Improving the specific,technical,economic,and environmental characteristics of piston engines(ICE)operating on alternative gaseous fuels is a pressing task for the energy and mechanical engineering industries.The aim ...Improving the specific,technical,economic,and environmental characteristics of piston engines(ICE)operating on alternative gaseous fuels is a pressing task for the energy and mechanical engineering industries.The aim of the study was to optimize the parameters of the ICE working cycle after replacing the base fuel(propane-butane blend)with syngas from wood sawdust to improve its technical and economic performance based on mathematical modeling.The modeling results were verified through experimental studies(differences for key parameters did not exceed 4.0%).The object of the study was an electric generator based on a single-cylinder spark ignition engine with a power of 1 kW.The article describes the main approaches to creating a mathematical model of the engine working cycle,a test bench for modeling verification,physicochemical properties of the base fuel(propane-butane blend),and laboratory syngas.It was shown that replacing the fuel from a propane-butane blend to laboratory syngas caused a decrease in engine efficiency to 33%(the efficiency of the base ICE was 0.179 vs.the efficiency of 0.119 for the converted ICE for the 0.59 kW power mode).Engine efficiency was chosen as the key criterion for optimizing the working cycle.As a result of optimization,the efficiency of the converted syngas engine was 6.1%higher than that of the base engine running on the propane-butane blend,and the power drop did not exceed 8.0%.Thus,careful fine-tuning of the working cycle parameters allows increasing the technical and economic characteristics of the syngas engine to the level of ICEs running on traditional types of fuel.展开更多
Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in th...Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources.In this study,a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed.The MoO_(3)precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis,and a structural modifier,Cu,was introduced by sputtering.The Cu deposited by sputtering affected the carburization and phase evolution processes.A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed,with theβ-Mo_(2)C exhibiting lattice distortions and defects.This defectiveβ-Mo_(2)C exhibits high reactivity,and facilitates the C=O hydrogenation process,showing a high reactivity of 83.1%yield in the hydrogenation of dimethyl oxalate.This work provides a new approach to the design and application of molybdenum carbide catalysts.展开更多
The production of medical waste(MW)is a growing concern,particularly in light of the increasing annual generation and the exacerbating effects of the COVID-19 pandemic.Traditional techniques such as incineration and l...The production of medical waste(MW)is a growing concern,particularly in light of the increasing annual generation and the exacerbating effects of the COVID-19 pandemic.Traditional techniques such as incineration and landfilling present significant limitations.In this study,a self-designed 50 kW arc plasma reactor was employed to conduct gasification experiments on nitrile-butadiene rubber(NBR)which served as a model of MWand a mixture of NBR/SiO_(2) which served as a model of glass-containing MW,using CO_(2)as the working gas.The CO_(2)thermal plasma gasification process not only ensures the safe and efficient disposal of MW,but also facilitates its effective conversion into H_(2)and CO,achieving a carbon conversion efficiency of 94.52%.The yields of H2 and CO reached 98.52%and 81.83%,respectively,and the specific energy consumption was as low as 3.55 kW·h·kg^(-1).Furthermore,the addition of SiO_(2) was found to inhibit the gasification of NBR and cause damage to the reactor.Therefore,it is recommended that glass waste should be removed prior to the treatment of MW.The CO_(2)thermal plasma gasification technology can not only eliminate environmental and health risks posed by MW,but also convert it into syngas for further utilization.This provides a promising approach to the harmless and resource disposal of MW,while also contributing to the comprehensive utilization of greenhouse gases.展开更多
Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we t...Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl_(2)O_(4)/zeolite catalysts by establishing a complete reaction network,consisting of methanol synthesis and conversion,water gas shift(WGS)reaction,olefin hydrogenation,and other relevant steps.The WGS reaction occurs very readily on ZnAl_(2)O_(4) surface whereas which is less active towards alkane formation via olefin hydrogenation,and the latter can be attributed to the characteristics of the H_(2) heterolytic activation and the weak polarity of olefins.The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations,which is sensitive to reaction conditions like space velocity and reaction temperature.Under a fixed ratio of active sites between oxide and zeolite components,the concept of the“impossible trinity”of high CO conversion,high olefin selectivity,and high space velocity can thus be manifested.This work thus provides a comprehensive kinetic picture on the direct STO conversion,offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.展开更多
A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalys...A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnA1Zr catalyst. After the on-line syngas conditioning at 450℃, the CO2/CO ratio in the blo- syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/（kgcatarh） MeOH with a methanol selectivity of 97.9% at 260 ~C and 5.05 MPa using conventional CuZnA1 catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.展开更多
Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical pro...Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.展开更多
Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried ...Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.展开更多
Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal ox...Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal oxide and calcium sulfate） to transfer heat and oxygen to the fuel. In this paper, the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor. Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process, showing some different features from the CLC. The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios. It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance. The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and ex- perimental results. It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.展开更多
A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were cha...A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.展开更多
Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Rene...Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Renewable energy can be used to drive this process for hydrogen production, especially solar energy. CeO2-Fe2O3 complex oxide oxygen carrier was prepared by the impregnation method and characterized by means of X-ray diffractometer (XRD), Raman spectroscopy (Raman) and hydrogen programmed reduction (H2-TPR). CH4 temperature programmed and isothermal reactions were adopted to test syngas production reactivity, and water splitting reaction was employed to investigate water-splitting activity. Moreover, two-step SRM performance was evaluated by a successive redox cycle. The results showed that CO-uncontaminated H2 and highly selective syngas (with H2/CO ratio close to 2) could be respectively obtained from two steps, and CeFeO3 formation was found in the first redox cycle and proved to be enhanced by the redox treatment. After 10 successive cycles, obvious CeFeO3 phase was detected, which may be responsible for favorable successive redox cycle performances.展开更多
The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producin...The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producing polymers.However,this remains a great challenge due to the low yield of aromatics and poor catalyst stability,which restrict further development.In recent years,extensive research has been reported on the design of effective catalysts and the optimization of operating conditions to obtain better catalytic performance.In this review,we focus on these related achievements and present a comprehensive overview of different kinds of catalysts,mainly including modified Fischer-Tropsch(FT)catalysts and composite catalysts,as well as their performance and reaction mechanisms.The thermodynamic analysis of the reactions involved in this innovative conversion process and the comparison of different methods are also described in detail in this updated review.Finally,the challenges and prospects for direct syngas conversion are discussed to provide general guidelines for the construction of a well-designed reaction route.展开更多
Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and ...Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.展开更多
This research focused on the feasibility of applying the forward and reverse combustion approach to the in situ gasification of lignite with the production of hydrogen-rich syngas(H_(2)and CO).The so-called forward co...This research focused on the feasibility of applying the forward and reverse combustion approach to the in situ gasification of lignite with the production of hydrogen-rich syngas(H_(2)and CO).The so-called forward combustion gasification(FCG)and reverse combustion gasification(RCG)approach in which oxygen and steam are simultaneously fed to the simulated system of underground coal gasification(UCG)was studied.A simulated system of UCG was designed and established.The underground conditions of the coal seam and strata were simulated in the system.The combustion gasification of lignite has been carried out experimentally for almost 6.5 days.The average effective content(H_(2)+CO)of syngas during the FCG phase was 62.31%and the maximum content was 70.92%.For the RCG phase the corresponding figures are 61.33%and 67.91%.Thus,the feasibility of using RCG way for UCG has been demonstrated.The temperature profiles have been provided by using of 85 thermocouples during the model experiment,which portrayed the several nephograms of thermal data in the gasifier were of significance for the prospective gasification processes.展开更多
The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was ex...The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...展开更多
Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their ca...Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity （WHSV） on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.展开更多
In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including...In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.展开更多
A series of Cu-based catalysts were developed for alkylation of benzene with syngas. The catalyst samples were prepared by the impregnation method, and were characterized by XRD, XRF, NH3-TPD, and TEM and evaluated in...A series of Cu-based catalysts were developed for alkylation of benzene with syngas. The catalyst samples were prepared by the impregnation method, and were characterized by XRD, XRF, NH3-TPD, and TEM and evaluated in a fixed bed reactor. The optimized reaction temperature of Cu/Al2O3/ZSM-5 catalyst was 350 ℃, while higher contents of copper were conducive to alkylation of benzene with syngas. The new medium strength acid centers in the catalyst created by Cu were beneficial to alkylation. Hydrogenation reaction of CO was executed on the metal centers without dissociation, Dimethyl ether(DME) was the major intermediate over Cu-based catalysts. Higher selectivity of methylation and lower selectivity of heavy aromatics were confirmed after the second metal(Zn, Mn, or V) was added to the copper catalyst. Cu was partly covered by Zn in the Cu-Zn/Al2O3/ZSM-5 catalyst leading to low dispersion and low activity of copper. Cu-Mn/Al2O3/ZSM-5 catalyst possessed the best yield of methylation product. Cu-Mn composite oxides were probably formed in fresh catalyst, which blocked the sintering of Cu in the reaction process. The loading of Cu decreased dramatically after the introduction of V, while causing an increase of the amount of medium strength acid centers at the same time. V prevented the sintering of copper particles during the reducing process and had a promoting effect on the activity of Cu.展开更多
Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatme...Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.展开更多
The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no ...The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.展开更多
LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a tw...LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation. The structure evolution of the sample as prepared was investigated by XRD, TPR and TEM techniques. For the former, the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNixO3. After reduction and reaction of CO methanation, its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3, in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell. For the latter, the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation, its chemical composites change to Ni/LaFeO3. Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition. In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor with different preparing method or preparing condition. Therefore, it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.展开更多
基金the Ministry of Science and Higher Education of the Russian Federation(Ural Federal University Program of Development within the Priority-2030 Program)is gratefully acknowledged.
