Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
The paper presents an energy performance assessment of CO2 removal for crude synthetic natural gas （SNG） upgrade by Selexol absorption process. A simplified process simulation of the Selexol process concerning power...The paper presents an energy performance assessment of CO2 removal for crude synthetic natural gas （SNG） upgrade by Selexol absorption process. A simplified process simulation of the Selexol process concerning power requirement and separation performance was developed. The assessment indicates that less pressure difference between crude SNG and absorption pressure favors the energy performance of CO2 removal process. When both crude SNG and absorption pressures are 20 bar, CO2 removal process has the best energy performance. The optimal specific power consumption of the CO2 removal process is 566 kJ/kgCO2. The sensitivity analysis shows that the CO2 removal efficiency would significantly influence the total power consumption of the removal process, as well as higher heating value （HHV） and CO2 content in SNG. However, the specific power consumption excluding crude SNG and SNG compressions changes little with the variance of CO2 removal efficiency. If by-product CO2 is compressed for CO2 capture, the process would turn into a CO2-sink for the atmosphere. Correspondingly, an increase of 281 kJ/kgCO2 in specific power consumption is required for compressing the separated CO2.展开更多
The objective of this investigation is to analyze the impact of the flue gas recirculation (FGR) ratio on the different energy inputs and outputs of a SNGCC power plant as well as its overall efficiency. Simulation re...The objective of this investigation is to analyze the impact of the flue gas recirculation (FGR) ratio on the different energy inputs and outputs of a SNGCC power plant as well as its overall efficiency. Simulation results indicate that increasing flue gas recirculation increases the energy consumed by the recirculation compressor and the energy produced by the gas turbine. On the other hand, it decreases the production of energy of the steam turbine and the energy consumed by the pump of the steam cycle. The overall energy efficiency of the SNGCC power plant is highest (41.09%) at a value of 0.20 of the flue gas recirculation. However, the flue gas composition with a FGR ratio of 0.37 is more suitable for effective absorption of carbon dioxide by amine solutions. Based on the low heating value (LHV) of hydrogen, the corresponding overall efficiency of the power plant is 39.18% and the net power output of the plant is 1273 kW for consumption of 97.5 kg/hr. of hydrogen.展开更多
This paper presents thermodynamic evaluations of the agriculture residual-to-SNG process by thermochemical conversion, which mainly consists of the interconnected fluidized beds, hot gas cleaning, fluidized bed methan...This paper presents thermodynamic evaluations of the agriculture residual-to-SNG process by thermochemical conversion, which mainly consists of the interconnected fluidized beds, hot gas cleaning, fluidized bed methanation reactor and Selexol absorption unit. The process was modeled using Aspen Plus soft-ware. The process performances, i.e., CH4 content in SNG~ higher heating value and yield of SNGexergy efficiencies with and without heat recovery, unit power consumption, were evaluated firstly. The results indicate that when the other parameters remain unchanged, the steam-to-biomass ratio at carbon boundary point is the optimal value for the process. Im proving the preheating temperatures of air and gasifying agent is beneficial for the SNG yield and exergy effi ciencies. Due to the effects of COz removal efficiency, there are two optimization objectives for the SNG produc tion process： （I） to maximize CH4 content in SNC or （II） to maximize SNG yield. Further, the comparison among different feedstocks indicates that the decreasing order of SNG yield is： corn stalk 〉 wheat straw 〉 rice straw. The evaluation on the potential of agriculture-based SNG shows that the potential annual production of agriculture re sidual-based SNG could be between 555 108 - 611 108 m3 with utilization of 100% of the available unexplored resources. The agriculture residual-based SNG could play a significant role on solving the big shortfall of China＇s natural gas supply in future.展开更多
Hydrate formation rate plays an important role in the making of hydrates for natural gas storage. The effect of sodium dodecyl sulfate (SDS), alkyl polysaccharide glycoside (APG) and cyclopentane (CP) on natural gas h...Hydrate formation rate plays an important role in the making of hydrates for natural gas storage. The effect of sodium dodecyl sulfate (SDS), alkyl polysaccharide glycoside (APG) and cyclopentane (CP) on natural gas hydrate formation rate, induction time and storage capacity was studied. Micellar surfactant solutions were found to increase hydrate formation rate in a quiescent system and improve hydrate formation rate and natural gas storage capacity. The process of hydrate formation includes two stages with surfactant presence. Hydrate forms quickly in the first stage, and then the formation rate is slowed down. Surfactants (SDS or APG) reduce the induction time of hydrate formation. The effect of an anionic surfactant (SDS) on gas storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduces the induction time of hydrate formation, but can not improve the natural gas storage capacity in hydrates.展开更多
The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via...The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.展开更多
