Plastic fats and margarines through fractionation,blending and interesterification of milk fat

Milk fat stearins and oleins were blended with high‐ and low‐melting natural fats to produce plastic fats, vanaspati substitute and confectionery fats. Margarines of improved nutritional value were also formulated. Fractionation was carried out using acetone, hexane, and isopropyl alcohol. The yield (wt‐%) of high‐melting stearin (HMS) from acetone and IPA was 13.0 ± 0.2 to 13.3 ± 0.1 after crystallization for 24 h at 20 °C. The melting point of the products was 49.0 ± 0.5 to 49.8 ± 0.6 °C. However, in hexane the yield of HMS was 12.2 ± 0.2% at 10 °C. The olein fractions were further fractionated at 10 °C from acetone and IPA, and at 0 °C from hexane, to obtain superoleins and low‐melting stearins (LMS). HMS fractions were blended with rice bran oil and cottonseed oil at the ratio 70 : 30 (wt/wt), and the superoleins were blended with sal fat and palm stearin at the ratios 40 : 60, 30 : 70 and 20 : 80 (wt/wt). The blends were interesterified (product melting point: 22.7 ± 0.04 to 39.3 ± 0.10 °C) chemically and enzymatically to prepare margarine. The penetration values (in 0.1 mm) of these margarines were noted to be 112 ± 1.52 to 145 ± 0.00.     

Preparation of plastic fats with zero <Emphasis Type="Italic">trans</Emphasis> FA from palm oil

A series of plastic fats containing no trans FA and having varying melting or plastic ranges, suitable for use in bakery, margarines, and for cooking purposes as vanaspati, were prepared from palm oil. The process of fractionating palm oil under different conditions by dry and solvent fractionation processes produced stearins of different yields. Melting characteristics of stearin fractions varied depending on the yield and the process. The lower-yield stearins were harder and had a wider plastic range than those of higher yields. The fractions with yields of about 35% had melting profiles similar to those of commercial vanaspati. The plastic range of palm stearins was further improved by blending them with corresponding oleins and with other vegetable oils. The plasticity or solid fat content varied depending on the proportion of stearin. Blends with higher proportions of stearins were harder than those with lower proportions. the melting profiles of some blends, especially those containing 40–60% stearin of about 25% yield and 40–60% corresponding oleins or mahua or rice bran oils, were similar to those of commercial vanaspati and bakery shortenings. These formulations did not contain any trans FA, unlike those of commercial hydrogenated fats. Thus, by fractionation and blending, plastic fats with no trans acids could be prepared for different purposes to replace hydrogenated fats, and palm oil could be utilized to the maximum extent.     

Sal olein and mahua olein for direct edible use

Vegetable butter oleins are obtained as by-products during the fractionation process employed for making cocoa butter substitutes from sal and mahua. Outlets for these olein portions would not only ensure total utilization of these nontraditional oils, but would also provide an extension of edible oil supplies. The normal analytical characteristics and fatty acid compositions of the olein portions obtained from sal and mahua fats were investigated under appropriate conditions of time and temperature. Sal olein was found to be rich in stearic (33.5–34.0%) and oleic acids (49.1–50.0), whereas mahua olein contained palmitic (18%), stearic (21%) and oleic (38%) acids. Projections from Schaal oven stability studies indicated that even without an antioxidant addition, the oleins could be stored for 4–5 months, and with 0.01% tertiary butyl hydroquinone, the storage life could be prolonged to over one year. Deep-fat frying experiments indicated that the oleins showed a slow buildup rate of total polar material and are quite suitable for such use.     

