JPS6124049B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adsorption fibrous filler, and more particularly to an adsorption fibrous filler for exchange of low-molecular ions, adsorption/desorption of medium- and high-molecular substances, and immobilization of physiologically active substances. BACKGROUND ART Conventionally, fibers made of polymers having various ion exchange abilities have attracted attention as adsorbents in place of activated carbon, zeolite, or ion exchange resins, and many proposals have been made. For example, JP-A-51-136590 discloses a fibrous ion exchanger with a length of 3 to 15 mm, and the publication describes that this fibrous ion exchanger has a spherical shape like an ion exchange resin. The ion exchange rate is slow and the ion exchange rate is low.
It has been stated that fibrous materials do not have the above drawbacks and have a relatively long lifespan, whereas they are easily destroyed due to sudden changes in osmotic pressure during regeneration, and their uniform filling is easily disrupted. There is. However, when fibrous ion exchangers are packed into a column as short fibers, the functional capacity per unit volume decreases due to their bulk, and when liquid is passed through the column after filling, the fibers are compressed into a sheet at the bottom of the column. , pressure loss increases rapidly, and functions such as ion exchange and adsorption deteriorate. On the other hand, in order to avoid this, for example, as described in JP-A-53-137889, ion exchange fibers in the form of granules in which ion exchange fibers are fused together are used as fibrous adsorbents. Not only does it reduce the characteristic large surface area, but when it is packed in a column, the liquid that passes through the column tends to drift, making it difficult for the liquid to come into uniform and complete contact with the surface of the fibers packed in the column. There are drawbacks. Furthermore, Japanese Patent Application Laid-Open No. 53-43676 discloses a reaction treatment apparatus for a liquid and a substrate, which has one large cylindrical shape formed by moving a continuous bundle of fibers in a spiral manner. However, this type of structure has low pressure loss,
It has the characteristic of not easily causing eye misalignment, but on the other hand, the filtration area is large and the liquid is passed radially between the cylindrical circumference and the center, making it difficult to obtain a uniform flow and causing short passes. Easy to do. For this reason, there is a drawback that the adsorption capacity of the fibers cannot be fully utilized. The purpose of the present invention is to prevent the uneven flow of the fluid after filling the column, the pressure loss due to compaction, and the like, without impairing the characteristics of the ion exchange fiber, which has a large surface area and excellent ion exchange ability and adsorption ability. The purpose is to provide an adsorbent made of ion-exchange fibers that eliminates clogging, etc., and the other purpose is to provide an adsorbent made of ion-exchange fibers that eliminates the problem of clogging.The other purpose is to provide an adsorbent that can be used not only for low-viscosity solutions containing low-molecular-weight inorganic ions, but also for high-viscosity liquids that are extremely prone to the above-mentioned drifting and compaction. An object of the present invention is to provide a fiber filler for adsorption that is useful for immobilizing enzymes used in decolorizing sugar solutions, isomerizing glucose, converting sucrose, etc., which require treatment. That is, the basic feature of the adsorption fiber filler of the present invention is that it is a cylindrical knitted article made of continuous filament yarns having an ion exchange group and a single filament fineness of 0.01 to 50 deniers (d); The length of the object in the cylindrical direction is 3 to 30 mm. The filament yarns constituting the fiber filler for adsorption of the present invention are fibers made of polymers having various known ion exchange groups, such as hydrogen ions, metal cations, hydroxide ions, inorganic anions, acidic gases and basic gases. , medium- and high-molecular-weight organic acids and organic bases,
Pigment substances, glucose isomerase, β-galactosidase, curcoamylase, urease,
proteins such as enzymes such as asparaginase,
