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CN1020551C - Process for froth flotation of useful components of minerals - Google Patents

Process for froth flotation of useful components of minerals Download PDF

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Publication number
CN1020551C
CN1020551C CN85109643A CN85109643A CN1020551C CN 1020551 C CN1020551 C CN 1020551C CN 85109643 A CN85109643 A CN 85109643A CN 85109643 A CN85109643 A CN 85109643A CN 1020551 C CN1020551 C CN 1020551C
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Prior art keywords
ore
carbon alkyl
trapping agent
alkyl
integer
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CN85109643A
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CN85109643A (en
Inventor
理查德·R·克利姆贝尔
罗伯特·D·翰森
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Dow Chemical Co
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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
    • B03D1/02—Froth-flotation processes
    • 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
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • 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
    • B03D1/012—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
    • 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

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  • Manufacture And Refinement Of Metals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Physical Water Treatments (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention is a collector and recovery process for recovering metal values from metal ores, the process comprising subjecting the metal ore in the form of an aqueous slurry to a froth flotation operation in the presence of the collector, wherein the collector used comprises a compound corresponding to the formula:in the formula: r, R1，R2And X, n, a and b are defined in the specification.

Description

Process for foam-floatation of useful component in ore
The invention relates to foam flotation method and from ore, reclaim the new method that the mineral useful component is used.
Method for floating is that a kind of processing is with the solid mineral that grinds, epipastic mineral for example, be suspended in the method for formed mixture in the liquid, method whereby, just solid mineral that can a part is such and other the solid mineral that grinds, for example other similar substance that is contained in earth and the ore is separated.This method is to blast gas (perhaps producing gas in flotation liquid on the spot) in liquid, thereby the upper strata at liquid produces the foam-like material that contains some solid mineral, simultaneously, other solid suspending components (part of not bubbling) in the ore is stayed in the liquid.Method for floating is based on such principle, promptly in the liquid of the solid suspended particle that wherein contains various different materials, introduce gas, just can cause wherein gas-selectively adhere on some solid particle that floats on a liquid, simultaneously, can not adhere on other the solid suspended particle again, thus make the particle that adhered to gas than liquid light some.Therefore, these solid particles form foam with regard to the upper strata that floats to liquid.
Up to the present, various reagent and the fusion of formed solid suspended substance are got up to improve foaming and capture process.The reagent that adds is classified according to role, and comprising for example, trapping agent is used for handling and comprises xanthate, the sulfide mineral of thionocarbamate and similar substance thereof; Foaming agent, foaming agent are used for the characteristic that pre-suspended substance forms stable foam, pine tar are for example arranged, the natural oils that eucalyptus oil is such etc.; Modifier, for example activator in order to make the mineral foaming under the situation that has trapping agent to exist, for example can adopt copper sulphate; Depressant, Cymag for example, depressant plays capture in order to stop trapping agent to the mineral grain that those hope are retained in the liquid, thereby stops these materials by carrier band, arrives liquid surface, becomes the part of foam; PH value conditioning agent is in order to reach best metallurgy effect, for example available lime, light ash, and similar substance.
It is highly important that, should be kept in mind that above-mentioned various additives are the character according to the processing ore, mineral species that desire reclaims, and other accrete character that cooperates is with it selected for use.
Method for floating has value especially in industrial operation, still, to the understanding of this phenomenon, from implementing angle of the present invention, be not necessary.As if this phenomenon has very big relation with the selectivity affinity on granular solid particles surface, and granular solid particles is suspended in the liquid that contains entrap gas, on the one hand, liquid is had a kind of affinity, and on the other hand, gas is had a kind of affinity again.
Floating principle has obtained application in the multi mineral separation method, comprising from the iron sulfide ore, for example optionally isolate the method for following mineral from pyrite, as if sulphuretted copper ore, sulfide zinc ore, the mineral of sulfide molybdenum ore and other kinds.
The trapping agent that is widely used in the metal useful component that reclaims sulfur compound is an xanthate, and thionocarbamate.The trapping agent that reclaims the metal useful component of sulfur compound is known, and has obtained using widely.Difficulty be to reclaim to contain the useful component of oxide ore do not possess the quality that is suitable for being suitable for fully commercial Application usually because be suitable for reclaiming the trapping agent of this class mineral useful component.
Industrial needs still to from metallic ore, reclaiming the metal useful component in the broad range, contain the mineral useful component of sulfide and contain all available trapping agent of mineral useful component of oxide comprising recovery.In addition, also need this trapping agent, promptly both can obtain the high-recovery of mineral useful component, simultaneously can obtain the mineral useful component again, that is to say, to the trapping agent of the high selectivity of that part of ore of not wishing to obtain reclaiming stone.
Specifically, the present invention is exactly a trapping agent used when reclaiming the metal useful component from ore, in the reclaimer operation process, the metallic ore under the moisture ore pulp form is carried out froth flotation handle, wherein, used trapping agent is to be equivalent to the compound shown in the following molecular formula:
Figure 851096433_IMG7
In the formula, R is-CH 2-,
Figure 851096433_IMG8
Perhaps
Its mixed base, n are 1 to 6 integer, perhaps (R) nBe (CH) mC three, and wherein, m is 0 to 6 integer; R and each R represent the alkyl with 1 to 22 carbon atom independently or have 1 to 22 carbon atom and have following substituent alkyl: one or more hydroxyl, amino, acyl group, alkoxyl, imino group, carbamoyl, carbonyl, thiocarbonyl, cyano group, hydroxyl sulfenyl, oxyl, hydrocarbon amino or hydrocarbon imino, its condition are that R can be divalent group, and two all direct and nitrogen atom bondings of valence link;
Figure 851096433_IMG9
R 3For H or have the alkyl of 1 to 22 carbon atom;
A is integer 0,1 or 2;
B is integer 0,1 or 2;
Its condition is, except following condition and, a and b sum equal 2, promptly when R be divalent group, and two valence links are all directly fashionable with nitrogen, in this case, a=1, and b=0 perhaps ought
Figure 851096433_IMG10
nFor
Figure 851096433_IMG11
mDuring C three, in this case, a+b=0; And the another one condition is, when X is
Figure 851096433_IMG12
The time, carbonyl moiety and R ' bonding get up.
The also relevant method that from metallic ore, reclaims the metal useful component of the present invention, this method comprises, under the condition that has collection agent to exist, the metallic ore that will be under the moisture ore pulp form carries out the froth flotation processing, its treatment conditions are such, be that the metal useful component is reclaimed in foam, wherein, used trapping agent comprises the compound that is equivalent to following molecular formula:
Figure 851096433_IMG13
In the formula, R is-CH 2-,
Figure 851096433_IMG14
, or
Its mixed base of person, n are 1 to 6 integer, perhaps
Figure 851096433_IMG15
nFor mC three, and wherein, m is 0 to 6 integer; R 1With each R 2Representative has the alkyl of 1 to 22 carbon atom independently, or has 1 to 22 carbon atom and have the alkyl of following substituted radical: one or more hydroxyl, amino, acyl group, alkoxyl, imino group, carbamoyl, carbonyl, thiocarbonyl, cyano group, carbonyl, sulfenyl, oxyl, hydrocarbon amino or hydrocarbon imino;
X is-S--O-,-N-R 3,
Figure 851096433_IMG17
R 3For hydrogen or have the alkyl of 1 to 22 carbon atom;
A is integer 0,1 or 2;
B is integer 0,1 or 2;
Its condition is, except following condition and, a and b sum be in 2, promptly when R be divalent group, and two valence links are during all directly with nitrogen atom bonding, in this case, a=1, and b=0 perhaps ought
Figure 851096433_IMG18
3 o'clock, in this case, a+b=0; And the another one condition is, when X is
Figure 851096433_IMG19
The time, carbonyl moiety and R 1Bonding gets up.
