FI81975C - FLOTATIONSSAMLARKOMPOSITION FOER UTVINNING AV METALLINNEHAOLLANDE SULFIDMINERAL ELLER SULFIDISERADE, METALLINNEHAOLLANDE OXIDMINERAL. - Google Patents

Description

1 81975

The present invention relates to a novel aggregating composition useful for recovering metal-containing sulfide minerals and sulfided metal-containing oxide minerals from ore.

Flotation is a method of treating a mixture of finely divided solid minerals suspended in a liquid, e.g. powdered ore, whereby some of these solids are separated from other finely divided solids, e.g. clay species and other similar substances in the ore by introducing gas into the liquid ( or by forming a gas in situ) to form a foamy mass containing certain solids on the surface of the liquid and leaving the other solid components of the ore in a suspended state (non-foamed). Flotation is based on the principle that the introduction of 20 gases into a liquid containing solids of various substances sucked into it causes some of the gas to adhere to certain slurry solids, but not others, and makes the particles to which the gas has adhered lighter than the liquid. In this case, these particles rise to the surface of the liquid, forming a foam.

Many blowing agents have been mixed into the suspension to improve the flotation process. Such added substances are classified according to the task to be performed: collectors for sulphide minerals, and these include e.g. xanthates, thionocarbamates and the like; blowing agents which enhance the ability of stable foams to form, e.g., natural oils such as tall oil and eucalyptus oil; modifiers such as activators to accelerate foaming in the presence of a collector, e.g. copper sulfate; dep-35 depressants, e.g., sodium cyanides, which seek to prevent the collector from acting in this capacity relative to a mineral which is desired to remain in the liquid and thus attempt to prevent it from migrating upwards and forming part of the foam; pH-5 is left to achieve optimal metallurgical results, e.g., lime, soda ash, and the like.

It is important to keep in mind that additives of the type described above are selected for use according to the nature of the ore, the mineral to be recovered (minerals) and the other additives used in conjunction with them.

Understanding the phenomena that make foaming a particularly valuable industrial operation is not essential to the practice of the present invention. However, the phenomena appear to be largely related to the selective affinity of the surface of the discrete solids slurried in the liquid containing the retained gas on the one hand for the liquid and on the other hand for the gas.

20 The flotation principle applies to a number of mineral separation processes, including the selective separation of metal sulfide minerals, such as those containing copper, zinc, lead, nickel, molybdenum and other metals, from iron-containing sulphide minerals such as pyrite and pyrrote.

Xanthates, dithiophosphates and thionocarbamates are commonly used collectors for the recovery of metal-containing sulfide minerals or sulfated metal-containing oxide minerals. These volatile sulfur-30 compounds are often released into the atmosphere through chimneys or are removed from such chimneys by an expensive and precisely fabricated cleaning device. Many non-ferrous metal-containing sulfide minerals or metal-containing oxide minerals are found in nature in ores, which also consist of iron-containing sulfide minerals.

3,81975

When iron-containing sulfide minerals are recovered in flotation processes in combination with non-ferrous metal-containing sulfide minerals and sulfided metal-containing oxide minerals, an excess of 5 sulfur is present, which is released in smelting processes, resulting in an undesirably high amount of sulfur present during smelting operations. What is required is a builder composition useful for the selective recovery of non-ferrous metal-containing sulfide minerals and sulfided metal-containing oxide minerals without recovering iron-containing sulfide minerals.

Of the commercially available collectors, xanthates, thionocarbamates, and dithiophosphates do not selectively recover non-ferrous sulfide minerals in the presence of ferrous sulfide minerals. In contrast, such collectors collect and recover all metal-containing sulfide minerals. What is required is a composite composition for use in flotation that selectively recovers non-ferrous metal-containing sulfide minerals or sulfidated metal-containing oxide minerals in the presence of ferrous sulfides.

This invention relates to a novel flotation collector composition useful for recovering non-ferrous metal-containing sulfide minerals and sulfided metal-containing oxide minerals from ore in a flotation process.

The new bulking agent is characterized in that it contains

(A) a hydrocarbon sulphide of formula I

R * -S-R2 (I) 10 to 90% by weight of said bulking agent, and 4,81975

b) an alkylthiocarbonate of formula II

X

7 11 R7-X-C-S * M * (II) 5

or thionocarbamate of formula III

S

. «(R0) .- N-C-Y (III) 10 (H) b

or thiophosphate of formula IV

R100 S \ II

PXM * (IV) R100 or mixtures thereof, wherein b) is present in an amount of 10 to 90% by weight of said composition, wherein R1 and R2 are independently a hydrocarbyl radical or a hydrocarbyl radical substituted by one or more hydroxy, cyano , a halogen, ether, hydrocarbyloxy or hydrocarbylthioether group, wherein R 1 and R 2 may together form an epithio ring structure with S, provided that S is attached to an aliphatic or cycloaliphatic carbon atom, with the additional proviso that the total carbon content of the hydrocarbon sulfide is 4 to 20 carbon atoms; R7 is a C1-20 alkyl group; R 8 is independently a C 1 -C 4 alkyl group; R9 is a C1-10 alkyl group; R 10 is independently hydrogen, a C 1-10 alkyl group or an aryl group; 35 M is an alkali metal cation; X is independently at each occurrence S or 0; 5,81975 Y is -S * M * or OR9; a is an integer 1 or 2; and b is an integer 0 or 1, with the proviso that a + b - 2, with the additional proviso that said metal-containing mineral is recovered in said foam.

The use of the novel collectors of this invention results in a surprisingly high recovery of non-ferrous metal-containing sulfide minerals or sulfided metal-containing oxide minerals and good selectivity for such non-ferrous metal-containing sulfide minerals when such metal-containing sulfide minerals are present. sulfided metal-containing oxydiminals are found in the presence of iron-containing sulfide minerals. These collectors show good recovery-15 ability and good kinetics.

