CN105642448A - Method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore - Google Patents
Method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore Download PDFInfo
- Publication number
- CN105642448A CN105642448A CN201511021887.3A CN201511021887A CN105642448A CN 105642448 A CN105642448 A CN 105642448A CN 201511021887 A CN201511021887 A CN 201511021887A CN 105642448 A CN105642448 A CN 105642448A
- Authority
- CN
- China
- Prior art keywords
- wolframite
- ore
- tungsten
- flotation
- concentrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B03D1/018—Mixtures of inorganic and organic compounds
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/005—Dispersants
-
- 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
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/025—Precious metal ores
Abstract
The invention discloses a method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore. According to the method, wolframite and scheelite mixed concentrate pulp is obtained through floatation enrichment of tungsten ore; and fatty acid, sodium sulfide, caustic soda and sodium silicate are sequentially added into the wolframite and scheelite mixed concentrate pulp, strong stirring and pulp mixing are performed, flotation separation is performed, the scheelite concentrate is obtained from flotation foam, and flotation tailings are the wolframite concentrate. By means of the method, wolframite and scheelite can be thoroughly separated, the quality of the scheelite concentrate is high, and the problems that products contain both wolframite and scheelite, and the quality of the scheelite concentrate is poor are solved; and the technological process is short, chemical agents are simple, operation is convenient, labor intensity is low, energy consumption is low, environmental protection and high efficiency are achieved, and not only is the beneficiation cost greatly reduced, but also the tungsten resource utilizing rate is remarkably increased.
Description
Technical field
The present invention relates to the method for a kind of high efficiency separation wolframite and white tungsten fine ore from tungsten ore, belong to tungsten ore resource field of comprehensive utilization.
Background technology
Tungsten is the rare metal of a kind of preciousness, it it is the element that in metallic element, fusing point is the highest, thermal expansivity is minimum, vapour pressure is minimum, it it is one of metallic element that density is the highest, tungsten has excellent mechanical behavior under high temperature, very high modulus of compression and Young's modulus, the high temperature creep-resisting performance of excellence, high specific conductivity and a series of special performance such as thermal conductivity and very high electron emission coefficient, is thus widely used in the every field such as civilian, industrial, military project. For a long time, the Mineral resources mainly wolframite of China's tungsten industry exploitation. According to the black tungsten reserves that Ministry of Land and Resources 2002 " China's Mineral resources annual report " announces, by 2000 the end of the year retained reserve (WO3) it is 144.05 ten thousand tons, account for whole nation tungsten ore and produce the 27.4% of total retained reserve, wherein A+B+C level (industry) reserves 53.6 ten thousand tons. And the selecting and purchasing total yield of China's tungsten is very low at present, serious waste of resources, existing wolframite reserves substantially exhaust or remain little.
In the ore dressing of tungsten minerals, from single sheelite or wolframite bed, reclaim tungsten concentrate be all relatively easy to, but for sheelite, wolframite symbiosis ore body, particularly the sheelite of fine fraction symbiosis, wolframite reclaim tungsten ore wherein with regard to relative difficult, mainly because of attach most importance to magnetic separation reclaim the embedding cloth of fine fraction sheelite, wolframite time be difficult to there is good index, usually adopt Bai Makuang, the method for wolframite bulk flotation often can obtain good index. The difficult point of sheelite, wolframite bulk flotation is to strengthen the flotation of Fine wolframite, it is to increase the flotation recovery rate of micro-size fraction wolframite. The main bugbear that wherein bulk flotation faces have following some: (1) sheelite has better natural flotability than wolframite. General oxide mineral collector is more weak to the collecting ability of wolframite, and the collecting of sheelite is relatively strong, therefore causes the flotation recovery rate of wolframite lower, and amount of metal loss is serious. (2) conventional collecting agent is more weak to the pH adaptability of ore pulp, and the best flotation pH interval of wolframite, sheelite is inconsistent.The best flotation pH of sheelite is interval usually between 7-9; The best flotation pH interval of wolframite is relatively wide, often because collecting agent kind difference changes greatly, generally fluctuates between 5-10. (3) wolframite is more crisp, more relatively easy than sheelite overground. When adopting bulk flotation sheelite, wolframite, as long as generally the abundant monomer dissociation of sheelite, wolframite and gangue mineral just can be made by primary grinding flow process. But owing to wolframite proportion is very big, in the closed circuit circulatory system of grind grading, wolframite that is levigate and that reach flotation requirement easily precipitates in screw classifier, and return grinding machine with sand return and regrind, therefore, entering the wolframite in flotation separation operation is all that granularity is relatively thin or even micro-size fraction, and these fine fraction wolframites are difficult to reclaim again, finally causing the total yield of wolframite lower, amount of metal loss is serious.
