JP7105967B2 - functional ingredient adsorbent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adsorbent used for adsorbing functional ingredients contained in various animals and plants, added to supplements, beverages, etc., or used as pharmaceuticals.

In recent years, people have become health conscious by extracting medically effective ingredients contained in various animals and plants, adding them to supplements, beverages, etc., or using them as pharmaceuticals. called the sex component.

Typical functional ingredients as described above are lecithin, astaxanthin, quercetin glycosides, chlorogenic acid and isoflavones.

Lecithin is represented, for example, by the following formula, contains phospholipids contained in egg yolks, soybeans, etc., has a penetrating action to permeate the skin and mucous membranes, and is used as a therapeutic agent for hemorrhoids and skin diseases. It is also used as a material for pharmaceutical liposomes and as a lipid emulsion for intravenous injection.

Astaxanthin is represented by the following formula and is a pigment substance contained in algae, shrimp, sea bream, salmon and the like. It has a high antioxidant effect and is thought to exhibit the function of protecting the body from ultraviolet rays and lipid peroxidation, and is used in supplements, health foods, skin care products, and the like.

Quercetin glycosides (eg, rutin) are represented by the following formula and are contained in buckwheat and citrus fruits. It has been reported to have antioxidant, anti-inflammatory, antiarteriosclerotic, cerebrovascular disease prevention, antitumor, hypotensive, and vasorelaxant effects, and is used as a pharmaceutical.

Chlorogenic acid is represented by the following formula and is contained in coffee beans and the like. It is thought to impart astringent, sour, and sweet tastes to water, etc., and is added to various beverages.

Isoflavones are contained in soybeans and the like, and are represented by the following formula. As a compound, it is generally marketed as genistein. It is said to have an effect of improving menopausal disorders and preventing osteoporosis, and is used as a supplement.

Any of the above functional ingredients are isolated and used by extraction from animals and plants containing them (see Patent Documents 1 to 5). Silica gel, alumina, activated carbon, etc. are used as agents, and detailed studies on adsorbents have not been conducted.

JP 2015-142560 A JP-A-05-068585 JP-A-54-101412 JP 2007-54056 A JP-A-08-283283

The inventors of the present invention have studied the adsorbents for the above functional ingredients, and found that so-called clay-based clay or its acid-treated material effectively adsorbs the functional ingredient from the above aqueous solution or alcohol solution of the functional ingredient. I got the knowledge that it is possible.

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

According to the present invention, an adsorbent used for adsorbing a functional ingredient selected from the group consisting of lecithin, astaxanthin, quercetin glycosides, chlorogenic acid and isoflavones,
Provided is an adsorbent comprising a dioctahedral smectite clay or an acid-treated product thereof.

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

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

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

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

<Adsorbent>
_In the present invention, the dioctahedral _- type smectite clay used as the adsorbent is considered to have been metamorphosed from volcanic rock, lava, etc. under the influence of seawater. The basic structure (unit layer) is a three-layer structure (unit layer) consisting of an octahedral layer--a SiO ₄ tetrahedral layer, and the tetrahedral layer and the octahedral layer are partially isomorphically substituted with a dissimilar metal. Between the laminated layers of the layered structure, cations such as Ca, K, and Na, hydrogen ions, and water molecules coordinated thereto are present. In addition, Mg and Fe (II) are 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 the crystal lattice is negative. It has an electric charge, and this negative electric charge is neutralized by metal cations and hydrogen ions existing between the basic layers.

Such a dioctahedral smectite clay exhibits a unique X-ray diffraction peak derived from its crystal structure. = 1.49 to 1.50 Å).

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

In the present invention, any of the above-described dioctahedral smectite clays can be used as long as they exhibit the above-described specific X-ray diffraction peaks.
Dioctahedral smectite clays generally have the following composition in terms of oxides, although they differ depending on the origin of the clay, the place of production, and even in the same place of production, the burial place (face).
SiO ₂ ; 50 to 75% by mass
Al ₂ O ₃ ; 11 to 25% by mass
Fe ₂ O ₃ ; 2 to 20% by mass
MgO; 2 to 7% by mass
CaO; 0.1 to 3% by mass
Na ₂ O; 0.1 to 3% by mass
K ₂ O; 0.1 to 3% by mass
Other oxides (TiO ₂ , etc.); 2% by mass or less Ig-loss (1050°C); 5 to 11% by mass

Dioctahedral smectite clay may contain a large amount of impurities such as quartz depending on the place of production. Therefore, the above dioctahedral smectite clay is subjected to refining operations such as stone sand separation, buoyancy beneficiation, magnetic beneficiation, elutriation, wind elutriation, etc., if necessary, and is used as an adsorbent to remove impurities as much as possible. .