One component of the novel bulking composition of this invention is a hydrocarbon containing one or more monosulfide units in which the sulfur atoms of the sulfide units are attached to non-aromatic carbon atoms, i.e., aliphatic or cycloaliphatic carbon atoms. A monosulfide unit here means a unit in which a sulfur atom is attached to only two carbon atoms of the hydrocarbon moiety. Such hydrocarbon compounds containing one or more of the monosulfide units used herein include those substituted with hydroxy, cyano, halogen, ether, hydrocarbonyloxy and hydrocarbonylthioether moieties. A non-aromatic carbon atom as used herein means a carbon atom that is not part of an aromatic ring.

In formula I, R 1 and R 2 are preferably an independent aliphatic, cycloaliphatic or aryl moiety, unsubstituted or substituted by one or more hydroxy, cyano, halogen, OR 3 or SR 3 moieties, wherein R 3 is a hydroxycarbyl radical, wherein R 1 and R 2 may be -35 together form a heterocyclic ring with S. R 1681975 and R 2 are more preferably an aliphatic or cycloaliphatic moiety, unsubstituted or substituted by one or more hydroxy, cyano, halogen, OR 3 or SR 3 moieties; wherein R 1 and R 2 may together form an epithio-5 ring structure with S. In an even more preferred embodiment, R 1 and R 2 do not combine to form an epithio ring structure with sulfur, and R 1 and R 2 are alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkenyl, unsubstituted or substituted with one or more hydroxy, halogen, cyano, In the OR3 or SR3 moiety where R3 is aliphatic or cycloaliphatic. In the most preferred embodiment, R 1 is methyl or ethyl. R2 is a C6- n-alkyl or alkenyl group. In the most preferred embodiment, R 1 and R 2 are not identical hydrocarbon moieties, i.

The monosulfide is asymmetric. R3 is preferably aliphatic or cycloaliphatic. More preferably, R 3 is alkyl, alkenyl, cycloalkyl or cycloalkenyl.

The total carbon content of the hydrocarbon portion of the hydrocarbon monosulfide should be such that the hydrocarbon sulfide is hydrophobic in nature in sufficient amount to cause the metal-containing sulfide mineral particles or sulfated metal-containing oxide mineral particles to adhere to the air / bubble interface. The total carbon content of the hydrocarbon monosulfide is then such that the minimum amount of carbons is 4, preferably 6 and more preferably 8. The maximum amount of carbons is 20, preferably 16 and more preferably 12.

In a preferred embodiment of this invention, the hydrocarbon sulfides useful in this invention have the formula (R 4) 2 -C-CH 2 (Id) N's / wherein R 4 is independently hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl. 1, hydroxy, cyano, halogen, OR 3 or SR 3, wherein aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl may be optionally substituted by hydroxy, cyano, halogen, OR 3 or SR 3 , wherein R 3 is a hydroxycarbyl radical, provided that the total carbon content of the hydrocarbon portion of the collector is such that the collector is sufficiently hydrophobic in nature to foam the metal-containing sulfide mineral or sulfidated metal-containing oxide mineral particles.

Examples falling within the scope of this invention are carbon-livetysulfideista metyylibutyylisulfidi, sulfide-methylpentyl, metyyliheksyylisulfidi, metyyliheptyylisul-sulfide metyylioktyylisulfidi, metyylinonyylisulfidi, methyl-15 lidekyylisulfidi, metyyliundekyylisulfidi, metyylidodekyy- sulphide, metyylisyklopentyylisulfidi, metyylisyklohek-syylisulfidi, metyylisykloheptyylisulfidi, oktyylisulfidi-methylcyclooctyl, etyylibutyylisulfidi, etyylipentyylisulfi-oxide, etyyliheksyylisulfidi, etyyliheptyylisulfidi, ethyl oktyylisulfidi 20, etyylinonyylisulfidi, etyylidekyylisulfi- chloride, etyyliundekyylisulfidi, etyylisykloheksyylisulfidi, etyylisykloheptyylisulfidi, etyylisyklo-oktyylisulfidi, propyylibutyylisulfidi, propyylipentyylisulfidi, propyl-heksyylisulfidi, propyyliheptyylisulfidi, propyylioktyyli 25-sulfide, propyylinonyylisulfidi, propyylidekyylisulfidi, propyyliundekyylisulfidi, propyl dodecyl sulfide, propyl cyclopentyl sulfide, propyl cyclohexyl sulfide, propyl cycloheptyl ulfidi, propyylisyklo-oktyylisulfidi, dibutyl sulfide, butyylipentyylisulfidi, butyylihek-30 syylisulfidi, butyyliheptyylisulfidi, butyylioktyylisulfi- chloride, butyylinonyylisulfidi, butyylidekyylisulfidi, butyl undekyylisulfidi, butyylidodekyylisulfidi, butyylisyklo-pentyylisulfidi, butyylisykloheksyylisulfidi, butyylisyk-loheptyylisulfidi, butyylisyklo-oktyylisulfidi, dipentyy-35 sulfides, pentyyliheksyylisulfidi, pentyyliheptyylisulfi- chloride, pentyylioktyylisulfidi, pentyylinonyylisulfidi, pentyl 81 975 β tyylidekyylisulfidi, pentyyliundekyylisulfidi, pentyl dodekyylisulfidi, pentyylisyklopentyylisulfidi, pentyl sykloheksyylisulfidi, pentyylisykloheptyylisulfidi, pen-tyylisyklo-oktyylisulfidi, diheksyylisulfidi, hexyl-5 heptyylisulfidi, heksyylioktyylisulfidi, sulfide heksyylinonyyli- , hexyldecylsulfide, hexylundecylsulfide, hexyldodecylsulfide, hexylcyclopentylsulfide, hexylcyclohexyl sulphide, hexylcycloheptyl sulphide, hexylcyclooctyl sulphide i diheptyylisulfidi, 10 heptyylioktyylisulfidi, heptyylinonyylisulfidi, heptyl dekyylisulfidi, heptyyliundekyylisulfidi, heptyylidodekyy-methyl sulphide, heptyylisyklopentyylisulfidi, heptyylisyklohek-syylisulfidi, heptyylisykloheptyylisulfidi, heptyylisyklo-oktyylisulfidi, dioctyl sulfide, oktyylinonyylisulfidi, 15 oktyylidekyylisulfidi, oktyyliundekyylisulfidi, oktyylido- dekyylisulfidi, oktyylisyklopentyylisulfidi, oktyylisyklo-heksyylisulfidi, oktyylisykloheptyylisulfidi, oktyylisyk- lo oktyylisulfidi, oktyylisyklododekyylisulfidi, dionyl sulfide, nonyylidekyylisulfidi, nonyyliundekyylisulfidi, 20 nonyylidodekyylisulfidi, nonyylisyklopentyylisulfidi, nyylisykloheksyylisulfidi weight, nonyylisykloheptyylisulfidi, nonyylisyklo-oktyylisulfidi, didekyylisulfidi, dekyyliun-dekyylisulfidi, dekyylidodekyylisulfidi, dekyylisyklopen-sulfide, dekyylisykloheksyylisulfidi, dekyylisyklo-25 heptyl sulfide and decyl cyclooctyl sulfide.

