JP2016002532A - Strontium adsorbent, production method thereof, and environment processing method using the same - Google Patents
Strontium adsorbent, production method thereof, and environment processing method using the same Download PDFInfo
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- JP2016002532A JP2016002532A JP2014125890A JP2014125890A JP2016002532A JP 2016002532 A JP2016002532 A JP 2016002532A JP 2014125890 A JP2014125890 A JP 2014125890A JP 2014125890 A JP2014125890 A JP 2014125890A JP 2016002532 A JP2016002532 A JP 2016002532A
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- strontium
- iron
- silicon
- oxide
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- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 96
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003463 adsorbent Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000003672 processing method Methods 0.000 title 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 14
- 230000002285 radioactive effect Effects 0.000 abstract description 13
- 239000002689 soil Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 2
- CZSABVBCTRZESY-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].OS(O)(=O)=O Chemical compound [O-2].[O-2].[Ti+4].OS(O)(=O)=O CZSABVBCTRZESY-UHFFFAOYSA-N 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 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 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CIOAGBVUUVVLOB-NJFSPNSNSA-N Strontium-90 Chemical compound [90Sr] CIOAGBVUUVVLOB-NJFSPNSNSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- -1 phosphate compound Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001631 strontium chloride Inorganic materials 0.000 description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 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
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 239000002901 radioactive waste Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000011065 in-situ storage 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SKMHHHHLLBKNKR-UHFFFAOYSA-M sodium;prop-2-enamide;prop-2-enoate Chemical compound [Na+].NC(=O)C=C.[O-]C(=O)C=C SKMHHHHLLBKNKR-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
本発明は、ストロンチウムを効率良く吸着し不溶化できる吸着材とその製造方法、並びにこの吸着材を用いた環境処理方法に関する。 The present invention relates to an adsorbent capable of efficiently adsorbing and insolubilizing strontium, a manufacturing method thereof, and an environmental treatment method using the adsorbent.
原子炉から排出される放射性廃棄物処理については、従来より、様々な方法が開発されている。特に、２０１１年の東日本大震災によって、原子炉爆発事故を引き起こした福島原子力発電所では、その後、廃炉作業が進められているものの、放射性物質で汚染された冷却水が排出され続けている一方で、汚染水は、密閉タンクに貯蔵する以外の対策が取られていない。このため、放射性汚染水の処理技術が注目されており、例えば、ストロンチウム９０等の、半減期の長い放射性物質を含む汚染水に、リン酸塩を添加して、放射性物質をリン酸化合物とした後、更に、塩化鉄及び／又は塩化アルミニウムを添加し中和して、生成する水酸化鉄及び／又は水酸化アルミニウムの沈殿中に、当該リン酸化合物を取り込んで不溶化する技術が知られている（特許文献１）。 Various methods have been developed for the treatment of radioactive waste discharged from nuclear reactors. In particular, at the Fukushima nuclear power plant that caused the nuclear explosion accident due to the 2011 Great East Japan Earthquake, while decommissioning work has been underway, cooling water contaminated with radioactive materials continues to be discharged. Measures other than storing contaminated water in a closed tank are not taken. For this reason, attention has been paid to the treatment technology of radioactive polluted water. For example, phosphate is added to contaminated water containing a radioactive substance having a long half-life such as strontium 90 to make the radioactive substance a phosphate compound. Further, there is known a technique in which iron phosphate and / or aluminum chloride is further added to neutralize, and the phosphate compound is taken in and insolubilized during precipitation of the resulting iron hydroxide and / or aluminum hydroxide. (Patent Document 1).
しかし、特許文献１の方法では、環境中に飛散した放射性物質の除染には、適用が難しいという問題がある。 However, the method of Patent Document 1 has a problem that it is difficult to apply to decontamination of radioactive materials scattered in the environment.
本発明者らは、鋭意研究を重ねた結果、ケイ素を含有する鉄酸化物は、ストロンチウムの吸着能力に優れ、吸着したストロンチウムを高度に不溶化でき、そうすると、当然のこととして、放射性ストロンチウムに対しても吸着能力が優れ、吸着した放射性ストロンチウムを高度に不溶化できることを見出して本発明を完成させた。 As a result of intensive studies, the present inventors have found that iron-containing oxides containing silicon have an excellent ability to adsorb strontium and can highly insolubilize the adsorbed strontium, and as a matter of course, against radioactive strontium, The present invention was completed by finding that the adsorbing ability was excellent and the adsorbed radioactive strontium could be highly insolubilized.
即ち、本発明は、（１）ケイ素を含有する鉄酸化物を含むことを特徴とするストロンチウム吸着材であり、（２）鉄化合物とケイ素化合物とを媒液中で中和し酸化することを特徴とするストロンチウム吸着材の製造方法であり、（３）ストロンチウムを含む環境中に当該ストロンチウム吸着材を投入してストロンチウムを吸着させることを特徴とする環境処理方法である。 That is, the present invention is (1) a strontium adsorbent containing an iron oxide containing silicon, and (2) neutralizing and oxidizing an iron compound and a silicon compound in a liquid medium. A method for producing a strontium adsorbing material, characterized in that (3) the strontium adsorbing material is introduced into an environment containing strontium to adsorb the strontium.
