CN1011765B - Froth Flotation Method for Sulfide Minerals - Google Patents

Abstract

Selective froth flotation for the recovery of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals in ores, in particular for the recovery of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals in ores, including ores in the state of aqueous Froth flotation is carried out in the presence of a large number of floating flotation collectors. The collector is a hydrocarbon containing one or more monosulfur chain members, wherein the C bonded to the sulfur atom is an aliphatic hydrocarbon or alicyclic hydrocarbon C. The collector The total carbon content of the hydrocarbon fraction renders the collector sufficiently hydrophobic to drive metal-bearing sulfide mineral or sulfide metal-bearing oxide mineral particles to the air/bubble interface and be recovered in the froth.

Description

This invention relates to froth flotation for the recovery of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals from ores using novel collectors.

Flotation is a method of treating a mixture of ground mineral solids, for example, using the property that some of the solid particles of the ore are suspended in a liquid to separate the powdered ore from other ground solid particles, such as clay or ore. Separated from other analogues, the method is to introduce a gas (or a gas provided on site) into the liquid, so that the upper part of the liquid generates a foamy substance containing some solid particles, leaving suspended (non-foamed) other ores solid component. The principle of flotation is to introduce a gas into a liquid containing suspended solid particles of different substances, causing some gas to attach to some suspended solids but not to other suspended solids, so that the particles attached to the gas are more Liquid is light. Thus, these particles rise to the top of the liquid to form foam.

Mix various flotation agents with the suspension to improve the foam method. These additives are divided into: collectors, used for sulfide minerals, including xanthates, thionocarbamate, etc.; foaming agents, which impart the property of forming stable foams, such as natural oils, such as pine oil and eucalyptus oil; modifiers, such as activators, such as copper sulfate, used to initiate flotation in the presence of collectors, such as copper sulfate; inhibitors, such as cyanide Sodium chloride, which helps to prevent the collector from interacting with the minerals that you want to keep in the liquid, thereby preventing the entrainment of inclusions to become part of the foam; PH value regulator, to achieve the best metallurgical effect, such as lime, soda ash etc.

It is important to remember that the above-mentioned types of additives are selected according to the nature of the ore, the nature of the minerals sought to be recovered, and the nature of other additives that are also used in the mixed system.

It is not essential to the practice of the present invention to understand some of the phenomena that make flotation a valuable commercial operation, however, the occurrence of these phenomena is related to the selective affinity of the surface of ground solid particles suspended in a liquid containing entrained gas to liquid and gas. are closely related.

This flotation principle is applicable to a large number of mineral separation methods to selectively separate metal sulfide minerals containing copper, zinc, lead, nickel, molybdenum and other metals from iron-containing sulfide minerals, such as pyrite and pyrrhotite is also one of them.

To recover metal-containing sulfide minerals or sulfide metal-containing oxide minerals, commonly used collectors are xanthate, dithiophosphate and thionocarbamate. Recovery of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals, other effective collectors are generally considered to be mercaptans, disulfides (R-SS-R) and polysulfides [R-(S) _n -R] , where n is 3 or greater.

the conversion of metal-bearing sulfide minerals or sulfide metal-bearing oxide minerals into more useful pure metals, often by smelting, a process that results in the formation of volatile sulfur compounds that are often released into the atmosphere through chimneys or removed from these chimneys by expensive, elaborate scrubbers. Of course, many ferrous metal-bearing sulfide minerals or metal-bearing oxide minerals are found in iron-bearing sulfide minerals such as pyrite and pyrrhotite.

When flotation is used to recover sulfide minerals containing ferrous metals and sulfide metal-containing oxide minerals together with iron-containing sulfide minerals, the sulfur content is too large and is released during the smelting process, resulting in Undesirably large amounts of sulfur are present. because Accordingly, there is a need for a method of selectively recovering ferrous metal-containing sulfide minerals and sulfide metal-containing oxide minerals without recovering iron-containing sulfide minerals such as pyrite and magnetite.

Among commercial collectors, xanthate, thionocarbamate, and dithiophosphate cannot selectively recover ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals. On the contrary, These collectors enrich and recover all metal-bearing sulfide minerals. Mercaptan collectors have an environmentally undesirable odor and are slow in flotation of metal-bearing sulfide minerals. Disulfides and polysulfides, when used as collectors, give low recoveries due to their slow movement. Therefore, mercaptans, disulfides and polysulfides are generally not used in industry. In addition, mercaptans, disulfides, and polysulfides cannot selectively recover ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals.

There is a need for a collector that can selectively recover ferrous metal-containing sulfide minerals and sulfide metal-containing oxide minerals in the presence of iron-containing sulfide minerals, such as pyrite and pyrrhotite.

