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Basic Oil Chemistry
Chapter 2
Basic Oil Chemistry Man has used vegetable oils for centuries. Oil bearing nuts and animal fats were consumed as sources of energy long before nutrition concepts were envisioned. Oils also were used early for lighting, as medicines, as cosmetics in religious ceremonies, and applied to weapons and utensils. The ancient oils of the Middle East, sesame and olive, were valued because of their long stability. Sunflower was cultivated in the Arizona–New Mexico area before the time of Christ, and seeds from the Missouri–Mississippi river basins were among the early plants transposed to Europe by explorers. Invention of the cotton gin in the late 1700s led to a major cotton export trade in the United States in the early 1800s, and to development of cottonseed oil as the first new oil of the Industrial Age in the mid-1800s. The continuous screw press, and early methods of caustic refining, bleaching, deodorization, winterization, and hydrogenation, including development of the first all vegetable shortening “Crisco” (shortened name for crystallized cottonseed oil) are among innovations developed. Processing of soybean, a crop first developed in China, led to further oil industry innovations including development of continuous solvent extractors and steam distillation technologies to reduce or remove the original raw flavor in the crude oil were developed in the mid-1900s. As flavor and stability improved, man expanded use of oils to: (1) cooking, (2) frying, (3) baking shortenings, (4) salad dressings, (5) food lubricants (like release agents in baking and candy making processes), (6) flavor carriers, and (7) dust-control agents. Each of the application requires oils with specific physical and chemical properties. Other oils, such as palm oil, regular canola oil, high oleic and low linolenic canola oil, high oleic sunflower oil, high oleic safflower oil, and so on were all commercialized much later than the animal fat and cottonseed oil.
2.1 COMPOSITION OF OIL All of the world’s matter is composed from approximately 108 elements. The smallest divisible stable particle of an element is called an “atom.” Compounds consist of atoms of two or more elements, with the smallest divisible stable particle called a “molecule.” Carbon (C), hydrogen (H), and oxygen (O) atoms are the principal building blocks of fats and oils. Practical Guide to Vegetable Oil Processing. http://dx.doi.org/10.1016/B978-1-63067-050-4.00002-7 Copyright © 2017 AOCS Press. Published by Elsevier Inc. All rights reserved.
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FIGURE 2.1 Formation of triglycerides.
Often, it is desirable to pictorially indicate relative positions of the elements in molecular structures. But, these must be carefully drawn by established convention, since the world exists in three dimensions, but only two dimensions are available for presentation on paper. In making such drawings, the knowledgeable chemist recognizes that some atoms only associate with others by extending links, while others only accept links. For example, each oxygen atom extends two links, while, each hydrogen atom accepts only one link. The chemistry of fats and oils is carbon chemistry, also known as “organic chemistry.” The carbon atom is unique in that it can either extend or accept a total of four links, with link givers, link receivers, or even with other carbon atoms. Oil is a mixture of 96–98% fatty acid triacylglycerols (commonly referred to as “triglycerides”), with the balance consisting of other fat-dispersible or fatsoluble compounds. Triglycerides consist of three fatty acids, which are substituted in the hydroxyl (alcoholic) sites of a glycerin (glycerol) backbone. The construction of a simple triglyceride is shown in Fig. 2.1, where each fatty acid is represented as a different “R.” Depending on the extent to which the three former hydroxyl groups of glycerol are replaced with fatty acids, the resulting compounds are known as follows. Monoglycerides are formed when one of the three hydroxyl groups of glycerol is replaced by a fatty acid. Diglycerides are formed when two of the three hydroxyl groups of glycerol are replaced by the same or different fatty acids. Triglycerides are formed when all three of the hydroxyl groups of glycerol are replaced by fatty acids (also referred as neutral oil).
A molecule of water is formed each time a fatty acid molecule replaces a hydroxyl group. Fig. 2.2 further shows the structures of monoglyceride, diglyceride, and triglyceride molecules. The major objective in refining and processing is to convert a shipment of purchased crude oil into the maximum possible amount of saleable “neutral oil” (triglycerides). Monoglycerides and diglycerides are formed when the neutral oil reacts with water molecules under undesirable storage and handling conditions. This reduces the yield of neutral oil in the refining process. It also creates poor quality refined oil. This will be discussed further in Chapter 11.
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FIGURE 2.2 Structures of mono-, di-, and triglycerides.
2.2 DISTINCTIONS BETWEEN OILS AND FATS A triglyceride molecule is called “oil” if it is liquid at ambient (room) temperature, and a “fat” if it is semisolid. Definitions of “room temperature” will vary greatly with the climate of the region. For example, “room temperature” in a tropical region can be >95°F (35°C), whereas that in a temperate region can be 68°F (20°C). A good example is coconut oil, which is liquid at room temperature in semitropical areas during the year except for the winter months when it becomes solid and might be called a “fat,” although coconut oil is always referred to as oil. Similarly, partially hydrogenated oil, which might be semisolid or solid at room temperature, is commonly referred to as oil. Products of reactions between hydroxyl groups and organic acids are called “esters” or sometimes “acyl- compounds.” The broad variety of products includes waxes made by esterification of long chain alcohols and long chain fatty acids, various food and industrial emulsifiers, noncaloric sucrose-based frying oils, fatty acid methyl ester solvents, and biodiesel fuels.
2.3 FATTY ACIDS IN COMMON VEGETABLE OILS Fatty acids are the building blocks of triglycerides. They generally contain 4–22 carbon atoms and are linear in structure. Sometimes, fatty acids are designated as “short chain” (4–8 carbon atoms), “medium chain” (10–12 carbon atoms), and “long chain” (14 or more carbon atoms). The following fatty acids are most common in vegetable oils: Saturated
Unsaturated
Lauric (C12) Palmitic (C16) Stearic (C18) Arachidic (C20) Behinic (C22)
Oleic (C18:1) Linoleic (C18:2) Linolenic (C18:3)
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Oleic acid, which has one double bond, is called a “monounsaturated fatty acid” while linoleic and linolenic acids are called “polyunsaturated fatty acids” because they contain more than one double bond (2 and 3, respectively).
2.3.1 Saturated and Unsaturated Fatty Acids A carbon atom with all four reaction sites of the carbon atom reacted with other elements is termed “saturated.” The structure of a fatty acid with an end carboxyl group (─COOH) is shown below.
In this example, only single carbon-to-carbon bonds exist, and the fatty acid is called “saturated.” Unsaturated fatty acids contain fewer hydrogen atoms than required to fully satisfy the valence of each carbon atom in the molecule. Thus, some carbon atoms are connected to each other with a “double bond” as shown in the following.
The double bonds in most vegetable oils (except for drying oils used in paints) contain two single bonds between the two double bonds in the chain. Most of the hydrogen in double bonds of natural fatty acids is found on the same side of the double bond, indicating a “cis position” (or “cisisomer”). But, some of the hydrogen atoms may move to the other side of the bond during hydrogenation process (chemical saturation of double bonds), to produce “trans-isomers.” These structures are further clarified in the following.
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Both cis and trans isomers are “unsaturated,” fatty acids. However, transformation of the cis to trans configuration raises the melt-point for the oil. A small conversion of cis to trans forms also occurs when oils are heated to very high temperature as during hydrogenation and deodorization.
2.4 TYPICAL BEHAVIOR OF FATTY ACIDS 2.4.1 Unsaturated Fatty Acids Unsaturated fatty acids are unstable and are very susceptible to oxidation even at ambient temperatures. They tend to: 1. readily oxidize when exposed to air or oxygen, 2. form aldehydes, ketones, etc., 3. form primarily oxidative polymers, and 4. form cyclic compounds.
2.4.2 Saturated Fatty Acids In contrast, saturated fatty acids are relatively stable. They do not oxidize in the presence of air or oxygen, but will decompose under high heat. They can produce: l l
thermal polymers toxins, such as acroleins
2.5 OBJECTIVES OF PROPER OIL PROCESSING The objective of proper oil processing is to obtain finished oil with the following traits: 1. long oxidative stability, 2. long thermal stability, 3. long flavor stability, 4. long storage stability, and 5. long shelf life of food products formulated with the oil. It is critical that processors understand the basic constituents of oil, its properties, and how to maintain process conditions that deliver oil with the quality standards listed previously.
