KR100367103B1 - The method for preventing flavor formation in Hydrogenated vegetable oil or Hydrogenated vegetable oil including CLA and Hydrogenated vegetable oil produced thereby - Google Patents

Abstract

The present invention relates to a method for inhibiting the generation of hardening odor of vegetable hardened oil containing vegetable hardened oil or conjugated linoleic acid (CLA: hereinafter abbreviated as CLA), and vegetable hardened oil prepared by the same method. The antioxidant is added after the decolorizing step in the refining step of the cured oil) and the curing step is performed.

According to the present invention, the production of vegetable hardened oil (including CLA vegetable hardened oil) can suppress the generation of various volatile compounds, which are the causes of hardening odor generated during the curing process, thereby improving flavor, and also the vegetable hardened oil according to the present invention. When it is applied to foods, the cured odor causing rejection is suppressed to a considerable extent, which has the advantage of increasing the value of products due to improved flavor.

Description

The method for preventing flavor formation in Hydrogenated vegetable oil or Hydrogenated vegetable oil including CLA and Hydrogenated vegetable oil produced according to the hardening odor generation of vegetable hardened oil (including CLA vegetable hardened oil)

The present invention is a method for inhibiting hardening odor generation of vegetable hardened oil (CLA: Conjugated Linoleic acid, hereinafter referred to as CLA) and vegetable hardened oil containing cured odor, In more detail, the present invention relates to a method of reducing volatile compounds to a significant extent by inhibiting the production of volatile compounds generated during the curing process (hydrogenation step).

The CLA is an unsaturated fatty acid having 18 carbon atoms and is known to have excellent effects such as lowering blood cholesterol, reducing body fat, and anticancer function in adults. The CLA can be formed under specific conditions during the curing process of vegetable oils and fats, but CLA vegetable hardened oils formed by this method have limitations in the application of foods and medicines due to the curing odor generated during curing.

1 illustrates various conventional oil and fat refining processes, and the conventional refining method includes a second process of first degumming crude oil extracted and pressing and denitralizing fats and oils through an electric degumming process, and an electric process. A third step of bleaching the fats and oils desorbed by using acidic clay, a fourth step of curing by hydrogenation after the electrobleaching process, and a final deodorization of the cured oil. It consists of 5 steps.

Vegetable hardening oil or CLA vegetable hardening oil prepared through the conventional refining process has been pointed out that a significant amount of volatile compounds, for example, aldehydes, alcohols, various acids and esters, etc., which cause curing odors, has been pointed out. There is no clear alternative to solve the problem, and when the vegetable hardening oil according to the conventional refining method is applied to the food as it is, it will adversely affect the flavor of the product due to the hardening odor, which may cause a decrease in the value of the product. .

The present inventors seek to find a fundamental solution to the problems caused by the conventional method for producing vegetable hardening oils (including CLA vegetable hardening oils), thereby greatly reducing hardening odors by suppressing the generation of volatile compounds, which are the causes of hardening odors. The present invention has been completed in view of the fact that it can be made.

Therefore, the present invention focuses on the fact that the cause of hardening odor is an oxidation product of fats, thereby minimizing the generation of volatile compounds by inhibiting oxidation of fats during the hardening (hydrogenation) process, thereby further improving flavor as hardening odor is reduced to a considerable extent. It is an object to provide dried vegetable hardened oil (including CLA vegetable hardened oil).

In addition, another object of the present invention is to improve the quality of the product by using a vegetable hardening oil reduced hardening odor as a raw material of various foods, thereby contributing to the development of the food industry.

1 is a process of refining vegetable cured oil of the prior art.

Figure 2 is a vegetable curing oil purification process of the present invention.

3 is a gas chromatograph of volatile compounds separated from CLA-cured soybean oil obtained by a conventional refining process.

Figure 4 is a gas chromatograph of volatile compounds separated from CLA hardened soybean oil obtained by the purification process of the present invention.

The present invention is to carry out a curing (hydrogenation) step by adding an antioxidant to the fats and oils to prevent oxidation of fat after the decolorization step in the purification process of vegetable oils and fats.

The hardening odor that occurs during hardening of vegetable oils is derived from various trace components such as phospholipids, calcium ions (Ca ²⁺ ), magnesium ions (Mg ²⁺ ) and iron ions (Fe ²⁺ ). It promotes and increases the production of causative aldehydes, alcohols, ketones and esters.

