WO2016052611A1 - 結晶性シリコチタネートの製造方法 - Google Patents
結晶性シリコチタネートの製造方法 Download PDFInfo
- Publication number
- WO2016052611A1 WO2016052611A1 PCT/JP2015/077715 JP2015077715W WO2016052611A1 WO 2016052611 A1 WO2016052611 A1 WO 2016052611A1 JP 2015077715 W JP2015077715 W JP 2015077715W WO 2016052611 A1 WO2016052611 A1 WO 2016052611A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crystalline silicotitanate
- mixed gel
- sio
- sodium
- titanium tetrachloride
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 64
- 239000010936 titanium Substances 0.000 claims abstract description 60
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 32
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 26
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 25
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- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 abstract description 15
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- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 2
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- 239000000499 gel Substances 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
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- 239000000843 powder Substances 0.000 description 5
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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 method for producing crystalline silicotitanate that can be suitably used for selectively and efficiently separating and recovering cesium or strontium in seawater.
- coprecipitation treatment is known as a treatment technique for wastewater containing radioactive substances (see Patent Document 1 below).
- the coprecipitation treatment is not effective and is currently being adsorbed and removed by an inorganic adsorbent such as zeolite (see Patent Document 2 below).
- Non-Patent Document 1 When radioactive cesium and radioactive strontium flow into seawater, an increase in the sodium concentration of seawater components acts to suppress the ion exchange reaction between cesium and the adsorbent (see Non-Patent Document 1 below). The problem is known.
- Crystalline silicotitanate is one of the inorganic adsorbents studied so far for the adsorption of cesium and / or strontium. Crystalline silicotitanates are known to have a plurality of types of compositions such as those with a Ti / Si ratio of 1: 1, 5:12, and 2: 1. It is known that there is crystalline silicotitanate in which is 4: 3.
- products 3B and 3C produced by hydrothermal treatment using an alkoxide of Ti (OET) 4 as a Ti source and colloidal silica as a Si source are three-dimensional from the X-ray diffraction pattern.
- Non-Patent Document 3 discloses a hydrothermal treatment of a crystalline silicotitanate having a Ti / Si ratio of 4: 3, titanium tetrachloride as a Ti source, and a highly dispersed SiO 2 powder as a Si source. The fact that it was manufactured by applying is described. This document describes that the synthesized crystalline silicotitanate has strontium ion exchange capacity.
- an object of the present invention is to provide an industrially advantageous method for producing crystalline silicotitanate which is effective in cesium adsorbents and further strontium adsorbents in seawater.
- a potassium compound is further added, and the mixed gel obtained with a specific ratio of A 2 O (where A represents an alkali metal of Na and K) and SiO 2 is hydrothermally treated.
- the first invention of the present invention is a first step of obtaining a mixed gel by mixing a silicic acid source, a sodium compound, titanium tetrachloride, and water, A second step of hydrothermal reaction of the mixed gel obtained in the first step,
- the present invention provides a method for producing a crystalline silicotitanate represented by O (wherein A represents an alkali metal of Na and K. In the formula, n represents 0 to 8).
- crystalline silicotitanate having excellent adsorption and removal characteristics of cesium and strontium can be produced even in seawater by an industrially advantageous method.
- FIG. 1 is an X-ray diffraction chart of the crystalline silicotitanate obtained in Examples 1 to 3.
- the present invention includes a first step of obtaining a mixed gel by mixing a silicic acid source, a sodium compound and, if necessary, a potassium compound, titanium tetrachloride, and water, and a mixed gel obtained by the first step. And a second step for hydrothermal reaction.
- the general formula Na 4 Ti 4 Si 3 O 16 .nH 2 O (where n is 0-8)
- silicate source used in the first step examples include sodium silicate.
- active silicic acid obtained by carrying out cation exchange of the alkali silicate namely, alkali metal salt of silicic acid is also mentioned.
