US3849265A - Electro-oxidative method for the recovery of molybdenum from sulfide ores - Google Patents

Electro-oxidative method for the recovery of molybdenum from sulfide ores Download PDF

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Publication number
US3849265A
US3849265A US00185502A US18550271A US3849265A US 3849265 A US3849265 A US 3849265A US 00185502 A US00185502 A US 00185502A US 18550271 A US18550271 A US 18550271A US 3849265 A US3849265 A US 3849265A
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United States
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slurry
molybdenum
rhenium
sulfide
solid
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US00185502A
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English (en)
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T Henrie
B Scheiner
R Lindstrom
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US Department of the Interior
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US Department of the Interior
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Priority to US00185502A priority Critical patent/US3849265A/en
Priority to AU47234/72A priority patent/AU478987B2/en
Priority to SE7212587A priority patent/SE396618B/xx
Priority to CA152,943A priority patent/CA1001993A/en
Priority to DE2248178A priority patent/DE2248178C3/de
Priority to ES407458A priority patent/ES407458A1/es
Priority to JP47098877A priority patent/JPS4842908A/ja
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Publication of US3849265A publication Critical patent/US3849265A/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
    • 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
    • C22B3/045—Leaching using electrochemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G47/00—Compounds of rhenium
    • 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
    • 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 This invention relates to a method for the dissolution of molybdenum and rhenium values in a sulfide-type source. These values are placed in a soluble and available form by pulverizing the source in a aqueous salt solution and el'ectro-oxidizing it in an electrolytic cell.
  • This invention relates to a novel and effective method for the recovery of molybdenum and rhenium from sulfide ores, concentrates or tailings. More particularly, it relates to the dissolution of molybdenum and rhenium values in sulfide and associated source materials by an electro-oxidation process.
  • the major sources of molybdenum and rhenium are sulfide-type ores and the like.
  • the classical recovery method is the use of multi-stage flotation techniques and roasting. This recovery method suffers from a number of disadvantages. Multi-stage flotation processes are relatively costly, molybdenum recovery is frequently low, and the roasting of sulfide concentrates causes heavy pollution of the atmosphere.
  • a further disadvantage of the roasting of sulfide ores is that rhenium values are volatilized and go out the stack.
  • molybdenum and rhenium can be converted to a soluble form and extracted from their ores by an electrolytic oxidation method.
  • an aqueous slurry of a solid sulfide-type source comprising molybdenum, rhenium, or molybdenum and rhenium, is electrolyzed while maintaining the pH of the slurry in the range 1 to 11.5, preferably 5.5 to 9.
  • the carrier liquid for the slurry is an aqueous brine or diluted aqueous brine solution.
  • a solid sulfide-type source as used herein is meant by definition, molybdenum sulfide (M08 or rhenium sulfide containing ores and sulfide ores containing molybdenite or rhenium sulfide as a component, for example, copper sulfide ores and the like, flotation concentrates of sulfide ores, ore tailings and the like.
  • M08 or rhenium sulfide containing ores and sulfide ores containing molybdenite or rhenium sulfide as a component for example, copper sulfide ores and the like, flotation concentrates of sulfide ores, ore tailings and the like.
  • the FIGURE is a schematic flow diagram illustrating a particular mode of the invention, utilizing a bipolar flow-through cell for the electro-oxidative dissolution of the molybdenum present in a sulfide ore.
  • tation tank 7 are joined by suitable transfer lines 4, 8, 9 and 2 and the unit is used in the electro-oxidation of an aqueous slurry (pulp) of a typical low-grade molybdenite ore, for example an ore containing about"0.2 weight percent of molybdenum sulfide, minor amounts of copper sulfide, iron sulfide and sulfur and having as the major components quartz and potassium feldspar.
  • a slurry of'the ore is charged to the cell 3, and the surge tank, 7.
  • the liquid component of the slurry is an aqueous brine solution containing about 10 weight percent chloride.
  • the solid component of the slurry is the above described ore which has been pulverized to below 35 mesh (US. Standard Mesh) with about percent of the solid being below 200 mesh.
  • Each 100 parts by weight of the slurry desirably contain about 10 parts of the pulverized ore.
  • the slurry is circulated as indicated,
  • the brine essentially stripped of its molybdenum content, is withdrawn from the [on exchange unit, 19, via line 21, and is desirably recycled to the process together with make-up brine as required to satisfy the concentration and volume conditions described above for the process.
  • the molybdenum values may be recovered via line 16.