Palm oil and palm kernel oil in food products

Cocoa butter equivalent (CBE) formulation, especially the compatibility of palm oil based CBE with cocoa butter, is of special interest to chocolate manufacturers. Traditionally palm oil is fractionated to obtain high-melting stearin and olein with a clear point of around 25 C, the latter serving as cooking oil. Recently, palm oil has been fractionated to recover an intermediate fraction known as palm mid-fraction (PMF), which is suitable for CBE formulations. Generally, production of PMF is based on a three-step procedure. However, a dry fractionation system, which includes selective crystallization and removal of liquid olein by means of a hydraulic press, has been developed. Iodine value, solid content (SFI) at different temperatures, cooling curves (Shukoff 0°) and triglyceride/fatty acid composition determination confirmed effectiveness of the procedure followed. A direct relationship between yield, quality of PMF and crystallization temperature during fractionation has been achieved. Yield of 60% for olein of IV 64–67 has been achieved. Yield of 30% for PMF of IV 36–38 and 10% for high melting stearin of IV of 20–22 are also being achieved. High-melting stearin may be used in oleochemical applications, soaps, food emulsifiers and other industrial applications such as lubricating oil. Olein fraction, especially after flash hydrogenation thereby reducing the IV to 62/64, has excellent frying and cooking oil characteristics. Palm olein is also suitable as dietary fat and in infant formulation. Studies on interesterification of high-melting stearin with olein showed possibilities to formulate hardstocks for margarine and spread formulations, even without using hydrogenated fat components. Palm kernel and coconut fats or fractions or derived products are used for confectionery products as partial CB replacers and as ice cream fats and coatings. Coconut oil also serves as a starting material for the production of medium-chain triglycerides.     

Isolation and Evaluation of Stearin and Olein Fractions from Rice Bran Oil Fatty Acid Distillate by Detergent Fractionation and Conversion into Neutral Glycerides by Autocatalytic Esterification Reaction

Detergent fractionation (Lanza process) offers a valuable separation process for edible oils that contain varying amounts of saturated and unsaturated fatty acids. The rice bran oil fatty acid distillate (RBOFAD), obtained as a major byproduct of rice bran oil deacidification refining process, was fractionated by detergent solution into a fatty acid mixture as follows: low-melting (19.00 °C) fraction of fatty acids as olein fraction (44.50 g/100 g) and high-melting (49.00 °C) fatty acids as stearin fraction (37.15 g/100 g). A high amount of palmitic acid (42.75 wt%) is present in stearin fraction, while oleic acid is higher (48.21 wt%) in the olein fraction. The stearin and olein fractions of RBOFAD with very high content of free fatty acids are converted into neutral glycerides by autocatalytic esterification reaction with a theoretical amount of glycerol at high temperatures (130–230 °C) and at a reduced pressure (30 mmHg). Acid value, peroxide value, saponification value, and unsaponifiable matters are important analytical parameters to identity for quality assurance. These neutral glyceride-rich stearin and olein fractions, along with unsaponifiable matters, can be used as nutritionally and functionally superior quality food ingredients in margarine and in baked goods as shortenings.     

Physico‐chemical properties of palm olein fractions as a function of diglyceride content in the starting material

Crude olein preparations with different amounts of diacylglycerols (DAG) were refined, bleached and deodorized (RBD) prior to the dry fractionation process. The RBD olein samples with different amounts of DAG were then individually fractionated into low‐melting (super olein) and high‐melting fractions (soft stearin). Physical and chemical characteristics, i.e. iodine value, cloud point, slip melting point, triacylglycerol (TAG) and DAG profile, fatty acid composition, thermal profile and solid fat content, of the super olein and soft stearin fractions were analyzed. The TAG profile obtained from the RBD olein having a low DAG content (0.89%) showed a higher amount of the diunsaturated TAG, i.e. dioleyl pamitoyl glycerol, in the olein fraction (57.3%). This, consequently, led to super olein fractions with a better iodine value (IV 65) and the cloud point at 1.3 °C, compared to non‐treated super olein (DAG 5%) with an IV of 60.5 and the cloud point at 4.1 °C.     

