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.
Some unidentified minor compounds have been observed in the residue from short-path distillation of transesterified palm oil that are not detected in the original palm oil. A method combining short-path distillation to enrich the unknowns with fractionation using solid-phase extraction is described. The fractionated components were identified using GC coupled with MS. The transesterified palm oil was found to contain methyl esters of up to C32 carbon atoms. In the very long chain FAME with carbon numbers > or = 20, both even and odd carbon numbers accounted for 0.26 wt%, with C24 and C26 being the major ones present in the residue after short-path distillation of transesterified palm oil.
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.
In this study we used a laser ablation technique for preparation of silver nanoparticles. The fabrication process was carried out by ablation of a silver plate immersed in palm oil. A pulsed Nd:YAG laser at a wavelength of 1064 nm was used for ablation of the plate at different times. The palm coconut oil allowed formation of nanoparticles with very small and uniform particle size, which are dispersed very homogeneously within the solution. The obtained particle sizes for 15 and 30 minute ablation times were 2.5 and 2 nm, respectively. Stability study shows that all of the samples remained stable for a reasonable period of time.
The melting curves of 11 vegetable oils have been characterised. Vegetable oil samples that were cooled at a constant rate (5 degrees C/min) from the melt showed between one and seven melting endotherms upon heating at four different heating rates (1, 5, 10 and 20 degrees C/min) in a differential scanning calorimeter (DSC). Triacylglycerol (TAG) profiles and iodine value analyses were used to complement the DSC data. Generally, the melting transition temperature shifted to higher values with increased rates of heating. The breadth of the melting endotherm and the area under the melting peak also increased with increasing heating rate. Although the number of endothermic peaks was dependent on heating rate, the melting curves of the oil samples were not straightforward in that there was no correlation between the number of endothermic peaks and heating rates. Multiple melting behaviour in DSC experiments with different heating rates could be explained by: (1) the melting of TAG populations with different melting points; and (2) TAG crystal reorganisation effects. On the basis of the corollary results obtained, vegetable oils and fats may be distinguished from their offset-temperature (Toff) values in the DSC melting curves. The results showed that Toff values of all oil samples were significantly (p < 0.01) different in the melting curves scanned at four different scanning rates. These calorimetric results indicate that DSC is a valuable technique for studying vegetable oils.
CO2 gasification of oil palm shell (OPS) char to produce CO through the Boudouard reaction (C + CO2 ↔ 2CO) was investigated under microwave irradiation. A microwave heating system was developed to carry out the CO2 gasification in a packed bed of OPS char. The influence of char particle size, temperature and gas flow rate on CO2 conversion and CO evolution was considered. It was attempted to improve the reactivity of OPS char in gasification reaction through incorporation of Fe catalyst into the char skeleton. Very promising results were achieved in our experiments, where a CO2 conversion of 99% could be maintained during 60 min microwave-induced gasification of iron-catalyzed char. When similar gasification experiments were performed in conventional electric furnace, the superior performance of microwave over thermal driven reaction was elucidated. The activation energies of 36.0, 74.2 and 247.2 kJ/mol were obtained for catalytic and non-catalytic microwave and thermal heating, respectively.
Many kinetics studies on methanolysis assumed the reactions to be irreversible. The aim of the present work was to study the dynamic modeling of reversible methanolysis of Jatropha curcas oil (JCO) to biodiesel. The experimental data were collected under the optimal reaction conditions: molar ratio of methanol to JCO at 6 : 1, reaction temperature of 60°C, 60 min of reaction time, and 1% w/w of catalyst concentration. The dynamic modeling involved the derivation of differential equations for rates of three stepwise reactions. The simulation study was then performed on the resulting equations using MATLAB. The newly developed reversible models were fitted with various rate constants and compared with the experimental data for fitting purposes. In addition, analysis of variance was done statistically to evaluate the adequacy and quality of model parameters. The kinetics study revealed that the reverse reactions were significantly slower than forward reactions. The activation energies ranged from 6.5 to 44.4 KJ mol⁻¹.
