JP4604221B2 - Sponge platinum deoxygenation method, hydrogen reduction furnace used in said method, and sponge platinum pulverization method - Google Patents
Sponge platinum deoxygenation method, hydrogen reduction furnace used in said method, and sponge platinum pulverization method Download PDFInfo
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Description
本発明は、スポンジ白金の脱酸素方法及び前記方法に使用する水素還元炉及びスポンジ白金の粉砕方法に関するものであり、より詳しく述べるならば、粒子径2mm以下で、王水溶解時に未溶解残渣が少なく、かつ溶解速度の速いスポンジ白金を効率よく安全に生産する、スポンジ白金の脱酸素装置及び方法に関する物である。 The present invention relates to a method for deoxygenating sponge platinum, a hydrogen reduction furnace used in the method, and a method for pulverizing sponge platinum. More specifically, the particle diameter is 2 mm or less, and undissolved residue is dissolved in aqua regia. The present invention relates to an apparatus and method for deoxidizing sponge platinum, which efficiently and safely produces sponge platinum having a low dissolution rate and a high dissolution rate.
スポンジ白金から酸素を除くには種々の方法があり、水素バーナーの還元炎で脱酸素する方法、高温加熱又は水素加熱還元による方法（非特許文献１）、真空中で加熱して脱酸素する方法（非特許文献１）等が取られている。 There are various methods for removing oxygen from sponge platinum, a method of deoxygenating with a reducing flame of a hydrogen burner, a method of high-temperature heating or hydrogen-heated reduction (Non-patent Document 1), a method of deoxygenating by heating in vacuum (Non-Patent Document 1) and the like are taken.
スポンジ白金の用途として、触媒関係の用途が増え、王水溶解時の未溶解残渣の低減、溶解速度の向上、粗粒のものを更に微粒に、微粒のものでも更なる微粉砕化が求められてきている。 Sponge platinum is used in many applications related to catalyst, reducing undissolved residue when dissolving aqua regia, improving dissolution rate, making coarse particles even finer, and even finer particles need to be further pulverized. It is coming.
水素バーナーの還元炎で脱酸素する方法は、図9に示す処理フローであり、王水溶解時の未溶解残渣を少なくすることが出来るが、スポンジ白金の焼結が進み、粒子径2mm以下のスポンジ白金の回収が困難であった。 The method of deoxygenation with a reducing flame of a hydrogen burner is the processing flow shown in FIG. 9, which can reduce the undissolved residue during aqua regia dissolution, but the sintering of sponge platinum has progressed, and the particle diameter is 2 mm or less. It was difficult to collect sponge platinum.
高温加熱による脱酸素では、PtO2の分解は赤熱することによってPtOまで進むが、最後の酸素は離し難いうえ、800℃以上の高温にすると、焼結が進み、粒子径2mm以下のスポンジ白金回収に支障をきたすこととなり、特許文献１の方法で精製したスポンジ白金は、王水溶解残渣が図10に示すように残り好ましくなく更に粉砕の作業性の面で、効率的に粉砕が出来ず触媒向けには出荷できないでいた。 In deoxygenation by high temperature heating, the decomposition of PtO 2 proceeds to PtO by red-hot, but the last oxygen is difficult to release, and at a high temperature of 800 ° C or higher, sintering progresses and recovery of sponge platinum with a particle diameter of 2 mm or less Sponge platinum purified by the method of Patent Document 1 is not preferred because the aqua regia dissolved residue remains as shown in FIG. 10, and in terms of pulverization workability, the catalyst cannot be efficiently pulverized. Could not be shipped to.
真空中での脱酸素の場合は、表1に示すように300℃程度から酸素放出が始まり、スポンジ白金中の酸素品位を500ppm以下にできるが、10-2Torr程度の真空度では、王水未溶解残渣の発生は、図11に400℃及び500℃の例を示すように抑えられない。なお、未溶解残渣のXPSによる形態分析の結果、PtOおよびPtO2が同定された。
水素還元による脱酸素は、安全面から敬遠されており、特許文献１、特許文献２等、水素を使わない還元方法が志向されている。 Deoxygenation by hydrogen reduction is avoided from the viewpoint of safety, and reduction methods that do not use hydrogen, such as Patent Document 1 and Patent Document 2, are aimed at.
