FI80834B - New collectors for selective flotation of sulphide minerals - Google Patents

Description

1 80834

This invention relates to novel collectors for the recovery of metal-containing sulfide minerals and sulfidated metal-containing oxide minerals by foaming from ores.

Flotation is a process in which a mixture of finely divided mineral material, e.g., powdered ore, is treated suspended in a liquid so that some of this solid is separated from other finely divided materials, e.g., clays and similar ore-containing materials by feeding gas (or generating gas in situ). resulting in a foam-like mass with certain solids on the surface while the other solid components of the ore remain suspended (non-foaming). Flotation is based on the principle that the introduction of a gas into a liquid in which solid particles of various substances are suspended causes the gas bubbles to selectively adhere to the suspended solids so that the particles adhered to the gas become lighter than the liquid. For this reason, these particles are able to rise to the surface of the liquid and form a foam.

To improve the flotation process, various flotation agents have been mixed into the suspension. Such additives are classified according to their mode of action: collectors for sulphide minerals, e.g. xanthates, thionocarbamates and the like, Foams which stabilize the formation of foam, e.g. natural oils such as tall oil and eucalyptus oil, modifiers such as activating starters , e.g. copper sulphate, depressants, e.g. sodium cyanide, which tend to prevent the action of the collector on the mineral desired to remain in the liquid, i.e. to prevent the substance from rising to the surface and forming a foam, pH adjusting agents for optimum metallurgical results, e.g. lime , soda ash and equivalent to 5 vat.

It is important to keep in mind that additives of the type described above are selected according to the nature of the ore, the mineral (s) to be recovered and the other additives used in addition to said additives.

The implementation of the present invention does not require an understanding of the phenomena which make foaming a particularly valuable industrial step. However, the phenomena appear to be largely related to the selective affinity of the surface of solid particles suspended in a liquid containing a retained gas for both liquid and gas.

The flotation principle is applied in a number of mineral separation processes, including the selective separation of such metal sulfide minerals and minerals containing copper, zinc, lead, nickel, molybdenum and other metals from ferrous sulfide minerals such as pyrite and pyrrhotite.

Collectors commonly used in the recovery of metal-containing sulfide minerals or sulfidated metal-containing oxide minerals include xanthates, dithio-phosphates and thionocarbamates. Other aggregators generally considered useful in the recovery of metal-containing sulfide minerals or sulfated metal-containing oxide minerals include mercaptans, disulfide-dit (R-SS-R), and polysulfides (R- (S) nR), where n is 3 or greater.

The conversion of metal-containing sulfide minerals or sulfidated metal-containing oxide minerals to a more useful pure metal space often takes place by a melting process. Such smelting processes can generate li 3 80834 volatile sulfur compounds. These volatile sulfur compounds are often released into the outside air through chimneys or removed from these chimneys with expensive and laborious scrubbers. In nature, many non-ferrous sulfide-5 minerals or metallic oxide metals occur with ferrous sulfide minerals such as pyrite and pyrrhotite. When ferrous sulfide minerals and non-ferrous sulfide minerals and sulfidated metallic oxide minerals are simultaneously recovered by IQ foaming, excess sulfur is present which is released in the smelting process and thus there is too much sulfur in smelting operations. There is a need for a process that allows for the selective recovery of non-ferrous sulfide minerals and sulfated metallic oxide minerals without the recovery of ferrous sulfide minerals such as pyrite and pyrrotite.

Of the commercial collectors, xanthates, thionocarbamates and dithiophosphates are not capable of selective recovery of non-ferrous sulfide minerals in the presence of ferrous sulfide minerals. On the contrary, these collectors collect and recover all metallic sulfide minerals. Mercaptan collectors have an environmentally disturbing odor and their kinetics are very slow in the flotation of metal-containing sulfide minerals. When using disulfide and polysulfide collectors, the yield is low and the kinetics are slow. Mercaptans, disulfide and polysulfides are not commonly used for commercial purposes. In addition, mercaptans, disulfides, and polysulfides are unable to selectively recover non-ferrous sulfide minerals in the presence of ferrous sulfide minerals.

There is a need for a flotation collector that selectively recovers non-ferrous metal-containing sulfide minerals or sulfided, metal-containing oxide minerals in the presence of ferrous sulfide minerals such as pyrite and pyrrotite.

