WO1991008676A1 - Huiles comestibles faiblement satures et leurs procedes de production par transesterification - Google Patents

Huiles comestibles faiblement satures et leurs procedes de production par transesterification Download PDF

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Publication number
WO1991008676A1
WO1991008676A1 PCT/US1990/007336 US9007336W WO9108676A1 WO 1991008676 A1 WO1991008676 A1 WO 1991008676A1 US 9007336 W US9007336 W US 9007336W WO 9108676 A1 WO9108676 A1 WO 9108676A1
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Prior art keywords
fatty acid
oil
fatty acids
unsaturated
transesterification
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PCT/US1990/007336
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English (en)
Inventor
Robert C. Dinwoodie
Michael T. Dueber
David K. Hayashi
R. G. Krishnamurthy
James J. Myrick
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Kraft General Foods, Inc.
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Publication of WO1991008676A1 publication Critical patent/WO1991008676A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone

Definitions

  • the present invention is directed to methods for preparing edible triglyceride vegetable oils having a very low level of saturated fatty acid components, and to enzymatic transesterification methods for producing such low-saturate, edible oil products.
  • Edible oils and fats typically primarily comprise various fatty acid triesters of glycerol with the structure of the fatty acid moieties and their distribution on the glycerol backbone determining the physical characteristics of the oil or fat.
  • the specific types of fatty acids also play an important role in diet and health. Fats and oils in general are a rich source of energy in the diet and are important in the synthesis of membranes and other essential cell components. Moreover, dietary fatty acid content may potentially be controlled to affect physiological
  • Natural vegetable oil triglycerides typically contain substantial amounts of esterified saturated fatty acids.
  • soybean oil may typically contain about 14-16 weight percent of esterified saturated fatty acids
  • natural canola oil may contain about 5-8 weight percent of esterified saturated fatty acids.
  • Soybean oil and canola oil typically contain, respectively, over 10 percent and over 3 percent by weight of esterified intermediate chain length saturated fatty acids, primarily palmitic acid. Accordingly, it would be desirable to economically produce or manufacture triglyceride oils having very low levels of saturated fatty acids, and particularly low levels of lauric, myristic and palmitic acids. Most food products prepared from vegetable oils having less than about 3.5 weight percent of esterified saturated fatty acids may be regarded as substantially free of such fatty acids for regulatory purposes.
  • fatty acid synthesis has many potential rate limiting enzymes as well as proteins, such as acetyl-CoA carboxylase,
  • ACP-acetyl transferase 3-oxoacyl ACP synthase, ACP malonyl transferase and acyl carrier protein.
  • Modifications of specific triglyceride synthesis entail changes in fatty acid composition dependent on acyl ACP thioesterase and various desaturase complexes, as well as acyltransferase enzymes which attach the fatty acid moieties to glycerol.
  • acyltransferase enzymes which attach the fatty acid moieties to glycerol.
  • Chemical and enzymatic transesterification are well known for modifying the fatty acid composition or distribution of triglyceride oils.
  • transesterification is based on the use of a chemical catalyst such as sodium methoxide or a sodium metal to promote the migration of the fatty acid moieties between glyceride molecules, to produce a random distribution of the fatty acid moieties.
  • a chemical catalyst such as sodium methoxide or a sodium metal to promote the migration of the fatty acid moieties between glyceride molecules, to produce a random distribution of the fatty acid moieties.
  • Enzymatic transesterification of triglycerides may also be used to modify the characteristics and/or
  • composition of triglycerides Such processes may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • vegetable oils may be used for selective interchange under relatively mild reaction conditions.
  • Extracellular microbial Upases are generally of three types, depending upon their specificity.
  • One group of upases is generally nonspecific, both as regards the position on the glycerol molecule which is hydrolyzed or esterified, and the nature of the fatty acid released or esterified.
  • such Upases catalyze the nonselective hydrolysis, alcoholysis and/or esterification (including transesterification) of fatty acid triglycerides.
  • the Upases produced by Candida cylindracae also known as C. rugosa (Benzonana, G. and S. Esposito, Biochim, Biophy. Acta. 231:15 (1971)),
  • a second group of lipases preferentially acts on the primary, 1- and 3- positions of the glycerol or
  • triglyceride molecule When a 1-,3- positionally specific lipase is used to catalyze the transesterification of a mixture of triglycerides or a mixture of triglyceride plus free fatty acid or monoester, the action of the enzyme is substantially confined to the 1- and 3- positions of the glycerol.
  • the lipases of Rhizoous delemar and Mucor miehei such as described in U.S. Patent 4,798,793, are examples of 1-,3- specific lipases.
  • a third group of lipases has substantial
  • Triglycerides containing medium chain saturated C 10 and C 8 fatty acids may exhibit some, albiet reduced,
  • delta-9 specific lipases which preferentially act on long-chain fatty acids containing a cis double bond in the 9 position are the lipase produced by the mold Goetrichum candidum
  • Enzymatic methods which may be use ⁇ to reduce the saturated fatty acid content of vegetable oils to levels below about 3.5 weight percent, and total levels of
  • FIGURE 1 is a process flow diagram for an embodiment of a single step batch or cocurrent continuous enzymatic transesterification reaction method for producing a low saturate triglyceride in accordance with the present invention having less than 3 weight percent esterified saturated fatty acids;
  • FIGURE 2 is a process flow diagram for a continuous countercurrent selective enzymatic reaction method utilizing a supercritical countercurrent gas stream for producing a low saturate triglyceride oil having less than 3 weight percent of esterified saturated fatty acids;
  • FIGURE 3 is a process flow diagram for another method of preparing a low-saturate edible oil by
  • FIGURE 4 is a process flow diagram of another embodiment of a transesterification method for
  • triglyceride oil having less than 3.5 and preferably less than 3 weight percent of esterified saturated fatty acid, and desirably less than 2, and more preferably less than 1 weight percent of intermediate chain length esterified saturated fatty acid.
  • Various aspects of the present invention are also directed to low saturate liquid vegetable oil products having less than 3.5 weight percent, and preferably less than 3 weight percent saturated fatty acid moieties, and specific unsaturated fatty acid distribution, which liquid vegetable oil products have desirable properties for use in food products such as mayonnaise, margarine, table spreads or salad dressings.
  • Such low saturate vegetable oil products will also desirably have less than about 2 and preferably less than 1 weight percent of intermediate chain saturated fatty acids.
  • intermediate chain saturated fatty acid is meant, lauric, myristic and palmitic acids having carbon chain lengths of C 12 , C 14 and C 16 ,
  • the weight percent of saturated or unsaturated fatty acid moieties in a margarine oil or vegetable oil glyceride composition is calculated based on the total weight of the fatty acids contained in the margarine oil. Also, as used herein, when referring to weight percent of one or more fatty acid moieties of a composition (such as the weight percentage of C 12 -C 16 fatty acids), the weight percent is calculated based on all of the fatty acids of the composition being fully hydrolyzed to free fatty acid. The weight percent of one or more species of fatty acid is then calculated as the weight percent of such one or more species based on the total weight of free fatty acids.
