TW201408366A - 放射性物質吸附材、吸附容器、吸附塔、及水處理裝置 - Google Patents
放射性物質吸附材、吸附容器、吸附塔、及水處理裝置 Download PDFInfo
- Publication number
- TW201408366A TW201408366A TW102118651A TW102118651A TW201408366A TW 201408366 A TW201408366 A TW 201408366A TW 102118651 A TW102118651 A TW 102118651A TW 102118651 A TW102118651 A TW 102118651A TW 201408366 A TW201408366 A TW 201408366A
- Authority
- TW
- Taiwan
- Prior art keywords
- titanate
- radioactive
- adsorbing material
- adsorption
- radioactive substance
- Prior art date
Links
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000012857 radioactive material Substances 0.000 title claims abstract description 20
- 239000003463 adsorbent Substances 0.000 title abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 45
- 239000000941 radioactive substance Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 22
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002734 clay mineral Substances 0.000 claims description 8
- 230000002285 radioactive effect Effects 0.000 claims description 8
- 230000001788 irregular Effects 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000011164 primary particle Substances 0.000 abstract description 9
- 238000010304 firing Methods 0.000 abstract description 8
- 238000005341 cation exchange Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 19
- 239000010936 titanium Substances 0.000 description 17
- 238000005469 granulation Methods 0.000 description 13
- 230000003179 granulation Effects 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 239000004113 Sepiolite Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000001913 cellulose Chemical class 0.000 description 7
- 229920002678 cellulose Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052624 sepiolite Inorganic materials 0.000 description 7
- 235000019355 sepiolite Nutrition 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- -1 sodium titanate ion Chemical class 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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
- 229910052719 titanium Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 238000011161 development Methods 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
- 239000007788 liquid Substances 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 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