Cation exchange groups such as sulfonic acid groups, phosphonic acid groups, and carboxylic acid groups that can ion exchange, adsorb, or immobilize bacterial bodies and cells, anion exchange groups such as various amino groups and ammonium groups, or iminodiacetic acid that can form chelates. or iminodipropionic acid groups, or fibers made of polymers that have groups such as aldehyde groups that covalently immobilize proteins such as enzymes in addition to ion exchange groups. In particular, fibers made of polymers having groups that immobilize proteins such as enzymes, physiologically active substances such as bacterial cells and cells are preferable. Furthermore, specifically, the filament yarn constituting the adsorption fiber filler of the present invention is a polyvinyl aromatic compound that has good chemical resistance and heat resistance, and into which various ion exchange groups can be introduced. That is, polystyrene, polyα-methylstyrene, polymethylstyrene, polyxylene, polychloromethylstyrene, or copolymers thereof, and polymers having fiber-forming ability such as polyolefin, polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, etc. A two-component polymer fiber consisting of is preferred. These two-component polymer fibers can be easily obtained by known mixed spinning and composite spinning techniques, but in particular, as the adsorption fiber filler of the present invention, the above-mentioned polymer having fiber-forming properties is used as an island component, and ion A multifilamentary sea-island type composite fiber in which the exchange group-introducing polymer is a sea component is preferred. In other words, by using such sea-island composite fibers, not only can they be easily organized into a cylindrical adsorption fiber filler, which will be described later, but they can also be used as adsorption fiber fillers to reduce the dimensional change of fibers during ion exchange and regeneration, for example. It can be used as an adsorption fiber filler with a small size and a stable shape. The single yarn fineness of the above filament yarn is approximately
0.01-50 denier (d), preferably 0.1-10d,
In particular, in order to obtain a fiber filler for adsorption with a significantly large surface area, it is preferably in the range of about 0.1 to 1 d. If the fineness is less than 0.01 denier, the mechanical strength will be weak and the yarn will break easily, and if it exceeds 50 denier, the functional speed and capacity will decrease. Next, it is important that the adsorption fiber filler according to the present invention is a knitted material made of the filament yarns, and that the shape thereof is cylindrical. Here, the term "knitted fabric" includes not only knitted fabrics widely used as clothing, but also knitted fabrics such as braided strings. As specific examples of knitted fabrics, those with different knitting structures on the front and back sides, such as single jersey knitting or single warp knitting, are preferably used. Date is about 20-500g/ ^m2 , preferably 50-300g/m2
m ² and the width is 5-100mm, preferably 10-50mm
Those within the range of can be mentioned. In addition, as the braided string, braided string obtained with a normal string making machine is used, and the total fineness D is about 1000.
-50000D, preferably 2500-20000D. However, the above-mentioned knitted fabrics, especially knitted fabrics, are not just knitted fabrics, but it is important that they have a cylindrical shape, and among such cylindrical knitted fabrics, those with a length of about 3 to 30 mm are is preferable,
Furthermore, those having a diameter of 4 to 15 mm are preferably applied. In other words, when the knitted material does not have a cylindrical shape, the adsorption fiber filler is weak during column filling;
Because the repulsive force is small, it tends to be difficult to handle and uniform filling becomes difficult. Moreover, if the length is not as described above, shape retention will be poor, liquid passage resistance will be large, handling will be troublesome, and it will be difficult to fill uniformly. An example of a knitted fabric having such a cylindrical shape is shown in the first example.
This will be explained in more detail with reference to FIGS. That is, FIGS. 1 to 5 are cross-sectional views showing one embodiment of the cylindrical knitted fabric which is the adsorption fiber filler of the present invention, and the knitted fabric having the above-mentioned length and width has one end thereof.
(1) is curled and has a cylindrical or cylindrical shape. This knitted fabric may have both ends closed as shown in Figure 1, or it may be separated as shown in Figure 2.
It's okay if it's off. Also, only one end may be curled in a spiral shape as shown in Figure 3, or both ends may be curled in a spiral shape as shown in Figures 4 and 5. A spirally curled one is preferable. Furthermore, when the knitted material is a braided string, it has a cylindrical cross section as shown in FIG. 1, has no ends, and is advantageous in terms of durability. Further, the filaments constituting the knitted fabric may be fused to each other along the fiber axis direction, and this fusion improves the morphology, dimensional stability, and mechanical stability of the adsorption fiber filler of the present invention. Strength is improved. However, the degree of fusion should be within a range that does not substantially reduce the functional speed and capacity of the adsorbent fibrous filler. The method for producing the adsorption fiber filler of the present invention includes:
