JPS648715B2 - - Google Patents
Info
- Publication number
- JPS648715B2 JPS648715B2 JP58156972A JP15697283A JPS648715B2 JP S648715 B2 JPS648715 B2 JP S648715B2 JP 58156972 A JP58156972 A JP 58156972A JP 15697283 A JP15697283 A JP 15697283A JP S648715 B2 JPS648715 B2 JP S648715B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- hydrochloric acid
- group
- copper
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 94
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 30
- 239000013522 chelant Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 150000002500 ions Chemical class 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- -1 arsenic ions Chemical class 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010828 elution Methods 0.000 claims description 9
- 229910001439 antimony ion Inorganic materials 0.000 claims description 8
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 description 27
- 229910052787 antimony Inorganic materials 0.000 description 24
- 239000003480 eluent Substances 0.000 description 18
- 238000004821 distillation Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001577 simple distillation Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 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 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Description
【発明の詳細な説明】
本発明は、銅電解液の浄液法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying a copper electrolyte.
現在、銅の電解製錬は、銅イオン、ニツケル及
びヒ素イオンからなる群より選ばれた１種又は２
種以上のイオンとアンチモンイオン、ビスマスイ
オン及び鉄イオンからなる群より選ばれた１種又
は２種以上の金属イオン（以下Sb、Bi又はFeイ
オンという。）とが共存し、かつ50ｇ／以上の
硫酸濃度を有する銅電解液を用いて行われてお
り、その液中のSb、Bi又はFeイオンの濃度があ
る一定のレベルを超えると、製品である電解銅の
品質に悪影響を及ぼすため、これらのイオンを除
去するための浄液が行われている。この銅電解液
の浄液は、脱銅電解法で行われている。しかしな
がら、この方法は、カソードで金属の析出と同時
に水素の発生を伴う電解採取法であるため、極め
て電力効率の低い方法であり、その上アルシンの
発生を伴うので作業環境上も好ましいものではな
かつた。また、このようにして電解採取したSb、
Bi又はFeイオンを含有する金属析出物から、銅
を回収するために、多大のエネルギーを要すると
いう欠点を有している。このような現状から、
Sb、Bi、Fe等の金属を簡単で、かつ環境保全上
の問題を有しない方法で、銅電解液から、工程外
に分離する方法の開発が緊急課題となつてきた。 Currently, copper electrolytic smelting involves one or two types selected from the group consisting of copper ions, nickel, and arsenic ions.
ions and one or more metal ions selected from the group consisting of antimony ions, bismuth ions, and iron ions (hereinafter referred to as Sb, Bi, or Fe ions) coexist, and in an amount of 50 g/or more. This is done using a copper electrolyte with a sulfuric acid concentration, and if the concentration of Sb, Bi, or Fe ions in the solution exceeds a certain level, it will have a negative effect on the quality of the electrolytic copper product. Purification is being carried out to remove these ions. Purification of this copper electrolyte is performed by copper removal electrolysis. However, this method is an electrowinning method that involves metal deposition at the cathode and hydrogen generation at the same time, so it is an extremely low power efficiency method, and it is also unfavorable in terms of the working environment because it also involves the generation of arsine. Ta. In addition, Sb electrolytically extracted in this way,
It has the disadvantage that a large amount of energy is required to recover copper from metal precipitates containing Bi or Fe ions. Due to this current situation,
It has become an urgent issue to develop a method for separating metals such as Sb, Bi, and Fe from a copper electrolyte in a simple manner that does not pose environmental protection problems outside of the process.
一方、最近、キレート樹脂が実用化され、溶液
中の金属イオンを吸着除去する方法が種々提案さ
れている。しかし、一般市販のキレート樹脂は、
前記した50ｇ／以上の高濃度の銅電解液中から
Bi、Sb、Feイオン吸着分離する能力を有せず、
したがつて、銅電解液の浄液に適用するのは不可
能であつた。 On the other hand, recently, chelate resins have been put into practical use, and various methods have been proposed for adsorbing and removing metal ions in solutions. However, commercially available chelate resins are
From the above-mentioned high concentration copper electrolyte of 50g/or more
Does not have the ability to adsorb and separate Bi, Sb, and Fe ions,
Therefore, it was impossible to apply it to the purification of copper electrolyte.
