Showing papers in "Journal of the American Oil Chemists' Society in 1999"

Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase

Abstract: Biodiesel derived from vegetable oils has drawn considerable attention with increasing environmental consciousness. We attempted continuous methanolysis of vegetable oil by an enzymatic process. Immobilized Candida antarctica lipase was found to be the most effective for the methanolysis among lipases tested. The enzyme was inactivated by shaking in a mixture containing more than 1.5 molar equivalents of methanol against the oil. To fully convert the oil to its corresponding methyl esters, at least 3 molar equivalents of methanol are needed. Thus, the reaction was conducted by adding methanol stepwise to avoid lipase inactivation. The first step of the reaction was conducted at 30°C for 10 h in a mixture of oil/methanol (1:1, mol/mol) and 4% immobilized lipase with shaking at 130 oscillations/min. After more than 95% methanol was consumed in ester formation, a second molar equivalent of methanol was added and the reaction continued for 14 h. The third molar equivalent of methanol was finally added and the reaction continued for 24 h (total reaction time, 48 h). This three-step process converted 98.4% of the oil to its corresponding methyl esters. To investigate the stability of the lipase, the three-step methanolysis process was repeated by transferring the immobilized lipase to a fresh substrate mixture. As a result, more than 95% of the ester conversion was maintained even after 50 cycles of the reaction (100 d).

Effects of free fatty acids on oxidative stability of vegetable oil

Abstract: The effect of free fatty acid (FFA) content on the susceptibility to thermooxidative degeneration of vegetable oils was determined by Rancimat analysis. A prooxidant effect of FFA was observed in all filtered oils, independently of lipidic substrate and of its state of hydrolytic and oxidative alteration. The intensity of this effect was related to FFA concentration, but regression analysis of the experimental data did not show a general correlation law between FFA concentration and induction time (I t). Different results were obtained for freshly processed virgin olive oils, characterized by postpressing natural suspension-dispersion: opposite behavior was observed of FFA content as regards oxidative stability, depending on the presence of suspended-dispersed material. This fact is of interest because the dispersed particles play a double stabilizing effect on both oxidative and hydrolytic degradation. These results showed that avoidance of oil filtration is highly desirable to extend olive oil’s shelf life.

The kinematic viscosity of biodiesel and its blends with diesel fuel

Abstract: As the use of biodiesel becomes more wide-spread, engine manufacturers have expressed concern about biodiesel’s higher viscosity. In particular, they are concerned that biodiesel may exhibit different viscosity-temperature characteristics that could result in higher fuel injection pressures at low engine operating temperatures. This study presents data for the kinematic viscosity of biodiesel and its blends with No. 1 and No. 2 diesel fuels at 75, 50, and 20% biodiesel, from close to their melting point to 100°C. The results indicate that while their viscosity is higher, biodiesel and its blends demonstrate temperature-dependent behavior similar to that of No. 1 and No. 2 diesel fuels. Equations of the same general form are shown to correlate viscosity data for both biodiesel and diesel fuel, and for their blends. A blending equation is presented that allows the kinematic viscosity to be calculated as a function of the biodiesel fraction.

Temperature and cultivar effects on soybean seed oil and protein concentrations

Abstract: The soybean [Glycine max (L.) Merr.] industry is interested in cultivar and climate effects on seed composition. These factors may underlie the known geographic variation in seed protein and oil concentrations. Regression analyses were used to test hypotheses of the effect of temperature and cultivar on oil and protein concentrations of soybean seed using a large data set from the U.S.A. Soybean Uniform Tests. The data set included 20 cultivars representing 10 maturity groups across 60 locations (latitude 29.4 to 47.5° N) for a total of 1863 cultivar by location by year observations. Temperature was determined for each observation as the average daily mean temperature from predicted first pod (first pod at least 5 mm long), using the SOYGRO phenology model, to observed maturity. The mean temperature ranged from 14.6 to 28.7°C among the observations. Linear, quadratic, and linear plateau regression models of oil and protein concentrations vs. temperature were evaluated. The quadratic model gave the best-adjusted R 2 values for oil and protein with temperature, of 0.239 and 0.003, respectively. The analyses showed that the oil concentration increased with increasing temperature and approached a maximum at a mean temperature of 28°C. Unaccounted variation in the protein concentration may be from other factors such as photoperiod, water stress, or high temperatures during seed fill. Protein plus oil had a linear relationship with temperature (adjusted partial R 2=0.183). These data document the contribution of climate and cultivar to geographic variability of oil and protein concentrations in the United States.