In a preferred embodiment of the invention, used trapping agent comprises and is equivalent to the compound shown in the following molecular formula:
Figure 851096433_IMG20
In the formula:
R 1For having 1 to 22 carbon atom alkyl or have one or more hydroxyl, amino, acyl group, the perhaps alkyl of alkoxyl;
12 2For having the alkyl of 1 to 6 carbon atom, alkyl-carbonyl with 1 to 6 carbon atom has 1 to 6 carbon atom and has amino, the alkyl of hydroxyl or acyl substituted group, perhaps have 1 to 6 carbon atom and have amino, the alkyl-carbonyl of hydroxyl or acyl substituted group;
And X, a, the definition of b and n is as mentioned above.
Trapping agent of the present invention unexpectedly makes the metal useful component in the broad range carry out flotation, comprising sulfide ore, and oxide ore and noble metal.In addition, this class trapping agent can improve the rate of recovery of mineral useful component, comprising improving oxide mineral, sulfide mineral and noble metal recovery rate.Not only make the unexpected height of the rate of recovery that reaches, and also unexpectedly high to the selectivity of the mineral useful component of desired recovery.
Preferred novel trapping agent provided by the invention comprises ω-(sulfenyl) alkylamine; The S-(CO-aminoalkyl) carbithionic acid ester: the N-(alkyl)-, ω-alkane diamine; (omega-amino-alkyl) hydrocarbon acid amides; ω-(oxyl-) alkylamine; Omega-amino-alkyl oxycarbonyl acid esters; Perhaps its mixture.Preferred trapping agent comprises ω-(sulfenyl) alkylamine; The N-(alkyl)-, ω-alkane diamine; And ω-(oxyl-) alkylamine; Perhaps its mixture.Very preferred trapping agent comprises ω-(sulfenyl) alkylamine; The N-(alkyl)-, ω-alkane diamine; Perhaps its mixture.And the class trapping agent that override is selected for use is ω-(sulfenyl) alkylamine.
In the molecular formula shown in the above-mentioned embodiment preferred, R preferentially selects the alkyl with 2 to 14 carbon atoms for use, and more preferably selects the alkyl with 4 to 11 carbon atoms for use.R 2Preferentially select alkyl for use or have the alkyl-carbonyl of 1 to 6 carbon atom with 1 to 6 carbon atom, more preferably select alkyl-carbonyl for use with 1 to 4 carbon atom, and the alkyl with 1 to 2 carbon atom that override is selected for use or have the alkyl-carbonyl of 1 to 2 carbon atom.R 3What preferentially select for use is hydrogen or the alkyl with 2 to 14 carbon atoms, what more preferably select for use is hydrogen or the alkyl with 4 to 11 carbon atoms, and override is selected for use be hydrogen a preferentially select for use be integer 0 or 1b preferentially select for use what be that integer 1 or 2n preferentially select for use is 1 to 4 integer, and override is selected for use be integer 2 or 3X preferentially select for use be-S--N '-R 3, perhaps-O-; More preferably select for use be-S-or-N '-R 3; And override is selected for use be-S-.
The S-(omega-amino-alkyl of preferentially selecting for use) the carbithionic acid ester is equivalent to following molecular formula:
In the formula, R 1, R 2, a, the definition of b and n is as mentioned above.
The ω that preferentially selects for use-(sulfenyl) alkylamine is equivalent to following molecular formula:
In the formula, R 1, R 2, a, the definition of b and n is as mentioned above.
In these embodiments, X is for-S-or be
Figure 851096433_IMG23
And R 1The alkyl of preferentially selecting for use with 4 to 10 carbon atoms.
The N-(alkyl of preferentially selecting for use) α, ω-alkane diamine is equivalent to following molecular formula:
Figure 851096433_IMG24
In the formula, R 1, R 2, R 3, a, the definition of b and n is as mentioned above.
The N-(omega-amino-alkyl of preferentially selecting for use) the hydrocarbon acid amides is equivalent to following molecular formula:
In the formula, R 1, R 2, R 3, a, the definition of b and n is as mentioned above.
In these embodiments, X is
Figure 851096433_IMG26
R 1And R 3It is 1 to 23 that the total number of carbon atoms in these two groups is preferentially selected for use, more preferably selects 2 to 16 for use, and override to select for use be 4 to 15.
The ω that preferentially selects for use-(oxyl-) alkylamine is equivalent to following molecular formula:
Figure 851096433_IMG27
In the formula, R 1, R 2, a, the definition of b and n is as mentioned above.
The omega-amino-alkyl carboxylic acid ester who preferably selects for use is equivalent to following molecular formula:
Figure 851096433_IMG28
In the formula, R 1, R 2, a, the definition of b and n is as mentioned above.In these embodiments, X is
Figure 851096433_IMG29
Perhaps-O-,
And R 1The alkyl that very preferably has 6 to 11 carbon atoms.
Hydrocarbon means the organic compound that contains carbon atom and hydrogen atom here.This term of employed hydrocarbon comprises following organic compound: alkane, olefine, alkine, cycloalkane, cycloolefin, cycloalkyne, aromatic, aliphatic series and cyclic aliphatic aromatic and alkyl substituted aromatic.Aliphatic series refers to straight chain and side chain here, and saturated and undersaturated hydrocarbon compound, that is to say alkane, alkene or alkynes.Cyclic aliphatic refers to saturated and undersaturated cyclic hydrocarbon here, also just says cycloolefin and cycloalkane.This term of aromatics refers to biaryl here, benzene, two aryl that naphthalene, phenanthrene, anthracene and alkylidene bridge link up.
Cycloalkane here refers to and comprises one, and two, the alkane of three or a plurality of rings.Cycloolefin refers to the monocycle with one or more pair key here, dicyclo and many cyclic groups.
