JP6021382B2 - Method for producing glyceride composition - Google Patents

Description

  The present invention relates to a method for producing a glyceride composition and a glyceride composition produced through the production method.

  In recent years, various attempts have been made to improve the flavor and stability of fats and oils. Various factors are related to the deterioration of quality such as the flavor and stability of fats and oils, and methods according to each factor have been reported. In addition, a large number of trace components present in fats and oils that are considered to be related to physiological activity have been reported.

  For example, Patent Document 1 discloses a glyceride fatty acid ester in a glyceride composition by deodorizing a glyceride composition containing 3-chloropropane-1,2-diol or the like under a specific temperature condition. A method of reducing is disclosed. Further, Patent Document 2 discloses a re-refined palm soft oil having a good flavor having a specific chromaticity by further performing a decoloring process and a deodorizing process on a refined palm soft oil subjected to at least a deodorizing process. Is disclosed. Moreover, in patent document 3, the refinement | purification process using the thin film type column which comprised the regular packing material, and the refinement | purification process using a tray type apparatus are combined, and trans-fatty acid content in all the constituent fatty acids is 1 mass% or less. A method for purifying fats and oils is disclosed.

  Moreover, in order to suppress the production | generation of an unpreferable compound on the flavor of fats and oils with deterioration by oxidation of fats and oils, the refined fats and oils are generally preserve | saved under low temperature. However, it is known that especially for palm-based fats and oils, a “returning substance” that causes deterioration of the flavor of fats and oils is generated during low-temperature storage. Although the details of the “returning substance” are not known, the presence of this substance in the refined fats and oils causes the flavor of the fats and oils to return to the state prior to purification, causing a flavor deterioration called “returning odor”. .

  For example, crude oil squeezed overseas is subjected to a refining process called a physical refining process, and is imported into Japan as so-called RBD oil (Refined Bleached Deodorized). Although most of imported RBD oil is re-refined in Japan, “returned substances” may be produced in fats and oils during storage of RBD oils at low temperatures. There has been a demand for a method capable of suppressing the above.

JP 2011-074358 A JP 2011-030482 A Japanese Patent No. 4516897

  This invention is made | formed in view of the above situations, and provides the method of suppressing the flavor deterioration of the fats and oils at the time of the preservation | save at low temperature.

  In the deodorization step, the present inventors can suppress the production of “return substances” that occur during storage at low temperatures by adding a predetermined amount of citric acid, ascorbic acid, or citric acid monoglyceride to the glyceride composition. As a result, the present invention has been completed. Specifically, the present invention provides the following.

(1) The manufacturing method of a glyceride composition including the process of adding either of the following to a glyceride composition in a deodorizing process.
(I) Citric acid in an amount of 0.5 ppm to 10 ppm in the glyceride composition (ii) Ascorbic acid in an amount of 5 ppm to 100 ppm in the glyceride composition, or (iii) 5 ppm or more in the glyceride composition Citric acid monoglyceride in an amount of 250 ppm or less

  (2) The production method according to (1), wherein the glyceride composition is palm oil.

  (3) The said deodorizing process is a manufacturing method as described in (1) or (2) performed on 210-265 degreeC temperature conditions.

  (4) A glyceride composition produced through the production method according to any one of (1) to (3) above.

  ADVANTAGE OF THE INVENTION According to this invention, the flavor deterioration of fats and oils at the time of the preservation | save under low temperature can be suppressed.

  Hereinafter, embodiments of the present invention will be specifically described. In the present invention, the glyceride is an ester bond of 1 to 3 fatty acids to glycerin. In addition to triglyceride (triacylglycerol), which is the main component of fats and oils, diglyceride (diacylglycerol), monoglyceride (monoacylglycerol) ).

  The method for producing a glyceride composition of the present invention includes a step of adding a predetermined amount of citric acid, ascorbic acid, or citric acid monoglyceride to the glyceride composition in the deodorization step.

(Citric acid, ascorbic acid, or citric acid monoglyceride)
As a result of studies by the present inventors, it has been found that the flavor deterioration of fats and oils may be caused by the following mechanism. That is, in the decolorization process of fats and oils, a peroxide having a hydroperoxide group (—OOH) present in the fats and oils is decomposed when heated in the presence of white clay or the like to produce 2-nonenal. The inventors of the present invention have identified that 2-nonenal and / or a derivative thereof produced in the decolorization step is one of substances that cause deterioration in the flavor of fats and oils during low-temperature storage, that is, one of “returning substances”. It was also found that 2-nonenal and / or its derivatives once produced in the decolorization process remained in the oil even after further deodorization process.

