Sunteți pe pagina 1din 18

Food Research International 40 (2007) 957974 www.elsevier.

com/locate/foodres

Review

Soapstock and deodorizer distillates from North American vegetable oils: Review on their characterization, extraction and utilization
Marie-Josee Dumont, Suresh S. Narine
*
Alberta Lipid Utilization Program, Department of Agricultural Food and Nutritional Science, 4-10 Agriculture/Forestry Centre, University of Alberta, Edmonton, Alberta, Canada T6G 2P5 Received 27 November 2006; accepted 5 June 2007

Abstract Soapstock and deodorizer distillates are the major by-products from vegetable oil rening. They have little commercial value and are sold at a fraction of the oil cost. However, their characterization reveals the presence of numerous types of compounds, which could be extremely valuable if extracted at low cost. The literature in this area is discontinuous and warrants the eort to produce a comprehensive review. The aim of this review is to combine and condense the body of research performed on these materials, as well as to suggest the best routes for characterization and extraction. Utilization of the components is also discussed. 2007 Elsevier Ltd. All rights reserved.
Keywords: Vegetable oils; Soapstock; Deodorizer distillate; Characterization; Extraction; Utilizations

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Crude oil refining. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Degumming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Chemical refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Physical refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Bleaching, winterization and deodorization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5. Other refining methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.1. Refining by membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Characterization of by-products obtained from oil refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Characterization of soapstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Characterization of deodorizer distillates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Characterization of acid oil water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Utilization of components from refining oil waste streams. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Soapstock and animal diet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Biodiesel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Drilling fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Specialized applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958 958 958 959 959 960 960 961 961 961 962 963 963 963 964 965 966

3.

4.

Corresponding author. Tel.: +1 780 492 9081; fax: +1 780 492 7174. E-mail address: Suresh.narine@ualberta.ca (S.S. Narine).

0963-9969/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodres.2007.06.006

958

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

5.

6.

4.4.1. Multigrade lubricating greases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.2. Biosurfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.3. Fatty acid modification diacylglycerols (DAG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.4. Derived films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Extraction of valuable components from soapstocks and deodorizer distillates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Soapstock. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1.1. Extraction of fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1.2. Extraction of gossypol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Extraction of deodorizer distillate components. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1. Extraction of tocopherols, sterols and squalene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1.1. Solvent extraction and crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1.2. Supercritical fluid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1.3. Enzymatic reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1.4. Molecular distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1.5. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

966 966 967 967 967 967 967 968 968 968 969 969 971 971 971 971 972 972

1. Introduction Edible oils are produced primarily from oilseeds. Total world production of important oilseeds is forecasted to reach 395 million tonnes for the 2005/2006 crop year1 of which Canada will contribute 14 million tonnes.2 The crude or unrened oils extracted from oilseeds generally consists of free fatty acids (FFA), mono-, di-, and triacylglycerides (MAGs, DAGs, and TAGs), phosphatides, pigments, sterols, tocopherols, glycerol, hydrocarbons, vitamins, proteins fragments, trace amounts of metals, glycolipids, pesticides and resinous and mucilaginous materials among others (Cheryan, 1998). The method chosen for oil extraction is highly dependent upon the nature of the oilseed, the economic feasibility of the extraction process and market demand. The rst step in producing oils for edible applications involve the separation of the oil (containing more than 90% TAGs) from other solid components of the seeds. For the majority of oilseeds, this is achieved by pressing followed by solvent extraction (Young, Biernoth, Krog, Davidson, & Gunstone, 1994). This crude oil is then rened in order to remove free fatty acids and other non-TAG components which contribute to undesirable avor, odor and appearance. Methods of treatment include deacidication, neutralization, bleaching, deodorization, etc. (Anderson, 1953). A signicant amount of by-products such as soapstocks, deodorizer distillates and acidic water are produced from crude oil rening processes, and these by-products are potentially harmful to the environment. In the United States for example, soybean oil rening processes potentially produce 100 million pounds of soapstock which retails at 1/10th the cost of the rened vegetable oil.3
http://www.fao.org/es/ESC/en/20953/21017/highlight_27527en.html. http://www.agr.gc.ca/mad-dam/e/sd1e/2006e/mar2006e.htm. 3 http://www.landandlivestockpost.com/technology/050102soybyproducts. htm.
2 1

Due to human population increase, the consumption of edible oils is expected to increase, thereby resulting in increased production of these by-products. It is therefore important to study and explore ways of mitigating their negative environmental impact as well as derive value added products. Signicant potential exists for the extraction of valuable and useful chemicals from these nonTAG waste products. In order to convert the waste from the oil rening process to value added materials, it is imperative that economically feasible chemical modication, identication and separation techniques be developed. This presents a considerable challenge given the chemical complexity of these waste materials. 2. Crude oil rening Crude oil is rened using several processes to remove undesirable components before making it available for human consumption. These processes are widely covered in the literature. This section provides information on the by-products produced after crude oil rening. Fig. 1 summarizes the conventional processing steps encountered from crude to rened rapeseed oil and Table 1 summarizes their advantages and disadvantages. 2.1. Degumming The rst rening step involves the removal of phospholipids using the degumming process. These molecules are either present in a hydratable or a non-hydratable form. The non-hydratable form occurs when the phospholipid is combined with calcium, magnesium or iron cations. This form must be treated with acid in order to convert them to hydrated gums. The hydratable form is treated by water degumming and directly converted into hydrated gums. These gums are then removed by centrifugation.

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

959

Crude oil Chemical refining Water degumming or Acid degumming

Physical refining

Bleaching

Winterization

Deodorization

Conventional chemical rening is time consuming and has several disadvantages. It has substantial energy requirements and the side products formed (soapstock and deodorizer distillate) are not environmentally friendly or commercially valuable. Furthermore, the chemical process leads to considerable oil loss; soapstock can hold as much as 50% of its weight of neutral oil. Despite having several disadvantages, it is still used in many industries because of the successful reduction of free fatty acid (FFA) content to the desired level. Miscella deacidication involves slight modication of the chemical rening process. In this process, the oil is mixed with hexane to create miscella. The miscella are mixed with sodium hydroxide in a neutralization step and then reacted with phosphatides. This process also induces decolorization. Soapstock are removed by centrifugation which results in minimal loss of neutral oil, however it is very expensive and solvent removal requires several steps. Miscella deacidication is almost only used for the rening of cottonseed oil because a lighter color of nal product is obtained compared to using the classical methods (Bhosle & Subramanian, 2005). 2.3. Physical rening Physical rening processes use steam stripping under vacuum to avoid chemical neutralization. It is a simplied operation that removes free fatty acids, unsaponiable substances, and pungent compounds and also reduces the amount of oil lost. It consumes less steam, water and power, and requires less capital investment than the chemical rening process (Cvengros, 1995). Two similar physical rening processes can be used depending on whether the raw material is a low phosphatide or high phosphatide crude oil. The physical treatment of low phosphatide crude oil consists of a series of steps involving dry degumming, dewaxingfractionationhydrogenation, steam distillation and deodorization. The treatment of high phosphatide crude oil consists of an acid rening or degumming step prior to dry degumming or bleaching. The low phosphatide crude oil treatment does not require additional acid rening or degumming steps (OBrien, 2004). According to a review on the subject (Cmolik & Pokorny, 2000), there

Refined oil

Fig. 1. Oil rening processing steps.

2.2. Chemical rening The degumming step is not always necessary prior to chemical rening. The best known and the most widely used chemical rening process is the caustic soda process. Phosphoric acid is added to the crude oil in order to precipitate the phospholipids; this is followed by the addition of an alkaline solution. The alkaline solution neutralizes the free fatty acids (reaction 1) and any excess phosphoric acid (reaction 2). Reaction of the alkaline solution with fatty acids leads to the formation of soap. The soapstock created is then continuously separated from crude oil by centrifugation (OBrien, 2004): RCOOH NaOH ! RCOONa H3 PO 3NaOH ! Na3 PO4 reaction 1 reaction 2

Table 1 Dierent rening methods and their advantages and disadvantages Rening type Chemical rening Advantages (1) (2) (3) (1) (2) (3) (1) (2) (1) Functional process Not restricted by the oil type Successful reduction of FFA Less expensive than chemical rening Less by-products generated than chemical rening Less energy consumed than chemical rening Non-polluting Low energy demand Minimal loss of oil Disadvantages (1) (2) (3) (1) (2) (3) (1) Production of side-products Expensive process Remove high % of oil Not suitable for all types of oils Requires high temperature and vacuum Can form side reaction products Improvement of equipment needed

Physical rening

Membrane Miscella deacidication

(1) Soapstock generated (2) Not suitable for all types of oil (3) Expensive

960

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

are seven dierent variations of physical rening procedures that can be applied depending on the type of plant design. Physical rening of crude vegetable oil has several advantages over traditional alkali rening processes. For example, there are improvements with regard to simplicity of the procedure, product yield, energy conservation, and reduced generation of environmental pollutants. There are also many drawbacks such as not all types of oils are suitable for this process (Hartman, 1978). The use of high temperatures and high vacuum often results in the formation of side products such as polymers and trans isomers (Sengupta & Bhattacharyya, 1992). 2.4. Bleaching, winterization and deodorization Carotenoids, chlorophyll pigments, residual soap, phospholipids, metals and oxidized products are removed by

bleaching. These components are absorbed by heated clay. Fig. 2 shows the chemical structures of zeaxanthin (a type of carotenoid found in corn), chlorophyll and L-a-phosphatidylcholine (a type of phospholipid found in soybean). The oil is then rapidly cooled (winterized) to solidify traces of wax, which are esters of fatty acids or long chain alcohols. These particles are then easily removed by ltration. Deodorization removes aldehydes, ketones and other volatile components that would otherwise impart avor and odor. 2.5. Other rening methods Several other rening processes are currently under development. Rening by membrane will be discussed in this review because it is a soapstock free process. The miscella deacidication process is also introduced in this
OH

(A)

HO

(B)

Mg
N N

O O

H3CO O O

(C)
H3C(CH2)14

O P O O O OO O +N

(CH2)7CH=CHCH2CH2CH2(CH2)4CH3

Fig. 2. Chemical structures of (a) zeaxanthin, (b) chlorophyll and (c) L-a-phosphatidylcholine.

