The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthes...The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.展开更多
Wustite-based catalyst for ammonia synthesis exhibits extremely high activity and easy to reduction under a wide range of conditions. The reaction kinetics of ammonia synthesis can be illustrated perfectly by both the...Wustite-based catalyst for ammonia synthesis exhibits extremely high activity and easy to reduction under a wide range of conditions. The reaction kinetics of ammonia synthesis can be illustrated perfectly by both the classical Temkin-Pyzhev and modified Temkin equations with optimized a of 0.5. The pre-exponent factors and activation energies at the pressures of 8.0 and 15.0MPa are respectively k0 = 1.09 x 1015, 7.35 X 1014Pa0.5.s-1, and E = 156.6, 155.5kJ-mol-1 derived from the classical Temkin-Phyzhev equation, as well as k0 = 2.45 X 1014, 1.83 X 1014Pa0.5s-1, and E = 147.7, 147.2kJ-mol-1 derived from the modified Temkin equation. Although the degree of reduction under isothermal condition is primarily dependent upon temperature, low pressure seems to be imperative for reduction under high temperature and low space velocity to be considered as a high activity catalyst. The reduction behavior with dry feed gas can be illustrated perfectly by the shrinking-sphere-particle model, by which the reduction-rate constants of 4248exp (-71680/KT) and 644exp (-87260/RT) were obtained for the powder (0.045-0.054mm) and irregular shape (nominal diameter 3.17 mm) catalysts respectively. The significant effect of particle size on reduction rate was observed, therefore, it is important to take into account the influence of particle size on reduction for the optimization of reduction process in industry.展开更多
基金Supported by the Natural Science Foundation of Zhejiang Province (No. 299015), the Development Plan of Youth Mainstay Teacher of the Education Ministry of China and the Special Foundation for Youth Talent by Zhejiang (RC9702).
文摘The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.
基金Supported by the National Natural Science Foundation of China (No. 29706011), the Natural Science Foundation of Zhejiang Province for the distinguished young scholars (No. RC9702) and the Ninth-five Key Project of China (No. 96-550-02-01).
文摘Wustite-based catalyst for ammonia synthesis exhibits extremely high activity and easy to reduction under a wide range of conditions. The reaction kinetics of ammonia synthesis can be illustrated perfectly by both the classical Temkin-Pyzhev and modified Temkin equations with optimized a of 0.5. The pre-exponent factors and activation energies at the pressures of 8.0 and 15.0MPa are respectively k0 = 1.09 x 1015, 7.35 X 1014Pa0.5.s-1, and E = 156.6, 155.5kJ-mol-1 derived from the classical Temkin-Phyzhev equation, as well as k0 = 2.45 X 1014, 1.83 X 1014Pa0.5s-1, and E = 147.7, 147.2kJ-mol-1 derived from the modified Temkin equation. Although the degree of reduction under isothermal condition is primarily dependent upon temperature, low pressure seems to be imperative for reduction under high temperature and low space velocity to be considered as a high activity catalyst. The reduction behavior with dry feed gas can be illustrated perfectly by the shrinking-sphere-particle model, by which the reduction-rate constants of 4248exp (-71680/KT) and 644exp (-87260/RT) were obtained for the powder (0.045-0.054mm) and irregular shape (nominal diameter 3.17 mm) catalysts respectively. The significant effect of particle size on reduction rate was observed, therefore, it is important to take into account the influence of particle size on reduction for the optimization of reduction process in industry.
