JP4483441B2 - Method for purifying rhodium from liquid containing high iridium and ruthenium - Google Patents
Method for purifying rhodium from liquid containing high iridium and ruthenium Download PDFInfo
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- JP4483441B2 JP4483441B2 JP2004205549A JP2004205549A JP4483441B2 JP 4483441 B2 JP4483441 B2 JP 4483441B2 JP 2004205549 A JP2004205549 A JP 2004205549A JP 2004205549 A JP2004205549 A JP 2004205549A JP 4483441 B2 JP4483441 B2 JP 4483441B2
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- 239000010948 rhodium Substances 0.000 title claims description 60
- 229910052703 rhodium Inorganic materials 0.000 title claims description 59
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims description 59
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 38
- 229910052741 iridium Inorganic materials 0.000 title claims description 36
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 23
- 239000007788 liquid Substances 0.000 title claims description 11
- 239000000243 solution Substances 0.000 claims description 31
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 30
- 238000000638 solvent extraction Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 235000010288 sodium nitrite Nutrition 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、白金族元素の一つであるロジウムの精製方法に関し、詳しくは、非鉄金属精錬工程や白金族含有物のリサイクル工程で発生する白金族含有酸性溶液から、溶媒抽出処理により高品位のロジウム溶液を得る方法に関する。 The present invention relates to a method for purifying rhodium, which is one of the platinum group elements, and more specifically, from a platinum group-containing acidic solution generated in a non-ferrous metal refining process or a recycling process of platinum group-containing substances, by high-quality solvent extraction. The present invention relates to a method for obtaining a rhodium solution.
従来、ロジウム、イリジウム及びルテニウムを含有する酸性溶液からロジウムを回収する方法として、トリブチルフォスフェイト等の有機溶媒を用いた溶媒抽出法が知られている（例えば、特開平８−２０９２５７号公報）。このような溶媒抽出法は、沈澱分離法と比較して非常に高い不純物分離効果が得られることから、工業的にも広く利用されている。 Conventionally, a solvent extraction method using an organic solvent such as tributyl phosphate is known as a method for recovering rhodium from an acidic solution containing rhodium, iridium and ruthenium (for example, JP-A-8-209257). Such a solvent extraction method is widely used industrially because a very high impurity separation effect is obtained as compared with the precipitation separation method.
しかし、白金及びイリジウムの溶媒抽出による分離は比較的容易に行うことができるものの、母液中のルテニウム濃度が高くなると、有機溶媒へのルテニウムの蓄積が起こるため、分相性の悪化を引き起こし、処理の継続が難しくなるという問題があった。また、イリジウムの溶媒抽出による分離は、イリジウム濃度が高くなるに従って抽残液中に残留するイリジウム濃度が高くなり、抽出処理を何回も繰り返さなければならないため、製品化日数や製造コストを増加させていた。 However, although the separation of platinum and iridium by solvent extraction can be performed relatively easily, if the ruthenium concentration in the mother liquor increases, ruthenium accumulates in the organic solvent. There was a problem that it was difficult to continue. In addition, the separation of iridium by solvent extraction increases the concentration of iridium remaining in the extraction liquid as the iridium concentration increases, and the extraction process must be repeated many times. It was.
溶媒抽出法以外のロジウムの精製方法として、ロジウムを含有する水溶液に亜硝酸ナトリウムを添加して、１００ｇ／ｌ以上のナトリウムイオンの存在下にロジウム化合物と反応させ、ロジウムをヘキサニトロロジウム酸ナトリウムとして結晶化させて分離した後、このヘキサニトロロジウム酸ナトリウムの結晶を水に溶解し、水溶性ナトリウム塩を添加することにより、再度ロジウムをヘキサニトロロジウム酸ナトリウムとして選択的に結晶化させる方法が提案されている（特開２００２−２５５５６３号公報）。 As a rhodium purification method other than the solvent extraction method, sodium nitrite is added to an aqueous solution containing rhodium and reacted with a rhodium compound in the presence of 100 g / l or more of sodium ions to convert rhodium into sodium hexanitrorhodate. After separation by crystallization, a method for selectively crystallizing rhodium as sodium hexanitrorhodate by dissolving the sodium hexanitrorhodate crystals in water and adding a water-soluble sodium salt is proposed. (JP 2002-255563 A).