The present invention is to prevent the formation of aldehydes, alcohols, ketones and esters as a direct cause of the curing odors by adding an antioxidant before curing to inhibit oxidation during the curing process of vegetable curing oils (including CLA vegetable curing oils) Disclosed are methods for significantly reducing the production of causative agents.

The antioxidants include TBHQ (tertiarybutylhydroquinone), PG (propyl gallate), BHA (butylhydrocycyanazole), BHT (butylhydrocycitoluene), and the like. It is preferred to add 0.05% by weight. If less than 0.005% by weight is not sufficient to suppress the oxidation occurring during the curing process, if it exceeds 0.05% by weight it is not preferable because more synergistic effect is difficult to expect.

Hereinafter, the manufacturing process of the vegetable hardening oil (including CLA vegetable hardening oil) of the present invention will be described in more detail with reference to the accompanying drawings.

Figure 2 shows the flow of refining process of the vegetable hardening oil (including CLA vegetable hardening oil) of the present invention used as a main raw material in food production, the first step of degumming crude oil, and degreased oil And a second step of drying and deoxidizing, a third step of adsorbing a trace component using an adsorbent such as acidic clay, followed by filtration and bleaching of the fat and oil which have been deoxidized. Deodorization was carried out by stripping dry steam to vegetable hardened oils (including CLA vegetable hardened oils) prepared by the fourth step and the electric process of adding an antioxidant to the fat and oil which had been decolorized by hydrogen and then curing (dehydrogenation). Deodorization is composed of the fifth process.

The degumming process of the first step is to remove impurities such as phospholipids, gums, carbohydrates, and proteins using aqueous solutions of oxalic acid and phosphoric acid. By adding 0.1 to 0.3% of crude oil to the extracted crude oil, 75% The impurities are removed by stirring at ˜95 ° C. for 20 minutes to 1 hour.

The fats and oils processed by the degumming process which is the first process contain free fatty acid. The free fatty acid is removed in a deoxidation process, which is a second process. The free fatty acid is removed by washing with water and drying by appropriately administering sodium hydroxide (20 bome) according to the acid value.

The decolorizing step of the third step of the step is a step of removing pigments such as microelements and natural pigments, such as chlorophyll and carotene, by physical adsorption of the fats and oils obtained through the electrical deoxidation process. The dye and the trace elements are removed by physical adsorption in a vacuum (10 mmHg) using an adsorbent composed of the same.

The curing step of the fourth step of the process is a step of adding hydrogen to the unsaturated fatty acid in the fat by a catalyst, in particular 0.5 to 5 kg / cm ³ under a nickel catalyst (0.3 to 0.5%) in order to induce CLA formation during the fat or oil The conditions which make it react at 160-230 degreeC, adding hydrogen at the pressure of are needed. According to Figure 3 it can be seen that the CLA is contained in the vegetable fat and oil through the curing process.

The deodorization process, which is the fifth step of the process, is a final process of purification to remove oily components and other volatile components in the vegetable hardened oil (including CLA vegetable hardened oil) obtained by the fourth process to obtain high stability and high flavor. The deodorizing process injects dry steam at a vacuum degree of 2 to 4 mmHg and a reaction temperature of 165 to 230 ° C. for about 25 minutes, and removes odorous components and other volatile components in fats and oils and finally removes the hardening odor (including CLA vegetable hardening oil). )

The present invention, unlike the conventional method of vegetable hardening oil (including CLA vegetable hardening oil) is cured by adding an antioxidant after the decolorization process to inhibit the oxidation during the curing process by inhibiting the formation of volatile compounds as a cause of the hardening odor cured Maximize the effect of reducing odor.

Vegetable oils suitable for the practice of the present invention include hardened oils (including CLA-containing hardened oils) processed using general edible oils such as soybean oil, jade oil, cottonseed oil, canola oil, sunflower seed oil, rice bran oil and safflower seed oil. It is most preferred in the practice of the present invention because it is easy to prepare a hardened oil having a high CLA content.

Vegetable hardening oil (including CLA vegetable hardening oil) of the present invention prepared by the above process has a good flavor state, such as milk noodle, processed milk, fermented milk, snacks, ice cream products, ice cream, processed chocolate, shortening margarine, confectionery, confectionary Sensory properties can be greatly improved by applying to foods such as breads and frozen foods.

Hereinafter, the content of the present invention will be further embodied by the examples. However, the following examples are only intended to illustrate the present invention, it is apparent to those skilled in the art that all inventions that fall within the same range do not depart from the scope of the present invention.

