CN1011945B - Method for froth flotation using collector composition - Google Patents

Abstract

This invention relates to novel compositions which are effective collectors for the recovery of ferrous metal-containing sulfide minerals and sulfidated metal-bearing oxide minerals from ores in froth flotation. It includes: (a) hydrocarbons containing one or more monothioether units, wherein the sulfur atoms bonded to the sulfur atoms are aliphatic or cycloaliphatic carbon atoms, and the total carbon content of the hydrocarbon moiety should be such that Hydrocarbons have sufficient hydrophobic character. Enables metal-bearing sulfide minerals or sulfidized metal-containing oxide mineral particles to be driven to the air-bubble interface: and (b) alkyl thiocarbonates: thionocarbamate, sulfophosphate or a mixture thereof.

Description

This invention relates to a novel collector composition suitable for the recovery of metal-containing sulfide minerals and sulfide metal-containing oxide minerals from ores by froth flotation.

Flotation is the process of treating a mixture of crushed mineral solids. For example, powdered ore is suspended in certain liquids whereby a portion of the solids is separated from another portion of comminuted solids such as clay and other similar substances present in the ore. By passing gas (or gas supplied on site) into the liquid, a layer of foam containing a certain solid can be generated on the upper part of the liquid, leaving other solid components in the unfoamed (suspended) ore. The flotation method is based on the principle that when the gas is passed into a liquid in which solid particles of different substances are suspended, some gas can be attached to some suspended solid particles, but not to other solid particles. In this way, By making the gas-attached particles lighter than the liquid, these particles will rise to the top of the liquid and form a foam.

Various flotation agents have been proposed to improve frothing by blending with the suspension. The functions of the above additives can be divided into: Collectors, for sulfur compounds, which include xanthate, thionocarbamate, etc. Examples of foaming agents with the property of forming stable foam are: Natural oils Such as pine oil and eucalyptus oil, modifiers such as activators, which induce flotation in the presence of collectors, such as copper sulfate, and inhibitors, such as sodium cyanide, which prevent the flotation collector from interacting with certain Minerals that should remain in the liquid act to prevent certain substances from being brought up to be part of the foam, pH regulators, to produce the best metallurgical effect, such as lime, soda ash, etc.

It should be remembered that the selection of the above-mentioned types of additives should be determined according to the nature of the ore, the minerals to be recovered and other additions selected at the same time.

Knowledge of the phenomena that make flotation a particularly valuable industrial operation is not necessary in order to practice the present invention. However, this phenomenon can be considered to have a lot to do with the selective affinity of the surface of powdered solid particles suspended in a liquid containing trapped gas, on the one hand for the liquid and on the other hand for the gas.

The principle of flotation is applied in the beneficiation process of several minerals to selectively separate sulfide minerals containing copper, zinc, lead, nickel, molybdenum and other metals from iron-containing sulfide minerals, such as pyrite and pyrrhotite Coming out is also one of them.

To recover metal-containing sulfide minerals or sulfide metal oxide minerals, commonly used collectors are xanthate, dithiophosphate and thionocarbamate. These volatile sulfur compounds are often released into the atmosphere through chimneys or are removed from these chimneys using expensive, refined scrubbers. It also occurs naturally in many ferrous metal-containing sulfide minerals or metal-bearing oxide minerals in ores composed of iron-bearing sulfide minerals. 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. Therefore, there is a need for a method for selectively recovering ferrous metal-containing sulfide minerals and sulfide metal-bearing oxide minerals without recovering iron-bearing sulfide minerals.

Among commercial collectors, xanthates, thionocarbamate esters, and dithiophosphates, do not selectively recover non-ferrous metal-containing sulfide minerals in the presence of iron-containing sulfide minerals . Instead, these flotation collectors indiscriminately capture and recover all metal-bearing sulfide minerals.

There is therefore a need for a flotation collector composition which selectively recovers non-ferrous metal-containing sulfide minerals or sulfided metal-containing oxide minerals in the presence of iron sulfides.

The present invention relates to novel compositions which, in froth flotation, are an efficient collector It can recover non-ferrous metal-bearing sulfide minerals and sulfide metal-bearing oxide minerals from ore. Novel compositions include:

(a) Hydrocarbons containing one or more monothioether units in which the carbon atom bound to the sulfur atom is aliphatic or cycloaliphatic and the total carbon content of the hydrocarbon moiety is such that the hydrocarbon has Sufficient hydrophobic properties to enable particles of metal-bearing sulfide minerals or sulfide metal-bearing oxide minerals to be repelled to the air-bubble interface; and

(b) Alkyl thiocarbonates, thionocarbamates, thiophosphates or mixtures thereof. The novel flotation collector of the present invention can efficiently recover non-ferrous metal-containing sulfide minerals or sulfided metal-containing oxide minerals. The novel flotation collector of the present invention has good selectivity for non-ferrous metal-containing sulfide minerals and sulfide metal-containing oxide minerals when they exist together. These collectors have good collection effect and good kinetic behavior.

