PL148165B1 - Novel collector for recovering from ores sulfide minerals containing non-ferrous metals or sulfidized oxide minerals containing metals by froth flotation - Google Patents

Description

The invention relates to a new collector for the recovery of non-ferrous metal-bearing sulphide minerals and metal-bearing sulphide oxide minerals from ores by froth flotation.* Flotation is a process of treating a mixture of finely divided solid minerals, e.g., powdered ore suspended in a liquid, in which a portion of such materials is separated from other finely divided solid particles, e.g., clays and other similar materials present in the ore, by introducing a gas (or generating a gas in situ) into the liquid so as to produce a frothed mass in which some of the solids are on top of the liquid and other solid ore components remain suspended (unfoamed). Some of the gas adheres to the suspended solids, causing the particles with the adhered gas to become lighter than the liquid and rise to the top of the liquid, creating foam. To improve the foaming process, various flotation additives are added to the suspension. These additives are classified according to their function, as follows: collectors, which for sulfide-containing minerals include xanthates, thionocarbamates, etc.; frothers, which impart the property of creating stable foam, e.g., natural oils such as pine oil and eucalyptus oil, etc.; modifiers, such as activators for inducing flotation in the presence of the collector, e.g., copper sulfate; depressants, e.g., sodium cyanide, which prevent the collector from acting on the mineral intended to remain in the liquid, thus preventing the substance from rising and forming part of the foam; pH regulators used to obtain optimal metallurgical results, e.g., lime, soda ash, etc. Additives of the types described above are selected for use depending on the nature of the ore and other additives to be used in combination with them, as well as the minerals to be recovered. The flotation principle is used in many mineral separation processes, including: The purpose of this process is to selectively separate such metal-bearing sulfide minerals as those containing copper, zinc, lead, nickel, molybdenum, and other metals from iron-bearing sulfide minerals such as pyrite and pyrrhotite.* Collectors commonly used to recover metal-bearing sulfide minerals or metal-bearing sulfided oxide minerals include xanthates, dithiophosphates, and thionokerbates.* Volatile sulfur compounds often pass into the atmosphere through factory stacks or are removed from stacks by expensive and complex scrubbing equipment. Many nonferrous metal-bearing sulfide minerals or metal-bearing oxide minerals occur in ores that also contain iron-bearing sulfide minerals. When iron-bearing sulfide minerals are recovered in flotation along with nonferrous metal-bearing sulfide minerals and metal-bearing sulfided oxide minerals, excess sulfur is present, which is released during the smelting process. Therefore, collectors are needed that can selectively recover nonferrous metal-bearing sulfide minerals and metal-bearing sulfided oxide minerals without recovering iron-bearing sulfide minerals. Known collectors! xanthates, thionocarbamates and dithiophosphates do not selectively act in the recovery of non-ferrous metal-bearing sulfide minerals in the presence of iron-bearing sulfide minerals, but will collect and recover all metal-bearing sulfide minerals. The collector of the invention comprises (a) a hydrophobic hydrocarbon monosulfide having 4-20 carbon atoms of the formula R-S-R, wherein R is an aliphatic, cycloaliphatic or aralkyl group, optionally substituted with one or more hydroxyl, cyano, halogen, ether, hydrocarbonoxy or hydrocarbonthioether groups, R is an aliphatic, cycloaliphatic, aromatic group or combinations thereof, containing 5-11 carbon atoms, further R and R may react to form a heterocyclic ring with sulfur, and the sulfur is bonded to an aliphatic or cycloaliphatic carbon atom, and /b/ a thiocarbonate, thionocarbamate, alkyl thiophosphate, or mixtures thereof. The novel collectors of the invention provide unexpectedly high recoveries of non-ferrous metal-containing sulfide minerals or metal-containing sulfided oxide minerals and exhibit good selectivity for these minerals when present in the presence of iron-containing sulfide minerals. Preferably, R and R represent an aliphatic or cycloaliphatic group optionally substituted with one or more hydroxyl, cyano, halogen, OR, or SR groups, and R and R together with the S atom represent heterocyclic ring* Particularly preferably R1 and R2 are alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl groups optionally substituted