JPH03249143A - Method for separating and recovering rhodium - Google Patents
Method for separating and recovering rhodiumInfo
- Publication number
- JPH03249143A JPH03249143A JP4826790A JP4826790A JPH03249143A JP H03249143 A JPH03249143 A JP H03249143A JP 4826790 A JP4826790 A JP 4826790A JP 4826790 A JP4826790 A JP 4826790A JP H03249143 A JPH03249143 A JP H03249143A
- Authority
- JP
- Japan
- Prior art keywords
- rhodium
- hydrochloric acid
- organic solvent
- copper
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910052703 rhodium Inorganic materials 0.000 title claims description 78
- 239000010948 rhodium Substances 0.000 title claims description 78
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims description 77
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003960 organic solvent Substances 0.000 claims abstract description 42
- 229910052718 tin Inorganic materials 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 28
- -1 tin halide Chemical class 0.000 claims abstract description 25
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010953 base metal Substances 0.000 claims abstract description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexanol group Chemical group C(C)C(CO)CCCC YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 16
- YQTPVZDDJNOGNJ-UHFFFAOYSA-N rhodium hydrochloride Chemical compound Cl.[Rh] YQTPVZDDJNOGNJ-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000605 extraction Methods 0.000 abstract description 9
- 239000002244 precipitate Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 238000000926 separation method Methods 0.000 description 8
- LHNRHYOMDUJLLM-UHFFFAOYSA-N 1-hexylsulfanylhexane Chemical compound CCCCCCSCCCCCC LHNRHYOMDUJLLM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ロジウムを含有する塩酸溶液からロジウムを
分離回収する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for separating and recovering rhodium from a rhodium-containing hydrochloric acid solution.
（従来技術とその問題点）
従来、卑金属を含有するロジウム塩酸溶液よりロジウム
を分離回収する方法は、亜硝酸ナトリウムを加えて卑金
属の水酸化物を生成させ、濾過分離したのち、濾過液に
塩化アンモニウムを加えて亜硝酸ロジウム酸塩として沈
澱させて濾過分離回収する方法が一般的である。(Prior art and its problems) Conventionally, the method of separating and recovering rhodium from a rhodium hydrochloric acid solution containing a base metal is to add sodium nitrite to generate a base metal hydroxide, separate it by filtration, and then add chloride to the filtrate. A common method is to add ammonium to precipitate nitrite as a rhodate salt, and then filter, separate and recover it.
しかし、この方法ではロジウムを完全に分離回収するこ
とができず、ロジウムを分離したのちの液中には１１０
０ＰＰ程度のロジウムが残ってしまい、これを回収する
のに極めて多くの労力を要するものである。However, this method cannot completely separate and recover rhodium, and after rhodium is separated, 110
Approximately 0 PP of rhodium remains, which requires an extremely large amount of effort to recover.
（発明の目的）
本発明は、上記従来法の欠点を解決するために成された
もので、ジアルキルスルフィドを含む有機溶媒を用いて
ロジウムを抽出し、該抽出した有機溶媒相に剥離剤を加
えてロジウムを分離するという簡便な方法で、しかも１
００％近い分離回収方法を提供することを目的とする。(Purpose of the Invention) The present invention was made to solve the drawbacks of the above-mentioned conventional methods. Rhodium is extracted using an organic solvent containing dialkyl sulfide, and a stripping agent is added to the extracted organic solvent phase. This is a simple method of separating rhodium using
The objective is to provide a separation and recovery method that achieves close to 00% separation and recovery.