本発明の吸着材は、ストロンチウム、放射性ストロンチウム等の吸着能力が高く、特に放射性ストロンチウムで汚染された水、土壌等を効果的に除染できる。従来のストロンチウム吸着材は、ナトリウムなどの夾雑イオンが存在すると、浄化対象のストロンチウムの吸着能力が低下することが知られているが、本発明の吸着材は夾雑イオンが存在しても優れた吸着能力を発揮する。 The adsorbent of the present invention has a high adsorption capacity for strontium, radioactive strontium, etc., and can effectively decontaminate water, soil, etc. contaminated with radioactive strontium. Conventional strontium adsorbents are known to have reduced ability to adsorb strontium to be purified when contaminated ions such as sodium are present. However, the adsorbent of the present invention is excellent in adsorption even when contaminated ions are present. Demonstrate ability.
本発明はストロンチウム吸着材であって、ケイ素を含有する鉄酸化物を含むことを特徴とする。本発明の吸着材は、ストロンチウムや放射性ストロンチウム等の吸着能力が優れているので、例えば、放射性ストロンチウムで汚染された水や土壌等の環境の除染に有用である。
ケイ素を含有する鉄酸化物の様態としては、（イ）鉄とケイ素の複合酸化物、（ロ）鉄酸化物とケイ素酸化物の混合物等が挙げられる。鉄とケイ素の複合酸化物は、鉄とケイ素と酸素から構成されるものであれば特に限定されず、同様に、鉄酸化物は、鉄と酸素から構成されるものであれば特に限定されず、ケイ素酸化物は、ケイ素と酸素から構成されるものであれば、特に限定されない。
（ロ）の様態には、鉄酸化物とケイ素酸化物の一様な混合物及び一様ではない混合物の双方がふくまれ、一様ではない混合物としては、例えば、鉄酸化物の表面等の一部にケイ素酸化物が偏在しているものが挙げられる。
The present invention is a strontium adsorbent, characterized by containing an iron oxide containing silicon. Since the adsorbent of the present invention has an excellent ability to adsorb strontium, radioactive strontium and the like, it is useful for decontamination of the environment such as water and soil contaminated with radioactive strontium.
Examples of the form of the iron oxide containing silicon include (a) a composite oxide of iron and silicon, (b) a mixture of iron oxide and silicon oxide, and the like. The composite oxide of iron and silicon is not particularly limited as long as it is composed of iron, silicon and oxygen. Similarly, the iron oxide is not particularly limited as long as it is composed of iron and oxygen. The silicon oxide is not particularly limited as long as it is composed of silicon and oxygen.
The mode (b) includes both uniform and non-uniform mixtures of iron oxide and silicon oxide. Examples of non-uniform mixtures include, for example, the surface of iron oxide. Examples thereof include those in which silicon oxide is unevenly distributed.
上記（イ）、（ロ）以外の様態として、（ハ）コア部の表面にシェル部を有するコア・シェル構造を成し、シェル部が鉄とケイ素の複合酸化物であるか、又は、鉄酸化物とケイ素酸化物との混合物であるものが挙げられる。
コア部の部材は、環境に二次的な汚染が生じないようなものであれば特に制限は無く、例えば、鉄酸化物、ケイ素酸化物、硫酸カルシウム、活性炭、ゼオライト、タルク等が挙げられ、中でも鉄酸化物が好ましい。鉄酸化物は前記と同様、鉄と酸素から構成されるものであればよく、化学組成がＦｅＯ、Ｆｅ３Ｏ４、Ｆｅ２Ｏ３、過還元マグネタイトＦｅＯｘ（１．０＜ｘ＜１．３３）、ベルトライドＦｅＯｘ（１．３３＜ｘ＜１．５）、ＦｅＯＨ、ＦｅＯＯＨ、Ｆｅ（ＯＨ）２等のいずれの酸化物も用いることができる。コア部とシェル部の鉄酸化物は同じであっても、異なっていてもよい。また、シェル部はコア部の全体を被覆するものであっても、一部を被覆するものであってもよい。
As modes other than the above (a) and (b), (c) a core-shell structure having a shell part on the surface of the core part, and the shell part is a composite oxide of iron and silicon, or iron The thing which is a mixture of an oxide and a silicon oxide is mentioned.
The core member is not particularly limited as long as secondary contamination does not occur in the environment, and examples thereof include iron oxide, silicon oxide, calcium sulfate, activated carbon, zeolite, and talc. Of these, iron oxide is preferable. The iron oxide may be composed of iron and oxygen as described above, and the chemical composition is FeO, Fe 3 O 4 , Fe 2 O 3 , overreduced magnetite FeO x (1.0 <x <1. 33), any oxide such as belt ride FeO x (1.33 <x <1.5), FeOH, FeOOH, Fe (OH) 2, etc. can be used. The iron oxides in the core part and the shell part may be the same or different. Further, the shell portion may cover the entire core portion or a portion thereof.