A component of the novel collector of the present invention is a hydrocarbon containing one or more monothioether units, wherein the sulfur atom of the thioether unit is combined with a non-aromatic carbon atom, i.e. aliphatic or cycloaliphatic carbon atoms bonded together. Here, a monothioether unit means a unit in which a sulfur atom is bonded to only two carbon atoms of the hydrocarbon moiety. Hydrocarbons, as used herein, contain one or more monothioether units, and include such compounds substituted with hydroxy, chloro, halo, ether, alkoxy, and alkoxy thioethers, and the like. The non-aromatic carbon atom as used herein refers to a carbon atom which is not part of an aromatic ring.

Suitable hydrocarbons containing monothioether units include compounds of the formula:

R ¹ -SR ² Ⅰ

In the formula, R ¹ and R ² are any hydrocarbon group or a hydrocarbon group substituted by one or more hydroxyl groups, cyano groups, halogen groups, ether groups, alkoxyl groups or hydrocarbon sulfides;

In the formula, R ^{and R} can be combined with S to form a heterocyclic structure; and from S to aliphatic or cycloaliphatic carbon atoms as a condition; also the total carbon content in the hydrocarbon sulfide should make the hydrocarbon have Sufficient hydrophobicity is conditioned so that the metal-containing sulfide mineral or sulfidized metal-containing oxide mineral particles can be driven to the air-bubble interface.

Preferably, R ^{and R} are optionally one or more hydrocarbyl, cyano, halo, OR ^{or SR} substituted or unsubstituted aliphatic, cycloaliphatic or aralkyl moieties, wherein R ³ is a hydrocarbyl group, and ^R1 and ^R2 can combine with S to form a heterocycle. R ¹ and R ² are preferably aliphatic or cycloaliphatic moieties substituted or unsubstituted with one or more hydroxycyano, halo, OR ³ or SR ³ , wherein R ¹ and R ² can be Combined with S to form a heterocycle. In a better embodiment, R ^{and R} are not combined with sulfur to form a heterocyclic ring, while R and ^R are substituted or unsubstituted with one or more of ^hydroxyl , halo, cyano, OR ^{or SR} Substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, wherein R ³ is aliphatic or cycloaliphatic. In the most preferred embodiment, R ¹ is methyl or ethyl, and R ² is C _6-11 alkyl or alkenyl. In the most preferred embodiment, ^R1 and ^R2 are not the same hydrocarbon moiety, that is, the monothioether is asymmetric. R ³ is preferably an aliphatic or cycloaliphatic group. ^R3 is preferably alkyl, cycloalkyl or cycloalkenyl.

In hydrocarbon monosulfides, the total carbon content of the hydrocarbon moiety must be such that the hydrocarbon sulfide has sufficient hydrophobic character to enable the particles of metal-bearing sulfide minerals or sulfidized metal-containing oxide minerals to be driven into the air-bubbles interface. Preferably, the total carbon content of the hydrocarbon monosulfide is, the minimum number of carbon atoms is 4, more preferably 6, most preferably 8, and the maximum number of carbon atoms is 20, more preferably 16, most preferably 12.

In another better embodiment of the present invention, useful hydrocarbon sulfides of the present invention, its corresponding molecular formula is:

(R ⁶ ) _3-n C(H) _n -SC(H) _n (R ⁶ ) _3-n Ic

In the formula, ^R is any hydrocarbon group, or a hydrocarbon group substituted with hydroxyl, cyano, halo, ether, hydroxyoxy or hydrocarbon thioether; wherein, ^two R can be combined to form a ring or be combined with a sulfur atom to form a hetero ring;

n is an integer of 0, 1, 2 or 3; the total carbon content of the hydrocarbyl part in the collector should make the collector have sufficient hydrophobic characteristics, so that the metal-containing sulfide mineral or sulfide-based metal-containing Oxide mineral particles can be driven to the air-bubble interface.

Preferably, R ^is substituted or unsubstituted aliphatic, cycloaliphatic, aryl, alkaryl or aralkyl with cyano, hydroxyl, halo, ^OR or ^SR , wherein R ³ as previously stated. More preferably, ^R6 is an aliphatic or cycloaliphatic moiety substituted or unsubstituted with hydroxy, cyano, aliphatic ether, cycloaliphatic ether, aliphatic thioether or cycloaliphatic thioether. Particularly preferably, R ⁶ is alkyl, alkenyl, cycloalkyl or cycloalkenyl. Preferably, one -C(H) _n (R ⁶ ) _3-n is methyl or ethyl and the other is C _6-11 alkyl or alkenyl. Preferably n is 1, 2 or 3, most preferably 2 or 3.

