KR101099938B1 - Method for particles having functional oil by high pressure carbon dioxide and polymer - Google Patents

Abstract

PURPOSE: A powdering method of functional oil using high pressure carbon dioxide and a carrier is provided to secure the functionality of the functional oil. CONSTITUTION: A powdering method of functional oil comprises the following steps: cooling carbon dioxide inflowing from a cylinder(100) into the temperature lower than 0 deg C using a cooler(120) to obtain liquid carbon dioxide; pressurizing the liquid carbon dioxide into high pressure carbon dioxide using a high pressure liquid pump(130); heating the carbon dioxide using a heater(150); inserting the functional oil and an edible carrier into a storage unit of a reactor(180) having a magnetic drive unit(170) in a ratio of 1-20:1; stirring the mixture of the carbon dioxide, the functional oil, and the carrier at 30-60 deg C for more than 30 minutes; and spraying the mixture in a separation tank(200), and obtaining particles.

Description

Method for powdering functional oil using high pressure carbon dioxide and carrier {Method for particles having functional oil by high pressure carbon dioxide and polymer}

The present invention relates to a method of powdering functional oils, and more particularly, to coating or collecting functional oils on a edible carrier using high pressure carbon dioxide as a solvent capable of dissolving the functional oils, for various industries such as food and cosmetics. It is about how to make it available to the field.

Functional oils used in health foods, such as DHA [docosahexaenoic acid], EPA [eicosapentaenoic acid], linolenic acid, linoleic acid, gamma linolenic acid, herbal extract functional oils, and other animal / plant-derived functional oils are high in carbon and high in unsaturated. Easily oxidized and the quality is lowered, there is a problem that makes it difficult to use. In addition, since it exists in a liquid state or a semi-solid state at room temperature and atmospheric pressure, industrial applicability is limited.

DHA and EPA among animal and plant-derived functional oils can improve the triglyceride in the blood and improve blood circulation when the daily intake is over 500mg, and gamma linolenic acid improves cholesterol, improves blood circulation, and other antioxidants. Immunity enhancement and endurance enhancement functionalities are disclosed in Korean Food and Drug Administration's Decree No. 2009-153.

In general, the technique of powdering functional oils in the food industry has been reported to be a spraying process, a coating process, an extrusion process, etc., but the spray drying method is known as the most economical commercialization process. Risch SJ. 1993, Encapsulation, ACS symposium series No 590. American Chemical Society, Washington DC, USA, pp. 2-7). However, since the drying temperature is dried at a relatively high temperature in the 130-300 ℃ range, there is a problem in that there is a possibility of the denaturation of the functional oil, acid dust, the production of trans fat.

On the other hand, high pressure carbon dioxide, which dissolves the functional oil and collects or coats it on the carrier, has a low critical pressure and a low critical temperature, which is relatively easy to use in the powdering process, is harmless to the human body, and manufactures powder particles. The separation and recovery of the solvent is easy (Yoon-Woo Lee, "Manufacturing Particles Using Supercritical Fluids" Hwahak konghak, vol. 41. No. 6, 679-688 (2003)).

The particle generation from gas saturated solutions (PGSS) applied in the present invention has been proposed by Weidner and Knez (EP744992, WO9521688), and the mixture formed after dissolving the high-pressure carbon dioxide and the functional material in the polymer carrier in the reactor is low. It is a process of manufacturing particle | grains by spraying in a separation tank equipped with a filter with pressure.

Therefore, the present invention is to powder the functional oil using an edible carrier and high pressure carbon dioxide so that the functional oil can be applied to various industrial fields while maintaining its functionality. In addition, another object of the present invention is to improve the oxidation stability of the functional oil powder and to control the size of the powder particles required in the field of application by controlling the temperature and pressure of the carbon dioxide to manufacture.

In order to achieve the above object, the apparatus used in the present invention comprises: a cooler which cools carbon dioxide introduced from a cylinder to 0 ° C. or less and changes the phase into a liquid phase; A high pressure liquid pump which receives the carbon dioxide and pressurizes it to a high pressure state; A reactor capable of being sealed and equipped with a stirring magnetic drive device (mgnetic drive) to put functional oil, an edible carrier and a high pressure carbon dioxide into an inner accommodating part, and to heat the mixture for 30 minutes or more to make a mixture of the functional oil and the carrier; The mixture is sprayed into a low pressure separation tank to separate carbon dioxide and functional particles and consists of a separation tank equipped with a filter for filtering the resulting particles. The method for producing the functional particles with the configured device consists of the following four steps.

