CN105413855B - A kind of method of tungsten rough concentrate cleaning and Purification - Google Patents
A kind of method of tungsten rough concentrate cleaning and Purification Download PDFInfo
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- CN105413855B CN105413855B CN201511022319.5A CN201511022319A CN105413855B CN 105413855 B CN105413855 B CN 105413855B CN 201511022319 A CN201511022319 A CN 201511022319A CN 105413855 B CN105413855 B CN 105413855B
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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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of method of tungsten rough concentrate cleaning and Purification, this method is by tungsten ore is broken, wet milling, obtains ore pulp；After gained ore pulp passes sequentially through deferrization, desulfurization, into roughing, under the conditions of roughing is 8.5~9.5 in pH values of pulp using metal ion match as collecting agent, and dry glass calcium mineral inhibitor is existing, roughing enrichment tungsten rough concentrate；The tungsten rough concentrate into gravity treatment, obtains tungsten concentrate, gravity tailings returns to roughing operation and further reclaims remaining tungsten mineral after defoaming and decentralized processing.This method is up to more than 90% to the rate of recovery of tungsten in tungsten ore, and flow is short, medicament is simple and convenient to operate, labor intensity is low, energy consumption is low, environment-friendly high-efficiency, not only significantly reduces cost but also significantly improves the utilization rate of tungsten resource.
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 valuable rare metal, is that fusing point highest, thermal coefficient of expansion be minimum in metallic element, vapour pressure is minimum
Element, be one of density highest metallic element, tungsten has excellent mechanical behavior under high temperature, very high modulus of compressibility and bullet
Property modulus, excellent Properties of High Temperature Creep, high electrical conductivity and the system of thermal conductivity and very high electron emission coefficiency etc. one
Row special performance, thus it is widely used in the every field such as civilian, industrial, military project.For a long time, the ore deposit of China's tungsten industry exploitation
It is mainly wolframite to produce resource.According to Ministry of Land and Resources 2002《Mineral Resources in China annual report》The black tungsten reserves announced, by
2000 end of the year reserves (WO3) it is 144.05 ten thousand tons, account for national tungsten ore produces total reserves 27.4%, wherein A+B+C levels
53.6 ten thousand tons of (industry) reserves.And the selecting overall recovery of China's tungsten is very low at present, serious waste of resources, existing wolframite reserves
Exhaust or remain little substantially.In face of the disappearance of the black the advantages of tungsten resources in China, it is necessary to increase white tungsten exploitation dynamics, improve white tungsten
Selecting and smelting technology, white tungsten resource recovery utilization rate is improved, to ensure China's tungsten industry sustainable development.
Scheelite ore type can be largely classified into:White tungsten-quartz (or silicate mineral), white tungsten-calcite, fluorite
(barite) type.Generally, white tungsten-quartz type ore ratio is easier to select；And white tungsten-fluorite, calcite (barite) type ore deposit
The difficult choosing of stone, is separated because tungsten is close and difficult with the floatability of calcic gangue mineral in vain.White tungsten floatation process is generally divided into roughing section
With selected section of two stages.Roughing section mainly for the purpose of eliminating gangue mineral to greatest extent, improves flotation operation concentration ratio.Roughing section
Normal temperature flotation typically is used, conventional pH regulators have：Sodium hydroxide, sodium carbonate, lime+sodium carbonate；Gangue inhibitor is universal
Use waterglass.The selected of white tungsten rough concentrate is that entirely the key of tungsten flotation, white tungsten floatation process classification typically press selected section in vain
Whether heat and be divided into heating flotation and normal temperature flotation.That is underflow high temperature method and normal temperature flotation method.Underflow high temperature method is sieve Peter
Husband's method.At present, white tungsten flotation production practices are widely used in.The method is that Soviet experts are sent out than get Luo Fu in late 1940s
Bright.Rough concentrate is concentrated into 70% or so concentration, increasing amount waterglass, and is heated up to more than 90 DEG C, strong mixing 30~
