CN105413855A - Method for cleaning and purification of tungsten rough concentrate - Google Patents
Method for cleaning and purification of tungsten rough concentrate Download PDFInfo
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- CN105413855A CN105413855A CN201511022319.5A CN201511022319A CN105413855A CN 105413855 A CN105413855 A CN 105413855A CN 201511022319 A CN201511022319 A CN 201511022319A CN 105413855 A CN105413855 A CN 105413855A
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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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/08—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
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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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for cleaning and purification of a tungsten rough concentrate. The method comprises the following steps: crushing tungsten ores and carrying out wet grinding to obtain ore pulp; sequentially removing iron and sulfur from the obtained ore pulp, and then carrying out roughing for enrichment of the tungsten rough concentrate under the conditions that a metal ion complex is adopted as a collecting agent, the pH value of the treated ore pulp is 8.5-9.5, and a dry glass calcium-containing mineral inhibitor exists; conducting defoaming and dispersing treatment on the tungsten rough concentrate, and then carrying out re-selection to obtain a tungsten concentrate; carrying out tailings re-selection and returning to the roughing operation, so as to further recover the remaining tungsten ores. Through adoption of the method, the recovery rate of tungsten in the tungsten ores reaches up to 90% or above; the method is short in procedure, simple in chemical agent, convenient to operate, low in labor intensity and energy consumption, and efficient in environmental protection; not only is the cost greatly reduced, but also the tungsten resource utilization ratio is remarkably improved.
Description
Technical field
The present invention relates to a kind of method of tungsten rough concentrate cleaning and Purification, belong to tungsten mine technical field.
Background technology
Tungsten is a kind of rare metal of preciousness, it is the element that in metallic element, fusing point is the highest, thermal coefficient of expansion is minimum, vapour pressure is minimum, it is one of metallic element that density is the highest, tungsten has excellent mechanical behavior under high temperature, very high modulus of compressibility and elastic modelling quantity, the Properties of High Temperature Creep of excellence, high electrical conductivity and a series of special performance such as thermal conductivity and very high electron emission coefficiency, 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 " Mineral Resources in China annual report " announces, by 2000 the end of the year reserves (WO
3) be 144.05 ten thousand tons, account for that national tungsten ore produces total reserves 27.4%, wherein A+B+C level (industry) reserves 53.6 ten thousand tons.And the selecting and purchasing overall recovery of China's tungsten is very low at present, serious waste of resources, existing wolframite reserves substantially exhaust or remain little.In the face of the disappearance of the black the advantages of tungsten resources of China, white tungsten exploitation dynamics must be strengthened, improve white tungsten selecting and smelting technology, improve white tungsten resource recovery utilization rate, to ensure China's tungsten industry sustainable development.
Scheelite ore type mainly can be divided into: white tungsten-quartz (or silicate mineral), white tungsten-calcite, fluorite (barite) type.Generally, white tungsten-quartz type ore more easily selects; And white tungsten-fluorite, calcite (barite) type ore difficulty are selected, because white tungsten is close with the floatability of calcic gangue mineral, difficulty is separated.White tungsten floatation process is generally divided into the section of roughly selecting and selected period two stages.The section of roughly selecting mainly to eliminate for the purpose of gangue mineral to greatest extent, improves flotation operation concentration ratio.The section of roughly selecting generally adopts normal temperature flotation, and conventional pH adjusting agent has: NaOH, sodium carbonate, lime+sodium carbonate; Gangue inhibitor generally uses waterglass.White tungsten rough concentrate selected is the key of whole white tungsten flotation, and whether white tungsten floatation process classification generally heats by selected section and is divided into heat flotation and normal temperature flotation.I.e. underflow high temperature method and normal temperature flotation method.Underflow high temperature method and Dinko Petrov method.At present, white tungsten flotation production practices are widely used in.This method is that Soviet experts is invented in late 