The invention relates to a froth flotation method for selectively recovering ferrous metal-containing sulfide minerals or sulfide metal-containing oxide minerals from ores. In particular, the present invention relates to a process for the recovery of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals from ores comprising froth flotation of the ore in the A collector is a hydrocarbon containing one or more monosulfur chain members, wherein the carbon atoms bonded to the sulfur atom are those of aliphatic or alicyclic hydrocarbons, and the total carbon content of the hydrocarbon part of the collector is such that the The absorbent has sufficient hydrophobic properties to cause particles of metal-bearing sulfide minerals or sulfide metal-containing oxide minerals to be driven to the air/bubble interface, under these conditions, metal-bearing sulfide minerals or sulfide metal-containing oxide minerals in Recycled from foam.

The effect of the new collector of the present invention is that the recovery rate of sulfide minerals containing ferrous metals or sulfide metal-containing oxide minerals is very high, and when metal-containing sulfide minerals or sulfide metal-containing oxide minerals appear in iron-containing sulfide In minerals, it has very high selectivity to ferrous metal-containing sulfide minerals and sulfide metal-bearing oxide minerals. These collectors showed good recovery and good kinematic performance.

The novel collector of the present invention is a hydrocarbon containing one or more monosulfide chain members, wherein the sulfur atoms of the sulfide chain members are bonded to the carbon atoms of non-aromatic hydrocarbons, i.e. the carbon atoms of aliphatic hydrocarbons or alicyclic hydrocarbons combine. Monosulfur mers are referred to here as -S-, in which the sulfur atom is bonded to only two carbon atoms of the hydrocarbon moiety. Hydrocarbon compounds containing one or more monosulfide mers as used herein include compounds substituted with hydroxy, cyano, halogen, ether, oxy and sulfide moieties. Non-aromatic carbon atoms refer here to carbon atoms that are not part of an aromatic ring.

Preferred hydrocarbons containing monosulfide chain members include hydrocarbons whose structural formula is consistent with R-S-R.

in

R ¹ and R ² are each independently a hydrocarbon group or a hydrocarbon group substituted with one or more hydroxyl, cyano, halogen atom, ether, alkoxy or alkyl sulfide moieties;

Wherein R ¹ and R ² are combined with S to form a heterocyclic structure; but S must be bonded to the carbon atoms of aliphatic hydrocarbons or alicyclic hydrocarbons; the total carbon content of the sulfide collector must make the sulfide collector have enough Hydrophobic properties to cause metal sulfide particles to be driven to the air/bubble interface.

Preferably R ^{and R} are each unsubstituted or aliphatic, cycloaliphatic or aralkyl substituted with one or more hydroxyl, cyano, halogen, ^OR or ^SR moieties , where ^R3 is a hydrocarbon group; here ^R1 and ^R2 can combine with S to form a heterocycle. R ¹ and R ² are preferably unsubstituted or aliphatic and alicyclic hydrocarbon moieties substituted with one or more hydroxyl, cyano, halogen atom, OR ³ or SR ³ moieties; wherein R ¹ and R ² can be Combined with S to form a heterocycle. In a preferred embodiment, R ¹ and R ² are not combined with each other to form a heterocycle with S, and R ¹ and R ² are unsubstituted or replaced with one or more hydroxyl, halogen, cyano, OR ³ or SR ³ substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, wherein R ³ is aliphatic or alicyclic. In a most preferred embodiment, each of R ^{and R} is alkyl or alkenyl, especially, ^R is methyl or ethyl, and ^R is C _6-11 alkyl or C _6-11 chain Alkenyl. In this preferred embodiment, ^R1 and ^R2 are not the same hydrocarbon moiety, ie the -sulfide is asymmetric. R ³ is preferably an aliphatic group or an alicyclic group. ^R3 is preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl.

The total carbon content of the hydrocarbon portion of the hydrocarbon-sulfide collector must be such that the sulfide collector has sufficient hydrophobic character to drive metal-bearing sulfide mineral or sulfide metal-bearing oxide mineral particles to the air/bubble interface. The hydrocarbon-sulfide collector has a total carbon content of at least 4, more preferably 6, and most preferably 8 carbons. The maximum carbon content is preferably 20, more preferably 16, most preferably 12.

Examples of cyclic compounds suitable for use in the present invention include the following structures:

Wherein, R ⁴ are respectively aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxyl, cyano, halogen atom, OR ³ or SR ³ , Here aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl can be replaced by hydroxyl, cyano, OR ³ or SR ³ etc. replaced.

