CN104263923B - The tungsten mineral material metallurgical technology of no pollution discharge can be achieved - Google Patents

The tungsten mineral material metallurgical technology of no pollution discharge can be achieved Download PDF

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Publication number
CN104263923B
CN104263923B CN201410528923.4A CN201410528923A CN104263923B CN 104263923 B CN104263923 B CN 104263923B CN 201410528923 A CN201410528923 A CN 201410528923A CN 104263923 B CN104263923 B CN 104263923B
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China
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clinker
leaching
raw material
ammonium
tungsten
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CN201410528923.4A
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CN104263923A (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
朱志成
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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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

A kind of metallurgical technology containing tungsten mineral material of achievable no pollution discharge, including：I circulates, and using weak caustic solution as leaching agent, leaches clinker, leaching slurry is washed through caused leached mud after separation of solid and liquid, cleaning solution feeds back to the agent of leaching ore deposit and reused；II circulates, and using at least part leached mud as dispensing, feeds back to the reuse of dispensing link；III circulates, and the gas that evaporation and crystal process is discharged, which is back to, leaches clinker link, recombines the agent of leaching ore deposit and uses；IV circulates, and the water that evaporation and crystal process is evaporated feeds back to the separation of solid and liquid link of leaching slurry, reuses；V circulates, and the slurries after crystallization is carried out with solid-liquor separation, solid phase obtains the final products of the element containing W after water washing and crystalline mother solution is back to the link for leaching clinker, reuses.Therefore, the present invention realizes whole non-wastewater discharge.

Description

The tungsten mineral material metallurgical technology of no pollution discharge can be achieved
Technical field
The present invention relates to a kind of tungsten mineral material metallurgical technology of achievable no pollution discharge, prepared by tungsten mineral material APT, belong to Tungsten smelting technical field.
Term " raw material " refers to tungsten mineral material, dispensing, after proportioning, and is milled to the mixed material of certain fineness.
Term " clinker " refer to tungsten mineral material, dispensing through it is levigate, be mixed into raw material, then after high-temperature roasting gained thing Material.
Term " mineralizer " refers to that the reaction between tungsten mineral material and dispensing or drop can be accelerated in raw material roasting process The material of low sintering temperature.
Background technology
In the prior art, the commercial run for preparing APT mainly comprises the following steps：Pass through caustic soda or soda leaching tungsten ore Raw material, obtain coarse sodium tungstate；Made the transition by solution purification-ion exchange or solvent extraction (or pass through ion exchange Or solvent extraction cleans and made the transition), obtain pure tungsten acid ammonium solution；Again by evaporative crystallization, APT products are obtained.
Following essential defect all be present in prior art：Using not circulating or half cycle process system, solution is not carried out With the circulation of supplies.Following technical problem at least be present in prior art：Waste water discharge opening, waste water pollution problem must be set Can not thoroughly it eradicate；Supplies are mostly expendable consumed product, and the leaching agent of leaching process is excessively used, these adminiclies Material corresponding processing step after completion of the reaction either in directly outer row or acid corresponding to needing to use or alkali and after it is outer again Row, supplies consumption is more, and production cost is high；Inevitably take part wolfram element out of in waste water, the wolfram element rate of recovery is low； Equipment investment is big, technological process length, and productivity ratio is relatively low, it is more difficult to realizes continuous production.
In such APT preparation process, auxiliary material consumption is larger, and produces a large amount of waste water；Sodium tungstate solution makes the transition During produce substantial amounts of high bisulfate waste liquor, evaporative crystallization mother liquor produces ammonia nitrogen waste water.
If the open circuit flow for having disposal of pollutants is become the closed circuit flow of no disposal of pollutants, it is not without technical Possibility, but input is possibly even more than profit, therefore, enterprise has to, selection discharge, as a result causes serious Environmental pollution.
The content of the invention
It is former from tungsten mineral it is an object of the invention to provide a kind of tungsten mineral material metallurgical technology of achievable no pollution discharge Material prepares APT, and its flow is short, solution reusable edible, contaminated wastewater are almost uprooted, cost is low, is easy to industrialization.
Therefore, according to an aspect of the invention, there is provided a kind of tungsten mineral material of achievable no pollution discharge is metallurgical Technique, APT is prepared from tungsten mineral material, is comprised the following steps：
1) by tungsten mineral material, dispensing it is levigate after, it is well mixed to prepare raw material；
2) raw material are calcined, obtain clinker, and clinker is crushed, it is levigate；
3) with ammonium carbonate, ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate, ammonium carbonate-CO2, ammonium carbonate-ammoniacal liquor-CO2, carbon Sour ammonium-ammoniacal liquor, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2, ammonium carbonate-ammoniacal liquor-wolframic acid Ammonium, ammonium carbonate-ammonium tungstate-CO2, ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2System leaches clinker；
4) leaching slurry washs through separation of solid and liquid and slag phase, obtains thick ammonium tungstate solution and leached mud, and part leached mud is made For dispensing return to step 1) carry out raw material configuration, remainder stockpiling；
5) thick ammonium tungstate solution purification and impurity removal；
6) solution separates out APT using evaporative crystallization after purifying, while obtains ammonia and carbon dioxide；
7) solid-liquor separation is carried out to the slurries after crystallization, obtains crystalline mother solution and solid phase, solid phase is through water and/or ammonium salt solution Washing, obtains APT products after drying, crystalline mother solution returns to step together with ammonia and carbon dioxide that step 6) obtains 3), and (can be by ammonium hydrogen carbonate or ammoniacal liquor and CO in the ammonium carbonate of supplement consumption2Part substitutes) Posterior circle leaching clinker.
Preferably, described tungsten mineral material includes, scheelite, wolframite, Scheelite-Wolframite Mixed Mine, and/or tungsten slurry；
Preferably, when raw material are prepared, the addition of calcareous material presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO +MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.0 meters, preferably 1.5-6.0, more preferably 3.0-4.0, more Preferably 3.3-3.6；Raw material granularity is not more than 200 μm, preferably not greater than 100 μm, more preferably not more than 45 μm；Raw material roast During burning, temperature is not less than 500 DEG C, preferably 800-1050 DEG C, more preferably 850-950 DEG C；
Preferably, mineralizer, preferably calcirm-fluoride are added in raw material process for preparation, to accelerate tungsten mineral material and dispensing Between reaction, significantly reduce sintering temperature；
Preferably, the time of raw material roasting is 0.5-8.0h, preferably 1.0-3.0h, more preferably 2.0h；Tungsten mineral is former Expect for scheelite when, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere；
Preferably, when tungsten mineral material is wolframite, Scheelite-Wolframite Mixed Mine, tungsten slurry, calcination atmosphere is neutral or reduction Property atmosphere, preferably neutral atmosphere；The granularity of clinker is not particularly limited, preferably not greater than 200 μm, further preferably for no more than 74 μm, further preferably for no more than 45 μm；
Preferably, the CO in Leaching Systems2A part is from the either business of stove (kiln) gas caused by raw material roasting process Product CO2, another part comes from CO caused by ammonium tungstate solution evaporation and crystal process2；
Preferably, CO2It can be passed through, can also be passed through before leaching in leaching process.
Preferably, leach carbonic acid ammonium concentration in initial system and be more than 20g- (NH4)2CO3/100g-H2O, it is preferably the system The concentration of its lower saturated solution, and ammonium hydrogen carbonate is then added in the form of solution or solid, the addition of ammonium hydrogen carbonate is not by spy Do not limit, the calcium in clinker is converted into 1.0 times of calcium carbonate aequum (theoretical amount), preferably theoretical amount 1.1-1.4 times, ammonium tungstate concentration is not particularly limited, as long as can ensure that the wolframic acid after tungsten fully leaches in clinker in resulting solution Ammonium concentration is no more than the equilibrium concentration under the system, and the addition of ammoniacal liquor is also not particularly limited, and preferably leaches initial NH in system3Weight/mass percentage composition be 0%~28%, more preferably 5%~20%, more preferably 5%~10%；Clinker Leaching process is carried out in enclosed system, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, carbon When sour ammonium-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-ammoniacal liquor-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach clinker, The absolute pressure of reaction system is not particularly limited, with ammonium carbonate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-CO2System, carbonic acid Ammonium-ammoniacal liquor-CO2System, ammonium carbonate-ammonium tungstate-CO2System, ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2System and ammonium carbonate-carbonic acid Hydrogen ammonium-ammonium tungstate-CO2When system leaches clinker, the absolute pressure of reaction system need to be controlled to be not less than 1atm, preferably 2atm；
Preferably, extraction temperature is not less than 5 DEG C, preferably 10-80 DEG C, more preferably 20-70 DEG C, more preferably 30-50 ℃；
Preferably, extraction time is not particularly limited, as long as can ensure that tungsten can be leached fully in clinker, preferably be soaked It is 0.5-8.0h to go out the time, and more preferably extraction time is 2-5h；Purification and impurity removal process include except molybdenum, phosphorus, tin, arsenic, silicon, iron, At least one of sodium, potassium, bismuth, antimony, calcium, magnesium process.
According to another aspect of the present invention, there is provided a kind of system for preparing APT, including：
1) grinding attachment A, tungsten mineral material, dispensing after batching metering, using grinding attachment A by various raw materials it is levigate, Mix, prepare the raw material with certain fineness and the uniformity；
2) calcining kiln (stove), the raw material of preparation is added in calcining kiln (stove) and are calcined, clinker is obtained after cooling；
3) grinding attachment B, the clinker burnt till are levigate using grinding attachment B；
4) leaching equipment, clinker are leached in leaching equipment；
5) filter plant, leaching slurry carry out filtration washing using filter plant；
6) impurity removing equipment, thick ammonium tungstate solution purification and impurity removal in impurity removing equipment；And
7) crystallizer, ammonium tungstate refined liquid evaporative crystallization in crystallizer.
Preferably, the grinding attachment A is selected from：Vibrating mill, ball mill, rod mill, autogenous tumbling mill, agitator mill, overhang roll Pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, airslide disintegrating mill.
Preferably, the calcining kiln (stove) includes：Static calcining kiln (stove) and dynamic roasting kiln (stove).
Preferably, the grinding attachment B is selected from：Vibrating mill, twin rollers, ball mill, rod mill, autogenous tumbling mill, Ball-stirring mill Machine, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, airslide disintegrating mill.
