JP4414214B2 - Treatment method of waste ion exchange resin - Google Patents
Treatment method of waste ion exchange resin Download PDFInfo
- Publication number
- JP4414214B2 JP4414214B2 JP2003426315A JP2003426315A JP4414214B2 JP 4414214 B2 JP4414214 B2 JP 4414214B2 JP 2003426315 A JP2003426315 A JP 2003426315A JP 2003426315 A JP2003426315 A JP 2003426315A JP 4414214 B2 JP4414214 B2 JP 4414214B2
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- JP
- Japan
- Prior art keywords
- exchange resin
- ion exchange
- solution
- waste
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims description 74
- 239000003456 ion exchange resin Substances 0.000 title claims description 67
- 229920003303 ion-exchange polymer Polymers 0.000 title claims description 67
- 239000002699 waste material Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000009279 wet oxidation reaction Methods 0.000 claims description 49
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 27
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 27
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003729 cation exchange resin Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 229910021487 silica fume Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 2
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims 2
- 150000002978 peroxides Chemical class 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 42
- 239000007788 liquid Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- -1 ammonium ions Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 239000002901 radioactive waste Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010849 combustible waste Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004503 fine granule Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Description
本発明は廃イオン交換樹脂の処理方法に関し、特に湿式酸化法で減容し、水酸化バリウムを利用して湿式酸化反応液のｐＨを調節するイオン交換樹脂の処理方法に関し、主に原子力発電所における各種浄化処理或いはその他関連分野の浄化処理に応用されるものに関する。 TECHNICAL FIELD The present invention relates to a method for treating a waste ion exchange resin, and more particularly to a method for treating an ion exchange resin in which the volume is reduced by a wet oxidation method and the pH of a wet oxidation reaction solution is adjusted using barium hydroxide. It is related with what is applied to the various purification processing in, or purification processing of other related fields.
現在の原子力発電所の大多数は軽水式反応炉（ｌｉｇｈｔ ｗａｔｅｒ ｒｅａｃｔｏｒ）ユニットであり、軽水を反応炉の冷却材（ｃｏｏｌａｎｔ）と中性子減速材（ｎｅｕｔｒｏｎ ｍｏｄｅｒａｔｏｒ）としている。原子炉水中に溶解したイオンが存在すれば、腐食性が増加するだけでなく、放射化生成物（ａｃｔｉｖａｔｉｏｎ ｐｒｏｄｕｃｔｓ）が発生してユニットの放射線量が増量する上、中性子捕獲反応（ｎｅｗｔｒｏｎ ｃａｐｔｕｒｅ ｒｅａｃｔｉｏｎｓ）が制御失効して中性子効率（ｎｅｕｔｒｏｎ ｅｃｏｎｏｍｙ）が低下する。これらの潜在的問題を解決するため、イオン交換樹脂は原発において広範な用途がある。原子炉水の浄化処理を行って脱鉱物質の補充原子炉水を提供する、原子炉水中の汚染物、例えば核燃料コンポーネントのピンホールから流出した中性子放射化生成物と分裂生成物などを除去する、冷却材の酸素含有量の低下、及び原子炉水中の腐食制御剤と化学添加剤の含有量のコントロールなどである。また、イオン交換樹脂は原子力發電所のプロセス廃水の処理にも使われている。 The majority of current nuclear power plants are light water reactor units, which use light water as a reactor coolant and a neutron moderator. The presence of dissolved ions in the reactor water not only increases the corrosivity, but also generates activation products and increases the radiation dose of the unit, as well as neutron capture reactions. Expires and the neutron efficiency decreases. In order to solve these potential problems, ion exchange resins have a wide range of uses in nuclear power plants. Purifies reactor water to provide demineralized supplemental reactor water, removes contaminants in reactor water, such as neutron activation products and fission products flowing out of nuclear fuel component pinholes Reducing the oxygen content of the coolant, and controlling the content of corrosion control agents and chemical additives in the reactor water. Ion exchange resins are also used to treat process wastewater at nuclear power plants.
原発ではイオン交換樹脂はビーズ状樹脂のほか、有効表面積を増加させるために粉末状イオン交換樹脂も使用している。粉末状イオン交換樹脂の比表面積はビーズイオン交換樹脂の百倍であり、非常に微小な粉末である。通常フィルターのコーティングに用いられ、イオン交換の機能のほか、水中に浮遊する固体微粒子の除去にも利用される。
ビーズ状イオン交換樹脂はイオン交換能力が減退したり核種に汚染されて放射性が高くなると再生が必要になる。数回再生して再利用できなくなると交換されて放射性廃棄物となる。粉末状イオン交換樹脂は一回の使用で多量の雑固体を吸着するので、普通再生せずに一回の使用で廃棄物として処理する。アメリカ電力研究所の統計では１９８２−１９８５年の湿性廃棄物に占める廃樹脂の産出量比率は、沸騰水型反応炉（ＢＷＲ、Ｂｏｉｌｉｎｇ Ｗａｔｅｒ Ｒｅａｃｔｏｒ）原発で粉末状廃樹脂が５０％、ビーズ状樹脂が２５％を占め、加圧水型反応炉（ＰＷＲ、Ｐｒｅｓｓｕｒｉｚｅｄ Ｗａｔｅｒ Ｒｅａｃｔｏｒ）原発で粉末状廃樹脂が７％、ビーズ状樹脂が４４％を占めた。台湾ではＢＷＲ原発で粉末状廃樹脂が３０％、ビーズ状樹脂が１１％、ＰＷＲ原発で粉末状廃樹脂が１％、ビーズ状樹脂が２３％を占めている。
At the nuclear power plant, in addition to the bead-shaped resin, a powdered ion-exchange resin is also used to increase the effective surface area. The specific surface area of the powdered ion exchange resin is one hundred times that of the bead ion exchange resin, and is a very fine powder. It is usually used for filter coating and is used for ion exchange function as well as removal of solid particles suspended in water.
The bead-type ion exchange resin needs to be regenerated if its ion exchange capacity is reduced or it is contaminated by nuclides and becomes highly radioactive. If it cannot be reused after being recycled several times, it is replaced and becomes radioactive waste. Since powder ion exchange resin adsorbs a large amount of miscellaneous solids in a single use, it is treated as a waste in a single use without being normally regenerated. According to the statistics of the American Electric Power Research Institute, the ratio of waste resin production to wet waste in 1982-1985 was 50% for powdered waste resin from the boiling water reactor (BWR), and bead-like resin. Accounted for 25%, and in the pressurized water reactor (PWR, Pressurized Water Reactor), powdered waste resin accounted for 7% and bead-shaped resin accounted for 44%. In Taiwan, BWRs account for 30% of powdered waste resin, 11% of beaded resin, PWRs account for 1% of powdered waste resin, and 23% of beaded resin.
