JP2019055368A - Functional component adsorbent - Google Patents

Abstract

To provide an adsorbent of a functional component sampled from animals and plants.SOLUTION: An adsorbent is used for the adsorption of a functional component selected from the group consisting of lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone, and comprises dioctahedral-type smectite clay or an acid processed product thereof.SELECTED DRAWING: None

Description

  The present invention relates to an adsorbent used for adsorption of functional components contained in various animals and plants, added to supplements and beverages, or used as pharmaceuticals.

  The health consciousness in recent years has extracted the component which has the medical effect contained in various animals and plants, and added this to a supplement, a drink, etc., or is used as a pharmaceutical etc., the component which has such a medical effect is a function. It is called a sex component.

  Representative examples of such functional components are lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone.

Lecithin is represented by the following formula, for example, contains phospholipids contained in egg yolk, soybeans and the like, has a penetrating action through the skin and mucous membranes, and is used as a therapeutic agent for wrinkles and skin diseases. It is also used as a material for pharmaceutical liposomes and fat emulsions for intravenous injection.

Astaxanthin is represented by the following formula and is a pigment substance contained in algae, shrimp, cocoons, cocoons and the like. It has a high antioxidant effect and is considered to exhibit a function of protecting the living body from ultraviolet rays and lipid peroxidation, and has applications such as supplements, health foods, and skin care products.

Quercetin glycosides (for example, rutin) are represented by the following formula and are included in buckwheat and citrus fruits. Antioxidant action, anti-inflammatory action, anti-arteriosclerotic action, prevention of cerebrovascular disease, antitumor effect, hypotensive action, vasorelaxant action, etc. have been reported and are used as pharmaceuticals.

Chlorogenic acid is represented by the following formula and is contained in coffee beans and the like. It is considered to give astringent tastes such as astringency, sourness and sweetness to water and the like, and is added to various beverages.

Isoflavone is contained in soybeans and is represented by the following formula. The compound is generally marketed as genistein or the like. It is said to be effective in improving menopause and preventing osteoporosis and is used as a supplement.

  Any of the above functional components is isolated and extracted for use from animals and plants containing these (see Patent Documents 1 to 5), but is used for isolation from the extract. As the agent, silica gel, alumina, activated carbon and the like are used, and detailed examination of the adsorbent has not been performed.

JP-A-2015-142560 Japanese Patent Laid-Open No. 05-068585 Japanese Patent Laid-Open No. 54-101212 JP 2007-54056 A Japanese Patent Laid-Open No. 08-283283

  As a result of studying the adsorbent for the functional component, the present inventors have found that the so-called clay clay or its acid-treated product effectively adsorbs the functional component from the aqueous solution or alcohol solution of the functional component. The knowledge that it is possible was obtained.

  Accordingly, an object of the present invention is to provide an adsorbent for functional components collected from animals and plants.

According to the present invention, an adsorbent used for adsorption of a functional component selected from the group consisting of lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone,
There is provided an adsorbent comprising dioctahedral smectite clay or an acid-treated product thereof.

  In the present invention, the dioctahedral smectite clay used as the adsorbent is called so-called acid clay, and the acid-treated product is called activated clay.

  That is, in the adsorbent of the present invention, by adding this adsorbent to an aqueous solution or alcohol solution containing the above functional components, various functional components can be adsorbed and isolated from the solution. it can.

  Further, the adsorbent of the present invention has high filterability and can be easily separated from the solution after the adsorption treatment.

2 is an X-ray diffraction chart derived from the plane index (06) of the adsorbent (acid clay) of the present invention used in Example 1. FIG. 4 is an X-ray diffraction chart derived from the surface index (06) of the adsorbent (weakly acid-treated clay) of the present invention used in Example 2. 6 is an X-ray diffraction chart derived from the plane index (06) of the adsorbent (active clay) of the present invention used in Example 3.

