CN1011765B - Process for foam flotation of s-contg. ore - Google Patents

Process for foam flotation of s-contg. ore

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Publication number
CN1011765B
CN1011765B CN86101682A CN86101682A CN1011765B CN 1011765 B CN1011765 B CN 1011765B CN 86101682 A CN86101682 A CN 86101682A CN 86101682 A CN86101682 A CN 86101682A CN 1011765 B CN1011765 B CN 1011765B
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China
Prior art keywords
thioether
mineral
ore
sulfide
alkyl
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CN86101682A
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Chinese (zh)
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CN86101682A (en
Inventor
理查德·R·克利姆贝尔
罗伯特·D·翰森
埃德温·J·斯特罗尼
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Dow Chemical Co
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Dow Chemical Co
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Publication of CN86101682A publication Critical patent/CN86101682A/en
Publication of CN1011765B publication Critical patent/CN1011765B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • 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-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

A froth flotation process for selectively recovering nonferrous metal containing sulfide minerals or sulfidized metal containing oxide minerals from ores. More particularly, this invention concerns a process for recovering metal containing sulfide minerals or sulfidized metal containing oxide minerals from an ore which comprises subjecting the ore, in the form of an aqueous pulp, to a froth flotation process in the presence of a flotating amount of a flotation collector wherein the collector has a hydrocarbon containing one or more monosulfide units, wherein the carbon atoms to which the sulfur atoms are bound are aliphatic or cycloaliphatic carbon atoms, the total carbon content of the hydrocarbon portion of the collector is such that the collector has sufficient hydrophobic character to cause the metal containing sulfide mineral or sulfidized metal containing oxide mineral particles to be driven to the air/bubble interface, under conditions such that the metal containing sulfide mineral or sulfidized metal containing oxide mineral is recovered in the froth.

Description

Process for foam flotation of S-contg. ore
The present invention relates to adopt new collector from ore, to reclaim the froth flotation method of the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration.
Floatation is to handle a kind of method of the mineral solids mixture that grinds, for example, the character of utilizing the part solid particle of ore to float on a liquid, make ore and other solid particle that grinds of claying into power, as other analog in clay or the ore separately, way is that a kind of gas (or on-the-spot a kind of gas that provides) is provided in liquid, makes liquid upper generate the foam material that contains some solid particle, stays (not foamy) other ore solid constituent of suspension.The flotation ratio juris is to introduce a kind of gas in the liquid of the SS that contains different material, causes some gases attached on some suspended solid, and non-cohesive on other suspended solid, thereby makes the particle that is attached with gas compare liquid light.Therefore, these particles rise to liquid upper and form foam.
Various flotation agent are mixed with suspension to improve foam method, and these additives are divided into by its action function: collecting agent, be used for sulfide mineral, and comprise xanthic acid salt, thionocarbamate etc.; Foaming agent, it gives the performance that forms stable foam, and natural oil for example is as pine tar and eucalyptus oil; Modifier for example is used to cause the activator of flotation, as copper sulphate in the presence of collecting agent; Inhibitor, Cymag for example, it helps to prevent that collecting agent from working with wishing the mineral matter that remains in the liquid, becomes foam segment thereby prevent from field trash carried secretly; The pH value conditioning agent, to reach best metallurgical effect, for example lime, soda ash or the like.
Remember that importantly above-mentioned various additives will be selected to use according to the character of the character of ore, the mineral of managing to reclaim and the character that is used for other additive of this mixed system simultaneously.
Understanding some phenomenons that make flotation become of great value industrial operation is not the essence that the present invention puts into practice, yet the appearance of these phenomenons has substantial connection with the milled solid particle surface that is suspended in the liquid that contains entrained gas to the selectivity affinity of liquids and gases.
This floating principle is applicable to a large amount of mineral separation methods, and from the iron content sulfide mineral, for example Selective Separation comes out also to belong to wherein row in pyrite, the magnetic iron ore the metal sulfide ore of cupric, zinc, lead, nickel, molybdenum and other metal.
Reclaim the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration, the collecting agent of common use has xanthates, dithiophosphates and thionocarbamate.Reclaim the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration, common think other effective collecting agent have mercaptan, disulphide (R-SS-R) and polysulfide [R-(S) n-R], wherein n is 3 or bigger.
The metal oxidation-containing mineral of metallic sulfide mineral or sulfuration is changed into more useful simple metal, often adopt method of smelting, this fusion process can cause the generation of volatile sulfur compounds, these volatile sulfur compoundses are often discharged into the atmosphere by chimney, are perhaps removed from these chimneys by washing facility costliness, that make meticulously.Certainly, at the iron content sulfide mineral, as finding many sulfide mineral or metallic oxide minerals that contain non-ferrous metal in pyrite and the magnetic iron ore.
When the sulfide mineral with floatation iron content when sulfide mineral that recovery contains non-ferrous metal is with the metal oxidation-containing mineral of sulfuration also reclaims, the content of sulphur is too big, in fusion process, discharge, cause having undesirable a large amount of sulphur during the smelting operation.Therefore, need a kind of selectively the recovery and contain the sulfide mineral of non-ferrous metal and the metal oxidation-containing mineral of sulfuration, and do not reclaim the iron content sulfide mineral, as the method for pyrite and magnetic iron ore.
