CN204162450U - A kind of system preparing ammonium tungstate solution - Google Patents
A kind of system preparing ammonium tungstate solution Download PDFInfo
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- CN204162450U CN204162450U CN201420580760.XU CN201420580760U CN204162450U CN 204162450 U CN204162450 U CN 204162450U CN 201420580760 U CN201420580760 U CN 201420580760U CN 204162450 U CN204162450 U CN 204162450U
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Abstract
A kind of system preparing ammonium tungstate solution, it is characterized in that, its leaching device and thin grog outlet, have leaching ore deposit agent entrance, leaching slurry outlet, feedback gas recovery port, the solution recovery port for separating of washing, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth.Also comprise raw material granularity controller, leaching agent consistency controller, Seed charge controller, leaching agent add-on controller, leach pH value controller, absolute pressure controller, extraction temperature controller, extraction time controller, initial liquid-solid ratio controller, final Leaching Systems liquid-solid ratio controller.The utility model can low cost, wastewater zero discharge, prepare the ammonium tungstate solution of higher concentration expeditiously.
Description
Technical field
The utility model relates to a kind of system preparing ammonium tungstate solution, belongs to tungsten metallurgical technology field.
Term " grog " refers to containing (AO)
x(WO
3)
y(BO)
zmaterial, wherein A, B are divalent metal element, (x+z)/y=3.
What term " raw material granularity controller " referred to makes the granularity of raw material be not more than 200 μm of controllers, and those skilled in the art can select its concrete structure.
Term " Seed charge controller " refers to and makes Seed charge be the controller of 0-15g/L, and those skilled in the art can select its concrete structure.
Term " leaching agent consistency controller " refers to and makes leaching agent concentration be greater than 10g-NH
4 +/ 100g-H
2the controller of O, those skilled in the art can select its concrete structure.
Term " leaching agent add-on controller " refers to that leaching agent add-on is at least makes AO and BO in grog be converted into the controller of 1.0 times of corresponding difficulty soluble salt aequum (theoretical amount), and those skilled in the art can select its concrete structure.
Term " leaching pH value controller " refers to the controller making Leaching Systems pH be not less than 8, and those skilled in the art can select its concrete structure.
Term " absolute pressure controller " refers to the controller making the absolute pressure of Leaching Systems be not less than 1atm, and those skilled in the art can select its concrete structure.
Term " extraction temperature controller " refers to and makes extraction temperature be the controller of 15 ~ 100 DEG C, and those skilled in the art can select its concrete structure.
Term " extraction time controller " refers to and makes extraction time be the controller of 0.1 ~ 10.0h, and those skilled in the art can select its concrete structure.
Term " initial liquid-solid ratio controller " refers to the controller making the initial liquid-solid ratio of Leaching Systems be not less than 1:1mL/g, and those skilled in the art can select its concrete structure.
Term " final Leaching Systems liquid-solid ratio controller " refers to that the liquid-solid ratio controlling final Leaching Systems is the controller of 3:1 ~ 10:1mL/g, and those skilled in the art can select its concrete structure.
Background technology
Ammonium tungstate solution is the important intermediate material of one in Tungsten smelting industry preparation APT process.
At present, the ammonium tungstate solution preparation method of industrial employing mainly contains:
1)
soda pressuring cooking method, take mainly tungsten ore as raw material, decomposed by caustic soda or the method such as soda pressuring cooking, first obtained sodium tungstate solution, then made the transition as ammonium tungstate solution by ion-exchange or solvent extraction, the method Problems existing comprises: greatly, supplies consumption is large for caustic soda or soda consumption; Extraction temperature is high, and operational condition is harsher; Transformation process produces a large amount of brine wastes, and environmental pollution is heavier; Complex process, cost is high;
2)
soda sintered method, tungsten minerals is mixed with soda and additive, leaches after sintering at 800 DEG C and obtain sodium tungstate solution, made the transition by removal of impurities, obtain ammonium tungstate solution.Although the method significantly can reduce the consumption of soda and reduce the discharge of acid-base waste fluid, return slag is many, energy consumption is high, cost is high, is progressively replaced by wet method;
3)
acid decomposition, obtain thick wolframic acid after tungsten minerals acid being decomposed, then be converted to ammonium tungstate solution, although these class methods significantly can reduce discharge of wastewater, exist equipment corrosion, acid pollution, to problems such as the bad adaptability of raw material;
4)
ammonium salt decomposition methodmainly comprise Neutral ammonium fluoride to decompose and ammonium phosphate decomposition, this method process sheelite directly can obtain ammonium tungstate solution, and impurity leaching yield is low, sheelite closed cycle smelting and wastewater zero discharge can be realized, but, have employed the expensive fluorine of price comparison, phosphorus compound, and its consumption is comparatively large, causes economy poor;
5)
tungsten ore roasting-ammoniacal liquor lixiviation process(CN102642871A), roasting after being mixed with silicon-dioxide by tungsten concentrate, obtains the burned material containing tungstic oxide, after ammoniacal liquor leaches, obtain ammonium tungstate solution, the emission problem of waste water can be solved, but ammoniacal liquor poor stability, easy decomposition, causes Leaching Systems pressure higher.