廃イオン交換樹脂の処理は、早期には直接固化で、固化剤の材料はセメント、高分子重合体あるいはアスファルトなどであった。これらの固化法はそれぞれ優劣があるが、一般には高分子重合体とアスファルトでの固化は固化体積が小さい。しかし、高分子重合体は価格が高く、操業コストも高い。アスファルトは強度が低く可燃性である。１９９７年３月日本でアスファルト固化操作で火災が発生し、重大な原発事故となった。セメント固化は操作が簡単で費用も低廉だが、廃イオン交換樹脂にイオン交換能力があるため、セメント固化体のカルシウムイオンなどと交換反応が起こり品質に影響する。また水分を吸収したり放出したりするため膨張や収縮が起こる。このような作用はビーズ状イオン交換樹脂で特に強く、ひどい場合固化体が膨張したりひび割れたりするため、セメント固化体の廃イオン交換樹脂のローディングが大きく制限され、固化後膨大な体積の固化体となってしまう。最終処分場が得にくく、処分費用も高騰している今日では直接固化は経済効率が悪い。 The treatment of the waste ion exchange resin was directly solidified at an early stage, and the material of the solidifying agent was cement, a polymer or asphalt. Each of these solidification methods is superior or inferior, but generally solidification with a high molecular weight polymer and asphalt has a small solidification volume. However, the polymer is expensive and the operation cost is high. Asphalt is low in strength and flammable. In March 1997, a fire broke out in Japan during the asphalt solidification operation, resulting in a serious nuclear accident. Cement solidification is easy to operate and inexpensive, but the waste ion exchange resin has an ion exchange capability, which causes an exchange reaction with calcium ions etc. in the cement solidified product, affecting the quality. In addition, since it absorbs and releases moisture, it expands and contracts. Such an action is particularly strong with bead-shaped ion exchange resin, and in severe cases, the solidified body expands or cracks, so the loading of the waste ion exchange resin in the cement solidified body is greatly limited, and the solidified body with a huge volume after solidification End up. It is difficult to obtain a final disposal site and disposal costs are soaring today.
現在のビーズ状廃イオン交換樹脂の処理においては、減容と安定化の二つが主要な目的であり、処理方法は乾式と湿式の二種に分けられる。乾式には焼却法、直接ガラス固化法、熱分解法などが含まれる。焼却法の開発が最も早く、一部の国では実施している。焼却の際には普通、廃ビーズ状イオン交換樹脂とその他可燃性廃棄物と混合して焼却する方法を採って硫黄酸化物、窒素酸化物やその他有害ガスの排出を制御する。放射性核種の排出制御も焼却法が解決しなければならない重要な問題である。揮発性のＣ−１４、トリチウムＣｓ−１３７等の核種の排出を効果的に回避できるか、そうでなければ放射性の高い廃棄物には予め核種を除去して放射性を低下させてから焼却しなければならない。 In the current processing of bead-like waste ion exchange resins, two main purposes are volume reduction and stabilization, and the processing methods are divided into two types, dry and wet. Dry methods include incineration, direct vitrification, and pyrolysis. Incineration laws are the fastest developing and in some countries. In incineration, waste bead-shaped ion exchange resin and other combustible waste are usually mixed and incinerated to control the emission of sulfur oxides, nitrogen oxides and other harmful gases. Radionuclide emission control is another important issue that the incineration method must solve. Emissions of nuclides such as volatile C-14 and tritium Cs-137 can be effectively avoided, or otherwise highly radioactive waste must be incinerated after removing the nuclides in advance and reducing the radioactivity. I must.
直接ガラス固化は、イオン交換樹脂のガラス溶融体が高温時に強い腐食作用をもつため、材料の腐食が最重要問題である。現在各種ガラス固化溶融炉技術が開発中である。中ではフランスＳＧＮ社開発のコールド・ウォール（ｃｏｌｄ ｗａｌｌ）溶融炉は腐食の問題が少なく、最も理想的な直接ガラス固化技術と謳っているが、商用システムは確立されていない。アメリカＭｏｌｔｅｎ Ｍｅｔａｌ Ｔｅｃｈｎｏｌｏｇｙ（ＭＭＴ）社が所謂Ｑ−ＣＥＰプロセス（Ｑｕａｎｔｕｍ−Ｃａｔａｌｙｔｉｃ Ｅｘｔｒａｃｔｉｏｎ Ｐｒｏｃｅｓｓ）を開発しており、密閉炉内で強還元性のある溶融鉄中でイオン交換樹脂中の気化できる成分を分解して気体にし、気化できない成分は溶融残渣を形成して効果的に減容と安定化を得ている。最終的な固化生成物は硫黄、珪素、ナトリウムなどを含む高活性鉄塊で、特別な容器に封入しなければならない。Ｑ−ＣＥＰシステムの建造コストは非常に高く、小容量の処理場の建設は大変不経済である。また、この方法は相当な量の硫化水素といった気体副産物を産出するので、その解決も難題である。 In direct vitrification, since the glass melt of the ion exchange resin has a strong corrosive action at high temperatures, the corrosion of the material is the most important problem. Various vitrification melting furnace technologies are currently under development. Among them, the cold wall melting furnace developed by SGN, France has few problems of corrosion and is said to be the most ideal direct vitrification technology, but no commercial system has been established. Molten Metal Technology (MMT) of the United States has developed a so-called Q-CEP process (Quantum-Catalytic Extraction Process), which decomposes components that can be vaporized in ion-exchange resin in molten iron that is highly reducing in a closed furnace As a result, the components that cannot be vaporized can form a molten residue and effectively reduce volume and stabilize. The final solidified product is a highly active iron mass containing sulfur, silicon, sodium, etc., which must be enclosed in a special container. The construction cost of the Q-CEP system is very high, and the construction of a small capacity treatment plant is very uneconomical. This method also produces a significant amount of gaseous by-products such as hydrogen sulfide, and its solution is also a challenge.
アメリカＴｈｅｒｍｏ Ｃｈｅｍ Ｉｎｃ．は高温水蒸気改質法（ｓｔｅａｍ ｒｅｆｏｒｍｉｎｇ）を開発している。イオン交換樹脂を高温で熱分解（ｐｙｒｏｌｙｓｉｓ）させ、同時に改質により可燃ガスを生成して燃料とする。この方法も重大な材料腐食問題を抱えており、前途の如何には時間の証明が必要である。
超臨界水酸化法（Ｓｕｐｅｒ Ｃｒｉｔｉｃａｌ Ｗａｔｅｒ Ｏｘｉｄａｔｉｏｎ、ＳＣＷＯ）の研究はまだ初歩段階であり、使用する高温・高圧臨界水は、イオン交換樹脂の分解生成物（硫酸など）を含有すると同様に強い腐食性をもつので、材料腐食問題が非常に重大で、実用には程遠い。
United States Thermo Chem Inc. Has developed a high temperature steam reforming process. The ion exchange resin is pyrolyzed at a high temperature, and at the same time, a combustible gas is generated by reforming to obtain a fuel. This method also has a serious material corrosion problem, and time proof is required.
