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 subject of the invention is a new collector for recovering sulphide minerals containing non-ferrous metals and metal-containing sulphide minerals from ores by foam flotation. Flotation is a process of treating a mixture of finely divided solid minerals, e.g. powdered ore suspended in a liquid, as a result of which part of such materials are separated from other finely divided solid particles, e.g., aluminum and other similar materials found in the ore by introducing gas / or generating gas in situ / into the liquid so as to produce a foamed mass in which part of the body becomes solid. The iron is on top of the liquid and the other solid components of the ore remain suspended (not foamed). Some of the gas sticks to parts of the suspended solids, which causes the particles with the adhered gas to become lighter than the liquid and rise to the top of the liquid to form foam.

Various flotation additives are added to the slurry to improve the foaming process. Such additives are classified according to the function they perform and so: collectors, which for sulphide-containing minerals include xanthates, thionocarbamates, etc., foaming agents, which give a stable foam-forming property, e.g. natural oils such as pine oil and eucalyptus oil, etc. Modifiers such as activators to induce flotation in the presence of the collector, for example copper sulphate; depressants, eg sodium cyanide, which prevent the collector from acting on the mineral, the ointments remain in the liquid, and the plaster thus prevents the substance from floating up and forming some foam; pH regulators for 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, and on the minerals desired to be recovered.

The flotation principle is used in many mineral separation processes, including selectively separates metal-containing sulphide minerals such as copper, zinc, lead, nickel, molybdenum and other metals from iron-containing sulphide minerals such as pyrite and pyrrhotite * For collectors commonly used for recovery Metal-containing sulfide minerals or metal-containing oxide sulfide minerals include xanthates, dithiophosphates and thionocerbamates. Volatile sulfur compounds often enter the atmosphere through factory chimneys or are removed from chimneys by expensive and complex washing facilities.

Many non-ferrous metal-containing sulfide minerals or metal-containing oxide minerals are found in ores that also contain iron-containing sulfide minerals. When iron-containing sulphide minerals are recovered from the flotation process together with non-ferrous sulphide minerals and metal-containing sulphide minerals, an excess of sulfur occurs which is released during the smelting process. A means of acting as collectors is therefore required which are capable of selectively recovering non-ferrous sulphide minerals and metal-containing sulphide minerals without recovering iron-containing sulphide minerals. Known collectors! xanthates, thionocarbamates and dithiophosphates do not act selectively in the recovery of sulphide minerals containing non-ferrous metals in the presence of iron-containing sulphide minerals, but crops and recovers all metal-containing sulphide minerals. The collector according to the invention consists of a monosulfide / hydrophobic hydrophobic 1 weight of 4-20 carbon atoms of formula R -SR, in which R is aliphatic, cycloaliphatic or aralkyl, optionally substituted with one or more hydroxyl, cyano, halogen, ether, hydrocarbyl or hydrocarbyl thioether groups, 2 R is the group aliphatic, cycloaliphatic, aromatic or combinations thereof, containing 1 2 * 5-11 carbon atoms, in addition, R and R can heal the sulfur heterocyclic ring, and sulfur is linked to an aliphatic or cycloalliphatic carbon atom and / b / thio - an alkyl carbonate, thionocarbamate, thiophosphate or mixtures thereof * N These collectors according to the invention have unexpectedly high recoveries of non-ferrous sulphide minerals or metal-containing sulphidized oxide minerals, and show good selectivity to these minerals when present in the presence of iron-containing sulphide minerals, and R and R preferably are an aliphatic or cycloaliphatic group optionally substituted with one or more hydroxy, cyano, halogen, OR or SR groups 1 2 and R and R together with the S atom represent a heterocyclic ring * Particularly preferably 1 2 R IR represents an alkyl, alkenyl, alkynyl group, cycloalkyl or cycloalkenyl optionally substituted with one or more hydroxyl, halogen, cyano, OR or SR 3 3 3 groups, where R is aliphatic or cycloaliphatic, and most preferably and more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl is * 2 methyl or ethyl groups, R is a group e Cgali-alkyl or alkenyl * Most preferably R and R are different, i.e. * monosulfide is asymmetric * The total carbon content of the hydrocarbon portion of the hydrocarbon monosulfide is such that the monosulfide is sufficiently hydrophobic to cause the transfer of particles of a metal sulfide containing mineral or Sulfide oxide metal containing air / bubble interface. Preferably the monosulfide contains 4 carbon atoms, more preferably 6 atoms and most preferably 8 carbon atoms. The maximum carbon content is 20 atoms, more preferably 16 and most preferably 12 atoms.