High‐performance liquid chromatography evaluation of phenols in olive fruit, virgin olive oil, vegetation waters, and pomace and 1D‐ and 2D‐nuclear magnetic resonance characterization

Abstract: Phenolic compounds are the most important antioxidants of virgin olive oil. This paper reports on the application of solid phase extraction (SPE) in the separation of phenolic compounds from olive fruit, olive oil, and by-products of the mechanical extraction of the oil and the complete spectroscopic characterization by nuclear magnetic resonance of demethyloleuropein and verbascoside extracted from olive fruit. SPE led to a higher recovery of phenolic compounds from olives than did liquid/liquid extraction. SPE also was used to separate phenolic compounds from pomaces and vegetation waters. Phenylacid and phenyl-alcohol concentrations in extracts obtained from SPE and liquid/liquid extraction were not significantly different (P<0.05). The recovery of the dialdehydic form of elenolic acid linked to 3,4-(dihydroxyphenyl)ethanol and an isomer of oleuropein aglycon, however, was low.

Depression of pour points of vegetable oils by blending with diluents used for biodegradable lubricants

Abstract: Low-temperature properties need improvement before vegetable oils can receive wider recognition as biodegradable lubricants. Effects of dilution with major biodegradable fluids, namely poly alpha olefin (PAO 2), diisodecyl adipate (DIDA), and oleates, as well as impact of pour point depressant (PPD), were investigated. Since solidification of mixed unsaturated triacylglycerols is a complex thermodynamic process, the study was limited to pour point determinations. Vegetable oils demonstrated higher pour points with increased saturation and molecular weight. Cis unsaturation and hydroxy groups favored lower pour points. Dilution with oleates appeared less effective than dilution with PAO 2 and DIDA. Addition of 1% PPD (w/w) depressed pour points down to −33°C for canola and −24°C for high-oleic sunflower oils. However, neither higher amounts of PPD nor incorporation of diluent produced further depression. Depression of pour points was not proportional to the amount of diluent and ceased with further dilution. Low-temperature performance of vegetable oils limits their prospect as biodegradable lubricants, but well-balanced usage of PPD and diluents can deliver some improvements.

Oxidation of sunflower oil during storage

Abstract: Effects of temperature and oxygen concentration on oxidative deterioration during storage of crude sunflower oils, obtained by pressing and solvent extraction, were studied. Oxidation was monitored through several analytical and chromatographic methods that determine chemical and physical changes or analyze specific oxidation compounds at different stages of the process: peroxide value, p-anisidine value, free fatty acids, weight gain, total content and distribution of polar compounds, and composition of fatty acids. Extracted oil showed a higher oxidative stability than pressed oil. Oxidative deterioration was strongly dependent on temperature, oxygen availability, and the ratio of exposed surface to sample volume. A kinetic model of two series reactions was developed to represent oxidation rate in terms of peroxide value, the reaction rate constants and their temperature dependence being evaluated by nonlinear regression. Finally, good correlations between the percentage of polar compounds or oxidized triglyceride monomers and the peroxide value were found.

Composition and thermal profile of crude palm oil and its products

Abstract: 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.

