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WO2020017538A1 - Échangeur d'ions inorganiques, son procédé de production et procédé de purification d'eau contenant du strontium radioactif - Google Patents

Échangeur d'ions inorganiques, son procédé de production et procédé de purification d'eau contenant du strontium radioactif Download PDF

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Publication number
WO2020017538A1
WO2020017538A1 PCT/JP2019/028032 JP2019028032W WO2020017538A1 WO 2020017538 A1 WO2020017538 A1 WO 2020017538A1 JP 2019028032 W JP2019028032 W JP 2019028032W WO 2020017538 A1 WO2020017538 A1 WO 2020017538A1
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Prior art keywords
ion exchanger
inorganic ion
alkali metal
powder
strontium
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English (en)
Japanese (ja)
Inventor
裕延 沖
飯田　正紀
義之 佐野
前川　文彦
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2020531334A priority Critical patent/JP7400716B2/ja
Publication of WO2020017538A1 publication Critical patent/WO2020017538A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/09—Inorganic material
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange

Definitions

  • the present invention relates to an inorganic ion exchanger and a method for producing the same.
  • the present invention also relates to a method for purifying water containing radioactive strontium, using the inorganic ion exchanger.
  • alkali metal titanate compounds are ionized. Methods have been proposed for use as exchangers.
  • the alkali metal titanate compound used as the ion exchanger include a layered structure alkali metal titanate having a TiO 5 triangular bipyramidal chain structure and a layered alkali metal titanate having a TiO 6 octahedral chain structure.
  • Patent Document 1 a silicic acid source, a sodium and / or potassium compound, titanium tetrachloride, and water are mixed to obtain a mixed gel, and the mixed gel is obtained by a hydrothermal reaction.
  • Crystalline silico titanates Patent Document 2 and the like are known.
  • As an alkali metal titanate compound potassium tetratitanate K 2 Ti 4 O 9 is known to be able to exchange potassium ions for calcium ions by taking in water between crystal layers (Non-Patent Document 1).
  • the conventional method using a synthetic zeolite-based adsorbent or a cation exchange resin or the conventional method using an alkali metal titanate compound as an ion exchanger has a problem that the ability to remove radioactive strontium is not sufficient.
  • the problem to be solved by the present invention is to use an inorganic ion exchanger capable of removing radioactive strontium until the radioactive strontium falls below a reference value, a method for producing the inorganic ion exchanger, and using the inorganic ion exchanger.
  • Another object of the present invention is to provide a method for purifying water containing radioactive strontium.
  • the present inventor has found that an inorganic ion exchanger containing a layered titanate containing at least one selected from the group consisting of an alkali metal salt and an alkali metal carbonate in a crystal structure has high ion exchange ability, The present inventors have found that radioactive strontium can be removed from water containing radioactive strontium with high efficiency, and have completed the present invention.
  • the present invention relates to the following [1] to [10].
  • the layered titanate is, xA 2 O ⁇ TiO 2 ⁇ yH 2 O ⁇ zA 2 CO 3 (A represents Li, K, Na, at least one element selected from Rb and Cs, x, y and z are respectively represented by 0.02 ⁇ x ⁇ 2.0, y ⁇ 0.05 and z ⁇ 0.015).
  • the inorganic ion exchange according to [1], wherein body.
  • the layered titanate has a diffraction peak having a maximum point in a range of a diffraction angle (2 ⁇ ) of 1 ° or more and 8 ° or less in a powder X-ray diffraction pattern measured using CuK ⁇ radiation.
  • a diffraction angle (2 ⁇ ) of 1 ° or more and 8 ° or less in a powder X-ray diffraction pattern measured using CuK ⁇ radiation.
