A study of rice bran oil refining

Examination of a number of rice bran oils revealed the presence of monoglycerides (0.5–1.4%) and other hydroxylated compounds such as diglycerides and glucosides. The hydroxyl numbers of the samples ranged from 8.5 to 27, depending on their acidity. On the assumption that the inordinately high refining losses of rice bran oil are due, along with the acidity, to the presence of hydroxylated compounds, the hydroxyl numbers of several samples of that oil were reduced by progressive acetylation with acetic anhydride. This was accompanied by gradual reduction of the refining losses, which seems to support the above mentioned assumption.     

Edible quality rice bran oil from high ffa rice bran oil by miscella refining

Rice bran oils high in free fatty acids (FFA) can be converted to cooking oil having low unsaponifiable matter and light color by a combination of miscella dewaxing and miscella refining.     

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.     

Effect of the full refining process on rice bran oil composition and its heat stability

The effects of the chemical refining process on the minor compounds of rice bran oil and its heat stability were investigated. After 8 h of heating, about 50% and 30% of total tocopherols remained in crude and refined rice bran oil, respectively. The individual tocopherols were differently affected by the refining process. The order of heat stability of tocopherols and tocotrienols in crude oil was found to be different from that in fully refined oil. A similar tendency was observed for sterols. After 8 h of heating, 65% and 72% of total sterols, and 14% and 46% of sterol esters, of crude or fully refined rice bran oil, respectively, disappeared. The heating process led to a 4% and 10.3% increase in polymer contents in crude and refined rice bran oil, respectively. Although refined rice bran oil showed good heat stability, when compared to crude oil its heat stability was decreased to some extent.     

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.     

Thermal gradient deacidification of crude rice bran oil utilizing supercritical carbon dioxide

The effect of isothermal and temperature gradient operation of a supercritical fluid fractionation column on the composition of rice brain oil (RBO) fractions has been studied. Application of a temperature gradient along the column was found to be beneficial in reducing the triacylglycerol (TAG) lost in the extract fraction. Utilization of higher temperature in the stripping section improved free fatty acid (FFA) removal from crude RBO. FFA acid content of the extract increased, and TAG content decreased with respect to time during the fractionation runs. Increasing the CO₂ flow rate from 1.2 to 2 L/min did not affect the extract composition significantly. By using the above approach, it is possible to obtain RBO fractions with similar total sterol ester content [∼23 high-performance liquid chromatographic area (HPLC) %, ferulic plus fatty acid esters] to that of the commercially available sterol ester-enriched (ca. 21 HPLC area % fatty acid esters) margarines/spreads.     

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.     

Influence of viscosity on wax settling and refining loss in rice bran oil

The role of viscosity on was settling and refining loss in rice bran oil (RBO) has been studied with model systems of refined peanut oil and RBO of different free fatty acids contents. Wax was the only constituent of RBO that significantly increased the viscosity (81.5%) of oil. Monoglycerides synergistically raised the viscosity of the oil (by 114.2%) and lowered the rate of wax settling. Although a reduction in the viscosity of the oil significantly decreased the refining loss, the minimum loss attained was still 20% more than the theoretically predicted value. This led us to conclude that some chemical constituents, such as monoglycerides, must be removed before dewaxing; thereafter, oryzanol and phospholipids have to be removed. One can get an oil free of wax, recover other by-products and reduce processing losses.     

Deacidifying rice bran oil by solvent extraction and membrane technology

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.     

Physical refining of rice bran oil in relation to degumming and dewaxing

Physical refining of rice bran oil (RBO) with acidity between 4.0 and 12.4% has been investigated in relation to degumming and dewaxing pretretments. It appears that physical refining after combined low-temperature (10°C) degumming-dewaxing produces good-quality RBO with respect to color, free fatty acid, oryzanol, and tocopherol content.     

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.     

Extraction and purification of oryzanol from rice bran oil and rice bran oil soapstock

Oryzanol is an important value-added co-product of the rice and rice bran-refining processes. The beneficial effects of oryzanol on human health have generated global interest in developing facile methods for its separation from rice bran oil soapstock, a by-product of the chemical refining of rice bran oil. In this article we discuss the isolation of oryzanol and the effect that impurities have on its extraction and purification. Presented are the principles behind the extraction (solid-liquid or liquid-liquid extraction, and other methods) of these unit operations covered in selected patents. Methods other than extraction such as crystallization or precipitation-based or a combination of these unit operations also are reviewed. The problems encountered and the ways to solve them during oryzanol extraction, such as prior processing and compositional variation in soapstock, resistance to mass transfer, moisture content and the presence of surface active components, which cause emulsion formation, are examined. Engineering inputs required for solving problems such as saponification, increasing mass transfer area, and drying methods are emphasized. Based on an analysis of existing processes, those having potential to work in large-scale extraction processes are presented.     

Factors affecting refining losses in rice (Oryza sativa L.) bran oil

Components of rice bran oil have been assessed for their effect on refining losses. Rice bran oil used in the study had the following (percent) analysis: free fatty acids, 6.8; phosphatides, 1.25; wax, 2.85; monoglycerides, 1.67; diglycerides, 4.84, and oryzanol, 1.85; the rest (80.74) was mostly triglycerides. The phosphatides and mono- and diglycerides had no noticeable effect on refining losses at levels of up to 2% in the oil. Waxes and oryzanol increased the refining losses substantially. In model experiments where these were incorporated into peanut oil individually and in combination, the wax at as low a level as 1% increased the refining losses by about 80% more than control and the refining losses increased with concentration of wax. Oryzanol had a similar effect. When wax and oryzanol were present together in the oil, the effect was synergistic—the refining losses were higher than the sum of their individual effects. Phosphatides, mono- and diglycerides tended to reduce the adverse effect of wax and oryzanol. The main components responsible for higher than normal refining losses in rice bran oil have been identified as wax and oryzanol.     