Fatty acid and tocopherol contents and oxidative stability of walnut oils

Abstract: Walnuts (Juglans regia L) were collected during the 1997 harvest from 13 different cultivars of trees grown in a replicated trial in an experimental orchard at Lincoln University Two US commercial cultivars (Tehama and Vina), three European commercial cultivars (Esterhazy, G139, G120), and eight New Zealand selections (Rex, Dublin’s Glory, Meyric, Stanley, Mckinster, 150, 151, 153) were evaluated Total lipids were analyzed for fatty acids by capillary gas chromatography, tocopherols by high-performance liquid chromatography, and oxidation stability by Rancimat The total oil content of the nuts ranged from 642 to 689% while the stability of the oil ranged from 39 to 78 h The oleic acid content of the oils ranged from 127 to 204% of the total fatty acids, while 18:2 content ranged from 570 to 625% and the 18:3 contents ranged from 107 to 162% Reduced stability of the oil as measured by the Rancimat method appears to be correlated to higher levels of 18:2 in the extracted oil The total tocopherol contents of these nuts ranged from 2685 to 4360 µg/g oil γ-Tocopherol dominated the profile while α-tocopherol was only 6% of the total content Peroxide values of the fresh oil were measured spectrophotometrically to give an indication of the overall stability The levels of total tocopherols when combined with the level of unsaturation in the oil in a multiple regression analysis had a significant relationship (R 2=452%, P<0001) with the peroxide value in the oil

Antioxidant activities of α- and γ-tocopherols in the oxidation of rapeseed oil triacylglycerols

Abstract: Antioxidant properties of 5 to 500 µg/g levels of α-and γ-tocopherols, in the oxidation of rapeseed oil triacylglycerols (RO TAG), were studied at 40°C in the dark. Each tocopherol alone and in a mixture was studied for its stability in oxidizing RO TAG. Also the effects of tocopherols on the formation of primary and secondary oxidation products of RO TAG were investigated. Both tocopherols significantly retarded the oxidation of RO TAG. At low levels (≤50 µg/g), α-tocopherol was more stable and was a more effective antioxidant than γ-tocopherol. At higher α-tocopherol levels (>100 µg/g), there was a relative increase in hydroperoxide formation parallel to consumption of α-tocopherol, which was not found with γ-tocopherol. Therefore, γ-tocopherol was a more effective antioxidant than α-tocopherol at levels above 100 µg/g. As long as there were tocopherols present, the hydroperoxides were quite stable and no volatile aldehydes were formed. In a mixture, α-tocopherol protected γ-tocopherol from being oxidized at the addition levels of 5+5 and 10+10 µg/g but no synergism between the tocopherols was found. α-Tocopherol was less stable in the 500+500 µg/g mixture than when added alone to the RO TAG. No prooxidant activity of either tocopherol or their mixture was found.

Tocopherols in breeding lines and effects of planting location, fatty acid composition, and temperature during development

Abstract: As the use of tocopherols as natural antioxidants increases, it is economically and agronomically important to determine the range, composition, and factors that affect their levels in oilseed crops, a major commercial source. In this study, tocopherols were quantified from seeds of wheat, sunflower, canola, and soybean. The breeding lines analyzed possessed a broad range of economically important phenotypic traits such as disease or herbicide resistance, improved yield and agronomic characteristics, and altered storage oil fatty acid composition. Complete separation of all four native tocopherols was achieved using normal-phase high-performance liquid chromatography with ultraviolet detection. Total tocopherol concentration among wheat germ oil samples ranged from 1947 to 4082 µg g−1. Total tocopherol concentration ranges varied from 534 to 1858 µg g−1 in sunflower, 504 to 687 µg g−1 in canola, and 1205 to 2195 µg g−1 among the soybean oils surveyed. Although the composition of tocopherols varied substantially among crops, composition was stable within each crop. Total tocopherol concentration and the percentage linolenic acid were correlated positively in soybean oils with modified and unmodified fatty acid compositions. Tocopherol concentration and degree of unsaturation were not correlated in sunflower or canola seeds with genetically altered fatty acid composition. These findings suggest that breeding for altered storage oil fatty acid composition did not negatively impact tocopherol concentrations in sunflower and canola as they apparently did in soybeans. When 12 soybean breeding lines were grown at each of five locations, significant correlations were observed among planting location, breeding line, tocopherol concentration, and fatty acid composition. Analysis of seeds that matured under three different controlled temperature regimes suggests that the relationship between tocopherol concentration level and unsaturated fatty acids in commodity (not genetically modified for fatty acid composition) oil types is due to temperature effects on the biosynthesis of both compounds.