with one or more hydroxyl, halogen, cyano, OR or SR groups, wherein R1 is an aliphatic or cycloaliphatic group, and most preferably an alkyl, alkenyl, cycloalkyl or cycloalkenyl group* Most preferably R1 is a methyl or ethyl group, R1 is a C1-alkyl or alkenyl group* Most preferably R1 and R2 are different, i.e. the monosulfide is asymmetric* The total carbon content of the hydrocarbon portion of the monosulfide hydrocarbon is such that the monosulfide has a sufficiently hydrophobic character to effect transfer of mineral particles The monosulfide comprises 4 carbon atoms, more preferably 6 carbon atoms, and most preferably 8 carbon atoms. The maximum carbon content is 20 carbon atoms, more preferably 16 carbon atoms, and most preferably 12 carbon atoms. Examples of cyclic hydrocarbon sulfides included in the collector according to the invention are cyclic compounds of formula Ia shown in the drawing, wherein R independently represents a hydrogen atom, an aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, a hydroxyl group, a cyano group, a halogen, an OR group, a SR group, wherein the aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups may be optionally substituted with a hydroxyl group, a cyano group, a halogen, an OR group or a SR group, etc., and compounds of formula Ib, wherein R represents a branched or straight chain group. alkylene, alkenyl or alkylene 3 3 optionally substituted with a hydroxyl, cyano, halogen, OR or SR group. Another preferred sulphide used in the composition according to the invention is a compound of the formula /R/3-nC/H/n-S-O/H/n/R/3-n# wherein the R groups independently represent a hydrocarbon residue optionally substituted with a hydroxyl, cyano, halogen, ether, hydrocarbonoxy or hydrocarbonthioether group, or two R groups can react and form a cyclic or heterocyclic ring with an S atom, n is an integer 0, 1, 2 or 3. Preferably, R is an aliphatic, cycloaliphatic, aryl, alkylaryl or aralkyl group, optionally substituted with a cyano group, hydroxy, halogen, OR or SR group, wherein R has the meaning defined above* Most preferably, R is an alkyl, alkenyl, cycloalkyl or cycloalkenyl group* Most preferably, one of the -C/H/ /R /3-n groups is a methyl or ethyl group and the other is an alkyl or C~ ** alkenyl group. A preferred sulfide is also a compound of formula Ic, wherein R has the meaning defined above. Examples of hydrocarbon sulfides used as component(s) of the collector of the invention include: methyl butyl, methyl pentyl, methyl hexyl, methyl heptyl, methyl octyl, methyl nonyl, methyl decyl, methyl undecyl, methyl dodecyl, methyl cyclopentyl, methyl cyclohexyl, methyl cycloheptyl, methyl cyclooctyl, ethyl butyl, ethyl pentyl, ethyl hexyl, ethyl heptyl, ethyl octyl, ethyl nonyl, ethyl decyl. ethyl-undecyl, ethyl-dodecyl, ethyl-cyclopentyl, ethyl-cyclohexyl, ethyl-cycloheptyl, ethyl-cyclooctyl, propyl-butyl, propyl-pentyl, propyl-hexyl, propyl-heptyl, propyl-octyl, propyl-nonyl, propyl-decyl, propyl-undecyl, propyl-dodecyl, propyl-cyclopentyl, propyl-cyclohexyl, propyl-cycloheptyl, propyl-cyclooctyl, dibutyl, butyl-pentyl, butyl-hexyl, butyl-heptyl, butyl-octyl, butyl-nonyl, butyl-decyl, butyl-undecyl, butyl-dodecyl, butyl-cyclopentyl, butyl-cyclohexyl, butyl-cycloheptyl, butyl-cyclooctyl, dipentyl, pentyl-hexyl, pentyl-heptyl, pentyl-octyl, pentyl-nonyl, pentyl-decyl, pentyl-undecyl, pentyl-dodecyl, pentyl-cyclopentyl, pentyl-cyclohexyl, pentyl-cycloheptyl, pentyl-cyclooctyl, dihexyl, hexyl-heptyl, hexyl-octyl, hexyl-nonyl, hexyl-decyl, hexyl-undecyl, hexyl-dodecyl, hexyl-cyclopentyl, hexyl-cyclohexyl, hexyl-cycloheptyl, hexyl-cyclooctyl, diheptyl, heptyl-octyl, heptyl-nonyl, heptyl-decyl, heptyl-undecyl, heptyl-dodecyl, heptyl-cyclopentyl, heptyl-cyclohexyl, heptyl-cycloheptyl, heptyl-cyclooctyl, dioctyl, octyl-nonyl, octyl-decyl, octyl-undecyl, octyl-dodecyl, octyl-cyclopentyl, octyl-cyclohexyl, octyl-cycloheptyl, octyl-cyclooctyl, octyl-cyclodecyl, dinonyl, nonyl-decyl, nonyl-undecyl, nonyl-dodecyl, nonyl-cyclopentyl, nonyl-cyclohexyl, nonyl-cycloheptyl, nonyl-cyclooctyl, didecyl, decyl-undecyl, decyl-dodecyl, decyl-cyclopentyl, decyl-cyclohexyl, decyl-cycloheptyl, decyl-cyclooctyl*, decyl, dibutyl, dipentyl, dihexyl, diheptyl, dioctyl*. The second component of the collector according to the invention is an alkyl thiocarbonate, thionocarbamate, thiophosphate or mixtures thereof. Alkyl thiocarbonates herein mean those compounds which contain an alkyl thiocarbonate group and at least one alkyl group which is sufficiently hydrophobic to cause the transfer of sulfide mineral particles associated therewith. A preferred alkyl thiocarbonate is a compound of formula 2, wherein R is a C1-alkyl group, X is