This invention relates to a flotation process for the selective recovery of non-ferrous metal-containing sulfide minerals or sulfidated metal-containing oxide minerals from ores. More particularly, this invention relates to a process for recovering metallic sulfide minerals or sulfided metallic oxide minerals from ore, characterized in that the ore in the form of an aqueous slurry is foamed in the presence of a foaming amount of a flotation collector consisting of 1Q hydrocarbons containing one or more monosulfurized the carbon atoms to which the sulfur atom (s) are attached are aliphatic or cycloaliphatic carbon atoms, and the total number of carbon atoms in the hydrocarbon portion of the collector is such that the collector is sufficiently hydrophobic to drive the metal-containing sulfide mineral or sulfidized under conditions such that the metallic sulfide mineral or sulfated metallic oxide mineral is recovered from the foam.

The novel collectors of this invention achieve a surprisingly high level of non-ferrous metal-containing sulfide minerals or sulfated, metal-containing oxide minerals; recovery and surprisingly good selectivity for such non-ferrous sulfide minerals and sulfated metallic oxide minerals when such metallic sulfide minerals or sulfated metallic oxide minerals co-exist with ferrous sulfide minerals. These ko-30 collectors are characterized by good recovery and good kinetics.

The novel collector of this invention is a hydrocarbon containing one or more monosulfide units in which sulfur atoms are attached to non-aromatic carbon atoms, i.e., aliphatic or cycloaliphatic carbon atoms.

II

5 80834 hin. By monosulfide unit is meant herein a unit in which a sulfur atom is attached to only two carbon atoms of the hydrocarbon moiety. As used herein, such hydrocarbon compounds containing one or more monosulfide units include said compounds substituted with a hydroxy, cyano, halogen, ether, hydrocarbyloxy and hydrocarbyl thioether moiety. As used herein, a non-aromatic carbon atom means a carbon atom that is not part of an aromatic ring.

10 Preferred hydrocarbons containing monosulfide units are hydrocarbons of the formula:

1 2 R -S-K

wherein R 2 is a methyl or ethyl group or a hydrocarbyl radical or a hydrocarbyl radical substituted by one or more hydroxy, cyano, halogen, ether, hydrocarbyloxy or hydrocarbyl thioether moieties; R 2 is an aliphatic, cycloaliphatic, aromatic - a group or a combination thereof having from 5 to 11 carbon atoms, 1 2 20 and R and R may form a heterocyclic ring structure with S provided that S is attached to an aliphatic or cycloaliphatic carbon atom and with the further proviso that the total number of carbon atoms in the sulfide collector is such that the sulfide collector 25 is sufficiently hydrophobic to drive the metal sulfide particles to the air-bubble interface.

1 2 R and R are preferably, independently of one another, an aliphatic, cycloaliphatic or aralkyl moiety unsubstituted or substituted by one or more hydroxy, cyano, halogen, OR or SR moieties, 3 12 in which R is a hydrocarbyl radical and R and R can form a heterocyclic ring with 1 2 S. More preferably, R and R are an aliphatic or cycloaliphatic moiety unsubstituted or substituted by one 35 or more hydroxy, cyano, halogen, OR or 3 12 SR moieties, and R and R may form a heterocyclic ring with S . In a preferred embodiment, R and R do not together with S form a heterocyclic 1 2 ring and R and R are alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl unsubstituted or substituted by one or more hydroxy, halo with a gene, cyano, OR or SR moiety where R is aliphatic or cycloaliphatic. In a most preferred embodiment, R and R are independently alkyl or alkenyl, especially R 1 is methyl or ethyl and R is a C 1 -C 4 alkyl or C 8 -C 4 alkenyl group. In the most preferred embodiment, R 1 and R 2 are not the same hydrocarbon moiety, i.e., the monosulfide is asymmetric.

3 R is preferably aliphatic or cycloaliphatic.

3 R is more preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl.

The total number of carbon atoms in the hydrocarbon portion of the hydrocarbon monosulfide collector must be such that the sulfide collector is sufficiently hydrophobic to drive particles of metal-containing sulfide mineral or sulfidated metal oxide mineral to the air-bubbles interface. The total number of carbon atoms in the hydrocarbon monosulfide collector is preferably such that the minimum number of carbon atoms is 4, more preferably 6, and most preferably 8. The maximum number of carbon atoms is preferably 2Q, more preferably 16, and most preferably 12.

Examples of cyclic compounds useful in this invention include those having the following formulas:

<R4 <, C-C- (R '), and R5 S

2 wherein R 1 and R 2 * are independently hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxy, cyano, halogen.

