KR101394644B1 - Method for Preparing Low Bound 3-MCPD Edible Oil - Google Patents

Abstract

The present invention relates to a method for producing an edible oil having reduced bound-3-MCPD (bound-3-monochloropropane-1,2-diol) in edible oil, and more particularly, The present invention relates to a method for producing edible oil by reducing the content of diacylglycerol (DG) to 0.5% or less to reduce the binding type 3-MCPD to 0.5 ppm or less.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for preparing edible oil with reduced binding 3-MCPD (Method for Preparing Low Bound 3-MCPD Edible Oil)

The present invention relates to a method for producing an edible oil having reduced bound-3-MCPD (bound-3-monochloropropane-1,2-diol) in edible oil, and more particularly, The present invention relates to a method for producing edible oil by reducing the content of diacylglycerol (DG) to 0.5% or less to reduce the binding type 3-MCPD to 0.5 ppm or less. At this time, the method of refining the edible oil is changed from the conventional milking → fumigation → deoxidation → discoloration → deodorization process → milking → defection → discoloration → thin film distillation deoxidation → deodorization process.

Free-3-monochloropropane-1,2-diol (MCPD) has been identified as a risk carcinogen, which was detected in 1996 in acid-digested liver. Free-form-3-MCPD is produced when chlorine in hydrochloric acid is combined with glycerol in the process of decomposition of residual oil in defatted soybean into glycerol and fatty acid by hydrochloric acid at high temperature.

Binding-3-MCPD is a form in which free fatty acids are attached to free-3-MCPD (Fig. 1). Although the risk of combined-type 3-MCPD has not yet been scientifically proven, it is suggested that the combined type 3-MCPD may be converted to free-3-MCPD in the process of digestion and absorption in the human body, The risk of the combined type 3-MCPD is continuously monitored in the European Food and Drug Administration as well as in Europe. Binding-3-MCPD is detected in some edible oils that undergo refining at high temperatures (Ref. 1). The refining process of edible fats generally proceeds to the harvesting, milking, de-fining, deoxidation, decolorization and deodorization processes of the oil seeds. In this dehydration process, most of the bound-type 3-MCPD is produced, which is attributed to the high temperature. In this case, diacylglycerol and chlorine (Fig. 2, Reference 2). In particular, the content of bound-3-MCPD is highly correlated with the concentration of diacylglycerol (FIG. 3). Diacylglycerol in edible oil is produced by decomposing triacylglycerol into diacylglycerol by lipase present in the seed cell until milking after oil seed harvesting (Fig. 4) . Therefore, inhibition and elimination of diacylglycerol production in edible oils can be considered as an effective method for inhibiting the production of bound 3-MCPD in the final purified edible oil. Edible oil is used as a heating medium for cooking or as a seasoning or fragrance, rather than directly ingested like other foods. In particular, food processing companies use edible oil for drying and cooking purposes. Therefore, not only the stability of edible oils but also safety issues are very important in food processing industry.

Therefore, edible oil with reduced binding-3-MCPD is considered to be necessary to provide safe food to consumers in view of food processing companies that mass-produce hot-water products and fat-containing foods. It is necessary to develop a technique to reduce the binding-type 3-MCPD that is likely to be designated.

The present invention relates to the development of a coupled 3-MCPD reduction technology suspected of carcinogenic risk in edible oils to ensure the safety of edible oils used for daily cooking.

This is due to the fact that diacylglycerol, which is a causative substance of bound 3-MCPD contained in edible oil during the purification process, is removed by thin-film distillation to minimize the production of bound type 3-MCPD in the edible oil do.

One aspect of the present invention provides a method for producing an edible oil with bound-3-monochloropropane-1,2-diol (MB-3-monochloropropane-1,2-diol) reduced in milking, deodorizing, decoloring, thin film distillation and deodorization steps .

At this time, the conditions of the thin film distillation may be a pressure of 0.001 mbar to 0.05 mbar, a temperature of 230 to 300 ° C, and a feed rate of 100 to 700 rpm.