In commercial collecting agent, xanthic acid salt, thionocarbamate class and phosphordithiic acid salt can't optionally reclaim the sulfide mineral that contains non-ferrous metal in the presence of the sulfide mineral of iron content, otherwise, these collecting agent enrichments and all metallic sulfide minerals of recovery.The mercaptan collecting agent has the undesirable smell of environmental protection, and very slow to the flotation speed of metallic sulfide mineral.When disulphide and polysulfide were used as collecting agent, because motion is slow, the rate of recovery that provides was low.Therefore, industrial mercaptan, disulphide and the polysulfide of not using usually.In addition, mercaptan, disulphide and polysulfide can't selective recovery contain the sulfide mineral of non-ferrous metal in the presence of the sulfide mineral of iron content.
Need a kind of sulfide mineral, exist down, can selective recovery contain the collecting agent of the metal oxidation-containing mineral of the sulfide mineral of non-ferrous metal and sulfuration as pyrite and magnetic iron ore in iron content.
The present invention relates to a kind of from ore selective recovery contain the foam flotation method of the metal oxidation-containing mineral of the sulfide mineral of non-ferrous metal or sulfuration.Particularly, the present invention relates to a kind of metal oxidation-containing mineral that from ore, reclaims metallic sulfide mineral or sulfuration, comprise that ore carries out froth flotation with the state of moisture ore pulp under the situation that a large amount of floating collecting agents exist, wherein collecting agent is a kind of hydrocarbon that contains one or more single sulphur chain links, be aliphatic hydrocarbon or alicyclic carbon atom wherein with sulphur atom key carbon atom even, and the total carbon of collecting agent hydrocarbon part causes collecting agent to have enough hydrophobic performances, particle with the metal oxidation-containing mineral that causes metallic sulfide mineral or sulfuration is driven into the air/gas bubbles interface, under these conditions, the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration reclaims in foam.
New collector effect of the present invention is, the rate of recovery to the metal oxidation-containing mineral of the sulfide mineral that contains non-ferrous metal or sulfuration is very high, and when the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration appeared in the sulfide mineral of iron content, it was very high to the selectivity of the metal oxidation-containing mineral of the sulfide mineral that contains non-ferrous metal and sulfuration.These collecting agents demonstrate the good rate of recovery and good exercise performance.
New collector of the present invention is a kind of hydrocarbon, and it contains one or more single sulphur chain links, wherein, and the sulphur atom of sulfide chain link and the carbon atom of non-aromatics, i.e. aliphatic hydrocarbon or alicyclic carbon atom bonding.Single sulphur chain link refers to-S-here, wherein, sulphur atom only with two carbon atom bondings of hydrocarbon part.The hydrocarbon compound that contains one or more single sulphur chain links used herein comprises the compound that is replaced with hydroxyl, cyano group, halogen, ether, oxyl and alkyl thioether part.The non-aromatics carbon atom refers to the carbon atom that does not belong to the aromatic ring part here.
The hydro carbons that preferably contains single sulphur chain link comprises the hydro carbons that structural formula conforms to R-S-R.
Wherein
R 1And R 2The alkyl that is respectively alkyl separately or is replaced with one or more hydroxyls, cyano group, halogen atom, ether, oxyl or alkyl thioether part;
R wherein 1And R 2Combine with S and form heterocycle structure; But S must connect with aliphatic hydrocarbon or alicyclic carbon atom key; Total phosphorus content of sulfide collecting agent must make the sulfide collecting agent have enough hydrophobic performances, is driven into the air/gas bubbles interface to cause metal sulfide grain.
R preferably 1And R 2Be respectively unsubstituted separately or with one or more hydroxyls, cyano group, halogen atom, OR 3Or SR 3Aliphatic group, alicyclic group or aralkyl that part is replaced, wherein R 3It is alkyl; R herein 1And R 2Can combine with S and form heterocycle.R 1And R 2Preferably unsubstituted or with one or more hydroxyls, cyano group, halogen atom, OR 3Or SR 3Aliphatic hydrocarbon and alicyclic part that part is replaced; R wherein 1And R 2Can combine with S and form heterocycle.In preferred embodiments, R 1And R 2Do not combine each other and S formation heterocycle, and R 1And R 2Be unsubstituted or with one or more hydroxyls, halogen atom, cyano group, OR 3Or SR 3The alkyl that is replaced, alkenyl, alkynyl group, cycloalkyl or cycloalkenyl group, wherein R 3Be aliphatic group or alicyclic group.In optimum implementation, R 1And R 2Be respectively alkyl or alkenyl separately, especially, R 1Be methyl or ethyl, and R 2Be C 6-11Alkyl or C 6-11Alkenyl.In this optimum implementation, R 1And R 2Be not identical hydrocarbon part, promptly this-sulfide is asymmetric.R 3With aliphatic group or alicyclic group is good.R 3Preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl group.
Thereby total phosphorus content of hydrocarbon part must make the sulfide collecting agent possess enough hydrophobic propertys the metal oxidation-containing mineral particle of metallic sulfide mineral or sulfuration is driven on the air/gas bubbles interface in hydrocarbon-sulfide collecting agent.The carbon number of hydrocarbon-total phosphorus content of sulfide collecting agent is minimum to be 4, is more preferably 6, and preferably 8.Maximum phosphorus content better is 20, is more preferably 16, preferably 12.
