CN86101495A - The collector composition that is used for the pneumatic flotation of mineral effective constituent - Google Patents
The collector composition that is used for the pneumatic flotation of mineral effective constituent Download PDFInfo
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- CN86101495A CN86101495A CN86101495.2A CN86101495A CN86101495A CN 86101495 A CN86101495 A CN 86101495A CN 86101495 A CN86101495 A CN 86101495A CN 86101495 A CN86101495 A CN 86101495A
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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
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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
- B03D1/01—Organic compounds containing nitrogen
-
- 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
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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
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of collector composition can be used for froth-flotation method and reclaim containing metal sulfide mineral, containing metal oxide mineral, the metal oxide mineral of sulfuration materialization and the metal that exists with metallic state from ore, and said composition is made of two kinds of collecting agents.A kind of collecting agent is the organic compound that contains 4 carbon atoms and one or more single thio-ether units at least, and the carbon atom that links to each other with sulphur atom is aliphatic series or alicyclic carbon atom.Another kind of collector is ω-(sulfenyl) alkylamine preferably, S-(ω-aminoalkyl) alkyl thioester, N-(alkyl)-α, ω-alkyl diamine, (ω-aminoalkyl) alkyl acyl ammonia, ω-(-oxyl) alkylamine, ω-aminoalkyl supercarbonate, ω-(sulfenyl)-alkylamine or their mixture.
Description
The invention relates to novel collector, be used to reclaim metallic sulfide mineral, the metallic oxide mineral of sulfuration materialization, metallic oxide mineral and with the metal that metallic state exists, the four class mineral of being mentioned here refer to the metal-containing minerals that is obtained through pneumatic flotation by ore.
Flotation process is a kind of processing finely disintegrated mineral solids mixture, it is the processing method of Powdered ore, at this, the ore of pulverizing floated on a liquid in this liquid, produce a kind of foam-like material by importing a kind of gas (or a kind of gas is provided on the spot), this foam-like material contains some solid that is in liquid upper, and stay in the ore other solid ingredient of suspend (bubbling), thereby make the Powdered ore solid part and other finely powdered solid that are suspended in certain liquid, as clay and other similar substance of being present in the ore are separated.
The principle of flotation process institute foundation is, a kind of gas importing is contained in the liquid of different suspended matter solid particulates, here some gases produce sticking power to some suspended solids does not then have sticking power to other suspended solids, makes the particle that is attached with gas compare liquid light.Therefore, these particles are with regard to the top that rises to liquid and form foam.
Various flotation agent are mixed with suspension to improve the floatation process method.According to role, these flotation agent can be divided into: collector, as xanthate, thionocarbamate etc.; Generate the pore forming material of stable foam easily, as natural oil, pine tar, Oil of Eucalyptus; Properties-correcting agent is for example induced the activator of flotation effect, as copper sulfate in the presence of collector; Inhibitor, as sodium cyanide, it helps to prevent that collector from working to the mineral that hope is retained in the liquid, thereby prevents that these materials are with up a formation foamy part; The PH conditioning agent is as lime, soda ash, in order to produce best metallurgical effect; And other material.
Make method for floating become the understanding of phenomenon of a valuable especially industrial operation to implementing the present invention and inessential.As if the phenomenon that makes method for floating become valuable especially industrial operation mainly is such, and the granular solids surface that is suspended in the liquid that contains entrap gas is relevant with the selection affinity of gas on the other hand with liquid on the one hand.According to the character of ore, the mineral of attempting to reclaim and other additive that is used with it select to be used for the specialist additive of floating operation.
Flotation is applied in some mineral separation processes methods, comprises optionally separating with pyrrhotite as pyrite such as the metal-containing minerals and the iron content sulfide mineral of cupric, zinc, lead, nickel, molybdenum and other metal.
In collector, be generally used for reclaiming metallic sulfide mineral or sulfuration materialization metallic oxide ore be xanthogenate, dithiophosphates and thion carbaminate.Usually other the useful collector of metallic oxide mineral that is considered to reclaiming metal-containing minerals or sulfuration materialization is a mercaptan, disulphide (R-SS-R) and polysulfide [R-(S)
n-R], n is more than 3 or 3 here.
The metallic oxide mineral of metallic sulfide mineral or sulfuration materialization is converted into more useful pure state metal normally realized by melting technology.This melter's artistic skill generates volatile sulphur compound, and these volatile sulphur compounds generally spill in the atmosphere through chimney and go, or are removed by expensive and complicated washing plant through these chimneys.Sulfide mineral that contains non-ferrous metal that many natures are found or metallic oxide mineral are present in and contain iron sulfide mineral, in pyrite and pyrrhotite.When the iron content sulfide mineral reclaims in the lump with the metallic oxide mineral of sulfurized that contains the sulfide mineral of non-ferrous metal, then in fusion process, there is the excessive sulphur of overflowing in floatation process.Need a kind of processing method, it only optionally reclaims sulfide mineral that contains non-ferrous metal and the metallic oxide mineral that vulcanizes materialization, does not contain iron sulfide mineral and do not reclaim as pyrite and this class of pyrrhotite.
As for industrial collector xanthogenate, thion carbaminate and dithiophosphates, can not contain in the presence of the iron sulfide mineral, optionally reclaim the sulfide mineral that contains non-ferrous metal; On the contrary, these collectors capture and reclaim all metallic sulfide minerals.The thio-alcohol collector has the undesirable smell of environment, and its speed is very slow in the flotation of metallic sulfide mineral.And disulphide and polysulfide, its recovery rate is also very slow as collector the time.Thereby industrial mercaptan, disulphide and the polysulfide of generally not adopting.In addition, this three classes sulphide flotation collecting agent can not contain in the presence of the iron sulfide mineral, optionally reclaims the sulfide mineral that contains non-ferrous metal.
In sum, need a kind of like this collector, it can in the presence of iron content sulfide mineral and pyrite and pyrrhotite, optionally reclaim large-scale metal-containing minerals with the goodish rate of recovery.
Therefore, on the one hand, the present invention relates to the collector composition that the metal-containing minerals flotation is used, said composition comprises:
(a) as shown in the formula compound:
R
1-X-（R）
n-Q
Ⅰ
At this, Q represents
-N(R
2) a(H) and b herein a+b equal 2,
-N=Y, Y is S, O, alkylene group or substituted alkylene herein,
Three N, or
R
1And R
2Be C arbitrarily
1-22Alkyl, C
1-22Saturated or the undersaturated heterocycle of substituted hydrocarbon radical;
Y+p+m=n herein, wherein n is 1～6 integer, and y, p and m are arbitrarily 0 or 1～6 integer, and each part arbitrarily order occurs;
X is-S--O-,-N-R
3,
R herein
3Be hydrogen, C
1-22Alkyl or C
1-22Substituted hydrocarbon radical;
(b) contain the hydro carbons of single thio-ether units
R
5-S-R
6
Ⅷ
Herein
R
5And R
6It arbitrarily be alkyl or by the alkyl of one or more alkyl, cyano group, fontanel element, ether,-oxyl or the replacement of hydrocarbon thioether;
Herein
R
5And R
6Can combine with S and form heterocycle structure; But S must be connected on aliphatics or the alicyclic carbon atom, it is proper in to have enough hydrophobicitys that the total carbon content of the sulfide of hydrocarbon is kept, and causes the metallic oxide ore composition granule of metallic sulfide mineral or sulfuration materialization to be driven on the interface of air/gas bubbles.
