Experimental Kinetics and Mechanistic Modeling of the Oxidation of Simple Mixtures in Near-Critical Water

The oxidation of organics in supercritical aqueous waste streams is an appealing waste treatment complement to the current technologies of incineration, land application, and deep-well injection. A novel kinetics lumping strategy is assessed through the confrontation of experimental kinetics for the...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 1994-11, Vol.33 (11), p.2554-2562
Main Authors: Boock, Lori Torry, Klein, Michael T
Format: Article
Language:English
Subjects:
540220 > Environment, Terrestrial-- Chemicals Monitoring & Transport-- (1990-)
ACETIC ACID
ALCOHOLS
CARBOXYLIC ACIDS
CHEMICAL ENGINEERING
CHEMICAL REACTIONS
DECOMPOSITION
ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
ENGINEERING
ENVIRONMENTAL SCIENCES
EQUATIONS
HYDROLYSIS
HYDROXY COMPOUNDS
KINETIC EQUATIONS
LYSIS
MATHEMATICAL MODELS
MONOCARBOXYLIC ACIDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC WASTES
OXIDATION
SOLVOLYSIS
SUPERCRITICAL STATE
WASTES 320305 > Energy Conservation, Consumption, & Utilization-- Industrial & Agricultural Processes-- Industrial Waste Management
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Summary:The oxidation of organics in supercritical aqueous waste streams is an appealing waste treatment complement to the current technologies of incineration, land application, and deep-well injection. A novel kinetics lumping strategy is assessed through the confrontation of experimental kinetics for the hydrothermal oxidation of mixtures of simple alcohols and acetic acid with the predictions of a mechanistic model. According to this lumping strategy, each of the elementary steps in the reaction model was lumped into one of eight reaction families. Each reaction family, in turn, was assigned an Arrhenius A factor, a Polanyi relation slope [alpha] = 0.5, and a Polanyi parameter E[sub 0]* determined via optimization to previous pure component experimental data only. Quantitative prediction of the kinetics of mixtures of these components was achieved by adjusting only the A factor for the H-abstraction reaction family to the value log[sub 10] A (L/mol[center dot]s) = 8.3, characteristic of H-abstraction for secondary alcohols. In short, the 167 rate constants of the mechanistic model were predicted by the eight reaction family parameter vectors such that an excellent correlation (r[sup 2] = 0.987) existed between experimental and predicted yields.
ISSN:0888-5885
1520-5045
DOI:10.1021/ie00035a005