CN110015775A - A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy - Google Patents
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy Download PDFInfo
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- CN110015775A CN110015775A CN201811630859.5A CN201811630859A CN110015775A CN 110015775 A CN110015775 A CN 110015775A CN 201811630859 A CN201811630859 A CN 201811630859A CN 110015775 A CN110015775 A CN 110015775A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/96—Methods for the preparation of sulfates in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a kind of resource type treating methods of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps: defluorinating agent is added in fluorine-containing alkaline waste water, is then stirred, generates fluoride precipitating, the alkaline waste water after collecting fluorine removal；Fluoride precipitating is successively filtered, washed, is dried, anhydrous fluoride is obtained；Anhydrous fluoride is mixed with the concentrated sulfuric acid, is reacted under the conditions of 150-300 DEG C of temperature, collects obtain HF, sulfate respectively；Calcium hydroxide is added in alkaline waste water after fluorine removal and carries out depth defluorination reaction, the fluorine content in waste water is set to be less than 0.001g/l, then it by being concentrated by evaporation, produces to obtain ammonium sulfate product, the condensed water that evaporating concentration process generates can return to tantalum and niobium hydrometallurgy production process.Method resource utilization of the invention is high, no waste water or excessive waste residue, substantially realization wastewater zero discharge, and the value of the product of output is high, and defluorinating agent can be recycled, and processing cost is low.
Description
Technical field
The invention belongs to fluoride waste Treatment process fields, and in particular to a kind of fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy
Resource type treating method.
Background technique
A large amount of fluorine-containing alkaline waste water is generated during tantalum and niobium hydrometallurgy, main component is ammonium fluoride and ammonium sulfate
And free ammonia, PH 9-11, fluorine content 10-80g/l, ammonia-nitrogen content 20-140g/l, sulfate radical 10-120g/l, it is a kind of
High fluorine high ammonia-nitrogen wastewater.
Currently, conventional treatment method in the prior art be with lime fluorinion in waste water, sulfate radical with calcirm-fluoride,
The form of calcium sulfate slag removes, and ammonia recycles ammonium hydroxide by way of blow-off method removes or strips ammonia still process in remaining waste water.Process at
This height, water treatment effect are difficult to up to standard, and need to carry out advanced treating can be only achieved discharge standard, while generate a large amount of fluorine-containing
Waste residue forms new pollutant, it is difficult to thoroughly solve environmental issue.Fluorine in waste water is not recycled, and causes resource
Waste.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of fluorine-containing alkalinity of tantalum and niobium hydrometallurgy
The resource utilization of the resource type treating method of waste water, this method is high, and no waste water or excessive waste residue are basic to realize waste water zero
The value of the product of discharge, output is high, and defluorinating agent can be recycled, and processing cost is low.
The purpose of the present invention adopts the following technical scheme that realization:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, which is characterized in that including following step
It is rapid:
Fluoride precipitates generation step: defluorinating agent being added in fluorine-containing alkaline waste water, is then stirred, fluorination is generated
Object precipitating, the alkaline waste water after collecting fluorine removal；Fluoride precipitating is successively filtered, washed, is dried, anhydrous fluorination is obtained
Object；
Reaction step: anhydrous fluoride is mixed with the concentrated sulfuric acid, reacts under the conditions of 150-300 DEG C of temperature, receives respectively
Collection obtains HF, sulfate；
Depth defluorinate step: calcium hydroxide is added in the alkaline waste water after fluorine removal and carries out depth defluorination reaction, makes waste water
In fluorine content be less than 0.001g/l, then through evaporation and concentration, produce to obtain ammonium sulfate product.
Further, further include that sulfate utilizes step: the sulfate that reaction step is obtained returns to fluorine as defluorinating agent
It is recycled in compound precipitating generation step.
Further, further including HF utilizes step: by HF that reaction step obtains after freezing, compressing, being made high-purity
The anhydrous hydrogen fluoride of degree.
Further, further include that HF utilizes step: dense hydrofluoric acid is made in the HF water absorption that reaction step obtains.
Further, further include that HF utilizes step: the HF that reaction step obtains directly is sold or returned outside tantalum niobium wet process smelting
Refine production process.
Further, the defluorinating agent is lithium sulfate.
Further, in fluoride precipitating generation step, the additional amount of defluorinating agent is by fluorinated volume and sulfuric acid in fluoride waste
The 0.9-1.1 coefficient of lithium theory reacting dose calculates.