The concentration of tocols from rice bran oil deodorizer distillate using solvent

Tocols (tocopherols + tocotrienols) have been concentrated efficiently from rice bran oil (RBO) deodorizer distillate using solvent at low temperature. The levels of total tocols, total tocopherols, and total tocotrienols in RBO deodorizer distillate (starting material) were 31.5, 14.9, and 16.6 mg/g, respectively. Nine different solvents were tested, and acetonitrile was selected as the optimal solvent for concentrating tocols from the RBO deodorizer distillate. There was a significant (p <0.05) increase in the tocol level of the liquid fractions with decreasing temperature, for incubation temperatures up to –20 °C. In addition, significant differences (p <0.05) were observed in the relative percentages of α‐tocopherol, γ‐tocopherol, α‐tocotrienol, and γ‐tocotrienol between the raw sample and liquid fractions obtained at different temperatures using acetonitrile as the solvent. The concentration of the tocols from the RBO deodorizer distillate was temperature dependent, and a maximum of 89.9 mg/g was attained in the liquid fraction at – 40 °C. The relative percentage of tocotrienol homologs in the liquid fraction obtained at – 40 °C was approximately 80%. With acetonitrile as the solvent, the optimal temperature for concentrating the tocols from RBO deodorizer distillate was –20 °C when yield was considered.     

A novel process for physically refining rice bran oil through simultaneous degumming and dewaxing

A new process for the physical refining of rice bran oil through combined degumming and dewaxing was developed on a laboratory scale and then demonstrated on a commercial scale. The simultaneous degumming and dewaxing of the crude oil with a solution of water and CaCl₂, followed by crystallization at a low temperature (20°C), facilitated precipitation of the hydratable and nonhydratable phosphatides along with the wax, which enabled its separation and reduction to a greater extent. Bleaching and subsequent winterization (20°C) of this oil further reduced the phosphorus content to less than 5 ppm. Thus, these pretreatment steps enabled the physically refined rice bran oil to meet commercially acceptable levels for color, FFA content, and cloud point values (10–12 Lovibond units in a 1-in, cell, <0.25%, and 4–5°C, respectively) with very low neutral oil loss; this has not been observed hitherto. Rice bran oil is known for its high levels of bioactive phytochemicals, such as oryzanol, tocols, and sterols. The process reported here could retain more than 80% of these micronutrients in the end product. This paper was previously presented at the 95th AOCS Annual Meeting and Expo, Cincinnati, Ohio, May 9–12, 2004     

Comparison of solvent extraction characteristics of rice bran pretreated by hot air drying,steam cooking and extrusion

Rice bran was pretreated by hot air drying, steam cooking and extrusion before solvent extraction of oil. The extractions were conducted in a glass column percolator (i.d. 120 mm), packed to a depth of 90 cm and using n-hexane at 60 C and gravity feed. Fines (defined as<0.5 mm) in raw bran were significantly reduced by steam cooking and extrusion treatments. Extruded rice bran (ERB) was pelletized and had a bulk density 1.5 times higher than the other products. Regardless of the weight of bran loaded in the percolator, extraction time to reach 1% residual oil was decreased in the order of 116, 67 and 10 min for hot air-dried rice bran (HARB), steam-cooked rice bran (SRB) and ERB, respectively. This was due to increases in the percolation rate of SRB by 2 times and by 9 times for ERB compared to HARB. The solvent/bran ratio for extraction to 1% residual oil was decreased by nearly half, from 3.18 for HARB and 3.12 for SRB to 1.77 for ERB.     

Comparison of steam and nitrogen in the physical deacidification of soybean oil

Deacidification in physical refining is one of the most sensitive steps in refining edible vegetable oils because of its large impact on the quality of the oil. The removal of volatile compounds such as FFA is accomplished at elevated temperatures and a high vacuum with a stripping gas, usually steam. The aim of this work was to verify, at the laboratory level, the advantages of using an alternative stripping gas, nitrogen, instead of steam. An ideal vapor-liquid equilibrium model (IVLE) was used to compare the stripping capacities of steam and nitrogen and to analyze the effects of various operational parameters (temperature, pressure, amount of stripping gas) on the residual acidity of the oil. There was no clear evidence that nitrogen showed a higher capacity to strip FFA than steam. The IVLE model seemed suitable to describe FFA laboratory distillation by using steam or nitrogen, provided the final residual content of FFA was not too low.     

Experimental data and modeling of rice bran oil extraction kinetics using ethanol as solvent

The extraction kinetics of rice bran oil (RBO), free fatty acids (FFA), and oryzanol using ethanol (0 and 6.3 mass % of water) at 40°C–70°C were investigated. High extraction temperatures increased the yields of RBO and oryzanol by increasing the diffusivity of the solvent, regardless of its water content. Two models that permitted the estimation of mass transfer and diffusion coefficients were fitted to the oil extraction data with low average relative deviations (≤5.92%). The diffusion coefficient (1.93–7.46 × 10^–10 m²?s^–1) increased with increasing temperature and decreasing hydration of the solvent.