1940s than get Luo Fu.Be concentrated into the concentration of about 70% by rough concentrate, strengthen water gaging glass, and heat to more than 90 DEG C, strong mixing 30 ~ 60 minutes, then dilutes normal temperature flotation.This method, to ore strong adaptability, is widely used in each white tungsten ore dressing plant.Calcium mineral (fluorite, calcite etc.) due to association is close with scheelite floatability and enter froth pulp simultaneously, is separated quite difficulty further.Arrive being separated of white tungsten and association calcium mineral, the difference of white tungsten and association calcium mineral floatability must be caused.Adopting Dinko Petrov method can successfully diffeential floatation scheelite from the white tungsten rough concentrate of association calcium mineral, be that waterglass causes from white tungsten is different with the ability of association calcium mineral surface desorption collecting agent because under Dinko Petrov method condition.Under Dinko Petrov method condition, scheelite still keeps good floatability, and fluorite, calcite are suppressed due to the desorb of surperficial collecting agent.Thus achieve effectively being separated of white tungsten and these calcic gangue minerals.Dinko Petrov method need be heated flotation, and energy consumption is high, and cost is high, complicated operation, and working condition is poor, so, adopt new technology and realize desirability and the inevitable requirement that white tungsten normal temperature flotation is era development.Early 1970s, first 731 oxidized paraffin wax black and white tungsten normal temperature flotation method initiates at China's Gan Nan tungsten ore and obtains production application.This method, compared with Dinko Petrov method, is more paid attention to roughly selecting operation, is emphasized the cooperative effect of carbonic acid and waterglass, make the HSiO in ore pulp
- 3remain on the concentration range of optimal inhibition.Then do collecting agent with selective 731 stronger oxidized paraffin wax soaps, improve and roughly select concentration ratio.In rough concentrate, add a large amount of waterglass time selected carry out long-time (more than 30min) strong agitation, then dilute conventional flotation, whole dressing process carries out under normal temperature condition.This method is simple to operate, and cost is low, but to the adaptability of ore not as good as Dinko Petrov method.731 normal temperature methods obtain the application of wider model on the skarn type scheelite mountain based on quartz, also have application in recent years in the practice of white tungsten-fluorite, calcite type scheelite stone.
The FLOTATION SEPARATION of scheelite and the calcium mineral such as fluorite, calcite is one of world's ore dressing difficult problem.And scheelite mainly originates in skarns tungsten deposit.During scheelite this kind of with fatty acid collecting agent flotation, the floatability due to calcium mineral (fluorite, calcite) is close with scheelite enters froth pulp simultaneously.At present, the selected general employing Dinko Petrov method of white tungsten.But heating method cost is high, complicated operation, and working condition is poor, traditional normal temperature concentration process costs is high, ore bad adaptability, and roughly select operation and selected operation tomography, recycled in its entirety rate is low.
Summary of the invention
Tungsten technique is selected to there is calcium mineral separation difficulty for conventional fat acid, waterglass consumption is large, roughly select selected operation separation difficulty, the problems such as the rate of recovery is low, the object of the invention is to be to provide a kind of flow process short, energy consumption is low, cost is low, and realize containing tungsten mineral (scheelite under without calcium mineral inhibitor condition, wolframite, wolfram ocher etc.) the method for efficient flotation separation enrichment, this method solving prior art adopts a large amount of waterglass inhibitor to bring tungsten ore organic efficiency low, concentrate, the problems such as mine tailing sedimentation concentration difficulty, and bed surface fouling in reuse adoption process, the defects such as separative efficiency is low.
In order to realize above-mentioned technical purpose, the invention provides a kind of method of tungsten rough concentrate cleaning and Purification, the method is tungsten ore is broken, wet milling, obtains ore pulp; Gained ore pulp is successively by after deferrization, desulfurization, and enter and roughly select, roughly selecting with metal ion match is collecting agent, is 8.5 ~ 9.5 in pH values of pulp, and under dry glass calcium mineral inhibitor existent condition, roughly selects enrichment tungsten rough concentrate; Described tungsten rough concentrate, after froth breaking and dispersion treatment, enters gravity treatment, obtains tungsten concentrate.
