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.     

The use of biodiesel as a green polymerization solvent at elevated temperatures

BACKGROUND: Many important polymers are produced via solution polymerization. The solvent maintains a low viscosity, which provides many practical advantages related to heat transfer, mixing and material handling. Despite these advantages, commonly used solvents often present health and environmental problems. In an effort to replace these toxic solvents, a ‘green’ polymerization solvent, namely canola‐based FAME (fatty acid methyl ester or biodiesel), was used for solution polymerizations at an elevated temperature. RESULTS: Homopolymerizations of methyl methacrylate, styrene, butyl acrylate and vinyl acetate in FAME were studied at different solvent concentrations at 120 °C. Chain transfer to solvent rate constants (C_fs) were obtained for each polymer system and Arrhenius parameters for C_fs, i.e. E_a and A, were also calculated. These new solvent data were employed in a polymerization simulator to predict rate of polymerization and number‐ and weight‐average molecular weights for these commercially important systems. Model predictions showed reasonable agreement with experimental data. CONCLUSION: FAME fulfills the demands as a polymerization solvent. From an ecological perspective, FAME provides an environmentally friendly alternative to common solvents. From an industrial perspective, using FAME as a high‐boiling polymerization solvent can increase productivity by enabling polymerizations at elevated temperatures. Copyright © 2008 Society of Chemical Industry     

Monitoring milk fat fractionation: Filtration properties and crystallization kinetics

The effect of fractionation temperature, residence time, and agitation rate on the chemical composition of the stearin and olein milk fat fractions was studied. During fractionation, filtration properties of the crystal suspension were monitored; crystallization kinetics was determined by ¹H NMR. Higher fractionation temperatures result in a lower stearin yield, more oil entrapment, and a lower final solid fat content of the crystal suspension. On the other hand, the chemical composition of the resulting fractions is not influenced. Longer residence times lead to longer filtration times and lower oil entrapment, whereas the yield is not affected. Longer residence times induced lower growth rates, but chemical composition is not influenced. Agitation rates varying from 10 to 15 rpm have no influence on the chemical composition of stearin and olein milk fat fractions. Higher agitation rates decrease the filtration quality and increase stearin yield, causing a softer stearin. In designing and monitoring milk fat fractionation, filtration experiments and the assessment of crystallization kinetics are valuable techniques, but compositional chemical analysis is not favorable.     

Effect of phospholipids on isothermal crystallisation and fractionation of milk fat

Milk fats with different concentrations of water and phospholipids (PL) were crystallised isothermally under static conditions and their crystallisation behaviour was monitored by Differential Scanning calorimetry (DSC) and pulsed nuclear magnetic resonance (pNMR). The Avrami and the Gompertz models, which were fitted by non‐linear regression, described the crystallisation process. A significant effect of phospholipid concentration was observed using both techniques (DSC and pNMR). Especially the induction time and the Avrami growth rate constant were altered: higher amounts of PL delayed the onset of static crystallisation. A similar effect of PL on the crystallisation kinetics was observed in a small‐scale fractionation. Moreover, the filtration time of the crystal suspension and melting properties of the stearin were strongly affected by the presence of higher concentrations of PL. These observations emphasise the importance of the adequate removal of PL during anhydrous milk fat production.     

Weak gels of fat crystals in oils at low temperatures and their fractal nature

The formation of fat crystal gels in soybean oil has been studied by sedimentation in a low concentration region at 10–25°C. At 10°C, weak gels were formed with 1% crystals, and no gels formed at concentrations of 2–5%. At temperatures of 15–25°C, no gels were formed at concentrations of 1–5%, and samples sedimented. Stronger gels of fat crystals were formed with ∼10% fat crystals at all temperatures examined. Formation of weak gels is a consequence of the fractal nature of fat crystal aggregates and sediments. At low temperature, the interaction is weak. The fractal dimension is then high, and the floc size is large for low crystal concentrations. These large flocs form a three-dimensional network that act as a weak gel and withstand gravitational force. When the temperature is increased, the fat crystal interaction becomes stronger, fractal dimension decreases, and floc size decreases. Smaller flocs have a higher density, pack more easily, and sediment. Similar effects are observed when the concentration of fat crystals is increased at low temperature due to a decrease in floc size.     

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.     

Characterisation of chicken fat dry fractionation at the pilot scale

Chicken fat was processed by dry fractionation to obtain a solid fraction at ambient temperature. Crystallisation and separation were performed using industrial‐type procedures. Crystal formation and changes were monitored, while determining the composition, physical characteristics and thermal behaviour of the initial fat and resulting fractions. Dry fractionation, under the described conditions, produced stearin that resembled other animal fats such as lard and tallow and with better physical features than the initial fat stock. The results of this study also highlighted the mechanisms involved during the dry fractionation process.     

Elastic properties of a tungsten monocarbide-based metalloceramic at low temperatures

Translated from Steklo i Keramika, No. 3, pp. 20–21, March, 1990.     

Liquid column fractionation: a method of solvent fractionation of coal liquefaction and petroleum products

A method is described for the solvent fractionation of coal liquefaction and petroleum products which is both reproducible and considerably more rapid than many conventional solvent fractionation techniques. This method involves sequential elution of a sample injected onto an inert liquid Chromatographic column. Applications of this method to coal liquefaction and petroleum products are given.     

The structure of physically adsorbed layers on graphite at low temperatures

A very brief outline of recent results with references to literature is given.     

Maturation study of low fat Chanco cheese made with homogenized milk

The purpose of this study was to evaluate the influence the use of homogenization of different proportions of milk--which allow to increase the yield in the process and probably to improve sensorial characteristics of the cheese--has on the ripening of low fat Chanco cheese. Five treatments (three replicates each) were studied, two corresponded to control (normal fat and low fat) and the other three treatments were low fat using partially homogenized milk in the following percentages of the total volume of milk; 12.5, 25 and 50%. Standard methodology was used to monitor the evolution of ripening in terms of moisture, fat and total protein content, ripening index (NS/NT%), lipolysis (ADV), pH, sensorial quality and micro structure of the product. The low fat treatments with homogenized milk showed less fat losses in the whey and consequently increased yields. This study allowed us to know the low fat Chanco cheese maturation profile, low fat treatments with homogenisation showed a higher degree of lipolysis than the non--homogenized low-fat control although it was lower than normal fat control. No differences in terms of the development of proteolysis were observed. The low--fat homogenized treatments did not show improvement in the flavor neither in the cheese firmness probably due to the short ripening period (21 days) of this cheese variety, nevertheless T3 presented some advantages which could be improved applying simultaneously another technological helps.     

Fundamental studies of NOx storage at low temperatures

A commercial NO_x storage catalyst (Pt, BaO and alumina containing) was investigated by temperature programmed desorption (TPD) experiments in the temperature range 100–400 °C. The catalyst stored a substantial amount of NO_x at 100 °C using NO + O₂. Nitrites or loosely bound NO species are suggested for this storage, since no NO was oxidised at this low temperature. In addition, the released NO_x during the temperature ramp consisted of mainly NO and at lower temperatures the NO₂ dissociation is limited. Water and CO₂ was found to decrease the storage substantially, 92% for the NO + O₂ adsorption at 100 °C. The total storage for 60 min using NO₂ + O₂ at 200 °C was similar when introducing CO₂ and H₂O. However, the initial total uptake of NO_x was decreased. Initially we probably formed loosely bound NO_x species, which likely are strongly influenced by water and CO₂. After longer time periods are barium nitrates probably formed and they can remove the carbonates by forming stable nitrates, thus resulting in the same total uptake of NO_x.