Rice bran oil. V. The stability and processing characteristics of some rice bran oils

1. The extraction, processing, characteristics, and stability properties of nine batches of hexane-extracted rice bran oil were investigated. The oils were refined, bleached, and deodorized and their color and stability determined. Samples of the bleached oils were hydrogenated to approximately shortening consistency, deodorized, and the stability of the hydrogenated products determined.
2. Pilot plant extractions of five batches of rice bran yielded crude oils equivalent to 91% of the hexane-soluble portions of the bran.
3. The nine crude oils whose content of free fatty acids ranged from 2.0 to 6.3% were refined by the cup method with losses ranging from 12.0 to 23.5% although the neutral oil content of six crude rice bran oils ranged from 89.9 to 92.6%.
4. The Lovibond color of the nine refined oils ranged from 35 yellow and 4.5 red to 70 yellow and 9.5 red, and the color of the bleached oils ranged from 15 yellow and 1.5 red to 35 yellow and 3.2 red.
5. Steam-refining, employed in conjunction with alkali-refining, proved effective as a means of reducing the losses in refining rice bran oil.
6. The nine batches of refined, bleached, and deodorized rice bran oils had iodine values ranging from 101.3 to 105.7 and stabilities averaging 24 hours.
7. Nine bleached oils hydrogenated to approximate shortening consistency had iodine values averaging approximately 66 and stabilities averaging 370 hours.
8. Refined, bleached, and deodorized rice bran oil is bland but has some tendency toward flavor reversion.
9. The most outstanding characteristics of rice bran oil is its exceptional stability after hydrogenation.

     

Effect of caustic refining,solvent refining and steam refining on the deacidification and color of rice bran oil

Degummed rice bran oil was deacidified by caustic, solvent and steam refining processes. The steam refining process was optimized through a series of experiments with varying refining times (1–5 hr), temperatures (220–280 C) and amounts of steam (4–20%), at a pressure of 4 mmHg. The most significant factors affecting the degree of deacidification were the refining temperature and amount of steam. The correlation coefficient between quadratic equation obtained and experimental results was 0.96. Acid value and color of steam refined oil were not as good as those of caustic refined oil, but steam refining showed better retention of natural antioxidants than caustic or solvent refining. Steam refining is preferred for deacidification of rice bran oil because of reduced neutral oil loss and elimination of soap production. The important criteria in selecting a deacidification process are known to be the degree of deacidification, neutral oil loss, effect on bleaching and production of soapstock (2,8–10). In comparing caustic refining, solvent refining and steam refining, caustic refining of degummed rice bran oil resulted in satisfactory acid values and color but showed the worst result in neutral oil loss and produced large amounts of soapstock. Solvent refining was not shown to be efficient because of poor deacidification, high losses of neutral oil and darkening of color. Steam refining also was less effective than caustic refining in deacidification and bleaching. However, the degree of deacidification could be improved by development of a process to remove all the free fatty acids (8), and the color problem could be eliminated by including a preliminary bleaching step before steam distillation (10). The application of steam refining to rice bran oil will result in many advantages such as reduced neutral oil loss, no production of soap, and the production of high purity, industrial fatty acids.     

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.     

Wax composition of sunflower seed oils

Waxes are natural components of sunflower oils, consisting mainly of esters of FA with fatty alcohols, that are partially removed in the winterization process during oil refining. The wax composition of sunflower seed as well as the influence of processing on the oil wax concentration was studied using capillary GLC. Sunflower oils obtained by solvent extraction from whole seed, dehulled seed, and seed hulls were analyzed and compared with commercial crude and refined oils. The main components of crude sunflower oil waxes were esters having carbon atom numbers between 36 and 48, with a high concentration in the C₄₀−C₄₂ fraction. Extracted oils showed higher concentrations of waxes than those obtained by pressing, especially in the higher M.W. fraction, but the wax content was not affected significantly by water degumming. The hull contribution to the sunflower oil wax content was higher than 40 wt%, resulting in 75 wt % in the crystallized fraction. The oil wax content could be reduced appreciably by hexane washing or partial dehulling of the seed. Waxes in dewaxed and refined sunflower oils were mainly constituted by esters containing fewer than 42 carbon atoms, indicating that these were mostly soluble and remained in the oil after processing.     

