Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient...Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient methanol synthesis catalysts from the vast composition space remains a significant challenge.Here we present a machine learning framework for accelerating the development of high space-time yield(STY)methanol synthesis catalysts.A database of methanol synthesis catalysts has been compiled,consisting of catalyst composition,preparation parameters,structural characteristics,reaction conditions and their corresponding catalytic performance.A methodology for constructing catalyst features based on the intrinsic physicochemical properties of the catalyst components has been developed,which significantly reduced the data dimensionality and enhanced the efficiency of machine learning operations.Two high-precision machine learning prediction models for the activities and product selectivity of catalysts were trained and obtained.Using this machine learning framework,an efficient search was achieved within the catalyst composition space,leading to the successful identification of high STY multielement oxide methanol synthesis catalysts.Notably,the CuZnAlTi catalyst achieved high STYs of 0.49 and 0.65 g_(MeOH)/(g_(catalyst)h)for CO_(2)and CO hydrogenation to methanol at 250℃,respectively,and the STY was further increased to 2.63 g_(Me OH)/(g_(catalyst)h)in CO and CO_(2)co-hydrogenation.展开更多
Anatase TiO2 nanosheets（-ns-） with dominant exposed {001} facets were used as support to load copper,and the synthesized Cu/TiO2-ns catalysts were evaluated for CO2 hydrogenation to methanol. Under the reaction cond...Anatase TiO2 nanosheets（-ns-） with dominant exposed {001} facets were used as support to load copper,and the synthesized Cu/TiO2-ns catalysts were evaluated for CO2 hydrogenation to methanol. Under the reaction conditions, P = 3.0 MPa, T = 260 ℃, V（N2）：V（H2）：V（CO2） = 8：69：23 and gas hourly space velocity（GHSV） = 3600 mL g-1h-1, the methanol yield reached an appealing high value, 5.6%. Copper-loading amount, calcination temperature and reduction atmosphere have been investigated in this work, which significantly influence the particle sizes of copper and/or the defect concentration in TiO2, then leading to different catalytic performance. Characterizations of XRD, EPR, CO2-TPD and FTIR demonstrate that higher specific surface area of Cu is good for the hydrogenation of CO2 and adequate amount of Ti3＋ plays important roles in CO2 activation. Both of them facilitate high turnover frequency（TOF） of methanol formation.展开更多
Methanol （CH3OH） is an important industrial chemical with a wide variety of uses. Industrial methanol synthesis catalysts are typically composed of Cu, Zn, and AI, but the use of catalysts incorporating rare earth e...Methanol （CH3OH） is an important industrial chemical with a wide variety of uses. Industrial methanol synthesis catalysts are typically composed of Cu, Zn, and AI, but the use of catalysts incorporating rare earth elements has been shown to improve the catalytic performance. Due to their unique chemical and physical properties, the use of rare earth elements （scandium, yttrium, and the lanthanides） in catalysis in general has continued to increase over the past few decades, while the use of rare earth in methanol synthesis catalysts has not, despite often improving pertbrmance. The ability of several of the rare earth elements （Pr, Ce, Eu, Tb, Yb） to easily switch between oxidation states makes them beneficial for many different types of catalysts. However, for methanol synthesis the surface basicity is an important property, and the basic nature of the rare earth elements can be used to tune the basicity of catalysts. A small number of correlations between rare earth properties and catalytic performance have been observed, but often do not apply to other catalysts. Properties such as strength of basic sites, ionic radius, and etec- tronegativity have been found to correlate with performance results such as activity or selectivity.展开更多
The aging process of pure copper precursors and copper-zinc binary precursorswere studied by XRD, TG-DTG and TPR techniques. The catalytic activity and stability of CuO/ZnOwere tested using fixed-bed flow reactor, and...The aging process of pure copper precursors and copper-zinc binary precursorswere studied by XRD, TG-DTG and TPR techniques. The catalytic activity and stability of CuO/ZnOwere tested using fixed-bed flow reactor, and the physical properties of the catalysts and Cuspecies were characterized with N_2 adsorption and N_2O passivation method, respectively. For theCu-Zn binary system prepared at the precipitating condition of pH=8.0 and temperature=80℃, theinitial phase was a mixture of copper nitrate hydroxide Cu_2(NO_3)(OH)_3, georgeite and hydrozinciteZn_5(CO_3)_2(OH)_6. By increasing the duration of its aging time, the phase of Cu_2(NO_3)(OH)_2first transited to georgeite, and then interdiffused into Zn_5(CO_3)_2(OH)_6 and resulted in two newphases: rosasite (Cu,Zn)_2CO_3(OH)_2 and au-richalcite (Zn,Cu)_5(CO_3)_2(OH)_6. The former phasewas much easier to be formed than the latter one, while the latter phase was more responsible forthe activity of methanol synthesis than the former one. It is found that the composition andstructure of the precursors altered obviously after the colour transition point. The experimentalresults showed that methanol synthesis is a structure-sensitive catalytic reaction.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