2.6 NONTRIGLYCERIDE COMPONENTS OF OILS As mentioned earlier, crude vegetable oils generally contain 96–98% triglycerides. Although these components are present in small amounts, they can be very influential in determining overall stability and performance of the oil. They may be grouped as:
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1. major nontriglyceride components 2. minor nontriglyceride components
2.6.1 Major Nontriglycerides The following components generally are present at high levels in the crude oil and can be measured as percentages: 1. phospholipids 2. free fatty acids (FFA) 3. diglycerides 4. monoglycerides
2.6.1.1 Phospholipids These compounds are also known as phosphatides or gums. Their levels are generally expressed in parts per million of phosphorus. The five major groups of phospholipids found in most vegetable oils are: 1. phosphatidylcholine 2. phosphatidylethanolamine 3. phosphatidylinositol 4. phosphatidylserine 5. phosphatidic acid Typical phospholipids contents of common vegetable oils are shown in Table 2.1.
TABLE 2.1 Phospholipids Contents of Selected Vegetable Oils Oil type
Phospholipids content (%)
Phosphorusa content (ppm)
Crude soybean oil
1–3
317–950
Degummed soybean
0.32–0.64
100–200
Crude corn oil
0.7–0.9
222–285
Crude peanut (groundnut) oil
0.3–0.6
95–190
Crude canola oil
1.8–3.5
570–1104
Superdegummed canola oil
0.13–0.16
41–51
Crude sunflower oil
0.5–0.9
159–285
Crude safflower oil
0.4–0.6
127–190
Crude palm oil
0.06–0.95
19–30
a
The relationship between phospholipids and phosphorus contents is: phosphorous (ppm) = [phosphatides (%) × 104]/31.7.
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2.6.2 Hydratable and Nonhydratable Phospholipids Two types of phospholipids are present in crude oils from the standpoint of their affinity for water: 1. Hydratable phospholipids 2. Nonhydratable phospholipids Treatment with water at 140–158°F (60–70°C) hydrates some of the phospholipids in crude oils, which settle out or can be separated by centrifugation. For example, 600–800 ppm phosphorus in crude soybean oil can be reduced to 200 ppm or less by simple water degumming. Phospholipids, which are not removed by water alone are considered “nonhydratable.” The objective of acid-pretreatment of crude oil is to convert nonhydratable phospholipids into hydratable forms by sequestering (drawing away) absorbed bivalent cations (like calcium and magnesium metals) which interfere with their hydratability. Various methods for degumming crude oil are described in Chapter 3.
2.6.3 Free Fatty Acids Fatty acids, separated from triglyceride molecules, are called “free fatty acids, “FFA” and dissociate into two moieties—a link-accepting hydrogen ion and the link-giving residual. Formation of FFA in the oil of stored oilseeds is a natural occurrence, initiated by “lipase” enzymes. A small amount of FFA also formed during seed crushing and subsequent handling and storage of the crude oil. Fatty acids bound in triglycerides are still reactive in oxidation and hydrogenation processes. Amounts of FFA in crude oil vary with the oil species and history of the sample. Typical FFA values in selected crude oils are shown in Table 2.2.
2.6.4 Monoglycerides and Diglycerides Degradation of crude oils into FFA always is accompanied by formation of diglycerides and monoglycerides. These compounds have emulsifying
TABLE 2.2 Typical Free Fatty Acid (FFA) Content of Common Crude Vegetable Oils Oil type
FFA content (%)
Most seed oils
0.5–1.5
Crude palm oil
1–4
Crude cottonseed oil
0.5–3
Extra virgin olive oil
<0.8
Virgin olive oil
<2
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properties and can negatively impact on oil losses in refining and processing, and also on performance of the final oil. This will be discussed later in Chapter 11. Typical levels of monoglycerides and diglycerides in various fully processed oils are shown in Table 11.3.
2.6.5 Minor Nontriglycerides Minor nontriglyceride components of crude oil, present in parts per million levels, include: 1. tocopherols and tocotrienols 2. sterols and sterol esters 3. volatile and nonvolatile compounds formed from decomposition of the triglycerides 4. color compounds 5. trace metals
2.6.6 Tocopherols Tocopherols are naturally occurring antioxidants in vegetable oils, and one of nature’s protections against oil oxidation. Four types of tocopherols are present: alpha, beta, gamma, and delta. Sometimes, these forms are identified by Greek letters α, β, γ, and δ, respectively. Alpha (α) tocopherol provides protection to the oil against photooxidation (oxidation under visible light). Functions of beta (β) tocopherol, found at very low concentrations in oils, are not fully known. Gamma (γ) and delta (δ) tocopherols protect oil against autoxidation. Autoxidation is the primary pathway for oil oxidation, with oil degradation occurring even in absence of light. This type of oxidation process occurs during processing, storage, distribution of oil as well as food ingredients containing oils and during food products manufacture and their storage. The reaction is initiated by formation of a free radical from the unsaturated oil by a metal initiator. The reaction propagates and continues until either oxygen or unsaturated fatty acids are exhausted in the oil. Photooxidation can occur in unsaturated fatty acids when oil is exposed to ultraviolet rays and a metal initiator is present in the oil. This reaction is called photochemical reaction. This is a relatively slow reaction process like autoxidation. Photooxidation occurs to the oil in presence of a sensitizer like chlorophyll (or its oxidation products) when exposed to visible light. This reaction is very rapid and is 1500 times faster than autoxidation. Tocotrienols, another group of natural antioxidants, have attracted strong attention to palm and rice bran oils, which contain 300–500 and 400 ppm of these compounds, respectively. Tocotrienols are especially effective against autoxidation. Autoxidation reaction mechanism is shown in Table 2.3. Rice bran oil and corn oil also contain ferulic acid, an excellent antioxidant at high
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TABLE 2.3 Monoglycerides and Diglycerides Present in Fully Processed Oils Oil type
Monoglyceride (%)
Diglyceride (%)
Most seed oils
0.2–0.4
<0.5
Palm oil
0.5–3
3–7
FIGURE 2.3 Structures of tocopherols and tocotrienols.
temperatures. Rice bran oil contains another group of antioxidants known as oryzanols, which are extremely effective as antioxidants at high temperature applications like frying and baking. Sesame seed oil contains sesamolin, sesamol, sesaminol, and episesaminol antioxidants, which are not present in other seed oils. Further, palm oil contains CO Enzyme Q-10 a unique antioxidant not present in the seed oils. The structures of tocopherols and tocotrienols in Fig. 2.3 and the typical tocol contents of various oils are shown in Table 2.4.
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TABLE 2.4 Tocols Contents in Crude Oils (ppm) Sunflower
Cottonseed
Soybean
Corn oil
Palm oila
Canola
Alpha
403–935
402
90–120
191
129–215
290
Beta
ND–45
1.5
ND
—
22–37
—
Gamma
ND–34
572
740–1020
942
19–32
382
Delta
ND–7
75
240–300
42
10–20
13.4
Alpha
NDa
ND
ND
23
44–73
ND
Beta
ND
ND
ND
—
44–73
ND
Gamma
ND
ND
ND
—
260–437
ND
Delta
ND
ND
ND
—
70–117
ND
Total tocols
440–1520
1050
1130– 1450
1198
600–1000
685
Tocopherols
Tocotrienols
ND, Nondetectable. a Palm oil contains +CO enzyme Q-10 = 15–30 ppm.
Tocotrienols have three additional double bonds compared to tocopherols, which might be the reason for their improved antioxidant effects over tocopherols.
2.6.7 Sterols and Sterol Esters Phytosterols and phytosterol esters are often present in low concentrations similar to tocopherols and other antioxidants mentioned previously. These compounds also have antioxidant properties, although this property has not been studied as extensively as with the tocopherols. However, sterols and their derivatives have been studied more extensively in human nutrition. Like tocopherols, different types of sterols and derivatives exist, with type and concentration varying with the oil species. Sterols and sterol ester contents of common vegetable oils are shown in Table 2.5.