The example that is applicable to cyclic compound of the present invention comprises following structure:
Wherein, R 4Be respectively aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, hydroxyl, cyano group, halogen atom, OR 3Or SR 3, aryl, alkaryl, aralkyl, alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group can be determined on a case-by-case basis by hydroxyl, cyano group, OR herein 3Or SR 3Replace Deng part.
The present invention another preferably in the preferred embodiment, collecting agent of the present invention meets molecular formula
Wherein
R 6Be respectively alkyl, or the alkyl that is replaced with hydroxyl, cyano group, halogen atom, ether, oxyl or alkyl thioether part; Two R herein 6Group can combine and S formation ring or heterocycle;
N is an integer 0,1,2 or 3; But total phosphorus content of collecting agent hydrocarbon part must make collecting agent have enough hydrophobic performances, is driven into the air/gas bubbles interface with the particle of the metal oxidation-containing mineral that causes metallic sulfide mineral or sulfuration.
Preferred R 6Be unsubstituted or with cyano group, hydroxyl, halogen atom, OR 3Or SR 3Aliphatic group, alicyclic group, aryl, alkaryl or aralkyl that part is replaced, wherein R 3Limit as mentioned.More preferred R 6Be fatty group or alicyclic group unsubstituted or that replaced with hydroxyl, cyano group, halogen atom, fatty hydrocarbyl ether, alicyclic hydrocarbon-ether, aliphatic hydrocarbon thioether or alicyclic thioether part.More preferred R 6Be alkyl, thiazolinyl, cycloalkyl or cycloalkenyl group part.Most preferably, have one-C(H) n(R 6) 3-nBe methyl or ethyl part, another is C 6-11Alkyl or C 6-11Thiazolinyl.N is good with 1,2 or 3, with 2 or 3 for better.
Contain single sulphur chain link R preferably 1-S-R 2(R wherein 1And R 2Qualification as mentioned) hydrocarbon is the standard method with known technology, for example makes R 2-H and R 1-SH prepared in reaction, R wherein 1And R 2Limit as mentioned.
The example of compound comprises methyl butyl sulfide in the scope of the invention, the methyl amyl thioether, methyl hexyl thioether, the methylheptyl thioether, the Methyl Octyl thioether, methyl nonyl thioether, methyl decyl thioether, methyl undecyl thioether, 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 cyclopenta 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, propyl group undecyl thioether, propyl group dodecyl thioether, propyl group cyclopenta thioether, propyl group cyclohexyl thioether, propyl group suberyl thioether, propyl group ring octyl group thioether, dibutyl sulfide ether, 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 cyclopenta thioether, butyl cyclohexyl thioether, butyl suberyl thioether, butyl ring octyl group thioether, the diamyl thioether, amyl group hexyl thioether, amyl group heptyl thioether, amyl group octyl group thioether, amyl group nonyl thioether, amyl group decyl thioether, amyl group undecyl thioether, amyl group dodecyl thioether, amyl group cyclopenta thioether, amyl group cyclohexyl thioether, amyl group suberyl thioether, amyl group ring octyl group thioether, two own thioethers, hexyl heptyl thioether, hexyl octyl group thioether, hexyl nonyl thioether, hexyl decyl thioether, hexyl undecyl thioether, hexyl dodecyl thioether, hexyl cyclopenta thioether, hexyl cyclohexyl thioether, hexyl suberyl thioether, hexyl ring octyl group thioether, two hepta-thioethers, heptyl octyl group thioether, heptyl nonyl thioether, heptyl decyl thioether, heptyl undecyl thioether, heptyl dodecyl thioether, heptyl cyclopenta thioether, heptyl cyclohexyl thioether, heptyl suberyl thioether, heptyl ring octyl group thioether, two hot thioethers, octyl group nonyl thioether, the octyl-decyl thioether, octyl group 11 thioethers, octyl group dodecyl thioether, octyl group cyclopenta thioether, octyl group cyclohexyl thioether, octyl group suberyl thioether, octyl group ring octyl group thioether, octyl group ring decyl thioether, two the ninth of the ten Heavenly Stems thioether, nonyl decyl thioether, nonyl undecyl thioether, nonyl dodecyl thioether, nonyl cyclopenta thioether, nonyl cyclohexyl thioether, nonyl suberyl thioether, nonyl ring octyl group thioether, the didecyl thioether, decyl undecyl thioether, decyl dodecyl thioether, decyl cyclopenta thioether, decyl cyclohexyl thioether, decyl suberyl thioether and decyl ring octyl group thioether.Sulfide 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, dibutyl sulfide ether, diamyl thioether, two own thioethers, two hepta-thioethers and two hot thioethers preferably.
Herein, hydrocarbon system refers to the organic compound of a kind of carbon containing and hydrogen atom.Term " hydrocarbon " comprises following organic compound: the aromatic hydrocarbons that alkanes, alkenes, alkyne hydro carbons, cycloalkane, cyclenes hydro carbons, cycloalkyne, aromatic hydrocarbons, aliphatic series and alicyclic aralkyl hydro carbons and alkyl replace.
Herein, aliphatic hydrocarbon means straight chain and side chain, saturated and undersaturated hydrocarbon compound, i.e. alkanes, olefines or alkynes class.Alicyclic means saturated and undersaturated cyclic hydrocar-bons, i.e. cycloolefin and cycloalkane.