The stearin fraction of palm-based diacylglycerol (PDAGS) was produced from dry fractionation of palm-based diacylglycerol (PDAG). Bakery shortening blends were produced by mixing PDAGS with either palm mid fraction, PMF (PDAGS/PMF), palm olein, POL(PDAGS/POL) or sunflower oil, SFO (PDAGS/SFO) at PDAGS molar fraction of XPDAGS=0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%. The physicochemical results obtained indicated that C16:0 and C18:1 were the dominant fatty acids for PDAGS/PMF and PDAGS/POL, while C18:1 and C18:2 were dominant in the PDAGS/SFO mixtures. SMP and SFC of the PDAGS were reduced with the addition of PMF, POL and SFO. Binary mixtures of PDAGS/PMF had better structural compatibility and full miscibility with each other. PDAGS/PMF and PDAGS/SFO crystallised in β'+β polymorphs in the presence of 0.4-0.5% PDAGS while PDAGS/POL resulted in β polymorphs crystal. The results gave indication that PDAGS: PMF at 50%:50% and 60%:40% (w/w) were the most suitable fat blend to be used as bakery shortening.
The aim of this study was to investigate the effect of atmospheric frying followed by drainage under vacuum on the stability of oil, compared to similar frying with drainage at atmospheric pressure. Changes in the oil were assessed by the free fatty acid (FFA) content, p-anisidine value (AnV), colour, viscosity, fatty acid profile and concentration of tocols. The rate of FFA formation in the case of vacuum drainage was found to be about half that of atmospheric drainage. Oil deterioration by oxidation and polymerisation was also reduced by the use of vacuum drainage. The AnV of the oil after vacuum drainage was lower by about 12%, the total colour difference was improved by 14% and viscosity was slightly reduced after 5 days of frying, compared to the values for oil that had been drained at atmospheric pressure. There was a reduction in the loss of polyunsaturated fatty acids in the case of vacuum drainage after 5 days of frying but differences in retention of tocols were only evident in the first two days of frying.
High PHA production and storage using palm oil mill effluent (POME) was investigated using a laboratory batch Bio-PORec® system under aerobic-feeding conditions. Results showed that maximum PHA was obtained at a specific rate (q(p)) of 0.343 C-mol/C-molh when air was supplied at 20 ml/min. The PHA yield was found to be 0.80 C-mol/C-mol acetic acid (HAc) at microaerophilic condition and the mass balance calculation showed that PHA production increased up to 15.68±2.15 C-mmol/cycle. The experiments showed that short feeding rate, limited requirements for electron acceptors (e.g. O(2), NO(3)) and nutrients (N and P) showed lower tendency of glycogen accumulation and contributed more to PHA productivity.
Hydrodistillation of the fresh leaves of Alpinia mutica afforded 0.005% colourless essential oil. GC and GC-MS analysis revealed the presence of 33 components accounting for 92.9% of the total oil, dominated by 20 sesquiterpenes (76.7%) and 10 monoterpenes (8.3%). The major constituent was found to be β-sesquiphellandrene which was 29.2% of the total oil. Soxhlet extraction, followed by repeated column chromatography of the dried leaves yielded two phenolic compounds, identified as 5,6-dehydrokawain and aniba dimer A, together with one amide assigned as auranamide. The structures of these compounds were determined by using spectroscopic analysis. Antibacterial screening of the essential oil, the crude and isolated compounds showed weak to moderate inhibitory activity.
In this study, optical and thermal properties of normal grade and winter grade palm oil biodiesel were investigated. Surface Plasmon Resonance and Photopyroelectric technique were used to evaluate the samples. The dispersion curve and thermal diffusivity were obtained. Consequently, the variation of refractive index, as a function of wavelength in normal grade biodiesel is faster than winter grade palm oil biodiesel, and the thermal diffusivity of winter grade biodiesel is higher than the thermal diffusivity of normal grade biodiesel. This is attributed to the higher palmitic acid C(16:0) content in normal grade than in winter grade palm oil biodiesel.
The essential oils obtained by hydrodistillation of the rhizomes of Alpinia aquatica Rosc. syn. Alpinia melanocarpa and Alpinia malaccensis Roscoe were analysed by capillary gas chromatography and gas chromatography-mass spectrometry. Eighteen compounds, representing 98.4% of the essential oil were identified in A. aquatica rhizome oil, with β-sesquiphellandrene in 36.5% being the major constituent, while 20 compounds representing 99.7% of the rhizome oil of A. malaccensis were identified, among which methyl (E)-cinnamate (78.2%) was the major constituent.
Red fruit (Pandanus conoideus Lam) is endemic plant of Papua, Indonesia and Papua New Guinea. The price of its oil (red fruit oil, RFO) is 10-15 times higher than that of common vegetable oils; consequently, RFO is subjected to adulteration with lower price oils. Among common vegetable oils, canola oil (CaO) and rice bran oil (RBO) have similar fatty acid profiles to RFO as indicated by the score plot of principal component analysis; therefore, CaO and RBO are potential adulterants in RFO.
