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Rice Bran Oil
Frank T. Orthoefer 1. INTRODUCTION Rice oil, also called rice bran oil, has been used extensively in Asian countries such as Japan, Korea, China, Taiwan, Thailand, and Pakistan (1, 2). It is the preferred oil in Japan for its subtle flavor and odor. Interest in rice oil in the United States was initiated after WWII, primarily to provide an additional revenue stream to the rice miller. More recently, interest in rice oil escalated with its identification as a ‘‘healthy oil’’ that reduces serum cholesterol (3, 4). Three facilities were constructed in the United States to produce rice oil (5). The first facility began operation in the late 1950s, and a second facility was started in the 1960s. Both were shut down in the early 1980s because of economics. A third production facility began operation in the early 1990s and continues producing both bulk and packaged oils for the domestic and export markets. Attempts at further development of rice oil production have not been successful because of high capital requirement to construct an oil extraction plant and refining facility and limited availability of stabilized rice bran (6). Rice oil is a minor constituent of rough rice when compared with the carbohydrate and protein content. Two major classes of lipids are present: those internal within the endosperm and those associated with the bran. The internal lipids contribute to the nutritional, functional, and sensory qualities of rice (7). Rice bran is the main source of rice oil. The majority of available bran continues to be used for animal feeds without being extracted for the oil. The food industry

Bailey’s Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

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uses minor quantities of stabilized rice bran as a source of dietary fiber, protein, and desirable oil. This chapter reviews the source and composition of rice bran oil, its nutritional characteristics, production, and refining of the oil and its applications.

2. COMPOSITION OF RICE AND RICE BRAN LIPIDS The structure of the rice kernel is given in Figure 1. Lipids are present as spherosomes or lipid droplets less than 1.5 mm in diameter in the aleurone layer, less than 1.0 mm in the subaleurone layer, and less than 0.7 mm in the embryo of the rice grain (7, 9). Most of the lipids in the endosperm are associated with protein bodies and the starch granules as bound lipids (10). The lipids are broadly classified as nonstarch and starch lipids (Table 1). The majority of the lipids are the nonstarch lipids. Starch lipids consist primarily of lysophospholipids, triacylglycerols, and free fatty acids (13). Major phospholipid species are lysophophatidylethanolamine and lysophosphatidylcholine. The major fatty acids are palmitic and linoleic acids along with oleic acid. Minor amounts of monoacylglycerols, diacylglycerols, and sterols are also found. Glycolipids found are diglycosyl monoacylglycerols and monoglycosyl monoacylglycerols. The component sugars are galactose and glucose. The nonstarch lipids in the aleurone, subaleurone, and germ layers were 86–91% neutral lipids, 2–5% glycolipids, and 7–9% phospholipids, although these are variable because of different milling degrees (11). The fatty acid composition of

Figure 1. Relative proportion of major rice caryopsis components (8).

COMPOSITION OF RICE AND RICE BRAN LIPIDS

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TABLE 1. Lipid Composition of Rice and its Fractions (7, 9, 11, 12).a Nonwaxy Nonstarch Lipids in Rice Fractions Starch Lipid in —————————————————— ——————— Brown Milled Hull Brown Milled Bran Germ Polish Rice Rice 2.7 181 94 6 23 35 38 4 86 71 7 5 9 4 4 <1 — 0.8 190 100 6 33 21 40 6 82 58 15 8 10 9 4 2 1 18.3 184 99 6 23 37 36 4 89 76 4 4 7 3 3 <1 — 30.2 189 101 34 24 36 37 3 91 79 4 2 7 3 3 <1 — 10.8 0.6 .05

Property

Lipid content 0.4 Saponification no. 145 Iodine no. 69 Unsaponifiable matter 26 Fatty acid composition Wt % of total Palmitic 18 Oleic 42 Linoleic 28 Others 12 Neutral lipids, % of total lipids 64 Triglyceride — Free fatty acids — Glycolipids, % of total lipids 25 Phospholipids, % total lipids 11 Phosphotidylcholine — Phosphatidylethanolamine — Lysophosphatidylcholine — Lysophosphatidylethanolamine —
a

23 35 38 4 87 72 5 5 8 3 3 <1 —

46 12 38 4 28 4 20 19 53 4 5 21 22

45 11 40 4 26 2 21 16 58 4 5 23 25

Based on 6% bran-germ, 4% polish, and 90% milled rice from brown rice.

nonstarch lipids showed 22–25% palmitic, 37–41% oleic acid, and 37–41% linoleic acid (Table 2). The brown rice non-starch lipids was 14–18% in germ, 39–41% in bran, 15–21% in polish, and 25–33% in milled rice. The composition was 83–87% triacylglycerol together with 7–9% free fatty acids, diacylglycerols, sterols together with sterol esters, hydrocarbons, and wax. Oil extracted from rice bran contained 20.1% total lipid, 89.2% neutral lipids, 6.8% glycolipid, and 4.0% phospholipid (14). A component of rice bran oil that has promise as a nutraceutical compound is g-oryzanol (15). g-Oryzanol was first isolated from soapstock from rice oil

TABLE 2. Major Lipid Classes of Crude Bran Oil Extracted from Raw Rice Bran and Their Fatty Acid Composition (14). Fatty Acid Composition (%) —————————————————————————————————————————— Lipid classa wt% 14:0 16:0 18:0 18:1 18:2 18:3 20:0 saturated unsaturated TL NL GL PL
a

20.1 89.2 6.8 4.0

.40 0.43 0.09 0.11

22.21 23.41 27.34 22.13

2.21 1.88 0.28 0.16

38.85 37.24 36.45 38.11

34.58 35.29 35.76 39.32

1.14 0.61 1.07 0.68 0.18 0.17

25.43 26.40 27.61 22.40

74.57 73.60 72.39 77.60

TL ¼ total lipids; NL ¼ neutral lipids (nonpolar lipid and free fatty acids); GL ¼ glycolipids; PL ¼ phospholipids.