本発明は、粒子径2mm以下のスポンジ白金であり、王水溶解時に未溶解残渣が少なく、かつ溶解速度の速いスポンジ白金を効率よく安全に生産する、スポンジ白金の脱酸素装置及び方法を提案するものである。 The present invention proposes a sponge platinum deoxygenation apparatus and method for efficiently and safely producing sponge platinum having a particle diameter of 2 mm or less, having little undissolved residue when dissolved in aqua regia and having a high dissolution rate. Is.
本発明は、脱酸素時の温度を800℃以下にすれば、市販の電動ミルで粉砕できる程度の焼結状態となること、かつ、王水溶解時の未溶解残渣の形態分析の結果PtO及びPtO2が同定され、800℃以下の脱酸素温度で王水溶解時の未溶解残渣を少なくするためには、水素気流中での脱酸素が有効であるとの点に着目したものである。 In the present invention, if the temperature during deoxygenation is 800 ° C. or lower, the sintered state is such that it can be pulverized by a commercially available electric mill, and the result of morphological analysis of undissolved residue during dissolution of aqua regia PtO and PtO 2 were identified, in order to reduce the undissolved residue at aqua regia dissolution at 800 ° C. or less of the oxygen temperature, in which oxygen in a hydrogen stream in is focused on a point to be effective.
また、空気の存在下で、スポンジ白金中に残存する（NH4）2PtCl6上に乾燥した水素ガスを通じると爆発する危険があり、これを回避すれば安全に水素還元が行えるとの知見に基づいたものである。 In addition, there is a danger of explosion if dry hydrogen gas is passed over (NH 4 ) 2 PtCl 6 remaining in sponge platinum in the presence of air, and if this is avoided, hydrogen can be reduced safely It is based on.
すなわち、本発明は
（１）スポンジ白金中の酸素を除去するに際して、スポンジ白金を予め粒子径2mm以下に粉砕し、水素還元処理を600℃〜800℃にて行い、脱酸素を行うことにより、回収スポンジ白金の王水溶解時溶解速度を向上させるとともに、王水溶解時の未溶解残渣を低減することを特徴とするスポンジ白金の脱酸素方法。
（２）上記（１）において、スポンジ白金の脱酸素を行う前に、スポンジ白金を予め600℃〜800℃で加熱し、スポンジ白金中のアンモニウム塩を分解した後、水素還元処理を行うスポンジ白金の脱酸素方法。
That is, in the present invention, (1) when removing oxygen in sponge platinum, sponge platinum is previously pulverized to a particle size of 2 mm or less, hydrogen reduction treatment is performed at 600 ° C. to 800 ° C., and deoxygenation is performed. A method for deoxygenating sponge platinum, characterized by improving the dissolution rate of recovered sponge platinum during aqua regia dissolution and reducing undissolved residues during aqua regia dissolution.
(2) In the above (1), before deoxidizing the sponge platinum, the sponge platinum is heated in advance at 600 ° C. to 800 ° C. to decompose the ammonium salt in the sponge platinum and then subjected to hydrogen reduction treatment. Deoxygenation method.
（３）スポンジ白金の脱酸素工程において使用する水素還元炉に装入するスポンジ白金を、数個の磁性容器に小分けして装入し、容器破損時の影響を少なくする上記（１）もしくは（２）のいずれかに記載のスポンジ白金の脱酸素方法。（４）800℃以下の温度において脱酸素した後、スポンジ白金を電動ミルにより粉砕し、粒子径2mm以下のスポンジ白金を回収することを特徴とするスポンジ白金の回収方法。
(3) Sponge platinum charged in the hydrogen reduction furnace used in the deoxidation process of sponge platinum is divided into several magnetic containers and charged to reduce the influence when the container breaks (1) or ( 2) The method for deoxygenating sponge platinum according to any one of the above. (4) A method for recovering sponge platinum, comprising deoxygenating at a temperature of 800 ° C. or lower and then pulverizing the sponge platinum with an electric mill to recover sponge platinum having a particle diameter of 2 mm or less.