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7 80834 3 3. .

ni, OR or SR, of which aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl may be optionally substituted with hydroxy, 3.3 cyano, OR or SR and the like and R is ra or branched alkylene, alkenylene or alkynylene unsubstituted or substituted by hydroxy, cyano, halogen, OR or SR, provided that at least one R 'is not hydrogen.

In another preferred embodiment of this invention, the assemblers of this invention are of the formula: (R 6) 3 -nC (H) nSC <H> n <R 6> 3-n wherein R 1 is independently hydrocarbyl or hydrocarbyl substituted with hydroxy, cyano with a halogen, halogen, hydrocarbyloxy or hydrocarbylthioether moiety and two R moieties may 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 number of carbon atoms in the hydrocarbon portion of the collector is such that the collector is sufficiently hydrophobic to drive particles of metal-containing sulfide mineral or sulfidated metal-containing oxide mineral to the air-bubbles interface.

R 1 is preferably an aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl unsubstituted or substituted by a cyano, hydroxy, halogen, OR 1 or SR 3 moiety, wherein R is as defined above. More preferably, R is an aliphatic or cycloaliphatic moiety unsubstituted or substituted by a hydroxy, cyano, halo gene, aliphatic ether, cycloaliphatic ether, aliphatic thioether or cycloaliphatic ether moiety. Even more preferably, R is an alkyl, alkenyl, cycloalkyl or cycloalkenyl moiety. Most preferably, one ~ c (H) n (R 2) 3 n is a methyl or ethyl moiety and the other is 8,80834

C 1 -C 4 alkyl or C 1 -C 4 alkenyl moiety. n is preferably 1, 2 or 3 and more preferably 2 or 3.

The preferred monosulfide unit-containing carbohydrate of formula R-SR, wherein R and R are as defined above, is prepared by standard methods in the art, e.g., by reacting R-H with compound 1 -R-SH, wherein R and R denote as above.

Examples of compounds within the scope of this invention are metyylibutyylisulfidi, metyylipentyylisulfi di-1Q, metyyliheksyylisulfidi, metyyliheptyylisulfidi, methyl tyylioktyylisulfidi, metyylinonyylisulfidi, metyylidekyy-methyl sulphide, metyyliundekyylisulfidi, di-metyylidodekyylisulfi, metyylisyklopentyylisulfidi, metyylisykloheksyylisul-sulfide metyylisykloheptyylisulfidi, methylcyclooctyl ^ 5-octyl sulfide, etyylibutyylisulfidi, etyylipentyylisulfidi, etyyliheksyylisulfidi, etyyliheptyylisulfidi, etyyliok-sulfide, etyylinonyylisulfidi, etyylidekyylisulfidi, etyyliundekyylisulfidi, etyylidodekyylisulfidi, etyylisyk-lopentyylisulfidi, etyylisykloheksyylisulfidi, etyylisyk-2q loheptyylisulfidi, etyylisyklo-oktyylisulfidi, propyl butylsulphide, propyylipentyylisulfidi, propyyliheksyylisulf -amide, propyyliheptyylisulfidi, propyylioktyylisulfidi, propyylinonyylisulfidi, propyl dececyl sulfide, propyl undecyl sulfide, propyl dodecyl sulfide, propyl cyclo-pentyl sulfide, propyl lisykloheksyylisulfidi, propyl sykloheptyylisulfidi, propyylisyklo-oktyylisulfidi, di-butylsulphide, butyylipentyylisulfidi, butyyliheksyyli sulfide, butyyliheptyylisulfidi, butyylioktyylisulfidi, butyylinonyylisulfidi, butyylidekyylisulfidi, butyyliunde-30 sulfide, butyylidodekyylisulfidi, butyylisyklopen-sulfide, butyylisykloheksyylisulfidi, butyylisyklo-heptyylisulfidi, butyylisyklo-oktyylisulfidi, dipentyylisulf idi, pentylhexyl sulfide, pentylheptyl sulfide, pentyl octyl sulfide, pentyl nonyl sulfide, pentyl 35 decyl sulfide, pentyl undecyl sulfide, pentyl dodecyl sulfide, pentyl cyclopentyl sulfide, pentyl cyclo

