To enhance sulfur adsorption and reactive activity, ordered mesoporous Cu-ZnO-Al2O3 adsorbents were prepared by a novel one-pot evaporation-induced self-assembly strategy using P123 as a structure-directing agent and ...To enhance sulfur adsorption and reactive activity, ordered mesoporous Cu-ZnO-Al2O3 adsorbents were prepared by a novel one-pot evaporation-induced self-assembly strategy using P123 as a structure-directing agent and ethanol as the solvent for reactive adsorption desulfurization. The metal oxide precursor molecules around P123 micellized, and self-assembly simultaneously occurred during evaporation from an ethanol solution at 60 °C, leading to the formation of the p6 mm hexagonal symmetry mesoporous structure. Characterization results prove that the Cu-ZnO-Al2O3 adsorbents possess an ordered mesoporous structure with high thermal stability, large surface area（386–226 m2/g）, large pore volume（0.60–0.46 cm3/g）, and good dispersion of ZnO and Cu, which is beneficial for transforming S-compounds to ZnO. The sulfur saturation capacity of the ordered-mesoporous-structure Cu-ZnO-Al2O3 adsorbents is larger（49.4 mg/g） than that of the unordered mesoporous structure（13.5 mg/g）.展开更多
A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al mol...A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al molar ratio of 1:1:0.5 exhibited the best performance for glycerol hydrogenolysis,and thus selected for kinetic investigation.Under elimination of external and internal diffusion limitation,kinetic experiments were performed in an isothermal fixed-bed reactor at a hydrogen pressure range of 3.0-5.0 MPa and a temperature range of 493-513 K. Based on a dehydration-hydrogenation two-step hydrogenolysis mechanism,a two-site Langmuir-Hinshelwood kinetic model taking into account competitive adsorption of glycerol,acetol and propylene glycol was proposed and successfully fitted to the experimental data.The average relative errors between observed and predicted outlet concentrations of glycerol and propylene glycol were 6.3%and 7.6%,respectively.The kinetic and adsorption parameters were estimated by using the fourth-order Runge-Kutta method together with the Rosenbrock algorithm.The activation energies for dehydration and hydrogenation reactions were 86.56 and 57.80 kJ·mol-1,respectively.展开更多
基金support by the National Natural Science Foundation of China(21676300)~~
文摘To enhance sulfur adsorption and reactive activity, ordered mesoporous Cu-ZnO-Al2O3 adsorbents were prepared by a novel one-pot evaporation-induced self-assembly strategy using P123 as a structure-directing agent and ethanol as the solvent for reactive adsorption desulfurization. The metal oxide precursor molecules around P123 micellized, and self-assembly simultaneously occurred during evaporation from an ethanol solution at 60 °C, leading to the formation of the p6 mm hexagonal symmetry mesoporous structure. Characterization results prove that the Cu-ZnO-Al2O3 adsorbents possess an ordered mesoporous structure with high thermal stability, large surface area（386–226 m2/g）, large pore volume（0.60–0.46 cm3/g）, and good dispersion of ZnO and Cu, which is beneficial for transforming S-compounds to ZnO. The sulfur saturation capacity of the ordered-mesoporous-structure Cu-ZnO-Al2O3 adsorbents is larger（49.4 mg/g） than that of the unordered mesoporous structure（13.5 mg/g）.
基金Supported by the National＇High Technology Research and Development Program of China （2008AA05Z405）, the National Natural Science Foundation of China （20706018） and the Program for Changjiang Scholars and Innovative Research Team in University（IRT0721）.
文摘A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al molar ratio of 1:1:0.5 exhibited the best performance for glycerol hydrogenolysis,and thus selected for kinetic investigation.Under elimination of external and internal diffusion limitation,kinetic experiments were performed in an isothermal fixed-bed reactor at a hydrogen pressure range of 3.0-5.0 MPa and a temperature range of 493-513 K. Based on a dehydration-hydrogenation two-step hydrogenolysis mechanism,a two-site Langmuir-Hinshelwood kinetic model taking into account competitive adsorption of glycerol,acetol and propylene glycol was proposed and successfully fitted to the experimental data.The average relative errors between observed and predicted outlet concentrations of glycerol and propylene glycol were 6.3%and 7.6%,respectively.The kinetic and adsorption parameters were estimated by using the fourth-order Runge-Kutta method together with the Rosenbrock algorithm.The activation energies for dehydration and hydrogenation reactions were 86.56 and 57.80 kJ·mol-1,respectively.