Examples of cyclic hydrocarbon sulfides in the collector according to the invention are cyclic compounds of formula Ia shown in the figure, in which R is independently hydrogen, aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups, cyano, halogen, OR, SR groups, where the aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups may be optionally substituted with hydroxy, 3 3 5 Io, cyano, halogen, OR or SR groups etc. * and the compounds of formula Ib in which R 148 165 3 represents a branched or straight chain alkylene, alkenyl or alkynylene group 3 3 optionally substituted with hydroxyl, cyano, halogen, OR or SR group • Another preferred sulfide used in the composition of the invention is the compound of 6 6 formula (R / 3_nC / H / nS-0 / H / n / R / 3_n # in which the R groups independently represent a hydrocarbon residue optionally substituted hydroxy, cyano, halogen, ether, hydrocarbyl, or hydro-thioether or two R groups may heal and form a cyclic or heterocyclic ring with an S atom, n is an integer 0, 1, 2 or 3.

Preferably R is aliphatic, cycloaliphatic, aryl, alkylaryl or aralkyl, optionally substituted cyano, hydroxy, halogen, OR or SR 3,336 or SR group, in which R is as defined * Most preferably R is alkyl, alkenyl, cycloalkyl or cycloalkenyl * Most preferably, one of the -C / H / / R / 3-n groups is methyl or ethyl and the other is alkyl or C ** alkenyl.

A preferred sulfide is also the compound of Formula 1c, wherein R is as defined above * Examples of hydrocarbon sulfides used as collector component (s) according to 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, ethyl-heptyl, ethyl-octyl, ethyl-nonyl, ethyl-decyl * ethyl-undecyl, ethyl-dodecyl, ethyl-cyclopentyl, ethyl-cyclohexyl, ethyl-cycloheptyl, ethyl-cyclooctyl, propyl-propyl propyl hexyl, propyl heptyl, propyl octyl, propyl nonyl, propyl decyl, propyl undecyl, propyl dodecyl, propyl cyclopentyl, propyl cyclohexyl, propyl cyan cloheptyl, propyl-cyclooctyl, dibutyl, butyl-pentyl, butyl-hexyl, butyl-heptyl, butyl-octyl, butyl-nonyl, butyl-decyl, butyl-undecyl, butyl-dodecyl, butyl-cyclopentyl, butyl-dodecyl, butyl-cyclopentyl butyl cycloheptyl, butyl cyclooctyl, dipentyl, pentyl hexyl, pentyl heptyl, pentyl octyl, pentyl nonyl, pentyl decyl, pentyl undecyl, pentyl dodecyl pentyl pentyl pentyl pentyl pentyl pentyl pentyl pentyl pentyl cycloheptyl, pentyl cyclooctyl, dihexyl, hexyl heptyl, hexyl octyl, hexyl nonyl, hexyl decyl, hexyl undecyl, hexyl dodecyl, hexyl cyclopentyl, hexyl cyclopentyl, hexyl cyclopentyl, hexyl cyclopentyl, hexyl cyclopentyl, hexyl cyclopentyl diheptyl, heptyl octyl, heptyl nonyl, heptyl decyl, heptyl undecyl, heptyl dodecyl, heptyl cyclopentyl, heptyl cyclohexyl, heptyl -cycloheptyl, heptyl-cyclo-octyl, dioctyl, octyl-nonyl, octyl-decyl, octyl-undecyl, octyl-dodecyl, octyl-cyclopentyl, octyl-cyclohexyl, octyl-cycloheptyl, octyl-cycloheptyl, octyl-cyclodecyl , nonyl decyl, nonyl undecyl, nonyl dodecyl, nonyl cyclopentyl, nonyl cyclohexyl, nonyl cycloheptyl, nonyl cyclooctyl, didecyl, decyl undecyl, decyl decyl decyl, decyl decyl decyl decyl decyl decyl cyclohexyl, decyl-cycloheptyl, decyl-cyclooctyl * decyl, dibutyl, dipentyl, dihexyl, diheptyl, dioctyl * The second component of the collector according to the invention is thiocarbonate, thionocarbamate, thiophosphate, alkylcarbonates or their mixtures hereof thiophosphate carbonate and at least one alkyl group which is sufficiently hydrophobic to cause the transfer of associated with them a metal-containing sulphide mineral or a sulphidized oxide mineral containing a metal at the air / bubble interface * The preferred alkyl thiocarbonate is the compound of formula 2, where R is an alkyl group C, X is independently S or 0, M is a metal cation * Preferred alkyl thiocarbonates include alkyl monothiocarbonates, dithlocarbonates, or trithiocarbonates * Preferred monothiocarbonates shown in Figure 2a in which R IM has the meanings defined above * Examples of preferred alkyl monothiocarbonates4 148 165 are monothiocarbonate sodium monotropylcarbonate, is Sodium Isobutyl Carbonate, Sodium Amylcarbonate, Potassium Ethyl Carbonate, Potassium Isopropyl Monoxycarbonate, Potassium Isobutyl Monocarbonate, Amyl Potassium Monocarbonate.

