CN104386754B - A kind of technique for preparing ammonium tungstate solution - Google Patents

A kind of technique for preparing ammonium tungstate solution Download PDF

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Publication number
CN104386754B
CN104386754B CN201410527623.4A CN201410527623A CN104386754B CN 104386754 B CN104386754 B CN 104386754B CN 201410527623 A CN201410527623 A CN 201410527623A CN 104386754 B CN104386754 B CN 104386754B
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ammonium
leaching
carbonate
technique according
solution
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CN104386754A (en
Inventor
李小斌
崔源发
周秋生
李建圃
齐天贵
徐双
刘桂华
林国荣
彭志宏
李继红
徐向明
王霖
王一霖
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Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
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Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten

Abstract

A kind of technique for preparing ammonium tungstate solution, it is with containing (AO)x(WO3)y(BO)zMaterial as raw material, wherein A, B is divalent metal element, (x+z)/y=3;The granularity of raw material is not more than 200 μm;Seed charge is 0 15g/L;The selection principle for leaching agent solution comprises at least:With containing NH in itself containing the material that can participate in recombining the leaching agent, leaching agent in the reactant of the raw material4 +, concentration is more than 10g NH4 +/100g‑H2O;Leaching agent addition is at least make AO and BO in clinker be converted into corresponding difficulty soluble salt aequum (theoretical amount) 1.0 times;Leaching Systems pH is controlled to be not less than 8;Leach in confined conditions, the absolute pressure of Leaching Systems is not less than 1atm, and extraction temperature is 15~100 DEG C, and extraction time is 0.1~10.0h, and the initial liquid-solid ratio of Leaching Systems is not less than 3:1mL/g, the final liquid-solid ratio of Leaching Systems is reduced by way of multistage charging, after the completion of leaching, leaching slurry obtains ammonium tungstate solution through separating, washing.The present invention can low cost, wastewater zero discharge, the ammonium tungstate solution for expeditiously preparing higher concentration.

Description

A kind of technique for preparing ammonium tungstate solution
Technical field
The present invention relates to a kind of technique for preparing ammonium tungstate solution, belong to tungsten metallurgical technology field.
Background technology
Ammonium tungstate solution is a kind of important intermediate material during the industrially prepared APT of Tungsten smelting.
At present, the ammonium tungstate solution preparation method industrially used mainly has:
1)Soda pressuring cooking method, mainly using tungsten ore as raw material, decomposed by caustic soda or the methods of soda pressuring cooking, made first Sodium tungstate solution, ammonium tungstate solution is then transformed into by ion exchange or solvent extraction, the problem of this method is present includes: Caustic soda or soda dosage are big, and supplies consumption is big;Extraction temperature is high, and operating condition is harsher;Transformation process produces a large amount of Brine waste, environmental pollution is heavier;Complex process, cost are high;
2)Soda sintered method, by tungsten mineral and soda and additive mixed sintering, then leach and obtain sodium tungstate solution, lead to Removal of impurities transition is crossed, obtains ammonium tungstate solution.Although this method can be greatly lowered the dosage of soda and reduce acid-base waste fluid Discharge, but return slag is more, high energy consumption, cost are high, is progressively substituted by wet method;
3)Acid decomposition, thick wolframic acid is obtained after tungsten mineral is decomposed with acid, ammonium tungstate solution is reconverted into, although such side Discharge of wastewater can be greatly reduced in method, but equipment corrosion, acid pollution be present, to the bad adaptability of raw material the problems such as;
4)Ammonium salt decomposition method, mainly include ammonium fluoride decomposition and ammonium phosphate decompose, method processing scheelite can be obtained directly Ammonium tungstate solution is obtained, and impurity leaching rate is low, it is possible to achieve scheelite closed cycle smelting and wastewater zero discharge, however, using The somewhat expensive fluorine of price, phosphorus compound, and its consumption is larger, cause economy poor;
5)Tungsten ore roasting-ammoniacal liquor lixiviation process(CN102642871A) it is calcined, obtains after, tungsten concentrate is mixed with silica Burned material containing tungstic acid, ammonium tungstate solution is obtained after ammoniacal liquor leaches, the emission problem that can solve waste water, but ammoniacal liquor is steady Qualitative difference, easily decompose, cause Leaching Systems pressure higher.
In the prior art, or the various techniques for preparing ammonium tungstate solution are arranged with having to high pollution to pursue low cost Put, otherwise zero-emission must be exchanged for high cost.If allowing discharge thoroughly to be handled, need to fund input even than life Production is made a profit more.Therefore, various enterprises is for profit, selection low cost, but seriously pollutes environment, destroys ecology, It is degrading the survival condition of the mankind, it is difficult to realize sustainable development.
Preferable state is can to develop low cost, zero-emission, the efficient new technology for preparing ammonium tungstate solution. However, although prior art experienced long-term arduous exploration, but always all can not be accomplished.
