Isopropanol fractionation of butter oil and characteristics of fractions

Fractionation of butter oil from isopropanol and characterization of the chemical composition and the melting properties of the fractions obtained have been investigated. Butter oil was fractionated from isopropanol (1∶4 wt/vol) at 15 to 30°C. The yields of stearins and oleins were dependent on the temperature employed during fractionation. Thus, 24.8 to 48.9% of stearins and 51.5 to 75.2% of oleins could be obtained as the crystallization temperature varied from 15 to 30°C. The stearin fractions displayed a distinct variation in the fatty acid compositions. The palmitic acid content of the stearin fractions varied from 39.1 to 44.0%, and that of stearic from 15.1 to 16.8%, respectively. The olein fractions contained 43.2% stearic acid, and 2.4 to 2.8% palmitoleic acid (C16∶1). The solid fat content values of the stearin fractions obtained were 62–67, 39–50, and 21–25 at 10, 20, and 30°C, respectively. From the results, it is evident that anhydrous milk fat can be fractionated at relatively high temperatures from isopropanol to produce stearin and olein fractions of specific composition and properties.     

Chemical and thermal characteristics of milk-fat fractions isolated by a melt crystallization

Anhydrous milk fat (AMF) was fractionated by a two-stage dry fractionation process to produce three fractions: high melting (HMF), middle melting (MMF), and low melting (LMF). The HMF (m.p. 42°C) exhibited a broad melting range similar to a plastic fat. The MMF (m.p. 33°C) resembled the original AMF (m.p. 31°C), but with slightly higher solid fat content. The LMF (m.p. 16°C) was liquid at ambient temperature. Differences in the thermal properties of these fractions were attributed to the triacylglycerols (TAG) and their fatty acid composition. Saturated TAG with carbon numbers of 36–54 were concentrated in the HMF; whereas unsaturated TAG of carbon number 36–54 predominated in the LMF. Likewise, the long-chain saturated fatty acids were significantly higher and the long-chain unsaturated fatty acids were significantly lower in the HMF fraction. Binary blends of milk-fat fractions with a range of melting profiles were produced by mixing HMF with AMF, MMF, or LMF. Laboratory-prepared fractions were similar to commercially available fractions.     

Effect of milk fat fractions on fat bloom in dark chocolate

Anhydrous milk fat was dissolved in acetone (1∶4 wt/vol) and progressively fractionated at 5°C increments from 25 to 0°C. Six solid fractions and one 0°C liquid fraction were obtained. Melting point, melting profile, solid fat content (SFC), fatty acid and triglyceride profiles were measured for each milk fat fraction (MFF). In general, there was a trend of decreased melting point, melting profile, SFC, long-chain saturated fatty acids and large acyl carbonnumbered triglycerides with decreasing fractionation temperature. The MFFs were then added to dark chocolate at 2% (w/w) addition level. In addition, two control chocolates were made, one with 2% (w/w) full milk fat and the other with 2% (w/w) additional cocoa butter. The chocolate samples were evaluated for degree of temper, hardness and fat bloom. Fat bloom was induced with continuous temperature cycling between 26.7 and 15.7°C at 6-h intervals and monitored with a colorimeter. Chocolate hardness results showed softer chocolates with the 10°C solid fraction and low-melting fractions, and harder chocolates with high-melting fractions. Accelerated bloom tests indicated that the 10°C solid MFF and higher-melting fractions (25 to 15°C solid fractions) inhibited bloom, while the lowermelting MFFs (5 and 0°C solid fractions and 0°C liquid fraction) induced bloom compared to the control chocolates.     