60 minutes, then dilute normal temperature flotation.The method is widely used to ore strong adaptability in each white tungsten ore dressing plant.By
Similar temperament is swum in the calcium mineral (fluorite, calcite etc.) and scheelite of association and enters froth pulp simultaneously, is further divided
From extremely difficult.Reach the separation of white tungsten and association calcium mineral, it is necessary to cause white tungsten and association calcium mineral floatability
Difference.Using Dinko Petrov method can the successfully diffeential floatation scheelite from the white tungsten rough concentrate of association calcium mineral, be because
Under the conditions of Dinko Petrov method, waterglass is different with the ability of association calcium mineral surface desorption collecting agent from white tungsten and causes
's.Under the conditions of Dinko Petrov method, scheelite remains in that good floatability, and fluorite, calcite are due to surface collecting agent
Desorption and be suppressed.It is achieved thereby that white tungsten and these calcic gangue minerals efficiently separate.Dinko Petrov method need to heat floating
Choosing, high energy consumption, cost is high, and complex operation, working condition is poor, so, adopt new technology and realize that white tungsten normal temperature flotation is epoch hair
The desirability of exhibition and inevitable requirement.In the early 1970s, the black and white tungsten normal temperature flotation method of 731 oxidized paraffin waxs is first in China Jiangxi
Certain southern tungsten ore is initiated and obtains production application.The method more payes attention to roughing operation, emphasizes carbonic acid and water compared with Dinko Petrov method
The cooperative effect of glass, make the HSiO in ore pulp- 3It is maintained at the concentration range of optimal inhibition.Then 731 that selectivity is stronger are used
Oxidized paraffin wax soap does collecting agent, improves roughing concentration ratio.A large amount of waterglass are added when selected in rough concentrate to carry out for a long time
(more than 30min) strong agitation, then conventional flotation is diluted, whole dressing process is carried out under normal temperature condition.This method is simple to operate,
Cost is low, but to the adaptability of ore not as good as Dinko Petrov method.731 normal temperature methods are on the skarn type scheelite mountain based on quartz
Obtain wider model application, in recent years white tungsten-fluorite, calcite type scheelite stone practice in also have application.
The FLOTATION SEPARATION of the calcium mineral such as scheelite and fluorite, calcite is one of world's ore dressing problem.And scheelite master
Originate in skarns tungsten deposit.During scheelite this kind of with fatty acid collecting agent flotation, due to calcium mineral (fluorite, calcite)
Floatability it is close with scheelite while enter froth pulp.At present, white tungsten is selected typically uses Dinko Petrov method.But heat
Method cost is high, and complex operation, working condition is poor, and traditional normal temperature concentration process costs are high, ore bad adaptability, roughing operation and essence
Industry tomography is elected to be, recycled in its entirety rate is low.
The content of the invention
Selecting tungsten technique to exist for conventional fat acid, calcium mineral separation is difficult, waterglass dosage is big, the selected operation of roughing
The problems such as separation is difficult, the rate of recovery is low, the purpose of the present invention are to be to provide that a kind of flow is short, energy consumption is low, cost is low, and in nothing
The method that the efficient flotation separation containing tungsten mineral (scheelite, wolframite, wolfram ocher etc.) is enriched with is realized under the conditions of calcium mineral inhibitor, should
Method solves prior art and brings tungsten ore organic efficiency low using a large amount of waterglass inhibitor, and concentrate, mine tailing sedimentation concentration are stranded
The problems such as difficult, and in reuse adoption process the defects of bed surface fouling, low separation efficiency.
In order to realize above-mentioned technical purpose, the invention provides a kind of method of tungsten rough concentrate cleaning and Purification, this method is
Tungsten ore is crushed, wet milling, obtain ore pulp；After gained ore pulp passes sequentially through deferrization, desulfurization, into roughing, roughing is with metal
Under the conditions of ionic complex is collecting agent, is 8.5~9.5 in pH values of pulp, and dry glass calcium mineral inhibitor is existing, slightly
Choosing enrichment tungsten rough concentrate；The tungsten rough concentrate, into gravity treatment, obtains tungsten concentrate after defoaming and decentralized processing.