Modifications of butter stearin by blending and interesterification for better utilization in edible fat products

This work primarily aims to further modify the stearin fractions, obtained from anhydrous milk fat, after fractionation by dry process and by solvent process using isopropanol, for extending their scope of utilization in edible fat products. Butter stearin fractions, on blending with liquid oils like sunflower oil and soybean oil in different proportions, offer nutritionally important fat products with enriched content of essential fatty acids like C_18∶2 and C_18∶3. The butter stearin fraction from isopropanol fractionation, when interesterified with individual liquid oils by Mucor miehei lipase as a catalyst, yields fat products having desirable properties in making melange spread fat products with reasonable content of polyunsaturated fatty acids and almost zero trans fatty acid content.     

Formulation of zero-<Emphasis Type="Italic">trans</Emphasis> acid shortenings and margarines and other food fats with products of the oil palm

The fruit of the oil palm yields two types of oil. The flesh yields 20–22% of palm oil (C16∶0 44%, C18∶1 39%, C18∶2 10%). This represents about 90% of the total oil yield. The other 10%, obtained from the kernel, is a lauric acid oil similar to coconut oil. Palm oil is semisolid, and a large part of the annual Malaysian production of about 14 million tonnes is fractionated to give palm olein, which is widely used for industrial frying, and palm stearin, a valuable hard stock. Various grades of the latter are available. Formulae have been developed by straight blending and by interesterification of palm oil and palm kernel oil to produce shortenings and margarines using hydrogenated fats to give the consistency required. Products that include these formulations are cake shortenings, vanaspati (for the Indian subcontinent), soft and brick margarines, pastry margarines, and reduced fat spreads. Other food uses of palm products in vegetable-fat ice cream and cheese, salad oils, as a peanut butter stabilizer, and in confectioners fats are discussed briefly here.     

Comparison of lipase-transesterified blend with some commercial solid frying shortenings in Malaysia

A transesterified experimental solid frying shortening was prepared from a palm stearin/palm kernel olein blend at 1∶1 ratio (by weight) by using Rhizomucor miehei lipase at 60°C for 6 h. The fatty acid (FA) and triacylglycerol compositions, polymorphic forms, melting and cooling characteristics, slip melting point (SMP), and solid fat content (SFC) of the transesterified blend were then compared with five commercial solid frying shortenings (three domestic and two imported) found in Malaysia. All the domestic shortenings contained nonhydrogenated palm oil or palm olein and palm stearin as the hard stock, whereas the imported frying shortenings were formulated from soybean oil and cottonseed oil and contained high level of β′ crystals. Trans FA were also found in these samples. The lipase-transesterified blend was found to be more β′-tending than the domestic samples. The SMP of the transesterified blend (47.0°C) fell within the range of the domestic samples (37.8–49.7°C) but was higher than the imported ones (42.3–43.0°C). All samples exhibited similar differential scanning calorimetry cooling profiles, with a narrow peak at the higher temperatures and a broad peak at the lower temperatures, even though their heating thermograms were quite different. Imported samples had flatter SFC curves than both the experimental and domestic samples. The domestic samples were found to have better workability or plasticity at higher temperatures than the imported ones, probably because they were formulated for a tropical climate.     

Fractionation of lauric oils

The different methods of edible oil fractionation are reviewed, and the applicability of these to the fractionation of palm kernel and coconut oils is discussed. Crystallization from solvents such as acetone, hexane or 2-nitro-propane, is the most easily understood and most convenient for small-scale laboratory trials, but the cost of solvents and the need to flameproof plants makes it uneconomical for an industrial undertaking. Dry crystallization is commonly employed, and there are several methods, described here, for subsequent separation of solid stearin from liquid olein. Chemical and physical properties of the separated stearins and oleins depend on fractionation conditions and on the yields sought. These are reviewed. The properties of the fractions may be further modified by hydrogenation, interesterification, blending or combinations of these techniques. Many sophisticated confectionery fats are manufactured from lauric stearins and their methods of manufacture and product applications are reviewed. A commercial operation must take care to find a good outlet for the secondary fractionation products (or byproducts) however, and useful outlets for these secondary fractions are therefore considered in addition to those of the main product.     

