The influence of sonoluminescence transesterification on biodiesel physicochemical properties was investigated and the results were compared to those of traditional mechanical stirring. This study was conducted to identify the mechanistic features of ultrasonication by coupling statistical analysis of the experiments into the simulation of cavitation bubble. Different combinations of operational variables were employed for alkali-catalysis transesterification of palm oil. The experimental results showed that transesterification with ultrasound irradiation could change the biodiesel density by about 0.3kg/m(3); the viscosity by 0.12mm(2)/s; the pour point by about 1-2°C and the flash point by 5°C compared to the traditional method. Furthermore, 93.84% of yield with alcohol to oil molar ratio of 6:1 could be achieved through ultrasound assisted transesterification within only 20min. However, only 89.09% of reaction yield was obtained by traditional macro mixing/heating under the same condition. Based on the simulated oscillation velocity value, the cavitation phenomenon significantly contributed to generation of fine micro emulsion and was able to overcome mass transfer restriction. It was found that the sonoluminescence bubbles reached the temperature of 758-713K, pressure of 235.5-159.55bar, oscillation velocity of 3.5-6.5cm/s, and equilibrium radius of 17.9-13.7 times greater than its initial size under the ambient temperature of 50-64°C at the moment of collapse. This showed that the sonoluminescence bubbles were in the condition in which the decomposition phenomena were activated and the reaction rate was accelerated together with a change in the biodiesel properties.
Biodiesel with improved yield was produced from microalgae biomass under simultaneous cooling and microwave heating (SCMH). Nannochloropsis sp. and Tetraselmis sp. which were known to contain higher lipid species were used. The yield obtained using this novel technique was compared with the conventional heating (CH) and microwave heating (MWH) as the control method. The results revealed that the yields obtained using the novel SCMH were higher; Nannochloropsis sp. (83.33%) and Tetraselmis sp. (77.14%) than the control methods. Maximum yields were obtained using SCMH when the microwave was set at 50°C, 800W, 16h of reaction with simultaneous cooling at 15°C; and water content and lipid to methanol ratio in reaction mixture was kept to 0 and 1:12 respectively. GC analysis depicted that the biodiesel produced from this technique has lower carbon components (<19 C) and has both reasonable CN and IV reflecting good ignition and lubricating properties.
Nannochloropsis sp. wet biomass was directly transesterified under microwave (MW) irradiation in the presence of methanol and various alkali and acid catalyst. Two different types of direct transesterification (DT) were used; one step and two step transesterification. The biodiesel yield obtained from the MWDT was compared with that obtained using conventional method (lipid extraction followed by transesterification) and water bath heating DT method. Findings revealed that MWDT efficiencies were higher compared to water bath heating DT by at least 14.34% and can achieve a maximum of 43.37% with proper selection of catalysts. The use of combined catalyst (NaOH and H2SO4) increased the yield obtained by 2.3-folds (water bath heating DT) and 2.87-folds (MWDT) compared with the one step single alkaline catalyst respectively. The property of biodiesel produced by MWDT has high lubricating property, good cetane number and short carbon chain FAME's compared with water bath heating DT.
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.
Transesterification reaction of Jatropha curcas oil with methanol was carried out in the presence of ash generated from Palm empty fruit bunch (EFB) in a heterogeneous catalyzed process. The ash was doped with KOH by impregnation to achieve a potassium level of 20 wt.%. Under optimum conditions for the EFB-catalyzed (65 °C, oil/methanol ratio of 15, 90 min, 20 wt.% EFB ash catalyst) and the KOH-EFB-catalyzed reactions (65 °C, oil/methanol ratio of 15, 45 min, 15 wt.% of KOH doped EFB ash), biodiesel (>98%) with specifications higher than those stipulated by European biodiesel quality standard EN 14214 was obtained.
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).
New polyurethane (PU) nanocomposites were prepared from a dispersion of 0 - 5% montmorillonite (MMT) clay with isocyanate and soya oil polyol that was synthesized via transesterification of triglycerides to reduce petroleum dependence. FT-IR spectra indicate the presence of hydrogen bonding between nanoclay and the polymer matrix, whereas the exfoliated structure of clay layers was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Optical microscopy, mechanical and thermal analyses were done to investigate significant improvement of the nanocomposites. The results showed PU-3% nanoclay (NC) showed optimum results in mechanical properties such as tensile and flexural strength but the lowest in impact strength.
