EFFECT OF DEGUMMING PROCESS ON CHROMATOGRAPHIC SEPARATION OF CAROTENES FROM CRUDE AND DEGUMMED PALM OIL

Carotene from crude palm oil (CPO) and degummed palm oil (DPO) was separated using synthetic polymer adsorption chromatography. Diaion HP-20 adsorbent was used for reverse-phase chromatography and column temperature was kept at 50C. Both 2-propanol and n-hexane were used as the first and the second eluting solvents, respectively. Phosphoric acid was used to remove the minor components in CPO in the degumming process. The turbidity of DPO was lower than that of CPO and the retention time in the column for DPO was shorter (21.3 min) compared to CPO (29 min) due to the removal of the minor components by phosphoric acid. Degumming process caused a reduction of 1.67 mg of total carotene content and 55.67 ppm of carotene concentration in CPO. This is probably due to the removal of carotenoids during the degumming process. After column chromatography, carotene recovery for CPO was 30.23% and 54.82% for the first and second fractions, respectively. On the other hand, carotene recovery for DPO was 33.91% for the first fraction and 46.25% for the second fraction. This indicated that the separation of carotene in CPO was more efficient than DPO in the column chromatography due to the longer retention time in the column.     

OPTIMIZATION OF CAROTENE RECOVERY FROM HYDROLYZED PALM OLEIN IN ADSORPTION COLUMN CHROMATOGRAPHY USING RESPONSE SURFACE METHODOLOGY

Response Surface Methodology (RSM) for optimization of carotene recovery from hydrolyzed palm olein (HCPOlein) in adsorption chromatography was carried out. The level and interaction of three independent variables was investigated: column temperature (50 to 60C), oil loading (25 to 200 g), and mobile phase flow rate (6 to 60 mL/min). Based on the response as percentage of carotene recovery from 50 g of HP-20 adsorbent, the optimum conditions were achieved at 200 g of oil loading, column temperature at 55C, and flow rate at 33 mL/min. Up to 98% of carotene recovery was obtained under these conditions. Interaction of oil-oil, oil-flow rate and flow rate-flow rate could enhance the percentage of carotene recovery. However, oil and flow rate as single factors could significantly reduce percentage of carotene recovery. Oil loading as a single factor could positively influence the amount of carotene adsorbed. However, flow rate as a single factor and oil-oil interaction could negatively influence the amount of carotene adsorbed. The mean of difference (MD) of the experimental and predicted data for percentage of carotene recovery and the amount of carotene adsorbed were very small, −0.0067 and 0.0133, respectively. The probability (P) value showed no significant lack-of-fit for both equations in this model.     

PROCESSING OF CRUDE PALM OIL WITH CERAMIC MICROFILTRATION MEMBRANE

Membrane separation technology offers a potential application in the processing of crude palm oil. Ceramic membranes with different pore diameters (0.45 and 0.2 micron) were used to conduct the study on micromembrane process. Quality parameters of membrane-processed oils examined included free fatty acid (FFA), carotene, fatty acid composition (FAC), phosphorus and iron contents. The effect of operating parameters such as transmembrane pressure, feed flow and time on permeate flux were evaluated. It was found that 'Ceraflo'ceramic membrane with a pore size of 0.45 micron was only able to reject 14% of phosphorus from the crude oil. Ceramic membrane with pore size of 0.2 micron showed a better phosphorus rejection of 56.8%. The permeate was found to contain 7.13 ppm of phosphorus. The 0.2 micron membrane was also able to remove more than 80% of the iron from crude palm oil. Pore sizes for both membranes were not small enough to remove other components such as FFA, and carotene. Both membranes showed a similar trend in which the permeate flux increased with transmembrane pressure and feed flow until a certain limit where the flux declined with increasing pressure and feed flow. The limits in transmembrane pressures for membrane with pore sizes of 0.45 and 0.2 micron were 1.65 and 1.25 bar, respectively. Whereas the limits in feed flow for 0.45 micron and 0.2 micron membranes were 9.2 and 9.8 L/min     

