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WO2021112163A1 - Corps moulé en oxyde de manganèse stratifié et son procédé de fabrication - Google Patents

Corps moulé en oxyde de manganèse stratifié et son procédé de fabrication Download PDF

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Publication number
WO2021112163A1
WO2021112163A1 PCT/JP2020/044990 JP2020044990W WO2021112163A1 WO 2021112163 A1 WO2021112163 A1 WO 2021112163A1 JP 2020044990 W JP2020044990 W JP 2020044990W WO 2021112163 A1 WO2021112163 A1 WO 2021112163A1
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Prior art keywords
manganese oxide
molded product
layered manganese
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layered
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English (en)
Japanese (ja)
Inventor
陵二 田中
尚登 西山
藤井　康浩
望水 井手
由布子 深田
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Sagami Chemical Research Institute
Tosoh Corp
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Sagami Chemical Research Institute
Tosoh Corp
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Priority to JP2021562706A priority Critical patent/JP7638899B2/ja
Publication of WO2021112163A1 publication Critical patent/WO2021112163A1/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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • 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 a layered manganese oxide molded product and a method for producing the same.
  • the operation of adsorbing and separating harmful or useful ions from an aqueous solution using a solid phase adsorbent is important as a separation technique because it does not involve concentration of a high-cost aqueous solution.
  • the adsorption of strontium ions is particularly important because strontium is produced in a large amount in fission products in uranium fission-type nuclear power generation and the strontium concentration has a low wastewater standard value.
  • Manganese oxide has been widely known as a material capable of selectively adsorbing and separating strontium.
  • Patent Document 1 discloses a layered manganese oxide having sodium ions in the layers, which is synthesized by a solid phase reaction method in which a manganese raw material and a sodium raw material are mixed and fired as an adsorbent for strontium ions in seawater.
  • Patent Document 2 discloses a layered manganese oxide having potassium ions in the layers, which is also synthesized by a solid-phase reaction method in which a manganese raw material and a potassium raw material are mixed and fired as an adsorbent for strontium ions in seawater. There is.
  • Non-Patent Document 1 As an adsorbent for radionuclides containing strontium, a burnesite-type layered manganese oxide is disclosed in Non-Patent Document 1. This substance is obtained by reacting a manganese hydroxide sol with magnesium permanganate and aging under high alkaline conditions (pH 13.7) for 7 days.
  • the bulk density of the molded product prepared from the layered manganese oxide powder synthesized by the solid phase reaction method and the inorganic binder is often low.
  • the bulk density is high without containing components such as a binder other than the adsorbent.
  • the layered manganese oxide molded product synthesized by the solid-phase reaction method has poor shape retention during water flow. If the shape retention is poor, there is a disadvantage that the layered manganese oxide molded product becomes muddy and difficult to handle when it is pulverized to block the flow path of the adsorption tower or when the layered manganese oxide molded product is taken out from the adsorption tower. Therefore, it is expected that the use of a layered manganese oxide molded product synthesized by the solid-phase reaction method for the treatment of contaminated water at a nuclear power plant will cause a big problem when disposing of the radioactive molded product.
  • the present invention solves these problems and provides a layered manganese oxide molded product that simultaneously establishes sufficient strontium adsorption performance, mechanical strength, and shape retention without any trouble.
  • a solid phase synthesis method in which raw materials are mixed and calcined, or a reaction between a permanganate and a manganese salt in an aqueous solution is performed.
  • an inorganic binder and a thickener composed of an organic substance are added and kneaded, then molded into a noodle shape using an extrusion molding machine, dried, and then crushed. A complicated manufacturing process was required.
  • the present invention solves this problem, and the layered manganese oxide molded product of the present invention can be produced by a simple process such as filtration, drying, and crushing after a wet reaction.
  • the present inventor has found that the strength, shape retention and adsorption performance are all satisfied at a high level. , The present invention has been completed. That is, the present invention has the following configurations.
  • the layered manganese oxide molded product according to one aspect of the present invention is composed of a layered manganese oxide containing at least an alkali metal and manganese, and has a crushing strength of 1000 mN or more and 5000 mN or less as measured by a microcompression tester. It has, does not contain an inorganic binder and an organic component, and 90% or more of all the granules are granules having a particle size of 0.2 mm or more and 1.7 mm or less, and a bulk density of 0.9 g / cm 3 or more.
  • the present invention has both strontium adsorption performance, mechanical strength, and shape retention, and is a layered manganese oxide that does not contain a binder that is inert to adsorption.
  • the molded product can be provided by a simple and cost-effective manufacturing method.
  • the layered manganese oxide molded product of the present invention is composed of a layered manganese oxide containing at least an alkali metal and manganese.
  • the layered A-Mn oxide represented by the composition formula A x MnO 2 and represented by at least one alkali metal selected from sodium and potassium differs in the size of the crystal lattice in the dry and wet states. It is preferable in that there is no such thing and it is possible to suppress the collapse of the molded body during water flow.
  • the alkali metal at least one of sodium and potassium can be used, and a mixture of both alkali metals may be used.
  • the alkali metal potassium is preferable because it can suppress changes in lattice volume during drying and wetting of the layered manganese oxide molded product of the present invention and can maintain shape retention during water flow.