1) mixing the functional oil with an edible carrier and injecting the reactor;

2) injecting carbon dioxide, a solvent which dissolves the functional oil to be collected and coated on the carrier, at high pressure (70 to 300 bar) in the reactor;

3) making a mixture of the functional oil and the carrier by heating (30-60 ° C.) with stirring for 30 minutes or more so that the high-pressure carbon dioxide and the functional oil and the edible carrier are completely mixed;

And 4) separating the carbon dioxide and the generated functional particles by spraying the separation tank.

As described above, when the particles are manufactured according to the present invention, the particle size can be controlled while maintaining the functionality of the functional oil, and the particles having excellent oxidation stability can be obtained, and thus can be actively used in various industrial fields as a health functional material. . In addition, palatability and applicability can be greatly improved, and carbon dioxide, a solvent used, can be recovered at least 95%, which is economical and environmentally friendly.

1 is a block diagram of a granulation apparatus used in the present invention.
2 is a flowchart of a method for producing particles of functional oil according to the present invention.
Figure 3 shows the results of FT-IR analysis of β-CD, DHA, EPA and the resulting particles
Figure 4 shows the results of the FT-IR analysis using γ-CD, chitosan, DHA and EPA
Figure 5 shows the results of the FT-IR analysis using starch, DHA and EPA
Figure 6 shows the results of the FT-IR analysis using β-CD, purslane extract
7 shows the results of observing β-CD and the produced particles by SEM.
8 is a graph of the equation obtained according to the response surface analysis
※ Explanation of code for main part of drawing
100: CO ₂ cylinder 110: ball valve
120: cooler 130: high pressure liquid pump
140: check valve (for preventing backflow) 150: heating means
160: pressure gauge 170: magnetic drive device for stirring
180: reactor 190: needle valve for injection
200: primary separation tank 210: filter
220: ball valve 230: secondary separation tank

Hereinafter, looking at each preferred embodiment according to the present invention. In the drawings, the same components or parts are to be noted with the same reference numerals as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

1 is a block diagram of a particle generating device according to the present invention, Figure 2 is a flow chart of the method for producing particles of the functional oil according to the present invention.

The present invention provides particles having DHA, EPA, beta carotene, Linoleic acid, Linolenic acid, known as functional oils, coated or adsorbed on edible carriers for oxidative stability and various industrial applications.

Thus, as shown in FIG. 1, the cylinder 100 including carbon dioxide and a cooler 120 for cooling the carbon dioxide flowing from the cylinder 100 to 0 ° C. or lower to change into a liquid phase are provided. The high-pressure liquid pump 130 is connected to the high-pressure liquid pump 130 to receive and pressurize the liquid carbon dioxide by the cooler 120 to make a high-pressure state. Supply to 180. At this time, the internal pressure of the reactor to configure a pressure of 70 to 300 bar.

The reactor 180 can be sealed and can withstand high pressure, and is equipped with a heating means 150 and a magnetic drive device 170 for stirring.

On the other hand, the receiving portion of the reactor 180 to be configured with a functional oil and an edible carrier in advance. The functional oil is made by using only one of DHA, EPA, beta carotene, Linoleic acid, Linolenic acid or by mixing two or more oils. The DHA, EPA is usually extracted from fish, seals, etc., but also includes plant-derived DHA, EPA. In addition, the edible carrier may be one of betacyclodextrin, gammacyclodextrin, chitosan, starch, or a mixture of two or more carriers. In addition, the mixing weight ratio of the edible carrier and the functional oil contained in the reactor 180 is preferably 1: 1 to 20: 1.

The high pressure carbon dioxide and the functional oil, and the edible carrier, are heated at 30 ° C. to 60 ° C. in the reactor 180 accommodating part and stirred at 100 to 1000 rpm for 30 minutes or more. After stirring, the high pressure carbon dioxide and the functional oil, and an edible carrier are injected into the separation tank 200 at a low pressure to separate carbon dioxide and the functional particles, and the separation tank 200 equipped with a filter 210 for filtering the generated particles. Recover particles from This produces particles that contain functional oils.

An embodiment of the present invention having the characteristics as described above will be described in more detail below.

① Reagent

DHA and EPA were purchased from AK Biotech Co., Ltd. with more than 70% purity and stored for freezing. Herb extracts containing beta-carotene, Linoleic acid, and Linolenic acid were used in 50 ℃, An extract extracted with 300 bar supercritical carbon dioxide was used. Betacyclodextrin and gammacyclodextrin were used as pharmacological samples of WACKER (USA), and chitosan was used by purchasing medium molecular weight of Sigma. Starch was purchased from Deoksan Chemical and all other experimental materials were purchased from the special reagent.

