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By-Product Utilization
M. D. Pickard 1. BY-PRODUCTS OF SEED PROCESSING 1.1. Soybean The by-products resulting from the processing, i.e., solvent extraction, of, soybean in the major producing countriesArgentina, Brazil, and the United States (1) are defatted protein meal and, to the extent that the beans are dehulled prior to extraction, hulls (2). A portion of the separated hulls may also be added back to the meal. Over 90% of the protein meal obtained from processing in the United States is used directly as livestock feed, after appropriate heat treatment (toasting) to inactivate trypsin inhibitors and other antinutritive factors (2, 3). Relatively minor quantities are milled into our or grits, primarily for edible applications, or used in the preparation of protein concentrates and isolates having food, feed, and industrial applications (3). Utilization of Soybean Meal in Animal Feeds. Soybean meal is the most extensively used of the oilseed meals and serves as a protein supplement for all classes of animals. It has become the standard to which all other protein sources are compared, and its quality, acceptance, and reputation are widely known (4). The meal contains from 44 to 50% crude protein and from 2500 to 2800 kcal of metabolizable energy per kilogram, depending on the amount of hull present and the species of animal being fed. Dehulling increases the metabolizable energy values by about 5% for cattle and 12% or more for pigs and poultry (5).

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

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Soybean meal is an excellent protein supplement for lactating dairy cattle and for calves following weaning, as it is highly palatable and well digested. It also serves well as the supplemental protein in rations for growing and fattening cattle. However, in many ruminant feeding applications, soybean meal may not be cost competitive with other proteinaceous and nonprotein-nitrogenous ingredients (4, 5). Extensive research related to the development of protected or rumen bypass protein from soybean meal has resulted in the development of commercial products (4), which should increase the utilization of soybean meal in ruminant feeds. Nearly 80% of the soybean meal consumed in the United States is fed to nonruminants. Soybean meal is the most economic high-quality protein available to feed manufacturers; hence it assumes a dominant role (3, 4). Cereal-based rations for pigs and poultry may contain soybean meal as the only protein supplement, as a previous requirement for the inclusion of some animal or marine origin protein has been supplanted by the addition of lysine, methionine, and vitamin B12, where economics dictate (5). Soybean meal is used effectively in the formulation of pet foods, particularly for dogs, where simple cornsoybean meal mixtures perform as well as complex diets containing high levels of animal protein, and at substantially lower cost (4). Rapid growth in aquaculture over the last 1015 years has resulted in signicant new opportunities for utilization of soybean meal in nsh and shrimp diets. Whether additional heat processing of soybean meal to further reduce levels of antinutritional factors or supplementation with lysine or methionine or both is benecial to performance appears to be species dependent (4, 6). Utilization of Soybean Hulls. Soybean hulls are high in cellulose but low in lignin and, therefore, highly digestible by ruminants (4, 7). In fact, the digestible energy content of soybean hulls, for ruminants, approaches that of grain (7). Consequently, soybean hulls may be used, to economic advantage, in high-forage diets in lieu of grain, with various additional functional advantages. For growing cattle and sheep, replacing grain with soybean hulls eliminates the risk of acidosis and reduces the negative effect of starch on ber digestion. In the case of lactating cows or ewes, soybean hulls can replace a signicant portion of the grain in a grainforage diet with no reduction in fat content or milk yield (4, 7). Soybean hulls are seeing increasing use in human food as a source of dietary ber. Fiber-enriched pasta and white bread appear to be the most popular vehicles for inclusion of soybean hulls at this time. Edible Products Derived from Soybean Meal. The primary edible products derived from soybean meal/akes are our/grits (at 50% protein), protein concentrates (containing 6570% or more of protein) and protein isolates (90% protein). The nutritional quality, availability, price, and functionality of these products has resulted in substantial usage in a wide variety of food and feed products. Given current trends in food consumption, strong growth in the use of soy protein products in foods appears assured (8, 9). A number of excellent articles on the manufacture of soy protein products exist; processing will not be described in detail here (8, 1013). Soybean our and grits are essentially ground soybean meal/ake products differing primarily in particle size, both having received heat treatment appropriate to

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their required functionality and expected end use. Flours and grits are primarily employed as fat and water binders in baked goods and pet foods and as raw material in the manufacture of soy sauce. Residual beany avor and poor mouthfeel limit the use of soy our and grits in many applications. Soy ours containing lecithin or various levels of fat (soybean oil) are also commercially available (8, 12, 13). Protein concentrates with improved avor and functionality relative to soy our may be prepared from undenatured soy our/akes by a variety of processes including acid or alcohol leaching, alkaline extraction, heat denaturation followed by aqueous leaching, and membrane ltration. Products are ultimately spray or dispersion dried. Currently, acid-and alcohol-washed products dominate the marketplace and are available in a variety of functionalities for use wherever the nutritional, fat and water binding, emulsication, foaming, or viscosity modifying characteristics of casein or nonfat dry milk would otherwise be exploited. Typical applications of soy protein concentrates include comminuted meat products, baked goods, baby foods, cereals, milk replacers, pet foods, and snacks. The expanding market for meat extenders and substitutes employs extrusion-texturized soy concentrates that, when rehydrated, possess to a remarkable extent the chewiness and mouthfeel of meat (8, 10, 12, 13). Protein isolates are produced from undenatured soy our/akes by dilute alkaline extraction and subsequent acidication of the protein extract to the isoelectric point, approximately pH 4.5. The precipitated protein curd is recovered by centrifugation, washed, slurried in water, and usually neutralized prior to being spray dried. Ultraltration or other protein recovery techniques may also be employed in isolate production. Soy protein isolates are relatively expensive but highly functional. Their binding, emulsication, foaming, and nutritional properties are exploited in a variety of products including comminuted meats, dairy-type products, and infant formulas (8, 1113). Due to their inherent insolubility at acidic pH, pectinaggregated soy isolate particles show potential as clouding agents in citrus beverages (14). Soy isolates may be modied by hydrolysis, addition of substituent groups, or texturization (spinning), thereby expanding their range of functionalities and applications (12, 13). Industrial Uses of Soybean Protein Products. The historical, current, and potential industrial use of soybean proteins has been described recently in excellent fashion (15, 16). Consequently, this topic will be discussed only briey here. The early promise of plastics manufactured from acid- and formaldehyde-treated isolated soy protein was never realized, for economic and functional reasons. Soy our has seen signicant use in glues for plywood and other laminated wood products. These have been displaced by petroleum-based glues that exhibit superior microbial and water resistance. Textile bers prepared from soy isolate or our never saw commercial production due to poor wet strength and an unpleasant odor when wet. Soy protein isolate is currently used in paper-coating applications (15, 16). Potential new uses for soy protein are driven primarily by environmental concerns and the search for new value-added uses for agricultural commodities. In addition, prices for petroleum-based polymers have increased relative to prices for