（５）スポンジ白金の脱酸素工程において使用する水素還元炉が、アルゴン置換時にはガスを炉底から吹込み炉頂から抜き出し、水素使用時にはガスを炉頂から吹込み炉底から抜き出す水素還元炉。 (5) A hydrogen reduction furnace in which the hydrogen reduction furnace used in the deoxidation process of the sponge platinum draws gas from the furnace bottom when the argon is replaced, and draws gas from the furnace top when the hydrogen is used.
（７）スポンジ白金の脱酸素工程において使用する水素還元炉のシール部の冷却を水冷却とし、断水等の異常時には炉内ガスが、自動的にアルゴンガスに切り替わる水素還元炉。
（８）スポンジ白金を予め粗粉砕し、真空度10-5Torr以下、処理温度600〜800℃の条件において、スポンジ白金中の酸素を除去し、回収スポンジ白金の王水溶解時溶解速度を向上させるとともに、王水溶解時の未溶解残渣を低減するスポンジ白金の脱酸素方法。
である。
(7) A hydrogen reduction furnace in which the cooling of the seal part of the hydrogen reduction furnace used in the deoxygenation process of sponge platinum is water cooling, and the gas in the furnace is automatically switched to argon gas in the event of an abnormality such as water outage.
(8) Sponge platinum is coarsely pulverized in advance, and oxygen in the sponge platinum is removed under conditions of a vacuum of 10 -5 Torr or less and a processing temperature of 600 to 800 ° C, and the dissolution rate of the recovered sponge platinum during aqua regia dissolution is improved. Sponge platinum deoxygenation method that reduces undissolved residue during aqua regia dissolution.
It is.
本発明によれば、
（１）粒子径2mm以下のスポンジ白金で、王水溶解時に未溶解残渣が少なく、かつ溶解速度の速いスポンジ白金を効率よく安全に生産することが可能となる。
（２）簡易な方法により、スポンジ白金の粉砕が可能となった。
（３）スポンジ白金からの脱酸素を安全に容易に出来る炉を提供できる。
According to the present invention,
(1) Sponge platinum having a particle diameter of 2 mm or less, which has few undissolved residues when dissolved in aqua regia and has a high dissolution rate, can be produced efficiently and safely.
(2) Sponge platinum can be pulverized by a simple method.
(3) A furnace capable of safely and easily deoxidizing from sponge platinum can be provided.
（水素気流中での脱酸素方法）
以下水素気流中において、脱酸素する方法を説明する。
本発明の対象のスポンジ白金は、酸化スポンジ白金を含むもの更には、（NH4）2PtCl6をも含むものも対象とする。
特に、空気の存在下で、乾燥した（NH4）2PtCl6上に乾燥した水素ガスを通じると爆発する危険があるため操業上は、注意を要する。
ただ、下記に記述するように予めスポンジ白金を予熱し、上記アンモニウム塩を分解しておくことにより、爆発の危険が回避される。
そこで、スポンジ白金の脱酸素に使用する水素還元炉は、不活性ガスで空気を追い出し、リークチェックを行いガス漏れのない事を確認してから、水素ガスを流しつつ昇温を開始する。
不活性ガスによる空気の追い出しを確実に実施するためには、空気より重いガスを炉底から通し、炉頂で抜き出すのが効果的である。また、脱酸素時の炉内反応を均一にするには、水素ガスを炉頂から吹込み、炉底から抜き出すことが好ましい。（図６参照）
(Deoxygenation method in a hydrogen stream)
Hereinafter, a method for deoxygenation in a hydrogen stream will be described.
