JPWO2010126136A1 - Method for inhibiting the formation of chloropropanols and their forming substances in glyceride oils - Google Patents

Abstract

An object of this invention is to suppress the production | generation of 3-chloropropanediol and 3-chloropropanediol fatty acid ester which are chloropropanols, and those formation substances from glyceride fats and oils. 3-Chloropropane, which is a chloropropanol in fats and oils, by reducing the content of partial glycerides in the fats and oils by adsorbent treatment, alkaline treatment, or heating prior to heating steps such as decolorization and deodorization in the fats and oils purification process. Production of diol, 3-chloropropanediol fatty acid ester and their forming substances can be suppressed.

Description

The present invention relates to a method for inhibiting the production of chloropropanols and their forming substances in glyceride oils and fats.

Chloropropanol is a general term for substances in which chlorine is bonded to propanol, but 3-chloropropanediol, which is one of these substances, has conventionally been produced in small quantities as a by-product when mainly producing amino acid solutions such as soy sauce. It is known and is said to be produced by the presence of lipids and salt in the process of cooking food.

Recently, it has been clarified that edible fats and oils exist in the form of esters in which 3-chloropropanediol is bonded to fatty acids. (Non-Patent Document 1)

Furthermore, recently, it has been reported that glycidol fatty acid esters are present as forming substances in the process of producing chloropropanols in glyceride oils. (Non-Patent Document 2)

For 3-chloropropanediol fatty acid ester, there is no regulation that the allowable intake is determined, but in Europe, all the fatty acids that bind to 3-chloropropanediol fatty acid ester are released and 3-chloropropanediol Therefore, it is desirable to develop a technique for reducing 3-chloropropanediol fatty acid esters in glyceride oils and fats.

There is no toxicological data for glycidol fatty acid esters, but it is desirable to develop a technique for reducing glycidol fatty acid esters in glyceride fats and oils, as with chloropropanols.

Zelinkova Z, Svekovskka B, Velisek J, Dolezal M. et al. Fatty acid esters of 3-chloropropane-1,2-diol in editable oils. Food Add Contam. 2006 Dec; 23 (12): 1290-1298 Dr. Rudiger Weisshaar / Fatty acid esters of 3-MCPD: Overview of occurrence in different types of foods (ILSI Europe Workshop in association with the European Commission: 5-6 February 2009 Brussels, Belgium) (http://europe.ilsi.org/ NR / rdonlyres / A1D194E7-BFA2-4A23-A673-15F1905300D5 / 0 / Speaker6Weisshaar.pdf)

An object of this invention is to provide the method of suppressing production | generation of 3-chloropropanediol and 3-chloropropanediol fatty acid ester which are chloropropanols in glyceride fats, and glycidol fatty acid ester which is those formation substances.

The present inventors have found that chloropropanols in glyceride oils and their substances are increased by a decolorization process, particularly a deodorization process, which is a normal oil refining process, and heat treatment such as frying and oven cooking. Also gained the knowledge that From this knowledge, as a result of intensive research on the above problems, the glyceride fat is treated with an adsorbent and / or alkali before heat treatment, or the diglyceride content in the fat is reduced. The inventors have found that chloropropanols in glyceride fats and oils and the formation of glycidol fatty acid esters, which are the forming substances thereof, can be suppressed, and have completed the present invention.

