JPH05186840A - Method for recovering metal of platinum group from catalyst with metallic foil carrier - Google Patents
Method for recovering metal of platinum group from catalyst with metallic foil carrierInfo
- Publication number
- JPH05186840A JPH05186840A JP288792A JP288792A JPH05186840A JP H05186840 A JPH05186840 A JP H05186840A JP 288792 A JP288792 A JP 288792A JP 288792 A JP288792 A JP 288792A JP H05186840 A JPH05186840 A JP H05186840A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- platinum group
- foil carrier
- metal
- metal foil
- 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
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、ステンレスおよび、
Fe−Cr−Al等の金属材料を用いた、金属箔担体に触媒活
性成分として白金族金属を含むコート層が塗布されて成
る金属箔担体触媒から白金族金属を効率良く回収する方
法に関する。This invention relates to stainless steel and
The present invention relates to a method for efficiently recovering a platinum group metal from a metal foil carrier catalyst comprising a metal foil carrier coated with a coating layer containing a platinum group metal as a catalytically active component using a metal material such as Fe-Cr-Al.
【０００２】[0002]
【従来の技術】従来の貴金属回収方法としては、例えば
塩酸、王水等に代表される酸溶解法があり、セラミック
担体触媒からの白金族金属回収方法としてよく知られて
いる。また、金属箔担体触媒を水酸化ナトリウム溶液で
浸出処理し、白金族金属をブラック状で回収するアルカ
リ溶解法もまたよく知られている。2. Description of the Related Art As a conventional noble metal recovery method, there is an acid dissolution method typified by hydrochloric acid, aqua regia, etc., which is well known as a platinum group metal recovery method from a ceramic carrier catalyst. Further, an alkali dissolution method in which a metal foil carrier catalyst is leached with a sodium hydroxide solution to recover a platinum group metal in a black form is also well known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、酸溶解
方法は金属箔担体並びに白金族金属も溶解するため、多
大な量の薬品を必要とするうえに加えて、溶解後の白金
族金属の分離、精製工程で効率的に分離回収する為に中
和を行なう必要があり、この結果、金属箔担体原料であ
る金属の水酸化物が析出する為、効率の低下を招き工業
的に最適な方法とは言えない。また、アルカリ溶解法の
問題点としては、現在のほとんどの自動車用触媒に酸化
セリウムを含有させたアルミナが使用されているという
ことがある。自動車のような高温下で長時間使用された
触媒では、酸化セリウムが４価になっている。４価の酸
化セリウムは、水酸化ナトリウムには不溶であるため、
これを還元して３価の酸化セリウムにする必要がある。
これまでのアルカリ溶解法では、このアルミナに含有さ
れている酸化セリウムが、水酸化ナトリウムに不溶であ
るため多大な量の薬品を必要としており、しかも長い時
間を必要としているため、やはり工業的に最適な方法と
は言えないという問題点があった。However, since the acid dissolution method dissolves the metal foil carrier as well as the platinum group metal, a large amount of chemicals is required, and in addition, separation of the platinum group metal after dissolution, It is necessary to perform neutralization for efficient separation and recovery in the refining process, and as a result, metal hydroxide, which is a metal foil carrier raw material, precipitates, leading to a decrease in efficiency and an industrially optimum method. I can't say. Another problem with the alkali dissolution method is that most of the current automobile catalysts use alumina containing cerium oxide. Cerium oxide is tetravalent in catalysts used for a long time at high temperatures such as automobiles. Tetravalent cerium oxide is insoluble in sodium hydroxide,
It is necessary to reduce this to trivalent cerium oxide.
In the conventional alkali dissolution method, the cerium oxide contained in this alumina requires a large amount of chemicals because it is insoluble in sodium hydroxide, and also requires a long time. There was a problem that it was not the optimal method.