In prior art, prepare the various technique of ammonium tungstate solution or discharge with having to high pollution for pursuing low cost, or zero release must be exchanged for high cost.If allow discharge be processed thoroughly, need fund input even produce make a profit more than.Therefore, low cost, in order to profit, is selected by various enterprises, but serious environment pollution, destroy ecology, be degrading the survival condition of the mankind, be difficult to realize Sustainable development.
Desirable state it is possible to develop low cost, wastewater zero discharge, the high efficiency novel process preparing ammonium tungstate solution.But although prior art experienced by long-term arduous exploration, all not having can be accomplished always.
Utility model content
The purpose of this utility model is to provide a kind of system preparing ammonium tungstate solution, its can low cost, wastewater zero discharge, prepare the ammonium tungstate solution of higher concentration expeditiously.
For this reason, the utility model provides a kind of system preparing ammonium tungstate solution, it is characterized in that, its leaching device and thin grog outlet, have leaching agent entrance, leaching slurry outlet, feedback gas recovery port, the solution recovery port for separating of washing, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth.
Preferably, raw material granularity controller and leaching agent consistency controller is at least also comprised.
Preferably, Seed charge controller is also comprised.
Preferably, leaching agent add-on controller is also comprised.
Preferably, leaching pH value controller is also comprised.
Preferably, absolute pressure controller is also comprised.
Preferably, extraction temperature controller is also comprised.
Preferably, extraction time controller is also comprised.
Preferably, initial liquid-solid ratio controller is also comprised.
Preferably, final Leaching Systems liquid-solid ratio controller is also comprised.
According to the utility model, supplies are no longer expendable consumed products, the leaching agent of leaching process recycles, even if the excessive use of supplies, corresponding processing step also no longer direct outer row after completion of the reaction, no longer need to use corresponding acid or alkali neutralization, therefore, supplies consumption significantly reduces, and production cost significantly reduces.
According to the utility model, after the pre-treatment to tungsten mineral material, adopt volatile salt-bicarbonate of ammonia-ammonium tungstate solution system or volatile salt-ammonium tungstate-CO
2solution system or volatile salt-ammoniacal liquor-ammonium tungstate solution system leaches tungsten minerals grog, and leaching condition is gentle, and leaching agent is cheap, be easy to get, and supplies reusable edible, can eliminate the discharge of wastewater in production process in theory.
Accompanying drawing explanation
Fig. 1 is according to the system architecture schematic diagram preparing ammonium tungstate solution of the present utility model.
Embodiment
Below, will in conjunction with specific embodiments, further the utility model is described.
As shown in Figure 1, raw material preparation facilities 10 has raw mineral materials dosage entrance 11 and dosage entrance 12 (being preferably also provided with mineralising dosage entrance 13), raw material fine mill (containing vortex mixer) 14, raw material outlet 15 and leached mud receiving port 16; Roasting kiln (stove) 20 exports 15 through feeding measurement device with raw material silo and raw material and is communicated with, and has heating unit, attemperator (preferably also comprising refrigerating unit 21) and thick grog outlet 22; Grog fine mill 30 exports 22 through grog storehouse with thick grog and is communicated with, and has ore grinding device and thin grog outlet 31; Leaching device 40 and thin grog outlet 31, there is leaching ore deposit agent entrance 41, leaching slurry outlet 42, feedback gas recovery port, solution recovery port, slag phase washings recovery port 45, crystal seed entrance (preferably, also comprise commercial carbon dioxide and pass into mouth 47) for separating of washing;
According to the utility model, the preprocessing process of tungsten mineral material also comprises:
Raw material preparation controller 100, wherein, under the control of proportion scale controller 101, by levigate to tungsten mineral material (sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry) and a certain amount of calcareous material (i.e. mineralizer), afterwards, mix, to obtain raw material; And
The raw material prepared, under the effect of maturing temperature controller 201, are carried out roasting, obtain grog by sinter leaching controller 200.Raw material preparation controller 100 makes the add-on of calcareous material be at least by generation Ca
3wO
6and/or Ca
2feWO
61.0 times of theoretical amount, are preferably 1.1-1.5 doubly, are more preferably 1.2 times.