That is, the present invention provides (1). (2) A method for suppressing the production of chloropropanols and their forming substances in glyceride fats and oils, characterized by subjecting the glyceride fats and oils to an adsorbent treatment and / or an alkali treatment before the treatment in which the glyceride fats are heated to 100 ° C. or higher. The method (3) according to (1), wherein the heat treatment temperature of the glyceride fat is 150 ° C. or higher. The method according to (2), wherein the adsorbent treatment and / or alkali treatment is performed at a product temperature of the glyceride fat of less than 150 ° C. (5) The method according to (3), wherein the adsorbent treatment and / or the alkali treatment are performed at a product temperature of glyceride fat of 60 to 95 ° C. The method (6) according to any one of (1) to (5), wherein the adsorbent is silica gel and / or coconut shell activated carbon. (7) A method for suppressing the production of chloropropanols and their forming substances in a glyceride oil or fat, characterized by subjecting the glyceride oil or fat to a partial glyceride reduction treatment before the treatment for heating the glyceride oil or fat to 100 ° C. or higher. (8) The method according to (6), wherein the partial glyceride reduction treatment is a method using a partial glyceride-specific lipase. The method according to (6) or (7), wherein the diglyceride content in the glyceride fat is reduced to 2% by weight or less by partial glyceride reduction treatment. A method for producing refined palm oil (RBDPO), which comprises purifying crude palm oil (CPO) after one or more treatments selected from adsorbent treatment, alkali treatment and partial glyceride reduction treatment (10). (9) Purified palm oil (RBDPO) obtained by the production method according to (9), wherein the chloropropanol and its forming substance are 3.5 ppm or less, the iodine value is 50 to 55, and the rising melting point is 33 to 39 ° C.
(11). (10) Palm oil fat obtained by processing the refined palm oil (RBDPO) or its olein fraction according to (10).

According to the method of the present invention, it is possible to suppress the production of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid esters and glycidol fatty acid esters which are the substances forming them in glyceride oils.

The present invention is described in detail below.

Examples of glyceride oils and fats to which the method of the present invention can be applied include raw materials such as soybean, rapeseed, safflower, corn, sunflower, cottonseed, rice, olive, palm, palm, palm kernel, sesame, cow, pig, and fish. And unrefined fats and oils obtained by squeezing, extracting, crudely refined fats and oils obtained by filtering and centrifuging unrefined fats, and glyceride fats and oils obtained by esterification reaction of fatty acid and glycerin.

Examples of the glyceride oil to which the method of the present invention can be applied include soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, Although it can apply also to edible refined fats and oils, such as sesame oil, beef tallow, pork tallow, and fish oil, among these, it can apply preferably to palm system fats and oils, especially crude palm oil (CPO).

The method of the present invention includes a refining process such as degumming, deoxidation, decolorization, deodorization, dewaxing, etc. to obtain refined palm oil (RBDPO) from crude palm oil (CPO) obtained by squeezing oil palm pulp, It can be preferably applied in the step of further purifying the refined palm oil (RBDPO) such as decolorization and deodorization.

The method of the present invention relates to a method for suppressing the production of chloropropanols in glyceride fats and glycidol fatty acid esters which are the forming substances thereof, but the chloropropanols in glyceride fats and glycidol fatty acid esters which are the forming substances are Since it is considered that oils and fats are produced by being heated at a high temperature, it is necessary to apply the method of the present invention described below before the treatment in which the oils and fats are heated to a high temperature of 100 ° C or higher, particularly 150 ° C or higher. It is.

In the method of the present invention, the treatment of heating the glyceride fat to 100 ° C. or higher, further 150 ° C. or higher, is a step of decolorization or deodorization when purifying the glyceride fat or oil, or hydrogenating the glyceride fat to harden the fat. Manufacturing processes such as manufacturing, processes for producing transesterified oils and fats using glycerides and fats and chemical catalysts, and cooking processes such as frying, frying, or heating as a spray oil when used for cooking. Is mentioned.

The method of the present invention is a chloropropanol and its forming substance by treating a glyceride oil / fat heated to 100 ° C. or higher, particularly 150 ° C. or higher, with an adsorbent treatment of the glyceride oil / fat before the heating treatment. It is characterized by reducing chlorine compounds and diglycerides, which are considered to be causative substances for the formation of glycidol fatty acid esters, from glyceride oils and fats. Of these adsorbents, silica gel and coconut shell activated carbon are preferably used. Moreover, it is preferable to use activated carbon which has not been subjected to chemical activation treatment as the adsorbent.

As a method of adsorbent treatment, 0.1 to 5% by weight of an adsorbent is added to glyceride oil and fat, and the mixture is heated for a certain period of time at 50 to 80 ° C., preferably 50 to 110 ° C., 0.5 to 100 Torr. And a method of stirring and contacting under reduced pressure.
The adsorbent treatment is a decolorization step before the deodorization step in the glyceride fat refining step, and the treatment step can be simplified by performing the adsorbent treatment simultaneously with the decolorization treatment.