<Adsorbent>
In the present invention, dioctahedral smectite clay used as the adsorbent is believed to volcanic rock and lava is modified under the influence of sea water, a major component dioctahedral smectite SiO ₄ tetrahedral layers -AlO ₆ The basic structure (unit layer) is a three-layer structure composed of octahedral layers-SiO ₄ tetrahedral layers, and these tetrahedral layers and octahedral layers are partially replaced with different metals. Between stacked layers having a layer structure, cations such as Ca, K, and Na, hydrogen ions, and water molecules coordinated therewith exist. In addition, Mg or Fe (II) is substituted for part of Al in the octahedral layer of the basic three-layer structure, and Al is substituted for part of Si in the tetrahedral layer, so that the crystal lattice is negative. The negative charge is neutralized by metal cations and hydrogen ions existing between the basic layers.

  Such a dioctahedral smectite clay exhibits a characteristic X-ray diffraction peak derived from its crystal structure. For example, in X-ray diffraction measurement, a diffraction peak derived from the plane index (06) is 2θ = 62 degrees (d = 1.49 to 1.50 mm).

  Such smectite clays include acid clay, bentonite, fuller's earth, and the like, and exhibit different characteristics depending on the type and amount of metal cations existing between the basic layers, the amount of hydrogen ions, and the like. For example, bentonite has a large amount of Na ions present between the basic layers, and therefore, the pH of the dispersion suspended in water is high, generally on the high alkali side, and has high swellability with respect to water. Furthermore, it shows the property of gelling and solidifying. On the other hand, in the acid clay, the amount of hydrogen ions present between the basic layers is large, and therefore, the pH of the dispersion suspended and dispersed in water is low, generally on the acidic side, and swellable with water. However, compared with bentonite, its swelling property is generally low, and it does not cause gelation.

In the present invention, as the dioctahedral smectite clay, any of the above can be used as long as it exhibits the above-mentioned characteristic X-ray diffraction peak.
The dioctahedral smectite clay generally has the following composition in terms of oxide, although it differs depending on the origin of the clay, the place of production, the same place of production, and the buried place (face).
SiO _2; 50 to 75 wt%
Al ₂ O ₃ ; 11 to 25% by mass
Fe ₂ O ₃ ; 2 to 20% by mass
MgO; 2-7% by mass
CaO; 0.1-3 mass%
Na ₂ O; 0.1 to 3 wt%
K ₂ O; 0.1 to 3 wt%
Other oxides (TiO _2, etc.); 2 wt% or less Ig-loss (1050 ℃); 5~11 wt%

  In addition, dioctahedral smectite clay may contain a large amount of impurities such as quartz depending on the production area. Therefore, the dioctahedral smectite clay is used as an adsorbent in which impurities are removed as much as possible by subjecting it to refining operations such as stone sand separation, buoyancy beneficiation, magnetic beneficiation, elutriation, wind drought, etc. if necessary. .

  In the present invention, among the above-mentioned dioctahedral smectite clays, those having a low content of alkali metal or alkaline earth metal contained between the basic layers, specifically, those called acid clay or fuller's earth are suitable. In particular, those having a pH of 6 or less at 25 ° C. in a 5% by mass suspension are preferably used from the viewpoint of filterability and the like.

In the present invention, the acid-treated product of the above dioctahedral smectite clay can also be used as an adsorbent for the functional component.
This acid-treated product is called activated clay, and is obtained by eluting Al and Mg components by acid treatment to such an extent that the basic layer structure of the dioctahedral smectite clay is not destroyed. Therefore, the activated clay, like dioctahedral smectite clay (non-acid-treated product), shows a diffraction peak derived from the plane index (06), and the specific surface area is increased, usually 100 m ² / g or more, In particular, it has a BET specific surface area of 250 m ² / g or more. In addition, such activated clay has a lower amount of solid acid than that which has not been acid-treated because Al and Mg acting as solid acid sites are eluted by the acid treatment described above. However, when an organic acid is used or when the acid treatment is weakened (weak acid treatment), the amount of solid acid is generally high because the solid acid spots covered with impurities are exposed.
Therefore, in general, dioctahedral smectite clay (for example, acid clay) or acid-treated products thereof (for example, activated clay, weak acid-treated clay) has a solid acid amount of Ho ≦ −3.0 of 0.01 to 0.70 mmol / g. It is in the range of -dry cray or higher.