Sponge platinum which is an object of the present invention includes those containing platinum oxide oxide and those containing (NH 4 ) 2 PtCl 6 .
In particular, there is a danger of explosion if dry hydrogen gas is passed over dry (NH 4 ) 2 PtCl 6 in the presence of air, so care must be taken during operation.
However, as described below, the risk of explosion is avoided by preheating sponge platinum in advance and decomposing the ammonium salt.
Therefore, a hydrogen reduction furnace used for deoxygenation of sponge platinum expels air with an inert gas, performs a leak check and confirms that there is no gas leak, and then starts raising the temperature while flowing hydrogen gas.
In order to reliably carry out the purge of air with an inert gas, it is effective to pass a gas heavier than air from the bottom of the furnace and extract it at the top of the furnace. Further, in order to make the reaction in the furnace at the time of deoxygenation uniform, it is preferable to blow hydrogen gas from the top of the furnace and extract it from the bottom of the furnace. (See Figure 6)
上記、不活性ガスによる空気の追い出しだけでも十分であるが、水素還元による脱酸素に供するスポンジ白金に（NH4）2PtCl6が含有されないように、600℃〜800℃、好ましくは750℃〜800℃で大気中あるいは、不活性ガス中において、予熱し、（NH4）2PtCl6を分解しておくことが好ましい。
水素との接触が無ければ、爆発を生じないからである。
また、スポンジ白金を予め粗粉砕し、粒子径20mm以下にしておくことが望ましい。スポンジ白金粒子の表面積を出来るだけ大きくしておくためである。
さらに、水素還元炉では、600〜800℃において、処理する。水素によるスポンジ白金中の脱酸素が効率的に行われる温度だからである。
600℃より低い温度では、脱酸素が効率的に行われず、王水溶解残渣が少ないスポンジ白金が生産できなくなるからである。
また、800℃より高い温度であると焼結が進み、粉砕が良好に出来ないためである。更に王水溶解残渣を減少できなくなる要因となる。
Although the above-described purge of air with an inert gas is sufficient, the sponge platinum used for deoxygenation by hydrogen reduction does not contain (NH 4 ) 2 PtCl 6 , 600 ° C. to 800 ° C., preferably 750 ° C. to It is preferable to preheat at 800 ° C. in the air or in an inert gas to decompose (NH 4 ) 2 PtCl 6 .
This is because if there is no contact with hydrogen, no explosion occurs.
In addition, it is desirable to coarsely pulverize the sponge platinum in advance so that the particle diameter is 20 mm or less. This is to keep the surface area of the sponge platinum particles as large as possible.
Furthermore, in a hydrogen reduction furnace, it processes at 600-800 degreeC. This is because the temperature at which deoxygenation in sponge platinum by hydrogen is efficiently performed.
This is because at temperatures lower than 600 ° C., deoxygenation is not performed efficiently, and sponge platinum with few aqua regia dissolution residues cannot be produced.
Further, if the temperature is higher than 800 ° C., sintering proceeds and pulverization cannot be performed satisfactorily. Furthermore, it becomes a factor that the aqua regia dissolution residue cannot be reduced.
（水素還元炉）
なお、スポンジ白金の脱酸素に使用される水素還元炉は、通常の加熱防止機構、ドラフト機構のほかに、シール部からのガス漏れ防止対策、停電時対策が供せられていることが好ましい。
図７に示すように、シール部の熱変形、シール部からのガス漏洩時の着火を防止するため、加熱ヒーター断熱材末端部からシール部までの距離（２）を100mm以上取り、シール部の冷却は炉心管側に冷却パイプ（３）を溶接、炉蓋側は水冷ジャケット（４）を設置することが好ましい。
(Hydrogen reduction furnace)
In addition, it is preferable that the hydrogen reduction furnace used for deoxidation of sponge platinum is provided with measures for preventing gas leakage from the seal portion and measures for power failure in addition to the normal heating prevention mechanism and draft mechanism.
