Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high...Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.展开更多
Pd/YZ-Al2O3 （Y and Zr modified Al2O3, and hereafter, labelled as A1） catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy （XPS）, NO-temperature progra...Pd/YZ-Al2O3 （Y and Zr modified Al2O3, and hereafter, labelled as A1） catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy （XPS）, NO-temperature programmed desorption （NO-TPD）, Nz-adsorption/desorption （Branauer-Emmet-Teller BET method）, X-ray diffraction （XRD） and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles （NGVs） operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order： Pd/Al 〉 Pd/Ce/Al 〉 Pd/La/Al 〉 Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.展开更多
Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared viaacidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation ofliquid hydrocarbons. ZSM-5 (SiO_2/Al_2O_3...Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared viaacidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation ofliquid hydrocarbons. ZSM-5 (SiO_2/Al_2O_3=30) was loaded with different metals (Cr, Cu and Ga)according to the acidic ion-exchange method to produce metal-loaded ZSM-5 zeolite catalysts. XRD,NMR, FT-IR and N_2 adsorption analyses indicated that Cr and Ga species managed to occupy thealuminum positions in the ZSM-5 framework. In addition, Cr species were deposited in the pores ofthe structure. However, Cu oxides were deposited on the surface and in the mesopores of the ZSM-5zeolite. An acidity study using TPD-NH_3, FT-IR, and IR-pyridine analyses revealed that the totalnumber of acid sites and the strengths of the Broensted and Lewis acid sites were significantlydifferent after the acidic ion exchange treatment. Cu loaded HZSM-5 is a potential catalyst fordirect conversion of methane to liquid hydrocarbons. The successful production of gasoline via thedirect conversion of methane depends on the amount of aluminum in the zeolite framework and thestrength of the Broensted acid sites.展开更多
The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, thedirect catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many stud...The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, thedirect catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many studies have been devoted to this field in the past decades. Electrocatalysis is considered asan important alternative approach for the direct conversion of methane into value-added chemicals, al-though many other innovative methods have been developed. This review highlights recent advances inelectrocatalytic conversion of methane to ethylene and methanol, two important chemicals. The electro-catalytic systems efficient for methane conversions are summarized with an emphasis on catalysts andelectrolytes. The effects of reaction conditions such as the temperature and the acid-base property of thereaction medium are also discussed,展开更多
The direct conversion of methane using a dielectric barrier discharge has been experimentally studied. Experiments with different values of flow rates and discharge voltages have been performed to investigate the effe...The direct conversion of methane using a dielectric barrier discharge has been experimentally studied. Experiments with different values of flow rates and discharge voltages have been performed to investigate the effects on the conversion and reaction products both qualitatively and quantitatively. Experimental results indicate that the maximum conversion of methane has been 80% at an input flow rate of 5 ml/min and a discharge voltage of 4 kV. Experimental results also show that the optimum condition has occurred at a high discharge voltage and higher input flow rate. In terms of product distribution, a higher flow rate or shorter residence time can increase the selectivity for higher hydrocarbons. No hydrocarbon product was detected using the thermal method, except hydrogen and carbon. Increasing selectivity for ethane was found when Pt and Ru catalysts presented in the plasma reaction. Hydrogenation of acetylene in the catalyst surface could have been the reason for this phenomenon as the selectivity for acetylene in the products was decreasing.展开更多
At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons （C2-C4） and aromatics （C6-C10）, through its reaction over rare metals modi...At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons （C2-C4） and aromatics （C6-C10）, through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.展开更多