Polymorphism of milk fat studied by differential scanning calorimetry and real-time X-ray powder diffraction

Abstract: The crystallization behavior of milk fat was investigated by varying the cooling rate and by isothermal solidification at various temperatures while monitoring the formation of crystals by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). Three different polymorphic crystal forms were observed in milk fat: γ, α, and β′. The β-form, occasionally observed in previous studies, was not found. The kind of polymorph formed during crystallization of milk fat from its melted state was dependent on the cooling rate and the final temperature. Moreover, transitions between the different polymorphic forms were shown to occur upon storing or heating the milk fat. The characteristic DSC heating curve of milk fat is interpreted on the basis of the XRD measurements, and appears to be a combined effect of selective crystallization of triglycerides and polymorphism.

Rapid monitoring of transesterification and assessing biodiesel fuel quality by near‐infrared spectroscopy using a fiber‐optic probe

Abstract: Vegetable oil esters, particularly methyl esters, are being explored and used as alternative diesel fuel (biodiesel). The transesterification reaction which yields the methyl esters can be monitored for completion by near-infrared (NIR) spectroscopy using a fiber-optic probe. Although the NIR method is less sensitive than gas chromatography (GC) for quantifying minor components, by correlation with existing GC or other analytical data, biodiesel fuel quality can be assessed through the NIR method. The NIR method is easier and faster to use than GC.

Effects of Natural and Synthetic Antioxidants on Changes in Refined, Bleached, and Deodorized Palm Olein During Deep-Fat Frying of Potato Chips

Abstract: The effects of antioxidants on the changes in quality characteristics of refined, bleached, and deodorized (RBD) palm olein during deep-fat frying (at 180°C) of potato chips for 3.5 h/d for seven consecutive days in five systems were compared in this study. The systems were RBD palm olein without antioxidant (control), with 200 ppm butylated hydroxytoluene (BHT), 200 ppm butylated hydroxyanisole (BHA), 200 ppm oleoresin rosemary, and 200 ppm sage extract. Fried oil samples were analyzed for peroxide value (PV), thiobarbituric acid (TBA) value, iodine value (IV), free fatty acid (FFA) content, polymer content, viscosity, E1% 1 cm at 232 and 268 nm, color, fatty acid composition, and C18:2/C16:0 ratio. Sensory quality of the potato chips fried in these systems prior to storage was also evaluated. The storage stability of fried potato chips for 14 wk at ambient temperature was also determined by means of the TBA values and sensory evaluation for rancid odor. Generally, in the oil, oleoresin rosemary gave the lowest rate of increase of TBA value, polymer content, viscosity, E1% 1 cm at 232 and 268 nm compared to control and three other antioxidants. The order of effectiveness (P BHA > sage extract > BHT > control. Prior to storage, the sensory evaluation of fried potato chips for each system showed that there was no significant (P>0.05) difference in terms of flavor, odor, texture, and overall acceptability. The same order of effectiveness (P 0.05) difference in sensory evaluation for rancid odor during storage periods.

Antioxidant activity of flavonol aglycones and their glycosides in methyl linoleate

Abstract: The antioxidant activities of the flavonol aglycones, quercetin and myricetin, and their selected glycosides were compared in bulk methyl linoleate oxidized at 40°C. Methyl linoleate hydroperoxide formation, hydroperoxide isomer distribution, and ketodiene formation were followed by using high-performance liquid chromatography (HPLC) analysis. The aglycones, quercetin and myricetin, were consistently more active in bulk methyl linoleate than their glycosides and more active than α-tocopherol at 500 and 1000 µM. At 50 µM, the order of activity was myricetin > α-tocopherol > quercetin, and the order of activity of quercetin and its derivatives was quercetin > quercitrin > isoquercitrin > rutin. Myricitrin was slightly less active than myricetin. The sugar moiety was shown to have a marked effect on the antioxidant activity of flavonols. The rhamnoside derivatives, quercitrin and myricitrin, both possessed activity close to that of their corresponding aglycones. The different activities of glycosides could be partly explained by different solubilities and by differences in oxidizability of glycosides containing a monosaccharide or disaccharide at the C3 position. The effect on hydroperoxide isomer distribution indicates that α-tocopherol was a more effective hydrogen donor than flavonoids, although flavonoids were more effective in inhibiting oxidation of methyl linoleate.

