JP2017095768A - Nickel element recovery method - Google Patents
Nickel element recovery method Download PDFInfo
- Publication number
- JP2017095768A JP2017095768A JP2015229553A JP2015229553A JP2017095768A JP 2017095768 A JP2017095768 A JP 2017095768A JP 2015229553 A JP2015229553 A JP 2015229553A JP 2015229553 A JP2015229553 A JP 2015229553A JP 2017095768 A JP2017095768 A JP 2017095768A
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- Prior art keywords
- nickel
- aqueous solution
- solution
- extraction
- liquid
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- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 339
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000011084 recovery Methods 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 79
- 239000000243 solution Substances 0.000 claims abstract description 70
- 238000007747 plating Methods 0.000 claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 229910003307 Ni-Cd Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- -1 phosphite ions Chemical class 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ASYPQLBYSSYEBE-UHFFFAOYSA-N 2-chloro-n,n-dioctylacetamide Chemical compound CCCCCCCCN(C(=O)CCl)CCCCCCCC ASYPQLBYSSYEBE-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- ZSBDPRIWBYHIAF-UHFFFAOYSA-N N-acetyl-acetamide Natural products CC(=O)NC(C)=O ZSBDPRIWBYHIAF-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- OJVGGGLUMMGWLC-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]acetamide Chemical compound CCCCCCCCN(C(=O)COCC(N)=O)CCCCCCCC OJVGGGLUMMGWLC-UHFFFAOYSA-N 0.000 description 3
- UHSURKDCQCGNGM-UHFFFAOYSA-N 5-(2-hydroxyimino-2-phenylethyl)nonan-2-ol Chemical compound CCCCC(CCC(C)O)CC(=NO)C1=CC=CC=C1 UHSURKDCQCGNGM-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 2
- USMJATUIRDERER-UHFFFAOYSA-N 2-[carboxymethyl-[2-(dioctylamino)-2-oxoethyl]amino]acetic acid Chemical compound CCCCCCCCN(CCCCCCCC)C(=O)CN(CC(O)=O)CC(O)=O USMJATUIRDERER-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 CN(*)C(CN(CC(O)=O)CC(O)=O)=O Chemical compound CN(*)C(CN(CC(O)=O)CC(O)=O)=O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- OOBIYKZOAIQDEC-UHFFFAOYSA-N dodecyl pyridine-3-carboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CN=C1 OOBIYKZOAIQDEC-UHFFFAOYSA-N 0.000 description 2
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 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 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 description 1
- CNDWHJQEGZZDTQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetamide Chemical compound NC(=O)COCC(N)=O CNDWHJQEGZZDTQ-UHFFFAOYSA-N 0.000 description 1
- KOHUSHSNNOEPFN-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]acetic acid Chemical compound CCCCCCCCN(C(=O)COCC(O)=O)CCCCCCCC KOHUSHSNNOEPFN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- GQZXNSPRSGFJLY-UHFFFAOYSA-M dioxidophosphate(1-) Chemical compound [O-]P=O GQZXNSPRSGFJLY-UHFFFAOYSA-M 0.000 description 1
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- AHDVQERFCJZEAX-UHFFFAOYSA-N dodecyl pyridine-4-carboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=NC=C1 AHDVQERFCJZEAX-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Physical Water Treatments (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、ニッケル元素の回収方法に関し、より詳しくは使用済み無電解ニッケルめっき液等のニッケル含有水溶液からニッケル元素を効率的に回収することができるニッケル元素の回収方法に関する。 The present invention relates to a nickel element recovery method, and more particularly to a nickel element recovery method capable of efficiently recovering nickel element from a nickel-containing aqueous solution such as a used electroless nickel plating solution.
無電解ニッケルめっき法は、複雑な形状の部品に均一な厚さのニッケルめっき皮膜を施すことができるため、電子部品や精密機械部品などの生産に欠かせない表面処理技術である。無電解ニッケルめっき液には、多くの場合、硫酸ニッケル（ニッケル供給源）、次亜リン酸ナトリウム（還元剤）、有機酸（錯化剤・緩衝剤）等が含まれており、めっきに使用するとニッケルが消費され、次亜リン酸ナトリウムは酸化されて亜リン酸ナトリウムとなり、還元力が低下することとなる。そのため、随時硫酸ニッケル、次亜リン酸ナトリウム及びｐＨ調節剤として水酸化ナトリウムをめっき液に補充しながら使用する必要がある。しかしながら、繰り返して使用するうちに、硫酸イオン、ナトリウムイオン、亜リン酸イオン、被めっき物の表面から溶出した亜鉛や鉄などがめっき液中に蓄積し、めっき性能が悪くなるため、ある程度まで使用しためっき液は廃液として処分されている。そのため、環境保全および資源の安定確保の観点から、使用済み無電解ニッケルめっき液からニッケルを回収し、資源循環システムを構築する必要がある。 The electroless nickel plating method is a surface treatment technology that is indispensable for the production of electronic parts, precision machine parts, and the like because a nickel plating film having a uniform thickness can be applied to parts having complicated shapes. In many cases, electroless nickel plating solution contains nickel sulfate (nickel supply source), sodium hypophosphite (reducing agent), organic acid (complexing agent / buffering agent), etc. Then, nickel is consumed, sodium hypophosphite is oxidized to sodium phosphite, and the reducing power is reduced. Therefore, it is necessary to use nickel sulfate, sodium hypophosphite, and sodium hydroxide as a pH adjuster while supplementing the plating solution as needed. However, as it is repeatedly used, sulfate ions, sodium ions, phosphite ions, zinc and iron eluted from the surface of the object to be plated accumulate in the plating solution, and the plating performance deteriorates. The plating solution is disposed as a waste solution. For this reason, it is necessary to recover the nickel from the used electroless nickel plating solution and to build a resource circulation system from the viewpoint of environmental preservation and resource stability.
無電解ニッケルめっき液からニッケルを回収する方法としては、溶媒抽出法を用いて無電解めっき液からニッケルを抽出する方法が提案されている。例えば、２−ヒドロキシ−５−ノニルアセトフェノンオキシムを抽出剤として用いて、無電解ニッケルめっき廃液からニッケルを抽出する方法が開示されている（例えば、非特許文献１参照）。
しかしながら、上記の方法では無電解ニッケルめっき液のｐＨ調整を行わないで抽出を行った場合、ニッケルの抽出率が３５％程度と十分な値が得られていない。ｐＨを中性から弱アルカリ性に調整すればニッケルの抽出率が向上するが、ｐＨ調整にコストと手間がかかり、また、ニッケルが水酸化物として沈殿し、抽出に悪影響を及ぼすことが予想される。さらには、ニッケルの抽出速度が低く、効率良く回収できないという問題もある。
As a method for recovering nickel from the electroless nickel plating solution, a method for extracting nickel from the electroless plating solution using a solvent extraction method has been proposed. For example, a method for extracting nickel from an electroless nickel plating waste liquid using 2-hydroxy-5-nonylacetophenone oxime as an extractant is disclosed (for example, see Non-Patent Document 1).
However, in the above method, when extraction is performed without adjusting the pH of the electroless nickel plating solution, a sufficient value of nickel extraction rate of about 35% is not obtained. Adjusting the pH from neutral to weakly alkaline improves the extraction rate of nickel, but it takes cost and labor to adjust the pH, and nickel is precipitated as a hydroxide and is expected to have a negative effect on extraction. . Furthermore, there is also a problem that nickel extraction rate is low and cannot be efficiently recovered.
他の例として、２−ヒドロキシ−５−ノニルアセトフェノンオキシムに加速剤として有機リン酸系抽出剤（例えば、ジ（２−エチルヘキシル）リン酸（Ｄ２ＥＨＰＡ）や２−エチルヘキシルホスホン酸モノ−２−エチルヘキシルエステル（ＰＣ−８８Ａ））を添加して、無電解ニッケルめっき廃液からニッケルを抽出する方法が開示されている（例えば、非特許文献１参照）。
しかしながら、上記の方法では無電解ニッケルめっき液のｐＨ調整を行わないで抽出を行った場合、ニッケルの抽出率が十分な値ではない。そのため、ｐＨを中性領域に調整する必要があるが、ｐＨ調整にコストと手間がかかる。また、ニッケルの抽出平衡時間まで１０分程度かかり、十分な抽出速度も得られていない。さらには、有機リン酸系抽出剤による２−ヒドロキシ−５−ノニルアセトフェノンオキシムの分解やナトリウムを同時に抽出するため、高純度のニッケルを得ることが困難であることが指摘されている。
Other examples include 2-hydroxy-5-nonyl acetophenone oxime and organic phosphoric acid-based extractants (eg, di (2-ethylhexyl) phosphoric acid (D2EHPA) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) as accelerators. (PC-88A)) is added to extract nickel from electroless nickel plating waste liquid (for example, see Non-Patent Document 1).
