WO2020183946A1 - Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin - Google Patents

Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin Download PDF

Info

Publication number
WO2020183946A1
WO2020183946A1 PCT/JP2020/002906 JP2020002906W WO2020183946A1 WO 2020183946 A1 WO2020183946 A1 WO 2020183946A1 JP 2020002906 W JP2020002906 W JP 2020002906W WO 2020183946 A1 WO2020183946 A1 WO 2020183946A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst metal
aqueous solution
recovering
tin
catalytic metal
Prior art date
Application number
PCT/JP2020/002906
Other languages
French (fr)
Japanese (ja)
Inventor
大介 吉井
Original Assignee
松田産業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 松田産業株式会社 filed Critical 松田産業株式会社
Publication of WO2020183946A1 publication Critical patent/WO2020183946A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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

Definitions

  • the present invention relates to a method and a recovery device for recovering a catalyst metal from an aqueous solution containing a catalyst metal coprecipitated with tin.
  • the catalyst metal When electroless plating is performed on the surface of plastic, glass, etc., it is necessary to support the catalyst metal on the surface to be plated as a pretreatment, and palladium (Pd), which is a noble metal, is selected as the catalyst metal. It is common to be done. Further, as a method of supporting the metal, a method is adopted in which the object to be plated is immersed in a catalyst solution in which a catalyst metal salt and stannous chloride are mixed, and the catalyst metal is deposited on the surface to be plated by the reducing power of tin (Sn). There is.
  • the washing water after washing contains hydrochloric acid in addition to palladium chloride and tin chloride (or a complex thereof) as main components, although it depends on the type of catalyst metal.
  • the hydrochloric acid concentration is 0.005 mol / L or less.
  • the precious metal is recovered by entrusting the liquid to a recovery company, or a precious metal recovery device is installed in the process and the recovered material adsorbed with the precious metal is outsourced to the recovery company. Is being collected.
  • the pH of the catalyst solution rises to 2 to 3
  • tin in the catalyst solution precipitates, and the precipitate also precipitates.
  • the catalyst metal also coprecipitates in the object. Therefore, in order to recover the catalyst metal in the washing water, it is necessary to recover the tin precipitate itself containing the catalyst metal, but there is a problem that filtration and sedimentation separation are difficult because the particle size of the precipitate is small and the specific gravity is small. There is. Therefore, the catalyst metal is often not recovered from the washing water, but since the catalyst metal is expensive, it is required to recover the catalyst metal in the washing liquid as well as the catalyst liquid. ..
  • Patent Document 1 describes a method in which a tin precipitate containing a catalyst metal in washing water is solid-liquid separated by a method such as centrifugation, and the precipitate is dissolved and recovered with hydrochloric acid / hydrogen peroxide solution.
  • Patent Document 2 describes a method in which a tin precipitate containing a catalyst metal in washing water is filtered using a porous filter, and the precipitate separated by backwash is decomposed into hydrochloric acid / hydrogen peroxide solution and recovered. ing.
  • Patent Documents 3 and 4 an acid is added to the washing water to adjust the pH to 0.8 to 5 mol / L to suppress the formation of tin precipitate, the pore radius is 1 nm or less, and the pore volume is 45 to 500 mm 3 /.
  • a method of passing the liquid through activated carbon which is g and recovering the liquid is described.
  • An object of the present invention is to provide a method for easily recovering a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin.
  • the catalyst metal is eluted by holding an aqueous solution containing the catalyst metal coprecipitated with tin, and the eluted catalyst metal is used. It is characterized by being separated and collected.
  • the present invention it is possible to provide a method for easily separating a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin. This makes it possible to easily recover the catalyst metal (precious metal) such as palladium in the washing water, which has been conventionally discarded.
  • a catalyst metal such as palladium coprecipitated with tin.
  • the object to be plated is immersed in a catalyst solution in which a catalyst metal salt and stannous chloride are mixed, and the catalyst metal is supported on the surface to be plated.
  • the catalyst metal precious metals Au (gold), Ag (silver), Pt (platinum), Pd (palladium), Rh (rhodium), Ir (iridium), Ru (lutenium), Os (osmium) are used. In particular, Pd is mainly used.
  • the object to be plated on which the catalyst metal is supported is immersed in washing water made of pure water or the like to wash the excess catalyst solution. Therefore, the washing water after washing contains a catalyst metal which is a noble metal.
  • the catalyst metal Since the catalyst metal is expensive, it is required to recover the catalyst metal in the washing water. However, in the washing water, the catalyst metal is co-precipitated with tin, and the precipitate has a fine particle size and a small specific gravity, so that it is filtered. And sedimentation was difficult. In such a situation, the present inventor noticed that the color of the washing water changed from light brown to transparent when the washing water containing the catalyst solution was allowed to stand overnight.
  • an embodiment of the present invention is characterized in that an aqueous solution containing a catalyst metal coprecipitated with tin is held, the catalyst metal is eluted, and the eluted catalyst metal is separated and recovered. To do.
  • the holding in the present embodiment includes not only allowing the aqueous solution to stand still, but also flowing the aqueous solution by stirring or passing the liquid.
  • only the dissolved catalyst metal can be separated and recovered by holding the catalyst metal in the precipitate until it elutes.
  • the initiation of elution varies depending on various factors such as concentration, pH, and liquid temperature, but what is important in the present invention is to retain the catalytic metal until it elutes spontaneously.