The present invention also relates to from ore to reclaim the processing method of metal-containing minerals, the collector that this method is included in floating amount exists down, and the metal-containing minerals that exists with the form of water slurry is recovered in foam through the foam floating process method.
The large-scale metal-containing minerals of collector compositions energy flotation of the present invention, and these collector compositions have good recovering effect and selectivity to needed metal-containing minerals.
In a desirable processing method of the present invention, the process that described collector is used to reclaim metallic sulfide mineral from ore or vulcanizes the metallic oxide mineral of materialization.This method comprises, in the presence of the collector mixture of floating amount, being driven into the air/gas bubbles interface at the metallic oxide ore stone granulate that is enough to make metallic sulfide mineral or sulfuration materialization is condition, make ore with the form of aqueous slurry through the foam floating process process and in foam, be recovered.
Collector composition of the present invention has produced the unexpected high-recovery of the mineral that contain non-ferrous metal, to these and the high selectivity that contains the non-ferrous metal mineral that contains the iron sulfide mineral coexistence.
Component (a) in the collector composition of the present invention is a component as top (I) formula.Though not statement especially also should be understood in the water medium of low PH in formula I, particularly in acid medium, component (a) can exist with the form of salt.In this formula, R is-(CH)-p,
Their mixture is favourable, and at this p+m+y=n, wherein n is 1～6 integer, and preferable is 2 or 3.R
1With each R
2Be C
1～C
22Alkyl or the C that replaces by one or more hydroxyls, amino, phosphono, alkoxyl group, imino-, formamyl, carbonyl, thiocarbonyl, cyano group, fontanel element, ether, carboxyl, sulfenyl,-oxyl, hydrocarbon amino or hydrocarbon imino
1-22Alkyl is favourable.As be substituted R
1And R
2It is favourable being replaced by one or more hydroxyls, fontanel element, amino, phosphono or alkoxyl group.Q is preferable to be-N(R
2) a(H) b a+b=2 herein.
Advantageously, R
1And R
2The total number of carbon atoms be 6 or more, R
1With C
2-14Alkyl or the C that replaces by one or more hydroxyls, amino, phosphono or alkoxyl group
2-14Alkyl is good, and that more desirable is C
4-11Alkyl; R
2With C
1-6Alkyl, C
1-6Alkyl carbonyl or C
1-6Substituted alkyl or alkyl carbonyl are good, and that more desirable is C
1-4Alkyl or C
1-4Alkyl carbonyl or C
1-6Alkyl or the C that replaces by amino, hydroxyl or phosphono
1-6Alkyl carbonyl, that the most desirable is C
1-2Alkyl or C
1-2Alkyl carbonyl.In addition, R is with-(CH
2)-p or
For good, preferablely be-(CH
2)-p; N is good with 1～4 integer, and the most desirable is 2 or 3; X with-S-,
R
3Or-O-is good, preferablely be-S-or
R
3, the most desirable is-S-; R
3With hydrogen or C
1-14Alkyl is good, and preferable is hydrogen or C
1-11Alkyl, the most desirable is hydrogen.
As mentioned above, component (a) comprises as S-(omega-amino-alkyl) the alkyl thioester:
ω-(sulfenyl) alkylamine and ω-(sulfenyl) alkylamide:
The N-(alkyl)-and α, ω-alkane diamine:
N-(omega-amino-alkyl) hydrocarbon acid amides:
ω-(-oxyl) alkylamine:
Alkyl acid omega-amino-alkyl ester:
R herein
1, R
2, R
3, a, b and n be as the front limited, in formula II-VII, when X be-S-or,
The time, R
1With C
4-10Alkyl is good; When X is
Or
The time, radicals R
1And R
3Total carbon number to be good between about 1 and 23, preferable is between 2 and 16, the most desirable is between 4 and 15; When X is
Or-during O-, R
1That the most desirable is C
6-11Alkyl.
As previously mentioned, the compound of desirable component (a) comprises ω-(sulfenyl) alkylamine, N-(alkyl)-α, ω-alkane diamines, N-(omega-amino-alkyl) the hydrocarbon acid amides, the mixture of ω-(-oxyl) alkylamine or above-claimed cpd.The compound of more desirable component (a) comprises ω-(sulfenyl) alkylamine, ω-(sulfenyl) alkylamide, N-(alkyl)-α, ω-alkane diamines, N-(omega-amino-alkyl) the hydrocarbon acid amides, or the mixture of above-claimed cpd.Best component (a) compound is following a few class: ω-(sulfenyl) alkylamine, for example own sulfenyl of 2-() ethamine and ω-(sulfenyl) alkylamine, for example own sulfenyl of ethyl 2-() ethanamide.
The ω of formula III-people such as (sulfenyl) alkylamine Ke Yong Bei Lazuo Paderewski are at United States Patent (USP) 4,086, and 273; French Patent 1,519,829 and the method preparation narrated of this smooth organic chemistry complete works of Bayer (Beilstein, 4,4th Ed., 4th Supp., 1655(1979)).
The N-(omega-amino-alkyl of formula V) but hydrocarbyl amide usage assistant is difficult to understand at United States Patent (USP) 4,326,067 Acta Polon Pharm, 19,277, this smooth organic chemistry complete works (Beilstein of (1962) and Bayer, 4,4th Ed., 3rd Supp., 587(1962)) described method preparation.
The ω of formula VI-(-oxyl) alkylamine can use English Patent 869,409 and Hao Baisi at United States Patent (USP) 3,397, the preparation of method described in 238.
The alkyl thioic acid sulfoacid S-(omega-amino-alkyl of formula II) but the ester expense she wait the people at United States Patent (USP) 3,328,442 and this smooth organic chemistry complete works of Bayer (Beilstein, 4,4th Ed., 4th Ed., 4th Supp., 1657(1979)) institute's narration method preparation.
The alkyl of formula VII acid omega-amino-alkyl ester can be used JACS (J.Am.Chem.Soc., 83,4835(1961)) and this smooth organic chemistry complete works (Beilstein of Bayer, 4,4th Ed., 4th Supp., the method preparation of 1413,1785(1979)) being narrated.
Formula IV N-(alkyl)-and α, ω-alkane diamines can prepare with known processing method, and wherein an example is Deutsches Wirtschafts Patent 98,519 described methods.
Component in the collector composition (b) is an organic compound, and it contains at least 4 carbon atoms and one or more single thio-ether units, and the sulphur atom of single thio-ether units is connected the non-aromatic carbon atom here, promptly on aliphatics or the alicyclic carbon atom.Single thio-ether units refers to the carbon atom that each sulphur atom only connects two non-aromatic parts here, for example only is connected in the unit on hydrocarbon two carbon atoms partly.Hydrocarbon compound can comprise one or more single thio-ether units, and comprises the compound that is replaced by hydroxyl, cyano group, fontanel element, ether,-oxyl and hydrocarbon thioether.
