Direct conversion of methane to C_2 hydrocarbons via cold plasma reactionwith catalysts has been studied at room temperature and atmospheric pressure. Methane can beconverted into C_2 hydrocarbons in different selecti...Direct conversion of methane to C_2 hydrocarbons via cold plasma reactionwith catalysts has been studied at room temperature and atmospheric pressure. Methane can beconverted into C_2 hydrocarbons in different selectivity depending on the form of the reactor, powerof plasma, flow rate of methane, ratio of N_2/CH_4 and nature of the catalysts. The selectivity toC_2 hydrocarbons can reach as high as 98.64%, and the conversion of methane as high as 60% and theyield of C_2 hydrocarbons as high as 50% are obtained. Coking can be minimized under the conditionsof: proper selection of the catalysts, appropriate high flow rate of inlet methane and suitableratio of N_2 to CH_4. The catalyst surface provides active sites for radical recombination.展开更多
The infrared emission spectra of methane, H, CH' and C_2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C_2 hydrocarbons were studied. The experiment shows that ...The infrared emission spectra of methane, H, CH' and C_2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C_2 hydrocarbons were studied. The experiment shows that methane decomposition can be divided into three periods as the reaction proceeds. In the first period, a large number of free radicals were formed. While in the last period, the formation of C_2 hydrocarbons and the decrease of free radicals were observed. The time and conditions of methane decomposition and formation of C_2 hydrocarbons are different.展开更多
Methane conversion has been studied using gliding arc plasma in the presence of argon.The process was conducted at atmospheric pressure and ambient temperature.The focus of this research was to develop a process of co...Methane conversion has been studied using gliding arc plasma in the presence of argon.The process was conducted at atmospheric pressure and ambient temperature.The focus of this research was to develop a process of converting methane to C2 hydrocarbons and hydrogen. The main parameters,including the CH4/Ar mole ratio,the CH4 flow rate,the input voltage,and the minimum electrode gap,were varied to investigate their effects on methane conversion rate, product distribution,energy consumption,carbon deposit,and reaction stability.The specific energy requirement（SER） was used to express the energy utilization efficiency of the process and provided a practical guidance for optimizing reaction conditions for improving energy efficiency. It was found that the carbon deposition was not conducive to methane conversion,and the gliding arc plasma discharge reached a stable state twelve minutes later.Optimum conditions for methane conversion were suggested.The maximum methane conversion rate of 43.39%was obtained under the optimum conditions.Also,C2 hydrocarbons selectivity,C2 hydrocarbons yield,H2 selectivity, H2 yield and SER were 87.20%,37.83%,81.28%,35.27%,and 2.09 MJ/mol,respectively.展开更多
The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion,because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on...The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion,because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule.The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure.It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage.The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons.Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane.The proper methane flow rate was 20-40 ml/min （corresponding residence time 10-20 s）.The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology.It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor.The breakdown voltage of methane VB,min derived from the Paschen law equation was established.展开更多
The infrared emission spectra of methane, H, CH and C2 hydrocarbons in natural gas were measured. The process of methane decomposition and C2 hydrocarbons formation was investigated. The experiment showed that the tim...The infrared emission spectra of methane, H, CH and C2 hydrocarbons in natural gas were measured. The process of methane decomposition and C2 hydrocarbons formation was investigated. The experiment showed that the time and conditions of methane decomposition and C2 hydrocarbons formation were different. Methane conversion rate increased with the increase in the current and decrease in the amount of methane. Furthermore, an examination of the reaction mechanisms revealed that free radicals played an important role in the chain reaction.展开更多
This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temper...This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temperature, and system pressure on equilibrium composition, conversion, selectivity and yield were studied. In addition, carbon and no carbon formation regions were also considered at various reaction temperatures and CO2/CH4 feed ratios in the reaction system at equilibrium. It was found that the reaction temperature above 1100 K and CO2/CH4 ratio=1 were favourable for synthesis gas production with H2/CO ratio unity, while carbon dioxide oxidative coupling of methane （CO2 OCM） reaction to produce ethane and ethylene is less favourable thermodynamically. Numerical results indicated that the no carbon formation region was at temperatures above 1000 K and CO2/CH4 ratio larger than 1.展开更多
The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmo...The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 ml · min-1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons is 76%, and the total selectivity of C2 hydrocarbons and C3 hydrocarbons is nearly 100%. The conversion of methane increases with the increase of voltage and decreases with the flow of methane increase; the selectivity of C2 hydrocarbons decreases with the increase of voltage and increases with the flow of methane increase. The selectivity of C2 hydrocarbons is improved with catalyst for conversion of natural gas to C2 hydrocarbons in plasma field. Methane molecule collision with radicals is mainly responsible for product formation.展开更多
Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-M...Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.展开更多
The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture an...São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture and storage(BECCS)activities.The current study presents the hydrocarbon viability evaluations and CO_(2)storage prospects,focusing on the sandstone units of the Rio Bonito Formation.The objective is to apply petrophysical evaluations with geochemical inputs in predicting future hydrocarbon(gas)production to boost CO_(2)storage within the study location.The study used data from eleven wells with associated wireline logs(gamma ray,resistivity,density,neutron,and sonic)to predict potential hydrocarbon accumulation and fluid mobility in the investigated area.Rock samples(shale and carbonate)obtained from depths>200 m within the study location have shown bitumen presence.Organic geochemistry data of the Rio Bonito Formation shale beds suggest they are potential hydrocarbon source rocks and could have contributed to the gas accumulations within the sandstone units.Some drilled well data,e.g.,CB-1-SP and TI-1-SP,show hydrocarbon(gas)presence based on the typical resistivity and the combined neutron-density responses at depths up to 3400 m,indicating the possibility of other hydrocarbon members apart from the heavy oil(bitumen)observed from the near-surface rocks samples.From the three-dimensional(3-D)model,the free fluid indicator(FFI)is more significant towards the southwest and southeast of the area with deeper depths of occurrence,indicating portions with reasonable hydrocarbon recovery rates and good prospects for CO_(2)injection,circulation and permanent storage.However,future studies based on contemporary datasets are required to establish the hydrocarbon viability further,foster gas production events,and enhance CO_(2)storage possibilities within the region.展开更多
Natural gas is not only playing an increasing important role in energy and chemicals supplies in 21st century but is also the second most important component of the greenhouse gases. Clean and direct conversion of met...Natural gas is not only playing an increasing important role in energy and chemicals supplies in 21st century but is also the second most important component of the greenhouse gases. Clean and direct conversion of methane to C 2 hydrocarbons (ethane, ethene and acetylene) through AC and DC plasma catalysis enhanced by electric field was studied at low temperature ranging from 50?℃ to 100?℃, atmospheric pressure and low power conditions. The influence of form of the electrode, distance between the electrodes, voltage, diameter of reactor, flow of inlet methane, N 2/CH 4(mole) and 20 catalysts were tested under low temperature plasma. The results indicated that best form of the electrode was plate; the better distance between the electrode was 5mm; the appropriate voltage was 38V(AC);the apparent diameter of reactor was 17mm, the likely flow range flux of inlet methane was 60—80?ml·min -1 , the suitable ratio of N 2/CH 4 (mole) was 0.5—1.0.The yield of C 2 hydrocarbons was the highest on V 2O 5,ZnO(5%)/ZSM-5-38 catalyst, the yield of ethene was the highest on La 0.8 Sr 0.2 CrO 3,ZnO catalyst. The results are better than those obtained through conventional reaction of oxidation coupling of methane.展开更多
文摘Direct conversion of methane to C_2 hydrocarbons via cold plasma reactionwith catalysts has been studied at room temperature and atmospheric pressure. Methane can beconverted into C_2 hydrocarbons in different selectivity depending on the form of the reactor, powerof plasma, flow rate of methane, ratio of N_2/CH_4 and nature of the catalysts. The selectivity toC_2 hydrocarbons can reach as high as 98.64%, and the conversion of methane as high as 60% and theyield of C_2 hydrocarbons as high as 50% are obtained. Coking can be minimized under the conditionsof: proper selection of the catalysts, appropriate high flow rate of inlet methane and suitableratio of N_2 to CH_4. The catalyst surface provides active sites for radical recombination.
基金Financially supported by aspecial fund of the Education Committee of Shaanxi province(No.2000K13-G19and2002K09-G21)
文摘The infrared emission spectra of methane, H, CH' and C_2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C_2 hydrocarbons were studied. The experiment shows that methane decomposition can be divided into three periods as the reaction proceeds. In the first period, a large number of free radicals were formed. While in the last period, the formation of C_2 hydrocarbons and the decrease of free radicals were observed. The time and conditions of methane decomposition and formation of C_2 hydrocarbons are different.
基金supported by National Natural Science Foundation of China(Nos.21176175,- 20606023)
文摘Methane conversion has been studied using gliding arc plasma in the presence of argon.The process was conducted at atmospheric pressure and ambient temperature.The focus of this research was to develop a process of converting methane to C2 hydrocarbons and hydrogen. The main parameters,including the CH4/Ar mole ratio,the CH4 flow rate,the input voltage,and the minimum electrode gap,were varied to investigate their effects on methane conversion rate, product distribution,energy consumption,carbon deposit,and reaction stability.The specific energy requirement（SER） was used to express the energy utilization efficiency of the process and provided a practical guidance for optimizing reaction conditions for improving energy efficiency. It was found that the carbon deposition was not conducive to methane conversion,and the gliding arc plasma discharge reached a stable state twelve minutes later.Optimum conditions for methane conversion were suggested.The maximum methane conversion rate of 43.39%was obtained under the optimum conditions.Also,C2 hydrocarbons selectivity,C2 hydrocarbons yield,H2 selectivity, H2 yield and SER were 87.20%,37.83%,81.28%,35.27%,and 2.09 MJ/mol,respectively.
