One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst（PTC）, quaternary ammonium, combined with sodium hydroxide as catalysts was investigat...One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst（PTC）, quaternary ammonium, combined with sodium hydroxide as catalysts was investigated. Butanal was subjected for detail investigations to study the effect of parameters. It was found that the selectivity of cyclic aldol tetramer depends greatly on the operating conditions of the reaction, especially the PTC/butanal molar ratio. The average selectivity of 2-hydroxy-6-propyl-l, 3, 5-triethyl-3-cyclohexene-1-carboxaldehyde（HPTECHCA） was 54.41% using tetrabutylammonium chloride combined with 14%（mass fraction） Na OH as catalysts at 60 ℃for 2 h with a PTC-to-butanal molar ratio of 0.09：1. Pentanal was more likely to generate cyclic aldol tetramer compared with other aldehydes under the optimum experimental conditions. Recovery of the PTC through water washing followed by adding enough sodium hydroxide from the washings was also demonstrated.展开更多
Bimetallic Co /Fe catalysts supported on carbon nanotubes( CNTs) were prepared,and niobium( Nb) was added as promoter to the 70 Co ∶30Fe /CNT catalyst. The physicochemical properties of the catalysts were characteriz...Bimetallic Co /Fe catalysts supported on carbon nanotubes( CNTs) were prepared,and niobium( Nb) was added as promoter to the 70 Co ∶30Fe /CNT catalyst. The physicochemical properties of the catalysts were characterized,and the catalytic performances were analyzed at the same operation conditions( H_2 ∶CO( volume ratio) = 2 ∶1,p = 1 MPa,and t = 260 ℃) in a tubular fixed-bed microreactor system. The addition of Nb to the bimetallic catalyst decreases the average size of the oxide nanoparticles and improves the reducibility of the bimetallic catalyst. Evaluation of the catalyst performance in a Fischer-Tropsch reaction shows that the catalyst results in high selectivity to methane,and the selectivity to C_(5+) increased slightly in the bimetallic catalyst unlike that in the monometallic catalysts. The addition of 1% Nb to the bimetallic catalyst increases CO conversion and selectivity to C_(5+). Meanwhile,a decrease in methane selectivity is observed.展开更多
Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means...Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction （XRD）, temperature programmed reduction （TPR）, hydrogen temperature programmed desorption （H2-TPD） and O2 titration. Co-support compound formation can be detected in catalyst system by XRD. For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O4 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3O4 crystallites （reduction at 320 ℃） and cobalt oxide-alumina interaction species （reduction at above 400 ℃）. Increasing Co loading results in the increase of Co3O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.展开更多
The effect of ethylene diamine tetraacetic acid(EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings(NS) supported cobalt(Co) catalyst was investigated in the conversio...The effect of ethylene diamine tetraacetic acid(EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings(NS) supported cobalt(Co) catalyst was investigated in the conversion of syngas(H^(2+) CO) to hydrocarbons by Fischer-Tropsch synthesis(FTS). The unmodified Co/NS and modified Co/NS-EDTA catalysts were synthesized via an impregnation method. The prepared Co/NS and Co/NS-EDTA catalysts were characterized before the FTS reaction by BET surface area,X-ray diffraction(XRD),transmission electron microscopy(TEM),temperature programmed reduction(TPR),X-ray photoelectron spectroscopy(XPS),differential thermal analysis(DTA) and thermogravimetric analysis(TGA) in order to find correlations between physico-chemical properties of catalysts and catalytic performance. FTS was carried out in a quartz fixedbed microreactor(H_2/CO of 2 ∶1,230 ℃ and atmospheric pressure) and the products trapped and analyzed by GC-TCD and GC-MS to determine CO conversion and reaction selectivity. The experimental results indicated that the modified Co/NS-EDTA catalyst displayed a more-dispersed phase of Co_3O_4 nanoparticles(10.9%) and the Co_3O_4 average crystallite size was about 12.4 nm. The EDTA modified catalyst showed relatively higher CO conversion(70.3%) and selectivity toward C_(6-18)(JP-8,Jet A and diesel) than the Co/NS catalyst(C_(6-14))(JP-4).展开更多
基金Project(2013AA064102)supported by the National High-Tech Research Program of ChinaProject(11JJ6014)supported by the Hunan Provincial Natural Science Foundation of China
文摘One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst（PTC）, quaternary ammonium, combined with sodium hydroxide as catalysts was investigated. Butanal was subjected for detail investigations to study the effect of parameters. It was found that the selectivity of cyclic aldol tetramer depends greatly on the operating conditions of the reaction, especially the PTC/butanal molar ratio. The average selectivity of 2-hydroxy-6-propyl-l, 3, 5-triethyl-3-cyclohexene-1-carboxaldehyde（HPTECHCA） was 54.41% using tetrabutylammonium chloride combined with 14%（mass fraction） Na OH as catalysts at 60 ℃for 2 h with a PTC-to-butanal molar ratio of 0.09：1. Pentanal was more likely to generate cyclic aldol tetramer compared with other aldehydes under the optimum experimental conditions. Recovery of the PTC through water washing followed by adding enough sodium hydroxide from the washings was also demonstrated.
