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Phenol oxidation in supercritical water in a well-stirred continuous reactor

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Abstract

A well-stirred reactor for phenol and acetic acid oxidation in supercritical water is considered. A mathematical model of an adiabatic reactor is formulated. A numerical algorithm for solving the model equations using the homotopy method is developed. The model takes into account specific features of processes under supercritical conditions, namely, the changes in the thermodynamic properties (enthalpy, heat capacity, and critical parameters) of mixtures with a change in pressure and temperature. The thermodynamic properties are calculated by methods of nonideal thermodynamics. It is shown that there is a multiplicity of steady-state solutions at various reactor performances. The results of numerical analysis of the effect of the inlet flow temperature, the amount of methanol (fuel) fed, and the total pressure on the reactor performance are presented.

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Abbreviations

C i :

concentration of the ith component, g-mol/l

c p :

specific heat of the mixture, J/(mol K)

Fi :

function defined by Eq. (7)

\(\bar H_i \) :

partial molar enthalpy of the ith component, J/mol

H m :

enthalpy of the mixture, J/mol

N:

total molar flow rate, g-mol/s

N r :

number of chemical reactions

N s :

number of the components of the reaction mixture

n i :

molar flow rate of the ith component, g-mol/s

P:

pressure, MPa

Q heat :

heat flow rate required for heating the initial mixture from the temperature T 0 to the temperature T ad, J/s

Q react :

heat flow rate produced in the exothermic reaction, J/s

q i :

rate of formation or consumption of the ith component, g-mol/(l s)

R:

rate of acetic acid oxidation by reaction (2), g-mol/(l s)

R 1 :

rate of phenol oxidation by reaction (1), g-mol/(l s)

R 2 :

rate of phenol oxidation by reaction (3), g-mol/(l s)

T:

temperature, K

V m :

molar volume of the mixture, l/mol

V R :

reactor volume, 1

y:

vector of mole fractions of components of dimension N s

y i :

mole fraction of the ith component

γ:

coefficient of change in the molar flow rate in the reactor

ΔT ad :

temperature difference due to adiabatic heating of the reaction mixture

τ:

conditional contact time, (l s)/g-mol

Ac:

acetic acid

ad:

adiabatic

cr:

critical

Me:

methanol

m:

mixture

out:

reactor outlet

Ph:

phenol

0:

reactor inlet

References

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, pr. akademika Lavrent’eva 5, Novosibirsk, 630090, Russia

    A. Yermakova, P. E. Mikenin & V. I. Anikeev

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  1. A. Yermakova
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  2. P. E. Mikenin
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  3. V. I. Anikeev
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Original Russian Text © A. Yermakova, P.E. Mikenin, V.I. Anikeev, 2006, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2006, Vol. 40, No. 2, pp. 184–190.

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Yermakova, A., Mikenin, P.E. & Anikeev, V.I. Phenol oxidation in supercritical water in a well-stirred continuous reactor. Theor Found Chem Eng 40, 168–174 (2006). https://doi.org/10.1134/S0040579506020096

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  • DOI: https://doi.org/10.1134/S0040579506020096

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