CN86101646A - The new collector composition that is used for froth flotation method - Google Patents

The new collector composition that is used for froth flotation method Download PDF

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CN86101646A
CN86101646A CN86101646.7A CN86101646A CN86101646A CN 86101646 A CN86101646 A CN 86101646A CN 86101646 A CN86101646 A CN 86101646A CN 86101646 A CN86101646 A CN 86101646A
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alkyl
thioether
mineral
hydrocarbon
described method
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CN1011945B (en
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理查德·R·克里姆贝尔
罗伯特·D·翰森
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Dow Chemical Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/014—Organic compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/025—Precious metal ores

Abstract

The present invention relates to novel composition, in froth flotation method, is a kind of effective collecting agent, can reclaim the metallic oxide mineral that contains nonmetallic sulfide mineral and sulfuration materialization from ore.It comprises: the hydrocarbon that (a) contains one or more single thio-ether units, wherein, the sulphur atom that combines with sulphur atom be aliphatic series or cyclic aliphatic carbon atom, simultaneously, the total carbon content of hydrocarbon part should be to make hydrocarbon have enough hydrophobic propertys, and the metallic oxide ore composition granule of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface; (b) alkylthio carbonate; Thion carbaminate, thiophosphate or its mixture.

Description

The new collector composition that is used for froth flotation method
The invention relates to a kind of novel collector composition, it is suitable for adopting froth flotation method, reclaims the metallic oxide mineral of metallic sulfide mineral and sulfuration from ore.
Floatation is to handle the method for the mineral solids mixture of pulverizing.For example, powder ore is suspended in some liquid, the solid that a part of whereby solid is pulverized from another part is separated as being present in clay the ore and other similar material.By in liquid, feeding gas (or by on-the-spot gas supplied), can produce the foam that one deck contains certain solid at liquid upper, other solid constituent in residual (suspension) ore that does not foam down.The principle of floatation basis is, when feeding gas in the liquid that is suspended with the different material solid particle, some gases are sticked on the solid particle of some suspension, and do not stick on other solid particle, like this, just make the particle that is stained with gas lighter than liquid, these particles will rise to the liquid upper strata and form foam.
Various flotation agent have been arranged by improving the method for foaming with the suspended substance fusion.The function of above-mentioned additive can be divided into: collecting agent, be used for sulfide, it comprises xanthates, thion carbaminate etc., example with foaming agent of the performance that forms stable foam has: natural oils such as pine tar and eucalyptus oil, and modifier such as activator are in the presence of collecting agent, can bring out the flotation effect, copper sulphate for example, inhibitor is as Cymag, it can stop flotation collector and certain mineral that should stay in the liquid to work, a part that stops certain material to be brought up whereby to become foam, the PH conditioning agent can produce best metallurgical effect, lime for example, soda ash etc.
Should remember that selecting for use of above-mentioned various additives should be according to the character of ore, the mineral of attempting to reclaim and other additives of selecting for use simultaneously decide.
In order to implement the present invention, become the phenomenon of valuable especially industrial operation to making floatation, understanding be unnecessary.Yet this phenomenon can think, and is suspended in the mealy solid particle surface of containing in the liquid of depositing gas, and on the one hand to liquid, the selective affinity to gas has much relations on the other hand.
Floating principle is applied in the ore dressing process of some mineral, and from containing iron sulfide mineral, for example Selective Separation comes out also to belong to wherein row in pyrite, the magnetic iron ore the sulfide mineral of cupric, zinc, lead, nickel, molybdenum and other metal.
Reclaim the metal oxide mineral of metallic sulfide mineral or sulfuration, normally used collecting agent has xanthates, dithiophosphates and thionocarbamate.These volatile sulfur compoundses are often discharged into the atmosphere by chimney, or adopt washing facility expensive, that make with extra care to remove from these chimneys.Also naturally in the ore that iron sulfide mineral forms be present in many sulfide mineral or metallic oxide minerals that contain non-ferrous metal by containing.When the sulfide mineral with floatation iron content when recovery contains the metal oxidation-containing mineral of the sulfide mineral of non-ferrous metal or sulfuration also reclaims together, the content of sulphur is too big, in fusion process, discharge, cause having undesirable a large amount of sulphur during the smelting operation.Therefore, need a kind of selective recovery to contain the sulfide mineral of non-ferrous metal and the metallic oxide mineral of sulfuration, do not contain iron sulfide mineral and do not reclaim.
In commercial collecting agent, xanthic acid salt, thion carbaminate and dithiophosphates in the presence of the sulfide mineral of iron content, can not optionally reclaim the sulfide mineral that contains nonferrous metal.On the contrary, these flotation collectors all capture the indiscriminate ground of all metallic sulfide minerals and reclaim.
Therefore need a kind of flotation collector composition, it can optionally reclaim sulfide that contains nonferrous metal or the metallic oxide mineral that vulcanizes materialization in the presence of the sulfide of iron.
The present invention relates to novel composition, in froth flotation method, is a kind of effective collecting agent, can reclaim sulfide mineral that contains nonferrous metal and the metallic oxide mineral that vulcanizes materialization from ore.New compositions comprises:
(a) contain the hydrocarbon of one or more single thio-ether units, wherein, the carbon atom that combines with sulphur atom is carbon atom aliphatic series or cyclic aliphatic, simultaneously, the total carbon content of hydrocarbon part should be to make hydrocarbon have enough hydrophobic propertys, and the metallic oxide ore composition granule of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface; With
(b) alkylthio carbonate, thion carbaminate, thiophosphate or its mixture.Collecting agent composition for flotation of coal of the present invention, metallic oxide mineral energy high efficiente callback for sulfide mineral that contains nonferrous metal or sulfuration materialization, simultaneously, when the metallic oxide mineral of these metallic sulfide and sulfuration materialization when the sulfide mineral of iron content exists, collecting agent composition for flotation of coal of the present invention has good selectivity to the sulfide mineral that contains nonferrous metal and the metallic oxide mineral of sulfuration materialization.These collecting agents have good collecting effect and good dynamic behavior.
