FI82395C - Collector compositions for flotation of minerals - Google Patents

Description

1 82395

This invention relates to novel collectors for recovering metal-containing sulfide minerals, sulfidized metal-containing oxide minerals and metals present in the metal space, and all four groups of minerals are referred to herein as metal-containing minerals, from ores by foaming.

Flotation is the process of treating a mixture of finely divided solid minerals, e.g., powdered ore suspended in a liquid, whereby some of such solids are separated from other finely divided solids, e.g., clays and other similar ores, by introducing gas (or forming gas in). in situ) to form a foam mass containing a particular solid on top of the liquid and to exclude other suspended (non-foamed) solid components. Flotation is based on the principle that the introduction of a gas into a liquid, which contains solid particles of various materials suspended therein, causes some of the gas to adhere to certain suspended solids but not others, and makes the particles to which the gas is attached lighter than the liquid. . Thus, these particles of 25 rise to the surface of the liquid and form a foam.

Various blowing agents have been mixed into the suspension to improve the flotation process. Such added substances are classified according to their function: aggregators such as xanthates, thionocarbamates, etc .; foaming agents which help to form a stable foam, e.g. natural oils such as tall oil and eucalyptus oil; modifiers such as activators, e.g. copper sulphate, to initiate foaming in the presence of a collector, suppressants, e.g. sodium cyanide, which seek to prevent the collector from acting as such on the mineral desired; remaining in the liquid and thus preventing the substance from migrating upwards and forming part of the foam; pH regulators for optimal metallurgical results, e.g. limestone, soda ash, etc.

In the practice of the present invention, it is not essential to define the phenomenon which makes flotation a particularly valuable industrial operation. However, the phenomenon which makes flotation a particularly valuable industrial operation appears to be largely related to the selective affinity of the surface of particulate solids suspended in a liquid containing a gas on the one hand and in a gas on the other. The specific additives used in the flotation operation are selected according to the nature of the ore, the minerals to be recovered, and other additives used in combination with them.

Flotation is used in a variety of mineral separation processes, including the selective separation of metal-containing minerals such as copper, zinc, lead, nickel, molybdenum, and other metal-20 and iron-containing sulfide minerals, e.g., pyrite and pyrrotite.

Collectors commonly used for metal-containing sulphide minerals or sulphidised *. xanthates, dithiophosphates and thionocarbamates. Other aggregators generally considered useful in the recovery of metal-containing minerals or sulfidized metal-containing oxide minerals include mercaptans, disulfides (R-SS-R), and polysulfides / R- (S) n ~ R7 if -30 sa n is 3 or bigger.

Conversion of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals to a more useful, pure metal state is achieved; often used in smelting processes. Such smelting processes can lead to the formation of volatile sulfur compounds. Such volatile sulfur compounds are often released into the atmosphere through chimneys or are removed from such chimneys by an expensive and advanced scrubber. Many non-ferrous, metal-containing sulfide minerals or metal-containing oxide minerals naturally occur in the presence of iron-containing sulfide minerals such as pyrite and pyrrotite. When iron-containing sulfide minerals are recovered in flotation processes together with non-iron-containing metal-containing sulfide minerals and sulfidated metal-containing oxide minerals, excess sulfur is present which is released in the smelting processes. There is a need for a method for selectively recovering non-ferrous metal-containing sulfide minerals and sulfidized metal-containing oxide minerals without recovering iron-containing sulfide minerals such as pyrite and pyrrotite.

Of the commercial collectors, xanthates, thionocarbamates, and dithiophosphates do not selectively recover non-ferrous metal-containing sulfide minerals-20 and iron-containing sulfide minerals. On the contrary, such collectors collect and recover all metal-containing sulfide minerals. Mer captan assemblers are environmentally undesirable. . nature and are kinetically very slow metal ... 25 in the flotation of sulfide minerals. Disulfides and polysulfides used as aggregators give low yields and slow kinetics. Therefore, mercaptans, disulfide and and polysulfides are generally not used commercially. Furthermore, mercaptans, disulfides, and polysulfides do not selectively recover non-ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals.

Due to the above, there is a need for a flotation collector that selectively recovers, in relatively good yields, widely metal-containing minerals from ores in the presence of iron-containing sulfide minerals such as pyrite and pyrrhotite.

Thus, in one aspect, the present invention is a collector assembly for foaming metal-containing minerals, the combination comprising: (a) a compound of the formula:

R1-X- (R) -Q I

n 10 wherein Q is -N (R 2) (H), where a + b = 2, -N = Y, where Y is S, O, a hydrocarbylene radical or a substituted hydrocarbylene radical, N, or -N 2 cyclic a ring in which the cyclic ring is saturated or unsaturated and may additionally contain heteroatoms but must contain an N atom, 1 2 R and R are independently a C 1 -C 22 "* 1Ydr ° carbyl radical, a C 1 -C 22 substituted hydrocarbyl radical or saturated -20 saturated or unsaturated heterocyclic ring, 0

II

R is (-C-) y (-CH 2 -Jp (CBQB4m 0 * 25 where y + p 0 m = n, where n is an integer from 1 to 6 and y, p and m are independently 0 or an integer from append 1 to 6 and each portion may occur in random order, 1 3 30 X is -S -, - O-, -NR, 0 OR3 0

Il II I II

-C-S-, -C-N-, or -C-O-, • wherein R is hydrogen, a C 1-22 hydrocarbyl radical or a substituted hydrocarbyl radical, and 82395 (b) hydrocarbons containing monosulfide units of the formula:

R5-S-R6 VIII

Wherein R 1 and R 2 are each independently a hydrocarbyl radical or a hydrocarbyl radical substituted with one or more hydroxy, cyano, halogen, ether, hydrocarbyloxy or hydrocarbyl thioether moieties wherein R 1 and R 2 are may together form a heterocyclic ring structure with S, provided that S is attached to an aliphatic or cycloaliphatic carbon atom; further provided that the total carbon content of the hydrocarbon sulfide is such that it is sufficiently hydrophobic in nature to cause particles of the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral to drift to the air / bubble interface.