The content of the invention
It is an object of the invention to provide a kind of technique for preparing ammonium tungstate solution, its low cost, non-wastewater discharge, efficiently Rate.
Another object of the present invention is to provide a kind of method for preparing ammonium tungstate solution, and it can efficiently, cleanly Prepare the ammonium tungstate solution of higher concentration.
Therefore, the invention provides a kind of technique for preparing ammonium tungstate solution, it is with containing (AO)x(WO3)y(BO)zMaterial As raw material, wherein A, B is divalent metal element, (x+z)/y=3;The granularity of raw material is not more than 200 μm;Seed charge is 0-15g/L;The selection principle for leaching agent solution comprises at least:It can participate in recombining this with the reactant of the raw material containing The material of leaching agent, leaching agent contain NH in itself4 +, concentration is more than 10g-NH4 +/100g-H2O;Leaching agent addition is at least theory 1.0 times of amount;Leaching Systems pH is controlled to be not less than 8;Leach in confined conditions, the absolute pressure of Leaching Systems is not less than 1atm, extraction temperature are 15~100 DEG C, and extraction time is 0.1~10.0h, and the initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/ G, the final liquid-solid ratio of Leaching Systems is reduced by way of multistage charging, after the completion of leaching, leaching slurry obtains through separating, washing To ammonium tungstate solution.
Preferably, including following technical characteristic at least one:
Leaching agent also contains CO in itself3 2-And/or HCO3 -, the material for participating in recombining the leaching agent is NH3、CO2;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 are Ca;And/or
CO is passed through in enclosed system2
The exploration and practice of the present inventor for many years shows that those skilled in the art does not have motivation to go research that tungsten mineral is former Material makes the transition and how made the transition.Even if take into account transition, selectively leaching agent and improve leach performance be still related to it is multiple Factor, these factors often all mutually restrict, interactional, are not separate, still have after orthogonal design Infinite possibility combination, and technical scheme excellent enough can not be predicted, " experiment of limited number of time " can not possibly obtain each factor Appropriate value, technical scheme excellent enough is not " apparent ".
According to the present invention, tungsten directly enters solution with wolframic acid ammonium form, it is not necessary to turns by ion exchange or solvent extraction Type;In used auxiliary material, carbon dioxide and ammonium carbonate are cheap and easily-available, and utilization rate is high;Leaching process pressure is low, operation Simply;Obtained ammonium tungstate solution concentration is higher, to the preparation process moment-less influence of follow-up ammonium paratungstate;Ammonium carbonate salts system Be easy to circulate in APT preparation process, so as to fundamentally it is economical solve in applicable industry production due to discharge of wastewater and Caused pollution problem, realizes clean manufacturing.
According to the present invention, with " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " carbonic acid Ammonium-ammonium tungstate-ammoniacal liquor " system is non-obvious as leachate, because:Weak acid or alkalescent system do not handle white tungsten The relatively low raw material of the chemical reactivities such as ore deposit, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry (or treatment effeciency is extremely low).Tungsten smelting It is industrial typically to use strong acid (such as hydrochloric acid) or highly basic (such as sodium hydroxide) property system at present and soaked under high temperature, hyperbaric environment Go out tungsten mineral material, and " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate ", " ammonium carbonate-ammonium tungstate-CO2", " ammonium carbonate-ammonium tungstate-ammonia Water " belongs to alkalescent system, and raw material, which has to pass through transition step, could realize leaching.
According to the present invention, from " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " carbonic acid Ammonium-ammonium tungstate-ammoniacal liquor " solution system is leached, and Leaching Systems material changes into ammonia and carbon dioxide after crystallisation step, Just it can return and fill into Leaching Systems, so as to realize that it is recycled, thoroughly abandon traditional open circuit and circulating system or do not opened Road half cycle system, has eradicated discharge of wastewater, has been truly realized green metallurgical.
According to the present invention, the tungsten leaching effect that can have not only been obtained when leachate is admittedly higher, leaching, liquid-solid ratio is small When 10, the leaching rate of tungsten does not also decline in clinker, WO in gained leachate3Concentration still can economically industrialized production.
According to the present invention, using ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate solution system or ammonium carbonate-ammonium tungstate-CO2Solution System or ammonium carbonate-ammonium tungstate-ammonia spirit system leach clinker, when it is 4 to leach liquid-solid ratio, remain to obtain preferable tungsten Leaching effect, WO in gained leachate3Concentration is higher, is adapted to very much industrialized production.
According to the present invention, supplies are no longer expendable consumed products, and the leaching agent of leaching process recycles, even if auxiliary Help material to be excessively used, arrange corresponding processing step is also no longer directly outer after completion of the reaction, it is no longer necessary to acid corresponding to use or Person's alkali neutralizes, and therefore, supplies consumption is greatly decreased, and production cost is greatly reduced.
