Thermal degradation of FA and catfish and menhaden oils at different refining steps

The thermal degradation (weight loss) of individual FA and of catfish and menhaden oils collected from different refining steps was investigated by thermogravimetric analysis. The heat resistance of FA was partially dependent on chain length and degree of unsaturation. The weight loss of catfish and menhaden oils increased with increased heating temperatures, regardless of the oil refining process. All oil samples (except crude catfish oil) were decomposed after the heating temperature reached 550°C. Based on the thermogravimetric curves, the following thermal stability sequence at different refining steps for both catfish and menhaden oils was proposed: crude > degummed > neutralized > bleached > deodorized oils.     

Effects of processing steps on the contents of minor compounds and oxidation of soybean oil

The processes of degumming, alkali refining, bleaching and deodorization removed 99.8% phospholipids, 90.7% iron, 100% chlorophyll, 97.3% free fatty acids and 31.8% tocopherols from crude soybean oil. The correlation coefficient between the removals of phosphorus and iron in soybean oil during processing was r = 0.99. The relative ratios of α-, β -, γ- and δ-tocopherols in crude oil, degummed oil, refined oil, bleached oil and deodorized soybean oil were almost constant, γ- and δ -tocopherols represented more than 94% of tocopherols in soybean oil. The order of oxidation stability of oil is crude > deodorized > degummed > refined > bleached oil.     

Oxidative stability of high-fatty acid rice bran oil at different stages of refining

The contents of natural antioxidants and the oxidative stability of rice bran oils at different refining steps were determined. Tocopherols and oryzanols were constant in crude and degummed oils but decreased in alkali-refined, bleached and deodorized oils. The process of degumming, alkali-refining, bleaching and deodorization removed 34% of the tocopherols and 51% of the oryzanols. During storage of deodorized oil for 7 wk, 34% of the tocopherols and 19% of the oryzanols were lost. The maximum weight gain, peroxide value and anisidine value were obtained from alkali-refined oil during storage. The order of oxidation stability was crude ≥ degummed > bleached = deodorized > alkali-refined oil.     

Effects of processing on the quality and stability of three unconventional Sudanese oils

In a refining experiment, on a laboratory scale, crude oils from Sclerocarya birrea (SCO), sorghum bugs (SBO), water‐extracted melon bugs (MBO H₂O) and solvent‐extracted melon bugs (MBO SOL) were processed by alkali refining. Quality changes were characterized by the determination of free fatty acids (FFA), peroxide value, tocopherols, sterols, phosphatides and stability against oxidation (Rancimat test). In addition, the fatty acid composition was determined. It is clear that the contents of phosphatides, peroxides, tocopherols, sterols as well as oxidative stability were reduced during processing, while FFA were nearly totally removed. The content of phosphorus was reduced in SCO, SBO, MBO H₂O and MBO SOL by 26, 19, 12, and 78%, respectively, while complete oil processing removed 95, 99, 96 and 99% of the FFA in crude oils, respectively. The level of total tocopherols decreased during processing by 38.7, 83.8, 100, and 33.3%, respectively. The color decreased through the processing steps up to bleaching; then, in the deodorization step, it darkened sharply in all samples. No change in the fatty acid composition was observed. The order of oxidation stability was crude > degummed > deodorized > neutralized > bleached, in SCO; and crude > degummed > neutralized > bleached = deodorized, in MBO H₂O; and crude > degummed > deodorized > neutralized > bleached in MBO SOL; while in SBO, the order of oxidative stability was deodorized > crude > degummed > neutralized = bleached. Total sterols decreased by 42–92% in the processed oils, compared with crude oils.     

Deacidification of high-acid rice bran oil by reesterification with monoglyceride

Autocatalytic esterification of free fatty acids (FFA) in rice bran oil (RBO) containing high FFA (9.5 to 35.0% w/w) was examined at a high temperature (210°C) and under low pressure (10 mm Hg). The study was conducted to determine the effectiveness of monoglyceride in esterifying the FFA of RBO. The study showed that monoglycerides can reduce the FFA level of degummed, dewaxed, and bleached RBO to an acceptable level (0.5±0.10 to 3.5±0.19% w/w) depending on the FFA content of the crude oil. This allows RBO to be alkali refined, bleached, and deodorized or simply deodorized after monoglyceride treatment to obtain a good quality oil. The color of the refined oil is dependent upon the color of the crude oil used.     