Technical scheme, collecting agent is used as by the extremely strong metal ion match of selectivity so that roughing is made
Industry realizes the efficient flotation separation enrichment containing tungsten mineral (scheelite, wolframite, wolfram ocher etc.) under the conditions of without calcium mineral inhibitor,
Roughing operation concentration ratio is up to more than 50 times, and the rate of recovery is more than 85%, and being elected to be industry for subsequent fine creates favorable conditions；Selected operation
Make full use of and gangue mineral granularity, difference of specific gravity separated with difficulty containing tungsten mineral, the efficiently concentrating containing tungsten mineral is realized by gravity treatment,
Operation recovery is up to more than 90%, thoroughly substitutes heating concentration operation.The combining to have given full play to of flotation and gravity treatment contain tungsten ore
Thing and gangue mineral greatly improve WO in the difference of floatability, proportion, granularity etc.3The rate of recovery.Relatively existing skill
Art, the cancellation of waterglass not only solve prior art and bring tungsten ore organic efficiency low using a large amount of waterglass inhibitor, essence
The problems such as ore deposit, mine tailing sedimentation concentration difficulty, and in reuse adoption process the defects of bed surface fouling, low separation efficiency.
Preferable scheme, metal ion match are 200~500g/t with respect to the addition of raw ore.
Preferable scheme, metal ion match are formed by ligand and metallic ion coordination；
Metal ion is Fe3+、Fe2+、Pb2+、Cu2+、Zn2+、Al3+、Mn2+、Ni2+Or Ca2+；
Described ligand has the structure of formula 1；
Wherein,
R is phenyl, substituted-phenyl or C6~C8Alkyl.
The coordination mol ratio of preferable scheme, metal ion and ligand is 1:2、1:4、1:8 or 1:16.
The preparation method of the metal ion match collecting agent of the present invention specifically includes following steps：
The first step, the esterification of carboxylic acid
Carboxylic acid is mixed with excessive absolute alcohol, is slowly added to concentrated acid, and adds several zeolites, 70~80 DEG C is heated to and returns
After flowing 1~2h, excessive alcohol is distilled out with distilling apparatus, Liquid Residue obtains corresponding carboxylate after 3~5 washings；
Described carboxylate has the structure of formula 2：
Wherein,
R is phenyl, substituted-phenyl or C6~C12Alkyl；
R1For methyl or ethyl；
Second step, freeization of hydroxylamine hydrochloride
Hydroxylamine hydrochloride is added in single-necked flask, and adds absolute ethyl alcohol, stirring cooling, adds hydrogen thereto in a water bath
Sodium oxide molybdena, 1~2h is stirred in a water bath, filters off except insoluble matter, produces free hydrochloric acid hydroxylamine solution；
3rd step, the synthesis of ligand
Free hydrochloric acid hydroxylamine solution and methanol solvate are added into the three-necked flask with electric mixer and dropping funel,
At 45~55 DEG C, the carboxylate obtained by the agitation and dropping first step, 30~45min is reacted after being added dropwise, produces ligand；
4th step, the synthesis of complex
Soluble metallic salt is added into the solution obtained by the 3rd step under agitation, in 35~45 DEG C of insulation reaction l
~2h, produce metal ion match collecting agent；The mol ratio of metal salt and ligand is 1:2、1:4、1:8 or 1:16；It is solvable
Property metal salt be containing Fe3+、Fe2+、Pb2+、Cu2+、Zn2+、Al3+、Mn2+、Ni2+Or Ca2+Soluble metallic salt.
Preferable scheme, tungsten ore is broken, ore grinding to granularity meets that -200 mesh grade mass percentage contents account for more than 55%,
Tungsten ore can ensure that tungstenic degree of dissociation of mineral monomer is more than 90% by broken, ore grinding to appropriate granularity.
Preferable scheme, rougher process ensure that ore pulp mass percent concentration is 30~55%.
Preferable scheme, magnetic separation deferrization process by the mass percentage content of the magnetic iron ore in tungsten ore be reduced to 10% with
Under.
