CN205838591U - A kind of by sulfuric acid treatment wolframite to prepare the system of tungstate solution - Google Patents
A kind of by sulfuric acid treatment wolframite to prepare the system of tungstate solution Download PDFInfo
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Abstract
A kind of by sulfuric acid treatment wolframite to prepare the system of tungstate solution, including: wolframite device transition, there is isomerization container and filter transition, isomerization container has sulfuric acid solution entrance, wolframite entrance and the outlet of isomerization liquid, and transition, filter had isomerization liquid entrance, filtrate (liquid transition and material outlet transition；Make the transition material dissolving device, and it is positioned at the downstream of described wolframite device transition, connects with described wolframite device transition, has mixing reactor and dissolution filter；Make the transition filtrate processing means, it is positioned at the downstream of material dissolving device described transition, connect with material dissolving device described transition, there is filtrate crystallisation container transition and crystal filter, the filtrate crystallisation container that makes the transition has ammonium salt and adds entrance, crystal filter has the outlet of Ferrous ammonium sulfate crystal and crystalline mother solution exports, and crystalline mother solution outlet connects with sulfuric acid solution entrance.This utility model resolution ratio is high, energy consumption is low, pollution-free, low cost.
Description
Technical field
This utility model relates to the system that a kind of tungsten mineral material processes and prepares tungstate solution, particularly a kind of by sulfur
Acid treatment wolframite, with the method preparing tungstate solution, belongs to Tungsten smelting technical field.
Term " h 2 so 4 concentration controller " refers to, with H2SO4Quality meter H2SO4＞ 400g/L (preferably 500-
H 2 so 4 concentration controller 700g/L)；
Term " wolframite transition liquid-solid ratio controller " refers to, liquid-solid ratio be 2:1-10:1 (preferably 5:2-5:1, more excellent
Elect 3:1 as) wolframite transition liquid-solid ratio controller；
Term " wolframite temperature controller transition " refers to, temperature be ＞ 70 DEG C (preferably 70-100 DEG C, more preferably 90-100
DEG C) wolframite transition temperature controller；
Term " wolframite isomerization time controller " refers to, the time is ＞ 3h (preferably 3-10h, more preferably 5-
Wolframite isomerization time controller 8h)；
Term " wolframite Task-size Controlling device " refers to, the wolframite Task-size Controlling device of no more than 100 μm (preferably ＜ 30 μm)；
Term " ammonium salt solution consistency controller " refers to, concentration is with theoretical gauge excess ＞ 50g/L (preferably excess ＞
Ammonium salt solution consistency controller 100g/L)；
Term " sodium salt solution consistency controller " refers to, the theoretical gauge that concentration consumes with wolframic acid filter cake is not less than theoretical amount
Sodium salt solution consistency controller；
Term " transition material dissolution liquid-solid ratio controller " refers to, liquid-solid ratio be 2:1-6:1 (preferably 3:1-5:1, more preferably
Material dissolution transition liquid-solid ratio controller 3:1)；
Term " material leaching temperature controller transition " refers to, temperature is thing transition of 10-50 DEG C (preferably 15-35 DEG C)
Material leaching temperature controller；
Term " material dissolution response time controller transition " refers to, the described response time is 0.5-5h (preferably 1-3h)
Material dissolution transition response time controller；
Term " transition, filtrate processed ammonium salt theoretical amount controller " refers to, ammonium salt is selected from ammonium sulfate, ammonia, ammonium carbonate, carbon
Filtrate transition of acid hydrogen ammonium (preferably sulfuric acid ammonium) processes ammonium salt theoretical amount controller；
Term " transition filtrate treatment temperature controller " refers to, temperature be 50-80 DEG C (preferably 55-80 DEG C, more preferably 60-
70 DEG C) filtrate treatment temperature controller transition；
Term " WO3Mass percent " refer to, containing WO3Mass percent is the WO of the preferred ＞ of 10%-75% 40%3Quality
Percentage ratio controller；
Term " ammonium salt solution entrance " refers to, ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc.
Containing energy and Ca2+Form the ammonium salt solution entrance (preferably sal volatile entrance) of the anion of settlement；
Term " sodium salt solution entrance " refers to, sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate, sodium phosphate etc.