  • A is an alkali metal
  • x represents the A / Mn molar ratio, that is, the range of x can be represented by 0.2 ⁇ x ⁇ 0.6, among which 0.3 ⁇ x ⁇ 0.5.
  • the layered manganese oxide molded product of the present invention has high strontium adsorption performance, which is more preferable.
  • the layered manganese oxide molded product containing both alkali metals of sodium and potassium and having 0.4 ⁇ x ⁇ 0.6 has higher strontium adsorption performance.
  • the oxygen composition varies slightly due to the formation of an empty lattice, it can be regarded as an integer value of 2. Further, water may be contained between the layers of the layered manganese oxide constituting the manganese oxide molded product of the present invention or between the particles.
  • the interlayer distance between the constituent layered manganese oxides is 7.0 angstroms or more and 7.3 angstroms or less. Is preferable. If this range is exceeded, the inside of the molded product may be distorted due to the volume change from the dry state to the wet state, and the layered manganese oxide molded product of the present invention may collapse.
  • the interlayer distance of the layered manganese oxide molded product of the present invention is the lowest angular diffraction peak of the powder X-ray diffraction pattern, and the 001 peak position (angle) when assigned by hexagonal crystals is converted into the plane spacing (angstrom). It can be obtained by.
  • the FWHM is preferably 0.4 ° or more and 3.5 ° or less, more preferably 0.4 ° or more and 3.0 ° or less, and further preferably 0.7 ° or more and 2.2 ° or less.
  • the FWHM of the 001 peak when assigned as a hexagon in the powder X-ray diffraction experiment is 2.5 ° or more. It was found that the layered manganese oxide molded product having a temperature of 3.5 ° or less has higher strontium adsorption performance.
  • the layered manganese oxide molded product of the present invention is characterized in that it exhibits a high crushing strength of 1000 mN or more and 5000 mN or less as measured by a microcompression tester. If it is less than 1000 mN as measured by a microcompression tester, the mechanical strength is insufficient, and if it exceeds 5000 mN, the porosity is impaired and the strontium adsorption performance is lowered. From the viewpoint of shape retention and strontium adsorption performance, the crushing strength is preferably 2000 mN or more and 4000 mN or less.
  • the layered manganese oxide molded product of the present invention preferably has a stirring wear degree of 15% by weight or less, which is an index for evaluating the shape retention of the molded product during water flow.
  • the degree of agitation wear can be measured in accordance with JIS-K-1464 (wear test of industrial desiccant).
  • the layered manganese oxide molded product of the present invention is characterized by containing no inorganic binder and no organic component.
  • the fact that the inorganic binder and the organic component are not contained means that the measurement means is below the detection limit.
  • the adsorption performance can be improved, and the strength and shape retention of the molded product can be maintained.
  • Colloidal particles such as silicon, aluminum, titanium and zirconium components, as well as layered or fibrous silicates, specifically bentonite and sepiolite, can be listed as common inorganic binders of the present invention.
  • the layered manganese oxide molded product does not contain these.
  • the molded product does not contain an organic component, and it is preferable that the carbon concentration in the molded product is 3000 ppm or less, that is, not more than the detection limit of each measuring means.
  • the carbon concentration in the molded product is 3000 ppm or less, that is, not more than the detection limit of each measuring means.
  • it can be obtained by back-calculating from the amount of CO or CO 2 produced by high-temperature combustion of a sample.
  • the layered manganese oxide molded product of the present invention does not contain an inorganic binder or an organic thickener, all the molded products function for adsorption and increase the bulk density, so that the amount of the layered manganese oxide molded product is larger than that of a fixed volume adsorption tower. It can be filled with heavy adsorbents. Furthermore, despite the fact that no binder is used, it is possible to achieve strong mechanical strength and shape retention during water flow only by electrostatic agglomeration of particles.
  • 90% or more of the whole grains are granules having a particle size of 0.2 mm or more and 1.7 mm or less. If the particle size of 0.2 mm or more and 1.7 mm or less is less than 90% of the whole grains, the particle size distribution becomes wide and the performance of the adsorption tower deteriorates. If the particles having a particle size of less than 0.2 mm exceed 10% of the total particles, there is an adverse effect that the pressure loss increases when the molded product is filled in the adsorption tower. On the other hand, when the particles exceeding 1.7 mm exceed 10% of the whole grains, the liquid contact surface area is reduced, so that the adsorption performance is significantly lowered.
  • the whole grains have a particle size of 0.2 mm or more and 1.7 mm or less. Further, it is preferable that the particle size of 90% or more of the whole grain is 0.3 mm or more and 1.0 mm or less. These are the particle sizes that are assumed to be filled in the adsorption tower of the actual contaminated water treatment facility of a nuclear power plant.
  • the layered manganese oxide molded product of the present invention is characterized by having a bulk density of 0.9 g / cm 3 or more. 1.0 g / cm 3 or more is preferable. If the bulk density is less than 0.9 g / cm 3 , the weight of the molded product that can be filled in a constant volume is reduced, so that the adsorption capacity is reduced.