independently S or O, and M is an alkali metal cation. Preferred alkyl thiocarbonates include alkyl monothiocarbonates, dithiocarbonates, or trithiocarbonates. Preferred monothiocarbonates are represented by formula 2a, wherein R and M are as defined above. Examples of preferred alkyl monothiocarbonates are sodium ethyl monothiocarbonate, sodium isopropyl monothiocarbonate, sodium isobutyl monothiocarbonate, sodium amyl ... potassium ethyl monooxycarbonate, potassium isopropyl monooxycarbonate, potassium isobutyl monooxycarbonate, potassium amyl monooxycarbonate. Alkyl dithiocarbonates are usually called xanthates*. Preferred dithiocarbonates are represented by formula 2b, where R and M are as defined above. Preferred alkyl dithiocarbonates include potassium ethyl dithiocarbonate, sodium ethyl dithiocarbonate, potassium amyl dithiocarbonate, sodium amyl dithiocarbonate, potassium isopropyl dithiocarbonate, sodium isopropyl dithiocarbonate, sec-butyl sodium dithiocarbonate, potassium ec-butyl dithiocarbonate, sodium isobutyl dithiocarbonate, potassium isobutyl dithiocarbonate, etc. Preferred trithiocarbonates are represented by the formula 2cf wherein R and M are as defined above. Examples of alkyl trithiocarbonates are isobutyl sodium trithiocarbonate and sodium trithiocarbonate. isobutyl potassium* g Preferred trionocarbamates are represented by formula 3, wherein R is independently - + 9 9 an alkyl group ci_n* Y is -SM or -OR , wherein R is an alkyl group, a is an integer 1 or 2, b is an integer 0 or 1, and at b must equal 2* Preferred thionocarbamates include dialkyl dithiocarbamates and alkyl thionocarbamates* Preferred dialkyl dithiocarbamates are represented by formula 3a, wherein M is as defined above and R is independently an alkyl group ci_n* Examples of preferred dialkyl dithiocarbamates include methyl butyl dithiocarbamate, methyl isobutyl dithiocarbamate, dithiocarbamate methyl sec-butyl dithiocarbamate, methyl propyl dithiocarbamate, methyl isopropyl dithiocarbamate, ethyl butyl dithiocarbamate, ethyl isobutyl dithiocarbamate, ethyl sec-butyl dithiocarbamate, ethyl propyl dithiocarbamate, ethyl isopropyl dithiocarbamate. Preferred alkyl thionocarbamates are represented by formula 3b, wherein R is as defined above and R is a C 1 - C 1 1 alkyl group. Examples of preferred alkyl thionocarbamates include N-methyl butyl thionocarbamate, N-methyl isobutyl thionocarbamate, N-methyl sec-butyl thionocarbamate, N-methylpropyl, N-methylisopropylthionocarbamate, N-ethylbutylthionocarbamate, N-ethylisobutylthionocarbamate, N-ethylsec.butylthionocarbamate, N-ethylpropylthionocarbamate, N-ethylisopropylthionocarbamate. Among these, N-ethylisopropylthionocarbamate and N-ethylisobutylthionocarbamate are particularly preferred. Preferred thiophosphates are those represented by formula 4, wherein the groups R independently represent hydrogen, a C1-C2 alkyl group or an aryl group, X represents oxygen or sulfur, and M represents an alkali metal cation. Preferred thiophosphates include monoalkyldithiophosphates, dialkyldithiophosphates, diaryldithiophosphates, and monothiophosphates. * Preferred monoalkyl dithiophosphates are represented by formula 4a, wherein R and M are as defined above. * Examples of preferred monoalkyl dithiophosphates include ethyl dithiophosphate, propyl dithiophosphate, isopropyl dithiophosphate, butyl dithiophosphate, sec-butyl dithiophosphate, isobutyl dithiophosphate. * Preferred dialkyl and diaryl dithiophosphates are represented by formula 4b, wherein R and M are as defined above. * Examples of dial! dithiophosphates are Preferred dialkyl monothiophosphates include diethyl sodium dithiophosphate, disec-butyl sodium dithiophosphate, diisobutyl sodium dithiophosphate, diisoamyl sodium dithiophosphate, dicresyl sodium dithiophosphate. Preferred dialkyl monothiophosphates include diethyl sodium monothiophosphate, disec-butyl sodium monothiophosphate, diisobutyl sodium monothiophosphate, diisoamyl sodium monothiophosphate. R is preferably C2-6 alkyl, particularly preferably C3-12 alkyl; R is preferably C4 alkyl, most preferably C3-3 alkyl; R is preferably C2-0 alkyl, particularly preferably C2-6 alkyl, most preferably C3-4 alkyl; R-0 is preferably C2-3 alkyl or cresyl; and Preferably, the composition according to the invention consists of a) a hydrocarbon sulfide of the formula R-S-R, wherein R and R have the meanings given above, in an amount of from about 10% by weight to about 90% by weight; and b) an alkyl thiocarbonate of the formula II, a thionocarbamate of the formula III, a thiophosphate of the formula IV, or a mixture thereof, in an amount of from about 10% by weight to about 90% by weight. 