Processing for industrial fatty acids - II

Fatty acids are produced industrially from tallow, palm oil, palm stearin, palm kernel oil and coconut oil. The current and future supply situations of these raw materials and market economics favor palm stearin and palm kernel oil as major raw materials for fatty acids. The Malaysian oleochemical industry has adopted high-temperature and high-pressure “splitting” of triglycerides. Variations in product yields occurring in the processing of tallow and palm stearin and of coconut oil and palm kernel oil are indicated. Developments on the enzymic hydrolysis of triglycerides to fatty acids have been made, particularly in Japan. Enzymic hydrolysis at low temperature has the advantage of energy conservation compared to the high-temperature and pressure-splitting process. But enzymic hydrolysis is only applicable to triglycerides of low titre, such as palm kernel oil.     

Application of FTIR Spectroscopy for the Determination of Virgin Coconut Oil in Binary Mixtures with Olive Oil and Palm Oil

Rapid Fourier transform infrared (FTIR) spectroscopy combined with attenuated total reflectance (ATR) was applied for quantitative analysis of virgin coconut oil (VCO) in binary mixtures with olive oil (OO) and palm oil (PO). The spectral bands correlated with VCO, OO, PO; blends of VCO and OO; VCO and PO were scanned, interpreted, and identified. Two multivariate calibration methods, partial least square (PLS) and principal component regression (PCR), were used to construct the calibration models that correlate between actual and FTIR-predicted values of VCO contents in the mixtures at the FTIR spectral frequencies of 1,120–1,105 and 965–960 cm⁻¹. The calibration models obtained were cross validated using the “leave one out” method. PLS at these frequencies showed the best calibration model, in terms of the highest coefficient of determination (R ²) and the lowest of root mean standard error of calibration (RMSEC) with R ² = 0.9992 and RMSEC = 0.756, respectively, for VCO in mixture with OO. Meanwhile, the R ² and RMSEC values obtained for VCO in mixture with PO were 0.9996 and 0.494, respectively. In general, FTIR spectroscopy serves as a suitable technique for determination of VCO in mixture with the other oils.     

Application of FTIR spectroscopy in determining sesamol in sesame seed oil

A new analytical method was developed for determining sesamol in sesame seed oil by FTIR spectroscopy. Sesamol was also spiked at 0 to 1000 mg/kg in freshly refined, bleached, and deodorized palm olein (RBDPOo) and groundnut (peanut) oil. FTIR spectra were recorded using a transmission (NaCl) cell accessory at room temperature, and the partial least squares regression statistical method was used to derive calibration models for each oil. The standard errors of calibration were 6.07, 5.88, and 4.24 mg/100 g for sesame, RBDPOo, and groundnut oils, with coefficients of determination (R ²) of 0.9947, 0.9940, and 0.9662, respectively. The calibration models were validated by the “leave-one-out” cross-validation method, and the R ² of validation, the standard errors of prediction, and SD of the differences for repeatability and accuracy were computed. Our results support the premise that FTIR spectroscopy is an efficient and accurate method for determining minor components such as sesamol in edible oils.     

Rapid methods for determination of free fatty acids contents in fatty oils

Rapid qualitative and quantitative methods for determining the free fatty acid (FFA) contents in common oils and fats are reported. Qualitative method is based on the type of color developed in the presence of BDH indicators (Universal and “678”) when a known excess of alkali is added to an alcoholic solution of oil or fat. By this method, low (0.0–0.25), medium (0.26–0.99) and high (1.0 and above) FFA levels in fatty oils may be distinguished. Quantitative method is a simplified modification of the usual procedure of determining the FFA contents of oils and fats by titration against standard alkali solution in the presence of BDH Universal or “678” indicator. The results of the rapid methods agree well with those of the standard AOCS method.     

