Superoxide radical and UV irradiation in ultrasound assisted oxidative desulfurization (UAOD): A potential alternative for greener fuels

This study is aimed at improving the current ultrasound assisted oxidative desulfurization (UAOD) process by utilizing superoxide radical as oxidant. Research was also conducted to investigate the feasibility of ultraviolet (UV) irradiation-assisted desulfurization. These modifications can enhance the process with the following achievements: (1) Meet the upcoming sulfur standards on various fuels including diesel fuel oils and residual oils; (2) More efficient oxidant with significantly lower consumption in accordance with stoichiometry; (3) Energy saving by 90%; (4) Greater selectivity in petroleum composition. Currently, the UAOD process and subsequent modifications developed in University of Southern California by Professor Yen's research group have demonstrated high desulfurization efficiencies towards various fuels with the application of 30% wt. hydrogen peroxide as oxidant. The UAOD process has demonstrated more than 50% desulfurization of refractory organic sulfur compounds with the use of Venturella type catalysts. Application of quaternary ammonium fluoride as phase transfer catalyst has significantly improved the desulfurization efficiency to 95%. Recent modifications incorporating ionic liquids have shown that the modified UAOD process can produce ultra-low sulfur, or near-zero sulfur diesels under mild conditions with 70°C and atmospheric pressure.;Nevertheless, the UAOD process is considered not to be particularly efficient with respect to oxidant and energy consumption. Batch studies have demonstrated that the UAOD process requires 100 fold more oxidant than the stoichiometic requirement to achieve high desulfurization yield. The expected high costs of purchasing, shipping and storage of the oxidant would reduce the practicability of the process. The excess use of oxidant is not economically desirable, and it also causes environmental and safety issues. Post treatments would be necessary to stabilize the unspent oxidant residual to prevent the waste stream from becoming reactive or even explosive.;High energy consumption is another drawback in the UAOD process. A typical 10 minutes ultrasonication applied in the UAOD process to achieve 95% desulfurization for 20g of diesel requires 450 kJ of energy, which is equivalent to approximately 50% of the energy that can be provided by the treated diesel. This great expenditure of energy is impractical for industries to adopt.;In this study, modifications of the UAOD process, including the application of superoxide and selection of catalysts, were applied to lower the oxidant dosage and to improve the applicability towards heavy-distillates such as residual oil. The results demonstrated that the new system required 80% less oxidant as compared to previous generations of UAOD process without the loss of desulfurization efficiency.;The new system demonstrated its suitability towards desulfurizing commercial mid-distillates including jet fuels, marine gas oil and sour diesel. This process also demonstrated a new method to desulfurize residual oil with high desulfurization yields. The new process development has been supported by Eco Energy Solutions Inc., Reno, Nevada and Intelligent Energy Inc., Long Beach, California.;A feasibility study on UV assisted desulfurization by replacing ultrasound with UV irradiation was also conducted. The study demonstrated that the UV assisted desulfurization process consumes 90% less energy than the comparable process using ultrasonication.;These process modifications demonstrated over 98% desulfurization efficiency on diesel oils and more than 75% on residual oils with significantly less oxidant and energy consumption. Also the feasibility to desulfurize commercial sour heavy oil was demonstrated. Based on the UAOD process and the commercialized modifications by Wan and Cheng, the feasible applications of superoxide and UV irradiation in the UAOD process could provide deep-desulfurization on various fuels with practical cost.