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WO1987003222A1 - Compositions collectrices pour la flottation par ecumage de valeurs minerales - Google Patents

Compositions collectrices pour la flottation par ecumage de valeurs minerales Download PDF

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Publication number
WO1987003222A1
WO1987003222A1 PCT/US1986/000342 US8600342W WO8703222A1 WO 1987003222 A1 WO1987003222 A1 WO 1987003222A1 US 8600342 W US8600342 W US 8600342W WO 8703222 A1 WO8703222 A1 WO 8703222A1
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Prior art keywords
omega
sulfide
hydrocarbyl
composition
minerals
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PCT/US1986/000342
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English (en)
Inventor
Richard R. Klimpel
Robert D. Hansen
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Dow Chemical Co
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Dow Chemical Co
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Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to BR8607004A priority Critical patent/BR8607004A/pt
Priority to RO12922786A priority patent/RO100034B1/ro
Publication of WO1987003222A1 publication Critical patent/WO1987003222A1/fr
Priority to SU874203131A priority patent/RU1839638C/ru
Priority to NO873156A priority patent/NO168408C/no
Priority to FI873288A priority patent/FI82395C/fi
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • 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
    • B03D1/014—Organic compounds containing phosphorus
    • 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
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • 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
    • B03D2203/025—Precious metal ores

