JPS63270421A - Method for recovering platinum group metals from platinum group metallic oxide electrode - Google Patents
Method for recovering platinum group metals from platinum group metallic oxide electrodeInfo
- Publication number
- JPS63270421A JPS63270421A JP62104133A JP10413387A JPS63270421A JP S63270421 A JPS63270421 A JP S63270421A JP 62104133 A JP62104133 A JP 62104133A JP 10413387 A JP10413387 A JP 10413387A JP S63270421 A JPS63270421 A JP S63270421A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- platinum group
- platinum
- binder
- group metal
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- -1 platinum group metals Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 17
- 239000007772 electrode material Substances 0.000 claims description 16
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、食塩電解等の各種電気化学反応に利用される
白金族金属酸化物が被覆された電極から該白金族金属酸
化物を金属として回収するための方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is directed to the production of platinum group metal oxides as metals from electrodes coated with platinum group metal oxides used in various electrochemical reactions such as salt electrolysis. Concerning methods for collection.
（従来技術とその問題点）
食塩電解によるカセイソーダと塩素の製造を始めと、す
る各種電解反応に以前から金属電極が採用されていた。(Prior art and its problems) Metal electrodes have long been used in various electrolytic reactions, including the production of caustic soda and chlorine through salt electrolysis.
しかし通常の金属電極は過電圧が比較的高いこと及び特
に食塩電解の際に発生するカセイソーダと塩素に対する
耐久性に欠けるため、多くの用途において十分な性能を
有し得なかった。However, conventional metal electrodes do not have sufficient performance in many applications because of their relatively high overvoltage and lack of durability, especially against caustic soda and chlorine generated during salt electrolysis.
この欠点を解消するために提案されたのが、白金、イリ
ジウム及びルテニウム等の白金族金属の酸化物を電極活
性物質と被覆して成る白金族金属酸化物電極、いわゆる
寸法安定性電極である。To overcome this drawback, a platinum group metal oxide electrode, a so-called dimensionally stable electrode, has been proposed in which an oxide of a platinum group metal such as platinum, iridium, or ruthenium is coated with an electrode active material.
該金属酸化物電極は特に食塩電解の際に発生するカセイ
ソーダ及び塩素に対する耐久性に優れ、しかも塩素過電
圧が低いため使用電力が低下して経済的な操業を行うこ
とを可能にしている。しかしながら該電極も電極活性物
質の活性が使用するに従い低下するため、数年毎に電極
活性物質のりコーティングを行わなければならない。リ
コーティングを行うためにはまず前記電極活性物質の基
材からの剥離を行う必要があり、この剥離方法として従
来から次の３種の方法が採用されているがそれぞれ付記
する欠点を有している。The metal oxide electrode has particularly excellent durability against caustic soda and chlorine generated during salt electrolysis, and has a low chlorine overvoltage, which reduces power consumption and enables economical operation. However, since the activity of the electrode active material decreases with use, the electrode must be coated with electrode active material glue every few years. In order to perform recoating, it is first necessary to peel off the electrode active material from the base material, and the following three methods have been conventionally adopted for this peeling method, but each has the following disadvantages. There is.
第１の機械的剥離ではサンドブラストやグラインダーを
使用して電極活性物質を剥離しているがこの方法による
と、生ずる多量のエメリー中に白金族金属が混じって白
金族濃度が低くなって回収が困難になり、又基材にエメ
リーが食い込み基材の損傷に繋がる。第２の物理的剥離
は電極基材に熱衝撃を与え基材と電極活性物質間の歪み
を利用して剥離させる方法であるが、熱衝撃で電極活性
物質を剥離させる際に電極を損傷し、電極の再使用時に
歪みが生じやすい。又この第１及び第２の方法では白金
族金属の全剥離成分に対する比が低く、回収率や回収コ
ストの面でも問題が残っている。第３の化学的剥離では
、電極活性物質中に例えばルテニウム及びイリジウムの
ような王水等に容易に溶解しない物質が含まれるため完
全に回収することが困難である。In the first mechanical stripping, the electrode active material is stripped using sandblasting or a grinder, but with this method, platinum group metals are mixed in the large amount of emery that is generated, reducing the platinum group concentration and making recovery difficult. Also, the emery will dig into the base material, leading to damage to the base material. The second physical peeling method is to apply a thermal shock to the electrode base material and use the strain between the base material and the electrode active material to peel it off, but when the electrode active material is peeled off by thermal shock, the electrode is damaged. , distortion is likely to occur when the electrode is reused. Furthermore, in the first and second methods, the ratio of platinum group metal to the total exfoliated components is low, and problems remain in terms of recovery rate and recovery cost. In the third type of chemical stripping, it is difficult to completely recover the electrode active material because it contains substances such as ruthenium and iridium that are not easily dissolved in aqua regia.