様態（イ）、(ロ)のケイ素含有量、または、様態（ハ）のシェル部のケイ素含有量は、Ｆｅ／Ｓｉで表される鉄酸化物中の鉄とのモル比で、１／０．１〜１／１０．０の範囲であれば、ストロンチウムの吸着能力が一層高くなるので好ましく、１／０．１〜１／５．０の範囲が更に好ましい。ケイ素を含有する鉄酸化物（以下、ケイ素含有鉄酸化物という場合がある）の形状は、球状、塊状等の等方性形状、針状、板状等の異方性形状等の制限を受けず、本願発明の目的を達成できる限りいずれの形状でもよく、ＢＥＴ法による比表面積が１０〜１００ｍ２／ｇの範囲にあれば好ましい。 The silicon content of the mode (b) or (b) or the silicon content of the shell part of the mode (c) is 1/0 in terms of a molar ratio with iron in the iron oxide represented by Fe / Si. The range of 0.1 to 1 / 10.0 is preferable because the adsorption ability of strontium is further increased, and the range of 1 / 0.1 to 1 / 5.0 is more preferable. The shape of silicon-containing iron oxides (hereinafter sometimes referred to as silicon-containing iron oxides) is limited by isotropic shapes such as spheres and lumps, and anisotropic shapes such as needles and plates. Any shape is possible as long as the object of the present invention can be achieved, and it is preferable if the specific surface area by the BET method is in the range of 10 to 100 m 2 / g.
鉄酸化物には、詳細には、様態（イ）、(ロ)の鉄酸化物や、様態（ハ）のシェル部の鉄酸化物には、ケイ素以外の無機元素、例えば、アルミニウム、マグネシウム、マンガン等が含まれていてもよい。ケイ素以外の無機元素の含有量は、アルミニウムであれば、Ｆｅ／Ａｌで表される鉄酸化物中の鉄とのモル比で、１／０．００５〜１／２．０の範囲が好ましい。
更に、様態(イ)、（ロ）における鉄酸化物、及び、様態（ハ）におけるシェル部の鉄酸化物に磁着性を付与するとストロンチウムを吸着させた後、磁別によって分離できる。様態（ハ）において、シェル部及びコア部の双方に鉄酸化物に用いた場合はコア部またはシェル部の少なくとも一方の鉄酸化物に磁着性を付与すれば磁別によって分離できる。
In detail, the iron oxide includes, in particular, the iron oxides of the modes (A) and (B) and the iron oxide of the shell part of the mode (C), inorganic elements other than silicon, such as aluminum, magnesium, Manganese etc. may be contained. If the content of inorganic elements other than silicon is aluminum, the molar ratio with iron in the iron oxide represented by Fe / Al is preferably in the range of 1 / 0.005 to 1 / 2.0.
Furthermore, when magnetic adhesion is imparted to the iron oxides in the modes (A) and (B) and the iron oxide in the shell in the mode (C), strontium is adsorbed and then separated by magnetic separation. In the aspect (c), when iron oxide is used for both the shell part and the core part, it can be separated by magnetic separation if magnetic adhesion is imparted to at least one iron oxide of the core part or the shell part.
本発明のストロンチウム吸着材には、ケイ素含有鉄水酸化物以外にも、必要に応じて、(a)他の吸着材（活性炭、ゼオライト、キレート樹脂等）、(b)粘土鉱物（ベントナイト、タルク、クレー等）、(c)有機高分子（アニオン系有機高分子（ポリアクリル酸ソーダ、アクリル酸−アクリル酸エステル共重合体、アクリル酸ソーダ−アクリルアミド共重合体、カルボキシメチルセルロースソーダ塩、デンプン−アクリル酸−アクリル酸ソーダ共重合体、酢酸ビニル−マレイン酸ソーダ共重合体等）、非イオン系有機高分子（ポリアクリルアミド、アルキルセルロース、ポリエチレンオキサイド等）等）、(d)固化材（セメント、石灰等）及び固化遅延剤（クエン酸等）、(e)分散剤等が配合されていてもよい。 In addition to the silicon-containing iron hydroxide, the strontium adsorbent of the present invention includes (a) other adsorbents (activated carbon, zeolite, chelate resin, etc.), (b) clay minerals (bentonite, talc, as necessary) , Clay), (c) organic polymer (anionic organic polymer (polyacrylic acid soda, acrylic acid-acrylic acid ester copolymer, sodium acrylate-acrylamide copolymer, carboxymethylcellulose soda salt, starch-acrylic) Acid-sodium acrylate copolymer, vinyl acetate-sodium maleate copolymer, etc.), nonionic organic polymers (polyacrylamide, alkyl cellulose, polyethylene oxide, etc.), (d) solidifying material (cement, lime) Etc.) and a solidification retarder (citric acid etc.), (e) a dispersant, etc. may be blended.