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- 229920002125 Sokalan® Polymers 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 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
- 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
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000394 mitotic effect Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
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- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
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- 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
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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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- B01J20/041—Oxides or hydroxides
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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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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/10—Oxides or hydroxides
-
- 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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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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- 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)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本發明係提供一種吸附容量多之放射性物質吸附材。本發明之放射性物質吸附材係含有化學式以M2Ti2O5(M為一價陽離子)表示之鈦酸鹽。M2Ti2O5係陽離子交換容量大，熱性亦安定，於酸、鹼等之耐藥品性亦優異，適宜作為水處理用之吸附材。於此鈦酸鹽中加入黏結劑而成形之後，藉燒成而機械強度提昇，可抑制輸送中等所施加之振動或衝擊等造成的破碎，或投入於水時之一次粒子的脫落。
Description
本發明係關於一種放射性物質吸附材、填充此放射性物質吸附材而成之吸附容器及吸附塔、與適用此吸附容器或吸附塔之水處理裝置。
放射性鍶90Sr係與輻射性銫同樣地，半衰期長，又，為對水之擴散性高的核分裂生成物，期望處理受放射性鍶污染之水的系統之改良。
水中之放射性鍶係已知可以正鈦酸吸附而除去(非專利文獻1)。
吸附放射性鍶之鈦酸鈉離子交換體的製造方法已提出一種使含氫氧化鈦以醇與氫氧化鈉所構成之液體漿液化而加熱，過濾、乾燥後，破碎、分級而製造鈉/鈦莫耳比為0.6以下之顆粒狀的鈦酸鈉之方法(專利文獻1)。
[專利文獻1]：特許第4428541號公報
[非專利文獻1]：久保田益光外，”群分離法之開發：無機離子交換體管柱法之含90Sr及134Cs的廢液之處理法的開發”JAERI-M82-144(1982)
記載於專利文獻1之方法所製造的顆粒狀之鈦酸鈉係交換陽離子之鈉/鈦的莫耳比低，故吸附容量小。
記載於專利文獻1之方法所製造的顆粒狀之鈦酸鈉係因為一次粒子之凝集體，強度弱，若輸送中等所施加之振動或衝擊等被粉碎而微粒化，或投入於水中，凝集體之崩壞一次粒子脫落。因此，此微粉化之粒子或一次粒子使吸附塔之過濾器堵塞，或通過吸附塔過濾器，帶有放射線之微粉從吸附塔洩漏。
本發明之第1目的在於提供一種吸附容量多之放射性物質吸附材。
本發明之第2目的在於提供一種機械強度優，微粉等之洩漏無問題，作為水處理材而處理性優之放射性物質吸附材。
本發明之第3目的在於提供一種填充此放射性物質吸附材而成之吸附容器及吸附塔、與適用此吸附容器或吸附塔之水處理裝置。
本發明人等發現以M2Ti2O5(M為一價陽離子)所示之鈦酸鹽於放射性物質吸附量優異。又，發現於此鈦酸鹽之粉末加入黏結劑而成形為特定大小之粒狀體，進一步燒成所製造之放射性物質吸附材係機械強度優，無微粉等之洩漏，作為水處理材而處理性優。
本發明係依據如此之見識所達成者，以下為要旨。
[1]一種放射性物質吸附材，其特徵係含有化學式以M2Ti2O5(M為一價陽離子)所示之鈦酸鹽。