Currently, the chemically-assisted esterification to manufacture butyl butyrate employs corrosive homogeneous acid catalyst and liberates enormous quantities of hazardous by-products which complicate downstream treatment processes. This study aimed to identify the optimized esterification conditions, and the kinetic aspects of the enzyme-assisted synthesis of butyl butyrate using immobilized Candida rugosa lipase activated by chitosan-reinforced nanocellulose derived from raw oil palm leaves (CRL/CS-NC). The best process variables that gave the maximum conversion degree of butyl butyrate by CRL/CS-NC (90.2%) in just 3 h, as compared to free CRL (62.9%) are as follows: 50 °C, 1:2 M ratio of acid/alcohol, stirring rate of 200 rpm and a 3 mg/mL enzyme load. The enzymatic esterification followed the ping pong bi-bi mechanism with substrate inhibition, revealing a ˜1.1-fold higher Ki for CRL/CS-NC (55.55 mM) over free CRL (50.68 mM). This indicated that CRL/CS-NC was less inhibited by the substrates. Butanol was preferred over butyric acid as reflected by the higher apparent Michaelis-Menten constant of CRL/CS-NC for butanol (137 mM) than butyric acid (142.7 mM). Thus, the kinetics data conclusively showed that CRL/CS-NC (Vmax 0.48 mM min-1, Keff 0.07 min-1 mM-1) was catalytically more efficient than free CRL (Vmax 0.35 mM min-1, Keff 0.06 min-1 mM-1).
The Lipase-catalyzed synthesis of glyceryl monocaffeate (GMC) in choline chloride-urea of natural deep eutectic solvent (NADES) media is reported to provide amphiphilic character to caffeic acid (CA). The modification of CA into GMC could potentially increase its solubility and widen the application of CA's biological activities in water and oil-based systems. The high conversion was achieved when the reaction was carried out with the addition of more than 20 %v/v water, at a high molar ratio of glycerol and 40°C. It was found that the lipase-catalyzed transesterification of ethyl caffeate (EC) and glycerol in choline chloride-urea of DES media obeyed ping-pong bi-bi mechanism with Vmax = 10.9 mmol.min-1, KmEC = 126.5 mmol and KmGly = 1842.7 mmol.
Pretreatment of the high free fatty acid rubber seed oil (RSO) via esterification reaction has been investigated by using a pilot scale hydrodynamic cavitation (HC) reactor. Four newly designed orifice plate geometries are studied. Cavities are induced by assisted double diaphragm pump in the range of 1-3.5 bar inlet pressure. An optimised plate with 21 holes of 1mm diameter and inlet pressure of 3 bar resulted in RSO acid value reduction from 72.36 to 2.64 mg KOH/g within 30 min of reaction time. Reaction parameters have been optimised by using response surface methodology and found as methanol to oil ratio of 6:1, catalyst concentration of 8 wt%, reaction time of 30 min and reaction temperature of 55°C. The reaction time and esterified efficiency of HC was three fold shorter and four fold higher than mechanical stirring. This makes the HC process more environmental friendly.
The present work investigates the proficiency of green silver oxide nanocatalyst synthesised from Monotheca buxifolia (Falc.) Dcne. leaves extract, and their application for biodiesel synthesis from novel Prunus bokhariensis seed oil (non-edible). The seed oil content of 55% and FFA content of 0.80 mg KOH/g were reported. Several analytical tools (EDX, FT-IR, SEM and XRD) were used to characterise the Ag2O nanocatalyst. Maximum (89%) FAME yield of the PBSOB (Prunus bokhariensis seed oil biodiesel) was achieved at ambient transesterification conditions i.e. 3.5 wt% nanocatalyst loading, 2.5 h reaction time, 130 °C of reaction temperature and 12:1 alcohol to oil ratio. The synthesised PBSOB was additionally characterised by analytical methods like, GC-MS and FT-IR. The different aspects of fuel were identified i.e. flash point (84 °C), kinematic viscosity (4.01 cSt @ 40 °C), sulphur content (0.0003 wt %), density (0.853 kg/L) and acid number (0.167 mg KOH/g). All the above properties were verified and agreed well with biodiesel international standards (European Union (14214), China GB/T (20828) and ASTM (6751, 951). In general, Prunus bokhariensis seed oil and Ag2O nanocatalyst seem to be remarkably active, cheap and stable candidates for the biodiesel industry in future.
The fatty acid methyl ester (FAME) production from dairy effluent scum as a sustainable energy source using CaO obtained from organic ash over titanium dioxide nanoparticles (TNPs) as the transesterification nano-catalyst has been studied. The physical and chemical properties of the synthesized catalysts were characterized, and the effect of different experimental factors on the biodiesel yield was studied. It was revealed that the CaO-TiO2 nano-catalyst displayed bifunctional properties, has both basic and acid phases, and leads to various effects on the catalyst activity in the transesterification process. These bifunctional properties are critical for achieving simultaneous transesterification of dairy scum oil feedstock. According to the reaction results, the catalyst without and with a low ratio of TNPs showed a low catalytic activity. In contrast, the 3Ca-3Ti nano-catalyst had the highest catalytic activity and a strong potential for reusability, producing a maximum biodiesel yield of 97.2% for a 3 wt% catalyst, 1:20 oil to methanol molar ratio for the dairy scum, and a reaction temperature of 70 °C for a period of 120 min under a 300 kPa pressure. The physical properties of the produced biodiesel are within the EN14214 standards.
