The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinet...The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinetic data were obtained under the following conditions： 490-530 °C, space velocity of 3600？6000 mL·h-1·g-1 and 3/1 molar ratio for CO2/C3H8 under normal pressure. Based on Langmuir-Hinshelwood mechanism, the kinetic models were established, and they were validated by statistical analysis. The parameters were estimated using Simplex Method combined with Universal Global Optimization Algorithm. The model, taking the surface reaction process as the rate-determining step, is the best one in agreement with the experimental data.展开更多
Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TP...Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.展开更多
Two novel diphoshinoamine ligands have been synthesized. Combination of Cr（Ⅲ） and methylaluminoxane（MAO） generated active catalytic system which can catalyze tetramerization of ethylene with high catalytic activi...Two novel diphoshinoamine ligands have been synthesized. Combination of Cr（Ⅲ） and methylaluminoxane（MAO） generated active catalytic system which can catalyze tetramerization of ethylene with high catalytic activity up to 2.5×10^6 g/mol Cr.h and high selectivity to produce 1-octene （Cs in products is being 89.80 wt%）.展开更多
A series of catalysts were prepared using the kneading molding method and the impregnation method as well as the dry mix method by using different raw materials. By using X-ray diffraction (XRD), X-ray photoelectron s...A series of catalysts were prepared using the kneading molding method and the impregnation method as well as the dry mix method by using different raw materials. By using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR) techniques, we studied the relationship between the catalyst performance and the Cr-Al interaction in the catalytic dehydrogenation of isobutane. The results demonstrated that the Cr-Al interaction in the catalyst had a direct influence on the catalytic activity and the selectivity of isobutene. The catalysts prepared using the kneading molding method had higher catalytic activity and isobutene selectivity than those prepared using the dry mix method. By comparison, XRD, XPS, and TPR results showed that the greater the Cr-Al interaction in the catalyst was, the higher the catalytic activity was. Here, we propose a mechanism of isobutane dehydrogenation.展开更多
A novel powder catalyst Cu-Cr-O applied to the synthesis of carbon nanotubes （CNTs） was developed, which was prepared via ammonia precipitation method. Techniques of thermo-gravimetric/ differential scanning calorim...A novel powder catalyst Cu-Cr-O applied to the synthesis of carbon nanotubes （CNTs） was developed, which was prepared via ammonia precipitation method. Techniques of thermo-gravimetric/ differential scanning calorimeter （TG-DSC）, X-ray diffraction （XRD） as well as scanning electron microscopy （SEM） and transmission electron microscopy （TEM） have been employed to characterize the thermal decomposition procedure, crystal phase and micro structural morphologies of the as-synthesized materials, respectively. The results show that carbon nanotubes are successfully synthesized using Cu-Cr-O as catalyst when the precursors are calcined at 400, 500, 600, and 700 ℃. The results indicate that the calcination of the Cu-Cr-O catalyst at 600 ℃ is an effective method to get MWCNT with few nano-tube defects or amorphous carbons.展开更多
The Cu/Cr base catalysts were prepared by impregnation. XRD and TPR technology were applied to characterize the catalysts. The result showed that the Cu/Cr base catalysts performed much better than the conventional Cu...The Cu/Cr base catalysts were prepared by impregnation. XRD and TPR technology were applied to characterize the catalysts. The result showed that the Cu/Cr base catalysts performed much better than the conventional Cu/Zn/Al catalysts. The stability of the catalysts was enhanced by promoters such as K, Mg, Ni, Y. But the promoters reduced the initial activity of the catalysts. The promoters except Y improved the selectivity apparently.展开更多
The dehydrogenation reaction of ethane over Cr/CeO2 catalysts in presence of CO2 was studied with fixed-bed micro-reactor. The Cr/CeO2 catalysts of different Cr loading have been synthesized using impregnation techniq...The dehydrogenation reaction of ethane over Cr/CeO2 catalysts in presence of CO2 was studied with fixed-bed micro-reactor. The Cr/CeO2 catalysts of different Cr loading have been synthesized using impregnation techniques. The Cr/CeO2 system has already been found to be active and selective in the reaction at around 740 ℃. The function of carbon dioxide is to remove coke and hydrogen to accelerate dehydrogenation of ethane. The results of catalysts characterizations indicated that Cr3+ and Cr6+ occurred on the surface of the catalysts. The 1.2 mmol Cr/100m2 CeO2 catalyst sample with a monolayer dispersion of Cr on CeO2 support showed a stronger surface acidity and a maximum yield of ethylene of about 35.5% at 36.6% conversion of ethane.展开更多
