JPS6050193A - Method for purifying silver electrolytic solution - Google Patents
Method for purifying silver electrolytic solutionInfo
- Publication number
- JPS6050193A JPS6050193A JP15713283A JP15713283A JPS6050193A JP S6050193 A JPS6050193 A JP S6050193A JP 15713283 A JP15713283 A JP 15713283A JP 15713283 A JP15713283 A JP 15713283A JP S6050193 A JPS6050193 A JP S6050193A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- silver
- resin
- lead
- ion exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明に、鉄電解工程において析出銀の品質ケ向上させ
るために銀型ＭＫＩＬ中の不純物を効果的に除去する銀
電解液の浄液方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying a silver electrolyte that effectively removes impurities in silver-type MKIL in order to improve the quality of deposited silver in an iron electrolytic process.
銀の電解精錬法に、通電隔膜でカ・こっ左粗銀ケ陽極と
し、硝酸酸性硝酸銀液を用い、陰極純銀板１１でに不銹
鋼板上に純銀を析出させる。典型的な例で汀、不銹鋼板
の固定陰極ケ使用し、陰極面紮往復運動する掻き落し装
置により陰極面」二に樹枝状に生成した析出銀を収集し
ている。In the electrolytic refining method of silver, pure silver is deposited on a non-rusting steel plate using a pure silver plate 11 as a cathode using a nitric acid acidic silver nitrate solution using a conductive diaphragm as an anode and an acidic silver nitrate solution. In a typical example, a fixed cathode made of a rustless steel plate is used, and precipitated silver formed in a dendritic form on the cathode surface is collected by a scraping device that moves back and forth between the cathode surface and the cathode surface.
陽極粗銀中に含寸れる不純物とじてげ、金、白金、パラ
ジウム、銅、鉛、テルル、ビスマスその他がある。この
うち金、白金およびパラジウムに電化列７１ｉらいって
銀エリも責な金属であるため、大部分が電解液中に溶出
せず、陽極スライムとして残存する。寸た銅、鉛、テル
ルおよびビスマスに陽極粗銀から電解液中に溶出するが
、本来析出銀とともに電析することにない。だが、実際
の操業でに、パラジウムも若干電Ｍ液中に溶出しそして
陰極に析出するし、また銅お工び鉛も、電解液中の濃度
が上昇すると、月着巻込み電析て析出銀ケ汚染すること
になる。Impurities contained in the anode crude silver include gold, platinum, palladium, copper, lead, tellurium, bismuth, and others. Among these metals, gold, platinum, and palladium are metals that are responsible for the electrification series 71i, as well as silver, so most of them are not eluted into the electrolytic solution and remain as anode slime. Copper, lead, tellurium, and bismuth are eluted from the anode crude silver into the electrolyte, but they are not originally deposited together with the precipitated silver. However, during actual operation, some palladium is eluted into the electrolytic solution and deposited on the cathode, and when the concentration in the electrolytic solution increases, palladium is also deposited in the electrolytic solution. This will cause silver contamination.
銀電解液中の不純物濃度ｔあるレベル以下に抑制するた
め、種々の対策が行われている。従来力・ら行われて’
、Ａ ｆ（代表的な一つの対策としてげ、銀電解液ｒ回
分またに連続で抜き出し、七の液力・ら銅板での置換析
出によりまたに塩化銀として沈殿させることにエリ銀？
回収し、セして不純物を含んだ液に廃棄する刀・またに
処理回収工程に伺す処理方式がある。だが、この方式で
に、抜き出した電解液と同量の硝酸酸性硝酸銀溶液を新
もだに調製して電解液に添加する必要があるため、薬品
代増加の不利があり、加えて析出銀の再溶解により銀の
工程内滞留量増加の問題がある。し女、かって、このよ
うな不利および問題のない効果的な銀電解液の浄化方法
が要望されている。Various measures have been taken to suppress the impurity concentration t in the silver electrolyte below a certain level. Conventional force/ra done'
, A f (One typical countermeasure is to extract the silver electrolyte r times in succession, and then precipitate it as silver chloride by displacement precipitation on a copper plate using the same liquid force as described above.)