According to the present invention, after the pretreatment of tungsten mineral material, using ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate solution body System or ammonium carbonate-ammonium tungstate-CO2Solution system or ammonium carbonate-ammonium tungstate-ammonia spirit system leach tungsten mineral clinker, leaching Go out mild condition, leaching agent is cheap, is easy to get, and supplies reusable edible, can eliminate the waste water in production process in theory Discharge.
Brief description of the drawings
Fig. 1 is the system structure diagram for preparing ammonium tungstate solution according to the present invention.
Embodiment
Below, will in conjunction with specific embodiments, further the present invention will be described.
As shown in figure 1, raw material preparation facilities 10 has raw mineral materials dosage entrance 11 and dosage entrance 12 (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 connects through feeding measurement device and raw material silo with raw material outlet 15, and there is heater, attemperator (preferably also to include Cooling device 21) and thick clinker outlet 22;Clinker fine mill 30 connects through clinker storehouse with thick clinker outlet 22, has ore grinding Device and thin clinker outlet 31;Leaching device 40 and thin clinker outlet 31, there is leaching agent entrance 41, leaching slurry to export 42nd, feedback gas recovery port, the solution recovery port for separating, washing, slag phase cleaning solution recovery port 45, crystal seed entrance be (preferably Ground, in addition to commercial carbon dioxide are passed through mouth 47);
According to the present invention, the preprocessing process of tungsten mineral material also includes:
Raw material prepare controller 100, wherein, under the control of proportion scale controller 101, by tungsten mineral material (white tungsten Ore deposit, wolframite, Scheelite-Wolframite Mixed Mine, and/or tungsten slurry) it is levigate with a certain amount of calcareous material (i.e. mineralizer), afterwards, mixing Uniformly, to obtain raw material;And
Sinter leaching controller 200, in the presence of sintering temperature controller 201, the raw material prepared are calcined, Obtain clinker.Raw material prepare controller 100 and the addition of calcareous material are at least by generation Ca3WO6Or Ca2FeWO6It is theoretical 1.0 times of amount, preferably more preferably 1.1-1.5 times, 1.2 times.
When raw material are prepared, the mineralizer of supplying is fluoride, it is therefore preferable to calcirm-fluoride.Raw material, which prepare controller 100, to be made The addition for obtaining the mineralizer is the 0.5-7% (mass percent), preferably 1-3% of dry tungsten mineral material amount quality.
Raw material, which prepare controller 100, has raw mill fine granularity controller 102 so that the granularity that raw material are levigate is less than 96 μ M, preferably less than 45 μm.
Sinter leaching controller 200 has sintering temperature controller 201 so that sintering temperature is not less than 500 DEG C, preferably not Less than 800 DEG C (sintering temperature is 800~1050 DEG C, preferably 850~950 DEG C).
Sinter leaching controller 200 has roasting time controller 202 so that roasting time 0.5-8.0h, is preferably 1.0~3.0h.Raw material are calcined 2.0h at 850~950 DEG C.
Sinter leaching controller 200 has calcination atmosphere controller 203 so that roasting process is controllable to:Neutral atmosphere, Or oxidizing atmosphere or reducing atmosphere.
When described tungsten mineral material is containing Fe relatively low scheelites, calcination atmosphere is not particularly limited;And described tungsten When raw mineral materials is containing scheelite higher Fe, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, calcination atmosphere to be neutral or Reducing atmosphere, preferably neutral atmosphere.For the tungsten mineral material containing Fe, it is necessary to be calcined under neutral or reducing atmosphere, And cooled down under neutral or reducing atmosphere, it is calcined and cools down preferably under neutral atmosphere;Or for the tungsten containing wolframite Raw mineral materials makes iron therein be converted into Fe, it is necessary to be calcined in an oxidizing atmosphere2O3, manganese is converted into Mn2O3
According to the present invention, with containing (AO)x(WO3)y(BO)zMaterial as raw material, wherein A, B is divalent metal element, x For the natural number more than 2, y is natural number, and z is 0 or 1;X+z+y=4;Preferably, x=3, y=1, z=0;Or x=2, y =1, z=1.
Raw material granularity controller 401 causes the granularity of raw material to be not more than 200 μm, preferably less than 45 μm;
Seed charge controller 402 make it that Seed charge is 0-15g/L, and preferably Seed charge is 10g/L, crystal seed For carbonate, preferably calcium carbonate or the material containing calcium carbonate;
The selection principle for leaching agent solution comprises at least:It can participate in recombining this with the reactant of the raw material containing The gas of leaching agent, leaching agent contain NH in itself4 +, concentration is more than 10g-NH4 +/100g-H2O;
Leaching agent adds amount controller 403 and make it that leaching agent addition is at least 1.0 times of theoretical amount, and the ammonium carbonate- Ammonium hydrogen carbonate and ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, ammonium hydrogen carbonate addition is at least 1.0 times of theoretical amount, excellent Elect 1.1~1.4 times as;
Leaching pH value controller 404 causes Leaching Systems pH to be not less than 8;
Leach in confined conditions, absolute pressure controller 405 causes the absolute pressure of Leaching Systems to be not less than 1atm, soaks The absolute pressure for going out system is preferably 1.5-2.5atm, more preferably 2atm.