Alkyl refers to the organic group that contains carbon atom and hydrogen atom here.This term of employed alkyl comprises following organic group: alkyl, thiazolinyl, cycloalkyl, cycloalkenyl group, aryl, the aralkyl and the alkaryl of aliphatic series and cyclic aliphatic.Aliphatic series refer to straight chain here with side chain, and the saturated hydrocarbon chain that closes with insatiable hunger that is to say alkyl, thiazolinyl or alkynyl.Cyclic aliphatic refers to saturated and undersaturated cyclic hydrocarbon chain here, that is to say, and cycloalkenyl group, cycloalkyl, this term of aryl refers to biaryl here, xenyl, phenyl, naphthyl, phenanthryl, anthryl and two aryl that linked up by alkylidene bridge.Alkaryl refers to alkyl here, the aryl substituent of thiazolinyl or alkynyl substituted, and wherein, the definition of aryl is as mentioned above.Aralkyl here refers to the alkyl after the aryl replacement, thiazolinyl or alkynyl, and wherein, the definition of aryl is as mentioned above.The alkene aryl refers to the group that comprises an alkene part and an aromatic hydrocarbons part at least here, and comprises that one of them above olefin group alternately has those groups of more than one aryl.Alkyl with 1 to 20 carbon atom comprises methyl straight chain and side chain, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.Alkyl with 1 to 5 carbon atom comprises methyl, ethyl, propyl group, butyl and amyl group.
Cycloalkyl here refers to and comprises one, and two, the alkyl of three or a plurality of rings.Cycloalkenyl group refers to the monocycle that comprises one or more pair key here, dicyclo and many cyclic groups.Cyclenes also refers to the cycloalkenyl group that those have two or more two keys here.
Method provided by the present invention can be used for reclaiming the metal useful component by foam flotation method from metallic ore.Metallic ore refers to the former state metallic ore that comes out from underground mining here, comprising the metal useful component that is blended together with gangue.Gangue refers to those materials that must separate valueless at all here from the metal useful component.This method can be used to reclaim metal oxide, metal sulfide and other metal useful component.
Can effectively utilize the sulfide ore that these compounds reclaim and comprise the ore that contains copper sulfide, the ore that contains zinc sulphide contains the ore of molybdenum sulfide, contains the ore of cobalt sulfide, the ore that contains nickel sulfide, the ore that contains aluminium sulfide contains the ore of arsenones, contains the ore of silver sulfide, the ore that contains chromic sulfide, the ore that contains aurosulfo contains the ore of platinum sulfide, and the ore that contains uranium sulfide.Available method of the present invention comes therefrom by the froth flotation process that the object lesson of the sulfide ore of sulphide-rich comprises, for example contains the ore of copper: chessylite (CuS) for example, vitreous copper (Cu 2S), chalcopyrite (CuFeS 2), vallerite (Cu 2Fe 4S 7) or (Cu 3Fe 4S 7), bornite (Cu 5FeS 4), chalmersite (Cu 2SFe 4S 5) enargite [Cu 3(As 1Sb) S 4], tetrahedrite (Cu 3S 6S 2), tennantite (Cu 12As 4S 13), brochantite [Cu 4(OH) 6SO 4], hydroxyl copper mine [Cu 3SO 4(OH) 4], famatinite [Cu 3(S bA s) S 4] and bournonite (PbCuSbS 3); Contain plumbous ore: galena (PbS) for example; The ore that contains antimony: stibnite (Sb for example 2S 3); The ore that contains zinc: zincblende (ZnS) for example; The ore that contains silver: stephanite (Ag for example 5SbS 4), and silver ore (Ag 2S); The ore that contains chromium: daubreelite (FeSCrS for example 3); And contain platinum and contain the ore of palladium: for example cooperite [Pt(AsS) 2].
The oxide ore that method of the present invention is suitable for comprises the ore that contains Cu oxide, the ore that contains aluminum oxide, the ore that contains ferriferous oxide, the ore that contains iron titanium oxide, the ore that contains magnesium aluminum oxide contains the ore of siderochrome oxide, contains the ore of titanium oxide, the ore that contains Mn oxide, the ore that contains the ore of tin-oxide and contain uranium oxide.Can adopt method of the present invention by foam flotation method therefrom the object lesson of the oxide ore of enriched in metals oxide comprise the ore that contains copper: cuprite (Cu for example 2O), black copper ore (CuO) hole Cui Shi [Cu 2(OH) 2CO 3], chessylite [Cu 3(OH) 2(CO 3) 2], atacamite [Cu 2Cl(OH) 3], chrysocolla (CuSiO 3); The ore that contains aluminium: corundum for example; The ore that contains zinc: for example zincite (ZnO), and smithsonite (ZnCO 3); The ore that contains iron: for example bloodstone and magnetic iron ore; The ore that contains chromium: chromite (FeOCr for example 2O 3); Contain iron and contain the ore of titanium: ilmenite for example; Contain magnesium and contain the ore of aluminium: spinelle for example; Contain iron and contain the ore of chromium: chromite for example; The ore that contains titanium: rutile for example; The ore that contains manganese ore: pyrolusite for example; The ore that contains tin: cassiterite for example; With the ore that contains uranium: ulrichile for example; And the ore of rich uranium: pitch blende [U for example 2O 5(U 3O 8)] and pittinite (UO 3NH 2O).
Other metal useful component that is suitable for reclaiming with method provided by the invention includes the ore of gold: pin gold and silver (AuAgTe for example 2) and gold mine (AuTe); The ore that contains platinum and contain palladium: sperrylite (PtAs for example 2); The ore that contains silver; Silver ore (AgTe for example 2).
In preferred specific embodiments of the present invention, the useful composition of mineral that contains oxide or contain sulfide is reclaimed.In preferred specific embodiments of the present invention, copper sulfide, nickel sulfide, vulcanized lead, zinc sulphide or molybdenum sulfide useful component are reclaimed.In the present invention, in the most preferred specific embodiments, the copper sulfide useful component is reclaimed.
The required rate of recovery of the useful composition of metal that the working concentration of trapping agent of the present invention can obtain reclaiming according to hope and regulating arbitrarily.Specifically, its working concentration depends on the kind of the concrete metal useful component that need to reclaim, and desires to carry out the grade of the ore of froth flotation, to the quality requirement of the metal useful component that reclaimed, and the kind of the concrete mineral useful component that is reclaimed.The working concentration that trapping agent of the present invention is preferentially selected for use is that the ore of per metric ton froth flotation restrains to 250 gram trapping agents with 5, and the working concentration of more preferably selecting for use is that the ore of per metric ton froth flotation restrains to 100 gram trapping agents with 10.
In general, foam flotation method of the present invention requires to use foaming agent.At well-known in the art any foaming agent,, all be suitable for as long as can reach the rate of recovery to the metal useful component of desired recovery.And, in foam flotation method of the present invention, expection can with the present technique field in well-known other trapping agent form under the form of mixture and use trapping agent of the present invention.
Known in the present technique field and can with the form of trapping agent composition mixture provided by the present invention under the trapping agent that is applied can reach trapping agent for this to the required rate of recovery of the desired metal useful component that obtains.
In the present invention, the object lesson of operable known trapping agent comprises single thiocarbonic acid hydrocarbyl carbonate, dithiocarbonic acids Arrcostab, the trithiocarbonic acid Arrcostab, dialkyl dithiocarbamate, thion alkyl carbamate, dialkyl group sulphur, dialkyl dithiophosphate and diaryl, the single thiophosphate dialkyl, sulfo-acyl chlorides, two thio-acid dialkyl and diaryl esters, alkyl hydrosulfide, Minerec (XanH 2Ogen formateg), xanthate flows 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 Fen Ji phosphoric acid and salt thereof, esters of sulfosuccinic acids (Sulfosuccinates), sulfo-glass amic acid esters, primary amine, secondary amine, tertiary amine, quaternary ammonium salt, Fixanol, guanidine, and alkyl propane diamine.
