CN104263921B - System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops - Google Patents

System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops Download PDF

Info

Publication number
CN104263921B
CN104263921B CN201410527649.9A CN201410527649A CN104263921B CN 104263921 B CN104263921 B CN 104263921B CN 201410527649 A CN201410527649 A CN 201410527649A CN 104263921 B CN104263921 B CN 104263921B
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
CN201410527649.9A
Other languages
Chinese (zh)
Other versions
CN104263921A (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
申雷霆
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 CN201410527649.9A priority Critical patent/CN104263921B/en
Publication of CN104263921A publication Critical patent/CN104263921A/en
Application granted granted Critical
Publication of CN104263921B publication Critical patent/CN104263921B/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

Landscapes

  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a metallurgical system for a tungsten mineral raw material. A leaching device of the metallurgical system is provided with an absolute pressure controller for a leaching system, an ammonium carbonate concentration controller for the leaching system, a leaching agent addition controller, a controller for controlling the pH of the leaching system, a leaching temperature controller, a leaching time controller, an initial liquid-solid ratio controller for the leaching system, a final initial liquid-solid ratio controller for the leaching system, a leaching agent inlet, a leaching slurry outlet, a feedback gas recovery opening, a crystallizing slurry separated washing liquid recovery opening, a slag-phase washing solution recovery opening and a crystal seed inlet, wherein a solid-liquid separating device for the leaching slurry is provided with a leaching slag feedback opening, a washing solution feedback outlet and a receiving opening of evaporation and crystallization condensed water; a crystallizing device is provided with a gas feedback opening for feeding back gas to the leaching device; a liquid-solid separating device for the crystallizing slurry is provided with an outlet for returning the crystallizing mother solution to the leaching device, a solid-phase water washing inlet and an outlet of tungsten products. According to the system disclosed by the invention, the waste water pollution is thoroughly eradicated. The system has the advantages of less consumption of auxiliary materials, simple flow, good convenience for operation, low production cost and high efficiency.