Technical scheme of the present invention, by selective extremely strong metal ion match as collecting agent, make to roughly select operation and achieve efficient flotation separation enrichment containing tungsten mineral (scheelite, wolframite, wolfram ocher etc.) under without calcium mineral inhibitor condition, roughly select operation concentration ratio up to more than 50 times, the rate of recovery is greater than 85%, creates favorable conditions for subsequent fine is elected to be industry; Selected operation makes full use of and is separated gangue mineral granularity, difference of specific gravity containing tungsten mineral with difficulty, realizes the efficiently concentrating containing tungsten mineral by gravity treatment, and operation recovery, up to more than 90%, thoroughly replaces heating concentration operation.Flotation and combining of gravity treatment have given full play to containing tungsten mineral and the difference of gangue mineral in floatability, proportion, granularity etc., greatly improve WO
3the rate of recovery.Hinge structure, waterglass cancellation not only solve prior art and adopt a large amount of waterglass inhibitor to bring tungsten ore organic efficiency low, the problems such as concentrate, mine tailing sedimentation concentration difficulty, and the defect such as bed surface fouling in reuse adoption process, separative efficiency be low.
Preferred scheme, the addition of the relative raw ore of metal ion match is 200 ~ 500g/t.
Preferred scheme, metal ion match is formed by ligand and metallic ion coordination;
Metal ion is Fe
3+, Fe
2+, Pb
2+, Cu
2+, Zn
2+, Al
3+, Mn
2+, Ni
2+or Ca
2+;
Described ligand has formula 1 structure;
Wherein,
R is phenyl, substituted-phenyl or C
6~ C
8alkyl.
Preferred scheme, the coordination mol ratio of metal ion and ligand is 1:2,1:4,1:8 or 1:16.
The preparation method of metal ion match collecting agent of the present invention specifically comprises the following steps:
The first step, the esterification of carboxylic acid
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 distilling apparatus, Liquid Residue obtains corresponding carboxylate after 3 ~ 5 washings;
Described carboxylate has formula 2 structure:
Wherein,
R is phenyl, substituted-phenyl or C
6~ C
12alkyl;
R
1for methyl or ethyl;
Second step, freeization of hydroxylamine hydrochloride
Hydroxylamine hydrochloride is added in single port flask, and add absolute ethyl alcohol, stir cooling in a water bath, add NaOH wherein, stir 1 ~ 2h in a water bath, filter and remove insoluble matter, obtain free hydrochloric acid hydroxylamine solution;
3rd step, the synthesis of ligand
In the there-necked flask with electric mixer and dropping funel, add free hydrochloric acid hydroxylamine solution and methanol solvate, at 45 ~ 55 DEG C, the carboxylate of agitation and dropping first step gained, dropwises rear reaction 30 ~ 45min, obtains ligand;
4th step, the synthesis of 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 metal ion match collecting agent; The mol ratio of slaine and ligand is 1:2,1:4,1:8 or 1:16; Soluble metallic salt is for containing Fe
3+, Fe
2+, Pb
2+, Cu
2+, Zn
2+, Al
3+, Mn
2+, Ni
2+or Ca
2+soluble metallic salt.
Preferred scheme, tungsten ore is broken, ore grinding to granularity meets-200 order grade mass percentage content and accounts for more than 55%, through broken, ore grinding to suitable granularity, tungsten ore can ensure that tungstenic degree of dissociation of mineral monomer is greater than 90%.
Preferred scheme, rougher process ensures that ore pulp mass percent concentration is 30 ~ 55%.
Preferred scheme, the mass percentage content of the magnetic iron ore in tungsten ore is reduced to less than 10% by magnetic separation deferrization process.
More preferably scheme, WO in tungsten ore
3mass percentage content be greater than 0.05%, wherein, be at least one in scheelite, ferberite, huebnerite, wolfram ocher etc. containing tungsten mineral, gangue mineral is mainly garnet, calcite, fluorite, barite and silicate mineral.
More preferably scheme, WO in tungsten rough concentrate
3grade is greater than 7%, and main gangue mineral is calcite, fluorite, magnetic iron ore and part silicate mineral.
More preferably scheme, WO in tungsten concentrate
3grade is greater than 65%.
Preferred scheme, defoaming treatment combines realization by chemical froth breaking and mechanical defoaming.
More preferably scheme, chemical froth breaking adopts kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C
7~ C
9alcohols at least one as defoamer.