Composite supports CeO2-ZrO2-Al2O3（CZA） and CeO2-ZrO2-Al2O3-La2O3（CZALa） were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and N...Composite supports CeO2-ZrO2-Al2O3（CZA） and CeO2-ZrO2-Al2O3-La2O3（CZALa） were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles （NGVs） operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction （XRD） and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction （H2-TPR） and oxygen storage capacity （OSC） measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.展开更多
In this paper, a cylindrical dielectric barrier discharge （DBD） reactor has been developed for the conversion of methane into hydrogen and other valuable chemicals. The effects of a wide range of processing paramete...In this paper, a cylindrical dielectric barrier discharge （DBD） reactor has been developed for the conversion of methane into hydrogen and other valuable chemicals. The effects of a wide range of processing parameters including discharge power, residence time and frequency on the performance of plasma methane conversion reaction have been investigated. The results show that the CH4 DBD could be characterized as a typical filamentary discharge with a microdis-charge zone in each half-cycle of the applied voltage. The conversion of CH4 reaches a maximum of 25.2% at a feed flow rate of 50 mL-min-1, a discharge power of 45 W and an excitation frequency of 20 kHz. It is found that the residence time of methane in the discharge zone has the most significant effect on both methane conversion and hydrogen yield, which are significantly higher at higher residence time.展开更多
Progress in natural gas conversion in China is presented in this paper, including processes of natural gas to synthesis gas （syngas）, syngas to liquid hydrocarbons, oxygenates synthesis, methanol to olefins （MTO）,...Progress in natural gas conversion in China is presented in this paper, including processes of natural gas to synthesis gas （syngas）, syngas to liquid hydrocarbons, oxygenates synthesis, methanol to olefins （MTO）, methane to aromatics and oxidative coupling of methane （OCM）.展开更多
CexZr1-xO2 mixed oxides with different Ce/Zr ratios were prepared by coprecipitation. The characterizations of mixed oxides were studied by X-ray diffraction (XRD) and H2-TPR. And the performances were tested in a fix...CexZr1-xO2 mixed oxides with different Ce/Zr ratios were prepared by coprecipitation. The characterizations of mixed oxides were studied by X-ray diffraction (XRD) and H2-TPR. And the performances were tested in a fixed-bed quartz reactor. The results indicated that lattice oxygen of CexZr1-xO2 could oxidate methane to syngas and the incorporation of zirconium into the ceria lattice could improve the O2- mobility. The Ce0.7Zr0.3O2 had the best activity in investigative temperature ranging from 600 to 900 ℃. Effects of reaction time on H2/CO ratio were studied at 850 ℃ when using Ce0.7Zr0.3O2 as catalyst. The results indicated that the ratio was closed to 2 values in the first 10 min, however, it rapidly increased with reaction time after >10 min. The possible reason was that the direct partial oxidation of methane reaction was dominant in the first 10 min. However, the methane pyrogenation was responsible for the rapid increase of H2/CO ratio after 10 min. Thus, if syngas with H2/CO ratio of 2 wanted to be obtained, the reaction time needed to be controlled.展开更多
Non-oxidative conversion of methane to olefins,aromatics and hydrogen(MTOAH) has been reported recently over metal single sites such as iron and platinum.The reaction was proposed to involve catalytic activation of me...Non-oxidative conversion of methane to olefins,aromatics and hydrogen(MTOAH) has been reported recently over metal single sites such as iron and platinum.The reaction was proposed to involve catalytic activation of methane followed by gas phase C-C coupling of methyl radicals.This study using H atom Rydberg Tagging time-of-flight technique provides direct experimental evidence for the formation of hydrogen radicals during MTOAH reaction over a catalytic quartz wall reactor containing embedded iron species(denoted as Fe-reactor).Fe-reactor gives 7.3% methane conversion at 1273 K with 41.2% selectivity toward C2(ethane,ethylene and acetylene) and 31.8% toward BTX(benzene,toluene and xylene),respectively.The enhancing effects of hydrogen radicals on overall MTOAH performance are validated by cofeeding hydrogen donor benzene,which provides an additional route of methane activation apart from catalytic activation.展开更多
