US3326947A

US3326947A - Process for removing the halphen test response from alkali refined cottonseed oil

Info

Publication number: US3326947A
Application number: US327560A
Authority: US
Inventors: Eric T Rayner; Harold P Dupuy
Original assignee: Individual
Current assignee: Individual
Priority date: 1963-12-02
Filing date: 1963-12-02
Publication date: 1967-06-20
Anticipated expiration: 1984-06-20

Description

United States Patent PROCESS FOR REMOVING THE HALPHEN TEST RESPONSE FROM ALKALI REFINED COTTON- SEED OIL Eric T. Rayner and Harold P. Dupuy, New Orleans, La.,

assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Dec. 2, 1963, Ser. No. 327,560

3 Claims. (Cl. 260-424) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to a process for removing the Halphen test response from (alkali refined) cottonseed oil and has as its object the production of cottonseed oils that react negatively to the Halphen test.

Cottonseed oil, in addition to the major fatty acid constituents, is reported to contain from a fraction of one percent to about two percent of malvalic acid. Malvalic acid reacts positively to the so-called Halphen test. Cottonseed oil also reacts positively to the Halphen test as do the seed oils of many malvaceous plants.

It is known that acids containing the cyclopropene ring (i.e., malvalic and sterculic acids), when included in the rations of laying hens, are capable of producing certain abnormalities, such as pink egg whites, salmon colored, enlarged, fluid yolks, and reduced hatchability. In addition, it has been reported that a correlation exists between the intensity of the Halphen test as applied to the residual oil in the cottonseed meal component of a poultry ration and the occurrence of abnormalities in stored intact eggs.

Prolonged heating of cottonseed oil has been reported to eliminate the Halphen test response but this is not practical for cottonseed oil, the intended end use for which is an edible use, since prolonged heating of vegetable oils in the presence of air is known to produce toxic polymers.

Certain halogen containing mineral acids are also reported to effect a reduction of or the destruction of Halphen test response, but the addition of such extraneous halogenated materials to cyclopropenoid-containing edible oils is per se most undesirable.

In general, the process of our invention which We use to eliminate the Halphen test response from cottonseed oil comprises treating a previously alkali refined oil with at least about four equivalents, based on the cyclopropene acid content of the oil, of certain naturally occurring monobasic fatty acids of vegetable origin, such as capric acid or cottonseed fatty acids, and employing therewith a temperature of up to 235 C. for an interval of about two hours to completely eliminate the Halphen test response. This heat treatment, conducted under inert atmosphere in a standard deodorizing flask, is followed by a conventional deodorization procedure, as by heating under vacuum, carried out at 235 C. for a period of about one hour. The deodorization process functions not only to remove remaining odors and flavors from the oil, but additionally reduces the acid content of the oil to below that of the original alkali refined oil used as starting material. Although capric acid and cottonseed fatty acids are equally efficacious in eliminating the Halphen test response from cottonseed oil when used according to the methods set forth in this invention; it is, however, our opinion that the use of the lower molecular weight and lower boiling capric acid may ofier an advantage with respect to ease of removal from the oil. Use of capric acid should permit lower deodorization temperatures for shorter periods of time.

As will be appreciated by those versed in the art of vegetable oil refining, the heating of crude oil at even the relatively low temperatures required by our process tends to fix the naturally occurring color bodies and make diflicult the production of a finished oil with acceptable color characteristics. The use, however, of alkali refined oil in our process of Halphen test response inactivation circumvents completely the color problems which might otherwise arise in using crude cottonseed oil.

Thus our invention comprises a simple two-step process for Halphen test response inactivation which is suitable for commercial use, utilizing conventional procedures and existing processing equipment.

While specific reaction times, reaction temperatures, and acid concentrations have been outlined in our examples, they are not to be construed as the only operable combinations for effectively eliminating the Halphen test response from alkali refined cottonseed oil. By increasing acid concentrations lower temperatures and reduced reaction times may be employed. Similarly, an increase in the variables of time and temperature would allow the use of reduced acid concentrations.