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CH3O H
4

3

2 1 7 8

5

6

CH CH COOR (ROH see below) ROH = campesterol = O sitosterol = cycloartenol = 24 methylene-cycloartenol = cyclobranol

Figure 2. Major ferulates in oryzanol (9).

refining (16). Although originally thought to be a single compound, it is now known to be a mixture of steryl and other triterpenyl esters of ferulic acids (cycloartenyl ferulate, 24 methylenecycloartenyl ferulate, and b sitosterol ferulate and campesteryl ferulate) (Figure 2). It is present at 1.5–2.9% of rice bran oil with a m.p. of 138.5 C. The oryzanol content is dependent on rice grain variety with long grain rice at 6.42 mg/g and medium grain rice at 5.17 mg/g (17). Tocopherols and tocotrienols (tocols) are present in rice oil (Figure 3). Crude rice bran oil was found to contain, per 100 g of oil, 19–46 mg of a-tocopherol, 1–3 mg of b-tocopherol, 1–10 mg of g-tocopherol, and 0.4–0.9 mg of d-tocopherol, 14–33 mg of a-tocotrienol, and 9-69 mg of g-tocotrienol (18, 19) (Table 3). The mean tocol content was 93 mg/100 g for crude oil and 50 mg/100 g for refined oil (19). Close to 370 mg/100 g has been reported (20). Rice bran stabilization and storage (21) and method of extraction (22) affects the concentration of tocols in the oil. g-Tocotrienol is more stable and persists to a greater extent during storage than other tocols (21). Other factors influencing toco content are milling and variety (17, 23). Long-grain varieties have higher levels of tocotrienols than medium grain rice (17).
R3 R2 HO R1 Tocopherols (T) R3 R2 HO R1 Tocotrienols (T3)
Figure 3. Structure of tocopherol and tocotrienol (9).

O R1 α-T(3) β-T(3) γ-T(3) δ-T(3) CH3 H3 H H R2 CH3 H CH3 H R3 CH3 CH3 CH3 CH3

O

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TABLE 3. Tocopherol and Tocotrienol Concentrations (mg/100g) in Raw Rice Bran and Commercially Available Refined Oil (14). Source Rice bran Brown ricea Crude oila Refined oil
a

a-T 6.3 0.63 31.50 8.2

b-T 0.9 0.09 4.50

g-T 3.20 0.32 16.00 12.80

d-T 0.20 0.02 1.00 1.3

a-T3 3.8 0.38 19.0 2.1

g-T3 12.0 1.2 60.0 42.9

d-T3 0.7 0.07 3.5 3.5

Calculated values.

Waxes are present as long-chain fatty acid esters with fatty alcohols, methanol, and ethanol. Fatty acid analysis showed that behenic (C:22), lignoceric (C:24), and palmitic acids (C:16) are the major fatty acid for longer alkyl esters and oleic and palmitic for the shorter alkyl esters (Table 4) (24). The major alcohols found are for longer alkyl esters. These are as follows:

TABLE 4. Fatty Acids of Sterol and Alkyl Esters, Alcohols of Longer Alkyl Esters, and Alkanes and Alkenes of Rice Bran Waxy Lipids (24). Fatty Acids Composition of: —————————————————————————————————————————— Carbon and Alcohols of Double Bond Longer Alkyl Shorter Alkyl Longer Alkyl No. Sterol Esters Esters Esters Alkane Alkenes 14.0 16.0 18:0 18:1 18:2 18:3 20:0 22:0 23:0 24:0 25:0 26:0 27:0 28:0 29:0 30:0 31:0 32:0 33:0 34:0 35:0 36:0 37:0 0.6 11.1 1.0 33.1 51.1 2.0 0.7 — — — — — — — — — — — — — — — — 1.8 23.8 3.8 2.9 0.3 — 3.6 32.6 31.2 — — — — — — — — — — — — — — 2.2 35.5 0.8 60.2 1.5 — — — — — — — — — — — — — — — — — — — — — — — — 0.1 2.0 — 11.2 — 6.3 — 12.5 — 19.1 — 10.5 (5.1) — 6.6 (18.3) — 3.0 (5.4) — — — — — — — — — 1.3 0.2 2.0 0.8 9.5 3.6 46.5 3.0 23.7 1.4 6.5 0.7 0.8 — — — — — — — — — — — — — — 7.9 1.3 38.8 0.9 20.8 0.5 18.8 1.4 8.4 0.1 1.6

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Major alcohols: Tetratriacontanol Triacontanol Dotriacontanol Octacosanol Tetracosanol

C34:0 C30:0 C32:0 C28:0 C24:0

Straight-chain alkanes, alkenes, and branched-chain alkenes (squalene) are detected in the hydrocarbon fraction. The squalene content is 120 mg/100 g. Hard and soft waxes are recovered from crude rice bran oil with m.p. of 79.5 C and 74 C (25). The hard wax consists of 64.5% fatty alcohols, 33.5% fatty acids, and 2% hydrocarbons. Soft wax includes 51.8% fatty alcohols, 46.2% fatty acids, and 2% hydrocarbons.