A kind of component of new collector of the present invention is, contains the hydrocarbon of one or more single thio-ether units, wherein, the sulphur atom of thio-ether units and the carbon atom of non-aromatics, promptly the carbon atom of aliphatic series or cyclic aliphatic combines.Here, single thio-ether units is meant that in this element, sulphur atom only combines with the carbon atom of two hydrocarbon parts.At this used hydrocarbon, contain one or more single thio-ether units, also comprise and use hydroxyl, chloro, halogen, ether, this compound that oxyl and hydrocarbon thioether etc. replace.Said herein non-aromatic carbon atom is meant, is not the carbon atom of aromatic ring part.
The hydrocarbon that is suitable for that contains single thio-ether units comprises the compound that meets following molecular formula:
R 1-S-R 2Ⅰ
In the formula, R 1And R 2Be any alkyl or by one or more hydroxyls, cyano group, halogen, ether, the alkyl that oxyl or hydrocarbon thioether replace;
In the formula, R 1And R 2Can combine with S and form heterocycle structure; And the carbon atom that is attached to aliphatic series or cyclic aliphatic from S is condition; Also should be able to make hydrocarbon have enough hydrophobic propertys, the metallic oxide mineral particle of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface be condition with the total carbon content in the hydrocarbon thioether.
Best, R 1And R 2Be arbitrarily one or more hydroxyls, cyano group, halogen, OR 3Or SR 3That replace or unsubstituted aliphatic series, the part of the aralkyl of cyclic aliphatic, wherein, R 3Be alkyl, and R 1And R 2Can combine with S and form heterocycle.R 1And R 2Preferable is with one or more hydroxyl cyano group, halogen, OR 3Or SR 3That replace or part unsubstituted aliphatic series or cyclic aliphatic, wherein, R 1And R 2Can combine with S and form heterocycle.In the better implement scheme, R 1And R 2Do not combine and form heterocycle, simultaneously R with sulphur 1And R 2Be to use one or more hydroxyls, halogen, cyano group, OR 3Or SR 3That replace or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl or cycloalkenyl group, wherein, R 3Be aliphatic series or cyclic aliphatic.In optimum implementation, R 1Be methyl or ethyl, R 2Be C 6-11Alkyl or alkenyl.In best embodiment, R 1And R 2Not same hydroxyl part, that is to say that single thioether is asymmetric.R 3With aliphatic series or cycloaliphatic groups is good.R 3Preferably alkyl, cycloalkyl or cycloalkenyl group.
In the hydrocarbon list thioether, the total carbon content of hydrocarbon part must be to make the hydrocarbon thioether have enough hydrophobic propertys, and the metallic oxide mineral particle of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface.Best, total carbon content is in the hydrocarbon list thioether, and minimum carbon number is 4, more preferably 6, preferably 8.Maximum carbon content is 20, more preferably 16, preferably 12.
Among the present invention, the example of the cyclic compound of hydrocarbon thioether class comprises following structure:
Figure 86101646_IMG4
In the formula, R 4Be arbitrarily aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, hydroxyl, cyano group, halogen, OR 3Or SR 3, wherein, aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group can arbitrarily be used hydroxyl, cyano group, halogen, OR 3Or SR 3Deng replacing; While R 5Be to use hydroxyl, cyano group, halogen, OR 3Or SR 3That replace or alkylidene unsubstituted straight chain or side chain, alkenylene, alkynylene.
In another kind of better implement scheme of the present invention, the hydrocarbon thioether class useful to the present invention, its corresponding molecular formula is:
（R 6） 3-nC（H） n-S-C（H） n（R 6） 3-nⅠc
In the formula, R 6Be any alkyl, or use hydroxyl, cyano group, halogen, ether, the alkyl that hydroxyl oxygen base or hydrocarbon thioether replace; Wherein, two R 6Can combine in conjunction with the formation ring or with sulphur atom and form heterocycle;
N is an integer 0,1,2 or 3; In collecting agent, the total carbon content of hydrocarbyl portion, should make collecting agent have enough hydrophobic propertys is condition, and the metallic oxide mineral particle of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface.
Preferably, R 6For using cyano group, hydroxyl, halogen, OR 3Or SR 3That replace or unsubstituted aliphatic series, cyclic aliphatic, aryl, alkaryl or aralkyl, wherein, R 3As previously mentioned.Preferablely be R 6For using hydroxyl, cyano group, aliphatic ether, cyclic aliphatic ether, replace or the unsubstituted aliphatic or alicyclic part of aliphatic thioether or cyclic aliphatic thioether.Particularly preferably, R 6Be alkyl, thiazolinyl, cycloalkyl or cycloalkenyl group.Best, one-C(H) n(R 6) 3-nBe methyl or ethyl, and another is C 6-11Alkyl or alkenyl.N is good with 1,2 or 3, preferably 2 or 3.