Extraction temperature controller 406 causes extraction temperature for 15~100 DEG C, more preferably 30~70 DEG C,
Extraction time controller causes extraction time to be 0.1~10.0h, more preferably 0.5~4.0h,
Initial liquid-solid ratio controller 407 causes the initial liquid-solid ratio of Leaching Systems to be not less than 1:1mL/g, preferably 10:1-4: 1mL/g,
The final liquid-solid ratio of Leaching Systems is reduced by way of multistage charging, after the completion of leaching, leaching slurry is through separation Washing, obtains ammonium tungstate solution.Preferably, by two sections of chargings, the liquid-solid ratio for controlling final Leaching Systems is 3:1~4:1mL/ g。
According to the present invention, Ca3WO6It is easily decomposes in ammonium salt solution, in order to prepare ammonium tungstate solution.The system of the present invention The method of standby ammonium tungstate solution includes:By Ca3WO6And/or Ca2FeWO6Mixed material be added in ammonium salt solution system, Leach under confined conditions, after the completion of leaching, leaching slurry obtains ammonium tungstate solution through separating, washing.
Preferably, the Ca3WO6And Ca2FeWO6Can be that artificial synthesized pure compound or tungsten mineral material pass through What is obtained after processing contains Ca3WO6And/or Ca2FeWO6Mixture;Ca3WO6And/or Ca2FeWO6Mixed material granularity not More than 200 μm, preferably less than 45 μm;Described ammonium salt solution system, can be ammonium carbonate-ammonium bicarbonate soln system, carbon Sour ammonium-CO2Solution system, ammonium carbonate-ammonia spirit system or ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, Ammonium carbonate-ammonium tungstate-CO2Solution system, ammonium carbonate-ammonium tungstate-ammonia spirit system.
Preferably, with ammonium carbonate-ammonium bicarbonate soln system or ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system or Ammonium carbonate-ammonia spirit system or ammonium carbonate-ammonium tungstate-ammonia spirit system leach Ca3WO6Or Ca2FeWO6When, leach body The absolute pressure of system is not particularly limited;With ammonium carbonate-CO2Or ammonium carbonate-ammonium tungstate-CO2Solution system leaches Ca3WO6Or Ca2FeWO6When, CO is passed through in leaching process2, control the absolute pressure of Leaching Systems to be not less than 1atm, preferably 1.5- 2.5atm, more preferably 2atm.
Preferably, Leaching Systems carbonic acid ammonium concentration is more than 20g- (NH4)2CO3/100g-H2O, preferably saturation ammonium carbonate Solution.Ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate and ammonium carbonate-ammonium tungstate-CO2In solution system, ammonium tungstate concentration is not also by special Limitation, as long as meeting Ca3WO6Or Ca2FeWO6In tungsten fully leach after, in resulting solution ammonium tungstate concentration be no more than its at this Solubility in system.
Preferably, the ammonium carbonate-ammonium hydrogen carbonate and ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, ammonium hydrogen carbonate add Enter 1.0 times that amount is at least theoretical amount, preferably 1.1~1.4 times.
Preferably, described ammonium carbonate-ammoniacal liquor and ammonium carbonate-ammonium tungstate-ammonia spirit system, the addition of ammoniacal liquor is not yet It is particularly limited, as long as the pH that leach initial system can be adjusted to more than 8.0, preferably leaches NH in initial system3 Content be 0%~28%, more preferably 5%~20%, more preferably 5%~10%;
Preferably, Leaching Systems pH is controlled to be not less than 8.Extraction temperature is not particularly limited, as long as can make Ca3WO6Or Ca2FeWO6In tungsten fully leach, preferably 15~100 DEG C, more preferably 30~50 DEG C;Extraction time is not limited especially System, as long as Ca can be made3WO6Or Ca2FeWO6In tungsten fully leach, preferably in 0.1~10.0h, more preferably 0.5~ 4.0h。
Preferably, the initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/g, preferably 10:1-4:1mL/g.
Preferably, it can reduce the final liquid-solid ratio of Leaching Systems by way of multistage charging, preferably pass through two sections Charging, the liquid-solid ratio for controlling final Leaching Systems are 3:1~4:1mL/g.
Preferably, described sal volatile also can be by ammonium bicarbonate soln and ammoniacal liquor or ammoniacal liquor and CO2Part substitutes.
