ADVANCED OXIDATION PROCESS

Horwitz, Colin P; Collins, Terrence J

doi:10.2172/824769

Title: ADVANCED OXIDATION PROCESS

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Abstract

The design of new, high efficiency and cleaner burning engines is strongly coupled with the removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from fuels. Oxidative desulfurization (ODS) wherein these dibenzothiophene derivatives are oxidized to their corresponding sulfoxides and sulfones is an approach that has gained significant attention. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) convert in a catalytic process dibenzothiophene and its derivatives to the corresponding sulfoxides and sulfones rapidly at moderate temperatures (60 C) and ambient pressure. The reaction can be performed in both an aqueous system containing an alcohol (methanol, ethanol, or t-butanol) to solubilize the DBT and in a two-phase hydrocarbon/aqueous system where the alcohol is present in both phases and facilitates the oxidation. Under a consistent set of conditions using the FeBF{sub 2} TAML activator, the degree of conversion was found to be t-butanol > methanol > ethanol. In the cases of methanol and ethanol, both the sulfoxide and sulfone were observed while for t-butanol only the sulfone was detected. In the two-phase system, the alcohol may function as an inverse phase transfer agent. The oxidation was carried out using two different TAML activators. In homogeneous solution, approximately 90% oxidation of the DBTmore »« less

Authors:: Horwitz, Colin P; Collins, Terrence J

Publication Date:: Wed Oct 22 00:00:00 EDT 2003

Research Org.:: Carnegie Mellon University (US)

Sponsoring Org.:: (US)

OSTI Identifier:: 824769

DOE Contract Number:: FC26-02NT41625

Resource Type:: Technical Report

Resource Relation:: Other Information: PBD: 22 Oct 2003

Country of Publication:: United States

Language:: English

Subject:: 10 SYNTHETIC FUELS; ALCOHOLS; DESIGN; DESULFURIZATION; EFFICIENCY; ENGINES; ETHANOL; HYDROGEN PEROXIDE; METHANOL; OXIDATION; REMOVAL; SULFONES; SULFOXIDES; SULFUR

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                    Horwitz, Colin P, and Collins, Terrence J. ADVANCED OXIDATION PROCESS.  United States: N. p., 2003. 
        Web.  doi:10.2172/824769.

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                    Horwitz, Colin P, & Collins, Terrence J. ADVANCED OXIDATION PROCESS.  United States.  https://doi.org/10.2172/824769

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                    Horwitz, Colin P, and Collins, Terrence J. 2003.  
        "ADVANCED OXIDATION PROCESS".  United States.  https://doi.org/10.2172/824769.  https://www.osti.gov/servlets/purl/824769.

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@article{osti_824769,

  title        = {ADVANCED OXIDATION PROCESS},

  author       = {Horwitz, Colin P and Collins, Terrence J},

  abstractNote = {The design of new, high efficiency and cleaner burning engines is strongly coupled with the removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from fuels. Oxidative desulfurization (ODS) wherein these dibenzothiophene derivatives are oxidized to their corresponding sulfoxides and sulfones is an approach that has gained significant attention. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) convert in a catalytic process dibenzothiophene and its derivatives to the corresponding sulfoxides and sulfones rapidly at moderate temperatures (60 C) and ambient pressure. The reaction can be performed in both an aqueous system containing an alcohol (methanol, ethanol, or t-butanol) to solubilize the DBT and in a two-phase hydrocarbon/aqueous system where the alcohol is present in both phases and facilitates the oxidation. Under a consistent set of conditions using the FeBF{sub 2} TAML activator, the degree of conversion was found to be t-butanol > methanol > ethanol. In the cases of methanol and ethanol, both the sulfoxide and sulfone were observed while for t-butanol only the sulfone was detected. In the two-phase system, the alcohol may function as an inverse phase transfer agent. The oxidation was carried out using two different TAML activators. In homogeneous solution, approximately 90% oxidation of the DBT could be achieved using the prototype TAML activator, FeB*, by sonicating the solution at near room temperature. In bi-phasic systems conversions as high as 50% were achieved using the FeB* TAML activator and hydrogen peroxide at 100 C. The sonication method yielded only {approx}6% conversion but this may have been due to mixing.},

  doi          = {10.2172/824769},

  url          = {https://www.osti.gov/biblio/824769},
  journal      = {},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Wed Oct 22 00:00:00 EDT 2003},

  month        = {Wed Oct 22 00:00:00 EDT 2003}

}

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ADVANCED OXIDATION PROCESS

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The removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from automotive fuels is an integral component in the development of cleaner burning and more efficient automobile engines. Oxidative desulfurization (ODS) wherein the dibenzothiophene derivative is converted to its corresponding sulfoxide and sulfone is an attractive approach to sulfur removal because the oxidized species are easily extracted or precipitated and filtered from the hydrocarbon phase. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) catalytically convert dibenzothiophene and its derivatives rapidly and effectively at moderate temperatures (50-60 C) and ambient pressure to the corresponding sulfoxides and sulfones. The oxidation process canmore »« less
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