As shown in FIG. 7, in order to prevent thermal deformation of the seal part and ignition at the time of gas leakage from the seal part, the distance (2) from the end of the heater insulation to the seal part is taken 100 mm or more, For cooling, it is preferable to install a cooling pipe (3) on the furnace tube side and a water cooling jacket (4) on the furnace lid side.
断水時、停電時等の異常時には、炉内ガスが、自動的に不活性ガス（例えば アルゴンガス）に切り替わることが好ましく、図２で示す断水警報装置を設置し、レベル異常時には、炉内吹込みガスバルブを切り替えるようにする（図６参照）。
図６に示すように、空気よりも重いアルゴンガスは、V1→V2→V3を経由して炉底から炉頂に吹き込まれV4（３方バルブ）→V5を経由して室外に放出される。
一方、水素ガスは、V6→V7→V4（３方バルブ）を経由して炉頂から炉底に吹き込まれV8を経由して室外に放出される。
It is preferable that the gas in the furnace automatically switches to an inert gas (for example, argon gas) when there is an abnormality such as when there is a water outage or power outage. The intake gas valve is switched (see FIG. 6).
As shown in FIG. 6, argon gas heavier than air is blown from the furnace bottom to the top of the furnace via V1 → V2 → V3 and released to the outside via V4 (three-way valve) → V5.
On the other hand, hydrogen gas is blown from the top of the furnace to the bottom of the furnace via V6 → V7 → V4 (three-way valve) and released to the outside via V8.
なお、図２の断水警報装置は、透明塩ビ等の材質で作製し、内槽底板孔から水が抜き出されていることを目視で確認できるようにすることが重要である。
スポンジ白金の脱酸素時に、水素還元炉に装入するスポンジ白金は、磁性の容器４〜７個に小分けして装入し、加熱時の容器破損による影響を極力少なくする装入方法を取ることが好ましい。
2 is made of a material such as transparent polyvinyl chloride, and it is important to be able to visually confirm that water has been extracted from the inner tank bottom plate hole.
Sponge platinum to be charged into the hydrogen reduction furnace when deoxidizing the sponge platinum should be charged into 4 to 7 magnetic containers, and the charging method to minimize the effects of container damage during heating. Is preferred.
スポンジ白金のような貴金属を処理する場合は、処理速度を速め、工程内仕掛を減らし、金利負担を極力低減することが重要である。スポンジ白金の脱酸素に使用する水素還元炉は、加熱部と炉心部が分離可能であり、脱酸後の冷却速度を速め、生産性を向上させ得る構造の物を採用することが望ましい。
冷却速度の向上策としては、炉心管を抜き出すタイプと加熱部を開放するタイプがあるが、設置面積も少なく構造も簡単な加熱部を開放するタイプを採用することが好ましい（図８参照）。
なお、開放した後に、扇風機等で強制冷却することがさらに好ましく、炉心管は急激な熱ショックにも耐えうるように、SUS製の炉心管にすることが好ましい。
より具体的には、図８に示すように、水素還元時は上側加熱ヒーターを下ろし（位置（５））、冷却時は上側加熱ヒーターを上げ（位置（６））冷却速度を速める。
When processing precious metals such as sponge platinum, it is important to increase the processing speed, reduce the in-process work, and reduce the interest rate burden as much as possible. It is desirable that the hydrogen reduction furnace used for deoxidation of sponge platinum adopts a structure that can separate the heating part and the core part, increase the cooling rate after deoxidation, and improve the productivity.
As a measure for improving the cooling rate, there are a type in which the core tube is extracted and a type in which the heating unit is opened, but it is preferable to adopt a type in which the heating unit having a small installation area and a simple structure is opened (see FIG. 8).
It is more preferable to forcibly cool with an electric fan or the like after opening, and the core tube is preferably a SUS core tube so that it can withstand a sudden heat shock.
More specifically, as shown in FIG. 8, the upper heater is lowered during hydrogen reduction (position (5)), and the upper heater is raised during cooling (position (6)) to increase the cooling rate.