Description

Prepare the system of apt by the many closed loops of tungsten mineral material
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 after high-temperature roasting gained material.
Term " mineralizer " refers to accelerate the reaction between tungsten mineral material and dispensing or reduction roasting in raw material roasting process The material of temperature.
Background technology
In prior art, the commercial run preparing apt mainly comprises the steps: by caustic soda or soda leaching tungsten mineral Raw material, obtains coarse sodium tungstate；By solution purification-ion exchange or solvent extraction transition (or pass through ion exchange or molten Agent abstraction impurity removal simultaneously makes the transition), obtain pure tungsten acid ammonium solution；Pass through evaporative crystallization again, obtain apt product.
All there is essential defect as follows in prior art: all using not circulating or half cycle process system, be not carried out whole circulation industrials Skill.At least there is following technical problem in prior art: must arrange waste water discharge opening, waste water pollution problem cannot thoroughly be eradicated； Supplies are mostly expendable consumed product, and the leaching agent of leaching process is excessively used, and these supplies walk in corresponding technique Or rapid after completion of the reaction directly outer row need using in corresponding acid or alkali and after outer again arrange, supplies consume many, Production cost is high；Inevitably take part wolfram element out of in waste water, the wolfram element response rate is low；Equipment investment is big, technique stream Journey is long, and productivity ratio is relatively low it is more difficult to realization continuously produces.
In such apt preparation process, auxiliary material consumption is larger, and produces a large amount of waste water；Sodium tungstate solution made the transition Substantial amounts of high bisulfate waste liquor is produced, evaporative crystallization mother solution produces ammonia nitrogen waste water in journey.
If the open circuit flow process having discharge of wastewater is become does not have the closed circuit flow process of discharge of wastewater, it is not without technical possibility Property, but input is possibly even more than profit, for this reason, enterprise has to select discharge, result leads to serious environment Pollution.
Content 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 is almost uprooted, low cost, be easy to industrialization.
For this reason, according to an aspect of the invention, it is provided a kind of method preparing apt from tungsten mineral material, the method bag Include following steps:
1), after will be levigate to tungsten mineral material, dispensing, mix homogeneously prepares raw material；
2) raw material are carried out with roasting, obtains grog, and grog is crushed, levigate；
3) with ammonium carbonate, ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate, ammonium carbonate-co2, ammonium carbonate-ammonia-co2, carbon Sour ammonium-ammonia, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2, ammonium carbonate-ammonia-ammonium tungstate, Ammonium carbonate-ammonium tungstate-co2, ammonium carbonate-ammonia-ammonium tungstate-co2System leaches grog；
4) leaching slurry washs through solid-liquid separation and slag phase, obtains thick ammonium tungstate solution and leached mud, and part leached mud is as joining Material return to step 1) carry out raw material configuration, remainder is stored up；
5) thick ammonium tungstate solution purification and impurity removal；
6) after purifying, solution adopts evaporative crystallization to separate out apt, obtains ammonia and carbon dioxide simultaneously；
7) solid-liquor separation is carried out to the serosity after crystallization, obtains crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution, Apt product, crystalline mother solution and step 6 is obtained after drying) return to step 3 together with the ammonia that obtains and carbon dioxide), and (can be by ammonium hydrogen carbonate or ammonia and co in the ammonium carbonate supplementing loss2Part substitutes) Posterior circle leaching grog.
Preferably, described tungsten mineral material includes scheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry；
Preferably, when raw material are prepared, the addition of leached mud at least generates ca by the tungsten making in tungsten mineral material3wo6With/ Or 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 40μm；During raw material roasting, temperature is to be not less than 500 DEG C, preferably 800-1050 DEG C, more preferably 800-950 DEG C；
Preferably, add mineralizer in raw material process for preparation, preferably calcium fluoride, to accelerate between tungsten mineral material and dispensing Reaction, significantly reduce sintering temperature；
Preferably, the time of raw material roasting is 0.5-8.0h, preferably 1.0-3.0h, more preferably 2.0h；Tungsten mineral material is During scheelite, calcination atmosphere is not particularly limited, preferably neutral or oxidizing atmosphere；
Preferably, when tungsten mineral material is wolframite, Scheelite-Wolframite Mixed Mine, tungsten slurry, calcination atmosphere is neutral or reproducibility gas Atmosphere, preferably neutral atmosphere；The granularity of grog is not particularly limited, preferably not greater than 200 μm, further preferably for being not more than 74 μm, further preferably for being not more than 45 μm；
Preferably, the co in Leaching Systems2A part is derived from stove (kiln) gas or commodity produced by raw material roasting process co2, another part is from co produced by ammonium tungstate solution evaporation and crystal process2；
Preferably, co2Can be passed through it is also possible to be passed through before leaching in leaching process.
Preferably, leach carbonic acid ammonium concentration in initial system and be more than 20g- (nh4)2co3/100g-h2O, is preferably under this system The concentration of its saturated solution, and ammonium hydrogen carbonate is then added in the form of solution or solid, the addition of ammonium hydrogen carbonate is not especially limited System, preferably not less than makes the calcium in grog be converted into caco31.0 times of aequum (theoretical amount), more preferably theoretical amount 1.1-1.4 times, ammonium tungstate concentration is not particularly limited, as long as can ensure that the ammonium tungstate in resulting solution after tungsten fully leaches in grog Concentration is less than the equilibrium concentration under this system, and the addition of ammonia is also not particularly limited, and preferably leaches initial system Middle nh3Weight/mass percentage composition be 0%～28%, more preferably 5%～20%, more preferably 5%～10%；The leaching of grog Process is carried out in enclosed system, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, ammonium carbonate When-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-ammonia-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach grog, reactant The absolute pressure of system is not particularly limited, with ammonium carbonate-co2System, ammonium carbonate-ammonium hydrogen carbonate-co2System, ammonium carbonate-ammonia Water-co2System, ammonium carbonate-ammonium tungstate-co2System, ammonium carbonate-ammonia-ammonium tungstate-co2System and ammonium carbonate-ammonium hydrogen carbonate- Ammonium tungstate-co2When system leaches grog, the absolute pressure of reaction system need to be controlled to be not less than 1atm, preferably 2atm；
Preferably, extraction temperature is not less than 5 DEG C, preferably 10-80 DEG C, more preferably 20-70 DEG C, more preferably 30-50 DEG C；
Preferably, extraction time is not particularly limited, as long as can ensure that in grog, tungsten can fully leach, when preferably leaching Between be 0.5-8.0h, more preferably extraction time be 2-5h；Purification and impurity removal process include except molybdenum, phosphorus, stannum, arsenic, silicon, ferrum, Sodium, potassium, bismuth, antimony, calcium, at least one of magnesium process.
According to another aspect of the present invention, there is provided a kind of method described in employing claim 1 prepares the system of apt, Including:
1) grinding attachment a, tungsten mineral material, dispensing after batching metering, using grinding attachment a by levigate for various raw materials, Mix, preparation has the raw material of certain fineness and the uniformity；
2) calcining kiln (stove), the raw material of preparation is added roasting in calcining kiln (stove), obtains grog after cooling；
3) grinding attachment b, the grog burning till adopts grinding attachment b levigate；
4) leaching equipment, grog is leached in leaching equipment；
5) filter plant, leaching slurry carries out filtration washing using filter plant；
6) impurity removing equipment, thick ammonium tungstate solution purification and impurity removal in impurity removing equipment；And
7) crystallizer, ammonium tungstate refined liquid evaporative crystallization in crystallizer.
Preferably, described grinding attachment a is selected from: vibrating mill, ball mill, rod mill, autogenous tumbling mill, agitator mill, outstanding Roller pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, jet mill.
Preferably, described calcining kiln (stove) includes: static calcining kiln (stove) and dynamic roasting kiln (stove).
Preferably, described grinding attachment b is selected from: vibrating mill, twin rollers, ball mill, rod mill, autogenous tumbling mill, stirring Grinding machine, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc mill, Raymond mill, jet mill.
Preferably, described leaching equipment can be an independent leaching equipment it is also possible to 2-4 leaching equipment is used in series.
Preferably, described leaching equipment can be leaching equipment or ball milling leaching equipment.
Preferably, described leaching equipment can seal, and can bear 3atm 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, attemperator in described decleaning tank.
The industrial process with respect to existing apt for the present invention, has an advantage in that:
1) achieve the closed cycle being prepared solution during apt by tungsten mineral material, thus apt life can be eradicated in theory The problem of environmental pollution being caused due to a large amount of discharge of wastewater during product；
2) pass through tungsten mineral material roasting makes the transition, so that wolfram element is changed and be contained in the material easily being 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 again can be used as tungsten mineral Dispensing in raw material transformation process and recycle；
3) tungsten mineral grog is leached using the ammonium carbonate salts system of low cost, easily circulation, directly obtain ammonium tungstate solution, cancel Transition step from sodium tungstate solution to ammonium tungstate solution, flow process is simple；
4) recycling due to multiple supplies, supplies consumption is greatly reduced, and processing charges is greatly lowered；
5) simple to operate, it is easy 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 Water-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-co2” Or " ammonium carbonate-ammonia-ammonium tungstate-co2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2" or " ammonium carbonate-co2" or " carbon Sour ammonium-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-co2" system is non-obvious as leachate, this is because: alkalescence System do not process the relatively low raw material of the chemical reactivities such as scheelite, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry (or process Extremely inefficient).Tungsten smelting industry typically adopt at present strong acid (example hydrochloric acid) or highly basic (as sodium hydroxide) gonosome system and high temperature, Tungsten mineral material is leached under environment under high pressure, and " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate ", " ammonium carbonate-ammonium tungstate-co2", " carbon Sour ammonium-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 through raw material transition step Enable to leach.
According to the present invention, from " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-co2" or " ammonium carbonate- Ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-co2” Or " ammonium carbonate-ammonia-ammonium tungstate-co2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2" or " ammonium carbonate-co2" or " carbon Sour ammonium-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-co2" system leached, Leaching Systems material converts after crystallisation step Become ammonia and carbon dioxide, just can replenish Leaching Systems, it is achieved thereby that the whole of supplies recycle, thoroughly get rid of Abandon traditional open circuit not circulating system or open circuit half cycle system, eradicated disposal of pollutants, be truly realized green metallurgical.
According to the present invention, the tungsten leaching effect that not only can obtain when leachate compares high admittedly, it is less than 10 leaching liquid-solid ratio When, in grog, the leaching rate of tungsten does not also decline, wo in gained leachate3Concentration still enough industrialized production.
According to the present invention, using " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-co2" or " ammonium carbonate- Ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " ammonium carbonate-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-co2” Or " ammonium carbonate-ammonia-ammonium tungstate-co2" or " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2" or " ammonium carbonate-co2" or " carbon Sour ammonium-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-co2" system leaching grog, when leaching liquid-solid ratio for 4, remain to obtain Preferably 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 setting waste residue outlet, no longer need to arrange waste water discharge opening, waste water is arranged The pollution problem put has obtained thorough elimination.
According to the present invention, supplies are no longer expendable consumed products, and the leaching agent of leaching process recycles, even if adminicle Material is excessively used, and also no longer directly arranges outward it is no longer necessary to use in corresponding acid or alkali after completion of the reaction in corresponding processing step With therefore, supplies consumption is greatly decreased, and production cost is greatly reduced.
According to the present invention it is achieved that circulation metallurgical technology, " waste water " of conventional process systems is blotted squeezing only, is thoroughly avoided portion Wolfram element is divided to be emitted in vain, therefore, the wolfram element response rate also improves.
According to the present invention, achievable integrated production, the working environment in workshop can greatly improve, and equipment investment return rate substantially carries Height, technological process shortens, and productivity ratio is largely increased, it is possible to achieve continuous automated production.
According to the present invention, increased the pretreatment process of tungsten mineral material, using " ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate " or " ammonium carbonate-ammonium tungstate-co2" or " ammonium carbonate-ammonia-ammonium tungstate " or " ammonium carbonate-ammonia " or " ammonium carbonate " or " carbon Sour ammonium-ammonium hydrogen carbonate " or " ammonium carbonate-ammonia-co2" or " ammonium carbonate-ammonia-ammonium tungstate-co2" or " ammonium carbonate-bicarbonate Ammonium-ammonium tungstate-co2" or " ammonium carbonate-co2" or " ammonium carbonate-ammonium tungstate " or " ammonium carbonate-ammonium hydrogen carbonate-co2" system Leach tungsten mineral grog, leaching condition is gentle, leaching agent is cheap, be easy to get, supplies reusable edible, can disappear in theory Except the discharge of wastewater in production process.
According to the present invention, completely disengage from prior art it is proposed that a kind of brand-new theory and the technique of preparing apt, saved The sodium tungstate solution transition step of a large amount of waste water can be produced, directly obtain ammonium tungstate solution, be inherently eliminated apt production During waste water discharge, and achieve recycling of supplies and solution.
According to the present invention, technological process is simple, easy to operate, low production cost, non-wastewater discharge, and environmental pollution is reduced to Low degree.
Brief description
Fig. 1 is a kind of process chart being prepared apt by tungsten mineral material according to the present invention.
Fig. 2 is a kind of principle schematic diagram. of the system being prepared apt by tungsten mineral material according to the present invention.
Specific embodiment
1-2 is described further to embodiments of the invention below in conjunction with the accompanying drawings.
As shown in figure 1, the metallurgical technology containing tungsten mineral material of the present invention comprises the following steps:
Raw mineral materials containing w 100 and dispensing mn (m represents cation, and n represents anion) proportioning is made to become raw material 101；