SEPARATION OF TOCOPHEROLS AND TOCOTRIENOLS FROM PALM FATTY ACID DISTILLATE USING HYDROLYSIS-NEUTRALIZATION-ADSORPTION CHROMATOGRAPHY METHOD

Vitamin E from palm fatty acid distillate (PFAD) was concentrated in this study by removing the extraneous matters, especially free fatty acids (FFA) and acylglycerols. Original PFAD used in this study contained 85 and 13.7% of FFA and acylglycerols, respectively. Acylglycerols in PFAD were first hydrolyzed using commercially available immobilized Candida antarctica lipase at 60C for 6 h. The fatty acids liberated, together with the existing FFA were then removed by neutralization. Hydrolysis followed by neutralization step concentrated vitamin E from an initial amount of 0.37 to 4.32%. Hydrolysis was an important step as without hydrolysis, neutralization could only concentrate vitamin E to 1.80%. Oil extracted from hydrolyzed and neutralized PFAD was then subjected to a normal-phase silica adsorption chromatography. The column was first eluted with hexane followed by isopropanol. A large amount of acylglycerols was removed during the first elution, while vitamin E was desorbed by isopropanol, with a recovery of >90%. Vitamin E concentration after hydrolysis, neutralization and adsorption chromatography was 15.2%. The method described in this study offers an alternative for the existing separation methods. It could be applied as one of a series of steps in producing high-purity vitamin E concentrates.     

VISCOELASTIC PROPERTIES OF TABLE MARGARINE PREPARED FROM LIPASE-CATALYZED TRANSESTERIFIED MIXTURES OF PALM STEARIN AND PALM KERNEL OLEIN

A controlled-stress rheometer was used to evaluate dynamic viscoelastic (VE) performance of an experimental table margarine prepared from a transesterified palm stearin (PS):palm kernel olein (PKO) mixture (40:60 ratio) using Rhizomucor miehei lipase as the biocatalyst. Comparison was made using a commercial table margarine made of palm oil and palm kernel oil. The experiments were carried out over a period of three months with the margarines kept at 20 and     

RANDOMNESS TEST OF FATTY ACIDS DISTRIBUTION IN TRIACYLGLYCEROL MOLECULES OF PALM OIL

For food purposes, the palm oil is generally fractionated to solid (stearin) and liquid (olein) fractions. Distribution of fatty acids in triacylglycerols of palm oil determines the fate of fractionation in terms of yield and quality of the products, specifically the liquid fraction or olein. The more trisaturated and triunsaturated and the less mono- and disaturated will yield higher and better quality olein. There are six types of fatty acids found in the palm oil, but only 14 combinations are found in the triacylglycerols. In this study, such combinations were statistically tested to determine whether or not the fatty acids are randomly distributed, and if it was not, toward which direction the regulatory agent works. The distribution of fatty acids in the palm oil triacylglycerols was found to be nonrandomly distributed. Unfortunately, the palm tended to form 11.98% higher disaturated triacylglycerols, −7.4% less triunsaturated, and −4.25% less trisaturated compared to when the arrangement was random. If manipulation could be induced in such a way that the synthesis of triacylglycerols becomes random, the triunsaturated and trisaturated triacylglycerol proportion expectedly would increased to 12.57% and 12.43%, respectively. Such manipulation can be done in the plant through genetic engineering, or in the harvestedpuit through application of stimulant, or in the oil through chemical or enzymatic transesterification.     

OPTIMIZATION OF CHEMICAL TRANSESTERIFICATION OF PALM OIL USING RESPONSE SURFACE METHODOLOGY

The effect of catalyst concentration (0.1–0.5% methoxide powder), temperature (50–92C), and time (30–480 min) of chemical transesterification was studied to determine the optimum condition for maximizing concentration of triunsaturated and trisaturated triacylglycerols (TG) in palm oil. TG compositions of the oil were analysed using high-performance liquid chromatography. The optimum condition of the process was determined using statistical response surface methodology. The results showed that the triunsaturated and trisaturated TG responses followed a second order form of the treatments with R²= 0.83 and 0.85, respectively. The triunsaturated TG reached a maximum concentration by using 0.36% catalyst at 78C and 360 min reaction time, whereas the trisaturated TG with 0.36% catalyst at 81C and 325 min reaction time. Considering the two responses, it was concluded that the overall optimum condition could be achieved at 0.36% of catalyst at 78–81C and 325–360 min reaction time. Such conditions increased trisaturated TG in palm oil by 2.34 times and triunsaturated TG by 1.54 times.     

