JP2018012092A - Iodate and/or antimony adsorbent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an iodate and/or antimony adsorbent that can adsorb and remove iodate and/or antimony, without breakthrough over a long time, from liquid containing the iodate and/or antimony, even when allowing the passage of it at high speed, and prevents the desorption of an inorganic ion adsorbent.SOLUTION: An iodate and/or antimony adsorbent is in the form of a porous granular molding containing an inorganic ion adsorbent and an organic polymer resin. A most frequent pore diameter of the porous granular molding is 0.08-0.70 μm when measured with an iodate and/or antimony adsorbent mercury porosimeter. There are also provided a method for producing the adsorbent, and a dispersion of the adsorbent.SELECTED DRAWING: None

Description

  The present invention relates to an adsorbent that adsorbs iodic acid and / or antimony in a liquid, a method for producing the adsorbent, an apparatus including the adsorbent, and a dispersion of the adsorbent.

  In a nuclear facility, waste water discharged from a reactor containment vessel or pressure vessel contains radioactive substances such as radioactive iodic acid and radioactive antimony. For this reason, these wastewaters cannot be discharged out of the nuclear facilities as they are, and it is necessary to reduce the radioactive substances in the wastewater below the regulation value. In particular, wastewater containing a large amount of radioactive material continues to be discharged at the Fukushima nuclear power plant due to the effects of the accident. Radioactive substances are adsorbed and removed by filling the tank with adsorbents suitable for the respective radioelements and passing waste water therethrough.

  In the following Patent Document 1, an iodic acid scavenger containing an inorganic oxide such as zeolite, alumina, silica, and titania as a carrier and containing Pd by an ion exchange method, a dipping method, or the like is filled in a water tank and placed in iodine. A method for removing iodic acid from wastewater containing acid ions is disclosed.

JP 2013-104727 A International Publication No. 2011/062277 Specification International Publication No. 2005/056175 Specification

  However, since the iodic acid trapping material disclosed in Patent Document 1 has a small amount of ion adsorbent, the iodic acid is not adsorbed from the stage where the amount of the adsorbing treatment liquid is small when being used in the adsorbing treatment. In addition, a phenomenon of so-called breakthrough is observed, and since an inorganic oxide is used as a support, the pore diameter is small and iodic acid is difficult to reach the inside of the trapping material. When subjected to adsorption treatment at a high liquid flow rate, that is, when subjected to adsorption treatment with a short contact time between the liquid and the iodic acid capture material, the adsorption treatment only contributes to the adsorption treatment near the surface of the iodic acid capture material. There is also a problem that a breakthrough phenomenon is observed from the stage where the amount of liquid is small, and the amount of trapping material that becomes waste increases due to an increase in the exchange frequency of the iodic acid trapping material.

  The problem to be solved by the present invention is that iodine can adsorb and remove iodic acid and / or antimony from a liquid containing iodic acid and / or antimony without breaking through for a long period even when it is passed at high speed. It is to provide an acid and / or antimony adsorbent.

  As a result of intensive studies and experiments conducted to solve the above-mentioned problems, the present inventors have found an adsorbent in the form of a porous granular molded body containing an inorganic ion adsorbent and an organic polymer resin, In which the mode pore diameter measured by a mercury porosimeter of iodic acid and / or antimony adsorbent mercury porosimeter is used as iodic acid and / or antimony adsorbent for liquid treatment As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention is as follows.
[1] Iodic acid and / or antimony adsorbent in the form of a porous granular molded article containing an inorganic ion adsorbent and an organic polymer resin, the iodic acid and / or antimony of the porous granular molded article The iodic acid and / or antimony adsorbent, characterized in that the mode pore diameter measured with an adsorbent mercury porosimeter is 0.08 to 0.70 μm.
[2] The iodic acid and / or antimony adsorbent according to the above [1], wherein an open surface area ratio of the porous granular molded body is 5% or more and less than 30%.
[3] The above-mentioned [1] or [3], wherein the ratio of the most frequent pore diameter to the median diameter (moderation pore diameter / median diameter) measured with a mercury porosimeter of the porous granular compact is 0.80 to 1.30. Iodic acid and / or antimony adsorbent according to 2].
[4] The iodic acid and / or antimony adsorbent according to any one of [1] to [3], wherein the porous granular molded body has a specific surface area measured by a mercury porosimeter of 10 to 100 m ² / cm ^3. .
[5] The iodic acid and / or antimony adsorbent according to any one of [1] to [4], wherein the porous granular molded body is in the form of spherical particles having an average particle diameter of 100 to 2500 μm.
[6] The inorganic ion adsorbent is represented by the following formula (I):
_{MN x O n · mH 2 O} ······ (I)
{Wherein _x is a number from 0 to 3, _n is a number from 1 to 4, m is a number from 0 to 6, and M and N are independently of each other Ti, Zr, Sn, Sc. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge , A metal element selected from the group consisting of Nb and Ta. } The iodic acid and / or antimony adsorbent according to any one of [1] to [5], which contains at least one metal oxide represented by
[7] The metal oxide is the following (a) to (c):
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) activated alumina,
The iodic acid and / or antimony adsorbent according to [6], selected from any group of
[8] The organic polymer resin is selected from the group consisting of ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyethersulfone (PES), and polyvinylidene fluoride (PVDF). The iodic acid and / or antimony adsorbent according to any one of [1] to [7], which is at least one kind.
[9] The following steps:
(1) A step of obtaining a slurry by pulverizing and mixing an organic polymer resin good solvent and an inorganic ion adsorbent,
(2) A step of obtaining a mixed slurry by dissolving an organic polymer resin and a water-soluble polymer in the slurry obtained in step (1),
(3) A step of obtaining a molded product by molding the mixed slurry obtained in step (2),
(4) The step of promoting the solidification of the molded product obtained in step (3) by controlling the temperature and humidity of the space where the molded product contacts, and (5) The step of promoting solidification in step (4) The obtained molded product is solidified in a poor solvent of the organic polymer resin to obtain a porous molded body,
The manufacturing method of the iodic acid and / or antimony adsorption material in any one of said [1]-[8] containing.
[10] A column having a treated water inlet and outlet and filled with the iodic acid and / or antimony adsorbent according to any one of [1] to [8], and a treatment obtained from the outlet. An iodic acid and / or antimony adsorption apparatus comprising a detector for detecting iodic acid and / or antimony in water.
[11] A dispersion of iodic acid and / or antimony adsorbent, wherein the iodic acid and / or antimony adsorbent according to any of [1] to [8] is dispersed in water.

