WO2012029379A1 - Recovery method for high purity platinum - Google Patents
Recovery method for high purity platinum Download PDFInfo
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- WO2012029379A1 WO2012029379A1 PCT/JP2011/064096 JP2011064096W WO2012029379A1 WO 2012029379 A1 WO2012029379 A1 WO 2012029379A1 JP 2011064096 W JP2011064096 W JP 2011064096W WO 2012029379 A1 WO2012029379 A1 WO 2012029379A1
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- platinum
- ruthenium
- aqua regia
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
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- 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
Definitions
- the present invention relates to a high-purity platinum recovery method for recovering high-purity platinum in a high yield from scraps such as platinum alloys containing platinum and ruthenium as a component, particularly magnetic material targets.
- the impurities as described above cause a decrease in the performance of the recording medium, the hard disk, and the semiconductor device element, and may cause splash, abnormal discharge, particles, and the like during the sputtering, thereby reducing the properties of the thin film.
- acid such as aqua regia and removing the residue
- the acid dissolved with platinum and ammonium chloride solution are reacted to precipitate and recover as ammonium chloroplatinate. Platinum is recovered by baking.
- Magnetic thin films containing platinum as a main component of constituent elements or a part of constituent elements are often containing ruthenium as a part of the constituent elements. Since ruthenium is a platinum group element, its properties are similar and it is difficult to separate platinum and ruthenium. Ruthenium is an impurity unless platinum and ruthenium are separated, except in special cases where even if ruthenium is mixed in platinum, there is no particular problem with the properties of the material. Since platinum itself is a very expensive material, it must be recovered with good yield. Several techniques for recovering platinum have been proposed in the patent literature. The following are introduced below. What is an efficient recovery method for separating ruthenium from platinum and recovering high-purity platinum? I can not say.
- Patent Document 1 when platinum is extracted as an ammonium chloride salt by extracting platinum, the pH of the gold-containing platinum group metal-containing chloride-containing aqueous solution is adjusted to perform two-stage neutralization and filtration. Techniques for separating are disclosed. Patent Document 2 below discloses a technique for removing impurities ruthenium by heating to high temperature in an oxygen gas stream against ammonium chloroplatinate or platinum.
- Patent Document 3 when ruthenium is separated from a platinum group-containing solution by oxidative distillation, the pH of the solution is adjusted, and then sodium bromate is used to convert ruthenium to ruthenium tetroxide for oxidative distillation.
- Patent Document 4 listed below discloses a method for producing platinum powder in which, when ammonium chloroplatinate is formed, fine ammonium chloroplatinate is obtained using a dispersion stabilizer in an ammonium chloride solution, and this is baked at a low temperature. Has been.
- Patent Document 5 discloses a method for recovering high-purity platinum in which platinum-containing scraps are dissolved with an acid, reacted with an ammonium chloride solution, precipitated and recovered as ammonium chloroplatinate, and roasted to obtain a platinum sponge. It is disclosed.
- Patent Document 6 after a platinum-containing scrap is dissolved with an acid, it is reacted with an ammonium chloride solution, and precipitated and recovered as ammonium chloroplatinate, and the remaining platinum is recovered using an ion exchange resin and activated carbon. The technology is described.
- the present invention is a platinum alloy for sputtering, in particular, target scrap containing platinum used for forming a magnetic thin film (used target) or scraps generated in the manufacturing process of the target, cutting scrap, flat grinding scrap. It is possible to efficiently remove cobalt, chromium, copper, iron, nickel, silicon and the like mixed in scrap such as ruthenium contained in platinum alloy scrap for sputtering, and thereby platinum and
- the present invention provides a method for recovering high-purity platinum that can be reused for a platinum-containing target at a low cost and in a high yield.
- the present invention 1) Dissolve a platinum alloy containing ruthenium in aqua regia and remove the residue, then react the platinum-dissolved acid with an ammonium chloride solution to precipitate an ammonium chloroplatinate salt.
- This ammonium chloroplatinate salt Of high purity platinum to obtain platinum sponge by reducing platinum, wherein the acid in which platinum is dissolved and ammonium chloride solution are reacted at a temperature of 40 ° C or higher 2
- the platinum alloy containing ruthenium is A method for recovering high-purity platinum according to 1) or 2), wherein the ruthenium concentration of a solution dissolved in water is 6 g / L or less.
- the present invention also provides: 4) The ruthenium content as an impurity in the platinum sponge obtained by roasting ammonium chloroplatinate is 2% or less, 1) to 3) 5) The high purity platinum recovery method according to 4), wherein the ruthenium content is 1% or less. 6) The ruthenium-containing platinum alloy is a scrap of a magnetic material target. A method for recovering high-purity platinum according to any one of 1) to 5), wherein the platinum recovery rate from the scrap is 99% or more.