3. MILLING OF RICE Today’s modern rice mills efficiently separate hulls from paddy rice followed by bran removal (Figure 4) (6). Milling consists of rubber roll dehullers, paddy separators, abrasive milling (whitening), and possibly friction mills. The bran and polish consist mainly of the outer layers of rice caryopsis. These include the pericarp, seed coat, nucellus, aleurone layer, germ, and part of the subaleurone layer of the starchy endosperm. Rice bran makes up 5–8% of rough rice, and the polish may account for an additional 2–3% (5). Commercial rice bran is a fine, floury material made up of the outer layers of the brown rice plus pulverized germ, some hull fragments, and some endosperm (white rice fragments) (8). The particle size distribution of the bran is shown in Table 5 (26). The particle size of the bran varies significantly with type of milling and milling condition. The composition of the bran also varies as a function of milling degree (Table 6) (27). Generally, a low degree of milling is practiced. Rice bran is rich in lipids, proteins, minerals, vitamins, phytin, trypsin inhibitor, lipase, and lectin (hemeagglutinins) (5). Compared with other cereal brans, rice bran with germ is a little higher in fat content but comparable in protein, fiber, and ash (Table 7). The high phosphorous content is among the highest of the cereal grains. Rice bran is also high in silica probably because of the presence of rice hull fragments. Bran is high in B vitamins and tocopherol, but it contains only a little Vitamin A and C (28). Rice bran and germ are used in animal feeds as a low-cost source of protein and oil (6). ‘‘Rice mill feed’’ is a combined product produced by huller mills, where dehulling and milling is a single processing step (5). Raw rice bran, when dehulling is a separate processing step, has about four times the oil content (17–20%) of rice mill feed (6). Parboiled rice bran produced by cooking of rough rice prior to milling has a greater oil content, usually above 20%, than raw rice bran. The higher oil content may be caused by less endosperm contamination, better extractability of the oil

MILLING OF RICE

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Steps in Rice Milling Rough Rice

Screening

Destoning

Dehulling

Polishing

Bran

Grading and sizing

Milled Rice

Figure 4. Steps in rice milling.

TABLE 5. Particle-Size Distribution (%) of Raw and Heat-Stabilized Brans (26). Mesh 18 18–30 30–50 50–80 80–100 <100 Particle Size (mm) >1000 1000–595 595–297 297–177 177–149 <149 Raw Bran 0 2.4 30.0 12.2 8.5 46.7 Moist Heat-Stabilized Bran 0 18.6 32.7 18.5 10.8 19.4

TABLE 6. Variation in Rice Bran Composition as a Function of the Degree of Milling (27). Degree of Milling (%) 1st Cone 2nd Cone 3rd Cone 4th Cone
a

Protein 17–0 17.6 17.0 16.7

Fat 17.7 17.1 16.5 14.2

Bran Composition (%) Fiber Ash 10.5 10.3 5.7 5.7 9.8 9.4 8.4 7.5

NFEa 45.0 45.2 52.5 55.9

0–3 3–6 6–9 9–10

Nitrogen-free extract.

TABLE 7 Composition (% at 14% Moisture) of Rice Bran and Polish and Other Cereal Brans (26). Rice —————————————— Bran Polish Constituent Crude protein (% N Â 6.25) Crude fat (%) Crude fiber (%) Available carbohydrates (%) Crude ash (%) Calcium (mg/g) Magnesium (mg/g) Phosphorus (mg/g) Phytin phosphorus (mg/g) Silica (mg/g) Zinc (mg/g) Thiamine (B1) (mg/g) Riboflavin (B2) (mg/g) Niacin (mg/g) 12.0–5.6 15.0–19.7 7.0–11.4 31.1–52.3 6.6–9.9 0.3–1.2 5–13 11–25 9–22 6–11 43–258 12–24 1.8–4.3 267–499 11.8–13.0 10.1–12.4 2.3–3.2 51.1–55.0 5.2–7.3 0.5–0.7 6–7 10–22 12–17 2–3 17–60 3–19 1.7–2.4 224–389

Wheat Bran 14.5–15. 2.9–4.3 6.8–10.4 50.7–59.2 4.0–6.5 1.2–1.3 5.6 9–13 10 2 105 5.4–7.0 2.4–8.0 181–550

Corn Bran 7.8–11.5 4.4–8.1 2.6–9.4 58.9–62.6 1.9–3.4 0.3–0.4 2.5 1–6 — — — 4.2 1.5 —

Barley Bran 11.5 2.8 9.6 58.4 3.6 2.8 — 5–8 3.1 — 21 — — —

Rye Bran 14.6 2.6 6.6 58.0 4.2 0.9–1.2 — 7.2–10.5 6.9 — 56 2.5 0.2 22.6

Oat Bran Shorts 8.8–16.2 3.0–6.8 20.5 61.4 6.3 0.9 3.0 8.1 — — — 4.1 3.3 1.5

Sorghum Bran 7.7–15.0 4.6–4.7 7.4–9.1 54.3–64.1 2.1–3.0 — — — — — — — — —

Millet Bran 11.5 8.0 — 56.0 10.5 0.8 4.0 — — — 10.6 — —

ENZYMES IN RICE BRAN

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by solvents, and outward movement of the oil from aleurone and germ cells to the bran layer (28). The final physical and chemical nature of bran depends on the following: 1. 2. 3. 4. 5. Rice variety Treatment of the grain before milling Type of milling system Degree of milling Fractionation that occurs during milling (29).

The preferred method for milling of rice that gives hulls, bran, and milled rice is referred to as ‘‘multistage’’ or ‘‘multiple break’’ where shellers (dehullers), polishers, and whiteners are used. The hull is first removed in shellers, and the dehulled brown rice undergoes subsequent whitening operations. The amount of contaminants in the bran affects the total lipid content. Contaminants are broken rice and layers from the endosperm. Addition of calcium carbonate, usually at 0.25% of rough rice as a milling aid during whitening, further reduces the oil content. Other milling aids such as diatomaceous earth and ground limestone have also been used. In developing countries, most rice is milled in a one-stage (huller) mill that removes hull, bran, and germ as a single mixture. It is estimated that less than 25% of rough rice is fractionated into hull and bran fractions (29).