. . The invention also relates to a method for containing metal; to recover minerals from the ore, wherein the ore is subjected to a flotation process in the form of an aqueous mass in the presence of a foamable amount of a flotation collector, under conditions such that the metal-containing minerals are recovered in the foam.

The collector assemblies of this invention are capable of foaming widely metal-containing minerals. Furthermore, such collector combinations provide good yields and selectivity for the desired metal-containing minerals.

The collector combination described in the preferred process of this invention is used in a process for recovering metal-containing sulfide minerals or sulfidized metal-containing oxide minerals from an ore, subjecting the ore in the form of an aqueous mass of the drift of the oxide mineral 5 particles to the air / bubble interface and to be recovered in the foam.

The collector combination of the present invention results in a surprisingly high recovery of non-ferrous metallic minerals and a higher selectivity for such non-ferrous metallic minerals when such metal-containing minerals are present in the presence of iron-containing sulfide minerals.

Component (a) 15 of the assembler assembly of the present invention is a component of formula (I) above. Although not specifically shown in formula (I), it should be understood that in a low pH aqueous medium, preferably an acid-containing one, component (a) may be present in the form of a salt. In this formula, R is preferably 20 (-CH, -) s „© ® or mixtures thereof, where p + m + y = n, where n is an integer from 1 to 6, preferably 2 or 3. R and R are each is preferably a C 1-22 hydrocarbyl radical or a C 1-22 hydrocarbyl radical substituted by one or more hydroxy, amino, phosphonyl, alkoxy, · 1 'imino, carbamyl, carbonyl, thiocarbonyl, cyano, halogen -, ether, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbyl. When substituted, R or R is preferably substituted with one or more hydroxy,> · ·

II

· 7 82395

halogen, amino, phosphonyl or alkoxy moiety. Q

2 is preferably -N (R) (H), where a + b = 2.

a ö 1 2

More preferably, R and R have a total of six or more carbon atoms, and R 1 is preferably C 2-4 hydro-carbyl or C 2-4 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl or 2 alkoxy groups. , more preferably C4-11 hydrocarbyl; and R is preferably C 1-6 alkyl, C 1-6 alkylcarbonyl or C 1-6 substituted alkyl or alkylcarbonyl, more preferably C 1-6 alkyl or C 1-6 alkylcarbonyl or C 1-6 alkyl or C 1-6 alkyl; C 1-6 alkylcarbonyl substituted with an amino, hydroxy or phosphonyl group, and most preferably C 1-2 alkyl or C 1-2 alkylcarbonyl. In addition, R is preferably - (CHO) - or 2 p ©.

20 more preferably - (CH-) -, n is preferably an integer less than

- P

paste 1-4, most preferably 2 or 3; X is preferably -S-, V: 3 3 * · -NR or -O-, more preferably -S- or -NR, most preferably V. 3 -S-, and R is preferably hydrogen or C 1-14 hydrocarbyl. * more preferably hydrogen or C 1-4 hydrocarbyl, most preferably hydrogen.

As described, component (a) contains compounds such as:

O

R1-C-SfCH2irlN-fR2) a 30 <H) b n omega- (hydrocarbylthio) alkylamines and omega- (hydro-35-carbylthio) alkylamides: »· • · • • s 82395 R1-S-fCH2-> nMiR2) a; <ä) b 5 111 N- (hydrocarbyl) -alpha, omega-alkanediamines: R (H) b 10

IV

N- (Onega-aminoalkyl) hydrocarbon amides: 0

R 2 -C -NfCH- (NfR 2) b 15 '3 2 n * D

R3 (H) a

V

omega- (hydrocarbyloxy) alkylamines: R1-O ^ CH2 ^ nN ^ R2) a (H) b

.? VI

25 .. and omega-aminoalkyl hydrocarbonates: 0 R1-CO4CH2 ^ nN4R2) a 30 <*> b

VII

12 3 where R, R, R, a, b and n are the same as previously defined. In formulas II to VII, when X is -S- or 9 82395 o

II

-c-s-R 3 is preferably C 1-6 hydrocarbyl when X is 50 R 3

If f is -N- or -C-N-13

R

The total amount of carbon in the groups R3 and R3 is preferably between 1 and 23, more preferably between 2 and 16 and most preferably between 4 and 15; and when X is

O

II

-CO- or -O-R 3 is most preferably C 1-6 hydrocarbyl.

Of the above, the preferred component (a) includes omega- (hydrocarbylthio) alkylamine, N- (hydrocarbyl) alpha, omega-alkanediamine, omega- (hydrocarbyloxy-20si) alkylamines. N- (omega-aminoalkyl) hydrocarbon amides, omega- (hydrocarbylthio) alkylamide or mixtures thereof. More preferred compounds of component (a) include *. · Omega- (hydrocarbylthio) alkylamines, N- (hydrocarbyl) - * ·· alpha, omega-alkanediamines, N- (omega-aminoalkyl) carbon *: hydrogenamides, omega- (hydrocarbylthio) ) alkylimide or mixtures thereof. The most preferred class of compounds of component (a) are omega- (hydrocarbylthio) alkylamines, for example 2- (hexylthio) ethylamine, and omega- (hydrocarbylthio) alkylamide, for example ethyl 2- (hexylthio) ethyl-amide.

The omega- (hydrocarbylthio) alkylamines of formula III can be prepared by the methods contained in Berazosky® et al. U.S. Patent 4,086,273, FR Patent 1,519,829; and Beilstein, 4, 4th ed., 4. Supp. 1655 (1979).

N- (omega-aminoalkyl) hydrocarbon amides of formula V can be prepared by the methods described in U.S. Patent 4,326,067 to Fazion 10,829,595 to Acta Polon Pharm, 19, 277 (1962); and Beilstein, 4, 4th ed., 3rd ed., 587 (1962).

The omega- (hydrocarbyloxy) alkyl-5-amines of formula VI can be prepared by the methods described in GB Patent 869,409 and Hobbs U.S. Patent 3,397,238.

S- (omega-aminoalkyl) hydrocarbon thioates of formula II can be prepared by the methods described by Gaye et al., U.S. Patent 3,328,442; and Beilstein 10 4, 4th ed., 4th ed., 1657 (1979).