[2]如[1]項之放射性物質吸附材，其中前述鈦酸鹽係平均粒徑為1~150μm。
[3]如[1]或[2]項之放射性物質吸附材，其中前述化學式以K2Ti2O5所示。
[4]如[3]項之放射性物質吸附材，其中前述鈦酸鹽具有於不規則方向延伸複數突起物之形狀。
[5]如[1]~[4]項中任一項之放射性物質吸附材，其中前述放射性物質為放射性鍶。
[6]如[1]~[5]項中任一項之放射性物質吸附材，其中前述鈦酸鹽為使用黏結劑而成形為粒徑150~3000μm之範圍。
[7]如[6]項之放射性物質吸附材，其中前述黏結劑為黏土礦物。
[8]如[7]項之放射性物質吸附材，其中前述黏土礦物為鎂鋁海泡石(Attapulgite)。
[9]如[6]~[8]項中任一項之放射性物質吸附材，其中前述成形後，進一步以500~900℃之溫度範圍燒成而成。
[10]一種吸附容器，其係填充如[1]~[9]項中任一項之放射性物質吸附材。
[11]一種吸附塔，其係填充如[1]~[9]項中任一項之放射性物質吸附材。
[12]一種水處理裝置，其係具備如[10]項之吸附容器或如[11]項之吸附塔。
以M2Ti2O5(M為一價陽離子)所示之鈦酸鹽係放射性物質之吸附容量大於其他之鈦酸鹽。
於此鈦酸鹽之粉末中加入黏結劑而成形之後，藉燒成所製造之放射性物質吸附材係機械強度高，可抑制輸送中等所施加之振動或衝擊等造成的破碎，或投入於水時之一次粒子的脫落。因此，可防止因微粉粒子之吸附塔過濾器的堵塞，或帶有放射線之微粉的洩漏。
圖1係表示實施例1及比較例2、3之結果的圖表。
以下，詳細說明本發明之實施形態，但以下說明之實
施形態係用以容易理解本發明者，並非限定任何本發明，本發明係在不超出其要旨的範圍，可使以下之實施形態所揭示的各要素進行各種變更而實施。
本發明之放射性物質吸附材其特徵係含有以M2Ti2O5所示之鈦酸鹽。M為一價陽離子。
鈦酸鹽一般以M2TinO2n+1所示，作為陽離子交換體之鈦酸鹽係n愈大，鈦酸鹽每一分子之陽離子交換位址變少，故陽離子交換容量變小。
陽離子交換容量之點係理想上為M2TiO3，但以M2TiO3所示之鈦酸鹽係非常不安定，藉加熱等立即改性成M2Ti2O5。
M2Ti2O5係熱性安定，於酸、鹼等之耐藥品性優異，適宜作為水處理用之吸附材。
本發明所使用之以M2Ti2O5所示之鈦酸鹽的一價陽離子M係陽離子交換性優異，故宜為鉀。若依Y.Q.Jia，J.Solid State Chem.，95(1991)184，鍶之離子半徑與鹼金屬元素的離子半徑係如下表，K係略大於Sr之離子半徑，適宜作為陽離子交換體。
一價陽離子M為鉀之K2Ti2O5係若以一般熔融法等進行合成，成為纖維形狀，但如記載於WO2008/123046，一邊使鈦源及鉀源以機械化學粉碎一邊混合後，使其粉碎混合物以650~1000℃燒成之製法，俾可形成為在不規則方向延伸複數突起物之形狀。具有該形狀之鈦酸鹽的造粒體係粉體強度高，可增大短徑大小，故可控制陽離子交換速度。
以M2Ti2O5所示之鈦酸鹽宜為平均粒徑在1~150μm之範圍的粉末狀。平均粒徑係可藉例如雷射繞射式粒度分布測定裝置測定。
平均粒徑為1~150μm之鈦酸鹽粉末係吸附容量大，又，在後面之成形步驟中在操作面優異。亦即，若平均粒徑為1μm以上，不會產生因飛濺或靜電造成之容器附著等製造上的難點。若平均粒徑為150μm以下，不會因比表面積的降低使得吸附容量亦降低。
因此，在本發明中，宜使用如此之粒徑的鈦酸鹽粉末。鈦酸鹽粉末的平均粒徑更宜為4~30μm。
在本發明中，較佳係使如上述之鈦酸鹽粉末形成特定之大小而使用，尤其宜成形後，以特定之條件燒成而使用。
使鈦酸鹽粉末成形所得到之成形體的形狀或大小係填充於吸附容器或吸附塔，只要為適應於通入含放射性物質之水的形狀即可，可為例如球狀、立方體形狀、長方體形狀、圓柱形狀等之定形粒狀體，亦可為不定形狀體。若考
量對吸附容器或吸附塔之填充性，宜為球狀粒狀體。
形成鈦酸鹽粉末之方法係無特別限定，但可舉例如使用黏結劑等而使鈦酸鹽粉末成形為粒狀體之方法。
上述黏結劑係可舉例如蒙脫土、鎂鋁海泡石(Attapulgite)、海泡石(Sepiolite)、英石(Allophane)、埃洛石(halloysite)、絲狀鋁英石(Imogolite)、高嶺石(kaolinite)等之黏土礦物；矽酸鈉、矽酸鈣、矽酸鎂、偏矽酸鈉、偏矽酸鈣、偏矽酸鎂、偏矽酸鋁酸鈉、偏矽酸鋁酸鈣、偏矽酸鋁酸鎂等之矽酸鹽化合物等。此等係可1種單獨使用，亦可混合2種以上而使用。
此等之中，黏結劑係就可廉價地製造之點，宜為使用較化成品之矽酸鹽化合物更天然物之黏土礦物，進一步，即使在黏土礦物中，就粒狀體之機械強度之點，宜為使用鎂鋁海泡石或海泡石等之纖維狀的黏土礦物。
成形時，宜亦同樣地添加可得到造粒所需要之塑性的可塑劑。上述可塑劑可舉例如澱粉、玉米澱粉、糖蜜、乳糖、纖維素、纖維素衍生物、明膠、糊精、阿拉伯膠、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。此等係可1種單獨使用，亦可混合2種以上而使用。
以特定之混合比混合鈦酸鹽與黏結劑與可塑劑之後，造粒成形，乾燥後，燒成，機械強度提昇，可抑制輸送中等所施加之振動或衝擊等造成的破碎，或投入於水時之一
次粒子的脫落。
黏結劑之使用量係無特別限定，相對於鈦酸鹽粉末1質量份，宜為0.1~0.5質量份。若黏結劑之使用量太少，所得到之粒狀體的強度弱，恐輸送中等所施加之振動或衝擊等而破碎，或投入於水時之一次粒子的脫落。若黏結劑之使用量太多，陽離子交換之活性部位的以M2Ti2O5所示之鈦酸鹽之比率變小，故陽離子交換容量(放射性物質吸附量)變小。
