JP2019209223A - Fiber bundle-like adsorbent - Google Patents

Abstract

To provide an adsorption module agent having low permeation resistance and excellent in adsorption performance even at high flow rate.SOLUTION: An adsorbent adsorption module in this invention comprises plural fiber bundles and a housing storing the fiber bundles. The fiber bundle includes adsorptive monofilaments of 10,000 or more but 100,000,000 or less, and the diameter D of the monofilament is 100 nm or more but 500 nm or less. Besides, the porosity y in the fiber bundle is 20-75 vol% and the porosity z out of the fiber bundle is 5-50 vol%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a fiber bundle adsorbent suitable for removing harmful substances in water and a method for producing the fiber bundle adsorbent.

  In recent years, in the field of water treatment such as water purification, wastewater treatment and seawater desalination, for example, removal of arsenic contained in groundwater, phosphorus contained in wastewater, fluorine, heavy metal elements, boron contained in seawater, etc. The demand is growing. For these harmful substances, adsorption removal with an adsorbent is being studied as one of the methods for removing them from water.

  Various shapes such as particles, fibers, and powders are used as the shape of the adsorbent, and these adsorbents are used by being filled in a container such as a tank or a column. However, when water is passed at a high flow rate, it is necessary to increase the adsorption rate by maintaining a high specific surface area in order to maintain the adsorption performance.

  For example, Patent Document 1 discloses an adsorbent that effectively adsorbs (ion exchange) phosphorus contained in wastewater by introducing ion exchange groups using porous cellulose having a high specific surface area as a base material. ing.

  Patent Document 2 discloses a high specific surface area capable of effectively removing strontium in radioactive polluted water by generating barium silicate through a process of reacting barium hydroxide with a soluble alkali metal salt of silicic acid. An adsorbent is disclosed.

JP 2013-103207 A JP 2016-83656 JP

  The adsorbents described in Patent Documents 1 and 2 have a problem that a high permeation resistance is produced when water is passed under a high flow rate condition.

  In view of the background of such prior art, the present invention has an object to provide an adsorption module having a small permeation resistance and excellent adsorption performance even at a high flow rate in removing harmful substances contained in a fluid such as water or gas. To do.

  In order to achieve the above object, as a result of intensive studies to solve the above problems, it has been found that an adsorption module capable of solving the problems can be provided by having the following configuration, and the present invention has been completed.

That is, the adsorption module of the present invention is an adsorption module comprising a plurality of fiber bundles and a housing that accommodates the fiber bundles, and the fiber bundles have an adsorption property of 10,000 or more and 100 million or less. The fiber contains fibers, the diameter D of the single fiber is 100 nm or more and 500 nm or less, the void fraction y in the fiber bundle is 20 vol% or more and 75 vol% or less, and the void fraction z outside the fiber bundle is 5 vol% or more and 50 vol%. The adsorption module has a volume% or less.
Fiber filling rate x = A / P
Porosity in fiber bundle y = B / (A + B)
Porosity outside fiber bundle z = 1-x / (1-y)
A: Fiber volume in fiber bundle B: Cavity volume in fiber bundle C: Cavity volume outside fiber bundle P: Housing capacity P = A + B + C

  In the adsorption module, fluid flows through the gaps between the single fibers and between the fiber bundles and between the housing and the fiber bundles. In the present invention, the balance between the gap between the single fibers and the gap between the fiber bundles and between the housing and the fiber bundle reduces the permeation resistance and provides high adsorption performance even at high flow rates. Suitable for realization.

It is sectional drawing which shows one Embodiment of the module of this invention.

1. Adsorption Module An adsorption module 1 that is an embodiment of the present invention will be described below with reference to the drawings.

(1) Module Configuration As shown in FIG. 1, the adsorption module 1 of this embodiment includes a plurality of fiber bundles 2 and a housing 3 that accommodates the fiber bundles 2.