Although there are various methods without particular limitation, it is preferable to use multicore sea-island type composite spinning using the polyvinyl aromatic compound as a sea component and a fiber-forming polymer, preferably polyolefin, as an island component. The obtained filament yarns are doubled and knitted, and then cut into the predetermined dimensions to create a knitted string-like article. Next, pull it in the longitudinal direction to curl at least one end, or use a string making machine to create a braided string, and use these as they are.
Alternatively, it can be obtained by cutting the length to the above length, performing various chemical treatments, and introducing an ion exchange group. The adsorption fiber filler of the present invention has a cylindrical shape, so it is strong and has high repulsion.
It is easy to handle and uniformly fill columns, etc., and the fluid passing through the column does not drift. Furthermore, it is knitted without losing the large surface area of fibers, and substantially retains the functional speed and capacity of a fiber form, which is highly effective in practical use. In particular, even if the packing density is sufficiently high for enzyme-immobilized products, the flow resistance of high viscosity fluids is small, and the adsorption fiber filler does not become economically compacted, so it can maintain the specified performance for a long time. Hold. However, by setting the packing density of the adsorption fiber packing material of the present invention into a column or the like in the range of 0.15 to 0.35 g/cm ³ , the performance is significantly improved. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A chip blend consisting of 80 parts of polystyrene and 20 parts of polypropylene was used as a sea component and polypropylene was used as an island component, so that the sea-island ratio was 50:50.
A multicore sea-island type composite fiber was obtained by melt-composite spinning (island component: 16) at ℃ and then drawing 5 times (single fiber fineness: 4.3 denier, strength: 2.8 g/d). The drawn yarn (total fineness 70 denier) is knitted into a tube using a tube knitting machine with a diameter of 9cm, cut into 5cm widths, and curled from both ends in a spiral shape by applying tension in a direction parallel to the cut surface. A cylindrical knitted string-like article in the form of links was obtained. 5 parts of paraformaldehyde,
Immerse in a crosslinking solution consisting of 25 parts of acid and 70 parts of concentrated sulfuric acid at 90°C.
A crosslinking reaction was carried out for 2 hours to insolubilize the polystyrene as a sea component. Next, it was chloromethylated and trimethylammoniumated using a known method and dried. By further cutting this braided material into 8 mm pieces, a spirally curled cylindrical adsorption fiber filler was obtained (anion exchange capacity: 2.4 milliequivalents/
g, basis weight 100g/m ² ). No change in shape was observed in the two adsorption fiber fillers made of these cylindrical braided materials (the braided material before and after cutting) even when both were stirred in water. Example 2 The drawn yarn obtained in Example 1 was combined so that the total fineness was 210 denier, and wound around 16 bobbins.
A hollow braided string was produced using a string making machine. Next, it was subjected to reaction treatment according to the method of Example 1 and dried. By cutting this braided string to 8 mm, a cylindrical adsorption fiber filler was obtained (anion exchange capacity
2.3 meq/g, total fineness 7000 denier). This fiber filler for adsorption showed no change in shape even when stirred in water. Example 3 The adsorption fiber filler consisting of the knitted fabric and braided string obtained in Example 1 and Example 2 was made into a chlorine type, and 0.24 g/ml was placed in a cylindrical hollow container with an inlet at the top and an outlet at the bottom. An anion exchange reaction column for decolorizing a sugar solution was obtained by packing the same volume at a density of . Add 60 brix of cane sugar solution (absorbance value 7.5 at 410 mμ, using a 10 cm cell) to this column.
The absorbance value of the effluent was measured by flowing at a flow rate of 70° C. and SV10, and the change in decolorization rate was investigated. Table 1 shows the results and liquid flow resistance. As a comparative example, the drawn yarn obtained in Example 1 was used as Example 1.
After performing the same reaction treatment and air-drying, using a device filled with yarn cut into 8 mm pieces at a density of 0.24 g/ml and 0.12 g/ml, the results of examining the change in decolorization rate and liquid flow resistance using the above method are as follows. It is shown in Table 1. The column made of the adsorption fiber packing material of the present invention has a decolorizing performance close to that of a column made of cut fiber (thread), and has low liquid flow resistance. Columns made of threads have extremely high resistance to liquid passage, making them difficult to use in practice; lowering the packing density improves liquid permeability, but
The functional capacity becomes smaller and the decolorization rate decreases significantly.

