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.     

Enzymatic interesterification of palm stearin and palm kernel olein

Palm stearin (POs) and palm kernel olein (PKOo) blends were modified by enzymatic interesterification (IE) to achieve the physical properties of margarine fats. POs and PKOo are both products of the palm oil industry that presently have limited use. Rhizomucor miehei lipase (Lipozyme IM 60) was used to catalyze the interesterification of oil blends at 60°C. The progress of interesterification was monitored by following changes in triacylglyceride composition. At 60°C interesterification can be completed in 5 h. Degrees of hydrolysis obtained through IE for all blends were decreased from 2.9 to 2.0 by use of dry molecular sieves. The solid fat contents of POs/PKOo 30:70 and 70:30 interesterified blends were 9.6 and 18.1 at 20°C, and 0 and 4.1 at 35°C, respectively. The slip melting point (SMP) of POs/PKOo 30:70 was 40.0°C before interesterification and 29.9°C after IE. For POs/PKOs 70:30, SMP was 47.7 before and 37.5°C after IE. These thermal characteristics of interesterified POs/PKOo blend ratios from 30:70 to 70:30 were comparable to those of commercial margarines. Results showed that IE was effective in producing solid fats with less than 0.5% trans.     

Application of palm olein in the production of zero‐trans Iranian vanaspati through enzymatic interesterification

The utilization of palm olein in the production of zero‐trans Iranian vanaspati through enzymatic interesterification was studied. Vanaspati fat was made from ternary blends of palm olein (POL), low‐erucic acid rapeseed oil (RSO) and sunflower oil (SFO) through direct interesterification of the blends or by blending interesterified POL with RSO and SFO. The slip melting point (SMP), the solid fat content (SFC) at 10–40 °C, the carbon number (CN) triacylglycerol (TAG) composition, the induction period (IP) of oxidation at 120 °C (IP₁₂₀) and the IP of crystallization at 20 °C of the final products and non‐interesterified blends were evaluated. Results indicated that all the final products had higher SMP, SFC, IP of crystallization and CN 48 TAG (trisaturated TAG), and lower IP₁₂₀, than their non‐interesterified blends. However, SMP, SFC, IP₁₂₀, IP of crystallization and CN 48 TAG were higher for fats prepared by blending interesterified POL with RSO and SFO. A comparison between the SFC at 20–30 °C of the final products and those of a commercial low‐trans Iranian vanaspati showed that the least saturated fatty acid content necessary to achieve a zero‐trans fat suitable for use as Iranian vanaspati was 37.2% for directly interesterified blends and 28.8% for fats prepared by blending interesterified POL with liquid oils.     

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.     

Effect of enzymatic transesterification with flaxseed oil on the high-melting glycerides of palm stearin and palm olein

The effects of enzymatic transesterification on the melting behavior of palm stearin and palm olein, each blended separately with flaxseed oil in the ratio of 90∶10 and catalyzed by various types of lipases, were studied. The commercial lipases used were Lipozyme IM, Novozyme 435, and myceliumbound lipases of Aspergillus flavus and A. oryzae. The slip melting point (SMP) of the palm stearin/flaxseed oil (PS/FS) mixture transesterified with lipases decreased, with the highest drop noted for the mixture transesterified with Lipozyme IM. However, when palm stearin was replaced with palm olein, the SMP of the palm olein/flaxseed oil (PO/FS) mixture increased, with the commercial lipases causing an increase of 41 to 48% compared to the nontransesterified material. As expected, the solid fat content (SFC) of the transesterified PS/FS was lower at all temperatures than that of the nontransesterified PS/FS sample. In contrast, all transesterified PO/FS increased in SFC, particularly at 10°C. Results from DSc and HPLC analyses showed that the high-melting glycerides, especially the tripalmitin of palm stearin, were hydrolyzed. Consequently, 1,3-dipalmitoylglycerol was found to accumulate in the mixture. There was no difference in the FA compositions between the transesterified and nontransesterified mixtures.     

