US20130026049A1 - Method for recovering valuable metals - Google Patents

Method for recovering valuable metals Download PDF

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Publication number
US20130026049A1
US20130026049A1 US13/640,379 US201113640379A US2013026049A1 US 20130026049 A1 US20130026049 A1 US 20130026049A1 US 201113640379 A US201113640379 A US 201113640379A US 2013026049 A1 US2013026049 A1 US 2013026049A1
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Prior art keywords
flotation
stage
redox potential
adjusted
sulfidizing
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US13/640,379
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English (en)
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Jaakko Leppinen
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Outotec Oyj
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Outotec Oyj
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Assigned to OUTOTEC OYJ reassignment OUTOTEC OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEPPINEN, JAAKKO
Publication of US20130026049A1 publication Critical patent/US20130026049A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/02Froth-flotation processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • C22B11/042Recovery of noble metals from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/02Ores
    • B03D2203/025Precious metal ores
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the invention relates to a method for recovering valuable metals, such as lead, silver and gold from the residue of an electrolytic zinc process.
  • zinc concentrate In addition to zinc, zinc concentrate also contains other valuable metals such as lead, silver and gold, and the recovery of these has a remarkable significance when observing the zinc process as a whole. The behavior of these elements must be taken into account when making process changes.
  • metallic zinc is electrolytically produced from zinc sulfide concentrate, the concentrate is first conducted either as a whole or in parts into roasting, where the zinc sulfide of the concentrate is oxidized into oxide, because zinc oxide is easier to leach than sulfide. The major part of the zinc oxide is leached in a neutral leaching stage into zinc sulfide.
  • part of the concentrate forms zinc-bearing ferrite, the leaching of which requires a higher acid content than the leaching of oxides, and this leaching stage is called strong acid leaching.
  • this leaching stage is called strong acid leaching.
  • a zinc sulfide solution as well as an effluent that mainly contains the iron and sulfur from the concentrate, as well as the lead and valuable metals therefrom.
  • the tendency is more and more towards processes where the concentrate or at least part thereof is leached directly, without roasting.
  • the U.S. patent publication 5,120,353 describes some methods for recovering precious metals in connection with the zinc process. According to said publication, strong acid leaching is carried out in conditions where the iron is mainly in a solution, and the created precipitate contains the elemental sulfur, as well as a small quantity of sulfides that remain undissolved.
  • the precipitate can be conducted directly to pyrometallurgical treatment, or sulfur can be flotated from the precipitate, whereafter the non-flotated residue containing lead sulfate and precious metals can be conducted to pyrometallurgical treatment.
  • the U.S. patent publication 3,968,032 describes a method for recovering lead and zinc from a zinc process residue by flotation.
  • lead is mainly present as sulfate
  • silver is mainly present as sulfide.
  • the method is based on selecting the flotation conditions so that both lead and silver are flotated. If the quantity of zinc and elemental sulfur in the residue is high, flotation is carried out in two stages, when it can normally be carried out in one single stage. When flotation is carried out in two stages, the precipitate is suspended and conducted first to rougher flotation, where collectors are added therein. In rougher flotation, silver, sulfur and zinc are flotated, but lead is not flotated.
  • the overflow from the flotation is conducted to scavenger flotation and cleaner flotation, so that there is obtained a concentrate rich in silver.
  • the pH of the cleaner flotation stage is adjusted to be within the range 2-4.5.
  • the residue is conducted to a second flotation stage, into which there also is fed a sulfidizing agent, such as sodium sulfide, for activating the lead sulfate, and the employed flotation reagents are xanthates and/or dithiophosphates for flotating the lead. If both lead and silver should be recovered from the residue with a high yield, said lead and silver must, according to the method, be flotated separately, i.e. the method requires a two-stage flotation.
  • ferritic leach residue obtained from a neutral leaching stage is processed by conducting it to a sulfidizing stage. After the sulfidizing reactions have taken place, the obtained slurry is conducted to a flotation stage, and the sulfides are flotated. In the flotation stage, the sulfidic phase, the ferritic phase and the solution phase are separated. The aim is to obtain the lead and silver sulfides in the flotation concentrate as completely as possible.
