Two novel and highly accurate hybrid models were developed for the prediction of the flammability limits (lower flammability limit (LFL) and upper flammability limit (UFL)) of pure compounds using a quantitative structure-property relationship approach. The two models were developed using a dataset obtained from the DIPPR Project 801 database, which comprises 1057 and 515 literature data for the LFL and UFL, respectively. Multiple linear regression (MLR), logarithmic, and polynomial models were used to develop the models according to an algorithm and code written using the MATLAB software. The results indicated that the proposed models were capable of predicting LFL and UFL values with accuracies that were among the best (i.e. most optimised) reported in the literature (LFL: R2 = 99.72%, with an average absolute relative deviation (AARD) of 0.8%; UFL: R2 = 99.64%, with an AARD of 1.41%). These hybrid models are unique in that they were developed using a modified mathematical technique combined three conventional methods. These models afford good practicability and can be used as cost-effective alternatives to experimental measurements of LFL and UFL values for a wide range of pure compounds.
Deep eutectic solvents (DESs) are green solvents developed as an alternative to conventional organic solvents and ionic liquids to extract nitrogen compounds from fuel oil. DESs based on p-toluenesulfonic acid (PTSA) are a new solvent class still under investigation for extraction/separation. This study investigated a new DES formed from a combination of tetrabutylphosphonium bromide (TBPBr) and PTSA at a 1:1 molar ratio. Two sets of ternary liquid-liquid equilibrium experiments were performed with different feed concentrations of nitrogen compounds ranging up to 20 mol% in gasoline and diesel model fuel oils. More than 99% of quinoline was extracted from heptane and pentadecane using the DES, leaving the minutest amount of the contaminant. Selectivity was up to 11,000 for the heptane system and up to 24,000 for the pentadecane system at room temperature. The raffinate phase's proton nuclear magnetic resonance (1H-NMR) spectroscopy and GC analysis identified a significantly small amount of quinoline. The selectivity toward quinoline was significantly high at low solute concentrations. The root-mean-square deviation between experimental data and the non-random two-liquid (NRTL) model was 1.12% and 0.31% with heptane and pentadecane, respectively. The results showed that the TBPBr/PTSADES is considerably efficient in eliminating nitrogen compounds from fuel oil.
Removal of nitrogen and sulfur compounds from diesel fuel is essential to comply with the increasing stringent regulations. The extraction capability of two deep eutectic solvents, namely, tetrabutylphosphoniumbromide/ethylene glycol, TBPBr/EG, with molar ratio 1:2, and tetrabutylammoniumbromide/ethylene glycol, TBABr/EG, with molar ratio 1:2, in simultaneously extracting basic nitrogen, nonbasic nitrogen, and sulfur compounds represented by pyridine, indoline, and dibenzothiophene (DBT) from n-hexadecane, was investigated. Two pseudo-ternary phase diagrams of (TBPBr/EG + (pyridine + indoline + DBT) + n-hexadecane) and (TBABr/EG + (pyridine + indoline + DBT) + n-hexadecane) were predicted via a conductor-like screening model for real solvents (COSMO-RS) and experimentally validated at 298.15 K and 1 atm. Both solvents showed zero cross-contamination, indicating the suitability of all solvents as extraction solvents. The tie lines obtained for both COSMO-RS and experiments were in agreement and had root-mean-square deviation (RMSD) values of less than 5% for both systems. Selectivity and distribution ratio calculated indicates the suitability of both solvents in extracting sulfur and nitrogen compounds from hexadecane. Two new parameters, namely, extraction efficiency, α, and extraction affinity, β, were introduced to ease the performance comparison of both solvents. TBPBr/EG shows a slightly better performance than TBABr/EG. Other than that, the presence of multiple solutes shows low effects on the performance of these solvents.