Omega-aminoalkyl hydrocarbonates of formula VII can be prepared by the methods described in J. Am. Chem. Soc., 83, 4835 (1961); Beilstein 4, 4th ed., 4th ed., 1413 (1979); and Beilstein 15 4, 4th ed., 4th ed., 1785 (1979).

The N- (hydrocarbyl) -alpha, omega-alkanediamines of formula IV can be prepared by a method well known in the art. One example is the method described in DD Patent 98,510.

Component (b) of the collector assembly is an organic compound containing at least four carbon atoms and one or more monosulfide units in which the sulfur atoms of the sulfide units are attached to non-aromatic carbon atoms, i. aliphatic or cycloaliphatic carbon liatoms. A monosulfide unit here means a unit in which each sulfur atom is attached to two carbon atoms of only the non-aromatic moiety, for example, to two carbon atoms of the hydrocarbon moiety only. Hydrocarbon compounds may contain one or more monosulfide units and include compounds substituted on the hydroxyl, cyano, halogen, ether, hydrocarbyl, 1, hydroxy and hydrocarbyl thioether moieties.

| # Preferred organic compounds containing: 1 monosulfide units include those corresponding to the formula:

V 'R5-S-R6 IX

II

»N 82395 wherein R 1 and each are independently a hydrocarbyl radical or a hydrocarbyl radical substituted by one or more hydroxy, cyano, halogen, ether, hydrocarbyloxy or hydrocarbyl thioether moieties; wherein R 1 and R 2 may combine to form a heterocyclic ring structure with S; provided that S is attached to an aliphatic or cycloaliphatic carbon atom; further provided that the total carbon content of the sulphide moiety is such that the sulphide moiety has a sufficiently hydrophobic nature to cause the metal-containing sulfide mineral particles to drift to the air / bubble interface.

The specific R5 and R6 groups most preferably used herein depend on various factors, including component (a) to be used, ore to be treated, etc. In general, to provide the required hydrophobic nature, a monosulfide compound of formula IX contains at least four, more preferably six, and most preferably eight. carbon atoms. The maximum number of carbon atoms in the monosulfite-20 di compound is preferably 20, more preferably 16 and most preferably 12.

5 6

Preferably R and R are independently an aliphatic, cycloaliphatic or aralkyl moiety, unsubstituted or substituted with one or more hydroxy, cyano, halogen, -OR or -SR moieties, wherein R is a hydrocarbyl radical; R and R may combine to form a heterocyclic ring with S. R 1 and R 2 are more preferably an aliphatic or cycloaliphatic moiety, unsubstituted or substituted by one or more cyano, halogen, hydroxy, OR or SR moieties, wherein R 2 is a hydrocarbyl radical; wherein R 1 and R 2 may together form a heterocyclic ring with S.

In a more preferred embodiment, R 1 and R 5 do not form a heterocyclic ring with S, and R and R 35 are each independently alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, unsubstituted or substituted with one or more hydroxy, halogen, cyano, OR or SR, wherein R is aliphatic or cycloaliphatic. In the most preferred embodiment, 5 6 R and R are not the same hydrocarbon moiety, i. monosulfide 7 5 is asymmetric. R is preferably aliphatic or cycloaliphatic. R 7 is more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl. In a most preferred embodiment, R 1 and R 6 are independently alkyl or alkenyl, preferably R 1 * is methyl or ethyl and R 1 is C 1 -C 4 alkyl or a C 1-6 alkenyl group, for example ethyl octyl sulfide.

Examples of cyclic compounds that can be used as the monosulfide compound of formula IX include the following structures: (r8) 2 - (^ P- <R8) 2 and 0 g wherein R is independently hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, 7-cycloalkenyl, hydroxy, cyano, halogen, OR or 7 SR group, wherein the aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group may optionally be be substituted by hydroxy, cyano, halogen, OR or SR, etc .; wherein 7 R is a hydrocarbyl group, preferably an aliphatic or cycloaliphatic, more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl; and R is straight or branched alkylene or alkenylene or alkynylene, unsubstituted or substituted by hydroxy, cyano, halogen, 7.7 OR or SR.

A preferred compound useful as component (b) in this invention corresponds to the formula: i3 82395 5

(R4> 3-nC (H) n * S'C <H) n (R4) 3-n tal (r8> 2 * C \ ', F2 X _ xa S

g wherein R is as previously defined; 4 R is independently hydrocarbyl or hydrocarbyl substituted with hydroxy, cyano, halogen, ether, hydrocarbyloxy or hydrocarbylthioether moieties; wherein the two R moieties may be taken together to form a cyclic ring or a sulfur atom of a heterocyclic ring; n is an integer 0, 1, 2 or 3; provided that the total hydrocarbon content of the hydrocarbon portion of the collector is such that the collector is sufficiently hydrophobic in nature to cause particles of the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral to drift to the air / bubble interface.

4

In the above formula, R is preferably an aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl group, unsubstituted or substituted by cyano, halo * · '·' 77 7. . with a gene, hydroxy, OR or SR group, wherein R is 4 as defined above. More preferably, R is an aliphatic or cycloaliphatic group, unsubstituted or substituted by a hydroxy, cyano, halogen, aliphatic ether, cycloaliphatic ether, aliphatic thioether or cycloaliphatic thioether group.

4

Even more preferably, R is an alkyl, alkenyl, cycloalkyl or cycloalkenyl moiety. Most preferably, one -C (H) n (R 41) 2 -n is a methyl or ethyl group and the other is: a C 1 -C 4 alkyl or C 1 -C 4 alkenyl group. Preferably n; V: is 1, 2 or 3 and most preferably 2 or 3.

Preferred hydrocarbon-containing monosulfide units of the formula R 1 -SR **, in which R 1 and R 2 are as defined above, are prepared by standard methods known from the art n 82395, e.g. by reacting R 1 -H with R 1 -SH, wherein R 1 and R 2 are as defined above.