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agricultural products (1517). Examples of products currently under development include biodegradable plastics, edible soy protein lms and soy proteincarbohydrate lms intended to reduce packaging waste, and a soy our-recycled paper composite material (sold under the trademark Environ) with the appearance of granite and the handling characteristics of hardwood. In addition, soy protein-based glues and adhesives and textile bers, with functional characteristics superior to products from earlier efforts, are being developed (15, 16, 18, 19). Still another use is as a feedstock for fermentations. 1.2. Rapeseed/Canola Rapeseed has become an important crop in the temperate zones of the world, with production in more than 30 countries on 5 continents. The productive capacity of the crop and the nutritive value of its protein have made rapeseed a leading potential source of food and feed protein ingredients. Oilseed rapeseed was grown in India over 3000 years ago, and at least 2000 years ago in China and Japan. It is not clear when rapeseed oil became a food oil in addition to its use as a fuel for lamp lighting and for soap and candles. Throughout most of the long history of this crop, the cake or meal was used as a fertilizer or soil conditioner, a practice that persists today in China and Japan (5). The early nutritional experiences with the meal were probably not encouraging as the meal was unpalatable. Glucosinolates present in the meal release goitrogenic factors, such as oxazolidinethione, isothiocyanates, and thiocyanates, when hydrolyzed by the enzyme, myrosinase, also present in the seed/meal. These compounds interfere with iodine uptake and thyroxine synthesis by the thyroid gland. Under certain conditions, highly toxic nitriles may also be produced (5). Processing techniques that inactivate myrosinase and, therefore, prevent glucosinolate hydrolysis have become standard operating practice around the world (20, 21). Typically, seed containing 610% moisture is rapidly heated to 8090 C. A second deterrent to the use of rapeseed meal as a nutritional supplement is its high ber content. Most rapeseed varieties have a dark, hard seed coat containing a condensed polyphenolbased complex that contributes a substantial amount of ber to commercial rapeseed meal (22). The reduction of glucosinolate levels in rapeseed through extensive plant breeding programs has provided a major breakthrough in the utilization of rapeseed meal. The meal is becoming increasingly available as a protein supplement for animal nutrition as more of the genetically improved varieties, known as canola, are grown. Canola is a trademark name and a generic term to distinguish specic seed varieties containing less than 2% of erucic acid in the oil fraction and having a solid component containing less than 30 mmol/g of glucosinolates. Successful feeding of canola meal still requires knowledge of its glucosinolate status as well as the age and class of animal involved (23, 24). Composition of Canola Meal. Canola meal is an internationally traded commodity. Excellent summary information on canola meal composition has been developed to aid the animal feed industry (25). Canola meal contains 3638% crude

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protein and a favorable assortment of essential amino acids in its protein. It is higher in crude ber, at 12%, than is soybean meal and consequently has lower metabolizable energy values (19002300 kcal/kg, depending on the species being fed). The crude ber is largely in the hull fraction, which comprises 1625% of the meal. Hulls are poorly digested, especially by nonruminants, and are largely responsible for the relatively low metabolizable energy values. Dehulling would improve metabolizable energy values, but hull utilization and loss of oil and cotyledon material in the hulls remains problematic (5). Use in Animal Feeds. Pigs. Canola meal is a proven supplemental protein source in pig diets. Although poor palatability and reduced digestibility with young (620 kg) pigs prevent its use at levels higher than 25% of supplemental protein, research has conrmed that canola meal is a desirable supplemental dietary protein for growing, nishing, and reproducing swine. Canola meal can be used at 5075% of the supplemental protein source in diets for growing (2060 kg) pigs and as the sole supplementary dietary source for nishing pigs (60100 kg) and dry and nursing sows (26). Poultry. Canola meal is widely accepted for use in poultry diets. It is usually limited to 10% of the diet in layer feeds because of increased bird mortality at higher levels. Long-term studies of egg production show no effect of canola meal on the number of eggs produced per bird. However, there is a small decrease in egg size due to slightly lower feed intake. Canola meal and rapeseed meal have an interesting effect on brown-shelled layers. These birds are decient in an enzyme responsible for the breakdown of trimethylamine. As canola and rapeseed have high levels of choline and sinapine (precursors of trimethylamine), the eggs of these layers have a shy taint. For this reason, a maximum of 3% of canola meal may be used in the diets of brown-shelled egg layers. There is no concern about increased mortality at high canola meal inclusion rates for growing poultry such as broilers, turkeys, pullets, or waterfowl. When grower diets are appropriately balanced for energy and levels of digestible amino acids, canola meal can be effectively used as the major supplemental protein source (27, 28). Beef and dairy cattle. Canola meal has gained widespread acceptance as a protein supplement in beef and dairy rations. Research has shown its effectiveness in a variety of production and management situations. Lactation trials have demonstrated that canola meal will maintain or slightly improve milk production relative to soybean meal-based rations. Improved milk production may in part reect the amino acid content of the bypass protein fraction of canola meal. In beef cattle rations, animal performance has been shown to meet or exceed industry standards when canola meal is incorporated. Canola meal can be used as the sole protein supplement in rations for growing and nishing cattle (29). Use as Human Food. Rapeseed, as a protein source for humans, has many obstacles to overcome. The glucosinolate and ber contents require application of new processing technology (22, 30) to eliminate antinutritional qualities. Rapeseed ours, protein concentrates, and isolates are lower in protein but higher in crude ber and ash contents than corresponding soybean products. Rapeseed ours are comparable to soybean our in water adsorption and give much higher fat adsorption, oil

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emulsication, and whippability values. Rapeseed our viscoamylograph curves exhibit high viscosities but poor gelation properties. The utilization of rapeseed products may also be limited by green or brown colors in aqueous systems (31). Other Uses. Rapeseed or canola meal has been used as a fermentation substrate. It has been included as an additive in compost for commercial button mushroom (Agaricus bisporus) production with good success (32). Canola meal has also been tested as a substrate for xylanase production by Trichoderma reesei. Results from this work indicate that the hydrolysis of canola meal by this enzyme system might be useful in converting this material to fermentable sugars that could be further processed to expensive end products such as solvents and chemicals (33). 1.3. Sunower Sunower Meal. The vegetable oil extraction industry produces three types of sunower meal: undehulled meal containing 28% protein and 2528% ber, partially dehulled meal containing 3537% protein and 18% ber, and double-dehulled sunower meal containing 4042% protein and 1214% ber. Thus, the composition of sunower meal is dependent on the efciency of the dehulling process (34). The protein concentration and amino acid composition of sunower meal also vary with the source of seed, and high-temperature processing may have a deleterious effect on its lysine content. Generally, however, sunower meal exhibits a well-balanced amino acid composition with an essential amino acid index of 68, compared to 79 for soybean meal and 100 for whole egg (35). The energy content of sunower meal compares favorably with that of other oilseed meals and increases as the residual oil content increases and as the ber content decreases. Sunower meal also compares favorably with other oilseed meals as a source of calcium and phosphorus (36) and is an excellent source of water-soluble B-complex vitamins, namely nicotinic acid, thiamine, pantothenic acid, riboavin, and biotin. Sunower meal contains the polyphenolic compound, chlorogenic acid, which results in a yellow-green coloration following oxidation in the presence of alkali. The production of protein isolates and concentrates from sunower meal/our would require the removal or inactivation of chlorogenic acid (35, 37). Use as Animal Feed. Sunower meal can be fed to all classes of livestock. Most sunower meal is fed to ruminants and is comparable, nutritionally, to cottonseed meal. High levels of sunower meal are used in dairy, beef, and sheep rations (5). For swine, low-ber sunower meal is inferior to soybean meal as the sole source of supplemental protein. This inferior performance is the result of lower palatability and nutrient content. In swine rations, with 2030% of the protein from sunower meal, rates of gain are similar to soybean meal, but larger quantities of meal are required. Lysine supplementation reduces this requirement. Studies have indicated that sunower meal can effectively replace 50% of the soybean meal in growingnishing swine rations. Higher rates of utilization are possible as animals increase in weight because of the decreased requirement for essential amino acids (38).