しかし、この方法の場合、通常１回の結晶化では十分な純度のロジウムの結晶が得られないため再結晶化が必要であるうえ、ヘキサニトロロジウム酸アンモニウムは高温でも水に溶解しにくいため操作が面倒であった。また、ロジウムを含む原液が多様化している現状において、特にイリジウムやルテニウムの含有量が高い原液では、高純度のロジウムを回収することが難しい場合があった。 However, in this method, it is necessary to recrystallize since rhodium crystals with sufficient purity cannot be obtained by one crystallization, and ammonium hexanitrorhodate is difficult to dissolve in water even at high temperatures. Was troublesome. In addition, in the present situation where stock solutions containing rhodium are diversified, it is sometimes difficult to recover high-purity rhodium particularly in a stock solution having a high content of iridium or ruthenium.
このような現状から、ロジウムに対するイリジウム及びルテニウムの濃度比が比較的高い溶液から、簡単な手段により且つ低コストで、高品位のロジウム溶液を回収する方法が望まれていた。 Under such circumstances, there has been a demand for a method for recovering a high-quality rhodium solution from a solution having a relatively high concentration ratio of iridium and ruthenium to rhodium by a simple means and at a low cost.
本発明は、上記した従来技術の問題点に鑑み、ロジウムに対するイリジウム及びルテニウムの濃度比が比較的高い原料溶液であっても、溶媒抽出を用いた簡単な手段により且つ低コストで、高品位のロジウム溶液を回収する方法を提供することを目的とする。 In view of the above-mentioned problems of the prior art, the present invention provides a high-quality, low-cost, simple method using solvent extraction, even for a raw material solution having a relatively high concentration ratio of iridium and ruthenium to rhodium. It is an object to provide a method for recovering a rhodium solution.
本発明者らは、上記目的を達成するために鋭意研究を重ねた結果、ロジウムを含む原料溶液からイリジウムやルテニウムなど他の白金族元素の粗分離を行った後に溶媒抽出を行うこと、並びに、溶媒抽出前の粗分離の方法として、原料溶液に亜硝酸ナトリウムを添加し且つ液中の塩濃度を上昇させることにより、ロジウムをヘキサニトロロジウム酸ナトリウムの結晶として沈澱させる方法が有効であることを見出した。 As a result of intensive research to achieve the above object, the present inventors have conducted solvent extraction after roughly separating other platinum group elements such as iridium and ruthenium from a raw material solution containing rhodium, and As a rough separation method before solvent extraction, it is effective to add sodium nitrite to the raw material solution and increase the salt concentration in the solution to precipitate rhodium as sodium hexanitrorhodate crystals. I found it.
本発明は、かかる知見に基づいてなされたものであり、ロジウム、イリジウム及びルテニウムを含有する酸性溶液に亜硝酸ナトリウムを添加して中和し、同時に若しくはその前又は後の少なくともいずれかで塩濃度を上昇させることにより、ロジウムをヘキサニトロロジウム酸ナトリウムの結晶として沈澱させた後、固液分離によりロジウムをイリジウム及びルテニウムと粗分離し、得られたヘキサニトロロジウム酸ナトリウムの沈澱を塩酸溶解し、この溶解液中に残留したイリジウム及びルテニウムを溶媒抽出により除去することを特徴とする。 The present invention has been made on the basis of such knowledge, neutralized by adding sodium nitrite to an acidic solution containing rhodium, iridium and ruthenium, and at the same time or at least either before or after the salt concentration , Rhodium was precipitated as sodium hexanitrorhodate crystals, then rhodium was roughly separated from iridium and ruthenium by solid-liquid separation, and the resulting sodium hexanitrorhodate precipitate was dissolved in hydrochloric acid. It is characterized in that iridium and ruthenium remaining in the solution are removed by solvent extraction.
上記本発明のロジウム精製方法においては、前記亜硝酸ナトリウムの添加により、酸性溶液のｐＨを５〜７に中和することが好ましい。また、上記本発明のロジウム精製方法においては、前記溶媒抽出に用いる有機溶媒としてトリブチルフォスフェイト系有機溶媒を使用することが好ましい。 In the rhodium purification method of the present invention, it is preferable to neutralize the pH of the acidic solution to 5 to 7 by adding the sodium nitrite. In the rhodium purification method of the present invention, it is preferable to use a tributyl phosphate organic solvent as the organic solvent used for the solvent extraction .