- Active silicic acid is obtained by cation exchange by bringing an aqueous alkali silicate solution into contact with, for example, a cation exchange resin.
- a sodium silicate aqueous solution usually called water glass (water glass No. 1 to No. 4 etc.) is preferably used. This is relatively inexpensive and can be easily obtained.
- an aqueous potassium silicate solution is suitable as a raw material.
- the aqueous alkali silicate solution is diluted with water as necessary.
- the cation exchange resin used when preparing the active silicic acid can be appropriately selected from known ones and is not particularly limited.
- the alkali silicate aqueous solution is diluted with water so that the silica has a concentration of 3% by mass or more and 10% by mass or less.
- a strong acidic or weakly acidic cation exchange resin to dealkalize. Further, if necessary, it can be deanioned by contacting with an OH type strongly basic anion exchange resin.
- an active silicic acid aqueous solution is prepared.
- various proposals have already been made, and any known contact conditions can be adopted in the present invention.
- Examples of the sodium compound used in the first step include sodium hydroxide and sodium carbonate. Among these sodium compounds, when sodium carbonate is used, carbon dioxide gas is generated. Therefore, it is preferable to use sodium hydroxide that does not generate such gas from the viewpoint of smoothly promoting the neutralization reaction.
- Examples of the potassium compound include potassium hydroxide and potassium carbonate. Among these potassium compounds, when potassium carbonate is used, carbon dioxide gas is generated. Therefore, it is preferable to use potassium hydroxide that does not generate such gas from the viewpoint of smoothly promoting the neutralization reaction.
- the ratio of the number of moles of K to the number of moles of A defined below exceeds 0% to 40%, particularly 5% to 30% in the mixed gel. It is more preferable to add a sodium compound and a potassium compound so that it becomes the following.
- sodium silicate or potassium silicate is used as the above-mentioned silicate source, the sodium silicate or silicate The amount of sodium ion or potassium ion contained in potassium is included in the calculation of the number of moles of A.
- the number of moles of A is obtained by the following formula.
- Number of moles of A number of moles of sodium ions derived from sodium silicate + number of moles of potassium ions derived from potassium silicate + number of moles of sodium ions derived from sodium compounds other than sodium silicate + derived from potassium compounds other than potassium silicate
- titanium tetrachloride is used as a titanium source.
- other titanium compounds such as titanium oxide are used as a titanium source, unreacted titanium oxide remains or crystalline siliconates other than crystalline silicon titanate having a molar ratio of Ti: Si of 4: 3 are formed.
- titanium tetrachloride is used as the titanium source.
- the titanium tetrachloride used in the first step can be used without particular limitation as long as it is industrially available.
- the addition amount of the silicic acid source and titanium tetrachloride may be set to an amount such that Ti / Si, which is the molar ratio of Ti derived from titanium tetrachloride and Si derived from the silicon source in the mixed gel, has a specific ratio. This is one of the characteristics of the method for producing crystalline silicotitanate.
- Ti / Si which is the molar ratio of Ti derived from titanium tetrachloride and Si derived from the silicon source in the mixed gel.
- This is one of the characteristics of the method for producing crystalline silicotitanate.
- titanium tetrachloride is used as the titanium source, but the silicic acid source and titanium tetrachloride are added to the mixed solution in such an amount that the molar ratio of Ti / Si is 0.32. Yes.
- the silicic acid source and titanium tetrachloride are added in such amounts that the Ti / Si molar ratio is 1.2 or more and 1.5 or less.
- the Ti / Si ratio in the mixed gel is set within the above-mentioned molar range, it is easy to obtain a crystalline silicotitanate having a high degree of crystallinity. It has been found that the adsorption performance of cesium is particularly improved when used as an adsorbent. From this viewpoint, the ratio of Ti / Si in the mixed gel is more preferably 1.3 or more and 1.4 or less.
