JP5555424B2 - Purification method of alkaline aqueous solution - Google Patents
Purification method of alkaline aqueous solution Download PDFInfo
- Publication number
- JP5555424B2 JP5555424B2 JP2008522390A JP2008522390A JP5555424B2 JP 5555424 B2 JP5555424 B2 JP 5555424B2 JP 2008522390 A JP2008522390 A JP 2008522390A JP 2008522390 A JP2008522390 A JP 2008522390A JP 5555424 B2 JP5555424 B2 JP 5555424B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- alkaline aqueous
- weight
- basic anion
- hydroxide
- 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.)
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- 239000007864 aqueous solution Substances 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 54
- 238000000746 purification Methods 0.000 title claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 120
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 239000012535 impurity Substances 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 150000001450 anions Chemical class 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000011736 potassium bicarbonate Substances 0.000 claims description 12
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 12
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 235000011181 potassium carbonates Nutrition 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical group [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 36
- 235000011121 sodium hydroxide Nutrition 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000000835 fiber Substances 0.000 description 21
- 238000012545 processing Methods 0.000 description 21
- 235000012431 wafers Nutrition 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 238000005349 anion exchange Methods 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- -1 for example Substances 0.000 description 12
- 235000011118 potassium hydroxide Nutrition 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 239000013522 chelant Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 150000003377 silicon compounds Chemical class 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000057 synthetic resin Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 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 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000005341 cation exchange Methods 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical group OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical group OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical group NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000768 polyamine Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/32—Purification; Separation by absorption or precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/024—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/26—Purification by precipitation or adsorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Description
本発明は、アルカリ水溶液に含まれる金属不純物の濃度を、また、必要に応じてケイ素化不純物及び炭酸不純物の濃度も、非常に低い濃度にまで精製することのできるアルカリ水溶液の精製方法に関する。 The present invention relates to a method for purifying an aqueous alkali solution that can purify the concentration of metal impurities contained in the aqueous alkali solution and, if necessary, the concentration of siliconization impurities and carbonic acid impurities to a very low concentration.
アルカリは、シリコンウェーハを製造する際に生成される加工変質層を除去するエッチング工程や、ｐＨ調整及び緩衝目的でコロイダルシリカ等の研磨剤と組み合わせて研磨工程で用いられる。また、アルカリは、研磨工程の後のウェット洗浄でも用いられることが多い。エッチング工程では、水酸化ナトリウムや水酸化カリウム、研磨工程では水酸化ナトリウム、水酸化カリウム、水酸化テトラメチルアンモニウム、アンモニア、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム及び炭酸水素カリウム、洗浄工程ではアンモニアが用いられる。 Alkali is used in the polishing process in combination with an abrasive such as colloidal silica for the purpose of pH adjustment and buffering for the purpose of pH adjustment and buffering, in order to remove the work-affected layer produced when the silicon wafer is produced. Further, the alkali is often used in wet cleaning after the polishing step. In the etching process, sodium hydroxide and potassium hydroxide, in the polishing process, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and in the cleaning process, ammonia is contained. Used.
アルカリ、例えば、水酸化ナトリウムは食塩の電解によって製造されており、生成した水酸化ナトリウムは、数ｐｐｍオーダーの各種金属不純物を含有している。これらの金属不純物中で、例えば、銅とニッケルは、シリコンウェーハに浸透し、残存して電気特性を変化させるなどシリコンウェーハ表面の平坦化を阻害する。そのため、これら金属不純物を含むアルカリ水溶液はエッチング剤として使うことができない。また、カルシウム、マグネシウム、マンガン、鉄、コバルト、亜鉛、アルミニウム、鉛などの金属は、シリコンウェーハの内部には拡散しづらいものの表面に残渣として残り、やはり電気特性などを阻害する。そのため、アルカリエッチング工程や研磨工程において使用される薬液、研磨液にこれら金属不純物が含有していると、その薬液、研磨液の使用が後段の洗浄工程の負荷となる。仮に銅、ニッケルの様なウェーハ内部に拡散しやすい金属とカルシウム、マグネシウム、マンガン、鉄、コバルト、亜鉛、アルミニウム、鉛などのウェーハ表面に留まる金属とについて、その濃度による影響を比較した場合、拡散しやすい金属の濃度は表面に留まる金属にくらべ、時として１／１０〜１／１０００に低減しなければならない場合がある。 Alkali, for example, sodium hydroxide is produced by electrolysis of sodium chloride, and the produced sodium hydroxide contains various metal impurities on the order of several ppm. Among these metal impurities, for example, copper and nickel penetrate into the silicon wafer and remain to inhibit the planarization of the surface of the silicon wafer, for example, by changing electrical characteristics. Therefore, an alkaline aqueous solution containing these metal impurities cannot be used as an etching agent. In addition, metals such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead are difficult to diffuse inside the silicon wafer, but remain as a residue on the surface, which also hinders electrical characteristics and the like. Therefore, when these metal impurities are contained in the chemical solution and polishing liquid used in the alkali etching process and polishing process, the use of the chemical liquid and polishing liquid becomes a burden on the subsequent cleaning process. If the influence of the concentration of a metal such as copper or nickel that easily diffuses inside the wafer and the metal that remains on the wafer surface such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, or lead is compared, the diffusion In some cases, the concentration of the metal that is easy to do has to be reduced to 1/10 to 1/1000 compared to the metal that remains on the surface.
また、アルカリエッチングにおいて、水酸化ナトリウムや水酸化カリウムは、使用量を減らすことによるコスト低減を目的に、循環再利用されることがある。その場合、シリコンウェーハから溶け出したシリコンや空気雰囲気中の酸素がアルカリエッチング液に溶解することで、例えば、アルカリ水溶液が水酸化ナトリウムの場合、ケイ酸ナトリウム（Ｎａ２ＳｉＯ３）が発生し、ウェーハの表面に残渣として残存し、後段の洗浄が困難になってしまう。これを防止する為には、新しいアルカリ液の補充量を増加させ回収率を落とす方法がある。In alkali etching, sodium hydroxide or potassium hydroxide may be recycled for the purpose of reducing costs by reducing the amount used. In that case, silicon dissolved from the silicon wafer and oxygen in the air atmosphere are dissolved in the alkaline etching solution. For example, when the alkaline aqueous solution is sodium hydroxide, sodium silicate (Na 2 SiO 3 ) is generated, It remains as a residue on the surface of the wafer, making subsequent cleaning difficult. In order to prevent this, there is a method of reducing the recovery rate by increasing the replenishment amount of a new alkaline solution.
さらに、空気雰囲気中の二酸化炭素は次式のようにアルカリ水溶液に容易に溶解する。
ＮａＯＨ＋ＣＯ２ → ＮａＨＣＯ３
２ＮａＨＣＯ３ → Ｎａ２ＣＯ３＋Ｈ２
そのため、本来アルカリ成分として純度を保持しなければならないＮａＯＨがＮａ２ＣＯ３となり、エッチングに寄与しなくなるので、二酸化炭素の溶解量を低減する必要がある。また、当然の事ながら、主成分であるアルカリ金属や水酸化物等の濃度が変化するとエッチング処理に多大な影響を及ぼす。Furthermore, carbon dioxide in the air atmosphere is easily dissolved in an alkaline aqueous solution as shown in the following formula.
NaOH + CO 2 → NaHCO 3
2NaHCO 3 → Na 2 CO 3 + H 2
Therefore, NaOH that originally has to maintain purity as an alkali component becomes Na 2 CO 3 and does not contribute to etching, so it is necessary to reduce the amount of dissolved carbon dioxide. As a matter of course, if the concentration of the alkali metal or hydroxide as the main component changes, the etching process is greatly affected.
しかし、研磨工程のスラリー中のようにＮａ２ＳｉＯ３やＮａ２ＣＯ３が混入していても殆ど影響を及ぼさない状態や、あるいは必要として添加されている状態からアルカリ水溶液に含まれる金属不純物だけを選択的に低減しなければならない場合もある。アルカリを精製する手段として、再結晶法、蒸留法等が挙げられるが、何れもかなりな熱エネルギーを要し、装置も大掛かりで、運転管理も複雑となる。However, only the metal impurities contained in the alkaline aqueous solution from the state in which Na 2 SiO 3 or Na 2 CO 3 is mixed, such as in the slurry of the polishing process, has little effect or is added as necessary. May have to be reduced selectively. As means for purifying the alkali, there are a recrystallization method, a distillation method, and the like, but all of them require considerable heat energy, a large apparatus, and complicated operation management.
これに対し、容易に低コストでアルカリを精製する手段として、例えば、金属不純物を含んだ高濃度水酸化ナトリウム水溶液を、ヤシ殻系活性炭を硝酸で処理した後に賦活したものと接触させ、金属不純物を吸着除去する方法が提案されている（特開２００４−３４４７１５号公報）。しかし、これでは専用の活性炭を準備する必要があるため、コスト上昇を招いてしまう。また、鉄を１００ｐｐｂ程度にまで精製できるが、銅やニッケルについては１００ｐｐｂ程度にまで精製できるだけで要求水準を満たすに至っていない。また、活性炭は素材に含まれている亜鉛やアルミなどの金属不純物が溶出し、これらは硝酸で賦活しても低減することは困難である。従って金属不純物の除去要求項目が鉄に限定されれば良いが、銅やニッケル等多項目になった場合は使用が困難となる。 On the other hand, as a means for easily purifying the alkali at low cost, for example, a high concentration sodium hydroxide aqueous solution containing metal impurities is brought into contact with the activated carbon shell activated carbon after being treated with nitric acid. Has been proposed (Japanese Patent Laid-Open No. 2004-344715). However, this necessitates the preparation of dedicated activated carbon, which leads to an increase in cost. Moreover, although iron can be refined to about 100 ppb, copper and nickel can only be refined to about 100 ppb and do not satisfy the required level. Moreover, activated carbon elutes metal impurities such as zinc and aluminum contained in the material, and these are difficult to reduce even if activated by nitric acid. Accordingly, it is sufficient that the metal impurity removal requirement item is limited to iron, but it becomes difficult to use when there are many items such as copper and nickel.