The importance of glycerol in the fatty acid industry

Historically, glycerol, a valuable by product of the fatty acid insutry, is priced higher in the market-place than any of the common fatty acids. Glycerol “credit” from fat-splitting, frequently in time of economic stress, makes the difference between a profitable stearic acid operation and an economically unsound one. Theoretical yields of glycerol for the common fats and oils range from 9–13.5%; practical plant yields, corrected for FFA and upgrading yield losses, are 9–12.8% on 100% glycerol basis, or 10.3–14.8% on an 88% glycerol basis. Glycerol “credit” per pound of fatty acid ranges from 1 to 3 cents/pound. Upgrading “sweetwaters” from splitting operations in the fatty acid industry requires removal of dissolved salts, elimination of color, and fat and oil impurities, concentration (evaporation of water) and/or distillation. For Twitchellized sweetwaters this generally involves (a.) lime treatment. (b.) filtration, (c.) evaporation to half-crude, (d.) precipitation of excess lime, (e.) filtration, (f.) evaporation to a concentration of 88–90%, and probably, (g.) distillation. For autoclave or continuous process sweetwaters the upgrading includes (a.) light lime treatment, (b.) filtration, (c.) evaporation concentration to 88–90%, and probably, (d.) distillation. Glycerol may also be upgraded by ion-exchange processing followed by evaporation concentration in which distillation may be eliminated. Ion-exclusion (Dow process) is also feasible. Many special triglyceride products are required of different fatty acid homolog distribution than those of the parent or hydrogenated fats and oils. These are prepared by splitting the fats or hydrogenated oils, fractionating the fatty acids, upgrading the glycerol, and recombining the desired fractionated acids with glycerol by reesterification. One example is high lauric triglyceride from coconut oil suited for use as a coco butter substitute.     

Rapid quantitative determination of free fatty acids in fats and oils by fourier transform infrared spectroscopy

Rapid direct and indirect Fourier transform infrared (FTIR) spectroscopic methods were developed for the determination of free fatty acids (FFA) in fats and oils based on both transmission and attenuated total reflectance approaches, covering an analytical range of 0.2–8% FFA. Calibration curves were prepared by adding oleic acid to the oil chosen for analysis and measuring the C=O band @ 1711 cm^–1 after ratioing the sample spectrum against that of the same oil free of fatty acids. For fats and oils that may have undergone significant thermal stress or extensive oxidation, an indirect method was developed in which 1% KOH/methanol is used to extract the FFAs and convert them to their potassium salts. The carboxylate anion absorbs @ 1570 cm^–1, well away from interfering absorptions of carbonyl-containing oxidation end products that are commonly present in oxidized oils. Both approaches gave results comparable in precision and accuracy to that of the American Oil Chemists’ Society reference titration method. Through macroprogramming, the FFA analysis procedure was completely automated, making it suitable for routine quality control applications. As such, the method requires no knowledge of FTIR spectroscopy on the part of the operator, and an analysis takes less than 2 min.     

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.     

Soap and related products: Palm and lauric oil

There are three main methods for producing soap: direct saponification of fats and oils, neutralization of fatty acids and saponification of fatty acid methyl esters. Our unique process of soapmaking, based on the methyl ester saponification method, is described here. By this process, high-quality toilet soaps can be produced from palm stearin and palm kernel oil as well as tallow and coconut oil. A new sulfonation process was developed to produce high-quality α-SFMe (α-sulfo fatty acid methyl ester) from palm stearin as the starting material. Quality and performance of α-SFMe bear comparison with those of LAS, AES, AS or AOS. Thus α-SFMe is a promising surfactant for detergents and will contribute to expanding the use of palm oil in the near future.     

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.     

Quality assessment of industrial prefried french fries

An industrial production of prefried french fries using palm oil as a frying medium was studied over a period of 12 days. Samples of oils and french fries were withdrawn once a day. The quality of both the oil and the french fries was assessed using two types of tests. Some tests, such as the determination of free fatty acid (FFA) and the determination of thiobarbituric acid value (TBA), oxifritest and Food Oil Sensor correspond to what was used by a quality control laboratory. More elaborate techniques such as the determination of polar components, polymers and cyclic fatty acid monomers (CFAM) were also used. Only small increases of FFA, TBA, polar components and polymers were observed. However, in the case of palm oil, which contains a high percentage of diglycerides, it is more reliable to determine the quality of the oil using the amount of polymers instead of polar components which may include some diglycerides. Thus a high “polar components” value (up to 20–25%) would not necessarily reflect an altered sample. The maximum amount of CFAM detected was 0.1% and they did not seem to be preferentially adsorbed on the french fries. These results, along with the sensory evaluations, showed that the french fries obtained in these production conditions were of good quality as far as the fat was concerned.     

Effects of Crude Rice Bran Oil Components on Alkali-Refining Loss

The effects of minor components in crude rice bran oil (RBO) including free fatty acids (FFA), rice bran wax (RBW), γ-oryzanol, and long-chain fatty alcohols (LCFA), on alkali refining losses were determined. Refined palm oil (PO), soybean oil (SBO) and sunflower oil (SFO) were used as oil models to which minor component present in RBO were added. Refining losses of all model oils were linearly related to the amount of FFA incorporated. At 6.8% FFA, the refining losses of all the model oils were between 13.16 and 13.42%. When <1.0% of LCFA, RBW and γ-oryzanol were added to the model oils (with 6.8% FFA), the refining losses were approximately the same, however, with higher amounts of LCFA greatly increased refining losses. At 3% LCFA, the refining losses of all the model oils were as high as 69.43–78.75%, whereas the losses of oils containing 3% RBW and γ-oryzanol were 33.46–45.01% and 17.82–20.45%, respectively.     