In another preferred embodiment of the present invention, the collector of the present invention conforms to the molecular formula

in

R ⁶ are hydrocarbon groups respectively, or hydrocarbon groups substituted with hydroxyl, cyano, halogen atom, ether, alkoxy or alkyl sulfide; here two R ⁶ groups can be combined with S to form a ring or heterocycle;

n is an integer of 0, 1, 2, or 3; provided that the total carbon content of the hydrocarbon portion of the collector must be such that the collector has sufficient hydrophobic properties to cause particles of metal-bearing sulfide minerals or sulfide metal-bearing oxide minerals to be Drive to the air/bubble interface.

Preferred R ⁶ is unsubstituted or aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl substituted with cyano, hydroxyl, halogen atom, OR ³ or SR ³ moiety, wherein R ³ As defined above. More preferably R is ^{an aliphatic} or alicyclic group which is unsubstituted or substituted with a hydroxyl group, a cyano group, a halogen atom, an aliphatic ether, an alicyclic ether, an aliphatic thioether or an alicyclic thioether group base. More preferably ^R6 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl moiety. Most preferably, one -C(H) _n ( ^R6 ) _3-n is a methyl or ethyl moiety and the other is a _C6-11 alkyl or _C6-11 alkenyl. n is preferably 1, 2 or 3, more preferably 2 or 3.

Preferred hydrocarbons containing monosulfide segments R ¹ -SR ² (wherein R ¹ and R ² are as defined above) are prepared by standard methods known in the art, e.g. by reacting R ² -H with R ¹ -SH , wherein R ¹ and R ² are as defined above.

Examples of compounds within the scope of the present invention include methyl butyl sulfide, methyl pentyl sulfide, methyl hexyl sulfide, methyl heptyl sulfide, methyl octyl sulfide, methyl nonyl sulfide, methyl Decyl sulfide, methyl undecyl sulfide, methyl dodecyl sulfide, methyl cyclopentyl sulfide, methyl cyclohexyl sulfide, methyl cycloheptyl sulfide, methyl cycloheptyl sulfide Octyl sulfide, ethyl butyl sulfide, ethyl amyl sulfide, ethyl hexyl sulfide, ethyl heptyl sulfide, ethyl octyl sulfide, ethyl nonyl sulfide, ethyl decyl Sulfide, ethyl undecyl sulfide, ethyl dodecyl sulfide, ethyl cyclopentyl sulfide, ethyl cyclohexyl sulfide, ethyl cycloheptyl sulfide, ethyl cyclooctyl sulfide ether, propyl butyl sulfide, propyl pentyl sulfide, propyl hexyl sulfide, propyl heptyl sulfide, propyl octyl sulfide, propyl nonyl sulfide, propyl decyl sulfide, Propyl undecyl sulfide, propyl dodecyl sulfide, propyl cyclopentyl sulfide, propyl cyclohexyl sulfide, propyl cycloheptyl sulfide, propyl cyclooctyl sulfide, di Butyl sulfide, butyl pentyl sulfide, butyl hexyl sulfide, butyl heptyl sulfide, butyl octyl sulfide, butyl nonyl sulfide, butyl decyl sulfide, butyl undecyl sulfide, Butyl dodecyl sulfide, butyl cyclopentyl sulfide, butyl cyclohexyl sulfide, butyl cycloheptyl sulfide, Butyl cyclooctyl sulfide, dipentyl sulfide, amyl hexyl sulfide, amyl heptyl sulfide, amyl octyl sulfide, amyl nonyl sulfide, amyl decyl sulfide, amyl undecane Amyl sulfide, pentyl dodecyl sulfide, pentyl cyclopentyl sulfide, pentyl cyclohexyl sulfide, pentyl cycloheptyl sulfide, pentyl cyclooctyl sulfide, dihexyl sulfide, hexyl Heptyl sulfide, hexyl octyl sulfide, hexyl nonyl sulfide, hexyl decyl sulfide, hexyl undecyl sulfide, hexyl dodecyl sulfide, hexyl cyclopentyl sulfide, hexyl cyclohexyl sulfide Ether, hexyl cycloheptyl sulfide, hexyl cyclooctyl sulfide, diheptyl sulfide, heptyl octyl sulfide, heptyl nonyl sulfide, heptyl decyl sulfide, heptyl undecyl sulfide , Heptyl dodecyl sulfide, Heptyl cyclopentyl sulfide, Heptyl cyclohexyl sulfide, Heptyl cycloheptyl sulfide, Heptyl cyclooctyl sulfide, Dioctyl sulfide, Octyl nonyl sulfide , octyl decyl sulfide, octyl undecyl sulfide, octyl dodecyl sulfide, octyl cyclopentyl sulfide, octyl cyclohexyl sulfide, octyl cycloheptyl sulfide, octyl ring Octyl sulfide, octyl cyclodecyl sulfide, dinonyl sulfide, nonyl decyl sulfide, nonyl undecyl sulfide, nonyl dodecyl sulfide, nonyl cyclopentyl sulfide , nonylcyclohexylsulfide, nonylcyclohexylsulfide, nonylcyclohexylsulfide, didecylsulfide, decylundecylsulfide, decyldodecylsulfide, decylcyclo Amyl sulfide, decyl cyclohexyl sulfide, decyl cycloheptyl sulfide, and decyl cyclooctyl sulfide. Preferred sulfides include methylhexylsulfide, methylheptylsulfide, methyloctylsulfide, methylnonylsulfide, methyldecylsulfide, ethylhexylsulfide, ethylheptylsulfide Sulfide, ethyl octyl sulfide, ethyl nonyl sulfide, ethyl decyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diheptyl sulfide, and dioctyl sulfide.