Examples of compounds falling within the scope of the present invention are metyylibutyylisulfidi, methyl-5 pentyylisulfidi, metyyliheksyylisulfidi, methylheptyl sulfide, metyylioktyylisulfidi, metyylinonyylisulfidi, metyylidekyylisulfidi, metyyliundekyylisulfidi, methyl dodekyylisulfidi, metyylisyklopentyylisulfidi, methyl sykloheksyylisulfidi, metyylisykloheptyylisulfidi, methyl-10 lisyklo-oktyylisulfidi, etyylibutyylisulfidi, etyylipen-sulfide, etyyliheksyylisulfidi, etyyliheptyylisulfi-oxide, etyylioktyylisulfidi, etyylinonyylisulfidi, ethyl sulfide, etyyliundekyylisulfidi, etyylidodekyylisul-sulfide etyylisyklopentyylisulfidi, etyylisykloheksyylisul-15 sulfide etyylisykloheptyylisulfidi, etyylisyklo-oktyylisul-sulfide propyylibutyylisulfidi, propyylipentyylisulfidi, the pro-pyyliheksyylisulfidi, propyyliheptyylisulfidi , propyl octyl sulfide, propyl nonyl sulfide, propyl dececyl sulfide, propyl undecyl sulfide, propyl dodecyl sulfide, propyl cyclopentyl sulfide di, propylcyclohexyl sulfide, propyylisykloheptyylisulfidi, propyylisyklo-oktyylisulfidi, dibutyl sulfide, butyylipentyylisulfidi, butyyliheksyylisulfidi, butyyliheptyylisulfidi, butyl oktyylisulfidi, butyylinonyylisulfidi, butyylidekyylisul 25-sulfide butyyliundekyylisulfidi, butyylidodekyylisulfidi, butyylisyklopentyylisulfidi, butyylisykloheksyylisulfidi, butyylisykloheptyylisulfidi, butyylisyklo-oktyylisulfidi, dipentyylisulfidi, pentyyliheksyylisulfidi , pentyylihep-sulfide, pentyylioktyylisulfidi, pentyylinonyylisul-30 sulfide pentyylidekyylisulfidi, pentyyliundekyylisulfidi, pentyylidodekyylisulfidi, pentyylisyklopentyylisulfidi, pentyylisykloheksyylisulfidi, di-pentyylisykloheptyylisulfi, pentyylisyklo-oktyylisulfidi, diheksyylisulfidi, hexyl 'syyliheptyylisulfidi, heksyylioktyylisulfidi, hexyl nonyylisulfidi 35, heksyylidekyylisulfidi, heksyyliundekyy - *. ·. sulphide, hexyldodecyl sulphide, hexylcyclopentene

II

15 82395 sulfide, heksyylisykloheksyylisulfidi, heksyylisyk-loheptyylisulfidi, heksyylisyklo-oktyylisulfidi, dihep-sulfide, heptyylioktyylisulfidi, heptyylinonyylisul-sulfide heptyylidekyylisulfidi, heptyyliundekyylisulfidi, 5 heptyylidodekyylisulfidi, heptyylisyklopentyylisulfidi, heptyylisykloheksyylisulfidi, heptyylisykloheptyylisulfi-oxide, heptyylisyklo-oktyylisulfidi, dioctyl sulfide, ok tyylinonyylisulfidi, oktyylidekyylisulfidi , oktyyliunde-sulfide, oktyylidodekyylisulfidi, oktyylisyklopen-10 sulfide, oktyylisykloheksyylisulfidi, oktyylisyklo-heptyylisulfidi, oktyylisyklo-oktyylisulfidi, dinonyl sulfide, nonyylidekyylisulfidi, nonyyliundekyylisulfidi, nonyylidodekyylisulfidi, nonyylisyklopentyylisulfidi, well-nyylisykloheksyylisulfidi, nonyylisykloheptyylisulfidi, 15 nonyylisyklo-oktyylisulfidi, didekyylisulfidi, dekyyliun-dekyylisulfidi , decyldodecyl sulfide, decylcyclopentyl sulfide, decylcyclohexyl sulfide, decylcycloheptyl sulfide and decyl at-oktyylisulfidi. More preferred sulfides include methylhexyl sulfide, methylheptyl sulfide, methyl octyl sulfide, methyl nonyl. lisulfide, methyldecyl sulfide, ethylhexyl sulfide, ethylheptyl sulfide, ethyl octyl sulfide, ethyl nonyl sulfide, ethyl decyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diheptyl sulfide, and di-oxy sulfide.

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 aromatic compounds.

Aliphatic as used herein means straight and branched and saturated and unsaturated hydrocarbon compounds, i.e. alkanes, alkenes or alkynes. Cycloaliphatic here means saturated and unsaturated cyclic hydrocarbons, i.e. cycloalkenes and cycloalkanes.

Cycloalkane means an alkane containing one, two, three or more cyclic rings. Cycloal-5 kene 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 hydrocarbyl includes the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cycloaliphatic aralkyl and alkaryl. The term aryl as used herein means biaryl, biphenyl, phenyl, naphthyl, phenanthrenyl, anthracenyl, and two aryl groups linked together by an alkylene group bridge. Alkaryl as used herein means an alkyl, alkenyl- or alkynyl-substituted aryl substituent, wherein aryl is as previously defined. Aralkyl as used herein means an alkyl group in which the aryl is as previously defined.

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

Halogen here means a chlorine, bromine or jo group.

Hydrocarbylene as used herein means an organic radical containing carbon and hydrogen atoms which must be attached to the nitrogen atom by a double bond. The term hydrocarbylene includes the following organic compounds: alkenyl, cycloalkenyl and aralkylene, wherein aryl - is defined as before.

Heterocyclic ring as used herein means both saturated and unsaturated heterocyclic rings, including the -N-cyclic ring. The heterocyclic ring 17 82395 may contain one or more N, O or S atoms. Examples of suitable heterocyclic rings are pyridine, pyrazole, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, coumarin, carbazole, acridine, imidazole, oxazole, thiazole, pyridazine, pyrimidine, pyrimidine, pyridine imine, oxirane, azetidine, oxetane, titanium, pyrrole, pyrrolidine, tetrahydrofuran, isoxazole, piperidine, azepine and the like.