  If the iodic acid and / or antimony adsorbent according to the present invention is used, iodic acid and / or antimony can be adsorbed without breaking through for a long time even when a liquid containing iodic acid and / or antimony is passed at high speed. Can be removed.

2 is an electron micrograph (magnification 10,000 times) showing an outer surface of a porous granular molded body obtained in Example 1. FIG. FIG. 3 is a pore distribution diagram plotting logarithmic differential pore volume and integrated pore volume against pore diameter measured with a mercury porosimeter of the porous granular molded body obtained in Example 1. It is the pore distribution diagram which plotted the logarithm differential pore volume with respect to the pore diameter measured with the mercury porosimeter of the porous granular molding obtained in Example 1 and Comparative Examples 1, 2, and 3. The schematic of the manufacturing apparatus of the porous granular molding in this embodiment is shown.

  Hereinafter, modes for carrying out the present invention (hereinafter, also referred to as “present embodiment”) will be described in detail below. In addition, this invention is not limited to embodiment, It can implement in various deformation | transformation within the range of the summary.

(Iodic acid and / or antimony adsorbent for liquid treatment)
The iodic acid and / or antimony adsorbent for liquid treatment of the present embodiment is an iodic acid and / or antimony adsorbent in the form of a porous granular molded body containing an inorganic ion adsorbent and an organic polymer resin, The iodic acid and / or antimony adsorbent, characterized in that the mode pore diameter of the porous granular compact measured with an iodic acid and / or antimony adsorbent mercury porosimeter is 0.08 to 0.70 μm. It is. The porous granular molded body has communication holes and a porous structure.
The iodic acid and / or antimony adsorbent of the present embodiment adsorbs and removes iodic acid and / or antimony without breaking through for a long time even when a liquid containing iodic acid and / or antimony is passed at high speed. Can do.

The porous granular molded body in the present embodiment has a mode pore diameter measured by a mercury porosimeter of 0.08 to 0.70 μm, preferably 0.10 to 0.60 μm, preferably 0.20 to 0.00. More preferably, it is 50 μm.
As shown in FIG. 3, in the present embodiment, the mode pore diameter (mode diameter) is a logarithmic differential pore volume (dV / d (logD) with respect to the pore diameter measured with a mercury porosimeter, where V Is the mercury intrusion volume, and D is the pore diameter.) In the plot of the figure, it means the pore diameter at which the value of the logarithmic differential pore volume is maximum, and is based on volume.

The mercury porosimeter is an apparatus for evaluating the pore size of a porous material by a mercury intrusion method, and has a relatively large pore distribution (mesopore (several nm)) that cannot be measured by a gas adsorption method (BET method). Suitable for measurement of macropores (several hundreds of μm).
In this embodiment, by measuring the mode pore diameter with a mercury porosimeter, the porous structure (framework structure) of the porous granular compact is characterized in detail, and the median diameter and specific surface area are measured with the mercury porosimeter. By doing so, the porous structure (skeleton structure) of the porous granular molded body can be characterized in detail.
If the mode pore diameter is 0.08 μm or more, the adsorbed substance such as iodic acid or antimony is sufficient as the pore diameter of the communicating holes for diffusing into the porous molded body, and the diffusion rate is increased. On the other hand, if the most frequent pore diameter is 0.70 μm or less, the voids of the porous granular compact become small, and the abundance of inorganic ion adsorbent in the unit volume becomes dense. Ions can be adsorbed.

The opening ratio of the outer surface of the porous granular molded body is preferably 5% or more and less than 30%, more preferably 7% or more and 28% or less, and further preferably 10% or more and 25% or less.
In the present embodiment, the outer surface opening ratio means a ratio of the sum of the opening areas of all the holes in the area of the visual field obtained by observing the outer surface of the porous granular molded body with a scanning electron microscope.
When the outer surface opening ratio is 5% or more, the diffusion rate of the substance to be adsorbed such as iodic acid and antimony into the porous molded body is increased. Since there are many inorganic ion adsorbents on the outer surface of the conductive granular molded body, ions in water can be reliably adsorbed even when the liquid is passed through at high speed.
In the present embodiment, the outer surface opening ratio is measured by observing the outer surface of the porous granular molded body at 10,000 times. Specifically, the outer surface aperture ratio can be measured by the method described in the examples.

In the porous granular molded body according to the present embodiment, the ratio of the most frequent pore diameter to the median diameter (moderation pore diameter / median diameter) measured with a mercury porosimeter is preferably 0.80 to 1.30. It is more preferably 85 to 1.25, and further preferably 0.90 to 1.20.
In the present embodiment, the median diameter means the pore diameter with respect to the median of the range of the maximum value and the minimum value of the integrated pore volume in the integrated pore volume distribution, and is based on the volume.
When the ratio of the most frequent pore diameter / median diameter is close to 1.0, the pore diameter distribution of the porous granular molded body is uniform, which is suitable for high-speed water flow treatment.
When the pore size is small and a dense layer (skin layer) is present near the outer surface of the porous granular molded body, a large void (maximum pore size layer) is likely to be formed inside the skin layer (inner direction of the molded body). A ratio of the most frequent pore diameter / median diameter of 0.80 to 1.30 means that no skin layer is present in the porous granular molded body.

Porous particulate molded body in the present embodiment, it is preferable that the specific surface area measured by a mercury porosimeter is 10 to 100 m ² / cm ^3, more preferably 11~90m ² / cm ^3, 12~50m ² More preferably, it is / cm ³ .
If the specific surface area is 10 m ² / cm ³ or more, since the amount of the inorganic ion adsorbent supported is large and the pore surface area is large, sufficient adsorption performance during high-speed water passage can be obtained, while the specific surface area is 100 m ^2. If it is / cm ³ or less, the inorganic ion adsorbent is firmly supported, so the strength of the porous granular molded body is high.

