JP4524433B2 - Separation and recovery of noble metal elements for quantitative analysis - Google Patents
Separation and recovery of noble metal elements for quantitative analysis Download PDFInfo
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Description
本発明は、定量分析を目的として貴金属元素含有試料から貴金属元素を分離回収する方法であって、特にＩＣＰ（高周波誘導結合プラズマ）を利用した分析に供するためのサンプル調製に好適な貴金属元素の分離回収方法に関するものである。 The present invention is a method for separating and recovering a noble metal element from a noble metal element-containing sample for the purpose of quantitative analysis, and particularly separation of a noble metal element suitable for sample preparation for analysis using ICP (high frequency inductively coupled plasma). It relates to the collection method.
従来、貴金属元素を定量分析するための分析サンプル調製手法として、ＮiＳ−マット法，乾式試金−灰吹法，Ｔe共沈法などが知られている。 Conventionally, NiS-mat method, dry assay-ash blowing method, Te coprecipitation method, and the like are known as analytical sample preparation methods for quantitative analysis of noble metal elements.
ＮiＳ−マット法は、試料を酸化ニッケル，硫黄，炭酸ソーダ，ホウ砂，珪砂，食塩などとともに加熱溶融して硫化ニッケルボタンを作り、これを塩酸に溶解して濾過することにより白金族元素を分離回収するものである。
乾式試金−灰吹法は、試料を酸化鉛，硫黄，炭酸ソーダ，ホウ砂，珪砂，食塩などとともに加熱溶融して、鉛ボタンとともに貴金属元素を分離回収するものである。
Ｔe共沈法は、試料をアルカリ溶剤，酸化剤とともに加熱溶融して溶融塩とし、これを冷却して得た固形物を塩酸中に溶解させ、共沈剤Ｔeを添加してＳnＣl2等の還元剤で貴金属元素を沈殿させることにより貴金属元素を分離回収するものである。
In the NiS-mat method, a nickel sulfide button is made by heating and melting a sample together with nickel oxide, sulfur, sodium carbonate, borax, silica sand, salt, etc., and this is dissolved in hydrochloric acid and filtered to separate platinum group elements. It is to be collected.
In the dry assay-ash blowing method, a sample is heated and melted with lead oxide, sulfur, sodium carbonate, borax, silica sand, salt, etc., and a precious metal element is separated and recovered together with a lead button.
In the Te coprecipitation method, a sample is heated and melted together with an alkaline solvent and an oxidizing agent to form a molten salt, and the solid obtained by cooling this is dissolved in hydrochloric acid, and the coprecipitation Te is added to add SnCl 2 or the like. The noble metal element is separated and recovered by precipitating the noble metal element with a reducing agent.
ＮiＳ−マット法および乾式試金−灰吹法は、いずれも工程が長く、分析結果が判明するまでに長時間を要するという欠点がある。
Ｔe共沈法は、白金族元素の回収率にバラツキが多く、元素によっては、還元に熟成時間を要し、実際より低めの値を示すという問題がある。また、シリカ系石油化学触媒などの分析においてはゲル状の含水ケイ酸が発生し、共沈後の濾過ができなくなる場合があるという問題もある。
Both the NiS-matt method and the dry assay-ash blowing method have the disadvantage that the process is long and a long time is required until the analysis result is revealed.
The Te coprecipitation method has a large variation in the recovery rate of platinum group elements, and depending on the element, there is a problem that it takes a ripening time for reduction and shows a lower value than actual. Further, in the analysis of silica-based petrochemical catalysts, there is a problem that gel-like hydrous silicic acid is generated and filtration after coprecipitation may not be possible.
本発明は、迅速な分析が可能なＴe共沈法をベースとした新たな貴金属元素の分離回収方法を開発し提供することで、Ｔe共沈法の上記問題の解決を図ることを目的とする。 An object of the present invention is to develop and provide a new method for separating and recovering precious metal elements based on a Te coprecipitation method capable of rapid analysis, and to solve the above problems of the Te coprecipitation method. .
発明者らは種々検討の結果、共沈剤としてＴeとＡsを複合添加したとき、共沈による沈殿物中の白金族元素の回収率が短い熟成時間でも飛躍的に向上し、しかも安定することを見出した。また白金族以外のＡu，Ａgについてもこの共沈法で回収可能であることがわかった。さらに、ゲル状含水ケイ酸の生成による濾過不能を防止するには、溶融塩生成過程においてホウ酸ナトリウムＮa2Ｂ4Ｏ7の添加、および段階的な昇温パターンを採用することが極めて有効であることを見出した。本発明はこれらの知見に基づいて完成したものである。 As a result of various studies, the inventors have found that when Te and As are added together as a coprecipitation agent, the recovery rate of the platinum group elements in the precipitate by coprecipitation can be dramatically improved and stabilized even in a short ripening time. I found. It was also found that Au and Ag other than the platinum group can be recovered by this coprecipitation method. Furthermore, in order to prevent the inability to filter due to the formation of gel-like hydrous silicic acid, it is extremely effective to add sodium borate Na 2 B 4 O 7 and adopt a stepwise heating pattern in the molten salt formation process. I found out. The present invention has been completed based on these findings.