At present, what black and white tungsten bulk flotation often adopted is that sheelite, wolframite are first carried out enrichment by normal temperature flotation, then carries out black and white tungsten separation by high gradient magnetic separator, then respectively sheelite, wolframite is carried out floating and enriching. But in high magnetic separation technique, black and white tungsten separation efficiency is relatively low, carrying a large amount of white tungsten secretly, carry a large amount of black tungsten in white tungsten secretly in black tungsten, in follow-up refining process, particularly in white tungsten heating concentration process, black tungsten loss is serious. Therefore, how utilizing wolframite, sheelite physico-chemical property difference a kind of efficient, succinct black and white tungsten separating technology of exploitation, the efficient utilization for tungsten resource is significant.
Summary of the invention
For tradition high-gradient high magnetic separation technique, black and white tungsten separation efficiency is low, mutually select the problems such as operation recovery is low containing serious, subsequent fine, technical program of the present invention lies in providing a kind of flotability of making full use of between black, sheelite and flotation rate difference, by control flotation conditions, it is achieved the method for the efficient flotation separation of black and white tungsten; The method flow process is short, medicament is simple, easy to operate, labour intensity is low, energy consumption is low, environment-friendly high-efficiency, not only significantly reduces cost but also significantly improves the utilization ratio of tungsten resource; Compared to tradition high magnetic separation technique, the separation of the method black and white tungsten is thorough, white tungsten fine ore quality height, solves the problems such as black and white tungsten in product contains mutually, white tungsten fine ore poor quality.
In order to realize above-mentioned technical purpose, the present invention provides the method for a kind of high efficiency separation wolframite and white tungsten fine ore from tungsten ore, and the method is that by flotation I enrichment, tungsten ore is obtained black and white tungsten collective concentrate ore pulp; Described black and white tungsten collective concentrate ore pulp is after concentrated, adding lipid acid, sodium sulphite, caustic soda and water glass successively, under 800��1200r/min speed, strong stirring is sized mixing 1��2h, carries out flotation II separation, obtaining white tungsten fine ore from flotation froth, flotation tailings is wolframite.
The technical scheme of the present invention makes full use of the flotability between black, sheelite and flotation rate difference, using lipid acid as collecting agent, water glass as dispersion agent and inhibitor, sodium sulphite is as vulcanizing agent and resolves agent, caustic soda as pH adjusting agent, sized mixing by long-time strong stirring, the high efficiency separation of the wolframite in black and white tungsten collective concentrate and white tungsten fine ore can be realized, solve the problems such as black and white tungsten in product contains mutually, white tungsten fine ore poor quality.
Preferred scheme, black and white tungsten collective concentrate slurry concentrating is 40��70% to mass percent concentration, and the flotation reagent that flotation I remains is removed.Black and white tungsten collective concentrate ore pulp is preferably sized mixing in higher concentrations, is conducive to the separation of black and white tungsten ore. In order to avoid flotation reagent that flotation I remains on the impact of follow-up flotation II, flotation I preferably the overwhelming majority be removed.
Preferred scheme, the add-on of the relative raw ore of lipid acid is 1��2kg/t.
Preferred scheme, the add-on of the relative raw ore of sodium sulphite is 5��8kg/t.
Preferred scheme, the add-on of the relative raw ore of caustic soda is 1��2.5kg/t.
Preferred scheme, the add-on of the relative raw ore of water glass is 60��100kg/t. The effect of a large amount of water glass is for promoting that lipid acid collecting agent is resolved at wolframite and gangue mineral surface.