Supercritical CO2 degumming and physical refining of soybean oil

A hexane-extracted crude soybean oil was degummed in a reactor by counter-currently contacting the oil with supercritical CO₂ at 55 MPa at 70°C. The phosphorus content of the crude oil was reduced from 620 ppm to less than 5 ppm. Degummed feedstocks were fed (without further processing,i.e., bleaching) directly to a batch physical refining step consisting of simultaneous deacidification/deodorization (1 h @ 260°C and 1–3 mm Hg) with and without 100 ppm citric acid. Flavor and oxidative stability of the oils was evaluated on freshly deodorized oils both after accelerated storage at 60°C and after exposure to fluorescent light at 7500 lux. Supercritical CO₂-processed oils were compared with a commercially refined/bleached soybean oil that was deodorized under the same conditions. Flavor evaluations made on noncitrated oils showed that uncomplexed iron lowered initial flavor scores of both the unaged commercial control and the CO₂-processed oils. Oils treated with .01% (100 ppm) citric acid had an initial flavor score about 1 unit higher and were more stable in accelerated storage tests than their uncitrated counterparts. Supercritical CO₂-processed oil had equivalent flavor scores, both initially and after 60°C aging and light exposure as compared to the control soybean oil. Results showed that bleaching with absorbent clays may be eliminated by the supercritical CO₂ counter-current processing step because considerable heat bleaching was observed during deacidification/deodorization. Colors of salad oils produced under above conditions typically ran 3Y 0.7R.     

Effect of processing on the oxidative stability of low erucic acid turnip rapeseed (Brassica rapa) oil

The effect of various processing conditions on the composition and the oxidative stability of mechanically pressed (90–95°C) rapeseed oil was investigated. The five different rapeseed oils included crude (nondegummed), superdegummed, steam stripped (at 140°C for 4h, nondegummed), physically refined (degummed, bleached and deodorized at 240°C), and cold pressed (40°C) oils. Oils were autoxidized in the dark at 60°C and under light at 25°C. Oxidation was followed by measuring changes in the peroxide values (PV) and the consumption of tocopherol and carotenoid was measured. In the dark the oils reached PVs of 10 meq/kg in the order: cold pressed > superdegummed > steam stripped ≅ crude > refined. However, under light conditions the order changed as follows: cold pressed > crude ≅ steam stripped > superdegummed > refined. Processing had no effect on fatty acid composition nor α-tocopherol content of the oils. Superdegumming and steam stripping decreased the carotenoid content of the oils while cold pressing and refining reduced also chlorophyll, γ-tocopherol and phosphorus content of the oils.     

Oil production from catfish viscera

Oil was extracted from catfish viscera and purified (degummed, neutralized, bleached, and deodorized). The yield of catfish oil after purification was 65.7%. The major yield loss took place during the degumming process. The FA found in crude catfish visceral oil were 14∶0, 16∶0, 16∶1, 18∶0, 18∶1, 18∶2, 18∶3, 20∶0, 20∶1, 20∶2, 20∶3, 20∶4, and 22∶6, the predominant FA being 18∶1, 16∶0, 18∶2, and 18∶0. The total unsaturated FA in the purified catfish oil amounted to 67.7%. The combined n−3 FA content of the purified catfish oil was 4.6 mg/g of oil. The purified catfish oil contained 1.21 mg/g DHA. FFA, water activity, and some mineral contents decreased during purification. Bleaching removed pigments, thus resulting in oil with greater lightness and less yellowness.     

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.     

Zu den Veränderungen von Rapsöl und Leinöl während der Verarbeitung

Changes of rapeseed and linseed oil during processing During processing of crude oil in a large oil mill, three samples each of rapeseed and linseed were investigated at each processing stage, i.e. press oil, solvent-extracted oil, mixed oil, and degummed/caustic refined oil. In the case of rapeseed also bleached and desodorized oils (230°C; 3.0 mbar for 2 h) were investigated. Rapeseed and linseed oil showing the typical major fatty acids contained less than 1% trans-isomeric fatty acids (trans fatty acids = TFA). Linseed oil had a similar TFA-concentration as rapeseed oil, and the concentrations did not change during the processing stages up to degummed/caustic refined oil, and were also unchanged in the bleached rapeseed oil. Desodorization of rapeseed oil, however, trebled the TFA concentration to 0.58%. The detected tocopherol patterns were typical of rapeseed and linseed oils. There was no difference between mixed oil and degummed/caustic refined oil in the total concentration of tocopherols. Neither had bleaching any effect. Rapeseed oil desodorization diminished total tocopherol concentration by 12% from 740 mg/kg to 650 mg/kg. Due to degumming/caustic refining the phosphorus concentration of both oils decreased to less than a tenth compared to mixed oil. Other elements determined in degummed/caustic refined rapeseed oil were not detectable (manganese < 0.02 mg/kg, iron < 0.4 mg/kg, copper < 0.02 mg/kg, lead < 10 μg/kg) or only as traces zink 0.1 mg/kg, cadmium 2 μg/kg). In linseed oil, which initially showed a higher trace compounds concentration, a significant decrease was found by degumming/caustic refining. Iron could not be detected. There were traces of zinc, manganese, copper, lead, and cadmium. There was no difference between the acid values of rapeseed and linseed crude oil. Acid value decreased drastically already during the degumming/caustic refining stage. The crude linseed oils had a higher peroxide value, anisidine value and diene value than the corresponding crude rapeseed oils. With peroxide values of ≤ 0.1 mEq O₂/kg found in almost all investigated rapeseed oils, no effect of refining could be detected. The anisidine value showed an increase after bleaching. Desodorization trebled the diene value.     