The BET specific surface area and the solid acid amount of the activated clay described above vary depending on the degree of acid treatment, and if the acid treatment is strongly performed within the range where the basic skeleton of the smectite clay does not vary, the BET specific surface area increases, The amount of acid will decrease.
For example, as an activated clay obtained by a very weak acid treatment, JP 2009-072759 by the present applicant discloses an acid-treated product called a semi-activated clay as a polylactic acid depolymerization catalyst. Such semi-active clay can also be used as an adsorbent for functional components in the present invention.

Dioctahedral smectite clay is roughly crushed, kneaded, and acid-treated under a predetermined condition using an aqueous acid solution having a predetermined concentration.
The acid treatment is performed by adding dioctahedral smectite clay from which impurities have been removed to an aqueous acid solution and mixing and stirring. The acid aqueous solution used for the acid treatment is not particularly limited, but a sulfuric acid aqueous solution is generally used from the viewpoint of cost, environmental impact, and the like.

  The acid treatment conditions may be set as appropriate according to the physical properties of the target activated clay (BET specific surface area and solid acid amount). For example, when an aqueous sulfuric acid solution is used, the water contained in the raw clay is also an aqueous sulfuric acid solution. The amount of sulfuric acid aqueous solution calculated as constituting the water is usually 250 to 800 parts by mass per 100 parts by mass of raw clay (as 110 ° C. dry matter), and the concentration of sulfuric acid aqueous solution at that time is about 1 to 15% by mass (weak acid treatment) Or what is necessary is just to perform an acid treatment on the conditions which become 15-45 mass% (general acid treatment). In the acid treatment, heating can be performed as necessary.

The activated clay obtained by such acid treatment generally has the following chemical composition in terms of oxide.
SiO _2; 50 to 85 wt%
Al ₂ O _3; 8~23 wt%
Fe ₂ O _3; 1~10 wt% MgO; 1 to 5 wt% or less CaO; 0.1 to 2 wt% or less Na ₂ O; 0.1 to 1 wt%
K ₂ O; 0.1 to 1 wt%
Other oxides (TiO _2, etc.); 2 wt% or less Ig-loss (1050 ℃); 4~9 wt%

The activated clay, which is an acid-treated product of such a dioctahedral smectite clay, has excellent filterability in connection with being subjected to acid treatment.
That is, the smectite clay (acid clay) that has not been subjected to acid treatment has a large interlayer containing cations such as Na between the basic layers, and thus exhibits high swellability with respect to water. It is considered that filterability is poor due to fine dispersion. However, in activated clay, a part of the base component in the smectite clay reacts with the acid to become an insoluble binder for certain types of water, alcohol, etc. It is considered that fine dispersion is suppressed and excellent filterability is exhibited.

<Use as adsorbent>
The above-mentioned dioctahedral smectite clay or its acid-treated product is classified to an appropriate particle size (for example, 150 mesh pass) and used as an adsorbent for functional components.
In the present invention, lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone are selected as such functional components.

That is, the functional component in the liquid is obtained by adding the adsorbent to an aqueous solution of the functional component obtained in the process of collecting the functional component or an alcohol solution such as ethanol and stirring for an appropriate time. Can be adsorbed. Furthermore, the functional component can be adsorbed by introducing it into an aqueous solution containing the above functional component obtained by various synthetic reactions using enzymes, microorganisms or the like, or an alcohol solution such as ethanol.
The aqueous solution or alcohol solution is not particularly limited in the concentration of the functional component and the amount of adsorbent used, but may be a dilute solution of preferably 5% by mass or less, and usually 0.001 per 100 parts by mass of the solution. What is necessary is just to use about 25 mass parts adsorbent.
After the adsorption, the adsorbent in which the functional component is adsorbed can be isolated by performing filtration by a known means.
There is no restriction | limiting in particular in the discharge | release method of the adsorbed functional component, It implements by a conventionally well-known solvent extraction method etc. For example, it is possible to recover the functional component by putting it into pure water and releasing the adsorbed functional component by subjecting it to a stirring operation such as ultrasonic vibration, and by concentrating or removing the solvent.

