CN104412329B - 放射性物质吸附材料、吸附容器、吸附塔、及水处理装置 - Google Patents
放射性物质吸附材料、吸附容器、吸附塔、及水处理装置 Download PDFInfo
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- CN104412329B CN104412329B CN201380028418.7A CN201380028418A CN104412329B CN 104412329 B CN104412329 B CN 104412329B CN 201380028418 A CN201380028418 A CN 201380028418A CN 104412329 B CN104412329 B CN 104412329B
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- Prior art keywords
- sorbing material
- radioactive substance
- water
- titanate
- adsorption tower
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- 239000000941 radioactive substance Substances 0.000 title abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 13
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- 239000002245 particle Substances 0.000 claims description 11
- 229960000892 attapulgite Drugs 0.000 claims description 10
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- 238000000034 method Methods 0.000 abstract description 17
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- 239000010936 titanium Substances 0.000 description 17
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 8
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- 229910052712 strontium Inorganic materials 0.000 description 6
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- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 4
- -1 sodium titanate ion Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004113 Sepiolite Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
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- 229910052624 sepiolite Inorganic materials 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 235000012241 calcium silicate Nutrition 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
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- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
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- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 235000019013 Viburnum opulus Nutrition 0.000 description 1
- 244000071378 Viburnum opulus Species 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- NMVPEQXCMGEDNH-TZVUEUGBSA-N ceftazidime pentahydrate Chemical compound O.O.O.O.O.S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)\C(=N/OC(C)(C)C(O)=O)C=2N=C(N)SC=2)CC=1C[N+]1=CC=CC=C1 NMVPEQXCMGEDNH-TZVUEUGBSA-N 0.000 description 1