II

9 80 834 heksyylisulfidi, pentyylisykloheptyylisulfidi, pentyl, cyclo-oktyylisulfidi, diheksyylisulfidi, heksyyliheptyyli sulfide, heksyylioktyylisulfidi, heksyylinonyylisulfidi, heksyylidekyylisulfidi, heksyyliundekyylisulfidi, hexyne-5 lidodekyylisulfidi, heksyylisyklopentyylisulfidi, hexyne-lisykloheksyylisulfidi, heksyylisykloheptyylisulfidi, hex-yylisyklo-oktyylisulfidi, diheptyylisulfidi, heptyyliok-sulfide , heptyylinonyylisulfidi, heptyylidekyylisul-sulfide heptyyliundekyylisulfidi, heptyylidodekyylisulfidi, IQ heptyylisyklopentyylisulfidi, heptyylisykloheksyylisulfidi, heptyylisykloheptyylisulfidi, heptyylisyklo-oktyylisulfi-oxide, dioctyl sulfide, oktyylinonyylisulfidi, octyl-sulfide, oktyyliunddkyylisulfidi, oktyylisodekyyli sulfide, oktyylisyklopentyylisulfidi, oktyylisykloheksyyli-15 sulfide, oktyylisykloheptyylisulfidi, oktyylisyklo-octyl sulphide, octylcyclophenyl sulphide, dinonyl sulphide, nonyl dececyl sulphide, nonyl undecyl sulphide, nonyl dodecyl sulphide fidi, nonylcyclopentyl sulfide, nonyl-cyclohexyl sulfide, nonyl-cycloheptyl sulfide, nonyl-20-cyclooctyl sulfide, didecyl sulfide, decylundecyl sulfide, decylisecyl sulfecyl, decyl-cyclopentyl sulfyl, decyl-cyclopentylsulf More preferred sulfides are methylhexyl sulfide, methylheptyl sulfide, methyl octyl sulfide, methyl nonyl sulfide, methyl dececyl sulfide, ethyl hexyl sulfide, ethyl heptyl sulfide, dihydroxy sulfyl, ethyl diisyl sulfide, ethyl dinyl sulfide, ethyl dide di] di

Hydrocarbon here means an organic compound containing carbon and hydrogen atoms. By hydrocarbon is meant the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aromatics, aliphatic and cycloaliphatic aralkanes, and alkyl-substituted aromatics.

10 80834

By aliphatic is meant herein straight or branched and saturated and unsaturated hydrocarbon compounds, i.e. alkanes, alkenes or alkynes. By cyclo-aliphatic is meant herein saturated and unsaturated cyclic hydrocarbons, i.e. cycloalkenes and cycloalkanes.

Cycloalkane means an alkane having one, two, three or more cyclic rings. By cycloalkene is meant mono-, di- and polycyclic groups having one or more double bonds.

Hydrocarbyl as used herein means an organic radical containing carbon and hydrogen atoms. By hydrocarbyl is meant the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cyclo-alkenyl, aryl, aliphatic and cycloaliphatic Aral-alkyl and alkaryl. By aryl is meant herein biaryl, biphenylyl, phenyl, naphthyl, phenanthrenyl, anthracenyl and two aryl groups interposed with an alkylene group. Alkaryl as used herein means an alkyl, alkenyl or alkynyl-substituted aryl substituent, wherein aryl is as defined above. Aralkyl as used herein means an alkyl group in which aryl is as defined above.

C 1 -C 20 alkyl means straight or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl; , tridecyl, tetradecyl, pentadeyl, hexadecyl, heptadecyl, octadecyl, nonadeyl and eicosyl.

Halogen as used herein means chlorine, bromine or iodine groups.

The process of the present invention is useful for recovering metallic sulfide minerals and sulfided metallic oxide minerals by foaming from ores. By ore is meant herein a material taken from the ground and the ore comprises the desired metallic minerals in admixture with the side rock.

li n 80834

By side stone is meant here that part of the material which is worthless and has to be separated from the desired metal-containing minerals.

In a preferred embodiment, metal-containing sulfide minerals of tal-5 are taken. In a more preferred embodiment of the present invention, metal sulfide-containing minerals containing copper, nickel, lead, zinc or molybdenum are recovered. Preferred metal sulfide-containing minerals are also mine-10 radals, which have good natural hydrophobicity in the non-oxidized state. By the phrase "non-oxidized hydrophobicity" is meant a freshly ground mineral or fresh-surfaced mineral that tends to float on the surface without the addition of a collector.