Preferred scheme, lipid acid is C6��C18Saturated fatty acid and salt, and/or C6��C18Unsaturated fatty acids and salt.
Preferred scheme, flotation I, under adding condition without calcium mineral inhibitor, adopts metal ion match as collecting agent; Described metal ion match is formed by ligand and metallic ion coordination;
Described metal ion is Fe3+��Fe2+��Pb2+��Cu2+��Zn2+��Al3+��Mn2+��Ni2+Or Ca2+;
Described ligand has formula 1 structure;
Wherein,
R is phenyl, substituted-phenyl or C6��C12Alkyl.
The present invention adopts and selects metal ion match can realize the efficiently concentrating of black and white tungsten collective concentrate when unrestraint agent as collecting agent, for the separation of follow-up black and white tungsten ore provides technical foundation.
The coordination mol ratio of more preferably scheme, metal ion and ligand is 1:2,1:4,1:8 or 1:16.
Metal ion match collecting agent in the technical scheme of the present invention is formed by hydroximic acid ligand and metallic ion coordination, there is five yuan, six yuan, the coordination monomer of 6-5 or 5-5 chelate ring in parallel, and then form the metal ion match of monokaryon, double-core or multinuclear.
The preparation method of the metal ion match collecting agent of the present invention specifically comprises the following steps:
The first step, the esterification of carboxylic acid
Being mixed with excessive absolute alcohol by carboxylic acid, slowly add concentrated acid, and add several zeolites, after being heated to 70��80 DEG C of backflow 1��2h, distill out excessive alcohol with water distilling apparatus, debris obtains corresponding carboxylicesters after 3��5 washings;
Described carboxylicesters has formula 2 structure:
Wherein,
R is phenyl, substituted-phenyl or C6��C12Alkyl;
R1For methyl or ethyl;
2nd step, freeization of oxammonium hydrochloride
Oxammonium hydrochloride is added in single port flask, and add dehydrated alcohol, stir cooling in a water bath, add sodium hydroxide wherein, stir 1��2h in a water bath, filter and remove insolubles, obtain free hydroxylamine hydrochloride solution;
3rd step, the synthesis of ligand
Adding free hydroxylamine hydrochloride solution and methanol solvate in the there-necked flask with electric mixer and dropping funnel, at 45��55 DEG C, the carboxylicesters of agitation and dropping the first step gained, reacts 30��45min, obtains ligand after dropwising;
4th step, the synthesis of title complex
In the solution of the 3rd step gained, add soluble metallic salt under agitation, at 35��45 DEG C of insulation reaction l��2h, obtain hydroximic acid/metal ion match collecting agent; The mol ratio of metal-salt and hydroximic acid is 1:2,1:4,1:8 or 1:16; Soluble metallic salt is for containing Fe3+��Fe2+��Pb2+��Cu2+��Zn2+��Al3+��Mn2+��Ni2+Or Ca2+Soluble metallic salt.
Preferred scheme, flotation I comprises a thick essence two and sweeps operation.
More preferably scheme, in flotation I process, the consumption of collecting agent is 300��500g/t, and the pH of flotation system is 6��10.
More preferably scheme, the grade of flotation I gained black and white tungsten collective concentrate is greater than 40%, and wherein, tungsten is with WO3Metering.
Preferred scheme, flotation II comprises a thick essence two and sweeps operation.
More preferably scheme, after the separating obtained froth product of flotation II carries out dephosphorization treatment by dilute hydrochloric acid and/or dust technology, washing, drying, obtain white tungsten fine ore; Wherein, the mass percent concentration of dilute hydrochloric acid and/or dust technology is 10��20%, and the consumption of dilute hydrochloric acid and/or the relative white tungsten fine ore of dust technology is 5��10L/t.
More preferably scheme, the separating obtained mine tailing of flotation II obtains wolframite through concentrated, sedimentation; Wherein, adding Tai-Ace S 150 and/or sulfuric acid destroys the dissemination of water glass in concentrated, settling process, the add-on of wolframite is 1��3kg/t by Tai-Ace S 150 and/or sulfuric acid phase.
The lipid acid of the present invention's employing, sodium sulphite, caustic soda, water glass are all commercially available conventional dose, or can directly obtain with reference to existing document.