采用固定床反应器,研究了Cu Cr Ca Ba催化剂上糠醛常压选择加氢制2 甲基呋喃的反应.详细考察了反应条件对催化性能的影响.结果表明,添加Ca Ba助剂显著提高了催化剂对目的产物的选择性,Cu Cr Ca Ba催化剂在200～220℃,液时空速0.2～0.6h...采用固定床反应器,研究了Cu Cr Ca Ba催化剂上糠醛常压选择加氢制2 甲基呋喃的反应.详细考察了反应条件对催化性能的影响.结果表明,添加Ca Ba助剂显著提高了催化剂对目的产物的选择性,Cu Cr Ca Ba催化剂在200～220℃,液时空速0.2～0.6h-1,氢醛摩尔比6～16的条件下,具有良好的活性和选择性,糠醛转化率 99.8%,2 甲基呋喃选择性 90.3%.展开更多
基金supported by the National Natural Science Foundation of China (No. 21006109)the Postdoctoral Science Foundation of China (No. 20080430581)the CASKC Wang Post-Doctoral Fellowship
文摘The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinetic data were obtained under the following conditions： 490-530 °C, space velocity of 3600？6000 mL·h-1·g-1 and 3/1 molar ratio for CO2/C3H8 under normal pressure. Based on Langmuir-Hinshelwood mechanism, the kinetic models were established, and they were validated by statistical analysis. The parameters were estimated using Simplex Method combined with Universal Global Optimization Algorithm. The model, taking the surface reaction process as the rate-determining step, is the best one in agreement with the experimental data.
基金supported by the Natural Science Foundation of Shandong Provence of China(ZR2013BM008)
文摘Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.
文摘Two novel diphoshinoamine ligands have been synthesized. Combination of Cr（Ⅲ） and methylaluminoxane（MAO） generated active catalytic system which can catalyze tetramerization of ethylene with high catalytic activity up to 2.5×10^6 g/mol Cr.h and high selectivity to produce 1-octene （Cs in products is being 89.80 wt%）.
文摘A series of catalysts were prepared using the kneading molding method and the impregnation method as well as the dry mix method by using different raw materials. By using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR) techniques, we studied the relationship between the catalyst performance and the Cr-Al interaction in the catalytic dehydrogenation of isobutane. The results demonstrated that the Cr-Al interaction in the catalyst had a direct influence on the catalytic activity and the selectivity of isobutene. The catalysts prepared using the kneading molding method had higher catalytic activity and isobutene selectivity than those prepared using the dry mix method. By comparison, XRD, XPS, and TPR results showed that the greater the Cr-Al interaction in the catalyst was, the higher the catalytic activity was. Here, we propose a mechanism of isobutane dehydrogenation.
基金Supported by National Natural Science Foundation of China(No.51201107)Key Basic Research Project of Shanghai Committee of Science and Technology in China(10JC1411800)
文摘A novel powder catalyst Cu-Cr-O applied to the synthesis of carbon nanotubes （CNTs） was developed, which was prepared via ammonia precipitation method. Techniques of thermo-gravimetric/ differential scanning calorimeter （TG-DSC）, X-ray diffraction （XRD） as well as scanning electron microscopy （SEM） and transmission electron microscopy （TEM） have been employed to characterize the thermal decomposition procedure, crystal phase and micro structural morphologies of the as-synthesized materials, respectively. The results show that carbon nanotubes are successfully synthesized using Cu-Cr-O as catalyst when the precursors are calcined at 400, 500, 600, and 700 ℃. The results indicate that the calcination of the Cu-Cr-O catalyst at 600 ℃ is an effective method to get MWCNT with few nano-tube defects or amorphous carbons.
文摘The Cu/Cr base catalysts were prepared by impregnation. XRD and TPR technology were applied to characterize the catalysts. The result showed that the Cu/Cr base catalysts performed much better than the conventional Cu/Zn/Al catalysts. The stability of the catalysts was enhanced by promoters such as K, Mg, Ni, Y. But the promoters reduced the initial activity of the catalysts. The promoters except Y improved the selectivity apparently.
文摘The dehydrogenation reaction of ethane over Cr/CeO2 catalysts in presence of CO2 was studied with fixed-bed micro-reactor. The Cr/CeO2 catalysts of different Cr loading have been synthesized using impregnation techniques. The Cr/CeO2 system has already been found to be active and selective in the reaction at around 740 ℃. The function of carbon dioxide is to remove coke and hydrogen to accelerate dehydrogenation of ethane. The results of catalysts characterizations indicated that Cr3+ and Cr6+ occurred on the surface of the catalysts. The 1.2 mmol Cr/100m2 CeO2 catalyst sample with a monolayer dispersion of Cr on CeO2 support showed a stronger surface acidity and a maximum yield of ethylene of about 35.5% at 36.6% conversion of ethane.