（問題点を解決するための手段）
本発明は、卑金属を含むロジウム塩酸溶液より、ジアル
キルスルフィドを抽出剤として含有する有機溶媒を用い
てロジウムを抽出する方法において、該ロジウム塩酸溶
液の塩酸濃度を０． ５〜１２規定に調節し、２価のハ
ロゲン化スズをロジウムに対するモル比で１． ５〜１
２倍、及びハロゲン化銅をロジウムに対するモル比で１
．５〜１２倍添加したのち、前記ジアルキルスルフィド
を抽出剤として含有し、さらに改質剤として高級アルコ
ールを含有する有機溶媒によりロジウムを抽出し、ロジ
ウムを抽出した有機溶媒相を０．５規定〜ｌ規定の希塩
酸で洗浄したのちロジウムを硫化物として沈澱分離させ
ることを特徴とするロジウムの分離回収方法で、前記２
価のハロゲン化スズが塩化第一スズでありハロゲン化銅
が塩化第二銅であるロジウムの分離回収方法で、前記改
質剤としての高級アルコールが２エチルヘキサノールで
あるロジウムの分離回収方法である。(Means for Solving the Problems) The present invention provides a method for extracting rhodium from a rhodium hydrochloric acid solution containing a base metal using an organic solvent containing dialkyl sulfide as an extractant, in which the hydrochloric acid concentration of the rhodium hydrochloric acid solution is 0. The molar ratio of divalent tin halide to rhodium is 1. 5-1
2 times, and 1 molar ratio of copper halide to rhodium.
．． After adding 5 to 12 times, rhodium is extracted with an organic solvent containing the dialkyl sulfide as an extractant and a higher alcohol as a modifier, and the organic solvent phase from which rhodium has been extracted is heated to 0.5 N to 1 A rhodium separation and recovery method characterized by washing with specified dilute hydrochloric acid and then precipitating and separating rhodium as sulfide.
This is a rhodium separation and recovery method in which the tin halide is stannous chloride and the copper halide is cupric chloride, and the higher alcohol as the modifier is 2-ethylhexanol. .
卑金属を含むロジウム塩酸溶液の塩酸濃度は、０．５〜
１２規定として調節して、ハロゲン化スズ（２価）をロ
ジウムに対するモル比で１． ５〜１２倍とし、ハロゲ
ン化銅をロジウムに対するモル比で１．５〜１２倍とな
るように加えて攪拌する。The hydrochloric acid concentration of rhodium hydrochloric acid solution containing base metal is 0.5 to
The molar ratio of tin (divalent) halide to rhodium is adjusted to 12N. The molar ratio of copper halide to rhodium is 1.5 to 12 times, and the mixture is stirred.
ロジウム塩酸溶液の塩酸濃度を０． ５〜１２規定とす
るのは、０．５規定以下ではロジウムを抽出する際に水
酸化物が生成して抽出操作の妨害となり、１２規定以上
では不純物の抽出が増加するからで、好ましくは１〜６
規定である。The hydrochloric acid concentration of the rhodium hydrochloric acid solution was set to 0. The reason why it is set to 5 to 12N is because if it is less than 0.5N, hydroxide will be generated when extracting rhodium and will interfere with the extraction operation, and if it is more than 12N, the extraction of impurities will increase. ~6
It is a regulation.
２価のハロゲン化スズ及びハロゲン化銅を加える理由は
ジアルキルスルフィドを抽出剤として含有する有機溶媒
を用いてロジウムを抽出する際の抽出率を向上させるた
めであるが、２価のハロゲン化スズ及びハロゲン化銅の
作用はロジウムクロロ錯体中の塩化物イオンが塩化スズ
イオン及び塩化銅イオンによって置換され抽出されやす
い化学種になったためと思われる。The reason for adding divalent tin halide and copper halide is to improve the extraction rate when extracting rhodium using an organic solvent containing dialkyl sulfide as an extractant. The action of copper halide is thought to be due to the fact that chloride ions in the rhodium chloro complex were replaced by tin chloride ions and copper chloride ions, making them easily extractable chemical species.
２価のハロゲン化スズの添加量はロジウム塩酸溶液中の
ロジウムに対するモル比で１，５〜１２倍でよ（、好ま
しくは９〜１２倍である。The amount of divalent tin halide added is preferably 1.5 to 12 times the molar ratio of rhodium in the rhodium hydrochloric acid solution (preferably 9 to 12 times).