  In FIG. 1, for convenience of explanation, the longitudinal direction of the fiber bundle 2 (same as the longitudinal direction of the single fiber 5 included in the fiber bundle) is drawn so as to coincide with the longitudinal direction of the housing 3. In other words, it is drawn so that the radial direction of the fiber bundle 2 (that is, the single fiber) and the radial direction of the housing 3 coincide. However, the direction of the fiber bundle 2 is not limited to this, and can be in various directions. For example, the fiber bundle 2 may constitute a woven fabric or a knitted fabric.

(2) Fiber bundle The fiber bundle 2 includes 10,000 or more and 100 million or less single fibers 5. The single fiber will be described later.

  In FIG. 1, the cross section of the fiber bundle 2 is circular, but the cross sectional shape of the fiber bundle is not particularly limited, and may be irregular. Examples of the “deformed” cross section include a polygonal shape, a flat shape, a lens shape, and a so-called multi-lobal shape such as a trilobal section and a six-leaf section. The multi-lobal shape is a shape having the same number of concave portions as three to eight convex portions.

  The fiber bundle diameter Db is represented by Db = (d1 + d2) / 2 by the diameter d1 of the smallest circle including the fiber bundle section and the diameter d2 of the largest circle that fits inside the fiber bundle section.

  The number of single fibers in the fiber bundle is 10,000 or more and 100 million or less. The surface area of the flow path in a fiber bundle becomes large because the number of single fibers in a fiber bundle is 10,000 or more. Moreover, a high permeation | transmission flow rate can be obtained because the number of the single fibers in a fiber bundle is 100 million or less.

(3) Single fiber (3-1) Shape The cross-sectional shape of the single fiber is not particularly limited. As the cross-sectional shape of the single fiber, for example, a shape similar to the shape exemplified for the fiber bundle can be adopted. The preferred cross-sectional shape of the single fiber is irregular. The irregular shape increases the specific surface area and the gap when forming the fiber bundle, so that the representative diameter of the voids described later is sufficiently larger than the single fiber diameter, resulting in low permeation resistance.

  In the case of an irregular cross section, the degree of irregularity of the fiber cross sectional shape is preferably 2.0 or more and 6.0 or less. The irregularity referred to here is a value obtained by dividing the diameter of the smallest circle including the entire cross section by the largest diameter that fits in the cross sectional shape. By setting the degree of irregularity to 2.0 or more, irregularities in the irregular section become large, and the effect of increasing the gap when the specific surface area and the fiber assembly are obtained can be sufficiently exhibited. On the other hand, when the degree of profile is 6.0 or less, the fiber is not easily damaged in each step, and problems such as yarn breakage are easily avoided.

  The diameter Di of the single fiber may be 100 nm or more and 500 nm or less. When the fiber diameter is 100 nm or more, the strength as a base material is maintained, and the single fiber is not broken under a high flow rate condition. Moreover, it needs to be 1000 nm or less, and it is more preferable that it is 500 nm or less. When the fiber diameter is 1000 nm or less, a sufficient specific surface area is obtained, and excellent adsorption performance is exhibited under high flow rate conditions.

  The single fiber diameter Di described here is determined from the average of the circumscribed circle radius R and the inscribed circle radius r of each single fiber. For the circumscribed circle radius R and the inscribed circle radius r, for example, 20 single fibers are randomly selected from a cross-sectional image obtained by CT scan, and the circumscribed circle and the inscribed circle are drawn by image analysis software. It is calculated by averaging.

(3-2) Adsorbability The single fiber has adsorbability. The configuration that the single fiber has for adsorbing the target substance is not limited to a specific one. For example, a single fiber may have a base material and adsorbent particles supported on the surface of the base material, or a polymer that is grafted to the surface of the single fiber and has an adsorbing functional group side chain. You may have.

(3-2-1) Structure of single fiber having base material and adsorbent particles (a) Base material The material constituting the base material is not particularly limited. For example, polyolefin, halogenated polyolefin, polyacrylonitrile, polyvinyl compound, polycarbonate, Mainly composed of poly (meth) acrylate, polysulfone, polyethersulfone, polyamide, polyester, cellulose ester and the like. Here, the “main component” means that the content is 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more.