2.6.8 Volatile and Nonvolatile Compounds Autoxidation generates a large number of oil decomposition products, including: 1. primary oxidation products, for example, peroxide value (PV). 2. Secondary oxidation products, for example, aldehydes, ketenes, etc. 3. Tertiary oxidation products, for example, alcohols, acids, oxidation polymers, epoxides, cyclic fatty acids, and so on. The majority of these compounds has low molecular weight and volatilizes as the oil is heated. But, some fatty acid derivatives are too large and do not
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TABLE 2.5 Sterol Compounds and Their Levels in Common Crude Vegetable Oils (ppm) Type of sterols
Soybean
Canola Sunflower
Corn oil
Palm
Brassicasterol
ND–12.3
950
ND–9.2
ND–44.2
ND
3,600
1,348.8–2,990 4,384–14,718.6 150.6–434.7
Beta-sitosterol 918–2,460 Campesterol
284.4–992.2 1,900
177.6–593.4
1,488–5,326.1
56.1–192.5
Stigmasterol
268.2–783.1 35
168–529
344–1,701.7
25.5–97.3
Delta5 avenasterol
34.2–151.7
130
ND–317.4
336–1,812.2
ND–19.6
Delta7 stigmastenol
25.2–213.2
76
168–1104
80–928.2
0.6–16.8
Delta7 avenasterol
18–188.6
160
74.4–243.8
56–596.7
ND–35.7
Total sterols
1,800–4,100 6,900
2,400–4,600
8,000–22,100
300–700
ND, Nondetectable.
volatilize. These compounds have distinct effects on oil and product flavors and their stability, which will be discussed in Chapter 12.
2.6.9 Color Compounds The main color compounds in vegetable oils are carotenes and chlorophylls, although other chromophoric compounds also are present. Among the vegetable oils, palm oil contains the highest amount of carotenes. On the other hand, soybean and canola contain the highest amounts of chlorophylls. Most of the carotenes are removed from the oil by heat bleaching in deodorization described later. Most of the chlorophylls are removed from the oil during the bleaching process using bleaching clay. Most of the carotenes are retained in the deodorized palm oil called the “red palm oil,” using a very special process. This oil is sold as a naturally rich-in-carotene oil. The carotene content of this oil is 500–600 ppm, compared to 600–800 ppm in crude palm oil (CPO). Benefits of carotenes for human eyesight have been demonstrated in human studies in India and the Far East, and red palm oil is promoted for this nutritional property. This oil also has higher tocopherol and tocotrienol contents than the conventionally processed palm oil or palm olein.
2.6.10 Trace Metals Trace metals are undesirable in processed oils because they initiate the autoxidation reaction and shorten storage stabilities of oils and food products formulated
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with them. The most common metals found in the crude oil are: iron, calcium, magnesium, and sometimes very low levels of copper. Toxic “heavy metals” may also be present in very low concentrations in crude oils. Trace metals are removed from the crude oil by the bleaching clay, and bound by citric acid after the deodorization process. This will be discussed later in Chapters 6 and 12.
2.7 OIL ANALYSIS USED IN VEGETABLE OIL INDUSTRY AND THEIR SIGNIFICANCE Vegetable oil is analyzed at various stages of processing. Each analysis provides specific information to the processor as well as to the users. The most commonly conducted analyses in oil processing plants are listed in the following with brief descriptions.
Analysis Iodine value (IV) • Cyclohexane–acetic acid method • NIR method • Calculated from GLC • Cyclohexane method FFA • Crude and refined fats and oils Acid value • Of fats and oils PV • Isooctane method • Chloroform methoda para Anisidine value (pAV) Soap in oil • Titrimetric method • Conductivity method Conjugated dienes Polar material (TPM) Polymerized triglycerides Solid fat index (SFI) Solid fat content (SFC) Fatty acid composition (FAC) • Capillary GLC method • Packed column method trans fatty acid (TFA) • trans of partially hydrogenated oils by GLC-IR • cis, cis and trans isomers by GLCa • Isomers isolated by FTIR • By capillary GLC method a
Surplus method—either superseded or obsolete.
Method of Analysis (Version) AOCS Method Cd 1d-92 (09) Cd 1e-01 (09) Cd 1c- 85 (09) Cd 1b-87 (12) Ca 5a-40 (12) Cd 3d-63 (09) Cd 8b-90 (11) Cd 8-53 (03) Cd 18-90 (97) Cc 17-95 (09) Cc 15-60 (89) Ti 1a-64(09) Cd 20-91 (09) Cd 22-91 (09) Cd 10-57 (95) Ca 5a-40 (12) Ce 1e-91(01) Ce 1c-89 (95) Cd 14b-93 (95) Ce 1c-89 (95) Cd 14-95 (09) Ce 1f-96 (09)
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Bleaching test • For refined cottonseed oil • For refined soybean oil • For refined sunflower oil Lovibond color Wesson (Lovibond) method Color (per ISO Standard) Color (automated method) Chlorophyll pigment Refined and bleached oils Crude vegetable oils Crude vegetable oils Trace metals By AAS (Cr, Cu, Fe, Ni) By graphite furnace AAS (Cr, Cu, Fe, Ni, Mn) By graphite furnace direct (Cu, Fe, Ni) By graphite furnace AAS (Pb only) By ICP-OES (all metals) Phosphorus in oils By AAS By ICP-OES By IO method Smoke point, flash point, and fire point Cleveland open cup method Melt point Capillary tube method Mettler dropping point Slip melting point Slip melting point, ISO Standard Wiley methoda
Cc 8a-52 (12) Cc 8b-52 (11) Cc 8b-52 (11) Cc 13b-45 (09) Cc 13e-92 (09) Cc 13j-97 (09) Cc 13d-55 (09) Cc 13i-96 (13) Cc 13k-13 (13) Ca 15-75 (09) Ca 18-79 (09) Ca 18b-91 (09) Ca 18c-91 (09) Ca 17-01 (09) Ca 12b-92 (09) Ca 20-99 (09) Ca 12a-02 (09) Cc 9a-48 (09) Cc 1-25 (09) Cc 18-80 (09) Cc 3-25 (09) Cc 3b-92 (09) Cc 2-38 (91)
a
Surplus method—could be considered obsolete.
Active oxygen method (AOM)a Oil stability index(OSI) Refining loss • Degummed, expeller soybean oil • Degummed hydraulic and extracted soybean oil • Extracted and reconstituted prepressed cottonseed oil • Vegetable oils crude Neutral oil • Loss • In soap stock Unsaponifiable matter Saponification value Mono and diglycerides • By capillary GLC • By HPLC-ELSD
Cd 12-57 (93) Cd 12b-92 (09) Ca 9a-52 (09)
Ca 9F-57 (09) G5 -40 (09) Ca 6a-40 (11) Cd 3-25 (13) Cd 11b-91 (09) Cd 11d-96 (09)
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Mono, di and triglycerides • By silica gel chromatography Alfa monoglycerides Moisture and volatiles (butter fat, margarines, oils) • By hot plate method • Vacuum oven method (except coconut oil) • By distillation method • By Karl Fischer method Alkalinity • Of fats and oils • In soda soap and products Acetone insoluble matter • In lecithin
Cd 11c-93 (09) Cd 11-57 (11) Ca 2b 38-(09) Ca 2d-25 (09) Ca 2a = 45 (09) Ca 2e-84 (09) Cd 3e-02 (09) Da 7-48 (09) Ja 4-46 (11)
a
Surplus method—could be considered obsolete.
2.8 SIGNIFICANCE OF THE ANALYTICAL METHODS AND RESULTS 2.8.1 Iodine Value This method determines the degree of unsaturation in the oil. The results are expressed as grams of iodine absorbed per 100 g of the oil sample. Oils with higher unsaturation show higher IV values. Iodine values of most common crude vegetable oils are listed in Table 2.6.
2.8.2 Free Fatty Acids This method determines the amount of FFA present in the oil. Generally, results are expressed as percent oleic acid for seed oils. It is expressed as percent palmitic acid for palm oil and palm oil derivatives, and as percent lauric acid for palm kernel or coconut oils.
TABLE 2.6 Typical Iodine Values of Common Refined Vegetable Oils Oil type
Typical iodine value
Soybean
132
Canola
120
Sunflower oil
128
Cottonseed oil
110
Palm oil
50
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2.8.3 Acid Value The acid value for oil is the number of mg of potassium hydroxide required to neutralize the free acid in 1 g of the oil. For easy reference: AV = 1.99 FFA (%)
2.8.4 Peroxide Value This method measures the primary state of oxidative of the unsaturated fatty acids in oil. The fatty acid can be in the form of FFA or as part of a triglyceride molecule. This method measures all substances in the oil, which oxidize potassium iodide under conditions of the method as milliequivalents of peroxide per 1000 g of oil or fat. PV of freshly bleached as well as deodorized oil must be “zero.”