In the present embodiment, the specific surface area is defined by the following equation.
Specific surface area (m ² / cm ³ ) = S (Hg) (m ² / g) × bulk specific gravity (g / cm ³ )
Here, S (Hg) means the pore surface area (m ² / g) per unit weight of the porous granular molded body. The pore surface area is measured using a mercury porosimeter after the porous granular compact is vacuum-dried at room temperature. Specifically, the pore surface area can be measured by the method described in Examples.
The measuring method of bulk specific gravity is as follows.
The porous granular molded body is spherical, columnar, hollow cylindrical, etc., and the one having a short shape is an apparent 1 mL ³ mL of the porous granular molded body in a wet state using a graduated cylinder or the like. Measure the volume. Then, the weight is obtained by vacuum drying at room temperature, and the bulk specific gravity is calculated as weight / volume.
The porous molded body is in the form of a thread, a hollow fiber, a sheet or the like, and the one having a long shape measures the cross-sectional area and the length when wet, and calculates the volume from the product of both. Then, the weight is obtained by vacuum drying at room temperature, and the bulk specific gravity is calculated as weight / volume.

The porous granular molded body in the present embodiment is substantially spherical, preferably has an average particle size of 100 to 2500 μm, more preferably 150 to 2000 μm, and 200 to 1500 μm. More preferably.
The porous granular molded body in the present embodiment is preferably spherical particles, and the spherical particles may be not only true spherical but also elliptical spherical.
If the average particle size is 100 μm or more, it is suitable for high-speed water treatment because the pressure loss is small when the porous granular compact is filled into a column or tank, etc. On the other hand, if the average particle size is 2500 μm or less. For example, the surface area when the porous molded body is filled in a column or tank can be increased, and ions can be reliably adsorbed even when the liquid is passed through at high speed.
In the present embodiment, the average particle diameter means a median diameter of a sphere equivalent diameter obtained from an angular distribution of scattered light intensity of diffraction by laser light, assuming that the porous granular molded body is spherical.

(Organic polymer resin)
The organic polymer resin constituting the porous granular molded body in the present embodiment is not particularly limited, but is preferably a resin that can be made porous by wet phase separation.
Examples of organic polymer resins include polysulfone polymers, polyvinylidene fluoride polymers, polyvinylidene chloride polymers, acrylonitrile polymers, polymethyl methacrylate polymers, polyamide polymers, polyimide polymers, cellulose polymers, and ethylene vinyl. Examples include alcohol copolymer polymers and many types.
Among these, ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyethersulfone (PES), and polyfluoride are preferred because of their non-swelling property and biodegradability in water and ease of production. Vinylidene chloride (PVDF) is preferred.
The polyethersulfone preferably has a hydroxyl group at the terminal. By having a hydroxyl group as a terminal group, the porous granular molded body of this embodiment can exhibit excellent carrying performance of an inorganic ion adsorbent. In addition, since the organic polymer resin having high hydrophobicity has a hydroxyl group at the terminal, hydrophilicity is improved and fouling is hardly generated in the porous granular molded body.

(Inorganic ion adsorbent)
The inorganic ion adsorbent contained in the porous granular molded body in the present embodiment means an inorganic substance that exhibits an ion adsorption phenomenon or an ion exchange phenomenon.
Examples of the natural-based inorganic ion adsorbent include various mineral substances such as zeolite and montmorillonite.
Specific examples of various minerals include aluminosilicate kaolin minerals with a single layer lattice, bilayered muscovite, sea green stone, Kanuma soil, pyrophyllite, talc, feldspar with a three-dimensional framework structure , Zeolite and montmorillonite.
Examples of the synthetic inorganic ion adsorbent include metal oxides, polyvalent metal salts, insoluble hydrated oxides, and the like. Examples of the metal oxide include a composite metal oxide, a composite metal hydroxide, and a metal hydrated oxide.

The inorganic ion adsorbent is an object to be adsorbed, and in particular, from the viewpoint of phosphorus adsorption performance, the following formula (I):
_{MN x O n · mH 2 O} ··· (I)
It is preferable that it is a metal oxide represented by these.
In the above formula _{(I), x} is a number from 0 to _{3, n} is a number from 1 to 4, m is a number of Less than six, M and N are independently of each other, Ti, Zr , Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni , V, Ge, Nb, and Ta.
The metal oxide is a non-hydrated (unhydrated) metal oxide in which m in the above formula (I) is 0, but a metal hydrated oxide (hydrated metal) in which m is a value other than 0 Oxide).

In the metal oxide in the case where _x in the above formula (I) is an integer other than 0, each metal element contained is regularly distributed throughout the oxide with regularity and contained in the metal oxide. It is a composite metal oxide represented by a chemical formula in which the composition ratio of each metal element is fixed.
Specifically, those forming a perovskite structure, a spinel structure, etc., nickel ferrite (NiFe ₂ O ₄ ), zirconium hydrous ferrite (Zr · Fe ₂ O ₄ · mH ₂ O, where m is 0 .5 to 6) and the like.
The inorganic ion adsorbent may contain a plurality of types of metal oxides represented by the above formula (I).

The inorganic ion adsorbent is at least one selected from the following groups (a) to (c) from the viewpoint of excellent adsorption performance of iodic acid, antimony, phosphorus, boron, fluorine and / or arsenic. Preferably there is.
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) Activated alumina.

A material selected from any one of the groups (a) to (c) may be used, or a material selected from any one of the groups (a) to (c) may be used in combination. The materials in each of the groups (a) to (c) may be used in combination. When used in combination, it may be a mixture of two or more materials selected from any one of the groups (a) to (c), and two or more groups of the groups (a) to (c) The mixture of 2 or more types of materials chosen from these may be sufficient.
The inorganic ion adsorbent may contain aluminum sulfate-added activated alumina from the viewpoint of low cost and high adsorptivity.

As the inorganic ion adsorbent, in addition to the metal oxide represented by the above formula (I), a metal element other than the above M and N is further dissolved, from the viewpoint of the adsorptivity of inorganic ions and the production cost. More preferred.
For example, a hydrated zirconium oxide represented by ZrO ₂ · mH ₂ O (m is a numerical value other than 0) in which iron is dissolved is mentioned.

Examples of the polyvalent metal salt include the following formula (II):
M ²⁺ _(1-p) M ³⁺ _p (OH ⁻ ) _{(2 + p-q)} (A ⁿ⁻ ) _{q / r} (II)
And hydrotalcite compounds represented by:
In the above formula (II), M ²⁺ is at least one divalent metal ion selected from the group consisting of Mg ²⁺ , Ni ²⁺ , Zn ²⁺ , Fe ²⁺ , Ca ²⁺ and Cu ²⁺ .
M ³⁺ is at least one trivalent metal ion selected from the group consisting of Al ³⁺ and Fe ³⁺ .
A ⁿ⁻ is an n-valent anion.
0.1 ≦ p ≦ 0.5, 0.1 ≦ q ≦ 0.5, and r is 1 or 2.
The hydrotalcite compound represented by the above formula (II) is preferable because the raw material is inexpensive as an inorganic ion adsorbent and the adsorptivity is high.
Examples of insoluble hydrated oxides include insoluble heteropolyacid salts and insoluble hexacyanoferrates.