MONITORING OF TRANSESTERIFICATION OF PALM OIL BY DIFFERENTIAL SCANNING CALORIMETRY

Chemical transesterification was conducted to obtain triacylglycerol ( TG) containing maximum concentrations of trisaturated and triunsaturated TG in palm oil. Catalyst (sodium methoxide) concentration of 0.1–0.5%, reaction temperature of 50–92C and reaction time of 30–480 min were applied in 20 treatments. Concentrations of trisaturated and triunsaturated TG, as well as melting points and iodine values were monitored by differential scanning calorimetric (DSC) techniques. The results showed that maximum trisaturated and triunsaturated TG achieved for refined-bleached-deodorized (RBD) palm oil were 17.10 and 7.50%, respectively, using 0.42% catalyst, at 58C in 389 min. These amounts were higher compared to control (untransesterified) RBD palm oil i.e 7.45 and 4.92%, respectively. The melting points of the products were higher compared to the control, while the iodine values were not significantly changed in all of the treatments.     

COMPARISON OF THE FRYING PERFORMANCE OF REFINED, BLEACHED AND DEODORIZED PALM OLEIN AND COCONUT OIL

The frying performance of refined, bleached and deodorized palm olein (RBDPO) and refined, bleached and deodorized coconut oil (RBDCO) was compared in this study. The oils were studied during intermittent frying of potato chips at 180C for 5 h/day for 5 consecutive days. The indices used for assessment of frying performance of the oils were fatty acid composition (FAC), peroxide value (PV), anisidine value (AnV), % free fatty acid (FFA), iodine value (IV), % polar component, polymer content, color, viscosity, smoke point and foaming tendency. The results showed that RBDPO was superior to RBDCO in frying performance in terms of % FFA, iodine value, foaming tendency and smoke point. However, RBDCO performed better than RBDPO with respect to % polar component, polymer content, resistance to oxidation, color and viscosity. Flavor evaluation showed that potato chips fried in RBDPO were preferred by the panelists.     

ADSORPTION ISOTHERM STUDIES OF PALM CAROTENE EXTRACTION BY SYNTHETIC POLYMER ADSORBENT

The use of different synthetic polymer resin adsorbents, including HP 20, Exa 31, Exa 32 and Exa 50 for the removal of carotenes from crude palm oil was investigated. The adsorption of carotene was determined using several adsorption isotherm models such as Langmuir and Scatchard plots. The Langmuir adsorption model was found to be sufficient to describe the adsorption of carotenes by using these four types of resins, suggesting that the process was favorable, saturable and an equilibrated mechanism. A curve of Scatchard transformation plot showed that the adsorption involves multiple binding sites. The maximum uptake capacity of all resins used in isopropanol (IPA) was about 5 fold higher than the maximum uptake capacity obtained in n-hexane. The adsorbent found to be most efficient for carotene was HP 20 for experiment carried out in IPA. The carotenes concentration obtained by HP 20 in IPA was 31.44 mg/L compared to 7.12 mg/L obtained in n-hexane.     