② Check for collection or coating

The prepared particles were analyzed using Nicolet (USA) MAGNA-IR 560 FT-IR Spectrometer to confirm the collection or coating of the functional oil. Scan range 400-4000 cm ^-1 .

③ distribution of particles

In order to confirm the distribution of the produced particles, the analysis was performed using a LS 13320 Laser Diffraction Partical Size Analyzer manufactured by BECKMAN COULTER (USA). The analysis range was 0.4-2000 micrometers.

④ Crude fat analysis

In order to measure the crude fat content of the produced particles, it was analyzed using a Bhi-811 crude fat extractor manufactured by Bhi (Switzerland). The instrument is equipped with three automatic extraction processes, extraction, washing and drying, and can process four samples simultaneously. The solvent used was an ether special reagent.

⑤ Fatty acid analysis

Fatty acid was analyzed using the crude fat extractor from the resulting particles. The extracted oil was analyzed by GC-FID (Hewlett Packard 5890) after methylation according to AOAC method. In the pretreatment method, 0.05 g of the extract was weighed into a round flask equipped with a reflux condenser, and 3 ml of 0.5 N NaOH in methanol was added thereto, followed by bathing at 75 for 30 minutes. After the bath was cooled for 10 minutes, 3 ml of BF ₃ in methanol (Supelcotm) was added thereto, followed by bathing at 75 for 25 minutes and cooling for 10 minutes. After cooling, 3 ml of hexane and 1 ml of 10% NaCl solution were added, followed by shaking for 30 seconds. Fatty acid composition analyzed by GC-FID was quantified compared to the peak of the standard (FAME MIX., DHA, EPA standard).

 Instrument Hewlett packard 5890 Column FUSED SILICA Capilary Column-SP ^TM -2560
(100m film thickness, Supelco) Carrier gas He 1ml / min Split ratio 10: 1 Detector (FID) Temperature 250 ℃ Injector Temperature 200 ℃ Oven temperature profile 130 ° C., hold 3 min; increase 4 ℃ / min to 240 ℃,
hold 10min

Table 1 shows gas chromathography analysis conditions in fatty acid analysis.

⑥ Particle microstructure

The microstructure of the particles was observed using a scanning electron microscope (HITACHI S-2400, Japan).

⑦ Evaluation of storage stability of particles

The acid value was selected as an indicator for the denaturation of the functional oil coated and collected on the particles. The acid value (AV) was measured according to the General Test Method and the Chemical Test Method of the Food Code.

⑧ Statistical Analysis

Experiments on particle manufacturing conditions were carried out by setting up the experimental range for the extraction factor (X ₁ ) and extraction pressure (X ₂ ), which are considered as independent variables (Xi) important for the process by carrying out a central synthesis plan. The code was encoded in stages, and the experiment was set to 10 spheres according to the central synthesis plan. In addition, the dependent variable (Yn) affected by these independent variables, that is, crude fat content (Y ₁ ), particle size (Y ₂ ), and the like were measured and used in the regression analysis. Regression prediction was performed by using SAS (statistical analysis system) program to predict the optimal condition as Yn value according to the carbon dioxide temperature and pressure.

Extraction condition -2 -One 0 One 2 X ₁ Temperature 30 37.5 45 52.5 60 X ₂ Pressure (bar) 100 150 200 250 300

Look at the results above.

① Recovery rate

Sample T (℃) P (bar) Oil recovery (%) B-cd + DHA / EPA-1 30 200 16.1 B-cd + DHA / EPA-2 37.5 150 28.3 B-cd + DHA / EPA-3 37.5 250 42.0 B-cd + DHA / EPA-4 45 300 51.7 B-cd + DHA / EPA-5 45 200 49.3 B-cd + DHA / EPA-6 45 200 55.0 B-cd + DHA / EPA-7 45 100 66.0 B-cd + DHA / EPA-8 52.5 150 63.4 B-cd + DHA / EPA-9 52.5 250 62.1 B-cd + DHA / EPA-10 60 200 63.0 r-cd + DHA / EPA 45 200 53.7 Chitosan + DHA / EPA 45 200 59.5 Starch + DHA / EPA 45 200 51.8 B-cd + purslane extract 45 200 70.7

Table 3 is the reaction conditions of different conditions, and shows the functional oil recovery of the particles prepared therein. The amount of particles produced in the total 26 g of the carrier and the functional oil entering the reactor under each condition was 20 g ± 1 g, which was almost the same considering the loss in recovering the particles from the reactor. However, the functional oil recovery showed a significant difference for each condition, and the recovery rate shown in Table 3 refers to the amount of oil coated and collected on the particles in the total 6 g of the functional oil entering the reactor.