The desirable organic compound that contains single thio-ether units comprises those that meet following formula
R
5-S-R
6
Ⅸ
R herein
5And R
6It arbitrarily be alkyl or by the alkyl of one or more hydroxyls, cyano group, fontanel element, ether,-oxyl or the replacement of hydrocarbon thioether; R herein
5And R
6Can combine and form the heterocycle structure that contains S; But S must be connected on fat or the alicyclic carbon atom, and the total carbon content of sulfide part also must be kept proper, makes sulfide partly have enough hydrophobicitys, so that metallic sulfide mineral stone granulate is driven on the air/gas bubbles interface.
The specific R that most helps using
5And R
6Group depends on various factors, comprises the component (a) that is adopted, processed particular ore or the like.In general, for supplying with needed hydrophobic property, the monosulphide compounds of formula IX contains 4 at least, and preferable is 6, is preferably 8 carbon atoms.Carbon atom in the monosulphide compounds is good with 20 at most, and preferable is 16, is preferably 12.
R
5And R
6Can be arbitrarily unsubstituted or by one or more hydroxyls, cyano group, fontanel element ,-OR
7Or-SR
7Aliphatic, alicyclic or aralkyl moiety, the R herein that replace
7Be alkyl, R
5And R
6Can combine with sulphur and form heterocycle.R
5And R
6Preferable is unsubstituted or by one or more cyano group, fontanel element, hydroxyl, OR
7Or SR
7The aliphatics and alicyclic part, the wherein R that replace
7Be alkyl, wherein R
5And R
6Can contain the S heterocycle in conjunction with formation.In a preferable specific examples, R
5And R
6Do not contain S heterocycle, R in conjunction with forming
5And R
6Arbitrarily be unsubstituted or by one or more hydroxyls, fontanel element, cyano group, OR
7Or SR
7The alkyl, alkenyl, alkynyl group, cycloalkyl or the cycloalkenyl group that replace, wherein R is an aliphatics or alicyclic.In most preferred embodiment, R
5And R
6Be hydrocarbyl portion inequality, promptly single thioether is asymmetric.R
7With aliphatics or alicyclic be good.R
7Preferable is alkyl, alkenyl, cycloalkyl or cycloalkenyl group.In most preferred embodiment, R
5And R
6Be alkyl or alkenyl, particularly R arbitrarily
5Be methyl or ethyl, R
6Be C
6-11Alkyl or C
6-11Alkenyl, for example ethyl octyl group thioether.
The example of the ring compound of the monosulphide of available formula IX comprises following structure:
R wherein
8Be aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, hydroxyl, cyano group, fontanel element, OR arbitrarily
7Or SR
7Group, wherein aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group can be arbitrarily by hydroxyl, cyano group, fontanel element, OR
7Or SR
7Replace Deng group; R wherein
7Be alkyl, desirable is aliphatics or alicyclic, and preferable is alkyl, alkenyl, cycloalkyl or cycloalkenyl group; R
9For unsubstituted or by hydroxyl, cyano group, fontanel element, OR
7Or SR
7Alkylidene group or the alkylene group or the inferior alkynyl group of the straight or branched that group replaces.
A preferential compound as component (b) of the present invention meets following formula:
（R
4）
3-nC（H）
n-S-C（H）
n（R
4）
3-n
Ⅹ
Herein
R
4It arbitrarily be alkyl or with the alkyl of hydroxyl, cyano group, fontanel element, ether,-oxyl or the replacement of alkyl thioether; Two portions R wherein
4Can be combined into ring or form heterocycle with sulphur atom;
N is an integer 1,2 or 3; But the total carbon content of the hydrocarbon of collector part must be kept the proper collector that makes and have enough hydrophobicitys, causes the metallic oxide ore stone granulate of metallic sulfide mineral or sulfuration materialization to be driven on the air/gas bubbles interface.
In aforementioned formula, R
4Can be taken as unsubstituted or by cyano group, fontanel element, hydroxyl, OR
7Or SR
7That group replaces is aliphatic, alicyclic, aryl, alkaryl or aralkyl group, and wherein R limits as the front.R
4More desirable is aliphatics or alicyclic group unsubstituted or that replace with hydroxyl, cyano group, fontanel element, fatty ether, alicyclic ethers, aliphatics thioether or alicyclic thioether.Even preferable R
4Be alkyl, alkenyl, cycloalkyl or cycloalkenyl group part.The most desirable, one-C(H) n(R
4)
3-nR in the group
4Be methyl or ethyl; R in another same group
4Be C
6-11Alkyl or C
6-11Alkenyl group.N can be taken as 1,2 or 3, more can be taken as 2 or 3.
Comparatively desirable formula R
5-S-R
6The shown hydrocarbon that contains single thio-ether units, wherein R
5And R
6As preceding qualification, available known standard technology method preparation is as with R
6-H and R
5-SH reaction is at this R
5And R
6Still as preceding qualification.
Examples of compounds in this patent scope comprises methyl butyl sulfide, the methyl amyl thioether, methyl hexyl thioether, the methylheptyl thioether, the Methyl Octyl thioether, methyl nonyl thioether, methyl decyl thioether, the methyl undecyl heats up in a steamer ether, methyl dodecyl thioether, the methylcyclopentyl thioether, the methylcyclohexyl thioether, methyl suberyl thioether, methyl ring octyl group thioether, the ethyl-butyl thioether, the ethyl pentyl group thioether, the ethylhexyl thioether, ethyl heptyl thioether, ethyl octyl group thioether, ethyl nonyl thioether, ethyl decyl thioether, ethyl undecyl thioether, ethyl dodecyl thioether, ethyl cyclopentyl thioether, ethyl cyclohexyl thioether, ethyl suberyl 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, the propyl group undecyl heats up in a steamer ether, propyl group dodecyl thioether, propyl group cyclopentyl 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, the butyl octyl thioether, butyl nonyl thioether, butyl decyl thioether, butyl undecyl thioether, butyl dodecyl thioether, butyl cyclopentyl 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, the amyl group undecyl heats up in a steamer ether, amyl group dodecyl thioether, amyl group cyclopentyl 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, hexyl undecyl thioether, hexyl dodecyl thioether, hexyl cyclopentyl thioether, hexyl cyclohexyl thioether, hexyl suberyl thioether, hexyl ring octyl group thioether, the diheptyl thioether, heptyl octyl group thioether, heptyl nonyl thioether, heptyl decyl thioether, the heptyl undecyl heats up in a steamer ether, heptyl dodecyl thioether, heptyl cyclopentyl thioether, heptyl cyclohexyl thioether, heptyl suberyl thioether, heptyl ring octyl group thioether, the dioctyl thioether, octyl group nonyl thioether, the octyl-decyl thioether, octyl group undecyl thioether, octyl group dodecyl thioether, octyl group cyclopentyl thioether, octyl group cyclohexyl thioether, octyl group suberyl thioether, octyl group ring octyl group thioether, the dinonyl thioether, nonyl decyl thioether, the nonyl undecyl heats up in a steamer ether, nonyl dodecyl thioether, nonyl cyclopentyl thioether, nonyl cyclohexyl thioether, nonyl suberyl thioether, nonyl ring octyl group thioether, the didecyl thioether, decyl undecyl thioether, decyl dodecyl thioether, decyl cyclopentyl thioether, decyl cyclohexyl thioether, decyl suberyl thioether and 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.