When raw material are prepared, the mineralizer allocated into is fluorochemical, is preferably Calcium Fluoride (Fluorspan).Raw material preparation controller 100 makes the add-on of described mineralizer be the 0.5-7% (mass percent) of dry tungsten mineral material amount quality, is preferably 1 ~ 3%.
Raw material preparation controller 100 has raw mill fine granularity controller 102, and the granularity making raw material levigate is less than 96 μm, is preferably less than 45 μm.
Sinter leaching controller 200 has maturing temperature controller 201, makes maturing temperature be not less than 500 DEG C, is preferably not less than 800 DEG C (maturing temperature is 800 ~ 1050 DEG C, is preferably 850 ~ 950 DEG C).
Sinter leaching controller 200 has roasting time controller 202, makes roasting time be 0.5-8.0h, is preferably 1.0 ~ 3.0h.Raw material are roasting 2.0h at 850 ~ 950 DEG C.
Sinter leaching controller 200 has calcination atmosphere controller 203, makes: when described tungsten mineral material is the sheelite containing Fe is lower, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere; And described tungsten mineral material is when being containing higher sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or the tungsten slurry of Fe, calcination atmosphere be neutral or reducing atmosphere, preferably neutral atmosphere.
According to the utility model, to contain (AO)
x(WO
3)
y(BO)
zmaterial as raw material (grog), wherein A, B are divalent metal element, (x+z)/y=3.
Raw material granularity controller 401 makes the granularity of raw material be not more than 200 μm, is preferably less than 45 μm;
Seed charge controller 402 makes Seed charge be 0-15g/L, and preferred Seed charge is 10g/L, and crystal seed is carbonate, preferred calcium carbonate or the material containing calcium carbonate;
The selection principle of leaching agent solution at least comprises: with in the reactant of described raw material containing the gas again synthesizing this leaching agent can be participated in, leaching agent itself contains NH
4 +, concentration is greater than 10g-NH
4 +/ 100g-H
2o;
Leaching agent add-on controller 403 makes leaching agent add-on be at least 1.0 times of theoretical amount, described volatile salt-bicarbonate of ammonia and volatile salt-ammonium tungstate-ammonium bicarbonate soln system, bicarbonate of ammonia add-on is at least 1.0 times of theoretical amount, is preferably 1.1 ~ 1.4 times;
Leaching pH value controller 404 makes Leaching Systems pH be not less than 8;
Leach in confined conditions, absolute pressure controller 405 makes the absolute pressure of Leaching Systems be not less than 1atm, and the absolute pressure of Leaching Systems is preferably 1.5-2.5atm, is more preferably 2atm.
Extraction temperature controller 406 makes extraction temperature be 15 ~ 100 DEG C, is more preferably 30 ~ 50 DEG C,
Extraction time controller makes extraction time be 0.1 ~ 10.0h, is more preferably 0.5 ~ 4.0h,
Initial liquid-solid ratio controller 407 makes the initial liquid-solid ratio of Leaching Systems be not less than 1:1mL/g, is preferably 10:1-4:1mL/g,
The mode of being fed in raw material by multistage reduces the final liquid-solid ratio of Leaching Systems, and after having leached, leaching slurry, through separating, washing, obtains ammonium tungstate solution.Preferably, fed in raw material by two sections, the liquid-solid ratio controlling final Leaching Systems is 3:1 ~ 4:1mL/g.
According to the utility model, Ca
3wO
6be easy to decompose, so that prepare ammonium tungstate solution in ammonium salt solution.The method preparing ammonium tungstate solution of the present utility model comprises: by Ca
3wO
6and/or Ca
2feWO
6mixture join in ammonium salt solution system, leach in confined conditions, after having leached, leaching slurry, through separating, washing, obtains ammonium tungstate solution.
Preferably, described Ca
3wO
6and Ca
2feWO
6can be the pure compound of synthetic, also can be tungsten mineral material obtain after treatment containing Ca
3wO
6and/or Ca
2feWO
6mixture; Ca
3wO
6and/or Ca
2feWO
6the granularity of mixture be not more than 200 μm, be preferably less than 45 μm; Described ammonium salt solution system can be volatile salt-ammonium bicarbonate soln system, volatile salt-ammonium tungstate-ammonium bicarbonate soln system, volatile salt-CO
2solution system, also can be volatile salt-ammonium tungstate-CO
2solution system, volatile salt-ammonia soln system, volatile salt-ammonium tungstate-ammonia soln system.