15 Ores to which these compounds may be applied include sulphide mineral ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and mixtures thereof. Examples of metallic sulfide-20 minerals that can be enriched by the flotation process of this invention include copper-containing minerals such as covellite (CuS), chalcosite (Cu2S), chalcopyrite (CuFeS2), vallerite (Cu ^ e ^ Sy or Cu ^ Fe ^ Sy ), bornite (Cu3-FeS ^), cubanite (Cu ^ Fe ^ S ^), enargite 25 / Cu ^ (As- ^ Sb) S ^ 7i tetrahedrit (Cu3SbS2), tennantite (Cu ^ As ^ S ^) / brocantite (OH) gSO 4, antkererite / Cu 2 SO 2 (OH) ¢ 7, famatinite / Cu 2 (SbAs) S lead-containing minerals such as lead flux (PbS); antimony-containing minerals such as stibnite 30 (Sb2S3); zinc-containing minerals such as sphalerite (ZnS); silver-bearing minerals such as stefanite (Ag2SbS2) and argentite (Ag2S); chromium-containing minerals such as daubrelite (FeSCrS 2); nickel-containing minerals such as pentlandite (iFeNiJgS ^); molybdenum-containing minerals such as molybdenite (MoS2) and platinum and i2 80834 palladium-containing minerals such as cooperite (PMAsS). Preferred metal-containing sulfide minerals are molybdenite (MoS2), chalcopyrite (CuFeS2) * lead (PbS), sphalerite (ZnS), bornite (CuFeS2) and pentlan-5 dite / (FeNi) gSg7.

Sulfidated metal-containing oxide minerals are minerals that are treated with a sulfidation chemical so that such minerals acquire the properties of a sulfide mineral, whereby the minerals can be recovered by flotation using collectors to recover the sulfide minerals. Sulfidation results in oxide minerals of a sulfide nature. Oxide minerals are sulfidated by contacting them with compounds that react with the minerals to form a sulfur bond. Such methods are known in the art. Such compounds include sodium hydrosulfide, sulfuric acid and corresponding sulfur-containing salts such as sodium sulfide.

Sulphidated metal-containing oxide minerals to which this method is applicable include oxide minerals containing copper, aluminum, iron, tungsten, molybdenum, magnesium, chromium, nickel, titanium, manganese, tin, uranium, and mixtures thereof. Examples of metal-containing oxide minerals that can be enriched by the deposition process of this invention include copper-containing minerals such as cuprite (Cu 2 O), Teno-rite (CuO), malachite 7 ~ (Cu 2 OH) 2 C® 3 ^ 'azurite-tt; · - / Cu 3 (OH) 2 (COg) 27, attackamide / Cu2Cl (OH) ^ 7 / chrysococcus (CuSiOg); aluminum-containing minerals such as corundum; zinc-30-rich minerals such as zincite (ZnO) and smithso-rivet (ZnCOg); tungsten-containing minerals such as tungsten (Fe, Mn) WO; nickel-containing minerals such as bun-senite (NiO); molybdenum-containing minerals such as wulfenite (PbMoO 2) and powellite (CaMoO 2); ferrous minerals such as hematite and magnetite; chromium silicon i3 80834 other minerals such as chromite (FeOC2O2); ferrous and titanium-containing minerals such as ilmenite; magnesium and aluminum-containing minerals such as Spinelli; iron-chromium-containing minerals such as chromite; titanium-containing minerals such as rutile; manganese-containing minerals such as pyrolucite; tin-containing minerals such as cassiterite and uranium-containing minerals such as uranium rivet and uranium-containing minerals such as pitch flash * * 205 ^ U3 ° 8 ^ 3a (UO ^ ni ^ O).

The use concentration of the collectors of this invention can be anything that achieves the desired recovery of the desired minerals. The application concentration depends in particular on the mineral (s) to be recovered in each case, the concentration of the ore to be foamed, the desired quality of the mineral to be recovered and the mineral to be recovered in each case. The concentration of the collectors of this invention is preferably 0.001-1.0 kg per ton of ore, more preferably about 0.010-0.2 kg of collector per ton of ore to be foamed.

In the flotation process of the present invention, flotation agents are preferably used. Any blowing agent known in the art is suitable which results in the recovery of the desired mineral.

The blowing agents useful in this invention are all blowing agents known in the art with which the desired mineral can be recovered. Examples of such blowing agents are C 1 -C 0 alcohols, pine oils, cresols, C 1 -C 4 alkyl ethers of polypropylene glycols, dihydroxylates of polypropylene glycols, glycols, fatty acids, soaps, alkylaryl sulfonates. In addition, mixtures of such blowing agents can also be used. All blowing agents that promote ore separation by flotation can be used in this invention.

