In this study, the methanolysis process of sunflower oil was investigated to get high methyl esters (biodiesel) content using sodium methoxide. To reach to the best process conditions, central composite design (CCD) through response surface methodology (RSM) was employed. The optimal conditions predicted were the reaction time of 60 min, an excess stoichiometric amount of alcohol to oil ratio of 25%w/w and the catalyst content of 0.5%w/w, which lead to the highest methyl ester content (100%w/w). The methyl ester content of the mixture from gas chromatography analysis (GC) was compared to that of optimum point. Results, confirmed that there was no significant difference between the fatty acid methyl ester content of sunflower oil produced under the optimized condition and the experimental value (P ≥ 0.05). Furthermore, some fuel specifications of the resultant biodiesel were tested according to American standards for testing of materials (ASTM) methods. The outcome showed that the methyl ester mixture produced from the optimized condition met nearly most of the important biodiesel specifications recommended in ASTM D 6751 requirements. Thus, the sunflower oil methyl esters resulted from this study could be a suitable alternative for petrol diesels.
In the current research work, effect of microwave irradiation energy on the esterification of palm fatty acid distillate (PFAD) to produce PFAD methyl ester / biodiesel was intensively appraised. The PFAD is a by-product from refinery of crude palm oil consisting >85% of free fatty acid (FFA). The esterification reaction process with acid catalyst is needed to convert the FFA into fatty acid methyl ester or known as biodiesel. In this work, fabricated microwave-pulse width modulation (MPWM) reactor with controlled temperature was designed to be capable to increase the PFAD biodiesel production rate. The classical optimization technique was used in order to study the relationship and the optimum condition of variables involved. Consequently, by using MPWM reactor, mixture of methanol-to-PFAD molar ratio of 9:1, 1 wt.% of sulfuric acid catalyst, at 55°C reaction temperature within 15 min reaction time gave 99.5% of FFA conversion. The quality assessment and properties of the product were analyzed according to the American Society for Testing and Materials (ASTM), European (EN) standard methods and all results were in agreement with the standard requirements. It revealed that the use of fabricated MPWM with controlled temperature was significantly affecting the rate of esterification reaction and also increased the production yield of PFAD methyl ester.
Mycelium-bound lipase (MBL), from a locally isolated Geotrichum candidum strain, was produced and characterized as a natural immobilized lipase. A time course study of its lipolytic activity in 1 L liquid broth revealed the maximum MBL activity at 4 h for mycelium cells harvested after 54 h. The yield and specific activity of MBL were 3.87 g/L dry weight and 508.33 U/g protein, respectively, while less than 0.2 U/mL lipase activity was detected in the culture supernatant. Prolonged incubation caused release of the bound lipase into the growth medium. The growth pattern of G. candidum, and production and properties of MBL were not affected by the scale. The stability of mycelia harboring lipase (MBL), harvested and lyophilized after 54 h, studied at 4 °C depicted a loss of 4.3% and 30% in MBL activity after 1 and 8 months, while the activity of free lipase was totally lost after 14 days of storage. The MBL from G. candidum displayed high substrate selectivity for unsaturated fatty acids containing a cis-9 double bond, even in crude form. This unique specificity of MBL could be a direct, simple and inexpensive way in the fats and oil industry for the selective hydrolysis or transesterification of cis-9 fatty acid residues in natural triacylglycerols.
This study demonstrates the potential of Na-silica waste sponge as a source of low cost catalyst in the transesterification of waste cooking oil aided by ultrasound. In this work an environmentally friendly and efficient transesterification process using Na-loaded SiO2 from waste sponge skeletons as a solid catalyst is presented. The results showed that the methyl esters content of 98.4±0.4wt.% was obtainable in less than an hour (h) of reaction time at 55°C. Optimization of reaction parameters revealed that MeOH:oil, 9:1; catalyst, 3wt.% and reaction duration of 30min as optimum reaction conditions. The catalyst is able to tolerant free fatty acid and moisture content up to 6% and 8%, respectively. In addition, the catalyst can be reused for seven cycles while maintaining the methyl esters content at 86.3%. Ultrasound undoubtedly assisted in achieving this remarkable result in less than 1h reaction time. For the kinetics study at 50-60°C, a pseudo first order model was proposed, and the activation energy of the reaction is determined as 33.45kJ/mol using Arrhenius equation.
