CN104388670B - The tungsten mineral material metallurgical system of omnidistance non-pollution discharge - Google Patents

The tungsten mineral material metallurgical system of omnidistance non-pollution discharge Download PDF

Info

Publication number
CN104388670B
CN104388670B CN201410528734.7A CN201410528734A CN104388670B CN 104388670 B CN104388670 B CN 104388670B CN 201410528734 A CN201410528734 A CN 201410528734A CN 104388670 B CN104388670 B CN 104388670B
Authority
CN
China
Prior art keywords
leaching
grog
raw material
ammonium
tungsten
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410528734.7A
Other languages
Chinese (zh)
Other versions
CN104388670A (en
Inventor
李小斌
崔源发
周秋生
李建圃
齐天贵
徐双
刘桂华
林国荣
彭志宏
李继红
徐向明
朱志成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
Original Assignee
Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd, Central South University filed Critical Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Priority to CN201410528734.7A priority Critical patent/CN104388670B/en
Publication of CN104388670A publication Critical patent/CN104388670A/en
Application granted granted Critical
Publication of CN104388670B publication Critical patent/CN104388670B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

A kind of metallurgical system of tungsten mineral material, including: raw material preparation facilities, it has leached mud receiving port；Calcining kiln, it has the outlet of thick grog；Grog fine mill, it has the outlet of thin grog；Leaching device, it has leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase cleaning mixture recovery port, crystal seed entrance；The equipment for separating liquid from solid of leaching slurry, it has leached mud feedback port, washing liquid feedback exports, the receiving port of evaporative crystallization condensed water, and this equipment for separating liquid from solid connects with the crystal seed entrance of leaching device in feeding back to the way of leached mud receiving port of raw material preparation facilities；At least first class purification knot screen；Crystallization apparatus, it has the gas feedback mouth feeding back to leaching device；The liquid-solid separation device of slurry, it has crystalline mother solution and is back to the outlet of leaching device and the outlet of tungsten product.The present invention has eradicated contaminated wastewater, and supplies consumption is greatly decreased, and production cost is low.