次に、本発明は、ストロンチウム吸着材の製造方法であって、鉄化合物とケイ素化合物とを媒液中で中和し酸化することを特徴とする。様態（イ）のケイ素含有鉄酸化物は、（i）鉄化合物とケイ素化合物を混合した後、中和剤を添加して中和し酸化するか、又は、（ii）ケイ素化合物を中和剤として用いて、鉄化合物とケイ素化合物とを中和し酸化することで得られる。一方、様態（ロ）では、(iii）鉄化合物を中和し酸化後、ケイ素化合物を中和し酸化するか、または、（iv）鉄化合物を中和し、ケイ素化合物を中和した後、酸化することで得られ、中和剤の添加は、鉄化合物の添加後やケイ素化合物の添加後に行うことも、鉄化合物、ケイ素化合物と同時に平行添加することもできる。更に、様態（ハ）では、コア部となる基材の存在下で、鉄化合物とケイ素化合物とを中和し酸化して、コア部の表面に、ケイ素を含有の鉄酸化物を含むシェル部を形成する。酸化は中和前、中和中、中和後のいずれのタイミングで行ってもよい。
鉄化合物、ケイ素化合物の中和方法は、所望するコア部の様態に応じて、（ｉ）〜（iv）のいずれかを選択する。様態（ハ）でコア部に鉄酸化物を用いる場合は、予め調製した鉄酸化物を用いてもよく、あるいは、鉄化合物溶液の一部を中和、酸化して生成させた鉄酸化物をコア部として、引き続き（ｉ）〜（iv）の方法を適用してもよい。
Next, the present invention is a method for producing a strontium adsorbent, characterized in that an iron compound and a silicon compound are neutralized and oxidized in a liquid medium. The silicon-containing iron oxide of the mode (I) is either (i) mixed with an iron compound and a silicon compound and then neutralized by adding a neutralizing agent, or (ii) the silicon compound is neutralized. And obtained by neutralizing and oxidizing an iron compound and a silicon compound. On the other hand, in the embodiment (b), (iii) after neutralizing and oxidizing the iron compound, neutralizing and oxidizing the silicon compound, or (iv) neutralizing the iron compound and neutralizing the silicon compound, The neutralizing agent can be added after the addition of the iron compound or the silicon compound, or can be added simultaneously with the iron compound and the silicon compound. Further, in the embodiment (c), the shell portion containing the iron oxide containing silicon on the surface of the core portion is obtained by neutralizing and oxidizing the iron compound and the silicon compound in the presence of the base material to be the core portion. Form. The oxidation may be performed at any timing before, during or after neutralization.
As a method for neutralizing the iron compound and the silicon compound, any one of (i) to (iv) is selected according to the desired state of the core part. When iron oxide is used for the core in the embodiment (c), a pre-prepared iron oxide may be used, or an iron oxide produced by neutralizing and oxidizing part of the iron compound solution may be used. You may apply the method of (i)-(iv) continuously as a core part.
中和ｐＨは、(i)、(ii)の方法であれば、３．０〜７．０の範囲が好ましく、５．０〜７．０の範囲が更に好ましく、(iii)、（iv）の方法であれば、鉄化合物、ケイ素化合物の好ましい中和ｐＨは、それぞれ７．０〜１０．０の範囲、４．０〜７．０の範囲である。酸化は、中和剤の添加前、添加中あるいは添加後の媒液中に、酸化剤を投入して行う。中和及び酸化時の温度は、２５〜８０℃の範囲が好ましい。鉄酸化物の酸化数は、酸化還元電位の測定により、酸化率を制御することで調整できる。アルミニウム、マンガン、マグネシウム等の、ケイ素以外の無機元素を含有させる場合は、例えば、鉄化合物の中和後で、ケイ素化合物の中和前に無機元素の化合物を添加する等して、（i）〜（iv）の方法に応じ、適当なタイミングで、当該無機元素化合物を中和し酸化する。 The neutralization pH is preferably in the range of 3.0 to 7.0, more preferably in the range of 5.0 to 7.0 in the methods (i) and (ii), and (iii) and (iv) If it is the method of this, the preferable neutralization pH of an iron compound and a silicon compound is the range of 7.0-10.0, and the range of 4.0-7.0, respectively. Oxidation is performed by adding an oxidizing agent into a liquid medium before, during or after the addition of the neutralizing agent. The temperature during neutralization and oxidation is preferably in the range of 25 to 80 ° C. The oxidation number of the iron oxide can be adjusted by controlling the oxidation rate by measuring the oxidation-reduction potential. In the case of containing an inorganic element other than silicon, such as aluminum, manganese, magnesium, etc., for example, by adding an inorganic element compound after neutralization of the iron compound and before neutralization of the silicon compound, (i) The inorganic element compound is neutralized and oxidized at an appropriate timing according to the methods (iv) to (iv).
（i）、(iii)、（iv）の方法で中和に用いる中和剤としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、炭酸ナトリウム等のアルカリ金属の炭酸塩、アンモニウムガス、アンモニア水、炭酸アンモニウム等のアンモニウム化合物等の公知の塩基性化合物、及び、塩酸、硫酸、硝酸、有機酸等の公知の酸性化合物を用いることができる。
また、酸化剤としては、空気、酸素、オゾン等の酸化性ガスや、過酸化水素等の酸化性化合物を用いることができ、特に、空気は経済的で取り扱い易く、工業的に有利である。
鉄化合物としては硫酸鉄、塩化鉄等が、ケイ素化合物としては、ケイ酸ナトリウム、ケイ酸カリウム等が挙げられる。硫酸法酸化チタンの製造工程で副生する硫酸には、鉄成分として硫酸鉄が含まれているので、この副生硫酸を、鉄化合物を含む媒液とし、ケイ素化合物を添加して用いると、低コストで有害物質吸着材を得ることができ、副生硫酸の処理・再利用にも寄与できる。媒液には、水等の水系媒液を用いるのが工業的に好ましく、前記のように鉄化合物を含む副生硫酸であってもよい。
Examples of the neutralizing agent used for neutralization by the methods (i), (iii), and (iv) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate. Known basic compounds such as salts, ammonium gas, aqueous ammonia, ammonium compounds such as ammonium carbonate, and known acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, and organic acids can be used.
