Intermediates and kinetics for phenol gasification in supercritical water

Chad M. Huelsman, Phillip E. Savage

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

We processed phenol with supercritical water in a series of experiments, which systematically varied the temperature, water density, reactant concentration, and reaction time. Both the gas and liquid phases were analyzed post-reaction using gas chromatographic techniques, which identified and quantified the reaction intermediates and products, including H 2, CO, CH 4, and CO 2 in the gas phase and twenty different compounds - mainly polycyclic aromatic hydrocarbons - in the liquid phase. Many of these liquid phase compounds were identified for the first time and could pose environmental risks. Higher temperatures promoted gasification and resulted in a product gas rich in H 2 and CH 4 (33% and 29%, respectively, at 700°C), but char yields increased as well. We implicated dibenzofuran and other identified phenolic dimers as precursor molecules for char formation pathways, which can be driven by free radical polymerization at high temperatures. Examination of the trends in conversion as a function of initial water and phenol concentrations revealed competing effects, and these informed the kinetic modeling of phenol disappearance. Two different reaction pathways emerged from the kinetic modeling: one in which rate ∝ [phenol] 1.73[water] -16.60 and the other in which rate ∝ [phenol] 0.92[water] 1.39. These pathways may correspond to pyrolysis, which dominates when there is abundant phenol and little water, and hydrothermal reactions, which dominate in excess water. This result confirms that supercritical water gasification of phenol does not simply follow first-order kinetics, as previous efforts to model phenol disappearance had assumed.

Original languageEnglish (US)
Pages (from-to)2900-2910
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number8
DOIs
StatePublished - Feb 28 2012

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gasification
Phenol
Gasification
phenols
Kinetics
Water
kinetics
water
Gases
liquid phases
Carbon Monoxide
Liquids
methylidyne
vapor phases
Reaction intermediates
reaction intermediates
water temperature
Polycyclic Aromatic Hydrocarbons
polycyclic aromatic hydrocarbons
Free radical polymerization

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Intermediates and kinetics for phenol gasification in supercritical water",
abstract = "We processed phenol with supercritical water in a series of experiments, which systematically varied the temperature, water density, reactant concentration, and reaction time. Both the gas and liquid phases were analyzed post-reaction using gas chromatographic techniques, which identified and quantified the reaction intermediates and products, including H 2, CO, CH 4, and CO 2 in the gas phase and twenty different compounds - mainly polycyclic aromatic hydrocarbons - in the liquid phase. Many of these liquid phase compounds were identified for the first time and could pose environmental risks. Higher temperatures promoted gasification and resulted in a product gas rich in H 2 and CH 4 (33{\%} and 29{\%}, respectively, at 700°C), but char yields increased as well. We implicated dibenzofuran and other identified phenolic dimers as precursor molecules for char formation pathways, which can be driven by free radical polymerization at high temperatures. Examination of the trends in conversion as a function of initial water and phenol concentrations revealed competing effects, and these informed the kinetic modeling of phenol disappearance. Two different reaction pathways emerged from the kinetic modeling: one in which rate ∝ [phenol] 1.73[water] -16.60 and the other in which rate ∝ [phenol] 0.92[water] 1.39. These pathways may correspond to pyrolysis, which dominates when there is abundant phenol and little water, and hydrothermal reactions, which dominate in excess water. This result confirms that supercritical water gasification of phenol does not simply follow first-order kinetics, as previous efforts to model phenol disappearance had assumed.",
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Intermediates and kinetics for phenol gasification in supercritical water. / Huelsman, Chad M.; Savage, Phillip E.

In: Physical Chemistry Chemical Physics, Vol. 14, No. 8, 28.02.2012, p. 2900-2910.

Research output: Contribution to journalArticle

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AB - We processed phenol with supercritical water in a series of experiments, which systematically varied the temperature, water density, reactant concentration, and reaction time. Both the gas and liquid phases were analyzed post-reaction using gas chromatographic techniques, which identified and quantified the reaction intermediates and products, including H 2, CO, CH 4, and CO 2 in the gas phase and twenty different compounds - mainly polycyclic aromatic hydrocarbons - in the liquid phase. Many of these liquid phase compounds were identified for the first time and could pose environmental risks. Higher temperatures promoted gasification and resulted in a product gas rich in H 2 and CH 4 (33% and 29%, respectively, at 700°C), but char yields increased as well. We implicated dibenzofuran and other identified phenolic dimers as precursor molecules for char formation pathways, which can be driven by free radical polymerization at high temperatures. Examination of the trends in conversion as a function of initial water and phenol concentrations revealed competing effects, and these informed the kinetic modeling of phenol disappearance. Two different reaction pathways emerged from the kinetic modeling: one in which rate ∝ [phenol] 1.73[water] -16.60 and the other in which rate ∝ [phenol] 0.92[water] 1.39. These pathways may correspond to pyrolysis, which dominates when there is abundant phenol and little water, and hydrothermal reactions, which dominate in excess water. This result confirms that supercritical water gasification of phenol does not simply follow first-order kinetics, as previous efforts to model phenol disappearance had assumed.

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