There is a treatment method that involves collecting, disposing of, and disposing of the liquid in a liquid containing impurities. However, with this method, it is necessary to prepare a new nitric acid-acidic silver nitrate solution in the same amount as the electrolyte extracted and add it to the electrolyte, which has the disadvantage of increased chemical costs. There is a problem that the amount of silver retained in the process increases due to remelting. There is a need for an effective method for purifying silver electrolytes that is free from such disadvantages and problems.
本発明！Ｆ−よれば、銀イオンのは刀・に主たる不純物
としてパラジウムイオン、ビスマスイオン、銅イオンお
よび鉛イオンを含有する銀電解ｉ’ｌｌ’に第一のキレ
ート***換樹脂および第二のキレート性イオン交換樹脂
により二段階で適切に処理するなら、それらの不純物全
効果的に吸着除去できることがわかった。This invention! According to F-, a first chelating exchange resin and a second chelating ion are added to a silver electrolyte containing palladium ions, bismuth ions, copper ions and lead ions as main impurities. It has been found that all of these impurities can be effectively adsorbed and removed if treated appropriately in two stages with an exchange resin.
刀・くして本発明に、銀電解精錬プロセスから回分また
に連続で抜き出した銀イオンのほかに主１でる不純物と
してパラジウムイオ／、ビスマスイオン、銅イオンおよ
び鉛イオンを含有する銀電解液を第一のキレート性イオ
ン交換樹脂に接触させてそれらのパラジウムおよび銅？
当該第一樹脂に吸着させる工程および得られた銀イオン
のは力・に主たる不純物として鉛イオンを含有する処理
液全第二のキレ−１・性イオン交換樹脂に接触させてそ
の鉛？当該兎二樹脂に吸着させる工８ヶ含む銀電解液の
浄化方法ケ提供する。In the present invention, in addition to silver ions extracted batchwise or continuously from a silver electrolytic refining process, a silver electrolyte containing main impurities such as palladium ion, bismuth ion, copper ion, and lead ion is used. Palladium and copper in contact with one chelating ion exchange resin?
In the step of adsorbing the silver ions to the first resin, the entire treatment solution containing lead ions as the main impurity is brought into contact with the second pure ion exchange resin to remove the lead. A method for purifying a silver electrolyte including adsorption to the resin is provided.
本発明方法によって浄液した処理液に、そのまず、１友
に好寸しぐげ活性炭処理をしグで後、銀電解槽に繰返し
使用することができる。本発明方法に使用した結果ある
レベル以上のパラジウム、ビスマスおよび銅？吸着含有
するに到った第一のキレート性イオン交換樹脂およびあ
るレベル以上の鉛？吸着含有するに到った第二のキレー
ト性イオン交換樹脂に、それぞれ無機酸て溶離再生して
再使用するのが有利である。The treated solution purified by the method of the present invention is first treated with activated carbon, and then can be used repeatedly in a silver electrolytic cell. Palladium, bismuth and copper above a certain level as a result of use in the method of the invention? The first chelating ion exchange resin that adsorbed and contained lead above a certain level? It is advantageous to elute and regenerate the second chelating ion exchange resin that has been adsorbed with an inorganic acid and reuse it.
銀電解液に、遊離ＨＮ０，５〜１０？／Ｊ！−そしてＡ
ｇ６０〜５０ｆ／／ｌの農産のものが一般的であり、電
解進行中に不純物濃度が上昇してＰｔ−１，５〜２０
ｍ９／、ｌ、Ｃｕ１〜３ ｆｌ／ｌ、Ｂｉ １〜５ ｍ
９／１．”ＣしてＰｂ１〜６７／ｌとなる。このような
電解液ケ回分゛庄女に連続で抜き出して本発明の方法に
付すことができる。Free HN0.5-10 in silver electrolyte? /J! -And A
Agricultural products with a weight of 60 to 50 f//l are common, and as the impurity concentration increases during electrolysis, Pt-1,5 to 20
m9/, l, Cu1-3 fl/l, Bi 1-5 m
9/1. The electrolytic solution can be continuously extracted in batches and subjected to the method of the present invention.