Cycloalkane means the alkane that contains one, two, three or more rings.Cycloolefin means a ring, two ring and the many cyclic groups that contain one or more pairs of keys.
Herein, alkyl means the organic group that contains carbon and hydrogen atom.Term " alkyl " comprises following organic group: alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, aryl, aliphatic hydrocarbon and alicyclic aralkyl and alkaryl.Herein, term " aryl " means diaryl, diphenyl, phenyl, naphthyl, phenanthryl, anthryl and two aromatic yl groups that get up with the alkylidene group bridge joint.Herein, alkaryl means the aryl that alkyl, alkenyl or alkynyl replace, and wherein aryl limits as mentioned.Herein, aralkyl means alkyl group, and wherein aryl limits as mentioned.
C 1-20Alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl and the eicosyl group of straight or branched.
Herein, halogen means chlorine, bromine or iodine group.
Method of the present invention is applicable to the metal oxidation-containing mineral that reclaims metallic sulfide mineral and sulfuration with froth flotation method from ore.Herein, ore means the mineral reserve of exploiting out in the ground, comprises the metallic mineral of being wanted that mix with gangue.Herein, gangue means does not have to be worth and that part of material that need separate with the metal-containing minerals of being wanted.
One preferably among the embodiment, reclaim metallic sulfide mineral.In a better implement example, reclaim the sulfide mineral of cupric, nickel, lead, zinc or molybdenum.In most preferred embodiment, reclaim the sulfide mineral of cupric.In addition, metallic preferably sulfide mineral is that those have high hydrophobic mineral under non-oxide state.Term " hydrophobicity under non-oxide state " expression is just to have exploited the mineral that the mineral that come out have unsalted surface, might flotation under the condition of not adding collecting agent.
Ore comprises the ore that contains copper, zinc, molybdenum, cobalt, nickel, lead, arsenic, silver, chromium, gold, platinum, uranium and their sulfide thereof, and these compounds are useful.Can adopt method of the present invention, comprise copper-bearing mineral with the example of the containing metal sulfide mineral of froth flotation method enrichment, for example covellite (CuS), 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(AsSb) S 4], tetrahedrite (Cu 3SbS 2), tennantite (Cu 12As 4S 13), brochantite [Cu 4(OH) 6SO 4], antleritel [Cu 3SO 4(OH) 4], famatinite [Cu 3(SbAs) S 4] and bournonite (PbCuSbS 3); Contain lead minerals, for example galena (PbS); Antimony-containing mineral, for example stibnite (Sb 2S 3); Zinc-bearing mineral, for example zincblende (ZnS); Silver containing mineral, for example stephanite (Ag 5SbS 4) and argentite (Ag 2S); Contain chrome mineral, for example Yun county sulphur ferrochrome (FeSCrS 3); Nickel-containing mineral, for example pentlandite [(FeNi) 9S 8]; Molybdenum-bearing mineral, for example molybdenite (MoS 2) and the mineral of platiniferous and palladium, for example cooperite [Pt(ass) 2].Metallic preferably sulfide mineral comprises molybdenite (MoS 2), chalcopyrite (CuFeS 2), galena (PbS), zincblende (ZnS), bornite (Cu 5FeS 4) and pentlandite [(FeNi) 9S 8].
The metal oxidation-containing mineral of sulfuration is so a kind of mineral, and it is handled through the sulfur vulcanization chemistries product, in order that give some characteristics of this mineral sulfide mineral, makes this mineral can adopt the collecting agent that reclaims sulfide mineral to carry out froth flotation and reclaims.The result of oxide mineral sulfuration has the characteristic of sulfide mineral.Oxide mineral vulcanizes by contacting with the compound of its reaction generation sulfide linkage or similar sulfide linkage with some.These class methods are well-known technology.These compounds comprise sodium bisuflide, sulfuric acid and relevant sulfur-bearing salt, as vulcanized sodium.
The metal oxidation-containing mineral of the sulfuration of this method practicality comprises the oxide mineral that contains copper, aluminium, iron, tungsten, molybdenum, magnesium, chromium, nickel, titanium, manganese, tin, uranium and composition thereof.Can adopt method of the present invention to comprise copper-bearing mineral, as cuprite (Cu with the example of the metallic oxide mineral of froth flotation enrichment 2O), black copper ore (CuO), malachite [(Cu 2OH) 2CO 3], chessy copper [Cu 3(OH) 2(CO 3) 2], cyanogen copper mine [Cu 2Cl(OH) 3], chrysocolla (CuSiO 3); Aluminum-containing mineral is as diamond dust; Zinc-bearing mineral is as red tungsten ore (Fe, Mn) WO 4; Nickel-containing mineral is as bunsenite (NiO); Molybdenum-bearing mineral is as wulfenite (PbMoO 4) and powellite (CaMoO 4); Iron-bearing mineral is as bloodstone and magnetic iron ore; Contain chrome mineral, as chromite (FeCr 2O 3); The mineral of iron content and iron are as ilmenite; The mineral that contain magnesium and aluminium are as spinelle; The mineral of iron content and chromium are as chromite; Titaniferous ore is as rutile; Manganese-bearing mineral is as pyrolusite; Contain tin mineral, as cassiterite; And uranium bearing mineral, as uranium ore; And uranium bearing mineral, as the blue or green uranium ore [U of soup 2O 5(U 3O 8)] and pittinite (UO 3nH 2O); Zinc-bearing mineral is as zincblende (ZnO), smithsonite (ZnCO 3).