Greenhouse gases are known to play an important role in global warming.In this study,we determined the effects of selected soil and climate variables on nitrous oxide(N2O),methane(CH4),and carbon dioxide(CO2)emissions...Greenhouse gases are known to play an important role in global warming.In this study,we determined the effects of selected soil and climate variables on nitrous oxide(N2O),methane(CH4),and carbon dioxide(CO2)emissions from a tropical grassland fertilized with chicken slurry,swine slurry,cattle slurry,and cattle compost.Cumulative N2O emissions did not differ between treatments and varied from 29.26 to 32.85 mg N m^-2.Similarly,cumulative CH4 emissions were not significantly different among the treatments and ranged from 6.34 to 57.73 mg CH4 m^-2.Slurry and compost application induced CO2 emissions that were significantly different from those in the control treatment.The CH4 conversion factors measured were 0.21%,1.39%,4.39%,and 5.07%for cattle compost,chicken slurry,swine slurry,and cattle slurry,respectively,differing from the recommendations of the Intergovernmental Panel on Climate Change(IPCC).The fraction of added Nemitted as N2O was 0.39%,which was lower than the IPCC default value of 2%.Our findings suggest that N2O emissions could be mitigated by replacing synthetic fertilizer sources with either biofertilizer or compost.Our results indicate the following:N2O emission was mainly controlled by soil temperature,followed by soil moisture and then soil NH^"content;CH4 fluxes were mainly controlled by soil moisture and chamber headspace temperature;and CO2 fluxes were mainly controlled by chamber headspace temperature and soil moisture.展开更多
Methane conversion to C2 hydrocarbons has been investigated with the addition of hydrogen in a plasma reactor of abnormal glow discharge at atmospheric pressure. The aim of this experiment is to minimize coke formatio...Methane conversion to C2 hydrocarbons has been investigated with the addition of hydrogen in a plasma reactor of abnormal glow discharge at atmospheric pressure. The aim of this experiment is to minimize coke formation and improve discharge stability. The typical conditions in the experiment are 300 ml of total feed flux and 400 W of discharge power. The experimental results show that methane conversion is from 91.6% to 35.2% in mol, acetylene selectivity is from 90.2% to 57.6%, and ethylene selectivity is approximately from 7.8% to 3.6%, where the coke increases gradually along with the increase of CH4/H2 from 2 ： 8 to 9 ： 1. A stable discharge for a considerable running time can be obtained only at a lower ratio of CH4/H2 = 2：8 or 3： 7. These phenomena indicate that the coke deposition during methane conversion is obviously reduced by adding a large amount of hydrogen during an abnormal glow discharge. A qualitative interpretation is presented, namely, with abundant hydrogen, the possibility that hydrogen molecules are activated to hydrogen radicals is increased with the help of the abnormal glow discharge. These hydrogen radicals react with carbon radicals to form C2 hydrocarbon products. Therefore, the deposition of coke is restrained.展开更多
Plasma methane (CH_4) conversion in gliding arc discharge was examined. Theresult data of experiments regarding the performance of gliding arc discharge were presented in thispaper. A simulation which is consisted som...Plasma methane (CH_4) conversion in gliding arc discharge was examined. Theresult data of experiments regarding the performance of gliding arc discharge were presented in thispaper. A simulation which is consisted some chemical kinetic mechanisms has been provided toanalyze and describe the plasma process. The effect of total gas flow rate and input frequencyrefers to power consumption have been studied to evaluate the performance of gliding arc plasmasystem and the reaction mechanism of decomposition. Experiment results indicated that the maximumconversion of CH_4 reached 50% at the total gas flow rate of 1 L/min. The plasma reaction wasoccurred at the atmospheric pressure and the main products were C (solid), hydrogen, and acetylene(C_2H_2). The plasma reaction of methane conversion was exothermic reaction which increased theproduct stream temperature around 30-50℃.展开更多
Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of metha...Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.展开更多