The use of vegetable oil-based ester as a base fluid in synthetic drilling fluid has become a trend in drilling operations due to its environmental advantages. The transesterification reaction of palm oil methyl ester (POME) with 2-ethylhexanol (2EH) produced 98% of palm oil-based ethylhexyl ester in less than 30 minutes. Since the transesterification reaction of POME with 2EH is a reversible reaction, its kinetics was studied in the presence of excess EH and under vacuum. The POME-to-EH molar ratio and vacuum pressure were held constant at 1:2 and 1.5 mbar respectively and the effects of temperature (70 to 110°C) were investigated. Using excess of EH and continual withdrawal of methanol via vacuum promoted the reaction to complete in less than 10 minutes. The rate constant of the reaction (k) obtained from the kinetics study was in the range of 0.44 to 0.66 s⁻¹ and the activation energy was 15.6 kJ.mol⁻¹. The preliminary investigations on the lubrication properties of drilling mud formulated with palm oil-based 2EH ester indicated that the base oil has a great potential to substitute the synthetic ester-based oil for drilling fluid. Its high kinematic viscosity provides better lubrication to the drilling fluid compared to other ester-based oils. The pour point (-15°C) and flash point (204°C) values are superior for the drilling fluid formulation. The plastic viscosity, HPHT filtrate loss and emulsion stability of the drilling fluid had given acceptable values, while gel strength and yield point could be improved by blending it with proper additives.
Blends of palm stearin (PS), palm kernel oil (PKO) and soybean oil (SBO) at certain proportions were formulated using a mixture design based on simplex-lattice (Design Expert 8.0.4 Stat-Ease Inc., Minneapolis, 2010). All the 10 oil blends were subjected to chemical interesterification (CIE) using sodium methoxide as the catalyst. The solid fat content (SFC), triacylglycerol (TAG) composition, thermal properties (DSC), polymorphism and microstructural properties were studied. Palm-based trans-free table margarine containing ternary mixture of PS/PKO/SBO [49/20/31 (w/w)], was optimally formulated through analysis of multiple isosolid diagrams and was found to have quite similar SMP and SFC profile as compared to the commercial table margarine. This study has shown chemical interesterification are effective in modifying the physicochemical properties of palm stearin, palm kernel oil, soybean oil and their mixtures.
The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel.
Increase in volume of biodiesel production in the world scenario proves that biodiesel is accepted as an alternative to conventional fuel. Production of biodiesel using alkaline catalyst has been commercially implemented due to its high conversion and low production time. For the product and process development of biodiesel, enzymatic transesterification has been suggested to produce a high purity product with an economic, environment friendly process at mild reaction conditions. The enzyme cost being the main hurdle can be overcome by immobilization. Immobilized enzyme, which has been successfully used in various fields over the soluble counterpart, could be employed in biodiesel production with the aim of reducing the production cost by reusing the enzyme. This review attempts to provide an updated compilation of the studies reported on biodiesel production by using lipase immobilized through various techniques and the parameters, which affect their functionality.
This review tracks a decade of dynamic kinetic resolution developments with a biocatalytic inclination using enzymatic/microbial means for the resolution part followed by the racemization reactions either by means of enzymatic or chemocatalyst. These fast developments are due to the ability of the biocatalysts to significantly reduce the number of synthetic steps which are common for conventional synthesis. Future developments in novel reactions and products of dynamic kinetic resolutions should consider factors that are needed to be extracted at the early synthetic stage to avoid inhibition at scale-up stage have been highlighted.
The lipase-catalyzed interesterification of refined, bleached, deodorized palm olein with iodine value (IV) of 62 was studied in a pilot continuous packed-bed reactor operating at 65 degrees C. Sn-1,3 specific immobilized enzyme; Lipozyme TL IM (Thermomyces Lanuginosa) from Novozyme A/S was used in this study. The interesterification reaction produced fully solidified fats at ambient temperature due to the production of trisaturated triacylglycerols (TAG) (PPP and PPS, where P = palmitic acid, S = stearic acid). The reaction also increased the percentage of triunsaturated TAG (OLL, OLO, and OOO, where O = oleic acid, L = linoleic acid). The interesterified product was then dry fractionated at temperatures of 9, 12, 15, 18, and 21 degrees C to separate the saturated fats from the unsaturated. The results show that IV of olein increased when the fractionation temperature (T(FN)) decreased. The highest IV of olein was 72, obtained from T(FN) at 9 degrees C. After interesterification and laboratory-scale fractionation, the olein fractions contained higher unsaturation content ranging from 64.7% to 67.7% compared to the starting material (58.3%), while the saturation content was reduced from 41.7% to the range of 32.3% to 35.3%. The yields of these oleins were low with the range of 24.8% to 51.8% due to the limitation of the vacuum filtration. Ten kilograms of pilot-scale fractionation with membrane press filter was used to determine the exact olein yield. At T(FN) of 12 degrees C, 67.1% of olein with saturation content of 33.9% was obtained.