すなわち、上記目的を達成するために、
貴金属含有試料、例えばＰt，Ｐd，Ｒh，Ａu，Ａgの１種以上を含む貴金属含有試料を溶解させた塩酸に、共沈剤としてＴeとＡsを複合添加し、ＳnＣl2といった還元剤を作用させて貴金属元素をＴe，Ａsに随伴させて沈殿させる工程、
得られた沈殿物を濾過して回収する工程、
を有する定量分析を目的とした貴金属元素の分離回収方法、例えば特にＰt，ＰdまたはＲhの定量分析を目的とした貴金属元素の分離回収方法が提供される。
That is, to achieve the above purpose,
Te and As are added together as a coprecipitation agent to hydrochloric acid in which a noble metal-containing sample, for example, a noble metal-containing sample containing one or more of Pt, Pd, Rh, Au, and Ag is dissolved, and a reducing agent such as SnCl 2 is allowed to act. Precipitating a precious metal element with Te and As,
Collecting the resulting precipitate by filtration,
There is provided a method for separating and collecting a noble metal element for the purpose of quantitative analysis having, for example, a method for separating and collecting a noble metal element, particularly for the purpose of quantitative analysis of Pt, Pd or Rh.
また、
[1] 白金族元素を含む貴金属含有試料をＮaＫＣＯ3，Ｎa2Ｏ2などのアルカリ溶剤およびＮa2Ｂ4Ｏ7とともに、昇温過程において１回以上の恒温保持を行いながら段階的に昇温して加熱溶融することにより、貴金属元素の溶融塩を作り、これを冷却して固形物を得る工程、
[2] 前記固形物を塩酸中に完全に溶解させる工程、
[3] 得られた塩酸に共沈剤としてＴeとＡsを複合添加し、ＳnＣl2といった還元剤を作用させて加熱し貴金属元素をＴe，Ａsに随伴させて沈殿させる工程、
[4] 得られた沈殿物を濾過して回収する工程、
を有し、前記工程[1]においては、工程[4]での濾過がゲル状含水ケイ酸の存在により不可能にならないように、Ｎa2Ｂ4Ｏ7の添加量と、段階的昇温過程における恒温保持回数および各恒温保持温度における保持時間をコントロールして含水ケイ酸の生成量を抑制する定量分析を目的とした貴金属元素の分離回収方法が提供される。
Also,
[1] Precious metal-containing sample containing platinum group elements, together with alkaline solvent such as NaKCO 3 and Na 2 O 2 and Na 2 B 4 O 7 And making a noble metal element molten salt by heating and melting, and cooling this to obtain a solid,
[2] A step of completely dissolving the solid in hydrochloric acid,
[3] A step of adding Te and As as a coprecipitation agent to the obtained hydrochloric acid, precipitating the precious metal element with Te and As by heating with a reducing agent such as SnCl 2 ,
[4] A step of filtering and collecting the obtained precipitate,
In the step [1], the amount of Na 2 B 4 O 7 added and the stepwise temperature rise so that the filtration in the step [4] is not impossible due to the presence of the gel-like hydrous silicic acid. There is provided a method for separating and recovering a noble metal element for the purpose of quantitative analysis for suppressing the amount of hydrous silicic acid produced by controlling the number of constant temperature holdings in the process and the holding time at each constant temperature holding temperature.
ここで、「工程[4]での濾過がゲル状含水ケイ酸の存在により不可能にならない」とは、工程[4]で使用する濾過方法（例えば１μｍのメンブレンフィルターを用いた吸引濾過など）において、ゲル状含水ケイ酸が濾過フィルターを目詰まりさせて数十分の時間をかけても沈殿を含む溶液の全量が濾過しきれないような状況、にならないことをいう。
また、「Ｎa2Ｂ4Ｏ7の添加量と、段階的昇温過程における恒温保持回数および各恒温保持温度における保持時間をコントロールして含水ケイ酸の生成量を抑制する」とは、工程[3]における溶液の加熱の際、含水ケイ酸の生成量は、Ｎa2Ｂ4Ｏ7の添加量や、恒温保持回数，各恒温保持温度における保持時間によって変動するので、これらの条件因子を実状に合うように組み合わせて含水ケイ酸の生成量を抑制することを意味する。
Here, “the filtration in step [4] is not impossible due to the presence of the gel-like hydrous silicic acid” means that the filtration method used in step [4] (for example, suction filtration using a 1 μm membrane filter, etc.) The gel-like hydrous silicic acid clogs the filtration filter and does not result in a situation where the entire amount of the solution containing the precipitate cannot be filtered even if it takes several tens of hours.
“The amount of Na 2 B 4 O 7 added, the number of isothermal holdings in the stepwise temperature rising process, and the holding time at each isothermal holding temperature are controlled to suppress the amount of hydrous silicic acid produced” When heating the solution in [3], the amount of hydrous silicic acid varies depending on the amount of Na 2 B 4 O 7 added, the number of constant temperature holding times, and the holding time at each constant temperature holding temperature. This means that the amount of hydrous silicic acid produced is suppressed by combining them so as to meet the requirements.