- Cobalt, chromium, copper, iron, nickel, silicon, etc. mixed into scraps such as scrap containing platinum-containing target scrap (used target) for sputtering or scraps generated in the target manufacturing process, cutting scraps, flat scraps, etc. are relatively easy.
- it has an excellent effect of efficiently separating ruthenium, which is a platinum group element contained in the magnetic material target, from platinum.
- a scrap containing platinum and ruthenium and further containing cobalt, chromium, copper, iron, nickel, silicon and the like as impurity elements is first dissolved with an acid.
- Aqua regia is used as the acid for dissolution.
- aqua regia is used, dissolution is sufficiently achieved, and since nitrogen oxides and hydrogen are generated at the same time, there is an advantage that hydrogen is diluted and there is no danger of explosion.
- platinum does not readily dissolve in the initial stage, but platinum gradually dissolves well.
- an acid in which platinum is dissolved is reacted with an ammonium chloride solution to precipitate ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystals.
- an ammonium chloride solution to precipitate ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystals.
- aqua regia in which platinum is dissolved to the ammonium chloride solution.
- it is common knowledge to try to add an ammonium chloride solution to aqua regia in which platinum is dissolved.
- ammonium chloroplatinate is redissolved and hardly precipitated, and platinum remains in the solution.
- a phenomenon in which the yield of platinum falls is observed.
- the problem is that ruthenium separation has not been studied in the scrap. This is because the formation of a magnetic film or the addition of ruthenium as a constituent element of the target has not been widely performed, so that the separation of ruthenium has not been a major problem. However, it is urgent at present. On the other hand, since ruthenium is a platinum group element as described above, separation from platinum is not easy. The present invention provides a technique for easily and efficiently separating this.
- the high purity platinum recovery method of the present invention involves dissolving a ruthenium-containing platinum alloy with aqua regia, removing the residue, and then reacting an acid in which platinum is dissolved with an ammonium chloride solution to obtain an ammonium chloroplatinate salt.
- the acid in which the platinum is dissolved and the ammonium chloride solution are reacted at a temperature of 40 ° C. or higher.
- the upper limit of the temperature is not particularly limited, but it can be said that the upper limit of the temperature is preferably 100 ° C. or less at which the liquid does not evaporate.
- the process until obtaining the sponge can be said to be a conventional technique.
- it was difficult to separate ruthenium and the intended separation was not realized.
- the platinum recovery rate was improved, and the ruthenium content in the platinum salt could be reduced. This was a very unexpected result.
- the technique of reducing the chloroplatinic acid ammonium salt to obtain a platinum sponge is a relatively simple and efficient manufacturing process, and this technique on the extension line enables the separation of ruthenium. Although this looks simple at first glance, as described above, it was difficult to predict and a dramatic effect was obtained.
- the platinum concentration of a solution obtained by dissolving a platinum alloy containing ruthenium with aqua regia is preferably 15 g / L or more. This is because, when the platinum concentration is reduced to less than 15 g / L, the solubility of the platinum salt increases, so that the platinum recovery rate from scrap decreases (less than 99%).
- the platinum content in scrap is usually 30% by weight or more.
- the platinum concentration in the solution is much higher than 15 g / L, diluted with a large amount of water. As long as it is not, the concentration never falls below 15 g / L.
- the concentration of ruthenium is high and the platinum content is relatively low, if the concentration is lower than 15 g / L as it is, the aqua regia can be dissolved by mixing with scrap having a high platinum content.
- the ruthenium concentration of a solution obtained by dissolving a platinum alloy containing ruthenium with aqua regia is 6 g / L or less.
- the reaction temperature is also affected, but if the ruthenium concentration exceeds 6 g / L, ruthenium tends to enter precipitates. To reduce this ruthenium concentration, it is only necessary to dilute with water. However, since the platinum concentration of the liquid is decreased, mutual adjustment is necessary.
- the ruthenium content as an impurity in the platinum sponge obtained by baking the chloroplatinic acid ammonium salt is 2% or less, further 1% or less. Can do. Furthermore, it is possible to achieve a platinum recovery rate of 99% or more from scrap of a magnetic material target containing a platinum alloy containing ruthenium.
- the present invention provides a method for recovering such high-purity platinum.
- Example 1 In Example 1, a scrap of a magnetic material target containing platinum, cobalt, chromium and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to have a platinum concentration of 30 g / L and a ruthenium concentration of 5 g / L. The aqua regia solution. This aqua regia solution and ammonium chloride were reacted at 45 ° C. to obtain ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystals. Next, it was baked at 800 ° C. to obtain a platinum sponge, and the platinum recovery rate from the aqua regia solution and the ruthenium content rate as impurities were measured. The results are shown in Table 1.