<Example 1>

Phosphoric acid was added to the soybean crude oil extracted from soybean, and 0.3% phosphoric acid of soybean oil was stirred for 30 minutes at 85 ° C. After removing impurities such as phospholipid, gum, carbohydrate, and protein, sodium hydroxide (20bome) was maintained there 0.3% of the free fatty acid was removed, washed with water, and dried at 105 ° C. Pigment and trace elements were removed by physical adsorption under vacuum (10 mmHg) for 30 minutes using 8% by weight of acidic clay compared to oils and fats maintained by the electric process. TBHQ 100mg / kg oil is added to oils and fats to remove pigments and trace elements, and reacted at 230 ℃ with hydrogen at 0.5kg / cm ³ under nickel catalyst (0.5%) to contain CLA. One cured soybean oil was obtained.

CLA-containing hardened soybean oil obtained through the above curing process was injected with dry steam for 25 minutes at a vacuum degree of 4 mmHg and a reaction temperature of 230 ° C. to remove odorous components and other volatile components in oils and fats, thereby obtaining CLA-cured soybean oil finally cured. .

<Example 2>

CLA-cured soybean oil was obtained in the same manner as in Example 1 except that TBHQ 200 mg / kg oil was added to the fat and fat after the decolorization process.

<Example 3>

CLA-cured soybean oil was obtained in the same manner as in Example 1, except that TBHQ 500 mg / kg oil was added to the fat and fat after the decolorization process.

<Example 4>

CLA-cured soybean oil was obtained in the same manner as in Example 1 except that TBHQ 50 mg / kg oil was added to the fat and fat after the decolorization process.

Test Example 1 Component Identification and Quantitative Experiments on Volatile Compounds in Cured Soybean Oil

In order to compare the relative content of various volatile compounds known as the causative agent of hardening odor, the CLA hardened soybean oil prepared according to Example 2 and CLA hardened soybean oil by the conventional refining process were used as a control. Volatile compounds were isolated and identified in each of the two samples and their relative contents were measured.

Gas Chromatography Operating Conditions

Volatile compounds were concentrated from CLA-cured soybean oil using solid phase microextraction (SPME) technology and separated by gas chromatography. The fiber used was 75mm carboxen-PDMS. For adsorption of volatiles, CLA-cured soybean oil samples were accurately weighed 5.0g into 30ml-capacity serum bottles, and airtight and sealed using silicon-lined rubber septa and aluminum caps. Then, after heating at 100 ° C. for 60 minutes on a hot plate, 75 mm carboxyl-PDMS fiber was injected into a serum bottle and volatile compounds were adsorbed for 10 minutes. Carboxen-PDMS fibers adsorbed with volatile compounds were desorbed for 1 minute in a gas chromatograph injector (250 ° C.) and injected into gas chromatography. The gas chromatography oven temperature was kept isothermal at 50 ° C. for 1 minute and then increased to 200 ° C. at a rate of 4 ° C. per minute. The column used was a capillary column (Supeco Wax 60m X 0.22mm) and helium was used as the carrier gas. The detector used a flame ionization detector (FID) to calculate the peak area, and the temperature was 260 ° C. Gas chromatography-mass spectrometry (GC-MS) was used to identify volatile compounds, and the analysis column and analysis conditions were the same as those of gas chromatography. A snipping port mounted on gas chromatography was used.

3 and 4 show gas chromatographic results of volatile compounds separated from CLA-cured soybean oil and CLA-cured soybean oil according to the present invention.

In addition, Table 1 shows the results of identifying the peaks of the volatile compounds of CLA-cured soybean oil to which the conventional purification process is applied, and show the odor characteristics and strength of the volatile compounds.

A total of 35 compounds were identified in the experiment, most of which were aldehydes, alcohols, acids and esters and the like. Among them, 15 volatile compounds with odor strength above medium (++) and 5 compounds with strong (+++) or more were identified (peak number 13, 15, 22, 23, 29). The above volatile compounds are 4-azido-heptane, 2-octenal, (E) -2-nonenal [(E) -2-nonenal], unknown, ( E) -2-undekenal [(E) -undecenal], which was found to lead the odor of CLA-cured soybean oil.

Table 2 shows the peak area of the gas chromatograph for the volatiles of the conventional CLA-cured soybean oil and CLA-cured soybean oil obtained by the purification process of the present invention. According to the results of the experiment, it was confirmed that the amount of volatile compounds of the CLA-cured soybean oil of the present invention was significantly less than that of the general CLA-cured soybean oil. The total peak area of the sum of the peaks 1 to 35 was 259,523 for general CLA-cured soybean oil and 157,092 for specially treated CLA-cured soybean oil, corresponding to about 60.5%.

