Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
Comparative studies of four common-used anode gas diffusion layers(A-GDLs),namely carbon cloth,carbon paper,carbon paper based on XC-72(in short XC-72)and GDL made of carbon nanotubes(CNT)for direct methanol fuel cell...Comparative studies of four common-used anode gas diffusion layers(A-GDLs),namely carbon cloth,carbon paper,carbon paper based on XC-72(in short XC-72)and GDL made of carbon nanotubes(CNT)for direct methanol fuel cells(DMFCs)were carried out and discussed.The results of scanning electron microscope(SEM),mercury intrusion porosimeter(MIP)and electrochemical test show that CNT has large pore size distribution in pore size of 1000-3000nm and the largest total porosity compared with those of the other three.Carbon paper and XC-72show disadvantageous influences on cell performances at high current density,because carbon paper has many large pores which are unsuited for water transport,while XC-72has many small pores which are unsuited for gas transport.Though cell with carbon cloth has the highest methanol diffusion coefficient,it shows a little lower performance than that with CNT due to its thickness.Anode polarization(AP)results also display that the cell with CNT has the least methanol mass transfer resistance.As a result,the cell with CNT shows the best performance with the highest limiting current density and peak power density of 460 mA·cm^(-2)and 110mW·cm^(-2),respectively.展开更多
Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an ove...Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an overview of state-of-the-art investigations on methanol reforming is critically summarized, including the detailed introduction of methanol conversion pathways from the perspective of fuel cell applications, various advanced materials design for catalytic methanol conversion, as well as the development of steam methanol reformers. For the section of utilization pathways, reactions such as steam reforming of methanol, partial oxidation of methanol, oxidative steam reforming of methanol, and sorption-enhanced steam methanol reforming were elaborated;For the catalyst section, the strategies to enhance the catalytic activity and other comprehensive performances were summarized;For the reactor section, the newly designed steam methanol reformers were thoroughly described. This review will benefit researchers from both fundamental research and fuel cell applications in the field of catalyzing methanol to hydrogen.展开更多
Electrochemically exfoliated graphene(EEG)is a kind of high-quality graphene with few oxygen-containing functional groups and defects on the surface,and thereby is more suitable as catalyst support than other carbon m...Electrochemically exfoliated graphene(EEG)is a kind of high-quality graphene with few oxygen-containing functional groups and defects on the surface,and thereby is more suitable as catalyst support than other carbon materials such as extensively used reduced graphene oxide(rGO).However,it is difficult to grow functional materials on EEG due to its inert surface.In this work,ultra-small Pt nanocrystals(~2.6 nm)are successfully formed on EEG and show better electrocatalytic activity towards methanol oxidation than Pt catalysts on r GO.The outstanding catalytic properties of Pt catalysts on EEG can be attributed to the fast electron transfer through EEG and high quality of Pt catalysts such as small grain size,high dispersibility and low oxidation ratio.In addition,SnO2 nanocrystals are controllably generated around Pt catalysts on EEG to raise the poison tolerance of Pt catalysts through using glycine as a linker.Owing to its outstanding properties such as high electrical conductivity and mechanical strength,EEG is expected to be widely used as a novel support for catalysts.展开更多
This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investi...This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.展开更多
Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO ...Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO selectivity were investigated.M ethanol conversion was increased considerably in the range of about 240-300,after which it increased at a slightly lower rate.The used feed flowrate,steam to methanol molar ratio and carrier gas flowwere 1.2-9.0 m L/h,1.2-5.0 and 20-80 m L/min,respectively.Reducing the feed flowrate increased the H_2 production rate.It was found that an increase in the water to methanol ratio and decreasing the carrier gas flowrate slightly increases the H2production rate.Increasing the water to methanol ratio causes the lowest temperature in which CO formation was observed to rise,so that for the ratio of 5.0 no CO formation was detected in temperatures lower than 375℃.In all conditions,by approaching the complete conversion,increasing the main product concentration,increasing the temperature and contact time,and decreasing the steam to methanol ratio,the CO selectivity was increased.These results suggested that CO was formed as a secondary product through reverse water-gas shift reaction and did not participate in the methanol steam reforming reaction mechanism.展开更多
PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing ...PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.展开更多
Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were ...Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were carried out to characterize the morphology, composition and the electrochemical properties of the PtRu/C catalyst. The results revealed that the PtRu nanoparticles with small average particle size (≈2.5 nm), and highly dispersed on the carbon support. The PtRu/C catalyst exhibited high catalytic activity and anti poisoned performance than that of the JM PtRu/C. It is imply that the modified polyol method is efficient for PtRu/C catalyst preparation.展开更多
In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first react...In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first reaction of DMC synthesis(the reaction of urea with methanol to methyl carbamate(MC)),the reaction kinetics can be described as the first order with respect to the concentrations of both methanol and urea.For the second reaction of DMC synthesis(the reaction of MC with methanol to DMC),the results exhibit characteristics of zero-order reaction.For Zn-containing catalyst,the first reaction is neglected in the kinetics model since its rate is much faster than the second reaction.The macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model,in which a side reaction in forming process of DMC is incorporated since it decreases the yield of DMC drastically at high temperature.The activation energy of the reaction from MC to DMC is 104 kJ/mol while that of the side reaction of DMC is 135 kJ/mol.The highest yield of DMC is 23%.展开更多
Cation ion-exchange resin particles （CERP）/polyethersulfone （PES） hybrid catalytic membranes were prepared by immerse phase inversion for the esterification of different free fatty acids （FFAs） （such as, dodeca...Cation ion-exchange resin particles （CERP）/polyethersulfone （PES） hybrid catalytic membranes were prepared by immerse phase inversion for the esterification of different free fatty acids （FFAs） （such as, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecadienoic acid） with methanol. The membranes were characterized by SEM, ion-exchange capacity and swelling degree test. It is found that dodecanoic acid has the highest FFAs conversion among the four acids for its stronger acidic and reactivity. Different effects of membrane annealing temperature, reaction temperature, molar ratio of methanol to FFAs and catalytic membrane loading on the esterification were investigated by the esterification of dodecanoic acid with methanol. The dodecanoic acid conversion reaches 97.5% trader the optimal condition when the esterification reaction lasted for 8 h.展开更多
The developing status of world large-scale methanol production technology is analyzed and Linda's JW low-pressure methanol synthesis reactor with uniform temperature is described. JW serial reactors have been succ...The developing status of world large-scale methanol production technology is analyzed and Linda's JW low-pressure methanol synthesis reactor with uniform temperature is described. JW serial reactors have been successfully introduced in and applied in Harbin Gasification Plant and the productivity has been increased by 50% and now nine sets of equipments are successfully running in Harbin Gasification Plant,Jiangsu Xinya, Shandong Kenli,Henan Zhongyuan, Handan Xinyangguang,' Shanxi Weihua and Inner Mongolia Tianye. Now it has manufacturing the reactors of 300,000 t/a for Liaoning Dahua. Some solutions for the structure problems of 1000 ～5000 t/d methanol synthesis rectors are put forward.展开更多
Base on industrial research and experience, the process of methanol distillation is analyzed,and above all, a new concept of high pressure flowsheet and low pressure flowsheet is defined. The new configuration helps t...Base on industrial research and experience, the process of methanol distillation is analyzed,and above all, a new concept of high pressure flowsheet and low pressure flowsheet is defined. The new configuration helps to handle problems encountered in many factories in China. The inter influence between process and column internal pattern is also pointed out. Recommendation of new column internal designs is given. Finally, industrial examples tell the how the new concept works and the possibility of combining process to give more opens to solve engineering problems.展开更多
As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular...As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.展开更多