2.8.5 para Anisidine Value pAV is defined by convention as 100 times the optical density of a solution containing 1 g of oil and 100 mL of a mixture of solvent and reagents specified in the test method, measured in a 1-cm cuvette at 350 nm. This test measures some of the secondary oxidation compounds of oils and fats generated from the decomposition of the peroxides. Specifically, 2-alkenals and 2, 4-dienals are measured by this method. Freshly deodorized oil may have a pAV content of 2–6.
2.8.6 Soap in Oil This titrimetric method determines alkalinity in the oil as parts per million sodium oleate. Presence of soap in bleached oil indicates poor bleaching. Properly refined and bleached oil must have zero soap content. Soap in bleached oil can cause numerous production and quality problems which will be discussed later.
2.8.7 Conjugated Dienes This spectrophotometric method determines diene linkages of unsaturated fatty acids present in oil in terms of percent of oil. This is a measure to understand the onset of autoxidation reaction, and will be discussed later in Chapter 12.
2.8.8 Polar Material (TPM) This method determines the total amount of polar materials present in the oil by column chromatography. It is used as a measure of oxidative degradation for oil, especially in frying processes.
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2.8.9 Polymerized Triglycerides This method determines polymerized triglycerides in fats and oils by a gelpermeation method, and indicates the degree of thermal and oxidative abuse of the oil.
2.8.10 Solid Fat Index This is a dilatometric method which determines the combined volume of solid and liquid in the sample at specific temperatures. It is an empirical measure of solids fat content in a sample of oil at specified temperatures. The information is used in formulating shortenings, margarines, and spreads.
2.8.11 Solid Fat Content This Nuclear Magnetic Resonance Spectrometry (NMR) method estimates the amount of fat solids present in the oil (fat) sample at specific temperatures. It is also used in formulating shortenings, margarines, and spreads, and originally was developed for the emerging modern palm oil industry.
2.8.12 Fatty Acid Composition This capillary method identifies the fatty acids in a fat or oil by analysis of the sample’s fatty acid methyl esters by capillary gas–liquid chromatography. The fatty acid methyl esters are prepared according to AOCS Method Ce 2-66 (09). This method does not identify cis or trans isomers.
2.8.13 Fatty Acid Composition The packed column method is especially suitable for analyzing hydrogenated fat because it is capable of providing (1) fatty acids identities and compositions, and (2) TFA and cis–cis methylene-interrupted unsaturation. This method yields slightly lower trans values as compared to the infrared spectrophotometric method (AOCS Method Cd 14-61).
2.8.14 trans Fatty Acid TFA in hydrogenated fat is becoming increasingly critical for the vegetable oil industry.
2.8.15 Refined and Bleached Color Test These methods are available applicable to refined cottonseed oil soybean and sunflower oils. These tests are particularly helpful to predict the color of the deodorized oil that could be obtained from a given crude oil.
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2.8.16 Lovibond Color Method Cc 13b-45 (09) compares the oil color by comparing against colored glasses. This method can be used to measure color of all normal oils provided there is no turbidity in the sample. Method Cc 13e-92 (09) is preferred by the British Standard Lovibond International trade. Method Cc 13j-97 (09) is suitable for measuring colors of all refined, bleached, and deodorized vegetable oils and also filtered and deodorized tallow. The Automated method gives results in the AOCS-Tintometer (Wesson method) or the Lovibond color scale. Lovibond color can be used to track degree of removal of color bodies present in the original crude oil. Each type of oil has a characteristic Lovibond Red color. A higher color indicates problems either with the oil or the process. These will be discussed in detail later in Chapters 6, 8, and 12.
2.8.17 Chlorophyll Pigments This spectrophotometric method determines the concentration of chlorophyll in expelled, refined, and bleached oils by measuring absorption at 630, 670, and 710 nm wavelengths. This method is not applicable to hydrogenated oils, deodorized oils, or finished products.
2.8.18 Trace Metals (ICP) The ICP method, or Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), is used for quantitative determination of calcium, copper, iron, magnesium, nickel, silicon, lead, sodium, and cadmium in oil, when these impurities are present in the solubilized form in the oil. Suspended material, such as bleaching clay or nickel catalyst cannot be detected by this method. The detection level by this method is extremely low and precise.
2.8.19 Trace Metals (Atomic Absorption Method) This method is suitable for crude oil and partially refined oil. It can determine copper, chromium iron and nickel as low as 0.1 ppm in the oil.
2.8.20 Phosphorus (Graphite Furnace) This method determines the phosphorus content in parts per million. It involves vaporization of the oil in a suitable graphite furnace and an atomic absorption spectrophotometer for reading.
2.8.21 Phosphorus (ICP) This method quantitatively determines the phosphorus level in oil by using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES).
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2.8.22 Smoke Point, Flash Point, and Fire Point (Cleveland Open Cup method) Smoke point is directly related to the amount of FFA in the oil, and also to the amounts of monoglycerides and diglycerides present in the oil. The flash point of solvent-extracted crude oil must be checked at receipt to make sure it is higher than 300°F (149°C). The smoke point for the degummed soybean oil or crude sunflower oil is 250°F (121°C) maximum, according to the Trading rules of NIOP.
2.8.23 Melt Point (Capillary Tube Method) The complete melting point of fat is determined by this method.
2.8.24 Melt Point (Mettler Drop Point Method) The temperature at which the fat sample becomes soft and flows under the specific conditions of the test is measured by this method. This is an approximate method for melt point because one can see higher melting solids in the melted sample even at a temperature higher than the melt point determined by this method.
2.8.25 Active Oxygen Method (AOM) This method measures the time in hours needed for the PV of a sample to reach 100 mEq when tested under the conditions specified. This is a measure of the primary oxidative stability of oil. AOM provides good information oil stability for salad dressing and applications that do not require high temperature treatment for the oil. Most oil processors and end users stopped using this method because the following method is found to be more useful to determine the oxidative stability of the oil.
2.8.26 Oil Stability Index (OSI) This method provides the tertiary oxidative state for the oil. In oil applications, OSI is a better measure of oil stability while processing of foods formulated with the oil and is subjected to high temperature. The apparent basic difference between OSI and AOM is that OSI estimates the time required to exhaust antioxidants present in the sample and begins accumulating peroxides, while AOM measures the total time required for the sample to degrade to the 100 mEq PV. The OSI method provides better information about the secondary and tertiary oxidation of the oil. This will be discussed further in Chapter 12.
2.8.27 Refining Loss There are several methods for the test that apply to different oils as listed previously.
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2.8.28 Neutral Oil Loss 2.8.28.1 In Refining The total natural oil of natural fats and oils consisting essentially of triglycerides and unsaponifiable matter is determined by this method. The fatty acids and miscellaneous nonfat substances are removed by passing through a column of activated alumina. The loss is the difference between the amount of feed and that recovered, expressed as percent. This method is satisfactory for cottonseed, soybean, peanut (groundnut), linseed, coconut, and sunflower oils. 2.8.28.2 In Soap Stock There is always a certain amount of neutral oil that remains in the soap stock that is discharged from the primary separator in caustic refining process. This method allows one to determine the amount of neutral oil in the soap stock.
2.8.29 Unsaponifiable Matter Unsaponifiable matter include those substances frequently found dissolve in fats and oils, which cannot be saponified by the usual caustic treatment, but are soluble in ordinary fat and oil solvents. Included in this group are high aliphatic alcohols, sterols, pigments, and hydrocarbons. This method is applicable to normal animal and vegetable oils and fats but is not applicable to marine oils and the feed-grade fats.
2.8.30 Saponification Value This method is defined as the number of milligrams of KOH required to saponify 1 g of the oil sample. This method is important in the soap making industry. This method is applicable for vegetable oils, deodorizer distillates, and sludges.
BIBLIOGRAPHY Food Codex Alimentarius Commission Standard 210.(1999). Bockisch, M., 1993. Fats and Oils Handbook. AOCS Publication, USA. Gupta, M.K., 2017. Practical Guide to Vegetable Oil Processing. AOCS Publication, Peoria, IL, USA, 2007. Muller-Mulot, W., 1976. J. Am. Oil Chem. Soc. 53, 732. Ooi, C.K., Choo, Y.M., Yap, S.C., Basiron, Y., Ong, A.S.H., 1994. Recovery of carotenoids from palm oil. J. Am. Oil Chem. Soc. 71, 423–426. Slover, H.T., Lehmann, J., Valis, R.J., 1969. Vitamin in foods: determination of tocols and tocotrienols. J. Am. Oil Chem. Soc. 46, 417–420.