The alkyl dithiocarbonates are usually referred to as xanthogens * Preferred dithiocarbo- nates are shown in formula 2b, wherein R 1M has the meanings defined above.

Preferred alkyl dithiocarbonates include potassium ethyl dithiocarbonate, sodium ethyl dithiocarbonate, amyl potassium dithiocarbonate, sodium amyl dithiocarbonate, isopropyl potassium dithiocarbonate, isopropyl sodium dithiocarbonate, sodium eutecarbonate sodium dithiocarbonate. * potassium butyl, sodium isobutyl dithiocarbonate, potassium isobutyl dithiocarbonate, etc. * Preferred trithiocarbonates are represented by the formula 2cf where R and M have the above-defined meanings * Examples of alkyl trithiocarbonates are isobutyl sodium trithiocarbonate and isobutyl potassium trithiocarbonate * isobutyl trithiocarbonate is the formula 3, where R is independently - + 9 9 C1 and n * Y is -SM or -OR, where R is an alkyl group and is an integer 1 or 2, b is an integer 0 or 1, where atb must equal 2 * Preferred dialkyl thionocarbamates include dialkyl dithiocarbamates and alkyl thionocarbamates * Preferred dialkyl dithiocarbamates pr is formula 3a, where M is as defined above and the R groups are not strictly a C1in alkyl group. Examples of preferred dialkyl dithiocarbamates include methyl butyl dithiocarbamate, methyl isobutyl dithiocarbamate, methyl isobutyl dithiocarbamate, methyl secithibutyl dithiocarbamate, methyl secedithiocarbamate, Methyl isopropyl ethyl butyl dithiocarbamate, ethyl isobutyl dithiocarbamate, ethyl sec * butyl dithiocarbamate, ethyl propyl dithiocarbamate, ethyl isopropyl dithiocarbamate * The preferred formula is R, denoted with R, and R is represented by the 3 denotes a C1-1 alkyl group. Examples of preferred alkyl thionocarbamates include N-methyl-butyl thionocarbamate, N-methyl isobutyl thionocarbamate, N-methyl sec-butyl thionocarbamate, N-methyl propyl thionocarbamate, N-methyl thionocarbamate -isopropyl, N-ethyl butyl thionocarbamate, N-ethyl isobut thionocarbanate ylu, N-ethyl-sec-butyl thionocarbamate, N-ethyl-propyl thionocarbamate, N-ethyl-isopropyl thionocarbamate * Among these, N-ethyl isopropyl se-thionocarbamate and N-ethyl-isobutyl thionocarbamate are particularly preferred * Preferred thiophosphates are presented Formula 4, where the R groups are independently hydrogen, C * -O alkyl or aryl groups, X is oxygen or sulfur, and M is an alkali metal cation * Preferred thiophosphates include monoalkyl dithiophosphates, dialkyl dithiophosphates, diaryl dithiophosphates and monothiophosphates * The 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, isobutyl dithiophosphate by formula 4b, where R and M are known as above connection * Examples of dial dithiophosphates! These include sodium diethyl dithiophosphate, sodium disodium butyl dithiophosphate, sodium diisobutyl dithiophosphate, sodium diisoamyl dithiophosphate, sodium dicresyl dithiophosphate * Preferred dialkyl monothiophosphates are as shown in R11 and M, Preferred monothiophosphates include sodium diethyl monothiophosphate, sodium di-butyl monothiophosphate, sodium diisobutyl monothiophosphate, sodium diisoamyl monothiophosphate. R 7 is preferably C2 * 6 alkyl, particularly preferably C3-12 * alkyl, R preferably is C1-4 alkyl, most preferably C1-3 alkyl, R preferably is C2-O "alkyl, more preferably C2-6 alkyl, and most preferably C3-4 • R-O alkyl is preferably C2-3 alkyl or cresyl * and Preferably the composition of the invention consists of a hydrocarbon sulfide of formula R -SR wherein R and R are as defined above in an amount of about 10% by weight. up to about 90% by weight of the alkyl thiocarbonate of the formula 2, the thiocarbamate of the formula 3, the thiophosphate of the formula 4 or mixtures thereof in an amount of from about 10% by weight to about 90% by weight * Especially preferably the composition according to the invention consists of / about 20 -80% 1 2 by weight of hydrocarbon sulfide of formula R-SR and b / about 20-80% by weight of alkyl thiocarbonate of formula II, thiocarbamate of formula III, thiophosphate of formula IV or mixtures thereof * Particularly preferably, the composition according to the invention consists of / about 30-70% by weight of hydrocarbon sulfide of formula R -S-R and b) about 30-70% by weight of alkyl thiocarbonate of formula II, thiocarbamate of formula III, thiophosphate of formula IV or mixtures thereof.

