JPS6340578B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for adsorbing ionic high molecular weight substances. More specifically, the present invention relates to a method of adsorbing ionic high molecular weight substances with an ion exchanger. BACKGROUND ART Conventionally, in fields requiring adsorption of ionic high molecular weight substances, methods of adsorption by treatment with an ion exchanger have been widely used. and,
In particular, the adsorption method using a high water content ion exchanger has high adsorption performance for ionic high molecular weight substances.
It has excellent characteristics. However, as the water content increases, the filtration resistance increases, and when used in a column, the liquid permeability resistance becomes extremely large.
This has the fatal drawback that treatment with an ion exchanger becomes difficult. The present inventors have arrived at the present invention as a result of intensive studies aimed at improving these drawbacks in a method of treating and adsorbing ionic high molecular weight substances with a high water content ion exchanger. That is, in the process of treating and adsorbing a liquid containing an ionic high molecular weight substance with an ion exchanger having a water content of 1.0 or more, the present invention requires that ion exchange fibers having an opposite charge be mixed in an amount of 0.01% or more per dry weight. This invention relates to a method for adsorbing ionic high molecular weight substances. The present invention provides a process for treating and adsorbing an ionic high molecular weight substance with a high water content ion exchanger.
On the other hand, we have surprisingly found that by mixing ion exchange fibers with opposite charges, the filtration resistance and liquid passage resistance can be significantly reduced without deteriorating the performance of the ion exchanger. The present invention provides an adsorption method using an ion exchanger that is extremely superior to conventional methods in various fields. The ion exchanger constituting the present invention means an insoluble ion exchanger having an ion exchange group. Specific examples include natural polymers such as polysaccharides such as cellulose, Cephadex, and alogalose, and synthetic organic polymers (ion exchange polymers) such as polystyrene, polyphenol, polyvinyl alcohol, polyacrylic, and polyamide. Examples include known organic ion exchangers into which ion exchange groups have been introduced. Examples of the shape of the ion exchanger include powder, fine particles, fibers, and membranes, but fibers are particularly preferred in terms of ease of handling and effectiveness. Among these, ion-exchange fibers based on fibers made of an ion-exchange polymer and a reinforcing polymer are preferred because they have sufficient operational mechanical strength and shape retention. According to the present invention, the water content of the ion exchanger is important in terms of the adsorption performance of ionic high molecular weight substances and is usually 1.0 or more, but if it is too small, the adsorption performance will decrease, and if it is too large, it will be difficult to handle. Therefore, the range is preferably 1.5 to 100, and most preferably 2.0 to 20. The moisture content here refers to the Na type (Cl type) cation (anion) exchanger that is immersed in distilled water and then heated in a household centrifugal dehydrator.
The weight (W) was immediately measured by centrifugal dehydration for a minute to remove surface moisture, and the weight (W ₀ ) was determined after being completely dried, and the value was determined from the following formula. Water content = W - W ₀ / W ₀ The ion exchange fiber constituting the present invention is usually an insoluble synthetic organic ion fiber with a diameter of 0.01 to 100μ, preferably 1 to 100μ, which is obtained by introducing an ion exchange group into the above-mentioned ion exchange polymer. means replacement fiber. Among them, fibers made of ion-exchange polymers and reinforcing polymers, preferably multicore mixed or composite fibers with ion-exchange polymers as the main sheath component and reinforcing polymers as the core component, are used as base materials. Ion-exchange fibers may be used as long as they have sufficient mechanical strength and shape retention for operation. The proportion of the reinforcing polymer is usually 10 to 90%, but if it is too small, the mechanical strength will be weakened, and if it is too large, the adsorption performance will be reduced, so a range of 20 to 80% is preferable.
As the ion exchange polymer, poly(monovinyl aromatic compounds), particularly polystyrene compounds, are preferred because they have excellent chemical resistance and heat resistance, and can be produced by repeating the operation many times over a long period of time. Further, as the reinforcing polymer, poly-α-olefins such as polypropylene and polyethylene are preferable because they have excellent chemical resistance. The fibers may also be partially fibrillated. The moisture content of the oppositely charged ion exchange fibers in the present invention is extremely important for the effectiveness of the present invention, and is usually
1.0 or more, but if it is too small, you will have to increase the mixing amount, and if it is too large, it will be difficult to handle, so 1.5 to 100 is preferable, especially