  • Kd Qeq / Ceq (1)
  • Kd is the partition coefficient (ml / g)
  • Ceq is the strontium concentration in the aqueous solution when the equilibrium is reached (mol / ml)
  • Qeq is strontium per unit weight of the inorganic ion exchanger when the equilibrium is reached. (Denotes the adsorption amount (mol / g), respectively)
  • [6] The method for producing an inorganic ion exchanger according to any one of [1] to [5], wherein the following steps (1) and (2) are sequentially performed. How to make exchangers.
  • Step (1) mixing the titanium compound powder with an excess amount of at least one powder selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates
  • Step (2) the step (1) [7] a step of heating the mixture obtained in the above at a temperature of 700 ° C. or more and 1500 ° C. or less, wherein the following steps (3) and (4) are sequentially performed. Production method.
  • Step (3) a step of washing the inorganic ion exchanger obtained in the step (2) with water
  • Production method. [9] The method for producing an inorganic ion exchanger according to any one of [6] to [8], wherein in the step (1), a powder of an alkali metal sulfate is further mixed.
  • the inorganic ion exchanger of the present invention has a high ion exchange capacity and can remove radioactive substances from water containing radioactive substances with high efficiency. For this reason, when removing a radioactive substance from a radioactive waste liquid, the amount used as an inorganic ion exchanger can be reduced, the purification cost can be reduced, and the amount of radioactive waste can be reduced. Further, the inorganic ion exchanger of the present invention can be used for removing heavy metals from well water, recovering valuable resources from seawater, and removing harmful substances from contaminated soil.
  • 3 is a powder X-ray diffraction pattern of the layered titanate obtained in Example 1.
  • 3 is a 13 C-NMR spectrum of the layered titanate obtained in Example 1.
  • the inorganic ion exchanger of the present invention contains, in its crystal structure, a layered titanate containing at least one selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates.
  • alkali metal carbonate contained in the crystal structure of the layered titanate include, for example, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and the like. Or two or more of them may be contained in combination.
  • Examples of the alkali metal bicarbonate contained in the crystal structure of the layered titanate include, for example, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, and the like. May be contained alone or in combination of two or more.
  • the form of the inorganic ion exchanger of the present invention is not particularly limited, and examples thereof include powder, granules, particles, columns, spheres, pellets, honeycomb molded bodies, and porous molded bodies. , Alumina, zirconia, cordierite or the like may be supported on a support. Since the ion exchanger is generally used in a method of packing a column and passing a radioactive waste liquid or the like, the ion exchanger is in the form of granules or particles having a size of about 1 mm and is fragile even if it is in contact with water for a long time. It is preferable that the form is not changed.
  • xA 2 O ⁇ TiO 2 ⁇ yH 2 O ⁇ zA 2 CO 3 (A is Li, K, Na, at least one selected from Rb and Cs X, y, and z each represent a numerical value of 0.02 ⁇ x ⁇ 2.0, y ⁇ 0.05, and z ⁇ 0.015).
  • x is preferably 0.05 ⁇ x ⁇ 1.0, and more preferably 0.1 ⁇ x ⁇ 0.5.
  • y is preferably 0.05 ⁇ y ⁇ 3.0, and more preferably 0.1 ⁇ y ⁇ 2.0.
  • z is preferably 0.015 ⁇ z ⁇ 1.5, and more preferably 0.02 ⁇ z ⁇ 1.0.
  • the zA 2 CO 3 may be zAHCO 3 , and the hydrogen ion in this case is obtained from yH 2 O. Therefore, if the said zA 2 CO 3 is ZAHCO 3, the layered titanate, xA 2 O ⁇ TiO 2 ⁇ (y-z) H 2 O ⁇ zAHCO 3 ⁇ zAOH (A is Li, K, Na , Rb and Cs represent at least one element selected from the group consisting of x, y and z, each of which represents a value of 0.02 ⁇ x ⁇ 2.0, y ⁇ 0.05 and z ⁇ 0.015); Become.