The method of high efficiency separation wolframite and white tungsten fine ore from tungsten ore of the present invention specifically comprises the following steps:
The first step: black and white tungsten bulk flotation
Adopting black and white tungsten bulk flotation technique, take metal ion match as collecting agent, flotation pH is 6��10, sweeps through a thick essence two and obtains WO3The collective concentrate that grade is greater than 40%;
2nd step: concentrate the concentration escapes the medicine
The collective concentrate of the first step gained being proceeded to thickner, and promotes that foam dispersion is broken with high pressure spraying, after concentrated, underflow mass percent concentration reaches 40��70%, and overflow water suspended solid mass content is less than 0.1%;
3rd step: size mixing-resolve
Thickener underflow is proceeded to agitation vat, add lipid acid collecting agent 1��2kg/t (raw ore), sodium sulphite 5��8kg/t (raw ore), caustic soda 1��2.5kg/t (raw ore), water glass 60��100kg/t (raw ore) successively, and with the speed high speed strong stirring of 800��1200r/min, the time of sizing mixing is 1��2h;
4th step: flotation separation
The ore pulp that 3rd step has been starched being entered flotation machine and carries out flotation separation, after sweeping operation through one thick two through two, froth product is white tungsten fine ore, and mine tailing is wolframite;
5th step: concentrate product treatment
Add dilute hydrochloric acid and/or nitric acid to the white tungsten froth product of the 4th step gained to stir 1��2h and carry out dephosphorization treatment, then it is qualified high-quality white tungsten fine ore after washing drying, the mass percent concentration of dilute hydrochloric acid or dust technology is 10��20%, and the consumption of dilute hydrochloric acid and/or the relative white tungsten fine ore of dust technology is 5��10L/t; Flotation tailings adds Tai-Ace S 150 and/or the dissemination of sulfuric acid destruction water glass, promotes wolframite rapid subsidence, after filtration drying, be wolframite; The add-on of wolframite is 1��3kg/t by Tai-Ace S 150 and/or sulfuric acid phase.
Hinge structure, the useful effect that the technical scheme of the present invention is brought:
1, achieved the efficient flotation separation of black and white tungsten by the technical scheme of the present invention, compared to tradition high magnetic separation technique, the separation of the method black and white tungsten is thorough, white tungsten fine ore quality height, solves the problems such as black and white tungsten in product contains mutually, white tungsten fine ore poor quality.
2, the technical scheme flow process of the present invention is short, medicament is simple, easy to operate, labour intensity is low, energy consumption is low, environment-friendly high-efficiency, not only significantly reduces cost but also significantly improves the utilization ratio of tungsten resource.
3, the preferred technical solution of the present invention coordinates collecting agent that black and white tungsten mixing tungsten ore is carried out efficient floating and enriching by metal ion, for the separation of follow-up black and white tungsten ore provides good precondition.
Accompanying drawing explanation
[Fig. 1] is phenyl oxime acid/lead metal ionic complex collecting agent obtained in embodiment 1 and the infrared spectrogram containing tungsten minerals: a is metal ion match collecting agent, and b is tungsten ore, and c is after metal ion and tungsten ore effect.
[Fig. 2] is o-hydroxy-phenyl oxime acid/aluminum metal ionic complex collecting agent obtained in embodiment 2 and the infrared spectrogram containing tungsten minerals: a is metal ion match collecting agent, b tungsten ore, after c metal ion and tungsten ore effect.
Embodiment
Following examples are that the content to the present invention illustrates further, instead of the scope of restriction the claims in the present invention protection.
Embodiment 1
The phenylformic acid of 1mol/L is mixed with the anhydrous methanol of 3mol/L, slowly adds 30mL concentrated acid, add several zeolites, be heated to 75 DEG C of backflow 2h. Distilling out excessive methyl alcohol with water distilling apparatus, debris obtains corresponding ester after 3 washings; Oxammonium hydrochloride 2.2mol is added in single port flask, and adds 50mL ethanol, stir cooling in a water bath, add sodium hydroxide 88g wherein, stir 2h in a water bath, filter away insoluble free azanol, obtain free oxammonium hydrochloride; Free oxammonium hydrochloride and 25mL methyl alcohol is added in the there-necked flask with electric mixer and dropping funnel, at 45 DEG C, the ester 1.7mol of agitation and dropping gained, 45min is reacted after dropwising, lead nitrate 0.5mol is added under agitation in the solution of the 3rd step gained, 40 DEG C of insulation reaction 2h, obtain described title complex collecting agent.