- the platinum recovery rate reached 99.5%, and the ruthenium content in the platinum salt decreased to 0.5% by weight. This ruthenium content was sufficiently reduced in the case of using recycled platinum as a target. Further, if the reaction temperature between the aqua regia solution and ammonium chloride is 40 ° C. or higher, the same platinum purity and ruthenium reduction can be achieved.
- the roasting temperature is not particularly limited and can be adjusted as appropriate, and the temperature at which a platinum sponge is usually obtained can be arbitrarily selected. The same applies hereinafter.
- Example 2 the scrap of the magnetic material target containing platinum, cobalt, chromium, and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to obtain a platinum concentration of 18 g / L and a ruthenium concentration of 3 g / L.
- the aqua regia solution This aqua regia solution and ammonium chloride are reacted at 90 ° C. to precipitate ammonium chloroplatinate salt, which is roasted at 800 ° C. to form a platinum sponge.
- Platinum recovery rate and impurities from the aqua regia solution The ruthenium content as was measured. The results are shown in Table 1.
- the platinum recovery rate reached 99.3%, and the ruthenium content in the platinum salt decreased to 0.3% by weight. This ruthenium content was sufficiently reduced in the case of using recycled platinum as a target. Further, if the reaction temperature between the aqua regia solution and ammonium chloride is 40 ° C. or higher, the same platinum purity and ruthenium reduction can be achieved.
- Example 3 In Example 3, the scrap of the magnetic material target containing platinum, cobalt, chromium and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to have a platinum concentration of 16 g / L and a ruthenium concentration of 5 g / L.
- the aqua regia solution This aqua regia solution and ammonium chloride are reacted at 50 ° C. to precipitate an ammonium chloroplatinate salt, which is baked at 800 ° C. to form a platinum sponge.
- the ruthenium content was measured. The results are shown in Table 1.
- the platinum recovery rate reached 99.2%, and the ruthenium content in the platinum salt decreased to 1.7% by weight. This ruthenium content was sufficiently reduced in the case of using recycled platinum as a target. Further, if the reaction temperature between the aqua regia solution and ammonium chloride is 40 ° C. or higher, the same platinum purity and ruthenium reduction can be achieved.
- Cobalt, chromium, copper, iron, nickel, silicon, etc. mixed in scrap such as scraps, cutting scraps, flat polishing scraps, etc., generated in the manufacturing process of platinum for sputtering and platinum-containing targets are removed in a relatively simple process, It has an excellent effect that high-purity platinum that can be reused for platinum and a target containing these can be recovered in a high yield.
- ruthenium which is said to be particularly difficult to separate from platinum, has the effect that it can be reduced in a relatively simple method, so it is useful to recover high-purity platinum at a low cost and in a high yield. Can provide a simple method.
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Abstract
Description
これらの薄膜は、白金等を含有する合金製のターゲットをアルゴンガス等の不活性雰囲気下でスパッタリングすることにより形成される。 In recent years, with the great progress of semiconductor integrated circuits, various thin films have been formed for circuit design and formation of various electric and electronic elements. Among them, platinum is used for magnetic thin films for recording media or semiconductor materials. A specific thin film is also formed using the alloy sputtering target contained. Such platinum alloy targets often contain ruthenium as an alloy element.
These thin films are formed by sputtering an alloy target containing platinum or the like in an inert atmosphere such as argon gas.
ターゲットへの製作工程では、溶解鋳造後にインゴットの鍛造・圧延等の塑性加工又は切削等の機械加工さらにはバッキングプレートへの接合工程により、ターゲットに接触する部分の汚染が起きる。特に機械加工の切削工具や周辺の加工具を構成する材料からの重金属等の汚染が著しい。
白金は高価な材料なので、これを回収して再使用する必要があるが、上記のような汚染が入った材料はそのままでは使用できないという問題がある。 At the stage where this target is manufactured, a large amount of cutting material such as cutting waste is generated. These are all scrap. Used targets are also scrap.
In the manufacturing process for the target, contamination of the portion in contact with the target occurs after melt casting by plastic processing such as forging and rolling of the ingot or mechanical processing such as cutting, and further by a joining process to the backing plate. In particular, the contamination of heavy metals and the like from materials constituting machining tools and peripheral processing tools is remarkable.
Since platinum is an expensive material, it needs to be recovered and reused, but there is a problem that the contaminated material cannot be used as it is.
通常、白金含有スクラップを王水等の酸で溶解し残渣を除去した後、白金を溶解した酸と塩化アンモニウム溶液を反応させて塩化白金酸アンモニウムとして沈殿回収し、さらにこの塩化白金酸アンモニウムを焙焼することにより白金を回収することが行われている。 The impurities as described above cause a decrease in the performance of the recording medium, the hard disk, and the semiconductor device element, and may cause splash, abnormal discharge, particles, and the like during the sputtering, thereby reducing the properties of the thin film.