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Rations for laying chickens could incorporate low-ber sunower meal, to a level of 50% of the protein concentrate portion, without signicantly reducing egg production (39). Higher levels of addition are possible with lysine supplementation but may cause egg staining due to the presence of chlorogenic acid in the meal (35). Metabolizable energy trials with laying hens yielded a value of 2205 kcal/kg (dry matter basis) for dehulled, solvent-extracted meal (38). The use of sunower meal is often limited by its availability. Adequate volumes, available on a sustained and consistent basis, would ensure a high utilization of sunower meal in animal nutrition. Despite its dark appearance, lower energy, and higher ber content, as compared to soybean meal, sunower meal is a competitive product with potential for continued improvement through the use of tail-end screening to further reduce its ber content (40). Use in Human Foods. Confectionery sunowers have a history of use in the snack trade and the trend continues (41). The roasted seed has a pleasant nutty avor. Dehulled and roasted sunower kernels can be used as a nut substitute in many confectionery and bakery formulas. Physical and organoleptic analysis of color, avor, texture, and acceptance indicate that a 1015 min roast at 177 C is the most desirable processing technique (37). Chemical and physical analysis of hexane-extracted sunower meal indicates that discoloration due to the oxidation of chlorogenic acid is a problem. An attractive cream color, relatively bland avor, and excellent stability are possible if the processing conditions do not induce chlorogenic acid oxidation. Unfortunately, the conventional methods of making protein isolates promote the oxidation of chlorogenic acid. Studies have shown that organic solvents produce good extraction of polyphenols from sunower seed and meal (42). The physicochemical properties of proteins from such extracted meals indicate no signicant differences in amino acid content and only slight changes in nitrogen solubility due to protein denaturation. Sunower our and protein isolates have excellent emulsion and whipping properties and thus have great potential as functional agents and protein supplements in human food products, provided the polyphenols are removed or care is taken to prevent their oxidation (36). Sunower Hulls. Chemical composition of sunower hulls. The hull, a byproduct of oil extraction, comprises 2228% of the total weight of oilseed sunower and may be removed before or immediately following oil extraction or may remain in the meal. Sunower hulls contain: 4% crude protein; 5% lipid material, including wax, hydrocarbons, fatty acids, sterols, and triterpenic alcohols; 50% carbohydrates, principally cellulose and lignin; 26% reducing sugars, of which the majority is xylose; and 2% ash (35). The high ber content and low protein and energy content of sunower hulls reduce their nutritional value. Use in animal feeds. Hulls can be used in ruminant feeds when nely ground and mixed with other ingredients. When adequate energy is provided, sunower hull pellets may be used as a portion of the roughage component in ruminant rations due to their high content of cellulose and lignin. They are used to add bulk to concentrated rations and to absorb liquids such as molasses. Sunower hulls are sold to feed manufacturers and livestock feeders at prices comparable to those of other ingredients (38).

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Hulls as a source of fuel. The utilization of sunower hulls as a source of fuel has been studied. The heat value of hulls alone is 19.2 MJ/kg, whereas the heat value of hulls and meal combined is 23.6 MJ/kg. The higher heat value suggests that the combination of hulls and meal makes a better fuel (43). In many countries, the burning of sunower hulls offers an alternative to higher priced fuels. The resulting ash has a high percentage of potassium and can be used as a fertilizer (34). Hulls have been pressed into cylinders with wood waste and sold as re logs (35). It has been reported that because of their high content of reducing sugars, it is possible to produce furfural and ethyl alcohol from sunower hulls (40). Sunower hulls also represent a source of lignocellulosic material for acid hydrolysis and fermentation. As a lignocellulosic waste material, sunower hulls can be hydrolyzed with acid to yield material suitable for the production of single-cell protein (44). Purple-hulled sunowers contain anthocyanin, which may be useful as a natural red food colorant. North Dakota State University has extracted, quantied, and scaled up processing techniques to extract the pigment. Economic analysis suggests that the processing of these unique hulls may be economically justiable (45). Sunower Stalks. Finely chopped and dried stalks could be used as deburring and polishing abrasives in the metal manufacturing industry and are a replacement for peat moss in plant starter mix. It has been reported that stalks are easily processed and decolorized by existing pulping and ber processing techniques. The processed material can be made into acoustical tile. This material weighs less than 60% of standard acoustical tile and has better sound absorbency and strength (46). Sunower heads and stalks also represent a potential source of low-methoxyl pectin for use in low-sugar jams and jellies (47, 48). 1.4. Safower Safower is a minor oilseed crop limited in production by environmental constraints and by the plants spiny nature. Unless the seed is well dehulled, the oilcake resulting from oil extraction will have a high ber content. Undecorticated oil cake has a protein content of 2022% and an end use as manure. In contrast, removal of the hull improves the protein content to 40%, making it acceptable as cattle feed despite low lysine levels. Leftover hulls and husks are added to cattle feed or are used to manufacture cellulose, insulation, and abrasives (5, 49). 1.5. Cottonseed Gossypol is a yellow-green polyphenolic pigment contained in discrete bodies in cotton leaves, stems, roots, and seeds. This form of gossypol is readily extractable with 70% aqueous acetone. The glands are ruptured during processing and the released pigment structures are highly reactive with other cottonseed components such as protein. The gossypol binds to the biologically available lysine, effectively reducing the concentration available to an animal. Gossypol also causes toxic effects in monogastric animals, including humans. An additional complication related to the presence of gossypol is the production of dark-colored pigments

