Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub&...Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.展开更多
The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases ...The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.展开更多
The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium prese...The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.展开更多
A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonate...A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.展开更多
Magnetically recyclable porous sodium dodecyl sulfate(SDS)/Fe2O3 hybrids,which combine the porous structure of Fe2O3 and hydrophobicity of SDS,have been successfully synthesized for the first time.Porous Fe2O3 has bee...Magnetically recyclable porous sodium dodecyl sulfate(SDS)/Fe2O3 hybrids,which combine the porous structure of Fe2O3 and hydrophobicity of SDS,have been successfully synthesized for the first time.Porous Fe2O3 has been first pyrolyzed from MIL-100(Fe)using a simple two-step calcination route.Then,the obtained porous Fe2O3 nanoparticles have been self-assembled with SDS molecules and yielded hydrophobic SDS/Fe2O3 hybrids.The porous SDS/Fe2O3 hybrids have been demonstrated to be highly efficient for the denitrification of pyridine under visible light irradiation.The pyridine removal ratio has reached values as high as 100%after irradiation for 240 min.Combining the results of a series of experimental measurements,it was concluded that the superior photocatalytic performance of SDS/Fe2O3 hybrids could be attributed to(i)the fast electron transport owing to the unique porous structure of Fe2O3,(ii)the superior visible light absorption of Fe2O3 nanoparticles,and(iii)the“bridge molecule”role of SDS efficiently improving the separation and transfer across the interfacial domain of SDS/Fe2O3 of photogenerated electron-hole pairs.More significantly,after the catalytic reaction,the SDS/Fe2O3 hybrids could be easily recovered using magnets and reused during subsequent cycles,which indicated their stability and recyclability.展开更多
A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of ...A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of vacancy and antisite were also calculated. The present calculations are in agreement with the experimental data and the theoretical results obtained by other authors.展开更多
The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The ef...The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The effects of solution pH,initial concentration of Pb2+ions,contact time,and temperature on the amount of Pb2+adsorbed were investigated.Adsorption isotherms,adsorption kinetics,and thermodynamic analysis were also studied.The results showed that the maximum adsorption capacity of the Fe3O4@SiO2@DMSA composite is 50.5 mg/g at 298 K,which is higher than that of Fe3O4 and Fe3O4@SiO2 magnetic nanoparticles.The adsorption process agreed well with Langmuir adsorption isotherm models and pseudo second-order kinetics.The thermodynamic analysis revealed that the adsorption was spontaneous,endothermic and energetically driven in nature.展开更多
Molybdenum disilicide （MoSi2） sheath and aluminum oxide （Al2O3） core blended powders were fabricated by spray drying. A derived coating material was produced for the application as microwave absorbers using the as...Molybdenum disilicide （MoSi2） sheath and aluminum oxide （Al2O3） core blended powders were fabricated by spray drying. A derived coating material was produced for the application as microwave absorbers using the as prepared powders by atmospheric plasma spray （APS） technology. The effects of MoSi2/Al2O3 mass ratio on the dielectric and physical mechanical properties of the composite coatings were investigated. When the MoSi2 content of the composites increases from 0 to 45%, the flexure strength and fracture toughness improve from 198 to 324 MPa and 3.05 to 4.82 MPa-m1/2 then decline to 310 MPa and 4.67 MPa-m1/2, respectively. The dielectric loss tangent increases with increasing MoSi2 content, and the real part of permittivity decreases conversely over the frequency range of 8.2-12.4 GHz. These effects are due to the agglomeration of early molten MoSi2 particles and the increase of the electrical conductivity with increasing MoSi2 content.展开更多