In the present invention, among the dioctahedral smectite clays mentioned above, those having a low content of alkali metals or alkaline earth metals 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 mass % suspension are preferably used from the viewpoint of filterability and the like.

In addition, in the present invention, the acid-treated dioctahedral smectite clay can also be used as an adsorbent for functional components.
This acid-treated product is called activated clay, and is obtained by eluting Al and Mg by acid-treating the dioctahedral smectite clay to such an extent that the basic layer structure is not destroyed. Therefore, the activated clay, like the dioctahedral smectite clay (non-acid-treated product), exhibits a diffraction peak derived from the plane index (06) and has an increased specific surface area, 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, since Al and Mg, which act as solid acid sites, are eluted from the activated clay by the acid treatment, the amount of solid acid is lower than that of non-acid-treated clay. However, when an organic acid is used or when the degree of acid treatment is weakened (weak acid treatment), the amount of solid acid generally increases, probably because the solid acid sites covered with contaminants or the like are exposed.
Therefore, in general, a dioctahedral smectite-based clay (eg, acid clay) or an acid-treated product thereof (eg, activated clay, weakly acid-treated clay) has a solid acid content of Ho≦−3.0 of 0.01 to 0.70 mmol/g. - in the range of dry clay and above.

The BET specific surface area and the amount of solid acid of the above-mentioned activated clay vary depending on the degree of acid treatment, and if the acid treatment is performed strongly within the range where the basic skeleton of the smectite clay does not change, the BET specific surface area increases and the solid acid content increases. The amount of acid will decrease.
For example, Japanese Patent Application Laid-Open No. 2009-072759 by the present applicant discloses an acid-treated product called semi-activated clay as a catalyst for polylactic acid depolymerization as an activated clay obtained by very weak acid treatment. Semi-activated clay can also be used as an adsorbent for functional ingredients in the present invention.

Dioctahedral smectite clay is coarsely pulverized, kneaded, and acid-treated under predetermined conditions using an acid aqueous solution of a predetermined concentration.
The acid treatment is carried out by adding the dioctahedral smectite clay from which contaminants have been removed into an acid aqueous solution and mixing and stirring. The aqueous acid solution used for the acid treatment is not particularly limited, but an aqueous sulfuric acid solution is generally used from the viewpoint of cost, environmental impact, and the like.

The acid treatment conditions may be appropriately set according to the desired physical properties of the activated clay (BET specific surface area and solid acid content). is usually 250 to 800 parts by mass per 100 parts by mass of the raw material clay (as dried at 110°C), and the concentration of the sulfuric acid aqueous solution at that time is about 1 to 15% by mass (weak acid treatment). Alternatively, the acid treatment may be carried out under conditions such that the content becomes 15 to 45% by mass (general acid treatment). In the acid treatment, heating can be carried out if necessary.

The activated clay obtained by such acid treatment generally has the following chemical composition in terms of oxide.
SiO ₂ ; 50 to 85% by mass
Al ₂ O ₃ ; 8 to 23% by mass
Fe ₂ O ₃ : 1 to 10% by mass MgO: 1 to 5% by mass CaO: 0.1 to 2% by mass Na ₂ O: 0.1 to 1% by mass
K ₂ O; 0.1 to 1% by mass
Other oxides (TiO ₂ , etc.); 2% by mass or less Ig-loss (1050°C); 4 to 9% by mass

Activated clay, which is an acid-treated dioctahedral-type smectite clay, has excellent filterability associated with the acid treatment.
That is, smectite clay that has not been acid-treated (acidic clay) has large interlayers containing cations such as Na between the basic layers. It is believed that filterability is poor due to fine dispersion. However, in activated clay, some of the base components in the smectite clay react with acid and form a kind of binder that is insoluble in water, alcohol, etc., and binds particles together. It is considered that fine dispersion is suppressed and excellent filterability is exhibited.

<Use as adsorbent>
The dioctahedral smectite clay or its acid-treated clay described above 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 glycosides, chlorogenic acid and isoflavones are selected as such functional ingredients.

