US3426896A - Flotation of bulk concentrates of molybdenum and copper sulfide minerals and separation thereof - Google Patents

Flotation of bulk concentrates of molybdenum and copper sulfide minerals and separation thereof Download PDF

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US3426896A
US3426896A US481420A US3426896DA US3426896A US 3426896 A US3426896 A US 3426896A US 481420 A US481420 A US 481420A US 3426896D A US3426896D A US 3426896DA US 3426896 A US3426896 A US 3426896A
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molybdenum
copper
flotation
isothiouronium
collector
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US481420A
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Robert E Baarson
Charles L Ray
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Armour Industrial Chemical Co
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Armour Industrial Chemical Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/04—Frothers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores

Definitions

  • This invention relates to the flotation of bulk concentrates of molybdenum and copper sulfide minerals and separation thereof, and more particularly to the flotation of molybdenum and copper minerals from metallic sulfide ores containing molybdenum, copper and iron minerals and to the subsequent separation of molybdenum minerals from the copper-bearing ores.
  • An object of the present invention is to provide, in a froth flotation process for the treatment of metallic sulfide ores containing molybdenum, copper and iron minerals, collectors which alone or in synergistic use with common collectors, have better rejection of iron and less affinity for siliceous materials whereby higher recoveries of molybdenum and copper are obtained. Another object is to provide new and improved collectors or combinations of collectors for the recovery of molybdenum and also copper minerals. A further object is to provide a novel process for the separation of molybdenum and copper concentrates in a flotation system. Other specific objects and advantages will appear as the specification proceeds.
  • S-substituted isothiouronium salts are preferably prepared by refluxing an alcoholic solution of thiourea with a fatty halide or with an aromatic halide and are represented by the following formula:
  • R is an aliphatic (straight chain or branched chain), cycloaliphatic, or aromatic hydrocarbon group having 2 or more but not more than 24 carbon atoms and preferably not more than 8 carbon atoms, or mixtures thereof, and where X is a halide such as Cl, Br, I, etc. Best results have been obtained when the hydrocarbon group has from 4 to 10 carbon atoms. Other methods of preparation of the collectors may be employed.
  • the isothiouronium halide compounds thus derived are employed to condition the metallic sulfide pulp together with a frother, if desired, such as methyl amyl alcohol or a polypropylene glycol ether, and following the conditioning, flotation is conducted in the usual manner to effect a bulk concentration and recovery of the molybdenum and copper minerals.
  • a frother such as methyl amyl alcohol or a polypropylene glycol ether
  • flotation is conducted in the usual manner to effect a bulk concentration and recovery of the molybdenum and copper minerals.
  • a sulfide ore containing copper, iron and molybdenum sulfides is ground to a finely-divided state, and a water pulp of the finely-divided ore is mixed or conditioned with about 0.03 lb. of the collector and about 0.03 lb. of
  • the bulk concentrates obtained as described are then subjected to a process to separate the copper and molybdenum minerals into their respective concentrates.
  • Any of a number of chemical depressant agents may be employed to achieve the subsequent separation of the molybdenum and copper minerals by depressing the copper, such as, for example, Nokes reagents, sodium hydroxide, lime, potassium permanganate, hydrogen peroxide, sodiumsulfide, sodium ferrocyanide, etc. Heat alone is effective in bringing about some depression of the copper minerals.
  • the molybdenum concentrate and copper concentrate may be thereafter subjected to further upgrading operations in order to produce a higher grade of copper or molybdenum concentrate.
  • the quantities of collector required may range from about 0.005 lb. to about 0.5 lb. per ton of dried ore treated. The required quantities depend upon the nature of the ore treated and upon the particular collector utilized.
  • collectors may be designated as benzyl-, ethyl-, isopropyl-, n-butyl-, n-amyl-, isoamyl-, 2-ethylhexyl-, n-octyl-, l-methyloctyl-, dodecyl-, laury1-, tetradecyl-, and tallow isothiouronium chloride, and other satls as defined above where the fatty halide or aromatic halide has from 2 to 24 or, preferably, from 2 to 18 carbon atoms and including mixtures of said halides.
  • the preferred collectors have from 4 to 10 carbon atoms in the collector molecules and include n-butyl isothiouronium chloride, n-amyl isothiouronium chloride, and Z-ethyl hexyl isothiouronium chloride.
  • collectors are either water-soluble or waterdispersible it is preferred to apply them to flotation as water solutions or water dispersions ranging from about 1% to about 10% active by weight.
  • Sulfhydryl collectors include the alkyl or aryl dithiophosphates, dithio carbonates (xanthates), dithiocarbamates, thiocarbamates, thioureas, xanthogen formates, mercaptobenzthiazoles, and the like, commonly used for flotation treatment of metallic sulfide ores.
  • n-butyl isothiouronium chloride or n-amyl isothiouronium chloride or 2-ethylhexyl isothiouronium chloride with such collectors as isopropyl ethyl thionocarbamate or sodium or potassium xanthates having from 2 to 12 carbon atoms.
  • collectors as isopropyl ethyl thionocarbamate or sodium or potassium xanthates having from 2 to 12 carbon atoms.
  • n-butyl isothiouronium chloride ionizes with a positive charge and can combine with the sulphur atom of copper sulfide mineral, while the negatively-charged portion of the isopropyl ethyl thionocarbamate normally combines with the copper atom. Either of these collectors can complex with the individual copper or sulfur atoms. It is possible that the synergistic effect is caused by a filling in the voids on the surface coating that may be left by the use of one of these compounds alone.