Examples of hydrocarbon thioethers within the scope of the present invention include: methyl butyl sulfide, methyl pentyl sulfide Alkyl sulfide, methyl hexyl sulfide, methyl heptyl sulfide, methyl octyl sulfide, methyl nonyl sulfide, methyl decyl sulfide, methyl+-alkyl sulfide, methyl+ Dialkyl sulfide, methyl cyclopentyl sulfide, methyl cyclohexyl sulfide, methyl cycloheptyl sulfide, methyl cyclooctyl sulfide, ethyl butyl sulfide, ethyl amyl sulfide , ethyl hexyl sulfide, ethyl heptyl sulfide, ethyl octyl sulfide, ethyl nonyl sulfide, ethyl decyl sulfide, ethyl + monoalkyl sulfide, ethyl + dialkyl Thioether, ethyl cyclopentyl sulfide, ethyl cyclohexyl sulfide, ethyl cycloheptyl sulfide, ethyl cyclooctyl sulfide, propyl butyl sulfide, propyl pentyl sulfide, propyl hexyl sulfide Sulfide, propyl heptyl sulfide, propyl octyl sulfide, propyl nonyl sulfide, propyl decyl sulfide, propyl + monoalkyl sulfide, propyl + dialkyl sulfide, propyl Cyclopentyl sulfide, Propyl cyclohexyl sulfide, Propyl cycloheptyl sulfide, Propyl cyclooctyl sulfide, Dibutyl sulfide, Butyl pentyl sulfide, Butyl hexyl sulfide, Butyl heptyl sulfide butyl sulfide, butyl octyl sulfide, butyl nonyl sulfide, butyl decyl sulfide, butyl + monoalkyl sulfide, butyl + dialkyl sulfide, butyl cyclopentyl sulfide, butyl cyclohexyl sulfide , Butyl cycloheptyl sulfide, Butyl cyclooctyl sulfide, Diamyl sulfide, Amyl hexyl sulfide, Amyl heptyl sulfide, Amyl octyl sulfide, Amyl nonyl sulfide, Pentyl decyl Thioether, pentyl + monoalkyl sulfide, pentyl + dialkyl sulfide, pentyl cyclopentyl sulfide, pentyl cyclohexyl sulfide, pentyl cycloheptyl sulfide, pentyl cyclooctyl sulfide Ether, dihexyl sulfide, hexyl heptyl sulfide, hexyl octyl sulfide, hexyl nonyl sulfide, hexyl decyl sulfide, hexyl + monoalkyl sulfide, hexyl + dialkyl sulfide, hexyl cyclopentyl sulfide Hexyl cyclohexyl sulfide, hexyl cyclohexyl sulfide, hexyl cycloheptyl sulfide, hexyl cyclooctyl sulfide, diheptyl sulfide, heptyl octyl sulfide, heptyl nonyl sulfide, heptyl decyl sulfide , heptyl + monoalkyl sulfide, heptyl + dialkyl sulfide, heptyl cyclopentyl sulfide, heptyl cyclohexyl sulfide, heptyl cycloheptyl sulfide, heptyl cyclooctyl sulfide, Dioctyl sulfide, octyl nonyl sulfide, octyl decyl sulfide, octyl + monoalkyl sulfide, octyl + dialkyl sulfide, octyl cyclopentyl sulfide, octyl cyclohexyl sulfide , octyl cycloheptyl sulfide, octyl cyclooctyl sulfide, octyl cyclodecyl sulfide, dinonyl sulfide, nonyldecyl sulfide, nonyl + monoalkyl sulfide, nonyl + Dialkylsulfide, Nonylcyclopentylsulfide, Nonyl cyclohexyl sulfide, nonyl cycloheptyl sulfide, nonyl cyclooctyl sulfide, didecyl sulfide, decyl + monoalkyl sulfide, decyl + dialkyl sulfide, decyl cyclo Amyl sulfide, Decyl cyclohexyl sulfide, Decyl cycloheptyl sulfide, Decyl cyclooctyl sulfide. More preferred thioethers include: methylhexylsulfide, methylheptylsulfide, methyloctylsulfide, methylnonylsulfide, methyldecylsulfide, ethylhexylsulfide, ethylheptylsulfide Ethyl sulfide, ethyl octyl sulfide, ethyl nonyl sulfide, ethyl decyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diheptyl sulfide and dioctyl sulfide base sulfide.

The second component of the novel collector compositions of this invention is an alkyl thiocarbonate, thionocarbamate, thiophosphate, or mixtures thereof. As used herein, alkyl thiocarbonates refer to compounds containing a thiocarbonate moiety and at least one alkyl group, wherein the alkyl group has sufficient hydrophobic Metal oxide mineral particles are driven to the air-bubble interface. A preferred alkyl thiocarbonate has the formula:

In the formula, R ⁷ is C _1-20 alkyl;

X in each case may be S or O respectively;

M is an alkali metal cation.

Preferable alkyl thiocarbonates include alkyl-thiocarbonates, alkyl dithiocarbonates or alkyl trithiocarbonates.

A preferred alkyl-thiocarbonate has the formula:

In the formula, R ⁷ and M are the same as defined above.

Examples of desirable alkyl-thiocarbonates include ethyl-sodium thiocarbonate, isopropyl-sodium thiocarbonate, isobutyl-sodium thiocarbonate, amyl-sodium thiocarbonate, ethyl- Potassium thiocarbonate, Potassium isopropyl-thiocarbonate, Potassium-isobutyl-thiocarbonate, Potassium-isobutyl-thiocarbonate and Potassium-amyl-thiocarbonate.

Alkyl dithiocarbonates are generally referred to as xanthates. The molecular formula of desirable alkyl dithiocarbonates is:

In the formula, R ⁷ and M are the same as defined above.