In order to study the nature of gas hydrate in porous media,the formation and dissociation processes of methane hydrate in loess were investigated.Five cooling rates were applied to form methane hydrate.The nucleation...In order to study the nature of gas hydrate in porous media,the formation and dissociation processes of methane hydrate in loess were investigated.Five cooling rates were applied to form methane hydrate.The nucleation times of methane hydrate formation at each cooling rate were measured for comparison.The experimental results show that cooling rate is a significant factor affecting the nucleation of methane hydrate and gas conversion.Under the same initial conditions,the faster the cooling rate,the shorter the nucleation time,and the lower the methane gas conversion.Five dissociating temperatures were applied to conduct the dissociation experiment of methane hydrate formed in loess.The experimental results indicated that the temperature evidently controlled the dissociation of methane hydrate in loess and the higher the dissociating temperature,the faster the dissociating rates of methane hydrate.展开更多
At ambient temperature and pressure, C2H2 and H2 are the dominating products from pure methane conversion under pulsed corona discharge (PCD). When the energy density of 194-1788 kJ/mol was applied, 7%-30% of C2H2 yie...At ambient temperature and pressure, C2H2 and H2 are the dominating products from pure methane conversion under pulsed corona discharge (PCD). When the energy density of 194-1788 kJ/mol was applied, 7%-30% of C2H2 yield and 6%-35% of H2 yield per pass have been obtained. These results are higher than the maximum thermodynamic yield of C2H2 (5.1%) and H2 (3.8%) at 100 kPa and 1100 K, respectively. Thereby, pulsed corona discharge is a very effective tool for “beyond-thermal-equilibrium” conversion of methane to C2H2 and H2 at ambient temperature and pressure. In the PCD energy density range of 339-822 kJ/mol, the carbon distribution of the methane conversion products is found to be: C2H2 86%-89%, C2H2 4%-6%, C2H4 4%-6%, C3 ～2%, C4 ～1%. Through comparison of the product from pure methane, ethane and ethylene conversion at the same discharge conditions, it can be concluded that three pathways may be responsible for the C2H2 formation via CHX radicals produced from the collisions of CH4 molecules with energized electrons in the PCD plasma: (i) C2H2 is formed directly from free radical reactions, (ii) C2H2 is formed through the dehydrogenation of C2H4, which is formed via free radical reactions primarily, and (iii) C2H6 is the primary product and then dehydrogenates to C2H4 (secondary product) and followed by C2H4 dehydrogenation to C2H2.展开更多
基金This project was supported financially by the National Natural Science Foundation of China(21908079,21902009,21707052)Natural Science Foundation of Jiangsu Province(BK20201345)+3 种基金the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF2005)Startup Funding at Jiangnan University(1045210322190170,1045281602190010,1042050205204100)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108)Fundamental Research Funds for the Central Universities(JUSRP11905,JUSRP52004B).
文摘Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.
基金supported by the Key Program of National Natural Science Foundation of China (20333030)the National High Technology Research and Development Program of China (863 Program, No. 2006AA06Z347)the National Natural Science Foundation of China (No. 20773090)
文摘Pd/YZ-Al2O3 （Y and Zr modified Al2O3, and hereafter, labelled as A1） catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy （XPS）, NO-temperature programmed desorption （NO-TPD）, Nz-adsorption/desorption （Branauer-Emmet-Teller BET method）, X-ray diffraction （XRD） and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles （NGVs） operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order： Pd/Al 〉 Pd/Ce/Al 〉 Pd/La/Al 〉 Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.
文摘Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared viaacidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation ofliquid hydrocarbons. ZSM-5 (SiO_2/Al_2O_3=30) was loaded with different metals (Cr, Cu and Ga)according to the acidic ion-exchange method to produce metal-loaded ZSM-5 zeolite catalysts. XRD,NMR, FT-IR and N_2 adsorption analyses indicated that Cr and Ga species managed to occupy thealuminum positions in the ZSM-5 framework. In addition, Cr species were deposited in the pores ofthe structure. However, Cu oxides were deposited on the surface and in the mesopores of the ZSM-5zeolite. An acidity study using TPD-NH_3, FT-IR, and IR-pyridine analyses revealed that the totalnumber of acid sites and the strengths of the Broensted and Lewis acid sites were significantlydifferent after the acidic ion exchange treatment. Cu loaded HZSM-5 is a potential catalyst fordirect conversion of methane to liquid hydrocarbons. The successful production of gasoline via thedirect conversion of methane depends on the amount of aluminum in the zeolite framework and thestrength of the Broensted acid sites.