RAPID DETERMINATION OF PEROXIDE VALUE IN CRUDE PALM OIL PRODUCTS USING FOURIER TRANSFORM INFRARED SPECTROSCOPY

A rapid Fourier transform infrared (FTIR) spectroscopic technique coupled with fixed NaCl cell (1 mm pathlength) was developed to measure peroxide value (PV) in crude palm oil (CPO) and crude palm kernel oil (CPKO). Calibration standards were prepared by oxidizing CPO in a fermentor at 60C over a period of 24 h. A partial least squares (PLS) calibration model for predicting PV was developed based on the 3710–3210 cm^-1spectral region with reference to a single-point baseline at 3710 cm^-1. The optimization of calibration factors was guided by the predicted residual error sum of squares (PRESS) test. The standard deviation (SD) of the calibration obtained was 0.46 PV over the range of 0.51–17.82 PV and the correlation coefficient (R2) was 0.998. The model was validated with an independent set of samples consisting of both laboratory and field samples. The overall SD for the validation set was sligthly higher (SD = 1.46 PV) with R2 of 0.989. Thus, it was demonstrated that PV measured by FTIR techniques was comparable to that obtained by the chemical method. The FTIR method has the     

PRODUCTION OF PALM OIL REFERENCE MATERIALS FOR THE DETERMINATION OF SOLID FAT CONTENT

ABSTRACT

Three palm oil reference materials were produced for solid fat content analysis employing the Malaysian Palm Oil Board (MPOB) Test Methods. Thirteen laboratories participated in the characterization study, where the solid fat content in palm oil, palm olein and palm stearin were identified at temperature range from 0 to 45C. The consensus values were calculated based on the acceptability of statistical results from collaborating laboratories. Both of the consensus values and their uncertainties (%) for each reference material are as follows: 71.12 ± 1.82% (0C), 54.07 ± 1.05% (10C), 37.44 ± 0.88% (15C), 24.18 ± 1.09% (20C), 13.32 ± 0.86% (25C), 7.64 ± 0.28% (30C), 4.05 ± 0.14% (35C) and 1.25 ± 0.49% (40C) for SFC of palm oil, 66.32 ± 1.93% (0C), 43.53 ± 1.32% (10C), 22.50 ± 0.78% (15C), 6.68 ± 1.14% (20C) and 1.40 ± 0.35% (25C) for SFC of palm olein, and 78.09 ± 1.23% (0C), 67.66 ± 0.71% (10C), 56.29 ± 1.18% (15C), 44.37 ± 1.13% (20C), 30.22 ± 1.25% (25C), 20.08 ± 0.58% (30C), 13.72 ± 0.32% (35C), 8.97 ± 0.72% (40C) and 5.06 ± 0.41% (45C) for solid fat content of palm stearin.

PRACTICAL APPLICATIONS

The implementation of the ISO 17025 accreditation should be encouraged for testing laboratories to assure the traceability of analysis performed. This accreditation requires the use of certified reference materials to ensure that the analysis performed is parallel to the ISO 17025 standards. However, the unavailability of palm oil reference materials will affect the implementation of such standards for laboratories that are performing palm oil analyses. Hence, this study is aimed to characterize and certify the palm oil reference materials for determination of solid fat content. The establishment of this study is hoped to increase the credibility of laboratories, which are involved in the palm oil analysis. This will also promote the Malaysia Palm Oil Board as a center for the certification of palm oil reference materials.     

QUALITY CHANGES OF REFINED-BLEACHED-DEODORIZED (RBD) PALM OLEIN, SOYBEAN OIL AND THEIR BLENDS DURING DEEP-FAT FRYING

The quality changes of refined, bleached and deodorized palm olein (RBDPO) and soybean oil (SBO) and their blends were investigated in this study. The oils were studied during intermittent frying of potato chips at 180PT5C for 5 h per day for 5 consecutive days. The indices used for assessment of changes in quality of the oils were fatty acid composition (FAC), peroxide value (PV), anisidine value (AnV), % free fatty acid (FFA), iodine value (IV), % polar component, polymer content, color, viscosity, smoke point and foaming tendency. The results showed that RBDPO was superior to SBO in frying performance in terms of resistance to oxidation, changes in IV, AnV, foaming tendency, % polar component and polymer content. However, SBO performed better than RBDPO with respect to color, viscosity, FAA content and smoke point. Sensory evaluation showed that potato chips fried in both RBDPO and SBO were equally acceptable by the panelists.     

