Theoretical And Experimental Study On Anharmonic Effect Of High-temperature Pyrolysis Reaction In The Combustion Chamber

This paper mainly includes three aspects of research work, the first part is the study on anharmonic effect of the unimolecular reaction of CH2(D2)FO. The second part is the study on anharmonic effect of the unimolecular reaction of C2H2O2. The last part is the comparative study with dual-pressure pyrolysis experiments and supercritical pyrolysisIn the first part, study on the unimolecular reaction for CH2FO and CD2FO is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6-311++G(3df,3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of500-5000K and microcanonical system at total energy of19.05-71.68kcal/mol. The results indicate that the anharmonic effect and isotope effect are very small for the three channels, and the anharmonic rate constants, around109-1011s-1, are close to the experimental prediction reasonably.In the second part, study on the unimolecular reaction for C2H2O2is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6-311++G(3df,3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of500-4000K and microcanonical system at total energy of58.73-74.7kcal/mol. The results indicate that the anharmonic effect is very small for the three channels, and the anharmonic rate constants are close to the experimental prediction reasonably.In the last part of the work, we experimentally thermal physical characteristics of hydrocarbon fuels under supercritical conditions and dual-pressure pyrolysis, which were compared to obtain the advantages of dual-pressure pyrolysis. In the beginning of the phase transition at supercritical pressures, the density of the fuel, etc. to ensure that the phase transition, gasification after the completion of kerosene through throttling, so kerosene steam cracker at higher temperatures, the cleavage reaction at lower pressure carried out, can be achieved to improve the gas production rate and cracking chemical heat sink to reduce cracking coking purposes. Then we studied heat transfer area of tube wall temperatures, which can be specific guidance in future experiments.