The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method a...The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.展开更多
Nickel-based catalysts represent the most commonly used systems for CO methanation.We have successfully prepared a Ni catalyst system supported on two-dimensional plasma-treated vermiculite（2D-PVMT）with a very low N...Nickel-based catalysts represent the most commonly used systems for CO methanation.We have successfully prepared a Ni catalyst system supported on two-dimensional plasma-treated vermiculite（2D-PVMT）with a very low Ni loading（0.5 wt%）.The catalyst precursor was subjected to heat treatment via either conventional heat treatment（CHT）or the plasma irradiation method（PIM）.The as-obtained CHT-Ni/PVMT and PIM-Ni/PVMT catalysts were characterized with scanning electron microscopy（SEM）,energy dispersive X-ray（EDX）,X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）,inductively coupled plasma-atomic emission spectroscopy（ICP-AES）and high-angle annular dark field scanning transmission electron microscopy（HAADF-STEM）.Additionally,CHT-NiO/PVMT and PIM-NiO/PVMT catalysts were characterized with hydrogen temperature programmed reduction（H2-TPR）.Compared with CHT-Ni/PVMT,PIM-Ni/PVMT exhibited superior catalytic performance.The plasma treated catalyst PIM-Ni/PVMT achieved a CO conversion of93.5%and a turnover frequency（TOF）of 0.8537 s^-1,at a temperature of 450℃,a gas hourly space velocity of 6000 ml·g^-1·h^-1,a synthesis gas flow rate of 65 ml·min^-1,and a pressure of 1.5 MPa.Plasma irradiation may provide a successful strategy for the preparation of catalysts with very low metal loadings which exhibit excellent properties.展开更多
CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resis...CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeOsupport prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N-adsorption–desorption, temperature-programmed reduction（TPR）, X-ray diffraction（XRD）, Raman spectroscopy（RS） and scanning electron microscope（SEM）. The results indicated that the saturated monolayer loading MoOon Ce-3 support was lower than 5% and there were some crystalline MoOparticles on the surface of the Mo/Ce-3. The preparation method of CeOhad a big influence on the specific surface area, the crystalline of CeO, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.展开更多
The objective of the first part of the investigation was to use Aspen Plus software and the Redlich-Kwong-Soave equation of state in order to simulate an adiabatic methanation reactor for the production of synthetic n...The objective of the first part of the investigation was to use Aspen Plus software and the Redlich-Kwong-Soave equation of state in order to simulate an adiabatic methanation reactor for the production of synthetic natural methane (SNG) using 1 kg/hr<span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">of carbon dioxide. In this paper, we define the Synthetic Natural Gas Combined Cycle (SNGCC) as a combined cycle power plant where the fuel is synthetic natural gas (SNG) produced by a methanation reactor. The feed of the methanation reactor is the recycled stream of carbon dioxide of a CO<sub>2</sub> capture unit treating the flue gas of the SNGCC power plant. The objective of the second part of the investigation is the utilization of Aspen plus software with SRK equation of state for the simulation of the SNGCC power plant. The metallurgical limitation of the gas turbine was fixed at 1300<sup><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°<span style="font-family:Verdana;white-space:normal;"></span></span></sup></span></span>C in this investigation. For effective absorption by amine solutions, the molar percentage of CO<sub>2</sub> in the flue gas should be higher than 10%. Moreover, in order to reduce technical problems linked to oxidative degradation of amine in the CO<sub>2</sub> capture plant, the percentage of O<sub>2</sub> in the flue gas should also be lower than 5%. To reach this goal, the primary air for combustion has 10% excess air (compared to stoichiometric air) and 37% of the flue </span><span style="font-family:Verdana;">gas leaving the SNGCC is recirculated as the secondary air for cooling the</span><span style="font-family:Verdana;"> turbine</span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">.</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> As a result, the concentration of CO<sub>2</sub> and O<sub>2</sub></span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of the flue gas entering the CO<sub>2</sub> capture unit were respectively equal to 10.2% and 2.01%. The simulation results of the SNGCC power plant indicate that 6.6 MJ of electricity are produced for each kg of carbon dioxide recycled from the CO<sub>2</sub> capture unit of the power plant. In other terms, the production of the 24.88 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of synthetic natural gas (SNG) consumes 62.36 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of recycled carbon dioxide and 16.4 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of hydrogen. The SNG produced by the methanation reactor of the power plant generates 114 kW of electricity. It is assumed in this paper that the hydrogen needed for the methanation of carbon dioxide is a product of a catalytic reforming plant that produces gasoline from heavy naphta fraction of an atmospheric distillation unit of crude oil.</span></span></span>展开更多