SHELF-LIFE OF FRIED POTATO CHIPS USING RBD PALM OLEIN, SOYBEAN OIL AND THEIR BLENDS

Shelf-life of potato chips fried in refined, bleached and deodorized palm olein (RBDPO), soybean oil (SBO) and their blends was evaluated. Potato slices were fried for 130 s at 180 PT 5C at 30 min intervals over a period of 5 h/day for 5 consecutive days. Indicators of frying oil quality with the shelf-life of fried products chosen were total polar component and acid value. This study indicated that RBDPO was better than SBO for the preparation of fried potato chips in terms of shelf-life of products. The blends were also slightly better than SBO with increasing proportion of RBDPO. However, the effects were minimal on the rate of development of rancidity in fried products beyond the fourth day of frying in the frying medium.     

A study on monitoring of frying performance and oxidative stability of cottonseed and palm oil blends in comparison with original oils

Blending polyunsaturated oils with highly saturated or monounsaturated oils has been studied extensively; however, in literature there is negligible information available on the blending of refined cottonseed oil with palm olein oil. Blending could enhance the stability and quality of cottonseed oil during the frying process. In the present study, the effects of frying conditions on physicochemical properties of the palm olein-cottonseed oil blends (1:0, 3:2, 1:1, 2:3, and 0:1, w/w) were determined and compared to the pure oils. The frying process of frozen French fries was performed in duplicate at 170 ± 5°C for 10 h without interruption. The oil degradations were characterized during deep-frying applications; peroxide, free fatty acid, and iodine value by standardized methods, fatty acid profile by using a gas chromatography-flame ionization detector, polar and polymeric compounds by using the high-performance size exclusion chromatography/evaporative light scattering detector technique. The present study clearly indicated that the oxidative and frying performances of pure palm olein oil and cottonseed oil significantly improved by blending application. Results clearly indicated that the frying performance of cottonseed oil significantly improved by the blending with palm olein oil. Except that free fatty acid content, all the physicochemical variables were significantly influenced by type of pure and blend oils. By increasing the proportion of palm olein oil in cottonseed oil, the levels of polyunsaturated fatty acids decreased, while saturated fatty acid content increased. The progression of oxidation was basically followed by detecting polar and polymeric compounds. The fastest increments for polar and polymeric compounds were found as 6.30% level in pure cottonseed oil and as 7.07% level in 40% cottonseed oil:60% palm olein oil blend. The least increments were detected as 5.40% level in 40% cottonseed oil:60% palm olein oil blend and 2.27% level in 50% cottonseed oil:50% palm olein oil blend. These levels were considerably below the acceptable levels recommended by the official codex. Therefore, the present study suggested that blending of cottonseed oil with palm olein oil provided the oil blends (50% cottonseed oil:50% palm olein oil and 40% cottonseed oil:60% palm olein oil, w/w) with more desirable properties for human nutrition.     

MICROSTRUCTURE of PEANUT BUTTER STABILIZED WITH PALM OIL

Free oil separation is a problem in "natural" peanut butter. Studies have indicated that palm oil functions as an effective stabilizer in peanut butter. This study was undertaken to determine the effect of palm oil on microstructural features of peanut butter. Samples containing 0, 1.5 and 2.5% palm oil and a control containing hydrogenated vegetable oils were prepared and stored at 0C and 45C for 130 days. Microstructure was examined by light microscopy. Addition of palm oil in peanut butter markedly increased spatial distribution of protein bodies and cell wall fragments when compared to nonstabilized products. Palm oil has potential as a stabilizer in peanut butter, but shelf-life stability is likely to be less than that achieved with presently used stabilizers, at elevated temperatures due to a less stable microstructure resulting in a lower level of solid dispersion in the continuous oil phase.     