- the total amount of the SiO 2 equivalent silicic acid source concentration and the TiO 2 equivalent titanium tetrachloride concentration in the mixed gel is 2.0 mass% to 40 mass%, preferably 3 to 30 mass%, more preferably 5 to 5 mass%. 20% by mass is preferable from the viewpoint of obtaining crystalline silicotitanate with high yield.
- the molar ratio of A 2 O / SiO 2 in the mixed gel is 0.5 or more and 2.5 or less, preferably 0.6 or more and 1.1 or less.
- the ratio of A 2 O / SiO 2 in the mixed gel is set to the above molar range, the above-mentioned physical properties of the crystalline silicotitanate are high in X-ray diffraction.
- the silicic acid source, sodium compound, potassium compound added if necessary, and titanium tetrachloride can each be added to the reaction system in the form of an aqueous solution. In some cases, it can be added in the form of a solid. Further, in the first step, if necessary, the concentration of the mixed gel can be adjusted using pure water for the obtained mixed gel.
- the silicic acid source, the sodium compound, the potassium compound added if necessary, and titanium tetrachloride can be added in various addition orders.
- a mixed gel can be obtained by adding titanium tetrachloride to a mixture of a silicic acid source, a sodium compound and a potassium compound to be added if necessary, and water (this addition order is described below). Or simply “Implementation of (1)”).
- the implementation of (1) is preferable in that the generation of chlorine from titanium tetrachloride is suppressed.
- an aqueous solution of activated silicic acid obtained by cation exchange of alkali silicate, titanium tetrachloride and water It is also possible to adopt a mode in which a sodium compound and a potassium compound to be added if necessary are added to a mixture of these. Even when this order of addition is adopted, a mixed gel can be obtained in the same manner as in the execution of (1) (this addition order may be simply referred to as “the execution of (2)” hereinafter). Titanium tetrachloride can be added in the form of an aqueous solution or solid form. Similarly, the sodium compound and optionally added potassium compound can also be added in the form of an aqueous solution or solid form.
- the total concentration of sodium and potassium (A 2 O concentration) in the mixed gel is 0.5% by mass or more in terms of Na 2 O. It is preferable to add so that it may become 15.0 mass% or less, especially 0.7 mass% or more and 13 mass% or less.
- the total Na 2 O equivalent mass of sodium and potassium in the mixed gel and the total Na 2 O equivalent concentration of sodium and potassium in the mixed gel (hereinafter referred to as “total concentration of sodium and potassium (the potassium compound is used in the first step) If not, it is referred to as “sodium concentration”).
- sodium silicate When sodium silicate is used as the silicate source, the sodium component in the sodium silicate simultaneously becomes the sodium source in the mixed gel. Therefore, the “Na 2 O equivalent mass (g) of sodium in the mixed gel” mentioned here is counted as the sum of all sodium components in the mixed gel. Similarly, “Na 2 O equivalent mass (g) of potassium in the mixed gel” is also counted as the sum of all potassium components in the mixed gel.
- titanium tetrachloride stepwise or continuously as an aqueous titanium tetrachloride solution over a certain period of time in order to obtain a uniform gel.
- a peristaltic pump etc. can be used suitably for addition of titanium tetrachloride.
- the mixed gel obtained in the first step may be aged at 10 ° C. or higher and 100 ° C. or lower for a time period of 0.1 hour or longer and 5 hours or shorter before performing a hydrothermal reaction which is the second step described later. From the viewpoint of obtaining a uniform product.
- the aging step may be performed, for example, in a stationary state, or may be performed in a stirring state using a line mixer or the like.
- the mixed gel obtained in the first step is subjected to a hydrothermal reaction as the second step to obtain crystalline silicotitanate.
- the hydrothermal reaction is not particularly limited as long as the crystalline silicotitanate can be synthesized.
- the temperature is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower, preferably 6 hours or longer and 90 hours or shorter, more preferably 12 hours or longer and 80 hours or shorter.
- React under pressure The reaction time can be selected according to the scale of the synthesizer.