  • AOCS official method Ce 1-62 (81) may be used to determine the weight percent of respective fatty acids of an oil or fat composition.
  • a high-unsaturate vegetable oil such as canola (low erucic acid rapeseed) oil, high oleic safflower oil, high oleic sunflower oil, high linoleic safflower oil, high linoleic sunflower, corn oil, olive oil, peanut oil, soybean oil or mixtures thereof, having from about 4 weight percent to about 18, weight percent of saturated fatty acids with respect to the total fatty acid content of the vegetable oil is provided for
  • Canola oil is a
  • the vegetable oil should best be refined and bleached oil which is substantially free of proteinaceous and other nonglyceride components which might poison or otherwise interfere with transesterification enzymes.
  • Canola oil typically comprises in the range of from about 5 to about 7 weight percent of saturated fatty acid moieties. However, the saturated fatty acids of canola oil (and other vegetable oils) is not randomly
  • canola oil typically may have an overall stearic acid content of about 1.5 - 2 weight percent based on the total fatty acid content of the oil, with from about 2 to about 3 weight percent of the fatty acid moieties in the 1- and 3- positions being stearic acid and less than about 1 weight percent of the fatty acids in the secondary 2- position being stearic acid.
  • canola oil may typically have an overall palmitic acid content of about 4 weight percent, with about 6 weight percent of the fatty acid groups in the 1- and 3- positions being palmitic acid and less than about 1 weight percent of the fatty acid groups in the 2- position being palmitic acid.
  • the saturated fatty acids of the primary 1- and 3- positions are selectively removed, and replaced with unsaturated fatty acids by selective transesterification reaction.
  • transesterification is meant an exchange of fatty acid moiety or acyl radical at a
  • glyceride oxygen or hydroxyl group which includes
  • the high unsaturate vegetable oil such as canola oil is combined with an unsaturated fatty acid transesterification
  • component selected from the group consisting of free fatty acids, fatty acid monoesters of lower alkyl monohydric alcohols (e.g., methanol, ethanol and propane), and
  • unsaturated fatty acid transesterification component should comprise at least about 98 weight percent of unsaturated fatty acids having a chain length of from 12 to about 22 carbon atoms, and less than 2 weight percent of saturated fatty acids having a carbon chain length in the range of from 12 to 18 carbon atoms based on the total fatty acid content of the transesterification component.
  • the fatty acid transesterification component comprises less than 0.75 weight percent and preferably less than 0.5 weight percent of intermediate chain saturated fatty acids, by weight, based on the fatty acid content of the
  • the high-unsaturate vegetable oil such as canola oil and the unsaturated fatty acid are combined in a weight ratio of vegetable oil to unsaturated fatty acid
  • transesterification component in the range of from about 1:10 to about 4:1 in batch reaction processes (which may utilize multiple reaction steps), and typically in the range of from about 1:2 to about 2:1 in single stage batch or cocurrent reactions to provide a transesterification mixture.
  • the ratio of reactants may be selected to provide a desired degree of substitution under the reacrion
  • the ratio of reactants and the composition of the unsaturated fatty acid transesterification component may be selected to provide specific compositions of the transesterified low saturate oil, in terms of unsaturated fatty acid composition. For example, nutritionally desirable unsaturated fatty acids in
  • transesterification enzyme which is desirably a 1-, 3- specific transesterification enzyme such as an immobilized lipase from Mucor miehei as described in U.S. Patent
  • transesterification mixture is contacted with the immobilized enzyme under time and temperature conditions for substantially equilibrating the fatty acid content in the 1- and 3- positions of the
  • the enzymatic transesterification reaction produces a transesterified triglyceride component and a transesterified fatty acid component.
  • the reaction time may range from about 0.5 hour to about 100 hours, depending upon the concentration and activity of the lipase and the temperature of the reaction mixture.
  • the transesterification reaction will desirably be carried out at a temperature in the range of from about 20o c. to about 80o C., and more preferably in the range of from about 40o C. to about 70o C.
  • equilibrate is meant that the transesterification reaction is at least about 50 percent complete, and preferably at least 90 percent complete. Lower equilibrium
  • transesterification conditions e.g., 50-90 percent
  • a transesterified fatty acid component is separated from the transesterified glyceride component of the transesterification mixture.
  • the transesterified glyceride component has less than 3 weight percent esterified saturated fatty acid content, based on the total weight of the glyceride.
  • the transesterified glyceride component will comprise less than 3.5 weight percent of saturated fatty acids based on the total weight of fatty acids in the transesterified glyceride component, and may preferably have less than 3 weight percent of esterified saturated fatty acids, and for specific uses may desirably comprise less than two weight percent of
  • the transesterified fatty acid component separated from the transesterification mixture is fractionated to separate the unsaturated fatty acids from saturated fatty acids, to provide a recycle unsaturated fatty acid source material comprising less than 2 weight percent and preferably less than 1 weight percent of saturated fatty acids, based on the total weight of fatty acids in the source material.
  • the recycle fatty acid source material is combined in a recyclic manner with the high unsaturate vegetable oil such as canola oil as an unsaturated fatty acid
  • transesterification component as previously described, to produce low-saturate triglyceride oils in accordance with the present invention.
  • the recyclic use of the unsaturated fatty acid components is important to the economics of the process.
  • the fractionation of saturated fatty acids from the fatty acid mixture to provide such a low level of saturated fatty acid content is a difficult fractionation step and may be carried out by a variety of procedures, such as vacuum distillation, selective urea adduction and/or selective adsorption chromatography.
  • the saturated fatty acids are difficult to remove from unsaturated fatty acids at low concentration levels.
  • Solvent crystallization at low temperatures may be used to remove at least a portion of the saturated fatty acid content, although typically such solvent crystallization procedures do not reduce the saturated fatty acid content to levels below about 2-3 weight percent of the fatty acid mixture.
  • solvent crystallization fractionation procedures may be used to reduce the saturated fatty acid content for subsequent procedures such as molecular distillation, urea adduction or other selective absorption fractionation procedures. It is important that the technique utilized ultimately provide a separation such that an unsaturated fatty acid recycle component having less than 2 weight percent by weight, based on the total weight of the fatty acids of the recycle component, and preferably less than 1 weight percent, is provided for recyclic transesterification use. Desirably, at least about 90 weight percent of the unsaturated fatty acid component from the transesterification reaction will be recovered for recyclic use.
  • enzymatic transesterification is utilized to reduce the level of saturated fatty acids in a triglyceride vegetable oil by the addition of unsaturated fatty acids in a ratio
  • the enzymatic transesterification reaction may be driven to a desired targeted fatty acid composition in accordance with the present invention.
  • enzymatic transesterification processes may produce oils with less than 3.5 weight percent of saturated fatty acids and preferably less than 3 weight percent saturated fatty acids, based on the total fatty acid content.
  • oils with less than 3.5 weight percent of saturated fatty acids and preferably less than 3 weight percent saturated fatty acids, based on the total fatty acid content.
  • interesterified oils having reduced levels of saturated fatty acid contents of 1.6%, 1.0% and 0.9%, respectively, may be readily provided.
  • such low saturate products may be provided having a substantially 1:1 ratio of monounsaturates to polyunsaturates.