Fractionation of menhaden oil and partially hydrogenated menhaden oil: Characterization of triacylglycerol fractions

Menhaden oil (MO) and partially hydrogenated menhaden oil (PHMO) were dry-fractionated and solvent-fractionated from acetone. After conversion to fatty acid methyl esters, the compositional distribution of saturated, monounsaturated, trans, and n−3 polyunsaturated fatty acids (PUFA) in the isolated fractions was determined by gas chromatography. Acetone fractionation of MO at −38°C significantly increased the n−3 PUFA content in the liquid fractions over that of starting MO (P<0.05). For PHMO, liquid fractions obtained by low-temperature crystallization (−38, −18, and 0°C) from acetone showed significant increases (P<0.05) in monounsaturated fatty acid (MUFA) content over that of the starting PHMO. For selected MUFA-enriched fractions, reversed-phase high-performance liquid chromatography (HPLC) was used to separate, isolate, and characterize the major triacylglycerol (TAG) molecular species present. Thermal crystallization patterns for these fractions also were determined by differential scanning calorimetry (DSC). The results demonstrated that under the appropriate conditions it is possible to dry-fractionate or solvent-fractionate MO and PHMO into various solid and liquid fractions that are enriched in either saturated, monounsaturated, polyunsaturated, or the n−3 classes of fatty acids. Moreover, characterization of these TAG fractions by reversed-phase HPLC gives insight into the compositional nature of the TAG that are concentrated into the various fractions produced by these fractionation processes. Finally, the DSC crystallization patterns for the fractions in conjunction with their fatty acid compositional data allow for the optimization of the fractionation schemes developed in this study. This information allows for the production of specific TAG fractions from MO and PHMO that are potentially useful as functional lipid products.     

Composition and thermal properties of Rhea oil and its fractions

The rhea (Rhea americana) is a large running bird of the ratite family, native to South America. Oil extracted from rhea fat tissue is used in cosmetic manufacture. Here, the thermal behaviour and the fatty acid and triacylglycerol composition of Uruguayan rhea oil are studied. The results are compared with those obtained from two commercial samples of emu oil. The fatty acid profiles of emu and rhea oils are similar. Small variations are reflected in the non‐identical thermal behaviour of the oils. The solid content of both oils is fairly similar at room temperature. Thus, emu oil and rhea oil may replace one another in certain formulations, without resulting in important changes in physicochemical behaviour. The semisolid rhea oil was fractionated in two successive stages: an olein was obtained at 15 °C, which was refractionated at 10 °C. The thermogram of the olein obtained by cooling at 15 °C does not have the peak found at 34 °C in the thermogram of the original oil and is a softer product than the original oil. A further stage of fractionation of this olein produced a new liquid phase of slightly different thermal behaviour from that of the original olein. This product has a solid fat index around 7% at 15 °C and has melted completely at 20 °C. This second olein has more appropriate physical characteristics than those of the olein obtained from the first fractionation when used in liquid cosmetic formulations.     

Column Fractionation of Canola Oil Deodorizer Distillate Using Supercritical Carbon Dioxide

Semi-continuous column fractionation of canola oil deodorizer distillate using supercritical CO₂ (SCCO₂) was carried out to determine the feasibility of value-added processing of this feed material for the recovery of bioactive components such as sterols and tocopherols and to determine the effect of operating conditions [pressure (20, 25 MPa using a temperature gradient of 70–100 °C), temperature (70, 100 °C) and a linear temperature gradient (70–100 °C at 25 MPa)] on extract yield and separation efficiency. Total extract yield increased significantly (p ≤ 0.05) with pressure, whereas at isobaric conditions (25 MPa) the highest yield was obtained at the lowest temperature tested (70 °C). Fractionation efficiency was reflected in the composition of fractions and was affected by operating conditions. Residue composition was determined by extract yield in addition to selectivity. Use of the thermal gradient (70–100 °C) decreased the content of volatiles, free fatty acids and tocopherols while increasing sterol content significantly (p ≤ 0.05) to a level of 40% (GC area %) in the residue obtained at 25 MPa. The findings indicate the potential of canola oil deodorizer distillate as a source of sterols and warrant further research on the countercurrent column fractionation to improve the separation efficiency.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.     

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.     

Purification of Biorefinery Lignin with Alcohols

After hydrothermal pretreatment and enzymatic hydrolysis of wheat straw, a slurry rich in lignin but with a high content of inorganic substances, especially silica, and residual carbohydrates is produced. This slurry was used to develop an ethanol organosolv separation method to produce silica-free lignin fractions. The addition of para toluene sulphonic acid (PTSA) and the use of two alternative long-chain alcohols, oleyl alcohol or nonylphenol, were tested. In every reaction, two lignin fractions were produced and their molecular size and elemental composition were characterized. The yield of each fraction and the change in MWD were studied as a function of temperature and solid to liquid ratio. At 100, 150, and 200°C and with the use of PTSA, high-purity lignin fractions were obtained. After lignin fractionation with nonylphenol, a liquid silica-free product with high lignin content was obtained in yields between 17 and 72%.     