可塑劑之使用量係無特別限定，相對於鈦酸鹽粉末1質量份，宜為0.01~0.1質量份。若可塑劑之使用量為上述範圍內，可有效地成形鈦酸鹽粉末。
若考量製造成本，使用之可塑劑宜為水，進一步係若與水接觸，具有增黏之性質，宜為併用藉其黏化作用有助於粒子間之結合的物質與水。若考量此點，宜併用水與纖維素衍生物或PVA等作為可塑劑。
併用水與纖維素衍生物及/或PVA作為可塑劑時，在黏結劑之水與纖維素衍生物及/或PVA的摻合比(質量基準)宜為1000：1~10：1。若摻合比為此範圍內，可有效地成形鈦酸鹽粉末。
使用黏結劑與可塑劑而成形鈦酸鹽之粉末的方法，可舉例如混合鈦酸鹽粉末與鎂鋁海泡石等之黏結劑，使混合有可塑劑之水與纖維素衍生物等之黏性流體添加於鈦酸鹽與鎂鋁海泡石之混合粉末同時並造粒成形之方法，使鎂鋁海泡石等之黏結劑與纖維素的可塑劑直接混合於粉體之鈦
酸鹽粉末，一邊添加水等之液體，同時並造粒成形之方法等。
此造粒成形法具體上係可舉例如使用鼓型造粒機、皿型造粒機等之轉動造粒法；Flexomix、粒子造粒機等之混合攪拌造粒法；螺桿型押出造粒機、輥輪型押出造粒機、刮刀型押出造粒機、自己成形型押出造粒機等之押出造粒法；打錠形造粒機、塊狀形造粒機等之壓縮造粒法；在吹起之流體(主要為空氣)中一邊保持使鈦酸鹽粉末與黏結劑浮游懸濁之狀態，一邊噴霧水或醇等之黏結劑而造粒的流動層造粒法等，但若考量成形為粒狀體，宜為轉動造粒法或混合攪拌造粒法。
如此做法所得到之鈦酸鹽的粒狀體之大小係就粒徑為150~3000μm，宜為300~2000μm。若此粒狀體之大小大於上述範圍，表面積變小，故放射性物質吸附能降低，若小，恐從吸附塔之過濾器洩漏。粒狀體之粒徑係若粒狀體為球狀，相當於其直徑，其他之形狀時，使該粒狀體以2片之平行板挾住時，指其板之間隔成為最大的部位之長度(2片之板的間隔)。
在本發明中係宜使成形之鈦酸鹽的粒狀體在空氣環境下、500~900℃燒成，藉此燒成，黏結劑粉末與鈦酸鹽粉末被燒結，粒子強度提高。在此燒成處理中，若燒成溫度未達500℃，未燒結部位殘存而粒子強度變弱，若超過900℃，對鈦酸鹽結晶之構造造成影響而吸附性能降低。
燒成時間係亦依燒成溫度、粒狀體之大小而異，但一
般為0.5~10小時左右。
本發明之放射性物質吸附材係宜填充於在下部或上部具有過濾器構造之吸附容器或吸附塔而使用，使放射性物質、尤其含有放射性鍶之污染水通入於該吸附容器或吸附塔而可有效地適用除去放射性物質之水處理裝置。
以下，舉例實施例及比較例而更具體地說明本發明。
使氧化鈦418.94g及碳酸鉀377.05g以漢歇爾混合機混合，一邊使所得到之混合物以振動研磨粉碎，一邊混合0.5小時。使所得到之粉碎混合物50g填充於研缽，以電爐以780℃進行燒成4小時，使燒成物以鎚磨機進行粉碎，得到於不規則方向具有延伸複數突起物之形狀的二鈦酸鉀。平均粒徑為20μm。
使氧化鈦117.50g、碳酸鉀58.75g及氯化鉀23.50g以漢歇爾混合機混合，使所得到之混合物50g填充於研缽，以電爐以1000℃進行燒成4小時，將燒成物投入於溫水中，敲碎，過濾，乾燥，得到四鈦酸鉀纖維。
在以下中比較例1之放射性物質吸附材係使用專利文獻1所示之顆粒狀的鈦酸鈉之市售品商品名「SrTreat」
(Fortum公司製)。
比較例2之放射性物質吸附材係使用合成例2所得到之四鈦酸鉀，比較例3之放射性物質吸附材係使用8鈦酸鉀(商品名「Tismo」化學式：K2Ti8O17，大塜化學公司製)。
於合成例1所得到之二鈦酸鉀粉末400g中加入鎂鋁海泡石粉末80g作為黏結劑，藉混合攪拌造粒機(商品名「VG-01」、Powrex公司製)，以旋轉數400rpm高速攪拌。其後，徐緩地加入4重量%之聚乙烯醇溶液190g，藉轉動造粒使粒子成長為雪人式。使所得到之造粒體以105℃乾燥2小時後，以金屬製之篩分級成粒徑300~1180μm。使經分級之粒狀體以電器高溫爐在空氣環境下、以600℃燒成2小時。
分別計量實施例1之放射性物質吸附材與比較例1之放射性物質吸附材1g，投入於錐形燒杯後，添加自來水(栃木縣野木町水)99g而輕輕搖混後，依據JIS K0101(工業用水試驗方法)，計測上清液之濁液而評估耐一次粒子脫落性。
計測濁度之結果，實施例1之放射性物質吸附材濁度為1.9，但比較例1之放射性物質吸附材濁度為230。
從此結果，可知實施例1之放射性物質吸附材，較比較例1之放射性物質吸附材，更大幅地降低水中之一次粒子的脫落。
分別計量實施例1之放射性物質吸附材與比較例2,3之放射性物質吸附材1g，投入於塑膠容器。於各別之塑膠容器中，加入溶解於自來水(栃木縣野木町水)之水溶液100ml以使安定同位素之氯化鍶成為鍶濃度10mg/l。分別振動30分、1小時、2小時、4小時後，以0.45μm之過濾膜過濾，使濾液導入於ICP-MS而定量濾液中之鍶濃度。結果表示於圖1中。
從圖1可知鍶濃度係實施例1之放射性物質吸附材時可降低至最低濃度。
使用特定之態樣而詳細說明本發明，但不脫離本發明之意旨與範圍，可各種之變更係熟悉此技藝者所熟知。
又，在本申請案係依據2012年5月29日所申請之日本專利申請(特願2012-122215)，其全體藉引用而被援用。
Claims (12)
- 一種放射性物質吸附材，其係含有化學式以M2Ti2O5(M為一價陽離子)所示之鈦酸鹽。
- 如申請專利範圍第1項之放射性物質吸附材，其中前述鈦酸鹽係平均粒徑為1~150μm。
- 如申請專利範圍第1或2項之放射性物質吸附材，其中前述化學式以K2Ti2O5所示。