  The inorganic ion adsorbent contained in the porous granular molded body according to the present embodiment contains an impurity element mixed due to the production method and the like as long as the function of the porous granular molded body according to the present embodiment is not hindered. You may do it. Examples of impurity elements that may be mixed include nitrogen (nitrate, nitrite, ammonium), sodium, magnesium, sulfur, chlorine, potassium, calcium, copper, zinc, bromine, barium, and hafnium. It is done.

  The iodic acid and / or antimony adsorbent for liquid processing according to the present embodiment has an outer surface inorganic surface diameter of 0.08 to 0.70 μm as the most frequent pore diameter of the porous granular molded body measured with a mercury porosimeter. Because it is a porous granular molded product with a large amount of ion adsorbent, it can reliably adsorb iodic acid and / or antimony even if it is passed through at high speed, and the inside of the porous molded product of iodic acid and / or antimony It is also excellent in osmotic diffusion adsorption.

  Using the iodic acid and / or antimony adsorbent of this embodiment packed in a suitable column etc., connected in series or in parallel before and after the column or removal system packed with an adsorbent that adsorbs other ionic species. can do. The iodic acid and / or antimony adsorbent of the present embodiment can be used as an iodic acid and / or antimony adsorption column packed in a column or the like, and the selectivity of iodic acid and / or antimony even in a high space velocity state. Excellent adsorption performance.

[Method for producing porous molded body]
The method for producing a porous granular molded body in this embodiment is obtained by (1) a step of pulverizing and mixing an organic polymer resin good solvent and an inorganic ion adsorbent to obtain a slurry, and (2) a step (1). A step of dissolving the organic polymer resin and the water-soluble polymer in the slurry, (3) a step of molding the slurry obtained in step (2), (4) the molded product obtained in step (3), A step of promoting the solidification by controlling the temperature and humidity of the space part in contact with the molded product, and (5) the solidified product obtained in step (4) is a poor solvent for the organic polymer resin. Including the step of solidifying therein.

(Process (1): Grinding / mixing process)
In the step (1), a good solvent of the organic polymer resin and the inorganic ion adsorbent are pulverized and mixed to obtain a slurry.
By finely grinding the inorganic ion adsorbent in a good solvent of the organic polymer resin, the inorganic ion adsorbent can be made into fine particles. As a result, the inorganic ion adsorbent supported on the porous granular compact after molding has few secondary aggregates.

<Good solvent for organic polymer resin>
The good solvent for the organic polymer resin in the step (1) is not particularly limited as long as the organic polymer resin is stably dissolved in excess of 1% by mass under the production conditions of the porous granular molded body. There can be used known ones.
Examples of the good solvent include N-methyl-2pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), and the like.
Only 1 type may be used for a good solvent, and 2 or more types may be mixed and used for it.

<Crushing and mixing means>
In the step (1), the pulverization / mixing means used for obtaining the slurry is not particularly limited as long as it can be pulverized / mixed together with the inorganic ion adsorbent and the good solvent of the organic polymer resin. .
As the pulverization / mixing means, for example, a means used in a physical crushing method such as pressure-type fracture, mechanical grinding, ultrasonic treatment or the like can be used.
Specific examples of the pulverization / mixing means include generator shaft type homogenizers, blenders such as Waring blenders, media agitating mills such as sand mills, ball mills, attritors and bead mills, jet mills, mortars and pestles, rabies, and ultrasonic treatment equipment. Etc.
Among them, a medium stirring mill is preferable because it has high grinding efficiency and can grind even a high viscosity.
The diameter of the ball used in the medium stirring mill is not particularly limited, but is preferably 0.1 to 10 mm. If the ball diameter is 0.1 mm or more, the ball mass is sufficient, so that the pulverization force is high and the pulverization efficiency is high.
The material of the balls used in the medium agitating mill is not particularly limited, but various kinds of metals such as iron and stainless steel, oxides such as alumina and zirconia, and non-oxides such as silicon nitride and silicon carbide. A ceramic etc. are mentioned. Among them, zirconia is excellent in that it has excellent wear resistance and has less contamination to the product (mixed wear).

<Dispersant>
In the step (1), a known dispersion of a surfactant or the like in a good solvent of an organic polymer resin mixed with an inorganic ion adsorbent when pulverizing and mixing within a range that does not affect the structure of the porous granular molded body An agent may be added.

(Process (2): Dissolution process)
In step (2), the organic polymer resin and the water-soluble polymer are dissolved in the slurry obtained in step (1) to obtain a molding (mixed) slurry.
The addition amount of the organic polymer resin is preferably such that the ratio of organic polymer resin / (organic polymer resin + water-soluble polymer + organic polymer resin good solvent) is 3 to 40% by mass. More preferably, it is 4-30 mass%. When the content of the organic polymer resin is 3% by mass or more, a porous granular molded body having high strength is obtained. On the other hand, when the content is 40% by mass or less, a porous granular molded body having high porosity is obtained. It is done.

<Water-soluble polymer>
The water-soluble polymer in the step (2) is not particularly limited as long as it is compatible with the good solvent of the organic polymer resin and the organic polymer resin.
As the water-soluble polymer, any of natural polymers, semi-synthetic polymers and synthetic polymers can be used.
Examples of natural polymers include guar gum, locust bean gum, carrageenan, gum arabic, tragacanth, pectin, starch, dextrin, gelatin, casein and collagen.
Examples of the semisynthetic polymer include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl starch, and methyl starch.
Examples of the synthetic polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, and polyethylene glycols such as tetraethylene glycol and triethylene glycol.
Among them, a synthetic polymer is preferable from the viewpoint of improving the supportability of the inorganic ion adsorbent, and polyvinylpyrrolidone and polyethylene glycols are more preferable from the viewpoint of improving the porosity.
The mass average molecular weight of polyvinyl pyrrolidone and polyethylene glycol is preferably 400 to 35,000,000, more preferably 1,000 to 1,000,000, and 2,000 to 100,000. More preferably.
If the mass average molecular weight is 2,000 or more, a porous granular molded article having a high surface opening property can be obtained. On the other hand, if the mass average molecular weight is 1,000,000 or less, the viscosity of the slurry at the time of molding is low so that molding is possible. Tend to be easier.
The mass average molecular weight of the water-soluble polymer can be measured by dissolving the water-soluble polymer in a predetermined solvent and performing gel permeation chromatography (GPC) analysis.