In accordance with the present invention, it is further possible to use the i480834 collectors of the present invention in admixture with other collectors known in the art. Collectors known in the art that can be used in admixture with the collectors of this invention are collectors that achieve the desired recovery of the desired mineral. Useful in this invention are examples of collectors alkyylimonotiokarbonaatit, alkyyliditiokarbonaatit, alkyl-litritiokarbonaatit, dialkyyliditiokarbonaatit, alkylthio nokarbamaatit, dialkyylitioureat, monoalkyyliditiofosfaa- "LQ sulfonates, dialkyl, and diaryldithiophosphate, dialkyylimono-thiophosphates, dialkyl, and diaryylitiofosfonyylikloridit, dialkyl, and diaryyliditiofosfonaatit, alkyylimerkaptaa-nit , xanthogen formates, xanthate esters, mercaptobenzothiazoles, fatty acids and salts of fatty acids, alkyl-sulfuric acids and their salts, alkyl and alkaryl sulfonic acids and their salts, alkylphosphoric acids and their salts, alkyl and aryl sulphosate, amines, secondary amines, tertiary amines, quaternary ammonium salts, alkylpyridinium salts, guanidine and alkylpropylenediamines.

Selected embodiments. The following examples are intended to illustrate the invention without, however, limiting the scope of the invention. Unless; 25 unless otherwise stated, all parts and accessories are by weight.

The performance of the described flotation methods is expressed in the following examples by the flotation rate constant and the recovery rate after an infinitely long time 3q. These values are calculated from the formula »" R * 11 - Hfe-i where is the mineral recovery quotient at time t, 35 k is the rate constant of the recovery rate and is the mineral

II

is 80834 recovery fraction after infinitely long time. The recovery rate at different time points was determined experimentally and these values were placed in the equation and obtained and k. The above formula is explained in Klimpel, 5 "Selection of Chemical Reagents for Flotation", Chapter 45, pp. 907-934, Mineral Processing Plant Design, 2nd Edition, 1980, ΑΙΜΕ (Denver).

Esimerkki_J.

Flotation of Copper-Containing Sulphide Mineral 10 This example tested the ability of several collectors of the present invention to foam copper-containing sulfide minerals. 500 g of Western Canadian copper ore, a relatively good quality, slightly pyrite-containing calcopyrite ore, was placed in a rod mill with a length of 2.5 cm of rods with 257 g of deionized water and ground 420 rpm at 60 rpm and a particle distribution was obtained, where 25% was less than 100 mesh. Lime was also added to the rod mill, the amount of which depended on the desired pH in the subsequent flotation step. The powder-20 slurry was transferred to a 1500 ml cell of an Agitair flotation machine. The flotation cell was stirred at 1150 rpm and the pH was adjusted to 8.5 by adding more lime.

A collector (8 g / ton) was added to the flotation cell, followed by a one minute conditioning time, and the flotation agent DOWFROTH 250 (18 g / ton) was added to this residue.

With one minute still standardized, the air supply to the flotation cell was started at a rate of 4.5 liters per minute and an automatic foam peeler was started. Foam samples were taken at 0.5, 1.5, 3, 5, and 8 minutes. Foam-30 samples and flotation waste were dried in an oven overnight. The dried samples were weighed, divided into suitable samples for analysis, ground to a suitable fineness and dissolved in acid for analysis. Samples were analyzed by DC plasma spectrograph. The results are summarized in 35 Tables I.

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Example_ 2 5 Flotation of copper-molybdenum ore

The ore containing homogeneous chalcopyrite and molybdenum mineral was bagged so that each bag contained 1200 g. In pre-foaming, a batch of 1200 g and 800 ml of tap water were ground for 14 minutes in a ball mill with 10 balls of different sizes (particle distribution comprised about 13% + 100 mesh). This slurry was transferred to a 1500 ml Agi-tair flotation cell equipped with an automatic peeler. The pH of the slurry was adjusted to 10.2 with lime. No other adjustments were made during the test. The standard wetting agent was methyl isobutylcarbinol (MIBC). The four-step pre-frothing diagram was as follows:

Phase 1:

Collector = 0.0042 kg / ton MIBC = 0.015 kg / ton, 2o = conditioning = 1 minute, flotation, concentrate recovery = 1 minute Step 2:

Collector = 0.0021 kg / ton MIBC = 0.005 kg / ton, 25 = standardization = Q, 5 minutes, flotation, concentrate recovery = 1.5 minutes Step 3:

Collector = 0.0016 kg / ton MIBC = 0.005 kg / ton, 30 = conditioning = 0.5 minutes, flotation, concentrate recovery = 2.0 minutes Step 4:

Collector = 0.0033 kg / ton MIBC = 0.005 kg / ton, 35 = standardization = 0.5 minutes, flotation, concentrate recovery = 2.5 minutes 2o 80834

The results are summarized in Table II.