Basic Oil Chemistry Man has used vegetable oils for centuries. Oil bearing nuts and animal fats were consumed as sources of energy long before nutrition concepts were envisioned. Oils also were used early for lighting, as medicines, as cosmetics in religious ceremonies, and applied to weapons and utensils. The ancient oils of the Middle East, sesame and olive, were valued because of their long stability. Sunflower was cultivated in the Arizona–New Mexico area before the time of Christ, and seeds from the Missouri–Mississippi river basins were among the early plants transposed to Europe by explorers. Invention of the cotton gin in the late 1700s led to a major cotton export trade in the United States in the early 1800s, and to development of cottonseed oil as the first new oil of the Industrial Age in the mid-1800s. The continuous screw press, and early methods of caustic refining, bleaching, deodorization, winterization, and hydrogenation, including development of the first all vegetable shortening “Crisco” (shortened name for crystallized cottonseed oil) are among innovations developed. Processing of soybean, a crop first developed in China, led to further oil industry innovations including development of continuous solvent extractors and steam distillation technologies to reduce or remove the original raw flavor in the crude oil were developed in the mid-1900s. As flavor and stability improved, man expanded use of oils to: (1) cooking, (2) frying, (3) baking shortenings, (4) salad dressings, (5) food lubricants (like release agents in baking and candy making processes), (6) flavor carriers, and (7) dust-control agents. Each of the application requires oils with specific physical and chemical properties. Other oils, such as palm oil, regular canola oil, high oleic and low linolenic canola oil, high oleic sunflower oil, high oleic safflower oil, and so on were all commercialized much later than the animal fat and cottonseed oil.
2.1 COMPOSITION OF OIL All of the world’s matter is composed from approximately 108 elements. The smallest divisible stable particle of an element is called an “atom.” Compounds consist of atoms of two or more elements, with the smallest divisible stable particle called a “molecule.” Carbon (C), hydrogen (H), and oxygen (O) atoms are the principal building blocks of fats and oils. Practical Guide to Vegetable Oil Processing. http://dx.doi.org/10.1016/B978-1-63067-050-4.00002-7 Copyright © 2017 AOCS Press. Published by Elsevier Inc. All rights reserved.
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FIGURE 2.1 Formation of triglycerides.
Often, it is desirable to pictorially indicate relative positions of the elements in molecular structures. But, these must be carefully drawn by established convention, since the world exists in three dimensions, but only two dimensions are available for presentation on paper. In making such drawings, the knowledgeable chemist recognizes that some atoms only associate with others by extending links, while others only accept links. For example, each oxygen atom extends two links, while, each hydrogen atom accepts only one link. The chemistry of fats and oils is carbon chemistry, also known as “organic chemistry.” The carbon atom is unique in that it can either extend or accept a total of four links, with link givers, link receivers, or even with other carbon atoms. Oil is a mixture of 96–98% fatty acid triacylglycerols (commonly referred to as “triglycerides”), with the balance consisting of other fat-dispersible or fatsoluble compounds. Triglycerides consist of three fatty acids, which are substituted in the hydroxyl (alcoholic) sites of a glycerin (glycerol) backbone. The construction of a simple triglyceride is shown in Fig. 2.1, where each fatty acid is represented as a different “R.” Depending on the extent to which the three former hydroxyl groups of glycerol are replaced with fatty acids, the resulting compounds are known as follows. Monoglycerides are formed when one of the three hydroxyl groups of glycerol is replaced by a fatty acid. Diglycerides are formed when two of the three hydroxyl groups of glycerol are replaced by the same or different fatty acids. Triglycerides are formed when all three of the hydroxyl groups of glycerol are replaced by fatty acids (also referred as neutral oil).
A molecule of water is formed each time a fatty acid molecule replaces a hydroxyl group. Fig. 2.2 further shows the structures of monoglyceride, diglyceride, and triglyceride molecules. The major objective in refining and processing is to convert a shipment of purchased crude oil into the maximum possible amount of saleable “neutral oil” (triglycerides). Monoglycerides and diglycerides are formed when the neutral oil reacts with water molecules under undesirable storage and handling conditions. This reduces the yield of neutral oil in the refining process. It also creates poor quality refined oil. This will be discussed further in Chapter 11.
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FIGURE 2.2 Structures of mono-, di-, and triglycerides.
2.2 DISTINCTIONS BETWEEN OILS AND FATS A triglyceride molecule is called “oil” if it is liquid at ambient (room) temperature, and a “fat” if it is semisolid. Definitions of “room temperature” will vary greatly with the climate of the region. For example, “room temperature” in a tropical region can be >95°F (35°C), whereas that in a temperate region can be 68°F (20°C). A good example is coconut oil, which is liquid at room temperature in semitropical areas during the year except for the winter months when it becomes solid and might be called a “fat,” although coconut oil is always referred to as oil. Similarly, partially hydrogenated oil, which might be semisolid or solid at room temperature, is commonly referred to as oil. Products of reactions between hydroxyl groups and organic acids are called “esters” or sometimes “acyl- compounds.” The broad variety of products includes waxes made by esterification of long chain alcohols and long chain fatty acids, various food and industrial emulsifiers, noncaloric sucrose-based frying oils, fatty acid methyl ester solvents, and biodiesel fuels.
2.3 FATTY ACIDS IN COMMON VEGETABLE OILS Fatty acids are the building blocks of triglycerides. They generally contain 4–22 carbon atoms and are linear in structure. Sometimes, fatty acids are designated as “short chain” (4–8 carbon atoms), “medium chain” (10–12 carbon atoms), and “long chain” (14 or more carbon atoms). The following fatty acids are most common in vegetable oils: Saturated
Unsaturated
Lauric (C12) Palmitic (C16) Stearic (C18) Arachidic (C20) Behinic (C22)
Oleic (C18:1) Linoleic (C18:2) Linolenic (C18:3)
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Oleic acid, which has one double bond, is called a “monounsaturated fatty acid” while linoleic and linolenic acids are called “polyunsaturated fatty acids” because they contain more than one double bond (2 and 3, respectively).
2.3.1 Saturated and Unsaturated Fatty Acids A carbon atom with all four reaction sites of the carbon atom reacted with other elements is termed “saturated.” The structure of a fatty acid with an end carboxyl group (─COOH) is shown below.
In this example, only single carbon-to-carbon bonds exist, and the fatty acid is called “saturated.” Unsaturated fatty acids contain fewer hydrogen atoms than required to fully satisfy the valence of each carbon atom in the molecule. Thus, some carbon atoms are connected to each other with a “double bond” as shown in the following.
The double bonds in most vegetable oils (except for drying oils used in paints) contain two single bonds between the two double bonds in the chain. Most of the hydrogen in double bonds of natural fatty acids is found on the same side of the double bond, indicating a “cis position” (or “cisisomer”). But, some of the hydrogen atoms may move to the other side of the bond during hydrogenation process (chemical saturation of double bonds), to produce “trans-isomers.” These structures are further clarified in the following.
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Both cis and trans isomers are “unsaturated,” fatty acids. However, transformation of the cis to trans configuration raises the melt-point for the oil. A small conversion of cis to trans forms also occurs when oils are heated to very high temperature as during hydrogenation and deodorization.
2.4 TYPICAL BEHAVIOR OF FATTY ACIDS 2.4.1 Unsaturated Fatty Acids Unsaturated fatty acids are unstable and are very susceptible to oxidation even at ambient temperatures. They tend to: 1. readily oxidize when exposed to air or oxygen, 2. form aldehydes, ketones, etc., 3. form primarily oxidative polymers, and 4. form cyclic compounds.
2.4.2 Saturated Fatty Acids In contrast, saturated fatty acids are relatively stable. They do not oxidize in the presence of air or oxygen, but will decompose under high heat. They can produce: l l
thermal polymers toxins, such as acroleins
2.5 OBJECTIVES OF PROPER OIL PROCESSING The objective of proper oil processing is to obtain finished oil with the following traits: 1. long oxidative stability, 2. long thermal stability, 3. long flavor stability, 4. long storage stability, and 5. long shelf life of food products formulated with the oil. It is critical that processors understand the basic constituents of oil, its properties, and how to maintain process conditions that deliver oil with the quality standards listed previously.