Phase properties of mixtures of ceramides

Ceramides have been proposed to have a central role in the function of the stratum corneum. Ceramides also influence the phase properties of model skin lipid mixtures, but the relevance of this to the stratum corneum function is controversial. Because the stratum corneum contains several classes of ceramides, the type of ceramides used in model mixtures of stratum corneum lipid lamellae may be important. Thus, the properties of α-hydroxy fatty acid containing (HFAC) and nonhydroxy fatty acid containing (NFAC) ceramides and their mixtures have been investigated. Ceramides were obtained by the conversion of purified bovine brain cerebrosides. Isolated, anhydrous HFAC underwent an endothermic solid to liquid transition at 92°C. With hydration, an endothermic transition at 71.8°C was observed which was accompanied by a reduction in the birefringence. The enthalpy increased from 66 to 89 J/g with a 20-d storage time. These thermal properties are very similar to those observed with hydroxy fatty acid containing cerebrosides. In contrast, anhydrous nonhydroxy fatty acid containing ceramides underwent a broad endothermic transition over the temperature range of 50–90°C. When hydrated, the initial endothermic transition was interrupted by an exothermic transition that was followed immediately by a second endothermic transition. During these thermal changes, there was a loss of birefringence, and with completion of the second endothermic transition, a nonbirefringent liquid was observed. NFAC samples, stored at 70°C for 5 min, cooled, and then rescanned, displayed only one endotherm at 75°C. The thermal behavior of mixtures of HFAC and NFAC was relatively simple, with a progressive decrease and broadening in the temperature of the phase transition as the proportion of NFAC increased up to weight fractions of NFAC of 0.7. At lower weight fractions, a plateau in thetransition temperature as a function of weight fraction was observed. Even at a weight fraction of 0.1 HFAC, no transition to a nonbirefringent liquid state was observed. The high enthalpic changes observed with mixtures of HFAC and NFAC are consistent with the proposed central role that ceramides have in the mechanical and permeability properties of the skin. Moreover, the marked difference in the properties of these two similar lipids may help to explain some of the properties of the stratum corneum.     

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.     

Crystalline fractionation of hydrogenated sunflowerseed oil

Crystalline fractionation of hydrogenated sunflowerseed oil was performed and the chemical composition of the separated fractions at different temperatures was determined. The results show that the triglycerides obtained after a short retention time (less than 16.4 min) were enriched in the low-temperature fractions (lower than 22°C), the triglycerides of long retention time (more than 21.5 min) were concentrated in the higher-temperature fractions (higher than 30°C), and the triglycerides of medium retention time (between 16.4 and 21.5 min) were concentrated in the medium-temperature fractions (22°C to 30°C). The partition ratio of triglycerides with retention times of 8.8, 12.5, 16.5, 21.5 and 29.1 minutes was increased as a function of the fractionation temperature.     

The fractionation of milk fat from a solvent at low temperatures

Summary A procedure for fractionating milk fat from a solvent at low temperatures has been developed. This procedure consists of freezing out fractions of the fat from solvent (Skelly Solve A) at progressively lower temperatures —7°, —13°, —23°, —53°C., with the remaining filtrate taken as a final fraction. In physical appearance these fractions vary from a dry white powder to a reddish-yellow oil; in melting point from 53°C. to —10.6°C.; in iodine number from 8.29 to 58.37; and in saponification equivalent from 262.8 to 235.2. The saponification equivalents do not change in the same order as the other properties mentioned. This fat fractionation effects a simplification of milk fat and makes available less complex portions of the natural glyceride mixtures for detailed study of the composition, configuration, and other properties. Some of these studies are now being carried out and will be reported later.     