Table II

Copper / molybdenum ore from western Canada

Collector Dosage Cu ffolyb. Avg. Avg. Avg. 2 g / t R-71 R-71 Cu content ^ Mo content2 Fe content A 11f2 0.776 0.725 0.056 0.00181 0.254 B 11.2 0.710 0.691 0.093 0.00325 0.149 B 6.7 0.730 0.703 0, .118 0.00390 0.155 B 22.4 0.756 0.760 0.105 0.00-346 0.161 10 c 11.2 0.699 0.697 0.107 0.00386 0.164 C 22r4 0.723 0.723 0.112 0.00392 0.142 A = potassium amyl xanthate, not Example B of this invention = 1.2- epithiooctane 15 C = hexylmethyl sulfide 1 = R-7 is the experimental partial recovery after 7 minutes 2 = the proportion of said metal in the total weight recovered from the foam The use of the collectors of this invention has a significant effect on both the ) and a significant reduction in pyrite in the concentrate as measured by the reduction in the Fe content of the product. This is true regardless of the dosage used. This means lower feed to the smelter by weight and less sulfur emissions per unit of metal produced.

Example 3 Flotation of Western Canadian copper-nickel ore rich in iron sulfide mineral pyrrothi; in the form of a tin.

A series of samples were taken from the pre-frothing-35 bone-conducting feed channels of the plant and the samples were placed in n 2i 80834 buckets so that each received about 1200 g of solids. The slurry contained chalcopyrite and pentlandite mineral. The contents of each bucket were then run with a time-recovery profile in a Denver cell using an automatic peeler and an automatic slurry leveling device, and individual concentrates were collected at 1.0, 3.0, 6.0, and 12.0 minutes. Collectors were added all at once and allowed to standardize for one minute before defoaming was initiated. The dosing of the collectors was 0.028 kg / -10 tons of flotation feed. Individual concentrates were dried, weighed, ground, and statistically representative samples of the concentrates were prepared for analysis. Recoveries and total major fractions as a function of time were calculated using standard material balance equations 15.

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li 23 80834 The collectors of the present invention achieve copper recovery comparable to that achieved with sodium methyl xanthate; the collectors of this invention achieve much higher flotation rates.

The collectors of this invention achieve lower nickel recovery than sodium xylantate, but also much lower recovery of unwanted ferrous sulfide pyrrhotite. This is evidenced by the R-value of pyrrotite and the increase in the selectivity of the nickel sulphide mineral, by about 50% compared to the undesired ferrous sulphide mineral pyrrothite.

Example 4

Foaming of Central Canadian Pb-Zn-Cu-Ag Multimetal Ore 15 Homogeneous 1000 g ore samples were prepared.

The ore contained lead, sphererite, chalcopyrite and argentite minerals. In each flotation run, a sample, 500 mL of tap water, and 7.5 mL of SC 2 solution were added to the tan condenser. A grinding time of 6.5 minutes was used to prepare bait with 90% of the particles less than 200 mesh (75 microns). After grinding, the contents of the mill were transferred to a cell equipped with an automatic foam peeler and the cell was connected to a standard Denver flotation device.

25 A two-stage flotation was then performed. In step I, copper-lead-silver pre-foaming was performed and in step II zinc pre-foaming. To initiate the flotation of step I, 1.5 g / kg Na 2 O 2 (pH 9-9.5) was added and then the collector (s) was added. The slurry was then conditioned for 5 minutes with air and stirring. This was followed by a 2 minute conditioning during which time only mixing was performed. MIBC blowing agent (then a standard dose of 0.015 ml / kg) was then added. The concentrate was recovered after 5 minutes of flotation and was designated copper-lead-35 preconcentrate.

24 80834

Step II was performed by adding 0.5 kg / t CuSO 4 · to the cell waste of step I. The pH was then adjusted to 10.5 by adding lime. This was followed by conditioning for 5 minutes, during which time only mixing was performed.

The pH was then checked and adjusted back to 10.5. At this point, the collector (s) was added, followed by conditioning for 5 minutes, which included mixing alone. MIBC blowing agent (then a constant dose of 0.020 ml / kg) was then added. The concentrate was recovered after 5 to 10 minutes and was designated zinc preconcentrate.

Concentrate samples were dried, weighed, and appropriate samples prepared for X-ray analysis. Yields and proportions were calculated from the analytical values using conventional material balance equations.

In addition to the procedure described above, experiments were also performed in which a lower pH was used in step I (not added when the pH became 8.5) and only enough lime was added in step II to a pH of 9.5. Even at lower pH, 0.3 kg / ton CuSO 4 was added.

