Reexamination Certificate
2001-11-27
2002-06-25
Carr, Deborah D. (Department: 1621)
Reexamination Certificate
active
06409649
ABSTRACT:
FIELD OF INVENTION
This invention relates to an improved process for preparation of conjugated linoleic acid (CLA) that overcomes the high input cost of alkali and solvent by recycling alkali and glycerol mixtures derived from triglyceride transesterification. Surprisingly, the alkali in the recycled solutions supports a vigorous reaction and the crude nature of the mixture does not contribute to undesirable colours in the CLA produced using these products.
BACKGROUND OF THE INVENTION
Conjugated linoleic acid is the trivial name given to a series of eighteen carbon diene fatty acids with conjugated double bonds. Applications of conjugated linoleic acid vary from treatment of medical conditions such as anorexia (U.S. Pat. No. 5,430,066) and low immunity (U.S. Pat. No. 5,674,901) to applications in the field of dietetics where CLA has been reported to reduce body fat (U.S. Pat. No. 5,554,646) and to inclusion in cosmetic formulae (U.S. Pat. No. 4,393,043).
CLA shows similar activity in veterinary applications. In addition, CLA has proven effective in reducing valgus and varus deformity in poultry (U.S. Pat. No. 5,760,083), and attenuating allergic responses (U.S. Pat. No. 5,585,400). CLA has also been reported to increase feed conversion efficiency in animals (U.S. Pat. No. 5,428,072). CLA-containing bait can reduce the fertility of scavenger bird species such as crows and magpies (U.S. Pat. No. 5,504,114).
Industrial applications for CLA also exist where it is used as a lubricant constituent (U.S. Pat. No. 4,376,711). CLA synthesis can be used as a means to chemically modify linoleic acid so that it is readily reactive to Diels-Alder reagents (U.S. Pat. No. 5,053,534). In one method linoleic acid was separated from oleic acid by first conjugation, then reaction with maleic anhydride followed by distillation (U.S. Pat. No. 5,194,640).
Conjugated linoleic acid occurs naturally in ruminant depot fats. The predominant form of CLA in ruminant fat is the cis,trans-9,11-octadecadienoic acid which is synthesized from linoleic acid in the rumen by micro-organisms like
Butryvibrio fibrisolvens.
The level of CLA found in ruminant fat is in part a function of dietary cis,cis-9,12-octadecadienoic acid and the level of CLA in ruminant milk and depot fat may be increased marginally by feeding linoleic acid (U.S. Pat. No. 5,770,247).
CLA may also be prepared by any of several analytical and preparative methods. Pariza and Ha pasteurized a mixture of butter oil and whey protein at 85° C. for 5 minutes and noted elevated levels of CLA in the oil (U.S. Pat. No. 5,070,104). CLA produced by this mechanism is predominantly a mixture of cis,trans-9,11-octadecadienoic acid and trans,cis-10,12-octadecadienoic acid.
CLA has also been produced by the reaction of soaps with strong alkali bases in molten soaps, alcohol, and ethylene glycol monomethyl ether (U.S. Pat. Nos. 2,389,260, 2,242,230 & 2,343,644). These reactions are inefficient as they require the multiple steps of formation of the fatty acid followed by production of soap from the fatty acids, and subsequently increasing the temperature to isomerize the linoleic soap. The CLA product is generated by acidification with a strong acid (sulfuric or hydrochloric acid) and repeatedly washing the product with brine or CaCl
2
.
CLA has been synthesized from fatty acids using SO
2
in the presence of a sub-stoichiometric amount of soap forming base (U.S. Pat. No. 4,381,264). The reaction with this catalyst produced predominantly the all trans configuration of CLA.
Efficient synthesis of cis,trans-9,11-octadecadienoic from ricinoleic acid has been achieved (U.S. Pat. No. 5,892,074). This synthesis, although efficient, uses expensive elimination reagents such as 1,8-diazobicyclo-(5,4,0)-undecene. For most applications the cost of the elimination reagent increases the production cost beyond the level at which commercial production of CLA is economically viable.