該モル比が１． ５倍以下ではロジウムの抽出率が５０
％以下で効果が不十分であり、１２倍以上では添加効果
が同じとなるため経済性に欠けるからである。The molar ratio is 1. If it is 5 times or less, the rhodium extraction rate is 50
% or less, the effect is insufficient, and if it is 12 times or more, the effect will be the same, which is uneconomical.
ハロゲン化銅の添加量はロジウム塩酸溶液中のロジウム
に対するモル比で１． ５〜１２倍でよく、好ましくは
９〜１２倍である。The amount of copper halide added is 1.0 molar ratio to the rhodium in the rhodium hydrochloric acid solution. It may be 5 to 12 times, preferably 9 to 12 times.
該モル比が１．５倍以下ではロジウムの抽出速度はハロ
ゲン化銅を添加しない時と同様で効果が不十分であり、
１２倍以上では添加効果が同じとなるため経済性に欠け
るからである。When the molar ratio is less than 1.5 times, the extraction rate of rhodium is the same as when no copper halide is added, and the effect is insufficient.
This is because if the amount is 12 times or more, the effect of addition will be the same, resulting in a lack of economic efficiency.
次いでジアルキルスルフィドを抽出剤として含有し、さ
らに改質剤として高級アルコールを含有する有機溶媒と
して、ジアルキルスルフィドとしてはジーｎ−へキシル
スルファイド等で、その濃度は有機溶媒中に２０体積％
前後に希釈してもちいればよい。Next, an organic solvent containing a dialkyl sulfide as an extractant and a higher alcohol as a modifier is used as the dialkyl sulfide, such as di-n-hexyl sulfide, whose concentration is 20% by volume in the organic solvent.
All you have to do is dilute it before and after use.
また、改質剤としての高級アルコールは２エチルヘキサ
ノール等で、実質的に水不溶性で且つ有機相に保有され
るもので炭素数は６〜１５が好ましく飽和炭化水素であ
ればよ（、その濃度は有機溶媒中に２０体積％前後加え
て用いる。In addition, the higher alcohol used as a modifier is 2-ethylhexanol, etc., which is substantially water-insoluble and retained in the organic phase, preferably has 6 to 15 carbon atoms, and is preferably a saturated hydrocarbon (and its concentration is used by adding about 20% by volume to an organic solvent.
該改質剤を加える理由は、ロジウムの抽出率を高めるた
めに加えた２価のハロゲン化スズ等の影響により、抽出
剤としてのジアルキルスルフィトが繰り返し使用してゆ
くと変質して、有機溶媒相と塩酸溶液相との分離をさせ
にく（する沈澱物が生成してくるのを防止させることが
でき、その作用は明らかではないが、該沈澱物を溶解さ
せることと考えられる。The reason for adding this modifier is that due to the influence of divalent tin halide, etc. added to increase the extraction rate of rhodium, the dialkyl sulfite used as an extractant changes in quality with repeated use, and the organic solvent It is possible to prevent the separation of the hydrochloric acid solution phase and the hydrochloric acid solution phase from forming a precipitate, and although its effect is not clear, it is thought to dissolve the precipitate.
有機溶媒としてはパラフィン系炭化水素でよく、例えば
５ｔｉｅｌｌｓｏｌＤ７０等である。The organic solvent may be a paraffinic hydrocarbon, such as 5tiellsol D70.
２価のハロゲン化スズ及びハロゲン化銅を添加し、塩酸
濃度を調節したロジウム塩酸溶液とジアルキルスルフィ
ドを抽出剤として含有し、さらに改質剤として高級アル
コールを含有する有機溶媒を体積比で１：１−１：２で
混合し攪拌を十分に行いロジウムを抽出する。An organic solvent containing divalent tin halide and copper halide, a rhodium hydrochloric acid solution with adjusted hydrochloric acid concentration, dialkyl sulfide as an extractant, and a higher alcohol as a modifier in a volume ratio of 1:1. Mix at a ratio of 1-1:2 and stir thoroughly to extract rhodium.