That is, the above adsorbent is added to an aqueous solution or an alcoholic solution such as ethanol of the functional component obtained in the process of extracting the functional component, and the functional component in the solution is stirred for an appropriate time. can be adsorbed. Furthermore, the functional component can be adsorbed by adding it to an aqueous solution or an alcoholic solution such as ethanol containing the functional component obtained by various synthetic reactions using enzymes, microorganisms, and the like.
The above aqueous solution or alcohol solution is not particularly limited in the functional ingredient concentration and the amount of adsorbent used, but it may be a dilute solution of preferably 5% by mass or less, and usually 0.001 per 100 parts by mass of the solution. Up to 25 parts by mass of adsorbent may be used.
After adsorption, filtration can be performed by a known means to isolate the adsorbent on which the functional component is adsorbed.
There is no particular limitation on the method for releasing the adsorbed functional ingredient, and it is carried out by a conventionally known solvent extraction method or the like. For example, it is put into pure water and subjected to a stirring operation such as ultrasonic vibration to release the adsorbed functional component, and the functional component can be recovered 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. Dioctahedral-type smectite-based clay, which does not have a
The recovered functional ingredients are used for various beverages, supplements, pharmaceuticals, and the like, depending on the type.

The excellent effects of the present invention will be explained by the following experimental examples.

(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 adsorbent concentration was 5% by mass, and after stirring for 30 minutes, the pH was measured with a pH meter HM-30R manufactured by DKK Toa.

(3) Adsorption test A test solution composed of the functional component and solvent shown in Table 1 was used to evaluate the adsorption capacity for each component. The adsorption capacity was defined as the amount (mg) that can be adsorbed by 1 g of the adsorbent, and was measured by the following method, and the calculated values are shown in Table 2.
First, each functional ingredient was dissolved in a solvent to obtain a functional ingredient solution with a concentration of 0.2 g/L. 30 g of this solution was weighed into a 50 ml capacity centrifuge tube, 1 g of adsorbent (3.3% by mass relative to the liquid) was added, and the mixture was stirred at 150 rpm with a horizontal shaker (AS ONE Shaking Bath SB-13) to 2.5. Time was shaken.
Next, the liquid was treated with a centrifugal separator (CR22GIII manufactured by Hitachi Koki Co., Ltd.) at a centrifugal acceleration of 18000 rpm for 20 minutes to obtain a supernatant liquid (sample liquid). The absorbance of the sample solution was measured with a spectrophotometer (SPECTROPHOTOMETER UV-3600 manufactured by Shimadzu Corporation). At this time, if there is an effect of leaching and desalination of the test powder, subtract the absorbance when the test powder is added to the solvent in which each component is not dissolved in advance and perform the same operation, from the absorbance of the sample solution, and calculate the corrected absorbance of the sample solution. and Then, using a calibration curve prepared in advance showing the relationship between component concentration and absorbance, the component remaining amount of the sample solution was calculated, and the value obtained by subtracting 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 the average value was used.

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

(Example 1)
Acid clay Mizuka Ace No. manufactured by Mizusawa Chemical Industry Co., Ltd.; 20 (pH 4.9). An X-ray diffraction chart is shown in FIG.

(Example 2)

220 ml of a 5% by mass sulfuric acid aqueous solution was placed in a beaker and heated to 90°C. 30 g of the acid clay of Comparative Example 1 was added thereto, and the mixture was stirred while the liquid temperature was maintained at 90° C., and acid treatment was performed for 30 minutes. After 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 weakly acid-treated clay powder (pH 3.1). The obtained weak acid-treated clay powder was measured by an XRD measurement device. An X-ray diffraction chart is shown in FIG.

(Comparative example 1)
Silicon dioxide Mizukasorb C-6 (pH 6.5) manufactured by Mizusawa Chemical Industry Co., Ltd.;

(Comparative example 2)
Composite adsorbent Mizukalife F-2G (pH 8.9) mainly composed of silicon dioxide and magnesium oxide manufactured by Mizusawa Chemical Industry Co., Ltd.

(Example 3)
Active clay Galleon Earth V2 (pH 3.5) manufactured by Mizusawa Chemical Industry Co., Ltd.; An X-ray diffraction chart is shown in FIG.

Claims (1)

An adsorbent used for adsorbing quercetin glycosides,
An adsorbent comprising acid clay of dioctahedral type smectite clay.

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