Properties of soaps derived from distilled palm stearin and palm kernel fatty acids

Soaps made from blends of distilled palm stearin (PS) and palm (PK) kernel fatty acids were evaluated for total fatty matter, sodium chloride content, moisture content, hardness, Hunter whiteness, foamability, iodine value, titer value, and acid value. Data showed that these soaps had properties similar to palm-based soaps made from distilled palm oil and palm kernel fatty acids. The soaps showed good whiteness (greater than 80%) and foamability. Total fatty matter ranged from 10–18%, sodium chloride content was 0.5%, and free caustic was 0.1% except for blend 8 containing 10 PS:90 PK, which had a free caustic of 0.03%. Initial penetration value, a reflection of soap hardness, ranged from 32–126 mm, with an average value of 54 mm. This value is within the range of the best blends of palm-based soaps (50–63 mm). There was no obvious trend observed. Penetration value, however was found to stabilize after a month of storage with an average value of 19.4 mm. Soap with this hardness value is relatively hard and therefore should be blended with a small amount of soft oils.     

Comparison of solvent systems on extraction,quality characteristics,and volatile compounds of palm kernel oil

Hexane (HEX) and dichloromethane (DCM) have been used to extract oils from various sources due to their expansive solubility and low volatility that ease removal at low temperatures. However, environmental and health concerns make them undesirable solvents. The aim of this study was to evaluate the extraction efficiency and physicochemical characteristics of palm kernel oil (PKO) extracted with the addition of acetone in HEX-acetone (1:1, vol/vol) and DCM-acetone (1:1, vol/vol) mixtures as an alternative to DCM and HEX alone. PKO extracted with co-solvent systems had better quality characteristics compared with single solvent extracts. The oil recovered, free fatty acid content, peroxide value and other quality characteristics, and thermal properties were within the range for PKO, and similar oils as stipulated in standards. Monounsaturated fatty acid content in PKO was up to 70% of which lauric acid was the most abundant (48%–52%). A total of 50 volatile compounds were identified by GC–MS in all the extracts including amide (1), alcohol (1), aldehydes (2), ketones (3), acids (6), esters (6) and hydrocarbons (31) with higher numbers of volatiles in the HEX extracts compared to the DCM extracts. Dodecanoic acid, hexanal, and 2-undecanone were the most abundant acid, aldehyde, and ketone, respectively. Principal component analysis (PCA) differentiated the volatiles identified on the polar and non-polar columns with 88.2% and 8.8%, and 67.3% and 19.6% of the variation accounted for by PC1 and PC2, respectively, with several common volatile components forming a cluster from all the solvents used.     

Lubrication properties of trimethylolpropane esters based on palm oil and palm kernel oils

Due to the global drive towards biodegradable products, trimethylolpropane [2‐ethyl‐2‐(hydroxymethyl)‐1, 3‐propanediol] (TMP) esters based on palm and palm kernel oils were synthesized, their lubrication properties evaluated, and their potential as base stock for biodegradable lubricants assessed. Two types of TMP esters were considered: palm kernel (PKOTE) and palm oil (PPOTE) TMP esters, derived from palm oil and palm kernel methyl esters, respectively. Lubrication properties such as viscosity, viscosity index (VI) and pour point (PP) were determined according to methods of the American Society for Testing and Materials. Wear and friction properties were evaluated using a four‐ball test machine, while oxidative stability was studied with the Penn State Micro‐oxidation thin‐film test. High VI ranges between 170 to 200 were recorded for these base stocks. PP were relatively high, between 4 to —1 °C, but were improved to at least —33 °C in high oleic palm oil TMP esters. The effects of chemical structure and impurities on wear properties and oxidative stability were also studied. The presence of methyl esters was found to improve wear, but hydroxyl groups in mono‐ and diesters had negative effects at high concentrations. Differences in chemical structures of PKOTE and PPOTE were shown to affect friction and wear results. Both base fluids exhibit oxidative stability comparable to other high oleic base fluids.     

