JP2013155391A - Recovery method of ruthenium - Google Patents
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- JP2013155391A JP2013155391A JP2012014606A JP2012014606A JP2013155391A JP 2013155391 A JP2013155391 A JP 2013155391A JP 2012014606 A JP2012014606 A JP 2012014606A JP 2012014606 A JP2012014606 A JP 2012014606A JP 2013155391 A JP2013155391 A JP 2013155391A
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- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 72
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000011084 recovery Methods 0.000 title claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007800 oxidant agent Substances 0.000 claims abstract description 37
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 19
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 15
- 230000033116 oxidation-reduction process Effects 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 33
- 239000002253 acid Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000007789 gas Substances 0.000 description 26
- -1 platinum group metals Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Gas Separation By Absorption (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は白金族金属を含む溶液からルテニウムを効率よく回収する方法に関する。 The present invention relates to a method for efficiently recovering ruthenium from a solution containing a platinum group metal.
白金族金属を含む溶液からルテニウムを分離し回収する方法として、ルテニウムの揮発性を利用した酸化蒸留方法が知られている。白金族金属のうち、ルテニウム(Ｒｕ)とオスミウム(Ｏｓ)の酸化物は揮発性を有するので他の白金族金属から蒸留して分離することができる。例えば特公平０１−３０８９６号公報（特許文献１）には、白金族金属を含む溶液に臭素酸ナトリウムを加えてルテニウム等を四酸化物にし、これを蒸留して分離回収する方法が記載されている。 As a method for separating and recovering ruthenium from a solution containing a platinum group metal, an oxidative distillation method using the volatility of ruthenium is known. Of the platinum group metals, ruthenium (Ru) and osmium (Os) oxides are volatile and can be separated from other platinum group metals by distillation. For example, Japanese Patent Publication No. 01-30896 (Patent Document 1) describes a method in which sodium bromate is added to a solution containing a platinum group metal to form ruthenium or the like into a tetraoxide, and this is distilled and separated and recovered. Yes.
このルテニウムの酸化蒸留法について、蒸留した四酸化ルテニウムを臭素酸ナトリウム溶液のトラップ槽に導入して白金等のミストを捕集すると共に四酸化ルテニウムの還元を防止して収率を高める方法が知られている（特開２００６−１６１０９６号公報：特許文献２）。また、ルテニウムの酸化蒸留法を利用してルテニウム含有スクラップからルテニウムを回収する方法も知られている（特開２００９−２０３４８６号公報：特許文献３）。 As for this ruthenium oxidative distillation method, a method is known in which distilled ruthenium tetroxide is introduced into a trap tank of a sodium bromate solution to collect mist such as platinum and prevent the reduction of ruthenium tetroxide to increase the yield. (Japanese Patent Laid-Open No. 2006-161096: Patent Document 2). Also known is a method of recovering ruthenium from ruthenium-containing scraps using an oxidation distillation method of ruthenium (Japanese Patent Laid-Open No. 2009-203486: Patent Document 3).
従来のルテニウム酸化蒸留法では、反応槽にルテニウム含有溶液を入れておき、そこに酸化剤を添加してルテニウムを酸化蒸留させていた。ところが、この方法では、実用段階で反応槽が大型になるとルテニウムの回収率は８０%程度が限度になると云う問題がある。この理由は、反応槽が大型になると溶液の撹拌効率や加熱効率の低下によって、反応槽内に昇温が不十分な部分が生じ、酸化反応が不均一になることが影響している。 In the conventional ruthenium oxidative distillation method, a ruthenium-containing solution is placed in a reaction tank, and an oxidizing agent is added thereto to oxidatively distill ruthenium. However, this method has a problem that the recovery rate of ruthenium is limited to about 80% when the reaction tank becomes large in practical use. The reason for this is that when the reaction tank becomes large, a portion where the temperature rise is insufficient in the reaction tank due to a decrease in the stirring efficiency and heating efficiency of the solution, and the oxidation reaction becomes uneven.
また、ルテニウム酸化蒸留法では、酸化剤の必要量を一度に全量添加すると、酸化剤が十分に溶解せずに底部に固まってしまい、反応槽底部のドレイン口が詰まってしまうと云う問題を生じるので、酸化剤はゆっくり少量づつ添加する必要があり、また、発生する四酸化ルテニウムは腐食性ガスであるので、酸化剤の添加口は小さく形成されており、少量の酸化剤がゆっくり添加される。このため、従来のルテニウム酸化蒸留法では、溶液中のルテニウムが十分な量の酸化剤に接する状態を形成し難い。 In addition, in the ruthenium oxidative distillation method, if the necessary amount of oxidant is added all at once, the oxidant is not sufficiently dissolved and solidifies at the bottom, and the drain port at the bottom of the reaction tank is clogged. Therefore, it is necessary to add the oxidant slowly in small amounts, and since the generated ruthenium tetroxide is a corrosive gas, the addition port of the oxidant is formed small, and a small amount of oxidant is slowly added. . For this reason, in the conventional ruthenium oxidative distillation method, it is difficult to form a state in which ruthenium in the solution is in contact with a sufficient amount of the oxidizing agent.