Here, hydrocarbon refers to an organic compound containing carbon and hydrogen atoms. The term "hydrocarbon" includes the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aromatics, aliphatic and cycloaliphatic aromatic alkanes and alkyl-substituted of Aromatics.

Here, aliphatic hydrocarbons refer to linear and branched, saturated and unsaturated hydrocarbon compounds, ie alkanes, alkenes or alkynes. Alicyclic hydrocarbons refer to saturated and unsaturated cyclic hydrocarbons, namely cycloalkenes and cycloalkanes.

Cycloalkanes refer to alkanes containing one, two, three or more rings. Cycloalkenes refer to monocyclic, bicyclic and polycyclic groups containing one or more double bonds.

Here, the hydrocarbon group refers to an organic group containing carbon and hydrogen atoms. The term "hydrocarbyl" includes the following organic groups: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl and alkaryl of aliphatic and cycloaliphatic hydrocarbons. Herein, the term "aryl" refers to diaryl, diphenyl, phenyl, naphthyl, phenanthrenyl, anthracenyl and two aryl groups bridged by an alkylene group. Herein, alkaryl refers to an alkyl, alkenyl or alkynyl substituted aryl group, wherein aryl is as defined above. Here, aralkyl refers to an alkyl group in which the aryl group is as defined above.

C _1-20 alkyl includes linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Tridecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl and Eicosyl groups.

Here, halogen refers to chlorine, bromine or iodine groups.

The method of the present invention is suitable for recovering metal-bearing sulfide minerals and sulfide metal-containing oxide minerals from ores by froth flotation. As used herein, ore refers to mineral deposits extracted from the earth, including desired metal-bearing minerals mixed with gangue. Here, gangue refers to that portion of material that has no value and needs to be separated from the desired metal-bearing mineral.

In a preferred embodiment, metal-bearing sulfide minerals are recovered. in a better reality In an embodiment, sulfide minerals containing copper, nickel, lead, zinc or molybdenum metals are recovered. In a preferred embodiment, copper-containing sulfide minerals are recovered. In addition, preferred metal-containing sulfide minerals are those that have high hydrophobicity in the non-oxidized state. The term "hydrophobic in the non-oxidized state" denotes minerals that are freshly mined and have a fresh surface, with the possibility of flotation without the addition of collectors.

Ores include those containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and their sulfides, which compounds are useful. Examples of metal-bearing sulfide minerals that can be enriched by froth flotation using the method of the present invention include copper-bearing minerals such as indodorite (CuS), chalcopyrite ( _Cu2S ), chalcopyrite ( _CuFeS2 ), chalcopyrite (Cu ₂ Fe ₄ S ₇ ) or Cu ₃ Fe ₄ S ₇ ), bornite (Cu ₅ FeS ₄ ), chalcopyrite (Cu ₂ SFe ₄ S ₅ ), chalcopyrite[ Cu ₃ (AsSb) S ₄ ], tetrahedrite (Cu ₃ SbS ₂ ), arsenite (Cu ₁₂ As ₄ S ₁₃ ), copper sulfate hydrocollagenite [Cu ₄ (OH) ₆ SO ₄ ], copperite [Cu ₃ SO ₄ (OH) ₄ ], styroite [Cu ₃ (SbAs)S ₄ ], and chakraite (PbCuSbS ₃ ); lead-bearing minerals, such as galena (PbS); antimony-bearing minerals, such as Antimonite (Sb ₂ S ₃ ); zinc-bearing minerals, such as sphalerite (ZnS); silver-bearing minerals, such as brittleite (Ag ₅ SbS ₄ ) and argentite (Ag ₂ S); chromium-bearing minerals, Such as ferrosulfur chromium (FeSCrS ₃ ); nickel-containing minerals such as pentlandite [(FeNi) ₉ S ₈ ]; molybdenum-containing minerals such as molybdenite (MoS ₂ ) and platinum and palladium-containing minerals such as sulfur Arsenoplatinite [Pt(ass) ₂ ]. Preferred metal-bearing sulfide minerals include molybdenite (MoS ₂ ), chalcopyrite (CuFeS ₂ ), galena (PbS), sphalerite (ZnS), bornite (Cu ₅ FeS ₄ ) and nickel Pyrite [(FeNi) ₉ S ₈ ].

