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.
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.
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.
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.
Kojic acid is widely used to inhibit the browning effect of tyrosinase in cosmetic and food industries. In this work, synthesis of kojic monooleate ester (KMO) was carried out using lipase-catalysed esterification of kojic acid and oleic acid in a solvent-free system. Response Surface Methodology (RSM) based on central composite rotatable design (CCRD) was used to optimise the main important reaction variables, such as enzyme amount, reaction temperature, substrate molar ratio, and reaction time along with immobilised lipase from Candida Antarctica (Novozym 435) as a biocatalyst. The RSM data indicated that the reaction temperature was less significant in comparison to other factors for the production of a KMO ester. By using this statistical analysis, a quadratic model was developed in order to correlate the preparation variable to the response (reaction yield). The optimum conditions for the enzymatic synthesis of KMO were as follows: an enzyme amount of 2.0 wt%, reaction temperature of 83.69°C, substrate molar ratio of 1:2.37 (mmole kojic acid:oleic acid) and a reaction time of 300.0 min. Under these conditions, the actual yield percentage obtained was 42.09%, which is comparably well with the maximum predicted value of 44.46%. Under the optimal conditions, Novozym 435 could be reused for 5 cycles for KMO production percentage yield of at least 40%. The results demonstrated that statistical analysis using RSM can be used efficiently to optimise the production of a KMO ester. Moreover, the optimum conditions obtained can be applied to scale-up the process and minimise the cost.
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.
A new class of biocomposites based on oil palm empty fruit bunch fiber and poly(butylene adipate-co-terephthalate) (PBAT), which is a biodegradable aliphatic aromatic co-polyester, were prepared using melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 wt% and characterized. Chemical treatment of oil palm empty fruit bunch (EFB) fiber was successfully done by grafting succinic anhydride (SAH) onto the EFB fiber surface, and the modified fibers were obtained in two levels of grafting (low and high weight percentage gain, WPG) after 5 and 6 h of grafting. The FTIR characterization showed evidence of successful fiber esterification. The results showed that 40 wt% of fiber loading improved the tensile properties of the biocomposite. The effects of EFB fiber chemical treatments and various organic initiators content on mechanical and thermal properties and water absorption of PBAT/EFB 60/40 wt% biocomposites were also examined. The SAH-g-EFB fiber at low WPG in presence of 1 wt% of dicumyl peroxide (DCP) initiator was found to significantly enhance the tensile and flexural properties as well as water resistance of biocomposite (up to 24%) compared with those of untreated fiber reinforced composites. The thermal behavior of the composites was evaluated from thermogravimetric analysis (TGA)/differential thermogravimetric (DTG) thermograms. It was observed that, the chemical treatment has marginally improved the biocomposites' thermal stability in presence of 1 wt% of dicumyl peroxide at the low WPG level of grafting. The improved fiber-matrix surface enhancement in the chemically treated biocomposite was confirmed by SEM analysis of the tensile fractured specimens.
A mathematical model describing chemical kinetics of transesterification of palm-based methyl esters with trimethylolpropane has been developed. The model was developed by utilizing nonlinear regression method, which is an efficient and powerful way to determine rate constants for both forward and reverse reactions. A comparison with previous study which excludes the reverse reactions was made. The model was based on the reverse mechanism of transesterification reactions and describes concentration changes of trimethylolpropane, monoesters and diesters production. The developed model was validated against data from the literature. The reaction rate constants were determined using MATLAB version 7.2 and the ratios of rate constants obtained were well in agreement with those reported in the literature. A good correlation between model simulations and experimental data was observed. It was proven that both methods were able to predict the rate constants with plausible accuracy.
Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol.
The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil.
The chemical production of methyl oleate using chemically synthesized fatty acid alcohols and other toxic chemicals may lead to significant environmental hazards to mankind. Being a highly valuable fatty acid replacement raw material in oleochemical industry, the mass production of methyl oleate via environmentally favorable processes is of concern. In this context, an alternative technique utilizing Candida rugosa lipase (CRL) physically adsorbed on multi-walled carbon nanotubes (MWCNTs) has been suggested. In this study, the acid-functionalized MWCNTs prepared using a mixture of HNO3 and H2SO4 (1:3 v/v) was used as support for immobilizing CRL onto MWCNTs (CRL-MWCNTs) as biocatalysts. Enzymatic esterification was performed and the efficiency of CRL-MWCNTs was evaluated against the free CRL under varying conditions, viz. temperature, molar ratio of acid/alcohol, solvent log P, and enzyme loading. The CRL-MWCNTs resulted in 30-110 % improvement in the production of methyl oleate over the free CRL. The CRL-MWCNTs attained its highest yield (84.17 %) at 50 °C, molar ratio of acid/alcohol of 1:3, 3 mg/mL of enzyme loading, and iso-octane (log P 4.5) as solvent. Consequently, physical adsorption of CRL onto acid-functionalized MWCNTs has improved the activity and stability of CRL and hence provides an environmentally friendly means for the production of methyl oleate.