In the present invention, operable foaming agent is included in the present technique field known and can reach any foaming agent to the rate of recovery of the mineral useful component of desired recovery.The object lesson of this class foaming agent comprises the alcohols with 5 to 8 carbon atoms, pine tar class, cresols class, the alkyl ether with 1 to 4 carbon atom of polypropylene glycol, the dihydroxy thing of polypropylene glycol, glycols, fatty acid, soap class, alkarylsulphonic acid salt and similar substance thereof.And, also can use the mixture of these foaming agents.In the present invention, all are suitable for all can using by the foaming agent of foam flotation method enrichment ore.
Used ω-(sulfenyl) alkyl amine can adopt Berazosky etc. at United States Patent (USP) 4,086, disclosed method in 273; French Patent (FRP) 1,519, disclosed method in 829; Perhaps adopt " Beilstein, 4,4+hEd, 4th Supp, 1655(1979) " described in method make.Used (omega-amino-alkyl) hydrocarbon acid amides can adopt Fazio at United States Patent (USP) 4,326, the method for being narrated in 067; The method of being narrated in " Acta Polen Pharm, 19,277(1962) "; Perhaps adopt the method for being narrated in " Beilstein, 4,4th Ed, 3rd Supp, 587(1962) " to make.Used-(oxyl-) alkylamine can adopt method illustrated in the BP 869,409; Perhaps adopt Hobbs at United States Patent (USP) 3,397, illustrated method makes in 238.Used S-(omega-amino-alkyl) carbothioic acid ester can adopt Faye etc. at United States Patent (USP) 3,328, illustrated method in 442; Perhaps adopt " Beilstein, 4,4th Ed, 4th Supp, 1657(1979) " in illustrated method make.Used omega-amino-alkyl oxycarbonyl acid esters can adopt " JAmChemSoc, 83,4835(1961) " in illustrated method: " Beilstein, 4th Ed, 4th Supp, 1413(1979) " in illustrated method; Perhaps adopt " Beiltein, 4th Ed, 4th Supp, 1785(1979) " in illustrated method make.Used N-(alkyl)-and α, the W-alkane diamine can adopt that well-known method makes in the present technique field, and one of them instantiation is to adopt that illustrated method prepares in the Deutsches Wirtschafts Patent 98,510.
For the present invention is described, provided the following example, still, embodiment can not be interpreted as it is restriction to the scope of the present invention or claim here.Except as otherwise noted, otherwise all umber and marks all calculate by weight.
In the following example, be to come the operating characteristic of described foam flotation method is described by speed constant and the mineral yield in the unlimited time that provides floating operation.These numerical value all adopt following formula to calculate:
r＝R［1- (1－e -kt)/(kt) ］
In the formula: r is the mineral useful component amount that reclaims in time t, and K is the speed constant of recovery rate, and R is the mineral useful component amount that is reclaimed in the infinite time that calculates.With the mineral yield of measuring in different time, then, this series of values substitution aforesaid equation just can be obtained R and K value.In " selection of chemistry of Flotation reagent " that RKlimipel showed [see the 45th chapter, the 907th～934 page, the design of mineral processing scheme, second edition, 1980, AIME(DenVer)], above-mentioned formula is described.
Embodiment 1
The froth flotation of copper sulfide
In the present embodiment, tested the situation that several trapping agent provided by the invention is used for the floating cupric sulfide useful component.In rod mill, add Chilean copper mine stone 500 grams compressed in advance, i.e. chalcopyrite copper sulfide ore and 257 gram deionized waters.Granularity is that about 75 microns or littler particle accounts for 80.2% in this copper mine stone.According to the needed pH value of floating operation subsequently, also in this rod mill, add a certain amount of lime, then, this rod mill rotates the ore pulp that will grind to form like this in 360 weeks with 60 rev/mins rotating speed and changes air-blowing flotation device (Agitair over to
Figure 851096433_IMG30
In the flotation cell of 1500 millis Flotation machine).Stir this flotation cell with 1150 rev/mins speed, when needed, add lime again the pH value is adjusted to 10.5.
In this flotation cell, add trapping agent (its adding rate is 50 gram/metric tons), then, modulate one fen clock time, add foaming agent immediately, DOWFROTH
Figure 851096433_IMG31
The trade mark of 250[Dow Chemical Company (The Dow Chem-ical Company)], and its adding rate is 40 gram/metric tons through after the modulating time of another minute, blasts air with the speed of 4.5 liters of per minutes in this flotation cell, and starts automatic de-bubble paddle.0.5,1.5,3,5 and 8 minutes time point takes out foam sample, makes the dry mistake of foam sample in baking oven, simultaneously flotation tailing.With the samples weighing of drying, be divided into suitable assay sample, and will pulverize to reach satisfactory fine granularity, to be dissolved in the acid then and analyze.Analyze these samples with direct current plasma again.
The trapping agent that is used for Chilean copper mine stone copper sulfide useful component float test is listed in the table I, and the table I shows, belongs to the rate of recovery that the interior all cpds of the scope of the invention can improve the copper sulfide useful component effectively.In the table I, also listed the basic example that is used for comparison, wherein do not adopt trapping agent.Should be noted that selected trapping agent of the present invention is not the compound of optimum performance in the table I, and the compounds of just a bit selecting for use arbitrarily, wherein shown the rate of recovery of mineral useful component and optionally significantly improve effect.(seeing Table I)
Embodiment 2
According to 1 li described method of embodiment, with middle African cupric oxide ore (Cu 2O) carry out froth flotation, wherein used foaming agent is DOWFROTH
Figure 851096433_IMG32
The trade mark of 250(Dow Chemical Company), its consumption is 40 gram/metric tons.Flotation experimental results is listed in the table II, and used trapping agent A and B are selected from the table I.(seeing Table II)
A is C 6H 13-S CH 2
Figure 851096433_IMG34
2-NH 2
B is C 7H15
Figure 851096433_IMG35
-NH
Figure 851096433_IMG36
CH 2) 2-NH 2
C is a sodium isopropyl xanthate, is not embodiment of the present invention.
As everyone knows, in mining industry, existing industrial trapping agent, for example sodium isopropyl xanthate flotation oxide mineral very effectively.Therefore, with use concentration be 160 gram/tons general trapping agent C by comparison, trapping agent A is only with 80 gram/tons, when half the working concentration that is the application concentration of trapping agent C carries out flotation, will make the rate of recovery of copper useful component improve 84.4%, this point is very beat all.When with the trapping agent A of concentration 160 gram/tons, its performance and general trapping agent C can see that the rate of recovery of copper useful component has improved 148% by comparison.The yield of the copper useful component when trapping agent of the present invention can improve flotation ferriferous oxide ore widely, this fact has shown another kind of situation again, promptly with existing trapping agent by comparison, the trapping agent that provides by requirement of the present invention is not too responsive to the existence form of the mineral that contain metal, that is to say, no matter mineralizer or oxide.