  • the layered manganese oxide molded product of the present invention contains at least a metal salt aqueous solution containing manganese, an alkali metal aqueous solution and an oxidizing agent having an alkali metal / manganese molar ratio of 2 or more and 10 or less, and the oxidation-reduction potential of the reaction solution is based on a saturated caromel electrode.
  • step 2 in which the precipitated substance is thermally cured at 40 ° C. or higher and 200 ° C. or lower after filtration.
  • the manganese-containing metal salt aqueous solution used in step 1 can be prepared by dissolving the manganese-containing metal salt in water.
  • the metal salt containing manganese include water-soluble manganese sulfate (II), manganese chloride (II), manganese nitrate (II), manganese acetate (II), and the like, and even if it is anhydrous, it is a hydrate. There may be.
  • manganese sulfate (II) is most suitable in consideration of waste liquid treatment, corrosiveness, and raw material cost. Further, manganese and other metal ions can be mixed and used as long as the formation of the layered manganese oxide is not inhibited.
  • the alkaline earth metal concentration in the metal salt aqueous solution is low, and the total alkaline earth metal concentration must be less than 1500 ppm.
  • the total alkaline earth metal concentration is preferably less than 1000 ppm, more preferably 500 ppm, and even more preferably less than 100 ppm.
  • the total concentration (metal concentration) of all metals such as manganese in the metal salt aqueous solution is arbitrary, but the metal concentration affects productivity, so 1.0 mol / L or more is preferable, and 2.0 mol / L or more is preferable. More preferred.
  • the alkali metal aqueous solution used in step 1 can be prepared by dissolving the alkali metal compound in water.
  • the alkali metal compound for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or the like is suitable from the viewpoint of water solubility, cost, and pH adjustment.
  • the alkali metal concentration of the alkali metal aqueous solution can be exemplified as 1 mol / L or more from the viewpoint of productivity.
  • the alkali metal / manganese molar ratio is 2 or more and 10 or less.
  • manganese tetraoxide (Mn 3 O 4 ) is by-produced, and if it exceeds 10, manganese tetraoxide (Mn 3 O 4 ) is by-produced. From the viewpoint of strontium adsorption performance, it is preferably 3 or more and 8 or less.
  • Examples of the oxidizing agent used in step 1 include hydrogen peroxide, oxygen, air, and peroxodisulfate.
  • Examples of the peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate.
  • hydrogen peroxide solution, oxygen or air is preferable in terms of ease of raw material procurement and cost. Further economically, oxygen or air is preferable, and air is more preferable. Gases such as air and oxygen are added by bubbling in a mixed aqueous solution using a bubbler or the like.
  • a mixed aqueous solution is obtained by adjusting the redox potential of the reaction solution in step 1 to ⁇ 0.2 V or more and 0.6 V or less based on the saturated calomel electrode, and the layered manganese oxide of the present invention is precipitated from the mixed aqueous solution.
  • the redox potential range is exceeded, Mn 3 O 4 and permanganate are produced as by-products. Since Mn 3 O 4 is inactive for strontium adsorption, its formation leads to a decrease in strontium adsorption performance. Similarly, if the redox potential range is exceeded, the strength of the layered manganese oxide molded product of the present invention decreases.
  • a more preferable redox potential range is ⁇ 0.1 V or more and 0.5 V or less based on the saturated calomel electrode.
  • the redox potential of the reaction solution is a value based on a general standard hydrogen electrode, and can be obtained by a commercially available redox potential meter.
  • the redox potential can be controlled by the supply amount of the oxidizing agent and the reaction temperature.
  • the temperature at which the aqueous metal salt solution containing manganese, the aqueous alkali metal solution and the oxidizing agent are mixed is 0 ° C. or higher and 100 ° C. or lower. If the mixing temperature is less than 0 ° C., the oxidation reaction may not proceed and the reaction solution may solidify, and if it exceeds 100 ° C., particle growth proceeds and the desired dense aggregate cannot be obtained. Since the oxidation reaction is likely to proceed and the layered manganese oxide is more likely to be precipitated, the temperature is preferably 40 ° C. or higher and 80 ° C. or lower.
  • the metal salt aqueous solution containing manganese, the alkali metal aqueous solution and the oxidizing agent are mixed in step 1, either a batch type or a continuous type reaction may be used.
  • the pH at the end of mixing is preferably 7 or more and 14 or less, and the pH and the oxidation-reduction potential of the reaction solution can be appropriately adjusted by controlling the charging rate of either a metal salt containing manganese or an aqueous alkali metal solution.
  • the method of adding the metal aqueous solution and the alkali metal aqueous solution it is preferable to keep the alkali metal / manganese molar ratio constant and then drop them at a constant velocity at the same time because a dense molded body having high strength and adsorption performance can be obtained.
  • at least the required power for stirring at the time of mixing the metal salt aqueous solution containing manganese, the alkali metal aqueous solution and the oxidizing agent is required to be 0.5 kW / m 3 or more.
  • stirring power is insufficient such that the required power for stirring is less than 0.5 kW / m 3 , a by-product phase is generated and the desired dense aggregate cannot be obtained.