Containing energy and Ca2+Form the sodium salt solution entrance (preferably sodium carbonate entrance) of the anion of settlement；
Term " sulfuric acid solution addition controller " refers to, the theoretical gauge consumed with ammonium tungstate is not less than the sulfur of theoretical amount
Acid solution addition controller；
Term " reaction temperature controller " refers to, the reaction temperature controller of 45-95 DEG C；
Term " mixing speed controller " refers to, the mixing speed control of 50-80 rev/min (preferably 60-65 rev/min)
Device processed.
Background technology
Industrial, the essential mineral of tungstenic is wolframite and scheelite.Although wolframite reserves are few, account for gross reserves not enough
30%, but wolframite resource is prone to exploitation, selects smelting difficulty little, has innate advantage for comparing scheelite.
For the process technique of wolframite, mainly have following several:
Soda pressure leaching method, by tungsten mineral material and soda (Na at a temperature of 180-230 DEG C2CO3) solution carries out instead
Should, make tungsten enter solution with sodium tungstate form, and ferrum, calcium, manganese enter slag phase with carbonate (part ferrum is with oxide) form, from
And realizing initial gross separation, the method is applicable to process scheelite and Scheelite-Wolframite Mixed Mine, improves soda consumption and adds appropriate
Wolframite just can be processed under conditions of NaOH.But, soda pressure leaching method temperature requirement is high, requires that liquid-solid ratio is big, phase simultaneously
Answer the ground big energy consumption of ore pulp equipment volume high, and, wolframite and Na2CO3The reaction of solution is more complicated, is actually needed more
Na2CO3, discomposing effect is poor more than scheelite.
NaOH decomposition technique, by the WO in wolframite3All it is converted into solubility sodium tungstate and enters aqueous solution, and ferrum, manganese, calcium
Separate with tungsten Deng all entering slag with forms such as the oxide of indissoluble or hydroxide.The method mainly for the treatment of wolframite,
During processing scheelite, with wolframite that calcium content is high, alkali consumption is big, causes a large amount of harmful salt discharge, and processing cost is high, and
Being easy to back reaction during slurry dilution, residue washing, slag tungstenic increases.Alkali decomposition process processes wolframite technology
Maturation, is widely used, though but alkali consumption relatively soda pressure leaching method reduced, but still the 1.5-of Need Hierarchy Theory amount multiple
4.5 times, separate for follow-up tungsten alkali and alkali circulation brings difficulty.
Hydrochloric acid decomposition technique, by the WO in wolframite3Precipitating with the form of wolframic acid, ferrum, manganese enter with soluble-salt
Solution, thus realize separating.Hydrochloric acid decomposition method flow process is short, low cost, but hydrochloric acid volatilization is serious in catabolic process, operating environment
Deteriorate, Cl-Serious to equipment corrosion, have a large amount of containing Cl simultaneously-Discharge of wastewater, causes environmental pollution.
Other decomposition technique report processing wolframite is less." the wolframite acid of Zhao Zhongwei seminar of Central South University research
Method novel technology for extracting is studied ", utilize sulphuric acid to replace HCl treatment wolframite, but it uses limit edging when processing wolframite
Leaching, higher to equipment requirements, and add hydrochloric acid or NaCl to improve resolution ratio, the most inherently solve Cl-Corrosion
The problem volatilized with HCl, and less to the further treatment research of subsequent solution and wolframic acid.
Utility model content
The purpose of this utility model be to provide a kind of by sulfuric acid treatment wolframite to prepare the system of tungstate solution, its point
Solution rate is high, energy consumption is low, pollution-free, low cost, easy to operate, environmental friendliness.
To this end, this utility model provides a kind of system being prepared tungstate solution by sulfuric acid treatment wolframite, its feature
It is, including:
Wolframite transition device, its have isomerization container and transition filter, this isomerization container has sulphuric acid
Solution inlet, wolframite entrance and the outlet of isomerization liquid, this transition filter there is isomerization liquid entrance, filtrate transition goes out
Mouth and material outlet transition；
Make the transition material dissolving device, and it is positioned at the downstream of described wolframite device transition, with described wolframite device transition
Connection, has mixing reactor and dissolution filter, and this mixing reactor has material inlet transition, ammonium salt or sodium salt solution and enters
Mouth and dissolution taphole, it is molten that this dissolution filter has dissolution solution inlet, sludge outlet, ammonium tungstate solution or sodium tungstate
Liquid exports；And
Transition filtrate processing means, it is positioned at the downstream of material dissolving device described transition, with described material dissolution transition
Device connects, and has filtrate crystallisation container and crystal filter transition, and filtrate crystallisation container had ammonium salt and added entrance transition this, should
Crystal filter has the outlet of Ferrous ammonium sulfate crystal and crystalline mother solution exports, and crystalline mother solution outlet is with sulfuric acid solution entrance even
Logical.