Hydrocarbon refers to contain the organic compound of carbon and hydrogen atom herein.Term " hydrocarbon " comprises following organic compound: alkane, alkene, alkynes, naphthenic hydrocarbon, cycloolefin, cycloalkyne, aromatic hydrocarbon, aliphatic and alicyclic virtue reach the aromatic hydrocarbon that is replaced by alkyl for alkane.
Wherein aliphatics refers to straight chain and side chain, saturated and undersaturated hydrocarbon polymer, i.e. alkane, alkene and alkynes.Wherein alicyclicly refer to saturated and undersaturated ring-type hydrocarbon polymer, i.e. cycloolefin and naphthenic hydrocarbon.
Naphthenic hydrocarbon refers to and contains one, two, three or the alkane of a plurality of rings.Cycloolefin refers to, the two or more cyclic group that contains one or more pairs of keys.
Wherein alkyl refers to contain the organic group of carbon atom and hydrogen atom.Term " alkyl " comprises following organic group: alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl, aliphatics and alicyclic aralkyl and alkaryl, term " aryl " two aryl referring to di-aryl, biphenylyl, phenyl, naphthyl, phenanthryl, anthryl and connect by the alkenyl raise wherein.Wherein alkaryl refers to the aromatic substituent that replaces with alkyl, alkenyl or alkynyl group, and aryl such as front limit.Wherein aralkyl refers to an alkyl, and its aryl moiety such as front limit.
The C alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and the eicosyl of straight chain and side chain.
Wherein halogen refers to chlorine, bromine or iodine.
Refer to contain the carbon atom that links to each other with nitrogen-atoms by two keys and the organic group of hydrogen atom at this alkylene, the term alkylene comprises following organic group: alkenyl, cycloalkenyl group and Fang Dai alkene, aryl such as front limit here.
Wherein heterocycle refers to comprise one-N-ring filling and undersaturated heterocycle.Heterocycle can comprise one or more N, O or S atom.Suitable heterocyclic example is: pyridine, pyrazoles, furans, thiophene, indoles, cumarone, thionaphthene, quinoline, isoquinoline 99.9, tonka bean camphor, carbazole, acridine, imidazoles, oxazole, thiazole, pyridazine, pyrimidine, pyrazine, purine, aziridine, oxyethane, azetidine, Evil butane, 1,3-epithio propane, pyrroles, tetramethyleneimine, tetrahydrofuran (THF), isoxazole, piperidines, azepines (azepine
) and other.
Composition of the present invention is to be made of component of capacity (a) and component (b), the amount of each component that the effective collector that obtains metal-containing minerals through the foam floating process method from ore with preparation helps adopting most during in the preparation said composition is complied with the specific components (a) that adopted and (b), the particular ore of desire processing and the desired recovery rate that reaches and selectivity and change.Desirable composition contains 10% to the 90%(weight of having an appointment), preferable is 20% to 80%(weight) component (a) and about 10 to 90%(weight), preferable is 20% to 80%(weight) component (b).Composition of the present invention is such even more desirable, promptly contains 30% to the 70%(weight of having an appointment) component (a) and about 30% to 70%(weight) component (b).
Processing method of the present invention is useful to adopting froth-flotation method to reclaim metal-containing minerals from ore.Wherein ore refers to extraction ground and includes the desired metal-containing minerals that exists with the form of mixtures with mine tailing.Wherein mine tailing refers to almost valueless or valueless in the mineral, the part that need separate with desired metal-containing minerals.
Collector composition of the present invention can be used for reclaiming metal-containing minerals by the processing method of pneumatic flotation.In a preferable embodiment of the present invention, the mineral of cupric, nickel, lead, zinc or molybdenum are reclaimed.Also want among the preferable embodiment copper-bearing mineral to be reclaimed at one.To be those have the very mineral of high hydrophobicity in oxidation state not to same desirable containing metal sulfide mineral.Term " in the hydrophobicity of oxidation state not " is applicable to just ground mineral or has the mineral that can demonstrate the clean surface of buoyant tendency when not adding collector.
These compounds can be used for some mineral, and these mineral comprise the sulfide mineral of cupric, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and composition thereof.The example that available processing method of the present invention is carried dense containing metal sulfide mineral by pneumatic flotation comprises copper-bearing mineral, for example: covellite (Cu S), copper glance (Cu
2S), chalcopyrite (Cu Fe S
2), vallerite (Cu
2Fe
4S
7Or Cu
3Fe
4S
7), purple copper (Cu
5Fe S
4), cubanite (Cu
2SFe
4S
5), enargite [Cu
3(As Sb) S
4], tetrahedrite (Cu
3Sb S
2), tennantite (Cu
12As
4S
13), brochantite [Cu
4(OH)
6SO
4], antlerite [Cu
3SO
4(OH)
4], famatinite [Cu
3(Sb As) S
4] and wheel ore (Pb Cu Sb S
3); Contain lead minerals, for example: lead glance (Pb S); Antimony-containing mineral, for example: white antimony (Sb
2S
3); Zinc-bearing mineral, for example: zink sulphide (Zn S); Silver containing mineral, for example: stephanite (Ag
5Sb S
4) and vitreous silver ore (Ag
2S); Contain chrome mineral, for example: daubreelite ore deposit (Fe SCr S
3); Nickel-containing mineral.For example: pentlandite [(Fe Ni)
9S
8]; Molybdenum-bearing mineral, for example: molybdenum glance (Mo S
2); Platiniferous and contain the palladium mineral, for example: cooperite [Pt(As S)
2].Desirable metallic sulfide mineral comprises molybdenum glance (Mo S
2), chalcopyrite (Cu Fe S
2), lead glance (Pb S), zink sulphide (Zn S), purple copper (Cu
5Fe S
4) and pentlandite [(Fe Ni)
9S
8].
The metallic oxide mineral of sulfuration materialization is the mineral of handling with a kind of sulfuration agent, so that these mineral have the characteristic of sulfide mineral, reclaims these mineral so just can use the collector that reclaims sulfide mineral with froth-flotation method.Sulfuration makes oxide mineral have the characteristic of sulfide mineral.Oxide mineral is through curing with the compound reaction, and these compounds and mineral reaction generate sulfide linkage or produce avidity.Such processing method is known.This compounds comprises Sodium sulfhydrate, sulfuric acid and contains sulfosalt such as sodium sulphite.
This processing method can be used for vulcanizing the metallic oxide mineral and the oxide mineral of materialization, and these mineral comprise the oxide mineral that contains copper, aluminium, iron, titanium, magnesium, chromium, tungsten, molybdenum, manganese, tin, uranium and composition thereof.Can use processing method of the present invention and in pneumatic flotation, be carried the example of dense metallic oxide mineral and comprise copper-bearing mineral, for example: ruby copper (Cu
2O), tenorite (CuO), malachite [Cu
2(OH)
2CO
3], copper lazur [Cu
3(OH)
2(CO
3)
2], atacamite [Cu
2Cl(OH)
3], chrysocolla (Cu Si O
3); Aluminum-containing mineral, for example: the hard rock ore deposit; Zinc-bearing mineral, for example: zincite (Zn O) and smithsonite (Zn CO
3); Contain tungsten ore, for example; Wolframite [(Fe, Mu) WO
4]; Nickel-containing mineral, for example: krennerite (Ni O); Molybdenum-bearing mineral, for example: wulfenite (Pb Mo O
4) and powellite (Ca Mo O
4); Iron-bearing mineral, for example: rhombohedral iron ore and magnetite; Contain chrome mineral, for example: chromite (Fe OCr
2O
3); The iron content titaniferous ore, for example: ilmenite; Contain the magnesium aluminum-containing mineral, for example: spinel; Iron content contains chrome mineral, for example: chromite; Titaniferous ore, for example: rutile; Manganese-bearing mineral, for example: pyrolusite contains tin mineral, for example: cassiterite; And uranium bearing mineral, for example uraninite (uraninte); And the product uranium mineral, for example: uraninite (pitchblende) [U
2O
5(U
3O
8)] and gummite (UO
3N H
2O).