As the oxidant, an oxidizing gas such as air, oxygen, ozone, or an oxidizing compound such as hydrogen peroxide can be used. In particular, air is economical and easy to handle and is industrially advantageous.
Examples of the iron compound include iron sulfate and iron chloride, and examples of the silicon compound include sodium silicate and potassium silicate. Since the sulfuric acid produced as a by-product in the manufacturing process of sulfuric acid method titanium oxide contains iron sulfate as an iron component, when this by-product sulfuric acid is used as a liquid medium containing an iron compound and a silicon compound is added, A hazardous substance adsorbent can be obtained at low cost, and can contribute to the treatment and reuse of by-product sulfuric acid. It is industrially preferable to use an aqueous medium such as water as the medium, and it may be a by-product sulfuric acid containing an iron compound as described above.
ケイ素含有鉄酸化物を生成させた後、固液分離してストロンチウム吸着材を得る。固液分離後は、必要に応じて、乾燥し、乾式粉砕する。固液分離には、例えば、フィルタープレス、ロールプレス等を用いることができる。乾燥には、例えば、バンド式ヒーター、バッチ式ヒーター等を用いることができる。乾式粉砕には、例えば、ハンマーミル、ピンミル等の衝撃粉砕機、解砕機等に摩砕粉砕機、ジェットミル等の気流粉砕機、スプレードライヤー等の噴霧乾燥機等を用いることができる。 After producing the silicon-containing iron oxide, solid-liquid separation is performed to obtain a strontium adsorbent. After solid-liquid separation, if necessary, dry and dry pulverize. For solid-liquid separation, for example, a filter press, a roll press, or the like can be used. For example, a band heater, a batch heater, or the like can be used for drying. For the dry pulverization, for example, an impact pulverizer such as a hammer mill or a pin mill, a pulverizer or the like, a grinding pulverizer, an airflow pulverizer such as a jet mill, or a spray dryer such as a spray dryer can be used.
また、本発明は環境処理方法であって、ストロンチウムを含む環境中に前記ストロンチウム吸着材を投入してストロンチウムを吸着させることを特徴とする。水や土壌の環境中に含まれるストロンチウムを吸着させるには、水処理、土壌処理等で用いられている公知の方法を用いることができる。例えば、水処理では、本発明のストロンチウム吸着材を、ストロンチウムを含む水に投入し、ストロンチウムを吸着不溶化させた後、濾別すればよい。あるいは本発明のストロンチウム吸着材を処理塔に充填したり、フィルターに担持させて用いたりすることもできる。このような充填塔やファイルターは、原子力プラントから発生する放射性ストロンチウム汚染水の処理にも有用である。地下水の処理では、例えば、土壌中に本発明のストロンチウム吸着材を含む層を形成し、この層を地下水が透過する際に、地下水に含まれるストロンチウムを吸着させることもできる。土壌処理では、ストロンチウムを含む土壌に直接投入する所謂原位置浄化法に有用であり、土壌に投入する方法には特に制限は無く、(a)土壌を掘り起こし本発明のストロンチウム吸着材と混合した後埋め戻す、(b)スラリー状にした本発明のストロンチウム吸着材を土壌に注入する等、土壌の性状、地形等に応じて適宜選択できる。また、水処理、土壌処理のいずれにおいても、当該鉄酸化物が磁着性を有していると、ストロンチウムを吸着させた後、分離する必要が生じれば、磁別することで容易に分離できる。 The present invention is also an environmental treatment method, wherein the strontium adsorbent is introduced into an environment containing strontium to adsorb strontium. In order to adsorb strontium contained in the environment of water or soil, a known method used in water treatment, soil treatment or the like can be used. For example, in the water treatment, the strontium adsorbent of the present invention may be added to water containing strontium to adsorb and insolubilize strontium, and then filtered. Alternatively, the strontium adsorbent of the present invention can be packed in a processing tower or used by being supported on a filter. Such packed towers and filers are also useful for treating radioactive strontium contaminated water generated from nuclear power plants. In the treatment of groundwater, for example, a layer containing the strontium adsorbent of the present invention is formed in soil, and strontium contained in the groundwater can be adsorbed when the groundwater permeates through this layer. In soil treatment, it is useful for the so-called in-situ purification method, which is directly put into soil containing strontium, and there is no particular limitation on the method of putting it into the soil. (A) After digging up the soil and mixing it with the strontium adsorbent of the present invention It can be appropriately selected according to the properties of the soil, topography, etc., such as backfilling, or (b) pouring the strontium adsorbent of the present invention into a slurry. In both water treatment and soil treatment, if the iron oxide has magnetic adhesion, it is easily separated by magnetic separation if it is necessary to separate it after adsorbing strontium. it can.
