CN104263975B - There is the tungsten mineral material metallurgical technology of multiple closed loop - Google Patents

There is the tungsten mineral material metallurgical technology of multiple closed loop Download PDF

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Publication number
CN104263975B
CN104263975B CN201410528250.2A CN201410528250A CN104263975B CN 104263975 B CN104263975 B CN 104263975B CN 201410528250 A CN201410528250 A CN 201410528250A CN 104263975 B CN104263975 B CN 104263975B
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grog
leaching
ammonium
raw material
solution
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CN104263975A (en
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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
童潇依
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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

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Abstract

A kind of metallurgical technology containing tungsten mineral material, including: make raw mineral materials become raw material with dispensing proportioning；Roasting raw material, to be transformed into grog；Use weak caustic solution to leach grog, reclaim the solution that each link feeds back；Leaching slurry being carried out solid-liquid separation, washs slag mutually, cleaning mixture feeds back to grog and leaches link (I closed loop), and at least part of leached mud feeds back to raw material configuration link (ii closed loop) as dispensing；Thick solution is carried out purification and impurity removal；Solution after purifying is evaporated crystallization；The gas discharged is back to leach the step (ii I closed loop) of grog, and the water evaporated feeds back to the solid-liquid separation link (iv closed loop) of leaching slurry；Serosity after crystallization is carried out solid-liquor separation, and solid phase is washed through water and/or ammonium salt solution, i.e. obtains the final products containing W element after drying；And crystalline mother solution also returns to the step (V closed loop) leaching grog, to this end, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.

Description

There is the tungsten mineral material metallurgical technology of multiple closed loop
Technical field
The present invention relates to a kind of method being prepared APT by tungsten mineral material, 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 " grog " refer to tungsten mineral material, dispensing through levigate, be mixed into raw material, then the material of gained after high-temperature roasting.
Term " mineralizer " refers to the reaction that can accelerate between tungsten mineral material and dispensing in raw material roasting process or reduces roasting The material of temperature.
Background technology
In prior art, the commercial run preparing APT mainly comprises the steps: by caustic soda or soda leaching tungsten mineral Raw material, it is thus achieved that coarse sodium tungstate；Exchanged by solution purification-ion or solvent extraction is made the transition and (or exchanged by ion or molten Agent abstraction impurity removal also makes the transition), it is thus achieved that pure tungsten acid ammonium solution；Pass through evaporative crystallization again, it is thus achieved that APT product.
All there is following essence defect in prior art: all uses and do not circulate or half cycle process system, be not carried out whole circulation industrial Skill.At least there is techniques below problem in prior art: must arrange waste water discharge opening, and waste water pollution problem cannot thoroughly be eradicated； Supplies are mostly expendable consumed product, and the leaching agent of leaching process is excessively used, and these supplies walk in corresponding technique Rapid outer row otherwise need to use in corresponding acid or alkali and after outer row again, supplies consume many, Production cost is high；Inevitably taking part wolfram element in waste water out of, the wolfram element response rate is low；Equipment investment is big, technique stream Journey is long, and productivity ratio is relatively low, it is more difficult to realize producing continuously.
In such APT preparation process, auxiliary material consumes relatively big, and produces a large amount of waste water；Sodium tungstate solution made the transition Producing substantial amounts of high bisulfate waste liquor in journey, evaporative crystallization mother solution produces ammonia nitrogen waste water.
If the open circuit flow process having discharge of wastewater being become and there is no the closed circuit flow process of discharge of wastewater, it is not without technical possibility Property, but input is possibly even more than profit, to this end, enterprise has to select discharge, result causes serious environment Pollute.
Summary of the invention
It is an object of the invention to provide a kind of method preparing APT from tungsten mineral material, its flow process is short, solution reusable edible, Environmental pollution is almost uprooted, low cost, be prone to industrialization.
To this end, according to an aspect of the invention, it is provided a kind of method preparing APT from tungsten mineral material, the method bag Include following steps:
1) by tungsten mineral material, after dispensing is levigate, mix homogeneously prepares raw material；
2) raw material are carried out roasting, it is thus achieved that grog, and grog is crushed, levigate；
3) with ammonium carbonate, ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate, ammonium carbonate-CO2, ammonium carbonate-ammonia-CO2, carbon Acid ammonium-ammonia, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2, ammonium carbonate-ammonia-ammonium tungstate, Ammonium carbonate-ammonium tungstate-CO2, ammonium carbonate-ammonia-ammonium tungstate-CO2System leaches grog；
4) leaching slurry washs mutually through solid-liquid separation and slag, obtains thick ammonium tungstate solution and leached mud, and part leached mud is as joining Material returns step 1) carry out raw material configuration, remainder is stored up；
5) thick ammonium tungstate solution purification and impurity removal；
6) after purifying, solution uses evaporative crystallization to separate out APT, obtains ammonia and carbon dioxide simultaneously；
7) serosity after crystallization being carried out solid-liquor separation, obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution, APT product, crystalline mother solution and step 6 is i.e. obtained after drying) return to step 3 together with the ammonia that obtains and carbon dioxide), and Ammonium carbonate in supplementary loss (can be by ammonium hydrogen carbonate or ammonia and CO2Part substitutes) Posterior circle leaching grog.
Preferably, described tungsten mineral material includes, scheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry；
Preferably, during raw material preparation, the addition of leached mud 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 For 3.0-4.0, more preferably 3.3-3.6；Raw material granularity is not particularly limited, preferably not greater than 200 μm, the most not More than 100 μm, more preferably not more than 40 μm；During raw material roasting, temperature for being not less than 500 DEG C, preferably 800-1050 DEG C, More preferably 850-950 DEG C；
Preferably, raw material process for preparation adds mineralizer, preferably calcium fluoride, to accelerate between tungsten mineral material and dispensing 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 material is During scheelite, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere；
Preferably, when tungsten mineral material is wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, calcination atmosphere is neutral or goes back Originality atmosphere, preferably neutral atmosphere；The granularity of grog is not particularly limited, preferably not greater than 200 μm, is further preferably It is not more than 74 μm, is further preferably no more than 45 μm；
Preferably, the CO in Leaching Systems2A part is from stove (kiln) gas or commodity produced by raw material roasting process CO2, another part is from CO produced by ammonium tungstate solution evaporation and crystal process2；
Preferably, CO2Can be passed through in leaching process, it is also possible to be passed through before leaching.
Preferably, leach ammonium carbonate concentration in initial system and be more than 20g-(NH4)2CO3/100g-H2O, is preferably under this system The concentration of its saturated solution, ammonium hydrogen carbonate then adds with the form of solution or solid, and the addition of ammonium hydrogen carbonate is limited the most especially System, preferably not less than makes the calcium in grog be converted into CaCO31.0 times of aequum (theoretical amount), more preferably theoretical amount 1.1-1.4 times, ammonium tungstate concentration is not particularly limited, if the ammonium tungstate that can ensure that after tungsten fully leaches in grog in gained solution Concentration is less than the equilibrium concentration under this system, and the addition of ammonia is also not particularly limited, and preferably leaches initial system Middle NH3Weight/mass percentage composition be 0%～28%, more preferably 5%～20%, more preferably 5%～10%；The leaching of grog Process is carried out in enclosed system, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, ammonium carbonate When-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-ammonia-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach grog, reactant The absolute pressure of system is not particularly limited, with ammonium carbonate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-CO2System, ammonium carbonate-ammonia Water-CO2System, ammonium carbonate-ammonium tungstate-CO2System, ammonium carbonate-ammonia-ammonium tungstate-CO2System and ammonium carbonate-ammonium hydrogen carbonate- Ammonium tungstate-CO2When system leaches grog, the absolute pressure of reaction system need to be controlled 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 DEG C；
Preferably, extraction time is not particularly limited, as long as can ensure that in grog, tungsten can fully leach, when preferably leaching Between be 0.5-8.0h, more preferably extraction time be 2-5h；Purification and impurity removal process include except molybdenum, phosphorus, stannum, arsenic, silicon, ferrum, Sodium, potassium, bismuth, antimony, calcium, magnesium process at least one；
According to another aspect of the present invention, it is provided that a kind of method used described in claim 1 prepares the system of APT, Including:
1) grinding attachment A, tungsten mineral material, dispensing after batching metering, use grinding attachment A by levigate for various raw materials, Mixing, preparation has the raw material of certain fineness and the uniformity；
2) raw material of preparation are added roasting in calcining kiln (stove), obtain grog after cooling by calcining kiln (stove)；
3) grinding attachment B, the grog burnt till uses grinding attachment B levigate；
4) leaching equipment, grog leaches in leaching equipment；
5) filter plant, leaching slurry uses filter plant to carry out filtration washing；
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, described grinding attachment A is selected from: vibrating mill, ball mill, rod mill, autogenous tumbling mill, agitator mill, outstanding Roller pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, jet mill.
Preferably, described calcining kiln (stove) including: static calcining kiln (stove) and dynamic roasting kiln (stove).
Preferably, described grinding attachment B is selected from: twin rollers, vibrating mill, ball mill, rod mill, autogenous tumbling mill, stirring Grinding machine, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, jet mill.
Preferably, described leaching equipment can be an independent leaching equipment, it is also possible to 2-4 leaching equipment is used in series.
Preferably, described leaching equipment can be leaching equipment, it is also possible to be ball milling leaching equipment.
Preferably, described leaching equipment can seal, and can bear 4atm pressure.