Immobilized Candida antarctica lipase-catalyzed esterification of adipic acid and oleyl alcohol was investigated in a solvent-free system (SFS). Optimum conditions for adipate ester synthesis in a stirred-tank reactor were determined by the response surface methodology (RSM) approach with respect to important reaction parameters including time, temperature, agitation speed, and amount of enzyme. A high conversion yield was achieved using low enzyme amounts of 2.5% w/w at 60 degrees C, reaction time of 438 min, and agitation speed of 500 rpm. The good correlation between predicted value (96.0%) and actual value (95.5%) implies that the model derived from RSM allows better understanding of the effect of important reaction parameters on the lipase-catalyzed synthesis of adipate ester in an organic solvent-free system. Higher volumetric productivity compared to a solvent-based system was also offered by SFS. The results demonstrate that the solvent-free system is efficient for enzymatic synthesis of adipate ester.
In this work, the esterification of free fatty acids (FFA) in waste cooking oil catalysed by ferric sulphate was studied as a pre-treatment step for biodiesel production. The effects of reaction time, methanol to oil ratio, catalyst concentration and temperature on the conversion of FFA were investigated on a laboratory scale. The results showed that the conversion of FFA reached equilibrium after an hour, and was positively dependent on the methanol to oil molar ratio and temperature. An optimum catalyst concentration of 2 wt.% gave maximum FFA conversion of 59.2%. For catalyst loadings of 2 wt.% and below, this catalysed esterification was proposed to follow a pseudo-homogeneous pathway akin to mineral acid-catalysed esterification, driven by the H(+) ions produced through the hydrolysis of metal complex [Fe(H(2)O)(6)](3+) (aq).
This study reports the conversion of Jatrophacurcas L. oil to biodiesel catalyzed by sulfated zirconia loaded on alumina catalyst using response surface methodology (RSM), specifically to study the effect of interaction between process variables on the yield of biodiesel. The transesterification process variables studied were reaction temperature, reaction duration, molar ratio of methanol to oil and catalyst loading. Results from this study revealed that individual as well as interaction between variables significantly affect the yield of biodiesel. With this information, it was found that 4h of reaction at 150°C, methanol to oil molar ratio of 9.88 mol/mol and 7.61 wt.% for catalyst loading gave an optimum biodiesel yield of 90.32 wt.%. The fuel properties of Jatropha biodiesel were characterized and it indeed met the specification for biodiesel according to ASTM D6751.
Kojic acid monooleate is a fatty acid derivative of kojic acid which can be widely used as a skin whitening agent in a cosmetic applications. In avoiding any possible harmful effects from chemically synthesized product, the enzymatic synthesis appears to be the best way to satisfy the consumer demand nowadays. The ability of immobilized lipase from Rhizomucor meihei (lipozyme RMIM) to catalyze the direct esterification of kojic acid and oleic acid was investigated. Response Surface Methodology (RSM) and 5-level-4-factor central composite rotatable were employed to evaluate the effects of synthesis parameters such as enzyme amount (0.1-0.4 g), temperature (30-60 degrees C), substrate molar ratio (1-4 mmol, kojic acid:oleic acid) and reaction time (24-48 h) on percentage molar conversion to kojic acid monooleate. Analysis of the product using TLC, GC and FTIR showed the presence of kojic acid monooleate. The optimal conditions for the enzymatic reaction were obtained after analysis with backward elimination using 0.17 g of enzyme and 4 mmol of substrate at 52.50 degrees C for 42 h. Under these conditions the esterification percentage was 37.21%. The results demonstrated that response surface methodology can be applied effectively to optimize the lipase-catalysed synthesis of kojic acid monooleate. The optimum conditions can be used to scale up the process.