Effect of temperature on linolenic acid loss and 18:3 Δ9-cis, Δ12-cis, Δ15-trans formation in soybean oil

Oil was extracted from soybeans, degummed, alkalirefined and bleached. The oil was heated at 160, 180, 200, 220 and 240°C for up to 156 h. Fatty acid methyl esters were prepared by boron trifluoride-catalyzed transesterification. Gas-liquid chromatography with a cyanopropyl CPSil88 column was used to separate and quantitate fatty acid methyl esters. Fatty acids were identified by comparison of retention times with standards and were calculated as area % and mg/g oil based on 17:0 internal standard. The rates of 18:3ω3 loss and 18:3 Δ9-cis, Δ12-cis, Δ15-trans (18:3c,c,t) formation were determined, and the activation energies were calculated from Arrhenius plots. Freshly prepared soy oil had 10.1% 18:3ω3 and no detectable 18:3c,c,t. Loss of 18:3ω3 followed apparent first-order kinetics. The first-order rate constants ranged from .0018±.00014 min⁻¹ at 160°C to .083±.0033 min⁻¹ at 240°C. The formation of 18:3c,c,t did not follow simple kinetics, and initial rates were estimated. The initial rates (mg per g oil per h) of 18:3c,c,t formation ranged from 0.0031±0.0006 at 160°C to 2.4±.24 at 240°C. The Arrhenius activation energy for 18:3ω3 loss was 82.1±7.2 kJ mol⁻¹. The apparent Arrhenius activation energy for 18:3c,c,t formation was 146.0±13.0 kJ mol⁻¹. The results indicate that small differences in heating temperature can have a profound affect on 18:3c,c,t formation. Selection of appropriate deodorization conditions could limit the amount of 18:3c,c,t produced.     

Quality Changes and Tocopherols and γ-Orizanol Concentrations in Rice Bran Oil During the Refining Process

The quality changes and the concentrations of tocopherols and γ-oryzanol, during successive steps of rice bran oil refining (RBO), were studied. For this purpose, samples of crude, degummed, neutralized, bleached, dewaxed and deodorized RBO were taken from an industrial plant and analyzed. The moisture, pH, acidity, peroxide value and unsaponifiable matter, were determined. The fatty acid composition was evaluated by GC, and the concentrations of tocopherols and γ-oryzanol were determined using HPLC with fluorescence and UV–Vis detection, respectively. To identify γ-oryzanol components, fractions of the HPLC eluant were collected and analyzed using mass spectrometry. Oil refining reduced the peroxide value and acidity to 1 and 3% of the values obtained in crude RBO, respectively. The fatty acid composition were not significantly altered during refining. The concentrations of the tocopherols in RBO followed the order α > (β + γ) > δ. The total concentration of tocopherols was 26 mg/100 g, and remained practically unaltered during refining. Up to nine components were distinguished in γ-oryzanol. After collecting the elution fractions, up to six components were identified by electrospray mass spectrometry. Refining reduced the total concentration of γ-oryzanol to 2% of its initial value.     