本発明方法に使用できるキレ−１・性イオン交換樹脂に
公知であり、刀・つ市場人手できる。１でとえは官能基
としてアミノカルボ／酸基を有するキレート性イオン交
換樹脂に、１ことえば一般式（式中Ｍにアルカリ金属原
子寸たげ水素原子ケ表わし、そしてＲ１およびＲ２に−
ｃｔ′１．それが水素原子寸た。は炭素数１〜３のアル
・＼′ルツ（ケ表ね−ノー）の化合物とフェノールおよ
びアルデヒドとを架橋三次元化して得られ、特開昭５４
−１２１２４１号公報によれば酸性電気亜鉛ノソギ浴中
の鉄イオン濃度を低減できることが知られている。不発
明方〃くの実施に使用できるアミノカルボン酸基ケ有す
る市販のキレート性イオン交換樹脂としてＩｒｆｆ、ユ
ニチカ（株）社ノ＠ユニセレソク［ＪＲ−１０、［］Ｒ
−２０、ｔＪＦｌ、、、−３０，０Ｒ−４０および０Ｒ
−５０、住友化学工業（株）社の■スミギｖ−１−Ｑ、
−１０ＨＲオ、ＩびＭＣ−，３０゜オルガノ（株）社の
■アンバー°ライトＪＲＣ−７１８および三菱化成工業
（株ン社の■ダイヤイオンＣＲ−１０がある。ア好ノカ
ルボン酸基ケ官能基トスるキレート性イオン交換樹脂の
ほが、アεノアルキルリン酸基？官能基とするキレート
性イオン交換樹脂たとえばユニチカ（株）社の■ユニセ
レツクＵＲ−５３００Ｔお工び住友化学工業（株）社の
■スミキレートＥＳ−４６７、ポリアミン基を官能基と
するキレート性イオン交換樹脂たとえば住友化学工業（
株）社の■スミキレートＫＡ−８５０および三菱イしＲ
工業［株） 社の■ダイヤイオノＣ！Ｒ−２０；’ｊら
びにピリジン基勿官能基とするキレート性イオン交換樹
脂たとえば住友化学工業（株）社の■スミキレー）ＯＲ
−２も本発明方法の実施に使用できる。The ion exchange resins that can be used in the method of the present invention are well known and available on the market. In Example 1, a chelating ion exchange resin having an aminocarbo/acid group as a functional group is combined with a general formula (where M represents an alkali metal atom and a hydrogen atom, and R1 and R2 represent -
ct'1. It was the size of a hydrogen atom. is obtained by three-dimensionally cross-linking a C1-3 Al\\'rutsu (Kebone-no) compound with phenol and aldehyde, and is disclosed in JP-A-54
According to Japanese Patent No. 121241, it is known that the iron ion concentration in an acidic electrolytic zinc bath can be reduced. As a commercially available chelating ion exchange resin having an aminocarboxylic acid group that can be used in the implementation of the uninvented method, Irff, Unitika Co., Ltd. @ UNICERESOK [JR-10, []R
-20, tJFl, , -30, 0R-40 and 0R
-50, Sumigi v-1-Q of Sumitomo Chemical Co., Ltd.
-10HR O, I and MC-, 30° Organo Co., Ltd.'s ■Amberlite JRC-718 and Mitsubishi Chemical Industries, Ltd.'s ■Diaion CR-10. The chelating ion exchange resin that is mixed with an ε-noalkyl phosphate group is a chelating ion exchange resin that has a functional group, such as Unitika Co., Ltd.'s ■Uniselect UR-5300T, Sumitomo Chemical Co., Ltd.'s ■ Sumikylate ES-467, a chelating ion exchange resin containing a polyamine group as a functional group, such as Sumitomo Chemical (
Ltd.'s Sumikilate KA-850 and Mitsubishi IshiR
Kogyo Co., Ltd.'s ■Diaiono C! R-20: Chelating ion exchange resin containing pyridine and pyridine functional groups, such as Sumikire from Sumitomo Chemical Co., Ltd.
