JP2671094B2 - Immobilized polymer tannin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an immobilized polymer tannin. The immobilized polymer tannin according to the present invention well adsorbs proteins, iron, alkaloid substances, etc. present in water and various aqueous solutions, and thus is useful as, for example, a protein adsorbent for brewing, a water purification treatment agent, a wastewater treatment agent, etc. Is.

[0002]

2. Description of the Related Art As is well known, tannins are used for purification of brewing water and clarification of sake because they adsorb proteins and iron existing in water.

Conventionally, various techniques have been proposed in which tannins are used in the above-mentioned applications in the form of immobilized tannins, such as tannin compounds and water-insoluble and hydrophilic polymers. (See JP-B-55-7225 and JP-B-55-40234) and a technique using a hydrous gel composition obtained by allowing peroxodisulfate to act on liquid persimmon astringent (Japanese Patent Laid-Open Publication No. Hei. Two
9742) and the like.

However, as far as the inventors of the present invention know, no technique has yet been proposed for firmly immobilizing tannins using a granular hydrophobic resin as a carrier.

[0005]

DISCLOSURE OF THE INVENTION The present inventor will fill a column etc. with the immobilized tannin if it can be strongly immobilized on a carrier made of a granular hydrophobic resin without impairing the adsorption ability of tannins. It is believed that the adsorption capacity of tannins can be efficiently utilized, and the realization of that is a technical issue, and as a result of numerous experiments and trial production, the present invention has been completed. .

[0006]

The above technical objects can be achieved by the present invention as described below. That is, the present invention, the polymer tannin is adsorbed and fixed in a film state on the particle surface of the hydrophobic synthetic resin particles or hydrophobic natural resin particles, and
The immobilized polymer tannin is characterized in that the molecules of the film polymer tannin are crosslinked.

The immobilized polymer tannin according to the present invention is prepared by dissolving the polymer tannin in an aqueous alcohol solution,
Next, the hydrophobic synthetic resin particles or the hydrophobic natural resin particles are dispersed in this solution, and then the alcohol content is removed from this dispersion liquid to disperse the polymer particles on the surface of the resin particles dispersed in the liquid. Is adsorbed and fixed in a film state, and then the resin particles having the polymer tannin adsorbed and fixed in a film state are collected and dispersed in an acidic aqueous solution, and a crosslinking agent is used to form a film on the particle surface of the resin particles. It is obtained by a method for producing an immobilized polymeric tannin, which comprises cross-linking the molecules of the adsorbed / fixed polymeric tannin and then collecting and washing the resin particles.

The immobilized polymer tannin according to the present invention as described above can be used by being packed in a column or the like as an adsorbent for proteins, iron, alkaloid substances and the like existing in water and various aqueous solutions.

Next, the structure of the present invention will be described in more detail. The polymer tannin in the present invention is condensed tannin (proanthocyanidin polymer) or hydrolyzed tannin, and specific examples thereof include commercially available purified persimmon astringent liquid, tannic acid and the like.

The hydrophobic synthetic resin particles in the present invention are those obtained by processing a highly hydrophobic synthetic resin such as styrene type or phenol type into granular materials, glass beads modified with phenyl groups or hydrocarbon groups, and silica gel resin particles. Further, the hydrophobic natural resin particles are obtained by processing a natural polymer resin modified with a highly hydrophobic residue into a granular material, and all have a particle diameter of about 300 to 1200 μm and are porous. It is preferable to select a granular material. Specifically, as the former, it is Diaion HP (trade name: manufactured by Mitsubishi Kasei Co., Ltd .: a synthetic resin particle composed of a styrene-divinylbenzene skeleton, and various particle diameters depending on the product number). And Amberlite XAD (trade name: made by Organo Corporation:
And the like, and the latter includes phenylcellulofine (trade name: manufactured by Seikagaku Corporation), phenyl agarose resin (manufactured by Sigma: USA), and the like.

Preferred production conditions for obtaining the immobilized polymer tannin of the present invention are as follows.

First, in dissolving the high molecular weight tannin in an aqueous alcohol solution, an alcohol aqueous solution of about 20 to 70% is prepared by using ethanol, methanol or the like as the alcohol, and the high molecular weight tannin is added to the high molecular weight tannin. Add and dissolve to a concentration of about 0.5 to 2%. The polymer tannin can be added in the form of an alcohol (eg ethanol) solution.

Next, in dispersing the resin particles in an alcohol aqueous solution in which the polymer tannin is dissolved,
It is desirable to wash and place the resin particles, and washing can be performed in the order of acetone → methanol → ethanol according to a conventional method. The amount of dispersion is preferably 1: 3 to 1:20 in volume ratio of the resin particles: an aqueous alcohol solution in which the polymer tannin is dissolved.