Preferably, material outlet transition is the outlet of wolframic acid filter cake.
Preferably, h 2 so 4 concentration controller, wolframite liquid-solid ratio controller transition, wolframite temperature transition are also included
Controller, wolframite isomerization time controller and/or wolframite Task-size Controlling device.
Preferably, also include that ammonium salt solution consistency controller or sodium salt solution consistency controller, the material dissolution that makes the transition are liquid-solid
Than controller, material leaching temperature controller transition and/or material dissolution response time controller transition.
Preferably, also include make the transition filtrate process ammonium salt theoretical amount controller, transition filtrate treatment temperature controller and/or
Pressure controller.
Preferably, described wolframite entrance is Scheelite-Wolframite Mixed Mine entrance；Described wolframite entrance has containing WO3Quality hundred
Proportion by subtraction controller.
Preferably, ammonium tungstate solution outlet purifies with crystallisation vessel, described crystal filter and a separator successively with one
Connection, this crystal filter has APT solid outlet and crystalline mother solution outlet；Crystalline mother solution outlet enters with one second sulfuric acid solution
Mouthful connection, this separator has wolframic acid outlet and sinks tungsten mother liquor outlet, and wolframic acid outlet connects with material dissolving device transition, sinks tungsten
Mother liquor outlet and a calcium carbonate add entrance, a reaction temperature controller, a time controller, material dissolving device described transition even
Logical.
Preferably, the second sulfuric acid solution entrance has sulfuric acid solution addition controller.
Preferably, transition, filtrate processing means had stirring paddle, and this stirring paddle is folding paper, Bu Lumajinshi or ribbon
Formula.
Preferably, this stirring paddle has mixing speed controller.
This utility model uses sulphuric acid to decompose wolframite (mainly with FeWO4Meter), react such as formula (1), by wolframite
WO3With H2SO4Form precipitation, ferrum, manganese etc. enter solution；Process in leaching adds ammonium salt or sodium salt, wolframic acid is converted into
Tungstates, as a example by adding ammonium carbonate, reaction is such as formula (2)；In the sulphuric acid filtrate with ferrous sulfate, add ammonium salt, obtain sulphuric acid
Ferrous ammonium crystal, filtrate fills into return after sulphuric acid and processes wolframite ammonium sulfate as a example by adding ammonium sulfate, and reaction is such as formula (3).
H2SO4+FeWO4=FeSO4+H2WO4 (1)
H2WO4+(NH4)2CO3=(NH4)2WO4+H2O+CO2 (2)
FeSO4+(NH4)2SO4+6H2O=(NH4)2SO4·FeSO4·6H2O (3)
Compared with prior art, this utility model has the advantage that
(1) use sulfuric acid treatment wolframite, overcome Cl in tradition hydrochloric acid decomposition technique-Seriously corroded and HCl volatilization are asked
Topic；
(2) adjuvant used is common ammonium salt and sodium salt, is conveniently easy to get, it is easy to large-scale production；
(3) during dissolution obtains ammonium tungstate solution, carry out at normal temperatures, it is easy to produce, save energy and reduce the cost and its point
Solution rate is up to more than 98.5%；
(4) during dissolution obtains sodium tungstate solution, carry out at normal temperatures, it is easy to produce, and the consumption of sodium salt is
During theoretical amount, slag tungstenic is less than 4%, largely reduces the consumption of sodium salt, alleviates the processing load of follow-up sodium salt；
(5) achieving the comprehensive utilization of material, it is sub-that the ferrous sulfate that transition, filtrate produced in processing can be used for extracting sulfuric acid
Ferrum ammonium, non-pollutant discharge, environmental friendliness；
(6) equipment is simple, easy to operate, it is easy to industrial applications.
(7) combination of " wolframite transition " and " material dissolution transition " two steps, not only can realize normal pressure operation and have
Effect reduces energy consumption, and total overall reaction process does not all have rigors to reaction unit, it is simple to implement industrialization.
(8) the low-grade wolframite of high impurity, black tungsten flotation tailing, Scheelite-Wolframite Mixed Mine can be processed.
(9) tungsten recovery rate is stable more than 98%, up to more than 99.5% during the higher scheelite of process, and supplies
Consuming few, economy is strong.