さらに、水酸化ナトリウム水溶液に含まれる金属不純物を低減する方法として、陽イオン交換膜を用いた水酸化ナトリウム水溶液の電解による精製方法が知られている（特開２００２−３１７２８５号公報）。この方法によれば、水酸化ナトリウム水溶液中の金属不純物は１０ｐｐｂ以下にできるとされている。しかし、この方法は設備投資が高額となり、装置が複雑になるために精製コストが高く、運転管理が難しいという欠点がある。 Furthermore, as a method for reducing metal impurities contained in an aqueous sodium hydroxide solution, a purification method by electrolysis of an aqueous sodium hydroxide solution using a cation exchange membrane is known (Japanese Patent Laid-Open No. 2002-317285). According to this method, it is said that the metal impurities in the sodium hydroxide aqueous solution can be 10 ppb or less. However, this method has the disadvantages of high capital investment, complicated equipment, high purification costs, and difficult operation management.
さらに、水酸化ナトリウム、水酸化カリウム、水酸化テトラメチルアンモニウム、アンモニア、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウムなどを含むアルカリ水溶液は、単独での使用以外に、例えば、研磨用スラリーの添加剤として使用される。しかし、金属不純物を仮に１００ｐｐｂ以下に低減した高純度のアルカリ水溶液を使用箇所まで高純度の状態で維持する為には、アルカリ水溶液の製造工場やタンクローリ等の移送用手段、アルカリ水溶液を使用するウェーハ製造工場や半導体デバイス製造工場において、接続・供給配管やドラム・タンク等の容器を金属溶出が少ないフッ素樹脂等の高価な素材でライニングしたり、その素材を用いて製造したりしなければならない。また、ウェーハ製造工場や半導体デバイス製造工場で使用したアルカリ水溶液をリサイクルしたい場合でも、製造工程等から副生成的に発生する金属により汚染を受け、再使用が不可能な為、廃棄せざるを得ない。 Further, an alkaline aqueous solution containing sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc. is used, for example, as a slurry for polishing. Used as an additive. However, in order to maintain a high-purity alkaline aqueous solution in which metal impurities are reduced to 100 ppb or less in a high-purity state up to the point of use, a transportation means such as an alkaline aqueous solution manufacturing plant or a tank truck, a wafer using an alkaline aqueous solution In manufacturing factories and semiconductor device manufacturing factories, containers such as connection / supply pipes and drums / tanks must be lined with or made of expensive materials such as fluororesins with little metal elution. Even if it is desired to recycle the alkaline aqueous solution used in wafer manufacturing plants or semiconductor device manufacturing plants, it must be discarded because it is contaminated by by-product metal from the manufacturing process and cannot be reused. Absent.
また、従来、金属不純物の除去に用いられている陽イオン交換樹脂を用いた水溶液の精製法では、高濃度にアルカリ成分が含まれている場合には、アルカリ成分も金属不純物と同様に樹脂と反応するため、金属不純物を選択的に除去することができない。したがって、さらに適切な処理を施さないと主成分であるアルカリ成分の濃度が変化してしまう恐れがある。
上述したように、従来のアルカリ水溶液は、金属不純物を含んでいるため、シリコンウェーハのエッチング、研磨工程、洗浄工程のような用途に使用する為には一般的な製造方法、例えば、電解法等、だけで製造されたままでは使用は困難である。そのため、再結晶や蒸留、陽イオン交換膜法などを用いざるを得ない。しかし、これらの方法は、エネルギー効率が悪く、装置も大型、複雑で運転管理が容易ではなく、精製コストも高くなってしまう。このため、特に、カルシウム、マグネシウム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、アルミニウム、鉛などの金属不純物を極力少なくすることができる簡便なアルカリ水溶液の精製方法の開発が望まれている。また、主成分であるアルカリ水溶液の濃度を変化させずに、ケイ酸アルカリ、炭酸不純物の除去や、金属不純物を選択的に除去しなければならない。 As described above, since the conventional alkaline aqueous solution contains metal impurities, it is a general manufacturing method such as an electrolytic method for use in applications such as etching, polishing and cleaning of silicon wafers. It is difficult to use it as it is. Therefore, recrystallization, distillation, a cation exchange membrane method, etc. must be used. However, these methods are inefficient in energy, the apparatus is large and complicated, operation management is not easy, and purification costs are high. For this reason, in particular, development of a simple method for purifying an alkaline aqueous solution that can reduce metal impurities such as calcium, magnesium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, and lead as much as possible is desired. Further, it is necessary to remove alkali silicate and carbonic acid impurities and to selectively remove metal impurities without changing the concentration of the alkaline aqueous solution as the main component.
本発明は、かかる従来の課題を解決すべくなされたもので、シリコンウェーハのエッチング、研磨工程、洗浄工程のような用途に使用される、比較的高濃度のアルカリ水溶液に含まれる前述不純物を簡便な方法で速やかに除去することのできるアルカリ水溶液の精製方法を提供することを目的とする。アルカリ水溶液としては、水酸化ナトリウム、水酸化カリウム、水酸化テトラメチルアンモニウム、アンモニア、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム及び炭酸水素カリウム及びその他のアルカリを含むものが挙げられる。 The present invention has been made in order to solve the above-described conventional problems, and can easily remove the impurities contained in a relatively high concentration alkaline aqueous solution used for applications such as etching, polishing and cleaning of silicon wafers. It is an object of the present invention to provide a method for purifying an alkaline aqueous solution that can be quickly removed by a simple method. Examples of the alkaline aqueous solution include those containing sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and other alkalis.
本発明のアルカリ水溶液の精製方法は、金属不純物を含むアルカリ水溶液を、繊維状又はビーズ状の強塩基性陰イオン交換体、弱塩基性陰イオン交換体及びキレート化材並びに賦活させた後に硝酸に接触させた活性炭から選択される少なくとも一種の材料に接触させることを特徴とする。 The method for purifying an alkaline aqueous solution of the present invention comprises an alkaline aqueous solution containing metal impurities, a fibrous or beaded strong basic anion exchanger, a weak basic anion exchanger, a chelating agent, and a nitric acid after activation. It is made to contact with at least 1 type of material selected from the contacted activated carbon.
また、本来アルカリ水溶液（中でも代表的ものとして水酸化ナトリウム水溶液等）は、強塩基性陰イオン交換体及び弱塩基性陰イオン交換体等の再生剤として使用されるものである。しかし、本発明では、予め強塩基性陰イオン交換体及び弱塩基性陰イオン交換体の末端基をＯＨ型に処理しておくことで、アルカリ水溶液中では陰イオンとして存在する多くの金属化学種（不純物）を取り除くことが可能となり、かつアルカリ水溶液の濃度が変化しないことを特徴とする。 In addition, alkaline aqueous solutions (particularly, sodium hydroxide aqueous solutions, etc., are typically used as regenerants for strong basic anion exchangers and weak basic anion exchangers). However, in the present invention, by treating the end groups of the strongly basic anion exchanger and weakly basic anion exchanger with OH type in advance, many metal chemical species that exist as anions in an alkaline aqueous solution are used. (Impurities) can be removed, and the concentration of the aqueous alkali solution does not change.
更に、ＯＨ型に処理した繊維状又はビーズ状の強塩基性陰イオン交換体は、陰イオンとして存在する多くの金属不純物以外にも、ケイ酸化合物、炭酸根、硫酸根、塩素根等の不純物を除去することが可能である。また、ケイ素化不純物、炭酸不純物と金属不純物を含むアルカリ水溶液から、繊維状又はビーズ状の弱塩基性陰イオン交換体及びキレート化材並びに賦活させた後に硝酸に接触させた活性炭から選択される少なくとも一種の材料中に接触させ、金属不純物だけを除去することができる。 Furthermore, the fibrous or bead-like strong basic anion exchanger treated to OH type has impurities such as silicate compounds, carbonate radicals, sulfate radicals, chlorine radicals in addition to many metal impurities present as anions. Can be removed. Further, at least selected from an alkaline aqueous solution containing siliconized impurities, carbonic acid impurities and metal impurities, fibrous or beaded weakly basic anion exchangers and chelating agents, and activated carbon that has been activated and then contacted with nitric acid Only metal impurities can be removed by contact in a kind of material.
アルカリ水溶液を、繊維状又はビーズ状の強塩基性陰イオン交換体、弱塩基性陰イオン交換体及びキレート化材並びに賦活させた後に硝酸に接触させた活性炭から選択される少なくとも一種、目的によっては二種以上の材料に接触させるには、例えば、これら材料をカラム又は塔中に充填して、この中に精製すべきアルカリ水溶液を通水するか、精製すべきアルカリ水溶液を収容した反応槽中に、これらの材料を添加して精製すべきアルカリ水溶液を流動化させた後濾過すればよい。このとき、繊維状又はビーズ状の強塩基性陰イオン交換体、弱塩基性陰イオン交換体及びキレート化材はカートリッジフィルター状にしてもよい。 At least one selected from an aqueous alkaline solution selected from a fibrous or beaded strong basic anion exchanger, a weak basic anion exchanger, a chelating agent, and activated carbon that has been activated and then contacted with nitric acid, depending on the purpose In order to contact two or more kinds of materials, for example, these materials are packed in a column or a column, and an alkaline aqueous solution to be purified is passed therethrough, or in a reaction vessel containing an alkaline aqueous solution to be purified. In addition, these materials may be added and the aqueous alkaline solution to be purified may be fluidized and then filtered. At this time, the fibrous or beaded strong basic anion exchanger, weak basic anion exchanger, and chelating material may be in the form of a cartridge filter.