- the water-containing crystalline silicotitanate obtained in the second step can be dried, and the obtained dried product can be pulverized or pulverized as necessary to form a powder (including granules).
- the hydrous crystalline silicotitanate may be extruded from an aperture member in which a plurality of apertures are formed to obtain a rod-shaped molded body, and the obtained rod-shaped molded body may be dried to form a columnar shape.
- the dried rod-shaped molded body may be formed into a spherical shape, or may be pulverized or pulverized into particles.
- pulverization refers to an operation of loosening particles that are gathered into a lump
- pulverization refers to an operation of applying mechanical force to the loosened solid particles to make them finer
- the true circle equivalent diameter of the opening is preferably 0.1 mm or more and 10 mm or less, and more preferably 0.3 mm or more and 5 mm or less.
- the true circle equivalent diameter here is a diameter of a circle calculated from the area when the area of one hole is a circle area.
- the drying temperature after extrusion molding can be, for example, 50 ° C. or more and 200 ° C. or less.
- the drying time can be 1 hour or more and 120 hours or less.
- the dried rod-shaped molded body can be used as an adsorbent as it is, or may be used after being loosened. Moreover, you may grind
- the powdery crystalline silicotitanate obtained by these various methods is preferably further classified and then used as an adsorbent from the viewpoint of increasing the adsorption efficiency of cesium and / or strontium.
- a first sieve having a nominal opening prescribed in JISZ8801-1 of 1000 ⁇ m or less, particularly 710 ⁇ m or less.
- it is also preferable to carry out using the 2nd sieve whose said nominal opening is 100 micrometers or more, especially 300 micrometers or more.
- the crystalline silicotitanate obtained by the production method of the present invention has a general formula; Na 4 Ti 4 Si 3 O 16 .nH 2 when only the sodium compound is used in the first step.
- a crystalline silicotitanate represented by O (wherein n represents 0 to 8) is obtained as a single phase in X-ray diffraction, and in the first step, a sodium compound and a potassium compound are obtained.
- general formula; general formula; A 4 Ti 4 Si 3 O 16 .nH 2 O (wherein A represents an alkali metal of Na and K. In the formula, n represents 0 to 8).
- the crystalline silicotitanate represented by) is obtained as a single phase.
- a crystalline silicotitanate having a Ti: Si molar ratio of 4: 3 and a Ti: Si molar ratio other than 4: 3, or Na 4 Ti 9 O 20 ⁇ mH 2 O, K 4 Ti 9 O 20 ⁇ mH 2 O, (Na y K (1-y) ) 4 Ti 9 O 20 ⁇ mH 2 O (wherein y is greater than 0 and less than 1, m
- y is greater than 0 and less than 1, m
- the second feature of the crystalline silicotitanate obtained by the production method of the present invention is that it does not contain titanium oxide as an impurity.
- the crystalline silicotitanate obtained by the production method of the present invention is particularly excellent in cesium adsorption / removal properties, and in addition, has high strontium adsorption / removal properties.
- the crystalline silicotitanate can be molded according to a conventional method if necessary, and the molded product obtained thereby can be suitably used as an adsorbent for cesium and / or strontium.
- Examples of the molding process include granulation for forming a powdery crystalline silicotitanate or a powdery adsorbent containing it into a granular form, and slurrying a powdered crystalline silicotitanate to obtain calcium chloride, etc.
- Examples thereof include a method in which a powdery crystalline silicotitanate or a powdery adsorbent containing the same is attached to the surface and / or the inside of the shaped substrate and fixed to form a sheet.
- the granulation method include known methods such as stirring and mixing granulation, rolling granulation, extrusion granulation, crushing granulation, fluidized bed granulation, spray drying granulation (spray drying), and compression granulation.
- a binder and a solvent may be added and mixed as necessary.
- the binder known ones such as polyvinyl alcohol, polyethylene oxide, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, starch, cornstarch, molasses, lactose, gelatin , Dextrin, gum arabic, alginic acid, polyacrylic acid, glycerin, polyethylene glycol, polyvinylpyrrolidone and the like.