Cu/ZnO catalysts were prepared by the co-precipitation method with the addition of OP-10 （polyoxyethylene octylphenol ether） and were chemically and structurally characterized by means of XRD, BET, H2-TPR, CO-TPD an...Cu/ZnO catalysts were prepared by the co-precipitation method with the addition of OP-10 （polyoxyethylene octylphenol ether） and were chemically and structurally characterized by means of XRD, BET, H2-TPR, CO-TPD and N20-titration. The effect of OP-10 addition on the activity of Cu/ZnO for the slurry phase methanol synthesis at 150℃ was evaluated. The results showed that Cu/ZnO prepared with addition of 8% OP-10 （denoted as C8） exhibited the promoted activity for the methanol synthesis. The conversion of CO and the STY （space time yield） of methanol were 42.5% and 74.6% higher than those of Cu/ZnO prepared without addition of OP-10 （denoted as CO）, respectively. The precursor of C8 contained more aurichalcite and rosasite, and the concerted effect of Cu-Zn in C8 was found to be stronger than that in CO. Compared with CO, C8 showed smaller particle size, lower reduction temperature and larger BET and Cu surface areas.展开更多
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
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
An accurate one-dimensional, heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall, and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor u...An accurate one-dimensional, heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall, and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor under periodic reversal of flow direction is presented. Adjustable parameters in this model are the effectiveness factors for each of the three reactions occurring in the synthesis and a factor for the bed to wall heat transfer coefficient correlation. Experimental data were used to evaluate these parameters and reasonable values of these parameters were obtained. The model was found to closely predict the reactor performance under a wide range of operating conditions, such as carbon oxide concentrations, volumetric flow rate, and cyclic period.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 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
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
Titanium-modified (-alumina supported CuO catalyst has been prepared and used to methanol synthesis from CO_2 hydrogenation. The addition of Ti to the CuO/(-Al_2O_3 catalyst made the copper in the catalyst exist in m...Titanium-modified (-alumina supported CuO catalyst has been prepared and used to methanol synthesis from CO_2 hydrogenation. The addition of Ti to the CuO/(-Al_2O_3 catalyst made the copper in the catalyst exist in much smaller crystallites. The effect of the loading of Ti on the activity and selectivity to methanol from CO_2 hydrogenation was investigated. The activity was found to increase with the increasing of surface area of metallic copper, but it is not a linear relationship.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
Methanol synthesis via CO_(2)conversion is a“green carbon”route for mitigating the greenhouse effect and recycling carbon resources.However,despite the widespread use of copper-based systems for methanol synthesis i...Methanol synthesis via CO_(2)conversion is a“green carbon”route for mitigating the greenhouse effect and recycling carbon resources.However,despite the widespread use of copper-based systems for methanol synthesis in recent decades,the chemical state of the active Cu species remains controversial.In this study,various Cu/ZnO/SBA-15 catalysts possessing different interfacial structures were engineered by atomic layer deposition(ALD).The optimized Cu/50c-ZnO/SBA-15 afforded the highest mass-specific methanol formation rate of 211.7 gMeOH·kgcat^(-1)·h^(-1)under the conditions of 250℃ and 3.0 MPa.In-depth characterizations indicated that the electronic state of Cu could be modulated by engineering the interfacial structures of the Cu/ZnO series catalysts,and the Cu cation sites(Cu^(δ+)and Cu^(+))are the active centers for methanol synthesis reaction rather than the Cu^(0)sites.Mechanistic analysis demonstrated that HCO_(3)^(*)and CO_(3)^(*)were slowly transformed to HCOO*and further hydrogenated to methanol following the formate-methoxy intermediate route.This work provides an improved understanding of the origin of the methanol synthesis active centers and emphasizes the potential for fabricating next-generation Cu-based catalysts via ALD.展开更多