Preferably, Ca is leached by volatile salt-ammonium bicarbonate soln system or volatile salt-ammonium tungstate-ammonium bicarbonate soln system or volatile salt-ammonia soln system or volatile salt-ammonium tungstate-ammonia soln system
3wO
6or Ca
2feWO
6time, the absolute pressure of Leaching Systems is not particularly limited; With volatile salt-CO
2, or volatile salt-ammonium tungstate-CO
2solution system leaches Ca
3wO
6or Ca
2feWO
6time, in leaching process, pass into CO
2, the absolute pressure controlling Leaching Systems is not less than 1atm, is preferably 1.5-2.5atm, is more preferably 2atm.
Preferably, Leaching Systems volatile salt concentration is greater than 20g-(NH
4)
2cO
3/ 100g-H
2o, is preferably saturated sal volatile.Volatile salt-ammonium tungstate-bicarbonate of ammonia and volatile salt-ammonium tungstate-CO
2in solution system, ammonium tungstate concentration is also not particularly limited, as long as meet Ca
3wO
6or Ca
2feWO
6in tungsten fully leach after, in gained solution, ammonium tungstate concentration is no more than its solubleness in this system.
Preferably, described volatile salt-bicarbonate of ammonia and volatile salt-ammonium tungstate-ammonium bicarbonate soln system, bicarbonate of ammonia add-on is at least 1.0 times of theoretical amount, is preferably 1.1 ~ 1.4 times.
Preferably, control Leaching Systems pH and be not less than 8.Extraction temperature is not particularly limited, as long as can make Ca
3wO
6or Ca
2feWO
6in tungsten fully leach, be preferably 15 ~ 100 DEG C, be more preferably 30 ~ 50 DEG C; Extraction time is not particularly limited, as long as can make Ca
3wO
6or Ca
2feWO
6in tungsten fully leach, be preferably at 0.1 ~ 10.0h, be more preferably 0.5 ~ 4.0h.
Preferably, the initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/g, is preferably 10:1-4:1mL/g.
Preferably, the mode can fed in raw material by multistage, reduces the final liquid-solid ratio of Leaching Systems, and feed in raw material preferably by two sections, the liquid-solid ratio controlling final Leaching Systems is 3:1 ~ 4:1mL/g.
Preferably, described sal volatile also can by ammonium bicarbonate soln and ammoniacal liquor or ammoniacal liquor and CO
2some substitute.
Ca in ammonium carbonate salt solution system
3wO
6leaching main chemical reactions comprise:
Ca
3WO
6+3(NH
4)
2CO
3+2H
2O＝3CaCO
3+(NH
4)
2WO
4+4NH
4OH (1)
Ca
3WO
6+(NH
4)
2CO
3+2CO
2＝3CaCO
3+(NH
4)
2WO
4(2)
Ca
3WO
6+3NH
4HCO
3＝3CaCO
3+(NH
4)
2WO
4+NH
4OH+H
2O (3)
Ca
3WO
6+2NH
3+3CO
2+H
2O＝3CaCO
3+(NH
4)
2WO
4(4)
2NH
4OH+CO
2＝(NH
4)
2CO
3+H
2O (5)
(NH
4)
2CO
3+CO
2+H
2O＝2NH
4HCO
3(6)
As (the NH in solution
4)
2wO
4when concentration is higher, especially there is a large amount of NH
4oH deposits in case, (NH
4)
2wO
4the high reactivity CaCO that can generate with leaching process
3there is secondary reaction, generate the CaWO being difficult to be leached by ammonium carbonate salt solution
4, cause tungsten loss.Principal reaction may be:
CaCO
3+2NH
4OH Ca(OH)
2+(NH
4)
2CO
3(7)
Ca(OH)
2+(NH
4)
2WO
4＝CaWO
4+2NH
4OH (8)
Reaction (8) is more easily carried out, and generally reacts (7) and be difficult to carry out, but at Ca
3wO
6leaching process in newborn CaCO
3active high, reaction (7) is then likely carried out, and carries out NH along with leaching process
4oH and (NH
4)
2wO
4concentration constantly increase, reaction (7) and react (8) strengthened, finally cause (NH
4)
2wO
4when concentration is higher, the loss of tungsten increases.Therefore, in airtight Leaching Systems, CO is passed into
2, the NH in rapid neutralization solution
4oH, makes reaction (7) be suppressed; Simultaneously by adding CaCO
3crystal seed, makes newborn CaCO
3grow up rapidly at seed surface, reduce its activity, the carrying out of further inhibited reaction (7).Thus be expected to (the NH simultaneously obtaining high density
4)
2wO
4solution and high tungsten leaching yield.
