Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation ...Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.展开更多
Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (T...Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spec-troscopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.展开更多
The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors p...The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].展开更多
Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in d...Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.展开更多
The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared an...The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.展开更多
The catalytic activity of ceria-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditio...The catalytic activity of ceria-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.展开更多
Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction interme...Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction intermediate in this reaction, creating a different reaction pathway. The formation of crystalline phases and characteristic morphology of the co-precipitated precursors during the co-precipitation step were important factors in obtaining an efficient Cu/ZnO catalyst with a high dispersion of metallic copper,which is one of the main active sites for methanol synthesis. The acidic properties of the Cu/ZnO catalyst were also revealed as important factors, since alcohol esterification is considered the rate-limiting step in alcohol-assisted low-temperature methanol synthesis. As a consequence, bifunctionality of the Cu/ZnO catalyst such as metallic copper and acidic properties was required for this reaction. In this respect, the copper content（X） strongly affected the catalytic activity of the Cu/ZnO;catalysts, and accordingly, the Cu/ZnO;.5 catalyst with a high copper dispersion and sufficient acid sites exhibited the best catalytic performance in this reaction.展开更多
Highly active CNT-promoted co-precipitated Cu-ZnO-Al_2O_3 catalysts,symbolized as Cu_iZn_jAl_k-x%CNTs, were prepared, and their catalytic activity for once-throughmethanol synthesis from syngas was investigated. The r...Highly active CNT-promoted co-precipitated Cu-ZnO-Al_2O_3 catalysts,symbolized as Cu_iZn_jAl_k-x%CNTs, were prepared, and their catalytic activity for once-throughmethanol synthesis from syngas was investigated. The results illustrated that, under the reactionconditions (at 493 K, 5.0 MPa, the volume ratio of H_2/CO/CO_2/N_2= 62/30/5/3, GHSV= 4000 h^(-1),the observed single-pass CO-conversion and methanol-STY over a Cu_6Zn_3Al_1-12.5%CNTs catalystreached 64% and 1210 mg/(h-g), which was about 68% and 66% higher than those (38% and 730 mg/(h·g))over the corresponding CNT-free catalyst, Cu-6Zn_3Al_1, respectively. The characteristic studies ofthe catalysts revealed that appropriate incorporation of a minor amount of the CNTs into theCu_iZn_jAl_k brought about little change in the apparent activation energy of the methanol synthesisreaction, however, led to a considerable increase in the catalyst's active Cu surface area andpronouncedly enhanced the stationary-state concentration of active hydrogen-adspecies on the surfaceof the functioning catalyst, which would be favorable to increasing the rate of the COhydro-genation reactions. Moreover, the operation temperature for methanol synthesis over theCNT-promoted catalysts can be 10-20 degrees lower than that over the corresponding CNT-free contrastsystem, which would contribute considerably to an increase in equilibrium CO-conversion andCH_3OH-yield.展开更多
A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7...A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.展开更多
the effects of reduction procedure, reaction temperature andcomposition of feed gas on the activity of a CuO-ZnO-Al_2O_3 catalystfor liquid phase methanol synthesis were studied. An optimizedprocedure different from c...the effects of reduction procedure, reaction temperature andcomposition of feed gas on the activity of a CuO-ZnO-Al_2O_3 catalystfor liquid phase methanol synthesis were studied. An optimizedprocedure different from conventional ones was developed to obtainhigher activity and better stability of the catalyst. Both CO andCO_2 in the feed gas were found to be necessary to maintain theactivity of catalyst in the synthesis process. Reaction temperaturewas limited up to 523 K, otherwise the catalyst will be deactivatedrapidly.展开更多
In this paper several rare earth oxides were added into methanol synthesis catalyst by solid-mixing method to improve the activity of methanol synthesis catalyst. Nd2O3, CeO2, La2O3 and Sm2O3 decrease the catalyst act...In this paper several rare earth oxides were added into methanol synthesis catalyst by solid-mixing method to improve the activity of methanol synthesis catalyst. Nd2O3, CeO2, La2O3 and Sm2O3 decrease the catalyst activity, while Pr2O3, Gd2O3 and Eu2O3 increase the methanol yield.展开更多
The NC310 type catalyst for methanol synthesis developedby the SINOPEC Research Institute of NanjingChemical Company has passed the appraisal of researchachievements organized by the Science and TechnologyDivision of ...The NC310 type catalyst for methanol synthesis developedby the SINOPEC Research Institute of NanjingChemical Company has passed the appraisal of researchachievements organized by the Science and TechnologyDivision of the Sinopec Corp. The group of specialistsattending the appraisal meeting has recognized that thiscatalyst has reached the internationally advanced level interms of its overall catalytic performance.展开更多