Definitions

  • This invention concerns novel collectors for the recovery of metal-containing sulfide minerals, sulfidized metal-containing oxide minerals, metal-containing oxide minerals and metals occurring in the metallic state, all four mineral groups referred to herein as metal-containing minerals, from ores by froth flotation.
  • Flotation is a process of treating a mixture of finely divided mineral solids, e.g., a pulverulent ore, suspended in a liquid whereby a portion of such solids is separated from other finely divided solids, e.g., clays and other like materials, present in the ore by introducing a gas (or providing a gas in situ) in the liquid to produce a frothy mass containing certain of the solids on the top of the liquid, and leaving suspended (unfrothed) other solid components of the ore.
  • a gas or providing a gas in situ
  • Flotation is based on the principle that introducing a gas into a liquid containing solid particles of different materials suspended therein causes adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, these particles rise to the top of the liquid to form a froth.
  • collectors such as xanthates, thionocarbamates and the like
  • frothers which facilitate the forming of a stable froth, e.g., natural oils such as pine oil and eucalyptus oil
  • modifiers such as activators to induce flotation in the presence of a collector, e.g., copper sulfate
  • depressants e.g., sodium cyanide, which tend to prevent a collector from functioning as such on a mineral which it is desired to retain in the liquid, and thereby discourage a substance from being carried up and forming a part of the froth
  • pH regulators e.g., lime and soda ash, to produce optimum metallurgical results; and the like.
  • Flotation is employed in a number of mineral separation processes including the selective separation of such metal-containing minerals as those containing copper, zinc, lead, nickel, molybdenum, and other metals from iron-containing sulfide minerals, e.g. pyrite and pyrrhotite.
  • collectors commonly used for the recovery of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals are xanthates, dithiophosphates, and thionocarbamates.
  • Other collectors commonly recognized as useful in the recovery of metal- -containing minerals or sulfidized metal-containing oxide minerals are mercaptans, disulfides (R-SS-R) and polysulfides [R-(S) n -R], wherein n is 3 or greater.
  • metal-containing sulfide minerals or sulfidized metal-containing oxide minerals is often achieved by smelting processes. Such smelting processes can result in the formation of volatile sulfur compounds. These volatile sulfur compounds are often released to the atmosphere through smokestacks, or are removed from such smoke stacks by expensive and elaborate scrubbing equipment. Many nonferrous metal-containing sulfide minerals or metal-containing oxide minerals are found naturally in the presence of iron-containing sulfide minerals, such as pyrite and pyrrhotite.
  • the xanthates, thionocarbamates, and dithiophosphates do not selectively- recover nonferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals.
  • collectors collect and recover all metal-containing sulfide minerals.
  • the mercaptan collectors have an environmentally undesirable order and are very slow kinetically in the flotation of metal-containing sulfide minerals.
  • the disulfides and polysulfides when used as collectors, give low recoveries with slow kinetics. Therefore, the mercaptans, disulfides, and polysulfides are not generally used commercially. Furthermore, the mercaptans, disulfides and polysulfides do not selectively recover nonferrous metal-containing sulfide minerals in the present of iron-containing sulfide minerals.
  • a flotation collector which will selectively recover, at relatively good recovery rates, a broad range of metal-containing minerals in the presence of iron-containing sulfide minerals such as pyrite and pyrrhotite.
  • the present invention is a collector composition for the floatation of metal-containing minerals which comprises: (a) a compound of the formula:
  • Y is S, O, a hydrocarbylene radical or a substituted hydrocarbylene radical
  • R 1 and R 2 are independently a C 1-22 hydrocarbyl radical, a C 1-22 substituted hydrocarbyl radical, or a saturated or unsaturated heterocyclic ring;
  • y + p + m n, where n is an integer from 1 to 6, and y, p and m are independently 0 or an integer from 1 to 6, and each moiety can occur in a random sequence;
  • R 3 is hydrogen, a C 1-22 hydrocarbyl radical or a C 1-22 sukstituted hydrocarbyl radical
  • R 5 and R 6 are independently a hydrocarbyl radical or a hydrocarbyl radical substituted with one or more hydroxy, cyano, halo, ether, hydrocarbyloxy or hydrocarbyl thioether moieties;
  • R 5 and R 6 may combi.ne to form a heterocyclic ring structure with S; with the proviso that S is bound to an aliphatic or cycloaliphatic carbon atom; with the further proviso that the total carbon content of the hydrocarbon sulfide be such that it has sufficient hydrophobic character to cause the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral particles to be driven to an air/bubble interface.
  • the invention also concerns a process for recovering metal-containing minerals from an ore which comprises subjecting the ore, in the form of an aqueous pulp, to a froth flotation process in the presence of a flotating amount of a flotation collector under conditions such that the metal-containing minerals are recovered in the froth.
  • the collector compositions of this invention are capable of floating a broad range of metal-containing minerals. Furthermore, such collector compositions also give good recoveries and selectivity towards the desired metal-containing minerals.
  • the described collector composition is employed in a process for recovering metal-containing sulfide minerals or sulfidized metal-containing oxide minerals from an ore, which method comprises subjecting the ore, in the form of an aqueous pulp, to a froth flotation process in the presence of a flotating amount of the collector composition at conditions sufficient to cause the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral particles to be driven to the air/bubble interface and recovered in the froth.
  • the collector composition of this invention results in a surprisingly high recovery of nonferrous metal-containing minerals and a high selectivity toward such nonferrous metal-containing minerals when such metal- -containing minerals are found in the presence of iron- -containing sulfide minerals.
  • Component (a) of the collector composition of this invention is a component of formula (I) above.
  • component (a) in aqueous medium of lower pH, preferably acidic, component (a) can exist in the form of a salt.
  • R is advantageously -(CH 2 )- p
  • R 1 and each R 2 is advantageously a C 1 _ 22 hydrocarbyl radical or a C 1-22 hydrocarbyl radical substituted with one or more hydroxy, amino, phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano, halo, ether, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbylimmo groups. If substituted, R 1 and R 2 are advantageously substituted with one or more hydroxy, halo, amino, phosphonyl or alkoxy moieties.
  • R 1 and R 2 total 6 or more with R 1 preferably being a C 2-14 hydrocarbyl or a C 2-14 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl or alkoxy groups, more preferably a C 4-11 hydrocarbyl; and R 2 preferably being a C 1-6 alkyl, C 1-6 alkylcarbonyl or C 1-6 -substituted alkyl or alkylcarbonyl, more preferably a C 1-4 alkyl or C 1-4 alkylcarbonyl or a C 1-6 alkyl or C 1-6 alkylcarbonyl substituted with an amino, hydroxy or phosphonyl group, and most preferably a C 1-2 alkyl or C 1-2 alkylcarbonyl.
  • R is preferably being a C 2-14 hydrocarbyl or a C 2-14 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl or alkoxy groups, more preferably a C 4-11 hydrocarbyl
  • n is preferably an integer from 1 to 4, most preferably 2 or 3; X is prefer ⁇
  • R 3 is preferably hydrogen or C 1-14 hydrocarbyl, more preferably hydrogen or C 1-11 hydrocarbyl, most preferably hydrogen.
  • the component (a) includes compounds such as the S-(omega-aminoalkyl) hydrocarbon thioates:
  • omega-(hydrocarbylthio)alkylamines and omega- (hydrocarbylthio)alkylamides
  • R 1 is preferably a C 4-10 hydrocarbyl
  • the total carbon content of the groups R 1 and R 3 is preferably between about 1 and 23, more preferably 2 and 16, and most preferably 4 and 15; and when X is
  • R 1 is most preferably C 6-11 hydrocarbyl
  • the preferred component (a) compound includes omega-(hydrocarbylthio)alkylamine, N-(hydrocarbyl)-alpha,omega-alkanediamine, N-(omega- -aminoalkyl)hydrocarbon amides, omega-(hydrocarbyloxy-)alkylamine, omega-(hydrocarbylthio)alkylamides, or a mixture thereof. More preferred component (a) compounds include omega-(hydrocarbylthio)alkylamines, omega-(hydrocarbylthio)alkylamides, N-(hydrocarbyl)-
  • component (a) compounds are the omega- (hydrocarbylthio)alkylamines, for example, 2-(hexylthio)ethyl- amine and omega- (hydrocarbylthio)alkylamides, for example, ethyl 2-(hexylthio)ethylamide.
  • omega-(hydrocarbylthio)alkylamines of formula III can be prepared by the processes disclosed in Berazosky et al., U.S. Patent 4,086,273; French Patent 1,519,829; and Beilstein, 4, 4th Ed., 4th Supp., 1655 (1979).
  • N-(omega-aminoalkyl) hydrocarbon amides of formula V can be prepared by the processes described in Fazio, U.S. Patent 4,326,067 Acta Polon Pharm, 19, 277 (1962); Beilstein, 4, 4th Ed., 3rd Supp., 587 (1962).
  • the omega-(hydrocarbyloxy)alkylamines of formula VI can be prepared by the processes described in British Patent 869,409; and Hobbs, U.S. Patent 3,397,238.
  • S-(omega-aminoalkyl) hydrocarbon thioates of formula II can be prepared by the processes described in Faye et al., U.S. Patent 3,328,442; and Beilstein, 4, 4th Ed., 4th Supp., 1657 (1979).
  • omega-aminoalkyl hydrocarbonoates of formula VII can be prepared by the process described in J. Am. Chem. Soc, 83, 4835 (1961); Beilstein, 4, 4th Ed., 4th Supp., 1413 (1979) and Beilstein, 4, 4th Ed., 4th Supp., 1785 (1979).
  • N-(hydrocarbyl)-alpha,omega-alkanediamines of formula IV can be prepared by the process well-known in the art.
  • One example is the process described in East German Patent 98,510.
  • Component (b) of the collector composition is an organic compound which contains at least 4 carbon atoms and one or more monosulfide units wherein the sulfur atoms of the sulfide units are bound to nonaromatic carbon atoms, i.e., aliphatic or cycloaliphatic carbon atoms.
  • Monosulfide unit refers herein to a unit wherein each sulfur atom is bound to two carbon atoms of a non-aromatic moiety only, for example to two carbon atoms of a hydrocarbon moiety only.
  • the hydrocarbon compounds can contain one or more monosulfide units, and include such compounds which are substituted with hydroxyl, cyano, halo, ether, hydrocarbyloxy and hydrocarbyl thioether moieties.
  • Preferred organic compounds containing monosulfide units include those corresponding to the formula
  • R 5 and R 6 are independently a hydrocarbyl radical or a hydrocarbyl radical substituted with one or more hydroxy, cyano, halo, ether, hydrocarbyloxy or hydrocarbyl thioether moieties; wherein R 5 and R 6 may combine to form a heterocyclic ring structure with S; with the proviso that S is bound to an aliphatic or cycloaliphatic carbon atom; with the further proviso that the total carbon content of the sulfide portion be such that the sulfide portion have sufficient hydrophobic character to cause the metal-containing sulfide mineral particles to be driven to the air/bubble interface.
  • the specific R 5 and R 6 groups most advantageously employed herein are dependent on a variety of factors including the component (a) employed, the specific ore being treated and the like.
  • the monosulfide compound of formula IX contains at least 4, more preferably 6, and most preferably 8, carbon atoms.
  • the maximum number of carbon atoms in the monosulfide compound is preferably 20, more preferably 16, and most preferably 12.
  • R 5 and R 6 are independently an aliphatic, cycloaliphatic or aralkyl moiety, unsubstituted or substituted with one or more hydroxy, cyano, halo, -OR 7 or -SR 7 moieties, wherein R 7 is a hydrocarbyl radical; R 5 and R 6 may combine to form a heterocyclic ring with S.
  • R 5 and R 6 are more preferably an aliphatic or cycloaliphatic moiety, unsubstituted or substituted with one or more cyano, halo, hydroxy, OR 7 or SR 7 moieties, wherein R 7 is a hydrocarbyl radical; wherein R 5 and R 6 may combine to form a heterocyclic ring with
  • R 5 and R 6 do not combine to form a heterocyclic ring with S and R 5 and
  • R 6 are independently alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, unsubstituted or substituted with one or more hydroxy, halo, cyano, O R 7 or S R 7 moieties, wherein R 7 is aliphatic or cycloaliphatic.
  • R 5 and R 6 are not the same hydrocarbon moiety, that is, the monosulfide is asymmetrical.
  • R 7 preferably being aliphatic or cycloaliphatic.
  • R 7 is more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl.
  • R 5 and R 6 are independently alkyl or alkenyl, particularly R 5 is methyl or ethyl and R 6 is a C 6-11 alkyl or C 6-11 alkenyl group, for example, ethyl octyl sulfide.
  • cyclic compounds which can be employed as the monosulfide compound of formula IX include the following structures:
  • R 8 is independently hydrogen, an aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxy, cyano, halo, OR 7 or SR 7 group, wherein the aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group may optionally be substituted with a hydroxy, cyano, halo, OR 7 or SR 7 group, and the like; wherein R 7 is a hydrocarbyl group, preferably aliphatic or cycloaliphatic, more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl; and R 9 is a straight- or branched- alkylene or -alkenylene or
  • a preferred compound useful as component (b) in this invention corresponds to the formula:
  • R 4 is independently hydrocarbyl, or hydrocarbyl substituted with a hydroxy, cyano, halo, ether, hydrocarbyloxy or hydrocarbyl thioether moiety; wherein two R 4 moieties may combine to form a cyclic ring or heterocyclic ring with the sulfur atom; n is an integer of 0, 1, 2 or 3; with the proviso that the total carbon content of the hydrocarbon portion of the collector is such that the collector has sufficient hydrophobic character to cause the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral particles to be driven to the air/bubble interface.
  • R 4 is preferably an aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl group, unsubstituted or substituted with a cyano, halo, hydroxy, OR 7 or SR 7 group, wherein R 7 is as herembefore defined. More preferably, R 4 is an aliphatic or cycloaliphatic group, unsubstituted or substituted with a hydroxy, cyano, halo, aliphatic ether, cycloaliphatic ether, aliphatic thioether or cycloaliphatic thioether group.
  • R 4 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl moiety.
  • one -C(H) n (R 4 ) 3-n is a methyl or ethyl group, and the other is a C 6-11 alkyl or C 6-11 alkenyl group.
  • n is 1, 2 or 3, and more preferably 2 or 3.
  • R 5 -S- R 6 The preferred hydrocarbon containing monosulfide units of the formula R 5 -S- R 6 , wherein R 5 and R 6 are defined as above, are prepared by standard methods known in the art, e.g. reacting R 6 -H with R 5 -SH, where
  • R 5 and R 6 are defined as above.