In addition, in enclosed system, CO is passed into
2, can also CO be improved
2utilization ratio.
embodiment 1:
By calcium carbonate (analytical pure) and tungstic oxide (analytical pure) by CaO/WO
3after molecular ratio 3.1:1 mixing, in retort furnace, at 800 DEG C, react 2h synthesize Ca
3wO
6, the Ca of synthesis
3wO
6levigate rear mistake 325 mesh sieve (<45 μm).Then 5.0g Ca is taken
3wO
6with 50g analytical pure volatile salt, join together in micro-reaction still, then add 50mL deionized water, airtight and unlatching is stirred, at 80 DEG C, leach 0.5h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 92.90%.
embodiment 2:
Take the Ca of synthesis in 5.0g embodiment 1
3wO
6, 0.5g analytical pure calcium carbonate and 30g analytical pure volatile salt, join together in micro-reaction still, then add 50mL deionized water, and pH value is 9.7, and airtight and unlatching is stirred, at 15 DEG C, leach 10h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 96.16%.
embodiment 3
Take the Ca of synthesis in 5.0g embodiment 1
3wO
6, 0.5g analytical pure calcium carbonate and 30g analytical pure volatile salt, join together in micro-reaction still, then add 50mL deionized water, and airtight and unlatching is stirred, at 30 DEG C, leach 4h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 98.76%.
embodiment 4:
Certain sheelite (WO
3mass percentage is 49.53%, CaO mass percentage 19.10%), calcium carbonate (analytical pure) is by CaO/WO
3after mixing that molecular ratio 3.1:1 is levigate, then in retort furnace, react 2h at 800 DEG C and obtain grog, X-ray diffraction analysis result shows, tungsten is wherein all with Ca
3wO
6form exist, by levigate for grog rear mistake 325 mesh sieve (-45 μm).Take 50.0g grog, adding 50ml volatile salt concentration is in the leach liquor of 500g/L, agitation leach 2 hours at 100 DEG C in airtight stirring digester.After leaching completes, adopt vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 86.39%.
embodiment 5:
By 19.0g WO
3(analytical pure) is all dissolved in 100mL ammoniacal liquor (analytical pure, 25 ~ 28%) at 80 DEG C in encloses container, obtained ammoniacal liquor-ammonium tungstate solution.Take 10.0g analytical pure calcium carbonate, in the micro-reaction still joined, then add 50mL ammoniacal liquor-ammonium tungstate solution (NH
4oH concentration is approximately 170g/L, WO
3concentration is 190g/L), airtight and unlatching is stirred, and reacts 4h at 80 DEG C.After having reacted, reaction ore pulp adopts vacuum filtration, records WO in filtrate
3concentration is 45.16g/L, shows the WO in solution
3lose in a large number due to secondary reaction.The X-ray diffraction result of reaction slag shows that dominant is wherein CaWO mutually
4and CaCO
3.
embodiment 6:
By 19.0g WO
3(analytical pure) is all dissolved into 100mL ammoniacal liquor (analytical pure at 80 DEG C in encloses container, 25 ~ 28%) in, passing into the pH that carbon dioxide (technical pure) adjusts solution is again about 9.5, obtained volatile salt-ammonium tungstate solution.Take 10.0g analytical pure calcium carbonate, add in micro-reaction still, then add 50mL volatile salt-ammonium tungstate solution (WO
3concentration is 190g/L), airtight and unlatching is stirred, and reacts 4h at 80 DEG C.After having reacted, reaction ore pulp adopts vacuum filtration, records WO in filtrate
3concentration is 186g/L, and comparative example 4, illustrates and increases stripping system carbonate concentration, can slow down secondary reaction.
embodiment 7:
Take 5g grog, and 1.0g analytical pure calcium carbonate and 100g analytical pure volatile salt, join in beaker together, then add 100mL deionized water, open and stir, and pass into CO
2gas, the pH of maintenance system is about 9.0, at 50 DEG C, leach 1h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 96.73%.In conjunction with the embodiments 4 ~ 6, illustrate that passing into carbonic acid gas at leaching process effectively can suppress secondary reaction.