基金supported by the SINOPEC(No.415069)the National Natural Science Foundation of China (Nos.21690082,91545203 and 21503176)
文摘The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, thedirect catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many studies have been devoted to this field in the past decades. Electrocatalysis is considered asan important alternative approach for the direct conversion of methane into value-added chemicals, al-though many other innovative methods have been developed. This review highlights recent advances inelectrocatalytic conversion of methane to ethylene and methanol, two important chemicals. The electro-catalytic systems efficient for methane conversions are summarized with an emphasis on catalysts andelectrolytes. The effects of reaction conditions such as the temperature and the acid-base property of thereaction medium are also discussed,
文摘The direct conversion of methane using a dielectric barrier discharge has been experimentally studied. Experiments with different values of flow rates and discharge voltages have been performed to investigate the effects on the conversion and reaction products both qualitatively and quantitatively. Experimental results indicate that the maximum conversion of methane has been 80% at an input flow rate of 5 ml/min and a discharge voltage of 4 kV. Experimental results also show that the optimum condition has occurred at a high discharge voltage and higher input flow rate. In terms of product distribution, a higher flow rate or shorter residence time can increase the selectivity for higher hydrocarbons. No hydrocarbon product was detected using the thermal method, except hydrogen and carbon. Increasing selectivity for ethane was found when Pt and Ru catalysts presented in the plasma reaction. Hydrogenation of acetylene in the catalyst surface could have been the reason for this phenomenon as the selectivity for acetylene in the products was decreasing.
基金supported by the National Natural Science Foundation of China (Grants No. 20273021)the Key Project of Shanghai Science and Technology Committee (No. 05JC14070, 06DZ05025, 0552nm042, 08JC1408600)Scientific Research Foundation of the Education Department of Heilongjiang Province (No.11544005)
文摘At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons （C2-C4） and aromatics （C6-C10）, through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.
基金supported by the National Natural Science Foundation of China (No. 20773090, 20803049)the National High Technology Researchand Development Program of China (863 Program, No. 2006AA06Z347)the Specialized Research Fund for the Doctoral Program of Higher Education(20070610026)
文摘Composite supports CeO2-ZrO2-Al2O3（CZA） and CeO2-ZrO2-Al2O3-La2O3（CZALa） were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles （NGVs） operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction （XRD） and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction （H2-TPR） and oxygen storage capacity （OSC） measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.
文摘In this paper, a cylindrical dielectric barrier discharge （DBD） reactor has been developed for the conversion of methane into hydrogen and other valuable chemicals. The effects of a wide range of processing parameters including discharge power, residence time and frequency on the performance of plasma methane conversion reaction have been investigated. The results show that the CH4 DBD could be characterized as a typical filamentary discharge with a microdis-charge zone in each half-cycle of the applied voltage. The conversion of CH4 reaches a maximum of 25.2% at a feed flow rate of 50 mL-min-1, a discharge power of 45 W and an excitation frequency of 20 kHz. It is found that the residence time of methane in the discharge zone has the most significant effect on both methane conversion and hydrogen yield, which are significantly higher at higher residence time.
基金the National Natural Science Foundation of China (20490201,20306016)
文摘Progress in natural gas conversion in China is presented in this paper, including processes of natural gas to synthesis gas （syngas）, syngas to liquid hydrocarbons, oxygenates synthesis, methanol to olefins （MTO）, methane to aromatics and oxidative coupling of methane （OCM）.