基金supprted by Short Term Internal Research Fund Universiti Teknologi PETRONAS(0153AA-D06)the Ministry of Education(Higher Education Department)under MyRA Incentive Grant for CO2-Rich Natural Gas Value Chain Program
文摘Bimetallic Co /Fe catalysts supported on carbon nanotubes( CNTs) were prepared,and niobium( Nb) was added as promoter to the 70 Co ∶30Fe /CNT catalyst. The physicochemical properties of the catalysts were characterized,and the catalytic performances were analyzed at the same operation conditions( H_2 ∶CO( volume ratio) = 2 ∶1,p = 1 MPa,and t = 260 ℃) in a tubular fixed-bed microreactor system. The addition of Nb to the bimetallic catalyst decreases the average size of the oxide nanoparticles and improves the reducibility of the bimetallic catalyst. Evaluation of the catalyst performance in a Fischer-Tropsch reaction shows that the catalyst results in high selectivity to methane,and the selectivity to C_(5+) increased slightly in the bimetallic catalyst unlike that in the monometallic catalysts. The addition of 1% Nb to the bimetallic catalyst increases CO conversion and selectivity to C_(5+). Meanwhile,a decrease in methane selectivity is observed.
文摘Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction （XRD）, temperature programmed reduction （TPR）, hydrogen temperature programmed desorption （H2-TPD） and O2 titration. Co-support compound formation can be detected in catalyst system by XRD. For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O4 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3O4 crystallites （reduction at 320 ℃） and cobalt oxide-alumina interaction species （reduction at above 400 ℃）. Increasing Co loading results in the increase of Co3O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.
文摘The effect of ethylene diamine tetraacetic acid(EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings(NS) supported cobalt(Co) catalyst was investigated in the conversion of syngas(H^(2+) CO) to hydrocarbons by Fischer-Tropsch synthesis(FTS). The unmodified Co/NS and modified Co/NS-EDTA catalysts were synthesized via an impregnation method. The prepared Co/NS and Co/NS-EDTA catalysts were characterized before the FTS reaction by BET surface area,X-ray diffraction(XRD),transmission electron microscopy(TEM),temperature programmed reduction(TPR),X-ray photoelectron spectroscopy(XPS),differential thermal analysis(DTA) and thermogravimetric analysis(TGA) in order to find correlations between physico-chemical properties of catalysts and catalytic performance. FTS was carried out in a quartz fixedbed microreactor(H_2/CO of 2 ∶1,230 ℃ and atmospheric pressure) and the products trapped and analyzed by GC-TCD and GC-MS to determine CO conversion and reaction selectivity. The experimental results indicated that the modified Co/NS-EDTA catalyst displayed a more-dispersed phase of Co_3O_4 nanoparticles(10.9%) and the Co_3O_4 average crystallite size was about 12.4 nm. The EDTA modified catalyst showed relatively higher CO conversion(70.3%) and selectivity toward C_(6-18)(JP-8,Jet A and diesel) than the Co/NS catalyst(C_(6-14))(JP-4).