  • the solid content concentration in the slurry obtained by mixing the raw material liquid in step 1 needs to be 1 wt% or more and 5 wt% or less. A high concentration is desirable to ensure productivity, but if it exceeds 5 wt%, a dense aggregate tends not to be obtained. At this time, in order to achieve both production efficiency and precision, 3 wt% or more and 4 wt% or less are preferable.
  • step 2 the method for filtering the layered manganese oxide precipitated in step 1 is not particularly limited as long as solid-liquid separation is possible.
  • a belt filter, a filter press, a pressure filtration device, an ultrafiltration device and the like can be used.
  • the layered manganese oxide may be washed during filtration.
  • the temperature at which the layered manganese oxide is thermoset to produce the layered manganese oxide molded product of the present invention is 40 ° C. or higher from the viewpoint of shape retention of the layered manganese oxide molded product of the present invention. It is carried out at 200 ° C. or lower, and is preferably carried out at 40 ° C. or higher and 160 ° C. or lower.
  • the thermosetting treatment may also serve as a treatment for drying the filtered cake of the layered manganese oxide obtained by filtration.
  • thermosetting treatment is performed after the filtered cake is in its original shape or is appropriately crushed or molded.
  • the time of the thermosetting treatment is appropriately determined according to the progress of curing. As described above, by setting the drying conditions to be mild, a granular molded product which is a high-hardness and high-density agglomerate can be obtained. Therefore, the thermosetting conditions (drying shape, temperature, time of the filtered cake) are appropriately set. Achieved by controlling. Rotary drying and flash drying are not suitable because they tend to form particles with a particle size of less than 0.2 mm.
  • 90% or more of the total granules have a particle size of 0.2 mm or more by thermosetting the filtered cake and then crushing and classifying the cake as necessary. It is performed so that the particles are 0.7 mm or less.
  • the crushing method is not particularly limited, and general crushers such as cone crushers, crusher type crushers such as roll crushers, cutter mills, stamp mills, ring mills, roller mills, jet mills, hammer mills, rotary mills (ball mills), It can be performed by a mill type crusher such as a vibration mill.
  • either dry classification or wet classification can be used, and a hydraulic classification machine, a sedimentation classification machine, a mechanical classification machine, an air flow classification machine, a gravity classification machine, a cyclone type classification machine, a sieving type classification machine, etc. can be appropriately used.
  • a hydraulic classification machine a sedimentation classification machine, a mechanical classification machine, an air flow classification machine, a gravity classification machine, a cyclone type classification machine, a sieving type classification machine, etc.
  • the layered manganese oxide molded product of the present invention can be used, for example, for adsorbing strontium adsorbents or other heavy metals.
  • strontium adsorbent As a strontium adsorbent, it is useful for selectively adsorbing strontium from a treatment liquid in which a large amount of coexisting ions are present.
  • the present invention has the following configuration.
  • A is an alkali metal containing at least sodium and potassium, 0.4 ⁇ x ⁇ 0.6, and is assigned as a hexagon in a powder X-ray diffraction experiment.
  • a mixed aqueous solution is obtained by mixing at -0.2 V or more and 0.6 V or less, a temperature of 0 ° C. or more and 100 ° C. or less, and a required stirring power per unit volume of 0.5 kW / m 3 or more, and in the mixed aqueous solution.
  • the solid content concentration of the slurry is precipitated at 1 wt% or more and 5 wt% or less, and then the precipitated substance is thermally cured at 40 ° C. or higher and 200 ° C. or lower after filtration.
  • the precipitated substance to be precipitated in the mixed aqueous solution is bucelite having an interlayer distance of 9 angstroms or more and 10 angstroms or less, and the precipitated substance has an interlayer distance of 7.0 angstroms or more and 7.3 angstroms or less in the heat curing process.
  • the elemental composition analysis of the obtained sample was performed by inductively coupled plasma emission spectrometry (ICP method). That is, a measurement solution was prepared by dissolving the sample powder under pressure with hydrogen peroxide solution and hydrofluoric acid. The elemental composition of the obtained sample was analyzed by measuring the obtained measurement solution using an inductively coupled plasma emission spectrometer (trade name: OPTIMA3000DV, manufactured by PERKIN ELMER).
  • ICP method inductively coupled plasma emission spectrometry
  • the crushing strength of the sample was measured using a microcompression tester (trade name: MCT-510, manufactured by Shimadzu Corporation). The crushing strength was measured by applying a load to the sample with a diamond platen. Randomly taken out molded granules were placed on a sample table, the diamond platen was automatically lowered, and the test force when the particles collapsed was taken as the crushing strength. The crushing strength was the test force when the displacement of the diamond platen under load was the largest. From the observation with a microscope, the displacement that seems to be the fine movement of the particles before the collapse was excluded. ) This measurement was repeated 25 times, and the average value was taken as the crushing strength of the molded product.
  • simulated seawater A Ca 2+ : 5ppm, Mg 2+ : 2ppm, Sr 2+ : 5ppm, Cs + : 1ppm, pH 7 object to be treated A
  • NaCl 0.3%
  • pH 7 to be treated liquid B (hereinafter referred to as “simulated seawater B”) was prepared, and further, the liquid to be treated A was prepared with a 1N-NaOH aqueous solution.
