JP2010234339A - Treatment liquid for refining crude ion exchange resin - Google Patents
Treatment liquid for refining crude ion exchange resin Download PDFInfo
- Publication number
- JP2010234339A JP2010234339A JP2009087809A JP2009087809A JP2010234339A JP 2010234339 A JP2010234339 A JP 2010234339A JP 2009087809 A JP2009087809 A JP 2009087809A JP 2009087809 A JP2009087809 A JP 2009087809A JP 2010234339 A JP2010234339 A JP 2010234339A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- ion exchange
- treatment liquid
- crude
- chelating agent
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 141
- 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 abstract description 138
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 133
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 133
- 238000007670 refining Methods 0.000 title abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 69
- 239000002738 chelating agent Substances 0.000 claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 33
- 238000000746 purification Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 abstract description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 17
- 239000011707 mineral Substances 0.000 abstract description 17
- 238000011109 contamination Methods 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 20
- -1 iron ions Chemical class 0.000 description 18
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 2
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DIWZKTYQKVKILN-VKHMYHEASA-N (2s)-2-(dicarboxymethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(C(O)=O)C(O)=O DIWZKTYQKVKILN-VKHMYHEASA-N 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 229920013653 perfluoroalkoxyethylene Polymers 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
本発明は、粗イオン交換樹脂の精製用の処理液に関する。 The present invention relates to a treatment liquid for purification of a crude ion exchange resin.
近年、電気・電子分野の各種製品（以下、電気・電子製品とも記す。）の製造において、高性能化・高品質化の要求が高まっており、これらの製品の製造工程に使用する各種材料について高純度化が望まれている。 In recent years, there has been a growing demand for higher performance and higher quality in the manufacture of various products in the electrical and electronic fields (hereinafter also referred to as electrical and electronic products), and various materials used in the manufacturing process of these products. High purity is desired.
特に、半導体、液晶ディスプレイや有機ＥＬディスプレイ等の画像表示装置、ＣＭＯＳやＣＣＤ等の撮像素子、ＤＶＤやＣＤ等の光学記録媒体の製造においては、超純水等の洗浄水やレジスト液に代表される各種の液状剤が用いられる。ここで、前記の液状剤が、イオン性の不純物として、カルシウムイオン、マグネシウムイオン、鉄イオン、銅イオン、亜鉛イオン等の種々の金属イオンを含む場合には、製造される電気・電子製品の品質に大きな影響が出る場合がある。このため、電気・電子製品の製造に用いられる液状剤は、不純物、特に金属イオンを略含まない高純度のものが望まれている。 In particular, in the production of semiconductors, image display devices such as liquid crystal displays and organic EL displays, imaging elements such as CMOS and CCD, and optical recording media such as DVDs and CDs, such as cleaning water and resist solutions such as ultrapure water. Various liquid agents are used. Here, when the liquid agent contains various metal ions such as calcium ions, magnesium ions, iron ions, copper ions, and zinc ions as ionic impurities, the quality of the electrical / electronic products produced May have a significant impact on For this reason, the liquid agent used in the manufacture of electrical / electronic products is desired to have a high purity substantially free of impurities, particularly metal ions.
このような金属イオン含有量の少ない液状剤は、一般的にはイオン交換樹脂により精製されて製造されている。しかし、イオン交換樹脂中にも微量ながら金属不純物が含まれる場合があり、このような場合には、液状剤への金属イオンの溶出により高純度の液状剤を得にくい問題がある。 Such a liquid agent having a low metal ion content is generally produced by being purified by an ion exchange resin. However, a small amount of metal impurities may be contained in the ion exchange resin, and in such a case, there is a problem that it is difficult to obtain a high-purity liquid agent by elution of metal ions into the liquid agent.
上記のイオン交換樹脂が含有する金属による問題を解決するため、例えば、金属イオンを含有するイオン交換樹脂と、金属不純物量が１ｍｇ／Ｌ以下である高純度の鉱酸の水溶液とを特定の条件下に接触させて、イオン交換樹脂の金属イオンの含有量を低減させる技術が提案されている（特許文献１）。 In order to solve the problems caused by the metal contained in the ion exchange resin, for example, an ion exchange resin containing metal ions and an aqueous solution of a high-purity mineral acid having a metal impurity amount of 1 mg / L or less are used under specific conditions. A technique for reducing the content of metal ions in the ion exchange resin by bringing them into contact with each other is proposed (Patent Document 1).
しかし、不純物である金属イオンの含有量が非常に少ない鉱酸の水溶液は非常に高価である。このため、特許文献１に開示される方法では、イオン交換樹脂の精製に多大な費用がかかる問題がある。 However, an aqueous solution of a mineral acid having a very small content of metal ions as impurities is very expensive. For this reason, in the method disclosed in Patent Document 1, there is a problem that the purification of the ion exchange resin is very expensive.
また、特許文献１に開示される方法は、イオン交換樹脂の精製操作において、鉱酸の水溶液が接触する部材（鉱酸の水溶液を輸送するポンプや配管等）も、金属イオンにより汚染されていない非常に清浄なものである必要があり、イオン交換樹脂の精製装置自体を高度にクリーン化するために多大な費用がかかる。 In addition, in the method disclosed in Patent Document 1, in the refining operation of the ion exchange resin, a member (a pump, a pipe, or the like that transports the mineral acid aqueous solution) that is in contact with the mineral acid aqueous solution is not contaminated with metal ions. It needs to be very clean, and it takes a great deal of money to highly clean the ion exchange resin purifier itself.
本発明は、以上の実情に鑑みてなされたものであり、必ずしも金属イオンの含有量が少ない鉱酸の水溶液を用いなくとも、また、必ずしも金属イオンによる汚染が極度に少ない装置を必ずしも用いることなく粗イオン交換樹脂の金属イオン含有量を低減できる、粗イオン交換樹脂の精製に用いられる処理液、及び、精製イオン交換樹脂の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and without necessarily using an aqueous solution of a mineral acid having a low content of metal ions, and without necessarily using an apparatus with extremely low contamination by metal ions. It aims at providing the processing liquid used for the refinement | purification of a crude ion exchange resin which can reduce metal ion content of a crude ion exchange resin, and the manufacturing method of a refined ion exchange resin.
さらに本発明は、前記の精製イオン交換樹脂の製造方法により低コストで製造された高品質の精製イオン交換樹脂を用いて精製された液剤を提供することを目的とする。 Furthermore, an object of this invention is to provide the liquid agent refine | purified using the high quality purified ion exchange resin manufactured at low cost by the manufacturing method of the said purified ion exchange resin.