Microwave-assisted synthesis is known to accelerate the transesterification process and address the issues associated with the conventional thermal process, such as the processing time and the energy input requirement. Herein, the effect of microwave irradiation on the transesterification of palm oil methyl ester (PME) with trimethylolpropane (TMP) was evaluated. The reaction system was investigated through five process parameters, which were reaction temperature, catalyst, time, molar ratio of TMP to PME and vacuum pressure. The yield of TMP triester at 66.9 wt.% and undesirable fatty soap at 17.4% were obtained at 130 °C, 10 mbar, sodium methoxide solution at 0.6 wt.%, 10 min reaction time and molar ratio of TMP to PME at 1:4. The transesterification of palm oil-based methyl ester to trimethylolpropane ester was 3.1 folds faster in the presence of microwave irradiation. The total energy requirement was markedly reduced as compared to the conventional heating method. The findings indicate that microwave-assisted transesterification could probably be an answer to the quest for a cheaper biodegradable biolubricant.
Interesterification reaction involves rearrangement of the fatty acid radicals on the glycerol backbone, either randomly (chemical interesterification) or regioselectivity (enzymatic interesterification). Refined, bleached and deodourised palm oil (RBDPO) and palm kernel oil (RBDPKO) were blended in ratios from 25:75 to 75:25 (wt/wt). All blends were subjected to enzymatic (EI) and chemical interesterification (CI) using Lipozyme TL IM (4% w/w) and sodium methoxide (0.2% m/m) as the catalysts, respectively. The effect of EI and CI on the triacylglycerol (TAG) composition, thermal behaviour, polymorphism, crystal morphology and crystallisation kinetics were studied. The aim of this research is to characterise the nature of crystals in food product for certain desired structure. The crystallisation behaviour discussed in this study involves microstructure (PLM), polymorphism (XRD), thermal properties and crystallisation kinetics by DSC. The alteration in TAG composition was greater after CI as compared to EI with the reduction of LaLaLa (from 11.00% to 5.15%) and POO (from 14.28% to 4.87%). The DSC complete melting and crystallisation temperature of blend with 75% PO increased after CI, from 39.58 °C to 41.67 °C and from -30.84 °C to -28.33 °C, respectively. EI contributed to finer crystals than CI. However, the β' and β polymorph mixture and crystallisation kinetics (n = 2) of PO-PKO blends did not change after CI and EI. The knowledge on controlling crystallisation of RBDPO and RBDPKO blends is vital for proper processing condition like margarine production.
The potential of new trimetallic (Ce, Cu, La) loaded montmorillonite clay catalyst for synthesizing biodiesel using novel non-edible Celastrus paniculatus Willd seed oil via two-step transesterification reaction has been reported along with catalyst characterization. Transesterification reaction was optimized and maximum biodiesel yield of 89.42% achieved under optimal operating reaction states like; 1:12 oil to methanol ratio, 3.5% of catalyst amount, 120 °C of reaction temperature for 3 h. The predicted and experimental biodiesel yields under these reaction conditions were 89.42 and 89.40%, which showing less than 0.05% variation. Additionally, optimum biodiesel yield can be predicted by drawing 3D surface plots and 2D contour plots using MINITAB 17 software. For the characterization of the obtained biodiesel, analysis including the GC/MS, FT-IR, 1H NMR and 13C NMR were applied. The fuel properties of obtained biodiesel agrees well with the different European Union (EU-14214), China (GB/T 20828), and American (ASTM-951, 6751) standards.
Citric acid (CA) can be found naturally in fruits and vegetables, particularly citrus fruit. CA is widely used in many fields but its usage as a green modifying agent and binder for wood is barely addressed. Esterification is one of the most common chemical reactions applied in wood modification. CA contains three carboxyl groups, making it possible to attain at least two esterification reactions that are required for crosslinking when reacting with the hydroxyl groups of the cell wall polymers. In addition, the reaction could form ester linkages to bring adhesivity and good bonding characteristics, and therefore CA could be used as wood binder too. This paper presents a review concerning the usage of CA as a wood modifying agent and binder. For wood modification, the reaction mechanism between wood and CA and the pros and cons of using CA are discussed. CA and its combination with various reactants and their respective optimum parameters are also compiled in this paper. As for the major wood bonding component, the bonding mechanism and types of wood composites bonded with CA are presented. The best working conditions for the CA in the fabrication of wood-based panels are discussed. In addition, the environmental impacts and future outlook of CA-treated wood and bonded composite are also considered.
Catalytic esterification of glycerol with oleic acid (OA) was optimized over hydrophobic mesoporous zirconia-silica heterogeneous acid catalyst (ZrO2-SiO2-Me&Et-PhSO3H) and benchmarked with commercial catalysts (Aquivion and Amberlyst 15) in order to examine the effect of catalyst acidity on conversion, yield and product selectivity. The process optimisation results showed an 80% conversion with a 59.4% glycerol mono-oleate (GMO) and 34.6% glycerol dioleate (GDO) selectivities corresponding to a combined GMO and GDO selectivity of 94.8% at equimolar OA-to-glycerol ratio, 160°C reaction temperature, 5 wt% catalyst concentration with respect to the OA weight and 4 h reaction time. This work reveals that the hydrophobic and mild acidic ZrO2-SiO2-Me&Et-PhSO3H catalyst outperformed Amberlyst 15 and Aquivion with a yield of 82% and GMO selectivity of 60%. It is found that catalyst acidity is a key parameter for catalytic activity and conversion rate. Nevertheless, high acidity/acid strength reduced the product yield in the glycerol esterification of OA.