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.
Diacylglycerol (DAG) and triacylglycerol (TAG) as responses on optimization of DAG production using a dual response approach of response surface methodology were investigated. This approach takes the molecular equilibrium of DAG into account and allows for the optimization of reaction conditions to achieve maximum DAG and minimum TAG yields. The esterification reaction was optimized with four factors using a central composite rotatable design. The following optimized conditions yielded 48 wt % DAG and 14 wt % TAG: reaction temperature of 66.29 degrees C, enzyme dosage of 4 wt %, fatty acid/glycerol molar ratio of 2.14, and reaction time of 4.14 h. Similar results were achieved when the process was scaled up to a 10 kg production in a pilot packed-bed enzyme reactor. Lipozyme RM IM did not show any significant activity losses or changes in fatty acid selectivity on DAG synthesis during the 10 pilot productions. However, lipozyme RM IM displayed higher selectivity toward the production of oleic acid-enriched DAG. The purity of DAG oil after purification was 92 wt %.
Several binary and ternary medium- and long-chain triacylglycerol (MLCT)-enriched margarine formulations were examined for their solid fat content, heating profile, polymorphism and textural properties. MLCT feedstock was produced through enzymatic esterification of capric and stearic acids with glycerol. The binary formulations were produced by mixing MLCT feedstock blend (40%–90%) and palm olein (10%–60%) with 10% increments (w/w). Solid fat profiles of commercial margarines were used as a reference to determine the suitability of the formulations for margarine production. The solid fat content of the binary formulations of MO 82 and MO 91 (M, MLCT, O, palm olein) were similar to the commercial margarines at 25°C which met the basic requirement for efficient dough consistency. Ternary formulations using reduced MLCT feedstock blend proportion (from 80%–90% to 60%–70%) were also developed. The reduction of MLCT feedstock blend was
done as it had the highest production cost (3USD/kg) in comparison to palm olein (0.77USD/kg) and palm stearin (0.7USD/kg). The proportions of 5%–15% of palm stearin were substituted with palm olein in MO 64 and MO 73 (M, MLCT; O, palm olein) formulations with 5% increment (w/w). As a result, MOS 702010 and MOS 603010 (M, MLCT; O, palm olein; S, palm stearin) margarine formulations showed similar SFC % to the commercial margarines at 25ºC. These formulations were subsequently chosen to produce margarines. The onset melting and complete melting points of MLCT-enriched margarine formulations were high (51.04ºC –57.93ºC) due to the presence of a high amount of long chain saturated fatty acids. Most of the formulations showed β΄- crystals. MOS 702010 was selected as the best formulation due to values for textural parameters comparable (P
Non-edible bio-oil derived from lignocellulosic biomass could be used as environmentally friendly lubricant-ester base stock for maritime and road-type transportations. However, the use of crude bio-oil with highly oxygenated compounds required further upgrading to yield ester that mimicked the characteristics of Group V base oil (polyolesters). In this study, bio-oil based polyolesters was produced via esterification using green biopolymer alginate acid catalyst (Al-Alg). The bio-oil compounds used were acetic acid (AcA), propionic acid (PrA) and levulinic acid (LA), while polyols such as neopentyl glycol (NPG), trimethylolpropane (TMP) and pentaerythritol (PE) were used. Optimization studies revealed that NPG-PrA ester gave the best ester purity of 100%, with 95% of diester selectivity under optimum conditions of 15 wt% Al-Alg, 8 h, 6:1 PrA:NPG and 140 °C. The produced polyolesters showed potential lube characteristics with viscosity index of 76, kinematic viscosity of 2.3 mm2 s-1 at 40 °C and oxidative induction time of 15 min at 100 °C. Furthermore, a reusability study of the Al-Alg catalyst indicated high NPG-PrA diester selectivity (above 90%) for 8 consecutive cycles. The physico-chemical properties of spent Al-Alg catalyst were also discussed.