4. ENZYMES IN RICE BRAN Rice bran contains active enzymes (30). Germ and the outer layers of the caryopsis have higher enzyme activities. Some enzymes that are present include a-amylase, b-amylase, ascorbic acid oxidase, catalase, cytochrome oxidase, dehydrogenase, deoxyribonuclease, esterase, flavin oxidase, a and b-glycosidase, invertase, lecithinase, lipase, lipoxygenase, pectinase, peroxidase, phosphatase, phytase, proteinase, and succinate dehydrogenase. Particularly lipase, but also lipoxygenase and peroxidase, are probably most important commercially because they affect the keeping quality and shelf life of rice bran. Lipase promotes the hydrolysis of the oil in the bran into glycerol and free fatty acids (FFA) (5). The lipase has been studied extensively. In the intact grain, the lipases are localized in the testa-cross layer of the rice grains while the oil is in the aleurone and subaleurone layers and in the germ (26, 26a). The germ, where 60% of the lipase occurs, is similarly compartmentalized. During milling, the enzyme and substrate are bought together. The rate of FFA formation is highly dependent on environmental conditions. Formation of 5–7% free fatty acids per day has been reported (29). Up to 70% FFA has been reported for a single month of bran storage. Production of FFA in a clean U.S.-produced bran is shown in Figure 5 (31). Rice

474
90 80 70 60 FFA (%) 50 40 30 20 10 0

RICE BRAN OIL

20

40

60 80 Time (number of Days)

100

120

140

Figure 5. Free fatty acid (FFA) increase in raw bran during a 135-day storage period (8).

bran oil contains 2–4% FFA at the time of milling. Less than 5% FFA is desirable for producing rice bran oil because high FFA results in high refining losses. The composition of crude rice bran oil produced by hexane extraction of stabilized bran is shown in Table 8. Lipase has a molecular weight of about 40,000 Da and an isoelectric point (pI) of 8.56 (32). It is activated by calcium and inhibited by heavy metals. The optimum pH is 7.5–8.0, and the optimum temperature is 37 C. It is inactivated by heating at 60 C for 15 minutes. Rice bran lipase preferentially hydrolyzes fatty acids from the

TABLE 8. Crude Rice Bran Oil Composition (8). Lipid Type Saponifiable lipids Neutral lipids Triacylglycerols Diacylglycerols Monoacylglycerols Free fatty acids Waxes Glycolipids Phospholipids Unsaponifiable lipids Phytosterols Sterol esters Triterpene alcohols Hydrocarbons Tocopherols Percent 90–96 88–89 83–86 3–4 6–7 2–4 6–7 6–7 4–5 4–2 43 10 28 18 1

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1 and 3 positions in the triacylglycerol molecules. Two subunits are suggested for lipase, and these are held together by disulfide bonds. A second rice bran lipase has a pI of 9.1 and an optimum temperature of 27 C (33). It has a high specificity for triacylglycerols having short-chain fatty acids. The enzyme, lipoxygenase, is associated with the oxidation of the polyunsaturated fatty acids (PUFA) having a cis, cis-pentadiene structure. The carbonyl products from the degradation, particularly hexanal, have been implicated in the stale flavor of rice. Lipoxygenase activity is highest in the germ fraction. Three forms of lipoxygenase have been isolated differing in pH optimum and specificity (34).

5. STABILIZATION OF RICE BRAN The instability of rice bran has long been associated with lipase activity (35). As long as the kernel is intact, lipase is physically isolated from the lipids (29). Even dehulling disturbs the surface structure allowing lipase and oil to mix. Oil in intact bran contains 2–4% free fatty acids (2). Once bran is milled from the kernel, a rapid increase in the FFA occurs. In high humidity storage, the rate of hydrolysis is 5–10% per day and about 70% in a month as shown earlier. The objectives of rice bran stabilization are as follows:      Arrest lipase and lipoxygenase activity. Improve oil extraction efficiency. Reduce fines in crude oil. Sterilize the bran. Reduce color development.

The lipoxygenase and peroxidase enzymes also have a negative impact on the oxidative state of the bran (Table 9). Further degradation of the oil occurs as reflected in an increase in peroxide and thiobarbituric acid value and a decrease in iodine value. Both lipoxygenase and peroxidase enzymes are inactivated with lipase inactivation.
TABLE 9. Changes in the Composition of Bran Lipids During Storage of Milyang 23 Rice Bran at 30 C and 80% RH (28). Storage Period (weeks) —————————————————————————————————————————— Oil Property 0 1 2 3 4 5 Free fatty acids (% as oleic acid) Peroxide value (meq/kg) Iodine value (%) TBAa (mg of malonaldehyde) equivalents/Kg
a

3.6 32.8 96.8 0.5

33.0 73.2 90.2 0.8

40.3 96.0 85.4 1.1

45.8 109.3 83.2 0.7

61.8 90.6 79.0 0.7

68.2 91.0 74.7 0.6

Thiobarbituric acid.

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Lipase activity results in hydrolytic rancidity. There is little or no change in flavor of the bran with an increase in FFA (5). Lipoxygenase activity, however, increases with the presence of FFA resulting in oxidative rancidity (36). It is oxidative deterioration that is responsible for the flavor and odor of rancid rice bran. Peroxidase is used as a convenient index of lipase activity. The inactivation temperature for lipases and associated enzymes is dependent on the moisture content. At 4% moisture, inactivation temperature for lipoxygenase is 40 C, lipase is 55 C, and peroxidase is 70 C (28). Methods for stabilization of rice bran have been reviewed (37). These include dry heating, wet heating, and extrusion. The most practical method has been the use of extrusion or expansion methods. In retained heating methods (dry heat), a simple hot air drying reduces the moisture content to 3–4%. The bran must be kept dry in moisture-proof containers, or the rehydrated bran will regain its lipase activity. If the bran is heated in the presence of moisture, the lipase is permanently denatured. The types of retained-moisture heating methods include extrusion cookers and sealed rotating drums. Extrusion cooking results in both lipase denaturation and bran sterilization. When pressure is released, part of the superheated moisture evaporates with little or no drying being required. Expanders or expellers are also used to permit addition of moisture (wet heating) through steam and the formulation of colletts or pellets from the bran. The colletts aid handling and oil extraction. Extrusion (dry heat) cookers have been ideal for stabilization because excess moisture is not added, eliminating the need for drying. The heating of the bran occurs through conversion of mechanical energy of the screw drive to heat the bran. Temperatures used for stabilization vary from 100 to 140 C. The bran is kept hot for 3–5 minutes after extrusion to ensure lipase inactivation. The hot bran is then cooled using ambient air. Extrusion cooking of the bran was pioneered by the Western Regional Research Laboratory (28, 29, 29a). Dry extrusion was found more suitable for stabilizing bran to be used as a food ingredient (38). Stabilization within 1 hour after milling is considered ideal for bran quality. Wet heating is more effective for bran stabilization for oil extraction than is dry heating. Lipase is inactivated in 3 minutes at 100 C (37). The equipment that can be used include steam cookers, blanchers, autoclaves, and screw extruders with injected steam and water (30). Extrusion with steam injection and up to 10% added water reduces the temperature required for lipase inactivation. Temperatures are reduced to 100–120 C. Product may be held at 100 C for 1.5–3.0 minutes before drying to a stable moisture content. Bran expands as it exits the extruder, and water flashes to steam (8). Porous pellets assist in solvent percolation during oil extraction. Fines are agglomerated as well. Addition of water/steam to bran during wet extrusion requires drying after stabilization. Hot air is simply passed through a bed of pellets. Although this increases the cost of stabilization, lipase inactivation is permanent with less nutritional damage to the bran. The recovered oil is lighter in color with lower refining losses.