Usually, after scraping platinum-containing scrap with acid such as aqua regia and removing the residue, the acid dissolved with platinum and ammonium chloride solution are reacted to precipitate and recover as ammonium chloroplatinate. Platinum is recovered by baking.
白金中にルテニウムが混入していても材料の特性に特に問題とならないという特殊なケースを除いて、白金とルテニウムを分離しない限り、ルテニウムが不純物となる。白金自体は非常に高価な材料なので収率良く回収する必要がある。
白金を回収するという技術について、特許文献にいくつか提案されているので、それを下記に紹介するが、白金からルテニウムを分離し、高純度の白金を回収するための効率的な回収方法とは言えない。 Magnetic thin films containing platinum as a main component of constituent elements or a part of constituent elements are often containing ruthenium as a part of the constituent elements. Since ruthenium is a platinum group element, its properties are similar and it is difficult to separate platinum and ruthenium.
Ruthenium is an impurity unless platinum and ruthenium are separated, except in special cases where even if ruthenium is mixed in platinum, there is no particular problem with the properties of the material. Since platinum itself is a very expensive material, it must be recovered with good yield.
Several techniques for recovering platinum have been proposed in the patent literature. The following are introduced below. What is an efficient recovery method for separating ruthenium from platinum and recovering high-purity platinum? I can not say.
下記特許文献2には、塩化白金酸アンモニウム又は白金に対して、酸素ガスの気流中で、高温に加熱し、不純物ルテニウムを除去する技術が開示されている。 In Patent Document 1 below, when platinum is extracted as an ammonium chloride salt by extracting platinum, the pH of the gold-containing platinum group metal-containing chloride-containing aqueous solution is adjusted to perform two-stage neutralization and filtration. Techniques for separating are disclosed.
Patent Document 2 below discloses a technique for removing impurities ruthenium by heating to high temperature in an oxygen gas stream against ammonium chloroplatinate or platinum.
下記特許文献4には、塩化白金酸アンモニウムを形成する際に、塩化アンモニウム溶液に分散安定化剤を用いて微細な塩化白金酸アンモニウムを得、これを低温で焼成する白金粉末の製造方法が開示されている。 In Patent Document 3 below, when ruthenium is separated from a platinum group-containing solution by oxidative distillation, the pH of the solution is adjusted, and then sodium bromate is used to convert ruthenium to ruthenium tetroxide for oxidative distillation. However, a technique for separating and recovering ruthenium is disclosed.
Patent Document 4 listed below discloses a method for producing platinum powder in which, when ammonium chloroplatinate is formed, fine ammonium chloroplatinate is obtained using a dispersion stabilizer in an ammonium chloride solution, and this is baked at a low temperature. Has been.
下記特許文献6には、白金含有スクラップを酸で溶解した後、塩化アンモニウム溶液と反応させ、塩化白金酸アンモニウムとして沈殿回収し、後液に残存する白金をイオン交換樹脂、活性炭を用いて回収する技術が記載されている。 Patent Document 5 below discloses a method for recovering high-purity platinum in which platinum-containing scraps are dissolved with an acid, reacted with an ammonium chloride solution, precipitated and recovered as ammonium chloroplatinate, and roasted to obtain a platinum sponge. It is disclosed.
In Patent Document 6 below, after a platinum-containing scrap is dissolved with an acid, it is reacted with an ammonium chloride solution, and precipitated and recovered as ammonium chloroplatinate, and the remaining platinum is recovered using an ion exchange resin and activated carbon. The technology is described.
1)ルテニウムを含有する白金合金を王水で溶解し、残渣を除去した後、白金を溶解した酸と塩化アンモニウム溶液とを反応させて塩化白金酸アンモニウム塩を析出させ、この塩化白金酸アンモニウム塩を還元して白金スポンジを得る高純度白金の回収方法であって、前記白金を溶解した酸と塩化アンモニウム溶液とを40°C以上の温度で反応させることを特徴とする高純度白金の回収方法
2)ルテニウムを含有する白金合金を王水により溶解した液の白金濃度を15g/L以上とすることを特徴とする1)記載の高純度白金の回収方法
3)ルテニウムを含有する白金合金を王水により溶解した液のルテニウム濃度を6g/L以下とすることを特徴とする1)又は2)記載の高純度白金の回収方法、を提供する。 The present invention
1) Dissolve a platinum alloy containing ruthenium in aqua regia and remove the residue, then react the platinum-dissolved acid with an ammonium chloride solution to precipitate an ammonium chloroplatinate salt. This ammonium chloroplatinate salt Of high purity platinum to obtain platinum sponge by reducing platinum, wherein the acid in which platinum is dissolved and ammonium chloride solution are reacted at a temperature of 40 ° C or higher 2) The method for recovering high-purity platinum according to 1), wherein the platinum concentration of a solution in which a platinum alloy containing ruthenium is dissolved in aqua regia is 15 g / L or more 3) The platinum alloy containing ruthenium is A method for recovering high-purity platinum according to 1) or 2), wherein the ruthenium concentration of a solution dissolved in water is 6 g / L or less.