  • the layered titanate has a diffraction point (2 ⁇ ) having a maximum point in a range of 1 ° or more and 8 ° or less, preferably 2 ° or more and 7 ° or less in a powder X-ray diffraction pattern measured using CuK ⁇ radiation. It preferably has a peak.
  • the distance is 1.1 nm to 8.8 nm, preferably 1.3 nm to 4.4 nm.
  • the diffraction angle (2 ⁇ ) of the diffraction peak can be calculated from a diffraction pattern obtained by correcting a diffraction peak pattern obtained by actual powder X-ray diffraction with a baseline.
  • This baseline correction can be performed by fitting a background curve obtained from a compound having no diffraction peak in the diffraction angle range to be calculated.
  • the layered titanate has low crystallinity in which the half value width of the diffraction peak is 3 ° or more at 2 ⁇ . As the half width of the diffraction peak increases, the crystallinity decreases, and as the half width of the diffraction peak decreases, the crystallinity increases.
  • the layered titanate in the present invention is preferably a low crystalline compound having a half value width of the diffraction peak of 3 ° or more at 2 ⁇ , more preferably a low crystalline compound of 3 ° or more and 10 ° or less. .
  • the half width of the diffraction peak can be calculated from the diffraction pattern obtained by correcting the diffraction peak pattern obtained by actual powder X-ray diffraction with a baseline. This baseline correction can be performed by fitting a background curve obtained from a compound having no diffraction peak in the diffraction angle range to be calculated.
  • the half width can be obtained after peak separation. Peak separation can be performed by approximating Gaussian basic waveforms by superimposition and performing curve fitting on each of the overlapping peaks.
  • the inorganic ion exchanger of the present invention contains at least one selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates in the crystal structure of the layered titanate. It has a structure in which the interlayer distance between titanic acids is widened by the intervening carbonate or alkali metal bicarbonate.
  • a conventional inorganic ion exchanger containing a layered titanate has a structure containing water molecules between layers of titanic acid, and the interlayer distance between titanic acids is widened.
  • the inorganic ion exchanger of the present invention can further incorporate water molecules into the crystal structure. That is, the inorganic ion exchanger of the present invention includes those containing water molecules and at least one selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates in the crystal structure of the layered titanate. I do. When containing both water molecules and at least one selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates, only water molecules or from the group consisting of alkali metal carbonates and alkali metal bicarbonates It can be expected that the technical effects of the present invention will be exhibited synergistically as compared with the case where only at least one selected type is included.
  • Partition coefficient of inorganic ion exchanger When the inorganic ion exchanger of the present invention is dispersed in an aqueous solution containing strontium, the alkali metal in the inorganic ion exchanger undergoes an exchange reaction with strontium in the aqueous solution, strontium is incorporated into the inorganic ion exchanger, and strontium is incorporated. Inorganic ion exchangers can be formed. This reaction is an equilibrium reaction represented by the following formula. The more the equilibrium is inclined toward the side of strontium incorporation (to the right), the higher the amount of strontium incorporation can be.
  • A represents an alkali metal
  • IEX represents an inorganic ion exchanger
  • the strontium uptake capacity of the inorganic ion exchanger can be represented by a partition coefficient Kd represented by the following formula (1) when the inorganic ion exchanger is dispersed in an aqueous alkaline strontium solution having a pH of 12 or more.
  • Kd Qeq / Ceq (1)
  • Kd is the partition coefficient (ml / g)
  • Ceq is the strontium concentration (mol / ml) in the solution when the equilibrium reaction is reached
  • Qeq is the inorganic ion when the equilibrium is reached in the equilibrium reaction.
  • the inorganic ion exchanger of the present invention is dispersed in an aqueous solution containing strontium, and then the strontium concentration in the aqueous solution is measured, and the time is determined by determining the time at which the change in the concentration stops. But usually for 3-5 hours.
  • the partition coefficient Kd of the inorganic ion exchanger of the present invention is preferably at least 30,000 ml / g, more preferably at least 100,000 ml / g, even more preferably at least 500,000 ml / g.