This technology can be used for other metal-containing minerals, and these mineral comprise metal-containing minerals, for example: sylvanite (Au Ag Te
2) and calaverite (Au Te); Platiniferous contains the palladium mineral, for example: sperrylite (Pt As
2); And silver containing mineral, for example: telluric silver (Au Te
2).Also comprise the metal that exists with metallic state, for example gold and silver, copper.
Collector composition of the present invention can use under any concentration, and needed mineral are carried out desired recovery.The concentration of using especially depends on the specific mineral that desire reclaims, and the grade of ore of experience foam floating process reclaims desired quality of mineral and the certain minerals that needs to reclaim to desire.Collector composition of the present invention is desirable with ore per ton with 5 concentration that restrain 1000 grams, preferable is that PMT (Per metric ton) stands ore usefulness collector 10 grams of pneumatic flotation between 200 grams, usually, for obtaining best synergisticing performance, best is from low consumption level, increase the consumption level then, until reaching desired effect.Result of weighted average when the synergy measuring result that is defined as two or more component mixtures surpasses each component and uses separately herein.This term means that also the result compares under such condition, promptly each to test employed collector gross weight identical.
In foam floating process of the present invention, be good to use pore forming material.Pore forming material has been known by prior art and has been related to purpose of the present invention.Any pore forming material that needed metal-containing minerals is reclaimed all suits.The pore forming material that the useful pore forming material of the present invention is comprised the mineral of sophisticated recyclable needs on any industrial technology.The example of these pore forming materials comprises C
5-8Alcohol, the C of pine tar, cresols, polypropylene glycol
1-4Alkyl oxide, polypropylene glycol dihydroxyl acid esters, dibasic alcohol, lipid acid, soap class, alkyl be for aromatic yl sulphonate etc., and can use the mixture of these pore forming materials.All pore forming materials that are suitable for the froth-flotation method finished ore all can be applied to the present invention.
In processing method of the present invention, can expect that the collector composition that constitutes composition of the present invention can mix use with other sophisticated technically collector herein.
Collector composition of the present invention also can with a certain amount of sophisticated technically collector and usefulness, fully needed mineral are carried out needed recovery.The example of other useful in the present invention collector comprises the dialkyl thiourea of thiocarbonic acid SOH, alkyl, dialkyl group and trialkyl ester, carbamic alkyl of thion and dialkyl, the phosphorodithioic acid mono alkyl ester, the dialkyl group of phosphorodithioic acid and diaryl ester, the monothio phosphate dialkyl ester, the phosphorodithioic acid diaryl ester, diaryl and dialkyl sulfide substituted phosphorus oxychloride, phosphonodithioic acid dialkyl group and diaryl ester, alkyl sulfhydryl, methyl xanthate, mercaptobenzothiazole, lipid acid and soap, alkylsurfuric acid and salt thereof, alkyl and alkyl are for aryl sulfonic acid and salt thereof, alkylphosphonic acid carboxylic acid and salt thereof, alkyl and aryl phosphoric acids and salt thereof, sulfosuccinate, sulphosuccinamate, primary amine, secondary amine, tertiary amine and quaternary ammonium salt, Fixanol, guanidine and alkyl propylene diamine.
Enumerate the following example only for the purpose of description, do not constitute limitation of the scope of the invention.Except as otherwise noted, all umbers and by weight than weight average.
In an embodiment, described bubbling process is to represent by the relative yield of specified time.
The pneumatic flotation of embodiment 1-copper/molybdenum ore
One group of bag that contains 1200 gram homogeneous phase copper/molybdenum ores, (sample number is 1～8) provided by Canada West to contain chalcopyrite and molybdenum glance mineral substance.Every bag of ore was milled 14 minutes in a spherical runner milling from water with 800 milliliters, runner milling the blended Ball-type packing can be made about 13% greater than 100 purpose abrasive particles.The mud that produces is removed paddle with automatic bubble deliver to 1500 milliliters of Agitair flotation cells.With lime the pH value of every part of mud is adjusted to 10.2.No longer adjust pH value at duration of test.With the level Four rougher flotation flowsheet shown in following, come Floatation of Copper and molybdenum with standard methyl isobutyl carbinol (MIBC) pore forming material shown in the table 1 and collector or associating collector.
1 grade: collector-0.0042 kg/ton *
MIBC-0.015 kg/ton * *
-regulate-1 minute
-flotation-enrichment ore dressing 1 minute
2 grades: collector-0.0021 kg/ton *
MIBC-0.005 kg/ton * *
-regulate-0.5 minute
-flotation-enrichment ore dressing 1.5 minutes
3 grades: collector-0.0016 kg/ton *
MIBC-0.005 kg/ton * *
-regulate-0.5 minute
-flotation-enrichment ore dressing 2.0 minutes
4 grades: collector-0.0033 kg/ton *
MIBC-0.005 kg/ton * *
-regulate-0.5 minute
-flotation-enrichment ore dressing 2.5 minutes
* handle the kilogram number of ore per ton with collector or collector composition.
* handles the kilogram number of ore per ton with pore forming material.
The bubble flotation experimental results is listed in the table I.
The table I
Cu Moly Cu Moly
Test number collector R-7
2R-7
2Grade
3Grade
3
1＊ A 0.688 0.682 0.063 0.00233
2＊ B 0.770 0.713 0.028 0.00125
3＊ C 0.710 0.691 0.093 0.00325
4＊ D 0.699 0.697 0.107 0.00386
5 C/A 0.766 0.768 0.052 0.00157
6 C/B 0.732 0.750 0.081 0.00275
7 D/A 0.759 0.764 0.050 0.00170
8 D/B 0.743 0.755 0.091 0.00316
* not embodiments of the invention
A=C
6H
13S(CH
2)
2NH
2R-7
2It is test every batch of rate of recovery after 7 minutes.
In the pneumatic flotation test of carrying out on No. 1～8, sample, the collecting agent composition contains every kind of collecting agent and respectively is 50%(weight).
With relevant statistical error 95% fiducial interval of Cu R-7 value in the table I be ± 0.010.For example, in the table I, be 0.688 ± 0.010 to be 0.678 to 0.698 with the scope of statistics of collecting agent A corresponding C u R-7 value.
With the relevant statistical error of Mo R-7 value in the table I be ± 0.015.
Obviously, with the collector mixture of this invention 7 minutes Cu and Mo not yield meet or exceed the result of weighted average of 7 minutes yields that use one-component; Produced synergy.