However, in the above method, when extraction is performed without adjusting the pH of the electroless nickel plating solution, the nickel extraction rate is not a sufficient value. Therefore, it is necessary to adjust the pH to a neutral region, but it takes cost and labor to adjust the pH. Moreover, it takes about 10 minutes until the nickel equilibration time, and a sufficient extraction rate is not obtained. Furthermore, it has been pointed out that it is difficult to obtain high-purity nickel because decomposition of 2-hydroxy-5-nonylacetophenone oxime with an organic phosphate-based extractant and extraction of sodium simultaneously.
他の例として、Ｄ２ＥＨＰＡとニコチン酸ドデシルとの混合物、または、Ｄ２ＥＨＰＡとイソニコチン酸ドデシルとの混合物を用いて、無電解ニッケルめっき廃液からニッケルを抽出する方法が開示されている（例えば、特許文献１参照）。
しかしながら、上記の方法では２種類の抽出剤を使用するため抽出操作が煩雑となる。また、Ｄ２ＥＨＰＡによるニコチン酸ドデシル及びイソニコチン酸ドデシルの分解やナトリウムを同時に抽出するため、高純度のニッケルを得ることが困難であることが指摘され
ている。
As another example, a method for extracting nickel from an electroless nickel plating waste solution using a mixture of D2EHPA and dodecyl nicotinate or a mixture of D2EHPA and dodecyl isonicotiate is disclosed (for example, Patent Documents). 1).
However, in the above method, since two types of extractants are used, the extraction operation becomes complicated. Further, it has been pointed out that it is difficult to obtain high-purity nickel because decomposition of dodecyl nicotinate and dodecyl isonicotinate by D2EHPA and extraction of sodium at the same time are performed.
さらに本発明者は、以前、ジグリコールアミド酸の骨格を持つ２−（２−（ジオクチルアミノ）−２−オキソエトキシ）酢酸（以下、「ＤＯＤＧＡＡ」と略す場合がある。）を抽出剤として開発した。しかし、この抽出剤はニッケルに対しては抽出能が十分ではないものと言える（例えば、非特許文献２参照。）。 Furthermore, the present inventor has previously developed 2- (2- (dioctylamino) -2-oxoethoxy) acetic acid (hereinafter sometimes abbreviated as “DODGAA”) having a diglycolamide acid skeleton as an extractant. did. However, it can be said that this extractant has insufficient extraction ability for nickel (see, for example, Non-Patent Document 2).
本発明は、使用済み無電解ニッケルめっき液等のニッケル含有水溶液からニッケル元素を効率的に回収することができるニッケル元素の回収方法を提供することを目的とする。 An object of the present invention is to provide a nickel element recovery method that can efficiently recover nickel element from a nickel-containing aqueous solution such as a used electroless nickel plating solution.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、特定のニトリロ酢酸ジアセトアミド化合物又はその塩の存在下で抽出を行うことにより、ニッケル元素を効率的に回収方法することができることを見出し、本発明を完成させた。
即ち、本発明は以下の通りである。
＜１＞ ニッケル含有水溶液を準備する準備工程、並びに下記一般式（１）で表される化合物又はその塩の存在下、前記準備工程で準備したニッケル含有水溶液と有機溶媒を接触させて、ニッケル元素（Ｎｉ）を抽出する液液接触工程を含む、ニッケル元素の回収方法。
（式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ同一種又は異種の炭化水素基を表す。但し、Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基の炭素数の合計が、８〜６４である。）
＜２＞ 前記準備工程で準備したニッケル含有水溶液のｐＨが、７．０以下である、＜１＞に記載のニッケル元素の回収方法。
＜３＞ さらに前記液液接触工程で接触させたニッケル含有水溶液と有機溶媒を分液する分液工程、及び前記分液工程で分液した有機溶媒に、前記分液工程で分液したニッケル含有水溶液とは別の酸性水溶液を接触させる逆抽出工程を含む、＜１＞又は＜２＞に記載のニッケル元素の回収方法。
＜４＞ 前記ニッケル含有水溶液が、電解ニッケルめっき液、使用済み電解ニッケルめっき液、無電解ニッケルめっき液、使用済み無電解ニッケルめっき液、廃Ｎｉ−Ｃｄ電池を浸出して得られる溶液、又は含ニッケル鉱を浸出して得られる溶液である、＜１＞〜＜３＞の何れかに記載のニッケル元素の回収方法。
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention can efficiently recover nickel element by performing extraction in the presence of a specific nitriloacetic acid diacetamide compound or a salt thereof. The present invention has been completed.
That is, the present invention is as follows.
<1> A preparation step of preparing a nickel-containing aqueous solution, and in the presence of a compound represented by the following general formula (1) or a salt thereof, the nickel-containing aqueous solution prepared in the preparation step and an organic solvent are brought into contact with each other to thereby form a nickel element A method for recovering nickel element, comprising a liquid-liquid contact step of extracting (Ni).
(In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent the same or different hydrocarbon group, provided that R 1 , R 2 , R 3 , and R 4 are hydrocarbons. The total number of carbon atoms in the group is 8 to 64.)
<2> The nickel element recovery method according to <1>, wherein the nickel-containing aqueous solution prepared in the preparation step has a pH of 7.0 or less.
<3> Furthermore, the nickel-containing aqueous solution separated in the liquid separation step is separated into the liquid separation step for separating the nickel-containing aqueous solution and the organic solvent brought into contact in the liquid-liquid contact step, and the organic solvent separated in the liquid separation step. The method for recovering nickel element according to <1> or <2>, comprising a back extraction step in which an acidic aqueous solution different from the aqueous solution is contacted.
<4> The nickel-containing aqueous solution is an electrolytic nickel plating solution, a used electrolytic nickel plating solution, an electroless nickel plating solution, a used electroless nickel plating solution, a solution obtained by leaching a waste Ni-Cd battery, or The method for recovering nickel element according to any one of <1> to <3>, which is a solution obtained by leaching nickel ore.
本発明によれば、使用済み無電解ニッケルめっき液等のニッケル含有水溶液からニッケル元素を効率的に回収することができるニッケル元素の回収方法を提供することができる。 According to the present invention, it is possible to provide a nickel element recovery method that can efficiently recover nickel element from a nickel-containing aqueous solution such as a used electroless nickel plating solution.
本発明を説明するに当たり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限り以下の内容に限定されるものではなく、適宜変更して実施することができる。 In describing the present invention, specific examples will be described. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.
＜ニッケル元素の回収方法＞
本発明の一態様であるニッケル元素の回収方法（以下、「本発明の回収方法」と略す場合がある。）は、ニッケル含有水溶液を準備する準備工程（以下、「準備工程」と略す場合がある。）、並びに下記一般式（１）で表される化合物又はその塩の存在下、前記準備工程で準備したニッケル含有水溶液と有機溶媒を接触させて、ニッケル元素（Ｎｉ）を抽出する液液接触工程（以下、「液液接触工程」と略す場合がある。）を含むことを特徴とする。
（式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ同一種又は異種の炭化水素基を表す。但し、Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基の炭素数の合計が、８〜６４である。）
本発明者らは、ニッケル元素の回収方法について鋭意検討を重ねた結果、一般式（１）で表される化合物又はその塩の存在下で抽出を行うことにより、ニッケル含有水溶液からニッケル元素を効率的に回収することができることを見出したのである。
一般式（１）で表される化合物は、ニトリロ三酢酸の２つのカルボキシル基がジアルキルアミンによってアミド化された構造となっているが、構造内に含まれる第三級アミノ基、アミド基、及びカルボキシル基が、ニッケル元素との結合に非常に適しているものと考えられる。そして、水素イオン濃度やアニオン濃度によって、それぞれの金属元素に対する親和性が変化するため、ニッケル元素を選択的に抽出することを可能とし、さらに炭化水素基の炭素数等によって有機溶媒との親和性を制御できるため、溶媒抽出法による回収に適しているのである。
なお、「その塩」とは、一般式（１）で表される化合物とイオン等によって形成される
塩を意味し、塩を形成するためのイオンの種類は特に限定されないものとする。
また、「一般式（１）で表される化合物又はその塩の存在下」とは、通常有機溶媒に一般式（１）で表される化合物又はその塩が存在していることを意味し、予め有機溶媒に含有させていても、或いはニッケル含有水溶液と有機溶媒を接触させるときに別途一般式（１）で表される化合物又はその塩を添加するものであってもよいものとする。
以下、「準備工程」、「液液接触工程」等について、詳細に説明する。
<Recovery method of nickel element>
The nickel element recovery method (hereinafter may be abbreviated as “recovery method of the present invention”), which is an embodiment of the present invention, may be abbreviated as “preparation step” (hereinafter referred to as “preparation step”). In addition, in the presence of the compound represented by the following general formula (1) or a salt thereof, the liquid solution for extracting nickel element (Ni) by bringing the nickel-containing aqueous solution prepared in the preparation step into contact with an organic solvent. It includes a contact step (hereinafter sometimes abbreviated as “liquid-liquid contact step”).