90% by weight* Particularly preferably, the composition according to the invention consists of a) about 20-80% by weight of a hydrocarbon sulfide of the formula R-S-R and b) about 20-80% by weight of an alkyl thiocarbonate of the formula II, a thionocarbamate of the formula III, a thiophosphate of the formula IV or a mixture thereof. Particularly preferably, the composition according to the invention consists of a) about 30-70% by weight of a hydrocarbon sulfide of the formula R-S-R and b) about 30-70% by weight of an alkyl thiocarbonate of the formula II, a thionocarbamate of the formula III, a thiophosphate of the formula IV or a mixture thereof. The new collector according to the invention gives higher recovery, often with a higher metal content, than could be obtained using single components as a collector. Metal content herein means the fractional amount of the desired metal contained in the material collected in the froth.* By using the collector according to the invention, it is preferred to recover metal-containing sulphide minerals such as copper, nickel, lead, zinc or molybdenum, and especially copper-containing sulphide minerals.* By using the collector according to the invention, it is possible to recover metal-containing sulphide minerals which have a high natural hydrophobicity in the unoxidized state.* The term "hydrophobicity in the unoxidized state" refers to a freshly mined mineral or a mineral which has a fresh surface and is subject to flotation without the addition of a collector.* Ores for which the collectors according to the invention are useful include sulphide mineral ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, chromium, gold, platinum, uranium and their mixtures* Examples of sulphide minerals that can be concentrated by froth flotation using the method according to the invention are copper-containing minerals, such as covell (CuS), chalcocite (Cu2S), chalcopyrite (CuFeSg), valerite (CUgFe.Sy or Cu^FeAS7), tetrahedrite /Cu^bSg/, bornite /CUgFeS^/, cubanite /Cu2SFe4Sg/, enargite /^Cug/As^Sb/S.J^, tenanthite /Cu12As4S13/, brochentite ZTCu4/0H/6S04-7, antlerite 2TCu3S04/-0H/4_7, feraetynite Z~Cu3/ SbAs/S4-7 * burnonite /PbCuSbS3/ and minerals containing lead, such as galenite /PbS/, minerals containing antimony, such as antimonite /Sb2S3/, minerals containing zinc, such as sphalerite /ZnS/, minerals containing silver, such as stephanite /AgJSbS^/ and argentite /Ag2S/, minerals containing chromium, such as borolite /FeSCrSg/, minerals containing nickel, such as pentlandite ZVFeNi/gSe-7#, minerals containing molybdenum, such as molybdenite /MoSg/, minerals containing platinum and palladium, such as cuperite iCPt/AsS/2#7* Minerals Metal-containing sulfided oxide minerals are minerals that have been treated with a sulfiding agent to produce minerals that have sulfide mineral properties and can then be recovered by froth flotation using collectors that recover sulfide minerals. Oxide minerals are sulfided by contacting them with a compound that reacts with the minerals to form a bond with sulfur or to induce an affinity for sulfur. These methods are well known in the art. Such compounds include sodium hydrosulfide, sulfuric acid, and related sulfur-containing salts, such as sodium sulfide. Sulfided oxide minerals for which the collector of the invention is useful include copper, aluminum, iron, titanium, tungsten, molybdenum, magnesium, chromium, nickel, manganese, tin, uranium, and mixtures thereof. Examples of metal-containing oxide minerals that can be concentrated by froth flotation using the collector of the invention include copper-containing minerals such as cuprite (Cu20H), tenorite (Cu20H), malachite (Cu20H), azurite Z~Cu3/0H/2/C03/2_7, atacamite /Cu2Cl/0H/3/, chrysocolla /CuSiO3/j, aluminum-containing minerals such as corundum, zinc-containing minerals such as zincite /ZnO/ and smithsonite6 148 165 /ZnC03/#, tungsten-containing minerals such as wolframite ZVF«»Mn/W04_7, nickel-containing minerals such as bunsenite /NiO/, molybdenum-containing minerals such as wulfenite /PbMoCK/ and powellite /CaMoO/, iron-containing minerals such as hematite and magnetite, chromium-containing minerals such as chromite /FeOCrpOg/, iron- and titanium-containing minerals, Such as ilmenite, aluminum and magnesium-containing minerals such as spinel, iron and chromium-containing minerals such as chromite, titanium-containing minerals such as rutile, manganese-containing minerals such as pyrolutite, tin-containing minerals such as cassiterite, uranium-containing minerals such as uraninite, and uranium-containing minerals such as, for example, pitch (U0^5/U3O8^) and gummite (U03nH2O). The collectors according to the invention can be used in any concentrations