本発明の環境処理方法は、ストロンチウムの浄化能力に優れ、放射性ストロンチウムの除染に有用である。従来のストロンチウム吸着材では、浄化対象となる放射性ストロンチウム以外に、ナトリウム等の無機イオンが含まれる環境下では、浄化対象のストロンチウムの吸着能力が低下することが知られているが、本発明では、このような夾雑イオンの存在下でも、十分な吸着能力を有している。 The environmental treatment method of the present invention is excellent in the ability to purify strontium and is useful for decontamination of radioactive strontium. In the conventional strontium adsorbent, it is known that the adsorption capacity of strontium to be purified is reduced in an environment containing inorganic ions such as sodium other than radioactive strontium to be purified. Even in the presence of such contaminating ions, it has a sufficient adsorption capacity.
本発明の吸着材は、中性下では長期に渡って優れたストロンチウム吸着能を維持でき、一方、酸性下では、容易にストロンチウムを脱離させることができる。このため、放射性ストロンチウムの除染に用いた吸着材を、濾別、磁別等の手段で、環境中から分離、回収し、水中に分散させ、分散液のｐＨを酸性に調整すれば、吸着材から放射性ストロンチウムを除去できる。除去後の吸着材は再使用が可能となり、放射性ストロンチウムが溶出した水を濃縮すれば、放射性廃棄物の量を大幅に低減できる。ストロンチウムを脱離させるｐＨは、３．０以下が好ましい。 The adsorbent of the present invention can maintain an excellent ability to adsorb strontium for a long time under neutral conditions, while it can easily desorb strontium under acidic conditions. Therefore, if the adsorbent used for decontamination of radioactive strontium is separated and recovered from the environment by means of filtration, magnetic separation, etc., dispersed in water, and the pH of the dispersion is adjusted to acidic, Radioactive strontium can be removed from the material. The removed adsorbent can be reused, and the amount of radioactive waste can be greatly reduced by concentrating the water from which radioactive strontium is eluted. The pH at which strontium is eliminated is preferably 3.0 or less.
以下に本発明の実施例を示すが、本発明はこれらに制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
実施例１（様態（イ）：（ii）の方法）
硫酸第一鉄を総Ｆｅ量として７．６５ｇ／リットル含む、硫酸法酸化チタンの製造工程から発生した副生硫酸２リットルを７０℃に昇温した。撹拌して、４８００ミリリットル／分の流速で副生硫酸中に空気を吹き込みながら、１３．３重量％の濃度のケイ酸ナトリウム水溶液９２０ミリリットルを添加して中和し、酸化率６４．５％まで酸化した。酸化後の溶液のｐＨは、６．０１であった。得られた生成物を濾過、洗浄し、恒温乾燥機内で窒素注入しながら６０℃の温度で２４時間乾燥して、Ｆｅ／Ｓｉ比で１／３．９７のケイ素を含む、本発明のストロンチウム吸着材（試料Ａ）を得た。
Example 1 (Mode (I): Method (ii))
2 liters of by-product sulfuric acid generated from the production process of sulfuric acid method titanium oxide containing ferrous sulfate as a total Fe amount of 7.65 g / liter was heated to 70 ° C. While stirring, air is blown into the by-product sulfuric acid at a flow rate of 4800 ml / min, and neutralized by adding 920 ml of a sodium silicate aqueous solution having a concentration of 13.3% by weight to an oxidation rate of 64.5% Oxidized. The pH of the solution after oxidation was 6.01. The obtained product is filtered, washed, dried at a temperature of 60 ° C. for 24 hours while injecting nitrogen in a constant temperature dryer, and containing silicon having an Fe / Si ratio of 1 / 3.97. A material (sample A) was obtained.
実施例２（様態（イ）：（ii）の方法）
実施例１において、ケイ酸ナトリウム水溶液の添加量を１１００ミリリットルとし、ケイ酸ナトリウム水溶液の添加前に、Ａｌ２Ｏ３として８．１重量％濃度の硫酸アルミニウム水溶液１００ミリリットルを添加して、酸化率を６５．４％とした以外は実施例１と同様にして、Ｆｅ／Ｓｉ／Ａｌ比で１／４．７５／０．７６のケイ素及びアルミニウムを含む、本発明のストロンチウム吸着材（試料Ｂ）を得た。
Example 2 (Mode (I): Method (ii))
In Example 1, the amount of sodium silicate aqueous solution added was 1100 milliliters, and before the addition of sodium silicate aqueous solution, 100 milliliters of an aluminum sulfate aqueous solution having a concentration of 8.1% by weight as Al 2 O 3 was added. The strontium adsorbent of the present invention (sample B) containing silicon and aluminum having a Fe / Si / Al ratio of 1 / 4.75 / 0.76 in the same manner as in Example 1 except that the content was 65.4%. Got.