A range of 2.0 to 20 is most preferred. The forms of such ion-exchange fibers include staple fibers, filament yarns, felts, woven fabrics, non-woven fabrics,
Any known forms such as uneven objects, fiber bundles, string-like objects, and paper, as well as cut aggregates, can be used. Especially 0.1~30mm, preferably 0.5~10mm
When mixed with an ion exchanger, the short fiber form has excellent bulkiness, good liquid permeability, and excellent effectiveness. Ion exchange groups in the present invention include cation exchange groups such as sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, aminocarboxylic acid groups, and aminophosphoric acid groups, primary to tertiary amino groups, quaternary ammonium groups,
Examples include anion exchange groups such as polyamine groups and amidoxime groups. The ion exchange group is appropriately selected depending on the type of ionic polymer. The present invention utilizes a batch method in which an ion exchanger and an ion exchange fiber with an opposite charge are added to a liquid containing an ionic high-molecular weight substance, stirred, and then overtreated to adsorb the mixture, and a fixed layer is formed by mixing the two. Examples include a fixed bed method in which a solution containing an ionic high molecular weight substance is passed through the solution after treatment, and the latter method is particularly preferred since it is easy to operate. Among these, a method in which a liquid containing an ionic high molecular weight substance is passed through a column filled with the mixture is particularly preferred because of its high adsorption performance. Although the mixing method is arbitrary, a method of adding the ion-exchange fiber-containing liquid to the ion-exchanger-containing liquid under stirring is particularly preferable because mixing is performed sufficiently. The mixing ratio of ion exchange fiber to ion exchanger in the present invention is usually 0.01% or more per dry weight. This mixing ratio varies somewhat depending on the water content of the fibers, but if it is too small, the effect of the present invention cannot be fully exhibited, and if it is too large, uneven flow may occur when packed in a column. A range of 0.1 to 50% is preferred, especially a range of 1 to 30%, especially a range of 1 to 10%. Also polyamide, polyester, Teflon,
Reinforcing fibers such as glass, in particular short fibers, can optionally be mixed at the same time. The ionic high molecular weight substance as used in the present invention means a high molecular weight substance that is adsorbed on an ion exchanger. Specific examples include antibiotics such as streptomycin and penicillin, dyes in various sugar solutions,
Pigments in blood and plasma, pigment substances such as dyes, proteins, glycoproteins, nuclear proteins, lipoproteins, peptides, enzymes, pyrogens, bacterial cells,
Microorganisms, protein substances whose main components are peptides such as cells such as red blood cells, white blood cells, and platelets, nucleic acids such as viruses, hormones, nucleotides, alkaloids, lipids, steroids, iron oxide,
Examples include colloidal substances such as inorganic colloidal substances such as iron hydroxide and silica, and organic colloidal substances. The method of the present invention is particularly excellent in adsorbing protein substances, nucleic acids, and colloid substances;
It is particularly effective for adsorbing protein substances. The method of the present invention can be applied to the removal, immobilization, recovery, purification, concentration, and separation of the ionic high molecular weight substances. Moreover, according to the method of the present invention, it is possible to achieve extremely high performance adsorption of ionic high molecular weight substances from the liquid to be treated, and to do so efficiently and efficiently without worrying about problems such as filtration resistance and liquid flow resistance. This has the advantage that it can be carried out stably. Examples are shown below, but the invention is not limited thereto. Example 1 An aqueous solution containing a predetermined amount of cation exchange fibers with a water content of 1.5 or 3.0 is added to an aqueous solution containing 20 parts of anion exchange fibers with a water content of 4.5 under stirring and mixed, and then packed into a column to increase the liquid flow resistance. I looked into it. Table 1 shows the results of liquid passage resistance relative to the case where cation exchange fiber was not mixed (comparative example). A mixture of 20 parts of the above anion exchange fiber and 4 parts of cation exchange fiber with a moisture content of 3.0 was mixed with a 0.1% bovine blood albumin aqueous solution (0.05M, PH7.0 phosphate buffer).
10,000 parts were added and stirred at room temperature for 3 hours to adsorb albumin on the anion exchanger. Next, the amount of albumin in the filtrate after filtration was determined to determine the amount of adsorption, which was 300 mg/g (anion exchange fiber).
As a comparative example, the adsorption amount was determined using the same procedure for a product that did not contain cation exchange fibers.
300 mg/g, but the method of the present invention was far superior in terms of filterability. From the above results, it can be seen that the method of the present invention has very low filtration resistance and liquid passage resistance, and has the same adsorption amount as the comparative example.

