WO1987003221A1 - Nouveaux collecteurs permettant la flottation par ecumage de mineraux - Google Patents

Nouveaux collecteurs permettant la flottation par ecumage de mineraux Download PDF

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Publication number
WO1987003221A1
WO1987003221A1 PCT/US1986/000341 US8600341W WO8703221A1 WO 1987003221 A1 WO1987003221 A1 WO 1987003221A1 US 8600341 W US8600341 W US 8600341W WO 8703221 A1 WO8703221 A1 WO 8703221A1
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Prior art keywords
omega
alkyl
composition
hydrocarbyl
hydrocarbylthio
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PCT/US1986/000341
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English (en)
Inventor
Richard R. Klimpel
Robert D. Hansen
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The Dow Chemical Company
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Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to BR8607003A priority Critical patent/BR8607003A/pt
Publication of WO1987003221A1 publication Critical patent/WO1987003221A1/fr
Priority to SU874203123A priority patent/RU1837985C/ru
Priority to SE8702988A priority patent/SE8702988L/xx
Priority to NO873155A priority patent/NO168991C/no
Priority to FI873287A priority patent/FI873287A/fi

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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
    • B03D1/01—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
    • B03D1/012—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
    • B03D1/014—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

Definitions

  • This invention concerns compositions useful as 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, e.g., copper sulfate to induce flotation in the presence of a collector
  • 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 to produce optimum metallurgical results, e.g., lime, soda ash; 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.
  • 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 atomsphere through smokestacks, or are removed from such smokestacks by expensive and elaborate scrubbing equipment. Many nonferrous metal-containing sulfide minerals or metal-containing oxide minerals are formed naturally in the presence of iron-containing sulfide minerals, such as pyrite and pyrrhotite.
  • 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 presence of iron-containing sulfide minerals.
  • a flotation collector which will selectively recover, at relatively good recovery rates, a broad range of metal-containing minerals from ores in the presence of iron-containing sulfide minerals such as pyrite and pyrrhotite.
  • the present invention in one aspect, is a collector composition which comprises:
  • Y is S, O, a hydrocarbylene radical or a substituted hydrocarbylene radical
  • cyclic ring is saturated or unsaturated and may contain additional hetero atoms, but must contain the N;
  • 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 is hydrogen, a C 1-22 hydrocarbyl radical or a substituted C 1-22 hydrocarbyl radical; and (b) an alkyl thiocarbonate, a thionocarbamate, a thiophosphate, a thiocarbanilide, a thiophosphinate, a mercaptan, a xanthogen formate, a xanthic ester or mixture thereof.
  • the invention also concerns a process for recovering metal-containing sulfide 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 novel collector composition of this invention often gives higher recoveries, often with better grade, than can be achieved with the use of either collector component alone.
  • the described collector composition is employed in a process for recovering metal-containing sulfide minerals on sulfidized metal-containing oxide 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 the collector composition at conditions sufficient to cause the metal-containing sulfide mineral or sulfidized metalcontaining 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 higher 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 low 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 are 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 hydrocarbylimino groups. If substituted, R 1 or R 2 is advantageously substitued with one or more hydroxy, halo, amino, phosphonyl or alkoxy moiety.
  • Q is preferably -N(R 2 ) a (H) b where a + b equals 2. More advantageously, the carbon atoms in 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 a C 1-2 alkyl or C 1-2 alky
  • n is preferably an integer from 1 to 4, most preferably 2 or 3;