実施例３（様態（ロ）：（iii）の方法）
純水２リットルに、硫酸第一鉄・７水和物１００ｇを添加し、撹拌、溶解して水溶液とした。その後、撹拌を継続して、液温を７０℃に昇温し、４８００ミリリットル／分の流速で水溶液中に空気を吹き込みながら、５重量％の濃度の水酸化ナトリウム水溶液を添加しｐＨ５．７に中和した。次いで、１３．３重量％の濃度のケイ酸ナトリウム水溶液５７３ミリリットルを添加し、ｐＨを１０．０とした後、９．８重量％の濃度の硫酸でｐＨ６．０に中和して、酸化率７３．９％まで酸化した。得られた生成物を、実施例１と同様に、濾過、洗浄、乾燥して、Ｆｅ／Ｓｉ比で１／１．８８のケイ素を含む、本発明のストロンチウム吸着材（試料Ｃ）を得た。
Example 3 (Mode (b): Method of (iii))
100 g of ferrous sulfate heptahydrate was added to 2 liters of pure water, stirred and dissolved to obtain an aqueous solution. Thereafter, stirring was continued, the liquid temperature was raised to 70 ° C., and 5% by weight sodium hydroxide aqueous solution was added to pH 5.7 while blowing air into the aqueous solution at a flow rate of 4800 ml / min. Neutralized. Next, 573 ml of a sodium silicate aqueous solution having a concentration of 13.3% by weight was added to adjust the pH to 10.0, and then neutralized to pH 6.0 with sulfuric acid having a concentration of 9.8% by weight to obtain an oxidation rate. Oxidized to 73.9%. The obtained product was filtered, washed, and dried in the same manner as in Example 1 to obtain a strontium adsorbent (sample C) of the present invention containing silicon having a Fe / Si ratio of 1 / 1.88. .
実施例４（様態（ハ）：（ii）の方法）
硫酸第一鉄を総Ｆｅ量として８．６７ｇ／リットル含む、硫酸法酸化チタンの製造工程から発生した副生硫酸２リットルを７０℃に昇温した。撹拌して、先ず、市販のマグネタイト（Ｆｅ３Ｏ４）６．０ｇを添加し、次いで、水酸化アルミニウム０．５ｇを添加した後、４８００ミリリットル／分の流速で副生硫酸中に空気を吹き込みながら、１３．３重量％の濃度のケイ酸ナトリウム水溶液６２６ミリリットルを添加して中和し、酸化率７１．５％まで酸化した。酸化後の溶液のｐＨは、６．０であった。得られた生成物を、実施例１と同様にして、濾過、洗浄し、乾燥して、コア・シェル構造を有し、コア部がマグネタイトであり、シェル部がＦｅ／Ｓｉ／Ａｌ比で１／２．３９／０．０２のケイ素及びアルミニウムを含む、本発明のストロンチウム吸着材（試料Ｄ）を得た。
Example 4 (Mode (c): Method (ii))
2 liters of by-product sulfuric acid generated from the production process of sulfuric acid method titanium oxide containing 8.67 g / liter of ferrous sulfate as a total Fe amount was heated to 70 ° C. First, 6.0 g of commercially available magnetite (Fe 3 O 4 ) was added, and 0.5 g of aluminum hydroxide was added, and then air was blown into the by-product sulfuric acid at a flow rate of 4800 ml / min. However, the solution was neutralized by adding 626 ml of an aqueous sodium silicate solution having a concentration of 13.3% by weight, and oxidized to an oxidation rate of 71.5%. The pH of the solution after oxidation was 6.0. The obtained product was filtered, washed and dried in the same manner as in Example 1 to have a core-shell structure, the core part was magnetite, and the shell part was 1 in Fe / Si / Al ratio. A strontium adsorbent of the present invention (sample D) containing /2.39/0.02 silicon and aluminum was obtained.
比較例１
市販のγ−Ｆｅ２Ｏ３を、比較対象のストロンチウム吸着材（試料Ｅ）とした。
Comparative Example 1
Commercially available γ-Fe 2 O 3 was used as a strontium adsorbent for comparison (sample E).
比較例２
市販のレピドクロサイト鉄酸化物（ＦｅＯＯＨ）を、比較対象のストロンチウム吸着材（試料Ｆ）とした。
Comparative Example 2
Commercially available lipidocrosite iron oxide (FeOOH) was used as a strontium adsorbent (sample F) for comparison.
比較例３
Ｆｅとして６．７ｇ／リットルの濃度の硫酸第一鉄・７水和物水溶液７リットルを４５℃に昇温した。撹拌して、４８００ミリリットル／分の流速で溶液中に空気を吹き込みながら、ｐＨが８．５となるように５重量％の濃度の水酸化ナトリウム水溶液を添加して中和し、酸化率１００％まで酸化した後、得られた生成物を、実施例１と同様にして、濾過、洗浄し、乾燥して、比較対象のストロンチウム吸着材（試料Ｇ）とした。
Comparative Example 3
7 liters of ferrous sulfate heptahydrate aqueous solution having a concentration of 6.7 g / liter as Fe was heated to 45 ° C. While stirring, air was blown into the solution at a flow rate of 4800 ml / min, and neutralized by adding a 5% by weight sodium hydroxide aqueous solution so that the pH was 8.5, and the oxidation rate was 100%. Then, the obtained product was filtered, washed and dried in the same manner as in Example 1 to obtain a comparative strontium adsorbent (sample G).