More preferably scheme, WO in tungsten ore3Mass percentage content be more than 0.05%, wherein, be white tungsten containing tungsten mineral
At least one of ore deposit, ferberite, huebnerite, wolfram ocher etc., gangue mineral are mainly garnet, calcite, fluorite, barite
And silicate mineral.
More preferably scheme, WO in tungsten rough concentrate3Grade is more than 7%, and main gangue mineral is calcite, fluorite, magnet
Ore deposit and part silicate mineral.
More preferably scheme, WO in tungsten concentrate3Grade is more than 65%.
Preferable scheme, defoaming treatment are realized by chemistry defoaming and mechanical defoaming joint.
More preferably scheme, chemistry defoaming is using kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C7~C9Alcohols at least
One kind is used as defoamer.
More preferably scheme, described mechanical defoaming are high-pressure fog and mechanical agitation, and high-pressure fog pressure is 0.5Mpa
More than, 300~800r/min of mechanical agitation speed.
Preferable scheme, decentralized processing process is to adjust pH values of pulp to more than 9.5 by pH regulators, while is added scattered
Agent strengthens particle dispersion.
More preferably scheme, pH regulators are at least one of sodium carbonate, sodium hydroxide, sodium acid carbonate.PH regulator masters
Make particle surface band like charges, promote particle to disperse.
More preferably scheme, dispersant are at least one of calgon, prodan, polyacrylic acid, polyethylene glycol.
More preferably scheme, gravity treatment pass through shaking table, spiral chute, outstanding shake gravity concentrator or swirl separator realization.Pass through weight
WO in tungsten concentrate after choosing3Grade is more than 65%, and gravity tailings returns to rougher process.
Preferable scheme, waterglass and other any inhibitor are added without in floatation process.
Preferable scheme, process of sizing mixing are inflation Strong shear stirring.
Calgon of the present invention, prodan, polyacrylic acid, polyethylene glycol, sodium carbonate, sodium hydroxide, carbon
Sour hydrogen sodium, kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C7~C9Alcohols etc. belong to commercially available conventional dose.
The tungsten ore deferrization process of the present invention is using the conventional magnetic separation deferrization technique in this area.
The tungsten ore sweetening process of the present invention is used as collecting agent using the conventional floatation desulphurization in this area using butylamine black powder etc..
The method of the tungsten rough concentrate cleaning and Purification of the present invention specifically includes following steps：
The first step：Broken, ore grinding, deferrization, desulfurization
Ore is after broken, ore grinding, and granularity meets that -200 mesh grade weight/mass percentage compositions are more than 55%, tungstenic mineral monomer
Degree of dissociation is more than 90%, and magnet mineral content is less than 10% after strong magnetomechanical magnetic separation deferrization；Magnetic tailing passes through floatation desulphurization ore deposit；
Second step：Dosing is sized mixing floating and enriching
The mass percent concentration of ore pulp is 30~55%, and the pH that pH regulators regulation ore pulp is added into ore pulp is 8.5
~9.5, metal ion match collecting agent is then added, and floating and enriching is carried out after 3~5min of Aerated stirring, froth pulp is
For tungsten rough concentrate, WO3Grade is more than 7%, and tungsten recovery rate is more than 85%；
3rd step：Rough concentrate defoaming pretreatment
Defoamer, dispersant are added into the rough concentrate foam obtained by second step, and roughing foam is destroyed with high-pressure fog,
Mixing speed is 300~800r/min, and as gravity treatment is to ore deposit after lather collapse eliminates；
4th step：Gravity treatment efficiently concentrating
Ore pulp obtained by 3rd step is subjected to Gravity separation through gravitational separation equipment, produces tungsten concentrate WO3Grade is more than 65%, tail
Ore deposit returns to roughing operation after thickening pond concentrates.
Compared with the prior art, the beneficial effect that technical scheme is brought：
1st, technical scheme employs the complex conduct that the extremely strong ligand of selectivity is formed with metal ion
Collecting agent, realize under the conditions of dry glass and other any inhibitor to containing tungsten mineral (scheelite, wolframite, wolfram ocher etc.)
