By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was as...By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.展开更多
The interface of slab track laid in cold regions is prone to debonding under the coupling of freeze-thaw cyclesand temperature loads.Based on the composite specimen tests,the parameters of cohesive zone model were obt...The interface of slab track laid in cold regions is prone to debonding under the coupling of freeze-thaw cyclesand temperature loads.Based on the composite specimen tests,the parameters of cohesive zone model were obtained andused in a simulation model of CRTS III prefabricated slab track to study the interlayer damage.The results show that 1)the digital image correlation(DIC)technique can accurately capture the strain field changes on the interface of compositespecimens under splitting and shear loading;2)when the temperature gradient is−40℃/m−60℃/m,the interfacedamage of the slab track is minimal and presents different patterns of expansion under positive and negative temperaturegradients,each corresponding to damage of the cohesive element dominated by shear stress and normal tensile stress,respectively;3)the reduction of the elastic modulus at the concrete base after freeze-thaw inhibits interface damage andleads to a higher starting temperature gradient load,but cracking can occur on the concrete base after 150 freeze-thaws.For this reason,in the light of damage control of both the interface and concrete base,the elastic modulus of the concretebase is 54%or over that without freeze-thaw cycles.展开更多
文摘By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.
基金Project(52425213)supported by the National Science Fund for Distinguished Young Scholars of ChinaProjects(52278461,52308467)supported by the National Natural Science Foundation of China+1 种基金Projects(2021YFF0502100,2021YFB2600900)supported by the National Key R&D Program of ChinaProject(2022JDTD0015)supported by the Sichuan Province Youth Science and Technology Innovation Team,China。
文摘The interface of slab track laid in cold regions is prone to debonding under the coupling of freeze-thaw cyclesand temperature loads.Based on the composite specimen tests,the parameters of cohesive zone model were obtained andused in a simulation model of CRTS III prefabricated slab track to study the interlayer damage.The results show that 1)the digital image correlation(DIC)technique can accurately capture the strain field changes on the interface of compositespecimens under splitting and shear loading;2)when the temperature gradient is−40℃/m−60℃/m,the interfacedamage of the slab track is minimal and presents different patterns of expansion under positive and negative temperaturegradients,each corresponding to damage of the cohesive element dominated by shear stress and normal tensile stress,respectively;3)the reduction of the elastic modulus at the concrete base after freeze-thaw inhibits interface damage andleads to a higher starting temperature gradient load,but cracking can occur on the concrete base after 150 freeze-thaws.For this reason,in the light of damage control of both the interface and concrete base,the elastic modulus of the concretebase is 54%or over that without freeze-thaw cycles.