【０００４】[0004]
【課題を解決するための手段】この発明は、このような
従来の問題点に着目してなされたもので、金属箔担体を
溶解することなく短時間で、且つ、酸化セリウムを含有
するアルミナ層を溶解し白金族金属をブラック状即ち微
細な金属状態とすることで、簡便且つ、効率的に回収す
方法を提供するものである。以下、この発明について説
明する。The present invention has been made by paying attention to such conventional problems, and it is an alumina layer containing cerium oxide in a short time without dissolving the metal foil carrier. The present invention provides a method for recovering platinum group metal in a black state, that is, a fine metal state, by simply and efficiently recovering the platinum group metal. The present invention will be described below.
【０００５】本発明は、金属箔担体触媒から白金族金属
を回収する方法において、金属箔担体に白金族金属を担
持した触媒を水酸化ナトリウムとヒドラジンを含む水溶
液中で超音波振動を与え浸出する。The present invention is a method of recovering a platinum group metal from a metal foil carrier catalyst, wherein a catalyst in which a platinum group metal is supported on a metal foil carrier is leached by ultrasonic vibration in an aqueous solution containing sodium hydroxide and hydrazine. .
【０００６】水酸化ナトリウムを用いると、金属箔担体
の溶出がおさえられ効率的に触媒層を溶解する。ヒドラ
ジンは酸化セリウムを還元して、水酸化ナトリウムに効
率的に溶解させることができ、白金、パラジウム等の白
金族金属をブラック状にして回収する為効率の良い分
離、精製が図れる。When sodium hydroxide is used, elution of the metal foil carrier is suppressed and the catalyst layer is efficiently dissolved. Hydrazine can reduce cerium oxide and can be efficiently dissolved in sodium hydroxide. Since platinum group metals such as platinum and palladium are recovered in a black state, efficient separation and purification can be achieved.
【０００７】白金族金属を含む酸化セリウムを含有する
アルミナ層は、水酸化ナトリウムに溶解し、水酸化セリ
ウムとアルミン酸ナトリウムとなり、濾過する事で容易
に白金族金属と分離が可能になる。The alumina layer containing cerium oxide containing a platinum group metal is dissolved in sodium hydroxide to form cerium hydroxide and sodium aluminate, which can be easily separated from the platinum group metal by filtering.
【０００８】[0008]
【作用】次に作用を説明する。金属箔担体触媒の触媒層
は、金属箔担体表面に酸化セリウムを含有したガンマ−
又はデルタ−アルミナのごとき活性アルミナ層を塗布し
た後、白金、ロジウム、パラジウム等の白金族金属塩を
含浸担持している。この活性アルミナ中の酸化セリウム
はヒドラジンにより還元され、アルミナと共に水酸化ナ
トリウム溶液中に容易に溶解し水酸化セリウムとアルミ
ン酸ナトリウムの溶液となるが、白金族金属は溶解しな
い為ブラック状で分離が可能になる。[Operation] Next, the operation will be described. The catalyst layer of the metal foil carrier catalyst is a gamma-containing catalyst containing cerium oxide on the surface of the metal foil carrier.
Alternatively, after coating an activated alumina layer such as delta-alumina, a platinum group metal salt such as platinum, rhodium or palladium is impregnated and supported. The cerium oxide in this activated alumina is reduced by hydrazine and easily dissolves with alumina in sodium hydroxide solution to form a solution of cerium hydroxide and sodium aluminate, but the platinum group metal does not dissolve and is separated in black. It will be possible.
【０００９】[0009]
【実施例】以下、この発明を実施例及び、比較例により
説明する。実施例１ Fe−20Cr−５Alを酸化処理し、酸化セリウムを含有した
ガンマ−アルミナ層を塗布した金属箔体に、Pt 1.46g、
Rh 0.146g を担持した触媒(400セル、1.3L) を20重量％
の水酸化ナトリウム、1.0 重量％のヒドラジンを含む水
溶液３L に浸漬し、超音波振動を与え80℃に加熱し４時
間浸出した。その後放冷し、吸引濾過装置を用いて濾過
し、白金とロジウムを分離した。この結果、白金、ロジ
ウムの回収率はPt＝98％、Rh＝95％であった。尚回収率
は回収された白金とロジウムを再度王水に溶解し、液重
量及び純度分析を行い重量を求め、この重量から溶出率
を求めて算出した。EXAMPLES The present invention will be described below with reference to examples and comparative examples. Example 1 Pt 1.46 g was added to a metal foil body in which Fe-20Cr-5Al was oxidized and a gamma-alumina layer containing cerium oxide was applied.