Physical and chemical properties of trans-free fats produced by chemical interesterification of vegetable oil blends

Fat blends, formulated by mixing a highly saturated fat (palm stearin or fully hydrogenated soybean oil) with a native vegetable oil (soybean oil) in different ratios from 10:90 to 75:25 (wt%), were subjected to chemical interesterification reactions on laboratory scale (0.2% sodium methoxide catalyst, time=90 min, temperature=90°C). Starting and interesterified blends were investigated for triglyceride composition, solid fat content, free fatty acid content, and trans fatty acid (TFA) levels. Obtained values were compared to those of low- and high-trans commercial food fats. The interesterified blends with 30–50% of hard stock had plasticity curves in the range of commercial shortenings and stick-type margarines, while interesterified blends with 20% hard stock were suitable for use in soft tubtype margarines. Confectionery fat basestocks could be prepared from interesterified fat blends with 40% palm stearin or 25% fully hydrogenated soybean oil. TFA levels of interesterified blends were low (0.1%) compared to 1.3–12.1% in commercial food fats. Presented at the 88th AOCS Annual Meeting and Expo, May 11–14, 1997, Seattle, Washington.     

Enzymatic interesterification of tallow-sunflower oil mixtures

In an effort to improve the physical and/or thermal characteristics of solid fats, the enzymatic interesterification of tallow and butterfat with high-oleic sunflower oil and soybean oil was investigated. The two simultaneously occurring reactions, interesterification and hydrolysis, were followed by high-performance liquid chromatography of altered glycerides and by gas-liquid chromatography of liberated free fatty acids. The enzymes used in these studies were immobilized lipases that included either a 1,3-acyl-selective lipase or acis-9-C₁₈-selective lipase. The degree of hydrolysis of the fat/oil mixtures was dependent upon the initial water content of the reaction medium. The extent of the interesterification reaction was dependent on the amount of enzyme employed but not on the reaction temperature over the range of 50–70°C. Changes in melting characteristics of the interesterified glyceride mixtures were followed by differential scanning calorimetry of the residual mixed glycerides after removal of free fatty acids. Interesterification of the glyceride mixes with the two types of enzymes allowed for either a decrease or increase in the solid fat content of the initial glyceride mix.     

Physical Properties of <Emphasis Type="Italic">trans</Emphasis>-Free Bakery Shortening Produced by Lipase-Catalyzed Interesterification

Lipase-catalyzed interesterified solid fat was produced with fully hydrogenated soybean oil (FHSBO), and rapeseed oil (RSO) and palm stearin (PS) in a weight ratio of 15:20:65, 15:40:45 and 15:50:35. The interesterified fats contained palmitic (27.8–44.6%), stearic (15.6–16.2%), oleic (27.5–36.5%) and linoleic acids (8.0–13.5%). After interesterification of the blends, the physical properties of the products changed and showed lower melting points and solid fat contents, different melting and crystallization behaviors as well as the formation of more stable crystals. The produced interesterified fats (FHSBO:RSO:PS 15:20:65, 15:40:45 and 15:50:35 blends) contained desirable crystal polymorphism (β′ form) as determined by X-ray diffraction spectroscopy, a long plastic range with solid fat content of 51–63% at 10 °C to 4–12% at 40 °C, and melting points of 39 (15:50:35), 42 (15:50:45) and 45 °C (15:20:65). However, a reduction in tocopherols (α and γ) content and a reduced oxidative stability were observed in the interesterified fats. The physical properties of the interesterifed fats were influenced by the amount of PS, resulting in more hardness and higher solid fat contents for 15:20:65 than 15:40:45 and 15:50:35 blends. The present study suggested that the produced interesterified fats containing trans-free fatty acids could be used as alternatives to hydrogenated types of bakery shortenings.     

Physico-chemical characteristics of palm-based oil blends for the production of reduced fat spreads

The effect of blending and interesterification on the physicochemical characteristics of fat blends containing palm oil products was studied. The characteristics of the palm-based blends were tailored to resemble oil blends extracted from commercial reduced fat spreads (RFS). The commercial products were found to contain up to 20.4% trans fatty acids, whereas the palm-based blends were free of trans fatty acids. Slip melting point of the blends varied from 26.0–32.0°C for tub, and 30.0–33.0°C for block RFS. Solid fat content at 5 and 10°C (refrigeration temperature), respectively, varied from 10.9–19.7% and 8.5–17.6% for tub, and 28.2–38.6% and 20.8–33.5% for block RFS. Melting enthalpy of the tub RFS varied from 35.0–54.3 J/g and that of block RFS varied from 58.0–75.4 J/g. To produce block RFS, 65% palm oil (PO) and 18% palm kernel olein (PKOo) could be added in a ternary blend with sunflower oil (SFO), but only 47% PO and 10% PKOo are suggested for tub RFS. Higher proportion of PO, i.e., 72% for block RFS and 65% for tub RFS, could be used after the ternary blend was interesterified. Although a ternary blend of palm olein (POo)/SFO/PKOo was not suitable for RFS formulation, after interesterification as much as 90% POo and 26% PKOo could be used in the block RFS formulation. For tub RFS a maximum of 30% POo was found suitable.     