The combination of this invention is prepared by using sufficient amounts of component (a) and component (b) to produce an efficient collector for collecting metal-containing minerals from ores by a flotation process. The amounts of each component most preferably used in the preparation of the combination will vary depending on the specific components (a) and (b) used, the particular ore to be treated and the desired degrees of selectivity. The combination preferably comprises from about 10 to about 90, more preferably from 20 to 80% by weight of component (a) and from about 10 to about 90, more preferably from 20 to 80% by weight of component (b). More preferably, the combination of the present invention comprises from about 30% to about 70% by weight of component (a) and from about 30% to about 70% by weight of component (b).

. The process of this invention is useful for recovering metal-containing minerals from ores by foaming. Ore here means a material as taken from the soil and contains the desired metal-containing minerals in admixture with the side rock. Side sideline here means that part of the substance which has little or no value and which must be separated from the desired metal-containing minerals.

The collector combination of the present invention is preferably used in the recovery of metal-containing minerals by a flotation process. In a more preferred embodiment of the present invention, minerals containing copper, nickel, lead, zinc or molybdenum are recovered.

is 82395

In a more preferred embodiment, copper-containing minerals are recovered. Preferred metal-containing sulfide minerals are also those with high natural hydrophobicity in the non-oxidized state. The term "hydro-5 phobicity in the non-oxidized state" means a freshly ground mineral or a mineral with a fresh surface that indicates a tendency to foam without the addition of a collector.

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. Examples of metal-containing sulfide minerals that can be concentrated by flotation using the process of this invention include copper-containing minerals such as covellite (CuS), calcosite (Cu2S), chalcopyrite (CuFeS2>, vallerite (Cu2Fe2S) or Du ^ Fe ^ S ^), bornite (Cu ^ FeS ^), cubanite (Cu ^ Fe ^ S, -), enargite / Cu ^ (As- ^ Sb) S ^ 7, tetrahedral (Cu2SbS2), tennantite (Cu ^ Fe As ^ S ^), bronchantite 20 / Cu ^ (OH) gSO4 J, antlerite / "Cu ^ SO ^ (OH), famatinite ^ Cu-j (SbAd) S4J and bournonite (PbCuSbS ^)? Lead-containing · Minerals such as lead (PbS), antimony-containing minerals such as stabnite (Sb), zinc-containing minerals such as zinc scintillation (ZnS), silver-containing minerals such as stefanite ( Ag ^ SbS ^) and argentite (Ag2S), chromium-containing minerals such as daubrelite (FeSCrS ^), nickel-containing minerals, k for example pentlandite Z * (FeNi) gSg7; molybdenum-containing minerals such as molybdenite (MoS2); platinum and palladium-containing minerals such as cooperite / PtiAbS). Preferred metal-containing sulfide minerals include molybdenite (MoS2), chalcopyrite (CuFeS2), lead (PbS), zinc scintillation (ZnS), bornite (CuFeS2) and pentlandite (*N) (FeNi). ^ S ^.

i9 82395

Sulfidized metal-containing oxide minerals are minerals that are treated with a sulfidizing chemical to impart the characteristics of the sulfide mineral to such minerals, and thus the minerals can be recovered by flotation using collectors that collect sulfide minerals. Sulfinization results in oxide minerals with the characteristics of a sulfide mineral. Oxide minerals are sulfidized by contact with compounds that react with the minerals to form a sulfur-10 bond or affinity. Such methods are well known in the art. Such compounds include sodium hydrogen sulfide, sulfuric acid and the like sulfur-containing salts such as sodium sulfide.

Sulfidized metal-containing oxydimines and oxide minerals for which this method is useful include oxide minerals containing copper, aluminum, iron, titanium, magnesium, chromium, tungsten, molybdenum, manganese, tin, uranium, and mixtures thereof. Examples of metal-containing oxide minerals that can be concentrated by flotation using the process of this invention include copper-containing minerals such as · / cuprite (Cu 2 O), tenorite (CuO), malachite / Cu 2 (OH) 2 - CO37, azurite / "Cu 2 (OH) ) 2 (CO 2) 2, attackamide ZCu 2 Cl-25 (OH) γ, chrysococcal (CuSiO 2), aluminum-containing minerals such as corundum, zinc-containing minerals such as zincite (ZnO) and smitsonite (ZnCO 2), tungsten-containing minerals, such as tungsten / '(FejMniWO ^; nickel-containing minerals such as bunzenite (NiO); molybdenum-containing minerals such as wulfenite (PbMoO ^) and powellite (CaMoO ^); iron-containing minerals such as hematite and magnetite; chromium-containing minerals , such as chromite (FeOCr 2), ores containing iron and titanium, such as ilmenite, magnesium 35 and minerals containing aluminum, such as Spinelli, containing iron-chromium minerals such as chromite, titanium-containing minerals such as rutile; manganese-containing minerals such as pyrolucite; tin-containing minerals such as cassiterite; and uranium-containing minerals such as uranite; and uranium-containing minerals, such as uranium pitch (* U2®5 ^ U3 ° 8 ^ 3a 9unm ^ 't “ti (U03nH2O).

Other metal-containing minerals for which this method is useful include gold-containing minerals such as sulvanite (AuAgTe2) and fish-10 verite (AuTe); platinum and palladium-containing minerals such as sperrylite (PtAs2); and silver-containing minerals such as hessite (AgTe2). These also include metals present in the metal space, e.g., gold, silver, and copper.

The collector combinations of this invention can be used at any concentration that provides the desired yield of the desired minerals. In particular, the concentration used depends on the minerals to be recovered, the quality of the mal-20 min to be taken into the flotation process, the desired: quality of the minerals to be recovered and the mineral to be recovered.

Preferably, the collector combination of the present invention is used in concentrations of 5 g to 100 g per ton of ore, more preferably about 10 to 200 g of collector per ton of ore introduced into the flotation. In general, in order to achieve optimal synergistic behavior, it is most advantageous to start at low dosage levels and increase the dosage level until the desired effect is obtained. The synergism is defined herein as the measured result of a mixture of two or more components exceeding the average weighed results of each component used alone. The term also indicates that the results are compared under conditions in which the total weight of the collector used is the same for each experiment.