that ensure the desired recovery of the desired minerals. The concentration depends in particular on the minerals to be recovered, on the quality of the ore subjected to froth flotation, on the desired quality of the mineral to be recovered. Preferably, the collectors according to the invention are used in concentrations of 0.001 to 1.0 kg per ton. ore, especially in the range between 0.010 and 0.2 kg of collector per ton of ore subjected to froth flotation. The collectors of the invention can be used in admixture with other collectors known in the art. Examples of such collectors are dialklythioureas, diarylthiophosphonyl chlorides, dialkyl and dlaryl dithiophosphonates, alkyl mercaptans, xanthogen formates, xanthates, mercaptobenzothazoles, fatty acids and fatty acid salts, alkyl sulfuric acids and their salts, alkyl and aryl sulfonic acids and their salts, alkyl phosphoric acids and their salts, aryl phosphoric acids and their salts, sulfosuccinates, sulfosuccinates, primary amines, secondary amines, amines, tertiary amines, quaternary ammonium salts, alkylpyridinium salts, guanidine, and alkylpropylenediamines. The examples below are given 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. Synergism has also been demonstrated in that the results obtained using a blend of two or more components exceed the average weight results for each component used alone. Comparable results were obtained using the same total amount of collector in each experiment. The DOWFROTH 1263 frother used in the examples is a polypropylene oxide-butylene oxide methyl ether having a molecular weight of approximately 400. Example I Froth flotation of molybdenum-copper ore from Western Canada. 1200 g bags of homogeneous ore containing chalcopyrite and molybdenite were prepared. The primary flotation procedure consisted of grinding the 1200 g charge with 800 ml of tap water for 14 minutes in a mixed ball mill (resulting in approximately 13 percent product fineness above 100 mesh). The resulting pulp was transferred to a 1500 ml Agitair flotation cell equipped with an automatic paddle defoamer. The pH of the slurry was adjusted to 10.2 using quicklime. The pH was not further adjusted during the test. Methyl isobutyl carbinol (MIBC) was used instead of the standard frother. The following is a schematic of the four-stage primary flotation. STEP 1: Collector - 0.0042 kg/tonne MIBC - 0.015 kg/tonne conditioning - 1 minute flotation - collect concentrate for 1 minute STEP 2: Collector - 0.0021 kg/tonne MIBC - 0.005 kg/tonne conditioning - 0.5 minutes flotation - collect concentrate for 1.5 min* STEP 31 Collector - 0.0016 kg/tonne MIBC - 0.005 kg/tonne conditioning - 0.5 minutes flotation - collect concentrate for 2.0 minutes 148 165 7 STEP 41 Collector - 0.0033 kg/tonne MIBC - 0.005 kg/tonne conditioning - 0.5 minutes flotation - collect concentrate for 2.5 minutes The results are summarized in Table 1. Table 1 , Collector , R_72 , R_?2 , 2avart.3 , cont.3 ¦ , Potassium amyl xanthate and i i i i 0.776 0.725 0.056 0.00181 1 1,2-epithiooctane ' 0.710 ' 0.691 ' 0.093 » 0.00325 ' , mixture 50/50 , 0.794 , 0.766 , 0.054 § 0.00177 , of potassium amyl xanthate and 1,2-epithiooctane 1 methyl hexyl ' 0.699 ' 0.697 ' 0.107 ' 0.00386 ' , Bleszanina 50/50 , 0.790 , 0.793 , 0.056 , 0.00169 , potassium amyl xanthate 1 methyl hexyl sulride i i i i i no This is an example according to the invention 2 R-7 is the fractional part of the recovery after 7 minutes ^ content means the fractional content of the specific metal present in the total mass collected in the foam* The 95% confidence area of the statistical error associated with the experimentally obtained R-7 values for Cu in Table 1 is ± 0.010* Therefore, the statistical range of the R-7 values for Cu in Table 1 obtained using potassium amyl xanthate is 0.776 £ 0.010 or 0.766 to 0f786* However, the statistical error associated with the R-7 values for Mo in Table 1 is +.015*. Taking these limitations into account, it is clearly seen that the recoveries of Cu and Mo within 7 minutes using the collector mixture according to the invention exceed the recoveries that could be expected in the same time taking into account the weight average results obtained when using the individual components individually, which indicates the occurrence of synergism. Example II* Froth flotation of copper-nickel ore from Eastern Canada. Copper-nickel ores containing chalcopyrite, pentlandite, and pyrrhotite were subjected to flotation using 0.0028 kg/tonne of DOWFROTH 1263 frother and 0.28 kg/tonne of polypropylene oxide methyl ether and butylene of molecular weight 400/. A series of samples was transferred from the pretreatment feeder and placed in approximately 1200 g buckets. The contents of each bucket were used to conduct time-recovery measurements in a Denver cell equipped with an automatic paddle device and a pulp level control device, with individual concentrates selected at 1.0, 3.0, 6.0, and 12.0 minutes.