Description

The tungsten mineral material metallurgical system of omnidistance non-pollution discharge
Technical field
The present invention relates to a kind of system 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 the material of sintering temperature.
Background technology
In prior art, the commercial run preparing APT mainly comprises the steps: by caustic soda or soda leaching tungsten mineral material, it is thus achieved that coarse sodium tungstate；Exchanged by solution purification-ion or solvent extraction make the transition (or exchanged by ion or solvent extraction remove impurity and make 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 technology.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, these supplies corresponding processing step after completion of the reaction directly outer row otherwise need to use in corresponding acid or alkali and after outer row again, supplies consume many, and 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, and technological process 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；Producing substantial amounts of high bisulfate waste liquor in sodium tungstate solution transformation process, evaporative crystallization mother solution produces ammonia nitrogen waste water.
If the open circuit flow process having discharge of wastewater being become and not having the closed circuit flow process of discharge of wastewater, being not without technical probability, but input is possibly even more than profit, to this end, enterprise has to select discharge, result causes serious environmental pollution.
Summary of the invention
It is an object of the invention to provide a kind of system preparing APT from tungsten mineral material, its flow process is short, solution reusable edible, environmental pollution are 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 comprises the 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, ammonium carbonate-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 returns step 1 as dispensing) 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 is 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 is i.e. obtained after drying, crystalline mother solution and step 6) return to step 3 together with the ammonia that obtains and carbon dioxide), and (can be by ammonium hydrogen carbonate or ammonia and CO at the ammonium carbonate of supplementary consumption2Part 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 at least generates Ca by the tungsten made in tungsten mineral material3WO6、Ca2FeWO6And/or Ca2MnWO61.0 times of theoretical amount, preferably 1.1-1.5 times, more preferably 1.1-1.2 times；Raw material granularity is not particularly limited, preferably not greater than 200 μm, more preferably 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 the reaction between tungsten mineral material and dispensing, significantly reduces sintering temperature；
Preferably, the time of raw material roasting is 0.5-8.0h, preferably 1.0-3.0h, more preferably 2.0h；When tungsten mineral material is 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, tungsten slurry, calcination atmosphere is neutral or reducing atmosphere, preferably neutral atmosphere；The granularity of grog is not particularly limited, preferably not greater than 200 μm, is further preferably no more than 74 μm, is further preferably no more than 45 μm；
Preferably, the CO in Leaching Systems2A part of from stove (kiln) gas or commodity CO produced by raw material roasting process2, 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 the concentration of its saturated solution under this system, and ammonium hydrogen carbonate then adds with the form of solution or solid, and the addition of ammonium hydrogen carbonate is not particularly limited, and preferably not less than makes the calcium in grog be converted into CaCO31.0 times of aequum (theoretical amount), more preferably 1.1-1.4 times of theoretical amount, ammonium tungstate concentration is not particularly limited, as long as the ammonium tungstate concentration that can ensure that after tungsten fully leaches in grog in gained solution is less than the equilibrium concentration under this system, the addition of ammonia is also not particularly limited, and preferably leaches NH in initial system3Weight/mass percentage composition be 0%～28%, more preferably 5%～20%, more preferably 5%～10%；The leaching process of grog is carried out in enclosed system, when leaching grog 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, the absolute pressure of reaction system is not particularly limited, with ammonium carbonate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-CO2System, ammonium carbonate-ammonia-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, preferably extraction time is 0.5-8.0h, and more preferably extraction time is 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 system using said method to prepare APT, including:
1) grinding attachment A, tungsten mineral material, dispensing, after batching metering, use grinding attachment A that levigate for various raw materials, mixing, preparation are had 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, overhang roll 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, agitator mill, 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 the problem of environmental pollution caused due to a large amount of discharge of wastewater in APT production process can be eradicated in theory；
2) by tungsten mineral material roasting is made the transition, make wolfram element change to be contained in the material easily leached by ammonium carbonate salt solution, achieve the low-temp extraction of tungsten, reduce the energy expenditure in leaching process and cost, meanwhile, leached mud can recycle as the dispensing in tungsten mineral material transformation process again；
3) use low cost, the ammonium carbonate salts system of easily circulation leaches tungsten mineral grog, directly obtains ammonium tungstate solution, eliminates step transition from sodium tungstate solution to ammonium tungstate solution, and 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" 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 " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system is non-obvious as leachate, this is because: alkalescence system does not processes the raw material (or treatment effeciency is extremely low) that the chemical reactivities such as scheelite, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry are relatively low.Tungsten smelting industry typically uses strong acid (example hydrochloric acid) or highly basic (such as sodium hydroxide) gonosome system at present and leaches tungsten mineral material under high 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 could realize leaching through raw material step transition.
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 " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" system leaches; Leaching Systems material changes into ammonia and carbon dioxide after crystallisation step; just can replenish Leaching Systems; it is achieved thereby that the whole of supplies recycle; thoroughly abandoned 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, when leaching liquid-solid ratio less than 10, 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 " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-CO2" 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, the pollution problem of discharge of wastewater has obtained thorough elimination.
According to the present invention, supplies are no longer expendable consumed products, the leaching agent of leaching process recycles, even if supplies are excessively used, corresponding processing step outer row, it is no longer necessary to use corresponding acid or alkali to neutralize, 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 part wolfram element to be emitted in vain, and 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 significantly improves, and 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 " 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" system leaches tungsten mineral grog, leaching condition is gentle, and leaching agent is cheap, be easy to get, and supplies reusable edible can eliminate the discharge of wastewater in production process in theory.
According to the present invention, completely disengage from prior art, propose a kind of brand-new theory preparing APT and technique, save sodium tungstate solution step transition that can produce a large amount of waste water, directly obtain ammonium tungstate solution, it is inherently eliminated the discharge of waste water in APT production process, and achieves 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 minimum level.
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 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 leaches 300, and in circular response, reclaim the solution (containing leaching agent) that each link feeds back, and according to being actually needed the weak base AN supplementing consumption；
Leaching slurry is carried out solid-liquid separation 400, obtain the thick solution containing A and containing W ion and the leached mud containing M, slag is washed mutually, cleaning mixture feeds back to grog and leaches link (I closed loop), according to actual needs, take at least part of leached mud feed back to raw material configuration link (ii closed loop) as dispensing, if leached mud has remainder, then store 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, the gas relevant to element A will be discharged and the gas relevant with N element is back to leach the step (ii I closed loop) of grog 300, and the water evaporated 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, to obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution, i.e. obtains the final products (preferably again dissolve solid phase and crystallize, to obtain the higher final products of purity) 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.
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), raw material fine mill (containing vortex mixer) 14, raw material outlet 15 and leached mud receiving port 16；
Calcining kiln (stove) 20, it connects with raw material outlet 15 with raw material silo through feeding measurement device, has heater, attemperator (the most also including chiller 21), atmosphere (oxidizing atmosphere, reducing atmosphere, neutral atmosphere) control 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, it is with thin grog outlet 31, there is leaching agent entrance 41, leaching slurry outlet 42, feedback gas recovery port 43, slurry separating, washing liquid recovery port 44, slag phase cleaning mixture recovery port 45, crystal seed entrance 46 (preferably, also including 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, having the filtration washing device 50 of leached mud containing dispensing element, the thick taphole 51 containing wolfram element, leached mud feedback port 52, the extremely residue outlet 53 of leached mud heap warehousing, washing liquid feedback outlet 54, the receiving port 55 of evaporative crystallization condensed water, this equipment for separating liquid from solid connects with the crystal seed entrance 46 of leaching device 40 in feeding back to the way of 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 have purification and impurity removal agent entrance and impurity collector, and afterbody has the smart taphole 62 (preferably, afterbody adds extractor fan) containing wolfram element；
Crystallization apparatus 70, its entrance 71 connects with the thick taphole 62 containing wolfram element, has slurry outlet 72, feeds back to gas feedback mouth 73 and the condensation-water drain 74 (preferably having the thick solution evaporation cerium sulphate crystal device of tungsten product) of leaching device；