Dimethyl ether(DME) is amongst one of the most promising alternative,renewable and clean fuels being considered as a future energy carrier.In this study,the comparative catalytic performance of the halogenated γ-Al 2...Dimethyl ether(DME) is amongst one of the most promising alternative,renewable and clean fuels being considered as a future energy carrier.In this study,the comparative catalytic performance of the halogenated γ-Al 2 O 3 prepared from two halogen precursors(ammonium chloride and ammonium fluoride) is presented.The impact of ultrasonic irradiation was evaluated in order to optimize both the halogen precursor for the production of DME from methanol in a fixed bed reactor.The catalysts were characterized by SEM,XRD,BET and NH 3-TPD.Under reaction conditions where the temperature ranged from 200 to 400 ℃ with a WHSV = 15.9 h-1was found that the halogenated catalysts showed higher activity at all reaction temperatures.However,the halogenated alumina catalysts prepared under the effect of ultrasonic irradiation showed higher performance of γ-Al 2 O 3 for DME formation.The chlorinated γ-Al 2 O 3 catalysts showed a higher activity and selectivity for DME production than fluorinated versions.展开更多
Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Ptx-Sny catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5 mol/L H2SO4 and...Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Ptx-Sny catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5 mol/L H2SO4 and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt. Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Ptx-Sny/Ti towards the methanol oxidation reaction is reported. Consequently, the Ptx-Sny/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.展开更多
In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and t...In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and tri-metallic(Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism.展开更多
In this work,fullerene was modified by platinum,ruthenium,tin and tungsten nanoparticles.The material was characterized by XRD,ICP-OES and TEM micrograph.The average nanoparticle size on fullerene was 5-8 nm.The appli...In this work,fullerene was modified by platinum,ruthenium,tin and tungsten nanoparticles.The material was characterized by XRD,ICP-OES and TEM micrograph.The average nanoparticle size on fullerene was 5-8 nm.The application of this material was investigated as a catalyst for methanol oxidation in direct methanol fuel cell.A glassy carbon electrode was modified by Pt/Ru/Sn/W fullerene and electrocatalytic activity of the electrode toward methanol oxidation in basic medium has been demonstrated and investigated using cyclic voltammetry.The catalyst showed good reactivity for methanol oxidation.展开更多
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
文摘Comparative studies of four common-used anode gas diffusion layers(A-GDLs),namely carbon cloth,carbon paper,carbon paper based on XC-72(in short XC-72)and GDL made of carbon nanotubes(CNT)for direct methanol fuel cells(DMFCs)were carried out and discussed.The results of scanning electron microscope(SEM),mercury intrusion porosimeter(MIP)and electrochemical test show that CNT has large pore size distribution in pore size of 1000-3000nm and the largest total porosity compared with those of the other three.Carbon paper and XC-72show disadvantageous influences on cell performances at high current density,because carbon paper has many large pores which are unsuited for water transport,while XC-72has many small pores which are unsuited for gas transport.Though cell with carbon cloth has the highest methanol diffusion coefficient,it shows a little lower performance than that with CNT due to its thickness.Anode polarization(AP)results also display that the cell with CNT has the least methanol mass transfer resistance.As a result,the cell with CNT shows the best performance with the highest limiting current density and peak power density of 460 mA·cm^(-2)and 110mW·cm^(-2),respectively.
基金Project(51876224)supported by the National Natural Science Foundation of ChinaProject(2020CX008)supported by the Innovation-Driven Project of Central South University,China。
文摘Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an overview of state-of-the-art investigations on methanol reforming is critically summarized, including the detailed introduction of methanol conversion pathways from the perspective of fuel cell applications, various advanced materials design for catalytic methanol conversion, as well as the development of steam methanol reformers. For the section of utilization pathways, reactions such as steam reforming of methanol, partial oxidation of methanol, oxidative steam reforming of methanol, and sorption-enhanced steam methanol reforming were elaborated;For the catalyst section, the strategies to enhance the catalytic activity and other comprehensive performances were summarized;For the reactor section, the newly designed steam methanol reformers were thoroughly described. This review will benefit researchers from both fundamental research and fuel cell applications in the field of catalyzing methanol to hydrogen.