Roasting raw material 200, promote it and chemical reaction occur, to be transformed into the grog containing m with containing w ion, so that grog obtains Obtain high chemical reactivity；
(the excessive highly basic of thorough abandoning tradition leaches prejudice) grog is leached using weak base an (a is cation) solution, so that grog Leach 300, and in circular response, reclaim the solution that each link feeds back, and supplement loss according to being actually needed Weak base an；
Solid-liquid separation 400 is carried out to leaching slurry, obtains the thick solution containing a with containing w ion and the leached mud containing m, to slag Mutually wash, cleaning mixture feeds back to grog and leaches link (the i-th closed loop), according to actual needs, takes at least part of leached mud to feed back to Raw material configuration link (the i-th i closed loop), as dispensing, if leached mud has remainder, are stored up；
At least first class purification remove impurity 500 (afterbody can add extractor fan) is carried out to the thick solution containing a with containing w ion；
Solution after purifying is evaporated crystallizing 600, to separate out the intermediate products containing w element；Meanwhile, will discharge with The related gas of a element and the gas related to n element are back to the step (the i-th ii closed loop) leaching grog 300, and evaporate The water going out feeds back to the solid-liquid separation link (the i-th v closed loop) of leaching slurry 300；
Solid-liquor separation 700 is carried out to the serosity after crystallization, to obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution Wash, obtain the final products containing w element after drying and (preferably solid phase is dissolved again and crystallize, to obtain purity more High final products)；And crystalline mother solution also returns to the step (v closed loop) leaching grog,
For this reason, this technique comprises multiple closed cycles, whole non-wastewater discharge.
As shown in Fig. 2 the metallurgical system of the tungsten mineral material of the present invention includes successively:
Raw material preparation facilitiess 10, it has raw mineral materials dosage/metering entrance 11 and dosage/metering entrance 12 (preferably also sets Have mineralising agent dose/metering entrance 13), raw material fine mill (containing vortex mixer) 14, raw material outlet 15 and leached mud receiving port 16；
Calcining kiln (stove) 20, it is connected with raw material outlet 15 with raw material silo through feeding measurement device, has heater, insulation dress Put (preferably also including chiller 21) and thick grog outlet 22；
Grog fine mill 30, it is connected with thick grog outlet 22 through grog storehouse, has ore grinding device and thin grog outlet 31；
Leaching device 40, it has leaching agent entrance 41, leaching slurry outlet 42, feedback gas with thin grog outlet 31 Body recovery port 43, slurry separating, washing liquid recovery port 44, slag phase cleaning mixture recovery port 45, crystal seed entrance 46 are (preferably, Also include carbon dioxide and be passed through mouth 47)；
Leaching slurry equipment for separating liquid from solid (preferably defecator), it is connected with leaching slurry outlet 42, has element containing dispensing The filtration washing device 50 of leached mud, containing the thick taphole 51 of wolfram element, leached mud feedback port 52, leach slag muck to remaining The outlet 53 of warehousing, washing liquid feedback outlet 54, the receiving port 55 of evaporative crystallization condensed water, this equipment for separating liquid from solid is feeding back to Connect with the crystal seed entrance 46 of leaching device 40 in the way of leached mud receiving port 16 of raw material preparation facilitiess 10；
At least first class purification knot screen 60, the entrance 61 of the first order is connected with the thick taphole 51 containing wolfram element, at different levels There is purification and impurity removal agent entrance and impurity collector, (preferably, afterbody has smart taphole 62 containing wolfram element Rear stage adds extractor fan)；
Crystallization apparatus 70, its entrance 71 is connected with the smart taphole 62 containing wolfram element, has slurry outlet 72, anti- It is fed to gas feedback mouth 73 and the condensation-water drain 74 (preferably there is smart solution evaporation cerium sulphate crystal device) of leaching device；
The liquid-solid separation device 80 of slurry, it is connected with slurry outlet 72, has crystalline mother solution and is back to leaching dress The outlet 83 putting 40 outlet 81, solid phase wash water entrance 82 and tungsten product (preferably, is dissolved, crystallizes, is carried with next stage Pure subsystem connection).
According to the present invention, by tungsten mineral material with a certain amount of calcareous material and mineralizer after levigate, mix homogeneously obtains raw material； When raw material are prepared, the addition of calcareous material at least generates ca by the tungsten making in tungsten mineral material3wo6And/or ca2fewo6 And/or ca2mnwo61.0 times of theoretical amount, preferably 1.1-1.5 times, more preferably 1.1-1.2 times；
When raw material are prepared, for fluoride it is therefore preferable to calcium fluoride, the addition of calcium fluoride is that dry tungsten mineral is former to the mineralizer allocated into The 0.5-7% (mass percent) of doses, preferably 1-3% (mass percent)；Raw material granularity is not particularly limited, preferably not More than 200 μm, more preferably not more than 100 μm, more preferably not more than 40 μm；Raw material sintering temperature is not less than 500 DEG C, Preferably raw material sintering temperature is 800～1050 DEG C, more preferably 850～950 DEG C；Roasting time is not particularly limited, and temperature is low Then need to extend roasting time, for making the tungsten in raw material be fully converted into ca3wo6、ca2fewo6And/or ca2mnwo6, Preferably roasting time is 0.5-8.0h, more preferably 1.0～3.0h, roasting 2.0h more preferably at 850～950 DEG C.
For scheelite raw material, calcination atmosphere is not particularly limited, preferably neutral or oxidizing atmosphere；For wolframite, black White tungsten composite ore and/or tungsten slurry raw material, calcination atmosphere is neutral or reducing atmosphere, preferably neutral atmosphere.The present invention will Containing ca3wo6、ca2fewo6And/or ca2mnwo6Mixed material be added in ammonium salt solution system, in airtight condition Lower leaching, after the completion of leaching, the separated washing of leaching slurry, obtain ammonium tungstate solution.
Preferably, described ca3wo6And/or ca2fewo6And/or ca2mnwo6Can be the pure compound of synthetic, Can also be tungsten mineral material obtain after treatment containing ca3wo6And/or ca2fewo6And/or ca2mnwo6Mixing Thing (grog)；ca3wo6And/or ca2fewo6And/or ca2mnwo6Mixed material granularity be not more than 200 μm, excellent Elect as less than 45 μm；Described ammonium salt solution system, can be ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate system, ammonium carbonate-wolframic acid Ammonium-co2System, ammonium carbonate-ammonia-ammonium tungstate system, ammonium carbonate-ammonia-water systems, Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate System, ammonium carbonate-ammonia-co2System, ammonium carbonate-ammonia-ammonium tungstate-co2System, ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2 System, ammonium carbonate-co2System, ammonium carbonate-ammonium tungstate system, can also be ammonium carbonate-ammonium hydrogen carbonate-co2System.
Preferably, with Ammonium Carbonate system, ammonium carbonate-ammonium hydrogen carbonate system, ammonium carbonate-ammonia-water systems, ammonium carbonate-ammonium hydrogen carbonate- Ammonium tungstate system, ammonium carbonate-ammonia-ammonium tungstate system and ammonium carbonate-ammonium tungstate system leach ca3wo6And/or ca2fewo6 And/or ca2mnwo6When, the absolute pressure of Leaching Systems is not particularly limited；With ammonium carbonate-co2System, ammonium carbonate-carbon Sour hydrogen ammonium-co2System, ammonium carbonate-ammonia-co2System, ammonium carbonate-ammonium tungstate-co2System, ammonium carbonate-ammonia-ammonium tungstate -co2System and ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2System leaches ca3wo6And/or ca2fewo6And/or ca2mnwo6When, leaching process is passed through co2, control the absolute pressure of Leaching Systems to be not less than 1atm, preferably 1.5-2.5atm, more preferably 2atm.
Preferably, Leaching Systems carbonic acid ammonium concentration is more than 20g- (nh4)2co3/100g-h2The ammonium carbonate of o, preferably saturation is molten Liquid.
Preferably, described ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-co2, ammonium carbonate-ammonia-ammonium tungstate, carbon Sour ammonium-ammonium tungstate, ammonium carbonate-ammonia-ammonium tungstate-co2With ammonium carbonate-ammonium hydrogen carbonate-ammonium tungstate-co2In solution system, wolframic acid Ammonium concentration is also not particularly limited, as long as meeting ca3wo6And/or ca2fewo6And/or ca2mnwo6In tungsten abundant After leaching, in resulting solution, ammonium tungstate concentration is less than its dissolubility in this system.
Preferably, described ammonium carbonate-ammonium hydrogen carbonate, ammonium carbonate-ammonium tungstate-ammonium hydrogen carbonate, ammonium carbonate-ammonium hydrogen carbonate-co2And carbon Sour ammonium-ammonium hydrogen carbonate-ammonium tungstate-co2Solution system, ammonium hydrogen carbonate addition is not particularly limited, preferably not less than theoretical amount 1.0 times, more preferably the 1.1～1.4 of theoretical amount times.
Preferably, described ammonium carbonate-ammonia-ammonium tungstate, ammonium carbonate-ammonia-ammonium tungstate-co2, ammonium carbonate-ammonia and ammonium carbonate- Ammonia-co2In solution system, the addition of ammonia is also not particularly limited, and preferably leaches nh in initial system3Quality Percentage composition is 0%～28%, more preferably 5%～20%, more preferably 5%～10%.
Preferably, Leaching Systems ph is controlled to be not less than 8.0.Extraction temperature is not less than 5 DEG C, preferably 10-80 DEG C, more preferably For 20-70 DEG C, more preferably 30-50 DEG C；Extraction time is not particularly limited, as long as ca can be made3wo6And/or ca2fewo6 And/or ca2mnwo6In tungsten fully leach, preferably 0.5-8.0h, more preferably extraction time be 2.0-5.0h.
Preferably, the initial liquid-solid ratio of Leaching Systems is not less than 1:1ml/g, preferably 10:1-4:1ml/g.
Preferably, the final liquid-solid ratio of Leaching Systems by way of multistage feeds, can be reduced, preferably pass through two sections and feed, 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 are a large amount of nh4In the presence of oh, (nh4)2wo4 The high activity caco that can generate with leaching process3There is secondary response, generate and to be difficult to be leached by ammonium carbonate salt solution cawo4, lead to 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 in ca3wo6Leaching process in newborn caco3Activity is high, and reaction (1) is then possible to carry out, and carries out nh with leaching process4Oh and (nh4)2wo4Dense Degree is continuously increased, and reaction (1) and reaction (2) are strengthened, and ultimately result in (nh4)2wo4When concentration is higher, the loss of tungsten increases. Therefore, it is passed through co in airtight Leaching Systems2, the rapid nh neutralizing in solution4Oh, makes reaction (1) be suppressed；With When by add caco3Crystal seed, makes newborn caco3Grow up rapidly in seed surface, reduce its activity, suppress anti-further Answer the carrying out of (1).Thus be expected to obtain (the nh of high concentration simultaneously4)2wo4Solution and high tungsten leaching rate.
Additionally, being passed through co in enclosed system2, co can also be improved2Utilization rate.
According to embodiments of the invention, by thick ammonium tungstate solution purification and impurity removal, the method for purification and impurity removal is not particularly limited, as long as In solution after purification the impurity such as p, as, si, mo, s, sn, sb, k, na, ca, mg content meet prepare qualified Apt product quality requires.According to one embodiment of present invention, can be removed in ammonium tungstate solution using the sedimentation method Impurity, thus prepares ammonium tungstate refined liquid.
According to embodiments of the invention, ammonium tungstate refined liquid can be taken apt, the bar of evaporative crystallization using evaporative crystallization legal system Part is not particularly limited.According to one embodiment of present invention, at 95 DEG C, it is 6.5 that ammonium tungstate solution is evaporated to ph, After washing through solid-liquid separation and product, the apt product purity of acquisition meets 0 grade of product standard in gb/t10116-2007.
Embodiment 1: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.1 times of theoretical amount, (main component is caco to allocate grog leached mud into3) and mineralizer calcium fluoride carry out levigate, Raw material are obtained, the addition of calcium fluoride is 5.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm after mixing, Then, in roaster, under air atmosphere, 800 DEG C of roasting 2.0h, obtain grog.Clinker cooling to room temperature, with vibration Ore mill is levigate, grog granularity≤45 μm.Weigh 5.0g levigate after grog be added to ventilation and mechanical stirring device anti- Answer in kettle, be simultaneously introduced 50g- (nh4)2co3/100g-h2The sal volatile 50ml of o is simultaneously airtight, then passes to co2 Gas, the absolute pressure controlling reaction system is 2atm, reacts 5h at 80 DEG C.After reaction terminates, leach ore pulp using true Empty sucking 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%, fe weight/mass percentage composition is 5.90%) By generation ca3wo6And ca2fewo61.5 times of theoretical amount, allocate into grog leached mud carry out levigate, mix after obtain raw material, Raw material granularity≤45 μm, then, in shaft furnace, under weak reducing atmosphere, 950 DEG C of roasting 3.0h, obtain grog.Grog is cold But to room temperature, levigate with ball mill, grog granularity≤45 μm.Weigh 20.0g grog and be added to band ventilation and mechanical agitation dress In the reactor put, it is simultaneously introduced 35g- (nh4)2co3/100g-h2The sal volatile 100ml of o airtight, Ran Houtong Enter co2Gas, the absolute pressure controlling reaction system is 2atm, reacts 4h at 70 DEG C.After reaction terminates, leach ore deposit Slurry adopts 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%, fe weight/mass percentage composition is 14.08%, mn Weight/mass percentage composition is 2.25%) by generation ca3wo6And ca2fewo6And ca2mno61.13 times of theoretical amount, allocate into Grog leached mud and calcium fluoride carry out levigate, mix after obtain raw material, the addition of calcium fluoride is dry tungsten mineral material amount 7% (mass percent), raw material granularity≤40 μm, then, in pipe type calciner, under neutral atmosphere, roasting 6.0h at 800 DEG C, Obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, Built-in ammonium carbonate saturated solution, and 1.0 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, at 80 DEG C Lower reaction 4h.After reaction terminates, leach ore pulp and adopt 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 adopts evaporative crystallization to separate out apt, obtains simultaneously Ammonia and carbon dioxide, carry out solid-liquor separation to the serosity after crystallization, obtain crystalline mother solution and solid phase, solid phase is through water washing Obtain apt product afterwards, apt product reaches 0 grade of product standard of country and requires；The ammonia obtaining returns together with carbon dioxide To leaching equipment, and supplementing lossAmmonium carbonatePosterior circle leaches grog.
Embodiment 4: by certain wolframite (wo3Weight/mass percentage composition is 42.17%, fe weight/mass percentage composition is 11.34%) by life Become ca3wo6And ca2fewo61.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after given birth to 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, after clinker cooling to room temperature, use Ball-stirring mill Levigate, grog granularity≤45 μm；Leaching equipment selection ball milling digester, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.1 times of addition ammonium hydrogen carbonate；Grog is put into leaching equipment, reacts 4h at 40 DEG C.After reaction terminates, leach ore pulp and adopt With vacuum filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3 but supplementCarbon Sour hydrogen ammonium and ammonia.
Embodiment 5: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo62.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition is 3% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster neutral atmosphere Roasting 4h at 870 DEG C, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤45 μm；Leaching sets The leaching tanks of alternative band stirring, built-in ammonium carbonate saturated solution, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Will be ripe Leaching equipment put into by material, and being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 5%) and airtight, Ran Houtong Enter carbon dioxide, the absolute pressure controlling Leaching Systems is 2atm, react 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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤45 μm, then, roasting 7h at 1000 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with centrifugal mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and ammonium carbonate is dense Spend for 35g- (nh4)2co3/100g-h2O, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching set Standby, react 9h at 40 DEG C.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 of country and requires.