最近、上述の従来法の欠点を改良するため、ア
ミノメチレンホスホン酸基を有するフエノール系
キレート樹脂（例えば、ユニチカ社製ユニセレツ
ク
UR−330T）で、銅電解液を処理して、Sb、
Bi又はFeイオンを吸着除去する方法が提案され、
注目をあびている（昭和58年日本鉱業会春季年会
予稿集185〜186頁参照。）。この中でキレート樹脂
に吸着したSb、Bi又はFeの各金属イオンは４規
定程度の塩酸水溶液で溶離され得ることが記載さ
れている。 Recently, in order to improve the above-mentioned drawbacks of the conventional method, copper electrolyte was treated with a phenolic chelate resin having an aminomethylene phosphonic acid group (for example, Uniselect UR-330T manufactured by Unitika), and Sb,
A method of adsorbing and removing Bi or Fe ions has been proposed,
It is attracting a lot of attention (see Proceedings of the 1981 Japan Mining Society Spring Annual Meeting, pp. 185-186). It is described that metal ions such as Sb, Bi, or Fe adsorbed on the chelate resin can be eluted with an aqueous solution of about 4N hydrochloric acid.
しかし、溶離液に４規定程度の塩酸水溶液を用
いると、Sb、Bi又はFeの溶離を十分行うために
は、多量の塩酸液量を必要とするという問題点が
あつた。 However, when an aqueous solution of about 4N hydrochloric acid is used as an eluent, there is a problem in that a large amount of hydrochloric acid solution is required to sufficiently elute Sb, Bi, or Fe.
また、Sb、Bi又はFeの各イオンを吸着したキ
レート樹脂から、これらの金属イオンを溶離して
樹脂を再生する場合の塩酸濃度は、高ければ高い
ほど溶離率は向上するが、Sb等の金属イオンを
含有する塩酸から塩酸のみを分離回収すること
は、塩酸濃度が高いほど困難になり、コストアツ
プになるという問題点がある。 In addition, when regenerating the resin by eluating these metal ions from a chelate resin that has adsorbed Sb, Bi, or Fe ions, the higher the hydrochloric acid concentration, the better the elution rate; There is a problem in that the higher the concentration of hydrochloric acid, the more difficult it becomes to separate and recover only hydrochloric acid from the hydrochloric acid containing ions, resulting in increased costs.
上記の方法を実施するうえだ、採算があるかど
うかの分岐点は、金属イオンを吸着したキレート
樹脂の溶離剤として用いた塩酸をいかに安価に、
かつ安定して回収するかという点にある。 The key point in implementing the above method is whether it is profitable or not.
There is also the issue of whether it can be collected stably.
これまで、Sb、Bi又はFeの各イオンを含有し
た４規定程度の塩酸溶離液から、塩酸と金属イオ
ンとを分離回収する方法として、TBP（トリブチ
ルフオスフエート）等を用いる溶媒抽出法、アニ
オン交換樹脂を用いる吸着法、硫化水素を用いて
塩酸溶離液中のアンチモン、ビスマスを硫化物と
して沈殿除去する方法などが考えられるが、これ
らの方法はいずれもランニングコスト、操業安定
性、回収された塩酸の濃度、品位等の点で問題が
あつた。 Until now, as a method for separating and recovering hydrochloric acid and metal ions from a hydrochloric acid eluent containing Sb, Bi, or Fe ions at a concentration of about 4N, solvent extraction methods using TBP (tributyl phosphate), etc., and anion Possible methods include an adsorption method using an exchange resin, and a method that uses hydrogen sulfide to precipitate and remove antimony and bismuth in the hydrochloric acid eluent as sulfides, but these methods all have problems with running costs, operational stability, and recovery. There were problems with the concentration and quality of hydrochloric acid.