* Chemicals were added during the 1-minute conditioning period, before defoaming began.* Addition of reagents was not a separate step.* Individual concentrates were dried, weighed, ground, and statistically representative test samples were prepared. The results are summarized in Table 2.6. 148 165 Table 2, Amyl Xanthate Collector and sodium 1 1,2-epithiooctane * and dibutyl sulfide1 50/50 mixture of 1,2-epithiooctane and sodium amyl xanthate 1 ' 1 50/50 mixture of dibutyl sulfide and sodium amyl xanthate and ! Cu 2 R-12* 0.930 1 0.927 0.928 0.927 ' 0.931 ' Ni 9 R-12* 0.839 0.751 0.630 0.844 ' 0.824 ' Pyrrhotite R-12z ' ' 0.358 ' 1 0.247 ' 0.190 , 0.344 0.245 1 no This is an example The R-12 invention is a fractional recovery obtained experimentally after 12 minutes. All the Cu recoveries obtained within 12 minutes, presented in Table 2, are so high (reaching the theoretical limit of 1.0) that the statistical limits of the 95% confidence interval for the R-12 value for Ni in Table 2 are disregarded. The 95% confidence level of the R-12 value for Ni in Table 2 is +0.012. It is clearly seen that using the collector mixture according to the invention, Ni recoveries are obtained that significantly exceed the expected recovery based on the weight average results obtained using each component individually, confirming the existence of synergism. Example III. Froth flotation of a Pb/Zn/Cu/Ag complex ore from Central Canada. A homogeneous 1000 g sample of the ore containing galenite was prepared, Sphalerite, chalcopyrite, and argentite. For each flotation run, the sample was fed to a rod mill along with 500 ml of tap water and 7.5 ml of S02 solution. Within 6.5 minutes of grinding, a feed containing 90% of particles with a fineness of less than 200 mesh (75 µm) was obtained. After grinding, the contents were transferred to a cell equipped with automatic planar removal paddles, and the cell was connected to a standard Denver flotation mechanism. Two-stage flotation was then performed. In the first stage, copper/lead/silver ores were recovered, and in the second stage, zinc ores were recovered. To begin the first stage of flotation, 1.5 g/kg of Na2CO3 (pH 9 to 9.5) was added, followed by the collector(s). The slurry was then conditioned for 5 minutes with air and agitation. The flotation stage II consisted of adding 0.5 kg/tonne of CuSO4 to the residue in the cell after stage I. The pH was adjusted to 10.5 by adding quicklime, followed by a 5-minute conditioning period with stirring only. The pH was checked again and adjusted to 10.5 with lime. At this point, the collector(s) were added, followed by another 5-minute conditioning period with stirring only. The flotation stage II was then added, followed by another 5-minute conditioning period with stirring only. The flotation stage II was then added, followed by a 5-minute conditioning period with stirring only. The flotation stage II was then added, followed by a 5-minute conditioning period with stirring only. The flotation stage II was then added, followed by a 5-minute conditioning period with stirring only. The flotation stage II was then added, and the concentrate was collected for 5 minutes and designated as zinc preliminary concentrate. Samples of the concentrates were dried, weighed, and prepared. appropriate samples for testing using X-ray techniques*. Using the data from the analyses, recovery and content values were calculated according to mass balance formulas. The results are summarized in Table 3.148 165 Table 3, Transition-1, Run i, : H 1 2 r i 3 §1 Stage /initial/ "Cu/Pb LZn 'Cu/Pb v*n (cu/Pb Iso Collector A B A C , D D , C D 1 B 1 D Dose pH g/t ' ¦ 5 7.5 20 15 12.5 20 15 i 5 7.5 35 i 9'5 '10.5 , 9.5 '10.5 i 9.5 '10.5 Ag R-52 0.886 0.052 ,0.778 'O.103 ¦0.891 10.030 Cont. 0.275 - 0.312 - 0.272 - Cu R-52 0.941 1 0.030 0.893 1 0.048 ¦ 0.942 ( 0.018 1 Pb 3 2 Conc* ¦ R-5 0.107 ,0.794 10.077 0.136 i 0.662 - '0.145 0.110 "0.795 - %0.045 1 Zr\ 3 2 Cont. ¦ R-5 0.050, 0.220 1 0.782 0.057, 0.145 '0.812 0.052 '0.218 ,0.570 3. Concentration* • , 0.48 ' and 0.497 1 0.532 , A - sodium ethyl xanthate B - dithiophosphate C - oxycarbamate D - dihexyl sulfate 1 2 3 not for the example according to the invention R-5 means the actual recovery after 5 minutes con- tent* means the fractional content of a specific metal contained in the total mass collected in the froth* Table 3 presents the conditions for duplicate tests which enable a comparison of recoveries