Ca in ammonium carbonate salt solution system3WO6Leaching main chemical reactions include:
Ca3WO6+3(NH4)2CO3+2H2O=3CaCO3+(NH4)2WO4+4NH4OH (1)
Ca3WO6+(NH4)2CO3+2CO2=3CaCO3+(NH4)2WO4 (2)
Ca3WO6+3NH4HCO3=3CaCO3+(NH4)2WO4+NH4OH+H2O (3)
Ca3WO6+2NH3+3CO2+H2O=3CaCO3+(NH4)2WO4 (4)
2NH4OH+CO2=(NH4)2CO3+H2O (5)
(NH4)2CO3+CO2+H2O=2NH4HCO3 (6)
As (the NH in solution4)2WO4When concentration is higher, especially there are a large amount of NH4In the presence of OH, (NH4)2WO4Meeting With the high activity CaCO of leaching process generation3Generation secondary response, generation are difficult to the CaWO leached by ammonium carbonate salt solution4, cause Tungsten loss.Key reaction is probably:
CaCO3+2NH4OH Ca(OH)2+(NH4)2CO3 (7)
Ca(OH)2+(NH4)2WO4=CaWO4+2NH4OH (8)
Reaction (8) is easier to carry out, and generally reacts (7) and be difficult to, but in Ca3WO6Leaching process in it is newborn CaCO3Active high, reaction (7) is then possible to carry out, and with the carry out NH of leaching process4OH and (NH4)2WO4Concentration not Disconnected increase, reacts (7) and reaction (8) is strengthened, and ultimately results in (NH4)2WO4The loss increase of tungsten when concentration is higher.Therefore, CO is passed through in closed Leaching Systems2, the rapid NH neutralized in solution4OH, suppressed reaction (7);Pass through addition simultaneously CaCO3Crystal seed, make newborn CaCO3Grown up rapidly in seed surface, reduce its activity, further suppress the progress of reaction (7).From And it is expected to obtain (the NH of high concentration simultaneously4)2WO4Solution and high tungsten leaching rate.
In addition, CO is passed through in enclosed system2, CO can also be improved2Utilization rate.
Embodiment 1:
CaO/WO is pressed by calcium carbonate (analysis is pure) and tungstic acid (analysis is pure)3Molecular proportion 3.1:After 1 mixing, in Muffle furnace In 2h synthesis Ca is reacted at 800 DEG C3WO6, the Ca of synthesis3WO6325 mesh sieves of levigate mistake afterwards (<45μm).Then 5.0g is weighed Ca3WO6Pure ammonium carbonate is analyzed with 50g, is added to together in micro-reaction kettle, adds 50mL deionized waters, closed and unlatching is stirred Mix, 0.5h is leached at 80 DEG C.After the completion of leaching, filter cake is washed with deionized three times using vacuum filtration in leaching slurry.Tungsten Leaching rate be 92.90%.
Embodiment 2:
Weigh the Ca synthesized in 5.0g embodiments 13WO6, the pure calcium carbonate of 0.5g analyses and 30g analyze pure ammonium carbonate, added together Enter into micro-reaction kettle, add 50mL deionized waters, pH value 9.7 is closed and open stirring, and 10h is leached at 15 DEG C. After the completion of leaching, filter cake is washed with deionized three times using vacuum filtration in leaching slurry.The leaching rate of tungsten is 96.16%.
Embodiment 3
Weigh the Ca synthesized in 5.0g embodiments 13WO6, the pure calcium carbonate of 0.5g analyses and 30g analyze pure ammonium carbonate, added together Enter into micro-reaction kettle, add 50mL deionized waters, it is closed and open stirring, leach 4h at 30 DEG C.After the completion of leaching, Filter cake is washed with deionized three times using vacuum filtration in leaching slurry.The leaching rate of tungsten is 98.76%.
Embodiment 4:
Certain scheelite (WO3Weight/mass percentage composition is 49.53%, CaO weight/mass percentage compositions 19.10%), calcium carbonate (analysis It is pure) press CaO/WO3Molecular proportion 3.1:After 1 levigate mixing, 2h is then reacted at 800 DEG C in Muffle furnace and obtains clinker, X ray spreads out Penetrate analysis result to show, tungsten therein is all with Ca3WO6Form exist, by clinker it is levigate after cross 325 mesh sieves (- 45 μm).Claim 50.0g clinkers are taken, are added in the leachate that 50ml carbonic acid ammonium concentration is 500g/L, in closed stirring digester at 100 DEG C Leaching 2 hours.After the completion of leaching, using vacuum filtration, filter cake is washed with deionized three times.The leaching rate of tungsten is 86.39%.