The liquid-solid separation device 80 of slurry, it connects with slurry outlet 72, there is crystalline mother solution and be back to the outlet 83 (preferably, dissolve with next stage, crystallize, purify subsystem and connect) of the outlet 81 of leaching device 40, solid phase wash water entrance 82 and tungsten product.
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 at least generates Ca by the tungsten made in tungsten mineral material3WO6、Ca2FeWO6And/or Ca2MnWO61.0 times of theoretical amount, preferably 1.1-1.5 times, more preferably 1.1-1.2 times.
During raw material preparation, the mineralizer allocated into is fluoride, it is therefore preferable to calcium fluoride, and the addition of calcium fluoride is the 0.5-7% (mass percent) of dry tungsten mineral material amount, preferably 1-3% (mass percent)；Raw material granularity is not particularly limited, preferably not greater 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, and 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, needs to extend roasting time, for making the tungsten in raw material be fully converted into Ca3WO6、Ca2FeWO6And/or Ca2MnWO6, preferably roasting time is 0.5-8.0h, more preferably 1.0～3.0h, more preferably roasting 2.0h at 850～950 DEG C.
For scheelite raw material, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere；For wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry raw material, calcination atmosphere is neutral or reducing atmosphere, preferably neutral atmosphere.
The present invention will contain Ca3WO6、Ca2FeWO6And/or Ca2MnWO6Mixed material join in ammonium salt solution system, leach in confined conditions, after having leached, the separated washing of leaching slurry, obtain ammonium tungstate solution.
Preferably, described Ca3WO6、Ca2FeWO6And/or Ca2MnWO6Can be the pure compound of synthetic, it is also possible to be tungsten mineral material obtain after treatment containing Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6Mixture (grog)；Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6The granularity of mixed material be not more than 200 μm, preferably less than 45 μm；Described ammonium salt solution system, can be ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-ammonium tungstate-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-CO2System, ammonium carbonate-CO2System, ammonium carbonate-ammonium tungstate system, can also be ammonium carbonate-ammonium hydrogen carbonate-CO2System.
Preferably, Ca is leached by 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 system3WO6And/or Ca2FeWO6And/or Ca2MnWO6Time, the absolute pressure of Leaching Systems is not particularly limited；With ammonium carbonate-CO2System, ammonium carbonate-ammonium hydrogen carbonate-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 Ca3WO6、Ca2FeWO6And/or Ca2MnWO6Time, leaching process is passed through CO2, control the absolute pressure of Leaching Systems not less than 1atm, 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 sal volatile.
Preferably, described ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-CO2, ammonium carbonate-ammonia-ammonium tungstate, ammonium carbonate-ammonium tungstate, ammonium carbonate-ammonia-ammonium tungstate-CO2With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2In solution system, ammonium tungstate concentration is also not particularly limited, as long as meeting Ca3WO6And/or Ca2FeWO6And/or Ca2MnWO6In tungsten fully leach after, in gained solution ammonium tungstate concentration be 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-CO2With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-CO2Solution system, ammonium hydrogen carbonate addition is not particularly limited, preferably not less than 1.1～1.4 times of 1.0 times of theoretical amount, more preferably 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 system3Weight/mass percentage composition be 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 20-70 DEG C, more preferably 30-50 DEG C；Extraction time is not particularly limited, as long as Ca can be made3WO6And/or Ca2FeWO6And/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, by the way of multistage feeds, can reduce the final liquid-solid ratio of Leaching Systems, 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)2WO4The high activity CaCO that can generate with leaching process3There is secondary response, generate the CaWO being difficult to be leached by ammonium carbonate salt solution4, 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)2WO4Concentration be continuously increased, reaction (1) and react (2) strengthened, 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；Simultaneously by adding CaCO3Crystal seed, makes newborn CaCO3Grow up rapidly at seed surface, reduce its activity, suppress to react the carrying out of (1) further.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 of purification and impurity removal is not particularly limited, as long as in solution, the content of the impurity such as P, As, Si, Mo, S, Sn, Sb, K, Na, Ca, Mg meets and prepares qualified APT product quality and require after Jing Huaing.According to one embodiment of present invention, the sedimentation method can be used to remove the impurity in ammonium tungstate solution, thus prepare ammonium tungstate refined liquid.
According to embodiments of the invention, ammonium tungstate refined liquid employing evaporative crystallization legal system can be taken APT, the condition of evaporative crystallization 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.1 times of theoretical amount, allocate grog leached mud into and (are mainly composed of CaCO3) 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, levigate with vibrating mill, grog granularity≤45 μm.Weigh 5.0g levigate after grog join band ventilation and mechanical stirring device reactor in, be simultaneously introduced 50g-(NH4)2CO3/100g-H2The sal volatile 50mL of O is the most airtight, then passes to CO2Gas, the absolute pressure controlling reaction system is 2atm, reacts 5h at 80 DEG C.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 97.15%.
Embodiment 2: by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 63.75%, and Fe weight/mass percentage composition is 5.90%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate, mixing and obtain raw material, raw material granularity≤45 μm, then, in shaft furnace, under weak reducing atmosphere, and 950 DEG C of roasting 3.0h, obtain grog.Clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm.Weigh in the reactor that 20.0g grog joins band ventilation and mechanical stirring device, be simultaneously introduced 35g-(NH4)2CO3/100g-H2The sal volatile 100mL of O is the most airtight, then passes to CO2Gas, the absolute pressure controlling reaction system is 2atm, reacts 4h at 70 DEG C.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 87.17%.
Embodiment 3: by certain wolframite (WO3Weight/mass percentage composition is 62.40%, and Fe weight/mass percentage composition is 14.08%, and Mn weight/mass percentage composition is 2.25%) by generating Ca3WO6And Ca2FeWO6And Ca2MnO61.13 times of theoretical amount, allocate grog leached mud into 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, clinker cooling is to after room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.0 times of theoretical amount；Grog is put into leaching equipment, at 80 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 97.13%.Then, by thick ammonium tungstate solution purification and impurity removal, after purification, solution uses evaporative crystallization to separate out APT, obtain ammonia and carbon dioxide simultaneously, serosity after crystallization is carried out solid-liquor separation, obtaining crystalline mother solution and solid phase, solid phase i.e. obtains APT product after water washs, and 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 certain wolframite (WO3Weight/mass percentage composition is 42.17%, and Fe weight/mass percentage composition is 11.34%) by generating Ca3WO6And Ca2FeWO61.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster, under week reduction atmosphere, 850 DEG C of roasting 5.0h, obtain grog, clinker cooling is to after room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects ball milling digester, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.1 times of theoretical amount；Grog is put into leaching equipment, at 40 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 97.78%.Then, similar embodiment 3 but supplementAmmonium hydrogen carbonate and ammonia。
Embodiment 5: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO62.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at roaster neutral atmosphere 870 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with twin rollers, 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 1.3 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%) and airtight, then pass to carbon dioxide, the absolute pressure controlling Leaching Systems is 2atm, reacts 5h at 30 DEG C.After reaction terminates, leach ore pulp 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 7h at roaster neutral atmosphere 1000 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with centrifugal mill, 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 98.99%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 7: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO62.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤40 μm, then, roasting 5h at roaster neutral atmosphere 950 DEG C, obtain grog, clinker cooling is to after 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 mixed solution, and according to 1.4 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 is 9.5%) and airtight, then, it being passed through carbon dioxide, the absolute pressure controlling Leaching Systems is 3atm, reacts 6h 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 99.01%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 8: by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) by generating Ca3WO62.67 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤40 μm, then, roasting 3h at roaster reducing atmosphere 940 DEG C, obtain grog, after clinker cooling to room temperature；Leaching equipment selects the leaching tanks of band stirring, built-in unsaturated carbonate ammonium and the WO Han 120g/L3Ammonium tungstate mixed solution, and according to 1.4 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 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO60.5 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 1.5h at roaster neutral atmosphere 965 DEG C, obtain 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: by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, and Fe weight/mass percentage composition is 7.18%) by generating Ca3WO6And Ca2FeWO60.4 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, and then roasting 3h at roaster neutral atmosphere 500 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm；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, at 28 DEG C, reacts 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO63.0 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤200 μm, then, roasting 4h at roaster neutral atmosphere 950 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤40 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.1 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.77 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤100 μm, then, roasting 2.5h at roaster neutral atmosphere 845 DEG C, obtain grog, clinker cooling is to after 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, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 5.9%) and airtight, then, be passed through carbon dioxide, 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.2 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 1h at roaster neutral atmosphere 870 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with jet mill, grog granularity≤74 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 20%) 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 96.15%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate.