Sesame oil.I. Properties of a solvent-extracted sesame oil

Summary Data and information have been presented with respect to the extraction, processing characteristics, and the chemical and physical characteristics of oil obtained from white sesame seed. Extraction of sesame seed with hexane yielded a crude oil low in free fatty acids and in color. The oil was refined with caustic soda under a variety of conditions with low losses and bleached with comparatively small quantities of several bleaching earths each of which produced a light-colored oil. Data have been presented on progressive changes which occurred in the composition, stability, plasticity, and refractive index of the fat during selective hydrogenation of the refined and bleached oils. Sesame oil hydrogenated to shortening consistency exhibited extremely high stability when tested by the accelerated active oxygen method. This stability confirms previous suggestions that sesame oil contains one or more antioxidants of greater activity than those present in most of the other vegetable oils of commerce. Presented at the International Sesame Conference, Clemson Agricultural College, Clemson, South Carolina, August 15–16, 1949. Trainee at the Southern Regional Research Laboratory, August 26, 1947 to April 1, 1948. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Refining and Bleaching of Peanut Miscella

The effects of type of crude miscella, oil content in miscella, concentrations of caustic soda solutions, method of mixing and temperature on the refining of high f. f. a. dark coloured peanut miscellas were investigated. Very effective removal of free fatty acids and decolorisation of the peanut miscellas were achieved by treating at 45-60% oil content with 16°-20° Bé caustic soda solution at room temperature (ca. 32 ± 1° C). Good bleaching of refined miscella samples also at room temperature with commercial acid treated earth and active charcoal was possible. Refined oils had 0.02-0.06% f. f. a. with 94-99% colour removed. Successful commercial possibilities are indicated.     

The total degumming process

A novel degumming process is described that is applicable to both undegummed and water-degummed oils. Such totally degummed oils have residual iron contents below 0.2 ppm Fe and residual phosphorus contents that average below 5 ppm P. Therefore, they can be physically refined to yield a stable refined oil while using the same level of bleaching earth commonly used for alkali refined oils prior to deodorization. They can also be alkali refined with reduced oil loss to yield a soapstock that only requires slight acidification for fatty acid recovery, and thus avoids the strongly polluting soap splitting process. The total degumming process involes dispersing a non-toxic acid such as phosphoric acid or citric acid into the oil, allowing a contact time, and then mixing a base such as caustic soda or sodium silicate into the acid-in-oil emulsion. This keeps the degree of neutralization low enough to avoid forming soaps, because that would lead to increased oil loss. Subsequently, the oil is passed to a centrifugal separator where most of the gums are removed from the oil stream to yield a gum phase with minimal oil content. The oil stream is then passed to a second centrifugal separator to remove all remaining gums to yield a dilute gum phase which is recycled. Washing and drying or in-line alkali refining complete the process. After the adoption of the total degumming process, in comparison with the classical alkali refining process, an overall yield improvement of approximately 0.5% has been realized. It did not matter whether the totally degummed oil was subsequently alkali refined, bleached and deodorized, or bleached and physically refined.     

Note on gossypol and its relation to color fixation in cottonseed oil

1. The crude oils studied contained from 0.00 to 0.04% gossypol.
2. Much of the gossypol added to crude cottonseed oils disappeared in one hour.
3. The disappearance of gossypol from refined, bleached, and deodorized cottonseed oil, from highly purified tripelargonin, and from ethyl acetate is demonstrable after the lapse of one hour.
4. It is suggested that the initial reaction of gossypol in the oils is an ester exchange reaction.
5. It is further suggested that secondary reactions result in the production of a red coloration product that is not removable from the oil by the standard refining and bleaching methods.

     

Extraction and refining of edible oil from extrusion-stabilized rice bran

Rice bran oil extracted from extrusion-stabilized bran was processed to a high quality salad oil. Stabilization prevented free fatty acid formation in rice bran prior to solvent extraction of the oil and thus increased the yield of refined oil. The flake form of the stabilized bran allowed rapid solvent percolation and efficient lipid extraction. Degumming soon after extraction removed a larger proportion of the gums and waxes and resulted in a higher yield of refined oil than if this procedure was delayed. Alkali refining was found to be most efficient with a concentration of 16° Bé (2.77M) NaOH and 0.5% NaOH excess. Acid activated clay was effective in removing color from the refined oil, and the addition of charcoal did not improve bleaching ability. Stabilization temperatures, within the range studied, did not appear to affect the bleached oil color. Color was measured spectrophotometrically at 537 and 612 nm.     

