Acylation desulfurization of oil via reactive adsorption

Abstract

Excellent desulfurization is achieved via reactive adsorption using Friedel-Crafts acylation materials, that is, acylating reagents and Lewis acids, such as acetyl chloride (AC) and AlCl 3 , being named as acylation desulfurization (ACDS). For model oil, thiophenic compounds, namely, dibenzothiophene, benzothiophene, and thiophene, are removed completely by AC-AlCl 3 within 30 min at room temperature. In this process, thiophenic compounds are acylated by AC under the catalysis of AlCl 3 , and the acylated derivatives are stronger base than original ones due to incorporation of O-containing carbonyl group (C@O) and, thus, adsorbed more easily by AlCl 3 via Lewis acid-base complexation. Further, ACDS mechanism is identified by acylated product characterization and quantum chemistry calculation. Satisfactorily, ACDS is still effective for toluene-rich and real oils, and real oil quality is improved with desulfurization proceeding.Note: (1) k represents rate constant obtained from Supporting Information;(2) desulfurization yield is the data at 30 min reaction time; and (3) Conditions: fivefold AlCl 3 , twofold AC, 303 K.

Alkylation of thiophenic compounds catalyzed by deep eutectic solvents

“…In the initial phase of the process, some of these solid catalysts have high catalytic activity and selectivity, but later the formation of carbon deposition will cause rapidly decaying reactivity, especially at high temperature [9]. Later, the desulfurization via the Friedel-Crafts reaction catalyzed by AlCl 3 or AlCl 3 base liquid at room temperature was investigated [10][11][12]. The appearance and composition of AlCl 3 based liquid are similar to traditional chloroaluminate ionic liquids, which have been investigated for isobutane/2-butene and benzene/dodecene alkylation at room temperature [13,14].…”

[HDMF]Cl-based DES as highly efficient extractants and catalysts for oxidative desulfurization of model oil

“…Meanwhile, it is difficult to remove dibenzothiophene (DBT) and its derivatives due to space hindrance. 5 In order to overcome the shortcomings of HDS, some non-HDS technologies such as adsorption desulfurization (ADS), 6,7 oxidative desulfurization (ODS), [8][9][10] biological desulfurization (BDS) 11 and extractive desulfurization 12 have been widely investigated. Among them, the oxidative desulfurization has become a hot topic because of its potential advantages such as mild reaction conditions and high desulfurization rate for dibenzothiophene (DBT) and its derivatives.…”

“…Li et al 31 reported that C 5 H 9 NO$0.3FeCl 3 was used as an extractant as well as a catalyst in ODS and the removal rate of DBT was 97% in 3 h. Chen et al 32 synthesized [C 4 mim]Cl/3ZnCl 2 and 99.9% sulphur-removal rate could be obtained. Dong et al 33 found that the removal rate of DBT can reach up to 100% using [C 6 3 MPy]Cl/FeCl 3 as extractants and catalysts in ODS. In the process of desulfurization of oil, N,Ndimethylformamide (DMF) is oen selected as an effective extractant.…”

Efficient Extractive Desulfurization of Fuel Oils Using N‐Pyrrolidone/Alkylphosphate‐Based Ionic Liquids

“…Besides, HDS requires critical operational conditions like large catalyst bed, high temperature, high pressure and hydrogen consumption to obtain ultra-deep desulfurization, which is not economically suitable for future refinery. Therefore, alternative and complementary desulfurization technologies are heavily investigated, such as adsorptive desulfurization, [11,[13][14][15][16][17][18][19][20][21][22][23][24] biodesulfurization, [25][26][27][28][29][30][31][32] extractive desulfurization and oxidative desulfurization. [54][55][56][57][58][59][60][61][62][63][64][65] Among them, extractive desulfurization (EDS) is one most promising technique for industrial application because of its simple operation procedures, low process cost, decent desulfurization efficiency and regeneration availability.…”