  • simulated seawater C a pH 12 object to be treated C having NaCl: 0.3%, Ca 2+ : 5 ppm, Mg 2+ : 0 ppm, Sr 2+ : 5 ppm, Cs +: 1 ppm.
  • treatment liquids A to C treated simulated seawater
  • the strontium concentration in the treatment liquid was measured by inductively coupled plasma emission spectrometry (ICP method).
  • the strontium concentration was determined by measuring the treatment liquid using a general inductively coupled plasma emission spectrometer (trade name: OPTIMA3000DV, manufactured by PERKIN ELMER).
  • the strontium concentration of the simulated seawater before the adsorption test is C 0 (mg / L)
  • the strontium concentration of the treatment solution is C (mg / L)
  • C / C 0 is the unit from the start of the simulated seawater flow to the sampling time.
  • VV total simulated seawater flow volume per adsorbent volume
  • ⁇ Measuring method of particle weight fraction corresponding to particle size of 0.2 mm or more and 1.7 mm or less The sample was passed through a metal sieve with an opening of 1.7 mm (10 mesh) and an opening of 0.21 mm (70 mesh).
  • the weight fraction of the granular material corresponding to the particle size of 0.2 mm to 1.7 mm is the weight A of the granular material above the sieve with a mesh opening of 1.7 mm and the weight A under the sieve with a mesh opening of 0.21 mm, and the weight B of the whole granular material. It was calculated by the following formula.
  • Granular material weight fraction (%) corresponding to a particle size of 0.2 mm or more and 1.7 mm or less 100 ⁇ (BA) / B ⁇ Calculation method of required power for stirring>
  • the required stirring power per unit volume was calculated by the following formula.
  • Np Np ⁇ ⁇ ⁇ n 3 ⁇ d 5
  • Pv P / V (P: Power required for stirring [W], Pv: Power required for stirring per volume [kW / m 3 ], ⁇ : Density [kg / m 3 ], n: Rotation speed [rps], d: Blade span [m] , Np: power number [-], V: volume [L])
  • Np power number
  • 10 L reaction tank, 1.1 L reaction tank for paddle blade, and 1.8 for paddle blade were used.
  • ⁇ density is 1.22 g / cc
  • d blade span is 10 L reaction tank
  • paddle blade is 128 mm
  • 1 L reaction tank paddle blade is 80 mm
  • V volume is 10 L reaction tank ⁇ 5 L ( Example 3) 1L reaction vessel ⁇ 0.7L (Examples 1 and 4 and Comparative Examples 2 and 3) and 0.3L (Comparative Example 4) were used.
  • Example 1 300 g of pure water was placed in a reaction vessel having an internal volume of 1 L, and the temperature was raised and maintained at 40 ° C. Separately, manganese sulfate was dissolved in pure water to prepare a metal salt aqueous solution containing 0.82 mol / L manganese sulfate.
  • the alkaline earth concentration of the metal salt aqueous solution was Ca 10 ppm, Mg 7 ppm, and other alkaline earth metals were below the detection limit.
  • the metal salt aqueous solution was added to the reaction vessel at a supply rate of 10 g / min. At the same time, 35% hydrogen peroxide solution was added as an oxidizing agent into the reaction vessel at a supply rate of 5.4 g / min.
  • a 4-blade paddle blade having an outer diameter of 80 mm was used and rotated at 600 ppm.
  • the power required for stirring at that time was 10 kW / m 3 .
  • a 5 mol / L potassium hydroxide aqueous solution (alkali metal aqueous solution) was continuously added for 30 minutes so that the redox potential was ⁇ 0.055 V based on the saturated calomel electrode.
  • the K / Mn molar ratio was 4.7 when the metal salt aqueous solution and the 35% hydrogen peroxide solution were supplied.
  • the obtained slurry is filtered, washed with pure water, and then the washed wet cake is dried at 60 ° C. for 5 hours and thermoset to cause agglomerates of layered manganese oxide (K 0.34 MnO 2).
  • K 0.34 MnO 2 layered manganese oxide
  • the lumpy agglomerates were crushed by tapping with an alumina mortar and pestle. After that, it is passed through a mesh with a mesh opening of 0.6 mm, and what remains on the mesh with a mesh opening of 0.3 mm is collected to classify the product into 0.3 to 0.6 mm to obtain a layered manganese oxide molded product. It was.
  • the obtained layered manganese oxide molded product was found to have a layered crystal structure by measurement of powder X-ray diffraction, and was consistent with a diffraction pattern derived from a burnesite-type crystal structure in which potassium ions were present between layers.
  • the interlayer distance was 7.12 angstroms, and the FWHM of the 001 peak when it was assigned to the hexagonal crystal was 1.500 °.
  • the K / Mn molar ratio measured by elemental composition was 0.34.
  • the bulk density of the obtained layered manganese oxide molded product was 1.18 g / cm 3 , the crushing strength was 2339 mN, and the degree of agitation wear was 2.15% by weight. There was no change in the shape of the layered manganese oxide molded product before and after the measurement of the degree of stirring wear.
  • the silicon, aluminum, titanium and zirconium concentrations of the molded product were below the detection limit, and the carbon concentration was below the detection limit (3000 ppm or less).