Sulphided metal-bearing oxide minerals are minerals that have been treated with sulphiding chemicals in order to impart some of the characteristics of sulphide minerals to the mineral so that it can be subjected to froth flotation using collectors that recover sulphide minerals Recycle. The result of sulfidation of oxidized minerals has the properties of sulfide minerals. Oxidized minerals are vulcanized by contact with compounds that react with it to form sulfur bonds or similar sulfur bonds. Such methods are well known techniques. These compounds include sodium hydrosulfide, sulfuric acid and related sulfur-containing salts, such as sodium sulfide.

Sulphided metal-containing oxide minerals useful for the present method 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 froth flotation using the method of the present invention include copper-containing minerals such as cuprite (Cu ₂ O), cuprite (CuO), malachite [(Cu ₂ OH ) ₂ CO ₃ ], azurite [Cu ₃ (OH) ₂ (CO ₃ ) ₂ ], cyanite [Cu ₂ Cl (OH) ₃ ], chrysocolla (CuSiO ₃ ); aluminum-containing minerals, such as carborundum ; zinc-containing minerals, such as red tungsten ore (Fe, Mn) WO ₄ ; nickel-containing minerals, such as green nickel ore (NiO); molybdenum-containing minerals, such as color molybdenite (PbMoO ₄ ) and molybdenum tungsten calcium ore (CaMoO ₄ ); iron-containing minerals, such as hematite and magnetite; chromium-containing minerals, such as chromite (FeCr ₂ O ₃ ); iron- and iron-containing minerals, such as ilmenite; magnesium- and aluminum-containing minerals, such as spinel; minerals containing iron and chromium, such as chromite; minerals containing titanium, such as rutile; minerals containing manganese, such as pyrolusite; minerals containing tin, such as cassiterite; and minerals containing uranium, such as uranite; Uranium-bearing minerals, such as uranite [U ₂ O ₅ (U ₃ O ₈ )] and uranite (UO _3n H ₂ O); zinc-bearing minerals, such as sphalerite (ZnO), smithsonite ( ZnCO ₃ ).

The collectors of the present invention can be used at any concentration that confers the desired In particular, the concentration employed depends on the particular mineral being recovered, the grade of the ore undergoing froth flotation, the amount of mineral desired to be recovered, and the specific mineral to be recovered. Preferably, the collector of the present invention is used at a concentration of 0.001 kg to 1.0 kg per ton of ore, most preferably, about 0.010 to 0.2 kg of collector per ton of ore is used for froth flotation.

The froth flotation process of the present invention preferably uses a frother, any known frother capable of achieving the desired mineral recovery.

Frothing agents useful in the present invention include any known frothing agent capable of achieving the desired mineral recovery. Examples of such foaming agents include C _5-8 alcohols, pine oils, cresols, polypropylene glycol C _1-4 alkyl ethers, polypropylene glycol dihydroxylates, propylene glycol, fatty acids, soaps, Alkaryl sulfonates and the like. Additionally, blends of these blowing agents can also be used. All foaming agents suitable for froth flotation beneficiation can be used in the present invention.

In addition, in the method of the present invention, it should be noted that the collector of the present invention can be mixed with other known collectors. Known collectors that may be used in admixture with the collectors of the present invention are those collectors that will impart the desired recovery of the minerals desired to be recovered. Examples of collectors useful in the present invention include alkyl monothiocarbonates, alkyl dithiocarbonates, alkyl trithiocarbonates, dialkyl dithiocarbonates, alkyl thiocarbonates, Carbonyl carbonates, dialkylthioureas, monoalkyl dithiophosphates, dialkyl and diaryl dithiophosphates, dialkyl monothiophosphates, dialkyl and Diarylthiophosphonochlorides, Dialkyl and Diaryldithiophosphonates, Alkylthiols, Xanthoformates, Xanthates, Mercaptobenzothiazoles, Fatty Acids and fatty acid salts, alkyl sulfates and their salts, alkyl and alkaryl sulfonic acids and their salts, alkyl phosphoric acids and their salts, alkyl and aryl phosphoric acids and their salts, sulfur succinic acid Classes, sulfosuccinamide esters, primary amines, secondary amines, tertiary amines, quaternary ammonium salts. Alkylpyridinium salts, guanidines and alkylpropylenediamines.

specific embodiment

The following examples can be used to illustrate the present invention, but are not intended to limit the scope of the present invention. Unless otherwise stated, fractions and decimals are by weight.