Crystallization and fractionation of milk fat

Recent progress in understanding milk fat crystallization and fractionation is reviewed. Extent of fat solidification in butter can be altered by variations in thermal treatment of cream prior to churning. Because of its compositional complexity, milk fat rarely exhibits polymorphism. As with mixtures of closely related triglycerides, milk fat forms solid solutions. A typical milk fat begins melting below −40 C, maximum melting occurs at 15–18 C, and the highest melting fraction appears 20–37 C as a shoulder on the main peak. Dispersion of fat in emulsions increases its tolerance to supercooling, thereby altering the properties and composition of the solid phase. Most studies of milk fat fractionation have used progressive fractional crystallization, either of the melt or of solutions. Both procedures result in fractions showing larger changes in mp than in composition. The high melting glyceride fraction, ca. 5% total fat, influences crystallization out of proportion to concentration. The Alfa-Laval system, using an aqueous suspension of partially crystalline fat, produces two fractions. Typical high melting fractions have softening points ca. 3C higher than the original fat. The softening point of typical low melting fractions is lowered 10 C. Refractionation is easier with the high melting fraction. Melting thermograms of these fractions show them as resembling fractions prepared from melted fat. One of eight papers presented at the Symposium “Milk Lipids,” AOCS Fall Meeting, Ottawa, Canada, September 1972.     

In Situ Observation and Physical–Chemical Characteristics of Rambutan (Nephelium lappaceum L.) Kernel Olein Crystals Obtained from Acetone Fractionation

Hard fat stocks containing highly saturated fats are a necessary ingredient for fabrication of trans-free plastic fats. Crystal fractions obtained from the fractionation of fats naturally containing saturated fatty acids (SFA) may be a promising approach to produce the desired hard fat stocks. Influences of cooling rate (0.4, 2.0 and 10.0 °C·min⁻¹) and fractionation temperature (15 and 20 °C) on the formation of solid fat crystals of rambutan (Nephelium lappaceum L.) kernel olein (RKOle) during acetone fractionation were examined using in situ observation with polarized light microscopy (PLM). The resulting stable crystals were then separated and characterized by their iodine values, fatty acid compositions, crystal polymorphism, solid fat index, and melting behavior. PLM results showed that cooling rate affected crystal formation. Entrained oil on the surface and number of small crystals increased at higher cooling rates of RKOle. Stable crystals were obtained at a cooling rate of 2.0 °C·min⁻¹ and 6 hours, which had lower iodine value and contained more SFA with a higher amount of solid fat than incipient RKOle. Crystals fractionated at 20 °C were larger in size, fewer in number, and had less entrained oil compared to those fractionated at 15 °C. Their main polymorph was the β' form with a melting range comparable to common fully hydrogenated oils. Results suggested that RKOle crystals have potential for use as hard fat stocks for various purposes.     

Characterization of the high-melting glyceride fraction isolated from cottonseed oil stearin by fractional crystallization in isopropanol

Cottonseed oil stearin is generally produced commercially from cottonseed oil by winterization. In Egypt, the byproduct stearin is often used for lower-priced industrial applications. It can be turned into a high-value, cost-effective edible product by further fractionation to produce low-melting cottonseed oil stearin (LMCS) and a higher melting cottonseed oil stearin (HMCS). In the present investigation, isopropyl alcohol (IPA) helps to obtain good fractionation of HMCS having useful solidification and melting properties. The advantage of using IPA is that fractionation can be carried out at higher temperatures than hexane with better separation efficiency. A direct relationship between yield, quality of HMCS, and crystallization temperature during fractionation with IPA was achieved. HMCS could be fractionated from IPA at 4°C in a much higher yield but the melting point and the solid fat contents were much lower than that fractionated at 18°C. The thermal profile of the HMCS fractionated with hexane lies between those fractionated at 4 and 18°C with IPA. On the other hand, all the LMCS fractions could be considered as good quality salad oils.     

Properties of coal tar characterized by slight pyrolysis

The behavior of coal tars with different levels of pyrolysis in thermal fractionation is compared in the laboratory. The properties and group composition of the nonboiling residues (medium-temperature pitch) obtained by the distillation of coal tars at different temperatures, in comparable conditions, is investigated. The results indicate that the distillation of tars characterized by slight pyrolysis is accompanied by vigorous destruction processes, also affecting the α₁ fraction (t = 335–350°C), with subsequent reactions among the destruction products, leading to active increase in the α₁ and α₂ fractions (t ≥ 350°C). This is a significant difference between tars characterized by light pyrolysis and considerable pyrolysis.     