Phase behavior and extended phase scheme of static cocoa butter investigated with real-time X-ray powder diffraction

Abstract: A complete isothermal phase-transition scheme of cocoa butter under static conditions is presented, based on time-resolved X-ray powder diffraction experiments. In contrast to what is known from literature, not only β V, but also β VI can be obtained directly through transformation from β′. Another remarkable result is that β′ exists as a phase range rather than as two separate phases. Within this β′ phase range no isothermal phase transitions have been observed. More detailed information concerning the observed cocoa butter polymorphs was obtained by determination of melting ranges, using time-resolved X-ray powder diffraction. Also standard X-ray powder diffraction patterns of the γ, the α, and the two β phases and parts of the β′ phase range have been recorded. The observed phase behavior of cocoa butter has been explained based on the concept of individual crystallite phase behavior of cocoa butter

Studies on the Enzymatic Synthesis of Lipophilic Derivatives of Natural Antioxidants

Abstract: The esterification of some natural antioxidants such as cinnamic acid derivatives and ascorbic acid in non-aqueous media, catalyzed by immobilized lipases from Candida antarctica and Rhizomucor miehei, was investigated. The alcohol chain length affected the rate of esterification of cinnamic acids by both lipases. Higher reaction rates were observed when the esterification was carried out with medium- or long-chain alcohols. The rate also depended on aromatic acid structure. The reactivity of the carboxylic function of the cinnamic acids was affected by electron-donating substituents in the aromatic ring. Higher yields were observed for the esterification of p-hydroxyphenylacetic acid (97%) catalyzed by C. antarctica lipase and for the esterification of cinnamic acid (59%) catalyzed by R. miehei lipase. Candida antarctica lipase was more suitable for producing ascorbic acid fatty esters, catalyzing with a relatively high yield (up to 65% within 24 h) the regioselective esterification of ascorbic acid with various fatty acids in 2-methyl-2-propanol. The reaction rate and yield depended on the fatty acid chain length and on the molar ratio of reactants. All ascorbic acid fatty esters produced by this procedure exhibited a significant antioxidant activity in a micellar substrate composed of linoleic acid.

Shear strength and water resistance of modified soy protein adhesives

Abstract: Soy protein polymers recently have been considered as alternatives to petroleum polymers to ease environmental pollution. The use of soy proteins as adhesives for plywood has been limited because of their low water resistance. The objective of this research was to test the water resistance of adhesives containing modified soy proteins in walnut, maple, poplar, and pine plywood applications. Gluing strength and water resistance of wood were tested by using two ASTM standard methods. Glues with modified soy proteins had stronger bond strength than those containing unmodified soy proteins. Plywood made with glue containing urea-modified proteins had higher water resistance than those bonded with glues containing alkali-modified and heat-treated proteins. After three 48-h cycles of water-soaking, followed by 48 h of air-drying, no delamination was observed for either walnut or pine specimens glued with the urea-modified soy protein adhesives. Gluing strength for wood species with smooth and oriented surface structure was lower than for those with rough, randomly oriented, surface structures. Wood species with greater expansion of dimensions during water-soaking had a higher delamination rate than those showing less expansion.

Predicting the surface tension of biodiesel fuels from their fatty acid composition

Abstract: The emergence of biodiesel fuels as diesel fuel substitutes has led to several studies on their properties. Surface tension, which plays a role in atomization, has lacked attention compared to other properties. This paper presents a method to predict the surface tension of biodiesel fuels based on the fatty acid composition. Several binary, ternary, and quaternary mixtures of fatty acid ethyl ester gas chromatographic (GC) standards were prepared, and we found that a mass-average equation predicted the surface tension of these mixtures within ±3.5% of their measured values. Six complex mixtures of fatty acid methyl ester GC standards that simulated typical oils used as biodiesel fuels were also prepared. For these complex mixtures the predicted surface tensions of the mixtures, calculated from a mass-average equation, were 2–6% higher than the measured values. A mass-average equation was developed in which we used a weighted surface tension for the individual components, and we found that this method predicted the surface tension of the simulated oils within ±4.5% of their measured values. Five natural vegetable oils were used to produce biodiesel fuels by the transesterification process. The predicted surface tensions of these fuels were all within ±3.5% of their measured values. The surface tensions of 15 biodiesel types were then predicted, based on their fatty acid composition as published in the literature. These results show that the differences in surface tension between biodiesel types are not the main cause of the reported differences in engine tests.