Embodiment 7: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 950 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, is ground with planet mill Carefully, grog granularity≤45 μm；Leaching equipment selects the leaching tanks of band stirring, built-in unsaturated carbonate ammonium and containing 20g/lwo3Tungsten Sour ammonium mixed solution, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, is simultaneously introduced ammonia (make nh in infusion solution3Weight/mass percentage composition is 9.5%) and airtight, then, it is passed through carbon dioxide, control and leach body The absolute pressure of system is 3atm, reacts 6h at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three Secondary.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 generation ca3wo62.67 times of theoretical amount, Allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤40 μm, then, in 940 DEG C of roaster reducing atmosphere Lower roasting 3h, obtains grog, after clinker cooling to room temperature；Leaching equipment selects the leaching tanks with stirring, built-in unsaturated carbonate Ammonium and wo containing 120g/l3Ammonium tungstate mixed solution, and according to 1.4 times of theoretical amount addition ammonium hydrogen carbonate；Grog is put into Leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 10%) and airtight, anti-at 30 DEG C Answer 4h.After reaction terminates, leach ore pulp, with pure water filter cake three times.The leaching rate of tungsten is 97.51%.Then, it is similar to Embodiment 3 but supplement ammonia and co2.
Embodiment 9: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo60.5 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, raw material Granularity≤45 μm, then, roasting 1.5h at 965 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with twin rollers, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, carbonic acid ammonium concentration For 67g- (nh4)2co3/100g-h2O, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, 6.5h is reacted at 18 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 29.30%.
Embodiment 10: by certain Scheelite-Wolframite Mixed Mine (wo3Weight/mass percentage composition is 43.20%, fe weight/mass percentage composition is 7.18%) By generation ca3wo6And ca2fewo60.4 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, Raw material granularity≤45 μm, then roasting 3h at 500 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, Levigate with vibrating mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and ammonium carbonate is dense Spend for 50g- (nh4)2co3/100g-h2O, and 1.25 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching set Standby, react 3.5h at 28 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten For 9.76%.
Embodiment 11: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 950 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, is ground with vibrating mill Carefully, grog granularity≤40 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.1 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Quality hundred Content is divided to be 10%) and airtight, react 4.5h at 27 DEG C.After reaction terminates, leach ore pulp filter pressing, use 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo60.77 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, the addition of calcium fluoride For 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤100 μm, then, in 845 DEG C of roaster neutral atmosphere Lower roasting 2.5h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put Enter leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 5.9%) and airtight, then, lead to Enter carbon dioxide, the absolute pressure controlling Leaching Systems is 2.5atm, react 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%, fe weight/mass percentage composition is 0.43%) by life Become 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 870 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, uses jet mill Levigate, grog granularity≤74 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to theory 1.4 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Quality Percentage composition is 20%) and airtight, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, filtered with pure water 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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorination The addition of calcium is 0.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤50 μm, then, in roaster Roasting 2h at 920 DEG C of atmosphere of property, obtains grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤45 μm； Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 2h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times. The leaching rate of tungsten is 98.22%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 15: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.13 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤45 μm, then, roasting 2h at 960 DEG C of roaster neutral atmosphere, 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 presses According to reason 1.2 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, Leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 98.35%.Then, similar embodiment 3, apt Product reaches 0 grade of product standard of country and requires.
Embodiment 16: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.37 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤61 μm, then, roasting 2h at 970 DEG C of roaster oxidizing atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with ball mill, grog granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.4 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts 4h at 55 DEG C.After reaction terminates, leaching Go out ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.31%.Then, similar embodiment 3, apt produces Product reach 0 grade of product standard of country and require.
Embodiment 17: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤53 μm, then, roasting 0.5h at 990 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with planet mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and presses According to reason 1.5 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, reacts 2h at 62 DEG C.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 of country and requires.
Embodiment 18: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.57 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤74 μm, then, roasting 2h at 980 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with high pressure disc mill, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and 1.6 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 3.5h at 75 DEG C.Reaction terminates Afterwards, 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 of country and requires.
Embodiment 19: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 For 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, in 880 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put Enter leaching equipment, being simultaneously introduced ammonia (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%, fe weight/mass percentage composition is 0.43%) by life Become 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 For 5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, in 860 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with tower mill, grog granularity≤45 μm；Leaching equipment Select leaching tanks, built-in unsaturated carbonate ammonium and wo containing 60g/l with stirring3Ammonium tungstate mixed solution；Grog is put into leaching Go out equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 15%) and airtight, then pass to dioxy Change carbon gas, the absolute pressure controlling Leaching Systems is 1.2atm, react 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, co2 And ammonium carbonate.
Embodiment 21: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 880 DEG C of roaster reducing atmosphere, obtains grog, after clinker cooling to room temperature, uses vibrating mill Levigate, grog granularity≤45 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to theory 1.4 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Quality Percentage composition is 10.0%) and airtight, then pass to carbon dioxide, the absolute pressure controlling Leaching Systems is 1.5atm, 3.8h is reacted at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 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%, fe weight/mass percentage composition is 0.43%) by life Become 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 880 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, Grog granularity≤45 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.4 times of addition ammonium hydrogen carbonate；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes the percent mass of nh3 in infusion solution Content is 7.4%) and airtight, then, it is passed through carbon dioxide, the absolute pressure controlling Leaching Systems is 1.9atm, 3.8h is reacted at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 38.35%. Then, similar embodiment 3 but supplement ammonia and co2.
Embodiment 23: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo60.5 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, raw material Granularity≤33 μm, then, roasting 5h at 965 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, use Vibrating mill is levigate, grog granularity≤74 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, carbonic acid ammonium concentration For 80g- (nh4)2co3/100g-h2O, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, 6.5h is reacted at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 22.96%.Then, similar embodiment 3.
Embodiment 24: by certain Scheelite-Wolframite Mixed Mine (wo3Weight/mass percentage composition is 43.20%, fe weight/mass percentage composition is 7.18%) By generation ca3wo6And ca2fewo60.97 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, The addition of calcium fluoride is 2% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤30 μm, then, in roaster Roasting 3h at 850 DEG C of neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤74 μm； Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 80g- (nh4)2co3/100g-h2O, and 1.25 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 4h at 28 DEG C.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%, fe weight/mass percentage composition is 0.43%) by life Become 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 950 DEG C of roaster oxidizing atmosphere, obtains grog, after clinker cooling to room temperature, is ground with ball mill Carefully, grog granularity≤45 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching Go out equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 20%) and airtight, react at 27 DEG C 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo60.77 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, the addition of calcium fluoride For 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤41 μm, then, in 845 DEG C of roaster neutral atmosphere Lower roasting 2.5h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤83 μm；Leaching equipment selects Select ball milling infuser, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching Go out equipment, be simultaneously introduced ammonia (weight/mass percentage composition making nh3 in infusion solution is 9.8%) airtight, reaction at 37 DEG C 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%, fe weight/mass percentage composition is 5.86%) by life Become ca3wo6And ca2fewo61.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorination The addition of calcium is 2.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤61 μm, then, in roaster Roasting 1h at 870 DEG C of atmosphere of property, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm； Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount； Grog is put into leaching equipment, reacts 8.0h at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo6And ca2mno61.5 times of theoretical amount, allocate manganese spar into and limestone carries out levigate mixing After obtain raw material, raw material granularity≤14 μm, then, roasting 2h at 920 DEG C of roaster neutral atmosphere, obtain grog, grog After being cooled to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, and built-in ammonium carbonate is satisfied And solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 5h at 43 DEG C. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 98.42%.Then, it is similar in fact Apply example 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 29: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.63 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤42 μm, then, roasting 2h at 960 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with planetary mills, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to 1.2 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leaching Go out ore pulp sucking filtration, with pure water filter cake 2 times.The leaching rate of tungsten is 97.35%.Then, similar embodiment 3, apt produces Product reach 0 grade of product standard of country and require.
Embodiment 30: by certain scheelite (wo3Weight/mass percentage composition is 60.94%) by generation ca3wo6And ca2mnwo6 1.53 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 980 DEG C of roaster neutral atmosphere, obtains 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 1.5 times according to theoretical amount Add ammonium hydrogen carbonate；Grog is put into leaching equipment, reacts 4h at 50 DEG C.After reaction terminates, leach ore pulp sucking filtration, use Pure water filter cake 4 times.The leaching rate of tungsten is 97.99%.Then, similar embodiment 3, apt product reaches 0 grade of country Product standard requires.
Embodiment 31: by certain scheelite (wo3Weight/mass percentage composition is 60.94%) by generation ca3wo61.43 times of theoretical amount, Allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤48 μm, then, in 970 DEG C of roaster neutral atmosphere Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm；Leaching equipment selects Select leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching Go out equipment, react 4h at 55 DEG C.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 of country and requires.
Embodiment 32: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.63 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤38 μm, then, roasting 1h at 990 DEG C of roaster oxidizing atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with ball mill, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to 1.5 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts 4h at 62 DEG C.After reaction terminates, leaching Go out ore pulp sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 97.78%.Then, similar embodiment 3, apt produces Product reach 0 grade of product standard of country and require.