Preferable alkyl dithiocarbonates include potassium ethyl dithiocarbonate, sodium ethyl dithiocarbonate, potassium pentyl dithiocarbonate, sodium pentyl dithiocarbonate, isopropyl dithiocarbonate Potassium, sodium isopropyl dithiocarbonate, sodium sec-butyl dithiocarbonate, potassium sec-butyl dithiocarbonate, sodium isobutyl dithiocarbonate, potassium isobutyl dithiocarbonate, etc.

The molecular formula of desirable alkyl trithiocarbonates is:

In the formula, R ⁷ and M are the same as defined above.

Examples of alkyl trithiocarbonates include sodium isobutyl trithiocarbonate and potassium isobutyl trithiocarbonate.

The molecular formula of desirable thionocarbamate (ester) is:

In the formula, R ⁸ is C _1-10 alkyl in each case;

Y is -S ^- M ⁺ or -OR ⁹ , wherein R ⁹ is C _1-10 alkyl;

a is the integer 1 or 2; and

b is an integer 0 or 1, where a+b must equal 2.

Preferred thionocarbamate salts include dialkyldithiocarbamate and alkylthionocarbamate. The corresponding molecular formula for the most preferred dialkyldithiocarbamate is:

In the formula, M is the same as specified above; R ⁸ are respectively C _1-10 alkyl.

Preferred dialkyl dithiocarbamates include: Methylbutyl dithiocarbamate, Methylisobutyl dithiocarbamate, Methyl-sec-butyl dithiocarbamate Salt, Methylpropyl Dithiocarbamate, Methyl Isopropyl Dithiocarbamate, Ethyl Butyl Dithiocarbamate, Ethyl Isobutyl Dithiocarbamate salt, ethyl sec-butyl dithiocarbamate, ethyl propyl dithiocarbamate and ethyl isopropyl dithiocarbamate.

The molecular formula of desirable alkylthionocarbamate is:

In the formula, R ⁸ is the same as specified above, and R ⁹ is a C _1-10 alkyl group.

Examples of desirable alkylthionocarbamate include: butyl N-methylthionocarbamate, isobutyl N-methylthionocarbamate, sec-butyl N-methylthionocarbamate, N -Propyl methylthionocarbamate, isopropyl N-methylthionocarbamate, butyl N-ethylthionocarbamate, isobutyl N-ethylthionocarbamate, N-ethylthio Methyl-sec-butyl carbocarbamate, propyl N-ethylthionocarbamate and isopropyl N-ethylthionocarbamate. More preferred thionocarbamate includes: isopropyl N-ethylthionocarbamate and isobutyl N-ethylthionocarbamate.

The preferred molecular formula for phosphorothioate is generally:

In the formula, R ¹⁰ can be hydrogen, C _1-10 alkyl or aryl respectively;

X is oxygen or sulfur; and

M is an alkali metal cation.

Alternative thiophosphates include: monoalkyl dithiophosphates, dialkyl dithiophosphates, diaryl dithiophosphates and dialkyl monothiophosphates. The molecular formula of desirable monoalkyl dithiophosphate is:

In the formula, R ¹⁰ and M are the same as defined above.

Examples of desirable monoalkyl dithiophosphates include: ethyl dithiophosphate, propyl dithiophosphate, isopropyl dithiophosphate, ethyl dithiophosphate, sec-butyl Dithiophosphate and isobutyldithiophosphate.

Alternative dialkyl and diaryl dithiophosphates have the formulas:

In the formula, R ¹⁰ and M are the same as defined above.

Examples of dialkyl and diaryl dithiophosphates include: diethyl sodium dithiophosphate, di-sec-butyl sodium dithiophosphate, diisobutyl sodium dithiophosphate, diisoamyl dithiophosphate Sodium Thiophosphate and Sodium Dihydroxytoluene Dithiophosphate.

The molecular formula of optional dialkyl monothiophosphate is:

In the formula, R ¹⁰ and M are the same as defined above.

Preferred monothiophosphate salts include: sodium diethyl-thiophosphate, sodium di-sec-butyl-thiophosphate, sodium diisobutyl-thiophosphate and sodium diisoamyl-thiophosphate.

R ⁷ is preferably a C _2-16 alkyl group, most preferably a C _3-12 alkyl group. R ⁸ is preferably C _1-4 alkyl, most preferably C _1-3 alkyl. R ⁹ is preferably a C _2-10 alkyl group, especially a C _2-6 alkyl group, most preferably a C _3-4 alkyl group. R ¹⁰ is preferably C _2-8 alkyl or hydroxytolyl.

The composition of the present invention preferably comprises: (a) a hydrocarbon thioether of formula I and (b) an alkylthiocarbonate of formula II, a thionocarbamate of formula III, and a compound of formula IV Thiophosphate salts or mixtures thereof in such proportions that the composition is an effective collector for metal-bearing sulfide minerals and sulfide metal-bearing oxide minerals during froth beneficiation.

The compositions of the present invention may comprise: (a) from about 10% to about 90% by weight of a hydrocarbon thioether of formula I; and (b) from about 10% to about 90% by weight of an alkane of formula II. thiocarbonate, thionocarbamate of formula III, thiocarbonate of formula IV or mixtures thereof.

More preferably, the compositions of the present invention comprise: (a) from about 20% to about 80% by weight of a hydrocarbon sulfide of formula I; and (b) from about 20% to about 80% by weight of a hydrocarbon sulfide of formula An alkylthiocarbonate of II, a thionocarbamate of formula III, a phosphorothioate of formula IV or a mixture thereof.