Further, in fluoride precipitating generation step, mixing time is 1.5-2.5 hours.
Further, in reaction step, the mass ratio of anhydrous fluoride and the concentrated sulfuric acid is 0.4-0.6:1, and reaction temperature is
150-300℃。
Further, in depth defluorinate step, the mass volume ratio of the alkaline waste water after calcium hydroxide and fluorine removal is 10-
30 ㎏/side, the time of depth defluorination reaction are 1-2 hours.
The beneficial effects of the present invention are:
The present invention precipitates generation step by fluoride and generates fluoride precipitating；By fluoride precipitating successively by filtering,
Washing, drying, obtain anhydrous fluoride；Anhydrous fluoride is mixed with the concentrated sulfuric acid, it is anti-under the conditions of 150-300 DEG C of temperature
It answers, collects obtain the alkaline waste water after HF, sulfate and fluorine removal respectively；Then hydrogen-oxygen is added in the alkaline waste water after fluorine removal
Change calcium and carry out depth defluorination reaction, the fluorine in waste water is made to be less than 10ppm, then by being concentrated by evaporation, produces to obtain ammonium sulfate production
Product；Meanwhile the invention also includes sulfate, and step and HF to be utilized to utilize step.Therefore, method resource utilization of the invention
Height, fluorine, ammonia, sulfate radical are recycled with product form substantially, are comprehensively utilized；Without waste water or excessive waste residue, basic realize is given up
Water zero discharge；Output value of the product is high, there is certain economic benefit；Defluorinating agent is recycled, and processing cost is low.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: defluorinating agent being added in fluorine-containing alkaline waste water, is then stirred, fluorination is generated
Object precipitating, the alkaline waste water after collecting fluorine removal；Fluoride precipitating is successively filtered, washed, is dried, anhydrous fluorination is obtained
Object；
Reaction step: anhydrous fluoride is mixed with the concentrated sulfuric acid, reacts under the conditions of 150-300 DEG C of temperature, receives respectively
Collection obtains HF, sulfate；
Depth defluorinate step: calcium hydroxide is added in the alkaline waste water after fluorine removal and carries out depth defluorination reaction, makes waste water
In fluorine content be less than 0.001g/l, then through evaporation and concentration, produce to obtain ammonium sulfate product.
Further include that sulfate utilizes step as mode is further carried out: the sulfate that reaction step is obtained as
Defluorinating agent returns to be recycled in fluoride precipitating generation step.
As mode is further carried out, further include that HF utilizes step: the HF that reaction step is obtained is by freezing, pressure
After contracting, the anhydrous hydrogen fluoride of high-purity is made.
Further include that HF utilizes step as mode is further carried out: the HF water absorption that reaction step obtains is made
Dense hydrofluoric acid.
Further include that HF utilizes step as mode is further carried out: the HF that reaction step obtains directly is sold or returned outside
Return tantalum and niobium hydrometallurgy production process.
As the mode that further carries out, the defluorinating agent is lithium sulfate, and property is that its fluoride is insoluble or be insoluble in
Water, but its sulfate can dissolve.
As the mode that further carries out, fluoride is precipitated in generation step, and the additional amount of defluorinating agent is by fluoride waste
The 0.9-1.1 coefficient of fluorinated volume and lithium sulfate theory reacting dose calculates.
As the mode that further carries out, fluoride is precipitated in generation step, and mixing time is 1.5-2.5 hours.
As the mode that further carries out, in reaction step, the mass ratio of anhydrous fluoride and the concentrated sulfuric acid is 0.4-0.6:
1, reaction temperature is 150-300 DEG C.
As the mode that further carries out, in depth defluorinate step, the quality of the alkaline waste water after calcium hydroxide and fluorine removal
Volume ratio is 10-30 ㎏/side, and the time of depth defluorination reaction is 1-2 hours.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained by buying pattern outside fixed.
