RU1839638C - Collector composition for ore flotation containing nonferrous metals - Google Patents

Abstract

The collector composition for flotation of ores containing non-ferrous metals contains a compound of the formula R-X- (R) -Q. where Q-rpynna —N (R2) a (H) b, where A + 1e 2; -And Y, where Y is S, O, optionally substituted hydrocarbylene; -N or -N cyclic ring, wherein the cyclic ring is saturated or unsaturated and may contain additional heteroatoms. however, it must contain a nitrogen atom, R and R — each independently possibly substituted C — C — hydroxyzril or saturated or unsaturated heterocyclic ring; R-rpynna; O (-C-) (-CH2-) - (- CHOH Y- where y + p + mn, where n is an integer from 1 to 6, y, p. And m are each independently 0 or an integer from 1 to 6 , and each part may occur in a random sequence; X-groups -S-, -0-, IM -R О О RО 3 II I) I3II -С- S-, -С -N- or-CQ-, where R is hydrogen, possibly substituted by C-C-hydrocarbyl, in an amount of 10 - 90% by weight of the composition. The composition also includes hydrocarbons containing monosulfide units of the formula R -SR, 56 where R and R are each independently hydrocarbyl radical optionally substituted with one or more cyano, halo, ether, hydrocarbyloxy or hydrocarbylthioether residues, R nR can be combined to form a heterocyclic a ring structure with S, provided that S is attached to a carbon atom of an aliphatic or cycloaliphatic series, with the further condition that the total carbon content of the hydrocarbon sulfide is C — C in an amount of 90 d about 10% by weight of the composition. 16 s.p. f-ly. Wh SL sz

Description

The invention relates to new reservoirs for recovering metal-containing sulfide minerals, sulfidated metal-containing oxide minerals, metal-containing oxide minerals and metals occurring in a metallic state (all four groups of minerals mentioned here relate to metal-containing minerals) from ore reserves using foam floatation Flotation is the process of treating a mixture of finely divided mineral solids, such as pulverized ores, suspended in a liquid, by whereby part of such solids is separated from other finely divided solids, for example clay and other similar materials present in the ore, by introducing gas (or creating In situ gas) into the liquid to obtain a foam containing a certain amount of solid particles on the surface of the liquid and leaving subsidized (non-foamed) other solid ore components. Flotation is based on the principle that the introduction of gas into a liquid containing solid particles of various materials suspended in it causes gas to adhere to certain suspended solid particles and does not adhere to others, and also causes particles to adhere to gas lighter than fluid. These particles rise to the surface of the liquid to form a foam.

To accelerate the foaming process, various flotation agents are mixed with the suspension. These agents are classified according to their function: collectors, such as xanthates, thionocarbamates, etc., foaming agents that promote the formation of stable foams, for example natural oils, such as pine oil and eucalyptus oil, modifiers such as activators , to create flotation in the presence of a collector, for example copper sulfate, depressants, for example sodium cyanide, which tend to prevent the collector from acting as tachyx with respect to the mineral that needs to be stored injuring - in a liquid, and thereby preventing the transfer of the substance and the formation of part of the foam, pH adjusters, for example lime and soda ash, to obtain optimal metallurgical results and the like. . Understanding the phenomena that contribute to making flotation an extremely valuable industrial process is not a -1 days long practice of the present invention. The phenomena that give flotation a particularly valuable industrial character are largely associated with

selective means of the surface of solid bodies of microscopic dimensions suspended in a liquid containing a gas inclusion, for a liquid on the one hand, for a gas on the other

Specific additives used in flotation are selected in accordance with the nature of the ore, mineral (s) to be recovered, as well as other additives that should be used in combination with these additives. Flotation is used in a whole series of mineral separation processes, including the selective separation of such metal-containing minerals that contain

0 copper, zinc, lead, nickel, molybdenum and other metals from iron-containing sulfide minerals, such as pyrite and pyrrhotite.

Among the collectors commonly used for the extraction of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals are xanthates, dithiophosphates and thionocarbamates. Other collectors

0 commonly recognized as useful in the recovery of metal-containing minerals or sulfidized metal-containing oxide minerals are mercaptans, disulfides (R-SS-R) and half-sulfides R-I S I h-R, where h is 3 or more.

Conversion of metal-containing sulfide minerals or sulfided metal-containing oxide minerals to

A more suitable state of pure metal is often achieved by smelting processes. Such smelting processes can lead to the formation of volatile sulfur compounds. These compounds are often released.

5 to the atmosphere through chimneys or are extracted from such chimneys using expensive and sophisticated equipment. Many sulfide minerals containing non-ferrous metals or metal-containing oxide minerals are naturally found in the presence of iron-containing minerals such as pyrite and pyrrhotite. When iron-containing sulfide minerals are recovered through flotation processes together with non-ferrous sulfide minerals and sulfated metal-containing oxide minerals, excess sulfur is present which is released during the smelting process. NeoG HPLM way

selectively recovering non-ferrous metal-containing sulfide minerals and sulfated metal-containing oxide minerals without recovering iron-sulfide minerals such as pyrite and pyrrhotite.

From among industrial collectors, xanthohecates, thionocarbamates and dithiophosphates cannot selectively extract non-ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals. On the contrary, such collectors collect and recover all metal-containing sulfide minerals. Mercaptan reservoirs have an environmentally undesirable order and are very kinetically slow during the flotation of metal-containing sulfide minerals. Disulfides and polysulfides when used as reservoirs provide low recovery rates with slow kinetics. Consequently, mercaptans, disulfides and polysulfides are generally not used commercially. In addition, mercaptans, disulfides, and polysulfides do not selectively extract non-ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals.

Thus, there is a need for a flotation collector that selectively extracts at a relatively good reduction rate a wide range of metal-containing minerals in the presence of iron-containing sulfide minerals such as pyrite and pyrrhotite.