- 如申請專利範圍第3項之放射性物質吸附材，其中前述鈦酸鹽具有於不規則方向延伸複數突起物之形狀。
- 如申請專利範圍第1~4項中任一項之放射性物質吸附材，其中前述放射性物質為放射性鍶。
- 如申請專利範圍第1~5項中任一項之放射性物質吸附材，其中前述鈦酸鹽為使用黏結劑而成形為粒徑150~3000μm。
- 如申請專利範圍第6項之放射性物質吸附材，其中前述黏結劑為黏土礦物。
- 如申請專利範圍第7項之放射性物質吸附材，其中前述黏土礦物為鎂鋁海泡石(Attapulgite)。
- 如申請專利範圍第6~8項中任一項之放射性物質吸附材，其中前述成形後，進一步以500~900℃之溫度範圍燒成而成。
- 一種吸附容器，其係填充如申請專利範圍第1~9項中任一項之放射性物質吸附材。
- 一種吸附塔，其係填充如申請專利範圍第1~9項 中任一項之放射性物質吸附材。
- 一種水處理裝置，其係具備如申請專利範圍第10項之吸附容器或如申請專利範圍第11項之吸附塔。
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| 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 |
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| TWI619549B TWI619549B (zh) | 2018-04-01 |
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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 |
| EP0855992A1 (en) * | 1995-10-20 | 1998-08-05 | AlliedSignal Inc. | Partially crystalline layered sodium titanate |
| 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 |
| EP2130798B1 (en) * | 2007-04-04 | 2018-05-16 | Otsuka Chemical Co., Ltd. | Potassium titanate, process for production of the same, friction materials, and resin compositions |
| 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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2012
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2013
- 2013-05-21 US US14/403,009 patent/US20150306594A1/en not_active Abandoned
- 2013-05-21 CN CN201380028418.7A patent/CN104412329B/zh active Active
- 2013-05-21 RU RU2014152675A patent/RU2629961C2/ru active
- 2013-05-21 EP EP13796716.2A patent/EP2860735B1/en active Active
- 2013-05-21 WO PCT/JP2013/064028 patent/WO2013179940A1/ja active Application Filing
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2016
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| Publication number | Publication date |
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| EP2860735A4 (en) | 2016-02-24 |
| CN104412329B (zh) | 2017-10-13 |
| US20150306594A1 (en) | 2015-10-29 |
| EP2860735A1 (en) | 2015-04-15 |
| WO2013179940A1 (ja) | 2013-12-05 |
| CN104412329A (zh) | 2015-03-11 |
| TWI619549B (zh) | 2018-04-01 |
| RU2629961C2 (ru) | 2017-09-05 |
| JP2013246145A (ja) | 2013-12-09 |
| JP6106952B2 (ja) | 2017-04-05 |
| RU2014152675A (ru) | 2016-07-20 |
| US20160314864A1 (en) | 2016-10-27 |
| EP2860735B1 (en) | 2017-06-28 |
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