Within the scope of the present invention, the example of hydrocarbon thioether class comprises: methyl butyl sulfide, the methyl amyl thioether, methyl hexyl thioether, the methylheptyl thioether, the Methyl Octyl thioether, methyl nonyl thioether, methyl decyl thioether, a methyl+alkyl thioether, methyl+dialkyl sulfide, the methylcyclopentyl thioether, methylcyclohexyl thioether, methyl suberyl thioether, methyl ring octyl group thioether, the ethyl-butyl thioether, ethyl pentyl group thioether, ethylhexyl thioether, ethyl heptyl thioether, ethyl octyl group thioether, ethyl nonyl thioether, ethyl decyl thioether, an ethyl+alkyl thioether, ethyl+dialkyl sulfide, ethyl cyclopenta thioether, ethyl cyclohexyl thioether, ethyl ring hepta-thioether, ethyl ring octyl group thioether, propyl group butyl thioether, propyl group amyl group thioether, propyl group hexyl thioether, the propylheptyl thioether, propyl group octyl group thioether, propyl group nonyl thioether, propyl group decyl thioether, a propyl group+alkyl thioether, propyl group+dialkyl sulfide, propyl group cyclopenta thioether, propyl group cyclohexyl thioether, propyl group suberyl thioether, propyl group ring octyl group thioether, butyl sulfide, butyl amyl group thioether, butyl hexyl thioether, butyl heptyl thioether, butyl octyl thioether, butyl nonyl thioether, butyl decyl thioether, a butyl+alkane thioether, butyl+dialkyl sulfide, butyl cyclopenta thioether, butyl cyclohexyl thioether, butyl suberyl thioether, butyl ring octyl group thioether, diamyl sulfide, amyl group hexyl thioether, amyl group heptyl thioether, amyl group octyl group thioether, amyl group nonyl thioether, amyl group decyl thioether, an amyl group+alkyl thioether, amyl group+dialkyl sulfide, amyl group cyclopenta thioether, amyl group cyclohexyl thioether, amyl group suberyl thioether, amyl group ring octyl group thioether, the dihexyl thioether, hexyl heptyl thioether, hexyl octyl group thioether, hexyl nonyl thioether, hexyl decyl thioether, a hexyl+alkyl thioether, hexyl+dialkyl sulfide, hexyl cyclopenta thioether, hexyl cyclohexyl thioether, hexyl suberyl thioether, hexyl ring octyl group thioether, diheptyl thioether, heptyl octyl group thioether, heptyl nonyl thioether, heptyl decyl thioether, a heptyl+alkyl thioether, heptyl+dialkyl sulfide, heptyl cyclopenta thioether, heptyl cyclohexyl thioether, heptyl suberyl thioether, heptyl ring octyl group thioether, the dioctyl thioether, octyl group nonyl thioether, octyl-decyl thioether, an octyl group+alkyl thioether, octyl group+dialkyl sulfide, octyl group cyclopenta thioether, octyl group cyclohexyl thioether, octyl group suberyl thioether, octyl group ring octyl group thioether, octyl group ring decyl thioether, dinonyl thioether, nonyl decyl thioether, a nonyl+alkyl thioether, nonyl+dialkyl sulfide, nonyl cyclopenta thioether, nonyl cyclohexyl thioether, nonyl suberyl thioether, nonyl ring octyl group thioether, didecyl thioether, a decyl+alkyl thioether, decyl+dialkyl sulfide, decyl cyclopenta thioether, decyl cyclohexyl thioether, decyl suberyl thioether, decyl ring octyl group thioether.Preferable thioether comprises: methyl hexyl thioether, methylheptyl thioether, Methyl Octyl thioether, methyl nonyl thioether, methyl decyl thioether, ethylhexyl thioether, ethyl heptyl thioether, ethyl octyl group thioether, ethyl nonyl thioether, ethyl decyl thioether, butyl sulfide, diamyl sulfide, dihexyl thioether, diheptyl thioether and dioctyl thioether.
Second component of new collector composition of the present invention is alkylthio carbonate, thion carbaminate, thiophosphate, or their mixture.At this, alkylthio carbonate refers to the compound that contains the thiocarbonate part and contain an alkyl at least, wherein, alkyl has enough hydrophobic propertys, so that the metallic oxide mineral particle of metallic sulfide mineral or sulfuration materialization is driven on air-bubble interface.The corresponding molecular formula of desirable alkylthio carbonate is:
Figure 86101646_IMG5
In the formula, R 7Be C 1-20Alkyl;
X can be arbitrarily S or O in each case;
M is an alkali metal cation.
Desirable alkylthio carbonate comprises alkyl-thiocarbonate, alkyl dithiocarbonate or alkyl trithiocarbonate.
The corresponding molecular formula of desirable alkyl-thiocarbonate is:
Figure 86101646_IMG6
In the formula, R 7With M with stipulate previously identical.
The example of desirable alkyl-thiocarbonate comprises ethyl-sodium thiocarbonate, isopropyl-sodium thiocarbonate, isobutyl group-sodium thiocarbonate, amyl group-sodium thiocarbonate, ethyl-potassium thiocarbonat, isopropyl-potassium thiocarbonat, isobutyl group-potassium thiocarbonat, isobutyl group-potassium thiocarbonat and amyl group-potassium thiocarbonat.
The alkyl dithiocarbonate typically refers to yellow true hydrochlorate.The corresponding molecular formula of desirable alkyl dithiocarbonate is:
Figure 86101646_IMG7
In the formula, R 7With M with stipulate previously identical.
Desirable alkyl dithiocarbonate comprises potassium ethyl dithiophosphate, ethyl dithiocarbonic acids sodium, diamyl disulfide is for potash, diamyl disulfide is for sodium carbonate, isopropyl dithio magnesium phosphate isopropyl dithiocarbonic acids sodium, sec-butyl dithiocarbonic acids sodium, sec-butyl potassium dithiocarbonate, isobutyl group dithiocarbonic acids sodium, isobutyl group potassium dithiocarbonate etc.
The corresponding molecular formula of desirable alkyl trithiocarbonate is:
Figure 86101646_IMG8
In the formula, R 7With M with stipulate previously identical.
The example of alkyl three thiocarbonates comprises isobutyl group trithiocarbonic acid sodium and isobutyl group trithiocarbonic acid potassium.
The corresponding molecular formula of desirable thion carbaminate is:
Figure 86101646_IMG9
In the formula, R 8Be any one C in each case 1-10 alkyl;
Y is-S -M +Or OR 9Be C 1-10 alkyl;
A is integer 1 or 2; With
B is integer 0 or 1, must equal 2 at this a+b.
Best thion carbaminate comprises dialkyl dithiocarbamate and alkyl sulfide carbonyl amino formates.The corresponding molecular formula of best dialkyl dithiocarbamate is:
In the formula, M with stipulate previously identical; R 8Be any one C 1-10Alkyl.
Desirable dialkyl dithiocarbamate comprises: the methyl butyl dithiocar-bamate, the methyl-isobutyl dithiocar-bamate, methyl sec-butyl dithiocar-bamate, the methyl-propyl dithiocar-bamate, the isopropyl methyl dithiocar-bamate, ethyl-butyl dithiocar-bamate, ethyl isobutyl group dithiocar-bamate, ethyl sec-butyl dithiocar-bamate, ethyl propyl dithiocar-bamate and ethyl isopropyl dithiocar-bamate.
