Date of Award

Fall 1995

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemical Engineering - (Ph.D.)

Department

Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Robert Benedict Barat

Third Advisor

Dana E. Knox

Fourth Advisor

Lev N. Krasnoperov

Fifth Advisor

Michael R. Booty

Abstract

This study presents experimental data on the decomposition of methanol in several different reaction environments - fuel lean to stoichiometric at a temperature range of 873 and 1073 K and a pressure range of I and 5 atm. Methane fuel is also added in several of the systems studied in order to provide experimental data to understand the methanol addition effect on the methane oxidation.

Computer codes: ThermCal, ThermSrt and ThermCvt have been developed for the thermal property calculations of stable molecules by the Benson group additivity method and of radicals by the NJIT hydrogen bond increment method.

Pressure dependent rate coefficients have been expressed using Chebyshev polynomials adopted for complex chemical activated reaction systems in this study, as well as unimolecular decomposition reactions. This method has also been tested and shows significant improvement over two convention methods, Troe's and SRI. The Levenberg-Marquardt algorithm has been incorporated with the QRRK code, CHEMACT, for the fitting of Chebyshev polynomials.

A pressure dependent mechanism which consists 147 species and 448 elementary reactions, based on thermochemical kinetic principals has been developed and calibrated by the experimental data. The reaction mechanisms (models) include pathways for formation of higher molecular weight products, such as the formation of methyl ethers. This accurate model based on principles of thermochemical kinetics and statistical mechanics will not only provide fundamental understanding, but can be used to suggest directions toward process optimization for experimental testing.

A pressure dependent mechanism which consists 147 species and 448 elementary reactions, based on thermochemical kinetic principals has been developed and calibrated by the experimental data. The reaction mechanisms (models) include pathways for formation of higher molecular weight products, such as the formation of methyl ethers. This accurate model based on principles of thermochemical kinetics and statistical mechanics will not only provide fundamental understanding, but can be used to suggest directions toward process optimization for experimental testing.

The mechanism is validated with methanol oxidation and pyrolysis experimental data and serves as a basis to build upon during the subsequent efforts on higher molecular weight oxygenated hydrocarbon (MTBE in this study). The methanol addition shows dramatic acceleration effect on the methane oxidation experimentally and predicted by the model.

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