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

961

review because it is used mostly for rening cottonseed oil. 2.5.1. Rening by membrane Membrane rening is a simple process oering many advantages over conventional processes. In the membrane rening process, dierent compounds are separated based on the dierence between their molecular weights, particle shapes and particle sizes. The membrane-based technology is being actively investigated and is sought as an alternative to chemical and physical rening because it is non-polluting and has a low energy demand. Raman, Cheryan, and Rajagopalan (1996) have shown that by using a nanoltration process, no alkali is required and no soapstock is formed. The membrane rening process is very promising but several diculties must be surmounted before it can replace conventional rening methods. Several research groups are actively working to improve the equipment, enhance the eciency and increase the selectivity of the membranes (Lin, Rhee, & Koseoglu, 1997). For example, studies have demonstrated that it is possible to remove phosphorous, water and FFA by a single ltration step (Pioch, Largueze, Graille, Ajana, & Rouviere, 1998; Koris & Vatai, 2002). However, sterols that have benecial health eects are also removed from the oil (Hadi, Pioch, & Ajana, 2005). 3. Characterization of by-products obtained from oil rening 3.1. Characterization of soapstocks Soapstocks are mostly wet lipidic mixtures. Their physico-chemical properties tend to change with the type of vegetable oil source, seed processing, and handling and storage conditions. To limit chemical changes that can occur in the mixture, the American Oil Chemists Society (AOCS) has developed recommended handling and storage conditions (method G1-40). The AOCS has also developed several other protocols: extraction of neutral oil and volatile solvent content (method G5-40), measurement of neutral oil content (method G5-40), extraction of fatty matter (method G3-53) and more specically extraction of fatty matter for palm and coconut soapstock (method G4-40) (Firestone, 1998). The compositional determination of soapstock began in the mid-nineteen fties. At that time, the recorded data were acid and iodine values, unsaponiable matter content, volatile matter content, free fatty acid content and neutral oil and ash contents (El-Shattory, 1979; Keith, Bell, & Smith, 1955; Stansbury, Cirino, & Pastor, 1957). The rheological characteristics of soapstock were studied later (Hiraldo, Herrera, Luque, & Montes, 1989). The rst attempt to characterize soapstock was achieved in 1987 (Waliszewski, 1987). Since then, three other papers have described methods for the characterization of soapstock (Dowd, 1996, 1998; Durant, Dumont, & Narine, 2006). Waliszewski (1987) utilized gas chromatography (GC) for the fatty acid analysis of soybean, sunower, saf-

ower, cotton seed and corn germ soapstock. Waliszewski et al. neutralized the soapstock mixture with acid and decreased the viscosity with addition of ethanol prior to the GC analysis. The analysis of fatty compounds requires rigorous labor, especially in the case of soapstock, where the mixture has components with diering degrees of polarity. The author was able to quantify fatty acids that have similar retention times (for example linoleic and linolenic acid) without the need for derivatization prior to chromatographic analysis. This research was the rst introduction to the analysis of soapstock by gas chromatography. Since the publication of this research, derivatization techniques have been introduced for the characterization of these materials (Dowd, 1996, 1998; Durant et al., 2006). It was in 1996 that a complete characterization of soapstock was accomplished. Dowd (1996) characterized 39 samples of cottonseed soapstock. In this work, Dowd carried out some of the AOCS protocols such as total fatty acid and neutral oil extraction (G3-53 and G5-40 respectively), analysis of nitrogen (Ba 4e-93) and total gossypol content (Ba 8-78). Analysis of soapstock was performed using gas chromatographymass spectroscopy (GCMS). Sample preparation required a drying step followed by derivatization using pyridine, hexamethyldisilazane (HMDS) and triuoroacetic acid (TFA). The silyl derivatives were found to be more volatile, less polar, thermally more stable and could displace chromatographic peaks of soap counterions at the same position of their corresponding free fatty acids. From this work, cottonseed soapstock was found to be mainly composed of moisture and solvent (approx. 49%), fatty acids (approx. 60% on a dry basis), organic phosphates, monoglycerides, diglycerides, triglycerides, sterols, polyalcohols, carbohydrates and other miscellaneous components including gossypol. The majority of these classes of organic compounds are found in dierent types of soapstock, however gossypol (a polyphenolic compound) is found only in cottonseed sources. Dowd (1996) found a gossypol content of 7.5% in cottonseed soapstock. Dowd (1996, 1998) reported that the amount of fatty acids extracted by solvent (using AOCS ocial method G3-53) was found to be in accordance with the results given by GC and phosphorus analysis but the percentage of neutral oil recovered from soapstock was dierent from the AOCS method G5-40. Dowd (1998) also found that the amount of saturated fatty acids was higher than their concentration within the rened oil. Dowd explained these results by the fact that saturated fatty acids in several vegetable oils (i.e. corn, cottonseed, sunower, soybean and saower) are positioned on the triglyceride backbone at the sn-1 and sn-3 positions. These fatty acids are released from the triglyceride because hydrolysis by chemicals and enzymatic glycerides occurs generally at these positions. The fatty acid composition of dierent sources of soapstock is presented in Table 2. Although Dowds study allowed for the total composition of soapstock to be determined, the choice of a more polar column may have helped with the separation of

962

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

Table 2 Fatty acid content of dierent soapstock sources Fatty acids Concentration (%) reported on a dry basis Cottonseed (Dowd, 1996) Myristic acid Palmitic acid Palmitoleic acid Stearic acid Oleic acid Linoleic acid Linolenic acid Arachidic acid 0.24 9.31 0.18 0.96 6.07 16.50 nd 0.077 Corn (Dowd, 1998) 0.031 8.62 tr 0.507 9.36 17.8 nd 0.076 Peanut (Dowd, 1998) 0.066 8.62 tr 0.458 11.6 7.75 nd tr Canola (Durant et al., 2006) nd 4.63 0.15 nd 15.57 3.31 0.24 0.12

nd = not detected; tr = traces.

compounds such as TMS-esters of linoleic and linolenic acid. In addition, the high temperatures utilized caused a partial degradation of the fatty acids. Application of the derivatization technique used by Dowd (1996, 1998) coupled with a medium polar column (instead of a low polarity column) allowed for the separation of linoleic and linolenic acid (Durant et al., 2006). This application of Dowds derivatization technique also has the advantage of allowing the separation of monoolein and monolinolein which have similar retention times. In addition, this method was successful at separating components of deodorizer distillate samples (discussed below). 3.2. Characterization of deodorizer distillates Deodorizer distillates are complex mixtures like soapstocks. Their commercial value however, is mainly dependent on their tocopherol content. In fact, the majority of research published covers the characterization and recuperation of high-value chemicals such as tocopherols and sterols that are present in the deodorizer distillates. There are few publications relating to the full analysis and characterization of the mixture. Table 3 presents the tocopherol and sterol content of some deodorizer distillate sources. As with soapstocks, methods have also been developed by the AOCS for the characterization of deodorizer distillates. Method CE3-74 is one such method and involves the
Table 3 Tocopherol and sterol content of dierent deodorizer distillate sources Component Concentration (g/100 g) Soybean (Verleyen et al., 2001) d-Tocopherol b-Tocopherol c-Tocopherol a-Tocopherol Brassicasterol Campesterol Stigmasterol Sitosterol 5.00 0.44 11.00 0.82 nd 5.36 4.46 8.12 Sunower (Verleyen et al., 2001) nd nd 0.3 4.76 nd 1.58 2.04 8.60 Rapeseed (Verleyen et al., 2001) 0.25 0.16 2.41 1.12 2.2 3.65 nd 5.15 Canola (Durant et al., 2006) 6.56 nd 13.51 0.55 nd 2.59 2.27 2.66

nd = not detected.

use of gas liquid chromatography (GLC) with a packed glass column. Saponication is preferred prior to performing the GC analysis to diminish potential overlapping peaks in the tocopherol region. This procedure provides a rough estimation of the tocopherol and sterol content. However, the chromatogram does not show any saponied matter (mainly fatty acids) because saponication neutralizes such compounds. According to literature (Feeter, 1974; Marks, 1988), the use of a packed column, therefore, is not a suitable method for the separation of components from the deodorizer distillates. Research by Feeter (1974) using packed column gas chromatography analysis showed that this method is not suitable for the separation of the trimethylsilyl ether derivatives of b-, c- and d- tocopherols that co-elute with sterols. The author also identied at least ve other pairs of co-eluted compounds. Avoiding the saponication step does not resolve the co-elution problem (Marks, 1988). However, the method could be useful for a rough estimation of the tocopherol and sterol content, but sample preparation is 23 times longer than capillary gas chromatography (Marks, 1988) which is also a more accurate technique. Capillary gas chromatography is a simpler, faster technique that can lead to the characterization of all the components in deodorizer distillates depending on parameters such as the distillate pre-treatment and the choice of column. It has been found that saponication is not necessary when utilizing this method. Not all characterization carried out using this technique have been successful without coelution but the resolution is denitively better than the GC analysis utilizing a packed column This can be rationalized by the low impedance of the capillary column allowing for the use of a very long column which provides very high eciencies. Verleyen et al. (2001), by means of this technique, characterized several types of deodorizer distillates such as soybean, canola, sunower and corn. This study involved the characterization of both saponied and derivatized deodorizer distillates. Comparing chromatograms of the above two studies, it was discovered that free fatty acids are not present after saponication of the samples. Furthermore, numerous peaks located in the region before the sterols and tocopherols remain unidentied. Some of these peaks appear at the same retention time as the identied fatty acid peaks. The authors also report two pairs of compounds that co-eluted when the distillates were derivatized. Brassiscasterol and a-tocopherol co-eluted as well as c- and d-tocopherol. The authors state that the separation of the latter pair of compounds could only be achieved by using high performance liquid chromatography (HPLC), contradicting the results reported earlier by De Greyt, Petrauskaite, Kellens, and Huyghebaert (1998) who performed HPLC analysis on dierent types of vegetable oils. The methodology based on the silylation derivatization technique described earlier (Section 3.1) could provide assistance with the co-elution issue (Durant et al., 2006). HMDS used in the silyl derivatization step is a milder base

