By calcinating commercial silica gel at 1500℃or adding Na2C2O4 and then calcinating at 850℃,α cristobalite was formed.On the basis of the vibration spectroscopy of silica support,Na W Mn/SiO2 catalyst was character...By calcinating commercial silica gel at 1500℃or adding Na2C2O4 and then calcinating at 850℃,α cristobalite was formed.On the basis of the vibration spectroscopy of silica support,Na W Mn/SiO2 catalyst was characterized by Raman spectroscopy.The results show that the structure of support and the interaction among metal components have significant effect on the dispersion and the structure of metal sites,and the tetrahedrally coordinated formed on α cristobalite surface is the most possible site of methane activation with high C2 selectivity.展开更多
The effects of operating parameters on oxidative coupling of methane （OCM） over Na-W-Mn/SiO2 catalyst have been studied at elevated pressures of 0.2, 0.3 and 0.4 MPa under low gaseous hourly space velocity （GHSV） ...The effects of operating parameters on oxidative coupling of methane （OCM） over Na-W-Mn/SiO2 catalyst have been studied at elevated pressures of 0.2, 0.3 and 0.4 MPa under low gaseous hourly space velocity （GHSV） and low temperature conditions. Experimental results show that when the operating pressure is increased, C2＋ yield slightly decreases, while the maximum ratio of ethylene to ethane remains unchanged. Moreover, it has been found empirically that increase of pressure does not affect the catalyst behavior permanently, the catalyst recovers its original low pressure performance without hysteresis behavior by reducing the pressure. Under the investigated conditions, when oxygen is completely consumed, the increase of GHSV leads to improvement in C2 selectivity, while C3＋ and COx selectivities decrease slightly. The C2＋ selectivity increases by increase of nitrogen diluent in the feed, but the C3＋ hydrocarbons selectivities decrease with increase of nitrogen since it is possible that further dilution at high pressure may reduce the probability of collision between CH3 and C2＋ hydrocarbons. During the stability test at high pressure, the catalyst performance remains unchanged throughout the 20 h running. The fresh and used catalysts were characterized using XRD, SEM and N2 adsorption-desorption methods. It was found that the phase transformation of the support from α-cristobalite to tridymite and quartz does not have obvious effect on catalyst performance at high pressure.展开更多
A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on t...A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. From the characterization results, it is found that the addition of S and P to the Na-W-Mn-ZffSiO2 catalyst helps the formation of active phases, such as α-cristobalite, Na2WO4, ZrO2, and Na2SO4. Moreover, the addition of S and P increases the concentration of surface-active oxygen species by improving the migration of active components from the bulk phase to the surface of the catalyst. According to the activity test, impressive methane conversion and C2 hydrocarbons yield were obtained at a low temperature of 1023 K over the six-component Na-W-Mn-Zr-S-P/SiO2 catalyst, which contained 2 wt% S and 0.4 wt% P simultaneously. The deactivation of Na-W-Mn-Zr-S-P/SiO2 was due to the loss of surface active components.展开更多
Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane （OCM） were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the be...Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane （OCM） were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.展开更多
The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction ...The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.展开更多
A series of Mn-Mo-W-O_x/TiO_2-SiO_2 catalysts was modified with CeO_2 using an extrusion molding method. The catalytic activities of the obtained catalysts were tested for the synergistic catalytic removals of CO, NO ...A series of Mn-Mo-W-O_x/TiO_2-SiO_2 catalysts was modified with CeO_2 using an extrusion molding method. The catalytic activities of the obtained catalysts were tested for the synergistic catalytic removals of CO, NO and C_3H_8. The ratio of catalyst composition on catalytic activities for NH_3-SCR was optimized, which reveals that the molar ratio of Ti/Si was 9：1 and the catalyst containing 1.5 wt% CeO_2 and 12 wt% Mn-Mo-W-O_x exhibits the best catalytic performances. These samples were characterized by XRD, N_2-BET, Py-IR, NH_3-TPD, SEM/element mapping, H_2-TPR and XPS, respectively. Results show that the optimal catalyst exhibits more than 99% NO conversion, 86% CO conversion and 100% C_3H_8 conversion under GHSV of 5000 h^（-1）. In addition, the GHSV has little influence on removal of NO when it is less than 15,000 h^（-1）. Furthermore, the addition of CeO_2 will enhance the surface acidity, increase Mn^（4＋）concentration and inhibit the grain growth, which are favorable for the excellent catalytic performance.Anyway,the 1.5 wt% CeO_2-12 wt% Mn-Mo-W-O_x/TiO_2-SiO_2 possesses outstanding redox properties,abundant acid sites and high Mn^（4＋） concentration, which provide a guarantee for synergistic catalytic removal of CO, NO and HC.展开更多
文摘By calcinating commercial silica gel at 1500℃or adding Na2C2O4 and then calcinating at 850℃,α cristobalite was formed.On the basis of the vibration spectroscopy of silica support,Na W Mn/SiO2 catalyst was characterized by Raman spectroscopy.The results show that the structure of support and the interaction among metal components have significant effect on the dispersion and the structure of metal sites,and the tetrahedrally coordinated formed on α cristobalite surface is the most possible site of methane activation with high C2 selectivity.
