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Kinetics and Mechanism of the Co-Oxidation of Aldehydes and Model Organic Sulfur Compounds in Studies Related to the Oxo-Desulfurization of Fuel Oil and Coal

Citation

Bone, Russell Leslie (1981) Kinetics and Mechanism of the Co-Oxidation of Aldehydes and Model Organic Sulfur Compounds in Studies Related to the Oxo-Desulfurization of Fuel Oil and Coal. Dissertation (Ph.D.), California Institute of Technology. https://resolver.caltech.edu/CaltechETD:etd-10052006-105445

Abstract

Reaction rates and mechanisms in the oxidation of organic sulfur compounds by perbenzoic acid generated in situ from benzaldehyde autoxidation were investigated. Dibenzothiophene and diphenyl sulfide were utilized as model sulfur compounds typical of those present in residual oil and coal. The aromatic nature of a fuel medium was simulated by bromobenzene solvent. Reaction samples were quantitatively analyzed primarily by means of high-pressure liquid chromatography. Diffusion of oxygen, peracid decomposition, and direct oxidation of aldehyde by peracid were found to limit the formation of peracid. Activation energies for decomposition of the peracid and for direct oxidation of the aldehyde by peracid were obtained and used to explain the maximum in oxidation efficiency with respect to temperature observed for dibenzothiophene. Perbenzoic acid was found to be selective in oxidizing diphenyl sulfide and dibenzothiophene to the corresponding sulfoxides and sulfones. At 75°C, diphenyl sulfide was only oxidized approximately twice as rapidly as dibenzothiophene, in contrast with the higher rates reported by other investigators. Both sulfur compounds were found to inhibit the rate of benzaldehyde autoxidation.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemical Engineering
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemical Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Corcoran, William Harrison (advisor)
  • Gavalas, George R. (co-advisor)
Thesis Committee:
  • Gavalas, George R. (chair)
  • Corcoran, William Harrison
  • Shair, Fredrick H.
  • Kalvinskas, John J.
Defense Date:22 January 1981
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
JPLUNSPECIFIED
Bechtel CorporationUNSPECIFIED
Beaumont FoundationUNSPECIFIED
Record Number:CaltechETD:etd-10052006-105445
Persistent URL:https://resolver.caltech.edu/CaltechETD:etd-10052006-105445
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3932
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:13 Oct 2006
Last Modified:02 Dec 2020 01:12

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