New FTIR method for the determination of FFA in oils

A rapid, practical, and accurate FTIR method for the determination of FFA in edible oils was developed. Analogous to the AOCS titration procedure, the FTIR FFA determination is effected by an acid/base reaction but directly measures the product formed rather than utilizing an end point based on an electrode potential or color change. A suspension of a weak base, potassium phthalimide (K-phthal) in 1-propanol (1-PrOH), is used to convert the FFA present in oils to their carboxylate salt without causing oil saponification, and differential spectroscopy is used to circumvent matrix effects. Samples are first diluted with 1-PrOH, then split, with one-half treated with the K-phthal reagent and the other half with 1-PrOH (blank reagent), their spectra collected, and differential spectra obtained to ratio out the invariant spectral contributions from the oil sample. Quantification of the percentage of FFA in the oil, expressed as %oleic acid, based on measurement of the peak height of the ν (COO⁻) absorption of the FFA salt formed, yielded a calibration with an SE of <0.020% FFA over the range of 0–4%. The method was validated by standard addition and the analysis of Smalley check samples, the results indicating that the analytical performance of the FTIR procedure is as good as or better than that of the standard titrimetric procedure. As structured, the FTIR procedure is a primary method, as calibration is not dependent on reference values provided by another method, and has performance criteria that could lead to its consideration as an instrumental AOCS procedure for FFA determination. The FTIR portion of the analysis is automatable, and a system capable of analyzing ∼60 samples/h was developed that could be of benefit to laboratories that carry out a large number of FFA analyses per day.     

Palm oil analysis in adulterated sesame oil using chromatography and FTIR spectroscopy

This study highlights the application of two analytical techniques, namely GC‐FID and FTIR spectroscopy, for analysis of refined‐bleached‐deodorized palm oil (RBD‐PO) in adulterated sesame oil (SeO). Using GC‐FID, the profiles of fatty acids were used for the evaluation of SeO adulteration. The increased concentrations of palmitic and oleic acids together with the decreased levels of stearic, linoleic, and linolenic acids with the increasing contents of RBD‐PO in SeO can be used for monitoring the presence of RBD‐PO in SeO. Meanwhile, FTIR spectroscopy combined with multivariate calibration of partial least square (PLS) has been successfully developed for the detection and quantification of RBD‐PO in SeO using the combined frequencies of 3040–2995, 1660–1654, and 1150–1050 cm^?1. The values of coefficient of determination (R²) for the relationship between actual versus FTIR‐calculated values of RBD‐PO in SeO and root mean square error of calibration (RMSEC) obtained are 0.997 and 1.32% v/v, respectively. In addition, using three factors, the root mean square error of prediction (RMSEP) value obtained using the developed PLS calibration model is relatively low, i.e., 1.83% v/v. Practical Application: The adulteration practice is commonly encountered in fats and oils industry. It involves the replacement of high value edible oils such as sesame oil with the lower ones like palm oil. Gas chromatography and FTIR spectroscopy can be used as reliable and accurate analytical techniques for detection and quantification of palm oil in sesame oil.     

Zinc deficiency and activities of lipogenic and glycolytic enzymes in liver of rats fed coconut oil or linseed oil

In previous studies, zinc-deficient rats force-fed a diet with coconut oil as the major dietary fat developed a fatty liver, whereas zinc-deficient rats force-fed a diet with linseed oil did not. The present study was conducted to elucidate the reason for this phenomenon. In a bifactorial experiment, rats were fed zinc-adequate or zinc-deficient diets containing either a mixture of coconut oil (70 g/kg) and safflower oil (10 g/kg) (“coconut oil diet”) or linseed oil (80 g/kg) (“linseed oil diet”) as a source of dietary fat, and activities of lipogenic and glycolytic enzymes in liver were determined. In order to ensure adequate food intake, all the rats were force-fed. Zinc-deficient rats on the coconut oil diet developed a fatty liver, characterized by elevated levels of triglycerides with saturated and monounsaturated fatty acids. These rats also had markedly elevated activities of the lipogenic enzymes acetyl-CoA carboxylase, fatty acid synthase (FAS), glucose-6-phosphate dehydrogenase (G6PDH), 6-phosphogluconate dehydrogenase (6PGDH), and citrate cleavage enzyme, whereas activities of malic enzyme and glycolytic enzymes were not different compared with zinc-adequate rats on the coconut oil diet. In contrast, rats receiving the linseed oil diet had similar triglyceride concentrations regardless of zinc status, and activities of lipogenic enzymes and glycolytic enzymes were not different between the two groups. Zinc-deficient rats fed either type of dietary fat exhibited statistically significant correlations between activities of FAS, G6PDH, 6PGDH and concentrations of saturated and monounsaturated fatty acids in liver. The concentrations of serum lipids were elevated in zinc-deficient rats fed either type of dietary fat. These results demonstrate that fatty liver in zinc-deficient rats on the coconut oil diet is caused by elevated activities of lipogenic enzymes, and not by disturbed lipid secretion from liver. Dietary linseed oil prevents both the elevation of lipogenic enzyme activity and fatty liver in zinc-deficient rats.     