  • concentration of the electrolyte (salt) may vary from a minor amount, for example 0.1 weight percent up to the saturation value. Best results are, in general, experienced when the concentration is in about the 7 to 20, preferably 9 to weight percent range. The use of brine concentrations above about 15 weight percent and below about 7 percent is relatively inefficient.
  • Alkali metal, ammonium and alkaline earth metal salts, especially the chlorides (water soluble substantially ionized salts), and mixtures of these salts are satisfactory electrolytes for use in the process.
  • Sodium chloride is preferred for a number of reasons including low cost.
  • the Slurry The particle sizing and solids content of the slurry may vary over a substantial range. In general a useful dissolution of molybdenum sulfide values in a pulverized solid feed is experienced when the particles are sized to pass through a 35 mesh screen.
  • the solid content of the slurry may vary over a wide range.
  • the slurry must be pumpable. For practical purposes at least about 1 part of solid per 100 parts of slurry should be present. In general, good results are obtained when the solid content of the slurry is in the range 1 to parts per 100 parts (weight).
  • a solid content of l to 15 parts to 100 parts solution is preferred when treating higher grade ores or concentrates, whereas a solid content of 30 to 40 parts to 100 parts solution is preferred when treating low grade ores.
  • Slurry pH Molybdenum pH i.e., values can be electro-oxidized over a large range of pI-I,i.e., from about 1 to l 1.5. Excellent results are in general experienced when the slurry pH is maintained in the range 5 to 9, preferably 5.5. to 6.5.
  • Sulfuric acid is a by-product of the oxidation; therefore in order to maintain the pH, a suitable inorganic base must be added during the course of the oxidative extraction of the molybdenum.
  • Alkali metal and ammonium carbonates and hydroxide and the like are useful for this purpose.
  • a solid such as Na CO I-I O is especially desirable since the addition in the solid form results in no appreciable dilution of the slurry. The contrary is the case where the addition is by the use of an aqueous solution of a suitable base.
  • the slurry temperature may vary over a range, i.e, from above the freezing point and below the boiling point of the aqueous brine.
  • the slurry temperature should be in the range below about 55C and above about C.
  • temperature control may be effected easily by one or more ordinary electrolysis parameters, including variations in salt concentration, pulp density, current density, size and shape of the cell and the surge tank, and electrode spacing.
  • Examples 14 16 show that for a given slurry there is an optimum treatment rate which when exceeded results in a less efficient utilization of power. However, a wide range of treatment rates can be employed and yet result in a satisfactory molybdenum dissolution and recovery. The rate desirably used for a particular slurry is readily determinable by routine tests, for example as illustrated in examples 9 11.
  • the current density, amperes per square inch of electrode, may vary over a range.
  • the examples l7 19 of Table 5 carried out as Example 1 except with the current density as noted, for a given slurry, electrode spacing and the like, there is an optimium current density (as related to power utilization, cell sizing and capital costs).
  • the electrolysis unit requirements of the method of the invention may be satisfied by use of a standard cell arrangement and should include sufficient agitation to prevent settling of the particulate solid component of the slurry.
  • the bipolar flow through the type cell as illustrated in the FIGURE is preferred.
  • an ordinary plate cell is often advantageously employed, especially for the electro-oxidation of a low grade ore.
  • Graphite electrodes are in general most satisfactory for use in the method.
  • Other materials of .construction such as copper, iron and the like are also suitable for use in fabricating the cathode.
  • Anodes constructed of PbO or Ru0 coated materials and the like are also suitable.
  • the spacing between the electrodes may vary somewhat depending upon the particle sizing of the solid, the concentration of the electrolyte and the like. In general a spacing of about one-half inch is satisfactory.
  • H Time The time required to achieve a satisfactory recovery of the molybdenum and rhenium values in a solid feed varies depending upon the degree of recovery desired,
  • the brine concentration, the current density used and the like variables In general a useful recovery can be effected in a process in which the average residence time of the slurry in the cell (electrode portion) is in the range 1 to 20 hours. In general, best results, in terms of economic factors, obtain from the use of average residence times in the range 2.5 to 5 hours.
  • a pumpable slurry said slurry being a mixture of a pulverized solid and a carrier liquid, said solid being a sulfide-type source of molybdenum, or rhenium or of molybdenum and rhenium; and said carrier liquid being an aqueous salt solution; contacting said slurry with an anode and cathode; providing current through said anode and cathode, while maintaining the slurry at a pH of to 9 and temperature of to 55C, and thereby electrolyzing said slurry to electro-oxidize said molybdenum and rhenium; and