Embodiment 3
According to embodiment 1 described method, use trapping agent of the present invention and, will contain copper sulfide, nickel sulfide at several trapping agents well known in the art, platinum, Canada's middle part sulfide ore of palladium and golden useful component carries out a series of froth flotation test.Used foaming agent is DOWFROTH
Figure 851096433_IMG37
The trade mark of 1263(Dow Chemical Company), working concentration is that the working concentration of 0.00625 pound of/ton (3.12 gram/metric ton) trapping agent is that the foam that produced in 0.0625 pound of/ton (31.2 gram/metric ton) floatation process is 0.5,1.0,2.0,4.0,7.0,11.0 and on 16.0 minutes time point, collect.Result of the test is listed in the table III, and trapping agent wherein is selected from the table I.(seeing Table III)
The table III shows, with three kinds of preferred general industries with trapping agent by comparison, two kinds of new compounds that provide by requirement of the present invention, the i.e. operating position of OHTEA and NOPA.Testing used ore is the complex ore that contains various metal useful components.The operating characteristic of used trapping agent is that the rate of recovery value with the copper useful component compares.Clearly, just reclaim metallic nickel, platinum, palladium and gold, trapping agent OHTEA is superior.When reclaiming metallic nickel, with Z-211
Figure 851096433_IMG38
Situation by comparison, the R-16 value of OHTEA has only increase slightly, still, just reclaims magnetic iron ore, its value has quite unexpected and is crucial reduction, has promptly reduced by 15.5%.For platinum and palladium, this substantial improvement also shows and has reduced mine tailing, and for gold, it is worth about equally.
When with the present technique field in the best known trapping agent that adopted by comparison, trapping agent NOPA has the good rate of recovery concerning copper and mickel.And with table in general trapping agent by comparison, this trapping agent is showing superior operating characteristic aspect the R-16 value of magnetic iron ore reducing.With those known trapping agents by comparison, can also be clear that very that the rate of recovery of nickel is dominant with the ratio of the rate of recovery of magnetic iron ore, that is to say that ratio has improved 30%.Because the major part in the floating product is unwanted sulphur-containing substance, so, if want to reduce requirement to smelting furnace, the selectivity of NOPA is very important.
Embodiment 4
The froth flotation of copper sulfide
In the present embodiment, make the float test of copper sulfide useful component with several trapping agents provided by the invention.500 gram Canada West copper mine stones are put into the rod mill that is mounted with 1 inch grinding rod, be added with 257 gram deionized waters in this rod mill, this copper mine stone that is added is the quite high and chalcopyrite sulfo-copper mine stone pyritiferous hardly of grade, making this rod mill rotate 420 then under 60 rev/mins rotating speed changes, and is lower than 100 purposes and accounts for 25% size distribution state so that make ore reach granularity.According to the size of desired pH value in the follow-up floatation process, also in this rod mill, add a certain amount of lime.Change the ore pulp that so grinds to form over to air-blowing flotation device (Agitair
Figure 851096433_IMG39
) 1500 milliliters flotation cell in.Stir this flotation cell with 1150 rev/mins rotating speeds, and where necessary, add some lime in addition again, its pH value is adjusted to 8.5.
Add trapping agent in this flotation cell, its addition is 8 gram/metric tons, places then 1 minute, waits then to add foaming agent, DOWFROTH again The trade mark of 250(Dow Chemical Company), its addition is 18 gram/metric tons.After other 1 minute time of placement, beginning blasts air in this flotation cell, and its speed is 4.5 liters/minute, and starts automatic de-bubble paddle.0.5,1.5,3.5 and 8 minutes time point takes out foam sample.In baking oven, make the foam sample dried overnight, simultaneously flotation tailing.The weighing drying sample is divided into and moves a part suitable analytic sample, and pulverizes to guarantee reaching satisfactory fine granularity, is dissolved in the acid then and analyzes.Adopt these samples of direct-current plasma analysis of spectral method, analysis result is listed in the table IV, and wherein, the compound of embodiment 1 to 32 is single-row in following:
1. there is not trapping agent
Figure 851096433_IMG41
3.(the S(CH tert-butyl group) 2) 2NH 2
Figure 851096433_IMG43
5.
Figure 851096433_IMG44
6.（C 4H 9） 2-N-（CH 2） 2NH 2
Figure 851096433_IMG45
8.
Figure 851096433_IMG46
9.
Figure 851096433_IMG47
Figure 851096433_IMG48
13.C 8H 17S-（CH 2） 3NH 2
14.C 6H 13S（CH 2） 2NCS
Figure 851096433_IMG49
Figure 851096433_IMG50
23.C 8H 17S（CH 2） 2NH 2
24.C 4H 9S（CH 2） 2NH 2·HCl
Figure 851096433_IMG51
31.NH 2-CH 2-CH（OH）-CH 2-O-CH 2-CH（C 2H 5）-C 4H 9
32.C 6H 13-S（CH 2）C≡N
1* is not embodiments of the invention (seeing Table IV and table V)
The different sulfide ore of various compound test that embodiment 4 uses in the scope of the invention, with the exception of this, similar with embodiment 1.Test does not plan to point out most preferred embodiment of trapping agent of the present invention, but, can be clear that very much from result of the test, just reclaim the copper useful component, with the result of the test of no trapping agent by comparison, used whole compounds all show very superior operating characteristic.When with known general trapping agent by comparison, with regard to the particular ore of institute's flotation, these general trapping agents are optimum, trapping agent provided by the present invention can show the superior rate of recovery and selectivity.
Embodiment 5
The froth flotation of copper sulfide and molybdenum sulfide
At first make packed homogeneous ore, heavy 1200 grams of each bag.The rough floatation process is in the ball mill of a band stirring-type spherical material charging aperture, with 800 cubic centimetres running water with 1200 gram chargings grindings 14 minutes, (is the grinding ore pulp more than 13% of accounting for about 100 orders thereby obtain granularity).Such ore pulp is changed in the A500 flotation cell, wherein be furnished with automatic defoaming device, and the pH value of this ore pulp is transferred to 10.2 with lime.In process of the test, no longer carry out the adjusting of pH value.Used general foaming agent is methyl isobutyl carbinol (MIBC).Carry out 4 grades of rough floatation operating processes then.
The 1st grade: trapping agent-0.0042 kilogram/ton
MIBC-0.015 kilogram/ton
-placed-1 minute
-flotation-collection enrichment ore deposit 1 minute
The 2nd grade: trapping agent-0.0021 kilogram/ton
MIBC-0.005 kilogram/ton
-placed-0.5 minute
-flotation-collection enrichment ore deposit 1.5 minutes
3rd level: trapping agent-0.0016 kilogram/ton
MIBC-0.005 kilogram/ton
-placed-0.5 minute
-flotation-collection enrichment ore deposit 2 minutes
The 4th grade: trapping agent-0.0033 kilogram/ton
MIBC-0.005 kilogram/ton
-placed-0.5 minute
-flotation-collection enrichment ore deposit 2.5 minutes (seeing Table V)
1, ore pulp lime treatment useless, its pH value transfers to 8.2.