Accompanying drawing explanation
Fig. 1 is that the structural principle according to the system being prepared tungstate solution by sulfuric acid treatment wolframite of the present utility model shows
It is intended to.
Detailed description of the invention
For ease of understanding this utility model, it is as follows that this utility model enumerates embodiment.Described embodiment only helps reason
Solve this utility model, be not construed as concrete restriction of the present utility model.In the case of without departing from this utility model technological thought,
According to ordinary skill knowledge and customary means, make various replacement and change, model of the present utility model all should be included in
In enclosing.
Include as it is shown in figure 1, prepared the system of tungstate solution by sulfuric acid treatment wolframite:
Wolframite device 10 transition, it has isomerization container 11 and filter 12 transition, this isomerization container 11
Having sulfuric acid solution entrance 13, wolframite entrance 14 and an isomerization liquid outlet 15, this, filter 12 had isomerization transition
Liquid entrance 16, filtrate (liquid 17 transition and material outlet 18 transition；
Make the transition material dissolving device 20, and it has mixing reactor 21 and dissolution filter 22, and this mixing reactor 21 has
Having material inlet 23 transition, ammonium salt or sodium salt solution entrance 24 and dissolution taphole 25, this dissolution filter 22 has dissolution
Solution inlet 26, sludge outlet 27, ammonium tungstate solution or sodium tungstate solution outlet 28；And
Transition filtrate processing means 30, it has filtrate crystallisation container 31 and crystal filter 32 transition, this transition filtrate
Crystallisation vessel 31 has ammonium salt and adds entrance 33, material inlet 36 transition and liquid to be filtered outlet 37, and this crystal filter 32 has
There are liquid to be filtered entrance 38, Ferrous ammonium sulfate crystal outlet 34 and crystalline mother solution outlet 35, crystalline mother solution outlet 35 and sulphuric acid
Solution inlet 13 connects.
Transition, material outlet 18 was the outlet of wolframic acid filter cake.
Particularly, wolframite device 10 transition also includes:
H 2 so 4 concentration controller 1, its range is at least with H2SO4Quality meter H2SO4＞ 400g/L, preferably 500-
700g/L；
Wolframite liquid-solid ratio controller 2 transition, its range is at least 2:1-10:1, preferably 5:2-5:1, and more preferably 3:
1；
Wolframite temperature controller 3 transition, its range is at least temperature ＞ 70 DEG C, preferably 70-100 DEG C, more preferably 90-
100℃；
Wolframite isomerization time controller 4, its range is at least ＞ 3h, preferably 3-10h, more preferably 5-8h；
And/or,
Wolframite Task-size Controlling device 5, its range is at least not more than 100 μm, preferably ＜ 30 μm.
Transition, material dissolving device 20 also included:
Ammonium salt consistency controller 6, its range is at least concentration with theoretical gauge excess ＞ 50g/L, preferably excess ＞ 100g/
L, or sodium salt solution consistency controller 6, its range is at least concentration and is not less than theoretical with the theoretical gauge that wolframic acid filter cake consumes
Amount；
Make the transition material dissolution liquid-solid ratio controller 7, and its range is at least 2:1-6:1, preferably 3:1-5:1, more preferably 3:1；
Make the transition material leaching temperature controller 8, and its range is at least 10-50 DEG C, preferably 15-35 DEG C；And/or,
Make the transition material dissolution response time controller 9, and its range is at least 0.5-5h, preferably 1-3h.
Transition, filtrate processing means 30 also included:
Transition, filtrate processed ammonium salt theoretical amount controller 51, and ammonium salt is selected from ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, excellent
Select ammonium sulfate；
Make the transition filtrate treatment temperature controller 52, and its range is at least 50-80 DEG C, preferably 55-80 DEG C, more preferably 60-70
℃；And/or,
Pressure controller 53.
Described wolframite entrance 14 is Scheelite-Wolframite Mixed Mine entrance；
Described wolframite entrance 14 has containing WO3Mass percent controller 19, its range is at least 10%-75%, excellent
Select ＞ 40%.
Described ammonium salt solution entrance 24 contains for ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc.
Energy and Ca2+Form the ammonium salt solution entrance of the anion of settlement, preferably sal volatile entrance；
Described sodium salt solution entrance 24 contains for sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate, sodium phosphate etc.
Energy and Ca2+Form the sodium salt solution entrance of the anion of settlement, preferably sodium carbonate entrance.