  • X is preferably -S-, -N '-R 3 , or -O-, more preferably -S- or -N'-R 3 , most preferably -S-; and
  • 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 -
  • omega-(hydrocarbylthio)alkylamines and omega(hydrocarbylthio)alkyl amides f f the N-(hydrocarbyl)-alpha,omega-alkanediamines:
  • omega-(hydrocarbyloxy-)alkylamines f > f
  • omega-aminoalkyl hydrocarbonoates f f
  • R 1 , R 2 , R 3 , a, b and n are as hereinbefore defined.
  • R 1 is preferably a C 4-10 hydrocarbyl
  • the total carbon content of the groups R 1 and R 3 is preferably between 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.
  • (a) compound includes omega-(hydrocarbylthio)alkylamine, N-(hydrocarbyl)-alpha,omega-alkanediamine,
  • omega-(hydrocarbyloxy-)alkylamines N-(omega-aminoalkyl)hydrocarbon amide, omega-(hydrocarbylthio)- alkylamide or mixtures thereof.
  • More preferred component (a) compounds include omega-(hydrocarbylthio)- alkylamines, N-(hydrocarbyl)-alpha,omega-alkanediamines, N-(omega-aminoalkyl)hydrocarbon amides, omega-(hydrocarbylthio)alkylamide or mixtures thereof.
  • the most preferred class of component (a) compounds are the omega-(hydrocarbylthio)alkylamines and omega-(hydrocarbylthio)alkylamide.
  • Especially preferred compounds are 2-(hexylthio)ethylamine and 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
  • 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); and Beilstein, 4, 4th Ed., 3rd Supp., 587 (1962).
  • 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.
  • the 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).
  • the 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.
  • the second component (b) of the collector composition of this invention is an alkyl thiocarbonate, a thionocarbamate, a thiocarbanilide, a thiophosphate, thiophosphinates, mercaptan, xanthogen formate, xanthic ester and mixtures thereof.
  • Preferred second component (b) collectors are an alkyl thiocarbonate, a thionocarbamate, a thiophosphate or mixtures thereof.
  • Preferred thiocarbonates are the alkyl thiocarbonates represented by the structural formula: (VII wherein
  • R 4 is a C 1-20 , preferably C 2-16 , more preferably C 3-12 alkyl group; Z 1 and Z 2 are independently a sulfur or oxygen atom; and M + is an alkali metal cation.
  • alkyl monothiocarbonates examples include sodium ethyl monothiocarbonate, sodium isopropyl monothiocarbonate, sodium isobutyl monothiocarbonate, sodium amyl monothiocarbonate, potassium ethyl monothiocarbonate, potassium isopropyl monothiocarbonate, potassium isobutyl monothiocarbonate, and potassium amyl monothiocarbonate.
  • Preferred alkyl dithiocarbonates include potassium ethyl dithiocarbonate, sodium ethyl dithiocarbonate, potassium amyl dithiocarbonate, sodium amyl dithiocarbonate, potassium isopropyl dithiocarbonate, sodium isopropyl dithiocarbonate, sodium sec-butyl dithiocarbonate, potassium sec-butyl dithiocarbonate, sodium isobutyl dithiocarbonate, potassium isobutyl dithiocarbonate, and the like.
  • alkyl trithiocarbonates include sodium isobutyl trithiocarbonate and potassium isobutyl trithiocarbonate. It is often preferred to employ a mixture of an alkyl monothiocarbonate, alkyl dithiocarbonate and alkyl trithiocarbonate.
  • Preferred thionocarbamates correspond to the formula
  • R 5 is independantly a C 1-10 , preferably a C 1-4 , more preferably a C 1-3 , alkyl group;
  • Y is -S -M + or -OR 6 , wherein R 6 is a C 2-10 , Preferably a C 2-6 , more preferably a C 3-4 , alkyl group; c is the integer 1 or 2; and d is the integer 0 or 1, wherein c+d must equal 2.
  • dialkyl dithiocarbamates examples include methyl butyl dithiocarbamate, methyl isobutyl dithiocarbamate, methyl sec-butyl dithiocarbamate, methyl propyl dithiocarbamate, methyl iso propyl dithiocarbamate, ethyl butyl dithiocarbamate, ethyl isobutyl dithiocarbamate, ethyl sec- -butyl dithiocarbamate, ethyl propyl dithiocarbamate, and ethyl isopropyl dithiocarbamate.
  • Exampies of preferred alkyl thionocarbamates include N-methyl butyl thionocarbamate, N-methyl isobutyl thionocarbamate, N-methyl sec-butyl thionocarbamate, N-methyl propyl thionocarbamate, N-methyl isopropyl thionocarbamate, N-ethyl butyl thionocarbamate, N-ethyl isobutyl thionocarbamate, N-ethyl sec-butyl thionocarbamate, N-ethyl propyl thionocarbamate, and N-ethyl isopropyl thionocarbamate.
  • N-ethyl isopropyl thionocarbamate and N-ethyl isobutyl thionocarbamate are most preferred.
  • R 7 is independently hydrogen or a C 1-10 , preferably C 2-8 , alkyl group or an aryl, preferably an aryl group having from 6-10 carbon atoms, most preferably cresyl;
