A reaction network model for phenol oxidation in supercritical water

Journal Article · Tue Aug 01 04:00:00 EDT 1995 · AIChE Journal

DOI:https://doi.org/10.1002/aic.690410805· OSTI ID:106218

Gopalan, S; Savage, P E ^[1]

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1. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

Dilute aqueous solutions of phenol were oxidized in a flow reactor at 420, 440, 460 and 480 C at 250 atm. Phenol disappearance kinetics followed the trends exhibited by previously published data obtained at T < 420 C. By merging the two sets of data, a global rate law for phenol disappearance kinetics valid between 380 and 480 C was determined to be rate = 10{sup 2.34} exp({minus}12.4/RT)[{phi}OH]{sup 0.85}[O{sub 2}]{sup 0.50}[H{sub 2}O]{sup 0.42}. Undesired multiring products, whose formation was reported previously at the lower temperatures, continued to form in high selectivities at these higher temperatures. Reaction products were classified into three categories: dimers, gases, and a remainder that included products from ring-opening reactions. A global reaction network that describes the transformation of phenol into these product groups was developed. Steps in the network are: parallel oxidation paths for phenol that form dimers and ring-opening and other products, secondary decomposition of dimers to ring-opening and other products, and oxidation of the ring0opening and other products to carbon oxides. The experimental product yields were used to determine optimal values for the reaction orders and rate constants for each step in the network. This quantitative reaction model shows that dimerization is the dominant primary path for phenol consumption. High temperatures and long residence times reduce the concentration of dimers in the reactor effluent and maximize the gas yield. High oxygen concentrations also increase the gas yield. The quantitative reaction network model is consistent with previously published product yields for T = 380--420 C.

• DOE Contract Number: FG22-92PC92536
• OSTI ID: 106218
• Journal Information: AIChE Journal, Journal Name: AIChE Journal Journal Issue: 8 Vol. 41; ISSN AICEAC; ISSN 0001-1541
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
54 ENVIRONMENTAL SCIENCES
BY-PRODUCTS
CARBON DIOXIDE
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
DIMERIZATION
MATHEMATICAL MODELS
OXIDATION
PHENOL
REACTION INTERMEDIATES
SUPERCRITICAL STATE
WASTE WATER
WATER TREATMENT
WATER VAPOR