本発明によれば、イリジウムやルテニウムなどのロジウム以外の白金族元素濃度が高い原料溶液から、先ずイリジウム及びルテニウムを簡単に粗分離することができ、小量残留したイリジウム及びルテニウムは更に溶媒抽出にて除去することができる。従って、原料溶液中に含まれるイリジウム及びルテニウムの濃度に左右されることなく、例えばイリジウム及びルテニウム濃度がロジウム濃度よりも高い場合であっても、粗分離後に更に特別な操作をすることなく、溶媒抽出だけで高品位のロジウム溶液を得ることができる。 According to the present invention, first, iridium and ruthenium can be easily roughly separated from a raw material solution having a high platinum group element concentration other than rhodium such as iridium and ruthenium. Can be removed. Therefore, without depending on the concentrations of iridium and ruthenium contained in the raw material solution, for example, even when the iridium and ruthenium concentrations are higher than the rhodium concentration, the solvent is not subjected to further special operation after the rough separation. A high-quality rhodium solution can be obtained only by extraction.
本発明のロジウム精製方法では、前処理としての簡単な粗分離と溶媒抽出とを組み合わせることにより、白金族元素の中でも特にロジウム、イリジウム及びルテニウムを含有する酸性溶液から、高品位のロジウム溶液を得るものである。特に簡単な前処理により大部分のイリジウム及びルテニウムを粗分離することが可能であり、これによって特にルテニウムの溶媒中への蓄積を充分に抑制することができるので、その後の溶媒抽出により不純物（特にイリジウム）を分離して高品位のロジウム溶液を得ることができる。 In the rhodium purification method of the present invention, a high-quality rhodium solution is obtained from an acidic solution containing rhodium, iridium and ruthenium, among other platinum group elements, by combining simple rough separation and solvent extraction as pretreatment. Is. In particular, a large amount of iridium and ruthenium can be roughly separated by a simple pretreatment, and in particular, accumulation of ruthenium in the solvent can be sufficiently suppressed. Iridium) can be separated to obtain a high-quality rhodium solution.
即ち、酸性溶液中でヘキサクロロロジウム酸イオンとなっているロジウムは、亜硝酸ナトリウムを添加して中和することによりヘキサニトロロジウム酸ナトリウムの錯体となり、更に塩濃度を上昇させることによりヘキサニトロロジウム酸ナトリウムの結晶として沈澱する。その際、イリジウム及びルテニウムも、それぞれヘキサニトロイリジウム酸ナトリウム及びヘキサニトロルテニウム酸ナトリウムとなるが、塩濃度を上昇させたときロジウムの溶解度が比較的低く、イリジウム及びルテニウムの溶解度が高いため、これらの溶解度差により相互分離が可能である。 That is, rhodium, which is hexachlororhodate ion in an acidic solution, becomes a complex of sodium hexanitrorhodate by adding sodium nitrite to neutralize it, and by further increasing the salt concentration, hexanitrorhodate. Precipitate as sodium crystals. At that time, iridium and ruthenium also become sodium hexanitroiridate and sodium hexanitroruthenate, respectively, but when the salt concentration is increased, the solubility of rhodium is relatively low and the solubility of iridium and ruthenium is high. Mutual separation is possible due to the difference in solubility.
上記前処理において、亜硝酸ナトリウムの添加は８０〜９０℃程度の高温で行い、亜硝酸ナトリウムによる中和の目標ｐＨは５〜７とすることが好ましい。また、この亜硝酸ナトリウムの添加と同時に、若しくは、その前又は後に、あるいはこれらの２回以上で、液中の塩濃度を上昇させる。液中の塩濃度は９０ｇ／ｌ以上に上昇させることが好ましく、塩濃度を上げる手段としては、液を濃縮するか、又は食塩などのナトリウム塩を添加することが望ましい。 In the pretreatment, sodium nitrite is preferably added at a high temperature of about 80 to 90 ° C., and the target pH for neutralization with sodium nitrite is preferably 5 to 7. Further, the salt concentration in the liquid is increased simultaneously with the addition of sodium nitrite, before or after the addition, or two or more times thereof. The salt concentration in the liquid is preferably increased to 90 g / l or more. As a means for increasing the salt concentration, it is desirable to concentrate the liquid or add a sodium salt such as sodium chloride.
尚、上記前処理における反応の終点は、一般的には反応中の母液の色が薄黄色となれば終点とするが、不純物の濃度により母液の色は多様に変化するため、分析により残留するロジウム濃度を判断して終点を定めることが望ましい。 The end point of the reaction in the pretreatment is generally the end point when the color of the mother liquor during the reaction becomes light yellow, but the color of the mother liquor changes variously depending on the concentration of impurities, and therefore remains after analysis. It is desirable to determine the end point by judging the rhodium concentration.