<Table 1> Volatile Compounds from CLA Cured Soybean Oil

N0. Compound ^{a, b} Ri ^c Flavor Fi ^d One Methoxyethane ^a 785 - 2 Pentanal ^{a, b} + unknown 954 Oxidized fat ++ 3 Nucleic Acid Egg ^{a, b} 1068 pool ++ 4 4-pentanal ^{a, b} 1139 - 5 1-butanol ^{a, b} 1151 - 6 Heptane ^{a, b} 1210 Fat, butter, medication + 7 (E) -2-nucleic acid ^{a, b} 1275 Fat + 8 1-pentanol ^{a, b} 1305 - 9 Octanal ^{a, b} 1359 Oxidized fat ++ 10 2,3-octanedione ^a 1411 - 11 (E) -2-heptenal ^{a, b} 1424 Fat ++ 12 1-nucleic acid ^{a, b} 1446 - 13 4-azido-heptane ^a 1456 butter +++ 14 3-methyl-1,5-pentadiol ^a 1494 Rubber, oxidized fat ++ 15 2-octenal ^{a, b} 1536 Fat, butter ++++ 16 1-octen-3-ol ^{a, b} 1559 Fat ++ 17 1-heptanol ^{a, b} 1567 Fat, butter ++ 18 1,1-heptanediol, diacetate ^a 1588 Fat ++ 19 Decanal ^{a, b} 1610 - 20 Nucleosanic acid, pentyl ester ^a 1616 - 21 (E, E) -2,4-heptadiene ^a 1629 Oxidized fat + 22 (E) -2-nonenal ^{a, b} 1654 Oxidized fat ++++ 23 Unknown 1660 Oxidized fat ++++ 24 1-octanol ^{a, b} 1670 Oxidized fat ++ 25 4-methyl-1-heptanol ^a 1705 - 26 (Z) -2-dekenal ^a 1744 Fat + 27 1-nonanol ^{a, b} 1755 - 28 Heptyl hexanoate ^a 1773 - 29 (E) -2-undekenal ^a 1819 Fat margarine ++++ 30 3,4-dimethyl-2,5-furandione ^a 1838 Fat ++ 31 (E, E) -2,4-decadienal ^{a, b} 1853 Fat + 32 Nucleosanic acid ^{a, b} 1881 - 33 Heptanoic acid ^{a, b} 1834 - 34 Octanoic acid ^{a, b} 1980 - 35 Nonanoic acid ^{a, b} 2020 -

a) Identified by mass spectrometry

b) Identified by comparison of retention indices of authentic compounds

c) Kovat's Retension Indices

d) FI, flavor intensity are divided by 4 categories (++++, very strong

; +++, strong; ++, medium; +, weak;-, none)

<Table 2> Peak Area Comparison of Volatile Compounds in CLA Cured Soybean Oil Prepared by General and Special Tablets

No. Peak area (electronic counts) General refined CLA soybean oil CLA soybean oil of the present invention One <100 100 2 11,878 8,437 3 12,996 10,718 4 + 5 10,764 5,447 6 10,146 5,740 7 15,690 7,438 8 6,019 4,925 9 14,123 9,693 10 5,391 9,964 11 34,031 24,593 12 2,600 1,508 13 100 100 14 19,022 10,489 15 20,738 7,498 16 1,038 1,531 17 4,012 1,721 18 3,483 2,037 19 + 20 3,901 210 21 7,593 8,567 22 16,658 4,417 23 100 100 24 6,344 3,423 25 100 100 26 20,535 12,489 27 1,053 256 28 100 100 29 9,769 2,822 30 8,631 3,623 31 100 100 32 3,697 1,088 33 6,083 6,113 34 1,247 936 35 1,481 779 sum 259,523 157,092

The total peak areas of the five volatile compounds with strong odor intensity (+++, ++++) were 47,369 and 14,937 for normal CLA hardened soybean oil and CLA hardened soybean oil of the present invention, respectively. This means that when the odor intensity is strong only (+++, +++), the CLA hardened soybean oil of the present invention corresponds to about 31.5% compared to the normal hardened soybean oil. The above results demonstrate that the purification process of the present invention significantly inhibits the production of volatile compounds contained in CLA-cured soybean oil.

The results are also the results of sensory evaluation conducted on 25 adult men and women as a noodle prepared by a known manufacturing method using the CLA-cured soybean oil of the present invention according to Example 3 and the CLA-cured soybean oil of Table 3 below. Is in agreement.