Partition coefficient of diglycerides in crystallization of palm oil

Crystallization of palm oil with and without solvent was carried out over a temperature range of 10–25°C. The yields of olein, the diglyceride contents, and compositions of the stearin and olein phases were determined by thin-layer and gas-liquid chromatography. The three major diglycerides, analyzed as C₃₂, C₃₄, and C₃₆, are mainly dipalmitoyl glycerol, palmitoyloleoyl glycerol, and dioleoyl glycerol. In crystallization without solvent, C₃₂ (PP) had a strong affinity for the stearin fraction and C₃₆ diglycerides concentrated in the olein phase. The partition coefficient of diglycerides between the olein and stearin phases was temperature-dependent and was influenced by the type of solvent used. Although solvent enhances the diglyceride partition into the olein phase, partitioning is more effective at low temperatures and with acetone as the solvent for fractionation.     

Composition and thermal profile of crude palm oil and its products

Gas-liquid chromatography and high-performance liquid chromatography (HPLC) were used to determine fatty acids and triglyceride (TG) compositions of crude palm oil (CPO), refined, bleached, and deodorized (RBD) palm oil, RBD palm olein, and RBD palm stearin, while their thermal profiles were analyzed by differential scanning calorimeter (DSC). The HPLC chromatograms showed that the TG composition of CPO and RBD palm oil were quite similar. The results showed that CPO, RBD palm oil, RBD olein, and superolein consist mainly of monosaturated and disaturated TG while RBD palm stearin consists mainly of disaturated and trisaturated TG. In DSC cooling thermograms the peaks of triunsaturated, monosaturated and disaturated TG were found at the range of −48.62 to −60.36, −25.89 to −29.19, and −11.22 to −1.69°C, respectively, while trisaturated TG were found between 13.72 and 27.64°C. The heating thermograms of CPO indicated the presence of polymorphs β₂′, α, β₂′, and β₁. The peak of CPO was found at 4.78°C. However, after refining, the peak shifted to 6.25°C and became smaller but more apparent as indicated by RBD palm oil thermograms. The heating and cooling thermograms of the RBD palm stearin were characterized by a sharp, high-melting point (high-T) peak temperature and a short and wide low-melting point (low-T) peak temperature, indicating the presence of occluded olein. However, for RBD palm olein, there was only an exothermic low-T peak temperature. The DSC thermograms expressed the thermal behavior of various palm oil and its products quite well, and the profiles can be used as guidelines for fractionation of CPO or RBD palm oil.     

Production of margarine fats by enzymatic interesterification with silica-granulated Thermomyces lanuginosa lipase in a large-scale study

Interesterification of a blend of palm stearin and coconut oil (75∶25, w/w), catalyzed by an immobilized Thermomyces lanuginosa lipase by silica granulation, Lipozyme TL IM, was studied for production of margarine fats in a 1- or 300-kg pilot-scale batch-stirred tank reactor. Parameters and reusability were investigated. The comparison was carried out between enzymatic and chemical interesterified products. Experimentally, Lipozyme TL IM had similar activity to Lipozyme IM for the interesterification of the blend. Within the range of 55–80°C, temperature had little influence on the degree of interesterification for 6-h reaction, but it had slight impact on the content of free fatty acids (FFA). Drying of Lipozyme TL IM from water content 6 to 3% did not affect its activity, whereas it greatly reduced FFA and diacylglycerol contents in the products. Lipozyme TL IM was stable in the 1-kg scale reactor at least for 11 batches and the 300-kg pilot-scale reactor at least for nine batches. Due to regiospecificity of the lipase (sn-1,3 specific), enzymatically interesterified products had different fatty acid distribution at sn-2 position from the chemically randomized products, implying the potential nutritional benefits of the new technology. Presented at the 91st American Oil Chemists' Society Annual Meeting in San Diego, April 28, 2000.     