- the solvent various solvents such as an aqueous solvent and an organic solvent can be used.
- the granulated product obtained by granulating the water-containing crystalline silicotitanate obtained by the production method of the present invention is suitable as an adsorbent for a water treatment system having an adsorption vessel and an adsorption tower filled with a radioactive substance adsorbent.
- a water treatment system having an adsorption vessel and an adsorption tower filled with a radioactive substance adsorbent.
- the shape and size of the granular product obtained by granulating the water-containing crystalline silicotitanate is filled in an adsorption vessel or packed tower, and treated water containing cesium and / or strontium is passed through. It is preferable to adjust the shape and size as appropriate so as to adapt to this.
- a granular product obtained by granulating the water-containing crystalline silicotitanate obtained by the production method of the present invention is recovered by magnetic separation from water containing cesium and / or strontium by further containing magnetic particles.
- magnetic particles include metals such as iron, nickel, and cobalt, or powders of magnetic alloys based on these metals, metal oxides such as iron trioxide, iron sesquioxide, cobalt-added iron oxide, barium ferrite, and strontium ferrite. Examples thereof include powders of magnetic system.
- the granulation operation described above may be performed in a state where magnetic particles are contained.
- X-ray diffraction Bruker D8 AdvanceS was used. Cu-K ⁇ was used as the radiation source. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 0.1 ° / sec. ICP-AES: Varian 720-ES was used. The Cs and Sr adsorption tests were performed with a Cs measurement wavelength of 697.327 nm and a Sr measurement wavelength of 216.596 nm.
- Standard samples used were Cs: 100 ppm, 50 ppm and 10 ppm aqueous solutions containing 0.3% NaCl, and Sr: 100 ppm, 10 ppm and 1 ppm aqueous solutions containing 0.3% NaCl.
- -Titanium tetrachloride aqueous solution 36.48% aqueous solution manufactured by Osaka Titanium Technologies Co., Ltd.
- ⁇ Titanium dioxide Ishihara Sangyo ST-01.
- Simulated seawater 0.3% NaCl aqueous solution containing 100 ppm of Cs and Sr was used as simulated seawater.
- Simulated seawater is composed of NaCl (99.5%): 3.0151 g, SrCl ⁇ 6H 2 O (99%): 0.3074 g, CsNO 3 (99%): 0.1481 g, H 2 O: 996.5294 g. I got it.
- Titanate was obtained.
- the concentration of SiO 2 in the mixed gel was 2.47%, the concentration of TiO 2 was 6.46%, and the concentration of Na 2 O was 3.32%.
- the composition judged from the X-ray diffraction structure of the obtained crystalline silicotitanate is shown in Table 2 below. As a result, the presence of titanium oxide as an impurity was confirmed.
- the crystalline silicotitanate having a Ti: Si molar ratio of 4: 3 can be obtained in a single phase. It can be seen that this crystalline silicotitanate can adsorb and remove Cs and Sr contained in the simulated seawater with a high adsorption rate. It can also be seen that by adopting the conditions of Example 2, the adsorption performance of cesium and strontium is further improved.