In some of the following examples, the performance of the froth process is described in terms of calculated flotation rate constants and recovery over infinite time. These values are calculated using the following formula:

r=R _∞ [l- (le ^-kt )/(kt) ]

Among them: γ is the ratio of recovered minerals in time t, k is a constant for the recovery rate, and R is the calculated share of minerals that will be recovered in infinite time. The quantity recovered in different time is determined experimentally, and this series of values are substituted into the equation to obtain R and K. The above formula was published in Chapter 45 (pages 907-934) of the book "Selection of Chemical Agents for Flotation" edited by Klimpel in the second edition of American Society of Mining, Metallurgy and Petroleum Engineers (Denver) in 1980. Concentrator Design" is described.

Example 1 - Froth Flotation of Copper-Containing Sulfide Minerals

In this example, several collectors of the invention were tested for flotation of copper-containing sulfide minerals. Put 500 grams of Western Canada Tong ore with a relatively high grade of chalcopyrite and a little bit of pyrite and 257 grams of deionized water into a rod mill equipped with a 1-inch (2.5 cm) grinding rod , and grind at a speed of 60 rpm for 420 revolutions to provide particles with a particle size distribution of less than 100 meshes accounting for 25%. Add some lime according to the desired pH value of the subsequent flotation. The ground pulp is conveyed to the 1500ml flotation cell of the Agitair flotation machine. The flotation cell was stirred at a speed of 1150 rpm, and further lime was added to adjust the pH value to 8.5.

Add the collector (8 g/ton) to the flotation cell, and add the foaming agent DOWFROTH 250 (18 g/ton) after adjusting for 1 minute. After adjusting again for 1 minute, feed air into the flotation cell at a speed of 4.5 liters/minute, and start the automatic defoaming slurry. Foam samples were taken at 0.5, 1.5, 3, 5 and 8 minutes. These froth samples were oven dried overnight along with the flotation tailings. The dried sample is weighed, divided into samples suitable for analysis, crushed to the appropriate fineness, and dissolved in acid for analysis. The sample was analyzed with a DC plasma spectrograph, and the analysis results are compiled in Table 1.

1. R-8 is the experimental recovery rate represented by decimals after 8 minutes

2. Selectivity is calculated by dividing the recovery rate of copper at 8 minutes by the recovery rate of gangue at 8 minutes

3. Not the embodiment of the present invention

Experiments show that the recovery rate and recovery balance of these collectors of the present invention are better than those of mercaptan and polysulfide collectors.

Example 2 - Froth flotation of copper molybdenum ore

Prepare several bags of the same ore containing chalcopyrite and molybdenite minerals, each containing 1200 grams. The roughing step is 1200 grams of feed and 800 milliliters of tap water in a bag of ball mills with mixing balls (mills that reach 100 mesh and account for more than 13%) and grind for 14 minutes. The pulp is sent to the 1500ml flotation tank of Ajitai flotation machine equipped with automatic slurry defoaming system. Use lime to adjust the pH value of the pulp to 10.2, and no further adjustment here will be made in the test. The four-stage rough flotation scheme is as follows:

Stage 1: Collector - 0.0042 kg/ton

MIBC-0.015 kg/ton

- Adjustment time - 1 minute

- Float - Concentrate captured in 1 minute

Stage 2: Collector - 0.0021 kg/ton

MIBC-0.005 kg/ton

- Adjustment time - 0.5 minutes

- Floats - 1.5 mins caught concentrate

Stage 3: Collector - 0.0016 kg/ton

MIBC-0.005 kg/ton

- Adjustment time - 0.5 minutes

- Float - 2.0 Minutes Captured Concentrate

Stage 4: Collector - 0.0030 kg/ton

MIBC-0.005 kg/ton

- Adjustment time - 0.5 minutes

- Floats - 2.5 minutes of concentrated ore harvested

The results are compiled in Table 2.

Table 2

Froth Flotation of Copper/Molybdenum Ore in Western Canada

Collector Dosage Copper Molybdenum Average Copper Average Molybdenum Iron Average

g/t R-7′ R-7′ Grade ² Grade ² Grade ²

A 11.2 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 0.00346 0.161

C 11.2 0.699 0.697 0.107 0.00386 0.164

C 22.4 0.723 0.723 0.112 0.00382 0.142

Potassium A-pentylxanthate, not an example of the invention

B-1,2-cyclothioctane

C-Hexyl Methyl Sulfide

1.-R-7 is the experimental recovery expressed as a decimal after 7 minutes

2.-Grade is the fraction of the total recycled weight of a specific metal in the foam

