US3767543A - Process for the electrolytic recovery of copper from its sulfide ores - Google Patents

Process for the electrolytic recovery of copper from its sulfide ores Download PDF

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Publication number
US3767543A
US3767543A US00157281A US3767543DA US3767543A US 3767543 A US3767543 A US 3767543A US 00157281 A US00157281 A US 00157281A US 3767543D A US3767543D A US 3767543DA US 3767543 A US3767543 A US 3767543A
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Prior art keywords
copper
solution
electrolysis
iron
cathode
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US00157281A
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English (en)
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W Hazen
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Cyprus Mines Corp
Hazen Research Inc
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Hazen Research Inc
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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
    • 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
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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

  • ABSTRACT An improvement in the ferric chloride leach recovery of copper from its sulfide ores which comprises recovery of the copper from the leach solution after removal of sulfur by electrolysis rather than by conventional cementation with added iron.
  • ferric chloride leaching method Another effort to solve the problem of recovery of copper values from copper sulfide minerals is the ferric chloride leaching method. This method has been studied at great length in various laboratories and particularly in the Canadian Department of Mines many years ago. (See Investigations in Ore Dressing and Metallurgy 1924, Canada, Department of Mines, Mines Branch, John McLeish, Director, No. 643.) In this process, the copper sulfide minerals are agitated with a hot solution containing a high concentration of ferric chloride. The ferric chloride acts as an oxidizing agent to attack the copper bearing sulfide minerals thereby converting the sulfide to elemental sulfur and putting the copper in solution as copper chloride. To the extent that iron is present in the sulfide mineral, as for example in chalcopyrite, this iron is dissolved as ferrous chloride and the associated sulfur is oxidized to elemental sulfur as is the case with the copper sulfide.
  • the ferric chloride leaching has very little effect upon the mineral pyrite when present by itself but, in general, will attack most sulfides such as pyrrhotite, chalcopyrite, chalcocite, sphalerite, and the like.
  • the sulfur remains in the residue as elemental sulfur.
  • the ferric chloride is reduced to ferrous chloride.
  • the slurry is removed from the leaching vessel and sulfur is separated by any standard method such as filtration or countercurrent decantation thereby separating it from the metal. It can be seen that this is obviously a great advantage because the sulfur has been converted to a form that can be recovered and sold while the metallic elements remain in solution as chlorides for subsequent treatment.
  • the leach solution containing copper chloride and ferrous chloride is treated by cementation in which metallic iron is added to the solution and the copper thereby precipitated as cement copper.
  • This procedure increases the quantity of iron in solution which must be removed eventually and produces a copper of relatively low grade that must be purified and retreated.
  • the solution remaining after electrolytic removal of copper and contained lead is then subjected to a second electrolysis where the iron is removed by deposition on a cathode in an electrolytic cell and some of the ferrous chloride in the anolyte is oxidized to ferric chloride, thus regenerating the leaching reagent for reuse.
  • the amount of electrolytic iron which must be recovered is the total amount dissolved from the original concentrate feed and the amount which was added during the cementation for removal of the copper.
  • the disadvantage of the recovery of the copper in this way is that the copper which is produced is of relatively low grade and is made expensive because of the cost of the iron which is added.
  • this added quantity of iron must then be removed from the circuit by electrolysis in the next stage thereby requiring a considerable increase in the size of the electrolytic circuit that is required for the total iron removal with consequent increase in the cost for recovery of the copper.
  • the iron in the solution after the electrolytic removal of copper is recovered by conventional electrolysis. This amount of iron is, of course, restricted to that which existed in the concentrate. Other metals are recovered by conventional means.
  • the electrolyte media contains essentially ferrous chloride and cupric chloride as does the electrolyte medium used in the tests.
  • a diaphragm cell was used in all tests. It consisted of a l,500 cc cathode compartment separated from a 300 cc anode compartment by a Dynel filter cloth diaphragm. The anode compartment was equipped with a solution overflow. The anode was high purity graphite and had approximately a 0.1 sq.ft. area immersed. The cathode was a sheet of 22-gauge copper with approximately 0.33 sq.ft. submerged. During each of the tests, ferrous chloride electrolyte medium was continuously added to the cathode compartment. This solution flowed through the diaphragm into the anode compartment and out of the cell. The pH of the electrolyte was maintained at about 2.3 or below.
  • the electrolytic reactions are reduction of the copper to metal at the cathode and oxidation of ferrous iron to ferric at the anode. If insufficient ferrous iron is available for oxidation, chlorine is also produced at the anode.
  • the cell was filled with electrolyte medium which contained 65 g/l copper and 135 g/l iron. Approximately cc/hr of g/l ferrous chloride solution was added to the cathode compartment and 12 amps were passed through the cell. After 8 hours of operation when practically all of the copper was plated out the test was terminated.
  • the cathode had increased in weight by 1 16 grams. The voltage used was, of course, below the voltage requirement for the deposition of iron.
  • the bulk of the cathode deposit was hard and coherent, but about 10 grams was spongy and contained only 70% copper. Data collected during the run are shown in the following table.
  • the iron in solution is electrolytically recovered in a subsequent stage by conventional electrolysis with simultaneous formation of ferric chloride which is recycled to the initial leach stage in a commercial process for treatment of copper sulfide concentrate.
  • Tests were run at various current densities to determine the most favorable current density ranges for forming spongy or coherent copper deposits, and to test the efficiency of the process as applied to low copper content electrolytes which correspond to electrolytes resulting from leaching low copper content concentrates.
  • the copper content of the used catholyte from the first test was increased to 2 g/l copper by the addition of cupric chloride.
  • the solution added to the cathode compartment during electrolysis contained 180 g/l ferrous iron and 36 g/l copper.
  • the solution was added at approximately cc/hr while 12 amps were passed through the cell. Approximately 36 grams of copper were added to the cell. At no time was the catholyte above 0.66 g/l copper. Approximately all of the copper in solution was deposited at the cathode, half of which was coherent and the remainder spongy.
  • the fourth test was also similar to those of the second test except that only 6 amps were used and the solution lows:
  • Efiective current density a.s.f. Deposit (cathode) description 80 All spongy. 40 Half spongy. Coherent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US00157281A 1971-06-28 1971-06-28 Process for the electrolytic recovery of copper from its sulfide ores Expired - Lifetime US3767543A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15728171A 1971-06-28 1971-06-28
ZA735063A ZA735063B (en) 1971-06-28 1973-07-25 Process for the electrolytic recovery of metals

Publications (1)

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US3767543A true US3767543A (en) 1973-10-23

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US00157281A Expired - Lifetime US3767543A (en) 1971-06-28 1971-06-28 Process for the electrolytic recovery of copper from its sulfide ores

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US (1) US3767543A (enrdf_load_stackoverflow)
AU (1) AU5699073A (enrdf_load_stackoverflow)
BE (1) BE802736A (enrdf_load_stackoverflow)
CA (2) CA1028651A (enrdf_load_stackoverflow)
DE (1) DE2337577A1 (enrdf_load_stackoverflow)
FR (1) FR2240956B1 (enrdf_load_stackoverflow)
GB (1) GB1427228A (enrdf_load_stackoverflow)
NL (1) NL7309176A (enrdf_load_stackoverflow)
SE (1) SE7310272L (enrdf_load_stackoverflow)
ZA (1) ZA735063B (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901776A (en) * 1974-11-14 1975-08-26 Cyprus Metallurg Process Process for the recovery of copper from its sulfide ores
US3926752A (en) * 1973-04-09 1975-12-16 John C Loretto Direct recovery of metals from sulphide ores by leaching and electrolysis
US3930969A (en) * 1974-06-28 1976-01-06 Cyprus Metallurgical Processes Corporation Process for oxidizing metal sulfides to elemental sulfur using activated carbon
US4384890A (en) * 1982-02-10 1983-05-24 Phelps Dodge Corporation Cupric chloride leaching of copper sulfides
US4544460A (en) * 1981-06-09 1985-10-01 Duval Corporation Removal of potassium chloride as a complex salt in the hydrometallurgical production of copper
US4545972A (en) * 1981-06-09 1985-10-08 Duval Corporation Process for recovery of metal chloride and cuprous chloride complex salts
US4594132A (en) * 1984-06-27 1986-06-10 Phelps Dodge Corporation Chloride hydrometallurgical process for production of copper
US5622615A (en) * 1996-01-04 1997-04-22 The University Of British Columbia Process for electrowinning of copper matte
US10060040B2 (en) * 2014-03-07 2018-08-28 Basf Se Methods and systems for controlling impurity metal concentration during metallurgic processes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2823714A1 (de) * 1978-05-31 1979-12-06 Kammel Roland Verfahren zur gewinnung von blei aus bleisulfid enthaltendem material
SE8504290L (sv) * 1985-09-16 1987-03-17 Boliden Ab Forfarande for selektiv utvinning av bly ur komplexa sulfidmalmer
RU2380437C2 (ru) * 2007-11-01 2010-01-27 Институт вулканологии и сейсмологии ДВО РАН Способ извлечения меди из оксидных или сульфидных руд и их концентратов

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE66547C (de) * RUDOLPH KOEPP & CO. in Oestrich i. Rheingau Gewinnung von Antimon
US333815A (en) * 1886-01-05 silvee
US415738A (en) * 1889-11-26 Hermann a
US805969A (en) * 1904-11-25 1905-11-28 Noak Victor Hybinette Separation of metals.
US1128315A (en) * 1912-06-05 1915-02-16 Pacific Securities Company Ltd Process of circulating solution for electrolysis.
US1434088A (en) * 1919-10-11 1922-10-31 Niels C Christensen Process of treating lead-zinc sulphide ores
US1435891A (en) * 1919-10-13 1922-11-14 Niels C Christensen Process of treating lead-zinc sulphide ores
US1441063A (en) * 1919-10-08 1923-01-02 Miels C Christensen Process of treating sulphide ores of lead, silver, and copper
US1456784A (en) * 1919-09-30 1923-05-29 Cons Mining & Smelting Co Process of treating ores containing galena
US1485909A (en) * 1919-10-08 1924-03-04 Niels C Christensen Process of treating sulphide ores of lead, silver, and copper
US1539713A (en) * 1919-10-13 1925-05-26 Niels C Christensen Process of treating lead-zinc sulphide ores
US1726258A (en) * 1922-12-04 1929-08-27 Niels C Christensen Process of treating oxidized ores of lead
US3464904A (en) * 1964-12-21 1969-09-02 Banner Mining Co Method for treating metallic sulfide compounds

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US333815A (en) * 1886-01-05 silvee
US415738A (en) * 1889-11-26 Hermann a
DE66547C (de) * RUDOLPH KOEPP & CO. in Oestrich i. Rheingau Gewinnung von Antimon
US805969A (en) * 1904-11-25 1905-11-28 Noak Victor Hybinette Separation of metals.
US1128315A (en) * 1912-06-05 1915-02-16 Pacific Securities Company Ltd Process of circulating solution for electrolysis.
US1456784A (en) * 1919-09-30 1923-05-29 Cons Mining & Smelting Co Process of treating ores containing galena
US1485909A (en) * 1919-10-08 1924-03-04 Niels C Christensen Process of treating sulphide ores of lead, silver, and copper
US1441063A (en) * 1919-10-08 1923-01-02 Miels C Christensen Process of treating sulphide ores of lead, silver, and copper
US1434088A (en) * 1919-10-11 1922-10-31 Niels C Christensen Process of treating lead-zinc sulphide ores
US1435891A (en) * 1919-10-13 1922-11-14 Niels C Christensen Process of treating lead-zinc sulphide ores
US1539713A (en) * 1919-10-13 1925-05-26 Niels C Christensen Process of treating lead-zinc sulphide ores
US1726258A (en) * 1922-12-04 1929-08-27 Niels C Christensen Process of treating oxidized ores of lead
US3464904A (en) * 1964-12-21 1969-09-02 Banner Mining Co Method for treating metallic sulfide compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Principles of Electroplating & Electroforming by Blum et al., 3rd ed.; 1949, pgs. 68 69. *
The Electromotive Series, Simple Methods for Analyzing Plating Solutions, 7th ed, 1949, Hanson Van Winkle Munning Co., p. 20. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926752A (en) * 1973-04-09 1975-12-16 John C Loretto Direct recovery of metals from sulphide ores by leaching and electrolysis
US3930969A (en) * 1974-06-28 1976-01-06 Cyprus Metallurgical Processes Corporation Process for oxidizing metal sulfides to elemental sulfur using activated carbon
US3901776A (en) * 1974-11-14 1975-08-26 Cyprus Metallurg Process Process for the recovery of copper from its sulfide ores
US4544460A (en) * 1981-06-09 1985-10-01 Duval Corporation Removal of potassium chloride as a complex salt in the hydrometallurgical production of copper
US4545972A (en) * 1981-06-09 1985-10-08 Duval Corporation Process for recovery of metal chloride and cuprous chloride complex salts
US4384890A (en) * 1982-02-10 1983-05-24 Phelps Dodge Corporation Cupric chloride leaching of copper sulfides
US4594132A (en) * 1984-06-27 1986-06-10 Phelps Dodge Corporation Chloride hydrometallurgical process for production of copper
US5622615A (en) * 1996-01-04 1997-04-22 The University Of British Columbia Process for electrowinning of copper matte
US10060040B2 (en) * 2014-03-07 2018-08-28 Basf Se Methods and systems for controlling impurity metal concentration during metallurgic processes

Also Published As

Publication number Publication date
BE802736A (fr) 1974-01-24
FR2240956A1 (enrdf_load_stackoverflow) 1975-03-14
SE7310272L (enrdf_load_stackoverflow) 1975-01-27
CA1034077A (en) 1978-07-04
GB1427228A (en) 1976-03-10
ZA735063B (en) 1974-06-26
CA1028651A (en) 1978-03-28
NL7309176A (nl) 1975-01-06
AU5699073A (en) 1974-12-19
DE2337577A1 (de) 1975-02-27
FR2240956B1 (enrdf_load_stackoverflow) 1977-09-09

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Owner name: CYPRUS MINES CORPORATION; A CORP OF DE, COLORAD

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CYPRUS METALLURGICAL PROCESSES CORPORATION;REEL/FRAME:004020/0240

Effective date: 19820615

Owner name: CYPRUS MINES CORPORATION; 7000 SOUTH YOSEMITE ST.,

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CYPRUS METALLURGICAL PROCESSES CORPORATION;REEL/FRAME:004020/0240

Effective date: 19820615