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in the oil and meal that cannot be removed by conventional rening and bleaching operations (50, 51). The adverse physiological effects of free gossypol on monogastric animals may be counteracted by making free gossypol a bound form during processing, either by precooking, followed by pressure and shearing in a screw-expeller, or by binding to ferrous salts (50, 51). A polar solvent, such as aqueous acetone, acetonehexane water, or hexaneacetic acid, may then be used to extract residual free gossypol from the meal (51). The presence of bound gossypol reduces the protein efciency ratio, presumably by reducing the availability of lysine. Care is required to prevent thermal damage to protein, which would further decrease the nutritive value of the meal (51). Utilization of glandless cottonseed strains is an alternative to the extensive seed treatment necessary to lower the gossypol content. The goal of plant selection programs has been to minimize the total gossypol concentration in the raw material (50). The Hopi Moencopi variety (Gossypium hirsutum var. punctatum) was used in the late 1940s by McMichael to produce plants with almost complete elimination of pigment glands from leaves and bolls. His ndings stimulated an exploration of commercial-type cotton crosses with glandless lines when the results were nally reported in 1959 (52). Presently, the glandless strains that have been developed are not widely produced due to concerns related to the inuence of these gossypol-free characteristics on the yield and the quality of the commercially more valuable cotton ber. Studies indicate that this concern is unfounded. An additional concern that has been addressed is that gossypol and related terpenoids are natural insecticides, such that the use of glandless cotton may encourage insect preference for the glandless cotton. It has been shown that insects do not prefer either strain (52). Despite the presence of gossypol, interest in the cottonseed cake has developed as a result of its high content of protein, the valuable component in cottonseed byproducts (51). A number of commercial products from defatted cottonseed have been extensively used in the past. Proo our was produced from 1939 to 1975, and contained 5560% protein and 4.5% fat (52). This product was a nonallergenic dietary protein source contributing functionalities such as emulsication, antioxidation, and water absorption to bakery-type products. Commercial production was suspended due to the limited market, but it is still produced for nonfood industrial purposes (52). Incaprina, or INCAP Vegetable Mixture 9, was produced in the 1950s and 1960s and contained 38% cottonseed our. It had a content of 0.05% free gossypol that was high enough to warrant supplementing the product with lysine to offset binding losses. Incaprina was vital as a low-cost vegetable protein source in South America (52). In addition to human consumption, the postoil extraction cake is also used for animal feed and, in the past, as fertilizer. Cottonseed Meal. Cottonseed meal is second only to soybean meal with respect to the quantity produced worldwide. This by-product of oil extraction is used in rations for cattle, sheep, goats, horses, and mules. Neither glandless nor normal cottonseed meal is palatable to young pigs (5). Broiler poultry feeds often contain cottonseed meal, with the potential to cause depressed weight gain and reduced feed efciency (53). Cottonseed meal is not

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used in layer feeds since the gossypol produces a yellow discoloration of the yolks and whites of the eggs. Ferrous iron is added to most poultry diets containing cottonseed (5). A recent study of low-gossypol cottonseed meal found that it successfully replaced soybean meal in the diet of broiler chickens with no harmful effects (53). A number of alternative uses for cottonseed meal exist. Adhesive and ber production have used cottonseed meal as a protein source. Plastics that contain cottonseed meal in equal parts with cottonseed hulls and phenolic resin have excellent ow properties, a short curing cycle, water resistance, and strength (50). Cottonseed Hulls. Hulls are used as roughage in animal feed and as mulch and soil conditioner. Additional uses for cottonseed hulls include fuel, insulation, and a xylose and furfural source. Rafnose derived from cottonseed hulls is used in culture media (50). 1.6. Palm The major producers of oil palm products are located in the equatorial tropics and include Malaysia, Nigeria, Indonesia, China, Zaire, and Cameroon (54). Palm fruit, when pressed, yields approximately 43% of crude palm oil and 57% of press cake, which consists of 35% pericarp (ber) and 65% nuts. Palm nuts consists of 83% shells and 17% kernels, which, when pressed, yield approximately 50% of each of palm kernel oil and palm kernel cake (55). Palm Kernel Cake. Palm kernel cake (PKC) protein is of average quality, which, at a level of 19%, is the lowest of the commercial oil cakes. The positive characteristics of PKC are a valuable calcium to phosphorous ratio, a 48% carbohydrate level, a 5% oil content, and a 13% ber content (54). The gritty texture of PKC limits its use in feed for monogastric animals. It is used in poultry diets at an optimum level of 15% in broiler and 20% in layer diets and provides 1500 kcal/kg of metabolizable energy (56). Pig diets may contain PKC if blood meal is added as a supplement. Pigs will consume 2030% of PKC in their rations if it is introduced gradually to young animals, which otherwise nd it distasteful. The use of PKC results in a rmer pork (57). Ninety-ve percent of the 430,000 tons of PKC produced annually in Malaysia is exported to Europe. European farmers use a ration containing 710% of PKC for dairy cattle (58). The high ber of PKC is necessary for dairy cattle to prevent metabolic and digestive problems. Each adult animal requires 23 kg each day. The level of ber found in PKC prevents deciency problems in lactating cows and may increase the fat content of the milk (57). Palm Fiber. Palm press ber or pericarp ber includes not only palm press ber from the oil extraction process but also empty fruit bunches and kernel shells. Its high ber and lignin content, comparable to wood, and low palatability limit its use in animal feed (55). It exhibits very slow digestion in the bovine rumen such that processing to increase its nutrient content is required prior to use (59). Supplementation with molasses, urea, and vitamins allows palm press ber to be

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used as a ber source. Urea produces an alkaline effect on the ber and adds nitrogen to the feed. The predominant use of palm press ber is as biomass fuel for oil mill plants. The palm press ber and kernel shells are burned to produce steam for generation of electricity. The potential heat energy of palm ber is 4420 MJ/kg and of the shell 4848 MJ/kg. One ton of shells and ber used for fuel produces 578 kg of steam. For example, Malaysia required 413 million kWh of electricity in 1985 to process 20.65 million tons of fresh fruit bunches. The industry, therefore, by burning palm shells and ber, saved 140 million liters of diesel fuel that would have been required to produce this amount of electricity. This source of energy has saved the palm oil industry in a monetary sense and is a convenient disposal method for ber and shell wastes (60). The ash from the burning of this solid waste does not contain sufcient nutrients to be used as a fertilizer, and dumping creates an airborne hazard and pollutant (58). It has been incorporated in concrete as a replacement for cement with a slight increase in the setting time but within American and British standards (58). Palm shells are composed of 20% free carbon and are suitable for production of charcoal or activated charcoal. Empty bunch waste can also be used as a eld mulch (55). 1.7. Coconut Coconut palms have the greatest economic value and distribution of all the palms and are considered the most useful of all plants, after grasses. Coconut products service both local and international markets (61). Copra Cake. Copra cake is a by-product of oil extraction from coconut. The dehusked coconut is split and the meat is scraped from the kernel cup and dried. The oil is extracted via expeller or solvent processes from the dried coconut meat copra. This product is available throughout the year, making it a cheap local source of animal feed. The cake is ground to meal for use in feed for poultry, cattle, sheep, and swine. Copra cake can be used as a substitute for sh meal in swine feed but may cause constipation. Germany has been an importer of the majority of the cake produced in the Philippines (61). There are problems associated with the use of copra cake in feed. As the amount of cake in the feed increases, its palatability decreases. Copra meal tends to be less digestible than fresh coconut meal. Despite a protein content of greater than 20%, the addition of methionine and lysine improves growth and feed utilization. The method of oil extraction does not appear to inuence the quality of meal produced. Neither expeller-extracted nor solvent-extracted copra meal, at levels of 1014% in poultry diets, caused any difference in egg production, mortality, or efciency of feed conversion (61). Coconut Flour. Coconut our is produced from the shredded kernel, dried in a continuous countercurrent drier, and subsequently extracted with solvent to remove the residual oil. The white meal produced contains 25% protein and 65% carbohydrate, as well as various minerals and vitamins (62). This coconut product