The new collector according to the invention gives a higher recovery, often with a higher metal content than could be obtained by using single components as a collector. The metal content here means the fractional amount of molten metal contained in the material collected in the foam * Using the collector according to the invention, metal-containing sulphide minerals are preferably recovered * Especially preferably copper, nickel, lead, zinc or molybdenum are recovered, especially copper-containing sulphide minerals * By using the collector according to the invention, it is possible to recover metal sulphide-containing minerals that exhibit high natural unoxidised hydrophobicity * The term "unoxidised hydrophobicity" refers to a freshly extracted mineral or a mineral that has fresh surfaces and flotates without the addition of a collector * Ores for which suitable collectors in accordance with the invention include sulphide mineral ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, chromium, gold, platinum, uranium and mixtures thereof * Examples of sulphide minerals which can be concentrated by route of foam flotation by according to the invention, there are copper minerals, such as e.g. covelin / CuS /, chalcosine / Cu2S /, chalcopyrite / CuFeSg /, valerite /CUgFe.Sy or Cu ^ FeAS7 /, tetrahedrite / Cu ^ bSg /, bornite / CUgFeS ^ /, kubanit / Cu2SFe4Sg /, enargite / ^ Cug / As ^ Sb / SJ ^, tenantit / Cu12As4S13 /, brochentyt ZTCu4 / 0H / 6S04-7, antlerite 2TCu3S04 / -0H / 4_7, feraetyn'ite Z ~ Cu3 / SbAs / S4-7 * burnonite / PbCuSbS3 / and lead-containing minerals, such as galenite / PbS /, antimony-containing minerals, such as, for example, antimonite / Sb2S3 /, zinc-containing minerals, such as, for example, sphalerite / ZnS /, silver-containing minerals, such as, for example, stefanite / AgJSbS ^ / and argentite / Ag2S /, chromium-containing minerals, such as, for example, dobrolite / FeSCrSg /, nickel-containing minerals, such as, for example, pentlanite ZVFeNi / gSe-7 # minerals containing molybdenum such as, for example, molybdenite / MoSg /, minerals containing platinum and palladium, such as, for example, cuprite iCPt / AsS / 2 # 7 * Oxide minerals sulphated with Bending metal are minerals that have been treated with a sulphidizing agent so as to obtain minerals that have the properties of a sulphide mineral and can then be recovered by foam flotation using collectors that recover the sulphide minerals. Oxide minerals are sulfated by contact with a compound that reacts with the minerals to form a bond with sulfur or to develop an affinity for sulfur * These are methods well known in the art * Such compounds include sodium bisulfide, sulfuric acid and sulfur-containing salt derivatives such as sodium sulfide * Sulfided oxide minerals for which a collector in accordance with 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 may be concentrated by froth flotation by means of a collector according to the invention se minerals containing copper, such as cuprite / CuJO /, tenorite / CuO /, malachite £ "/ Cu20H / 2C03_7, azurite Z ~ Cu3 / 0H / 2 / C03 / 2_7, attackamite (Cu 2 Cl (OH) 3), chrysocolla (CuSiO 3), aluminum-containing minerals, such as corundum, zinc-containing minerals, such as zincite (ZnO), and smitsonite (ZnCO 3), and tungsten-containing minerals, such as, for example, Tungsten ZVF «» Mn / W04_7, nickel-containing minerals such as, for example, Bunsenite / NiO /, Molybdenum-containing minerals, such as, for example, Wulfenite / PbMoCK / and Powelite / 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 minerals such as spinel, iron and chromium minerals such as chromite, titanium containing minerals such as such as rutile, manganese-containing minerals such as pyrolyte, tin-containing minerals such as cassiterite, uranium-containing minerals such as uraninite, and uranium-containing minerals such as, for example, tar / Uo ^ 5 / U308 ^ and gumite / U03nH20 /.