Physical properties of lipase‐catalyzed interesterification of palm stearin with canola oil blends

Interesterified blends of hard palm stearin (IV of 11) and canola oil (hPS/CO) in ratios of 20 : 80, 30 : 70, 40 : 60, 50 : 50, 60 : 40 and 70 : 30 were prepared using immobilized Thermomyces lanuginosus lipase (Lipozyme TL IM). Comparison of physical properties was carried out between non‐interesterified and enzymatically interesterified products by monitoring their slip melting point (SMP), solid fat content (SFC), melting thermogram and polymorphism behavior. The Lipozyme TL IM‐catalyzed interesterification significantly modified the physical properties of the hPS:CO blends. The results showed that all the interesterified blends had lower SMP and SFC than their unreacted blends. The SMP result showed that the interesterified blends of hPS/CO 40 : 60, 50 : 50 and 60 : 40 could be useful for stick margarine and shortening applications, respectively. From the SFC analysis, the interesterified blends of hPS/CO 40 : 60 have SFC curves similar to vanaspati. The interesterified blends of hPS/CO 50 : 50 and 60 : 40 have SFC curves similar to margarines, puff pastry margarine and shortening. Interesterification had replaced the higher‐ and lower‐melting triacylglycerols by the middle‐melting triacylglycerols, yielding mixtures of lower SMP and SFC, compared to the original palm stearin. X‐ray diffraction analysis indicated the appearance of β' crystals in all the interesterified hPS/CO blends from predominantly β‐type oils.     

Physical properties of Pseudomonas and Rhizomucor miehei lipase-catalyzed transesterified blends of palm stearin:palm kernel olein

The physical properties of Pseudomonas and Rhizomucor miehei lipase-catalyzed transesterified blends of palm stearin:palm kernel olein (PS:PKO), ranging from 40% palm stearin to 80% palm stearin in 10% increments, were analyzed for their slip melting points (SMP), solid fat content (SFC), melting thermograms, and polymorphic forms. The Pseudomonas lipase caused a greater decrease in SMP (15°C) in the PS:PKO (40:60) blend than the R. miehei lipase (10.5°C). Generally, all transesterified blends had lower SMP than their unreacted blends. Pseudomonas lipase-catalyzed blends at 40:60 and 50:50 ratio also showed complete melting at 37°C and 40°C, respectively, whereas for the R. miehei lipase-catalyzed 40:60 blend, a residual SFC of 3.9% was observed at 40°C. Randomization of fatty acids by Pseudomonas lipase also led to a greater decrease in SFC than the rearrangement of fatty acids by R. miehei lipase. Differential scanning calorimetry results confirmed this observation. Pseudomonas lipase also successfully changed the polymorphic forms of the unreacted blends from a predominantly β form to that of an exclusively β′ form. Both β and β′ forms existed in the R. miehei lipase-catalyzed reaction blends, with β′ being the dominant form.     

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.     

Comparative Study of Table Margarine Prepared from Moringa oleifera Seed Oil‐Palm Stearin Blend and Commercial Margarines: Composition,Thermal, and Textural Properties

This study aims to produce an oleic acid‐rich table margarine from Moringa oleifera seed oil (MoO)‐palm stearin (PS) blend (70:30, w/w) and compare its composition, thermal behavior, and textural properties during storage with those of commercial margarines (CM1 and CM2). The major fatty acid in MoO/PS blend, CM1 and CM2 is oleic acid (67.85%, 38.54%, and 35.35%, respectively). Hence, many of their triacylglycerols are derived from the acid. MoO/PS blend has a higher complete melting temperature (43.50 °C) compared to CM1 (35.50 °C) and CM2 (35.53 °C). The solid fat content (SFC) of MoO/PS blend at 10 °C (28.7%) is lower than CM1 (32%) and CM2 (68.4%). However, the MoO/PS blend has a higher SFC (6.47%) at 35 °C compared to CMs. At 20 °C, the viscosity of experimental blend margarine (EBM) decreases but CM1 and CM2 increase at the end of the storage study. After 8 weeks of storage, all margarines are harder and CM2 is the hardest. The adhesiveness of EMB and CM2 is similar to the fresh samples while CM1 is more adhesive after storage. In short, it is possible to produce an oleic acid‐enriched margarine from MoO/PS blend that has better textural properties. Practical Applications: Moringa oleifera seed oil is one of the superior oils that contains high levels of oleic acid. However, its high iodine value and low melting point limit its application in the production of margarine. This study shows that direct blending of M. oleifera seed oil with palm stearin could produce margarine with high oleic acid contents and better textural properties in terms of viscosity, hardness, and adhesiveness. The informative data provide supporting evidence for blending of M. oleifera seed oil with palm stearin to produce margarine that could overcome the issues that hinder the M. oleifera seed oil from being produced into margarine.     