本発明者らは、粗イオン交換樹脂の精製に用いる処理液にキレート剤を含有させることにより、比較的金属イオン含有量の多い溶媒を処理液の成分として用いた場合でも、粗イオン交換樹脂の金属イオン含有量を低減することが可能となることを見出し、本発明を完成するに至った。具体的には、本発明は以下のようなものを提供する。 The present inventors include a chelating agent in the treatment liquid used for purification of the crude ion exchange resin, so that even when a solvent having a relatively high metal ion content is used as a component of the treatment liquid, It has been found that the metal ion content can be reduced, and the present invention has been completed. Specifically, the present invention provides the following.
（１） キレート剤を含有する粗イオン交換樹脂の精製用の処理液。 (1) A treatment liquid for purification of a crude ion exchange resin containing a chelating agent.
（２） 前記処理液中の前記キレート剤の含有量が、前記処理液中の２価以上の全金属イオンの含有量（モル）に対して０．５から５０倍モルである（１）の処理液。 (2) The content of the chelating agent in the treatment liquid is 0.5 to 50 times mol of the content (mole) of divalent or higher valent metal ions in the treatment liquid. Treatment liquid.
（３） 粗イオン交換樹脂をキレート剤により処理された処理液と接触させて精製する工程を含む精製イオン交換樹脂の製造方法。 (3) A method for producing a purified ion exchange resin comprising a step of purifying a crude ion exchange resin by contacting with a treatment liquid treated with a chelating agent.
（４） 前記キレート剤の使用量が、前記キレート剤により処理される前の処理液中における、２価以上の全金属イオンの含有量（モル）に対して０．５から５０倍モルである（３）の精製イオン交換樹脂の製造方法。 (4) The amount of the chelating agent used is 0.5 to 50 times the mol of the content (moles) of all or more divalent metal ions in the treatment liquid before being treated with the chelating agent. (3) A method for producing a purified ion exchange resin.
（５） （３）又は（４）の方法により製造された精製イオン交換樹脂により精製された液剤。 (5) The liquid agent refine | purified with the refined ion exchange resin manufactured by the method of (3) or (4).
本発明によれば、粗イオン交換樹脂の精製に用いる処理液として、必ずしも高価な高純度の溶媒を用いることなく、また、必ずしも金属イオンによる汚染が極度に少ない装置を用いることなく、粗イオン交換樹脂の金属イオン含有量を低減することが可能となる。 According to the present invention, as a treatment liquid used for purification of a crude ion exchange resin, a crude ion exchange is not necessarily performed without using an expensive high-purity solvent, and without necessarily using an apparatus with extremely low contamination by metal ions. It becomes possible to reduce the metal ion content of the resin.
以下、本発明の一実施形態を説明するが、これに本発明が限定されるものではない。 Hereinafter, although one embodiment of the present invention is described, the present invention is not limited to this.
本出願の明細書及び特許請求の範囲において、「粗イオン交換樹脂」とは、金属イオンを含み本発明の処理液による精製の対象となるイオン交換樹脂であり、例えば、新規に製造されたイオン交換樹脂、又は、超純水やレジスト液等の製造工程において精製に使用されたイオン交換樹脂を意味する。 In the specification and claims of the present application, the “crude ion exchange resin” is an ion exchange resin that contains metal ions and is subject to purification by the treatment liquid of the present invention. It means an exchange resin or an ion exchange resin used for purification in the production process of ultrapure water, a resist solution or the like.
以下、本発明の粗イオン交換樹脂の生成用の処理液について説明する。 Hereinafter, the treatment liquid for producing the crude ion exchange resin of the present invention will be described.
［粗イオン交換樹脂の精製用の処理液］
本発明の、粗イオン交換樹脂の精製用の処理液は、添加剤としてキレート剤を含むものである。本発明の処理液は、所望によりフィルター等により異物を除去した後に使用することが好ましい。以下、キレート剤及び処理液の主成分となる溶媒をそれぞれ説明する。
[Treatment liquid for purification of crude ion exchange resin]
The treatment liquid for purification of the crude ion exchange resin of the present invention contains a chelating agent as an additive. The treatment liquid of the present invention is preferably used after removing foreign substances with a filter or the like as desired. Hereinafter, each of the chelating agent and the solvent as the main component of the treatment liquid will be described.
本発明の処理液は、キレート剤を含むことにより、処理液中の金属イオンがキレートされ、処理液中の金属イオンが粗イオン交換樹脂に吸着されにくくなるため、粗イオン交換樹脂を良好に精製することができる。また、本発明の処理液を用いて粗イオン交換樹脂を精製する場合、粗イオン交換樹脂の精製装置が金属イオンにより汚染されていたとしても、精製装置に付着する金属イオンはキレート剤によりキレートされるため、粗イオン交換樹脂が精製装置に付着していた金属イオンにより汚染されにくい。 Since the treatment liquid of the present invention contains a chelating agent, metal ions in the treatment liquid are chelated, and the metal ions in the treatment liquid are less likely to be adsorbed to the crude ion exchange resin. can do. In addition, when the crude ion exchange resin is purified using the treatment liquid of the present invention, the metal ions adhering to the purification apparatus are chelated by the chelating agent even if the crude ion exchange resin purification apparatus is contaminated with metal ions. Therefore, the crude ion exchange resin is not easily contaminated by the metal ions attached to the purification apparatus.
本発明の処理液に用いるキレート剤は、処理液に加えることにより良好な金属キレート作用を示すものであれば特に制限されない。キレート剤の具体例としては、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、ヒドロキシエチルエチレンジアミン三酢酸（ＨＥＤＴＡ）１，２−シクロヘキサンジアミン四酢酸（ＣｙＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ＥＤＴＡ−ＯＨ、グリコールエーテルジアミン四酢酸（ＧＥＤＴＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、１，３−プロパンジアミン四酢酸（ＰＤＴＡ）、１，３−ジアミノ−２−ヒドロキシプロパン四酢酸（ＤＰＴＡ−ＯＨ）、ヒドロキシエチルイミノ二酢酸（ＨＩＤＡ）、ジヒドロキシエチルグリシン（ＤＨＥＧ）、ジカルボキシメチルグルタミン酸（ＣＭＧＡ）、エチレンジアミンジコハク酸（ＥＤＤＳ）、又はポリマーキレート剤（カルボキシメチルポリエチレンイミン等）等が挙げられる。これらのキレート剤は２種以上のものを組み合わせて用いてもよい。キレート剤はナトリウム又はカリウム等のアルカリ金属塩の形で使用することもできる。 The chelating agent used in the treatment liquid of the present invention is not particularly limited as long as it shows a good metal chelate action when added to the treatment liquid. Specific examples of chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA) 1,2-cyclohexanediaminetetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DTPA), EDTA -OH, glycol ether diamine tetraacetic acid (GEDTA), triethylenetetramine hexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH) , Hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), dicarboxymethyl glutamic acid (CMGA), ethylenediamine disuccinic acid (EDDS), or polymer chelating agent (carboxymethyl polyethylene) Imine etc.) and the like. These chelating agents may be used in combination of two or more. The chelating agent can also be used in the form of an alkali metal salt such as sodium or potassium.
