KR101833932B1 - Adsorption filter for refining extra virgin oil by adsorbing selectively sour components contained in extra virgin oil and the method of refining using the same - Google Patents

Abstract

The present invention relates to an adsorption filter for refining an extra virgin olive oil by selectively adsorbing rancidity factors contained in the extra virgin olive oil and a refining method using the adsorption filter. The adsorption filter of the present invention comprises: a body which has an accommodation space and includes an upper opening and a lower opening; an adsorption layer which is located in the accommodation space of the body to selectively adsorb the rancidity factors contained in the extra virgin olive oil, and includes modified porous silica gel particles having a hydroxyl group and an amine group introduced thereto and modified porous sepiolite particles having the hydroxyl group introduced thereto at a weight ratio of 1:10 to 5:1; and a pair of olive oil permeable supports which are each located on the top surface and the bottom surface of the adsorption layer and support and fix the adsorption layer to the accommodation space of the body. The adsorption filter according to the present invention is useful in refining the extra virgin olive oil containing the rancidity factors into an extra virgin olive oil with improved rancidity stability by selectively adsorbing the rancidity factors contained in the extra virgin olive oil such as free fatty acids, peroxides, pigment factors, and the like with little effect on amounts of useful components contained in the extra virgin olive oil.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorption filter for selectively adsorbing and refining acidic factors contained in extra virgin olive oil, and a purification method using the same. BACKGROUND ART [0002]

TECHNICAL FIELD The present invention relates to an adsorption filter for selectively adsorbing and purifying a rancidity factor contained in extra virgin olive oil and a purification method using the same.

Extra virgin olive oil is a vegetable oil obtained by squeezing olives under conditions that do not cause denaturation without chemical purification. Extra virgin olive oil contains nutrients such as squalene and terpenes and has been reported to exhibit effects such as flavor improvement, antioxidation, blood lipid improvement, and amelioration. In particular, tocopherol and phenolic compounds And it is getting more and more popular.

In the West, extra virgin olive oil is used as a raw seasoning to be applied at room temperature, but it is also used in high temperature cooking such as frying in Korea. Extra virgin olive oil is unstable at high temperatures and can produce toxic substances such as benzopyran, which could act as a carcinogenic ingredient. Therefore, there is a great need to reduce the acidic factors such as free fatty acids, peroxides, and pigment factors contained in extra virgin olive oil in order to improve the high temperature stability without affecting the content of functional components such as tocopherol and phenolic compounds have.

As a method for purifying olive oil, the Sharpe's alkali refining method is well known. The Sharpe's alkali refining method is effective in the general soybean oil process, but is not suitable for the olive oil refining process which contains various nutrients. That is, by refining at a high level of water and alkaline high temperature, various nutrients in olive oil are removed and not only the characteristic of olive oil itself is lost, but also wastewater generated in large quantities after washing is problematic.

Korean Patent Registration No. 10-1498284 discloses a method for producing a polyurethane foam, which comprises: a step of mixing olive oil with 30 to 35% water and stirring to separate the oil from water; mixing the separated oil with an adsorbent and then removing the adsorbent from the oil; And a high-temperature vacuum deodorization step of volatilizing and removing the residual odor component of the oil from which the impurities have been removed. This patented technique is a method in which high-temperature safety is improved by supplementing the conventional edible oil-refining method with lukewarm water instead of alkaline aqueous solution, but still has the above-mentioned problems due to the use of water.

Journal of Food Engineering 65 (2004) 303-309 compared and analyzed the purification effect of extra virgin olive oil impurities using various separating membranes. In this paper, by using extra - virgin olive oil with various pore size membranes such as ultrafiltration and microfiltration, it is possible to greatly reduce the foreign substances contained in the retentate. However, it is difficult to reduce acid factors such as free fatty acids, peroxides, and pigment factors dissolved in extra virgin olive oil only by using these membranes.

Korean Patent No. 10-1498284

Journal of Food Engineering 65 (2004) 303-309

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been made in view of the above technical background, and it is an object of the present invention to provide a process for producing acidulant factors contained in extra virgin olive oil, such as free fatty acids, peroxides and coloring matters without affecting the content of useful components in extra virgin olive oil And an adsorption filter for purification of extra virgin olive oil which can improve stability of rancidity by selective adsorption.

Another object of the present invention is to provide a method for selectively absorbing acidic factors contained in extra virgin olive oil, such as free fatty acids, peroxides, and pigment factors, with little effect on the content of useful components contained in extra virgin olive oil, The present invention provides a method for purifying an extra virgin olive oil.