4)塩化白金酸アンモニウム塩を焙焼して得られる白金スポンジ中の不純物としてのルテニウム含有量を2%以下とすることを特徴とする1)~3)のいずれか一項に記載の高純度白金の回収方法
5)ルテニウム含有量を1%以下とすることを特徴とする4)記載の高純度白金の回収方法
6)ルテニウムを含有する白金合金が磁性材ターゲットのスクラップであって、該スクラップからの白金回収率が99%以上であることを特徴とする1)~5)のいずれか一項に記載の高純度白金の回収方法、を提供する。 The present invention also provides: 4) The ruthenium content as an impurity in the platinum sponge obtained by roasting ammonium chloroplatinate is 2% or less, 1) to 3) 5) The high purity platinum recovery method according to 4), wherein the ruthenium content is 1% or less. 6) The ruthenium-containing platinum alloy is a scrap of a magnetic material target. A method for recovering high-purity platinum according to any one of 1) to 5), wherein the platinum recovery rate from the scrap is 99% or more.
王水を用いると溶解が十分達成され、また溶解時に窒素酸化物と水素が同時に発生するので、水素が希釈され爆発の危険性がないという利点がある。王水を使用した場合、初期においては白金がなかなか溶解しないが、次第に白金が良く溶けるようになる。 In the present invention, a scrap containing platinum and ruthenium and further containing cobalt, chromium, copper, iron, nickel, silicon and the like as impurity elements is first dissolved with an acid. Aqua regia is used as the acid for dissolution. Although it is possible to dissolve with other acids, for example, when dissolved with hydrochloric acid, the dissolution is incomplete, and hydrogen is generated and there is a possibility of hydrogen explosion.
When aqua regia is used, dissolution is sufficiently achieved, and since nitrogen oxides and hydrogen are generated at the same time, there is an advantage that hydrogen is diluted and there is no danger of explosion. When aqua regia is used, platinum does not readily dissolve in the initial stage, but platinum gradually dissolves well.
この残渣を除去した後、白金を含有する溶液に水酸化ナトリウム(NaOH)等の苛性アルカリを添加しpHを3~6に調整して中和し、コバルト、銅等を水酸化物として沈殿させ、これを濾過除去する。
溶液にパラジウムが含有している場合には、コバルト、銅等の水酸化物を沈殿除去した後、溶媒抽出によりパラジウムを抽出する。パラジウム抽出後、該抽出されたパラジウムをアンモニアで逆抽出し、パラジウム含有液を還元剤、例えばヒドラジン等で還元して高純度パラジウムスポンジを回収することができる。 After dissolution of the platinum-containing scrap with acid, impurities such as tantalum oxide (Ta 2 O 5 ) and boron oxide (B 2 O 3 ) that are residues are removed.
After removing the residue, the solution containing platinum is neutralized by adding caustic such as sodium hydroxide (NaOH) to adjust the pH to 3-6, and cobalt, copper, etc. are precipitated as hydroxides. This is filtered off.
When palladium is contained in the solution, the palladium, such as cobalt and copper, is precipitated and removed, and then extracted by solvent extraction. After the palladium extraction, the extracted palladium can be back-extracted with ammonia, and the palladium-containing liquid can be reduced with a reducing agent such as hydrazine to recover a high-purity palladium sponge.
通常、白金を溶解した王水に塩化アンモニウム溶液を添加しようとするのが常識であるが、このような手法をとると塩化白金酸アンモニウムが再溶解し、析出し難くなり、液に白金が残存し、白金の収率が落ちる現象が見られる。 Next, an acid in which platinum is dissolved is reacted with an ammonium chloride solution to precipitate ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystals. In this case, it is desirable to add aqua regia in which platinum is dissolved to the ammonium chloride solution.
Usually, it is common knowledge to try to add an ammonium chloride solution to aqua regia in which platinum is dissolved. However, when such a method is used, ammonium chloroplatinate is redissolved and hardly precipitated, and platinum remains in the solution. However, a phenomenon in which the yield of platinum falls is observed.
