JPH03141117A - Method for selectively separating and recovering indium - Google Patents
Method for selectively separating and recovering indiumInfo
- Publication number
- JPH03141117A JPH03141117A JP27845389A JP27845389A JPH03141117A JP H03141117 A JPH03141117 A JP H03141117A JP 27845389 A JP27845389 A JP 27845389A JP 27845389 A JP27845389 A JP 27845389A JP H03141117 A JPH03141117 A JP H03141117A
- Authority
- JP
- Japan
- Prior art keywords
- indium
- group
- hydrophobic compound
- solution containing
- solution
- 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.)
- Pending
Links
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 49
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 30
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- -1 N- nitrosohydroxyamino group Chemical group 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000004957 naphthylene group Chemical group 0.000 claims abstract description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 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 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 3
- GXCSNALCLRPEAS-CFYXSCKTSA-N azane (Z)-hydroxyimino-oxido-phenylazanium Chemical compound N.O\N=[N+](/[O-])c1ccccc1 GXCSNALCLRPEAS-CFYXSCKTSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000013522 chelant Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical compound ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PTPLXVHPKMTVIW-FPLPWBNLSA-N (Z)-hydroxyimino-oxido-phenylazanium Chemical compound O\N=[N+](/[O-])c1ccccc1 PTPLXVHPKMTVIW-FPLPWBNLSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PAQKRBLMHQTWAS-UHFFFAOYSA-N azane;n-hydroxy-n-naphthalen-1-ylnitrous amide Chemical compound N.C1=CC=C2C(N(N=O)O)=CC=CC2=C1 PAQKRBLMHQTWAS-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IAFPDMZRLPCYAB-UHFFFAOYSA-N n-hydroxy-n-naphthalen-1-ylnitrous amide Chemical compound C1=CC=C2C(N(N=O)O)=CC=CC2=C1 IAFPDMZRLPCYAB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はインジウムの選択分離回収法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for selective separation and recovery of indium.
さらに詳しくは特定の疎水性化合物を用いて溶液中のイ
ンジウムを選択的に分離回収する方法に関するものであ
る。More specifically, the present invention relates to a method for selectively separating and recovering indium in a solution using a specific hydrophobic compound.
インジウムは、近年、半導体分野等の発展によりその需
要は著しく増大しつつある。インジウムは鉄や銅などと
異なり単独の鉱石をもたない、インジウムは主として亜
鉛原鉱石であるせん亜鉛鉱の製練残渣、煙灰あるいは、
アルミニウム原鉱石であるボーキサイトのアルカリ浸出
残渣などにわずかに含まれているため、分離１回収には
様々な工夫がなされ、多くの手間と費用がかけられてい
る。すなわち、単純なプロセスで、弊害が少なく、経済
的に、効率よくガリウムを分離２回収できる技術の開発
は期待され、商業的価値も大きい。さて、現在、工業的
規模で実施されているインジウムの分離回収には、上記
残渣からの酸性水溶液を対象とし、（１）アルミニウム
、亜鉛あるいはカドミウムを該酸性水溶液に浸漬し、置
換析出する方法（２）硫酸溶液を硫化水素処理および水
酸化処理したのち、亜鉛あるいはアルミニウムにより置
換析出する方法（３）溶媒抽出による方法（４）イミノ
ジ酢酸基を機能基にもつキレート樹脂を用いた吸着分離
法などが実施あるいは提案されている。Demand for indium has been increasing significantly in recent years due to developments in the semiconductor field and the like. Unlike iron and copper, indium does not exist as a single ore.
Because it is contained in small amounts in the alkali leaching residue of bauxite, which is a raw aluminum ore, various methods have been used to separate and recover it, requiring a lot of effort and expense. In other words, the development of a technology that can economically and efficiently separate and recover gallium with few harmful effects through a simple process is expected and has great commercial value. Now, the separation and recovery of indium currently carried out on an industrial scale targets an acidic aqueous solution from the above-mentioned residue, and involves (1) immersing aluminum, zinc or cadmium in the acidic aqueous solution and precipitating it by displacement ( 2) A method in which a sulfuric acid solution is treated with hydrogen sulfide and hydroxylated, followed by substitutional precipitation with zinc or aluminum. (3) A method by solvent extraction. (4) An adsorption separation method using a chelate resin having an iminodiacetic acid group as a functional group. are being implemented or proposed.