A double-input–multi-output linearized system is developed using the state-space method for dynamic analysis of methanation process of coke oven gas.The stability of reactor alone and reactor with feed-effluent heat ...A double-input–multi-output linearized system is developed using the state-space method for dynamic analysis of methanation process of coke oven gas.The stability of reactor alone and reactor with feed-effluent heat exchanger is compared through the dominant poles of the system transfer functions.With single or double disturbance of temperature and CO concentration at the reactor inlet,typical dynamic behavior in the reactor,including fast concentration response,slow temperature response and inverse response,is revealed for further understanding of the counteraction and synergy effects caused by simultaneous variation of concentration and temperature.Analysis results show that the stability of the reactor loop is more sensitive than that of reactor alone due to the positive heat feedback.Remarkably,with the decrease of heat exchange efficiency,the reactor system may display limit cycle behavior for a pair of complex conjugate poles across the imaginary axis.展开更多
Nanosized NiO,CeO_(2) and NiO-CeO_(2) mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical compositio...Nanosized NiO,CeO_(2) and NiO-CeO_(2) mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical composition,structure,morphology and texture.On the catalysts submitted to the same reduction pretreatment adopted for the activity tests the surface basic properties and specific metal surface area were also determined.NiO and CeO_(2) nanocrystals of about 4 nm in size were obtained,regardless of the Ni/Ce molar ratio.The Raman and X-ray photoelectron spectroscopy results proved the formation of defective sites at the NiO-CeO_(2) interface,where Ni species are in strong interaction with the support.The microcalorimetric and Fourier transform infrared analyses of the reduced samples highlighted that,unlike metallic nickel,CeO_(2) is able to effectively adsorb CO_(2),forming carbonates and hydrogen carbonates.After reduction in H2 at 400°C for 1 h,the catalytic performance was studied in the CO and CO_(2) co-methanation reaction.Catalytic tests were performed at atmospheric pressure and 300°C,using CO/CO_(2)/H_(2) molar compositions of 1/1/7 or 1/1/5,and space velocities equal to 72000 or 450000 cm^(3)∙h^(-1)∙gcat^(-1).Whereas CO was almost completely hydrogenated in any investigated experimental conditions,CO_(2) conversion was strongly affected by both the CO/CO_(2)/H_(2) ratio and the space velocity.The faster and definitely preferred CO hydrogenation was explained in the light of the different mechanisms of CO and CO_(2) methanation.On a selected sample,the influence of the reaction temperature and of a higher number of space velocity values,as well as the stability,were also studied.Provided that the Ni content is optimized,the NiCe system investigated was very promising,being highly active for the CO_(x) co-methanation reaction in a wide range of operating conditions and stable(up to 50 h)also when submitted to thermal stress.展开更多
For better performances of Ni-based catalysts at low temperatures,Ni/SiC catalyst doped with a little amount of additive La was successfully prepared.The catalytic CO methanation activity tests showed that 3%La-Ni/SiC...For better performances of Ni-based catalysts at low temperatures,Ni/SiC catalyst doped with a little amount of additive La was successfully prepared.The catalytic CO methanation activity tests showed that 3%La-Ni/SiC catalyst was excellent at a low reaction temperature(95.9%CO conversion and 85.1%CH4 selectivity at250℃)with a superior stability compared with Ni/SiC(3.4%CO conversion and 0%CH4 selectivity at 250℃).This can be attributed to that the addition of La can markedly improve the dispersibility of active metal Ni and reduce the particle sizes of Ni nanoparticles or clusters,and can also regulate the interaction between active components and supports.Moreover,the high thermal conductivity and thermal stability could avoid the generation of hot spots in the catalyst bed.These results will promote the development of highly active Ni-based catalysts for the low-temperature methanation reaction.展开更多
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
基金supported by the Special Fund for Major State Basic Research Projects of China(2010CB732206)
文摘The paper presents an energy performance assessment of CO2 removal for crude synthetic natural gas （SNG） upgrade by Selexol absorption process. A simplified process simulation of the Selexol process concerning power requirement and separation performance was developed. The assessment indicates that less pressure difference between crude SNG and absorption pressure favors the energy performance of CO2 removal process. When both crude SNG and absorption pressures are 20 bar, CO2 removal process has the best energy performance. The optimal specific power consumption of the CO2 removal process is 566 kJ/kgCO2. The sensitivity analysis shows that the CO2 removal efficiency would significantly influence the total power consumption of the removal process, as well as higher heating value （HHV） and CO2 content in SNG. However, the specific power consumption excluding crude SNG and SNG compressions changes little with the variance of CO2 removal efficiency. If by-product CO2 is compressed for CO2 capture, the process would turn into a CO2-sink for the atmosphere. Correspondingly, an increase of 281 kJ/kgCO2 in specific power consumption is required for compressing the separated CO2.