In the method of the present invention, glyceride oils and fats heated to 100 ° C. or higher, particularly 150 ° C. or higher are preferably subjected to alkali treatment before heating, and the alkali agent may be an alkali metal or alkaline earth. Metal hydroxides and carbonates can be used. Specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate, and the like can be used.

As an alkali treatment method, sodium hydroxide is added to glyceride oil and fat in an amount of 0.8 to 1.2 times the neutralization equivalent of free fatty acid, and after stirring, centrifuged, removed from the foots, further washed with water and stirred. Thereafter, a method of centrifuging, removing the aqueous layer, and dehydrating under heating and reduced pressure can be used.

The adsorbent treatment and / or alkali treatment, which is the method of the present invention, generates chloropropanols and their forming substances in glyceride fats and oils at high temperatures, so that the temperature of glyceride fats is less than 150 ° C., more preferably 100. It is preferable to carry out at a temperature below 60 ° C., more preferably 60 to 95 ° C.

Further, according to another method of the present invention, it is preferable that the diglyceride content in the glyceride oil or fat is set to 2% by weight or less before the heating treatment with respect to the glyceride oil or fat heated to 100 ° C or higher, particularly 150 ° C or higher. . When the diglyceride content in the glyceride oil is high, the amount of 3-chloropropanediol and 3-chloropropanediol fatty acid ester which are chloropropanols in the glyceride oil and glycidol fatty acid ester which is a substance forming them increases by heating. Since there is a tendency, it is not preferable.

Methods for reducing the diglyceride content in glyceride oils include distillation, chromatographic separation, and lipase treatment. Among these, the present invention is a lipase that specifically acts on partial glycerides such as diglycerides. A method for reducing the diglyceride content by an enzyme treatment such as the above is preferable because it is simple and does not go through a heating step that is exposed to a high temperature, and the method described in JP-A No. 62-61590 can be preferably applied.

Since glyceride oils and fats are heated at a high temperature of 80 to 270 ° C. during the decolorization process, particularly during the deodorization process, glycerides and fats are likely to increase chloropropanols and their forming substances in the oils and fats. It is known that the method of the present invention is carried out before the above decolorization step and / or deodorization step, which is heated to 100 ° C. or higher, particularly 150 ° C. or higher, so that The production of certain glycidol fatty acid esters can be suppressed.

The glyceride oil obtained by the method of the present invention suppresses the production of 3-chloropropanediol and 3-chloropropanediol fatty acid esters that are chloropropanols and glycidol fatty acid esters that are their forming substances. The contents of chloropropanols and the glycidol fatty acid ester which is a substance forming the chloropropanols are measured by the following method with reference to the following documents.
(Determination of total 3-chloropropane-1,2-diol (3-MCPD) in editable oils by cleavage of MCPD esters with sodium method. Eur. J. Lipid 83, Sci.

First, 0.1 g of fat / oil is dissolved in 1 ml of t-butyl methyl ether, 250 μl of 20 μg / ml internal standard substance (3-MCPD-d ₅ ethyl acetate solution) is added, and NaOCH ₃ solution (0.5 mol / l NaOCH ₃ in MeOH) is added. ) After mixing with 1 ml, let stand at room temperature for 10 minutes. Subsequently, 3 ml of hexane, 3 ml of NaCl solution (NaCl 200 g / 1 l of water) and 0.1 ml of glacial acetic acid are added, and after stirring, the upper layer is removed. Furthermore, 3 ml of hexane is added, and after stirring, the upper layer is removed. Then, a phenylboronic acid solution (1 g of phenylboronic acid was dissolved in acetone: water = 19: 1, 4 ml) was added and stirred, then left at 80 ° C. for 20 minutes, allowed to cool to room temperature, and then 2 ml of hexane was added and stirred. The upper layer is subjected to GS-MS analysis.
Note that the GC-MS, the molecular ion peak m / z 196 (3-MCPD ), quantified using m / z 201 (3-MCPD -d 5).