[Table] Example 2 In an aqueous solution containing 20 parts of a cation exchange fiber with a moisture content of 7.5 converted into Ca type with an aqueous calcium chloride solution,
After adding and mixing an aqueous solution containing a predetermined amount of anion exchange fiber with a water content of 2.0 or 4.5 under stirring, the column was filled and the liquid passage resistance was examined. Table 2 shows the relative liquid passage resistance results for the case where no anion exchange fiber was mixed (comparative example). 20 parts of the Ca-type cation exchange fiber has a water content of 4.5.
0.1% of a mixture of 4 parts of anion exchange fiber
10,000 parts of bovine blood hemoglobin aqueous solution (0.05M, PH6.6 phosphate buffer) was added and stirred at room temperature for 3 hours to adsorb hemoglobin onto the cation exchanger. Next, the amount of hemoglobin in the filtrate after filtration was determined to determine the amount of adsorption, which was 400 mg/g (cation exchange fiber). As a comparative example, the adsorption amount was determined in the same manner using a product without anion exchange fibers, and it was found to be 400 mg/g, but the method of the present invention was far superior in terms of filterability. From the above results, it can be seen that the method of the present invention has a very small filtration resistance and the same adsorption performance as that of the comparative example.

[Table] Example 3 The liquid passage resistance was examined by the method of Example 2, except that a powdered cation exchange resin with a water content of 5.0 was used as the cation exchanger. Table 3 shows the relative liquid passage resistance results for the case where no anion exchange fiber was mixed (comparative example). Further, when the amount of hemoglobin adsorbed was examined by the method of Example 2, it was found to be 100 mg/g (powdered cation exchange resin) in both cases. The above results show that the present invention is also effective for powdered cation exchange resins.

[Table] The cation exchange fibers, anion exchange fibers, and powdered cation exchange resins used in Examples 1 to 3 and each comparative example were manufactured by the following method. Multicore sea-island composite fiber (undrawn yarn) [sea component (polystyrene polypropylene)/island component (polypropylene) = (474)/49 (number of islands 16, fiber diameter
34μ)] to a length of 1 mm to obtain a cut fiber. 1 part by weight of the cut fiber was mixed with commercially available 1 part by weight.
In addition to the crosslinking/sulfonation solution consisting of 7.5 parts by volume of grade sulfuric acid and 0.15 parts by weight of paraformaldehyde,
After reaction treatment for a period of time, it was washed with water. Next, by treating with alkali and washing with water, a cation exchange fiber having a sulfonic acid group and a water content of 1.5 was obtained (exchange capacity: 2.8 meq/g-Na). A cation exchange fiber with a moisture content of 3.0 was obtained in the same manner as above except that 0.04 parts by weight of paraformaldehyde was used (exchange capacity 3.0 meq/g-Na).
In addition, a cation exchange fiber with a moisture content of 7.5 was obtained in the same manner as above except that 0.015 parts by weight of paraformaldehyde was used (exchange capacity 3.2 meq/g).
−Na). One part by weight of the cut fiber was added to a crosslinking solution consisting of 5 parts by volume of commercially available primary sulfuric acid, 0.5 parts by volume of water and 0.2 parts by weight of paraformaldehyde, and a crosslinking reaction was carried out at 80°C for 4 hours. Then chloromethyl ether
The crosslinked thread was added to a solution consisting of 8.5 parts by volume and 1.5 parts by volume of stannic chloride, and the mixture was reacted at 30°C for 1 hour. After the reaction was completed, it was washed with 10% hydrochloric acid, distilled water, and acetone.
chloromethylated yarn in 30% trimethylamine aqueous solution
The mixture was added to 10 parts by volume, aminated at 30°C for 1 hour, and washed with water. By further treating with hydrochloric acid and washing with water, an anion exchange fiber with a water content of 2.0 having trimethylammonium methyl groups was obtained (exchange capacity
2.4 meq/g-Cl). In addition, the water content was determined in the same manner as above, except that the crosslinking reaction was carried out at 60°C for 2 hours.
4.5 anion exchange fibers were obtained (exchange capacity 2.1 meq/g-Cl). The polystyrene chips were processed in a grinder to obtain powdered polystyrene with a particle size of 50-250 μm. A powdered cation exchange resin having a water content of 5.0 was obtained in the same manner as above except that 0.02 parts by weight of paraformaldehyde was used (exchange capacity: 4.5 meq/g-Na).

Claims (1)

[Claims] 1. Water content of liquid containing ionic high molecular weight substance is 1.0.
A method for adsorbing an ionic high molecular weight substance, characterized in that in the above-mentioned process of treating and adsorbing with an ion exchanger, 0.01% or more of ion exchange fiber having an opposite charge is mixed per dry weight.