table 3

Froth Flotation of Cu/Ni Ore in Eastern Canada

Collector Copper Nickel Copper Nickel Magneto Yellow Selection

iron minerality ²

K R K K R R-12′ R-12′ R-12′

C ₅ H ₁₁ OCS ₂ Na 5.71 0.94 3.35 0.866 0.931 0.849 0.393 2.16

Sodium amyl xanthate

8.22 0.938 2.24 0.790 0.927 0.751 0.247 3.04

C ₄ H ₉ SC ₄ H ₉ 9.61 0.937 2.95 0.656 0.928 0.630 0.190 3.32

1. R-12 is the experimental recovery expressed as a decimal after 12 minutes

2. Selectivity is calculated by dividing nickel recovery by pyrrhotite recovery at 12 minutes

The use of the collectors of the present invention has both an improvement in the overall concentrate grade (the desired fraction of metal-bearing sulfide minerals in the final flotation product) and a substantial reduction in pyrite in the concentrate as measured by the decline in iron specks in the product. Great effect. This is independent of the dose used. This means less material is fed into the furnace and less sulfur is emitted per unit of metal produced.

Example 3 - Froth flotation of eastern Canadian copper/nickel ore containing significant iron sulfide minerals in the form of pyrrhotite.

Several samples were withdrawn from the feeder to the plant's roughing warehouse and placed in containers to provide approximately 1200 grams of solids. The pulp contains chalcopyrite minerals and pentlandite minerals. Time-recovery curves were then prepared for the individual concentrates selected at 1.0, 3.0, 6.0 and 12.0 minutes using the contents of each vessel on a Denver flotation cell using automatic slurry and constant slurry level equipment, The collector was added in one-minute increments for the specified 1 minute period prior to beginning defoaming. The dosage of the collector is 0.028 kg per ton of flotation feed. The individual concentrates were dried, weighed, ground and prepared into probability equal samples for analysis. The time-dependent recovery rate and the total grade of the selected raw ore are calculated using standard material balance equations.

The collectors of the present invention give copper recoveries comparable to sodium amyl xanthate; the collectors of the present invention give much higher flotation rates. The collectors of the present invention give lower nickel recoveries than sodium amylxanthate, but also provide much lower recoveries of the unwanted iron sulfide pyrrhotite, comparable to the _R12 of pyrrhotite. A 50% increase in the selectivity of the value and nickel sulfide mineral over the unwanted pyrrhotite sulfide is seen.

Example 4 - Froth Flotation of Pb/Zn/Cu/Ag Composite Ore in Central Canada

A number of homogeneous 1000 gram samples of ore were prepared. The ore contains the minerals galena, sphalerite, chalcopyrite and argentite. For each flotation, mix a sample with 500 ml Water was added to the rod mill along with 7.5 ml of SO solution. Mill for 6.5 minutes to prepare 90% feed below 200 mesh (75 microns). After grinding, the material is moved into flotation cells equipped with automatic paddles for defoaming, which are connected to a standard Denver flotation machine.

Then two stages of flotation are carried out. In the first stage, the rougher copper/lead/silver float is taken out, and in the second stage, the rougher zinc float is taken out. At the beginning of the first stage of flotation, add 1.5 grams of Na ₂ CO ₃ per kilogram (PH value is 9 to 9.5), and then add collectors (types). Thereafter, the pulp was aired and agitated for 5 minutes as prescribed, followed by a conditioning period of 2 minutes. Then add foaming agent MIBC (standard is 0.015 ml/kg). Concentrate was collected at 5 minutes of flotation and labeled as copper/lead rougher concentrate.

The second stage of flotation consisted of adding _CuSO4 at 0.5 kg/t to the residue of the first stage flotation cell, then adding lime to adjust the pH value to 10.5, followed by stirring only during the adjustment period which lasted 5 minutes, and then re- Check the pH and adjust back to 10.5 with lime. At this point, the collector was added, followed by stirring only for the specified 5 minute period. Then add foaming agent MIBC (standard is 0.020 ml/kg). Concentrate was collected at 5 minutes and identified as zinc rough concentrate.

Concentrate samples are dried, weighed and suitable samples prepared for analysis by X-ray methods. Recovery and grade are calculated using standard mass balance formulas and using assay data.

In addition to the above steps, tests were also carried out when the pH value of the first stage was low (without adding Na ₂ CO ₃ , the pH value was 8.5) and when only sufficient lime was added in the second stage, and the pH value was 9.5. Add CuSO ₄ at 0.3 kg/ton, and the pH value is also low.