  • the lead and silver sulfide minerals are synthetically made, oxidation takes place extremely rapidly owing to their structure and finely divided composition.
  • air is used as a flotation gas in an electrochemically uncontrolled space, the flotation properties of lead and silver sulfides are quickly weakened, and flotation cannot take place.
  • the flotation of a metal sulfate, such as lead sulfate, is extremely troublesome, which makes the recovery of valuable metals even more difficult.
  • the object of the invention is to introduce a new and more efficient way to separate valuable metals, such as gold, lead and silver, from the leaching residue of zinc.
  • the method according to the invention relates to recovering valuable metals, such as lead, silver and gold from the residue of an electrolytic zinc process, so that the residue from the zinc process is suspended and sulfidized in order to convert the lead and silver compounds into sulfidic form, and further flotated for creating a flotation concentrate containing valuable metals, in which case the sulfidizing and flotation processes are electrochemically controlled, so that the content of the sulfide ions to be fed into the sulfidizing stage is by means of the redox potential adjusted to be on a level where the grain size of the created valuable metal sulfides is sufficient for flotating them, and the redox potential of the flotation stage is adjusted to be within a range where the collector chemical is adhered to the mineral to be flotated, but sulfides are not oxidized.
  • the electrochemical adjusting concept according to the invention it is possible to create optimal flotation conditions for sulfide minerals, in which collector chemicals are adhered
  • the redox potential of the process is measured and adjusted in the sulfidizing stage, in at least one stage.
  • the redox potential is measured and adjusted in the flotation stage, in at least one stage.
  • the redox potential of the slurry is measured by precious metal electrodes, or by metal, glassy carbon or mineral electrodes, or by combinations thereof.
  • a suitable reducing chemical is added in the slurry in the flotation stage in order to adjust the redox potential to a desired level.
  • inert gas is fed in the flotation stage in order to adjust the redox potential to a desired level.
  • a gas mixture is fed in the flotation stage, said gas mixture containing partly inert gas and partly air.
  • At least part of the gas to be removed from the flotation stage is recirculated back to flotation.
  • the gas to be removed is made use of in adjusting the flotation.
  • At least part of the metal-bearing flotation concentrate created in the flotation stage is returned back to sulfidation.
  • the flotation of valuable metals is carried out in one stage.
  • the quantity of the sulfide ion to be fed in the sulfidizing stage is stoichiometric with respect to the quantity of silver and lead contained in the slurry.
  • Sulfide ions are conducted to the solution by using at least one chemical from the following group: Na 2 S, NaHS, Ca(HS) 2 and H 2 S.
  • the pH is adjusted to be within the range 1-4.
  • the redox potential is adjusted to be within the range ⁇ 50-+350 mV vs. SHE.
  • in sulfidizing the redox potential is adjusted to be within the range ⁇ 250- ⁇ 0 mV vs. SHE.
  • FIG. 1 is a block diagram illustrating a method according to the invention.
  • FIG. 1 illustrates a method according to the invention for recovering valuable metals from the leaching residue obtained from the electrolytical production of zinc by utilizing a sulfidation-flotation method.
  • the method is applied to the residue from so-called strong acid leaching, the major part of the iron being dissolved in the preceding process stages, but the method can also be applied to other residues of the zinc process, or to intermediate products, such as the residue from neutral leaching.
  • lead is generally present in sulfate form, silver in sulfate or chloride compounds and gold mainly in elemental form.
  • lead and silver compounds are converted to corresponding sulfides in a closed reactor, by using a stoichiometric quantity of sulfide with respect to lead and silver.
  • the sulfide may be for example in one of the following forms: Na 2 S, NaHS Ca(HS) 2 or H 2 S.
  • the reactions that take place in sulfidizing are as follows:
  • the solid slurry is conducted to a flotation stage, where flotation is carried out in flotation cells by using typical collector chemicals for sulfide minerals, frothing agents and, when necessary, also depressing reagents.
  • collector chemicals suitable for said stages are for example xanthates, dithiophosphates and dithiophosphinates.
  • the flotation stage includes rougher flotation, scavenger flotation and cleaner flotation, by means of which the aim is to maximize both the yield and the product content.
  • the flotation of the valuable metals to be recovered generally takes place in one single stage, whereas the method referred to in connection with the prior art requires two separate stages for recovering silver and lead.