embodiment 8:
Take grog obtained in 5.0g embodiment 3,0.75g analytical pure calcium carbonate and 50g analytical pure volatile salt, join in micro-reaction still together, add 50mL deionized water again, airtight unlatching is stirred, leach 1h at 80 DEG C after, then add grog obtained in 5.0g embodiment 3, continue to leach 1h at 80 DEG C.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 96.40%.
embodiment 9
Take the Ca of 2.5g synthesis
3wO
6, 0.5g analytical pure calcium carbonate and 30g analytical pure volatile salt, join together in micro-reaction still, then add 50mL deionized water, and airtight and unlatching is stirred, at 30 DEG C, leach 1h; Add the Ca of 2.5g synthesis again
3wO
6, leach 4h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 98.98%.
embodiment 10
Take 5g grog, 0.5g analytical pure calcium carbonate and 30g analytical pure volatile salt, join together in micro-reaction still, then add 50mL deionized water, and airtight and unlatching is stirred, at 40 DEG C, leach 1h; Add 5g grog again and pass into CO
2, leach 10h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 92.33%.
embodiment 11
Take 5g grog, 0.5g analytical pure calcium carbonate and 30g analytical pure volatile salt, join in micro-reaction still together, then add 50mL deionized water and 5ml ammonium tungstate solution (WO
3concentration 160g/L), airtight and unlatching is stirred, at 40 DEG C, leach 1h; Add the volatile salt of 2g grog and 10g again, leach 10h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 95.33%.
embodiment 12:
Take grog obtained in 5.0g embodiment 3,0.5g analytical pure calcium carbonate and 50g analytical pure volatile salt, join in micro-reaction still together, then add volatile salt-ammonium tungstate solution (WO obtained in 50mL embodiment 4
3concentration is 190g/L), airtight and pass into CO
2gas, the pressure of maintenance system is 2atm, opens and stirs, at 80 DEG C, leach 1h.After leaching completes, leaching slurry adopts vacuum filtration, with deionized water wash filter cake three times.The leaching yield of tungsten is 98.73%.
embodiment 13:
Take 100.0g sheelite (WO
3mass percentage is 60.34%, Fe mass percentage is 4.73%), by generating Ca
3wO
6and Ca
2feWO
6allocate calcium carbonate into, after carrying out levigate mixing, obtain raw material for 1.1 times of theoretical amount.Then, in stoving oven, under weak reducing atmosphere, 950 DEG C of roasting 4.0h, obtain grog, and its X-ray diffraction analysis result shows, the tungstenic thing existed in grog only has Ca mutually
3wO
6and Ca
2feWO
6.Grog ball mill is levigate, and cross 325 mesh sieves (grog granularity≤45 μm), take 5.0g levigate after grog put into agitation leach equipment, add 50ml unsaturated carbonate ammonium solution, and add bicarbonate of ammonia according to 1.5 times of theoretical amount; 4h is reacted at 62 DEG C.After reaction terminates, leach ore pulp suction filtration, with 100mL pure water filter cake 5 times.The leaching yield of tungsten is 97.78%.
embodiment 14:
By levigate for the grog ball mill obtained after sintering in embodiment 13 to crossing 80 mesh sieves (granularity <200 μm), take the levigate rear grog of 5.0g, put into ball milling leaching plant, add 50ml ammoniacal liquor-sal volatile, (NH in solution
3mass percentage be 5%, volatile salt concentration is 400g/L); 5h is reacted at 40 DEG C.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 95.71%.
embodiment 15:
By levigate for the grog ball mill obtained after sintering in embodiment 13 to crossing 800 mesh sieves (granularity <18 μm), take the levigate rear grog of 10.0g, put into agitation leach equipment, add 50ml ammoniacal liquor-volatile salt-ammonium tungstate solution (NH in solution
3mass percentage be 20%, volatile salt concentration is 400g/L, WO
3concentration is 100g/L); 5h is reacted at 40 DEG C.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 98.49%.
embodiment 16:
Take levigate rear grog in 5.0g embodiment 12, put into agitation leach equipment, (volatile salt concentration is 400g/L, WO to add 50ml volatile salt-ammonium tungstate solution
3concentration is 120g/L), then add the bicarbonate of ammonia of theoretical amount 1.3 times; 5h is leached at 40 DEG C.After leaching terminates, leach ore pulp suction filtration, use pure water filter cake.The leaching yield of tungsten is 97.24%.
