Catalytic Oxidative Desulfurization of Fuel by H₂O₂ In Situ Produced via Oxidation of 2-Propanol

Abstract

A novel integrated process is proposed for the catalytic oxidative desulfurization of fuel oil, in which the oxidant H 2 O 2 is in situ generated by oxidizing 2-propanol with oxygen, and its feasibility is evaluated in terms of the S-conversion of 3-methylthiophene (3-MT), benzothiophene (BT), and dibenzothiophene (DBT) in octane under varying conditions. The catalysis of [π-C 5 H 5 NC 16 H 33 ] 3 [PW 4 O 16 ] is found to be much superior to H 3 PW 12 O 40 and [(C 4 H 9 ) 4 N] 3 [PW 12 O 40 ] due to its good dispersivity in oil and adsorptivity for S-compounds. Some influencing factors for the S-conversion were studied, viz., time, temperature, various S-compounds, and the amount of 2-propanol, initiator, oxygen, and catalyst. All factors that favor the production of the 2-propanol radicals affect the desulfurization rate remarkably. Both BT and DBT can be removed efficiently at mild conditions (1.4 MPa O 2 , 90 °C) in 6 h with S-conversion above 96%, and the resulting sulfones can be separated via settling or filtration.

Adsorptive Desulfurization of Diesel Oil by Alkynyl Carbon Materials Derived from Calcium Carbide and Polyhalohydrocarbons

“…Polycyclic aromatic sulfur heterocycles (PASHs) like benzothiophene (BT), dibenzothiophene (DBT), and their alkyl-derivatives in fuel oil are difficult to remove using the conventional hydrodesulfurization (HDS) process. , For their deep removal, harsh process conditions of higher temperature and pressure, longer reaction time, and a larger reactor are indispensible . Thus, it is necessary to develop alternative technologies for the efficient removal of these refractory sulfurs, e.g., adsorption desulfurization (ADS), − oxidative desulfurization (ODS), − and extraction desulfurization (EDS). − Therein, ADS may be more prospective since it can run at ambient temperature and pressure and thus with lower energy consumption. , For the ADS method, the key is to develop efficient sorbents with high adsorption capacity and selectivity for PASHs. Till now, many kinds of industrial sorbents have been studied for the ADS process, e.g., metal ion exchanged zeolites, carbon-based materials, , metal organic framework materials (MOFs), − molecular sieves, active alumina, etc.…”

Competition Adsorption, Equilibrium, Kinetic, and Thermodynamic Studied over La(III)-loaded Active Carbons for Dibenzothiophene Removal

“…If the sulfur level reduces to 0.1 ppmwS, the volume of catalyst bed will have to be increased seven times as that of the current HDS catalyst bed; however, the reductive desulfurization process requires higher operation temperature and pressure for kinetics and bigger reactor sizes, all of these involve an unavoidable and significant capital investment, which are more expensive than before. − Furthermore, reductive desulfurization process can cause a significant reduction of the octane number due to the nonselective hydrogenation of olefins and aromatics and consume more hydrogen . Hence, several new desulfurization technologies, such as adsorption, extraction, oxidation, and bioprocess, have been explored for producing clean fuel. − Among them, adsorption desulfurization (ADS) is superior to others, because ADS can be accomplished at mild environmental conditions …”

Desulfurization of diesel fuel with nickel boride in situ generated in an ionic liquid

“…So many countries have implemented stringent legislation to regulate the sulfur content of transportation fuels. 1,2 To meet the increasingly stringent environmental regulations, many deep desulfurization processes have been developed in the past few years such as alkylation, 3 extraction, [4][5][6][7] oxidation, [8][9][10][11][12] adsorption, [13][14][15][16][17][18][19] membrane separation, 20,21 and bio-desulfurization. 22 In addition, reductive desulfurization is also of importance both in the laboratory and in industry.…”