In addition, although the said method is employ | adopted as a measuring method of the glycidol fatty acid ester which is 3-chloropropanediol fatty acid ester and its formation substance of Germany (Deutsche Gesellchaft fur Fettwissenschaft: DGF), in this method, glyceride Hydrolysis of 3-chloropropanediol fatty acid ester in fats and oils and glycidol fatty acid ester which is a forming substance thereof, and all 3-chloropropanediol fatty acid esters present in glyceride fats and oils and glycidol fatty acid ester as a forming substance thereof as 3-MCPD Measuring.
“With this method, three compounds, and the other forms of the three-MCPD uncertain the conditions, three-dimensionally, and the first and second. 2-diol (3-MCPD esters) and 3-MCPD forming subnets: DGF Standard Methods Section C-Fats / C-III 18 (09))

According to the method of the present invention, the production of chloropropanols and their forming substances in the glyceride oil refining step is effectively suppressed, and the iodine value obtained by degumming, decolorizing and deodorizing CPO (crude palm oil). The content of chloropropanols and their forming substances in RBDPO (refined palm oil) having a melting point of 50 to 55 and a rising melting point of 33 to 39 ° C. can be suppressed to 3.5 ppm or less, and further can be suppressed to 3 ppm or less.

The palm oil obtained by processing the refined palm oil (RBDPO) obtained by the method of the present invention or the olein fraction obtained by further fractionation has a low content of chloropropanols and its forming substances, When used as a frying oil, even if it is exposed to a heating process such as cooking, the production of chloropropanols and their forming substances can be suppressed.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition,% in an example means a basis of weight.

Adsorbent treatment was performed by adding 3% by weight of fine powder silica to raw palm oil obtained by degumming crude palm oil (CPO / acid value = 7.8) and stirring at 70 ° C. and 20 Torr for 10 minutes. . After the adsorbent treatment, 1% by weight of white clay was added, decolorized at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The obtained refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and its forming substances of 3.5 ppm.

Adsorbent treatment was performed by adding 3% by weight of coconut shell activated carbon to raw palm oil obtained by degumming crude palm oil (CPO / acid value = 7.8) and stirring at 70 ° C. and 20 Torr for 10 minutes. . After the adsorbent treatment, 1% by weight of white clay was added, decolorized at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The obtained refined palm oil (RBDPO / IV: 52.2, rising melting point: 36.5 ° C.) had a content of 2.9 ppm of chloropropanols and its forming substance.

After adding 6.7% by weight of sodium hydroxide to raw palm oil obtained by degumming crude palm oil (CPO / acid value = 7.8), stirring at 3000 rpm for 3 minutes, centrifuging, removing foots, Further, 20% by weight of water was added, and the mixture was stirred at 3000 rpm for 3 minutes and then centrifuged. After removing the aqueous layer, dehydration treatment was performed at 110 ° C. and 20 Torr for 10 minutes. After alkali treatment, 1% by weight of white clay was added, decolorized at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The resulting refined palm oil (RBDPO / IV: 52.2, rising melting point: 36.5 ° C.) had a content of 2 ppm of chloropropanols and its forming substances.

10% by weight of water and 1% by weight of lipase (lipase G “Amano” 50 [manufactured by Amano Enzyme Co., Ltd.]) are added to raw palm oil degummed with crude palm oil (CPO / acid value = 7.8). The reaction was stirred at 43 ° C. for 3 hours. The diglyceride content after lipase treatment was 0.4%. After the lipase treatment, 1% by weight of white clay was added, decolorized at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The obtained refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and the forming substances thereof of 3.1 ppm.

Crude palm oil (CPO / acid value = 7.8) was degummed with raw palm oil, 1% by weight of white clay and 0.5% by weight of finely divided silica were added, and at 110 ° C. and 20 Torr for 10 minutes, simultaneously with decolorization. An adsorbent treatment was performed, and a deodorization treatment was further performed at 250 ° C. and 2 Torr for 90 minutes. The obtained refined palm oil (RBDPO / IV: 52.2, rising melting point: 36.5 ° C.) had a content of 3.9 ppm of chloropropanols and its forming substances.