  • the concentration of the catalytic metal in the precipitate is maintained until it becomes almost zero. As shown in the examples, there are some in which elution is observed after about 24 hours and some in which elution can be confirmed after about 16 days.
  • an adsorbent such as an ion exchange resin or a chelate resin
  • the cleaning water including the catalyst metal
  • the catalyst metal eluted in the aqueous solution can be recovered with the adsorbent at any time.
  • the aqueous solution in which the catalyst metal is eluted can be put into a container in which the adsorbent is installed, and the catalyst metal can be recovered by the adsorbent.
  • tin elution with the passage of time can hardly be confirmed, and it exists as a tin precipitate.
  • This tin precipitate can be collected using a filter or the like.
  • the recovery time of the eluted catalyst metal and the recovery time of the tin precipitate are not particularly limited. It can be appropriately determined in consideration of the structure, efficiency, etc. of the recovery device.
  • a holding tank for holding the aqueous solution (washing water) in which tin and the catalyst metal are co-precipitated for a certain period of time to elute the catalyst metal, and an adsorbent such as an ion exchange resin are installed.
  • a recovery device provided with a recovery tank for recovering the catalyst metal eluted in the adsorbent can be used.
  • the recovery efficiency can be improved by installing the adsorbent in the lower part of the recovery tank and passing water by pressing it against the adsorbent using the upward flow from the water supply pipe also installed in the lower part of the recovery tank. it can.
  • a discharge pipe can be provided at the top of the recovery tank to allow the tin precipitate to overflow. Water can be supplied from the raw water tank to the recovery tank using a pump.
  • a recovery device provided with a recovery tank in which an adsorbent such as an ion exchange resin for recovering the catalyst metal is installed can be used.
  • the aqueous solution is held in the filter tank for a certain period of time to elute the catalyst metal to separate the catalyst metal and the tin precipitate, and only the separated tin precipitate is recovered by the filter.
  • the aqueous solution from which the tin precipitate has been separated and recovered can be supplied to a recovery tank, and the catalyst metal can be recovered in the recovery tank.
  • water can be supplied to each tank using a pump.
  • Example 1 An aqueous solution in which tin and palladium are co-precipitated (Pd: 1 mg / L, Sn: 125 mg / L, pH: 2 to 3) is maintained at a liquid temperature of about 18 ° C. to 23 ° C., and Pd and Pd in the aqueous solution are maintained over time.
  • the concentration of Sn was measured.
  • the concentration of Pd in the aqueous solution did not change much until the holding time was 24 hours, but after 24 hours, the concentration of Pd in the aqueous solution increased sharply (see FIG. 1). After that, when about 50 hours had passed, Pd was almost eluted.
  • Example 2 An aqueous solution in which tin and palladium are co-precipitated (Pd: 1.7 mg / L, Sn: 57 mg / L, pH: 2 to 3) is maintained at a liquid temperature of about 5 ° C to 10 ° C, and is added to the aqueous solution for each elapsed day.
  • the concentrations of Pd and Sn were measured.
  • the concentration of Pd in the aqueous solution did not change much until the retention period was about 20 days, but after about 20 days, the concentration of Pd in the aqueous solution increased sharply (see FIG. 3). After that, when about 30 days had passed, Pd was almost eluted.
  • FIG. 5 shows a specific recovery device for recovering the catalyst metal from the aqueous solution (washing water) containing the catalyst solution.
  • washing water Pd: 0.5 mg / L, Sn: 100 to 200 mg / L
  • Pd 0.5 mg / L
  • Sn 100 to 200 mg / L
  • a catalyst solution was put into the holding tank 1.
  • it was held in the holding tank 1 for about 50 hours for the purpose of elution (ionization) of Pd.
  • a container 4 recovery tank
  • the adsorbent is flowed upward from the water supply pipe 5 provided at the bottom of the recovery tank using the pump 2. The liquid was passed by pushing it up.
  • the ionized Pd was recovered by the adsorbent, while the Sn precipitate passed through the gap of the adsorbent and was discharged from the overflow pipe 6 provided on the upper side surface of the recovery tank. From the above, Pd could be selectively recovered.
  • FIG. 6 shows another specific recovery device for recovering the catalyst metal from the aqueous solution (washing water) containing the catalyst solution.
  • washing water Pd: 0.5 mg / L, Sn: 100 to 200 mg / L
  • the liquid was passed through a bag filter (filter tank 10) filled with a bag-shaped filter 9 having a retention particle diameter of 1 ⁇ m, and the bag filter 9 was retained for about 50 hours for the purpose of elution (ionization) of Pd.
  • the Sn precipitate was recovered by the bag filter 9, and the ionized Pd aqueous solution was passed through a cylinder (recovery tank 11) filled with 25 L of the adsorbent 12 in the subsequent stage in which the ionized Pd aqueous solution was arranged in series.
  • a cylinder recovery tank 11
  • the washing water is continuously passed.
  • the present invention can provide a method for easily recovering a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin. As a result, the catalyst metal (precious metal) in the washing water that has been discharged (discarded) can be recovered.
  • the present invention is particularly useful in the recycling field of recovering valuable metals from wastewater containing valuable metals discharged in the electroless plating process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for recovering a catalytic metal from an aqueous solution including a catalytic metal, the method characterized by retaining an aqueous solution including a catalytic metal co-precipitated with tin to elute the catalytic metal, and separating and recovering the eluted catalytic metal. The purpose of the present invention is to provide a method for recovering a catalytic metal easily from an aqueous solution including the catalytic metal, such as palladium, co-precipitated with tin. As a result, the catalytic metal (noble metal) in discharged (discarded) wash water can be recovered. The present invention is useful in the field of recycling for recovering valuable metals from wastewater that contains valuable metals and was discharged in an electroless plating process.