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is used as a high-protein additive to enrich other ours such as wheat, rice, and corn our. Coconut our has properties compatible with those of wheat our in the preparation of bread, biscuits, and other food products (62). The protein quality of coconut our may be very high (lysine, 19%; cystine, 89%; histidine, 56%; methionine, 39%), making it desirable for use in baby food and convalescent food drinks. Its content of essential amino acids may be reduced, however, if excessive heat is generated during mechanical oil extraction. The our also possesses a relatively high crude ber content (62). Coconut Shell. The coconut shell comprises 27% of a dehusked nut by weight. This by-product of oil production has many local uses. Coconut shell has a composition similar to that of hardwoods but has a slightly higher lignin content and a lower cellulose content (61). In southern India and Sri Lanka, the shells are used directly as fuel in villages and small holdings and by local industries such as laundries, bakeries, and iron foundries. Charcoal is manufactured using a simple process. The air surrounding burning shells is limited, encouraging slow carbonization rather than ash production. This process takes place in a kiln over a 3-day period with careful consideration given to the balance of conditions and time. The nal product represents 30% of the original weight of the shells (61). Charcoal is a preferred fuel as it produces no waste material when burned. Hot embers emit infrared wavelengths that are valuable in the cooking of foods such as sh, meat, or tubers. Coconut shell produces heat energy at a level of 23 MJ/kg whereas shell charcoal produces 30 MJ/kg. Shell charcoal is also used to manufacture calcium carbide and the carbon electrodes of electric batteries. Both shell and charcoal generate producer gas. Reactors utilizing this product are sold for refrigeration, water pumping, and ground and marine vehicle operation (63). Destructive distillation of the shell produces some interesting substances. Upon exposure to very high heat in the absence of air, the shell forms products from all three phases (gaseous, liquid, and solid) as noncondensible gases, pyroligneous liquor, settled tar, and retort charcoal will be generated. The pyroligneous liquor, a dark red and odorous liquid, yields acetic acid, methanol (locally called wood naptha), and a variety of other products. The liquor may be used as boiler fuel, and noncondensible gases may be compressed in cylinders for use as domestic cooking gas (62). Coconut shell is the source of two other products, coconut shell our and activated charcoal. Powdered coconut shell is used in the plastics industry as a compound ller for synthetic resin glues. It is also used as a ller and extender of phenolic molding powders that give a smooth and lustrous nish to molded articles, thereby improving their resistance to moisture and heat. Activated charcoal is an adsorbent for toxic agents. It has been used in gas masks, but can also be used to remove odors and industrial stench. As well, this by-product is a contact catalyst used to facilitate some industrial chemical reactions (61). Coconut Husk. The husk represents 35% of the intact, mature coconut by weight. A number of products are derived from this by-product of oil production. Particles of husks may be consolidated with little or no adhesive (64). Pith is

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chipped with the husk material to produce the best bonding characteristics. The resulting self-bonding chips can be formed into boards of varying densities that are strong, durable, water repellent, and re retardant. These boards are used as low-cost construction products such as roong panels. Boards with a density of less than 400 kg/m3 are used for thermal insulation whereas medium-density boards of 500900 kg/m3 are used in construction and furniture (64). A combination of 25% nely ground coconut husk and 75% andesitic sand by volume has been used as a potting medium in nurseries (65). Coir. Coir is a valuable and versatile ber derived from the coconut husk. The best quality coir is produced from green coconut, which is more difcult to harvest and has a lower copra yield than more mature coconut. The amount of copra and the quantity of coir produced are inversely related (61). Husks must be retted to manufacture coir. This process involves holding the husks under water, away from air, with mud and leaves for a period of a few months to a year. Fermentation is accomplished by short rod bacteria such as Pseudomonas, Rerobacter, and Bacillus. The microbial process is a polyphenolic degradation in which the pectic substances are decomposed. Slow moving and slightly saline water in a natural source speeds the process and produces a better quality ber (66). 1.8. Groundnut Groundnut is comparable in nutritional value to more expensive animal-derived foods. Protein from this oilseed has the highest quality of the vegetable proteins, equivalent to casein. The oilseed cake from commercial-grade groundnuts is used for animal feed, whereas solvent-extracted edible-grade groundnut cake is milled into our (67). The digestibility of groundnut meal is high when it is well dehulled. Groundnut meal is lower in available lysine than soybean meal but contains a greater quantity of sulfur amino acids (5). Peanut our has an amino acid content comparable to that of raw and roasted peanuts, indicating that moderate heat treatment does not alter the amino acid composition (67). A new process for peanut our production has been developed that requires treatment of the seed with both heat and moisture prior to oil extraction. The our end product is white and bland, contains 65% protein, and is devoid of peanut avor. This allows the addition of this product to a variety of food products without disturbing color, avor, or texture. A high-quality our has been used in the treatment of hemophiliac patients (67). Protein produced from solvent-extracted meal has been used as a thickening agent in soups, baby foods, high-protein foods, institutional meals, and meat products. Groundnut proteins have also been used to manufacture a soft, wool-like, cream-colored ber, adhesive products such as plywood glue and wettable glue, and for paper coating. Fermentation of peanut protein with microorganisms increases the level of some essential amino acids. Rhizopus oligosporus is widely used to produce a tempehlike product (68). A similar product, oncom or ontjom, is produced in Indonesia using the fermenting agent Neurospora sitophila (51). The difference

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between the two products is the red color of oncom, derived from the red hyphae of N. sitophila. The seed coat of peanut is a commercial source of tannins and thiamin and sees limited use in feeds, primarily as a bulking agent in reduced-calorie pet foods. The presence of the seedcoat in meal may lead to a decrease in the availability of lysine (5). This apparent waste product is also used as mulch, fuel, litter for poultry houses, and in the production of a high-grade activated charcoal. The hull of the peanut is low in crude protein and exhibits low digestibility. This has limited the utilization of this by-product, although use as a source of roughage for ruminants has been reported (69). Physical and chemical treatments of the hulls have been applied to promote digestibility, with little success (69,70). Hulls are generally considered waste products. 1.9. Olive Olive oil is produced in warm-temperature and subtropical regions where the olive tree grows well. The fruit develops maximum oil content during the mid-November to February or March period in the Mediterranean basin and from May to June in the Southern Hemisphere. Ninety percent of the olives grown is used to produce oil (71). Initial extraction of oil from oil fruit produces a cake of fruit skin, pulp, and kernel known as olive pomace or orujos. The value of this primary by-product of oil extraction depends on its oil and water contents, which are, in turn, determined by the method of oil extraction employed and the operating conditions. Pressure extraction yields a residue containing 45% oil, whereas classical presses leave 812% oil in the pomace (72). Pomace ours are used as animal feed due to their high content of protein, which is also of high quality. Secondary oil extraction from the pomace produces olive pomace oil containing large amounts of free fatty acids and is considered an inferior oil compared to virgin olive oil. Pomace must be dried in long revolving horizontal cylinders through which hot air is passed before the oil can be extracted (73). The exhausted olive pomace is called kernel wood or orujillo. This product has few uses due to its low protein content and its high content of woody and cellulosic materials (73). Kernel wood is predominantly used as fuel for operation of the processing plant. Ash from kernel wood is used as fertilizer because of its potassium, phosphorus, and calcium content. The low value of this by-product negatively inuences the overall value of olive products, contributing to the high price for olive oil (71). 1.10. Sesame Sesame has declined in international trade due to a market preference for other oilseeds that are cheaper and easier to produce, such as groundnut. World trade tends to be in whole seed with only a small amount moving as oil and cake. There is great value in dehulling if the product is to be used as a foodstuff, as removal of the hull lowers the oxalic and phytic acid levels in the meal. The presence of these