-2 can also be used to carry out the method of the invention.
本発明の実施に当ってに、寸ず被処理液すなわち銀電解
精錬プロセス力・ら抜き出した浄液式れるべき銀電解液
ケ第一のキレート性イオン交換樹脂に接触袋せる。接触
に、第−樹脂紫充填した第一カラムに被処理液を通液す
ることにエリ行うのが便利である。大抵の場合通液速度
（’ＳＶ） ｌｄ １〜１０１／ｈｒ、処理温度に周囲
温度でよい。この操作にＪ：す、第一のキレート性イオ
ン交換樹脂に、被処理液中のパラジウム、ビスマスおよ
び銅ケ選択的に吸着する。その結果、得られる処理液の
パラジウム、ビスマスお工び銅レベルにいずれ’ｂ １
ｍ’；ｌ／ｌとなるが、銀および鉛に第一樹脂にほと
んど吸着されず処理前濃度とほぼ同様の濃度ＴＭ中に残
留する。In carrying out the present invention, the silver electrolyte extracted from the liquid to be treated, ie, the silver electrolytic refining process, is placed in a contact bag with the first chelating ion exchange resin. It is convenient to carry out the contact by passing the liquid to be treated through the first column filled with the first resin. In most cases, the liquid passing rate ('SV) ld may be 1 to 101/hr, and the processing temperature may be ambient temperature. In this operation, palladium, bismuth, and copper in the liquid to be treated are selectively adsorbed onto the first chelating ion exchange resin. As a result, the palladium, bismuth, and copper levels of the resulting treatment solution will eventually reach 'b 1.
m'; l/l, but silver and lead are hardly adsorbed by the first resin and remain in the concentration TM which is almost the same as the concentration before treatment.
そこで、本発明方法でに、主たる不純物として鉛イオン
を含有する７１）ような第一カラｌ、力・らの処理液ケ
第二のキレート性イオン交換樹脂と接触させる。用いる
第二樹脂に、第一カラムに用いた第一樹脂と同種寸たげ
異種のキレート性イオン交換樹脂であることができる。Therefore, in the method of the present invention, a first treatment solution such as 71) containing lead ions as a main impurity is brought into contact with a second chelating ion exchange resin. The second resin used can be a chelating ion exchange resin of the same type or different size as the first resin used in the first column.
接触げ、やげり第二樹脂を充填した第二カラムに、咀−
力ラムからの処理液を通液することにより行うのが便利
である。After contacting, the second column filled with the second resin is filled with mastication.
It is convenient to carry out this by passing the processing liquid from the power ram.
大抵の場合、通液速度（ＳＶ） Ｉ’Ｉ １−５１．／
ｂｒ、処理温度に周囲温度でよい。この操作にエリ第二
樹脂汀、第一カラム力）らの処理液中の銀をほとんど吸
着することなく鉛を選択的に吸着する。その結果、銀濃
度に実質的に変化せす、鉛濃度が１０〃ｌノ／を以下Ｖ
Ｃなった液が得られる。In most cases, the liquid passing rate (SV) I'I 1-51. /
br, the processing temperature may be ambient temperature. This operation selectively adsorbs lead without adsorbing much of the silver in the treatment solution. As a result, the lead concentration is less than 10 l/V, causing a substantial change in the silver concentration.
A liquid of C is obtained.