Methanol synthesis via CO_(2) hydrogenation stands as a pivotal avenue for CO_(2) conversion and fixation,garnering extensive investigation.Diverse reactor configurations and energy supplies,alongside a spectrum of ca...Methanol synthesis via CO_(2) hydrogenation stands as a pivotal avenue for CO_(2) conversion and fixation,garnering extensive investigation.Diverse reactor configurations and energy supplies,alongside a spectrum of catalyst formulations,have been developed to enhance reaction metrics including conversion,selectivity,productivity,and stability.Integrating state-of-the-art Cu-based catalysts from thermal catalysis into a photothermal reactor yielded notable results,achieving an overall CO_(2) conversion of 98%and methanol selectivity of 86%.Utilizing the liquid out/gas in concept(LOGIC)reactor,in which only the catalyst bed is irradiated to raise its temperature,facilitated the condensation of products(H_(2)O and CH3OH),due to their low vapor pressure.The lower concentration of products in vapor phases ensured the continuous progress of the reaction.The synergistic integration of reactor design and catalyst fabrication could capitalize on the strengths of both components and lead to enhanced performance in methanol synthesis.展开更多
A series of palladium-modified(Pd-modified)CuO-ZnO-Al_(2)O_(3)(CZA)catalysts with various Pd loadings(0.3 wt%to 2.4 wt%)were prepared using the wetness impregnation method,on two CZA supports with different structures...A series of palladium-modified(Pd-modified)CuO-ZnO-Al_(2)O_(3)(CZA)catalysts with various Pd loadings(0.3 wt%to 2.4 wt%)were prepared using the wetness impregnation method,on two CZA supports with different structures that are CZA-aged precursor composed of a mixture of zincian-malachite and hydrotalcite-like phases(CZA-zH),and CuO-ZnO-Al_(2)O_(3)metal oxide nanoparticles(CZA-MO).Enhancement on catalytic activity can be observed on both Pd-modified CZA catalysts in a temperature range of 180-240℃for methanol synthesis via CO_(2)hydrogenation.Pd/CZA-zH catalysts exhibited a more efficient and stable production of methanol at a relatively low reaction temperature of 180℃for 100 hrs of reaction.The improvement of activity is mainly ascribed to a higher surface area and abundant oxygen-containing functional groups(e.g.,-OH)of CZA-zH support,which is beneficial for better adsorption and distribution of Pd promoter.Hydrogen temperature programmed reduction and X-ray photoelectron spectroscopy results demonstrated a better interaction between Pd and Cu on Pd/CZA-zH catalysts via enhanced reducibility of CuO,and peak shift of Cu to a lower binding energy.The difference in the efficient utilization of hydrogen spillover effect of Pd promoter over two CZA supports resulted in the different performances for methanol synthesis under mild reaction co℃nditions.展开更多
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LDT23E06012E06)National Key R&D Program of China(2023YFC3710800)+3 种基金the National EnergySaving and Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)Pioneer R&D Program of Zhejiang Province-China(2024SSYS0066,2023C03016)National Natural Science Foundation of China(42341208)Zhejiang Energy Group Research Fund(ZNKJ-2023-100)。
文摘Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient methanol synthesis catalysts from the vast composition space remains a significant challenge.Here we present a machine learning framework for accelerating the development of high space-time yield(STY)methanol synthesis catalysts.A database of methanol synthesis catalysts has been compiled,consisting of catalyst composition,preparation parameters,structural characteristics,reaction conditions and their corresponding catalytic performance.A methodology for constructing catalyst features based on the intrinsic physicochemical properties of the catalyst components has been developed,which significantly reduced the data dimensionality and enhanced the efficiency of machine learning operations.Two high-precision machine learning prediction models for the activities and product selectivity of catalysts were trained and obtained.Using this machine learning framework,an efficient search was achieved within the catalyst composition space,leading to the successful identification of high STY multielement oxide methanol synthesis catalysts.Notably,the CuZnAlTi catalyst achieved high STYs of 0.49 and 0.65 g_(MeOH)/(g_(catalyst)h)for CO_(2)and CO hydrogenation to methanol at 250℃,respectively,and the STY was further increased to 2.63 g_(Me OH)/(g_(catalyst)h)in CO and CO_(2)co-hydrogenation.
基金financially supported by the National Natural Science Foundation of China (no. 91645119, 21207039, B5151050)the Fundamental Research Funds for the Central Universities (No.2017ZD076)+2 种基金Guangzhou science and technology plan (201607010095)the Natural Science Foundation of Guangdong Province, China (Grant no. S2011010000737)State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, P.R. China (No. 201602)
文摘Anatase TiO2 nanosheets（-ns-） with dominant exposed {001} facets were used as support to load copper,and the synthesized Cu/TiO2-ns catalysts were evaluated for CO2 hydrogenation to methanol. Under the reaction conditions, P = 3.0 MPa, T = 260 ℃, V（N2）：V（H2）：V（CO2） = 8：69：23 and gas hourly space velocity（GHSV） = 3600 mL g-1h-1, the methanol yield reached an appealing high value, 5.6%. Copper-loading amount, calcination temperature and reduction atmosphere have been investigated in this work, which significantly influence the particle sizes of copper and/or the defect concentration in TiO2, then leading to different catalytic performance. Characterizations of XRD, EPR, CO2-TPD and FTIR demonstrate that higher specific surface area of Cu is good for the hydrogenation of CO2 and adequate amount of Ti3＋ plays important roles in CO2 activation. Both of them facilitate high turnover frequency（TOF） of methanol formation.