② Check FT-IR of particles

FT-IR analysis of the particles was performed to confirm coating and collection of the functional oil. As shown in FIGS. 3, 4, 5, and 6, the peaks of 2900 cm ⁻¹ and 1700 cm which were not observed in food carriers such as betacyclodextrin, gammacyclodextrin, chitosan, and starch in the IR spectrum were observed in DHA and EPA. ^-1 peak was observed in the produced particles. In addition, peaks that were not seen in betacyclodextrin but only in purslane extract were observed in the produced particles. This feature is judged as a result showing that the functional oil is coated or collected on the food carrier.

③ Check the distribution of particles

Sample T (℃) P (bar) Mean of Particle Size (㎛) B-cd 122.20 B-cd + DHA / EPA-1 30 200 45.67 B-cd + DHA / EPA-2 37.5 150 25.91 B-cd + DHA / EPA-3 37.5 250 50.14 B-cd + DHA / EPA-4 45 300 37.06 B-cd + DHA / EPA-5 45 200 29.03 B-cd + DHA / EPA-6 45 200 15.95 B-cd + DHA / EPA-7 45 100 40.31 B-cd + DHA / EPA-8 52.5 150 41.39 B-cd + DHA / EPA-9 52.5 250 21.95 B-cd + DHA / EPA-10 60 200 37.01 r-cd 48.04 r-cd + DHA / EPA 45 200 21.52 Chitosan 196.00 Chitosan + DHA / EPA 45 200 375.60 Starch 44.46 Starch + DHA / EPA 45 200 43.77 B-cd + purslane extract 45 200 261.00

As shown in Table 4, as a result of particle distribution analysis, betacyclodextrin was found to have a different particle average distribution according to the temperature and pressure of each carbon dioxide, and the size was reduced 3 to 9 times after the reaction by adding DHA and EPA. However, the reaction resulted from the addition of purslane extract, which resulted in larger particles. In the case of gammacyclodextrin, the particle size was reduced by about 2 times, but in starch, the particle size was almost the same, and chitosan was increased.

④ Crude fat content analysis

sample T (℃) P (bar) Crude Fat (%) B-cd + DHA / EPA-1 30 200 4.35 B-cd + DHA / EPA-2 37.5 150 7.65 B-cd + DHA / EPA-3 37.5 250 11.35 B-cd + DHA / EPA-4 45 300 13.97 B-cd + DHA / EPA-5 45 200 13.31 B-cd + DHA / EPA-6 45 200 14.86 B-cd + DHA / EPA-7 45 100 17.83 B-cd + DHA / EPA-8 52.5 150 17.11 B-cd + DHA / EPA-9 52.5 250 16.77 B-cd + DHA / EPA-10 60 200 17.00 r-cd + DHA / EPA 45 200 14.50 Chitosan + DHA / EPA 45 200 16.06 Starch + DHA / EPA 45 200 13.99 B-cd + purslane extract 45 200 19.36

The results of analyzing the crude fat content of the produced particles are shown in Table 5. In the purified and degreased carrier, the crude fat content was different according to the functional oil type and carbon dioxide reaction conditions.

⑤ Fatty acid analysis

Composition Content (%) β-CD +
DHA / EPA Chitosan +
DHA / EPA γ-CD +
DHA / EPA Starch +
DHA / EPA Palmitic acid 0.9 1.1 0.7 1.1 Stearic acid 3.7 5.3 3.3 4.0 Oleic acid 7.3 9.6 5.6 6.1 Elaidic acid 2.9 3.8 2.2 2.4 Linoleic acid 0.8 0.8 0.5 0.5 Archidic acid 1.4 1.9 1.2 1.4 cis-11-Eicosenoic acid 2.8 4.0 2.3 2.5 r-Linolenic acid 0.9 1.2 0.7 0.8 Linolenic acid 0.8 0.9 0.7 0.7 cis-11, 14-Eicosadienoic acid 0.4 0.6 0.4 2.5 Behenic acid 1.0 1.3 0.9 1.0 cis-8, 11, 14-Eicosatrienoic acid 1.8 2.4 1.6 1.6 Erucic acid 0.7 0.8 0.6 0.5 cis-11, 14, 17-Eixosatrienoic acid 0.3 0.3 0.3 0.3 Arachidonic acid 0.2 0.3 0.2 0.2 Tricasanoic acid 2.7 2.6 2.6 2.6 Lignoceric acid 0.3 0.9 0.6 0.7 cis-13, 16-Docosadienoic acid 2.0 1.5 1.4 1.4 EPA 36.9 33.1 37.9 36.3 Nervonic acid 1.8 2.6 1.6 1.7 DHA 30.6 25.1 34.5 31.9 Sum 100.0 100.0 100.0 100.0

Fatty acid analysis showed that the functional oils, DHA and EPA, were 67.5%, 58.1%, 72.4%, and 68.1% for each carrier, and gamma cyclodextrin had the highest coating or capture rate.