  Specific examples of polyolefin include polyethylene and polypropylene.

  Specific examples of the halogenated polyolefin include polyvinyl chloride, PTFE, and polyvinylidene fluoride.

  Specific examples of the polyamide include nylon 6, nylon 66, nylon 11, and nylon 12.

  Specific examples of the polyester include an aromatic polyester composed of an aromatic dicarboxylic acid portion and a glycol portion, an aliphatic polyester composed of an aliphatic dicarboxylic acid and a glycol portion, a polyester composed of a hydroxycarboxylic acid, and a copolymer thereof. Can be mentioned.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Specific examples of the glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and the like.

  Specific examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and the like.

  Polyesters can also be copolymerized within a range that does not greatly change their properties. Examples of the copolymer component include 5- (alkali metal) sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid, and polyvalent carboxylic acids other than the above-described aromatic dicarboxylic acids.

  Specific examples of the cellulose ester include, for example, cellulose acetate, cellulose propionate, cellulose butyrate, mixed cellulose ester in which three hydroxyl groups present in the glucose unit of cellulose are blocked with two or more acyl groups, and derivatives thereof. Etc.

  Moreover, these materials may combine 2 or more types, and may contain additives other than the said illustration. Additives here include other polymers, plasticizers, antioxidants, organic lubricants, crystal nucleating agents, organic particles, inorganic particles, end-capping agents, chain extenders, ultraviolet absorbers, infrared absorbers, and coloring prevention. Agents, matting agents, antibacterial agents, antistatic agents, deodorants, flame retardants, weathering agents, antistatic agents, antioxidants, ion exchange agents, antifoaming agents, colored pigments, fluorescent whitening agents, dyes, etc. Can be mentioned.

(B) Adsorbent particles The composition of the adsorbent particles is not particularly limited, and may include, for example, at least one metal selected from silver, copper, iron, titanium, zirconium, and cerium. The metal contained in the adsorptive particles can be arbitrarily selected depending on the object to be adsorbed.

  For example, when the adsorption target is boron, arsenic, phosphorus, or fluorine ions, the adsorbent particles preferably contain at least one compound selected from metal oxides, metal hydroxides, and metal hydrates. .

  Moreover, it is preferable that the particulate adsorbent particles contain a metal hydroxide or a metal hydroxide from the viewpoint of adsorption capacity.

  Examples of metal hydroxides and metal hydroxides include rare earth element hydroxides, rare earth element hydroxides, zirconium hydroxide, hydrous zirconium oxide, iron hydroxide, and hydrous iron oxide. As rare earth elements, scandium Sc of atomic number 21 and yttrium Y of 39 according to the periodic table of elements, lanthanoid elements of 57 to 71, that is, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, cadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu are applicable. For example, if the adsorption target is arsenic, the preferred element is cerium. Tetravalent cerium is preferred. Mixtures of these hydroxides and / or hydrous oxides are also useful.

  The water content of the metal particles is preferably 1% by mass or more, and more preferably 5% by mass or more. When the content is 1% by mass or more, an adsorption site can be imparted to the inside of the particle, and the adsorption capacity is sufficient. Moreover, it is preferable that it is 30 mass% or less, and it is more preferable that it is 20 mass% or less. By being 30% by mass or less, the density of the adsorption sites inside the particles can be increased, and the adsorption capacity is sufficient.

(3-2-2) Configuration in which the single fiber has a graft polymer As a component that contributes to the adsorptivity of the single fiber, the single fiber includes a polymer having a side chain that is grafted to the surface of the single fiber and includes an adsorptive functional group. But you can.

  The kind of the adsorptive functional group is not particularly limited, and examples thereof include a functional group containing one or more elements selected from nitrogen, sulfur, phosphorus, and oxygen. These elements have high affinity with metals. Specifically, the adsorptive functional group is preferably at least one selected from the group consisting of an amino group, an aryl sulfide group, an arylalkyl sulfide group, a phosphate group, and a carboxylic acid group. Or an arylalkylsulfide group, more preferably an ethylenediamine group or a benzyl mercaptan group.

(4) Gaps in fiber bundle In the adsorption module of the present invention, the voids in the fiber bundle (void ratio in the fiber bundle) are 20 vol% or more and 75 vol% or less. When the porosity is 20% by volume or more, sufficient flow paths can be secured and excellent water flow performance can be exhibited. On the other hand, when the porosity is 75% by volume or less, sufficient contact between single fibers is secured, and the structure of the fiber bundle is stabilized.

The void fraction y in the fiber bundle is expressed by the following formula.
y = B / (A + B)
A: Fiber volume in the fiber bundle B: Void volume in the fiber bundle The void inside the fiber bundle refers to a region where no structure exists in the fiber bundle.

  The fiber volume A in the fiber bundle and the void volume B in the fiber bundle are obtained by, for example, obtaining an image of a cross section (cross section) perpendicular to the longitudinal direction of the fiber bundle by CT scan and binarizing the image by image analysis software. Calculated. In the example shown in FIG. 1, the hatched portion (triangle) in the enlarged view surrounded by the dotted line is the single fiber 5, and the white portion 42 is the void in the fiber bundle. In calculating the porosity y, the area of each region may be regarded as a volume.

  In the cross-sectional image of the fiber bundle, the outer edge of the fiber bundle is defined by the outer edge of the single fiber (outermost single fiber) located at the outermost part of the fiber bundle and the common tangent of two adjacent outermost single fibers. . A + B is the apparent volume of the fiber bundle including voids. When calculating the porosity based on the cross-sectional area, the area of the region surrounded by the outer edge of the outermost single fiber in the cross-sectional image of the fiber bundle and the common tangent of two adjacent outermost single fibers is the fiber bundle. The apparent volume (A + B).

(5) Space outside fiber bundle The void ratio outside fiber bundle is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 25% by volume or more. When the void ratio outside the fiber bundle is 1% by volume or more, the fluid is dispersed inside the fiber bundle and the outside of the fiber bundle, and the permeation resistance during water passage can be reduced. When the void ratio outside the fiber bundle is 10% by volume or more, the fluid is easily dispersed from the outside of the fiber bundle, and the permeation resistance during water passage can be reduced. Moreover, it is preferable that the porosity outside a fiber bundle is 50 volume% or less. When the void ratio outside the fiber bundle is 50% by volume or less, the strength of the fiber structure is secured, and a higher order structure composed of single fibers and fiber bundles is maintained.

The void outside the fiber bundle is a portion (indicated by reference numeral “4” in FIG. 1) excluding the void in the fiber bundle in the void (region where no fiber is present) in the housing. That is, the volume of the fiber bundle outer space is a value obtained by subtracting the apparent volume (A + B) of the fiber bundle from the housing capacity, and the fiber bundle outer void ratio z is expressed by the following equation.
z = C / P
= {P- (A + B)} / P
= 1-x / (1-y)
P: Housing capacity P = A + B + C
C: void volume outside the fiber bundle x: fiber filling rate x = A / P
The porosity outside the fiber bundle is calculated, for example, by binarizing a cross-sectional image obtained by CT scan using image analysis software.

(6) Fiber structure The fiber bundle can be used as an adsorbent as it is, but it may constitute a fiber structure.
The fiber structure is composed of a plurality of fiber bundles, and examples thereof include woven fabrics, knitted fabrics, and nonwoven fabrics.

The woven structure of the fiber structure is not particularly limited. For example, a three-layer structure such as a plain weave, a diagonal weave, and a satin weave, a changed structure, a changed structure such as a changed oblique weave, a vertical double weave, a weft double weave, etc. One-sided double weave, vertical pile weave such as warp velvet, towel, velor, etc., weft pile weave such as benjin, weft velvet, velvet, cole heaven and the like. In addition, the textile fabric which has these woven structures can be woven by a normal method using normal looms, such as a rapier loom and an air jet loom.
There is an opening (hereinafter referred to as op) as a value indicating the distance between fiber bundles constituting the woven or knitted fabric, and is defined by the following equation.
op (μm) = {25400 / n (pieces / inch)} − Db (1)
n (piece / inch): number of meshes per inch of woven or knitted fabric, Db: diameter of fiber bundle (μm) constituting the woven or knitted fabric
A value op / Db obtained by dividing the opening by the fiber bundle diameter is 0.5 or more, preferably 0.7 or more, and more preferably 0.8 or more. Moreover, it is 3.0 or less, it is preferable that it is 2.5 or less, and it is still more preferable that it is 2.0 or less. When op / Db is 0.5 or more, clogging is unlikely to occur during water flow, and permeation resistance is unlikely to increase. By being 3.0 or less, when the raw water is passed through the filter for liquid filtration, the removal target component in the raw water can be suitably removed without causing a short pass of the raw water.

  The kind of knitted fabric is not particularly limited, and may be a weft knitted fabric or a newly knitted fabric. Preferred examples of the weft knitting structure include flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, bristle knitting, and the like. Preferred examples include single atlas knitting, double cord knitting, half tricot knitting, back hair knitting, jacquard knitting and the like. The knitting can be knitted by a normal method using a normal knitting machine such as a circular knitting machine, a flat knitting machine, a tricot knitting machine, and a Raschel knitting machine.

The basis weight of these woven or knitted fabrics is 300 g / m ² or more, preferably 350 g / m ² or more, more preferably 400 g / m ² or more. Moreover, it is 1500 g / m ² or less, preferably 1000 g / m ² or less, and more preferably 800 g / m ² or less. When the basis weight of the woven or knitted fabric is 300 g / m ² or more, the component to be removed in the raw water can be suitably removed without causing a short pass of the raw water when the filter for liquid filtration is used. Moreover, it is hard to produce clogging by being 1500 g / m < ² > or less, and the permeation | transmission resistance at the time of water flow can be made small.

(7) Housing As shown in FIG. 1, the housing 3 is a cylindrical member and accommodates the fiber bundle 2 therein.

  However, in the present invention, the shape of the housing is not limited to a cylinder. As the cross-sectional shape of the housing, various shapes can be adopted as in the cross-sectional shape of the fiber bundle.

2. Fiber surface treatment When a single fiber has a substrate and particles carried on the substrate, it is preferable to perform a surface treatment of the substrate. By performing the surface treatment of the base material, a functional group is induced on the surface of the base material, and the functional group and the metal particle interact to support the metal particle on the base material in a state where the particle size is small. It becomes possible. Alternatively, it is possible to induce a functional group on the surface of the base material and to graft a polymer having an adsorbing functional group side chain starting from the functional group.

  The surface treatment method is not particularly limited, and examples include corona discharge treatment, plasma treatment, alkali treatment, electron beam radiation treatment, photochemical treatment such as vacuum ultraviolet treatment, and chemical treatment such as sulfonation, amination, carboxylation, and nitration. It is done.

  The corona discharge treatment and the plasma treatment are preferably performed in an atmosphere of a specific gas because the efficiency of inducing a functional group is good. Examples of the gas include oxygen, nitrogen, carbon dioxide gas, and mixed gas thereof. The processing intensity at that time can be arbitrarily set. The chemical treatment method is not particularly limited, and examples thereof include sulfonation using sulfuric acid, amination using ammonia, and carboxylation using carbon dioxide.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

(Example 1)
Plain weaving using a fiber bundle having a bundle diameter of 500 μm in which a polyethylene terephthalate fiber having an irregularity of 1.0 and a fiber diameter of 300 nm and a nylon fiber having an irregularity of 2.0 and a fiber diameter of 100 nm are bundled in a ratio of 1: 3. A woven fabric was produced with a warp bundle and a weft bundle having a mesh number of 40 (pieces / inch).

  Next, both surfaces of the woven fabric were subjected to corona discharge treatment in a nitrogen atmosphere at a surface treatment strength of 30 W · min / m 2. The obtained woven fabric was immersed in a nano-colloid solution of cerium oxide (solvent: water, concentration: 5%) at room temperature for 1 day. Then, the excess nano colloidal solution of cerium oxide was removed by washing with water.

  Further, the woven fabric was immersed in a 4.0% by mass aqueous sodium hydroxide solution for 72 hours to dissolve the polyethylene terephthalate fiber, thereby obtaining an adsorbent in which cerium oxide was bonded to the functional group of the nylon fiber.

  The adsorbent obtained by the above production method was laminated with a porosity of 10% on a 10.0 cm cubic container having a top surface and a bottom surface having a diameter of 6.0 cm, and the top surface port of the container was connected to a booster pump and the bottom surface port of the container to a flow meter. . When a 60% by mass arsenic acid aqueous solution was diluted with distilled water and raw water having a concentration of 50 ppb in terms of arsenic was fed from the upper surface of the container at a water pressure of 60 kPa, the permeate flow rate from the lower surface of the container was 6.1 L / min. It was. Further, when the arsenic concentrations of the raw water and the permeate were quantified by ICP emission analysis, the arsenic removal rate was 87%.

(Example 2)
Polyethylene terephthalate fiber having an irregularity of 2.0 and a fiber diameter of 500 nm was immersed in a 4% by mass sodium hydroxide aqueous solution for 0.5 hour.
A liquid obtained by mixing glycerol diglycidyl ether and ethylenediamine in a molar ratio of 1: 1 to this fiber is made of nylon having about 750,000 polyethylene terephthalate fibers and a degree of deformation of 2.0 and a fiber diameter of 500 nm using a nozzle having a diameter of 250 μm. A hot air drying oven at 200 ° C. was delivered over 10 minutes while bundling and coating approximately 250,000 fibers. Then, the low molecule which has not couple | bonded with the fiber was removed by water washing.

  Further, this fiber bundle is bundled in a columnar shape with a diameter of 10.0 cm and immersed in 3.7% by mass of hydrochloric acid for 72 hours to dissolve nylon fibers and obtain an adsorbent in which amino groups are bonded to polyethylene terephthalate fibers. It was.

  The adsorbent obtained by the above production method is filled in a cylindrical container having a diameter of 10.3 cm and a height of 30 cm having a mouth having a diameter of 6.0 cm on the upper surface and the lower surface, and bonded with bisphenol to the gap between the outermost surface of the adsorbent and the inner wall of the container. The container upper surface port where the agent was packed and fixed was connected to a booster pump and the container lower surface port to a flow meter. When a 60% by mass aqueous arsenic acid solution was diluted with distilled water and raw water having a concentration of 50 ppb in terms of arsenic was sent from the upper surface of the container at a water pressure of 60 kPa, the permeate flow rate from the lower surface of the container was 3.8 L / min. It was. Further, when the arsenic concentrations in the raw water and the permeate were quantified by ICP emission analysis, the arsenic removal rate was 85%.

(Comparative Example 1)
Using a fiber bundle with a bundle diameter of 500 μm obtained by bundling nylon fibers with an irregularity of 2.0 and a fiber diameter of 100 nm, a woven fabric was produced using a plain weaving machine with a mesh number of warp bundles and weft bundles of 50 (pieces / inch).

  Next, both surfaces of the woven fabric were subjected to corona discharge treatment in a nitrogen atmosphere at a surface treatment strength of 30 W · min / m 2. The obtained woven fabric was immersed in a nano-colloid solution of cerium oxide (solvent: water, concentration: 5%) at room temperature for 1 day. Thereafter, the excess cerium oxide nanocolloid solution was removed by washing with water to obtain an adsorbent in which cerium oxide was bonded to the functional group of the nylon fiber.

  The adsorbent obtained by the above production method was laminated with a porosity of 10% on a 10.0 cm cubic container having a top surface and a bottom surface having a diameter of 6.0 cm. . When a 60% by mass aqueous arsenic acid solution was diluted with distilled water and raw water having a concentration of 50 ppb in terms of arsenic was sent from the upper surface of the container at a water pressure of 60 kPa, the permeate flow rate from the lower surface of the container was 2.0 L / min. It was. Further, when the arsenic concentrations of the raw water and the permeate were quantified by ICP emission analysis, the arsenic removal rate was 18%.

(Comparative Example 2)
Polyethylene terephthalate fiber having an irregularity of 2.0 and a fiber diameter of 500 nm was immersed in a 4% by mass sodium hydroxide aqueous solution for 0.5 hour.
To this liquid in which glycerol diglycidyl ether and ethylenediamine are mixed at a molar ratio of 1: 1, the above-mentioned polyethylene terephthalate fiber and a nylon fiber having an irregularity of 2.0 and a fiber diameter of 500 nm are mixed with a fiber number ratio of 1: 3 and a diameter of 10 After being bundled and immersed in a cylindrical shape having a height of 0.0 cm and a height of 30 cm, the solution was drained, and then left standing in a hot air drying furnace at 200 ° C. for 10 minutes. Then, the low molecule which has not couple | bonded with the fiber was removed by water washing.

  Furthermore, the nylon fiber was dissolved by immersing in 3.7% by mass of hydrochloric acid for 72 hours to obtain an adsorbent in which an amino group was bonded to the polyethylene terephthalate fiber.

  The adsorbent obtained by the above production method is filled in a cylindrical container with a diameter of 10.3 cm and a height of 30 cm having a mouth with a diameter of 6.0 cm on the upper surface and lower surface, and bisphenol adheres to the gap between the outermost surface of the adsorbent and the inner wall of the container. The container upper surface port where the agent was packed and fixed was connected to a booster pump and the container lower surface port to a flow meter. When a 60% by mass aqueous arsenic acid solution was diluted with distilled water and raw water having a concentration of 50 ppb in terms of arsenic was sent from the upper surface of the container at a water pressure of 60 kPa, the permeate flow rate from the lower surface of the container was 0.2 mL / min. It was. Further, when the arsenic concentrations in the raw water and the permeate were quantified by ICP emission analysis, the arsenic removal rate was 99%.

  The adsorption module of the present invention removes harmful substances contained in fluids such as water and gas, specifically, arsenic contained in groundwater, phosphorus contained in wastewater, fluorine, boron contained in seawater, etc. It can be preferably used for removal of water.

DESCRIPTION OF SYMBOLS 1 Module 2 Fiber bundle 3 Housing | casing 4 Fiber bundle outer space 5 Single fiber 42 Fiber bundle inner space

Claims (6)

An adsorption module comprising a plurality of fiber bundles and a housing for housing the fiber bundles,
The fiber bundle includes a single fiber having an adsorptivity of 10,000 to 100 million,
The diameter D of the single fiber is 100 nm or more and 500 nm or less, and
The void ratio y in the fiber bundle is 20 vol% or more and 75 vol% or less,
An adsorption module having a fiber bundle outer porosity z of 5% by volume to 50% by volume.
Fiber filling rate x = A / P
Porosity in fiber bundle y = B / (A + B)
Porosity outside fiber bundle z = 1-x / (1-y)
A: Fiber volume in fiber bundle B: Cavity volume in fiber bundle C: Cavity volume outside fiber bundle P: Housing capacity P = A + B + C The adsorption module according to claim 1, wherein the single fiber includes a base material and adsorptive particles supported on the surface of the base material. The adsorption module according to claim 2, wherein the adsorptive particles are one or more compounds selected from the group consisting of metal oxides, metal hydroxides, and metal hydrates. The adsorption module according to claim 3, wherein the compound includes one or more metals selected from the group consisting of cerium, zirconium, and iron. The fiber bundle adsorbent according to claim 1, wherein the single fiber has a polymer having a side chain that is grafted on a surface thereof and includes an adsorptive functional group. The adsorption module according to claim 5, wherein the adsorptive functional group is one or more functional groups selected from the group consisting of an amino group, an aryl sulfide group, an arylalkyl sulfide group, a phosphate group, and a carboxylic acid group.

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