Ammonium tungstate solution outlet 28, purification are sequentially communicated with crystallisation vessel 41, crystal filter 42 and separator 43, this knot
Brilliant filter 42 has APT solid outlet 44 and crystalline mother solution outlet 45；Crystalline mother solution outlet 45 and the second sulfuric acid solution entrance
46 connections, this separator 43 has wolframic acid outlet 47 and heavy tungsten mother liquor outlet 48, wolframic acid outlet 47 and material dissolving device transition
20 connections, heavy tungsten mother liquor outlet 48 and CaCO3Add entrance 49,45-95 DEG C of reaction temperature controller 54, time controller 55, turn
Type material dissolving device 20 connects.Second sulfuric acid solution entrance 46 has sulfuric acid solution addition controller 56, and its range is at least
Theoretical gauge for consuming with ammonium tungstate is not less than theoretical amount.Transition, filtrate processing means 30 had stirring paddle, such as, and stirring paddle
Can be folding paper or Bu Lumajinshi, helical-ribbon type.
Stirring paddle has mixing speed controller 57, and its range is at least 50-80 rev/min, preferably 60-65 rev/min
Clock.
Embodiment 1:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 10min, granularity ＜
30μm；Compound concentration is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 2:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 10min, granularity ＜
30μm；Compound concentration is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 30 DEG C, reacts 2h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 3:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
20μm；Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, the response time
7h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 150g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 25 DEG C, reacts 1h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 4:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
20μm；Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, the response time
7h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 25 DEG C, reacts 1h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 4% in filtering residue.
Embodiment 5:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 200g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 35 DEG C, reacts 3h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 6:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 35 DEG C, reacts 3h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 7:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 40 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 8:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 40 DEG C, reacts 2h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 2% in filtering residue.
Embodiment 9:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 10:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 30 DEG C, reacts 2h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 11:
Certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 56%), Scheelite-Wolframite Mixed Mine and water 1:1 are in vibromill wet grinding
10min, granularity ＜ 30 μm；Compound concentration is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature
100 DEG C, response time 8h, it is filtrated to get material transition, its X-ray diffraction analysis result shows, present in grog, thing is the most not
Containing CaWO4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 12:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:2 are in vibromill wet grinding 10min, granularity ＜
30μm；Compound concentration is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 30 DEG C, reacts 2h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 13:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.3 are in vibromill wet grinding 20min, granularity
＜ 20 μm；Compound concentration is the sulfuric acid solution of 500g/L；Being mixed with solution by mineral aggregate, liquid-solid ratio 3:1, temperature 95 DEG C, during reaction
Between 7h, be filtrated to get material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 150g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 25 DEG C, reacts 1h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 14:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.2 are in vibromill wet grinding 20min, granularity
＜ 20 μm；Compound concentration is the sulfuric acid solution of 500g/L；Being mixed with solution by mineral aggregate, liquid-solid ratio 3:1, temperature 95 DEG C, during reaction
Between 7h, be filtrated to get material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 25 DEG C, reacts 1h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 4% in filtering residue.
Embodiment 15:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
4h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 200g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 35 DEG C, reacts 3h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 16:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.1 are in vibromill wet grinding 15min, granularity
＜ 25 μm；Compound concentration is the sulfuric acid solution of 400g/L；Being mixed with solution by mineral aggregate, liquid-solid ratio 5:1, temperature 90 DEG C, during reaction
Between 8h, be filtrated to get material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 35 DEG C, reacts 3h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 17:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 40 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 18:
Certain scheelite (WO3Weight/mass percentage composition is 56%), scheelite and water 1:1 are in vibromill wet grinding 20min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 300g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 50 DEG C, reacts 6h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 2% in filtering residue.
Embodiment 19:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 2:5 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 350g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by above-mentioned transition
Material adds solution, and liquid-solid ratio is 3:1, and temperature is 60 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ in filtering residue
1%.
Embodiment 20:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜
25μm；Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, the response time
8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, temperature
It is 30 DEG C, reacts 2h, be filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
According to this utility model, the implementation of the preparation system of tungstate solution includes step:
Make wolframite make the transition, carry out normal pressure or reaction under high pressure, obtain make the transition filtrate and material transition, to overcome tradition hydrochloric acid
Cl in decomposition technique-Seriously corroded and HCl volatilization problems；
Making filtrate transition be comprehensively utilized, solid phase can be used for producing side-product, and non-pollutant discharge, liquid phase circulation
Make the transition to participating in wolframite；
Make material dissolution transition, use the adjuvant being conveniently easy to get and being prone to large-scale production, operation under normal pressure or high pressure, obtain
To tungstate solution.