In order to achieve the above object, an adsorption filter for purifying extra virgin olive oil according to the present invention comprises:

A body having a receiving space, the body having an upper opening and a lower opening;

The modified porous silica gel particles having a hydroxyl group and an amine group introduced therein and the modified porous periolite particles having a hydroxyl group introduced thereinto are adsorbed in an amount of 5: 1 to 1 : ≪ / RTI > 2 by weight; And

And a pair of olive oil-permeable supports positioned on the upper and lower surfaces of the adsorption layer and supporting and fixing the adsorption layer in the accommodation space of the body.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, it is preferable that the modified porous silica gel particles have an average particle diameter of 100 to 200 μm and an average particle diameter of the pores present in the modified porous silica gel particles is 2 to 10 nm desirable.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, the average particle diameter of the modified porous sepiolite particles is 100 to 200 μm, the average particle diameter of the pores present in the modified porous sepiolite particles is 5 to 20 μm, 20 nm. More preferably, the average particle diameter of the pores present in the modified porous sepiolite particles is 1.5 to 3 times larger than the average particle diameter of the pores present in the modified porous silica gel particles.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, it is preferable that the modified porous silica gel particles and the modified porous sepiolite particles are contained in a weight ratio of 3: 1 to 1: 1.

The adsorption filter for purification of extra virgin olive oil according to the present invention is characterized in that it comprises a separation membrane which is located between the upper surface of the adsorption layer and the support, between the lower surface of the adsorption layer and the support, or both, As shown in FIG.

The method for purifying extra virgin olive oil according to the present invention comprises:

(S1) preparing an adsorption filter having the above-described configuration;

(S2) introducing and passing extra virgin olive oil through the adsorption filter to selectively adsorb a rancidity factor contained in extra virgin olive oil; And

(S3) recovering the result of (S2) to the storage tank.

In the method for purifying extra virgin olive oil according to the present invention, it is preferable to further include the step of filtering foreign matters contained in extra virgin olive oil between steps (S1) and (S2) or between steps (S2) and (S3) .

First, the adsorption filter for purification of extra virgin olive of the present invention is characterized in that the modified porous silica gel particles and the modified porous sepiolite particles provided in the adsorption layer have little effect on useful components contained in extra virgin olive oil, It is useful for purifying an extra virgin olive oil with improved rancidity stability by selectively adsorbing the acidic factors contained in extra virgin olive oil such as peroxides and pigment elements.

Second, the process for purifying extra virgin olive oil according to the present invention does not use water and does not discharge wastewater, and a large amount of extra virgin olive oil can be continuously purified, thereby improving productivity and economy.

Third, the purified extra virgin olive oil according to the present invention can reduce the free fatty acid value, the peroxide value and the pigment factor content, thus providing the olive oil with improved reliability and safety to consumers.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given below, serve to further the understanding of the technical idea of the invention. And should not be construed as limiting.
1 is a schematic cross-sectional view of an adsorption filter for purifying extra virgin olive according to a preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

1 is a schematic cross-sectional view of an adsorption filter for purifying extra virgin olive according to a preferred embodiment of the present invention.

Referring to FIG. 1, the adsorption filter for purifying extra virgin olive of the present invention has a body 1 having an accommodation space and an upper opening and a lower opening. The body 1 is generally made of a metal material such as stainless steel, but is not limited thereto.

The adsorption layer (2) is filled and placed in the receiving space of the body (1). The adsorbent layer (2) performs a function of selectively adsorbing a rancidity factor contained in extra virgin olive oil to be purified. That is, the adsorption layer 2 selectively adsorbs sour and lyophilic factors such as free fatty acids, peroxides and pigment elements contained in extra virgin olive oil, while hardly adsorbing useful components contained in extra virgin olive oil such as tocopherol and phenolic compounds Should be removed. For this purpose, the adsorption layer (2) of the present invention simultaneously contains modified porous silica gel particles into which hydroxyl groups and amine groups have been introduced and modified porous particulate particles into which hydroxyl groups have been introduced.

The modified porous silica gel particles contained in the adsorption layer (2) of the present invention are composed of a chemical compound (SiO ₂ ) of silicon and oxygen and are chemically treated with dehydrated porous silica gel particles to form hydroxyl groups And an amine group are introduced. The hydroxyl group and the amine group are functional groups that are friendly to the acidic factors such as free fatty acids, so that the porous silica gel particles more efficiently adsorb the acidic factors.

