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.
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
Microwave assisted extraction treatments showed the higher pectin yields of 10.07% and 8.83% in pretreated samples by microwave and 9.4% and 8% in the extraction of dried after microwave treatment in lemon peel and apple pomace samples, respectively. Lemon peel pectin in pretreated samples by microwave and extraction of dried after microwave treatment showed the higher degree of esterification 71.8% and 70%, respectively, while apple pomace revealed 68% and 65.4% in same treatments. Furthermore, lemon peel pectin exhibited the highest galacturonic content of 74.5% in extraction of pretreated samples by microwave, while apple pomace pectin indicated the higher galacturonic acid content of 70.5% and 70% in both extraction of dried after microwave treatment and extraction of dried samples. Texture analysis of jellies prepared by various extracted pectin indicated the highest fracturability in the microwave-assisted drying treatment of 33 N and 32.5 N for apple pomace and lemon peel pectin, respectively.
Octenyl succinic anhydride (OSA) modified sago starch was prepared in order to improve the emulsification properties of native starch. In the present study, the major factors affecting esterification were investigated with respect to OSA concentration, pH and reaction time using response surface methodology (RSM) based on central composite rotatable design (CCRD) to obtain the highest value of degree of substitution (DS). Results shown that the optimum conditions for OSA concentration, pH and reaction time were 5.00%, pH 7.20 and 9.65 h, respectively. At optimum condition, the esterification of sago starch with OSA resulted in DS value of 0.0120. The DS increased linearly with the increase in amount of OSA, whilst pH and reaction time show a curvature trend on the value of DS. The value of DS was found to be significantly affected by all the three variables. The experimental values under optimum condition were in good consistent with the predicted values (0.0131), which suggested that the optimisation by RSM is more efficient process than conventional optimisation.
Due to its environment-friendly and replenishable characteristics, biodiesel has the potential to substitute fossil fuels as an alternative source of energy. Although biodiesel has many benefits to offer, manufacturing biodiesel on an industrial scale is uneconomical as a high cost of feedstock is required. A novel sulfonated and magnetic catalyst synthesised from a palm kernel shell (PMB-SO3H) was first introduced in this study for methyl ester or biodiesel production to reduce capital costs. The wasted palm kernel shell (PKS) biochar impregnated with ferrite Fe3O4 was synthesised with concentrated sulphuric acid through the sulfonation process. The SEM, EDX, FTIR, VSM and TGA characterization of the catalysts were presented. Then, the optimisation of biodiesel synthesis was catalysed by PMB-SO3H via the Response Surface Methodology (RSM). It was found that the maximum biodiesel yield of 90.2% was achieved under these optimum operating conditions: 65 °C, 102 min, methanol to oil ratio of 13:1 and the catalyst loading of 3.66 wt%. Overall, PMB-SO3H demonstrated acceptable catalysing capability on its first cycle, which subsequently showed a reduction of the reusability performance after 4 cycles. An important practical implication is that PMB-SO3H can be established as a promising heterogeneous catalyst by incorporating an iron layer which can substantially improve the catalyst separation performance in biodiesel production.
The data presented in this article were generated through the gas chromatography (GC) with a flame ionization detector (FID). The flaxseed oil was converted into fatty acid methyl ester (FAME) then used in the GC with FID and observe the retention time of different fatty acid present in the flaxseed oil. The observed retention time was compared with the standard fatty acid to confirm the specific fatty acid presence in the flaxseed oil. The part of the data is used in the article "Optimization of the process variable for biodiesel production by transesterification of flaxseed oil and produced biodiesel characterizations" Renewable Energy journal (Ahmad et al., 2019).
Biodiesels and biolubricants are synthetic esters produced mainly via a transesterification of other esters from bio-based resources, such as plant-based oils or animal fats. Microwave heating has been used to enhance transesterification reaction by converting an electrical energy into a radiation, becoming part of the internal energy acquired by reactant molecules. This method leads to major energy savings and reduces the reaction time by at least 60% compared to a conventional heating via conduction and convection. However, the application of microwave heating technology alone still suffers from non-homogeneous electromagnetic field distribution, thermally unstable rising temperatures, and insufficient depth of microwave penetration, which reduces the mass transfer efficiency. The strategy of integrating multiple technologies for biodiesel and biolubricant production has gained a great deal of interest in applied chemistry. This review presents an advanced transesterification process that combines microwave heating with other technologies, namely an acoustic cavitation, a vacuum, ionic solvent, and a supercritical/subcritical approach to solve the limitations of the stand-alone microwave-assisted transesterification. The combined technologies allow for the improvement in the overall product yield and energy efficiency. This review provides insights into the broader prospects of microwave heating in the production of bio-based products.