Description

錫と共沈した触媒金属含有水溶液からの触媒金属の回収方法及び回収装置Method and device for recovering catalyst metal from aqueous solution containing catalyst metal coprecipitated with tin
　本発明は、錫と共沈した触媒金属を含有する水溶液から触媒金属を回収する方法及び回収装置に関する。 The present invention relates to a method and a recovery device for recovering a catalyst metal from an aqueous solution containing a catalyst metal coprecipitated with tin.
　プラスチック、ガラス等の表面に無電解めっきを行う際には、その前処理として、触媒金属を被めっき面に担持させることが必要であり、触媒金属としては、貴金属であるパラジウム（Ｐｄ）が選定されることが一般的である。また、担持させる手法として、触媒金属塩と塩化第一錫を混合した触媒液に被めっき物を浸漬し、錫（Ｓｎ）の還元力によって被めっき面に触媒金属を析出する方法が採られている。 When electroless plating is performed on the surface of plastic, glass, etc., it is necessary to support the catalyst metal on the surface to be plated as a pretreatment, and palladium (Pd), which is a noble metal, is selected as the catalyst metal. It is common to be done. Further, as a method of supporting the metal, a method is adopted in which the object to be plated is immersed in a catalyst solution in which a catalyst metal salt and stannous chloride are mixed, and the catalyst metal is deposited on the surface to be plated by the reducing power of tin (Sn). There is.
　触媒液に浸漬して触媒金属を担持させた後は、洗浄水（主に純水）に被めっき物を浸漬することで、余剰の触媒液が洗浄される。洗浄後の洗浄水には、触媒金属の種類にもよるが、主成分として、塩化パラジウム及び塩化錫（もしくはそれらの錯体）のほか、塩酸が含まれる。また、塩酸濃度については、０．００５ｍｏｌ／Ｌ以下である。 After being immersed in the catalyst solution to support the catalyst metal, the excess catalyst solution is washed by immersing the object to be plated in cleaning water (mainly pure water). The washing water after washing contains hydrochloric acid in addition to palladium chloride and tin chloride (or a complex thereof) as main components, although it depends on the type of catalyst metal. The hydrochloric acid concentration is 0.005 mol / L or less.
　ところで、使用済みの触媒液や洗浄後の洗浄水中には、高価な触媒金属（貴金属）が含まれるため、これを回収する必要がある。使用済みの触媒液については、通常、液ごと回収業者に委託して貴金属を回収するか、あるいは、工程内に貴金属回収装置を設置して、貴金属を吸着させた回収物を回収業者に委託して回収する、ことが行われている。 By the way, since the used catalyst solution and the washing water after washing contain an expensive catalyst metal (precious metal), it is necessary to recover it. For used catalyst liquids, usually, the precious metal is recovered by entrusting the liquid to a recovery company, or a precious metal recovery device is installed in the process and the recovered material adsorbed with the precious metal is outsourced to the recovery company. Is being collected.
　一方、洗浄水中の触媒液については、１００倍程度希釈されることで、触媒液（ｐＨ＜１）のｐＨが２～３に上昇して、触媒液中の錫が沈殿し、また、その沈殿物中に触媒金属も共沈する。したがって、洗浄水中の触媒金属を回収するためには、触媒金属を含む錫沈殿物自体を回収する必要があるが、沈殿物の粒径が細かく比重が小さいため、濾過や沈降分離が困難という問題がある。そのため、洗浄水からは、触媒金属の回収が行われていないことが多いが、触媒金属は高価であることから、触媒液と同様、洗浄液中の触媒金属についても回収することが求められている。 On the other hand, when the catalyst solution in the washing water is diluted about 100 times, the pH of the catalyst solution (pH <1) rises to 2 to 3, and tin in the catalyst solution precipitates, and the precipitate also precipitates. The catalyst metal also coprecipitates in the object. Therefore, in order to recover the catalyst metal in the washing water, it is necessary to recover the tin precipitate itself containing the catalyst metal, but there is a problem that filtration and sedimentation separation are difficult because the particle size of the precipitate is small and the specific gravity is small. There is. Therefore, the catalyst metal is often not recovered from the washing water, but since the catalyst metal is expensive, it is required to recover the catalyst metal in the washing liquid as well as the catalyst liquid. ..
　洗浄水中の触媒金属を回収する方法としては、以下の技術が知られている。
　例えば、特許文献１には、洗浄水中の触媒金属を含む錫沈殿を遠心分離などの手法で固液分離して、塩酸／過酸化水素水にて沈殿を溶解し回収する方法が記載されている。
　特許文献２には、洗浄水中の触媒金属を含む錫沈殿を、多孔質フィルターを使用して濾過し、逆洗浄にて分離した沈殿を塩酸／過酸化水素水分解して回収する方法が記載されている。
　特許文献３、４には、洗浄水に酸を添加しｐＨを０．８～５ｍｏｌ／Ｌに調整して錫沈殿の生成を抑制し、細孔半径１ｎｍ以下、細孔容積４５～５００ｍｍ3／ｇである活性炭に通液して回収する方法が記載されている。 The following techniques are known as a method for recovering the catalyst metal in the washing water.
For example, Patent Document 1 describes a method in which a tin precipitate containing a catalyst metal in washing water is solid-liquid separated by a method such as centrifugation, and the precipitate is dissolved and recovered with hydrochloric acid / hydrogen peroxide solution. ..
Patent Document 2 describes a method in which a tin precipitate containing a catalyst metal in washing water is filtered using a porous filter, and the precipitate separated by backwash is decomposed into hydrochloric acid / hydrogen peroxide solution and recovered. ing.
In Patent Documents 3 and 4, an acid is added to the washing water to adjust the pH to 0.8 to 5 mol / L to suppress the formation of tin precipitate, the pore radius is 1 nm or less, and the pore volume is 45 to 500 mm 3 /. A method of passing the liquid through activated carbon which is g and recovering the liquid is described.
特開２００１－３０３１４８号公報Japanese Unexamined Patent Publication No. 2001-303148 特許第６２３６３１１号Patent No. 6236311 特開２０１７－１３３１０９号公報Japanese Unexamined Patent Publication No. 2017-133109 特開２０１７－１３３１１０号公報JP-A-2017-133110
　本発明は、錫と共沈したパラジウムをはじめとする触媒金属を含有する水溶液から、簡便に、触媒金属を回収する方法を提供することを課題とする。 An object of the present invention is to provide a method for easily recovering a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin.