2.6 NONTRIGLYCERIDE COMPONENTS OF OILS As mentioned earlier, crude vegetable oils generally contain 96–98% triglycerides. Although these components are present in small amounts, they can be very influential in determining overall stability and performance of the oil. They may be grouped as:
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1. major nontriglyceride components 2. minor nontriglyceride components
2.6.1 Major Nontriglycerides The following components generally are present at high levels in the crude oil and can be measured as percentages: 1. phospholipids 2. free fatty acids (FFA) 3. diglycerides 4. monoglycerides
2.6.1.1 Phospholipids These compounds are also known as phosphatides or gums. Their levels are generally expressed in parts per million of phosphorus. The five major groups of phospholipids found in most vegetable oils are: 1. phosphatidylcholine 2. phosphatidylethanolamine 3. phosphatidylinositol 4. phosphatidylserine 5. phosphatidic acid Typical phospholipids contents of common vegetable oils are shown in Table 2.1.
TABLE 2.1 Phospholipids Contents of Selected Vegetable Oils Oil type
Phospholipids content (%)
Phosphorusa content (ppm)
Crude soybean oil
1–3
317–950
Degummed soybean
0.32–0.64
100–200
Crude corn oil
0.7–0.9
222–285
Crude peanut (groundnut) oil
0.3–0.6
95–190
Crude canola oil
1.8–3.5
570–1104
Superdegummed canola oil
0.13–0.16
41–51
Crude sunflower oil
0.5–0.9
159–285
Crude safflower oil
0.4–0.6
127–190
Crude palm oil
0.06–0.95
19–30
a
The relationship between phospholipids and phosphorus contents is: phosphorous (ppm) = [phosphatides (%) × 104]/31.7.
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2.6.2 Hydratable and Nonhydratable Phospholipids Two types of phospholipids are present in crude oils from the standpoint of their affinity for water: 1. Hydratable phospholipids 2. Nonhydratable phospholipids Treatment with water at 140–158°F (60–70°C) hydrates some of the phospholipids in crude oils, which settle out or can be separated by centrifugation. For example, 600–800 ppm phosphorus in crude soybean oil can be reduced to 200 ppm or less by simple water degumming. Phospholipids, which are not removed by water alone are considered “nonhydratable.” The objective of acid-pretreatment of crude oil is to convert nonhydratable phospholipids into hydratable forms by sequestering (drawing away) absorbed bivalent cations (like calcium and magnesium metals) which interfere with their hydratability. Various methods for degumming crude oil are described in Chapter 3.
2.6.3 Free Fatty Acids Fatty acids, separated from triglyceride molecules, are called “free fatty acids, “FFA” and dissociate into two moieties—a link-accepting hydrogen ion and the link-giving residual. Formation of FFA in the oil of stored oilseeds is a natural occurrence, initiated by “lipase” enzymes. A small amount of FFA also formed during seed crushing and subsequent handling and storage of the crude oil. Fatty acids bound in triglycerides are still reactive in oxidation and hydrogenation processes. Amounts of FFA in crude oil vary with the oil species and history of the sample. Typical FFA values in selected crude oils are shown in Table 2.2.
2.6.4 Monoglycerides and Diglycerides Degradation of crude oils into FFA always is accompanied by formation of diglycerides and monoglycerides. These compounds have emulsifying
TABLE 2.2 Typical Free Fatty Acid (FFA) Content of Common Crude Vegetable Oils Oil type
FFA content (%)
Most seed oils
0.5–1.5
Crude palm oil
1–4
Crude cottonseed oil
0.5–3
Extra virgin olive oil
<0.8
Virgin olive oil
<2
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properties and can negatively impact on oil losses in refining and processing, and also on performance of the final oil. This will be discussed later in Chapter 11. Typical levels of monoglycerides and diglycerides in various fully processed oils are shown in Table 11.3.
2.6.5 Minor Nontriglycerides Minor nontriglyceride components of crude oil, present in parts per million levels, include: 1. tocopherols and tocotrienols 2. sterols and sterol esters 3. volatile and nonvolatile compounds formed from decomposition of the triglycerides 4. color compounds 5. trace metals
2.6.6 Tocopherols Tocopherols are naturally occurring antioxidants in vegetable oils, and one of nature’s protections against oil oxidation. Four types of tocopherols are present: alpha, beta, gamma, and delta. Sometimes, these forms are identified by Greek letters α, β, γ, and δ, respectively. Alpha (α) tocopherol provides protection to the oil against photooxidation (oxidation under visible light). Functions of beta (β) tocopherol, found at very low concentrations in oils, are not fully known. Gamma (γ) and delta (δ) tocopherols protect oil against autoxidation. Autoxidation is the primary pathway for oil oxidation, with oil degradation occurring even in absence of light. This type of oxidation process occurs during processing, storage, distribution of oil as well as food ingredients containing oils and during food products manufacture and their storage. The reaction is initiated by formation of a free radical from the unsaturated oil by a metal initiator. The reaction propagates and continues until either oxygen or unsaturated fatty acids are exhausted in the oil. Photooxidation can occur in unsaturated fatty acids when oil is exposed to ultraviolet rays and a metal initiator is present in the oil. This reaction is called photochemical reaction. This is a relatively slow reaction process like autoxidation. Photooxidation occurs to the oil in presence of a sensitizer like chlorophyll (or its oxidation products) when exposed to visible light. This reaction is very rapid and is 1500 times faster than autoxidation. Tocotrienols, another group of natural antioxidants, have attracted strong attention to palm and rice bran oils, which contain 300–500 and 400 ppm of these compounds, respectively. Tocotrienols are especially effective against autoxidation. Autoxidation reaction mechanism is shown in Table 2.3. Rice bran oil and corn oil also contain ferulic acid, an excellent antioxidant at high
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TABLE 2.3 Monoglycerides and Diglycerides Present in Fully Processed Oils Oil type
Monoglyceride (%)
Diglyceride (%)
Most seed oils
0.2–0.4
<0.5
Palm oil
0.5–3
3–7
FIGURE 2.3 Structures of tocopherols and tocotrienols.
temperatures. Rice bran oil contains another group of antioxidants known as oryzanols, which are extremely effective as antioxidants at high temperature applications like frying and baking. Sesame seed oil contains sesamolin, sesamol, sesaminol, and episesaminol antioxidants, which are not present in other seed oils. Further, palm oil contains CO Enzyme Q-10 a unique antioxidant not present in the seed oils. The structures of tocopherols and tocotrienols in Fig. 2.3 and the typical tocol contents of various oils are shown in Table 2.4.
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TABLE 2.4 Tocols Contents in Crude Oils (ppm) Sunflower
Cottonseed
Soybean
Corn oil
Palm oila
Canola
Alpha
403–935
402
90–120
191
129–215
290
Beta
ND–45
1.5
ND
—
22–37
—
Gamma
ND–34
572
740–1020
942
19–32
382
Delta
ND–7
75
240–300
42
10–20
13.4
Alpha
NDa
ND
ND
23
44–73
ND
Beta
ND
ND
ND
—
44–73
ND
Gamma
ND
ND
ND
—
260–437
ND
Delta
ND
ND
ND
—
70–117
ND
Total tocols
440–1520
1050
1130– 1450
1198
600–1000
685
Tocopherols
Tocotrienols
ND, Nondetectable. a Palm oil contains +CO enzyme Q-10 = 15–30 ppm.
Tocotrienols have three additional double bonds compared to tocopherols, which might be the reason for their improved antioxidant effects over tocopherols.
2.6.7 Sterols and Sterol Esters Phytosterols and phytosterol esters are often present in low concentrations similar to tocopherols and other antioxidants mentioned previously. These compounds also have antioxidant properties, although this property has not been studied as extensively as with the tocopherols. However, sterols and their derivatives have been studied more extensively in human nutrition. Like tocopherols, different types of sterols and derivatives exist, with type and concentration varying with the oil species. Sterols and sterol ester contents of common vegetable oils are shown in Table 2.5.