(In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent the same or different hydrocarbon group, provided that R 1 , R 2 , R 3 , and R 4 are hydrocarbons. The total number of carbon atoms in the group is 8 to 64.)
As a result of intensive studies on a method for recovering nickel element, the present inventors have efficiently extracted nickel element from an aqueous solution containing nickel by performing extraction in the presence of the compound represented by the general formula (1) or a salt thereof. It was found that it can be recovered automatically.
The compound represented by the general formula (1) has a structure in which two carboxyl groups of nitrilotriacetic acid are amidated with dialkylamine, but a tertiary amino group, an amide group, and It is considered that the carboxyl group is very suitable for bonding with nickel element. And the affinity for each metal element changes depending on the hydrogen ion concentration and anion concentration, so it is possible to selectively extract nickel element, and the affinity with organic solvent by the number of carbons of the hydrocarbon group, etc. Therefore, it is suitable for recovery by a solvent extraction method.
The “salt thereof” means a salt formed by the compound represented by the general formula (1) and ions, and the kind of ions for forming the salt is not particularly limited.
Further, “in the presence of the compound represented by the general formula (1) or a salt thereof” means that the compound represented by the general formula (1) or a salt thereof is usually present in an organic solvent, The compound represented by the general formula (1) or a salt thereof may be added in advance when the nickel-containing aqueous solution and the organic solvent are brought into contact with each other.
Hereinafter, the “preparation step”, “liquid-liquid contact step”, and the like will be described in detail.
準備工程は、ニッケル含有水溶液を準備する工程であるが、準備するニッケル含有水溶液の具体的種類やニッケル元素の含有量は特に限定されない。ニッケル含有水溶液の具体的種類としては、電解ニッケルめっき液、使用済み電解ニッケルめっき液、無電解ニッケルめっき液、使用済み無電解ニッケルめっき液、廃Ｎｉ−Ｃｄ電池を浸出して得られる溶液、含ニッケル鉱を浸出して得られる溶液等が挙げられる。また、例えば使用済み無電解ニッケルめっき液は、めっき条件などによって異なるが、ニッケル元素以外に、２０〜１００ｇ／Ｌのナトリウム元素（Ｎａ）、５〜７０ｇ／Ｌの硫酸イオン、１０〜２０ｇ／Ｌの次亜リン酸イオン（Ｈ２ＰＯ２ −）、１５〜１１０ｇ／Ｌの亜リン酸イオン（ＨＰＯ３ ２−）、３０〜５０ｇ／Ｌの有機酸（例えば、乳酸、プロピオン酸、リンゴ酸、コハク酸等）が含まれており、ｐＨは、通常、４．０〜７．０の範囲にある。
ｐＨ３．０〜ｐＨ６．０であると、ニッケル元素をより効率的に回収することができるため、ニッケル含有水溶液をそのまま使用するほか、ニッケル含有水溶液に酸や塩基を添加して、ｐＨを調整してもよい。但し、ｐＨを調整しなくてもニッケル元素を効率的に回収することができる点が本発明の回収方法の利点の１つである。なお、使用する酸の具体的種類は、特に限定されないが、塩酸、硫酸、硝酸、リン酸、亜リン酸、次亜リン酸等の無機酸が挙げられる。塩酸を使用する場合、水溶液は塩化物イオン（Ｃｌ−）を含み、硫酸を使用する場合、水溶液は硫酸イオン（ＳＯ４ ２−）を含み、硝酸を使用する場合、水溶液は硝酸イオン（ＮＯ３ −）を含み、リン酸を使用する場合、水溶液はリン酸イオン（ＰＯ４ ３−、ＨＰＯ４ ２−、Ｈ２ＰＯ４ −）を含み、亜リン酸を使用する場合、水溶液は亜リン酸イオン（ＨＰＯ３ ２−、Ｈ２ＰＯ３ −）を含み、次亜リン酸を使用する場合、水溶液は次亜リン酸イオン（Ｈ２ＰＯ２ −）を含むと表現することができる。
Although a preparation process is a process of preparing nickel-containing aqueous solution, the specific kind of nickel-containing aqueous solution to prepare and content of nickel element are not specifically limited. Specific types of nickel-containing aqueous solutions include electrolytic nickel plating solutions, used electrolytic nickel plating solutions, electroless nickel plating solutions, used electroless nickel plating solutions, solutions obtained by leaching waste Ni-Cd batteries, Examples include a solution obtained by leaching nickel ore. In addition, for example, the used electroless nickel plating solution varies depending on plating conditions and the like, but in addition to nickel element, 20 to 100 g / L sodium element (Na), 5 to 70 g / L sulfate ion, 10 to 20 g / L. Hypophosphite ion (H 2 PO 2 − ), 15 to 110 g / L phosphite ion (HPO 3 2− ), 30 to 50 g / L organic acid (eg, lactic acid, propionic acid, malic acid, PH is usually in the range of 4.0-7.0.
When the pH is 3.0 to 6.0, the nickel element can be recovered more efficiently, so the nickel-containing aqueous solution is used as it is, and the pH is adjusted by adding an acid or base to the nickel-containing aqueous solution. May be. However, one of the advantages of the recovery method of the present invention is that nickel element can be recovered efficiently without adjusting the pH. In addition, although the specific kind of acid to be used is not specifically limited, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, are mentioned. When hydrochloric acid is used, the aqueous solution contains chloride ions (Cl − ), when sulfuric acid is used, the aqueous solution contains sulfate ions (SO 4 2− ), and when nitric acid is used, the aqueous solution is nitrate ions (NO 3 - ) And phosphoric acid is used, the aqueous solution contains phosphate ions (PO 4 3− , HPO 4 2− , H 2 PO 4 − ), and when phosphorous acid is used, the aqueous solution is phosphorous acid. In the case of containing ions (HPO 3 2− , H 2 PO 3 − ) and using hypophosphorous acid, the aqueous solution can be expressed as containing hypophosphite ions (H 2 PO 2 − ).
液液接触工程は、一般式（１）で表される化合物又はその塩の存在下、前記準備工程で準備したニッケル含有水溶液と有機溶媒を接触させて、ニッケル元素（Ｎｉ）を抽出する工程であるが、一般式（１）で表される化合物又はその塩の具体的種類は、特に限定されず、目的に応じて適宜選択することができる。
（式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ同一種又は異種の炭化水素基を表す。但し、Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基の炭素数の合計が、８〜６４である。）
Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ同一種又は異種の炭化水素基を表しているが、「炭化水素基」とは、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよいことを意味する。
Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基の炭素数の合計は、８〜６４であるが、好ましくは１６以上、より好ましくは２４以上であり、好ましくは５６以下、より好ましくは４８以下である。
Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基のそれぞれの炭素数は、通常２以上、好まし
くは４以上、より好ましくは６以上であり、通常１６以下、好ましくは１４以下、より好ましくは１２以下である。
Ｒ１、Ｒ２、Ｒ３、Ｒ４としては、エチル基（−Ｃ２Ｈ５）、ｎ−プロピル基（−ｎＣ３Ｈ７）、ｉ−プロピル基（−ｉＣ３Ｈ７）、ｎ−ブチル基（−ｎＣ４Ｈ９）、ｔ−ブチル基（−ｔＣ４Ｈ９）、ｎ−ペンチル基（−ｎＣ５Ｈ１１）、ｎ−ヘキシル基（−ｎＣ６Ｈ１３）、ｎ−ヘプチル基（−ｎＣ７Ｈ１５）、ｎ−オクチル基（−ｎＣ８Ｈ１７）、２−エチルヘキシル基（−ＣＨ２ＣＨ（Ｃ２Ｈ５）Ｃ４Ｈ９）、ｎ−ノニル基（−ｎＣ９Ｈ１９）、ｎ−デシル基（−ｎＣ１０Ｈ２１）、ｎ−ウンデシル基（−ｎＣ１１Ｈ２３）、ｎ−ドデシル基（−ｎＣ１２Ｈ２５）、ｎ−トリデシル基（−ｎＣ１３Ｈ２７）、ｎ−テトラデシル基（−ｎＣ１４Ｈ２９）、ｎ−ペンタデシル基（−ｎＣ１５Ｈ３１）、ｎ−ヘキサデシル基（−ｎＣ１６Ｈ３３）、シクロヘキシル基（−ｃＣ６Ｈ１１）、フェニル基（−Ｃ６Ｈ５）、ナフチル基（−Ｃ１０Ｈ７）等が挙げられる。この中でも、ｎ−ヘキシル基（−ｎＣ６Ｈ１３）、ｎ−オクチル基（−ｎＣ８Ｈ１７）、２−ジエチルヘキシル基（−ＣＨ２ＣＨ（Ｃ２Ｈ５）Ｃ４Ｈ９）、ｎ−デシル基（−ｎＣ１０Ｈ２１）、ｎ−ドデシル基（−ｎＣ１２Ｈ２５）等が特に好ましい。
The liquid-liquid contact step is a step of extracting nickel element (Ni) by contacting the nickel-containing aqueous solution prepared in the preparation step with an organic solvent in the presence of the compound represented by the general formula (1) or a salt thereof. However, the specific type of the compound represented by the general formula (1) or a salt thereof is not particularly limited and can be appropriately selected depending on the purpose.
