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
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
Chromium acetylacetonate and bis(diphenylphosphino)isopropylamine were coordinated in situ and supported on methylaluminoxane-modified silica. The catalyst structure and effects of reaction temperature, reaction press...Chromium acetylacetonate and bis(diphenylphosphino)isopropylamine were coordinated in situ and supported on methylaluminoxane-modified silica. The catalyst structure and effects of reaction temperature, reaction pressure and Al/Cr molar ratio on ethylene tetramerization were investigated in detail. Chromium was uniformly and firmly immobilized on the support and could not be leached off by methylaluminoxane. The supported catalyst, upon being activated with methylaluminoxane, exhibited catalytic activity of 1.70×107 g/(mol Cr·h) for ethylene tetramerization to form 1-octene at a reaction temperatures of 80 ℃, a pressure of 2.0 MPa and an Al/Cr molar ratio of 300. The supported catalyst presented a good tolerance to high temperature.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.
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%）.
基金supported by the National Natural Science Foundation of China (U1162114)the PetroChina Innovation Foundation (2012D-5006-0501)+2 种基金the Tianjin Municipal Education Commission of China (20110505)the Natural Science Foundation of Tianjin (12JCQNJC06000)the Program for New Century Excellent Talents in University (NCET-07-0142)
文摘Chromium acetylacetonate and bis(diphenylphosphino)isopropylamine were coordinated in situ and supported on methylaluminoxane-modified silica. The catalyst structure and effects of reaction temperature, reaction pressure and Al/Cr molar ratio on ethylene tetramerization were investigated in detail. Chromium was uniformly and firmly immobilized on the support and could not be leached off by methylaluminoxane. The supported catalyst, upon being activated with methylaluminoxane, exhibited catalytic activity of 1.70×107 g/(mol Cr·h) for ethylene tetramerization to form 1-octene at a reaction temperatures of 80 ℃, a pressure of 2.0 MPa and an Al/Cr molar ratio of 300. The supported catalyst presented a good tolerance to high temperature.