実施例１〜４で得られた試料Ａ〜Ｄの内容を、表１に取り纏めた。 The contents of Samples A to D obtained in Examples 1 to 4 are summarized in Table 1.
評価１
実施例１〜４、比較例１〜３の試料Ａ〜Ｇ各２ｇを、塩化ストロンチウムを溶解してストロンチウム濃度を１０ｍｇ／リットルとした試験液２００ミリリットルに加えた。２４時間振盪後、遠心分離機を用い、回転数３０００ｒｐｍで２０分間かけて遠心分離した。遠心分離した上澄み液（１）を０．４５μｍのフィルターでろ過してから、ストロンチウムの濃度を、発光分析装置（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｈｉｅｎｔｉｆｉｃ社製：ｉＣＡＰ Ｑ ＩＣＰ−ＭＳ）により測定した。
Evaluation 1
2 g of each of samples A to G of Examples 1 to 4 and Comparative Examples 1 to 3 was added to 200 ml of a test solution in which strontium chloride was dissolved to adjust the strontium concentration to 10 mg / liter. After shaking for 24 hours, the mixture was centrifuged at 3000 rpm for 20 minutes using a centrifuge. The centrifuged supernatant (1) was filtered through a 0.45 μm filter, and the strontium concentration was measured with a luminescence analyzer (manufactured by Thermo Fisher Scientific: iCAP Q ICP-MS).
評価２
実施例１〜４（試料Ａ〜Ｄ）、比較例２（試料Ｆ）について、評価１を行った後の試料０．５ｇに純水５０ミリリットルを添加し、評価１と同様にして、再度遠心分離し、上澄み液（２）中のストロンチウムの濃度を測定した。
Evaluation 2
For Examples 1 to 4 (Samples A to D) and Comparative Example 2 (Sample F), 50 ml of pure water was added to 0.5 g of the sample after the evaluation 1, and the centrifugation was performed again in the same manner as the evaluation 1. After separation, the concentration of strontium in the supernatant (2) was measured.
結果を表２に示す。
本発明のストロンチウム吸着材は、優れたストロンチウムの吸着能力を有しており、また、一旦、吸着したストロンチウムは脱離し難く、ストロンチウムが高度に不溶化されていることが判る。
The results are shown in Table 2.
The strontium adsorbent of the present invention has an excellent ability to adsorb strontium, and once adsorbed strontium is difficult to desorb, it can be seen that strontium is highly insolubilized.
評価３
実施例１〜４の試料Ａ〜Ｄ各２ｇを、塩化ストロンチウムを溶解してストロンチウム濃度を下記表３記載の濃度とし、更にナトリウム濃度が１重量％となるように塩化ナトリウムを添加した試験液２００ミリリットルに加えた。評価１と同様にして、ストロンチウムの除去率を算出した。
Evaluation 3
Test solutions 200 in which 2 g of each of Samples A to D of Examples 1 to 4 were dissolved in strontium chloride to adjust the strontium concentration to the concentrations shown in Table 3 below, and sodium chloride was added so that the sodium concentration was 1% by weight. Added to milliliters. In the same manner as in Evaluation 1, the removal rate of strontium was calculated.
結果を表３に示す。
本発明のストロンチウム吸着材は、夾雑イオンの存在下でも、十分なストロンチウムの吸着能力を有していることが判る。
The results are shown in Table 3.
It can be seen that the strontium adsorbent of the present invention has sufficient strontium adsorption ability even in the presence of impurity ions.
評価４
実施例１〜４の試料Ａ〜Ｄについて、各１０ｇを、塩化ストロンチウムを溶解してストロンチウム濃度を１ｍｇ／リットルとした試験液１リットルに加えた。評価１と同様にして、ストロンチウム吸着試験を行った。この吸着試験後の試料に純水を加え試験溶液とし、ｐＨをシュウ酸とシュウ酸アンモニウムを用いて３．０に調整した。その後、評価２と同様にして、ストロンチウムの溶出率を算出した。
Evaluation 4
For Samples A to D of Examples 1 to 4, 10 g of each was added to 1 liter of a test solution in which strontium chloride was dissolved to give a strontium concentration of 1 mg / liter. A strontium adsorption test was conducted in the same manner as in Evaluation 1. Pure water was added to the sample after this adsorption test to obtain a test solution, and the pH was adjusted to 3.0 using oxalic acid and ammonium oxalate. Thereafter, the elution rate of strontium was calculated in the same manner as in Evaluation 2.
結果を表４に示す。
本発明のストロンチウム吸着材は、水中でｐＨを酸性に調整することにより、ストロンチウムが容易に脱離することが判る。
The results are shown in Table 4.
It can be seen that the strontium adsorbent of the present invention is easily desorbed by adjusting the pH to be acidic in water.
本発明の吸着材は、放射性ストロンチウムで汚染された水、土壌等の除染に有用である。
The adsorbent of the present invention is useful for decontamination of water, soil and the like contaminated with radioactive strontium.
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