An ab initio investigation of hydrocarbon radical β-scission reaction kinetics

Xiaobo Zheng, Paul Blowers

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Hydrocarbon thermal cracking reactions are the key steps in petroleum refinery processes, and the mechanism is generally accepted to involve free-radical reactions. The MP2 ab initio method was applied to study β-scission reactions of propyl, butyl, and neopentyl radicals. The CBS-RAD(MP2) method was created as a modification of the CBS-RAD method. The method had the least root mean square error for heats of reaction and activation energy calculations for 15 hydrocarbon cracking reactions with less computational cost compared with the G2 and G3 methods. Work applying Transition State Theory and RRKM theory was done to estimate the reaction rate constants for hydrocarbon cracking reactions. The CBS-RAD(MP2) method had excellent agreement with the experimental data, indicating its reliability as a method for studying other large hydrocarbon cracking reactions. A reaction kinetic model with pressure and temperature effects was also proposed, which could be easily applied to different reaction conditions without performing additional expensive and complicated calculations. This is an abstract of a paper presented at the AIChE Annual Meeting and Fall Showcase (Cincinnati, OH 10/30/2005-11/4/2005).

Original languageEnglish (US)
Title of host publicationAIChE Annual Meeting Conference Proceedings
PublisherAmerican Institute of Chemical Engineers
Volume2005
ISBN (Print)0816909962, 9780816909964
StatePublished - 2005
Event05AIChE: 2005 AIChE Annual Meeting and Fall Showcase - Cincinnati, OH, United States
Duration: Oct 30 2005Nov 4 2005

Other

Other05AIChE: 2005 AIChE Annual Meeting and Fall Showcase
CountryUnited States
CityCincinnati, OH
Period10/30/0511/4/05

Fingerprint

Reaction kinetics
Hydrocarbons
Free radical reactions
Petroleum refineries
Pressure effects
Mean square error
Thermal effects
Reaction rates
Rate constants
Activation energy
Costs
Hot Temperature

ASJC Scopus subject areas

  • Energy(all)

Cite this

Zheng, X., & Blowers, P. (2005). An ab initio investigation of hydrocarbon radical β-scission reaction kinetics. In AIChE Annual Meeting Conference Proceedings (Vol. 2005). American Institute of Chemical Engineers.

An ab initio investigation of hydrocarbon radical β-scission reaction kinetics. / Zheng, Xiaobo; Blowers, Paul.

AIChE Annual Meeting Conference Proceedings. Vol. 2005 American Institute of Chemical Engineers, 2005.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Zheng, X & Blowers, P 2005, An ab initio investigation of hydrocarbon radical β-scission reaction kinetics. in AIChE Annual Meeting Conference Proceedings. vol. 2005, American Institute of Chemical Engineers, 05AIChE: 2005 AIChE Annual Meeting and Fall Showcase, Cincinnati, OH, United States, 10/30/05.
Zheng X, Blowers P. An ab initio investigation of hydrocarbon radical β-scission reaction kinetics. In AIChE Annual Meeting Conference Proceedings. Vol. 2005. American Institute of Chemical Engineers. 2005
Zheng, Xiaobo ; Blowers, Paul. / An ab initio investigation of hydrocarbon radical β-scission reaction kinetics. AIChE Annual Meeting Conference Proceedings. Vol. 2005 American Institute of Chemical Engineers, 2005.
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AB - Hydrocarbon thermal cracking reactions are the key steps in petroleum refinery processes, and the mechanism is generally accepted to involve free-radical reactions. The MP2 ab initio method was applied to study β-scission reactions of propyl, butyl, and neopentyl radicals. The CBS-RAD(MP2) method was created as a modification of the CBS-RAD method. The method had the least root mean square error for heats of reaction and activation energy calculations for 15 hydrocarbon cracking reactions with less computational cost compared with the G2 and G3 methods. Work applying Transition State Theory and RRKM theory was done to estimate the reaction rate constants for hydrocarbon cracking reactions. The CBS-RAD(MP2) method had excellent agreement with the experimental data, indicating its reliability as a method for studying other large hydrocarbon cracking reactions. A reaction kinetic model with pressure and temperature effects was also proposed, which could be easily applied to different reaction conditions without performing additional expensive and complicated calculations. This is an abstract of a paper presented at the AIChE Annual Meeting and Fall Showcase (Cincinnati, OH 10/30/2005-11/4/2005).

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