文摘Improving the specific,technical,economic,and environmental characteristics of piston engines(ICE)operating on alternative gaseous fuels is a pressing task for the energy and mechanical engineering industries.The aim of the study was to optimize the parameters of the ICE working cycle after replacing the base fuel(propane-butane blend)with syngas from wood sawdust to improve its technical and economic performance based on mathematical modeling.The modeling results were verified through experimental studies(differences for key parameters did not exceed 4.0%).The object of the study was an electric generator based on a single-cylinder spark ignition engine with a power of 1 kW.The article describes the main approaches to creating a mathematical model of the engine working cycle,a test bench for modeling verification,physicochemical properties of the base fuel(propane-butane blend),and laboratory syngas.It was shown that replacing the fuel from a propane-butane blend to laboratory syngas caused a decrease in engine efficiency to 33%(the efficiency of the base ICE was 0.179 vs.the efficiency of 0.119 for the converted ICE for the 0.59 kW power mode).Engine efficiency was chosen as the key criterion for optimizing the working cycle.As a result of optimization,the efficiency of the converted syngas engine was 6.1%higher than that of the base engine running on the propane-butane blend,and the power drop did not exceed 8.0%.Thus,careful fine-tuning of the working cycle parameters allows increasing the technical and economic characteristics of the syngas engine to the level of ICEs running on traditional types of fuel.
文摘Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources.In this study,a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed.The MoO_(3)precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis,and a structural modifier,Cu,was introduced by sputtering.The Cu deposited by sputtering affected the carburization and phase evolution processes.A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed,with theβ-Mo_(2)C exhibiting lattice distortions and defects.This defectiveβ-Mo_(2)C exhibits high reactivity,and facilitates the C=O hydrogenation process,showing a high reactivity of 83.1%yield in the hydrogenation of dimethyl oxalate.This work provides a new approach to the design and application of molybdenum carbide catalysts.
基金supported by the National Key Research and Development Program of China(2016YFB0301800)the National High Technology Research and Development Program of China(2015AA020201).
文摘The production of medical waste(MW)is a growing concern,particularly in light of the increasing annual generation and the exacerbating effects of the COVID-19 pandemic.Traditional techniques such as incineration and landfilling present significant limitations.In this study,a self-designed 50 kW arc plasma reactor was employed to conduct gasification experiments on nitrile-butadiene rubber(NBR)which served as a model of MWand a mixture of NBR/SiO_(2) which served as a model of glass-containing MW,using CO_(2)as the working gas.The CO_(2)thermal plasma gasification process not only ensures the safe and efficient disposal of MW,but also facilitates its effective conversion into H_(2)and CO,achieving a carbon conversion efficiency of 94.52%.The yields of H2 and CO reached 98.52%and 81.83%,respectively,and the specific energy consumption was as low as 3.55 kW·h·kg^(-1).Furthermore,the addition of SiO_(2) was found to inhibit the gasification of NBR and cause damage to the reactor.Therefore,it is recommended that glass waste should be removed prior to the treatment of MW.The CO_(2)thermal plasma gasification technology can not only eliminate environmental and health risks posed by MW,but also convert it into syngas for further utilization.This provides a promising approach to the harmless and resource disposal of MW,while also contributing to the comprehensive utilization of greenhouse gases.