  • Such starting feedstock materials may also readily be converted to oils having a 2:1:1 weight ratio of omega-9 :omega-6:omega-3 unsaturated fatty acid content.
  • canola oil may also be readily interesterified to produce an oil with a 2:1:1 weight ratio of omega-9:omega-6:omega-3 esterified unsaturated fatty acids, and a saturated fatty acid content of 2.1%.
  • the free fatty acids which are used to drive the reaction are recycled by separation of saturated fatty acids from unsaturated fatty acids.
  • triglycerides from free fatty acids may also be utilized in specific embodiments of such methods.
  • the saturated fatty acid distribution of vegetable oils such as canola oil is non-random, and is predominantly distributed at the 1-, 3- positions of the vegetable oil glycerides. Accordingly, by utilizing a 1-, 3- specific lipase such as previously described, the transesterification reaction may be limited to the 1-, 3- positions containing the predominant amount of saturated acids in the vegetable oil, without
  • lipases While 1-, 3- specific lipases are preferred for use with oils such as canola oil in which the saturated fatty acids are concentrated in the 1- and 3- positions, other lipases may also be used, particularly in oils which do not significantly concentrate saturated fatty acids in the 1-, 3- positions or which nevertheless have excessive saturated fatty acid amounts at every glyceride position. For example, it may be more economical to use a
  • non-specific lipase such as the lipase from Candida ruoosa to enable the reduction of stoichiometric amounts of free fatty acids in oils in which all three positions on the triglyceride will desirably be available for exchange.
  • FIGURE 1 Illustrated in FIGURE 1 is a schematic diagram of a system 100 for producing edible low saturate triglyceride oils in accordance with the present invention. As shown in
  • the system 100 comprises a linseed oil storage vessel 102 to provide a source high in linolenic acid, a sunflower, safflower, corn or soybean oil storage vessel 104 to
  • a source high in linoleic acid and a high oleic sunflower, high oleic safflower or olive oil storage vessel 106 to provide a source high in oleic acid.
  • one or more of these high linolenic, high linoleic or high oleic source triglycerides is conducted through a conduit 108 to a hydrolysis reactor such as membrane reactor 110 for hydrolysis of the fatty acids of the oil.
  • the reactor 110 may utilize a basic hydrolysis catalysts such as sodium hydroxide, sodium methoxide or an immobilized non-specific lipase to fully hydrolyze the triglyceride source material, or may utilize an immobilized unsaturated fatty acid-specific lipase, as previously described, to hydrolyze substantially only the unsaturated fatty acid components of the source
  • the fatty acid components which may include saturated fatty acid components from the source
  • the fatty acid separator 120 may utilize any appropriate separation technology, and, for example may be a separator such as a low temperature molecular distillation column, a urea adduction separator, ["Fatty Acids, Their Chemistry, Properties, Production and Uses", Part 3, K.S. Markley, Ed., Interscience Publishers, 1964], or a selective separation technology, and, for example may be a separator such as a low temperature molecular distillation column, a urea adduction separator, ["Fatty Acids, Their Chemistry, Properties, Production and Uses", Part 3, K.S. Markley, Ed., Interscience Publishers, 1964], or a selective
  • the separation step performed by the separator 120 is an important step in the method and, as will be described
  • unsaturated fatty acid transesterification mixture 122 comprising less than about 2 weight percent of saturated fatty acids, and preferably less than about 1 weight percent fatty acids is produced by the separator 120.
  • a saturated fatty acid stream 118 is discharged from the separator, and may be utilized for other purposes such as the preparation of hard fats, soaps or chemical synthesis.
  • the unsaturated transesterification fatty acid mixture 122 is combined with refined canola oil from storage vessel 130.
  • the canola oil may typically have a saturated fatty acid content which is concentrated in the 1-, 3- position, as shown in the following table:
  • the unsaturated fatty acid and canola oil are combined in a weight ratio in the range of from about 0.4 to about 3 of fatty acid to canola oil, to provide a canola oil - fatty acid transesterification reaction mixture 132 which is saturated or supersaturated with water by heat exchanger 134, and water saturator 136, as shown in
  • the heat exchanger 134 heats the mixture 132 of canola oil and unsaturated fatty acids to approximately the desired reaction temperature of the transesterification reaction, which will preferably be in the range of from about 40o C. to about 70o C.
  • the heated transesterification mixture 135 is conducted into the water saturator 136, which desirably is a column of anionic resin such as the AmberLite IRA-900 anionic resin product of Rohm and Haas, which is saturated with water.
  • the anionic resin in addition to rapidly saturating the canola oil-unsaturated fatty acid mixture with water, may also function to remove impurities which may poison or adversely affect the enzyme in the subsequent enzymatic transesterification reaction step.
  • the reaction mixture 138 which is discharged from the water saturator 136 is saturated or supersaturated with water, and in this regard, may typically comprise from about 0.2 to about 0.8 weight percent cf water.
  • the mixture 138 may be supersaturated by slightly cooling a water-saturated reaction mixture. The saturation or supersaturation of the mixture 138 with water is necessary to maintain the utility of the resin-bound
  • transesterification enzyme in the transesterification reaction which will now be described in more detail.
  • the water-saturated or supersaturated reaction mixture 138 is introduced into an transesterification reactor 140, which in the illustrated embodiment 100 contains an immobilized 1-, 3- positionally specific transesterification lipase immobilized on or within an organopolymeric resin, such as the Novo 3A lipase product of Novo Industries, which is an immobilized 1-, 3- positionally specific lipase derived from Mucor miehei, as described herein.
  • the fatty acids of the fatty acid source and the fatty acids of the 1-, 3- positions of the canola oil are substantially equilibrated in the reactor 140 to provide an transesterification reaction product mixture 142 which is conducted to a triglyceride/fatty acid membrane separator 150.
  • the mixture 142 generally contains from about 2 to about 8 weight percent of diglycerides produced by the action of the enzyme and water, but may contain up to about 15 weight percent of diglycerides, depending on factors including water content and reaction conditions.
  • the life time of the immobilized lipase system is important in commercial production, and may be monitored by means of an assay system to determine the half-life of the immobilized lipase system
  • immobilized lipase in the canola oil reactor 140 As previously indicated, impurities in both the fatty acids and canola oil may accumulate on the resin and affect the enzymatic activity, and accordingly, pure materials should best be used in the reaction.
  • the illustrated triglyceride/fatty acid separator 150 may be a separator apparatus which separates the fatty acid components including those produced in the reaction from the di- and triglyceride components by any appropriate methods, such as by selective absorption fractionation processes, subcritical liquified gas (e.g., propane) countercurrent extraction ["Liquid-Liquid Extraction
  • fatty acid component may be separated with the fatty acid component if desired by selective adsorption fractionation processes, countercurrent selective solvent treatment processes, or other suitable procedures, depending upon desired composition and food product utilization of the
  • transesterified vegetable oil 160 is transesterified
  • the transesterified di- and triglyceride product 160 has an esterified saturated fatty acid content of less than 3.5 weight percent, and may be used in a wide variety of food products, such as liquid margarine or cooking oils, mayonnaise and salad dressings, to provide products having extremely low lsvels of saturated fat. High levels of diglycerides together with very low levels of
  • monoglycerides which may be provided in the process may be particularly desirable in the manufacture of certain emulsified food products containing such low saturate content oils.