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- 235000019425 dextrin Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000004992 fission Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 235000013379 molasses Nutrition 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- 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
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- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/10—Oxides or hydroxides
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- 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
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- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明提供一种吸附容量多的放射性物质吸附材料。本发明的放射性物质吸附材料含有化学式通过M2Ti2O5(M为一价阳离子)表示的钛酸盐。M2Ti2O5的阳离子交换容量大，并且对热稳定，并且对酸、碱等的耐药品性也优异，适宜作为水处理用的吸附材料。在此钛酸盐中加入粘结剂而成型后，通过烧成而机械强度提升，能够抑制输送中等所施加的振动或冲击等造成的破碎或投入于水中时的一次粒子的脱落。
Description
技术领域
本发明涉及一种放射性物质吸附材料、填充此放射性物质吸附材料而成的吸附容器及吸附塔、以及适用此吸附容器或吸附塔的水处理装置。
背景技术
放射性锶90Sr与放射性铯同样地，是半衰期长并且对水的扩散性高的核分裂生成物，期望对受放射性锶污染的水进行处理的系统的改良。
已知水中的放射性锶可以通过正钛酸吸附而除去(非专利文献1)。
作为吸附放射性锶的钛酸钠离子交换体的制造方法，已提出一种以醇与氢氧化钠所构成的液体使含氢氧化钛浆液化而加热，并在过滤、干燥后，进行破碎、分级而制造钠/钛摩尔比为0.6以下的颗粒状的钛酸钠的方法(专利文献1)。
现有技术文献
专利文献
专利文献1：日本特许第4428541号公报；
非专利文献
非专利文献1：久保田益光等，群分离法的开发：无机离子交换体管柱法的含90Sr及134Cs的废液的处理法的开发，JAERI–M82–144(1982)。
发明内容
发明要解决的课题
通过专利文献1中记载的方法制造的颗粒状的钛酸钠，作为交换阳离子的钠/钛的摩尔比低，因此，吸附容量小。
通过专利文献1中记载的方法制造的颗粒状的钛酸钠，是一次粒子的凝集体，因此，强度弱，受到在输送中等所施加的振动或冲击等被粉碎而微粒化，或者投入于水中，由于凝集体的崩坏而一次粒子脱落。因此，此微粉化的粒子或一次粒子，会使吸附塔的过滤器堵塞，或通过吸附塔过滤器，带有放射线的微粉从吸附塔泄漏。
本发明的第1目的在于提供一种吸附容量多的放射性物质吸附材料。
本发明的第2目的在于提供一种机械强度优异，无微粉等的泄漏的问题，作为水处理材料而处理性优异的放射性物质吸附材料。
本发明的第3目的在于提供一种填充此放射性物质吸附材料而成的吸附容器及吸附塔、以及适用此吸附容器或吸附塔的水处理装置。
解决课题的方法
本发明人等发现，通过M2Ti2O5(M为一价阳离子)表示的钛酸盐，放射性物质吸附量优异。另外，还发现在此钛酸盐的粉末中加入粘结剂而成型为规定的大小的粒状体，进一步烧成所制造的放射性物质吸附材料，其机械强度优异，无微粉等的泄漏，作为水处理材料的处理性优异。
本发明是根据上述的见识而达成的，以下为其要旨。
[1]一种放射性物质吸附材料，其特征在于，其含有化学式通过M2Ti2O5表示的钛酸盐，M为一价阳离子。
[2]如[1]所述的放射性物质吸附材料，其中，前述钛酸盐的平均粒径是1～150μm。
[3]如[1]或[2]所述的放射性物质吸附材料，其中，前述化学式通过K2Ti2O5表示。
[4]如[3]所述的放射性物质吸附材料，其中，前述钛酸盐具有在不规则方向延伸复数个突起物的形状。
[5]如[1]～[4]中任一项所述的放射性物质吸附材料，其中，前述放射性物质是放射性锶。
[6]如[1]～[5]中任一项所述的放射性物质吸附材料，其中，使用粘结剂将前述钛酸盐成型为粒径150～3000μm的范围而成。
[7]如[6]所述的放射性物质吸附材料，其中，前述粘结剂是粘土矿物。
[8]如[7]所述的放射性物质吸附材料，其中，前述粘土矿物是绿坡缕石(Attapulgite)。
[9]如[6]～[8]中任一项所述的放射性物质吸附材料，其中，在前述成型后进一步以500～900℃的温度范围进行烧成而成。