文摘The objective of this investigation is to analyze the impact of the flue gas recirculation (FGR) ratio on the different energy inputs and outputs of a SNGCC power plant as well as its overall efficiency. Simulation results indicate that increasing flue gas recirculation increases the energy consumed by the recirculation compressor and the energy produced by the gas turbine. On the other hand, it decreases the production of energy of the steam turbine and the energy consumed by the pump of the steam cycle. The overall energy efficiency of the SNGCC power plant is highest (41.09%) at a value of 0.20 of the flue gas recirculation. However, the flue gas composition with a FGR ratio of 0.37 is more suitable for effective absorption of carbon dioxide by amine solutions. Based on the low heating value (LHV) of hydrogen, the corresponding overall efficiency of the power plant is 39.18% and the net power output of the plant is 1273 kW for consumption of 97.5 kg/hr. of hydrogen.
基金supported by the Special Fund for Major State Basic Research Projects of China (2010CB732206, 2013CB228106)the Scientific Research Foundation of Graduate School of Southeast University (YBJJ1219)
文摘This paper presents thermodynamic evaluations of the agriculture residual-to-SNG process by thermochemical conversion, which mainly consists of the interconnected fluidized beds, hot gas cleaning, fluidized bed methanation reactor and Selexol absorption unit. The process was modeled using Aspen Plus soft-ware. The process performances, i.e., CH4 content in SNG~ higher heating value and yield of SNGexergy efficiencies with and without heat recovery, unit power consumption, were evaluated firstly. The results indicate that when the other parameters remain unchanged, the steam-to-biomass ratio at carbon boundary point is the optimal value for the process. Im proving the preheating temperatures of air and gasifying agent is beneficial for the SNG yield and exergy effi ciencies. Due to the effects of COz removal efficiency, there are two optimization objectives for the SNG produc tion process： （I） to maximize CH4 content in SNC or （II） to maximize SNG yield. Further, the comparison among different feedstocks indicates that the decreasing order of SNG yield is： corn stalk 〉 wheat straw 〉 rice straw. The evaluation on the potential of agriculture-based SNG shows that the potential annual production of agriculture re sidual-based SNG could be between 555 108 - 611 108 m3 with utilization of 100% of the available unexplored resources. The agriculture residual-based SNG could play a significant role on solving the big shortfall of China＇s natural gas supply in future.
文摘Hydrate formation rate plays an important role in the making of hydrates for natural gas storage. The effect of sodium dodecyl sulfate (SDS), alkyl polysaccharide glycoside (APG) and cyclopentane (CP) on natural gas hydrate formation rate, induction time and storage capacity was studied. Micellar surfactant solutions were found to increase hydrate formation rate in a quiescent system and improve hydrate formation rate and natural gas storage capacity. The process of hydrate formation includes two stages with surfactant presence. Hydrate forms quickly in the first stage, and then the formation rate is slowed down. Surfactants (SDS or APG) reduce the induction time of hydrate formation. The effect of an anionic surfactant (SDS) on gas storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduces the induction time of hydrate formation, but can not improve the natural gas storage capacity in hydrates.
