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Title: Acetic acid oxidation and hydrolysis in supercritical water

Abstract

Acetic acid (CH{sub 3}COOH) hydrolysis and oxidation in supercritical water were examined from 425--600 C and 246 bar at reactor residence times of 4.4 to 9.8 s. Over the range of conditions studied, acetic acid oxidation was globally 0.72 {+-} 0.15 order in acetic acid and 0.27 {+-} 0.15 order in oxygen to a 95% confidence level, with an activation energy of 168 {+-} 21 kJ/mol, a preexponential factor of 10{sup 9.9{+-}1.7}, and an induction time of about 1.5 s at 525 C. Isothermal kinetic measurements at 550 C over the range 160 to 263 bar indicated that pressure or density did not affect the rate of acetic acid oxidation as much as was previously observed in the oxidation of hydrogen or carbon monoxide in supercritical water. Major products of acetic acid oxidation in supercritical water are carbon dioxide, carbon monoxide, methane, and hydrogen. Trace amounts of propenoic acid were occasionally detected. Hydrolysis or hydrothermolysis in the absence of oxygen resulted in approximately 35% conversion of acetic acid at 600 C, 246 bar, and 8-s reactor residence time. Regression of the limited hydrolysis runs assuming a reaction rate first-order in organic gave a global rate expression with a preexponential factormore » of 10{sup 4.4{+-}1.1} and an activation energy of 94 {+-} 17 kJ/mol.« less

Authors:
; ;  [1]
  1. Massachusetts Inst. of Tech., Cambridge, MA (United States)
Publication Date:
OSTI Identifier:
118818
Resource Type:
Journal Article
Journal Name:
AIChE Journal
Additional Journal Information:
Journal Volume: 41; Journal Issue: 9; Other Information: PBD: Sep 1995
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; ACETIC ACID; OXIDATION; HYDROLYSIS; HAZARDOUS MATERIALS; WASTE PROCESSING; WASTE WATER; AQUEOUS SOLUTIONS; SUPERCRITICAL STATE; CHEMICAL REACTION KINETICS; REGRESSION ANALYSIS; REACTION INTERMEDIATES; ORGANIC COMPOUNDS

Citation Formats

Meyer, J C, Marrone, P A, and Tester, J W. Acetic acid oxidation and hydrolysis in supercritical water. United States: N. p., 1995. Web. doi:10.1002/aic.690410910.
Meyer, J C, Marrone, P A, & Tester, J W. Acetic acid oxidation and hydrolysis in supercritical water. United States. https://doi.org/10.1002/aic.690410910
Meyer, J C, Marrone, P A, and Tester, J W. 1995. "Acetic acid oxidation and hydrolysis in supercritical water". United States. https://doi.org/10.1002/aic.690410910.
@article{osti_118818,
title = {Acetic acid oxidation and hydrolysis in supercritical water},
author = {Meyer, J C and Marrone, P A and Tester, J W},
abstractNote = {Acetic acid (CH{sub 3}COOH) hydrolysis and oxidation in supercritical water were examined from 425--600 C and 246 bar at reactor residence times of 4.4 to 9.8 s. Over the range of conditions studied, acetic acid oxidation was globally 0.72 {+-} 0.15 order in acetic acid and 0.27 {+-} 0.15 order in oxygen to a 95% confidence level, with an activation energy of 168 {+-} 21 kJ/mol, a preexponential factor of 10{sup 9.9{+-}1.7}, and an induction time of about 1.5 s at 525 C. Isothermal kinetic measurements at 550 C over the range 160 to 263 bar indicated that pressure or density did not affect the rate of acetic acid oxidation as much as was previously observed in the oxidation of hydrogen or carbon monoxide in supercritical water. Major products of acetic acid oxidation in supercritical water are carbon dioxide, carbon monoxide, methane, and hydrogen. Trace amounts of propenoic acid were occasionally detected. Hydrolysis or hydrothermolysis in the absence of oxygen resulted in approximately 35% conversion of acetic acid at 600 C, 246 bar, and 8-s reactor residence time. Regression of the limited hydrolysis runs assuming a reaction rate first-order in organic gave a global rate expression with a preexponential factor of 10{sup 4.4{+-}1.1} and an activation energy of 94 {+-} 17 kJ/mol.},
doi = {10.1002/aic.690410910},
url = {https://www.osti.gov/biblio/118818}, journal = {AIChE Journal},
number = 9,
volume = 41,
place = {United States},
year = {Fri Sep 01 00:00:00 EDT 1995},
month = {Fri Sep 01 00:00:00 EDT 1995}
}