methods proves challenging.This study introduces novel rate transient analysis methods incorporating evaluation processes based on the conventional flowing material balance method and the Blasingame type-curve method to examine fractured gas wells producing water.By positing a gas-water two-phase equivalent homogenous phase that considers characteristics of mobile water,gas,and high stress sensitivity,the conventional single-phase rate transient analysis methods can be applied by integrating the phase's characteristics and defining the phase's normalized parameters and material balance pseudotime.The rate transient analysis methods based on the equivalent homogenous phase can be used to quantitatively assess the parameters of wells and gas reservoirs,such as original gas-in-place,fracture half-length,reservoir permeability,and well drainage radius.This facilitates the analysis of production dynamics of fractured wells and well-controlled areas,subsequently aiding in locating residual gas and guiding the configuration of well patterns.The specific evaluation processes are detailed.Additionally,a numerical simulation mechanism model was constructed to verify the reliability of the developed methods.The methods introduced have been successfully implemented in field water-producing gas wells within tight gas reservoirs containing mobile water.展开更多
Multiple-metal catalysts (Ni-Mn-Ce-K/bauxite) for Water-Gas Shift (WGS) reaction were prepared by impregnation, and the catalytic structure and properties were investigated by N2 physical, XRD, H2-TPR, and CO-TPD....Multiple-metal catalysts (Ni-Mn-Ce-K/bauxite) for Water-Gas Shift (WGS) reaction were prepared by impregnation, and the catalytic structure and properties were investigated by N2 physical, XRD, H2-TPR, and CO-TPD. The results indicated that the addition of 7.5% CeO2 improved the activity of the WGS reaction obviously, and also increased the specific surface area and pore volume of the catalysts. The addition of CeO2 decreases the reduction temperature, enhanced the adsorption and activation of H2O2, and improved the adsorption content of CO. Besides, active sites were not changed and the number of active sites on catalysts did not increase obviously.展开更多
Various copper promoted Au/ZnO-CuO catalysts with different atomic ratios of Cu to Zn prepared by means of co-precipitation were tested for the low temperature water-gas shift(WGS) reaction. The catalytic activity o...Various copper promoted Au/ZnO-CuO catalysts with different atomic ratios of Cu to Zn prepared by means of co-precipitation were tested for the low temperature water-gas shift(WGS) reaction. The catalytic activity of the catalyst depends largely on the ratio of Cu to Zn. The addition of an appropriate amount of copper can considerably improve both the catalytic activity and the stability of the catalyst in comparison with those of copper-free Au/ZnO cata- lysts. The enhanced reducibility of copper oxide in the Au/ZnO-CuO ternary-component catalysts, which was confirmed by H2-TPR, may be related to the high activity and stability of the catalyst for the low temperature WGS reaction.展开更多
Co-Mo/MgO-Al2O3 catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction. The assay results indicate that the presulfided Co-Mo/MgO-Al2O3 catalys...Co-Mo/MgO-Al2O3 catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction. The assay results indicate that the presulfided Co-Mo/MgO-Al2O3 catalyst exhibits an excellent catalytic activity and stability. XRD and EPR characterization results show that the O-S exchange might occur during the impregnation, leading to the formation of (NH4)2MoS4 (or (NH4)zMoxSy) precursor, which was then thermally decomposed and reduced to MoS2. The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides, consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.展开更多
The performance of La2-x M x CuO4 perovskites (where M=Ce,Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorpt...The performance of La2-x M x CuO4 perovskites (where M=Ce,Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure),suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2+ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.展开更多
Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models of the water-gasshift (WGS) reaction over a nano-structured iron catalyst under Fischer-Tropsch synth...Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models of the water-gasshift (WGS) reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis (FTS) reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.展开更多
Cu-Ce-La mixed oxides were prepared by three precipitation methods (coprecipitation, homogeneous precipitation, and deposition precipitation) with variable precipitators and characterized using X-ray diffraction, BE...Cu-Ce-La mixed oxides were prepared by three precipitation methods (coprecipitation, homogeneous precipitation, and deposition precipitation) with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 (111) framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3+ or Ce^4+ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide (crystalline) and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.展开更多
Cu/CeO2-ZrO2 catalysts for water-gas shift (WGS) reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of...Cu/CeO2-ZrO2 catalysts for water-gas shift (WGS) reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% (atom fraction), Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52304044,52222402,52234003,52174036)Sichuan Science and Technology Program(Nos.2022JDJQ0009,2023NSFSC0934)+2 种基金Key Technology R&D Program of Shaanxi Province(2023-YBGY-30)the Science and Technology Cooperation Project of the CNPC-SWPU Innovation Alliance(Grant No.2020CX030202)the China Postdoctoral Science Foundation(Grant No.2022M722638)。
文摘Due to the dissimilarity among different producing layers,the influences of inter-layer interference on the production performance of a multi-layer gas reservoir are possible.However,systematic studies of inter-layer interference for tight gas reservoirs are really limited,especially for those reservoirs in the presence of water.In this work,five types of possible inter-layer interferences,including both absence and presence of water,are identified for commingled production of tight gas reservoirs.Subsequently,a series of reservoir-scale and pore-scale numerical simulations are conducted to quantify the degree of influence of each type of interference.Consistent field evidence from the Yan'an tight gas reservoir(Ordos Basin,China)is found to support the simulation results.Additionally,suggestions are proposed to mitigate the potential inter-layer interferences.The results indicate that,in the absence of water,commingled production is favorable in two situations:when there is a difference in physical properties and when there is a difference in the pressure system of each layer.For reservoirs with a multi-pressure system,the backflow phenomenon,which significantly influences the production performance,only occurs under extreme conditions(such as very low production rates or well shut-in periods).When water is introduced into the multi-layer system,inter-layer interference becomes nearly inevitable.Perforating both the gas-rich layer and water-rich layer for commingled production is not desirable,as it can trigger water invasion from the water-rich layer into the gas-rich layer.The gas-rich layer might also be interfered with by water from the neighboring unperforated water-rich layer,where the water might break the barrier(eg weak joint surface,cement in fractures)between the two layers and migrate into the gas-rich layer.Additionally,the gas-rich layer could possibly be interfered with by water that accumulates at the bottom of the wellbore due to gravitational differentiation during shut-in operations.