The pneumatic flotation of embodiment 2-Cu/Ni ore
With one group from Canadian east-10 order ore sample, be divided into 900 the gram samples.This ore contains chalcopyrite, pentlandite and pyrrhotite material.All tests are injected 9 liters/minute air draught with 1500 milliliters of (Agitair) flotation cells, finish drilling with the velocity conditions of 900 rev/mins (rpm) and finish.Before the flotation, the barreling 1080 on rod mill of per minute sample is changeed.Before barreling, add 600 ml waters, and adjust the pH value to 9.2 of mud with enough lime.After the barreling, ore particles size 200 orders (75 microns).The barreling ore pulp injects flotation and pH value is transferred to 9.2(with lime or sulfuric acid).
Finish nine grades of comprehensive flotation operations.Preceding level Four is to select mutually, and back Pyatyi is selected.After level Four is roughly selected, add sulfuric acid and adjust pH value to 9.2; Cu SO is added to Pyatyi and seven grades (0.015 kilograms per tonne), and the pore forming material of use is DowFROth 250.
The adding speed of pore forming material and collector is shown in table II A.
Table II A
When level collecting agent consumption is regulated time D OWFROTH250 flotation
(kg/ton) (minute) between consumption (kg/ton) (minute)
1 0.028 1.0 0.012 1
2 0.012 0.5 - 2
3 0.008 0.5 - 2
4 0.004 0.5 0.004 2
5 0.012 0.5 0.003 2
6 0.006 0.5 0.004 2
7 0.007 0.5 0.002 2
8 0.006 0.5 0.001 2
9 0.007 0.5 0.001 2
With the finished product drying, weigh and finish metal analysis.Calculate recovery ratio and grade with the reference material balanced type.The results are shown in table II B.
Table II B
Cu Cu Ni Ni pyrrhotite
Test number collector R-7
2R-17
3R-7
2R-17
3R-7
2
1
1A 0.969 0.980 0.730 0.948 0.398
2
1B 0.958 0.971 0.533 0.710 0.258
3
4A+B 0.963 0.978 0.670 0.931 0.331
B＝C
4H
9SC
4H
9
1 is not example of the present invention.
2 R-7 are the recovery ratio (expression decimally) of (slightly making the pond) after 7 minutes
3 R-17 are the recovery ratio (expression decimally) of (scavenging agent) after 17 minutes
4 in experiment 3, and the ratio of A and B collecting agent is the weight percent of every kind of collecting agent of 50/50().
In this embodiment, after 7 minutes, the recovery ratio of minimum pyrrhotite recovery ratio and the highest Cu and Ni may be main, because this moment, what will remove mainly was the high mineral of sulphur content.Adopted common flotation process in the time of 17 minutes, it is the highest that the recovery ratio of Cu and Ni may reach.And therefore the recovery ratio of Cu, can not carry out effective statistical near theoretical limit in the time of 7 and 17 minutes.
Obviously, use collecting agent mixture of the present invention, in the time of 7 minutes, obtain low pyrrhotite recovery ratio and high Ni recovery ratio value.And, collecting agent mixture of the present invention, at 17 minutes, the recovery ratio of Ni also was high.Statistical error 90% fiducial interval relevant with Ni R-7 be ± 0.015, and Ni R-17 is ± 0.006; Pyrrhotite R-7 is ± 0.012.Ni recovery ratio surface is that synergy has caused needed low pyrrhotite recovery ratio.
One group of comprehensive mineral samplers of the 1000 uniform Pb/Zn/Cu/Ag of gram that provides by Canada middle part (Central Canada).This ore contains lead glance, zink sulphide, chalcopyrite and vitreous silver ore material.Flotation test each time, ore and 500 milliliters are from water and 7.5 milliliters of SO
2Solution is added in the tumbling mill together.Made 90% with 6.5 minutes barreling time and have the ore of particle size less than 200 orders (75 microns).After the barreling, mud delivered to the flotation cell that automatic bubble removes paddle is housed, flotation cell is connected standard Denver flotation unit.
Then, finish the two-stage flotation, the 1st grade is that copper/lead/silver is roughly selected, and the 2nd grade is that zinc is roughly selected.During the 1st grade of beginning, add Na
2CO
31.5 gram/kilogram ore (pH value is 9 to 9.5) adds collecting agent then.With ventilation stream and stirring ore pulp was handled 5 minutes.Then stirred separately again 2 minutes.Methylate isobutyl carbinol (MIBC) frothing agent (0.020 ml/kg standard metering) subsequently.Concentrate was through flotation collecting 5 minutes and be labeled as zinc rougher concentrate.
In the pond after the 1st grade of flotation, add Cu SO0.5 kg/ton in the resistates, by adding lime, its pH value being transferred to 10.5, then through stirring and adjusting 5 minutes.Detect pH value at last and PH is recalled to 10.5 with lime.At this moment, add collector, then regulate 5 minutes while stirring, add methyl isobutyl carbinol (MIBC) pore forming material (standard dose is 0.020 ml/kg) later on.Concentrate is labeled as zinc rougher concentrate after 5 minutes collection.
With the concentrate sample drying, weigh and the sample supply of preparation used with the quantitative analysis of x-ray technology.Utilize analytical data, use the standard quality balanced type to calculate every batch of recovery ratio and grade.The results are shown in the table III.
Cu/Pb flotation (1 grade) in 95% fiducial interval of 5 minutes recovery ratio statistical error is: Ag, ± 0.01; Cu, ± 0.01; Pb, ± 0.02.Experiment 1 and 4 every grade of tests of all using single collecting agent.
* non-example of the present invention.
A-dihexyl thioether
The own sulfenyl of B-2-() ethamine
The own sulfenyl of C-ethyl 2-() ethanamide
R-5 is 5 minutes every batch of actual recovery ratio
In the I level of test 2, the collecting agent of dosing the I level adding one-component of two kinds of collecting agent mixtures of the present invention and experiment 1 with less dosage (less than 24%) compares, and obtains high slightly Ag and Cu recovery ratio and obvious higher Pb recovery ratio
In a similar fashion, with the 1 grade comparison of collecting agent mixture of the present invention with test 1 or 4, the result has higher Ag recovery ratio, high slightly Cu recovery ratio and very high P recovery ratio in the I level of test 3.Note, the Ag that is not recovered in the I level, Cu or Pb have lost during the course.
The I in all four tests of table III and the Zn overall recovery factor of II level are near the 1.0(theoretical limit), so can not carry out statistical effectively.
Claims (20)
1, a kind of method that reclaims metal-containing minerals from ore, this method comprise, in the presence of an amount of collector composition, the ore of water slurry shape carried out pneumatic flotation, and the collector composition has:
(a) the following compound of molecular formula: R
1-X-(R)
n-Q
I
Wherein Q is:
-N (R
2) a (H) b, a+b equals 2 here,
-N=Y, Y is S here, O, alkylene group or substituted alkylene,
Three N, or-
, ring is saturated or undersaturated here, and can contain additional heteroatoms, but must contain N;
R
1And R
2Be arbitrarily C
1-22Alkyl, substituted C
1-22Hydrocarbyl group, or saturated or unsaturation and heterocycle;
R is
Y+p+m=n wherein, n is the integer between 1 to 6, and y, p and m are arbitrarily the integers between 0 or 1 to 6, and every can produce by stochastic sequence;
X is-S-,-O-,
R herein
3Be hydrogen, C
1-22Alkyl or substituted C
1-22Alkyl;
(b) molecular formula that contains the hydrocarbon of single thio-ether units is
R
5-S-R
6
R wherein
5And R
6Be arbitrarily alkyl or by one or more hydroxyls, cyano group, fontanel element, ether, the alkyl that-oxyl or hydrocarbon thioether replace; R wherein
5And R
6Can be in conjunction with the heterocycle structure that forms band S; The S item is connected on aliphatics or the alicyclic carbon atom; And the total carbon content of hydrocarbon thioether has enough hydrophobic propertys, makes the containing metal oxide ore composition granule of the metallic sulfide mineral or the materialization that cures be driven into the interface of air/gas bubbles.