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The stabilized bran may be stored for extended periods, although extraction should be completed within 1 month for best quality oil (39). Parboiling of rice is also an example of wet heat stabilization. The lipase in rough rice is completely inactivated by either autoclaving for 3–20 minutes or by parboiling. Other stabilization methods that have been investigated are as follows: 1. Refrigeration to reduce the rate of hydrolysis (8) 2. Lowing pH to reduce lipase activity (4) 3. Chemical additions such as sodium metabisulfite (39a)

6. RICE BRAN TO RICE BRAN OIL Rice bran is the source of rice bran oil (30). Various commercial efforts to extract the oil have been made over the past 50 years. Initially, use of the oil in traditional foods was targeted. More recent efforts have emphasized the nutritional benefits of rice bran oil. Rice bran oil with a low free fatty acid content can be extracted with hexane from extrusion stabilized bran. The process flow is shown in Figure 6. Nonstabilized bran, although having a high free fatty acid, can also be used for production of oil. With nonstabilized bran, the extraction is similar to that of extracting a fine powder. Preprocessing of the bran through an extruder, expander, or expeller may be used to form either a flake or pellet that results in improved solvent flow through an extraction bed (40). Flaked bran with only 7–12% passing a 25 mesh screen gave a percolation through a 60-cm bed of 563–620 L/m2/min. The oil extraction rate

Rice bran

Stabilization

Pellets

Hexane extraction

Desolventizing

Crude rice bran oil
Figure 6. Process for rice oil production (8).

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was rapid, with 96% of the oil being removed in 5 minutes and only 0.7% residual oil remaining after 1 hour of extraction. Earlier methods to recover the oil used hydraulic pressing (28). In a Japanese system for pressing, the raw bran is cleaned by sifting and air classification to remove whole and broken grains and hulls, and, in some instances, to recover rice germ. The bran is then steam cooked, dried, prepressed, and finally expeller pressed. Hexane extraction may be batch, battery, or continuous type (12). All three systems were recently operating in Japan. Continuous systems operate in Brazil, Burma, Egypt, India, Mexico, Taiwan, Thailand, and the United States. The bran in the most efficient systems is stabilized, pelletized, and, if required, dried. After the pretreated bran is placed in the extractor, hexane is pumped in and allowed to percolate through the bran to extract the oil. Countercurrent extraction is used. The miscella (solvent plus oil) is passed through filters to remove the bran fines before evaporation for solvent and crude oil recovery. The production of fines from expander stabilized bran depends on stabilization condition (38). Flake size is larger if expanded at 120 C, but the flakes are fragile and easily broken. Flakes with high moisture content were more resistant to breakage. Final bran moisture was about 6%. Pelletizing of the bran improves percolation and minimizes fines in the miscella. Pellets are 6–8 mm in diameter. Moistening during palletizing reduces the fines problem. Parboiled bran does not produce the hard pellets found for raw bran possibly because of protein denaturation during parboiling (33). Binding of the fines in the pellet is assisted by starch gelatinization during heating of the bran. Parboiled bran also presents problems with sticking to dryer surfaces resulting in self-ignition in the dryer. Prior mixing with raw bran alleviates the problem. The X-M process combines solvent extraction and milling of the rice (41). Brown rice is pretreated with warm rice oil (0.5%) for 2–3 hours to soften the bran. The rice is then milled in the presence of a rice oil miscella. The solvent slurry is then removed from the rice and the rice oil is recovered. Advantages are that stabilization is not required and the resultant oil had a minimum FFA level. This process is no longer used. Extraction of rice bran oil by supercritical fluid has been investigated (5). Minor reductions in oil yield may occur. The oil yield with supercritical CO2 is 17.98%, with CO2–ethanol 18.23%, and with hexane 20.21%.

7. REFINING OF THE OIL The color of crude rice bran oil is dark greenish brown to light yellow depending on the condition of the bran, extraction method, and composition of the bran. The pigments include carotene, chlorophyll, and Maillard browning products (12, 28). Oil from parboiled rice bran is generally darker in color than oil from raw rice bran. The composition of crude rice bran oil has a major effect on refining. The crude oil typically contains up to 0.5% bran fines and 0.5–5% wax. Agitated storage tanks are required. Heated tanks and lines also are necessary to prevent crystallization of

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waxes. Refining losses may be in excess of ten times the FFA when the crude oil has a relatively low FFA (<10%). Lower refining losses of approximately two times the FFA have been reported (2, 6, 40). Refining of crude rice oil involves dewaxing, degumming, neutralization of free fatty acids, bleaching to improve color, and steam deodorization. Refined rice bran oil is a light yellow color (Lovibond 3.0 R 30Y) with a mild background odor and flavor reminiscent of rice. Similar to peanut oil, the flavor and odor are complementary to the flavor of many fried foods, such as fish, chicken, and chips.