基金Project supported by the National Natural Science Foundation of China (20476079)
文摘The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift (RWGS) reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2+ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.
文摘Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO(x)-Al2O3 catalyst and the contents of Mo^5+, Mo^4+, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.
基金the National Key Research and Development Program of China(No.2016YFB0600900)the National Natural Science Foundation of China(Nos.21676194 and 21873067)for their support。
文摘The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.
基金Supported by the Iranian Nano Technology Initiative Council and Petroleum University of Technology
文摘In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H2-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez(MoO4)3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez(MoO4)3 phase has low reducibility, therefore the Fe2(MoO4)3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.
基金supported by the Ministry of Sciences and Technology of China (863 Programs) (2006AA05Z115, 2007AA05Z104)
文摘Three-dimensionally ordered macro-porous (3DOM) TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy(SEM), X-ray diffractometer(XRD), high-resolution transmission electron microscopy(HRTEM) and temperature programmed reducfion(TPR) techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift (WGS) reaction in a wide temperature range (180-360 ℃). The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.
基金Supported by the International S&T Cooperation Program of China(ISTCP,2014DFE70150)the National Key R&D Program of China(2018YFC1901200)+1 种基金the Scientific Research Foundation of Graduate School of Southeast University(YBJJ1803)the UK-China Joint Research and Innovation Partnership Fund provided by China Scholarship Council and The British Council(201703780063)。
文摘The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promotion effect of Re on the methanation coupling with water gas shift of biogas was investigated from the perspective of activation energy.It was found that CH4 and CO2 formation rates,which separately represented the reaction rate of methanation and water gas shift,were both enhanced after Re addition compared to non-added catalyst.Two kinetics models including empirical model and K-model were employed and from the results of calculation,it showed that Re selectively decreased the activation energy of methanation reaction and had little impact on the activation energy of water gas shift.The increased CO2 formation rate was owing to the assistance of accelerated H2O production from methanation rather than the activation energy change in water gas shift.
基金financial support from the National Natural Science Foundation of China(21832001 and 21771009)the Beijing National Laboratory for Molecular Sciences(BNLMSCXXM-202104)。
文摘The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.
基金financially supported by the National Natural Science Foundation of China (22279118, 22279117, 22075254,31901272)the Top-Notch Talent Program of Henan Agricultural University (30501034)。
文摘The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.
基金supported by the Ministry of Sciences and Technology of China (863 programs, No 2006AA05Z115 and 2007AA05Z104)the National Natural Science Foundation of China (No. 20976121)
文摘Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift (WGS) reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles homogeneously dispersed on the supports with the particle size in the range of 1-2 nm. The reducibility of the catalysts was characterized by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of WGS reactor.
文摘A numerical model of hydraulic fracture propagation is introduced for a representative reservoir(Yuanba continental tight sandstone gas reservoir in Northeast Sichuan).Different parameters are considered,i.e.,the interlayer stress difference,the fracturing discharge rate and the fracturing fluid viscosity.The results show that these factors affect the gas and water production by influencing the fracture size.The interlayer stress difference can effectively control the fracture height.The greater the stress difference,the smaller the dimensionless reconstruction volume of the reservoir,while the flowback rate and gas production are lower.A large displacement fracturing construction increases the fracture-forming efficiency and expands the fracture size.The larger the displacement of fracturing construction,the larger the dimensionless reconstruction volume of the reservoir,and the higher the fracture-forming efficiency of fracturing fluid,the flowback rate,and the gas production.Low viscosity fracturing fluid is suitable for long fractures,while high viscosity fracturing fluid is suitable for wide fractures.With an increase in the fracturing fluid viscosity,the dimensionless reconstruction volume and flowback rate of the reservoir display a non-monotonic behavior,however,their changes are relatively small.