The table V shows, concerning copper and molybdenum, has reached the obvious high grade than trapping agent A.With regard to copper, the minimum improvement value of grade is more than 10%, and the highest improvement value is 77%.And concerning molybdenum, the minimum improvement value of grade is about 30%, and the highest improvement value of optimization is about 122%.This improvement can significantly reduce to smelt the load of smelting furnace in the operation process.
Concerning iron, any test also of using trapping agent B of the present invention shows that the grade of iron has reduced widely, with general trapping agent A by comparison, approximately reduced by 50%, quite few unwanted pyrite is only collected in this explanation.In the process of collecting the metal sulfide useful component, be extremely beneficial to this beat all selectivity of sulphur ferrous components ferrous components to the downstream process of smelting operation, because this can reduce separating out of sulphur.
Embodiment 6
The froth flotation of the nickel/cobalt ore of western australia
At first preparation is in the nickel/cobalt ore charging of 750 grammes per square metres under the ore pulp form (wherein containing 30% solid).Test is Agitair with flotation cell
Figure 851096433_IMG52
LA-500 type flotation cell wherein is furnished with automatic de-bubble paddle, and its running rate is 60 rev/mins.General operation sequence is, at first adds CuSO with 0.2 kilogram/tonne consumption 4, placed 7 minutes, add guar gum with 0.14 kilogram/ton consumption, as the depressant of talcum, and add trapping agent with 0.16 kilogram/tonne consumption, add foaming agent (for example can add triethoxybutane) then, thereby make the suitable foam bed.Collect the operation in enrichment ore deposit and carry out 5 minutes (being denoted as rough floatation enrichment ore deposit).Then, the consumption with 0.16 kilogram/tonne adds trapping agent in the remaining composition in flotation cell, and the while is with 0.07 kilogram/tonne consumption adding guar gum and required foaming agent, collect the operation in enrichment ore deposit and carry out 9 minutes (flotation ore deposit in the middle of being denoted as), and remaining composition is referred to as flotation tailing in the flotation cell.After this, rough floatation enrichment ore deposit is changed in the littler flotation cell, with 0.08 kilogram/tonne consumption to wherein adding trapping agent, and the while is with 0.14 kilogram/tonne consumption adding guar gum, but do not add any foaming agent, collect the operation in enrichment ore deposit and carry out 3 minutes (being denoted as the purification enrichment ore deposit), and the composition in the flotation cell is the purification mine tailing.Sample, is measured with the x-ray analysis method after the drying through filtering.The rate of recovery is calculated with the standard method on the metallurgy, the results are shown in the precious VI of this test, wherein, below the used compound tabulation of embodiment 1 to 5:
1. ethyl sulphur ortho acid sodium
2.C 6H 13S（CH 2） 2NH 2
Figure 851096433_IMG53
4.（C 4H 9） 2-N-（CH 2） 2NH 2
Figure 851096433_IMG54
* not embodiments of the invention (seeing Table VI)
The plant model test of the data represented continous way industry floatation process in the table VI.The listed data in " flotation tailing " hurdle are most important data, and it has shown actual metal loss amount, that is to say, the numerical value in the flotation tailing hurdle is more little, and the loss amount of metal is just few more.General easy to carryly catch agent by comparison with industrial in the art, the superiority of the trapping agent of the present invention of described test is clearly, just reclaim the rate of recovery of nickel, numerical value in the flotation tailing hurdle is strained and reduced by 8% most, and the numerical value in the floating mine tailing hurdle has unexpectedly reduced by 81% at most to the greatest extent.For cobalt, except trapping agent 3, also reached similar improvement effect.
Embodiment 7
The froth flotation in the Pb/Zn/Cu/Ag grandidierite ore deposit at Canada middle part
The even ore sample that at first prepares 1000 grammes per square metres.In each float test, sample added fill 500 expound one's ideas in writing centimetre running water and 7.5 milliliters of SO 2In the rod mill of solution.Adopt 6.5 minutes milling time of San, thereby make flotation feed, wherein 90% particle has the granularity less than 200 orders (75 microns).After the grinding, ore pulp is changed in the flotation cell that automatic de-bubble paddle is housed, there is the Denver flotation device of standard in this flotation cell team.
Then, carry out the floating operation of two-stage, at the 1st grade, rough floatation copper/lead/silver, and in the II level, rough floatation zinc.In order to begin I level floating operation, add NCO with the consumption of 1/5 gram/kilogram, and the pH value is transferred to 8.5, add trapping agent subsequently.Then, blasting under air and the while stirring condition, this ore pulp was handled 5 minutes.After this, only under agitation handled two minutes, then, add methyl isobutyl carbinol (MIBC) foaming agent (general addition is 0.015 milliliter/kilogram).In 5 minutes floatation process, collect the enrichment ore deposit, it is shown copper/plumbous rough floatation enrichment ore deposit.
II level floating operation comprises that the consumption with 0.3 kilogram/tonne adds CuSO in the material that is left after the flotation of I level in flotation cell 4Then, add lime, the pH value is transferred to 9.5.After this, it was handled 5 minutes, at this moment only stir.Measure its pH value subsequently again, and add lime again and regulate, allow it be returned to 9.5.At this moment, add trapping agent,, at this moment only stir with post processing 5 minutes.Add methyl isobutyl carbinol (MIBC) foaming agent (general addition is 0.020 milliliter/kilogram) then.Collected the enrichment ore deposit at 5 minutes in the clock time, it is denoted as zinc rough floatation enrichment ore deposit.
Enrichment sample ore product are dry, and weighing is made suitable sample then and is measured to use x-ray technology.At last, use measured data, calculate with regard to available logical mass balance formula and reclaim real-valued and grade.(seeing Table VII)
The table VII shows, industrial optimized general trapping agent, when its with trapping agent of the present invention relatively the time, the operating characteristic aspect recovery metal useful component.In test 1 I level flotation, employing be the composition of general trapping agent A and B, and in the flotation of II level, employing be the composition of general trapping agent A and C.In test 2 I level flotation, employing be the general trapping agent B and the trapping agent D of the present invention of roughly equivalent.In test 2 II level flotation, employing be trapping agent D of the present invention.
The purpose of this test is to keep the rate of recovery value of silver and copper in the flotation of I level, and improve the rate of recovery of zinc in the flotation of II level.Result of the test shows that trapping agent D has roughly kept the rate of recovery value of silver and copper, is improved simultaneously on grade.The most important thing is, in the II level flotation step of test 2, the rate of recovery value (R-5) and the grade of zinc, the general trapping agent with respect in the test 1 has improved 3% and 6% respectively.