Super critical water oxidation (SCWO) research is still in its infancy, and high-temperature and high-pressure critical water used is highly corrosive if it contains decomposition products (such as sulfuric acid) of ion-exchange resins. Therefore, the material corrosion problem is very serious and far from practical use.
イギリスＡＥＡ社では既に湿式酸化法を成功させている。硫酸第一鉄を触媒に、過酸化水素を酸化剤に、消石灰をｐＨ調節剤として、温度約１００℃、ｐＨ３−４のもと、ビーズ状廃イオン交換樹脂の酸化分解を行って有機成分を二酸化炭素と水に分解する。報道によると、この方法はイオン交換樹脂４０リットルの処理に、５０ｗｔ％過酸化水素１６０キログラム、濃硫酸１キログラム、消石灰６キログラム、及び０．５キログラム以下の消泡剤を消費する。 UK AEA has already succeeded in wet oxidation. Using ferrous sulfate as a catalyst, hydrogen peroxide as an oxidant, slaked lime as a pH regulator, oxidative decomposition of the bead-like waste ion exchange resin at a temperature of about 100 ° C. and pH 3-4, Decomposes into carbon dioxide and water. According to reports, this method consumes 160 kg of 50 wt% hydrogen peroxide, 1 kg of concentrated sulfuric acid, 6 kg of slaked lime, and less than 0.5 kg of antifoaming agent in the treatment of 40 liters of ion exchange resin.
廃イオン交換樹脂は陽イオン交換型と陰イオン交換型の二つの型があり、異なる化学成分をもっている。強酸型の陽イオン交換樹脂と強アルカリ型の陰イオン交換樹脂を過酸化水素で湿式酸化を行う総合反応（ｏｖｅｒ−ａｌｌ ｒｅａｃｔｉｏｎ）を以下に示す。
陽イオン交換樹脂湿式酸化反応
Cation exchange resin wet oxidation reaction
湿式酸化反応液のｐＨの制御には、酸類或いはアルカリ類を添加して調節する必要がある。一般に消石灰（水酸化カルシウム）或いは水酸化ナトリウムを添加することが多い。水酸化カルシウムの添加で硫酸は硫酸カルシウムを形成し、主に硫酸カルシウムを含む湿式酸化廃液を生成する。この種の廃液を固化すると、硫酸カルシウムがセメント中のアルミン酸三石灰（３ＣａＯ・Ａｌ2Ｏ3）に作用してゆっくりと低密度のエトリンガイト（ｅｔｔｒｉｎｇｉｔｅ）を生成し、固化体を次第に膨張させひいては亀裂を発生させ、重大な品質問題となる。この問題を避けるには固化体の廃棄物ローディングを大幅に低下させねばならず、廃棄物固化体の体積が大幅に増大する。このほか、硫酸カルシウムは廃液中で結晶しやすく、配管に付着して閉塞させるので搬送が難かしく、操作上の困難となる。
湿式酸化槽で蒸発する水蒸気を冷却して得られる凝結水には核種が含まれる可能性があり、少量の有機物の含有は避けられない。処理を施さなければ総有機炭素（ｔｏｔａｌ ｏｒｇａｎｉｃ ｃａｒｂｏｎ、ＴＯＣ）濃度が高すぎ、凝縮水を排出できない、再利用困難といった問題となる。
In order to control the pH of the wet oxidation reaction solution, it is necessary to adjust by adding acids or alkalis. In general, slaked lime (calcium hydroxide) or sodium hydroxide is often added. With the addition of calcium hydroxide, the sulfuric acid forms calcium sulfate, producing a wet oxidation waste liquid containing mainly calcium sulfate. When this kind of waste liquid is solidified, calcium sulfate acts on trilime aluminate (3CaO.Al 2 O 3 ) in the cement to slowly produce low-density ettringite, and the solidified body is gradually expanded. Cracks become a serious quality problem. In order to avoid this problem, the waste loading of the solidified body must be greatly reduced, and the volume of the solidified solid body is greatly increased. In addition, calcium sulfate tends to crystallize in the waste liquid and adheres to the piping and is blocked, making it difficult to transport and difficult to operate.
The condensed water obtained by cooling the water vapor evaporated in the wet oxidation tank may contain nuclides, and the inclusion of a small amount of organic matter is inevitable. If the treatment is not performed, the total organic carbon (TOC) concentration is too high, and the condensed water cannot be discharged.
現行の廃イオン交換樹脂の湿式酸化法の、（１）処理時に反応液は高い腐食性があり、材料腐食問題が重大である、（２）産出する廃液は主に硫酸と硫酸塩から成り、固化が容易でなく、廃液固化で生成する固化体の体積が大きく、イオン交換樹脂で得られる減容効果が帳消しになる、（３）湿式酸化操作の制御が難しく、反応で生成する気泡は激しい沸騰現象を起こしやすい、といった欠点を解決する。 In the current wet ion exchange resin wet oxidation method, (1) the reaction liquid is highly corrosive during processing and the material corrosion problem is serious. (2) The waste liquid produced mainly consists of sulfuric acid and sulfate. Solidification is not easy, the volume of the solidified product produced by solidification of the waste liquid is large, and the volume reduction effect obtained with the ion exchange resin is canceled out. (3) It is difficult to control the wet oxidation operation, and bubbles generated by the reaction are intense To solve the shortcomings of boiling easily.
本発明は、廃イオン交換樹脂の処理方法としてイオン交換樹脂を湿式酸化法で減容する。本発明はまた、廃イオン交換樹脂の処理方法を提供し、イオン交換樹脂を湿式酸化法で減容した後、更に湿式酸化残渣と廃液スラリーを高効率で固化する。 In the present invention, the volume of the ion exchange resin is reduced by a wet oxidation method as a treatment method of the waste ion exchange resin. The present invention also provides a method for treating a waste ion exchange resin. After the volume of the ion exchange resin is reduced by a wet oxidation method, the wet oxidation residue and the waste liquid slurry are further solidified with high efficiency.