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Abstract
Description
したがって本発明の課題は、海水中においてもセシウムの吸着材、更にはストロンチウムの吸着材にも有効な結晶性シリコチタネートの工業的に有利な製造方法を提供することにある。
また、第一工程において、更にカリウム化合物を添加し、A2O(式中、AはNa及びKのアルカリ金属を示す。)とSiO2のモル比が特定比として得られる混合ゲルを水熱反応させることで、海水からのセシウム及びストロンチウムの吸着材として有用な結晶性シリコチタネートが効率よく得られることを見出し、本発明を完成するに到った。
第一工程により得られた混合ゲルを水熱反応させる第二工程とを有し、
第一工程において、混合ゲルに含まれるTiとSiとのモル比がTi/Si=1.2以上1.5以下で、且つNa2OとSiO2のモル比がNa2O/SiO2=0.5以上2.5以下となるように、ケイ酸源、ナトリウム化合物と、四塩化チタンとを添加することを特徴とする一般式;Na4Ti4Si3O16・nH2O(式中、nは0~8を示す。)で表される結晶性シリコチタネートの製造方法を提供するものである。
本発明は、ケイ酸源と、ナトリウム化合物及び必要により添加するカリウム化合物と、四塩化チタンと、水とを混合して混合ゲルを得る第一工程と、第一工程により得られた混合ゲルを水熱反応させる第二工程とを有するものである。
本発明において、前記第一工程において、ナトリウム化合物及びカリウム化合物のうちナトリウム化合物のみを用いた場合は、一般式;Na4Ti4Si3O16・nH2O(式中、nは0~8を示す。)で表されるTi:Si=4:3のモル比の結晶性シリコチタネートがX線回折的に単相のものとして得られる。
また、前記第一工程において、ナトリウム化合物及びカリウム化合物を併用して用いる場合、一般式;A4Ti4Si3O16・nH2O(式中、AはNa及びKのアルカリ金属を示す。式中、nは0~8を示す。)で表されるTi:Si=4:3のモル比の結晶性シリコチタネートがX線回折的に単相のものとして得られる。
なお、一般式;A4Ti4Si3O16・nH2O(式中、AはNa及びKのアルカリ金属を示す。式中、nは0~8を示す。)で表される結晶性シリコチタネートにおいて、更に詳細な組成については定かではないが、一般式;Na4Ti4Si3O16・nH2O及びK4Ti4Si3O16・nH2Oを含むか、或いは(NaxK(1-x))4Ti4Si3O16・nH2O(式中、xは0超1未満)であると本発明者らは推測している。従って、本発明においてA4Ti4Si3O16・nH2O単相とは、X線回折的にこれらのTi:Si=4:3のモル比の結晶性シリコチタネート以外の結晶性シリコチタネートや、Na4Ti9O20・mH2O、K4Ti9O20・mH2O、(NayK(1-y))4Ti9O20・mH2O(式中、yは0超1未満)、TiO2等の副性物が観察されてないことを意味する。
いては、従来、様々な提案が既にあり、本発明ではそれら公知のいかなる接触条件も採用することができる。
また、カリウム化合物としては、例えば、水酸化カリウム、炭酸カリウム等が挙げられる。これらのカリウム化合物のうち、炭酸カリウムを用いると炭酸ガスが発生するため、そのようなガスの発生がない水酸化カリウムを用いることが、中和反応を円滑に進める観点から好ましい。
Aのモル数=ナトリウム化合物由来のナトリウムイオンのモル数+カリウム化合物由来のカリウムイオンのモル数
なお、上述したケイ酸源としてケイ酸ソーダ又はケイ酸カリを用いる場合、該ケイ酸ソーダやケイ酸カリ中に含まれるナトリウムイオンやカリウムイオンの量は、Aのモル数の算出に含める。この場合、Aのモル数は下記の式で求められる。
Aのモル数=ケイ酸ソーダ由来のナトリウムイオンのモル数+ケイ酸カリ由来のカリウムイオンのモル数+ケイ酸ソーダ以外のナトリウム化合物由来のナトリウムイオンのモル数+ケイ酸カリ以外のカリウム化合物由来のカリウムイオンのモル数