白金族金属酸化物電極の電極活性物質の主成分は白金、
イリジウム及びルテニウムの酸化物であるが、これらは
比較的強固に基材に結合しているため、従来技術により
これらを電極基材を損傷することなく完全に剥離して回
収することは不可能である。The main component of the electrode active material of the platinum group metal oxide electrode is platinum,
These are iridium and ruthenium oxides, but because they are relatively strongly bonded to the base material, it is impossible to completely peel off and recover them using conventional techniques without damaging the electrode base material. be.
（発明の目的）
本発明は、前記従来技術では達成し得なかった白金族金
属酸化物電極から白金族金属を電極基材を損傷すること
なく剥離し回収する方法を提供することを目的とする。(Objective of the Invention) An object of the present invention is to provide a method for peeling off and recovering platinum group metal from a platinum group metal oxide electrode without damaging the electrode base material, which could not be achieved with the prior art. .
（問題点を解決するための手段）
本発明は、電極基材上に、バインダーを介して少なくと
も白金、イリジウム及びルテニウムの白金族金属酸化物
を含む電極活性物質が被覆された電極から前記白金族金
属を回収する方法において、還元剤を使用して前記金属
酸化物を還元して金属状とし、次いで該電極を塩酸と硝
酸を含む水溶液で処理して前記金属状とされた白金とイ
リジウムの少なくとも一部を溶出させ、その後前記電極
を陽極としてフッ素化合物を含む電解液中で電解して前
記金属の残部と前記バインダーを剥離し回収することを
特徴とする白金族金属酸化物電極からの白金族金属の回
収方法である。(Means for Solving the Problems) The present invention provides an electrode base material coated with an electrode active material containing platinum group metal oxides of at least platinum, iridium, and ruthenium via a binder. In a method for recovering metals, the metal oxide is reduced to a metallic state using a reducing agent, and then the electrode is treated with an aqueous solution containing hydrochloric acid and nitric acid to form at least one of platinum and iridium, which has been made into a metallic state. A platinum group metal from a platinum group metal oxide electrode is characterized in that a part of the metal is eluted and then electrolyzed in an electrolytic solution containing a fluorine compound using the electrode as an anode to peel off and recover the remaining metal and the binder. This is a method of recovering metals.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に使用する白金族金属酸化物電極自身は公知のも
のである。つまり電極基材はチタンを主とする材料から
成り、該電極基材上に酸化チタン、酸化ジルコニウム及
び酸化錫等のバインダーを介して、少なくとも白金、イ
リジウム及びルテニウムの白金族金属酸化物を含む電極
活性物質が被覆されて成っている。The platinum group metal oxide electrode itself used in the present invention is well known. In other words, the electrode base material is made of a material mainly composed of titanium, and the electrode base material contains at least platinum group metal oxides of platinum, iridium, and ruthenium via a binder such as titanium oxide, zirconium oxide, and tin oxide. It is coated with an active substance.
該電極の電極活性物質を本発明により剥離し回収するに
は、まずヒドラジン、水素化ホウ素ナトリウム（ＳＢＨ
）及び亜硫酸塩のような還元剤で電極基材を処理して白
金族金属酸化物を還元し白金族金属とする。該処理は通
常の還元条件で行えばよく、例えば二塩酸ヒドラジン等
の還元剤溶液中に室温で数分〜数時間電極を浸漬するこ
とにより白金族金属に還元することができる。In order to peel off and recover the electrode active material of the electrode according to the present invention, first, hydrazine, sodium borohydride (SBH
) and a reducing agent such as a sulfite to reduce the platinum group metal oxide to a platinum group metal. This treatment may be carried out under normal reducing conditions, and the electrode can be reduced to a platinum group metal by, for example, immersing the electrode in a solution of a reducing agent such as hydrazine dihydrochloride at room temperature for several minutes to several hours.