The amount of the water-soluble polymer added is such that the ratio of water-soluble polymer / (water-soluble polymer + organic polymer resin + organic polymer resin good solvent) is 0.1 to 40% by mass. Is preferable, it is more preferable that it is 0.5-30 mass%, and it is further more preferable that it is 1-10 mass%.
If the addition amount of the water-soluble polymer is 0.1% by mass or more, the porous granule includes a fibrous structure that forms a three-dimensional continuous network structure on the outer surface and inside of the porous granular molded body If the molded body can be obtained uniformly and, on the other hand, the addition amount of the water-soluble polymer is 40% by mass or less, the outer surface opening ratio is appropriate, and the presence of the inorganic ion adsorbent on the outer surface of the porous granular molded body Since the amount is large, an adsorbent capable of reliably adsorbing ions even when the liquid is passed through at high speed can be obtained.

(Process (3): Molding process)
In step (3), the slurry (molding (mixed) slurry) obtained in step (2) is formed. The molding slurry is a mixed slurry of an organic polymer resin, a good solvent for the organic polymer resin, an inorganic ion adsorbent, and a water-soluble polymer.
The form of the porous granular molded body of the present embodiment can take any form such as a spherical shape, a thread shape, a sheet shape, a hollow fiber shape, a cylindrical shape, and a hollow cylindrical shape, depending on the method for forming the forming slurry.

The method of forming into a particulate form is not particularly limited. For example, the rotation of forming a droplet by scattering the forming slurry stored in the container from a nozzle provided on the side surface of the rotating container. The nozzle method etc. are mentioned. By the rotary nozzle method, it can be formed into a particulate form having a uniform particle size distribution.
Specifically, a method of spraying a molding slurry from a 1-fluid nozzle or a 2-fluid nozzle and coagulating it in a coagulation bath can be mentioned.
The diameter of the nozzle is preferably 0.1 to 10 mm, and more preferably 0.1 to 5 mm. If the nozzle diameter is 0.1 mm or more, droplets are likely to scatter, while if it is 10 mm or less, the particle size distribution can be made uniform.
Centrifugal force is represented by centrifugal acceleration, preferably 5 to 1500 G, more preferably 10 to 1000 G, and even more preferably 10 to 800 G.
If the centrifugal acceleration is 5G or more, the formation and scattering of droplets are easy, while if it is 1500G or less, the molding slurry is discharged without being in the form of a thread, and it is possible to suppress the widening of the particle size distribution. it can. Since the particle size distribution is narrow, the flow path of water becomes uniform when the column is filled with porous granular compacts, so even if it is used for ultra-high-speed water flow treatment, ions (adsorption object) leak out from the beginning of water flow. It has the advantage that it does not break through.

Examples of the method of forming into a thread-like or sheet-like form include a method of extruding a forming slurry from a spinneret or die having a corresponding shape and solidifying the slurry in a poor solvent.
As a method for forming a hollow fiber-like porous granular formed body, it can be formed in the same manner as a method for forming a thread-like or sheet-like porous granular formed body by using a spinning nozzle comprising an annular orifice.
As a method for forming a cylindrical or hollow cylindrical porous granular molded body, when extruding a molding slurry from a spinning nozzle, it may be solidified in a poor solvent while being cut, or after solidifying into a thread shape. You can cut it.

(Process (4): Solidification promotion process)
In the step (4), until the molded product obtained in the step (3) is solidified in a poor solvent, the temperature and humidity of the space part in contact with the molded product are controlled to promote solidification.
By the step (4), the mode pore diameter and the outer surface opening ratio measured with a mercury porosimeter can be adjusted, and a molded body having a high abundance of inorganic ion adsorbents can be obtained. In addition, it is possible to provide a porous granular molded body that can remove phosphorus ions at a high speed and has a large adsorption capacity.
As shown in FIG. 4, the temperature and humidity of the space are controlled by covering the space between the coagulation tank in which the poor solvent is stored and the rotating container with a cover, and adjusting the temperature of the poor solvent.
The temperature of the space is preferably 20 to 90 ° C, more preferably 25 to 85 ° C, and further preferably 30 to 80 ° C.
If the temperature of the space is 20 ° C. or higher, the outer surface opening ratio of the porous molded body is high. On the other hand, if it is 90 ° C. or lower, the nozzle opened in the rotating container is not easily clogged with slurry and is stable for a long time. Thus, a porous granular molded body can be produced.
The humidity of the space is preferably 65 to 100%, more preferably 70 to 100%, and even more preferably 75 to 100% in terms of relative humidity with respect to temperature.
When the relative humidity is 65% or more, the outer surface opening ratio of the porous granular molded body is high. On the other hand, when the relative humidity is 100% or less, the nozzle opened in the rotating container is not easily clogged with slurry, and is stable for a long time. A molded body can be produced.

(Process (5): Solidification process)
In step (5), the molded product obtained in step (4) whose coagulation is promoted is solidified in a poor solvent to obtain a porous granular molded body.

<Poor solvent>
As the poor solvent in the step (5), a solvent having an organic polymer resin solubility of 1% by mass or less can be used under the conditions of the step (5). For example, water, alcohols such as methanol and ethanol, ethers And aliphatic hydrocarbons such as n-hexane and n-heptane. Among these, water is preferable as the poor solvent.

In step (5), a good solvent is brought in from the preceding step, and the concentration of the good solvent changes at the start and end of the coagulation step. Therefore, it may be a poor solvent in which a good solvent is added in advance, and it is preferable to perform the coagulation step by controlling the concentration while separately adding water or the like so as to maintain the initial concentration.
By adjusting the concentration of the good solvent, the structure (outer surface opening ratio and particle shape) of the porous granular molded body can be controlled.
When the poor solvent is water or a mixture of a good solvent of organic polymer resin and water, the content of the good solvent of the organic polymer resin is preferably 0 to 80% by mass in the coagulation step, and 0 to 60% by mass. % Is more preferable.
When the content of the good solvent of the organic polymer resin is 80% by mass or less, an effect of improving the shape of the porous granular molded body is obtained.
The temperature of the coagulating liquid is preferably 40 to 100 ° C., more preferably 50 to 100 ° C., and 60 to 100 ° C. from the viewpoint of controlling the temperature and humidity of the space portion in the step (4). More preferably.