The content of diacylglyrol in the thin film distilled edible oil may be 0.5% or less.

In addition, the content of bound-3-monochloropropane-1,2-diol in edible fats with reduced bound-3-MCPD (bound-3-monochloropropane-1,2-diol) ppm.

The present invention utilizes thin film distillation to effectively remove diacylglycerol, which is a substance causing binding 3-MCPD present in edible fats, at a temperature of 230 to 300 ° C, a pressure of 0.001 to 0.05 mbar, The infusion rate includes about 100 to 700 rpm. The diacylglycerol content of the bound type 3-MCPD is 0.5% or less and the content of the bound type 3-MCPD is 0.5 ppm or less. .

The above-mentioned diacylglycerol, which is a substance causing the binding 3-MCPD in the native plant-derived oil, is usually present in less than 10%.

In addition, diacylglycerol significantly increases the content of bound 3-MCPD in proportion to the content of diacylglycerol in the high-temperature deodorization process during the cooking oil refining process (FIG. 3).

Therefore, in the present invention, diacylglycerol (diacylglycerol), which is a causative substance of bound type 3-MCPD, is removed efficiently by thin film distillation to a degree of 0.5% or less, and deodorization is performed to remove the edible oil Can be manufactured.

The thin-film distillation method utilizes the difference in boiling point according to the molecular weight. After the thin film is formed into a uniform thin film at vacuum and high temperature, the free fatty acid and diacylglycerol having a relatively small molecular weight are vaporized and separated Method.

Such a thin film distillation method can use a commonly used thin film still. The thin film still is provided with a rotating wiper in the cylindrical heat transfer passage with a heating jacket, and the oil is supplied from the upper portion of the heat transfer cylinder and distributed in the circumferential direction by a distributor installed on the upper portion of the rotor blades , And is stirred by the rotor blades, and flows through the heat transfer walls while forming a uniform and stable liquid film by the operation of flowing the oil by the rams. In the meantime, free fatty acids in the fat and substances having a relatively small molecular weight such as diacylglycerol are heated and vaporized by a jacket heating source, and they are separated and removed by condensation.

The refined fat may be natural vegetable oils, such as, but not limited to, palm oil, palm olein oil, palm kernel oil, rice bran oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, processed oil or a combination thereof.

Thin-film distillation can effectively remove diacylglycerol, which is a causative substance of bound 3-MCPD, and reduce binding-type 3-MCPD to 0.5 ppm or less even if it is subjected to a deodorization process in which high temperature is applied during the holding and refining process .

Figure 1 is a structural formula of free 3-MCPD and coupled 3-MCPD.
Figure 2 shows the mechanism of production of bound 3-MCPD in edible oil.
Figure 3 shows the correlation of the production of bound 3-MCPD by DG content.
Figure 4 shows the hydrolysis process of triacylglycerol in edible oil by lipase.
5 compares the maintenance and purification processes according to the conventional (a) and the present invention (b).
FIG. 6 is a graph showing a result of calculating a function satisfying a content of diacylglycerol of 0.5% or less according to a temperature and a holding inflow rate at a pressure of 0.001 mbar.
FIG. 7 is a graph showing a result of calculating a function satisfying a content of diacylglycerol of 0.5% or less according to a temperature and a holding flow rate at a pressure of 0.05 mbar.

The present invention relates to a process for the purification of a natural plant-derived fat containing less than 10% of diacylglycerol. In the present invention, thin-film distillation is used to purify diacylglycerol the present invention relates to a method for efficiently removing diacylglycerol.

In detail, the present invention relates to a purification method of removing a free fatty acid, diacylglycerol, contained in a fat by using a thin film distillation before the deodorization process, in an amount of not more than 0.5%, and then deodorizing the product.

[Experimental Example 1]

Experimental examples were carried out under the conditions of thin film distillation at a temperature of 190 to 300 DEG C, a pressure of 0.001 to 0.05 mbar, and a feed rate of 100 to 700 rpm. The removal of diacylglycerol from Experimental Example 1 was carried out as shown in Table 1 using the minitab program, and the results are shown in Table 2.