The compositions of the present invention preferably comprise: (a) about 30 to 70% by weight of a hydrocarbon sulfide of formula I; and (b) about 30 to 70% by weight of an alkylsulfide of formula II Substituted carbonate, thionocarbamate of formula III, phosphorothioate of formula IV or mixtures thereof. In the most preferred embodiment of the present invention, the molecular formula is that the hydrocarbon thioether of I is to the thiocarbonate of II, the thionocarbamate of III, the phosphorothioate of IV or their The ratio of the mixture should be such that in the froth flotation process, the recovery rate of metal-containing sulfide minerals or sulfide metal oxide minerals should be higher than that of any component used alone under the same amount. results that can be obtained. The amount of collector used is preferably, when the molecular formula in the composition is the component (b) of II, III or IV, when this amount is used alone, with the same amount of Molecular formula is compared with the hydrocarbon sulfide of I, can obtain higher rate of recovery.

The novel collector compositions of the present invention provide higher recoveries and often higher metal grades than when either component of the collector is used alone. Grade refers to the relative amount of useful metal contained in the raw material collected by the foam.

Here it refers to organic compounds containing carbon atoms and hydrogen atoms. Hydrocarbons include the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aromatics, aliphatic and cycloaliphatic aranes and alkyl-substituted aromatics.

Aliphatic here means straight-chain and branched, saturated and unsaturated hydrocarbons, ie alkanes, alkenes or alkynes. Cycloaliphatic here means saturated and unsaturated cyclic hydrocarbons, ie cyclic hydrocarbons and naphthenes.

Naphthenic refers to alkanes containing one, two, three or more rings. Cycloalkenes refer to mono-, bi- or polycyclic groups containing one or more double bonds.

Hydrocarbyl refers here to an organic group containing carbon and hydrogen atoms. Hydrocarbyl groups include the following organic groups: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cycloaliphatic aryl and alkaryl. Aryl here means biaryl, biphenyl, phenyl, naphthyl, phenanthrenyl, anthracenyl and two aryl groups bridged by an alkylene group. Alkaryl refers here to an aryl substituent substituted by an alkyl, alkenyl or alkynyl group wherein the aryl group is as previously defined. Aralkyl refers here to an alkyl group in which the aryl group is as defined above.

C _1-20 alkyl includes: straight chain and branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.

Halo here refers to chlorine, bromine, iodine groups.

The novel collector compositions of the present invention are effective for the recovery of metal-bearing sulfide minerals and sulfide metal-containing oxide minerals from ores by froth flotation. ore here is Refers to raw material taken from a mining area, which contains the desired metal-bearing minerals mixed with gangue. Gangue here refers to that part of the raw material that has no value and needs to be separated from the desired metal-bearing minerals.

In a preferred embodiment, metal-containing sulfide minerals may be reverted. In a more preferred embodiment of the invention, sulfide minerals containing copper, nickel, lead, zinc, or molybdenum are recovered. In the most preferred embodiment, copper-containing sulfide minerals are recovered. There are also some better metal-bearing sulfide minerals which are inherently highly hydrophobic in the unoxidized state. The term "hydrophobic" in the unoxidized state applies to freshly ground minerals or minerals with a fresh surface that indicate that flotation can be performed without the addition of collectors.

Ores suitable for use with these compositions include: sulphide ores containing copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and mixtures thereof. Examples of metal-containing sulfide minerals that can be enriched by froth flotation using the method of the present invention include: copper-containing minerals, for example, copper ore (CuS), chalcocite (Cu ₂ S) chalcocite ore (CuFeS ₂ ), chalcopyrite (Cu ₂ Fe ₄ S ₇ or Cu ₃ Fe ₄ S ₇ ) copper ore (Cu ₃ S ₆ S ₂ ), bornite (Cu ₅ FeS ₄ ), chalcopyrite ( Cu ₂ SFe ₄ S ₅ ), arsenite [Cu ₃ (AS ₁ S ₆ ) S ₄ ] arsenite (C _u12 AS ₄ S ₁₃ ), bileite [Cu ₄ (OH) ₆ SO ₄ ] block Cuprosite [Cu ₃ SO ₄ (OH) ₄ ], styroxite [Cu ₂ (S ₆ AS)S ₄ ], and challite (P _b G _u S ₆ S ₃ ); minerals containing lead, e.g., Galena (P _b S); antimony-bearing minerals, e.g., stibnite (Sb ₂ S ₃ ); zinc-bearing minerals, e.g., sphalerite (ZnS); silver-bearing minerals, e.g., argentite (Ag ₂ SbS ₄ ) and argentite (Ag ₂ S); chromium-containing minerals such as troilite (FeSCrS ₃ ); nickel-containing minerals such as pyridoxite [(FeNi) ₉ S ₃ ]; molybdenum-containing minerals; eg, molybdenite (MoS ₂ ) and platinum- and palladium-containing minerals, eg, pyroplatinite [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 nickelite [FeNi) ₉ S ₈ ].