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

963

in comparison to the commonly utilized N,O-bistrimethylsilyltriuoroacetamide (BSTFA) (Marks, 1988; Verleyen et al., 2001) but the HMDS silylation method requires TFA as a catalyst. The use of a medium polar column with these silylation conditions allowed for successful separation of fatty acids, sterols, tocopherols and glycerides. This method also successfully separated brassiscasterol and atocopherol as well as c- and d- tocopherols. The use of expensive techniques such as capillary supercritical uid chromatographymass spectroscopy also does not appear to be a suitable method and could be considered as one of the less successful techniques due to high cost and time consumption. Snyder, Taylor, and King (1993) utilized this technique and focused on the tocopherol, squalene and sterol characterization of deodorizer distillate samples. The author suggested that presence of high molecular weight species such as DAGs and TAGs make characterization very dicult. However, this technique was successful for the characterization of tocopherols, squalene and sterols. It may be possible to entirely characterize the distillate utilizing this method, but further research involving temperature and pressure must be carried out to compare the eects on the separation of all the components of the distillate. To illustrate this particular problem, Table 4 shows the thermophysical properties of some pure compounds found in soybean deodorizer distillates (Araujo, Machado, & Meireles, 2001). As can be seen in Table 4, the critical temperature and pressure for oleic and linoleic acid almost overlap. Another potentially expensive method has been developed by Ramamurthi and McCurdy (1993) involving lipase-catalyzed modication of fatty acids. This analysis was carried out on canola, mixed and soy distillates. The volatile fractions were removed by vacuum distillation, concentrating the tocopherol and sterol fractions. Their characterization was achieved using GC. However, the temperatures suggested by this method are not appropriate and did not provide good resolution of peaks. 3.3. Characterization of acid oil water Acid oil water is a by-product of vegetable oil rening that is heavily contaminated with fatty matter. Acid oil water has almost no economic value and as a consequence limited publications are available on this subject. To our knowledge, there are only two papers (Johansen, Sivasothy, Dowd, Reilly, & Hammond, 1996; Mag, Green, & Kwong,
Table 4 Critical temperature and pressure of pure compounds found in soybean deodorizer distillates Compounds Palmitic acid Oleic acid Linoleic acid a-Tocopherol Stigmasterol Squalene Critical temperature (C) 507 523 523 624 576 565 Critical pressure (atm) 14.5 12.3 12.2 8.09 9.09 6.44

1983) that actually report on acid oil water characterization. The main objectives for the above mentioned research was to characterize the mixture and lower the fat content. The fat content of waste water must be below 150 ppm in order to be discharged to municipal sewers (Mag et al., 1983). Mag et al. (1983) have studied the recovery of acid oil by continuous acidulation of soapstock. They have demonstrated that continuous acidulation of soapstock, decantation of the bulk acid oil from acid water and acid water treatment in a coalescer (for further separation of the emulsied acid oil) can reduce the fat content of acid water to below 150 ppm. Johansen et al. (1996) have analyzed acid water from soybean, canola, sunower, peanut, cottonseed and corn oil soapstock using three methods: (1) GC and electronionization MS, (2) GC and chemical-ionization MS and (3) HPLC with strong-acid ion exchange resin. With the exception of the lactic acid (obtained from anaerobic fermentation of soapstock or unrened vegetable oil), all identied peaks can be linked to components found in the plant tissues. All major low-molecular weight organic components that have been identied for each source of acid water are presented in Table 5. 4. Utilization of components from rening oil waste streams This section discusses the dierent valuable soapstock and deodorizer distillate compounds that are currently used for direct industrial applications or have been investigated for potential high-value and novel applications. 4.1. Soapstock and animal diet Soapstocks are increasingly being used as an animal feed additive, particularly in pig and poultry diets. It has no harmful eects (beyond gossypol) and can be used in a similar way to fat since it contains a high concentration of fatty acids. Gossypol is a toxic substance that needs to be removed from cottonseed soapstock sources prior to being used for animal feedstock. Extraction of gossypol will be covered in a later section. When soapstock is added into meal, it can improve the palatability, increase the energy density of the diet, reduce dust, help heat stress conditions, and improve pelleting of feed products by reducing feed particle separation. It also minimizes the build up of feed particles on equipment used for feed mixing at the mill. However, long chain fatty acids are dicult to digest in animals (Johnson & McClure, 1973), therefore soapstock must be added in small amounts (approximately 3.5%) (Bock et al., 1991). The percentage of polyunsaturated fatty acids contained in a soapstock mixture is another parameter that has to be taken into consideration. A broilers taste can depend on the percentage of polyunsaturated fatty acids in the diet (Lipstein, Bornstein, & Budowski, 1970). More recently (Pardio, Landin, Waliszewski, Badillo, & Perez-Gil, 2001), it has been shown that the addition of up to 1% of

964

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

Table 5 Major low-molecular weight organic compounds found in dierent sources of acid water Compounds Concentration (g/L) Canola Phosphoric acid a-Glycerophosphate b-Glycerophosphate Glycerol Myo-Inositol Myo-Inositol-1-phosphate a-Glycerophospho-1-myo-inositol 0.85 0.34 0.03 0.13 0.02 0.03 0.04 Corn 0.82 0.82 0.11 0.11 1.21 0.81 Cottonseed 0.07 12.4 6.17 19.4 3.63 6.31 0.20 Peanut 0.04 Trace 0.01 0.03 0.03 Soybean 0.79 0.55 0.40 0.47 0.44 0.75 1.18 Sunower 1.17 14.0 3.47 5.96 1.57 4.10 0.27

polyunsaturated fatty acids from soybean soapstock to broilers diet from one to seven weeks of age increased their weight by approximately 1.7 g. Cottonseed soapstock which is widely used to supplement animal diets contains gossypol, the predominant cottonseed plant pigment and major toxic ingredient (Adams, Geissman, & Edwards, 1960; Kovacic, 2003). As discussed earlier, in order to produce cottonseed edible oil, gossypol is typically removed during the oil rening process and ends up in the soapstock. Therefore, soapstock has to be added in a limited amount (Kuk & Tetlow, 2005) since 0.1% of gossypol is the upper limit that chickens can absorb without having growth rate problems (Lipstein & Bornstein, 1964a). A comparative study between acidulated cottonseed and soybean soapstocks in chicken feed has shown that chicken lipid oxidation is lower when the animals are fed with acidulated soybean soapstock (Bartov, Lipstein, & Bornstein, 1974). Soybean oil soapstock which is produced on a massive scale is considered to be a suitable substitute for soybean or corn oil in soybean meal-sorghum animal diets (Bartov et al., 1974) and does not aect the composition of hen egg yolk (Pardio et al., 2005). However, a recent study (Bruce et al., 2006) showed that the addition of soybean soapstock to pigs and roasters diet can decrease the amino acid digestibility and induce subsequent problems such as growth performance. 4.2. Biodiesel The use of biodiesel over conventional diesel has several advantages. It substantially decreases emission of carbon

dioxide, particulate matter, carbon monoxide, sulfur oxide, volatile organic compounds and unburned hydrocarbons but it increases nitrogen oxide emission which causes respiratory problems when found at the ground level (Fernando & Jha, 2006; Usta et al., 2005). Production of biodiesel reduces fuel costs by 25% in comparison to diesel (Haas, 2005), however, biodiesel cannot be produced in sucient quantity to meet the demand of a whole country. For example, only 14% of the US demand in diesel per year could be satised if all the animal and vegetable fat content in the country was utilized for its production (Van Gerpen, 2005). As previously mentioned, soapstocks are a good source of fatty acids, and are cheap in comparison to vegetable oil. Conversion of their FAs to FAMEs or fatty acid alkyl esters (FAAEs) has been studied for use in biodiesel formulations. Table 6 summarizes the major conversion methods investigated so far (Haas, Bloomer, & Scott, 2000; Haas, Michalski, Runyon, Nunez, & Scott, 2003a; Haas & Scott, 1996; Tuter, Aksoy, Gilbaz, & Kursun, 2004). Haas et al. (2000) and Haas et al. (2002) carried out the esterication of fatty acids from soapstock by saponication of glycerides and phosphoglycerides by alkaline hydrolysis followed by an acid-catalyzed esterication of the remaining salt of fatty acids. These steps ensure the total hydrolysis of the mixture. Complete esterication was achieved by adding FFA:methanol:acid in the proportion of 1:30:5. After 10 min, the reaction was 99% complete. This method requires subsequent washes with NaCl, NaHCO3 and Ca(OH)2 to remove the free fatty acids from the remaining solution (Haas et al., 2003a).

Table 6 Comparison between the dierent methods used for the conversion of fatty acids into fatty acids methyl esters or fatty acids alkyl esters Author Haas and Scott (1996) Tuter et al. (2004) Haas et al. (2000) Method Enzymatic catalysis Enzymatic catalysis Hydrolysisesterication Conversion FFA to FAAEs 63% FFA to FAAEs 50% to 63% Esterication completed at 99% Advantage of the method Not signicant Not signicant (1) Short reaction time (2) High esterication percentage (1) Low amount of solvent (2) No by-product Disadvantage of the method Low conversion factor Low conversion factor (1) (2) (3) (1) (2) (3) High amount of solvent Purication by washes By-product generated Purication by washes Needs two esterications Long reaction time

Haas et al. (2003)

Hydrolysisesterication

High level of esterication

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

965

The main drawback of the method is the formation of sodium sulfate in large amounts when acid is added to the soapstock alkaline solution. This by-product can lead to high disposal costs. Splitting soapstock with a strong acid (discussed later) is an ecient method for converting FFA to FAMEs without formation of sodium sulfate as by-product. The addition of acid to soapstock separates the mixture into two layers. The organic layer is mainly composed of FFA, acylglycerols, pigments and other lipophilic materials. In order to signicantly reduce the content of FFA in the organic layer, a saponication step prior to the addition of acid is carried out. This decreases the FFA content to >5% and is further reduced to 0.2% when a second esterication step is carried out (Haas et al., 2003a). Without saponication, the acid catalyzed method was unsuccessful for the esterication process resulting in 15% of FA remaining in the oil after 14 h (Haas et al., 2003a). It was found that varying the proportion of FFA:methanol:acid to 1:1.8:0.17 was benecial in comparison to the previous study (Haas et al., 2000). Conversion of soapstock into acid oil water is one of the best methods to use since it has a high conversion ratio, low solvent requirement and does not generate solid sodium sulfate in the product. Sodium sulfate is still created but it dissolves with the incorporation of acid and is removed with the water layer. A similar approach and recovery of methyl esters has also been reported by Marin, Mateos, and Mateos (2003). The conversion of FA into alkyl fatty acid esters by an enzymatic process has also been investigated. This route is the least ecient. Two research groups have found that for an initial mixture of soybean oil deodorizer distillate, the conversion was approximately 63% (Haas & Scott, 1996; Tuter et al., 2004) and using a mixture of corn oil deodorizer distillate, the conversion was found to be approximately 50% (Tuter et al., 2004). Using methanol with a catalyst, at a temperature of 80 200 C and a pressure higher than 17 atm, fatty acids are convert to their esters (Luxem & Troy, 2004a, 2004b), but this still does not signicantly improve upon the method developed by Haas, Scott, Michalski, and Runyon (2003b). 4.3. Drilling uids Drilling uids are mainly water-based or oil-based. Oil based drilling uids are essentially constituted of an oil phase generally comprised of diesel mineral oil, esters, nalkanes and olens, and an aqueous dispersed phase comprised of water, brine and alcohol. The remainder consists of organophilic clay, calcium chloride, brine, surfactants and weighting additives (copolymers and modied asphalts that control the rheological properties) (Quintero, 2002). Water based drilling uids are comprised of water, organophilic clay as a weighting agent and additives to give the desired properties. Although water-based drilling uid is more environmentally friendly, it has major disadvantages