Collecting agent of the present invention can any concentration use, these concentration values give the mineral of managing to want with the desirable rate of recovery, particularly, the concentration that is adopted depends on the certain minerals that is recovered, the grade of ore of carrying out froth flotation, the desired mineral quality that is recovered and with the certain minerals that is recovered.Better be that collecting agent of the present invention uses with the concentration of 0.001 kilogram～1.0 kilograms in ore per ton, preferably, is used for froth flotation with about 0.010～0.2 kilogram of collecting agent of ore per ton.
Froth flotation method of the present invention is preferably used foaming agent, and any known foaming agent that can reach the mineral recovery rate of wanting all is suitable for.
The foaming agent of practicality of the present invention comprises any known foaming agent that can reach the mineral recovery rate of wanting.The example of this class foaming agent comprises C 5-8Alcohols, pine tar class, cresols class, polypropylene glycol C 1-4Alkyl ether, polypropylene glycol dihydroxy thing class, propandiols, fatty acid, soap class, alkarylsulphonic acid salt or the like.In addition, also can use the admixture of these foaming agents.The foaming agent of all suitable froth flotation method ore dressings all can use in the present invention.
In addition, in the method for the invention, it should be noted that collecting agent of the present invention can mix use with other collecting agent of having known.Can mix the known collecting agent that uses with collecting agent of the present invention and be and to give those collecting agents that the mineral of wanting to reclaim reach the desirable rate of recovery.The example of the collecting agent of practicality of the present invention comprises alkyl monothiocarbonic acid salt, alkyl dithiocarbonic acids salt, alkyl trithiocarbonic acid salt, the dialkyl dithio carbonate, alkyl thion carbonate, the dialkyl thiourea class, one alkyl dithiophosphoric acid salt, dialkyl group and diaryl phosphordithiic acid salt, dialkyl group monothio phosphoric acid salt, dialkyl group and diaryl sulfo-phosphonic chloride class, dialkyl group and diaryl phosphonodithioic acid salt, the alkyl sulfide alcohols, xanthogen formate ester class, the xanthate class, the mercaptobenzothiazoler class, fatty acid and fatty acid salt, alkyl sulfide acids and salt thereof, alkyl and alkarylsulphonic acid class and its esters, alkyl phosphoric acid class and its esters, alkyl and aryl phosphoric acids class and its esters, the sulfo-succinic acids, sulfo-succinamide ester class, the primary amine class, the secondary amine class, tertiary amines, quaternary ammonium salt.Alkyl pyridine salt, guanidine and alkyl propane diamine class.
Specific embodiment
Following embodiment can be used to illustrate the present invention, is used for limiting scope of the present invention absolutely not.Unless otherwise mentioned, mark and decimal all are by weight.
In more following embodiment, the performance of the foam method of being narrated is represented with the rate of recovery in flotation velocity constant of obtaining and endless time.These numerical value calculate with following formula:
r=R ∞[l- (l-e -kt)/(kt) ]
Wherein: γ is the ratio that reclaims mineral at t in the time, and k is a constant for recovery rate, R be calculate will reclaim the share of mineral in the endless time.The quantity that reclaims in the different time is determined with experimental technique, and this series of values substitution equation is obtained R and K.Above-mentioned formula has explanation in " flotation with the selection of a chemical agent " book the 45th chapter (the 907th～934 page) " ore dressing plant design " that second edition in 1980 the printing crin Pei Er of U.S. mining and metallurgy SPE (Denver city) (Klimpel) writes.
The froth flotation of embodiment 1-copper containing sulfurized ore
In this embodiment, several collecting agents of the present invention are carried out the float test of copper containing sulfurized ore.500 grams are contained chalcopyrite product bit comparison height slightly to be contained the red ore of a little pyritous Canada West and 257 and restrains deionized waters and put into the rod mill that 1 inch (2.5 centimetres) frotton is housed, and grind 420 with 60 rev/mins speed and change, so that being provided, size distribution accounts for 25% particle less than 100 purposes.Add some lime according to the desirable pH value of back flotation.The ore pulp that grinds is transported in 1500 milliliters of flotation cells of A Jitai (Agitair) flotation device.Flotation cell stirs with 1150 rev/mins speed, and further adds lime pH value is adjusted to 8.5.
Collecting agent (8 gram/ton) is added flotation cell, regulated the back through 1 minute and add foaming agent DOWFROTH 250(18 gram/ton).After regulating 1 minute once more,, and start automatic foam removal slurry with 4.5 liters/minute speed bubbling air in the flotation cell.In the time of 0.5,1.5,3,5 and 8 minute, take foam sample away.These foam samples are dried in baking oven with flotation tailing and are spent the night.The samples weighing of drying is divided into the sample that is fit to analyze usefulness, is crushed to suitable fineness, and is dissolved in the acid for analyzing usefulness.This sample is analyzed with DC plasma spectrograph, and analysis result is compiled in table 1.
Figure 86101682_IMG3
Figure 86101682_IMG4
Figure 86101682_IMG6
1.R-8 be the experiment rate of recovery of representing decimally after 8 minutes
Selectivity be the rate of recovery of copper during with 8 minutes during divided by 8 minutes the rate of recovery of gangue calculate
3. the non-embodiment of the invention
Experiment shows that the recovery rate of these collecting agents of the present invention and recovery balance are all good than mercaptan and polysulfide collecting agent.