It is our opinion that the carboxyl group of the fatty acid we employ reacts with the material responsible for Halphen test response thus rendering it inactive. Although we are by no means certain that this is the mechanism of our process, inability to explain the reaction in no way detracts from the etficacy of the process. We are able to demonstrate by chemical test the complete elimination of Halphen test response in cottonseed oils treated by our process.

The A.O.C.S. Halphen test, Ofiicial Method Cb 1-25, was used for measuring Halphen test response in our examples which follow:

Examples Portions of alkali refined cottonseed oil were heated under nitrogen at 235 C. for two-hour intervals with four equivalents, based on cyclopropene acid content of the oil, of capric acid or cottonseed fatty acids. Immediately following this heat treatment the oils were deodorized at 235 C. for one hour, employing conventional deodorizing methods. The resulting oils were then tested for the Halphen test response. Some selected data from the manifold experiments which we performed for the purpose of establishing optimum operating limitations for our method are shown in tabular form in Table I.

TABLE I [The treatment of alkali refined cottonseed oil with monobasic fatty acids to eliminate the Halphen test response] Concentration Heat Treatment Acid Value 3 Halphen Acid Test 4 Percent (M) Eqv. C. Hrs. Original Deodorized Oil Oil 1 Equivalents based on 0.63% cyclopropenoid content expressed as malvalic acid. 2 Hours of heating in all cases consisted of two hours under inert gas at atmospheric pressure followed by one hour of vacuum deodorization.

3 Determined by A.O.C.S. Halphen Test, Oificial Method Cb 125.

4 This oil was heated one hour at 235 0., but deodorized at only 200 for two hours.

5 Expressed as percent oleic acid.

Having thus described our invention, We claim: 1. A process for eliminating Halphen test response in alkali refined cottonseed oil comprising (a) treating the alkali refined cottonseed oil in an inert atmosphere at a temperature of 235 C. for a period of about two hours with at least about four equivalents, based on the cyclopropene acid content of the oil, of capric acid, and (b) deodorizing by heating under vacuum at 235 C. for an'additional period of about one hour the oil obtained in Step (a) above. 2. A process for eliminating Halphen test response in alkali refined cottonseed oil comprising (a) treating the alkali refined cottonseed oil in an inert atmosphere at a temperature of 235 C. for a period of about two hours with at least about four equivalents, based on the cyclopropene acid content of the oil, of cottonseed fatty acids, and (b) deodorizing by heating under vacuum at 235 C.

for an additional period of about one hour the oil obtained in Step (a) above. 3. A process for eliminating Halphen test response in 5 alkali refined cottonseed oil comprising of capric acid and cottonseed fatty acids, and

(b) deodorizing by heating under vacuum at 235 C. for an additional period of about one hour the oil obtained in Step (a) above.

No references cited.

ALEX MAZEL, Primary Examiner. ANTON H. SUTTO, ANNE MARIE TIGHE,

Assistant Examiners.

Claims

3. A PROCESS FOR ELIMINATING HALPHEN TEST RESPONSE IN ALKALI REFINED COTTONSEED OIL COMPRISING (A) TREATING THE ALKALI REFINED COTTONSEED OIL IN AN INERT ATMOSPHERE AT A TEMPERATURE OF 235*C. FOR A PERIOD OF ABOUT TWO HOURS WITH AT LEAST ABOUT FOUR EQUIVALENTS, BASED ON THE CYCLOPROPENE ACID CONTENT OF THE OIL, OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF CARPIC ACID AND COTTONSEED FATTY ACIDS, AND (B) DEODORIZING BY HEATING UNDER VACUUM AT 235*C. FOR AN ADDITIONAL PERIOD OF ABOUT ONE HOUR THE OIL OBTAINED IN STEP (A) ABOVE.