本発明によれば、貴金属含有試料の化学分析において、ＩＣＰを利用した分析に供するためのサンプルを調製する際、従来のＴe共沈法では回収率にバラツキが生じやすかった白金族元素を高い回収率で安定的に回収することが可能になった。また、シリカ系石油化学触媒などの試料を濾過する際に問題となっていたゲル状の含水ケイ酸による濾過不良も解消された。したがって本発明は、白金族元素を含む貴金属含有試料の分析精度の向上および分析作業性の向上に寄与するものである。 According to the present invention, in the chemical analysis of a noble metal-containing sample, when preparing a sample for analysis using ICP, a high recovery of platinum group elements in which the recovery rate of the conventional Te coprecipitation method is likely to vary is high. It became possible to recover stably at a high rate. Moreover, the filtration defect by the gel-like hydrous silicic acid which was a problem when filtering samples, such as a silica-type petrochemical catalyst, was also eliminated. Therefore, the present invention contributes to improvement in analysis accuracy and analysis workability of a noble metal-containing sample containing a platinum group element.
本発明では、貴金属元素含有試料として、例えば自動車排ガス浄化用触媒，石油化学系触媒，リサイクル原料，鉱石，湿式製錬残渣，スラッジ等を分析対象とすることができる。本発明は、このような貴金属含有試料を完全に溶解させた溶液を用意し、この溶液から貴金属元素を共沈現象によって沈殿させることによって分離回収する。従来、共沈剤としてはＴeが使用されていた。しかしその場合、白金族元素の回収率が低めになるという不具合が生じていた。本発明では共沈剤としてＴeとＡsを複合で添加する。Ｔe＋Ａsの複合添加により白金族元素を共沈させた場合、メカニズムは十分に解明されていないが、その回収率を飛躍的に高め、かつ安定させることが可能となるのである。特にＰt，Ｐd，Ｒhの１種以上を含む場合、その回収率の大きな向上効果が認められる。 In the present invention, as a noble metal element-containing sample, for example, automobile exhaust gas purification catalyst, petrochemical catalyst, recycled raw material, ore, hydrometallurgical residue, sludge and the like can be analyzed. The present invention prepares a solution in which such a noble metal-containing sample is completely dissolved, and separates and collects the noble metal element from the solution by precipitating by a coprecipitation phenomenon. Conventionally, Te has been used as a coprecipitation agent. However, in that case, there has been a problem that the recovery rate of the platinum group element is low. In the present invention, Te and As are added in combination as coprecipitation agents. When the platinum group element is co-precipitated by the combined addition of Te + As, the mechanism has not been fully elucidated, but the recovery rate can be dramatically increased and stabilized. In particular, when one or more of Pt, Pd, and Rh are included, a significant improvement in the recovery rate is recognized.
貴金属含有試料が完全に溶解した溶液にＴe＋Ａsの共沈剤を添加し、これを７０〜８５℃程度に加温した状態で還元剤を加え、その後２０〜６０分程度煮沸するとよい。Ｔe＋Ａsの共沈剤は、例えば溶解操作が簡便に行え、後工程への妨害要素がないＴeＯ2とＡs2Ｏ3に塩酸を加えてこれらを完全に溶解し、これに水を加えて希釈した溶液として添加することができる。還元剤としては例えばＳnＣl2を塩酸によって溶解し、水で希釈したものが使用できる。Ｔe＋Ａsの共沈剤の添加量としては、試料中に含まれる貴金属元素の合計量１〜３０ｍｇに対して、Ｔe：３０〜７０ｍｇ＋Ａs：３０〜７０ｍｇを含む共沈剤を添加すると効果的である。 A coprecipitate of Te + As is added to a solution in which the precious metal-containing sample is completely dissolved, and the reducing agent is added in a state where the coprecipitate is heated to about 70 to 85 ° C., and then boiled for about 20 to 60 minutes. Te + As coprecipitate can be dissolved easily by adding hydrochloric acid to TeO 2 and As 2 O 3 , which do not interfere with subsequent processes, for example, and can be easily dissolved, and diluted with water. It can be added as a solution. As the reducing agent, for example, SnCl 2 dissolved in hydrochloric acid and diluted with water can be used. As the addition amount of the Te + As coprecipitation agent, it is effective to add a coprecipitation agent containing Te: 30-70 mg + As: 30-70 mg with respect to the total amount of noble metal elements contained in the sample of 1-30 mg.
次に、得られた沈殿物を濾過する。メンブレンフィルターに堆積した沈殿物は、塩酸で洗浄し、さらに水で洗浄することが望ましい。沈殿物はフィルターごとビーカーに移し、濾過の器具をビーカー上で硝酸溶液で洗浄する。その後、ビーカーに硝酸溶液と塩酸を加えてフィルターごと液中で加熱し、沈殿物を溶解させる。沈殿物が完全に溶解してからフィルターを取り除き、これをビーカー上で水洗することで前記沈殿物に由来する貴金属元素は完全に回収される。 The resulting precipitate is then filtered. It is desirable to wash the deposit deposited on the membrane filter with hydrochloric acid and then with water. The precipitate is transferred to the beaker together with the filter, and the filtration apparatus is washed with a nitric acid solution on the beaker. Thereafter, a nitric acid solution and hydrochloric acid are added to the beaker, and the whole filter is heated in the solution to dissolve the precipitate. After the precipitate is completely dissolved, the filter is removed, and the precious metal element derived from the precipitate is completely recovered by washing with water in a beaker.