基金supported by the National Key R&D Program of China(2016YFA0202801)the National Natural Science Foundation of China(21403213,21673226)+1 种基金the"Transformational Technologies for Clean Energy and Demonstration"Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21040200)the "Hundred Talents Programme" of the Chinese Academy of Sciences~~
文摘Heterogeneous gold nanocatalysts have both inspired researchers with their unique catalytic performance and frustrated them due to the contradictions observed in their activities and stabilities.A recent breakthrough has shown that gold nanoparticles(NPs)can retain their catalytically active size over a MgGa2O4 spinel support upon sintering at high temperatures.Herein,we report the catalytic activity of anti-sintering AuGMgGa2O4 for use in water gas shift reaction(WGSR)and catalytic combustion reactions,and the promoting effect of ceria.Upon adding ceria to 800℃-aged AuGMgGa2O4,the CO conversion in the WGSR was increased from ~1.5% to ~34.0% at 450 ℃,and the “light-off” temperatures(T50)for methane combustion and CO oxidation were decreased by ~80 and ~100 ℃,respectively.Characterizations using XRD,HAADF-STEM,EDS mapping,H2-TPR,XPS,and DRIFTs confirmed the proximate contact of Au with ceria and their significant synergistic effect,which thereby combined the benefits of ceria toward the dissociation of H2O or O2 and the Au NPs toward activating CO or CH4.These results show that this stepwise stabilization-activation strategy is efficient for rationally constructing stable and active gold nanocatalysts,which may open up possibilities for the wide application of gold nanocatalysts at elevated temperatures.
文摘Tight gas reservoirs with mobile water exhibit multi-phase flow and high stress sensitivity.Accurately analyzing the reservoir and well parameters using conventional single-phase rate transient analysis methods proves challenging.This study introduces novel rate transient analysis methods incorporating evaluation processes based on the conventional flowing material balance method and the Blasingame type-curve method to examine fractured gas wells producing water.By positing a gas-water two-phase equivalent homogenous phase that considers characteristics of mobile water,gas,and high stress sensitivity,the conventional single-phase rate transient analysis methods can be applied by integrating the phase's characteristics and defining the phase's normalized parameters and material balance pseudotime.The rate transient analysis methods based on the equivalent homogenous phase can be used to quantitatively assess the parameters of wells and gas reservoirs,such as original gas-in-place,fracture half-length,reservoir permeability,and well drainage radius.This facilitates the analysis of production dynamics of fractured wells and well-controlled areas,subsequently aiding in locating residual gas and guiding the configuration of well patterns.The specific evaluation processes are detailed.Additionally,a numerical simulation mechanism model was constructed to verify the reliability of the developed methods.The methods introduced have been successfully implemented in field water-producing gas wells within tight gas reservoirs containing mobile water.
基金the Natural Science Foundation of Fujian Province of China (U0650011)the "Little Invention and Little Creation" of Fu-jian Province Innovation and Development Committee of China
文摘Multiple-metal catalysts (Ni-Mn-Ce-K/bauxite) for Water-Gas Shift (WGS) reaction were prepared by impregnation, and the catalytic structure and properties were investigated by N2 physical, XRD, H2-TPR, and CO-TPD. The results indicated that the addition of 7.5% CeO2 improved the activity of the WGS reaction obviously, and also increased the specific surface area and pore volume of the catalysts. The addition of CeO2 decreases the reduction temperature, enhanced the adsorption and activation of H2O2, and improved the adsorption content of CO. Besides, active sites were not changed and the number of active sites on catalysts did not increase obviously.
文摘Various copper promoted Au/ZnO-CuO catalysts with different atomic ratios of Cu to Zn prepared by means of co-precipitation were tested for the low temperature water-gas shift(WGS) reaction. The catalytic activity of the catalyst depends largely on the ratio of Cu to Zn. The addition of an appropriate amount of copper can considerably improve both the catalytic activity and the stability of the catalyst in comparison with those of copper-free Au/ZnO cata- lysts. The enhanced reducibility of copper oxide in the Au/ZnO-CuO ternary-component catalysts, which was confirmed by H2-TPR, may be related to the high activity and stability of the catalyst for the low temperature WGS reaction.
文摘Co-Mo/MgO-Al2O3 catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction. The assay results indicate that the presulfided Co-Mo/MgO-Al2O3 catalyst exhibits an excellent catalytic activity and stability. XRD and EPR characterization results show that the O-S exchange might occur during the impregnation, leading to the formation of (NH4)2MoS4 (or (NH4)zMoxSy) precursor, which was then thermally decomposed and reduced to MoS2. The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides, consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.
文摘The performance of La2-x M x CuO4 perovskites (where M=Ce,Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure),suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2+ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.
文摘Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models of the water-gasshift (WGS) reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis (FTS) reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.
基金the Scientific Research Foundation for Returned Scholars of Ministry of Education, Inner Mongolia Natural Science Foundation (20041001)Chunhui Plan Ministry of Education and Inner Mongolia Talented Person Foundation
文摘Cu-Ce-La mixed oxides were prepared by three precipitation methods (coprecipitation, homogeneous precipitation, and deposition precipitation) with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 (111) framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3+ or Ce^4+ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide (crystalline) and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.
文摘Cu/CeO2-ZrO2 catalysts for water-gas shift (WGS) reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% (atom fraction), Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.