Above embodiment is only and exemplarily Ca is described
3wO
6, Ca
2feWO
6can be leached by ammonium carbonate salt solution system, it should be appreciated by those skilled in the art, the tungsten in tungsten ore makes tungsten wherein change Ca into through other pretreatment process
3wO
6and/or Ca
2feWO
6after, also by ammonium carbonate salt solution system, tungsten wherein can be leached, obtain ammonium tungstate solution.
The utility model provides a kind of system preparing ammonium tungstate solution, it is characterized in that, its leaching device and thin grog outlet, have leaching ore deposit agent entrance, leaching slurry outlet, feedback gas recovery port, the solution recovery port for separating of washing, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth.Also comprise raw material granularity controller, leaching agent consistency controller, Seed charge controller, leaching agent add-on controller, leach pH value controller, absolute pressure controller, extraction temperature controller, extraction time controller, initial liquid-solid ratio controller, final Leaching Systems liquid-solid ratio controller.The utility model can low cost, wastewater zero discharge, prepare the ammonium tungstate solution of higher concentration expeditiously.
According to the utility model, decompose Ca by ammonium salt solution system
3wO
6and/or Ca
2feWO
6, make Ca and Fe wherein be separately converted to CaCO
3and/or FeCO
3enter slag phase, tungsten enters solution with the form of ammonium tungstate, adds bicarbonate of ammonia or passes into CO
2suppress ammonium tungstate in solution to generate calcium wolframate with the calcium carbonate reaction in slag, thus realize being separated of calcium and tungsten, the ammonium tungstate solution of acquisition higher concentration and higher WO
3leaching yield.
According to the utility model, do not need through step transition, directly can obtain ammonium tungstate solution, the decomposition nut liquid of separating out after APT through evaporative crystallization can return Leaching Systems, realize solution circulated, fundamentally solve the problem that in APT production process, wastewater discharge is many, environmental pollution is heavy, and reduce supplies consumption.
A kind of system preparing ammonium tungstate solution that the utility model provides, it is to contain (AO)
x(WO
3)
y(BO)
zmaterial as raw material, wherein A, B are divalent metal element; Seed charge is 0-15g/L; The selection principle of leaching agent solution at least comprises: with in the reactant of described raw material containing the material again synthesizing this leaching agent can be participated in, leaching agent itself contains NH
4 +, concentration is greater than 10g-NH
4 +/ 100g-H
2o; Leaching agent add-on is at least 1.0 times of theoretical amount; Control Leaching Systems pH and be not less than 8; Leach in confined conditions, the absolute pressure of Leaching Systems is not less than 1atm, extraction temperature is 15 ~ 100 DEG C, extraction time is 0.1 ~ 10.0h, the initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/g, and the mode of being fed in raw material by multistage reduces the final liquid-solid ratio of Leaching Systems, after having leached, leaching slurry, through separating, washing, obtains ammonium tungstate solution.
Preferably, comprise following technical characteristic at least one of them:
Leaching agent itself is also containing CO
3 2-and/or HCO
3 -, the gas participating in again synthesizing this leaching agent is NH
3, CO
2; X+z+y=4; Preferably, x=3, y=1, z=0; Or, x=2, y=1, z=1;
A is Ca, and B is Fe (or Mn), or A and B is Ca; And/or
CO is passed in enclosed system
2.
According to the utility model, tungsten directly enters solution with ammonium tungstate form, does not need to make the transition through ion-exchange or solvent extraction; In the auxiliary material used, carbonic acid gas and volatile salt are cheaply easy to get, and utilization ratio is high; Leaching process pressure is low, simple to operate; Obtained ammonium tungstate solution concentration is higher, to the preparation process moment-less influence of follow-up ammonium paratungstate; Ammonium carbonate salts system is easy to circulation in APT preparation process, thus fundamentally economy can solve the pollution problem caused due to discharge of wastewater in applicable industry production, realizes cleaner production.
According to the utility model, with " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO
2" or " volatile salt-ammonium tungstate-ammoniacal liquor " system as leach liquor non-obvious, this is because: weak acid or the process of the weakly alkaline system raw material (or processing efficiency is extremely low) that chemical reactivities such as sheelite, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry are not lower.Tungsten smelting industry generally adopts at present strong acid (example hydrochloric acid) or highly basic (as sodium hydroxide) gonosome system and leach tungsten mineral material under high temperature, hyperbaric environment, and " volatile salt-bicarbonate of ammonia-ammonium tungstate ", " volatile salt-ammonium tungstate-CO
2", " volatile salt-ammonium tungstate-ammoniacal liquor " all belong to weakly alkaline system, raw material has to pass through transition step could realize leaching.