  • Z is oxygen or sulfur; and
  • M is an alkali metal cation.
  • those preferably employed include the monoalkyl dithiophosphates (one R 7 is hydrogen and the other R 7 is a C 1-10 alkyl and Z is S-), dialkyl dithiophosphates (both R 7 are C 1-10 alkyl and Z is S-), dialkyl monothiophosphate (both R 7 are a C 1-10 alkyl and Z is O-), and diaryl dithiophosphate (both R 7 are aryl and Z is S-)
  • Examples of preferred monoalkyl dithiophosphates include ethyl dithiophosphate, propyl dithiophosphate, isopropyl dithiophosphate, butyl dithiophosphate, sec-butyl dithiophosphate, and isobutyl dithiophosphate.
  • Examples of dialkyl or diaryl dithiophosphates include sodium diethyl dithiophosphate, sodium di-sec-butyl dithiophosphate, sodium diisobutyl dithiophosphate, sodium diisoamyl dithiophosphate and sodium dicresyl dithiophosphate.
  • Preferred monothiophosphates include sodium diethyl monothiophosphate, sodium di-sec-butyl monothiophosphate, sodium diisobutyl monothiophosphate, and sodium diisoamyl monothiophosphate.
  • Thiocarbanilides (dialkyl thioureas) are represented by the general structural formula:
  • R 11 is individually H or a C 1-6 , preferably a C 1-3 , hydrocarbyl.
  • Thiophosphinates are represented by the general structural formula:
  • R 12 is independently an alkyl or aryl group, preferably an alkyl group having from 1 to 12, more preferably an alkyl group having from 1 to 8 carbon atoms. Most preferably, each R 12 is isobutyl.
  • Mercaptan collectors are preferably alkyl mercaptans represented by the general structural formula:
  • R 13 is an alkyl group, preferably an alkyl group having at least 10, more preferably from 10 to 16, carbon atoms.
  • R 14 is an alkyl group having from 1 to 7, preferably from 2 to 6 carbon atoms and R 15 is an alkyl group having 1 to 6, preferably 2 to 4, more preferably 2 or 3, carbon atoms.
  • Xanthic esters are preferably compounds of the general structural formula:
  • R 16 is an allyl group having from 2 to 7 carbon atoms
  • R 17 is an alkyl group having from 1 to 7 carbon atoms
  • Preferred compounds for use as component (b) herein are the thiocarbonates, thionocar- bamates and the thiophosphates due to the surprisingly high recoveries and selectivities towards metal-containing minerals which can be achieved.
  • 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, hydrocarbon 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 polycylic groups containing one or more double bonds.
  • Hydrocarbyl means herein an organic radical containing carbon and hydrogen atoms. The term 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 branchedchain methyl, ethyl, propyl, butyl, pentyl, hexyl, neptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
  • 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 compounds 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, thiethane, 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 amount of components (a) and (b) are selected such that the recovery of metal-containing minerals in a froth flotation process is higher than either component could recover at the same weight dosage.
  • a particularly preferred composition of the present invention comprises (a) an omega-(hydrocarbylthio)alkylamine, N-(hydrocarbyl)-alpha,omega-alkanedi- amine, N-(omega-aminoalkyl)hydrocarbon amide, omega- (hydrocarbylthio)alkylamide or mixtures thereof; and (b) an alkyl thiocarbonate which comprises an alkyl monothiocarbonate, alkyl dithiocarbonate or alkyl trithiocarbonate.
  • 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 metal 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.
  • 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.
  • CuS covellite
  • CuFeS 2 chalcocite
  • CuFeS 2 chalco- pyrite
  • valleriite Cu 2 Fe 4 S 7 or Cu 3 Fe 4 S 7
  • bornite Cu 5 FeS 4
  • cubanite
  • Preferred metal-containing sulfide minerals include molybdenite (MoS 2 ), chalcopyrite (CuFeS 2 ), galena (PBS), sphalerite (ZnS), bornite (Cu 5 FeS 4 ), and pent- landite [(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.
  • 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 compositions of this invention can be used in any concentration which gives the desired recovery of the desired minerals.
  • 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 minerals to be recovered, and the particular mineral which is being recovered.
  • the collector compositions of this invention are used in concentrations 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 which give the desired recovery of desired minerals.
  • examples of such other collectors useful in this invention include dialkyl and diaryl thiophosphonyl chlorides, 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, sulfosuccinates, sulfosuccinamates, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkyl pyridinium salts, guanidine, and alkyl propylene diamines.
  • Example 1 Froth Flotation of a Cu/Ni Ore
  • the 95 percent confidence levels of statistical error associated with Cu R-12 and Ni R-12 experimental values in Table I are ⁇ 0.008 and ⁇ 0.013, respectively.
  • the statistical range of R-12 values for Ni in Table I is 0.842 ⁇ 0.013 Or 0.829 to 0.855. Applying these limits clearly indicates that the recoveries of Cu and Ni with the collector blends of this invention exceed the 12 minute recoveries that would be expected from a weighted average effect of the individual components used alone. Synergism has occurred in the metal recovery with the additional benefit of getting lower undesired pyrrhotite recovery.
  • Example 2 Froth Flotation of a Complex Pb/Zn/Cu/Ag Ore
  • the ore contained galena, sphalerite, chalcopyrite and argentite.
  • 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 frother was then added (standard dose of 0.020 ml/kg). Concentrate was collected for 8 minutes and labeled as zinc rougher concentrate.
  • the 95 percent confidence levels of statistical error in the 8 minute recovery data of the Cu/Pb flotation are for Ag, ⁇ 0.01; Cu, ⁇ 0.01; and Pb, ⁇ 0.02.
  • Run 2 represents the test where single components were used in each stage.
  • Stage I of Run 3 the addition of the two component blend of this invention as compared to the single component collector of Stage I of Run 2 gave significantly more Ag, Cu and Pb recovery. Ag, Cu and Pb values not recovered in Stage I were lost to this process and discarded.
  • Example 3 Froth Flotation of CuO Ore Uniform 500 g samples of copper oxide ore, containing malachite mineral, from Western Australia were prepared as a slurry, previously adjusted to a pH of 10.4 by lime, using an Agitar 1500 ml cell. A series of initial floats (denoted as a sulfide float) were performed on these samples using the various collectors set forth in Table II at a dosage of 350 g/metric ton of ore. One minute of conditioning time was employed. The concentrate was removed for 3 minutes using a triethoxy butane frother as required. The recovered concentrate was then analyzed.
  • Oxide floats were then conducted on the samples by first adding 500 g/metric ton of sodium hydrosulfide to the cell residue. Following this addition, there was a two-minute condition period. A one-minute concentrate and a two- to five-minute concentrate were collected using a triethoxy butane frother as required. Twenty grams of potassium amyl xanthate and 35 grams of sodium hydrosulfide were added per ton of ore to the cell residue and conditioned for one minute. A five-minute concentrate was then collected. An additional 20 grams of potassium amyl xanthate and 35 grams of sodium hydrosulfide per ton of ore were added to the cell residue and conditioned for one minute. A five-minute concentrate was then collected. The collected concentrates and tails were dried, weighed and analyzed for total copper content using standard analytical techniques. The results are presented in Table III.
  • the statistical confidence levels of the experimental Cu recovery values in the 15 minute oxide float is ⁇ 0.018. It is clear that the collector blends of this invention gave copper recoveries in the oxide float that significantly exceed those recoveries that would be expected from a weighted average effect of each component used alone. In addition, there are desirable benefits in improving the grade of the copper mineral floated with the blends of this invention.
  • a large dry feed sample of nickel/cobalt ore, containing pentlandite and cobalt-containing mineral, from Western Australia was collected from which a series of test samples (750 grams) were prepared in slurry form.
  • test samples 750 grams
  • an Agitar 1500 ml cell outfitted with a froth removal paddle was employed except for the final cleaner float which was done with a smaller cell and froth removed by hand.
  • the flotation procedure employed consisted of first adding 0.2 kg of CuSO 4 per metric ton of ore, conditioning the resulting mixture for 7 minutes, adding 0.1 kg/ton collector and conditioning for 3 minutes. The mixture was then transferred from the conditioning vessel to the cell.

