Thermal Decomposition of Substituted Phenols in Supercritical Water

Christopher J. Martino, Phillip E. Savage

Research output: Contribution to journalArticle

64 Citations (Scopus)

Abstract

The thermal decomposition of cresols, hydroxybenzaldehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions and in the absence of oxygen at 460°C and 250 atm for residence times around 10 s. Thermolysis under these conditions produced conversions of less than 10% for o-, m-, and p-cresol, whereas hydroxybenzaldehydes and nitrophenols were much more reactive. Global rate expressions are reported for the thermolysis of each hydroxybenzaldehyde and nitrophenol isomer. Phenol was a major product from the decomposition of all of the substituted phenols studied. For a given substituent, ortho-substituted phenols reacted more rapidly than the other isomers. For a given substituted position, nitrophenols reacted more rapidly than hydroxybenzaldehydes, which in turn reacted more rapidly than cresols. These results demonstrate that the treatment of CHO- and NO2-substituted phenols by oxidation in supercritical water will involve the oxidation of thermal decomposition products in addition to the oxidation of the original compounds.

Original languageEnglish (US)
Pages (from-to)1385-1390
Number of pages6
JournalIndustrial and Engineering Chemistry Research
Volume36
Issue number5
DOIs
StatePublished - Jan 1 1997

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Nitrophenols
Phenols
Cresols
Pyrolysis
Thermolysis
Water
Isomers
Oxidation
Phenol
Oxygen
Decomposition
4-cresol

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

Cite this

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abstract = "The thermal decomposition of cresols, hydroxybenzaldehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions and in the absence of oxygen at 460°C and 250 atm for residence times around 10 s. Thermolysis under these conditions produced conversions of less than 10{\%} for o-, m-, and p-cresol, whereas hydroxybenzaldehydes and nitrophenols were much more reactive. Global rate expressions are reported for the thermolysis of each hydroxybenzaldehyde and nitrophenol isomer. Phenol was a major product from the decomposition of all of the substituted phenols studied. For a given substituent, ortho-substituted phenols reacted more rapidly than the other isomers. For a given substituted position, nitrophenols reacted more rapidly than hydroxybenzaldehydes, which in turn reacted more rapidly than cresols. These results demonstrate that the treatment of CHO- and NO2-substituted phenols by oxidation in supercritical water will involve the oxidation of thermal decomposition products in addition to the oxidation of the original compounds.",
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Thermal Decomposition of Substituted Phenols in Supercritical Water. / Martino, Christopher J.; Savage, Phillip E.

In: Industrial and Engineering Chemistry Research, Vol. 36, No. 5, 01.01.1997, p. 1385-1390.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Thermal Decomposition of Substituted Phenols in Supercritical Water

AU - Martino, Christopher J.

AU - Savage, Phillip E.

PY - 1997/1/1

Y1 - 1997/1/1

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AB - The thermal decomposition of cresols, hydroxybenzaldehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions and in the absence of oxygen at 460°C and 250 atm for residence times around 10 s. Thermolysis under these conditions produced conversions of less than 10% for o-, m-, and p-cresol, whereas hydroxybenzaldehydes and nitrophenols were much more reactive. Global rate expressions are reported for the thermolysis of each hydroxybenzaldehyde and nitrophenol isomer. Phenol was a major product from the decomposition of all of the substituted phenols studied. For a given substituent, ortho-substituted phenols reacted more rapidly than the other isomers. For a given substituted position, nitrophenols reacted more rapidly than hydroxybenzaldehydes, which in turn reacted more rapidly than cresols. These results demonstrate that the treatment of CHO- and NO2-substituted phenols by oxidation in supercritical water will involve the oxidation of thermal decomposition products in addition to the oxidation of the original compounds.

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