更に、混合ゲル中のK含有量は、K2O換算で、A2Oのうち、特に好ましくは5以上30モル%とすると、セシウム及びストロンチウムの吸着性能が、さらに向上したものが得られる観点から好ましい。
化合物も、その水溶液の形態又は固体の形態で添加することができる。
混合ゲル中におけるナトリウム及びカリウムの合計のNa2O換算質量(g)=(前記のAのモル数ー四塩化チタン由来の塩化物イオンのモル数)×0.5×Na2O分子量
混合ゲル中におけるナトリウム及びカリウムの合計のNa2O換算の濃度(質量%)=混合ゲル中におけるナトリウム及びカリウムの合計のNa2O換算質量/{混合ゲル中の水分量+混合ゲル中におけるナトリウム及びカリウムの合計のNa2O換算質量}×100
、デキストリン、アラビアゴム、アルギン酸、ポリアクリル酸、グリセリン、ポリエチレングリコール、ポリビニルピロリドン等を挙げることができる。溶媒としては水性溶媒や有機溶媒等各種のものを用いることができる。
この場合、含水状態の結晶性シリコチタネートを造粒加工して得られる顆粒状のものの形状や大きさは、吸着容器や充填塔に充填して、セシウム及び/又はストロンチウムを含む処理水を通水するのに適応するようにその形状及び大きさを適宜調整することが好ましい。
含水状態の結晶性シリコチタネートを造粒加工した顆粒状のものに磁性粒子を含有させる方法としては、例えば、前述した造粒加工操作を磁性粒子を含有させた状態で行えばよい。
・X線回折:Bruker社 D8 AdvanceSを用いた。線源としてCu-Kαを用いた。測定条件は、管電圧40kV、管電流40mA、走査速度0.1°/secとした。
・ICP-AES:Varian社720-ESを用いた。
Csの測定波長は697.327nm、Srの測定波長は216.596nmとしてCs及びSrの吸着試験を行った。標準試料はNaClを0.3%含有したCs:100ppm、50ppm及び10ppmの水溶液、並びにNaClを0.3%含有したSr:100ppm、10ppm及び1ppmの水溶液を使用した。
・ケイ酸カリウム:日本化学工業株式会社製(SiO2:26.5%、K2O:13.5%、H2O:60.00%、SiO2/K2O=3.09)。
・ケイ酸ナトリウム:日本化学工業株式会社製(SiO2:28.96%、Na2O:9.37%、H2O:61.67%、SiO2/Na2O=3.1)。
・苛性カリ:固体試薬 水酸化カリウム(KOH:85%)。
・苛性ソーダ水溶液;工業用25%水酸化ナトリウム(NaOH:25%、H2O:75%)。
・四塩化チタン水溶液:株式会社大阪チタニウムテクノロジーズ社製36.48%水溶液。
・二酸化チタン:石原産業ST-01。
・模擬海水:Cs及びSrをそれぞれ100ppm含有した0.3%NaCl水溶液を模擬海水とした。模擬海水はNaCl(99.5%):3.0151g、SrCl・6H2O(99%):0.3074g、CsNO3(99%):0.1481g、H2O:996.5294gを混合して得た。
<結晶性シリコチタネートの合成>
(1)第一工程
ケイ酸ソーダ、25%苛性ソーダ、85%苛性カリ及び純水を表1に示す量で混合し撹拌して混合水溶液を得た。この混合水溶液に、表1に示す量の四塩化チタン水溶液をペリスタポンプで0.5時間にわたって連続的に添加して混合ゲルを製造した。当該混合ゲルは、四塩化チタン水溶液の添加後、1時間にわたり室温(25℃)で静置熟成した。
第一工程で得られた混合ゲルをオートクレーブに入れ、1時間かけて表1の温度まで昇温したのち、この温度を維持しながら撹拌下に反応を行った。反応後のスラリーをろ過、洗浄、乾燥して塊状の結晶性シリコチタネートを得た。得られた結晶性シリコチタネートのX線回折構造から判断される組成を以下の表2に示す。また、結晶性シリコチタネートをICPにより組成分析を行いNa量とK量をそれぞれNa2O換算のK2O換算で表し、その結果を表2に併記した。また、実施例1~3で得られた結晶性シリコチタネートのX線回折チャートを図1に示す。