以上の方法によりロジウムを抽出した有機溶媒相と分離
した塩酸溶液中にはロジウム濃度はｌｐｐｍ以下にする
ことができる。By the above method, the rhodium concentration in the hydrochloric acid solution separated from the organic solvent phase from which rhodium was extracted can be reduced to 1 ppm or less.
上記の方法でロジウムを抽出した有機溶媒相にはスズ及
び銅も抽出されるため、希塩酸で該ロジウムを抽出した
有機溶媒相を洗浄することで、スズ及び銅を溶離させ除
去することができる。Since tin and copper are also extracted in the organic solvent phase from which rhodium has been extracted by the above method, tin and copper can be eluted and removed by washing the organic solvent phase from which rhodium has been extracted with dilute hydrochloric acid.
スズ及び銅を溶離させるための希塩酸濃度は０．５規定
以上であればよく、６規定以上ではスズの溶離効率が低
下するので好ましくない。The concentration of dilute hydrochloric acid for eluting tin and copper may be 0.5N or more, and a concentration of 6N or more is not preferable because the tin elution efficiency decreases.
スズ及び銅を溶離させた有機溶媒相に硫化水素を吹き込
むか硫化ナトリウムを加えてロジウムの硫化物を生成さ
せ、沈澱となったロジウム硫化物を濾過分離し、１０８
３ （３００ａｏｎＨｇ） ’Ｃで加熱して金属ロジウ
ムとして回収分離でき、該金属ロジウムの純度は９９ｗ
ｔ％前後で回収率は９９％以上とすることができるもの
である。Hydrogen sulfide is blown into the organic solvent phase from which tin and copper have been eluted, or sodium sulfide is added to generate rhodium sulfide, and the precipitated rhodium sulfide is separated by filtration.
It can be recovered and separated as metal rhodium by heating at 3 (300aonHg)'C, and the purity of the metal rhodium is 99W.
The recovery rate can be 99% or more at around t%.
また、ロジウムを硫化物として沈澱させ分離した有機溶
媒は、繰り返し使用することができ、上記の方法によれ
ばおおむね１０回の繰り返し操作に耐えられるものであ
る。Further, the organic solvent in which rhodium is precipitated and separated as a sulfide can be used repeatedly, and according to the above method, it can withstand approximately 10 repeated operations.
以下、本発明に係わる実施例を記載するが、該実施例は
本発明を限定するものではない。Examples related to the present invention will be described below, but the examples are not intended to limit the present invention.
（実施例１）
ロジウム５ｇ／Ｉ、鉄５ｇ／Ｉ！、ニッケル５ｇ／Ｉ、
亜鉛１ｇ／Ｉ！、錫（ＩＶ）Ｉｇ／［を含む３Ｎ塩酸溶
液ｌｌに２価の塩化スズ５０ｇ及び塩化銅２５ｇを加え
、抽出剤としてジーｎ−へキシルスルフィド２０ｖｏ１
％と改質剤として２工チルヘキサノール２０ｖｏ１％を
含むパラフィン系炭化水素である５ｈｅｌｌｓｏｌＤ７
０ （シェル化学型）の有機溶媒を２１加えて１時間攪
拌し静置して塩酸相と有機溶媒相とを分離した。(Example 1) Rhodium 5g/I, iron 5g/I! , nickel 5g/I,
Zinc 1g/I! , 50 g of divalent tin chloride and 25 g of copper chloride were added to 1 liter of 3N hydrochloric acid solution containing tin(IV) Ig/[, and 20 vol of di-n-hexyl sulfide was added as an extractant.
% and 5hellsol D7, which is a paraffinic hydrocarbon containing 20vol 1% of 2-functional tylhexanol as a modifier.
0 (shell chemical type) organic solvent was added, stirred for 1 hour, and left to stand to separate the hydrochloric acid phase and the organic solvent phase.