しかしながら、これらの諸方法はそれぞれ種々の欠点を
有する。（１）および（２）の方法では、添加金属より
イオン化傾向が小さい金属が存在している場合には、イ
ンジウムとその金属の分離は不可能となる。（３）の溶
媒抽出法は、大量の亜鉛、アルミニウムが共存している
系においては選択性が低く、大量の溶媒を使用するため
、溶媒溶出による水層の汚染といった問題がある。また
、（４）のイミノジ酢酸系キレート樹脂による方法は、
インジウムに対する選択性が低い点やインジウムを含む
溶液と該キレート樹脂が接触する際の速度に細かい制限
を加えなければならず、また、該キレート樹脂の価格、
耐酸性、耐熱性も考慮すると充分満足する方法とは言い
難い。However, each of these methods has various drawbacks. In methods (1) and (2), if a metal whose ionization tendency is smaller than that of the added metal is present, it is impossible to separate indium from that metal. The solvent extraction method (3) has low selectivity in systems where large amounts of zinc and aluminum coexist, and since a large amount of solvent is used, there are problems such as contamination of the aqueous layer due to solvent elution. In addition, the method (4) using iminodiacetic acid-based chelate resin,
It is necessary to place small restrictions on the low selectivity for indium and the speed at which the chelate resin contacts a solution containing indium, and the price of the chelate resin.
Considering acid resistance and heat resistance, it is difficult to say that this method is fully satisfactory.
この様な諸事情により、半導体部門等の電子産業分野の
発展に伴い金属インジウムの需要が著しく拡大している
にもかかわらず、未だ工業的規模で経済的にも充分満足
できるインジウムの分離。Due to these circumstances, even though the demand for metallic indium has increased significantly with the development of the electronic industry such as the semiconductor sector, it is still difficult to separate indium on an industrial scale and economically.
回収方法は確立されていない。そこで、本発明者らは上
記不都合を克服した新規なインジウムの分離１回収方法
を確立すべ（鋭意検討を重ねた結果、特定のキレート剤
がインジウムを選択的に抽出することを見出し、本発明
に到達した。Collection method has not been established. Therefore, the present inventors established a new method for separating and recovering indium that overcomes the above-mentioned disadvantages (as a result of extensive studies, they discovered that a specific chelating agent selectively extracts indium, and the present invention Reached.
すなわち、本発明は一般式Ｒ１＠Ｒｚ’ｒ；Ｎ−ｏ−ｘ
（たＮ＝０
だし、ＲＩは炭素数３ないし３０の直鎖状、分岐状ある
いは脂環状のアルキル基あるいはアルケニル基を、Ｒ２
はフェニレン基、ナフチレン基、ヒドロフェニレン基あ
るいはヒドロナフチレン基を、Ｘは水素原子、無機ある
いは有機のアンモニウムイオンあるいはナトリウムある
いはカリウムなどのアルカリ金属を、ｎは０．１．２を
それぞれ示す。）で表わされるＮ−ニトロソヒドロキシ
アミノ基を有する疎水性化合物をガリウムを含む溶液と
接触せしめることを特徴とするガリウムの選択的分離回
収法を提供することにある。That is, the present invention is based on the general formula R1@Rz'r;N-o-x
(N=0 However, RI represents a linear, branched or alicyclic alkyl group or alkenyl group having 3 to 30 carbon atoms, R2
represents a phenylene group, a naphthylene group, a hydrophenylene group, or a hydronaphthylene group, X represents a hydrogen atom, an inorganic or organic ammonium ion, or an alkali metal such as sodium or potassium, and n represents 0.1.2. An object of the present invention is to provide a method for selectively separating and recovering gallium, which is characterized in that a hydrophobic compound having an N-nitrosohydroxyamino group represented by the following formula is brought into contact with a solution containing gallium.
本発明で用いられる前記一般式Ｒ＋−（ＲｚｈＮ−０−
Ｘζ
Ｎ、０
で表わされるＮ−ニトロソヒドロキシアミノ基を有する
疎水性化合物としては、Ｒ１として例えば、プロピル、
ヘキシル、オクチル、ドデシル、オクタデシル、エイコ
シル、トコシル、トリアンコンチル、プロペニル、ヘキ
セニル、オクテニル、ドデセニル、オクタデセニル、エ
イコセニル、トコセニル、トリアンコンテニル、シクロ
プロピル。The general formula R+-(RzhN-0-
Examples of the hydrophobic compound having an N-nitrosohydroxyamino group represented by Xζ N,0 include propyl,
Hexyl, octyl, dodecyl, octadecyl, eicosyl, tocosyl, triancontenyl, propenyl, hexenyl, octenyl, dodecenyl, octadecenyl, eicosenyl, tocosenyl, triancontenyl, cyclopropyl.