文摘The effects of operating parameters on oxidative coupling of methane （OCM） over Na-W-Mn/SiO2 catalyst have been studied at elevated pressures of 0.2, 0.3 and 0.4 MPa under low gaseous hourly space velocity （GHSV） and low temperature conditions. Experimental results show that when the operating pressure is increased, C2＋ yield slightly decreases, while the maximum ratio of ethylene to ethane remains unchanged. Moreover, it has been found empirically that increase of pressure does not affect the catalyst behavior permanently, the catalyst recovers its original low pressure performance without hysteresis behavior by reducing the pressure. Under the investigated conditions, when oxygen is completely consumed, the increase of GHSV leads to improvement in C2 selectivity, while C3＋ and COx selectivities decrease slightly. The C2＋ selectivity increases by increase of nitrogen diluent in the feed, but the C3＋ hydrocarbons selectivities decrease with increase of nitrogen since it is possible that further dilution at high pressure may reduce the probability of collision between CH3 and C2＋ hydrocarbons. During the stability test at high pressure, the catalyst performance remains unchanged throughout the 20 h running. The fresh and used catalysts were characterized using XRD, SEM and N2 adsorption-desorption methods. It was found that the phase transformation of the support from α-cristobalite to tridymite and quartz does not have obvious effect on catalyst performance at high pressure.
基金supported by the National Natural Science Foundation of China (20676116)
文摘A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. From the characterization results, it is found that the addition of S and P to the Na-W-Mn-ZffSiO2 catalyst helps the formation of active phases, such as α-cristobalite, Na2WO4, ZrO2, and Na2SO4. Moreover, the addition of S and P increases the concentration of surface-active oxygen species by improving the migration of active components from the bulk phase to the surface of the catalyst. According to the activity test, impressive methane conversion and C2 hydrocarbons yield were obtained at a low temperature of 1023 K over the six-component Na-W-Mn-Zr-S-P/SiO2 catalyst, which contained 2 wt% S and 0.4 wt% P simultaneously. The deactivation of Na-W-Mn-Zr-S-P/SiO2 was due to the loss of surface active components.
基金supported by the financial support from National Natural Science Foundation of China (20676116)
文摘Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane （OCM） were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.
文摘The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.
基金Project supported by the National Key Research and Development Program of China(2016YFC0205500)National Natural Science Foundation of China(51772149)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘A series of Mn-Mo-W-O_x/TiO_2-SiO_2 catalysts was modified with CeO_2 using an extrusion molding method. The catalytic activities of the obtained catalysts were tested for the synergistic catalytic removals of CO, NO and C_3H_8. The ratio of catalyst composition on catalytic activities for NH_3-SCR was optimized, which reveals that the molar ratio of Ti/Si was 9：1 and the catalyst containing 1.5 wt% CeO_2 and 12 wt% Mn-Mo-W-O_x exhibits the best catalytic performances. These samples were characterized by XRD, N_2-BET, Py-IR, NH_3-TPD, SEM/element mapping, H_2-TPR and XPS, respectively. Results show that the optimal catalyst exhibits more than 99% NO conversion, 86% CO conversion and 100% C_3H_8 conversion under GHSV of 5000 h^（-1）. In addition, the GHSV has little influence on removal of NO when it is less than 15,000 h^（-1）. Furthermore, the addition of CeO_2 will enhance the surface acidity, increase Mn^（4＋）concentration and inhibit the grain growth, which are favorable for the excellent catalytic performance.Anyway,the 1.5 wt% CeO_2-12 wt% Mn-Mo-W-O_x/TiO_2-SiO_2 possesses outstanding redox properties,abundant acid sites and high Mn^（4＋） concentration, which provide a guarantee for synergistic catalytic removal of CO, NO and HC.