More preferably scheme, described mechanical defoaming is high-pressure fog and mechanical agitation, and high-pressure fog pressure is more than 0.5Mpa, mechanical agitation speed 300 ~ 800r/min.
Preferred scheme, dispersion treatment process is regulate more than pH values of pulp to 9.5 by pH adjusting agent, adds dispersant simultaneously and strengthens particle dispersion.
More preferably scheme, pH adjusting agent is at least one in sodium carbonate, NaOH, sodium acid carbonate.PH adjusting agent mainly makes particle surface band like charges, promotes Granular composite.
More preferably scheme, dispersant is at least one in calgon, prodan, polyacrylic acid, polyethylene glycol.
More preferably scheme, gravity treatment is by shaking table, spiral chute, outstanding shake gravity concentrator or swirl separator realization.By WO in the tungsten concentrate after gravity treatment
3grade is greater than 65%, and gravity tailings returns rougher process.
Preferred scheme, does not add waterglass and other any inhibitor in floatation process.
Preferred scheme, process of sizing mixing is the stirring of inflation Strong shear.
The calgon that the present invention relates to, prodan, polyacrylic acid, polyethylene glycol, sodium carbonate, NaOH, sodium acid carbonate, kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C
7~ C
9alcohols etc. all belong to commercially available conventional dose.
Tungsten ore deferrization process of the present invention adopts the magnetic separation deferrization technique of this area routine.
Tungsten ore sweetening process of the present invention adopts the floatation desulphurization of this area routine, using butylamine black powder etc. as collecting agent.
The method of tungsten rough concentrate cleaning and Purification of the present invention specifically comprises the following steps:
The first step: fragmentation, ore grinding, deferrization, desulfurization
Ore is after fragmentation, ore grinding, and granularity meets-200 order grade mass percentage and is greater than 55%, and tungstenic degree of dissociation of mineral monomer is greater than 90%, and after strong magnetic machine magnetic separation deferrization, magnetic iron ore content is less than 10%; Magnetic tailing is by floatation desulphurization ore deposit;
Second step: dosing is sized mixing floating and enriching
The mass percent concentration of ore pulp is 30 ~ 55%, and in ore pulp, add pH adjusting agent regulate the pH of ore pulp to be 8.5 ~ 9.5, then add metal ion match collecting agent, and carry out floating and enriching after Aerated stirring 3 ~ 5min, froth pulp is tungsten rough concentrate, WO
3grade is greater than 7%, and tungsten recovery rate is greater than 85%;
3rd step: rough concentrate froth breaking pretreatment
In the rough concentrate foam of second step gained, add defoamer, dispersant, and roughly select foam with high-pressure fog destruction, mixing speed is 300 ~ 800r/min, and lather collapse is gravity treatment to ore deposit after eliminating;
4th step: gravity treatment efficiently concentrating
The ore pulp of the 3rd step gained is carried out Gravity separation through gravitational separation equipment, obtains tungsten concentrate WO
3grade is greater than 65%, and mine tailing returns and roughly selects operation after thickening pond is concentrated.
Hinge structure, the beneficial effect that technical scheme of the present invention is brought:
1, technical scheme of the present invention have employed complex that selective extremely strong ligand and metal ion formed as collecting agent, achieve under dry glass and other any inhibitor condition the efficiently concentrating containing tungsten mineral (scheelite, wolframite, wolfram ocher etc.), roughly select operation concentration ratio up to more than 50 times, the rate of recovery is greater than 85%, creates favorable conditions for subsequent fine is elected to be industry; Make full use of on this basis and be separated gangue mineral granularity, difference of specific gravity containing tungsten mineral with difficulty, realize the efficiently concentrating containing tungsten mineral by gravity treatment, operation recovery, up to more than 90%, thoroughly replaces heating concentration operation.By the associating of flotation in conjunction with gravity treatment, give full play to containing tungsten mineral and the difference of gangue mineral in floatability, proportion, granularity etc., greatly improved WO
3the rate of recovery.