The collectors according to the invention can be used at any concentration that ensures the expected recovery of the collected minerals * The concentration depends in particular on the minerals to be recovered, on the quality of the ore subjected to foam flotation, on the desired quality of the recovered mineral * Preferably, the collectors according to the invention are used at concentrations of 0.001 to 1.0 kg per ton of ore, especially in the range between 0.010 and 0.2 kg of collector per ton of ore to be flotated. * The collectors according to the invention may be used in a mixture with other collectors known in the art. dialkylthioureas, diarylthiophosphonyl chlorides, dialkyl and daryl dithlophosphonates, alkyl mercaptans, xanthogen formates, xanthates, mercaptobenzotlazoles, fatty acids and salts of fatty acids, alkylsulfuric acids and their salts, their alkylphosphoric and alkylsulfonic acids and their alkylphosphoric acids arylphosphoric acids and their salts, sulfosuccinates, sulfosuccinates ns, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkylpyridinium salts, guanidine and alkylpropylene diamines * The examples below are merely illustrative and should not be construed as limiting the scope of the invention * Unless otherwise stated, all parts and fractions means parts by weight * It has also been found the existence of synergism, as the results obtained with a mixture of two or more ingredients outweigh the Average weight results for each of the components used separately * The compared results were obtained using the total amount of the collector in each experiment * The DOWFROTH 1263 foamer used in the examples is a methyl ether of polypropylene oxide and butylene oxide with a molecular weight of approx. 400 * Foam and ore flotation -Copper from Western Canada * Prepared homogeneous red bags containing chalcopyrite and molybdenite, 1,200 g each. The preflotation procedure consists of grinding a 1200 g charge with 800 ml of tap water for 14 minutes in a ball mill with a mixed charge of spheres (which is approximately 13 percent of the product with a size greater than 100 mesh). The resulting pulp was transferred to a 1500 ml Agitair flotation cell. equipped with an automatic paddle system to remove foam * the pH of the slurry was adjusted to 10.2 using quicklime * During the test, the pH was not corrected anymore * The standard frother was made with methyl-isobutyl carbinol / MIBC / * The diagram below is a four-stage initial flotation * STEP 1: Collector - 0.0042 kg / ton MIBC - 0.015 kg / tonne conditioning - 1 minute flotation - collect concentrate for 1 minute STEP 2: Collector - 0.0021 kg / ton MIBC - 0.005 kg / tonne conditioning - 0.5 minutes flotation - collect concentrate for 1.5 minutes * STEP 31 Collector - 0.0016 kg / ton MIBC - 0.005 kg / ton conditioning - 0.5 minutes flotation - collect concentrate for 2.0 minutes 148 165 7 STEP 41 K olector - 0.0033 kg / ton MIBC - 0.005 kg / ton 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, 2a, 3, contained 3 ¦, Potassium amyliiii xanthogenate 0.776 0.725 0.056 0.00181 1 1,2-epithioctane '0.710' 0.691 '0.093 »0.00325', mixture 50/50, 0.794, 0.766, 0.054 § 0.00177, amyl-% potassium xanthogen and 1,2-epithioctane 1 methyl sulfide '0.699' 0.697 '0.107' 0.00386 ', hexyl iiiii, Bleszanina 50/50, 0.790, 0.793, 0.056, 0.00169, potassium amyl xanthate 1 methyl hexyl sulride 1 iiiii no This is an example according to the invention 2 R-7 is a fractional fraction of recovery after 7 minutes ^ content denotes the fractional content of a specific metal found throughout mass collected in foam * 95% confidence area of the statistical error related to the experimentally obtained R-7 values for Cu in Table 1 is ± 0.010 * Thus, the statistical range of R-7 values for Cu in Table 1 obtained using amyl potassium xanthate is £ 0.776 0.010 or 0.766 to 0f786 * Whereas stat The actual error related to the R-7 values for Mo in Table 1 is +, 0.015 * Taking these limitations into account, it is clearly visible that the recoveries of Cu and Mo within 7 minutes using the collector mixture according to the invention exceed the recovery that could be expected in the same taking into account the weight average results obtained when using the individual ingredients individually, which proves the existence of synergism.