Efficiently concentrating, roughing operation concentration ratio are up to more than 50 times, and the rate of recovery is more than 85%, and being elected to be industry for subsequent fine creates favourable bar
Part；Make full use of on this basis and gangue mineral granularity, difference of specific gravity are separated with difficulty containing tungsten mineral, realized by gravity treatment and contain tungsten ore
The efficiently concentrating of thing, operation recovery are up to more than 90%, thoroughly substitute heating concentration operation.Pass through the connection of flotation combination gravity treatment
Close, given full play to containing tungsten mineral and gangue mineral in the difference of floatability, proportion, granularity etc., greatly improved WO3
The rate of recovery.
2nd, the medicament that technical scheme uses is simple, eliminates making for traditional waterglass calcium mineral inhibitor
With, not only solve prior art and bring tungsten ore organic efficiency low using a large amount of waterglass calcium mineral inhibitor, concentrate, mine tailing
The problems such as sedimentation concentration difficulty, and in reuse adoption process the defects of bed surface fouling, low separation efficiency.
3rd, tungsten ore purification can be achieved in technical scheme at normal temperatures, and energy consumption is low, and cost is low.
4th, technical scheme flow is short, easy to operate, labor intensity is low, environment-friendly high-efficiency.
Brief description of the drawings
【Fig. 1】For obtained phenyl oxime acid/lead metal ionic complex collecting agent in embodiment 1 and containing the infrared of tungsten mineral
Spectrogram：A is metal ion match collecting agent, and b is tungsten ore, and c is after metal ion acts on tungsten ore.
【Fig. 2】For obtained o-hydroxy-phenyl oxime acid/aluminum metal ionic complex collecting agent in embodiment 2 and containing tungsten mineral
Infrared spectrogram：A is metal ion match collecting agent, b tungsten ores, c metal ions with after tungsten ore effect.
【Fig. 3】For the cycloalkyl oxime acid/nickel metal ion match collecting agent prepared in embodiment 3 and containing the red of tungsten mineral
External spectrum figure：A metal ion match collecting agents, b tungsten ores, after c metal ions act on tungsten ore.
Embodiment
Following examples are that present disclosure is further illustrated, rather than the model of limitation the claims in the present invention protection
Enclose.
Embodiment 1
1mol/L benzoic acid is mixed with 3mol/L absolute methanol, is slowly added to 30mL concentrated acids, adds several zeolites,
It is heated to 80 DEG C of backflow 2h.Excessive methanol is distilled out with distilling apparatus, Liquid Residue obtains corresponding ester after 5 washings；By salt
Sour azanol 2.2mol is added in single-necked flask, and adds 50mL ethanol, and stirring cooling, adds sodium hydroxide thereto in a water bath
88g, 2h is stirred in a water bath, filter away insoluble free azanol, produce free hydrochloric acid azanol；To with electric mixer
With free hydroxylamine hydrochloride and 25mL methanol are added in the three-necked flask of dropping funel, at 45 DEG C, the ester obtained by agitation and dropping
1.7mol, 45min is reacted after being added dropwise, adds plumbi nitras 0.5mol into the solution obtained by the 3rd step under agitation,
40 DEG C of insulation reaction 2h, produce the metal ion match collecting agent.Fig. 1 metal ion match collecting agent and its and tungstenic
Infrared spectrum analysis (a metal ion match collecting agents, b tungsten ores, c metal ions and the infrared spectrum after tungsten ore effect of mineral
Analysis).
Persimmon bamboo plantation tungsten tin molybdenum bismuth polymetallic ore is handled using this process, desulfurization mine tailing adjusts pH by sodium carbonate and is
9.0, the metal ion match collecting agent 400g/t of preparation is added, inflation, which is sized mixing, stirs 5min, rough concentrate WO319.70%, to
Tbp 50g/t, calgon 100g/t, mixing speed 500r/min, high-pressure fog pressure are added in rough concentrate
For 10Mpa, ore pulp obtains tungsten concentrate WO through table concentration after bubble collapse373.56%, the overall rate of recovery 82.45%.