次いで電極活性物質を還元した電極を塩酸及び硝酸を含
む溶液で処理して還元された電極活性物質中の大部分の
白金と一部のイリジウムを溶出する。ここで使用する塩
酸及び硝酸を含む溶液とは一般に王水を意味するが、厳
密な意味での王水（濃塩酸と濃硝酸の３：１体積比の混
合溶液）だけでな（、他の体積比の溶液あるいは他の成
分を含む溶液も包含する。前記した白金、イリジウム及
びルテニウムのうち白金は前記塩酸及び硝酸を含む溶液
に可溶であり、５０〜８０℃程度に数時間加熱すると殆
どの白金が溶出する。又イリジウムも塩酸及び硝酸を含
む溶液に若干溶解し、同程度の加熱で一部溶出する。Next, the electrode with the reduced electrode active material is treated with a solution containing hydrochloric acid and nitric acid to elute most of the platinum and some of the iridium in the reduced electrode active material. The solution containing hydrochloric acid and nitric acid used here generally means aqua regia, but it is not only aqua regia in the strict sense (a mixed solution of concentrated hydrochloric acid and concentrated nitric acid in a 3:1 volume ratio) (but also other It also includes solutions containing volume ratios or solutions containing other components.Of the platinum, iridium, and ruthenium mentioned above, platinum is soluble in the solution containing hydrochloric acid and nitric acid, and most of it is dissolved when heated to about 50 to 80°C for several hours. Platinum is eluted.Iridium is also slightly dissolved in a solution containing hydrochloric acid and nitric acid, and is partially eluted by heating to the same degree.
この時点で電極は電極基材とその上に被覆されたバイン
ダー及び微量の白金と、イリジウム及びルテニウムの被
覆層から成り、該被覆層は、白金及びイリジウムが溶出
した部分が空洞となっているため多孔質である。At this point, the electrode consists of an electrode base material, a binder coated on it, a small amount of platinum, and a coating layer of iridium and ruthenium. Porous.
次いでこの電極をフッ素化合物、例えばフッ化水素やフ
ッ化水素アンモンを含む電解浴中で電解して酸化チタン
等のバインダーと、残っている白金族金属、つまりイリ
ジウム、ルテニウム及び微量の白金を剥離する。なお該
電解は加熱して行ってもよいが、室温下での電解でも十
分であり、電解時間も数十分から２時間程度で十分であ
り、５〜１５分程度の電解を数回繰り返すようにしても
よい。該電解により白金族金属は黒色の微粉末となって
剥離し回収される。該電解による剥離機構は次のように
、つまり前記フッ素化合物のＦ−イオンが多孔質被覆層
を通って電極基材に達し、該電極基材のチタンを一部エ
ッチングして前記白金族金属及びバインダーの被覆を浮
き上がらせて剥離すると考えることができる。This electrode is then electrolyzed in an electrolytic bath containing a fluorine compound, such as hydrogen fluoride or ammonium hydrogen fluoride, to strip off the binder such as titanium oxide and the remaining platinum group metals, i.e. iridium, ruthenium, and trace amounts of platinum. . The electrolysis may be performed by heating, but electrolysis at room temperature is also sufficient, and the electrolysis time is from several tens of minutes to about 2 hours, and it is recommended to repeat electrolysis for about 5 to 15 minutes several times. You can also do this. As a result of the electrolysis, the platinum group metal becomes black fine powder, which is exfoliated and recovered. The peeling mechanism by electrolysis is as follows: F- ions of the fluorine compound reach the electrode base material through the porous coating layer, partially etching the titanium of the electrode base material, and removing the platinum group metal and It can be thought of as lifting the binder coating and peeling it off.
これらの処理により前記白金族金属酸化物電極から該電
極を損傷することなく、電極活性物質及びバインダーが
完全に除去され、より以上の処理を必要とせずにリコー
ティングを実施することができる。These treatments completely remove the electrode active material and binder from the platinum group metal oxide electrode without damaging the electrode, and recoating can be performed without the need for further treatment.
以下本発明の実施例を記載するが、該実施例は本発明を
限定するものではない。Examples of the present invention will be described below, but the examples are not intended to limit the present invention.
（実施例）
チタン基材上に、酸化白金、酸化イリジウム及び酸化ル
テニウムを８８：１２：５のモル比で被覆して成るメツ
シュ状の金属酸化物電極を、０．２重量％の二塩酸ヒド
ラジン溶液に室温で１時間浸漬して前記酸化物を十分還
元した。(Example) A mesh-like metal oxide electrode consisting of a titanium substrate coated with platinum oxide, iridium oxide and ruthenium oxide in a molar ratio of 88:12:5 was coated with 0.2% by weight of hydrazine dihydrochloride. The oxide was sufficiently reduced by immersing it in the solution at room temperature for 1 hour.