Most preferred sulfides and are methylhexyl sulfide, methylheptyl sulfide, methyl octyl sulfide, methyl aminoyl sulfide, methyl dececyl sulfide, ethyl hexyl sulfide di, ethyl heptyl sulfyl, ethyl octyl sulfide, ethyl ocinyl decyl, ethyl amino-30 nyl sulfide, ethyl sulfide, ethyl sulfide.

Another component of the novel bulking composition of this invention is alkylthiocarbonate, thiono-carbamate, thiophosphate, or mixtures thereof. Alkylthio 9,81975 carbonates as used herein refer to compounds containing a thiocarbonate moiety and at least one alkyl moiety, the alkyl moiety being hydrophobic in nature to cause the associated metal-containing sulfide mineral moieties or sulfidated metal-containing oxide mineral moieties to adhere. interface.

Preferred alkyl thiocarbonates of formula II are alkyl monothiocarbonates, alkyl dithiocarbonates or alkyl trithiocarbonates.

Preferred alkyl monothiocarbonates have the formula 0 7 11 R 7 -O-C-S'M * (Ha) 15 wherein R 7 and M are as defined above.

Examples of preferred alkyl monothiocarbonates are sodium ethyl monothiocarbonate, matrix isopropyl monothiocarbonate, sodium isobutyl monothiocarbonate, sodium methyl monothiocarbonate, potassium methyl monothiocarbonate, potassium isopropyl monothiocarbonate, potassium isopropyl monothiocarbonate,

Alkyl dithiocarbonates are generally referred to as xanthates. Preferred alkyl dithiocarbonates have the formula 25

S

7 M

R7-O-C-S'M * (Hb) wherein R7 and M are as defined above.

Preferred alkyl dithiocarbonates are potassium ethyl dithiocarbonate, sodium ethyl dithiocarbonate, potassium dithiocarbonate, sodium methyl dithiocarbamate, potassium isopropyl dithiocarbonyl, sodium dopropyl di-thiocarbonate, sodium sec-butyl dithiocarbonate, sodium sec-butyl dithiocarbonate, sodium sec-butyl dithiocarbonate,

Preferred alkyl trithiocarbonates have the formula 10 81 975

5 S

R7-S-C-S'M * (He) wherein R7 and M are as defined above.

Examples of alkyl trithiocarbonates are sodium isobutyl trithiocarbonate and potassium isobutyl trithiocarbonate.

Preferred thionocarbamates of formula III are dialkyldithiocarbamates and alkylthionocarbamates. Preferred dialkyldithiocarbamates have the formula 15

R8 S

II

(purple) 20 wherein M is as defined above; and R 8 is independently a C 1-10 alkyl group.

Examples of preferred dialkyl dithiocarbamates are methyl butyl dithiocarbamate, methyl isobutyl dithiocarbamate, methyl sec-butyl dithiocarbamate, methyl propyl dithiocarbamate, ethyl isopropyl dithiocarbamate, ethyl butyl dithiocarbamate, ethyl butyl dithiocarbamate, -ditiokarbamaatti.

Preferred alkylthionocarbamates have the formula

S

R 8 -NH-C-OR 9 (IIIb) 35 wherein R 8 is as defined above; and R9 is

Ci-io "alkyl group.

11 81975

Examples of preferred alkylthionocarbamates are N-methylbutylthionocarbamate, N-methylisobutylthionocarbamate, N-methyl-sec-butylthionocarbamate, N-methylpropylthionocarbamate, N-methylisopropyl-5-thionocarbamate, N-ethylbutamocarbamate, N-ethylbutylthio -ethyl sec-butylthionocarbamate, N-ethylpropylthionocarbamate and N-ethylisopropylthionocarbamate. The most preferred thionocarbamates are N-ethyl isopropylthionocarbamate and N-ethyl-10-isobutylthionocarbamate.

Preferred thiophosphates of formula IV are monoalkylthiophosphate, dialkyldithiophosphate, diaryldithiophosphate and dialkyl monothiophosphate. Preferred monoalkyl dithiophosphates have the formula 15

R10 0 S

P-S'M * (IVa) H0 / 20 where R10 and M are as defined above.

Examples of preferred monoalkyl dithiophosphates are ethyl dithiophosphate, propyl dithiophosphate, isopropyl dithiophosphate, butyl dithiophosphate, sec-butyl dithiophosphate and isobutyl dithiophosphate.