2.6.8 Volatile and Nonvolatile Compounds Autoxidation generates a large number of oil decomposition products, including: 1. primary oxidation products, for example, peroxide value (PV). 2. Secondary oxidation products, for example, aldehydes, ketenes, etc. 3. Tertiary oxidation products, for example, alcohols, acids, oxidation polymers, epoxides, cyclic fatty acids, and so on. The majority of these compounds has low molecular weight and volatilizes as the oil is heated. But, some fatty acid derivatives are too large and do not
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TABLE 2.5 Sterol Compounds and Their Levels in Common Crude Vegetable Oils (ppm) Type of sterols
Soybean
Canola Sunflower
Corn oil
Palm
Brassicasterol
ND–12.3
950
ND–9.2
ND–44.2
ND
3,600
1,348.8–2,990 4,384–14,718.6 150.6–434.7
Beta-sitosterol 918–2,460 Campesterol
284.4–992.2 1,900
177.6–593.4
1,488–5,326.1
56.1–192.5
Stigmasterol
268.2–783.1 35
168–529
344–1,701.7
25.5–97.3
Delta5 avenasterol
34.2–151.7
130
ND–317.4
336–1,812.2
ND–19.6
Delta7 stigmastenol
25.2–213.2
76
168–1104
80–928.2
0.6–16.8
Delta7 avenasterol
18–188.6
160
74.4–243.8
56–596.7
ND–35.7
Total sterols
1,800–4,100 6,900
2,400–4,600
8,000–22,100
300–700
ND, Nondetectable.
volatilize. These compounds have distinct effects on oil and product flavors and their stability, which will be discussed in Chapter 12.
2.6.9 Color Compounds The main color compounds in vegetable oils are carotenes and chlorophylls, although other chromophoric compounds also are present. Among the vegetable oils, palm oil contains the highest amount of carotenes. On the other hand, soybean and canola contain the highest amounts of chlorophylls. Most of the carotenes are removed from the oil by heat bleaching in deodorization described later. Most of the chlorophylls are removed from the oil during the bleaching process using bleaching clay. Most of the carotenes are retained in the deodorized palm oil called the “red palm oil,” using a very special process. This oil is sold as a naturally rich-in-carotene oil. The carotene content of this oil is 500–600 ppm, compared to 600–800 ppm in crude palm oil (CPO). Benefits of carotenes for human eyesight have been demonstrated in human studies in India and the Far East, and red palm oil is promoted for this nutritional property. This oil also has higher tocopherol and tocotrienol contents than the conventionally processed palm oil or palm olein.
2.6.10 Trace Metals Trace metals are undesirable in processed oils because they initiate the autoxidation reaction and shorten storage stabilities of oils and food products formulated
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with them. The most common metals found in the crude oil are: iron, calcium, magnesium, and sometimes very low levels of copper. Toxic “heavy metals” may also be present in very low concentrations in crude oils. Trace metals are removed from the crude oil by the bleaching clay, and bound by citric acid after the deodorization process. This will be discussed later in Chapters 6 and 12.
2.7 OIL ANALYSIS USED IN VEGETABLE OIL INDUSTRY AND THEIR SIGNIFICANCE Vegetable oil is analyzed at various stages of processing. Each analysis provides specific information to the processor as well as to the users. The most commonly conducted analyses in oil processing plants are listed in the following with brief descriptions.
Analysis Iodine value (IV) • Cyclohexane–acetic acid method • NIR method • Calculated from GLC • Cyclohexane method FFA • Crude and refined fats and oils Acid value • Of fats and oils PV • Isooctane method • Chloroform methoda para Anisidine value (pAV) Soap in oil • Titrimetric method • Conductivity method Conjugated dienes Polar material (TPM) Polymerized triglycerides Solid fat index (SFI) Solid fat content (SFC) Fatty acid composition (FAC) • Capillary GLC method • Packed column method trans fatty acid (TFA) • trans of partially hydrogenated oils by GLC-IR • cis, cis and trans isomers by GLCa • Isomers isolated by FTIR • By capillary GLC method a
Surplus method—either superseded or obsolete.
Method of Analysis (Version) AOCS Method Cd 1d-92 (09) Cd 1e-01 (09) Cd 1c- 85 (09) Cd 1b-87 (12) Ca 5a-40 (12) Cd 3d-63 (09) Cd 8b-90 (11) Cd 8-53 (03) Cd 18-90 (97) Cc 17-95 (09) Cc 15-60 (89) Ti 1a-64(09) Cd 20-91 (09) Cd 22-91 (09) Cd 10-57 (95) Ca 5a-40 (12) Ce 1e-91(01) Ce 1c-89 (95) Cd 14b-93 (95) Ce 1c-89 (95) Cd 14-95 (09) Ce 1f-96 (09)
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Bleaching test • For refined cottonseed oil • For refined soybean oil • For refined sunflower oil Lovibond color Wesson (Lovibond) method Color (per ISO Standard) Color (automated method) Chlorophyll pigment Refined and bleached oils Crude vegetable oils Crude vegetable oils Trace metals By AAS (Cr, Cu, Fe, Ni) By graphite furnace AAS (Cr, Cu, Fe, Ni, Mn) By graphite furnace direct (Cu, Fe, Ni) By graphite furnace AAS (Pb only) By ICP-OES (all metals) Phosphorus in oils By AAS By ICP-OES By IO method Smoke point, flash point, and fire point Cleveland open cup method Melt point Capillary tube method Mettler dropping point Slip melting point Slip melting point, ISO Standard Wiley methoda
Cc 8a-52 (12) Cc 8b-52 (11) Cc 8b-52 (11) Cc 13b-45 (09) Cc 13e-92 (09) Cc 13j-97 (09) Cc 13d-55 (09) Cc 13i-96 (13) Cc 13k-13 (13) Ca 15-75 (09) Ca 18-79 (09) Ca 18b-91 (09) Ca 18c-91 (09) Ca 17-01 (09) Ca 12b-92 (09) Ca 20-99 (09) Ca 12a-02 (09) Cc 9a-48 (09) Cc 1-25 (09) Cc 18-80 (09) Cc 3-25 (09) Cc 3b-92 (09) Cc 2-38 (91)
a
Surplus method—could be considered obsolete.
Active oxygen method (AOM)a Oil stability index(OSI) Refining loss • Degummed, expeller soybean oil • Degummed hydraulic and extracted soybean oil • Extracted and reconstituted prepressed cottonseed oil • Vegetable oils crude Neutral oil • Loss • In soap stock Unsaponifiable matter Saponification value Mono and diglycerides • By capillary GLC • By HPLC-ELSD
Cd 12-57 (93) Cd 12b-92 (09) Ca 9a-52 (09)
Ca 9F-57 (09) G5 -40 (09) Ca 6a-40 (11) Cd 3-25 (13) Cd 11b-91 (09) Cd 11d-96 (09)
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Mono, di and triglycerides • By silica gel chromatography Alfa monoglycerides Moisture and volatiles (butter fat, margarines, oils) • By hot plate method • Vacuum oven method (except coconut oil) • By distillation method • By Karl Fischer method Alkalinity • Of fats and oils • In soda soap and products Acetone insoluble matter • In lecithin
Cd 11c-93 (09) Cd 11-57 (11) Ca 2b 38-(09) Ca 2d-25 (09) Ca 2a = 45 (09) Ca 2e-84 (09) Cd 3e-02 (09) Da 7-48 (09) Ja 4-46 (11)
a
Surplus method—could be considered obsolete.
2.8 SIGNIFICANCE OF THE ANALYTICAL METHODS AND RESULTS 2.8.1 Iodine Value This method determines the degree of unsaturation in the oil. The results are expressed as grams of iodine absorbed per 100 g of the oil sample. Oils with higher unsaturation show higher IV values. Iodine values of most common crude vegetable oils are listed in Table 2.6.
2.8.2 Free Fatty Acids This method determines the amount of FFA present in the oil. Generally, results are expressed as percent oleic acid for seed oils. It is expressed as percent palmitic acid for palm oil and palm oil derivatives, and as percent lauric acid for palm kernel or coconut oils.
TABLE 2.6 Typical Iodine Values of Common Refined Vegetable Oils Oil type
Typical iodine value
Soybean
132
Canola
120
Sunflower oil
128
Cottonseed oil
110
Palm oil
50
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2.8.3 Acid Value The acid value for oil is the number of mg of potassium hydroxide required to neutralize the free acid in 1 g of the oil. For easy reference: AV = 1.99 FFA (%)
2.8.4 Peroxide Value This method measures the primary state of oxidative of the unsaturated fatty acids in oil. The fatty acid can be in the form of FFA or as part of a triglyceride molecule. This method measures all substances in the oil, which oxidize potassium iodide under conditions of the method as milliequivalents of peroxide per 1000 g of oil or fat. PV of freshly bleached as well as deodorized oil must be “zero.”