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Treatment Of Sludge (AREA)
US00185502A 1971-10-01 1971-10-01 Electro-oxidative method for the recovery of molybdenum from sulfide ores Expired - Lifetime US3849265A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00185502A US3849265A (en) 1971-10-01 1971-10-01 Electro-oxidative method for the recovery of molybdenum from sulfide ores
AU47234/72A AU478987B2 (en) 1971-10-01 1972-09-28 Electro-oxidative method forthe recovery of molybdenum and rhenium from sulfide ores
SE7212587A SE396618B (sv) 1971-10-01 1972-09-29 Forfarande for utlosningav molybden och rhenium fran en molybden och/eller rhenium innehallande sulfidmalm genom eletrolys
CA152,943A CA1001993A (en) 1971-10-01 1972-09-29 Electro-oxidative method for the recovery of molybdenum from sulfide ores
DE2248178A DE2248178C3 (de) 1971-10-01 1972-09-30 Verfahren zur Aufbereitung und Gewinnung von Molybdän und/oder Rhenium
ES407458A ES407458A1 (es) 1971-10-01 1972-09-30 Metodo para la obtencion de molibdeno y de renio de minera-les sulfurosos.
JP47098877A JPS4842908A (enrdf_load_stackoverflow) 1971-10-01 1972-10-02

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US (1) US3849265A (enrdf_load_stackoverflow)
JP (1) JPS4842908A (enrdf_load_stackoverflow)
CA (1) CA1001993A (enrdf_load_stackoverflow)
DE (1) DE2248178C3 (enrdf_load_stackoverflow)
ES (1) ES407458A1 (enrdf_load_stackoverflow)
SE (1) SE396618B (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102754A (en) * 1976-10-06 1978-07-25 Electrooxidation Systems, Inc. Ore treatment electrolytic cell
EP0039873A3 (en) * 1980-05-07 1982-01-13 Metals Technology & Instrumentation, Inc. Method of producing metals and metalloids by cathodic dissolution of their compounds in electrolytic cells, and metals and metalloids produced
CN104032127A (zh) * 2014-06-10 2014-09-10 中南大学 一种矿浆电解法从镍钼矿中浸出钼的工艺
RU2529142C1 (ru) * 2013-02-20 2014-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Забайкальский государственный университет" (ФГБОУ ВПО "ЗабГУ") Способ извлечения молибдена из техногенных минеральных образований
US20150122667A1 (en) * 2013-11-05 2015-05-07 Korea Institute Of Geoscience And Mineral Resources Method of leaching molybdenum from sulfide mineral containing molybdenum and copper through electrolytic oxidation scheme