(In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent the same or different hydrocarbon group, provided that R 1 , R 2 , R 3 , and R 4 are hydrocarbons. The total number of carbon atoms in the group is 8 to 64.)
R 1 , R 2 , R 3 , and R 4 each represent the same or different hydrocarbon group, but the “hydrocarbon group” is not limited to a linear saturated hydrocarbon group, -It means that each may have a carbon unsaturated bond, a branched structure, and a cyclic structure.
The total number of carbon atoms of the hydrocarbon groups of R 1 , R 2 , R 3 and R 4 is 8 to 64, preferably 16 or more, more preferably 24 or more, preferably 56 or less, more preferably Is 48 or less.
The carbon number of each of the hydrocarbon groups of R 1 , R 2 , R 3 , and R 4 is usually 2 or more, preferably 4 or more, more preferably 6 or more, and usually 16 or less, preferably 14 or less, more Preferably it is 12 or less.
R 1 , R 2 , R 3 , and R 4 include an ethyl group (—C 2 H 5 ), an n-propyl group ( —n C 3 H 7 ), an i-propyl group ( —i C 3 H 7 ), n- butyl (- n C 4 H 9) , t- butyl (- t C 4 H 9) , n- pentyl (- n C 5 H 11) , n- hexyl group (- n C 6 H 13 ), n-heptyl (- n C 7 H 15) , n- octyl group (- n C 8 H 17) , 2- ethylhexyl group (-CH 2 CH (C 2 H 5) C 4 H 9), n - nonyl group (- n C 9 H 19) , n- decyl group (- n C 10 H 21) , n- undecyl group (- n C 11 H 23) , n- dodecyl group (- n C 12 H 25) , n- tridecyl group (- n C 13 H 27) , n- tetradecyl (- n C 14 H 29) , n- Ntadeshiru group (- n C 15 H 31) , n- hexadecyl group (- n C 16 H 33) , cyclohexyl (- c C 6 H 11) , phenyl group (-C 6 H 5), naphthyl group (-C 10 H 7 ) and the like. Among this, n- hexyl group (- n C 6 H 13) , n- octyl group (- n C 8 H 17) , 2- di-ethylhexyl group (-CH 2 CH (C 2 H 5) C 4 H 9) , n- decyl group (- n C 10 H 21) , n- dodecyl group (- n C 12 H 25) are particularly preferred.
一般式（１）で表される化合物としては、下記式で表されるものが挙げられる。
また、一般式（１）で表される化合物から形成される塩の種類としては、アンモニウム塩、リチウム塩、ナトリウム塩、カリウム塩、塩酸塩、硝酸塩、硫酸塩、酢酸塩等が挙げられる。
Examples of the compound represented by the general formula (1) include those represented by the following formula.
Examples of the salt formed from the compound represented by the general formula (1) include ammonium salt, lithium salt, sodium salt, potassium salt, hydrochloride, nitrate, sulfate, acetate, and the like.
一般式（１）で表される化合物又はその塩の製造方法は、特に限定されず、公知の有機合成法を適宜組み合わせて製造することができるが、下記（ｉ）〜（ｉｉｉ）の工程を含む製造方法が挙げられる。
（ｉ）２−ハロゲン化アセチルハライドに対するジアルキルアミンの求核置換反応によって、２−ハロゲノ−Ｎ，Ｎ−ジアルキルアセトアミドを得る工程。
（ｉｉ）２−ハロゲノ−Ｎ，Ｎ−ジアルキルアセトアミドに対するイミノジ酢酸の求核置換反応によって、ニトリロ三酢酸誘導体を得る工程。
（ｉｉｉ）ニトリロ三酢酸誘導体の１つのカルボキシル基をジアルキルアミンでアミド化することによって、一般式（１）で表される化合物又はその塩を得る工程。
なお、下記式で表される化合物は、市販されており、適宜入手して一般式（１）に該当する幅広い化合物を製造することができる。
(I) A step of obtaining 2-halogeno-N, N-dialkylacetamide by nucleophilic substitution reaction of dialkylamine with 2-halogenated acetyl halide.
(Ii) A step of obtaining a nitrilotriacetic acid derivative by nucleophilic substitution reaction of iminodiacetic acid with 2-halogeno-N, N-dialkylacetamide.
(Iii) A step of obtaining a compound represented by the general formula (1) or a salt thereof by amidating one carboxyl group of a nitrilotriacetic acid derivative with a dialkylamine.
In addition, the compound represented with a following formula is marketed, and it can acquire suitably and can manufacture the wide compound applicable to General formula (1).
液液接触工程の操作手順は、特に限定されず、溶媒抽出法に利用される公知の操作手順を適宜選択することができる。例えば、任意の容器にニッケル含有水溶液と有機溶媒を投入し、振とう機等を用いてニッケル含有水溶液と有機溶媒を十分に混合した後、遠心分離によって相分離させて、分液を行うことが挙げられる。また、容器の代わりに向流抽出装置等の抽出装置や分液漏斗等の公知の抽出装置又は抽出器具を用いることもできる。
また、一般式（１）で表される化合物又はその塩の存在下でニッケル含有水溶液と有機溶媒を接触させる方法は、例えば下記（イ）〜（ハ）の方法が挙げられる。
（イ）一般式（１）で表される化合物又はその塩を含む有機溶媒溶液を、容器内等でニッケル含有水溶液と接触させる方法。
（ロ）一般式（１）で表される化合物又はその塩を含むニッケル含有水溶液を、容器内等で有機溶媒と接触させる方法。
（ハ）一般式（１）で表される化合物又はその塩とニッケル含有水溶液と有機溶媒をそれぞれ容器等に投入し、接触させる方法。
この中でも、（イ）の方法が特に好ましい。
The operation procedure of the liquid-liquid contact step is not particularly limited, and a known operation procedure used for the solvent extraction method can be appropriately selected. For example, a nickel-containing aqueous solution and an organic solvent are charged into an arbitrary container, and after sufficiently mixing the nickel-containing aqueous solution and the organic solvent using a shaker or the like, phase separation is performed by centrifugal separation. Can be mentioned. Moreover, well-known extraction apparatuses or extraction instruments, such as an extraction apparatus, such as a countercurrent extraction apparatus, a separatory funnel, can also be used instead of a container.
Examples of the method of bringing the nickel-containing aqueous solution into contact with the organic solvent in the presence of the compound represented by the general formula (1) or a salt thereof include the following methods (a) to (c).
(A) A method of bringing an organic solvent solution containing the compound represented by the general formula (1) or a salt thereof into contact with a nickel-containing aqueous solution in a container or the like.
(B) A method of bringing a nickel-containing aqueous solution containing the compound represented by the general formula (1) or a salt thereof into contact with an organic solvent in a container or the like.
(C) A method in which the compound represented by the general formula (1) or a salt thereof, a nickel-containing aqueous solution, and an organic solvent are put into a container or the like and brought into contact with each other.
Among these, the method (A) is particularly preferable.
一般式（１）で表される化合物又はその塩の使用量（存在量）は、特に限定されず、目的に応じて適宜選択することができるが、有機溶媒中の濃度として、通常０．０１〜１．１ｍｏｌ／Ｌの範囲であり、好ましくは０．１〜０．５ｍｏｌ／Ｌの範囲である。 The amount (abundance) of the compound represented by the general formula (1) or a salt thereof is not particularly limited and can be appropriately selected according to the purpose. It is the range of -1.1 mol / L, Preferably it is the range of 0.1-0.5 mol / L.