obtained when using the mixture of collectors according to the invention with the recoveries obtained with the individual components used individually* From the comparison of Cu/Pb flotation (stage 1) - run 2 using only collector D with Cu/Pb flotation (stage 1) - run 3 using the mixture collectors D - B shows that a higher recovery of Ag, Cu and Pb was obtained using the collector mixture according to the invention. The 95% confidence level of the statistical error for Ag is ± 0.01, for Cu ± 0.01 and for Pb ± 0.02. The comparison of Zn flotation (stage 11) - run 3 with Zn flotation (stage 11) - run 2 also shows an obvious increase in Zn recovery associated with the use of the collector mixture compared to a single component. The 95% confidence level of the statistical error for Zn is ± 0.01. "" Other runs in which single collectors were used in different stages are not shown in Table 3 because many components used individually simply do not lead to results that would be meaningful for comparison. For example: collector B used alone in stage I for Cu and Pb gives less than 0.500 recovery. Example IV* Froth flotation of a complex Cu/Mo ore from South America. 500 g of Cu/Mo, containing sulfide minerals containing mainly copper and molybdenite, was placed in a rod mill with 2.5 cm rods along with 257 g of deionized water and some quicklime. The mixture was then ground for 350 revolutions at 60 rpm to obtain a suitable fineness. The ground slurry was transferred to a 1500 ml Agitar flotation cell equipped with an automatic paddle froth removal system. The slurry was stirred at 1150 rpm and the pH adjusted to the appropriate value (shown in Table 4) using more lime or hydrochloric acid. At this point, the cell collector(s) (45 g/tonne) was added to the flotation cell, followed by a 1-minute conditioning period during which DOWFROTH10 148 165 frother (34.4 g/tonne) was added. After the additional conditioning period, air was introduced into the flotation cell at a rate of 4.5 l/min for 1 minute, and an automatic stirrer was used to remove foam. Foam samples were taken after 0.5, 1.5, 3.0, 5.0, and 8.0 minutes. The samples were dried overnight in an oven together with the flotation tailings. The dried samples were weighed, pulverized to a suitable fineness for dissolution, and dissolved in acid for analysis in the DC Plasma Spectrograph. The results are summarized in Table 4. Table 4: Process and ± 1 2 ¦ 3 and 4 and 5 and 6 Collectors ^Isopropyl ethyl thionocarbamate \j Ethyl octyl sulfide ^Isopropyl ethyl thionocarbamate ( Sodium isopropyl xanthate \_Ethyl octyl sulfide fIsopropyl ethyl thionocarbamate \j Ethyl octyl sulfide /Isopropyl ethyl thionocarbamate 1Sodium isopropyl xanthate VjEthyl octyl sulfide Dose 1 g/ton 1 22.7 , 22.7 1 45.4 11.4 » 11.4 22.7 22.7 22.7 45.4 11.4 11.4 22.7 , PH L _ _ _ 10.5 1 10.5 10.5 8.0 8.0 8.0 8.0 . CU 2 1 R-8* 1 0.891 1 0.854 and 0.893 and 0.912 and 0.887 , 0.901 . M0 2 1 R-8^ L _____ _l 1 0.742 ' 0.791 ' and 0.808 and 0.780 • 0.822 and 0.831 (not an example according to the invention) 2 R-8 means fractional recovery after 8 minutes All Cu recoveries achieved within 8 minutes shown in Table A are so high (reaching the theoretical limit of 1.0) that statistical confidence limits are not taken into account. 95% confidence level The statistical error for Mo recovery over 8 minutes is +.012. It is clearly seen that the collector mixtures according to the invention give significantly higher Mo recoveries than the recoveries that would result from the values obtained for the individual components used separately. For example, the Mo recovery in run 3 significantly exceeds the recovery expected from the results of runs 1 and 2. A synergistic effect occurs here. Patent claims 1. A new collector for the recovery of non-ferrous metal-containing sulfide minerals or metal-containing sulfided oxide minerals from ores by froth flotation, characterized in that it consists of (a) a hydrophobic hydrocarbon monosulfide containing 4-20 carbon atoms of the formula R-S-R, wherein R is an aliphatic, cycloaliphatic or aralkyl, optionally substituted with one or more hydroxyl, cyano, halogen, ether, hydrohydroxy or carbon-2 dorothioether groups, R denotes an aliphatic, cycloaliphatic, aromatic or combination thereof, containing 5-11 carbon atoms, in addition R and R can be formed heterocyclic ring with sulfur, and the sulfur is associated with an aliphatic or cycloaliphatic carbon atom and with /b/ thiocarbonate, thiocarbamate, alkyl phosphorothioate or mixtures thereof. 