2, the medicament of technical scheme employing of the present invention is simple, eliminate the use of traditional waterglass calcium mineral inhibitor, not only solving prior art adopts a large amount of waterglass calcium mineral inhibitor to bring tungsten ore organic efficiency low, the problems such as concentrate, mine tailing sedimentation concentration difficulty, and the defect such as bed surface fouling in reuse adoption process, separative efficiency be low.
3, technical scheme of the present invention can realize tungsten ore purification at normal temperatures, and energy consumption is low, and cost is low.
4, technical scheme flow process of the present invention is short, easy to operate, labour intensity is low, environment-friendly high-efficiency.
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 mineral: 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 mineral: a is metal ion match collecting agent, b tungsten ore, after c metal ion and tungsten ore effect.
[Fig. 3] be preparation in embodiment 3 cycloalkyl oxime acid/nickel metal ion match collecting agent and containing the infrared spectrogram of tungsten mineral: a metal ion match collecting agent, b tungsten ore, after c metal ion and tungsten ore effect.
Detailed description of the invention
Following examples further illustrate content of the present invention, instead of the scope of restriction the claims in the present invention protection.
Embodiment 1
The benzoic acid of 1mol/L is mixed with the absolute methanol of 3mol/L, slowly adds 30mL concentrated acid, add several zeolites, be heated to 80 DEG C of backflow 2h.Distill out excessive methyl alcohol with distilling apparatus, Liquid Residue obtains corresponding ester after 5 washings; Hydroxylamine hydrochloride 2.2mol is added in single port flask, and adds 50mL ethanol, stir cooling in a water bath, add NaOH 88g wherein, stir 2h in a water bath, filter away insoluble free azanol, obtain free hydrochloric acid azanol; Free hydroxylamine hydrochloride and 25mL methyl alcohol is added in the there-necked flask with electric mixer and dropping funel, at 45 DEG C, the ester 1.7mol of agitation and dropping gained, dropwise rear reaction 45min, plumbi nitras 0.5mol is added under agitation in the solution of the 3rd step gained, 40 DEG C of insulation reaction 2h, obtain described metal ion match collecting agent.Fig. 1 metal ion match collecting agent and with the infrared spectrum analysis (a metal ion match collecting agent, b tungsten ore, infrared spectrum analysis after c metal ion and tungsten ore effect) containing tungsten mineral.
Utilize this process process persimmon bamboo plantation tungsten tin molybdenum bismuth polymetallic ore, desulfurization mine tailing is 9.0 by sodium carbonate adjustment pH, adds the metal ion match collecting agent 400g/t of preparation, and inflation is sized mixing and stirred 5min, rough concentrate WO
319.70%, in rough concentrate, add tbp 50g/t, calgon 100g/t, mixing speed is 500r/min, and high-pressure fog pressure is 10Mpa, and after bubble collapse, ore pulp obtains tungsten concentrate WO through table concentration
373.56%, the overall rate of recovery 82.45%.
Persimmon bamboo plantation tungsten floatation process result of the test
| Product | Productive rate/% | WO 3/％ | WO 3The rate of recovery/% |
| Concentrate | 0.51 | 73.56 | 82.45 |
| Mine tailing | 99.49 | 0.08 | 17.55 |
| Sulphur tail | 100.00 | 0.45 | 100.00 |
Embodiment 2
The salicylic acid of 1mol/L is mixed with the absolute methanol of 3mol/L, slowly adds 30mL concentrated acid, add several zeolites, be heated to 75 DEG C of backflow 1h.Distill out excessive methyl alcohol with distilling apparatus, Liquid Residue obtains corresponding ester after 5 washings; Hydroxylamine hydrochloride 2.2mol is added in single port flask, and adds 50mL ethanol, stir cooling in a water bath, add NaOH 88g wherein, stir 1.5h in a water bath, filter away insoluble free azanol, obtain free hydrochloric acid azanol; Free hydroxylamine hydrochloride and 25mL methyl alcohol is added in the there-necked flask with electric mixer and dropping funel, at 45 DEG C, the ester 1.7mol of agitation and dropping gained, dropwise rear reaction 45min, aluminum sulfate 0.25mol is added under agitation in the solution of the 3rd step gained, 40 DEG C of insulation reaction 2h, obtain described metal ion match collecting agent.Fig. 2 metal ion match collecting agent and with the infrared spectrum analysis (a metal ion match collecting agent, b tungsten ore, infrared spectrum analysis after c metal ion and tungsten ore effect) containing tungsten mineral.