有機溶媒としては、ケロシン等の石油系溶媒；ヘキサン、イソオクタン、ドデカン等の脂肪族炭化水素系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；クロロホルム、ジクロロメタン等のハロゲン系溶媒；ドデシルアルコール、オクタノール等の高級アルコール系溶媒等を挙げることができる。なお、有機溶媒は、単独でも２種以上を混合して使用してもよい。 Organic solvents include petroleum solvents such as kerosene; aliphatic hydrocarbon solvents such as hexane, isooctane and dodecane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; halogen solvents such as chloroform and dichloromethane; dodecyl Examples thereof include higher alcohol solvents such as alcohol and octanol. In addition, an organic solvent may be used individually or in mixture of 2 or more types.
接触させるニッケル含有水溶液と有機溶媒の容積比（水溶液／有機溶媒）は、特に限定されず、目的に応じて適宜選択することができるが、通常１以上である。 The volume ratio of the nickel-containing aqueous solution to be brought into contact with the organic solvent (aqueous solution / organic solvent) is not particularly limited and can be appropriately selected depending on the purpose, but is usually 1 or more.
本発明の回収方法は、前述の準備工程及び液液接触工程を含むものであれば、その他については特に限定されないが、さらに下記の分液工程及び逆抽出工程を含むことが特に好ましい。
・液液接触工程で接触させたニッケル含有水溶液と有機溶媒を分液する分液工程
・分液工程で分液した有機溶媒に、分液工程で分液したニッケル含有水溶液とは別の酸性水溶液を接触させて逆抽出する逆抽出工程
The recovery method of the present invention is not particularly limited as long as it includes the above-described preparation step and liquid-liquid contact step, but it is particularly preferable to further include the following liquid separation step and back extraction step.
-Separation process for separating the nickel-containing aqueous solution and the organic solvent brought into contact with each other in the liquid-liquid contact process-An acidic aqueous solution different from the nickel-containing aqueous solution separated in the liquid separation process into the organic solvent separated in the liquid separation process Back-extraction process for back-extraction by contacting
分液工程で分液したニッケル含有水溶液とは別の酸性水溶液は、逆抽出に利用できるものであれば特に限定されないが、そのｐＨは、準備工程で準備したニッケル含有水溶液のｐＨよりも低く調整されていることが好ましく、その水素イオン濃度は０．１ｍｏｌ／Ｌ以上、より好ましくは０．２ｍｏｌ／Ｌ以上である。なお、使用する酸としては、特に限定されないが、塩酸、硫酸、硝酸、リン酸、亜リン酸、次亜リン酸等の無機酸が挙げられる。 The acidic aqueous solution different from the nickel-containing aqueous solution separated in the liquid separation step is not particularly limited as long as it can be used for back extraction, but the pH is adjusted to be lower than the pH of the nickel-containing aqueous solution prepared in the preparation step. The hydrogen ion concentration is preferably 0.1 mol / L or more, more preferably 0.2 mol / L or more. In addition, although it does not specifically limit as an acid to be used, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, are mentioned.
以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention can be modified as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
＜合成例１：テトラオクチルニトリロ酢酸ジアセトアミド（ＴＯＮＴＡＤＡ）の合成＞
下記反応式で表される反応によって、２−クロロ−Ｎ，Ｎ−ジオクチルアセトアミド（以下、「ＣｌＤＯＡＡ」と略す場合がある。）を合成した。
ジオクチルアミン２５ｇ（１０１ｍｍｏｌ）を１００ｍＬの脱水ジクロロメタンに溶解させ、さらにトリエチルアミン１０．３２ｇ（１０１ｍｍｏｌ）を加えて氷浴で撹拌した
。この溶液に脱水ジクロロメタン１０ｍＬに溶解させた塩化クロロアセチル１４．１ｇ（１２１ｍｍｏｌ）を、氷浴中アルゴン置換の下、ゆっくり滴下した。滴下後、室温で３時間撹拌して反応を終了した。反応後、０．１ｍｏｌ／Ｌ塩酸１００ｍＬで３回、超純水１００ｍＬで４回分液を行い、回収した有機相を硫酸ナトリウムで脱水した。硫酸ナトリウムをろ過し、エバポレーターにより溶媒を減圧留去した。さらに、カラムクロマトグラフィー（シリカゲル、展開溶媒 ヘキサン：酢酸エチル＝３：１）により精製を行った。溶媒を完全に減圧留去し、黄色粘性液体２８．１ｇ（収率：８７．５％）を得た。得られた合成物を核磁気共鳴法（ＮＭＲ）、元素分析、マトリックス支援レーザー脱離イオン化飛行時間型質量分析装置（ＭＡＬＤＩ−ＴＯＦ／ＭＳ）を用いて同定したところ、２−クロロ−Ｎ，Ｎ−ジオクチルアセトアミド（ＣｌＤＯＡＡ）であることを確認した。
<Synthesis Example 1: Synthesis of tetraoctylnitriloacetic acid diacetamide (TONTADA)>
2-Chloro-N, N-dioctylacetamide (hereinafter sometimes abbreviated as “ClDOAA”) was synthesized by a reaction represented by the following reaction formula.
25 g (101 mmol) of dioctylamine was dissolved in 100 mL of dehydrated dichloromethane, and 10.32 g (101 mmol) of triethylamine was further added, followed by stirring in an ice bath. To this solution, 14.1 g (121 mmol) of chloroacetyl chloride dissolved in 10 mL of dehydrated dichloromethane was slowly added dropwise under argon substitution in an ice bath. After dropping, the reaction was terminated by stirring at room temperature for 3 hours. After the reaction, liquid separation was performed 3 times with 100 mL of 0.1 mol / L hydrochloric acid and 4 times with 100 mL of ultrapure water, and the collected organic phase was dehydrated with sodium sulfate. Sodium sulfate was filtered, and the solvent was distilled off under reduced pressure using an evaporator. Furthermore, purification was performed by column chromatography (silica gel, developing solvent hexane: ethyl acetate = 3: 1). The solvent was completely distilled off under reduced pressure to obtain 28.1 g (yield: 87.5%) of a yellow viscous liquid. The obtained compound was identified using nuclear magnetic resonance (NMR), elemental analysis, matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF / MS), and 2-chloro-N, N -Dioctylacetamide (ClDOAA) was confirmed.
下記反応式で表される反応によって、２，２’−（２−（ジオクチルアミノ）−２−オクソエチルアザンジイル）二酢酸（以下、「ＤＯＮＴＡＭＡ」と略す場合がある。）を合成した。
水酸化ナトリウム３．３ｇ（８０ｍｍｏｌ）を超純水２５０ｍＬに溶解し、さらにイミノジ酢酸１０．６５ｇ（８０ｍｍｏｌ）を溶解させた。溶解後、５ｍｏｌ／Ｌ水酸化ナトリウム水溶液を１２ｍＬ、ｐＨ試験紙が青色になるまで加え、さらにエタノール２３０ｍＬを加えて撹拌した。ＣｌＤＯＡＡ １２．７ｇ（４０ｍｍｏｌ）をエタノール２０ｍＬに溶解させ、アルゴン置換後、室温で撹拌しながらゆっくり滴下した。滴下後、８５℃で１７．５時間還流した。還流中、ｐＨが１１程度になるように随時５ｍｏｌ／Ｌ水酸化ナトリウム水溶液を加え、さらに同体積のエタノールを加えた。反応溶液からエバポレーターによりエタノールのみ留去した。残った水溶液をジエチルエーテル１００ｍＬで３回分液を行った。得られた水溶液を撹拌しながら３ｍｏｌ／Ｌ塩酸３０ｍＬを加え、生じた白色沈殿物をろ過により回収した。得られた沈殿物を超純水１００ｍＬで２回洗浄し、真空乾燥後、アセトンとヘキサンを用いて再沈殿により精製を行い、白色粉末１２．９ｇ（収率：７７．８％）を得た。得られた合成物を核磁気共鳴法（ＮＭＲ）、元素分析、マトリックス支援レーザー脱離イオン化飛行時間型質量分析装置（ＭＡＬＤＩ−ＴＯＦ／ＭＳ）を用いて同定したところ、２，２’−（２−（ジオクチルアミノ）−２−オクソエチルアザンジイル）二酢酸（ＤＯＮＴＡＭＡ）であることを確認した。
2,2 ′-(2- (Dioctylamino) -2-oxoethylazanediyl) diacetic acid (hereinafter sometimes abbreviated as “DONTAMA”) was synthesized by a reaction represented by the following reaction formula.