Preferably, described filter plant is pumping and filtering device, filtering equipment and/or natural filtration groove.
Preferably, described impurity removing equipment is decleaning tank, filter plant and/or subsider.
Preferably, it is provided with agitating device in described decleaning tank.
The present invention industrial process relative to existing APT, has an advantage in that:
1) achieve and prepared the closed cycle of solution during APT by tungsten mineral material, thus it is raw to eradicate APT in theory The problem of environmental pollution caused due to a large amount of discharge of wastewater during product；
2) by tungsten mineral material roasting is made the transition, make wolfram element change and be contained in the material easily leached by ammonium carbonate salt solution, Achieving the low-temp extraction of tungsten, reduce the energy expenditure in leaching process and cost, meanwhile, leached mud again can be as tungsten mineral Dispensing in raw material transformation process and recycle；
3) use low cost, the ammonium carbonate salts system of easily circulation leaches tungsten mineral grog, directly obtains ammonium tungstate solution, cancels Step transition from sodium tungstate solution to ammonium tungstate solution, flow process is simple；
4) recycling due to multiple supplies, supplies consumption is greatly reduced, and processing charges is greatly lowered；
5) simple to operate, it is simple to control, it is easy to commercial Application.
According to the present invention, with " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" system or " carbonic acid Ammonium-ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia -CO2" or " ammonium carbonate-ammonia-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" non-obvious as leachate, this is because: weak base Gonosome system do not process the relatively low raw material of the chemical reactivities such as scheelite, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry (or place Manage extremely inefficient).Tungsten smelting industry typically uses strong acid (example hydrochloric acid) or highly basic (such as sodium hydroxide) gonosome system and at present at height Leaching tungsten mineral material under temperature, environment under high pressure, and " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate ", " ammonium carbonate-ammonium tungstate-CO2”、 " ammonium carbonate-ammonia-ammonium tungstate ", " ammonium carbonate-ammonia ", " ammonium carbonate ", " ammonium carbonate-ammonium hydrogen carbonate ", " ammonium carbonate-ammonia -CO2", " ammonium carbonate-ammonia-ammonium tungstate-CO2", " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2", " ammonium carbonate-CO2”、 " ammonium carbonate-ammonium tungstate " and " ammonium carbonate-ammonium hydrogen carbonate-CO2" system belongs to alkalescence system, it is necessary to make the transition through raw material Step could realize leaching.
According to the present invention, select " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate- Ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-CO2” Or " ammonium carbonate-ammonia-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " carbon Acid ammonium-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system leaches, Leaching Systems material converts after crystallisation step Become ammonia and carbon dioxide, just can replenish Leaching Systems, it is achieved thereby that the whole of supplies recycle, thoroughly get rid of Abandon traditional open circuit not circulating system or open circuit half cycle system, eradicated disposal of pollutants, be truly realized green metallurgical.
According to the present invention, the tungsten leaching effect that not only can obtain when leaching liquid-solid comparison and being high, leaching liquid-solid ratio less than 10 Time, in grog, the leaching rate of tungsten does not declines, WO in gained leachate3Concentration still enough industrialized production.
According to the present invention, use " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate- Ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-CO2” Or " ammonium carbonate-ammonia-ammonium tungstate-CO2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " carbon Acid ammonium-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system system leaching grog, when leaching liquid-solid ratio and being 4, 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, only arrange waste residue outlet, no longer need to arrange waste water discharge opening, waste water is arranged The pollution problem put has obtained thorough elimination.
According to the present invention, supplies are no longer expendable consumed products, and the leaching agent of leaching process recycles, though adminicle Material is excessively used, corresponding processing step outer row, it is no longer necessary to use in corresponding acid or alkali With, therefore, supplies consumption is greatly decreased, and production cost is greatly reduced.
According to the present invention, it is achieved that circulation metallurgical technology, it is clean that " waste water " of conventional process systems is blotted squeezing, thoroughly avoids portion Dividing wolfram element to be emitted in vain, therefore, the wolfram element response rate also improves.
According to the present invention, can realize integrated production, the working environment in workshop can greatly improve, and equipment investment return rate substantially carries Height, technological process shortens, and productivity ratio is largely increased, it is possible to achieve continuous print automated production.
According to the present invention, add the pretreatment process of tungsten mineral material, use " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-CO2" or " ammonium carbonate-ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " carbon Acid ammonium-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-CO2" or " ammonium carbonate-ammonia-ammonium tungstate-CO2" or " ammonium carbonate-bicarbonate Ammonium-ammonium tungstate-CO2" or " ammonium carbonate-CO2" or " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system Leaching tungsten mineral grog, leaching condition is gentle, and leaching agent is cheap, be easy to get, and supplies reusable edible can disappear in theory Except the discharge of wastewater in production process.
According to the present invention, completely disengage from prior art, it is proposed that a kind of brand-new theory preparing APT and technique, saved Sodium tungstate solution step transition of a large amount of waste water can be produced, directly obtain ammonium tungstate solution, be inherently eliminated APT production During the discharge of waste water, and achieve recycling of supplies and solution.
According to the present invention, technological process is simple, and easy to operate, production cost is low, non-wastewater discharge, and environmental pollution is reduced to Low degree.
Accompanying drawing explanation
Fig. 1 is a kind of process chart being prepared APT by tungsten mineral material according to the present invention.
Fig. 2 is the structural principle schematic diagram of a kind of system being prepared APT by tungsten mineral material according to the present invention.
Detailed description of the invention
Embodiments of the invention are described further by 1-2 below in conjunction with the accompanying drawings.
As it is shown in figure 1, the metallurgical technology containing tungsten mineral material of the present invention comprises the following steps:
Make to become raw material 101 containing W raw mineral materials 100 and dispensing MN (M represents that cation, N represent anion) proportioning；
Roasting raw material 200, promote it and chemical reaction occur, to be transformed into containing M and the grog containing W ion, so that grog obtains Obtain high chemical reactivity；
Weak base AN (A is cation) solution is used to leach (the excessive highly basic of thorough abandoning tradition leaches prejudice) grog, so that grog Leach 300, and in circular response, reclaim the solution that each link feeds back, and supplement loss according to being actually needed Weak base AN；
Leaching slurry is carried out solid-liquid separation 400, obtains the thick solution containing A and containing W ion and the leached mud containing M, to slag Washing mutually, cleaning mixture feeds back to grog and leaches link (I closed loop), according to actual needs, takes at least part of leached mud and feeds back to Raw material configuration link (ii closed loop), as dispensing, if leached mud has remainder, are then stored up；
At least first class purification remove impurity 500 (afterbody can add extractor fan) is carried out to containing A and the thick solution containing W ion；
It is evaporated crystallizing 600 to the solution after purifying, to separate out the intermediate products containing W element；Meanwhile, will discharge with Gas and the gas relevant to N element that element A is relevant are back to leach the step (ii I closed loop) of grog 300, and evaporate The water gone out feeds back to the solid-liquid separation link (iv closed loop) of leaching slurry 300；
Serosity after crystallization is carried out solid-liquor separation 700, and to obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution Wash, i.e. obtain the final products containing W element after drying and (preferably solid phase dissolved again and crystallize, to obtain purity more High final products)；And crystalline mother solution also returns to the step (V closed loop) leaching grog,
To this end, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
As in figure 2 it is shown, the metallurgical system of the tungsten mineral material of the present invention includes successively:
Raw material preparation facilities 10, it has raw mineral materials entrance 11 and ingredient inlets 12 (is preferably also provided with mineralizer entrance 13； Preferably, each entrance is additionally provided with quantifier/dosimeter), raw material fine mill (containing vortex mixer) 14, raw material outlet 15 and leach Slag receiving port 16；
Calcining kiln (stove) 20, it connects with raw material outlet 15 with raw material silo through feeding measurement device, has heater, insulation dress Put (the most also including chiller 21), atmosphere (oxidizing atmosphere, reducing atmosphere, neutral atmosphere) controls device and thick grog Outlet 22；
Grog fine mill 30, it connects with thick grog outlet 22 through grog storehouse, has ore grinding device and thin grog outlet 31；
Leaching device 40, itself and thin grog outlet 31, there is leaching agent entrance 41, leaching slurry outlet 42, feedback gas Body recovery port 43, slurry separating, washing liquid recovery port 44, slag phase cleaning mixture recovery port 45, crystal seed entrance 46 are (preferably, Also include that carbon dioxide is passed through mouth 47)；
The equipment for separating liquid from solid (preferably defecator) of leaching slurry, it connects with leaching slurry outlet 42, has containing dispensing unit The filtration washing device 50 of the leached mud of element, thick taphole 51 containing wolfram element, leached mud feedback port 52, to remaining leached mud The outlet 53 of heap warehousing, washing liquid feedback outlet 54, the receiving port 55 of evaporative crystallization condensed water, this equipment for separating liquid from solid is in feedback Connect with the crystal seed entrance 46 of leaching device 40 to the way of the leached mud receiving port 16 of raw material preparation facilities 10；
At least first class purification knot screen 60, the entrance 61 of the first order connects with the thick taphole 51 containing wolfram element, at different levels Having purification and impurity removal agent entrance and impurity collector, afterbody has smart taphole containing wolfram element 62 (preferably, Rear stage adds extractor fan)；
Crystallization apparatus 70, its entrance 71 connects with the thick taphole 62 containing wolfram element, has slurry outlet 72, anti- The gas feedback mouth 73 and the condensation-water drain 74 that are fed to leaching device (preferably have the thick solution evaporation cerium sulphate crystal of tungsten product Device)；
The liquid-solid separation device 80 of slurry, it connects with slurry outlet 72, has crystalline mother solution and is back to leach dress The outlet 83 of outlet 81, solid phase wash water entrance 82 and the tungsten product of putting 40 (preferably, is dissolved with next stage, crystallize, is carried Pure subsystem connects).