THE RECOVERY OF USED FRYING OILS WITH VARIOUS ADSORBENTS

The recovery of used frying oils is of commercial and economic importance. One additional reuse of recovered oil could provide considerable savings to the food processors. Seven commonly used filter aids: Silasorb, Britesorb, HB 600, Purifry, Frypowder, Activated Carbon, and Magnesol, as well as two commercially unavailable adsorbents, Sorbead AF and Calsilite were studied. A number of AOCS official methods were used to evaluate their adsorptiveness, free fatty acids (FFA), conjugated diene value (CDV), total polar components (TPC), oxidative stability index (OSI), color and viscosity (V). High performance size exclusion chromatography was employed to determine the amount of polymers and low molecular weight compounds. When heated to 150C prior to filtration, HB 600 was found to reduce FFA content by 84.5%. Frypowder improved oil stability by 38.3%, and Magnesol lightened oil color by 46.3%. After statistical analysis of the data, five of them were selected, two or three of which were blended to obtain the most effective combination. The blending of HB 600 and Magnesol reduced FFA and TPC by 90.8–93.7% and 6.0–17.8%, respectively, and improved oil stability by 23.4–24.7%. The adsorbent combinations have potential for use in practical frying operation to improve the functional and healthy aspects of used frying oils.     

Preparation of palm olein enriched with medium chain fatty acids by lipase acidolysis

Medium chain (MC) fatty acids, caprylic (C8:0) and capric (C10:0) were incorporated into palm olein by 1,3-specific lipase acidolysis, up to 36% and 43%, respectively, when added as mixtures or individually after 24 h. It was found that these acids were incorporated into palm olein at the expense of palmitic and oleic acids, the former being larger in quantity and reduction of 18:2 was negligible. The modified palm olein products showed reduction in higher molecular weight triacylglycerols (TGs) and increase in concentration of lower molecular weight TGs compared to those of palm olein. Fatty acids at sn-2 position in modified products were: C10:0, 4%; C16:0, 13%; C18:1, 66%; and C18:2, 15.4%. DSC results showed that the onset of melting and solids fat content were considerably reduced in modified palm olein products and no solids were found even at and below 10 °C and also the onset of crystallisation was considerably lowered. The cloud point was reduced and iodine value dropped from 55.4 to 38 in modified palm olein. Thus, nutritionally superior palm olein was prepared by introducing MC fatty acids with reduced palmitic acid through lipase acidolysis.     

A high performance liquid chromatography method for determination of furfural in crude palm oil

A modified steam distillation method was developed to extract furfural from crude palm oil (CPO). The collected distillates were analysed using high performance liquid chromatography (HPLC) coupled with an ultraviolet diode detector at 284 nm. The HPLC method allowed identification and quantification of furfural in CPO. The unique thermal extraction of CPO whereby the fresh fruit bunches (FFB) are first subjected to steam treatment, distinguishes itself from other solvent-extracted or cold-pressed vegetable oils. The presence of furfural was also determined in the fresh palm oil from FFB (without undergoing the normal extraction process), palm olein, palm stearin, olive oil, coconut oil, sunflower oil, soya oil and corn oil. The chromatograms of the extracts were compared to that of standard furfural. Furfural was only detected in CPO. The CPO consignments obtained from four mills were shown to contain 7.54 to 20.60 mg/kg furfural.     

Directed interesterification of a brazilian palm oil and analysis of the original and interesterified oil and its fractions

A commercial sample of the Brazilian palm oil from the north eastern State of Bahia after neutralisation, washing and drying was interesterified in the presence of sodium-potassium alloy (NaK) at 30°C in a nitrogen atmosphere. The catalyst was destroyed by addition of water in a carbon dioxide atmosphere and the interesterified oil was crystallised from light petroleum, yielding an olein and stearin fraction. The fatty acid and triacylglycerol composition of the neutralised oil was determined by gas chromatography (g.c.) and high-performance liquid chromatography (h.p.l.c.) respectively and was shown to be similar to that of Malaysian and African palm oil. The compositions of the interesterified Brazilian oil and its liquid and solid fractions were also determined. The physicochemical characteristics of the olein obtained by interesterification with NaK, such as iodine value (96.8) and its softening point (below ?8°C) indicated its suitability for the use as salad oil.