本発明は硫酸鉄を触媒とし、過酸化水素を酸化剤としてイオン交換樹脂の分解と酸化を行う。反応溶液のｐＨを上昇するには水酸化バリウムを使用し、反応溶液のｐＨを降下するには硫酸を使用する。図１のフローに示すように、実施プロセスは、
（１）イオン交換樹脂を硫酸第一鉄溶液中に入れ、溶液を攪拌しつつ９０℃以上、沸点以下の温度に加熱する。
（２）過酸化水素を（１）の溶液中に添加し、硫酸或いは水酸化バリウムで溶液のｐＨを湿式酸化法で適当な範囲に調節する。
（３）過酸化水素添加期間中に温度が沸点に達した時、溶液を自然に沸騰させ、生成する水蒸気と二酸化炭素を冷却コンデンサを経て凝縮水を収集し、総有機炭素（ＴＯＣ）と核種濃度を低下させる処理を行った後、回収して再利用するか或いは排出する。二酸化炭素は、濾過後放出する。
（４）十分な量の過酸化水素を添加して湿式酸化反応を完了した後、溶液中に水酸化バリウムを添加して溶液のｐＨを上昇させるとともに、溶液中の硫酸イオンが硫酸バリウムを形成するようにし、同時にアンモニウムイオンが水酸化アンモニウム或いはアンモニアの形態で溶液から逸脱するようにする。
（５）溶液から逸脱した水酸化アンモニウム或いはアンモニアをアンモニア分解装置を経て、水素ガスと窒素ガスを生成し、生成した水素ガスを空気と接触反応させて水とする。
（６）（４）のスラリーに固化剤を添加して均一に混合し、静置して硬化させる。
In the present invention, ion exchange resin is decomposed and oxidized using iron sulfate as a catalyst and hydrogen peroxide as an oxidizing agent. Barium hydroxide is used to raise the pH of the reaction solution, and sulfuric acid is used to lower the pH of the reaction solution. As shown in the flow of FIG.
(1) An ion exchange resin is placed in a ferrous sulfate solution, and the solution is heated to a temperature not lower than 90 ° C. and not higher than the boiling point while stirring the solution.
(2) Hydrogen peroxide is added to the solution of (1), and the pH of the solution is adjusted to an appropriate range by wet oxidation with sulfuric acid or barium hydroxide.
(3) When the temperature reaches the boiling point during the hydrogen peroxide addition period, the solution is boiled naturally, and the water vapor and carbon dioxide produced are collected through a cooling condenser, and the condensed water is collected. Total organic carbon (TOC) and nuclide After the process of reducing the concentration, it is collected and reused or discharged. Carbon dioxide is released after filtration.
(4) After a sufficient amount of hydrogen peroxide is added to complete the wet oxidation reaction, barium hydroxide is added to the solution to raise the pH of the solution, and sulfate ions in the solution form barium sulfate. At the same time, the ammonium ions deviate from the solution in the form of ammonium hydroxide or ammonia.
(5) Ammonium hydroxide or ammonia deviating from the solution is passed through an ammonia decomposing apparatus to produce hydrogen gas and nitrogen gas, and the produced hydrogen gas is brought into contact with air to form water.
(6) A solidifying agent is added to the slurry of (4), mixed uniformly, and allowed to stand to cure.
本発明の方法で、湿式酸化反応液の安定化処理を簡易に行えるように、ｐＨを調節する酸類には特に硫酸を選び、ｐＨを調節するアルカリ類には特に水酸化バリウムを選ぶ。水酸化バリウムを中和剤として採用することで以下の長所が得られる。（１）水酸化バリウムは硫酸と硫酸アンモニウムを転化して硫酸バリウムにすることができ、硫酸バリウムは不溶性且つ比重が非常に高い（約４．５）固体で、安定性が高く、埋封後には固化体構造内で骨材の効果を発揮し、生成する固化体の容積が小さい上、固化体の機械的強度も増進する。（２）エトリンガイトを生成しないので、固化体の膨張や亀裂の問題が発生せず、安定性の良好な固化体が得られる。（３）形成する硫酸バリウムは堅固な硬い微細顆粒で、粘着して集結することなく、溶液中に分散しやすいため流動搬送が容易、且つ混合しやすく操作が非常に容易である。（４）水酸化バリウムは硫酸イオンに対する安定化効果に優れ、ｐＨの調節効果も良く、廃液の腐食性低下の効果も良好である。 In order to facilitate the stabilization treatment of the wet oxidation reaction solution by the method of the present invention, sulfuric acid is particularly selected as the acid for adjusting the pH, and barium hydroxide is particularly selected as the alkali for adjusting the pH. By using barium hydroxide as a neutralizing agent, the following advantages can be obtained. (1) Barium hydroxide can convert sulfuric acid and ammonium sulfate into barium sulfate. Barium sulfate is an insoluble and very high specific gravity (about 4.5) solid, highly stable, and after embedding The aggregate effect is exhibited in the solidified body structure, and the volume of the solidified body to be generated is small, and the mechanical strength of the solidified body is also increased. (2) Since ettringite is not generated, problems of expansion and cracking of the solidified body do not occur, and a solidified body having good stability can be obtained. (3) The barium sulfate to be formed is a hard, hard fine granule that does not stick together and is easy to disperse in the solution, so that it is easy to flow and mix, and is very easy to operate. (4) Barium hydroxide has an excellent stabilizing effect against sulfate ions, a good pH adjusting effect, and a good effect of reducing the corrosiveness of the waste liquid.
湿式酸化の効率と反応液のｐＨ制御は密接な関係がある。本発明の実験結果が示すように、水酸化バリウムによる湿式酸化反応液のｐＨ調節効果は、一般に使用する水酸化カルシウムや水酸化ナトリウムに比べはるかに良好で、ｐＨの安定制御に加えて使用量も少なく、最終廃棄物産出量減量にも役立つ。実験結果によると、陽イオン交換樹脂の湿式酸化反応液のｐＨは０．５から４に制御するとよく、１から３であれば尚良い。陰イオン交換樹脂には、ｐＨは１．５から４に制御するとよく、２から３．５に制御すれば尚良い。陰イオン交換樹脂と陽イオン交換樹脂を含む湿式酸化反応液は、ｐＨを１から４に制御するとよく、１．５から３に制御すると尚良い。反応液のｐＨ制御が適当な範囲とすると過酸化水素の消費量を減少できる。実験結果が示すように、等体積比の陰・陽混合イオン交換樹脂では、ｐＨを２前後に制御すると混合イオン交換樹脂１リットル当りに消費する５０％過酸化水素は約３．５〜５リットルの間であり、過酸化水素の添加速度が遅いほど過酸化水素の消費が少ない。 The efficiency of wet oxidation and the pH control of the reaction solution are closely related. As shown by the experimental results of the present invention, the pH adjustment effect of the wet oxidation reaction solution by barium hydroxide is much better than the calcium hydroxide and sodium hydroxide that are generally used, and the amount used in addition to the stable control of pH. This is also useful for reducing the amount of final waste produced. According to the experimental results, the pH of the wet oxidation reaction solution of the cation exchange resin is preferably controlled from 0.5 to 4, and more preferably from 1 to 3. For anion exchange resins, the pH may be controlled from 1.5 to 4, and more preferably from 2 to 3.5. The wet oxidation reaction solution containing an anion exchange resin and a cation exchange resin may be controlled to have a pH of 1 to 4 and more preferably 1.5 to 3. When the pH control of the reaction solution is within an appropriate range, the consumption of hydrogen peroxide can be reduced. As the experimental results show, with an equal volume ratio of yin and yang mixed ion exchange resin, when the pH is controlled around 2, 50% hydrogen peroxide consumed per liter of mixed ion exchange resin is about 3.5 to 5 liters. The slower the addition rate of hydrogen peroxide, the less hydrogen peroxide is consumed.