2, by the described method of claim 1, wherein component (a) is ω-(sulfenyl) alkylamine, S-(omega-amino-alkyl) alkyl thioester, the N-(alkyl)-α, ω-alkane diamine, (ω-aminoalkyl) hydrocarbyl amide, ω-(-oxyl) alkylamine, ω-aminoalkyl supercarbonate, ω-(sulfenyl) alkylamide or their mixture.It is effective collector concerning the metallic ore material in the pneumatic flotation process that component (a) and consumption (b) should make composition of the present invention.
3, by the described method of claim 1, wherein n is 2 or 3.
4, by the described method of claim 3, wherein comprise:
(a) from about 10% to 90%(weight) ω-(sulfenyl) alkylamine, S-(omega-amino-alkyl) alkyl thioester, the N-(alkyl)-α, ω-alkane diamine, (ω-aminoalkyl) hydrocarbyl amide, ω-(-oxyl) alkylamine, ω-aminoalkyl supercarbonate, ω-(sulfenyl) alkylamide or their mixture;
(b) content about 10% is to 90%(weight) sulfide compound, its corresponding molecular formula is (R
4)
3-nC(H)
n-S-C(H)
n(R
4)
3-n,
R wherein
4Be alkyl or by alkyl, cyano group, fontanel element, ether,-oxyl, or the alkyl that replaces of alkyl thioether; But two R combining form rings or with sulphur atom form heterocycle; N is 0,1,2 or 3 integer.
5, by the described method of claim 4, wherein comprise:
(a) by 20% to 80%(weight) ω-(sulfenyl) alkylamine, the N-(alkyl)-α, ω-alkyl group-diamine, (ω-aminoalkyl) hydrocarbyl amide, ω-(-oxyl) alkylamine, ω-(sulfenyl) alkylamide or their mixture;
(b) by about 20% to 80%(weight) sulfide compound.
6, by the described method of claim 1, wherein metal-containing minerals reclaims in foam.
7, by the described method of claim 6, the metalliferous mineral cupric that wherein in foam, reclaims, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium gold, platinum, uranium or their mixture.
8, by the described method of claim 7, the metal sulfide ore that wherein reclaims in foam is a molybdenum glance, chalcopyrite, lead glance, zink sulphide, purple copper, or pentlandite.
9, by the described method of claim 8, wherein the concentration of collector composition is that 0.01 to 1.0 kilogram/PMT (Per metric ton) is used for the ore of pneumatic flotation.
10, by the described method of claim 3, wherein R
5And R
6It is hydrocarbon part inequality.
11, by the described method of claim 1, wherein the containing metal sulfide mineral has high natural mercapto water-based in non-oxide attitude.
12, by the described method of claim 1, wherein R
1And R
2Be C arbitrarily
1-22Alkyl or by one or more hydroxyls, amino, phosphono, alkoxyl group, imido grpup, carbamyl, carbonyl, thiocarbonyl, cyano group, hydroxyl, sulfenyl,-oxyl, the C alkyl that hydrocarbon amino and hydrocarbon imino are replaced.
13, by the described method of claim 2, wherein the corresponding molecular formula of compound (a) is:
R in the formula
1Be C
2-14Alkyl or by one or more hydroxyls, amino, the C that phosphono and alkyl replace
2-14Alkyl; R
2Be C
1-6Alkyl, or C
1-6Alkyl carbonyl, or C
1-6Alkyl or by amino, the C that hydroxyl or phosphono replace
1-6Alkyl carbonyl; A is 0 or 1, and b is 1 or 2, and a+b=2.
14, by the described method of claim 1, wherein R
5And R
6Any for to use one or more hydroxyls, cyano group, the plain OR of fontanel
7Or SR
7Replace or unsubstituted aliphatics alicyclic or aralkyl moiety, R
7Be alkyl, R
5And R
6But the heterocycle of combining form band sulphur.
15, by the described method of claim 14, wherein the total carbon content of sulfide compound is 4～20 carbon atoms.
16, by the described method of claim 15, wherein R
5And R
6Be arbitrarily to use one or more hydroxyls, cyano group, the plain OR of fontanel
7Or SR
7Replace or unsubstituted alkyl alkenyl, alkynyl group, cycloalkyl or cycloalkenyl group, R
7Be fatty group or alicyclic group; R
5And R
6Can not be in conjunction with forming heterocycle structure.
17, by the described method of claim 5, wherein R is-CH
2-or
R
1Be C
2-14Alkyl; R
2Be C
1-6Alkyl or C
1-6Alkyl carbonyl; R
3Be hydrogen or C
1-14Alkyl; R
5And R
6Be arbitrarily alkyl or alkenyl, R
5And R
6The total number of carbon atoms is 6 to 16; A is integer 0 or 1; B is integer 1 or 2; N is an integer 1 to 4.
18, by the described method of claim 4, wherein R
1Be C
4-11Alkyl; R
2Be C
1-4Alkyl or C
1-4Alkyl carbonyl; R
3Be hydrogen or C
1-11Alkyl; R
5Be C
1-2Alkyl; R
6Be C
6-11Alkyl or alkenyl; X-S-,
Or-O-; N is integer 2 or 3.
19, by claim 1 or 2 described methods, wherein component (a) is the own sulfenyl of 2-() ethamine or the own sulfenyl of ethyl 2-() ethanamide.