また、本発明は、低濃度から高濃度まで（例えば、アルカリ濃度０．０１〜５０重量％）のアルカリ水溶液に対して適用することができる。 In addition, the present invention can be applied to an alkaline aqueous solution having a low concentration to a high concentration (for example, an alkali concentration of 0.01 to 50% by weight).
本発明に使用する強塩基性陰イオン交換体、弱塩基性陰イオン交換体及びキレート化材としては、耐アルカリ性の合成樹脂繊維又は合成樹脂ビーズに、強塩基性陰イオン交換基、弱塩基性陰イオン交換基又はキレート官能基を結合させたものを使用することができる。また、これらの構造としては、ゲル型、ハイポーラス型、ポーラス型、マクロポーラス型又はマクロレテキュラ型が挙げられ、特に、比表面積の大きいハイポーラス型、ポーラス型、マクロポーラス型又はマクロレテキュラ型が好ましいものとして挙げられる。 As the strongly basic anion exchanger, weakly basic anion exchanger and chelating agent used in the present invention, an alkali-resistant synthetic resin fiber or synthetic resin bead, a strongly basic anion exchange group, a weakly basic Those having an anion exchange group or a chelate functional group bound thereto can be used. Further, examples of these structures include gel type, high porous type, porous type, macroporous type, and macroreticular type, and in particular, high porous type, porous type, macroporous type, or macroreticular type having a large specific surface area. A mold is preferable.
耐アルカリ性の合成樹脂繊維又は合成樹脂ビーズのベースとなる合成樹脂としては、ポリビニルアルコール、スチレン−ジビニルベンゼン共重合体、ポリサルホン、ポリフェニルサルホン、ポリヒドロキシメタクリレート、ポリエチレン、ポリプロピレン、アラミド、ＰＦＡ（テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体）、ＰＴＦＥ（ポリテトラフルオロエチレン）系樹脂等が例示されるが、汎用性、価格の点でポリビニルアルコール、スチレン−ジビニルベンゼン共重合体、アラミド、ポリサルホン、ポリフェニルサルホン等が好適である。これらの合成樹脂は、高濃度のアルカリ水溶液、例えば、５０％水酸化ナトリウム水溶液に対しても高い耐性を有している。これらは、単独でも複数種類を組み合わせても使用することができる。 The synthetic resin used as the base of the alkali-resistant synthetic resin fiber or synthetic resin beads includes polyvinyl alcohol, styrene-divinylbenzene copolymer, polysulfone, polyphenylsulfone, polyhydroxymethacrylate, polyethylene, polypropylene, aramid, PFA (tetra Fluoroethylene / perfluoroalkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene) resin, etc. are exemplified, but in terms of versatility and price, polyvinyl alcohol, styrene-divinylbenzene copolymer, aramid, polysulfone, Polyphenylsulfone and the like are preferred. These synthetic resins have high resistance to a high concentration aqueous alkali solution, for example, a 50% aqueous sodium hydroxide solution. These can be used alone or in combination of a plurality of types.
このようなベースとなる合成樹脂に結合される強塩基性陰イオン交換基としては、第４級アミン基が例示され、弱塩基性陰イオン交換基としては第１級アミン基、第２級アミン基、第３級アミン基等が例示され、キレート化基としてはエチレンジアミン三酢酸基のようなポリアミノポリカルボン酸基、イミノ二酢酸基、イミノ酢酸基、アミノ燐酸基、燐酸基、ポリアミン基、チオ化合物類基等が例示される。 Examples of the strong basic anion exchange group bonded to the base synthetic resin include a quaternary amine group, and the weak basic anion exchange group includes a primary amine group and a secondary amine group. Groups, tertiary amine groups and the like. Examples of chelating groups include polyaminopolycarboxylic acid groups such as ethylenediaminetriacetic acid groups, iminodiacetic acid groups, iminoacetic acid groups, aminophosphoric acid groups, phosphoric acid groups, polyamine groups, thiols. Compound groups and the like are exemplified.
本発明で使用する硝酸で処理した活性炭の炭素材料は、ヤシ殻、石炭、石油ピッチ、フェノール樹脂などいずれでもよく、活性炭は繊維状又はビーズ状などの形状のものを使用することができる。本発明で活性炭を処理する硝酸濃度は、６．５Ｎ以上が好ましく、処理時間として１時間以上活性炭と接触させることが好ましい。また本発明で使用する繊維状又はビーズ状の硝酸で処理した活性炭は、カートリッジフィルター状にしてもよい。 The carbon material of activated carbon treated with nitric acid used in the present invention may be any of coconut shell, coal, petroleum pitch, phenol resin, etc., and the activated carbon may be in the form of fibers or beads. The concentration of nitric acid for treating activated carbon in the present invention is preferably 6.5 N or more, and the treatment time is preferably contacted with activated carbon for 1 hour or more. The activated carbon treated with the fibrous or beaded nitric acid used in the present invention may be in the form of a cartridge filter.
これらの使用方法としては次のものが挙げられる。強塩基性陰イオン交換体、弱塩基性陰イオン交換体、キレート化材及び硝酸で処理した活性炭から選ばれる材料のうち１種又は２種以上をカラム又は塔中に充填し、２種以上の場合には混合又は積層の形で充填し、あるいは２種以上を各々個別にカラム又は塔中に充填した後に連結し、これらに精製すべきアルカリ水溶液を通液して使用することができる。
また、強塩基性陰イオン交換体、弱塩基性陰イオン交換体、キレート化材、硝酸で処理した活性炭から選ばれる材料のうち１種又は２種以上を同一反応槽内に積層又は混合し、精製すべきアルカリ水溶液を流動化させ、次いでフィルターで濾過し使用することができる。The following are mentioned as these usage methods. One or more materials selected from strong basic anion exchangers, weakly basic anion exchangers, chelating materials and activated carbon treated with nitric acid are packed in a column or tower, and two or more In some cases, the mixture can be packed or stacked, or two or more of them can be individually packed into a column or column and then connected, and an aqueous alkali solution to be purified can be passed through them for use.
Also, one or more materials selected from strong basic anion exchangers, weak basic anion exchangers, chelating materials, and activated carbon treated with nitric acid are laminated or mixed in the same reaction tank, The aqueous alkaline solution to be purified can be fluidized and then filtered and used.
本発明の方法は、アルカリ水溶液のアルカリの濃度が高濃度であっても使用できることが特徴であり、アルカリの濃度が０．０１重量％以上、特に０．１重量％以上であっても精製が可能である。 The method of the present invention is characterized in that it can be used even when the alkali concentration of the aqueous alkali solution is high, and purification is possible even when the alkali concentration is 0.01 wt% or more, particularly 0.1 wt% or more. Is possible.
本発明の方法によれば、金属除去処理を行ったアルカリ水溶液中の金属濃度、例えば、カルシウム、マグネシウム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、アルミニウム、鉛などの濃度を５０ｐｐｂ以下に精製することが可能である。
本発明による金属不純物の除去は、例えば、図１に示すようにアルカリの濃度が高濃度のもとでは、金属は負電荷の水酸化物錯イオンを形成していることから、陰イオン交換体を用いることができ、さらに、アルカリ水溶液中に多量に存在する陰イオンである水酸化物イオン共存下でも陰イオン交換基と親和性の高い水酸化物錯イオンが選択的に吸着除去されることによると考えられる。
このとき、キレート化材の場合には、負電荷の水酸化物錯イオンは、その水酸化物イオンの代わりにキレート化材が金属イオンと結合することで除去されると考えられ、金属イオンと配位子である水酸化物イオンとの結合よりも強いキレート力を有する官能基を用いることが好ましい。According to the method of the present invention, the metal concentration in the alkaline aqueous solution subjected to the metal removal treatment, for example, the concentration of calcium, magnesium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, lead, etc. is purified to 50 ppb or less. Is possible.
The removal of metal impurities according to the present invention can be performed, for example, as shown in FIG. 1, since the metal forms a negatively charged hydroxide complex ion under a high alkali concentration. In addition, hydroxide complex ions having high affinity with anion exchange groups can be selectively adsorbed and removed even in the presence of hydroxide ions, which are anions present in large amounts in an alkaline aqueous solution. It is thought that.
At this time, in the case of the chelating material, it is considered that the negatively charged hydroxide complex ions are removed by bonding the chelating material to the metal ions instead of the hydroxide ions. It is preferable to use a functional group having a chelating power stronger than the bond with a hydroxide ion that is a ligand.
本発明によれば、低濃度から高濃度までのアルカリ水溶液に含まれる金属不純物を簡便な方法で速やかに除去することができる。 According to the present invention, metal impurities contained in an alkaline aqueous solution having a low concentration to a high concentration can be quickly removed by a simple method.
具体的には、銅及びニッケルの場合、その濃度を３ｐｐｂ以下、条件によっては０．１ｐｐｂ以下まで、除去率では５０％以上の除去を達成することが可能である。また、本発明は実施例で示す水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、アンモニア、水酸化テトラメチルアンモニウム溶液の他、水酸化リチウム、水酸化セシウム等のアルカリ金属水酸化物溶液や水酸化バリウム等のアルカリ土類金属水酸化物溶液、セルロース等のアルカリ性水溶性高分子水溶液、酢酸アンモニウムなどの有機アルカリ水溶液の精製にも適用することができる。 Specifically, in the case of copper and nickel, it is possible to achieve removal of 50% or more in terms of the removal rate, with the concentration being 3 ppb or less, depending on conditions, to 0.1 ppb or less. In addition, the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, tetramethylammonium hydroxide solution, lithium hydroxide, cesium hydroxide, etc. It can also be applied to the purification of alkaline earth metal hydroxide solutions such as barium hydroxide, alkaline earth metal hydroxide solutions such as barium hydroxide, alkaline water-soluble polymer aqueous solutions such as cellulose, and organic alkaline aqueous solutions such as ammonium acetate.