湿式反応終了時には、前述のように反応液中の陽イオン交換樹脂の投入量の多少に応じて等量の硫酸アンモニウムを含有する。この硫酸アンモニウムにはやはり水酸化バリウムを添加して転化を行う。反応を下に示す。
本発明は、製造工程で発生するアンモニアと総有機炭素（ｔｏｔａｌ ｏｒｇａｎｉｃ ｃａｒｂｏｎ、ＴＯＣ）を含む冷却凝結水でも十分且つ清潔に処理し、二次汚染防止を確保する。アンモニアは発生後即アンモニア分解器へ導入され、高温と触媒（ｃａｔａｌｙｓｔ）接触のもと、窒素と水素に分解される。水素は分解装置の出口で空気と接触して酸化されて水となり、窒素と一緒に排出される。反応を以下に示す。
湿式酸化槽で蒸発する水蒸気を冷却して得られる凝結水は核種を含んでいる可能性があり、また少量の有機物含有は避けられない。処理を行わなければ総有機炭素（ｔｏｔａｌ ｏｒｇａｎｉｃ ｃａｒｂｏｎ、ＴＯＣ）濃度が高すぎ、凝結水の排出或いは再利用が困難になる。この問題を解決するために本発明は凝結水のＴＯＣ低下処理後に、イオン交換樹脂床を経て含まれるかもしれない核種を取り除く。実験結果では、本発明の凝結水ＴＯＣ含有量はおよそ数十から数百ｐｐｍの間であった。ＴＯＣ低下処理は高度酸化法或いは過酸化化合物の添加によって行う。高度酸化法は、オゾンと紫外線照射により、過酸化化合物は過酸化カルシウムと過硫酸ナトリウムなどを含む。実験により高度酸化法と過酸化化合物のどちらも良好な効果が証明された。処理後の凝結水はＴＯＣ濃度が必要に応じて数十から数ｐｐｍ以下にまで低下でき、回収再利用や排出が可能である。 Condensed water obtained by cooling the water vapor evaporated in the wet oxidation tank may contain nuclides, and a small amount of organic matter is inevitable. Without treatment, the total organic carbon (TOC) concentration is too high, making it difficult to discharge or reuse condensed water. In order to solve this problem, the present invention removes nuclides that may be contained through the ion exchange resin bed after the TOC reduction treatment of condensed water. The experimental results show that the condensed water TOC content of the present invention is between about several tens to several hundred ppm. The TOC reduction treatment is performed by an advanced oxidation method or addition of a peroxide compound. The advanced oxidation method uses ozone and ultraviolet irradiation, and the peroxide compound includes calcium peroxide and sodium persulfate. Experiments have shown that both advanced oxidation methods and peroxide compounds have good effects. The condensed water after treatment can be reduced to tens to several ppm or less if necessary, and can be recovered, reused and discharged.
本発明の湿式酸化廃液の固化に使用する固化剤は特に調整して成る。セメントとシリカフューム（ｓｉｌｉｃａ ｆｕｍｅ）、フライアッシュ（ｆｌｙ ａｓｈ）、高炉スラグ（ｂｌａｓｔ ｆｕｒｎａｃｅ ｓｌａｇ ｐｏｗｄｅｒ）などのポゾラン材料（ｐｏｚａｏｌａｎｉｃ ｍａｔｅｒｉａｌｓ）を含むほか、固化体の長期安定性と品質均一性を確保し且つ操作性を増進するため、状況に応じて珪酸塩、燐酸塩、及びカルシウム、珪素、マグネシウム、アルミニウム、鉄とジルコニウムなどの酸化物或いは塩類を選択して添加する。これにより本発明により製造する固化体は良好な機械的強度（ｍｅｃｈａｎｉｃａｌ ｓｔｒｅｎｇｔｈ）、耐凍融性（ｆｒｅｅｚｉｎｇ ａｎｄ ｔｈａｗｉｎｇ ｒｅｓｉｓｔａｎｃｅ）、耐水浸性（ｗａｔｅｒ ｉｍｍｅｒｓｉｏｎ ｒｅｓｉｓｔａｎｃｅ）を具え、更に優れた長期安定性と均一な品質を具える。 The solidifying agent used for solidifying the wet oxidation waste liquid of the present invention is particularly prepared. In addition to pozzolanic materials such as cement and silica fume, fly ash, blast furnace slag powder, etc., ensuring long-term stability and quality uniformity of solidified bodies In order to improve the properties, silicates, phosphates, and oxides or salts such as calcium, silicon, magnesium, aluminum, iron and zirconium are selectively added depending on the situation. As a result, the solidified product produced according to the present invention has good mechanical strength, freezing and thawing resistance, water immersion resistance, and excellent long-term stability and uniformity. Have quality.
本発明は衆知技術の欠点に対する良好な解決対策を有し、重大な腐食問題を回避するとともに、優れた減容効果を具え、且つ操作制御も十分安定している。生成する最終廃棄物固化体の品質は優良で、クリーン（清潔）処理の要求にも適合している。 The present invention has a good solution to the drawbacks of the known art, avoids serious corrosion problems, has an excellent volume reduction effect, and is sufficiently stable in operation control. The quality of the final waste solids produced is excellent and meets the requirements for clean processing.