[10]一种吸附容器，其填充有[1]～[9]中任一项所述的放射性物质吸附材料而成。
[11]一种吸附塔，其填充有[1]～[9]中任一项所述的放射性物质吸附材料而成。
[12]一种水处理装置，其具备[10]所述的吸附容器或[11]所述的吸附塔。
发明的效果
通过M2Ti2O5(M为一价阳离子)表示的钛酸盐，与其他的钛酸盐相比，其放射性物质的吸附容量大。
在此钛酸盐的粉末中加入粘结剂而成型后，通过烧成所制造的放射性物质吸附材料，其机械强度高，能够抑制输送中等所施加的振动或冲击等造成的破碎，或投入于水时的一次粒子的脱落。因此，可防止微粉粒子造成的吸附塔过滤器的堵塞，或带有放射线的微粉的泄漏。
附图说明
图1是表示实施例1及比较例2、3的结果的图表。
具体实施方式
以下，详细说明本发明的实施方式，但以下说明的实施方式用以容易理解本发明，并非限定任何本发明，本发明在不超出其要旨的范围，可对以下的实施方式所公开的各要素进行各种变更而实施。
本发明的放射性物质吸附材料，其特征在于，其含有通过M2Ti2O5表示的钛酸盐。M为一价阳离子。
钛酸盐一般通过M2TinO2n+1表示，作为阳离子交换体的钛酸盐，n越大，钛酸盐每一分子的阳离子交换位点变少，因此，阳离子交换容量变小。
在阳离子交换容量方面考虑，理想上为M2TiO3，但是通过M2TiO3表示的钛酸盐，非常不稳定，通过加热等立即改性成M2Ti2O5。
M2Ti2O5对热稳定，对酸、碱等的耐药品性优异，适宜作为水处理用的吸附材料。
本发明所使用的通过M2Ti2O5表示的钛酸盐的一价阳离子M，从阳离子交换性优异方面考虑，优选为钾。根据Y.Q.Jia，J.Solid State Chem.，95(1991)184，锶的离子半径与碱金属元素的离子半径如下表所示，K的离子半径比Sr的离子半径稍大，适宜作为阳离子交换体。
表1
| 配位数 | 4 | 6 | 8 | 9 | 10 | 12 |
| Sr | 1.18 | 1.26 | 1.36 | 1.44 | ||
| Li | 0.59 | 0.76 | 0.92 | |||
| Na | 0.99 | 1.02 | 1.18 | 1.24 | 1.39 | |
| K | 1.37 | 1.38 | 1.51 | 1.64 | ||
| Rb | 1.52 | 1.61 | 1.66 | 1.72 | ||
| Cs | 1.67 | 1.74 | 1.81 | 1.88 | ||
| Fr | 1.80 |
一价阳离子M为钾的K2Ti2O5，若以通常的熔融法等进行合成，则成为纤维形状，但是如WO2008/123046中的记载所示，一边使钛源及钾源以机械化学方式(Mechanochemical)粉碎一边混合后，使其粉碎混合物以650～1000℃进行烧成的制造方法，可形成为在不规则方向延伸复数个突起物的形状。具有该形状的钛酸盐的造粒体，其粉体强度高，可增大短径尺寸，因此，可控制阳离子交换速度。
通过M2Ti2O5表示的钛酸盐，优选为平均粒径在1～150μm的范围的粉末状。平均粒径，可通过例如激光绕射式粒度分布测定装置测定。
平均粒径为1～150μm的钛酸盐粉末，其吸附容量大，并且，在后面的成型工序中在操作方面优异。也即，若平均粒径为1μm以上，则不会产生因飞溅或静电造成的容器附着等制造上的难点。若平均粒径为150μm以下，则不会因比表面积的降低使得吸附容量也降低。
因此，在本发明中，优选使用如此的粒径的钛酸盐粉末。钛酸盐粉末的平均粒径，更优选为4～30μm。
在本发明中，较优选使如上述的钛酸盐粉末形成规定的大小而使用，特别地，优选在成型后，以规定的条件进行烧成后使用。
使钛酸盐粉末成型所得到的成型体的形状或大小，只要是适应填充于吸附容器或吸附塔并使含放射性物质的水通入的形状即可，可为例如球状、立方体形状、长方体形状、圆柱形状等的固定形状的粒状体，也可为不定形的形状。若考虑到对吸附容器或吸附塔的填充性，则优选为球状粒状体。
作为形成钛酸盐粉末的方法，无特别限定，但可举例如使用粘结剂等而使钛酸盐粉末成型为粒状体的方法。
作为上述粘结剂，可举例如膨润土(Bentonite)、绿坡缕石(Attapulgite)、海泡石(Sepiolite)、水铝英石(Allophane)、埃洛石(halloysite)、伊毛缟石(Imogolite)、高岭石(kaolinite)等的粘土矿物；硅酸钠、硅酸钙、硅酸镁、偏硅酸钠、偏硅酸钙、偏硅酸镁、偏硅酸铝酸钠、偏硅酸铝酸钙、偏硅酸铝酸镁等的硅酸盐化合物等。这些可单独使用1种，也可混合2种以上而使用。
这些中，作为粘结剂，从可廉价地制造方面考虑，优选为使用比作为化学合成品的硅酸盐化合物更天然物的粘土矿物，进一步，即使在粘土矿物中，从粒状体的机械强度方面考虑，优选为使用绿坡缕石或海泡石等的纤维状的粘土矿物。
在成型时，优选也同样地添加可得到造粒所需要的塑性的增塑剂。作为上述增塑剂，可举例如淀粉、玉米淀粉、糖蜜、乳糖、纤维素、纤维素衍生物、明胶、糊精、阿拉伯胶、藻酸、聚丙烯酸、甘油、聚乙二醇、聚乙烯醇(PVA)、聚乙烯基吡咯烷酮(PVP)、水、甲醇、乙醇等。这些可单独使用1种，也可混合2种以上使用。
以规定的混合比例混合钛酸盐、粘结剂与增塑剂后，进行造粒成型，使其干燥后，进行烧成，由此，能够提升机械强度，并且可抑制输送中等所施加的振动或冲击等造成的破碎，或投入于水时的一次粒子的脱落。