　上記の課題を解決するため、本発明の一実施形態に係る触媒金属の回収方法は、錫と共沈した触媒金属を含有する水溶液を保持して触媒金属を溶出させ、溶出させた触媒金属を分離、回収することを特徴とする。 In order to solve the above problems, in the method for recovering the catalyst metal according to the embodiment of the present invention, the catalyst metal is eluted by holding an aqueous solution containing the catalyst metal coprecipitated with tin, and the eluted catalyst metal is used. It is characterized by being separated and collected.
　本発明によれば、錫と共沈したパラジウムをはじめとする触媒金属を含有する水溶液から、簡便に、触媒金属を分離する方法を提供することができる。これにより、従来は廃棄されていた洗浄水中のパラジウムなどの触媒金属（貴金属）を簡便に回収することが可能となる。 According to the present invention, it is possible to provide a method for easily separating a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin. This makes it possible to easily recover the catalyst metal (precious metal) such as palladium in the washing water, which has been conventionally discarded.
本発明の実施例１に係る経時変化によるＰｄ濃度の推移を示すグラフである。It is a graph which shows the transition of the Pd concentration by the time change which concerns on Example 1 of this invention. 本発明の実施例１に係る経時変化によるＳｎ濃度の推移を示すグラフである。It is a graph which shows the transition of Sn concentration by the time change which concerns on Example 1 of this invention. 本発明の実施例２に係る経時変化によるＰｄ濃度の推移を示すグラフである。It is a graph which shows the transition of the Pd concentration by the time change which concerns on Example 2 of this invention. 本発明の実施例２に係る経時変化によるＳｎ濃度の推移を示すグラフである。It is a graph which shows the transition of Sn concentration by the time change which concerns on Example 2 of this invention. 本発明の実施例３に係る装置概略図（その１）である。It is a schematic diagram (the 1) of the apparatus which concerns on Example 3 of this invention. 本発明の実施例４に係る装置概略図（その２）である。It is a schematic diagram (No. 2) of the apparatus which concerns on Example 4 of this invention.
　無電解めっき工程では、触媒金属塩と塩化第一錫を混合した触媒液に、被めっき物を浸漬して、被めっき面に触媒金属を担持させることが行われている。触媒金属としては貴金属であるＡｕ（金）、Ａｇ（銀）、Ｐｔ（白金）、Ｐｄ（パラジウム）、Ｒｈ（ロジウム）、Ｉｒ（イリジウム）、Ｒｕ（ルテニウム）、Ｏｓ（オスミウム）が使用され、特に、Ｐｄが主に使用される。その後、触媒金属を担持させた被めっき物は純水等からなる洗浄水に浸漬して、余剰の触媒液が洗浄される。したがって洗浄後の洗浄水には、貴金属である触媒金属が含まれることになる。 In the electroless plating step, the object to be plated is immersed in a catalyst solution in which a catalyst metal salt and stannous chloride are mixed, and the catalyst metal is supported on the surface to be plated. As the catalyst metal, precious metals Au (gold), Ag (silver), Pt (platinum), Pd (palladium), Rh (rhodium), Ir (iridium), Ru (lutenium), Os (osmium) are used. In particular, Pd is mainly used. After that, the object to be plated on which the catalyst metal is supported is immersed in washing water made of pure water or the like to wash the excess catalyst solution. Therefore, the washing water after washing contains a catalyst metal which is a noble metal.
　触媒金属は高価であることから洗浄水中の触媒金属を回収することが求められるが、洗浄水中、触媒金属は錫と共沈しており、その沈殿物は粒径が細かく比重が小さいため、濾過や沈降分離が困難であった。このような状況において、本発明者は、触媒液を含有する洗浄水を一晩静置していたところ、洗浄水の色が淡い茶褐色から透明になっていることに気が付いた。 Since the catalyst metal is expensive, it is required to recover the catalyst metal in the washing water. However, in the washing water, the catalyst metal is co-precipitated with tin, and the precipitate has a fine particle size and a small specific gravity, so that it is filtered. And sedimentation was difficult. In such a situation, the present inventor noticed that the color of the washing water changed from light brown to transparent when the washing water containing the catalyst solution was allowed to stand overnight.
　そして、該洗浄水中のＰｄ濃度を測定したところ、Ｐｄ濃度が著しく高くなっていることを確認した。このことから、本発明者は、錫と共沈したパラジウムをはじめとする触媒金属は、時間の経過とともにイオン化して溶出するとの知見が得られた。このような知見に基づき、本発明の実施形態は、錫と共沈した触媒金属を含有する水溶液を保持して、触媒金属を溶出させ、溶出させた触媒金属を分離、回収することを特徴とする。
なお、本実施形態における保持には、水溶液を静置することの他、撹拌や通液によって水溶液を流動させる場合も含むものである。 Then, when the Pd concentration in the washing water was measured, it was confirmed that the Pd concentration was remarkably high. From this, the present inventor has obtained the finding that the catalyst metal such as palladium coprecipitated with tin is ionized and eluted with the passage of time. Based on such findings, an embodiment of the present invention is characterized in that an aqueous solution containing a catalyst metal coprecipitated with tin is held, the catalyst metal is eluted, and the eluted catalyst metal is separated and recovered. To do.
The holding in the present embodiment includes not only allowing the aqueous solution to stand still, but also flowing the aqueous solution by stirring or passing the liquid.
　本発明の実施形態では、沈殿物中から触媒金属が溶出するまで保持することにより、溶け出した触媒金属のみを分離、回収することができる。溶出の開始は、濃度、ｐＨ、液温などの諸要因によって変動するが、本発明において重要なことは、触媒金属が自然に溶出するまで保持することである。好ましくは、沈殿物中の触媒金属の濃度が、ほぼゼロになるまで保持する。実施例で示すように、約２４時間後に溶出が見られるものや約１６日後になってから、溶出が確認できるものもある。 In the embodiment of the present invention, only the dissolved catalyst metal can be separated and recovered by holding the catalyst metal in the precipitate until it elutes. The initiation of elution varies depending on various factors such as concentration, pH, and liquid temperature, but what is important in the present invention is to retain the catalytic metal until it elutes spontaneously. Preferably, the concentration of the catalytic metal in the precipitate is maintained until it becomes almost zero. As shown in the examples, there are some in which elution is observed after about 24 hours and some in which elution can be confirmed after about 16 days.