The froth flotation of embodiment 2-copper-molybdenum ore
Prepare several bags of same ores that contain chalcopyrite and molybdenite thing, every bag contains 1200 grams.Roughly selecting step and be 1200 gram chargings and 800 ml tap waters has in the ball mill that mixes ball (reach 100 orders and account for grinding machine more than 13%) in one bag, grinds 14 minutes.Ore pulp is delivered in the flotation cell of 1500 milliliters in the A Jitai flotation device that is equipped with automatic slurry foam-removing system.With lime the pH value of ore pulp is transferred to 10.2, no longer further transfers herein in the test, four sections rough floatation schemes are as follows:
The 1st section: collecting agent-0.0042 kilogram/ton
MIBC-0.015 kilogram/ton
-adjusting time-1 minute
The concentrate of-floating thing-1 minute collecting
The 2nd section: collecting agent-0.0021 kilogram/ton
MIBC-0.005 kilogram/ton
-adjusting time-0.5 minute
The concentrate of-floating thing-1.5 minute collecting
The 3rd section: collecting agent-0.0016 kilogram/ton
MIBC-0.005 kilogram/ton
-adjusting time-0.5 minute
The concentrate of-floating thing-2.0 minute collecting
The 4th section: collecting agent-0.0030 kilogram/ton
MIBC-0.005 kilogram/ton
-adjusting time-0.5 minute
The concentrate of-floating thing-2.5 minute collecting
The results are compiled in table 2.
Table 2
The froth flotation of Canada West copper/molybdenum ore
The average iron of the average molybdenum of collector dosage copper molybdenum copper is average
Gram/ton R-7 ' R-7 ' grade 2Grade 2Grade 2
A????11.2????0.776????0.725????0.056????0.00181????0.254
B????11.2????0.710????0.691????0.093????0.00325????0.149
B????6.7????0.730????0.703????0.118????0.00390????0.155
B????22.4????0.756????0.760????0.105????0.00346????0.161
C????11.2????0.699????0.697????0.107????0.00386????0.164
C????22.4????0.723????0.723????0.112????0.00382????0.142
The A-amylic potassium xanthate, non-embodiments of the invention
B-1,2-epithio octane
C-hexyl methyl thioether
1.-R-7 be the experiment rate of recovery of representing decimally after 7 minutes
2.-grade is the content that special metal is represented in total recovery weight decimally in the foam
Table 3
The froth flotation of Canada's east Cu/Ni ore
Collecting agent copper ambrose alloy nickel magnetic is yellow to be selected
Iron ore 2
K????R????K????R????R-12′????R-12′????R-12′
C 5H 11OCS 2Na 5.71 0.94 3.35 0.866 0.931 0.849 0.393 2.16
Amylic sodium xanthogenate
8.22 0.938 2.24 0.790 0.927 0.751 0.247 3.04
C 4H 9SC 4H 99.61 0.937 2.95 0.656 0.928 0.630 0.190 3.32
1.R-12 be the experiment rate of recovery of representing decimally after 12 minutes
2. selectivity is that the rate of recovery of nickel is calculated divided by the rate of recovery of magnetic iron ore during with 12 minutes
The use of collecting agent of the present invention all has very big effect to pyritous decline greatly in the concentrate that improves total grade of concentrate (share of desired containing metal sulfide mineral in the final floating product) and the decline by iron sample in the product and record.This and used dosage indifference.This means that the material of sending into smelting furnace is less, the sulphur that production per unit metal is emitted is less.
The froth flotation of embodiment 3-Canada east copper/nickel ores, ore contains the iron sulfide mineral that exists with the magnetic iron ore form in a large number.
From the batcher that send factory to roughly select the warehouse, extract several samples, and put into container so that about 1200 gram solids to be provided.Ore pulp contains brass mineral and pentlandite mineral.Then, on Denver (Denver) flotation cell, use slurry and constant slurry face equipment automatically with the material in each container, be used in selected in 1.0,3.0,6.0 and 12.0 minutes each concentrate time of making-rate of recovery curve, before the beginning foam-expelling, in 1 fen clock time of regulation, once add collecting agent.The dosage of this collecting agent is 0.028 kilogram of flotation charging per ton.Each concentrate drying, weigh, grind and make sample for the probability equalization of analyzing usefulness.Calculate total grade of the rate of recovery relevant and selected raw ore with the time with the material balance equation of standard.
Collecting agent of the present invention provide can with amylic sodium xanthogenate copper recovery relatively; Collecting agent of the present invention obtains much higher flotation rate.The rate of recovery that collecting agent of the present invention obtains nickel is lower than amylic sodium xanthogenate, but the rate of recovery of the undesired iron sulfide magnetic iron ore that provides is also much lower, this can with the R of magnetic iron ore 12Optionally increasing than having more of undesired iron sulfide magnetic iron ore of value and Ni sulphide mine thing 50% found out.
The froth flotation of embodiment 4-Canada middle part Pb/Zn/Cu/Ag complex ore
The 1000 gram ore samples that prepare some homogeneous.This ore contains galena, zincblende, chalcopyrite and argentite mineral.Each flotation adds rod mill with a duplicate samples with 500 ml tap waters and 7.5 milliliters of SO solution.Ground 6.5 minutes, and be used for account for 90% the charging of preparation less than 200 orders (75 microns).After grinding, the flotation cell of foam-expelling with automatic slurry is equipped with in the material immigration, this flotation cell is connected on Denver's flotation device of standard.