該分離した塩酸相中のロジウムをＩＣＰにより分析した
ところ１ ｍ ｇ ／ １であった。Rhodium in the separated hydrochloric acid phase was analyzed by ICP and found to be 1 mg/1.
また、有機溶媒相中にはロジウムとスズと銅が抽出され
ていた。Additionally, rhodium, tin, and copper were extracted into the organic solvent phase.
該有機溶媒相に０． ５規定塩酸ＩＩ！を加え１時間攪
拌し静置したのち塩酸相を分離する操作を３回繰り返し
た。0.0% to the organic solvent phase. 5N Hydrochloric acid II! was added, stirred for 1 hour, allowed to stand, and then the hydrochloric acid phase was separated. This operation was repeated three times.
上記の０．５規定塩酸相３Ｉ！中にはスズ及び銅が溶離
していただけでロジウムは検出できなかった。Above 0.5N hydrochloric acid phase 3I! Only tin and copper were eluted, but no rhodium was detected.
スズ及び銅を溶離させた有機溶媒相に硫化水素ガスを吹
き込みながら、７０℃に加温して５時間その状態を維持
させてのち、硫化水素ガスの吹き込みを止め、放冷して
沈澱を濾過分離し、該沈澱を１２００ （３００ｍｍＨ
ｇ） ’Ｃで焼成したところロジウム９９ｗｔ％の純度
のものが５．０５ｇ得られた。While blowing hydrogen sulfide gas into the organic solvent phase in which tin and copper were eluted, the mixture was heated to 70°C and maintained at that temperature for 5 hours.Then, the blowing of hydrogen sulfide gas was stopped, the mixture was allowed to cool, and the precipitate was filtered. Separate the precipitate at 1200 (300 mmH)
g) When fired at 'C, 5.05 g of rhodium with a purity of 99 wt% was obtained.
また、沈澱を濾過分離したのちの有機溶媒相にはロジウ
ムが１０ｐｐｍ以下であった。Furthermore, rhodium was found to be 10 ppm or less in the organic solvent phase after the precipitate was separated by filtration.
以上の結果からロジウムの回収率は９９．９８％であっ
た。From the above results, the recovery rate of rhodium was 99.98%.
（比較例１）
ロジウム５ｇ／ｌ、鉄５ ｇ／！！、ニッケル５ｇ／ｌ
、亜鉛１ ｇｅｌ！、錫（ＩＶ） １ｇ／ｌを含む３
Ｎ塩酸溶液１ｊ７に、抽出剤としてジーｎ−へキシルス
ルフィド２０ｖｏ１％含むパラフィン系炭化水素である
５ｈｅｌｌｓｏｌＤ７０ （シェル化学型）の有機溶媒
を２１加えて５時間攪拌し静置して塩酸相と有機溶媒相
とを分離した。(Comparative Example 1) Rhodium 5g/l, iron 5g/! ! , nickel 5g/l
, zinc 1 gel! , containing 1 g/l of tin(IV) 3
To the N-hydrochloric acid solution 1j7, 21% of an organic solvent of 5hellsol D70 (shell chemical type), which is a paraffinic hydrocarbon containing 20vol% of di-n-hexyl sulfide as an extractant, was added, stirred for 5 hours, and left to stand to form the hydrochloric acid phase and the organic solvent. The phases were separated.
該分離した塩酸相中のロジウムをＩＣＰにより分析した
ところ５ｇ／βであった。Rhodium in the separated hydrochloric acid phase was analyzed by ICP and found to be 5 g/β.
また、有機溶媒相中にはロジウムが抽出されていなかっ
た。Moreover, rhodium was not extracted into the organic solvent phase.