Sulphided metal-bearing oxide minerals are minerals that have been treated with sulphiding agents, thereby rendering them characteristic of sulphide minerals so that they can be recovered using the same collectors used to recover sulphide minerals in froth flotation. As a result of sulfidation, oxidized minerals can take on the characteristics of sulfides. Oxidized minerals can be sulfided by contact with compounds capable of reacting with the mineral to form sulfur bonds or affinities. These methods are well known in the art. Such compounds include: sodium hydrosulfide, sulfuric acid and related sulfur-containing salts, such as sodium sulfide.

Sulfurized oxide minerals suitable for use in the process include: oxide minerals containing copper, aluminum, iron, titanium, tungsten, molybdenum, magnesium, chromium, nickel manganese, tin, uranium and mixtures thereof. Examples of metal-containing oxidized minerals that can be enriched by the froth flotation method used in the present invention include: copper-containing minerals such as cuprite (Cu ₂ O), cuprite (GuO), malachite [( Cu ₂ OH) ₂ CO ₃ ], bluenite [Cu ₃ (OH) ₂ (CO ₃ ) ₂ ], chloratackite [Cu ₂ Cl(OH) ₃ ], chrysoporite (CuSiO ₃ ); aluminum-containing Minerals, such as corundum ore; zinc-containing minerals, such as zincite (ZnO) and zinc ore (ZnCO ₃ ); tungsten-containing minerals, such as wolframite [(Fe,Mn)WO ₄ ]; nickel-containing Minerals, such as green nickel ore (NiO); molybdenum-containing minerals, such as colored molybdenite (PbMoO ₄ ) and molybdenum-tungsten calcium ore (CaMoO ₄ ); iron-containing minerals, such as hematite and magnetite; Minerals containing chromium, such as chromite (FeOCr ₂ O ₃ ), minerals containing iron and titanium, such as ilmenite; minerals containing magnesium and aluminum. Such as spinel; iron-containing chromium minerals, such as chromite; titanium-containing minerals, such as rutile; manganese-containing minerals, such as pyrolusite; tin-containing minerals, such as cassiterite, uranium-containing minerals, such as mica Uranium ore and uranium-producing minerals, such as pitch platinum ore [U ₂ O ₅ (U ₃ O ₈ )] and fat lead uranium ore (UO ₃ hH ₂ O).

Any concentration used with the collectors of this invention should result in satisfactory recovery of the desired mineral. In particular, the concentrations used will depend on the individual minerals being recovered, the grade of the ore being treated by froth beneficiation, the desired amount of minerals to be recovered and the specific minerals desired to be recovered. The concentration of the collector used in the present invention is based on the ore used in froth flotation, generally 0.001 to 1.0 kg per metric ton of ore, preferably 0.010 to 0.2 kg per metric ton of ore.

In the froth flotation process of the present invention, it is preferable to use a frother, and all kinds of frothers known in the art to enable the recovery of the desired minerals are suitable.

Frothing agents suitable for use in the present invention include any frothing agent known in the art which recovers the desired mineral. Examples of these foaming agents include: B _5-8 alcohols, pine oil, cresol, C _1-4 alkyl ethers of polypropylene glycol, dihydroxy compounds of polypropylene glycol, glycols, fatty acids, soaps, alkanes Aryl sulfonates, etc. Additionally, blends of these blowing agents may also be used. In froth flotation, all frothers suitable for ore beneficiation can be used in the present invention.

In addition, according to the method of the present invention, the collector of the present invention can be mixed with other collectors well known in the art for use. Collectors known in the art which may be used in combination with the collectors of this invention should provide satisfactory recovery of the desired minerals. Examples of collectors suitable for use in the present invention include: dialkylthioureas, dialkyl and diaryl thiophosphoryl chlorides, dialkyl and diaryl dithiophosphates, alkylthiols, xanthogen Acid formate

uanidine)和烷基丙邻二胺。(Xanthogen formats), xanthates, benzothiazoles, 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 acid and its salts, sulfosuccinates, sulfosuccinate amides, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, alkylpyridinium salts, guanidine (

uanidine) and alkyl propane diamines.

specific implementation plan

The following examples can further illustrate the present invention, but are not meant to limit the scope of the present invention. All parts and percentages are by weight unless otherwise indicated. Synergy is used herein to mean a blend of two or more components whose measured results exceed the weighted average results of each component used alone. This term also implies that, for each test, the results are compared where the total amount of collector used is equal.

Example 1:

Froth Flotation of Copper-Molybdenum Ore from Western Canada

Homogeneous ore containing chalcopyrite and molybdenite, prepared in packs of 1200 grams. The roughing tank flotation method is to grind 1200 grams of ore with 800 milliliters of tap water in a ball mill equipped with mixing balls for 14 minutes (produce about 13% of 100 mesh particles. This slurry is transferred to a machine with automatic slurry The pH of the slurry was adjusted to 10.2 with lime. No additional pH adjustments were made during the test period. The standard frother was methyl isobutyl Base methanol (MIBC).Four-stage rougher cell flotation method followed.