  • Table 1 shows the measurement results of the layered manganese oxide molded product. Further, the powder X-ray diffraction pattern of the layered manganese oxide is shown in FIG. 1, and the scanning electron microscope image (SEM image) of the layered manganese oxide is shown in FIG.
  • Example 2 Manganese nitrate hexahydrate (Kanto Chemical Co., Ltd., 98%), 52.83 g, is dissolved in a small amount of water, and a volumetric flask is used to increase the volume to 600 mL to 0.3 mol / L to produce manganese nitrate.
  • An aqueous manganese solution was prepared. 47.61 g of potassium hydroxide (KOH) was dissolved in a small amount of water, and 51.60 mL of hydrogen peroxide solution (H 2 O 2 , 35%) was added thereto (H 2 O 2 + KOH aqueous solution). It was prepared to 600 mL using a volumetric flask. At this time, the KOH concentration was 1.2 mol / L and the H 2 O 2 concentration was 1.0 mol / L.
  • KOH potassium hydroxide
  • a 600 mL aqueous manganese nitrate solution was transferred to a 2000 mL beaker, and 600 mL of an H 2 O 2 + KOH aqueous solution was slowly added thereto with stirring using a magnetic stirrer. After stirring for 10 minutes, the stirring is stopped and the mixture is allowed to stand for 1 hour, the obtained solid is filtered under reduced pressure using a filter paper, washed with 3000 mL of water, and dried in a dryer at 60 ° C. for 1 day. Heat-cured with. The dried product was a glossy lumpy aggregate, and the yield was 21.12 g.
  • the lumpy agglomerate was placed in an alumina mortar and crushed with a pestle.
  • the crushed pieces after crushing are opened, passed through a 0.6 mm mesh, and the residue remaining on the mesh with a mesh opening of 0.3 mm is collected to classify the crushed pieces into 0.3 to 0.6 mm and layered manganese oxide.
  • a molded product was obtained.
  • FIG. 3 shows the powder X-ray diffraction patterns of the wet sample A obtained after filtration and cleaning and the sample B thermoset at 60 ° C. for one day.
  • Sample A can be attributed to buserite with an interlayer distance of 9.37 angstroms
  • sample B can be attributed to burnesite with an interlayer distance of 7.09 angstroms.
  • the FWHM of the 001 peak was 1.212 °.
  • the precipitated substance is bucelite having an interlayer distance of 9 angstroms or more and less than 10 angstroms, and changes to burnesite having an interlayer distance of 7 angstroms in the heat curing process. It was confirmed that
  • the obtained layered manganese oxide molded product had a bulk density of 1.19 g / cm 3 , a crushing strength of 3426 mN, and a stirring wear degree of 2.87% by weight. There was no change in the shape of the layered manganese oxide molded product before and after the measurement of the degree of stirring wear.
  • the silicon, aluminum, titanium and zirconium concentrations of the molded product were below the detection limit, and the carbon concentration was below the detection limit (3000 ppm or less).
  • Table 1 shows the measurement results of the layered manganese oxide molded product. Further, a scanning electron microscope image (SEM image) of the layered manganese oxide is shown in FIG.
  • Example 3 2800 g of pure water was placed in a reaction vessel having an internal volume of 10 L, and the temperature was raised and maintained at 60 ° C. Separately, manganese sulfate was dissolved in pure water to prepare a metal salt aqueous solution containing 2.0 mol / L manganese sulfate.
  • the alkaline earth concentration of the metal salt aqueous solution was Ca 22 ppm, Mg 15 ppm, and other alkaline earth metals were below the detection limit.
  • the metal salt aqueous solution was added to the reaction vessel at a supply rate of 35 g / min. At the same time, 35% hydrogen peroxide solution was added into the reaction vessel as an oxidizing agent at a supply rate of 13 g / min.
  • the obtained slurry is filtered, washed with pure water, and then the washed wet cake is dried at 60 ° C. for 5 hours and thermoset to cause agglomerates of layered manganese oxide (K 0.35 MnO 2). I got something.
  • the lumpy agglomerates were crushed by tapping with an alumina mortar and pestle. After that, a mesh with a mesh opening of 0.6 mm is passed through, and what remains on the mesh with a mesh opening of 0.3 mm is collected to classify the mixture into 0.3 to 0.6 mm to obtain a layered manganese oxide molded product. It was.
  • the obtained layered manganese oxide molded product contained a slight by-product phase by powder X-ray diffraction measurement, but it was found that the main phase was a burnesite-type oxide in which potassium ions were present between layers.
  • the interlayer distance was 7.09 angstroms, and the FWHM of the 001 peak when it was assigned to the hexagonal crystal was 1.167 °.
  • the K / Mn molar ratio measured by elemental composition was 0.35.
  • the bulk density of the obtained layered manganese oxide molded product was 1.39 g / cm 3 , the crushing strength was 1591 mN, and the degree of agitation wear was 4.02% by weight. There was no change in the shape of the layered manganese oxide molded product before and after the measurement of the degree of stirring wear.
  • the silicon, aluminum, titanium and zirconium concentrations of the molded product were below the detection limit, and the carbon concentration was below the detection limit (3000 ppm or less).