  • the isothiouronium salts have been discovered to be particularly effective in floating molybdenum concentrates while also floating copper concentrates therewith.
  • the common reagents such as isopropyl ethyl thionocarbamate or sodium isopropyl xanthate, etc.
  • Ethyl isothiouronium Cl Z-200 is a designation for isopropyl thionocarbamate, and Z-11 is a desgination for sodium isopropyl xanthate. This combination of these collectors is considered standard for the type of ore tested.
  • Example II A South American ore (2.85% Cu and 0.7% Moconsidered a high grade ore) was crushed and ground ttor 12 minutes in a laboratory rod mill to a mesh of grind containing 20.3% 'by weight of plus 65 mesh size particles and 30.0% by weight of minus 200 mesh size particles.
  • Grind was at solids and the amount of collector added to the mill varied with the collectors tested.
  • the bulk flotation pH level varied between 11.3 and 11.7.
  • the ground pulps were diluted to about 20% solids in a 1,000 gram stainless steel Denver flotation cell of (1800 In the above Table I,
  • Table II illustrates that the combined use of alkylisothiouronium chloride with a sulfhydryl collector, such as Z-200, provides a synergistic improvement in the recovery of molybdenum and copper when compared to the use of the alkylisothiouronium collector used alone or with a collector system considered standard for the ore tested.
  • the Z-200 is a collector which is normally classed as an anionic collector (exhibiting a negative charge) while the alkylisothiouronium chloride is a cationic collector which ionizes with a positive charge.
  • Two such reagents would normally be considered chemically incompatible and yet compatibility in the process is illustrated in the above data.
  • Example 111 A low .grade Cu-Mo ore from a mining company in the Southwestern United States was crushed to minus 10 mesh and ground with lime in a laboratory rod mill. The ground feed to flotation contained 5.1% by weight of plus 65 mesh particles and 49.4% by weight of minus 200 mesh particles.
  • the pulp was transferred to a Denver laboratory flotation machine, diluted to proper pulp density and the pH adjusted to that required, if necessary.
  • Table IV illustrates an advantage in the use of aryl or alkyl isothiouronium ohloride compounds for the recovery of molybdenum and copper minerals.
  • Table III illustrates an advantage in the use of alkyl- Example V isothiouronium chloride reagents alone or in combination with other promoters such as potassium 'amyl xanthate to provide improved recovery of molybdenum and copper.
  • Example IV A low grade Cu-Mo ore (0.81% Cu and 0.008% Mo) from Southeastern United States was crushed to minus 10 mesh, and was mixed and split samples. These were ground in a laboratory rod mill with enough lime to give the desired pH to the diluted pulp. The ground ore contained an average of 0.7% by weight of plus 65 mesh particles and 59.5% by weight of minus 200 mesh particles.
  • the thickened copperamolybdenum bulk cleaner concentrate was subjected to the particular depressant system being tested by conditioning in a stainless steel beaker with an air-driven mixer.
  • the conditioned pulps were then diluted in a 250 gram stainless steel Denver flotation cell (1200 r.p.m.), pH adjusted to 7.0-7.3 (except when the sodium sulfide depressant system was used, in which case the pH level was near 12.0), conditioned for 2 minutes and floated 4 minutes.
  • the rougher Mo concentrate thus obtained was then subjected to a second addition of the depressant system being tested.
  • the conditioned pulp was then diluted to flotation density in a 250 gram stainless steel Denver flotation cell (1000 r.p.rn.), pH adjusted to 7.0-7.3, conditione for 1 minute and floated for 3 minutes.
  • Table V illustrates the advantage of using alkylisothiouronium chloride reagents, alone or in combination with other reagents for recovery of copper and particularly molybdenum, utilizing Nokes LR 744 depressant for separation of molyzdenum minerals and copper minerals from bulk concentrates.
  • Table V also illustrates the effectiveness of alkylisothiouronium compounds, alone or in combination with other reagents, utilizing depressants such as sodium ferrocyanide, sodium sulfide, or potassium permanganate. It can be seen that the alkylisothiouronium reagents, when used with the sodium ferrocyanide, show much improved recovery of molybdenum over recoveries obtained when Nokes LR 744 reagent was used, while at the same time greater filterability of the molybdenum concentrates and also of the copper concentrates was obtained, the filtering operation being accomplished in much less time compared for instance to the results obtained with Nokes LR 744 reagent which is by nature a dispersing agent.
  • depressants such as sodium ferrocyanide, sodium sulfide, or potassium permanganate.
  • halide 1 in which the salt is n-amyl- 8.
  • a process for the separation of metallic sulfide ores containing molybdenum, copper and iron minerals the steps of conditioning a water suspension of such ores in finely-divided condition with a collector selected from the group consisting of n-butyl isothiouronium chloride, n-amyl isothiouronium chloride, and Z-ethylhexyl isothiouronium chloride, with isopropyl ethyl thionocarbamate, introducing a frothing agent and air to float the molybdenum and copper concentrates away from said iron, and subsequently depressing the copper to recover the molybdenum concentrate.
  • a collector selected from the group consisting of n-butyl isothiouronium chloride, n-amyl isothiouronium chloride, and Z-ethylhexyl isothiouronium chloride, with isopropyl ethyl thionocarbamate
  • a process for the separation of metallic sulfide ores containing molybdenum, copper and iron minerals the steps of conditioning a water suspension of such ores in finely-divided condition with a collector selected from the group consisting of n-butyl isothiouronium chloride, n-amyl isothiouronium chloride, and Z-ethylhexyl isothiouronium chloride, with sodium isopropyl xanthate, introducing a frothing agent and air to float the molybdenum and copper concentrates away from said iron, and subsequently depressing the copper to recover the molybdenum concentrate.
  • a collector selected from the group consisting of n-butyl isothiouronium chloride, n-amyl isothiouronium chloride, and Z-ethylhexyl isothiouronium chloride, with sodium isopropyl xanthate

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912623A (en) * 1973-08-17 1975-10-14 Anaconda Co Flotation recovery of molybdenum
US4022686A (en) * 1975-03-13 1977-05-10 Sumitomo Metal Mining Co., Limited Flotation process for copper ores and copper smelter slags
US4040950A (en) * 1974-08-01 1977-08-09 American Cyanamid Company Concentration of ore by flotation with solutions of aqueous dithiophosphates and thionocarbamate as collector
US4231859A (en) * 1979-11-27 1980-11-04 The United States Of America As Represented By The Secretary Of The Interior Molybdenite flotation
WO1987000088A1 (en) * 1985-07-09 1987-01-15 Phlotec Services, Inc. Process for the selective separation of a copper molybdenum ore
US4789392A (en) * 1984-09-13 1988-12-06 The Dow Chemical Company Froth flotation method
US4797202A (en) * 1984-09-13 1989-01-10 The Dow Chemical Company Froth flotation method
US4822483A (en) * 1984-09-13 1989-04-18 The Dow Chemical Company Collector compositions for the froth flotation of mineral values
US5295585A (en) * 1990-12-13 1994-03-22 Cyprus Mineral Company Method for achieving enhanced copper-containing mineral concentrate grade by oxidation and flotation
US5846407A (en) * 1996-06-17 1998-12-08 Fuerstenau; Douglas W. Pyrite depressant useful in flotation separation
US5853571A (en) * 1996-06-17 1998-12-29 Harris; Guy H. Pyrite depressant useful in flotation separation
US5855771A (en) * 1996-06-17 1999-01-05 Fuerstenau; Douglas W. Pyrite depressant useful in floation separation
CN106423576A (zh) * 2016-09-30 2017-02-22 长春黄金研究院 一种斑岩型铜钼矿铜钼浮选工艺
US9839917B2 (en) 2013-07-19 2017-12-12 Evonik Degussa Gmbh Method for recovering a copper sulfide concentrate from an ore containing an iron sulfide
CN108525841A (zh) * 2018-03-12 2018-09-14 北京矿冶科技集团有限公司 一种铜矿石伴生钼选别方法
US10413914B2 (en) 2012-01-27 2019-09-17 Evonik Degussa Gmbh Enrichment of metal sulfide ores by oxidant assisted froth flotation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1950537A (en) * 1932-08-11 1934-03-13 Barthelemy Edmond Mari Camille Method for the differential flotation of sulphureted copper and zinc ores
US2336868A (en) * 1941-09-06 1943-12-14 American Cyanamid Co Concentration of acidic minerals
US2664199A (en) * 1952-08-27 1953-12-29 Phelps Dodge Corp Flotation recovery of molybdenite
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
US3093666A (en) * 1957-04-01 1963-06-11 Armour & Co Isothiouronium compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1950537A (en) * 1932-08-11 1934-03-13 Barthelemy Edmond Mari Camille Method for the differential flotation of sulphureted copper and zinc ores
US2336868A (en) * 1941-09-06 1943-12-14 American Cyanamid Co Concentration of acidic minerals
US2664199A (en) * 1952-08-27 1953-12-29 Phelps Dodge Corp Flotation recovery of molybdenite
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
US3093666A (en) * 1957-04-01 1963-06-11 Armour & Co Isothiouronium compounds

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912623A (en) * 1973-08-17 1975-10-14 Anaconda Co Flotation recovery of molybdenum
US4040950A (en) * 1974-08-01 1977-08-09 American Cyanamid Company Concentration of ore by flotation with solutions of aqueous dithiophosphates and thionocarbamate as collector
US4022686A (en) * 1975-03-13 1977-05-10 Sumitomo Metal Mining Co., Limited Flotation process for copper ores and copper smelter slags
US4231859A (en) * 1979-11-27 1980-11-04 The United States Of America As Represented By The Secretary Of The Interior Molybdenite flotation
US4789392A (en) * 1984-09-13 1988-12-06 The Dow Chemical Company Froth flotation method
US4797202A (en) * 1984-09-13 1989-01-10 The Dow Chemical Company Froth flotation method
US4822483A (en) * 1984-09-13 1989-04-18 The Dow Chemical Company Collector compositions for the froth flotation of mineral values
WO1987000088A1 (en) * 1985-07-09 1987-01-15 Phlotec Services, Inc. Process for the selective separation of a copper molybdenum ore
US5295585A (en) * 1990-12-13 1994-03-22 Cyprus Mineral Company Method for achieving enhanced copper-containing mineral concentrate grade by oxidation and flotation
US5846407A (en) * 1996-06-17 1998-12-08 Fuerstenau; Douglas W. Pyrite depressant useful in flotation separation
US5853571A (en) * 1996-06-17 1998-12-29 Harris; Guy H. Pyrite depressant useful in flotation separation
US5855771A (en) * 1996-06-17 1999-01-05 Fuerstenau; Douglas W. Pyrite depressant useful in floation separation
US10413914B2 (en) 2012-01-27 2019-09-17 Evonik Degussa Gmbh Enrichment of metal sulfide ores by oxidant assisted froth flotation
US9839917B2 (en) 2013-07-19 2017-12-12 Evonik Degussa Gmbh Method for recovering a copper sulfide concentrate from an ore containing an iron sulfide
CN106423576A (zh) * 2016-09-30 2017-02-22 长春黄金研究院 一种斑岩型铜钼矿铜钼浮选工艺
CN108525841A (zh) * 2018-03-12 2018-09-14 北京矿冶科技集团有限公司 一种铜矿石伴生钼选别方法
CN108525841B (zh) * 2018-03-12 2020-11-06 北京矿冶科技集团有限公司 一种铜矿石伴生钼选别方法

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