得られた液をシラップ状まで濃縮し、さらに塩酸と水を加えて加熱溶解した後、この液をメスフラスコで定容し、ＩＣＰ発光分析に供すればよい。 The obtained liquid is concentrated to a syrup shape, and further, hydrochloric acid and water are added and dissolved by heating. Then, this liquid is fixed in a volumetric flask and subjected to ICP emission analysis.
ところで、前記の共沈反応に供するための「貴金属含有試料を完全に溶解させた溶液」を得るには、従来例えば、当該試料をアルカリ溶剤とともに加熱溶融して溶融塩とし、これを冷却して得た固形物を塩酸中に溶解させる手法が用いられていた。しかしながら、石油化学系触媒をはじめ、分析対象である貴金属含有試料にはシリカが多量に含まれている場合が多い。このような試料の溶融塩を作り、塩酸溶解した際、含水ケイ酸が生成しやすく、これが共沈後の濾過においてフィルターを目詰まりさせるという事態を招く。この場合、濾過が不可能となる。 By the way, in order to obtain a “solution in which a noble metal-containing sample is completely dissolved” for use in the coprecipitation reaction, conventionally, for example, the sample is heated and melted together with an alkaline solvent to form a molten salt, which is then cooled. A method of dissolving the obtained solid in hydrochloric acid has been used. However, the precious metal-containing samples to be analyzed, including petrochemical catalysts, often contain a large amount of silica. When a molten salt of such a sample is prepared and dissolved in hydrochloric acid, hydrous silicic acid is likely to be generated, which leads to a situation where the filter is clogged during filtration after coprecipitation. In this case, filtration becomes impossible.
そこで本発明では、分析対象試料の溶融塩を作る際に、吸引濾過等の迅速な濾過手段が可能な程度に含水ケイ酸の生成量を抑制させる。その手段としては、i) Ｎa2Ｂ4Ｏ7（ホウ酸ナトリウム）を加えた溶融塩を作り、かつ、ii) 溶融に至るまでの昇温過程で１回以上の恒温保持を行うという段階的な昇温パターンを採る。 Therefore, in the present invention, when the molten salt of the sample to be analyzed is made, the amount of hydrous silicic acid produced is suppressed to such an extent that rapid filtration means such as suction filtration is possible. As a means to do so, i) make Na 2 B 4 O 7 (sodium borate) molten salt, and ii) keep it at least once in the temperature rising process until melting. A warm pattern.
発明者らの検討の結果、共沈時における含水ケイ酸の生成量を低減するには、Ｎa2Ｂ4Ｏ7を適量添加することが有利であり、また、昇温時に恒温保持を行うことが有利であることがわかった。したがって、これらの条件因子を実状に合うように組み合わせることにより含水ケイ酸の生成量を抑制することができる。溶融状態は概ね６００℃以上で実現されるが、例えば、Ｎa2Ｂ4Ｏ7：０.５ｇ，ＲＴ→３００℃×１０分→６００℃×１０分→８００℃×３０分のような昇温パターンが考えられる。
より具体的には、試料１ｇに対して、Ｎa2Ｂ4Ｏ7を０.３〜１ｇ添加し、室温から溶融状態に至るまでの昇温過程において、第１段保持：３００℃±２０℃で５〜２０分保持、第２段保持：６００℃±２０℃で５〜２０分保持の２回の恒温保持を行い、最終的に８００℃±１０℃で２０〜６０分溶融保持するという、段階的昇温過程を含むヒートパターンを採用すると、ＳiＯ2を約８０質量％含む石油化学系触媒を分析する場合でも、共沈後の吸引濾過（１μｍのメンブレンフィルター使用）が十分に可能となる。
As a result of the study by the inventors, it is advantageous to add an appropriate amount of Na 2 B 4 O 7 in order to reduce the amount of hydrous silicic acid produced during coprecipitation, and to maintain a constant temperature when the temperature is raised. Was found to be advantageous. Therefore, the production amount of hydrous silicic acid can be suppressed by combining these condition factors so as to match the actual conditions. The molten state is generally realized at 600 ° C. or higher. For example, Na 2 B 4 O 7 : 0.5 g, RT → 300 ° C. × 10 minutes → 600 ° C. × 10 minutes → 800 ° C. × 30 minutes Possible patterns.
More specifically, 0.3 to 1 g of Na 2 B 4 O 7 is added to 1 g of the sample, and the first stage is maintained in the temperature rising process from room temperature to the molten state: 300 ° C. ± 20 ° C. Hold for 5 to 20 minutes at 2nd stage: 600 ° C. ± 20 ° C. Hold for 5 to 20 minutes, and finally hold at 800 ° C. ± 10 ° C. for 20 to 60 minutes. When a heat pattern including a stepwise temperature rise process is employed, even when a petrochemical catalyst containing about 80% by mass of SiO 2 is analyzed, suction filtration (using a 1 μm membrane filter) after coprecipitation is sufficiently possible. .