文摘Methanol （CH3OH） is an important industrial chemical with a wide variety of uses. Industrial methanol synthesis catalysts are typically composed of Cu, Zn, and AI, but the use of catalysts incorporating rare earth elements has been shown to improve the catalytic performance. Due to their unique chemical and physical properties, the use of rare earth elements （scandium, yttrium, and the lanthanides） in catalysis in general has continued to increase over the past few decades, while the use of rare earth in methanol synthesis catalysts has not, despite often improving pertbrmance. The ability of several of the rare earth elements （Pr, Ce, Eu, Tb, Yb） to easily switch between oxidation states makes them beneficial for many different types of catalysts. However, for methanol synthesis the surface basicity is an important property, and the basic nature of the rare earth elements can be used to tune the basicity of catalysts. A small number of correlations between rare earth properties and catalytic performance have been observed, but often do not apply to other catalysts. Properties such as strength of basic sites, ionic radius, and etec- tronegativity have been found to correlate with performance results such as activity or selectivity.
文摘The aging process of pure copper precursors and copper-zinc binary precursorswere studied by XRD, TG-DTG and TPR techniques. The catalytic activity and stability of CuO/ZnOwere tested using fixed-bed flow reactor, and the physical properties of the catalysts and Cuspecies were characterized with N_2 adsorption and N_2O passivation method, respectively. For theCu-Zn binary system prepared at the precipitating condition of pH=8.0 and temperature=80℃, theinitial phase was a mixture of copper nitrate hydroxide Cu_2(NO_3)(OH)_3, georgeite and hydrozinciteZn_5(CO_3)_2(OH)_6. By increasing the duration of its aging time, the phase of Cu_2(NO_3)(OH)_2first transited to georgeite, and then interdiffused into Zn_5(CO_3)_2(OH)_6 and resulted in two newphases: rosasite (Cu,Zn)_2CO_3(OH)_2 and au-richalcite (Zn,Cu)_5(CO_3)_2(OH)_6. The former phasewas much easier to be formed than the latter one, while the latter phase was more responsible forthe activity of methanol synthesis than the former one. It is found that the composition andstructure of the precursors altered obviously after the colour transition point. The experimentalresults showed that methanol synthesis is a structure-sensitive catalytic reaction.
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）.
基金supported by the Chinese Ministry of Science & Technology (2005CCA00700)Spring Scenery Plan (2006) and Program for New Century Excellent Talents in University (NCET-08-0872) from the Chinese Ministry of Education
文摘Cu/ZnO catalysts were prepared by the co-precipitation method with the addition of OP-10 （polyoxyethylene octylphenol ether） and were chemically and structurally characterized by means of XRD, BET, H2-TPR, CO-TPD and N20-titration. The effect of OP-10 addition on the activity of Cu/ZnO for the slurry phase methanol synthesis at 150℃ was evaluated. The results showed that Cu/ZnO prepared with addition of 8% OP-10 （denoted as C8） exhibited the promoted activity for the methanol synthesis. The conversion of CO and the STY （space time yield） of methanol were 42.5% and 74.6% higher than those of Cu/ZnO prepared without addition of OP-10 （denoted as CO）, respectively. The precursor of C8 contained more aurichalcite and rosasite, and the concerted effect of Cu-Zn in C8 was found to be stronger than that in CO. Compared with CO, C8 showed smaller particle size, lower reduction temperature and larger BET and Cu surface areas.
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The authors are grateful for financial support from the National Natural Science Foundation of China (No. 29476223) and the Ministry of Chemical Industry of China (No. 95-23-01).
文摘An accurate one-dimensional, heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall, and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor under periodic reversal of flow direction is presented. Adjustable parameters in this model are the effectiveness factors for each of the three reactions occurring in the synthesis and a factor for the bed to wall heat transfer coefficient correlation. Experimental data were used to evaluate these parameters and reasonable values of these parameters were obtained. The model was found to closely predict the reactor performance under a wide range of operating conditions, such as carbon oxide concentrations, volumetric flow rate, and cyclic period.
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.