実施例１
図２に実施例に使用する実験装置を示す。４，０００ｍｌのガラスビーカー１を３つの孔のあるガラスの蓋で覆い、ガラス蓋の中間の孔Ａにモータ２によって駆動されるフッ素樹脂攪拌器３を設け、別の孔を投入口Ｂ、もう一つの孔を出口Ｃとする。出口Ｃと回流管４、薄膜除霧器５及び冷却凝縮管６を連結する。湿式酸化で生成する混合気体は出口Ｃから流出し、薄膜除霧器５を経過する時、混合気体に含まれる水霧（ｗａｔｅｒ ｍｉｓｔ）が除かれて大きい水滴を形成し、回流管４を経て反応層７内に回流する。水蒸気と二酸化炭素は薄膜除霧器５を通過して冷却凝集管６に入ると、水蒸気は冷却されて凝縮して水と成り、収集ビン８内に収集した後、更に必要に応じてＴＯＣ低下と脱核種などの処理を行う。二酸化炭素はその他凝集されない気体と共に排出される。冷却凝縮管の出口には別途凝結水が回流するフッ素樹脂管９を設け、必要があればフッ素樹脂管上の栓を開けて凝結水を反応ビーカー内に回流させ、液位を調節できる。
Example 1
FIG. 2 shows an experimental apparatus used in the examples. A 4,000
湿式酸化操作開始の時は、陽イオン樹脂（Ａｍｂｅｒｌｉｔｅ ２００Ｃ、Ｄｏｗ Ｃｈｅｍｉｃａｌ Ｃｏ．）４０ｍｌ（乾燥重量１８．０５グラム）と陰イオン樹脂（ＩＲＡ−４０２、Ｄｏｗｅｘ）６０ｍｌ（乾燥重量１９．８８グラム）及び０．０６Ｍ硫酸鉄溶液１，０００ｍｌの順にビーカー内に入れ、濃硫酸を加えて溶液の初期ｐＨを２前後に調節する。ビーカーを電熱板上に置いて加熱しつつ攪拌モータを起動して攪拌し、溶液温度が９５℃に達した時、定量ポンプ（ｍｅｔｅｒｉｎｇ ｐｕｍｐ）で５０％過酸化水素を１２．５ｍｌ／分の流量でビーカー内に注入し、イオン交換樹脂を酸化分解させる。過酸化水素の注入開始後、反応溶液は沸点に達する。温度を９８℃から沸点の間に維持する。その過程で気泡が発生した場合には適量の消泡剤（Ｄｏｗ Ｃｏｒｎｉｎｇ社製 Ｑ２−３４４７）を即時加えて抑制する。水酸化バリウム一水和物粉末を添加して溶液のｐＨを調節し、１．９±０．１の間にする。蒸発のため液位が下がった場合は純水を補充して液位を安定維持する。 At the start of the wet oxidation operation, 40 ml of cation resin (Amberlite 200C, Dow Chemical Co.) (dry weight 18.05 grams), 60 ml of anionic resin (IRA-402, Dowex) (dry weight 19.88 grams) and Put 0.06M iron sulfate solution in the order of 1,000 ml in a beaker and add concentrated sulfuric acid to adjust the initial pH of the solution to around 2. When a beaker is placed on an electric heating plate and heated, the agitation motor is started and agitated. When the solution temperature reaches 95 ° C., 50% hydrogen peroxide is flowed at a flow rate of 12.5 ml / min with a metering pump. Inject into a beaker to oxidatively decompose the ion exchange resin. After the start of hydrogen peroxide injection, the reaction solution reaches the boiling point. The temperature is maintained between 98 ° C. and boiling point. If bubbles are generated in the process, an appropriate amount of antifoaming agent (Q2-3447 manufactured by Dow Corning) is immediately added to suppress the bubbles. Barium hydroxide monohydrate powder is added to adjust the pH of the solution to between 1.9 ± 0.1. When the liquid level drops due to evaporation, pure water is replenished to keep the liquid level stable.
３０分ごとに陽イオン交換樹脂４０ｍｌと陰イオン６０ｍｌ及び過酸化水素３７５ｍｌを加え、最後の樹脂を投入後、過酸化水素を予定していた消費量まで加える。材料投入完了後、反応液を引き続き９８℃から沸点の温度に３０分間維持し、過酸化水素を十分に反応させる。実験の総過程で合計樹脂３．５リットル、過酸化水素１５．５７５リットル、消泡剤１７．８グラム、水酸化バリウム一水和物２７グラムを加えた。樹脂酸化分解液の体積を１０００ｍｌに調整した後、サンプリングを行いＴＯＣ分析して酸化分解効率を計算する。 Every 30 minutes, 40 ml of cation exchange resin, 60 ml of anions and 375 ml of hydrogen peroxide are added, and after the last resin is added, hydrogen peroxide is added to the expected consumption. After completion of the material charging, the reaction solution is continuously maintained at a temperature from 98 ° C. to the boiling point for 30 minutes to sufficiently react hydrogen peroxide. During the entire course of the experiment, 3.5 liters of total resin, 15.575 liters of hydrogen peroxide, 17.8 grams of antifoam, and 27 grams of barium hydroxide monohydrate were added. After adjusting the volume of the resin oxidative decomposition solution to 1000 ml, sampling is performed and TOC analysis is performed to calculate the oxidative decomposition efficiency.
続いて湿式酸化廃液中の硫酸塩の転化を行う。まず水酸化バリウム一水和物粉末４８５グラムを添加して得られた湿式酸化廃液を、攪拌して温度を９８℃前後に維持し、硫酸アンモニウムを硫酸バリウムに転化させる。水酸化バリウムを添加する過程でアンモニアが放出され、これをアンモニア分解器（ａｍｍｍｏｎｉａ ｄｉｓｓｏｃｉａｔｏｒ）１０に導入する。アンモニア分解器を電熱加温し、内部に水酸化ニッケルを配置してアンモニアの分解触媒とし、温度を７００℃に保ち、アンモニア或いは水酸化アンモニウム気体が通過するとアンモニアと水酸化アンモニウムは窒素と水素に分解される。水素は出口で空気と接触すると、空気中の酸素と反応して水となる。本実験で最後に排出するガスに含まれる窒素酸化物濃度は５０ｐｐｍより低いことが測定された。このプロセスで、湿式酸化廃液中の遊離硫酸イオンは不溶性の硫酸バリウムに転化され、アンモニウムイオンはアンモニアとなって析出し、スラリー内に残らず、最終的に窒素と水に転化される。このようにして得られたスラリーのｐＨは１０．５である。
Subsequently, the sulfate in the wet oxidation waste liquid is converted. First, the wet oxidation waste liquid obtained by adding 485 grams of barium hydroxide monohydrate powder is stirred to maintain the temperature at around 98 ° C., thereby converting ammonium sulfate to barium sulfate. In the process of adding barium hydroxide, ammonia is released and is introduced into an
次に、得られたスラリーの固化処理を行う。スラリーを加熱して余分な水分を追い出し、スラリーの水分含有量を調節して、固化を行う際、水と固化剤の重量が適当な比率になるようにする。濃縮処理を経た濃縮スラリーの体積は７３４ｍｌ、重量は１，２０８グラムであり、含まれる水の重量は５７６グラムであった。この濃縮スラリーを別の混合器内に注ぎ、攪拌しながら固化剤７５７グラムをゆっくり加え（水／固化剤重量比を０．７６にする）、１５分間攪拌して均一に混合した後、得られたスラリーを直径５ｃｍ、高さ１１ｃｍのポリエチレン製の型に注ぎ、円柱型の固化体を製造した。固化体を２８日間養生後、型をはずし、両端を平らに切って直径５ｃｍ、高さ１０ｃｍ、両端が平坦なサンプルに成型した。これを米国原子力規制委員会（ＵＳＮＲＣ、ＵＳ Ｎｕｃｌｅａｒ Ｒｅｇｕｌａｔｏｒｙ Ｃｏｍｍｉｓｓｉｏｎ）の測定方法に従って耐圧強度と凍融（ｆｒｅｅｚｉｎｇ ａｎｄ ｔｈａｗｉｎｇ）等の品質テストを行った。実験条件と測定結果を表１と表２に示す。