本発明が有効であるアルカリ水溶液の濃度は、水酸化ナトリウムでは０．０１〜５０重量％、水酸化カリウムでは０．０１〜５０重量％、炭酸ナトリウムでは０．０１〜２３重量％、炭酸カリウムでは０．０１〜５０重量％、炭酸水素ナトリウムでは０．０１〜８重量％、炭酸水素カリウムでは０．０１〜５０重量％、アンモニアでは０．０１〜３０重量％、水酸化テトラメチルアンモニウムでは０．０１〜２５重量％の濃度が好ましく、より好ましくは水酸化ナトリウムでは０．１〜５０重量％、水酸化カリウムでは０．１〜５０重量％、炭酸ナトリウムでは０．１〜２３重量％、炭酸カリウムでは０．１〜５０重量％、炭酸水素ナトリウムでは０．１〜５０重量％、炭酸水素カリウムでは０．１〜５０重量％、アンモニアでは０．１〜３０重量％、水酸化テトラメチルアンモニウムでは０．１〜２５重量％の濃度である。特に、水酸化ナトリウムでは５〜５０重量％、水酸化カリウムでは５〜５０重量％、炭酸ナトリウムでは５〜２３重量％、炭酸カリウムでは５〜５０重量％、炭酸水素ナトリウムでは５〜８重量％、炭酸水素カリウムでは５〜５０重量％、アンモニアでは５〜３０重量％、水酸化テトラメチルアンモニウムでは５〜２５重量％の高濃度領域が好ましく、このとき本発明が最も効果を発揮する。 The concentration of the aqueous alkaline solution in which the present invention is effective is 0.01 to 50% by weight for sodium hydroxide, 0.01 to 50% by weight for potassium hydroxide, 0.01 to 23% by weight for sodium carbonate, 0.01 to 50 wt%, 0.01-8 wt% for sodium hydrogen carbonate U beam, from 0.01 to 50 wt% potassium hydrogen carbonate, 0.01 to 30 wt% with ammonia, the tetramethylammonium hydroxide A concentration of 0.01 to 25% by weight is preferred, more preferably 0.1 to 50% by weight for sodium hydroxide, 0.1 to 50% by weight for potassium hydroxide, 0.1 to 23% by weight for sodium carbonate, 0.1 to 50% by weight potassium carbonate, 0.1 to 50 wt% in sodium hydrogen carbonate U beam, 0.1 to 50 wt% potassium hydrogen carbonate, 0.1 to 3 in ammonia Wt%, the tetramethylammonium hydroxide at a concentration of 0.1 to 25 wt%. In particular, 5 to 50% by weight sodium hydroxide, 5-50 wt% potassium hydroxide, 5 to 23 wt% sodium carbonate, 5 to 50 wt% potassium carbonate, 5-8 weight by sodium hydrogen carbonate U beam %, 5 to 50% by weight for potassium hydrogen carbonate, 5 to 30% by weight for ammonia, and 5 to 25% by weight for tetramethylammonium hydroxide are preferred. The present invention is most effective.
次に、本発明の実施例について説明する。 Next, examples of the present invention will be described.
試料用のアルカリ水溶液として、旭硝子（株）製の５０％水酸化ナトリウム水溶液、旭硝子（株）製の４８％水酸化カリウム水溶液、和光純薬工業（株）製特級の炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、関東化学（株）製の２８〜３０％の特級アンモニア水、水酸化テトラメチルアンモニウム五水和物、セルロース、富山薬品工業（株）製の７０％酢酸アンモニウム水溶液を用いて以下の方法で精製した。なお、実験を行う際の溶解、希釈等の操作にはすべて超純水を用いた。また、特に濃度の依存性を見る為に、希釈し金属不純物量が少なくなった０．１重量％及び０．０１重量％水酸化ナトリウムについては、検討対象である金属をそれぞれ１０ｐｐｂ前後になる様に添加して精製処理を実施した。 As an alkaline aqueous solution for the sample, 50% aqueous sodium hydroxide solution manufactured by Asahi Glass Co., Ltd., 48% potassium hydroxide aqueous solution manufactured by Asahi Glass Co., Ltd., special grade sodium carbonate, potassium carbonate, carbonic acid manufactured by Wako Pure Chemical Industries, Ltd. Sodium hydrogen, potassium hydrogen carbonate, 28-30% special grade ammonia water manufactured by Kanto Chemical Co., Ltd., tetramethylammonium hydroxide pentahydrate, cellulose, 70% ammonium acetate aqueous solution manufactured by Toyama Pharmaceutical Co., Ltd. And purified by the following method. Note that ultrapure water was used for all operations such as dissolution and dilution during the experiment. In particular, in order to see the dependency of concentration, 0.1 wt% and 0.01 wt% sodium hydroxide diluted to reduce the amount of metal impurities, the metal to be studied is about 10 ppb each. And purified.
金属不純物の測定は、ＩＣＰ−ＭＳ（パーキンエルマー社製 ＥＬＡＮＤＲＣ−II）により行った。また、ケイ素化合物並びに無機炭酸の測定は、ケイ素化合物をＩＣＰ−ＡＥＳ（（株）リガク製 ＣＩＲＯＳ１２０）、無機炭酸をＮＤＩＲ法（（株）島津製作所製 ＴＯＣ５０００Ａ）にて行った。なお、以下の実施例及び比較例で使用した処理装置及び処理体は、次の通りのものである。 Measurement of metal impurities was performed by ICP-MS (ELANDRC-II manufactured by PerkinElmer). The silicon compound and inorganic carbonic acid were measured by ICP-AES (CIROS120 manufactured by Rigaku Corporation) for the silicon compound and NDIR method (TOC5000A manufactured by Shimadzu Corporation) for the inorganic carbonic acid. In addition, the processing apparatus and the processing body which were used by the following examples and comparative examples are as follows.
処理装置：
処理体充填カラム ３／４インチＰＦＡカラム ２００ｍｍ
（ＰＦＡ：テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体）
試験系及び使用タンクの材質 ＰＴＦＥ（ポリテトラフルオロエチレン）
ポンプ （（株）イワキ社製 ベローズポンプ ＦＳ−１５ＨＴ）Processing equipment:
Processing body packed column 3/4 inch PFA column 200mm
(PFA: tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer)
Test system and tank material PTFE (Polytetrafluoroethylene)
Pump (Iwaki Co., Ltd. Bellows Pump FS-15HT)
使用した処理体：
（Ａ）強塩基性陰イオン交換繊維：
メーカー：（株）ニチビ
商品名：ＩＥＦ−ＳＡ
母材：ポリビニルアルコール
官能基：第４級アミン基
形状：直径１００μｍ、長さ２〜５ｍｍ繊維状Used treatment body:
(A) Strongly basic anion exchange fiber:
Manufacturer: Nichibi Corporation
Product Name: IEF-SA
Base material: Polyvinyl alcohol
Functional group: quaternary amine group
Shape: Diameter 100μm, length 2-5mm fiber
（Ｂ）弱塩基性イオン交換繊維：
メーカー：（株）ニチビ
商品名：ＩＥＦ−ＷＡ
母材：ポリビニルアルコール
官能基：第１級〜第３級アミン基
形状：直径１００μｍ、長さ２〜５ｍｍ繊維状(B) Weakly basic ion exchange fiber:
Manufacturer: Nichibi Corporation
Product Name: IEF-WA
Base material: Polyvinyl alcohol
Functional group: primary to tertiary amine group
Shape: Diameter 100μm, length 2-5mm fiber
（Ｃ）弱塩基性陰イオン交換樹脂：
メーカー：ロームアンドハースジャパン（株）
商品名：ＤＵＯＬＩＴＥ Ａ３７８Ｄ
母材：スチレン・ジビニルベンゼン共重合体
官能基：第１級〜第３級アミン基
形状：直径４００〜６５０μｍのビーズ状(C) Weakly basic anion exchange resin:
Manufacturer: Rohm and Haas Japan Co., Ltd.
Product Name: DUOLITE A378D
Base material: Styrene / divinylbenzene copolymer
Functional group: primary to tertiary amine group
Shape: Bead shape with a diameter of 400-650 μm
（Ｄ）エチレンジアミン三酢酸・イミノ二酢酸混合キレート樹脂
メーカー：（株）日立ハイテクノロジー
商品名：ノビアスＣＨＥＬＡＴＥ−ＰＡ１
母材：ポリヒドロキシメタクリレート
官能基：エチレンジアミン三酢酸基、イミノ二酢酸基
形状：４５〜９０μｍのビーズ状(D) Ethylenediaminetriacetic acid / iminodiacetic acid mixed chelate resin
Manufacturer: Hitachi High-Technology Corporation
Product Name: NOBIAS CHELATE-PA1
Base material: Polyhydroxymethacrylate
Functional groups: ethylenediaminetriacetic acid group, iminodiacetic acid group
Shape: 45-90 μm beads
（Ｅ）キレート繊維：
メーカー：（株）ニチビ
商品名：ＩＥＦ−ＩＡｃ
母材：ポリビニルアルコール
官能基：イミノ酢酸基
形状：直径１００μｍ、長さ２〜５ｍｍ繊維状(E) Chelate fiber:
Manufacturer: Nichibi Corporation
Product Name: IEF-IAc
Base material: Polyvinyl alcohol
Functional group: iminoacetic acid group
Shape: Diameter 100μm, length 2-5mm fiber
（Ｆ）強塩基性陰イオン交換樹脂：
メーカー：ロームアンドハースジャパン（株）
商品名：Ａ２０１ＣＬ
母材：スチレン・ジビニルベンゼン共重合体
官能基：第４級アミン基
形状：粒径５００〜７５０μｍのビーズ状(F) Strongly basic anion exchange resin:
Manufacturer: Rohm and Haas Japan Co., Ltd.
Product name: A201CL
Base material: Styrene / divinylbenzene copolymer
Functional group: quaternary amine group
Shape: Bead shape with particle size of 500-750 μm
（Ｇ）強酸性陽イオン交換樹脂：
メーカー：ロームアンドハースジャパン（株）
商品名：ＤＵＯＬＩＴＥ Ｃ２５５ＬＦＨ
母材：スチレン・ジビニルベンゼン共重合体
官能基：スルホン酸基
形状：粒径５５０μｍのビーズ状(G) Strongly acidic cation exchange resin:
Manufacturer: Rohm and Haas Japan Co., Ltd.