Sodium hydroxide 3.3 g (80 mmol) was dissolved in ultrapure water 250 mL, and further iminodiacetic acid 10.65 g (80 mmol) was dissolved. After dissolution, 12 mL of 5 mol / L sodium hydroxide aqueous solution was added until the pH test paper turned blue, and further 230 mL of ethanol was added and stirred. 12.7 g (40 mmol) of ClDOAA was dissolved in 20 mL of ethanol, purged with argon, and then slowly added dropwise with stirring at room temperature. After dropping, the mixture was refluxed at 85 ° C. for 17.5 hours. During the reflux, a 5 mol / L aqueous sodium hydroxide solution was added as needed so that the pH was about 11, and the same volume of ethanol was further added. Only ethanol was distilled off from the reaction solution with an evaporator. The remaining aqueous solution was subjected to liquid separation three times with 100 mL of diethyl ether. While stirring the obtained aqueous solution, 30 mL of 3 mol / L hydrochloric acid was added, and the resulting white precipitate was collected by filtration. The obtained precipitate was washed twice with 100 mL of ultrapure water, vacuum dried, and purified by reprecipitation using acetone and hexane to obtain 12.9 g of white powder (yield: 77.8%). . The obtained compound was identified using nuclear magnetic resonance (NMR), elemental analysis, matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF / MS), and 2,2 ′-(2 -(Dioctylamino) -2-oxoethylazanediyl) diacetic acid (DONTAMA).
下記反応式で表される反応によって、テトラオクチルニトリロ酢酸ジアセトアミド（以下、「ＴＯＮＴＡＤＡ」と略す場合がある。）を合成した。
合成したＤＯＮＴＡＭＡ ４．３５ｇ（１０．５ｍｍｏｌ）を１２０ｍＬの脱水ジクロロメタンに懸濁させた。水溶性カルボジイミド（ＷＳＣ）２．１６ｇ （１１．０４ｍｍ
ｏｌ）を脱水ジクロロメタン１２０ｍＬに溶かし、室温で撹拌しながらアルゴン置換の下、ゆっくり滴下し、１時間撹拌を行った。撹拌後、ジオクチルアミン２．７２ｇ（１１．０４ｍｍｏｌ）を脱水ジクロロメタン１０ｍＬに溶かし、室温で撹拌しながらアルゴン置換の下、ゆっくり滴下した。滴下後、４０℃で２４時間還流した。反応後、１ｍｏｌ／Ｌ塩酸２００ｍＬで３回、超純水２００ｍＬで４回分液を行い、回収した有機相を硫酸ナトリウムで脱水した。硫酸ナトリウムをろ過し、エバポレーターにより溶媒を減圧留去した。さらに、カラムクロマトグラフィー（シリカゲル、展開溶媒 酢酸エチル）により精製を行った。溶媒を完全に減圧留去し、無色透明液体４．３１ｇ（収率：６４．３％）を得た。得られた合成物を核磁気共鳴法（ＮＭＲ）、元素分析、マトリックス支援レーザー脱離イオン化飛行時間型質量分析装置（ＭＡＬＤＩ−ＴＯＦ／ＭＳ）を用いて同定したところ、テトラオクチルニトリロ酢酸ジアセトアミド（ＴＯＮＴＡＤＡ）であることを確認した。なお、図１に１Ｈ ＮＭＲの結果を示す。
１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，２５℃）: δ０．８８（ｍ，１２Ｈ，ＣＨ３），１．２８（ｓ，４０Ｈ，ＣＨ３（ＣＨ２）５），１．５２（ｍ，８Ｈ，ＣＨ２ＣＨ２Ｎ），３．１０（ｔ，４Ｈ，ＣＨ２Ｎ），３．３０（ｔ，４Ｈ，ＣＨ２Ｎ），３．４８（ｓ，２Ｈ，ＮＣＨ２ＣＯＯＨ），３．６７（ｓ，４Ｈ，ＮＣＨ２Ｃ＝Ｏ）．
Tetraoctylnitriloacetic acid diacetamide (hereinafter sometimes abbreviated as “TONTADA”) was synthesized by a reaction represented by the following reaction formula.
The synthesized DONTAMA (4.35 g, 10.5 mmol) was suspended in 120 mL of dehydrated dichloromethane. Water-soluble carbodiimide (WSC) 2.16 g (11.04 mm
ol) was dissolved in 120 mL of dehydrated dichloromethane, and slowly added dropwise under argon substitution while stirring at room temperature, followed by stirring for 1 hour. After stirring, 2.72 g (11.04 mmol) of dioctylamine was dissolved in 10 mL of dehydrated dichloromethane and slowly added dropwise under argon substitution while stirring at room temperature. After the dropwise addition, the mixture was refluxed at 40 ° C. for 24 hours. After the reaction, liquid separation was performed 3 times with 200 mL of 1 mol / L hydrochloric acid and 4 times with 200 mL of ultrapure water, and the collected organic phase was dehydrated with sodium sulfate. Sodium sulfate was filtered, and the solvent was distilled off under reduced pressure using an evaporator. Further, purification was performed by column chromatography (silica gel, developing solvent ethyl acetate). The solvent was completely distilled off under reduced pressure to obtain 4.31 g of colorless transparent liquid (yield: 64.3%). The obtained compound was identified using nuclear magnetic resonance (NMR), elemental analysis, matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF / MS), and tetraoctylnitriloacetic acid diacetamide ( TONTADA). In addition, the result of 1 H NMR is shown in FIG.
1 H NMR (400 MHz, CDCl 3 , 25 ° C.): δ 0.88 (m, 12 H, CH 3 ), 1.28 (s, 40 H, CH 3 (CH 2 ) 5 ), 1.52 (m, 8 H, CH 2 CH 2 N), 3.10 (t, 4H, CH 2 N), 3.30 (t, 4H, CH 2 N), 3.48 (s, 2H, NCH 2 COOH), 3.67 ( s, 4H, NCH 2 C = O).
＜合成例２：ジオクチルジグリコールアミド酸（ＤＯＤＧＡＡ）の合成＞
比較として、ジオクチルジグリコールアミド酸（以下、「ＤＯＤＧＡＡ」と略す場合がある。）を準備した。ＤＯＤＧＡＡは、下記反応式で表される反応によって合成した。なお、ＤＯＤＧＡＡの合成方法については、本発明者らが既に報告しているH. Naganawa et
al., Solvent Extr. Res. Dev., Jpn, 2007, 14, 151-159.等を参照することができる。
無水ジグリコール酸４．１７ｇ（０．０３６ｍｏｌ）を三角フラスコに入れ、４０ｍＬのジクロロメタンに懸濁させた。滴下漏斗にジクロロメタン１０ｍＬに溶解させたオクチルアミン７ｇ（０．０２８４ｍｏｌ）を入れ、氷浴の下、撹拌しながらゆっくり滴下した。滴下後、室温で一晩撹拌し、溶液が透明になっていることを確認し、反応を終了した。超純水で中性になるまで４回分液を行い、水溶性不純物を除去した。分液後の溶液を硫酸ナトリウムで脱水し、硫酸ナトリウムを濾過により取り除いた。エバポレーターにより溶媒を減圧留去した後、真空ポンプで完全に溶媒を除去した。ヘキサンで溶液が透明になるまで３回再結晶を行い、凍結乾燥機で完全に乾燥させた。白色粉末。収量９．５７ｇ、収率９４．２％。得られた合成物は元素分析及び１Ｈ ＮＭＲにより、ＤＯＤＧＡＡであることを確認した。
<Synthesis Example 2: Synthesis of dioctyl diglycolamide acid (DODGAA)>
For comparison, dioctyl diglycol amide acid (hereinafter sometimes abbreviated as “DODGAA”) was prepared. DODGAA was synthesized by a reaction represented by the following reaction formula. Regarding the method for synthesizing DODGAA, H. Naganawa et al.
al., Solvent Extr. Res. Dev., Jpn, 2007, 14, 151-159.
Diglycolic anhydride (4.17 g, 0.036 mol) was placed in an Erlenmeyer flask and suspended in 40 mL of dichloromethane. The dropping funnel was charged with 7 g (0.0284 mol) of octylamine dissolved in 10 mL of dichloromethane and slowly added dropwise with stirring in an ice bath. After the dropwise addition, the mixture was stirred overnight at room temperature, and it was confirmed that the solution was transparent, and the reaction was completed. Liquid separation was performed 4 times until neutrality with ultrapure water to remove water-soluble impurities. The separated solution was dehydrated with sodium sulfate, and sodium sulfate was removed by filtration. After the solvent was distilled off under reduced pressure with an evaporator, the solvent was completely removed with a vacuum pump. Recrystallization was performed 3 times until the solution became transparent with hexane, and the solution was completely dried with a freeze dryer. White powder. Yield 9.57 g, yield 94.2%. The obtained synthesized product was confirmed to be DODGAA by elemental analysis and 1 H NMR.