  • Examples of compounds within the scope of this invention include methylbutyl sulfide, methylpentyl sulfide, methylhexyl sulfide, methylheptyl sulfide, methyloctyl sulfide, methylnonyl sulfide, methyldecyl sulfide, methylundecyl sulfide, methyldodecyl sulfide, methylcyclopentyl sulfide, methylcyclohexyl sulfide, methylcycloheptyl sulfide, methylcyclooctyl sulfide, ethylbutyl sulfide, ethylpentyl sulfide, ethylhexyl sulfide, ethylheptyl sulfide, ethyloctyl sulfide, ethy
  • More preferred sulfides include methylhexyl sulfide, methyl- heptyl sulfide, methyloctyl sulfide, methylnonyl sulfide, methyldecyl sulfide, ethylhexyl sulfide, ethylheptyl sulfide, ethyloctyl sulfide, ethylnonyl sulfide, ethyldecyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diheptyl sulfide, and dioctyl sulfide.
  • Hydrocarbon means herein an organic compound containing carbon and hydrogen atoms.
  • the term hydrocarbon includes the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aromatics, aliphatic and cycloaliphatic aralkanes and alkyl-substituted aromatics.
  • Aliphatic refers herein to straight and branched-chain, and saturated and unsaturated, hydro carbon compounds, that is, alkanes, alkenes or alkynes. Cycloaliphatic refers herein to saturated and unsaturated cyclic hydrocarbons, that is, cycloalkenes and cycloalkanes.
  • Cycloalkane refers to an alkane containing one, two, three or more cyclic rings. Cycloalkene refers to mono-, di- and polycyclic groups containing one or more double bonds.
  • Hydrocarbyl means herein an organic radical containing carbon and hydrogen atoms.
  • hydrocarbyl includes the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cycloaliphatic aralkyl and alkaryl.
  • aryl refers herein to biaryl, biphenylyl, phenyl, naphthyl, phenanthrenyl, anthracenyl and two aryl groups bridged by an alkylene group.
  • Alkaryl refers herein to an alkyl-, -alkenyl or alkynyl-substituted aryl substituent, wherein aryl is as defined hereinbefore.
  • Aralkyl means herein an alkyl group, wherein aryl is as defined hereinbefore.
  • C 1-20 alkyl includes straight- and branched-
  • Halo means herein a chloro, bromo, or iodo group.
  • Hydrocarbylene means herein an organic radical- -containing carbon and hydrogen atoms which must be attached to the nitrogen atom by a double bond.
  • hydrocarbylene includes the following organic radicals alkenyl, cycloalkenyl and aralkylene where aryl is defined as before.
  • a heterocyclic ring means herein both saturated and unsaturated heterocyclic rings including an -N-cyclic ring.
  • the heterocyclic ring may include one or more N, O or S atoms.
  • suitable heterocyclic rings are pyridine, pyrazole, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, coumarin, carbazole, acridine, imidazole, oxazole, thiazole, pyridazine, pyrimidine, pyrazine, purine, ethylenimine, oxirane, azetidine, oxetane, thietane, pyrrole, pyrrolidine, tetrahydrofuran, isoxazole, piperidine, azepine and others.
  • the composition of the present invention is prepared using sufficient amounts of component (a) and component (b) to prepare an effective collector for metal-containing minerals from ores in a froth flotation process.
  • the amounts of each component most advantageously employed in preparing the composition will vary depending on the specific components (a) and (b) employed, the specific ore being treated and the desired rates of recovery and selectivity.
  • the composition preferably comprises from about 10 to about 90, more preferably from 20 to 80, percent by weight, of component (a), and from about 10 to about 90, more preferably from 20 to 80, percent by weight, of component (b).
  • the composition of this invention even more preferably comprises from about 30 to about 70 percent by weight of component (a) and from about 30 to about 70 percent by weight of component (b).
  • the process of this invention is useful for the recovery by froth flotation of metal-containing minerals from ores.
  • An ore refers herein to the material as it is taken out of the ground and includes the desired metal-containing minerals in admixture with the gangue.
  • Gangue refers herein to that portion of the material which is of little or no value and needs to be separated from the desired metal-containing minerals.
  • the collector composition of this invention is preferably employed in the recovery, in a froth flotation process, of metal-containing minerals.
  • minerals containing copper, nickel, lead, zinc, or molybdenum are recovered.
  • minerals containing copper are recovered.
  • metal-containing sulfide minerals are those which have high natural hydrophobicity in the unoxidized state. The term "hydrophobicity in the unoxidized state" applies to a freshly ground mineral or a mineral having a fresh surface which demonstrates a tendency to float without collector addition.
  • Ores for which these compounds are useful include sulfide mineral ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and mixtures thereof.
  • metal-containing sulfide minerals which may be concentrated by froth flotation using the process of this invention include copper-bearing minerals such as, for example, covellite (CuS), chalcocite (Cu 2 S), chalco- pyrite (CuFeS 2 ), valleriite (Cu 2 Fe 4 S 7 or Cu 3 Fe 4 S 7 ) , bornite (Cu 5 FeS 4 ), cubanite (Cu 2 SFe 4 S 5 ), enargite [Cu 3 (As 1 Sb)S 4 ], tetrahedrite (Cu 3 SbS 2 ), tennantite (Cu 12 As 4 S 13 ), brochantite [Cu 4 (OH) 6 SO 4 ], antlerite [Cu
  • Preferred metal-containing sulfide minerals include molybdenite (MoS 2 ), chalcopyrite (CuFeS 2 ), galena (PbS), sphalerite (ZnS), bornite (Cu 5 FeS 4 ), and pentlandite ([(FeNi) 9 S 8 ].
  • Sulfidized metal-containing oxide minerals are minerals which are treated with a sulfidization chemical, so as to give such minerals sulfide mineral characteristics, so the minerals can be recovered in froth flotation using collectors which recover sulfide minerals. Sulfidization results in oxide minerals having sulfide mineral characteristics. Oxide minerals are sulfidized by contact with compounds which react with the minerals to form a sulfur bond or affinity. Such methods are well-known in the art. Such compounds include sodium hydrosulfide, sulfuric acid and related sulfur containing salts such as sodium sulfide.
  • Sulfidized metal-containing oxide minerals and oxide minerals for which this process is useful include oxide minerals containing copper, aluminum, iron, titanium, magnesium, chromium, tungsten, molybdenum, manganese, tin, uranium and mixtures thereof.
  • iron-containing minerals such as hematite and magnetite
  • chromium-containing minerals such as chromite (FeOCr 2 O 3 )
  • iron- and titanium-containing minerals such as ilmenite
  • magnesium- and aluminum- -containing minerals such as spinel
  • iron-chromium- -containing minerals such as chromite
  • titanium-con- taining minerals such as rutile
  • manganese-containing minerals such as pyrolusite
  • tin-containing minerals such as cassiterite
  • uranium-containing minerals such as uraninite
  • uranium-bearing minerals such as, for example, pitchblende [U 2 O 5 (U 3 O 8 )] and gummite (UO 3 nH 2 O).
  • metal-containing minerals for which this process is useful include gold-bearing minerals, such as sylvanite (AuAgTe 2 ) and calaverite (AuTe); platinum- and palladium-bearing minerals, such as sperrylite (PtAs 2 ); and silver-bearing minerals, such as hessite (AgTe 2 ). Also included are metals which occur in a metallic state, e.g. gold, silver and copper.
  • the collector composition of this invention can be used in any concentration which gives the desired recovery of the desired minerals.
  • the concentration used is dependent upon the particular minerals to be recovered, the grade of the ore to be subjected to the froth flotation process, the desired quality of the mineral to be recovered, and the particular mineral which is being recovered.
  • the collector composition of this invention is used in a concentration of 5 grams (g) to 1000 g per metric ton of ore, more preferably between about 10 g and 200 g of collector per metric ton of ore to be subjected to froth flotation.
  • g grams
  • collector composition of this invention is used in a concentration of 5 grams (g) to 1000 g per metric ton of ore, more preferably between about 10 g and 200 g of collector per metric ton of ore to be subjected to froth flotation.
  • Synergism is defined herein as when the measured result of a blend of two or more components exceeds the weighted average results of each component when used alone. This term also implies that the results are compared under the condition that the total weight of the collector used is the same for each experiment.
  • frothers are well-known in the art and reference is made thereto for the purposes of this invention. Any frother which results in the recovery of the desired metal-containing mineral is suitable.
  • Frothers useful in this invention include any frothers known in the art which give the recovery of the desired mineral. Examples of such frothers include C 5-8 alcohols, pine oils, cresols, C 1-4 alkyl ethers of polypropylene glycols, dihydroxylates of polypropylene glycols, glycols, fatty acids, soaps, alkylaryl sulfonates, and the like. Furthermore, blends of such frothers may also be used. All frothers which are suitable for beneficiation of ores by froth flotation can be used in this invention.
  • collector combination which makes up the composition of this invention can be used in mixtures with other collectors well-known in the art.
  • the collector composition of this invention may also be used with an amount of other collectors known in the art, sufficient to give the desired recovery of desired mineral.
  • examples of such other collectors useful in this invention include dialkyl thioureas, alkyl, dialkyl and trialkyl thiocarbonates, alkyl and dialkyl thionocarbamates, monoalkyl dithiophosphates, dialkyl and diaryl dithiophosphates, dialkyl monothiophosphates, diaryl dithiophosphates, dialkyl and diaryl thiophosphonyl chlorides, dialkyl and diaryl dithiophosphonates, alkyl mercaptans, xanthogen formates, mercapto benzothiazoles, fatty acids and salts of fatty acids, alkyl sulfuric acids and salts thereof, alkyl and alkaryl sulfonic acids and salts thereof, alkyl phosphoric acids and salts thereof, alkyl and aryl phosphoric acids and salts thereof,
  • a series of bags (Sample Nos . 1-8) containing 1200 g of homogeneous copper/molybdenum ore, containing chalcopyrite and molybdenite minerals, from Western Canada were prepared.
  • the ore in each bag was ground using 800 ml of tap water for 14 minutes in a ball mill having a mixed ball charge to produce approximately a 13 percent plus 100 mesh grind.
  • the resulting pulp was transferred to an Agitair 1500 ml flotation cell outfitted with an automated froth removal paddle.
  • the pH of each slurry was adjusted to 10.2 using lime. No further pH adjustments were made during the test.
  • a standard methyl isobutyl carbinol (MIBC) frother and the collectors or collector combinations set forth in Table I were employed to float the copper and molybdenum using a four-stage rougher flotation scheme as set forth below.
  • MIBC methyl isobutyl carbinol
  • 3 Grade is the fractional content of the specified metal in total weight collected in the froth.
  • the collector composition comprises 50 weight percent of each collector.
  • the 95 percent confidence level of statistical error associated with the Cu R-7 value in Table I is ⁇ 0.010.
  • the statistical range of R-7 values for Cu in Table I associated, for example, with collector A is 0.688 ⁇ 0.010 or 0.678 to 0.698.
  • the recoveries of Cu and Mo at 7 minutes with the collector blends of this invention match or exceed the 7 minute recoveries that would be expected from a weighted average effect of the components used alone; synergism has occurred.
  • a series of samples of -10 mesh ore from Eastern Canada were divided into 900 g samples.
  • the ore contained chalcopyrite, pentlandite, and pyrrhotite minerals. All tests were performed using an Agitair 1500 ml cell operated at a speed of 900 rpm with an air flow of 9.0 liters/minute.
  • each sample was ground in a rod mill for 1080 revolutions.
  • 600 ml of water were added along with sufficient lime to adjust the slurry pH to 9.2.
  • the ore had a particle size less than 200 mesh (75 microns).
  • the rod mill contents were emptied into the float cell and the pH adjusted to 9.2 (using either lime or sulfuric acid).
  • a complex nine-stage flotation sequence was performed. The first four stages are referred to as rougher float and stages five through nine as scavenger float. After stage 4, sulfuric acid was added to adjust the pH to 9.2; CuSO 4 was added to stage 5 and stage 7 (0.015 kg/metric ton). The frother used was DOWFROTH ® 250.
  • the lowest pyrrhotite recovery and highest Cu and Ni recoveries possible after 7 minutes are important, as it is at this time point that the major rejection of high sulfur containing mineral occurs.
  • the Cu and Ni recoveries are to be the highest possible using normal flotation logic.
  • Cu recoveries were approaching the theoretical limit of 1.0 at both 7 and 17 minutes, so statistically significant comparisions were not possible.
  • Ni recovery of Ni at 7 minutes using a collector blend of this invention gave a high value with low pyrrhotite.
  • the Ni recovery at 17 minutes with the blend of this invention is high.
  • the 95 percent confidence level of statistical error associated with Ni at R-7 is ⁇ 0.015 and at R-17 is ⁇ 0.006; pyrrhotite at R-7 is ⁇ 0.012.
  • Ni recovery shows that synergism has occurred with desired lower recovery of pyrrhotite.
  • a series of uniform 1000 g samples of a complex Pb/Zn/Cu/Ag ore from Central Canada were prepared.
  • the ore contained galena, sphalerite, chal- copyrite, and argentite minerals.
  • a sample was added to a rod mill along with 500 ml of tap water and 7.5 ml of SO 2 solution.
  • Six and one-half minutes of mill time were used to prepare the feed such that 90 percent of the ore had a particle size of less than 200 mesh (75 microns).
  • the contents were transferred to a cell fitted with an automated paddle for froth removal, and the cell was attached to a standard Denver flotation mechanism.
  • Stage I being a copper/lead/silver rougher float and Stage II being a zinc rougher float.
  • Stage II being a zinc rougher float.
  • 1.5 g/kg of Na 2 CO 3 was added (pH of 9 to 9.5), followed by the addition of the collector(s).
  • the pulp was then conditioned for 5 minutes with air and agitation. This was followed by a 2-minute condition period with agitation only.
  • a methyl isobutyl carbinol (MIBC) frother was then added (standard dose of 0.015 ml/kg).
  • MIBC methyl isobutyl carbinol
  • the Stage II flotation consisted of adding 0.5 kg/metric ton of CuSO 4 to the cell remains of Stage I.
  • the pH was then adjusted to 10.5 with lime addition. This was followed by a condition period of 5 minutes with agitation only. The pH was then rechecked and adjusted back to 10.5 with lime. At this point, the collector(s) were added, followed by a five-minute condition period with agitation only.
  • a methyl isobutyl carbinol (MIBC) frother was then added (standard dose of 0.020 ml/kg). Concentrate was collected for 5 minutes and labeled as zinc rougher concentrate.
  • MIBC methyl isobutyl carbinol
  • the 95 percent confidence levels of statistical error in the 5 minute recovery data of the Cu/Pb flotation are for Ag, ⁇ 0.01; Cu, ⁇ 0.01; and Pb, ⁇ 0.02.
  • Runs 1 and 4 represent the tests where single components were used in each stage.
  • Stage I of Run 2 the addition of the two component blend of this invention at less dosage (24% less) as compared to the single component collector of Stage I of Run 1, gave slightly more Ag and Cu recovery and significantly more Pb recovery.