A synergistic effect of the activated limestone-based catalyst (LBC) and microwave irradiation on the transesterification of waste cooking oil (WCO) was screened using a two-level factorial design and response surface methodology. The catalyst was prepared using a wet-impregnation method and was characterised for its surface element, surface morphology, surface area and porosity. The reaction was performed in a purpose-built continuous microwave assisted reactor (CMAR), while the conversion and yield of biodiesel were measured using a gas chromatography. The results showed that the catalyst loading, methanol to oil molar ratio and the reaction time significantly affect the WCO conversion. The optimum conversion of oil to biodiesel up to 96.65% was achieved at catalyst loading of 5.47 wt%, methanol to oil molar ratio of 12.21:1 and the reaction time of 55.26 min. The application of CMAR in this work reduced the transesterification time by about 77% compared to the reaction time needed for a conventional reactor. The biodiesel produced in this work met the specification of American Society for Testing and Materials (ASTM D6751). Engine test results shows the biodiesel has a lower NOx and particulate matters emissions compared to petrodiesel.
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.
The present study defines a novel green method for the synthesis of the nickel oxide nanocatalyst by using an aqueous latex extract of the Ficus elastic. The catalyst was examined for the conversion of novel Brachychiton populneus seed oil (BPSO) into biodiesel. The Brachychiton populneus seeds have a higher oil content (41 wt%) and free fatty acid value (3.8 mg KOH/g). The synthesised green nanocatalyst was examined by the Fourier transform infrared (FT-IR) spectroscopy, energy dispersive X-Ray (EDX) spectroscopy, X-Ray diffraction (XRD) spectroscopy and scanning electron microscopy (SEM). The obtained results show that the synthesised green nanocatalyst was 22-26 nm in diameter and spherical-cubic in shape with a higher rate of catalytic efficiency. It was utilised further for the conversion of BPSO into biofuel. Due to the high free fatty acid value, the biodiesel was synthesised by the two-step process, i.e., pretreatment of the BPSO by means of acid esterification and then followed by the transesterification reaction. The acidic catalyst (H2SO4) was used for the pretreatment of BPSO. The optimum condition for the transesterification of the pretreated BPSO was 1:9 of oil-methanol molar ratio, 2.5 wt % of prepared nanocatalyst concentration and 85 °C of reaction temperature corresponding to the highest biodiesel yield of 97.5 wt%. The synthesised biodiesel was analysed by the FT-IR and GC-MS technique to determine the chemical composition of fatty acid methyl esters. Fuel properties of Brachychiton populneus seed oil biodiesel (BPSOB) were also examined, compared, and it falls in the prescribed range of ASTM standards.
In this study, carbon-silica based acid catalysts derived from rice husks (RH) were successfully synthesised using microwave (MW) technology. The results showed that MW sulphonation produced Sulphur (S) content of 17.2-18.5 times higher than in raw RH. Fourier-transform Infrared Spectroscopy (FTIR) showed peak at 1035 cm-1 which corresponded to O˭S˭O stretching of sulphonic (-SO3H) group. XRD showed sulfonated RH catalysts (SRHCs) have amorphous structure, and through SEM, broadening of the RH voids and also formation of pores is observed. RH600 had the highest surface area of 14.52 m2/g. SRHCs showed high catalytic activity for esterification of oleic acid with methanol with RH600 had the highest initial formation rate (6.33 mmolL-1min-1) and yield (97%). The reusability of the catalyst showed gradually dropped yield of product for every recycle, which might be due to leaching of -SO3H. Finally, esterification of oil recovered from palm oil mill effluent (POME) with methanol achieved a conversion of 87.3% free fatty acids (FFA) into fatty acid methyl esters (FAME).
Acidolysis to incorporate oleic acid into refined, bleached and deodorized (RBD) palm olein (IV 56) using various lipases (enzymes) as catalysts to increase the oleic content of the oil was investigated. Immobilised lipases (lipase PLG, Lipozyme TL IM, Lipozyme RM IM and Novozym 435) and non-immobilised lipase (lipase PL) were used in this study to compare the effectiveness of the selected lipases in catalyzing the reaction to produce a high oleic oil. The results showed that the TAG of OLO/OOL content was increased at least 4 fold and OOO content was increased at least 3 fold when a 5% enzyme load was used. Lipase PL showed the greatest increase in tri-unsaturated triacylglycerols (TAGs) content. A pilot scale experiment conducted using TL IM enzyme, followed by recovery of the oil and fractionation allows the production of oils with varying oleic contents. A high oleic content of 56% was achievable.
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.
Recent research suggesting the existence of potential source of pectin from roselle calyces. Pectin was successfully extracted from seven different varieties of roselle calyces. Pectin extraction was conducted using hydrochloric acid (HCl, 0.03 N, pH 1.5) or ammonium oxalate (0.25% w/v, pH 4.6) at 85⁰C for 1 h. Chemical characteristics of the HCl- and ammonium oxalate extracted pectin were compared. Results indicated that ammonium oxalate exhibited greater efficiency in pectin extraction than HCl. Highest pectin yield at 18.7% was obtained by ammonium oxalate extraction of roselle calyx variety Acc.6 compared to only 9.77% by HCl extraction. The lowest pectin yield at 11.3% and 5.78% were observed respectively in ammonium oxalate and HCl extractions of roselle calyx variety UKMR-3. Some important characteristics of ammonium oxalate extracted pectin of roselle Acc.6 were 5.98% moisture, 3.81% ash, 4.64% methoxyl content, 42.24% anhydrouronic acid (AUA) and degree of esterification (DE) 60%. This study suggested that the high DE% roselle pectin is an alternative source of pectin for food industry.