E r clade II * Copper-nickel ore foam flotation from Eastern Canada, Copper-nickel ore containing chalcopyrite, pentlandite and pyrrhotite was flotated using 0.0028 kg / ton of DOWFROTH 1263 frother and a collector of 0.28 kg / ton / methyl ether of polypropylene and butylene oxide with a molecular weight of 400 /. Sample series were transferred from a pretreatment feeder and placed in a kublsch for approximately 1,200 g. The contents of each kubl were used to measure the time-recovery relationship in a Denver cell equipped with an automatic paddle and a constant pulp level device, with the individual concentrates selected in the run 1.0, 3.0, 6.0 and 12.0 minutes * Chemicals were added over a 1 minute conditioning time, before the foam removal began * The addition of reagents was not a separate step * The individual concentrates were dried, weighed, milled and statistically representative samples for testing were prepared. The results are summarized in Table 2.6 148 165 Table 2, Collector Amyl and sodium xanthate 1 1,2-epithioctane * and dibutyl sulfide 1 50/50 mixture of 1,2-eplthiooctane and sodium amyl xanthate 1 1 50/50 ¦ mixture of dibutyl sulfide ii 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' Pyrotin R-12z '' 0.358 '1 0.247' 0.190, 0.344 0.245 1 no This is an example according to the invention R -12 There is a fractional part of recovery experimentally obtained after 12 minutes. All the 12-minute Cu recoveries shown in Table 2 are so high (they reach the theoretical limits of 1.0) that the statistical confidence limits * of the 95% level of confidence are not taken into account. the confidence of the R-12 for Ni values in Table 2 is +0.012. It is clearly visible that by using the mixture constituting the collector according to the invention, Ni recoveries are obtained that significantly exceed the recovery expected on the basis of the weight average results obtained when using each of the components individually, which confirms the occurrence of synergism.

Example III. Foam flotation of Pb / Zn / Cu / Ag complex ore from Centrelal Canada.

A homogeneous 1000 g sample of an ore containing galenite, sphalerite, chalco-pyrite and argentite was prepared. For each course of flotation, the sample was introduced into the pretreatment mill with 500 ml of tap water and 7.5 ml of SO2 solution. During 6.5 minutes of grinding, a batch containing 90% particles was obtained with a fineness of less than 200 mesh (75 µm). After milling, the contents were transferred to a cell equipped with automatic blades to remove planes and the cell attached to a standard Denver flotation mechanism.

A two-stage flotation was then performed. In the 1st stage, copper / lead / silver ore was recovered, and in the 2nd stage - zinc ore. To start the 1st stage of flotation, 1.5 g / kg of Na 2 CO 3 (pH 9 to 9.5) was added, followed by the collector (s). The slurry was then conditioned for 5 minutes with air exposure and agitation. It was further conditioned for 2 minutes with mixing only, after which the MIBC frother / standard dose of 0.015 ml / kg / was added * The concentrate was collected for 5 minutes of flotation, which was determined as a preliminary copper / lead concentrate * The second flotation step was to add 0.5 kg / ton CuSO. to remain in the cell after stage I. The pH was adjusted to 10.5 by adding quicklime, followed by a 5-minute conditioning period with mixing only. The pH was checked again and adjusted to 10.5 with lime. At this point, the collector (s) was added and again there was a 5 minute conditioning period with mixing only. The MIBC frother (standard dose 0.020 ml / kg) was then added. The concentrate was harvested for 5 minutes and designated as zinc pre-concentrate. Concentrate samples were dried, weighed and appropriate samples were prepared for testing using X-ray techniques. * Using the data from the analysis, the recovery and content values were calculated according to the mass balance formulas. The results are summarized in Table 3.148 165 Table 3, Pre-1, gear i,: H 1 2 ri 3 §1 Stage / preliminary / "Cu / Pb LZn 'Cu / Pb v * n (cu / Pb Izo Kole-, which ABAC, DD, CD 1 B 1 D Dose pH g / t '¦ 5 7.5 20 15 12.5 20 15 and 5 7.5 35 and 9'5 '10, 5, 9.5 '10, 5 and 9, 5 '10.5 Ag R-52 0.886 0.052, 0.778 'O, 103 ¦0.891 10.030 Content 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 Content * ¦ R -5 0.107, 0.794 10.077 0.136 and 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.