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  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

Une composition collectrice qui est utile pour extraire des minéraux de sulfure contenant des métaux, des minéraux d'oxyde contenant des métaux sulfurés, des minéraux d'oxyde contenant des métaux, et des métaux présents à l'état métallique dans des minerais lors d'un processus de flottation par écumage, comprend deux collecteurs. L'un de ces collecteurs est un composé organique contenant au moins quatre atomes de carbone et un ou plusieurs unités de monosulfure, dans lequel les atomes de carbone auquel sont liés les atomes de soufre sont des carbones aliphatiques ou cycloaliphatiques. L'autre collecteur est de préférence une oméga-(hydrocarbylthio)alkylamine, S-(oméga-aminoalkyle)-hydrocarbyle thioate, N-(hydrocarbyle)-alpha,oméga-alkane-diamine, un amide d'hydrocarbure (oméga-aminoalkyle), une oméga-(hydrocarbyloxy)alkylamine, un oméga-aminoalkyl hydrocarbonoate, un oméga-(hydrocarbylthio)-alkylamide ou un mélange de ceux-ci.
PCT/US1986/000342 1985-11-29 1986-02-18 Compositions collectrices pour la flottation par ecumage de valeurs minerales Ceased WO1987003222A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR8607004A BR8607004A (pt) 1985-11-29 1986-02-18 Composicoes coletoras para a flotacao de espuma de valores minerais
RO12922786A RO100034B1 (en) 1985-11-29 1986-12-18 Collecting composition for foam floating of minerals
SU874203131A RU1839638C (ru) 1985-11-29 1987-07-22 Коллекторна композици дл флотации руд, содержащих цветные металлы
NO873156A NO168408C (no) 1985-11-29 1987-07-28 Kollektormaterialer for flotasjon av metallholdige mineraler, samt fremgangsmaate for utvinning av slike mineraler
FI873288A FI82395C (fi) 1985-11-29 1987-07-28 Samlarkompositioner foer flotation av mineraler.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80288285A 1985-11-29 1985-11-29
US802,882 1985-11-29

