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     

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.     

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.     

Extraction of rice bran oil using aqueous media

Aqueous extraction of oil from rice bran was studied on a laboratory scale and the resulting product was examined. The following process parameters influencing oil extraction were individually investigated: pH of aqueous media, extraction temperature, extraction time, agitation speed and rice bran‐to‐water ratio. Extraction temperature and pH were found to be the main factors influencing oil extraction. The highest oil yield was obtained at pH 12.0, extraction temperature 50 °C, extraction time 30 min, agitation speed 1000 rpm, and rice bran‐to‐water ratio 1.5‐to‐10. The quality of aqueous‐extracted oil in terms of free fatty acid, iodine value and saponification value was similar to a commercial sample of rice bran oil and hexane‐extracted oil, but the peroxide value was higher. Furthermore, the colour of aqueous‐extracted oil was paler than solvent‐extracted oil. © 2000 Society of Chemical Industry     

Lipase‐catalyzed production of biodiesel from rice bran oil

Biodiesel has attracted considerable attention as an alternative fuel during the past decades. The main hurdle to the commercialization of biodiesel is the cost of the raw material. Use of an inexpensive raw material such as rice bran oil is an attractive option to lower the cost of biodiesel. Two commercially available immobilized lipases, Novozym 435 and IM 60, were employed as catalyst for the reaction of rice bran oil and methanol. Novozym 435 was found to be more effective in catalyzing the methanolysis of rice bran oil. Methanolysis of refined rice bran oil and fatty acids (derived from rice bran oil) catalyzed by Novozym 435 (5% based on oil weight) can reach a conversion of over 98% in 6 h and 1 h, respectively. Methanolysis of rice bran oil with a free fatty acid content higher than 18% resulted in lower conversions (<68%). A two‐step lipase‐catalyzed methanolysis of rice bran oil was developed for the efficient conversion of both free fatty acid and acylglycerides into fatty acid methyl ester. More than 98% conversion can be obtained in 4–6 h depending on the relative proportion of free fatty acid and acylglycerides in the rice bran oil. Inactivation of lipase by phospholipids and other minor components was observed during the methanolysis of crude rice bran oil. Simultaneous dewaxing/degumming proved to be efficient in removing phospholipids and other minor components that inhibit lipase activity from crude rice bran oil. Copyright © 2005 Society of Chemical Industry     

Use of rice bran oil and epoxidized rice bran oil in carbon black–filled natural rubber–polychloroprene blends

In the present study we report the results obtained on the use of rice bran oil (RBO), a naturally occurring nontoxic oil, and its epoxidized variety (epoxidized RBO, or ERBO) in the compounding and vulcanization of different natural rubber–chloroprene rubber (NR–CR) blends. The processability, cure characteristics, and physical properties of the blends prepared with these oils were compared with those of control mixes prepared with aromatic oil. The optimum cure time and scorch time values of the different blends prepared with these oils were found to be lower than those of the respective control blends prepared with aromatic oil. Evaluation of physical properties of the different experimental blends showed that replacement of aromatic oil with these oils did not adversely affect their physical properties. Because RBO contains a good amount of free fatty acids it was tried as a coactivator in addition to its role as a processing aid. The level of these oils required for the blend preparation was optimized in a Brabender plasticorder. Physical properties such as tensile strength, elongation at break, tear strength, swelling index, and abrasion loss, for example, were evaluated for both experimental and control mixes. Comparison of cure characteristics and physical properties of the blends prepared with aromatic oil and with these oils showed that these oils could be used in place of aromatic oil in the above blends. It is also to be noted that aromatic oil is of petroleum origin and is reported to be carcinogenic. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4084–4092, 2003     

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.     

Enzymatic process for extracting oil and protein from rice bran

Enzymatic extraction of oil and protein from rice bran, using a commercial protease (Alcalase), was investigated and evaluated by response surface methodology. The effect of enzyme concentration was most significant on oil and protein extraction yields, whereas incubation time and temperature had no significant effect. The maximal extraction yields of oil and protein were 79 and 68%, respectively. Further, the quality of oil recovered from the process in terms of free fatty acid, iodine value, and saponification value was comparable with solvent-extracted oil and commercial rice bran oil, but the peroxide value was higher.     