According to the present invention, by tungsten mineral material and a certain amount of calcareous material and mineralizer after levigate, mix homogeneously obtains raw material； During raw material preparation, the addition of calcareous material presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/WO3 Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.0 meters, preferably 1.5-6.0, more preferably 3.0-4.0, more preferably For 3.3-3.6；
During raw material preparation, the mineralizer allocated into is fluoride, it is therefore preferable to calcium fluoride, and the addition of calcium fluoride is that dry tungsten mineral is former The 0.5-7% (mass percent) of doses, preferably 1-3% (mass percent)；Raw material granularity is not particularly limited, and is preferably not More than 200 μm, more preferably not more than 100 μm, more preferably not more than 40 μm；Raw material sintering temperature is not less than 500 DEG C, Preferably raw material sintering temperature is 800～1050 DEG C, more preferably 850～950 DEG C；Roasting time is not particularly limited, and temperature is low Then need to extend roasting time, for making the tungsten in raw material be fully converted into Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6, preferably roasting time is 0.5-8.0h, more preferably 1.0～3.0h, more preferably roasts at 850～950 DEG C Burn 2.0h.
For scheelite raw material, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere；For wolframite, black White tungsten composite ore and/or tungsten slurry raw material, calcination atmosphere is neutral or reducing atmosphere, preferably neutral atmosphere.
The present invention will contain Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Mixed material join ammonium salt solution body In system, leach in confined conditions, after having leached, the separated washing of leaching slurry, obtain ammonium tungstate solution.
Preferably, described Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Can be the pure compound of synthetic, Can also be tungsten mineral material obtain after treatment containing Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Mixing Thing (grog)；Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6The granularity of mixed material be not more than 200 μm, excellent Elect as less than 45 μm；Described ammonium salt solution system, can be ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-wolframic acid Ammonium-CO2System, ammonium carbonate-ammonia-ammonium tungstate system, ammonium carbonate-ammonia-water systems, Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate System, ammonium carbonate-ammonia-CO2System, ammonium carbonate-ammonia-ammonium tungstate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2 System, ammonium carbonate-CO2System, ammonium carbonate-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-ammonium hydrogen carbonate- Ammonium tungstate system, ammonium carbonate-ammonia-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach Ca3WO6And/or Ca2FeWO6 And/or Ca2MnWO6Time, the absolute pressure of Leaching Systems is not particularly limited；With ammonium carbonate-CO2System, ammonium carbonate-carbon Acid hydrogen ammonium-CO2System, ammonium carbonate-ammonia-CO2System, ammonium carbonate-ammonium tungstate-CO2System, ammonium carbonate-ammonia-ammonium tungstate -CO2System and ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2System leaches Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Time, leaching process is passed through CO2, the absolute pressure controlling Leaching Systems is not less than 1atm, is preferably 1.5-2.5atm, more preferably 2atm.
Preferably, Leaching Systems ammonium carbonate concentration is more than 20g-(NH4)2CO3/100g-H2O, the most saturated ammonium carbonate is molten Liquid.
Preferably, described ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-CO2, ammonium carbonate-ammonia-ammonium tungstate, carbon Acid ammonium-ammonium tungstate, ammonium carbonate-ammonia-ammonium tungstate-CO2With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2In solution system, wolframic acid Ammonium concentration is also not particularly limited, as long as meeting Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6In tungsten abundant After leaching, in gained solution, ammonium tungstate concentration is less than its dissolubility in this system.
Preferably, described ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium hydrogen carbonate-CO2And carbon Acid ammonium-ammonium hydrogen carbonate-ammonium tungstate-CO2Solution system, ammonium hydrogen carbonate addition is not particularly limited, preferably not less than theoretical amount 1.0 times, more preferably 1.1～1.4 times of theoretical amount.
Preferably, described ammonium carbonate-ammonia-ammonium tungstate, ammonium carbonate-ammonia-ammonium tungstate-CO2, ammonium carbonate-ammonia and ammonium carbonate- Ammonia-CO2In solution system, the addition of ammonia is also not particularly limited, and preferably leaches NH in initial system3Quality Percentage composition is 0%～28%, more preferably 5%～20%, more preferably 5%～10%.
Preferably, Leaching Systems pH is controlled 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 Ca can be made3WO6And/or Ca2FeWO6 And/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, the final liquid-solid ratio of Leaching Systems by the way of multistage feeds, can be reduced, preferably by two sections of chargings, The liquid-solid ratio controlling final Leaching Systems is 3:1～4:1mL/g.
Preferably, described sal volatile also can be by ammonium bicarbonate soln and ammonia or ammonia and CO2Part substitutes.
As (the NH in solution4)2WO4When concentration is higher, especially there is a large amount of NH4In the presence of OH, (NH4)2WO4 The high activity CaCO that can generate with leaching process3There is secondary response, generate and to be difficult to be leached by ammonium carbonate salt solution CaWO4, cause tungsten loss.Dominant response is probably:
Ca(OH)2+(NH4)2WO4=CaWO4+2NH4OH (2)
Reaction (2) is easier to carry out, and generally reacts (1) and be difficult to, but at Ca3WO6Leaching process in newborn CaCO3Activity is high, and reaction (1) is the most likely carried out, and carries out NH along with leaching process4OH and (NH4)2WO4Dense Degree is continuously increased, and reaction (1) and reaction (2) are strengthened, and ultimately result in (NH4)2WO4When concentration is higher, the loss of tungsten increases. Therefore, in airtight Leaching Systems, it is passed through CO2, neutralize rapidly the NH in solution4OH, makes reaction (1) be suppressed；With Time by add CaCO3Crystal seed, makes newborn CaCO3Growing up rapidly at seed surface, reduce its activity, suppression is anti-further Answer the carrying out of (1).Thus it is expected to obtain (the NH of high concentration simultaneously4)2WO4Solution and high tungsten leaching rate.
Additionally, be passed through CO in enclosed system2, it is also possible to improve CO2Utilization rate.
According to embodiments of the invention, by thick ammonium tungstate solution purification and impurity removal, the method for purification and impurity removal is not particularly limited, as long as After purification in solution the content of the impurity such as P, As, Si, Mo, S, Sn, Sb, K, Na, Ca, Mg meet prepare qualified APT product quality requires.According to one embodiment of present invention, the sedimentation method can be used to remove in ammonium tungstate solution Impurity, thus prepares ammonium tungstate refined liquid.
According to embodiments of the invention, ammonium tungstate refined liquid employing evaporative crystallization legal system can be taken APT, the bar of evaporative crystallization Part 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 to pH, After solid-liquid separation and product wash, it is thus achieved that APT product purity 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 Weight/mass percentage composition is 0.43%) (it is mainly composed of CaCO with grog leached mud3) and mineralizer calcium fluoride carry out levigate, mixing After obtain raw material, the addition of calcium fluoride is 5.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, Then, in roaster, under air atmosphere, 800 DEG C of roasting 2.0h, obtain grog.Clinker cooling is to after room temperature, with vibration Ore mill is levigate, grog granularity≤45 μm.Weigh 5.0g levigate after grog join band ventilation and mechanical stirring device anti- Answer in still, be simultaneously introduced 50g-(NH4)2CO3/100g-H2The sal volatile 50mL of O is the most airtight, then passes to CO2 Gas, the absolute pressure controlling reaction system is 2atm, reacts 5h at 80 DEG C.After reaction terminates, leach ore pulp and use true Empty sucking filtration, with pure water filter cake three times.In grog, the leaching rate of tungsten is 97.15%.
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 is 5.90%) with grog leached mud carry out levigate, mixing 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 grog.Clinker cooling is to room temperature After, levigate with ball mill, grog granularity≤45 μm.Weigh 20.0g grog and join band ventilation and the reaction of mechanical stirring device In still, it is simultaneously introduced 35g-(NH4)2CO3/100g-H2The sal volatile 100mL of O is the most airtight, then passes to CO2Gas Body, the absolute pressure controlling reaction system is 2atm, reacts 4h at 70 DEG C.After reaction terminates, leach ore pulp and use vacuum Sucking filtration, with pure water filter cake three times.In grog, the leaching rate of tungsten is 87.17%.
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 is 14.08%, and Mn weight/mass percentage composition is 2.25%) and grog leached mud and calcium fluoride Carry out levigate, mixing after obtain raw material, the addition of calcium fluoride is 7% (mass percent) of dry tungsten mineral material amount, raw material Granularity≤40 μm, then, in pipe type calciner, under neutral atmosphere, roasting 6.0h at 800 DEG C, obtain grog, grog is cold But to after room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in ammonium carbonate is saturated Solution, and according to 1.0 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 80 DEG C, reacts 4h.Instead After should terminating, leach ore pulp and use vacuum filtration, 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, after purification, solution uses evaporative crystallization to separate out APT, obtains ammonia and carbon dioxide simultaneously Gas, carries out solid-liquor separation to the serosity after crystallization, obtains crystalline mother solution and solid phase, and solid phase i.e. obtains APT after water washs Product, APT product reaches 0 grade of product standard-required of country；The ammonia obtained returns to leaching equipment together with carbon dioxide, And in supplementary lossAmmonium carbonatePosterior circle leaches grog.