  • the free fatty acids in product stream 162 are separated from the fractionation solvent (if used) by appropriate recovery apparatus 170, which is recycled to separator 150, to provide a recovered fatty acid stream 172 and recovered solvent 174.
  • the recovered fatty acid stream 172 contains saturated fatty acids from the canola oil 130, and from the unsaturated fatty acid stream 122 as a result of the transesterification reaction.
  • This fatty acid recycle stream is conducted to the separator 120 for separation of the fatty acid
  • Amounts of saturated fatty acid recovered, and unsaturated fatty acids lost by the separator 120 or in other processing are made up by fatty acids from the source tanks 102, 104, 106 as needed to provide the proper
  • low saturated oil may be produced by batch or continuous transesterification reaction methods to produce
  • oils with desired fatty acid compositions.
  • Such oils may be selected for fatty acid composition based on the fatty acid composition of the starting oil and the fatty acid composition and relative proportions of the fatty acids used in the reaction.
  • subcritical fluids which selectively extract and transport the fatty acid may desirably be utilized to provide
  • solubility of fatty acid esters such as fatty acid methyl and ethyl esters are typically an inverse function of molecular weight of the fatty acid monoester under various conditions.
  • solubility of fatty acids is inversely proportional to molecular weight of the fatty acid, although fatty acids are typically less soluble in supercritical gases, than corresponding fatty acid lower alkyl monoesters of corresponding molecular weight because of the associative or hydrogen bonding characteristics of the fatty acids.
  • the respective solubilities of fatty acids, fatty acid esters and triglycerides in carbon dioxide are also a function of temperature and partial pressure of CO 2 at relatively low supercritical pressures.
  • An embodiment of continuous transesterification process which moves a fatty acid or fatty acid monoester component countercurrent to triglyceride flow, and which also removes such fatty acid transesterification reaction components from the transesterified glyceride, is
  • a source of canola oil 212 or other vegetable oil having a low (e.g., preferably less than 10 weight percent, and more preferably less than 7 weight percent) esterified saturated fatty acid content is provided as a starting material.
  • An unsaturated fatty acid (or fatty acid low alkyl monoester such as a mixture of unsaturated fatty acid methyl or ethyl esters) derived from canola oil having less than 2 weight percent and preferably less than 1 weight percent of saturated fatty acids is provided as a
  • methyl or ethyl esters may be provided by appropriate purification procedures such as fractional crystallization, solvent/solvent extraction, urea adduct fractionation, selective absorption
  • the canola oil 212 may be conducted through a column containing a water-saturated anionic exchange resin to remove non-triglyceride impurities which might poison the enzyme, and condition the oil 212 for the reaction.
  • the column is packed with an immobilized lipase enzyme, which is immobilized on an organic or inorganic, high surface area substrate such as porous ceramic rings or pellets, organic substrates such as crosslinked ion
  • the surface area of the column packing is very large in order to promote interesterification reaction (e.g., more than 750 square meters of surface area per cubic meter), and to promote equilibrium dissolution of the low molecular weight components in the supercritical fluid.
  • the unsaturated fatty acid (or preferably lower alkyl monoester) component 220 is introduced into a first unsaturated fatty acid (or preferably lower alkyl monoester) component 220 .
  • transesterification reactor 214 together with canola oil 212, for transesterification to produce a low saturate triglyceride.
  • An immobilized 1-, 3- specific enzyme 222 such as previously described may be used for
  • transesterification lipase such as the nonspecific enzyme of Candida cylindracae or Candida ruoosa. may be used.
  • dried lipase-containing microorgansism cells and mycelia may also be used as a transesterification enzyme, either retained in the reaction zone, or conducted
  • supercritical carbon dioxide or another supercritical fluid such as an ethane-propane mixture of a fluorocarbon gas having a supercritical temperature for example in the range of from about 30o C. to about 80o C
  • a supercritical temperature for example in the range of from about 30o C. to about 80o C
  • carbon dioxide pressures in the range of from about 1100 psi to about 4500 (e.g., 2000-3000 psi for ethyl esters of oleic, linoleic and linolenic acids), at a reaction temperature in the range of, for example, from about 30o C. to about 70o C., are particularly preferred to provide relatively high fatty acid and/or fatty acid monoester solubility, while
  • the supercritcal fluid may contain a small amount of water vapor to maintain the catalyst and to facilitate fatty acid solubility.
  • the temperature cannot exceed the operating temperature of the enzyme, which will be damaged at high temperatures. In this regard, at lower
  • reaction temperature should be selected (e.g., 35o - 55o C.) which maximizes throughput rate for countercurrent transport of the fatty acid monoester, and the
  • transesterification reaction rate which is provided by the enzyme to achieve transesterification of the triglyceride and the fatty acid or fatty acid monoester.
  • Fatty acid lower alkyl monoesters are substantially more soluble in the supercritical fluid than the corresponding acids, and accordingly are preferred reactants.
  • the supercritical gas also serves as a diluent of the triglyceride phase to increase the reaction rate. If it is desired to operate the countercurrent column at a temperature higher than the lipase enzyme can tolerate, a plurality of enzyme reaction zones 215 may be distributed along the column 214 which may be operated at a lower temperature, with appropriate heating and cooling means for fluid pumped therebetween. In this manner, the transesterification reaction and countercurrent gradient functions may be separately
  • the supercritical carbon dioxide is less dense than the downwardly moving canola oil stream at pressures and temperatures used in the system of FIGURE 2 (e.g., 35-70o C., 1500-3500 psia).
  • the pressure, temperature, column distances and flow rates of fatty acid or fatty acid monoester and carbon dioxide are selected so that in the zone 228 between the point of introduction of the carbon dioxide and the point 222 of introduction of the
  • the fatty acid or fatty acid monoester is progressively dissolved from the triglyceride into the upwardly moving supercritical CO 2 stream; the acid or fatty acid monoester components
  • unsaturated acid or monoester component 220 introduced in the column 214 may desirably be selected to be in the range of from about 5:1 to about 50:1, under conditions to maximize solubility of the fatty acid or preferably fatty acid monoester component while minimizing the solubility of the triglyceride component phase.
  • the unsaturated acid component 220 undergoes transesterification with the triglyceride component.
  • the composition of the fatty acid or fatty acid monoester which enters the countercurrent transesterification zone 226 from the monoester stripping zone 224 will be different from the composition of the fatty acid or monoester 220 introduced into the column 214 at least in part because of the transesterification which occurs in the stripping
  • the transesterified triglyceride product which may have substantially all fatty acid and fatty acid monoester components removed therefrom, is withdrawn from outlet 218.
  • the ratio of triglyceride components to the unsaturated acid or monoester component 220 to achieve a desired degree of transesterification of the canola oil triglyceride is substantially greater in the system of FIGURE 2 than the ratio of triglyceride to fatty acid or monoester utilized to achieve an equivalent degree of transesterification in a one or two step batch reaction.