基金the National Natural Science Foundation of China (50574046)National Natural Science Foundationof Major Research Projects (90610035)High School Doctoral Subject Special Science and Research Foundation of Ministry of Education (20040674005)
文摘CexZr1-xO2 mixed oxides with different Ce/Zr ratios were prepared by coprecipitation. The characterizations of mixed oxides were studied by X-ray diffraction (XRD) and H2-TPR. And the performances were tested in a fixed-bed quartz reactor. The results indicated that lattice oxygen of CexZr1-xO2 could oxidate methane to syngas and the incorporation of zirconium into the ceria lattice could improve the O2- mobility. The Ce0.7Zr0.3O2 had the best activity in investigative temperature ranging from 600 to 900 ℃. Effects of reaction time on H2/CO ratio were studied at 850 ℃ when using Ce0.7Zr0.3O2 as catalyst. The results indicated that the ratio was closed to 2 values in the first 10 min, however, it rapidly increased with reaction time after >10 min. The possible reason was that the direct partial oxidation of methane reaction was dominant in the first 10 min. However, the methane pyrogenation was responsible for the rapid increase of H2/CO ratio after 10 min. Thus, if syngas with H2/CO ratio of 2 wanted to be obtained, the reaction time needed to be controlled.
基金supported by the Chinese Academy of Sciences (XDB10020202)the National Natural Science Foundation of China (Grant Nos. 21621063, 21425312, 21761132035)the National Key R&D Program of China (2017YFA0403402)。
文摘Non-oxidative conversion of methane to olefins,aromatics and hydrogen(MTOAH) has been reported recently over metal single sites such as iron and platinum.The reaction was proposed to involve catalytic activation of methane followed by gas phase C-C coupling of methyl radicals.This study using H atom Rydberg Tagging time-of-flight technique provides direct experimental evidence for the formation of hydrogen radicals during MTOAH reaction over a catalytic quartz wall reactor containing embedded iron species(denoted as Fe-reactor).Fe-reactor gives 7.3% methane conversion at 1273 K with 41.2% selectivity toward C2(ethane,ethylene and acetylene) and 31.8% toward BTX(benzene,toluene and xylene),respectively.The enhancing effects of hydrogen radicals on overall MTOAH performance are validated by cofeeding hydrogen donor benzene,which provides an additional route of methane activation apart from catalytic activation.
基金This work was funded by the Sao Paulo Research Foundation(FAPESP),Brazil(Nos.2012/06718-8 and 2017/11274-5).
文摘Greenhouse gases are known to play an important role in global warming.In this study,we determined the effects of selected soil and climate variables on nitrous oxide(N2O),methane(CH4),and carbon dioxide(CO2)emissions from a tropical grassland fertilized with chicken slurry,swine slurry,cattle slurry,and cattle compost.Cumulative N2O emissions did not differ between treatments and varied from 29.26 to 32.85 mg N m^-2.Similarly,cumulative CH4 emissions were not significantly different among the treatments and ranged from 6.34 to 57.73 mg CH4 m^-2.Slurry and compost application induced CO2 emissions that were significantly different from those in the control treatment.The CH4 conversion factors measured were 0.21%,1.39%,4.39%,and 5.07%for cattle compost,chicken slurry,swine slurry,and cattle slurry,respectively,differing from the recommendations of the Intergovernmental Panel on Climate Change(IPCC).The fraction of added Nemitted as N2O was 0.39%,which was lower than the IPCC default value of 2%.Our findings suggest that N2O emissions could be mitigated by replacing synthetic fertilizer sources with either biofertilizer or compost.Our results indicate the following:N2O emission was mainly controlled by soil temperature,followed by soil moisture and then soil NH^"content;CH4 fluxes were mainly controlled by soil moisture and chamber headspace temperature;and CO2 fluxes were mainly controlled by chamber headspace temperature and soil moisture.
基金National Natural Science Foundation of China (No. 10475060)
文摘Methane conversion to C2 hydrocarbons has been investigated with the addition of hydrogen in a plasma reactor of abnormal glow discharge at atmospheric pressure. The aim of this experiment is to minimize coke formation and improve discharge stability. The typical conditions in the experiment are 300 ml of total feed flux and 400 W of discharge power. The experimental results show that methane conversion is from 91.6% to 35.2% in mol, acetylene selectivity is from 90.2% to 57.6%, and ethylene selectivity is approximately from 7.8% to 3.6%, where the coke increases gradually along with the increase of CH4/H2 from 2 ： 8 to 9 ： 1. A stable discharge for a considerable running time can be obtained only at a lower ratio of CH4/H2 = 2：8 or 3： 7. These phenomena indicate that the coke deposition during methane conversion is obviously reduced by adding a large amount of hydrogen during an abnormal glow discharge. A qualitative interpretation is presented, namely, with abundant hydrogen, the possibility that hydrogen molecules are activated to hydrogen radicals is increased with the help of the abnormal glow discharge. These hydrogen radicals react with carbon radicals to form C2 hydrocarbon products. Therefore, the deposition of coke is restrained.