キレート剤の使用量は、本発明の目的を阻害しない範囲で特に限定されない。キレート剤の使用量は、キレート剤を配合する前の処理液の主成分となる溶媒に含まれる２価以上の全金属イオンの含有量（モル）に対して、０．５から５０倍モル用いるのが好ましく、１から１０倍モル用いるのがより好ましい。なお、２価以上の全金属イオンの含有量を定めるための金属種としては処理液中の濃度が０．１μｇ／Ｌ以下と微量であるものは含まない。 The amount of chelating agent used is not particularly limited as long as the object of the present invention is not impaired. The amount of the chelating agent used is 0.5 to 50 times the mol of the total content (mole) of divalent or higher metal ions contained in the solvent that is the main component of the treatment liquid before blending the chelating agent. It is preferable to use 1 to 10 moles. In addition, as a metal seed | species for determining content of all the metal ions more than bivalence, the thing in which the density | concentration in a process liquid is 0.1 microgram / L or less is not included.
処理液の主成分の溶媒中の金属イオン含有量は、フレームレス原子吸光法やＩＣＰ−ＭＳ法により測定することができる。特にＩＣＰ−ＭＳ法は一度に多数の金属イオン含有量を測定することができるので好適に用いることができる。 The metal ion content in the main component solvent of the treatment liquid can be measured by flameless atomic absorption method or ICP-MS method. In particular, the ICP-MS method can be preferably used because it can measure a large number of metal ion contents at one time.
キレート剤の使用量は処理液の金属イオン含有量を測定することにより定めるのが好ましい。しかし、金属イオンの測定は煩雑な作業を伴い時間もかかるため、処理液の主成分の溶媒が、金属により極端に汚染されていないことが明らかである、例えば、試薬として流通しているものである場合、特定の範囲の量のキレート剤を用いてもよい。かかる場合の、キレート剤の具体的な使用量は、処理液中のキレート剤の濃度が２００μｇ／Ｌから１０，０００μｇ／Ｌ、より好ましくは２５０μｇ／Ｌから１，０００μｇ／Ｌとなる量である。 The amount of chelating agent used is preferably determined by measuring the metal ion content of the treatment liquid. However, since measurement of metal ions is complicated and takes time, it is clear that the main component solvent of the treatment liquid is not extremely contaminated by the metal. For example, it is distributed as a reagent. In some cases, a specific range of amounts of chelating agent may be used. In such a case, the specific amount of the chelating agent used is such that the concentration of the chelating agent in the treatment liquid is 200 μg / L to 10,000 μg / L, more preferably 250 μg / L to 1,000 μg / L. .
キレート剤の使用量が過少量である場合には、粗イオン交換樹脂の金属含有量を十分に低減できない場合がある。キレート剤を過剰に用いても本発明の効果は損なわれないが、費用に対して格別高い効果が得られるわけではない。なお、遊離酸型のキレート剤を用いた場合には溶解性の点で問題が生じる場合があり、アルカリ金属塩等の塩型のキレート剤を用いた場合には精製イオン交換樹脂中にアルカリ金属イオン等に由来する不純物が増加するため、あまり過剰に用いることはできない。 If the amount of chelating agent used is too small, the metal content of the crude ion exchange resin may not be sufficiently reduced. Even if the chelating agent is used excessively, the effect of the present invention is not impaired, but an extremely high effect on the cost is not obtained. When a free acid type chelating agent is used, there may be a problem in terms of solubility. When a salt type chelating agent such as an alkali metal salt is used, an alkali metal is contained in the purified ion exchange resin. Since impurities derived from ions and the like increase, it cannot be used excessively.
次いで、処理液の主成分について説明する。本発明の処理液の主成分は、本発明の目的を阻害しない限り特に限定されず、水を含む水性の液体でもよく、水を含まない非水性の液体であってもよい。 Next, the main components of the treatment liquid will be described. The main component of the treatment liquid of the present invention is not particularly limited as long as the object of the present invention is not impaired, and may be an aqueous liquid containing water or a non-aqueous liquid not containing water.
水性の液体の具体例としては、純水、有機酸の水溶液や鉱酸の水溶液等の酸性水溶液、金属水酸化物の水溶液、金属炭酸塩の水溶液、塩基性含窒素有機化合物の水溶液等の塩基性水溶液等が挙げられる。水性の液体は、本発明の目的を阻害しない範囲で水溶性有機溶剤を含んでもよい。水溶性有機溶剤の具体例としては、メタノール、エタノール、エチレングリコール等のアルコール類、アセトン等のケトン類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等の含窒素極性有機溶媒等が挙げられる。 Specific examples of the aqueous liquid include pure water, an acidic aqueous solution such as an aqueous solution of an organic acid or an aqueous solution of a mineral acid, an aqueous solution of a metal hydroxide, an aqueous solution of a metal carbonate, an aqueous solution of a basic nitrogen-containing organic compound, or the like. Aqueous solution and the like. The aqueous liquid may contain a water-soluble organic solvent as long as the object of the present invention is not impaired. Specific examples of the water-soluble organic solvent include alcohols such as methanol, ethanol and ethylene glycol, ketones such as acetone, nitrogen-containing polar organic solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone. It is done.
水性の液体の中では、粗イオン交換樹脂の金属イオン含有量を低減させる効果に優れることから、鉱酸の水溶液が特に好適に用いられる。鉱酸の水溶液の具体例としては、塩酸水溶液、硫酸水溶液、硝酸水溶液、リン酸水溶液等の水溶液が挙げられる。鉱酸の水溶液としては、安価で取り扱いが容易であること等から塩酸水溶液を用いるのが特に好ましい。鉱酸の水溶液は二種以上を混合して用いてもよい。 Among aqueous liquids, an aqueous solution of mineral acid is particularly preferably used because of its excellent effect of reducing the metal ion content of the crude ion exchange resin. Specific examples of the aqueous solution of mineral acid include aqueous solutions such as aqueous hydrochloric acid, aqueous sulfuric acid, aqueous nitric acid, and aqueous phosphoric acid. As the aqueous solution of mineral acid, it is particularly preferable to use an aqueous hydrochloric acid solution because it is inexpensive and easy to handle. A mixture of two or more mineral acid solutions may be used.
使用する酸の種類にもよるが、本発明の処理液の主成分として鉱酸の水溶液を使用する場合の、処理液中の鉱酸の濃度は、通常、１から１５質量％、より好ましくは４から１０質量％である。鉱酸の濃度が低すぎる場合には、イオン交換樹脂と接触させる水性液体の使用量が増えたり、イオン交換樹脂の処理時間に長時間要する場合がある。鉱酸の濃度が高すぎる場合には、イオン交換樹脂の処理に用いる装置が酸による腐食を受けたりする場合がある。 Although depending on the type of acid used, the concentration of the mineral acid in the treatment liquid when using an aqueous solution of mineral acid as the main component of the treatment liquid of the present invention is usually 1 to 15% by mass, more preferably 4 to 10% by mass. When the concentration of the mineral acid is too low, the amount of the aqueous liquid used for contact with the ion exchange resin may increase, or the treatment time of the ion exchange resin may take a long time. When the concentration of the mineral acid is too high, an apparatus used for processing the ion exchange resin may be corroded by acid.