compared to oil based drilling uids. Water-based drilling uid is generally less stable at higher temperatures and osmosis of water into the drilling formation causes borehole destabilization and corrosion of the drilling apparatus. Oil-based drilling uids are rich in non-degradable aromatic components and are very toxic for the environment, especially when used in oshore drilling where it is dicult to remove all the drilling mud from the cuttings (Durrieu, Zurdo, Rabion, Fraisse, & Guillerme, 2003; Goncalves, De Oliveira, & Aragao, 2004). There is limited literature available evaluating the use of soapstock and their derivatives in drilling uid preparations, and to our knowledge, no literature is available on the utilization of deodorizer distillate in drilling uid preparations. A possible reason for this could be that current research focuses on the recovery of tocopherols and sterols from deodorizer distillate, as already discussed in this review. Most research groups investigating the use of soapstock in drilling uid preparations are based in Eastern Europe and Russia, and focus on the use of cottonseed which is their domestic crop. The majority of work discussed in this section involves the use of soapstock or soapstock derivatives as additives to improve viscosity or rheological properties of the preparation. Typically, soapstocks are distilled and fatty acids are added to the drilling mud in concentrations varying from 2% to 25% (wt basis) (Kendis, Zakolodyazhnyi, & Roshchupkin, 1980; Leshchinskij & Davidenko, 1984; Mironenko, Kuksov, Parpiev, & Makhmudov, 1989; Motyleva et al., 1982; Zaionts et al., 1970). It is claimed that improvement of the adhesive and stability properties of the lubricant can be achieved via addition of hydrons from the distillation of fatty acids. Later on, it was found (Khasanov et al., 1988) that optimum results were achieved by adding hydrons in a proportion of 15% to 30% (mass). It has also been reported that the overall structural properties of commercial water-based well drilling uids can be enhanced by addition of soapstock (Klimashkin, Polyakov, Khashimov, Mamadzhanov, & Khodzhaeva, 1984), sulfate soap (Kendis et al., 1980) and lubricating additives (Motyleva et al., 1982). Other research groups have utilized derivatives of soapstock as drilling uid additives (Aronova, Zainutdinov, Sataev, & Akhmedov, 1977) and evaluated the use of polyethylene glycol monoesters of fatty acids, recovered from cottonseed soapstock, as a surfactant for clay based drilling uids. It was found that at the level used (0.25% wt basis), the soapstock additive was able to reduce both viscosity and shear stress. However, it has a tendency to form soaps in an alkali medium which is a concern as most drilling uids are alkali in nature. Literature on the use of soapstock and soapstock derivatives in drilling uid compositions is focused on cottonseed and castor oil, other oil sources have yet to be evaluated. The existing literature was published between 1970 and 1989 and the research was mainly conducted in Russia, where cottonseed and castor are readily available.

966

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

Therefore, it is necessary to investigate soapstock and deodorizer distillates from other seed sources such as linseed and canola, which are rich in free fatty acids. The use of such a cheap feedstock in conjunction with an invert emulsion or a synthetic base emulsion could decrease the economic burden and thus increase the use of these environment friendly bases. However, the use of soapstock has many shortcomings. First, the ester based oil formulations currently available contain mostly C12C16 fatty acids with limited C18 fatty acids and have high pour points. Any addition or substitution of long chain saturated fatty acids, which are known to impart high melting points, will lead to higher pour points (Mueller et al., 1999). For these reasons, the use of canola and ax soapstock and deodorizer distillate in the drilling uid compositions could lead to several problems. As reported in the literature, fatty acid content of soapstock and deodorizer distillate is a reection of the parent oil composition (Dowd, 1998). In addition, canola and linseed oils consist mainly of long chain C18 fatty acids, which are detrimental to the pour point. The high content ($80%) of unsaturated fatty acids in canola and linseed ($90%) result in them having lower melting points than their saturated counterparts. This could potentially lessen the problem of pour point but introduce the problem of oxidative instability. Oxidation which triggers the breakdown of the carbon chain structure increases with the increase of the number of double bonds and could lead to alterations in the rheological properties of the drilling uid if it occurs to an appreciable extent. Many additives are utilized in the production of drilling uid to impart desired physical properties. There is potential for utilization of fatty acids obtained from soapstocks and deodorizer distillates to synthesize additives to replace existing additives that confer toxicity to the nal formulation. Possible additives that could be synthesized from fatty acids derived from soapstock and deodorizer distillate include emulsiers (fatty acids, fatty acid soaps and fatty acid derivatives), oil wetting agents (fatty acids, crude tall oil) and rheology modiers (fatty acids and polymeric fatty acids) (Ellice, Helmy, & Shumate, 1996). Tapping into such an economical source of fatty acids for direct use as base oils in drilling uid preparations or for the synthesis of additives could be commercially protable. It would therefore be possible, in addition to economic gains, to address some environmental issues surrounding drilling uids. Following the strong current trend to develop environmentally acceptable replacements for the petroleum and mineral oil based drilling uids, interest towards the potential of deodorizer distillates and soapstocks of oil rening as sources of fatty acids is rapidly increasing. Current research is primarily focused on the use of cottonseed and castor soapstocks in the drilling operations. Waste streams of canola and axseed oil reneries have limited use and research into their uses in drilling operations has potential. Further research on these sources will hopefully provide the drilling industry with economical and environ-

mentally friendly alternatives to petroleum based drilling uids. 4.4. Specialized applications This section covers multigrade lubricating greases, gossypol, biosurfactants and derived lms. Despite the limited literature on derived lms, this subject has been added due to its importance in medical applications. 4.4.1. Multigrade lubricating greases Multigrade lubricating greases are used in many sectors like the automotive, machine tools and electrical motor sectors. They are semi-solid colloidal compounds basically composed of uid lubricant and a gelling agent (thickener). The thickener is a soap or a non-soap component that holds the uid lubricant and additives together. Soap thickeners are essentially composed of fatty acid soaps of lithium, calcium, sodium, aluminum or barium. The chemical structure, viscosity and rheological properties of lubricating greases have a direct impact on their performance (Adhvaryu, Sung, & Erhan, 2005; Delgado, Valencia, Sanchez, Franco, & Gallegos, 2006; Leslie, 1998). The use of fatty acids from soapstock as a thickener for multigrade lubricating grease has been investigated by El-Adly (2000) and Al-Wakeel and El-Adly (2005). Soapstock is treated with alkali (saponication) to recover fatty acids prior to their addition to lubricating oil. The addition of cottonseed soapstock increases the viscosity of the oil and it behaves like a Bingham plastic. This high viscosity is due to the sodium salt of soapstock which forms crystals and a brous structure (El-Adly, 2000). The chemical and physical properties of the grease can be modied by adding oil shale ller, which is a dark ne-grained sedimentary rock composed of layers of compressed clay, silt, or mud. The described method in which new greases are formed through addition of fatty acids obtained from soapstock is a cheap process. However, interest in developing this methodology has been limited to one group of researchers (Al-Wakeel & El-Adly, 2005). 4.4.2. Biosurfactants Soapstock and post-renery fatty acids have been used as substrates for glycolipid (Bednarski, Adamczak, Tomasik, & Plaszczyk, 2004) and rhamnolipid biosynthesis (Benincasa, Contiero, Manresa, & Moraes, 2002). The aim is to create a microbiological surfactant with standard characteristics such as antimicrobial activity, non-toxicity, biodegradability, capacity of reducing surface and inter-phase tension as well as reduce the production cost. Production of the rhamnolipid biosurfactant has been achieved using sunower oil soapstock. The addition of soapstock and post-renery fatty acids as substrates for glycolipids biosynthesis by yeast has shown positive eects. A 70% yield has been achieved (Benincasa, Abalos, Oliveira, & Manresa, 2004) for the production of rhamnolipid biosurfactants. Also, production of rhamnolipids has been achieved using

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

967

soybean soapstock with a yield of 75% (Nitschke et al., 2005). Research in this area is economically interesting since it does not involve modication of soapstock. 4.4.3. Fatty acid modication diacylglycerols (DAG) Fatty acids, the main component of deodorizer distillates, are mostly used as additives for animal food, as medium-grade soaps for laundry and dry cleaning operations, building maintenance and industrial cleaners, car wash liquids, cutting oils, plus food and dairy plant cleaners (Sonntag, 1985). DAGs are valuable compounds which can be produced from the modication of fatty acids from deodorizer distillate. Some DAGs can prevent body fat accumulation and recent research has involved investigating their role in the prevention of diabetes (Mori et al., 2005; Nagata & Saito, 2006). DAGs also have application in the food and cosmetic industries. It has been shown (Lo, Baharin, Tan, & Lai, 2004a; Lo, Baharin, Tan, & Lai, 2004b) that the production of 1,3-DAG from corn oil and soybean deodorizer distillates is possible by lipase-catalyzed esterication of glycerol with fatty acids. However, comparison of the cost of enzyme versus the cost of nal product (DAGs) makes the method economically unfeasible. Since DAGs are fairly cheap, the literature covering their synthesis from fatty acids is limited. 4.4.4. Derived lms Soapstock derived lms from cottonseed and saower soapstock have been considered as potential materials for chemical encapsulation or target delivery in animals and humans because of their zwitterionic properties (Kuk & Ballew, 1999). Soapstocks are freeze-dried to remove low boiling point components and solvents. The soapstock is then submitted to a mechanical pulverization process where ne particles are created. These ne particles are then dissolved in a solvent and cast at room temperature, dried in the atmosphere and separated from the substrate. Applying this simple procedure on cottonseed and safower soapstock (Kuk & Ballew, 1999), produced a lm having similar lipid composition (phosphatidylcholine 25 35%, phosphatidylethanolamine 1525% and phosphatidylinositol 510%) as the lms used for drug delivery in humans. The lm has also been considered for cosmetics and dermal drug applications since it is water soluble and forms a mesophase. However, the source of soapstock used must be free from gossypol and an extra step is required to remove this toxic compound from cottonseed soapstock. 5. Extraction of valuable components from soapstocks and deodorizer distillates 5.1. Soapstock Soapstock has a variety of end uses, such as a nutrient source for microorganisms, feedstock for chemical reac-