Embodiment 5:
By 19.0g WO3(analysis pure) be all dissolved into closed container at 80 DEG C 100mL ammoniacal liquor (analysis is pure, 25 ~28%) in, ammoniacal liquor-ammonium tungstate solution is made.Weigh 10.0g and analyze pure calcium carbonate, in the micro-reaction kettle being added to, then add Enter 50mL ammoniacal liquor-ammonium tungstate solution (NH4OH concentration is about 170g/L, WO3Concentration is 190g/L), it is closed and open stirring, and 4h is reacted at 80 DEG C.After the completion of reaction, reaction ore pulp is using vacuum filtration, and it is 45.16g/L to measure WO3 concentration in filtrate, table WO3 in bright solution is largely lost due to secondary response.The X-ray diffraction result of reaction slag shows that main thing therein is mutually CaWO4And CaCO3
Embodiment 6:
By 19.0g WO3(analysis pure) be all dissolved into closed container at 80 DEG C 100mL ammoniacal liquor (analysis is pure, 25 ~28%) in, then be passed through carbon dioxide (technical pure) adjustment solution pH be 9.5 or so, be made ammonium carbonate-ammonium tungstate it is molten Liquid.Weigh 10.0g and analyze pure calcium carbonate, add in micro-reaction kettle, add 50mL ammonium carbonates-ammonium tungstate solution (WO3Concentration For 190g/L), it is closed and open stirring, and react 4h at 80 DEG C.After the completion of reaction, reaction ore pulp is surveyed using vacuum filtration Obtain WO in filtrate3Concentration is 186g/L, comparative example 4, illustrates to increase dissolution system carbonate concentration, can slow down secondary counter Should.
Embodiment 7:
5g clinkers are weighed, and 1.0g analyzes pure calcium carbonate and 100g and analyzes pure ammonium carbonate, is added to together in beaker, then 100mL deionized waters are added, open stirring, and be passed through CO2Gas, the pH of maintenance system is 9.0 or so, is leached at 50 DEG C 1h.After the completion of leaching, filter cake is washed with deionized three times using vacuum filtration in leaching slurry.The leaching rate of tungsten is 96.73%.In conjunction with the embodiments 4~6, illustrate that secondary response can effectively be suppressed by being passed through carbon dioxide in leaching process.
Embodiment 8:
Obtained clinker in 5.0g embodiments 3 is weighed, 0.75g analyzes pure calcium carbonate and 50g and analyzes pure ammonium carbonate, adds together Enter into micro-reaction kettle, add 50mL deionized waters, it is closed to open stirring, after leaching 1h at 80 DEG C, add 5.0g Obtained clinker in embodiment 3, continue to leach 1h at 80 DEG C.After the completion of leaching, leaching slurry using vacuum filtration, spend from Sub- water washing filter cake is three times.The leaching rate of tungsten is 96.40%.
Embodiment 9:
Weigh the Ca of 2.5g synthesis3WO6, the pure calcium carbonate of 0.5g analyses and 30g analyze pure ammonium carbonate, are added to together micro In reactor, 50mL deionized waters are added, it is closed and open stirring, leach 1h at 30 DEG C;Again plus 2.5g synthesis Ca3WO6, leach 4h.After the completion of leaching, filter cake is washed with deionized three times using vacuum filtration in leaching slurry.The leaching of tungsten Rate is 98.98%.
Embodiment 10:
5g clinkers are weighed, 0.5g analyzes pure calcium carbonate and 30g and analyzes pure ammonium carbonate, is added to together in micro-reaction kettle, Add 50mL deionized waters, it is closed and open stirring, leach 1h at 40 DEG C;Again plus 5g clinkers and it is passed through CO2, leach 10h. After the completion of leaching, filter cake is washed with deionized three times using vacuum filtration in leaching slurry.The leaching rate of tungsten is 92.33%.
Embodiment 11:
5g clinkers are weighed, 0.5g analyzes pure calcium carbonate and 30g and analyzes pure ammonium carbonate, is added to together in micro-reaction kettle, Add 50mL deionized waters and 5ml ammonium tungstate solutions (WO3Concentration 160g/L), it is closed and open stirring, leached at 40 DEG C 1h;Again plus 2g clinkers and 10g ammonium carbonate, 10h is leached.After the completion of leaching, leaching slurry uses deionized water using vacuum filtration Wash filter cake three times.The leaching rate of tungsten is 95.33%.
Embodiment 12:
Obtained clinker in 5.0g embodiments 3 is weighed, 0.5g analyzes pure calcium carbonate and 50g and analyzes pure ammonium carbonate, adds together Enter into micro-reaction kettle, add obtained ammonium carbonate-ammonium tungstate solution (WO in 50mL embodiments 43Concentration is 190g/L), It is closed and be passed through CO2Gas, the pressure of maintenance system is 2atm, opens stirring, 1h is leached at 80 DEG C.After the completion of leaching, leaching Go out slurries using vacuum filtration, filter cake is washed with deionized three times.The leaching rate of tungsten is 98.73%.