Refining crude cottonseed oil dissolved in hexane

Measurements were made of the surface tensions of mixtures of cottonseed oil and hexane and of their interfacial tensions against water and caustic soda solutions. Attempts were made to study the reaction rate between the two phases. The results show that in caustic refining of hexane miscellas the caustic is readily dispersed into the oil-hexane phase. Refining losses were found to be lower for miscellas containing less than 70% oil. Concentrations as low as 40% were refined successfully. The losses were inversely related to the viscosity of the solution. Sponsored by the Texas Engineering Experiment Station and the Cotton Research Committee of Texas, College Station, Texas.     

Refining cottonseed oil at high rates of shear

Summary Ten crude cottonseed oils obtained from different areas in the South and Southwest were refined with and without the use of high-shear agitation in the step involving the initial mixing of the crude oil and caustic soda solution. In each instance the use of high shear produced a lower color in the refined oil. The improvement with some oils was not marked because they either refined very well by the ordinary method or failed for some unexplained reason to respond readily to high-shear mixing. However a good proportion of the oils which were quite dark after refining by the ordinary method refined to a much lighter oil when high shear was used. It was established that in high shear refining the color of the refined oil decreased as the temperature at which high shear was used decreased, the time at high shear increased, and the rate at which shear was applied increased. However an increase in the latter above a certain value had no effect. Also it was found that the color of the refined oil decreased as the amount and strength of the caustic soda solution increased. Absorption spectra of some of the processed oils indicated that high shear was more effective than ordinary mixing in removing from an oil the gossypol-like and carotenoid color bodies. Presented at the 28th fall meeting of The American Oil Chemists’ Society, Minneapolis, Minn., Oct. 11–13, 1954. One of the laboratories of the Southern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Reducing Oil Losses in Alkali Refining

Neutralization is an important step in the chemical refining of edible oils. Free fatty acids (FFA) are generally removed in neutralization as sodium soaps but neutral oil is also entrapped in the emulsion and removed with the soap during centrifugation. Thus, alkali neutralization causes a major loss of neutral oil in the chemical refining of edible oils. The effects of demulsifiers (NaCl, KCl, Na₂SO₄ and tannic acid) on reducing alkali refining losses of refined palm, soybean, and sunflower oils (used as model oils) incorporated with FFA from rice bran oil were investigated. Adding small amounts of demulsifiers to the alkali neutralization step significantly reduced neutral oil loss of these model oils. All demulsifiers except for tannic acid had similar effects on refining losses in all oil model systems. The optimum demulsifier content was 1.0 % (w/w of oil).     

Effect of Subcritical Carbon Dioxide Extraction and Bran Stabilization Methods on Rice Bran Oil

The extraction of rice bran oil using the conventional organic solvent‐based Soxhlet method involves hazardous chemicals, whereas supercritical fluid extraction is a costly high‐temperature operating system. The subcritical carbon dioxide Soxhlet (SCDS) system, which operates at a low temperature, was evaluated for the extraction of rice bran oil in this study. In addition, rice bran that had been subjected to steam or hot‐air stabilization were compared with unstabilized rice bran (control). The yields; contents of tocopherols, tocotrienols and oryzanol; fatty acid profiles; and the oxidative stabilities of the extracted rice bran oils were analyzed. The yields using hexane and SCDS extraction were approximately 22 and 13–14.5 %, respectively. However, oil extracted using the SCDS system contained approximately 10 times more oryzanol and tocol compounds and had lower free fatty acid levels and peroxide values compared with hexane‐extracted oil. Overall, SCDS extraction of steamed rice bran represents a promising method to produce premium‐quality rice bran oil.     

Effects of Crude Rice Bran Oil Components on Alkali-Refining Loss

The effects of minor components in crude rice bran oil (RBO) including free fatty acids (FFA), rice bran wax (RBW), γ-oryzanol, and long-chain fatty alcohols (LCFA), on alkali refining losses were determined. Refined palm oil (PO), soybean oil (SBO) and sunflower oil (SFO) were used as oil models to which minor component present in RBO were added. Refining losses of all model oils were linearly related to the amount of FFA incorporated. At 6.8% FFA, the refining losses of all the model oils were between 13.16 and 13.42%. When <1.0% of LCFA, RBW and γ-oryzanol were added to the model oils (with 6.8% FFA), the refining losses were approximately the same, however, with higher amounts of LCFA greatly increased refining losses. At 3% LCFA, the refining losses of all the model oils were as high as 69.43–78.75%, whereas the losses of oils containing 3% RBW and γ-oryzanol were 33.46–45.01% and 17.82–20.45%, respectively.     