The corresponding molecular formula of desirable alkyl thionocarbamate is:
Figure 86101646_IMG11
In the formula, R 8With stipulate previously identical, R 9Be C 1-10Alkyl.
The example of desirable alkyl thionocarbamate comprises: N-methyl thion butyl carbamate, N-methyl thion isobutyl carbamate, N-methyl thion ammonia sec.-butyl formate, N-methyl thion carbamic acid propyl ester, N-methyl thion carbamic acid isopropyl ester, N-ethyl thion butyl carbamate, N-ethyl thion isobutyl carbamate, the amino first of N-ethyl thion secondary butyl ester, N-ethyl thion carbamic acid propyl ester and N-ethyl thion carbamic acid isopropyl ester.Preferable thionocarbamate comprises: N-ethyl thion carbamic acid isopropyl ester and N-ethyl thion isobutyl carbamate.
The corresponding molecular formula of desirable thiophosphate is generally:
In the formula, R 10Can be arbitrarily hydrogen, C 1-10Alkyl or aryl;
X is oxygen or sulphur; With
M is an alkali metal cation.
Available thiophosphate comprises: monoalkyl dithiophosphates, dialkyl dithiophosphate, diaryl dithiophosphates and dialkyl group monothio phosphate.The corresponding molecular formula of a desirable alkyl dithiophosphoric acid salt is:
Figure 86101646_IMG13
In the formula, R 10With M with stipulate previously identical.
The example of a desirable alkyl dithiophosphoric acid salt comprises: Aerofloats, propyl disulfide be for phosphate, isopropyl dithiophosphates, Aerofloats, sec-butyl dithiophosphates and isobutyl dithiophosphates.
Available dialkyl group and diaryl dithiophosphates meet molecular formula and are:
Figure 86101646_IMG14
In the formula, R 10With M with stipulate previously identical.
The example of dialkyl group and diaryl dithiophosphates comprises: diethyldithioposphoric acid sodium, two sec-butyl phosphordithiic acid sodium, diisobutyl phosphordithiic acid sodium, diisoamyl phosphordithiic acid sodium and vesorcinol phosphordithiic acid sodium.
Available dialkyl group monothio phosphate meets molecular formula:
Figure 86101646_IMG15
In the formula, R 10With M with stipulate previously identical.
Desirable-thiophosphate comprises: diethyl-sodium thiophosphate, two sec-butyls-sodium thiophosphate, diisobutyl-sodium thiophosphate and diisoamyl-sodium thiophosphate.
R 7To select C for use 2-16Alkyl is good, preferably C 3-12Alkyl.R 8To select C for use 1-4Alkyl is good, preferably C 1-3Alkyl.R 9To select C for use 2-10Alkyl is good, especially C 2-6Alkyl, preferably C 3-4Alkyl.R 10To select C for use 2-8Alkyl or cresyl are good.
Composition of the present invention preferably comprises: (a) molecular formula is the hydrocarbon thioether of I and (b) molecular formula is the alkylthio carbonate of II, molecular formula is the thion carbaminate of III, molecular formula is the thiophosphate of IV or their mixture, the ratio of composition should make, in the froth flotation process, composition is effective collecting agent to the metallic oxide mineral of metallic sulfide mineral and sulfuration materialization.
Composition of the present invention can comprise: (a) about by weight 10% to about 90% molecular formula is the hydrocarbon thioether of I; (b) about by weight 10% to about 90% molecular formula is the alkylthio carbonate of II, and molecular formula is the thion carbaminate of III, and molecular formula is the thiophosphate of IV or their mixture.
Composition more preferably of the present invention comprises: (a) about by weight 20% to about 80% molecular formula is the hydrocarbon thioether of I; (b) about by weight 20% to about 80% molecular formula is the alkylthio carbonate of II, and molecular formula is the thion carbaminate of III, and molecular formula is the thiophosphate of IV or their mixture.
Composition of the present invention preferably comprises: (a) about by weight 70% molecular formula is the hydrocarbon thioether of I; (b) about by weight 70% molecular formula is the alkylthio carbonate of II, and molecular formula is the thion carbaminate of III, and molecular formula is the thiophosphate of IV or their mixture.In optimum implementation of the present invention, molecular formula is that the hydrocarbon thioether of I is the thiocarbonate of II to molecular formula, molecular formula is the thion carbaminate of III, molecular formula is the ratio of the thiophosphate or their mixture of IV, should make in the froth flotation process, the rate of recovery of oxide mineral to the metal of metallic sulfide mineral or sulfuration materialization should be higher than under the situation of same consumption getable result when any component is wherein used separately.Consumption when collecting agent uses preferably, the molecular formula in composition is an II, the component of III or IV (b) when using separately with this consumption, is that the hydrocarbon thioether of I is compared with the molecular formula of same consumption, can obtain the higher rate of recovery.
New collector composition of the present invention is compared during with arbitrary composition in the independent use collecting agent, can obtain the higher rate of recovery, with obtaining higher metal content often.Grade is meant the relative quantity of contained useful metal in the raw material that foam collects.
Here refer to and contain carbon atom and hydrogen atom item organic compound.Hydrocarbon comprises following organic compound: alkane, alkene, alkyne, cycloalkanes, cyclenes, cycloalkyne, aromatic compounds, the tea compounds of group that replaces with the aralkyl of cyclic aliphatic and alkyl of aliphatic series.
Aliphatic series be meant straight chain here with side chain, saturated undersaturated hydrocarbon, just alkane, alkene or alkyne.Cyclic aliphatic is meant saturated and undersaturated cyclic hydrocarbon, just cyclenes and cycloalkanes here.
Cycloalkanes is meant and contains one, two, and the alkane of three or more rings.Cyclenes is meant the list that contains one or more pairs of keys, two or many cyclic groups.