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.     

Degumming rice bran oil using phospholipase‐A1

The efficacy of enzymatic degumming was assessed using the third generation phospholipase‐A₁, Lecitase®‐Ultra (EC 3.1.1.3) from Thermomyces lanuginosa/Fusarium oxysporum with different qualities of crude rice bran oil. The phosphorus content in the oil reduced to ～10 mg/kg from an initial level of 390 mg/kg after 2 h of incubation period at 50°C. However, in the solvent‐phase degumming, there was practically no phospholipid reduction at lower water content (2%) due to the poor contact between the highly nonpolar solvent and the aqueous phase (citric acid, NaOH, and enzyme solutions). Increasing the water content to 20% reduced the phosphorus level in the degummed‐oil to 71 mg/kg but did not match the performance of oil‐phase degumming. The degumming efficiency of Lecitase®‐Ultra was effective in oil‐phase and suitable for practical application. Solvent‐phase enzymatic degumming offers more benefits but needs greater efforts to overcome the challenges.     

Rapid equilibrium extraction of rice bran oil at ambient temperature

Rapid equilibrium extraction of soybean flour has been effective in obtaining an oil with reduced phospholipid content. This technique was examined to obtain a low phospholipid and low free fatty acid rice bran oil (RBO). The amount of RBO extracted with hexane from 1 g of rice bran at 22°C was measured over a 10-min period. The amount of oil extracted from variable amounts of bran with a fixed volume of solvent was also studied. Ninety percent of the oil was extracted in one minute, with 93% of the total RBO being extracted after ten minutes. This compares with the 98% yield obtained from soy flour, but increasing the amount of bran used did not reduce the extraction rate. This extraction method produced a good quality RBO with low phospholipid, low free fatty acid and low peroxide values.     

Improved oil treatment conditions for soft degumming

“Soft degumming” is a new physicochemical degumming process. It involves the complete elimination of phospholipids by using a chelating agent, EDTA, in the prescence of an emulsifying additive. To study the optimal cost of the process, a laboratory study was undertaken to find a method based on substituting the emulsifying additive by endogenous phospholipids. The phospholipids were first extracted from the oil by an initial hot-water treatment. In a second stage, a solution containing a chelating agent was incorporated. The mixture was then vigorously stirred to form an emulsion. The degummed oil was obtained after centrifugation. A comparative study carried out on several oils provided an indication of the efficiency of this alternative procedure. The phospholipid content of the processed oils was about 5 ppm phosphorus.     

Enzyme‐assisted water‐extraction of oil and protein from rice bran

Enzymatic water‐extraction of oil and proteins from rice bran was studied in a laboratory‐scale set‐up. The effects of the following enzymes – Celluclast 1.5L, hemicellulase, Pectinex Ultra SP‐L, Viscozyme L, Alcalase 0.6L and papain – on oil and protein extraction yields, and the level of reducing sugars in the extract were investigated. The results showed that Alcalase was most effective in enhancing oil and protein extraction yields. Papain was found to be superior to all carbohydrase enzymes but it gave lower yields than Alcalase. Celluclast 1.5L, hemicellulase, Pectinex Ultra SP‐L and Viscozyme L did not affect yields significantly but increased the level of reducing sugars in the extract. © 2002 Society of Chemical Industry     