Embodiment 1:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 311.7 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 2000L, then stir 2
Hour, generate fluoride precipitating；Alkaline waste water after collecting fluorine removal, fluorine content 1.8g/l；Fluoride precipitating is successively passed through
It is filtered, washed, dries, obtain 145 ㎏ lithium fluoride solids；
Reaction step: 145 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 280 ㎏ concentration are 98%, in 200 DEG C of temperature
It is reacted 1.5 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 38% of 250L, the HF
Solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 94%；The lithium sulfate that 310 ㎏ are obtained after reaction is solid
Body is recycled as defluorinating agent；
Depth defluorinate step: the calcium hydroxide that 25 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1.5 hours, filtering obtain the liquid that 1860L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling
Obtain 195 ㎏ ammonium sulfate；Crystalline mother solution return be recycled, and evaporating concentration process generate steam obtain after cooling it is dense
The weak aqua ammonia that degree is 0.05%, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:102g/l, (NH4)2SO4: 96g/l, PH 9.0.
Through examining, the rate of recovery of the fluorine of the present embodiment is 94%.
Embodiment 2:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 300 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 2000L, then stir 1.5
Hour, fluoride precipitating, the alkaline waste water after collecting fluorine removal are generated, fluorine content is fluorine in wastewater content 3.6g/l；By fluoride
Precipitating is successively filtered, washed, dries, and obtains 138 ㎏ lithium fluoride solids；
Reaction step: 138 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 240 ㎏ concentration are 98%, in 250 DEG C of temperature
It is reacted 2 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 40.5% of 210L, the HF
Solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 84%；The lithium sulfate that 297 ㎏ are obtained after reaction is solid
Body is recycled as defluorinating agent；
Depth defluorinate step: the calcium hydroxide that 35 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1 hour, filtering obtain the liquid that 1890L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling obtains
To 205 ㎏ ammonium sulfate；Crystalline mother solution, which returns, to be recycled, and the steam that evaporating concentration process generates obtains concentration after cooling
For 0.03% weak aqua ammonia, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:102g/l, (NH4)2SO4: 96g/l, PH 9.0.
Through calculating, the rate of recovery of the fluorine of the present embodiment is 84%.
Embodiment 3:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 342 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 2000L, then stir 2.5
Hour, generate fluoride precipitating；Alkaline waste water after fluorine removal, fluorine content 0.3g/l；Fluoride precipitating was successively passed through
Filter, washing, drying, obtain 146 ㎏ lithium fluoride solids；
Reaction step: 146 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 360 ㎏ concentration are 98%, in 300 DEG C of temperature
It is reacted 1.5 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 38.6% of 255L, should
HF solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 98.5%；The sulfuric acid of 310 ㎏ is obtained after reaction
Lithium solid is recycled as defluorinating agent；Alkaline waste water after collecting fluorine removal, fluorine content g/l；
Depth defluorinate step: the calcium hydroxide that 20 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 2 hours, filtering obtain the liquid that 1910L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling obtains
To 185 ㎏ ammonium sulfate；Crystalline mother solution, which returns, to be recycled, and the steam that evaporating concentration process generates obtains concentration after cooling
For 0.04% weak aqua ammonia, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:102g/l, (NH4)2SO4: 96g/l, PH 9.0.
Through examining, the rate of recovery of the fluorine of the present embodiment is concentration 98.5%.
Embodiment 4:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 450 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 2000L, then stir 1.5
Hour, generate fluoride precipitating；Alkaline waste water after collecting fluorine removal, fluorine content 1.3g/l；Fluoride precipitating is successively passed through
It is filtered, washed, dries, obtain 210 ㎏ lithium fluoride solids；
Reaction step: 210 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 450 ㎏ concentration are 98%, in 250 DEG C of temperature
It is reacted 2 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 38.5% of 360L, the HF
Solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 95.8%；The lithium sulfate of 445 ㎏ is obtained after reaction
Solid is recycled as defluorinating agent；
Depth defluorinate step: the calcium hydroxide that 30 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1.5 hours, filtering obtain the liquid that 1900L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling
Obtain 320 ㎏ ammonium sulfate；Crystalline mother solution return be recycled, and evaporating concentration process generate steam obtain after cooling it is dense
The weak aqua ammonia that degree is 0.06%, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:146g/l, (NH4)2SO4: 127g/l, PH are
9.0。
Through examining, the rate of recovery of the fluorine of the present embodiment is concentration 95.8%.