本発明者らは、上述の事情に鑑み、銅電解液の
浄液法としては、キレート樹脂法が最も有効であ
ると確信し、簡単な工程で、しかも環境保全上の
問題を有しない銅電解液の浄液法を提供すること
を目的として鋭意研究した結果、特定の濃度を有
する塩酸水溶液を用いてキレート樹脂からのSb、
Bi又はFeの溶離を行うと、極めて効率良くSb、
Bi又はFeが溶離され、かつ、その溶離液を蒸留
すると、水と塩酸との共沸により極めて高収率
で、かつ高品位の塩酸が回収され、回収された塩
酸がそのまま再び溶離液として使用でき、上記の
目的が全て達成しうることを見い出し、本発明を
完成した。 In view of the above-mentioned circumstances, the present inventors believe that the chelate resin method is the most effective method for purifying copper electrolytes, and believe that copper electrolysis is a simple process and does not pose any environmental protection problems. As a result of intensive research aimed at providing a liquid purification method, we found that Sb,
When Bi or Fe is eluted, Sb,
When Bi or Fe is eluted and the eluent is distilled, hydrochloric acid of extremely high yield and high quality is recovered by azeotroping with water and hydrochloric acid, and the recovered hydrochloric acid is used as the eluent again as it is. The inventors have discovered that all of the above objects can be achieved, and have completed the present invention.
すなわち、本発明は銅イオン、ニツケルイオン
及びヒ素イオンからなる群より選ばれた１種又は
１種以上のイオンとSb、Bi又はFeイオンとが共
存し、かつ50ｇ／以上の硫酸濃度を有する銅電
解液をキレート形成基としてアミノメチレンホス
ホン酸基を有するキレート樹脂と接触させて該銅
電解液中のSb、Bi又はFeイオンを吸着分離する
に際し、該キレート樹脂に吸着したSb、Bi又は
Feイオンを5.5〜6.5規定の塩酸水溶液で溶離させ
ることを特徴とする銅電解液の浄液法である。 That is, the present invention provides copper ions in which one or more ions selected from the group consisting of copper ions, nickel ions, and arsenic ions coexist with Sb, Bi, or Fe ions, and which has a sulfuric acid concentration of 50 g/or more. When Sb, Bi or Fe ions in the copper electrolyte are adsorbed and separated by contacting the electrolyte with a chelate resin having an aminomethylene phosphonic acid group as a chelate-forming group, the Sb, Bi or Fe ions adsorbed on the chelate resin are
This is a copper electrolyte purification method characterized by eluting Fe ions with a 5.5-6.5N hydrochloric acid aqueous solution.
本発明に用いられるアミノメチレンホスホン酸
基を有するキレート樹脂としては、例えば、特開
昭56−133319号公報に記載されているフエノール
系キレート樹脂があげられ、そのような樹脂は例
えば次のような方法で製造することができる。す
なわち、一級又は二級のアルキルアミノ基を含有
するフエノール誘導体に、鉱酸の存在下で、ホル
ムアルデヒドと亜リン酸を反応させ、アミノ基の
プロトンの一部又は全部をメチレンホスホン酸に
置換させ、しかる後フエノール類とアルデヒド類
とを反応させゲル化させることにより製造するこ
とができる。そのときに用いる一級又は二級のア
ルキルアミノ基を含有するフエノール誘導体とし
ては、チロシン、アンモニアレゾール、サリチル
アミノ等、鉱酸としては、塩酸、硫酸、フエノー
ル類としては、フエノール、レゾルシン、アルデ
ヒド類としては、ホルムアルデヒド、アセトアル
デヒドが好ましい。また、本発明に用いられるフ
エノール系キレート樹脂の形状は、好ましくは粒
状が用いられるが、繊維状、板状等いかなる形状
でもよい。 Examples of the chelate resin having an aminomethylene phosphonic acid group used in the present invention include the phenolic chelate resin described in JP-A-56-133319, and such resins include, for example, the following. It can be manufactured by the method. That is, a phenol derivative containing a primary or secondary alkylamino group is reacted with formaldehyde and phosphorous acid in the presence of a mineral acid to replace some or all of the protons of the amino group with methylenephosphonic acid, It can then be produced by reacting phenols and aldehydes to form a gel. Phenol derivatives containing a primary or secondary alkylamino group used at that time include tyrosine, ammoniaresol, salicylamino, etc. Mineral acids include hydrochloric acid, sulfuric acid, and phenols include phenol, resorcinol, and aldehydes. is preferably formaldehyde or acetaldehyde. Further, the shape of the phenolic chelate resin used in the present invention is preferably granular, but it may be in any shape such as fibrous or plate-like.