（真空中での脱酸素方法）
真空処理においては、高真空度である10-5Torr以下、処理温度を600〜800℃の条件において処理を行うと効率よく脱酸素が成される。これにより、スポンジ白金中の酸素が300ppmより少なくなり、王水溶解残渣も少ないスポンジ白金が生産できる。
しかしながら、高真空発生（10-5Torr以下）装置が必要となり、メンテナンス等も考えると、水素気流中において脱酸素することが好ましい。
以下真空中での脱酸素方法について説明する。
図１の真空炉昇温時の温度，真空度経時変化で示すように、PtO2、PtOの分解が600℃付近で起こっている（真空度が低下している）ことから、脱酸素温度は真空中で行うのであれば、600℃以上が好ましい。
スポンジ白金の粉砕に使用する電動ミルは、スポンジ白金粉の静電気による付着を防止するため、オールステンレス製の物が好ましい。
またスポンジ白金の脱酸素温度が800℃以上であると、スポンジ白金の焼結が進み、粉砕が困難になるとともに、電動ミル（市販のビーチブレンダー）で粉砕した場合、ビーチブレンダーのカッター部が破損し製品への混入が懸念され好ましくない。
よって、真空中において脱酸素を行うのであれば、600〜800℃において行うことが望ましい。
(Deoxygenation method in vacuum)
In vacuum processing, deoxidation is efficiently performed when processing is performed under conditions of a high vacuum of 10 −5 Torr or less and a processing temperature of 600 to 800 ° C. Thereby, oxygen in the sponge platinum is less than 300 ppm, and sponge platinum with less aqua regia dissolution residue can be produced.
However, an apparatus for generating a high vacuum (10 −5 Torr or less) is required, and considering maintenance and the like, it is preferable to deoxygenate in a hydrogen stream.
The deoxygenation method in vacuum will be described below.
As shown in the temperature rise of the vacuum furnace in Fig. 1 and the time-dependent change in the degree of vacuum, the decomposition of PtO 2 and PtO occurs at around 600 ° C (the degree of vacuum is reduced). If it is performed in a vacuum, 600 ° C. or higher is preferable.
The electric mill used for pulverizing sponge platinum is preferably made of all stainless steel in order to prevent adhesion of sponge platinum powder due to static electricity.
If the deoxidation temperature of sponge platinum is 800 ° C or higher, sintering of the sponge platinum will progress, making it difficult to grind, and when grinding with an electric mill (commercially available beach blender), the beach blender's cutter will be damaged. However, it is not preferable because it may be mixed into the product.
Therefore, if deoxygenation is performed in a vacuum, it is desirable to perform at 600 to 800 ° C.
（実施例1）
10-5Torr真空下での脱酸素、水素気流中での脱酸素、従来法での脱酸素を行ったスポンジ白金の酸素分析及び王水未溶解残渣確認試験を行った。
表２に酸素分析結果、図３に王水未溶解残渣比較試験結果を示す。
10-5Torr×600℃及び水素気流×800℃で脱酸したスポンジ白金が、スポンジ白金中酸素≦300ppmとなり、かつ王水溶解残渣も少なく出来ることが確認された。
10-5Torr×600℃という条件でも、スポンジ白金中酸素≦300ppmで王水溶解残渣も少ないスポンジ白金が生産できるが、高真空発生装置が必要となり、メンテナンス等も考えると、水素気流中の脱酸素が好ましい。
（実施例２）
(Example 1)
Oxygen analysis of 10-5 Torr vacuum, deoxygenation in a hydrogen stream, deoxygenation by conventional methods, and aqua regia undissolved residue confirmation test were performed.
Table 2 shows the oxygen analysis results, and FIG. 3 shows the aqua regia undissolved residue comparison test results.
It was confirmed that sponge platinum deoxidized at 10 −5 Torr × 600 ° C. and hydrogen stream × 800 ° C. has oxygen in sponge platinum ≦ 300 ppm and can reduce aqua regia dissolution residue.
Even under the condition of 10 -5 Torr × 600 ° C, sponge platinum can produce oxygen in the sponge platinum ≦ 300ppm and few aqua regia dissolved residues, but a high vacuum generator is required and considering maintenance, etc. Oxygen is preferred.
(Example 2)
水素還元炉で脱酸素したスポンジ白金と、他社のスポンジ白金の王水溶解時溶解速度及び王水溶解残渣確認試験を行った。
水素還元により脱酸素したスポンジ白金が、溶解速度も速く、王水溶解残渣量も少ない結果であった。
なお、水素気流中800℃で脱酸素したスポンジ白金は、焼結の進んだB社品に比べ図5に示すごとく焼結が進んでいないため粒子間に適度な空隙を有している。このため、図４で示すように溶解速度が速くなっており、王水溶解残渣も少ないと考えられる。
（実施例３）
Sponge platinum deoxygenated in a hydrogen reduction furnace and other companies' sponge platinum were dissolved in aqua regia and dissolved water residue and aqua regia dissolved residues were confirmed.
Sponge platinum deoxygenated by hydrogen reduction had a high dissolution rate and a small amount of aqua regia dissolution residue.
Sponge platinum deoxygenated at 800 ° C. in a hydrogen stream has moderate voids between the particles because sintering is not progressing as shown in FIG. For this reason, as shown in FIG. 4, the dissolution rate is high, and it is considered that there are few aqua regia dissolution residues.
(Example 3)
熱処理温度を800℃以下に下げたスポンジ白金は、市販のビーチブレンダーによる粉砕が可能となり、下記の比較例1に比べて、粉砕速度を7kg/人・時間まで増加することが出来た。
（比較例１）
800℃より上の高温で熱処理したスポンジ白金は、焼結が進み、2mm以下のスポンジ白金を回収するために、SUSヘラ等による粗粉砕後、乳鉢等による微粉砕を行っており、1.5〜2kg/人・時間程度の粉砕速度であった。
（実施例４）
Sponge platinum whose heat treatment temperature was lowered to 800 ° C. or lower could be pulverized with a commercially available beach blender, and compared with Comparative Example 1 below, the pulverization rate could be increased to 7 kg / person · hour.
(Comparative Example 1)
Sponge platinum heat-treated at a high temperature above 800 ° C is sintered, and in order to collect sponge platinum of 2 mm or less, after coarse pulverization with SUS spatula etc., fine pulverization with mortar etc., 1.5-2kg / The grinding speed was about man / hour.
Example 4
水素還元炉の加熱部を開放し、扇風機で強制冷却した場合と、開放しないで冷却した場合の冷却速度を比較した。
加熱部を開放し、扇風機で強制冷却した場合、800℃から100℃まで約1時間程度で降温でき、1日に2バッチの操業が可能となった。下記の比較例2に比べて効率が良かった。
（比較例２）
加熱部を開放しない場合は、冷却時間が4時間以上かかり、1日1バッチのみの操業となった。
The heating rate of the hydrogen reduction furnace was opened, and the cooling rate was compared between when forced cooling with a fan and when cooling without opening.
When the heating unit was opened and forced cooling was performed with a fan, the temperature could be lowered from 800 ° C to 100 ° C in about 1 hour, and two batch operations per day became possible. The efficiency was better than that of Comparative Example 2 below.
(Comparative Example 2)
When the heating unit was not opened, the cooling time took more than 4 hours, and only one batch per day was operated.
Claims (7)
スポンジ白金中の酸素を除去するに際して、スポンジ白金を予め粒子径2mm以下に粉砕し、水素還元処理を600℃〜800℃にて行い、脱酸素を行うことにより、回収スポンジ白金の王水溶解時溶解速度を向上させるとともに、王水溶解時の未溶解残渣を低減することを特徴とするスポンジ白金の脱酸素方法。
When removing oxygen in sponge platinum, sponge platinum is pulverized to a particle size of 2 mm or less in advance, hydrogen reduction treatment is performed at 600 ° C to 800 ° C, and deoxygenation is performed. A method for deoxygenating sponge platinum, characterized by improving dissolution rate and reducing undissolved residue during dissolution of aqua regia.
請求項１において、スポンジ白金の脱酸素を行う前に、スポンジ白金を予め600℃〜800℃で加熱し、スポンジ白金中のアンモニウム塩を分解した後、水素還元処理を行うことを特徴とするスポンジ白金の脱酸素方法。
2. The sponge according to claim 1, wherein the sponge platinum is heated at 600 ° C. to 800 ° C. in advance to decompose the ammonium salt in the sponge platinum and then subjected to hydrogen reduction treatment before deoxidation of the sponge platinum. Platinum deoxygenation method.
The sponge platinum charged to hydrogen reduction furnace for use in the deoxidation step of the sponge platinum, was charged in portions to several magnetic container, according to claim, characterized in that to reduce the impact at the time of containment failure 1 or The method for deoxygenating sponge platinum according to claim 2 .
800℃以下の温度において脱酸素した後、スポンジ白金を電動ミルにより粉砕し、粒子径2mm以下のスポンジ白金を回収することを特徴とするスポンジ白金の粉砕方法。
A method for pulverizing sponge platinum, comprising deoxygenating at a temperature of 800 ° C. or less and then pulverizing the sponge platinum with an electric mill to collect the sponge platinum having a particle diameter of 2 mm or less.
スポンジ白金の脱酸素工程において使用する水素還元炉が、アルゴン置換時にはガスを炉底から吹込み炉頂から抜き出し、水素使用時にはガスを炉頂から吹込み炉底から抜き出すことを特徴とする水素還元炉。
The hydrogen reduction furnace used in the deoxygenation process of sponge platinum is characterized in that gas is extracted from the bottom of the furnace when argon is replaced, and gas is extracted from the bottom of the furnace when hydrogen is used. Furnace.
Hydrogen reduction is characterized by having a safety device in which the cooling part of the hydrogen reduction furnace used in the deoxidation process of sponge platinum is water-cooled, and the gas in the furnace automatically switches to argon gas in the event of an abnormality such as water outage Furnace.
スポンジ白金を予め粗粉砕し、真空度10-5Torr以下、処理温度600〜800℃の条件において、スポンジ白金中の酸素を除去し、回収スポンジ白金の王水溶解時溶解速度を向上させるとともに、王水溶解時の未溶解残渣を低減することを特徴とするスポンジ白金の脱酸素方法。
Sponge platinum was coarsely pulverized in advance, under conditions of vacuum degree 10 -5 Torr or less, treatment temperature 600 ~ 800 ° C., removing oxygen in sponge platinum, improving the dissolution rate of recovered sponge platinum when dissolved in aqua regia, A method for deoxygenating sponge platinum, characterized by reducing undissolved residues when dissolving aqua regia.
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| JP2004277128A JP4604221B2 (en) | 2004-09-24 | 2004-09-24 | Sponge platinum deoxygenation method, hydrogen reduction furnace used in said method, and sponge platinum pulverization method |
| CNB2005100821818A CN1318620C (en) | 2004-09-24 | 2005-07-04 | Spongy platinum deoxidation method and hydrogen reducing furnace using the method and spongy platinum crushing method |
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| CN110964920A (en) * | 2018-09-28 | 2020-04-07 | 荆门市格林美新材料有限公司 | Method for recovering refined platinum from crude ammonium chloroplatinate |
| CN113340101A (en) * | 2021-06-15 | 2021-09-03 | 莱芜成威电子材料有限公司 | Bell jar furnace protective gas inflation device and bell jar furnace protective gas inflation method |
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| JP2002180140A (en) * | 2000-12-14 | 2002-06-26 | Nippon Mining & Metals Co Ltd | Purification method of platinum sponge |
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