Embodiment 14: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤50 μm, then, roasting 2h at roaster neutral atmosphere 920 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with agitator mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, at 38 DEG C, reacts 2h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 98.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 15: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.13 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 2h at roaster neutral atmosphere 960 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤200 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 98.35%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 16: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.37 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤61 μm, then, roasting 2h at roaster oxidizing atmosphere 970 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, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put into leaching equipment, at 55 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 97.31%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 17: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.17 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤53 μm, then, roasting 0.5h at roaster neutral atmosphere 990 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with planet mill, grog granularity≤45 μm；Leaching equipment selects leaching device, 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, at 62 DEG C, reacts 2h.After reaction terminates, leach ore pulp sucking filtration, with pure water 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.57 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤74 μm, then, roasting 2h at roaster neutral atmosphere 980 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with high pressure disc mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.6 times of theoretical amount；Grog is put into leaching equipment, at 75 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.01%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 19: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 8.2%) and airtight, then pass to carbon dioxide, 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 1h at roaster neutral atmosphere 860 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with tower mill, grog granularity≤45 μm；Leaching equipment selects 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 15%) and airtight, then pass to carbon dioxide, the absolute pressure controlling Leaching Systems is 1.2atm, reacts 6h at 35 DEG C.After reaction terminates, leach ore pulp filter pressing, with pure water 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.67 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤36 μm, then, roasting 1h at roaster reducing atmosphere 880 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibrating 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 1.4 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 10.0%) and airtight, then pass to carbon dioxide, the absolute pressure controlling Leaching Systems is 1.5atm, 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 42.75%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 22: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.6 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain 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, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog being put into leaching equipment, is simultaneously introduced ammonia (making the weight/mass percentage composition of NH3 in infusion solution is 7.4%) airtight, then, is passed through carbon dioxide, the absolute pressure controlling Leaching Systems is 1.9atm, 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 38.35%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 23: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO60.5 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤33 μm, then, roasting 5h at roaster neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibrating mill, 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, at 20 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 22.96%.Then, similar embodiment 3.
Embodiment 24: by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, and Fe weight/mass percentage composition is 7.18%) by generating Ca3WO6And Ca2FeWO60.97 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 3h at roaster neutral atmosphere 850 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with twin rollers, 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 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤28 μm, then, roasting 4h at roaster oxidizing atmosphere 950 DEG C, obtain grog, clinker cooling is to after 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 NH in infusion solution3Weight/mass percentage composition be 20%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.35%.Then, similar embodiment 3 but supplement ammonia.
Embodiment 26: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.77 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤41 μm, then, roasting 2.5h at roaster neutral atmosphere 845 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤83 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia (making the weight/mass percentage composition of NH3 in infusion solution is 9.8%) airtight, at 37 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 68.65%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonia and CO2。
Embodiment 27: by certain scheelite (WO3Weight/mass percentage composition is 52.27%, and Fe weight/mass percentage composition is 5.86%) by generating Ca3WO6And Ca2FeWO61.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤61 μm, then, roasting 1h at roaster neutral atmosphere 870 DEG C, obtain grog, clinker cooling is to after 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, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；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 97.10%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 28: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO6And Ca2MnO61.5 times of theoretical amount, allocate manganese spar into and limestone carry out levigate mixing after obtain raw material, raw material granularity≤14 μm, then, roasting 2h at roaster neutral atmosphere 920 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.63 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤42 μm, then, roasting 2h at roaster neutral atmosphere 960 DEG C, obtain grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 certain scheelite (WO3Weight/mass percentage composition is 60.94%) by generating Ca3WO6And Ca2MnWO61.53 times of theoretical amount, allocate manganese spar into and grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤44 μm, then, roasting 1.5h at roaster neutral atmosphere 980 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects leaching device, 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, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp sucking filtration, with 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-required of country.
Embodiment 31: by certain scheelite (WO3Weight/mass percentage composition is 60.94%) by generating Ca3WO61.43 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤48 μm, then, roasting 2h at roaster neutral atmosphere 970 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, at 55 DEG C, reacts 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.63 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤38 μm, then, roasting 1h at roaster oxidizing atmosphere 990 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects leaching device, 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, 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 certain scheelite (WO3Weight/mass percentage composition is 60.94%) by generating Ca3WO61.7 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤63 μm, then, roasting 2h at roaster neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.3 times of theoretical amount；Grog is put into leaching equipment, at 75 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 97.51%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 34: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO6And Ca2MnWO61.7 times of theoretical amount, allocate manganese spar into and grog leached mud carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 6.0% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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, at 32 DEG C, react 3.8h.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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO6And Ca2MnWO61.7 times of theoretical amount, allocate manganese spar into and grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤36 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp filter pressing, with pure water 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.83 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤37 μm, then, roasting 1h at roaster reducing atmosphere 880 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, grog granularity≤53 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.15 times of theoretical amount；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 carbon dioxide, 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.73 times of theoretical amount, allocate into after limestone carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤24 μm, then, roasting 3h at roaster reducing atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO63.33 times of theoretical amount, allocate siderite into and grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤38 μm, then, roasting 1h at roaster neutral atmosphere 950 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, 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, at 40 DEG C, reacts 9h.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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.7 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 1.0% (mass percent) of dry tungsten mineral material amount, raw material granularity≤33 μm, then, roasting 8h at roaster neutral atmosphere 895 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, 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 1.9 times of theoretical amount；Grog is put into leaching equipment, at 20 DEG C, reacts 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 certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) by generating Ca3WO61.3 times of theoretical amount, allocate into and obtain raw material after limestone carries out levigate mixing, raw material granularity≤40 μm, then, roasting 3h at roaster reducing atmosphere 940 DEG C, obtain 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 NH in infusion solution3Weight/mass percentage composition be 12%) and airtight, at 50 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 92.31%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 41: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.17 times of theoretical amount, allocate into after limestone carries out levigate mixing and 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, roasting 1.5h at roaster neutral atmosphere 965 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤74 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 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 certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, and Fe weight/mass percentage composition is 7.18%) by generating Ca3WO6And Ca2FeWO61.2 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤25 μm, then, roasting 3h at roaster neutral atmosphere 850 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 70g-(NH4)2CO3/100g-H2O, and according to 1.2 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 40 DEG C, reacts 3.5h.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, APT product reaches 0 grade of product standard-required of country.