⑥ Particle microstructure

FIG. 7 shows the results of SEM analysis of the carrier betacyclotextrin and the results of SEM analysis of betacyclodextrin including DHA and EPA at 40 ° C. and 100 bar. In both samples, the shape of the particles was not significantly different, but the size of the particles showed a big difference.

⑦ Storage stability

division Experiment elapsed date start date 8 days later 16 days later In 23 days 31st DHA, EPA Raw Material 35 ℃ 0.45 0.51 0.56 0.58 0.61 60 ℃ 0.45 0.56 0.59 0.72 0.76 particle 35 ℃ 0.49 0.51 0.53 0.56 0.56 60 ℃ 0.49 0.52 0.54 0.60 0.62

70% DHA, EPA ester raw materials used in the experiment and particles prepared at 45 ℃ and 100 bar conditions were stored in a glass bottle for 35 days at 35, 60 ℃ and the results of the acid value change is shown in Table 7 Indicated. Compared with DHA and EPA raw materials, the acid value of the prepared particles is less changed with time, and functional oils are trapped in the carrier, thus increasing storage stability. The initial acid value analysis start date indicates that the high acid value of the particles is due to contact with air when DHA and EPA are added during the particle manufacturing process.

⑧ Statistical analysis-establishment of optimal conditions

In order to set the optimum conditions for producing the functional particles, the recovery rate of the functional oils obtained under the conditions of 10 holes designed by the central synthesis plan using the extraction temperature and the extraction pressure as independent variables is shown in Table 3 above. Response surface regression was performed using each result, and a regression equation for the dependent variable (recovery rate) was obtained as shown in Table 8. The response surface graph is shown in FIG. 8. As can be seen from the obtained regression equation and graph, high temperature and low pressure increase the functional oil recovery rate, but when the pressure of carbon dioxide decreases below the critical point, the solubility in the functional oil is drastically reduced, and thus the ability to coat and capture the carrier is reduced. When the temperature is high, the optimum condition was determined at 60 ° C. and 74 bar in consideration of the modification of the functional oil.

Response Second order Polynominals R ² Recovery (%) Y _recovery = 188.128571 + 8.498413X ₁ + 0.135286X ₂ -0.053810X ₁ ² -0.01X ₁ X ₂ + 0.000719X ₂ ² 0.9377

Claims (2)

The high pressure to cool the carbon dioxide flowing from the cylinder 100 containing the carbon dioxide to 0 ℃ or less to change the phase to a liquid phase, the liquid carbon dioxide by the cooler 120 to be pressurized to make a high pressure state Reactor 180 equipped with a liquid pump 130, a heating means 150 for preheating the low temperature carbon dioxide through heat exchange in a high pressure state, can be sealed and withstand high pressure, and equipped with a magnetic drive device for stirring 170. A functional oil and an edible carrier are formed in advance in the receiving portion of the reactor 180 using a high pressure carbon dioxide and a functional oil, and the edible carrier is stirred at the reactor 180 receiving portion for at least 30 minutes, and then a low pressure separation tank is used. It is sprayed to 200 to separate the carbon dioxide and the functional particles, and to recover the particles in the separation tank 200 equipped with a filter 210 for filtering the generated particles. Method for generating particles with the functionality for oil and food carrier as ranging. The method of claim 1,
The functional oil may be made of only one of DHA, EPA, beta-carotene, Linoleic acid, Linolenic acid, or a mixture of two or more oils, and the edible carrier may be one of betacyclodextrin, gammacyclodextrin, chitosan, and starch. Mixing two or more carriers to be used, the mixing weight ratio of the edible carrier and functional oil contained in the reactor 180 is 1: 1 to 20: 1 so that carbon dioxide and functional oil, edible at 70 to 300 bar pressure The carrier is heated to 30 ° C. to 60 ° C. in the reactor 180 accommodating part, stirred at 100 to 1000 rpm for 30 minutes or more, and then sprayed the carbon dioxide, the functional oil, and the edible carrier to a low pressure separation tank 200. Particle production method using a functional oil and a carrier for food, characterized in that the particles are recovered.

Images