[Table] Example 4 Polypropylene is used as the island component, polystyrene 53
After melt-spinning at 250°C (number of islands: 18) using a mixture of 5 parts of polypropylene and 6 parts of polypropylene as the sea component at a sea-island ratio of 41:59, a multicore sea-island type was created by stretching 5 times. Obtained composite fiber (single fineness
1.9 denier, strength 2.4 g/d). The threads were combined to have a total fineness of 240 denier, wound around 16 bobbins, and a hollow braided string was produced using a string making machine.
Braided string, 22 parts of sulfuric acid, 104 parts of nitrobenzene,
It was immersed in a crosslinking solution containing 0.3 parts of paraformaldehyde and reacted at room temperature for 6 hours. After washing with distilled water and methanol and drying, it was immersed in sulfuric acid and reacted at 90°C for 2 hours to sulfonate it. By cutting this braided string into 10 mm pieces, a cylindrical cation-exchangeable adsorption fiber filler was obtained (cation exchange capacity: 3.0 meq./
g, total fineness 6000 denier). Example 5 0.7 part of methylolacrylamide and 0.02 part of paraformaldehyde were added to 1.0 part of the braided string obtained in Example 4.
After adding a solution consisting of 1 part, 10 parts of sulfuric acid, and 10 parts of nitrobenzene and reacting at room temperature for 2 hours to produce acrylamide methylation, the mixture was treated with 20% dimethylamine-methanol under reflux for 2 hours to produce β-dimethylaminopropionamide methylation. did. 50 ml of suspension containing bacterial cell fragments from which glucose isomerase has been extracted (activity titer) per 1 g of reaction-treated braided string
After stirring at 50° C. for 6 hours, the braided string was taken out, added to 2.5 ml of 0.1% glutaraldehyde (PH 8.0), and treated at room temperature for 30 minutes.
Next, after drying with hot air at 60° C. for 1 hour, the material was cut to obtain 1.25 g of a cylindrical fiber filler for glucose isomerization and adsorption (total fineness of 10,000 denier). The enzyme activity titer was 8000 U/g. In addition, the activity titer of the enzyme is 0.6M glucose and 0.01M glucose as substrate solution.
Using Mgcl ₂ (PH8.2), 1 hour reaction at 60℃
The amount of enzyme that produces mg of fructose was defined as 1U. Next, the fiber filler for glucose isomerization adsorption cut into various lengths was placed in a cylindrical hollow container.
Table 2 shows the results of examining handleability, uniformity of filling, and liquid permeability when packed to a density of 0.20 g/ml. When the cut length was less than 3 mm, the handleability (shape retention) and liquid permeability deteriorated, and when it exceeded 30 mm, the handleability and filling uniformity deteriorated.

