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US20150361523A1 - Use of oxygenated or polyoxygenated inorganic weak acids, or derivatives, residues and waste thereof, in order to increase the recovery of copper and/or the concentration of copper in processes for the leaching or bioleaching of copper minerals - Google Patents

Use of oxygenated or polyoxygenated inorganic weak acids, or derivatives, residues and waste thereof, in order to increase the recovery of copper and/or the concentration of copper in processes for the leaching or bioleaching of copper minerals Download PDF

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Publication number
US20150361523A1
US20150361523A1 US14/758,141 US201314758141A US2015361523A1 US 20150361523 A1 US20150361523 A1 US 20150361523A1 US 201314758141 A US201314758141 A US 201314758141A US 2015361523 A1 US2015361523 A1 US 2015361523A1
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Prior art keywords
copper
polyoxygenated
oxygenated
acid
minerals
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US14/758,141
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English (en)
Inventor
Carlos SCHUFFER AMELLER
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QUIBORAX SA
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QUIBORAX SA
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Publication of US20150361523A1 publication Critical patent/US20150361523A1/en
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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • 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
    • 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

  • This invention concerns the use of oxygenated or polyoxygenated weak inorganic acids, in any concentration, and their derivatives, residues, and solid waste in copper ore leaching or bioleaching, using sulfuric acid or its derivatives.
  • oxygenated or polyoxygenated weak acids such as boric acid, its derivatives, minerals containing boron, borax, their derivatives, residues, and solid and liquid waste from plants producing boric acid and borax, and phosphoric acid, their minerals, derivatives, residues, and solid waste, in copper mineral leaching or bioleaching, using sulfuric acid or its derivatives.
  • the invention also concerns a leaching and bioleaching process in which an oxygenated or polyoxygenated weak acid, such as boric or phosphoric acid, is added as part of the process.
  • an oxygenated or polyoxygenated weak acid such as boric or phosphoric acid
  • the traditional leaching process of copper minerals is a hydrometallurgical process, consisting of the recovery of copper from the minerals, which are separated by applying a solution of sulfuric acid and water.
  • the subprocesses that occur in leaching are:
  • the copper concentration increases by approximately 5 times through ionic extraction.
  • the PLS solution is mixed with a solution of paraffin and organic resin to extract the copper from it.
  • the resin selectively attracts the copper ions (Cu +2 ), thus obtaining both a resin-copper complex and a low-level copper solution, called raffinate, which is reused in the leaching process and is recovered in the byproduct solutions.
  • the resin-copper complex is treated independently with an acid-rich electrolytic solution that causes the copper to release from the resin and bind with the electrolyte. This is the solution that is taken to the electrowinning plant.
  • Bioleaching is the conventional leaching process, catalyzed biologically and applied to sulfur minerals due to the necessity of increasing their dissolution kinetics.
  • bioleaching is a chemical process, mediated by water and atmospheric oxygen, as well as a biological process, mediated by microorganisms.
  • Oxygen is used as an oxidant by microorganisms in leaching environments. Carbon dioxide is used as a carbon source to produce their cellular structure or to generate biomass.
  • patent EP160463B1 describes a process to produce a leaching solution composed of water, monoethanolamine, and a monoethanolamine salt.
  • the salt is produced by adding an acid, such as carbonic, phosphoric, sulfuric, boric, nitiric, hydrofluoric, chlorhydric, oxalic, malonic, gallic, citric, ascorbic, formic, acetic, or propionic acid, or a mixture of them.
  • the acid is only added to for the purpose of making a salt, and it is not added directly or as a mineral to create the leaching solution.
  • the principal solvent acid mentioned is carbonic acid, which is formed in the process by injecting carbon dioxide and air, thus establishing that the process is thereby easier to control and monitor.
  • Borate compounds are used in the non-metallic mining industry.
  • One of the main boron compounds is ulexite (NaCaB 5 O 9 .8H 2 O); this naturally-occurring borate is used in non-metallic mining to produce or extract boric acid, borax, and other derivatives.
  • boron derivatives such as borax and boric acid, have been used as fertilizers and preservatives in the food industry.
  • borax which is a soluble borate, is used in mining together with ammonium as an iron and steel smelting mixture due to its ability to reduce the mixture melting point and thereby eliminate the iron oxide contaminant from the system. Additionally, the use of borax has been described in the smelting of gold and silver jewelry.