During the flotation process of the present invention, the use of flotation agents is preferred. Foaming agents 21 82395 are well known in the art and are referred to for the purposes of this invention. Any blowing agent that results in the recovery of the desired metal-containing mineral is suitable. Foaming agents useful in this invention include any blowing agents known in the art that provide the desired finale. Examples of such blowing agents include C5-8 alcohols, tall oils, cresols, C 1-4 alkyl ethers of polypropylene glycols, dihydroxyates of polypropylene glycols, glycols, fatty acids, soaps, edetoxides, etc., alkylaryl sulfonates can be used. Any blowing agents suitable for the recovery of ores by flotation can be used in this invention.

Furthermore, in the method of the present invention, it is contemplated that the collector combination that forms the combination of this invention may be used in admixture with other collectors well known in the art.

The collector combination of the present invention can be used with other collectors known in the art in an amount to provide the desired yield of the desired mineral. Examples of such other collectors useful in this invention include dialkyl thioureas, alkyl, dialkyl and trialkyl thiocarbonates, alkyl and dialkyl thionocarbamates, monoalkyl, lithithiophosphates, dialkyl and diarylate dithiophytophosphates. and diarylthiophosphonyl chlorides, dialkyl and diaryl dithiophosphonates, alkyl mercaptans, xanthene gene formats, mercaptobenzothiazoles, fatty acids and salts of fatty acids, alkyl sulfuric acids and their salts, alkyl and alkaryl sulfonic acids and their salts, alkyl and alkaryl sulfonic acids and their salts : phosphoric acids and their salts, sulphosuccinates, sulpho- ···. zinc amates, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkylpyridine salts, guanidine and alkylpropylene diamines.

Specific implementations

The following examples are included for illustrative purposes only and are not to be construed as limiting the scope of the invention. Unless otherwise indicated, all parts and fractions are by weight.

The operation of the flotation processes described in the examples is shown by giving a fractional amount recovered over a specified time.

Example 1

Foaming of copper and molybdenum

A series of bags (Samples Nos. 1 to 8) were prepared containing 1,200 g of homogeneous copper / molybdenum-15 ore containing chalcopyrite and molybdenite minerals from western Canada. The ore in each bag was ground using 800 ml of tap water for 14 minutes in a ball mill with a mixed ball load to give a grinding of about 13% plus 100 mesh. The resulting mass 20 was transferred to an Agitar 1,500 ml flotation cell with an automatic defoamer. The pH of each slurry was adjusted to 10.2 with lime. No further pH adjustments were made during the test. Normal methyl isobutylcarbinol (MIBC) blowing agent and the 25 collectors or combinations of collectors shown in Table I were used to foam copper and molybdenum using the four-step pre-foaming scheme shown below.

Step 1: collector - 0.0042 kg / tn * MIBC - 0.015 kg / tn ** 30 - coaching - 1 min - flotation - concentrate collection 1 min

Step 2: collector - 0.0021 kg / tn * MIBC - 0.005 kg / tn ** - coaching - 0.5 min • 35 - flotation - concentrate collection 1.5 min li 23 82395

Step 3: collector - 0.0016 kg / tn * MIBC - 0.005 kg / tn ** - coaching - 0.5 min - flotation - concentrate collection 2.0 min 5 Step 4: collector - 0.0033 kg / tn * MIBC - 0.005 kg / tn ** - coaching - 0.5 min - flotation - concentrate collection 2.5 min * kg collector or collector combination per tonne of ore to be processed ** kg flocculant per tonne of ore to be processed

The results of the flotation test are summarized in Table I.

Table I

15, Cu Möly Cu, Möly

Drive No. Collector1 R-72 R-72 quality1 quality 1 * A 0.688 0.682 0.063 0.00233 2 * B 0.770 0.713 0.028 0.00125 3 * C 0.710 0.691 0.093 0.00325 20 4 * D 0.699 0.697 0.107 0.00386 Ϋ 5 C / A 0.766 0.768 0.052 0.00157: .V 6 C / B 0.732 0.750 0.081 0.00275 7 D / A 0.759 0.764 0.050 0.00170 8 D / B 0.743 0.755 0.091 0.00316 25 * Not an example of this invention 1A = CgH.-SfCH-J-NW 2R-7 is an experimental fraction A ™ “yield after seven minutes ... at 30 o / cc2h5 '· * lB s 3The class is a fractional of the specified -I.' ® metal *. * 'contents in total weight.' ** collected in foam

35 H

1C = C, H, --C-CH-, *: 6 13/2 s: 1 ° = C6H13-S-CH3 24 82395

When performing flotation testing on Samples Nos. 1-8, the collector combination comprises 50% by weight of each collector.

The 95% confidence limit for the statistical error associated with the Cu R-7 value in Table I is t 0.010. Thus, for example, the statistical range of the amounts of Cu R-7 in Table I related to collector A is 0.688 t 0.010 or 0.678 -0.698.

The statistical error associated with the Mo R-7 values in Table I is ί 0.015.

Are the yields of Cu and Mo at seven minutes for the collector compositions of the present invention as good or better than the yields of seven minutes that could be expected from the weighed average effect when used with the components alone? synergism has occurred.

15 Example 2

Flotation of Cu / Ni ore

A series of -10 mesh ore samples from Eastern Canada were divided into 900 g samples. The ore contained chalcopyrite, pentlandite and pyrrolite minerals. All tests were performed using an Agitair 1,500 ml cell operated at 900 rpm and an air flow of 9.0 rpm. Prior to flotation, each sample was ground in a rod mill for 1,080 revolutions. Prior to grinding, 600 ml of water and sufficient lime were added to adjust the pH in the slurry to 9.2. After grinding, the ore had a particle size of less than 200 mesh / 75. The contents of the rod mill were emptied into the flotation cell and the pH was adjusted to 9.2 (using either lime or sulfuric acid).

A complex nine-stage dosing cycle was performed. The first four flotations are called pre-flotation and steps five through nine are called cleaning flotation. After step 4, sulfuric acid was added to adjust the pH to 9.2; CuSO 4 was added to step 5 and step 7 (0.015 kg / tn). The blowing agent used was 35 D0WFR0THR 250.

The amounts of blowing agent and collector added are shown in Table IIA.