シクロヘキシル、シクロオクチル、ジシクロプロピル、
ジシクロヘキシル、ジシクロオクチル、トリシクロプロ
ピル、トリシクロヘキシル、トリシクロオクチル、シク
ロプロペニル、シクロヘキセニル、シクロオクテニル、
ジシクロプロペニル。cyclohexyl, cyclooctyl, dicyclopropyl,
Dicyclohexyl, dicyclooctyl, tricyclopropyl, tricyclohexyl, tricyclooctyl, cyclopropenyl, cyclohexenyl, cyclooctenyl,
Dicyclopropenyl.
ジシクロへキセニル、ジシクロオクテニル、トリシクロ
プロペニル、トリシクロヘキセニル、あるいはトリシク
ロオクテニル基またはこれらの基と同等の疎水性をもつ
置換基を有するＮ−ニトロソヒドロキシルアミン、Ｎ−
ニトロソフェニルヒドロキシルアミンおよびＮ−ニトロ
ソナフチルヒドロキシルアミンあるいはこれらのフェニ
ル基およびナフチル基の水素添加物およびＮ−ニトロソ
ヒドロキシルアミンあるいはこれらの無機あるいは有機
アンモニウム塩あるいはナトリウムあるいはカリウムな
どのアルカリ金属塩を挙げることができる。特に、疎水
性置換基を有するＮ−二トロソフェニルヒドロキシルア
ミンアルモニウム塩アルいはＮ−ニトロソナフチルヒド
ロキシルアミンアンモニウム塩が好ましく用いられる。N-nitrosohydroxylamine, N- having dicyclohexenyl, dicyclooctenyl, tricyclopropenyl, tricyclohexenyl, or tricyclooctenyl group or a substituent having hydrophobicity equivalent to these groups
Mention may be made of nitrosophenylhydroxylamine and N-nitrosonaphthylhydroxylamine or their hydrogenated products of phenyl and naphthyl groups and N-nitrosohydroxylamine or their inorganic or organic ammonium salts or alkali metal salts such as sodium or potassium. can. In particular, N-nitrosophenylhydroxylamine aluminum salt or N-nitrosonaphthylhydroxylamine ammonium salt having a hydrophobic substituent is preferably used.
本発明におけるインジウムを含む溶液とはインジウム含
有溶液であればことさら限定されるわけではない。例え
ば、工業的な亜鉛の製造過程で得られるせん亜鉛鉱の浸
出残渣の酸性水溶液、アルミニウムの原料であるボーキ
サイトの浸出残渣の酸性水溶液などが挙げられる。The indium-containing solution in the present invention is not particularly limited as long as it is an indium-containing solution. Examples include an acidic aqueous solution of the leaching residue of splenite obtained in the industrial process of manufacturing zinc, and an acidic aqueous solution of the leaching residue of bauxite, which is a raw material for aluminum.
本発明によるインジウムを含む溶液からインジウムを選
択的に分離回収するには、単にインジウムを含む溶液と
上記疎水性化合物を接触するだけでよく、接触の方法に
ついて特に限定されるものではなく、一般にインジウム
を含む溶液に疎水性化合物をそのまま加え撹拌する方法
、疎水性化合物を円筒型カラムに充填し、これにインジ
ウムを含む溶液を通液する方法、あるいは疎水性化合物
を疎水性の有機溶剤に溶解せしめ、これにインジウムを
含む溶液を接触せしめるいわゆる溶媒抽出法等が採用さ
れる。しかし、装置、操作の簡便さ、処理能力、効率の
良さ等を考慮すると、インジウムを含む溶液に疎水性化
合物をそのまま加え攪拌する方法を採用するのが好まし
い。疎水性化合物の使用量は溶液中のインジウム濃度に
よって適宜選択される。実施温度は５〜７０℃で好まし
くは１０〜５０℃である。また、接触時間は通常数分以
上で十分である。さらに、インジウムを含む溶液は酸性
が好ましく、ｐＨが０付近から５、特にｐＨ１〜４が好
ましい。In order to selectively separate and recover indium from an indium-containing solution according to the present invention, it is sufficient to simply contact the indium-containing solution with the above-mentioned hydrophobic compound, and there are no particular limitations on the method of contact. A method in which a hydrophobic compound is directly added to a solution containing indium and stirred, a method in which the hydrophobic compound is packed in a cylindrical column and a solution containing indium is passed through the column, or a method in which the hydrophobic compound is dissolved in a hydrophobic organic solvent. , a so-called solvent extraction method is employed in which this is brought into contact with a solution containing indium. However, in consideration of ease of equipment, operation, processing capacity, efficiency, etc., it is preferable to adopt a method in which the hydrophobic compound is directly added to a solution containing indium and stirred. The amount of the hydrophobic compound used is appropriately selected depending on the indium concentration in the solution. The operating temperature is 5 to 70°C, preferably 10 to 50°C. Further, a contact time of several minutes or more is usually sufficient. Furthermore, the solution containing indium is preferably acidic, with a pH of around 0 to 5, particularly preferably 1 to 4.