特に本発明においては、官能基としてイミノビ
ス（メチレンホスホン酸）を有し、樹脂母体とし
てフエノール・ホルマリン樹脂を有するフエノー
ル系キレート樹脂（ユニセレツク
UR−3300T）
が好ましい。 In particular, in the present invention, a phenolic chelate resin (UNISELECT UR-3300T) having iminobis (methylene phosphonic acid) as a functional group and a phenol/formalin resin as a resin matrix is used.
is preferred.
本発明で銅電解液とキレート樹脂とを接触させ
るには、連続式でも回分式でも実施することがで
きるが、連続式で行う方が有利である。連続式で
行う場合には、キレート樹脂を充填塔又は多孔板
塔に充填し、銅電解液をSV0.5〜20、好ましくは
１〜５ １／hrで、温度を室温ないし80℃で通液
させればよい。また、銅電解液の流れの方向は、
上昇流、下降流のいづれでもよい。 In the present invention, the contact between the copper electrolyte and the chelate resin can be carried out either continuously or batchwise, but it is more advantageous to carry out the process continuously. In the case of continuous operation, the chelate resin is packed in a packed tower or a perforated plate tower, and the copper electrolyte is passed through at a rate of SV 0.5 to 20, preferably 1 to 5 1/hr, at a temperature of room temperature to 80°C. Just let it happen. In addition, the direction of the flow of the copper electrolyte is
It can be either an upward flow or a downward flow.
本発明において、例えばSb、Bi及びFeイオン
を含有し、かつ200ｇ／の遊離硫酸を含有する
銅電解液を、フエノール系キレート樹脂に、連続
式で、通液を行つた場合の樹脂Sb、Bi又はFeイ
オンの吸着量は、原液のSb、Bi及びFeイオン濃
度によつても異なるが、Biは４〜10ｇ／−
Resin、Sbは８〜30ｇ／−Resin、Feは10〜40
ｇ／−Resinである。 In the present invention, for example, when a copper electrolyte containing Sb, Bi, and Fe ions and 200 g of free sulfuric acid is continuously passed through a phenolic chelate resin, the resin Sb, Bi The adsorption amount of Fe ions also varies depending on the Sb, Bi, and Fe ion concentrations of the stock solution, but Bi is 4 to 10 g/-
Resin, Sb is 8 to 30g/-Resin, Fe is 10 to 40
g/-Resin.
本発明において、キレート樹脂に吸着された
Sb、Bi又はFeイオンは5.5〜6.5規定の塩酸水溶液
で溶離させることが必要である。この塩酸水溶液
を用いることによりSb、Bi又はFeイオンの溶離
率は向上し、しかも塩酸を効率良く回収すること
ができる。この溶離液とキレート樹脂との接触方
法は、カラム法、バツチ法いずれを用いてもよい
が、好ましくはカラム法が用いられる。カラム法
を用いる場合の5.5〜6.5規定の塩酸水溶液の通液
量は、１〜５／−樹脂、好ましくは２〜３
／−樹脂である。また、溶離の際の通液温度
は10℃〜60℃、好ましくは20℃〜30℃である。ま
たカラム法で溶離を行う時の塩酸水溶液の通液速
度はSV0.5〜５（１／Ｈ）、好ましくはSV1〜２で
ある。 In the present invention, the adsorbed to the chelate resin
Sb, Bi or Fe ions must be eluted with a 5.5-6.5N hydrochloric acid aqueous solution. By using this aqueous hydrochloric acid solution, the elution rate of Sb, Bi, or Fe ions is improved, and moreover, hydrochloric acid can be efficiently recovered. The method of contacting the eluent with the chelate resin may be either a column method or a batch method, but preferably a column method is used. When using the column method, the amount of 5.5 to 6.5N hydrochloric acid aqueous solution passed is 1 to 5/- resin, preferably 2 to 3
/-Resin. Further, the liquid passing temperature during elution is 10°C to 60°C, preferably 20°C to 30°C. Further, when performing elution by the column method, the passing rate of the aqueous hydrochloric acid solution is SV 0.5 to 5 (1/H), preferably SV 1 to 2.