tions, fertilizer ingredient and more importantly fatty acid source for biodiesel and animal feedstock. This section will deal with the extraction of fatty acids and gossypol. As mentioned earlier, gossypol is a toxic substance that needs to be removed from cottonseed soapstock sources prior to being used for animal feedstock. 5.1.1. Extraction of fatty acids Fatty acids are the major component of soapstock, after water has been extracted. They represent approximately 10% of the soapstock composition on a wet basis. As fatty acids are mainly used in animal feed, the extraction process must be cheap in order to be justied. These fatty acid recovery methods include: organic solvent extraction, supercritical uid extraction (SFE) using CO2 coupled with an enzymatic-based reaction and soapstock splitting using a mineral acid. These literature methods, however, do not specify how the waste is disposed of after extraction. AOCS method G3-53 reports the saponication of soapstock followed by acidulation as a fatty acid recovery method. This method is ecient at recovering the fatty matter but does require 575 mL of petroleum ether for every 10 g of soapstock. In order to reduce the amount of solvent used, King, Taylor, Snyder, and Holliday (1998) compared fatty acid material recovered by the G3-53 method and a SFE/SFR (supercritical uid reaction) method. Table 7 shows the result of fatty matter/fatty acid recovery for three samples of soapstock (soybean (a), soybean (b) and corn (c)) using the above mentioned methods. It is clear from Table 7 that the two methods result in a similar average of the recovered matter. Although the SFE/ SFR method in this study only required 1.8 mL of solvent, it is not economically viable compared to method G3-53 due to the cost of expensive enzymes also used in the process. Furthermore, the authors have found a signicant difference in the percentage of fatty acid recovery between the two soybean soapstock samples. As these two samples were obtained from two dierent companies, it can be assumed that one of the samples has been chemically modied or treated by a dierent processing method. Slight dierences can occur in terms of concentration of components within the same type of soapstock but from Dowds research
Table 7 Comparison of fatty matterfatty acid recovery using AOCS method G3/ 53 and SFE/SFR Soapstock type Soybean-based soapstock (a) G3-53 (%) Average: 31.05 SD: 0.48 RSD: 1.55 Average: 11.03 SD: 0.02 RSD: 0.19 Average: 38.84 SD: 0.86 RSD: 2.22 SFE/SFR (%) Average: 32.63 SD: 0.24 RSD: 0.72 Average: 12.28 SD: 0.07 RSD: 0.60 Average: 39.52 SD: 0.33 RSD: 0.84

Soybean-based soapstock (b)

Corn oil-based soapstock (c)

SD: Standard deviation, RSD: relative standard deviation.

968

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

(Dowd, 1996) which reports the characterization of soapstock from dierent regions, it can be seen that signicant dierences in percentage of components is unlikely. Another way of extracting fatty acids has been developed by Haas, Cichowicz, Jun, and Scott (1995). It requires the use of the lipase, Lipozyme I-20, to achieve hydrolysis of all the TAGs, 70% of the phosphatidylethanolamine and 20% of the phosphatidylcholine present in soybean soapstock samples. The method required a high ratio of organic solvent to soapstock (8 mL/0.5 g) and an appreciable amount of lipase (50 mg). This method is therefore not recommended for the extraction of a low-value compound such as fatty acids. In industry, the main process used for fatty acid extraction is called soapstock splitting and is commonly used because it is a low cost, facile method. The general process consists of soapstock acidulation with sulfuric acid and then separation of fatty matter from the acid water (Gervajio, 2005). However, sulfuric acid is very severe on the hardware used in the process. The corrosion of pipes can occur because of the use of concentrated acid, and this has been addressed in some patents and papers (Asbeck & Walter, 1991; Du & Segers, 1982; Gadefaix & Klere, 1974; Oester, Hall, Zilch, & Anderson, 1997; Piazza & Haas, 1999). To date, this is the most cost-ecient method. 5.1.2. Extraction of gossypol Gossypol has been a compound of interest since the early 20th century. It is a polyphenolic compound which is present in cottonseed soapstock (Fig. 3). It has been found that acidulated soapstock stored at room temperature for a period of 6 to 10 months decreases gossypol content from 80% to 50%. The authors related the gossypol decrease with its duration in a basic mixture (Lipstein & Bornstein, 1964b). There is a method that allows a partial recovery with high purity of this minor component from soapstock. It consists of acid treatment to hydrolyze covalently bonded gossypol, partitioning of gossypol into an organic phase and then washing the residue several times. The gossypol
OH OH O O OH HO HO CH(CH 3 ) 2

is then concentrated by vacuum distillation and nally crystallized. This process led to a recovery of approximately 58% gossypol with a purity of 99% after a single recrystallization (Dowd & Pelitire, 2001). Gossypol has anti-tumor (Xu et al., 2005) and anti-viral properties (Keller, Birch, Leach, Tyssen, & Grith, 2003) and hence research in this area has attracted great interest. 5.2. Extraction of deodorizer distillate components Literature on the characterization is mainly based on the identication and quantication of tocopherol and sterol content in deodorizer distillates and deals with their extraction and recovery. Although, there are some isolated publications or patents reported investigating the extraction of brassiscasterol from rapeseed distillates, such as Kirchers paper (Kircher & Rosenste, 1973). 5.2.1. Extraction of tocopherols, sterols and squalene Extensive research has been carried out to determine the best methods to extract and recover tocopherol from distillates. This recovery can be a worthy process because the vegetable oil rening process leads to a signicant tocopherol loss from the crude oil to the deodorizer distillate. The majority of tocopherol loss occurs during the deodorization process (Copeland & Belcher, 2003; Verleyen et al., 2002) where the amount of tocopherol decreases by 23% (Gogolewski, Nogala-Kalucka, & Szeliga, 2000). The neutralization and bleaching steps together cause a loss of approximately 10.1% of tocopherol (Gogolewski et al., 2000). The four isomers of tocopherol (a, b, c and d) (Fig. 4) are generally found in the distillate mixture and are also known as vitamin E. Tocopherols must be concentrated to 60% and free from fatty acids in order to be sold as vitamin E. The presence of squalene (Fig. 5) is not detrimental to the tocopherols mixture; however the cost of vitamin E increases with its purity. Squalene is itself an important commercial compound that is found in the distillates and is generally used in the cosmetic industry as a moisturizer. These minor components have excellent commercial value. The main challenge is to separate them from each other, especially in the case of the following pairs of components: tocopherolsqualene, tocopherolfatty acids, tocopherolsterol and sterolsqualene. To separate these components, the literature proposes these main methods: solvent extraction and crystallization (Lin & Koseoglu, 2003; Moreira & Baltanas, 2004), supercritical carbon dioxide extraction (SC-CO2) (Buczenko, de Oliveira, & von Meien, 2003; Chang, Chang, Lee, Lin, & Yang, 2000; Mendes, Pessoa, Coelho, & Uller, 2005; Mendes, Pessoa, & Uller, 2002; Mendes, Uller, & Pessoa, 2000; Nagesha, Manohar, & Sankar, 2004; Wang, Goto, Sasaki, & Hirose, 2004), enzymatic reaction (Nagao et al., 2005; Ramamurthi, Bhirud, & McCurdy, 1991; Shimada et al., 2000; Watanabe, Nagao, Hirota, Kitano, & Shimada, 2004; Weber, Weitkamp, & Mukherjee, 2002) and the

HO CH(CH 3 ) 2

Fig. 3. Chemical structure of gossypol.

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

969

(A)
HO

(B)
HO

(C)

HO

(D)

HO

Fig. 4. Chemical structures of (a) a-tocopherol, (b) b-tocopherol, (c) c-tocopherol and (d) d-tocopherol.

pressure, but the amount of solvent required is still very high and the use of such quantities does not lead to an environmentally friendly process. It is also noted that extraction with solvent requires laborious manipulations. Research in this area is not very extensive due to the low recovery and low purity of sterols and tocopherols (Moreira & Baltanas, 2004; Lin & Koseoglu, 2003). 5.2.1.2. Supercritical uid extraction. Supercritical carbon dioxide extraction is a process where carbon dioxide passes through a mixture of interest at a certain temperature and pressure until it reaches an extractor. This process is used because supercritical carbon dioxide has a low viscosity, a high diusivity and a low surface tension that provides selective extraction, fractionation and purication, allowing its penetration in micro- and macro-porous materials. The major advantage of this method is the easy post-reaction separation of the components by depressurization. Another advantage is the low temperatures used for the majority of the experimentations because carbon dioxide has a critical temperature of 31.1 C (see Fig. 6). However, the use of high pressure conditions makes the system energetically expensive but can be economically viable at a rate of production superior to 25% using conditions of approximately 90 atm and 40 C (Mendes et al., 2002). At these

Fig. 5. Chemical structure of squalene.

molecular distillation process (Martins, Batistella, MacielFilho, & Wolf-Maciel, 2006; Martins, Ito, Batistella, & Maciel, 2006). However, all of these methods are at a trialerror stage and there is no literature available as yet that actually conrms the total separation of all of these compounds. 5.2.1.1. Solvent extraction and crystallization. Solvent extraction and crystallization are mainly used to recover sterols over tocopherols. This process has the advantage of not causing tocopherol oxidation and does not use high

970

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

120 100 Pressure (atm) 80 60 40 20 0 1 6 11 16 21 26 31 36 41 Temperature C Gas Liquid Supercritical Fluid

Fig. 6. Phase diagram of carbon dioxide.

specic conditions, only fatty acids are separated from tocopherol (Mendes et al., 2005). An increase in pressure and temperature increases the oil extraction and tocopherol recovery, although dierent pressuretemperature systems need to be used in order to separate the dierent components. Chang et al. (2000) worked on the separation of several distillate components. Their supercritical uid extraction apparatus had a separation and an extraction unit. Free fatty acids, squalene and tocopherols were recovered in the extract and the sterols were recovered in the ranates. The average tocopherol concentration factor was 1.38, which means that the mixture in the extract did not separate. However, the author mentioned that with the increase of CO2 volume, the separation factor can reach 1.7, but the poor increase in the concentration factor does not justify the raise in gas volume. The following research groups focused on the separation of the problematic pairs using synthetic mixtures: Mendes et al. (2000), Mendes et al. (2005), Wang et al. (2004), Nagesha et al. (2004), Ramamurthi et al. (1991), Shimada et al. (2000), Watanabe et al. (2004), Nagao et al. (2005), Weber et al. (2002), Martins, Batistella, et al. (2006), Martins, Ito, et al. (2006), Sumner, Barnicki, and Dol (1995), Nagesha, Subramanian, and Sankar (2003) and Maza (1992).