Determination of free fatty acids in crude palm oil and refined-bleached-deodorized palm olein using fourier transform infrared spectroscopy

A rapid direct Fourier transform infrared (FTIR) spectroscopic method using a 100 μ BaF₂ transmission cell was developed for the determination of free fatty acid (FFA) in crude palm oil (CPO) and refined-bleached-deodorized (RBD) palm olein, covering an analytical range of 3.0–6.5% and 0.07–0.6% FFA, respectively. The samples were prepared by hydrolyzing oil with enzyme in an incubator. The optimal calibration models were constructed based on partial least squares (PLS) analysis using the FTIR carboxyl region (C=O) from 1722 to 1690 cm⁻¹. The resulting PLS calibrations were linear over the range tested. The standard errors of calibration (SEC) obtained were 0.08% FFA for CPO with correlation coefficient (R ²) of 0.992 and 0.01% FFA for RBD palm olein with R ² of 0.994. The standard errors of performance (SEP) were 0.04% FFA for CPO with R ² of 0.998 and 0.006% FFA for RBD palm olein with R ² of 0.998, respectively. In terms of reproducibility (r) and accuracy (a), both FTIR and chemical methods showed comparable results. Because of its simpler and more rapid analysis, which is less than 2 min per sample, as well as the minimum use of solvents and labor, FTIR has an advantage over the wet chemical method.     

Dehulling of palm kernel of oil palm (Elaeis guineensis) to obtain superior-grade palm kernel flour and oil

A novel method has been developed for the removal of the thin, dark-brown skin, called testa, from the palm kernel of the oil palm (Elaeis guineensis) by chemical treatment. Studies carried out for this purpose included physical or mechanical means, dry or wet heat, solvents and other chemicals. Of the procedures tried, treatment with hydrochloric acid (HCl) resulted in complete removal of the testa, producing a pearl-white palm kernel. All other treatments were found to be ineffective. Based on our laboratory studies, semi-large-scale trials were made with 4N HCl for continuous dehulling of palm kernel in an abrasive peeling machine for the preparation of superiorgrade kernel flour and oil.     

Determination of free fatty acids in palm oil by near-infrared reflectance spectroscopy

A near-infrared (NIR) spectroscopy calibration was developed for the determination of free fatty acids (FFA) in crude palm oil and its fractions based on the NIR reflectance approach. A range of FFA concentrations was prepared by hydrolyzing oil with 0.15% (w/w) lipase in an incubator at 60°C (200 rpm). Sample preparation was performed in Dutch cup, and the spectra were measured in duplicate for each sample. The optimized calibration models were constructed with multiple linear regression analysis based on C=O overtone regions from 1850–2050 nm. The best wavelength combinations were 1882, 2010, and 2040 nm. Multiple correlation coefficients squared (R ²) were: 0.994 for crude palm oil, 0.961 for refined-bleached-deodorized (RBD) palm olein, and 0.971 for RBD palm oil. Calibrations were validated with an independent set of 8–10 samples. R ² of validation were 0.997, 0.943, and 0.945, respectively. The developed method was rapid, with a total analysis time of 5 min, and environmentally friendly, and its accuracy was generally good for raw-material quality control.     

Design and testing of continuous acid-catalyzed esterification reactor for high free fatty acid mixed crude palm oil

Using acid-catalyzed esterification, a continuous reactor, containing four separate continuous stirred tank reactors (CSTR's), was designed and used to reduce the free fatty acid (FFA) content of mixed crude palm oil (MCPO). A six-blade disk turbine and four baffles were installed in each of the four reactors to enhance mixing. The complete reactor was tested using response surface methodology (RSM). A 5-level, 4-factor, central composite design (CCD) was employed to optimize the four important reaction variables (methanol/oil ratio; sulfuric acid/oil ratio; speed of the stirrer; and residence time) to reduce the FFA content of the MCPO to less than 1 wt.% of oil. Multiple regression analysis was used to derive a polynomial equation to predict the FFA content of the product. This was then used to indicate optimal conditions for reducing the FFA in mixed crude palm oil to less than 1 wt.%.     

Enzymatic incorporation of stearic acid into a blend of palm olein and palm kernel oil: Optimization by response surface methodology

Response surface methodology was used to model the incorporation of stearic acid into a blend of palm olein and palm kernel oil in hexane using the sn-1,3-regiospecific lipase Lipozyme RM IM. The factors investigated were incubation time, temperature, and substrate molar ratio. A second-order model with interaction was used to fit the experimental data. The coefficients of determination, R ² and Q ², were 0.96 and 0.90, respectively. The adjusted R ² was 0.95. The regression probability was less than 0.001, and the model showed no lack of fit. Also, a linear relationship was observed between the predicted and observed values. All parameters studied had positive effects on incorporation of stearic acid, with substrate molar ratio having the greatest effect. The interaction terms of substrate molar ratio with temperature and time also had positive effects on incorporation, whereas the effect of the squared term of substrate molar ratio was negative. The quadratic terms of temperature and time, as well as their interaction term, had no significant effect on incorporation at α_0.05. Model verification was done by performing a chi-square test, which showed that there was no significant difference between predicted values and a new set of observed responses.     