Variation in fatty acid composition of the different acyl lipids in seed oils from fourSesamum species

Seeds from different collections of cultivatedSesamum indicum Linn. and three related wild species [specifically,S. alatum Thonn.,S. radiatum Schum and Thonn. andS. angustifolium (Oliv.) Engl.] were studied for their oil content and fatty acid composition of the total lipids. The wild seeds contained less oil (ca. 30%) than the cultivated seeds (ca. 50%). Lipids from all four species were comparable in their total fatty acid composition, with palmitic (8.2–12.7%), stearic (5.6–9.1%), oleic (33.4–46.9%) and linoleic acid (33.2–48.4%) as the major acids. The total lipids from selected samples were fractionated by thin-layer chromatography into five fractions: triacylglycerols (TAG; 80.3–88.9%), diacylglycerols (DAG; 6.5–10.4%), free fatty acids (FFA; 1.2–5.1%), polar lipids (PL; 2.3–3.5%) and steryl esters (SE; 0.3–0.6%). Compared to the TAG, the four other fractions (viz, DAG, FFA, PL and SE) were generally characterized by higher percentages of saturated acids, notably palmitic and stearic acids, and lower percentages of linoleic and oleic acids in all species. Slightly higher percentages of long-chain fatty acids (20∶0, 20∶1, 22∶0 and 24∶0) were observed for lipid classes other than TAG in all four species. Based on the fatty acid composition of the total lipids and of the different acyl lipid classes, it seems thatS. radiatum andS. angustifolium are more related to each other than they are to the other two species.     

Clarity of blends of double-fractionated palm olein with low-erucic acid rapeseed oil

Double-fractionated palm olein (DfPOo) fractions with iodine values (IV) of 60 and 65 were each blended with low-erucic acid rapeseed (LEAR) oil in various proportions. Clarities of the blends at different temperatures were determined. Maximum levels of DfPOo-IV60 and DfPOo-IV65 in blends that remained clear at 20°C for at least 120 d were 40 and 80%, respectively. At 15°C, the maximum levels were 10 and 40%, and at 10°C, 10 and 20%, respectively. At 5°C, only a blend of 10% DfPOo-IV65 in LEAR remained clear for 120 d. Maximum levels of DfPOo-IV60 and DfPOo-IV65 in blends that passed the cold test were 30% for both palm oleins. Maximum levels of the palm oleins in blends with LEAR were higher than those of blends with soybean oil. Cloud points were lower in palm olein/LEAR blends than those of palm olein/soybean oil blends, probably because LEAR contains less saturated fatty acids than soybean oil.     

Cocoa butter extender from Simarouba glauca fat

Simarouba glauca is a rich source of fat, having a melting point of about 29°C and consisting of palmitic (12.5%), stearic (27%) and oleic (56%) as major fatty acids. It consists of about 30% of symmetrical monounsaturated-type triacylglycerols and appears to be a good source of fat for preparation of cocoa butter (CB) extender. The stearin fraction (35% yield) obtained by solvent fractionation showed an increased supercooling property and a sudden rise in temperature during solidification compared to native fat as shown by cooling curves. The fraction had a narrow melting range and consisted of a high content (66%) of symmetrical monounsaturated-type triacylglycerols like CB. The fraction was compatible with CB even at 50% substitution. In addition, the fraction did not affect the formation of stable or other polymorphic forms of CB at different tempering conditions. The fraction obtained by dry fractionation also had properties similar to that obtained by solvent fractionation. The conditions of the fractionation determine the yield of stearin, which in turn alters the melting characteristics of the fractions. The stearin obtained after removal of about 60–65% olein was found to be suitable as a CB extender to replace up to 25% of CB in chocolate products.     