Alkyl is meant the organic group of carbon containing and hydrogen atom here.Alkyl comprises following organic group: alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, aryl, aliphatic series with the aryl base and the alkaryl of cyclic aliphatic.Aryl is meant biaryl here, xenyl, phenyl, naphthyl, phenanthryl, anthryl and by two alkylene-bridged aryl.Alkaryl here is meant by alkyl, the aryl substituent that alkenyl or alkynyl replaces, wherein aryl with stipulate previously identical.Aralkyl is meant alkyl group here, aryl wherein with stipulate previously identical.
C 1-20Alkyl comprises: straight chain and methyl side chain, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, groups such as nonadecyl and eicosyl.
Halogen is meant chlorine, bromine, iodine group here.
New collector composition of the present invention is effective for reclaim metallic sulfide mineral with froth flotation method from ore with the metallic oxide mineral that vulcanizes materialization.Ore is meant the raw material of taking from the mining area here, and it contains the needed metal-containing minerals that mixes with gangue.Gangue is meant nugatory that part in the raw material here, need separate from needed metallic mineral.
In embodiment preferably, recyclable metallic sulfide mineral.In better implement scheme of the present invention, recyclable cupric, nickel, lead, zinc, or the sulfide mineral of molybdenum.In best embodiment, the sulfide mineral of recyclable cupric.Some better metallic sulfide minerals are also arranged, and they are under the state of oxidation not, and itself just has very high hydrophobicity.The hydrophobicity under the state of oxidation not " this term, be applicable to the mineral that newly grind or have the mineral of unsalted surface that these mineral show, when not adding collecting agent, just can carry out flotation.
Be suitable for using the ore of these compositions to comprise: to contain copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, the sulfide ore of uranium and their mixture.Adopt method of the present invention, the metallic sulfide mineral of borrowing froth flotation method can carry out enrichment, the example comprises: the mineral of cupric, for example, copper mine (CuS), vitreous copper (Cu 2S) chalcopyrite (CuFeS 2), vallerite (Cu 2Fe 4S 7Or Cu 3Fe 4S 7) copper mine (Cu 3S 6S 2), the copper mine (Cu of class 5FeS 4), chalmersite (Cu 2SFe 4S 5), enargite (Cu 3(AS 1S 6) S 4) domeykite (Cu 12AS 4S 13), warringtonite (Cu 4(OH) 6SO 4), piece copper rock (Cu 3SO 4(OH) 4), famatinite (Cu 3(S 6AS) S 4) and bournonite (P 6CuS 6S 3); Leaded mineral, for example, galena (P 6S); The mineral that contain antimony, for example, stibnite (Sb 2S 3); The mineral that contain zinc, for example, zincblende (ZnS); The mineral of argentiferous, for example, stephanite (Ag 2SbS 4) and argentite (Ag 2S); The mineral that contain chromium, for example, sulphur chrome ore iron (FeSCrS falls from the sky or outer space 3) nickeliferous mineral, for example, pentlandite ((FeNi) 9S 8); The mineral that contain molybdenum; For example, molybdenite (MoS 2) and the mineral of platiniferous and palladium, for example, cooperite (Pt(AsS) 2).Preferable metallic sulfide mineral comprises: molybdenite (MoS 2), chalcopyrite (CuFeS 2), galena (PbS), zincblende (ZnS), the copper mine (Cu of class 5FeS 4) and pentlandite (FeNi) 9S 8).
The metallic oxide mineral of sulfuration materialization is the mineral of handling with sulfuration materialization agent, thereby makes its feature with sulfide mineral, so just can adopt the collecting agent that is used for reclaiming sulfide mineral in froth flotation method to reclaim these mineral.The result of sulfuration materialization can make oxide mineral have the feature of sulfide.Oxide mineral can be by contacting the materialization that cures with reacting the compound that forms sulfide linkage or affinity with these mineral.These methods are known technically.This compounds comprises: sodium bisuflide, the salt of sulfuric acid and relevant sulfur-bearing is as vulcanized sodium.
The oxide mineral that is applicable to the sulfuration materialization of this method comprises: the oxide mineral of cupric, aluminium, iron, titanium, tungsten, molybdenum, magnesium, chromium, nickel manganese, tin, uranium and their mixture.The froth flotation method that adopts the present invention to use, the example that can carry out the metallic oxide mineral of enrichment comprises: the mineral of cupric, as cuprite (Cu 2O), black copper ore (CuO), Kong Shi ((Cu 2OH) 2CO 3), chessylite (Cu 3(OH) 2(CO 3) 2), atacamite (Cu 2Cl(OH) 3), silicon hole stone (CuSiO 3); The mineral that contain aluminium are as the corundum ore deposit; The mineral that contain zinc are as zincite (ZnO) and zinc ore (ZnCO 3); The mineral of tungstenic, for example, wolframite ((Fe, Mn) WO 4); Nickeliferous mineral, for example, bunsenite (NiO); The mineral that contain molybdenum, for example, wulfenite (PbMoO 4) and powellite (CaMoO 4); The mineral of iron content are as bloodstone and magnetic iron ore; The mineral that contain chromium are as chromite (FeOCr 2O 3), the mineral of iron content and titanium are as ilmenite; The mineral that contain magnesium and aluminium.As spinelle; The mineral of iron content and chromium are as chromite; The mineral of titaniferous are as rutile; The mineral that contain manganese are as pyrolusite; The mineral of stanniferous, as cassiterite, the mineral of uranium-bearing are as the mineral of mica uranium ore and product uranium, for example pitch platinum ore (U 2O 5(U 3O 8)) and pittinite (UO 3HH 2O).
The employed arbitrary concentration of collecting agent of the present invention should be able to make needed mineral obtain the satisfied rate of recovery.Particularly, employed concentration should depend on the various mineral that are recovered, the grade of the ore handled with the froth flotation method, the desired mineral quality that is recovered and the certain minerals of required recovery.The concentration of collecting agent used in the present invention is benchmark with the ore that carries out froth flotation, is generally the per metric ton ore with 0.001 to 1.0 kilogram, is preferably, and the per metric ton ore is with 0.010 to 0.2 kilogram.