Embodiment 13:
Weigh 100.0g scheelites (WO3Weight/mass percentage composition is 60.34%, Fe weight/mass percentage compositions for 4.73%), By generation Ca3WO6And Ca2FeWO61.1 times of supplying calcium carbonate of theoretical amount, raw material are obtained after carrying out levigate mixing.Then, roasting Burn in stove, under weak reducing atmosphere, 950 DEG C of roasting 4.0h, obtain clinker, its X-ray diffraction analysis result shows, is deposited in clinker Tungstenic thing mutually only have Ca3WO6And Ca2FeWO6.Clinker ball mill is levigate, and crosses 325 mesh sieves (clinker granularity≤45 μm), Weigh 5.0g it is levigate after clinker be put into leaching equipment, add 50ml unsaturated carbonate ammonium salt solutions, and according to the 1.5 of theoretical amount Ammonium hydrogen carbonate is added again;4h is reacted at 62 DEG C.After reaction terminates, leach ore pulp and filter, with 100mL pure waters filter cake 5 times. The leaching rate of tungsten is 97.78%.
Embodiment 14:
The clinker ball mill that obtained after being sintered in embodiment 13 is levigate to 80 mesh sieve (granularities excessively<200 μm), weigh Clinker after 5.0g is levigate, is put into ball milling leaching equipment, adds 50ml ammoniacal liquor-sal volatile, (NH in solution3Quality hundred It is 5% to divide content, and carbonic acid ammonium concentration is 400g/L);5h is reacted at 40 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Wash filter cake 5 times.The leaching rate of tungsten is 95.71%.
Embodiment 15:
The clinker ball mill that obtained after being sintered in embodiment 13 is levigate to 800 mesh sieve (granularities excessively<18 μm), weigh Clinker after 10.0g is levigate, leaching equipment is put into, adds 50ml ammoniacal liquor-ammonium carbonate-ammonium tungstate solution (NH in solution3Matter It is 20% to measure percentage composition, and carbonic acid ammonium concentration is 400g/L, WO3Concentration is 100g/L);5h is reacted at 40 DEG C.Reaction terminates Afterwards, leach ore pulp to filter, with pure water filter cake 5 times.The leaching rate of tungsten is 98.49%.
Embodiment 16:
Levigate rear clinker in 5.0g embodiments 12 is weighed, leaching equipment is put into, it is molten to add 50ml ammonium carbonates-ammonium tungstate (carbonic acid ammonium concentration is 400g/L, WO to liquid3Concentration is 120g/L), add the ammonium hydrogen carbonate of 1.3 times of theoretical amount;Soaked at 40 DEG C Go out 5h.After leaching terminates, leach ore pulp and filter, with pure water filter cake.The leaching rate of tungsten is 97.24%.
Above example only exemplarily illustrates Ca3WO6、Ca2FeWO6It can be leached by ammonium carbonate salt solution system, this The technical staff in field should be understood that the tungsten in tungsten ore makes tungsten therein be changed into Ca through other preprocess methods3WO6 And/or Ca2FeWO6Afterwards, tungsten therein can also be leached with ammonium carbonate salt solution system, obtains ammonium tungstate solution.
According to the present invention, tungstenic raw material and calcareous material are calcined at high temperature and prepare Ca3WO6, obtained Ca3WO6Can be with Leached under the conditions of relatively mild by ammonium carbonate salts (ammonium carbonate, ammonium hydrogen carbonate) solution, or in ammoniacal liquor-carbon dioxide system leaching Go out, carbon dioxide can be also passed through when being leached using ammonium carbonate salt solution, directly obtains ammonium tungstate solution.
It is not necessary according to the invention that being converted into the transition step of ammonium tungstate by sodium tungstate solution, wolframic acid can be directly obtained Ammonium salt solution, the decomposition nut liquid after evaporative crystallization separates out APT can return to Leaching Systems, realize that solution circulates, fundamentally solve The problem of wastewater discharge is more in APT production processes, environmental pollution is heavy, and reduce supplies consumption.
It is important to note that these embodiments are only examples, to illustrate the present invention, rather than limit the present invention's Scope.It should be appreciated by those skilled in the art:If without departing from the principle and method of the present invention, to technical solution of the present invention Details and form carry out modification and replacement, all within protection scope of the present invention.

Claims (17)

1. a kind of technique for preparing ammonium tungstate solution, it is characterised in that with containing (AO)x(WO3)y(BO)zMaterial as raw material, its Middle A, B are divalent metal element, (x+z)/y=3, x+z+y=4;The granularity of raw material is not more than 200 μm;Seed charge is 0- 15g/L;The selection principle for leaching agent solution comprises at least:Including in the reactant of the raw material can participate in recombining The material of the leaching agent, leaching agent contain NH in itself4 +, concentration is more than 10g-NH4 +/100g-H2O;The addition of leaching agent is at least The AO in clinker and BO is set to be converted into the theoretical amount needed for corresponding difficulty soluble salt;Leaching Systems pH is controlled to be not less than 8;In airtight condition Lower leaching, the absolute pressure of Leaching Systems are not less than 1atm, and extraction temperature is 15~100 DEG C, and extraction time is 0.1~10.0h, The initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/g, the final liquid-solid ratio of Leaching Systems, leaching are reduced by way of multistage charging After the completion of going out, leaching slurry obtains ammonium tungstate solution through separating, washing.