本発明の処理液の主成分として使用される非水性の液体の具体例としては、有機溶媒が挙げられる。本発明の処理液の主成分として使用できる有機溶媒の具体例としては、メタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、エチレングリコール等のアルコール類；アセトン、メチルエチルケトン、アセトフェノン等のケトン類；酢酸、プロピオン酸等の有機酸類；ジエチルエーテル、ジ−ｎ−プロピルエーテル、エチレングリコールジメチルエーテル等のエーテル類；トルエン、キシレン、クロロベンゼン等の芳香族溶媒；及び、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等の含窒素極性有機溶媒等が挙げられる。これらの有機溶媒の中では、粗イオン交換樹脂の金属イオン含有量を低減させる効果に優れることや、取り扱いやすいこと等から、アルコール類、有機酸類、又は含窒素極性有機溶媒を用いるのが好ましい。これらの有機溶媒は二種以上を混合して用いてもよい。 Specific examples of the non-aqueous liquid used as the main component of the treatment liquid of the present invention include organic solvents. Specific examples of the organic solvent that can be used as the main component of the treatment liquid of the present invention include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, and acetophenone; Organic acids such as propionic acid; ethers such as diethyl ether, di-n-propyl ether and ethylene glycol dimethyl ether; aromatic solvents such as toluene, xylene and chlorobenzene; and dimethylformamide, dimethylacetamide and N-methyl-2- Examples thereof include nitrogen-containing polar organic solvents such as pyrrolidone. Among these organic solvents, alcohols, organic acids, or nitrogen-containing polar organic solvents are preferably used because they are excellent in the effect of reducing the metal ion content of the crude ion exchange resin and are easy to handle. These organic solvents may be used as a mixture of two or more.
本発明の処理液は、前述のキレート剤を処理液の主成分である液体に所望の方法により溶解させることにより調製される。 The treatment liquid of the present invention is prepared by dissolving the aforementioned chelating agent in a liquid that is a main component of the treatment liquid by a desired method.
［精製イオン交換樹脂の製造方法］
本発明の精製イオン交換樹脂の製造方法は、粗イオン交換樹脂と、キレート剤により処理された処理液とを接触させる工程を含むものであれば特に限定されない。本発明の精製イオン交換樹脂の製造方法は、種々の方法により新規に製造された粗イオン交換樹脂の金属イオン含有量を低減させ、精製イオン交換樹脂を製造する方法でもよく、超純水やレジスト液等の製造工程において精製に使用され、金属イオンを吸着した粗イオン交換樹脂の金属イオン含有量を低減させ、精製イオン交換樹脂を製造する方法のいずれでもよい。
[Production method of purified ion exchange resin]
The method for producing a purified ion exchange resin of the present invention is not particularly limited as long as it includes a step of bringing a crude ion exchange resin into contact with a treatment liquid treated with a chelating agent. The method for producing a purified ion exchange resin of the present invention may be a method for producing a purified ion exchange resin by reducing the metal ion content of a crude ion exchange resin newly produced by various methods, such as ultrapure water or resist. Any method of producing a purified ion exchange resin by reducing the metal ion content of a crude ion exchange resin used for purification in a production process such as a liquid and adsorbing metal ions may be used.
本発明の精製イオン交換樹脂の製造方法において、キレート剤により処理される処理液は、前述の、粗イオン交換樹脂の精製用の処理液の主成分の溶媒と同様である。また本発明の精製イオン交換樹脂の製造方法において用いるキレート剤についても、前述の粗イオン交換樹脂の精製用の処理液の成分として用いるキレート剤と同様である。 In the method for producing a purified ion exchange resin of the present invention, the treatment liquid treated with the chelating agent is the same as the solvent of the main component of the treatment liquid for purification of the crude ion exchange resin described above. The chelating agent used in the method for producing the purified ion exchange resin of the present invention is the same as the chelating agent used as a component of the treatment liquid for purification of the above-mentioned crude ion exchange resin.
本発明の精製イオン交換樹脂の製造方法では、処理液をキレート剤により処理するが、キレート剤による処理により処理液に対して不溶性の粒子が生じる場合がある。かかる不溶性の粒子は、所望により、処理液への金属の溶出が少ないメンブレンフィルター等を用いて濾過し、処理液から除去してもよい。 In the method for producing a purified ion exchange resin of the present invention, the treatment liquid is treated with a chelating agent, but the treatment with the chelating agent may produce particles insoluble in the treatment liquid. Such insoluble particles may be removed from the treatment liquid by filtration using a membrane filter or the like with little metal elution into the treatment liquid, if desired.
本発明の精製イオン交換樹脂の製造方法では、処理液は、キレート剤により処理されたものであれば、粗イオン交換樹脂と接触する時点で、キレート剤を必ずしも含んでいる必要はない。ただし、処理液は、粗イオン交換樹脂と接触する時点で、キレート剤を含んでいるのが好ましい。精製装置に由来する金属イオンをキレートすることができ、粗イオン交換樹脂が精製装置に由来する金属イオンを吸着しにくいためである。 In the method for producing a purified ion exchange resin of the present invention, as long as the treatment liquid is treated with a chelating agent, it does not necessarily contain a chelating agent when it comes into contact with the crude ion exchange resin. However, it is preferable that the treatment liquid contains a chelating agent when it comes into contact with the crude ion exchange resin. This is because metal ions derived from the purification apparatus can be chelated, and the crude ion exchange resin hardly adsorbs metal ions derived from the purification apparatus.
本発明の精製イオン交換樹脂の製造方法において、キレート剤の使用量は、本発明の目的を阻害しない範囲で特に限定されない。キレート剤の使用量は、キレート剤により処理される前の処理液に含まれる２価以上の全金属イオンの含有量を測定し、それぞれの金属イオンの合計量（モル）に対して、０．５から５０倍モル用いるのが好ましく、１から１０倍モル用いるのがより好ましい。なお、２価以上の全金属イオンの含有量を定めるための金属種としては処理液中の濃度が０．１μｇ／Ｌ以下と微量であるものは含まない。 In the method for producing a purified ion exchange resin of the present invention, the amount of chelating agent used is not particularly limited as long as the object of the present invention is not impaired. The amount of the chelating agent used is determined by measuring the content of all metal ions having a valence of 2 or more contained in the treatment liquid before being treated with the chelating agent, and is 0. It is preferable to use 5 to 50 times mol, and more preferably 1 to 10 times mol. In addition, as a metal seed | species for determining content of all the metal ions more than bivalence, the thing in which the density | concentration in a process liquid is 0.1 microgram / L or less is not included.