次にSb、Bi又はFeイオンを含有する塩酸溶離
液から塩酸を回収するには、例えば、工業的に意
味のある蒸留が適用できる。この蒸留は、単蒸
留、多段蒸留いづれの方式でもよく、また常圧蒸
留、減圧蒸留のいづれの方法でもよい。この際、
６規定の塩酸水溶液は、塩酸と水とが共沸混合物
をつくるので、共沸条件で蒸留を行うのが好まし
い。したがつて、必要ならば塩酸溶離液に水もし
くは35％塩酸（12規定塩酸）を加え、単蒸留で約
95〜99％の収率で塩酸水溶液を回収することがで
きる。 Next, to recover hydrochloric acid from the hydrochloric acid eluent containing Sb, Bi, or Fe ions, for example, industrially meaningful distillation can be applied. This distillation may be carried out by either simple distillation or multi-stage distillation, and may also be carried out by atmospheric distillation or reduced pressure distillation. On this occasion,
In a 6N aqueous hydrochloric acid solution, hydrochloric acid and water form an azeotropic mixture, so it is preferable to distill under azeotropic conditions. Therefore, if necessary, add water or 35% hydrochloric acid (12N hydrochloric acid) to the hydrochloric acid eluent and use simple distillation to
Hydrochloric acid aqueous solution can be recovered with a yield of 95-99%.
また、本発明において、蒸留に供する塩酸溶離
液としては、溶離液中のアンチモンイオン、ビス
マスイオン、鉄イオンの金属イオンの合計の濃度
が３〜４ｇ／以上のものを用いるのが効率的で
あるので、キレート樹脂からの溶離液の画分のう
ち、金属イオン濃度の合計が３〜４ｇ／以下の
画分は、蒸留することなく、再びキレート樹脂の
溶離液として使用し、その後蒸留に供すれば、全
体としての蒸留量が減り、経済的である。また、
場合によつては溶離液の全量を再び塩酸溶離液の
塩酸濃度を共沸組成になるように微調整を行えば
よい。 Furthermore, in the present invention, it is efficient to use a hydrochloric acid eluent for distillation that has a total concentration of metal ions of antimony ions, bismuth ions, and iron ions of 3 to 4 g/or more. Therefore, among the fractions of the eluent from the chelate resin, the fractions with a total metal ion concentration of 3 to 4 g/or less are used again as the eluent for the chelate resin without being distilled, and then subjected to distillation. In this case, the overall amount of distillation is reduced, which is economical. Also,
In some cases, the total amount of the eluent may be finely adjusted again so that the hydrochloric acid concentration of the hydrochloric acid eluent has an azeotropic composition.
この蒸留によつて回収された塩酸水溶液は、共
沸組成である6N塩酸水溶液であるので、これを
そのまま再びキレート樹脂の溶離剤として用いる
ことができる。また、この回収された塩酸水溶液
中には、Sb、Bi又はFeイオンはほとんど含有さ
れていないので、極めて効率良く再溶離用の塩酸
水溶液として用いることができる。 Since the hydrochloric acid aqueous solution recovered by this distillation is a 6N hydrochloric acid aqueous solution having an azeotropic composition, it can be used as it is again as an eluent for the chelate resin. Furthermore, since this recovered hydrochloric acid aqueous solution contains almost no Sb, Bi, or Fe ions, it can be used extremely efficiently as a hydrochloric acid aqueous solution for re-elution.