8. DEWAXING Waxes can increase refining losses (8). The wax content of crude oil depends on the variety of rice, milling technique, method of oil extraction, and extraction temperature (2). Extraction temperature affects both the type of wax present and its quantity (42). For example, extraction at 50 C yields two to three times more wax than extraction at 20 C. Initial dewaxing may simply be gravity settling followed by decanting (43). The oil is gradually cooled to allow for wax crystallization followed by filtration or centrifugation to recover the wax sludge. The foots recovered may be added back to the defatted bran, sold as an animal feed oil, or further processed for oil recovery and wax purification. Wax recovery involves acetone washing and fractionation with isopropanol. The characteristics of the wax are as follows: Iodine value FFA (%) Phosphorous (%) M.P ( C) 11.1–17.6 2.1–7.3 0.01–0.15 75.3–79.9

Attempts have been made to recover the wax using cold and hot extraction (2). Wax yields of 1.29–1.82% of the crude oil are obtained. Continuous dewaxing of rice bran oil by chilling the oil or miscella to less than 20 C followed by filtration through plate and frame filters is practiced. Kinsey and Hummell (44) reported on the use of sodium silicate as an aid for dewaxing. The characteristics and physical properties of a purified rice bran wax are similar to carnauba wax (45). Additional dewaxing may be used during degumming and alkali refining (8). Dewaxing of refined, bleached oil by cooling to approximately 5 C followed by filtration is necessary for production of a high-grade, chill-proof oil.

9. DEGUMMING AND DEACIDIFICATION The phospholipids in rice oil are similar in composition to other oil sources. These may be recovered as rice lecithin (5). Production of food-grade lecithin requires

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prior removal of bran fines and waxes. Regular water degumming may be used. Temperatures above 80 C are required to prevent crystallization and removal of waxes with the gums. If food-grade lecithin is not being produced, filtration of bran fines is not required. Pretreatment with phosphoric or organic acid is necessary to remove nonhydratable phospholipids. Food-grade surfactants may be added to improve wax removal (46). Degumming at less than 50 C actually assists in wax removal. Wet gums may be added to defatted bran as a method for disposal (8). Both alkali and physical refining have been used for FFA removal (5). With alkali refining, batch or continuous methods may be used. Oil may be pretreated with phosphoric or organic acid for phospholipid hydration. The oil is then treated with 16–30 baume (Be0 ) caustic with 20– 40% excess. The soaps settle and may be recovered as ‘‘soapstock’’ or ‘‘foots’’ (47). Continuous refining consists of in-line mixers, heaters, and centrifuges (8). The combined oils plus alkali are rapidly heated to 55–70 C to assist in breaking the emulsion of hydrated soap in oil. In instances where neutralization is combined with dewaxing, separation is performed at 28–32 C. Water washing or post-neutralization treatment with silicates to remove final traces of soaps and phospholipids is the same as for conventional oils. Miscella refining, or refining while still in solvent, may also be used (47). Higher refining yields and good-quality neutralized oil with less color are advantages of miscella refining. Losses were near the calculated amount (48) based on titrated values. Rice oil miscella is often variable. Excessive losses may occur in refining of rice oil. A 5% FFA crude oil has losses ranging from 12% to 40% by the cup method. The cause of high refining losses is unknown. It is assumed the losses are caused by the presence of partial esters, oxidized components, and waxes, as well as high FFA acidity (8). Steam refining is practiced by various refineries in Japan and the United States (2). In calculating the amount of caustic required for caustic neutralization, the oil is titrated to a phenolphthalein end point. This titration endpoint includes not only the FFA, but also the oryzanol compounds. With the higher caustic addition, the oryzanol is transferred to the soapstock away from the oil. The nutritional benefit of these compounds is lost. An alternative indicator for titration uses alkali blue (8). This indicator reflects the acidity contributed only by the free fatty acids.

10. BLEACHING, HYDROGENATION AND DEODORERIZATION Standard methods are used for bleaching, hydrogenation, and deodorization of rice bran oil. Bleaching uses activated carbon or bleaching earth (47). Activated carbon is seldom used because of high cost and handling difficulties. Bleach clay dosage depends on the characteristics of the rice oil as well as that of the bleaching earth. Dosages range from 2% to 10%. Newer silica bleaching earths are more effective in reaching satisfactory oil colors.

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Deodorization or steam stripping is used to remove objectionable odors resulting from peroxides, aldehydes, and ketones as well as characteristic rice oil odors and flavors (12). The oil is heated to 220–250 C under 3–5-mm Hg vacuum. Semicontinuous deodorizer units are the most common types used. Other designs have been evaluated (43). After deodorization, the oil is cooled to 60 C and filtered. Storage of deodorized rice ban oil is the same as for other oils. Physical refining, also called steam refining, combines deacidification with deodorization. Physical refining is more efficient for high FFA oils giving better yields of neutralized oil than alkali refining (2).

11. WINTERIZATION In addition to wax removal, rice bran oil contains sufficient saturated and high melting glycerides to require winterization to gain a cold test of 5 hours (8, 43). Without winterization, dewaxed rice oil is frequently cloudy or turbid even at room temperature or slightly lower. Winterization consists of cooling the oil under defined rates and to specific temperatures followed by filtration. With rice oil, winterization consists of cooling 30– 35 C oil slowly at a uniform rate to 15 C over a 12-hour period with slow agitation, then further cooling to 4–5 C without agitation followed by holding over a 24– 48-hour period, allowing higher melting components to crystallize. The type of crystals formed depends on the cooling rate and the temperature differentials. Large, stable crystals are desired for filterability. Filter aids may be added to assist separation of the crystals from the viscous oil. Cold tests of the winterized oil of 5–7 hours are near maximum. Miscella winterization more effectively separates the high melting solids from rice oil. Hexane, acetone, and isopropyl acetate are among the solvents used. The miscella is slowly cooled to 15 C over 12 hours with agitation, then to 4– 5 C without agitation, and held for 24–48 hours before filtering.