An intensified esterification process was operated by circulating 10 l of reaction mixtures, consisting of palm oil fatty acid distillate (PFAD) and glycerol in hexane, through a packed-bed reactor (PBR) filled with 10 kg of delipidated rice bran lipase (RBL). The influence of the process parameters, such as reaction temperature and type of water-removal agent, on the performance of this intensified esterification process were investigated. The highest degree of esterification (61%) was achieved at a reaction temperature of 65 masculineC, using silica gels as the water-removal agent. Thin-layer chromatography (TLC) analysis showed that the major composition of the esterified product was diacylglycerol.
The influence of water activity and water content was investigated with farnesyl laurate synthesis catalyzed by Lipozyme RM IM. Lipozyme RM IM activity depended strongly on initial water activity value. The best results were achieved for a reaction medium with an initial water activity of 0.11 since it gives the best conversion value of 96.80%. The rate constants obtained in the kinetics study using Ping-Pong-Bi-Bi and Ordered-Bi-Bi mechanisms with dead-end complex inhibition of lauric acid were compared. The corresponding parameters were found to obey the Ordered-Bi-Bi mechanism with dead-end complex inhibition of lauric acid. Kinetic parameters were calculated based on this model as follows: V (max) = 5.80 mmol l(-1) min(-1) g enzyme(-1), K (m,A) = 0.70 mmol l(-1) g enzyme(-1), K (m,B) = 115.48 mmol l(-1) g enzyme(-1), K (i) = 11.25 mmol l(-1) g enzyme(-1). The optimum conditions for the esterification of farnesol with lauric acid in a continuous packed bed reactor were found as the following: 18.18 cm packed bed height and 0.9 ml/min substrate flow rate. The optimum molar conversion of lauric acid to farnesyl laurate was 98.07 ± 0.82%. The effect of mass transfer in the packed bed reactor has also been studied using two models for cases of reaction limited and mass transfer limited. A very good agreement between the mass transfer limited model and the experimental data obtained indicating that the esterification in a packed bed reactor was mass transfer limited.
Immobilized Candida antarctica lipase B-catalyzed esterification of xylitol and two fatty acids (capric and caproic acid) were studied in a solvent-free system. The Taguchi orthogonal array method based on three-level-four-variables with nine experiments was applied for the analysis and optimization of the reaction parameters including time, substrate molar ratio, amount of enzyme, and amount of molecular sieve. The obtained conversion was higher in the esterification of xylitol and capric acid with longer chain length. The optimum conditions derived via the Taguchi approach for the synthesis of xylitol caprate and xylitol caproate were reaction time, 29 and 18h; substrate molar ratio, 0.3 and 1.0; enzyme amount, 0.20 and 0.05g, and molecular sieve amount of 0.03g, respectively. The good correlation between the predicted conversions (74.18% and 61.23%) and the actual values (74.05% and 60.5%) shows that the model derived from the Taguchi orthogonal array can be used for optimization and better understanding of the effect of reaction parameters on the enzymatic synthesis of xylitol esters in a solvent-free system.
The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost.
Fatty acid methyl ester was produced from used vegetable cooking oil using Mg(1-)(x) Zn(1+)(x)O(2) solid catalyst and the performance monitored in terms of ester content obtained. Used vegetable cooking oil was employed to reduce operation cost of biodiesel. The significant operating parameters which affect the overall yield of the process were studied. The highest ester content, 80%, was achieved with the catalyst during 4h 15 min reaction at 188°C with methanol to oil ratio of 9:1 and catalyst loading of 2.55 wt% oil. Also, transesterification of virgin oil gave higher yield with the heterogeneous catalyst and showed high selectivity towards ester production. The used vegetable cooking oil did not require any rigorous pretreatment. Catalyst stability was examined and there was no leaching of the active components, and its performance was as good at the fourth as at the first cycle.
Kinetics of production of biodiesel by enzymatic methanolysis of vegetable oils using lipase has been investigated. A mathematical model taking into account the mechanism of the methanolysis reaction starting from the vegetable oil as substrate, rather than the free fatty acids, has been developed. The kinetic parameters were estimated by fitting the experimental data of the enzymatic reaction of sunflower oil by two types of lipases, namely, Rhizomucor miehei lipase (RM) immobilized on ion-exchange resins and Thermomyces lanuginosa lipase (TL) immobilized on silica gel. There was a good agreement between the experimental results of the initial rate of reaction and those predicted by the proposed model equations, for both enzymes. From the proposed model equations, the regions where the effect of alcohol inhibition fades, at different substrate concentrations, were identified. The proposed model equation can be used to predict the rate of methanolysis of vegetable oils in a batch or a continuous reactor and to determine the optimal conditions for biodiesel production.