基金supported by the Hundred Talents Program of the Chinese Academy of Sciences (CAS),State Key Laboratory of Multiphase Complex Systems of China (No.MPCS-2009-C-01)the National Key Technology R&D Program of China (No.2010BAC66B01)the Knowledge Innovation Program of the CAS (No.KGCX2-YW-396)
文摘The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.
文摘The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.
基金Supported by the National Natural Science Foundation of China(U1203293,21163015)the Doctor Foundation of Bingtuan(2013BB010)+1 种基金Program of Science and Technology Innovation Team in Bingtuan(2015BD003)Program for Changjiang Scholars,Innovative Research Team in University(IRT_15R46)
文摘Nickel-based catalysts represent the most commonly used systems for CO methanation.We have successfully prepared a Ni catalyst system supported on two-dimensional plasma-treated vermiculite（2D-PVMT）with a very low Ni loading（0.5 wt%）.The catalyst precursor was subjected to heat treatment via either conventional heat treatment（CHT）or the plasma irradiation method（PIM）.The as-obtained CHT-Ni/PVMT and PIM-Ni/PVMT catalysts were characterized with scanning electron microscopy（SEM）,energy dispersive X-ray（EDX）,X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）,inductively coupled plasma-atomic emission spectroscopy（ICP-AES）and high-angle annular dark field scanning transmission electron microscopy（HAADF-STEM）.Additionally,CHT-NiO/PVMT and PIM-NiO/PVMT catalysts were characterized with hydrogen temperature programmed reduction（H2-TPR）.Compared with CHT-Ni/PVMT,PIM-Ni/PVMT exhibited superior catalytic performance.The plasma treated catalyst PIM-Ni/PVMT achieved a CO conversion of93.5%and a turnover frequency（TOF）of 0.8537 s^-1,at a temperature of 450℃,a gas hourly space velocity of 6000 ml·g^-1·h^-1,a synthesis gas flow rate of 65 ml·min^-1,and a pressure of 1.5 MPa.Plasma irradiation may provide a successful strategy for the preparation of catalysts with very low metal loadings which exhibit excellent properties.
基金Financial supports from the National High Technology Research and Development Program of China(863 Project)(2015AA050504)the National Natural Science Foundation of China(21576203)
文摘CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeOsupport prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N-adsorption–desorption, temperature-programmed reduction（TPR）, X-ray diffraction（XRD）, Raman spectroscopy（RS） and scanning electron microscope（SEM）. The results indicated that the saturated monolayer loading MoOon Ce-3 support was lower than 5% and there were some crystalline MoOparticles on the surface of the Mo/Ce-3. The preparation method of CeOhad a big influence on the specific surface area, the crystalline of CeO, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.
文摘The objective of the first part of the investigation was to use Aspen Plus software and the Redlich-Kwong-Soave equation of state in order to simulate an adiabatic methanation reactor for the production of synthetic natural methane (SNG) using 1 kg/hr<span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">of carbon dioxide. In this paper, we define the Synthetic Natural Gas Combined Cycle (SNGCC) as a combined cycle power plant where the fuel is synthetic natural gas (SNG) produced by a methanation reactor. The feed of the methanation reactor is the recycled stream of carbon dioxide of a CO<sub>2</sub> capture unit treating the flue gas of the SNGCC power plant. The objective of the second part of the investigation is the utilization of Aspen plus software with SRK equation of state for the simulation of the SNGCC power plant. The metallurgical limitation of the gas turbine was fixed at 1300<sup><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°<span style="font-family:Verdana;white-space:normal;"></span></span></sup></span></span>C in this investigation. For effective absorption by amine solutions, the molar percentage of CO<sub>2</sub> in the flue gas should be higher than 10%. Moreover, in order to reduce technical problems linked to oxidative degradation of amine in the CO<sub>2</sub> capture plant, the percentage of O<sub>2</sub> in the flue gas should also be lower than 5%. To reach this goal, the primary air for combustion has 10% excess air (compared to stoichiometric air) and 37% of the flue </span><span style="font-family:Verdana;">gas leaving the SNGCC is recirculated as the secondary air for cooling the</span><span style="font-family:Verdana;"> turbine</span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">.