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Natural Science Foundation of Zhejiang province.
文摘Titanium-modified (-alumina supported CuO catalyst has been prepared and used to methanol synthesis from CO_2 hydrogenation. The addition of Ti to the CuO/(-Al_2O_3 catalyst made the copper in the catalyst exist in much smaller crystallites. The effect of the loading of Ti on the activity and selectivity to methanol from CO_2 hydrogenation was investigated. The activity was found to increase with the increasing of surface area of metallic copper, but it is not a linear relationship.
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supported by the National Key Research and Development Program of China(2022YFB4101800)the National Natural Science Foundation of China(22172032 and U22A20431).
文摘Methanol synthesis via CO_(2)conversion is a“green carbon”route for mitigating the greenhouse effect and recycling carbon resources.However,despite the widespread use of copper-based systems for methanol synthesis in recent decades,the chemical state of the active Cu species remains controversial.In this study,various Cu/ZnO/SBA-15 catalysts possessing different interfacial structures were engineered by atomic layer deposition(ALD).The optimized Cu/50c-ZnO/SBA-15 afforded the highest mass-specific methanol formation rate of 211.7 gMeOH·kgcat^(-1)·h^(-1)under the conditions of 250℃ and 3.0 MPa.In-depth characterizations indicated that the electronic state of Cu could be modulated by engineering the interfacial structures of the Cu/ZnO series catalysts,and the Cu cation sites(Cu^(δ+)and Cu^(+))are the active centers for methanol synthesis reaction rather than the Cu^(0)sites.Mechanistic analysis demonstrated that HCO_(3)^(*)and CO_(3)^(*)were slowly transformed to HCOO*and further hydrogenated to methanol following the formate-methoxy intermediate route.This work provides an improved understanding of the origin of the methanol synthesis active centers and emphasizes the potential for fabricating next-generation Cu-based catalysts via ALD.
基金supported by National Key R&D Program of China(2022YFE0114900)New Cornerstone Science Foundation,it has also received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 101022202.D.M.acknowledges support from the Tencent Foundation through the XPLORER PRIZE.Zeng would like to express gratitude to the China Postdoctoral Science Foundation(2021M700209,2024T170015)。
文摘Methanol synthesis via CO_(2) hydrogenation stands as a pivotal avenue for CO_(2) conversion and fixation,garnering extensive investigation.Diverse reactor configurations and energy supplies,alongside a spectrum of catalyst formulations,have been developed to enhance reaction metrics including conversion,selectivity,productivity,and stability.Integrating state-of-the-art Cu-based catalysts from thermal catalysis into a photothermal reactor yielded notable results,achieving an overall CO_(2) conversion of 98%and methanol selectivity of 86%.Utilizing the liquid out/gas in concept(LOGIC)reactor,in which only the catalyst bed is irradiated to raise its temperature,facilitated the condensation of products(H_(2)O and CH3OH),due to their low vapor pressure.The lower concentration of products in vapor phases ensured the continuous progress of the reaction.The synergistic integration of reactor design and catalyst fabrication could capitalize on the strengths of both components and lead to enhanced performance in methanol synthesis.
基金supported in part by the U.S.Department of Energy through contracts DE-FE0031909 and DE-FE0031909.
文摘A series of palladium-modified(Pd-modified)CuO-ZnO-Al_(2)O_(3)(CZA)catalysts with various Pd loadings(0.3 wt%to 2.4 wt%)were prepared using the wetness impregnation method,on two CZA supports with different structures that are CZA-aged precursor composed of a mixture of zincian-malachite and hydrotalcite-like phases(CZA-zH),and CuO-ZnO-Al_(2)O_(3)metal oxide nanoparticles(CZA-MO).Enhancement on catalytic activity can be observed on both Pd-modified CZA catalysts in a temperature range of 180-240℃for methanol synthesis via CO_(2)hydrogenation.Pd/CZA-zH catalysts exhibited a more efficient and stable production of methanol at a relatively low reaction temperature of 180℃for 100 hrs of reaction.The improvement of activity is mainly ascribed to a higher surface area and abundant oxygen-containing functional groups(e.g.,-OH)of CZA-zH support,which is beneficial for better adsorption and distribution of Pd promoter.Hydrogen temperature programmed reduction and X-ray photoelectron spectroscopy results demonstrated a better interaction between Pd and Cu on Pd/CZA-zH catalysts via enhanced reducibility of CuO,and peak shift of Cu to a lower binding energy.The difference in the efficient utilization of hydrogen spillover effect of Pd promoter over two CZA supports resulted in the different performances for methanol synthesis under mild reaction co℃nditions.