Recycling waste cooking vegetable oils by reclaiming and using these oils as biodiesel feedstocks is one of the promising solutions to address global energy demands. However, producing these biodiesels poses a significant challenge because of their poor physicochemical properties due the high free fatty acid content and impurities present in the feedstock, which will reduce the biodiesel yields. Hence, this study implemented the following strategy in order to address this issue: (1) 70 vol% of waste cooking vegetable oil blended with 30 vol% of Calophyllum inophyllum oil named as WC70CI30 used to alter its properties, (2) a three-stage process (degumming, esterification, and transesterification) was conducted which reduces the free fatty acid content and presence of impurities, and (3) the transesterification process parameters (methanol/oil ratio, reaction temperature, reaction time, and catalyst concentration) were optimized using response surface methodology in order to increase the biodiesel conversion yield. The results show that the WC70CI30 biodiesel has favourable physicochemical properties, good cold flow properties, and high oxidation stability (22.4 h), which fulfil the fuel specifications stated in the ASTM D6751 and EN 14214 standards. It found that the WC70CI30 biodiesel has great potential as a diesel substitute without the need for antioxidants and pour point depressants.
Recently, rubber seed oil (RSO) has been considered as a promising potential oil source for biodiesel production. However, RSO is a non-edible feedstock with a significant high free fatty acid (FFA) content which has an adverse impact on the process of biodiesel production. In this study, ultrasonic-assisted esterification process was conducted as a pre-treatment step to reduce the high FFA content of RSO from 40.14% to 0.75%. Response surface methodology (RSM) using central composite design (CCD) was applied to the design of experiments (DOE) and the optimization of esterification process. The result showed that methanol to oil molar ratio was the most influential factor for FFA reduction whereas the effect of amount of catalyst and the reaction were both insignificant. The kinetic study revealed that the activation energy and the frequency factor of the process are 52.577kJ/mol and 3.53×108min-1, respectively.
The extraction of pectin from dragon fruit (Hylocereus polyrhizus) peels under three different extraction conditions was identified as an alternative source of commercial pectin. In this work, dried alcohol-insoluble residues (AIR) of dragon fruit peels were treated separately with 0.25% ammonium oxalate/oxalic acid at a pH of 4.6 at 85oC; 0.03 M HCl at a pH of 1.5 at 85oC; and de-ionized water at 75oC. The pectin obtained from these methods was compared in terms of yield, physicochemical properties and chemical structure. Fourier Transform Infrared Spectroscopy (FTIR) was used in the identification of dragon fruit pectins. The results showed that the pectin yield (14.96-20.14% based on dry weight), moisture content (11.13-11.33%), ash content (6.88-11.55%), equivalent weight (475.64-713.99), methoxyl content (2.98-4.34%), anhydrouronic acid (45.25-52.45%) and the degree of esterification (31.05-46.96%) varied significantly (p < 0.05) with the various extraction conditions used. Pectin extracted with ammonium oxalate gave the highest yield of pectin, with high purity and low ash content. Based on the value of methoxyl content and the degree of esterification, dragon fruit pectin can be categorized as low-methoxyl pectin.
Biodiesel was produced via transesterification of palm oil with methanol in the presence of CaO-Nb2O5 mixed oxide catalyst. Response surface methodology (RSM) with central composite design (CCD) was performed to determine the optimum operating conditions and to optimize the biodiesel yield. In this study, the reaction variables being optimized were reaction time, catalyst loading and methanol to oil molar ratio. From the analysis of variance (ANOVA), the most influential parameter on biodiesel production was reaction time. The predicted yield was found in good agreement with the experimental value, with R2= 0.9902. The optimum biodiesel yield of 97.67% was achieved at 2.67 h reaction time, with 3.60 wt. % of catalyst and with methanol to oil molar ratio of 13.04. The high biodiesel yield can be correlated to the synergic effect of basicity between the metallic ions of CaO-Nb2O5 shown in the physicochemical analysis.
An investigation on a batch production of palm kernel oil polyol (PKO-p) was conducted via esterification and condensation.
The process design was thoroughly studied as a preliminary step for future upscaling. The process variables included
necessity of vacuum pump, controlling of heating rate, recording the production time, nitrogen gas flow and agitator
speed. About 250 mL PKO-p was successfully synthesized within 3 h. Vacuum pressure was applied to haul out moisture
from the system. The control of heating rate and production time are vital to avoid sudden oxidation.
In this study, solid coconut waste and CaO/PVA was used as raw material and catalyst respectively to produce biodiesel through in situ transesterification. Both, raw material and catalyst were packed in a packed bed reactor. The reaction was fixed for 3 h and the mixing was kept constant at 350 rpm. The highest biodiesel yield of 95% was obtained at reaction temperature of 61 °C with catalyst loading (CaO/PVA) of 2.29 wt% and methanol to solid ratio of 12:1. CaO-waste derived catalyst has been successfully proven to be utilized as heterogeneous base catalyst for the production of biodiesel from solid coconut waste.