Preferably, the leaching equipment can be an independent leaching equipment, can also the series connection of 2-4 leaching equipment make With.
Preferably, the leaching equipment can be leaching equipment or ball milling leaching equipment.
Preferably, the leaching equipment can seal, and can bear 4atm pressure.
Preferably, the filter plant is pumping and filtering device, filtering equipment, and/or natural filtration groove.
Preferably, the impurity removing equipment is decleaning tank, filter plant, and/or subsider.
Preferably, agitating device, and/or attemperator are provided with the decleaning tank.
The present invention the advantage is that relative to existing APT industrial process：
1) closed cycle that solution during APT is prepared by tungsten mineral material is realized, so as to which APT lifes can be eradicated in theory During production due to a large amount of discharge of wastewater and caused by problem of environmental pollution；
2) made the transition by the way that tungsten mineral material is calcined, wolfram element is changed the material for being contained in and easily being leached by ammonium carbonate salt solution In, the low-temp extraction of tungsten is realized, reduces the energy expenditure and cost in leaching process, meanwhile, leached mud can be used as tungsten again Dispensing in raw mineral materials transformation process and recycle；
3) tungsten mineral clinker is leached using low cost, the ammonium carbonate salts system easily circulated, directly obtains ammonium tungstate solution, take The transition step to have disappeared from sodium tungstate solution to ammonium tungstate solution, flow are simple；
4) recycling due to a variety of supplies, supplies consumption are greatly reduced, and processing charges is significantly Reduce；
5) it is simple to operate, it is easy to control, is easy to commercial Application.
According to the present invention, with " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate- Ammoniacal liquor-ammonium tungstate " or " ammonium carbonate-ammoniacal liquor " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammoniacal liquor-CO2" or " ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " ammonium carbonate- Ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system as leachate not it is clear that because：Alkalescent system The relatively low raw material of the chemical reactivities such as scheelite, wolframite, Scheelite-Wolframite Mixed Mine, tungsten slurry (or treatment effeciency is not handled It is extremely low).Tungsten smelting industry at present typically using strong acid (such as hydrochloric acid) or highly basic (such as sodium hydroxide) property system and high temperature, Leach tungsten mineral material under hyperbaric environment, and " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate ", " ammonium carbonate-ammonium tungstate-CO2", " carbonic acid Ammonium-ammoniacal liquor-ammonium tungstate ", " ammonium carbonate-ammoniacal liquor ", " ammonium carbonate ", " ammonium carbonate-ammonium hydrogen carbonate ", " ammonium carbonate-ammoniacal liquor-CO2”、 " ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2", " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2", " ammonium carbonate-CO2", " ammonium carbonate-tungsten Sour ammonium " and " ammonium carbonate-ammonium hydrogen carbonate-CO2" system belongs to alkalescent system, it is necessary to it could be realized by raw material transition step Leach.
According to the present invention, from " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " carbonic acid Ammonium-ammoniacal liquor-ammonium tungstate " or " ammonium carbonate-ammoniacal liquor " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammoniacal liquor- CO2" or " ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system leached, Leaching Systems material turns after crystallisation step Ammonia and carbon dioxide are melted into, Leaching Systems can be added to just, it is achieved thereby that the whole of supplies recycles, thoroughly Traditional open circuit not circulating system or open circuit half cycle system have been abandoned, disposal of pollutants has been eradicated, 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 leachate3The still enough industrialized productions of concentration.
According to the present invention, " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate-ammonia Water-ammonium tungstate " or " ammonium carbonate-ammoniacal liquor " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammoniacal liquor-CO2" or " ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " ammonium carbonate- Ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system leaching 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, using close circulation technology, waste residue outlet is only set, no longer needs to set waste water discharge opening, gives up The pollution problem of water discharge has obtained thorough elimination.
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, circulation metallurgical technology is realized, production system non-wastewater discharge, thoroughly avoids part wolfram element quilt Discharge in vain, therefore, the wolfram element rate of recovery also improves.
According to the present invention, integrated production can be achieved, the working environment in workshop can greatly improve, and equipment investment return rate is bright Aobvious to improve, technological process shortens, and productivity ratio is largely increased, it is possible to achieve continuous automated production.
According to the present invention, the pretreatment process of tungsten mineral material is added, using " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " Or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate-ammoniacal liquor-ammonium tungstate " or " ammonium carbonate-ammoniacal liquor " or " ammonium carbonate " or " carbonic acid Ammonium-ammonium hydrogen carbonate " or " ammonium carbonate-ammoniacal liquor-CO2" or " ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-tungsten Sour ammonium-CO2" or " ammonium carbonate-CO2" or " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system leaching tungsten mineral Clinker, leaching condition is gentle, and leaching agent is cheap, is easy to get, and supplies reusable edible, can eliminate in theory in production process Discharge of wastewater.
According to the present invention, prior art has been completely disengaged, it is proposed that a kind of brand-new theory and technique that prepare APT, save Go to produce the sodium tungstate solution transition step of a large amount of waste water, directly obtain ammonium tungstate solution, be inherently eliminated APT productions During waste water discharge, and realize recycling for supplies and solution.
According to the present invention, technological process is simple, easy to operate, and production cost is low, non-wastewater discharge pollution.
Brief description of the drawings
Fig. 1 is a kind of process chart that APT is prepared by tungsten mineral material according to the present invention.
Fig. 2 is the principle schematic diagram according to a kind of system that APT is prepared by tungsten mineral material of the present invention.
Embodiment
1-2 is described further to embodiments of the invention below in conjunction with the accompanying drawings.
As shown in figure 1, the metallurgical technology containing tungsten mineral material of the present invention comprises the following steps：
Make raw mineral materials containing W 100 and dispensing MN (M represents cation, and N represents anion) proportionings into raw material 101；
Raw material 200 are calcined, promotees it and chemically reacts, to be transformed into the clinker containing M and containing W ion, so that clinker obtains Obtain chemical reactivity；
The dissolving of weak base AN (A is cation) solution (the excessive highly basic of thorough abandoning tradition leaches prejudice) clinker is used, with Clinker is leached 300, and in circular response, reclaim the leachate that each link is fed back, and mend according to being actually needed Fill the weak base AN of consumption；
Separation of solid and liquid 400 is carried out to leaching slurry, the thick solution containing A and containing W ion and the leached mud containing M are obtained, to slag Mutually wash, cleaning solution feeds back to leaching agent (I closed loop), according to being actually needed, takes at least part leached mud to feed back to raw material and matches somebody with somebody Put link (II closed loop) and be used as dispensing, if leached mud has remainder, store up；
At least first class purification removal of impurities 500 is carried out to the thick solution containing A and containing W ion；
Crystallization 600 is evaporated to the solution after purification, to separate out the intermediate products of the element containing W；Meanwhile will discharge with The related gas of element A and the gas related to N element are back to the step of leaching clinker 300 (III closed loop), and evaporate Water feed back to the separation of solid and liquid link (IV closed loop) of leaching slurry 300；
Solid-liquor separation 700 is carried out to the slurries after crystallization, to obtain crystalline mother solution and solid phase, solid phase obtains after water washing The final products (preferably by solid phase dissolve and crystallize again, to obtain the final products of higher purity) of W elements must be contained； And crystalline mother solution is also returned to (V closed loop) the step of leaching clinker,
Therefore, the technique includes multiple closed cycles, whole non-wastewater discharge.
As shown in Fig. 2 the metallurgical system of the tungsten mineral material of the present invention includes successively：
Raw material preparation facilities 10, it has raw mineral materials dosage/metering entrance 11 and dosage/metering entrance 12 (excellent Choosing be additionally provided with mineralising agent dose/metering entrance 13), raw material fine mill (contain vortex mixer) 14, raw material export 15 and leached mud connect Closing in 16；
Calcining kiln (stove) 20, it is connected through feeding measurement device and raw material silo with raw material outlet 15, has heater, insulation Device (preferably also including cooling device 21) and thick clinker outlet 22；
Clinker fine mill 30, it is connected through clinker storehouse with thick clinker outlet 22, has ore grinding device and thin clinker outlet 31；
Leaching device 40, itself and thin clinker outlet 31, there is leaching ore deposit agent entrance 41, leaching slurry outlet 42, feedback Gas recovery port 43, slurry separating, washing liquid recovery port 44, slag phase cleaning solution recovery port 45, it is preferable that also including crystal seed Entrance 46 and carbon dioxide are passed through mouth 47；
The equipment for separating liquid from solid (preferably filter) of leaching slurry, it is connected with leaching slurry outlet 42, is had to contain and is matched somebody with somebody The filtration washing device 50 of the leached mud of material element, the thick taphole 51 containing wolfram element, leached mud feedback port 52, extremely remaining leaching The outlet 53 of slag muck warehousing, washing lotion feedback outlet 54, the receiving port 55 of evaporative crystallization condensed water, the equipment for separating liquid from solid are feeding back Connected into the way of the leached mud receiving port 16 of raw material preparation facilities 10 with the crystal seed entrance 46 of leaching device 40；
At least first class purification knot screen 60, the entrance 61 of the first order connect with the thick taphole 51 containing wolfram element, respectively Level has purification and impurity removal agent entrance and impurity collector, (preferably, afterbody has the smart taphole 62 containing wolfram element Afterbody adds extractor fan)；
Crystallization apparatus 70, its entrance 71 connect with the smart taphole 62 containing wolfram element, with slurry outlet 72, instead It is fed to the gas feedback mouth 73 and condensation-water drain 74 of leaching device (preferably with smart solution evaporative crystallization controller)；
The liquid-solid separation device 80 of slurry, it is connected with slurry outlet 72, and there is crystalline mother solution to be back to leaching Go out the outlet 81 of device 40, the outlet 83 of solid phase wash water entrance 82 and tungsten product (preferably, is dissolved with next stage, crystallized, carrying Pure subsystem connection).