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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, adding of calcium fluoride Enter 1.5% (mass percent) that amount is dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster, weak also Under originality atmosphere, 850 DEG C of roasting 5.0h, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity ≤45μm；Leaching equipment selects ball milling digester, built-in ammonium carbonate saturated solution, and adds carbonic acid according to 1.1 times of theoretical amount Hydrogen ammonium；Grog is put into leaching equipment, at 40 DEG C, reacts 4h.After reaction terminates, leach ore pulp and use vacuum filtration, use Pure water filter cake three times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3 but supplementAmmonium hydrogen carbonate and ammonia。
Embodiment 5: by CaO/WO3Molecular proportion is 6.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%), grog leached mud and calcium fluoride obtain raw material after carrying out levigate mixing, the addition of calcium fluoride For 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster neutral atmosphere 870 DEG C Lower roasting 4h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.3 times of theoretical amount；Grog is put Enter leaching equipment, be simultaneously introduced ammonia and (make NH in infusion solution3Weight/mass percentage composition be 5%) and airtight, then pass to two Carbon oxide gas, the absolute pressure controlling Leaching Systems is 2atm, reacts 5h at 30 DEG C.After reaction terminates, leach ore pulp With pure water filter cake three times.The leaching rate of tungsten is 98.51%.Then, similar embodiment 3 but supplementAmmonia and CO 2 。
Embodiment 6: by (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 7h at roaster neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with centrifugal mill, ripe Material granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 35g-(NH4)2CO3 /100g-H2O, and according to 1.3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 40 DEG C, reacts 9h. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.99%.Then, similar real Executing example 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 7: by CaO/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe matter Amount percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤40 μm, then, Roasting 5h at roaster neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with planet mill, grog Granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in unsaturated carbonate ammonium and containing 20g/LWO3Ammonium tungstate mixing Solution, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes leaching NH in solution3Weight/mass percentage composition is 9.5%) and airtight, then, it is passed through carbon dioxide, controls the exhausted of Leaching Systems It is 3atm to pressure, at 20 DEG C, reacts 6h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.Tungsten Leaching rate be 99.01%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 8: by CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) and grog Leached mud obtains raw material after carrying out levigate mixing, raw material granularity≤40 μm, then, and roasting at roaster reducing atmosphere 940 DEG C 3h, obtains grog, after clinker cooling to room temperature；Leaching equipment selects the leaching tanks of band stirring, built-in unsaturated carbonate ammonium and containing 120g/L WO3Ammonium tungstate mixed solution, and according to 1.4 times of theoretical amount addition ammonium hydrogen carbonate；Grog is put into leaching set Standby, it is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 10%) and airtight, at 30 DEG C, react 4h. After reaction terminates, leach ore pulp, with pure water filter cake three times.The leaching rate of tungsten is 97.51%.Then, similar embodiment 3 but supplement ammonia 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 is 2.04%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 1.5h at roaster neutral atmosphere 965 DEG C, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog Granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 67g-(NH4)2CO3 /100g-H2O, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 18 DEG C, reacts 6.5h. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 29.30%.Embodiment 10: press (CaO+FeO)/WO3Molecular proportion is 1.2, by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, Fe mass Percentage composition is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then in roasting Roasting 3h at stove neutral atmosphere 500 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity ≤45μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 50g-(NH4)2CO3 /100g-H2O, and according to 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts at 28 DEG C 3.5h.After reaction terminates, leach ore pulp sucking filtration, 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 Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤200 μm, then, Roasting 4h at roaster neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, ripe Material granularity≤40 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to the 1.1 of theoretical amount Add ammonium hydrogen carbonate again；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition It is 10%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times. The leaching rate of tungsten is 89.05%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 12: by CaO/WO3Molecular proportion is 2.3, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 1% (mass percent) of raw material amount, raw material granularity≤100 μm, then, roasting 2.5h at roaster neutral atmosphere 845 DEG C, Obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects the leaching of band stirring Go out groove, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, It is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 5.9%) and airtight, then, be passed through carbon dioxide gas Body, the absolute pressure controlling Leaching Systems is 2.5atm, reacts 4.5h at 27 DEG C.After reaction terminates, leach ore pulp sucking filtration, With pure water filter cake three times.The leaching rate of tungsten is 73.65%.Then, similar embodiment 3 but supplement ammonia and ammonium hydrogen carbonate.
Embodiment 13: by CaO/WO3Molecular proportion is 3.6, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 1h at roaster neutral atmosphere 870 DEG C, obtains grog, after clinker cooling to room temperature, levigate with jet mill, Grog granularity≤74 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 times add ammonium hydrogen carbonate；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Percent mass Content is 20%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three Secondary.The leaching rate of tungsten 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 0.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤50 μm, then, roaster neutral atmosphere 920 DEG C Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤45 μm；Leaching equipment Select leaching device, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into Leaching equipment, reacts 2h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching of tungsten Going out rate is 98.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 45 μm, then, roasting 2h at roaster neutral atmosphere 960 DEG C, obtain grog, after clinker cooling to room temperature, use rod milling Machine is levigate, grog granularity≤200 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theory 1.2 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, at 38 DEG C, reacts 5h.After reaction terminates, leach ore deposit Slurry sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 98.35%.Then, similar embodiment 3, APT product reaches To 0 grade of product standard-required of country.
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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 61 μm, then, roasting 2h at roaster oxidizing atmosphere 970 DEG C, obtain grog, after clinker cooling to room temperature, use ball Grinding machine is levigate, grog granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theory 1.4 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, at 55 DEG C, reacts 4h.After reaction terminates, leach ore deposit Slurry sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.31%.Then, similar embodiment 3, APT product reaches To 0 grade of product standard-required of country.
Embodiment 17: by CaO/WO3Molecular proportion is 6.5, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe Weight/mass percentage composition is 2.04%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤53 μm, then, Roasting 0.5h at roaster neutral atmosphere 990 DEG C, obtains grog, after clinker cooling to room temperature, levigate with planet mill, ripe Material granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.5 extraordinarily Enter ammonium hydrogen carbonate；Grog is put into leaching equipment, at 62 DEG C, reacts 2h.After reaction terminates, leach ore pulp sucking filtration, with pure Water washing filter cake 5 times.The leaching rate of tungsten is 96.78%.Then, similar embodiment 3 but supplement ammonium carbonate and ammonia, APT Product reaches 0 grade of product standard-required of country.
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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 74 μm, then, roasting 2h at roaster neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, use high pressure Disc mill is levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to reason 1.6 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, at 75 DEG C, reacts 3.5h.After reaction terminates, leaching Go out ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.01%.Then, similar embodiment 3, APT produces Product reach 0 grade of product standard-required of country.
Embodiment 19: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 0.5% (mass percent) of raw material amount, raw material granularity≤40 μm, then, roasting at roaster neutral atmosphere 880 DEG C 1h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution, and according to 1.4 times of theoretical amount addition ammonium hydrogen carbonate；Grog is put into leaching set Standby, it is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 8.2%) and airtight, then pass to carbon dioxide Gas, the absolute pressure controlling Leaching Systems is 3atm, reacts 3.8h at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, With pure water filter cake three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 20: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 5% (mass percent) of raw material amount, raw material granularity≤30 μm, then, roasting 1h at roaster neutral atmosphere 860 DEG C, Obtain grog, after clinker cooling to room temperature, levigate with tower mill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in unsaturated carbonate ammonium and the WO Han 60g/L3Ammonium tungstate mixed solution；Grog is put into leaching equipment, simultaneously Add ammonia and (make NH in infusion solution3Weight/mass percentage composition be 15%) and airtight, then pass to carbon dioxide, control The absolute pressure of Leaching Systems processed is 1.2atm, reacts 6h at 35 DEG C.After reaction terminates, leach ore pulp filter pressing, use pure water Washing filter cake three times.The leaching rate of tungsten is 98.03%.Then, similar embodiment 3 but supplement ammonia, CO2And ammonium carbonate.
Embodiment 21: by CaO/WO3Molecular proportion is 2.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤36 μm, then, Roasting 1h at roaster reducing atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, Grog granularity≤45 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 times add ammonium hydrogen carbonate；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Percent mass Content is 10.0%) and airtight, then passing to carbon dioxide, the absolute pressure controlling Leaching Systems is 1.5atm, at 32 DEG C Lower reaction 3.8h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 42.75%. Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 22: by CaO/WO3Molecular proportion is 1.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 1h at roaster neutral atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog Granularity≤45 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to 1.4 times of theoretical amount Add ammonium hydrogen carbonate；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes the weight/mass percentage composition of NH3 in infusion solution be 7.4%) and airtight, then, being passed through carbon dioxide, the absolute pressure controlling Leaching Systems is 1.9atm, anti-at 32 DEG C Answer 3.8h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 38.35%.Then, Similar embodiment 3 but supplement ammonia 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 33 μm, then, roasting 5h at roaster neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, with vibration Grinding machine is levigate, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 80g-(NH4)2CO3/100g-H2O, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, 6.5h is reacted at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, 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 is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 2% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤30 μm, then, roaster neutral atmosphere 850 DEG C Lower roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤74 μm；Leaching equipment selects Selecting ball milling infuser, built-in sal volatile, ammonium carbonate concentration is 80g-(NH4)2CO3/100g-H2O, and according to theoretical amount 1.25 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 28 DEG C, reacts 4h.After reaction terminates, leach ore pulp Sucking filtration, 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 ammonia.