  • the unsaturated acid or monoester 220 is introduced into the bottom of the column at a rate compared to the rate of introduction of canola oil which may, for example, be about half the proportion used in a batch reaction (e.g., 1:3 to 1:1 weight ratio of unsaturated acid component to canola oil).
  • the fatty acid or monoester component is dissolved in the upwardly moving supercritical CO 2 gas stream and carried into the transesterification zone 226, where it approaches equilibrium with the countercurrent oil flow through the action of the immobilized enzyme in the
  • the triglyceride phase mixture continuously undergoes transesterification reaction as it moves downwardly in the zone 226 containing lipase enzyme countercurrent to the flow of supercritical gas, such that the mixture has an increasing concentration of the desired triglyceride components as it moves down the column.
  • transesterified fatty acid or monoester having fatty acid or monoester components derived from the triglyceride in the upwardly moving supercritical gas stream, in the direction toward the point of introduction of the triglyceride.
  • Water vapor may be included in the carbon dioxide flow, the fatty acid ester flow and/or the triglyceride flow to accommodate the transesterification reaction, which may exceed the
  • Fatty acid components produced by hydrolysis reactions in the column 214 may also be removed by the supercritical carbon dioxide flow.
  • the transesterified fatty monoester or fatty acids dissolved in the supercritical CO 2 gas stream is carried from the column at outlet 216, through a pressure let-down system, where dissolved fatty acids or monoesters are taken out of supercritical solution as a result of pressure reduction.
  • the tank 232 may alternatively be heated to further reduce the solubility of the fatty acid monoester.
  • the solubility reduction may also be accomplished by a combination of a limited pressure reduction (e.g., by 500-1000 psi) and a temperature increase (e.g., to
  • the energy recovery system may comprise a piston or turbine engine 232 in which the dissolved fatty acid or monoester 234 are collected in the recovery system, so that the energy may be recovered for recompression of the carbon dioxide upon recyclic
  • the lower pressure CO 2 which is depleted in or free of dissolved fatty acids or monoesters, is
  • compressor 238 recompressed by compressor 238.
  • the carbon dioxide 236 which is separated from the fatty acid or monoester is conducted to compressor/thermal conditioner 238 where it is recompressed and reintroduced at the preselected operating temperature as previously discussed.
  • a heat-pump or other thermal connector 240 may be used to transfer heat between the compressor 238 and the decompression engine 232.
  • a portion of the extracted fatty acid components 234 may be recycled for reflux purposes to increase selectivity.
  • the flow rate of supercritical carbon dioxide (or other supercritical gas solvent) through the column 214 is correlated with the flow rate of fatty acid ester 220 so that it is adequate to transport and dissolve substantially all of the fatty acid monoester under the operating conditions, but dissolves a minimal amount of the initial canola oil and other triglyceride components.
  • the solubility of the fatty acid or fatty monoester components will desirably be greater than
  • triglycerides will be less than 10 percent of the dissolved fatty acid or monoester in the extracted product 234.
  • the separated fatty acid or monoester 234 may be purified in fractionation system 250 to separate purified unsaturated fatty acids 220 from other materials 252 in any suitable manner, and the unsaturated transesterification component 220 may be recycled for transesterification use.
  • FIGURE 3 moves a fatty acid or fatty acid monoester component countercurrent to triglyceride flow, utilizing a
  • the vegetable canola oil 312 to be transesterified is introduced into a high pressure column 314 at a point 324 intermediate the upper outlet 316 and the lower outlet 318.
  • the rate of introduction corresponds to the transesterification reaction rate
  • the column may be packed with an immobilized lipase enzyme as previously described, which is immobilized on an inorganic, high surface area substrate such as porous ceramic rings or pellets, or diatomaceous earth (e.g., Celite), or a suitable organic substrate such as an ion exchange resin substrate (e.g., Novo 3A lipase).
  • an immobilized lipase enzyme as previously described, which is immobilized on an inorganic, high surface area substrate such as porous ceramic rings or pellets, or diatomaceous earth (e.g., Celite), or a suitable organic substrate such as an ion exchange resin substrate (e.g., Novo 3A lipase).
  • Such packing may be in particulate film or fiber form, on
  • the column 314 may be used to establish concentration gradients and countercurrent flow in stages, and the immobilized enzyme 313 may be located in corresponding stages in a separate pressure vessel 315.
  • the surface area of the column packing should be very large in order to promote transesterification reaction (e.g., more than 750 square meters of surface area per cubic meter), and to promote equilibrium dissolution of the low molecular weight
  • a fatty acid or lower alkyl fatty acid monoester 320 such as a methyl or ethyl ester of an unsaturated fatty acid component (e.g., a mixture of unsaturated fatty acids or unsaturated fatty acid esters such as methyl or ethyl esters), which is desired to be transesterified with the triglyceride 312, is introduced into the column 314 at a point 322 intermediate the point 324 of introduction of triglyceride, and the lower outlet 318 at a rate which maximizes the desired transesterification reaction.
  • an unsaturated fatty acid component e.g., a mixture of unsaturated fatty acids or unsaturated fatty acid esters such as methyl or ethyl esters
  • the rate of introduction is about 0.25 to 1.0 the rate of vegetable oil input, lower ratios being used for higher purity (e.g., less than 0.5 or 0.25 weight percent saturated fatty acid content).
  • the transesterification reaction is conducted in a countercurrent manner, so that it is substantially more efficient than the batch reaction of the fatty acid and triglyceride component at the
  • liquified propane 309 is introduced at a position 319 near the bottom of the column 314 under pressure, flow rate and temperature conditions at which relatively low molecular weight fatty acids and monoesters are significantly dissolved, but at which the high
  • molecular weight triglycerides are less soluble and form a separate phase.
  • the temperature of course, cannot exceed the operating temperature of the enzyme, which will be damaged at high temperatures.
  • the propane may be introduced at a pressure of about 600 psi and a temperature of 70o C. at a rate of about 10 times the rate of introduction of fatty acid 320 on a weight ratio basis. If a lower temperature is
  • ethane or ethane/propane mixtures may be used.
  • the liquified propane gas also dissolves to some extent in the triglyceride phase and serves as a diluent to increase the reaction rate.
  • the liquified propane phase is less dense than the downwardly moving vegetable oil stream, having a density of 0.25-0.4 g/cm 3 , depending primarily on composition
  • distances and flow rates of fatty acids (or monoesters) and liquid propane are selected so that in the zone 324 between the point 319 of introduction of the pure liquified propane and the point 322 of introduction of the unsaturated fatty acid or monoester 320, the fatty acid or monoester
  • the fatty acid or monoester is substantially completely removed from the triglyceride stream 326 before it is discharged from the column at outlet 318. Because of countercurrent transesterification which occurs in the transesterification zones 313 (or in the column 314 in embodiments having lipase enzyme therein), the fatty acids or monoesters in the upwardly rising liquid propane
  • the transesterified triglyceride product is withdrawn from outlet 318. It contains an amount of propane which is an inverse function of
  • propane stripping column 327 which is removed in propane stripping column 327 and returned for recyclic use.