Product Name: DUOLITE C255LFH
Base material: Styrene / divinylbenzene copolymer
Functional group: sulfonic acid group
Shape: Bead shape with particle size of 550μm
（Ｈ）活性炭：
メーカー：三菱化学カルゴン（株）
商品名：Ｗ １０−３０
母材：ヤシ殻系
形状：粒径１０〜３５ｍｅｓｈ(H) Activated carbon:
Manufacturer: Mitsubishi Chemical Calgon Co., Ltd.
Product Name: W 10-30
Base material: Coconut shell system
Shape: particle size 10-35 mesh
（Ｉ）活性炭：
メーカー：三菱化学カルゴン（株）
商品名：Ｆｉｌｔｒａｓｏｒｂ ４００
母材：石炭系
形状：粒径１０〜３５ｍｅｓｈ(I) Activated carbon:
Manufacturer: Mitsubishi Chemical Calgon Co., Ltd.
Product Name: Filtrasorb 400
Base material: Coal
Shape: particle size 10-35 mesh
（Ｊ）限外濾過膜：
メーカー：（株）アドバンテック
商品名：ウルトラフィルターＱ０１００
母材：ポリサルホン
分画分子量：ＭＷＣＯ １００００
形状：直径７６ｍｍ薄膜(J) Ultrafiltration membrane:
Manufacturer: Advantech Co., Ltd.
Product name: Ultra Filter Q0100
Base material: Polysulfone
Molecular weight cut-off: MWCO 10,000
Shape: 76mm diameter thin film
（Ｋ）活性炭フィルター：
メーカー：（株）ロキテクノ
商品名：マイクロチャコールＭＣＫタイプ
母材：繊維状活性炭、ヤシ殻活性炭(K) Activated carbon filter:
Manufacturer: Loki Techno Co., Ltd.
Product Name: Micro Charcoal MCK Type
Base material: Fibrous activated carbon, coconut shell activated carbon
なお、以下の実施例及び比較例においては、使用した処理体は、上記（Ａ），（Ｂ），……の略号で表示した。ここで処理に用いた（Ａ），（Ｂ），（Ｃ），（Ｆ）のイオン交換体は、末端基が９０％以上ＯＨ基となっているものを使用した。 In the following examples and comparative examples, the used treatment bodies are indicated by the abbreviations (A), (B),. Here, the ion exchangers (A), (B), (C), and (F) used in the treatment were those having terminal groups of 90% or more as OH groups.
実施例１〜８、比較例２
（使用器具等の洗浄）
ＰＴＦＥ製タンク(容積１２００ｍｌ)、ＰＦＡ製カラム（φ３／４インチ、長さ２００ｍｍ）、サンプリング用ＰＥ（ポリエチレン）製容器(容積１０００ｍｌ)の全てを、金属汚染を排除するため、予め、１Ｎ硝酸に１時間以上浸漬させた後、超純水で流水洗浄した。洗浄に用いた硝酸は関東化学（株）製の電子工業用グレード(ＥＬ)であり、約１Ｎとなるよう超純水で希釈したものである。超純水は超純水製造システムで製造された金属含有量が各金属１ｐｐｔ以下、Ｓｉ５０ｐｐｔ以下、無機炭素１０ｐｐｂ以下のものである。Examples 1-8, Comparative Example 2
(Washing equipment used)
In order to eliminate metal contamination, the PTFE tank (volume: 1200 ml), PFA column (φ3 / 4 inch, length: 200 mm) and sampling PE (polyethylene) container (volume: 1000 ml) were all preliminarily washed with 1N nitric acid. After immersing for 1 hour or longer, it was washed with running ultrapure water. The nitric acid used for washing is an electronic industrial grade (EL) manufactured by Kanto Chemical Co., Inc., which is diluted with ultrapure water so as to be about 1N. The ultrapure water has a metal content of 1 ppt or less, Si50 ppt or less, and
上記洗浄方法で洗浄された器具をＰＴＦＥ製タンク、ＰＦＡカラム、の順にＰＦＡ配管で接続した。このシステムに超純水を通水しＰＦＡカラム出口でＰＥ容器に受けた時の試験系ブランクの分析結果を表１に示す。表から明らかなように、このシステムによる汚染は全くない。 The appliances cleaned by the above-described cleaning method were connected by PFA piping in the order of a PTFE tank and a PFA column. Table 1 shows the analysis results of the test system blank when ultrapure water was passed through this system and received in the PE container at the PFA column outlet. As can be seen from the table, there is no contamination by this system.
（処理操作）
対象のアルカリ水溶液の成分濃度が変化しないように末端基に処理を施した（Ａ）〜（Ｇ）の各種吸着体をＰＦＡカラム（φ３／４インチ、長さ２００ｍｍ）に充填した。また、（Ｈ）、（Ｉ）の活性炭は予め６．５Ｎ硝酸中に１時間浸漬洗浄した後に使用した。
充填は十分洗浄したＰＴＦＥ製の押し込み棒で軽く吸着体を押し込みながら徐々に充填し、カラム内部が密になるようにして充填した。(Processing operation)
Various adsorbents (A) to (G) that had been treated on the end groups so as not to change the component concentration of the target aqueous alkaline solution were packed in a PFA column (φ3 / 4 inch, length 200 mm). The activated carbons (H) and (I) were used after being immersed and washed in 6.5N nitric acid for 1 hour in advance.
The packing was carried out gradually by pushing the adsorbent lightly with a well-washed PTFE push rod so that the inside of the column became dense.
吸着体が充填されたＰＦＡカラムに超純水を１０ｍｌ／ｍｉｎで１２時間以上通液し、溶出してくる金属や有機物を十分洗い流した。ＰＴＦＥ製タンクの内部に水滴が残留しないようによく水を切り、試料のアルカリ水溶液である５０％ＮａＯＨを投入した。アルカリ水溶液が投入されたＰＴＦＥ製タンクと洗浄済みの充填物が詰まったＰＦＡカラムを１／４インチのＰＦＡチューブで接続し、ＰＦＡカラム出口にサンプリング容器を設置した。 Ultrapure water was passed through the PFA column packed with the adsorbent at 10 ml / min for 12 hours or more to sufficiently wash away the eluted metals and organic substances. Water was thoroughly drained so that no water droplets remained inside the PTFE tank, and 50% NaOH, which was an alkaline aqueous solution of the sample, was added. A PTFE tank filled with an alkaline aqueous solution and a PFA column packed with washed packing were connected by a 1/4 inch PFA tube, and a sampling vessel was installed at the PFA column outlet.
ＰＴＦＥ製タンクの上部から窒素ガスを導入し、容器内部の圧力を０．２ＭＰａまで加圧し流量調整バルブを操作してＰＦＡカラム出口から流出するアルカリ水溶液の流出速度を５ｍｌ／ｍｉｎ以下に調整した。流出してくるアルカリ水溶液のｐＨをｐＨ試験紙で測定し、供給したアルカリ水溶液と同じになったところでサンプルとしてＰＦＡカラム出口の液体をＰＥ容器に受けた。また、サンプルは供給したアルカリ水溶液と同じ成分濃度であること（例えば水酸化ナトリウムは入口出口のＮａ濃度を）を分析により確認した。 Nitrogen gas was introduced from the upper part of the PTFE tank, the pressure inside the container was increased to 0.2 MPa, and the flow rate adjusting valve was operated to adjust the flow rate of the alkaline aqueous solution flowing out from the PFA column outlet to 5 ml / min or less. The pH of the alkaline aqueous solution flowing out was measured with a pH test paper, and when it became the same as the supplied alkaline aqueous solution, the liquid at the outlet of the PFA column was received as a sample in the PE container. In addition, it was confirmed by analysis that the sample had the same component concentration as the supplied alkaline aqueous solution (for example, sodium hydroxide had a Na concentration at the inlet and outlet).
ＰＥ容器に受けたアルカリ水溶液は直ちに密栓し、ＩＣＰ−ＭＳ、ＩＣＰ−ＡＥＳ、ＮＤＩＲ法により金属、ケイ素化合物及び無機炭酸の分析を行なった。金属分析項目は、銅、ニッケルの様なウェーハ内部に拡散しやすい金属とカルシウム、マグネシウム、マンガン、鉄、コバルト、亜鉛、アルミニウム、鉛などのウェーハ表面に留まる金属とした。
ＩＣＰ−ＭＳによる分析では、分析器導入前の処理として必要に応じて固相抽出法によるＮａ及びＫ成分の除去を行った。The alkaline aqueous solution received in the PE container was immediately sealed and analyzed for metals, silicon compounds and inorganic carbonic acid by ICP-MS, ICP-AES, and NDIR methods. Metal analysis items were metals such as copper and nickel that easily diffused inside the wafer and metals that remained on the wafer surface, such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead.
In the analysis by ICP-MS, Na and K components were removed by a solid phase extraction method as necessary as a process before introducing the analyzer.
なお、この実施例及び以下の各実施例並びに比較例における処理体量は４０ｍｌ、試料通液速度は、５ｍｌ／ｍｉｎ以下、通液量は１０００ｍｌ、通液はすべて１回パスで、２０〜２５℃の温度条件で行ったが、２５℃以上のアルカリ水溶液でも使用部材の耐熱性があれば用いることができる。
結果を表２に示す。In this example and the following examples and comparative examples, the amount of treated body is 40 ml, the sample passing rate is 5 ml / min or less, the passing rate is 1000 ml, and the passing rate is 20 to 25 in one pass. Although it performed on the temperature conditions of (degreeC), even if it is 25 degreeC or more alkaline aqueous solution, if the heat resistance of a use member is available, it can be used.
The results are shown in Table 2.