基金Projects(21573023,21975030)supported by the National Natural Science Foundation of China。
文摘Electrochemically exfoliated graphene(EEG)is a kind of high-quality graphene with few oxygen-containing functional groups and defects on the surface,and thereby is more suitable as catalyst support than other carbon materials such as extensively used reduced graphene oxide(rGO).However,it is difficult to grow functional materials on EEG due to its inert surface.In this work,ultra-small Pt nanocrystals(~2.6 nm)are successfully formed on EEG and show better electrocatalytic activity towards methanol oxidation than Pt catalysts on r GO.The outstanding catalytic properties of Pt catalysts on EEG can be attributed to the fast electron transfer through EEG and high quality of Pt catalysts such as small grain size,high dispersibility and low oxidation ratio.In addition,SnO2 nanocrystals are controllably generated around Pt catalysts on EEG to raise the poison tolerance of Pt catalysts through using glycine as a linker.Owing to its outstanding properties such as high electrical conductivity and mechanical strength,EEG is expected to be widely used as a novel support for catalysts.
基金supported by the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(2023yjrc51)the National Natural Science Foundation of China(22172184)+2 种基金the Foundation of State Key Laboratory of Coal Conversion(J24-25-603)the Fundamental Research Project of ICC-CAS(SCJC-DT-2023-01)Weiqiao-UCAS Special Projects on Low-Carbon Technology Development(GYY-DTFZ-2022-015)。
文摘This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.
文摘Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO selectivity were investigated.M ethanol conversion was increased considerably in the range of about 240-300,after which it increased at a slightly lower rate.The used feed flowrate,steam to methanol molar ratio and carrier gas flowwere 1.2-9.0 m L/h,1.2-5.0 and 20-80 m L/min,respectively.Reducing the feed flowrate increased the H_2 production rate.It was found that an increase in the water to methanol ratio and decreasing the carrier gas flowrate slightly increases the H2production rate.Increasing the water to methanol ratio causes the lowest temperature in which CO formation was observed to rise,so that for the ratio of 5.0 no CO formation was detected in temperatures lower than 375℃.In all conditions,by approaching the complete conversion,increasing the main product concentration,increasing the temperature and contact time,and decreasing the steam to methanol ratio,the CO selectivity was increased.These results suggested that CO was formed as a secondary product through reverse water-gas shift reaction and did not participate in the methanol steam reforming reaction mechanism.
文摘PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.
文摘Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were carried out to characterize the morphology, composition and the electrochemical properties of the PtRu/C catalyst. The results revealed that the PtRu nanoparticles with small average particle size (≈2.5 nm), and highly dispersed on the carbon support. The PtRu/C catalyst exhibited high catalytic activity and anti poisoned performance than that of the JM PtRu/C. It is imply that the modified polyol method is efficient for PtRu/C catalyst preparation.
基金Project(2010ZC034) supported by the Science Foundation of Yunnan Province,ChinaProject(20105314120005) supported by the Research Fund for Doctor Program of Higher Education of China+2 种基金Project(11-12-609) supported by the Open Foundation of State Key Laboratory of Coal Conversion,ChinaProject(KKJD201051012) supported by the Scientific Research Fund of Yunnan Provincial Education Department,ChinaProject(2009-096) supported by the Analysis and Measure Foundation of Kunming University of Scienceand Technology,China
文摘In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first reaction of DMC synthesis(the reaction of urea with methanol to methyl carbamate(MC)),the reaction kinetics can be described as the first order with respect to the concentrations of both methanol and urea.For the second reaction of DMC synthesis(the reaction of MC with methanol to DMC),the results exhibit characteristics of zero-order reaction.For Zn-containing catalyst,the first reaction is neglected in the kinetics model since its rate is much faster than the second reaction.The macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model,in which a side reaction in forming process of DMC is incorporated since it decreases the yield of DMC drastically at high temperature.The activation energy of the reaction from MC to DMC is 104 kJ/mol while that of the side reaction of DMC is 135 kJ/mol.The highest yield of DMC is 23%.