Interest in biodiesel research has escalated over the years due to dwindling fossil fuel reserves. The implementation of a carbon-based solid acid catalyst in biodiesel production eradicates the separation problems associated with homogeneous catalysis. However, its application in the glycerol-free interesterification process for biodiesel production is still rarely being studied in the literature. In this study, novel environmentally benign catalysts were prepared from oil palm empty fruit bunch (OPEFB) derived activated carbon (AC) which is sustainable and low cost via direct sulfonation using concentrated sulfuric acid. The effects of synthesizing variables such as carbonization and sulfonation temperatures with different holding times towards the fatty acid methyl ester (FAME) yield in interesterification reaction with oleic acid and methyl acetate were investigated in detail. It was found that the optimum carbonization temperature and duration together with sulfonation temperature and duration were 600 °C, 3 h, 100 °C and 6 h, respectively. The catalyst possessed an amorphous structure with a high total acid density of 9.0 mmol NaOH g-1 due to the well-developed porous framework structure of the carbon support. Under these optimum conditions, the OPEFB derived solid acid catalyst recorded an excellent catalytic activity of 50.5% methyl oleate yield at 100 °C after 8 h with 50:1 methyl acetate to oleic acid molar ratio and 10 wt% catalyst dosage. The heterogeneous acid catalyst derived from OPEFB had shown promising properties that made them highly suitable for cost-effective and environmental-friendly glycerol-free biodiesel production.
Most substrate for esterification has the inherent problem of low miscibility which requires addition of solvents into the reaction media. In this contribution, we would like to present an alternative and feasible option for an efficient solvent-free synthesis of menthyl butyrate using a novel thermostable crude T1 lipase. We investigated the effects of incubation time, temperature, enzyme loading and substrate molar ratio and determined the optimum conditions. The high conversion of menthyl butyrate catalyzed by crude T1 lipase in a solvent-free system is greatly affected by temperature and time of the reaction media. The highest yield of menthyl butyrate was 99.3% under optimized conditions of 60 °C, incubation time of 13.15 h, 2.53 mg, 0.43% (w/w) enzyme to substrate ratio and at molar ratio of butyric anhydride/menthol 2.7:1. Hence, the investigation revealed that the thermostable crude T1 lipase successfully catalyzed the high-yield production of menthyl butyrate in a solvent-free system. The finding suggests that the crude T1 lipase was a promising alternative to overcome shortcomings associated with solvent-assisted enzymatic reactions.
The substitution of the oxyanion Q114 with Met and Leu was carried out to investigate the role of Q114 in imparting enantioselectivity on T1 lipase. The mutation improved enantioselectivity in Q114M over the wild-type, while enantioselectivity in Q114L was reduced. The enantioselectivity of the thermophilic lipases, T1, Q114L and Q114M correlated better with log p as compared to the dielectric constant and dipole moment of the solvents. Enzyme activity was good in solvents with log p < 3.5, with the exception of hexane which deviated substantially. Isooctane was found to be the best solvent for the esterification of (R,S)-ibuprofen with oleyl alcohol for lipases Q114M and Q114L, to afford E values of 53.7 and 12.2, respectively. Selectivity of T1 was highest in tetradecane with E value 49.2. Solvents with low log p reduced overall lipase activity and dimethyl sulfoxide (DMSO) completely inhibited the lipases. Ester conversions, however, were still low. Molecular sieves employed as desiccant were found to adversely affect catalysis in the lipase variants, particularly in Q114M. The higher desiccant loading also increased viscosity in the reaction and further reduced the efficiency of the lipase-catalyzed esterifications.
Site-directed mutagenesis of the oxyanion-containing amino acid Q114 in the recombinant thermophilic T1 lipase previously isolated from Geobacillus zalihae was performed to elucidate its role in the enzyme's enantioselectivity and reactivity. Substitution of Q114 with a hydrophobic methionine to yield mutant Q114M increased enantioselectivity (3.2-fold) and marginally improved reactivity (1.4-fold) of the lipase in catalysing esterification of ibuprofen with oleyl alcohol. The improved catalytic efficiency of Q114L was concomitant with reduced flexibility in the active site while the decreased enantioselectivity of Q114L could be directly attributed to diminished electrostatic repulsion of the substrate carboxylate ion that rendered partial loss in steric hindrance and thus enantioselectivity. The highest E-values for both Q114L (E-value 14.6) and Q114M (E-value 48.5) mutant lipases were attained at 50°C, after 12-16h, with a molar ratio of oleyl alcohol to ibuprofen of 1.5:1 and at 2.0% (w/v) enzyme load without addition of molecular sieves. Pertinently, site-directed mutagenesis on the Q114 oxyanion of T1 resulted in improved enantioselectivity and such approach may be applicable to other lipases of the same family. We demonstrated that electrostatic repulsion phenomena could affect flexibility/rigidity of the enzyme-substrate complex, aspects vital for enzyme activity and enantioselectivity of T1.