  On the other hand, there is a phenomenon called autoxidation of fats and oils, in which fats and oils react with oxygen in the air, producing carboxylic acid oxides and aldehydes that cause flavor deterioration. Light and metals promote this phenomenon. It is known to do. In order to retain a metal that promotes auto-oxidation and suppress auto-oxidation, compounds having a chelating effect such as citric acid, ascorbic acid, or citric acid monoglyceride have been conventionally added to fats and oils in the deodorization step. However, when the present inventors add a conventional amount of a compound having a chelating effect (for example, 20 to 1000 ppm of citric acid) to fats and oils in the deodorizing step, the amount of 2-nonenal produced in the fats and oils is increased. I found that it would increase.

  However, if a compound having a chelating effect such as citric acid is not added to fats and oils, the auto-oxidation of fats and oils cannot be suppressed, and the production of oxides and the like is promoted, and the flavor of fats and oils may deteriorate in a short time. There is. Moreover, if the refined fats and oils are not preserve | saved at low temperature, the oxidation of fats and oils will occur easily and the compound which is unpreferable on the flavor of fats and oils may produce | generate in a short time.

Therefore, as a result of intensive studies by the present inventors, in the deodorization step, the glyceride composition has a chelate effect in an amount smaller than the conventional amount,
(I) Citric acid in an amount of 0.5 ppm to 10 ppm in the glyceride composition (ii) Ascorbic acid in an amount of 5 ppm to 100 ppm in the glyceride composition, or (iii) 5 ppm to 250 ppm in the glyceride composition By adding any one of the amounts of citric acid monoglyceride, the formation of 2-nonenal in fats and oils during storage at low temperatures while suppressing the formation of unfavorable compounds due to the automatic oxidation of fats and oils and the flavor of fats and oils It was found that generation can be suppressed.

  The citric acid, ascorbic acid, or citric acid monoglyceride in the present invention can also be used in combination with other compounds having a chelating effect. Examples of other compounds having a chelating effect include phosphoric acid and C2-8 carboxylic acid.

(Deodorization process)
In the method for producing a glyceride composition of the present invention, the deodorization may be performed under a temperature condition of 210 to 265 ° C., preferably 215 to 260 ° C., more preferably used in a usual method for producing fats and oils. 215 to 245 ° C. Even if the glyceride composition is deodorized under a temperature condition lower than the temperature condition used in the normal method for producing fats and oils, by adding citric acid, ascorbic acid, or citric acid monoglyceride thereafter, 2-nonenal Formation can be preferably suppressed.

  Although the other conditions in a deodorizing process are not specifically limited, It is preferable to perform pressure reduction or water vapor | steam blowing, and it is more preferable to perform pressure reduction and water vapor | steam blowing. Further, the deodorization time is preferably 10 to 150 minutes, and more preferably 30 to 100 minutes.

  Although the apparatus used in a deodorizing process is not specifically limited, The tray type apparatus etc. which are used in manufacture of a normal deodorizing oil may be sufficient.

  Addition of citric acid, ascorbic acid, or citric acid monoglyceride to the glyceride composition in the deodorization step can be performed at any stage in the deodorization step. Since citric acid, ascorbic acid, or citric acid monoglyceride is decomposed and removed under the heating conditions of the deodorization process, in order to fully exhibit the chelating effect of citric acid, ascorbic acid, or citric acid monoglyceride, the end of the deodorization process It is preferable to add to. “The end of the deodorization process” will be described by taking a tray-type device as an example. The tray type apparatus includes a deodorizing tower having several trays. Deodorization of the glyceride composition is performed by heating the glyceride composition by exposure to water vapor or the like while lowering the glyceride composition from the upper tray to the lower tray of the deodorization tower. The stage in which the oil temperature of the glyceride composition descended in the lower tray in the deodorization tower reaches 110 to 180 ° C. can be called “the end of the deodorization process”. At this point, citric acid, ascorbic acid, or citric acid It is preferable to add an aqueous solution of monoglyceride.