次に、このようにして得た塩化白金酸アンモニウム((NH4)2PtCl6)結晶を600~1000°Cで焙焼して高純度白金スポンジを得る。これによって、白金の収率は97%に達し、比較的簡単な方法で高純度の白金が収率良く回収できる。以上の工程については、本特許出願人の前身である日鉱マテリアルズ(社名変更)が開発した特許文献6に開示された方法であり、効率的な高純度白金の回収方法である。 Therefore, in order to increase the yield of platinum, it is important to add aqua regia in which platinum is dissolved to the ammonium chloride solution.
Next, the ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystal thus obtained is roasted at 600 to 1000 ° C. to obtain a high purity platinum sponge. Thereby, the yield of platinum reaches 97%, and high-purity platinum can be recovered with high yield by a relatively simple method. About the above process, it is the method disclosed by the patent document 6 which the Nikko Materials (company name change) which is a predecessor of this patent applicant developed, and is an efficient collection method of high purity platinum.
一方、ルテニウムは上記の通り、白金族元素であるために、白金との分離は簡単ではない。本願発明は、これを簡単にかつ効率良く分離する技術を提供するものである。 The problem is that ruthenium separation has not been studied in the scrap. This is because the formation of a magnetic film or the addition of ruthenium as a constituent element of the target has not been widely performed, so that the separation of ruthenium has not been a major problem. However, it is urgent at present.
On the other hand, since ruthenium is a platinum group element as described above, separation from platinum is not easy. The present invention provides a technique for easily and efficiently separating this.
温度の上限は、特に制限はないが、液が蒸発しない100°C以下とするのが望ましいと言える。 The high purity platinum recovery method of the present invention involves dissolving a ruthenium-containing platinum alloy with aqua regia, removing the residue, and then reacting an acid in which platinum is dissolved with an ammonium chloride solution to obtain an ammonium chloroplatinate salt. In the method for recovering high-purity platinum obtained by precipitation and reduction of the ammonium chloroplatinate salt to obtain a platinum sponge, the acid in which the platinum is dissolved and the ammonium chloride solution are reacted at a temperature of 40 ° C. or higher.
The upper limit of the temperature is not particularly limited, but it can be said that the upper limit of the temperature is preferably 100 ° C. or less at which the liquid does not evaporate.
これは、一見単純に見えるが、上記にも述べたように、予想することは困難であり、飛躍的な効果を得るものであった。 That is, the technique of reducing the chloroplatinic acid ammonium salt to obtain a platinum sponge is a relatively simple and efficient manufacturing process, and this technique on the extension line enables the separation of ruthenium.
Although this looks simple at first glance, as described above, it was difficult to predict and a dramatic effect was obtained.
スクラップ中の白金含有率は通常30重量%以上あり、これを通常の条件で王水溶解した場合、溶解液中の白金濃度は15g/Lを大きく上回る濃度になっており、大量の水で希釈しない限り、濃度が15g/Lを下回ることはない。但し、ルテニウム含有率が高く、白金含有率が相対的に低い場合など、そのままでは濃度が15g/Lを下回る場合は、白金含有率の高いスクラップと混ぜて王水溶解を行えば良い。 In the high purity platinum recovery method of the present invention, the platinum concentration of a solution obtained by dissolving a platinum alloy containing ruthenium with aqua regia is preferably 15 g / L or more. This is because, when the platinum concentration is reduced to less than 15 g / L, the solubility of the platinum salt increases, so that the platinum recovery rate from scrap decreases (less than 99%).
The platinum content in scrap is usually 30% by weight or more. When this is dissolved in aqua regia under normal conditions, the platinum concentration in the solution is much higher than 15 g / L, diluted with a large amount of water. As long as it is not, the concentration never falls below 15 g / L. However, when the concentration of ruthenium is high and the platinum content is relatively low, if the concentration is lower than 15 g / L as it is, the aqua regia can be dissolved by mixing with scrap having a high platinum content.
上記反応温度にも影響するが、このルテニウム濃度を6g/Lを超えると、ルテニウムが析出物に入り易くなるからである。このルテニウム濃度を下げることは、水で薄めるだけで良い。しかし、逆に液の白金濃度を低下させることになるので、相互の調整が必要である。 In the method for recovering high-purity platinum according to the present invention, it is desirable that the ruthenium concentration of a solution obtained by dissolving a platinum alloy containing ruthenium with aqua regia is 6 g / L or less.
The reaction temperature is also affected, but if the ruthenium concentration exceeds 6 g / L, ruthenium tends to enter precipitates. To reduce this ruthenium concentration, it is only necessary to dilute with water. However, since the platinum concentration of the liquid is decreased, mutual adjustment is necessary.
