Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production

Sulfur compounds represent one of the most common impurities present in the crude oil. Sulfur in liquid fuel oil leads directly to the emission of SO2 and sulfate particulate matter (SPM) that endangers public health and community property; and reduces the life of the engine due to corrosion. Furthermore, the sulfur compounds in the exhaust gases of diesel engines can significantly impair the emission control technology designed to meet NOx and SPM emission standards. The research efforts for developing conventional hydrodesulfurization and alternative desulfurization methods such as selective adsorption, biodesulfurization, oxidation/extraction (oxidative desulfurization), etc. for removing these refractory sulfur compounds from petroleum products are on the rise. Research laboratories and refineries are spending huge amounts of money in finding a viable and feasible solution to reduce sulfur to a concentration of less than 10 mg l−1. This paper reviews the current status in detail of various desulphurization techniques being studied worldwide. It presents an overview of novel emerging technologies for ultra-deep desulfurization so as to produce ultra-low-sulfur fuels.

An evaluation of desulfurization technologies for sulfur removal from liquid fuels

Dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene are typical thiophenic sulfur compounds that exist in diesel fuels Using toluene solutions of the model compounds, experiments were carried out to compare the reactivity of the different dibenzothiophenes in oxidation reactions, a key step for oxidative desulfurizations A series of polyoxometalate/H2O2 systems were evaluated for dibenzothiophene oxidation The H2O2 solutions of phosphotungstic acid and its salt were very active catalyst systems for the model compound oxidation, while their molybdenum counterpart systems were much less active The H2O2 solutions of silicotungstic and silicomolybdic compounds were the least active catalyst systems for the reaction Oxidation reactivities decreased in the order of dibenzothiophene>4-methyldibenzothiophene>4,6-dimethyldibenzothiophene, the same reactivity trend that exists in HDS However, the oxidation of the dibenzothiophenes was achieved under mild reaction conditions and it was easy to increase reaction temperature or reaction time to achieve high oxidation conversions, even for the least reactive 4,6-dimethyldibenzothiophene Apparent activation energies of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene oxidation were 538, 560, and 587 kJ/mol, respectively These activation energies indicated a decrease in reactivity of dibenzothiophenes as methyl substitutes increased at the 4 and 6 positions on dibenzothiophene rings Interestingly, in a formic acid/H2O2 system, the oxidation reactivity of the dibenzothiophenes showed the reverse trend, suggesting that steric hindrance might play a role when bulky polyoxoperoxo species, which likely form in a hydrogen peroxide solution, act as catalysts

Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2 systems

Environmental concerns have introduced a need to remove sulfur-containing compounds from light oil. As oxidative desulfurization is conducted under very mild reaction conditions, much attention has recently been devoted to this process. In this contribution, the developments in selective removal of organosulfur compounds present in liquid fuels via oxidative desulfurization, including both chemical oxidation and biodesulfurization, are reviewed. At the end of each section, a brief account of the research directions needed in this field is also included.

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Oxidative processes of desulfurization of liquid fuels

The oxidation of sulfur compounds in kerosene was conducted with tert-butyl hydroperoxide (t-BuOOH) in the presence of various catalysts. The oxidation activities of dibenzothiophene (DBT) in kerosene for a series of Mo catalysts supported on Al2O3 with various Mo contents were estimated. The results show that the oxidation activity of DBT increased with increasing Mo content up to about 16 wt.% and decreased when Mo content was beyond this value. The oxidation of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT), and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) dissolved in decalin was also carried out on 16 wt.% Mo/Al2O3 catalyst with t-BuOOH to investigate the oxidation reactivities of these sulfur compounds. The results indicated that the oxidation reactivities of these sulfur compounds decreased in the order of DBT>4-MDBT>4,6-DMDBT⪢BT. Analyses of the oxidative reactions of the sulfur compounds suggested that the oxidative reaction of each sulfur compound can be treated as a first-order reaction. The oxidation mechanism is then discussed.

Oxidative desulfurization of fuel oil - Part I. Oxidation of dibenzothiophenes using tert-butyl hydroperoxide

The oxidation of model sulfur compounds (thiophene derivatives, benzothiophene derivatives, and dibenzothiophene derivatives), straight run-light gas oil (SR-LGO, S:  1.35 wt %), and vacuum gas oil (VGO, S:  2.17 wt %) were conducted with a mixture of hydrogen peroxide and formic acid. The thiophene derivatives with 5.696 to 5.716 electron densities on the sulfur atoms could not be oxidized at 50 °C. Benzo[b]thiophene with 5.739 electron density and other benzothiophene and dibenzothiophenes with higher electron densities could be oxidized. The sulfur compounds in SR-LGO and VGO appeared to be oxidized to a detectable levels (c.a., 0.01 wt % S) by GC-FPD analysis. The IR spectra of oxidized SR-LGO and VGO showed that sulfones were formed by oxidation. The removal of sulfur compounds by extraction became more effective for the oxidized samples than for the original samples. Lighter sulfur compounds were preferentially extracted. The extraction efficiencies of solvents, i.e., N,N‘-dimethylformamide (DMF), a...

Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction

Hydrogen exchange reaction between tritiated gaseous hydrogen with hydrogen on several catalysts were carried out using a fixed bed pulse flow reactor at 100–600°C and under 157 MPa The amounts of hydrogen uptake onto the catalysts were determined from the radioactivity balance of tritium between input and output It was found that the hydrogen exchange reaction occurred over γ-Al2O3, K/Al2O3 HY, and NaY but no hydrogen exchange was observed over SiO2 and sulfated zirconia as well as quartz sand Further, the process of hydrogen exchange was elucidated by analyzing in the wave shape of tritium pulse

Tamotsu Imai

Papers

Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction

62 Elucidation of behavior of hydrogen on solid catalysts using a tritium tracer method