Fast Solvent Screening for the Simultaneous Hydrodesulfurization and Hydrodenitrification of Diesel Oil Using Ionic Liquids

Abstract

1-Ethyl-3-methylimidazolium [EMIM], 1-ethylpyridinium [EPY], 1-ethyl-1-methylpyrrolidinium [EPYRO], 4-ethyl-4-methylmorpholium [EMMOR], 1-ethyl-1-methylpiperidinium [EMPIP], and 1,2,4-trimethylpyrazolium [TMPYZO] based cations along with 25 anions have been investigated as possible solvents for the simultaneous hydrodesulfurization (HDS) and hydrodenitrification (HDN) of diesel oil at T = 298.15 K. The infinite dilution activity coefficient (IDAC) of thiophene (TS), benzothiophene (BTS), dibenzothiophene (DBTS), pyrrole (PYR), indole (IND), indoline (INDI), carbazole (CAR), benzocarbazole (BCAR), pyridine (PY), quinoline (QU), and benzoquinoline (BQU) was predicted via the quantum chemical based COSMO-RS (COnductor like Screening MOdel for Real Solvents) model. Subsequently, the selectivity and capacity at infinite dilution were used as indicators for the possible screening of ionic liquids (ILs). [EMMOR], [EMPYRO], and [EMPIP] based cations gave lesser activity coefficient values at infinite dilution as compared to [EMIM], [EPY], and [TMPYZO] based cations. It was noted that [DMP], [BTA], [OcSu], and [MSACN] anions, having a different electronegative atom such as N (nitrogen), O (oxygen), and S (sulfur), respectively, play a significant role in increasing the selectivity. High activity coefficients at infinite dilution values were observed for basic nitrogen compounds as compared to the nonbasic nitrogen compounds irrespective of the cation and anion. Evidently, [EMMOR] and [EPYRO] gave higher solvent capacity values at infinite dilution irrespective of the aromatic nitrogen and sulfur compounds.

Study of Ionic Liquids as Entrainers for the Separation of Methyl Acetate–Methanol and Ethyl Acetate–Ethanol Systems Using the COSMO-RS Model

“…COSMO-RS is widely used for solubility and solvent evaluation of ionic liquids in vapor liquid equilibria, 42,43 liquid−liquid equilibria, 44 and hydrodesulfurization and denitrification of diesel oil. 45 Recently, the conceptual design of ionic liquids and the selection of a solvent and its optimization criteria have been documented by Jork et al, 46 especially for the aqueous azeotropic (THF+water) separation by varying the structure of the ionic liquids on the basis of the COSMO-RS predictions. Banerjee and Verma 47 performed the solvent evaluation to identify the potential ionic liquids for the separation of azeotropic mixtures of ethanol−water, 2-propanol−water, and THF−water with the combinations of 10 cations and 24 anions using the COSMO-RS approach.…”

Aromatic sulfur‐nitrogen extraction using ionic liquids: Experiments and predictions using an a priori model

“…This also agrees with our earlier findings based on COSMO-RS predictions. 9,11,24 It was shown from our previous work that a smaller cation like [EMIM] gave higher selectivity. 25 26 and UNIQUAC 27 models have been successfully used for the IL-based ternary LLE predictions.…”

Theoretical Study on Interactions between N-Butylpyridinium Nitrate and Thiophenic Compounds

“…The quantum chemical based COnductor-like Screening MOdel for Real Solvent (COSMO-RS) was used to predict the non-ideal liquid phase activity coefficient for mixtures containing 1-ethyl-3-methyl imidazolium thiocyanate [EMIM][SCN], thiophene, quinoline, pyridine, indoline, pyrrole, and water. 5 The use of mixed ionic liquids as possible alternatives for the removal of aromatics has been studied via COSMO (COnductor like Screening MOdel). 6 Kumar and Banerjee used the COSMO-RS predictions to evaluate the performance of 264 possible cation-anion pairs in the removal of thiophene from diesel oil.…”