Embodiment 33: by certain scheelite (wo3Weight/mass percentage composition is 60.94%) by generation ca3wo61.7 times of theoretical amount, Allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤63 μm, then, in 980 DEG C of roaster neutral atmosphere Lower roasting 2h, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects Select leaching device, built-in ammonium carbonate saturated solution, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching Go out equipment, react 0.5h at 75 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times.The leaching of tungsten Going out rate is 97.51%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 34: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 880 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog Granularity≤45 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution, and 1.5 times according to theoretical amount Add ammonium hydrogen carbonate；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 5.0%) and airtight, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.Tungsten Leaching rate be 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%, fe weight/mass percentage composition is 0.43%) by life Become 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, and roasting 1h at 880 DEG C of roaster neutral atmosphere, obtain grog, clinker cooling is extremely After room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturation Solution, and 1.5 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching Nh in solution3Weight/mass percentage composition be 5.0%) and airtight, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp Filter pressing, with pure water filter cake three times.The leaching rate of tungsten is 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo60.83 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, the addition of calcium fluoride For 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤37 μm, then, in 880 DEG C of roaster reducing atmosphere Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤53 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution, and 1.15 times of addition ammonium hydrogen carbonate according to theoretical amount；By grog Put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 4.1%) and airtight, then, It is passed through carbon dioxide, the absolute pressure controlling Leaching Systems is 1.3atm, react 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo60.73 times of theoretical amount, allocates into after limestone carries out levigate mixing and obtains raw material, the addition of calcium fluoride is dry 1.5% (mass percent) of tungsten mineral material amount, raw material granularity≤24 μm, then, at 880 DEG C of roaster reducing atmosphere Roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leaching equipment selects Ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, reacts 8.0h at 32 DEG C.Reaction terminates Afterwards, 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%, fe weight/mass percentage composition is 2.04%) by life Become 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, and roasting 1h at 950 DEG C of roaster neutral atmosphere, obtain grog, clinker cooling is extremely After room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, carbon Sour ammonium concentration is 58g- (nh4)2co3/100g-h2O, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into Leaching equipment, reacts 9h at 40 DEG C.After reaction terminates, leach ore pulp filter pressing, with pure water filter cake three times.The leaching of tungsten Going out rate is 96.93%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 39: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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, at 895 DEG C of roaster neutral atmosphere Roasting 8h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects With the leaching tanks of stirring, built-in ammonium carbonate saturated solution, and 1.9 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into Leaching equipment, reacts 6h at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching of tungsten Going out rate 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 generation ca3wo61.3 times of theoretical amount, Allocate into after limestone carries out levigate mixing and obtain raw material, raw material granularity≤40 μm, then, in 940 DEG C of roaster reducing atmosphere Lower roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten Nh in liquid3Weight/mass percentage composition be 12%) and airtight, react 4h at 50 DEG C.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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.17 times of theoretical amount, allocate into after limestone carries out levigate mixing and obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 0.7% (mass percent), raw material granularity≤30 μm, then, neutral in roaster Roasting 1.5h at 965 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm； Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 67g- (nh4)2co3/100g-h2O, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 20.0h at 10 DEG C.Reaction terminates Afterwards, 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 of country and requires.
Embodiment 42: by certain Scheelite-Wolframite Mixed Mine (wo3Weight/mass percentage composition is 43.20%, fe weight/mass percentage composition is 7.18%) By generation 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, and raw material granularity≤25 μm, then, in roasting Roasting 3h at 850 DEG C of stove neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm； Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 70g- (nh4)2co3/100g-h2O, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 3.5h at 40 DEG C.Reaction terminates Afterwards, 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 of country and requires.
Embodiment 43: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 845 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with vibromill, Grog granularity≤74 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching set Standby, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 28%) and airtight, react 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 96.01%.Then, it is similar in fact Apply example 3 but supplement ammonium carbonate, ammonia and co2.
Embodiment 44: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 For 5.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, in 845 DEG C of roaster neutral atmosphere Lower roasting 10h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤150 μm；Leaching equipment Select ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes infusion solution Middle nh3Weight/mass percentage composition be 7.5%) and airtight, react 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 98.49%.Then, similar embodiment 3 but supplement ammonia and co2.
Embodiment 45: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 1050 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with rod mill, Grog granularity≤45 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching set Standby, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 9.1%) and airtight, react 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 97.15%.Then, it is similar in fact Apply example 3 but supplement ammonium hydrogen carbonate, ammonia and co2.
Embodiment 46: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorination The addition of calcium is 6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, neutral in roaster Roasting 0.5h at 995 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm； Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times. The leaching rate of tungsten is 97.22%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 47: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.83 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorine The addition changing calcium is 2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster also Roasting 2h at 960 DEG C of originality atmosphere, obtains grog, after clinker cooling to room temperature, levigate with jet mill, grog granularity ≤20μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition carbonic acid according to theoretical amount Hydrogen ammonium；Grog is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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 of country will Ask.
Embodiment 48: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorination The addition of calcium is 3.5% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster Roasting 0.5h at 850 DEG C of atmosphere of property, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm； Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.5 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 4h at 50 DEG C.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 of country and requires.
Embodiment 49: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.37 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤53 μm, then, roasting 8h at 930 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with overhang roll pulverizer, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and 1.1 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 4h at 25 DEG C.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 of country and requires.
Embodiment 50: by certain scheelite (wo3Weight/mass percentage composition is 60.94%) by generation 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% (quality of dry tungsten mineral material amount Percent), raw material granularity≤53 μm, then, and roasting 1h at 910 DEG C of roaster neutral atmosphere, obtain grog, grog is cold But to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturation Solution, and 1.5 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 4h at 62 DEG C.Instead After should terminating, leach ore pulp sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 98.78%.Then, it is similar to and implement Example 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 51: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.57 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, fluorine The addition changing calcium is 2.8% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤74 μm, then, in roaster Roasting 2h at 900 DEG C of neutral atmosphere, obtains 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 1.6 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 1.5h at 75 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 Secondary.The leaching rate of tungsten is 95.01%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 52: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 For 3.3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in 880 DEG C of roaster neutral atmosphere Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten Nh in liquid3Weight/mass percentage composition be 8.0%) and airtight, react 3.8h at 50 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 96.15%.Then, similar embodiment 3 but supplement ammonia and co2.
Embodiment 53: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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, at 810 DEG C of roaster neutral atmosphere Roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with planetary mills, grog granularity≤45 μm；Leaching equipment selects With the leaching tanks of stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes infusion solution Middle nh3Weight/mass percentage composition be 5.5%) and airtight, react 6h at 45 DEG C.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%, fe weight/mass percentage composition is 0.43%) by life Become 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, in 880 DEG C of roaster reducing atmosphere Lower roasting 1h, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten In liquid, the weight/mass percentage composition of nh3 is 3.5%) and airtight, react 3.8h at 32 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 96.75%.Then, similar embodiment 3 but supplement ammonia and co2.
Embodiment 55: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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, at 750 DEG C of roaster neutral atmosphere Roasting 5h, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤100 μm；Leaching equipment selects Ball milling infuser, built-in ammonium carbonate saturated solution, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching Equipment, reacts 3.8h at 32 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching of tungsten Rate is 86.35%.
Embodiment 56: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.33 times of theoretical amount, allocate into after limestone carries out levigate mixing and obtain raw material, nodules ≤ 106 μm of degree, then, roasting 7h at 1000 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, use Vibromill is levigate, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 35g-(nh4)2co3/100g-h2O, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, 9h is reacted at 40 DEG C.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 of country and requires.
Embodiment 57: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 1200 DEG C of roaster neutral atmosphere, obtains 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 1.4 times according to theoretical amount Add ammonium hydrogen carbonate；Grog is put into leaching equipment, reacts 6h at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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 generation ca3wo62.67 times of theoretical amount, Allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤96 μm, then, in roaster reducing atmosphere Roasting 3h at 1400 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks of equipment choice band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes Nh in infusion solution3Weight/mass percentage composition be 6%) and airtight, react 4h at 30 DEG C.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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤45 μm, then, roasting 8h at 965 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with centrifugal mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and ammonium carbonate is dense Spend for 20g- (nh4)2co3/100g-h2O, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching set Standby, react 6.5h at 18 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten For 92.96%.Then, similar embodiment 3.
Embodiment 60: by certain Scheelite-Wolframite Mixed Mine (wo3Weight/mass percentage composition is 43.20%, fe weight/mass percentage composition is 7.18%) By generation ca3wo6And ca2fewo61.07 times of theoretical amount, allocate grog leached mud into and after calcium fluoride carries out levigate mixing 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 850 DEG C of roaster neutral atmosphere, obtains 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 according to theoretical amount 1.25 extraordinarily Enter ammonium hydrogen carbonate；Grog is put into leaching equipment, reacts 3.5h at 28 DEG C.After reaction terminates, leach ore pulp sucking filtration, use Pure water filter cake three times.The leaching rate of tungsten is 96.76%.Then, similar embodiment 3, apt product reaches 0 grade of country Product standard requires.
Embodiment 61: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo63.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition is 1% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster neutral atmosphere Roasting 4h at 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤96 μm；Leaching sets Alternative ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten Nh in liquid3Weight/mass percentage composition be 5.9%) and airtight, react 4.5h at 47 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammonia and co2.
Embodiment 62: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.07 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 2.8% (mass percent), raw material granularity≤45 μm, then, roaster neutrality gas Roasting 5h at 845 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks of equipment choice band stirring, built-in sal volatile, carbonic acid ammonium concentration is 40g- (nh4)2co3/100g-h2o；Will Leaching equipment put into by grog, and being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 4%) and airtight, at 45 DEG C Lower reaction 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 1.2% (mass percent), raw material granularity≤120 μm, then, roaster neutrality gas Roasting 3h at 870 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks of equipment choice band stirring, built-in sal volatile, carbonic acid ammonium concentration is 45g- (nh4)2co3/100g-h2o；Will Leaching equipment put into by grog, and being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 7.9%) and airtight, 15h is reacted at 5 DEG C.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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.5 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after given birth to Material, the addition of calcium fluoride is 5.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roasting Burn roasting 4h at 750 DEG C of stove neutral atmosphere, obtain grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity ≤45μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate saturated solution, and 1.2 times of addition carbonic acid according to theoretical amount Hydrogen ammonium；Grog is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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 of country will Ask.
Embodiment 65: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become 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, in roasting Burn roasting 15h at 760 DEG C of stove neutral atmosphere, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity ≤45μm；Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition carbonic acid according to theoretical amount Hydrogen ammonium；Grog is put into leaching equipment, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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 of country will Ask.
Embodiment 66: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material Granularity≤45 μm, then, roasting 8h at 980 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, use Ball mill is levigate, grog granularity≤45 μm；Leaching equipment selection leaching device, built-in ammonium carbonate saturated solution, and according to reason 4 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, reacts 4h at 50 DEG C.After reaction terminates, leach ore deposit Slurry sucking filtration, with pure water filter cake 4 times.The leaching rate of tungsten is 96.33%.Then, similar embodiment 3, apt product reaches Require to 0 grade of product standard of country.
Embodiment 67: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become 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, neutral in roaster Roasting 2h at 970 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤40 μm； Leaching equipment selects leaching device, built-in sal volatile, and carbonic acid ammonium concentration is 25g- (nh4)2co3/100g-h2O, and 1.4 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 0.5h at 80 DEG C.Reaction terminates Afterwards, 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 of country and requires.
Embodiment 68: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤53 μm, then, roasting 8h at 990 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with rod mill, grog granularity≤74 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts 4h at 62 DEG C.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 Reach 0 grade of product standard of country to require.