  • the higher the partition coefficient Kd the more the equilibrium is inclined toward the strontium incorporation side (right side), and the higher the strontium incorporation ability.
  • the partition coefficient Kd of the inorganic ion exchanger of the present invention since the partition coefficient Kd of the inorganic ion exchanger of the present invention is high, it has a high strontium uptake ability.
  • strontium adsorption a phenomenon in which an ion exchanger takes in strontium by ion exchange.
  • the inorganic ion exchanger of the present invention can be produced by sequentially performing the following steps (1) and (2).
  • a titanium compound powder and an excess amount of at least one kind of powder (hereinafter, also referred to as an alkali metal carbonate or the like) selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates are mixed.
  • the amount of the powder of the alkali metal carbonate or the like mixed with the powder of the titanium compound is not particularly limited as long as it is more than the amount of the powder of the titanium compound. Is preferably, more preferably, 150 mol% or more, and further preferably, 200 mol% or more.
  • the alkali metal carbonate and alkali metal bicarbonate used in the method for producing an inorganic ion exchanger of the present invention include the above-mentioned alkali metal carbonate and alkali metal bicarbonate.
  • Examples of the titanium compound used in the method for producing an inorganic ion exchanger of the present invention include titanium oxide, metatitanic acid, alkali metal titanate, and metal titanium. These may be used alone or may be used alone. A combination of more than one species may be used.
  • Examples of the alkali metal titanate include lithium titanate, sodium titanate, potassium titanate, rubidium titanate, and cesium titanate.
  • the reaction in the alkali metal carbonate melted at a high temperature in the step (2) Precipitation of the titanium compound and uneven reaction are suppressed.
  • the compound after the reaction and the melt of the excess alkali metal carbonate are cooled in a state of being immersed in the alkali metal sulfate powder, so that they are solidified and shrunk when they are shrunk. A gap is formed at the interface with the container, and the product obtained in the step (2) can be easily taken out of the production container.
  • the alkali metal sulfate is not particularly limited, and includes, for example, potassium sulfate and sodium sulfate.
  • Step (2) is a step of heating the mixture obtained in the above step (1) at a temperature of 700 ° C. or more and 1500 ° C. or less.
  • the heating time is preferably 30 minutes to 100 hours.
  • the titanium compound reacts with the alkali metal carbonate to generate a layered titanate.
  • An alkali metal carbonate can be contained in the crystal structure of the layered titanate.
  • the alkali metal bicarbonate is decomposed at a high temperature to become an alkali metal carbonate.
  • the container and the device used for heating have a structure and a mechanism capable of efficiently exhausting carbon dioxide gas.
  • the container preferably has a cutout for ventilation
  • the heating device preferably has a mechanism for sucking the exhaust gas and taking in the outside air little by little.
  • the alkali metal bicarbonate is formed by reacting a part of the alkali metal carbonate contained in the crystal structure in step (2) with water molecules and carbon dioxide supplied from the air or the like. It is.
  • the inorganic ion exchanger obtained in this manner is an inorganic ion exchanger containing a layered titanate containing no water molecule in the crystal structure.
  • the inorganic ion exchanger of the present invention further performs the following steps (3) and (4) in order to produce an inorganic ion exchanger containing a layered titanate further containing a water molecule in the crystal structure. be able to.
  • Step (3) a step of washing the inorganic ion exchanger obtained in the step (2) with water
  • Step (4) a step of drying the inorganic ion exchanger after the washing in the step (3)
  • the step (3) is a step of washing the inorganic ion exchanger obtained in the step (2) with water to remove excess alkali metal carbonate outside the crystal structure of the inorganic ion exchanger.
  • excess alkali metal carbonate outside the crystal structure of the inorganic ion exchanger is removed, and at the same time, the crystal structure of the layered titanate is removed. Water molecules are taken into the inside, and the interlayer distance of the titanic acid is further increased.