Embodiment 5:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 450 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 2000L, then stir 1.5
Hour, generate fluoride precipitating；Alkaline waste water after collecting fluorine removal, fluorine content 1.3g/l；Fluoride precipitating is successively passed through
It is filtered, washed, dries, obtain 210 ㎏ lithium fluoride solids；
Reaction step: 210 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 430 ㎏ concentration are 98%, in 150 DEG C of temperature
It is reacted 2 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 36.4% of 350L, the HF
Solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 88%；The lithium sulfate that 440 ㎏ are obtained after reaction is solid
Body is recycled as defluorinating agent；Alkaline waste water after collecting fluorine removal, fluorine content 0.05g/l；
Depth defluorinate step: the calcium hydroxide that 40 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1.5 hours, filtering obtain the liquid that 1860L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling
Obtain 295 ㎏ ammonium sulfate；Crystalline mother solution return be recycled, and evaporating concentration process generate steam obtain after cooling it is dense
The weak aqua ammonia that degree is 0.06%, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:146g/l, (NH4)2SO4: 127g/l, PH 9.0.
Through examining, the rate of recovery of the fluorine of the present embodiment is concentration 88%.
Embodiment 6:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 270 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 4000L, then stir 1.5
Hour, generate fluoride precipitating；Alkaline waste water after collecting fluorine removal, fluorine content 4.5g/l；Fluoride precipitating is successively passed through
It is filtered, washed, dries, obtain 135 ㎏ lithium fluoride solids；
Reaction step: 135 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 230 ㎏ concentration are 98%, in 150 DEG C of temperature
It is reacted 2 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 38.9% of 200L, the HF
Solution reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 81.6%；The lithium sulfate of 260 ㎏ is obtained after reaction
Solid is recycled as defluorinating agent；
Depth defluorinate step: the calcium hydroxide that 70 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1.5 hours, filtering obtain the liquid that 3880L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling
Obtain 225 ㎏ ammonium sulfate；Crystalline mother solution return be recycled, and evaporating concentration process generate steam obtain after cooling it is dense
The weak aqua ammonia that degree is 0.02%, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:48g/l, (NH4)2SO4: 42g/l, PH 9.0.
Through examining, the rate of recovery of the fluorine of the present embodiment is 81.6%.
Embodiment 7:
A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, comprising the following steps:
Fluoride precipitates generation step: 320 ㎏ lithium sulfates being added in the fluorine-containing alkaline waste water of 4000L, then stir 1.5
Hour, generate fluoride precipitating；Alkaline waste water after collecting fluorine removal, fluorine content 0.6g/l；Fluoride precipitating is successively passed through
It is filtered, washed, dries, obtain 149 ㎏ lithium fluoride solids；
Reaction step: 149 ㎏ lithium fluoride solids are mixed with the concentrated sulfuric acid that 310 ㎏ concentration are 98%, in 250 DEG C of temperature
It is reacted 2 hours under the conditions of degree；The gas generated with absorbing pure water reaction, obtains the HF solution of the concentration 40% of 220L, the HF is molten
Liquid reaches the C.P grades of pure hydrofluoric acid standards of chemistry, and the rate of recovery for converting fluorine is 92.3%；The lithium sulfate that 316 ㎏ are obtained after reaction is solid
Body is recycled as defluorinating agent；
Depth defluorinate step: the calcium hydroxide that 40 ㎏ are added in the alkaline waste water after fluorine removal carries out depth defluorination reaction,
Reaction 1.5 hours, filtering obtain the liquid that 3910L fluorine content is less than 0.001g/l, are then evaporated concentration, crystallisation by cooling
Obtain 245 ㎏ ammonium sulfate；Crystalline mother solution return be recycled, and evaporating concentration process generate steam obtain after cooling it is dense
The weak aqua ammonia that degree is 0.03%, can return for tantalum and niobium hydrometallurgy production process.
In the fluorine-containing alkaline waste water of 2000L, main component are as follows: NH4F:48g/l, (NH4)2SO4: 42g/l, PH 9.0.
Through examining, the rate of recovery of the fluorine of the present embodiment is concentration 92.3%.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy, which comprises the following steps:
Fluoride precipitates generation step: defluorinating agent being added in fluorine-containing alkaline waste water, is then stirred, it is heavy to generate fluoride
It forms sediment, the alkaline waste water after collecting fluorine removal；Fluoride precipitating is successively filtered, washed, is dried, anhydrous fluoride is obtained；
Reaction step: anhydrous fluoride is mixed with the concentrated sulfuric acid, reacts under the conditions of 150-300 DEG C of temperature, collects respectively
To HF, sulfate；
Depth defluorinate step: calcium hydroxide is added in the alkaline waste water after fluorine removal and carries out depth defluorination reaction, makes in waste water
Fluorine content is less than 0.001g/l, then by being concentrated by evaporation, produces to obtain ammonium sulfate product.
2. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that also
Step is utilized including sulfate: the sulfate that reaction step obtains being returned in fluoride precipitating generation step as defluorinating agent and is followed
Ring uses.
3. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that also
Step is utilized including HF: by HF that reaction step obtains after freezing, compressing, the anhydrous hydrogen fluoride of high-purity is made.
4. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that also
Step is utilized including HF: dense hydrofluoric acid is made in the HF water absorption that reaction step obtains.
5. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that also
Step is utilized including HF: the HF that reaction step obtains directly is sold or returned outside tantalum and niobium hydrometallurgy production process.
6. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that institute
Stating defluorinating agent is lithium sulfate.
7. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that fluorine
Compound precipitates in generation step, and the additional amount of defluorinating agent presses the 0.9- of fluorinated volume and lithium sulfate theory reacting dose in fluoride waste
1.1 coefficients calculate.
8. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that fluorine
Compound precipitates in generation step, and mixing time is 1.5-2.5 hours.
9. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that anti-
It answers in step, the mass ratio of anhydrous fluoride and the concentrated sulfuric acid is 0.4-0.6:1, and reaction temperature is 150-300 DEG C.
10. the resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy as described in claim 1, which is characterized in that
In depth defluorinate step, the mass volume ratio of the alkaline waste water after calcium hydroxide and fluorine removal is 10-30 ㎏/side, and depth defluorinate is anti-
The time answered is 1-2 hours.
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| CN201811630859.5A CN110015775A (en) | 2018-12-29 | 2018-12-29 | A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy |
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| CN201811630859.5A CN110015775A (en) | 2018-12-29 | 2018-12-29 | A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy |
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| CN201811630859.5A Pending CN110015775A (en) | 2018-12-29 | 2018-12-29 | A kind of resource type treating method of the fluorine-containing alkaline waste water of tantalum and niobium hydrometallurgy |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520924A (en) * | 2020-10-12 | 2021-03-19 | 九江学院 | Recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy |
| CN113233475A (en) * | 2021-04-16 | 2021-08-10 | 昆岳互联环境技术(江苏)有限公司 | Method for effectively removing mother liquor fluorine ions in ammonia desulphurization ammonium sulfate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774561A (en) * | 2015-03-27 | 2015-07-15 | 南昌大学 | Method for preparing rare earth polishing powder and recovering ammonium salt by using fluorine-containing niobium-tantalum wastewater |
| CN105948083A (en) * | 2016-04-28 | 2016-09-21 | 中南大学 | Environment-friendly separation and recovery method of fluorine in fluorine-containing waste liquid |
| CN106587424A (en) * | 2016-12-13 | 2017-04-26 | 广东致远新材料有限公司 | Resourceful treatment method for tantalum-niobium industrial fluorine-containing ammonia-nitrogen wastewater |
| CN108975586A (en) * | 2018-07-16 | 2018-12-11 | 肖平 | Fluorine-containing in tantalum and niobium hydrometallurgy, nitrogen-containing wastewater recovery and treatment method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774561A (en) * | 2015-03-27 | 2015-07-15 | 南昌大学 | Method for preparing rare earth polishing powder and recovering ammonium salt by using fluorine-containing niobium-tantalum wastewater |
| CN105948083A (en) * | 2016-04-28 | 2016-09-21 | 中南大学 | Environment-friendly separation and recovery method of fluorine in fluorine-containing waste liquid |
| CN106587424A (en) * | 2016-12-13 | 2017-04-26 | 广东致远新材料有限公司 | Resourceful treatment method for tantalum-niobium industrial fluorine-containing ammonia-nitrogen wastewater |
| CN108975586A (en) * | 2018-07-16 | 2018-12-11 | 肖平 | Fluorine-containing in tantalum and niobium hydrometallurgy, nitrogen-containing wastewater recovery and treatment method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520924A (en) * | 2020-10-12 | 2021-03-19 | 九江学院 | Recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy |
| CN113233475A (en) * | 2021-04-16 | 2021-08-10 | 昆岳互联环境技术(江苏)有限公司 | Method for effectively removing mother liquor fluorine ions in ammonia desulphurization ammonium sulfate |
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