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5164675A (en) * 1974-12-03 1976-06-04 Origin Electric Denkishujinsochino kadenhoho
JPS5393482A (en) * 1977-01-28 1978-08-16 Origin Electric Operation method of electric dust collector
JPS5670860A (en) * 1979-11-10 1981-06-13 Nagano Aichi Denki Kk Power source apparatus for electric dust collector
JPS60110351A (ja) * 1983-11-18 1985-06-15 Fuji Electric Co Ltd 電気集じん装置の起動方法
DE4439041C2 (de) * 1994-11-02 1998-08-13 Starck H C Gmbh Co Kg Verfahren zum Aufschluß und Rückgewinnung der metallischen Bestandteile aus rheniumhaltigen Superlegierungen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US410228A (en) * 1889-09-03 Jacob c
US2761829A (en) * 1951-06-29 1956-09-04 Norman H Dolloff Polarization prevention in electrolysis of sulfide ores
US3464904A (en) * 1964-12-21 1969-09-02 Banner Mining Co Method for treating metallic sulfide compounds
US3639222A (en) * 1970-10-30 1972-02-01 Us Interior Extraction of mercury from mercury-bearing materials
US3673061A (en) * 1971-02-08 1972-06-27 Cyprus Metallurg Process Process for the recovery of metals from sulfide ores through electrolytic dissociation of the sulfides
US3755104A (en) * 1971-03-02 1973-08-28 P Kruesi Process for the recovery of molybdenum and rhenium from sulfides by electrolytic dissolution

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3407127A (en) * 1965-07-06 1968-10-22 Chase Brass & Copper Co Method of recovering rhenium values from rhenium-containing scrap material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US410228A (en) * 1889-09-03 Jacob c
US2761829A (en) * 1951-06-29 1956-09-04 Norman H Dolloff Polarization prevention in electrolysis of sulfide ores
US3464904A (en) * 1964-12-21 1969-09-02 Banner Mining Co Method for treating metallic sulfide compounds
US3639222A (en) * 1970-10-30 1972-02-01 Us Interior Extraction of mercury from mercury-bearing materials
US3673061A (en) * 1971-02-08 1972-06-27 Cyprus Metallurg Process Process for the recovery of metals from sulfide ores through electrolytic dissociation of the sulfides
US3755104A (en) * 1971-03-02 1973-08-28 P Kruesi Process for the recovery of molybdenum and rhenium from sulfides by electrolytic dissolution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Khryashchev et al., Chemical Abstracts, Vol. 70, No. 4, Abstract 13618c, (p. 157), Jan. 1969. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102754A (en) * 1976-10-06 1978-07-25 Electrooxidation Systems, Inc. Ore treatment electrolytic cell
EP0039873A3 (en) * 1980-05-07 1982-01-13 Metals Technology & Instrumentation, Inc. Method of producing metals and metalloids by cathodic dissolution of their compounds in electrolytic cells, and metals and metalloids produced
RU2529142C1 (ru) * 2013-02-20 2014-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Забайкальский государственный университет" (ФГБОУ ВПО "ЗабГУ") Способ извлечения молибдена из техногенных минеральных образований
US20150122667A1 (en) * 2013-11-05 2015-05-07 Korea Institute Of Geoscience And Mineral Resources Method of leaching molybdenum from sulfide mineral containing molybdenum and copper through electrolytic oxidation scheme
CN104032127A (zh) * 2014-06-10 2014-09-10 中南大学 一种矿浆电解法从镍钼矿中浸出钼的工艺
CN104032127B (zh) * 2014-06-10 2016-07-06 中南大学 一种矿浆电解法从镍钼矿中浸出钼的工艺

Also Published As

Publication number Publication date
AU4723472A (en) 1974-04-04
CA1001993A (en) 1976-12-21
JPS4842908A (enrdf_load_stackoverflow) 1973-06-21
SE396618B (sv) 1977-09-26
DE2248178B2 (de) 1980-01-03
ES407458A1 (es) 1975-11-01
DE2248178A1 (de) 1973-04-05
DE2248178C3 (de) 1980-09-04

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