First stage: Collector - 0.0042 kg/ton

MIBC-0.015 kg/ton

- Conditioning - 1 minute

- Flotation - recovery of concentrate after 1 minute

The second stage: collector - 0.0021 kg/ton

MIBC-0.005 kg/ton

- Conditioning - 0.5 minutes

- Flotation - recovery of concentrate after 1.5 minutes

The third stage: collector - 0.0016 kg/ton

MIBC-0.005 kg/ton

- Conditioning - 0.5 minutes

- Flotation - recovery of concentrate after 2 minutes

Fourth stage: Collector - 0.0033 kg/ton

MIBC-0.005 kg/ton

- Conditioning - 0.5 minutes

- Flotation - recovery of concentrate after 2.5 minutes

The results are compiled in Table I.

1. Not an example of the invention

2. R-7 is the test recovery rate after 7 minutes (expressed in decimals)

3. Grade refers to the relative content of a specific metal contained in the total weight recovered in the froth.

In Table I, the 95% confidence interval for the statistical error of the CuR-7 test values is ±0.010. That is, in Table I, the CuR-7 values associated with potassium amylxanthate range statistically from 0.776±0.010, i.e. from 0.766 to 0.786. In Table I, the statistical error associated with the MoR-7 test values is ±0.015. It is clear from these data that after 7 minutes with the collector blend of the present invention, the recoveries of Cu and Mo exceed what would be expected to be obtained at 7 minutes from the weighted average effect when the individual components are used alone, A synergistic effect can be seen.

Example 2:

Froth Flotation of Copper-Nickel Ore from Eastern Canada

）1263起泡剂和0.28千克/吨的捕收剂进行浮选。一系列的样品从加料机输送到工厂的粗选槽中，并装在料斗中，每斗约装1200克的固体。每个料斗的装料可在丹佛（Denves）型池中按照时间-回收率分布图来进行，该池具有自动搅拌和保持恒定浆料水平面的装置，对各个选定的精矿在1.0、3.0、6.0和12.0分钟记录其回收率。在开始除去泡沫以前加入试剂。占用1分钟的调节时间。不用分段加试剂。将各精矿干燥、称重、研碎，并按统计方法抽取样品准备化验。结果汇编于表Ⅱ中。Copper/nickel ores containing chalcopyrite, pyrrhotite and pyrrhotite minerals with 0.0028 kg/t of DOWFROTH

) 1263 foaming agent and 0.28 kg/ton collector for flotation. A series of samples are conveyed from the feeder to the plant's rougher tank and loaded into hoppers, each containing approximately 1200 grams of solids. The charging of each hopper can be done according to the time-recovery profile in a Denves type tank with automatic agitation and means to maintain a constant slurry level at 1.0, 3.0 for each selected concentrate , 6.0 and 12.0 minutes to record the recovery rate. Reagents are added just before foam removal begins. Takes 1 minute of conditioning time. Do not add reagents in sections. Each concentrate is dried, weighed, and ground, and samples are taken for analysis according to statistical methods. The results are compiled in Table II.

1. Not an example of the invention

2. R-12 is the experimental recovery rate after 12 minutes (expressed in decimals)

In Table II, the copper recoveries after 12 minutes are all so high (close to the theoretical value of 1) that statistical confidence intervals cannot be used. In Table II, the 95% confidence interval for the NiR-12 data is ±0.012. Several clearly show that the collector blends of the present invention yield Ni recoveries well in excess of those expected in a weighted average of each component used individually; it can be seen that a synergistic effect occurs.

Example 3:

Froth flotation of Pb/Zn/Ag composite ores from central Canada

A homogeneous 1000 gram sample of ore containing galena, sphalerite, chalcopyrite and argentite was prepared. For each flotation test, the sample was initially charged to a rod mill along with 500 ml of tap water and 7.5 ml of material with particles smaller than 200 mesh (75 microns). After grinding, the material is transferred to tanks with self-agitating paddles for defoaming and standard Denver-type flotation mechanisms.

Then carry out two stage flotation. A copper/lead/silver rougher cell is used in the first stage and a zinc rougher cell in the second stage. To start the first stage of flotation, add 1.5 grams of sodium carbonate per kilogram of material (to make the pH 9 to 9.5), followed by the addition of collectors. The batch was then aired and conditioned with stirring for 5 minutes. Then, adjust for an additional 2 minutes with stirring only. Then add MIBC foaming agent (the standard dosage is 0.015 ml/kg. Collect the concentrate after 5 minutes of flotation and mark it as copper/lead rougher pool concentrate.

The second-stage flotation material is composed of the residue in the first-stage pool plus 0.5 kg/ton of copper sulfate. Lime is then added to adjust the pH to 10.5. Then adjust with stirring only for 5 minutes. Recheck the pH again and adjust back to 10.5 with lime. At this point, join the Collect and then condition for an additional 5 minutes with stirring only. Then add MIBC foaming agent (standard dosage is 0.020 ml/kg). Flotate for 5 minutes, collect the concentrate, and mark the zinc rougher concentrate.

The concentrate samples were dried, weighed and prepared for X-ray analysis. With the aid of assay data, calculate recovery and grade (both expressed as decimals) using standard mass balance formulas. The results are compiled in Table III.

For the two test conditions shown in Table III, it is logically permissible to compare the recoveries obtained with the collector blends of the present invention with those obtained using either collector component alone.