[Table] Example 6 Glucose isomerization was achieved by filling a cylindrical hollow container with an inlet at the top and an outlet at the bottom with the fiber filler for glucose isomerization and adsorption (cutting length 8 mm) obtained in Example 5. An enzyme reaction column for chemical reaction was obtained. Table 3 shows the results of examining the uniformity of filling, liquid permeability, and isomerization rate when packed at various densities. packing density
If it is less than 0.15g/ml, not only will the functional capacity decrease, but the uniformity of filling will deteriorate and the isomerization rate will decrease, and if it exceeds 0.35g/ml, the resistance to liquid passage will be very large and the liquid permeability will be poor. The uniformity of filling was also poor.
Isomerization rate is 3M with 0.005M magnesium sulfate
The conversion rate from glucose to fructose is shown when glucose (PH8.0) is passed through at 60°C at a flow rate of 18 ml/g (adsorbent)/hr.

【table】

[Table] ** Relative value of liquid resistance Example 7 Multicore sea-island composite fiber obtained in Example 4 (total fineness 80
Denier) was knitted into a tubular shape using a knitting machine, cut to a width of 5 cm, and tension was applied in the longitudinal direction to obtain a knitted string-like product that curled spirally from both ends.
This was subjected to chemical and biological treatment in the same manner as in Example 5, except that a solution consisting of 1.0 part of methylol acrylamide, 0.03 part of paraformaldehyde, 10 parts of sulfuric acid, and 1.0 part of nitrobenzene was used. Next, 60℃
After drying with hot air for 1 hour, the braided material was cut in the longitudinal direction at the center and further cut in the transverse direction to obtain 1.3 g of a cylindrical fiber filler for glucose isomerization and adsorption. The enzyme activity titer was 8400 U/g (basis weight 120 g/m ² ). Table 4 shows the results of examining the cutting length, handling properties, uniformity of filling, and liquid permeability using the method of Example 5. As a comparative example, the result of an adsorption fiber filler that was cut into 8 mm squares after being subjected to the same chemical and biological treatments as above without cutting the knitted material, forming at least one closed ring and not curling. are also shown in Table 4. When the cut length was less than 3 mm, the handleability (shape retention) and liquid permeability deteriorated, and when the cut length exceeded 30 mm, the handleability and filling uniformity deteriorated. In addition, the adsorption fiber filler made of a knitted material that forms at least one closed ring and is not curled has poor handling properties, poor filling uniformity, and poor liquid permeability.

【table】

[Table] * Comparative Example Example 8 The cylindrical fiber filler for glucose isomerization and adsorption obtained in Example 7 (cutting length: 8 mm) was filled in the same hollow container as in Example 6 to prepare a material for glucose isomerization. An enzyme reaction column was obtained. Table 5 shows the results of examining the uniformity of filling, liquid permeability, and isomerization rate when packed at various densities. If it is less than 0.15g/ml, not only will the functional capacity decrease, but the uniformity of filling will deteriorate and the isomerization rate will decrease, and if it exceeds 0.35g/ml, the resistance to liquid passage will be extremely large and the liquid permeability will be poor. The uniformity of filling was also poor. The isomerization rate indicates the conversion rate from glucose to fructose when the method of Example 5 was used and the liquid was passed at a flow rate of 20 ml/g (adsorbent)/hr.

[Table] ** Relative value of liquid flow resistance

[Brief explanation of the drawing]

1 to 5 are sectional views showing one embodiment of the adsorption fiber filler of the present invention, and in the figures, 1 indicates the end of the knitted material constituting the adsorption fiber filler.

Claims (1)

[Scope of Claims] 1. A cylindrical knitted fabric made of continuous filament yarn having an ion exchange group with a single yarn fineness of 0.01 to 50 deniers (d), wherein the length of the knitted fabric in the cylindrical direction is An adsorption fiber filler characterized by having a diameter of 3 to 30 mm. 2. The fibrous filler for adsorption according to claim 1, wherein the fibrous filler for adsorption is a filler for immobilizing a physiologically active substance.