  • the product obtained in the step (2) is preferably pulverized before the step (3).
  • a crusher a jaw crusher, a roll crusher, a hammer mill, or the like can be used.
  • the washing with water is preferably gentle so that the alkali metal carbonate and the like existing in the crystal structure of the ion exchanger are not removed. That is, by washing with an appropriate amount of water or washing with non-high-temperature water, more water molecules can be retained in the crystal structure.
  • washing with water involves slurrying with water at room temperature 3 to 10 times the weight of the product of step (2), then dewatering, and then 3% on the weight of the resulting dewatered cake. It is preferable to use a method of passing water of normal temperature having a weight of up to 10 times, or a method of repeating the slurrying and dehydration two to three times.
  • the step (4) is a step of drying the inorganic ion exchanger after the washing in the step (3). It may be possible to completely remove only water molecules and leave only alkali metal carbonates and the like in the crystal structure, but it is preferable to leave not only alkali metal carbonates and the like but also water molecules in the crystal structure. However, as compared with leaving only the alkali metal carbonate or the like in the crystal structure, the interlayer of the titanic acid can be made wider, and the technical effects of the present invention can be maximized. Therefore, in order to allow the water molecules incorporated in the crystal structure of the layered titanate in the step (3) to remain in the crystal structure even after the inorganic ion exchanger is dried in the step (4), The drying conditions are preferably mild.
  • step (3) and the step (4) a part of the water molecule taken into the crystal structure, a part of the alkali metal carbonate present in the crystal structure, and the water are supplied from water or air. Reacts with the carbon dioxide to form alkali metal bicarbonate.
  • the dried product of the inorganic ion exchanger obtained in the step (4) can be pulverized or pulverized to a powder as required. Further, the obtained powder of the inorganic ion exchanger may be subjected to a granulation treatment using a granulation aid to form a granulated body.
  • a granulation aid to form a granulated body.
  • the rolling granulation method fluidized bed granulation method, mixing stirring granulation method, extrusion granulation method, melt granulation method, spray granulation method, compression granulation method, A pulverization granulation method and the like can be mentioned.
  • the granulation aid examples include clay minerals such as bentonite, attapulgite, sepiolite, allophane, halloysite, imogolite, kaolinite; sodium silicate, calcium silicate, magnesium silicate, sodium metasilicate, calcium metasilicate, and metasilicate.
  • Silicate compounds such as magnesium, sodium metasilicate aluminate, calcium metasilicate aluminate, magnesium metasilicate aluminate; organic polymers such as polyvinyl alcohol, carboxymethyl cellulose, sucrose fatty acid ester, butadiene-styrene latex, and fluororesin Is mentioned. These may be used alone or in a combination of two or more.
  • the inorganic ion exchanger of the present invention uses the inorganic ion exchanger of the present invention, water containing a radioactive substance, specifically, water containing radioactive strontium can be purified, and radioactive strontium contained in the water can be removed.
  • the method for purifying water containing radioactive strontium includes a step of contacting water containing radioactive strontium with the inorganic ion exchanger of the present invention, and a step of separating the inorganic ion exchanger from water obtained after the contact. It can be carried out by performing it sequentially.
  • the method of contacting water containing radioactive strontium with the inorganic ion exchanger of the present invention is not particularly limited, for example, the inorganic ion exchanger may be a column or the like. Examples include a method of filling a container and passing water containing radioactive strontium, and a method of dispersing the inorganic ion exchanger of the present invention in water containing radioactive strontium.
  • the method for separating the inorganic ion exchanger from water obtained after contacting the water containing radioactive strontium with the inorganic ion exchanger of the present invention comprises the inorganic ion exchanger of the present invention.
  • the inorganic ion exchanger can be separated from water obtained after contacting water containing radioactive strontium with the exchanger.For example, by filling the inorganic ion exchanger into a container such as a column, the radioactive strontium is added.