(Porous granular molded product manufacturing equipment)
As illustrated in FIG. 4, the porous granular molded body manufacturing apparatus according to the present embodiment includes a rotating container (5) that scatters droplets by centrifugal force, and a coagulation tank (4) that stores a coagulating liquid. The space part cover (3) which covers the space part between a rotation container and a coagulation tank is comprised, and the control means which controls the temperature and humidity of a space part is provided.

The rotating container that scatters droplets by centrifugal force is not limited to a specific structure as long as it has a function of making the molding slurry into spherical droplets and scatters by centrifugal force. Examples include a rotating nozzle.
In the rotating disk, the forming slurry is supplied to the center of the rotating disk, the forming slurry spreads out in a film shape with a uniform thickness along the surface of the rotating disk, and is divided into droplets by centrifugal force from the periphery of the disk. Thus, fine droplets are scattered.
The rotating nozzle has a large number of through holes formed in the peripheral wall of the hollow disk-shaped rotating container, or is attached to the nozzle by penetrating through the peripheral wall. The forming slurry is supplied into the rotating container and the rotating container is rotated. At this time, the forming slurry is discharged from the through hole or nozzle by centrifugal force to form droplets.

The coagulation tank for storing the coagulation liquid is not limited to one having a specific structure as long as it has a function of storing the coagulation liquid. For example, the coagulation tank having a known upper surface opening or a cylinder arranged to surround the rotating container Examples thereof include a coagulation tank having a structure in which the coagulating liquid naturally flows down by gravity along the inner surface of the body.
The coagulation tank having an upper surface is a device that spontaneously drops liquid droplets scattered horizontally from the rotating container and captures the liquid droplets on the surface of the coagulation liquid stored in the coagulation tank having an upper surface opened.
A coagulation tank with a structure in which the coagulating liquid naturally flows down by gravity along the inner surface of the cylinder arranged so as to surround the rotating container allows the coagulating liquid to flow out at a substantially uniform flow rate in the circumferential direction along the inner surface of the cylinder. The apparatus captures and solidifies droplets in a coagulating liquid flow that naturally flows along the inner surface.

An apparatus for producing a porous granular molded body includes a space portion cover that covers a space portion between a rotating container and a coagulation tank, and the temperature and humidity control means of the space portion controls the temperature and humidity of the space portion. Means.
The space part cover that covers the space part is not limited to a specific structure as long as it has a function of isolating the space part from the external environment and making it easier to realistically control the temperature and humidity of the space part, For example, it can be a box shape, a cylindrical shape, and an umbrella shape.
Examples of the material of the cover include metal stainless steel and plastic. It can also be covered with a known heat insulating material in that it is isolated from the external environment. The cover may be partially opened to adjust the temperature and humidity.

The temperature and humidity control means of the space section need only have a function of controlling the temperature and humidity of the space section, and are not limited to specific means. For example, heaters such as an electric heater and a steam heater, and ultrasonic humidification And humidifiers such as a heating humidifier and the like.
In view of the simple structure, a means for heating the coagulation liquid stored in the coagulation tank and using the steam generated from the coagulation liquid to control the temperature and humidity of the space is preferable.

(Iodic acid and / or antimony adsorption device)
The iodic acid and / or antimony adsorbing device of the present embodiment includes a column having a treated water inlet and outlet and filled with the iodic acid and / or antimony adsorbent, and treated water obtained from the outlet. A detector for detecting iodic acid and / or antimony.
The iodic acid and / or antimony adsorbent obtained under the above production conditions is used in a state packed in a column having an inlet for introducing treated water and an outlet for outlet.
Here, the shape of the column is not particularly limited as long as it has an introduction port and a discharge port, and can take a cylindrical shape, a rectangular parallelepiped shape, or the like. The column material is not particularly limited as long as it has durability against the solvent contained in the treated water to be used, and is a glass-lined metal such as carbon steel, stainless steel, titanium, hastelloy, zirconium, or cast iron. Use metal-chemical-resistant resin lining, resin such as polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, and fiber reinforced plastics such as unsaturated polyester and vinyl ester reinforced with glass fiber, etc. Can do.
And in this embodiment, an iodic acid and / or antimony adsorption | suction apparatus is comprised by combining the said column and the detector which detects the iodic acid and / or antimony in the treated water obtained through the said outlet. be able to.

(Dispersion of iodic acid and / or antimony adsorbent)
The iodic acid and / or antimony adsorbent may be used by filling the column in the form of a dry solid, or in a state of a dispersion dispersed in a solvent without making a dry solid in the production process. It is also possible to fill. Therefore, one of the present embodiments can be a dispersion of iodic acid and / or antimony adsorbent in which the iodic acid and / or antimony adsorbent is dispersed in water.
The dispersion is easier to prevent powder from falling off due to the rubbing of the adsorbent, and easier to carry.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In addition, the physical property of the porous granular molded object was measured with the following method.

[Observation of porous granular compacts with a scanning electron microscope]
Observation of the porous molded body with a scanning electron microscope (SEM) was performed with a SU-70 scanning electron microscope manufactured by Meidari Seisakusho after the porous granular molded body was vacuum-dried at room temperature.
The porous granular molded body sample was held on a carbon adhesive tape / alumina sample stage and coated with osmium (Os) as a conductive treatment to obtain an outer surface SEM observation sample.

[Moderate pore diameter and median diameter of porous granular compacts]
The porous granular compact was vacuum-dried at room temperature and then measured with a mercury porosimeter (manufactured by Shimadzu Corporation, Shimadzu Autopore IV9500).

[Outside surface area ratio]
An image of the outer surface of a porous granular molded body photographed using a scanning electron microscope (SEM) is obtained by analyzing it using image analysis software (A image-kun (trade name) manufactured by Asahi Kasei Engineering Co., Ltd.). It was. More specifically, the obtained SEM image is recognized as a grayscale image, and the threshold value is manually adjusted so that the dark portion has an opening and the thin portion has a porous structure (skeleton structure). It divided | segmented into the opening part and the frame | skeleton part, and calculated | required the area ratio. In order to reduce an error in threshold determination, the same measurement was performed on 10 images, and an average value was calculated.