Water may be used in place of alcohols in the production of CLA by alkali isomerization of soaps (U.S. Pat. Nos. 2,350,583, 4,164,505). When water is used for this reaction it is necessary to perform the reaction in a pressure vessel whether in a batch (U.S. Pat. No. 2,350,583) or continuous mode of operation (U.S. Pat. No. 4,164,509). The process for synthesis of CLA from soaps dissolved in water still requires a complex series of reaction steps. Bradley and Richardson (
Industrial and Engineering Chemistry
February 1942 vol 34 no2 237-242) were able to produce CLA directly from soybean triglycerides by mixing sodium hydroxide, water and oil in a pressure vessel. Their method eliminated the need to synthesize fatty acids and then form soaps prior to the isomerization reaction. However, they reported that they were able to produce an oil with up to 40 percent CLA. Quantitative conversion of the linoleic acid in soybean oil to CLA would have produced an fatty acid mixture with approximately 54 percent CLA.
Commercial conjugated linoleic acid often contains a mixture of positional isomers that may include trans,cis-8,10-octadecadienoic acid, cis,trans-9,11-octadecadienoic acid, trans,cis-10,12-octadecadienoic acid, and cis,trans-11,13-octadecadienoic acid (Christie, W. W., G. Dobson, and F. D. Gunstone, (1997) Isomers in commercial samples of conjugated linoleic acid. J. Am. Oil Chem. Soc. 74, 11, 1231).
OBJECT OF INVENTION
The present invention relates to a method of production of CLA using vegetable oils, esters, fatty acids or soaps that are rich in linoleate moieties. The method uses alkali, formerly used for triglyceride transesterification, for conversion of the soaps in the soapstock to conjugated linoleate soaps. The method also uses crude glycerol derived from triglyceride transesterification as the solvent for CLA production. After the conjugation reaction the soaps may be extracted with acid to yield conjugated linoleic acid or with salts to yield soaps.
BRIEF STATEMENT OF INVENTION
By one aspect of this invention there is provided a process for producing conjugated linoleic acid from a material rich in linoleate moieties comprising; mixing said material with a waste alkaline glycerol derived from alkali transesterification of triglycerides, heating to a temperature above 170° C., cooling and separating said conjugated linoleic acid by the addition of at least one of the group consisting of a salt, a salt solution and an acid.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of the present invention quantitatively converts oils, soapstocks, fatty acids, soaps and esters rich in linoleate moieties to conjugated linoleic acid by reacting the same in a crude alkaline glycerol solution. The process is novel in that the crude alkali glycerol solution is prepared as a by-product of alkaline transesterification of triglycerides with a lower alcohol. Surprisingly, the recycled alkaline solution has sufficient reactivity to isomerize linoleate to conjugated linoleate moieties. The oils, soapstocks, fatty acids, soaps and esters may be added to the alkaline glycerol solution directly. However, as a unique embodiment of this invention the alkaline glycerol solution may be also used as a refining agent that extracts fatty acids from vegetable oils.
The conversion of linoleate moieties in vegetable oils, fatty acids, esters, soapstocks and soaps to conjugated linoleates is achieved by mixing the linoleate containing material with the alkaline glycerol solution and increasing the temperature to above 170° C. The vegetable oil, soaps, fatty acids, esters and soapstocks used may be derived from cottonseed, cucumber, grape seed, corn, safflower, soybean, sunflower or walnut or any other oil, wax or ester that is rich in linoleate. The reaction may proceed with the alkali present in the glycerol solution alone but additional alkali such as sodium metal, sodium hydroxide, sodium alkoxylate, potassium metal, potassium hydroxide or potassium alkoxylate or solutions thereof may be added to augment the reaction. The reaction proceeds at temperatures above 170° C. and the reaction accelerates with
Carr Deborah D.
Dowell & Dowell , P.C.
Her Majesty the Queen in right of Canada as represented by the
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