Test Example 2 Preparation of Noodles

In the mixer, flour and starch were mixed and kneaded with mixed water. Then, a cotton pad was formed on a roller, passed through an extruder to make noodles, and then steamed at 100 ° C. in a stick box. The steamed noodle was cut and put in a retainer, and then frying and cooling at 145 ° C. for 90 seconds using the CLA-cured soybean oil of the present invention in fryer to prepare ramen. The ramen prepared in this way contains about 18% CLA soybean cured oil, and the CLA content is about 0.9g per 100g of ramen products. For reference, studies have shown that ingestion of CLA of 0.6 to 6g / 1 day may have anti-cancer effects and decrease diet of body fat.

<Table 3> Sensory Evaluation Results.

division Intensity of smell Sensory evaluation General CLA Cured Soybean Oil 7.6 2.90 CLA curing oil of the present invention 2.5 4.35

* Smell intensity- 1: Very weak 3: Weak 5: Moderate 7: Strong 9: Very strong

* Sensory evaluation (5 points scale)-1: Very bad 2: Bad 3: Normal 4: Good 5: Very good * Number of testimonials-25 adult men and women.

In addition, the results are consistent with the sensory evaluation of 25 adult men and women with milk prepared by emulsifying the CLA-cured soybean milk of the present invention according to Test Example 3 and the general CLA-cured soybean milk of Table 4 below.

Test Example 3 Production of Milk

Milk cream was separated from crude oil to prepare skim milk, and 0.1% sucrose fatty acid ester was added to the skim milk, followed by stirring while warming to 65-70 ° C. The CLA-cured soybean oil was stirred with warming to 65-70 ° C., followed by addition of 0.2% glycerin fatty acid ester, followed by stirring for 5 minutes. The CLA soybean cured oil mixture solution was mixed with the skim milk mixture solution, stirred for 5 minutes, homogenized at 65-70 ° C., sterilized at 95 ° C. for 5 minutes, and cooled to 4 ° C. to prepare a finished product. The CLA content per 100 g of finished product was found to be about 154 mg.

<Table 4> Sensory Evaluation Results

division Intensity of smell Sensory evaluation General CLA Cured Soybean Oil 6.0 1.71 CLA curing oil of the present invention 2.8 4.30

* Strength of smell-1: Very weak, 3: Weak, 5: Medium, 7: Strong 9: Very strong

* Sensory evaluation (5 tablet scale)-1: Very bad 2: Bad 3: Normal 4: Good 5: Very good

Assessment staff: 25 adults

According to the present invention, the production of vegetable hardened oil (including CLA vegetable hardened oil) can suppress the generation of various volatile compounds which are the causes of hardening odor, thereby improving flavor, and furthermore, the vegetable hardened oil according to the present invention (including CLA vegetable hardened oil) ) Is applied to food, which can remove the hard odor that causes rejection to a considerable extent, thereby increasing the value of the product due to improved flavor.

Claims (9)

In the refining process consisting of degumming, deoxidizing and decolorizing processes of vegetable oils, and the manufacturing process of vegetable hardened oil composed of a curing process and a deodorizing process, Vegetable fat, characterized in that to suppress the generation of volatile compounds that cause curing odor by adding an antioxidant selected from the group of TBHQ, PG, BHA or BHT to the pre-cured fats and oils during the vegetable oil refining process Curing odor generation suppression method of curing oil delete The method of claim 1, wherein the vegetable fats and oils include soybean oil, jade oil, cottonseed oil, canola oil, sunflower seed oil, rice bran oil, and safflower seed oil. [Claim 2] The method of claim 1, wherein the antioxidant is added in an amount of 0.005 to 0.05% by weight relative to the content of vegetable fats and oils. The method of claim 1, wherein the remaining volatile compounds after the decolorizing process are further removed by stripping with dry steam during the deodorizing process. The method according to any one of claims 1 to 5, wherein the vegetable hardened oil is CLA vegetable hardened oil. Vegetable hardening oil for food additives with reduced hardening odor produced using the method of any one of claims 1 to 4. 8. The vegetable hardening oil for food additive according to claim 7, wherein the vegetable hardening oil is CLA vegetable hardening oil. According to claim 7 or 8, wherein the food to be applied to the edible vegetable hardened milk is milk noodle, processed milk, fermented milk, snacks, ice cream products, ice cream, processed chocolate, shortening margarine, confectionery, bakery, frozen food Vegetable hardening oil for food additives, characterized in that it is used in the manufacture of the product.