20% by weight of catalyst (400 cells, 1.3 L) carrying Rh 0.146 g
Was immersed in 3 L of an aqueous solution containing sodium hydroxide of 1.0% by weight of hydrazine, heated to 80 ° C. with ultrasonic vibration, and leached for 4 hours. Then, the mixture was allowed to cool and filtered using a suction filtration device to separate platinum and rhodium. As a result, the recoveries of platinum and rhodium were Pt = 98% and Rh = 95%. The recovery rate was calculated by re-dissolving the recovered platinum and rhodium in aqua regia, analyzing the liquid weight and the purity to determine the weight, and determining the elution rate from this weight.
【００１０】実施例２ 実施例１において酸化セリウムを含有したアルミナを塗
布した金属箔担体に、Pd 1.46g、Rh 0.146g を担持した
触媒 (400 セル、1.3L) を20重量％の水酸化ナトリウ
ム、1.0 重量％のヒドラジンを含む水溶液3Lに浸漬し超
音波振動を与え、80℃に加熱し４時間浸出した。以下、
実施例１と同様に処理した結果、パラジウム、ロジウム
の回収率はPd＝98％、Rh＝96％であった。 Example 2 A catalyst (400 cells, 1.3 L) in which 1.46 g of Pd and 0.146 g of Rh were supported on a metal foil carrier coated with alumina containing cerium oxide in Example 1 was added to 20% by weight of sodium hydroxide. Was immersed in 3 L of an aqueous solution containing 1.0% by weight of hydrazine, ultrasonically shaken, heated to 80 ° C. and leached for 4 hours. Less than,
As a result of treating in the same manner as in Example 1, the recovery rates of palladium and rhodium were Pd = 98% and Rh = 96%.
【００１１】実施例３ 実施例１で得た金属箔担体触媒を、850 ℃で100 時間実
エンジン排ガス中にさらした後、同様の方法で白金、ロ
ジウムを浸出し、分離操作を行なった。この結果、白金
とロジウムの回収率は、Pt＝98％、Rh＝96％であった。 Example 3 The metal foil carrier catalyst obtained in Example 1 was exposed to the exhaust gas of an actual engine at 850 ° C. for 100 hours, and then platinum and rhodium were leached in the same manner to carry out a separation operation. As a result, the recoveries of platinum and rhodium were Pt = 98% and Rh = 96%.
【００１２】比較例１ 実施例１と同様にして得た金属箔担体触媒を、王水中に
浸漬し、80℃で６時間浸出した結果全ての金属箔担体は
溶解した。白金族金属を取り出す為水酸化ナトリウムで
中和したところFe, Al, Crは水酸化物として沈澱し、白
金族金属との分離が不可能となった。 Comparative Example 1 The metal foil carrier catalyst obtained in the same manner as in Example 1 was immersed in aqua regia and leached at 80 ° C. for 6 hours. As a result, all the metal foil carriers were dissolved. When the platinum group metal was taken out and neutralized with sodium hydroxide, Fe, Al, and Cr precipitated as hydroxides, making it impossible to separate from the platinum group metal.