（実施例２）
ロジウム２０ ｇ／ｌを含むＩＮ塩酸溶液に、塩化第一
スズをロジウムに対するモル比で、１．５．３．６．９
．１２とし塩化銅をロジウムに対するモル比で１．５．
３．６．９．１２倍とし、抽出剤としてジーｎ−へキシ
ルスルフィド２０ｖｏ１％、２エチルヘキサノール２０
ｖｏ１％含むｓｈｅｌｌｓｏｌＤ７０ （シェル化学製
）の有機溶媒を体積比で１＝１とし、それぞれ２時間震
盪させてロジウムを抽出させたところ、下記表−１のよ
うな結果であった。(Example 2) In an IN hydrochloric acid solution containing 20 g/l of rhodium, stannous chloride was added at a molar ratio of 1.5.3.6.9 to rhodium.
．． 12, and the molar ratio of copper chloride to rhodium is 1.5.
3.6.9.12 times, di-n-hexyl sulfide 20vol 1%, 2ethylhexanol 20% as extractants.
When the organic solvent of shellsol D70 (manufactured by Shell Chemical Co., Ltd.) containing vol.
（実施例３）
ロジウムとスズと銅を実施例２と同様の操作で抽出した
有機溶媒相（ロジウムおよびスズはそれぞれ０．００１
モル／ ｄ ｍ ’含み、銅は０．００モル／ ｄ ｍ
’含む）よりスズ及び銅を溶離するため、希塩酸の濃
度を０．１．０．２．０．４．０．６．０．８規定とし
て体積比を１＝１で６０分間震置きせて溶離させたとこ
ろ４０％前後スズ■
及び銅は溶離したが、ロジウムはすべて溶離することは
なかった。(Example 3) An organic solvent phase in which rhodium, tin, and copper were extracted in the same manner as in Example 2 (Rhodium and tin were each 0.001
mol/d m ', copper is 0.00 mol/d m
In order to elute tin and copper from the sample), the concentration of dilute hydrochloric acid was set to 0.1.0.2.0.4.0.6.0.8, and the volume ratio was 1=1, and the mixture was shaken for 60 minutes. When eluted, approximately 40% tin and copper were eluted, but rhodium was not eluted at all.
また、ロジウムの塩酸溶液に塩化第一スズと塩化第一銅
を加え、塩酸濃度を２．４．６．８規定にそれぞれ調整
して、抽出剤としてジーｎ−へキシルスルフィド２０ｖ
ｏ１％、２エチルヘキサノール２０ｖｏ１％含む５ｈｅ
ｌｌｓｏｌＤ７０（シェル化学製）の有機溶媒を体積比
でｌ：ｌとし、それぞれ２時間震盪させてロジウムとス
ズを抽出させた有機溶媒相（ロジウムおよびスズはそれ
ぞれ０．００１モル／ ｄ ｍ ’含み、銅は０．００
モル／ ｄ ｍ ’含む）を０．１規定希塩酸を用いて
体積比１：１で６０分間震置きて、スズ及び銅の溶離を
行ったところ、下記表−２のような結果であった。In addition, stannous chloride and cuprous chloride were added to the hydrochloric acid solution of rhodium, and the hydrochloric acid concentration was adjusted to 2.4.6.8 normal, respectively, and di-n-hexyl sulfide was used as an extractant.
5he containing o1%, 2 ethylhexanol 20vol1%
The organic solvent phase was prepared by using llsol D70 (manufactured by Shell Chemical) at a volume ratio of 1:1 and shaking for 2 hours to extract rhodium and tin (containing 0.001 mol/d m' of rhodium and tin each, Copper is 0.00
When tin and copper were eluted by shaking for 60 minutes using 0.1 N dilute hydrochloric acid at a volume ratio of 1:1, the results were as shown in Table 2 below.
（以下余白）
表−２
（実施例４）
塩化銅を加えた量が、５ｇ、ｌＯｇ、１５ｇ、２０ｇ、
３０ｇ、とした以外は実施例Ｉと同様にロジウムの抽出
操作を行ったところ、下記表−３のような結果であった
。(The following is a blank space) Table 2 (Example 4) The amount of copper chloride added is 5 g, 10 g, 15 g, 20 g,
When the rhodium extraction operation was carried out in the same manner as in Example I except that the amount was 30 g, the results were as shown in Table 3 below.
（実施例５）
実施例１でロジウムを硫化物として沈澱させたのち、濾
過分離した有機溶媒を用いて繰り返しロジウムの抽出、
塩酸洗浄、ロジウムを硫化物として沈澱分離する操作を
行ったところ、１０回の繰り返し操作でもロジウムの抽
出率に変化はなく、塩酸溶液相と有機溶媒相の分離に妨
害するような沈澱の生成はみられなかった。(Example 5) After rhodium was precipitated as sulfide in Example 1, rhodium was extracted repeatedly using the filtered organic solvent.
When washing with hydrochloric acid and precipitating and separating rhodium as sulfide were performed, there was no change in the extraction rate of rhodium even after repeated operations 10 times, indicating that no precipitate was formed that would interfere with the separation of the hydrochloric acid solution phase and the organic solvent phase. I couldn't see it.
この結果から、抽出剤としてジーｎ−へキシルスルフィ
ド２０ｖｏ１％、２エチルヘキサノール２０ｖｏ１％含
む５ｈｅｌｌｓｏｌＤ７０ （シェル化学製）の有機溶
媒２１で、ロジウムを含む塩酸溶液をｌＯ１処理するこ
とができたことになる。From this result, it was possible to treat a hydrochloric acid solution containing rhodium by 1O1 using organic solvent 21 of 5hellsol D70 (manufactured by Shell Chemical) containing 20vol 1% di-n-hexyl sulfide and 20vol 1% 2-ethylhexanol as extractants. .
（比較例２）
改質剤として２エチルヘキサノールを加えなかった以外
は実施例１と同様に操作して、ロジウムを硫化物として
沈澱させ、濾過分離したのちの有機溶媒を実施例４と同
様に繰り返しロジウムの抽出、塩酸洗浄、ロジウムを硫
化物として沈澱分離する操作を行ったところ、塩酸溶液
相と有機溶媒相の分離に妨害する沈澱が生成し、操作続
行不可能となった。(Comparative Example 2) Rhodium was precipitated as a sulfide in the same manner as in Example 1 except that 2-ethylhexanol was not added as a modifier, and the organic solvent after separation by filtration was treated in the same manner as in Example 4. When we repeatedly extracted rhodium, washed it with hydrochloric acid, and precipitated and separated rhodium as sulfide, a precipitate was formed that interfered with the separation of the hydrochloric acid solution phase and the organic solvent phase, making it impossible to continue the operation.
（発明の効果）
以上の説明で明らかのように、本発明の方法によれば、
２価のハロゲン化スズをロジウムを含有する塩酸溶液に
ロジウムに対しモル比で９倍以上となるように加え、さ
らにハロゲン化銅をロジウムに対しモル比で９倍以上と
なるように加え、ジアルキルスルフィドを抽出剤として
用い、抽出剤を安定させるための改質剤として２エチル
ヘキサノール等の高級アルコールを加え、混合、攪拌し
て有機溶媒相にロジウムを短時間で抽出し、次いで、有
機溶媒相を分離し希塩酸で洗浄してのち、ロジウムを硫
化物として沈澱させ有機溶媒相から分離し、ロジウムの
硫化物は焼成して金属ロジウムとして分離回収すること
ができ、従来法では得られない回収率９９％以上とする
ことができるとともに、有機溶媒を繰り返し用いること
ができるという画期的な方法である。(Effects of the invention) As is clear from the above explanation, according to the method of the present invention,
Divalent tin halide is added to a rhodium-containing hydrochloric acid solution in a molar ratio of at least 9 times that of rhodium, and copper halide is added in a molar ratio of at least 9 times that of rhodium. Sulfide is used as an extractant, a higher alcohol such as 2-ethylhexanol is added as a modifier to stabilize the extractant, and rhodium is extracted into the organic solvent phase in a short time by mixing and stirring. After separating and washing with dilute hydrochloric acid, rhodium is precipitated as sulfide and separated from the organic solvent phase, and the rhodium sulfide can be separated and recovered as metallic rhodium by calcination, achieving a recovery rate that cannot be obtained with conventional methods. This is an epoch-making method that allows the organic solvent to be used repeatedly in addition to being able to achieve a concentration of 99% or more.