粘结剂的使用量，无特别限定，相对于钛酸盐粉末1质量份，优选为0.1～0.5质量份。若粘结剂的使用量过少，则所得到的粒状体的强度弱，有可能因输送中等所施加的振动或冲击等而破碎，或在投入于水中时一次粒子脱落。若粘结剂的使用量过多，则作为阳离子交换的活性部位的通过M2Ti2O5表示的钛酸盐的比率变小，因此，阳离子交换容量(放射性物质吸附量)变小。
增塑剂的使用量，无特别限定，相对于钛酸盐粉末1质量份，优选为0.01～0.1质量份。若增塑剂的使用量为上述范围内，则可有效地成型钛酸盐粉末。
若考虑制造成本，则使用的增塑剂优选为水，进一步地优选并用具有与水接触则增粘的性质并且通过其粘化作用有助于粒子间的结合的物质与水。若从该方面考虑，则作为增塑剂优选并用水与纤维素衍生物或PVA等。
作为增塑剂，并用水与纤维素衍生物和/或PVA时，在粘结剂中的水与纤维素衍生物和/或PVA的配合比(质量基准)优选为1000：1～10：1。若配合比为此范围内，则可有效地成型钛酸盐粉末。
作为使用粘结剂与增塑剂而成型钛酸盐的粉末的方法，可举例如混合钛酸盐粉末与绿坡缕石等的粘结剂，使混合有增塑剂的水与纤维素衍生物等的粘性流体一边添加于钛酸盐与绿坡缕石的混合粉末一边进行造粒成型的方法，使绿坡缕石等的粘结剂与纤维素等的增塑剂以粉体的状态混合于钛酸盐粉末，一边添加水等的液体一边进行造粒成型的方法等。
该造粒成型法，具体上可举例如使用鼓型造粒机、皿型造粒机等的转动造粒法；使用混合造粒机(Flexomix)、立式造粒机(Vertical granulator)等的混合搅拌造粒法；使用螺杆型挤出造粒机、辊型挤出造粒机、刀片型挤出造粒机、自己成型型挤出造粒机等的挤出造粒法；使用压片形造粒机、块状形造粒机等的压缩造粒法；在吹起的流体(主要为空气)中一边保持使钛酸盐粉末与粘结剂浮游悬浊的状态，一边喷雾水或醇等的粘结剂而造粒的流动层造粒法等，但从成型为粒状体方面考虑，优选为转动造粒法或混合搅拌造粒法。
如此做法所得到的钛酸盐的粒状体的大小，粒径为150～3000μm，优选为300～2000μm。若此粒状体的大小大于上述范围，表面积变小，因此，放射性物质吸附能力降低，若小，则有可能从吸附塔的过滤器泄漏。作为粒状体的粒径，若粒状体为球状，则为其直径，若为其他的形状，则是使该粒状体以2片的平行板挟住时，其板的间隔成为最大的部位的长度(2片的板的间隔)。
在本发明中，优选使成型的钛酸盐的粒状体在空气环境下，以500～900℃进行烧成，通过此烧成，粘结剂粉末与钛酸盐粉末被烧结，粒子强度提高。在此烧成处理中，若烧成温度未达500℃，则残存未烧结部位而粒子强度变弱，若超过900℃，则对钛酸盐结晶的结构造成影响而吸附性能降低。
烧成时间，根据烧成温度、粒状体的大小的不同而不同，但通常为0.5～10小时左右。
本发明的放射性物质吸附材料，优选填充于在下部或上部具有过滤器结构的吸附容器或吸附塔而使用，能够有效地适用于使含有放射性物质、尤其是含有放射性锶的污染水通入于该吸附容器或吸附塔而除去放射性物质的水处理装置。
实施例
以下，举例实施例及比较例而更具体地说明本发明。
合成例1：二钛酸钾的合成
使氧化钛418.94g及碳酸钾377.05g以亨舍尔混合机混合，一边使所得到的混合物以振动研磨机粉碎，一边混合0.5小时。使所得到的粉碎混合物50g填充于坩埚，以电炉以780℃进行烧成4小时，使烧成物以锤磨机进行粉碎，得到在不规则方向具有复数个突起物延伸的形状的二钛酸钾。平均粒径为20μm。
合成例2：四钛酸钾的合成
使氧化钛117.50g、碳酸钾58.75g及氯化钾23.50g以亨舍尔混合机混合，使所得到的混合物50g填充于坩埚，以电炉以1000℃进行烧成4小时，将烧成物投入于温水中，进行敲碎，过滤，干燥，得到四钛酸钾纤维。
在以下中，作为比较例1的放射性物质吸附材料，使用了专利文献1所示的颗粒状的钛酸钠的市售品，商品名“SrTreat”(Fortum公司制)。
作为比较例2的放射性物质吸附材料，使用了合成例2所得到的四钛酸钾，作为比较例3的放射性物质吸附材料，使用了8钛酸钾(商品名“ティスモ”，化学式：K2Ti8O17，大塚化学公司制)。
实施例1
在合成例1所得到的二钛酸钾粉末400g中加入绿坡缕石粉末80g作为粘结剂，通过混合搅拌造粒机(商品名“VG–01”、パウレック公司制)，以旋转数400rpm高速搅拌。其后，缓缓地加入4重量％的聚乙烯醇溶液190g，通过转动造粒使粒子滚雪球式成长。使所得到的造粒体以105℃干燥2小时后，以金属制的筛分级成粒径300～1180μm。使经分级的粒状体以电马弗炉在空气环境下、以600℃烧成2小时。
(耐一次粒子脱落性的评价)
分别计量实施例1的放射性物质吸附材料与比较例1的放射性物质吸附材料1g，投入于锥形烧杯后，添加自来水(日本栃木县野木町水)99g而轻轻摇混后，依据JIS K0101(工业用水试验方法)，计测上清液的浊液而评价耐一次粒子脱落性。
作为计测浊度的结果，实施例1的放射性物质吸附材料的浊度为1.9，与此相对，比较例1的放射性物质吸附材料的浊度为230。
从此结果可知，实施例1的放射性物质吸附材料，与比较例1的放射性物质吸附材料相比，更大幅地降低在水中的一次粒子的脱落。
(放射性物质吸附性能的评价)
分别计量实施例1的放射性物质吸附材料与比较例2、3的放射性物质吸附材料1g，投入于塑料容器(ポリ容器)。在各自的塑料容器中，加入以使稳定同位素的氯化锶溶解于自来水(日本栃木县野木町水)中成为锶浓度10mg/l的水溶液100ml。分别振动30分钟、1小时、2小时、4小时后，以0.45μm的膜过滤器过滤，使滤液导入于ICP–MS而定量滤液中的锶浓度。其结果表示于图1中。