Contents * •, 0.48 'and 0.497 1 0.532, A - sodium ethyl xanthate B - dithiophosphate C - trilonocarbamate D - dihexyl sulfide 1 2 3 not to ethane example according to the invention R-5 means actual recovery after 5 minutes content * means fractional content of specific metal contained in the total mass collected in the foam * Table 3 shows the conditions for double trials which make it possible to compare the recoveries obtained with the collector mixture according to the invention with the recoveries obtained with the individual components used individually. / Pb / stage 1 / - course 2 using the D collector alone with Cu flotation / Pb / stage 1 / - course 3 using a mixture of D collectors? B results that the higher recovery of Ag, Cu and Pb was obtained using the collector mixture according to the invention * 95% statistical error confidence level for Ag is ± 0.01, for Cu ± 0.01 and for Pb ± 0.02 * From the comparison of Zn / step 11 (run 3 with Zn flotation (step 11) - run 2 also shows an obvious increase in Zn recovery due to the use of a mixture of collectors in relation to a single component. 95% confidence level of the statistical error for Zn is 0.01.

"" Other runs where single collectors were used in different steps are not shown in Table 3 because many components used individually simply do not produce results that are relevant for comparison. For example, collector B, used alone in step I for Cu and Pb, gives less than 0.500 recoveries.

Example IV * Foam flotation of Cu / Mo complex ore from South America. 500 g of Cu / Mo, containing sulphide minerals mainly copper and molybdenite, was placed in a 2.5 cm rod mill along with 257 g of deionized water and some quicklime. The mixture was then milled for 350 revolutions at 60 rpm. receiving a suitably subtle fragmentation.

The ground slurry was transferred to a 1500 ml Agitar flotation cell equipped with an automatic paddle displacement paddle system * The slurry was mixed at 1150 rpm * and the pH was adjusted to the appropriate value (shown in Table 4) with more lime or hydrochloric acid * Including The collector (y) (45 g / ton) was added to the flotation cell followed by a 1 minute conditioning period in which the DOWFROTH10 148 165 frother (34.4 g / ton) was added. After additional conditioning for 1 minute, air was pulled into the flotation cell at 4.5 L / min. and an automatic agitator was dragged to remove foam. After 0.5, 1.5, 3.0, 5.0 and 8.0 minutes, foam samples were taken. The samples were dried overnight in an oven along with the flotation waste. The dried samples were weighed, pulverized to the appropriate degree of dissolution and dissolved in acid for analysis on a DC Plasma Spectrograph. The results are summarized in Table 4.

Table 4 Waveform i ± 1 2 ¦ 3 i 4 i 5 i 6 Collectors ^ Isopropyl ethyl thionocarbamate \ j Ethyl octyl sulfide ^ Isopropyl ethyl thionocarbamate (Isopropyl sodium xanthate \ _ Ethyl octyl fthion Ethyl isopropyl sulfide) -octyl / Isopropyl-ethyl thionocarbamate 1 Isopropyl-sodium xanthate Vj Ethyl-octyl sulfide Dose 1 g / ton 1 22.7, 22.7 1 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 is the fractional recovery after 8 minutes. Shown in Table A all Cu recoveries achieved in 8 minutes are so high (reaching the theoretical limits of 1.0) that the statistical limits of the confidence interval are not taken into account.The 95% confidence level of the statistical error for Mo recovery in 8 minutes is +0.0 12. It can be clearly seen that the collector mixture according to the invention gives much higher Mo recover than the recoveries which would result from the values obtained for the individual components used separately. For example, the Mo recovery in Run 3 clearly exceeds that expected from the results of Runs 1 and 2. There is synergism here.