文摘Plasma methane (CH_4) conversion in gliding arc discharge was examined. Theresult data of experiments regarding the performance of gliding arc discharge were presented in thispaper. A simulation which is consisted some chemical kinetic mechanisms has been provided toanalyze and describe the plasma process. The effect of total gas flow rate and input frequencyrefers to power consumption have been studied to evaluate the performance of gliding arc plasmasystem and the reaction mechanism of decomposition. Experiment results indicated that the maximumconversion of CH_4 reached 50% at the total gas flow rate of 1 L/min. The plasma reaction wasoccurred at the atmospheric pressure and the main products were C (solid), hydrogen, and acetylene(C_2H_2). The plasma reaction of methane conversion was exothermic reaction which increased theproduct stream temperature around 30-50℃.
基金supported by the National High-Tech Research and Development Program of China (No. 2006AA11A189)the Research on Novel Technology of Hydrogen Production from Oven Gas from Metallurgy Process (No. 07DZ12036)the National Key Technolo-gies Research and Development Program of China (No. 2006BA103A05)
文摘Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.
基金supported by the CAS Knowledge Innovation Key Project (Grant No. KZCX2-YW- 330)the National Science Fund Fostering Talents in Basic Research to Glaciology and Geocryology (Grant No. J0630966)the Special Project Fund of State Key Laboratory of Engineering of Frozen Soil(Grant No. SKLFSE-ZQ-07)
文摘In order to study the nature of gas hydrate in porous media,the formation and dissociation processes of methane hydrate in loess were investigated.Five cooling rates were applied to form methane hydrate.The nucleation times of methane hydrate formation at each cooling rate were measured for comparison.The experimental results show that cooling rate is a significant factor affecting the nucleation of methane hydrate and gas conversion.Under the same initial conditions,the faster the cooling rate,the shorter the nucleation time,and the lower the methane gas conversion.Five dissociating temperatures were applied to conduct the dissociation experiment of methane hydrate formed in loess.The experimental results indicated that the temperature evidently controlled the dissociation of methane hydrate in loess and the higher the dissociating temperature,the faster the dissociating rates of methane hydrate.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 20106003).
文摘At ambient temperature and pressure, C2H2 and H2 are the dominating products from pure methane conversion under pulsed corona discharge (PCD). When the energy density of 194-1788 kJ/mol was applied, 7%-30% of C2H2 yield and 6%-35% of H2 yield per pass have been obtained. These results are higher than the maximum thermodynamic yield of C2H2 (5.1%) and H2 (3.8%) at 100 kPa and 1100 K, respectively. Thereby, pulsed corona discharge is a very effective tool for “beyond-thermal-equilibrium” conversion of methane to C2H2 and H2 at ambient temperature and pressure. In the PCD energy density range of 339-822 kJ/mol, the carbon distribution of the methane conversion products is found to be: C2H2 86%-89%, C2H2 4%-6%, C2H4 4%-6%, C3 ～2%, C4 ～1%. Through comparison of the product from pure methane, ethane and ethylene conversion at the same discharge conditions, it can be concluded that three pathways may be responsible for the C2H2 formation via CHX radicals produced from the collisions of CH4 molecules with energized electrons in the PCD plasma: (i) C2H2 is formed directly from free radical reactions, (ii) C2H2 is formed through the dehydrogenation of C2H4, which is formed via free radical reactions primarily, and (iii) C2H6 is the primary product and then dehydrogenates to C2H4 (secondary product) and followed by C2H4 dehydrogenation to C2H2.