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  • Manufacture And Refinement Of Metals (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Saccharide Compounds (AREA)

Abstract

Une composition collectrice, destinée à être utilisée dans les procédés de flottation par écumage, comprend deux collecteurs. L'un des collecteurs est de préférence constitué de: oméga-(hydrocarbylthio)-alkylamine, thioate de S-(oméga-aminoalkyle) hydrocarbyle, N-(hydrocarbyle)-alpha, oméga-alkanédiamine, amide de (oméga-aminoalkyle) hydrocarbure, oméga-(hydrocarbyloxy)-alkylamine, hydrocarbonate d'oméga-aminoalkyle, oméga-hydrocarbylthio)alkylamide, ou d'un mélange de ces compositions. Le second collecteur est constitué de: thiocarbonate, thionocarbamate, thiophosphate, thiocarbinilide, thiophosphinate, mercaptan, formiate xanthogénique, ester xanthique, ou d'un mélange de ces compositions. Ladite composition collectrice permet la flottation d'une gamme étendue de minéraux contenant du métal.
PCT/US1986/000341 1985-11-29 1986-02-18 Nouveaux collecteurs permettant la flottation par ecumage de mineraux WO1987003221A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR8607003A BR8607003A (pt) 1985-11-29 1986-02-18 Novos coletores para flotacao de espuma de minerais
SU874203123A RU1837985C (ru) 1985-11-29 1987-07-24 Коллекторна композици дл пенной флотации металлосодержащих минералов
SE8702988A SE8702988L (sv) 1985-11-29 1987-07-28 Nya samlarreagenskompositioner for skumflotation av mineral
NO873155A NO168991C (no) 1985-11-29 1987-07-28 Samlerblanding for skumflotasjon av metallholdige mineraler
FI873287A FI873287A (fi) 1985-11-29 1987-07-28 Nya samlare foer flotation av mineraler.

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US80302685A 1985-11-29 1985-11-29
US803,026 1985-11-29

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WO1987003221A1 true WO1987003221A1 (fr) 1987-06-04

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CN (1) CN86101573A (fr)
AU (1) AU586471B2 (fr)
BR (1) BR8607003A (fr)
ES (1) ES8706047A1 (fr)
FI (1) FI873287A (fr)
PH (1) PH24537A (fr)
PL (1) PL147930B1 (fr)
RU (1) RU1837985C (fr)
SE (1) SE8702988L (fr)
WO (1) WO1987003221A1 (fr)
YU (1) YU45765B (fr)
ZA (1) ZA861171B (fr)
ZM (1) ZM1486A1 (fr)
ZW (1) ZW4286A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0298392A2 (fr) * 1987-07-07 1989-01-11 Henkel Kommanditgesellschaft auf Aktien Procédé et agents pour l'obtention par flottation de minéraux à partir de minerais sulfurés
WO1991002097A1 (fr) * 1989-08-04 1991-02-21 The Broken Hill Proprietary Company Limited Flottage d'ions avec des reactifs non-ioniques
FR2994534A1 (fr) * 2012-08-20 2014-02-21 Ceca Sa Collecteurs pour enrichissement de minerais
WO2015054381A1 (fr) * 2013-10-09 2015-04-16 Georgia-Pacific Chemicals Llc Compositions de collecteurs et leurs procédés de fabrication et d'utilisation
CN115155824A (zh) * 2022-07-05 2022-10-11 中南大学 一种从含锡细泥中回收锡的选矿方法

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ES8706045A1 (es) * 1985-11-29 1987-06-01 Dow Chemical Co Un procedimiento para recuperar 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
CN101455996B (zh) * 2007-12-10 2012-04-25 北京有色金属研究总院 单斜磁黄铁矿与方铅矿浮选分离工艺
CN101337206B (zh) * 2008-08-13 2011-02-02 中南大学 硫化矿浮选捕收剂及二酰基双硫脲应用方法和制备方法
CN101549326B (zh) * 2009-05-15 2012-07-04 江西理工大学 一种难选铜锌硫化矿浮选分离的工艺
CN104624384B (zh) * 2015-02-02 2017-02-22 山东建筑大学 一种低温型铁矿浮选捕收剂及其制备方法和应用
CN104826742B (zh) * 2015-05-19 2016-12-07 烟台恒邦化工助剂有限公司 一种硫化矿的复合捕收剂及其制备方法
CN108160336B (zh) * 2017-12-26 2020-11-03 中国地质科学院矿产综合利用研究所 一种碲铋矿浮选抑制剂及其制备方法和应用
CN109158217A (zh) * 2018-06-29 2019-01-08 昆明理工大学 一种硫化铜矿的浮选捕收剂
CN113692318B (zh) * 2019-04-19 2023-06-06 诺力昂化学品国际有限公司 包含n-酰化氨基酸的捕集剂组合物和处理非硫化矿的方法
CN111266195B (zh) * 2020-03-05 2021-09-07 中南大学 一种氧化锌矿浮选组合捕收剂及其应用
CN112657682B (zh) * 2021-03-16 2021-07-09 矿冶科技集团有限公司 硫化矿浮选捕收剂及其应用和硫化矿浮选方法
CN113262882B (zh) * 2021-07-21 2021-09-17 北京矿冶研究总院 阳离子捕收剂、制备方法及在磷矿反浮选中的应用