Table 8 summarizes the yield and concentration factor (C.F.) of pairs of compounds at dierent conditions of pressure (P) and temperature (T) obtained by Mendes and Chang. There are some interesting relationships and conclusions that can be deduced from this table. The binary mixture of tocopherol and squalene cannot be separated at low pressure conditions. An acceptable separation needs a raise in pressure to almost 200 atm (Mendes et al., 2005; Mendes et al., 2000). However, a recovery of 90% and a purity of 60% of a-tocopherol has been achieved using a pressure swing adsorption device, where the adsorption and desorption steps had pressure conditions of 158 and 296 atm, respectively (Wang et al., 2004). The ternary mixture of tocopherol, fatty acids and squalene behaved dierently from the tocopherolfatty acid binary mixture. For the same conditions of pressure (158 and 296 atm), the binary mixture had a total separation while the ternary mixture did not achieve any separation. Squalene and stigmasterol mixtures are also very dicult to separate. At low pressure conditions, the yield is less than 10% but at higher pressure, the yield is 76% although the compounds do not separate. It is important to note that low temperatures were used in these studies. A simulation of the phase equilibrium between the distillate components in a CO2 system using the Peng-Robinson Equation of State (EOS) model showed that at 70 C, the separation factor between fatty acids and squalene from tocopherols and sterols in soybean oil deodorizer distillates decreases as the pressure increases. The partition coecient (K) of several distillate compounds decreases following this order: squalene > fatty acids > tocopherols > stigmasterol (Araujo et al., 2001). Eq. (3) shows the Peng-Robinson Equation of state: P RT aT 2 V m b V m 2V m b b2 3

where P is the pressure, R the ideal gas constant, Vm the molar volume, and a and b are parameters related to the partition parameters between the dierent species. Table 8 suggests that the supercritical-CO2 process could be used for the separation of squalene, fatty acids

Table 8 Comparison between the yield and concentration factor (C.F.) of pairs of compounds and the dierent conditions of pressure (P) and temperature (T) used Mixture Chang et al. (2000) Mendes et al. (2000) Soybean deodorizer distillate 50% a-Tocopherol50% squalene 10% a-Tocopherol20% squalene70% fatty acids T (C) 90 top 70 bottom 80 39 80 39 80 40 40 40 40 40 P (atm) 306 148 89.0 148 89.0 148 89.0 345 345 148 89.0 Yield (%) 83.6 30.0 34.6 49.1 34.6 49.1 93.1 91.0 94.0 76.1 9.20 C.F. 1.38 1.23 a-Tocopherolsqualene: 16.7 a-Tocopherolsqualene: 1.80 a-TocopherolFA: 0.57 a-TocopherolFA: 1.03 Innite 55.4 104 1.00 8.60

Mendes et al. (2005)

TocopherolFA Tocopherolsqualene Tocopherolstigmasterol Squalenestigmasterol Squalenestigmasterol

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974

971

and tocopherols. In order to enhance the squalene, fatty acids and tocopherols separation, deodorizer distillate mixtures should be processed several times in supercritical-CO2 at dierent temperature and pressure conditions. However, there is no data reported regarding the reaction time of the mixture and this makes it impossible to estimate the operational cost. The major advantage of this method is the total removal of free fatty acids from the mixture. Other methodologies have been looked at but were unsuccessful for the separation of dierent pairs of components. An attempt at using similar methodology to Mendes et al. (2000) and Mendes et al. (2005) but using liquid gas petroleum instead of carbon dioxide did not change the poor concentration factor between the critical pairs of components (Buczenko et al., 2003). Another methodology was developed to focus more specically on the conversion of FFAs into fatty acid butyl esters (FABEs) (Nagesha et al., 2004). The authors (Nagesha et al., 2004) used immobilized Mucor miehei lipase in supercritical carbon dioxide at high pressure and obtained a maximum recovery of 88% and a FABE purity of 95%. 5.2.1.3. Enzymatic reaction. Enzymatic reactions are based on the principle of using enzymes for the conversion of a class of components into a dierent class in order to modify the chemical or physical characteristics of the original compound. The utilization of enzymes permits the concentration of tocopherols from the distillates by converting sterols to steryl esters, acylglycerols to free fatty acids and free fatty acids to fatty acid methyl esters (FAMEs). It is then easier to separate the components that have similar molecular weight by distillation. From published literature, it can be seen that the main disadvantages of the process are the numerous parameters such as moisture content, enzyme concentration, time, temperature and ratio of the reactants (Ramamurthi et al., 1991). The optimal conditions for these reactions have yet to be determined. Distillation of the deodorizer distillate mixture allows for the removal of high boiling point components such as fatty acid steryl esters, DAGs and TAGs. However, this distillation step can be carried out after the esterication of sterols and FFA, without signicantly aecting their conversion into steryl esters and FAMEs. The conversion of FFAs to FAMEs is an important step in the concentration and purication of tocopherols. If this step is omitted, the separation of FFA and tocopherols by distillation cannot be achieved due to their similar boiling points (Shimada et al., 2000). Furthermore, methanol used for the conversion of FFA to FAMEs inhibits sterol esterication. To avoid this problem, a lipase can be used to promote the esterication of sterols with free fatty acids and hydrolysis of acylglycerols should be carried out before esterication of the free fatty acids. The dierent components are then successfully separated by short path distillation since their boiling points are now suciently dierent. Two research groups (Nagao et al., 2005; Watanabe et al., 2004) have applied this procedure using Candida lipase for

the purication of tocopherol in soy oil deodorizer distillates. Both groups report a tocopherol purity of approximately 75% and a yield of approximately 88%. The conversion of sterols into their esters was 97% and their recovery was approximately 86%. One of the main disadvantages of this method is that the free fatty acids are not completely separated from the tocopherols. This method is also a time consuming process that requires a high ratio of solvent to lipase, both of which are expensive. Weber et al. (2002) has also reported the use of lipase for the conversion of sterols into steryl esters leading to a higher degree of purity (90%), however the methodology is more complex and involves deacidication, ash chromatography and solvent fractionation. 5.2.1.4. Molecular distillation. Molecular distillation allows for the separation of components by short exposure of a mixture to an elevated temperature under high vacuum conditions. Saponication of the distillate prior to molecular distillation raises the tocopherol recovery from 73.4% to 85.8% (Martins, Ito, et al., 2006). The major disadvantage in this case is the residual free fatty acids in the tocopherol mixture despite their signicant boiling point dierence (Martins, Batistella, et al., 2006; Martins, Ito, et al., 2006). This process is the most time ecient and economical method, however high purity of sterols or tocopherols cannot be achieved due to the similar boiling points of the components. 5.2.1.5. Other methods. There have also been limited literature reported on the following methods: (1) permeation of tocopherols from deodorizer distillates using a non-porous denser polymeric membrane (Nagesha et al., 2003), and (2) concentration of tocopherols and sterols by addition of melted deodorizer distillates to a solution of urea and alcohol which separate fatty acids from the mixture (Maza, 1992). Since these methods do not present any advantages over the main methods, they will not be discussed further. 6. Conclusion Literature on the characterization of soapstock and deodorizer distillates is very limited and only a few types of raw materials have been investigated. The bulk of the research carried out on soapstocks focuses on fatty acid utilization or transformation and research carried out on deodorizer distillates focuses on tocopherol extraction. However, economical information is missing for the extraction of tocopherols from distillates. The majority of literature found on the transformation of fatty acids from soapstock concerns principally biodiesel. Several methods that have been developed for the conversion of fatty acids into FAMEs show favorable results. Unfortunately, no economical viability has been assessed and no comparison between the methods has been carried out. This is critical missing information if the production of biodiesel from seed oil wastes is to be upgraded to an

972

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974 Bock, B. J., Brandt, R. T., Harmon, D. L., Anderson, S. J., Elliott, J. K., & Avery, T. B. (1991). Mixtures of wheat and high-moisture corn in nishing diets feedlot performance and in situ rate of starch digestion in steers. Journal of Animal Science, 69, 27032710. Bruce, K. J., Karr-Lilienthal, L. K., Zinn, K. E., Pope, L. L., Mahan, D. C., Fastinger, N. D., et al. (2006). Evaluation of the inclusion of soybean oil and soybean processing by-products to soybean meal on nutrient composition and digestibility in swine and poultry. Journal of Animal Science, 84, 14031414. Buczenko, G. M., de Oliveira, J. S., & von Meien, O. F. (2003). Extraction of tocopherols from the deodorized distillate of soybean oil with liqueed petroleum gas. European Journal of Lipid Science and Technology, 105, 668671. Chang, C. J., Chang, Y.-F., Lee, H.-z., Lin, J.-q., & Yang, P.-W. (2000). Supercritical carbon dioxide extraction of high-value substances from soybean oil deodorizer distillate. Industrial & Engineering Chemistry Research, 39, 45214525. Cheryan, M. (1998). Ultraltration and microltration handbook (2nd ed.). Lancaster, PA: Technomic Pub. Co., p. 527. Cmolik, J., & Pokorny, J. (2000). Physical rening of edible oils. European Journal of Lipid Science and Technology, 102, 472486. Copeland, D., & Belcher, M. W. (2003). Methods for recovery of fatty acids, tocopherols and sterols from oil deodorizer distillates, 2003-US 8463. Cvengros, J. (1995). Physical rening of edible oils. Journal of the American Oil Chemists Society, 72, 11931196. De Greyt, W. F., Petrauskaite, V., Kellens, M. J., & Huyghebaert, A. D. (1998). Analysis of tocopherols by gasliquid and high-performance liquid chromatography: A comparative study. Fett-Lipid, 100, 503507. Delgado, M. A., Valencia, C., Sanchez, M. C., Franco, J. M., & Gallegos, C. (2006). Inuence of soap concentration and oil viscosity on the rheology and microstructure of lubricating greases. Industrial & Engineering Chemistry Research, 45, 19021910. Dowd, M. K. (1996). Compositional characterization of cottonseed soapstocks. Journal of the American Oil Chemists Society, 73, 12871295. Dowd, M. K. (1998). Gas chromatographic characterization of soapstocks from vegetable oil rening. Journal of Chromatography A, 816, 185193. Dowd, M. K., & Pelitire, S. M. (2001). Recovery of gossypol acetic acid from cottonseed soapstock. Industrial Crops and Products, 14, 113123. Du, A. J., & Segers, J. C. (1982). Continuous soap stock splitting, US 4361517. Durant, A. A., Dumont, M.-J., & Narine, S. S. (2006). In situ silylation for the multicomponent analysis of canola oil by-products by gas chromatographymass spectrometry. Analytica Chimica Acta, 559, 227233. Durrieu, J., Zurdo, C., Rabion, A., Fraisse, L., & Guillerme, M. (2003). Process for using biodegradable drilling muds, US 6634442. El-Adly, R. A. (2000). Producing multigrade lubricating greases from animal and vegetable fat by-products. Synthetic Lubrication, 16, 323332. El-Shattory, Y. (1979). Statistical studies on physical and chemical characteristics, phospholipids and fatty acid constitution of dierent processed cottonseed soapstocks. Revue Francaise des Corps Gras, 26, 187190. Ellice, M., Helmy, S., & Shumate, T. G. (1996). Base oil for wellbore uids, GB 2297103. Feeter, D. K. (1974). Determination of tocopherols, sterols, and steryl esters in vegetable oil distillates and residues. Journal of the American Oil Chemists Society, 51, 184187. Fernando, S. H. C., & Jha, S. (2006). NOx reduction from biodiesel fuels. Energy & Fuels, 20, 376382. Firestone, D. (1998) (5th ed.). Methods and recommended practices of the American Oil Chemists Society (Vol. 5). Champaign, IL: AOCS Press, sections B, C and G.

industrial scale. Fatty acids from deodorizer distillates have not been considered for the production of biodiesel. At this point, for comparison purposes, it might be legitimate to try to make FAMEs from the distillates using the methods applied for the production of FAMEs from soapstock. Except for the direct use of soapstock in animal feeds, a limited number of papers have been published on this subject. Other utilization and transformations of the by-product are still at a primary stage. Although, these applications are original and so far successful, more research should be carried out for a full exploitation of soapstock and deodorizer distillate by-products. Acknowledgements The nancial support of Alberta Crop Industry Development Fund, NSERC, Bunge Corp., AVAC Ltd. and Archer Daniels Midland is gratefully acknowledged. We would also like to thank Drs. Xiaohua Kong and Hayley Wan for editing help. References
Adams, R., Geissman, T. A., & Edwards, J. D. (1960). Gossypol, a pigment of cottonseed. Chemical Reviews, 60, 555574. Adhvaryu, A., Sung, C., & Erhan, S. Z. (2005). Fatty acids and antioxidant eects on grease microstructures. Industrial Crops and Products, 21, 285291. Al-Wakeel, M. I., & El-Adly, R. A. (2005). A novel application of Egyptian oil shale as a ller in the production of lithium lubricating grease. Energy Sources, 27, 15111522. Anderson, A. J. C. (1953). Rening of oils and fats for edible purposes. London, New York: Academic Press, p. 204. Araujo, M. E., Machado, N. T., & Meireles, M. A. A. (2001). Modeling the phase equilibrium of soybean oil deodorizer distillates + supercritical carbon dioxide using the Peng-Robinson EOS. Industrial & Engineering Chemistry Research, 40, 12391243. Aronova, N. N., Zainutdinov, S. A., Sataev, I. K., & Akhmedov, K. S. (1977). Regulation of structure-formation processes in drilling uids using polyethylene glycol monoesters of soap stock fatty acids. In N. N. Kruglitskii (Ed.), Dispersnye Sistemy Bureniia (pp. 151152). Kiev: USSR Naukova Dumka. Asbeck, L. S., & Walter, W. L. (1991). Process for soap splitting without emulsion formation using a high temperature treatment, AN 104746. Bartov, I., Lipstein, B., & Bornstein, S. (1974). Dierential eects of dietary acidulated soybean oil soapstock, cottonseed oil soapstock and tallow on broiler carcass fat characteristics. Poultry Science, 53, 115124. Bednarski, W., Adamczak, M., Tomasik, J., & Plaszczyk, M. (2004). Application of oil renery waste in the biosynthesis of glycolipids by yeast. Bioresource Technology, 95, 1518. Benincasa, M., Abalos, A., Oliveira, I., & Manresa, A. (2004). Chemical structure, surface properties and biological activities of the biosurfactant produced by Pseudomonas aeruginosa LBI from soapstock. Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 85, 18. Benincasa, M., Contiero, J., Manresa, M. A., & Moraes, I. O. (2002). Rhamnolipid production by Pseudomonas aeruginosa LBI growing on soapstock as the sole carbon source. Journal of Food Engineering, 54, 283288. Bhosle, B. M., & Subramanian, R. (2005). New approaches in deacidication of edible oils a review. Journal of Food Engineering, 69, 481494.

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974 Gadefaix, R., & Klere, J. (1974). Splitting soapstock and apparatus for this, SU 3787460. Gervajio, G. C. (2005). Fatty acids and derivatives from coconut oil. Baileys Industrial Oil and Fat Products (6th Edition), 6, 156. Gogolewski, M., Nogala-Kalucka, M., & Szeliga, M. (2000). Changes of the tocopherol and fatty acid contents in rapeseed oil during rening. European Journal of Lipid Science and Technology, 102, 618623. Goncalves, J. T., De Oliveira, M. F., & Aragao, A. F. L. (2004). Compositions of oil-based biodegradable drilling uids and process for drilling oil and gas wells, US 2004002427. Haas, M. J. (2005). Improving the economics of biodiesel production through the use of low value lipids as feedstocks: Vegetable oil soapstock. Fuel Processing Technology, 86, 10871096. Haas, M. J., Bloomer, S., & Scott, K. (2000). Simple, high-eciency synthesis of fatty acid methyl esters from soapstock. Journal of the American Oil Chemists Society, 77, 373379. Haas, M. J., Bloomer, S., & Scott, K. (2002). Saponication and esterication process for the production of fatty acid alkyl esters from glyceridic oils or fats, US 6399800. Haas, M. J., Cichowicz, D. J., Jun, W., & Scott, K. (1995). The enzymatichydrolysis of triglyceridephospholipid mixtures in an organic-solvent. Journal of the American Oil Chemists Society, 72, 519525. Haas, M. J., Michalski, P. J., Runyon, S., Nunez, A., & Scott, K. M. (2003a). Production of FAME from acid oil, a by-product of vegetable oil rening. Journal of the American Oil Chemists Society, 80, 97102. Haas, M. J., & Scott, K. M. (1996). Combined nonenzymaticenzymatic method for the synthesis of simple alkyl fatty acid esters from soapstock. Journal of the American Oil Chemists Society, 73, 13931401. Haas, M. J., Scott, K. M., Michalski, P. J., & Runyon, S. (2003b). Lipid rich compositions, production of lipid rich compositions, production of fatty acid alkyl esters from heterogeneous lipid mixtures, 2003US602. Hadi, A., Pioch, D., & Ajana, H. (2005). Membrane-based simultaneous degumming and deacidication of vegetable oils. Innovative Food Science & Emerging Technologies, 6, 203212. Hartman, L. (1978). Deacidication of edible oils by short path distillation. Rivista Italiana delle Sostanze Grasse, 55, 191192. Hiraldo, A. M., Herrera, C. G., Luque, V. F., & Montes, C. G. (1989). Rheological characterization of sunower oil soapstocks. Revue Francaise Des Corps Gras, 36, 7177. Johansen, S. L., Sivasothy, A., Dowd, M. K., Reilly, P. J., & Hammond, E. G. (1996). Low-molecular weight organic compositions of acid waters from vegetable oil soapstocks. Journal of the American Oil Chemists Society, 73, 12751286. Johnson, R. R., & McClure, K. E. (1973). High fat rations for ruminants. 2. Eects of fat added to corn plant material prior to ensiling on digestibility and voluntary intake of silage. Journal of Animal Science, 36, 397406. Keith, F. W., Bell, V. G., & Smith, F. H. (1955). Continuous purication and acidulation of vegetable oil soapstock. Journal of the American Oil Chemists Society, 32, 517519. Keller, P. A., Birch, C., Leach, S. P., Tyssen, D., & Grith, R. (2003). Novel pharmacophore-based methods reveal gossypol as a reverse transcriptase inhibitor. Journal of Molecular Graphics & Modelling, 21, 365373. Kendis, M. S., & Zakolodyazhnyi, V. V., & Roshchupkin, E. D. (1980). Lubricant composition for boreholes, SU 715616. Khasanov, N. M., Mamadzhanov, K., Bash, S. M., Yureva, N., Khudoerbekova, K., & Kurbanov, A. N. (1988). Drilling uid, SU 1406140. King, J. W., Taylor, S. L., Snyder, J. M., & Holliday, R. L. (1998). Total fatty acid analysis of vegetable oil soapstocks by supercritical uid extraction/reaction. Journal of the American Oil Chemists Society, 75, 12911295. Kircher, H. W., & Rosenste, Fu (1973). Isolation of brassicasterol from steam deodorizer distillate of rapeseed oil some properties of its

973

acetate tetrabromide and its reduction to 22,23-dihydrobrassicasterol. Lipids, 8, 453458. Klimashkin, I. I., Polyakov, G. A., Khashimov, M. K., Mamadzhanov, U. D., & Khodzhaeva, M. G. (1984). Drilling mud, SU 1090700. Koris, A., & Vatai, G. (2002). Dry degumming of vegetable oils by membrane ltration. Desalination, 148, 149153. Kovacic, P. (2003). Mechanism of drug and toxic actions of gossypol: Focus on reactive oxygen species and electron transfer. Current Medicinal Chemistry, 10, 27112718. Kuk, M. S., & Ballew, A. G. (1999). The potential of soapstock-derived lm: Cottonseed and saower. Journal of the American Oil Chemists Society, 76, 13871392. Kuk, M. S., & Tetlow, R. (2005). Gossypol removal by adsorption from cottonseed miscella. Journal of the American Oil Chemists Society, 82, 905909. Leshchinskij, P. A., & Davidenko, A. N. (1984). Drilling tool lubricant, SU1120014. Leslie, A. D. (1998). Lithium complex grease with extended lubrication life, WO 9811180. Lin, K. M., & Koseoglu, S. S. (2003). Separation of sterols from deodorizer distillate by crystallization. Journal of Food Lipids, 10, 107127. Lin, L., Rhee, K. C., & Koseoglu, S. S. (1997). Bench-scale membrane degumming of crude vegetable oil: Process optimization. Journal of Membrane Science, 134, 101108. Lipstein, B., & Bornstein, S. (1964a). Studies with acidulated cottonseedoil soapstock. 1. Its use as fat supplement in practical broiler rations. Poultry Science, 43, 686693. Lipstein, B., & Bornstein, S. (1964b). Studies with acidulated cottonseedoil soapstock. 2. Attempts to reduce its gossypol content. Poultry Science, 43, 694701. Lipstein, B., Bornstein, S., & Budowski, P. (1970). Acidulated cottonseedoil soapstock. 4. Eects on the fatty acid composition of broiler carcass lipids. Poultry Science, 49, 16311638. Lo, S. K., Baharin, B. S., Tan, C. P., & Lai, O. M. (2004a). Enzymecatalyzed production and chemical composition of diacylglycerols from corn oil deodorizer distillate. Food Biotechnology, 18, 265278. Lo, S. K., Baharin, B. S., Tan, C. P., & Lai, O. M. (2004b). Lipasecatalysed production and chemical composition of diacylglycerols from soybean oil deodoriser distillate. European Journal of Lipid Science and Technology, 106, 218224. Luxem, F. J., & Troy, W. M. (2004a). Making alkyl esters using pressure, US 6768015. Luxem, F. J., & Troy, W. M. (2004b). Transesterication method for making fatty acid methyl esters for use in biodiesel from vegetable oil and methanol, US 2004254387. Mag, T. K., Green, D. H., & Kwong, A. T. (1983). Continuous acidulation of soapstock and recovery of acid oil. Journal of the American Oil Chemists Society, 60, 10081011. Marin, J. P., Mateos, F. B., & Mateos, P. A. (2003). Use of residual soapstock from the rening of edible vegetable oils to make biodiesel. Grasas y Aceites, 54, 130137. Marks, C. (1988). Determination of free tocopherols in deodorizer distillate by capillary gas-chromatography. Journal of the American Oil Chemists Society, 65, 19361939. Martins, P. F., Batistella, C. B., Maciel-Filho, R., & Wolf-Maciel, M. R. (2006). Comparison of two dierent strategies for tocopherols enrichment using a molecular distillation process. Industrial & Engineering Chemistry Research, 45, 753758. Martins, P. F., Ito, V. M., Batistella, C. B., & Maciel, M. R. W. (2006). Free fatty acid separation from vegetable oil deodorizer distillate using molecular distillation process. Separation and Purication Technology, 48, 7884. Maza, A. (1992). Process for separating mixed fatty acids from deodorant distillate using urea, US 5078920. Mendes, M. F., Pessoa, F. L. P., Coelho, G. V., & Uller, A. M. C. (2005). Recovery of the high aggregated compounds present in the deodorizer