Table I (A part)
The trapping agent kind:
Figure 851096433_IMG55
Copper Cu gangue Cu gangue
R 1R 2K R K R R-8 1R-8 1Selectivity 2
Heptyl hydrogen 5.15 0.716 3.16 0.099 0.714 0.100 7.1
Butyl hydrogen 4.62 0.699 2.31 0.091 0.693 0.091 7.6
Octyl group hydrogen 3.29 0.722 1.75 0.091 0.703 0.087 8.1
Basic hydrogen 4.14 0.730 2.19 0.095 0.724 0.094 7.7
Methyl hydrogen 3.92 0.490 3.51 0.064 0.479 0.064 7.5
Dodecyl hydrogen 2.31 0.605 1.94 0.048 0.586 0.047 12.5
Octyl group ethyl carbonyl 1.79 0.716 1.13 0.073 0.638 0.062 10.3
Basic ethyl carbonyl 5.55 0.670 3.78 0.081 0.662 0.080 8.3
1,1-dimethyl ethyl carbonyl 1.46 0.640 0.82 0.097 0.571 0.080 7.1
Decyl
1.R-8 represent the experiment rate of recovery value after 8 minutes
2. the gangue rate of recovery value of the copper recovery value when selectivity was by 8 minutes during by 8 minutes removed resulting calculated value
Table I (B part)
The trapping agent kind:
Figure 851096433_IMG56
Copper Cu gangue Cu gangue
R 1R 2N K R K R R-8 1R-8 1Selectivity 2
Nonyl phenyl hydrogen 2 2.61 0.583 3.48 0.080 0.572 0.081 7.1
Nonyl phenyl TOFA 32 2.22 0.430 3.41 0.116 0.410 0.112 3.7
Nonyl 3-aminopropyl 3 4.03 0.603 2.89 0.077 0.586 0.073 8.0
Nonyl hydrogen 3 3.41 0.685 2.82 0.079 0.658 0.077 8.5
Heptyl hydrogen 3 1.59 0.675 1.31 0.082 0.622 0.076 8.2
Nonyl phenylethyl carbonyl 2 2.44 0.358 2.94 0.054 0.341 0.053 6.4
Phenyl hydrogen 2 4.46 0.581 3.16 0.069 0.575 0.069 8.3
Phenylethyl carbonyl 2 2.56 0.295 4.04 0.071 0.287 0.070 4.1
1.R-8 represent the experiment rate of recovery after 8 minutes
2. the gangue rate of recovery value of the copper recovery value when selectivity is 8 minutes during by 8 minutes removed the calculated value that obtains
3. ready denier oil acid root
Table I (C part)
The trapping agent kind:
Figure 851096433_IMG57
Copper Cu gangue Cu gangue
R 1R 2R 3K R K R R-8 1R-8 1Selectivity 2
Butyl hydrogen butyl 4.61 0.628 3.12 0.056 0.622 0.057 10.9
Butyl ethyl carbonyl butyl 4.16 0.443 3.31 0.084 0.428 0.081 5.3
Ethyl hydrogen ethyl 3.55 0.488 3.37 0.056 0.475 0.056 8.5
Ethyl carbonyl hydrogen hydrogen 2.15 0.298 3.57 0.053 0.284 0.052 5.5
Heptyl carbonyl hydrogen hydrogen 5.66 0.636 3.68 0.095 0.630 0.094 6.7
Basic hydrogen is base 3.52 0.608 2.36 0.069 0.587 0.067 8.8
Basic ethyl carbonyl is based 1.5 4 0.438 1.06 0.080 0.394 0.068 5.8
Heptyl carbonyl hydrogen hydrogen 4.32 0.532 2.33 0.099 0.523 0.097 5.4
Nonyl carbonyl hydrogen hydrogen 5.22 0.669 3.06 0.091 0.654 0.089 7.3
The 4-[(2-carbonyl)-Ding oxygen hydrogen hydrogen 4.81 0.381 3.94 0.058 0.381 0.057 6.7
Base]-the 3-aminomethyl phenyl
6-(2-carbonyl-propyl group hydrogen hydrogen 3.06 0.438 2.82 0.062 0.422 0.061 7.0
-2-ethylhexyl
(N-propyl group)-8-(hydrogen hydrogen hydrogen 3.41 0.463 2.79 0.059 0.450 0.058 7.8
Base)-the 7-(hydroxyl)-hydrogen
The 5-(ethyl) octyl group
Tetrahydrochysene-ZH-pyrrole ethyl carbonyl hydrogen 3.27 0.295 6.37 0.073 0.289 0.073 4.0
The ketone group of muttering
1.R-8 represent the experiment rate of recovery value after 8 minutes
2. the gangue rate of recovery value of the copper alluvial when selectivity is 8 minutes during by 8 minutes removed the calculated value that obtains
Table I (D part)
Copper Cu gangue Cu gangue
Compound K R K R R-8 1R-8 1Selectivity 2
3-(N, the N-dimethyl) ammonia 4.02 0.455 2.71 0.086 0.439 0.083 5.3
Base propyl group-acid amides nonane
1,2-second two bases [nitrilo-2.68 0.318 2.74 0.076 0.306 0.072 4.2
Two (methyl-alkene)] } tetra methylene phosphonic acid
No trapping agent 2.63 0.298 3.20 0.060 0.289 0.098 4.9
1.R-8 represent the experiment rate of recovery value after 8 minutes
2. the gangue rate of recovery value of the copper recovery value when selectivity is 8 minutes during by 8 minutes removed the calculated value that obtains
3. not embodiments of the invention
The table II
Copper Cu
Trapping agent concentration gram/ton pH K R R-8
A 160 5.1 2.48 0.335 0.308
A 80 9.5 2.55 0.249 0.234
B 80 9.5 2.91 0.313 0.289
C 160 5.1 4.08 0.135 0.130
The table III
Copper nickel magnetic iron ore mine tailing 3
Trapping agent K R-4 1R-16 2R K R-4 1R-16 2R K R-16 2R Ot Pd Au
Yellow 5.4 .883 .934 .932, the 1.39 .696 .855 .876 of amyl group 0.49 0.275 .302 .0110 .0112 .0054
Ortho acid sodium * 4.7 .931 .958 1.00 0.87 .760 .889 .990 0.25 0.496 .612 .0071 .0100 .0049
Z-211 4*4.8 .885 .934 .936 1.94 .776 .890 .907 0.25 0.419 .540 .0054 .0094 .0048
OHTEA 56.4 .909 .942 .949 1.31 .245 .325 .323 1.02 0.185 .177 .0139 .0116 .0054
Aerofloat
3477 6*4.4 .816 .887 .879 1.81 .637 .799 .789 0.66 0.199 .198 .0117 .0124 .0064
MOPA 7
* not embodiments of the invention
1.4 the rate of recovery after minute
2.16 the rate of recovery after minute
3. per metric ton ounce-mine tailing is represented to be included in the gangue that floats and the amount of metal that does not obtain reclaiming
4. the trade mark of Dow Chemical Company-thion acid esters
5.OHTEA expression ω-(basic thio-ethylamine)