本実施例1においては、白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度30g/L、ルテニウム濃度5g/Lの王水溶解液とした。
この王水溶解液と塩化アンモニウムを45°Cで反応させて塩化白金酸アンモニウム塩((NH4)2PtCl6)結晶を得た。次に、それを800°Cで焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。この結果を表1に示す。 Example 1
In Example 1, a scrap of a magnetic material target containing platinum, cobalt, chromium and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to have a platinum concentration of 30 g / L and a ruthenium concentration of 5 g / L. The aqua regia solution.
This aqua regia solution and ammonium chloride were reacted at 45 ° C. to obtain ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) crystals. Next, it was baked at 800 ° C. to obtain a platinum sponge, and the platinum recovery rate from the aqua regia solution and the ruthenium content rate as impurities were measured. The results are shown in Table 1.
本実施例2においては、白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度18g/L、ルテニウム濃度3g/Lの王水溶解液とした。
この王水溶解液と塩化アンモニウムを90°Cで反応させて塩化白金酸アンモニウム塩を析出させ、それを800°Cで焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。
この結果を表1に示す。 (Example 2)
In Example 2, the scrap of the magnetic material target containing platinum, cobalt, chromium, and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to obtain a platinum concentration of 18 g / L and a ruthenium concentration of 3 g / L. The aqua regia solution.
This aqua regia solution and ammonium chloride are reacted at 90 ° C. to precipitate ammonium chloroplatinate salt, which is roasted at 800 ° C. to form a platinum sponge. Platinum recovery rate and impurities from the aqua regia solution The ruthenium content as was measured.
The results are shown in Table 1.
本実施例3においては、白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度16g/L、ルテニウム濃度5g/Lの王水溶解液とした。
この王水溶解液と塩化アンモニウムを50℃で反応させて塩化白金酸アンモニウム塩を析出させ、それを800℃で焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。
この結果を表1に示す。 (Example 3)
In Example 3, the scrap of the magnetic material target containing platinum, cobalt, chromium and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to have a platinum concentration of 16 g / L and a ruthenium concentration of 5 g / L. The aqua regia solution.
This aqua regia solution and ammonium chloride are reacted at 50 ° C. to precipitate an ammonium chloroplatinate salt, which is baked at 800 ° C. to form a platinum sponge. The ruthenium content was measured.
The results are shown in Table 1.
白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度12g/L、ルテニウム濃度2g/Lの王水溶解液とした。この場合、白金濃度は薄く、本願発明の15g/Lよりも低かった。
この王水溶解液と塩化アンモニウムを70°Cで反応させて塩化白金酸アンモニウム塩を析出させ、それを800°Cで焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。 (Comparative Example 1)
A scrap of a magnetic material target containing platinum, cobalt, chromium, and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to obtain an aqua regia solution having a platinum concentration of 12 g / L and a ruthenium concentration of 2 g / L. . In this case, the platinum concentration was thin and was lower than 15 g / L of the present invention.
This aqua regia solution and ammonium chloride are reacted at 70 ° C. to precipitate ammonium chloroplatinate salt, which is baked at 800 ° C. to form a platinum sponge. Platinum recovery rate and impurities from the aqua regia solution The ruthenium content as was measured.
白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度48g/L、ルテニウム濃度8g/Lの王水溶解液とした。この場合、ルテニウム濃度は、本願発明の上限とする6g/Lを超えていた。
この王水溶解液と塩化アンモニウムを70°Cで反応させて塩化白金酸アンモニウム塩を析出させ、それを800°Cで焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。 (Comparative Example 2)
A scrap of a magnetic material target containing platinum, cobalt, chromium and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to obtain an aqua regia solution having a platinum concentration of 48 g / L and a ruthenium concentration of 8 g / L. . In this case, the ruthenium concentration exceeded 6 g / L which is the upper limit of the present invention.
This aqua regia solution and ammonium chloride are reacted at 70 ° C. to precipitate ammonium chloroplatinate salt, which is baked at 800 ° C. to form a platinum sponge. Platinum recovery rate and impurities from the aqua regia solution The ruthenium content as was measured.
白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを王水に溶解して残渣を除去した後、水で薄めて白金濃度30g/L、ルテニウム濃度5g/Lの王水溶解液とした。この王水溶解液と塩化アンモニウムを30°Cで反応させて塩化白金酸アンモニウム塩を析出させ、それを800°Cで焙焼して白金スポンジとし、王水溶解液からの白金回収率及び不純物としてのルテニウム含有率を測定した。この場合、王水溶解液と塩化アンモニウムとを反応させる温度は、本願発明の条件である40°C以上を満たしていなかった。 (Comparative Example 3)
A scrap of a magnetic material target containing platinum, cobalt, chromium, and ruthenium was dissolved in aqua regia to remove the residue, and then diluted with water to obtain an aqua regia solution having a platinum concentration of 30 g / L and a ruthenium concentration of 5 g / L. . This aqua regia solution and ammonium chloride are reacted at 30 ° C. to precipitate ammonium chloroplatinate salt, which is roasted at 800 ° C. to form a platinum sponge. Platinum recovery rate and impurities from the aqua regia solution The ruthenium content as was measured. In this case, the temperature at which the aqua regia solution and ammonium chloride were reacted did not satisfy the condition of the present invention of 40 ° C. or higher.