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US1833740A (en) * 1926-03-19 1931-11-24 Peter C Reilly Process of ore flotation
US2011176A (en) * 1930-03-01 1935-08-13 Minerals Separation North Us Ore concentration
US2070634A (en) * 1935-07-05 1937-02-16 Du Pont Xanthic formates
US2185591A (en) * 1938-08-24 1940-01-02 American Cyanamid Co Dispersible thiocarbanilide
US2501269A (en) * 1946-06-26 1950-03-21 Minerec Corp Froth flotation of sulfide ores
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
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
CA1105156A (fr) * 1978-10-11 1981-07-14 William A. Rickelton Traduction non-disponible
US4326067A (en) * 1980-12-03 1982-04-20 The Dow Chemical Company Process for making N-(2-aminoethyl)amides

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ES8706045A1 (es) * 1985-11-29 1987-06-01 Dow Chemical Co Un procedimiento para recuperar minerales que contienen metales a partir de una mena

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Publication number Priority date Publication date Assignee Title
US1833740A (en) * 1926-03-19 1931-11-24 Peter C Reilly Process of ore flotation
US2011176A (en) * 1930-03-01 1935-08-13 Minerals Separation North Us Ore concentration
US2070634A (en) * 1935-07-05 1937-02-16 Du Pont Xanthic formates
US2185591A (en) * 1938-08-24 1940-01-02 American Cyanamid Co Dispersible thiocarbanilide
US2501269A (en) * 1946-06-26 1950-03-21 Minerec Corp Froth flotation of sulfide ores
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
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
CA1105156A (fr) * 1978-10-11 1981-07-14 William A. Rickelton Traduction non-disponible
US4326067A (en) * 1980-12-03 1982-04-20 The Dow Chemical Company Process for making N-(2-aminoethyl)amides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0298392A2 (fr) * 1987-07-07 1989-01-11 Henkel Kommanditgesellschaft auf Aktien Procédé et agents pour l'obtention par flottation de minéraux à partir de minerais sulfurés
EP0298392A3 (fr) * 1987-07-07 1991-01-09 Henkel Kommanditgesellschaft auf Aktien Procédé et agents pour l'obtention par flottation de minéraux à partir de minerais sulfurés
US5122289A (en) * 1987-07-07 1992-06-16 Henkel Kommanditgesellschaft Auf Aktien Collector composition for use in a froth flotation process for the recovery of minerals
WO1991002097A1 (fr) * 1989-08-04 1991-02-21 The Broken Hill Proprietary Company Limited Flottage d'ions avec des reactifs non-ioniques
FR2994534A1 (fr) * 2012-08-20 2014-02-21 Ceca Sa Collecteurs pour enrichissement de minerais
WO2014029932A1 (fr) * 2012-08-20 2014-02-27 Ceca S.A. Collecteurs pour l'enrichissement de minerais
WO2015054381A1 (fr) * 2013-10-09 2015-04-16 Georgia-Pacific Chemicals Llc Compositions de collecteurs et leurs procédés de fabrication et d'utilisation
US9511378B2 (en) 2013-10-09 2016-12-06 Georgia-Pacific Chemicals Llc Collector compositions and methods for making and using same
AU2014331945B2 (en) * 2013-10-09 2018-03-01 Georgia-Pacific Chemicals Llc Collector compositions and methods for making and using same
CN115155824A (zh) * 2022-07-05 2022-10-11 中南大学 一种从含锡细泥中回收锡的选矿方法
CN115155824B (zh) * 2022-07-05 2024-01-26 中南大学 一种从含锡细泥中回收锡的选矿方法

Also Published As

Publication number Publication date
PL147930B1 (en) 1989-08-31
RU1837985C (ru) 1993-08-30
JPS62129161A (ja) 1987-06-11
AU5459886A (en) 1987-07-01
PH24537A (en) 1990-08-03
BR8607003A (pt) 1987-12-01
ZA861171B (en) 1987-10-28
ES8706047A1 (es) 1987-06-01
SE8702988D0 (sv) 1987-07-28
YU22986A (en) 1988-06-30
FI873287A0 (fi) 1987-07-28
FI873287A (fi) 1987-07-28
PL257990A1 (en) 1987-06-15
ES552034A0 (es) 1987-06-01
AU586471B2 (en) 1989-07-13
CN86101573A (zh) 1987-06-03
ZM1486A1 (en) 1988-01-29
YU45765B (sh) 1992-07-20
ZW4286A1 (en) 1987-09-09
SE8702988L (sv) 1987-07-28

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