Preferred dialkyl and diaryl dithiophosphates have the formula R100 S \ ti ^ P-S “M * (IVb) R10O ^ ^ ^ 30 wherein R10 and M are as defined above.

Examples of dialkyl and diaryl dithiophosphates are sodium diethyl dithiophosphate, sodium di-sec-butyl dithiophosphate, sodium diisobutyl dithiophosphate, sodium diisoisamyl dithiophosphate and sodium dicresyl dithiophosphate.

i2 81 975

Preferred dialkyl monothiophosphates have the formula R100 S n P-O "M * (IVc) 5 R100 ^ wherein R10 and M are as defined above.

Preferred monothiophosphates are sodium diethyl monothiophosphate, sodium di-sec-butyl monothiophosphate, sodium diisobutyl monothiophosphate and sodium diisoamyl monothiophosphate.

R 7 is preferably C 2-16 alkyl, more preferably C 3-12 alkyl.

R a is preferably C 1-6 alkyl, more preferably C 1-6 alkyl.

R 9 is preferably C 2-10 alkyl, more preferably C 2-6 alkyl and most preferably C 3-4 alkyl.

R 10 is preferably C 2-8 alkyl or cresyl.

The composition of matter of the present invention preferably contains a) 20 to 80% by weight of a hydrocarbon sulfide of formula I; and b) 20 to 80% by weight of an alkyl thiocarbonate of the formula II, a thionocarbonate of the formula III, a thiophosphate of the formula IV or mixtures thereof.

More preferably, the composition of matter of this invention contains a) 30 to 70% by weight of a hydrocarbon sulfide of formula I; and b) 30 to 70% by weight of an alkyl thiocarbonate of the formula III, a thionocarbamate of the formula III, a thiophosphate of the formula IV or mixtures thereof.

In a most preferred embodiment of the invention, the ratio of the hydrocarbon sulphide of formula I to the alkyl thiocarbonate of formula II, the thionocarbamate of formula III, the thiophosphate of formula IV or mixtures thereof is such that metal-containing sulfide minerals or sulphidated, metal-containing the recovery in the flotation process is greater than either component alone could recover using the same weight of dosage. The dosage at which the collector is used is more preferably the dosage at which component b) of the compound composition of formula II, III or IV, when used alone, gives a higher yield than that of the hydrocarbon sulphide of formula I at such a level of use.

The novel flotation collector composition of this invention provides higher recoveries, often better metal quality, than can be achieved using either collector component alone. Grade (gra-15 de) is defined as the fraction of the desired metal contained in the foamed material.

Hydrocarbon here means 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 aralcans, and alkyl-substituted aromatics.

Aliphatic here means straight-chain and branched, both saturated and unsaturated hydrocarbon compounds, i.e. alkanes, alkenes or alkynes. Cycloaliphatic here means saturated or unsaturated cyclic hydrocarbons, i.e. cycloalkenes and cycloalkanes.

Cycloalkane1 means an alkane containing 1, 30, 2, 3 or more cyclic rings. Cycloalkene means mono-, di- and polycyclic groups containing one or more double bonds.

Hydrocarbyl here means an organic radical containing carbon and hydrogen atoms. The term "hydro-carbyl" includes the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, 14,875 aryl, aliphatic and cycloaliphatic aralkyl and alkaryl. The term "aryl" as used herein means biaryl, diphenyl, phenyl, naphthyl, phenanthrenyl, anthracenyl, and two aryl groups bridged with an alkylene group.

Alkaryl as used herein means an alkyl, alkenyl or alkynyl-substituted aryl substituent wherein aryl is as defined above. Aralkyl as used herein means an alkyl group in which the aryl is as defined above.

10 The term "C 1-20 alkyl" includes straight-chain and branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oc-tadecyl, nonadecyl and eicosyl groups.

Halogen means a chlorine, bromine or iodine group.

The novel aggregate compositions of this invention are useful for recovering metal-containing sulfide-20 minerals and sulfated metal-containing oxide minerals from ores by foaming. Ore here means a material as it is taken from the soil and which contains the desired metallic minerals mixed with the limestone. The limestone 25 here means that part of the material which has no value and which must be separated from the desired metallic minerals.

In a preferred embodiment of the invention, metal-containing sulfide minerals are recovered. In a more preferred embodiment of this invention, sulfide minerals containing copper, nickel, lead, zinc or molybdenum are recovered. In an even more preferred embodiment of the invention, copper-containing sulfide minerals are recovered. Also preferred metal sulfide-containing minerals are those which inherently have a high hydrophobicity in the non-oxidized state. The term "hydrophobicity in the non-oxidized state" refers to a freshly ground mineral or a mineral with a fresh surface that demonstrates the ability to float without the addition of a collector.

5 Ores for which these compositions are useful are sulphide mineral ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and mixtures thereof. Examples of metal-containing sulfide minerals that can be enriched by foaming using the process of this invention include copper-containing minerals such as covellite (CuS), chalcosite (Cu2S), chalcopyrite (CuFeS2), valerite (Cu2Fe4e4, Cu2Fe4S7, or Cu2Fe4S7) Cu3SbS2), 15 bornite (Cu5FeS4), cubanite (Cu2SFe4S5), enardite [Cu3 (As1Sb) S4], tennantite (Cu12As4S13), brocanite [Cu4 (OH) 6SO4], C3 (Cu4) SbAs) S4] and burnonite (PbCuSbS3); lead-containing minerals such as lead flux (PbS); antimony-containing minerals such as stibnite (Sb2S3); zinc-containing minerals such as zinc scintillation (ZnS); silver-containing minerals such as stefanite (Ag5SbS4) and silver luster (Ag2S); chromium-containing minerals such as dabrelite (FeSCrS3); nickel-25-containing minerals such as pentlandite [(FeNi) 9S8]; molybdenum-containing minerals such as molybdenite (MoS2); and platinum and palladium-containing minerals such as cooperite [Pt (AsS) 2]. Preferred metal-containing sulfide minerals are 30 molybdenite (MoS2), chalcopyrite (CuFeS2), lead flux (PbS), zinc scintillation (ZnS), bornite (Cu5FeS4) and pentlandite [(FeNi) 9S8].