Refining of rice bran oil by neutralization with calcium hydroxide

The applicability of calcium hydroxide (lime) in the neutralization of rice bran oil (RBO) was investigated. Crude RBO samples of three different free fatty acids (FFAs) (3.5–8.4 wt%) were degummed, dewaxed, bleached, and neutralized with lime and deodorized. The oils obtained thus were characterized by determining the color, peroxide value (PV), content of unsaponifiable matter (UM), and FFA. Conventionally practiced caustic soda neutralization (at 80–90°C) of FFA has in the present investigation been replaced by a high temperature (150–210°C) low pressure (2–4 mm Hg) reaction with lime. It was observed that neutralization with Ca(OH)₂ at high temperature (210°C) and under low pressure (2–4 mm Hg pressure) may substantially reduce the FFA content (0.8 wt%, after 2 h). The deodorized oil was found to be of acceptable color, PV, and content of UM and FFA. Neutralization of oil was also carried out by using NaHCO₃ and Na₂CO₃, nonconventional alkalies for neutralization, and the results were compared with NaOH and Ca(OH)₂. Overall recovery of oil in Ca(OH)₂ refining process (88.5 ± 0.6 wt%, for Sample 1 containing 8.4%‐wt FFA) was found to be more than other competitive processes studied.     

Thermal and flow properties of oils from salmon heads

Thermal and flow properties of unrefined oils from the heads of red or pink salmon were evaluated. Major thermal degradation of the salmon oils occurred between 200 and 450°C. Red and pink salmon oils were completely decomposed at 533 and 668°C, respectively. The phase transition of salmon oils occurred over a wide range of temperatures. The melting points of −69.6 to −0.36°C and −64.7 to 20.8°C were observed for red and pink salmon oils, respectively. The enthalpy was 40 j/g for red salmon oil and 39 j/g for pink salmon oil. Specific heat capacity ranges of 0.8 to 1.6 and 1.3 to 2.3 j/g/°C were observed for red and pink salmon oils, respectively. Both salmon oils exhibited Newtonian flow behavior. Red salmon oil required higher magnitudes of energy (kj·mol⁻¹) to flow than pink salmon oil. The viscosity of salmon oils was temperature-dependent and could be predicted by the Arrhenius equation.     

Sulfur content of rapessed oils

Sulfur contents in rapeseed oils were determined by reduction with Raney nickel, acidification, and titration of released H₂S with mercuric acetate. The sulfur contents decreased with successive steps of industrial processing, i.e., crude oil, 17–31 ppm S; degummed, 16 ppm; alkali refined, 4–9 ppm; bleached, 3–5 ppm; and deodorized, <1 ppm. Laboratory-extracted oil from sound seed contained no detectable sulfur, regardless of the glucosinolate content of the seed. Heating of the seed or addition of water to the seed prior to extraction increased the sulfur in the oil-less, however, for low-glucosinolate seed than for high-glucosinolate seed. Laboratory-extracted oils from green, frost-damaged, and bin-heated seed contained appreciable amounts of sulfur. Contribution No. 403, Department of Plant Science, University of Manitoba.     

Effect of water quality on degumming and stability of soybean oil

Solvent-extracted crude soybean oil was degummed with deionized distilled water containing various amounts of CaCO₃−MgCO₃ FeCl₂, and NaCl. The total phosphorus content remaining in the degummed oil was determined and the peroxide value of the degummed oil held at 98–101 C was measured daily for 10 days. The results were compared statistically with those from oil degummed with deionized distilled water as a control. It was found that 250 mg/L of CaCO₃−MgCO₃ significantly reduced the efficiency of the degumming process. FeCl₂ at concentrations of 150 and 250 μg/L and NaCl at 300 mg/L resulted in the removal of more phosphorus than the control at the 5% level of significance. Generally, the stability of the degummed oils decreased as the salt concentrations increased. The rate of oxidation was greater for oils degummed in the presence of FeCl₂ than of NaCl and CaCO₃−MgCO₃ under the same conditions.     

Quality of oil from damaged soybeans

Various processing steps were explored in an at-tempt to improve the quality of oil from field- and storage-damaged soybeans. A crude soybean oil (5.7% free fatty acid) commercially extracted from damaged soybeans was degummed in the laboratory with different reagents: water, phosphoric acid, and acetic anhydride. Two alkali strengths, each at 0.1 and 0.5% excess, were used to refine each degummed oil. After vacuum bleaching (0.5% activated earth) and deodorization (210 C, 3 hr), these oils were un-acceptable as salad oils. A flavor score of 6.0 or higher characterizes a satisfactory oil. Scores of water and phosphoric acid degummed oils ranged from 4.5 to 5.1, while acetic anhydride degummed oils aver-aged 5.6. Flavor evaluations of (phosphoric acid de-gummed) single- and double-refined oils (210 C deodorization) showed that the latter were signifi-cantly better. Flavor scores increased from 5.0 to about 6.0. To study the effects of deodorization tem-perature, the crude commercial oil was alkali-refined, water-washed and bleached with 0.5% activated earth, but the degumming step was omitted. Flavor evalua-tion of oil deodorized at 210, 230, and 260 C showed that each temperature increment raised flavor scores significantly. Further evaluations of specially proc-essed oils (water, phosphoric acid, and acetic anhy-dride degummed oils given single and double refinings and deodorized at 260 C) showed that deodorization temperature is the most important factor affecting the initial quality of oil from damaged beans. Flavor evaluations showed that hydrogenation and hydro-genation-winterization treatments produced oils of high initial quality, but with poorer keeping proper-ties than oils from normal beans. No evidence was found implicating nonhydratable phosphatides in the oil flavor problem. Iron had a deleterious effect in oils not treated with citric acid during deodorization. Presented at AOCS Meeting, Philadelphia, September 1974.     