Publications (1)

Publication Number Publication Date
WO1987003222A1 true WO1987003222A1 (fr) 1987-06-04

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PCT/US1986/000342 Ceased WO1987003222A1 (fr) 1985-11-29 1986-02-18 Compositions collectrices pour la flottation par ecumage de valeurs minerales

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JP (1) JPS62129160A (fr)
CN (1) CN1014247B (fr)
AU (1) AU588579B2 (fr)
BR (1) BR8607004A (fr)
CA (1) CA1268565A (fr)
ES (1) ES8706045A1 (fr)
FI (1) FI82395C (fr)
MX (1) MX173645B (fr)
PH (1) PH23458A (fr)
PL (1) PL147852B1 (fr)
RO (1) RO100034B1 (fr)
RU (1) RU1839638C (fr)
SE (1) SE461768B (fr)
WO (1) WO1987003222A1 (fr)
YU (1) YU45766B (fr)
ZA (1) ZA861170B (fr)
ZM (1) ZM1586A1 (fr)
ZW (1) ZW4186A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339856A3 (fr) * 1988-04-28 1991-01-16 The Dow Chemical Company Agents déprimants de la pyrite utilisables pour la séparation de la pyrite et du charbon
WO2018172307A1 (fr) 2017-03-23 2018-09-27 Akzo Nobel Chemicals International B.V. Procédé de traitement de minerais métalliques ou minéraux et composition de collecteur associée
WO2019113082A1 (fr) 2017-12-06 2019-06-13 Dow Global Technologies Llc Formulation de collecteur pour améliorer la récupération de métal dans des applications d'exploitation minière
EP3636346A1 (fr) 2018-10-08 2020-04-15 Nouryon Chemicals International B.V. Procédé de traitement de minerais et composition collectrice associée
CN114192273A (zh) * 2021-11-29 2022-03-18 浙江遂昌汇金有色金属有限公司 一种含贵金属固废无害化、资源化处理工艺
US20220266263A1 (en) * 2019-07-24 2022-08-25 Basf Se Collector composition
CN118179751A (zh) * 2024-04-11 2024-06-14 昆明理工大学 一种磁黄铁矿组合捕收剂及其制备方法和应用

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ES8706047A1 (es) * 1985-11-29 1987-06-01 Dow Chemical Co Un procedimiento para la recuperacion de minerales que contienen metales a partir de una mena
US5700369A (en) * 1997-01-14 1997-12-23 Guangzhou Institute Of Geochemistry Chinese Academy Of Sciences Process for adsorboaggregational flotation of Carlin type natural gold ore dressing
US8734757B2 (en) * 2008-04-04 2014-05-27 Bhp Billiton Ssm Development Pty Ltd. Odor control
CN102941160A (zh) * 2012-12-13 2013-02-27 贵州大学 一种硅酸盐矿物浮选捕收剂
CN110015727B (zh) * 2019-05-09 2021-07-09 安徽工业大学 一种电解气浮除去水体中微塑料的方法
CN111068924B (zh) * 2019-12-23 2020-10-16 中南大学 2-氰基-n-(取代氨甲酰)乙酰胺类化合物在含钙矿物浮选中的应用
CN114798184B (zh) * 2022-05-16 2024-01-23 北京盈翔科技有限公司 用于铜金矿浮选的高效起泡剂及其应用方法
CN115228594B (zh) * 2022-07-25 2025-01-07 中南大学 氧化锑矿的浮选预活化剂及其活化和浮选方法
CN115445779B (zh) * 2022-09-29 2024-08-23 中南大学 一种辉钼矿和方铅矿选择性浮选分离的药剂和方法
CN115739399B (zh) * 2022-12-22 2024-10-01 沈阳有色金属研究院有限公司 一种用于浮选有色金属硫化矿的复合捕收剂及其制备方法和应用
JPWO2024172017A1 (fr) * 2023-02-15 2024-08-22
CN118698748B (zh) * 2024-08-27 2024-11-12 中南大学 浮选镍硫化矿的捕收剂、浮选药剂和方法

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US2169313A (en) * 1938-09-24 1939-08-15 Minerals Separation North Us Concentration of metalliferous ores by flotation
US3328442A (en) * 1963-12-18 1967-06-27 Massachusetts College Of Pharm Anti-radiation compounds and their preparation
US3397238A (en) * 1965-11-16 1968-08-13 Pfizer & Co C Process for the preparation of alkyl ethers of amino-alcohols
US4086273A (en) * 1976-04-14 1978-04-25 The Dow Chemical Company Process for making beta-aminoethyl sulfides from aliphatic mercaptans and 2-oxazolines
US4326067A (en) * 1980-12-03 1982-04-20 The Dow Chemical Company Process for making N-(2-aminoethyl)amides

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PH23738A (en) * 1985-05-31 1989-11-03 Dow Chemical Co Novel collectors for the selective froth flotation of sulfide minerals
ZM1386A1 (en) * 1985-07-12 1988-12-30 Dow Chemical Co Novel collector compositions for froth flotation
ES8706047A1 (es) * 1985-11-29 1987-06-01 Dow Chemical Co Un procedimiento para la recuperacion de minerales que contienen metales a partir de una mena

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Publication number Priority date Publication date Assignee Title
US2169313A (en) * 1938-09-24 1939-08-15 Minerals Separation North Us Concentration of metalliferous ores by flotation
US3328442A (en) * 1963-12-18 1967-06-27 Massachusetts College Of Pharm Anti-radiation compounds and their preparation
US3397238A (en) * 1965-11-16 1968-08-13 Pfizer & Co C Process for the preparation of alkyl ethers of amino-alcohols
US4086273A (en) * 1976-04-14 1978-04-25 The Dow Chemical Company Process for making beta-aminoethyl sulfides from aliphatic mercaptans and 2-oxazolines
US4326067A (en) * 1980-12-03 1982-04-20 The Dow Chemical Company Process for making N-(2-aminoethyl)amides

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339856A3 (fr) * 1988-04-28 1991-01-16 The Dow Chemical Company Agents déprimants de la pyrite utilisables pour la séparation de la pyrite et du charbon
WO2018172307A1 (fr) 2017-03-23 2018-09-27 Akzo Nobel Chemicals International B.V. Procédé de traitement de minerais métalliques ou minéraux et composition de collecteur associée
EA039428B1 (ru) * 2017-03-23 2022-01-26 Норион Кемикалз Интернэшнл Б.В. Способ обработки металлических или минеральных руд и соответствующая композиция собирателей
AU2018237908B2 (en) * 2017-03-23 2022-07-21 Nouryon Chemicals International B.V. Process to treat metal or mineral ores and collector composition therefor
WO2019113082A1 (fr) 2017-12-06 2019-06-13 Dow Global Technologies Llc Formulation de collecteur pour améliorer la récupération de métal dans des applications d'exploitation minière
EP3636346A1 (fr) 2018-10-08 2020-04-15 Nouryon Chemicals International B.V. Procédé de traitement de minerais et composition collectrice associée
US20220266263A1 (en) * 2019-07-24 2022-08-25 Basf Se Collector composition
CN114192273A (zh) * 2021-11-29 2022-03-18 浙江遂昌汇金有色金属有限公司 一种含贵金属固废无害化、资源化处理工艺
CN118179751A (zh) * 2024-04-11 2024-06-14 昆明理工大学 一种磁黄铁矿组合捕收剂及其制备方法和应用

Also Published As

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SE461768B (sv) 1990-03-26
ZA861170B (en) 1987-10-28
YU23086A (en) 1988-06-30
MX173645B (es) 1994-03-22
SE8702987D0 (sv) 1987-07-28
CN86101495A (zh) 1987-06-03
ES8706045A1 (es) 1987-06-01
CN1014247B (zh) 1991-10-09
JPS62129160A (ja) 1987-06-11
BR8607004A (pt) 1987-12-01
FI82395B (fi) 1990-11-30
AU588579B2 (en) 1989-09-21
ZW4186A1 (en) 1987-09-09
PH23458A (en) 1989-08-07
ZM1586A1 (en) 1988-12-30
CA1268565A (fr) 1990-05-01
ES552033A0 (es) 1987-06-01
FI873288L (fi) 1987-07-28
RU1839638C (ru) 1993-12-30
RO100034B1 (en) 1992-05-25
YU45766B (sh) 1992-07-20
PL147852B1 (en) 1989-08-31
SE8702987L (sv) 1987-07-28
PL257989A1 (en) 1987-06-01
FI873288A0 (fi) 1987-07-28
AU5543786A (en) 1987-07-01
FI82395C (fi) 1991-03-11

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