Next, in removing the alcohol content from the dispersion liquid in which the resin particles are dispersed, it is necessary to gradually remove the alcohol content while maintaining the dispersion state. For this purpose, for example, vacuum concentration may be performed under rotation using a rotary evaporator. Usually, decompression (20-30mm
Hg) under reduced pressure while rotating in a temperature range of 25 to 35 ° C. for 6 to 48 hours to remove alcohol.
The polymeric tannin can be adsorbed and fixed in a film form on the surface of each of the resin particles. After completion of the alcohol removal step, the resin particles in the liquid are collected by filtration according to a conventional method, and the process proceeds to the next step. In this case, the resin particles are washed with water to remove excess polymer tannin and placed. .

Next, in order to crosslink between the molecules of the high molecular weight tannin adsorbed and fixed in a film state on the particle surface of the resin particles, phosphoric acid, hydrochloric acid, sulfuric acid, etc. are used to obtain an acidity of about pH 1-3. An aqueous solution is prepared and the resin particles are dispersed therein, and at the same time, aldehydes (eg formaldehyde, acetaldehyde, glutaraldehyde, furfural, acrolein, etc.), phosphorus-containing compounds (eg hexamethylenetetramine, trimethylolphosphine oxide, etc.) or S-triazine The crosslinking reaction is carried out using a known crosslinking agent such as. In the cross-linking reaction, the resin particles need to maintain a dispersed state. For this purpose, for example, a rotary evaporator may be used under rotation as in the above. Usually, under normal pressure, in the temperature range of 15 to 30 ° C., 6 to
If the crosslinking reaction is carried out for 48 hours, it is possible to sufficiently crosslink between the molecules of the polymer tannin that is adsorbed and fixed in the film state.

After completion of the above-mentioned crosslinking reaction step, the resin particles in which the polymer tannin is adsorbed and fixed in a film state on the particle surface, and the molecules of the film-like polymer tannin are crosslinked, According to a conventional method, the resin particles are collected by filtration, and the resin particles are sufficiently washed to remove the unreacted cross-linking agent adhering thereto, whereby the target immobilized polymer tannin can be obtained. If necessary, after the crosslinking reaction, prior to washing, a low molecular weight polyphenol such as phloroglucinol may be added to mask the unreacted crosslinking agent.

[0017]

First, it can be said that the phenomenon in which the polymeric tannin is adsorbed and fixed in the form of a film on the particle surface of the resin particles in the present invention is as follows. That is, when the resin particles are dispersed in the alcohol aqueous solution in which the polymer tannin is dissolved and the alcohol content is removed from the dispersion,
It can be presumed that the exposed hydrophobic group or the hydrophobic portion of the polymer tannin is adsorbed and fixed to the particle surface (nonpolar) of the resin particles by the hydrophobic bond. Then, since the alcohol content is gradually removed while maintaining the dispersed state of the resin particles, the concentrated polymer tannin is adsorbed and fixed in a substantially uniform film state. The adsorption / fixation by the hydrophobic bond and the crosslinking reaction in the next step under the above production conditions do not impair the adsorption ability of the polymer tannin.

Next, the immobilized polymer tannin according to the present invention is adsorbed and fixed in a film state on the particle surface of the resin particles as a carrier, and the molecules of the film polymer tannin are crosslinked. Since it is very strongly immobilized on the carrier, it can be packed in a column, etc.
High-molecular tannin is hardly released from the carrier.

In addition, when the immobilized polymer according to the present invention is packed in a column or the like and a liquid to be treated (for example, brewing water or liquor) is passed through the column, the carrier is a granular substance, which is high. Since the flow rate can be obtained, proteins and iron in the liquid to be treated can be efficiently adsorbed.

[0020]

EXAMPLES Examples of the present invention will be given below, but the present invention is not limited to the examples.

Example 1 Diaion HP-20 (trade name: manufactured by Mitsubishi Kasei Co., Ltd .: having a styrene-divinylbenzene skeleton) having the physical properties shown in Table 1 was used as the hydrophobic synthetic resin particles as a carrier. 100 g of these resin particles are added to 4 times the amount of acetone to obtain 12
After soaking for a period of time, it was filled in an open column and passed with 10 volumes of acetone, followed by passing with 10 volumes of methanol, and then washed with 5 volumes of ethanol, and further 50 times.
% Aqueous solution of ethanol. On the other hand, a commercially available purified persimmon astringent liquid was dissolved in a 50% ethanol aqueous solution to prepare 600 ml of a oyster tannin solution having a tannin concentration of 0.9%. 100 g of the resin particles after the washing and the above-mentioned oyster tannin solution 600
ml (ca. 606g) and put into a 2L eggplant-shaped flask, and depressurize (about 25mmHg) with a rotary evaporator.
At 25 ° C., while rotating, the solution was concentrated under reduced pressure for 24 hours to remove the ethanol content, and then the resin particles in the liquid were collected by filtration, washed with 10 times the amount of distilled water, As a result, 105 g of resin particles in which oyster tannin was adsorbed and fixed on the particle surface in a film state were obtained. Then formaldehyde 0.2
% And glutaraldehyde 0.2% dissolved in 50 mM
105 g of the above resin particles are added to 600 ml of the phosphoric acid aqueous solution of
After cross-linking with a rotary evaporator at 25 ° C. under atmospheric pressure for 12 hours while rotating, the resin particles in the liquid are collected by filtration, washed with 5 times amount of distilled water, and further 5 times. The product was washed with an amount of 30% ethanol aqueous solution to obtain the desired immobilized oyster tannin. The amount of total polyphenols of the immobilized oyster tannin obtained here was measured by the Folin-Ciocalteu method, and the unadsorbed amount was subtracted. As a result, it was 1.4 to 1.8 per 100 ml of resin particles.
It contained g oyster tannin. The immobilized oyster tannins obtained here were stored in a 30% ethanol aqueous solution at 4 ° C. for 5 days, and then subjected to the later-described adsorption capacity test.