実施例９、比較例３
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Example 9, Comparative Example 3
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
（Ｊ）の限外濾過膜は超純水で１２時間通水洗浄した後に使用した。また（Ｋ）の活性炭フィルターは予め６．５Ｎ硝酸中に１時間浸漬洗浄を行い、超純水で１２時間通水洗浄をした後に使用した。洗浄したフィルターは専用カートリッジに挿入し、ポンプでアルカリ水溶液を通液後に濾過液の金属、ケイ素化合物及び無機炭酸の濃度をＩＣＰ−ＭＳ、ＩＣＰ−ＡＥＳ、ＮＤＩＲ法により測定した。金属分析項目は、銅、ニッケルの様なウェーハ内部に拡散しやすい金属とカルシウム、マグネシウム、マンガン、鉄、コバルト、亜鉛、アルミニウム、鉛などのウェーハ表面に留まる金属とした。
結果を表２に示す。(Processing operation)
The ultrafiltration membrane (J) was used after washing with ultrapure water for 12 hours. The activated carbon filter (K) was preliminarily washed by immersion in 6.5N nitric acid for 1 hour and then washed with ultrapure water for 12 hours before use. The washed filter was inserted into a dedicated cartridge, and after passing through an alkaline aqueous solution with a pump, the concentrations of metal, silicon compound and inorganic carbonic acid in the filtrate were measured by ICP-MS, ICP-AES and NDIR methods. Metal analysis items were metals such as copper and nickel that easily diffused inside the wafer and metals that remained on the wafer surface, such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead.
The results are shown in Table 2.
以下の実施例１０〜４７は、実施例１〜９までで、特に銅、ニッケルの様なウェーハ内部に拡散しやすい金属について良好な除去結果が得られたものを対象として試験を行った。濾過液の金属分析項目は、銅、ニッケルの様なウェーハ内部に拡散しやすい金属と鉄、亜鉛、アルミニウム、鉛などのウェーハ表面に留まり、洗浄の負荷となり易い金属を対象とした。 Examples 10 to 47 below were Examples 1 to 9, and tests were performed on the metal that easily diffused into the wafer, such as copper and nickel, with good removal results. The metal analysis items of the filtrate were metals such as copper and nickel that easily diffuse inside the wafer, and metals that remain on the wafer surface such as iron, zinc, aluminum, and lead, and that easily become a load of cleaning.
実施例１０〜１２
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 10-12
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
上記と同様の方法で、実施例１０として（Ａ）の強塩基性陰イオン交換繊維及び（Ｂ）の弱塩基性陰イオン交換繊維を混合した試料、実施例１１として（Ａ）及び（Ｄ）のエチレンジアミン三酢酸・イミノ二酢酸混合キレート樹脂を混合した試料、実施例１２として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表３に示す。(Processing operation)
In the same manner as described above, a sample prepared by mixing the strongly basic anion exchange fiber of (A) and the weakly basic anion exchange fiber of (B) as Example 10, and (A) and (D) as Example 11 A sample prepared by mixing the ethylenediamine triacetic acid / iminodiacetic acid mixed chelate resin of Example 1, and a sample in which the mixture of (A) and (B) and (D) are arranged in series as Example 12 was packed in a column. Purification was performed in the same manner as in No. 8.
The results are shown in Table 3.
実施例１３〜１５、比較例４〜５
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 13-15, Comparative Examples 4-5
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象の５０％ＮａＯＨを超純水で希釈した０．１％ＮａＯＨに代え、実施例１３として（Ａ）及び（Ｂ）を混合した試料、実施例１４として（Ｃ）の弱塩基性陰イオン交換樹脂、実施例１５として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例４として（Ｇ）の強酸性陽イオン交換樹脂、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表４に示す。(Processing operation)
A sample in which (A) and (B) were mixed as Example 13 instead of 0.1% NaOH diluted with ultrapure water, 50% NaOH to be treated, and (C) a weakly basic anion as Example 14 The exchange resin, a mixture of (A) and (B) as Example 15 and a sample in which (D) were arranged in series, and a strongly acidic cation exchange resin of (G) as Comparative Example 4 were packed in a column, and Purification was performed in the same manner as in Examples 1-8.
The results are shown in Table 4.
実施例１６〜１８、比較例６〜７
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 16-18, Comparative Examples 6-7
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象の５０％ＮａＯＨを超純水で希釈した０．０１％ＮａＯＨに代え、実施例１６として（Ａ）及び（Ｂ）を混合した試料、実施例１７として（Ｃ）、実施例１８として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例６として（Ｇ）をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表５に示す。(Processing operation)
A sample in which (A) and (B) were mixed as Example 16 instead of 0.01% NaOH diluted with ultrapure water, 50% NaOH to be treated, Example 17 (C), Example 18 ( A sample in which the mixture of A) and (B) and (D) were arranged in series, (G) as a comparative example 6 was packed in a column, and purification treatment was performed in the same manner as in Examples 1-8.
The results are shown in Table 5.
実施例１９〜２１、比較例８〜９
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 19-21, Comparative Examples 8-9
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例１９〜２１では４８％ＫＯＨに代え、実施例１９として（Ａ）及び（Ｂ）を混合した試料、実施例２０として（Ｃ）、実施例２１として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例８として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表６に示す。(Processing operation)
The alkaline aqueous solution to be treated was replaced with 48% KOH in Examples 19 to 21, and a sample prepared by mixing (A) and (B) as Example 19, (C) as Example 20, (A) and as Example 21 A sample in which the mixture of (B) and (D) were arranged in series, (G) as Comparative Example 8 was packed in a column, and purification treatment was performed in the same manner as in Examples 1-8.
The results are shown in Table 6.
実施例２２〜２４、比較例１０〜１１
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 22-24, Comparative Examples 10-11
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例２２〜２４では２３％Ｎａ２ＣＯ３に代え、実施例２２として（Ａ）及び（Ｂ）を混合した試料、実施例２３として（Ｃ）、実施例２４として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例１０として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表７に示す。(Processing operation)
The alkaline aqueous solution to be treated was replaced with 23% Na 2 CO 3 in Examples 22 to 24, and a sample prepared by mixing (A) and (B) as Example 22, (C) as Example 23, and Example 24 ( A sample in which the mixture of A) and (B) and (D) were arranged in series, and (G) as Comparative Example 10 were packed in a column, and purification treatment was performed in the same manner as in Examples 1-8.
The results are shown in Table 7.
実施例２５〜２７、比較例１２〜１３
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 25-27, Comparative Examples 12-13
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例２５〜２７では５０％Ｋ２ＣＯ３に代え、実施例２５として（Ａ）及び（Ｂ）を混合した試料、実施例２６として（Ｃ）、実施例２７として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例１２として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表８に示す。(Processing operation)
In Example 25 to 27, the alkaline aqueous solution to be treated was replaced with 50% K 2 CO 3 , a sample in which (A) and (B) were mixed as Example 25, (C) as Example 26, and Example 27 ( A sample in which the mixture of A) and (B) and (D) were arranged in series, (G) as Comparative Example 12 was packed in a column, and purification treatment was performed in the same manner as in Examples 1-8.
The results are shown in Table 8.
実施例２８〜３０、比較例１４〜１５
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 28-30, Comparative Examples 14-15
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例２８〜３０では８％ＮａＨＣＯ３に代え、実施例２８として（Ａ）及び（Ｂ）を混合した試料、実施例２９として（Ｃ）、実施例３２として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例１４として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表９に示す。(Processing operation)
The alkaline aqueous solution to be treated was replaced with 8% NaHCO 3 in Examples 28 to 30, and a sample in which (A) and (B) were mixed as Example 28, (C) as Example 29, and (A) as Example 32 And the sample which arranged the mixture of (B) and (D) in series, (G) as the comparative example 14 was packed in the column, and the refinement | purification process was performed by the method similar to Examples 1-8.
The results are shown in Table 9.
実施例３１〜３３、比較例１６〜１７
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 31-33, Comparative Examples 16-17
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例３１〜３３では５０％ＫＨＣＯ３に代え、実施例３１として（Ａ）及び（Ｂ）を混合した試料、実施例３２として（Ｃ）、実施例３３として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例１６として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表１０に示す。(Processing operation)
The alkaline aqueous solution to be treated was replaced with 50% KHCO 3 in Examples 31 to 33, and a sample in which (A) and (B) were mixed as Example 31, (C) as Example 32, and (A) as Example 33 And the sample which arranged the mixture of (B) and (D) in series, (G) as the comparative example 16 was packed in the column, and the refinement | purification process was performed by the method similar to Examples 1-8.
The results are shown in Table 10.
実施例３４〜３６、比較例１８〜１９
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 34 to 36, Comparative Examples 18 to 19
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例３４〜３６では２８％アンモニア水に代え、実施例３４として（Ａ）及び（Ｂ）を混合した試料、実施例３５として（Ｃ）、実施例３６として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例１８として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表１１に示す。(Processing operation)
In Examples 34 to 36, the alkaline aqueous solution to be treated was replaced with 28% aqueous ammonia, and a sample prepared by mixing (A) and (B) as Example 34, (C) as Example 35, and (A) as Example 36 And the sample which arranged the mixture of (B) and (D) in series, (G) as the comparative example 18 was packed in the column, and the refinement | purification process was performed by the method similar to Examples 1-8.
The results are shown in Table 11.
実施例３７〜３９、比較例２０〜２１
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 37-39, Comparative Examples 20-21
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
処理対象のアルカリ水溶液を実施例３７〜３９では２５％水酸化テトラメチルアンモニウム水溶液に代え、実施例３７として（Ａ）及び（Ｂ）を混合した試料、実施例３８として（Ｃ）、実施例３９として（Ａ）及び（Ｂ）の混合体と（Ｄ）を直列に並べた試料、比較例２０として（Ｇ）、をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表１２に示す。(Processing operation)
The alkaline aqueous solution to be treated was replaced with a 25% tetramethylammonium hydroxide aqueous solution in Examples 37 to 39, a sample in which (A) and (B) were mixed as Example 37, (C) and Example 39 as Example 38. As a sample in which the mixture of (A) and (B) and (D) are arranged in series, and (G) as Comparative Example 20 are packed in a column, and purification treatment is performed in the same manner as in Examples 1-8. It was.