The role of fats and oils in cosmetics

The earliest emollients in the history of cosmetics were the naturally occurring animal fats and vegetable oils. These provided soothing and smoothing action on the skin and grooming effects on head and beard hair. For the most part, odor problems limited the interest in oils derived from fish. With the increasing sophistication of users and increasing understanding of the technology of these materials, the short-comings of natural fats and oils were overcome in several ways: (a) increased stability through use of antioxidants; (b) reduced odor through improved processing; (c) improved stability and diversification through chemical modification; (d) increased diversity through preparation of derivatives, and (e) substitution of mineral oil. Today the most important single cosmetic use of an unmodified natural fat or oil is that of castor oil as the base for lipsticks. Other unmodified oils have largely minor specialty uses, particularly in higher-priced cosmetics. These include almond oil, apricot kernel oil, sesame oil, safflower oil, wheat germ oil, avocado oil, turtle oil and mink oil. Cocoa butter is used to some extent in suntan products. Reconstituted fractionated coconut oil is widely used. Polyglycerol esters of fatty acids are increasing in importance. Hydrogenation has produced stable oils useful in cosmetics. Alkyl esters and monoglycerol esters of fatty acids offer a wider range of properties than the original oils. Improvements in the naturally occurring fats and oils have made it possible for them to compete in some characteristics, and current interest in “natural” cosmetics may turn the attention of the cosmetic chemist back to improved versions of the classical raw materials. One of five papers in the symposium “Fats and Oils in Cosmetics and Pharmaceuticals,” presented at the AOCS Meeting, Atlantic City, October 1971.     

Fatty Acid Composition,Oxidative Stability,and Radical Scavenging Activity of Vegetable Oil Blends with Coconut Oil

Coconut (Cocos nucifera) contains 55–65% oil, having C12:0 as the major fatty acid. Coconut oil has >90% saturates and is deficient in monounsaturates (6%), polyunsaturates (1%), and total tocopherols (29 mg/kg). However, coconut oil contains medium chain fatty acids (58%), which are easily absorbed into the body. Therefore, blends of coconut oil (20–80% incorporation of coconut oil) with other vegetable oils (i.e. palm, rice bran, sesame, mustard, sunflower, groundnut, safflower, and soybean) were prepared. Consequently, seven blends prepared for coconut oil consumers contained improved amounts of monounsaturates (8–36%, p < 0.03), polyunsaturates (4–35%, p < 0.03), total tocopherols (111–582 mg/kg, p < 0.02), and 5–33% (p < 0.02) of DPPH (2,2-diphenyl-1-picrylhydrazyl free radicals) scavenging activity. In addition, seven blends prepared for non-coconut oil consumers contained 11–13% of medium chain fatty acids. Coconut oil + sunflower oil and coconut oil + rice bran oil blends also exhibited 36.7–89.7% (p < 0.0005) and 66.4–80.5% (p < 0.0313) reductions in peroxide formation in comparison to the individual sunflower oil and rice bran oil, respectively. It was concluded that blending coconut oil with other vegetable oils provides medium chain fatty acids and oxidative stability to the blends, while coconut oil will be enriched with polyunsaturates, monounsaturates, natural antioxidants, and a greater radical scavenging activity.     