文摘Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl_(2)O_(4)/zeolite catalysts by establishing a complete reaction network,consisting of methanol synthesis and conversion,water gas shift(WGS)reaction,olefin hydrogenation,and other relevant steps.The WGS reaction occurs very readily on ZnAl_(2)O_(4) surface whereas which is less active towards alkane formation via olefin hydrogenation,and the latter can be attributed to the characteristics of the H_(2) heterolytic activation and the weak polarity of olefins.The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations,which is sensitive to reaction conditions like space velocity and reaction temperature.Under a fixed ratio of active sites between oxide and zeolite components,the concept of the“impossible trinity”of high CO conversion,high olefin selectivity,and high space velocity can thus be manifested.This work thus provides a comprehensive kinetic picture on the direct STO conversion,offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.
基金This work was supported by the National High Tech Research and Development Program （No.2009AA05Z435）, the National Basic Research Program of Ministry of Science and Technology of China （No.2007CB210206）, and the National Natural Science Foundation of China （No.50772107）.
文摘A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnA1Zr catalyst. After the on-line syngas conditioning at 450℃, the CO2/CO ratio in the blo- syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/（kgcatarh） MeOH with a methanol selectivity of 97.9% at 260 ~C and 5.05 MPa using conventional CuZnA1 catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.
基金Projects(51374004,51174105,51204083,51104074,51306084)supported by the National Natural Science Foundation of ChinaProjects(2012FD016,2014HB006)supported by the Applied Basic Research Program of Yunnan Province,ChinaProject(2010241)supported by the Analysis and Testing Foundation of Kunming University of Science and Technology,China
文摘Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.
基金financially supported by Independent Research Subject from Ministry of Science and Technology of China(No.2008BWZ005)
文摘Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.
基金Supported by the National~ Natural Science Foundation of China （20876079）, the Natural Science Funds for Distinguished Young Scholar in Shandong Province （JQ200904）, and Shandong Province Key Technologies Research and Development Program of China （2008GG 10006010, 2009GG 10007001）.
文摘Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal oxide and calcium sulfate） to transfer heat and oxygen to the fuel. In this paper, the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor. Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process, showing some different features from the CLC. The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios. It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance. The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and ex- perimental results. It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.
文摘A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.
基金Project support by the National Natural Science Foundation of China (50574046, 50774038)the Natural Science Foundation of Yunnan Prov-ince (2008E030M)+1 种基金the Research Fund for the Doctoral Program of Higher Education of China (20095314120005)2010 Innovation Fund of Kunming University of Science and Technology
文摘Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Renewable energy can be used to drive this process for hydrogen production, especially solar energy. CeO2-Fe2O3 complex oxide oxygen carrier was prepared by the impregnation method and characterized by means of X-ray diffractometer (XRD), Raman spectroscopy (Raman) and hydrogen programmed reduction (H2-TPR). CH4 temperature programmed and isothermal reactions were adopted to test syngas production reactivity, and water splitting reaction was employed to investigate water-splitting activity. Moreover, two-step SRM performance was evaluated by a successive redox cycle. The results showed that CO-uncontaminated H2 and highly selective syngas (with H2/CO ratio close to 2) could be respectively obtained from two steps, and CeFeO3 formation was found in the first redox cycle and proved to be enhanced by the redox treatment. After 10 successive cycles, obvious CeFeO3 phase was detected, which may be responsible for favorable successive redox cycle performances.
基金the National Key R&D Program of China(2016YFA0202804)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)+2 种基金the Youth Innovation Promotion Association CAS for financial supportthe National Natural Science Foundation of China(21506204,21476226)Dalian Science Foundation for Distinguished Young Scholars(2016RJ04)~~
文摘The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producing polymers.However,this remains a great challenge due to the low yield of aromatics and poor catalyst stability,which restrict further development.In recent years,extensive research has been reported on the design of effective catalysts and the optimization of operating conditions to obtain better catalytic performance.In this review,we focus on these related achievements and present a comprehensive overview of different kinds of catalysts,mainly including modified Fischer-Tropsch(FT)catalysts and composite catalysts,as well as their performance and reaction mechanisms.The thermodynamic analysis of the reactions involved in this innovative conversion process and the comparison of different methods are also described in detail in this updated review.Finally,the challenges and prospects for direct syngas conversion are discussed to provide general guidelines for the construction of a well-designed reaction route.
