Synthesis, characterization, and application of 1-butyl-3-methylimidazolium thiocyanate for extractive desulfurization of liquid fuel.

1-Butyl-3-methylimidazolium thiocyanate [BMIM]SCN has been presented on extractive desulfurization of liquid fuel. The FTIR, (1)H-NMR, and C-NMR have been discussed for the molecular confirmation of synthesized [BMIM]SCN. Further, thermal, conductivity, moisture content, viscosity, and solubility analyses of [BMIM]SCN were carried out. The effects of time, temperature, sulfur compounds, ultrasonication, and recycling of [BMIM]SCN on removal of dibenzothiophene from liquid fuel were also investigated. In extractive desulfurization, removal of dibenzothiophene in n-dodecane was 86.5 % for mass ratio of 1:1 in 30 min at 30 °C under the mild process conditions. [BMIM]SCN could be reused five times without a significant decrease in activity. Also, in the desulfurization of real fuels, multistage extraction was examined. The data and results provided in the present paper explore the significant insights of imidazolium-based ionic liquids as novel extractant for extractive desulfurization of liquid fuels.

Ultrasound assisted two-stage biodiesel synthesis from non-edible Schleichera triguga oil using heterogeneous catalyst: Kinetics and thermodynamic analysis.

Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H2SO4) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)2) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)2 concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step.

Optimization and Kinetic Studies on Biodiesel Production from Kusum (Schleichera triguga) Oil Using Response Surface Methodology.

In the present study, the low-cost non-edible kusum (Schleichera triguga) oil with a substantial amount of free fatty acid (FFA) was utilized for biodiesel synthesis. In pretreatment step, FFA was reduced by the acid catalyzed esterification method. Then, response surface method (RSM) in conjunction with centre composite design (CCD) containing 30 experimental runs were statistically employed for process optimization and kinetic study for the base catalyzed transesterification process. A statistical model predicted highest fatty acid methyl ester (FAME) yield of 97.37% at the optimal values of process parameters as follows: sodium methoxide concentration 0.9 wt% of oil, Methanol to oil molar ratio 9:1, temperature 58.9 ℃ and reaction time 58.5 min. Using these optimal parameters under experimental conditions in three independent replicates an actual FAME content of 98.14% was obtained which was in reasonable agreement with predicted one. The developed kinetic model suggested a 1.8(th) order reaction with activation energy of 31.42 kcal mol(-1) and frequency factor of 5.53×10(19) L mol(-1)min(-1). Furthermore, Important fuel properties of kusum oil biodiesel (KOB) was compared with ASTM 6751 and DIN EN 14214. The viscosity was found to be 5.34 Cst at 40 °C and the flash point was 152°C.

Ultrasound assisted biodiesel production from sesame (Sesamum indicum L.) oil using barium hydroxide as a heterogeneous catalyst: Comparative assessment of prediction abilities between response surface methodology (RSM) and artificial neural network (ANN).

The present study estimates the prediction capability of response surface methodology (RSM) and artificial neural network (ANN) models for biodiesel synthesis from sesame (Sesamum indicum L.) oil under ultrasonication (20 kHz and 1.2 kW) using barium hydroxide as a basic heterogeneous catalyst. RSM based on a five level, four factor central composite design, was employed to obtain the best possible combination of catalyst concentration, methanol to oil molar ratio, temperature and reaction time for maximum FAME content. Experimental data were evaluated by applying RSM integrating with desirability function approach. The importance of each independent variable on the response was investigated by using sensitivity analysis. The optimum conditions were found to be catalyst concentration (1.79 wt%), methanol to oil molar ratio (6.69:1), temperature (31.92°C), and reaction time (40.30 min). For these conditions, experimental FAME content of 98.6% was obtained, which was in reasonable agreement with predicted one. The sensitivity analysis confirmed that catalyst concentration was the main factors affecting the FAME content with the relative importance of 36.93%. The lower values of correlation coefficient (R(2)=0.781), root mean square error (RMSE=4.81), standard error of prediction (SEP=6.03) and relative percent deviation (RPD=4.92) for ANN compared to those R(2) (0.596), RMSE (6.79), SEP (8.54) and RPD (6.48) for RSM proved better prediction capability of ANN in predicting the FAME content.

Synthesis, characterization and application of 1-butyl-3 methylimidazolium chloride as green material for extractive desulfurization of liquid fuel.

The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, (1)H-NMR, and (13)C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30°C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency.

Effect of chain length of alcohol on the lipase-catalyzed esterification of propionic acid in supercritical carbon dioxide.

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.

Effect of chain length on enzymatic hydrolysis of p-nitrophenyl esters in supercritical carbon dioxide.

The effect of chain length on the enzymatic hydrolysis of various p-nitrophenyl esters was investigated. Specifically, the hydrolysis of various esters p-nitrophenyl butyrate (PNPB), p-nitrophenyl caprylate (PNPC), p-nitrophenyl laurate (PNPL), p-nitrophenyl myristate (PNPM) and p-nitrophenyl palmitate (PNPP) was studied in supercritical carbon dioxide (ScCO2) with lipase (Novozym 435). This indicates that the conversion of nitrophenyl esters decreases with increasing chain length. The effect of various parameters such as amount of water added, temperature, and enzyme loading was studied. The optimum temperature for the hydrolysis of PNPB and PNPC was 50 degrees C but was 55 degrees C for PNPL, PNPM, and PNPP in ScCO2. The reactions were also conducted in acetonitrile as the solvent, and it was found that the reactions reach equilibrium much faster in ScCO2 than in acetonitrile. The kinetics of the hydrolysis reactions were modeled using a Ping Pong Bi Bi model.

Synthesis of isoamyl laurate and isoamyl stearate in supercritical carbon dioxide.

The synthesis of isoamyl laurate and isoamyl stearate was studied in supercritical carbon dioxide with three lipases, Novozym 435, Lipolase 100T, and Candida rugosa. The maximum conversion of 37% and 53%, respectively for isoamyl laurate and isoamyl stearate was obtained when Novozym 435 was used. The effect of various parameters such as molar ratio of alcohol to acid, presence of water, time and temperature was investigated. An optimum temperature of 40-45 degrees C was observed for all reactions. The kinetics of reactions was fast and equilibrium was achieved in 2-3 h. Although the presence of excess alcohol did not reduce conversion, excess water reduced conversion significantly.