第二カラム刀）ら得られた処理液に、不純物の大部分が
除去きれており、銀電解の電解液として、その捷１、ま
たに好１しくに活性炭処理を施した後、所望なら銀およ
び硝酸濃度を調整した後、繰返し使用することができる
。この場合、第二カラム力）ら処理液に、その１才使用
すると、液組成が硝酸酸性であるため、樹脂力・らの微
量の溶出分により銀電解の析出形体に悪影響ケ及ぼすこ
とがあるので、この問題ケ解消する食−め活性炭による
後処理ヶ施した後電解槽に繰送するのが好ましい。Most of the impurities have been removed from the treatment solution obtained from the second column, and it can be used as an electrolyte for silver electrolysis. After adjusting the nitric acid concentration, it can be used repeatedly. In this case, if the second column is used in the processing solution for one year, since the liquid composition is acidic with nitric acid, the small amount of resin eluted may have an adverse effect on the silver electrolytic deposit form. Therefore, it is preferable to carry out a post-treatment with edible activated carbon to solve this problem, and then transfer it to an electrolytic cell.
第一および第二カラム中の使用済樹脂に、それぞれ無機
酸て溶離再生して再使用するのが有利である。パラジウ
ム、ビスマスお工び銅ｙｚ ６ ルレベル以上吸着した
第一カラム内の使用済２−樹脂にに、水洗後たとえば３
〜８Ｎの塩酸１ｋに６〜８Ｎの硫ｅｔ通液速度（ＳＶＩ
Ｏ，５〜３１／ｈｒで通液すると、吸着物質が溶離し
樹脂に再生されて再使用可能な状態になる。溶離ｉけパ
ラジウムの回収工程へ供給する。また、鉛を吸着した第
二カラム内の第二樹脂にに、たとえば０．５〜２Ｎの硝
酸を捷たに樹脂を水洗後１〜３Ｎの塩酸を通液速度（Ｓ
Ｖ）０．５〜３１／ｈｒで通液すると、吸着物質が溶離
し樹脂に再生されて再使用可能な状態となる。It is advantageous to regenerate the spent resin in the first and second columns by elution with an inorganic acid and reuse them. Palladium, Bismuth
The flow rate of 6-8N sulfuric acid to 1k of ~8N hydrochloric acid (SVI
When the liquid is passed at a rate of 0.5 to 31/hr, the adsorbed substances are eluted and regenerated into resin, making it possible to reuse it. The eluted palladium is supplied to the recovery process. In addition, the second resin in the second column that has adsorbed lead is washed with 0.5-2N nitric acid, washed with water, and then 1-3N hydrochloric acid is passed through the resin at a rate (S
V) When the liquid is passed at a rate of 0.5 to 31/hr, the adsorbed substance is eluted and regenerated into resin, making it possible to reuse it.
本発明方法によれば、従来ａ電解液中の不純物音低減す
るのに電解液を廃棄しその廃棄分に相当する新しい液を
補給していたため、析出銀の再溶解による経済的損失が
あったが、カ・ような損失ケ解消できるとともに、銀電
解中の不純物濃度を常時低濃度に抑制でき、その結果、
製品銀中の不純物レベルが低下し、高品質の製品銀を得
ることができる。According to the method of the present invention, conventionally, in order to reduce the noise of impurities in the electrolytic solution, the electrolytic solution was discarded and a new solution equivalent to the discarded amount was replenished, resulting in an economic loss due to redissolution of the deposited silver. However, it is possible to eliminate losses such as power, and to suppress the impurity concentration during silver electrolysis to a low concentration at all times.
The level of impurities in the product silver is reduced, and high quality product silver can be obtained.
以下具体例をあげて本発明？さらに説明する。The present invention is given below with specific examples. I will explain further.
実施例１
官能基としてアミノカルボン酸基ｋ 有−ｆるキレート
性イオン交換樹脂、ユニチカ（株）社の［Ｆ］ユニセレ
ツクＵＲ−５０，１［］Ｄｍｊ’、Ｈ第一カラノ、に第
一カラ上のカラムに銀電解液６００ ｍｌ ｆ Ｉ Ｄ
Ｏｍｌ／ｈｒ（ＳＶ＝１）で通液した。次いでその第一
カラム刀・らの処理液６５０ｒｄｆ、官能基としてアミ
ノアルキルリン酸基ケ有するキレート性イオン交換樹脂
、ユニチカ（株）社の■ユニ上１／ツクＵＲ−５３００
Ｔ、ｉｏｏｍｌ、’ｌ充填Ｌ ｆｃ Ｗ、二カラムに、
１００ ｒｕｌ／ ｈｒ ｊ ＳＶ−１）で通液した。Example 1 A chelating ion exchange resin with an aminocarboxylic acid group k as a functional group, [F] Uniselect UR-50,1[]Dmj', H Daiichi Karano, and Daiichi Karano, manufactured by Unitika Co., Ltd. Add 600 ml of silver electrolyte to the upper column.