Utilize this processing method process persimmon bamboo plantation tungsten tin molybdenum bismuth polymetallic ore, desulfurization mine tailing adjusts pH9.0 by sodium carbonate, adding lead ion phenyl hydroximic acid ligand collecting agent (mol ratio 1:4) 400g/t of preparation, inflation is sized mixing and is stirred 5min, sweeps flotation operation through a thick essence two and obtains WO3The black and white tungsten collective concentrate of 45%, collective concentrate is after thickener, put into agitation vat, ore pulp mass concentration 65%, add oleic acid, sodium sulphite, caustic soda 1Kg/t, 5Kg/t, 2Kg/t successively, then water glass (water glass amount is variable) is added, stirring velocity 1000r/min, high-speed stirring 1.5h, flotation separation is carried out after having sized mixing, froth product add 5Kg/t massfraction be 10% hydrochloric acid dephosphorization treatment after obtain white tungsten fine ore, flotation tailings adds the Tai-Ace S 150 of 2Kg/t, sedimentation, filtration, dry after be wolframite. Table 1 be water glass consumption on the impact of quality product, show that the too low meeting of water glass consumption causes white tungsten fine ore quality product not high, in concentrate, black and white tungsten is mutually containing relatively more serious.
Table 1 water glass consumption is on the impact of concentrate quality product
Embodiment 2
The Whitfield's ointment of 1mol/L is mixed with the anhydrous methanol of 3mol/L, slowly adds 30mL concentrated acid, add several zeolites, be heated to 80 DEG C of backflow 1h. Distilling out excessive methyl alcohol with water distilling apparatus, debris obtains corresponding ester after 5 washings; Oxammonium hydrochloride 2.2mol is added in single port flask, and adds 50mL ethanol, stir cooling in a water bath, add sodium hydroxide 88g wherein, stir 1.5h in a water bath, filter away insoluble free azanol, obtain free oxammonium hydrochloride; Free oxammonium hydrochloride and 25mL methyl alcohol is added in the there-necked flask with electric mixer and dropping funnel, at 48 DEG C, the ester 1.7mol of agitation and dropping gained, 45min is reacted after dropwising, Tai-Ace S 150 0.25mol is added under agitation in the solution of the 3rd step gained, 40 DEG C of insulation reaction 2h, obtain described title complex collecting agent.Fig. 2 is metal ion match collecting agent and with containing the Infrared spectroscopy (after a metal ion match collecting agent, b tungsten ore, c metal ion and tungsten ore effect Infrared spectroscopy) of tungsten minerals.
Utilize this processing method process pheasant tail tungsten tin molybdenum bismuth polymetallic ore, desulfurization mine tailing adjusts pH8.5 by sodium carbonate, adding adjacent hydroxyl oxime acid ligand collecting agent (mol ratio 1:4) 300g/t of aluminum ion, inflation is sized mixing and is stirred 5min, sweeps flotation operation through a thick essence two and obtains WO3The black and white tungsten collective concentrate of 49%, collective concentrate is after thickener, put into agitation vat, ore pulp mass concentration 55%, add ricinolic acid, sodium sulphite, caustic soda, water glass 1.5Kg/t, 6Kg/t, 1.5Kg/t, 60Kg/t successively, stirring velocity 1200r/min, high-speed stirring 2h, carry out flotation separation after having sized mixing, froth product add 10Kg/t massfraction be 10% hydrochloric acid dephosphorization treatment after obtain WO3The white tungsten fine ore of 72%, flotation tailings adds the sulfuric acid of 4Kg/t, is WO after sedimentation, filtration, drying3The wolframite of 36%. Table 2 be churning time on the impact of quality product, show that the too short meeting of churning time causes white tungsten fine ore quality product not high, in concentrate, black and white tungsten is mutually containing relatively more serious.