Origin of problems encountered in rice bran oil processing

Rice bran oil, not being a seed‐derived oil, has a composition qualitatively different from common vegetable oils and the conventional vegetable oil processing technologies are not adaptable without incurring huge losses. The oil's unusual high content of waxes, free fatty acids, unsaponifiable constituents, phospholipids, glycolipids and its dark color, all cause difficulties in the refining process. An attempt was made in this investigation to look into factors that are responsible for such difficulties and to develop suitable methodologies for physical refining of rice bran oil. Special attention was given to dewaxing, degumming and deacidification steps. The high content of glycolipids (∼6%) present in the oil was found to be a central problem and their removal appeared crucial for successful processing of the oil. We have also isolated and identified, for the first time, phosphorus‐containing glycolipids that are unique to this oil. These compounds prevent a successful degumming of the oil and their high surface activity leads to unusually high refining losses during alkali refining. A number of simple processes has been evolved, including 1) a simultaneous dewaxing and degumming process, 2) an unusual enzymatic process to degum the oil, 3) processes for the removal of the glycolipids including the phosphoglycolipids and 4) a process for the isolation of the glycolipids which may have potential applications in the food, cosmetic and pharmaceutical industries. The processing protocol suggested here becomes the first and only one to produce an oil with less than 5 ppm of phosphorus from crude rice bran oil, rendering it thus suitable for physical refining. We believe that the present results are very significant and should contribute to a better utilization of this valuable oil.     

米糠精制产品的应用

对米糠综合利用的途径进行了详细论述；并总结厂各种米糠精制产品在日用化工、医药工业、食品工业、精细化工领域的具体用途，包括米糠油的浸提技术，米糠油作为营养保健食品的开发利用，米糠油作为油脂化工原材料的深加工；米糠油精炼皂脚中提取游离脂肪酸及脂肪酸衍生物的制备；米糠脱水、脱臭、脱色的小皂化物提取谷甾醇、生育酚、谷维素的方法；米糠脱蜡副产物制备糠蜡和二十烷醇的利用及米糠饼(粕)提取植酸钙、植酸和肌醇的利用途径，最后提出了大力发展我国米糠产业的市场前景。     

Membrane degumming of crude soybean and rapeseed oils

Membrane separation in edible oil processing is a potential area for energy savings. However, technical and operating-cost-related barriers have impeded the successful application of membrane separation in food processing. Studies were undertaken with soybean and rapeseed oils in a magnetically stirred flat-membrane batch cell with two types of composite polymeric membranes at 3 MPa pressure and at a constant temperature of 40°C. The membranes were NTGS-1100 and NTGS-2100, and used silicon as the active layer and polysulfone and polyimide as support layers, respectively. The membrane selectively rejected phospholipids, the content being less than 240 mg/kg in the permeate without any pretreatment or dilution of crude oil with organic solvent. Long-term studies up to 97 days with soybean oil at two different pressures, 2 and 3 MPa, showed that the rejection of phosphatides was above 96% in most permeates. The permeate flux remained nearly constant but must be improved.     

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.     

First approach on rice bran oil extraction using limonene

Edible oil extraction with petroleum derivatives as solvents has caused safety, health, and environmental concerns everywhere. Thus, finding a safe alternative solvent will have a strong and positive impact on environments and general health of the world population, considering the scale of oil extraction operations worldwide. The extraction of oil from rice bran by d‐limonene and hexane (for comparison) has been carried out at their respective boiling points at various solvent‐to‐meal ratios and for various extraction times. The preliminary data suggested that the optimum solvent‐to‐meal ratio and extraction time required for d‐limonene extraction of rice bran oil to be 5:1 and 1 h respectively. The initial quality characteristics (free fatty acid content, oil color, phospholipid content) of crude oil extracted under these optimum conditions were analyzed using various analytical methods based on the standard methods of AOCS and were found to be comparable to the oil extracted with hexane. The initial positive result has paved the way for further studies on issues related to meal qualities as well as to a scale‐up of the method in the near future.     

Nutrition of rice bran oil in relation to its purification

A comparative nutritive study was made to show that the extent of purification markedly influences the nutritive characteristics of rice bran oil. The coefficient of digestibility was 93.8% when rice bran oil that had been purified by degumming, deacidifying, bleaching and deodorizing was fed to rats; whereas it was 94.8% when extremely pure rice bran oil, which was achieved by including an additional dewaxing step, was used. Rice bran oil without deodorization, but purified by other treatments, showed a 96.2% coefficient of digestibility, which is somewhat lower than that of groundnut oil. However, after a feeding experiment over three months, the highly purified rice bran oil showed better results than the other two purified samples of rice bran oil, and was sometimes better than groundnut oil in terms of total lipid, triglyceride and especially in cholesterol content in serum, liver and heart tissues.