Such modified porous silica gel particles can be produced by the following method.

First, a silica gel is prepared. Silica gel is a general-purpose adsorbent and is widely used for adsorption and recovery of moisture and solvents.

Then, the hydroxyl group is first introduced into the silica gel in the following manner. The silica gel is added to the sulfuric acid and the hydrogen peroxide solution to prepare a dispersion. At this time, the ratio of sulfuric acid is preferably 2 to 2.5 times that of hydrogen peroxide, and silica gel is added to the prepared mixed solution at a predetermined weight, for example, 2% by weight. When the inorganic particles are not properly dispersed, it is preferable to utilize ultrasonic treatment to improve the dispersibility. The thus-prepared silica gel dispersion is subjected to a reaction in a sealed vessel equipped with a reflux apparatus, for example, at 100 ^° C for 24 hours. The silica particles after completion of the reaction are solidified through a filtration process, and washed with a washing solution while stirring. The washing solution used herein may be water, alcohols, and the like.

Subsequently, the amine group is introduced in the following manner. The silica gel to which the hydroxyl group is introduced by the above-mentioned method is redispersed in a toluene solvent to activate it. The content of the hydroxyl-introduced silica dispersed at this time may be, for example, 2% by weight. 10% by weight of 3-aminopropyltrimethoxysilane was added to the prepared hydroxyl group-introduced silica gel dispersion, and the reaction was carried out at a temperature of 100 ^° C for 24 hours. After the reaction was completed, the dispersion was washed with toluene, n-hexane, and the like, separated using a filter paper, and then dried under a high-temperature vacuum to remove the remaining washing solvent to obtain modified porous silica gel particles having hydroxyl groups and amine groups introduced therein have.

The amine group substitution ratio of the modified porous silica gel particles into which amine groups have been introduced is preferably 40 to 70%.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, the modified porous silica gel particles preferably have an average particle diameter of 10 to 1,000 탆, more preferably 100 to 200 탆, and the modified porous silica gel particles Most preferably, the average pore size of the existing pores is 2 to 10 nm.

On the other hand, the modified porous sepiolite particles contained in the adsorption layer 2 of the present invention can be obtained by chemically treating particles of sepiolite, which is a clay stone called " sepiolite ", and introducing hydroxyl groups into the surface and / it means. Thus, the modified porous periolite particles have hydroxyl groups selectively absorbing the pigment in particular. Such modified porous sepiolite particles can be produced by the following method.

First, porous sepiolite particles are prepared. The chemical composition of sepiolite is Mg ₄ Si ₆ O ₁₅ (OH) ₂ .6H ₂ O. It has fibrous crystals, but is usually observed as an aggregate of minute crystals in clay, has an open channel structure, has an extreme porous crystal form with a specific surface area of 200 to 400 m ² / g and is widely used as an absorbent. After preparing sepiolite particles having a predetermined particle size (for example, 1 to 1000 μm, more preferably 100 to 200 μm), the sepiolite particles are added to an aqueous nitric acid solution to prepare a dispersion. At this time, the nitric acid aqueous solution is preferably diluted to 65% by weight, and for the prepared solution, sepiolite particles are added, for example, 10% by weight. The dispersion and reaction of the sepiolite particles and the washing process are the same as the process of introducing the hydroxyl group of the silica particles described above.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, the average particle diameter of the modified porous sepiolite particles is preferably 10 to 1,000 탆, more preferably 100 to 200 탆, and the modified porous periolite The average particle size of the pores present in the particles is preferably 5 to 20 nm. More preferably, the average particle diameter of the pores present in the modified porous sepiolite particles is 1.5 to 3 times larger than the average particle diameter of the pores present in the modified porous silica gel particles.

In the adsorption filter for purification of extra virgin olive oil according to the present invention, the content ratio of the modified porous silica particles and the modified porous sepiolite particles in the adsorption layer (2) is in the range of 5: 1 to 1: 2 , More preferably in a weight ratio of 3: 1 to 1: 1.

The adsorption layer 2 may be formed by uniformly mixing the modified porous silica gel particles with the modified porous sepiolite particles or by forming a layer of the modified porous silica gel particles and a layer of the modified porous sepiolite particles by one or more layers But is not limited thereto.

