WO2014156300A1 - Procédé de récupération de métaux précieux utilisant un système de solvant organique qui contient un halogénure - Google Patents
Procédé de récupération de métaux précieux utilisant un système de solvant organique qui contient un halogénure Download PDFInfo
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- WO2014156300A1 WO2014156300A1 PCT/JP2014/052415 JP2014052415W WO2014156300A1 WO 2014156300 A1 WO2014156300 A1 WO 2014156300A1 JP 2014052415 W JP2014052415 W JP 2014052415W WO 2014156300 A1 WO2014156300 A1 WO 2014156300A1
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- solvent system
- copper
- gold
- noble metal
- halide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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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
Definitions
- the present invention relates to a method for dissolving and recovering a noble metal, and a solvent system for use in the method.
- metal recycling from used products consists of separation and purification by smelting after collecting, dismantling, crushing, and physically selecting objects.
- smelting includes a dry method using melting and volatilization at high temperature and a wet method in which metal is dissolved in an aqueous solution system.
- the dry method is used for large-scale operations, and the wet method is said to be suitable for small-scale operations because it allows precise separation.
- noble metals such as gold
- powerful substances such as strong acid, chlorine gas, and cyanide aqueous solution are used, so a certain amount of capital investment is required, and the environmental burden due to waste liquid etc. large.
- the present inventors can dissolve and precipitate the target noble metal in a relatively short time by using an organic solvent system containing copper halide. As a result, the present invention has been completed. Furthermore, it has also been found that the noble metal can be precipitated by simply adding a small amount of water to the solution in which the noble metal is dissolved, thereby achieving a system that can reuse the solvent from which the water has been separated.
- a method for recovering a noble metal comprising the step (B) of (2) The method according to (1) above, wherein the copper halide is selected from copper (I) bromide or copper (II) bromide; (3) The method according to (1) or (2) above, wherein the aprotic polar organic solvent is selected from dimethyl sulfoxide, dimethylformamide, acetone, acetonitrile, tetrahydrofuran, propylene carbonate, or a mixture thereof; (4) The method according to any one of (1) to (3) above, wherein the solvent system further comprises a succinimide compound; (5) The method according to any one of (1) to (3) above, wherein the solvent system further comprises sodium halide or potassium halide; (6) The
- the method according to (6) further comprising the step (C) of obtaining a system; (8) The method according to (6) or (7), wherein the pH of the reducing agent water is 4 or less; (9) The method according to any one of (1) to (8), wherein the noble metal is selected from gold, palladium, silver, or platinum.
- the invention further provides: (10) A solvent system containing copper halide and an aprotic polar organic solvent used for dissolving and recovering noble metals; (11) The solvent system according to (10) above, wherein the copper halide is selected from copper (I) bromide or copper (II) bromide; (12) The solvent system according to (10) or (11) above, wherein the aprotic polar organic solvent is selected from dimethyl sulfoxide, dimethylformamide, acetone, acetonitrile, tetrahydrofuran, propylene carbonate or a mixture thereof; (13) The solvent system according to any one of (10) to (12), further comprising a succinimide compound; (14) The solvent system according to any one of the above (10) to (12), further comprising sodium halide or potassium halide; (15) The solvent system according to any one of (10) to (14), wherein the noble metal is selected from gold, palladium, silver, or platinum.
- the present invention it is possible to recover the noble metal in a short time and with very high efficiency by a simple procedure.
- the noble metal can be precipitated simply by adding water to the solution in which the noble metal is dissolved, it is revolutionary in that it is not necessary to use an organic compound for reducing and precipitating the noble metal.
- it can be reused again as a solvent system for precious metal dissolution, which is not only economical, but also minimizes wastewater treatment. It has the advantage that an environmentally conscious process that can be retained is achievable.
- the progress of the oxidation-reduction reaction can be visually recognized by the change in the color of the solution due to the coloration of the copper ions used, etc., and the mild low temperature of around 70 degrees without using a deleterious substance in the solvent system. Since the treatment can be performed under the conditions, it is more practical than the conventional technology in that it can be easily operated.
- FIG. 1 is a graph showing the time dependence of the amount of pure gold dissolved in a DMSO solution containing CuBr 2 .