</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> As a result, the concentration of CO<sub>2</sub> and O<sub>2</sub></span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of the flue gas entering the CO<sub>2</sub> capture unit were respectively equal to 10.2% and 2.01%. The simulation results of the SNGCC power plant indicate that 6.6 MJ of electricity are produced for each kg of carbon dioxide recycled from the CO<sub>2</sub> capture unit of the power plant. In other terms, the production of the 24.88 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of synthetic natural gas (SNG) consumes 62.36 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of recycled carbon dioxide and 16.4 kg/hr</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">of hydrogen. The SNG produced by the methanation reactor of the power plant generates 114 kW of electricity. It is assumed in this paper that the hydrogen needed for the methanation of carbon dioxide is a product of a catalytic reforming plant that produces gasoline from heavy naphta fraction of an atmospheric distillation unit of crude oil.</span></span></span>
基金Supported by the Major Research plan of the National Natural Science Foundation of China(91334101)the National Basic Research Program of China(2009CB219906)the National Natural Science Foundation of China(21276203)
文摘A double-input–multi-output linearized system is developed using the state-space method for dynamic analysis of methanation process of coke oven gas.The stability of reactor alone and reactor with feed-effluent heat exchanger is compared through the dominant poles of the system transfer functions.With single or double disturbance of temperature and CO concentration at the reactor inlet,typical dynamic behavior in the reactor,including fast concentration response,slow temperature response and inverse response,is revealed for further understanding of the counteraction and synergy effects caused by simultaneous variation of concentration and temperature.Analysis results show that the stability of the reactor loop is more sensitive than that of reactor alone due to the positive heat feedback.Remarkably,with the decrease of heat exchange efficiency,the reactor system may display limit cycle behavior for a pair of complex conjugate poles across the imaginary axis.
基金Open Access funding provided by Universita degli Studi di Cagliari.
文摘Nanosized NiO,CeO_(2) and NiO-CeO_(2) mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical composition,structure,morphology and texture.On the catalysts submitted to the same reduction pretreatment adopted for the activity tests the surface basic properties and specific metal surface area were also determined.NiO and CeO_(2) nanocrystals of about 4 nm in size were obtained,regardless of the Ni/Ce molar ratio.The Raman and X-ray photoelectron spectroscopy results proved the formation of defective sites at the NiO-CeO_(2) interface,where Ni species are in strong interaction with the support.The microcalorimetric and Fourier transform infrared analyses of the reduced samples highlighted that,unlike metallic nickel,CeO_(2) is able to effectively adsorb CO_(2),forming carbonates and hydrogen carbonates.After reduction in H2 at 400°C for 1 h,the catalytic performance was studied in the CO and CO_(2) co-methanation reaction.Catalytic tests were performed at atmospheric pressure and 300°C,using CO/CO_(2)/H_(2) molar compositions of 1/1/7 or 1/1/5,and space velocities equal to 72000 or 450000 cm^(3)∙h^(-1)∙gcat^(-1).Whereas CO was almost completely hydrogenated in any investigated experimental conditions,CO_(2) conversion was strongly affected by both the CO/CO_(2)/H_(2) ratio and the space velocity.The faster and definitely preferred CO hydrogenation was explained in the light of the different mechanisms of CO and CO_(2) methanation.On a selected sample,the influence of the reaction temperature and of a higher number of space velocity values,as well as the stability,were also studied.Provided that the Ni content is optimized,the NiCe system investigated was very promising,being highly active for the CO_(x) co-methanation reaction in a wide range of operating conditions and stable(up to 50 h)also when submitted to thermal stress.
基金the International Science and Technology Cooperation Project of Shihezi University(No.GJHZ201804)the International Science and Technology Cooperation Project of Bingtuan(No.2018BC002)。
文摘For better performances of Ni-based catalysts at low temperatures,Ni/SiC catalyst doped with a little amount of additive La was successfully prepared.The catalytic CO methanation activity tests showed that 3%La-Ni/SiC catalyst was excellent at a low reaction temperature(95.9%CO conversion and 85.1%CH4 selectivity at250℃)with a superior stability compared with Ni/SiC(3.4%CO conversion and 0%CH4 selectivity at 250℃).This can be attributed to that the addition of La can markedly improve the dispersibility of active metal Ni and reduce the particle sizes of Ni nanoparticles or clusters,and can also regulate the interaction between active components and supports.Moreover,the high thermal conductivity and thermal stability could avoid the generation of hot spots in the catalyst bed.These results will promote the development of highly active Ni-based catalysts for the low-temperature methanation reaction.