Persimmon bamboo plantation tungsten floatation process result of the test
| Product | Yield/% | WO3/ % | WO3The 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
1mol/L salicylic acid is mixed with 3mol/L absolute methanol, is slowly added to 30mL concentrated acids, adds several zeolites,
It is heated to 75 DEG C of backflow 1h.Excessive methanol is distilled out with distilling apparatus, Liquid Residue obtains corresponding ester after 5 washings；By salt
Sour azanol 2.2mol is added in single-necked flask, and adds 50mL ethanol, and stirring cooling, adds sodium hydroxide thereto in a water bath
88g, 1.5h is stirred in a water bath, filter away insoluble free azanol, produce free hydrochloric acid azanol；To with electric stirring
Free hydroxylamine hydrochloride and 25mL methanol are added in the three-necked flask of device and dropping funel, at 45 DEG C, obtained by agitation and dropping
Ester 1.7mol, 45min is reacted after being added dropwise, add aluminum sulfate into the solution obtained by the 3rd step under agitation
0.25mol, 40 DEG C of insulation reaction 2h, produce the metal ion match collecting agent.Fig. 2 metal ion match collecting agent and
Itself and the infrared spectrum analysis containing tungsten mineral are (after a metal ion match collecting agents, b tungsten ores, c metal ions and tungsten ore effect
Infrared spectrum analysis).
Using this process processing precious jade hilllock celestial being tungsten tin molybdenum bismuth polymetallic ore, desulfurization mine tailing adjusts pH by sodium carbonate and is
9.1, the metal ion match collecting agent 400g/t of preparation is added, inflation, which is sized mixing, stirs 5min, rough concentrate WO322.83%, to
Silicone oil 30g/t, prodan 100g/t, mixing speed 800r/min are added in rough concentrate, high-pressure fog pressure is 5Mpa, bubble
Ore pulp obtains tungsten concentrate WO through spiral chute gravity treatment after foam is broken369.11%, the overall rate of recovery 85.18%.
Precious jade hilllock celestial being tungsten floatation process result of the test
| Product | Yield/% | WO3/ % | WO3The 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
1mol/L aphthenic acids is mixed with 3mol/L absolute methanol, is slowly added to 30mL concentrated acids, adds several zeolites,
It is heated to 70 DEG C of backflow 1.5h.Excessive methanol is distilled out with distilling apparatus, Liquid Residue obtains corresponding ester after 3 washings；Will
Hydroxylamine hydrochloride 2.2mol is added in single-necked flask, and adds 50mL ethanol, and stirring cooling, adds hydroxide thereto in a water bath
Sodium 88g, stirs 1.5h in a water bath, filters away insoluble free azanol, produces free hydrochloric acid azanol；To with electric mixing
Mix and free hydroxylamine hydrochloride and 25mL methanol are added in the three-necked flask of device and dropping funel, at 50 DEG C, obtained by agitation and dropping
Ester 1.7mol, 45min is reacted after being added dropwise, adds nickel sulfate into the solution obtained by the 3rd step under agitation
0.125mol, 40 DEG C of insulation reaction 2h, produce the metal ion match collecting agent.Fig. 3 metal ion match collecting agents
And its (a metal ion match collecting agents, b tungsten ores, c metal ions act on tungsten ore with the infrared spectrum analysis containing tungsten mineral
Infrared spectrum analysis afterwards).
Using this process processing persimmon bamboo plantation bavin mountain high calcium polymetallic ore, desulfurization mine tailing adjusts pH by sodium carbonate and is
9.5, the metal ion match collecting agent 400g/t of preparation is added, inflation, which is sized mixing, stirs 5min, rough concentrate WO327.11%, to
Kerosene 80g/t, polyacrylic acid 40g/t, mixing speed 800r/min are added in rough concentrate, high-pressure fog pressure is 8Mpa, bubble
Ore pulp obtains tungsten concentrate WO through outstanding gravity treatment of shaking after foam is broken365.98%, the overall rate of recovery 84.34%.