Sulfidated metal-containing oxide minerals are minerals that have been treated with a sulfidation chemical so that such minerals have acquired the properties of a sulfide mineral, so that the minerals can be recovered in IE 81975 by flotation using collectors that recover sulfide minerals. Sulfidation results in oxide minerals with sulfide properties. The oxydiminals are sulfidated by contacting them with compounds that react with the minerals to form a sulfur bond or affinity. Such methods are well known in the art. Such compounds include sodium hydrogen sulfide, sulfuric acid and similar sulfur-containing salts such as sodium sulfide.

Sulfated oxydiminerals useful in this process include oxide minerals containing copper, aluminum, iron, titanium, tungsten, molybdenum, magnesium, chromium, nickel, manganese, tin, uranium, and mixtures thereof. Examples of metal-containing oxide minerals that can be enriched by foaming using the process of this invention include copper-containing minerals such as cuprite (Cu 2 O), tenorite (CuO), malachite [(Cu 2 OH) 2 CO 3], azurite [Cu 3 (OH) 2 (CO 3) 2], attackamide [Cu 2 Cl (OH) 3], aqueous copper silicate (CuSiO 3); aluminum-containing minerals such as corundum; zinc-containing minerals such as zincite (ZnO) and smitsonite (ZnCO 3); tungsten-containing minerals such as tungsten [(Fe, Mn) WO 4]; nickel-containing minerals such as bunzenite (NiO); mo-25 lybdenum-containing minerals such as wulfenite (PbMoO 4) and powellite (CaMoO 4); ferrous minerals such as hematite and magnetite; chromium-containing minerals such as chromite (FeO 2 Cr 2 O 3); ferrous and titanium-containing minerals such as ilmenite; magnesium- and aluminum-containing minerals such as Spinelli; iron and chromium-containing minerals such as chromite; titanium-containing minerals such as rutile; manganese-containing minerals such as pyrroleite; tin-bearing minerals such as cassiterite; and uranium-containing minerals such as uraninite; and uranium-35-containing minerals such as uranium pitch [U205 (U308)] and gumite (U03nH2O).

The collectors of this invention can be used at any concentration that provides the desired recovery of the desired minerals. In particular, the concentration used depends on the specific minerals to be recovered, the metal content of the ore for which the flotation process is to be carried out, the desired quality of the mineral recovered and the specific mineral recovered. The collectors according to the present invention are preferably used in concentrations of 0.001 to 1.0 kg per tonne of foamable ore, more preferably 0.010 to 0.2 kg collector per tonne of foamable ore.

The blowing agents are preferably used in the flotation method of this invention. Any blowing agent well known in the art, the use of which results in the recovery of the desired mineral, is suitable.

Examples of such blowing agents include C5-8 alcohols, tall oils, cresols, C1-4 alkyl ethers of polypropylene glycols, dihydroxylates of polypropylene glycols, glycols, fatty acids, soaps, alkylaryl sulfonates, and the like. In addition, mixtures of such blowing agents can also be used. All blowing agents suitable for enriching ores by flotation can be used in this invention.

The method of the present invention further contemplates that the collectors of the invention may be used in admixture with other collectors well known in the art. Collectors known in the art that can be used in admixture with the collectors of the invention are those that provide the desired recovery of the desired mineral. Examples of collectors useful in this invention include dialkylthioureas, dialkyl and diarylthiophosphonyl chlorides, dialkyl and diaryl dithiophosphonates, alkyl mercaptans, xanthene formates and alkylates, isothalap and alcohols of these, salts, alkylphosphoric acids and their salts, alkyl and aryl phosphoric acids and their salts, sulfosuccinates, sulfosuccinamates, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkylpyridinium salts, guanidine and alkylanidine. The following examples illustrate the invention.

Unless otherwise indicated, all parts and fractions are by weight. Synergism is defined herein as the case where the measured result obtained with a mixture of two or more components exceeds the weighted average results obtained with each component, when used alone. This term also means that the results are compared provided; 15 that the total weight of the collector used is the same for each experiment.

Example 1 Flotation of Copper / Molybdenum Ore from Western Canada 20 Homogeneous ore containing chalcopyrite and molybdenite minerals was bagged so that each bag contained 1,200 g. The pre-foaming process involved grinding a 1,200 g portion with 800 ml of tap water for 14 minutes in a ball mill with a mixed ball-25 composition (to obtain a product of which about 13% had a particle size of +100 mesh). This pulp was transferred to an Agitar branded 1,500 ml flotation cell equipped with an automated exhaust paddle system. The pH of the slurry was adjusted to 10.2 using lime. No further pH adjustments were made during the experiment. The standard blowing agent was methyl isobutylcarbinol (MIBC). A four-step pre-foaming process was then performed.

i9 81 975

Phase 1

Collector - 0.0042 kg / ton MIBC - 0.015 kg / ton - conditioning - 1 minute 5 - flotation - concentrate collection for one minute

Step 2

Collector - 0.0021 kg / ton MIBC - 0.005 kg / ton 10 - conditioning - 0.5 minutes - flotation - concentrate collection for 1.5 minutes

Step 3

Collector - 0.0016 kg / ton 15 MIBC - 0.005 kg / ton - conditioning - 0.5 minutes - flotation - concentrate collection for 2.0 minutes

Step 4 20 Collector - 0.0033 kg / ton MIBC - 0.005 kg / ton - conditioning - 0.5 minutes - flotation - concentrate collection for 2.5 minutes 25

The results are summarized in Table I.