  • the ratio of triglyceride component 312 to the unsaturated fatty acid component 320 to achieve a desired degree of transesterification of the triglyceride will be substantially greater in the countercurrent system than the ratio of triglyceride to fatty monoester necessary to achieve an equivalent degree of transesterification in a batch or cocurrent reaction, as previously discussed.
  • the fatty acid component is dissolved in the upwardly moving propane phase, and is continuously
  • a portion of the mixture is pumped from mixing stages in the column 314 to transesterification zones 313 containing a suitable transesterification enzyme.
  • the mixture continuously undergoes transesterification reaction in the separate zones 313, and is returned to the respective phase separation zones of the column 314, such that the mixture has an increasing concentration of the desired triglyceride as it moves down the column.
  • the columns 314 may be maintained at a higher temperature (e.g., 70-90o C.) at which phase separation is enhanced, while the lipase reaction zones 313 may be maintained at a lower temperature (e.g., 50-60o C.) at which the enzyme longevity and reaction are maximized, by appropriate heating and cooling of the streams conducted there between.
  • a higher temperature e.g., 70-90o C.
  • the lipase reaction zones 313 may be maintained at a lower temperature (e.g., 50-60o C.) at which the enzyme longevity and reaction are maximized
  • monoglycerides (and diglycerides) produced by hydrolysis reactions in the column 314 may also be (at least
  • the transesterified fatty acid component which is preferentially dissolved in the upwardly moving liquid propane phase is carried from the column at outlet 316 at e.g., 70-85o C., through heater/evaporator 330 where it is heated to 93o C. to evaporate pure propane 331 and then into separation tank 332, where dissolved fatty acid components 335 are taken out of solution as a result propane evaporation and temperature increase.
  • the exiting propane phase is heated to further reduce the solubility of the fatty acid (and any
  • the liquid propane exiting the column may be heated to 94-95o C., to create two phases in the
  • a portion (e.g., 20-50 weight percent) of the separated fatty acid component may be reintroduced into the top of the column 314 into a reflux zone to enhance the selectivity of the
  • the material 335 which contains 30-60 weight percent propane as well as some di and triglycerides (and perhaps very small amounts of monoglycerides) in addition to the fatty acid or monoester components, is conducted to a propane stripper 350 and from there the propane-free fatty acid components 352 (which may optionally first be hydrolyzed as previously described) are conducted to an appropriate separation system 352 for separation of the unsaturated fatty acid components in relatively pure form for recycle use.
  • the saturated fatty acid components 354 are separated from the unsaturated fatty acid components in a suitable separator 355.
  • the fatty acids (and any mono, di- and triglycerides) may be further utilized as desired.
  • the unsaturated fatty acid components may be esterified with ethanol and recycled.
  • the liquid propane which is separated from the fatty acids in the tank 332 is conducted to preheat the canola oil 312 and then to pump/thermal conditioner 334 where it is cooled to 70o - 75o C. and reintroduced at the preselected operating temperature. Because it has a very small amount of product fatty acids, it is introduced at an intermediate position in the column 314. A portion of the propane is evaporated at heater/propane boiler 330 and recompressed to produce a pure propane stream for fully stripping the fatty acids and lower molecular weight
  • components may also be separated by heating the propane stream in heater 330 to a temperature above the critical temperature (96-98o C.) of the propane (e.g., 100-110o C.) while maintaining the system at a pressure slightly above the critical pressure (42 atmospheres), such as 44-50 atmospheres. In this way, a substantial portion of the components 335 are separated in column 332, and the
  • supercritical propane gas may be reliquified by cooling to a temperature below the critical temperature for
  • the flow rate of liquified gas solvent through the column 314 is correlated with the flow rate of fatty acid ester 320 so that it is adequate to dissolve substantially all of the fatty acid or monoester under the operating conditions and remove it from the transesterified triglyceride 321.
  • urea adduction may be utilized to separate saturated fatty acid components from unsaturated fatty acids or monoesters to provide a
  • urea typically crystallizes in a tetragonal form, it forms complexes with straight chain fatty acids and lower alkyl monoesters in which the
  • straight chain fatty compound is included within a
  • saturated fatty acids form more stable urea complexes than unsaturated fatty acids of the same, carbon chain length.
  • the stability constants decrease by an order of magnitude in the series stearic, oleic and linoleic acids, respectively [Chapter XX Techniques of Separation E. Urea Complexes, p. 2309, et seq., K.S. Markley, Ed., supra].
  • Saturated monoesters may have greatly increased stability.
  • the stability of fatty acid complexes also increases with the carbon chain length of the fatty acid, and saturated monoesters of lower alkyl alcohols may have enhanced stability.
  • the urea complexes may be readily decomposed by adding water or other solvent to dissolve the urea, leaving the saturated fatty acid inclusion compounds as an oil or solid, depending upon the temperature of decomposition.
  • a small quantity of an acid such as hydrochloric acid may be utilized to prevent formation of emulsions by traces of ammonia soaps.
  • heating the urea complex with a solvent such as hydrocarbon solvent in which the urea is insoluble may also be used to extract the included
  • urea complexes have the melting point of urea, which is approximately 133o C.
  • urea adducts become less stable with increasing temperatures and decompose at a temperature below the melting point of urea, which is characteristic for a specific complex.
  • the dissociation temperature for stearic acid/urea adduct in the absence of any solvent is about 126o C.
  • the dissociation temperature of the palmitic acid/urea adduct in the absence of any solvent is about 114o C.
  • the dissociation temperature of the oleic acid/urea compound in the absence of any solvent is about 110o C.
  • the preferential activity of saturated fatty acids to form urea complexes may be used to remove substantially all of the stearic acid, and a substantial portion of the palmitic acid content of a saturated fatty acid stream in a liquid/solid countercurrent distribution method of
  • dissolved in appropriate solvent may be provided as a moving liquid phase, while the precipitated reaction products may serve as the stationary solid phase.
  • the character of the distribution curve obtained for a given mixture of fatty acids depends on the differences in the distribution coefficients for the individual acids when they are distributed between solid inclusion compounds and the organic solvent [W.N. sumerwell, J. Am. Chem. Soc., 79, 3411-3415 (1957)].
  • FIGURE 4 Illustrated in FIGURE 4, a continuous system for economically providing a transesterified low saturate vegetable oil in which the saturated fatty acids are removed by urea/unsaturated fatty acid inclusion reservoir compounds concomitantly with enzymatic acyl transfer reaction.
  • an unsaturated fatty acid/urea reservoir complex may be prepared which serves as an exchange reservoir for removal of saturated fatty acids.
  • Examples of compounds may be prepared in a suitable manner such as shown in FIGURE 4 by dissolving canola oil fatty acids or a fatty acid lower alkyl monoesters 402, (e.g., methyl or ethyl esters) in a suitable solvent.
  • canola oil fatty acids or a fatty acid lower alkyl monoesters 402, (e.g., methyl or ethyl esters) in a suitable solvent.
  • Methyl and ethyl esters are preferred because urea adducts of palmitic and stearic monoesters may have substantially higher stability constants than oleic acid or oleic acid monoesters, thereby facilitating saturated component removal.