溶融塩を作るには、白金族元素を含む貴金属含有試料を、アルカリ溶剤（例えばＮaＫＣＯ3，Ｎa2Ｏ2）、およびＮa2Ｂ4Ｏ7とともに加熱溶融する。上記ヒートパターンを採用する例だと、試料１ｇに対し、ＮaＫＣＯ3：５〜１０ｇ，Ｎa2Ｏ2：５〜１０ｇ，Ｎa2Ｂ4Ｏ7：０.３〜１ｇを添加すると、ＳiＯ2を約８０質量％含む試料で１μｍのメンブレンフィルターを使用した吸引濾過が十分可能となる。 To make a molten salt, a noble metal-containing sample containing a platinum group element is heated and melted together with an alkali solvent (for example, NaKCO 3 , Na 2 O 2 ) and Na 2 B 4 O 7 . In the example of adopting the above heat pattern, when NaKCO 3 : 5 to 10 g, Na 2 O 2 : 5 to 10 g, Na 2 B 4 O 7 : 0.3 to 1 g are added to 1 g of sample, SiO 2 is added. Suction filtration using a 1 μm membrane filter is sufficiently possible with a sample containing about 80% by mass.
〔白金属元素の共沈・回収実験〕
５００ｍＬビーカーに温純水１００ｍＬを入れ、放冷後、下記内容物１５.５ｇを、それが入った坩堝ごと前記ビーカーに移した。
（内容物）試料：１ｇ、ＫＮaＣＯ3：７ｇ、Ｎa2Ｏ2：７ｇ、Ｎa2Ｂ4Ｏ7：０.５ｇ
これに塩酸：水＝１：１の濃度の塩酸５０ｍＬを混合したのち、市販の標準液を用いてＰt：１ｍｇ，Ｐd：１ｍｇ，Ｒh：１ｍｇ相当量を上記ビーカーに添加し、「貴金属含有試料を溶解させた標準溶液」を作った。これを試液Ａと呼ぶ。
以下に述べる共沈剤の種類と同じロット数の試液Ａを用意した。
[Coprecipitation and recovery experiment of white metal elements]
100 mL of warm pure water was put into a 500 mL beaker, and after standing to cool, 15.5 g of the following contents were transferred to the beaker together with the crucible containing it.
(Contents) Sample: 1 g, KNaCO 3 : 7 g, Na 2 O 2 : 7 g, Na 2 B 4 O 7 : 0.5 g
After mixing 50 mL of hydrochloric acid with a concentration of hydrochloric acid: water = 1: 1, the equivalent amount of Pt: 1 mg, Pd: 1 mg, Rh: 1 mg was added to the beaker using a commercially available standard solution. A standard solution in which was dissolved. This is referred to as test solution A.
A test solution A having the same lot number as the type of coprecipitate described below was prepared.
一方、共沈剤としては、Ｔe濃度が４ｇ／Ｌ，１０ｇ／Ｌ，２０ｇ／Ｌの塩酸（以上、比較剤）、およびＴe：１０ｇ／Ｌ＋Ａs：１０ｇ／Ｌを含む塩酸（発明対象剤）を用意した。Ｔeは試薬のＴeＯ2を、Ａsは試薬のＡs2Ｏ3を用い、それぞれ塩酸に溶解させた。
また、還元剤として、ＳnＣl2を２８０ｇ／Ｌ溶解させた塩酸を用意した。
On the other hand, as a coprecipitation agent, hydrochloric acid containing Te concentrations of 4 g / L, 10 g / L, and 20 g / L (above, a comparative agent) and hydrochloric acid containing Te: 10 g / L + As: 10 g / L (invention target) Prepared. Te was dissolved in hydrochloric acid using TeO 2 as a reagent and As 2 O 3 as As.
As a reducing agent, hydrochloric acid in which SnCl 2 was dissolved at 280 g / L was prepared.
坩堝を洗い取り出した各試液Ａに、上記各共沈剤溶液５ｍＬを添加し、さらに水を加えることで、それぞれ液量を３３０ｍＬに調整した。これを約８０℃に加温した状態で上記還元剤（ＳnＣl2溶液）を２０ｍＬ添加し、その後、煮沸を３０分間行った。煮沸時の塩酸濃度は約１.４Ｎである。 The respective coprecipitate solutions 5 mL were added to each sample solution A from which the crucible was washed out, and water was further added to adjust the liquid volume to 330 mL. 20 mL of the above reducing agent (SnCl 2 solution) was added in a state of being heated to about 80 ° C., followed by boiling for 30 minutes. The concentration of hydrochloric acid during boiling is about 1.4N.