＜実施例１：ＴＯＮＴＡＤＡを用いたＮｉの抽出挙動＞
Ｎｉイオンを０．０１ｍＭ含んだｐＨ０．６〜５．８水溶液を調製した。このとき、ｐＨ１．０〜５．８の水溶液は２−モルホリノエタンスルホン酸（ＭＥＳ）緩衝液に硝酸又は水酸化ナトリウム水溶液を加えて調製した。ｐＨ１．０以下の水溶液については硝酸のみで調製した。
調製した水溶液と、それと同体積の１０ｍＭ ＴＯＮＴＡＤＡを含むイソオクタン溶液を混合し、２５℃で３０分間以上激しく振盪した。振盪後、両相を分取し、分取した水相はｐＨ測定を行い、硝酸水溶液で希釈後、誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ）を用いて、Ｎｉイオンの濃度を測定した。
一方、分取した有機相と、それと同体積の１Ｍ硝酸を混合し、２５℃で３０分間以上激
しく振盪することで逆抽出を行った。逆抽出相中のＮｉイオン濃度をＩＣＰを用いて測定した。得られたＮｉイオン濃度から抽出率を、有機相中の物質量／初期条件の物質量×１００で定義し、算出した。抽出結果を図２に示す。黒丸がＴＯＮＴＡＤＡを用いた抽出率の結果である。
<Example 1: Extraction behavior of Ni using TONTADA>
A pH 0.6-5.8 aqueous solution containing 0.01 mM of Ni ions was prepared. At this time, an aqueous solution having a pH of 1.0 to 5.8 was prepared by adding nitric acid or an aqueous sodium hydroxide solution to a 2-morpholinoethanesulfonic acid (MES) buffer solution. An aqueous solution having a pH of 1.0 or less was prepared using only nitric acid.
The prepared aqueous solution was mixed with an isooctane solution containing 10 mM TONTADA in the same volume, and shaken vigorously at 25 ° C. for 30 minutes or more. After shaking, both phases were separated, and the separated aqueous phase was subjected to pH measurement, diluted with an aqueous nitric acid solution, and then the Ni ion concentration was measured using an inductively coupled plasma mass spectrometer (ICP-MS).
On the other hand, the separated organic phase and the same volume of 1 M nitric acid were mixed, and back extraction was performed by shaking vigorously at 25 ° C. for 30 minutes or more. The Ni ion concentration in the back extraction phase was measured using ICP. The extraction rate was defined and calculated from the obtained Ni ion concentration by the amount of the substance in the organic phase / the amount of the substance in the initial condition × 100. The extraction result is shown in FIG. The black circle is the result of the extraction rate using TONTADA.
＜比較例１：ＤＯＤＧＡＡを用いたＮｉの抽出挙動＞
水相のｐＨを２．０〜５．８に調整し、抽出剤ＤＯＤＧＡＡをイソオクタン（５％ １−オクタノール）に溶解した有機相を用いたこと以外は、実施例１と同じ方法で抽出実験を行った。結果を図２に示す。白丸がＤＯＤＧＡＡを用いた抽出率の結果である。
<Comparative Example 1: Extraction behavior of Ni using DODGAA>
The extraction experiment was carried out in the same manner as in Example 1 except that the pH of the aqueous phase was adjusted to 2.0 to 5.8 and an organic phase in which the extractant DODGAA was dissolved in isooctane (5% 1-octanol) was used. went. The results are shown in FIG. The white circle is the result of the extraction rate using DODGAA.
＜比較例２及び３：Ｄ２ＥＨＰＡ又はＰＣ−８８Ａを用いたＮｉの抽出挙動＞
水相のｐＨを０．８〜７．０に調整し、抽出剤（ジ（２−エチルヘキシル）リン酸（Ｄ２ＥＨＰＡ）、２−エチルヘキシルホスホン酸モノ−２−エチルヘキシルエステル（ＰＣ−８８Ａ））をイソオクタンに溶解した有機相を用いたこと以外は、実施例１と同じ方法で抽出実験を行った。結果を図２に示す。黒三角がＤ２ＥＨＰＡを用いた抽出率の結果、白三角がＰＣ−８８Ａによる抽出率の結果である。
<Comparative Examples 2 and 3: Extraction behavior of Ni using D2EHPA or PC-88A>
The pH of the aqueous phase was adjusted to 0.8 to 7.0, and the extractant (di (2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC-88A)) was added to isooctane. An extraction experiment was performed in the same manner as in Example 1 except that the organic phase dissolved in was used. The results are shown in FIG. The black triangle is the result of the extraction rate using D2EHPA, and the white triangle is the result of the extraction rate using PC-88A.
（結果）
図２に示すように、合成例１の抽出剤（ＴＯＮＴＡＤＡ）を用いることで、ＮｉをｐＨ３．０以上で９９％以上抽出することができることが確認された。一方、その他の抽出剤（ＤＯＤＧＡＡ、Ｄ２ＥＨＰＡ、ＰＣ−８８Ａ）では、Ｎｉに対する抽出能が小さく、定量的な抽出が困難であった。特に無電解ニッケルめっき液に適用されるｐＨ領域（ｐＨ４．７付近）では、ＴＯＮＴＡＤＡの抽出率が１００％であるのに対し、ＤＯＤＧＡＡの抽出率が２０％、Ｄ２ＥＨＰＡの抽出率が５％、ＰＣ−８８ＡPの抽出率が０％であった。
(result)
As shown in FIG. 2, it was confirmed that 99% or more of Ni can be extracted at pH 3.0 or more by using the extractant (TONTADA) of Synthesis Example 1. On the other hand, other extractants (DODGAA, D2EHPA, PC-88A) have a small extraction ability with respect to Ni, making quantitative extraction difficult. In particular, in the pH range (around pH 4.7) applied to the electroless nickel plating solution, the extraction rate of TONTADA is 100%, whereas the extraction rate of DODGAA is 20%, the extraction rate of D2EHPA is 5%, PC The extraction rate of -88AP was 0%.
＜実施例２：ＴＯＮＴＡＤＡを用いた無電解ニッケルめっきモデル液からのＮｉの抽出＞
表１に示す組成の無電解ニッケルめっきモデルＡ液と無電解ニッケルめっきモデルＢ液を作製した。Ａ液には有機酸として乳酸が、Ｂ液には有機酸として乳酸、プロピオン酸、リンゴ酸、コハク酸が含まれている。無電解ニッケルめっきモデル液：ｐＨ調整剤（硫酸又は水酸化ナトリウム水溶液）＝４：１になるよう混合してｐＨを１．２〜６．０に調製し、１０ｍＭ Ｎｉ（ＳＯ４）２ストック水溶液を添加することで、Ｎｉイオン濃度を０．１ｍＭに調製した。調製した無電解ニッケルめっきモデル液と、それと同体積の１０ｍＭ ＴＯＮＴＡＤＡを含むイソオクタン溶液を混合し、２５℃で１時間激しく振盪した。
振盪後、両相を分取し、分取した水相はｐＨ測定を行い、硝酸水溶液で希釈後、ＩＣＰ−ＭＳを用いて、Ｎｉイオンの濃度を測定した。
An electroless nickel plating model A liquid and an electroless nickel plating model B liquid having the compositions shown in Table 1 were prepared. Liquid A contains lactic acid as an organic acid, and liquid B contains lactic acid, propionic acid, malic acid, and succinic acid as organic acids. Electroless nickel plating model solution: pH adjuster (sulfuric acid or sodium hydroxide aqueous solution) = 4: 1 mixed to adjust pH to 1.2-6.0, 10 mM Ni (SO 4 ) 2 stock aqueous solution Was added to adjust the Ni ion concentration to 0.1 mM. The prepared electroless nickel plating model solution was mixed with an isooctane solution containing the same volume of 10 mM TONTADA and shaken vigorously at 25 ° C. for 1 hour.
After shaking, both phases were separated, and the separated aqueous phase was subjected to pH measurement, diluted with an aqueous nitric acid solution, and then the concentration of Ni ions was measured using ICP-MS.