DSC study on the melting properties of palm oil, sunflower oil, and palm kernel olein blends before and after chemical interesterification

Changes in DSC melting properties of palm oil (PO), sunflower oil (SFO), palm kernel olein (PKOo), and their belends in various ratios were studied by using a combination of blending, and chemical interesterification (CIE) techniques and determining total melting (ΔH _f ) and partial melting (ΔH _i°C ) enthalpies. Blending and CIE significantly modified the DSC melting properties of the PO/SFO/PKOo blends. PO and blends containing substantial amounts of PO and PKOo experienced an increase in their DSC ΔH _f and ΔH _i°C following CIE. The DSC ΔH _f and ΔH _i°C of PKOo, blends of PO/SFO at 1∶1 and 1∶3 ratios, and all blends of PKOo/SFO significantly decreased after CIE. The DSC ΔH _f and ΔH _i°C of SFO changed little following CIE. Randomization of FA distribution within and among TAG molecules of PO and PKOo led to modification in TAG composition of the PO/PKOo blends and improved miscibility between the two fats and consequently diminished the eutectic interaction that occurred between PO and PKOo.     

Positional distribution of fatty acids in the triacylglycerols of developing oil palm fruit

The pattern of accumulation of triacylglycerols, their fatty acid compositions and the positional distribution of the fatty acids at thesn-2- andsn-1,3-positions of the triacylglycerol molecules at progressive stages of oil palm fruit development were determined. There was an exponential rate of increase of triacylglycerols and their fatty acids toward the end of fruit development. The fatty acid composition of the triacylglycerols in the early stages of development, prior to active accumulation, was more or less similar, but differed appreciably from the later stages, and the transition of fatty acid composition toward that of normal palm oil occurred at around 16 wk after anthesis (WAA) and stabilized at 20 WAA. All fatty acids increased in terms of absolute quantity. There was an overall consistency in fatty acid positional distribution, irrespective of development stage. More saturated fatty acids were found to be esterified at thesn-1,3-positions and more unsaturated fatty acids at thesn-2-position of triacylglycerol. Higher rate of incorporation of 16:0 at the 1,3-positions during the active phase of triacylglycerol synthesis was observed, while 18:1 acid exhibited a reverse trend.     

Effects of palm oil fatty acid on curing characteristics,reversion and fatigue life of various natural rubber compounds

The effects of palm oil fatty acid concentration (0, 1, 3, 5, 7 phr) and epoxidation on curing characteristics, reversion and fatigue life of carbon black filled natural rubber compounds have been studied. Three different types of natural rubber, SMR L, ENR 25 and ENR 50 having 0, 25 and 50 mol% of epoxidation and conventional sulphur vulcanization were used. The cure time t₉₀, scorch time t₂, M_HR − M_L (maximum torque − minimum torque) and fatigue life of all rubbers were found to increase with increasing palm oil fatty acid concentration. However, the reversion of all rubbers decreases with increasing palm oil fatty acid concentration. At similar concentrations of palm oil fatty acid, ENR 50 compounds exhibit the shortest scorch and cure times followed by ENR 25 and SMR L compounds. For reversion, SMR L compounds show the lowest value followed by ENR 50 and ENR 25 compounds, whereas for fatigue life, the highest value is obtained with ENR 50 compounds followed by ENR 25 and SMR L compounds. © 1999 Society of Chemical Industry     

Crystallisation and melting behaviour of palm kernel oil and related products by differential scanning calorimetry

Lauric oils are valuable sources for oils suitable for various food applications. They are particularly useful as cocoa butter substitutes for which steep solid fat content profiles are required. Palm kernel oil is one such fat, which upon fractionation and/or hydro‐genation provides a variety of oil fractions with different oil composition and properties. The stearins have excellent properties for confectionery fats, while the oleins can be further hydrogenated to improve their properties. This paper gives an overview of the properties of products of palm kernel oil, produced from fractionation and hydrogena‐tion. The melting and crystallisation properties from differential scanning calorimetry studies are discussed in relation to the triacylglycerols of the oils.     