The adsorbent of the present invention is particularly excellent in adsorbing egg yolk lecithin, soybean lecithin and astaxanthin.
In general, activated clay, which is an acid-treated product, is preferably used from the standpoint of filterability and the like, but quercetin glycoside (rutin) and soy isoflavone (genistein) are not acid-treated. No dioctahedral smectite clay shows better adsorptivity.
The recovered functional component is used for various beverages, supplements, pharmaceuticals, and the like depending on the type.

  The excellent effect of the present invention will be described by the following experimental example.

(1) X-ray diffraction Measured with RINT-Ultima IV (X-ray = CuKα ray) manufactured by Rigaku Corporation.

(2) pH
Adsorbent powder was added to ion-exchanged water so that the concentration of the adsorbent was 5% by mass, and the mixture was stirred for 30 minutes, and then measured with a pH meter HM-30R manufactured by Toa DKK.

(3) Adsorption test Using the test solution consisting of the functional component and the solvent shown in Table 1, the adsorption ability for each component was evaluated. The adsorption capacity was defined as the amount (mg) that 1 g of the adsorbent can be adsorbed, and measured by the following method.
First, each functional component was dissolved in a solvent to obtain a functional component solution having a concentration of 0.2 g / L. 30 g of this solution was weighed into a 50 ml centrifuge tube, 1 g of adsorbent (3.3% by mass with respect to the liquid) was added, and the mixture was shaken at 2.5 rpm at 150 rpm with a horizontal shaker (As One Shaking Bath SB-13). Shaking time.
Next, a supernatant liquid (sample liquid) treated with a centrifugal separator (CR22GIII manufactured by Hitachi Koki Co., Ltd.) at a centrifugal acceleration of 18000 rpm for 20 minutes was obtained. The absorbance of the sample solution was measured with a spectrophotometer (SPECTROTOPOMETER UV-3600 manufactured by Shimadzu Corporation). At this time, if there is an effect of leaching salts, etc. of the test powder, the absorbance when the same operation is performed by adding the test powder to the solvent in which each component is not dissolved in advance is subtracted from the absorbance of the sample solution, and the corrected absorbance of the sample solution It was. Then, the component residual amount of the sample solution was calculated using a calibration curve showing the relationship between the component concentration and the absorbance prepared in advance, and the value subtracted from the component amount before addition of the adsorbent was used as the component adsorption amount of the adsorbent. All tests were performed in duplicate and average values were used.

  Table 2 shows the results of the adsorption test for the adsorbent powders shown in the following Examples and Comparative Examples.

Example 1
Acid clay white mizuka ace No. made by Mizusawa Chemical Co., Ltd. 20 (pH 4.9). The X-ray diffraction chart is shown in FIG.

(Example 2)

In a beaker, 220 ml of 5 mass% sulfuric acid aqueous solution was taken and heated to 90 ° C. Thereto, 30 g of acid clay of Comparative Example 1 was added, and the mixture was stirred while maintaining the liquid temperature at 90 ° C., and acid treatment was performed for 30 minutes. After completion of the acid treatment, the acid-treated product was filtered and washed with water, and the washed filter cake was dried at 110 ° C., pulverized and classified to obtain a weak acid-treated clay powder (pH 3.1). The obtained weakly acid-treated clay powder was measured with an XRD measuring device. The X-ray diffraction chart is shown in FIG.

(Comparative Example 1)
Mizusawa Chemical Industry Co., Ltd. silicon dioxide Mizukasorb C-6 (pH 6.5).

(Comparative Example 2)
A composite adsorbent Mizuka Life F-2G (pH 8.9) mainly composed of silicon dioxide and magnesium oxide manufactured by Mizusawa Chemical Co., Ltd.

(Example 3)
Activated clay galleon earth V2 (pH 3.5) manufactured by Mizusawa Chemical Co., Ltd. An X-ray diffraction chart is shown in FIG.

Claims (1)

An adsorbent used for adsorption of a functional component selected from the group consisting of lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone,
An adsorbent comprising dioctahedral smectite clay or an acid-treated product thereof.