The solution was passed at Oml/hr (SV=1). Next, the first column treated solution 650rdf, a chelating ion exchange resin having an aminoalkyl phosphate group as a functional group, Uni-1/Tsuku UR-5300 from Unitika Co., Ltd.
T, iooml, 'l filling L fc W, into two columns,
100 rul/hr j SV-1).
銀電解液原液、第一カラムからの処理液および第二カラ
ム力・らの処理液の品位？表１に示す。What is the quality of the silver electrolyte stock solution, the treated liquid from the first column, and the treated liquid from the second column? It is shown in Table 1.
不純物を吸着した第一カラム中の樹脂に蒸留水２００ｒ
ｎｉｌｚ通水後、６Ｎ硫酸２００ ｍｌ ’ｙ １００
１ＪＬＩ／ｈｒ（ｓ’ｖ＝Ｂで通液し、次いで蒸留水２
ｏｏｍｌで洗滌した。カラムヶ通過させた和硫酸液と洗
滌液とを合体して溶離液４００鮮を得１で。不純物を吸
着した第二カラム中の樹脂に対してに、６Ｎ硫酸の代り
に６Ｎ塩酸ケ用いた以外ａ同様な処理ケ行った、帆−力
ラムおよび第二カラムからの溶離液の品位ケ表２に示す
。200r of distilled water is added to the resin in the first column that has adsorbed impurities.
After passing water through nilz, add 200 ml of 6N sulfuric acid 'y 100
1 JLI/hr (s'v=B, then distilled water 2
Washed with ooml. The Japanese sulfuric acid solution passed through the column and the washing solution were combined to obtain 400 ml of eluent. The resin in the second column that had adsorbed impurities was treated in the same manner as a, except that 6N hydrochloric acid was used instead of 6N sulfuric acid. Table of quality of the eluent from the ram and the second column. Shown in 2.
表 １ 銀電解原液および処理液の品位衣 ２ 溶離液
の品位
実施例２
被処理液として表３記載の組成？もった銀電解液ヲ使用
し、第一カラム中［［アミノアルキルリ／酸基官能基金
有するキレート性イオン交換樹脂（ユニチカ（株）社の
■ＵＲ−３３００Ｔ ） ｉ、その溶１ｊｉｌｌ 剤と
して６Ｎの塩酸ケ使用し、そして第二カラム中にはポリ
アミン基官能基ケ有するキレート性イオン交換樹脂（三
菱ｆヒ成工業（株）社の■ダイヤイオン０Ｒ−２０）
？その溶離剤として１Ｎ硝酸を使用した以外げ、実施例
１記載の操作ケ反復し左。Table 1 Quality of silver electrolytic stock solution and treatment solution 2 Quality of eluent Example 2 Composition listed in Table 3 as treated solution? Using the silver electrolyte that had been prepared, in the first column, a chelating ion exchange resin having an aminoalkyl group/acid group functional group (UR-3300T from Unitika Co., Ltd.) was added, and 6N was added as a solution. A chelating ion exchange resin using hydrochloric acid and having a polyamine functional group in the second column (Diaion 0R-20 from Mitsubishi F-Hisei Kogyo Co., Ltd.)
? The procedure described in Example 1 was repeated except that 1N nitric acid was used as the eluent.
結果ケ表３および表４に示す。The results are shown in Tables 3 and 4.
