EP1230406A2 - Procede permettant de recuperer des metaux de valeur - Google Patents

Procede permettant de recuperer des metaux de valeur

Info

Publication number
EP1230406A2
EP1230406A2 EP00985012A EP00985012A EP1230406A2 EP 1230406 A2 EP1230406 A2 EP 1230406A2 EP 00985012 A EP00985012 A EP 00985012A EP 00985012 A EP00985012 A EP 00985012A EP 1230406 A2 EP1230406 A2 EP 1230406A2
Authority
EP
European Patent Office
Prior art keywords
leachate solution
aqueous
liquid
process according
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.)
Withdrawn
Application number
EP00985012A
Other languages
German (de)
English (en)
Inventor
Werner Schwab
Ralf Kehl
Dietger KÖPPL
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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 Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1230406A2 publication Critical patent/EP1230406A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • 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 application relates to a multistage process for the recovery of valuable metals from aqueous, acidic leachate solutions.
  • a refining process dependent on the type of metal for example the electrolytic refining of copper.
  • the details of the leaching process are dependent on the type of valuable metal, the way in which it is bound in the ore and the type of materials accompanying the ore (gangue type) .
  • the ore is frequently leached using aqueous acids, for example sulphuric, hydrochloric or nitric acid, or alkalis such as ammonia/ammonium carbonate or ammonium sulphate.
  • aqueous acids for example sulphuric, hydrochloric or nitric acid, or alkalis such as ammonia/ammonium carbonate or ammonium sulphate.
  • US 4,571,387 describes a process for leaching sulphidic copper ores, for example chalcopyrite (CuFeS 2 ) , in which the copper ores are brought into contact with sulphide-oxidizing strains of the bacterium Thiobacillus ferrooxidans in acidic aqueous solution and Cu 2+ ions as well as sulphur and sulphate or sulphuric acid are formed by oxidation of the ore.
  • the Cu 2+ ions can then be processed further by liquid/liquid extraction.
  • a similar process is described in US 4,729,788 which discloses the use of thermophilic bacteria of the Sulfolobus type for leaching sulphidic gold or silver ores.
  • microbiological leaching has advantages over the classical methods (in particular, it requires less complicated and expensive plants and the amounts of inorganic acids or alkalis required for leaching can be reduced)
  • microbiological leaching does cause problems in the subsequent processing stage of solvent extraction (SX) .
  • SX solvent extraction
  • the resulting leachate solutions contain not only the desired high proportions of valuable metals but also, as an intrinsic aspect of the leaching process, relatively large amounts of accompanying elements such as iron.
  • the leachate solutions obtained have relatively high proportions of valuable metal ions.
  • microbiological leaching of sulphidic Cu ores (or ore concentrates) can give aqueous leachate solutions containing Cu ions in amounts of up to 50 g/1.
  • a further problem is posed by the accompanying metals in the leachate solution.
  • copper ores also contain iron which is likewise brought into solution by the leaching process. In the extraction process, this iron can lead to selectivity problems which reduce the yield of valuable metal. It is therefore a further object of the present invention to provide a process in which valuable metal ions can be extracted selectively and in economically viable yields from leachate solutions in which they are present in association with other metal ions.
  • the present application accordingly provides a multistage process for the recovery of valuable metals from an acidic, aqueous leachate solution in which valuable metal ions are present in concentrations of from 10 to 40 g/1, which process comprises
  • pH of the aqueous leachate solution is set to at least 1.2 and not more than 2.5 before and/or during the liquid/liquid extraction process (I) .
  • Valuable metals in the context of the present invention are metals from the group consisting of copper, silver, gold and palladium which can be brought in ionic form into the aqueous phase by leaching of their ores or ore concentrates obtained by flotation. It is immaterial whether the valuable metal is present in the ore in elemental or ionic form.
  • the ores typically contain the valuable metals in the form of oxides, sulphides, selenides, tellurides, carbonates, nitrates, silicates or halides.
  • leachate solutions containing copper ions as valuable metal .
  • the leachate solutions are therefore preferably obtained by leaching sulphidic ores, for example chalcopyrite or bornite.
  • further metal ions can be present in the leachate solutions .
  • These are preferably iron ions which are present in amounts of from 0.001 to 25 g/1.
  • the iron ions are preferably in the form of Fe 3+ ions with lesser amounts of Fe 2+ ions. From 60 to 99 mol% of Fe 3+ and from 40 to 1 mol% of Fe 2+ ions are preferably present.
  • particular preference is given to iron-containing leachate solutions containing virtually exclusively Fe 3+ ions .
  • the aqueous leachate solutions are obtained by biological leaching of ores containing valuable metals or their flotation concentrates using thermophilic microbes of the Sulfolobus type.
  • the ores or concentrates are leached with the aid of the thermophilic bacteria in the temperature range from 40°C to 90°C.
  • the aqueous, acidic leachate solution (feed) is introduced into a mixer/settler El and brought into contact with a solution of an organic complexing agent .
  • the organic phase is separated off and the pH of the remaining aqueous phase is adjusted by bringing the aqueous phase into contact with a suitable inorganic or organic base which may be present in solid form or as a solution or dispersion.
  • the aqueous phase which has thus been set to a pH in the range from 1.2 to 2.5 is again brought into contact with the organic complexing agents in further mixer/settlers E2 and E3 .
  • the aqueous phase resulting from the last extraction stage ( "raffinate" , solution depleted in copper) is discharged from the system.
  • the organic phase loaded with metal ions is then conveyed to step (II) and stripped in SI and S2 using a strongly acidic aqueous solution (H 2 S0 4 ) .
  • a strongly acidic aqueous solution H 2 S0 4
  • This is preferably carried out in mixer/settler systems, preferably using two mixer/ settlers connected in series.
  • the metal ions go back into the aqueous phase and can now be passed to a further recovery step (III) , preferably electrolysis (electrowinning) .
  • the organic complexing agents used in the liquid/liquid extraction (I) in the process of the invention are essentially hydrophobic compounds which undergo specific or nonspecific interactions and/or coordination with the valuable metal ions so as to balance and/or shield the charge of the valuable metal ion so that the polarity is reduced sufficiently for the solubility of the ions in the aqueous phase to be decreased while the solubility of the complex in the organic phase is increased.
  • Such complexing agents include particular phosphorus compounds, organic carboxylic acids, phenols, ketoximes, aldoximes and further chelating agents known m this context to those skilled in the art .
  • Examples of specific classes of substances are organic phosphoric, phosphonic or phosphimc acids, m particular d ⁇ (2- ethylhexyl) phosphoric acid or trioctylphosphme oxide (TOPO) , tributyl phosphate (TBP) or dibutyl carbmol (DBBP) , also acetylacetone, oxalic acid, citric acid, 2 , 2 ' -bipyridyl , salicylaldehyde or ethylenediammetetraacetic acid.
  • TOPO trioctylphosphme oxide
  • TBP tributyl phosphate
  • DBBP dibutyl carbmol
  • aldoximes and/or ketoximes as complexing agents.
  • Such compounds are commercially available under the trade name LIX from Henkel Corp .
  • step (I) is carried out using organic extractants containing from 1 to 35% by weight, preferably from 2 to 25% by weight and in particular from 2 to 20% by weight, of organic complexing agents.
  • the complexing agents are dissolved in suitable organic solvents, for example aliphatic or cycloaliphatic or else aromatic hydrocarbons or mixtures thereof, chlorinated hydrocarbons, ketones or ethers having high flash points (from at least 70°C to about 110°C) and also mixtures of these compounds.
  • the flow rates of the organic (O) and aqueous (A) phases can be or have to be matched as a function of the Cu concentration in the leachate solution ("advanced flow rates" of O/A) .
  • a Cu content of from about 12 to 15 g/1 in the leachate solution, it has been found to be advantageous to set an O/A ratio of from 1.6 to 2.0. This ratio can also be increased in principle, but the extraction performance then deteriorates .
  • the stripping of the loaded organic phase is preferably carried out using an aqueous sulphuric acid solution.
  • the aqueous solutions for stripping typically contain from 100 to 220 g/1 and m particular from 160 to 180 g/1 of H S0 .
  • the latter concentration is particularly preferred for subsequent Cu electrowinning, with the stripping solution (B.E.) containing about 30-35 g/1 of Cu.
  • the stripping stage (II) the acid-labile formation equilibrium of the valuable metal ion complexes is shifted back toward the starting compounds as a result of the high proton concentration.
  • the valuable metal ions are set free and go into the aqueous phase.
  • This acidic aqueous phase loaded with valuable metal ions is then subjected in (III) to known work-up procedures such as crystallization or, preferably, electrolysis in order to recover the valuable metal .
  • process step (I) namely the liquid/liquid extraction, is carried out is of particular importance, since the pH control according to the invention is carried out before and/or during this process step.
  • the pH control step can be carried out prior to introduction of the aqueous leachate solution into the extraction stage (I) .
  • This pH control prior to the extraction is preferably achieved by diluting the untreated leachate solution with water.
  • other methods of pH control described further below can, in principle, also be employed in this process step.
  • the dilution method is particularly advantageous when the leachate solution contains large amounts of iron ions which would precipitate in the form of solid iron hydroxides on addition of bases.
  • this method does produce comparatively large volume flows which require the entire plant to be made appropriately large.
  • the leachate solution is preferably diluted with two or three times its volume of water.
  • the pH control of the aqueous leachate solution is preferably carried out only after the first extraction step.
  • the term "aqueous leachate solution" is also used to refer to such a solution which has already been subjected to one or more extraction steps.
  • pH control can take the form, for example, of a titration using a suitable base.
  • the leachate solutions have pH values of less than 1.2, with typical values being in the range from 0.8 to 1.1.
  • the copper contents are from 10 to 40 g/1.
  • the iron contents can be in the range from 0.0001 to 25 g/1.
  • metal ions such as aluminium, lead, cadmium, calcium, chromium, cobalt, manganese, magnesium, sodium, nickel and zinc ions may be present in amounts of from 0.001 to 1.0 g/1.
  • inorganic bases are the oxides or hydroxides of alkali metals and/or alkaline earth metals, for example sodium hydroxide or calcium hydroxide (for example as "slaked lime” or “quicklime”).
  • sodium hydroxide or calcium hydroxide for example as "slaked lime” or "quicklime”
  • These solutions or slurries typically contain the inorganic base in amounts of from 10 to 30% by weight, preferably from 20 to 25% by weight.
  • the neutralization can also be carried out using solid bases.
  • Typical amounts of base solution are in the range from 5 to 30 g of base solution/litre of leachate solution.
  • organic bases such as tertiary amines can also be used for controlling the pH. These are marketed by the Applicant under the trade name ALAMINE ® . Quaternary ammonium compounds, for example of the ALIQUAT ® type (Henkel) , are also suitable.
  • the pH control step has to be carried out in the form of a separate SX stage, i.e. a separate extraction circuit. In such a procedure, the amines in the form of 30 - 40% strength by weight solutions in suitable solvents, e.g. kerosene, are brought into contact with the aqueous leachate solution.
  • the pH control of the aqueous leachate solution be carried out during a three-stage liquid/liquid extraction as shown in Figure 2, where the leachate solution is first brought into contact with the organic extractant in two mixer/ settlers, pH control is subsequently carried out and this is followed once more by a mixer/settler system for extraction using the organic extractant .
  • the process of the invention can be carried out continuously or batchwise. However, it is generally carried out continuously.
  • a leachate solution (feed) having a Cu concentration of 13.9 g/1 and a pH of 3.8 was used.
  • the iron content was 8 mg/1.
  • a further mixer/settler for adjusting the pH ( "pH adjustment") in which the organic phase loaded with valuable metal was brought into contact with an aqueous 25% strength by weight NaOH solution.
  • the extraction was carried out using a 30% v/v solution of LIX 973N ® in Shellsol ® D70 as organic phase in each case.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé exécuté en plusieurs étapes, permettant de récupérer des métaux de valeur à partir d'une solution aqueuse acide de lixaviat dans laquelle des ions de métaux de valeur sont présents selon des concentrations de 10 à 40 g/l. Ce procédé consiste I) à effectuer une extraction liquide/liquide à partir de la solution de lixaviat, ladite solution étant amenée au moins une fois en contact avec un agent d'extraction organique insoluble dans l'eau; II) puis à amener l'agent d'extraction chargé d'ions de métaux de valeur obtenus pendant l'étape (I) au moins une fois en contact avec une phase aqueuse acide, la majeure partie des ions de métaux de valeur étant transférée dans ladite phase aqueuse acide; III) et à soumettre la phase aqueuse acide obtenue à partir de l'étape (II) à un processus d'électrolyse ou de cristallisation afin de récupérer les métaux de valeur, le pH de la solution aqueuse de lixaviat étant au moins égal à 1,2 et inférieur ou égal à 2,5 avant et/ou pendant le processus d'extraction liquide/liquide (I).
EP00985012A 1999-11-20 2000-11-11 Procede permettant de recuperer des metaux de valeur Withdrawn EP1230406A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19955881 1999-11-20
DE19955881A DE19955881A1 (de) 1999-11-20 1999-11-20 Verfahren zur Gewinnung von Wertmetallen
PCT/EP2000/011184 WO2001038590A2 (fr) 1999-11-20 2000-11-11 Procede permettant de recuperer des metaux de valeur

Publications (1)

Publication Number Publication Date
EP1230406A2 true EP1230406A2 (fr) 2002-08-14

Family

ID=7929737

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00985012A Withdrawn EP1230406A2 (fr) 1999-11-20 2000-11-11 Procede permettant de recuperer des metaux de valeur

Country Status (7)

Country Link
EP (1) EP1230406A2 (fr)
AU (1) AU2157601A (fr)
CA (1) CA2391394A1 (fr)
DE (1) DE19955881A1 (fr)
MX (1) MXPA02004899A (fr)
PL (1) PL354899A1 (fr)
WO (1) WO2001038590A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101842504B (zh) 2007-05-21 2012-11-14 奥贝特铝业有限公司 从铝土矿石中提取铝和铁的工艺
EP2686458A4 (fr) 2011-03-18 2015-04-15 Orbite Aluminae Inc Procédés permettant de récupérer des éléments de terres rares à partir de matériaux renfermant de l'aluminium
EP3141621A1 (fr) 2011-05-04 2017-03-15 Orbite Aluminae Inc. Procédés de récupération de terres rares dans divers minerais
CN103842296B (zh) 2011-06-03 2016-08-24 奥贝特科技有限公司 用于制备赤铁矿的方法
JP2014526431A (ja) 2011-09-16 2014-10-06 オーバイト アルミナ インコーポレイテッド アルミナ及び様々な他の生成物の調製プロセス
EP2802675B1 (fr) 2012-01-10 2020-03-11 Orbite Aluminae Inc. Procédés de traitement de boue rouge
CA2903512C (fr) 2012-03-29 2017-12-05 Orbite Technologies Inc. Procedes de traitement de cendres volantes
US9290828B2 (en) 2012-07-12 2016-03-22 Orbite Technologies Inc. Processes for preparing titanium oxide and various other products
WO2014047728A1 (fr) 2012-09-26 2014-04-03 Orbite Aluminae Inc. Procédés pour la préparation d'alumine et de chlorure de magnésium par lixiviation par hcl de divers matériaux
EP2920114A4 (fr) 2012-11-14 2016-03-02 Orbite Aluminae Inc Procédé de purification d'ions aluminium
CN112981121B (zh) * 2021-02-05 2022-08-23 江西思远再生资源有限公司 一种沉淀法处理含镉废渣并制备高纯金属镉的方法

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Publication number Priority date Publication date Assignee Title
US4018865A (en) * 1976-03-29 1977-04-19 King Industries, Inc. Solvent-extraction process for recovery and separation of metal values
JPS5565332A (en) * 1978-11-13 1980-05-16 Toyo Eng Corp Recovering method for copper from ore
AU654322B2 (en) * 1991-02-27 1994-11-03 Mount Isa Mines Limited Biological leaching of transition ores
AR012179A1 (es) * 1997-03-27 2000-09-27 Billiton Sa Ltd Un procedimiento para la recuperacion de cobre
FR2798144B1 (fr) * 1999-09-07 2001-11-09 Rech S Geol Et Minieres Brgm B Procede et dispositif de traitement en continu de mineraux sulfures de cuivre

Non-Patent Citations (1)

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Title
See references of WO0138590A2 *

Also Published As

Publication number Publication date
DE19955881A1 (de) 2001-05-23
AU2157601A (en) 2001-06-04
PL354899A1 (en) 2004-03-22
CA2391394A1 (fr) 2001-05-31
WO2001038590A2 (fr) 2001-05-31
MXPA02004899A (es) 2003-10-14
WO2001038590A3 (fr) 2001-11-29

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