Particularly, following steps are specifically included:
1) wolframite transition: the sulfuric acid solution of preparation certain mass concentration, suitable liquid-solid ratio and temperature are controlled, will be certain
The wolframite of granularity adds and carries out isomerization in this sulfuric acid solution, after reaction terminates, filters, and obtains make the transition filtrate and thing transition
Material i.e. wolframic acid filter cake；
2) material dissolution transition: prepare certain density ammonium salt or sodium salt solution, control suitable liquid-solid ratio and temperature, will
Above-mentioned transition material with this ammonium salt or sodium salt solution hybrid reaction, after reaction certain time, filter, obtain ammonium tungstate solution or
(filtering residue Main Ingredients and Appearance is stone-like pulse to sodium tungstate solution, such as silicon dioxide, calcium mineral, remaining concrete composition and wolframite used
Raw material is relevant, if containing valuable constituent, can recycle further)；
3) transition, filtrate processed: adds the ammonium salt of theoretical amount to transition in filtrate, makes (NH in solution4)2SO4With FeSO4?
React under uniform temperature and occur that epitaxial, standing are cooled to Ferrous ammonium sulfate crystal and are fully crystallized precipitation, reduced pressure to solution surface
Filter, obtains Ferrous ammonium sulfate crystal, after filling into sulphuric acid, returns wolframite transformation process in crystalline mother solution.
Preferably, sulfuric acid treatment wolframite is used；
The solid phase that described solid phase can be used for producing in side-product is ferrous sulfate, and side-product is Ferrous ammonium sulfate；
Described tungstate solution is ammonium tungstate solution or sodium tungstate solution；
Described adjuvant is common ammonium salt and sodium salt；And/or, transition, material was wolframic acid filter cake,
When wolframite makes the transition, the sulfuric acid solution of preparation certain mass concentration, control suitable liquid-solid ratio and temperature, will be certain
The wolframite of granularity adds and carries out isomerization in this sulfuric acid solution, after reaction terminates, by being filtrated to get filtrate transition and turning
Type material, wherein,
Described wolframite can also be Scheelite-Wolframite Mixed Mine, containing WO3Mass percent is 10%-75% (preferably WO3Matter
Amount percentage ratio is ＞ 40%)；
Described certain mass concentration is with H2SO4Quality meter, H2SO4＞ 400g/L, preferably 500-700g/L；
Described suitable liquid-solid ratio is 2:1-10:1, preferably 5:2-5:1, more preferably 3:1；
Described suitable temperature is ＞ 70 DEG C, preferably 70-100 DEG C, more preferably 90-100 DEG C；
The wolframite isomerization time is ＞ 3h, preferably 3-10h, more preferably 5-8h；And/or
Described certain particle size is not more than 100 μm, the most described certain particle size ＜ 30 μm.
Preferably, when making that transition, filtrate was comprehensively utilized, filtrate added to transition the ammonium salt of theoretical amount, makes in solution
(NH4)2SO4With FeSO4Reacting at a certain temperature and epitaxial occur to solution surface, it is complete that standing is cooled to Ferrous ammonium sulfate crystal
Holocrystalline separates out, and filtration under diminished pressure obtains Ferrous ammonium sulfate crystal, after filling into sulphuric acid, returns wolframite and made the transition in crystalline mother solution
Journey, wherein,
Described ammonium salt is ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, preferably sulfuric acid ammonium；And/or,
Described uniform temperature is 50-80 DEG C, preferably 60-70 DEG C.
Preferably, when making material dissolution transition, prepare certain density ammonium salt or sodium salt solution, control suitable liquid-solid ratio
And temperature, by above-mentioned transition material with this ammonium salt or sodium salt solution hybrid reaction, after reaction certain time, filter tungsten by obtaining
Acid ammonium solution or sodium tungstate solution, wherein,
Described ammonium salt is that ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc. are containing energy and Ca2+Shape
Become the ammonium salt of the anion of settlement, preferably ammonium carbonate；Described certain density ammonium salt, its concentration is with theoretical gauge, mistake
Amount ＞ 50g/L, is preferably excess ＞ 100g/L；Described sodium salt be sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate,
Sodium phosphates etc. are containing energy and Ca2+Form the sodium salt of the anion of settlement, preferably sodium carbonate；Described certain density sodium
Salt, the theoretical gauge that its concentration consumes with wolframic acid filter cake, not less than theoretical amount；
The most suitable described liquid-solid ratio is 2:1-6:1, preferably 3:1-5:1, more preferably 3:1；
Described suitable temperature is 10-50 DEG C, preferably 15-35 DEG C；And/or,
Described reaction certain time is 0.5-5h, preferably 1-3h.