また、上記疎水性化合物を樹脂あるいはシリカゲル等に
担持あるいは固定化することによっても、インジウムの
選択的分離回収はもちろん可能であり、形状として、粉
末状、多孔質球状、繊維状、フィルム状、膜状あるいは
コロイド状等が挙げられる。さらに、上記疎水性化合物
の疎水性溶液を多孔質高分子膜に含浸させた含浸膜ある
いは界面活性剤によって安定化させた乳化膜等の液膜も
同様に用いられる。In addition, it is of course possible to selectively separate and recover indium by supporting or immobilizing the hydrophobic compound on a resin or silica gel, etc., and it can be in the form of powder, porous sphere, fiber, film, or membrane. For example, it may be in the form of a colloid or in the form of a colloid. Furthermore, liquid membranes such as an impregnated membrane in which a porous polymer membrane is impregnated with a hydrophobic solution of the above-mentioned hydrophobic compound or an emulsion membrane stabilized with a surfactant can also be used.
本発明によれば、単純な操作によってインジウムを含む
溶液からインジウムを選択的に分離回収できる。According to the present invention, indium can be selectively separated and recovered from a solution containing indium by a simple operation.
インジウムを吸着した疎水性化合物はさらに強い酸と接
触させることによってインジウムを溶離することができ
る。さらに、溶離液をそのままあるいは例えば、アルミ
ニウムで置換析出し、溶融水酸化カリウムの下で、溶融
したのち硫酸インジウムと食塩からなる溶液を調製し、
公知方法によって電解することによって高純度の金属イ
ンジウムを得ることができる。Indium can be eluted by further contacting the hydrophobic compound that has adsorbed indium with a strong acid. Further, the eluent is used as it is or, for example, aluminum is substituted for precipitation, and after melting under molten potassium hydroxide, a solution consisting of indium sulfate and common salt is prepared,
High purity metallic indium can be obtained by electrolysis using a known method.
公知の方法を用いてインジウムを分離回収する方法に比
較して、インジウムに対する選択性が高い。また、簡便
な操作で効率よく分離回収できる点、吸着したインジウ
ムはさらに強い酸性水溶液によって容易に溶離され、溶
離液をそのまま電解液とすることができるため、工業的
価値も大きい。The selectivity for indium is higher than the method of separating and recovering indium using a known method. In addition, it has great industrial value because it can be efficiently separated and recovered with simple operations, and the adsorbed indium can be easily eluted with a stronger acidic aqueous solution, and the eluate can be used as an electrolyte as it is.
以下、本発明を実施例によってさらに詳しく説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、本発明は以下の実施例に限定されるものではない
。Note that the present invention is not limited to the following examples.
実施例１−５
次の一般式で表わされるＮ−ニトロソヒドロキシアミノ
基を有する疎水性化合物微粉末５．０ｇを、ｐＨ１，５
に調整したインジウム１１５ｐｐｍ、亜鉛１３０００ｐ
ｐｍおよびアルミニウム１１００００ｐｐを含む水溶液
１００−に加え、室温で２時間攪拌後、ろ過してろ液を
分離した。得られた金属キレートは水洗後３モル／ｄＩ
ｌｆｆの硫酸５Ｑ、ｆｆｌを加え、室温で３０分間攪拌
し、ろ過することによってインジウムを溶離した回収液
を得た。結果を第１表に示す。Example 1-5 5.0 g of fine powder of a hydrophobic compound having an N-nitrosohydroxyamino group represented by the following general formula was mixed at pH 1.5.
Indium 115ppm, zinc 13000p adjusted to
pm and 110,000 pp of aluminum, and after stirring at room temperature for 2 hours, the mixture was filtered to separate the filtrate. The obtained metal chelate had a concentration of 3 mol/dI after washing with water.
lff sulfuric acid 5Q and ffl were added, stirred at room temperature for 30 minutes, and filtered to obtain a recovered solution in which indium was eluted. The results are shown in Table 1.