A comparison of the Cu/Pb flotation (stage 1) experiment alpha using collector D alone with the Cu/Pb flotation (stage 1) experiment using collector blend D+B showed that using this The inventive collector blend can obtain higher recovery rates of Ag, Cu, and Pb. The statistical error at the 95% confidence interval is ±0.01 for Ag, ±0.01 for Cu, and ±0.02 for Pb.

Comparing Zn Flotation (Second Stage) Trial 3 with Zn Flotation (Second Stage) Trial 2 also shows that the use of the admixture significantly increases Zn recovery over the use of either component alone. The 95% confidence interval of the statistical error is ±0.01 for Zn.

At various stages, other trials with individual components are not listed in Table 3 because sufficient meaningful comparative data could not be collected for many of the individual components when used alone. For example, for Cu and Pb, recoveries obtained with Collector B alone were less than 0.500 in the first stage.

Example 4:

Froth flotation of Cu/Mo composite ores from South America

A 500 gram batch of Cu/Mo ore with several copper-alloying sulfide minerals and molybdenite was placed in a rod mill fitted with a one-inch (2.5 cm) rod along with 257 grams of deionized water and a quantity of lime. The mixture is then spun 360 revolutions at 60 revolutions per minute to obtain a particle size distribution of appropriate fineness. The milled slurry was transferred to an Agitar type 1500 ml flotation cell with automatic paddle defoaming system. The slurry is stirred at a speed of 1150 revolutions per minute, and the pH value is adjusted to an appropriate value with more lime or hydrochloric acid (as shown in Table IV).

At this time, the collector is added to the flotation cell (45 g/ton), and then adjusted for 1 minute, at this time, the foaming agent DOWFROTH (DOWFROTH ) 250 (34.4 g/ton) for another minute, then start to feed air into the flotation cell at a rate of 4.5 liters/min, and start the automatic defoaming slurry at the same time. Foam samples were collected at 0.5, 1.5, 3.0, 5.0 and 8.0 minutes, respectively.

Samples and flotation slag were dried overnight in an oven. The dried sample was weighed, pulverized to the appropriate fineness for dissolution and finally dissolved in acid for analysis with a DC plasma spectrometer. The results are compiled in Table IV.

As can be seen from Table IV, after 8 minutes the recovery of Cu is so high (close to the theoretical value of 1.0) that statistical confidence intervals cannot be used.

The 95% confidence interval of the statistical error for the recovery of Mo after 8 min is ±0.012. It is clear that the collector blends of the present invention provide Mo recoveries well in excess of those indicated by analysis of the individual components alone. For example, the Mo recovery for Run 3 significantly exceeds that shown from the weighted average of Runs 1 and 2. A synergistic effect can be seen.

Claims (7)

1. Thereby 1, a kind of by making ore pass through the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration is reclaimed in froth flotation from ore method with the form of aqueous slurry in the presence of flotation collector, described collecting agent comprises:

   (a) be that benchmark content is the formula R of 10～90% (weights) in described collecting agent weight ¹-S-R ²Shown in the hydrocarbon thioether; With

   (b) be that benchmark content is alkylthio carbonate shown in the following formula of 10～90% (weights) in described collecting agent weight

   

   Or thiocarbamate shown in the following formula (or ester)

   

   Or the thiophosphate shown in the following formula

   

   Or their mixture, wherein

   R ¹Be methyl, ethyl, ether or hydrocarbon thioether group,

   R ²The C that combines for aliphatic, alicyclic, aromatics or they _5-11Group,

   R ⁷Be C _1-20Alkyl,

   R ⁸Be respectively C _1-10Alkyl,

   R ¹⁰Be respectively hydrogen, C _1-10Alkyl or aryl,

   M is an alkali metal cation,

   X is respectively S or O separately,

   Y is-S ^-M ⁺Or OR ⁹,

   R ⁹Be C _1-10Alkyl,

   A is integer 1 or 2, and

   B is integer 0 or 1, and condition is a+b=2.
2. 2, in accordance with the method for claim 1, wherein add

   (a) 20～80%(is heavy) described hydrocarbon thioether; With

   (b) 20～80%(weight) described alkylthio carbonate, thiocarbamate (or ester), thiophosphate or their mixture.
3. 3, in accordance with the method for claim 1, wherein said ether and thioether group R ¹With OR ³Or-SR ³Form exist, wherein:

   R ³Be alkyl,

   R ⁷Be C _2-16Alkyl,

   R ⁸Be C _1-4Alkyl,

   R ⁹Be C _2-10Alkyl,

   R ¹⁰Be C _2-8Alkyl or cresyl, and

   M is sodium or potassium cationic.
4. 4, in accordance with the method for claim 3, R wherein ⁷Be C _3-12Alkyl, R ⁸Be C _1-3Alkyl, R ⁹Be C _2-6Alkyl, R ¹⁰Be C _2-8Alkyl or cresyl.
5. 5, in accordance with the method for claim 1, wherein the total carbon content of hydrocarbon thioether is 6～16 carbon atoms.
6. 6, in accordance with the method for claim 5, R wherein ¹Be methyl or ethyl, R ²Be C _6-11Alkyl or C _6-11Thiazolinyl.
7. 7, in accordance with the method for claim 1, R wherein ¹And R ²It is not same alkyl.