20 81 975

Table I

Cu Mo Cu Mo

Collector R-7 (** R-7 (** Grade '*** Grade' *** 5 - potassium amyl xanthate '* 0,776 0,725 0,056 0,00181 1,2-epithiooctane1 * 0,710 0,691 0,093 0,00325 potassium amyl xanthate and 1.2- 50/50 mixture of epithiooctane 10 0.794 0.766 0.054 0.00177 methylhexyl sulfide '* 0.699 0.697 0.107 0.00386 50/50 mixture of potassium amyl xanthate and methylhexyl sulfide 0.790 0.793 0.056 0.00169 15 _ #) Example according to the invention **' R -7 is the partial yield of the test after 7 minutes *** '"Grade" is the proportion of specific metal contained in the total weight of the foam accumulated in the foam 20

The 95% confidence interval for the statistical error associated with the Cu R-7 test values in Table I is ± 0.010. In this case, the statistical range of the R-7 value of Cu for potassium amyl xanthate shown in Table I is 0.776 ± 0.010, i.e. 0.766 to 0.786. The statistical error associated with the R-7 experimental values of Mo shown in Table I is ± 0.015. The practical application of these limits clearly shows that the recovery of Cu and Mo in 7 minutes using the aggregate mixtures of this invention exceeds the recovery in 7 minutes that could be expected from the weighted average power achieved by a single component when used alone. Synergism has occurred.

2i 81975

Example 2

Foaming of copper / nickel ore from eastern Canada

Copper / nickel ore containing calopyrite, pentlandite and pyrrotite minerals was foamed using 0.0028 kg / ton D0WFR0TH * 1263 as a blowing agent and 0.28 kg / ton collector. A series of samples were taken from the feeder to the rougher bank of the plant and dispensed into buckets to give about 1,200 g of solid. The contents of each bucket were then used to provide a time / recovery profile in the Denver cell using an automated removal paddle and a mass removal level constant device for individual concentrates selected after 1.0, 3.0, 6.0, and 12.0 minutes. Chemicals were added and a conditioning time of one minute was used before defoaming was started. No stepwise addition of reagents was performed. Individual concentrates were dried, weighed, ground, and ti-20 mortally representative samples were prepared for analysis. The results are summarized in Table II.

Table II

Pyrro- 25 Cu Ni titre

Collector R-12 (** R-12 *** R-12 (* e sodium methyl xanthate (* 0.930 0.839 0.358 1.2-epithiooctane (* 0.927 0.751 0.247 30 dibutyl sulfide '* 0.928 0.630 0.190 1.2-epithiooctane and sodium ethyl xanthate 50 50/50 mixture 0.927 0.844 0.344 50/50 mixture of dibutyl sulfide and sodium sodium xanthate 0.931 0.824 0.245

Explanations of Table II: * 'Example not according to the invention **' R-12 is the partial yield obtained after 12 minutes in the experiment 22 81 975 5 The recoveries of Cu at 12 minutes are all so high in Table II (approaching the theoretical limit of 1.0), that the use of statistical confidence limits does not apply. The 95% confidence level for R-12 for nickel in Table II is ± 0.012. It will be appreciated that the aggregate compositions of this invention provide Ni yields that far exceed the recoveries that would be expected from the weighted average result achieved for each component when used alone. Synergism has occurred.

15 Example 3

Flotation of complex Pb / Zn / Cu-Ag ore from central Canada

Uniform 1,000 g ore samples containing lead leachate, zinc spacer, chalcopyrite and silver luster were prepared. For each flotation run, a sample was added to a rod mill along with 500 mL of tap water and 7.5 mL of SO 2 solution.

A grinding time of 6.5 minutes was used to make the product, 90% of which had a particle size of less than 200 mesh (75 microns). After grinding, the contents were transferred to a cell equipped with an automated paddle to remove foam, and the cell was attached to a standard Denver flotation mechanism.

30 A 2-stage flotation was then performed.

In step I a copper / lead / silver pre-concentrate (rouger) was used and in step II a zinc pre-concentrate was used. To begin the flotation of step I, 1.5 g / kg Na 2 CO 3 (pH 9-9.5) was added, followed by the addition of collector (s). The slurry was then conditioned for 5 minutes with air and stirring. This was followed by a 2-minute conditioning period of 23,81975, with exclusive mixing. MIBC blowing agent was then added (standard dose 0.015 ml / kg). The concentrate was collected for a flotation time of 5 minutes and this was marked as copper / lead pre-concentrate.

5 In phase II flotation, 0.5 kg / ton was added

CuSO 4 to the phase I cell residues. The pH was then adjusted to 10.5 by adding lime. This was followed by a 5 minute conditioning period with exclusive mixing. The pH was then checked again and adjusted back to 10.5 with lime. At this time, the collector (s) were added, followed by conditioning for 5 minutes, stirring exclusively. MIBC blowing agent (standard dose 0.020 ml / kg) was then added. The concentrate was collected for 5 minutes and this mer-15 was kited into zinc pre-concentrate.

Concentrate samples were dried, weighed, and suitable samples were prepared for X-ray examination. Using the experimental results, partial yields and metal concentrations (grades) were calculated using standard mass equilibration formulas. The results are summarized in Table III.

24 81 975 r> es oo σ 'n ^ ** ι w I ** 1 «. «.