  • the exchange reservoir inclusion compound crystals are formed by dissolving the canola fatty acids or
  • monoesters which comprise about 5-8 weight percent palmitic and stearic acids (or monoesters), in a suitable amount of a solvent such as ethanol or methanol 404 (and hexane if necessary), together with about 30-50 weight percent of urea 406, based on the weight of the fatty acids.
  • the solution is cooled in a crystallization vessel 408 to produce a first crop of urea inclusion crystals which comprise about 10-12 weight percent of the fatty acid component.
  • the first crop of urea inclusion crystals are separated as first crop product 410.
  • the first crop urea inclusion crystals are predominantly urea stearate and palmitate compounds, because of the tendency for the saturated fatty acid (or preferably monoester) to form urea inclusion compounds, leaving in solution at least 98-99% pure unsaturated fatty acids or monoesters in the
  • urea e.g., a 7:1 or more weight ratio of urea to remaining canola unsaturated fatty acids in the vessel 408, is then added and dissolved at elevated temperature. Upon cooling, a second crop of urea inclusion compounds is formed which are predominantly urea oleate and linoleate inclusion compound crystals, which form an exchange reservoir
  • exchange reservoir crystals 420 may be dried to remove solvent and used with an immobilized lipase enzyme 422 such as 1-,3- specific lipase from Mucor miehei immobilized on an ion exchange resin, such as the Novo 3A Lipase product of Novo described in U.S. Patent 4,798,793, in a weight ratio of 2:1 to about 10:1 unsaturated fatty acid urea inclusion reservoir crystals to immobilized enzyme/ionic resin component to form the packing 424 of an intraesterification reaction column 426.
  • the reservoir crystals are also placed, without an immobilized lipase component, as the packing into a column 430.
  • the urea reservoir crystals may be blended with, or alternated in layers with the
  • Canola oil fatty acids or preferably lower alkyl monoesters 402 are conducted through the column 430 at a temperature in the range of 20-110o C., preferably in the range of 40-60o C.
  • a temperature selected for maximum relative stability of the palmitic acid complex over the oleic acid complex may be selected if desired to maximize removal of the palmitic acid component. Because the urea complexes of stearic and palmitic acid or preferably monoester
  • the unsaturated discharge stream 432 may be blended with refined and bleached canola oil 440 in a weight ratio of from about 30:1 to about 1:1 canola oil to fatty acid component, and preferably in a range of from about 10:1 to about 3:1, to pro'duce a transesterification stream 436.
  • the canola oil transesterification stream 436 may be conducted through a water saturated ionic exchange resin column 434 (e.g., at a temperature of 40-70o C.) to saturate the oil/fatty acid (or monoester) blend 436 with water and remove impurities which might deactivate the enzyme.
  • a water saturated ionic exchange resin column 434 e.g., at a temperature of 40-70o C.
  • the saturated intraesterification stream 436 accordingly may have a limited amount of fatty acid
  • a suitable solvent such as butane, pentane, hexane or pressurized propane 440 may be used to reduce the viscosity of the transesterification stream 436 which is introduced into the interesterification column 426.
  • the stream 436 is conducted through the transesterification column 424 where the 1-, 3- fatty acid moieties of the canola oil are progressively released and exchanged with unsaturated fatty acid components of the stream 436 by the acyl transfer activity of the immobilized enzyme.
  • unsaturated fatty acid components may be initially present in the stream 436, may be produced by a small amount of hydrolysis from the water content of the stream, or may be derived from the unsaturated fatty acid urea adduct
  • a vacuum may be periodically or continuously applied to the column 426 with a slow nitrogen bleed to remove monohydric alcohol, increase the triglyceride content and decrease the diglyceride content of the stream, if desired.
  • the stream 436 is conducted through the column 426 at a rate, combined with the transesterification rate and inclusion compound exchange rate, which produces an output stream 450 comprising less than 3 weight percent of
  • the processing may be continued until the saturated fatty acid exchange capacity of the urea
  • the output stream 450 may be refined in any appropriate manner such as countercurrent solvent processing, to remove the fatty acid or monoester and any small amounts of urea.
  • triglyceride mixture may alternatively, or subsequently, be deodorized by conventional steam deodorization or
  • the urea inclusion reservoir component column packings 420, 424 may be replaced or rsgenerated
  • Such replacement and regeneration may be accomplished by redissolving the urea in a hydroxy solvent such as methanol to release and separate the saturated fatty acid inclusion compound, and recycling the urea in solvent-reformed unsaturated fatty acid reservoir
  • the packing 420 may be
  • a solvent such as hexane, liquified propane and/or unsaturated fatty acids 402 (which preferably may have had the saturated fatty acids removed therefrom) at a temperature sufficient to release the saturated fatty acid inclusion components, which may be up to a temperature above the decomposition temperature of the stearate and palmitate inclusion
  • inclusion compounds from the packing 420 in this manner may be cooled in the presence of unsaturated fatty acids compounds, thereby reforming the reservoir material as an unsaturated fatty acid complex.
  • Low molecular weight hydrocarbons such as hexane or petroleum ether, which form relatively unstable inclusion compounds, may be used to extract the saturated fatty acid component in such
  • Regeneration or solvents which do not form an inclusion compound, such as liquified propane may be used. It may be desirable to remove all such solvent following regeneration by methods such as vacuum treatment. Regeneration may be carried out on a continuous countercurrent basis with the "spent" inclusion compound packing 424 being continuously or periodically withdrawn from the bottom (countercurrent inlet) and regenerated material added at the top
  • X and Y type zeolites and/or silicalite having appropriate pore structures which
  • Countercurrent moving bed systems or simulated moving countercurrent bed systems may be used to facilitate continuous operation.
  • Example 1 Having generally described various aspects of the present low saturate vegetable oil products and methods which may be utilized to prepare such products, the invention will now be more particularly described with respect to the following specific examples.
  • Example 1
  • the FAD may be resolved into the five major fatty acids, palmitic (P), stearic (S), oleic (0), linoleic (L), linolenic (Ln) and all the remaining fatty acids designated as "other".
  • P palmitic
  • S stearic
  • oleic (0) linoleic
  • Ln linolenic
  • other all the remaining fatty acids designated as "other”.
  • a typical FAD of the fatty acid components is set forth in the following Table 1.
  • transesterified composition having a weight ratio of esterified monounsaturated fatty acids to polyunsaturated fatty acids of about 1:1.
  • FID fatty acid distribution
  • Run 3 A further reaction was conducted in the same manner with 0.02% TBHQ added as an antioxidant to prevent the formation of peroxides during the reaction which might interfere with the transesterification. Also, the lipase enzyme product concentration was doubled (0.750 grams lipase per gram of oil) to compensate for any other inhibition which might be occuring. Table 3 also
  • Run 4 - Runs 1-3 indicated that there was some contaminant in the canola oil which affected the lipase activity in such a way that the reaction could not reach equilibrium under those conditions.
  • Canola oil which affected the lipase activity in such a way that the reaction could not reach equilibrium under those conditions.