Experimental design of thin film distillation for reduction of diacylglycerol Temperature (° C) Inflow rate (rpm) Comparative Example - - Example 1 190 100 Example 2 300 100 Example 3 190 700 Example 4 300 700 Example 5 230 400 Example 6 260 400 Example 7 245 300 Example 8 245 500 Example 9 245 400 Example 10 245 400 Example 11 245 400 Example 12 245 400 Example 13 245 400

DG (%): Diacylglycerol (%)

DG (%) _ 0.001 mbar DG (%) _ 0.05 mbar Comparative Example 10 10 Example 1 3.20 6.20 Example 2 0.01 0.15 Example 3 8.50 9.50 Example 4 0.35 1.80 Example 5 0.62 0.75 Example 6 0.10 1.50 Example 7 0.25 0.55 Example 8 1.72 0.98 Example 9 0.42 0.62 Example 10 0.45 0.66 Example 11 0.50 0.60 Example 12 0.44 0.58 Example 13 0.52 0.62

According to Table 2, diacylglycerol is significantly influenced by temperature, pressure, and inflow rate during thin film distillation (p-value <0.05). Experiments were carried out at 0.001 mbar or 0.05 mbar, respectively. Diacylglycerol showed a significant effect on temperature and inflow rate at each pressure condition (p value <0.05).

The function satisfying 0.5% or less of diacylglycerol content at a temperature of 0.001 mbar and a holding inflow rate under the pressure of the Minitab program was obtained. The result is shown in FIG. According to FIG. 6, the diacylglycerol in the thin film distillation process during the refining process of the oil at the pressure of 0.001 mbar is effectively removed as the temperature is higher and the inflow rate is slower. When the temperature of the thin film is high and the inflow rate of the substrate is low, the retention time of the retention in the high temperature thin film is increased, so that the diacylglycerol having a larger molecular weight than the free fatty acid is effectively volatilized and diacylglycerol, Can be removed. Table 3 shows the processing conditions satisfying 0.5% or less of diacylglycerol in the conditions of FIG.

The maintenance inflow rate range according to the constant temperature condition at the pressure of 0.001 mbar Temperature (℃) Maintenance inflow rate (rpm) Less than 230 No conditions to satisfy 230 Below 100 250 190 or less 260 300 or less 270 Below 500 300 700 or less

In addition, a function satisfying a content of diacylglycerol of 0.5% or less according to the temperature and the maintenance inflow rate under a pressure of 0.05 mbar through the Minitab program was obtained. The result is shown in FIG. Diacylglycerol in the thin film distillation process during the refining process of the oil is more effectively removed as the temperature is higher and the holding inflow rate is lower. Table 4 shows the processing conditions satisfying 0.5% or less of diacylglycerol in the conditions of FIG.

Holding inflow rate range according to constant temperature condition at pressure 0.05 mbar Temperature (℃) Maintenance inflow rate (rpm) Less than 250 No conditions to satisfy 250 Below 100 260 200 or less 270 400 or less 290 700 or less 300 700 or less

[Experimental Example 2] Production of bound 3-MCPD according to deodorization temperature

The content of 3-MCPD was determined by the deodorization temperature of the diacylglycerol (diacylglycerol) content of 0.5% or less through the thin film distillation. Typically, when the content of diacylglycerol is 1.0%, the amount of bound 3-MCPD is significantly increased as the deodorization temperature is increased (Reference 3).

The content of diacylglycerol (0 ~ 0.5%) according to deodorization temperature was analyzed for the content of bound 3-MCPD in the oil after the thin film distillation process. In addition, acid value, water content (%) and color value (lovibond R) (5.25 ") were measured according to the standard specification of refined edible oil to evaluate whether it was suitable for refined edible oil.