2. The collector according to claim 1, characterized in that the thiocarbonate contains a compound of formula 2, in which R denotes the CU-D alkyl group, X independently denotes a sulfur or oxygen atom, M denotes an alkali metal cation as thionocarbamate comprises a compound of formula 3, wherein R independently represents a C1-1n alkyl group, Y represents a -+1~1Ugg-SM group, wherein M represents an alkali metal cation or an OR group, wherein R represents a C1-1n alkyl group, a is an integer 1 or 2, b is an integer 0 or 1, wherein a+b»2, and as a thiophosphate comprises a compound of formula 4, wherein R independently represents a hydrogen atom, a C1-1n alkyl group or an aryl group, M represents an alkali metal cation or an OR group, wherein R represents a C1-1Q alkyl group, X represents an oxygen or sulfur atom* 3* Collector according to claim 1, characterized in that it consists of /a/ about 10-90% % by weight of a hydrocarbon sulfide and /b/ about 10-90% by weight of a thiocarbonate, thionocarbamate, alkyl thiophosphate or a mixture thereof. 4. A collector as claimed in claim 3, wherein the collector comprises /a/ about 20-80% by weight of a hydrocarbon sulfide and /b/ about 20-80% by weight of a thiocarbonate, thionocarbamate, alkyl thiophosphate or a mixture thereof. 5. A collector as claimed in claim 1, wherein the collector comprises /a/ a hydrocarbon sulfide of the formula R -S-R , wherein R and R are independently an aliphatic, cycloaliphatic or aralkyl group optionally substituted with one or more hydroxyl, cyano, A collector according to claim 5, characterized in that R and R are cycloaliphatic or aliphatic groups, optionally substituted with one or more hydroxyl, cyano, halogen, OR or SR groups, wherein R and R can combine to form a heterocyclic ring, and the thiocarbonate comprises a compound of formula 2, wherein R is a C2-16 alkyl group, M is a sodium or potassium cation, the thiocarbamate comprises a compound of formula 3, wherein R is a C10 alkyl group, the thiophosphate comprises a compound of formula 4, wherein R is a C2-8 alkyl or cresyl group. A collector according to claim 5, characterized in that R and R are cycloaliphatic or aliphatic groups, optionally substituted with one or more hydroxyl, cyano, halogen, OR or SR groups, wherein R and R can combine 7. A collector as claimed in claim 6, wherein R and R are independently alkyl or alkenyl. 9. A collector as claimed in claim 8, wherein R is methyl or ethyl, and R is C-1-alkyl or C-1-alkenyl. 10. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 11. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 12. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 13. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 14. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 15. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 16. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 17. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 18. A collector as claimed in claim 1 or 4, wherein R is C-1-alkyl or C-1-alkenyl. 19 ... 6 6 hydrocarbon of the formula /R /3_nC/H/ -S-C/H/n-/R /3_n» in which the R groups independently represent an aliphatic or cycloaliphatic group optionally substituted with a hydroxyl, cyano, halogen, ether, hydrocarbonoxy or hydrocarbonthioether group, wherein two R groups can combine and form a cyclic or heterocyclic ring with an S atom, n is an integer 0, 1, 2 or 3, or of the formula 1c, in which R independently represents a hydrogen atom, an aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, optionally substituted with a hydroxyl, cyano, halogen, OR334 or SR group, in which R is a group aliphatic or cycloaliphatic and R represents a hydroxyl, cyano, halogen, OR or SR group. 11* A collector according to claim 10, characterized in that it consists of (a) a hydrocarbon sulfide and (b) an alkyl thiocarbonate, which includes an alkyl monothiocarbonate, an alkyl dithiocarbonate or alkyl trithiocarbonate* 1 2 12* A collector according to claim 1, characterized in that R and R represent different hydrocarbon residues* in gla* 13* A collector according to claim 1, characterized in that R contains 5-11 atoms. 14* A collector according to claim 1, characterized in that it contains a sulfide of formula la, wherein R is independently a hydrogen atom, an aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, optionally substituted with a hydroxyl, cyano, halogen or an OR or SR group or is a hydroxyl, cyano, halogen, OR or SR group. FORMULA 1a R" C — CH2 \ / S FORMULA 1c FORMULA Ib 7 " R -X- C-SM FORMULA 2 (RbL-N-C-Y a I (H)k PATTERN 3 R8K S \ I' „ rN-C-S"M+ PATTERN 3 a s 8 » 9 R -NH-C-OFT PATTERN 3b Rl0n S R °\H - ? P-S M R^O7 PATTERN Ab -X-M Rio.0X PATTERN 4 P-0 M Rl0o/ PATTERN Ac \ H P-S"M + HO PATTERN Aa Printing Studio of the Polish People's Republic. Edition 100 copies Price 400 PLN PL PL PL PL PL PL PL PL PL PL