  • Table 1 shows the measurement results of the layered manganese oxide molded product.
  • the powder X-ray diffraction pattern of the layered manganese oxide is shown in FIG. 5, and the scanning electron microscope image (SEM image) of the layered manganese oxide is shown in FIG.
  • Example 4 800 g of pure water was placed in a reaction vessel having an internal volume of 1 L having an extraction port at the top of the vessel, and the temperature was raised and maintained at 60 ° C.
  • manganese sulfate was dissolved in pure water to prepare a metal salt aqueous solution containing 0.90 mol / L manganese sulfate.
  • the metal salt aqueous solution was added to the reaction vessel at a supply rate of 10 g / min.
  • a 2.3 mol / L potassium hydroxide aqueous solution (alkali metal aqueous solution) was prepared and added to the reaction vessel at 19 g / min.
  • a 10% aqueous solution of sodium peroxodisulfate was prepared as an oxidizing agent and added to the reaction vessel at a supply rate of 18 g / min at the same time as the aqueous metal salt solution and the aqueous alkali metal solution.
  • the stirring power per volume at the time of mixing was 10 kW / m 3 .
  • the above operation was continuously performed for 4 hours.
  • the slurry that flowed out was sampled every 40 minutes.
  • the solid content concentration of the slurry that flowed out from 200 minutes to 240 minutes after the start of the experiment was 1.8 wt%.
  • layered manganese oxide Na 0.25 K 0.23 MnO 2
  • the lumpy agglomerates were crushed by tapping with an alumina mortar and pestle. After that, a mesh with a mesh opening of 0.6 mm is passed through, and what remains on the mesh with a mesh opening of 0.3 mm is collected to classify the mixture into 0.3 to 0.6 mm to obtain a layered manganese oxide molded product. It was.
  • the obtained layered manganese oxide molded product was found to have a layered crystal structure by measurement of powder X-ray diffraction, and was consistent with a diffraction pattern derived from a burnesite-type crystal structure in which potassium ions were present between layers.
  • the interlayer distance was 7.18 angstroms, and the FWHM of the 001 peak when it was assigned to the hexagonal crystal was 3.210 °.
  • the Na / Mn molar ratio was 0.25 and the K / Mn molar ratio was 0.23 as measured by the element composition.
  • the bulk density of the obtained layered manganese oxide molded product was 1.33 g / cm 3 , the crushing strength was 2069 mN, and the degree of agitation wear was 0.05% by weight. There was no change in the shape of the layered manganese oxide molded product before and after the measurement of the degree of stirring wear.
  • the silicon, aluminum, titanium and zirconium concentrations of the molded product were below the detection limit, and the carbon concentration was below the detection limit (3000 ppm or less).
  • Table 1 shows the measurement results of the layered manganese oxide molded product.
  • the powder X-ray diffraction pattern of the layered manganese oxide is shown in FIG. 7, and the scanning electron microscope image (SEM image) of the layered manganese oxide is shown in FIG.
  • the obtained potassium-type layered manganese oxide was found to have a layered crystal structure by measurement of powder X-ray diffraction, and was consistent with the diffraction pattern derived from the burnesite-type crystal structure in which potassium ions were present between layers.
  • the interlayer distance was 7.14 angstroms
  • the FWHM of the 001 peak when assigned to hexagonal crystals was 0.577 °
  • the K / Mn molar ratio determined from the elemental composition was 0.307.
  • Potassium-type layered manganese oxide 100 parts by weight Silica in silica sol: 16 parts by weight Water: 36 parts by weight CMC: 5 parts by weight Silica sol as an inorganic binder has a sol concentration of 48% by weight and average particles of silica particles in the sol.
  • a silica sol (trade name: Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd.) having a diameter average sol particle size of 0.02 ⁇ m was used.
  • CMC (trade name: Cellogen WS-D, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as a molding aid.
  • the obtained mixture was mixed with a Henschel mixer for 20 minutes and then extruded to obtain a cylindrical molded body having a diameter of 1.5 mm.
  • the obtained molded product was fired at 500 ° C. for 3 hours under an air flow of 25 L / min, crushed, passed through a mesh having an opening of 0.6 mm, and remained on a mesh having an opening of 0.3 mm. Was collected and classified into 0.3 to 0.6 mm to obtain a layered manganese oxide molded product.
  • the obtained layered manganese oxide molded product had a bulk density of 0.771 g / cm 3 , a crushing strength of 483 mN, and a stirring wear degree of 31.0% by weight. There was no change in the shape of the layered manganese oxide molded product before and after the measurement of the degree of stirring wear.
  • the concentrations of silicon, aluminum, titanium and zirconium in the molded product were 6.4 wt% of silicon.
  • the carbon concentration was below the detection limit (3000 ppm or less).
  • Table 1 shows the measurement results of the layered manganese oxide molded product. Further, the powder X-ray diffraction pattern of the layered manganese oxide is shown in FIG. 9, and the scanning electron microscope image (SEM image) of the layered manganese oxide is shown in FIG.