Antioxidant synergy of α‐tocopherol and phospholipids

Abstract: The prevention of oxidation of a refined sardine oil by α-tocopherol at 0.04%, by several phospholipids [phosphatidylcholine (PC), phosphatidylethanolamine (PE), and cardiolipin (CL)] at 0.5%, as well as by combinations of α-tocopherol with each phospholipid, was investigated. The evolution of the oxidation process during 1 mon at 40±2°C was followed by a series of methods, measuring peroxide value (PV), diene, triene, and polyene index, and absorbance at 430 nm, while α-tocopherol and phospholipid content were being monitoried. Among these indices, PV was found to be the most adequate to follow the process. PC was the most effective individual antioxidant as shown by the PV values obtained at the end of the storage period, which were 54.0, 83.4, 87.9, and 97.7 meq O2/kg for PC, CL, PE, and α-tocopherol, respectively. The highest synergistic effect was obtained with a mixture of α-tocopherol and PE, and the second and third best by mixtures made with PC and CL, respectively. The corresponding PV values recorded at the end of the period were 27.0, 35.0, and 58.0 meq O2/kg. The high degree of synergy between PE and tocopherol is probably due to the occurrence of a simultaneous antioxidant mechanism involving Maillard compounds.

Transesterification of heated rapeseed oil for extending diesel fuel

Abstract: Fatty acid methyl esters are well established as an alternative fuel called “biodiesel.” For economic reasons, used frying oil is an interesting alternative feedstock for biodiesel production. The chemical changes that occur during heating of rapeseed oil, especially the formation of polymers, were investigated. Heated rapeseed oil samples were transesterified with methanol and analyzed by size-exclusion chromatography. During heating, the amount of polymers in the starting oil increased up to 15 wt%, but only up to 5 wt% in the transesterified samples. So during transesterification, dimeric and trimeric triglycerides in the starting oil were mainly converted into monomeric and dimeric fatty acid methyl esters. The amount of polymeric fatty acid methyl esters had a negative influence on fuel characteristics. After 6 h of heating, the amount of Conradson carbon residue and after 16 h the viscosity exceeded that of the existing specifications for biodiesel. Therefore, the amount of polymers in waste oil is a good indicator for the suitability for biodiesel production.

Antioxidant activity in soybean oil of extracts from thompson grape bagasse

Abstract: The phenolic compounds of Thompson grape bagasse were extracted using a 95:5 (vol/vol) ethanol/water mixture. Measurement of the antioxidant activity in refined soybean oil of bagasse grape extract was performed by using two different methods, the Rancimat method and the Schaal oven method in conjunction with peroxide value determination. The antioxidant activity of the extract was compared to the tertiary butyl hydroquinone (TBHQ) and butylated hydroxyanisole (BHA) activity. The bagasse grape extract showed similar antioxidant activities in both methods employed. At all concentrations tested [0.1, 0.3 and 0.5% of total phenols (TP)] the extract exhibited appreciable activity, which exceeded the activity of BHA. At some concentrations (0.3 and 0.5% TP) the extract exhibited activity comparable to that of TBHQ. Bagasse is a byproduct with a high content of phenolic compounds and is a good source of natural antioxidants.

The effects of shear and temperature history on the crystallization of chocolate

Abstract: Experiments have been carried out on the tempering of chocolate using a temperature-controlled shearing rig with a concentric cylinder geometry. This design maximizes uniformity of shear rate during tempering in contrast to most tempering devices where shear is often concentrated in a small part of the chocolate mass. Samples were subsequently cooled in a differential scanning calorimeter (DSC) to monitor how the sample crystallized, and then reheated to gain further information on the melting points of the polymorphs formed. The results can be interpreted using established theories on the crystallization mechanism. It was found that at least two polymorphic forms could be generated. The higher melting form predominated provided the shear rate was high enough, the temper time long enough, the rewarm temperature low enough, and the DSC scan rate slow enough. For parameters affecting the nucleation stage (temper time and shear rate), it was found that the transition was a sharp one, reflecting the notion that seed crystals need to grow past a threshold point in order to be stably formed. Raising the rewarm temperature had the effect of destroying seed nuclei, but this was a more gradual process. The bimodal nature observed of the melting points compared to the more spread-out behavior of crystallization temperatures reflects the kinetic constraints found in crystallization which are not found on melting.