Sodium A-Ethylxanthate

B-dithiophosphate

C-thionocarbamate

A, B and C are non-embodiments of the present invention

D-1,2 Cyclothioctane

E-octyl methyl sulfide

1. R-5 is the actual recovery rate expressed in decimals after 5 minutes

2. Grade is the relative metal of a specific metal in the foam to the total weight collected

This is a complex flotation process which has shown quite amazing results in that the collector of the present invention can replace a complex mixture of three of the best collectors in the industry and at the usual pH and _CuSO4 The recoveries and grades of metals were basically consistent with those replaced, and were selected as the best industrial collectors (Tests 1, 2, 3). Corresponding tests (4, 5, 6) at lower pH and CuSO ₄ also showed that the collectors of the present invention significantly improved metal grades over those three commercial collectors. The result means that plant operations can save significantly on lime and CuSO. (The main reason for controlling the pH value of the first stage at 10.5 and the second stage at 9.5 is to improve selectivity. The main reason for adding CuSO ₄ is to improve the recovery rate of zinc while maintaining the grade). Note that the collectors of the present invention actually improve zinc recovery and maintain good grade when operating at low CuSO ₄ (5, 6).

Example 5 - Froth Flotation of Copper/Molybdenum Ore

500 grams of South American copper/molybdenum ore along with 257 grams of deionized water and some lime were placed in a rod mill fitted with 1 inch (2.5 cm) grinding rods and milled at 60 rpm for 360 revolutions to provide a particle size distribution Suitable fine particles (about 25% less than 100 mesh). The ground slurry containing various copper sulfide minerals and molybdenite is sent to the 1500ml flotation cell of the Ajitai flotation machine. The flotation cell is stirred at a speed of 1150 rpm, and the pH value is adjusted to 8.5 by adding lime or hydrochloric acid.

Collector was added to the flotation cells (45 g/t) followed by frother DOWFROTH 250 (36.4 g/t) over a 1 minute conditioning period. After adjusting for 1 minute, air is passed into the flotation cell at a speed of 4.5 liters/minute, and the automatic foam scraping is started. Foam samples were collected at 0.5, 1.5, 3, 5 and 8 minutes. The froth sample was dried overnight in an oven with the flotation tailings. The dried sample is weighed, divided into samples suitable for analysis, crushed to an appropriate fineness and then dissolved in acid for DC plasma spectrometer analysis. The results are compiled in Table 5.

table 5

Collector pH Copper Molybdenum Iron

R-8 ² R-8 ² R-8 ²

Xanthate/Thiono

Carbamate ¹ 10.5 0.891 0.742 0.398

Octyl ethyl sulfide 10.5 0.854 0.791 0.278

Xanthate/Thiono

Carbamate ¹ 8.0 0.912 0.780 0.422

Octyl ethyl sulfide 8.0 0.887 0.394 0.394

1. Non-inventive example (50/50 w/w mixture of sodium ethyl xanthate and sodium isopropyl ethylthionocarbamate)

2. R-8 is the experimental recovery rate represented by decimals after 8 minutes

The collectors of the present invention showed a significant increase in molybdenum recovery over the standard agent, however copper recovery was decreased. The recovery of ferrous sulfides also dropped very significantly as desired.

Example 6 - Froth Flotation of Copper Ore

The steps of Example 1 were repeated, using ores containing moderately high chalcopyrite and slightly pyrite-containing ores from the same mine as in Example 1, and the results obtained are compiled in Table 6.

1. R-8 is the experimental recovery rate represented by decimals after 8 minutes

2. Selectivity is calculated by dividing the recovery rate of copper at 8 minutes by the recovery rate of gangue at 8 minutes

3. Non-inventive embodiments

This example illustrates two points: 1) the effect of the hydrophobic portion of the collector; 2) a comparison of the compounds of the invention with a single component inorganic sulfide (NaS).

Claims (4)

1, a kind of method that reclaims the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration from ore comprising the pulp ore, adopts collecting agent to handle ore pulp through flotation, it is characterized in that efficient and selectivity in order to improve this method, and described collecting agent is a formula

R ¹-S-R ²Shown sulfide, wherein R ¹Be methyl or ethyl;

R ²Be C _5-11Aliphatic, alicyclic, aromatic group or their combination product, perhaps R ¹And R ²Combine and S forms ternary epithio circulus, condition is that the total carbon content of S and aliphatic series or cyclic aliphatic carbon atom bonding, sulfide collecting agent is 6-20 carbon atom and R ¹And R ²It is not identical alkyl.

2, in accordance with the method for claim 1, R wherein ¹Be methyl or ethyl, R ²Be C _6-11Alkyl or C _6-11Thiazolinyl.

3, in accordance with the method for claim 1, the working concentration of wherein said sulfide collecting agent treats that with 1000kg the ore of froth flotation is that benchmark is counted 0.001-1.0kg.

4, in accordance with the method for claim 1, wherein said epithio circulus is shown below:

R wherein ⁴Be respectively aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, hydroxyl, cyano group, halogen atom, OR ³Or SR ³, wherein aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, the visual concrete condition of cycloalkenyl group are by hydroxyl, cyano group, OR ³Or SR ³Replace R ³Be alkyl.