In froth flotation method of the present invention, preferably use foaming agent, to know technically, the various foaming agents that can make required mineral obtain reclaiming all are suitable for.
Be applicable to that foaming agent of the present invention comprises, know technically, can reclaim any foaming agent of required mineral.The example of these foaming agents comprises: B 5-8Alcohol, pine tar, cresols, the C of polypropylene glycol 1-4Alkyl ether, the dihydroxy compounds of polypropylene glycol, dihydroxylic alcohols, aliphatic acid, soap class, alkylaryl sulfonate etc.In addition, the blend of these foaming agents also can use.In froth flotation method, be suitable for all foaming agents of ore beneficiation, can both be used for the present invention.
In addition, by method of the present invention, collecting agent of the present invention can mix use with other collecting agent of knowing technically.Can mix with collecting agent of the present invention and use, the collecting agent of knowing technically should be able to make required mineral obtain satisfied recovery.The example that is applicable to collecting agent of the present invention comprises: dialkyl thiourea, dialkyl group and diaryl thiophosphoryl chloride, dialkyl group and diaryl dithiophosphates, alkyl hydrosulfide, xanthogen formate (Xanthogen formates), xanthate, basic benzothiazole, aliphatic acid and soap, alkylsurfuric acid and salt thereof, alkyl and alkarylsulphonic acid and salt thereof, alkyl phosphoric acid and salt thereof, alkyl and aryl phosphoric acids and salt thereof, sulfosuccinate, the sulfo-succinic acid amidic-salt, primary amine, secondary amine, tertiary amine, quaternary amine, Fixanol, guanidine (guanidine) and alkyl propylene diamine.
Specific embodiments
The following examples can further specify the present invention, but and do not mean that the scope of the present invention that limits.Except as otherwise noted, otherwise all umbers and percentage all calculate by weight.Synergism here is meant, when the blend of two or more a plurality of components, and the result of weighted average that its measurement result surpasses each component when using separately.This term also means, for each test, is comparative result under the situation that used collecting agent total amount equates.
Embodiment 1:
Froth flotation from the copper-molybdenum ore of Canada West
The even ore that contains chalcopyrite and molybdenite is prepared by every bag 1200 grams.The rougher floatation is first in the ball mill that mixes ball is housed, and the 1200 gram ore grindings that are added with 800 ml tap waters (were produced about particles on the 100th more than 13% in 14 minutes.This slurry is transferred in the 1500 milliliters of floation tanks of Ah's guitar (Agitair) type that have automatic slurry formula de-bubble system.With lime the PH of slurry is transferred to 10.2.No longer carrying out other PH at duration of test regulates.The foaming agent of standard is methyl isobutyl carbinol (MIBC).Carry out four sections rougher method for floating thereupon.
First section: collecting agent-0.0042 kg/ton
The MIBC-0.015 kg/ton
-regulate-1 minute
Reclaim concentrate after the-flotation-1 minute
Second section: collecting agent-0.0021 kg/ton
The MIBC-0.005 kg/ton
-regulate-0.5 minute
Reclaim concentrate after the-flotation-1.5 minute
The 3rd section: collecting agent-0.0016 kg/ton
The MIBC-0.005 kg/ton
-regulate-0.5 minute
Reclaim the feelings ore deposit after the-flotation-2 minute
The 4th section: collecting agent-0.0033 kg/ton
The MIBC-0.005 kg/ton
-regulate-0.5 minute
Reclaim concentrate after the-flotation-2.5 minute
The results are compiled in the table I.
Figure 86101646_IMG16
1. not example of the present invention
2.R-7 be to test the rate of recovery (expression decimally) after 7 minutes
3. grade is meant the relative amount of the special metal that is contained in the gross weight that reclaims in floating foam.
In the table I, 95% confidential interval of CuR-7 test value statistical error is ± 0.010.Just, in the table I, the scope of statistics of the CuR-7 value relevant with amylic potassium xanthate is 0.776 ± 0.010 promptly by 0.766 to 0.786.In the table I, the statistical error relevant with the MoR-7 test value be ± 0.015.Show clearly that by these data through after 7 minutes, the rate of recovery of Cu and Mo has surpassed each composition when using separately with collecting agent blend of the present invention, is expected the rate of recovery that obtained at 7 minutes by the weighted average effect; As seen synergistic effect has taken place.
Embodiment 2:
Froth flotation from the copper-nickel ores of Canadian east
Contain chalcopyrite, the copper/nickel ores of pentlandite and magnetic iron ore mineral is with the Dao Fuluosi (DOWFROTH of 0 0.0028 kg/ton
Figure 86101646_IMG17
) collecting agent of 1263 foaming agents and 0.28 kg/ton carries out flotation.A series of sample is transported to the rougher of factory from charger, and is contained in the material bucket, and every bucket is adorned the solid of 1200 grams approximately.The charging of each hopper can be in type pond, Denver (Denves) according to time-rate of recovery distribution map carries out, this pond had automatic stirring and keeps the device of constant slurry level, and each selected concentrate was write down its rate of recovery at 1.0,3.0,6.0 and 12.0 minutes.Beginning except that adding reagent before defoaming.Take 1 minute adjusting time.Add reagent without segmentation.With each concentrate drying, weigh, grind, and prepare chemical examination by the statistical method draw samples.The results are compiled in the table II.
Figure 86101646_IMG18
1. not example of the present invention
2.R-12 be to test the rate of recovery (expression decimally) after 12 minutes
In the table II, after 12 minutes, the rate of recovery of copper is all very high, and (near theoretical value 1) is so that can not use the confidential interval of statistics.In the table II, 95% confidential interval of NiR-12 data is ± 0.012.Data clearly show, the Ni rate of recovery that collecting agent blend of the present invention obtains has substantially exceeded those desired rate of recovery in weighted average when each component is used separately; As seen synergistic effect has taken place.
Embodiment 3:
Froth flotation from the Pb/Zn/Ag complex ore in the middle part of the Canada
Preparation contains the uniform 1000 gram ore samples of galena, zincblende, chalcopyrite and argentite.For each float test, earlier sample is added in the rod mill, add the material of the particle of 500 ml tap waters and 7.5 milliliters simultaneously less than 200 orders (75 microns).After grinding, material to be transferred in the pond, the pond has the automatic stirring arm that foam removal is used, and has the denver cell tool device of standard simultaneously.