  • Comparative Example 2 300 g of pure water was placed in a reaction vessel having an internal volume of 1 L, and the temperature was raised and maintained at 40 ° C. An aqueous metal salt solution containing manganese sulfate (manganese sulfate concentration 0.82 mol / L) containing an alkaline earth metal component for industrial use was used. The alkaline earth metal concentration in the metal salt aqueous solution was Ca 500 ppm, Mg 1400 ppm, and other alkaline earth metals were below the detection limit. Synthesis was carried out in the same manner as in Example 1 except that the alkaline earth metal concentrations of the manganese sulfate aqueous solution were different.
  • FIG. 11 shows a powder X-ray diffraction pattern of the dried sample after filtration and cleaning. Since almost no low-angle 001 peak showing a layered structure was observed, it was found that the manganese oxide was not a layered manganese oxide.
  • Table 1 shows the measurement results of the manganese oxide molded product.
  • Comparative Example 3 The synthesis was carried out in the same manner as in Example 1 except that the rotation speed of the stirring blade was reduced to 100 rpm and the required power for stirring was set to 0.4 kW / m 3.
  • FIG. 12 shows a powder X-ray diffraction pattern of the dried sample after filtration and cleaning.
  • Other birnessite type layered manganese oxide present potassium ions between layers, because the peak of MnOOH and Mn 3 O 4 is strongly observed, the sample was confirmed to be a mixture of these phases.
  • Table 1 shows the measurement results of the layered manganese oxide.
  • Comparative Example 4 100 g of pure water was placed in a reaction vessel having an internal volume of 1 L, and the temperature was raised and maintained at 40 ° C. Separately, manganese sulfate was dissolved in pure water to prepare a metal salt aqueous solution containing 2.0 mol / L manganese sulfate. The metal salt aqueous solution was added to the reaction vessel at a supply rate of 5 g / min.
  • a 10 mol / L potassium hydroxide aqueous solution (alkali metal aqueous solution) was added into the reaction vessel at a supply rate of 3.3 g / min, and a 35% hydrogen peroxide solution as an oxidizing agent was added at a supply rate of 1.6 g / min.
  • the K / Mn molar ratio was 3.0 when the metal salt aqueous solution and the 35% hydrogen peroxide solution were supplied.
  • the stirring power per volume at the time of mixing was 23 kW / m 3 .
  • a slurry in which layered manganese oxide was precipitated was obtained by the above operation.
  • the solid content concentration of the slurry was 6.2 wt%.
  • the obtained slurry is filtered, washed with pure water, and then the washed wet cake is dried at 60 ° C. for 5 hours and thermoset to cause agglomerates of layered manganese oxide (K 0.29 MnO 2).
  • K 0.29 MnO 2 layered manganese oxide
  • the lumpy agglomerates were crushed by tapping with an alumina mortar and pestle. After that, a mesh with a mesh opening of 0.6 mm is passed through, and what remains on the mesh with a mesh opening of 0.3 mm is collected to classify the mixture into 0.3 to 0.6 mm to obtain a layered manganese oxide molded product. It was.
  • the obtained layered manganese oxide molded product was found to have a layered crystal structure by measurement of powder X-ray diffraction, and was consistent with a diffraction pattern derived from a burnesite-type crystal structure in which potassium ions were present between layers.
  • the interlayer distance was 7.12 angstroms, and the FWHM of the 001 peak when it was assigned to the hexagonal crystal was 1.440 °.
  • the K / Mn molar ratio measured by elemental composition was 0.34.
  • Table 1 shows the measurement results of the layered manganese oxide molded product.
  • the layered manganese oxide molded product of the present invention can be used as an adsorbent for strontium.
  • it can be used as an adsorbent for selectively adsorbing strontium ions from treated water containing a large amount of coexisting cations, such as seawater containing radionuclides derived from a uranium fission reactor.

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Abstract

La présente invention concerne un corps moulé en oxyde de manganèse stratifié qui présente des performances élevées pour l'élimination sélective du strontium d'un liquide qui a servi à traiter l'eau contaminée d'une centrale nucléaire, et dans lequel coexistent des ions. L'invention concerne également un corps moulé en oxyde de manganèse stratifié configuré à partir d'un oxyde de manganèse stratifié qui contient au moins un métal alcalin et du manganèse, dans lequel : la résistance à l'écrasement telle que déterminée par une machine d'essai de microcompression est de 1 000 mN à 5 000 mN ; un liant inorganique et un composant organique ne sont pas substantiellement présents ; 90 % ou plus des particules parmi toutes les particules contenues dans le corps présentent un diamètre de particule de 0,2 mm à 1,7 mm ; et la densité apparente est de 0,9 g/cm3 ou plus. L'invention concerne également un procédé de production de ce corps moulé en oxyde de manganèse stratifié.
PCT/JP2020/044990 2019-12-06 2020-12-03 Corps moulé en oxyde de manganèse stratifié et son procédé de fabrication Ceased WO2021112163A1 (fr)

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JP2000203844A (ja) * 1998-05-22 2000-07-25 Toyota Central Res & Dev Lab Inc リチウム二次電池正極活物質用リチウムマンガン複合酸化物、その製造方法、およびそれを正極活物質に用いたリチウム二次電池
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JP7398049B2 (ja) 2019-12-06 2023-12-14 東ソー株式会社 ストロンチウム含有廃液の処理方法

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