20, by claim 1 or 19 described methods, wherein component (b) is an ethyl octyl group thioether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80288285A | 1985-11-29 | 1985-11-29 | |
| US802,882 | 1985-11-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101495A true CN86101495A (en) | 1987-06-03 |
| CN1014247B CN1014247B (en) | 1991-10-09 |
Family
ID=25184982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101495A Expired CN1014247B (en) | 1985-11-29 | 1986-02-17 | Collection method for recovery of metal-containing ore from ore |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS62129160A (en) |
| CN (1) | CN1014247B (en) |
| AU (1) | AU588579B2 (en) |
| BR (1) | BR8607004A (en) |
| CA (1) | CA1268565A (en) |
| ES (1) | ES8706045A1 (en) |
| FI (1) | FI82395C (en) |
| MX (1) | MX173645B (en) |
| PH (1) | PH23458A (en) |
| PL (1) | PL147852B1 (en) |
| RO (1) | RO100034B1 (en) |
| RU (1) | RU1839638C (en) |
| SE (1) | SE461768B (en) |
| WO (1) | WO1987003222A1 (en) |
| YU (1) | YU45766B (en) |
| ZA (1) | ZA861170B (en) |
| ZM (1) | ZM1586A1 (en) |
| ZW (1) | ZW4186A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700369A (en) * | 1997-01-14 | 1997-12-23 | Guangzhou Institute Of Geochemistry Chinese Academy Of Sciences | Process for adsorboaggregational flotation of Carlin type natural gold ore dressing |
| CN102056672A (en) * | 2008-04-04 | 2011-05-11 | Bhp比利通Ssm开发有限公司 | Odour control |
| CN110015727A (en) * | 2019-05-09 | 2019-07-16 | 安徽工业大学 | A kind of method that electrofloatation removes micro- plastics in water body |
| WO2021128771A1 (en) * | 2019-12-23 | 2021-07-01 | 中南大学 | Application of 2-cyano-n-(substituted carbamoyl) acetamide compound in calcium-containing mineral flotation |
| CN114798184A (en) * | 2022-05-16 | 2022-07-29 | 北京盈翔科技有限公司 | Efficient foaming agent for copper-gold ore flotation and application method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES8706047A1 (en) * | 1985-11-29 | 1987-06-01 | Dow Chemical Co | Novel collectors for froth flotation of minerals |
| US4826588A (en) * | 1988-04-28 | 1989-05-02 | The Dow Chemical Company | Pyrite depressants useful in the separation of pyrite from coal |
| CN102941160A (en) * | 2012-12-13 | 2013-02-27 | 贵州大学 | Flotation collector for silicate minerals |
| AU2018237908B2 (en) * | 2017-03-23 | 2022-07-21 | Nouryon Chemicals International B.V. | Process to treat metal or mineral ores and collector composition therefor |
| WO2019113082A1 (en) | 2017-12-06 | 2019-06-13 | Dow Global Technologies Llc | A collector formulation to enhance metal recovery in mining applications |
| EP3636346A1 (en) | 2018-10-08 | 2020-04-15 | Nouryon Chemicals International B.V. | Process to treat ores and collector composition therefor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2169313A (en) * | 1938-09-24 | 1939-08-15 | Minerals Separation North Us | Concentration of metalliferous ores by flotation |
| US3328442A (en) * | 1963-12-18 | 1967-06-27 | Massachusetts College Of Pharm | Anti-radiation compounds and their preparation |
| US3397238A (en) * | 1965-11-16 | 1968-08-13 | Pfizer & Co C | Process for the preparation of alkyl ethers of amino-alcohols |
| US4086273A (en) * | 1976-04-14 | 1978-04-25 | The Dow Chemical Company | Process for making beta-aminoethyl sulfides from aliphatic mercaptans and 2-oxazolines |
| US4326067A (en) * | 1980-12-03 | 1982-04-20 | The Dow Chemical Company | Process for making N-(2-aminoethyl)amides |
| PH23738A (en) * | 1985-05-31 | 1989-11-03 | Dow Chemical Co | Novel collectors for the selective froth flotation of sulfide minerals |
| ZM1386A1 (en) * | 1985-07-12 | 1988-12-30 | Dow Chemical Co | Novel collector compositions for froth flotation |
| ES8706047A1 (en) * | 1985-11-29 | 1987-06-01 | Dow Chemical Co | Novel collectors for froth flotation of minerals |
-
1986
- 1986-02-14 ES ES552033A patent/ES8706045A1/en not_active Expired
- 1986-02-14 CA CA000501882A patent/CA1268565A/en not_active Expired - Fee Related
- 1986-02-14 PH PH33418A patent/PH23458A/en unknown
- 1986-02-17 YU YU23086A patent/YU45766B/en unknown
- 1986-02-17 ZW ZW41/86A patent/ZW4186A1/en unknown
- 1986-02-17 CN CN86101495A patent/CN1014247B/en not_active Expired
- 1986-02-17 PL PL1986257989A patent/PL147852B1/en unknown
- 1986-02-17 ZM ZM15/86A patent/ZM1586A1/en unknown
- 1986-02-17 ZA ZA861170A patent/ZA861170B/en unknown
- 1986-02-17 MX MX001572A patent/MX173645B/en unknown
- 1986-02-18 AU AU55437/86A patent/AU588579B2/en not_active Ceased
- 1986-02-18 WO PCT/US1986/000342 patent/WO1987003222A1/en active IP Right Grant
- 1986-02-18 BR BR8607004A patent/BR8607004A/en not_active IP Right Cessation
- 1986-09-03 JP JP61207631A patent/JPS62129160A/en active Pending
- 1986-12-18 RO RO12922786A patent/RO100034B1/en unknown
-
1987
- 1987-07-22 RU SU874203131A patent/RU1839638C/en active
- 1987-07-28 FI FI873288A patent/FI82395C/en not_active IP Right Cessation
- 1987-07-28 SE SE8702987A patent/SE461768B/en not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700369A (en) * | 1997-01-14 | 1997-12-23 | Guangzhou Institute Of Geochemistry Chinese Academy Of Sciences | Process for adsorboaggregational flotation of Carlin type natural gold ore dressing |
| CN102056672A (en) * | 2008-04-04 | 2011-05-11 | Bhp比利通Ssm开发有限公司 | Odour control |
| CN102056672B (en) * | 2008-04-04 | 2013-12-04 | Bhp比利通Ssm开发有限公司 | Odour control |
| CN110015727A (en) * | 2019-05-09 | 2019-07-16 | 安徽工业大学 | A kind of method that electrofloatation removes micro- plastics in water body |
| WO2021128771A1 (en) * | 2019-12-23 | 2021-07-01 | 中南大学 | Application of 2-cyano-n-(substituted carbamoyl) acetamide compound in calcium-containing mineral flotation |
| CN114798184A (en) * | 2022-05-16 | 2022-07-29 | 北京盈翔科技有限公司 | Efficient foaming agent for copper-gold ore flotation and application method thereof |
| CN114798184B (en) * | 2022-05-16 | 2024-01-23 | 北京盈翔科技有限公司 | Efficient foaming agent for copper gold ore flotation and application method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FI82395C (en) | 1991-03-11 |
| JPS62129160A (en) | 1987-06-11 |
| WO1987003222A1 (en) | 1987-06-04 |
| CN1014247B (en) | 1991-10-09 |
| ES552033A0 (en) | 1987-06-01 |
| YU23086A (en) | 1988-06-30 |
| BR8607004A (en) | 1987-12-01 |
| FI873288A (en) | 1987-07-28 |
| YU45766B (en) | 1992-07-20 |
| MX173645B (en) | 1994-03-22 |
| ZM1586A1 (en) | 1988-12-30 |
| FI873288A0 (en) | 1987-07-28 |
| FI82395B (en) | 1990-11-30 |
| PH23458A (en) | 1989-08-07 |
| PL257989A1 (en) | 1987-06-01 |
| SE8702987D0 (en) | 1987-07-28 |
| AU5543786A (en) | 1987-07-01 |
| RO100034B1 (en) | 1992-05-25 |
| ZW4186A1 (en) | 1987-09-09 |
| ES8706045A1 (en) | 1987-06-01 |
| CA1268565A (en) | 1990-05-01 |
| SE461768B (en) | 1990-03-26 |
| RU1839638C (en) | 1993-12-30 |
| SE8702987L (en) | 1987-07-28 |
| ZA861170B (en) | 1987-10-28 |
| PL147852B1 (en) | 1989-08-31 |
| AU588579B2 (en) | 1989-09-21 |
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