Carry out bis flotation then.In first section, use copper/lead/silver-colored rougher, in second section, use the zinc rougher.For beginning to carry out first section flotation, every kilogram of material adds 1.5 gram sodium carbonate (making PH is 9 to 9.5), then adds collecting agent.Slurry bubbling air and stirring and adjusting are 5 minutes then.Then, only regulate 2 minutes again with stirring.(the standard consumption is 0.015 ml/kg then to add the MIBC foaming agent.Flotation was collected concentrate after 5 minutes, and put on copper/plumbous rougher concentrate.
Second section flotation material adds that by residue in first section pond the copper sulphate of 0.5 kg/ton constitutes.Add lime then PH is transferred to 10.5.Then only use stirring and adjusting 5 minutes.Reexamine PH again, and adjust back to 10.5 with lime.At this moment, add collection, then only use stirring and adjusting 5 minutes again.Add MIBC foaming agent (the standard consumption is 0.020 ml/kg) then.Flotation 5 minutes is collected concentrate, and is put on zinc rougher concentrate.
With the concentrate sample drying, weigh, prepare to be used for the X ray chemical examination.The number of chemical examination is trampled with the mass balance formula of standard not calculate recovery rate and grade (all with fractional representation).It the results are compiled in the table III.
In the table III two kinds of experimental conditions are arranged, the rate of recovery that obtains with collecting agent blend of the present invention compares with being used alone the obtainable rate of recovery of collecting agent component, logically allows.
Cu/Pb flotation (phase I) the test α that uses collecting agent D separately tested with the Cu/Pb flotation (phase I) of using collecting blend D+B compared, the result shows use collecting agent blend of the present invention, can obtain higher Ag, Cu, the Pb rate of recovery.Statistical error during 95% confidential interval is ± 0.01 to Ag, is ± 0.01 to Cu, is ± 0.02 to Pb.
Figure 86101646_IMG19
Zn flotation (second stage) tested with Zn flotation (second stage) test α comparing, also can illustrate and use blend than being used alone the rate of recovery that component can significantly improve Zn.95% confidential interval of statistical error to Zn be ± 0.01.
In the various stages, be not listed in the table 3 with other test of one-component, because many one-components can not be collected enough significant comparing data when using separately.For example, to Cu and Pb, in the phase I, when using collecting agent B separately, the resulting rate of recovery is less than 0.500.
Embodiment 4:
Froth flotation from the Cu/Mo complex ore in South America
Several sulfide mineral of copper and 500 grams Cu/Mo ores in batches of molybdenite of closing are arranged, put into the rod mill that one inch (2.5 centimetres) rod is housed, add 257 gram deionized water and a certain amount of lime simultaneously.Then, mixture changes with the speed rotation 360 that per minute 60 changes, to obtain the size distribution of suitable fineness.Slurry after grinding transferred to have in the floation tank of 1500 milliliters on Ah's guitar (Agitar) type of movable paddle type de-bubble system.Slurry stirs with the speed that per minute 1150 changes, and with more lime or hydrochloric acid pH value is adjusted to suitable value (shown in the table IV).
At this moment, collecting agent is added (45 gram/ton) in the floation tank, then regulate 1 minute, add foaming agent Dao Fuluosi (DOWFROTH this moment
Figure 86101646_IMG20
) 250(34.4 gram/ton) and place one minute again after, beginning is started automatic de-bubble oar simultaneously with speed bubbling air in floation tank of 4.5 liters/minute.Collected foam sample respectively at 0.5,1.5,3.0,5.0 and 8.0 minute.
Sample and floating slag dried overnight in baking oven.With the samples weighing of drying, in order to dissolve, it is crushed to suitable fineness, at last it is dissolved in the acid, so that analyze with the direct-current plasma spectrograph.The result is compiled in the table IV.
By the table IV as seen, after 8 minutes, the rate of recovery of Cu very high (near theoretical value 1.0), so that can not use the confidential interval of statistics.
To the rate of recovery of Mo after 8 minutes, 95% confidential interval of its statistical error is ± 0.012.Very clear, the rate of recovery of the Mo that collecting agent blend of the present invention is provided has substantially exceeded the shown rate of recovery of each component analysis of independent use.For example, the Mo rate of recovery of having tested obviously surpasses the rate of recovery that shows from test 1 and 2 weighted average.As seen synergistic effect has taken place.

Claims (20)

1, a kind of method that reclaims the metallic oxide mineral of metallic sulfide mineral or sulfuration materialization from ore is characterized in that this method comprises the ore with the aqueous slurry shape, in the presence of an amount of flotation collector, carries out froth flotation.Wherein, collecting agent comprises:
The hydrocarbon of [a] one or more single thio-ether units, wherein, the carbon atom that combines with sulphur atom is carbon atom aliphatic series or cyclic aliphatic, simultaneously, the total carbon content of hydrocarbon part should be to make hydrocarbon have enough hydrophobic propertys, so that the metallic oxide ore composition granule of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface and
[b] alkylthio carbonate, the thion carbaminate, thiophosphate or its mixture under such condition, make the sulfide mineral of metal or the metallic oxide mineral of sulfuration materialization be collected in the foam.
2, by the described method of claim 1, wherein (a) hydrocarbon thioether and (b) alkylthio carbonate, the carbonyl amino formates, the ratio of thiophosphate or its mixture, should make the collecting agent that makes in this ratio in the froth flotation process, can reclaim the metallic oxide mineral of metallic sulfide mineral and sulfuration materialization effectively.