  Whether or not the amount of 2-nonenal produced in the glyceride composition is suppressed can be confirmed by the following method. The glyceride composition is fractionated into a head space vial, and a volatile substance generated when heated at 50 to 100 ° C. for 30 to 100 minutes is adsorbed by an adsorbent. The adsorbent is reheated at 200 to 250 ° C. for 1 to 10 minutes at the gas chromatography inlet, and the volatile substance is applied to the gas chromatography column. Next, each isolated component is detected with a detector in the column, and 2-nonenal is identified, and then quantified with a reagent (manufactured by Wako Pure Chemical Industries, Ltd.).

(Glyceride composition)
In the method for producing a glyceride composition of the present invention, the glyceride composition is not particularly limited, but a refined oil or an unrefined oil may be used. According to the present invention, it is possible to preferably suppress the production of “return substances” in oils and fats stored at low temperatures regardless of refined oils and non-refined oils.

  Examples of the refined oil include rapeseed oil, soybean oil, rice oil, safflower oil, grape oil, sunflower oil, wheat germ oil, corn oil, cottonseed oil, sesame oil, peanut oil, flux oil, Edible oil such as sesame oil, olive oil, palm oil, palm kernel oil, coconut oil, mixed vegetable oil mixed with two or more of these, or palm olein, palm stearin, palm super olein, palm mid fraction, etc. In addition to fractionated oils, hydrogenated oils, transesterified oils, and the like, edible oils produced by a direct esterification reaction such as medium-chain fatty acid triglycerides can be used. Palm-based oils and fats (palm oil, palm kernel oil, palm olein, palm stearin, palm super olein, palm mid-fraction, etc.) and fractionated oils thereof are preferred because of the remarkable deterioration in flavor at low temperatures. In addition, according to the manufacturing method of the glyceride composition of this invention, the flavor deterioration at the time of the low temperature preservation | save by a "returning substance" can be preferably suppressed also in the blend fats and oils which mix | blended palm oil fat and other refined oils.

  There are chemical refining (chemical refining) and physical refining (physical refining) as methods for refining vegetable oil, and any refining method may be used. The former chemical refining is a method usually used for refining vegetable oils. Crude oil obtained by squeezing and extracting the plant as raw material is degummed, deoxidized, decolorized, and dewaxed. After being deodorized, it is refined and becomes refined oil.

  On the other hand, the latter physical refining is a method that is often performed with palm oil, palm oil or the like, and crude oil obtained by pressing palm or palm as a raw material is degummed, decolorized, or deoxidized. After being deodorized, it is refined and becomes refined oil.

(Glyceride composition obtained by the production method of the present invention)
The glyceride composition of the present invention is obtained by the above-described method for producing the glyceride composition of the present invention. According to the glyceride composition of the present invention, the amount of “returning substance” in the glyceride composition, that is, 2-nonenal, is suppressed, and the flavor deterioration of fats and oils is suppressed.

  Hereinafter, although it demonstrates still in detail based on the Example of this invention, this invention is not limited to these description at all.

  The following conditions were examined for the presence or absence of a low-temperature return odor in the glyceride composition, the inhibitory effect of 2-nonenal, fatty acid esters of glycidol and trans fatty acids, and the autooxidation inhibitory effect of the glyceride composition.

[Comparative Example 1]
RBD palm oil (produced in Malaysia or / and Indonesia) was decolored at 105-110 ° C. for 15-30 minutes in the presence of white clay, and then the white clay was removed by filtration to obtain a decolorized oil. Next, deodorizing treatment is performed at 255 ° C. for 80 to 100 minutes under reduced pressure while blowing water vapor into the decolorizing oil. When the oil temperature becomes 110 to 180 ° C. during the deodorizing treatment, citric acid is added to the glyceride composition. It added so that it might become 30 ppm in a composition. Next, filtration was performed to obtain a glyceride composition of Comparative Example 1.

[Comparative Example 2]
Except performing a deodorizing process at 245 degreeC, it processed by the method equivalent to the comparative example 1, and the glyceride composition of the comparative example 2 was obtained.

[Comparative Example 3]
Except not adding citric acid, it processed by the method equivalent to the comparative example 1, and obtained the glyceride composition of the comparative example 3.

[Comparative Example 4]
A glyceride composition of Comparative Example 4 was obtained by performing the same treatment as Comparative Example 1 except that the deodorization treatment was performed at 200 ° C. and citric acid was added to 30 ppm in the glyceride composition.