As BiVO4 is one of the most popular visible-light-responding photocatalysts, it has been widely used for visiblelight-driven water splitting and environmental purification. However, the typical photocatalytic activity...As BiVO4 is one of the most popular visible-light-responding photocatalysts, it has been widely used for visiblelight-driven water splitting and environmental purification. However, the typical photocatalytic activity of unmodified BiVO4 for the degradation of organic pollutants is still not impressive. To address this limitation, we studied Fe2O3-modified porous BiVO4 nanoplates. Compared with unmodified BiVO4, the Fe2O3-modified porous Bi VO4 nanoplates showed significantly enhanced photocatalytic activities in decomposing both dye and colorless pollutant models, such as rhodamine B(Rh B) and phenol,respectively. The pseudo-first-order reaction rate constants for the degradation of RhB and phenol on Fe2O3-modified BiVO4 porous nanoplates are 27 and 31 times larger than that of pristine Bi VO4, respectively. We also found that the Fe2O3 may act as an efficient non-precious metal co-catalyst, which is responsible for the excellent photocatalytic activity of Fe2O3/BiVO4.Graphical Abstract Fe2O3, as a cheap and efficient co-catalyst, could greatly enhance the photocatalytic activity of Bi VO4 porous nanoplates in decomposing organic pollutants.展开更多
A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure o...A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure of MCM-22 zeolite as evidenced by XRD and N2 adsorption measurements. It was deduced from TPR experiments that γ-Al2O3 phase favored the formation of polymolybdate or multilayered Mo oxide, while more Al2（MoO4）3 species were generated over MCM-22 zeolites. Alumina content in the support was directly related to the metathesis activity of ethene and butene-2 to propene. Mo species with higher valence （Mo6＋or Mo5＋） contributed more to the excellent performance of catalyst than metallic Mo. The best catalyst activity and stability was obtained over 3.0Mo/（MCM-22-30%Al2O3） under the reaction condition of 1.0 MPa and 125℃ using N2 as the pretreatment gas.展开更多
Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst...Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.展开更多
文摘Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.
基金Projects(51304091,U1302274)supported by the National Natural Science Foundation of ChinaProjects(2013FD009,2013FZ007)supported by Applied Basic Research Program of Yunnan Province,ChinaProject(2012HB009)supported by the Candidate Talents Training Fund of Yunnan Province,China
文摘The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.
基金supported by the National Natural Science Foundation of China(22078251)Hubei Province Key Research and Development Program(2023DJC167)the research project of Hubei Provincial Department of Education(D20191504).
文摘The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.
基金Supported by the National Natural Science Foundation of China(21276076)the Fundamental Research Funds for the Central Universities of China(WA1014003)State Key Laboratory of Chemical Engineering(SKL-ChE-10C06)
文摘A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.
基金supported by the National Natural Science Foundation of China(21603112,21806085)Natural Science Foundation of Fujian Province(2016J02692,2019J01837)+1 种基金Natural Science Foundation of Ningde Normal University(2018T03,2018Z02)the Program of Innovative Research Team in Science and Technology in Fujian Province University(IRTSTFJ)~~
文摘Magnetically recyclable porous sodium dodecyl sulfate(SDS)/Fe2O3 hybrids,which combine the porous structure of Fe2O3 and hydrophobicity of SDS,have been successfully synthesized for the first time.Porous Fe2O3 has been first pyrolyzed from MIL-100(Fe)using a simple two-step calcination route.Then,the obtained porous Fe2O3 nanoparticles have been self-assembled with SDS molecules and yielded hydrophobic SDS/Fe2O3 hybrids.The porous SDS/Fe2O3 hybrids have been demonstrated to be highly efficient for the denitrification of pyridine under visible light irradiation.The pyridine removal ratio has reached values as high as 100%after irradiation for 240 min.Combining the results of a series of experimental measurements,it was concluded that the superior photocatalytic performance of SDS/Fe2O3 hybrids could be attributed to(i)the fast electron transport owing to the unique porous structure of Fe2O3,(ii)the superior visible light absorption of Fe2O3 nanoparticles,and(iii)the“bridge molecule”role of SDS efficiently improving the separation and transfer across the interfacial domain of SDS/Fe2O3 of photogenerated electron-hole pairs.More significantly,after the catalytic reaction,the SDS/Fe2O3 hybrids could be easily recovered using magnets and reused during subsequent cycles,which indicated their stability and recyclability.
文摘A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of vacancy and antisite were also calculated. The present calculations are in agreement with the experimental data and the theoretical results obtained by other authors.