[0022]

[Table 1]

Example 2 Diaion HP-20 (described above) washed in Example 1 was used as the hydrophobic synthetic resin particles as the carrier. On the other hand, commercially available tannic acid (15 g) was dissolved in 50% ethanol aqueous solution to prepare tannic acid solution (600 ml). 100 g of the washed resin particles and 600 ml of the tannic acid solution were placed in a 2-liter eggplant-shaped flask, and concentrated under reduced pressure (about 25 mmHg) with a rotary evaporator at 25 ° C. for 24 hours under reduced pressure while rotating. After removing the ethanol content by filtration, the resin particles in the liquid are collected by filtration, washed with 10 times the amount of distilled water, and tannic acid is adsorbed and fixed in a film state on the particle surface. 110 g are obtained. Next, 600 ml of a 50 mM phosphoric acid aqueous solution containing 0.2% formaldehyde and 0.2% glutaraldehyde dissolved therein.
110 g of the above resin particles were added, and the mixture was subjected to a cross-linking reaction for 12 hours while rotating at 25 ° C. under normal pressure with a rotary evaporator, and then the resin particles in the liquid were collected by filtration, and 5 times amount of this was distilled. It was washed with water and further washed with 5 volumes of 30% ethanol aqueous solution to obtain the desired immobilized tannic acid. The immobilized tannic acid thus obtained was measured in the same manner as in Example 1, and it was found that the amount was 3.6 to 100 per 100 ml of resin particles.
It contained 4.7 g of tannic acid. The immobilized tannic acid obtained here was stored in a 30% ethanol aqueous solution at 4 ° C. for 5 days, and then subjected to the later-described adsorption capacity test.

Example 3 (Adsorption capacity test) A column packed with the immobilized oyster tannin obtained in Example 1 and a column packed with the immobilized tannic acid obtained in Example 2 were prepared. Bovine serum albumin, lysozyme, ovalbumin, ferrous sulfate ammonium salt, and caffeine were dissolved in acetate buffer at a concentration of 500 mg / 100 ml, and each sample solution was passed through at different flow rates (SV). The amount of each adsorption was quantified. Table 2 shows the results.
Shown in When the adsorbed amount was large, the adsorbed amount was measured after confirming that the sample came out to the passing liquid of the column by passing the sample liquid many times.

[0025]

[Table 2]

[0026]

EFFECTS OF THE INVENTION According to the present invention, as shown in the examples, it is possible to provide an immobilized polymer tannin in which the polymer tannin is firmly immobilized on a carrier made of a granular hydrophobic resin, and the immobilization is performed. High molecular weight tannin maintains the adsorption ability that tannins originally have, and can be used by packing in a column or the like, so that proteins, iron, alkaloid substances, etc. present in water or various aqueous solutions can be used. Efficient adsorption removal is possible. Therefore, it can be said that the industrial applicability of the present invention is very large.

Claims (2)

(57) [Claims] 1. A polymer tannin is adsorbed and fixed in a film state on the particle surface of a hydrophobic synthetic resin particle or a hydrophobic natural resin particle, and the molecules of the film-shaped polymer tannin are crosslinked. An immobilized polymer tannin characterized by the following. 2. A high molecular weight tannin is dissolved in an aqueous alcohol solution, and then hydrophobic synthetic resin particles or hydrophobic natural resin particles are dispersed in this solution, and then the alcohol content is removed from the dispersion solution to thereby remove the alcohol content from the solution. Polymeric tannin is adsorbed and fixed in a film state on the particle surface of the resin particles dispersed in, and then the resin particles in which this polymer tannin is adsorbed and fixed on the particle surface in a film state are collected and acidified. Immobilization characterized by collecting and washing the resin particles after cross-linking the molecules of the polymer tannin adsorbed and fixed in a film state on the particle surface of the resin particles by dispersing in an aqueous solution and using a crosslinking agent Method for producing polymerized tannin.