次いで該還元処理した電極を塩酸：硝酸＝６：１の混合
溶液に６０〜７０℃の加熱下１．５時間浸漬した。その
後該混合溶液を分析したところ塩化白金と若干量の塩化
イリジウムの存在が確認された。Next, the reduced electrode was immersed in a mixed solution of hydrochloric acid:nitric acid=6:1 for 1.5 hours under heating at 60 to 70°C. Thereafter, the mixed solution was analyzed and the presence of platinum chloride and a small amount of iridium chloride was confirmed.
次に５重量％のフッ化水素と５重量％のフッ化水素アン
モンを含む水溶液を電解液とし、前記電極を陽極とし、
金めっきしたステンレス板を陰極として、電流密度０．
２ Ａ／ｄｍ”、電圧４．２Ｖ（７）条件で１０分間電
解を行ったところ、黒色の微粉末が電解浴中の陽極の真
下に沈澱した。引き続き同じ電解操作を更に２回繰り返
したが最後の電解操作では黒色粉末の沈澱は生じなかっ
た。生じた沈澱は濾過により回収した。Next, an aqueous solution containing 5% by weight of hydrogen fluoride and 5% by weight of ammonium hydrogen fluoride is used as an electrolyte, and the electrode is used as an anode,
Using a gold-plated stainless steel plate as a cathode, the current density was 0.
When electrolysis was carried out for 10 minutes at 2 A/dm" and a voltage of 4.2 V (7), black fine powder was precipitated just below the anode in the electrolytic bath. The same electrolytic operation was repeated two more times, but No black powder precipitated during the final electrolytic operation, and the resulting precipitate was collected by filtration.
電解処理の終わった電極の表面を観察したところ、白金
、イリジウム及びルテニウム更にバインダーに由来する
ジルコニウムや錫は殆んど存在していなかった。When the surface of the electrode after electrolytic treatment was observed, platinum, iridium, and ruthenium, as well as zirconium and tin derived from the binder, were hardly present.
（発明の効果）
本発明は、少なくとも白金、イリジウム及びルテニウム
の白金族金属酸化物を含む電極活性物質が被覆された電
極から前記白金族金属を回収するに際して、還元された
前記白金族金属を塩酸と硝酸を含む水溶液で処理して白
金をほぼ完全に溶出させて回収し、残りのイリジウム及
びルテニウムとバインダーを電解により剥離し回収する
ようにしている。本発明方法では、従来のような機械的
あるいは物理的剥離のような過酷な操作をする必要がな
く比較的穏やかな電解条件で剥離回収することができ、
しかも主成分である白金が予めほぼ完全に除去されてい
るため、該電解も最小限の処理時間で完了し、電極基材
のリコーティングに支障が生ずるような損傷が生ずるこ
とがない。(Effects of the Invention) In the present invention, when recovering the platinum group metal from an electrode coated with an electrode active material containing platinum group metal oxides of at least platinum, iridium, and ruthenium, the reduced platinum group metal is The platinum is almost completely eluted and recovered by treatment with an aqueous solution containing nitric acid, and the remaining iridium, ruthenium and binder are separated and recovered by electrolysis. The method of the present invention does not require harsh operations such as conventional mechanical or physical peeling, and can be peeled and recovered under relatively mild electrolytic conditions.
Furthermore, since the main component, platinum, has been almost completely removed in advance, the electrolysis can be completed in a minimum processing time, and no damage that would impede recoating of the electrode base material occurs.
Claims (3)
金、イリジウム及びルテニウムの白金族金属酸化物を含
む電極活性物質が被覆された電極から前記白金族金属を
回収する方法において、還元剤を使用して前記金属酸化
物を還元して金属状とし、次いで該電極を塩酸と硝酸を
含む水溶液で処理して前記金属状とされた白金とイリジ
ウムの少なくとも一部を溶出させ、その後前記電極を陽
極としてフッ素化合物を含む電解液中で電解して前記金
属の残部と前記バインダーを剥離し回収することを特徴
とする白金族金属酸化物電極からの白金族金属の回収方
法。(1) A method for recovering platinum group metals from an electrode in which an electrode active material containing platinum group metal oxides of at least platinum, iridium, and ruthenium is coated on an electrode base material via a binder, using a reducing agent. to reduce the metal oxide to a metallic state, then treat the electrode with an aqueous solution containing hydrochloric acid and nitric acid to elute at least a portion of the metallic platinum and iridium, and then convert the electrode into an anode. A method for recovering a platinum group metal from a platinum group metal oxide electrode, which comprises electrolyzing in an electrolytic solution containing a fluorine compound to peel off and recover the remainder of the metal and the binder.