Embodiment 25: by CaO/WO3Molecular proportion is 4, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤28 μm, then, Roasting 4h at roaster oxidizing atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, ripe Material granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, It is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 20%) and airtight, at 27 DEG C, react 4.5h.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.35%.Then, similar enforcement Example 3 but supplement ammonia.
Embodiment 26: by CaO/WO3Molecular proportion is 2.3, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 4.5% (mass percent) of raw material amount, raw material granularity≤41 μm, then, roasting at roaster neutral atmosphere 845 DEG C 2.5h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤83 μm；Leaching equipment selects ball milling Infuser, built-in ammonium carbonate saturated solution, and according to 1.2 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, It is simultaneously introduced ammonia (making the weight/mass percentage composition of NH3 in infusion solution is 9.8%) airtight, at 37 DEG C, reacts 4.5h.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 68.65%.Then, similar enforcement Example 3 but supplement ammonium carbonate, ammonia 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 is 5.86%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 2.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤61 μm, then, roaster neutral atmosphere 870 DEG C Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put Enter leaching equipment, at 32 DEG C, react 8.0h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.Tungsten Leaching rate be 97.10%.Then, similar embodiment 3 but supplement ammonia 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%) carry out levigate mixing with manganese spar and limestone after obtain raw material, raw material granularity ≤ 14 μm, then, roasting 2h at roaster neutral atmosphere 920 DEG C, obtain grog, after clinker cooling to room temperature, with vibration Grind levigate, grog 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；Grog is put into leaching equipment, at 43 DEG C, reacts 5h.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 98.42%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 42 μm, then, roasting 2h at roaster neutral atmosphere 960 DEG C, obtain grog, after clinker cooling to room temperature, use planet Grind levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.2 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.35%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 30: by (CaO+MnO)/WO3Molecular proportion is 4.6, by certain scheelite (WO3Weight/mass percentage composition is 60.94%) obtaining raw material after carrying out levigate mixing with manganese spar and grog leached mud, raw material granularity≤44 μm, then, in roasting Roasting 1.5h at stove neutral atmosphere 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity ≤45μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds carbonic acid according to 1.5 times of theoretical amount Hydrogen ammonium；Grog is put into leaching equipment, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp sucking filtration, use pure water Filter cake 4 times.The leaching rate of tungsten is 97.99%.Then, similar embodiment 3, APT product reaches 0 grade of product standard of country to be wanted Ask.
Embodiment 31: by CaO/WO3Molecular proportion is 4.3, by certain scheelite (WO3Weight/mass percentage composition is 60.94%) with ripe Material leached mud obtains raw material, raw material granularity≤48 μm after carrying out levigate mixing, then, roast at roaster neutral atmosphere 970 DEG C Burn 2h, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects to stir Mix infuser, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching set Standby, at 55 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, use pure water filter cake.The leaching rate of tungsten is 97.74%. Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 38 μm, then, roasting 1h at roaster oxidizing atmosphere 990 DEG C, obtain grog, after clinker cooling to room temperature, use ball milling Machine is levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.5 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 62 DEG C, reacts 4h.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 33: by CaO/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition is 60.94%) with ripe Material leached mud obtains raw material, raw material granularity≤63 μm after carrying out levigate mixing, then, roast at roaster neutral atmosphere 980 DEG C Burn 2h, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects to stir Mix infuser, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.3 times of theoretical amount；Grog is put into leaching set Standby, at 75 DEG C, react 0.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten It is 97.51%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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%) carry out levigate mixing with manganese spar and grog leached mud after obtain raw material, fluorination The addition of calcium is 6.0% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤36 μm, then, in roaster Roasting 1h at property atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm； Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.5 times of theoretical amount； Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 5.0%) and airtight, 3.8h is reacted at 32 DEG C.After reaction terminates, leach ore pulp filter pressing, 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, ammonia 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 is 0.43%) carry out levigate mixing with manganese spar and grog leached mud after obtain raw material, raw material Granularity≤36 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, use Ball-stirring mill is levigate, grog granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and presses According to reason 1.5 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3 Weight/mass percentage composition be 5.0%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp filter pressing, with pure Water washing filter cake three times.The leaching rate of tungsten is 86.23%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, Ammonia and CO2。
Embodiment 36: by CaO/WO3Molecular proportion is 2.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 4.5% (mass percent) of raw material amount, raw material granularity≤37 μm, then, roasting at roaster reducing atmosphere 880 DEG C 1h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤53 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution, and according to 1.15 times of theoretical amount addition ammonium hydrogen carbonate；Grog is put into leaching Equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 4.1%) and airtight, then, be passed through dioxy Changing carbon gas, the absolute pressure controlling Leaching Systems is 1.3atm, reacts 9h at 32 DEG C.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 74.75%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, Ammonia and CO2。
Embodiment 37: by CaO/WO3Molecular proportion is 2.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with limestone carry out levigate mixing after obtain raw material, the addition of calcium fluoride is that dry tungsten mineral is former 1.5% (mass percent) of doses, raw material granularity≤24 μm, then, roasting 3h at roaster reducing atmosphere 880 DEG C, Obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, Built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, at 32 DEG C, reacts 8.0h.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 55.45%.Then, similar embodiment 3 but supplement ammonia 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 is 2.04%) carry out levigate mixing with siderite and grog leached mud after obtain raw material, raw material granularity ≤ 38 μm, then, roasting 1h at roaster neutral atmosphere 950 DEG C, obtain grog, after clinker cooling to room temperature, with vibration Grind levigate, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 58g-(NH4)2CO3/100g-H2O, and according to 1.3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, 9h is reacted at 40 DEG C.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.The leaching rate of tungsten is 96.93%. Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 39: by CaO/WO3Molecular proportion is 5.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 1.0% (mass percent) of raw material amount, raw material granularity≤33 μm, then, roasting at roaster neutral atmosphere 895 DEG C 8h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution, and according to 1.9 times of theoretical amount addition ammonium hydrogen carbonate；Grog is put into leaching set Standby, at 20 DEG C, react 6h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 95.01%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 40: by CaO/WO3Molecular proportion is 3.9, by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) and stone Lime stone obtains raw material after carrying out levigate mixing, raw material granularity≤40 μm, then, and roasting at roaster reducing atmosphere 940 DEG C 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3 Weight/mass percentage composition be 12%) and airtight, at 50 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, use pure water Washing filter cake three times.The leaching rate of tungsten is 92.31%.Then, similar embodiment 3 but supplement ammonia 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 limestone carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, at roaster neutral atmosphere 965 DEG C Roasting 1.5h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects Ball milling infuser, built-in sal volatile, ammonium carbonate concentration is 67g-(NH4)2CO3/100g-H2O, and according to theoretical amount 1.4 times add ammonium hydrogen carbonate；Grog is put into leaching equipment, at 10 DEG C, reacts 20.0h.After reaction terminates, leach ore pulp Sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 91.96%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
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 is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 2.6% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤25 μm, then, roaster neutral atmosphere 850 DEG C Lower roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects Selecting ball milling infuser, built-in sal volatile, ammonium carbonate concentration is 70g-(NH4)2CO3/100g-H2O, and according to theoretical amount 1.2 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 40 DEG C, reacts 3.5h.After reaction terminates, leach ore deposit Slurry sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.76%.Then, similar embodiment 3, APT product reaches To 0 grade of product standard-required of country.
Embodiment 43: by CaO/WO3Molecular proportion is 10, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤28 μm, then, Roasting 4h at roaster neutral atmosphere 845 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog Granularity≤74 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, It is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 28%) and airtight, at 27 DEG C, react 4.5h.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 96.01%.Then, similar enforcement Example 3 but supplement ammonium carbonate, ammonia and CO2。
Embodiment 44: by CaO/WO3Molecular proportion is 3.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 5.5% (mass percent) of raw material amount, raw material granularity≤40 μm, then, roasting at roaster neutral atmosphere 845 DEG C 10h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤150 μm；Leaching equipment selects ball milling Infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3's Weight/mass percentage composition is 7.5%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, use pure water Washing filter cake three times.The leaching rate of tungsten is 98.49%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 45: by CaO/WO3Molecular proportion is 4.5, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 6h at roaster neutral atmosphere 1050 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog Granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, It is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 9.1%) and airtight, at 32 DEG C, react 3.8h.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.15%.Then, similar enforcement Example 3 but supplement ammonium hydrogen carbonate, ammonia 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 6% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, roaster neutral atmosphere 995 DEG C Lower roasting 0.5h, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects Select leaching device, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching Go out equipment, at 38 DEG C, react 5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching of tungsten Rate is 97.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 2% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, roaster reducing atmosphere 960 DEG C Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with jet mill, grog granularity≤20 μm；Leaching sets Alternative leaching device, built-in ammonium carbonate saturated solution, and according to 1.2 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put Enter leaching equipment, at 38 DEG C, react 5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.Tungsten Leaching rate is 98.16%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 3.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, roaster neutral atmosphere 850 DEG C Lower roasting 0.5h, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects Select leaching device, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.5 times of theoretical amount；Grog is put into leaching Go out equipment, at 50 DEG C, react 4h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake 4 times.The leaching of tungsten Rate is 98.33%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 53 μm, then, roasting 8h at roaster neutral atmosphere 930 DEG C, obtain grog, after clinker cooling to room temperature, use overhang roll Pulverizer is levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to reason 1.1 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, at 25 DEG C, reacts 4h.After reaction terminates, leach Ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 94.22%.Then, similar embodiment 3, APT product Reach 0 grade of product standard-required of country.