  • Run 4 Florisil purified canola triglycerides with 0.02% TBHQ - Run 5 canola oil with 0.02% TBHQ
  • Run 5 Another lot of canola oil was also transesterified under suostantially identical parameters as described for Run 3, including .02 weight percent TBHQ as an antioxidant. Table 4 also illustrates the FAD of this product. This lot did not demonstrate any lipase
  • High oleic sunflower oil and high oleic safflower oil having low levels of saturated fatty acids were transesterified with substantially pure oleic and linoleic acids, substantially as described in Run 4 of Example 1.
  • Table 5 illustrates the starting FAD, and the FAD of the transesterified products:
  • An oil having very low saturated fatty acid content and a 2:1:1 weight ratio of omega-9:omega-6:omega-3 fatty acids is a nutritionally desirable product which is not naturally available.
  • Canola oil was transesterified with purified oleic, linoleic and linolenic acids as previously described for Run 4 of Example 1, with the addition of linolenic acid to the reaction mixture to prepare such a product. Table 6 illustrates these results:
  • transesterified oils had a very low target amount of less than 1.3 weight percent saturated fats.
  • a ratio of fatty acids: oil of 6.4:1 in the reaction mixture was utilized, in which the reaction mixture contained only 13.5% oil.
  • Transesterified canola oils having about 3 weight percent saturated fats may be more economically produced using lower ratios of unsaturated fatty acids to oil in the reaction mixture.
  • the calculations used to produce a canola oil with close to 3% saturates are shown in Tab
  • Canola oil (Kraft Food Ingredients Group) was transesterified using the procedure of Run 3, Example 1, with the proportion of reaction components as described hereinabove. The results from two trials were tabulated in Table 8:
  • canola oil may be transesterified with a fatty acid mixture derived from canola oil, from which saturated fatty acids have been removed.
  • transesterification reaction may be carried out using a canola oil unsaturated fatty acid:canola oil reaction weight ratio of 1.15:1 as described in Runs 1 and 2 of this Example, to provide a transesterified canola oil having less than 3 weight percent esterified saturated fatty acids, and an omega-9:omega-6:omega-3 esterified unsaturated fatty acid weight ratio of about 5-7:2-3:1.
  • novel low-saturate vegetable oils and methods for manufacturing such oils have been provided. Such methods can be used to produce oils with preselected unsaturated fatty acid compositions as a function of the composition of the starting oil and the fatty acids in the reactions.

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Abstract

Huiles végétales transestérifiées présentant une faible teneur en acides gras saturés, et leurs procédés de préparation en lots par transestérification enzymatique à co-courant et à contre-courant. Les matières grasses et les huiles comestibles constituent une source riche en énergie dans l'alimentation, et sont importantes dans la synthèse de membranes et d'autres constituants cellulaires.
PCT/US1990/007336 1989-12-18 1990-12-13 Huiles comestibles faiblement satures et leurs procedes de production par transesterification WO1991008676A1 (fr)

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EP0519561A1 (fr) * 1991-06-18 1992-12-23 Unilever N.V. Conversion enzymatique de triglycerides
GB2284615A (en) * 1991-06-27 1995-06-14 Sandoz Ltd Transesterified corn oil products
EP0687735A1 (fr) 1994-06-15 1995-12-20 SKW Trostberg Aktiengesellschaft Méthode pour transestérification enzymatique
EP0784694A1 (fr) * 1995-02-24 1997-07-23 Goemar S.A. Procedes enzymatiques d'enrichissement en acides gras polyinsatures
EP0953630A1 (fr) * 1991-06-27 1999-11-03 Novartis AG Produits de transestérification entre l'huile de mais et le glycérol et leur utilisation dans des compositions pharmaceutiques
US6258808B1 (en) 1991-06-27 2001-07-10 Novartis Ag Pharmaceutical composition
US6420355B2 (en) 1992-09-25 2002-07-16 Novartis Ag Pharmaceutical compositions containing cyclosporins
US6475519B1 (en) 1997-01-30 2002-11-05 Novartis Ag Oil-free pharmaceutical compositions containing cyclosporin A
US6582718B2 (en) 1992-05-13 2003-06-24 Novartis Ag Cyclosporin compositions
EP1510133A1 (fr) * 2003-09-01 2005-03-02 Belovo S.A., Egg Science & Technology Composition d'huile équilibrée
CN1326982C (zh) * 1992-06-12 2007-07-18 诺瓦蒂斯有限公司 玉米油和甘油的酯基转移产物及其制备方法
US9476008B2 (en) 2010-06-25 2016-10-25 Epax As Process for separating polyunsaturated fatty acids from long chain unsaturated or less saturated fatty acids
CN109640679A (zh) * 2016-08-12 2019-04-16 嘉吉公司 特种低饱和物菜籽油

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US5286633A (en) * 1991-06-18 1994-02-15 Van Den Bergh Foods Co., Division Of Conopco, Inc. Enzymatic triglyceride conversion
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US6844459B2 (en) 1991-06-27 2005-01-18 Novartis Ag Pharmaceutical Composition
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GB2284615B (en) * 1991-06-27 1996-02-14 Sandoz Ltd Transesterified corn oil products
EP0953630A1 (fr) * 1991-06-27 1999-11-03 Novartis AG Produits de transestérification entre l'huile de mais et le glycérol et leur utilisation dans des compositions pharmaceutiques
US6258808B1 (en) 1991-06-27 2001-07-10 Novartis Ag Pharmaceutical composition
US6582718B2 (en) 1992-05-13 2003-06-24 Novartis Ag Cyclosporin compositions
CN1326982C (zh) * 1992-06-12 2007-07-18 诺瓦蒂斯有限公司 玉米油和甘油的酯基转移产物及其制备方法
US6262022B1 (en) 1992-06-25 2001-07-17 Novartis Ag Pharmaceutical compositions containing cyclosporin as the active agent
US6420355B2 (en) 1992-09-25 2002-07-16 Novartis Ag Pharmaceutical compositions containing cyclosporins
EP0687735A1 (fr) 1994-06-15 1995-12-20 SKW Trostberg Aktiengesellschaft Méthode pour transestérification enzymatique
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US6475519B1 (en) 1997-01-30 2002-11-05 Novartis Ag Oil-free pharmaceutical compositions containing cyclosporin A
EP1510133A1 (fr) * 2003-09-01 2005-03-02 Belovo S.A., Egg Science & Technology Composition d'huile équilibrée
WO2005020698A1 (fr) * 2003-09-01 2005-03-10 Belovo S.A. Composition d'huile vegetale equilibree
US9476008B2 (en) 2010-06-25 2016-10-25 Epax As Process for separating polyunsaturated fatty acids from long chain unsaturated or less saturated fatty acids
CN109640679A (zh) * 2016-08-12 2019-04-16 嘉吉公司 特种低饱和物菜籽油
EP3496545A4 (fr) * 2016-08-12 2020-04-01 Cargill, Incorporated Huile de colza de spécialité à faible teneur en composés saturés
US11517025B2 (en) 2016-08-12 2022-12-06 Cargill, Incorporated Speciality low saturates canola oil

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KR910011144A (ko) 1991-08-07

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