C1 chemistry based on synthesis gas, methane, and carbon dioxide offers many routes to industrial chemicals. The reactions related to the synthesis of gas can be classified into direct and indirect approach for making...C1 chemistry based on synthesis gas, methane, and carbon dioxide offers many routes to industrial chemicals. The reactions related to the synthesis of gas can be classified into direct and indirect approach for making such products, such as acetic acid, dimethyl ether, and alcohol. Catalytic syngas processing is currently done at high temperatures and pressures, conditions that could be unfavorable for the life of the catalyst. Another issue of C1 chemistry is related to the methane-initiated process. It has been known that direct methane conversions are still suffering from low yields and selectivity of products resulting in unprofitable ways to produce products, such as higher hydrocarbons, methanol, and so on. However, many experts and researchers are still trying to find the best method to overcome these barriers, for example, by finding the best catalyst to reduce the high-energy barrier of the reactions and conduct only selective catalyst-surface reactions. The appli- cation of Yttria-Stabilized Zirconia （YSZ） and its combination with other metals for catalyzing purposes are increasing. The existence of an interesting site that acts as oxygen store could be the main reason for it. Moreover, formation of intermediate species on the surface of YSZ also contributes significantly in increasing the production of some specific products. Understanding the phenomena happening inside could be necessary. In this article, the use of YSZ for some C1 chemistry reactions was discussed and reviewed.展开更多
One-pot synthesis of dimethyl carbonate (DMC) from methanol, propylene oxide (PO) and carbon dioxide has been investigated using the basic zeolites as catalysts. Among the zeolites studied, Beta showed the best cataly...One-pot synthesis of dimethyl carbonate (DMC) from methanol, propylene oxide (PO) and carbon dioxide has been investigated using the basic zeolites as catalysts. Among the zeolites studied, Beta showed the best catalytic performance for DMC production. That the desilication of zeolite structure resulted in a hierarchical porosity of Beta, leading to more amount of KOH can be loaded on the surface of zeolite and therefore enhancing the base strength of the catalyst was proposed to be the reason for improved catalytic performance.展开更多
文摘Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.
基金Supported by the National Natural Science Foundation of China(N.29476223) and Ministry of Chemical Industry of China under a contract(No.95-23-01).
文摘Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spec-troscopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.
基金supported by the Nature Science Foundation of China(Grant 22262006,22068009)the Supported by Guizhou Provincial Science and Technology Projects(ZK[2023]ordinary 050,[2023]General 403)+4 种基金the Science and Technology Support Plan Projects of Guizhou Province(Grant(2018)2192)the Scientific and Technological Innovation Talents Team of Guizhou(2018-5607)the Science and Technology Foundation of Guizhou Province(20177254)the One hundred Person Project of Guizhou Province(No.20165655)the Innovation Group Project of Education Department in Guizhou Province(No.2021010)。
文摘The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].
基金supported by the National Basic Research Program of China (No. 2011CB201404)the financial support of the State Key Laboratory for Oxo Synthesis and Selective Oxidation (OSSO) of China
文摘Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.
文摘The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.
基金Clean Energy Facing the Future program at the Dalian Institute of Chemical Physics
文摘The catalytic activity of ceria-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.
基金supported by C1 Gas Refinery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science,ICT & Future Planning (2015M3D3A1A01064908)
文摘Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction intermediate in this reaction, creating a different reaction pathway. The formation of crystalline phases and characteristic morphology of the co-precipitated precursors during the co-precipitation step were important factors in obtaining an efficient Cu/ZnO catalyst with a high dispersion of metallic copper,which is one of the main active sites for methanol synthesis. The acidic properties of the Cu/ZnO catalyst were also revealed as important factors, since alcohol esterification is considered the rate-limiting step in alcohol-assisted low-temperature methanol synthesis. As a consequence, bifunctionality of the Cu/ZnO catalyst such as metallic copper and acidic properties was required for this reaction. In this respect, the copper content（X） strongly affected the catalytic activity of the Cu/ZnO;catalysts, and accordingly, the Cu/ZnO;.5 catalyst with a high copper dispersion and sufficient acid sites exhibited the best catalytic performance in this reaction.
基金This work Supported by National Nat. Sci. Foundation (No. 50072021) Fujian Provincial Nat. Sci. Foundation (No. 2001H017) of China.