Cocoa Butter Alternatives from Enzymatic Interesterification of Palm Kernel Stearin,Coconut Oil,and Fully Hydrogenated Palm Stearin Blends

Structured lipids (SL) were produced from enzymatic interesterification (EIE) of palm kernel stearin (PKS), coconut oil (CNO), and fully hydrogenated palm stearin (FHPS) blends in various mass ratios. The EIE reactions were performed at 60 °C for 6 hours using immobilized Lipozyme RM IM with a mixing speed of 300 rpm. The physicochemical properties, crystallization and melting behavior, solid fat content (SFC), crystal morphology and polymorphism of the physical blends (PB), and the SL were characterized and compared with commercial cocoa butter and cocoa butter alternatives (CBA). EIE significantly modified the triacylglycerol compositions of the fat blends, resulting in changes in the physical properties and the crystallization and melting behavior. SFC and slip melting point of all SL decreased from those of their counterpart PB. In particular, SL obtained from EIE of blends 60:10:30 and 70:10:20 (PKS:CNO:FHPS) exhibited a high potential to be used as trans-free CBA as they showed similar melting ranges, melting peak temperatures, and SFC curves to the commercial CBA with fine needle-like crystals and desirable β' polymorph.     

Effect of enzymatic transesterification on the melting points of palm stearin-sunflower oil mixtures

Transesterification with lipases may be used to convert mixtures of fats to plastic fats, making them more suitable for use in edible products. In our study, 1,3-specific (Aspergillus niger, Mucor javanicus, Rhizomucor miehei, Rhizopus javanicus, and Rhizopus niveus) and nonspecific (Pseudomonas sp. and Candida rugosa) lipases were used to transesterify mixtures of palm stearin and sunflower oil (PS-SO) at a 40:60 ratio in a solvent-free medium. The transesterified mixtures of PS-SO were analyzed for their percentage free fatty acids (FFA), degree and rate of transesterification, solid fat content, slip melting point (SMP), and melting characteristics by differential scanning calorimetry. Results indicated that Pseudomonas sp. lipase produced the highest degree (77.3%) and rate (50.0 h⁻¹) of transesterification, followed by R. miehei lipase at 32.7% and 27.1 h⁻¹, respectively. The highest percentage FFA liberated was also in the reaction mixtures catalyzed by Pseudomonas sp. (2.5%) lipase and R. miehei (2.4%). Pseudomonas-catalyzed mixtures produced the biggest drop in SMP (13.5°C) and showed complete melting at below body temperature. All results indicated conversion of the PS-SO mixtures to a more fluid product. The findings also suggest that the specificity of lipases may not play a significant role in lowering the melting point of the PS-SO mixtures.     

Trans-free vanaspati containing ternary blends of palm oil-palm stearin-palm olein and palm oil-palm stearin-palm kernel olein

Four samples of trans-free vanaspati were made using palm oil-palm stearin-palm olein (PO-POs-POo) blends (set A) and another four samples (set B) using palm oil-palm stearin-palm kernel olein (PO-POs-PKOo). Palm stearin iodine value [iodine value (IV), 30] and soft palm stearin (IV, 44) were used in this study. The products were evaluated for their physical and chemical properties. It was observed that most of the vanaspati were granular (grainy) and had a shiny appearance. Chemical analyses indicated that vanaspati consisting of PO-POs-POo had higher IV (47.7–52.4) than the PO-POs-PKOo vanaspati (37.5–47.3). The higher IV demonstrated by set A samples was due to their higher content of unsaturated fatty acids, 46.0–50.0% compared to 36.6–45.0% in set B. Decreasing the amount of palm oil while increasing palm stearin in the formulations resulted in higher slip melting points and higher yield values. Eutectic interaction was observed in PO-POs-PKOo blends. The β′ crystalline form was predominent in PO-POs-POo samples (set A). One formulation in set B exhibited β crystallinity. From the differential scanning calorimetry thermograms, samples in set B showed a high peak at the low-melting region as well as a high peak at the high-melting region. In set A, the peak at the low-melting region was relatively lower.     

Enzymatic interesterification of structured lipids containing conjugated linoleic acid with palm stearin for possible margarine production

Structured lipids containing conjugated linoleic acid as a functional ingredient were blended with palm stearin in the ratios of 30 : 70, 40 : 60, 50 : 50, 60 : 40 and 70 : 30 (wt/wt). The blends were subjected to enzymatic interesterification by Candida antarctica lipase. After interesterification of the blends, changes in the physical properties of the products, including lower melting points and solid fat contents along with different melting behaviors, were evidenced. Analysis of triacylglycerols (TAG) of the interesterified blends showed a decrease in the concentration of high‐melting TAG. X‐ray diffraction analysis revealed, that all the reacted blends were predominantly in the β' crystal form. The mixture could be used for the formulation of margarines or other, similar products.