本発明によれば、極めて経済的に、かつ安定し
て塩酸が回収できるので、キレート樹脂法による
銅電解液の浄液を経済的に行うことができる。 According to the present invention, hydrochloric acid can be recovered very economically and stably, so that purification of copper electrolyte by the chelate resin method can be carried out economically.
以下、実施例に基づき本発明をさらに具体的に
説明する。 Hereinafter, the present invention will be explained in more detail based on Examples.
実施例 １
銅イオンとして40ｇ／、ニツケルとして10
ｇ／、ヒ素イオンとして６ｇ／、アンチモン
イオンとして0.4ｇ／、ビスマスイオンとして
0.3ｇ／、鉄イオンとして0.5ｇ／の各イオン
を含有し、かつ遊離硫酸200ｇ／含有する銅電
解液135を、アミノメチレンホスホン酸をリガ
ンドとして有するキレート樹脂ユニセレツク
UR−3300T（ユニチカ社製）３を充填したカラ
ムに60℃、SV5（１／Ｈ）で通液した。Example 1 40g/as copper ion, 10g/as nickel
g/, 6g/ as arsenic ion, 0.4g/ as antimony ion, as bismuth ion
A chelate resin Uniselect containing copper electrolyte 135 containing 0.3g/, 0.5g/ as iron ions, and 200g/free sulfuric acid, and aminomethylenephosphonic acid as a ligand.
The solution was passed through a column packed with UR-3300T (manufactured by Unitika) 3 at 60°C and SV5 (1/H).
通液後の電解液組成、銅イオン40ｇ／、ニツ
ケルイオン10ｇ／、ヒ素イオン６ｇ／、アン
チモンイオン0.2ｇ／、ビスマスイオン0.2ｇ／
、鉄イオン0.3ｇ／であり、アンチモンイオ
ン、ビスマスイオン、鉄イオンが選択的にキレー
ト樹脂に吸着されていた。 Electrolyte composition after passing: copper ion 40g/, nickel ion 10g/, arsenic ion 6g/, antimony ion 0.2g/, bismuth ion 0.2g/
, 0.3 g/iron ion, and antimony ion, bismuth ion, and iron ion were selectively adsorbed on the chelate resin.
次に、カラムを水洗後、6.2規定の塩酸水溶液
６を、25℃、SV2（１／Ｈ）で通液し、樹脂に
吸着された金属イオンを溶離した。 Next, after washing the column with water, a 6.2N hydrochloric acid aqueous solution 6 was passed through the column at 25° C. and SV2 (1/H) to elute the metal ions adsorbed on the resin.
その結果、溶離液として、アンチモン4.3ｇ／
、ビスマス2.1ｇ／、鉄イオン4.1ｇ／を含
有する6.1規定の塩酸溶離液６が得られた。 As a result, 4.3 g of antimony/
A 6.1N hydrochloric acid eluent 6 containing 2.1 g of bismuth and 4.1 g of iron ions was obtained.
このときの溶離率は、アンチモン96％、ビスマ
ス93％、鉄91％であつた。 The elution rate at this time was 96% antimony, 93% bismuth, and 91% iron.
この溶離液を常圧の単蒸留で蒸留を行つたとこ
ろ、2.95の塩酸水溶液が留去分として回収でき
た。この塩酸水溶液は6.1規定の塩酸濃度を有し
ていた。 When this eluent was distilled by simple distillation at normal pressure, 2.95% of an aqueous hydrochloric acid solution was recovered as a distillate. This aqueous hydrochloric acid solution had a hydrochloric acid concentration of 6.1 normal.
また、回収塩酸水溶液中の金属イオンは、アン
チモンが30mg／の濃度で検出されたが、他の金
属イオンはほとんど検出されなかつた。 Furthermore, among the metal ions in the recovered hydrochloric acid aqueous solution, antimony was detected at a concentration of 30 mg/day, but almost no other metal ions were detected.