Table 2 churning time is on the impact of concentrate quality product
Embodiment 3
Utilize the celestial tungsten tin molybdenum bismuth polymetallic ore in this processing method process precious jade hilllock, desulfurization mine tailing adjusts pH7.8 by sodium carbonate, adding metallic ion coordination body collecting agent (prepared by embodiment 1) 500g/t, inflation is sized mixing and is stirred 5min, sweeps flotation operation through a thick essence two and obtains WO3The black and white tungsten collective concentrate of 53%, collective concentrate is after thickener, put into agitation vat, ore pulp mass concentration 72%, add sodium oleate, sodium sulphite, caustic soda, water glass 2Kg/t, 8Kg/t, 1Kg/t, 80Kg/t successively, stirring velocity 800r/min, high-speed stirring 1, carry out flotation separation after having sized mixing, froth product add 8Kg/t massfraction be 10% nitric acid dephosphorization treatment after obtain WO3The white tungsten fine ore of 73%, flotation tailings adds the sulfuric acid of 3Kg/t, is WO after sedimentation, filtration, drying3The wolframite of 36%. Table 3 be stirring intensity on the impact of quality product, show that the too low meeting of stirring intensity causes white tungsten fine ore quality product not high, in concentrate, black and white tungsten is mutually containing relatively more serious.
Table 3 water glass consumption is on the impact of concentrate quality product
Claims (10)
1. the method for high efficiency separation wolframite and white tungsten fine ore from a tungsten ore, it is characterised in that: tungsten ore obtains black and white tungsten collective concentrate ore pulp by flotation I enrichment; Described black and white tungsten collective concentrate ore pulp is after concentrated, adding lipid acid, sodium sulphite, caustic soda and water glass successively, under 800��1200r/min speed, strong stirring is sized mixing 1��2h, carries out flotation II separation, obtaining white tungsten fine ore from flotation froth, flotation tailings is wolframite.
2. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 1, it is characterised in that: described black and white tungsten collective concentrate slurry concentrating is 40��70% to mass percent concentration, and the flotation reagent that flotation I remains is removed.
3. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 1, it is characterised in that: the add-on of the relative raw ore of described lipid acid is 1��2kg/t; The add-on of the relative raw ore of described sodium sulphite is 5��8kg/t; The add-on of the relative raw ore of described caustic soda is 1��2.5kg/t;The add-on of the relative raw ore of described water glass is 60��100kg/t.
4. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 3, it is characterised in that: described lipid acid is C6��C18Saturated fatty acid and salt, and/or C6��C18Unsaturated fatty acids and salt.
5. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to the arbitrary item of Claims 1 to 4, it is characterised in that: described flotation I, under adding condition without calcium mineral inhibitor, adopts metal ion match as collecting agent; Described metal ion match is formed by ligand and metallic ion coordination;
Described metal ion is Fe3+��Fe2+��Pb2+��Cu2+��Zn2+��Al3+��Mn2+��Ni2+Or Ca2+;
Described ligand has formula 1 structure;
Wherein,
R is phenyl, substituted-phenyl or C6��C12Alkyl.
6. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 5, it is characterised in that: the coordination mol ratio of described metal ion and ligand is 1:2,1:4,1:8 or 1:16.
7. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 5, it is characterised in that: in flotation I process, the consumption of collecting agent is 300��500g/t, and the pH of flotation system is 6��10.
8. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 5, it is characterised in that: the grade of flotation I gained black and white tungsten collective concentrate is greater than 40%, and wherein, tungsten is with WO3Metering.
9. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to the arbitrary item of Claims 1 to 4, it is characterised in that: described flotation II comprises a thick essence two and sweeps operation.