  • the passed water When passing the containing water, the passed water may be fractionated as it is, and when the inorganic ion exchanger of the present invention is dispersed in the water containing radioactive strontium, the dispersed inorganic ion exchanger is used. Separating the inorganic ion exchanger from the contacted water using a container having a strainer structure at the top or bottom, etc. It can be carried out more.
  • ⁇ Metal element composition analysis> Using a mixed acid of hydrofluoric acid, nitric acid, and perchloric acid, the sample is decomposed by heating to 140 ° C. in a pressure-resistant sealed container made of Teflon (registered trademark) to form a nitric acid solution, and then containing a metal element by ICP-MS. The amount was analyzed.
  • Example 1 27.6 g of anhydrous potassium carbonate powder (400 mmol as K), 35 g of potassium sulfate powder and 8.0 g of anatase-type titanium dioxide powder (100 mmol as Ti) are well mixed in a mortar, put in an alumina crucible and placed at 950 ° C. for 20 minutes. Heated for hours. The product was coarsely crushed in a mortar, suspended in 500 g of deionized water and stirred for 1 hour. Next, the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing filtration under reduced pressure.
  • the obtained white powder was subjected to the powder X-ray diffraction measurement, and the diffraction pattern shown in FIG. 1 was obtained.
  • a broad peak having a maximum point at a diffraction angle of 8 ° or less was observed, suggesting a structure in which the layers of the layered material were irregularly spread.
  • the peak position of the lowest angle diffraction line was 6.8 °, and the half value width was 5.2 ° at 2 ⁇ .
  • the obtained white powder was subjected to the TG-MS analysis. As a result, the weight was reduced by 13%, and the generated gas was identified as H 2 O.
  • the obtained white powder was analyzed by 13 C-NMR, a chart shown in FIG.
  • Table 1 shows the results of the above analysis. From the results shown in Table 1, the white powder obtained above is a low-crystalline layered titanic acid containing water and at least one selected from the group consisting of potassium carbonate and potassium bicarbonate in the crystal structure. It was presumed to be potassium and had excellent strontium adsorption ability.
  • Example 2 10.4 g of anhydrous potassium carbonate powder (150 mmol as K), 13 g of potassium sulfate powder and 9.8 g of metatitanic acid powder (100 mmol as Ti) are well mixed in a mortar, put in an alumina crucible and heated at 900 ° C. for 20 hours. did. The product was coarsely crushed in a mortar, suspended in 350 g of deionized water and stirred for 1 hour. Next, the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing filtration under reduced pressure. The washed cake was dried with hot air at 50 ° C. to obtain a white powder.
  • the obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test.
  • Table 1 shows the results. From the results shown in Table 1, the obtained white powder was a low-crystalline layered potassium titanate containing water and at least one selected from the group consisting of potassium carbonate and potassium bicarbonate in the crystal structure. It was presumed that the compound had excellent strontium adsorption ability.
  • Example 3 21.2 g of anhydrous sodium carbonate powder was dissolved in 200 ml of water, and 240 g (100 mmol as Ti) of a 10% by weight aqueous solution of titanium sulfate was added dropwise over 30 minutes while stirring at room temperature. The produced titanium hydroxide was recovered by centrifugation, evaporated to dryness at 100 ° C., and ground in a mortar to obtain 11.3 g of titanium hydroxide powder. The total amount of the titanium hydroxide powder, 15.9 g of anhydrous sodium carbonate powder (300 mmol as Na), and 25 g of potassium sulfate powder were mixed well in a mortar, and placed in an alumina crucible and heated at 900 ° C. for 20 hours.
  • the product was coarsely crushed in a mortar, suspended in 500 g of deionized water and stirred for 1 hour. Next, the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing filtration under reduced pressure. The washed cake was dried with hot air at 50 ° C. to obtain a white powder. The obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test. Table 1 shows the results.