文摘Highly active CNT-promoted co-precipitated Cu-ZnO-Al_2O_3 catalysts,symbolized as Cu_iZn_jAl_k-x%CNTs, were prepared, and their catalytic activity for once-throughmethanol synthesis from syngas was investigated. The results illustrated that, under the reactionconditions (at 493 K, 5.0 MPa, the volume ratio of H_2/CO/CO_2/N_2= 62/30/5/3, GHSV= 4000 h^(-1),the observed single-pass CO-conversion and methanol-STY over a Cu_6Zn_3Al_1-12.5%CNTs catalystreached 64% and 1210 mg/(h-g), which was about 68% and 66% higher than those (38% and 730 mg/(h·g))over the corresponding CNT-free catalyst, Cu-6Zn_3Al_1, respectively. The characteristic studies ofthe catalysts revealed that appropriate incorporation of a minor amount of the CNTs into theCu_iZn_jAl_k brought about little change in the apparent activation energy of the methanol synthesisreaction, however, led to a considerable increase in the catalyst's active Cu surface area andpronouncedly enhanced the stationary-state concentration of active hydrogen-adspecies on the surfaceof the functioning catalyst, which would be favorable to increasing the rate of the COhydro-genation reactions. Moreover, the operation temperature for methanol synthesis over theCNT-promoted catalysts can be 10-20 degrees lower than that over the corresponding CNT-free contrastsystem, which would contribute considerably to an increase in equilibrium CO-conversion andCH_3OH-yield.
基金supportd by the NNSF of China(#29773037)the NSF of Fujian province(#E9910001 and#E0010006).|
文摘A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.
基金Work performed while the authors were at the Laboratory for Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Slovenia, and supported by the Ministry of Science and Technology of Slovenia (No. J2-0783).
文摘the effects of reduction procedure, reaction temperature andcomposition of feed gas on the activity of a CuO-ZnO-Al_2O_3 catalystfor liquid phase methanol synthesis were studied. An optimizedprocedure different from conventional ones was developed to obtainhigher activity and better stability of the catalyst. Both CO andCO_2 in the feed gas were found to be necessary to maintain theactivity of catalyst in the synthesis process. Reaction temperaturewas limited up to 523 K, otherwise the catalyst will be deactivatedrapidly.
文摘In this paper several rare earth oxides were added into methanol synthesis catalyst by solid-mixing method to improve the activity of methanol synthesis catalyst. Nd2O3, CeO2, La2O3 and Sm2O3 decrease the catalyst activity, while Pr2O3, Gd2O3 and Eu2O3 increase the methanol yield.
文摘The NC310 type catalyst for methanol synthesis developedby the SINOPEC Research Institute of NanjingChemical Company has passed the appraisal of researchachievements organized by the Science and TechnologyDivision of the Sinopec Corp. The group of specialistsattending the appraisal meeting has recognized that thiscatalyst has reached the internationally advanced level interms of its overall catalytic performance.
基金Project supported by the Global R&D Program of the Korea Foundation for International Cooperation of Science and Technology (KICOS)
文摘C1 chemistry based on synthesis gas, methane, and carbon dioxide offers many routes to industrial chemicals. The reactions related to the synthesis of gas can be classified into direct and indirect approach for making such products, such as acetic acid, dimethyl ether, and alcohol. Catalytic syngas processing is currently done at high temperatures and pressures, conditions that could be unfavorable for the life of the catalyst. Another issue of C1 chemistry is related to the methane-initiated process. It has been known that direct methane conversions are still suffering from low yields and selectivity of products resulting in unprofitable ways to produce products, such as higher hydrocarbons, methanol, and so on. However, many experts and researchers are still trying to find the best method to overcome these barriers, for example, by finding the best catalyst to reduce the high-energy barrier of the reactions and conduct only selective catalyst-surface reactions. The appli- cation of Yttria-Stabilized Zirconia （YSZ） and its combination with other metals for catalyzing purposes are increasing. The existence of an interesting site that acts as oxygen store could be the main reason for it. Moreover, formation of intermediate species on the surface of YSZ also contributes significantly in increasing the production of some specific products. Understanding the phenomena happening inside could be necessary. In this article, the use of YSZ for some C1 chemistry reactions was discussed and reviewed.
文摘One-pot synthesis of dimethyl carbonate (DMC) from methanol, propylene oxide (PO) and carbon dioxide has been investigated using the basic zeolites as catalysts. Among the zeolites studied, Beta showed the best catalytic performance for DMC production. That the desilication of zeolite structure resulted in a hierarchical porosity of Beta, leading to more amount of KOH can be loaded on the surface of zeolite and therefore enhancing the base strength of the catalyst was proposed to be the reason for improved catalytic performance.