The adsorbing layer 2 having the above-described structure is filled in the receiving space of the body 1 and is then placed on the upper surface and the lower surface of the adsorbing layer 2 by a pair of olive oil permeable supports 5, As shown in Fig. The supports 5, 6 are preferably made of metal, for example, with a radial skeleton structure, which allows the olive oil to flow in and out smoothly.

In the adsorption filter for purifying extra virgin olive oil according to the present invention, it is preferable that the adsorbing layer is formed between the upper surface of the adsorption layer 2 and the support 5, between the lower surface of the adsorption layer 2 and the support 6, (3, 4) for filtering the foreign substances contained in the exhaust gas. The separation membranes 3 and 4 can block the inflow of microorganisms such as filtration and bacteria of other foreign substances such as olive pulp and can prevent the particles constituting the adsorption layer 2 from being separated have. As the separation membranes 3 and 4, a cellulose separator used for a conventional water treatment separation membrane can be used. The average pore size can be adjusted to, for example, 1 to 10 μm.

The extra virgin olive oil is introduced into and passed through the adsorption filter for purifying the extra virgin olive oil having the above-mentioned structure to selectively adsorb the rancidity factors contained in the extra virgin olive oil, and the resulting product is recovered to the storage tank to purify the extra virgin olive oil .

In the method for purifying extra virgin olive oil according to the present invention, the step of filtering foreign matters contained in extra virgin olive oil between steps (S1) and (S2) or between steps (S2) and (S3) Further, foreign substances and the like can be further filtered.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example  One

Preparation of Modified Porous Silica Gel Particles

A silica gel (trade name: Alfa Aesar) having a pore size of 5 nm and a particle size of 120 탆 was prepared. Silica gel particles were added to sulfuric acid and hydrogen peroxide solution to prepare a dispersion. At this time, the ratio of the sulfuric acid was adjusted to 2 times as much as that of hydrogen peroxide, and 2% by weight of silica gel was added to the prepared solution. Ultrasonic treatment was applied to the dispersion to improve the dispersibility of the silica gel particles. The dispersion prepared by the above method was subjected to a reaction at a temperature of 100 ^° C. for 24 hours in a sealed container equipped with a reflux device. The silica gel particles that had undergone the reaction were collected in a solid state through filtration, washed with distilled water for 1 hour and washed twice.

The silica gel particles prepared using the above method were redispersed in a toluene solvent and activated. At this time, the content of dispersed silica was fixed to 2% by weight. 10% by weight of 3-aminopropyltrimethoxysilane was added to the silica gel dispersion and the reaction was carried out at 100 ^° C for 24 hours. The reaction-terminated dispersion was washed three times with toluene. The washed silica particles were separated using a filter paper and dried under high-temperature vacuum to remove residual washing solvent.

Modified porosity Sepiolite  Manufacturing of particles

Sepiolite having a pore size of 10 nm and a particle size of 180 占 퐉 (purchased from Daejun Chemical Co., Ltd.) was prepared. Sepiolite particles were added to an aqueous nitric acid solution to prepare a dispersion. At this time, the nitric acid aqueous solution was diluted to 65 wt% and sepiolite was added to the prepared solution at 10 wt%. Sepiolite dispersion, reaction, and washing proceeded in the same manner as the hydroxyl group introduction reaction of the silica gel particles.

Manufacture of adsorption filter

An adsorption filter of the kind shown in Fig. 1 was prepared.

A body 1 having a receiving space is prepared by using a metal having upper and lower openings. A mixture of the modified porous silica particles and the modified porous sepiolite particles prepared by the above-mentioned method was well packed in the body 1 to form the adsorption layer 2. Next, separation membranes surrounding the adsorption layers 2 and 3, 4, and adsorption layers 2 and separation membranes 3 and 4 were supported and fixed using metal supports 5 and 6, respectively. Here, the separation membranes 3 and 4 used a cellulose separation membrane having a pore size of 10 μm. The body and the support were made of stainless steel which was oxidized or chemically reacted at high temperatures. The silica of the absorbent layer and the sepiolite were mixed in a weight ratio of 1: 2, and a total weight of 3 g was put into the body.