及び亜硫酸塩から成る群から選択されるものである特許
請求の範囲第１項に記載の回収方法。(2) The recovery method according to claim 1, wherein the reducing agent is selected from the group consisting of hydrazine, sodium borohydride, and sulfite.
素アンモンである特許請求の範囲第１項又は第２項に記
載の回収方法。(3) The recovery method according to claim 1 or 2, wherein the fluorine compound is hydrogen fluoride and/or ammonium hydrogen fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62104133A JPS63270421A (en) | 1987-04-27 | 1987-04-27 | Method for recovering platinum group metals from platinum group metallic oxide electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62104133A JPS63270421A (en) | 1987-04-27 | 1987-04-27 | Method for recovering platinum group metals from platinum group metallic oxide electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63270421A true JPS63270421A (en) | 1988-11-08 |
Family
ID=14372608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62104133A Pending JPS63270421A (en) | 1987-04-27 | 1987-04-27 | Method for recovering platinum group metals from platinum group metallic oxide electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63270421A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS648228A (en) * | 1987-06-30 | 1989-01-12 | Tanaka Precious Metal Ind | Separation of platinum family metal of electrode from electrode substrate |
| JP2002088494A (en) * | 2000-09-13 | 2002-03-27 | Furuya Kinzoku:Kk | Method for recovering platinum group metal from metallic electrode |
| JP2002206122A (en) * | 2000-11-06 | 2002-07-26 | Dowa Mining Co Ltd | Method for recovering ruthenium metal |
| JP2002212650A (en) * | 2001-01-12 | 2002-07-31 | Furuya Kinzoku:Kk | Method for recovering platinum group metals from metallic electrode |
| CN106835163A (en) * | 2016-12-29 | 2017-06-13 | 铜陵有色金属集团股份有限公司 | For the cleaning of Ni―Ti anode noble metal surface plated film |
| WO2022138982A1 (en) * | 2020-12-25 | 2022-06-30 | パナソニックＩｐマネジメント株式会社 | Method for recovering platinum-group metal |
-
1987
- 1987-04-27 JP JP62104133A patent/JPS63270421A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS648228A (en) * | 1987-06-30 | 1989-01-12 | Tanaka Precious Metal Ind | Separation of platinum family metal of electrode from electrode substrate |
| JP2002088494A (en) * | 2000-09-13 | 2002-03-27 | Furuya Kinzoku:Kk | Method for recovering platinum group metal from metallic electrode |
| JP4607303B2 (en) * | 2000-09-13 | 2011-01-05 | 株式会社フルヤ金属 | Method for recovering platinum group metals from metal electrodes |
| JP2002206122A (en) * | 2000-11-06 | 2002-07-26 | Dowa Mining Co Ltd | Method for recovering ruthenium metal |
| JP2002212650A (en) * | 2001-01-12 | 2002-07-31 | Furuya Kinzoku:Kk | Method for recovering platinum group metals from metallic electrode |
| JP4700815B2 (en) * | 2001-01-12 | 2011-06-15 | 株式会社フルヤ金属 | Method for recovering platinum group metals from metal electrodes |
| CN106835163A (en) * | 2016-12-29 | 2017-06-13 | 铜陵有色金属集团股份有限公司 | For the cleaning of Ni―Ti anode noble metal surface plated film |
| CN106835163B (en) * | 2016-12-29 | 2018-11-23 | 铜陵有色金属集团股份有限公司 | Cleaning process for Ni―Ti anode surface noble metal plated film |
| WO2022138982A1 (en) * | 2020-12-25 | 2022-06-30 | パナソニックＩｐマネジメント株式会社 | Method for recovering platinum-group metal |
| JP7126185B1 (en) * | 2020-12-25 | 2022-08-26 | パナソニックＩｐマネジメント株式会社 | Method for recovering platinum group metals |
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