Carry out two-stage flotation then.At first section, take out and roughly select copper/lead/silver-colored floating thing, at second section, take out and roughly select the zinc floating thing.First section flotation begins, and per kilogram adds 1.5 gram Na 2CO 3(pH value is 9～9.5) then, adds collecting agent (class).Then, ore pulp is blowing air 5 minutes and stirring in accordance with regulations, then stirs at the conditioning period that lasts 2 minutes.Adding foaming agent MIBC(standard then is 0.015 milliliter/kilogram).Flotation is collected concentrate and is indicated it is that copper/lead is roughly selected concentrate in the time of 5 minutes.
Second section flotation comprises, with CuSO 4In the residue by one section flotation cell of 0.5 kilogram of/ton adding, add lime then pH value is adjusted to 10.5, then only stir, reexamine pH value then, and get back to 10.5 with the lime adjusting at the conditioning period that lasts 5 minutes.At this moment, add collecting agent, then during 5 minutes of regulation, only stir.Adding foaming agent MIBC(standard then is 0.020 milliliter/kilogram).Collect concentrate in the time of 5 minutes and indicate it is that zinc is slightly made concentrate.
The concentrate sample carries out drying, weighs and prepares suitable sample for the X ray methods analyst.Account formula and adopt determination data calculate recovery rate and grade by standard quality.
Except above-mentioned steps, (do not add Na in that first section pH value is lower yet 2CO 3, pH value is 8.5) and be to test in 9.5 o'clock at second section lime, pH value that only adds q.s.Add CuSO by 0.3 kilogram/ton 4, pH value is also lower.
Figure 86101682_IMG8
The A-sodium ethylxanthate
The B-dithiophosphates
The C-thionocarbamate
A, B and C are non-embodiments of the invention
D-1,2 epithio octanes
E-octyl group methyl thioether
1.R-5 be the actual recovered rate of representing decimally after 5 minutes
2. grade is the relative metal of special metal in the gross weight of collecting in the foam
This is the floatation of a complexity, and it shows quite surprising effect, and collecting agent promptly of the present invention can replace the complex mixture of the collecting agent of three kinds of industrial the bests, and at common pH value and CuSO 4The rate of recovery of following metal conforms to superseded substantially with grade, is selected as best industrial collecting agent (test 1,2,3).At low pH value and CuSO 4Corresponding test (4,5,6) shows that also collecting agent of the present invention can improve metal content significantly down, surpasses those three kinds of industrial collecting agents.Its result means the expense that factory's operation can be saved lime and CuSO greatly.(first section pH value is controlled at 10.5, the second sections pH values, and to be controlled at 9.5 main reason be to improve selectivity.Add CuSO 4Main reason be to improve the rate of recovery of zinc, keep grade simultaneously).Note, at CuSO 4Operation (5,6) under the lower situation, in fact collecting agent of the present invention has improved the rate of recovery of zinc and has kept good grade.
The froth flotation of embodiment 5-copper/molybdenum ore
500 gram South America copper/molybdenum ores and 257 gram deionized waters are put into the rod mill that 1 inch (2.5 centimetres) frotton is housed with some lime, change with 60 rev/mins speed mills 360, so that the suitable particulate of size distribution (accounting for 25% less than 100 purposes) to be provided.This contains 1500 milliliters the flotation cell that ore pulp is sent to the A Jitai flotation device that grinds of the sulfide mineral of various copper and molybdenite.This flotation cell stirs with 1150 rev/mins speed, and adds lime or hydrochloric acid transfers to 8.5 with pH value.
Collecting agent is added flotation cell (45 gram/ton), then in the conditioning period that lasts 1 minute, add foaming agent DOWFROTH 250(36.4 gram/ton).After the adjusting that lasts 1 minute, with 4.5 liters/minute speed air is fed flotation cell, and start and scrape the bubble slurry automatically.Collected foam sample at 0.5,1.5,3,5 and 8 minute.This foam sample is with flotation tailing dried overnight in baking oven.Dried samples weighing is divided into sample that be fit to analyze usefulness, is crushed to be dissolved in the acid after the suitable fineness and uses for the analysis of DC plasma spectrograph.It the results are compiled in table 5.
Table 5
Collecting agent pH copper molybdenum-iron
R-8 2R-8 2R-8 2
Xanthates/thion
Carbaminate 110.5 0.891 0.742 0.398
Octyl group ethyl thioether 10.5 0.854 0.791 0.278
Xanthates/thion
Carbaminate 18.0 0.912 0.780 0.422
Octyl group ethyl thioether 8.0 0.887 0.394 0.394
1. non-embodiments of the invention (mixture of the ethyl sodium sulfonate of 50/50 w/w and isopropyl ethyl thion carbamic acid sodium)
2.R-8 be the experiment rate of recovery of representing decimally after 8 minutes
Collecting agent of the present invention demonstrates molybdenum recovery has raising significantly than standard medicament, yet the rate of recovery of copper descends.The rate of recovery that contains iron sulfide descends with also achieving one's goal very significantly.