煮沸後の液を室温まで放冷したのち、１μｍのメンブレンフィルターを用いて吸引濾過した。フィルターに貯まった沈殿物を塩酸：水＝１：５の濃度の塩酸１０ｍＬで３回洗浄し、さらに水で数回洗浄した。洗浄後の沈殿物をフィルターごとビーカーに移し、濾過の器具をビーカー上で水洗し、硝酸５ｍＬを使用してさらに洗浄した。ビーカー縁から硝酸５ｍＬと塩酸１０ｍＬを加えた後、加熱し、沈殿物を溶解させた。沈殿物が完全に分解したのを確認後、フィルターを取り出し、ビーカー上で水洗した。このようにして沈殿物が完全に回収された液（沈殿物が全量溶解している液）を加熱することでシラップ状まで濃縮し（脱硝酸）、これに塩酸１０ｍＬと少量の水を加えて加熱溶解し、得られた液を１００ｍＬメスフラスコに定容した。 The solution after boiling was allowed to cool to room temperature, and then filtered with suction using a 1 μm membrane filter. The precipitate stored in the filter was washed three times with 10 mL of hydrochloric acid having a concentration of hydrochloric acid: water = 1: 5, and further washed several times with water. The washed precipitate was transferred to the beaker together with the filter, and the filtration device was washed with water on the beaker and further washed with 5 mL of nitric acid. Nitric acid (5 mL) and hydrochloric acid (10 mL) were added from the beaker edge and then heated to dissolve the precipitate. After confirming that the precipitate was completely decomposed, the filter was taken out and washed in a beaker. The liquid in which the precipitate was completely recovered in this way (the liquid in which the entire amount of the precipitate was dissolved) was heated to concentrate to syrup (denitrification), and 10 mL of hydrochloric acid and a small amount of water were added thereto. The resulting solution was heated and dissolved, and the volume of the resulting solution was adjusted to a 100 mL volumetric flask.
これをＩＣＰ発光分析装置（バリアン社製、VISTA）で測定し、貴金属元素を分析した。各元素とも５秒５回の積分時間とした。例えばＰt１０.０ｍｇ添加の試液で測定結果が９.９４ｍｇであれば、Ｐtの回収率は９９.４％となる。なお、計算上、回収率が１００％をわずかに超える場合もあるが、この場合ほぼ１００％とみなしてよい。
結果を表１に示す。
This was measured with an ICP emission analyzer (manufactured by Varian, VISTA) to analyze noble metal elements. The integration time was 5 seconds 5 times for each element. For example, if the measurement result is 9.94 mg with 10.0 mg of Pt added, the recovery rate of Pt is 99.4%. Note that, in the calculation, the recovery rate may slightly exceed 100%, but in this case, it may be regarded as almost 100%.
The results are shown in Table 1.
表１からわかるように、共沈剤としてＴeとＡsを複合添加することによって、Ｔe単独使用の場合よりも貴金属元素回収率は大幅に向上した。また、表１には示していないが、ＴeとＡsの複合添加により、回収率のバラツキも非常に小さくなることが確認された。本発明法により白金族元素の分析精度は大きく向上した。 As can be seen from Table 1, the combined recovery of Te and As as a coprecipitate significantly improved the precious metal element recovery rate compared to the case of using Te alone. Further, although not shown in Table 1, it was confirmed that the dispersion of the recovery rate was very small by the combined addition of Te and As. The analytical accuracy of platinum group elements has been greatly improved by the method of the present invention.
〔Ａu，Ａgの共沈・回収実験〕
市販の標準液を用いてＡu：２０ｍｇ，Ａg：２ｍｇ相当量をビーカーに添加した以外は、実施例１と同じ方法で「貴金属含有試料を溶解させた塩酸溶液」に相当する液（貴金属含有量は既知）を作った。これを試液Ｂと呼ぶ。
共沈剤はＴe：１０ｇ／Ｌ＋Ａs：１０ｇ／Ｌを含む塩酸（発明対象剤）を用意した。還元剤は実施例１と同じである。
実施例１と同じ方法で共沈および回収実験を行った。
その結果、回収率はＡu：９７.８％、Ａg：９７.１％であった。
Ａu，Ａgについては、白金族元素に比べて回収率は低いものの、回収率のバラツキは小さいため、ＴeとＡsの複合添加による共沈法を用いて白金族元素と同様に分析が可能であることが確かめられた。
[Co-precipitation and recovery experiment of Au and Ag]
A solution (noble metal content) corresponding to “a hydrochloric acid solution in which a noble metal-containing sample is dissolved” by the same method as in Example 1 except that a commercially available standard solution is used to add Au: 20 mg, Ag: 2 mg equivalent to the beaker. Made known). This is called reagent solution B.
As a coprecipitation agent, hydrochloric acid containing Te: 10 g / L + As: 10 g / L (invention target) was prepared. The reducing agent is the same as in Example 1.
Coprecipitation and recovery experiments were performed in the same manner as in Example 1.
As a result, the recoveries were Au: 97.8% and Ag: 97.1%.
As for Au and Ag, although the recovery rate is lower than that of the platinum group element, since the variation in the recovery rate is small, it can be analyzed in the same manner as the platinum group element using the coprecipitation method by the combined addition of Te and As. It was confirmed.
〔白金族元素とＡu，Ａgの同時共沈・回収実験〕
市販の標準液を用いてＰt：１ｍｇ，Ｐd：１ｍｇ，Ｒh：１ｍｇ相当量およびＡu：２０ｍｇ，Ａg：２ｍｇ相当量をビーカーに添加した以外は、実施例１と同じ方法で「貴金属含有試料を溶解させた塩酸溶液」に相当する液（貴金属含有量は既知）を作った。これを試液Ｃと呼ぶ。
共沈剤は、実施例１と同様に４種類（比較剤１種，発明対象剤３種）を用意した。還元剤も実施例１と同じである。
実施例１と同じ方法で共沈および回収実験を行った。
結果を表２に示す。
[Simultaneous coprecipitation and recovery experiment of platinum group elements and Au, Ag]
Except that Pt: 1 mg, Pd: 1 mg, Rh: 1 mg equivalent and Au: 20 mg, Ag: 2 mg equivalent were added to the beaker using a commercially available standard solution, the same method as in Example 1 was used. A solution corresponding to the “dissolved hydrochloric acid solution” was prepared (the noble metal content was known). This is referred to as test solution C.
Four types of coprecipitation agents (comparative agent 1 type, invention target agent 3 types) were prepared in the same manner as in Example 1. The reducing agent is the same as in Example 1.
Coprecipitation and recovery experiments were performed in the same manner as in Example 1.
The results are shown in Table 2.
表２からわかるように、共沈剤としてＴeとＡsを複合添加することによって、Ｔe単独使用の場合よりも元素間の回収率のバラツキが減少し、各貴金属元素ともほぼ１００％に近い回収率が達成できた。本発明法により、白金族元素とＡu，Ａgを含有する試料において、これらの元素の分析精度を同時に大きく向上できることが確認された。 As can be seen from Table 2, the combined addition of Te and As as coprecipitates reduces the variation in the recovery rate between elements compared to the case of using Te alone, and the recovery rate is almost 100% for each noble metal element. Was achieved. According to the method of the present invention, it was confirmed that the analysis accuracy of these elements can be greatly improved at the same time in a sample containing platinum group elements and Au and Ag.
〔共沈後の濾過性試験〕
試料としてＳiＯ2を約８０質量％含む石油化学系触媒を用い、ＫＮaＣＯ3，Ｎa2Ｏ2、あるいはさらにＮa2Ｂ4Ｏ7とともに５０ｍＬのアルミナ坩堝を用いて加熱溶融し、溶融塩を作った。その際、Ｎa2Ｂ4Ｏ7の添加量および昇温時のヒートパターンを種々変えた。溶融保持はいずれも８００℃×３０分とした。得られた溶融塩を冷却（放冷）して、固形物とし、これを塩酸に完全に溶解した。この「貴金属含有試料を溶解させた溶液」にＴe＋Ａsの共沈剤およびＳnＣl2の還元剤を添加して貴金属元素を共沈させ、沈殿を含む溶液について１μｍのメンブレンフィルターを用いた吸引濾過を試みた。
[Filterability test after coprecipitation]
Using a petrochemical catalyst containing about 80% by mass of SiO 2 as a sample, it was heated and melted with KNaCO 3 , Na 2 O 2 , or Na 2 B 4 O 7 in a 50 mL alumina crucible to make a molten salt. . At that time, the addition amount of Na 2 B 4 O 7 and the heat pattern at the time of temperature increase were variously changed. All the melt holdings were performed at 800 ° C. for 30 minutes. The obtained molten salt was cooled (cooled) and turned into a solid, which was completely dissolved in hydrochloric acid. A Te + As coprecipitation agent and a SnCl 2 reducing agent are added to the “solution in which the precious metal-containing sample is dissolved” to coprecipitate the precious metal element, and the solution containing the precipitate is subjected to suction filtration using a 1 μm membrane filter. It was.
共沈剤および還元剤は実施例１で用いたものと同じである。坩堝の内容物を塩酸に溶かす工程から「貴金属含有試料を溶解させた溶液」を処理して濾過する工程までの手順は、標準液によるＰt等の添加を行わない点を除き、実施例１と同様とした。
実験結果を表３に示す。
The coprecipitation agent and the reducing agent are the same as those used in Example 1. The procedure from the step of dissolving the contents of the crucible in hydrochloric acid to the step of processing and filtering the “solution in which the noble metal-containing sample is dissolved” is the same as in Example 1 except that Pt or the like is not added by the standard solution. Same as above.
The experimental results are shown in Table 3.