  • Boric acid is used in the manufacture of fiberglass, fire retardants, borosilicate glass, soaps, detergents, and certain pharmaceutical products.
  • boric acid it is used as an antiseptic, an antibacterial, to formulate insecticides, as well as in buffer solution compounds and as a food preservative.
  • boric acid is recognized as raw material in the manufacture of the monofibers that make up textile fiberglass, which is used as the structural base of plastics and circuitry. Additionally, the use of boric acid has been described as a manufacture material for dynamite and weapons of mass destruction.
  • oxygenated and polyoxygenated weak acids particularly inorganic acids, and more particularly, boric and phosphoric acid
  • boric and phosphoric acid as the proposed use in the invention in the leaching stage or bioleaching stage increases copper recovery from the ore in the leaching or bioleaching stage, and, at the same time, increases the copper concentration of the PLS solution, thereby increasing plant production and productivity without increasing water consumption, plant size, or waste generation.
  • the purpose of the invention is to incorporate an oxygenated or polyoxygenated weak acid in the irrigation system, or else to add a superior layer of another mineral that can generate a weak oxygenated or polyoxygenated acid to the leaching pile for the purpose of improving copper recovery and increasing the copper concentration in the PLS.
  • Another priority purpose of the invention is to incorporate a oxygenated or polyoxygenated weak acid to the bioleaching process, either by adding a weak acid directly to the bioleaching heap or else by adding another mineral that can generate the a weak acid for the purpose of improving copper recovery and increasing the copper concentration achieved in the process.
  • the invention concerns the use of boric acid, (in any concentration) its derivatives, minerals containing boron, borax, their derivatives, residues, and solid and liquid waste from plants producing boric acid and borax, and phosphoric acid, their minerals, derivatives, residues, and solid waste in copper mineral leaching or bioleaching, using sulfuric acid or its derivatives.
  • the invention also concerns the use of phosphoric acid, (in any concentration) its derivatives, minerals containing phosphorus, its derivatives, residues, and solid and liquid waste from plants producing phosphoric acid in copper mineral leaching and bioleaching, using sulfuric acid or its derivatives.
  • the invention also describes a leaching process in which a necessary amount of oxygenated or polyoxygenated weak acid, or a compound or a mineral that generates the same is added to the leaching process, and, at the same time, sulfuric acid is added to the leaching heap.
  • the necessary amount of weak acid will depend on the characteristics of the mineral to be leached.
  • Said addition of the weak acid to the leaching heap can occur in conjunction with the sulfuric acid, or it can be added simultaneously using the normal procedures for adding acid to the heap.
  • adding the oxygenated or polyoxygenated weak acid can also occur in situ in the leaching heap, by adding a mineral or a compound that generates said weak acid over the leaching heap. Due to the contact of the mineral or compound that generates the weak acid with sulfuric acid, this process will generate the weak acid in situ.
  • a similar process can be performed during the bioleaching process, in which the oxygenated or polyoxygenated weak acid can be added directly to the bioleaching process in conjunction with the sulfuric acid, or else it can be obtained in situ in the leaching heap by adding a mineral or compound that generates said weak acid in the leaching heap.
  • boric acid refers to H 3 BO 3 (trioxoboric (III) acid, B(OH) 3 , also called orthoboric acid), or its derivatives.
  • Boron minerals refers, without limitation, to ulexite, colemanite, kernite, pandermite, bakerite, datolite, elbaite, admontite, aksaite, ameghinite, ammonioborite, aristarainite, avogadrite, axinite, bandylite, barberiite, behierite, berborite, biringuccite, boracite, boralsilite, borax, borazon, borcarite, bormuscovite, cahnite, calciborite, carboborite, chambersite, charlesite, congolite, danburite, datolite, diomignite, dravite, dumortierite, eremeevite, ericaite,
  • Boron compounds refers, without limitation, to borax (Na 2 B 4 O 7 .10H 2 O or pentahydrate, sodium borate, sodium tetraborate, sodium heptaoxotetraborate), borates (compounds that contain boron oxoanions, with boron in oxidation state+3), boranes (boron hydrides).
  • phosphoric acid refers to H 3 PO 4 .
  • copper compounds refers, without limitation, to: phosphates, phosphonates, phosphoranes, phosphides, sodium hypophosphite, phosphine oxide, phosphorus pentafluoride, phosphorus trichloride, hexafluorophosphoric acid, phosphorus (III) and (V) acid, among others.
  • Phosphorus minerals refers, without limitation, to phosphoric rocks, such as, for example, lignite, andalusite, aheylite, aldermanite, alforsite, alluaudite, althausite, amblygonite, anapaite, apatite, arctite, ardealite, arupite, augelite, autunite, babefphite, barbosalite, baricite, barringerite, bassetite, bauxite, bearthite, belovite, benauite, beraunite, berlinite, bermanite, bertossaite, beryllonite, beusite, biphosphamite, bobierrite, boggildite, bonshtedtite, brabantite, bradleyite, brazilianite, brianite, britholite, Brushite, buchwaldite, cacoxenite, canaphite, cas
  • the samples used in leaching correspond to oxidized copper minerals, mainly chrysocolla (hydrated copper silicate).
  • 40 g of dry, ground mineral was massed from the samples, over which the base leaching solution, composed of 1000 mL of water, 61 mL of 5% H 2 SO 4 and, as proposed in the invention, variable amounts of boric acid, was added.
  • the resulting mixture was agitated for 30 minutes at room temperature (20-25° C.)
  • PLS pregnant leaching solution
  • a solvent extraction stage followed.
  • a mixture was prepared with CuPRO MEX 3506®, an organic extractant, dissolved to 10% v/v in Escaid® 110 (ExxonMobil Chemical).
  • the extractant solution was mixed with the PLS in agitation for 15 minutes in a decanting funnel, and the phases were separated.
  • the organic phase contains a high concentration of copper (RE), and it will be used in the stripping stage.
  • the aqueous phase returns to the leaching stage.
  • L lean electrolyte
  • This electrolyte was stripped with loaded organic (LO) solution in a decanting funnel and maintained in agitation for 15 minutes.
  • the organic solution was returned to the extraction stage, and the rich electrolyte (with a concentration over 40 g/L) entered the electrowinning stage.
  • the electrolyte obtained corresponded to the lean electrolyte.
  • the parameters for copper recovery were established according to the initial mass and the mass recovered in the various stages of the process.
  • PLS corresponds to the product obtained after treating the copper mineral with the leaching solution and LE is lean electrolyte.
  • the effects of a leaching solution composed of: water, 5% sulfuric acid, and variable amounts of boric acid were compared with a conventional leaching solution in a copper extraction process.
  • the tests were performed according to the abovementioned general protocol, using a leaching solution composed of 1000 mL of water, 61 mL of 5% sulfuric acid, and variable amounts of boric acid.
  • the overall amount of copper present in the initial mineral, in the post-filter fluid, and in the washing water, as well as the copper concentration in the PLS were measured (Table 2).
  • Table 2 presents the reactant volumes and masses used in the copper recovery process with the addition of boric acid in the leaching solution. Additionally, the copper concentration in the filtered fluid (PLS) and in the washing water (WW), and the percentage of copper in the remaining gangue were measured.
  • Copper mineral, 5% sulfuric acid, and water is mixed with ulexite (sodium pentahydrate borate and calcium) in amounts equivalent to 5, 10, 15, 20, and 25 g of boric acid, respectively.
  • ulexite sodium pentahydrate borate and calcium
  • This mixture is agitated for 30 minutes and then filtered, thereby obtaining the PLS, which is analyzed chemically to determine its copper (Cu) content.
  • the remaining solid (gangue) is washed with 250 mL of water.
  • the washing water (WW) is analyzed chemically to determine is copper content.
  • the wet gangue is dried, weighed, crushed, and homogenized so it can be analyzed chemically to determine its copper content.
  • the effect of a leaching solution composed of water, 5% sulfuric acid, and variable volumes of technical grade orthophosphoric acid concentrate in the copper mineral refinement process was determined.
  • the new leaching solution was tested by following the abovementioned protocol with a base solution composed of 1000 mL of water, 61 mL of 5% sulfuric acid, and various volumes of orthophosphoric acid added, as shown in Table 7.
  • orthophosphoric acid to the leaching solution generated a greater percentage of recovered copper in comparison with a conventional leaching solution (without orthophosphoric acid).
  • the maximum amount of recovered mineral occurred when 20.6 mL of orthophosphoric acid H 3 PO 4 was added to a concentration of 85 gr/L ( FIG. 4 ).
  • FIG. 1 Global process of copper recovery from minerals.
  • the figure shows the stages that comprise the general copper extraction procedure: leaching, extraction, stripping, and electrowinning, as well as the products and intermediate steps for each stage.
  • FIG. 2 Effect of a leaching solution with boric acid in copper recovery.
  • a) The graphic shows the increase in copper recovery percentage through the addition of boric acid (g) to the leaching solution.
  • the curve represents the increase in the copper concentration (g/L) contained in the PLS through the addition of boric acid (g) to the leaching solution during copper recovery.
  • FIG. 3 Effect of the addition of ulexite on copper recovery in the leaching process.
  • a) The graphic shows the increase in the copper recovery percentage through the addition of ulexite ore to the leaching solution.
  • the curve represents the increase in the copper concentration in the PLS through the addition of ulexite ore to the leaching solution during copper recovery.
  • FIG. 4 Effect of the addition of orthophosphoric acid in a leaching solution on copper recovery.
  • a) The graphic shows the increase in the copper recovery percentage through the addition of orthophosphoric acid (g) to the leaching solution.
  • the curve represents the increase in the copper concentration (g/L) in the PLS in comparison with the amount of boric acid (g) added to the leaching solution during the extraction process.

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US14/758,141 2012-12-28 2013-12-27 Use of oxygenated or polyoxygenated inorganic weak acids, or derivatives, residues and waste thereof, in order to increase the recovery of copper and/or the concentration of copper in processes for the leaching or bioleaching of copper minerals Abandoned US20150361523A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CL2012003727A CL2012003727A1 (es) 2012-12-28 2012-12-28 Uso de acidos debiles oxigenados, minerales, compuestos que los generen, para aumentar la recuperacion de cobre en el proceso de lixiviacion o biolixiviacion; procedimiento de lixiviacion o biolixiviacion de cobre que comprende a dichos acidos; y uso de desechos solidos y liquidos de planyas productoras de acidos debiles.
CL3727-2012 2012-12-28
PCT/CL2013/000097 WO2014100910A1 (es) 2012-12-28 2013-12-27 Uso de ácidos débiles inorgánicos, oxigenados o polioxigenados, sus derivados, residuos y desechos sólidos para aumentar la recuperación de cobre y/o la concentración de cobre en el proceso de lixiviación o biolixiviación de minerales de cobre

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CA (1) CA2896667A1 (es)
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PE (1) PE20151174A1 (es)
WO (1) WO2014100910A1 (es)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170321336A1 (en) * 2014-12-11 2017-11-09 Optimizacion De Procesos Mineros S.A. Electrowinning circuit and method for gathering of metal of interest by an ionic exchange interface
US10526685B2 (en) 2015-10-30 2020-01-07 Technological Resources Pty. Limited Heap leaching
CN110791653A (zh) * 2019-11-11 2020-02-14 浙江工商大学 一种利用含羟基磷灰石废物提铜的方法
US10563284B2 (en) 2018-05-09 2020-02-18 Technological Resources Pty. Limited Leaching copper-containing ores
US10563287B2 (en) 2017-04-06 2020-02-18 Technological Resources Pty. Limited Leaching copper-containing ores
CN113502397A (zh) * 2021-06-18 2021-10-15 昆明鼎邦科技股份有限公司 一种连续硫化生产设备

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SE543405C2 (en) * 2019-05-29 2021-01-05 Alfa Laval Corp Ab Method for joining metal parts
EP4380926A1 (en) 2021-08-02 2024-06-12 Basf Se (3-quinolyl)-quinazoline

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US1451734A (en) * 1920-01-29 1923-04-17 Irving Joseph Leaching of copper ores and recovery of copper
US3282682A (en) * 1961-08-31 1966-11-01 Powder Metals Corp Process for the extraction of copper
US4039404A (en) * 1975-05-19 1977-08-02 Kennecott Copper Corporation Cyclic process using A.C. for selective recovery of metals from materials containing same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170321336A1 (en) * 2014-12-11 2017-11-09 Optimizacion De Procesos Mineros S.A. Electrowinning circuit and method for gathering of metal of interest by an ionic exchange interface
US10526685B2 (en) 2015-10-30 2020-01-07 Technological Resources Pty. Limited Heap leaching
US10563287B2 (en) 2017-04-06 2020-02-18 Technological Resources Pty. Limited Leaching copper-containing ores
USRE50227E1 (en) 2017-04-06 2024-12-03 Technological Resources Pty Limited Leaching copper-containing ores
US10563284B2 (en) 2018-05-09 2020-02-18 Technological Resources Pty. Limited Leaching copper-containing ores
CN110791653A (zh) * 2019-11-11 2020-02-14 浙江工商大学 一种利用含羟基磷灰石废物提铜的方法
CN113502397A (zh) * 2021-06-18 2021-10-15 昆明鼎邦科技股份有限公司 一种连续硫化生产设备

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PE20151174A1 (es) 2015-08-09
WO2014100910A1 (es) 2014-07-03
CA2896667A1 (en) 2014-07-03

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