[Comparative Example 5]
The glyceride composition of Comparative Example 5 was obtained in the same manner as in Comparative Example 1 except that ascorbic acid was added to 1 ppm in the glyceride composition instead of citric acid.

[Comparative Example 6]
The glyceride composition of Comparative Example 6 was obtained in the same manner as in Comparative Example 1 except that ascorbic acid was added to 3 ppm in the glyceride composition instead of citric acid.

[Comparative Example 7]
A glyceride composition of Comparative Example 7 was obtained in the same manner as in Comparative Example 1 except that citric acid monoglyceride was added to 300 ppm in the glyceride composition instead of citric acid. In Table 4, “citric acid MG” indicates citric acid monoglyceride.

[Example 1]
Except for adding citric acid to 3 ppm in the glyceride composition, the treatment was carried out by the same method as in Comparative Example 1, and the glyceride composition of Example 1 was obtained.

[Example 2]
Except having added citric acid so that it might become 10 ppm in a glyceride composition, it processed by the method equivalent to the comparative example 1, and the glyceride composition of Example 2 was obtained.

[Example 3]
The glyceride composition of Example 3 was obtained by carrying out the treatment in the same manner as in Comparative Example 1 except that the deodorization treatment was performed at 245 ° C. and citric acid was added to 3 ppm in the glyceride composition.

[Example 4]
The glyceride composition of Example 4 was obtained by carrying out the deodorization treatment at 245 ° C. and carrying out the same treatment as in Comparative Example 1 except that citric acid was added to 10 ppm in the glyceride composition.

[Example 5]
The glyceride composition of Example 5 was obtained by performing the same treatment as in Comparative Example 1 except that citric acid was added to 1 ppm in the glyceride composition.

[Example 6]
A glyceride composition of Example 6 was obtained in the same manner as in Comparative Example 1, except that ascorbic acid was added to 10 ppm in the glyceride composition instead of citric acid.

[Example 7]
The glyceride composition of Example 7 was obtained by performing the same treatment as in Comparative Example 1 except that ascorbic acid was added instead of citric acid.

[Example 8]
A glyceride composition of Example 8 was obtained by performing the same treatment as in Comparative Example 1 except that ascorbic acid was added to 100 ppm in the glyceride composition instead of citric acid.

[Example 9]
A glyceride composition of Example 9 was obtained in the same manner as in Comparative Example 1, except that citric acid monoglyceride was added to 10 ppm in the glyceride composition instead of citric acid. In Table 4, “citric acid MG” indicates citric acid monoglyceride.

[Example 10]
A glyceride composition of Example 10 was obtained in the same manner as in Comparative Example 1 except that citric acid monoglyceride was added to 100 ppm in the glyceride composition instead of citric acid.

[Example 11]
A glyceride composition of Example 11 was obtained in the same manner as in Comparative Example 1, except that citric acid monoglyceride was added to 200 ppm in the glyceride composition instead of citric acid.

<Examination of presence or absence of return odor in glyceride composition>
Each glyceride composition was dispensed in an amount of 20 to 70 g in a 100 ml sample bottle and stored in a cool dark place at 5 ° C. after sealing. On the 14th day after storage, the sample bottle was taken out and dissolved by heating at 50 to 80 ° C., and then sensory evaluation was performed with a few grams in the mouth. In this case, the five-step evaluation was in accordance with the criteria described in Table 1.

  For each glyceride composition, the sensory evaluation result of “3 or more” was regarded as “low” low temperature return odor, and the sensory evaluation result of “less than 3” was defined as low temperature return odor “present”. . The results are shown in "Presence / absence of low temperature return odor" in Tables 2-4.

<Examination of 2-nonenal production amount in glyceride composition>
Each glyceride composition was dispensed in an amount of 20 to 70 g in a 100 ml sample bottle and stored in a cool dark place at 5 ° C. after sealing. Take out the sample bottle on the third day of storage, dispense 1-10 g of each glyceride composition into a headspace vial tube, and adsorb volatile substances generated when heated at 50-100 ° C. for 30-100 minutes Adsorbed with an agent. The adsorbent was reheated at 200 to 250 ° C. for 1 to 10 minutes at a gas chromatography inlet, and the volatile material was applied to a gas chromatography column. Subsequently, each component isolated in the column was detected with a detector, and 2-nonenal was identified, followed by quantification with a reagent manufactured by Wako Pure Chemical Industries (Wako Grade 1). The result is shown in "2-nonenal production amount" of Tables 2-4.

<Examination of fatty acid ester production amount of glycidol in glyceride composition>
The determination of the fatty acid ester (GE) of glycidol in the glyceride composition was carried out according to the German official method (DGF Standard Methods C-III 18 (09)). In this method, since the fatty acid ester of glycidol was converted into 3-chloropropane-1,2-diol (3-MCPD) when preparing the measurement sample, the fatty acid ester of glycidol was measured as free 3-MCPD.
After adding 50 μL of an internal standard substance (3-MCPD-d5 20 μg / mL solution) to 100 mg of the glyceride composition of each example and each comparative example, 1 mL of sodium methoxide solution (0.5 mol / L methanol) was added. In addition, the reaction was carried out at room temperature to saponify and decompose the ester. Next, 3 mL of brine (20%) containing a small amount of acetic acid and 3 mL of hexane were added to and mixed with this, and then hexane was removed. At this time, the fatty acid ester of glycidol is converted to 3-MCPD as the ester bond is broken. Thereafter, it was derivatized with 250 μL of an aqueous phenylboric acid solution (25%), extracted with 2 mL of hexane, and measured with a gas chromatograph mass spectrometer.
Using the chromatogram obtained by the measurement of the gas chromatograph mass spectrometer, the fatty acid ester of glycidol in the glyceride composition by comparing the ionic strength of 3-MCPD-d5 which is an internal standard and 3-MCPD Was calculated in terms of free 3-MCPD. The results are shown in “GE in glyceride composition” in Tables 2-4. In the table, “ND” indicates that the fatty acid ester of glycidol in the glyceride composition was not detected.

(GC-MS analysis conditions)
Analytical apparatus: Model name QP-2010, manufactured by Shimadzu Corporation Column: Product name HP-5MS (φ0.25 mm × 30 m), manufactured by Agilent Technology Oven temperature: 60 ° C. (1 min) to 120 ° C. (10 ° C./min) -190 ° C (6 ° C / min) -280 ° C (20 ° C / min)
Inlet temperature: 250 ° C
Column flow rate: 1.88 mL / min
Detector: MS (EI, SIM mode)
Splitless: 1 μL injection Carrier gas: He

<Examination of auto-oxidation of glyceride composition>
In order to study autooxidation of glyceride compositions, an automated oil stability (CDM) test was performed. The test method followed the standard oil analysis test method 2.5.1.2-1996. The results are shown in "CDM in glyceride composition" in Tables 2-4.

<Examination of conversion rate of trans fatty acid in glyceride composition>
The trans fatty acid conversion rate in the glyceride composition was determined as follows.
First, the trans fatty acid content in all the constituent fatty acids in the glyceride compositions of each Example and each Comparative Example was measured based on AOCS (American Official Chemistry's Society) Official Method Ce 1f-96.
Subsequently, the trans fatty acid conversion rate was calculated | required with the following formula. The results are shown in “Trans fatty acid conversion rate in glyceride composition” in Table 2.
・ Trans fatty acid conversion rate of unsaturated fatty acid (mass%) = ((trans isomer mass of unsaturated fatty acid constituting the refined fat / oil−trans isomer mass of unsaturated fatty acid constituting the fat / oil before purification)) / (Mass of total fatty acids constituting the oil before refining)) × 100

  From the results of Tables 2 to 4, in the deodorization step, (1) citric acid in an amount of 0.5 ppm to 10 ppm in the glyceride composition, (2) ascorbic acid in an amount of 5 ppm to 100 ppm in the glyceride composition, Or (3) In the glyceride composition to which citrate monoglyceride is added in an amount of 5 ppm to 250 ppm in the glyceride composition, the amount of 2-nonenal produced is small, there is no return odor, and the fatty acid of glycidol in the glyceride composition It was confirmed that the production of esters and trans fatty acids and the autoxidation of fats and oils can be suppressed.

Claims (2)

In deodorization step performed by the deodorizing temperature of two hundred ten to two hundred and forty-five ° C., the glyceride composition, see contains the step of adding citric acid in an amount equal to or less than the glyceride composition 3ppm least 0.5 ppm,
The citric acid is added to the glyceride composition after the glyceride composition is heated at 210 to 245 ° C and the oil temperature of the glyceride composition becomes 110 to 180 ° C.
A method for producing a glyceride composition.   The manufacturing method according to claim 1, wherein the glyceride composition is palm oil.