表３からわかるように、６００℃×２０分の１段階の恒温保持を行う場合、Ｎa2Ｂ4Ｏ7の添加量が５ｇ（試料１ｇに対する値、以下同様）で濾過が可能となった。これに対し、３００℃×１０分→６００℃×１０分の２段階の恒温保持を行うと、Ｎa2Ｂ4Ｏ7の添加量がわずか０.５ｇでも濾過が可能となった。すなわち、Ｎa2Ｂ4Ｏ7の添加量を多くするように、あるいは恒温保持の回数を増やし且つ１回の保持時間をあまり長くしないように、Ｎa2Ｂ4Ｏ7の添加量と、段階的昇温過程における恒温保持回数および各恒温保持温度における保持時間をコントロールすることで、濾過時の目詰まりを防止できることがわかった。
なお、フィルターの目詰まりを起こしたゲル状物質を分析したところ、ゲル状含水ケイ酸であることが確認された。
As can be seen from Table 3, in the case where the constant temperature holding at 600 ° C. × 1/20 was performed, filtration was possible with an addition amount of Na 2 B 4 O 7 of 5 g (value for 1 g of sample, the same applies hereinafter). On the other hand, when two-stage constant temperature holding at 300 ° C. × 10 minutes → 600 ° C. × 10 minutes was performed, filtration was possible even when the addition amount of Na 2 B 4 O 7 was only 0.5 g. That, Na 2 B 4 so as to increase the amount of O 7, or increasing the number of isothermal holding and once the holding time to not too long, the amount of Na 2 B 4 O 7, stepwise It was found that clogging during filtration can be prevented by controlling the number of constant temperature holdings in the temperature raising process and the holding time at each constant temperature holding temperature.
In addition, when the gel-like substance which caused clogging of the filter was analyzed, it was confirmed that it was gel-like hydrous silicic acid.
Claims (7)
得られた沈殿物を濾過して回収する工程、
を有する定量分析を目的とした貴金属元素の分離回収方法。 A step of adding Te and As as co-precipitating agents to hydrochloric acid in which a precious metal-containing sample is dissolved and precipitating the precious metal elements accompanying Te and As by acting a reducing agent;
Collecting the resulting precipitate by filtration,
A method for separating and recovering precious metal elements for the purpose of quantitative analysis.
得られた沈殿物を濾過して回収する工程、
を有するＰt，ＰdまたはＲhの定量分析を目的とした貴金属元素の分離回収方法。 Te and As are added as a coprecipitation agent to hydrochloric acid in which a noble metal-containing sample containing at least one of Pt, Pd, and Rh is dissolved, and a reducing agent is allowed to act to precipitate the noble metal element accompanying Te and As. The process of
Collecting the resulting precipitate by filtration,
A method for separating and recovering noble metal elements for the purpose of quantitative analysis of Pt, Pd or Rh.
得られた沈殿物を濾過して回収する工程、
を有するＰt，Ｐd，Ｒh，ＡuまたはＡgの定量分析を目的とした貴金属元素の分離回収方法。 Te and As are co-precipitated in hydrochloric acid in which a noble metal-containing sample containing at least one of Pt, Pd, and Rh and at least one of Au and Ag is dissolved, and a reducing agent is allowed to act on the noble metal element. A step of precipitating with Te and As,
Collecting the resulting precipitate by filtration,
A method for separating and recovering noble metal elements for the purpose of quantitative analysis of Pt, Pd, Rh, Au, or Ag having the above.
[2] 前記固形物を塩酸中に完全に溶解させる工程、
[3] 得られた塩酸に共沈剤としてＴeとＡsを複合添加し、還元剤を作用させて貴金属元素をＴe，Ａsに随伴させて沈殿させる工程、
[4] 得られた沈殿物を濾過して回収する工程、
を有する定量分析を目的とした貴金属元素の分離回収方法。 [1] A step in which a noble metal-containing sample is heated and melted together with an alkali solvent to form a molten salt of a noble metal element and cooled to obtain a solid,
[2] A step of completely dissolving the solid in hydrochloric acid,
[3] A step of adding Te and As as co-precipitating agents to the obtained hydrochloric acid and allowing a precipitating metal element to accompany Te and As by causing a reducing agent to act;
[4] A step of filtering and collecting the obtained precipitate,
A method for separating and recovering precious metal elements for the purpose of quantitative analysis.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06148390A (en) * | 1992-11-04 | 1994-05-27 | Sumitomo Metal Mining Co Ltd | Separating method for fission product noble metal |
| JPH08217460A (en) * | 1995-02-13 | 1996-08-27 | Sumitomo Metal Mining Co Ltd | Method for collectively separating and analyzing ruthenium, osmium and/or iridium |
| JPH08239721A (en) * | 1995-02-28 | 1996-09-17 | Sumitomo Metal Mining Co Ltd | Separation of platinum-group element and low-basicity impurity |
| JP2001207223A (en) * | 2000-01-25 | 2001-07-31 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from copper electrolytic slime |
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| JPH06148390A (en) * | 1992-11-04 | 1994-05-27 | Sumitomo Metal Mining Co Ltd | Separating method for fission product noble metal |
| JPH08217460A (en) * | 1995-02-13 | 1996-08-27 | Sumitomo Metal Mining Co Ltd | Method for collectively separating and analyzing ruthenium, osmium and/or iridium |
| JPH08239721A (en) * | 1995-02-28 | 1996-09-17 | Sumitomo Metal Mining Co Ltd | Separation of platinum-group element and low-basicity impurity |
| JP2001207223A (en) * | 2000-01-25 | 2001-07-31 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from copper electrolytic slime |
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