また、白金から分離することが難しいルテニウムの低減化が可能であるという結果を得ることができた。
上記においては、白金、コバルト、クロム、ルテニウムを含有する磁性材ターゲットのスクラップを用いて説明をしたが、他の不純物を有するスクラップにおいても同様に適用できるものである。 As described above, it is not only platinum, cobalt, chromium and ruthenium which are magnetic materials as scrap, but also many other impurities that come from scraps, cutting scraps, flat polishing scraps generated in the manufacturing process of the target containing platinum, For example, even though copper, iron, nickel, silicon and the like are contained, most of them can be removed, and high-purity platinum is obtained, and the yield of platinum reaches 99%.
In addition, it was possible to obtain a result that ruthenium, which is difficult to separate from platinum, can be reduced.
In the above description, the magnetic material target scrap containing platinum, cobalt, chromium, and ruthenium has been described. However, the present invention can be similarly applied to a scrap having other impurities.
Claims (6)
- ルテニウムを含有する白金合金を王水で溶解し、残渣を除去した後、白金を溶解した酸と塩化アンモニウム溶液とを反応させて塩化白金酸アンモニウム塩を析出させ、この塩化白金酸アンモニウム塩を還元して白金スポンジを得る高純度白金の回収方法であって、前記白金を溶解した酸と塩化アンモニウム溶液とを40°C以上の温度で反応させることを特徴とする高純度白金の回収方法。 A platinum alloy containing ruthenium is dissolved in aqua regia and the residue is removed. Then, an acid in which platinum is dissolved is reacted with an ammonium chloride solution to precipitate ammonium chloroplatinate, and this ammonium chloroplatinate is reduced. A high purity platinum recovery method for obtaining a platinum sponge by reacting an acid in which the platinum is dissolved with an ammonium chloride solution at a temperature of 40 ° C. or higher.
- ルテニウムを含有する白金合金を王水により溶解した液の白金濃度を15g/L以上とすることを特徴とする請求項1記載の高純度白金の回収方法。 The method for recovering high-purity platinum according to claim 1, wherein the platinum concentration of a solution obtained by dissolving a platinum alloy containing ruthenium with aqua regia is 15 g / L or more.
- ルテニウムを含有する白金合金を王水により溶解した液のルテニウム濃度を6g/L以下とすることを特徴とする請求項1又は2記載の高純度白金の回収方法。 The method for recovering high-purity platinum according to claim 1 or 2, wherein the ruthenium concentration of a solution obtained by dissolving a platinum alloy containing ruthenium in aqua regia is 6 g / L or less.
- 塩化白金酸アンモニウム塩を焙焼して得られる白金スポンジ中の不純物としてのルテニウム含有量を2%以下とすることを特徴とする請求項1~3のいずれか一項に記載の高純度白金の回収方法。 The high-purity platinum according to any one of claims 1 to 3, wherein the ruthenium content as an impurity in the platinum sponge obtained by roasting ammonium chloroplatinate is 2% or less. Collection method.
- ルテニウム含有量を1%以下とすることを特徴とする請求項4記載の高純度白金の回収方法。 The method for recovering high-purity platinum according to claim 4, wherein the ruthenium content is 1% or less.
- ルテニウムを含有する白金合金が磁性材ターゲットのスクラップであって、該スクラップからの白金回収率が99%以上であることを特徴とする請求項1~5のいずれか一項に記載の高純度白金の回収方法。 6. The high-purity platinum according to claim 1, wherein the ruthenium-containing platinum alloy is a scrap of a magnetic material target, and the platinum recovery rate from the scrap is 99% or more. Recovery method.
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CN103627902A (en) * | 2013-04-25 | 2014-03-12 | 上海派特贵金属有限公司 | Method for recovering rhodium from inactive noble metal catalyst |
AU2014201077B2 (en) * | 2013-03-05 | 2015-08-13 | Heraeus Precious Metals Gmbh & Co. Kg | Method for producing highly pure platinum powder, as well as platinum powder that can be obtained according to said method, and use thereof |
CN111926195A (en) * | 2020-06-24 | 2020-11-13 | 重庆材料研究院有限公司 | Method for preparing high-purity platinum from platinum alloy waste |
CN112126789A (en) * | 2020-09-17 | 2020-12-25 | 朱俊 | Chloroplatinic acid solution concentration process and equipment |
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