表 ３ 銀電解処理敢の品位
表 ４ 溶離液の品位
実施例６
１ｔの銀電解槽お工び１ｔの循環槽を備えた銀電解試験
装置を使用し、アミノカルボン酸基を官能基として含有
するキレート性イオン交換樹脂（ユニチカ社）■ユニセ
レツクＵＲ−５０） ５００ｍ１ｉ充填シた第一カラム
、アミノアルキルリン酸基ケ官能基として含有するキｌ
／ −１−性イオン交換樹脂（ユニチカ社の■ユニセレ
ソクＵＲ−３５００Ｔ ） ５００ｒｎｌｆ充填した第
二カラムおよび活性炭１．ｌ、 ｌｅ充填した第三カラ
ムをその順で前記装置の循環槽に連結して、表５に記載
した組成の電解液ケ循環槽カ・ら連続的ｖｒ−抜き出し
第一カラム、第二カラムおよび第三カラムにこの順で５
Ｖ＝１で６時間通液しセして処理液ケ循環槽に戻す本発
明１／ｉｌ−、Ｊ：る浄液紮組込んだ電解実験ケ行った
。Table 3 Quality table of silver electrolytic treatment 4 Quality of eluent Example 6 Using a silver electrolytic testing device equipped with a 1 ton silver electrolytic tank and a 1 ton circulation tank, a silver electrolytic treatment was carried out using an aminocarboxylic acid group as a functional group. Chelating ion-exchange resin (UNITIKA) UNISEREC UR-50) 500ml first column packed with aminoalkyl phosphate groups and chelating resins containing as functional groups
/ A second column packed with 500 rnlf of -1-characteristic ion exchange resin (Unitika's ■ UNISERESOKU UR-3500T) and activated carbon 1. The third columns filled with L and L are connected in that order to the circulation tank of the device, and the electrolyte solution having the composition listed in Table 5 is continuously extracted from the circulation tank of the first column, the second column, and 5 in this order in the third column
An electrolytic experiment was carried out incorporating a purifying liquid duct according to the present invention, in which the treated liquid was passed through at V=1 for 6 hours and then returned to the circulation tank.
６時間が経過した時点で循環槽力・ら浄液カラム群への
電解液の抜き出しおよび循環を停止し、電解槽と循環槽
との間で電解液ｒ循環させながら電解を継続し、その間
に第一お工び第二カラム中の樹脂の溶離再生を行った。When 6 hours have passed, the extraction and circulation of the electrolyte from the circulation tank to the purification column group is stopped, and electrolysis is continued while the electrolyte is circulated between the electrolysis tank and the circulation tank. Elution and regeneration of the resin in the first and second columns was carried out.
第一カラムに対する溶離再生ザイクルに、水洗２時間、
６Ｎ塩酸通液（ＳＶ＝１）２１９間次いで水洗２時間と
し、第二カラムに対する溶離再生ザイクルに、水洗２時
間、１Ｎ硝酸通液（５Ｖ＝１ ） ２時間次いで水洗２
時間とした。各カラムの樹脂の溶離再生処理が完了した
時点で、再び循環槽力・らの電解液の抜き出しを再開し
、本発明による浄液をした後電解液を循環槽に戻す工程
ケ組み込んだ銀電解を継続した。このような６時間の浄
液処理および６時間の溶離再生処理を反復しながら４日
間電解試験を行った。The elution regeneration cycle for the first column includes 2 hours of water washing;
6N hydrochloric acid (SV = 1) was passed for 219 hours, followed by water washing for 2 hours, and the elution regeneration cycle for the second column was followed by water washing for 2 hours, 1N nitric acid passing (5V = 1) for 2 hours, and then water washing for 2 hours.
It was time. When the elution and regeneration treatment of the resin in each column is completed, the extraction of the electrolyte from the circulation tank is restarted, and the process of returning the electrolyte to the circulation tank after purification according to the present invention is carried out. continued. An electrolytic test was conducted for 4 days while repeating such 6-hour liquid purification treatment and 6-hour elution regeneration treatment.
得られた析出銀の平均品位１ｃｊ、Ｐａ約０．０００２
％、Ｃｕ Ｏ，０００１％以下、Ｊ’ｂ Ｏ，０００１
％以下そしてＢｉＯ；０００１％以下であった。The average grade of the obtained precipitated silver was 1cj, Pa about 0.0002
%, Cu O,0001% or less, J'b O,0001
% or less and BiO;0001% or less.