The results are shown in Table 12.
実施例４０〜４２
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。Examples 40-42
(Washing equipment used)
The instrument used was washed in the same manner as above.
（処理操作）
実施例１〜８と同様の方法で、実施例４０の（Ｃ）及び（Ｆ）の混合体と（Ａ）及び（Ｂ）の混合体とをこの順番で直列に並べた試料、実施例４１の（Ａ）及び（Ｂ）の混合体と（Ｃ）及び（Ｆ）の混合体とをこの順番で直列に並べた試料、実施例４２の（Ｋ）と、（Ｃ）及び（Ｆ）の混合体並びに（Ａ）及び（Ｂ）の混合体をこの順番で直列に並べた試料をカラムに充填し、実施例１〜８と同様の方法で精製処理を行った。
結果を表１３に示す。(Processing operation)
A sample in which the mixture of (C) and (F) of Example 40 and the mixture of (A) and (B) were arranged in series in this order in the same manner as in Examples 1 to 8, Example 41 A sample in which the mixture of (A) and (B) and the mixture of (C) and (F) were arranged in series in this order, (K) of Example 42, and (C) and (F) A sample was prepared by arranging the mixture and the mixture of (A) and (B) in series in this order, and the column was packed, and purification was performed in the same manner as in Examples 1-8.
The results are shown in Table 13.
実施例４３、４４
（使用器具の洗浄）
ＰＴＦＥ製タンク（容積１２００ｍｌ）、サンプリング用ＰＥ（ポリエチレン）製容器（容積１０００ｍｌ）は全て金属汚染を排除するため予め、１Ｎ硝酸で１時間以上浸漬させた後超純水で流水洗浄した。
洗浄に用いた硝酸は関東化学（株）製の電子工業用グレード(ＥＬ)であり、約１Ｎとなるよう超純水で希釈したものであり、超純水は超純水製造システムで製造された金属含有量が各金属１ｐｐｔ以下、Ｓｉ５０ｐｐｔ以下、無機炭素１０ｐｐｂ以下のものである。Examples 43 and 44
(Washing equipment used)
The PTFE tank (volume 1200 ml) and the sampling PE (polyethylene) container (volume 1000 ml) were all immersed in 1N nitric acid for 1 hour or more in advance and washed with running ultrapure water to eliminate metal contamination.
The nitric acid used for washing is an electronic industrial grade (EL) manufactured by Kanto Chemical Co., Inc., diluted with ultrapure water to be about 1N, and ultrapure water is produced by an ultrapure water production system. The metal content of each metal is 1 ppt or less, Si 50 ppt or less, and
（処理操作）
実施例４３、４４としてＰＴＦＥ製タンク(容積１２００ｍｌ)の中で５０％ＮａＯＨ及び５０％ＫＯＨをそれぞれ（Ｃ）と２４時間接触させたバッチ法による精製処理を行った。
結果を表１４に示す。(Processing operation)
As Examples 43 and 44, purification was performed by a batch method in which 50% NaOH and 50% KOH were contacted with (C) for 24 hours in a PTFE tank (volume: 1200 ml), respectively.
The results are shown in Table 14.
実施例４５〜４７
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。
（処理操作）
実施例４５〜４７としてＰＴＦＥ製タンク（容積１２００ｍｌ）の中に５０％ＮａＯＨを貯留し、４インチシリコンウェーハを投入し、８０℃にて３時間加熱後、徐冷したものを比較例１０のアルカリ水溶液とした。これに（Ａ）を２４時間接触させたバッチ法及び（Ａ）と（Ｂ）を実施例１〜９と同様なカラムにて精製処理を行った。
結果を表１５に示す。Examples 45-47
(Washing equipment used)
The instrument used was washed in the same manner as above.
(Processing operation)
In Examples 45 to 47, 50% NaOH was stored in a PTFE tank (volume: 1200 ml), a 4-inch silicon wafer was charged, heated at 80 ° C. for 3 hours, and gradually cooled. An aqueous solution was obtained. A batch method in which (A) was contacted for 24 hours and (A) and (B) were purified using the same column as in Examples 1-9.
The results are shown in Table 15.
実施例４８〜４９、比較例２２〜２３
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。
（処理操作）
実施例４８〜４９、比較例２２として（Ａ）の強塩基性陰イオン交換繊維、（Ｅ）キレート繊維及び（Ｇ）強酸性陽イオン交換樹脂を２０ｍｌと７０％酢酸アンモニウム水溶液を２００ｍｌとをＰＥ製容器内で混合し、２４時間、バッチ法による精製処理を行った。
結果を表１６に示す。Examples 48-49, Comparative Examples 22-23
(Washing equipment used)
The instrument used was washed in the same manner as above.
(Processing operation)
In Examples 48 to 49 and Comparative Example 22, 20 ml of (A) strongly basic anion exchange fiber, (E) chelate fiber and (G) strongly acidic cation exchange resin and 200 ml of 70% aqueous ammonium acetate solution were added to PE. The mixture was mixed in a container and purified by a batch method for 24 hours.
The results are shown in Table 16.
実施例５０、比較例２４〜２５
（使用器具の洗浄）
上記と同様の方法で使用器具を洗浄した。
（処理操作）
実施例５０、比較例２４として（Ｅ）キレート繊維及び（Ｇ）強酸性陽イオン交換樹脂を２０ｍｌと１％セルロース水溶液を２００ｍｌとをＰＥ製容器内で混合し、２４時間、バッチ法による精製処理を行った。
結果を表１７に示す。Example 50, Comparative Examples 24-25
(Washing equipment used)
The instrument used was washed in the same manner as above.
(Processing operation)
As Example 50 and Comparative Example 24, 20 ml of (E) chelate fiber and (G) strongly acidic cation exchange resin and 200 ml of 1% cellulose aqueous solution were mixed in a PE container, and purified for 24 hours by a batch method. Went.
The results are shown in Table 17.
表２において、比較例１に示している金属不純物を含む未処理の５０％ＮａＯＨを用いて、実施例１〜９の処理を行った結果、金属不純物の除去能力を確認することができた。しかしながら実施例８や実施例９、実施例１１のように５０％ＮａＯＨと接触することで金属が溶出してくるケースも見られた。 In Table 2, the treatment of Examples 1 to 9 was performed using untreated 50% NaOH containing the metal impurities shown in Comparative Example 1, and as a result, the ability to remove metal impurities could be confirmed. However, as in Example 8, Example 9, and Example 11, there was a case where metal was eluted by contact with 50% NaOH.
ここで、５０％ＮａＯＨのような強アルカリ溶液中では、金属は陽イオン化学種として存在する割合が低いため、比較例２で示されるように、一般的な（Ｇ）の強酸性陽イオン交換樹脂では金属不純物が除去できない結果が得られた。一方、実施例１〜３、６のように陰イオン交換繊維や樹脂では効果的に金属不純物が除去できた。特に５０％ＮａＯＨのように炭酸不純物を吸収しやすい溶液の場合、強塩基性陰イオン交換基よりも弱塩基性陰イオン交換基の方が効果的に金属不純物を除去できる結果が得られた。また、実施例４及び実施例５のような特殊なキレート官能基を有する繊維や樹脂も金属不純物除去効果を発揮した。
しかし、比較例３のように限外濾過法を用いても微量な金属不純物は除去できなかった。Here, in a strong alkaline solution such as 50% NaOH, since the proportion of metal present as a cationic species is low, as shown in Comparative Example 2, a general (G) strongly acidic cation exchange is performed. The result that the metal impurities could not be removed by the resin was obtained. On the other hand, metal impurities could be effectively removed with anion exchange fibers and resins as in Examples 1 to 3 and 6. In particular, in the case of a solution that easily absorbs carbonic acid impurities such as 50% NaOH, a result that metal impurities can be effectively removed by weakly basic anion exchange groups than by strong basic anion exchange groups was obtained. Moreover, the fiber and resin which have a special chelate functional group like Example 4 and Example 5 also exhibited the metal impurity removal effect.
However, even if the ultrafiltration method was used as in Comparative Example 3, a trace amount of metal impurities could not be removed.
表３において、実施例１〜９の試験で良好であった処理方法を組み合わせた場合の効果を調べた結果、実施例１０〜１２のように飛躍的に金属不純物除去能力が上がることが示された。特に銅とニッケルについては、１．０ｐｐｂ以下までの除去が可能であった。 In Table 3, as a result of investigating the effect in the case of combining the processing methods that were good in the tests of Examples 1 to 9, it was shown that the metal impurity removal capability dramatically increased as in Examples 10 to 12. It was. In particular, copper and nickel could be removed to 1.0 ppb or less.
表４及び５では上記試験で特に良好であった実施例３、実施例１０及び実施例１２と同様の充填物にて実施し、比較例４として（Ｇ）の強酸性陽イオン交換樹脂を使用した場合を検討した。ここで比較例４では（Ｇ）での金属除去能力は確認できなかったが、比較例６では（Ｇ）が効果的に作用していることがわかった。すなわち、０．０１重量％ＮａＯＨ（ｐＨ＝１１．４）以下では金属が陽イオン化学種としても存在し、従来法の陽イオン交換法によって処理可能である。しかし、０．１重量％ＮａＯＨ（ｐＨ＝１２．４）程度の濃度では、従来法の陽イオン交換法では金属を除去することができず、本発明による精製方法が有効であった。 In Tables 4 and 5, the same packing as in Example 3, Example 10 and Example 12, which was particularly good in the above test, was used, and (G) strong acid cation exchange resin was used as Comparative Example 4 Considered the case. Here, in Comparative Example 4, the metal removal ability in (G) could not be confirmed, but in Comparative Example 6, it was found that (G) was acting effectively. That is, at 0.01 wt% NaOH (pH = 11.4) or less, metal exists as a cation chemical species and can be treated by a conventional cation exchange method. However, at a concentration of about 0.1 wt% NaOH (pH = 12.4), the metal cannot be removed by the conventional cation exchange method, and the purification method according to the present invention is effective.