Extra virgin olive oil was passed through the adsorption filter manufactured in the above-described configuration at 100 ^° C. Extra virgin olive oil was continuously introduced into the apparatus to carry out the purification process and treated with a maintenance of 320 g for a total of 1,000 minutes. The mass of the total used adsorbent layer is about 1 wt% based on the weight of olive oil, and the treatment rate is 19.2 g per hour. After the purification process, the average acid value, peroxide value, pigment content and the like, which are indicators of quality stability of olive oil composition and oil quality, were measured using a gas chromatography / mass spectrometer (GC / MS) Respectively.

division Pre-purification After purification Free fatty acid value (mg / g) 0.73 0.06 Peroxide value (meq / kg) 10 5 Pigment factor (ppm) 7.37 1.42 Phospholipid (ppm) 3 0 Fatty acid composition (%) C ₁₆ 10.4 10.4 C _{16: 1} 0.8 0.7 C ₁₇ 0.1 0.1 C _{17: 1} 0.1 0.1 C ₁₈ 3.2 3.2 C _{18: 1} 79.4 78.0 C _{18: 2} 4.5 5.6 C _{18: 3} 0.6 0.8 C ₂₀ 0.4 0.4 C _{20: 1} 0.3 0.3 C ₂₂ 0.2 0.2

As shown in Table 1, the representative acidity factors such as free fatty acids, peroxides, and pigment factors were significantly reduced. In particular, by keeping the composition of olive oil and removing the phospholipid suspended in fine solids, the acidity factor of the problem could be minimized without affecting the final component of olive oil.

Example  2

Using the adsorption filter of Example 1, Elstra virgin olive oil was purified in the same manner, and the extra virgin olive oil oxidation preventing component was measured according to the change of purification time. The measurement of the antioxidant component was carried out by using polyphenol and? -Tocopherol as a measurement index.

An analytical sample solution was prepared by dissolving 0.5 g of olive oil prepared in 5 ml of n-hexane to measure the antioxidant component of olive oil. The analytical sample prepared above was injected into a High Performance Liquid Chromatograph. The mobile phase solvent was a solution of n-hexane and isopropanol in a ratio of 99.5: 0.5 (volume: volume). The high-performance liquid chromatograph was equipped with a fluorescence detector to identify the separated polyphenol and alpha-tocopherol. The results are shown in Table 2.

Purification time (min) Polyphenol (mg / 100 g) Tocopherol (mg / 100 g) 0

0.213.3

0.2 8.26

0.37 30 14.8

0.1 8.24

0.07 60 18.6

0.1 8.23

0.14 90 15.3

0.2 8.18

0.15 120 16.1

0.2 8.20

0.07

As shown in Table 2, the purified olive oil according to the present invention shows that the antioxidant component contained in the olive oil is kept almost constant without being substantially reduced.

1: Body 2: Adsorbent layer
3: Membrane 4: Membrane
5: Support 6: Support

Claims (8)

A body having a receiving space, the body having an upper opening and a lower opening;
The modified porous silica gel particles having a hydroxyl group and an amine group introduced therein and the modified porous periolite particles having a hydroxyl group introduced thereinto are adsorbed in an amount of 5: 1 to 1 : ≪ / RTI > 2 by weight; And
And a pair of olive oil permeable supporters disposed on the upper and lower surfaces of the adsorption layer and supporting and fixing the adsorption layer in the accommodation space of the body, respectively. The method according to claim 1,
Wherein the modified porous silica gel particles have an average particle diameter of 100 to 200 m and an average particle diameter of pores existing in the modified porous silica gel particles is 2 to 10 nm. The method according to claim 1,
Wherein the average particle diameter of the modified porous sepiolite particles is 100 to 200 탆 and the average particle diameter of the pores present in the modified porous sepiolite particles is 5 to 20 nm. . The method of claim 3,
Wherein the average particle size of the pores present in the modified porous sepiolite particles is 1.5 to 3 times larger than the average particle size of the pores present in the modified porous silica gel particles. The method according to claim 1,
Wherein the modified porous silica gel particles and the modified porous sepiolite particles are contained in a weight ratio of 3: 1 to 1: 1. The method according to claim 1,
Further comprising a separation membrane located between the upper surface of the adsorption layer and the support, between the lower surface of the adsorption layer and the support, or both, to filter foreign substances contained in the extra virgin olive oil. (S1) preparing an adsorption filter according to claim 1;
(S2) introducing and passing extra virgin olive oil through the adsorption filter to selectively adsorb a rancidity factor contained in extra virgin olive oil; And
(S3) recovering the product of step (S2) to a storage tank. 8. The method of claim 7,
Further comprising the step of filtering the foreign substances contained in the extra virgin olive oil between the steps (S1) and (S2) or between the steps (S2) and (S3).

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