Embodiment 43: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO63.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤28 μm, then, roasting 4h at roaster neutral atmosphere 845 DEG C, obtain 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, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 28%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 96.01%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonia and CO2。
Embodiment 44: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 5.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 10h at roaster neutral atmosphere 845 DEG C, obtain grog, clinker cooling is to after 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 solution3Weight/mass percentage composition be 7.5%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.49%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 45: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.5 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 6h at roaster neutral atmosphere 1050 DEG C, obtain 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, 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.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.15%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 46: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at roaster neutral atmosphere 995 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 97.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 47: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.83 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at roaster reducing atmosphere 960 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with jet mill, grog granularity≤20 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 98.16%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 48: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 3.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at roaster neutral atmosphere 850 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects leaching device, 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, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake 4 times.The leaching rate of tungsten is 98.33%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 49: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.37 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤53 μm, then, roasting 8h at roaster neutral atmosphere 930 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with overhang roll pulverizer, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.1 times of theoretical amount；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 reaches 0 grade of product standard-required of country.
Embodiment 50: by certain scheelite (WO3Weight/mass percentage composition is 60.94%) by generating Ca3WO61.87 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤53 μm, then, roasting 1h at roaster neutral atmosphere 910 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects leaching device, 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, 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 98.78%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 51: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.57 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤74 μm, then, roasting 2h at roaster neutral atmosphere 900 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.6 times of theoretical amount；Grog is put into leaching equipment, at 75 DEG C, reacts 1.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 95.01%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 52: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 3.3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, 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 NH in infusion solution3Weight/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 filter cake three times.The leaching rate of tungsten is 96.15%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 53: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 1h at roaster neutral atmosphere 810 DEG C, obtain grog, clinker cooling is to after room temperature, levigate by planetary mills, 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 NH in infusion solution3Weight/mass percentage composition be 5.5%) and airtight, at 45 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 98.63%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 54: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.0 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤96 μm, then, roasting 1h at roaster reducing atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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；Grog is put into leaching equipment, is simultaneously introduced ammonia (making the weight/mass percentage composition of NH3 in infusion solution is 3.5%) 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 96.75%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 55: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO64.0 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, the addition of calcium fluoride is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 5h at roaster neutral atmosphere 750 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with twin rollers, grog granularity≤100 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put into leaching equipment, at 32 DEG C, reacts 3.8h.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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.33 times of theoretical amount, allocate into and obtain raw material after limestone carries out levigate mixing, raw material granularity≤106 μm, then, roasting 7h at roaster neutral atmosphere 1000 DEG C, obtain 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 embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 57: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO62.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 5h at roaster neutral atmosphere 1200 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.4 times of theoretical amount；Grog is put into leaching equipment, at 20 DEG C, reacts 6h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 78.01%.
Embodiment 58: by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) by generating Ca3WO62.67 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤96 μm, then, roasting 3h at roaster reducing atmosphere 1400 DEG C, obtain 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 NH in infusion solution3Weight/mass percentage composition be 6%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 81.51%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 59: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.17 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 8h at roaster neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, levigate with centrifugal mill, 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, 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 92.96%.Then, similar embodiment 3.
Embodiment 60: by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, and Fe weight/mass percentage composition is 7.18%) by generating Ca3WO6And Ca2FeWO61.07 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 3h at roaster neutral atmosphere 850 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, at 28 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO63.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at roaster neutral atmosphere 950 DEG C, obtain grog, clinker cooling is to after 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 solution3Weight/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 filter cake three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 62: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.07 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 5h at roaster neutral atmosphere 845 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, and built-in sal volatile, ammonium carbonate concentration is 40g-(NH4)2CO3/100g-H2O；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 4%) and airtight, at 45 DEG C, react 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 1.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤120 μm, then, roasting 3h at roaster neutral atmosphere 870 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；The leaching tanks of leaching equipment selection band stirring, built-in sal volatile, ammonium carbonate concentration is 45g-(NH4)2CO3/100g-H2O；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 7.9%) and airtight, at 5 DEG C, react 15h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 93.15%.Then similar embodiment 3 but supplement ammonium carbonate, ammonia and CO2。
Embodiment 64: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 5.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at roaster neutral atmosphere 750 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 97.22%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 65: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.13 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 15h at roaster neutral atmosphere 760 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 66: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.4 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 8h at roaster neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 4 times of theoretical amount；Grog is put into leaching equipment, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 4 times.The leaching rate of tungsten is 96.33%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 67: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.37 times of theoretical amount, allocate limestone into and fluorite carry out levigate mixing after obtain raw material, the addition of fluorite is 6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤48 μm, then, roasting 2h at roaster neutral atmosphere 970 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with agitator mill, grog granularity≤40 μm；Leaching equipment selects leaching device, and built-in sal volatile, ammonium carbonate concentration is 25g-(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 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 reaches 0 grade of product standard-required of country.