Density and viscosity of vegetable oils

Abstract: A generalized method was developed to estimate the liquid density of vegetable oils and fatty acids. The correlation for vegetable oils was based on fatty acid critical properties and composition of the oil. The correlations predicted the density of vegetable oils and fatty acids with an average absolute deviation of 0.21 and 0.77%, respectively. The present method is slightly more accurate in predicting vegetable oil density and simpler than the method of Halvorsen et al. Also, a method is introduced that predicts viscosity from density data, thus relating two key properties of vegetable oils.

Deacidifying rice bran oil by solvent extraction and membrane technology

Abstract: Crude rice bran oil containing 16.5% free fatty acids (FFA) was deacidified by extracting with methanol. At the optimal ratio of 1.8:1 methanol/oil by weight, the concentration of FFA in the crude rice bran oil was reduced to 3.7%. A second extraction at 1:1 ratio reduced FFA in the oil to 0.33%. The FFA in the methanol extract was recovered by nanofiltration using commercial membranes. The DS-5 membrane from Osmonics/Desal and the BW-30 membrane from Dow/Film Tec gave average FFA rejection of 93–96% and an average flux of 41 L/m2·h (LMH) to concentrate the FFA from 4.69% to 20%. The permeate, containing 0.4–0.7% FFA, can be nanofiltered again to recover more FFA with flux of 67–75 LMH. Design estimates indicate a two-stage membrane system can recover 97.8% of the FFA and can result in a final retentate stream with 20% FFA or more and a permeate stream with negligible FFA (0.13%) that can be recycled for FFA extraction. The capital cost of the membrane plant would be about $48/kg oil processed/h and annual operating cost would be about $15/ton FFA recovered. The process has several advantages in that it does not require alkali for neutralization, no soapstock nor wastewater is produced, and effluent discharges are minimized.

Classification of virgin olive oils of the two major cretan cultivars based on their fatty acid composition

Abstract: Fatty acid composition was determined for 105 virgin olive oil samples of the two dominant Cretan olive cultivars, Koroneiki and Mastoides, harvested from different producing areas at different maturity stages. The oils of the Koroneiki cultivar were characterized by lower concentrations of oleic and decaheptanoic and higher concentrations of linoleic and palmitic acids. Oils obtained from high-altitude locations were rich in monounsaturated fatty acids, while oils obtained from low-altitude locations had higher content of saturated fatty acids. Palmitic and palmitoleic acids increased with increasing altitude in both cultivars examined. The statistical analysis of the compositional data showed significant potential for the classification of the samples according to cultivar and location of origin.

Optimizing production of ethyl esters of grease using 95% ethanol by response surface methodology

Abstract: Previous research suggested that ethyl esters derived from recycled restaurant grease might be a potential source of biodiesel. Accordingly, response surface methodology (RSM) was employed to optimize reaction parameters—temperature, time, level of lipase, mole ratio of reactants—in the PS-30 lipase-catalyzed transesterification reaction of grease to ethyl esters using 95% ethanol. The regression equation obtained by a modified central composite design of RSM predicted optimal reaction conditions of 38.4°C, 2.47 h, 13.7 wt% lipase (PS-30), and a mole ratio of grease to ethanol of 1:6.6. Under these conditions the predicted optimal percentage ethyl ester yield was 85.4%. Subsequent experiments using the predicted parameter combinations indicated a trend where experimental percentage yields of ethyl ester were consistently lower than predicted values. In an effort to improve the experimental yield of esters, a second portion of PS-30 lipase was added without success; however, the addition of 5% SP435 one hour after the start of the initial reaction increased the yield of esters to >96%. Neither lipase PS-30 nor lipase SP435 alone, however, gave the RSM-predicted yield of ethyl esters.