Embodiment 50: by CaO/WO3Molecular proportion is 5.6, by certain scheelite (WO3Weight/mass percentage composition is 60.94%) with ripe Material leached mud obtains raw material after carrying out levigate mixing, and the addition of calcium fluoride is 2.5% (percent mass of dry tungsten mineral material amount Number), raw material granularity≤53 μm, then, and roasting 1h at roaster neutral atmosphere 910 DEG C, obtain grog, clinker cooling is extremely After room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, And according to 1.5 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 62 DEG C, reacts 4h.Reaction terminates After, leach ore pulp sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 98.78%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride Amount is 2.8% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤74 μm, then, roaster neutral atmosphere 900 DEG C Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select leaching device, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.6 times of theoretical amount；Grog is put into leaching Go out equipment, at 75 DEG C, react 1.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching of tungsten Going out rate is 95.01%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 52: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 3.3% (mass percent) of raw material amount, raw material granularity≤45 μm, then, roasting at roaster neutral atmosphere 880 DEG C 1h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3 Weight/mass percentage composition be 8.0%) and airtight, at 50 DEG C, react 3.8h.After reaction terminates, leach ore pulp sucking filtration, with pure Water washing filter cake three times.The leaching rate of tungsten is 96.15%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 53: by CaO/WO3Molecular proportion is 4.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 7% (mass percent) of raw material amount, raw material granularity≤40 μm, then, roasting 1h at roaster neutral atmosphere 810 DEG C, Obtain grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤45 μm；Leaching equipment selects the leaching of band stirring Go out groove, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Matter Amount percentage composition is 5.5%) and airtight, at 45 DEG C, react 6h.After reaction terminates, leach ore pulp sucking filtration, use pure water Filter cake three times.The leaching rate of tungsten is 98.63%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 54: by CaO/WO3Molecular proportion is 3.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 5% (mass percent) of raw material amount, raw material granularity≤96 μm, then, roasting at roaster reducing atmosphere 880 DEG C 1h, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects band stirring Leaching tanks, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH3 in infusion solution Weight/mass percentage composition be 3.5%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp sucking filtration, with pure Water washing filter cake three times.The leaching rate of tungsten is 96.75%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 55: by CaO/WO3Molecular proportion is 12, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is dry tungsten ore 1.5% (mass percent) of raw material amount, raw material granularity≤36 μm, then, roasting at roaster neutral atmosphere 750 DEG C 5h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤100 μm；Leaching equipment selects ball milling Infuser, built-in ammonium carbonate saturated solution, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, 3.8h is reacted at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, 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%, Fe weight/mass percentage composition is 2.04%) carry out levigate mixing with limestone after obtain raw material, raw material granularity≤106 μm, then, Roasting 7h at roaster neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog Granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 35g-(NH4)2CO3 /100g-H2O, and according to 1.3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 40 DEG C, reacts 9h. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 95.99%.Then, similar real Executing example 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 57: by CaO/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 5h at roaster neutral atmosphere 1200 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog Granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.4 times of additions of theoretical amount Ammonium hydrogen carbonate；Grog is put into leaching equipment, at 20 DEG C, reacts 6h.After reaction terminates, leach ore pulp sucking filtration, use pure water Washing filter cake three times.The leaching rate of tungsten is 78.01%.
Embodiment 58: by CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) with ripe Material leached mud obtains raw material after carrying out levigate mixing, and raw material granularity≤96 μm, then, at roaster reducing atmosphere 1400 DEG C Roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects The leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes infusion solution Middle NH3Weight/mass percentage composition be 6%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, use 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, Ammonia 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 45 μm, then, roasting 8h at roaster neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, with centrifugal Grinding machine is levigate, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 20g-(NH4)2CO3/100g-H2O, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, 6.5h is reacted at 18 DEG C.After reaction terminates, leach ore pulp sucking filtration, 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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorination The addition of calcium is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, neutral at roaster Roasting 3h at atmosphere 850 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching Go out equipment choice ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；Will Leaching equipment put into by grog, reacts 3.5h at 28 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three Secondary.The leaching rate of tungsten is 96.76%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 61: by CaO/WO3Molecular proportion is 9, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, at roaster neutral atmosphere 950 DEG C Roasting 4h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤96 μm；Leaching equipment selects Ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3 Weight/mass percentage composition be 5.9%) and airtight, at 47 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure Water washing filter cake three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 62: by CaO/WO3Molecular proportion is 3.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster neutral atmosphere 845 DEG C Lower roasting 5h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Selecting the leaching tanks of band stirring, built-in sal volatile, ammonium carbonate concentration is 40g-(NH4)2CO3/100g-H2O；Grog is put Enter leaching equipment, be simultaneously introduced ammonia and (make NH in infusion solution3Weight/mass percentage composition be 4%) and airtight, anti-at 45 DEG C Answer 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.65%.Then, Similar embodiment 3 but supplement ammonia and CO2。
Embodiment 63: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 1.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤120 μm, then, roaster neutral atmosphere 870 DEG C Lower roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select band stirring leaching tanks, built-in sal volatile, ammonium carbonate concentration is 45g-(NH4)2CO3/100g-H2O；Grog is put Enter leaching equipment, be simultaneously introduced ammonia and (make NH in infusion solution3Weight/mass percentage composition be 7.9%) and airtight, at 5 DEG C Reaction 15h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 93.15%.So Rear similar embodiment 3 but supplement ammonium carbonate, ammonia 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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorination The addition of calcium is 5.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, neutral at roaster Roasting 4h at atmosphere 750 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching Go out equipment choice ball milling infuser, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；By ripe Leaching equipment put into by material, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times. The leaching rate of tungsten is 97.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorination The addition of calcium is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, at roaster neutrality gas Roasting 15h at 760 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching Go out equipment choice leaching device, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.2 times of theoretical amount；By ripe Leaching equipment put into by material, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times. The leaching rate of tungsten is 97.35%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 45 μm, then, roasting 8h at roaster neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, use ball milling Machine is levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to theoretical amount 4 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 4 times.The leaching rate of tungsten is 96.33%.Then, similar embodiment 3, APT product reaches state 0 grade of product standard-required of family.
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 is 2.04%) carry out levigate mixing with limestone and fluorite after obtain raw material, the addition of fluorite Amount is 6% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤48 μm, then, roaster neutral atmosphere 970 DEG C Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤40 μm；Leaching equipment Selecting leaching device, built-in sal volatile, ammonium carbonate concentration is 25g-(NH4)2CO3/100g-H2O, and according to theory 1.4 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, at 80 DEG C, reacts 0.5h.After reaction terminates, leach Ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 96.36%.Then, similar embodiment 3, APT product Reach 0 grade of product standard-required of country.
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 is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity ≤ 53 μm, then, roasting 8h at roaster neutral atmosphere 990 DEG C, obtain grog, after clinker cooling to room temperature, use rod milling Machine is levigate, grog granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to theoretical amount 3 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, at 62 DEG C, reacts 4h.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake 5 times.The leaching rate of tungsten is 97.70%.Then, similar embodiment 3, APT product reaches state 0 grade of product standard-required of family.
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%) carry out levigate mixing with grog leached mud and fluorite after obtain raw material, fluorite Addition is 4% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster neutral atmosphere Roasting 2h at 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤40 μm；Leaching sets Alternative leaching device, built-in ammonium carbonate saturated solution, and according to 1.6 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put Enter leaching equipment, at 75 DEG C, react 3.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.Tungsten Leaching rate be 97.01%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 70: by CaO/WO3Molecular proportion is 3.2, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roaster neutral atmosphere 880 DEG C Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes leaching molten NH in liquid3Weight/mass percentage composition be 6.7%) and airtight, at 90 DEG C, react 0.5h.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 93.15%.Then similar embodiment 3 but supplement ammonia and CO2。
Embodiment 71: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 3.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤90 μm, then, roaster neutral atmosphere 860 DEG C Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and add ammonium hydrogen carbonate according to 1.1 times of theoretical amount；Grog is put Enter leaching equipment, at 45 DEG C, react 6h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.Tungsten Leaching rate is 97.09%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 72: by CaO/WO3Molecular proportion is 3.1, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 4.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster reducing atmosphere 880 DEG C Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤74 μm；Leaching equipment selects Select ball milling infuser, built-in ammonium carbonate saturated solution,；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes in infusion solution NH3Weight/mass percentage composition be 7.5%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp sucking filtration, With pure water filter cake three times.The leaching rate of tungsten is 97.75%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 73: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster neutral atmosphere 880 DEG C Lower roasting 9h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects Select ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes in infusion solution NH3Weight/mass percentage composition be 8.6%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp sucking filtration, With pure water filter cake three times.The leaching rate of tungsten is 98.65%.Then similar embodiment 3 but supplement ammonium carbonate, ammonia and CO2。
Embodiment 74: by CaO/WO3Molecular proportion is 3.7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster, under air atmosphere, 800 DEG C of roasting 2.0h, obtain grog.Clinker cooling is to after room temperature, levigate with vibrating mill, grog granularity≤45 μm.Claim Take 25.0g levigate after grog join band ventilation and mechanical stirring device reactor in, be simultaneously introduced 60g-(NH4)2CO3 /100g-H2The sal volatile 100mL of O is the most airtight, then, is passed through CO2Gas, controls the absolute pressure of reaction system For 2atm, at 80 DEG C, react 4h.After reaction terminates, leach ore pulp and use vacuum filtration, with pure water filter cake three times. In grog, the leaching rate of tungsten 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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorination The addition of calcium is 0.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm is then, in shaft furnace, weak Under reducing atmosphere, 1000 DEG C of roasting 3.0h, obtain grog.Clinker cooling is to after room temperature, levigate with ball mill, grog grain Degree≤45 μm.Weigh 30.0g levigate after grog join band ventilation and mechanical stirring device reactor in, be simultaneously introduced 45g-(NH4)2CO3/100g-H2The sal volatile 100mL of O is the most airtight, then passes to CO2Gas, controls reactant The absolute pressure of system is 2atm, reacts 4h at 70 DEG C.After reaction terminates, leach ore pulp and use vacuum filtration, wash with pure water Wash filter cake three times.In grog, the leaching rate of tungsten is 95.17%.