At this time, the bound 3-MCPD assay was analyzed using GC / MS using the DGF standard method (09) (Reference 4). 100 mg of the fat was dissolved in 0.5 ml of a mixture of tBME and ethyl acetate (tBME: ethyl acetate = 8: 2), and then 100 ul of the internal standard substance (3-MCPD-d ₅ ) Add 1 ml of sodium methoxide and allow to stand at room temperature for 10 minutes. Add 3 ml of hexane, 3 ml of a mixture of acetic acid and 20% sodium chloride (acetic acid: 20% NaCl = 1: 30), stir well and remove the organic solvent layer as the upper layer. 3 ml of hexane is added again to remove the organic solvent layer. Phenylbromonic acid (PBA), a derivatization reagent, is added to the water layer and derivatised at 80 ° C for 20 minutes. Add 3 ml of hexane and stir well and analyze by GC / MS.

Changes in the content of bound 3-MCPD in edible oils by deodorizing temperature Deodorization temperature Bound-3-MCPD (ppm) Acid value (%) moisture(%) Lovibond R (5.25 ") Comparative Example Refined palm oil 0.5 to 13 0.1 or less 0.011 3.0 Example 1 240 0.15 0.1 or less 0.012 2.9 Example 2 250 0.21 0.1 or less 0.011 2.8 Example 3 260 0.24 0.1 or less 0.013 2.7 Example 4 270 0.48 0.1 or less 0.011 2.5

* Binding type 3-MCPD content of refined palm oil (Reference 5)

* Refined palm oil in refined cooking oil Specification: acid value 0.1 or less, water content 0.1% or less, chromaticity (Lovibond R; 5.25 ") 3 or less (Reference 6)

In the case of the thin-film distillate containing 0 to 0.5% of diacylglycerol, the production of bound 3-MCPD was measured to be 0.5 ppm or less while increasing the maximum deodorization temperature to 270 ° C., No significant increase in binding 3-MCPD was observed.

Reference 1: Fatty acid esters of 3-MCPD: Overview of occurrence and exposure estimates, Rudiger WeiBhaar, Eur. J. Lipid Sci. Technol. 2011, 113, 304-308

Reference 2: What do we know about the molecular mechanism of 3-MCPD ester formation ?, Anja Katerina Karin Rahn and Varoujan Antranik Yaylana, Eur. J. Lipid Sci. Technol. 2011, 113, 323-329

References 3: Strategies for the reduction of 3-MCPD esters and related compounds in vegetable oils, Bertrand Matthaus, Frank Pudel, Peer Fehling, Klaus Vosmann and Anne Freudenstein, Eur. J. Lipid Sci. Technol. 2011, 113, 380-386

Reference 4: Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and glycidol esters, Deutsche Gesellschaft fur Fettwissenschaft e.V. (DGF), C-III 18 (09)

Reference 5: Fatty acid esters of glycidol in refined fats and oils, Rudiger WeiBhaar and Roland Perz, Eur. J. Lipid Sci. Technol. 2010, 112, 158-165

Reference 6: Quality Control Laboratories in Refineries. Er K L, Proceedings of Workshop on Quality in the Palm Oil Industry. August 2-3 1985. Kuala Lumpur. 203-208

Claims (4)

Milking, deodorizing, discoloring, thin-film distillation and deodorization steps,
Wherein the content of bound-3-monochloropropane-1,2-diol in which the content of diacylglyrol in the thin-film distilled edible oil is not more than 0.5% is reduced. The method according to claim 1,
The thin film distillation was carried out under the conditions of a pressure of 0.001 mbar to 0.05 mbar, a temperature of 230 to 300 ° C, and a feeding rate of 100 to 700 rpm. The bound type 3-MCPD (bound-3-monochloropropane-1,2-diol) &Lt; / RTI &gt; delete The method of claim 1,
The content of bound-3-MCPD (bound-3-monochloropropane-1,2-diol) in edible oils with reduced bound-3-MCPD (bound-3-monochloropropane-1,2-diol) Wherein the bound-3-monochloropropane-1,2-diol (MCPD) is reduced.

Images