25 82395 Ή

fO

tn 3 - • PC;

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O

c C 0ΒΝ0ΒΨΝΌ> Ό>

tU tNr-tOOPOOOO

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«I

Samples were dried, weighed and metal tested. Normal mass equilibrium formulas were used to calculate yields and grades. The results are summarized in Table IIB.

li 27 82395

B

μ μ

•B

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>> (O

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P -C

-μ p c

-μ O, -H

P - Ai Ι-H id O <Π O 3 nj (ö f4 m en e "m P o.

• h pv r »· m o -μ e 2 i - -« e -μ p

2 0 0 0 -H p X

-Ρ r — l P P <#> p λ; i e o • h e e

«N o Ή o ε -H -H

m r * co r- _ + i S

M 3 i — t O 'o o e 3 H O I - - * -: (C p

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Π φ * H LH

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Zi O ή

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V: * o o e. m. n 2 0 ^ NvOinvO -H .2 C id

Sf ^ O O O £ e rt S

.'- · u '___ a- ia id tn. . 2000 μ ia in id

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* -h C O O

. -f * m a) e λ; * U O C -H o * · A a. . * H r-1 ^ o * y e ^ ιβ i

_ E: θ id id M

2L * e ^ e .. 5? . J '* e e o ia e 2 Ä -H o -H -n S _ tn -H -μ

rX + S ν 'M jJ M I

O o as <5 λ; «<^ <2 <m <ΰ u W CJ μ 4-i en (Λ e Ή ro iH O ': id e SS ECO ia vO <·: ta O tn uo -μ r * in OP„ m ψ Γ " I- * o:; 'Γ15l hn n- iinii -ro

• <e · W 2 2 <C

* 2 * · OJ ro v 28 82 395 In this example, the lowest possible pyrrithite yields and the highest Cu and Ni yields after seven minutes are important because the main quenching of the high-sulfur mineral takes place at this time point. After 17 minutes, the yields of Cu and Ni are the highest possible using normal flotation logic. However, Cu yields approached the theoretical limit of 1.0 at both 7 and 17 minutes, and thus statistically significant comparisons were not possible.

The Ni yield after seven minutes using the aggregate mixture of the present invention clearly gave a high amount and a low amount of pyrrotite. The Ni yield at 17 minutes with the mixture according to the invention is also high. The 95% confidence level for the statistical error associated with Ni R-7 is ί 0,015 and for R-17 t 0,006; pyrrotite at R-7 is t 0.012. The Ni yield indicates that synergism has occurred and the desired lower yield of pyrrotite was obtained.

20 Example 3

Flotation of complex Pb / An / Cu / Ag ore

A series of congruent 1,000 g samples of the complex Pb / Zn / Cu / Ag ore from Central Chicken was prepared. The ore contained lead flux, zinc sparkle, chalcopyrite, and 25 argenite minerals. With each flotation, the sample was placed in a rod grinder and with it 500 ml of tap water and 7.5 ml of SC 2 solution. Six and a half minutes grinding time was used for preparation of the feed such that 90% of the ore had a particle size of less than 30 to 200 mesh (75 yum). After grinding, the contents were transferred to a cell with an automatic spatula to remove foam and the cell was attached to a normal Denver flotation mechanism.

Then two-stage flotation was performed -35 stage I was copper / lead / silver pre-foaming and stage II was zinc pre-foaming. To start the flotation of the phase I, 1.5 g / kg ^ 200 ^ (pH 9-9.5) was added and then the collector (s) were added. The mass was then cured for five minutes with air and stirring. This was followed by two minutes of coaching with just stirring. Li-5 was then adjusted with methyl isobutylcarbinol blowing agent (MIBC) (normal dose 0.015 ml / kg). The concentrate was collected five minutes after flotation and named copper / lead pre-concentrate.

In the flotation of stage II, 0.5 kg / t of CuSO 4 was added to the waste of stage I ken-10 non. The pH was then adjusted to 10.5 by adding lime. This was followed by a five-minute coaching session with just stirring. The pH was then checked and adjusted back to 10.5 with lime. At this point, the collector (s) was added, followed by a five to 15 minute training period with stirring only. Methyl isobutylcarbinol blowing agent (MIBC) (normal dose 0.020 ml / kg) was then added. The concentrate was collected for five minutes and designated zinc preconcentrate.

Concentrate samples were dried, weighed, and appropriate samples were prepared experimentally using X-ray technique. Using experimental data, fractional yields were calculated using normal mass equilibrium formulas. The results are summarized in Table III.

30 82395

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-H>, - P -P

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*. : .t · Η I +) C

^ ^ + JflN J) O

op rp es n ^. . -n h ‘n i i i m <e w 1 1, 4« <CO CJ as 3i 82395

The 95% confidence levels of the statistical error of the five minute recovery data for Cu / Pb flotation (Step I) are Ags t 0.01; For Cu t 0.01 and for Pb ί 0.02. Runs 1 and 4 represent tests in which individual components were used in each of the 5 steps.

In step 2 of run 2, the addition of a mixture of the two components of this invention at a lower dose (24% less) compared to the collector of one component of run 1, step I gave a slightly higher yield of Ag and Cu and a significantly higher yield of Pb.

Similarly, the collector mixtures of step 3 of this invention compared to either step 1 or step 4 of this invention gave a higher Ag yield, a slightly higher Cu yield, and a much higher Pb yield. Note that Ag, 15 Cu or Pb not recovered in step I is lost in the process.

The total Zn yields of steps I and II in all four yields of Table III on the run are so close to 1.0 (theoretical limit) that statistical comparisons are not valid.