この回収塩酸水溶液を再びアンチモン、ビスマ
ス、鉄を吸着したUR−3300Tカラムの溶離剤と
して用い、効率良くこれらの金属イオンの溶離を
行うことができた。 This recovered hydrochloric acid aqueous solution was again used as an eluent for the UR-3300T column that adsorbed antimony, bismuth, and iron, and these metal ions could be efficiently eluted.
なお、比較のため、4Nの塩酸水溶液６（液
量は上記実施例と同じ。）を用い、樹脂からのア
ンチモン、ビスマス、鉄の溶離を行つたところ、
溶離率はおのおの85％、83％、69％であり、この
程度の液量では溶離は完全に行えなかつた。 For comparison, antimony, bismuth, and iron were eluted from the resin using a 4N hydrochloric acid aqueous solution 6 (the liquid volume was the same as in the above example).
The elution rates were 85%, 83%, and 69%, respectively, and complete elution could not be performed with these liquid volumes.
次に、上記と同様にして溶離液を蒸留したが、
塩酸は効率良く回収されなかつた。 Next, the eluent was distilled in the same manner as above, but
Hydrochloric acid was not efficiently recovered.
Claims (1)
らなる群より選ばれた１種又は２種以上のイオン
とアンチモンイオン、ビスマスイオン及び鉄イオ
ンからなる群より選ばれた１種又は２種以上の金
属イオンとが共存し、かつ50ｇ／以上の硫酸濃
度を有する銅電解液を、キレート形成基としてア
ミノメチレンホスホン酸基を有するキレート樹脂
と接触させて該銅電解液中のアンチモンイオン、
ビスマスイオン及び鉄イオンからなる群より選ば
れた１種又は２種以上の金属イオンを吸着分離す
るに際し、該キレート樹脂に吸着したアンチモン
イオン、ビスマスイオン及び鉄イオンからなる群
より選ばれた１種又は２種以上の金属イオンを
5.5〜6.5規定の塩酸水溶液で溶離させることを特
徴とする銅電解液の浄液法。1. One or more ions selected from the group consisting of copper ions, nickel ions, and arsenic ions, and one or more metal ions selected from the group consisting of antimony ions, bismuth ions, and iron ions. A copper electrolyte having a sulfuric acid concentration of 50 g/ or more is brought into contact with a chelate resin having an aminomethylene phosphonic acid group as a chelate-forming group to remove antimony ions in the copper electrolyte,
When adsorbing and separating one or more metal ions selected from the group consisting of bismuth ions and iron ions, one type selected from the group consisting of antimony ions, bismuth ions, and iron ions adsorbed on the chelate resin. or two or more metal ions
A copper electrolyte purification method characterized by elution with a 5.5 to 6.5 normal hydrochloric acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58156972A JPS6050192A (en) | 1983-08-27 | 1983-08-27 | Purifying method of copper electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58156972A JPS6050192A (en) | 1983-08-27 | 1983-08-27 | Purifying method of copper electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6050192A JPS6050192A (en) | 1985-03-19 |
| JPS648715B2 true JPS648715B2 (en) | 1989-02-15 |
Family
ID=15639348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58156972A Granted JPS6050192A (en) | 1983-08-27 | 1983-08-27 | Purifying method of copper electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6050192A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227190A (en) * | 1985-03-29 | 1986-10-09 | Miyoshi Oil & Fat Co Ltd | Method for removing impurity metallic ion in copper electrolyte |
| CN103526230B (en) * | 2013-10-08 | 2015-12-09 | 铜陵有色金属集团股份有限公司金昌冶炼厂 | A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper |
| CN105714117A (en) * | 2016-02-19 | 2016-06-29 | 金川集团股份有限公司 | Method for preparing copper arsenate by using arsenic contained copper electrolyte |
| CN108517538B (en) * | 2018-04-08 | 2019-11-29 | 长沙华时捷环保科技发展股份有限公司 | The method of waste solution of copper electrolysis synthetical recovery processing |
-
1983
- 1983-08-27 JP JP58156972A patent/JPS6050192A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6050192A (en) | 1985-03-19 |
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