Stabilization of oils by microencapsulation with heated protein-glucose syrup mixtures

The use of proteins [whey protein isolate (WPI) or soy protein isolate (SPI) in combination with dried glucose syrup (DGS) for stabilization of microencapsulated spray-dried emulsions containing tuna oil, palm stearin, or a tuna oil-palm stearin blend was investigated. Pre-emulsions containing heated (100°C/30 min) protein-DGS mixtures and oils at oil/protein ratios of 0.75∶1 to 4.5∶1 were homogenized at two passes (35+10 or 18+8 MPa) and spray-dried to produce 20–60% oil powders. Microencapsulation efficiency decreased at lower homogenization pressure and as the oil load in the powder was increased beyond 50% but was independent of the type of oil encapsulated and the total solids (TS) content of the emulsions (24–33% TS) prior to drying. Oxidative stabilities of the powders, as indicated by headspace propanal values and PV after 4 wk of storage at 23°C, generally decreased with increasing oil content and homogenization pressure but increased with increasing TS of the emulsion prior to drying. Powder containing palm stearin was more stable to oxidation than powders containing a 1∶1 ratio of palm stearin and tuna oil or only tuna oil. Heated WPI-DGS formulations were superior to corresponding formulations stabilized by heated SPI-DGS, producing spray-dried powders with higher microencapsulation efficiency and superior oxidative stability.     

Effect of solvent polarity and fractionation temperature on the physicochemical properties of squid viscera stearin

Complete utilization of squid viscera oil was found to be feasible by solvent fractionation. The effects of solvent polarity and temperature on yield, soft melting point, fatty acid composition and solid fat content of the stearin were studied. Although yield increased with increasing solvent polarity and with decreasing fractionation temperature, the stearin obtained has a lower soft melting point. This makes it unsuitable as a table margarine. Operation at lower temperature also increased the operating cost. Solid fat content of the stearins fractionated at-1°C was 10% higher than of those at -5 or -9°C for all solvent polarities studied. Solid fat content of stearin increased with the decrease of solvent polarity at every tested temperature. The combined effects of polarity and fractionation temperature affect the soft melting point and solid fat content, which determine the commercial application of the stearin. The percentage of saturated fatty acids of stearin decreased with increasing solvent polarity, and the percentage of eicosapentaenoic acid (EPA) + docosahexaenoic acid (DHA) increased with solvent polarity and fractionation temperature. The percentage of EPA + DHA in stearin decreased with temperature, except for those from 5.1 p′ solvent. The practical fractionation condition is at -1 or -5°C with a solvent polarity of 5.1 p′. The stearin fraction can be made into a series of products, such as high EPA- and DHA-containing table margarine.     

D. K. Bhattacharyya,Modification of tallow fractions in the preparation of edible fat products

Investigation has been carried out with an intention to prepare shortening, margarine fat bases, and value-added edible fat products like cocobutter substitute from tallow. For this, tallow was fractionated at low (12 and 15 °C) and intermediate (25 °C) temperatures by solvent (acetone) fractionation process. The stearin fractions (yield: 23—40% (w/w) and slip melting point: 45—50.5 °C) thus obtained were blended and interesterified with liquid oils, such as sunflower, soybean, rice bran etc. by microbial lipase catalyzed route. The olein fractions (yield: 60—77% (w/w) and slip melting point: 21—32.5 °C) were also chemically interesterified (using NaOMe) and biochemically (using Rhizomucor miehei lipase, Lipozyme IM 20). The olein fractions were also blended with sal (Shorea robusta) fat, sal olein, and acidolysed karanja (Pongamia glabra) stearin. As revealed from their slip melting point and solid fat index, the products thus prepared were found to be suitable for shortening, margarine fat bases, and vanaspati substitute.     