  • the obtained white powder is a low-crystalline layered sodium titanate containing water and at least one selected from the group consisting of sodium carbonate and sodium bicarbonate in the crystal structure. It was presumed that the compound had excellent strontium adsorption ability.
  • Example 4 14.9 g of anhydrous lithium carbonate powder was dissolved in 200 ml of water, heated to 70 ° C., and 190 g (100 mmol as Ti) of a 10% by weight aqueous solution of titanium tetrachloride was added dropwise with stirring over 30 minutes. The generated titanium hydroxide was collected by centrifugation, evaporated to dryness at 100 ° C., and ground in a mortar to obtain 12.8 g of titanium hydroxide powder.
  • the total amount of the titanium hydroxide powder, 9.2 g (250 mmol as Li) of anhydrous lithium carbonate powder and 25 g of potassium sulfate powder were mixed well in a mortar, and placed in an alumina crucible and heated at 900 ° C. for 20 hours.
  • the product was coarsely crushed in a mortar, suspended in 500 g of deionized water and stirred for 1 hour.
  • the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing the reduced pressure filtration.
  • the washed cake was dried with hot air at 50 ° C. to obtain a white powder.
  • the obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test.
  • Table 1 shows the results. From the results shown in Table 1, the obtained white powder is a low-crystalline layered structure lithium titanate containing water and at least one selected from the group consisting of lithium carbonate and lithium hydrogen carbonate in the crystal structure. And had excellent strontium adsorption ability.
  • Comparative Example 2 1 g of the potassium titanate obtained in Comparative Example 1 was suspended in 60 g of deionized water and stirred for 48 hours. Then, the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 10 g of deionized water while continuing the reduced pressure filtration. The washed cake was air-dried at room temperature to obtain a white powder. The obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test. Table 1 shows the results.
  • the product was coarsely crushed in a mortar, suspended in 500 g of deionized water and stirred for 1 hour. Next, the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing filtration under reduced pressure. The washed cake was dried with hot air at 50 ° C. to obtain a white powder.
  • the obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test. Table 1 shows the results. From the results shown in Table 1, it was estimated that the obtained white powder was sodium titanate having a tunnel structure and containing no alkali metal carbonate or alkali metal carbonate in the crystal structure.
  • the total amount of the titanium hydroxide powder, 7.4 g of anhydrous lithium carbonate powder (200 mmol as Li), and 25 g of potassium sulfate powder were mixed well in a mortar, and placed in an alumina crucible and heated at 900 ° C. for 20 hours.
  • the product was coarsely crushed in a mortar, suspended in 500 g of deionized water and stirred for 1 hour.
  • the mixture was filtered under reduced pressure to form a dehydrated cake, and rinsed with 100 g of deionized water while continuing filtration under reduced pressure.
  • the washed cake was dried with hot air at 50 ° C. to obtain a white powder.
  • the obtained white powder was subjected to metal element composition analysis, C and H content measurement, powder X-ray diffraction, TG-MS analysis, 13 C-NMR and strontium adsorption test. Table 1 shows the results. From the results shown in Table 1, it was estimated that the obtained white powder was layered lithium titanate containing no alkali metal carbonate and no alkali metal carbonate in the crystal structure.
  • the layered titanates of Examples 1 to 4 each had a diffraction peak having a maximum point in the range of a diffraction angle (2 ⁇ ) of 1 ° or more and 8 ° or less, It was confirmed that the interlayer distance of titanic acid was large.
  • the titanates of Comparative Examples 1 to 4 have a diffraction angle (2 ⁇ ) of more than 8 °, and the interlayer distance of titanic acid is smaller than that of the layered titanates of Examples 1 to 4. Had become.
  • the layered titanates of Examples 1 to 4 had a half width of the diffraction peak of powder X-ray diffraction of 2 ⁇ , which was 3 ° or more, and were confirmed to be low crystalline titanates. .