Embodiment 69: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.57 times of theoretical amount, allocate grog leached mud into and fluorite carry out levigate mixing after given birth to Material, the addition of fluorite is 4% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster Roasting 2h at 980 DEG C of neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤40 μm； Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.6 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 3.5h at 75 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 Secondary.The leaching rate of tungsten is 97.01%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 70: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.07 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 2.5% (mass percent), raw material granularity≤36 μm, then, roaster neutrality gas Roasting 1h at 880 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks of equipment choice band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes Nh in infusion solution3Weight/mass percentage composition be 6.7%) and airtight, react 0.5h at 90 DEG C.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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 3.6% (mass percent), raw material granularity≤90 μm, then, roaster neutrality gas Roasting 1h at 860 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks of equipment choice band stirring, built-in ammonium carbonate saturated solution, and 1.1 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 6h at 45 DEG C.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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.03 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 4.8% (mass percent), raw material granularity≤45 μm, then, in roaster reproducibility Roasting 1h at 880 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity≤74 μm；Leaching Go out equipment choice ball milling infuser, built-in ammonium carbonate saturated solution,；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching Go out nh in solution3Weight/mass percentage composition be 7.5%) and airtight, react 3.8h at 32 DEG C.After reaction terminates, leach ore deposit Slurry 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 0.7% (mass percent), raw material granularity≤45 μm, then, roaster neutrality gas Roasting 9h at 880 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm；Leach Equipment choice ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching Nh in solution3Weight/mass percentage composition be 8.6%) and airtight, react 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 98.65%.Then similar embodiment 3 but supplement ammonium carbonate, ammonia Water and co2.
Embodiment 74: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.23 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 4.5% (mass percent), raw material granularity≤45 μm, then, in roaster, empty Under gas atmosphere, 800 DEG C of roasting 2.0h, obtain grog.Clinker cooling is to room temperature, levigate with vibrating mill, grog granularity ≤45μm.Weigh 25.0g levigate after grog be added to ventilation and mechanical stirring device reactor in, be simultaneously introduced 60g-(nh4)2co3/100g-h2The sal volatile 100ml of o is simultaneously airtight, then, is passed through co2Gas, controls reaction The absolute pressure of system is 2atm, reacts 4h at 80 DEG C.After reaction terminates, leach ore pulp and adopt vacuum filtration, use pure water Washing 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%, fe weight/mass percentage composition is 5.90%) By generation ca3wo6And ca2fewo61.5 times of theoretical amount, allocate grog leached mud into and calcium fluoride is carried out after levigate mixing To 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, to room temperature, uses ball mill Levigate, grog granularity≤45 μm.Weigh 30.0g levigate after grog be added to ventilation and mechanical stirring device reactor in, It is simultaneously introduced 45g- (nh4)2co3/100g-h2The sal volatile 100ml of o is simultaneously airtight, then passes to co2Gas, control The absolute pressure of reaction system processed is 2atm, reacts 4h at 70 DEG C.After reaction terminates, leach ore pulp and adopt 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%, fe weight/mass percentage composition is 15.08%) press Generate ca3wo6And ca2fewo61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate, mix 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, after clinker cooling to room temperature, use rod milling Machine is levigate, grog granularity≤45 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to reason 1.2 times of addition ammonium hydrogen carbonate of stoichiometric；Grog is put into leaching equipment, reacts 4h at 80 DEG C.After reaction terminates, leach Ore pulp adopts vacuum filtration, with pure water filter cake three times.The leaching rate of tungsten is 97.13%.Then, similar embodiment 3 is mended Fill the ammonium carbonate of loss.
Embodiment 77: by certain wolframite (wo3Weight/mass percentage composition is 42.17%, fe weight/mass percentage composition is 11.34%) press Generate ca3wo6And ca2fewo61.17 times of theoretical amount, allocate grog leached mud into and calcium fluoride is carried out after levigate mixing To 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, with stirring Grind levigate, grog granularity≤40 μm；Leaching equipment selection ball milling digester, built-in ammonium carbonate saturated solution, and according to theoretical amount 1.1 times addition ammonium hydrogen carbonate；Grog is put into leaching equipment, reacts 4h at 75 DEG C.After reaction terminates, leach ore pulp Using 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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo62.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition is 2.4% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤30 μm, then in roaster neutral atmosphere Roasting 4h at 870 DEG C, obtains grog, after clinker cooling to room temperature, levigate with planetary mills, grog granularity≤74 μm；Leaching sets Alternative ball milling infuser, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten Nh in liquid3Weight/mass percentage composition be 6.5%) and airtight, react 4h at 30 DEG C.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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤25 μm, then, roasting 7h at 1000 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with vibrating mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, built-in sal volatile, and ammonium carbonate is dense Spend for 60g- (nh4)2co3/100g-h2O, and 1.3 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching set Standby, react 9h at 40 DEG C.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 of country and requires.
Embodiment 80: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition is 3.2% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤45 μm, then, in roaster neutral atmosphere Roasting 5h at 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm；Leach The leaching tanks of equipment choice band stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes Nh in infusion solution3Weight/mass percentage composition be 10.0%) and airtight, the absolute pressure controlling Leaching Systems is 1.0atm, 12h is reacted at 20 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 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 generation ca3wo62.67 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 950 DEG C of roaster reducing atmosphere Lower roasting 3h, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching equipment selects Select the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes leaching molten Nh in liquid3Weight/mass percentage composition be 6.3%) and airtight, react 15h at 35 DEG C.After reaction terminates, leach ore pulp and take out Filter, with pure water filter cake three times.The leaching rate of tungsten is 91.51%.Then, ammonia and co are supplemented2.
Embodiment 82: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.2 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after given birth to Material, the addition of calcium fluoride is 4.1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roasting Burn roasting 1.5h at 965 DEG C of stove neutral atmosphere, obtain grog, after clinker cooling to room temperature, levigate with vibromill, grog granularity ≤60μm；Leaching equipment selects ball milling infuser, built-in ammonium carbonate-ammonium tungstate mixed solution, and carbonic acid ammonium concentration is 45g-(nh4)2co3/100g-h2O, wo in solution3Concentration is 40g/l, and 2 times of addition ammonium hydrogen carbonate according to theoretical amount； Grog is put into leaching equipment, reacts 6.5h at 18 DEG C.After reaction terminates, leach ore pulp sucking filtration, use 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 of country and requires.
Embodiment 83: by certain Scheelite-Wolframite Mixed Mine (wo3Weight/mass percentage composition is 43.20%, fe weight/mass percentage composition is 7.18%) By generation ca3wo6And ca2fewo61.1 times of theoretical amount, allocate grog leached mud into and calcium fluoride is carried out after levigate mixing To raw material, the addition of calcium fluoride is 2.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, Ran Hou Roasting 3h at 850 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog grain ≤ 45 μm of degree；Leaching equipment selects ball milling infuser, built-in sal volatile, and carbonic acid ammonium concentration is 40g- (nh4)2co3 /100g-h2O, and 1.25 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts at 42 DEG C 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 of country and requires.
Embodiment 84: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo63.0 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition is 0.55% (mass percent) of dry tungsten mineral material amount, and raw material granularity≤30 μm, then, in roaster neutral atmosphere Roasting 4h at 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leaching sets Leaching tanks, built-in unsaturated carbonate ammonium and the wo containing 60g/l of alternative band stirring3Ammonium tungstate mixed solution；Grog is put into Leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 9.1%) and airtight, anti-at 37 DEG C Answer 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%, fe weight/mass percentage composition is 0.43%) by life Become 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 845 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, uses overhang roll pulverizer Levigate, grog granularity≤74 μm；The leaching equipment leaching tanks with stirring for the selection, built-in ammonium carbonate saturated solution, and according to theory 1.2 times of addition ammonium hydrogen carbonate of amount；Grog is put into leaching equipment, reacts 4.5h at 45 DEG C.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%, fe weight/mass percentage composition is 0.43%) by life Become ca3wo61.27 times of theoretical amount, allocate grog leached mud into and calcium fluoride carry out levigate mixing after obtain raw material, calcium fluoride Addition be dry tungsten mineral material amount 1.5% (mass percent), raw material granularity≤45 μm, then, roaster neutrality gas Roasting 1h at 870 DEG C of atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm；Leach The leaching tanks with ball milling for the equipment choice, built-in supersaturation ammonium carbonate serosity, carbonic acid ammonium concentration is 100g (nh4)2co3/100g h2o；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 6.5%) and Airtight, react 3.8h at 52 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake three times.The leaching of tungsten Rate 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%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.5 times of theoretical amount, allocate limestone into and fluorite carry out levigate mixing after obtain raw material, firefly The addition of stone is 2.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in roaster reduction Roasting 2h at 920 DEG C of atmosphere of property, obtains grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm； Leaching equipment selects leaching device, built-in ammonium carbonate saturated solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Will Leaching equipment put into by grog, reacts 5h at 38 DEG C.After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 2 times. The leaching rate of tungsten is 98.12%.Then, similar embodiment 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 88: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.13 times of theoretical amount, (main component is to allocate the slag after grog in embodiment 86 leaches into caco3) and calcium fluoride carry out levigate mix after obtain raw material, the addition of calcium fluoride is 4.1% (matter of dry tungsten mineral material amount Amount percent), raw material granularity≤100 μm, then, and roasting 2h at 960 DEG C of roaster neutral atmosphere, obtain grog, grog After being cooled to room temperature, levigate with vibromill, grog granularity≤45 μm；Leaching equipment selects leaching device, and built-in ammonium carbonate is satisfied And solution, and 1.2 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching equipment, reacts 3h at 50 DEG C. After reaction terminates, leach ore pulp sucking filtration, with pure water filter cake 5 times.The leaching rate of tungsten is 98.39%.Then, it is similar in fact Apply example 3, apt product reaches 0 grade of product standard of country and requires.
Embodiment 89: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo61.4 times of theoretical amount, allocate the slag after grog leaches in embodiment 88 into and calcium fluoride is carried out Raw material are obtained, the addition of calcium fluoride is 0.2% (mass percent) of dry tungsten mineral material amount, raw material granularity after levigate mixing ≤ 74 μm, then, roasting 1.5h at 980 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, with shaking Levigate, grog granularity≤85 μm of dynamic mill；Leaching equipment selects ball milling infuser, built-in supersaturation ammonium carbonate serosity, and ammonium carbonate is dense Spend for 120g (nh4)2co3/100g h2O, and 1.5 times of addition ammonium hydrogen carbonate according to theoretical amount；Grog is put into leaching set Standby, react 6h at 70 DEG C.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 of country will Ask.
Embodiment 90: by certain scheelite (wo3Weight/mass percentage composition is 52.33%, fe weight/mass percentage composition is 2.04%) by life Become ca3wo6And ca2fewo62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw Material granularity≤80 μm, then, roasting 7h at 1000 DEG C of roaster neutral atmosphere, obtain grog, after clinker cooling to room temperature, Levigate with vibromill, grog granularity≤45 μm；Leaching equipment selection ball milling infuser, built-in ammonium carbonate saturated solution, and according to 1.3 times of addition ammonium hydrogen carbonate of theoretical amount；Grog is put into leaching equipment, reacts 24h at 40 DEG C.After reaction terminates, leaching Go out ore pulp sucking filtration, with pure water filter cake three times.The leaching rate of tungsten is 98.66%.Then, similar embodiment 3, apt produces Product reach 0 grade of product standard of country and require.
Embodiment 91: by certain scheelite (wo3Weight/mass percentage composition is 49.53%, fe weight/mass percentage composition is 0.43%) by life Become 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 950 DEG C of roaster neutral atmosphere, obtains grog, after clinker cooling to room temperature, levigate with ball mill, Grog granularity≤45 μm；Leaching equipment selects the leaching tanks with stirring, built-in ammonium carbonate saturated solution；Grog is put into leaching set Standby, being simultaneously introduced ammonia (makes nh in infusion solution3Weight/mass percentage composition be 13.0%) and airtight, react 20h at 40 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, it is similar in fact Apply example 3 but supplement ammonia and co2.
Embodiment 92: by certain tungsten slurry (wo3Weight/mass percentage composition is 16.22%) by generation 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 dry tungsten mineral material amount 6.5% (mass percent), raw material granularity≤45 μm, then, and roasting 0.5h at 750 DEG C of roaster reducing atmosphere, obtain ripe Material, after clinker cooling to room temperature, levigate with centrifugal mill, grog granularity≤45 μm；Leaching equipment selects ball milling infuser, interior Put ammonium carbonate saturated solution；Grog is put into leaching equipment, being simultaneously introduced ammonia (makes nh in infusion solution3Percent mass contain Measure as 8.5%) and airtight, react 4h at 45 DEG C.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 have motivation to go to consider the technology of the present invention , there is not employing " common knowledge " or " customary means " in design.Even so, even with design, it is related to Multiple factors are all often mutual restrictions, interactional, are not separate, even if using modern times such as orthogonal designs Change scientific method, still have infinite possible combination, and technical scheme excellent enough can not be predicted, " the reality of limited number of time Test " the suitable value of each factor can not possibly be obtained, technical scheme excellent enough is less " apparent ".
Above numerous embodiments of the present invention are not limitation of the invention.It will be understood to those skilled in the art that not inclined On the premise of the spirit of the present invention and design, modification 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 (13)

1. a kind of metallurgical system of tungsten mineral material is it is characterised in that this system includes successively:
Raw material preparation facilitiess, it has the receiving port feeding back leached mud that the Task-size Controlling device of mixed material and subsequent handling produce；
Grog preparation facilitiess, it includes calcining kiln/stove and grog fine mill；
Leaching device, it has the absolute pressure controller of Leaching Systems, Leaching Systems ammonium carbonate consistency controller, leaching agent add Enter amount controller, control Leaching Systems ph controller, extraction temperature controller, extraction time controller, Leaching Systems initial Liquid-solid ratio controller, Leaching Systems final liquid-solid ratio controller, 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 outlet, the connecing of evaporative crystallization condensed water Close up, this equipment for separating liquid from solid crystal seed entrance with leaching device in feeding back to the way of leached mud receiving port of raw material preparation facilitiess Connection；
At least first class purification knot screen, the entrance of first order purification and impurity removal device is connected with the thick taphole containing wolfram element, respectively Level purification and impurity removal device has purification and impurity removal agent entrance and impurity collector, and afterbody purification and impurity removal device has containing wolfram element Smart taphole；
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, solid phase wash water entrance and tungsten The outlet of product.
2. system according to claim 1 it is characterised in that: described raw material preparation facilitiess and/or grog fine mill choosing From: vibrating mill, twin rollers, ball mill, rod mill, autogenous tumbling mill, agitator mill, overhang roll pulverizer, tower mill, glue Body grinding machine, centrifugal mill, high pressure disc mill, Raymond mill, jet mill.
3. system according to claim 1 it is characterised in that: described calcining kiln/stove is static calcining kiln/stove or dynamic roasts Firing/stove.
4. system according to claim 1 it is characterised in that: described leaching device is an independent leaching equipment, or 2-4 leaching equipment of person is used in series.
5. system according to claim 1 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 sealing, and 3atm pressure can be born；
The liquid-solid separation device of the equipment for separating liquid from solid of described leaching slurry or slurry be pumping and filtering device, filtering equipment and/ Or natural filtration groove；And
Described purification and impurity removal equipment is decleaning tank, filter plant and/or subsider, be provided with described decleaning tank agitating device, Attemperator.
6. a kind of metallurgical technology containing tungsten mineral material is it is characterised in that this technique comprises the following steps:
Raw mineral materials containing w is made to become raw material with dispensing mn proportioning, wherein, m represents cation, and n represents anion；
Roasting raw material, promote it and chemical reaction occur, to be transformed into the grog containing m with containing w ion, so that grog obtains height Chemical reactivity；
Grog is leached using weak base an solution, so that grog leaches, and in circular response, reclaims each link and feed back Solution, and according to be actually needed supplement loss weak base an, wherein, a be cation；
Solid-liquid separation is carried out to leaching slurry, obtains the thick solution containing a with containing w ion and the leached mud containing m, to slag phase Washing, cleaning mixture feeds back to grog and leaches link, according to actual needs, takes at least part of leached mud to feed back to raw material configuration link As dispensing, if leached mud has remainder, store up；
At least first class purification remove impurity is carried out to the thick solution containing a with containing w ion；
Solution after purifying is evaporated crystallizing, to separate out the intermediate products containing w element；Meanwhile, will discharge and a unit The related gas of element and the gas related to n element are back to the step leaching grog, and the water evaporating feeds back to leaching slurry The solid-liquid separation link of liquid；
Solid-liquor separation is carried out to the serosity after crystallization, to obtain crystalline mother solution and solid phase, solid phase is washed through water and/or ammonium salt solution, The final products containing w element are obtained after drying；And crystalline mother solution also returns to the step to leaching grog,
Slurry after solid-liquor separation and/or washing, crystalline mother solution and washing liquid and the ammonia collected and carbon dioxide respectively or The leaching device of grog is fed back to, solid then or is obtained product apt after scrubbed drying after mixing, or entrance next stage dissolving, Crystallization, purification subsystem；Described tungsten mineral material includes scheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry；
For this reason, this technique comprises multiple closed cycles, whole non-wastewater discharge.
7. metallurgical technology according to claim 6 is it is characterised in that described transition is included tungsten mineral material, dispensing Levigate, mix homogeneously, to prepare raw material；Roasting is carried out to raw material, to obtain grog.
8. metallurgical technology according to claim 6 is it is characterised in that described weak base is ammonium carbonate, ammonium hydrogen carbonate, ammonia Water, ammonia+co2Gas, their any mixture and/or their any mixture with ammonium tungstate.
9. metallurgical system according to claim 1 it is characterised in that
Raw material preparation facilitiess have raw mineral materials dosage/metering entrance and dosage/metering entrance, raw material fine mill；
Calcining kiln/stove is through feeding measurement device and raw material silo and raw material outlet；
Grog fine mill is through grog storehouse and thick grog outlet；
The entrance of first order purification and impurity removal device is connected with the thick taphole containing wolfram element, at different levels have purification and impurity removal agent entrance with And impurity collector, afterbody has the smart taphole containing wolfram element；And/or
The entrance of crystallization apparatus is connected with the smart taphole containing wolfram element.
10. system according to claim 1 it is characterised in that: leaching device also includes carbon dioxide and is passed through mouth；Leach The equipment for separating liquid from solid of serosity is defecator；Afterbody purification and impurity removal device adds extractor fan；It is molten that crystallization apparatus have essence Liquid evaporative crystallization controller；And/or, the liquid-solid separation device of slurry is with next stage dissolving, crystallization, purification subsystem even Logical.
11. techniques according to claim 6 it is characterised in that: afterbody purification and impurity removal device adds extractor fan； And/or, solid phase is dissolved again and is crystallized, final products higher to obtain purity.
12. techniques according to claim 7 it is characterised in that: grog is carried out crushing, levigate.
13. systems according to claim 9 it is characterised in that: raw material preparation facilitiess are additionally provided with mineralizer metering/dosage and enter Mouthful；And/or, raw material fine mill contains vortex mixer.
CN201410527649.9A 2014-10-09 2014-10-09 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops Active CN104263921B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410527649.9A CN104263921B (en) 2014-10-09 2014-10-09 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410527649.9A CN104263921B (en) 2014-10-09 2014-10-09 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops

Publications (2)

Publication Number Publication Date
CN104263921A CN104263921A (en) 2015-01-07
CN104263921B true CN104263921B (en) 2017-01-18

Family

ID=52155494

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410527649.9A Active CN104263921B (en) 2014-10-09 2014-10-09 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops

Country Status (1)

Country Link
CN (1) CN104263921B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106636681A (en) * 2016-11-23 2017-05-10 江西稀有金属钨业控股集团有限公司 Tungsten-contained raw ore pretreatment system for realizing green metallurgy

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263972B (en) * 2014-10-09 2016-03-16 中南大学 There is the tungsten mineral material metallurgical system of multiple closed loop

Also Published As

Publication number Publication date
CN104263921A (en) 2015-01-07

Similar Documents

Publication Publication Date Title
CN104263973B (en) The method being prepared APT by the many closed loops of tungsten mineral material
CN104232942B (en) A kind of preprocess method of tungsten mineral material
CN106187330A (en) A kind of amorphous silica prepares the method for high-quality solubility in citric acid siliceous fertilizer
CN105271333A (en) Method for preparing monopotassium phosphate and aluminum hydroxide through potassium feldspar
CN104263975B (en) There is the tungsten mineral material metallurgical technology of multiple closed loop
CN110129552A (en) A method of vanadic sulfide material is prepared using containing vanadium leachate
CN101367538A (en) Method for preparing calcium sulphate with sulfate containing bittern and calcium containing bittern
CN104263971B (en) The system of APT is prepared by tungsten mineral material no pollution
CN109108049A (en) Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag
CN104263976B (en) The tungsten mineral material metallurgical technology of omnidistance non-pollution discharge
CN104263972B (en) There is the tungsten mineral material metallurgical system of multiple closed loop
CN105565350B (en) A kind of method that utilization aluminous fly-ash produces aluminum oxide
CN104388670B (en) The tungsten mineral material metallurgical system of omnidistance non-pollution discharge
CN102424409B (en) Method for preparing light magnesium carbonate
CN104263921B (en) System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops
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
CN204162765U (en) The metallurgical system of the tungsten mineral material of omnidistance non-pollution discharge
CN104263974B (en) The method being prepared APT by tungsten mineral material no effuent discharge
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
CN108070717B (en) The adverse current tandem for controlling liquid-solid ratio simultaneously and embathing completion liquid concentration embathes method and system
CN105858729B (en) A kind of system by sulfuric acid treatment wolframite to prepare tungstate solution
CN205838591U (en) A kind of by sulfuric acid treatment wolframite to prepare the system of tungstate solution
CN104263922B (en) The tungsten mineral material metallurgical system of no pollution discharge can be achieved

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