The froth flotation of embodiment 6-copper mine
The step, use that repeats embodiment 1 and different places, embodiment 1 same ore deposit, contain suitable high chalcopyrite and ore slightly pyritiferous, gained the results are compiled in table 6.
1.R-8 be the experiment rate of recovery of representing decimally after 8 minutes
Selectivity be the rate of recovery of copper during with 8 minutes during divided by 8 minutes the rate of recovery of gangue calculate
3. non-embodiments of the invention
This embodiment illustrates 2 points: the 1) influence of this collecting agent hydrophobic part; 2) comparison of the inorganic sulphide of compound of the present invention and single component (NaS).

Claims (4)

1, a kind of method that reclaims the metal oxidation-containing mineral of metallic sulfide mineral or sulfuration from ore comprising the pulp ore, adopts collecting agent to handle ore pulp through flotation, it is characterized in that efficient and selectivity in order to improve this method, and described collecting agent is a formula
R 1-S-R 2Shown sulfide, wherein R 1Be methyl or ethyl;
R 2Be C 5-11Aliphatic, alicyclic, aromatic group or their combination product, perhaps R 1And R 2Combine and S forms ternary epithio circulus, condition is that the total carbon content of S and aliphatic series or cyclic aliphatic carbon atom bonding, sulfide collecting agent is 6-20 carbon atom and R 1And R 2It is not identical alkyl.
2, in accordance with the method for claim 1, R wherein 1Be methyl or ethyl, R 2Be C 6-11Alkyl or C 6-11Thiazolinyl.
3, in accordance with the method for claim 1, the working concentration of wherein said sulfide collecting agent treats that with 1000kg the ore of froth flotation is that benchmark is counted 0.001-1.0kg.
4, in accordance with the method for claim 1, wherein said epithio circulus is shown below:
Figure 86101682_IMG1
R wherein 4Be respectively aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, hydroxyl, cyano group, halogen atom, OR 3Or SR 3, wherein aryl, alkaryl, aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, the visual concrete condition of cycloalkenyl group are by hydroxyl, cyano group, OR 3Or SR 3Replace R 3Be alkyl.
CN86101682A 1985-05-31 1986-02-17 Process for foam flotation of s-contg. ore Expired CN1011765B (en)

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ES8706045A1 (en) * 1985-11-29 1987-06-01 Dow Chemical Co Collector compositions for the froth flotation of mineral values
WO1993004783A1 (en) * 1991-08-28 1993-03-18 Commonwealth Scientific And Industrial Research Organisation Processing of ores
CN103945948B (en) * 2011-10-18 2017-08-25 塞特克技术公司 Foam flotation method
CN102631993A (en) * 2012-03-20 2012-08-15 北京矿冶研究总院 Method for flotation of copper sulphide ore
CN103977907B (en) * 2014-05-15 2016-03-23 中南大学 A kind of xanthic acid acyl ester collecting agent and methods for making and using same thereof
US9512071B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9505011B1 (en) * 2015-12-28 2016-11-29 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as mining chemical collectors
US10040758B2 (en) 2015-12-28 2018-08-07 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9512248B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US10011564B2 (en) 2015-12-28 2018-07-03 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10294200B2 (en) 2015-12-28 2019-05-21 Chevron Phillips Chemical Company, Lp Mixed branched eicosyl polysulfide compositions and methods of making same
CN106179767B (en) * 2016-09-23 2018-04-03 中南大学 A kind of application of the thiones flotation collector of 1,3,4 oxadiazole 2
CN108057525A (en) * 2017-11-27 2018-05-22 西北矿冶研究院 Flotation collector for improving associated gold of low-grade copper ore and copper-molybdenum ore and preparation method thereof
CN108499723B (en) * 2018-03-06 2020-12-15 昆明理工大学 Arsenic removal and resource comprehensive utilization method for arsenic-containing sulfur concentrate
CN109622234B (en) * 2018-11-16 2021-04-20 西北矿冶研究院 Copper sulfide ore combined collector suitable for grading and regrinding tailings
CN109550598B (en) * 2018-11-21 2019-09-24 中南大学 A kind of application of oxyl propyl thiocarbamide in metallic ore flotation
CN109365138B (en) * 2018-11-30 2021-03-05 河南城建学院 Novel composite flotation agent for flotation of copper-nickel sulfide ore
CN109731693B (en) * 2019-01-28 2021-09-14 西安建筑科技大学 Method for sulfurizing and floating copper-lead-zinc oxide ore by using cyanuric acid saturated solution
JP7299592B2 (en) * 2019-11-05 2023-06-28 国立大学法人九州大学 beneficiation method
CN110721817B (en) * 2019-11-29 2022-05-27 南华大学 Collecting agent for floating uranyl carbonate ions and application thereof
CN111266195B (en) * 2020-03-05 2021-09-07 中南大学 Zinc oxide ore flotation combined collecting agent and application thereof
WO2022044599A1 (en) * 2020-08-27 2022-03-03 独立行政法人石油天然ガス・金属鉱物資源機構 Method for selectively recovering arsenic-containing copper mineral, and flotation agent used in same
CN113369022B (en) * 2021-06-08 2023-01-10 金川镍钴研究设计院有限责任公司 Beneficiation method for high-calcium-magnesium type chalcopyrite
CN113477393B (en) * 2021-08-10 2022-10-28 南华大学 Method for leaching uranium from pyrite-containing carbonate type uranium ore

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