In situ diesel desulfurization in divided-cell trickle bed electrochemical reactor
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[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] Crude oil contains natural organic components such as organosulfur compounds, and these compounds largely remain in refined petroleum products such as gasoline, diesel and jet fuel products. During fuel combustion, sulfur was emitted as sulfur dioxide or sulfate, which is one of the main causes of air pollution and acid rain. The oil price is inversely proportional to the sulfur content because upgrade of heavy, high-sulfur-containing oil is much more difficult than the light feeds. Many regulations have been established by different countries to control sulfur level in fuels; in the U.S. the maximum required concentration is 15 ppm (parts per million) sulfur in diesel. The most commonly used technology to remove sulfur from diesel fuel is hydrodesulfurization (HDS). The major drawback of HDS is the harsh operating conditions that require high temperatures and pressures with consumption of a large amount of hydrogen. The HDS process is only able to reduce sulfur content to about 500 ppm in diesel. Further reduction requires more intense processing with a significant increase in hydrogen usage, particularly in removing the refractory sulfur compounds, such as benzothiophene (BT), dibenzothiophene (DBT), and their alkyl derivatives. In this dissertation, an efficient and cost-effective process for oxidation of organosulfur compounds (OSCs) in diesel has been developed and investigated. A divided-cell trickle bed electrochemical reactor (TBER) was first developed to produce hydrogen peroxide. The divided-cell trickle bed electrochemical reactor (TBER) has a porous cathode composed of carbon black and polytetrafluoroethylene. It was designed and fabricated to have hydrophobic and hydrophilic components for liquid and gas flows. Hydrogen peroxide generation was successfully demonstrated from reducing oxygen in concentrated alkaline electrolyte solutions. An important feature of the reactor was a cathode made with stainless steel meshes that divide it into four packed-bed cells. This division into sectional cathode resulted in a concentration of hydrogen peroxide that more than doubles that produced in an undivided cathode. The much-improved performance was attributed to the even distribution of the electrolyte and oxygen in the cathode bed, as well as an effective mass transport of oxygen from the gas phase to the electrolyte-cathode interface. After the successful production of hydrogen peroxide, the TBER was employed for in situ oxidation desulfurization of diesel fuel. The possibility of diesel desulfurization with in situ generated hydrogen peroxide in the presence of DBT was systematically investigated. The maximum concentration of hydrogen peroxide after two-hour electrolysis was 31.79 mM without diesel, whereas in the presence of 10% diesel (by volume) in the electrolyte was 18.0 mM. DBT was successfully oxidized in situ in the TBER, with conversion efficiency of 97.75% in six hours. To further improve the efficiency of the hydrogen peroxide production, cathode was modified with MnO2, a potentially more active catalyst for hydrogen peroxide production in alkaline electrolytes. It was found that incorporation of MnO2 indeed promoted in situ oxidation of DBT which was attributed to more hydrogen peroxide produced. The results showed the in situ oxidation process in the divided-cell TBER is a promising and environmentally friendly approach for desulfurization of diesel.
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