  • the electrochemical adjusting concept according to the invention makes it possible to create optimal flotation conditions for sulfide minerals, wherein collector chemicals are adhered to desired mineral surfaces, but harmful oxidation of sulfide minerals does not take place.
  • the sulfides formed in sulfidation such as sulfides of lead, silver and possibly zinc are so-called synthetic sulfides, and not natural minerals. Synthetic sulfides are formed in connection with precipitation, and they are extremely finely divided and therefore easily reoxidized. Therefore it is important that in the sulfidation and flotation stage, the redox potential is adjusted to be within the correct range.
  • the correct redox potential depends on several different factors, such as the collector used in flotation, the concentration of the valuable metals to be recovered, and the pH of the slurry.
  • the process adjusting methods according to the invention to be used in flotation are described below.
  • an inert gas such as nitrogen, or a mixture of air and an inert gas.
  • the adjusting can also be carried out by feeding in the slurry chemicals affecting the oxidation-reduction state, such as sodium sulfide, sodium hydrogen sulfide or sulfur dioxide.
  • Suitable conditions can also be achieved by recirculating the flotation gas, typically air, so that the share of oxygen in the gas is reduced. In that case the adjusting effect is reached for example by adding a suitable quantity of fresh air in the circulating gas mixture.
  • flotation chemicals such as collectors and frothing agents
  • the pH and redox potential of the slurry are adjusted to be correct for flotation.
  • the redox potential is maintained within a range where the lead sulfide and silver sulfide formed by sulfidation are not oxidized, and at the same time the electrochemical conditions are favorable for the collector chemicals to be adhered on the surfaces of the created minerals and gold.
  • the potential measured by a platinum electrode is within the range ⁇ 50-350 mV vs. SHE.
  • the type of the collector chemical used in the flotation process affects the redox potential.
  • the electrochemical adjusting method is utilized in the sulfidizing stage by using an optimal sulfide level in the solution. From the solution, there is measured the redox potential, which correlates with the active sulfide-ion content of the solution. If the sulfide content in the sulfidizing stage is high, it is strongly indicated by a negative potential. If, on the other hand, the sulfide level is low, the potential value gets more positive readings. With respect to the speed of precipitation, it is advantageous to use high sulfide ion content in the solution, but the drawback is that the created sulfide precipitate is too finely divided for flotation.
  • the composition of the supply material was as follows: Pb 19.3%, Ag 720 g/t, Au 2.3 g/t.
  • the material was mainly composed of zinc and iron compounds, gypsum and silicate minerals.
  • the sulfidation of the residue was carried out in a closed reactor, at the temperature of 50° C., with a pH of 1.5-3, by using a stoichiometric quantity of sulfide with respect to lead, which sulfide was fed in the slurry during 3 hours as a 2.5 M solution.
  • the slurry was subjected to flotation for concentrating lead, silver and gold.
  • the flotation process consisted of a rougher flotation stage and four cleaner flotation stages.
  • electrochemical adjusting was not applied in flotation, but it was carried out normally, with air as the flotation gas.
  • the pH of the slurry was adjusted to be 2.0, and the employed collector reagent was 450 g/t Aerophine 3418A (dithiophosphate derivative), and the employed frothing agent was 60 g/t Dowfroth 250.
  • the rougher flotation stage lasted 16 minutes, and the cleaner flotation stages lasted 5-10 minutes.
  • the redox potential measured by a platinum electrode was 120 mV vs. SHE, but as the aeration began, it rose rapidly to the level +450-600 mV vs. SHE.
  • the yield of lead in the fourth cleaner concentrate was 41.0%, and the content in the concentrate was 24.7%.
  • the yield of silver was 77.3%, and its content in the concentrate was 1740 g/t.
  • the yield of gold was 66.7%, and its content in the concentrate was 4.8 g/t.
  • the yield of lead in the fourth cleaner concentrate was 87.9%, and the content in the concentrate was 56.2%.
  • the corresponding readings were: yield 90.6% and 2160 g/t.
  • the yield of gold was 77.5%, and its content in the concentrate was 5.8 g/t.
  • the examples show that by adjusting the slurry potential in the flotation stage to a suitable range, the harmful oxidation of sulfide minerals could be prevented, at the same time, however, maintaining such electrochemical conditions that were favorable for flotation.
  • the redox potential suitable for the pH range 2-4 is typically within the range ⁇ 50-+350 mV vs. SHE.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
US13/640,379 2010-04-30 2011-04-28 Method for recovering valuable metals Abandoned US20130026049A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20100184 2010-04-30
FI20100184A FI122099B (fi) 2010-04-30 2010-04-30 Menetelmä arvometallien talteen ottamiseksi
PCT/FI2011/050385 WO2011135184A1 (en) 2010-04-30 2011-04-28 Method for recovering valuable metals

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US13/640,379 Abandoned US20130026049A1 (en) 2010-04-30 2011-04-28 Method for recovering valuable metals

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US (1) US20130026049A1 (ko)
EP (1) EP2563522B1 (ko)
JP (1) JP5786021B2 (ko)
KR (1) KR101423860B1 (ko)
CN (1) CN102869449B (ko)
BR (1) BR112012027912A2 (ko)
CA (1) CA2795397C (ko)
EA (1) EA020947B1 (ko)
FI (1) FI122099B (ko)
MX (1) MX345728B (ko)
PE (1) PE20130922A1 (ko)
WO (1) WO2011135184A1 (ko)
ZA (1) ZA201207731B (ko)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102614991A (zh) * 2012-03-19 2012-08-01 赤峰中色锌业有限公司 一种利用中矿再选法从高浸渣中回收银的浮选工艺
CN104451173B (zh) * 2014-12-11 2015-10-07 江西一元再生资源有限公司 一种从生物预氧化-炭浆法提金尾渣中浮选回收金的方法
CN104841564B (zh) * 2015-05-15 2017-08-18 西北矿冶研究院 一种铅银渣浮选组合捕收剂及应用工艺
CN105170309A (zh) * 2015-10-12 2015-12-23 长春黄金研究院 一种多金属含金矿石的铅锌分离方法
CN109107773B (zh) * 2018-08-17 2020-11-10 云南驰宏锌锗股份有限公司 一种高品位铅锌矿中回收铅硫混合精矿的电化学浮选方法
CN112536157B (zh) * 2020-11-19 2022-07-01 矿冶科技集团有限公司 一种高碳难选铅锌矿的选矿方法
KR102655006B1 (ko) 2022-01-06 2024-04-04 정병렬 광물을 이용한 유가금속의 회수방법

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3883421A (en) * 1972-09-12 1975-05-13 Dale Emerson Cutting Measurement of oxidation reduction potential in ore beneficiation
US4366127A (en) * 1980-09-30 1982-12-28 Outokumpu Oy Hydrometallurgical process for the recovery of lead, silver and gold, as well as zinc, from impure jarosite residues of an electrolytic zinc process
US4385038A (en) * 1980-09-30 1983-05-24 Outokumpu Oy Flotation recovery of lead, silver and gold as sulfides from electrolytic zinc process residues
US4561970A (en) * 1982-11-02 1985-12-31 Outokumpu Oy Process for the froth flotation of complex metal compounds
US5855770A (en) * 1994-11-25 1999-01-05 Boc Gases Australia Limited Base metal mineral flotation processes
US7219804B2 (en) * 2003-08-26 2007-05-22 Newmont Usa Limited Flotation processing including recovery of soluble nonferrous base metal values
US20090074607A1 (en) * 2007-09-18 2009-03-19 Barrick Gold Corporation Process for recovering gold and silver from refractory ores

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* Cited by examiner, † Cited by third party
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ES411058A1 (es) 1973-01-27 1975-12-01 Asturiana De Zinc Sa Procedimiento para concentrar por flotacion plomo y plata de productos que contienen el plomo de forma oxidada.
BE829988A (fr) * 1975-06-06 1975-10-01 Procede de traitement des residus de lixiviation des minerais de zinc
FI78990C (fi) * 1984-10-30 1989-10-10 Outokumpu Oy Foerfarande foer maetning och reglering av den elektrokemiska potentialen och/eller komponenthalten i en behandlingsprocess av vaerdematerial.
CA1333199C (en) * 1988-03-24 1994-11-22 Chang Young Choi Process for the recovery of silver from the pb/ag cake
FI88516C (fi) * 1990-02-16 1993-05-25 Outokumpu Oy Hydrometallurgiskt foerfarande foer behandling av zinksulfidhaltiga raoaemnen
CA2107963A1 (en) * 1992-10-09 1994-04-10 Nathaniel Arbiter Tailings retreatment
DE4238244C2 (de) * 1992-11-12 1994-09-08 Metallgesellschaft Ag Verfahren zur selektiven Flotation eines sulfidischen Kupfer-Blei-Zinkerzes
DE19710529A1 (de) * 1997-03-14 1998-09-17 Ruhr Zink Gmbh Verfahren zur Anreicherung von Silber oder anderen Wertmetallen durch Flotation aus einer Suspension, beispielsweise aus den Rückständen der Zinklaugung
JP3602329B2 (ja) * 1998-03-20 2004-12-15 同和鉱業株式会社 インジウム含有物からインジウムを回収する方法
KR20070019428A (ko) * 2005-08-12 2007-02-15 에스케이 주식회사 유기황화합물 제거용 탈황제, 이의 제조방법 및 이를이용한 유기황화합물의 제거방법
FI118473B (fi) * 2006-02-17 2007-11-30 Outotec Oyj Menetelmä kuparin talteenottamiseksi kuparisulfidimalmista
JP5046306B2 (ja) * 2008-08-27 2012-10-10 太平洋セメント株式会社 カルシウム成分及び鉛成分を含有する微粉末の処理方法並びに処理システム

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3883421A (en) * 1972-09-12 1975-05-13 Dale Emerson Cutting Measurement of oxidation reduction potential in ore beneficiation
US4366127A (en) * 1980-09-30 1982-12-28 Outokumpu Oy Hydrometallurgical process for the recovery of lead, silver and gold, as well as zinc, from impure jarosite residues of an electrolytic zinc process
US4385038A (en) * 1980-09-30 1983-05-24 Outokumpu Oy Flotation recovery of lead, silver and gold as sulfides from electrolytic zinc process residues
US4561970A (en) * 1982-11-02 1985-12-31 Outokumpu Oy Process for the froth flotation of complex metal compounds
US5855770A (en) * 1994-11-25 1999-01-05 Boc Gases Australia Limited Base metal mineral flotation processes
US7219804B2 (en) * 2003-08-26 2007-05-22 Newmont Usa Limited Flotation processing including recovery of soluble nonferrous base metal values
US20090074607A1 (en) * 2007-09-18 2009-03-19 Barrick Gold Corporation Process for recovering gold and silver from refractory ores

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CN102869449A (zh) 2013-01-09
EP2563522B1 (en) 2017-04-19
JP2013531129A (ja) 2013-08-01
MX2012012429A (es) 2012-11-29
CN102869449B (zh) 2016-02-10
KR20130029774A (ko) 2013-03-25
EA020947B1 (ru) 2015-02-27
FI122099B (fi) 2011-08-31
KR101423860B1 (ko) 2014-07-25
EP2563522A4 (en) 2014-01-22
AU2011247199A1 (en) 2012-12-13
ZA201207731B (en) 2013-06-26
EP2563522A1 (en) 2013-03-06
EA201291059A1 (ru) 2013-05-30
CA2795397C (en) 2017-01-03
PE20130922A1 (es) 2013-09-18
BR112012027912A2 (pt) 2016-08-16
JP5786021B2 (ja) 2015-09-30
WO2011135184A1 (en) 2011-11-03
CA2795397A1 (en) 2011-11-03
MX345728B (es) 2017-02-09
FI20100184A0 (fi) 2010-04-30

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