Embodiment 68: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.17 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤53 μm, then, roasting 8h at roaster neutral atmosphere 990 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 3 times of theoretical amount；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 97.70%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 69: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.57 times of theoretical amount, allocate grog leached mud into and fluorite carry out levigate mixing after obtain raw material, the addition of fluorite is 4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at roaster neutral atmosphere 980 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤40 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.6 times of theoretical amount；Grog is put into leaching equipment, at 75 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.01%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 70: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.07 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 1h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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 NH in infusion solution3Weight/mass percentage composition be 6.7%) and airtight, at 90 DEG C, react 0.5h.After reaction terminates, leach ore pulp sucking filtration, 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 3.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤90 μm, then, roasting 1h at roaster neutral atmosphere 860 DEG C, obtain grog, clinker cooling is to after 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, and adds ammonium hydrogen carbonate according to 1.1 times of theoretical amount；Grog is put into leaching equipment, at 45 DEG C, reacts 6h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.The leaching rate of tungsten is 97.09%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 72: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.03 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 4.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at roaster reducing atmosphere 880 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibromill, grog granularity≤74μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution,；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride 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≤45 μm, then, roasting 9h at roaster neutral atmosphere 880 DEG C, obtain grog, clinker cooling is to after 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, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.23 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 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.Weigh 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, the absolute pressure controlling reaction system is 2atm, reacts 4h at 80 DEG C.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 certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 63.75%, and Fe weight/mass percentage composition is 5.90%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in shaft furnace, under weak reducing atmosphere, 1000 DEG C of roasting 3.0h, obtain grog.Clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤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, the absolute pressure controlling reaction system is 2atm, reacts 4h at 70 DEG C.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 95.17%.
Embodiment 76: by certain wolframite (WO3Weight/mass percentage composition is 60.40%, and Fe weight/mass percentage composition is 15.08%) by generating Ca3WO6And Ca2FeWO61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate, mixing after obtain raw material, the addition of calcium fluoride is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in pipe type calciner, under neutral atmosphere, roasting 6.0h at 800 DEG C, obtain grog, clinker cooling is to after 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, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, at 80 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 97.13%.Then, similar embodiment 3 supplements the ammonium carbonate of loss.
Embodiment 77: by certain wolframite (WO3Weight/mass percentage composition is 42.17%, and Fe weight/mass percentage composition is 11.34%) by generating Ca3WO6And Ca2FeWO61.17 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 0.9% (mass percent) of dry tungsten mineral material amount, 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 selects ball milling digester, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.1 times of theoretical amount；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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO62.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 2.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then roasting 4h at roaster neutral atmosphere 870 DEG C, 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 solution3Weight/mass percentage composition be 6.5%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.09%.Then similar embodiment 3 but supplement ammonia and CO2。
Embodiment 79: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤25 μm, then, roasting 7h at roaster neutral atmosphere 1000 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with vibrating mill, grog 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 embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 80: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 3.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 5h at roaster neutral atmosphere 950 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with Raymond mill, grog granularity≤8 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 NH in infusion solution3Weight/mass percentage composition be 10.0%) and airtight, the absolute pressure controlling Leaching Systems is 1.0atm, reacts 12h 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 96.20%.Then, similar embodiment 3 but supplement ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 81: by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) by generating Ca3WO62.67 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 3h at roaster reducing atmosphere 950 DEG C, obtain 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 NH in infusion solution3Weight/mass percentage composition be 6.3%) and airtight, at 35 DEG C, react 15h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 91.51%.Then, ammonia and CO are supplemented2。
Embodiment 82: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.2 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 4.1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1.5h at roaster neutral atmosphere 965 DEG C, obtain grog, clinker cooling is to after 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 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 97.96%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 83: by certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 43.20%, and Fe weight/mass percentage composition is 7.18%) by generating Ca3WO6And Ca2FeWO61.1 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 2.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45μM, then roasting 3h at roaster neutral atmosphere 850 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in sal volatile, ammonium carbonate concentration is 40g-(NH4)2CO3/100g-H2O, and according to 1.25 times of addition ammonium hydrogen carbonate of theoretical amount；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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO63.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 0.55% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 4h at roaster neutral atmosphere 950 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects 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, at 37 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 98.72%.Then similar embodiment 3 but supplement ammonia and CO2。
Embodiment 85: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO60.9 times of theoretical amount, allocates into and obtains raw material after grog leached mud carries out levigate mixing, raw material granularity≤45 μm, then, roasting 2.5h at roaster neutral atmosphere 845 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with overhang roll pulverizer, grog granularity≤74 μm；Leaching equipment selects the leaching tanks of band stirring, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；Grog is put into leaching equipment, at 45 DEG C, reacts 4.5h.After reaction terminates, leach ore pulp sucking filtration, 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 certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at roaster neutral atmosphere 870 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects the leaching tanks of band ball milling, and built-in supersaturation ammonium carbonate serosity, ammonium carbonate concentration is 100g (NH4)2CO3/100g H2O；Grog is put into leaching equipment, is simultaneously introduced ammonia and (makes NH in infusion solution3Weight/mass percentage composition be 6.5%) and airtight, at 52 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 98.25%.Then similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, ammonia and CO2。
Embodiment 87: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.5 times of theoretical amount, allocate limestone into and fluorite carry out levigate mixing after obtain raw material, the addition of fluorite is 2.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at roaster reducing atmosphere 920 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of theoretical amount；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 98.12%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 88: by certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.13 times of theoretical amount, allocate the slag after grog leaches in embodiment 86 into and (are mainly composed of CaCO3) and calcium fluoride carry out levigate mixing after obtain raw material, 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, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.2 times of 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO61.4 times of theoretical amount, allocate the slag after grog in embodiment 88 leaches into 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, then, roasting 1.5h at roaster neutral atmosphere 980 DEG C, obtain grog, clinker cooling is to after 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, reacts 6h.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake 4 times.The leaching rate of tungsten is 97.23%.Then, 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 certain scheelite (WO3Weight/mass percentage composition is 52.33%, and Fe weight/mass percentage composition is 2.04%) by generating Ca3WO6And Ca2FeWO62.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤80 μm, then, roasting 7h at roaster neutral atmosphere 1000 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and adds ammonium hydrogen carbonate according to 1.3 times of theoretical amount；Grog is put into leaching equipment, at 40 DEG C, reacts 24h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.66%.Then, similar embodiment 3, APT product reaches 0 grade of product standard-required of country.
Embodiment 91: by certain scheelite (WO3Weight/mass percentage composition is 49.53%, and Fe weight/mass percentage composition is 0.43%) by generating Ca3WO61.33 times of theoretical amount, allocate into and obtain raw material after grog leached mud carries out levigate mixing, raw material granularity≤53 μm, then, roasting 10h at roaster neutral atmosphere 950 DEG C, obtain 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 NH in infusion solution3Weight/mass percentage composition be 13.0%) and airtight, at 40 DEG C, react 20h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 99.01%.Then, similar embodiment 3 but supplement ammonia and CO2。
Embodiment 92: by certain tungsten slurry (WO3Weight/mass percentage composition is 16.22%) by generating Ca3WO62.67 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, the addition of calcium fluoride is 6.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at roaster reducing atmosphere 750 DEG C, obtain grog, clinker cooling is to after room temperature, levigate with centrifugal mill, grog granularity≤45 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 solution3Weight/mass percentage composition be 8.5%) and airtight, at 45 DEG C, react 4h.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 94.51%.Then, similar embodiment 3 but supplement ammonium carbonate, ammonium hydrogen carbonate, 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 design of the present invention, there is not employing " common knowledge " or the problem of " customary means ".Even so, even with design, the multiple factors related to are the most all mutually restrictions, interactional, it is not separate, even if having employed the scientific method of the modernizations such as orthogonal design, still there is infinite may combining, and enough excellent technical scheme can not be doped, " experiment of limited number of time " can not obtain the suitable value of each factor, and 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 on the premise of without departing from the spirit of the present invention and design, 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 (12)