974

M.-J. Dumont, S.S. Narine / Food Research International 40 (2007) 957974 Ramamurthi, S., & McCurdy, A. R. (1993). Enzymatic pretreatment of deodorizer distillate for concentration of sterols and tocopherols. Journal of the American Oil Chemists Society, 70, 287295. Raman, L. P., Cheryan, M., & Rajagopalan, N. (1996). Deacidication of soybean oil by membrane technology. Journal of the American Oil Chemists Society, 73, 219224. Sengupta, R., & Bhattacharyya, D. K. (1992). A comparative-study between biorening combined with other processes and physical rening of high-acid mohua oil. Journal of the American Oil Chemists Society, 69, 11461149. Shimada, Y., Nakai, S., Suenaga, M., Sugihara, A., Kitano, M., & Tominaga, Y. (2000). Facile purication of tocopherols from soybean oil deodorizer distillate in high yield using lipase. Journal of the American Oil Chemists Society, 77, 10091013. Snyder, J. M., Taylor, S. L., & King, J. W. (1993). Analysis of tocopherols by capillary supercritical uid chromatography and mass-spectrometry. Journal of the American Oil Chemists Society, 70, 349354. Sonntag, N. O. V. (1985). Growth-potential for soybean oil products as industrial materials. Journal of the American Oil Chemists Society, 62, 928933. Stansbury, M. F., Cirino, V. O., & Pastor, H. P. (1957). Composition of acidulated cottonseed soapstocks as inuenced by commercial methods of processing seed and oil. Journal of the American Oil Chemists Society, 34, 539544. Sumner, C. E., Jr., Barnicki, S. D., Dol, M. D. (1995). Process for the production of sterol and tocopherol concentrates, US 5424457. Tuter, M., Aksoy, H. A., Gilbaz, E. E., & Kursun, E. (2004). Synthesis of fatty acid esters from acid oils using lipase B from Candida antarctica. European Journal of Lipid Science and Technology, 106, 513517. Usta, N., Ozturk, E., Can, O., Conkur, E. S., Nas, S., Con, A. H., et al. (2005). Combustion of biodiesel fuel produced from hazelnut soapstock/waste sunower oil mixture in a Diesel engine. Energy Conversion and Management, 46, 741755. Van Gerpen, J. (2005). Biodiesel processing and production. Fuel Processing Technology, 86, 10971107. Verleyen, T., Sosinska, U., Ioannidou, S., Verhe, R., Dewettinck, K., Huyghebaert, A., et al. (2002). Inuence of the vegetable oil rening process on free and esteried sterols. Journal of the American Oil Chemists Society, 79, 947953. Verleyen, T., Verhe, R., Garcia, L., Dewettinck, K., Huyghebaert, A., & De Greyt, W. (2001). Gas chromatographic characterization of vegetable oil deodorization distillate. Journal of Chromatography A, 921, 277285. Waliszewski, K. (1987). Fatty-acid composition of dierent oils and their soapstocks. Nutrition Reports International, 35, 8791. Wang, H. T., Goto, M., Sasaki, M., & Hirose, T. (2004). Separation of alpha-tocopherol and squalene by pressure swing adsorption in supercritical carbon dioxide. Industrial & Engineering Chemistry Research, 43, 27532758. Watanabe, Y., Nagao, T., Hirota, Y., Kitano, M., & Shimada, Y. (2004). Purication of tocopherols and phytosterols by a two-step in situ enzymatic reaction. Journal of the American Oil Chemists Society, 81, 339345. Weber, N., Weitkamp, P., & Mukherjee, K. D. (2002). Cholesterollowering food additives: Lipase-catalysed preparation of phytosterol and phytostanol esters. Food Research International, 35, 177 181. Xu, L., Yang, D. J., Wang, S. M., Tang, W. H., Liu, M. L., Davis, M., et al. (2005). ()-Gossypol enhances response to radiation therapy and results in tumor regression of human prostate cancer. Molecular Cancer Therapeutics, 4, 197205. Young, F. V. K., Biernoth, C. P. E., Krog, N., Davidson, N. G. J., & Gunstone, F. D. (1994). Processing of fats and oils, p. 58. Zaionts, O. L., Komar, V. Y., Pukas, A. I., Yarov, A. N., Kendis, M. S., Gilman, K. M., et al. (1970). Use of a new lubricating additive for drilling muds during diamond drilling of geological boreholes. Razvedka i Okhrana Nedr, 36, 3740.

distillate of the vegetable oils using supercritical uids. Journal of Supercritical Fluids, 34, 157162. Mendes, M. F., Pessoa, F. L. P., & Uller, A. M. C. (2002). An economic evaluation based on an experimental study of the vitamin E concentration present in deodorizer distillate of soybean oil using supercritical CO2. Journal of Supercritical Fluids, 23, 257265. Mendes, M. F., Uller, A. M. C., & Pessoa, F. L. P. (2000). Simulation and thermodynamic modeling of the extraction of tocopherol from a synthetic mixture of tocopherol, squalene and CO2. Brazilian Journal of Chemical Engineering, 17, 761769. Mironenko, O. N., Kuksov, A. K., Parpiev, S. K., & Makhmudov, T. M. (1989). Lignin-containing agent for treating drilling muds and waterbased buer uids, SU 1530635. Moreira, E. A., & Baltanas, M. A. (2004). Recovery of phytosterols from sunower oil deodorizer distillates. Journal of the American Oil Chemists Society, 81, 161167. Mori, Y., Nakagiri, H., Kondo, H., Murase, T., Tokimitsu, C., & Tajima, N. (2005). Dietary diacylglycerol reduces postprandial hyperlipidemia and ameliorates glucose intolerance in Otsuka Long-Evans Tokushima Fatty (OLETF) rats. Nutrition, 21, 933939. Motyleva, T. A., Sidorov, A. A., Evdokimov, B. V., Miller, M. G., Belov, V. I., Postolov, Y. M., Proskuryakov, V. A., Potekhin, V. M., & Ulyanov, Y. V. (1982). Lubricity agents for clay-containing drilling muds, SU 973585. Mueller, H., Herold, C. P., von Tapavicza, S., Grimes, D. J., Braun, J. M., & Smith, S. P. T. (1999). Use of selected ester oils in drilling uids and muds, RE 36066. Nagao, T., Kobayashi, T., Hirota, Y., Kitano, M., Kishimoto, C., Fujita, T., et al. (2005). Improvement of a process for purication of tocopherols and sterols from soybean oil deodorizer distillate. Journal of Molecular Catalysis B Enzymatic, 37, 5662. Nagata, J., & Saito, M. (2006). Eects of simultaneous intakes of indigestible dextrin and diacylglycerol on lipid proles in rats fed cholesterol diets. Nutrition, 22, 395400. Nagesha, G. K., Manohar, B., & Sankar, K. U. (2004). Enzymatic esterication of free fatty acids of hydrolyzed soy deodorizer distillate in supercritical carbon dioxide. Journal of Supercritical Fluids, 32, 137145. Nagesha, G. K., Subramanian, R., & Sankar, K. U. (2003). Processing of tocopherol and FA systems using a nonporous denser polymeric membrane. Journal of the American Oil Chemists Society, 80, 397402. Nitschke, M., Costa, S., Haddad, R., Goncalves, L. A. G., Eberlin, M. N., & Contiero, J. (2005). Oil wastes as unconventional substrates for rhamnolipid biosurfactant production by Pseudomonas aeruginosa LBI. Biotechnology Progress, 21, 15621566. OBrien, R. D. (2004). Fats and oils formulating and processing for applications (2nd ed.). Boca Raton, FL: CRC Press, pp. 6869. Oester, D. A., Hall, A., Zilch, K. T., & Anderson, K. W. (1997). Fat splitting process, US 5677160. Pardio, V. T., Landin, L. A., Waliszewski, K. N., Badillo, C., & Perez-Gil, F. (2001). The eect of acidied soapstocks on feed conversion and broiler skin pigmentation. Poultry Science, 80, 12361239. Pardio, V. T., Landin, L. A., Waliszewski, K. N., Perez-Gil, F., Diaz, L., & Hernandez, B. (2005). The eect of soybean soapstock on the quality parameters and fatty acid composition of the hen egg yolk. Poultry Science, 84, 148157. Piazza, J. G. J., & Haas, M. J. (1999). Method of rapid fat and oil splitting using a lipase catalyst found in seeds, US 5932458. Pioch, D., Largueze, C., Graille, J., Ajana, H., & Rouviere, J. (1998). Towards an ecientmembrane based vegetable oils rening. Industrial Crops and Products, 7(23), 8389. Quintero, L. (2002). An overview of surfactant applications in drilling uids for the petroleum industry. Journal of Dispersion Science and Technology, 23, 393404. Ramamurthi, S., Bhirud, P. R., & McCurdy, A. R. (1991). Enzymatic methylation of canola oil deodorizer distillate. Journal of the American Oil Chemists Society, 68, 970975.

S-ar putea să vă placă și