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components may decrease the bioavailability of calcium, magnesium, zinc, and, perhaps, iron. The protein content, acceptability, and enzymatic digestibility of the meal will also increase (74). There are problems associated with dehulling, however. It is difcult to remove the hull from sesame, and there will be an associated loss of minerals. Whole press cake has a bitter taste due to the presence of the testa and is best used for manure and soil conditioning (51, 75). Cake or meal from oil extraction contains 4050% protein when processed in a screw press and 5660% protein after solvent extraction. Sesame products have a pleasant avor and contain high levels of methionine and cysteine. The our produced from sesame meal has a high nutritive value compared to other oilseed ours (75). Sesame has specic uses in confectionery products such as halva, sesame seed cake, candies, and as a garnish on bread and rolls. Microatomized protein food for feeding unweaned babies represents another use for sesame and other oilseed ours when enriched in vitamins and minerals (75). 1.11. Linseed/Flax Linseed is grown predominately for its quick drying oil and for the ber from its stalks. Whole seed is often shipped without processing at the location of harvest (76). Oil cake contains approximately 30% protein and is used in feed for sheep, horses, and dairy and beef cattle. A high mucilage content endows many positive properties to the meal. Linseed meal is comparable to soybean meal in composition but energy and protein digestibility are lower than for most other oilseeds. Linseed meal endows bloom and mellowness to the hide, which is most valued in the preparation of animals for shows. These qualities can be attributed to residual oil in the cake, slight laxative effects, and appetite stimulation (5). Care must be taken when linseed meal is used as feed for poultry. It contains a vitamin B6 antagonist, N-(g-Lglutamyl)-amino-D-proline, such that supplemental vitamin B6 must be used to prevent any detrimental effects from occurring. Low levels of lysine and methionine must be balanced using supplements before linseed meal can be used for swine feed. In addition, the possible presence of hydrocyanic acid should be monitored since it varies in concentration according to growing conditions. The cake has seen limited use as a soil conditioner (77).

2. BY-PRODUCTS OF OIL REFINING 2.1. Lecithin Lecithin, an edible by-product of oil processing possessing a variety of useful functionalities, is primarily a mixture of phospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, and phosphatidic acid and contains minor quantities of other water-soluble or hydratable components such as glycolipids and oligosaccharides (78). The degumming of oil with

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water or a degumming agent such as citric acid, phosphoric acid, oxalic acid, acetic anhydride, or maleic anhydride yields a lecithin sludge and a degummed oil. Continuous agitated thin-lm evaporation removes the approximately 50% water content of the lecithin sludge, resulting in a highly viscous semiliquid or powdered product (79). Soybean is the predominant vegetable source of lecithin due to its availability and outstanding functional characteristics. Lecithin products from rapeseed and sunower are increasing in market share. Glandless cottonseed and corn are also potential commercial sources (7982). The composition of rapeseed lecithin is very similar to that of soybean but is considered to be of lower quality with respect to color, avor, taste, and general appearance. This product has been predominantly used as a dust control agent in rapeseed meal and is added to livestock and poultry feeds (79). The development of canola or low-erucic-rapeseed varieties and specialized rening processes have increased the use of rapeseed lecithin. Glanded cottonseed contains more phospholipids than any other oilseed with the exception of soybean. Solvent extraction methods, however, cause toxic gossypol to bind to the phospholipids. The resulting lecithin is dark brown in color, limiting its use in food products (81). Purication and Fractionation of Crude Lecithin. Purication consists of the removal of nonlecithin components such as carbohydrates, proteins, and other contaminants. Vegetable lecithin is more difcult to purify compared to other sources of lecithin because of its higher viscosity. The crude product obtained during degumming is contaminated with nes derived from seed material, hulls, and other seed impurities. Regulatory standards require that these contaminants be removed because of the high levels of iron and heavy metals in the impurities, which interfere with the oxidative stability of the products to which lecithin is added. Methods used for purication include ltration, which can be performed on the crude oil, lecithin, or miscella, partitioning between organic solvent and water or salt solution, dialysis, and adsorption on cellulose or Sephadex columns (80, 81, 83). Fractionation takes advantage of the varying solubilities of different phospholipids in different organic solvents. Many options are available for large scale production of marketable lecithin. The de-oiling process is one fractionation system in which the separation of neutral and polar lipids is based on the insolubility of polar lipids in acetone; more than 60% of lecithin consists of acetone-insoluble substances. Oily lecithin is combined with excess acetone and mixed vigorously, thereby solubilizing triglycerides in the acetone. This process is repeated, after which the polar lipid material is dried and sold as a light yellow powder or in the form of granules (79). De-oiling on a smaller scale can be accomplished using adsorption of lecithin, in a hexane solution, on a silica column. Also, a new technology has been developed for treating the lipid mixture with a supercritical uid. For example, carbon dioxide at a temperature of 40 C and a pressure of 300 bars has a solubility similar to that of liquid acetone. The gas may be recovered and reused. Oxidation of the lecithin does not occur since oxygen is displaced by carbon dioxide. As well, the absence of solvent residues in either the oil or the lecithin eliminates ammability and environmental concerns. This process, however, has

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a number of drawbacks, and its commercial feasibility has not been established (79). Crude fractions can be obtained by solvent fractionation treatments utilizing lower alcohols, such as ethanol, or alcoholwater mixtures. The product is a soluble fraction rich in phosphatidylcholine, whereas phosphatidic acid and phophatidylinositol predominate in the insoluble fraction. The shift in the ratio of phosphatidylcholine to phosphatidylethanolamine improves the emulsication and antispattering capabilities of the soluble fraction. The products of this process can be used as they are or can be further puried with adsorbents. The soluble fraction is an excellent oil-in-water emulsier and is predominately used in margarine. The acidic phospholipids of the insoluble fraction are used in water-in-oil systems. The chocolate manufacturing industry uses this fraction to increase the viscosity of chocolate masses, thereby reducing the requirement for cocoa butter (83, 84). It is not possible to obtain pure phospholipids from lecithin by solvent fractionation. Chromatographic adsorption processes are capable of separating this complex mixture but cannot be used, in practice, to generate large quantities of the pure phospholipids. Chromatographic adsorption methods include aluminum oxide with ethanol or chloroform/methanol, silica gel with a variety of solvent systems, and a diethylaminoethylcellulose system. A high price is demanded for puried phospholipids (83). Functionality and Utilization of Lecithin. There exist a number of functional groups in lecithin that can be modied. Phospholipid products derived by hydrolysis, hydroxylation, and acetylation are the most likely to be used commercially. Hydrolysis can be performed with phospholipase A, acid, or alkali. The resulting lecithin contains 56% or more of acetone-insoluble material. Products of hydrolysis have improved hydrophilic and emulsifying properties. Hydrolyzed lecithins are highly viscous or pasty uids and tend to be light brown to brown in color (85). The products resulting from hydroxylation of lecithin have improved oil-in-water emulsifying properties and improved water dispersibility. Acetylation of phosphatidylethanolamine creates improved uid and emulsifying properties, as well as improved water dispersion. Modication of the polar phosphoric acid ester or the glyceride moiety of phospholipids is legally restricted in the food industry (78). The wide range of functionalities of lecithin has been applied in a variety of industries, including pharmaceuticals, cosmetics, and food. Lecithin components have both lipophilic and hydrophilic groups that respond to changes in pH and differences in ionic strength. These charged surfactants stabilize emulsions of water and oil. The selection of the appropriate raw material and the use of techniques such as fractionation, modication, and compounding can be combined to generate the phospholipid characteristics best suited to a desired application. Different phospholipid and fatty acid combinations inuence solubility, emulsifying quality, the type of emulsion (whether oilwater or wateroil), instantizing properties, dietetic value, and sensitivity to oxidation (86). Lecithin acts as a lubricant and release agent between solids by coating the surface of the solids. A reduction of the surface tension and particle attraction occurs when lecithin coats solids in a solidliquid mixture, which allows for stable