実施例６
インジウム、亜鉛およびアルミニウムを含む溶液のｐｉ
を１．０に調整した以外は実施例１と同様に操作した。Example 6 Pi of a solution containing indium, zinc and aluminum
The same procedure as in Example 1 was carried out except that the value was adjusted to 1.0.
実施例７
疎水性化合物として、Ｒ，にｎ−ドデシル基を有するＮ
−ニトロソフェニルヒドロキシルアミンアンモニウム塩
４．０ｇを用いた以外は実施例１と同様に操作した。Example 7 As a hydrophobic compound, N having an n-dodecyl group in R,
The same procedure as in Example 1 was carried out except that 4.0 g of -nitrosophenylhydroxylamine ammonium salt was used.
実施例８
疎水性化合物として、Ｒ，にｎ−エイコシル基を有する
Ｎ−ニトロソフェニルヒドロキシルアミンアンモニウム
塩５．４ｇを用い、インジウム、亜鉛およびアルミニウ
ムを含む溶液のｐＨ；ｆｒ−１，０に調整した以外は実
施例１と同様に操作した。Example 8 Using 5.4 g of N-nitrosophenylhydroxylamine ammonium salt having an n-eicosyl group in R as a hydrophobic compound, the pH of a solution containing indium, zinc, and aluminum was adjusted to fr-1.0. The other operations were the same as in Example 1.
以上の結果を第２表に示す。The above results are shown in Table 2.
土粒■
実施例１で用いたＲ３がオクタデシル基、Ｒｔがフェニ
ル基であるＮ−ニトロソヒドロキシアミノ基を有する疎
水性化合物を用いる代わりに、Ｒ９が水素原子、Ｒ２が
フェニル基であるＮ−ニトロソヒドロキシアミノ基を有
する化合物を用いた以外は実施例１と同様に操作した。Soil Grain ■ Instead of using the hydrophobic compound having an N-nitrosohydroxyamino group in which R3 is an octadecyl group and Rt is a phenyl group as used in Example 1, an N-nitrosohydroxyamino compound in which R9 is a hydrogen atom and R2 is a phenyl group is used. The same procedure as in Example 1 was carried out except that a compound having a hydroxyamino group was used.
ろ液中の金属イオン濃度はインジウム７８ｐｐｍ、亜鉛
１２９００ρｐＨおよびアルミニウム９９００ ｐｐｍ
であった。また、回収液中のインジウム濃度は３５ｐｐ
ｍで回収率は３０％であった。The metal ion concentrations in the filtrate were indium 78 ppm, zinc 12900 ρpH, and aluminum 9900 ppm.
Met. In addition, the indium concentration in the recovered liquid was 35 pp.
The recovery rate was 30%.
Claims (2)
し、Ｒ＿１は 炭素数３ないし３０の直鎖状、分岐状あるいは脂環状の
アルキル基あるいはアルケニル基を、Ｒ＿２はフェニレ
ン基、ナフチレン基、ヒドロフェニレン基あるいはヒド
ロナフチレン基を、Ｘは水素原子、無機あるいは有機の
アンモニウムイオンあるいはナトリウムあるいはカリウ
ムのアルカリ金属を、ｎは０，１，２をそれぞれ示す。 ）で表わされるＮ−ニトロソヒドロキシアミノ基を有す
る疎水性化合物をインジウムを含む溶液と接触せしめる
ことを特徴とするインジウムの選択的分離回収法。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 is a linear, branched, or alicyclic alkyl group or alkenyl group having 3 to 30 carbon atoms, and R_2 is a phenylene group or naphthylene group. , a hydrophenylene group or a hydronaphthylene group, X is a hydrogen atom, an inorganic or organic ammonium ion, or an alkali metal such as sodium or potassium, and n is 0, 1, or 2, respectively. 1. A method for selectively separating and recovering indium, the method comprising bringing a hydrophobic compound having the following properties into contact with a solution containing indium.
を特徴とする特許請求の範囲第１項記載のインジウムの
選択的分離回収法。(2) The method for selectively separating and recovering indium according to claim 1, wherein the indium-containing solution is an acidic aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27845389A JPH03141117A (en) | 1989-10-27 | 1989-10-27 | Method for selectively separating and recovering indium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27845389A JPH03141117A (en) | 1989-10-27 | 1989-10-27 | Method for selectively separating and recovering indium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03141117A true JPH03141117A (en) | 1991-06-17 |
Family
ID=17597552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27845389A Pending JPH03141117A (en) | 1989-10-27 | 1989-10-27 | Method for selectively separating and recovering indium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03141117A (en) |
-
1989
- 1989-10-27 JP JP27845389A patent/JPH03141117A/en active Pending
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