According to the utility model, select " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO
2" or " volatile salt-ammonium tungstate-ammoniacal liquor " solution system leach; Leaching Systems material changes into ammonia and carbonic acid gas after crystallisation step; just can return and fill into Leaching Systems; thus realize its recycle; thoroughly abandoned traditional open circuit not circulating system or open circuit half circulating system; eradicated discharge of wastewater, really achieved green metallurgical.
According to the utility model, not only leach liquid-solid higher time the tungsten leaching effect that can obtain, when leaching liquid-solid ratio and being less than 10, in grog, the leaching yield of tungsten does not also decline, WO in gained leach liquor
3concentration still can suitability for industrialized production economically.
According to the utility model, adopt volatile salt-bicarbonate of ammonia-ammonium tungstate solution system or volatile salt-ammonium tungstate-CO
2solution system or volatile salt-ammonium tungstate-ammonia soln system leach grog, when leaching liquid-solid ratio is 4, still can obtain good tungsten leaching effect, WO in gained leach liquor
3concentration is higher, is very adapted to suitability for industrialized production.
Exploration and practice for many years shows, those skilled in the art does not have motivation go research by tungsten mineral material transition and how to make the transition.Even if take into account transition, the performance that selectively leaching agent and raising are leached still relates to multiple factor, these factors are all often restrictions mutually, interactional, be not separate, after orthogonal design, still have infinite may combining, and enough excellent technical scheme can not be predicted, " experiment of limited number of time " can not obtain the suitable value of each factor, and enough excellent technical scheme is not " obviously ".
It is important to note that these embodiments are only examples, in order to the utility model to be described, instead of limit scope of the present utility model.It should be appreciated by those skilled in the art: if do not depart from principle of the present utility model and method, the amendment carry out details and the form of technical solutions of the utility model and replacement, all within protection domain of the present utility model.
Claims (10)
1. prepare the system of ammonium tungstate solution for one kind, it is characterized in that, its leaching device and thin grog outlet, have leaching ore deposit agent entrance, leaching slurry outlet, feedback gas recovery port, the solution recovery port for separating of washing, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth.
2. system according to claim 1, is characterized in that, at least also comprises raw material granularity controller and leaching agent consistency controller.
3. system according to claim 1, is characterized in that, also comprises Seed charge controller.
4. system according to claim 1, is characterized in that, also comprises leaching agent add-on controller.
5. system according to claim 1, is characterized in that, also comprises leaching pH value controller.
6. system according to claim 1, is characterized in that, also comprises absolute pressure controller.
7. system according to claim 1, is characterized in that, also comprises extraction temperature controller.
8. system according to claim 1, is characterized in that, also comprises extraction time controller.
9. system according to claim 1, is characterized in that, also comprises initial liquid-solid ratio controller.
10. system according to claim 1, is characterized in that, also comprises final Leaching Systems liquid-solid ratio controller.
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|---|---|---|---|
| CN201420580760.XU CN204162450U (en) | 2014-10-09 | 2014-10-09 | A kind of system preparing ammonium tungstate solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420580760.XU CN204162450U (en) | 2014-10-09 | 2014-10-09 | A kind of system preparing ammonium tungstate solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819513A (en) * | 2016-03-17 | 2016-08-03 | 湖南懋天世纪新材料有限公司 | Method utilizing cold wind aeration technology to produce ultrafine APT |
| CN109368661A (en) * | 2018-11-28 | 2019-02-22 | 湖南懋天世纪新材料有限公司 | Surplus NH in alkalinity extraction tungsten production4+Utilization method |
| CN113816427A (en) * | 2021-10-21 | 2021-12-21 | 江西钨业股份有限公司 | Crystallization process of ammonium paratungstate |
-
2014
- 2014-10-09 CN CN201420580760.XU patent/CN204162450U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819513A (en) * | 2016-03-17 | 2016-08-03 | 湖南懋天世纪新材料有限公司 | Method utilizing cold wind aeration technology to produce ultrafine APT |
| CN105819513B (en) * | 2016-03-17 | 2017-09-19 | 湖南懋天世纪新材料有限公司 | A kind of method that ultra-fine APT is produced with cold wind aeration system |
| CN109368661A (en) * | 2018-11-28 | 2019-02-22 | 湖南懋天世纪新材料有限公司 | Surplus NH in alkalinity extraction tungsten production4+Utilization method |
| CN113816427A (en) * | 2021-10-21 | 2021-12-21 | 江西钨业股份有限公司 | Crystallization process of ammonium paratungstate |
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