12. CO-PRODUCTS FROM PROCESSING As with all oils, coproducts of refining represent a significant revenue stream. Waxes may be concentrated and refined to compete with other organic waxes. The hard, high melting waxes are preferred for most applications. Soapstock contains fatty acid soaps and, for oil that is caustically refined, oryzanol (5–10%). The soaps may be acidulated for feed use and the oryzanol isolated (16). Diethyl ether, alumina chromatography, and crystallization are used for purification of the oryzanol. The deodorizer distillate, about 1% of deodorizer feed, contains tocopherols, tocotrienols, and sterols (Table 10). The tocols are shown in Table 11 and the sterols in Table 12. Its value is similar to other oil distillates.

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TABLE 10. Rice Oil Deodorizer Distillate Composition (20). Component Free fatty acids Tocopherols Tocotrienols Sterols Squalene Monoacylglycerols, diacylglycerols, etc Percent (range) 25–40 1.5–3.0 4.0–6.0 15–25 15–25 15–25

TABLE 11. Approximate Tocol Composition of Rice Oil Distillate (20). Tocol (percent) ———————— Tocopherol Tocotrienols Alpha Beta Gamma Delta 67 3 30 tr. 21 tr. 77 2

TABLE 12. Sterol Composition of Rice Oil Deodorizer Distillate (20). Sterol Beta-sitosterol Stigmasterol Campesterol Delta-7-stigmasterol Delta-7-avenasterol Delta-5-avenasterol Others Percent 38 18 13 10 6 5 10

13. COMPOSITION OF REFINED RICE BRAN OIL A typical specification for finished rice bran oil is shown in Table 13. These are similar to that for other oils. Rice bran oil has a characteristic nutty, earthly flavor not unlike peanut oil. The fatty acid composition of rice bran oil is most similar to peanut or ground nut oil (Table 14) (8). Palmitic, oleic, and linoleic acids make up more than 90% of the fatty acids present. The major molecular species of triacylglycerols are palmitic-linolenic-oleic, oleic-linoleic-palmitic, palmitic-linoleic-linoleic, linolenic-linoleic-palmitic, and trioleic. As with peanut oil, rice bran oil is most suited for general frying and cooking applications.

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TABLE 13. Product Specification of Refined, Bleached, and Deodorized Rice Bran Oil (8). Characteristic Iodine value (Wijs method, g/100 g sample) Peroxide value (meq/kg) Moisture (%) Color (5.25-in Lovibond red) Free fatty acid (% as oleic) Flavor/odor Chlorophyll (ppb) Saponification value Unsaponifiable matter Smoke point Refractive index Specific gravity AOMa (hr)
a

Value 99–108 1.0 max 0.05 max 5.0 max 0.05 max 7 min 75 max 180–190 3–5 213 C 1,470–1,473 0.916 17.5

Active oxygen method.

TABLE 14. Chemical Composition of Rice Bran Oil (8). Physicochemical Parameters Acid value Iodine value Saponification value Unsaponifiable matter Fatty acid composition C14:0 C16:0 C18:0 C18:1 C18:2 C18:3 C20:0 C22:0 Value 1.2 100.0 211.8 4.2 Percent 0.6 21.5 2.9 38.4 34.4 2.2 — —

14. RICE BRAN OIL NUTRITION The initial interest in rice bran oil resulted from work with the stabilized rice bran. Rice bran was shown to be equivalent in serum cholesterol reduction to oat bran in hamster trials (Table 15) (1). Two clinical studies showed rice bran reduced serum low-density lipoprotein (LDL) cholesterol in humans (49,50). Defatted bran was less effective in lowering cholesterol than full fat bran (1). The cholesterol-lowering activity was concentrated in the unsaponifiable fraction of rice bran oil (Table 16) (51). Oryzanol was found to contribute to the hypocholesterolemic activity of rice

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TABLE 15. Effect of Rice and Oat Brans on Serum Cholesterol in Hamsters (1). Bran in Diet Cellulose (10%) Rice bran (47.8%) Defatted rice bran (24.7%) Parboiled rice bran (31.8%) Defatted parboiled rice bran (19.6%) Oat bran (53.7%) Serum Cholesterol (mg/dL) 395 270 347 297 377 289

TABLE 16. Hypocholesterolemic Activity of Unsaponifiable Matter of Rice Bran Oil in Rats (51). Diet Control (peanut oil) (10%) Rice bran oil (10%) Control þ 0.2% unsaponifiables Control þ 0.4% unsaponifiables
a

Total 374 228 387 243

Serum Cholesterola (mg/dL) HDL LDL þ VLDL 43 48 48 48 331 240 339 195

HDL ¼ high-density lipoprotein; LDL ¼ low-density lipoprotein; VLDL ¼ very low-density lipoprotein.

oil in rats (52) and primates (53). A clinical study with 3.1 g/day of rice bran oil unsaponifiables over a 12-month period resulted in a 14.1% reduction in total cholesterol and a 20.5% reduction on LDL-cholesterol (Table 17) (54). HDLcholesterol rose, and triacylglycerols decreased significantly. Tocotrienols, also present in rice bran oil, have been reported to reduce serum cholesterol (55). The refining method used in rice oil production affects the oryzanol content of finished oil (3). With alkali refining, most of the oryzanol is removed (Figure 7), whereas with steam or physical refining, most of the oryzanol (66%) remains in
TABLE 17. Effect of Daily Addition of Rice Bran Unsaponifiables (RBN) on Serum Lipids (mmol/L) in Hypercholesterolemic Subjects (54). Serum Lipidsa RBN Cholesterol LDL cholesterol HDL cholesterol Triacylglycerol/HDL RBN placebo Cholesterol LDL cholesterol HDL cholesterol Triacylglycerol/HDL
a

Start 6.18 Æ 0.33 4.28 Æ 0.37 0.17 Æ 0.02 2.16 Æ 0.35 5.70 Æ 0.21 3.95 Æ 0.18 0.21 Æ 0.06 1.54 Æ 0.31

12 months 5.31 Æ 0.20 3.40 Æ 0.18 0.24 Æ 0.02 1.21 Æ 0.21 6.06 Æ 0.32 4.05 Æ 0.31 0.22 Æ 0.01 1.55 Æ 0.20

p <0.05 <0.05 <0.025 <0.05 ns ns ns ns

LDL ¼ low-density lipoprotein, HDL ¼ high-density lipoprotein, ns ¼ not significant.