3, by claim 1 or 2 described methods, wherein the hydrocarbon thioether meets molecular formula:
R 1-S-R 2Ⅰ
Thiocarbonate meets molecular formula:
The thion carbaminate meets molecular formula:
Figure 86101646_IMG2
Meet molecular formula with thiophosphate:
Figure 86101646_IMG3
In the formula, R 1And R 2Be any one alkyl or by one or more hydroxyls, cyano group, halogen, ether, the alkyl that oxyl or hydrocarbon thioether replace;
In the formula, R 1And R 2Can combine with S and form heterocycle structure, the carbon atom that is attached to aliphatic series or cyclic aliphatic with S is a condition, and should have enough hydrophobic propertys from the total carbon content of hydrocarbon thioether, so that the metallic oxide mineral particle of metallic sulfide mineral or sulfuration materialization is driven on air-bubble interface;
R 7Be C 1-20Alkyl;
R 8Be any one C 1-10Alkyl;
R R 9Be C 1-10Alkyl;
R 10Can be arbitrarily hydrogen, C 1-10Alkyl or aryl;
M is an alkali metal cation;
X is arbitrarily S or O in each case;
Y is-S -M +Or OR 9;
A is integer 1 or 2; With
B is integer 0 or 1, at this a+b=2.
4, by the described method of claim 3, comprising:
(a) the hydrocarbon thioether is by weight between 10% and 90%; With
(b) alkylthio carbonate, the thion carbaminate, thiophosphate or its mixture are by weight between 10% and 90%.
5, by the described method of claim 4, comprising:
(a) the hydrocarbon thioether is by weight between 20% and 80%; With
(b) alkylthio carbonate, the thion carbaminate, thiophosphate or its mixture are by weight between 20 and 80%.
6, by claim 3 or 5 described method, wherein R 1And R 2Be arbitrarily to use one or more hydroxyls, cyano group, halogen, OR 3Or SR 3That replace or unsubstituted any one aliphatic series, part cyclic aliphatic or aralkyl;
R 3It is alkyl;
In the formula, R 1And R 2Can be with S in conjunction with forming heterocycle;
R 7Be C 2-16Alkyl;
R 8Be C 1-4Alkyl;
R 9Be C 2-10Alkyl;
R 10Be C 2-3Alkyl or hydroxy phenyl; With
M is sodium or potassium cationic.
7, by the described method of claim 6, wherein the total carbon content of hydrocarbon thioether is 4 to 20 carbon atoms.
8, by the described method of claim 7, wherein R 1And R 2Be to use one or more hydroxyls, cyano group, halogen, OR 3Or SR 3Replace or unsubstituted cyclic aliphatic or aliphatic part; In the formula, R 1And R 2Can combine with S and form heterocycle; R 7Be C 3-12Alkyl; R 8Be C 1-2Alkyl, R 9Be C 2-6Alkyl and R 10Be C 2-3Alkyl or cresyl.
9, by the described method of claim 8, wherein the total carbon content that had of hydrocarbon thioether is 6 to 16 carbon atoms.
10, by the described method of claim 9, wherein R 1And R 2It is arbitrarily alkyl or alkenyl.
11, by the described method of claim 10, wherein R 1Be methyl or ethyl, R 2Be C 6-11Alkyl or alkenyl.
12, by claim 3 or 5 described methods, wherein the hydrocarbon thioether meets molecular formula:
（R 6） 3-nC（H） n-S-C（H） n（R 6） 3-nⅠc
In the formula, R 6Be arbitrarily alkyl or use hydroxyl, cyano group, halogen, ether, the alkyl that oxyl or hydrocarbon thioether replace; In the formula, two R 6Can be in conjunction with forming ring or sulphur atom in conjunction with forming heterocycle;
N is an integer 0,1,2 or 3; Can make collecting agent have enough hydrophobic propertys with the total carbon content of hydrocarbon part in the collecting agent is condition, so that the metallic oxide ore composition granule of metallic sulfide mineral or sulfuration materialization can be driven on air-bubble interface.
13, by the described method of claim 12, comprising:
(a) hydrocarbon thioether; With
(b) comprise alkyl-thiocarbonate, the alkylthio carbonate of alkyl dithiocarbonate or alkyl trithiocarbonate.
14, by the described method of claim 13, wherein metallic sulfide mineral is recovered in the foam.
15, by the described method of claim 14, the metallic sulfide that wherein is recovered in the foam contains copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, gold, uranium or their mixture.
16, by the described method of claim 15, the metallic sulfide mineral that wherein is recovered in the foam is a molybdenite, chalcopyrite, galena, zincblende, class's copper mine or nickel chalcopyrite.
17, by the described method of claim 16, wherein the concentration of collecting agent should be 0.001 to 1.0, the ore of kilogram collecting agent/ton froth flotation.
18, by the described method of claim 3, wherein R 1And R 2It is hydrocarbyl portion inequality.
19, by the described method of claim 1, wherein metallic sulfide mineral is the mineral that have high intrinsic hydrophobic property under the state of oxidation not.
CN86101646A 1985-07-12 1986-02-17 Method for froth flotation using collector composition Expired CN1011945B (en)

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CN107442267A (en) * 2017-07-28 2017-12-08 西部矿业股份有限公司 A kind of microfine difficulty selects the method for floating of marmatite
CN108435432A (en) * 2018-04-03 2018-08-24 中南大学 A kind of combined flotation agent and its application for the carbon containing Pyrite-type gold ore flotation of high arsenic
CN108816521A (en) * 2018-05-22 2018-11-16 中南大学 Application of the trihydroxy benzene and its derivative as bismuth inhibitor in floatation process
CN110280394A (en) * 2019-06-09 2019-09-27 沈阳有研矿物化工有限公司 A kind of isopentyl xanthic acid propynyl ester and preparation method thereof
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CN107442267A (en) * 2017-07-28 2017-12-08 西部矿业股份有限公司 A kind of microfine difficulty selects the method for floating of marmatite
CN107442267B (en) * 2017-07-28 2019-03-15 西部矿业股份有限公司 A kind of microfine difficulty selects the method for floating of marmatite
CN108435432A (en) * 2018-04-03 2018-08-24 中南大学 A kind of combined flotation agent and its application for the carbon containing Pyrite-type gold ore flotation of high arsenic
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PH22952A (en) 1989-02-03
FI871017A (en) 1987-03-09

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