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27 80834

This is a complex flotation, which shows, quite significantly, that a complex mixture of three commercial, optimized collectors can be replaced by the collectors of the present invention to achieve the same metal recovery and proportion at normal pH and normal CuSO 2. , which have been chosen as optimal for commercial collectors (Experiments 1, 2, 3). The corresponding experiments (4, 5, 6) at lower pH and with a lower amount of CuSO 4 also show that the co-collectors of the present invention are able to significantly improve the proportions of metals compared to the three commercial collectors. From the point of view of plant operation, such a result can mean a significant adjustment of lime and CuSO 4 costs. (The main reason for adjusting the pH to 10.5 in Step I and 9.5 in Step II was to improve selectivity. The main reason for the addition of CuSO 4 was to improve zinc recovery and maintain the proportion). It should be noted that at times (5, 6) using a lower amount of CuSO 4, the collectors of the present invention actually improved the zinc recovery 20 and considered the proportion good.

I use the example)

Flotation of copper-molybdenum ore

To a rod mill with rods of 2.5 cm were added 500 g of South American copper-molybdenum ore: 25 and 257 g of deionized water and a prescribed amount of lime.

The mixture was ground 360 rpm at 60 rpm to obtain a particle distribution of suitable fineness (about 25% less than 100 mesh). The ground slurry containing various copper-containing sulfide minerals and molybdenite-30 was transferred to a 1500 ml cell of an Agitair flotation machine. The flotation cell was stirred at 1150 rpm and the pH was adjusted to 8.5 by the addition of either lime or hydrochloric acid.

A collector (45 g / ton) was added to the flotation cell and then conditioned for one minute during which time the flotation agent DOWFROTH® 250 (36.4 g / ton) was added. After a further minute of standardization, the air supply to the foam cell was started at a rate of 4.5 liters per minute and an automatic foam peeler was started. Foam samples were collected after 0.5, 1.5, 3, 5 and 8 minutes. Foam samples and flotation waste were dried overnight in an oven. The dried samples were weighed, divided into suitable samples for analysis, ground to ensure appropriate fineness, and dissolved in acid for analysis on a 10 DC plasma spectrograph. The results are summarized in Table V.

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The collectors of this invention significantly improve the recovery of molybdenum compared to the standard reagent, although the recovery of copper is lower. There is also a very significant, desired increase in the recovery of ferrous sulfide minerals.

Example ^ 6

Copper ore flotation

By repeating the procedure of Example 1 using a relatively pure ore containing chalcopyrite, which contained little pyrite and was obtained from a different location in the same well as in Example 1, the results summarized in Table VI were obtained.

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Claims (5)

32 80834 A process for recovering metallic sulfide minerals or sulfided metallic oxide minerals from ore, characterized in that the ore in the form of an aqueous slurry is foamed in the presence of a foamable amount of a flotation collector, wherein the collector consists of a monosulfide of the formula R 1 is -S-R 2 wherein R 1 is methyl, ethyl, epoxy or a group of formula -CH-CH- O or a hydrocarbon radical substituted by one or more cyano, halogen, ether or alkyl thioether, and R 2 is an aliphatic, cycloaliphatic or aromatic group or a combination thereof having from 5 to 11 carbon atoms, wherein R 1 and R 2 may combine to form an epithio ring structure provided that R1 and R2 are not the same hydrocarbon radicals and the sulfur atom is attached to aliphatic or cycloaliphatic carbon atoms, with the further proviso that the total carbon content of the sulfide collector is 5 to 20 carbon atoms, such that a metallic sulfide mineral or the metallic oxide mineral is recovered from the foam. Process according to Claim 1, characterized in that the total carbon content of the sulphide collector is 5 to 10 carbon atoms. Process according to Claim 1, characterized in that R 1 is methyl or ethyl and R 2 is C 6-10 alkyl or C 6-10 alkenyl. 33 80 8 34 Process according to Claim 1, characterized in that the sulphide collector is present at a concentration of 0.001 to 1.0 kg collector / ton of ore to be foamed. Process according to Claim 1, characterized in that the collector has the formula (R 4 -C-CMR 1) 2 S 10 in which R 1 and R 4 independently of one another denote hydrogen, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cyano, halogen, OR 3 or SR 3, wherein aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl may be optionally substituted by cyano, OR 3 or SR 3, wherein R 3 is a hydrocarbon radical, provided that at least one R1 is not hydrogen. 34 808 34