基金supported by the Ministry of Science and Technology of China (No.2017YFB0602201)the Chinese Academy of Sciences (XDA21020400)+2 种基金the National Natural Science Foundation of China (Grant nos.91645204, 21425312 and 21621063)the Youth Innovation Promotion Association of Chinese Academy of Sciences (2019184)the INCOE (International Network of Centers of Excellence) project coordinated by BASF SE
文摘Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.
基金The work has been supported by the National High Technology Research and Development Program 863 of China(2011AA050106)the Fundamental Research Funds for the Central Universities(2012YH01).
文摘This research focused on the feasibility of applying the forward and reverse combustion approach to the in situ gasification of lignite with the production of hydrogen-rich syngas(H_(2)and CO).The so-called forward combustion gasification(FCG)and reverse combustion gasification(RCG)approach in which oxygen and steam are simultaneously fed to the simulated system of underground coal gasification(UCG)was studied.A simulated system of UCG was designed and established.The underground conditions of the coal seam and strata were simulated in the system.The combustion gasification of lignite has been carried out experimentally for almost 6.5 days.The average effective content(H_(2)+CO)of syngas during the FCG phase was 62.31%and the maximum content was 70.92%.For the RCG phase the corresponding figures are 61.33%and 67.91%.Thus,the feasibility of using RCG way for UCG has been demonstrated.The temperature profiles have been provided by using of 85 thermocouples during the model experiment,which portrayed the several nephograms of thermal data in the gasifier were of significance for the prospective gasification processes.
基金Project supported by the National Natural Science Foundation of China (50574046, 50774038)the Research Fund for the Doctoral Program of Higher Education of China (20095314120005)+1 种基金the Natural Science Foundation of Yunnan Province (2008E030M) the Foundation of Kun-ming University of Science and Technology (KKZ3200927010)
文摘The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...
基金supported by the National Science and Technology Supporting Plan (No. 2006BAE02B02)
文摘Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity （WHSV） on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.
文摘In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.
文摘A series of Cu-based catalysts were developed for alkylation of benzene with syngas. The catalyst samples were prepared by the impregnation method, and were characterized by XRD, XRF, NH3-TPD, and TEM and evaluated in a fixed bed reactor. The optimized reaction temperature of Cu/Al2O3/ZSM-5 catalyst was 350 ℃, while higher contents of copper were conducive to alkylation of benzene with syngas. The new medium strength acid centers in the catalyst created by Cu were beneficial to alkylation. Hydrogenation reaction of CO was executed on the metal centers without dissociation, Dimethyl ether(DME) was the major intermediate over Cu-based catalysts. Higher selectivity of methylation and lower selectivity of heavy aromatics were confirmed after the second metal(Zn, Mn, or V) was added to the copper catalyst. Cu was partly covered by Zn in the Cu-Zn/Al2O3/ZSM-5 catalyst leading to low dispersion and low activity of copper. Cu-Mn/Al2O3/ZSM-5 catalyst possessed the best yield of methylation product. Cu-Mn composite oxides were probably formed in fresh catalyst, which blocked the sintering of Cu in the reaction process. The loading of Cu decreased dramatically after the introduction of V, while causing an increase of the amount of medium strength acid centers at the same time. V prevented the sintering of copper particles during the reducing process and had a promoting effect on the activity of Cu.
基金supported by the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Provincethe Ph.D.Programs Foundation of Liaocheng University(No.31805)the NSF of China(21263011,21376170)
文摘Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.
基金supported by the National Natural Science Foundation of China(21673214,U1732272)
文摘The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.
基金supported by the Financial support from the NSF of China(21066007)the NSF of Tianjin China(10JCZDJC23800)the NSF of Mongolia China(2009BS0203)
文摘LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation. The structure evolution of the sample as prepared was investigated by XRD, TPR and TEM techniques. For the former, the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNixO3. After reduction and reaction of CO methanation, its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3, in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell. For the latter, the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation, its chemical composites change to Ni/LaFeO3. Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition. In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor with different preparing method or preparing condition. Therefore, it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.