【００１３】比較例２ 実施例３と同様、エンジン排ガス中にさらした金属箔担
体触媒を、20重量％水酸化ナトリウム溶液５L 中に浸漬
し、80℃で一昼夜浸出した。放冷後濾過して白金族金属
を分離し、王水に溶解、脱硝後白金を塩化アンモニウム
で沈澱させる従来の分離法を用い白金とロジウムを分離
した。この結果、白金、ロジウムの回収率はPt＝82％、
Rh＝68％であった。 Comparative Example 2 As in Example 3, the metal foil carrier catalyst exposed to the engine exhaust gas was dipped in 5 L of 20% by weight sodium hydroxide solution and leached at 80 ° C. for a whole day and night. After cooling, the platinum group metal was separated by filtration, dissolved in aqua regia, denitrated, and then platinum was precipitated with ammonium chloride by a conventional separation method to separate platinum and rhodium. As a result, the recovery rate of platinum and rhodium was Pt = 82%,
Rh = 68%.
【００１４】[0014]
【発明の効果】以上説明してきたように、この発明によ
れば、その構成を水酸化ナトリウム、ヒドラジンを含む
溶液を用い超音波振動を与え、金属箔担体触媒からの白
金族金属の回収を行なうとした為、特に高温下にさらさ
れた使用済み触媒からの白金族金属の分離回収を高い効
率で、しかも少ない薬品と短い時間で行なうことが可能
になった。この為、今後発生するであろう使用済み金属
箔担体触媒から白金族金属を回収でき、資源の有効活用
が図れると言う事が期待できる。As described above, according to the present invention, ultrasonic vibration is applied to a solution containing sodium hydroxide and hydrazine to recover the platinum group metal from the metal foil carrier catalyst. As a result, it has become possible to separate and recover the platinum group metal from the used catalyst that has been exposed to a high temperature with high efficiency, a small amount of chemicals, and a short time. Therefore, it can be expected that the platinum group metal can be recovered from the used metal foil carrier catalyst, which will be generated in the future, and the effective use of resources can be achieved.
Claims (1)
ドラジンを含む溶液中に浸漬し、超音波振動を与えて浸
出し、触媒活性層として設けられている酸化セリウムを
含有するアルミナ層を溶解し、且つ、白金族金属をブラ
ック状で回収することを特徴とする金属箔担体触媒から
の白金族金属の回収方法。1. A metal foil carrier catalyst is dipped in a solution containing sodium hydroxide and hydrazine and leached by applying ultrasonic vibration to dissolve an alumina layer containing cerium oxide provided as a catalytically active layer. A method for recovering a platinum group metal from a metal foil carrier catalyst, characterized in that the platinum group metal is recovered in black form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP288792A JPH05186840A (en) | 1992-01-10 | 1992-01-10 | Method for recovering metal of platinum group from catalyst with metallic foil carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP288792A JPH05186840A (en) | 1992-01-10 | 1992-01-10 | Method for recovering metal of platinum group from catalyst with metallic foil carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05186840A true JPH05186840A (en) | 1993-07-27 |
Family
ID=11541872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP288792A Pending JPH05186840A (en) | 1992-01-10 | 1992-01-10 | Method for recovering metal of platinum group from catalyst with metallic foil carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05186840A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0648848A1 (en) * | 1993-09-21 | 1995-04-19 | Degussa Aktiengesellschaft | Process for the recovery of platinum group metals from exhaust gas catalysts for motor vehicles |
| US7740685B2 (en) | 2004-04-05 | 2010-06-22 | R.O. Processing, Inc. | Process for removal of the catalytic coating material from spent, defective or unused metal support catalytic converters |
| CN110527834A (en) * | 2018-05-23 | 2019-12-03 | 国家能源投资集团有限责任公司 | The method for handling waste flue gas denitration catalyst |
-
1992
- 1992-01-10 JP JP288792A patent/JPH05186840A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0648848A1 (en) * | 1993-09-21 | 1995-04-19 | Degussa Aktiengesellschaft | Process for the recovery of platinum group metals from exhaust gas catalysts for motor vehicles |
| US7740685B2 (en) | 2004-04-05 | 2010-06-22 | R.O. Processing, Inc. | Process for removal of the catalytic coating material from spent, defective or unused metal support catalytic converters |
| CN110527834A (en) * | 2018-05-23 | 2019-12-03 | 国家能源投资集团有限责任公司 | The method for handling waste flue gas denitration catalyst |
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