Enzymatic synthesis of symmetrical 1,3-diacylglycerols by direct esterification of glycerol in solvent-free system

Abstract: 1,3-Diacylglycerols were synthesized by direct esterification of glycerol with free fatty acids in a solvent-free system. Free fatty acids with relatively low melting points (<45°C) such as unsaturated and medium-chain saturated fatty acids were used. With stoichiometric ratios of the reactants and water removal by evaporation at 3 mm Hg vacuum applied at 1 h and thereafter, the maximal 1,3-diacylglycerol content in the reaction mixture was: 84.6% for 1,3-dicaprylin, 84.4% for 1,3-dicaprin, 74.3% for 1,3-dilinolein, 71.7% for 1,3-dieicosapentaenoin, 67.4% for 1,3-dilaurin, and 61.1% for 1,3-diolein. Some of the system’s parameters (temperature, water removal, and molar ratio of the reactants) were optimized for the production of 1,3-dicaprylin, and the maximal yield reached 98%. The product was used for the chemical synthesis of 1,3-dicapryloyl-2-eicosapentaenoylglycerol. The yield after purification was 42%, and the purity of the triacylglycerol was 98% (both 1,3-dicapryloyl-2-eicosapentaenoylglycerol and 1,2-dicapryloyl-3-eicosapentaenoylglycerol included) by gas chromatographic analysis, of which 90% was the desired structured triacylglycerol (1,3-dicapryloyl-2-eicosapentaenoylglycerol) as determined by silver ion high-performance liquid chromatographic analysis.

Long-term behavior of oil-based varnishes and paints I. Spectroscopic analysis of curing drying oils

Abstract: The curing of drying oils at 60°C has been investigated by Fourier transform infrared spectroscopy and Fourier transform Raman analysis of linseed oil and poppyseed oil. In the first step, hydroperoxides are formed (broad vibration band centered around 3425 cm−1) with concomitant conjugation and cis-trans isomerization of the double bonds (disappearance of cis bands at 3011 and 716 cm−1, appearance of trans conjugated and trans nonconjugated bands at 987 and 970 cm−1). The subsequent decomposition of hydroperoxides in the presence of oxygen leads to the formation of alcohols (nitrite band at 779 cm−1 after nitrogen monoxide treatment), aldehydes (bands at 2810 and 2717 cm−1 in gas phase), ketones (saturated and unsaturated at 1720 and 1698 cm−1, respectively), carboxylic acids (saturated and unsaturated acid fluorides identified at 1843 and 1810 cm−1 after SF4 treatment), and peresters or γ-lactones (near 1770 cm−1). A rapid decrease in the double-bond concentration is recorded when curing continues, and the formation of epoxides, characterized by a vibration band at 885 cm−1, is observed. Thermolysis experiments have suggested the proposal of a reaction of addition of peroxyl radicals on the conjugated double bonds as a probable mechanism. This mechanism explains both the rapid disappearance of conjugated double bonds and the formation of epoxides as intermediate products observed in the initial step of curing.

Acetone-stable nanofiltration membranes in deacidifying vegetable oil

Abstract: The separation of different vegetable oil/solvent mixtures with two types of nanofiltration membranes was studied. One type had a PEBAX [poly(amide-b-ether) copolymer] top layer, and the other had a cellulose-type top layer. These membranes were stable in acetone, ethanol, 2-propanol, and hexane, all important to the oleochemical industry. Permeabilities were highest for acetone, ±140 L/m2 · h · MPa, and lowest for hexane, which had negligible flux at 2 MPa. Permeabilities decreased with increasing triglyceride or free fatty acid (FFA) concentration. Rejection of triglycerides was constant over the concentration range tested, about 80–95%±5%, depending on the type of membrane used. These properties make membranes applicable for separating triglycerides from acetone by enhancing acetone recovery. Deacidification of triglycerides and FFA mixtures was possible (e.g., fatty acids were retained less than triglycerides). The permeate consisted almost entirely of fatty acids in acetone, and only small traces of triglycerides were found. This makes it feasible to selectively remove the fatty acids and reduce loss of triglycerides normally associated with deacidification.