KR20120135161A - A process for preparing low 3-mcpd-fs edible oil - Google Patents

Abstract

PURPOSE: A producing method of edible oil with reduced 3-MCPD-FS(3-chloro-1,2-propanediol forming substances) is provided to use an absorber to reduce the amount of 3-MCPD-FS which is harmful to human body. CONSTITUTION: A producing method of edible oil with reduced 3-MCPD-FS comprises a step of deodorizing and refining fats and oils, and a step of processing the refined fats and oils using activated carbon before filtering. The refined fats and oils includes soybean oil, corn oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, processed fat, or their mixture. [Reference numerals] (AA) Raw oil; (BB) Degumming; (CC) De-acidifying; (DD) Bleaching; (EE) Deodorizing; (FF) Absorbing; (GG) Filtering; (HH) Product

Description

A process for preparing low 3-MCCD-FS edible oil}

The present invention relates to a method for preparing edible oil, and more particularly to a method for producing edible oil with reduced 3-MCPD-FS (3-chloro-1,2-propanediol forming substances) having a risk of genotoxicity or carcinogenesis. It is about.

3-MCPD-FS (3-chloro-1,2-propanediol forming substances) is a generic term for substances that produce 3-MCPD (3-chloro-1,2-propanediol). MCPD, glycidol, and bound 3-MCPD, bound glycidol, in which fatty acids are bound to these substances. In edible oils and fats, 3-MCPD-FS in the form of a fatty acid bound is detected.

Bound 3-MCPD refers to 3-MCPD fatty acid esters (monoesters and diesters with higher fatty acids) and is known to be naturally produced in the manufacture or processing of foods containing fats and salts (sodium chloride). It is detected with 3-MCPD in a variety of foods, including breads (donuts), french fries, roasted coffee, and roasted malt. In addition, bound 3-MCPD is also detected in acid-mediated pickled olives and herring at low temperatures, particularly in vegetable fats and oils including refined olive oil (Seefelder, W. et al. ., Esters of 3-Chloro-1,2-propanediol (3-MCPD) in Vegetable Oils: Significance in the Formation of 3-MCPD, Food Additives & Contaminants.Part A, Chemistry, Analysis, Control, Exposure & Risk Assessment 4 : 391-400 (2008). Although the toxicity and ecological characteristics of the combined 3-MCPD are not exactly known, in some European countries there is a possibility that the combined 3-MCPD can be converted to 3-MCPD. It became.

3-MCPD is a colorless or pale yellow chemical of chloropropanol, which is produced when a small amount of glycerin reacts with hydrochloric acid during the process of hydrolysis of vegetable fats into glycerin and fatty acids when vegetable proteins are broken down into amino acids and fats. It is a kind. Although it is known that 3-MCPD is not carcinogenic to humans, animal experiments have shown the possibility of reducing fertility and sperm production and genotoxicity (Hamlet, CG et al., Chloropropanols and Chloroesters, in Process-Induced Food). Toxicants: Occurrence, Formation, Mitigation, and Health Risks, edited by Richard H. Stadler and David R. Lineback , John Wiley & Sons, Inc., pp. 175-214 (2009)). In 1996, 3-MCPD was detected in soups, soy sauce, and acid-decomposition-HVP of instant noodles, which are consumed not only in Korea, but also in many countries in Southeast Asia, as well as in Western countries. The limit is 0.02 ppm in the EU, 1.0 ppm in Canada, 0.2 ppm in Australia and 0.3 ppm in Korea.

Bound glycidol is a combination of one fatty acid in a glycidol substance, and the safety of the bound glycidol itself is not clear at present, but it may be digested and degraded in the body to release glycidol. Glycidol is classified as a carcinogenic risk to humans by the International Cancer Research Institute (IARC), and the safety of the combined glycidol contained in processed foods, especially in Europe and Japan. Discussion is underway. Currently, in the case of bound glycidol included in foods, there is no known method for analyzing glycidol alone, and a method of converting glycidol to 3-MCPD and calculating the total amount of 3-MCPD is used. It is reported that about 10-60% of 3-MCPD content is derived from glycidol (ILSI Europe Report 2009, 3- MCPD). esters in food products . in ILSI workshop, Brussels, Belgium). The mechanisms of the generation of these harmful or potentially harmful 3-MCPD-FS substances are not yet known.However, in 2004, HAMLET et al. Proposed the mechanism of conversion of bound 3-MCPD to 3-MCPD as follows. (Hamlet CG et al, Generation of monochloropropanediols (MCPDs) in model dough systems. 1. Leavened doughs. Journal of Agriculture and Food Chemistry , 2004, 52, 20592066).

1,3 or 1,2-diacylglycerol is produced by reaction of triacylglycerol and salt by heating during food manufacturing process and is an intermediate of cyclicacyloxonium 1,2-diacylchloropropane-1,2-diol, which is a 3-MCPD bound type, by hydrolysis and chlorine substitution through ions Hydrolysis reaction to produce 1 or 2-acyl-3-chloropropane-1,2-diol (1 or 2-acyl-3-chloropropane-1,2-diol), followed by hydrolysis reaction. To 3-MCPD. The reaction scheme of the production mechanism of 3-MCPD-FS is shown in FIG.

In the case of edible fats and oils, it is known that traces of chlorine compounds contained in raw materials or water are produced by reaction with fats and oils at high temperature conditions during the refining process. . The 3-MCPD-FS content detected in purified oils is on the order of 0.3-13 ppm (ILSI Europe Report 2009, 3-MCPD esters in food products . In ILSI workshop, Brussels, Belgium).

In order to reduce the harmfulness of 3-MCPD-FS, 3-chloro-1,2-propanediol is controlled by adjusting the concentration of hydrochloric acid in the production of acid-decomposed soy sauce, which is produced by hydrolyzing some foods, especially animal and plant proteins with hydrochloric acid. A method of preparing soy sauce with a minimum content of (MCPD) is known (Korean Patent Laid-Open Publication No. 1999-0075193). However, no method of reducing 3-MCPD-FS in edible oil or fat is known at all.

Accordingly, the present inventors have studied to prepare edible oils with reduced amount of 3-MCPD-FS, which may be harmful to the human body. As a result, the present inventors have developed a method of reducing 3-MCPD-FS in edible oils using an adsorbent. This completes the present invention.

Accordingly, it is an object of the present invention to provide a method for producing edible oils with reduced 3-MCPD-FS.

Another object of the present invention is to provide an edible fat with reduced 3-MCPD-FS prepared by the above method.

In order to achieve the above object,

In the manufacturing method of edible fats and oils, 3-MCPD-FS (3-chloro-1,2-propanediol forming substances) reduced edible oils and fats, which is treated by adding an adsorbent to the refined fats and oils which have undergone the deodorizing process. It provides a method of manufacturing.

The present invention also provides edible oils with reduced 3-MCPD-FS prepared according to the above production method.

Hereinafter, the present invention will be described in more detail.

In the present invention, as a result of studying to prepare edible oil with reduced content of 3-MCPD-FS which is usually present in the concentration of 0.3 ~ 13 ppm in the edible oil, 3 It was found that the content of -MCPD-FS can be significantly lowered. Thus, it is possible to provide edible fats and oils that have lowered the content of 3-MCPD-FS, which may be harmful to the human body even through a very simple process.

Thus, according to one aspect of the invention, the present invention

In the manufacturing method of edible fats and oils, 3-MCPD-FS (3-chloro-1,2-propanediol forming substances) reduced edible oils and fats, which is treated by adding an adsorbent to the refined fats and oils which have undergone the deodorizing process. It provides a method of manufacturing.

The refined fats and oils may be vegetable oils, for example, soybean oil, corn oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil, processed oil, or a combination thereof. It is not limited to this.

Processed fats and oils during the refined fats and oils, when the diacylglycerol content is used in more than 10% by weight, can see a significant 3-MCPD-FS reduction effect, the manufacturing method of the edible fat according to the present invention can be effectively used.

The adsorbent used in the manufacturing method of the edible fat and oil is food acceptable and can be used any adsorbent that can adsorb 3-MCPD-FS without degrading the quality of edible fat, acidic clay, activated carbon, Diatomaceous earth, or a combination thereof may be used. However, diatomaceous earth may be used to reduce the quality of fats and oils by darkening the color of fats and oils, and the adsorbent is preferably acidic clay, activated carbon, or a combination thereof.

In the manufacturing method of the edible fats and oils, the adsorbent may be used in a content of 0.5% by weight or more and 5.0% by weight or less of the refined fats and oils, if it does not fall within the above ranges may not sufficiently reduce 3-MCPD-FS, the above ranges If it overflows, the economy may be inferior to the effect.

In the manufacturing method, an adsorbent is added to the refined oils and oils subjected to the deodorizing process, stirred at 25-100 ° C., and the adsorbents are filtered to prepare edible oils with reduced 3-MCPD-FS. Preferably the stirring temperature may be carried out at 30-90 ℃. As the temperature increases in the temperature range, the 3-MCPD-FS reduction effect tends to increase. However, when the temperature is exceeded, the 3-MCPD-FS reduction effect may be lowered.

In the manufacturing method of the edible oil according to the present invention, the preparation of edible oil and fat is completed by passing the adsorption process by the adsorbent and the filtration process of the adsorbent in the refined fat and oil having undergone the deodorization process, and the conventional purification process of the edible fat and oil before the deodorization process. Can be rough. Such conventional edible fat and oil purification procedures are well known in the art. 2 is a flowchart illustrating a method of manufacturing edible oil according to one embodiment of the present invention.

Edible fats and oils prepared according to the manufacturing method of edible fats and oils according to the present invention is preferable because the content of 3-MCPD-FS is significantly reduced compared to the conventional edible fats and lower the risk that can be generated thereby.

Therefore, in another aspect, the present invention provides edible fats and oils reduced by 3-MCPD-FS prepared by the manufacturing method according to the present invention.

The edible oils and fats may contain 0.3 ppm or less of 3-MCPD-FS.

As described above, according to the method of the present invention, it is possible to prepare edible oils with a significantly reduced content of 3-MCPD-FS compared to conventional edible oils. Therefore, according to the manufacturing method of edible oils and fats of the present invention, it is desirable to provide edible fats and oils, which significantly lower the risk of genotoxicity and carcinogenicity, which have been caused by the presence of 3-MCPD-FS.

Figure 1 is a reaction scheme showing the production mechanism of 3-MCPD-FS (3-chloro-1,2-propanediol forming substances).
2 is a flowchart of a method of preparing edible oil according to an embodiment of the present invention.
3 is a graph showing the results of GC / MS analysis of 3-MCPD-FS content in edible oils prepared according to one embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto in any sense.

Preparation of Diacylglycerol-Containing Fat and Oil Composition (Control Edible Oil) 2

The diacylglycerol-containing fat or oil composition is prepared by mixing fatty acids derived from soybean oil with glycerol according to the method of Examples 1 and 5 specified in Korean Patent Publication No. 2004-0079402 and using 1,3-position specific lipase under vacuum drying. To prepare a liquid fat or oil composition containing a high diglyceride by carrying out the ester synthesis reaction, the obtained diglyceride high fat or oil composition was molecular distillation, decolorization and deodorization, the final glycerol composition is shown in Table 1 below The fatty acids were found to be 0.3% present in the glycerol composition.

Example 1-18: 3-MCPD-FS Reduction Treatment According to Adsorbent Type

Purified edible fats and oils by selecting acidic clay (DC-SUPER, Donghae Chemical Co., Ltd., Korea), activated carbon (MP-5020, Moorim Chemical Co., Ltd.), diatomaceous earth (Celite503, Celite Korea, Korea) It was. To the prepared diacylglycerol-containing fats and oils (control group) deodorized at 240 ℃ acidic clay, activated carbon, or diatomaceous earth was added 0.1 to 3.0% by weight in accordance with the conditions of Table 2, respectively, and stirred for 1 hour at 90 ℃ Processed. The adsorbent was then filtered to complete cooking oil with reduced 3-MCPD-FS content.

Example 19-22 3-MCPD-FS Reduction Treatment with Temperature

Acidic clay was used as the adsorbent, and cooking oil having reduced 3-MCPD-FS content was prepared while varying the reaction temperature. The acidic clay (DC-SUPER, Donghae Chemical Co., Ltd., Korea) was added 2.0 wt% to the cooking oil (control group) deodorized at 240 ° C to prepare a high content of diacylglycerol, and 30 ° C (Example 19) and 50 ° C. (Example 20), 90 degreeC (Example 21), and 120 degreeC (Example 22) were stirred for 1 hour, respectively. The adsorbent was then filtered to complete cooking oil with reduced 3-MCPD-FS content.

<Experimental Example>

3-MCPD-FS content analysis method

Gas chromatography / Mass spectrometer (GC / MS) was used to analyze 3-MCPD-FS content. Analytical conditions were performed under the same conditions as in Table 3 below.

100 mg of sample was dissolved in t-butylmethylate (tBME): ethyl acetate (EA) (8: 2, v / v, solvent A), and then 50 uL of 200 ppm internal standard and 1 ml of sodium methoxide (NaOCH). ₃ ) After adding the solution, leave at room temperature for 5-10 minutes. 3-MCPD-d ₅ is used as internal standard. 3 ml of hexane and acetic acid: 20% NaCl solution (1:30, v / v, solvent B) was added thereto, and then the upper organic solvent layer was removed. 250 ul of phenylboronic acid, a derivatization reagent, is added to the water layer and reacted at 80 ° C. for 20 minutes. At this time, derivatization of the standard material is also performed. After cooling to room temperature and extracted with 3ml hexane, the hexane layer is analyzed by GC / MS. Quantitative analysis is 196m / z (3-MCPD) and 201m / z (3-MCPD- d 5) ion was used as the qualitative character is 147m / z (3-MCPD) and 150m / z (3-MCPD- d 5 Ion was used.

Experimental Example 1: Analysis of 3-MCPD-FS content according to the type and concentration of adsorbent

The purified edible oils obtained in Examples 1 to 18 were analyzed for 3-MCPD-FS content according to the 3-MCPD-FS content analysis method. The results are shown in Table 4 below. In addition, the results of the 3-MCPD-FS content analysis for the purified edible oil obtained in Example 4 is shown in FIG.

According to the experimental results, there was a difference in the effect of reducing 3-MCPD-FS according to the type and concentration of the adsorbent to be treated. The most effective was activated carbon, which was reduced to 0.13 ppm after 3% treatment. Diatomaceous earth had a 3-MCPD-FS reduction effect depending on the treatment concentration, but the color of fats and fats became very dark, which resulted in a decrease in the quality of edible fats and oils. Both acidic clay and activated carbon were effective when 0.5 wt% or more was used, and when 0.25 wt% of acidic clay and 0.25 wt% of activated carbon were used, even when two adsorbents were mixed at 0.29 ppm as a result of 3-MCPD-FS analysis The same effect was shown.

Experimental Example 2: 3-MCPD-FS content analysis according to the treatment temperature

The purified edible oils obtained in Examples 19 to 22 were analyzed for 3-MCPD-FS content according to the 3-MCPD-FS content analysis method. The results are shown in Table 5 below.

According to the results, the 3-MCPD-FS content showed a tendency to decrease with increasing temperature. However, when the temperature is too high, the 3-MCPD-FS content increased, indicating that about 30-90 ° C. was the preferred temperature range.

Claims (7)

In the manufacturing method of edible fats and oils, 3-MCPD-FS (3-chloro-1,2-propanediol forming substances) reduced edible fats and oils, which is treated by adding activated carbon to the refined fats and oils which have undergone the deodorizing process. Manufacturing method. The method of claim 1, wherein the refined fats and oils are soybean oil, corn oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil, processed fats, or a combination thereof. . The method according to claim 1, wherein the refined fat or oil has a diacylglycerol content of 10% or more. The method of claim 1, wherein the activated carbon is 0.5% by weight or more of the refined fat or oil. The method of claim 1, wherein the activated carbon is treated at a temperature of 25 to 100 ° C. The edible fats and oils which reduced 3-MCPD-FS manufactured by the manufacturing method of any one of Claims 1-5. 7. The edible oil and fat according to claim 6, wherein the content of 3-MCPD-FS is 0.3 ppm or less.

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