Bavin mountain tungsten floatation process result of the test
| Product | Yield/% | WO3/ % | WO3The 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 (9)
- A kind of 1. method of tungsten rough concentrate cleaning and Purification, it is characterised in that：Tungsten ore is crushed, wet milling, obtain ore pulp；Gained After ore pulp passes sequentially through deferrization, desulfurization, into roughing, roughing using metal ion match as collecting agent, pH values of pulp be 8.5~ 9.5, and under the conditions of dry glass calcium mineral inhibitor is existing, roughing enrichment tungsten rough concentrate；The tungsten rough concentrate is through defoaming And after decentralized processing, into gravity treatment, obtain tungsten concentrate；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 the structure of formula 1；Wherein,R is phenyl, substituted-phenyl or C6~C8Alkyl.
- 2. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：The metal ion match Addition with respect to tungsten ore is 200~500g/t.
- 3. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：Described metal ion is with matching somebody with somebody The coordination mol ratio of position body is 1:2、1:4、1:8 or 1:16.
- 4. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：Described tungsten ore is broken, mill Ore deposit to granularity meets that -200 mesh grade mass percentage contents account for more than 55%；Ore pulp mass percent in described rougher process Concentration is 30~55%.
- 5. the method for the tungsten rough concentrate cleaning and Purification according to any one of Claims 1 to 4, it is characterised in that：Described tungsten WO in ore deposit3Mass percentage content be more than 0.05%, wherein, be scheelite, ferberite, huebnerite, wolfram ocher etc. containing tungsten mineral At least one of, gangue mineral is mainly garnet, calcite, fluorite, barite and silicate mineral；Described tungsten is thick WO in concentrate3Grade is more than 7%, and main gangue mineral is calcite, fluorite, magnetic iron ore and part silicate mineral；Described WO in tungsten concentrate3Grade is more than 65%.
- 6. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：Described defoaming treatment passes through Chemistry defoaming and mechanical defoaming joint are realized；Described chemistry defoaming is using kerosene, diesel oil, phosphonic acids tributyl, silicone oil, C7~C9 At least one of alcohols be used as defoamer；Described mechanical defoaming is high-pressure fog and mechanical agitation, and high-pressure fog pressure is More than 0.5Mpa, 300~800r/min of mechanical agitation speed.
- 7. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：Described decentralized processing process To adjust pH values of pulp to more than 9.5 by pH regulators, while add dispersant enhancing particle dispersion.
- 8. the method for tungsten rough concentrate cleaning and Purification according to claim 7, it is characterised in that：Described pH regulators are carbon At least one of sour sodium, sodium hydroxide, sodium acid carbonate；Described dispersant be calgon, prodan, polyacrylic acid, At least one of polyethylene glycol.
- 9. the method for tungsten rough concentrate cleaning and Purification according to claim 1, it is characterised in that：Described gravity treatment is by shaking Bed, spiral chute, outstanding shake gravity concentrator or swirl separator realization.
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| CN108913884B (en) * | 2018-07-23 | 2019-12-17 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for preparing crude sodium tungstate solution by decomposing wolframite concentrate at low alkali and high temperature and pressure |
| CN111013828A (en) * | 2019-12-12 | 2020-04-17 | 西藏华泰龙矿业开发有限公司 | Quick flotation device |
| CN111519047B (en) * | 2020-04-08 | 2022-04-29 | 厦门钨业股份有限公司 | Method for treating scheelite 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 |
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| US2373305A (en) * | 1942-10-07 | 1945-04-10 | American Cyanamid Co | Tungsten ore flotation |
| US3779265A (en) * | 1972-01-20 | 1973-12-18 | Dow Chemical Co | Apparatus for continuous measurement and control of flotation conditions |
| US6437194B2 (en) * | 1998-03-23 | 2002-08-20 | Mitsui Chemicals, Inc. | Process for preparing an alkylcyclohexanol alkylene oxide adduct |
| CN101269352B (en) * | 2008-05-05 | 2012-05-30 | 广州有色金属研究院 | Beneficiation method for black and white tungsten fine deposit |
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