Preferably, the process step of described ammonium tungstate solution is as follows:
1) ammonium tungstate solution purified, crystallize, obtain APT solid and crystalline mother solution；
2) in crystalline mother solution, sulfuric acid solution is added, isolated wolframic acid and heavy tungsten mother solution, wolframic acid return thing described transition
Material dissolution step；
3) heavy tungsten mother solution will add CaCO3, 45-95 DEG C react certain time (more than 0.5 hour, preferably 1.5-2.5
Hour) after, filter, obtain returning liquid containing ammonium, return liquid containing ammonium and return described material dissolution transition step.
Preferably, step 2) in, contained ammonium tungstate reacts generation wolframic acid precipitation to sulfuric acid solution with crystalline mother solution, and sulphuric acid is molten
The theoretical gauge that the addition of liquid consumes with ammonium tungstate, not less than theoretical amount.Preferably, step 3) in, reaction temperature is 55-80
DEG C, preferably 60-70 DEG C.
Preferably, step 3) in, it being stirred with stirring paddle during reaction, stirring paddle is folding paper or Bu Lumajinshi, spiral shell
Belt.
Preferably, the mixing speed of stirring paddle is 50-80 rev/min, preferably 60-65 rev/min.
Implementation of the present utility model specifically includes that
1) wolframite transition, the sulfuric acid solution of preparation certain mass concentration, the wolframite of certain particle size is added this solution
In react, liquid-solid ratio is 2:1-10:1, and temperature is ＞ 70 DEG C, and the response time is ＞ 3h, reaction terminate after be filtrated to get filter
Liquid and material transition；
2) material dissolution transition, prepares certain density ammonium salt or sodium salt solution, and liquid-solid ratio is 2:1-6:1, and temperature is 10-
50 DEG C, react 0.5-5h, after having reacted, be filtrated to get ammonium tungstate solution or sodium tungstate solution；
3) process of filtrate, adds theoretical amount in filtrate and obtains ammonium salt, (the NH in solution4)2SO4With FeSO4Necessarily
At a temperature of react and to solution surface epitaxial occur, stand and be cooled to Ferrous ammonium sulfate crystal and separate out completely, decompression excess obtains sulfur
Acid ferrous ammonium crystal, after filtrate fills into sulphuric acid, return processes wolframite.
Preferably, step 1) described in wolframite, it is also possible to be Scheelite-Wolframite Mixed Mine, containing WO3Mass percent is
10%-75%, granularity is not more than 100 μm, preferably WO3Mass percent is ＞ 40%, granularity ＜ 30 μm；
Preferably, step 1) described in the sulfuric acid solution of certain mass concentration, concentration is with H2SO4Quality meter, H2SO4＞
400g/L, preferably 500-700g/L；
Preferably, step 1) described in liquid-solid ratio be 2:1-10:1, preferably 3:1-5:1, more preferably 3:1；
Preferably, step 1) described in temperature be ＞ 70 DEG C, preferably 70-100 DEG C, more preferably 90-100 DEG C；
Preferably, step 1) described in response time be ＞ 3h, preferably 3-10h, more preferably 5-8h；
Preferably, step 2) described in ammonium salt be ammonia, ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate,
A series of ammonium salt such as ammonium phosphate, preferably ammonium carbonate, ammonia；
Preferably, step 2) described in certain density ammonium salt, concentration, with theoretical gauge, excess ＞ 50g/L, was preferably
Amount ＞ 100g/L；
Preferably, step 2) described in sodium salt be sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., silicon
Acid a series of sodium salt such as sodium, sodium phosphate, preferably sodium carbonate, sodium hydroxide；
Preferably, step 2) described in certain density sodium salt, concentration is theoretical gauge, not less than theoretical amount；
Preferably, step 2) described in liquid-solid ratio be 2:1-6:1, preferably 3:1-5:1, more preferably 3:1；
Preferably, step 2) described in temperature be 10-50 DEG C, preferably 15-35 DEG C；
Preferably, step 2) described in response time be 0.5-5h, preferably 1-3h；
Preferably, step 3) described in ammonium salt be ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, preferably ammonium sulfate；
Preferably, step 3) described in temperature be 50-80 DEG C, preferably 60-70 DEG C.