比較例１
比較例を示す。水酸化カルシウムや水酸化ナトリウムといった主に公知技術で使用される中和剤を使って、本発明の方法と衆知技術の優劣を比較する。
実施例１のプロセスを繰り返し、但し、水酸化バリウムの代わりに水酸化カルシウムを使って湿式酸化の反応液のｐＨを調節し、及び湿式酸化廃液のｐＨを上昇させてアンモニアを追い出す。湿式酸化反応時に、反応溶液のｐＨを同様に１．９±０．１の間に維持する。固化時は湿式酸化廃液の濃縮スラリーｐＨを同じく９．０３から９．０５の間に上昇させる。実施例１と同じ条件を採用し、固化時の濃縮スラリーの水分含有量も実施例１と同じ、水／固化剤重量比も同じとする。実験結果は表３、表４に示すように、湿式酸化時に反応液のｐＨ調整に消費した水酸化カルシウムは６８．２グラムであり、水酸化バリウム使用時（２７グラム）の２．５倍であり、モル数の計算では９倍に近く、水酸化バリウムを使用したｐＨの制御は水酸化カルシウム使用より安定、有効であることを示している。湿式酸化廃液の処理効果と品質面では、固化体をＵＳＮＲＣが規定する方法に従い２８日静置したものと凍融測定後の耐圧強度は、固化体が明らかな機械強度をもたないことを示した。固化体の比重は１．８６で、水酸化バリウム使用時の固化体比重（２．２２）の８４％であった。固化体体積は９８０ｍｌで、水酸化バリウム使用時（８８５ｍｌ）の１．１倍となった。湿式酸化操作のｐＨ制御、固化体品質、及び減容効率の各方面において、全て本発明の方法より劣る。
A comparative example is shown. The superiority and inferiority of the method of the present invention is compared with that of the publicly known technology using neutralizing agents mainly used in the known technology such as calcium hydroxide and sodium hydroxide.
The process of Example 1 is repeated, except that calcium hydroxide is used in place of barium hydroxide to adjust the pH of the wet oxidation reaction solution and the wet oxidation waste solution pH is raised to drive off ammonia. During the wet oxidation reaction, the pH of the reaction solution is similarly maintained between 1.9 ± 0.1. At the time of solidification, the concentrated slurry pH of the wet oxidation waste liquid is also raised between 9.03 and 9.05. The same conditions as in Example 1 are adopted, the water content of the concentrated slurry at the time of solidification is the same as in Example 1, and the water / solidifying agent weight ratio is also the same. As shown in Tables 3 and 4, the experimental results show that the calcium hydroxide consumed in adjusting the pH of the reaction solution during wet oxidation was 68.2 grams, 2.5 times that when using barium hydroxide (27 grams). In the calculation of the number of moles, it is close to 9 times, indicating that control of pH using barium hydroxide is more stable and effective than using calcium hydroxide. In terms of the treatment effect and quality of the wet oxidation waste liquid, the solidified body was allowed to stand for 28 days according to the method prescribed by USNRC and the pressure resistance after freezing and thawing measurement showed that the solidified body had no obvious mechanical strength. It was. The specific gravity of the solidified body was 1.86, 84% of the solidified body specific gravity (2.22) when barium hydroxide was used. The solidified body volume was 980 ml, which was 1.1 times that when using barium hydroxide (885 ml). It is inferior to the method of the present invention in all aspects of pH control, solidified product quality, and volume reduction efficiency of the wet oxidation operation.
比較例２
比較例１のプロセスを繰り返し、但し水酸化ナトリウム溶液を中和剤とする。実験結果を表５、表６に示す。実験で生成する硫酸塩は硫酸ナトリウムで、水溶性が高く且つ非常に活発な化合物である。固化時に硫酸ナトリウムを効果的に安定させるために、実施例１と同様の条件（実験１）を採用するほか、特に実験（実験２）を増加して、濃縮スラリー固化時に水分含有量を５７６グラムから９５０グラムに増加して、濃縮スラリー固化時に硫酸ナトリウムが完全に溶解状態となり、固化剤と作用して安定性の高い（即ち水溶性が低い）硫酸塩を形成するようにし、硫酸ナトリウムが結晶を形成して固化体内に包まれることを避け、安定化反応ができなくなり固化体が水分に接触したり温度湿度変化を受けて品質劣化することを防止した。
Comparative Example 2
The process of Comparative Example 1 is repeated except that sodium hydroxide solution is used as the neutralizing agent. The experimental results are shown in Tables 5 and 6. The sulfate produced in the experiment is sodium sulfate, which is a highly active compound with high water solubility. In order to effectively stabilize sodium sulfate at the time of solidification, the same conditions as in Example 1 (Experiment 1) were adopted, and in particular, the experiment (Experiment 2) was increased to increase the water content to 576 grams when concentrating the concentrated slurry. To 950 grams so that when the concentrated slurry is solidified, the sodium sulfate is completely dissolved and works with the solidifying agent to form a highly stable (ie, low water-soluble) sulfate salt. To prevent entrapment in the solidified body, preventing the stabilization reaction from occurring and preventing the solidified body from coming into contact with moisture or being subject to changes in temperature and humidity.
実験１の湿式酸化溶液のｐH調整時に水酸化ナトリウムを６８．７グラム消費した。水酸化バリウム使用（２７グラム）時の２．５４倍、モル数での計算では１２倍になり、水酸化ナトリウムでのｐH調節効果は水酸化バリウムより劣ることを示している。生成する固化体の体積は９６７ｍｌで、実施例１（８８５ｍｌ）より約１０％多い。固化体を２８日静置後の耐圧強度は５５ｋｇ／ｃｍ2であり、実施例１の１９１ｋｇ／ｃｍ2には程遠い。凍融測定後の耐圧強度は３２．４ｋｇ／ｃｍ2であった。同様に、ｐＨ制御、固化効率と固化体品質などにおいて実施例１に及ばない。
During the pH adjustment of the wet oxidation solution in
実験２で使用した水酸化ナトリウムは８８．１グラムであり、消費量は実験１より更に多かった。固化体を２８日間静置した後の耐圧強度は１５５ｋｇ／ｃｍ2と、実験１より優れているが、やはり実施例１の結果より劣る。凍融測定後の耐圧強度は１０８．５ｋｇ／ｃｍ2とこれも実験１より優れているが、実施例１の固化体には遠く及ばない。生成する固化体体積は１，３００ｍｌで、実験１より約１／３大きく、実施例１の水酸化バリウム使用時より約１／２大きくなった。
以上の実験比較から、本発明の方法は湿式酸化の反応条件制御においても、湿式酸化廃液の固化体の減容と固化体品質においても、全て衆知技術より優れた結果が得られることが証明された。
From the above experimental comparison, it is proved that the method of the present invention can obtain results superior to those of the publicly known technology both in the control of the reaction conditions of wet oxidation and in the volume reduction and quality of the solidified product of the wet oxidation waste liquid. It was.
１ ガラスビーカー
２ モータ
３ フッ素樹脂攪拌器
４ 回流管
５ 除霧器
６ 冷却凝縮管
７ 反応槽
８ 収集ビン
９ フッ素樹脂管
１０ 導管
１１ アンモニア分解器
１２ 加熱器
１３ 温度計
A 中間孔
B 投入口
C 出口
V１、V２、V３ バルブ
DESCRIPTION OF
A Intermediate hole
B inlet
Exit C
V1, V2, V3 valves
Claims (14)
そのｐＨを４以下の酸性領域に保つことを特徴とする廃イオン交換樹脂の処理方法。 Using iron sulfate as a catalyst, in the treatment method of the waste ion-exchange resin to perform the decomposition and oxidation of the ion exchange resins under acidic conditions using sulfuric acid hydrogen peroxide as oxidizing agent, barium hydroxide and the pH adjusting agent A method for treating a waste ion exchange resin, characterized in that the pH is kept in an acidic region of 4 or less using sulfuric acid .
（１）イオン交換樹脂を硫酸鉄溶液中に加えて溶液を攪拌しつつ９０℃以上、沸点以下の温度に加熱し、
（２）過酸化水素を（１）の加熱溶液中に添加し、硫酸を加えて反応条件を酸性とすると共に水酸化バリウム及び硫酸により溶液のｐＨを酸化反応に適した4以下の酸性領域に保って過酸化水素による湿式酸化反応を行い、
（３）過酸化水素による湿式酸化反応を完了した後、溶液中に水酸化バリウムを添加して溶液をアルカリ領域に転換して溶液中の硫酸イオンを硫酸バリウムとして沈殿させると共に、アンモニウムイオンを水酸化アンモニウム或いはアンモニアの形態で溶液から逸脱するようにし、
（４）（３）の反応溶液を濃縮して冷却後、固化剤を添加して均一に混合し、静置して硬化させる、
ことを特徴とする廃イオン交換樹脂の処理方法。 In the processing method of waste ion exchange resin,
(1) An ion exchange resin is added to an iron sulfate solution, and the solution is stirred and heated to a temperature of 90 ° C. or higher and a boiling point or lower,
(2) Hydrogen peroxide is added to the heated solution of (1), and sulfuric acid is added to make the reaction conditions acidic, and the pH of the solution is adjusted to an acidic region of 4 or less suitable for oxidation reaction with barium hydroxide and sulfuric acid. Keep wet oxidation reaction with hydrogen peroxide,
(3) After the wet oxidation reaction with hydrogen peroxide is completed, barium hydroxide is added to the solution to convert the solution to an alkaline region, and sulfate ions in the solution are precipitated as barium sulfate. To escape from solution in the form of ammonium oxide or ammonia,
(4) After concentrating and cooling the reaction solution of (3), a solidifying agent is added and mixed uniformly, and allowed to stand to cure.
A method for treating a waste ion exchange resin.
（１）イオン交換樹脂を硫酸鉄溶液中に加えて溶液を攪拌しつつ９０℃以上、沸点以下の温度に加熱し、
（２）過酸化水素を（１）の加熱溶液中に添加し、硫酸を加えて反応条件を酸性とすると共に水酸化バリウム及び硫酸により溶液のｐＨを酸化反応に適した4以下の酸性領域に保って過酸化水素による湿式酸化反応を行い、
（３）上記酸化反応で生成した水蒸気と二酸化炭素を冷却コンデンサを経て凝結水を収集し、該凝結水中の総有機炭素（ＴＯＣ）と核種濃度を低下させる処理を行った後、該凝結水を回収再利用或いは排出し、二酸化炭素は濾過後放出し、
（４）過酸化水素による湿式酸化反応を完了した後、溶液中に水酸化バリウムを添加して溶液をアルカリ領域に転換して溶液中の硫酸イオンを硫酸バリウムとして沈殿させると共に、アンモニウムイオンを水酸化アンモニウム或いはアンモニアの形態で溶液から逸脱するようにし、
（５）溶液から逸脱した水酸化アンモニウム或いはアンモニアを、アンモニア分解装置を経て分解し、水素ガスと窒素ガスを生成し、生成した水素ガスを空気と接触反応させて水とし、
（６）（４）の反応溶液に固化剤を添加して均一に混合し、静置して硬化させる
ことを特徴とする廃イオン交換樹脂の処理方法。 In the processing method of waste ion exchange resin,
(1) An ion exchange resin is added to an iron sulfate solution and the solution is stirred and heated to a temperature of 90 ° C. or higher and a boiling point or lower,
(2) Hydrogen peroxide is added to the heated solution of (1), and sulfuric acid is added to make the reaction conditions acidic, and the pH of the solution is adjusted to an acidic region of 4 or less suitable for oxidation reaction with barium hydroxide and sulfuric acid. Keep wet oxidation reaction with hydrogen peroxide,
(3) Water vapor and carbon dioxide generated by the oxidation reaction are collected through a cooling condenser, and condensed water is collected. After processing to reduce the total organic carbon (TOC) and nuclide concentration in the condensed water, the condensed water is Recovered, reused or discharged, carbon dioxide released after filtration,
(4) After the wet oxidation reaction with hydrogen peroxide is completed, barium hydroxide is added to the solution to convert the solution to an alkaline region, and sulfate ions in the solution are precipitated as barium sulfate. To escape from solution in the form of ammonium oxide or ammonia,
(5) Ammonium hydroxide or ammonia deviating from the solution is decomposed through an ammonia decomposing apparatus to generate hydrogen gas and nitrogen gas, and the generated hydrogen gas is contacted with air to form water.
(6) A method of treating a waste ion exchange resin, comprising adding a solidifying agent to the reaction solution of (4), mixing uniformly, and allowing to stand and cure.
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