Membrane degumming and dewaxing of rice bran oil and its refining

A combined degumming-dewaxing batch by filtration through a ceramic membrane followed by earth bleaching and physical or alkali refining was studied for crude rice bran oil. The results were compared with the conventional centrifugal process for gum and wax removal. The characteristics of the refined oils obtained by the two processes were comparable. However, the former process was promising with respect to higher recovery of oil and better recovery of the byproducts gum and wax. Oil content of the mixed gum-wax phase was 7.6–8.1%. The recovery of oil using the membrane technique was always 2–3% higher than the centrifugal process. The membrane process was also found to be more effective and the quality of the final product was acceptable.     

Properties and processing of corn oils obtained by extraction with supercritical carbon dioxide

Crude oils were extracted from wet- and dry-milled corn germs with supercritical carbon dioxide (SC-CO₂) at 50–90 C and 8,000–12,000 psi and were characterized for color, free fatty acids, phosphorus, refining loss, unsaponifiable matter, tocopherol and iron content. They were compared with commercial products. Extraction of wetmilled germ with SC-CO₂ has some advantages over the conventional prepress solvent method commonly used in the industry. For example, SC-CO₂ extraction of wet-milled germ at 50 C and 8,000 psi yields crude oil with a lower refining loss and a lighter color. After laboratory processing, a light-colored, bland salad oil is obtained. Crude, refined, bleached and deodorized oils from SC-CO₂-extracted dry-milled germ appear equivalent to those obtained by expeller pressing. Presented in part at AOCS meeting, Toronto, Ontario, Canada, May 1982.     

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.     

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.     

Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil

The effect of different processing steps of refining on retention or the availability of oryzanol in refined oil and the oryzanol composition of Indian paddy cultivars and commercial products of the rice bran oil (RBO) industry were investigated. Degumming and dewaxing of crude RBO removed only 1.1 and 5.9% of oryzanol while the alkali treatment removed 93.0 to 94.6% of oryzanol from the original crude oil. Irrespective of the strength of alkali (12 to 20° Be studied), retention of oryzanol in the refined RBO was only 5.4–17.2% for crude oil, 5.9–15.0% for degummed oil, and 7.0 to 9.7% for degummed and dewaxed oil. The oryzanol content of oil extracted from the bran of 18 Indian paddy cultivars ranged from 1.63 to 2.72%, which is the first report of its kind in the literature on oryzanol content. The oryzanol content ranged from 1.1 to 1.74% for physically refined RBO while for alkali-refined oil it was 0.19–0.20%. The oil subjected to physical refining (commercial sample) retained the original amount of oryzanol after refining (1.60 and 1.74%), whereas the chemically refined oil showed a considerably lower amount (0.19%). Thus, the oryzanol, which is lost during the chemical refining process, has been carried into the soapstock. The content of oryzanol of the commercial RBO, soapstock, acid oil, and deodorizer distillate were in the range: 1.7–2.1, 6.3–6.9, 3.3–7.4, and 0.79%, respectively. These results showed that the processing steps—viz., degumming (1.1%), dewaxing (5.9%), physical refining (0%), bleaching and deodorization of the oil—did not affect the content of oryzanol appreciably, while 83–95% of it was lost during alkali refining. The oryzanol composition of crude oil and soapstock as determined by high-performance liquid chromatography indicated 24-methylene cycloartanyl ferulate (30–38%) and campesteryl ferulate (24.4–26.9%) as the major ferulates. The results presented here are probably the first systematic report on oryzanol availability in differently processed RBO, soapstocks, acid oils, and for oils of Indian paddy cultivars.     

The purification of edible oils and fats

Originally, oils were not refined but with the introduction of solvent extraction, refining became necessary. Crude cottonseed oil was refined by treating the oil with caustic soda and the same process was used for all other oils that needed refining. The subsequent introduction of centrifugal separators converted the original batch process into a continuous process. Degumming was introduced to obtain lecithin but limited to soya bean oil. Physical refining was introduced for high acidity oils like palm oil after the oil had been degummed to low residual phosphorus levels in the dry degumming process, in which the oil is first of all treated with an acid and then with bleaching earth. In Europe, further degumming processes were developed that allowed seed oil to be physically refined and later phospholipase enzymes were introduced to reduce oil retention by the gums and improve oil yield. Given these various oil purification processes, the refiner must decide which process to use for which oil in which circumstances. The paper provides a survey of what to do and when. It also discusses several topics that require further investigation and development.