[Specific surface area and bulk specific gravity of porous granular compacts]
After the porous molded body was vacuum-dried at room temperature, a pore surface area S (Hg) per unit mass of the porous granular molded body was measured using a mercury porosimeter (manufactured by Shimadzu Corporation, Shimadzu Autopore IV9500 type) (m ² / G).
Next, the porous granular molded body wet with water was tapped using a graduated cylinder, and the apparent volume V (cm ³ ) was measured. Then, it vacuum-dried at room temperature and calculated | required the dry mass W (g) of the porous granular molding.
The specific surface area of the porous granular compact was determined from the following equation.
Specific surface area (m ² / cm ³ ) = S (Hg) (m ² / g) × bulk specific gravity (g / cm ³ )
Bulk specific gravity (g / cm ³ ) = W / V
In the above formula, S (Hg) is the surface area per unit mass (m ² / g) of the porous molded body, W is the dry mass (g) of the porous granular molded body, and V is its apparent volume ( cm ³ ).

[Average particle size of porous granular compact and average particle size of inorganic ion adsorbent]
The average particle diameter of the porous granular molded body and the average particle diameter of the inorganic ion adsorbent were measured with a laser diffraction / scattering particle size distribution analyzer (LA-950 (trade name) manufactured by HORIBA). Water was used as the dispersion medium. When measuring a sample using hydrated cerium oxide as an inorganic ion adsorbent, the refractive index was measured using the value of cerium oxide. Similarly, when a sample using hydrated zirconium oxide as an inorganic ion adsorbent was measured, the value of zirconium oxide was used as the refractive index.

[Example 1]
220 g of N-methyl-2pyrrolidone (NMP, Mitsubishi Chemical Co., Ltd.) and 200 g of hydrated cerium oxide powder (Iwatani Sangyo Co., Ltd.) having an average particle size of 30 μm were filled with 1.5 kg of a stainless steel ball having a diameter of 5 mmφ. This was put into a stainless steel ball mill pot with a volume of 1 L, and pulverized and mixed at 150 rpm for 150 minutes to obtain a yellow slurry. In the obtained slurry, 4 g of polyvinylpyrrolidone (PVP, BASF Japan Ltd., Luvitec K30 Powder (trade name)), 91.5% by mass of acrylonitrile, 8.0% by mass of methyl acrylate, sodium methallylsulfonate 0 10 g of an intrinsic viscosity [η] = 1.2 copolymer (organic polymer resin, PAN) consisting of 5% by mass is added, heated to 60 ° C. in a dissolving tank, and a stirring blade is used. The mixture was stirred and dissolved to obtain a uniform molding slurry solution.
The obtained molding slurry solution was heated to 60 ° C., and supplied to the inside of a cylindrical rotating container having a nozzle with a diameter of 4 mm on the side surface. The container was rotated, and droplets were discharged from the nozzle by centrifugal force (15 G). Formed. Subsequently, the space between the rotating container and the coagulation tank is covered with a polypropylene cover, and the space where the temperature of the space is controlled to 50 ° C. and the relative humidity is controlled to 100% is allowed to fly. 50% by mass of the coagulation liquid was heated to 80 ° C. and stored in a coagulation tank having an upper surface opening, and the molding slurry was coagulated.
Furthermore, washing | cleaning and classification were performed and the spherical porous molded object with an average particle diameter of 370 micrometers was obtained.
FIG. 1 shows an electron micrograph (magnification 10,000 times) showing the surface of the obtained porous granular molded body.

(Iodic acid flow adsorption test)
20 mL of the obtained granular compact was packed into a cylindrical column having an inner diameter of 15 mm. Artificial seawater (Osaka Yakuken Co., Ltd., Marine Art SF-1 (trade name)) diluted three-fold with pure water. Raw water with an iodine concentration of 10 mg / L prepared by dissolving sodium iodate in artificial seawater. The raw water was passed through the column at a downward flow rate of 10 h ⁻¹ (SV Space Velocity). The iodine concentration in the adsorption treated water flowing out from the lower part of the column was measured by ICP emission spectrometry. Table 1 below shows the penetration ratio with respect to the amount of adsorbent at the time when 1 mg / L iodine was detected in the treated water as the iodic acid 10% breakthrough penetration ratio.

(Antimony liquid adsorption test)
20 mL of the obtained granular compact was packed into a cylindrical column having an inner diameter of 15 mm. Antimony concentration 5 mg / L prepared by dissolving antimony (III) chloride in 3 times diluted artificial seawater obtained by diluting artificial seawater (Osaka Yakken Co., Ltd., Marine Art SF-1 (trade name)) with pure water 3 times The raw water was made to flow through the column at a descending flow rate of 10 h ⁻¹ (SV Space Velocity). And the antimony density | concentration in the adsorption processing water which flows out out of the column lower part was measured by ICP emission spectrometry. Table 1 below shows the penetration rate with respect to the amount of adsorbent at the time when 0.5 mg / L of antimony was detected in the treated water as antimony 10% breakthrough penetration rate.

[Example 2]
A spherical porous molded body was obtained in the same manner as in Example 1 except that the temperature of the coagulation liquid was 60 ° C., the temperature of the space was 37 ° C., and the relative humidity was 100%. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 3
A spherical porous molded body was obtained in the same manner as in Example 1 except that the amount of hydrated cerium oxide powder charged was increased from 200 g to 300 g. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 4
A spherical porous molded body was obtained in the same manner as in Example 1 except that the amount of hydrated cerium oxide powder charged was reduced from 200 g to 150 g. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 5
Spherical porous molding in the same manner as in Example 3 except that the porous molded body is molded using a nozzle having a nozzle diameter reduced from 4 mm to 3 mm provided on the side surface of the cylindrical rotating container. Got the body. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 6
Spherical porous molding similar to the method described in Example 3 except that the porous molded body is molded using a nozzle having a nozzle diameter increased from 4 mm to 5 mm on the side surface of the cylindrical rotating container. Got the body. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 7
160 g of dimethyl sulfoxide (DMSO, Kanto Chemical Co., Ltd.) is used as a good solvent for the organic polymer resin, and ethylene vinyl alcohol copolymer (EVOH, Nippon Synthetic Chemical Industry Co., Ltd., Soarnol E3803 (trade name)) is used as the organic polymer resin. A spherical porous molded body was obtained in the same manner as in Example 1 except that 20 g, the charged amount of hydrated cerium oxide powder was 250 g, the coagulating liquid was water, and the nozzle diameter was 5 mm. . In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 8
The organic polymer resin is polyethersulfone (Sumitomo Chemical Co., Ltd., Sumika Excel 5003PS (trade name), OH terminal grade, terminal hydroxyl group composition 90 (mol%)) 30 g, and the water-soluble polymer is polyethylene glycol (PEG 35,000, Merck) 4 g, the amount of hydrated cerium oxide powder was 100 g, the coagulating liquid was water, and the nozzle diameter was 5 mm. A molded body was obtained. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 1 below.