10. the method for high efficiency separation wolframite and white tungsten fine ore from tungsten ore according to claim 9, it is characterised in that: after the separating obtained froth product of flotation II carries out dephosphorization treatment by dilute hydrochloric acid and/or dust technology, washing, drying, obtain white tungsten fine ore; Wherein, the mass percent concentration of dilute hydrochloric acid and/or dust technology is 10��20%, and the consumption of dilute hydrochloric acid and/or the relative white tungsten fine ore of dust technology is 5��10L/t; The separating obtained mine tailing of flotation II obtains wolframite through concentrated, sedimentation; Wherein, adding Tai-Ace S 150 and/or sulfuric acid destroys the dissemination of water glass in concentrated, settling process, the add-on of wolframite is 1��3kg/t by Tai-Ace S 150 and/or sulfuric acid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021887.3A CN105642448B (en) | 2015-12-30 | 2015-12-30 | A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021887.3A CN105642448B (en) | 2015-12-30 | 2015-12-30 | A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105642448A true CN105642448A (en) | 2016-06-08 |
| CN105642448B CN105642448B (en) | 2018-07-27 |
Family
ID=56490390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511021887.3A Active CN105642448B (en) | 2015-12-30 | 2015-12-30 | A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105642448B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390537A (en) * | 2016-10-25 | 2017-02-15 | 洛阳栾川钼业集团股份有限公司 | Method for recovering fine-particle-grade scheelite in two-stage thickening manner |
| CN110152890A (en) * | 2019-06-05 | 2019-08-23 | 广东省资源综合利用研究所 | A kind of flotation and metallurgy method of white tungsten preenrichment concentrate dephosphorization |
| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111495579A (en) * | 2020-04-28 | 2020-08-07 | 赣州有色冶金研究所 | Method for recovering tungsten and tin from fine mud and coarse sand |
| CN112871456A (en) * | 2020-12-04 | 2021-06-01 | 崇义章源钨业股份有限公司 | Method for treating scheelite bulk concentrate |
| CN114657368A (en) * | 2022-03-01 | 2022-06-24 | 信丰华锐钨钼新材料有限公司 | High-efficiency treatment method for low-grade mixed tungsten ore containing high flotation agent |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100350A (en) * | 1985-04-01 | 1986-08-27 | 中南工业大学 | White tungsten fine ore and Scheelite-Wolframite Mixed Mine alkali decomposition and equipment |
| EP0201815A2 (en) * | 1985-05-11 | 1986-11-20 | Henkel Kommanditgesellschaft auf Aktien | Use of surfactant mixtures as flotation agents for non-sulfide ores |
| CN1210894A (en) * | 1996-04-02 | 1999-03-17 | 中南工业大学 | Producing pure tungsten compound using tungsten-containing material |
| CN101269352A (en) * | 2008-05-05 | 2008-09-24 | 广州有色金属研究院 | Beneficiation method for black and white tungsten fine deposit |
| US20100000913A1 (en) * | 2008-07-02 | 2010-01-07 | Georgia-Pacific Chemicals Llc | Collectors |
| CN101648157A (en) * | 2009-08-25 | 2010-02-17 | 广州有色金属研究院 | Beneficiation method of black and white tungsten mineral |
| CN102211053A (en) * | 2011-05-27 | 2011-10-12 | 广州有色金属研究院 | Method for separating black and white tungsten bulk flotation rough concentrates |
-
2015
- 2015-12-30 CN CN201511021887.3A patent/CN105642448B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100350A (en) * | 1985-04-01 | 1986-08-27 | 中南工业大学 | White tungsten fine ore and Scheelite-Wolframite Mixed Mine alkali decomposition and equipment |
| EP0201815A2 (en) * | 1985-05-11 | 1986-11-20 | Henkel Kommanditgesellschaft auf Aktien | Use of surfactant mixtures as flotation agents for non-sulfide ores |
| CN1210894A (en) * | 1996-04-02 | 1999-03-17 | 中南工业大学 | Producing pure tungsten compound using tungsten-containing material |
| CN101269352A (en) * | 2008-05-05 | 2008-09-24 | 广州有色金属研究院 | Beneficiation method for black and white tungsten fine deposit |
| US20100000913A1 (en) * | 2008-07-02 | 2010-01-07 | Georgia-Pacific Chemicals Llc | Collectors |
| CN101648157A (en) * | 2009-08-25 | 2010-02-17 | 广州有色金属研究院 | Beneficiation method of black and white tungsten mineral |
| CN102211053A (en) * | 2011-05-27 | 2011-10-12 | 广州有色金属研究院 | Method for separating black and white tungsten bulk flotation rough concentrates |