Claims (10)
1. one kind by sulfuric acid treatment wolframite to prepare the system of tungstate solution, it is characterised in that including:
Wolframite transition device, its have isomerization container and transition filter, this isomerization container has sulfuric acid solution
Entrance, wolframite entrance and the outlet of isomerization liquid, this transition filter have isomerization liquid entrance, filtrate (liquid transition and
Make the transition material outlet；
Make the transition material dissolving device, and it is positioned at the downstream of described wolframite device transition, connects with described wolframite device transition,
There is mixing reactor and dissolution filter, this mixing reactor have material inlet transition, ammonium salt or sodium salt solution entrance and
Dissolution taphole, this dissolution filter has dissolution solution inlet, sludge outlet, ammonium tungstate solution or sodium tungstate solution and goes out
Mouthful；And
Transition filtrate processing means, it is positioned at the downstream of material dissolving device described transition, with material dissolving device described transition
Connection, has filtrate crystallisation container and crystal filter transition, and filtrate crystallisation container had ammonium salt and added entrance transition this, this crystallization
Filter has the outlet of Ferrous ammonium sulfate crystal and crystalline mother solution exports, and crystalline mother solution outlet connects with sulfuric acid solution entrance.
System the most according to claim 1, it is characterised in that transition, material outlet was the outlet of wolframic acid filter cake.
System the most according to claim 1, it is characterised in that also include that h 2 so 4 concentration controller, wolframite make the transition
Liquid-solid ratio controller, wolframite temperature controller transition, wolframite isomerization time controller and/or wolframite Task-size Controlling
Device.
System the most according to claim 1, it is characterised in that also include that ammonium salt solution consistency controller or sodium salt solution are dense
Degree controller, material dissolution liquid-solid ratio controller transition, material leaching temperature controller transition and/or material dissolution reaction transition
Time controller.
System the most according to claim 1, it is characterised in that also include make the transition filtrate process ammonium salt theoretical amount controller,
Make the transition filtrate treatment temperature controller and/or pressure controller.
System the most according to claim 1, it is characterised in that described wolframite entrance is Scheelite-Wolframite Mixed Mine entrance；Institute
State wolframite entrance to have containing WO3Mass percent controller.
System the most according to claim 1, it is characterised in that ammonium tungstate solution outlet purifies and crystallisation vessel, institute with one
Stating crystal filter and a separator is sequentially communicated, this crystal filter has APT solid outlet and crystalline mother solution outlet；Crystallization
Mother liquor outlet and the connection of one second sulfuric acid solution entrance, this separator has wolframic acid outlet and the tungsten mother liquor outlet that sinks, and wolframic acid exports
Connecting with material dissolving device transition, heavy tungsten mother liquor outlet and a calcium carbonate add entrance, a reaction temperature controller, time control
Device processed, described material dissolving device connection transition.
System the most according to claim 7, it is characterised in that the second sulfuric acid solution entrance has sulfuric acid solution addition control
Device processed.
System the most according to claim 8, it is characterised in that transition, filtrate processing means had stirring paddle, this stirring paddle
For folding paper, Bu Lumajinshi or helical-ribbon type.
System the most according to claim 9, it is characterised in that this stirring paddle has mixing speed controller.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477288A (en) * | 2021-12-16 | 2022-05-13 | 中南大学 | Comprehensive utilization and treatment method for wolframite resources |
| CN116555595A (en) * | 2023-07-03 | 2023-08-08 | 赣南科技学院 | Novel decomposing agent for scheelite and method for decomposing scheelite |
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2016
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477288A (en) * | 2021-12-16 | 2022-05-13 | 中南大学 | Comprehensive utilization and treatment method for wolframite resources |
| CN114477288B (en) * | 2021-12-16 | 2024-01-09 | 中南大学 | Comprehensive utilization processing method for wolframite resources |
| CN116555595A (en) * | 2023-07-03 | 2023-08-08 | 赣南科技学院 | Novel decomposing agent for scheelite and method for decomposing scheelite |
| CN116555595B (en) * | 2023-07-03 | 2023-10-13 | 赣南科技学院 | Decomposing agent for scheelite and method for decomposing scheelite |
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