It is well mixed to obtain by tungsten mineral material and a certain amount of calcareous material and mineralizer after levigate according to the present invention Obtain raw material；When raw material are prepared, the addition of calcareous material presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/ WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.0 meters, preferably 1.5-6.0, more preferably 3.0-4.0, more preferably 3.3-3.6；
When raw material are prepared, the mineralizer of supplying is fluoride, it is therefore preferable to which calcirm-fluoride, the addition of calcirm-fluoride is dry tungsten ore The 0.5-7% (mass percent) of raw material amount, preferably 1-3% (mass percent)；Raw material granularity is less than 200 μm, is preferably Less than 45 μm；Raw material sintering temperature is not less than 500 DEG C；Raw material sintering temperature is 800~1050 DEG C, preferably 850~950 DEG C； Roasting time is not particularly limited, and temperature is low, needs to extend roasting time, to make the tungsten in raw material be fully converted into Ca3WO6With/ Or Ca2FeWO6And/or Ca2MnWO6, preferably roasting time is 0.5-8.0h, more preferably 1.0~3.0h, is more preferably existed 2.0h is calcined at 850~950 DEG C.
For scheelite raw material, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere；For black tungsten Ore deposit, Scheelite-Wolframite Mixed Mine, tungsten slurry raw material, calcination atmosphere are neutral or reducing atmosphere, preferably neutral atmosphere
The present invention will contain Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Mixed material be added to ammonium salt solution system In, leach in confined conditions, after the completion of leaching, leaching slurry obtains ammonium tungstate solution through separating, washing.
Preferably, the Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6It can be artificial synthesized pure compound, also may be used Be tungsten mineral material obtained after processing contain Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Mixture；Ca3WO6With/ Or Ca2FeWO6And/or Ca2MnWO6Mixed material granularity be not more than 200 μm, preferably less than 45 μm；Described ammonium salt is molten Liquid system, can be ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-ammonium tungstate-CO2System, ammonium carbonate-ammoniacal liquor-tungsten Sour ammonium system, ammonium carbonate-ammonia-water systems, Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammoniacal liquor-CO2System, Ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2System, ammonium carbonate-CO2System, carbonic acid Ammonium-ammonium tungstate system, can also be ammonium carbonate-ammonium hydrogen carbonate-CO2System.
Preferably, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, ammonium carbonate-bicarbonate Ammonium-ammonium tungstate system, ammonium carbonate-ammoniacal liquor-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach Ca3WO6And/or Ca2FeWO6 And/or Ca2MnWO6When, the absolute pressure of Leaching Systems is not particularly limited；With ammonium carbonate-CO2System, ammonium carbonate-bicarbonate Ammonium-CO2System, ammonium carbonate-ammoniacal liquor-CO2System, ammonium carbonate-ammonium tungstate-CO2System, ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2Body System and ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2System leaches Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6When, leaching During be passed through CO2, 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.
Preferably, the ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-CO2, ammonium carbonate-ammoniacal liquor-wolframic acid Ammonium, ammonium carbonate-ammonium tungstate, ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2In solution system, Ammonium tungstate concentration is also not particularly limited, as long as meeting Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6In tungsten fully leach Afterwards, ammonium tungstate concentration is no more than its solubility in the system in resulting solution.
Preferably, the ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium hydrogen carbonate-CO2 With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2Solution system, ammonium hydrogen carbonate addition are not particularly limited, and are preferably not less than 1.0 times of theoretical amount, more preferably the 1.1~1.4 of theoretical amount times.
Preferably, the ammonium carbonate-ammoniacal liquor-ammonium tungstate, ammonium carbonate-ammoniacal liquor-ammonium tungstate-CO2, ammonium carbonate-ammoniacal liquor and carbon Sour ammonium-ammoniacal liquor-CO2In solution system, the addition of ammoniacal liquor is also not particularly limited, and preferably leaches NH in initial system3Matter It is 0%~28% to measure percentage composition, more preferably 5%~20%, more preferably 5%~10%.
Preferably, Leaching Systems pH is controlled to be not less than 8.0.Extraction temperature is not less than 5 DEG C, preferably 10-80 DEG C, more preferably For 20-70 DEG C, more preferably 30-50 DEG C；Extraction time is not particularly limited, as long as can make Ca3WO6And/or Ca2FeWO6With/ Or Ca2MnWO6In tungsten fully leach, preferably 0.5-8.0h, more preferably extraction time are 2.0-5.0h.
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.
According to an embodiment of the invention, thick ammonium tungstate solution purification and impurity removal, the method for purification and impurity removal are not particularly limited, As long as the content of the impurity such as P, As, Si, Mo, S, Sn, Sb, Ca, Mg, K, Na meets to prepare qualified APT products in solution after purification Quality requirement.According to one embodiment of present invention, the precipitation method can be used to remove the impurity in ammonium tungstate solution, thus Prepare ammonium tungstate refined liquid.
According to an embodiment of the invention, ammonium tungstate refined liquid can be taken APT using evaporative crystallization legal system, evaporative crystallization Condition is not particularly limited.According to one embodiment of present invention, at 95 DEG C, it is 6.5 that ammonium tungstate solution is evaporated into pH, warp After separation of solid and liquid and product washing, the APT product purities of acquisition meet 0 grade of product standard in GB/T 10116-2007.
Embodiment 1：By CaO/WO3Molecular proportion is 3.3, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Measure percentage composition for 0.43%) with clinker leached mud (main component CaCO3) and mineralizer calcirm-fluoride carry out it is levigate, mix after Obtain raw material, the addition of calcirm-fluoride is 5.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, so Afterwards, in roaster, under air atmosphere, 800 DEG C of roasting 2.0h, clinker is obtained.After clinker cooling to room temperature, vibrating mill is used It is levigate, clinker granularity≤45 μm.Weigh 5.0g it is levigate after clinker be added to ventilation and mechanical stirring device reactor in, Add 50g- (NH simultaneously4)2CO3/100g-H2O sal volatile 50mL is simultaneously closed, then passes to CO2Gas, control reactant The absolute pressure of system is 2atm, reacts 5h at 80 DEG C.After reaction terminates, ore pulp is leached using vacuum filtration, uses pure water Filter cake is three times.The leaching rate of tungsten is 97.15% in clinker.
Embodiment 2：By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 63.75%, Fe weight/mass percentage composition for 5.90%) carried out with clinker leached mud it is levigate, mix after obtain raw material, raw material granularity≤ 45 μm, then, in shaft furnace, under weak reducing atmosphere, 950 DEG C of roasting 3.0h, obtain clinker.After clinker cooling to room temperature, use Ball mill is levigate, clinker granularity≤45 μm.20.0g clinkers are weighed to be added in the reactor with ventilation and mechanical stirring device, Add 35g- (NH simultaneously4)2CO3/100g-H2O sal volatile 100mL is simultaneously closed, then passes to CO2Gas, control reaction The absolute pressure of system is 2atm, reacts 4h at 70 DEG C.After reaction terminates, ore pulp is leached using vacuum filtration, is washed with pure water Wash filter cake three times.The leaching rate of tungsten is 87.17% in clinker.
Embodiment 3:By (CaO+FeO+MnO)/WO3Molecular proportion is 3.4, by certain wolframite (WO3Weight/mass percentage composition is 62.40%, Fe weight/mass percentage composition are that 14.08%, Mn weight/mass percentage compositions are 2.25%) to enter with clinker leached mud and calcirm-fluoride Row is levigate, mix after obtain raw material, the addition of calcirm-fluoride is 7% (mass percent) of dry tungsten mineral material amount, nodules ≤ 40 μm of degree, then, in pipe type calciner, under neutral atmosphere, 6.0h is calcined at 800 DEG C, obtains clinker, clinker cooling to room Wen Hou, clinker granularity≤45 μm levigate with rod mill；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and 1.0 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 80 DEG C.After reaction terminates, leaching Go out ore pulp using being filtered by vacuum, with pure water filter cake three times.The leaching rate of tungsten is 97.13%.Then, by thick ammonium tungstate solution Purification and impurity removal, solution separates out APT using evaporative crystallization after purification, while obtains ammonia and carbon dioxide, after crystallization Slurries carry out solid-liquor separation, obtain crystalline mother solution and solid phase, and solid phase obtains APT products after water washing, and APT products reach state 0 grade of product standard requirement of family；Obtained ammonia and carbon dioxide returns to leaching equipment together, and in supplement lossAmmonium carbonateAfterwards Circulating leaching clinker.
Embodiment 4:By (CaO+FeO)/WO3Molecular proportion is 3.0, by certain wolframite (WO3Weight/mass percentage composition is 42.17%, Fe weight/mass percentage composition is 11.34%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 1.5% (mass percent), raw material granularity≤45 μm, then, in roaster In, under week reduction atmosphere, 850 DEG C of roasting 5.0h, obtain clinker, after clinker cooling to room temperature, clinker levigate with Ball-stirring mill Granularity≤45 μm；Leaching equipment selects ball milling digester, built-in ammonium carbonate saturated solution, and 1.1 times according to theoretical amount add Ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 40 DEG C.After reaction terminates, ore pulp is leached using vacuum filtration, is used Pure water filter cake is three times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3 but supplementAmmonium hydrogen carbonate and ammoniacal liquor。
Embodiment 5:By CaO/WO3Molecular proportion is 6.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition for 0.43%), clinker leached mud and calcirm-fluoride carry out levigate mixing after obtain raw material, the addition of calcirm-fluoride is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasted at 870 DEG C of roaster neutral atmosphere 4h is burnt, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with twin rollers；Leaching equipment selection band stirring Leaching tanks, built-in ammonium carbonate saturated solution, and ammonium hydrogen carbonate are added according to 1.3 times of theoretical amount；Clinker is put into leaching to set It is standby, while add ammoniacal liquor and (make NH in infusion solution3Weight/mass percentage composition to be 5%) and closed, then pass to carbon dioxide gas Body, the absolute pressure for controlling Leaching Systems is 2atm, reacts 5h at 30 DEG C.After reaction terminates, ore pulp pure water is leached Filter cake is three times.The leaching rate of tungsten is 98.51%.Then, similar embodiment 3 but supplementAmmoniacal liquor and CO2 。
Embodiment 6:By (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, 2.04%) Fe weight/mass percentage compositions is carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤45 μm, so Afterwards, 7h is calcined at 1000 DEG C of roaster neutral atmosphere, obtains clinker, it is levigate with centrifugal mill after clinker cooling to room temperature, it is ripe Material granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 35g- (NH4)2CO3/ 100g-H2O, and 1.3 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 9h at 40 DEG C.Instead After should terminating, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 98.99%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 7:By CaO/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud, raw material granularity≤40 μm, then, is being roasted Burn and be calcined 5h at 950 DEG C of stove neutral atmosphere, obtain clinker, it is levigate with planet mill after clinker cooling to room temperature, clinker granularity≤ 45μm；Leaching equipment selection is with the leaching tanks stirred, built-in unsaturated carbonate ammonium and containing 20g/LWO3Ammonium tungstate mixed solution, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3 Weight/mass percentage composition is 9.5%) and closed, then, is passed through carbon dioxide, and the absolute pressure for controlling Leaching Systems is 3atm, react 6h at 20 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 99.01%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 8:By CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO316.22%) and clinker weight/mass percentage composition is Leached mud carries out obtaining raw material after levigate mixing, raw material granularity≤40 μm, then, is calcined at 940 DEG C of roaster reducing atmosphere 3h, obtains clinker, after clinker cooling to room temperature；The leaching tanks that leaching equipment selection band stirs, built-in unsaturated carbonate ammonium and contain 120g/L WO3Ammonium tungstate mixed solution, and add ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Clinker is put into leaching to set It is standby, while add ammoniacal liquor and (make NH in infusion solution3Weight/mass percentage composition to be 10%) and closed, react 4h at 30 DEG C.Instead After should terminating, ore pulp is leached, with pure water filter cake three times.The leaching rate of tungsten is 97.51%.Then, similar embodiment 3 but benefit Fill ammoniacal liquor and CO2。
Embodiment 9:By (CaO+FeO)/WO3Molecular proportion is 1.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 45 μm, then, 1.5h is calcined at 965 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, use twin rollers It is levigate, clinker granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 67g- (NH4)2CO3/100g-H2O, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, at 18 DEG C React 6.5h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 29.30%.Implement Example 10:By (CaO+FeO)/WO3Molecular proportion is 1.2, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe matter Amount percentage composition raw material granularity≤45 μm, is then roasting 7.18%) and after the levigate mixing of clinker leached mud progress to obtain raw material Burn and be calcined 3h at 500 DEG C of stove neutral atmosphere, obtain clinker, it is levigate with vibrating mill after clinker cooling to room temperature, clinker granularity≤ 45μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 50g- (NH4)2CO3/100g-H2O, And 1.25 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 3.5h at 28 DEG C.Reaction terminates Afterwards, leach ore pulp to filter, with pure water filter cake three times.The leaching rate of tungsten is 9.76%.
Embodiment 11:By CaO/WO3Molecular proportion is 9, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud, raw material granularity≤200 μm, then, is being roasted Burn and be calcined 4h at 950 DEG C of stove neutral atmosphere, obtain clinker, it is levigate with vibrating mill after clinker cooling to room temperature, clinker granularity≤ 40μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and 1.1 times according to theoretical amount add carbon Sour hydrogen ammonium；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition for 10%) simultaneously It is closed, react 4.5h at 27 DEG C.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake three times.The leaching rate of tungsten is 89.05%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 12:By CaO/WO3Molecular proportion is 2.3, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 1% (mass percent) of raw material amount, raw material granularity≤100 μm, then, it is calcined at 845 DEG C of roaster neutral atmosphere 2.5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selection band stirring Leaching tanks, built-in ammonium carbonate saturated solution, and ammonium hydrogen carbonate are added according to 1.2 times of theoretical amount；Clinker is put into leaching to set It is standby, while add ammoniacal liquor and (make NH in infusion solution3Weight/mass percentage composition to be 5.9%) and closed, then, be passed through carbon dioxide Gas, the absolute pressure for controlling Leaching Systems is 2.5atm, reacts 4.5h at 27 DEG C.After reaction terminates, leach ore pulp and filter, With pure water filter cake three times.The leaching rate of tungsten is 73.65%.Then, similar embodiment 3 but supplement ammoniacal liquor and ammonium hydrogen carbonate.
Embodiment 13:By CaO/WO3Molecular proportion is 3.6, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤45 μm, then, 1h is calcined at 870 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker grain levigate with airslide disintegrating mill ≤ 74 μm of degree；The leaching tanks that leaching equipment selection band stirs, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 extraordinarily Enter ammonium hydrogen carbonate；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition be 20%) it is and closed, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.Tungsten Leaching rate is 96.15%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate.
Embodiment 14:By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 0.5% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤50 μm, then, in roaster neutral atmosphere 2h is calcined at 920 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with agitator mill；Leaching is set Alternative leaching device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put Enter leaching equipment, react 2h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching of tungsten Rate is 98.22%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 15:By (CaO+FeO)/WO3Molecular proportion is 3.4, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 45 μm, then, 2h is calcined at 960 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, ground with rod mill Carefully, clinker granularity≤200 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.2 times of addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, With pure water filter cake 2 times.The leaching rate of tungsten is 98.35%.Then, similar embodiment 3, APT products reach national 0 grade of product mark Alignment request.
Embodiment 16:By (CaO+FeO)/WO3Molecular proportion is 4.1, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 61 μm, then, 2h is calcined at 970 DEG C of roaster oxidizing atmosphere, obtains clinker, after clinker cooling to room temperature, use ball mill It is levigate, clinker granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 times of addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 55 DEG C.After reaction terminates, leach ore pulp and filter, With pure water filter cake 2 times.The leaching rate of tungsten is 97.31%.Then, similar embodiment 3, APT products reach national 0 grade of product mark Alignment request.
Embodiment 17:By CaO/WO3Molecular proportion is 6.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe matter 2.04%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤53 μm, then, 0.5h is calcined at 990 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker grain levigate with planet mill ≤ 45 μm of degree；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.5 times according to theoretical amount add carbon Sour hydrogen ammonium；Clinker is put into leaching equipment, reacts 2h at 62 DEG C.After reaction terminates, leach ore pulp and filter, filtered with pure water Cake 5 times.The leaching rate of tungsten is 96.78%.Then, similar embodiment 3 but supplement ammonium carbonate and ammoniacal liquor, APT products reach country 0 The standard requirement of level product.
Embodiment 18:By (CaO+FeO)/WO3Molecular proportion is 4.7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 74 μm, then, 2h is calcined at 980 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, with high pressure mill Machine is levigate, clinker granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.6 times addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 3.5h at 75 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 2 times.The leaching rate of tungsten is 97.01%.Then, similar embodiment 3, APT products reach 0 grade of country The requirement of product standard.
Embodiment 19:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 0.5% (mass percent) of raw material amount, raw material granularity≤40 μm, then, it is calcined at 880 DEG C of roaster neutral atmosphere 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, Adding ammoniacal liquor (makes NH in infusion solution simultaneously3Weight/mass percentage composition to be 8.2%) and closed, then pass to carbon dioxide gas Body, the absolute pressure for controlling Leaching Systems is 3atm, reacts 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake is three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 20:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 5% (mass percent) of raw material amount, raw material granularity≤30 μm, then, 1h is calcined at 860 DEG C of roaster neutral atmosphere, Obtain clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with tower mill；Leaching equipment selection is with stirring Leaching tanks, built-in unsaturated carbonate ammonium and WO containing 60g/L3Ammonium tungstate mixed solution；Clinker is put into leaching equipment, added simultaneously Entering ammoniacal liquor (makes NH in infusion solution3Weight/mass percentage composition to be 15%) and closed, then pass to carbon dioxide, control leaching The absolute pressure for going out system is 1.2atm, reacts 6h at 35 DEG C.After reaction terminates, ore pulp press filtration is leached, is filtered with pure water Cake is three times.The leaching rate of tungsten is 98.03%.Then, similar embodiment 3 but supplement ammoniacal liquor, CO2And ammonium carbonate.
Embodiment 21:By CaO/WO3Molecular proportion is 2.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤36 μm, then, 1h is calcined at 880 DEG C of roaster reducing atmosphere, obtains clinker, after clinker cooling to room temperature, clinker grain levigate with vibrating mill ≤ 45 μm of degree；The leaching tanks that leaching equipment selection band stirs, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 extraordinarily Enter ammonium hydrogen carbonate；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition be 10.0%) it is and closed, carbon dioxide is then passed to, the absolute pressure for controlling Leaching Systems is 1.5atm, anti-at 32 DEG C Answer 3.8h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 42.75%.Then, class Like embodiment 3 but supplement ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 22:By CaO/WO3Molecular proportion is 1.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤45 μm, then, 1h is calcined at 880 DEG C of roaster neutral atmosphere, obtains clinker, it is levigate with ball mill after clinker cooling to room temperature, clinker granularity≤ 45μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and 1.4 times according to theoretical amount add carbon Sour hydrogen ammonium；Clinker is put into leaching equipment, while adds ammoniacal liquor (weight/mass percentage composition for making NH3 in infusion solution is 7.4%) And it is closed, then, carbon dioxide is passed through, the absolute pressure for controlling Leaching Systems is 1.9atm, reacts 3.8h at 32 DEG C. After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 38.35%.Then, it is similar to implement Example 3 but supplement ammoniacal liquor and CO2。
Embodiment 23:By (CaO+FeO)/WO3Molecular proportion is 1.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 33 μm, then, 5h is calcined at 965 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, use vibrating mill It is levigate, clinker granularity≤74 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 80g- (NH4)2CO3/100g-H2O, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, at 20 DEG C React 6.5h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 22.96%.Then, Similar embodiment 3.
Embodiment 24:By (CaO+FeO)/WO3Molecular proportion is 2.9, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe weight/mass percentage composition are 7.18%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 2% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤30 μm, then, in roaster neutral atmosphere 850 3h is calcined at DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with twin rollers；Leaching equipment selects Ball milling infuser, built-in sal volatile, carbonic acid ammonium concentration are 80g- (NH4)2CO3/100g-H2O, and according to theoretical amount 1.25 times of addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 28 DEG C.After reaction terminates, leach ore pulp and filter, With pure water filter cake three times.The leaching rate of tungsten is 95.71%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate And ammoniacal liquor.
Embodiment 25:By CaO/WO3Molecular proportion is 4, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud, raw material granularity≤28 μm, then, is being roasted Burn and be calcined 4h at 950 DEG C of stove oxidizing atmosphere, obtain clinker, it is levigate with ball mill after clinker cooling to room temperature, clinker granularity≤ 45μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, added simultaneously Entering ammoniacal liquor (makes NH in infusion solution3Weight/mass percentage composition to be 20%) and closed, react 4.5h at 27 DEG C.Reaction terminates Afterwards, leach ore pulp to filter, with pure water filter cake three times.The leaching rate of tungsten is 98.35%.Then, similar embodiment 3 but supplement Ammoniacal liquor.
Embodiment 26:By CaO/WO3Molecular proportion is 2.3, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 4.5% (mass percent) of raw material amount, raw material granularity≤41 μm, then, it is calcined at 845 DEG C of roaster neutral atmosphere 2.5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤83 μm levigate with ball mill；Leaching equipment selection ball milling leaching Go out device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, together When to add ammoniacal liquor (weight/mass percentage composition for making NH3 in infusion solution is 9.8%) and closed, react 4.5h at 37 DEG C.Reaction After end, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 68.65%.Then, similar embodiment 3 but Supplement ammonium carbonate, ammoniacal liquor and CO2。
Embodiment 27:By (CaO+FeO)/WO3Molecular proportion is 4.8, by certain scheelite (WO3Weight/mass percentage composition is 52.27%, Fe weight/mass percentage composition are 5.86%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 2.5% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤61 μm, then, in roaster neutral atmosphere 1h is calcined at 870 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with rod mill；Leaching equipment The leaching tanks with stirring, built-in ammonium carbonate saturated solution are selected, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；By clinker Leaching equipment is put into, reacts 8.0h at 32 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.Tungsten Leaching rate is 97.10%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 28:By (CaO+FeO+MnO)/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, nodules after manganese spar and the levigate mixing of lime stone progress ≤ 14 μm of degree, then, 2h is calcined at 920 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, with vibration It is levigate, clinker granularity≤45 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.2 times addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 5h at 43 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 2 times.The leaching rate of tungsten is 98.42%.Then, similar embodiment 3, APT products reach 0 grade of country The requirement of product standard.
Embodiment 29:By (CaO+FeO)/WO3Molecular proportion is 4.9, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 42 μm, then, 2h is calcined at 960 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, ground with planetary mills Carefully, clinker granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to the 1.2 of theoretical amount Ammonium hydrogen carbonate is added again；Clinker is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake 2 times.The leaching rate of tungsten is 97.35%.Then, similar embodiment 3, APT products reach 0 grade of product standard of country will Ask.
Embodiment 30:By (CaO+MnO)/WO3Molecular proportion is 4.6, by certain scheelite (WO3Weight/mass percentage composition is 60.94%) raw material are obtained after carrying out levigate mixing with manganese spar and clinker leached mud, raw material granularity≤44 μm, then, are being calcined 1.5h is calcined at 980 DEG C of stove neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 levigate with Ball-stirring mill μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.5 times according to theoretical amount add ammonium hydrogen carbonate； Clinker is put into leaching equipment, reacts 4h at 50 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 4 times. The leaching rate of tungsten is 97.99%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 31:By CaO/WO3Molecular proportion is 4.3, by certain scheelite (WO3Weight/mass percentage composition be 60.94%) with it is ripe Material leached mud carries out obtaining raw material after levigate mixing, raw material granularity≤48 μm, then, is roasted at 970 DEG C of roaster neutral atmosphere 2h is burnt, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with rod mill；Leaching equipment selection stirring leaching Go out device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, 4h is reacted at 55 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake.The leaching rate of tungsten is 97.74%.Then, Similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 32:By (CaO+FeO)/WO3Molecular proportion is 4.9, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 38 μm, then, 1h is calcined at 990 DEG C of roaster oxidizing atmosphere, obtains clinker, after clinker cooling to room temperature, ground with ball mill Carefully, clinker granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to the 1.5 of theoretical amount Ammonium hydrogen carbonate is added again；Clinker is put into leaching equipment, reacts 4h at 62 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake 5 times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3, APT products reach 0 grade of product standard of country will Ask.
Embodiment 33:By CaO/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition be 60.94%) with it is ripe Material leached mud carries out obtaining raw material after levigate mixing, raw material granularity≤63 μm, then, is roasted at 980 DEG C of roaster neutral atmosphere 2h is burnt, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with Ball-stirring mill；Leaching equipment selection stirring leaching Go out device, built-in ammonium carbonate saturated solution, and 1.3 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, 0.5h is reacted at 75 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching rate of tungsten is 97.51%. Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 34:By (CaO+MnO)/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe weight/mass percentage composition is 0.43%) with obtaining raw material, fluorine after manganese spar and the levigate mixing of clinker leached mud progress Change calcium addition be dry tungsten mineral material amount 6.0% (mass percent), raw material granularity≤36 μm, then, in roaster 1h is calcined at 880 DEG C of neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with Ball-stirring mill； Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and 1.5 times according to theoretical amount add bicarbonate Ammonium；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition to be 5.0%) and close Close, react 3.8h at 32 DEG C.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 35:By (CaO+MnO)/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe weight/mass percentage composition are raw 0.43%) and after manganese spar and the levigate mixing of clinker leached mud progress to obtain raw material Material granularity≤36 μm, then, 1h is calcined at 880 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, used Ball-stirring mill is levigate, clinker granularity≤45 μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and press According to reason 1.5 times of addition ammonium hydrogen carbonate of stoichiometric；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3's Weight/mass percentage composition is 5.0%) and closed, reacts 3.8h at 32 DEG C.After reaction terminates, ore pulp press filtration is leached, is washed with pure water Wash filter cake three times.The leaching rate of tungsten is 86.23%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 36:By CaO/WO3Molecular proportion is 2.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 4.5% (mass percent) of raw material amount, raw material granularity≤37 μm, then, it is calcined at 880 DEG C of roaster reducing atmosphere 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤53 μm levigate with vibromill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution, and 1.15 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching to set It is standby, while add ammoniacal liquor and (make NH in infusion solution3Weight/mass percentage composition to be 4.1%) and closed, then, be passed through carbon dioxide Gas, the absolute pressure for controlling Leaching Systems is 1.3atm, reacts 9h at 32 DEG C.After reaction terminates, leach ore pulp and filter, use Pure water filter cake is three times.The leaching rate of tungsten is 74.75%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 37:By CaO/WO3Molecular proportion is 2.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of lime stone progress, the addition of calcirm-fluoride is former for dry tungsten mineral 1.5% (mass percent) of doses, raw material granularity≤24 μm, then, 3h is calcined at 880 DEG C of roaster reducing atmosphere, Obtain clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with ball mill；Leaching equipment selects ball milling infuser, Built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, reacts 8.0h at 32 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 55.45%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 38:By (CaO+FeO)/WO3Molecular proportion is 10, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are raw 2.04%) and after siderite and the levigate mixing of clinker leached mud progress to obtain raw material Material granularity≤38 μm, then, 1h is calcined at 950 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, used Vibromill is levigate, clinker granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 58g-(NH4)2CO3/100g-H2O, and 1.3 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, 40 9h is reacted at DEG C.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake three times.The leaching rate of tungsten is 96.93%.So Afterwards, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 39:By CaO/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 1.0% (mass percent) of raw material amount, raw material granularity≤33 μm, then, it is calcined at 895 DEG C of roaster neutral atmosphere 8h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with vibromill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution, and 1.9 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, 6h is reacted at 20 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 95.01%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 40:By CaO/WO3Molecular proportion is 3.9, by certain tungsten slurry (WO316.22%) and stone weight/mass percentage composition is Lime stone carries out obtaining raw material after levigate mixing, raw material granularity≤40 μm, then, is calcined at 940 DEG C of roaster reducing atmosphere 3h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Matter It is 12%) and closed to measure percentage composition, reacts 4h at 50 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake Three times.The leaching rate of tungsten is 92.31%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 41:By (CaO+FeO)/WO3Molecular proportion is 6.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, the addition of calcirm-fluoride after the levigate mixing of lime stone progress For 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, in 965 DEG C of roaster neutral atmosphere Lower roasting 1.5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with ball mill；Leaching equipment selects Ball milling infuser, built-in sal volatile, carbonic acid ammonium concentration are 67g- (NH4)2CO3/100g-H2O, and according to the 1.4 of theoretical amount Ammonium hydrogen carbonate is added again；Clinker is put into leaching equipment, reacts 20.0h at 10 DEG C.After reaction terminates, leach ore pulp and filter, With pure water filter cake three times.The leaching rate of tungsten is 91.96%.Then, similar embodiment 3, APT products reach national 0 grade of product Standard requirement.
Embodiment 42:By (CaO+FeO)/WO3Molecular proportion is 3.6, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe weight/mass percentage composition are 7.18%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 2.6% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤25 μm, then, in roaster neutral atmosphere 3h is calcined at 850 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with ball mill；Leaching equipment Ball milling infuser is selected, built-in sal volatile, carbonic acid ammonium concentration is 70g- (NH4)2CO3/100g-H2O, and according to theoretical amount 1.2 times addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 3.5h at 40 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 98.76%.Then, similar embodiment 3, APT products reach 0 grade of country The requirement of product standard.
Embodiment 43:By CaO/WO3Molecular proportion is 10, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤28 μm, then, 4h is calcined at 845 DEG C of roaster neutral atmosphere, obtains clinker, it is levigate with vibromill after clinker cooling to room temperature, clinker granularity≤ 74μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, added simultaneously Entering ammoniacal liquor (makes NH in infusion solution3Weight/mass percentage composition to be 28%) and closed, react 4.5h at 27 DEG C.Reaction terminates Afterwards, leach ore pulp to filter, with pure water filter cake three times.The leaching rate of tungsten is 96.01%.Then, similar embodiment 3 but supplement Ammonium carbonate, ammoniacal liquor and CO2。
Embodiment 44:By CaO/WO3Molecular proportion is 3.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 5.5% (mass percent) of raw material amount, raw material granularity≤40 μm, then, it is calcined at 845 DEG C of roaster neutral atmosphere 10h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤150 μm levigate with twin rollers；Leaching equipment selection ball milling leaching Go out device, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Quality Percentage composition is 7.5%) and closed, reacts 4.5h at 27 DEG C.After reaction terminates, leach ore pulp and filter, filtered with pure water Cake is three times.The leaching rate of tungsten is 98.49%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 45:By CaO/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤45 μm, then, 6h is calcined at 1050 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity levigate with rod mill ≤45μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, simultaneously Adding ammoniacal liquor (makes NH in infusion solution3Weight/mass percentage composition to be 9.1%) and closed, react 3.8h at 32 DEG C.Reaction knot Shu Hou, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 97.15%.Then, similar embodiment 3 but benefit Fill ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 46:By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 6% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster neutral atmosphere 995 0.5h is calcined at DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤8 μm levigate with Raymond mill；Leaching equipment selects Leaching device, built-in ammonium carbonate saturated solution are selected, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching Go out equipment, react 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching rate of tungsten is 97.22%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 47:By (CaO+FeO)/WO3Molecular proportion is 5.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 2% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster reducing atmosphere 2h is calcined at 960 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤20 μm levigate with airslide disintegrating mill；Leach Equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；By clinker Leaching equipment is put into, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching of tungsten Extracting rate is 98.16%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 48:By (CaO+FeO)/WO3Molecular proportion is 4.2, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 3.5% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster neutral atmosphere 0.5h is calcined at 850 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤8 μm levigate with Raymond mill；Leaching equipment Leaching device, built-in ammonium carbonate saturated solution are selected, and 1.5 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into Leaching equipment, react 4h at 50 DEG C.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake 4 times.The leaching rate of tungsten For 98.33%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 49:By (CaO+FeO)/WO3Molecular proportion is 4.1, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 53 μm, then, 8h is calcined at 930 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, crushed with overhang roll Machine is levigate, clinker granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.1 times addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 25 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 2 times.The leaching rate of tungsten is 94.22%.Then, similar embodiment 3, APT products reach 0 grade of country The requirement of product standard.
Embodiment 50:By CaO/WO3Molecular proportion is 5.6, by certain scheelite (WO3Weight/mass percentage composition be 60.94%) with it is ripe Material leached mud obtains raw material after carrying out levigate mixing, and the addition of calcirm-fluoride is 2.5% (quality percentage of dry tungsten mineral material amount Number), raw material granularity≤53 μm, then, 1h is calcined at 910 DEG C of roaster neutral atmosphere, obtains clinker, clinker cooling to room temperature Afterwards, it is levigate with ball mill, clinker granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and presses According to reason 1.5 times of addition ammonium hydrogen carbonate of stoichiometric；Clinker is put into leaching equipment, reacts 4h at 62 DEG C.After reaction terminates, leach Ore pulp filters, with pure water filter cake 5 times.The leaching rate of tungsten is 98.78%.Then, similar embodiment 3, APT products reach state 0 grade of product standard requirement of family.
Embodiment 51:By (CaO+FeO)/WO3Molecular proportion is 4.7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after the levigate mixing of clinker leached mud progress, calcirm-fluoride adds Enter 2.8% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤74 μm, then, in roaster neutral atmosphere 2h is calcined at 900 DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment Leaching device, built-in ammonium carbonate saturated solution are selected, and 1.6 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into Leaching equipment, react 1.5h at 75 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching of tungsten Rate is 95.01%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 52:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 3.3% (mass percent) of raw material amount, raw material granularity≤45 μm, then, it is calcined at 880 DEG C of roaster neutral atmosphere 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with vibromill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Matter It is 8.0%) and closed to measure percentage composition, reacts 3.8h at 50 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Filter cake is three times.The leaching rate of tungsten is 96.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 53:By CaO/WO3Molecular proportion is 4.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 7% (mass percent) of raw material amount, raw material granularity≤40 μm, then, 1h is calcined at 810 DEG C of roaster neutral atmosphere, Obtain clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with planetary mills；Leaching of the leaching equipment selection with stirring Go out groove, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Quality Percentage composition is 5.5%) and closed, reacts 6h at 45 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake Three times.The leaching rate of tungsten is 98.63%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 54:By CaO/WO3Molecular proportion is 3.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 5% (mass percent) of raw material amount, raw material granularity≤96 μm, then, it is calcined at 880 DEG C of roaster reducing atmosphere 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with Ball-stirring mill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make the matter of NH3 in infusion solution It is 3.5%) and closed to measure percentage composition, reacts 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Filter cake is three times.The leaching rate of tungsten is 96.75%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 55:By CaO/WO3Molecular proportion is 12, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material after the levigate mixing of clinker leached mud progress, the addition of calcirm-fluoride is dry tungsten ore 1.5% (mass percent) of raw material amount, raw material granularity≤36 μm, then, it is calcined at 750 DEG C of roaster neutral atmosphere 5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤100 μm levigate with twin rollers；Leaching equipment selection ball milling leaching Go out device, built-in ammonium carbonate saturated solution, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, 3.8h is reacted at 32 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 86.35%.
Embodiment 56:By (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, 2.04%) Fe weight/mass percentage compositions is carry out obtaining after levigate mixing raw material with lime stone, raw material granularity≤106 μm, then, 7h is calcined at 1000 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity levigate with vibromill ≤45μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 35g- (NH4)2CO3/100g- H2O, and 1.3 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 9h at 40 DEG C.Reaction knot Shu Hou, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 95.99%.Then, similar embodiment 3, APT Product reaches 0 grade of product standard requirement of country.
Embodiment 57:By CaO/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud, raw material granularity≤45 μm, then, is being roasted Burn and be calcined 5h at 1200 DEG C of stove neutral atmosphere, obtain clinker, it is levigate with vibromill after clinker cooling to room temperature, clinker granularity≤ 74μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and 1.4 times according to theoretical amount add bicarbonate Ammonium；Clinker is put into leaching equipment, reacts 6h at 20 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three It is secondary.The leaching rate of tungsten is 78.01%.
Embodiment 58:By CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO316.22%) and clinker weight/mass percentage composition is Leached mud carries out obtaining raw material after levigate mixing, raw material granularity≤96 μm, then, is calcined at 1400 DEG C of roaster reducing atmosphere 3h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Matter It is 6%) and closed to measure percentage composition, reacts 4h at 30 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake Three times.The leaching rate of tungsten is 81.51%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 59:By (CaO+FeO)/WO3Molecular proportion is 3.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 45 μm, then, 8h is calcined at 965 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, use centrifugal mill It is levigate, clinker granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 20g- (NH4)2CO3/100g-H2O, and 1.4 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, at 18 DEG C React 6.5h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 92.96%.Then, Similar embodiment 3.
Embodiment 60:By (CaO+FeO)/WO3Molecular proportion is 3.2, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe weight/mass percentage composition is 7.18%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 1.5% (mass percent), raw material granularity≤45 μm, then, in roaster 3h is calcined at 850 DEG C of neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with vibromill； Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and 1.25 times according to theoretical amount add ammonium hydrogen carbonate； Clinker is put into leaching equipment, reacts 3.5h at 28 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three It is secondary.The leaching rate of tungsten is 96.76%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 61:By CaO/WO3Molecular proportion is 9, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud and calcirm-fluoride, and the addition of calcirm-fluoride is 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasted at 950 DEG C of roaster neutral atmosphere 4h is burnt, obtains clinker, after clinker cooling to room temperature, clinker granularity≤96 μm levigate with ball mill；Leaching equipment selection ball milling leaching Go out device, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Quality Percentage composition is 5.9%) and closed, reacts 4.5h at 47 DEG C.After reaction terminates, leach ore pulp and filter, filtered with pure water Cake is three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 62:By CaO/WO3Molecular proportion is 3.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in 845 DEG C of roaster neutral atmosphere Lower roasting 5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects band The leaching tanks of stirring, built-in sal volatile, carbonic acid ammonium concentration are 40g- (NH4)2CO3/100g-H2O；Clinker is put into leaching Equipment, while add ammoniacal liquor and (make NH in infusion solution3Weight/mass percentage composition to be 4%) and closed, react 4.5h at 45 DEG C. After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 97.65%.Then, it is similar to implement Example 3 but supplement ammoniacal liquor and CO2。
Embodiment 63:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 1.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤120 μm, then, in roaster neutral atmosphere 870 3h is calcined at DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects Leaching tanks with stirring, built-in sal volatile, carbonic acid ammonium concentration is 45g- (NH4)2CO3/100g-H2O；Clinker is put into leaching Go out equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition to be 7.9%) and closed, react at 5 DEG C 15h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 93.15%.Then it is similar real Apply example 3 but supplement ammonium carbonate, ammoniacal liquor and CO2。
Embodiment 64:By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 5.4% (mass percent), raw material granularity≤45 μm, then, in roaster 4h is calcined at 750 DEG C of neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with vibromill； Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Will Clinker is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.Tungsten Leaching rate be 97.22%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 65:By (CaO+FeO)/WO3Molecular proportion is 3.4, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 3% (mass percent), raw material granularity≤45 μm, then, in roaster 15h is calcined at 760 DEG C of atmosphere of property, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with rod mill；Leaching Go out equipment selection leaching device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Will be ripe Material is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.Tungsten Leaching rate is 97.35%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 66:By (CaO+FeO)/WO3Molecular proportion is 4.2, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 45 μm, then, 8h is calcined at 980 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, ground with ball mill Carefully, clinker granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to 4 times of theoretical amount Add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 50 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Wash filter cake 4 times.The leaching rate of tungsten is 96.33%.Then, similar embodiment 3, APT products reach 0 grade of product standard of country will Ask.
Embodiment 67:By (CaO+FeO)/WO3Molecular proportion is 4.1, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after lime stone and the levigate mixing of fluorite progress, fluorite adds Enter 6% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤48 μm, then, in roaster neutral atmosphere 970 2h is calcined at DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤40 μm levigate with agitator mill；Leaching equipment selects Leaching device, built-in sal volatile are selected, carbonic acid ammonium concentration is 25g- (NH4)2CO3/100g-H2O, and according to theoretical amount 1.4 times of addition ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 0.5h at 80 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 2 times.The leaching rate of tungsten is 96.36%.Then, similar embodiment 3, APT products reach 0 grade of country The requirement of product standard.
Embodiment 68:By (CaO+FeO)/WO3Molecular proportion is 6.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition 2.04%) to carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤ 53 μm, then, 8h is calcined at 990 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, ground with rod mill Carefully, clinker granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 3 times of theoretical amount Add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 62 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Wash filter cake 5 times.The leaching rate of tungsten is 97.70%.Then, similar embodiment 3, APT products reach 0 grade of product standard of country will Ask.
Embodiment 69:By (CaO+FeO)/WO3Molecular proportion is 4.7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, fluorite after clinker leached mud and the levigate mixing of fluorite progress Addition be dry tungsten mineral material amount 4% (mass percent), raw material granularity≤45 μm, then, in roaster neutrality gas 2h is calcined at 980 DEG C of atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤40 μm levigate with ball mill；Leaching is set Alternative leaching device, built-in ammonium carbonate saturated solution, and 1.6 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put Enter leaching equipment, react 3.5h at 75 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching of tungsten Extracting rate is 97.01%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 70:By CaO/WO3Molecular proportion is 3.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, in 880 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects band The leaching tanks of stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make in infusion solution NH3Weight/mass percentage composition to be 6.7%) and closed, react 0.5h at 90 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake is three times.The leaching rate of tungsten is 93.15%.Then similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 71:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 3.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤90 μm, then, in 860 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects band The leaching tanks of stirring, built-in ammonium carbonate saturated solution, and 1.1 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching Go out equipment, react 6h at 45 DEG C.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake three times.The leaching rate of tungsten is 97.09%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 72:By CaO/WO3Molecular proportion is 3.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 4.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster reducing atmosphere 880 1h is calcined at DEG C, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with vibromill；Leaching equipment selects Ball milling infuser, built-in ammonium carbonate saturated solution,；Clinker is put into leaching equipment, while add ammoniacal liquor (to make in infusion solution NH3Weight/mass percentage composition to be 7.5%) and closed, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake is three times.The leaching rate of tungsten is 97.75%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 73:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in 880 DEG C of roaster neutral atmosphere Lower roasting 9h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with ball mill；Leaching equipment selects ball Grind infuser, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3's Weight/mass percentage composition is 8.6%) and closed, reacts 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and filter, washed with pure water Wash filter cake three times.The leaching rate of tungsten is 98.65%.Then similar embodiment 3 but supplement ammonium carbonate, ammoniacal liquor and CO2。
Embodiment 74:By CaO/WO3Molecular proportion is 3.7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, and in roaster, air atmosphere Under, 800 DEG C of roasting 2.0h, obtain clinker.It is levigate with vibrating mill after clinker cooling to room temperature, clinker granularity≤45 μm.Claim Clinker after taking 25.0g levigate is added in the reactor with ventilation and mechanical stirring device, while adds 60g- (NH4)2CO3/ 100g-H2O sal volatile 100mL is simultaneously closed, then, is passed through CO2Gas, the absolute pressure for controlling reaction system are 2atm, 4h is reacted at 80 DEG C.After reaction terminates, ore pulp is leached using being filtered by vacuum, with pure water filter cake three times.Tungsten in clinker Leaching rate is 97.25%.
Embodiment 75:By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 63.75%, Fe weight/mass percentage composition is 5.90%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 0.5% (mass percent), raw material granularity≤45 μm, then, in shaft furnace, Under weak reducing atmosphere, 1000 DEG C of roasting 3.0h, clinker is obtained.It is levigate with ball mill after clinker cooling to room temperature, clinker granularity ≤45μm.Weigh 30.0g it is levigate after clinker be added in the reactor with ventilation and mechanical stirring device, while add 45g- (NH4)2CO3/100g-H2O sal volatile 100mL is simultaneously closed, then passes to CO2Gas, control the absolute pressure of reaction system Power is 2atm, reacts 4h at 70 DEG C.After reaction terminates, ore pulp is leached using being filtered by vacuum, with pure water filter cake three times.It is ripe The leaching rate of tungsten is 95.17% in material.
Embodiment 76:By (CaO+FeO)/WO3Molecular proportion is 3.8, by certain wolframite (WO3Weight/mass percentage composition is 60.40%, Fe weight/mass percentage composition are to obtain raw material after 15.08%) carrying out levigate, mixing with clinker leached mud and calcirm-fluoride, The addition of calcirm-fluoride is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, is roasted in tubular type Burn in stove, under neutral atmosphere, 6.0h is calcined at 800 DEG C, obtain clinker, after clinker cooling to room temperature, clinker levigate with rod mill Granularity≤45 μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and according to 1.2 times of theoretical amount Add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 80 DEG C.After reaction terminates, leach ore pulp and taken out using vacuum Filter, with pure water filter cake three times.The leaching rate of tungsten is 97.13%.Then, the ammonium carbonate of the supplement of similar embodiment 3 loss.
Embodiment 77:By (CaO+FeO)/WO3Molecular proportion is 3.5, by certain wolframite (WO3Weight/mass percentage composition is 42.17%, Fe weight/mass percentage composition is 11.34%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 0.9% (mass percent), raw material granularity≤45 μm.Then, in roaster In, under week reduction atmosphere, 950 DEG C of roasting 5.0h, obtain clinker, after clinker cooling to room temperature, clinker levigate with Ball-stirring mill Granularity≤40 μm；Leaching equipment selects ball milling digester, built-in ammonium carbonate saturated solution, and 1.1 times according to theoretical amount add Ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4h at 75 DEG C.After reaction terminates, ore pulp is leached using vacuum filtration, is used Pure water filter cake is three times.The leaching rate of tungsten is 96.78%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate.
Embodiment 78:By CaO/WO3Molecular proportion is 6.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 2.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then in 870 DEG C of roaster neutral atmosphere Lower roasting 4h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤74 μm levigate with planetary mills；Leaching equipment selects ball Grind infuser, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3's Weight/mass percentage composition is 6.5%) and closed, reacts 4h at 30 DEG C.After reaction terminates, leach ore pulp and filter, use pure water Filter cake is three times.The leaching rate of tungsten is 98.09%.Then similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 79:By (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, 2.04%) Fe weight/mass percentage compositions is carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤25 μm, so Afterwards, 7h is calcined at 1000 DEG C of roaster neutral atmosphere, obtains clinker, it is levigate with vibrating mill after clinker cooling to room temperature, it is ripe Material granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, carbonic acid ammonium concentration is 60g- (NH4)2CO3/ 100g-H2O, and 1.3 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 9h at 40 DEG C.Instead After should terminating, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 98.03%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 80:By CaO/WO3Molecular proportion is 3.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 3.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in 950 DEG C of roaster neutral atmosphere Lower roasting 5h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤8 μm levigate with Raymond mill；Leaching equipment selects Leaching tanks with stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make infusion solution Middle NH3Weight/mass percentage composition to be 10.0%) and closed, the absolute pressure for controlling Leaching Systems be 1.0atm, at 20 DEG C instead Answer 12h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 96.20%.Then, class Like embodiment 3 but supplement ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 81:By CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO316.22%) and clinker weight/mass percentage composition is Leached mud carries out obtaining raw material after levigate mixing, raw material granularity≤45 μm, then, is calcined at 950 DEG C of roaster reducing atmosphere 3h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selection is with stirring Leaching tanks, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Matter It is 6.3%) and closed to measure percentage composition, reacts 15h at 35 DEG C.After reaction terminates, leach ore pulp and filter, filtered with pure water Cake is three times.The leaching rate of tungsten is 91.51%.Then, ammoniacal liquor and CO are supplemented2。
Embodiment 82:By (CaO+FeO)/WO3Molecular proportion is 3.6, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) with obtaining raw material, fluorine after clinker leached mud and the levigate mixing of calcirm-fluoride progress Change calcium addition be dry tungsten mineral material amount 4.1% (mass percent), raw material granularity≤45 μm, then, in roaster 1.5h is calcined at 965 DEG C of neutral atmosphere, obtains clinker, levigate with vibromill after clinker cooling to room temperature, the μ of clinker granularity≤60 m；Leaching equipment selects ball milling infuser, and built-in ammonium carbonate-ammonium tungstate mixed solution, carbonic acid ammonium concentration is 45g- (NH4)2CO3/ 100g-H2O, WO in solution3Concentration is 40g/L, and 2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching to set It is standby, react 6.5h at 18 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 97.96%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 83:By (CaO+FeO)/WO3Molecular proportion is 3.3, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe weight/mass percentage composition are 7.18%), raw material, fluorine to be obtained after carrying out levigate mixing with clinker leached mud and calcirm-fluoride Change calcium addition be dry tungsten mineral material amount 2.2% (mass percent), raw material granularity≤45 μm, then in roaster 3h is calcined at 850 DEG C of atmosphere of property, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with rod mill；Leaching Go out equipment selection ball milling infuser, built-in sal volatile, carbonic acid ammonium concentration is 40g- (NH4)2CO3/100g-H2O, and according to 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；Clinker is put into leaching equipment, reacts 20h at 42 DEG C.After reaction terminates, leach Ore pulp filters, with pure water filter cake three times.The leaching rate of tungsten is 98.76%.Then, similar embodiment 3 but supplement ammonium carbonate And ammonium hydrogen carbonate, APT products reach 0 grade of product standard requirement of country.
Embodiment 84:By CaO/WO3Molecular proportion is 9, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud and calcirm-fluoride, and the addition of calcirm-fluoride is 0.55% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, in 950 DEG C of roaster neutral atmosphere Lower roasting 4h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects band The leaching tanks of stirring, built-in unsaturated carbonate ammonium and WO containing 60g/L3Ammonium tungstate mixed solution；Clinker is put into leaching equipment, Adding ammoniacal liquor (makes NH in infusion solution simultaneously3Weight/mass percentage composition to be 9.1%) and closed, react 4.5h at 37 DEG C.Instead After should terminating, ore pulp press filtration is leached, with pure water filter cake three times.The leaching rate of tungsten is 98.72%.Then similar embodiment 3 But supplement ammoniacal liquor and CO2。
Embodiment 85:By CaO/WO3Molecular proportion is 2.7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter 0.43%) amount percentage composition is carries out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤45 μm, then, 2.5h is calcined at 845 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker levigate with overhang roll pulverizer Granularity≤74 μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution, and according to 1.2 times of theoretical amount Add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 4.5h at 45 DEG C.After reaction terminates, leach ore pulp and filter, use is pure Water washing filter cake is three times.The leaching rate of tungsten is 81.65%.Then similar embodiment 3 but supplement ammoniacal liquor and CO2。
Embodiment 86:By CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) with obtaining raw material, the addition of calcirm-fluoride after clinker leached mud and the levigate mixing of calcirm-fluoride progress For 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in 870 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains clinker, after clinker cooling to room temperature, clinker granularity≤45 μm levigate with ball mill；Leaching equipment selects band The leaching tanks of ball milling, built-in supersaturated ammonium carbonate slurries, carbonic acid ammonium concentration are 100g (NH4)2CO3/100g H2O；Clinker is put Enter leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition to be 6.5%) and closed, at 52 DEG C React 3.8h.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 98.25%.Then Similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
Embodiment 87:By (CaO+FeO)/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are 2.04%) with obtaining raw material after lime stone and the levigate mixing of fluorite progress, fluorite adds Enter 2.6% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster reproducibility gas 2h is calcined at 920 DEG C of atmosphere, obtains clinker, after clinker cooling to room temperature, clinker granularity≤8 μm levigate with Raymond mill；Leaching is set Alternative leaching device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put Enter leaching equipment, react 5h at 38 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake 2 times.The leaching of tungsten Rate is 98.12%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 88:By (CaO+FeO)/WO3Molecular proportion is 3.4, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition are slag (the main component CaCO 2.04%) and in embodiment 86 after clinker leaching3) and Calcirm-fluoride obtains raw material after carrying out levigate mixing, and the addition of calcirm-fluoride is 4.1% (quality percentage of dry tungsten mineral material amount Number), raw material granularity≤100 μm, then, 2h is calcined at 960 DEG C of roaster neutral atmosphere, obtains clinker, clinker cooling to room Wen Hou, clinker granularity≤45 μm levigate with vibromill；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and 1.2 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 3h at 50 DEG C.After reaction terminates, leaching Go out ore pulp suction filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 98.39%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 89:By (CaO+FeO)/WO3Molecular proportion is 4.2, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition carry out levigate mixing for the slag 2.04%) and in embodiment 88 after clinker leaching and calcirm-fluoride After obtain raw material, the addition of calcirm-fluoride is 0.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤74 μm, Then, 1.5h is calcined at 980 DEG C of roaster neutral atmosphere, obtains clinker, it is levigate with vibromill after clinker cooling to room temperature, Clinker granularity≤85 μm；Leaching equipment selects ball milling infuser, and built-in supersaturated ammonium carbonate slurries, carbonic acid ammonium concentration is 120g (NH4)2CO3/100g H2O, and 1.5 times according to theoretical amount add ammonium hydrogen carbonate；Clinker is put into leaching equipment, at 70 DEG C React 6h.After reaction terminates, ore pulp press filtration is leached, with pure water filter cake 4 times.The leaching rate of tungsten is 97.23%.Then, class Like embodiment 3 but supplement ammonium carbonate and ammonium hydrogen carbonate, APT products reach 0 grade of product standard requirement of country.
Embodiment 90:By (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, 2.04%) Fe weight/mass percentage compositions is carry out obtaining after levigate mixing raw material with clinker leached mud, raw material granularity≤80 μm, so Afterwards, 7h is calcined at 1000 DEG C of roaster neutral atmosphere, obtains clinker, after clinker cooling to room temperature, clinker levigate with vibromill Granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and 1.3 times according to theoretical amount add Ammonium hydrogen carbonate；Clinker is put into leaching equipment, reacts 24h at 40 DEG C.After reaction terminates, leach ore pulp and filter, washed with pure water Wash filter cake three times.The leaching rate of tungsten is 98.66%.Then, similar embodiment 3, APT products reach 0 grade of product standard requirement of country.
Embodiment 91:By CaO/WO3Molecular proportion is 4, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe mass Percentage composition is to obtain raw material after 0.43%) carrying out levigate mixing with clinker leached mud, raw material granularity≤53 μm, then, is being roasted Burn and be calcined 10h at 950 DEG C of stove neutral atmosphere, obtain clinker, it is levigate with ball mill after clinker cooling to room temperature, clinker granularity≤ 45μm；Leaching tanks of the leaching equipment selection with stirring, built-in ammonium carbonate saturated solution；Clinker is put into leaching equipment, added simultaneously Entering ammoniacal liquor (makes NH in infusion solution3Weight/mass percentage composition to be 13.0%) and closed, react 20h at 40 DEG C.Reaction terminates Afterwards, leach ore pulp to filter, with pure water filter cake three times.The leaching rate of tungsten is 99.01%.Then, similar embodiment 3 but supplement Ammoniacal liquor and CO2。
Embodiment 92:By CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO316.22%) and clinker weight/mass percentage composition is Leached mud and calcirm-fluoride obtain raw material after carrying out levigate mixing, and the addition of calcirm-fluoride is 6.5% (matter of dry tungsten mineral material amount Measure percentage), raw material granularity≤45 μm, then, 0.5h is calcined at 750 DEG C of roaster reducing atmosphere, obtains clinker, clinker is cold But to after room temperature, clinker granularity≤45 μm levigate with centrifugal mill；Leaching equipment selects ball milling infuser, and built-in ammonium carbonate is satisfied And solution；Clinker is put into leaching equipment, while add ammoniacal liquor (to make NH in infusion solution3Weight/mass percentage composition for 8.5%) And it is closed, react 4h at 45 DEG C.After reaction terminates, leach ore pulp and filter, with pure water filter cake three times.The leaching rate of tungsten is 94.51%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor and CO2。
The exploration and practice repeatedly of the present inventor for many years shows that those skilled in the art does not have motivation to go to consider the present invention Technical concept, in the absence of using " common knowledge " or " customary means " the problem of.Even so, even with design, it is related to Multiple factors often all mutually restrict, it is interactional, be not separate, even if employing orthogonal design etc. The scientific method of modernization, still there is infinite possibility combination, and technical scheme excellent enough can not be predicted, it is " limited Secondary experiment " can not possibly obtain the appropriate value of each factor, and technical scheme excellent enough is less " apparent ".
It is more than the present invention that numerous embodiments are not limitation of the invention.It will be understood to those skilled in the art that On the premise of without departing from the spirit of the present invention and design, what any details and form to technical solution of the present invention was carried out repaiies Change, supplement, improve and replace, in the protection domain of appended claims.

Claims (8)

1. a kind of metallurgical technology containing tungsten mineral material of achievable no pollution discharge, the tungsten mineral material include wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, the metallurgical technology include：
I circulates, and using weakly alkaline solution as leaching agent, leaches fired with dispensing by tungsten mineral material and makes the transition ripe Material, leaching slurry being washed through caused leached mud after separation of solid and liquid, cleaning solution, which is fed back to, leaches link reuse, The weak base is ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor, ammoniacal liquor+CO2Gas, their any mixture, and/or they and wolframic acid Any mixture of ammonium；
II circulates, and using at least part leached mud as dispensing, feeds back to the reuse of dispensing link；
III is circulated, and at least first class purification is carried out to the thick solution containing W ion and is cleaned, the solution after purification is evaporated knot Crystalline substance, the gas that evaporation and crystal process is discharged, which is back to, leaches clinker link, recombines leaching agent use；
IV circulates, and the water that evaporation and crystal process is evaporated feeds back to the separation of solid and liquid link of leaching slurry, reuses；
V is circulated, and the slurries after crystallization are carried out with solid-liquor separation, and solid phase obtains the final products of the element containing W after water washing； And crystalline mother solution is back to the link for leaching clinker, reuse,
Therefore, the technique includes multiple closed cycles, whole non-pollution discharge,
In I circulation, raw mineral materials containing W is set to be matched with dispensing into raw material；Raw material are calcined, promotees it and chemically reacts, so as to Make its ripe material that makes the transition；W in clinker is leached using weak caustic solution, and in circular response, reclaims each link and feeds back Solution make leaching agent, and according to being actually needed supplement weak base；Separation of solid and liquid is carried out to leaching slurry, slag phase is washed, washed Wash liquid and feed back to leaching link；The transition is included tungsten mineral material, dispensing is levigate, well mixed, to prepare raw material, and Raw material are calcined, to obtain clinker, when raw material are prepared, the addition of calcareous material presses CaO/WO in raw material3、(CaO+ FeO)/WO3、(CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.0 meters；Raw material granularity is not more than 200 μ m；When raw material are calcined, temperature is not less than 500 DEG C；
Mineralizer calcirm-fluoride is added in raw material process for preparation, accelerates the reaction between tungsten mineral material and dispensing, reduces roasting Temperature；
CO in Leaching Systems2A part is from the either commodity CO of furnace gas, kiln gas caused by raw material roasting process2, another portion Divide and come from CO caused by ammonium tungstate solution evaporation and crystal process2, CO2It is passed through in leaching process or before leaching；
In V circulation, solid-liquor separation is carried out to the slurries after crystallization, to obtain crystalline mother solution and solid phase, solid phase through water and/or Ammonium salt solution is washed, and the final products of the element containing W are obtained after drying；And crystalline mother solution is also returned to the step of leaching clinker.
2. metallurgical technology according to claim 1, it is characterised in that in I circulation, clinker is crushed, be levigate.
3. metallurgical technology according to claim 1, it is characterised in that in II circulation, according to being actually needed, take at least Part leached mud feeds back to raw material configuration link as dispensing, the stockpiling of leached mud remainder.
4. metallurgical technology according to claim 1, it is characterised in that in V circulation, the solid phase of final products is carried out Dissolve and crystallize again, to obtain the final products of higher purity.
5. metallurgical technology according to claim 1, it is characterised in that when raw material are prepared, the addition of calcareous material is by life CaO/WO in material3、(CaO+FeO)/WO3、(CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.5-6.0； Raw material granularity is not more than 100 μm；When raw material are calcined, temperature is 800-1050 DEG C.
6. metallurgical technology according to claim 1, it is characterised in that when raw material are prepared, the addition of calcareous material is by life CaO/WO in material3、(CaO+FeO)/WO3、(CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 3.0-4.0； Raw material granularity is not more than 45 μm；When raw material are calcined, temperature is 850-950 DEG C.
7. metallurgical technology according to claim 1, it is characterised in that the control parameter of roasting includes raw material granularity, roasting Temperature, roasting time；Leaching parameter includes：The concentration of leaching agent, infusion solution pH value, leaching in clinker granularity, infusion solution Solution addition, leach absolute pressure, extraction temperature, extraction time.
8. metallurgical technology according to claim 1, it is characterised in that slurry is after solid-liquor separation and washing, crystallization Mother liquor and washing lotion feed back to the leaching device of clinker with the ammonia and carbon dioxide collected respectively or after mix, and solid then or passes through Product APT is made after washing and drying, or enters next stage dissolving, crystallization, purification subsystem.
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