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dispersion and suspension of the solid in the liquid. Lecithin also reduces surface tension and enhances emulsication in immiscible liquid mixtures (87). Lecithin makes up 0.51.0% of the composition of many cosmetic products. The surfactant properties are most valued for the skin feel that is produced. Longer wearing cosmetics evolve from pigments and particulates coated in lecithin since they have smoother surfaces, increased adhesion to the skin, and improved color stability. Due to lm adhesion, the presence of lecithin reduces the oily or greasy feeling of many products and reduces the transfer of cosmetics to clothing. The emulsication properties, ease of spreading, and wetting ability of lecithin are also utilized in cosmetic products (88). Lecithin may become a useful component of magnetic recording equipment due to its ability to act as a surfactant, thereby facilitating dispersion of magnetic particles on pigment surfaces. The magnetic and physical properties of the recording tape are enhanced as a result. For lecithin to be active in this capacity, it must function in a variety of solvents including methylethylketone, tetrahydrofuran, cyclohexane, and toluene. Another valuable property of lecithin is its ability to adsorb to the surface of a variety of pigments such as iron oxide, chromium dioxide, iron metal, and barium hexafurite (89). Industrial coatings, paints, and inks utilize lecithin because of its pigment dispersal characteristics. Lecithin binds to pigment surfaces allowing wetting of the pigment by the vehicle in which it is being dispersed. Lecithins with different functionalities can function in both oil-based and water-based formulations (87). The food industry relies on lecithin in bakery, beverage, and confectionery product development. The lecithin functionalities of emulsication, release, mixing and blending, and instantizing, many of which were discussed above, are put to use in many aspects of food production (86). Lecithin is used in baking as a dough conditioner for cookie, cake, and doughnut mixes with many positive effects including improved handling, a drier and more elastic dough, improved pan release, more uniform color, texture and grain, and decreased mixing time. Lecithin acts as a dispersor, aiding the mixing of unlike ingredients such as fat and our or sugar. The activity of lecithin as a surfaceactive agent has been shown to retard the rate of staling in yeast-leavened products. Lecithin plays a valuable role in the instantizing of beverage and food mixes by promoting the incorporation of powders into aqueous environments. Dry edible powders such as cake mixes, nutritional supplements, and milk powders can be quickly integrated into liquids such as milk or water with the aid of lecithin (90). The confectionery industry utilizes the emulsication, antistick, and viscosity properties of lecithin and benets from the concurrent effects of shelf-life extension, texture improvement, and decreased production costs (83). A product such as caramel will not blend correctly in the absence of lecithin. Uniform dispersion of fat, aided by lecithin, will decrease stickiness and provide tenderness for ease of cutting. The natural antioxidant properties of lecithin slow the decay of any product in which it is incorporated. Viscosity is very important in the chocolate industry where shape is often a requirement for consumer acceptability. High concentrations of butter, such as cocoa butter, impart high viscosity, which in turn makes

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production more efcient. Alternatively, lecithin may be used to provide a portion of the viscosity requirement and to eliminate greasiness in the nished product (84). 2.2. Rening By-Product Lipid (Soapstock) Rening by-product lipid, commonly referred to as RBL, results from the rening of crude oil, where continuous mixing of crude oil with a dilute sodium hydroxide solution produces a by-product consisting of free fatty acids, hydrolyzed phosphatides, and unsaponiable materials (91). Free fatty acids are the valued component in RBL, the composition of which varies with the oil source, oilseed condition at crushing, the oil removal method used, the solvent employed, the extent of extraction, and the rening conditions. Larger quantities of RBL are produced as the oil becomes more rened. The concentrations of free fatty acids, gums, and impurities, and the efciency of rening, inuence the amount of RBL formed. Rening byproduct lipid tends to be the item of lowest value produced in oil rening (92). Acidulation of RBL using sulfuric acid stabilizes it and reduces its weight for shipment. Debris such as phosphatides, proteins, and mucilaginous substances are present in varying quantities depending on the quality of degumming and rening and may cause emulsication to occur and prevent effective acidulation (91). The acidulation of RBL is the greatest wastewater producer in the rening system. Disposal of the efuent or acid water requires expensive treatment measures to comply with environmental regulations (91). The Daniels Fertilizer Company (Shrewsbury, Mass.) views this acid water as a potential resource. The use of nutrient chemicals in the rening, acidulation, and neutralization steps produces an acid water suitable for use as a liquid fertilizer. Vegetable oils are rened with caustic potash (KOH) instead of caustic soda (NaOH), and acidulation with sulfuric acid is followed by neutralization with ammonia rather than NaOH. This is an innovative method that closes the loop of agriculture processing (93). Animal feed is the dominant sink for RBL. Rening by-product lipid can be returned to meal to increase its weight and its fat content. This has been done to a level of 0.9% for cottonseed meal and 0.4% for soybean meal (91). Soybean RBL provides 6694 kcal/kg of digestible energy and 6599 kcal/kg of metabolizable energy to pigs (94). Rening by-product lipid not only increases caloric content but also provides essential fatty acids and increases food utilization. Rening by-product lipid may also be added to feed for purposes of dust control, appearance, ease of handling, and improved pelletability (95). Raw and acidulated RBL are combined in different ratios with animal tallow to produce soaps of varying characteristics. Palm oil and coconut oil are the dominant fatty acid sources for soap manufacturing. Coconut oil and tallow are complementary in fatty acid composition such that in combination they provide the ingredients of toilet soap (96). There has been speculation regarding the use of safower and sunower RBL in this capacity if alterations were made to processing methods. Cottonseed and soybean RBLs are available in large quantities but the cost of upgrading these to the quality necessary for use in toilet soap inhibits their use. Rening by-product lipid has been considered as a growth medium for microorganisms. It appears to provide a satisfactory supply of nutrients for growth, due

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in part to its high sodium content and its suitable trace element composition. Despite its residual oil content and high pH, many species of microorganisms will grow on this substrate (97).