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485

Oryzanol (ppm X thousand)

20

10

0 Crude Alkali refining Physical refining

Figure 7. Effect of the refining process on the oryzanol content of rice bran oil (8).

the oil (56). Physically refined rice oil gave a serum lipid response similar to that of crude rice bran oil. Various refining methods to preserve the oryzanol in the oil have been attempted. Sodium carbonate instead of sodium hydroxide has been partially successful in which two-thirds of the original oryzanol in the crude oil is preserved in the refined oil (57). Adding back unsaponifiables to the oil has been patented (58). Clinical trials have not been performed with high oryzanol rice bran oil. An unsaponifiable concentrate was prepared by extracting the soapstock, with hexane giving a deacidified concentrate with 30% unsaponifiable content.

15. RICE BRAN OIL UTILIZATION Rice bran oil is used in foods, feed, and industrial applications. Only high-quality oil is targeted to foods. The use of rice bran oil in Japan, where it is the largest volume domestically produced vegetable oil, is as a frying oil where its flavor is preferred over alternative oils. The oxidative stability of rice bran oil is equivalent to peanut oil and cottonseed oils in deep frying applications (Table 18) (8, 59).

TABLE 18. Frying Evaluation of Rice Oil (15-day results) (8). Days to Maximum Levelb —— ——————— —————— FFA FOS LY 3.91 5.62 6.87 7.22 3.74 3.46 3.92 4.07 6 7 8 7

Oil typea Rice (without additives) Rice (with additives) Peanut (with additives) Cottonseed (with additives)

LR 28.0 49.6 21.2 28.8

TPM 31.9 34.6 37.5 37.2

a Specifications. 40 lb (18.2 kg) gas fryers, frying temperature 350 F (177 C); hourly rotation: breaded chicken, fish, onion rings, French fries: 5-ppm dimethyl polysiloxane antifoam, 200-ppm tertiary butyl hydroguinone. b FFA ¼ free fatty acids, FOS ¼ food oil sensor; LY ¼ Lovibond yellow; LR ¼ Lovibond red; TPM ¼ total polar material.

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TABLE 19. Frying Results Using Blends of Rice and Soybean Oils (8). Total Polar Material (%) ——————————— 10 days 13 days 21.12 21.07 24.11 23.25 32.78 35.53 35.80 40.42

Oil Type Rice Peanut Rice/soybean 50:50 Rice/soybean 25:75

TABLE 20. Days at 145 F (62.8 C) Before Rancid Odor is Detected (8). Oil Type Rice (without additives) Rice (with additives) Peanut (without additives) Cottonseed (with additives) Days to Detect Rancid Odor 20 25 14 31

Blends of rice bran oil with soybean oil reduces the increase in total polar material (TPM) depending on the amount of rice bran oil in the blend (Table 19). Potato chips fried in rice bran oil show flavor and odor stability at elevated temperatures between that of peanut and cottonseed oils (Table 20). Winterized rice bran oil is an acceptable oil for salad dressing and mayonnaise. The hard fraction of rice bran oil may be used to replace the plastic fats in margarines and shortening. Hydrogenated rice bran oil is adaptable to specialty shortenings and margarines. The nonfood uses of rice bran oil are feed formulations, soaps, and glycerin. Waxes may be used as a carnauba wax replacement in confectionery, cosmetics, and polishing compounds products. Use of rice bran oil grows as a specialty ingredient in the cosmetic/personal care market. The demand is for natural, value-added healthy ingredients (60).

16. RICE OIL PRODUCTION (POTENTIAL) World rice production is greater than 500 million metric tons. Rice oil production is estimated at 722.2 thousand metric tons (Table 21). India, China, and Japan are the leading producers. More than half of rice is processed in small rice mills. This leaves approximately 20–25 million metric tons of bran available for oil production. The rice bran oil potential is, then, 3–4 million metric tons. In the United States, most bran is also produced in small rice mills scattered in rice production areas with insufficient bran production to justify oil extraction.

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TABLE 21. Production of Rice Bran Oil (61).* Country Bangladesh Brazil Cambodia China India Indonesia Japan Korea Republic of Korea Laos Burma Nepal Pakistan Sri Lanka Thailand Vietnam Total
*

Thousand Metric Tons 1.5 1.5 4.6 90.0 472.7 0.15 65.0 11.7 9.2 2.6 17.6 7.6 3.7 5.5 7.8 7.6 722.2

Does not include U. S. production, which is 15.9–18 thousand metric tons.

Production estimates are for less than 80 thousand metric tons. Only 15.9 to 18 thousand metric tons are produced currently in the United States at a single oil extraction facility. 17. SUMMARY Rice bran is an underused coproduct of rice milling. The value is partially captured through extraction and refining of the rice bran oil. The capital costs have limited the ability of the U.S. rice milling industry to capture this value. However, rice bran oil has performance properties competitive to other widely used oils. An additional advantage of rice bran oil is certainly its nutritional benefits, which include a balance of fatty acids meeting AHA recommendations. Rice oil contains a mixture of antioxidants and promotes cholesterol reduction beyond that of more unsaturated oils. Its taste and performance is complementary to salad, cooking, and frying applications. REFERENCES
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