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 is 15.08%) carry out levigate, mixing with grog leached mud and calcium fluoride after obtain raw material, The addition of calcium fluoride is 3% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in tubular type roasting In stove, under neutral atmosphere, roasting 6.0h at 800 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, ripe Material granularity≤45 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to the 1.2 of theoretical amount Add ammonium hydrogen carbonate again；Grog is put into leaching equipment, at 80 DEG C, reacts 4h.After reaction terminates, leach ore pulp and use true Empty sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.13%.Then, similar embodiment 3 supplements the carbon of loss Acid ammonium.
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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorine Change 0.9% (mass percent) that addition is dry tungsten mineral material amount of calcium, raw material granularity≤45 μm.Then, in roaster, Under week reduction atmosphere, 950 DEG C of roasting 5.0h, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog Granularity≤40 μm；Leaching equipment selection ball milling digester, built-in ammonium carbonate saturated solution, and according to 1.1 times of additions of theoretical amount Ammonium hydrogen carbonate；Grog is put into leaching equipment, at 75 DEG C, reacts 4h.After reaction terminates, leach ore pulp and use vacuum filtration, With pure water filter cake 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 Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 2.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then at roaster neutral atmosphere 870 DEG C Roasting 4h, obtains grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤74 μm；Leaching equipment selects Ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3 Weight/mass percentage composition be 6.5%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, use pure water Washing filter cake three times.The leaching rate of tungsten is 98.09%.Then similar embodiment 3 but supplement ammonia and CO2。
Embodiment 79: by (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤25 μm, then, Roasting 7h at roaster neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, ripe Material granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 60g-(NH4)2CO3 /100g-H2O, and according to 1.3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 40 DEG C, reacts 9h. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.03%.Then, similar real Executing example 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 80: by CaO/WO3Molecular proportion is 3.0, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 3.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster neutral atmosphere 950 DEG C Lower roasting 5h, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes leaching molten NH in liquid3Weight/mass percentage composition be 10.0%) and airtight, the absolute pressure controlling Leaching Systems is 1.0atm, at 20 DEG C Reaction 12h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 96.20%.So After, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 81: by CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) with ripe Material leached mud obtains raw material, raw material granularity≤45 μm after carrying out levigate mixing, then, roast at roaster reducing atmosphere 950 DEG C Burn 3h, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects band The leaching tanks of stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes in infusion solution NH3Weight/mass percentage composition be 6.3%) and airtight, at 35 DEG C, react 15h.After reaction terminates, leach ore pulp sucking filtration, use Pure water filter cake three times.The leaching rate of tungsten is 91.51%.Then, ammonia 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%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, fluorination The addition of calcium is 4.1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, neutral at roaster Roasting 1.5h at atmosphere 965 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤60 μm； Leaching equipment selects ball milling infuser, and built-in ammonium carbonate-ammonium tungstate mixed solution, ammonium carbonate concentration is 45g-(NH4)2CO3 /100g-H2O, WO in solution3Concentration is 40g/L, and according to 2 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching Go out equipment, at 18 DEG C, react 6.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching of tungsten Going out rate is 97.96%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 7.18%), obtain raw material, fluorine after carrying out levigate mixing with grog leached mud and calcium fluoride Changing 2.2% (mass percent) that addition is dry tungsten mineral material amount of calcium, raw material granularity≤45 μm, then in roaster neutrality Roasting 3h at atmosphere 850 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching Going out equipment choice ball milling infuser, built-in sal volatile, ammonium carbonate concentration is 40g-(NH4)2CO3/100g-H2O, and press According to reason 1.25 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, at 42 DEG C, reacts 20h.After reaction terminates, Leach ore pulp sucking filtration, 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 product reaches 0 grade of product standard-required of country.
Embodiment 84: by CaO/WO3Molecular proportion is 9, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 0.55% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roaster neutral atmosphere 950 DEG C Lower roasting 4h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks of band stirring, built-in unsaturated carbonate ammonium and the WO Han 60g/L3Ammonium tungstate mixed solution；Grog is put into leaching Equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 9.1%) and airtight, react at 37 DEG C 4.5h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.The leaching rate of tungsten is 98.72%.Then class Like embodiment 3 but supplement ammonia and CO2。
Embodiment 85: by CaO/WO3Molecular proportion is 2.7, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤45 μm, then, Roasting 2.5h at roaster neutral atmosphere 845 DEG C, obtains grog, after clinker cooling to room temperature, levigate with overhang roll pulverizer, Grog granularity≤74 μm；The leaching tanks of leaching equipment selection band stirring, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.2 times add ammonium hydrogen carbonate；Grog is put into leaching equipment, at 45 DEG C, reacts 4.5h.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 81.65%.Then similar embodiment 3 but supplement ammonia and CO2。
Embodiment 86: by CaO/WO3Molecular proportion is 3.8, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud and calcium fluoride after obtain raw material, the addition of calcium fluoride For 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roaster neutral atmosphere 870 DEG C Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Selecting the leaching tanks of band ball milling, built-in supersaturation ammonium carbonate serosity, ammonium carbonate concentration is 100g (NH4)2CO3/100g H2O；Will Leaching equipment put into by grog, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 6.5%) and airtight, 3.8h is reacted at 52 DEG C.After reaction terminates, leach ore pulp sucking filtration, 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, ammonia 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 is 2.04%) carry out levigate mixing with limestone and fluorite after obtain raw material, the addition of fluorite Amount is 2.6% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster reducing atmosphere Roasting 2h at 920 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leach Equipment choice leaching device, built-in ammonium carbonate saturated solution, and according to 1.2 times of addition ammonium hydrogen carbonate of theoretical amount；By grog Put into leaching equipment, at 38 DEG C, react 5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.Tungsten Leaching rate be 98.12%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required 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 is 2.04%) (it is mainly composed of CaCO with the slag after grog leaching in embodiment 863) and Calcium fluoride obtains raw material after carrying out levigate mixing, the addition of calcium fluoride is 4.1% (mass percent) of dry tungsten mineral material amount, Raw material granularity≤100 μm, then, roasting 2h at roaster neutral atmosphere 960 DEG C, obtain grog, clinker cooling is to room temperature After, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, at 50 DEG C, reacts 3h.After reaction terminates, Leach ore pulp sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 98.39%.Then, similar embodiment 3, APT Product reaches 0 grade of product standard-required 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 is 2.04%) with embodiment 88 in grog leach after slag and calcium fluoride carry out levigate mixing After obtain raw material, the addition of calcium fluoride is 0.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤74 μm, so After, roasting 1.5h at roaster neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibromill, Grog granularity≤85 μm；Leaching equipment selects ball milling infuser, and built-in supersaturation ammonium carbonate serosity, ammonium carbonate concentration is 120g (NH4)2CO3/100g H2O, and according to 1.5 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 70 DEG C Lower reaction 6h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake 4 times.The leaching rate of tungsten is 97.23%.So After, similar embodiment 3 but supplement ammonium carbonate and ammonium hydrogen carbonate, APT product reaches 0 grade of product standard-required of country.
Embodiment 90: by (CaO+FeO)/WO3Molecular proportion is 7, by certain scheelite (WO3Weight/mass percentage composition is 52.33%, Fe weight/mass percentage composition is 2.04%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤80 μm, then, Roasting 7h at roaster neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog Granularity≤45 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.3 times of additions of theoretical amount Ammonium hydrogen carbonate；Grog is put into leaching equipment, at 40 DEG C, reacts 24h.After reaction terminates, leach ore pulp sucking filtration, with pure Water washing filter cake three times.The leaching rate of tungsten is 98.66%.Then, similar embodiment 3, APT product reaches 0 grade of product of country Standard-required.
Embodiment 91: by CaO/WO3Molecular proportion is 4, by certain scheelite (WO3Weight/mass percentage composition is 49.53%, Fe Weight/mass percentage composition is 0.43%) carry out levigate mixing with grog leached mud after obtain raw material, raw material granularity≤53 μm, then, Roasting 10h at roaster neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog Granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, It is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 13.0%) and airtight, at 40 DEG C, react 20h.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 99.01%.Then, similar enforcement Example 3 but supplement ammonia and CO2。
Embodiment 92: by CaO/WO3Molecular proportion is 8, by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) with ripe Material leached mud and calcium fluoride obtain raw material after carrying out levigate mixing, and the addition of calcium fluoride is 6.5% (matter of dry tungsten mineral material amount Amount percent), raw material granularity≤45 μm, then, and roasting 0.5h at roaster reducing atmosphere 750 DEG C, obtain grog, ripe After material is cooled to room temperature, levigate with centrifugal mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in carbonic acid Ammonium saturated solution；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 8.5%) and airtight, at 45 DEG C, 4h is reacted.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.Tungsten Leaching rate be 94.51%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammonia and CO2。
The present inventor's exploration and practice repeatedly for many years shows, those skilled in the art does not has motivation to go to consider the technology of the present invention , there is not employing " common knowledge " or the problem of " customary means " in design.Even so, even with design, relate to Multiple factors are the most all mutually restrictions, interactional, are not separate, even if using the modern times such as orthogonal design Change scientific method, still have infinite may combining, and enough excellent the technical scheme, " reality of limited number of time can not be doped Test " the suitable value of each factor can not be obtained, enough excellent technical scheme is less " obviously ".