2.3. Spent Bleaching Earth Spent bleaching clay from oil rening contains substantial absorbed oil (2040% w/w). This product is both a problem and a potential source of recoverable oil. The problems of spent clay are well known (98). Fat-containing clays are prone to spontaneous combustion when in contact with air, particularly if the bleaching earth contains highly unsaturated oils. Spent clay also represents an environmental concern, both as a re hazard and as a threat to ground waters through fat-containing runoff when discarded in landlls. In addition, there is an economic loss of oil in the clay. Technical solutions to the recovery of oil from spent clay can be categorized into four areas: 1. Steam Treatment. This method, whereby steam is blown through the cake, is commonly practiced in reneries to reduce the oil content of the cake to approximately 20% (99). 2. Aqueous Extraction. In its simplest form, this procedure involves pumping 95 C water through the cake for approximately 30 min to reduce its oil content. The oil must then be separated from the water (98). A procedure employing extraction with sodium carbonate has been described (98, 99) where spent clay was mixed with an aqueous 5% sodium carbonate solution. The slurry was heated to 95 C and stirred slowly for 30 min. Although the procedure is simple, hot carbonated water sometimes failed to displace the fat. The quality of the resultant oil was low and disposal of residual slurry [containing clay, water, and salt (NaCl)] was difcult. Suggested methods of slurry disposal include inclusion in cement manufacture or blending into sandy soils to improve soil structure. Boiling the spent clay in a water suspension containing 1.52.5% concentrated sodium hydroxide as a surface-active agent has also been described (100). This procedure yielded a dark-colored oil that could only be used for technical purposes. After extraction, the residual slurry was centrifuged and the liquid efuent appropriately treated. The solid material was used as a landll material or as a replacement for earth or sand for the covering of refuse dumps (100). 3. Solvent Extraction. Spent clay oil recovery by solvent extraction with hexane may be accomplished after ltration, either directly from the cake in the lter or after the cake has been removed from the lter (99). Any exposure of the cake to air prior to extraction will cause rapid deterioration of the fatty material. Depending on the intended use of the oil, perchloroethylene or methyl chloride may be effectively employed as solvents (98).

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4. Pressure Extraction. The use of pressure (530 bars) in combination with water and sodium hydroxide has been shown to produce acid oils from spent clay that can be easily separated by decanting (98). Other options for recovery of oil from spent clay include mixing the spent clay lter cake with milled oilseeds en route to solvent extraction. This procedure is used in some reneries having associated crushing and rening plants and is convenient if the re hazard of the spent clay can be overcome and the level of addition is small enough to not signicantly alter the mineral content of the meal (99). Evaluations of spent bleaching clay as a feed supplement indicate that, for poultry diets, inclusion rates of up to 7.5% spent clay in diets produced no deleterious effects on feed intake, growth rate, or feed efciency (101). These results suggest that spent clay could be added to poultry feed at 0.52.0% which is similar to the amount of bentonite clay currently used as a pellet binder in poultry diets. The metabolizable energy (ME) of spent clay was determined to be 2870 kcal/kg (dry matter basis) but would vary with oil content. Other studies have also demonstrated the feeding value of spent clay (102). Spent clay and its associated disposal problems represent a concern for all reneries. Additional research may yield new and more valuable uses for this byproduct material. 2.4. Deodorizer Distillates Deodorizer distillate is the material collected from the steam distillation of vegetable oils, as it occurs in the process of deodorization or physical rening (103). The material has a sludgelike appearance and consistency so is often referred to as scum or scum oil. The use and value of deodorizer distillate is dependent on its composition. Deodorizer distillate is a complex mixture of tocopherols, sterols, esters of sterols, mixed fatty glycerides, hydrocarbons, and other materials contained in a substantial amount of fatty acids (104). If the material is high in unsaponiable components, the tocopherols can be used in the manufacture of natural source vitamin E and sterols for drug manufacture. The quality of the distillate is dependent on the feedstock oil composition, processing equipment, and operating conditions. Comparisons of the tocopherol and sterol contents from various oils indicate that some oils have appreciably higher contents of specic tocopherols and sterols (94). For example, sunower is high in a-tocopherol, whereas soybean is higher in g-tocopherol. As deodorization strips tocopherols and sterols from the oil, different feedstock oils yield different concentrations and types of tocopherols. Direct contact cooling of the deodorizer discharge vapor with a stream of circulating distillate is the most common method of condensing distillate vapor. Although designs of distillate recovery towers and their position in the deodorization system vary, the purpose remains the cooling of the vapor sufciently to condense most of the distillates (105). The operation of the deodorizer has a direct impact on distillate composition and quality. In general, higher deodorization temperatures, longer

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exposure times, and lower vapor pressures will increase the yield of distillate and decrease the tocopherol and sterol content remaining in the oil (103). Distillate is frequently collected and sold, representing value to the renery. The demand and value is based on the total tocopherol content, as it relates directly to the economics of vitamin E production. The value of distillate varies and has been as high as $1.45/kg ($0.65/lb) (103). End users of the distillate use a series of chemical and physical treatments such as saponication, esterication, and molecular distillation to separate tocopherols and sterols (106). Research has been conducted on the use of supercritical uid extraction to separate and concentrate tocopherols and sterols from the sludge (107). With the increasing interest in natural source antioxidants, such as tocopherols, and the use of both stigmasterol and b-sitosterol as raw materials for the production of progesterone and esterone by the pharmaceutical industry, it is likely that deodorizer distillates will continue to be an important by-product for some vegetable oil processors.

2.5. Spent Catalyst Catalysts are required in the hydrogenation of fats and oils. The most commonly used catalyst is nely divided nickel having a large surface area and used in a aked or granular form. The nickel component and clay support each make up 50% of the catalyst in a surrounding hydrogenated fat medium. Spent catalyst is removed from the hydrogenated oil using ltration methods such as plate and frame or pressure leaf-type lter presses. The recovered catalyst product contains nickel, clay materials, and residual fat or oil, as well as any ltration media used to aid in ltration of the physically ne spent catalyst. The heat content of spent catalyst ranges from 4500 to 8700 kcal/kg (108). The use of spent nickel catalyst in its posthydrogenation form is limited. The only available example of its use is by the M.A. Hanna Company (Cleveland, Ohio). This company mines and smelts nickel, producing a ferro-nickel product of primary use in the production of stainless steels. To conserve its nickel supplies, Hanna modied its system for feeding the production line to allow mixing of spent nickel catalyst with the nickel containing ores at up to 10% of the total nickel feed (108). Landlls have been the most popular depositories of spent nickel catalyst. Environmental concerns regarding the impact of nickel and conservation efforts to preserve nickel supplies have stimulated recycling and reclamation of the nickel component. Solvent extraction of organic material from the nickel is most effective with polar solvents such as isopropanol and methyl ethyl ketone (108). Incineration is another reclamation technique in use. The multiple-hearth furnace can operate under designed conditions for years with low maintenance and low energy consumption (108). The uid-bed incinerator is also very effective (108). Tests have shown that all organic compounds are decomposed and most carbon residue oxidized. The ash is of high nickel value being predominately

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composed of nickel oxide and silica. The energy input of these reclamation processing methods is fractional compared to the total heat content of spent catalyst. Generation of thermal energy through these processes has the potential for electricity generation as well. Spent nickel catalyst is a product with limited potential for further utilization. In the future, however, the entire composition of the spent catalyst, including the organic fraction, may be found to have value beyond heat generation (108).

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