Experimental Measurement of the Rate of Methyl tert-Butyl Ether Hydrolysis in Sub- and Supercritical Water

Experiments were conducted to measure the isothermal rate of methyl tert-butyl ether (MTBE) decomposition in water at hydrothermal conditions (T = 150−600 °C and P = 250 bar). The primary identified products of the reaction of MTBE were methanol, isobutene, and tert-butyl alcohol. An assumed first-o...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 2001-01, Vol.40 (1), p.67-74
Main Authors: Taylor, Joshua D, Steinfeld, Jeffrey I, Tester, Jefferson W
Format: Article
Language:English
Subjects:
Applied sciences
Chemistry
Exact sciences and technology
General purification processes
Kinetics and mechanisms
Organic chemistry
Pollution
Reactivity and mechanisms
Wastewaters
Water treatment and pollution
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Summary:Experiments were conducted to measure the isothermal rate of methyl tert-butyl ether (MTBE) decomposition in water at hydrothermal conditions (T = 150−600 °C and P = 250 bar). The primary identified products of the reaction of MTBE were methanol, isobutene, and tert-butyl alcohol. An assumed first-order rate constant for the hydrolysis of MTBE was determined at each temperature and showed a local maximum below the critical temperature of water (374 °C) followed by a local minimum above it. This behavior was modeled using an acid-catalyzed mechanism, which resulted in a rate expression with a first-order dependence on the concentration of H+. Because of the dramatic decrease in the ion dissociation constant of water (K w) in the critical region, the drop in the rate of reaction could be modeled quantitatively over the entire temperature range.
ISSN:0888-5885
1520-5045
DOI:10.1021/ie0006357