O o o «« 'ύ) Ό

G «0 M U

rs O (N in <n oo o

<N VO τί rH

(N «H 00 (S lf)« v *. *, * * »*

t o o o O O O

in £

* O f- (S

* in in in

'qj OIOIOI

£ 1 ffl o O o

° * M

0 c. Tf p- ts m m m • 'j t OI P · UJ N1 O' ^

ID P> O VO H f ~ O 1J

OS o o 'o' o 'o' O * jj

E

t "Ό O S

o n h $ H I H I H I ”J O σ 'o £ *“ α> £ 3 Ό 3 CJ <0 ® o -H O n 03 (N 00 2 n <J \ rf r * =

en O CO O σι O JS

t o o o o o o d

m iO

1 H <2 OS T) ^

> -l * H IM

M PH 5 M: m (N (M P 3 <0 2

* p »h Pn io w 3 H

o - «^ 1« 1 "ä s s t 3 2 ° ° ° § δ 2? 3 S 5 i g

<0 -H <11 S

E * σι «Ό Ncocr» HO 4-> e, e S

<i. oo m tv o σι n hh h n

If) OO Ot ^ H CO O Ό T3 p M

| > »Yyyy» 3 *

OS OOOOOO II 3C

moh 2 ei X in in tn m in in m2 O'- '' »» 2 σ \ O σι o σι O, om HH hm + J es - | s§ 3 G> - »» / ho -— ^ Jl » * 0 eve ✓— i ^ -o — r ^> —- s ^ i ® mr, (OO in '' m * mee rv OP vv, H -ri ® £

C \ inr'Oinoioininp'in P 2a) S

C O) cnhhcnh n f »® p S

<Λ H · * e s (0 e p a) p 5 i e e g

o 10 * d e S

0 _ W P 2 ® e.

^ SlO <a3 <OQQUQCQQ ^ C * £ ^ SS i 2 § ^ § C u 1 - V Λ S Ό o Η01Λ Ώ £ 3 <DU ζ 0 ° Oi (DM30. 0. CU E <0 G p _ 3 JC HP \> v \ 3 i «3

H 0) 0) 3 C 3 C i 3 C | H02CÄM

n ai ίο io Nivon Ivo n J u e - * o 2 h

> ~ X - / V ---, _ J 4J O ® 2 O

* y «h - * m .¾ -m

C P I „H

. Tl QS ‘a oi. i i oa _ fl r- H IN m - · ifl <· e u r:: o 25 81975

Table III then contains two experimental conditions which consistently make it possible to compare the recoveries associated with the use of the aggregate mixtures according to the present invention with those obtainable with the aggregate component, when used alone.

Comparing run 2 Cu / Pb flotation (step I) when using collector D alone to run 3 Cu / Pb flotation (step I) when using collector mixture D + B, the results show that the collector according to the invention - higher recovery yields of Ag, Cu and Pb obtained with the mixtures. The 95% confidence level for the statistical error is ± 0,01 for Ag, ± 0,01 for Cu and ± 0,02 for Pb.

15 Run 3 Zn flotation (stage III) compared to run 2

Zn flotation (Phase II) also describes an apparent increase in the recovery of Zn associated with the use of the mixture compared to the result obtained with the component alone. The 95% confidence level for the statistical error is ± 0.01 for Zn.

Other runs, using private components at different stages, are not shown in Table III, as many of the private components, alone, simply do not perform the task sufficiently to compile meaningful results for comparison.

For example, collector B, used alone in step I, gives a recovery of less than 0.500 for Cu and Pb.

Example 4 Flotation of Complex Cu / Mo Ore from South America A 500 g amount of Cu / Mo ore containing various copper-containing sulfide minerals and molybdenite was placed in a rod mill with an inch (2.5 cm) thickness. 975 bars, together with 257 g of deionized water and a certain amount of lime. The mixture was then ground 360 rpm at 60 rpm to obtain a suitable fine distribution of the particles. The ground slurry was transferred to an Agitar-branded 1,500 ml flotation cell equipped with an automated exhaust paddle system. The slurry was stirred at 1,150 rpm and the pH was adjusted to the appropriate value (shown in Table 4) with either additional lime or hydrochloric acid. At this time, the collector (s) was added to the flotation cell (45 g / ton), followed by a conditioning period of one minute during which the flotation agent DOW-FROTH * 250 (34.4 g / ton) was added. After an additional conditioning time of 1 minute, the air supply to the flotation cell was adjusted to 4.5 l / min and the automatic defoamer was started. Foam samples were collected after 0.5, 1.5, 3.0, 5.0 and 8.0 minutes.

The samples were dried overnight in an oven along with flotation concentrators. The dried samples were weighed-20, ground to the appropriate fineness for dissolution, and dissolved in acid for analysis on a DC Plasma Spectrograph. The results are summarized in Table IV.

27 81975

(M ~ ® O N -H

2J O'O CO CO CO., LTD

n t Z ^ CO CS CO CO

U— L «· *. * vs.

* «O °° ° OO

ce

«RH 'S · CO C ^ rH

g 1 σ 'in o \ h co o Q CO CO CO 00 O' COO 'I * s v *> * * OS O o o o o o

33 in in in O O O

Q. * * »*>" '

O O O CO 00 CO

rH rH rH

m

3 -H

μ c co c

O

C JJ

2 \ (ΊΝΐηΗΗ (Ν (Ί (Ν1ΠΗΗΝ

<tjNN'fHHNNN'tHHN

> (0 H 3 μ 0.1 μ

Jtf - τΗ Ή 3

Ji Ή μ μ -H H

3 ϋ P P -M ..3 -h + i - «® t! λ

3 3 1 <0 <0 <0 tS

<0 ® -H 6-HE -H (0 Ή · * c e- «§ · μ ® μ ® μ e μ g -h 2 μ and μ np« μ | μ p «μ® μ® ja® = 3 μ® «« ® «μ®« s βμ. * μ Λ! μ ®μ Sc · * c. ocoe χ c '“μ Ο (0 1 G ® C« 10® - Ε

gw-HOW-HOM-HCM-H S

OjK-o-H.XO-H.SOO.iiO S®

Η · Η · Ημμμμ · Η · Η · Ημ · Η S

μπμμΗμμΗ »μμΗμ« o

S 3> 1 * 3> ί> i 3 iH> i3 -¾ G

^ AH> i Q <CO> iO <®> iG <® 3,0> ιομμο · Ημο · Ηί> ιθ · Η 5 ® + ίμΗβμΗβμΗμ μΗ r en ®ο ·> ιμα? Η · Ηθ.> Ια> α> Η 5® μ - ^ o> iHo> iHo> i ^ o ^ o® ® Η (ομ> ι®μ> ι®μΗ®μ so O -H. * £ -H *>, -HX> 1 -H . * & o ^ eoasoaHoSeo «e O ^ 3 Ή O 3 -HO 3-HA 3 H“ a). * 0.ΗΗμ · ΗΗμ · ΗΗ0 · Η.-1 Τι® o μμί> ι & μίΗαμ> ιμμ> ι ®jc * Λμ> ιθμ> ιθμ> ιθ.μ> ι xo Ο (θμ®®μ®®μ®®μ -JC M c β μ ca -HG .0) μ g an <g V - «- '- | o + * co • h i O ω n h (i) n <* in i £> _ Γ <* «28 81 975

Cu recoveries after 8 minutes are all so high in Table IV (approaching the theoretical limit of 1.0) that the use of statistical confidence limits was not applied.

5 95% confidence level of statistical error

The recovery of Mo at 8 minutes is ± 0.012. The composite compositions of this invention clearly produce Mo recoveries that far exceed those that would be expected of the individual components when used alone. For example, the recovery of run Mo 2 clearly exceeds that expected from the weighted average of runs 1 and 2. Synergism has taken place.

Claims (10)

1. Flotation collector composition for the extraction of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals, characterized in that said collector composition contains a) hydrocarbon sulfide of the formula IR ^S-R2 (I) 10 - 90% by weight of said collector composition and b) alkylthiocarbonate of formula II XIII R'-X-C-S'M * (II) or thionocarbamate of formula III S 20 (R8) -N-C-Y (III) (H) b or thiophosphate of formula IV Or mixtures thereof, wherein (b) is 10 - 90 30% by weight of said composition, wherein formulas R 1 and R 2 are independently hydrocarbyl radical or hydrocarbyl radical substituted with a or more hydroxy, cyano, halogenether, hydrocarbyloxy or hydrocarbylthioether groups, wherein R1 and R2 may together form an epithelial structure with S, on the condition that S is bonded to an aliphatic or cycloaliphatic carbon atom; on the additional condition that the total carbon content of the hydrocarbon sulphide is 4 to 20 carbon atoms; R7 is a C1-20 alkyl group; R8 is independently a C1-4 alkyl group; 2. A composition according to claim 1, characterized in that it contains a) 20 - 80% by weight hydrocarbon sulfide and b) 20 - 80% by weight alkylthiocarbonate, thionocarbamate, thiophosphate or mixtures thereof. 3. A composition according to claim 1, characterized in that R 1 and R 2 are independently an aliphatic, cycloaliphatic or aralkyl group, unsubstituted or substituted by one or more hydroxy, cyano, halogen, OR3 or SR3. groups; R 3 is hydrocarbyl radical, wherein R 1 and R 2 together can form a heterocyclic ring with S; R7 is C2-16 alkyl; R 8 is -alkyl; R9 is C2-10 alkyl; R 10 is C 2-8 alkyl or cresyl; and 30 M is sodium or potassium cation. 4. A composition according to claim 1, characterized in that R1 and R2 are an aliphatic or cycloaliphatic group, unsubstituted or substituted by one or more hydroxy, cyano, halogen, OR3 or SR3 groups, wherein R1 and R 2 may together form an epitry ring with S, R 3 is hydrocarbyl radical, R 7 is C 3-12 alkyl, 81 81 975 R 8 is C 1-6 alkyl, R 9 is C 2-6 alkyl and R 10 is C 2-8 alkyl or cresyl. 5. A composition according to claim 4, characterized in that the total carbon content of the hydrocarbon sulfide is 6 to 16 carbon atoms. R 9 is a C 1-6 alkyl group; R10 is independently hydrogen, a C1-10 alkyl group or aryl group; M is alkali metal cation; X is independent in each case S or 0; Y is -S "M + or OR9; a is the integer 1 or 2; and b is the integer 0 or 1, which is the condition that a + b = 2, on the additional condition that said metal-containing mineral is recovered in said foam. 6. A composition according to claim 5, characterized in that R 1 and R 2 are independently an alkyl or an alkenyl. A composition according to claim 6, characterized in that R 1 is methyl or ethyl and R 2 is a C 6 -11 alkyl or C 6 -U alkenyl group. Composition according to claim 1, characterized in that the hydrocarbon sulphide has the formula Id 15 (R4) 2-C-CH 2 O / S (Id) wherein R 4 is independently hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl , alkynyl, cycloalkyl, cycloalkenyl, hydroxy, cyano, halogen, OR3 or SR3, wherein aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl may be optionally substituted by hydroxy, cyano, halogen, The OR3 or SR3 group, wherein R3 is hydrocarbyl radical, provided that the total carbon content of the hydrocarbon portion of the collector is such that the collector has sufficient hydrophobic character to permit flotation of the metal-containing sulfide mineral or sulfidized, metal-containing oxide mineral particles. 9. A composition according to claim 1, characterized in that R1 and R2 are not the same hydrocarbon groups. Process for the extraction of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals from an ore, characterized in that the ore in the form of an aqueous mass is subjected to a flotation process in the presence of a flotation collector in the amount of 0.01-1. 0 kg / ton of ore, the collector containing> the composition according to claim 1.