基金supported by the Research Foundation of SINOPEC under the Grant No. 404003the Research Foundation of Tianjin Scientific & Technology Committee under the Grant No. 043182611
文摘The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion,because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule.The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure.It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage.The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons.Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane.The proper methane flow rate was 20-40 ml/min （corresponding residence time 10-20 s）.The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology.It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor.The breakdown voltage of methane VB,min derived from the Paschen law equation was established.
基金supported by National Natural Science Foundation of ChinaDoctoral Foundation of Ministry of Education(20010698007)Returned Scholars Foundation of Ministry of Education(2001[345])
文摘The infrared emission spectra of methane, H, CH and C2 hydrocarbons in natural gas were measured. The process of methane decomposition and C2 hydrocarbons formation was investigated. The experiment showed that the time and conditions of methane decomposition and C2 hydrocarbons formation were different. Methane conversion rate increased with the increase in the current and decrease in the amount of methane. Furthermore, an examination of the reaction mechanisms revealed that free radicals played an important role in the chain reaction.
文摘This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temperature, and system pressure on equilibrium composition, conversion, selectivity and yield were studied. In addition, carbon and no carbon formation regions were also considered at various reaction temperatures and CO2/CH4 feed ratios in the reaction system at equilibrium. It was found that the reaction temperature above 1100 K and CO2/CH4 ratio=1 were favourable for synthesis gas production with H2/CO ratio unity, while carbon dioxide oxidative coupling of methane （CO2 OCM） reaction to produce ethane and ethylene is less favourable thermodynamically. Numerical results indicated that the no carbon formation region was at temperatures above 1000 K and CO2/CH4 ratio larger than 1.
基金This work was supported by the Science and Technology Development from the SINOPEC (Grant No. X500005) the National Natural Science Foundation of China (Grant No. 29776037).
文摘The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 ml · min-1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons is 76%, and the total selectivity of C2 hydrocarbons and C3 hydrocarbons is nearly 100%. The conversion of methane increases with the increase of voltage and decreases with the flow of methane increase; the selectivity of C2 hydrocarbons decreases with the increase of voltage and increases with the flow of methane increase. The selectivity of C2 hydrocarbons is improved with catalyst for conversion of natural gas to C2 hydrocarbons in plasma field. Methane molecule collision with radicals is mainly responsible for product formation.
基金This work was supported by the National Key Basic Research Project of China (No. 2001CCA03600).
文摘Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
基金sponsored by Fundação de Amparoa Pesquisa do Estado de São Paulo(FAPESP)(2014/50279-4,2020/15230-5,2021/06158-1)Shell Brasil.
文摘São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture and storage(BECCS)activities.The current study presents the hydrocarbon viability evaluations and CO_(2)storage prospects,focusing on the sandstone units of the Rio Bonito Formation.The objective is to apply petrophysical evaluations with geochemical inputs in predicting future hydrocarbon(gas)production to boost CO_(2)storage within the study location.The study used data from eleven wells with associated wireline logs(gamma ray,resistivity,density,neutron,and sonic)to predict potential hydrocarbon accumulation and fluid mobility in the investigated area.Rock samples(shale and carbonate)obtained from depths>200 m within the study location have shown bitumen presence.Organic geochemistry data of the Rio Bonito Formation shale beds suggest they are potential hydrocarbon source rocks and could have contributed to the gas accumulations within the sandstone units.Some drilled well data,e.g.,CB-1-SP and TI-1-SP,show hydrocarbon(gas)presence based on the typical resistivity and the combined neutron-density responses at depths up to 3400 m,indicating the possibility of other hydrocarbon members apart from the heavy oil(bitumen)observed from the near-surface rocks samples.From the three-dimensional(3-D)model,the free fluid indicator(FFI)is more significant towards the southwest and southeast of the area with deeper depths of occurrence,indicating portions with reasonable hydrocarbon recovery rates and good prospects for CO_(2)injection,circulation and permanent storage.However,future studies based on contemporary datasets are required to establish the hydrocarbon viability further,foster gas production events,and enhance CO_(2)storage possibilities within the region.
文摘Natural gas is not only playing an increasing important role in energy and chemicals supplies in 21st century but is also the second most important component of the greenhouse gases. Clean and direct conversion of methane to C 2 hydrocarbons (ethane, ethene and acetylene) through AC and DC plasma catalysis enhanced by electric field was studied at low temperature ranging from 50?℃ to 100?℃, atmospheric pressure and low power conditions. The influence of form of the electrode, distance between the electrodes, voltage, diameter of reactor, flow of inlet methane, N 2/CH 4(mole) and 20 catalysts were tested under low temperature plasma. The results indicated that best form of the electrode was plate; the better distance between the electrode was 5mm; the appropriate voltage was 38V(AC);the apparent diameter of reactor was 17mm, the likely flow range flux of inlet methane was 60—80?ml·min -1 , the suitable ratio of N 2/CH 4 (mole) was 0.5—1.0.The yield of C 2 hydrocarbons was the highest on V 2O 5,ZnO(5%)/ZSM-5-38 catalyst, the yield of ethene was the highest on La 0.8 Sr 0.2 CrO 3,ZnO catalyst. The results are better than those obtained through conventional reaction of oxidation coupling of methane.