Chemical and physical properties of the high melting glyceride fractions of commercial margarines

The fat obtained from nine commercial mar-garines purchased from Canada and the U.S.A. were crystallized from acetone at 15, 10, 5 and 0°C. The high melting triglyceride (HMG) fractions at 15°C contained high levels of palmitic and stearic acids. The 18:1 levels increased as fractionation temperature decreased. Triglyceride analysis re-vealed that the 11MG fractions contained high 1ev-els of carbon 54 and 52. The levels of trans iso-mers increased, whereas the trans levels in the 18:1 decreased with fractionation temperature. Mar-games made from canola oil exhibited β charac-teristics whereas canola-paim, soybean and corn margarines showed β¹ crystals. The fractions as crystallized from acetone, showed numerous X-ray short spacings, characteristic of β¹, β and in-termediate forms. Upon heating and cooling, the 15°C fraction showed β¹ or a and β¹ characteris-tics regardless of the polymorphic form present in the original margarines. The differential scan-ning calorimetry (DSC) melting points of these fractions varied from 53 to 50° C. The difference between the β and β¹ margarines could be related to the 16:0 and carbon 54 content of the 15°C frac-tion. In the β tending margarines the 16:0 content was below 11%, in the β¹ tending margarines above 17%. The carbon 54 content in the 15°C fraction of the β tending margarines was close to 70% and that of the β¹ tending margarines around 50%. The triglyceride C54 in the 15°C fraction is β tending and therefore should be kept as low as possible. In canola margarines this can be achieved by in-corporation of palm oil, preferably in a slightly hydrogenated form. Presented at the Annual Meeting, Canadian Section of AOCS, October, 1989, Halifax, Canada.     

Thermal adaptation affects the fatty acid composition of plasma phospholipids in trout

The adaptive changes in the fatty acid (FA) composition of plasma phospholipids (PL) in response to alterations in environmental water temperature were investigated in juvenile rainbow trout (Oncorhynchus mykiss). The changes observed during thermal adaptation from 22°C in summer to 8°C in winter were reproduced by laboratory cold acclimation (CA) at 6°C of 22°C-summer-acclimated animals. In cold-acclimated and winter-acclimated trout, the increase in the unsaturation of PL fatty acids was mainly due to an enrichment of approximately 7% in the total weight percentage of 22∶6n−3, while a concomitant significant decrease in the levels of 18∶0 and of the monoenoic n−9 FA was observed. A time course study revealed that the changes in PL fatty acids became significant after 10 d of CA and were complete after one month. These changes in the composition of the fatty acyl chains of plasma total PL indicate that the FA composition of plasma lipoprotein PL does not remain constant during thermal adaptation. This would suggest that plasma lipoproteins provide a rapid systemic supply of lipids containing more or less unsaturated FA during thermal adaptation of poikilothermic animals.     

Phase investigations of fats. II. Systems containing oleic and stearic acids and an organic solvent

1. The ternary systems oleic acid-stearic acid-commercial hexane and oleic acid-stearic acid-acetone containing varying amounts of the three components have been equilibrated at 0°C., −10°C., −20°C., −30°C., and −40°C.
2. From compositional data of the liquid and solid phases in equilibrium at each isotherm, ternary phase diagrams have been constructed. From these diagrams it is possible to predict the degree of separation which can be obtained with any given mixture of oleic and stearic acids, using either acetone or commercial hexane as solvent.
3. With practical solvent ratios the phase diagrams at −20°C., −30°C., and −40°C., exhibit closed areas representing liquid phase composition. The liquid phase boundaries have been established for each isotherm investigated.
4. The intersolubilizing effect of oleic acid on stearic acid, greater in commercial hexane than in acetone, and the possible formation of mixed crystals of oleic and stearic acid have been noted.
5. Oleic acid of high purity can be obtained as one of the practical applications of these data.