- FIG. 2 is a graph showing the time dependence of the amount of pure gold dissolved in a DMSO solution containing CuBr (0.5 mmol) and succinimide (0 to 20 mmol).
- FIG. 3 is a graph showing the time dependence of the amount of pure gold dissolved in a DMSO solution containing CuBr (2.5 mmol) and succinimide (0 to 20 mmol).
- FIG. 4 is a graph showing the time dependence of the amount of pure gold dissolved in a DMSO solution containing CuBr (0.5 to 2.0 mmol) and succinimide (10 mmol).
- FIG. 5 is a graph showing the time dependency of the amount of palladium dissolved in a DMSO solution containing CuBr (0.5 to 2.5 mmol) and succinimide (10 mmol).
- Preferred examples of the noble metal to be collected include gold, palladium, silver, and platinum, but other transition metals or so-called rare metals can also be collected.
- the recovery method of the present invention includes performing an arbitrary pretreatment step known in the technical field such as removing a polymer member on an electronic component containing a noble metal before performing the step A). Can be. Similarly, after performing the above-mentioned step B), it may be included to collect the precious metal deposited and further purify the precious metal by any method known in the art.
- the solvent system used in the above step A) is for dissolving a noble metal, and is typically an organic solvent containing copper halide.
- the configuration of the solvent system will be described below.
- the organic solvent is not particularly limited as long as it can dissolve a noble metal ion (gold ion or the like) generated by the oxidation-reduction reaction with copper halide, but a hydrophilic organic solvent is preferable and has a polarity.
- a protic organic solvent is preferred.
- examples of such aprotic polar organic solvents include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, acetonitrile, tetrahydrofuran (THF), dimethylacetamide, methyl acetate, ethyl acetate, butyl acetate, propyl acetate. And propylene carbonate. It can also be set as the mixed solvent containing these 2 or more types. Of these, DMSO is particularly preferred.
- the copper halide used in the present invention is copper fluoride, copper chloride, copper bromide, or copper iodide, and can be a monovalent or divalent salt, respectively.
- Preferred is copper (I) bromide (CuBr) or copper (II) bromide (CuBr 2 ).
- the noble metal to be collected is gold and palladium
- these copper bromides are suitable.
- other metal salts iron chloride
- FeCl 3 FeCl 3
- the amount of the copper halide contained in the solvent system increases as the amount of the noble metal dissolved increases. Typically, it is 50 mmol / L or more, preferably 100 mmol / L or more, more preferably 200 mmol / L or more. It is.
- the solvent system used in the present invention can contain a succinimide compound or an alkali metal halide as an auxiliary component for the purpose of further increasing the dissolution rate and amount of the noble metal.
- the succinimide compound may also include a succinimide (succinimide) having an arbitrary substituent and a succinimide derivative known in the art.
- the alkali metal halide is preferably sodium halide or potassium halide.
- the type of halogen is preferably one that dissociates in a solvent to produce the same halogen anion as the copper halide (that is, sodium bromide or potassium bromide in the case of copper bromide).
- the content of these additional components in the solvent system is not particularly limited, but it is used in the range of 0.5 to 10 times, preferably 2 to 5 times the concentration in the copper bromide solution. be able to.
- the reducing agent added in step B) in the recovery method of the present invention is a reagent for selectively precipitating and recovering noble metal ions dissolved in the solution in step A).
- a reagent for selectively precipitating and recovering noble metal ions dissolved in the solution in step A Preferably, water, ascorbic acid (L-ascorbic acid), sodium citrate or sodium borohydride (NaBH 4 ), but not limited thereto, among the reducing agents well known in the art. An appropriate one can be used instead.
- water is preferable to use water as the reducing agent in step B). Even if water is mixed with the above organic solvent, it can be easily removed by separation means such as separation of water after precipitation of the noble metal or volatilization of water by heating the solution. Therefore, it is possible to reuse the solvent system.
- separation means well known in the art for removing water from the organic solvent (for example, distillation and the like) can be used.
- the amount of water added is preferably in the range of 2 to 40 mL with respect to 10 mL of the solvent system from the viewpoint of the amount required for precipitating the precious metal and the efficiency of water removal for reusing the solvent system. ⁇ 20 mL is more preferred.
- the pH of the water is preferably 4 or less, more preferably 3 or less, and most preferably about 1.
- the pH can be appropriately adjusted by adding an acid such as sulfuric acid or hydrochloric acid. By setting it as this pH range, when using water as a reducing agent, the amount of undesirable precipitation of copper, other metals, etc. can be suppressed, and only the target gold can be efficiently precipitated.
- the recovery method of the present invention removes the water contained in the solvent system after depositing and recovering the noble metal in the above step (B), and again in the above step ( It further comprises a step (C) of obtaining a solvent system that can be used in A). Then, by repeating the steps (A) to (C), a recovery cycle in which solvent-based waste liquid is suppressed can be carried out.
- the experimental conditions are as follows. In 10ml of DMSO, and using copper bromide (II) (CuBr 2) a 223 mg (1 mmol) and a solvent system having dissolved therein 446 mg (2 mmol). A solvent system containing 2 mmol each of potassium bromide or sodium bromide was prepared. About 235 mg (1.2 mmol) of a gold fine wire ( ⁇ 0.2 mm) was used. The solution temperature was 70 ° C.
- FIG. 1 shows the time dependency of the dissolved amount of pure gold obtained in each solvent composition.
- CuBr 2 used here is easily soluble in water, noble metals such as gold were not dissolved at all in a system using water as a solvent. Therefore, the above result is It shows that it is possible to effectively dissolve noble metals such as gold by using a combination of CuBr 2 and DMSO which is an aprotic polar organic solvent.
- FIG. 2 shows the time dependence of the dissolved amount of pure gold when CuBr is kept constant at 0.5 mmol with respect to 10 ml of DMSO and succinimide is changed from 0 to 20 mmol.
- FIG. 3 shows the time dependence of the dissolved amount of pure gold when CuBr is kept constant at 2.5 mmol and succinimide is changed from 0 to 20 mmol.
- the dissolution amount was saturated at around 0.3 mmol, whereas when the succinimide was added, it was confirmed that the dissolution amount increased about twice.
- FIG. 4 shows the time dependency of the dissolved amount of pure gold when succinimide is kept constant at 10 mmol and CuBr is changed from 0 to 2.0 mmol.
- FIG. 5 shows the time dependency of the amount of dissolved palladium when succinimide is kept constant at 10 mmol and CuBr is changed from 0.5 to 2.5 mmol.
- the experimental conditions used are as follows. In 10ml of DMSO, and using copper bromide (II) (CuBr 2) a solvent system having dissolved therein 446 mg (2 mmol). A solvent system containing 1 mmol of potassium bromide was prepared. About 235 mg (1.2 mmol) of a gold fine wire ( ⁇ 0.2 mm) was added to the solution and dissolved at 70 ° C. for 24 hours. Thereafter, water was added to the solvent system in which gold was dissolved, and the gold deposited was filtered. The weight of the resulting precipitate was weighed, and the weight of gold and other components in the precipitate was quantitatively analyzed by ICP-AES method to determine the amount of gold deposited and the recovery rate. The results are shown in Table 2. The obtained results are shown in Table 3.
- the amount of gold dissolved was approximately 200 mg for all samples.
- the amount of precipitated gold was about 100 mg and the recovery rate was about 50%.
- the gold recovery rate was close to 90%. Even if the amount of water added was increased, the gold recovery rate was maintained at about 80%.
- SEM scanning electron microscope
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Abstract
Priority Applications (3)
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KR1020157022470A KR102156227B1 (ko) | 2013-03-27 | 2014-02-03 | 할로겐화구리 함유 유기 용매계를 이용한 귀금속의 회수 방법 |
CN201480012943.4A CN105026583A (zh) | 2013-03-27 | 2014-02-03 | 使用含卤化铜有机溶剂体系的贵金属回收方法 |
JP2015508138A JP6196662B2 (ja) | 2013-03-27 | 2014-02-03 | ハロゲン化銅含有有機溶媒系を用いた貴金属の回収方法 |
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JP2013066833 | 2013-03-27 | ||
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JP2013-127085 | 2013-06-18 |
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PCT/JP2014/052415 WO2014156300A1 (fr) | 2013-03-27 | 2014-02-03 | Procédé de récupération de métaux précieux utilisant un système de solvant organique qui contient un halogénure |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105154678A (zh) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | 一种废旧手机电子元件的高效环保提金方法 |
JP2020045543A (ja) * | 2018-09-21 | 2020-03-26 | 国立大学法人千葉大学 | 黄銅鉱からの銅の回収方法及びその回収方法に用いる溶媒系 |
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CN108179278B (zh) * | 2017-12-21 | 2019-09-20 | 浙江理工大学 | 一种贵金属提取液、制备方法及其应用 |
CN114807611A (zh) * | 2022-04-18 | 2022-07-29 | 上海第二工业大学 | 一种温和剥离电路板金镀层和分离回收基板中金属/非金属组分的方法 |
CN114807612A (zh) * | 2022-04-18 | 2022-07-29 | 上海第二工业大学 | 一种利用乙腈-无水氯化盐体系选择性回收固体废弃物中贵金属钯的方法 |
CN114807613A (zh) * | 2022-04-18 | 2022-07-29 | 上海第二工业大学 | 一种极性非质子溶剂反应体系选择性回收固体废物中贵金属金的方法 |
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JPH03249143A (ja) * | 1990-02-28 | 1991-11-07 | Tanaka Kikinzoku Kogyo Kk | ロジウムの分離回収方法 |
JPH04107230A (ja) * | 1990-08-28 | 1992-04-08 | Agency Of Ind Science & Technol | 鉱石から金及び銀の抽出方法 |
JPH073351A (ja) * | 1993-06-18 | 1995-01-06 | Agency Of Ind Science & Technol | 金の精製方法 |
JP2005008922A (ja) * | 2003-06-17 | 2005-01-13 | Japan Science & Technology Agency | 金又は白金を担持した金属水酸化物の生成方法及びこれを用いた金又は白金の回収方法 |
JP2005154892A (ja) * | 2003-10-27 | 2005-06-16 | Mitsubishi Chemicals Corp | 貴金属の溶解液及びこの溶解液を用いた貴金属の溶解・回収方法 |
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KR0145346B1 (ko) * | 1994-06-10 | 1998-08-17 | 케네스 앤. 한 | 할로겐 염을 이용하여 광물 또는 다른 귀금속 함유물질에서 귀금속을 추출하는 방법 |
CN101812591B (zh) * | 2009-02-20 | 2012-04-04 | 国立云林科技大学 | 废电路板的金、铜、硫酸铜、氯化铜废液回收方法 |
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- 2014-02-03 WO PCT/JP2014/052415 patent/WO2014156300A1/fr active Application Filing
- 2014-02-03 KR KR1020157022470A patent/KR102156227B1/ko active IP Right Grant
- 2014-02-03 CN CN201480012943.4A patent/CN105026583A/zh active Pending
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Patent Citations (5)
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JPH03249143A (ja) * | 1990-02-28 | 1991-11-07 | Tanaka Kikinzoku Kogyo Kk | ロジウムの分離回収方法 |
JPH04107230A (ja) * | 1990-08-28 | 1992-04-08 | Agency Of Ind Science & Technol | 鉱石から金及び銀の抽出方法 |
JPH073351A (ja) * | 1993-06-18 | 1995-01-06 | Agency Of Ind Science & Technol | 金の精製方法 |
JP2005008922A (ja) * | 2003-06-17 | 2005-01-13 | Japan Science & Technology Agency | 金又は白金を担持した金属水酸化物の生成方法及びこれを用いた金又は白金の回収方法 |
JP2005154892A (ja) * | 2003-10-27 | 2005-06-16 | Mitsubishi Chemicals Corp | 貴金属の溶解液及びこの溶解液を用いた貴金属の溶解・回収方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105154678A (zh) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | 一种废旧手机电子元件的高效环保提金方法 |
JP2020045543A (ja) * | 2018-09-21 | 2020-03-26 | 国立大学法人千葉大学 | 黄銅鉱からの銅の回収方法及びその回収方法に用いる溶媒系 |
JP7194975B2 (ja) | 2018-09-21 | 2022-12-23 | 国立大学法人千葉大学 | 黄銅鉱からの銅の回収方法及びその回収方法に用いる溶媒系 |
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KR20150136056A (ko) | 2015-12-04 |
JP6196662B2 (ja) | 2017-09-13 |
CN105026583A (zh) | 2015-11-04 |
KR102156227B1 (ko) | 2020-09-15 |
JPWO2014156300A1 (ja) | 2017-02-16 |
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