Above numerous embodiments of the present invention are not limitation of the invention.It will be understood to those skilled in the art that the most inclined On the premise of the spirit and design of the present invention, amendment that any details to technical solution of the present invention and form are carried out, supplement, Improve and replace, all in the protection domain of appended claims.

Claims (22)

1. the metallurgical technology containing tungsten mineral material, including: make raw mineral materials become raw material with dispensing proportioning；Roasting raw material, To be transformed into grog；Using weak caustic solution to leach grog, reclaim the solution that each link feeds back, described dispensing is containing CaCO3 Material, its addition presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is at least 1.0, and described weak base is ammonium carbonate, ammonium hydrogen carbonate, ammonia+CO2Gas, And their any mixture and/or their any mixture with ammonium tungstate；Leaching slurry is carried out solid-liquid separation, to slag Washing mutually, cleaning mixture feeds back to grog and leaches link, and at least part of leached mud feeds back to raw material configuration link as dispensing；To slightly Solution carries out purification and impurity removal；Solution after purifying is evaporated crystallization；The gas discharged is back to leach the step of grog, And the water evaporated feeds back to the solid-liquid separation link of leaching slurry；Serosity after crystallization is carried out solid-liquor separation, solid phase through water and / or ammonium salt solution washing, i.e. obtain the final products containing W element after drying；And crystalline mother solution also returns to the step leaching grog Suddenly, the CO in Leaching Systems2A part of from furnace gas/kiln gas produced by raw material roasting process or commodity CO2, another Partly from CO produced by ammonium tungstate solution evaporation and crystal process2, CO2Leaching process is passed through, or before leaching It is passed through；Leaching in initial system, if weak caustic solution is ammonium carbonate, its concentration is more than 20g-(NH4)2CO3/100g-H2O, To this end, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
2. the metallurgical technology containing tungsten mineral material, it is characterised in that this technique comprises the following steps:
Cation, N represent anion to make to become raw material, M to represent containing W raw mineral materials with dispensing MN proportioning；
Roasting raw material, promote it and chemical reaction occur, to be transformed into containing M and the grog containing W ion, so that grog obtains height Chemical reactivity；
Using weak base AN solution to leach grog, the excessive highly basic of thorough abandoning tradition leaches prejudice, and A is cation, so that ripe Material leaches, and in circular response, reclaims the solution that each link feeds back, and supplement the weak of consumption according to being actually needed Alkali AN, described weak base is ammonium carbonate, ammonium hydrogen carbonate, ammonia+CO2Gas, and their any mixture and/or they Any mixture with ammonium tungstate；
Leaching slurry is carried out solid-liquid separation, obtains the thick solution containing A and containing W ion and the leached mud containing M, to slag phase Washing, cleaning mixture feeds back to grog and leaches link, according to actual needs, takes at least part of leached mud and feed back to raw material configuration link As dispensing, if leached mud has remainder, then store up；
At least first class purification remove impurity is carried out to containing A and the thick solution containing W ion；
Solution after purifying is evaporated crystallization, to separate out the intermediate products containing W element；Meanwhile, will discharge and A unit Gas and the gas relevant to N element or root that element or root are correlated with are back to leach the step of grog, and the water evaporated feeds back Solid-liquid separation link to leaching slurry；
Serosity after crystallization is carried out solid-liquor separation, and to obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution, The final products containing W element are i.e. obtained after drying；And crystalline mother solution also returns to the step leaching grog,
CO in Leaching Systems2A part of from furnace gas/kiln gas produced by raw material roasting process or commodity CO2, another Partly from CO produced by ammonium tungstate solution evaporation and crystal process2, CO2Leaching process is passed through, or before leaching It is passed through；Leaching in initial system, if weak caustic solution is ammonium carbonate, its concentration is more than 20g-(NH4)2CO3/100g-H2O,
To this end, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that described tungsten mineral material include scheelite, Wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry；And/or described transition includes tungsten mineral material, dispensing is levigate, mixing Uniformly, to prepare raw material；Raw material are carried out roasting, to obtain grog.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that include following additional technical feature at least its One of: slurry after solid-liquor separation and washing, the ammonia of crystalline mother solution and washing liquid and collection and carbon dioxide respectively or Feeding back to the leaching device of grog after mixing, solid prepares product A PT then or after scrubbed drying, or enter next stage dissolve, Crystallization, purification subsystem；Described raw material granularity is not particularly limited；The temperature of raw material roasting is for being not less than 500 DEG C；And it is raw The time of material roasting is 0.5-8.0h.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that when described tungsten mineral material is scheelite, Calcination atmosphere is not particularly limited；And when described tungsten mineral material wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, roasting Atmosphere is neutral or reducing atmosphere.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that include following additional technical feature at least its One of: the granularity of grog is not particularly limited；Leaching ammonium carbonate concentration in initial system is the dense of its saturated solution under this system Degree；Ammonium hydrogen carbonate then adds with the form of solution or solid, and the addition of ammonium hydrogen carbonate is not particularly limited；The addition of ammonia Also it is not particularly limited；And ammonium tungstate concentration is not particularly limited, as long as can ensure that after in grog, tungsten fully leaches in gained solution Ammonium tungstate concentration less than the equilibrium concentration under this system.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that the leaching process of grog is in enclosed system Carry out, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate When system, ammonium carbonate-ammonia-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach grog, the absolute pressure of reaction system is not subject to Limit especially；With ammonium carbonate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-CO2System, ammonium carbonate-ammonia-CO2System, carbonic acid Ammonium-ammonium tungstate-CO2System, ammonium carbonate-ammonia-ammonium tungstate-CO2System and ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2System is soaked When going out grog, the absolute pressure of reaction system need to be controlled not less than 1atm.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that extraction temperature is not less than 5 DEG C；And/or, Extraction time is 0.5-8.0h.
Metallurgical technology the most according to claim 1 and 2, it is characterised in that purification and impurity removal process include except molybdenum, phosphorus, At least one in stannum, arsenic, silicon, ferrum, sodium, potassium, bismuth, antimony, calcium, magnesium.
Metallurgical technology the most according to claim 2, it is characterised in that in final products, dissolves again by solid phase And crystallization, to obtain the higher final products of purity.
11. metallurgical technologies according to claim 3, it is characterised in that carry out grog crushing, levigate.
12. metallurgical technologies according to claim 5, it is characterised in that addition presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is 1.5-6.0；Nodules Degree is no more than 200 μm；The temperature of raw material roasting is for being not less than 500 DEG C；And/or, the time of raw material roasting is 0.5-8.0h.
13. metallurgical technologies according to claim 12, it is characterised in that addition presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is 3.0-4.0, nodules Degree is no more than 100 μm, and the temperature of raw material roasting is 800-1050 DEG C, and/or, the time of raw material roasting is 1.0-3.0h.
14. metallurgical technologies according to claim 13, it is characterised in that addition presses CaO/WO in raw material3Or (CaO+FeO)/WO3Or (CaO+MnO)/WO3Or (CaO+FeO+MnO)/WO3Molecular proportion is 3.3-3.6, nodules Degree is no more than 40 μm, and the temperature of raw material roasting is 850-950 DEG C, and/or, the time of raw material roasting is 2.0h.
15. metallurgical technologies according to claim 5, it is characterised in that when described tungsten mineral material is scheelite, roasting Burning atmosphere is neutral or oxidizing atmosphere；And when described tungsten mineral material wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, Calcination atmosphere is neutral atmosphere.
16. metallurgical technologies according to claim 6, it is characterised in that the granularity of grog is no more than 200 μm；Carbonic acid The addition of hydrogen ammonium is no less than making the calcium in grog be converted into CaCO31.0 times of required theoretical amount；And/or, leach initial NH in system3Weight/mass percentage composition be 0%～28%.
17. metallurgical technologies according to claim 16, it is characterised in that the granularity of grog is no more than 74 μm；Carbonic acid The addition of hydrogen ammonium is to make the calcium in grog be converted into CaCO31.1-1.4 times of required theoretical amount；And/or, leach just initial body NH in system3Weight/mass percentage composition be 5%～20%.
18. metallurgical technologies according to claim 16, it is characterised in that the granularity of grog is no more than 45 μm；With/ Or, leach NH in initial system3Weight/mass percentage composition be 5%～10%.
19. metallurgical technologies according to claim 7, it is characterised in that the absolute pressure that need to control reaction system is 2atm.
20. metallurgical technologies according to claim 8, it is characterised in that extraction temperature is 10-80 DEG C；And/or, leach Time is not particularly limited, as long as can ensure that in grog, tungsten can fully leach.
21. metallurgical technologies according to claim 20, it is characterised in that extraction temperature is 20-70 DEG C.
22. metallurgical technologies according to claim 2, it is characterised in that extraction temperature is 30-50 DEG C.
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