Chemical and physical changes in cottonseed oil during deodorization

The effects of deodorization time and temperature on the physical and chemical properties of cottonseed oil were investigated. Higher temperatures and longer times lead to increases in free fatty acids, peroxide value, viscosity and refractive index while iodine value, unsaponifiable matter and induction period decreased.     

Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production

In this study, sulphuric acid (H₂SO₄) was used in the pretreatment of sludge palm oil for biodiesel production by an esterification process, followed by the basic catalyzed transesterification process. The purpose of the pretreatment process was to reduce the free fatty acids (FFA) content from high content FFA (> 23%) of sludge palm oil (SPO) to a minimum level for biodiesel production (> 2%). An acid catalyzed esterification process was carried out to evaluate the low content of FFA in the treated SPO with the effects of other parameters such as molar ratio of methanol to SPO (6:1-14:1), temperature (40-80 °C), reaction time (30-120 min) and stirrer speed (200-800 rpm). The results showed that the FFA of SPO was reduced from 23.2% to less than 2% FFA using 0.75% wt/wt of sulphuric acid with the molar ratio of methanol to oil of 8:1 for 60 min reaction time at 60 °C. The results on the transesterification with esterified SPO showed that the yield (ester) of biodiesel was 83.72% with the process conditions of molar ratio of methanol to SPO 10:1, reaction temperature 60 °C, reaction time 60 min, stirrer speed 400 rpm and KOH 1% (wt/wt). The biodiesel produced from the SPO was favorable as compared to the EN 14214 and ASTM D 6751 standard.     

Urea complexation for the rapid, ecologically responsible fractionation of fatty acids from seed oil

Urea complex formation is a classic method for fractionating fatty acids from seed and other oils. The method’s simplicity, ease of scaling, and ecological friendliness suggest its reevaluation in regard to modern fractionation challenges. In keeping with this, a simple, quick, inexpensive, robust, and environmentally friendly procedure was developed for reducing the saturated free fatty acid (FFA) content of saponified low-erucic acid rapeseed oil (LEAR). The process involves formation of a homogeneous 65°C solution of FFA and urea in 95% ethanol (5% water), followed by cooling of the resultant urea complex slurry to room temperature. The urea complex and liquid phases are separated by gravity filtration, and the urea isolated in each phase is removed by extraction with 60°C water. Saturated LEAR oil FFA preferentially formed urea complexes easily separated from the noncomplexed, mostly unsaturated FFA, the main product of interest. The effects of single- vs. double-stage fractionations and several other variables (component mass or volume ratios, temperature, ethanol solvent to water ratio) were preliminarily evaluated. Results demonstrated the robustness, reproducibility, and simplicity of the method.     

Relationship between slip melting point and pulsed NMR data of palm kernel oil

A quantitative relationship between slip melting point (SMP) of palm kernel oil and pulsed nuclear magnetic resonance (NMR) data was established. Regression analysis on the SMP and solid fat content (SFC) data by NMR afforded the following relationship: SMP (°C) = 0.03278 X (SFC 10) + 0.1458 X (SFC 20) + 19.1738 where SFC 10 was the solid fat content (%) at 10°C and SFC 20 was the solid fat content (%) at 20°C. The coefficient of multiple correlation was 0.87871. The equation was tested with 12 samples of crude and refined palm kernel oil. SMPs as determined indirectly by NMR correlated well with the conventional open capillary tube results (r = 0.99998). The maximum difference observed was 0.3°C. The correlation can be applied usefully for quality control.     