　その後、水溶液（洗浄水）中に溶出させた触媒金属を分離、回収する方法としては、イオン交換樹脂やキレート樹脂などの吸着材を用いて行うことができる。例えば、該吸着材が設置された容器に洗浄後の洗浄水（触媒金属を含む）を投入し、一定時間、保持することで、水溶液中に溶出していく触媒金属を随時、吸着材で回収するか、あるいは触媒金属が溶出した水溶液を吸着材が設置された容器に投入して、触媒金属を該吸着材で回収することができる。 After that, as a method of separating and recovering the catalyst metal eluted in the aqueous solution (washing water), an adsorbent such as an ion exchange resin or a chelate resin can be used. For example, by pouring the cleaning water (including the catalyst metal) after cleaning into the container in which the adsorbent is installed and holding it for a certain period of time, the catalyst metal eluted in the aqueous solution can be recovered with the adsorbent at any time. Alternatively, the aqueous solution in which the catalyst metal is eluted can be put into a container in which the adsorbent is installed, and the catalyst metal can be recovered by the adsorbent.
　一方、錫については、時間経過による溶出はほとんど確認できず、錫沈殿物として、存在する。この錫沈殿物については、フィルターなどを用いて、捕集することができる。水溶液（洗浄水）中に触媒金属を溶出分離した後は、溶出させた触媒金属の回収時期と錫沈殿物の回収時期の先後は特に問わない。回収装置の構造、効率等を考慮して、適宜決定することができる。 On the other hand, with respect to tin, elution with the passage of time can hardly be confirmed, and it exists as a tin precipitate. This tin precipitate can be collected using a filter or the like. After the catalyst metal is eluted and separated in the aqueous solution (washing water), the recovery time of the eluted catalyst metal and the recovery time of the tin precipitate are not particularly limited. It can be appropriately determined in consideration of the structure, efficiency, etc. of the recovery device.
　具体的な回収装置としては、錫と触媒金属とが共沈した水溶液（洗浄水）を一定時間保持して触媒金属を溶出させるための保持槽と、イオン交換樹脂などの吸着材が設置され、該吸着材において溶出した触媒金属を回収するための回収槽とを備えた、回収装置を用いることができる。
　このとき、吸着材を回収槽下部に設置し、同じく回収槽下部に設置された給水管から上方流を利用して、吸着材に押しつけるようにして通水することで、回収効率を高めることができる。また、回収槽の上部に排出管を設けて、錫沈殿物をオーバーフローさせることができる。なお、原水槽から回収槽へはポンプを用いて給水することができる。 As a specific recovery device, a holding tank for holding the aqueous solution (washing water) in which tin and the catalyst metal are co-precipitated for a certain period of time to elute the catalyst metal, and an adsorbent such as an ion exchange resin are installed. A recovery device provided with a recovery tank for recovering the catalyst metal eluted in the adsorbent can be used.
At this time, the recovery efficiency can be improved by installing the adsorbent in the lower part of the recovery tank and passing water by pressing it against the adsorbent using the upward flow from the water supply pipe also installed in the lower part of the recovery tank. it can. In addition, a discharge pipe can be provided at the top of the recovery tank to allow the tin precipitate to overflow. Water can be supplied from the raw water tank to the recovery tank using a pump.
　また、他の具体的な回収装置としては、錫と触媒金属とが共沈した水溶液（洗浄水）を貯蔵するための保管槽と、錫沈殿物を回収するためのフィルターが設けられたフィルター槽と、触媒金属を回収するためのイオン交換樹脂などの吸着材が設置された回収槽とを備えた、回収装置を用いることができる。
　当該装置においては、前記フィルター槽において水溶液を一定時間保持して触媒金属を溶出させて触媒金属と錫沈殿物とを分離し、分離した錫沈殿物のみを該フィルターにて回収し、次に、錫沈殿物が分離回収された水溶液を回収槽に給水し、該回収槽にて、触媒金属を回収することができる。なお、先の装置と同様、それぞれの槽へは、ポンプを用いて給水することができる。 Further, as other specific recovery devices, a storage tank for storing an aqueous solution (washing water) in which tin and a catalyst metal are co-settled, and a filter tank provided with a filter for recovering tin precipitates. And a recovery device provided with a recovery tank in which an adsorbent such as an ion exchange resin for recovering the catalyst metal is installed can be used.
In the apparatus, the aqueous solution is held in the filter tank for a certain period of time to elute the catalyst metal to separate the catalyst metal and the tin precipitate, and only the separated tin precipitate is recovered by the filter. The aqueous solution from which the tin precipitate has been separated and recovered can be supplied to a recovery tank, and the catalyst metal can be recovered in the recovery tank. As with the previous device, water can be supplied to each tank using a pump.
　次に、本発明の実施例等について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本発明はこれらの実施例に制限される必要はなく、明細書の記載される技術思想の範囲で解釈されるべきものである。 Next, examples and the like of the present invention will be described. It should be noted that the following examples are merely representative examples, and the present invention need not be limited to these examples and should be interpreted within the scope of the technical idea described in the specification. It is a thing.
（実施例１）
　錫とパラジウムが共沈した水溶液（Ｐｄ：１ｍｇ／Ｌ、Ｓｎ：１２５ｍｇ／Ｌ、ｐＨ：２～３）を、液温約１８℃～２３℃で保持し、経過時間ごとに水溶液中のＰｄ及びＳｎの濃度を計測した。その結果、保持時間が２４時間までは、水溶液中のＰｄの濃度はあまり変化がなかったが、２４時間以降、水溶液中のＰｄの濃度が急激に上昇した（図１参照）。その後、約５０時間経過した時点では、Ｐｄはほとんど溶出していた。一方、Ｓｎについては、溶出せず、沈殿物として残留していた（図２参照）。Ｐｄが溶出した水溶液を陽イオン交換樹脂やキレート樹脂などの吸着材を用いて、Ｐｄを吸着回収した。 (Example 1)
An aqueous solution in which tin and palladium are co-precipitated (Pd: 1 mg / L, Sn: 125 mg / L, pH: 2 to 3) is maintained at a liquid temperature of about 18 ° C. to 23 ° C., and Pd and Pd in the aqueous solution are maintained over time. The concentration of Sn was measured. As a result, the concentration of Pd in the aqueous solution did not change much until the holding time was 24 hours, but after 24 hours, the concentration of Pd in the aqueous solution increased sharply (see FIG. 1). After that, when about 50 hours had passed, Pd was almost eluted. On the other hand, Sn did not elute and remained as a precipitate (see FIG. 2). The aqueous solution in which Pd was eluted was adsorbed and recovered using an adsorbent such as a cation exchange resin or a chelate resin.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例２）
　錫とパラジウムが共沈した水溶液（Ｐｄ：１．７ｍｇ／Ｌ、Ｓｎ：５７ｍｇ／Ｌ、ｐＨ：２～３）を、液温約５℃～１０℃で保持し、経過日数ごとに水溶液中のＰｄ及びＳｎの濃度を計測した。その結果、保持日数が約２０日までは、水溶液中のＰｄの濃度はあまり変化がなかったが、約２０日経過後、水溶液中のＰｄの濃度が急激に上昇した（図３参照）。その後、約３０日経過した時点ではＰｄはほとんど溶出していた。一方、Ｓｎについては、溶出せず、沈殿物として残留していた（図４参照）。Ｐｄが溶出した水溶液を陽イオン交換樹脂やキレート樹脂などの吸着材を用いて、Ｐｄを吸着回収した。 (Example 2)
An aqueous solution in which tin and palladium are co-precipitated (Pd: 1.7 mg / L, Sn: 57 mg / L, pH: 2 to 3) is maintained at a liquid temperature of about 5 ° C to 10 ° C, and is added to the aqueous solution for each elapsed day. The concentrations of Pd and Sn were measured. As a result, the concentration of Pd in the aqueous solution did not change much until the retention period was about 20 days, but after about 20 days, the concentration of Pd in the aqueous solution increased sharply (see FIG. 3). After that, when about 30 days had passed, Pd was almost eluted. On the other hand, Sn did not elute and remained as a precipitate (see FIG. 4). The aqueous solution in which Pd was eluted was adsorbed and recovered using an adsorbent such as a cation exchange resin or a chelate resin.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（実施例３）
　触媒液を含む水溶液（洗浄水）から触媒金属を回収するための、具体的な回収装置を図５に示す。まず、触媒液を含む洗浄水（Ｐｄ：０．５ｍｇ／Ｌ、Ｓｎ：１００～２００ｍｇ／Ｌ）を保持槽１に投入した。次に、保持槽１にて、Ｐｄの溶出（イオン化）目的で約５０時間保持した。次に、吸着材３を２０Ｌほど充填した約２００Ｌの容器４（回収槽）に、ポンプ２を用いて、回収槽底部に設けられた給水管５から、該水溶液を上方流にて吸着材を押し上げるようにして、通液させた。イオン化したＰｄは該吸着材にて回収され、一方、Ｓｎ沈殿物は吸着材の隙間を通り抜け、回収槽の上部側面に設けられたオーバーフロー用の配管６より排出した。以上により、Ｐｄを選択的に回収することができた。 (Example 3)
FIG. 5 shows a specific recovery device for recovering the catalyst metal from the aqueous solution (washing water) containing the catalyst solution. First, washing water (Pd: 0.5 mg / L, Sn: 100 to 200 mg / L) containing a catalyst solution was put into the holding tank 1. Next, it was held in the holding tank 1 for about 50 hours for the purpose of elution (ionization) of Pd. Next, in a container 4 (recovery tank) of about 200 L filled with the adsorbent 3 by about 20 L, the adsorbent is flowed upward from the water supply pipe 5 provided at the bottom of the recovery tank using the pump 2. The liquid was passed by pushing it up. The ionized Pd was recovered by the adsorbent, while the Sn precipitate passed through the gap of the adsorbent and was discharged from the overflow pipe 6 provided on the upper side surface of the recovery tank. From the above, Pd could be selectively recovered.
（実施例４）
　触媒液を含む水溶液（洗浄水）から触媒金属を回収するための、他の具体的な回収装置を図６に示す。まず、触媒液を含む洗浄水（Ｐｄ：０．５ｍｇ／Ｌ、Ｓｎ：１００～２００ｍｇ／Ｌ）を保管槽７に投入した。次に、保持粒子径１μｍのバッグ状のフィルター９を充填したバッグフィルター（フィルター槽１０）に通液させて、バッグフィルター９にてＰｄの溶出（イオン化）目的で、約５０時間保持した。次に、バッグフィルター９でＳｎの沈殿物を回収すると共に、イオン化したＰｄ水溶液を、直列配置させた後段の、吸着材１２を２５Ｌ充填したボンベ（回収槽１１）を通液させた。これにより、ＰｄとＳｎをそれぞれ分離、回収できた。なお、この回収装置では、洗浄水を連続的に通液させている。 (Example 4)
FIG. 6 shows another specific recovery device for recovering the catalyst metal from the aqueous solution (washing water) containing the catalyst solution. First, washing water (Pd: 0.5 mg / L, Sn: 100 to 200 mg / L) containing a catalyst solution was put into the storage tank 7. Next, the liquid was passed through a bag filter (filter tank 10) filled with a bag-shaped filter 9 having a retention particle diameter of 1 μm, and the bag filter 9 was retained for about 50 hours for the purpose of elution (ionization) of Pd. Next, the Sn precipitate was recovered by the bag filter 9, and the ionized Pd aqueous solution was passed through a cylinder (recovery tank 11) filled with 25 L of the adsorbent 12 in the subsequent stage in which the ionized Pd aqueous solution was arranged in series. As a result, Pd and Sn could be separated and recovered, respectively. In this recovery device, the washing water is continuously passed.
　本発明は、錫と共沈したパラジウムをはじめとする触媒金属を含有する水溶液から、簡便に、触媒金属を回収する方法を提供することができる。これにより、これまで排出（廃棄）されていた洗浄水中の触媒金属（貴金属）を回収することができる。本発明は特に、無電解めっき工程で排出される有価金属を含有する排水から、該有価金属を回収するリサイクル分野において有用である。 The present invention can provide a method for easily recovering a catalyst metal from an aqueous solution containing a catalyst metal such as palladium coprecipitated with tin. As a result, the catalyst metal (precious metal) in the washing water that has been discharged (discarded) can be recovered. The present invention is particularly useful in the recycling field of recovering valuable metals from wastewater containing valuable metals discharged in the electroless plating process.
１　保持槽（洗浄水原水槽）
２　洗浄水送液ポンプ
３　吸着材
４　回収槽（吸着材充填槽）
５　給水管
６　排出管
７　保管槽（洗浄水原水槽）
８　洗浄水送液ポンプ
９　フィルター（フィルターエレメント）
１０　フィルター槽（フィルターハウジング）
１１　回収槽（吸着充填ボンベ）
１２　吸着材
　 1 Retention tank (washing water raw water tank)
2 Washing water pump 3 Adsorbent 4 Recovery tank (adsorbent filling tank)
5 Water supply pipe 6 Discharge pipe 7 Storage tank (washing water raw water tank)
8 Washing water pump 9 Filter (filter element)
10 Filter tank (filter housing)
11 Recovery tank (adsorption-filled cylinder)
12 Adsorbent

Claims (6)

  1. 　錫と共沈した触媒金属を含有する水溶液を保持して触媒金属を溶出させ、溶出させた触媒金属を分離、回収することを特徴とする触媒金属含有水溶液からの触媒金属の回収方法。 A method for recovering a catalyst metal from an aqueous solution containing a catalyst metal, which comprises holding an aqueous solution containing a catalyst metal co-precipitated with tin, eluting the catalyst metal, and separating and recovering the eluted catalyst metal.
  2. 　前記触媒金属が貴金属であることを特徴とする請求項１記載の触媒金属含有水溶液からの触媒金属の回収方法。 The method for recovering a catalyst metal from a catalyst metal-containing aqueous solution according to claim 1, wherein the catalyst metal is a noble metal.
  3. 　錫と触媒金属とが共沈した水溶液を一定時間保持して触媒金属を溶出させるための保持槽と、吸着剤が設置され、該吸着剤によって溶出した触媒金属を回収するための回収槽と、を備えた触媒金属含有水溶液からの触媒金属の回収装置。 A holding tank for holding the aqueous solution in which tin and the catalyst metal are co-precipitated for a certain period of time to elute the catalyst metal, and a recovery tank in which an adsorbent is installed and the catalyst metal eluted by the adsorbent is recovered. A device for recovering a catalyst metal from a catalyst metal-containing aqueous solution.
  4. 　前記回収槽において、吸着槽を回収槽下部に設置し、回収槽下部に設置された給水管から上方流を利用して、吸着材と押し付けるように通水することを特徴とする請求項３記載の触媒金属含有水溶液からの触媒金属の回収装置。 The third aspect of the present invention, wherein the adsorption tank is installed in the lower part of the recovery tank, and water is passed from the water supply pipe installed in the lower part of the recovery tank so as to be pressed against the adsorbent by using an upward flow. A device for recovering a catalyst metal from an aqueous solution containing a catalyst metal.
  5. 　前記回収層において、回収槽上部に排出管を設けて、錫沈殿物をオーバーフローさせることを特徴とする請求項３又は４記載の触媒金属含有水溶液からの触媒金属の回収装置。 The device for recovering a catalyst metal from a catalyst metal-containing aqueous solution according to claim 3 or 4, wherein a discharge pipe is provided in the upper part of the recovery tank in the recovery layer to overflow the tin precipitate.
  6. 　錫と触媒金属とが共沈した水溶液を一定時間保持して触媒金属と錫沈殿物とを分離し、分離した錫沈殿物をフィルターにて回収するフィルター槽と、錫沈殿物が分離回収された水溶液を給水し、吸着材によって触媒金属を回収するための回収槽と、を備えた触媒金属含有水溶液からの触媒金属の回収装置。
    　     A filter tank in which the aqueous solution in which tin and the catalyst metal were co-precipitated was held for a certain period of time to separate the catalyst metal and the tin precipitate, and the separated tin precipitate was recovered by a filter, and the tin precipitate were separated and recovered. A device for recovering a catalyst metal from a catalyst metal-containing aqueous solution, comprising a recovery tank for supplying an aqueous solution and recovering the catalyst metal with an adsorbent.
PCT/JP2020/002906 2019-03-14 2020-01-28 Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin WO2020183946A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019046632A JP6653778B1 (en) 2019-03-14 2019-03-14 Method and apparatus for recovering catalytic metal from aqueous solution containing catalytic metal co-precipitated with tin
JP2019-046632 2019-03-14

Publications (1)

Publication Number Publication Date
WO2020183946A1 true WO2020183946A1 (en) 2020-09-17

Family

ID=69624530

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/002906 WO2020183946A1 (en) 2019-03-14 2020-01-28 Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin

Country Status (3)

Country Link
JP (1) JP6653778B1 (en)
TW (1) TWI718865B (en)
WO (1) WO2020183946A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021117385A1 (en) * 2019-12-14 2021-06-17 松田産業株式会社 Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6411928A (en) * 1987-07-03 1989-01-17 Miyama Co Ltd Recovery of tin from waste liquid of catalyst
JP2001131652A (en) * 1999-10-28 2001-05-15 Kawasaki Kasei Chem Ltd Method for separating and recovering palladium
JP2001303148A (en) * 2000-04-20 2001-10-31 Hitachi Chem Co Ltd Method for treating waste water containing palladium
US20020119085A1 (en) * 2000-12-22 2002-08-29 Kinetico Incorporated Process for recovering palladium from a solution
JP2002326821A (en) * 2001-04-27 2002-11-12 Kawasaki Kasei Chem Ltd Method for separating and recovering palladium
JP2003147448A (en) * 2001-11-09 2003-05-21 Kawasaki Kasei Chem Ltd Method of recovering palladium
JP2006061764A (en) * 2004-08-24 2006-03-09 Univ Waseda Waste water treating method and waste water treating apparatus
CN107267762A (en) * 2017-07-01 2017-10-20 励福(江门)环保科技股份有限公司 A kind of method of Palladium recovery in palladium activation waste water
JP2018525220A (en) * 2015-08-19 2018-09-06 マクダーミッド エンソン インコーポレイテッド System and method for recovering catalytic noble metals from aqueous galvanic processing solutions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6411928A (en) * 1987-07-03 1989-01-17 Miyama Co Ltd Recovery of tin from waste liquid of catalyst
JP2001131652A (en) * 1999-10-28 2001-05-15 Kawasaki Kasei Chem Ltd Method for separating and recovering palladium
JP2001303148A (en) * 2000-04-20 2001-10-31 Hitachi Chem Co Ltd Method for treating waste water containing palladium
US20020119085A1 (en) * 2000-12-22 2002-08-29 Kinetico Incorporated Process for recovering palladium from a solution
JP2002326821A (en) * 2001-04-27 2002-11-12 Kawasaki Kasei Chem Ltd Method for separating and recovering palladium
JP2003147448A (en) * 2001-11-09 2003-05-21 Kawasaki Kasei Chem Ltd Method of recovering palladium
JP2006061764A (en) * 2004-08-24 2006-03-09 Univ Waseda Waste water treating method and waste water treating apparatus
JP2018525220A (en) * 2015-08-19 2018-09-06 マクダーミッド エンソン インコーポレイテッド System and method for recovering catalytic noble metals from aqueous galvanic processing solutions
CN107267762A (en) * 2017-07-01 2017-10-20 励福(江门)环保科技股份有限公司 A kind of method of Palladium recovery in palladium activation waste water

Also Published As

Publication number Publication date
TWI718865B (en) 2021-02-11
JP6653778B1 (en) 2020-02-26
JP2020146633A (en) 2020-09-17
TW202035713A (en) 2020-10-01

Similar Documents

Publication Publication Date Title
RU2386709C1 (en) Separation and exrtaction method of precious metals
WO2020183946A1 (en) Method and device for recovering catalytic metal from aqueous solution including catalytic metal coprecipitated with tin
JP2012126611A (en) Method for recovering selenium from copper electrolysis slime
EP1314788B1 (en) A method for recovering catalytic metals using a porous metal filter
US6800111B2 (en) Method for recovering catalytic metals
JP7197729B2 (en) Method and apparatus for recovering catalytic metal from aqueous solution containing catalytic metal coprecipitated with tin
WO2023097923A1 (en) Low-cost reducing agent for selective precipitation of noble metal ions
JP2010174336A (en) METHOD OF RECOVERING Ru AND/OR Ir FROM SOLUTION CONTAINING PLATINUM GROUP
JP4169640B2 (en) Method for recovering precious metals in solution
US3502434A (en) Process and apparatus for removing mercury from caustic soda solutions
JP3896423B2 (en) Method for recovering palladium from palladium-containing liquid
JP6205290B2 (en) Method for recovering gold or silver from cyanic waste liquid containing gold or silver
WO2020113325A1 (en) A method and a system for gold recovery from halogen extraction treatment
JP6933151B2 (en) How to recover selenium from copper electrolytic slime
JP5810639B2 (en) Method and apparatus for treating selenium-containing water
JPH0533071A (en) Method for separating and refining rhodium from aqueous solution
CN114481229B (en) Precious metal recovery method for precious metal refining wastewater
JP4885149B2 (en) Method for separating and recovering precious metals
KR20100002481U (en) Recovery of palladium from waste solution of palladium plating
JP5992796B2 (en) Method for separating and recovering precious metals
JP2013237918A (en) Bismuth adsorption column, bismuth recovering facility and bismuth recovering method
JP2003147448A (en) Method of recovering palladium
JP2024081069A (en) Valuable metal recovery device, and method of operating valuable metal recovery device
CN111254288A (en) Method and system for recovering gold from halogen extraction treatment substance
JPS59206019A (en) Apparatus for supplying and filtering corrosive liquid

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20768252

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20768252

Country of ref document: EP

Kind code of ref document: A1