Crude palm oil (CPO / acid value = 7.8) is degummed to raw palm oil, 1% by weight of white clay and 0.1% by weight of finely divided silica are added, and at 110 ° C. and 20 Torr for 10 minutes, simultaneously with decolorization An adsorbent treatment was performed, and a deodorization treatment was further performed at 250 ° C. and 2 Torr for 90 minutes. The obtained refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and its forming substances of 4.8 ppm.

10% by weight of water and 1% by weight of lipase (lipase G “Amano” 50 [manufactured by Amano Enzyme Co., Ltd.]) are added to raw palm oil degummed with crude palm oil (CPO / acid value = 7.8). The reaction was stirred at 43 ° C. for 3 hours. The diglyceride content after lipase treatment was 0.3%. After the lipase treatment, 1% by weight of white clay and 3% by weight of fine silica were added, adsorbent treatment was performed simultaneously with decolorization at 110 ° C. and 20 Torr for 10 minutes, and deodorization treatment was further performed at 250 ° C. and 2 Torr for 90 minutes. The resulting refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and the forming substances thereof of 2.0 ppm.

(Comparative Example 1)
Raw palm oil from which crude palm oil (CPO / acid value = 7.8) has been degummed is decolorized for 10 minutes at 1% by weight of white clay, 110 ° C., 20 Torr, and then deodorized at 250 ° C., 2 Torr for 90 minutes. It was. The obtained refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and the forming substances thereof of 6.0 ppm.

(Comparative Example 2)
Raw palm oil from which crude palm oil (CPO / acid value = 7.8) has been degummed is decolorized for 10 minutes at 1% by weight of white clay, 110 ° C., 20 Torr, and then deodorized at 250 ° C., 2 Torr for 90 minutes. It was. To the resulting refined palm oil, 3% by weight of fine powder silica was added, and the mixture was stirred at 70 ° C. and 20 Torr for 10 minutes to perform the adsorbent treatment. The obtained refined palm oil (RBDPO / IV: 52.2, ascending melting point: 36.5 ° C.) after the treatment with the adsorbent had a content of chloropropanols and its forming substances of 4.4 ppm.

The results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in the table.

table

Claims (11)

A method for suppressing the production of chloropropanols and their forming substances in glyceride fats and oils, characterized by subjecting the glyceride fats and oils to an adsorbent treatment and / or an alkali treatment before the treatment of heating the glyceride fats to 100 ° C. or higher. The method of Claim 1 that the heat processing temperature of the said glyceride fats and oils is 150 degreeC or more. The method according to claim 2, wherein the adsorbent treatment and / or the alkali treatment is performed at a product temperature of glyceride fat of less than 150 ° C. The method according to claim 3, wherein the adsorbent treatment and / or the alkali treatment is performed at a product temperature of glyceride oil of 60 to 95 ° C. The method according to any one of claims 1 to 5, wherein the adsorbent is silica gel and / or coconut shell activated carbon. A method for suppressing the production of chloropropanols and their forming substances in glyceride fats and oils, wherein partial glyceride reduction treatment is performed before the treatment of heating the glyceride fats to 100 ° C. or higher. The method according to claim 6, wherein the partial glyceride reduction treatment is a method using a partial glyceride-specific lipase. The method according to claim 6 or 7, wherein the diglyceride content in the glyceride fat is reduced to 2% by weight or less by the partial glyceride reduction treatment. A method for producing refined palm oil (RBDPO), comprising purifying crude palm oil (CPO) after one or more treatments selected from adsorbent treatment, alkali treatment and partial glyceride reduction treatment. A refined palm oil (RBDPO) having an iodine value of 50 to 55 and an rising melting point of 33 to 39 ° C., obtained by the production method according to claim 9, wherein the chloropropanols and substances forming the chloropropanol are 3.5 ppm or less. The palm oil fat which processes refined palm oil (RBDPO) of Claim 10, or its olein fraction.