Utilize this process process precious jade hilllock celestial tungsten tin molybdenum bismuth polymetallic ore, desulfurization mine tailing is 9.1 by sodium carbonate adjustment pH, adds the metal ion match collecting agent 400g/t of preparation, and inflation is sized mixing and stirred 5min, rough concentrate WO
322.83%, in rough concentrate, add silicone oil 30g/t, prodan 100g/t, mixing speed is 800r/min, and high-pressure fog pressure is 5Mpa, and after bubble collapse, ore pulp obtains tungsten concentrate WO through spiral chute gravity treatment
369.11%, the overall rate of recovery 85.18%.
Precious jade hilllock celestial tungsten floatation process result of the test
| Product | Productive rate/% | WO 3/％ | WO 3The rate of recovery/% |
| Concentrate | 0.53 | 69.11 | 85.18 |
| Mine tailing | 99.47 | 0.06 | 14.72 |
| Sulphur tail | 100.00 | 0.43 | 100.00 |
Embodiment 3
The aphthenic acids of 1mol/L is mixed with the absolute methanol of 3mol/L, slowly adds 30mL concentrated acid, add several zeolites, be heated to 70 DEG C of backflow 1.5h.Distill out excessive methyl alcohol with distilling apparatus, Liquid Residue obtains corresponding ester after 3 washings; Hydroxylamine hydrochloride 2.2mol is added in single port flask, and adds 50mL ethanol, stir cooling in a water bath, add NaOH 88g wherein, stir 1.5h in a water bath, filter away insoluble free azanol, obtain free hydrochloric acid azanol; Free hydroxylamine hydrochloride and 25mL methyl alcohol is added in the there-necked flask with electric mixer and dropping funel, at 50 DEG C, the ester 1.7mol of agitation and dropping gained, dropwise rear reaction 45min, nickelous sulfate 0.125mol is added under agitation in the solution of the 3rd step gained, 40 DEG C of insulation reaction 2h, obtain described metal ion match collecting agent.Fig. 3 metal ion match collecting agent and with the infrared spectrum analysis (a metal ion match collecting agent, b tungsten ore, infrared spectrum analysis after c metal ion and tungsten ore effect) containing tungsten mineral.
Utilize this process process persimmon bamboo plantation bavin mountain high calcium polymetallic ore, desulfurization mine tailing is 9.5 by sodium carbonate adjustment pH, adds the metal ion match collecting agent 400g/t of preparation, and inflation is sized mixing and stirred 5min, rough concentrate WO
327.11%, in rough concentrate, add kerosene 80g/t, polyacrylic acid 40g/t, mixing speed is 800r/min, and high-pressure fog pressure is 8Mpa, and after bubble collapse, ore pulp obtains tungsten concentrate WO through outstanding gravity treatment of shaking
365.98%, the overall rate of recovery 84.34%.
Bavin mountain tungsten floatation process result of the test
| product | productive rate/% | wO 3/ % | wO 3the rate of recovery/% |
| concentrate | 0.61 | 65.98 | 84.34 |
| mine tailing | 99.39 | 0.07 | 15.66 |
| sulphur tail | 100.00 | 0.47 | 100.00. |
Claims (10)
1. a method for tungsten rough concentrate cleaning and Purification, is characterized in that: tungsten ore is broken, wet milling, obtains ore pulp; Gained ore pulp is successively by after deferrization, desulfurization, and enter and roughly select, roughly selecting with metal ion match is collecting agent, is 8.5 ~ 9.5 in pH values of pulp, and under dry glass calcium mineral inhibitor existent condition, roughly selects enrichment tungsten rough concentrate; Described tungsten rough concentrate, after froth breaking and dispersion treatment, enters gravity treatment, obtains tungsten concentrate.
2. the method for tungsten rough concentrate cleaning and Purification according to claim 1, is characterized in that: the addition of the relative tungsten ore of described metal ion match is 200 ~ 500g/t.