Claims (17)

A collector reagent combination for flotation of metal-containing minerals, characterized in that it comprises, (a) a compound of formula RX-X- (R) nQ wherein Q is -N (R2) a (H) b, wherein a + b = 2, -N = Y, where Y is a sulfur or oxygen atom or a hydrocarbylene radical, which may be substituted, hN, or -N cyclic ring, wherein the cyclic ring is saturated or unsaturated and may contain additional heteroatoms, but must contain an N atom; R 1 and R 2 independently represent a C 18 hydrocarbyl radical, which may be substituted, or a saturated or unsaturated heterocyclic ring; O is R (-C-) y (-CH2-) p -frCHOH, where y + p + m = n, where n is an integer 1-6, 0 or an integer 1-6, and each proportion may occur in random sequence; X is -S -, - O-, -N-R 3, Wherein R3 is hydrogen, a C1.22 hydrocarbyl radical, which may be substituted; and 38 8 2 3 9 5 (b) hydrocarbons containing monosulfide units of formula 5 6 R -SR IX 5 wherein R 5 and R 6 independently represent a hydrocarbyl radical which may be substituted by one or more hydroxy, cyano, halogen, ether, hydrocarbyloxy or hydrocarbylthioether moieties; or R5 and R6 may together form a heterocyclic ring structure with S, provided that S is bonded to an aliphatic or cyclophatic carbon atom, and that the total carbon atom content of the hydrocarbon sulfide is such that the hydrocarbon sulfide is sufficiently hydrophobic for causing the metal-containing sulfide mineral or sulfided metal-containing oxide mineral particles to be driven to the air / bubble interface. Collector reagent combination according to claim 1, characterized in that R 1 and R 2 independently represent a C -, carbonyl, thiocarbonyl, cyano, carboxyl, hydrocarbylthio, hydrocarbylloxy, hydrocarbylamino or hydrocarbylimino groups. The collector reagent of claim 2, characterized in that (a) has the formula R1 ~ X "(CH- ·) - N-fR2) 2 n | and Ia <H> b D where R1 is a C2-14 hydrocarbyl radical which may be substituted by one or more hydroxy, amino, phosphonyl or alkoxy groups; R 2 is a C 1-6 alkyl, C 1-4 alkylcarbonyl group which may be substituted by an amino, hydroxy or phosphonyl group; a is 0 or 1 and b is 1 or 2 and a + b = 2. 39 82395 4. A combination according to claim 3, characterized in that n is 2 or 3. OH R1 is C2.14 hydrocarbyl; R 2 is C 1-4 alkyl or C 1-4 alkyl carbonyl; R3 is hydrogen or C1-14 hydrocarbyl; R5 and R6 independently represent an alkyl or an alkenyl group 10 and the sum of carbon atoms in (R5 + R6) is 6-16; a is the integer 0 or 1; b is the integer 1 or 2; and n is integers 1-4. 5. A combination according to claim 3, characterized in that the component (a) is omega- (hydrocarbylthio) alkylamine; S- (omega-aminoalkyl) -kolvätetioat; N- (hydrocarbyl) alpha, omega-alkanediamine; (Omega-aminoalkyl) -kolväteamid; omega- (hydrocarbyloxy) alkylamine; omega-amino noalkylhydrokarbonat; omega- (hydrocarbylthio) -alkylamid; or a mixture thereof. Combination according to claim 1, characterized in that R5 and R6 independently represent an aliphatic, cyclophatic or an aralkyl group which may be substituted by one or more hydroxy, cyano, halogen, OR7 or SR 7 radicals; R7 is a hydrocarbyl radical and R5 and R6 can together form a heterocyclic ring with S. 7. A combination according to claim 6, characterized in that the total carbon atom content of the sulphide compound is 4-20 carbon atoms. Combination according to claim 7, characterized in that R5 and R6 independently represent an alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl radical which may be substituted by one or more hydroxy, cyano, halogen -, OR7 or SR7-25 radicals; R 7 is an aliphatic or cycloaliphatic group; and R5 and R6 do not together form a heterocyclic ring structure. 9. A combination according to claim 5, characterized in that it comprises: (a) about 10 to 90% by weight of omega (hydrocarbylthio) alkylamine, S- (omega-aminoalkyl) hydrocarbon thioate, N- (hydrocarbyl) ) -alpha, omega-alkanediamine, (omega-aminoalkyl) hydrocarbon amide, omega- (hydrocarbyloxy) -alkylamine, omega-aminoalkyl-hydrocarbonate, omega- (hydrocarbylthio) alkylamide, or a mixture thereof; and (b) about 10 - 90% by weight of a sulfide compound of the formula H 5 (R 4) 3-nC (H) nSC (H) n (R 4> 3-n or 2 X Xa wherein the substituents R 4 independently represent a hydrocarbyl group, which may be substituted by a hydroxy, cyano, halogen, ether, hydrocarbyl oxy or hydrocarbyl toether group, or two R 4 substituents may together form a cyclic ring or a heterocyclic ring with the sulfur atom; and n is a hot 0, 1, 2 or 3; the substituents R8 independently represent a hydrogen, aryl, alkaryl, aralkyl, alkyl, , alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxy, cyano, halogen, OR7 or SR7 radical, wherein aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl or the cycloalkenyl group may be substituted by a hydroxy, cyano, halogen, OR7 or SR7 radical, wherein R7 is a hydrocarbyl group. The combination according to claim 9, characterized in that it comprises (a) about 20 to 80% by weight of omega (hydrocarbylthio) acylamine; S- (omega-aminoalkyl) kolvätetioat; N- (hydrocarbyl) alpha, omega-alkanediamine; (Omega-aminoalkyl) hydrocarbon amide; omega (hydrocarbylloxy) alkylamine; omega-aminoalkyl hydrocarbon; omega- (hydrokarbyItiö) alkylamido; or a mixture thereof and (b) about 20-80% by weight of the sulfide compound. 11. A combination according to claim 10, characterized in that R is -CH2 or 4 in 82395 H -O- Ι 12. A combination according to claim 9, characterized in that R 1 is C 4 -N-alkylcarbonyl; R2 is Combination according to claim 13, characterized in that X is -S-. Combination according to claim 5, characterized in that R5 and R6 are not the same hydrocarbon groups. 15. A combination according to claim 1, characterized in that the metal-containing sulfide mineral has a high natural hydrophobicity in the unoxidized state. C 1-4 alkyl or C 1-4 alkylcarbonyl; R 3 is hydrogen or hydrocarbyl; R 5 is C 1-2 alkyl; R6 is a C6-11 alkyl or alkenyl group; X is -S-, -N-R 3 or -O-; and n is the integer 2 or 3. Combination according to claim 1 or 5, characterized in that the component (a) is 2- (hexylthio) ethylamine or ethyl-2- (hexylthio) ethylamide. Combination according to claim 1 or 6, characterized in that the component (b) is ethylloctyl sulfide.