Sonocatalytic oxidative desulfurization of thiophene and its derivatives

Abstract

Currently, the sulfur level in diesels is limited to 10 and 15 ppm in Europe and USA respectively, since the organosulfur compounds available in fuels emit corrosive SO2 gases into atmosphere during combustion, thus leading to acid rain. A lot of processes such as hydrodesulfurization (HDS), oxidative desulfurization (ODS) etc. have been used to reduce sulfur level in fuels and ODS, which is alternative to conventional HDS, is much more efficient in removing benzothiophene (BT), dibenzothiophene (DBT) and their alkyl derivatives as compared with HDS and more economical. One of very powerful oxidation systems used in ODS is H2O2-formic acid and removal of alkyl-substituted derivatives of T, BT and DBT with this oxidation system is easier than that with H2O2-phosphotungstic acid catalyst system due to the steric hindrance of alkyl groups adjacent to sulfur atom because phosphotungstic acid is a bulky catalyst. In this work, oxidative desulfurization reactions of the model compounds, thiophene (T), 2-methylthiophene (2-MT) and 2,5-dimethylthiophene (2,5-DMT), which have the lowest reactivity in ODS, on sonication at low H2O2 (O) / F (formic acid) / S (organosulfur solution) volume ratios were carried out sequentially in the presence of tetrabutylammonium bromide (TBAB) as phase transfer catalyst at 30 and 40 degrees C. First, the solution of the relevant model sulfur compound in n-heptane was put into a steel batch reactor and later, reactions were performed by adding mixture of 35 % H2O2, formic acid and TBAB onto the organic phase. After each reaction cycle, the aqueous phase was removed by a separation funnel and the oxidative desulfurization reaction of the remaining treated organic phase was repeated three or four times with reuse of the same amounts of fresh hydrogen peroxide, formic acid and TBAB as in the first reactions at 30 and 40 degrees C for 15 min. After every reaction cycle, the sulfur compounds in heptane were analyzed by using GC with Sulfur Chemiluminescence Detector. Afterwards, the oxidative desulfurization reactions of the model sulfur compounds in heptane were performed for only one cycle in sonoreactor with total amount of oxidation reagents H2O2, formic acid and the same amount of TBAB used in the former multi-cycle reactions at 30 and 40 degrees C for 15 and 60 min. It was observed that the total conversions of model sulfur compounds obtained from multicycle reactions were higher than its conversions obtained from single-cycle reactions with total amount of oxidation reagents used in the multicycle reaction. The same method was also applied to diesel fuel sample and it was shown that high sulfur removal is reached. (C) 2012 Published by Elsevier Ltd.