The effect of bleaching and physical refining on color and minor components of palm oil

An industrially degummed Indonesian palm oil was bleached and steam refined in a pilot plant to study the effect of processing on oil color and on the levels of carotenoids and tocopherols. Five concentrations of one natural and two activated clays mixed with a fixed amount of synthetic silica were used for bleaching. For color measurement, the Lovibond method was compared to the CIE (Commission Internationale de l’Eclairage) L^*,a^*,b^* method. The results showed that the L^*,a^*,b^* method is repeatable and that the values found are highly correlated with the carotenoid content of bleached oil samples. The various clays and synthetic silica mixes removed 20–50% of the carotenoids in the degummed oil, depending on clay concentration and activity. For the two activated clays, pigment adsorption increased with clay amount. Steam refining totally destroyed carotenoids in the claytreated oils by heat bleaching. Total tocopherols in the crude oil amounted to 1000 mg/kg, with γ-tocotrienol as the main tocopherolic component followed by α-tocopherol, α-tocotrienol, and δ-tocotrienol. Tocopherol concentrations increased after the bleaching treatment with the most acid clay, and the increase was proportional to the amount of clay used. Both bleaching and steam refining changed the ratios between the various to copherolic components, especially increasing the relative concentration of α-tocotrienol in the refined oil. An average 80% tocopherol retention was obtained after the treatment with acid clay + synthetic silica and steam refining of palm oil.     

Pretreatment of corn oil for physical refining

Crude corn oil that contained 380 ppm of phosphorus and 5% of free fatty acids was degummed, bleached, and winterized for physical refining. The pretreatment and the steam-refining conditions were studied in pilot plant scale (2 kg/batch). The efficiency of wet degumming and of the total degumming processes, at different temperatures, was evaluated. TriSyl silica was tested as an auxiliary agent in the reduction of the phosphorus content before bleaching. The experimental conditions of the physical refining were: temperature at 240 or 250°C; 8 to 18 mbar vacuum, and distillation time varying from 1 to 3 h. Degumming at 10 or 30°C resulted in the removal of more phosphorus than at 70°C. Water degumming was more efficient than the processes of total degumming or acid degumming. Corn oil, degummed at 10 or 30°C, after bleaching passed the cold test, irrespective of the degumming agent used. Degumming and winterization took place simultaneously at these temperatures. The pretreatment was able to reduce the phosphorus content to less than 5 ppm. The amount of bleaching earth was reduced by carrying out dry degumming or by using silica before bleaching. Corn oil acidity, after physical refining, varied from 0.49 to 1.87%, depending on the residence time. Contrary to alkali refining, physical refining did not promote color removal due to the fixation of pigments present in the crude corn oil.     

Stabilization of seal blubber and menhaden oils with green tea catechins

Catechins, namely (−)epicatechin (EC), (−)epigallocatechin (EGC), (−)epicatechin gallate (ECG) and (−)epigallocatechin gallate (EGCG), were isolated from commercial Chinese green leaves. The antioxidant activity of isolated catechins was compared with those of α-tocopherol, butylated hydroxyanisole (BHA), butylated hydroxytolene (BHT) andtert-butylhydroquinone (TBHQ), all at 200 ppm, in refined, bleached and deodorized seal blubber oil and menhaden oil. The study was carried out under Schaal oven test conditions at 65°C over a 144-h period, except for weight gain measurements, which were continued for up to 200 h. Progression of oxidation was monitored by measuring changes in weight gain and values of peroxide, conjugated diene, and 2-thiobarbituric acid-reactive substances. Oils treated with tea catechins showed excellent oxidative stability as compared with samples that contained commonly used antioxidants, such as α-tocopherol, BHA, BHT, and TBHQ. The potency of catechins in prevention of oxidation of marine oils was in the decreasing order of ECG> EGCG> EGC> EC; ECG was slightly more effective than TBHQ in systems studied.