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.
Current study presents RSM based optimized production of biodiesel from palm oil using chemical and enzymatic transesterification. The emission behavior of biodiesel and its blends, namely, POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 was examined using diesel engine (equipped with tube well). Optimized palm oil fatty acid methyl esters (POFAMEs) yields were depicted to be 47.6 ± 1.5, 92.7 ± 2.5, and 95.4 ± 2.0% for chemical transesterification catalyzed by NaOH, KOH, and NaOCH3, respectively, whereas for enzymatic transesterification reactions catalyzed by NOVOZYME-435 and A. n. lipase optimized biodiesel yields were 94.2 ± 3.1 and 62.8 ± 2.4%, respectively. Distinct decrease in particulate matter (PM) and carbon monoxide (CO) levels was experienced in exhaust emissions from engine operating on biodiesel blends POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 comparative to conventional petroleum diesel. Percentage change in CO and PM emissions for different biodiesel blends ranged from -2.1 to -68.7% and -6.2 to -58.4%, respectively, relative to conventional diesel, whereas an irregular trend was observed for NOx emissions. Only POB-5 and POB-20 showed notable reductions, whereas all other blends (POB-40 to POB-100) showed slight increase in NOx emission levels from 2.6 to 5.5% comparative to petroleum diesel.
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.
The use of pseudo-infinite methanol in increasing the rate of esterification and transesterification reactions was studied using oil palm trunk (OPT) and sugarcane bagasse (SCB) derived solid acid catalysts. The catalysts were prepared by incomplete carbonisation at 400°C for 8h, followed by sulfonation at 150°C for 15h and characterised using TGA/DTA, XRD, FT-IR, SEM-EDS, EA and titrimetric determinations of acid sites. Under optimal reaction conditions, the process demonstrated rapid esterification of palmitic acid, with FAME yields of 93% and 94% in 45min for OPT and SCB catalysts, respectively. With the process, moisture levels up to 16.7% accelerated the conversion of low FFA oils by sulfonated carbon catalysts, through moisture-induced violent bumping. Moisture assisted transesterification of palm olein containing 1.78% FFA and 8.33% added water gave FAME yield of 90% in 10h, which was two folds over neat oil.
Lipase-catalyzed production of triethanolamine-based esterquat by esterification of oleic acid (OA) with triethanolamine (TEA) in n-hexane was performed in 2 L stirred-tank reactor. A set of experiments was designed by central composite design to process modeling and statistically evaluate the findings. Five independent process variables, including enzyme amount, reaction time, reaction temperature, substrates molar ratio of OA to TEA, and agitation speed, were studied under the given conditions designed by Design Expert software. Experimental data were examined for normality test before data processing stage and skewness and kurtosis indices were determined. The mathematical model developed was found to be adequate and statistically accurate to predict the optimum conversion of product. Response surface methodology with central composite design gave the best performance in this study, and the methodology as a whole has been proven to be adequate for the design and optimization of the enzymatic process.
Hydrocolloid from tamarillo (Solanum betaceum Cav.) puree was extracted using water and characterised for the first time. Proximate compositions of the extracted hydrocolloid were also determined. Functional characteristics such as water-holding capacity, oil-holding capacity, emulsifying activity, emulsion stability, foaming capacity and stability of the hydrocolloid were evaluated in comparison to that of commercial hydrocolloids. Its functional groups and degree of esterification were determined using Fourier Transform Infrared (FT-IR) spectroscopy. Monosaccharide profiling was done using reverse-phase high pressure liquid chromatography (RP-HPLC). Screening of various fruits for high hydrocolloid yield after water extraction resulted in tamarillo giving the highest yield. The yield on dry weight basis was 8.30%. The hydrocolloid constituted of 0.83% starch, 21.18% protein and 66.48% dietary fibre with 49.47% degree of esterification and the monosaccharides identified were mannose, ribose, rhamnose, galacturonic acid, glucose, galactose, xylose and arabinose. Higher oil-holding capacity, emulsifying activity and emulsion stability compared to commercial hydrocolloids propose its possible application as a food emulsifier and bile acid binder. Foaming capacity of 32.19% and good foam stabilisation (79.36% of initial foam volume after 2 h of foam formation) suggest its promising application in frothy beverages and other foam based food products. These findings suggest that water-extracted tamarillo hydrocolloid can be utilised as an alternative to low methoxyl pectin.
Medium- and long-chain triacylglycerol (MLCT) is a modified lipid containing medium- chain (C6-C12) and long-chain fatty acids (C14-C24) in the same triacylglycerol (TAG) molecule. It can be produced either through enzymatic (with 1,3 specific or nonspecific enzyme) or chemical methods. The specialty of this structured lipid is that it is metabolized differently compared to conventional fats and oils, which can lead to a reduction of fat accumulation in the body. Therefore, it can be used for obesity management. It also contains nutritional properties that can be used to treat metabolic problems. This review will discuss on the health benefits of MLCT, its production methods especially via enzymatic processes and its applications in food industries.
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.
Novel heterogeneous catalysts from calcium oxide (CaO)/calcined calcium carbonate (CaCO(3)) loaded onto different palm oil mill boiler ashes were synthesised and used in the transesterification of crude palm oil (CPO) with methanol to yield biodiesel. Catalyst preparation parameters including the type of ash support, the weight percentage of CaO and calcined CaCO(3) loadings, as well as the calcination temperature of CaCO(3) were optimised. The catalyst prepared by loading of 15 wt% calcined CaCO(3) at a fixed temperature of 800°C on fly ash exhibited a maximum oil conversion of 94.48%. Thermogravimetric analysis (TGA) revealed that the CaCO(3) was transformed into CaO at 770°C and interacted well with the ash support, whereas rich CaO, Al(2)O(3) and SiO(2) were identified in the composition using X-ray diffraction (XRD). The fine morphology size (<5 μm) and high surface area (1.719 m(2)/g) of the fly ash-based catalyst rendered it the highest catalytic activity.
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.
In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO2/Al2O3 membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor.
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).
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 objective of this research is to investigate the potential of transesterification of crude palm oil (CPO) to biodiesel at 30 degrees C. The mass transfer limitations problem crucial at 30 degrees C due to the viscosity of CPO has been addressed. The process parameters that are closely related to mass transfer effects like enzyme loading, agitation speed and reaction time were optimized. An optimum methanol to oil substrate molar ratio at 6.5:1 was observed and maintained throughout the experiments. The optimum operating condition for the transesterification process was found at 6.67 wt% of enzyme loading and at 150 rpm of agitation speed. The corresponding initial reaction and FAME yield obtained at 6 h were 89.29% FAME yield/hr and 85.01%, respectively. The 85% FAME yield obtained at 30 degrees C operation of CPO transesterification shows that the process is potentially feasible for the biodiesel synthesis.
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.
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.