Non-Patent Citations (3)
| Title |
|---|
| 孙传尧: "《选矿工程师手册 第3册 下 选矿工业实践》", 31 March 2015 * |
| 张泾生: "《现代选矿技术手册》", 28 February 2011 * |
| 胡岳华: "《矿物浮选》", 31 March 2014 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390537A (en) * | 2016-10-25 | 2017-02-15 | 洛阳栾川钼业集团股份有限公司 | Method for recovering fine-particle-grade scheelite in two-stage thickening manner |
| CN110152890A (en) * | 2019-06-05 | 2019-08-23 | 广东省资源综合利用研究所 | A kind of flotation and metallurgy method of white tungsten preenrichment concentrate dephosphorization |
| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111495579A (en) * | 2020-04-28 | 2020-08-07 | 赣州有色冶金研究所 | Method for recovering tungsten and tin from fine mud and coarse sand |
| CN111495579B (en) * | 2020-04-28 | 2022-04-12 | 赣州有色冶金研究所有限公司 | Method for recovering tungsten and tin from fine mud and coarse sand |
| CN112871456A (en) * | 2020-12-04 | 2021-06-01 | 崇义章源钨业股份有限公司 | Method for treating scheelite bulk concentrate |
| CN114657368A (en) * | 2022-03-01 | 2022-06-24 | 信丰华锐钨钼新材料有限公司 | High-efficiency treatment method for low-grade mixed tungsten ore containing high flotation agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105642448B (en) | 2018-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105642448A (en) | Method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore | |
| CN102658242B (en) | Mineral separation process of complex fluorite difficult to separate | |
| CN101444761B (en) | A floatation separation method of hamartite misch metal mine containing high content mengite | |
| CN110508402B (en) | Low-temperature-resistant double-acid-salt rare earth ore flotation collector and preparation method and application thereof | |
| CN102744152A (en) | Reverse/direct flotation technology of collophanite | |
| CN105618272B (en) | A kind of metal ion match collecting agent and its preparation method and application | |
| CN102896050A (en) | Pyrrhotite flotation inhibitor, preparation and application thereof, and copper-nickel sulfide ore beneficiation method | |
| CN102527492B (en) | Method for preparing super iron ore concentrate by using low-grade magnetic iron ore | |
| CN108624765A (en) | A kind of technique from the low-grade high efficiente callback of tailing containing rubidium rubidium | |
| CN105413855B (en) | A kind of method of tungsten rough concentrate cleaning and Purification | |
| CN104399592A (en) | Fluorite floatation process | |
| CN102527497B (en) | Beneficiation method for separating zinc sulfide ores from sulphur in wet-method zinc smelting slag | |
| CN103184334A (en) | Selection-smelting combined technology for treating mixed ore containing molybdenum, oxygen, sulfur and copper | |
| CN105734309B (en) | A kind of method that beryllium is extracted in the type beryllium from chrysoberyl | |
| CN102168159B (en) | Reducing agent for carrying out direct reduction roasting on limonite and hematite to produce reduced iron | |
| CN107899755B (en) | Synergist for flotation of refractory copper oxide ore | |
| CN102744159A (en) | Flotation method for improving copper sulfide core sorting indexes | |
| CN104846208A (en) | Method for comprehensively recovering gold and silver in lead-silver slag | |
| CN105642449B (en) | A kind of method that tungsten mine water cycle and collecting agent recycle | |
| CN102168174B (en) | Method for dephosphorizing high-phosphorus hematite | |
| CN103817011A (en) | Carbon inhibitor and application thereof in molybdenum-nickel flotation from high-carbon molybdenum-nickel ores | |
| CN102658234B (en) | Application method of defoaming agent to beneficiation and tailings discarding of stone coal vanadium ore and hydrometallurgy | |
| CN109499772A (en) | A kind of method of pyroxene in FLOTATION SEPARATION magnetic iron ore | |
| CN109954588A (en) | A kind of sesquichloride inhibitor and preparation method thereof and purposes | |
| CN102872978A (en) | Copper-zinc flotation process for minerals and products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170918 Address after: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Applicant after: Central South University Applicant after: Shizhuyuan Nonferrous Metal LLC, Hunan Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Applicant before: Central South University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |