Monitoring of Remaining Thiophenic Compounds in Liquid Fuel Desulphurization Studies Using a Fast HPLC-UV Method

Thiophenic compounds constitute a class of sulfur compounds derived by thiophene, containing at least one thiophenic ring. Their presence in fuels (crude oil, etc.) is important and can reach 3% m/m. The combustion of fuels leads to the formation of sulfur oxides a severe source of environmental pollution issues, such as acid rain with adverse effects both to humans and to the environment. To reduce such problems, the EU and other regulatory agencies worldwide set increasingly stringent regulations for sulfur content in fuels resulting in the necessity for intense desulphurization processes. However, most of these processes are inefficient in the total removal of sulfur compounds. Therefore, thiophenic compounds such as benzothiophenes and dibenzothiophenes are still present in heavier fractions of petroleum, therefore, their determination is of great importance. Until now, all HPLC methods applied in similar studies use gradient elution programs that may last more than 25 min with no validation results provided. To fill this gap, the aim of the present study was to develop and validate a simple and fast HPLC-UV method in order to be used as a useful monitoring tool in the evaluation studies of novel desulfurization technologies by means of simultaneous determination of dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene and dibenzothiophene sulfone in the desulfurization effluents.

Polyoxometalate Dicationic Ionic Liquids as Catalyst for Extractive Coupled Catalytic Oxidative Desulfurization

Wettability is an important factor affecting the performance of catalytic oxidative desulfurization. In order to develop an efficient catalyst for the extractive coupled catalytic oxidative desulfurization (ECODS) of fuel oil by H2O2 and acetonitrile, a novel family of imidazole-based polyoxometalate dicationic ionic liquids (POM-DILs) [Cn(MIM)2]PW12O40 (n = 2,4,6) was synthesized by modifying phosphotungstic acid (H3PW12O40) with double imidazole ionic liquid. These kinds of catalysts have good dispersity in oil phase and H2O2, which is conducive to the deep desulfurization of fuel oil. The catalytic performance of the catalysts was studied under different conditions by removing aromatic sulfur compound dibenzothiophene (DBT) from model oil. Results showed that [C2(MIM)2]PW12O40 had excellent desulfurization efficiency, and more than 98% of DBT was removed under optimum conditions. In addition, it also exhibited good recyclability, and activity with no significant decline after seven reaction cycles. Meanwhile, dibenzothiophene sulfone (DBTO2), the only oxidation product of DBT, was confirmed by Gas Chromatography-Mass Spectrometry (GC-MS), and a possible mechanism of the ECODS process was proposed.

Spectral-Luminescent and Electroluminescent Properties of Charge-Transfer Systems Based on Electron-Donating Diphenylamine Derivatives and Acceptors of Dibenzothiophene Sulfone and Phenanthridine

Spectral characteristics and luminescence under the photo- and electro-excitation of substituted dibenzthiophene sulfone and phenanthridine were studied in this paper. Diphenylamines are substituents introduced in the 2nd and 7th positions (linear configuration) or the 3rd and 6th positions (angular configuration) of dibenzthiophene sulfone or phenanthridine. All molecules show delayed fluorescence, both in solutions and films produced by thermal vacuum deposition. The value of the energy gap between the S1 and T1 states has been estimated and is shown to depend not only on the spatial arrangement of the fragments among themselves (linear or angular), but also on the nature of the substituent in diphenylamine. The highest electroluminescence brightness was found for the molecules, in which triplet levels are involved, both through the process of triplet-triplet annihilation and through thermally activated delayed fluorescence.

Ionothermal Synthesis of Metal Oxide-Based Nanocatalysts and Their Application towards the Oxidative Desulfurization of Dibenzothiophene

Herein, different types of metal-containing ionic liquid (IL) complexes and various metal oxide-based nanocatalysts have been successfully prepared (from ionic liquids) and applied for the oxidative desulfurization (ODS) of dibenzothiophene (DBT). The ILs complexes are comprised of N,N′-dialkylimidazolium salts of the type [RMIM-Cl]2[MCln], where [RMIM+] = 1 alkyl-3-methylimidazolium and M = Mn(II)/Fe(II)/Ni(II)/Co(II). These complexes were prepared using an easy synthetic route by refluxing the methanolic solutions of imidazolium chloride and metal chlorides under facile conditions. The as-prepared complexes were further used as precursors during the ionothermal and chemical synthesis of various metal oxide-based nanocatalysts. The resulting ILs salts and metal oxides NPs have been characterized by FT-IR, TGA, XRD, SEM, and TEM analysis. The results indicate that thermal and chemical treatment of ILs based precursor has produced different phases of metal oxide NPs. The calcination produced α-Fe2O3, Mn3O4, and Co3O4, NPs, whereas the chemical treatment of the ILs salts have led to the production of Fe3O4, Mn2O3, and α-Co(OH)2. All the as-prepared salts and metal oxide-based nanocatalysts were used as catalysts towards ODS of dibenzothiophene. The oxidation of dibenzothiophene was performed at atmospheric conditions using hydrogen peroxide as the oxygen donor. Among various catalysts, the thermally obtained metal oxide NPs such as α-Fe2O3, Mn3O4, and Co3O4, have demonstrated relatively superior catalytic activities compared to the other materials. For example, among these nanocatalysts, α-Fe2O3 has exhibited a maximum conversion (∼99%) of dibenzothiophene (DBT) to dibenzothiophene sulfone (DBTO2).

Light-Enhanced Adsorptive Desulfurization of Dibenzothiophene Using Supported TiO2-ZrO2

Combustion of diesel fuel containing sulfur compounds emits SOx into atmosphere causing acid rain and respiratory illness in human. Dibenzothiophene (DBT) is one of the most difficult sulfur compounds in diesel to be removed by hydrodesulfurization (HDS). To produce ultra-low sulfur diesel (<15 ppmw-S), severe operating condition is required. As a result, production cost is increase. In this work, we investigated an alternative method for sulfur removal called Light-enhanced Adsorptive Desulfurization or L-ADS using supported TiO2-ZrO2. The TiO2-ZrO2 was loaded on commercial γ-Al2O3, fumed silica (FS), silica gel (SG) and zeolite (Z30) by wet-impregnation method. Impact of these supports on DBT removal were focused. Characteristic of the supported TiO2-ZrO2 was analyzed by N2 adsorption-desorption, scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The presence of TiO2-ZrO2 greatly enhanced DBT removal compared to TiO2 and ZrO2. SG promoted DBT removal by facilitating the adsorption of dibenzothiophene sulfone (DBTO2), a product of DBT photocatalytic oxidation. Using TiO2-ZrO2/SG, 86% of sulfur was removed from 50 ppmw-S DBT/C16 within 4 h.