Example 9
Example except that hydrated zirconium oxide powder (Daiichi Rare Element Co., Ltd., R zirconium hydroxide (trade name)) dried in a constant amount in a dryer at 70 ° C. was used as the inorganic ion adsorbent. In the same manner as described in 1, a spherical porous molded body was obtained. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

Example 10
As an inorganic ion adsorbent, a hydrated zirconium oxide powder (Daiichi Rare Element Co., Ltd., R zirconium hydroxide (trade name)) dried at a constant weight in a dryer at 70 ° C. is used, and the nozzle diameter is 4 mm. A spherical porous molded body was obtained in the same manner as described in Example 7 except for the above. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

Example 11
As an inorganic ion adsorbent, a hydrated zirconium oxide powder (Daiichi Rare Element Co., Ltd., R zirconium hydroxide (trade name)) dried at a constant weight in a dryer at 70 ° C. is used, and the nozzle diameter is 4 mm. A spherical porous molded body was obtained in the same manner as described in Example 8 except for the above. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

Example 12
A spherical porous molded body was obtained in the same manner as in Example 1 except that the temperature of the coagulation liquid was 50 ° C., the temperature of the space was 31 ° C., and the relative humidity was controlled to 80%. . In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

[Comparative Example 1]
A porous granular molded body was obtained in the same manner as described in Example 2 except that the space between the rotating container and the coagulation tank was not covered with a polypropylene cover. At this time, the temperature of the space was 26 ° C. and the relative humidity was 63%. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

[Comparative Example 2]
A porous molded body was obtained with reference to Example 1 of Patent Document 2 (International Publication No. 2011/062277).
The spherical porous molded body is the same as the method described in Example 8, except that the space between the rotating container and the coagulation tank is not covered with a polypropylene cover, and the temperature of the coagulation liquid is 60 ° C. Got. At this time, the temperature of the space was 26 ° C. and the relative humidity was 63%. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

[Comparative Example 3]
A porous molded body was obtained with reference to Example 2 of Patent Document 3 (International Publication No. 2005/056175).
The spherical porous molded body is the same as the method described in Example 7 except that the space between the rotating container and the coagulation tank is not covered with a polypropylene cover, and the temperature of the coagulation liquid is 60 ° C. Got. At this time, the temperature of the space was 26 ° C. and the relative humidity was 63%. In the same manner as in Example 1, an iodic acid flow adsorption test and an antimony flow adsorption test were performed. The results are shown in Table 2 below.

  If the iodic acid and / or antimony adsorbent according to the present invention is used, iodic acid and / or antimony can be adsorbed without breaking through for a long time even when a liquid containing iodic acid and / or antimony is passed at high speed. Since it can be removed, it can be suitably used in iodic acid and / or antimony treatment methods.

DESCRIPTION OF SYMBOLS 1 Tank 2 Pump 3 Space part cover 4 Coagulation tank 5 Rotating container 6 Rotating shaft 7 Hose 8 Heater a Molding slurry b Opening c Space part d Coagulating liquid

Claims (11)

  Iodic acid and / or antimony adsorbent in the form of a porous granular molded body containing an inorganic ion adsorbent and an organic polymer resin, the iodic acid and / or antimony adsorbent mercury of the porous granular molded body The iodic acid and / or antimony adsorbent, wherein the mode pore diameter measured with a porosimeter is 0.08 to 0.70 μm.   The iodic acid and / or antimony adsorbent according to claim 1, wherein an opening ratio of the outer surface of the porous granular molded body is 5% or more and less than 30%.   The iodine according to claim 1 or 2, wherein a ratio of the mode pore diameter to the median diameter (mode pore diameter / median diameter) measured by a mercury porosimeter of the porous granular compact is 0.80 to 1.30. Acid and / or antimony adsorbent. The iodic acid and / or antimony adsorbent according to any one of claims 1 to ³ , wherein a specific surface area of the porous granular compact measured with a mercury porosimeter is 10 to 100 m ² / cm ³ .   The iodic acid and / or antimony adsorbent according to any one of claims 1 to 4, wherein the porous granular molded body is in the form of spherical particles having an average particle diameter of 100 to 2500 µm. The inorganic ion adsorbent is represented by the following formula (I):
_{MN x O n · mH 2 O} ······ (I)
{Wherein _x is a number from 0 to 3, _n is a number from 1 to 4, m is a number from 0 to 6, and M and N are independently of each other Ti, Zr, Sn, Sc. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge , A metal element selected from the group consisting of Nb and Ta. } The iodic acid and / or antimony adsorbent as described in any one of Claims 1-5 containing at least 1 type of metal oxide represented by these. The metal oxide is the following (a) to (c):
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) activated alumina,
The iodic acid and / or antimony adsorbent according to claim 6, which is selected from any group of   The organic polymer resin is at least one selected from the group consisting of ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyethersulfone (PES), and polyvinylidene fluoride (PVDF). The iodic acid and / or antimony adsorbent according to any one of claims 1 to 7. The following steps:
(1) A step of obtaining a slurry by pulverizing and mixing an organic polymer resin good solvent and an inorganic ion adsorbent,
(2) A step of obtaining a mixed slurry by dissolving an organic polymer resin and a water-soluble polymer in the slurry obtained in step (1),
(3) A step of obtaining a molded product by molding the mixed slurry obtained in step (2),
(4) The step of promoting the solidification of the molded product obtained in step (3) by controlling the temperature and humidity of the space where the molded product contacts, and (5) The step of promoting solidification in step (4) Solidifying the molded product in a poor solvent of the organic polymer resin to obtain a porous molded body,
The manufacturing method of the iodic acid and / or antimony adsorption material as described in any one of Claims 1-8 containing these.   A column having a treated water introduction port and a discharge port filled with the iodic acid and / or antimony adsorbent according to any one of claims 1 to 8, and iodic acid in the treated water obtained from the discharge port And / or a detector for detecting antimony, an iodic acid and / or antimony adsorption device.   A dispersion of iodic acid and / or antimony adsorbent, wherein the iodic acid and / or antimony adsorbent according to any one of claims 1 to 8 is dispersed in water.