  • the titanates of Comparative Examples 1 to 4 had a half width at half maximum of the diffraction peak of powder X-ray diffraction of 2 ⁇ , which was 1 ° or less, and were confirmed to be titanates with high crystallinity.
  • TG-MS it was confirmed that the layered titanates of Examples 1 to 4 contained water in the crystal structure.
  • the titanates of Comparative Examples 1, 2 and 4 did not contain water in the crystal structure.
  • the inorganic ion exchanger of the present invention has a high ion exchange capacity and can remove radioactive substances from water containing radioactive substances with high efficiency. For this reason, for example, removal of heavy metals from various waters such as well water, lake water, river water, rainwater, spring water, sewage water, factory water supply, medium water, sewage, etc., recovery of valuable resources from seawater, pollution It can also be used to remove harmful substances from soil.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne : un échangeur d'ions inorganiques qui a une capacité d'échange d'ions élevée et qui est capable d'éliminer une substance radioactive d'un déchet liquide radioactif avec une efficacité élevée ; et un procédé de purification d'eau contenant une substance radioactive, qui utilise cet échangeur d'ions inorganiques. La présente invention concerne : un échangeur d'ions inorganiques comprenant un titanate en couches contenant, dans une structure cristalline, au moins une substance choisie dans le groupe constitué par des carbonates de métaux alcalins et des hydrogénocarbonates de métaux alcalins ; un procédé de production dudit échangeur d'ions inorganiques ; et un procédé de purification d'eau contenant du strontium radioactif, qui utilise l'échangeur d'ions inorganiques.
PCT/JP2019/028032 2018-07-17 2019-07-17 Échangeur d'ions inorganiques, son procédé de production et procédé de purification d'eau contenant du strontium radioactif Ceased WO2020017538A1 (fr)

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CN115662670A (zh) * 2022-11-04 2023-01-31 中核四0四有限公司 一种将高放溶液中的硝酸锶转换为钛酸锶的方法及系统

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CN114689830B (zh) * 2022-05-06 2023-05-26 华电电力科学研究院有限公司 一种阴离子树脂的碳酸氢根交换容量检测方法及装置
CN115504504B (zh) * 2022-11-07 2023-07-28 攀钢集团研究院有限公司 降低偏钛酸中杂质铜元素含量的方法

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JPH07108178A (ja) * 1993-08-20 1995-04-25 Toagosei Co Ltd 粒状無機イオン交換体の製造方法
JP2000502595A (ja) * 1995-12-22 2000-03-07 イヴォ パワー エンジニアリング オサケ ユキチュア 粒状チタネートイオン交換体と、その製造方法
WO2017086056A1 (fr) * 2015-11-18 2017-05-26 国立大学法人香川大学 Adsorbant d'ions strontium et son procédé de production
JP2017209594A (ja) * 2016-05-23 2017-11-30 株式会社クボタ イオン交換材料、イオン交換体、イオン吸着装置、水処理システム、イオン交換材料の製造方法、及びイオン交換体の製造方法

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JPH07108178A (ja) * 1993-08-20 1995-04-25 Toagosei Co Ltd 粒状無機イオン交換体の製造方法
JP2000502595A (ja) * 1995-12-22 2000-03-07 イヴォ パワー エンジニアリング オサケ ユキチュア 粒状チタネートイオン交換体と、その製造方法
WO2017086056A1 (fr) * 2015-11-18 2017-05-26 国立大学法人香川大学 Adsorbant d'ions strontium et son procédé de production
JP2017209594A (ja) * 2016-05-23 2017-11-30 株式会社クボタ イオン交換材料、イオン交換体、イオン吸着装置、水処理システム、イオン交換材料の製造方法、及びイオン交換体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115662670A (zh) * 2022-11-04 2023-01-31 中核四0四有限公司 一种将高放溶液中的硝酸锶转换为钛酸锶的方法及系统

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