出願人 同和鉱業株式会社Applicant: Dowa Mining Co., Ltd.
Claims (1)
ウムイオン、ビスマスイオン、銅イオノお工び鉛イオン
を含有−する銀電解液ケ第一のキレート性イオン交換樹
脂に接触させてそれらの・ぐラジウム、ビスマスおよび
銅を当該第一樹脂に吸着させる工程および得られた銀イ
オンのは〃・に主たる不純物として鉛イオ／紮含有する
処理液を第二のキレート性イオン交換樹脂に接触させて
その鉛ケ当該第二樹脂に吸着させる工程を含む銀電解液
の浄液方法。 （２）銀イオンのは力・に主たる不純物としてノくラジ
ウムイオン、ビスマスイオン、銅イオンおよび鉛イオン
を含有する銀電１解液ケ第一のキレート性イオン交換樹
脂に接触爆せてそれらの・ζラジウム、ピースマスお工
び銅ｒ当該単一樹脂に吸着略せる工程、得られた銀イオ
ンのは力）に主たる不純物として鉛イオンヶ含有する処
理液？画工のキレート性イオン交換樹脂に接触させて七
の鉛ｒ当該樹脂に吸着させる工程、ならびにパラジウム
および銅を吸着した第一樹脂お工び鉛を吸着し１で第二
樹脂ケそれぞれ再使用のために無機酸で溶離再生する工
程ケ含む銀電解液の浄液方法。[Claims] The first chelating ion exchange resin contains a silver electrolyte containing (11 silver ions as main impurities) radium ions, bismuth ions, copper ions, and lead ions. The step of adsorbing the radium, bismuth and copper on the first resin by contacting them, and the process of adsorbing the resulting silver ions to the second chelating ion, using a treatment solution containing lead ions/ligophores as main impurities. A method for purifying a silver electrolyte comprising the step of bringing the lead into contact with an exchange resin and adsorbing the lead to the second resin. (2) When the silver ions are brought into contact with the first chelating ion exchange resin, the silver electrolyte containing radium ions, bismuth ions, copper ions and lead ions as the main impurities is detonated.・A processing solution that contains lead ions as the main impurity in ζ radium, peace mass processed copper r, a process that can be omitted by adsorption to the single resin, and the strength of the resulting silver ions)? A step in which lead is brought into contact with a painter's chelating ion-exchange resin and adsorbed to the resin, and the first resin adsorbs palladium and copper, which adsorbs the lead, and the second resin is used for reuse. A method for purifying a silver electrolyte, which includes a process of elution and regeneration with an inorganic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15713283A JPS6050193A (en) | 1983-08-30 | 1983-08-30 | Method for purifying silver electrolytic solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15713283A JPS6050193A (en) | 1983-08-30 | 1983-08-30 | Method for purifying silver electrolytic solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6050193A true JPS6050193A (en) | 1985-03-19 |
| JPS6144156B2 JPS6144156B2 (en) | 1986-10-01 |
Family
ID=15642899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15713283A Granted JPS6050193A (en) | 1983-08-30 | 1983-08-30 | Method for purifying silver electrolytic solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6050193A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7300639B2 (en) | 2002-12-03 | 2007-11-27 | Bristol-Myers Squibb Company | Process for removing metals from liquids |
| CN109399591A (en) * | 2018-12-26 | 2019-03-01 | 江苏新宏大集团有限公司 | A kind of preparation method of purification of wet process phosphoric acid |
-
1983
- 1983-08-30 JP JP15713283A patent/JPS6050193A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7300639B2 (en) | 2002-12-03 | 2007-11-27 | Bristol-Myers Squibb Company | Process for removing metals from liquids |
| CN109399591A (en) * | 2018-12-26 | 2019-03-01 | 江苏新宏大集团有限公司 | A kind of preparation method of purification of wet process phosphoric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6144156B2 (en) | 1986-10-01 |
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