Claims (3)
スルフィドを抽出剤として含有する有機溶媒を用いてロ
ジウムを抽出する方法において、該ロジウム塩酸溶液の
塩酸濃度を０．５〜１２規定に調節し、２価のハロゲン
化スズをロジウムに対するモル比で１．５〜１２倍及び
ハロゲン化銅をロジウムに対するモル比で１．５〜１２
倍添加したのち、前記ジアルキルスルフィドを抽出剤と
して含有し、さらに改質剤として高級アルコールを含有
する有機溶媒によりロジウムを抽出し、ロジウムを抽出
した有機溶媒相を０．５規定〜１規定の希塩酸で洗浄し
たのちロジウムを硫化物として沈澱分離させることを特
徴とするロジウムの分離回収方法。(1) In a method of extracting rhodium from a rhodium hydrochloric acid solution containing a base metal using an organic solvent containing dialkyl sulfide as an extractant, the hydrochloric acid concentration of the rhodium hydrochloric acid solution is adjusted to 0.5 to 12N, The molar ratio of tin halide to rhodium is 1.5 to 12 times, and the molar ratio of copper halide to rhodium is 1.5 to 12 times.
After the addition, rhodium is extracted with an organic solvent containing the dialkyl sulfide as an extractant and a higher alcohol as a modifier. A method for separating and recovering rhodium, which comprises washing the rhodium with water and then precipitating and separating the rhodium as a sulfide.
ハロゲン化銅が塩化第一銅もしくは塩化第二銅である請
求項１に記載のロジウムの分離回収方法。(2) The method for separating and recovering rhodium according to claim 1, wherein the divalent tin halide is stannous chloride and the copper halide is cuprous chloride or cupric chloride.
キサノールである請求項１に記載のロジウムの分離回収
方法。(3) The method for separating and recovering rhodium according to claim 1, wherein the higher alcohol as the modifier is 2-ethylhexanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4826790A JPH03249143A (en) | 1990-02-28 | 1990-02-28 | Method for separating and recovering rhodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4826790A JPH03249143A (en) | 1990-02-28 | 1990-02-28 | Method for separating and recovering rhodium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03249143A true JPH03249143A (en) | 1991-11-07 |
Family
ID=12798664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4826790A Pending JPH03249143A (en) | 1990-02-28 | 1990-02-28 | Method for separating and recovering rhodium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03249143A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5201942A (en) * | 1991-11-18 | 1993-04-13 | Mcgill University | Recovery of rhodium |
| WO2014156300A1 (en) * | 2013-03-27 | 2014-10-02 | 国立大学法人 東京大学 | Precious metal recovery method using copper halide-containing organic solvent system |
-
1990
- 1990-02-28 JP JP4826790A patent/JPH03249143A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5201942A (en) * | 1991-11-18 | 1993-04-13 | Mcgill University | Recovery of rhodium |
| WO2014156300A1 (en) * | 2013-03-27 | 2014-10-02 | 国立大学法人 東京大学 | Precious metal recovery method using copper halide-containing organic solvent system |
| CN105026583A (en) * | 2013-03-27 | 2015-11-04 | 国立大学法人东京大学 | Precious metal recovery method using copper halide-containing organic solvent system |
| KR20150136056A (en) * | 2013-03-27 | 2015-12-04 | 고쿠리츠다이가쿠호우진 도쿄다이가쿠 | Precious metal recovery method using copper halide-containing organic solvent system |
| JPWO2014156300A1 (en) * | 2013-03-27 | 2017-02-16 | 国立大学法人 東京大学 | Method for recovering noble metals using organic solvent system containing copper halide |
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