基金Project(2013DFA51290)supported by International S&T Cooperation Program of China
文摘The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The effects of solution pH,initial concentration of Pb2+ions,contact time,and temperature on the amount of Pb2+adsorbed were investigated.Adsorption isotherms,adsorption kinetics,and thermodynamic analysis were also studied.The results showed that the maximum adsorption capacity of the Fe3O4@SiO2@DMSA composite is 50.5 mg/g at 298 K,which is higher than that of Fe3O4 and Fe3O4@SiO2 magnetic nanoparticles.The adsorption process agreed well with Langmuir adsorption isotherm models and pseudo second-order kinetics.The thermodynamic analysis revealed that the adsorption was spontaneous,endothermic and energetically driven in nature.
基金Project (50572090) supported by the National Natural Science Foundation of ChinaProject (KP200901) supported by the States Key Laboratory of Solidification Processing in NWPU, China
文摘Molybdenum disilicide （MoSi2） sheath and aluminum oxide （Al2O3） core blended powders were fabricated by spray drying. A derived coating material was produced for the application as microwave absorbers using the as prepared powders by atmospheric plasma spray （APS） technology. The effects of MoSi2/Al2O3 mass ratio on the dielectric and physical mechanical properties of the composite coatings were investigated. When the MoSi2 content of the composites increases from 0 to 45%, the flexure strength and fracture toughness improve from 198 to 324 MPa and 3.05 to 4.82 MPa-m1/2 then decline to 310 MPa and 4.67 MPa-m1/2, respectively. The dielectric loss tangent increases with increasing MoSi2 content, and the real part of permittivity decreases conversely over the frequency range of 8.2-12.4 GHz. These effects are due to the agglomeration of early molten MoSi2 particles and the increase of the electrical conductivity with increasing MoSi2 content.
基金partial financial support from NSFC(51372173,51002107,and21173159)NSFC for Distinguished Young Scholars(51025207)+3 种基金Research Climb Plan of ZJED(pd2013383)Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure(SKL201409SIC)Xinmiao talent project of Zhejiang Province(2013R424060)College Students Research Project of Wenzhou University(14xk193)
文摘As BiVO4 is one of the most popular visible-light-responding photocatalysts, it has been widely used for visiblelight-driven water splitting and environmental purification. However, the typical photocatalytic activity of unmodified BiVO4 for the degradation of organic pollutants is still not impressive. To address this limitation, we studied Fe2O3-modified porous BiVO4 nanoplates. Compared with unmodified BiVO4, the Fe2O3-modified porous Bi VO4 nanoplates showed significantly enhanced photocatalytic activities in decomposing both dye and colorless pollutant models, such as rhodamine B(Rh B) and phenol,respectively. The pseudo-first-order reaction rate constants for the degradation of RhB and phenol on Fe2O3-modified BiVO4 porous nanoplates are 27 and 31 times larger than that of pristine Bi VO4, respectively. We also found that the Fe2O3 may act as an efficient non-precious metal co-catalyst, which is responsible for the excellent photocatalytic activity of Fe2O3/BiVO4.Graphical Abstract Fe2O3, as a cheap and efficient co-catalyst, could greatly enhance the photocatalytic activity of Bi VO4 porous nanoplates in decomposing organic pollutants.
基金supported by the National Natural Science Foundation of China (Grant No. 20903088 and 20773120)the Ministry of Science and Technology of China through the National Key Project of Fundamental Research (Grant No.2009CB623507)
文摘A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure of MCM-22 zeolite as evidenced by XRD and N2 adsorption measurements. It was deduced from TPR experiments that γ-Al2O3 phase favored the formation of polymolybdate or multilayered Mo oxide, while more Al2（MoO4）3 species were generated over MCM-22 zeolites. Alumina content in the support was directly related to the metathesis activity of ethene and butene-2 to propene. Mo species with higher valence （Mo6＋or Mo5＋） contributed more to the excellent performance of catalyst than metallic Mo. The best catalyst activity and stability was obtained over 3.0Mo/（MCM-22-30%Al2O3） under the reaction condition of 1.0 MPa and 125℃ using N2 as the pretreatment gas.
文摘Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.