基金Project(ZR2011BL005) supported by the Natural Science Foundation of Shandong Province,China
文摘Cation ion-exchange resin particles （CERP）/polyethersulfone （PES） hybrid catalytic membranes were prepared by immerse phase inversion for the esterification of different free fatty acids （FFAs） （such as, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecadienoic acid） with methanol. The membranes were characterized by SEM, ion-exchange capacity and swelling degree test. It is found that dodecanoic acid has the highest FFAs conversion among the four acids for its stronger acidic and reactivity. Different effects of membrane annealing temperature, reaction temperature, molar ratio of methanol to FFAs and catalytic membrane loading on the esterification were investigated by the esterification of dodecanoic acid with methanol. The dodecanoic acid conversion reaches 97.5% trader the optimal condition when the esterification reaction lasted for 8 h.
文摘The developing status of world large-scale methanol production technology is analyzed and Linda's JW low-pressure methanol synthesis reactor with uniform temperature is described. JW serial reactors have been successfully introduced in and applied in Harbin Gasification Plant and the productivity has been increased by 50% and now nine sets of equipments are successfully running in Harbin Gasification Plant,Jiangsu Xinya, Shandong Kenli,Henan Zhongyuan, Handan Xinyangguang,' Shanxi Weihua and Inner Mongolia Tianye. Now it has manufacturing the reactors of 300,000 t/a for Liaoning Dahua. Some solutions for the structure problems of 1000 ～5000 t/d methanol synthesis rectors are put forward.
文摘Base on industrial research and experience, the process of methanol distillation is analyzed,and above all, a new concept of high pressure flowsheet and low pressure flowsheet is defined. The new configuration helps to handle problems encountered in many factories in China. The inter influence between process and column internal pattern is also pointed out. Recommendation of new column internal designs is given. Finally, industrial examples tell the how the new concept works and the possibility of combining process to give more opens to solve engineering problems.
基金supported by the CAS Project for Young Scientists in Basic Research(YSBR-005)the National Natural Science Foundation of China(22325304,22221003 and 22033007)We acknowledge the Supercomputing Center of USTC,Hefei Advanced Computing Center,Beijing PARATERA Tech Co.,Ltd.,for providing high-performance computing services。
文摘As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.
文摘Dimethyl ether(DME) is amongst one of the most promising alternative,renewable and clean fuels being considered as a future energy carrier.In this study,the comparative catalytic performance of the halogenated γ-Al 2 O 3 prepared from two halogen precursors(ammonium chloride and ammonium fluoride) is presented.The impact of ultrasonic irradiation was evaluated in order to optimize both the halogen precursor for the production of DME from methanol in a fixed bed reactor.The catalysts were characterized by SEM,XRD,BET and NH 3-TPD.Under reaction conditions where the temperature ranged from 200 to 400 ℃ with a WHSV = 15.9 h-1was found that the halogenated catalysts showed higher activity at all reaction temperatures.However,the halogenated alumina catalysts prepared under the effect of ultrasonic irradiation showed higher performance of γ-Al 2 O 3 for DME formation.The chlorinated γ-Al 2 O 3 catalysts showed a higher activity and selectivity for DME production than fluorinated versions.
文摘Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Ptx-Sny catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5 mol/L H2SO4 and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt. Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Ptx-Sny/Ti towards the methanol oxidation reaction is reported. Consequently, the Ptx-Sny/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.
基金Fundamental Research Foundation of Sinopec(X505015)
文摘In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and tri-metallic(Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism.
基金Financial support from Renewable Energy Organization of Iran(SUNA)
文摘In this work,fullerene was modified by platinum,ruthenium,tin and tungsten nanoparticles.The material was characterized by XRD,ICP-OES and TEM micrograph.The average nanoparticle size on fullerene was 5-8 nm.The application of this material was investigated as a catalyst for methanol oxidation in direct methanol fuel cell.A glassy carbon electrode was modified by Pt/Ru/Sn/W fullerene and electrocatalytic activity of the electrode toward methanol oxidation in basic medium has been demonstrated and investigated using cyclic voltammetry.The catalyst showed good reactivity for methanol oxidation.