さらに、従来のルテニウムの酸化蒸留法では、酸化蒸留反応の終点は原料溶液量や蒸留温度などの反応条件に基づいて経験的に判定し、あるいは酸化反応槽や回収槽の溶液の色変化を目視観察して判断していた。しかし、反応時間を経験的に定めると、反応元液中のルテニウムの量が変動した場合などに対応できず、また反応槽や回収槽の溶液の色変化を目視確認する方法では微少な変化が分かり難く、作業者による誤差も大きいなどの問題があった。 Furthermore, in the conventional ruthenium oxidative distillation method, the end point of the oxidative distillation reaction is determined empirically based on the reaction conditions such as the amount of the raw material solution and the distillation temperature, or the color change of the solution in the oxidation reaction tank and the recovery tank is visually observed. I was observing and judging. However, if the reaction time is determined empirically, it cannot cope with the case where the amount of ruthenium in the reaction source solution fluctuates, and the method of visually confirming the color change of the solution in the reaction tank or the recovery tank causes a slight change. It was difficult to understand and there were problems such as large errors by the workers.
一方、酸化蒸留によって発生する四酸化ルテニウム蒸気は非常に不安定な腐食性ガスであるため、反応槽で四酸化ルテニウム量などを測定すると器具の腐食が進み、信頼性ある測定を長期間行うことが難しく、酸化反応を安定に制御し難しい問題があった。このような問題を解決するため、四酸化ルテニウムガスの吸収工程で副生するガスを利用して酸化反応の終点を把握する方法が検討されている（特願２０１０−１４８９２９号）。 On the other hand, ruthenium tetroxide vapor generated by oxidative distillation is a very unstable and corrosive gas. It was difficult to control the oxidation reaction stably. In order to solve such a problem, a method of grasping the end point of the oxidation reaction using a gas by-produced in the ruthenium tetroxide gas absorption process has been studied (Japanese Patent Application No. 2010-148929).
本発明は、大型の反応槽を用いても酸化反応の効率が良く、ルテニウムの回収率を高めることができるルテニウム回収方法を提供する。また、この回収方法にルテニウムの酸化反応の終点を把握する上記方法を組み込み、安定に酸化反応を制御することができるルテニウム回収方法を提供する。 The present invention provides a ruthenium recovery method capable of improving the efficiency of oxidation reaction and increasing the recovery rate of ruthenium even when a large reaction tank is used. Further, the above method for grasping the end point of the ruthenium oxidation reaction is incorporated in this recovery method, and a ruthenium recovery method capable of stably controlling the oxidation reaction is provided.
本発明は以下の構成からなるルテニウムの回収方法に関する。
〔１〕ルテニウムを含む白金族金属含有溶液から四酸化ルテニウムを蒸留させる工程、この四酸化ルテニウムを塩酸に吸収させて塩化ルテニウム酸溶液を回収する工程を有するルテニウムの回収方法において、加熱した酸化剤水溶液に上記白金族金属含有溶液を滴下することによって四酸化ルテニウムを蒸留させることを特徴とするルテニウムの回収方法。
〔２〕酸化剤として臭素酸ナトリウムを用い、反応槽に臭素酸ナトリウム水溶液を入れ、該水溶液のｐＨを１〜５に調整しながら、加熱した臭素酸ナトリウム水溶液に上記白金族金属含有溶液を滴下して酸化ルテニウムを蒸留させる上記[１]に記載するルテニウムの回収方法。
〔３〕蒸留した四酸化ルテニウムを塩酸に吸収させる工程において、該吸収工程から排出される副生ガスをアルカリ溶液に吸収させ、このアルカリ溶液の酸化還元電位の経時変化を測定することによってルテニウムの酸化反応の終点を把握する上記[１]または上記[２]に記載するルテニウムの回収方法。
〔４〕塩酸による吸収工程から排出される副生ガスを吸収したアルカリ溶液の酸化還元電位について、電位変化率が０.５mV/min以下の状態が３０分以上継続した段階を蒸留反応の終点とする上記[１]〜上記[３]の何れかに記載するルテニウムの回収方法。
The present invention relates to a ruthenium recovery method having the following configuration.
[1] In a ruthenium recovery method comprising a step of distilling ruthenium tetroxide from a platinum group metal-containing solution containing ruthenium, and a step of absorbing the ruthenium tetroxide in hydrochloric acid to recover a ruthenium chloride solution, a heated oxidant A method for recovering ruthenium, wherein ruthenium tetroxide is distilled by dropping the platinum group metal-containing solution into an aqueous solution.
[2] Using sodium bromate as an oxidizing agent, adding a sodium bromate aqueous solution to the reaction vessel, and dropping the platinum group metal-containing solution into the heated sodium bromate aqueous solution while adjusting the pH of the aqueous solution to 1 to 5 The ruthenium recovery method according to the above [1], wherein the ruthenium oxide is distilled.
[3] In the step of absorbing distilled ruthenium tetroxide in hydrochloric acid, the by-product gas discharged from the absorption step is absorbed in an alkaline solution, and the change in oxidation-reduction potential of the alkaline solution with time is measured. The method for recovering ruthenium according to the above [1] or [2], wherein the end point of the oxidation reaction is grasped.
[4] Regarding the oxidation-reduction potential of the alkaline solution that has absorbed the by-product gas discharged from the absorption step with hydrochloric acid, the stage in which the potential change rate is 0.5 mV / min or less continues for 30 minutes or more is defined as the end point of the distillation reaction. The method for recovering ruthenium according to any one of [1] to [3] above.
本発明の回収方法は、加熱した酸化剤水溶液にルテニウムを含む白金族金属含有溶液（元液）を滴下するので、大型の反応槽でも、ルテニウムが酸化剤に均一に接触して十分に酸化され、酸化反応の効率がよく、ルテニウムの回収率を高めることができる。また、酸化剤が加熱されているので、生成した四酸化ルテニウムがすぐに蒸留し、反応が早い。 In the recovery method of the present invention, since a platinum group metal-containing solution containing ruthenium (original solution) is dropped into a heated oxidant aqueous solution, ruthenium is uniformly contacted with the oxidant and sufficiently oxidized even in a large reaction vessel. The efficiency of the oxidation reaction is good, and the recovery rate of ruthenium can be increased. Further, since the oxidizing agent is heated, the produced ruthenium tetroxide is immediately distilled and the reaction is fast.
また、元液を供給するので、供給速度を調節して四酸化ルテニウムのガス発生をコントロールすることができ、反応槽内の突発的な泡立ちやガス発生などの過剰反応を防止することができる。さらに、反応効率が良いので酸化剤の必要量を従来の方法よりも少なくすることができる。 Further, since the original solution is supplied, it is possible to control the gas generation of ruthenium tetroxide by adjusting the supply rate, and it is possible to prevent excessive reactions such as sudden foaming and gas generation in the reaction tank. Furthermore, since the reaction efficiency is good, the required amount of the oxidizing agent can be reduced as compared with the conventional method.
従来の方法では、作業員が粉末の酸化剤を反応槽に供給しているが、本発明の方法では、反応槽に酸化剤水溶液を入れておき、これに元液を管路を通じて供給することができるので、作業が安全である。 In the conventional method, the worker supplies the powdered oxidant to the reaction tank. However, in the method of the present invention, the oxidant aqueous solution is placed in the reaction tank, and the original solution is supplied to the reaction tank through the pipeline. Work is safe.
さらに、本発明の回収方法では、蒸留した四酸化ルテニウムを塩酸に吸収させる際に副生するガスをアルカリ溶液に吸収させ、このアルカリ溶液の電位変化を測定して酸化蒸留の終点を把握する方法を採用すれば、酸化反応を制御するための測定器具を腐食性の四酸化ルテニウムに接触させる必要がなく、測定器具の腐食を避けることができ、酸化蒸留反応の進行を安定かつ正確に把握することができる。 Furthermore, in the recovery method of the present invention, a gas produced as a by-product when absorbing distilled ruthenium tetroxide into hydrochloric acid is absorbed in an alkali solution, and the potential change of the alkali solution is measured to grasp the end point of oxidative distillation. This eliminates the need for the measuring instrument to control the oxidation reaction to contact corrosive ruthenium tetroxide, avoids corrosion of the measuring instrument, and provides a stable and accurate grasp of the progress of the oxidative distillation reaction. be able to.
以下、本発明を具体的に説明する。
〔ルテニウムの回収方法〕
本発明の回収方法は、ルテニウムを含む白金族金属含有溶液から四酸化ルテニウムを蒸留させる工程、この四酸化ルテニウムを塩酸に吸収させて塩化ルテニウム酸溶液を回収する工程を有するルテニウムの回収方法において、加熱した酸化剤水溶液に上記白金族金属含有溶液を滴下することによって四酸化ルテニウムを蒸留させることを特徴とするルテニウムの回収方法である。
Hereinafter, the present invention will be specifically described.
[Ruthenium recovery method]
The recovery method of the present invention includes a step of distilling ruthenium tetroxide from a platinum group metal-containing solution containing ruthenium, and a step of recovering the ruthenium chloride solution by absorbing the ruthenium tetroxide in hydrochloric acid. A ruthenium tetroxide recovery method, wherein ruthenium tetroxide is distilled by dropping the platinum group metal-containing solution into a heated aqueous oxidizing agent solution.
また、本発明の回収方法は、加熱した酸化剤水溶液にルテニウムを含む白金族金属含有溶液を滴下して四酸化ルテニウムを蒸留させ、この四酸化ルテニウムを塩酸に吸収させて塩化ルテニウム酸溶液を回収するルテニウムの回収方法において、該吸収工程で排出される副生ガスをアルカリ溶液に吸収させ、このアルカリ溶液の酸化還元電位の経時変化を測定することによってルテニウムの酸化反応の終点を把握するルテニウムの回収方法である。 In addition, the recovery method of the present invention is a method in which a ruthenium-containing platinum group metal-containing solution is dropped into a heated aqueous oxidizing agent solution to distill ruthenium tetroxide, and the ruthenium tetroxide is absorbed by hydrochloric acid to recover a ruthenium chloride solution. In the ruthenium recovery method, the by-product gas discharged in the absorption step is absorbed into an alkaline solution, and the end point of the ruthenium oxidation reaction is determined by measuring the change over time in the oxidation-reduction potential of the alkaline solution. It is a collection method.
本発明の回収方法において、ルテニウムを含む白金族金属含有溶液は、例えば、銅電解スライムの塩酸浸出後液、使用済みスパッタリング用ターゲット材の塩酸浸出液などを用いることができる。 In the recovery method of the present invention, the platinum group metal-containing solution containing ruthenium can be, for example, a solution after copper electrolyte leaching of hydrochloric acid, a hydrochloric acid leaching solution of a used sputtering target material, or the like.
ルテニウムを含む白金族金属含有溶液からルテニウムを酸化して蒸留させる。四酸化ルテニウム（ＲｕＯ4）の沸点は約１３０℃であり、揮発性を有するので、ルテニウムを酸化して蒸留することによって他の白金族金属から分離することができる。 Ruthenium is oxidized and distilled from a platinum group metal-containing solution containing ruthenium. Since ruthenium tetroxide (RuO 4 ) has a boiling point of about 130 ° C. and is volatile, it can be separated from other platinum group metals by oxidizing and distilling ruthenium.
ルテニウムを酸化する酸化剤としては、アルカリ金属の塩素酸塩や臭素酸塩が好適に用いられ、例えば臭素酸ナトリウム（ＮａＢｒＯ3）が用いられる。 As the oxidizing agent for oxidizing ruthenium, alkali metal chlorates and bromates are preferably used. For example, sodium bromate (NaBrO 3 ) is used.
本発明の回収方法は、ルテニウムを含む白金族金属含有溶液（元液）に酸化剤を添加する従来の方法に代えて、反応槽に酸化剤溶液、例えば臭素酸ナトリウム水溶液を入れておき、該溶液のｐＨを１〜５、好ましくはｐＨ１〜４に調整しながら、加熱した酸化剤溶液にルテニウムを含む白金族金属含有溶液（元液）を滴下し、ルテニウムを酸化して蒸留させる。 In the recovery method of the present invention, instead of the conventional method of adding an oxidizing agent to a platinum group metal-containing solution (original solution) containing ruthenium, an oxidizing agent solution such as a sodium bromate aqueous solution is put in a reaction vessel, While adjusting the pH of the solution to 1 to 5, preferably pH 1 to 4, a platinum group metal-containing solution (original solution) containing ruthenium is dropped into the heated oxidant solution, and ruthenium is oxidized and distilled.
元液に酸化剤を添加する従来の方法では、反応槽が大型化すると、反応槽での元液の撹拌や加熱効果が不均一になりやすく、元液に含まれるルテニウムが十分に酸化剤に接触することができ難くなるので、酸化反応の効率が低く、ルテニウムの回収率が低下する。 In the conventional method of adding an oxidizing agent to the original solution, if the reaction vessel is enlarged, the stirring and heating effects of the original solution in the reaction vessel tend to be uneven, and the ruthenium contained in the original solution becomes a sufficient oxidizing agent. Since it becomes difficult to make contact, the efficiency of the oxidation reaction is low, and the ruthenium recovery rate decreases.
一方、本発明の回収方法では、加熱した酸化剤溶液に元液を滴下するので、滴下された元液に含まれるルテニウムが十分な量の酸化剤に接触することができ、大型の反応槽でも酸化反応の効率がよく、ルテニウムの回収率が向上する。さらに、酸化剤溶液が加熱されているので、生成した四酸化ルテニウム（ＲｕＯ4）をすぐに揮発させることができる。 On the other hand, in the recovery method of the present invention, since the original solution is dropped into the heated oxidant solution, ruthenium contained in the dropped original solution can contact a sufficient amount of the oxidant, and even in a large reaction tank. The efficiency of the oxidation reaction is good and the recovery rate of ruthenium is improved. Furthermore, since the oxidant solution is heated, the produced ruthenium tetroxide (RuO 4 ) can be volatilized immediately.
反応槽内のｐＨを１〜５、好ましくはｐＨ１〜４に調整しながら、加熱した酸化剤溶液に元液を滴下してルテニウムを酸化し、蒸留させる。酸化剤として臭素酸ナトリウム水溶液を用いる場合、この溶液のｐＨは６以上なので、そのまま元液を滴下すると、元液に含まれるルテニウムの多くは加水分解して水酸化物沈殿になり、酸化反応の効率が低下する。 While adjusting the pH in the reaction vessel to 1 to 5, preferably pH 1 to 4, the original solution is dropped into the heated oxidant solution to oxidize and distill ruthenium. When using a sodium bromate aqueous solution as the oxidizing agent, the pH of this solution is 6 or more. Therefore, when the original solution is added as it is, most of the ruthenium contained in the original solution is hydrolyzed to form a hydroxide precipitate. Efficiency is reduced.
また、臭素酸イオンはプロトン（水素イオン等）と反応することによって酸化剤として作用するので（2BrO3 - + 12H+ + 10e- → Br2 + 6H2O）、反応槽内はプロトンが存在するように酸性にすることが必要である。反応槽内がｐＨ５を超えると、酸化剤の機能が低下する。一方、ｐＨが１より低いと臭素酸ナトリウムが酸分解して酸化剤として機能しなくなるので、酸化反応中の反応槽内はｐＨ１以上に調整される。 Further, since the bromate ion acts as an oxidizing agent by reacting with protons (hydrogen ions, etc.) (2BrO 3 - + 12H + + 10e - → Br 2 + 6H 2 O), the reaction vessel is present protons It is necessary to make it acidic. When the inside of the reaction tank exceeds pH 5, the function of the oxidant is lowered. On the other hand, when the pH is lower than 1, sodium bromate is acid decomposed and does not function as an oxidizing agent, so the inside of the reaction tank during the oxidation reaction is adjusted to pH 1 or higher.
ルテニウムの酸化によって生成する四酸化ルテニウムの沸点は約１３０℃であるので、蓋をした反応槽内の酸化剤溶液を７０℃〜９０℃、好ましくは８０℃〜８５℃に加熱して、四酸化ルテニウムを蒸留させるとよい。 Since the boiling point of ruthenium tetroxide produced by ruthenium oxidation is about 130 ° C., the oxidant solution in the capped reaction vessel is heated to 70 ° C. to 90 ° C., preferably 80 ° C. to 85 ° C. Ruthenium should be distilled.
本発明の回収方法において、好ましくは、蒸留した四酸化ルテニウムを塩酸に吸収させて塩化ルテニウム酸溶液を回収する工程において、該吸収工程から排出される副生ガスをアルカリ溶液に吸収させ、このアルカリ溶液の酸化還元電位の経時変化を測定することによってルテニウムの酸化反応の終点を把握するとよい。 In the recovery method of the present invention, preferably, in the step of absorbing the distilled ruthenium tetroxide in hydrochloric acid to recover the ruthenium chloride solution, the by-product gas discharged from the absorption step is absorbed in the alkaline solution, The end point of the ruthenium oxidation reaction may be grasped by measuring the change over time of the oxidation-reduction potential of the solution.
具体的には、反応槽および蒸留した酸化ルテニウムを塩酸に吸収させる工程において、臭素ガスおよび塩素ガスが副生する。この副生ガスを例えば水酸化ナトリウム水溶液に吸収させ、副生ガスを吸収した水酸化ナトリウムの酸化還元電位を測定し、該電位の変化によってルテニウムの酸化反応の終点を把握する。 Specifically, bromine gas and chlorine gas are by-produced in the reaction tank and the step of absorbing distilled ruthenium oxide into hydrochloric acid. This by-product gas is absorbed in, for example, an aqueous sodium hydroxide solution, the oxidation-reduction potential of sodium hydroxide that has absorbed the by-product gas is measured, and the end point of the ruthenium oxidation reaction is grasped by the change in the potential.
例えば、基準値以下の電位変化率が一定時間継続すれば、酸化反応は終了したものと判断することができる。電位変化率〔(電位変化量)／(経過時間)〕は次式(１)によって測定することができる。
電位変化率〔ΔＥ／Δｔ〕ｎ＝〔Ｅn−Ｅ(n-1)〕／〔ｔn−ｔ(n-1)〕… (１)
式中、ΔＥは電位変化量、Δｔは単位時間、Ｅnはｎ測定時の電位、Ｅ(n-1)は(n-1)測定時の電位、ｔnはｎ測定時、ｔ(n-1)は(n-1)測定時。
For example, if the potential change rate below the reference value continues for a certain period of time, it can be determined that the oxidation reaction has ended. The potential change rate [(potential change amount) / (elapsed time)] can be measured by the following equation (1).
Potential change rate [ΔE / Δt] n = [En−E (n−1)] / [tn−t (n−1)] (1)
In the equation, ΔE is a potential change amount, Δt is a unit time, En is a potential at the time of n measurement, E (n-1) is a potential at the time of (n-1) measurement, tn is a potential at the time of n measurement, t (n-1 ) (N-1) when measuring.
電位変化率の基準値および定常状態の継続時間は適用される反応条件や装置構成によって定めればよい。例えば、電位変化率が０.５mV/min以下の状態が３０分以上継続した段階を蒸留反応の終点とすることができる。このような方法によって酸化蒸留反応の進行を安定かつ正確に把握することができる。 The reference value of the potential change rate and the duration of the steady state may be determined according to the applied reaction conditions and the apparatus configuration. For example, the end point of the distillation reaction can be a stage where the state where the potential change rate is 0.5 mV / min or less continues for 30 minutes or more. By such a method, the progress of the oxidative distillation reaction can be grasped stably and accurately.
〔装置構成〕
本発明の回収方法は、例えば、図１に示す装置によって実施することができる。
図示するように、反応槽１０はマントルヒータに設置されており、約７０℃〜９０℃に加熱されている。反応槽１０には酸化剤水溶液、例えば臭素酸ナトリウム水溶液が入っている。臭素酸ナトリウム水溶液には塩酸が加えられ、ｐＨ１〜５、好ましくはｐＨ１〜４に調整されている。
〔Device configuration〕
The recovery method of the present invention can be implemented, for example, by the apparatus shown in FIG.
As shown in the figure, the
反応槽１０は蓋９によって閉じられており、この蓋９を貫通して撹拌機８、管路７が設けられている。反応槽１０には送液ポンプ１７を通じて元液の供給槽１６が接続している。供給槽１６にはルテニウム(Ｒｕ)を含む白金族金属を含有する塩酸酸性溶液（元液）が入っている。この元液には水酸化ナトリウム(ＮａＯＨ)が加えられてｐＨ約１に調整されている。元液は送液ポンプ１７を通じて反応槽１０に少量づつ供給される。
The
反応槽１０において、臭素酸ナトリウム水溶液に元液が少量づつ添加され、該元液に含まれるルテニウムは、臭素酸ナトリウムによって酸化されて揮発性の四酸化ルテニウム（ＲｕＯ4）を生じ、このＲｕＯ4がガス化して蒸留し、同時に臭素ガス(Ｂｒ2)が副生する。
In the
反応槽１０には管路７を通じて回収槽１１が接続している。図示する装置例では回収槽１１が三段に設けられている。回収槽１１には塩酸が入っており、蒸留したＲｕＯ4ガスは回収槽１１に導入され、塩酸に吸収されて塩化ルテニウム酸溶液（Ｈ2ＲｕＣｌ6）になり、回収される。回収槽１１では塩素ガス（Ｃｌ2）が副生する。反応槽１０において副生したガス（主にＢｒ2）はＲｕＯ4ガスと共に回収槽１１に導入されるが、酸性であるので塩酸には殆ど吸収されず、回収槽１１において副生したガス（主にＣｌ2）と共に槽外に排出される。
A recovery tank 11 is connected to the
回収槽１１には管路７を通じて吸収槽１２が接続している。図示する装置例では吸収槽１２が二段に設けられている。吸収槽１２にはＮａＯＨ溶液（吸収液）が入っている。回収槽１１から排出された副生ガスは吸収槽１２に導入され、ＮａＯＨ溶液に吸収される。二段目の吸収槽１２にはＮａＯＨ溶液の酸化還元電位を測定するＯＲＰ計１５が設置されている。
An absorption tank 12 is connected to the recovery tank 11 through a pipe line 7. In the illustrated apparatus example, the absorption tank 12 is provided in two stages. The absorption tank 12 contains a NaOH solution (absorption liquid). By-product gas discharged from the collection tank 11 is introduced into the absorption tank 12 and absorbed by the NaOH solution. An
二段目の吸収槽１２には空槽１３が接続しており、さらに空槽１３には吸気ポンプ１４が接続している。反応槽１０から回収槽１１、吸収槽１２、空槽１３は管路７を通じて吸気ポンプ１４によって吸引されており、ＲｕＯ4蒸留ガスと副生ガスは吸引されて各槽に導入され、また吸気ポンプ１４によって流量が制御される。さらに空槽１３では吸引されたガス中のミストなどが捕集される。
An
回収槽１１から排出された副生ガスは吸収槽１２に導かれてＮａＯＨ溶液に吸収される。副生ガスを吸収したＮａＯＨ溶液の酸化還元電位がＯＲＰ計１５によって測定され、その経時変化、例えば、電位変化率が上記式(１)によって測定される。この電位変化率が基準値以下、例えば０.５mV/min以下であって、この基準値以下の電位変化率が３０分継続すれば酸化蒸留反応は終了したものと判断し、反応を停止する。
The by-product gas discharged from the recovery tank 11 is guided to the absorption tank 12 and absorbed by the NaOH solution. The oxidation-reduction potential of the NaOH solution that has absorbed the by-product gas is measured by the
以下、本発明の実施例を示す。図１に示す蒸留装置を用いてルテニウムの酸化蒸留を行なった。ルテニウム回収率はＲｕ回収率（％）＝(Ｒｕ回収量)／(反応前の元液中のＲｕ量)の式によって求めた。 Examples of the present invention will be described below. Ruthenium was oxidatively distilled using the distillation apparatus shown in FIG. The ruthenium recovery rate was determined by the formula Ru recovery rate (%) = (Ru recovery amount) / (Ru amount in the original solution before reaction).
〔実施例１〕
臭素酸ナトリウム２５６０ｇを水１０Ｌに溶解し、これに塩酸を添加してｐＨ４に調整して酸化剤水溶液を調製した。この酸化剤水溶液を反応槽１０に入れて８０℃に加熱した。一方、供給槽１６にはＲｕおよび白金族金属（Ｐｔ，Ｐｄ，Ｒｈ，Ｉｒ）を含む塩酸性溶液にＮａＯＨ水溶液を加えてｐＨ１.０に調整した元液（Ｒｕ濃度１５.２g/L、液量２５Ｌ）を入れ、この元液の全量を２時間かけて少量づつ反応槽１０に滴下した。反応槽１０は８０℃に加熱しながら撹拌し、送液ポンプ１７を用いて元液を供給槽１６から吸引して滴下しながら反応させた。反応槽１０で発生したＲｕＯ4蒸気を含む蒸留ガスは回収槽１１（６ＮのHCl水溶液）に導いてＲｕＯ4蒸気をＨＣｌ溶液に吸収させ、塩化ルテニウム酸（Ｈ2ＲｕＣｌ6）溶液として回収した。回収槽１１から排出された副生ガス（Ｂｒ2およびＣｌ2）は吸収槽１２（ＮａＯＨ水溶液）に導いて吸収させた。元液の全量を滴下して反応終了とした。反応終了後に回収槽１１に吸収されたＲｕ量から測定したＲｕ回収率は９６.８％であった。反応後の反応槽内液はｐＨ３.０であった。
[Example 1]
2560 g of sodium bromate was dissolved in 10 L of water, and hydrochloric acid was added to adjust the pH to 4 to prepare an aqueous oxidizing agent solution. This oxidizing agent aqueous solution was put into the
〔比較例１〕
実施例１と同様の元液２５Ｌを先に反応槽に入れ、反応槽の元液に粉末の臭素酸ナトリウム２５６０ｇを１６分かけて少量づつ添加し、反応槽の温度を８０℃に昇温して反応させた。蒸留後の処理は実施例１と同様に行なった。その結果、回収槽１１に吸収されたＲｕ量から測定したＲｕ回収率は７８.７％であり、実施例１のＲｕ回収率より大幅に低かった。反応後の反応槽内液はｐＨ４.５であった。
[Comparative Example 1]
First, 25 L of the same original solution as in Example 1 was put into the reaction vessel, 2560 g of powdered sodium bromate was added to the original solution of the reaction vessel little by little over 16 minutes, and the temperature of the reaction vessel was raised to 80 ° C. And reacted. The treatment after distillation was carried out in the same manner as in Example 1. As a result, the Ru recovery rate measured from the amount of Ru absorbed in the recovery tank 11 was 78.7%, which was significantly lower than the Ru recovery rate of Example 1. The solution in the reaction vessel after the reaction was pH 4.5.
〔実施例２〕
図１の装置において、吸収槽１２(２本目)（内液は4NのNaOH水溶液）の酸化還元電位変化をＯＲＰ計(vs Ag/AgCl)を用いて５分おきに測定し、上記式(１)に基いて電位変化量(mV/min)を算出し、酸化蒸留の終点を定めた以外は実施例１と同様にして元液の酸化蒸留を行った。電位変化率が０.５mV/min以下になってから３０分経過した時点で、反応槽１０の蒸気発生はほぼなくなり、電位変化率もほぼ０mV/minに落ち着いたので、反応を終了した。その結果、Ｒｕの回収率は９９.２％であった。
[Example 2]
In the apparatus of FIG. 1, the oxidation-reduction potential change of the absorption tank 12 (second) (inner solution is 4N NaOH aqueous solution) is measured every 5 minutes using an ORP meter (vs Ag / AgCl), and the above formula (1 The potential change (mV / min) was calculated based on), and the original solution was oxidatively distilled in the same manner as in Example 1 except that the end point of oxidative distillation was determined. When 30 minutes had elapsed since the potential change rate became 0.5 mV / min or less, the generation of steam in the
１０−反応槽、１１−回収槽、１２−吸収槽、１３−空槽、１４−吸気ポンプ、１５−ＯＲＰ計、１６−供給槽、１７−送液ポンプ 10-reaction tank, 11-recovery tank, 12-absorption tank, 13-empty tank, 14-intake pump, 15-ORP meter, 16-supply tank, 17-feed pump
Claims (4)
In a ruthenium recovery method comprising a step of distilling ruthenium tetroxide from a platinum group metal-containing solution containing ruthenium, and a step of absorbing the ruthenium tetroxide in hydrochloric acid to recover a ruthenium chloride solution, A method for recovering ruthenium, wherein ruthenium tetroxide is distilled by dropping a platinum group metal-containing solution.
Using sodium bromate as an oxidizing agent, placing a sodium bromate aqueous solution in the reaction vessel and adjusting the pH of the aqueous solution to 1 to 5, dropwise adding the platinum group metal-containing solution to the heated sodium bromate aqueous solution. The method for recovering ruthenium according to claim 1, wherein ruthenium oxide is distilled.
In the process of absorbing distilled ruthenium tetroxide in hydrochloric acid, the by-product gas discharged from the absorption process is absorbed in an alkali solution, and the change in oxidation-reduction potential of this alkali solution over time is measured to measure the oxidation reaction of ruthenium. The method for recovering ruthenium according to claim 1 or 2, wherein the end point is grasped.
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| JP2014043611A (en) * | 2012-08-27 | 2014-03-13 | Asahi Pretec Corp | Method for recovering ruthenium |
| CN103725903A (en) * | 2013-12-31 | 2014-04-16 | 新疆中泰化学股份有限公司 | Mercury-containing hydrochloric acid recovery plant |
| JP2018103078A (en) * | 2016-12-22 | 2018-07-05 | 住友金属鉱山株式会社 | Detoxification equipment and detoxification method |
| CN114981473A (en) * | 2020-06-01 | 2022-08-30 | 岩谷产业株式会社 | Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus |
| CN115028536A (en) * | 2022-06-27 | 2022-09-09 | 昆明贵金属研究所 | Preparation method of tetra-n-propyl ammonium perruthenate (VII) |
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| JP2010524672A (en) * | 2007-04-26 | 2010-07-22 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | Method for recovering ruthenium from a ruthenium-containing supported catalyst material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010524672A (en) * | 2007-04-26 | 2010-07-22 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | Method for recovering ruthenium from a ruthenium-containing supported catalyst material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014043611A (en) * | 2012-08-27 | 2014-03-13 | Asahi Pretec Corp | Method for recovering ruthenium |
| CN103725903A (en) * | 2013-12-31 | 2014-04-16 | 新疆中泰化学股份有限公司 | Mercury-containing hydrochloric acid recovery plant |
| JP2018103078A (en) * | 2016-12-22 | 2018-07-05 | 住友金属鉱山株式会社 | Detoxification equipment and detoxification method |
| CN114981473A (en) * | 2020-06-01 | 2022-08-30 | 岩谷产业株式会社 | Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus |
| CN115028536A (en) * | 2022-06-27 | 2022-09-09 | 昆明贵金属研究所 | Preparation method of tetra-n-propyl ammonium perruthenate (VII) |
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