2.8.5 para Anisidine Value pAV is defined by convention as 100 times the optical density of a solution containing 1 g of oil and 100 mL of a mixture of solvent and reagents specified in the test method, measured in a 1-cm cuvette at 350 nm. This test measures some of the secondary oxidation compounds of oils and fats generated from the decomposition of the peroxides. Specifically, 2-alkenals and 2, 4-dienals are measured by this method. Freshly deodorized oil may have a pAV content of 2–6.
2.8.6 Soap in Oil This titrimetric method determines alkalinity in the oil as parts per million sodium oleate. Presence of soap in bleached oil indicates poor bleaching. Properly refined and bleached oil must have zero soap content. Soap in bleached oil can cause numerous production and quality problems which will be discussed later.
2.8.7 Conjugated Dienes This spectrophotometric method determines diene linkages of unsaturated fatty acids present in oil in terms of percent of oil. This is a measure to understand the onset of autoxidation reaction, and will be discussed later in Chapter 12.
2.8.8 Polar Material (TPM) This method determines the total amount of polar materials present in the oil by column chromatography. It is used as a measure of oxidative degradation for oil, especially in frying processes.
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2.8.9 Polymerized Triglycerides This method determines polymerized triglycerides in fats and oils by a gelpermeation method, and indicates the degree of thermal and oxidative abuse of the oil.
2.8.10 Solid Fat Index This is a dilatometric method which determines the combined volume of solid and liquid in the sample at specific temperatures. It is an empirical measure of solids fat content in a sample of oil at specified temperatures. The information is used in formulating shortenings, margarines, and spreads.
2.8.11 Solid Fat Content This Nuclear Magnetic Resonance Spectrometry (NMR) method estimates the amount of fat solids present in the oil (fat) sample at specific temperatures. It is also used in formulating shortenings, margarines, and spreads, and originally was developed for the emerging modern palm oil industry.
2.8.12 Fatty Acid Composition This capillary method identifies the fatty acids in a fat or oil by analysis of the sample’s fatty acid methyl esters by capillary gas–liquid chromatography. The fatty acid methyl esters are prepared according to AOCS Method Ce 2-66 (09). This method does not identify cis or trans isomers.
2.8.13 Fatty Acid Composition The packed column method is especially suitable for analyzing hydrogenated fat because it is capable of providing (1) fatty acids identities and compositions, and (2) TFA and cis–cis methylene-interrupted unsaturation. This method yields slightly lower trans values as compared to the infrared spectrophotometric method (AOCS Method Cd 14-61).
2.8.14 trans Fatty Acid TFA in hydrogenated fat is becoming increasingly critical for the vegetable oil industry.
2.8.15 Refined and Bleached Color Test These methods are available applicable to refined cottonseed oil soybean and sunflower oils. These tests are particularly helpful to predict the color of the deodorized oil that could be obtained from a given crude oil.
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2.8.16 Lovibond Color Method Cc 13b-45 (09) compares the oil color by comparing against colored glasses. This method can be used to measure color of all normal oils provided there is no turbidity in the sample. Method Cc 13e-92 (09) is preferred by the British Standard Lovibond International trade. Method Cc 13j-97 (09) is suitable for measuring colors of all refined, bleached, and deodorized vegetable oils and also filtered and deodorized tallow. The Automated method gives results in the AOCS-Tintometer (Wesson method) or the Lovibond color scale. Lovibond color can be used to track degree of removal of color bodies present in the original crude oil. Each type of oil has a characteristic Lovibond Red color. A higher color indicates problems either with the oil or the process. These will be discussed in detail later in Chapters 6, 8, and 12.
2.8.17 Chlorophyll Pigments This spectrophotometric method determines the concentration of chlorophyll in expelled, refined, and bleached oils by measuring absorption at 630, 670, and 710 nm wavelengths. This method is not applicable to hydrogenated oils, deodorized oils, or finished products.
2.8.18 Trace Metals (ICP) The ICP method, or Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), is used for quantitative determination of calcium, copper, iron, magnesium, nickel, silicon, lead, sodium, and cadmium in oil, when these impurities are present in the solubilized form in the oil. Suspended material, such as bleaching clay or nickel catalyst cannot be detected by this method. The detection level by this method is extremely low and precise.
2.8.19 Trace Metals (Atomic Absorption Method) This method is suitable for crude oil and partially refined oil. It can determine copper, chromium iron and nickel as low as 0.1 ppm in the oil.
2.8.20 Phosphorus (Graphite Furnace) This method determines the phosphorus content in parts per million. It involves vaporization of the oil in a suitable graphite furnace and an atomic absorption spectrophotometer for reading.
2.8.21 Phosphorus (ICP) This method quantitatively determines the phosphorus level in oil by using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES).
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2.8.22 Smoke Point, Flash Point, and Fire Point (Cleveland Open Cup method) Smoke point is directly related to the amount of FFA in the oil, and also to the amounts of monoglycerides and diglycerides present in the oil. The flash point of solvent-extracted crude oil must be checked at receipt to make sure it is higher than 300°F (149°C). The smoke point for the degummed soybean oil or crude sunflower oil is 250°F (121°C) maximum, according to the Trading rules of NIOP.
2.8.23 Melt Point (Capillary Tube Method) The complete melting point of fat is determined by this method.
2.8.24 Melt Point (Mettler Drop Point Method) The temperature at which the fat sample becomes soft and flows under the specific conditions of the test is measured by this method. This is an approximate method for melt point because one can see higher melting solids in the melted sample even at a temperature higher than the melt point determined by this method.
2.8.25 Active Oxygen Method (AOM) This method measures the time in hours needed for the PV of a sample to reach 100 mEq when tested under the conditions specified. This is a measure of the primary oxidative stability of oil. AOM provides good information oil stability for salad dressing and applications that do not require high temperature treatment for the oil. Most oil processors and end users stopped using this method because the following method is found to be more useful to determine the oxidative stability of the oil.
2.8.26 Oil Stability Index (OSI) This method provides the tertiary oxidative state for the oil. In oil applications, OSI is a better measure of oil stability while processing of foods formulated with the oil and is subjected to high temperature. The apparent basic difference between OSI and AOM is that OSI estimates the time required to exhaust antioxidants present in the sample and begins accumulating peroxides, while AOM measures the total time required for the sample to degrade to the 100 mEq PV. The OSI method provides better information about the secondary and tertiary oxidation of the oil. This will be discussed further in Chapter 12.
2.8.27 Refining Loss There are several methods for the test that apply to different oils as listed previously.
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2.8.28 Neutral Oil Loss 2.8.28.1 In Refining The total natural oil of natural fats and oils consisting essentially of triglycerides and unsaponifiable matter is determined by this method. The fatty acids and miscellaneous nonfat substances are removed by passing through a column of activated alumina. The loss is the difference between the amount of feed and that recovered, expressed as percent. This method is satisfactory for cottonseed, soybean, peanut (groundnut), linseed, coconut, and sunflower oils. 2.8.28.2 In Soap Stock There is always a certain amount of neutral oil that remains in the soap stock that is discharged from the primary separator in caustic refining process. This method allows one to determine the amount of neutral oil in the soap stock.
2.8.29 Unsaponifiable Matter Unsaponifiable matter include those substances frequently found dissolve in fats and oils, which cannot be saponified by the usual caustic treatment, but are soluble in ordinary fat and oil solvents. Included in this group are high aliphatic alcohols, sterols, pigments, and hydrocarbons. This method is applicable to normal animal and vegetable oils and fats but is not applicable to marine oils and the feed-grade fats.
2.8.30 Saponification Value This method is defined as the number of milligrams of KOH required to saponify 1 g of the oil sample. This method is important in the soap making industry. This method is applicable for vegetable oils, deodorizer distillates, and sludges.
BIBLIOGRAPHY Food Codex Alimentarius Commission Standard 210.(1999). Bockisch, M., 1993. Fats and Oils Handbook. AOCS Publication, USA. Gupta, M.K., 2017. Practical Guide to Vegetable Oil Processing. AOCS Publication, Peoria, IL, USA, 2007. Muller-Mulot, W., 1976. J. Am. Oil Chem. Soc. 53, 732. Ooi, C.K., Choo, Y.M., Yap, S.C., Basiron, Y., Ong, A.S.H., 1994. Recovery of carotenoids from palm oil. J. Am. Oil Chem. Soc. 71, 423–426. Slover, H.T., Lehmann, J., Valis, R.J., 1969. Vitamin in foods: determination of tocols and tocotrienols. J. Am. Oil Chem. Soc. 46, 417–420.