1. a metallurgical system for tungsten mineral material, including: raw material preparation facilities, it has leached mud receiving port；Calcining kiln, it has the outlet of thick grog；Grog fine mill, it has the outlet of thin grog；Leaching device, it has leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase cleaning mixture recovery port, crystal seed entrance；The equipment for separating liquid from solid of leaching slurry, it has leached mud feedback port, washing liquid feedback exports, the receiving port of evaporative crystallization condensed water, and this equipment for separating liquid from solid connects with the crystal seed entrance of leaching device in feeding back to the way of leached mud receiving port of raw material preparation facilities；At least first class purification knot screen；Crystallization apparatus, it has the gas feedback mouth feeding back to leaching device；The liquid-solid separation device of slurry, it has crystalline mother solution and is back to the outlet of leaching device and the outlet of tungsten product.
2. the metallurgical system of a tungsten mineral material, it is characterised in that this metallurgical system includes successively:
Raw material preparation facilities, it has tungsten mineral material entrance and ingredient inlets, raw material fine mill, raw material outlet and leached mud receiving port；
Calcining kiln or roaster, it is through feeding measurement device and raw material silo and raw material outlet, has heater, attemperator, atmosphere control device and thick grog outlet；
Grog fine mill, it is through grog storehouse and thick grog outlet, has ore grinding device and the outlet of thin grog；
Leaching device, itself and thin grog outlet, there is leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase cleaning mixture recovery port, crystal seed entrance；
The equipment for separating liquid from solid of leaching slurry, it is with leaching slurry outlet, having the filtration washing device of leached mud containing dispensing element, the thick taphole containing wolfram element, leached mud feedback port, the extremely residue outlet of leached mud heap warehousing, washing liquid feedback outlet, the receiving port of evaporative crystallization condensed water, this equipment for separating liquid from solid connects with the crystal seed entrance of leaching device in feeding back to the way of leached mud receiving port of raw material preparation facilities；
At least first class purification knot screen, the entrance of the first order connects with the thick taphole containing wolfram element, and at different levels have purification and impurity removal agent entrance and impurity collector, and afterbody has the smart taphole containing wolfram element；
Crystallization apparatus, its entrance connects with the essence containing wolfram element/thick taphole, has slurry and export, feed back to gas feedback mouth and the condensation-water drain of leaching device；
The liquid-solid separation device of slurry, itself and slurry outlet, there is crystalline mother solution and be back to the outlet of leaching device, solid phase wash water entrance and the outlet of tungsten product.
System the most according to claim 1 and 2, it is characterised in that: raw material fine mill and/or described grog fine mill are selected from: vibrating mill, ball mill, twin rollers, rod mill, autogenous tumbling mill, agitator mill, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill or jet mill；And/or, described calcining kiln is static calcining kiln or dynamic roasting kiln, and described roaster is static roaster or dynamic roasting stove.
Metallurgical system the most according to claim 1 and 2, it is characterised in that: described leaching device is an independent leaching equipment, or 2-4 the leaching equipment being used in series.
Metallurgical system the most according to claim 1 and 2, it is characterised in that: include following additional technical feature at least one:
Described leaching device is leaching equipment or ball milling leaching equipment；
Described leaching device is the leaching equipment sealing and can bearing 4atm pressure；
Described equipment for separating liquid from solid is pumping and filtering device, filtering equipment and/or natural filtration groove；And
Described purification and impurity removal device is decleaning tank, filter plant and/or subsider, is provided with agitating device in decleaning tank.
6. a metallurgical technology for tungsten mineral material, described tungsten mineral material includes scheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, it is characterised in that
Use highly basic or strong acid contrary with leaching agent in prior art, use the weak base leaching agent contributing to forming local process circulation, its leachate produces two or more gas in evaporation and crystal process, each gas participates in synthesizing this leaching agent again, and the separating, washing liquid after crystallization recycles as leaching agent equally；And
Employing one dispensing transition, its by with tungsten mineral material generation chemical reaction, wolfram element is changed be contained in the intermediate material easily leached by described leaching agent, and leached mud also contains dispensing element, so that at least partly leached mud recycles as dispensing, include tungsten mineral material described transition, dispensing is levigate, mix homogeneously, to prepare raw material；Raw material are carried out roasting, to obtain grog,
To this end, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
7. metallurgical technology as claimed in claim 6, it is characterised in that this technique includes:
In tungsten mineral material, add dispensing transition, grind, mix homogeneously, roasting so that wolfram element changes and is contained in the intermediate material easily leached by described leaching agent；The means reclaiming at least part of leached mud are set in dispensing link；
Use selected leaching agent that intermediate material is leached, the means of leaching agent reacting gas that reclaim, the means of recovery slurry separating, washing liquid are set in this leaching link, reclaim the means of slag phase cleaning mixture and according to the means being actually needed supplementary leaching agent；
Leaching slurry is carried out solid-liquid separation, to obtain the thick solution containing wolfram element and the leached mud containing dispensing element, slag is washed mutually, cleaning mixture feeds back to leach link, according to actual needs, take at least part of leached mud to feed back as dispensing, to reuse dispensing, if leached mud has remainder, then store up；
Thick solution containing wolfram element is carried out at least first class purification remove impurity；
Solution after purifying is evaporated crystallization, to separate out the intermediate products containing wolfram element；Meanwhile, it is back to the gas discharged leach link, and the water evaporated feeds back to the solid-liquid separation link of 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, i.e. obtains the final products containing wolfram element after drying；And crystalline mother solution also returns to leaching link.
Metallurgical technology the most according to claim 6, it is characterized in that, slurry is after solid-liquor separation and/or washing, after the ammonia of crystalline mother solution and washing liquid and collection and carbon dioxide mix or feed back to the leaching device of grog respectively, solid then or prepares product A PT after scrubbed drying, or entrance next stage dissolves, crystallizes, purifies subsystem.
Metallurgical technology the most according to claim 6, it is characterised in that carry out grog crushing, levigate.
Metallurgical technology the most according to claim 6, it is characterised in that described weak base leaching agent is ammonium carbonate, ammonium hydrogen carbonate, ammonia, ammonia+CO2Gas, and their any mixture and/or their any mixture with ammonium tungstate.
11. metallurgical technologies according to claim 7, it is characterised in that be also added with mineralizer in tungsten mineral material；Afterbody purification and impurity removal adds convulsion measure；And/or, solid phase final products are dissolved again and crystallizes, to obtain the higher final products of purity.
12. metallurgical technologies according to claim 2, it is characterised in that: ingredient inlets is additionally provided with mineralizer entrance；Tungsten mineral material entrance and ingredient inlets are additionally provided with quantifier；Raw material fine mill contains vortex mixer；Calcining kiln or roaster also include chiller；Atmosphere control device is that oxidizing atmosphere controls device, reducing atmosphere controls device or neutral atmosphere controls device；Leaching device also includes that carbon dioxide is passed through mouth；The equipment for separating liquid from solid of leaching slurry is defecator；Afterbody purification and impurity removal device adds extractor fan；Crystallization apparatus has temperature controller, density controller, pH value controller；And/or, the outlet of tungsten product dissolves with next stage, crystallize, purify subsystem connects.
CN201410528734.7A 2014-10-09 2014-10-09 The tungsten mineral material metallurgical system of omnidistance non-pollution discharge Active CN104388670B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410528734.7A CN104388670B (en) 2014-10-09 2014-10-09 The tungsten mineral material metallurgical system of omnidistance non-pollution discharge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410528734.7A CN104388670B (en) 2014-10-09 2014-10-09 The tungsten mineral material metallurgical system of omnidistance non-pollution discharge