反応の終了後、ヘキサニトロロジウム酸ナトリウムの結晶沈澱と、ヘキサニトロイリジウム酸ナトリウム及びヘキサニトロルテニウム酸ナトリウムの溶液とに、固液分離する。得られたヘキサニトロロジウム酸ナトリウム(ＮＨ４)３［Ｒｈ(ＮＯ２)６］の結晶は、水に難溶性であるが、塩酸には簡単に溶解する。従って、この結晶沈澱を塩酸にて溶解し、再度ヘキサクロロロジウム酸の溶液とした後、溶媒抽出により不純物のイリジウム及びルテニウムを分離して、高品位のロジウム溶液を回収することができる。溶媒抽出に用いる溶媒としては、トリブチルフォスフェイト系有機溶媒が好ましい。 After completion of the reaction, solid-liquid separation is carried out into a crystal precipitate of sodium hexanitrorhodate and a solution of sodium hexanitroiridate and sodium hexanitroruthenate. The obtained crystals of sodium hexanitrorhodate (NH 4 ) 3 [Rh (NO 2 ) 6 ] are sparingly soluble in water but easily dissolved in hydrochloric acid. Accordingly, this crystal precipitate is dissolved in hydrochloric acid to form a hexachlororhodate solution again, and then the impurities iridium and ruthenium are separated by solvent extraction, whereby a high-quality rhodium solution can be recovered. As a solvent used for solvent extraction, a tributyl phosphate organic solvent is preferable.
これに対して、溶媒抽出処理前の前処理を行わず、イリジウム及びルテニウム濃度が高い溶液、特にルテニウム濃度が高い溶液を溶媒抽出する操作においては、ルテニウムが溶媒中に一部抽出されるものの、逆抽出時に水相へ遊離しないため、有機相の比重が高くなり、水相との相分離が悪化してしまう。また、ルテニウムの抽出により有機相が黒く着色するため、目視で有機相と水相との界面を判断することが難しくなり、総じて溶媒抽出処理が困難である。 On the other hand, in the operation of solvent extraction of a solution having a high iridium and ruthenium concentration, particularly a solution having a high ruthenium concentration without performing a pretreatment before the solvent extraction treatment, although ruthenium is partially extracted in the solvent, Since it is not liberated to the aqueous phase during back extraction, the specific gravity of the organic phase increases, and phase separation from the aqueous phase deteriorates. Moreover, since the organic phase is colored black by the extraction of ruthenium, it is difficult to visually determine the interface between the organic phase and the aqueous phase, and the solvent extraction process is generally difficult.
［実施例１（ビーカー試験）］
ロジウム、イリジウム及びルテニウムを含有する塩酸酸性溶液の約０.７リットルを、８０〜９０℃に昇温した後、亜硝酸ナトリウムの添加によりｐＨ６〜７まで中和し、同時に食塩を添加して塩濃度を上昇させることにより、ロジウムをヘキサニトロロジウム酸ロジウムの結晶として沈澱させた。その後、濃縮により溶液中の塩濃度を更に上昇させ、ロジウムの溶解度を下げた。この処理前と処理後の溶液及び得られたロジウム結晶を塩酸溶解した溶解液について、ロジウム、イリジウム、及びルテニウムの各濃度をＩＣＰ分析し、分配比を算出したところ、下記表１に示す結果が得られた。
[Example 1 (beaker test)]
About 0.7 liter of an acidic hydrochloric acid solution containing rhodium, iridium and ruthenium was heated to 80 to 90 ° C., neutralized to pH 6 to 7 by adding sodium nitrite, and simultaneously added with sodium chloride to give a salt. The rhodium was precipitated as rhodium hexanitrorhodate crystals by increasing the concentration. Thereafter, the salt concentration in the solution was further increased by concentration to lower the solubility of rhodium. The concentration of rhodium, iridium, and ruthenium was analyzed by ICP for the solution before and after the treatment and the solution obtained by dissolving the obtained rhodium crystals with hydrochloric acid, and the distribution ratio was calculated. The results shown in Table 1 below were obtained. Obtained.
上記の結果から分るように、亜硝酸ナトリウムによる処理前のルテニウム／ロジウム濃度比が約１７.３％であったものが、処理により得られた結晶の溶解液中では約０.７％となっており、分配比では約９４.５％のルテニウムを除去することができた。 As can be seen from the above results, the ruthenium / rhodium concentration ratio before the treatment with sodium nitrite was about 17.3%, but in the crystal solution obtained by the treatment, it was about 0.7%. In the distribution ratio, about 94.5% of ruthenium could be removed.
このロジウム結晶の塩酸溶解液をトリブチルフォスフェイトにて溶媒抽出したところ、溶媒抽出処理は問題なく実施することができ、抽残液中のイリジウム濃度は０.０１ｇ／リットル以下であった。従って、得られた抽出後液中のイリジウム／ロジウム濃度比は、処理前の約３.３％に対して、０.１％未満の良好な結果が得られた。 When this hydrochloric acid solution of rhodium crystals was subjected to solvent extraction with tributyl phosphate, the solvent extraction treatment could be carried out without any problem, and the iridium concentration in the extracted residue was 0.01 g / liter or less. Therefore, the iridium / rhodium concentration ratio in the obtained post-extraction liquid was less than 0.1% with respect to about 3.3% before the treatment.
［実施例２（スケールアップ試験）］
ロジウム、イリジウム及びルテニウムを含有する塩酸酸性溶液の約６０リットルを、８０〜９０℃に昇温した後、亜硝酸ナトリウムの添加によりｐＨ６〜７まで中和し、同時に食塩を添加して塩濃度を上昇させることにより、ロジウムをヘキサニトロロジウム酸ロジウムの結晶として沈澱させた。その後、濃縮により溶液中の塩濃度を更に上昇させ、ロジウムの溶解度を下げた。この処理前と処理後の溶液及び得られたロジウム結晶を塩酸溶解した溶解液について、ロジウム、イリジウム、及びルテニウムの各濃度をＩＣＰ分析し、分配比を算出したところ、下記表２に示す結果が得られた。
[Example 2 (scale-up test)]
About 60 liters of hydrochloric acid acidic solution containing rhodium, iridium and ruthenium was heated to 80-90 ° C., then neutralized to pH 6-7 by adding sodium nitrite, and at the same time, salt was added to adjust the salt concentration. By raising, rhodium was precipitated as rhodium hexanitrorhodate crystals. Thereafter, the salt concentration in the solution was further increased by concentration to lower the solubility of rhodium. The concentration of rhodium, iridium, and ruthenium was analyzed by ICP for the solution before and after the treatment and the solution obtained by dissolving the obtained rhodium crystals in hydrochloric acid, and the distribution ratio was calculated. The results shown in Table 2 below were obtained. Obtained.
上記の結果から分るように、亜硝酸ナトリウムによる処理前のルテニウム／ロジウム濃度比が約２６.５％であったものが、処理により得られた結晶の溶解液中では約１.３％となっており、分配比では約９５.７％のルテニウムを除去することができた。 As can be seen from the above results, the ruthenium / rhodium concentration ratio before the treatment with sodium nitrite was about 26.5%, but in the crystal solution obtained by the treatment, it was about 1.3%. In the distribution ratio, about 95.7% of ruthenium could be removed.
このロジウム結晶の塩酸溶解液をトリブチルフォスフェイトにて溶媒抽出したところ、溶媒抽出処理は問題なく実施することができ、抽残液中のイリジウム濃度は０.０１ｇ／リットル以下であった。従って、得られた抽出後液中のイリジウム／ロジウム濃度比は、処理前の約３.８％に対して、０.１％未満の良好な結果が得られた。 When this hydrochloric acid solution of rhodium crystals was subjected to solvent extraction with tributyl phosphate, the solvent extraction treatment could be carried out without any problem, and the iridium concentration in the extracted residue was 0.01 g / liter or less. Therefore, the iridium / rhodium concentration ratio in the obtained post-extraction liquid was less than 0.1% as compared with about 3.8% before the treatment.
［比較例］
上記実施例２のロジウム、イリジウム及びルテニウムを含有する塩酸酸性溶液（処理元液）を、亜硝酸ソーダによる中和処理をすることなく、そのまま溶媒抽出処理に使用した以外は、実施例２と同様な処理を行った。
[Comparative example]
The same as Example 2 except that the hydrochloric acid acidic solution (treatment liquid) containing rhodium, iridium and ruthenium of Example 2 above was used for the solvent extraction treatment as it was without neutralizing with sodium nitrite. Was processed.
その結果、有機溶媒のトリブチルフォスフェイト中にルテニウムの蓄積が起こり、溶媒抽出処理を継続することが困難な状態にまで有機相と水相との分相性が悪化した。
As a result, the accumulation of ruthenium in the tributyl phosphate of the organic solvent occurred, and the phase separation between the organic phase and the aqueous phase deteriorated to the point where it was difficult to continue the solvent extraction process.
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