Therefore, in one embodiment, the invention is a collector composition for flotation of metal-containing minerals, which includes

(B) a compound of the formula Ri-X- (R) n-Q. where Q-N (R2) a (H) b, where

-N-V, where V-S; 0, hydrocarbylene radical or substituted hydrocarbylene radical; -%

-N or -N, a cyclic ring, wherein the cyclic ring is saturated or unsaturated and may contain additional heteroatoms, but must contain an N atom;

RI and R2 are independently a Ci-C22 hydrocarbyl radical, a Ci-C22 radical of a substituted hydrocarbyl, or a saturated or unsaturated heterocyclic ring;

Q

R- ec-1UKn2- -snon-) t

where y + p + m n, where n is an integer from 1 to b;

y, p and m are independently 0 or an integer

 from 1 to 6, and each component can

meet in random order:, at

- $ -, - 0 -, - N- R

50О R3 О

 I L H

-C-S-, -C-N- OR -C-0- where P3 is hydrogen, a hydrocarbyl radical or a substituted hydrocarbyl radical;

(a) hydrocarbons; Containing monosulfide units of the formula

Rs-S-Re, where R3 and Re are independently

5 a hydrocarbyl radical, a hydrocarbyl radical substituted with one or more of the hydroxyl, cyano, gzlo, ether, hydrocarbyljms or hydroxybrbylthio ester moieties,

0 RS and Re can be combined to form a heterocyclic ring structure with 5 provided that S is attached to the carbon atom of an aliphatic or cyclo-zlathmic series, provided that the total carbon content of the hydrocarbon sulfide is such that it has sufficient hydrophobic character in order to bring the particles of the metal-free sulfide mineral or sulfidized metal-containing oxide mineral to the air-bubble interface.

The invention relates to a method for extracting metal-containing minerals

5 from an ore in which an aqueous pulp ore is subjected to a froth flotation process in the presence of a flotation amount of a flotation collector under such conditions that metal-containing minerals are recovered into the foam,

The collector compositions of this invention are capable of floating a wide range of metal-containing minerals. 5 Furthermore, such reservoir compositions provide good recovery rates and selectivities with respect to the desired letalliferous minerals.

0 The collector composition is used in a method for recovering metal-containing sulfide minerals or sulfidized metal-containing oxide minerals from an ore in which the ore is in the form of an aqueous

5 pulps are subjected to a foam flotation process in the presence of a flotation amount of the collector composition so as to cause particles of metal-containing sulfide minerals or sulfidized metal-containing oxide minerals to approach the air-bubble interface and be removed into the foam.

The inventive collector composition provides an extremely high percent recovery of non-ferrous metal-containing minerals and high selectivity for such non-ferrous metal-containing minerals when such metal-containing minerals are in the presence of iron-containing sulfide minerals.

Component (s) of the collector composition is a component of formula (1). Although not specifically indicated in formula (1), it should be understood that in an aqueous medium with a low pH, preferably acidic, component (a) may exist as a salt. In this formula, R preferably represents - (C2) -p or a mixture thereof, where p + m + y n, where n is an integer from 1 to 6, preferably 2 or 3; RI and each Ra is a radical C- | C22-hydrocarbyl or a C1-C22-hydrocarbyl radical substituted with one or more hydroxy, amino, phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, halo, ether, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino groups or hydrocarbimino. If substituted, RI and R2 are preferably substituted with one or more parts of hydroxy, halo, zmino, phosphonyl or alkoxy. Q is preferably N (R2) a (H) b, where.

More preferably, the carbon atoms in RI and R2 are a total of 6 or more, wherein RI is predominantly Ca Cm hydrocarbyl or C2 C14 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl groups or alkoxy, more preferably C4 Sc-hydrocarbyl. R2 is preferably Ci-Ce-alkyl, Ci-Ce-alkylcarbonyl, more preferably C1-C4-alkyl or C1-C4-alkylcarbonyl, or Ci-Ce-alkyl, or Ci-Ce-alkylcarbonyl substituted with amino, hydroxy or phosphinyl. and most preferably C1-Calkyl or C1-C2-alkylcarbonyl. In addition, R is preferably - (CH2) p- or

more preferably - {CH2) p-; h is preferably an integer from 1 to 4, most preferably 2 or 3; X is preferably —S—, —N — Rs or —0—,

5 more preferably —S— or —N — Ra, most preferably —S—; R3 is preferably hydrogen or C1-C14-hydrocarbyl, more preferably hydrogen or Cg-Cn-hydrocarbyl, most preferably hydrogen.

As described, component / a / includes compounds such as 5- {omega-aminoalkyl) hydrocarbonthioates

159

RrC-S4CH2- N4R2V t

(H) b (2.)

20 omega- (hydrocarbylthio) alkylamines and omega „- (hydrocarbylthio) alkylamides

RrS - ((R2V,

25№ 3)

- (hydrocarbyl) alpha, omega-alkanediamines. ) Q,

"S (n) b (h

- (omega-aminoalkyl) -hydrocarbons

RrO-N4CH2 N-fR2) b,}

. fi Mb

-omega- (hydrocarbyloxy) alkylamines

thirty

35

40

RrO - (- CH2-N-4R2) a,

CH) b

and omega-aminoalkylhydrocobono you

about

(L

4S Rrco4cH N4R, V M

{

where RI, R2, R3, a, b and n have the given meanings, In formulas 2-7, when X denotes -S- or

50o

II

p with D

RI is preferably 55 hydrocarbyl; when X is

About r

and I

-N-. -C-N.R

RrO - (- CH2-N-4R2) a,

CH) b

and omega-aminoalkylhydrocobono you

about

 Rrco4cH N4R, V

then the total carbon content of the RI and H3 groups is preferably about 1-23, more preferably 2-16. most preferably 4-15; when X is

ABOUT

II

—CORI is most preferably Ce-Ci i-hydrocarbyl.