从图1可知，锶浓度在实施例1的放射性物质吸附材料时可降低至最低浓度。
使用特定的方案而详细地说明了本发明，但本领域技术人员熟知，在不脱离本发明的意旨与范围内，可进行各种的变更。
另外，本申请是基于2012年5月29日提出的日本专利申请(特愿2012–122215)而提出的，其全体通过引用而被援用于此。
Claims (6)
1.一种水中的放射性锶的吸附材料，其含有通过化学式K2Ti2O5表示的钛酸盐造粒体，并且，前述钛酸盐造粒体使用粘结剂成型为粒径是150～3000μm的范围的成型体，前述钛酸盐造粒体具有在不规则方向延伸复数个突起物的形状，并且，前述粘结剂是粘土矿物，在前述成型后，进一步以500～900℃的温度范围进行烧成而成。
2.如权利要求1所述的水中的放射性锶的吸附材料，其中，前述钛酸盐造粒体的平均粒径是1～150μm。
3.如权利要求1所述的水中的放射性锶的吸附材料，其中，前述粘土矿物是绿坡缕石。
4.一种吸附容器，其填充有权利要求1～3中任一项所述的水中的放射性锶的吸附材料。
5.一种吸附塔，其填充有权利要求1～3中任一项所述的水中的放射性锶的吸附材料。
6.一种水处理装置，其具备权利要求4所述的吸附容器或权利要求5所述的吸附塔。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012122215A JP6106952B2 (ja) | 2012-05-29 | 2012-05-29 | 放射性物質吸着材、並びにそれを用いた吸着容器、吸着塔、及び水処理装置 |
| JP2012-122215 | 2012-05-29 | ||
| PCT/JP2013/064028 WO2013179940A1 (ja) | 2012-05-29 | 2013-05-21 | 放射性物質吸着材、吸着容器、吸着塔、及び水処理装置 |
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| CN104412329A CN104412329A (zh) | 2015-03-11 |
| CN104412329B true CN104412329B (zh) | 2017-10-13 |
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| RU (1) | RU2629961C2 (zh) |
| TW (1) | TWI619549B (zh) |
| WO (1) | WO2013179940A1 (zh) |
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| JP6197482B2 (ja) * | 2013-08-26 | 2017-09-20 | 栗田工業株式会社 | ストロンチウム吸着剤の製造方法 |
| JP6263066B2 (ja) * | 2014-03-27 | 2018-01-17 | 株式会社クボタ | 複合チタネートイオン交換体 |
| US9862247B2 (en) * | 2014-09-22 | 2018-01-09 | Ford Global Technologies, Llc | Directional climate control system with infrared targeting |
| CN104475008B (zh) * | 2014-12-19 | 2017-02-01 | 北京林业大学 | 一种高温co2吸附材料及其在吸附增强型产氢反应中的应用方法 |
| JP6407087B2 (ja) * | 2015-03-31 | 2018-10-17 | 株式会社クボタ | 複合イオン交換体並びにそれを備えたイオン吸着装置及び水処理システム |
| JP6928928B2 (ja) * | 2016-12-15 | 2021-09-01 | 東洋紡株式会社 | 放射性物質除去フィルタ、それを用いる放射性物質除去フィルタユニット及び放射性物質の除去方法 |
| JP7086524B2 (ja) | 2017-03-08 | 2022-06-20 | 株式会社荏原製作所 | アルカリ土類金属イオン吸着剤及びその製造方法並びにアルカリ土類金属イオン含有液処理装置 |
| JP6470354B2 (ja) * | 2017-07-05 | 2019-02-13 | 株式会社荏原製作所 | シリコチタネート成形体及びその製造方法、シリコチタネート成形体を含むセシウム又はストロンチウムの吸着剤、及び当該吸着剤を用いる放射性廃液の除染方法 |
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| US1697929A (en) * | 1925-06-02 | 1929-01-08 | Titanium Pigment Co Inc | Alkali-metal titanate and method of making same |
| US3328117A (en) * | 1963-05-10 | 1967-06-27 | Du Pont | Process for producing fibrous alkali metal titanates |
| JPS56100637A (en) * | 1980-01-16 | 1981-08-12 | Natl Inst For Res In Inorg Mater | Ion exchange material of cesium in aqueous solution and fixing method for cesium |
| US4373037A (en) * | 1981-05-29 | 1983-02-08 | Engelhard Corporation | Asbestos-free friction material incorporating attapulgite clay |
| FI821535L (fi) * | 1982-04-30 | 1983-10-31 | Jukka Kalevi Lehto | Foerfarande foer framstaellning av titanater |
| US4432893A (en) * | 1982-05-19 | 1984-02-21 | The United States Of America As Represented By The Department Of Energy | Precipitation-adsorption process for the decontamination of nuclear waste supernates |
| JPH0915389A (ja) * | 1995-06-27 | 1997-01-17 | Japan Atom Energy Res Inst | 放射性核種の吸着材及びその製造方法及び放射性廃棄物の減容処理方法 |
| RU2169118C2 (ru) * | 1995-10-20 | 2001-06-20 | Эллайдсигнал Инк. | Титанат натрия с частично кристаллической слоистой структурой |
| FI956222A0 (fi) * | 1995-12-22 | 1995-12-22 | Ivo International Oy | Framstaellning av granulaera titanatjonbytare |
| US5989434A (en) * | 1997-10-31 | 1999-11-23 | 3M Innovative Properties Company | Method for removing metal ions from solution with titanate sorbents |
| JP2001133594A (ja) * | 1999-11-05 | 2001-05-18 | Jgc Corp | 原子炉冷却水からの放射性核種の除去方法 |
| KR101428833B1 (ko) * | 2007-04-04 | 2014-08-08 | 오츠카 가가쿠 가부시키가이샤 | 티탄산칼륨, 그의 제조 방법, 마찰재 및 수지 조성물 |
| EP2243547A1 (en) * | 2009-04-20 | 2010-10-27 | Fortum OYJ | Novel sorbent, method of producing the same and the use thereof |
| CN202058473U (zh) * | 2011-03-16 | 2011-11-30 | 中科华核电技术研究院有限公司 | 一种放射性废物处理装置 |
| CN102347089B (zh) * | 2011-10-28 | 2013-10-23 | 衡阳师范学院 | 核电站安全壳内放射性核素吸附沉淀的方法及装置 |
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- 2013-05-21 RU RU2014152675A patent/RU2629961C2/ru active
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| RU2014152675A (ru) | 2016-07-20 |
| EP2860735A4 (en) | 2016-02-24 |
| CN104412329A (zh) | 2015-03-11 |
| TW201408366A (zh) | 2014-03-01 |
| JP2013246145A (ja) | 2013-12-09 |
| WO2013179940A1 (ja) | 2013-12-05 |
| EP2860735B1 (en) | 2017-06-28 |
| EP2860735A1 (en) | 2015-04-15 |
| JP6106952B2 (ja) | 2017-04-05 |
| RU2629961C2 (ru) | 2017-09-05 |
| TWI619549B (zh) | 2018-04-01 |
| US20150306594A1 (en) | 2015-10-29 |
| US20160314864A1 (en) | 2016-10-27 |
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