6. U.S.'s cyanogen is by the trade mark-phosphorodithioate of company.
7.NOPA represented-(oxygen base in the ninth of the ten Heavenly Stems) propylamine
The table IV
Copper gangue copper gangue
Embodiment K R K R R-8 R-8 selectivity
1＊ 2.11 .306 1.61 .068 .291 .066 4.4
2 4.19 .629 3.63 .140 .606 .136 4.5
3 3.65 .621 4.28 .121 .600 .121 5.0
4 3.79 .943 2.95 .196 .906 .189 4.8
5 2.69 .789 2.37 .160 .730 .148 4.9
6 2.04 .382 1.88 .0735 .358 .0692 5.2
7 3.86 .585 3.44 .118 .562 .114 4.9
8 2.36 .435 2.15 .0858 .409 .0815 5.0
9 5.16 .742 4.43 .157 .719 .153 4.7
10 2.38 .499 2.10 .100 .469 .0951 4.9
11 4.53 .869 3.59 .184 .838 .179 4.7
12 2.06 .448 1.80 .0895 .418 .0840 5.0
13 3.90 .572 3.22 .126 .551 .123 4.5
14 2.12 .863 1.59 .192 .809 .179 4.5
15 3.43 .534 2.90 .108 .513 .106 4.8
16 2.94 .424 2.45 .0841 .408 .0816 5.0
17 5.00 .641 4.33 .148 .622 .145 4.3
18 3.51 .682 3.01 .175 .649 .168 3.9
19 2.68 .451 2.29 .097 .429 .094 4.6
20 3.46 .449 2.96 .092 .431 .090 4.8
21 4.58 .909 3.44 .187 .878 .181 4.8
22 4.22 .540 3.60 .124 .523 .123 4.3
23 3.61 .514 2.96 .111 .493 .107 4.6
24 3.54 .542 3.21 .121 .520 .117 4.4
25 3.54 .832 2.73 .162 .802 .156 5.1
26 2.14 .367 1.61 .080 .345 .075 4.6
27 3.62 .520 2.98 .119 .501 .116 4.3
28 1.97 .848 1.56 .180 .788 .166 4.7
29 2，41 .308 2.11 .0676 .296 .066 4.5
30 2.35 .340 2.14 .0702 .324 .0676 4.8
31 2.25 .355 2.18 .0737 .338 .0710 4.8
32 7.17 .723 5.32 .156 .707 .155 4.6
1* is not embodiments of the invention
The table V
Copper/molybdenum ore that Canada West comes
Trapping agent consumption kilogram/metric ton copper recovery molybdenum recovery copper grade molybdenum grade iron grade
R-7 minute R-7 minute
A 0.0112 0.776 0.725 0.056 0.00181 0.254
B 0.0112 0.688 0.682 0.063 0.00233 0.108
B 0.0067 0.659 0.759 0.099 0.00402 0.137
B 0.0112 0.648 0.747 0.080 0.00314 0.127
A. amylic potassium xanthate (not being embodiments of the invention)
B.
The table VI
Nickel/the cobalt ore of western australia
Nickel recovery percentage cobalt rate of recovery percentage
Purification enrichment ore deposit, flotation ore deposit flotation tailing purified the middle flotation of mine tailing ore deposit in the middle of trapping agent purification enrichment ore deposit flotation tailing purified mine tailing
1＊ 62.4 7.3 24.9 5.4 66.9 12.0 16.7 4.4
2 75.8 3.1 10.0 11.1 72.2 9.5 8.4 9.9
3 74.4 6.7 7.8 11.1 63.8 15.4 8.0 12.8
4 57.1 4.0 9.3 29.6 65.1 7.3 7.3 20.3
5 56.0 1.4 12.3 30.3 62.4 8.5 3.0 26.2
* not embodiments of the invention
The table VII
The Pb/Zn/CuAg ore at Canada middle part
Flotation step trapping agent addition Ag Cu Pb Zn
(primary flotation) agent (kilogram/ton) R-5 grade R-6 grade R-6 grade R-5 grade
1＊Cu/Pb A 0.005 0.843 0.286 0.926 0.120 0.738 0.053 0.179 -
B 0.0075
Zn A 0.020 0.109 - 0.057 - 0.155 - 0.808 0.314
C 0.015
2Cu/Pb D 0.005 0.826 0.320 0.914 0.129 0.710 0.057 0.153 -
B 0.0045
Zn D 0.021 0.118 - 0.063 - 0.174 - 0.833 0.334
A, sodium ethylxanthate
B, phosphorodithioate
C、CHS（CH）NH
R-5 is the actual recovered rate after 5 minutes
* not embodiments of the invention

Claims (5)

1, from metal sulfide, metal oxide or noble metal, the method of selective recovery metal useful component from metallic ore, its step comprises that the metallic ore with moisture ore pulp form carries out the froth flotation operation in the presence of collection agent, condition is that the metal useful component is reclaimed in foam, it is characterized in that trapping agent comprises following compound.
Figure 851096433_IMG2
Wherein: R is-CH 2-
Figure 851096433_IMG3
Or its mixed base, n be 1-6 integer or-(R) n is-(CH 2) m-C=, wherein m is the integer of 0-6; R 1With each R 2Represent the following substituent 1-22 carbon alkyl of 1-22 carbon alkyl or band independently: one or more hydroxyls, amino, phosphono, alkoxyl, imino group; carbamoyl, carbonyl, thiocarbonyl, cyano group, carboxyl; sulfenyl, oxyl, hydrocarbon amino or hydrocarbon imino, its condition is R 2Can be divalent group, and two all direct and nitrogen atom bondings of valence link;
；
A is integer 0,1 or 2;
B is integer 0,1 or 2;
Its condition is that a and b sum are 2, just R 2Be divalent group and two valence links all directly and except the situation of nitrogen atom bonding, b=0 in this case, and a=1 or-(R)-n is-(CH 2) m-C=situation also except, in this case, a+b=0,
Another condition is to be at X The time, carbonyl and R 1Bonding, and the trapping agent addition is a 5-250 gram/metric ton.
2, according to the method for claim 1, it is characterized in that, the compound that said metallic ore flotation is used as shown in the formula:
Figure 851096433_IMG6
Wherein:
R 1Be 1-22 carbon alkyl or the following substituent 1-22 carbon alkyl of band: one or more hydroxyls, amino, phosphono or alkoxyl;
R 2Be 1-6 carbon alkyl, 1-6 carbon alkyl-carbonyl has amino, the 1-6 carbon alkyl of hydroxyl or phosphono, or have amino, the 1-6 carbon alkyl-carbonyl of hydroxyl or phosphono;
And X, a, the definition of b and n is according to claim 1.
3, according to the method for claim 2, it is characterized in that R 1Be 2-14 carbon alkyl; R 2Be 1-6 carbon alkyl or 1-6 carbon alkyl-carbonyl; A is integer 0 or 1, and b is integer 1 or 2; And n is the integer of 1-4.
4, according to the method for claim 3, it is characterized in that R 1Be 4-11 carbon alkyl; R 2Be 1-4 carbon alkyl or 1-4 carbon alkyl-carbonyl; N is integer 2 or 3; And X is-S-.
5, require according to aforesaid right in any one trapping agent, wherein this compound is selected from ω-(sulfenyl)-alkylamine; ω-(sulfenyl) alkylamide; Or S-(omega-amino-alkyl) carbothioic acid ester.
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