Bio‐ and auto‐catalytic esterification of high acid mowrah fat and palm kernel oil

An alternative process for the deacidification of high acid palm kernel oil (PKO) and mowrah fat, MF, was investigated by autocatalytic and enzyme (Mucor miehei)‐catalyzed esterification of free fatty acids (FFA). In the process monoglyceride (MG) or glycerol was used as esterifying agent. The results of the autocatalytic esterification process were compared with that of bioesterification with respect to reduction of FFA. For the former process the optimum reaction temperature and oil to MG or glycerol proportion were established. The optimum reaction temperature for PKO free fatty acids with stoichiometric quantity of glycerol is 160—165 °C (at 10 mm Hg pressure (1.33 kPa)) and after 6 h the FFA content is reduced to 1.6%, w/w, (from 25.0%, w/w, original). However, if a stoichiometric amount of MG is used as an esterifying agent the optimum esterification temperature is found to be 195—200 °C (at 10 mm Hg pressure (1.33 kPa)), and after 8 h the FFA content is reduced to 3.4%, w/w. On the contrary, biorefining of PKO at 60 °C temperature and 10 mm Hg pressure (1.33 kPa) using optimum (40% excess) quantity of glycerol or 50% excess MG reduces the FFA level to 1.2% and 0.7%, w/w, respectively. Similar study on bio‐ and auto‐catalytic esterification of MF was also carried out and got comparable results. The final products were then characterized.     

A modified method for determining free fatty acids from small soybean oil sample sizes

A modification of the AOCS Official Method Ca 5a-40 for determination of free fatty acids (FFA) in 0.3 to 6.0-g samples of refined and crude soybean oil is described. The modified method uses only about 10% of the weight of oil sample, alcohol volume, and alkali strength recommended in the Official Method. Standard solutions of refined and crude soybean oil with FFA concentrations between 0.01 and 75% were prepared by adding known weights of oleic acid. The FFA concentrations, determined from small sample sizes with the modified method, were compared with FFA percentages determined from larger sample sizes with the Official Method. Relationships among determinations obtained by the modified and official methods, for both refined and crude oils, were described by linear functions. The relationship for refined soybean oil had an R ² value of 0.997 and a slope of 0.99±0.031. The values for crude soybean oil are defined by a line with R ²=0.9996 and a slope of 1.01±0.013.     

Characterization of palm acid oil

Palm acid oil (PAO) is a by-product obtained from the alka-line refining of palm oil. It is used for making laundry soaps and for producing calcium soaps for animal feed formulations. The properties and composition of PAO may differ according to variations in the palm oil feedstock and the alkaline refining process. Because information on the characteristics of PAO is limited, this investigation aims to establish the properties of this product. Quality and oxidative parameters of 27 samples of PAO were determined. The six parameters analyzed were moisture and free fatty acid content, peroxide value, iodine value, saponification value and unsaponifiable matter. Headspace-gas-chromatographic (HSGC) analysis and gas-chromatographic analysis of the extract from Likens-Nickerson steam distillation of the samples were also carried out. Mean moisture content was 0.98%, free fatty acids 62.6% (palmitic acid), peroxide value 4.1 meq/kg, iodine value 50.2, saponification value 186 and unsaponifiable matter 0.53 HSGC profiles of a few samples showed the presence of one to three peaks, while the steam distillation extract showed the presence of aldehydes, ketones, furans and acids.     

Quantitative analysis of partial acylglycerols and free fatty acids in palm oil by 13C nuclear magnetic resonance spectroscopy

The chemical shifts, spin-lattice relaxation times (T ₁), and one-bond C−H coupling constants of the glycerol carbons of mono-, di-, and triacylglycerols in CDCI₃ solution are presented and discussed. The glycerol carbons have low T ₁ values (<1.0 s) and full nuclear Overhauser effect and also exhibit broader linewidths than the aliphatic carbons, suggesting that the glycerol carbons are at or near the T ₁ minimum for the dipole-dipole relaxation mechanism. Therefore, for quantitative measurement of the composition of partial acylglycerols (relative to the triacylglycerols) in palm oil, the nuclear magnetic resonance (NMR) spectrum of the β-carbons, which lie exclusively in the region δ68.3–72.1 ppm, should preferably be acquired at medium or low magnetic fields and at an elevated temperature in order to ensure that the condition for extremely narrow spectral lines is satisfied. The chemical shifts and spinlattice relaxation times of the aliphatic C-2 and C-3 carbons and of the carbonyl carbons (C-1) of acyl groups present in palm oil are also presented and discussed. The presence of free fatty acid in the palm oil is easily detected and quantified in the spectrum of the aliphatic carbons. The presence of partial acylglycerols in palm oil can also be detected and/or quantified in the NMR spectra of the C-2 and the carbonyl carbons. The quantitative analysis of the glycerol carbons of a known mixture of acylglycerols obtained by using this method is presented.