3号ケイ酸ソーダ90g、苛性ソーダ水溶液121.2g及び純水776.1gを混合し撹拌して混合水溶液を得た。この混合水溶液に、二酸化チタン68.2gにイオン交換水270gに混合分散したスラリーを前記混合液に5分間にわたり連続的に添加し混合ゲルを得た。当該混合ゲルは、二酸化チタンの添加後、1時間にわたり室温で熟成した。この混合ゲルをオートクレーブに入れ、1時間かけて170℃に昇温したのち、この温度を維持しながら撹拌下に24時間反応を行い、反応後のスラリーをろ過、洗浄、乾燥して結晶性シリコチタネートを得た。混合ゲル中のTiとSiとのモル比はTi:Si=2:1であった。混合ゲル中のSiO2の濃度は2.47%、TiO2の濃度は6.46%、Na2Oの濃度は3.32%であった。得られた結晶性シリコチタネートのX線回折構造から判断される組成を以下の表2に示す。結果として、不純物として酸化チタンの存在が確認された。
得られた塊状の結晶性シリコチタネートを乳鉢粉砕および600μmと300μmのフルイによる分級により顆粒状(300~600μm)とした。この顆粒状の結晶性シリコチタネートを、100mlのポリ容器に0.5g取り、模擬海水100.00gを添加し、蓋をした後、内容物を振り混ぜた。内容物の振り混ぜは、ポリ容器の倒立を10回行うことにより行った(以下同様)。その後、静置して1時間経過した後、再び内容物を振り混ぜ、約50mlを5Cのろ紙でろ過し、ろ過によって得られたろ液を採取した。また、残りの50mlはそのまま静置し、更に23時間後(最初に振り混ぜてから24時間後)に再び振り混ぜた。そして、5Cのろ紙でろ過し、ろ過によって得られたろ液を採取した。採取されたろ液を対象として、ICP-AESを用い、ろ液中のCs及びSrの含有量を測定した。その結果を以下の表3に示す。
Claims (6)
- ケイ酸源と、ナトリウム化合物と、四塩化チタンと、水とを混合して混合ゲルを得る第一工程と、
第一工程により得られた混合ゲルを水熱反応させる第二工程とを有し、
第一工程において、混合ゲルに含まれるTiとSiとのモル比がTi/Si=1.2以上1.5以下で、且つNa2OとSiO2のモル比がNa2O/SiO2=0.5以上2.5以下となるように、ケイ酸源、ナトリウム化合物と、四塩化チタンとを添加することを特徴とする一般式;Na4Ti4Si3O16・nH2O(式中、nは0~8を示す。)で表される結晶性シリコチタネートの製造方法。 - 前記第一工程において、更にカリウム化合物を添加し、A2O(式中、AはNa及びKのアルカリ金属を示す。)とSiO2のモル比がA2O/SiO2=0.5以上2.5以下の混合ゲルを調製し、該混合ゲルを水熱反応に付すことを特徴とする一般式;A4Ti4Si3O16・nH2O(式中、AはNa及びKのアルカリ金属を示す。式中、nは0~8を示す。)で表される結晶性シリコチタネートの製造方法。
- A2O中に含まれるK含有量がK2O換算で、0<K2O≦40モル%の範囲であることを特徴とする請求項2記載の結晶性シリコチタネートの製造方法。
- 前記第一工程において、混合ゲルに占めるSiO2換算のケイ酸源濃度とTiO2換算の四塩化チタン濃度の総量が2.0質量%以上40質量%以下となるように、ケイ酸源及び四塩化チタンを添加することを特徴とする請求項1乃至3の何れか一項に記載の結晶性シリコチタネートの製造方法。
- 請求項1ないし4のいずれか一項に記載の製造方法によって得られた結晶性シリコチタネートを用いたことを特徴とするセシウムの吸着材。
- 請求項1ないし4のいずれか一項に記載の製造方法によって得られた結晶性シリコチタネートを用いたことを特徴とするストロンチウムの吸着材。
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EP15847637.4A EP3190087A4 (en) | 2014-10-02 | 2015-09-30 | Method for producing crystalline silicotitanate |
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