Patent claims 1. New collector for recovering from ores sulphide minerals containing non-ferrous metals or metal-containing sulphide minerals by means of foam flotation, characterized by the fact that it consists of / a / hydrophobic hydrocarbon monosulfide containing 4- 20 carbon atoms of formula R -SR, where R is aliphatic, cycloaliphatic or aralkyl, optionally substituted with one or more hydroxyl, cyano, halogen, ether, hydrocarbyl or carbon-2-dorothioether groups, R is aliphatic, cycloaliphatic , aromatic or their combinations, containing 5-11 carbon atoms, in addition, R and R can be treated to form a heterocyclic ring with sulfur, and sulfur is bound to an aliphatic or cycloaliphatic carbon atom and to / b / thiocarbonate, an alkyl thiophosphate, or mixtures thereof. 2. Collector according to claim 1, characterized in that the thiocarbonate is the compound of formula 2, in which R is a CU-D alkyl group, X is independently a sulfur or oxygen atom, M is an alkali metal cation as a thiocarbamate, it contains a compound with of formula 3, in which R is independently a C1 and n alkyl group, Y is a group - + 1 ~ 1U gg -SM, in which M is an alkali metal cation or the group OR, in which R is a group C. An alkyl and is an integer 1 or 2, b is an integer 0 or 10 1, where a + b → 2, and the thiophosphate is a compound of formula 4, in which R is independently a hydrogen atom, a C group, and n alkyl or an aryl group, M is a cation alkali metal or group OR, in which R is a C1Q alkyl group, X is an oxygen or sulfur atom * 3 * Collector according to Claim 1, characterized in that it consists of / a / about 10-90% by weight of hydrocarbon sulfide and / b / about 10-90% by weight of thiocarbonate, thiocarbamate, thiophospho an alkyl rhenium or mixtures thereof. Collector according to claim 3, characterized in that it consists of / a / about 20-80% by weight of hydrocarbon sulfide and / b / about 20-80% by weight of thiocarbonate, thiocarbamate, alkyl thiophosphate or their mixture * 5 * Collector according to Claim 1, characterized in that it comprises / a) a hydrocarbyl sulfide of the formula R -SR, in which R and R are independently an aliphatic, cycloaliphatic or aralkyl group optionally substituted with one or more hydroxyl, cyano, 3 3 3 or halogen groups , the group OR or SR, R is a hydrocarbyl radical, where R and R can join and form a heterocyclic ring, and as a thiocarbonate it contains a compound of formula 2, in which R is a C2-16 alkyl group, M is a sodium cation or Potassium, as the thionocarbamate is a compound of formula III, in which R is a CA alkyl group, as thiophosphate is a compound of formula IV, in which R is a C2-8alkyl or cresyl group * 1 2 6 * Collector according to claim * 5, characterized by that R i R are cycloaliphatic or aliphatic groups, optionally substituted with one or more hydroxyl, cyano, halogen, OR or SR groups, where R and R may join 7 8 to form a heterocyclic ring with S, R is a C1-9 alkyl group, R is a 10-10-2 alkyl group and R is a C2 "alkyl or cresyl group." 7. A collector according to claim 6, characterized in that it contains a hydrogen sulphide in which the total carbon content is is 6-16 carbon atoms * 1 2 8 * Collector according to claim 7, characterized in that R and R independently represent an alkyl or alkenyl group * 9 * Collector according to claim 8, characterized in that R is a methyl group or ethyl, and R represents a C 1-6 alkyl or C 1-6 alkenyl group * 10 * Collector according to claim 1 or 4, characterized by containing a dihydrocarbon sulfide of the formula / R / 3_nC / H / -SC / H / n- / R / 3_n »in which the groups R independently represent an aliphatic or cycloaliphatic group, an optionally substituted hydro group xyl, cyano, halogen, ether, hydrocarbyloxy or hydrocarbylthioether, where two groups of R may join and form a cyclic or heterocyclic ring with the S atom, n is an integer 0, 1, 2 or 3, or of the formula lc, where R is independently hydrogen, aryl, alkylaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, 3 cycloalkenyl, optionally substituted hydroxy, cyano, halogen, OR 3 3 4 or SR, where R is aliphatic or cycloaliphatic, and R is a hydroxyl, cyano, halogen, OR or SR group. Collector according to claim 10, characterized in that it consists of (a) hydrocarbon sulfide and (b) alkyl thiocarbonate which comprises an alkyl monothiocarbonate, Alkyl dithiocarbonate or alkyl trithiocarbonate * 1 2 12 * Collector according to claim 1, characterized in that R and R denote different hydrocarbon * carbon * residues 13 * Collector according to claim 1, characterized in that R contains 5-11 atoms 14 * Collector according to claim 1, characterized in that it contains sulfide of formula Ia, in which R is independently hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups optionally substituted with 3,3 hydroxy, cyano, halogen or OR or SR or is hydroxy, cyano, halogen, OR or SR • 148 165 (rM2 —c ^ c - (rM2 s FORMULA 1a R "C - CH2 \ / S MODEL 1c MODEL Ib 7 "R -X- C-SM MODEL 2 (RbL-NCY a I (H) k MODEL 3 R8K S \ I '" rN-CS "M + MODEL 3 as 8» 9 R -NH-C -OFT PATTERN 3b Rl0n SR ° \ 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 PRL. Circulation 100 copies.

Price PLN 400