The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.
Decomposition of oil palm fruit press fiber (FPF) to various liquid products in subcritical water was investigated using a high-pressure autoclave reactor with and without the presence of catalyst. When the reaction was carried in the absence of catalyst, the conversion of solid to liquid products increased from 54.9% at 483 K to 75.8% at 603 K. Simultaneously, the liquid yield increased from 28.8% to 39.1%. The liquid products were sub-categorized to bio-oil (benzene soluble, diethylether soluble, acetone soluble) and water soluble. When 10% ZnCl(2) was added, the conversion increased slightly but gaseous products increased significantly. However, when 10% Na(2)CO(3) and 10% NaOH were added independently, the solid conversion increased to almost 90%. In the presence of catalyst, the liquid products were mainly bio-oil compounds. Although solid conversion increased at higher reaction temperature, but the liquid yield did not increase at higher temperature.
Fatty amides have been successfully synthesized from palm olein and urea by a one-step lipase catalyzed reaction. The use of immobilized lipase as the catalyst for the preparation reaction provides an easy isolation of the enzyme from the products and other components in the reaction mixture. The fatty amides were characterized using Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance ((1)H NMR) technique and elemental analysis. The highest conversion percentage (96%) was obtained when the process was carried out for 36 hours using urea to palm oil ratio of 5.2: 1.0 at 40 degrees C. The method employed offers several advantages such as renewable and abundant of the raw material, simple reaction procedure, environmentally friendly process and high yield of the product.
Palm oil is the richest source of natural carotenes, comprising 500-700 ppm in crude palm oil (CPO). Its concentration is found to be much higher in oil extracted from palm-pressed fiber, a by-product from the milling of oil palm fruits. There are 11 types of carotenes in palm oil, excluding the cis/trans isomers of some of the carotenes. Qualitative separation of these individual carotenes is particularly useful for the identification and confirmation of different types of oil as the carotenes profile is unique to each type of vegetable oil. Previous studies on HPLC separation of the individual palm carotenes reported a total analyses time of up to 100 min using C30 stationary phase. In this study, the separation was completed in <5 min. The qualitative separation was successfully carried out using a commonly used stationary phase, C18.
The effects of scanning rates (1, 5, 10 and 20 degrees C/min) on the DSC cooling profiles of 11 vegetable oils have been determined in order to monitor peak transition temperatures, onset temperatures and crystallisation enthalpies. Triacylglycerol (TAG) profiles and iodine value analyses were used to complement the DSC data. The melted samples exhibited complicated crystallising exotherms. As the cooling rate increased, the crystallisation temperature decreased and the breadth of the crystallisation exotherm on cooling from the melt increased. In addition, the intensity of the exothermic peak increased somewhat when the cooling rate was increased. At slow cooling rates, TAG had more time to interact. It is conceivable that, at a low cooling rate (1 degree C/min), a prominent exotherm would be observed on crystallisation of vegetable oils and fats. The occurrence of one exotherm upon cooling indicated the co-crystallisation of the TAG upon slow cooling. On the basis of the corollary results obtained, vegetable oils may be differentiated by their onset temperature (Ton) values in the DSC cooling curves. Generally, there was a shift of Ton toward lower values with increasing cooling rates.
Torrefaction process of biomass material is essential in converting them into biofuel with improved calorific value and physical strength. However, the production of torrefied biomass is loose, powdery, and nonuniform. One method of upgrading this material to improve their handling and combustion properties is by densification into briquettes of higher density than the original bulk density of the material. The effects of critical parameters of briquetting process that includes the type of biomass material used for torrefaction and briquetting, densification temperature, and composition of binder for torrefied biomass are studied and characterized. Starch is used as a binder in the study. The results showed that the briquette of torrefied rubber seed kernel (RSK) is better than torrefied palm oil shell (POS) in both calorific value and compressive strength. The best quality of briquettes is yielded from torrefied RSK at the ambient temperature of briquetting process with the composition of 60% water and 5% binder. The maximum compressive load for the briquettes of torrefied RSK is 141 N and the calorific value is 16 MJ/kg. Based on the economic evaluation analysis, the return of investment (ROI) for the mass production of both RSK and POS briquettes is estimated in 2-year period and the annual profit after payback was approximately 107,428.6 USD.