Publications (2)

Publication Number Publication Date
CN104388670A CN104388670A (en) 2015-03-04
CN104388670B true CN104388670B (en) 2016-08-24

Family

ID=52606626

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410528734.7A Active CN104388670B (en) 2014-10-09 2014-10-09 The tungsten mineral material metallurgical system of omnidistance non-pollution discharge

Country Status (1)

Country Link
CN (1) CN104388670B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108504858B (en) * 2018-01-23 2019-08-27 精细化学品集团有限公司 A kind of association Determination of Rare-Expensive Elements enrichment extraction separated structure
CN115055263A (en) * 2022-06-01 2022-09-16 浙江艾领创矿业科技有限公司 Fine grinding process for tungsten-containing mineral

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3911077A (en) * 1974-09-03 1975-10-07 Gte Sylvania Inc Tungsten recovery from tungsten ore concentrates by caustic baking
US4927794A (en) * 1985-06-26 1990-05-22 Chevron Research Company Leaching cobalt, molybdenum, nickel, and vanadium from spent hydroprocessing catalysts
CN102071313B (en) * 2011-01-29 2012-09-05 湖南辰州矿业股份有限公司 Method for treating tungsten-containing and molybdenum-containing slag produced in ammonium paratungstate production process
CN103343223B (en) * 2013-07-29 2016-01-20 中国环境科学研究院 The metal extraction process of multistage acidleach, washing and press filtration and integrated apparatus thereof
CN103725879A (en) * 2013-12-24 2014-04-16 戴元宁 Method for producing tungsten and tin chemical products through chemical metallurgical separation of tungsten-tin paragenic ore

Also Published As

Publication number Publication date
CN104388670A (en) 2015-03-04

Similar Documents

Publication Publication Date Title
CN106906359B (en) Lithium is collected from silicate mineral
CN104232942B (en) A kind of preprocess method of tungsten mineral material
CN103849774B (en) A kind of method that discarded SCR catalyst is recycled
CN104263973B (en) The method being prepared APT by the many closed loops of tungsten mineral material
CN104263975B (en) There is the tungsten mineral material metallurgical technology of multiple closed loop
CN107523702B (en) A kind of method that the pressure oxidation of sodium salt system prepares sodium pyroantimonate
CN110129552A (en) A method of vanadic sulfide material is prepared using containing vanadium leachate
CN104263976B (en) The tungsten mineral material metallurgical technology of omnidistance non-pollution discharge
CN104263971B (en) The system of APT is prepared by tungsten mineral material no pollution
CN104263972B (en) There is the tungsten mineral material metallurgical system of multiple closed loop
CN104388670B (en) The tungsten mineral material metallurgical system of omnidistance non-pollution discharge
CN204162765U (en) The metallurgical system of the tungsten mineral material of omnidistance non-pollution discharge
CN204162450U (en) A kind of system preparing ammonium tungstate solution
CN204162756U (en) The metallurgical system of the tungsten mineral material of no pollution discharge can be realized
CN104263974B (en) The method being prepared APT by tungsten mineral material no effuent discharge
CN104263921B (en) System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops
CN204162767U (en) There is the metallurgical system of the tungsten mineral material of multiple closed loop
CN104263923B (en) The tungsten mineral material metallurgical technology of no pollution discharge can be achieved
CN105969976A (en) Clean metallurgical process for preparing ammonium molybdate by using molybdenite concentrate
CN105861814A (en) Clean metallurgic method for preparing ammonium molybdate from molybdenite concentrates
CN103086433A (en) Method for preparing sodium dichromate by sodium-based molten salt oxidation continuous carbonization
CN204162768U (en) The system of APT is prepared by the many closed loops of tungsten mineral material
CN204162766U (en) The system of APT is prepared by tungsten mineral material no effuent discharge
CN104263922B (en) The tungsten mineral material metallurgical system of no pollution discharge can be achieved
CN104386754B (en) A kind of technique for preparing ammonium tungstate solution

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant