WO2024064154A2 - Réduction à base de gaz dans un affinage primaire de cuivre - Google Patents

Réduction à base de gaz dans un affinage primaire de cuivre Download PDF

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Publication number
WO2024064154A2
WO2024064154A2 PCT/US2023/033166 US2023033166W WO2024064154A2 WO 2024064154 A2 WO2024064154 A2 WO 2024064154A2 US 2023033166 W US2023033166 W US 2023033166W WO 2024064154 A2 WO2024064154 A2 WO 2024064154A2
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Prior art keywords
copper
solution
experiments
cuprous
psig
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PCT/US2023/033166
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English (en)
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WO2024064154A3 (fr
Inventor
Sumedh GOSTU
Daniel Duarte
Timothy L. MURRAY
Pablo CISTERNAS
David Dreisinger
Original Assignee
L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
American Air Liquide, Inc.
Incor
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Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude, American Air Liquide, Inc., Incor filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Publication of WO2024064154A2 publication Critical patent/WO2024064154A2/fr
Publication of WO2024064154A3 publication Critical patent/WO2024064154A3/fr

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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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions 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
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/20—Dry methods smelting of sulfides or formation of mattes from metal carbonyls

Definitions

  • the present invention relates to a process for using a mixture of CO and H2 to reduce and precipitate copper in primary copper refining.
  • Copper powder was produced using reduction gases in back end purification processes. There have been some industrial applications of the gas based reduction approaches to produce copper powder from ammoniacal and sulfate leaching media.
  • Evans et al. disclose (Evans et al. "Production of copper powder by hydrogen reduction techniques", Can Min Metal Bull 54.591 (1961 ): 530-538) a pilot scale production of copper powder. The process started off with air and ammonia assisted leaching of copper concentrates at 100 psig total pressure and 200°F, then extended to precursor mixtures containing 0.5% Cu, 29.7% S and 31.2% Fe: Pentalindite (Fe, Ni, S), chalcopyrite (CuFeS2). The produced copper powder was dried in the hydrogen atmosphere before packaging.
  • Joe O’Connor Joe O’Connor, Chemical Engineering, 1952, p164-168 discloses chemical refining of metals extending the process to recover copper from copper and brass copper to extract metallic copper from sulfidic float concentrates, in which high pressures and high temperatures have been harnessed.
  • Yurko, W. J. discloses ("Refining copper by acid leaching and hydrometallurgy.” Chem. Eng 73.18 (1966): 64-66) refining copper by acid leaching and hydrometallurgy. More specifically, Yurko discloses hydrogen reduction of acidic copper sulfate solutions from impure precipitates yields high-purity copper while regenerating sulfuric acid.
  • Peters et al. disclose ("A carbonyl-hydrometallurgy method for refining copper.” mmij-aime papers, May 24-27, 1972, Tokyo) a use of CO in the refining of copper. Carbonyl assisted refining is suitable for copper precursors in the form of powder, tailings or granulated.
  • Stenhouse discloses (Stenhouse, Joanne Helen, “Reduction of aqueous cupric sulfate by hydrogen, carbon monoxide, and their mixtures”, A thesis for the degree of master of science, University of British Columbia, 1982) reduction of aqueous cupric sulfate by hydrogen, carbon monoxide, and their mixtures.
  • the effect of increasing the copper sulfate concentration was to enhance the rate of reduction in both the hydrogen and carbon monoxide systems.
  • the rate of reduction was increased by increasing pressure, temperature, and the concentration of ammonium sulfate buffer. Under mixtures of H 2 and CO the rate of the reduction was intermediate between the rate under pure H 2 and pure CO.
  • Chemical Construction Corporation was a builder of natural gas plants for government and defense contracts and has many granted patents regarding the use of Hydrogen, Carbon Monoxide and Ammonia for the precipitation of copper in sulfate and ammonia media.
  • GB 691 ,1 15 discloses copper bearing and iron bearing minerals are treated to convert copper into copper sulfate.
  • a challenge in the production of copper included the production of a very high purity of copper (> 99.9%).
  • Ferrous sulfate is separated in the filtrate and copper is precipitated as copper sulfide.
  • the copper sulfide residue is enriched to convert it into a soluble copper salt.
  • the process claim is also extended to an oxidative treatment of slurry with air/Oxygen.
  • the copper sulfide precipitate cake is subjected to an exothermic reaction with Oxygen to convert insoluble sulfides to soluble sulfates at a temperature less than 325°C.
  • the cupric ions are reduced to cuprous with the help of CO gas flowing in.
  • the leached solution saturated with CO is then passed through a continuous autoclave at 100 to 150 psig CO pressure at a temperature regime of 200°C to 275°C.
  • the authors suggest operating at 60 to 70% theoretical precipitation throughput to obtain a 99.9% pure copper precipitate.
  • GB691 ,113 discloses a process of precipitating the copper to produce very high purity. Precipitation is carried out on copper solutions constituting copper mine waters, ammoniacal or carbonate leaching of ore or secondary scrap materials, acid leaching of oxide, carbonate or sulfide ores. Copper of electrolytic grade (99.9%) pure can be formed.
  • the leached solution is saturated with CO at 110°C- 150°C if ammoniacal solution is used for leaching, 150°C-300°C if sulfuric acid is used as a leaching media.
  • the saturated solution is precipitated in an autoclave at temperatures between 200°C - 250°C at a pressure of 300 - 700 psig for sufficient time to precipitate 99.9% pure copper recovered at 60 - 75% recovery.
  • GB 699,303 discloses an extraction of copper from copper bearing scrap with the addition of ammoniacal copper carbonate. Residual copper content after precipitating the copper powder is recycled.
  • the solution to be treated will be containing a maximum of 110 g/L Cu.
  • the reducing gas used for the study is not limited to CO and contains H 2 at a temperature regime of 350°F- 500°F. Partial pressure ratios of CO and H 2 were not provided.
  • GB 770, 112 discloses a precursor liquid to be used forthe reduction process extends to leaching of ores containing copper and at least one non-ferrous metal, usually nickel and or cobalt. Reduction is carried out in a pH regime less than 6.5 preferably between 3-4 by adjusting the free acid content to less than 20% and a buffer of ammonium sulfate to initiate selective leaching of copperv/s nickel or cobalt. Copper solutions containing less than 10 g/l copper are not used. Temperature of reduction was around 275°F at a finite pressure of reducing gas and a total pressure preventing boiling (600 - 900 psi). Reducing gas is selected from a group consisting of hydrogen, carbon monoxide and mixtures thereof.
  • GB 269,164 discloses the use of reducing gases CO and H 2 for the reduction of heavy metals from ammoniacal leach liquors at elevated temperatures and pressures. Reduction time, operating pressure and temperature dictate the purity of obtained precipitate. The patent claims to expand to heavy metals especially copper, use of CO and H 2 and corresponding mixtures for reduction. No ranges of temperatures, pressure and reduction times were provided.
  • GB 1252065 discloses extracting copper powders from ammoniacal leach solutions, a process extended to sulfate leach solutions from ores. Copper concentration in aqueous solution can range from 1 g/L to 30 g/L, Nickel is 1 to 150 g/L. CO can be used is pure CO or producer gas (CO+H2); H2 is not claimed for. The total pressure of CO used is 200 psig to 1200 psig at temperatures from 100°C to 250°C. The patent also claims the use of finely divided copper as seed material (0.01 - 0.1 g/l).
  • a process for reducing and precipitating copper in primary copper extraction comprising: adding a gas mixture of CO and H2 to a solution of CuSO4 forming a copper carbonyl (Cu(CO))2SO4; depressurizing the solution to decompose the copper carbonyl (Cu(CO))2SO4 to CU2SO4 and CO; disproportioning Cuprous sulfate to form Copper powder and Cupric sulfate; and precipitating the copper as a copper powder, wherein CO in the mixture of CO and H 2 ranges from 50% to 90%(v/v).
  • CO is 75% in the mixture of CO and H2.
  • a reaction temperature ranges from 150 to 240°C.
  • a reaction temperature ranges from 180 to 190°C.
  • a reaction temperature is 185°C.
  • a reaction pressure ranges from 400 to 1000 psig.
  • a reaction pressure ranges from 500 psig to 700 psig.
  • a reaction pressure is 600 psig.
  • a copper content in the solution ranges from 40 to
  • H2SO4 ranges 120-240 g/L in the solution.
  • H2SO4 is 150 g/L in the solution.
  • FeSC ranges from 1 to 10 g/L in the solution.
  • FeSC is free in the solution.
  • a purity of the copper powder is 99.9%.
  • FIG. 3 is ORP (mv) of reduced solutions collected from autoclave with calibration experiments
  • FIG. 4 is cuprous in solution High acid experiments, 150°C;
  • FIG. 5 is off gas analysis of gases extracted from autoclave in solution High acid experiments, 150°C;
  • FIG. 6a is cuprous (g/l) in experiments with high acid at 170°C;
  • FIG. 6b is cuprous (g/l) in experiments with high acid at 170°C;
  • FIG. 7a is gas analysis of off gas, atmosphere of autoclave with high acid at 170°C;
  • FIG. 7b is another gas analysis of off gas, atmosphere of autoclave with high acid at 170°C;
  • FIG. 8 is cuprous concentration in pregnant leach solution with high acid at high temperature 180°C and 190°C;
  • FIG. 9 is free acid concentration (g/L) in pregnant leach solution with high acid at high temperature 180°C and 190°C;
  • FIG. 10 is ORP (mv) of reduced solutions collected from autoclave with high acid at high temperature 180°C and 190°C;
  • FIG. 11 is cuprous in solution in experiments with varying CO% in feed: 73% CO, 27% H 2 ;
  • FIG. 12 is free acid in solution in experiments with varying CO% in feed' 73% CO, 27% H 2 ;
  • FIG. 13 is cuprous (g/l) in experiments with varying CO% in feed: higher% CO (75%, 80%) in feed syngas;
  • FIG. 14 is free acid (g/l) in experiments with varying C0% in feed: higher% CO (75%, 80%) in feed syngas;
  • FIG. 15 is ORP (mv) in the experiments v/s time with varying C0% in feed: higher% CO (75%, 80%) in feed syngas;
  • FIG. 16 is cuprous (g/l) in experiments with two different rich electrolyte solutions: Acid Variation;
  • FIG. 17 is free acid (g/l) in experiments with two different rich electrolyte solutions: Acid Variation;
  • FIG. 18 is ORP (mv) in the experiments v/s time with two different rich electrolyte solutions: Acid Variation;
  • FIG. 19 is cuprous (g/l) in experiments with two different rich electrolyte solutions: Acid Variation with Ferrous;
  • FIG. 20 is free acid (g/l) in experiments with two different rich electrolyte solutions: Acid Variation with Ferrous;
  • FIG. 21 is ORP (mv) in the experiments v/s time with two different rich electrolyte solutions: Acid Variation with Ferrous; and
  • FIG. 22 is a flowchart of an exemplary embodiment of a process for carbonyl based refining of copper according to the disclosed method.
  • the disclosed methods may be implemented on rich electrolytes exiting a solvent extraction circuit in primary copper hydrometallurgy operations.
  • the benefits of using the mixed gas (i.e., CO + H2) for precipitation of copper include a better control of parameters that affect the process, such as temperature, reaction time, total pressure, partial pressure ratio of CO and H 2 (pCO/pH2).
  • the disclosed method may achieve a total 80% of theoretical copper recovery that is close to the theoretical copper recovery, at a high purity > 99% of copper powder, such as, 99.9% purity.
  • the theoretical copper recovery is 50% according to Equations (4) and (6) below.
  • a total 80% of theoretical copper recovery is 80% x 50%.
  • the disclosed methods explore the possibility of using CO + H2 to reduce copper in solvent extraction (SX) rich electrolytes to Copper powder.
  • SX solvent extraction
  • the disclosed methods is believed to reduce the cost of copper by 20% comparing to the cost of copper produced by electrowinning owing to high energy requirements in electrowinning.
  • the advantages of the disclosed methods include: i) the disclosed methods are able to treat high copper in solution with high acid content Cu (> 40 g/L) as cuprous sulfate and sulfuric acid (> 120 g/L) in a rich electrolyte, and ii) the disclosed methods are able to tolerate high amounts of Fe (from 1 to 10 g/L) as ferrous sulfate in solution.
  • FIG. 22 is a flowchart of an exemplary embodiment of a process for carbonyl based refining of copper according to the disclosed method.
  • the syngas, CO + H2 is synthesized from a syngas mixing station.
  • CO and H2 gas lines are prepared and both lines are under 1000 psig pressure on delivery gauges.
  • a mass flow meter is connected to each of the two gas lines and when switching on the mass flow meters, the two gases, CO and H2, are mixed in the syngas mixing station.
  • CO and H2 gases each has a purity of 99.99% from a gas cylinder.
  • a desired quantity of cupric, iron salts and sulfuric acid solution is loaded into a pressure autoclave and the syngas CO and H2 from the syngas mixing station is also fed into the pressure autoclave.
  • Cupric sulfate CUSO4 is formed in the cupric, iron salts and sulfuric acid solution.
  • Copper reduction reaction occurs in the pressure autoclave once the cupric, iron salts and sulfuric acid solution and the syngas CO and FF are loaded into the pressure autoclave. Equations (4) - (6) below represent the possible reaction mechanism involved in the pressure autoclave.
  • the copper reduction reaction is usually conducted in the pressure autoclaves, to form a stable cuprous carbonyl complex (Cu(CO))2SO4.
  • cuprous carbonyl (Cu(CO))2SO4 is then depressurized to form cuprous sulfate CU2SO4 which later disproportionates (step 108) to form copper metal powder and cupric sulfate in an atmospheric reactor. Simultaneously, CO is generated.
  • the cuprous sulfate CU2SO4 is recycled back to the pressure autoclave for reduction and CO is recycled back to the syngas mixing station as CO feed. H2SO4 generated from the reduction reaction is also recycled back to the pressure autoclave.
  • liquid samples from the pressure autoclave are collected with a liquid sample vial in a period, such as 30 minute time intervals. This process may be accomplished using a 10 ml bomb sampler. The liquid sample vial is flushed with N2 prior to sample collection. The collected liquid sample is then filtered and collected. The liquids and solids from the liquid sample are stored. Repeat this process of the sample collection for kinetic samples at certain time intervals, for example, at 30 min intervals. After that, gas sample is collected and analyzed. Gas from the pressure autoclave headspace is used to analyze the gas composition right after the liquid sample is collected.
  • the disclosed methods may be conducted at a temperature greater than 150°C. Preferably, the temperature ranges from 150°C to 190°C, more preferably, the temperature being about 185°C. [0041] The disclosed methods may be conducted at a pressure ranging from 400 psig to 1000 psig, preferably, the pressure ranging from 500 psig to 700 psig, more preferably, the pressure being around 600 psig.
  • cupric concentration may range from 30 g/L to 80 g/L (i.e., Cu content in cupric); H2SO4 concentration may range from 120 g/L to 240 g/L; FeSC>4 concentration may range from 1 to 10 g/L (Fe content in FeSO4); ammonium sulfate concentration may range from 0.2 to 1 M if any.
  • a hastealloy based autoclave may be used as the pressure autoclave owing to intactness during reducing conditions.
  • the disclosed methods consist of an autoclave to conduct reduction and a gas cleaning and scrubbing.
  • a syngas station may be used to supply a specific composition of syngas, such as CO and H2, at a required pressure.
  • Periodic sampling e.g., periodic liquid sample collection, may be conducted in a triple vacuum plus N2 purged bomb sampler, the contents of the bomb sampler are taken to a glovebox for further analysis.
  • the triple vacuum plus N2 means 3 cycles of vacuum plus N2 purging. That is, the bomb sampler is purged with N2 and then vacuumed in a cycle. This cycle is conducted 3 times.
  • the disclosed methods include various chemical assays that may be performed on liquid, solid and gas samples generated in the experiments.
  • the liquid samples collected from the autoclave are sparged in N2 to hasten the disproportionation process.
  • the disclosed methods include Cuprous Titration performed on unsparged sample from autoclave.
  • Solution may be mixed with Ferric solution.
  • the resulting ferrous solution mixture is titrated with Cerric solution.
  • the amount of cuprous is then calculated.
  • the disclosed methods include Free Acid titration performed on sparged samples.
  • the samples may be buffered with CioHi2MgN2Na20s (Mg-EDTA) and MgCh.
  • the buffered solution is titrated with 0.1 M NaOH to give the free acid concentration.
  • the disclosed methods include gas analysis analyzed in a period, such as, every 60 mins in an Infrared (I R)/ Thermal Conductivity detector (I R/TCD).
  • I R Infrared
  • I R/TCD Thermal Conductivity detector
  • the disclosed methods include Copper concentration (mg/l) analysis.
  • Microwave Plasma - Atomic Emission Spectroscopy (MP-AES) is used to analyze the concentration of copper in the solution.
  • the disclosed methods include copper purity analysis. That is, solid analysis compared with pure copper metal.
  • the disclosed methods are capable of treating high copper (i.e., copper concentration ranging from 20 g/L to 80 g/L) in solution with high acid content (i.e., sulfuric acid concentration ranging from 100 g/L to 220 g/L);
  • the disclosed methods are able to tolerate high amounts of Fe (e.g., 1 to 10 g/L) as Ferrous sulfate in solution;
  • the disclosed methods do not require a specific free acid concentration to precipitate copper from rich electrolytes/cuprous sulfate; also don't need ammonium ions as part of the solution to speed up kinetics.
  • the disclosed methods are capable of producing copper powder having a purity of 99.9%.
  • Cuprous Titration Performed on unsparged sample from autoclave. Solution mixed with Ferric solution, the resulting ferrous solution was titrated with Cerric solution. The amount of cuprous was then back calculated.
  • Free Acid titration Performed on spareged sample. Sample was buffered with Mg-EDTA and MgCl2. The buffered solution was titrated with 0.1 M NaOH to give the free acid concentration.
  • the optimal temperature may be > 170°C;
  • Example 5 Experiments varying CO% in feed: 66.6% CO, 33.3% H2
  • Example 7 Experiments varying CO% in feed: higher% CO (75%, 80%) in feed syngas
  • Example 8 Experiments with two different rich electrolyte solutions: Acid Variation [0065]
  • the syngas used was at a total pressure 600 psig containing 75% CO 25% H2, temperature of 185°C and reaction time of 4h.
  • 50 g/L of copper was contained in the rich electrolyte solution.
  • Free acid content was varied in the rich electrolyte solution 150 g/L and 180 g/L. Results are presented as FIG. 16 to FIG. 18.
  • Table 6 is a summary of Examples 2-8.
  • Depressurization and disproportionation unit operation in the reaction mechanism may be carried outside the autoclave. After the stipulated reaction time, the contents in the autoclave may be collected in a separate vessel, copper may then be precipitated in a globe box under controlled conditions, such as in N2 atmosphere;
  • the disclosed method provides a better control of disproportionation reaction and morphology of precipitated copper powder
  • reaction time of reduction is ⁇ 2 hrs by employing high temperature.
  • references herein to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the invention.
  • the appearances of the phrase "in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term “some embodiments” or “implementation.”
  • high acid refers to a sulfuric acid concentration ranging from 100 g/L to 220 g/L in a solution according to the disclosed method.
  • high ammonium refers to an ammonium sulfate concentration ranging from 0.2 M to 1 M in a solution according to the disclosed method.
  • high copper refers to a copper concentration ranging from 20 g/L to 80 g/L in a solution according to the disclosed method.
  • high amounts of Fe refers to FeSC>4 concentration ranges from 1 to 10 g/L in a solution according to the disclosed method.
  • theoretical recovery or “theoretical copper recovery” refers to a maximum recovery of copper as copper power, i.e. , 50% according to Equations (4) and (6). That is, 2 moles of copper as cupric sulfate in solution produce a maximum of 1 mole of copper as powder by reduction with CO and H2. All of the copper recoveries mentioned hereforth are based on the maximum recovery of copper as copper powder (i.e. , theoretical recovery 50%). All of the copper recoveries mentioned hereforth are based on the definition of the theoretical recovery. For example, a 65% of theoretical copper recovery means a recovery of 65% multiplying the theoretical recovery (50%), which is 65% x 50%.
  • the term “or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances.
  • “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing i.e. anything else may be additionally included and remain within the scope of “comprising.” “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of' and “consisting of”; “comprising” may therefore be replaced by “consisting essentially of” or “consisting of’ and remain within the expressly defined scope of “comprising”.
  • Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
  • exemplary is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.

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Abstract

Dans des modes de réalisation de la présente invention, un procédé de réduction et de précipitation de cuivre dans une extraction primaire de cuivre comprend les étapes consistant à : ajouter un mélange gazeux de CO et de H2 à une solution de CuSO4 formant un carbonyle de cuivre (Cu(CO))2SO4 ; dépressuriser la solution pour décomposer le carbonyle de cuivre (Cu(CO))2SO4 en CU2SO4 et CO ; dismuter le sulfate cuivreux pour former de la poudre de cuivre et du sulfate cuivrique ; et à précipiter le cuivre sous la forme d'une poudre de cuivre, le CO dans le mélange de CO et de H2allant de 50 % à 90 %.
PCT/US2023/033166 2022-09-21 2023-09-19 Réduction à base de gaz dans un affinage primaire de cuivre WO2024064154A2 (fr)

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