3. the method for tungsten rough concentrate cleaning and Purification according to claim 2, is characterized in that: described metal ion match is formed by ligand and metallic ion coordination;
Described metal ion is Fe
3+, Fe
2+, Pb
2+, Cu
2+, Zn
2+, Al
3+, Mn
2+, Ni
2+or Ca
2+;
Described ligand has formula 1 structure;
Wherein,
R is phenyl, substituted-phenyl or C
6~ C
8alkyl.
4. the method for tungsten rough concentrate cleaning and Purification according to claim 3, is characterized in that: the coordination mol ratio of described metal ion and ligand is 1:2,1:4,1:8 or 1:16.
5. the method for tungsten rough concentrate cleaning and Purification according to claim 1, is characterized in that: described tungsten ore is broken, ore grinding to granularity meets-200 order grade mass percentage content and accounts for more than 55%; In described rougher process, ore pulp mass percent concentration is 30 ~ 55%.
6. the method for the tungsten rough concentrate cleaning and Purification according to any one of Claims 1 to 5, is characterized in that: WO in described tungsten ore
3mass percentage content be greater than 0.05%, wherein, be at least one in scheelite, ferberite, huebnerite, wolfram ocher etc. containing tungsten mineral, gangue mineral is mainly garnet, calcite, fluorite, barite and silicate mineral; WO in described tungsten rough concentrate
3grade is greater than 7%, and main gangue mineral is calcite, fluorite, magnetic iron ore and part silicate mineral; WO in described tungsten concentrate
3grade is greater than 65%.
7. the method for tungsten rough concentrate cleaning and Purification according to claim 1, is characterized in that: described defoaming treatment combines realization by chemical froth breaking and mechanical defoaming; Described chemical froth breaking adopts kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C
7~ C
9alcohols at least one as defoamer; Described mechanical defoaming is high-pressure fog and mechanical agitation, and high-pressure fog pressure is more than 0.5Mpa, mechanical agitation speed 300 ~ 800r/min.
8. the method for tungsten rough concentrate cleaning and Purification according to claim 1, is characterized in that: described dispersion treatment process, for regulating more than pH values of pulp to 9.5 by pH adjusting agent, adds dispersant simultaneously and strengthens particle dispersion.
9. the method for tungsten rough concentrate cleaning and Purification according to claim 8, is characterized in that: described pH adjusting agent is at least one in sodium carbonate, NaOH, sodium acid carbonate; Described dispersant is at least one in calgon, prodan, polyacrylic acid, polyethylene glycol.
10. the method for tungsten rough concentrate cleaning and Purification according to claim 1, is characterized in that: described gravity treatment is by shaking table, spiral chute, outstanding shake gravity concentrator or swirl separator realization.
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| CN106944245A (en) * | 2017-03-29 | 2017-07-14 | 江西省宏兴选矿设备制造有限公司 | A kind of complicated many golden metallic ores of W, mo, bi fluorite select technique |
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| CN111519047B (en) * | 2020-04-08 | 2022-04-29 | 厦门钨业股份有限公司 | Method for treating scheelite ore |
| CN115155823A (en) * | 2022-07-27 | 2022-10-11 | 湖南柿竹园有色金属有限责任公司 | Method for normal-temperature flotation and enrichment of high-calcium tungsten ore |
| CN115155823B (en) * | 2022-07-27 | 2023-08-22 | 湖南柿竹园有色金属有限责任公司 | Method for normal-temperature floatation enrichment of high-calcium tungsten ore |
| CN117019379A (en) * | 2023-08-10 | 2023-11-10 | 昆明理工大学 | Bubble control flotation method for argillaceous lepidolite ore |
| CN117019379B (en) * | 2023-08-10 | 2024-05-24 | 昆明理工大学 | Bubble control flotation method for argillaceous lepidolite ore |
| CN118022974A (en) * | 2024-04-10 | 2024-05-14 | 湖南有色新田岭钨业有限公司 | Screening and gravity separation combined mineral separation process for scheelite |
| CN118022974B (en) * | 2024-04-10 | 2024-06-07 | 湖南有色新田岭钨业有限公司 | Screening and gravity separation combined mineral separation process for scheelite |
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