It follows from the foregoing that, more preferably, the compound of component (a) includes omega- (hydrocarbylthio) alklamin, M- (hydrocarbyl) alpha, omega-alka go min, (omega-aminoalkyl), carbohydrodamides, omega (hydrocarbyl- si) alkylamine, omega- (hydrocarbylthio) alkylamides or them. mixtures. More preferred compounds of component (a) include omega- (hydrocarbylthio) alkylamines, omega- (hydrocarbylthio) alkylamides, - (hydrocarbyl) alpha, omega-alkanediamines, M- (omega-aminoalkyl) hydrocarbonamides, or mixtures thereof. Most preferred classes of compounds of component (a) include omega- (hydrocarbylthio) alkylamines, for example 2- (hexylthio) ethylamine, and omega- (hydrocarbylthio) alkylamides, for example ethyl 2- (hexylthio) ethylamide, "

Omega- (hydrocarbylthio} alkylamines of formula 3 can be prepared by methods disclosed by Berazosky et al., US Pat. No. 4,086,273. In French Patent No. 1,519,829 and in Bellstein 4.4th Edition, 4th Appendix, p.1755, 1979 .

M- (omega-aminoalkyl) hydrocarbonides of formula 5 can be prepared by methods described by Fazio, U.S. Patent No. 4,326,067 to Actapolon Phann, 19, 277 (1962), Bellstein 4, 4th Edition, 3rd Appendix, p. 587 , 1962.

Omega- (hydrocarbyloxy) alkylamines of formula 6 can be prepared by the methods described in UK Patent No. 869,409 and US Pat. No. 3,397,238.

5- {omega-aminoalkyl) hydrocarbonates of formula 2 can be prepared by methods described by Fayl et al. US Patent No. 3,328,442, and Bellstein, 4.4th Edition, 4th Appendix, p. 1785. 1979..

M- (hydrocarbyl) alpha, omega-alkanediamines of formula 4 can be prepared by methods well known in the art. One example is the method described in GDR N; 98510.

Component (a) of the collector composition is an organic compound that contains at least 4 carbon atoms and one or more monosulfide units, where the sulfur atoms of the sulfide units are bonded to aromatic carbon atoms, i.e. atoms of aliphatic or cycloaliphatic carbon. Monosulfide units here refer to units in which each sulfur atom is bonded to two carbon atoms of the non-aromatic part, for example, only two carbon atoms of the hydrocarbon part. Hydrocarbon

the compounds may contain one or more monosulfide units and include those substituted by hydroxy, cyano, halo, ether, hydrocarbylox and hydrocarbylthioether

parts of mi.

Preferred organic compounds containing monosulfide units include those of formula 8

RS - S - Re

(8)

compounds where Rs and Re are independently a hydrocarbyl radical or a hydrocarbyl radical substituted with one or more hydroxyl, cyano, halo, ether, hydroxybonyloxy or hydrocarbylthioether moieties, where Rs and Hb can be combined to form a heterocyclic

ring structure with S, provided that S is bonded to atoms of aliphatic or cycloaliphatic carbon, with the further condition that the total carbon content of the sulfide part is such that

the sulfide portion is sufficiently hydrophobic in order to bring the particles of the metal-containing sulfide mineral to the air-bubble interface.

The specific groups RS and Re, used here in the most advantageous way, depend on many

factors, including component (a) used, the particular ore to be processed, etc. To create the desired hydrophobic character, the monosulfide compound of formula 8 contains at least 4. more preferably 6, most preferably 8. carbon atoms. The maximum number of carbon atoms in a monosulfide compound is preferably 20, more preferably 16, most preferably 12.

Preferably, when Rg and Re independently represent an aliphatic, cycloaliphatic or aralkyl moiety unsubstituted or substituted by one or more hydroxy, cyano, halo, -OR or-SR moieties, where R is a hydrocarbyl radical, Rs and Re can be combined to form a heterocyclic ring with S. Rg and Re, more preferably represents an aliphatic or cycloaliphatic moiety unsubstituted or substituted by one or more cyano, halo, hydroxyl. OR or SR in portions where R is a hydrocarbyl radical. where RS and Re can combine to form a heterocyclic ring with S. In a more preferred embodiment of the present invention, RS and Re are not combined to form a heterocyclic ring with S, Rs and RG are independently alkyl, alkenyl , alkynyl, cycloalkyl or cycloalkenyl unsubstituted or substituted by one or more hydroxyl, halo, cyano, OR or SE moieties, where R is aliphatic or cycloaliphatic. In a most preferred embodiment, RS and Re are not the same hydrocarbon moiety, i.e. monosulfide is asymmetric. R is preferably aliphatic or cyclic aliphatic, more preferably R is alkyl, alkenyl, cycloalkyl or cycloalkenyl. In a most preferred embodiment, Rs and Re are independently alkyl or alkenyl, in particular RS is methyl or ethyl, and Re is Ce-Cs-alkyl or Ce-Cn-alkenyl, for example ethyl ethylsulfide ...;

Examples of cyclic compounds that can be used as a mono-ultphide compound of formula 8 include the following structures

toeVcx-xc- (a) 2 and fVs

where Re is hydrogen, aryl, alkaryl, aralkyl, alkyl. alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxy, cyano, halo, OR or SR group, where aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl. the cycloalkenyl group may optionally be substituted with Hydroxy, cyano. halo, OR or SR group, etc., where R is a hydrocarbyl group, preferably an aliphatic or cyclosliphatic, more preferably alkyl, alkenes, cycloalkyl or cycloalkenyl: Rg is normal or branched alkenyl, or alkenyl or alkynylene, unsubstituted or substituted hydroxyl. cyano, halo, OR or SR group.

A preferred compound suitable as component (a) of the present invention corresponds to the formula

(R4b-nC (H) n-S-t (H) n (R4) 3-n,

(9)

5 0 5 0 5 0 5

0

5

0 5

where 6c has the given meanings; R is independently hydrocarbyl or hydrocarbyl substituted with a hydroxyl, cyano, halo, ether, hydrocarbyloxy or hydrocarbylthioether moiety, where the two moieties of R4 may combine to form a cyclic ring or a heterocyclic ring with a sulfur atom;

n is an integer of 0, 1.2, or 3, provided that the total content of the hydrocarbon part of the collector is such that the collector is sufficiently hydrophobic to bring particles of a sulfated metal-containing oxide mineral to the air-bubble interface;

The FU in the above formula preferably denotes an aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl group unsubstituted or substituted by a cyano, halo, hydroxyl, OR or SR group, where R is as defined herein. More preferably, when R4 is an aliphatic or cycloaliphatic group unsubstituted or substituted by a hydroxyl, cyano, halo, aliphatic ester, cycloaliphatic ester, aliphatic thioether, preferably when R4 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl moiety. Most preferably, one —C (H) p (P4) zp represents a methyl or ethyl group, and the other represents a Ce-Cn-alkyl or Cb-Cc-alkenyl group, Preferably, if n is 1, 2 or 3 and more preferably 2 or 3.

Preferred hydrocarbon-containing monosulfide units of the formula Rs-S-Re, wherein RS and Re are given values, are prepared by standard methods, for example, by reacting Re-H with Rs-SH, where RS and Re are given values.

Examples of compounds within the scope of the present invention include methyl butyl sulfide, methyl pentyl sulfide, methyl hexyl sulfide, methyl heptyl sulfide, methyl oxyl sulfide. methyl noni l sulfide,

methyldecyl sulfide, methylundecylsulfonyl sulfide, decycloheptyl sulfide, decycfide, methyldodecyl sulfide, methylcyclo-looctyl sulfide. More preferred

pentyl sulfide, methylcyclohexyl sulfide, sulfides include methylhexyl sulfide,

methylcycloheptyl sulfide, methylcyclic methylheptyl sulfide, methyloctyl sulfide,

loctyl sulfide, ethyl butyl sulfide, 5 methylnonyl sulfide, methyldecyl sulfide,

ethyl pentyl sulfide. ethyl hexyl sulfide, ethyl hexyl sulfide, ethyl heptyl sulfide,

ethylheptyl sulphide, ethyl styl sulphide, ethyl styl sulphide. etmlnonyl sulfide,

ethylnonyl sulfide, ethyldecyl sulfide, ethyl ethyldecyl sulfide, disutyl sulfide, dipenlundecyl sulfide, ethyl dodecyl sulfide, thyl sulfide, dihexyl sulfide, diheptylethylcyclopentyl sulfide and ethylcyclohexyl sulfide and di-sulfide.

silsulphide, ethylcycloheptylsulphide, ethyl-Hydrocarbon means here organiccyclooctylsulphide. propylbutyl sulfide, cce a compound containing carbonylpropylpentyl sulfide atoms. propylhexyl genus and hydrogen, the term hydrocarbon

sulfide, propylheptyl sulfide, propi-includes the following organic soedyloxyl sulfide, propylnonyl sulfide, 15 non-alkanes, and kenes, alkynes, cycloalkapropyldecyl sulfide, pro:, ilundecyl, cycloalkenes, cycloalkenes, aromatics,

sulphide, n according to pildodecyl sulphide, aliphatic, and cyclo osliphatic aralpropyl cyclopentyl sulphide, propyl cans and alkyl-substituted aromatic

Cyclohexyl sulfide, propylcyclohep compounds.

thyl sulfide, propylcyclooctyl sulfide, 20 The term aliphatic refers to

dibutyl sulfide, butyl pentamyl sulfide, used here to saturated unsaturated carbonyl hexyl sulfide, butyl hexyl sulfide, hydrogen compounds with normal and

branched chain tylheptyl sulfide, butyloxy sulfide, i.e. alkanes, alkbutylnonyl sulfide, butyldecyl sulfide, us or alkynam.

butyl dodecyl sulfide, butyl undecylsulf-25 The term cycloaliphatic osmphide, butyl cyclopentyl sulfide, butyl cyclo-s, "here there are saturated and unsaturated hexyl sulfide, butyl cycloheptyl sulfide, cyclic hydrocarbons, i.e. cycloalbum / ylcyclooctyl sulfide, dipentyl sulfide, kanem and cycloalkenes, pentylhexyl sulfide, pentylheptyl sulfide, cycloalkane refers to alkane, contains pentyloctyl sulfide, pentylnonyl sulfide, one or two cyclodecyldecide. Cycloken refers to monodiphide, pentyldodecyl sulfide, pentylcyclo and polycyclic groups containing pentyl sulfide, pentylcyclohexyl sulfide, one or more double bonds, pentylcycloheptyl sulfide, pentylcyclohex, hydroxy cyclohexyl, sulfide, t-hexyloxyl sulfide, and hydrogen. The term Hmdrocarbyl including hexylnonyl sulfide, hexyl decyl sulfide, the following organic radicals: alfide, hexylundecyl sulfide, hexyl dodecyl, alkenyl, alkynyl, cycloalkyl, cyl sulfide, cycloalkyl-cycloalkyl-cycloalkyl-cyclohexylalkyl-cyclohexylalkyl-cyclohexylalkyl-cyclohexylalkyl , gentyl sulfide, hexyl cycle, octyl sulfide, dihegetl sulfide, The term ari refers here to bio-heptyloctyl sulfide, heptylnonyl sulfide, aryl, bifvnilyl, phenyl, naphtha-heptyldecyl sulfide, heptylundecium lsultyl, phenanthrenyl, anthracenyl feed, heptyldodecyl sulfide, heptylcyclo-45 and two aryl groups connected by mopentyl sulfide, heptylcyclohexyl sulfide, by sticky bonding via alkylene heptylcycloheptyl sulfide, heptylcyclic group.

loctyl sulfide, dioctyl sulfide, octyl-alkaryl refers here to alkyl -, - alkenonyl sulfide, octyldecyl sulfide, nyl or alkynyl substituted aryl

octylundecyl sulfide, octyldodecyl sulf-50 substituent, where aryl has the following

feed, octyl cyclopentyl sulfide, octyl cyclo values. Aralkyl here means alkylhexyl sulfide, octylcycloheptyl sulfide, a new group in which aryl has reduced ethylcyclooctyl sulfide, dinonyl sulfide, and other meanings.

nonyldecyl sulfide, nonylundecylsul-Cr-C20-alkyl includes methyl, ethyphide, nonyldodecyl sulfide, nonylcyclo-55 left, propyl, butyl, pentylopentyl sulfide, nonylcyclohexyl sulfide, zyu, hexyl, heptyl

nonylcycloheptyl sulfide, nonylcycloocononyl, decyl, undecyl, dodethyl sulfide, didecyl sulfide, decylundecyl, tridecyl, tetradecyl,

cylsulfide, decyldodecyl sulfoxide, pentadecyl, hexadecyl, heptadecylcyclopentyl sulfide, decylcyclohecyl, octadecyl, nonadecyl and

ykosilovy groups with a normal and branched chain.

Halo here means a chloro, bromo or mono group.

Hydrocarbylene here means organic radical carbon atoms of hydrogen, which must be attached to the nitrogen atom by a double bond. The term hydrocarbylene includes the following organic radicals: alkenide, cycloalkenyl aralkylene, where aryl has the indicated meanings.

A heterocyclic ring here means both saturated and unsaturated heterocyclic rings including an —N— cyclic ring. A heterocyclic ring may include 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, pyrazine, purine, ethyleneimine, oxiran, azetidine, oxetane, thietane, pyrrole, pyrrolidine, tetrahydrofuran, isoxaeol, piperidine, azepine and others.

The composition of the present invention is prepared using sufficient amounts of components (a) and components (b) to produce an effective collector for metal-containing minerals from ores in a foam flotation process. The amount of each component most advantageously used in the preparation of the composition varies depending on the specific components (a) and (b) used, the particular ore being processed, as well as the required extraction rates and selectivities. The composition preferably contains from about 10 to 90, more preferably from 20 to 80, wt.% Of component (a) and from about 10 to 90, more preferably from 20 to 80, wt.% Of component (b). The composition of the present invention even more preferably contains from about 30 to 70% by weight of component (a) and from about 30 to 70% by weight of component (b).

The method of the present invention is suitable for recovering metal-containing minerals from ore through foam flotation.

The term ore refers here to material extracted from the soil and includes the desired metal-containing minerals mixed with gangue.

The term waste rock means that part of the material that has little value or has no

values and requires separation from the desired metal-containing minerals.

The collector composition of the present invention is preferably used in the recovery of metal-containing minerals during foam flotation. In a more preferred embodiment of the present invention, minerals containing copper, nickel, zinc or molybdenum are recovered. In an even more preferred embodiment, minerals containing copper are recovered. Also preferred metal-containing sulfide minerals are 5 s. which have a high natural hydrophobicity in an unoxidized state. The term hydrophobicity in an unoxidized state applies to a freshly ground mineral or mineral

0 having a fresh surface that exhibits a tendency to flotation without the addition of a reservoir.

The ore for which these compounds are suitable includes sulfide ore minerals containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, plate, uranium, and mixtures thereof.

Examples of metal-containing sulfide minerals that can be enriched

Foam flotation using the present invention include copper-bearing minerals such as, for example, covellite (CuS), chalcosine (CuaS), chalcopyrite (CuFeSa), valerite (CuaFe S or CuaFesS), bornite

5 (CusFeS), cubanite (Cu2SFe4Ss), enargite Cu3 (AsiSb) S4, tetraerite (CuaSbib). tennantite (Cu2As4Si3), brocantite (Cu4 (OH) b504), antlerite Cis804 (OH) 4, famatinite Cu (SbAs) S4 and burnonite (PbCuSbSa); non-porous minerals such as, for example, galena (PbS); antimony-bearing minerals, such as, for example, stibnite (Zb3z3); zinc bearing minerals such as, for example, sphalerite (ZnS); silver bearing

5 minerals, such as, for example, stefanite (AgsSbS) and adhesivestone (Ag2S); chromium-bearing minerals, such as, for example, bonnet (FeSCrSa); nickel-bearing minerals, such as, for example, pentlandite (FeNiJgSe: molybdenum-bearing minerals, such as, for example, molybdenite (Mo $ 2); and platinum and palladium-bearing minerals, such as, for example, cuperite Pt (AsS) 2. Preferred metal-containing

5 sulfide minerals include molybdenite (Mo $ 2), chalcopyrite (CuFeS2), galena (PbS), sphalerite (ZnS), bornite (CusFeSn) and pentlandite (FeNiJgSsj.

Sulphided metal-containing oxide minerals are minerals that are treated with a sulphidating chemical in order to impart a sulphide mineral to such minerals so that the minerals can be recovered in the foam flotation process using collectors that recover sulphide minerals. Sulfidation results in oxide minerals having the characteristics of sulfide minerals. Oxide minerals sulfide by reaction with a compound that reacts with the minerals to form a sulfur bond or agent. Such methods are well known. These compounds include sodium hydrosulfide, sulfuric acid and related sulfide salts, such as sodium sulfide,

Sulfidated metal-containing oxide minerals and oxide minerals for which the present process is suitable 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 enriched with foam flotation using the present invention include copper-bearing minerals such as cuprite (CuAO), tenorite (CuO), malachite Cu2 (OH) aCO3, azurite Cis (OH) 2 (CO3) 2. atacamite Cu2C (OH} s, chrysocolla (CuSiOs); aluminum-bearing minerals such as cornwood; zinc-bearing minerals such as zincite (ZnO) and smitsonite (ZnCO); tungsten-bearing minerals such as tungsten (FeMn) WO-i nickel-bearing minerals such as bunsenite (MU); molybdenum-bearing minerals such as wulfenite (PbMoOz) and sedilite (CaMeO / i); iron-bearing minerals, such as hematite and magnetite; chromium-bearing minerals, such as chromite (ReОСг20э), iron and titanium-containing minerals. such as hard metal; magnesium and aluminum-containing minerals. such as spinel; iron and chromium-containing minerals such as chromite; titanium-containing minerals such as rutile; manganese-containing minerals such as pyrolusite; tin-containing minerals such as cassiterite; uranium-containing minerals such as uranite; as well as uranium-bearing minerals, such as, for example, the uranium resin UaOsfUaOs) and gummite (1U3 and Н20).

Other metal-containing minerals for which this method is suitable include gold-bearing minerals such as sylvane (AuAgTe2) and calaverite (AuTe); platinum and palladium-bearing minerals such as sperrylite (PtAsa); silver-bearing minerals such

like hessite (AgTeJ. Metals are also included. which are found in the metallic state, e.g. gold, silver and copper.

The collector composition of the present invention can be used at any concentration that provides the desired recovery of the necessary minerals. The concentration used depends on the particular recoverable mineral, the grade of ore subjected to the foam flotation process, the desired quality of the recoverable mineral, and the particular mineral to be recovered. It is preferable to use a collector composition in accordance with the present invention at a concentration of 5 g to 1000 g per metric ton of ore, more preferably in the range of about 10 to 200 g of collector per metric ton of ore subjected to a foam flotation process. In order to achieve an optimal synergistic effect, it is most preferable to start from low dosage levels and increase levels until the desired effect is achieved. Synergy is defined here as the concept that the measured result of a mixture of two or more components exceeds the weighted average results of each component when they are used separately: This term also implies that the results are compared under the condition that the total weight of the collector used is the same for each experiment.

While continuing the foam flotation process of the present invention, the use of foaming agents is preferred. Foaming agents are well known in the art. Any blowing agent that results in the recovery of the desired metal-containing mineral is suitable. The blowing agents useful in the present invention include any blowing agents known in the art that result in the recovery of the desired mineral. Examples of such blowing agents include Cs-Ce alcohols, pine oils, cresols, C1 to C4 alkyl ethers of polypropylene glycols. polypropylene glycol dihydroxylates, glycols, fatty acids, soaps, alkylaryl sulfonates, etc. In addition, mixtures of such blowing agents can be used. All blowing agents suitable for beneficiating ores through froth flotation may be used in the present invention. In addition, it is contemplated that the reservoir combination that constitutes the composition of the present invention may be used in mixtures with other reservoirs well known in the art. The inventive collector composition may also be used with an amount of other collectors known in the art sufficient to obtain the desired recovery of the desired mineral. Examples of such other collectors are dialkyl tiomo- Chevin, alkyl, dialkyl and trialki- lovye thiocarbonates, alkyl and dialkyl tmonokarbamaty, monoal kilo- stems dithiophosphates, dialkyl and diaryl dithiophosphates, dialkyl and diaryl tiofosfonilhloridy, dialkyl and diaryl dithiophosphonates, alkyl markaptany , xanthogen formates, mercaptobenzothiazoles, fatty acids and salts of fatty acids, alkyl sulfuric acids and their salts, alkyl and alkaryl sulfonic acids and their salts, alkyl phosphoric acids and their salts, alk l and ari phosphoric acids and their salts, sulfosuccinates, sulfosuccinamates, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkyl pyridinium salts, guanidine and alkyl propylene di-amines.

The following examples are included to illustrate and should not be construed as limiting the scope of the present invention. Unless otherwise indicated, all parts are weighted.

In the examples, the performance characteristics of the described foaming processes are shown in terms of the relative amount of extraction at the set time.

PRI me R 1. Penna flotation of copper / molybdenum ore,

A series of pockets (samples 1-8) are obtained containing 1200 g of homogeneous copper / molybdenum ore containing chalcopyrite and molybdenum, minerals obtained from western Canada. The ore in each pocket is crushed using 800 ml tap water for 14 minutes in a ball mill having a mixed ball feed to give approximately 13% plus 100 mesh. fineness of grinding. The resulting slurry was transferred to an 1500 ml Agltair flotation chamber equipped with an automatic foaming paddle, the pH of each pulp was adjusted to 10.2 using lime. No additional pH adjustments were made during the test. The standard methylmzobutylcarbonyl foaming agent (MIBK) and the collectors or collector combinations shown in Table 1 are used for the molybdenum copper floater using the four-stage coarse flotation scheme described below.

Stage: Collector 0.0042 kg / t MIBK 0.015 kg / t ™ 1 min regime Floats Collected concentrate for 1 min

Stage 2: Collector 0.0021 kg / tx MIBK 0.005 kg / tx

 0.5 min regimen Collected concentrate is floated for 1.5 mi

Stage 3: Collector 0.0016 kg / tx MIBK 0.005 kg / tx

0.5 min regimen Collected concentrate is floated for 2 min.

Stage 4: Collector 0.0033 kg / tx MIBK 0.005 kg / tx

 0.5 min. Flotate collected concentrate for 2.5 mi

x Use 1 kg of collector or collector composition per metric ton of ore processed

xx Use 1 kg of blowing agent per metric ton of ore processed. The results of the tests for foam flotation are summarized in table 1

In the foam flotation tests of samples 1-8, the collector composition contains 50% by weight of each collector.

The 95% confidence level of static error associated with the R-7 value for copper in Table 1 is 0.010. Thus, the static difference between the largest and smallest R-7 values for copper B, associated, for example, with collector A, is 0, 010, or 0.678-0.698.

The statistical error associated with the R-7 molybdenum values in Table 1 is +0.015,

It is clear that the extracts of copper and molybdenum in 7 minutes when using the collector mixtures of the present invention are equivalent or superior to the 7-minute extracts that would be expected from the weighted average effect of the components used separately. Thus, synergy occurs.

PRI me R 2. Penna flotation CuNi ORE.

A row of pockets with samples - 10 mesh. ores from Western Canada are separated into 900 g samples. The ore contains the minerals chalcopyrite, pentlandite and pyrrhotite. All tests were carried out using 1500 ml of an Agltalr flotation machine operating at 900 rpm with an air flow rate of 9 l / min. Before flotation, each sample was ground in a rod mill for 1080 rpm. Before grinding, 600 ml of water was added together with a sufficient amount of gravel to bring the pulp pH to 9.2. After grinding, the ore has a particle size of less than 200 mesh. (75 μm). The contents of the mill rods are poured into a flotation machine and the pH is adjusted to 9.2 using either lime or sulfuric acid. .

A nine-stage flotation sequence was carried out. The first four stages relate to coarse flotation, and stages 5-9 relate to rough flotation. After step 4, sulfuric acid was added in order to bring the pH to 9.2, and were added in step 5 and step 7 (0.016 kg / metric ton). Use a DOWFROTH 250 blowing agent.

Additional norms of the foaming agent and collector are given in table 2.

Samples are dried, weighed, and the metal is analyzed in the ore. Standard material balance formulas are used to calculate percent recovery and metal content in the total mass. The results are summarized in table.Z.

In this example, the lowest possible percent recovery of pyrrhotite and the highest possible percent recovery of copper and nickel after 7 minutes are important, since it is at this time that the main sorting of the high sulfur mineral occurs. After 17 minutes, the percent recovery of copper and nickel should be most possible using normal flotation logic. However, the percent recovery of copper is approximately the theoretical limit of 1.0 for both 7 and 17 minutes, so statistically important comparisons are not possible.

It is clear that nickel recovery after 7 minutes using the collector mixture of the present invention gives a high value with a low recovery percentage of pyrrhotite. In addition, the percentage of & treat

nickel after 17 minutes using the mixture of the present invention is high. The 95% confidence level of the statistical error associated with R-7 nickel is ± 0.015 and for R-17 it is 40.006, for pyrrhotite at R-7 it is +0.012. Nickel recovery indicates that synergism occurs at a desirable low percent recovery of pyrrhotite.

PRI me R 3. Penna flotation complex Pb Zn I Cu Au ore.

A series of uniform samples are obtained, weighing 1000 g of complex Pb I Zn ICu IAg ore, obtained from Central Canada. The ore contains galena, sphalerite, chalcopyrite and argentite. For each flotation run, a sample was added to a core mill along with 500 ml of tap water and 7.5 ml of SOa solution. A grinding time of 6.5 minutes is used to obtain the feed; 90% of the ore has a particle size of less than 200 mesh. (75 μm). After grinding, the contents are transferred to a flotation machine equipped with an automatic foam scavenger, and the machine is connected to a standard Denver flotation mechanism.

Then, two-stage flotation is carried out: stage I represents the crude coarse flotation of zinc. In order to prevent flotation of stage 1, 1.5 g / kg K a2CO3 (pH 9-9.5) was added, followed by collector (s). The pulp is then conditioned for 5 minutes with air and stirring. A 2-minute conditioning period followed by stirring only. Methylisobutylcarbonyl foaming agent (MNBF), a standard dose of 0.015 ml / kg, is then added. The concentrate is collected over a 5 minute flotation period and is labeled as coarse copper / lead concentrate.

Stage II flotation is the addition of 0.5 kg / metric ton of CuSO to the machine remaining from stage I, the pH is adjusted to 10.5 by the addition of isestocks. This is followed by a period of only mixing of 5 minutes. The pH is then re-checked and adjusted to 10.5 by the addition of lime. At this point, the collector (s) are added, followed by a five minute period of only mixing. Methylisobutylcarbinol (MIBK) blowing agent (standard dose 0.020 ml / kg) is then added. The concentrate is collected over a 5 minute flotation period and is labeled as zinc coarse concentrate.

Samples of the concentrate are dried, weighed and suitable samples are prepared lyre,

for analysis using an X-ray flaw detection method. Using analysis data, the relative percentages of recovery and grade are calculated using standard material balance formulas.

The results are summarized in table 4.

The 95% confidence levels of statistical error in these extracts after 5 minutes of Cu / Pb flotation (step 1) were for Ad ± 0.01: Cu ± 0.01 and P ± 0.02. Series 1 and 4 are tests in which single components are used in each step.

In stage 1 of series 2, the addition of the two-component mixture of the present invention at a low dosage (24% less) compared to the one-component collector of stage 1 of series 1 leads to the recovery of a slightly larger amount of Ad and Cu and a significantly larger quantity of Pb.

Similarly, the collector mixtures of the present invention in the series 3 stage as compared to stage 1 of either of the two series 1 or 4 result in a slightly higher percentage of C extracts, a higher percentage of Hd extraction, and a much higher percentage of Pb extraction. It should be noted that Hell, Cu or Pb not brought on in step 1 are lost to the process.

The total zinc recovery of stages I and II in all four test series of Table 4 is so close to 1 (theoretical limit) that statistical comparisons are not valid).

(56) USSR patent No. 1831373. cl. B 03 D 1/02. 1990.

About II

ss2n.6

x is not an example of the present invention.

lA C6Hl3S (CH2) 2NH2

U HttSfcHj)

V - indicates the experimental fractional extraction after 7 minutes

n 1s sbn1Gs-h: ng

Grade 3 - is the relative content of a particular metal in the total mass collected in the foam

Table 1

About II

ss2n.6

VT

A- CeHtfS / CH-J VWC B-GjHgSC Hg

1He is an example of the present invention,

2R-7 refers to relative recovery after 7 minutes (coarse flotation), 3R-17 refers to relative recovery of 17 milliliters ("flotation flotation"). 4B is test series 3, collector A and B are a mixture of 50-50 weight. % of each collector.

: Table 4

- Not an example of the present invention. A is dig-voxyl sulfide. B - 2- (hexylthio) ethylamine. C is ethyl 2- (hexylthio) ztilamide. R-5 indicates the actual fractional recovery after 5 minutes.

Table 2

Table 3

Claims (8)

The claims 1. COLLECTOR composition FOR FLOTATION OF NORES CONTAINING NON-FERROUS METALS, including component A - hydrocarbon sulfide of the formula Rs-s-re, where RS and Re are each independently a hydrocarbyl radical or a hydrocarbyl radical substituted with one or more hydroxyl, cyano, halo, ether, hydrocarbyloxy or hydrocarbyl thioether moieties, RS and Re can be combined with the formation of a heterocyclic ring with S, provided that the S atom is bonded to an aliphatic or cycloaliphatic carbon atom, characterized in that Chona additionally contains a component Ri-X- (R) n-Q, where Q is the group-N (R2) a (H) b; a + b 2; —N Y, where Y is S, O, a hydrocarbylene radical or a substituted hydrocarbylene radical; -N or -N cyclic ring, where the CEC-, ring is saturated or unsaturated and may contain additional heteroatoms, but must contain a nitrogen atom; RI and R2 are each independently Ci — Ca2 hydrocarbyl, Ci — C22 substituted hydrocarbyl, or a saturated or unsaturated heterocyclic ring; R-rpynna (-C-) y (-CH2-) p fCHpH m, where y + p + m n, where n denotes an integer from 1 to 6, and y, p and m independently mean 0 or an integer from 1 to b, and each part can occur in a random sequence, X-rpynna-S -, - 0, -N-R3 .9 9 9 -C-5, -C-N-, or -C-0-, where R3 is hydrogen, the radical Ci is Ј22 hydrocarbyl or the radical Ci is Ca2 of a substituted hydrocarbyl, in an amount of 10 - 90% by weight of the composition with a total carbon content of carbon sulfide C2 - Ci2 90 - 10% by weight of the composition. 2. The composition according to claim 1, wherein (Ri and RS are each independently Radical Ci-C22 hydrocarbyl or Ci - radical; Ј22 hydrocarbyl substituted with one or more hydroxyl, amino phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl. cyano, carboxyl, hydrocarbylthio. hydrocarbonyloxy, hydrocarbylamino or hydrocarbylimino groups. 3. The composition according to claim 2, characterized in that component B corresponds to the formula Ri-X (CH2) -n .Nf "2) e, (H) b 15 where Ri is a C2-Ci4 hydrocarbyl radical or a C2-Ci4 hydrocarbyl radical / substituted with one or more hydroxyl, amino, phosphonyl or alkoxy groups; 20 R2 Ci is Cb-alkyl, Ci is Ce-alkylcarbonyl, or Ci is Cb-alkyl, or Ci is Ce-alkylcarbonyl substituted with an amino, hydroxyl or phosphonyl group; 5 a 0 or 1; b 1 or 2; a + b 2, 4. The composition according to claim 3, wherein so that n 2 or 3. 0 5. The composition according to claim 3, wherein in that component B is omega-Hydrocarbyl thioalkylamine, 5- {omega-aminoalkyl) hydrocarbonothio, Hydrocarbyl) alpha, omega-alkanediamic, M- (6mega-aminoalkyl) hydrocarbonamide, omega-{hydrocarbyloxy) alkylamine , omega-aminoalkylhydrocarbonate, omega- (hydrocarbylthio) alkylamide, or a mixture thereof. 0 6. The composition according to claim 1, wherein R & and Re each independently means an aliphatic, cycloaliphatic or aralkyl moiety unsubstituted or substituted by one or more hydroxyl, cyano, halo, OR or SR moieties, R is a hydrocarbyl radical, and Rs and Re can be combined to form a heterocyclic ring with S. 7. The composition of claim 6, wherein the total carbon content of the sulfide compound is 4-20 carbon atoms. 8. The composition according to claim 7, characterized in that RS and Re each independently mean alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, unsubstituted or substituted by one or more hydroxyl, cyano, halo, OR or SR moieties, R o aliphatic or cycloaliph ttic. Rs and Re are not combined with ob-M- (hydrocarbyl) alpha, omega-alkanediamation of the heterocyclic ring, omega-aminoalkylhydrohydroamides 8, structures. omega- (hydroxybonyloxy) alkylamine. ome 9. The composition according to claim 5, wherein the composition is gammaalkylhydrocarbonate. omega- {hydtem that contains component B from 10 to 905 rockarbylthio) alkylamide or mixtures thereof and A wt.% omega- (hydrocarbylthio) alkylamine, from 20 to 80 wt.% sulfide compound 5- (omega-aminoalkyl) hydrocarbonthioate, nor M- {hydrocarbyl) -alpha, omega-alkanediam-11. The composition of claim 10, wherein on the. (omega-aminoalkyl) hydrocarbon, omea-JQ in that R is CH2 or ga- {hydrocarbyloxy) alylamine, Y omega-aminoalkylhydrocarbonate, omega-g (hydrocarbylthio) alkylamide or mixtures thereof and component A from 10 to 90 wt.% sulfide-f C14 g HydrocarbylL R2. Ct - C6-alkyl compound and sulfide compound 15 C1. c5-alkylcar6onyl, R3 is hydrogen corresponds to the formula C14. hydrocarbyl, Rs and Re - each (R4) 3-nC (H) nS is independently either alkyl or alkenyl and the sum of 1X1m of carbon atoms in Rs and Re is SC (H) n (R) 3-n „n 16, and 0 or 1, b - 1 or 2, n 1 - 4. MH (R8) 2-C.-C (R8) 212 - The composition of claim 9, wherein | Xal S in that Ri - Cd - Cn-hydrocarbyl: R2 - Cig where R4 is each independently hydrocarbyl, C4-alkyl or Ci - C4-alkylcarbonyl; P3 or hydrocarbyl, substituted hydroxyhydrogen or Ci-Cn-hydrocarbyl; Rs is Cinoy, cyano, halo, ether, hydrocarbyl-25-C2-alkyl; Re-Ce-Cn-aflKMn or alkenyl X si or hydrocarbylthioether parts, denotes S -, - N-R3 or-0 - p 2 or T where the two parts of R4 can be combined, - about Vnt tn a cyclic ring or a heterocycle wo X about V differs ring with a sulfur atom, v means 5-, p-integer 0, 1.2 or 3.30. The composition of claim 5, wherein Re is each independently hydrogen, aryl, so that Rs and Pb are not the same alkaryl, aralkyl, alkyl, alkenyl, the same Uglev ° The native part. vinyl, cycloalkyl, cycloalkenyl, hydro- - The composition according to claim 1, characterized in roxyl, cyano, halo, OR, or metal-containing sulfide groups, where aryl, alkaryl, 35 minerals are those which aralkyl, alkyl, alkenyl, have a high natural hydrophobalkynyl, cycloalkyl, cyclo-ness in an unoxidized state, the alkenyl group may be 16. The composition according to claim 1 or 5, wherein the composition is substituted by hydroxyl, cyano, wherein component B is halo, OR or SR group, where R is hydro-40 is 2-hexylthio) ethylamine or ethyl-2rocarbyl group. (hexylthio) ethylamide. 10. The composition according to claim 9, wherein | 17. The composition according to claim 1 or B is characterized in that it contains B from 20 to 80% by weight of omega so that component A is ga- (hydrocarbylthio) alkylamine, 5- (omega-a-ethylstylesulfide. aminoalkyl) hydrocarbonthioate .4b