[go: up one dir, main page]

WO2015152457A1 - Procédé de séparation et de récupération d'argent et d'étain à partir de boue d'anode - Google Patents

Procédé de séparation et de récupération d'argent et d'étain à partir de boue d'anode Download PDF

Info

Publication number
WO2015152457A1
WO2015152457A1 PCT/KR2014/003892 KR2014003892W WO2015152457A1 WO 2015152457 A1 WO2015152457 A1 WO 2015152457A1 KR 2014003892 W KR2014003892 W KR 2014003892W WO 2015152457 A1 WO2015152457 A1 WO 2015152457A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin
acid solution
silver
hydroxide
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/003892
Other languages
English (en)
Korean (ko)
Inventor
이강명
이기웅
김홍인
김광중
손현태
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SUNGEEL HITECH CO Ltd
Original Assignee
SUNGEEL HITECH CO Ltd
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 SUNGEEL HITECH CO Ltd filed Critical SUNGEEL HITECH CO Ltd
Publication of WO2015152457A1 publication Critical patent/WO2015152457A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/04—Obtaining tin by wet processes
    • 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 separating and recovering silver and tin from a cathode slime which is not electrochemically participated in electrolysis.
  • the soluble residue of the metal is called the anode slime when it is electrolyzed when it is electrolyzed.
  • electronic scrap wastes such as printed circuit boards and electronic parts are made of copper such as copper (Cu), iron (Fe), nickel (Ni), tin (Sn), lead (Pb), aluminum (Al), zinc About 30% of noble metal components such as gold (Au), silver (Ag), and palladium (Pd) are mixed.
  • the printed circuit board has the above-mentioned valuable noble metal in the printed circuit board, the edge connectors printed on the surface thereof, and the semiconductor elements such as ICs and transistors which are integrated circuits disposed thereon.
  • electronic scrap comprising an electronic component such as a printed circuit network of a valuable metal printed on a printed circuit board itself, an edge connector and an integrated circuit (IC) mounted on a printed circuit board, ) Is separated from a printed circuit board to recover valuable metals.
  • the method involves a complicated sorting process in various stages, separating plastics and valuable metals from each other, sorting the selected valuable metals back into a wet or dry smelting process
  • a refining process such as an electrochemical process is optionally used to finally sort and collect valuable metals such as Au, Ag, Pd, Cu and the like, such as precious metals, and recycle them.
  • Low-purity Cu anodes containing noble metals obtained by the refining process are usually dissolved in the anode and electrodeposited in high-purity Cu from the cathode, and the noble metals are concentrated in the anode slime.
  • silver and tin can not be separated and recovered, and the purity of silver and tin is low.
  • the present invention provides a method for selectively separating and recovering silver and tin from a cathode slime.
  • the present invention provides a method for manufacturing a lithium secondary battery, comprising: electrochemically injecting a cathode slime not participating in electrolysis into a strong acid solution; Washing the residue obtained in the filtration step to recover silver; And recovering tin from the residue by adding hydroxide to the filtration solution obtained in the filtration step and filtering the recovered tin and the tin from the anode slime.
  • the strong acid solution is a mixed solution of a hydrochloric acid solution and a nitric acid solution, and the hydrochloric acid solution and the nitric acid solution are mixed at a volume ratio of 1: 0.05-0.1.
  • the positive slurry and the strong acid solution are mixed at a liquid ratio of 45 to 55% (volume of positive slurry (g) / volume (ml) of strong acid solution).
  • the mixing of the positive slurry and the strong acid solution is performed at a temperature of 70 to 80 ° C.
  • the hydroxide may be selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, magnesium hydroxide, and iron hydroxide.
  • the hydroxide is characterized in that it is mixed with the filtrate solution in a liquid ratio of 15 to 25% (weight of hydroxide (g) / volume (ml) of filtration solution).
  • the antifoaming agent may further include a defoaming agent, and dimethylpolysiloxane or silica oil may be used as the defoaming agent.
  • the flocculant may further include one selected from the group consisting of polychlorinated aluminum, aluminum sulfate and ferric chloride, and the activated carbon may contain 10 to 30 wt% of tin %. ≪ / RTI >
  • silver and tin contained in the residue can be recovered in high purity from the residue (slime) which is not electrochemically dissolved when electrolysis is carried out using a metal as an anode, and selectively separated by silver and tin, .
  • FIG. 1 is a flowchart showing a method of separating and recovering silver and tin from a cathode slime according to the present invention.
  • FIG. 2 is a graph showing the concentration of elements contained in residues according to the amount of nitric acid added in the separation and recovery method of silver and tin from a cathode slime according to the present invention.
  • FIG. 3 is a graph showing the concentrations of metals contained in tin residues after silver recovery in the separation and recovery method of silver and tin from a cathode slime according to the present invention.
  • FIG. 4 is a graph showing the concentration of metal contained in the filtered solution after recovery of tin in the method of separating and recovering silver and tin from the anode slime according to the present invention.
  • FIG. 5 is a graph showing the filtration rate according to the addition of coagulant and activated carbon in the separation and recovery method of silver and tin from the anode slime according to the present invention.
  • the present invention relates to a method for producing a slurry, which comprises: mixing a slurry of a positive electrode into a strong acid solution and stirring the slurry;
  • the method of separating and recovering silver and tin from the cathode slime according to the present invention is capable of recovering silver and tin contained in the residue from the remaining slurry (slime) with high purity without electrochemically dissolving when electrolysis is carried out using a metal as an anode, And tin, and can be recovered at a high recovery rate.
  • FIG. 1 is a flowchart showing a method of separating and recovering silver and tin from a cathode slime according to the present invention.
  • the present invention will be described in detail with reference to Fig.
  • the method for separating and recovering silver and tin from the cathode slime according to the present invention includes a step (S10) of mixing a cathode slime which is not electrochemically dissolved in a strong acid solution, stirring the solution and filtering the slurry.
  • the cathode slime does not participate in electrochemical electrolysis, and the strong acid solution is a mixed solution of a hydrochloric acid solution and a nitric acid solution, 1: 0.05 to 0.1 by volume.
  • the volume ratio is less than 0.05, there is a problem in that silver and tin are contained in the residue as well as silver and the silver and tin can not be recovered.
  • the volume ratio is more than 0.1, lead content in the residue is increased to increase the impurity content There is a problem of increasing.
  • the concentration of the hydrochloric acid solution is 92 to 97%, and the concentration of the nitric acid solution is 3 to 8%.
  • the anode slime and the strong acid solution are mixed at a liquid ratio (anode slime weight (g) / volume (ml) of strong acid solution) of 45 to 55%.
  • a liquid ratio anode slime weight (g) / volume (ml) of strong acid solution
  • the solid-liquid ratio is less than 45%, there is a problem that a sufficient amount of metal is not dissolved because the anode slime is less than that of the strong acid solution, and when the solid ratio exceeds 55%, unreacted materials that have not reacted with strong acid are increased have.
  • the mixing of the positive slurry and the strong acid solution is preferably performed at a temperature of 70 to 80 ° C.
  • the temperature is lower than 70 ° C., there is a problem that copper or tin is contained in the residue after the filtration step to separate them from silver.
  • the temperature exceeds 80 ° C., the addition amount of defoamer and water for removing bubbles due to a violent reaction There is an increasing problem.
  • the method of separating and recovering silver and tin from the anode slime according to the present invention may further include an antifoaming agent during the stirring.
  • the antifoaming agent may be a silicone-based antifoaming agent and may remove bubbles or bubbles. Specifically, dimethylpolysiloxane, silica oil, etc. may be used.
  • a method for separating and recovering silver and tin from the cathode slime according to the present invention includes a step (S20) of washing the residue obtained in the filtration step to recover silver.
  • the filtration process When the filtration process is performed with a general filter paper or vacuum filtration, it can be separated into a residue and a filtrate solution.
  • the filtered residue contains a large amount of silver, and the silver can be recovered after washing it.
  • the method of separating and recovering silver and tin from the anode slime according to the present invention includes a step (S30) of adding hydroxide to the filtration solution obtained in the filtration step, and recovering tin from the filtrate by filtration.
  • the remaining filtrate after recovering the silver from the residue separated by the filtration process contains a large amount of tin.
  • hydroxide is added to adjust the pH of the filtrate to 1.1-1.5 to recover tin have.
  • the hydroxide may be one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, magnesium hydroxide and iron hydroxide, and the hydroxide may be used in an amount of 15-25% by weight of the filtrate solution (hydroxide weight (g) Volume (ml) of the solution).
  • the solid-liquid ratio is less than 15%, there is a problem that the amount of tin recovered is small.
  • the solid-liquid ratio exceeds 25% there is a problem that tin contains impurities such as lead and copper after silver recovery.
  • the method of separating and recovering silver and tin from the anode slime according to the present invention may further comprise a flocculant or activated carbon after the hydroxide addition.
  • the coagulant or activated carbon serves as a carrier capable of coagulating tin or supporting tin, and the coagulant may be one selected from the group consisting of polychlorinated aluminum, aluminum sulfate and ferric chloride, Is preferably contained in an amount of 10 to 30% by weight of the tin.
  • the activated carbon is contained in an amount of less than 10% by weight of tin, the filtration time is long. In the case of exceeding 30% by weight, the filtration time is not shortened further. proper.
  • Example 1 Separation of Silver and Tin from a Positive Slime 1
  • the filtrate was subjected to primary filtration using a filter paper to recover silver from the filtrate residue.
  • Table 1 below shows the ICP analysis results of the anode slime.
  • Example 2 Number of separations of silver and tin from the anode slime 2
  • Tables 2 and 3 below show that 10 kg of the anode slime is used (Example 1).
  • the filtrate obtained by the primary filtration process contained a large amount of tin
  • the residue obtained by the primary filtration process contained a large amount of Ag
  • silver was recovered from the residue.
  • the primary filtration residue recovery rate was 109.8%
  • the recovery of silver was 99% or more
  • the recovery rate of the primary filtration solution was 217.5%, and the tin content could be recovered to 99% or more.
  • Tables 4 and 5 below show that the positive electrode slime is used at 4 kg (Example 2).
  • the filtrate obtained by the primary filtration process contained a large amount of tin
  • the residue obtained by the primary filtration process contained a large amount of Ag
  • silver was recovered from the residue.
  • the primary filtration residue recovery rate was 119.5%
  • the recovery rate of silver was 99% or more
  • the recovery rate of the primary filtrate was 159.1%, indicating that the tin content could be recovered to 99% or more.
  • the hydrochloric acid solution and the nitric acid solution are preferably mixed in a volume ratio of 1: 0.05-0.1.
  • the residue obtained by filtration after adding sodium hydroxide exhibited a large amount of tin and a small amount of Ag at pH 1.1 to 1.5, but the amount of Ag was increased at a pH of 1.8 or more And the amount of Pb, Cu and Fe increases sharply as the pH is increased, so that it is preferable to add sodium hydroxide so that the pH is in the range of 1.1 to 1.5.
  • FIG. 3 is a graph showing the concentrations of metals contained in tin residues after silver recovery in the method of separating and recovering silver and tin from a cathode slime according to the present invention.
  • FIG. 4 is a graph showing the concentrations of metals and tin Which is a graph showing the concentration of the metal contained in the filtered solution after tin recovery in the method.
  • tin can be recovered by adding a flocculant or activated carbon.
  • activated carbon is faster than the use of flocculant.
  • filtration time was almost the same as that of using 30 wt% of activated carbon.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention se rapporte à un procédé pour la séparation et la récupération d'argent et d'étain à partir de boue d'anode, et plus particulièrement, à un procédé pour la séparation et la récupération d'argent et d'étain à partir de boue d'anode, comprenant les étapes consistant : à mettre de la boue d'anode, qui n'est pas électrochimiquement impliquée dans l'électrolyse, dans une solution d'acide fort pour agiter cette dernière et ensuite filtrer cette dernière; à récupérer de l'argent par lavage du résidu obtenu grâce à l'étape de filtration; et à récupérer de l'étain à partir du résidu par ajout d'un hydroxyde à une solution filtrée obtenue grâce à l'étape de filtration et filtration de cette dernière.
PCT/KR2014/003892 2014-03-31 2014-04-30 Procédé de séparation et de récupération d'argent et d'étain à partir de boue d'anode Ceased WO2015152457A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0037767 2014-03-31
KR20140037767A KR101481366B1 (ko) 2014-03-31 2014-03-31 양극 슬라임으로부터 은 및 주석의 분리회수방법

Publications (1)

Publication Number Publication Date
WO2015152457A1 true WO2015152457A1 (fr) 2015-10-08

Family

ID=52588706

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/003892 Ceased WO2015152457A1 (fr) 2014-03-31 2014-04-30 Procédé de séparation et de récupération d'argent et d'étain à partir de boue d'anode

Country Status (2)

Country Link
KR (1) KR101481366B1 (fr)
WO (1) WO2015152457A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3047421A1 (fr) * 2016-02-10 2017-08-11 Commissariat Energie Atomique Procede pour ralentir la dissolution d'un compose utilisant un agent anti-mousse
CN112441611A (zh) * 2020-12-07 2021-03-05 云南锡业锡化工材料有限责任公司 一种利用海绵锡及阳极泥制备二氧化锡的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102038954B1 (ko) 2018-04-10 2019-10-31 주식회사 어스텍 알칼리 프릿팅법을 이용한 폐 이차전지의 유가금속 분리방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002069544A (ja) * 2000-08-28 2002-03-08 Nikko Materials Co Ltd インジウムの回収方法
KR100367709B1 (ko) * 2000-05-29 2003-01-10 희성엥겔하드주식회사 폐액으로부터 백금족 금속의 회수방법
KR20040042696A (ko) * 2002-11-15 2004-05-20 주식회사 씨에스 이엔지 폐 ｉｔｏ 타겟으로부터 인듐을 회수하기 위한 방법
KR101199513B1 (ko) * 2010-10-21 2012-11-09 한국지질자원연구원 Ｐｂ-ｆｒｅｅ 폐솔더로부터 유가 금속의 회수방법
KR101336121B1 (ko) * 2011-11-30 2013-12-03 한국지질자원연구원 염산용액을 이용한 폐무연솔더 재활용 방법
KR101364520B1 (ko) * 2012-08-20 2014-02-19 한국해양대학교 산학협력단 염화철용액을 이용한 폐무연솔더 내 유용 금속 분리회수방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100367709B1 (ko) * 2000-05-29 2003-01-10 희성엥겔하드주식회사 폐액으로부터 백금족 금속의 회수방법
JP2002069544A (ja) * 2000-08-28 2002-03-08 Nikko Materials Co Ltd インジウムの回収方法
KR20040042696A (ko) * 2002-11-15 2004-05-20 주식회사 씨에스 이엔지 폐 ｉｔｏ 타겟으로부터 인듐을 회수하기 위한 방법
KR101199513B1 (ko) * 2010-10-21 2012-11-09 한국지질자원연구원 Ｐｂ-ｆｒｅｅ 폐솔더로부터 유가 금속의 회수방법
KR101336121B1 (ko) * 2011-11-30 2013-12-03 한국지질자원연구원 염산용액을 이용한 폐무연솔더 재활용 방법
KR101364520B1 (ko) * 2012-08-20 2014-02-19 한국해양대학교 산학협력단 염화철용액을 이용한 폐무연솔더 내 유용 금속 분리회수방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3047421A1 (fr) * 2016-02-10 2017-08-11 Commissariat Energie Atomique Procede pour ralentir la dissolution d'un compose utilisant un agent anti-mousse
WO2017137433A1 (fr) * 2016-02-10 2017-08-17 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede pour ralentir la dissolution d'un compose utilisant un agent anti-mousse
CN112441611A (zh) * 2020-12-07 2021-03-05 云南锡业锡化工材料有限责任公司 一种利用海绵锡及阳极泥制备二氧化锡的方法

Also Published As

Publication number Publication date
KR101481366B1 (ko) 2015-01-14

Similar Documents

Publication Publication Date Title
WO2021241944A1 (fr) Procédé de récupération de métal précieux à partir d'un matériau de déchet d'électrode d'une batterie secondaire au lithium à l'aide de carbonate de lithium
KR100860344B1 (ko) 납의 회수 방법
CN105112674B (zh) 一种废弃电路板全湿法回收工艺
CN105154680B (zh) 一种从废旧印制线路板表面选择性剥离金属金的方法
KR960009172B1 (ko) 구리분말과 금속 염화물의 동시 제조방법
KR101567499B1 (ko) Led 폐기물로부터 유가금속의 선별 회수 방법
WO2015152457A1 (fr) Procédé de séparation et de récupération d'argent et d'étain à partir de boue d'anode
WO2014030878A1 (fr) Procédé de séparation et de récupération de métaux utiles à partir de déchets de brasure sans plomb
WO2023128042A1 (fr) Méthode hydrométallurgique de récupération de sulfate de nickel
JP5070581B2 (ja) 貴金属の分離回収方法
WO2014178586A1 (fr) Procédé de récupération d'un acide et d'un métal du groupe du platine à partir d'une solution de lixiviation d'un catalyseur de déchets
WO2010090478A2 (fr) Procédé de lixiviation d'impuretés contenues dans des concentrés d'oxyde de molybdène
WO2014042390A1 (fr) Procédé de récupération de métaux à partir de cartes de circuit imprimé usagées
US20040179985A1 (en) Process for recovering metals, in particular precious metals, from electronic scrap
WO2020105861A1 (fr) Procédé de réutilisation de plastique à partir de déchets plastiques plaqués et de récupération de métaux de valeur à partir desdits déchets plastiques plaqués
JP2008106348A (ja) 亜鉛の分離回収方法
WO2017046687A1 (fr) Procédé de récupération de métaux précieux contenus dans des puces de cartes de circuits imprimés (pcb) de déchets
CN1136322C (zh) 萃取和回收银的方法
CN111500872A (zh) 低浓度含钯废液的回收处理方法
CN212925127U (zh) 废杂铜电解阳极泥中有价金属的回收装置
JP2012072480A (ja) ＩｎとＳｎの混合物からのＩｎの選択的回収方法
CN106636648B (zh) 一种含金属废弃物的综合回收分离方法
CN115710641A (zh) 一种金薄膜湿法刻蚀液中贵金属金的回收方法
WO2018092954A1 (fr) Procédé de récupération de métaux dérivés d'un alliage de cuivre
CN110541074A (zh) 白合金中提取锗和钴的提取方法

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: 14888020

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase
122 Ep: pct application non-entry in european phase

Ref document number: 14888020

Country of ref document: EP

Kind code of ref document: A1