一方、分取した有機相と、それと同体積の０．５Ｍ硫酸を混合し、２５℃で１時間激しく振盪することで逆抽出を行った。逆抽出相中のＮｉイオン濃度をＩＣＰ−ＭＳを用いて測定した。得られたＮｉイオン濃度から抽出率を、有機相中の物質量／初期条件の物質量×１００で定義し、算出した。無電解ニッケルめっきモデルＡ液の抽出結果を図３に、無電解ニッケルめっきモデルＢ液の抽出結果を図４に示す。 On the other hand, the extracted organic phase and the same volume of 0.5 M sulfuric acid were mixed, and back extraction was performed by shaking vigorously at 25 ° C. for 1 hour. The Ni ion concentration in the back extraction phase was measured using ICP-MS. The extraction rate was defined and calculated from the obtained Ni ion concentration by the amount of the substance in the organic phase / the amount of the substance in the initial condition × 100. The extraction result of the electroless nickel plating model A liquid is shown in FIG. 3, and the extraction result of the electroless nickel plating model B liquid is shown in FIG.
（結果）
無電解ニッケルめっき液には硫酸イオン、次亜リン酸イオン、亜リン酸イオン、有機酸等が高濃度に含まれており、これらがＮｉイオンと錯体を形成するために、抽出を阻害し、抽出率が低下することが問題とされていた。しかし、合成例１の抽出剤（ＴＯＮＴＡＤＡ）を用いることで、ニッケル水溶液と無電解ニッケルめっきモデルＡ液との間でニッケルの抽出挙動が同じであり、抽出率が低下しないことが確認された（図３）。さらに、無電解ニッケルめっきモデルＡ液よりも複数の有機酸を含む無電解ニッケルめっきモデルＢ液を用いても同様な抽出挙動を示し、抽出率は低下しなかった（図４）
(result)
The electroless nickel plating solution contains sulfate ions, hypophosphite ions, phosphite ions, organic acids, etc. at high concentrations, and these form complexes with Ni ions, thus inhibiting the extraction, The problem is that the extraction rate is lowered. However, by using the extractant (TONTADA) of Synthesis Example 1, it was confirmed that the nickel extraction behavior was the same between the nickel aqueous solution and the electroless nickel plating model A solution, and the extraction rate did not decrease ( FIG. 3). Furthermore, even when the electroless nickel plating model B liquid containing a plurality of organic acids was used rather than the electroless nickel plating model A liquid, the same extraction behavior was exhibited, and the extraction rate did not decrease (FIG. 4).
＜実施例３：ＴＯＮＴＡＤＡを用いた無電解ニッケルめっきモデル液からのＮｉの抽出における経時変化＞
表１に示す組成の無電解ニッケルめっきモデルＡ液と無電解ニッケルめっきモデルＢ液を作製した。無電解ニッケルめっきモデル液：ｐＨ調整剤（硫酸又は水酸化ナトリウム水溶液）＝４：１になるよう混合してｐＨを４．７に調製し、１０ｍＭ Ｎｉ（ＳＯ４）２ストック水溶液を添加することで、Ｎｉイオン濃度を０．１ｍＭに調製した。
調製した無電解ニッケルめっきモデル液と、それと同体積の１０ｍＭ ＴＯＮＴＡＤＡを含むイソオクタン溶液とを容量５ｍＬのポリプロピレンチューブに入れ、２５℃、回転振幅約３ｍｍ、振盪速度１８００ｒｐｍの条件で、振盪時間を変えてニッケルの抽出を行った。両相を分取後、分取した水相はｐＨ測定を行い、硝酸水溶液で希釈後、ＩＣＰ−ＭＳを用いて、Ｎｉイオンの濃度を測定した。
一方、分取した有機相と、それと同体積の０．５Ｍ硫酸を混合し、２５℃で１時間激しく振盪することで逆抽出を行った。逆抽出相中のＮｉイオン濃度をＩＣＰ−ＭＳを用いて測定した。得られたＮｉイオン濃度から抽出率を、有機相中の物質量／初期条件の物質量×１００で定義し、算出した。抽出結果を図５に示す。黒丸が無電解ニッケルめっきモデルＡ液の抽出結果、黒三角が無電解ニッケルめっきモデルＢ液の抽出結果である。
<Example 3: Change with time in extraction of Ni from electroless nickel plating model solution using TONTADA>
An electroless nickel plating model A liquid and an electroless nickel plating model B liquid having the compositions shown in Table 1 were prepared. Electroless nickel plating model solution: pH adjuster (sulfuric acid or sodium hydroxide aqueous solution) = 4: 1 by mixing so that pH is adjusted to 4.7, and 10 mM Ni (SO 4 ) 2 stock aqueous solution is added. The Ni ion concentration was adjusted to 0.1 mM.
The prepared electroless nickel plating model solution and an isooctane solution containing 10 mM TONTADA in the same volume are put into a 5 mL polypropylene tube, and the shaking time is changed under the conditions of 25 ° C., rotational amplitude of about 3 mm, and shaking speed of 1800 rpm. Nickel extraction was performed. After separating both phases, the separated aqueous phase was subjected to pH measurement, diluted with an aqueous nitric acid solution, and then the concentration of Ni ions was measured using ICP-MS.
On the other hand, the extracted organic phase and the same volume of 0.5 M sulfuric acid were mixed, and back extraction was performed by shaking vigorously at 25 ° C. for 1 hour. The Ni ion concentration in the back extraction phase was measured using ICP-MS. The extraction rate was defined and calculated from the obtained Ni ion concentration by the amount of the substance in the organic phase / the amount of the substance in the initial condition × 100. The extraction result is shown in FIG. The black circle is the extraction result of the electroless nickel plating model A solution, and the black triangle is the extraction result of the electroless nickel plating model B solution.
（結果）
無電解ニッケルめっき液には硫酸イオン、次亜リン酸イオン、亜リン酸イオン、有機酸などが高濃度に含まれており、これらがＮｉイオンと錯体を形成するために、抽出を阻害し、抽出速度が低下することが問題とされていた。しかし、図５に示すように、合成例１の抽出剤（ＴＯＮＴＡＤＡ）を用いることで、無電解ニッケルめっきモデルＡ液の場合、振盪開始後３分で９９％以上のニッケルを抽出することができ、抽出速度が速いことが確認された。一方、複数の有機酸を含む無電解ニッケルめっきモデルＢ液の場合は、振盪開始後２０分で約９４％、３０分で約９９％のニッケルを抽出することができた。
(result)
The electroless nickel plating solution contains sulfate ions, hypophosphite ions, phosphite ions, organic acids, etc. at high concentrations, and these form complexes with Ni ions, thus inhibiting the extraction, The problem is that the extraction speed is reduced. However, as shown in FIG. 5, in the case of the electroless nickel plating model A solution, 99% or more of nickel can be extracted 3 minutes after the start of shaking by using the extractant (TONTADA) of Synthesis Example 1. The extraction speed was confirmed to be fast. On the other hand, in the case of the electroless nickel plating model B solution containing a plurality of organic acids, about 94% of nickel was extracted 20 minutes after the start of shaking and about 99% of nickel was extracted 30 minutes.
本発明の回収方法は、電解ニッケルめっき液、使用済み電解ニッケルめっき液、無電解ニッケルめっき液、使用済み無電解ニッケルめっき液、廃Ｎｉ−Ｃｄ電池を浸出して得られる溶液、含ニッケル鉱を浸出して得られる溶液等からニッケル元素を回収するために利用することができる。 The recovery method of the present invention includes an electrolytic nickel plating solution, a used electrolytic nickel plating solution, an electroless nickel plating solution, a used electroless nickel plating solution, a solution obtained by leaching waste Ni-Cd batteries, and a nickel-containing ore. It can be used to recover nickel element from a solution obtained by leaching.
Claims (4)
（式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ同一種又は異種の炭化水素基を表す。但し、Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭化水素基の炭素数の合計が、８〜６４である。） In the presence of a preparation step for preparing a nickel-containing aqueous solution, and a compound represented by the following general formula (1) or a salt thereof, the nickel-containing aqueous solution prepared in the preparation step and an organic solvent are brought into contact with each other to obtain nickel element (Ni) A method for recovering nickel element, which includes a liquid-liquid contact step of extracting.
(In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent the same or different hydrocarbon group, provided that R 1 , R 2 , R 3 , and R 4 are hydrocarbons. The total number of carbon atoms in the group is 8 to 64.)
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| US10494329B2 (en) | 2017-09-22 | 2019-12-03 | Japan Atomic Energy Agency | Method for synthesizing tetraalkylnitriloacetic acid diacetamide compound |
| CN109535026B (en) * | 2017-09-22 | 2021-10-29 | 国立研究开发法人日本原子力研究开发机构 | Method for synthesizing tetraalkyl nitrilo acetic acid diacetyl amide compound |
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