The fractionation of marine-oil fatty acids with urea

Summary In two series of experiments, marine-animal-oil fatty acids were fractionated with urea using methanol as solvent. In the first series, menhaden-oil fatty acids were fractionated at 1°C. Almost all the saturated and monoenoic fatty acids were removed at mole ratios of 12∶1 to 13∶1. At higher ratios increasing amounts of the less stable dienoic fatty acids were precipitated. By the use of the appropriate ratio, fractions having iodine values above 300 were prepared. In the second series, fatty acids from the oils of menhaden, herring, tuna, seal, salmon eggs, and salmon heads and viscera were fractionated at a mole ratio of urea to fatty acid of 9.2∶1. At 25° and 1° the complexes were composed almost entirely of saturated and monoenoic fatty acids, but as the temperature was lowered to −30°, the content of dienoic fatty acids in the precipitates increased. Presented at the Regional American Chemical Society Meeting, Richland, Wash., June 11–12, 1954. One of the laboratories of the Branch of Commercial Fisheries, Fish and Wildlife Service, U. S. Department of the Interior.     

Monitoring milk fat fractionation: Effect of agitation, temperature, and residence time on physical properties

With the use of two central composite designs, the effects of agitation rate, fractionation temperature, and residence time on the thermal properties of the stearin and olein milk fat fractions were investigated. The main function of agitation during fat fractionation was suspending the crystal aggregates and enhancing the heat transfer. For the experimental conditions described here, crystal aggregation did not seem to be affected by agitation. The effect of fractionation temperature on the physical properties of the olein fraction was very significant. Triangle diagrams were shown to be a useful tool for monitoring and designing fractionation processes. They illustrate that oleins with similar melting properties can be produced over a range of yields of stearin, which is important from an industrial point of view. Crystallizer residence time, which influences production costs, clearly affects both stearin yield and olein melting properties. For any fractionation temperature, stearin fractions with virtually identical melting properties and yields can be obtained over a range of olein melting properties. Manipulation of both the fractionation temperature and residence time allows the fractionation process to be adapted to meet changing market demands for fractions with different melting properties.     

Production of High Oleic Palm Oils on a Pilot Scale

Refined, bleached and deodorized palm olein (RBD POo) with an iodine value (IV) of 62 was chemically interesterified with methyl oleate (MO) at a ratio of 50:50 (w/w). The reaction was carried out at 110 °C in the presence of sodium methoxide as a catalyst using a 100-kg pilot scale reactor. Randomization between 15 and 30 min resulted in less free fatty acid (FFA) formation and higher oleic content in the interesterified product as compared to longer reaction time of 60–90 min. Sodium methoxide-catalyzed ester interchange increased the oleic content of the interesterified product to more than 57% from its initial content of 45%. The product obtained also has an IV of more than 75. The interesterified oil was then subjected to dry fractionation in a 200-kg De Smet jacketed crystallizer at 8 °C to further enhance the oleic content of the liquid olein fraction. The resulted olein had an improved cloud point and higher IV of 81. The solid stearin had a slightly higher IV and oleic content as compared to normal palm stearin. The solid fat content was comparable to normal palm oil. The pilot scale study has proven a successful conversion of laboratory findings to a larger scale production and gave the most realistic information for possible commercialization.     

Utilization of high-melting palm stearin in lipase-catalyzed interesterification with liquid oils

Palm stearin with a melting point (m.p.) of 49.8°C was fractionated from acetone to produce a low-melting palm stearin (m.p.=35°C) and a higher-melting palm stearin (HMPS, m.p.=58°C) fraction. HMPS was modified by interesterification with 60% (by weight) of individual liquid oils from sunflower, soybean, and rice bran by means of Mucor miehei lipase. The interesterified products were evaluated for m.p., solid fat content, and carbon number glyceride composition. When HMPS was interesterified individually with sunflower, soybean or rice bran at the 60% level, the m.p. of the interesterified products were 37.5, 38.9, and 39.6°C, respectively. The solid fat content of the interesterified products were 30–35 at 10°C, 17–19 at 20°C, and 6–10 at 30°C, respectively. The carbon number glyceride compositions also changed significantly. C₄₈ and C₅₄ glycerides decreased remarkably with a corresponding increase of the C₅₀ and C₅₂ glycerides. All these interesterified products were suitable for use as trans acid-free and polyunsaturated fatty acid-rich shortening and margarine fat bases.