Long-term feeding of dietary oils alters lipid metabolism, lipid peroxidation, and antioxidant enzyme activities in a teleost (Anabas testudineus bloch)

Anabas testudineus (climbing perch), average body weight 21±1 g, were maintained in culture tanks and fed a 35% protein feed plus an additional supplementation of three dietary oils (20% each of coconut oil, palm oil, or cod liver oil). Body weight gain was similar among all groups. However, several hepatic lipogenic enzymes such as malic enzyme (ME), NADP-isocitrate dehydrogenase (ICDH), glucose-6-phosphate dehydrogenase (G6PDH), 6-phosphogluconate dehydrogenase (6PGDH) and β-hydroxy-β-methyl glutaryl CoA reductase (HMG CoA reductase) were assayed, and they responded differently. Hepatic ME and G6PDH activities showed a significant decrease in the coconut oil and palm oil groups, but there was no significant change in ICDH activity. The 6PGDH activities were reduced, whereas HMG CoA reductase activity was increased in the palm oil-treated group. Cholesterol synthesis in the liver and muscle increased in the palm oil-treated group, but liver phospholipids did not show any significant change in fish supplemented with oils rich in saturated fatty acids. Triacyl-glycerol and free fatty acid concentrations were high in the coconut oil- and palm oil-supplemented groups. Lipid peroxidation products such as thiobarbituric acid-reactive substances and conjugated dienes decreased in the same two groups. Antioxidant potential was high in all groups as evidenced by increased activity of superoxide dismutase, glutathione peroxidase, and glutathione content. The results of this study indicate that in fish, dietary lipids depress hepatic lipogenic activity as well as lipid peroxidation products by maintaining high levels of antioxidant enzymes.     

Multivariate determination of cloud point in palm oil using partial least squares and principal component regression based on FTIR spectroscopy

A rapid FTIR spectroscopic method was developed for quantitative determination of the cloud point (CP) in palm oil samples. Calibration samples were prepared by blending randomized amounts of palm olein and palm stearin to produce a wide range of CP values ranging between 8.3 and 47.9°C. Both partial least squares (PLS) and principal component regression (PCR) calibration models for predicting CP were developed by using the FTIR spectral regions from 3000 to 2800 and 1800 to 1600 cm⁻¹. The prediction capabilities of these calibration models were evaluated by comparing their standard errors of prediction (SEP) in an independent prediction set consisting of 14 palm oil samples. The optimal model based on PLS in the spectral range 1800-1600 cm⁻¹ produced lower SEP values (2.03°C) than those found with the PCR (2.31°C) method. FTIR in conjunction with PLS and PCR models was found to be a useful analytical tool for simple and rapid quantitative determination of CP in palm oil.     

Rapid Determination of Degradation in Frying Oils with Near-Infrared Spectroscopy

Measures of free fatty acids (FFA), total polar materials (TPM), and conjugated dienoic acids (CDA), typical indices of oil degradation, were analyzed in daily oil aliquots taken from soybean oils with different linolenic acid concentrations used to fry French fries. The oils also were scanned with a reflectance near-infrared spectrometer using a wavelength range of 350–2,500 nm. By using partial least squares and one-out cross validation, calibrations were developed to quantitatively determine FFA, TPM, and CDA by near-infrared spectroscopy (NIRS). The coefficients of determination (R ²) when compared to the standard methods were 0.973 for FFA, 0.984 for TPM, and 0.902 for CDA. NIRS was an accurate and fast method to determine FFA, TPM, and CDA in oxidized oils. The ability to obtain different parameters simultaneously makes NIRS a potentially valuable tool for food quality assurance.     

Fatty Acid Profile Including <Emphasis Type="Italic">Trans</Emphasis> Fatty Acid Content of Margarines Marketed in Mexico

In this study, the fatty acid profile of 42 margarines marketed in Mexico was identified and quantified including the total trans fatty acids (TFA). The ratio of the sum of cholesterol-lowering fatty acids CLFA (cis-oleic, linoleic and α-linolenic fatty acids) to the sum of cholesterol-raising fatty acids CRFA (C12:0, C14:0, C16:0, TFA) and the ω6/ω3 ratio were calculated to evaluate the nutritional quality of the margarine samples. The results showed that the high content of C12:0, C14:0 and C16:0 fatty acids in some samples indicated the use of coconut and palm oils instead of partially hydrogenated fatty acids in order to decreased TFA content. Of the samples, 33% had less than 1 g/100 g of fat which could be considered as “free from TFA” according to the Danish Legislation. The ω6/ω3 ratio ranged between 5.85:1 and 25.85:1, the ideal relation being 5–10:1. The CLFA/CRFA ranged from 0.46 to 3.10, being the recommended ratio as high as possible. Of the 42 margarines, only five samples had an acceptable fatty acid profile, that is, low TFA and saturated fatty acids, high monounsaturated fatty acids content and adequate ω6/ω3 and CLFA/CRFA ratios.