キレート剤の使用量は、により処理される前の処理液の金属イオン含有量を測定することにより定めるのが好ましい。しかし、金属イオンの測定は煩雑な作業を伴い時間もかかるため、処理液が、金属により極端に汚染されていないことが明らかである、例えば、試薬として流通しているものである場合、特定の範囲の量のキレート剤を用いてもよい。かかる場合の、キレート剤の具体的な使用量は、処理液中のキレート剤の濃度が２００μｇ／Ｌから１０，０００μｇ／Ｌ、より好ましくは２５０μｇ／Ｌから１，０００μｇ／Ｌとなる量である。 The amount of the chelating agent used is preferably determined by measuring the metal ion content of the treatment liquid before being treated. However, since measurement of metal ions is complicated and takes time, it is clear that the treatment liquid is not extremely contaminated with metal. For example, if the measurement is in circulation as a reagent, A range of amounts of chelating agent may be used. In such a case, the specific amount of the chelating agent used is such that the concentration of the chelating agent in the treatment liquid is 200 μg / L to 10,000 μg / L, more preferably 250 μg / L to 1,000 μg / L. .
本発明の精製イオン交換樹脂の製造方法により精製される粗イオン交換樹脂としては、例えば、強酸性陽イオン交換樹脂、弱酸性陽イオン交換樹脂、強塩基性陰イオン交換樹脂、弱塩基性陰イオン交換樹脂、キレート樹脂等を用いることができる。これらのイオン交換樹脂の中では、電気・電子製品の製造に用いる液状剤の金属イオンを良好に除去することから、強酸性陽イオン交換樹脂又は弱酸性陽イオン交換樹脂が好ましく、強酸性陽イオン交換樹脂が特に好ましい。 Examples of the crude ion exchange resin purified by the method for producing a purified ion exchange resin of the present invention include, for example, a strong acid cation exchange resin, a weak acid cation exchange resin, a strongly basic anion exchange resin, and a weakly basic anion. Exchange resins, chelate resins, and the like can be used. Among these ion exchange resins, a strong acid cation exchange resin or a weak acid cation exchange resin is preferable because it removes metal ions in a liquid agent used in the production of electrical / electronic products well. Exchange resins are particularly preferred.
本発明により処理される粗イオン交換樹脂が含有する金属イオンの種類は特に制限されないが、代表的な例としてはナトリウムイオン、カリウムイオン、リチウムイオン、カルシウムイオン、マグネシウムイオン、鉄イオン、銅イオン、亜鉛イオン、アルミニウムイオン、ニッケルイオン、クロムイオン、コバルトイオン、カドミウムイオン、及びマンガンイオンからなる群から選ばれる１種以上のものが挙げられる。これらの金属イオンの中で特に含有量の高いものは、ナトリウムイオン、カリウムイオン、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、鉄イオン、亜鉛イオンである。 The type of metal ion contained in the crude ion exchange resin treated according to the present invention is not particularly limited, but representative examples include sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, iron ion, copper ion, Examples thereof include one or more selected from the group consisting of zinc ions, aluminum ions, nickel ions, chromium ions, cobalt ions, cadmium ions, and manganese ions. Among these metal ions, those having a particularly high content are sodium ion, potassium ion, calcium ion, magnesium ion, aluminum ion, iron ion and zinc ion.
本発明の精製イオン交換樹脂の製造方法により精製される、粗イオン交換樹脂の金属イオン含有量は特に制限されないが、通常、全金属イオン含有量が１００００μｇ／Ｌ−Ｒ以下、より好ましくは５０００μｇ／Ｌ−Ｒ以下のものが用いられる。本発明の方法により粗イオン交換樹脂の精製を行う場合、キレート剤の効果により処理液中に含まれる金属成分がほとんど精製イオン交換樹脂に移行することがなく、極めて金属イオン含有量の少ない粗イオン交換樹脂を精製することができる。 The metal ion content of the crude ion exchange resin purified by the production method of the purified ion exchange resin of the present invention is not particularly limited, but usually the total metal ion content is 10,000 μg / LR or less, more preferably 5000 μg / LR or less is used. When the crude ion exchange resin is purified by the method of the present invention, the metal component contained in the treatment liquid is hardly transferred to the purified ion exchange resin due to the effect of the chelating agent, and the crude ion having a very low metal ion content. The exchange resin can be purified.
ここで、「／Ｌ−Ｒ」は、「水膨潤状態におけるイオン交換樹脂の体積１Ｌ当たり」を意味する。 Here, “/ LR” means “per 1 L volume of ion exchange resin in a water-swollen state”.
粗イオン交換樹脂又は精製イオン交換樹脂が含有する金属イオンの含有量は、下記の方法によって測定することができる。
＜イオン交換樹脂の金属イオン含有量測定方法＞
イオン交換樹脂を超純水で洗浄後、洗浄されたイオン交換樹脂１００ｍｌ（イオン交換樹脂粒子間の空間も含む体積）を清浄なプラスチック器に移し、これに濃度４％の分析用高純度塩酸５００ｍｌを加えて、２４時間振とうする。振とう後の塩酸中の金属濃度をＩＣＰ−ＭＳで分析する。この分析値から、単位樹脂量あたりの金属イオン含有量を算出する。
The content of metal ions contained in the crude ion exchange resin or the purified ion exchange resin can be measured by the following method.
<Method for measuring metal ion content of ion exchange resin>
After washing the ion exchange resin with ultrapure water, 100 ml of the washed ion exchange resin (the volume including the space between the ion exchange resin particles) is transferred to a clean plastic container, and 500 ml of high-purity hydrochloric acid for analysis with a concentration of 4% is added thereto. And shake for 24 hours. The metal concentration in hydrochloric acid after shaking is analyzed by ICP-MS. From this analysis value, the metal ion content per unit resin amount is calculated.
本発明において、粗イオン交換樹脂と、処理液とを接触させる方法は特に制限されない。粗イオン交換樹脂と処理液を接触させる方法の例としては、処理液の入った容器に粗イオン交換樹脂を入れ、静置下、又は攪拌下に粗イオン交換樹脂と処理液を接触させる方法や、連続的に通液可能な容器に粗イオン交換樹脂を充填した後、容器に連続的又は断続的に処理液を通液する方法等が挙げられる。ここで、連続的に通液可能な容器は、上部が開放されている椀型や瓶型の容器でもよく、処理液の入口と出口が個別に設けられたカラム等の容器であってもよい。 In the present invention, the method for bringing the crude ion exchange resin into contact with the treatment liquid is not particularly limited. Examples of the method for bringing the crude ion exchange resin into contact with the treatment liquid include a method in which the crude ion exchange resin is placed in a container containing the treatment liquid and the crude ion exchange resin is brought into contact with the treatment liquid while standing or stirring. Examples of the method include a method in which a crude ion exchange resin is filled in a container that can be continuously passed, and then a treatment liquid is continuously or intermittently passed through the container. Here, the container through which liquid can be continuously passed may be a bowl-shaped container or a bottle-shaped container having an open top, or may be a container such as a column in which an inlet and an outlet for processing liquid are individually provided. .
粗イオン交換樹脂と処理液の接触は、作業性に優れ、粗イオン交換樹脂の金属イオンが低減されやすいこと等から、通常、カラムに処理液を連続的に通液する方法により行われる。 The contact between the crude ion exchange resin and the treatment liquid is usually performed by a method in which the treatment liquid is continuously passed through the column because of excellent workability and easy reduction of metal ions in the crude ion exchange resin.
処理液をイオン交換樹脂が入った容器に通液する場合、処理液は一過式で通液させてもよく、循環式で通液させてもよい。処理液の通液方法は、イオン交換樹脂を常に金属イオン含有量の少ない処理液と接触させることができ、イオン交換樹脂の金属含有量を低減させる効果が高いことから、一過式であるのが好ましい。 When the treatment liquid is passed through a container containing an ion exchange resin, the treatment liquid may be passed in a transient manner or in a circulation manner. The treatment liquid flow-through method is a transient method because the ion exchange resin can always be brought into contact with a treatment liquid having a low metal ion content, and the effect of reducing the metal content of the ion exchange resin is high. Is preferred.
また、本発明の方法によれば、処理液がキレート剤を含んでいるため、処理液を循環させても処理液中に蓄積する金属成分はキレート剤とキレートを形成するので、処理液からイオン交換樹脂への金属イオンの移動は起こりにくい。このため、処理液の使用量が少なくてすみ、低コストで粗イオン交換樹脂を生成することができる点で、処理液の通液方法として循環式を用いるのも好ましい。 Further, according to the method of the present invention, since the treatment liquid contains a chelating agent, the metal component accumulated in the treatment liquid forms a chelate with the chelating agent even when the treatment liquid is circulated. The migration of metal ions to the exchange resin is unlikely to occur. For this reason, it is also preferable to use a circulation method as a method for passing the treatment liquid in that the amount of the treatment liquid used is small and a crude ion exchange resin can be produced at a low cost.
処理液を粗イオン交換樹脂が入った容器に通液する場合の、送液手段は特に制限されない。典型的には、渦巻きポンプ、プランジャーポンプ、ダイヤフラムポンプ等の所望のポンプが挙げられる。 There is no particular limitation on the liquid feeding means when the treatment liquid is passed through the container containing the crude ion exchange resin. Typically, desired pumps, such as a vortex pump, a plunger pump, a diaphragm pump, are mentioned.
本発明の方法では、処理液がキレート剤を含むため、処理液と接触する部材は金属イオンを高度に除去された清浄なものを必ずしも用いる必要はない。しかし、処理液が接触する部材に付着する金属イオンの影響を排除するために、処理液が接触する部材は、粗イオン交換樹脂と処理液を接触させる前に流体により洗浄されているのが好ましい。流体としては、処理液が接触する部材の金属イオンの付着量を低減することができれば特に制限されず、気体、液体のいずれも用いることができる。処理液と接触する部材を洗浄する流体としては液体が好ましい。洗浄に使用される液体としては、例えば、純水、超純水、粗イオン交換樹脂の精製に用いる処理液等が挙げられ、これらの中では粗イオン交換樹脂の処理に用いる処理液がより好ましい。 In the method of the present invention, since the treatment liquid contains a chelating agent, it is not always necessary to use a clean member from which metal ions have been removed to a high degree. However, in order to eliminate the influence of metal ions adhering to the member in contact with the treatment liquid, the member in contact with the treatment liquid is preferably washed with a fluid before bringing the crude ion exchange resin into contact with the treatment liquid. . The fluid is not particularly limited as long as the amount of metal ions attached to the member in contact with the processing liquid can be reduced, and either gas or liquid can be used. A liquid is preferable as the fluid for cleaning the member in contact with the processing liquid. Examples of the liquid used for cleaning include pure water, ultrapure water, and a treatment liquid used for purification of the crude ion exchange resin. Among these, a treatment liquid used for the treatment of the crude ion exchange resin is more preferable. .
本発明において用いる、粗イオン交換樹脂を充填する容器、処理液を送液するポンプ、処理液を通液するチューブ又はパイプ、処理液の流量を制御するバルブ等の処理液に接触する部材は金属成分を含有しない材料により構成されるものが好ましい。 In the present invention, a member that contacts the processing liquid, such as a container filled with a crude ion exchange resin, a pump for feeding the processing liquid, a tube or pipe for passing the processing liquid, a valve for controlling the flow rate of the processing liquid, is a metal. What is comprised with the material which does not contain a component is preferable.
ここで金属成分を含有しない材料は、全く金属成分を含有しないものには限定されず、処理液への金属の溶出の影響が出ない量の、触媒、可塑剤、安定剤等の添加剤や充填材等の金属含有成分を含むものも含む。 Here, the material containing no metal component is not limited to a material containing no metal component at all, and additives such as catalysts, plasticizers, stabilizers, etc. in amounts that do not affect the elution of the metal into the treatment liquid. Including those containing metal-containing components such as fillers.
本発明で用いる金属成分を含有しない材料としては、安価で、加工が容易であり、金属溶出の問題が少ないことから合成樹脂材料が好ましい。本発明において用いる合成樹脂材料の好適な例としては、フッ素樹脂、ポリプロピレン、ポリエチレン、ＡＢＳ、ポリエーテルエーテルケトン又はこれらの樹脂の混合組成物等の熱可塑性樹脂や、エポキシ樹脂等の熱硬化性樹脂が挙げられる。これらの合成樹脂材料の中では、処理液の種類によらず高い耐薬品性を有することからフッ素樹脂が好ましい。フッ素樹脂の例としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロアルコキシエチレン共重合体（ＰＦＡ）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、ビニリデンフルオライド樹脂（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、ビニルフルオライド樹脂（ＰＶＦ）等が挙げられる。 A material not containing a metal component used in the present invention is preferably a synthetic resin material because it is inexpensive, easy to process, and has few problems of metal elution. Preferred examples of the synthetic resin material used in the present invention include thermoplastic resins such as fluororesin, polypropylene, polyethylene, ABS, polyether ether ketone, or a mixture of these resins, and thermosetting resins such as epoxy resins. Is mentioned. Among these synthetic resin materials, fluororesins are preferred because they have high chemical resistance regardless of the type of treatment liquid. Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), and tetrafluoroethylene-hexafluoropropylene copolymer. Examples thereof include a polymer (FEP), a vinylidene fluoride resin (PVDF), an ethylene-chlorotrifluoroethylene copolymer (ECTFE), a polychlorotrifluoroethylene (PCTFE), and a vinyl fluoride resin (PVF).
粗イオン交換樹脂と処理液を接触させる際の温度は、粗イオン交換樹脂が変質、変形、又は破損しない限り特に制限されず、０から６０℃が好ましく、より１０から４０℃がより好ましい。かかる温度範囲で粗イオン交換樹脂と処理液を接触させれば、粗イオン交換樹脂に変形等の悪影響がみられず、処理液の流動性を確保することができる。 The temperature at which the crude ion exchange resin is brought into contact with the treatment liquid is not particularly limited as long as the crude ion exchange resin is not altered, deformed, or broken, and is preferably 0 to 60 ° C, more preferably 10 to 40 ° C. When the crude ion exchange resin is brought into contact with the treatment liquid in such a temperature range, the crude ion exchange resin is not adversely affected by deformation and the like, and the fluidity of the treatment liquid can be ensured.
粗イオン交換樹脂と処理液との接触時間は、粗イオン交換樹脂の金属イオン含有量を所望の量まで低減可能である限り特に制限されない。典型的な接触時間は、２０時間以上、より好ましくは２４時間以上である。 The contact time between the crude ion exchange resin and the treatment liquid is not particularly limited as long as the metal ion content of the crude ion exchange resin can be reduced to a desired amount. Typical contact times are 20 hours or longer, more preferably 24 hours or longer.
処理液に用いた溶媒が鉱酸の水溶液等の純水以外のものである場合には、処理液により精製して得られた精製イオン交換樹脂を純水で洗浄するのが好ましく、超純水で洗浄することがより好ましい。精製イオン交換樹脂の洗浄に、純水と超純水のいずれを用いるかは、精製イオン交換樹脂の金属イオン含有量に応じて適宜定めればよい。精製イオン交換樹脂の洗浄に超純水を用いる場合でも、超純水の使用量はイオン交換樹脂に付着する処理液を置換できる最小量でよいため、粗イオン交換樹脂の精製にかかるコストには大きく影響しない。純水や超純水による精製イオン交換樹脂の洗浄により、本発明の方法により得られた精製イオン交換樹脂を用いて電気・電子製品の製造に用いられる液剤を精製する際の液剤への鉱酸等の混入や、処理液に溶出した金属イオンによる精製イオン交換樹脂の再汚染を防ぐことができる。 When the solvent used in the treatment liquid is other than pure water such as an aqueous solution of a mineral acid, it is preferable to wash the purified ion exchange resin obtained by purification with the treatment liquid with pure water. It is more preferable to wash with. Whether pure water or ultrapure water is used for washing the purified ion exchange resin may be appropriately determined according to the metal ion content of the purified ion exchange resin. Even when ultrapure water is used for cleaning purified ion exchange resin, the amount of ultrapure water used is the minimum amount that can replace the treatment liquid adhering to the ion exchange resin. There is no significant effect. Mineral acid into the liquid agent when purifying the liquid agent used in the manufacture of electrical and electronic products using the purified ion exchange resin obtained by the method of the present invention by washing the purified ion exchange resin with pure water or ultrapure water It is possible to prevent contamination of the purified ion exchange resin due to metal ions eluted in the treatment liquid.
以上説明した本発明の精製イオン交換樹脂の製造方法により、比較的金属イオン含有量の高い処理液を用いる場合や、粗イオン交換樹脂の精製装置が高度にクリーン化されていない場合でも、金属イオン含有量の少ない高品質の精製イオン交換樹脂を得ることが可能となる。 Even when a treatment liquid having a relatively high metal ion content is used by the method for producing a purified ion exchange resin of the present invention described above, or when a crude ion exchange resin purification apparatus is not highly cleaned, metal ions are used. It becomes possible to obtain a high-quality purified ion exchange resin with a low content.
本発明の精製イオン交換樹脂の製造方法により得られる精製イオン交換樹脂は金属イオン含有量の少ない高品質のものであり、種々の液剤の精製に好適に利用される。本発明により得られる精製イオン交換樹脂により精製される液剤の具体例としては、塩酸、フッ化水素酸、過酸化水素、リン酸、酢酸、フッ化アンモニウム水溶液等の薬液；メタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、アセトン、メチルエチルケトン、トルエン、キシレン、ジメチルスルホキシド、テトラヒドロフラン、プロピレングリコールモノメチルエーテルアセテート等の有機溶媒；液晶用フォトレジスト、カラーフィルター材料、配向膜、液晶混合物、封止材、偏光板、反射板、オーバーコート剤、洗浄用超純水等のフラットパネルディスプレイ材料；及び、半導体用レジスト、剥離剤、反射防止膜、バッファコート膜用塗布剤、層間絶縁膜塗布剤、洗浄用超純水等の半導体製造材料等が挙げられる。 The purified ion exchange resin obtained by the method for producing a purified ion exchange resin of the present invention is of high quality with a low metal ion content, and is suitably used for the purification of various liquid agents. Specific examples of the liquid agent purified by the purified ion exchange resin obtained by the present invention include chemicals such as hydrochloric acid, hydrofluoric acid, hydrogen peroxide, phosphoric acid, acetic acid, and ammonium fluoride aqueous solution; methanol, ethanol, n- Organic solvents such as propyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, toluene, xylene, dimethyl sulfoxide, tetrahydrofuran, propylene glycol monomethyl ether acetate; photoresists for liquid crystals, color filter materials, alignment films, liquid crystal mixtures, sealing materials, polarizing plates , Reflectors, overcoat agents, flat panel display materials such as ultrapure water for cleaning; and resists for semiconductors, release agents, antireflection films, coating agents for buffer coat films, interlayer insulating film coating agents, ultrapure for cleaning Semiconductor manufacturing materials such as water .
以下、具体例によってさらに本発明を説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited thereto.
［実施例１、実施例２及び比較例］
内径４００ｍｍ×高さ５００ｍｍのアクリル樹脂製の円筒容器に、強酸性陽イオン交換樹脂（ＫＲ−ＵＣ１、栗田工業株式会社製）５００ｍＬを充填した。
[Example 1, Example 2 and Comparative Example]
A cylindrical container made of acrylic resin having an inner diameter of 400 mm and a height of 500 mm was filled with 500 mL of strongly acidic cation exchange resin (KR-UC1, manufactured by Kurita Kogyo Co., Ltd.).
実施例１で用いた処理液は、濃度３５質量％工業用塩酸（合成塩酸、鶴見曹達株式会社製）を超純水により希釈して得た濃度４質量％の塩酸水溶液に対し、処理液中３００μｇ／Ｌ濃度となるようにエチレンジアミン四酢酸（キシダ化学株式会社製）を添加して調製した。実施例２で用いた処理液は、エチレンジアミン四酢酸をエチレンジアミン四酢酸二ナトリウム塩（二水和物）（キシダ化学株式会社製）に変える事の他は同様にして調製した。比較例では、キレート剤を添加しない濃度４質量％の塩酸水溶液を処理液として用いた。なお、超純水は、市水を超純水製造装置（栗田工業株式会社製、クリアクア（登録商標））で処理したものを用いた。また、濃度３５％の工業用塩酸に含まれるＩＣＰ−ＭＳで測定した金属イオン含有量を表１に示す。 The treatment liquid used in Example 1 was used in the treatment liquid with respect to a 4 mass% hydrochloric acid aqueous solution obtained by diluting 35 mass% industrial hydrochloric acid (synthetic hydrochloric acid, manufactured by Tsurumi Soda Co., Ltd.) with ultrapure water. Ethylenediaminetetraacetic acid (manufactured by Kishida Chemical Co., Ltd.) was added to prepare a concentration of 300 μg / L. The treatment liquid used in Example 2 was prepared in the same manner except that ethylenediaminetetraacetic acid was changed to ethylenediaminetetraacetic acid disodium salt (dihydrate) (manufactured by Kishida Chemical Co., Ltd.). In the comparative example, an aqueous hydrochloric acid solution having a concentration of 4% by mass without adding a chelating agent was used as the treatment liquid. In addition, the ultrapure water used what processed city water with the ultrapure water manufacturing apparatus (The Kurita Industrial Co., Ltd. make, Clearqua (trademark)). Table 1 shows the metal ion content measured by ICP-MS contained in industrial hydrochloric acid having a concentration of 35%.
次いで、処理液との接液部分が非金属材料で構成されるポンプ（ＥＨＮ−Ｂ２１ＦＣ２Ｒ、株式会社イワキ製）を用いて、処理液供給速度２５０ｍＬ／ｈｒ、処理時間２４時間の条件で、円筒容器に処理液を一過式で通液し、強酸性陽イオン交換樹脂の精製を行った。 Next, using a pump (EHN-B21FC2R, manufactured by Iwaki Co., Ltd.) whose wetted part with the processing liquid is made of a non-metallic material, a cylindrical container under the conditions of a processing liquid supply speed of 250 mL / hr and a processing time of 24 hours Then, the treatment solution was passed in a transient manner to purify the strongly acidic cation exchange resin.
精製処理後に、下記方法に従って、イオン交換樹脂の金属含有量を測定した。精製前のイオン交換樹脂の含有金属量を１とした場合の精製後のイオン交換樹脂の金属含有量を表２に記す。 After the purification treatment, the metal content of the ion exchange resin was measured according to the following method. Table 2 shows the metal content of the ion exchange resin after purification when the metal content of the ion exchange resin before purification is 1.
＜イオン交換樹脂の金属イオン含有量測定方法＞
イオン交換樹脂を超純水で洗浄後、洗浄されたイオン交換樹脂１００ｍｌ（イオン交換樹脂粒子間の空間も含む体積）を清浄なプラスチック器に移し、これに濃度４％の分析用高純度塩酸５００ｍｌを加えて、２４時間振とうする。振とう後の塩酸中の金属濃度をＩＣＰ−ＭＳで分析する。この分析値から、単位樹脂量あたりの金属イオン含有量を算出する。
<Method for measuring metal ion content of ion exchange resin>
After washing the ion exchange resin with ultrapure water, 100 ml of the washed ion exchange resin (the volume including the space between the ion exchange resin particles) is transferred to a clean plastic container, and 500 ml of high-purity hydrochloric acid for analysis with a concentration of 4% is added thereto. And shake for 24 hours. The metal concentration in hydrochloric acid after shaking is analyzed by ICP-MS. From this analysis value, the metal ion content per unit resin amount is calculated.
表２より、処理液にキレート剤を所定量配合した実施例１及び実施例２では、イオン交換樹脂中の、カルシウムイオン、鉄イオン、銅イオン、及び亜鉛イオンの含有量が良好に低減されたことが分かる。一方、比較例では、ナトリウムイオン及び鉄イオンの含有量こそ低減されたものの、カルシウムイオン、銅イオン、亜鉛イオンについては、かえって含有量が増加する結果となった。 From Table 2, in Example 1 and Example 2 which mix | blended the chelating agent with the predetermined amount to the process liquid, content of calcium ion, iron ion, copper ion, and zinc ion in ion exchange resin was reduced favorably. I understand that. On the other hand, in the comparative example, although the contents of sodium ions and iron ions were reduced, the contents of calcium ions, copper ions, and zinc ions were increased.
実施例１及び実施例２により、キレート剤としてエチレンジアミン四酢酸二ナトリウム塩（二水和物）を用いたナトリウムイオン含有量の多い処理液では精製イオン交換樹脂中のナトリウムイオン含有量を低減することはできないが、キレート剤として遊離酸のエチレンジアミン四酢酸を用いて処理液中のナトリウムイオンの含有量を低くすることにより、精製イオン交換樹脂のナトリウムイオンの含有量が良好に低減されることが分かる。 According to Example 1 and Example 2, in a treatment solution having a high sodium ion content using ethylenediaminetetraacetic acid disodium salt (dihydrate) as a chelating agent, the sodium ion content in the purified ion exchange resin should be reduced. However, it is understood that the sodium ion content of the purified ion exchange resin can be reduced satisfactorily by reducing the sodium ion content in the treatment liquid using ethylenediaminetetraacetic acid as a free acid as a chelating agent. .
これらの結果より、本願発明の処理液は、キレート剤を添加しない工業用塩酸では精製できない、カルシウムイオン、鉄イオン、銅イオン、及び亜鉛イオンの含有量が少ない高純度の粗イオン交換樹脂をさらに精製する場合に特に有用であることが分かる。 From these results, the treatment liquid of the present invention is a high-purity crude ion exchange resin with a low content of calcium ions, iron ions, copper ions, and zinc ions that cannot be purified by industrial hydrochloric acid without adding a chelating agent. It turns out to be particularly useful when purifying.
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| JP2010234297A (en) * | 2009-03-31 | 2010-10-21 | Kurita Water Ind Ltd | Method of regenerating ion exchange resin and ultrapure water producing apparatus |
| JP2014121709A (en) * | 2014-03-31 | 2014-07-03 | Kurita Water Ind Ltd | Method for preventing ion exchange resin from being contaminated with boron |
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| KR102346812B1 (en) * | 2019-10-30 | 2022-01-04 | 주식회사 삼양사 | Method for preparing ion exchange resin with reduced metal impurity content |
| KR102499164B1 (en) * | 2020-10-27 | 2023-02-14 | 주식회사 삼양사 | Method for preparing ion exchange resin with reduced content of metallic impurities |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010234297A (en) * | 2009-03-31 | 2010-10-21 | Kurita Water Ind Ltd | Method of regenerating ion exchange resin and ultrapure water producing apparatus |
| JP2014121709A (en) * | 2014-03-31 | 2014-07-03 | Kurita Water Ind Ltd | Method for preventing ion exchange resin from being contaminated with boron |
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