2. technique according to claim 1, it is characterised in that leaching agent also contains CO in itself3 2-And/or HCO3 -, participate in again The material for synthesizing the leaching agent is NH3、CO2;X=3, y=1, z=0;Or x=2, y=1, z=1;A is Ca, and B be Fe or Mn, or A and B are Ca;And/or CO is passed through in enclosed system2
3. technique according to claim 1, it is characterised in that the granularity of raw material is less than 200 μm;Crystal seed is carbonate;It is brilliant Kind addition is 10g/L;And/or the absolute pressure of Leaching Systems is 1.5-2.5atm.
4. technique according to claim 1, it is characterised in that Leaching Systems carbonic acid ammonium concentration is more than 20g- (NH4)2CO3/ 100g-H2O;And/or ammonium carbonate-ammonium hydrogen carbonate and ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, ammonium hydrogen carbonate addition At least 1.0 times of theoretical amount.
5. technique according to claim 1, it is characterised in that 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/or by two sections of chargings, control final Leaching Systems Liquid-solid ratio is 3:1~4:1mL/g.
6. technique according to claim 1, it is characterised in that the Ca in tungsten mineral material3WO6And Ca2FeWO6Closed to be artificial Into pure compound, or tungsten mineral material obtained after processing contain Ca3WO6And/or Ca2FeWO6Mixture.
7. technique according to claim 1, it is characterised in that the Ca in tungsten mineral material3WO6And/or Ca2FeWO6It is mixed The granularity of compound material is not more than 200 μm.
8. technique according to claim 1, it is characterised in that be that ammonium carbonate-ammonium hydrogen carbonate is molten using ammonium salt solution system Liquid system, ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, ammonium carbonate-CO2Solution system or ammonium carbonate-ammonium tungstate-CO2 Solution system, ammonium carbonate-ammonia spirit system, ammonium carbonate-ammonium tungstate-ammonia spirit system.
9. technique according to claim 8, it is characterised in that the solution of the ammonium carbonate is by ammonium bicarbonate soln and ammonia Water or ammoniacal liquor and CO2Part substitutes.
10. technique according to claim 1, it is characterised in that be passed through CO in closed Leaching Systems2, neutralize rapidly molten NH in liquid4OH;Simultaneously by adding CaCO3Crystal seed, make newborn CaCO3Grown up rapidly in seed surface, reduce its activity, with (the NH of high concentration is obtained simultaneously4)2WO4Solution and high tungsten leaching rate.
11. technique according to claim 3, it is characterised in that the granularity of raw material is less than 45 μm;Crystal seed is calcium carbonate or contained There is the material of calcium carbonate;And/or the absolute pressure of Leaching Systems is 2atm.
12. technique according to claim 4, it is characterised in that Leaching Systems ammonium carbonate is the sal volatile of saturation; And/or ammonium carbonate-the ammonium hydrogen carbonate and ammonium carbonate-ammonium tungstate-ammonium bicarbonate soln system, ammonium hydrogen carbonate addition are theory 1.1~1.4 times of amount.
13. technique according to claim 5, it is characterised in that extraction temperature is 30~50 DEG C;Extraction time be 0.5~ 4.0h;And/or the initial liquid-solid ratio of Leaching Systems is 10:1-4:1mL/g.
14. technique according to claim 7, it is characterised in that Ca3WO6And/or Ca2FeWO6Mixed material granularity it is small In 45 μm.
15. technique according to claim 8, it is characterised in that with ammonium carbonate-ammonium bicarbonate soln system, ammonium carbonate-tungsten Sour ammonium-ammonium bicarbonate soln system, ammonium carbonate-ammonia spirit system, ammonium carbonate-ammonium tungstate-ammonia spirit system leach Ca3WO6 Or Ca2FeWO6When, the absolute pressure of the solution system of leaching agent is not particularly limited;With ammonium carbonate-CO2Or ammonium carbonate-wolframic acid Ammonium-CO2Solution system leaches Ca3WO6Or Ca2FeWO6When, CO is passed through in leaching process2, control the absolute pressures of Leaching Systems Not less than 1atm.
16. technique according to claim 15, it is characterised in that the absolute pressure for controlling Leaching Systems is 1.5- 2.5atm。
17. technique according to claim 16, it is characterised in that the absolute pressure for controlling Leaching Systems is 2atm.
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