以下の表６〜１２に示した実施例１９〜３９でも以上の処理と同様に試験を行い、ほぼ同様の結果が得られた。ただし炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウムを用いた場合は、（Ａ）の強塩基性陰イオン交換繊維が炭酸化学種の影響を受け、多少除去能力が低下している傾向が見られた。また、表９及び表１０で示されるように炭酸水素ナトリウム及び炭酸水素カリウムでは、弱塩基性であるため、従来の陽イオン交換法も効果がある結果も得られた。 In Examples 19 to 39 shown in Tables 6 to 12 below, tests were performed in the same manner as the above treatment, and almost the same results were obtained. However, when sodium carbonate, potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate is used, the strong basic anion exchange fiber of (A) is affected by the carbonic acid chemical species, and the removal ability tends to be somewhat reduced. It was seen. In addition, as shown in Tables 9 and 10, sodium hydrogen carbonate and potassium hydrogen carbonate are weakly basic, so that results obtained by the conventional cation exchange method were also obtained.
そして、表１３に示した実施例４０〜４２でも、以上の処理と同様に試験を行ったところ、強塩基性陰イオン交換繊維、弱塩基性陰イオン交換繊維、強塩基性陰イオン交換樹脂、弱塩基性陰イオン交換樹脂を組み合わせた場合には特に優れた金属不純物除去能力を有することがわかった。 And also in Examples 40 to 42 shown in Table 13, when a test was performed in the same manner as the above treatment, a strongly basic anion exchange fiber, a weakly basic anion exchange fiber, a strongly basic anion exchange resin, It has been found that when a weakly basic anion exchange resin is combined, it has a particularly excellent ability to remove metal impurities.
表１４に示したバッチ法による精製処理である実施例４３及び４４でも、実施例３及び２０と同等あるいはそれ以上に金属不純物除去能力がある結果が得られた。 Also in Examples 43 and 44, which are the purification processes by the batch method shown in Table 14, results with metal impurity removal ability equivalent to or higher than those in Examples 3 and 20 were obtained.
表１５に示した実施例４５〜４７でも、以上の処理と同様に試験を行ったところ、特にケイ素化合物、無機炭酸が強塩基性陰イオン交換繊維にて除去精製されていることがわかった。逆に弱塩基性陰イオン交換繊維では、ケイ素化合物、無機炭酸が除去されていないことがわかった。これより、ケイ素化合物及び無機炭酸の除去精製の必要性の有無によって使いわけることができることがわかった。 Also in Examples 45 to 47 shown in Table 15, when tests were performed in the same manner as the above treatment, it was found that particularly silicon compounds and inorganic carbonic acid were removed and purified with strong basic anion exchange fibers. Conversely, it was found that the silicon compound and inorganic carbonic acid were not removed from the weakly basic anion exchange fiber. From this, it was found that the silicon compound and the inorganic carbonic acid can be used properly depending on the necessity of removal and purification.
表１６に示した７０％酢酸アンモニウム水溶液（ｐＨ＝１０．０）において、実施例４８〜４９の（Ａ）及び（Ｅ）で効果が確認でき、比較例２２の（Ｇ）では効果が確認できなかった。その理由として、高濃度に酢酸イオンやアンモニウムイオンが存在するため、それらとの金属の錯体を形成し、（Ｇ）では除去できない金属化学種として存在していると考えられる。そして、負電荷の酢酸−金属錯体が（Ａ）では電気的に吸着され、（Ｅ）では酢酸イオンまたはアンモニウムイオンよりも強力な配位結合力によって吸着されたと考えられる。 In the 70% aqueous solution of ammonium acetate (pH = 10.0) shown in Table 16, the effects can be confirmed in (A) and (E) of Examples 48 to 49, and the effect can be confirmed in (G) of Comparative Example 22. There wasn't. The reason for this is that acetate ions and ammonium ions are present at high concentrations, so that metal complexes with them are formed, and it is considered that they exist as metal species that cannot be removed by (G). Then, it is considered that the negatively charged acetic acid-metal complex was electrically adsorbed in (A) and adsorbed in (E) with a stronger coordination bond force than acetate ions or ammonium ions.
表１７に示した１％セルロース水溶液（ｐＨ＝１１.０）において、実施例５０の（Ｅ）及び比較例２４の（Ｇ）で効果が確認できた。この結果より、比較例６と同様に金属が陽イオン化学種としても存在していると考えられる。 In the 1% cellulose aqueous solution (pH = 11.0) shown in Table 17, the effect could be confirmed in (E) of Example 50 and (G) of Comparative Example 24. From this result, it is considered that the metal exists also as a cationic species as in Comparative Example 6.
本発明は、金属不純物を含有するアルカリ水溶液の精製において広く利用することができる。 The present invention can be widely used in the purification of an alkaline aqueous solution containing metal impurities.
Claims (7)
前記アルカリ水溶液が、０．０１〜５０重量％の水酸化ナトリウム、０．０１〜５０重量％の水酸化カリウム、０．０１〜３０重量％のアンモニア、０．０１〜２５重量％の水酸化テトラメチルアンモニウム、５〜２３重量％の炭酸ナトリウム、５〜５０重量％の炭酸カリウム、５〜８重量％の炭酸水素ナトリウム又は５〜５０重量％の炭酸水素カリウム、であることを特徴とするアルカリ水溶液の精製方法。 A method for purifying an alkaline aqueous solution, wherein an alkaline aqueous solution containing metal impurities is contacted with a fibrous weakly basic anion exchanger to remove metallic impurities,
The alkaline aqueous solution was 0.01 to 50% by weight sodium hydroxide, 0.01 to 50% by weight potassium hydroxide, 0.01 to 30% by weight ammonia, 0.01 to 25% by weight tetrahydroxide. Alkaline aqueous solution, characterized in that it is methylammonium, 5 to 23% by weight sodium carbonate, 5 to 50% by weight potassium carbonate, 5 to 8% by weight sodium bicarbonate or 5 to 50% by weight potassium bicarbonate. Purification method.
前記アルカリ水溶液が、０．０１〜５０重量％の水酸化ナトリウム、０．０１〜５０重量％の水酸化カリウム、０．０１〜３０重量％のアンモニア、０．０１〜２５重量％の水酸化テトラメチルアンモニウム、５〜２３重量％の炭酸ナトリウム、５〜５０重量％の炭酸カリウム、５〜８重量％の炭酸水素ナトリウム又は５〜５０重量％の炭酸水素カリウム、であることを特徴とするアルカリ水溶液の精製方法。 A method for purifying an alkaline aqueous solution in which an alkaline aqueous solution containing a siliconized impurity, a carbonic acid impurity, and a metal impurity is brought into contact with a fibrous weakly basic anion exchanger to remove only the metal impurity,
The alkaline aqueous solution was 0.01 to 50% by weight sodium hydroxide, 0.01 to 50% by weight potassium hydroxide, 0.01 to 30% by weight ammonia, 0.01 to 25% by weight tetrahydroxide. Alkaline aqueous solution, characterized in that it is methylammonium, 5 to 23% by weight sodium carbonate, 5 to 50% by weight potassium carbonate, 5 to 8% by weight sodium bicarbonate or 5 to 50% by weight potassium bicarbonate. Purification method.
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| JP5053587B2 (en) * | 2006-07-31 | 2012-10-17 | 東亞合成株式会社 | High-purity production method of alkali metal hydroxide |
| JP2009167036A (en) * | 2008-01-11 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
| JP5369440B2 (en) * | 2008-01-11 | 2013-12-18 | 東亞合成株式会社 | Method for producing high-purity alkali metal carbonate aqueous solution and continuous production method for high-purity alkali metal carbonate aqueous solution |
| JP2009167050A (en) * | 2008-01-15 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
| JP5311227B2 (en) * | 2009-08-05 | 2013-10-09 | 野村マイクロ・サイエンス株式会社 | Anion exchanger, its pretreatment method and regeneration method, and purification method and purification apparatus of alkaline aqueous solution |
| JP2011051833A (en) * | 2009-09-02 | 2011-03-17 | Nomura Micro Sci Co Ltd | Method for purification of alkaline aqueous solution |
| JP2014188514A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Process for producing purified alkali metal aqueous solution |
| JP5648231B2 (en) * | 2013-05-22 | 2015-01-07 | 野村マイクロ・サイエンス株式会社 | Purification method of alkaline aqueous solution |
| CN112999694A (en) * | 2021-03-24 | 2021-06-22 | 沧州信联化工有限公司 | Raw material refining device for processing tetramethylammonium hydroxide and use method thereof |
| CN115744934B (en) * | 2022-11-29 | 2024-03-22 | 福建省龙德新能源有限公司 | Preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate |
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| US2789036A (en) * | 1952-12-27 | 1957-04-16 | Diamond Alkali Co | Purification of concentrated alkali metal hydroxide by ion exchange |
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| WO2006018985A1 (en) * | 2004-08-06 | 2006-02-23 | Asahi Kasei Chemicals Corporation | Method for purifying aqueous alkaline solution |
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| US2789036A (en) * | 1952-12-27 | 1957-04-16 | Diamond Alkali Co | Purification of concentrated alkali metal hydroxide by ion exchange |
| JPS52149297A (en) * | 1976-06-07 | 1977-12-12 | Toyo Soda Mfg Co Ltd | Purification of caustic soda aq. solution |
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| WO2006018985A1 (en) * | 2004-08-06 | 2006-02-23 | Asahi Kasei Chemicals Corporation | Method for purifying aqueous alkaline solution |
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