CN104263975A - Metallurgical technology with multiple closed cycles for tungsten mineral raw materials - Google Patents

Metallurgical technology with multiple closed cycles for tungsten mineral raw materials Download PDF

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Publication number
CN104263975A
CN104263975A CN201410528250.2A CN201410528250A CN104263975A CN 104263975 A CN104263975 A CN 104263975A CN 201410528250 A CN201410528250 A CN 201410528250A CN 104263975 A CN104263975 A CN 104263975A
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grog
leaching
raw material
volatile salt
tungsten
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CN201410528250.2A
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CN104263975B (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
童潇依
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Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
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Jiangxi Rare Earth and Rare Metals Tungsten Group Holding Co Ltd
Central South University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a metallurgical technology for tungsten mineral raw materials. The technology comprises the following steps: proportioning the mineral raw materials and ingredients to obtain raw materials; roasting the raw materials to enable the raw materials to be transformed into clinker; using a weak alkali solution to leach the clinker, and recovering solutions fed back from all the links; performing solid-liquid separation on leached slurry, washing leached residues, feeding back washing liquid to a clinker leaching link (a first closed cycle), and feeding back at least part of the leached residues to a raw material preparing link (a second closed cycle) as the ingredients; performing purification and residue-removing on crude solutions; evaporating and crystallizing the purified solutions; returning released gases to the clinker leaching step (a third closed cycle), and feeding back evaporated water to a solid-liquid separation link (a fourth closed cycle) of leaching the slurry; performing the solid-liquid separation on the crystallized slurry, washing a solid phase through water and/or an ammonium salt solution, and drying the washed solid phase to obtain a final product containing W elements; returning crystallized mother liquid to the clinker leaching step (a fifth closed cycle). Therefore, the technology disclosed by the invention comprises the multiple closed cycles, and the situation of zero waste water discharge in the whole process is realized.

Description

There is the tungsten mineral material metallurgical technology of multiple closed loop
Technical field
The present invention relates to a kind of method being prepared APT by tungsten mineral material, belong to Tungsten smelting technical field.
Term " raw material " refers to tungsten mineral material, batching, after proportioning, and is milled to the mixture of certain fineness.
Term " grog " refers to tungsten mineral material, prepare burden through levigate, be mixed into raw material, then after high-temperature roasting the material of gained.
Term " mineralizer " refers to the reaction can accelerated in raw material roasting process between tungsten mineral material and batching or the material reducing maturing temperature.
Background technology
In prior art, the commercial run of preparation APT mainly comprises the steps: by caustic soda or soda leaching tungsten mineral material, obtains coarse sodium tungstate; By solution purification-ion-exchange or solvent extraction transition (or by ion-exchange or solvent extraction removal of impurities and make the transition), obtain pure tungsten acid ammonium solution; Again by evaporative crystallization, obtain APT product.
All there is following essential defect in prior art: all adopts and do not circulate or half circulation technology system, do not realize whole circulation technology.At least there is following technical problem in prior art: must arrange waste water discharge opening, and waste water pollution problem cannot thoroughly be eradicated; Supplies are mostly expendable consumed product, and the excessive use of the leaching agent of leaching process, these supplies corresponding processing step after completion of the reaction directly outer row otherwise to need to use in corresponding acid or alkali and after outer row again, supplies consumption is many, and production cost is high; In waste water, inevitably take part W elements out of, the W elements rate of recovery is low; Facility investment is large, and technical process is long, and productivity is lower, more difficultly realizes continuous seepage.
In such APT preparation process, auxiliary material consumption is comparatively large, and produces a large amount of waste water; Produce a large amount of high bisulfate waste liquors in sodium tungstate solution transformation process, evaporative crystallization mother liquor produces ammonia nitrogen waste water.
If do not have the closed circuit flow process of discharge of wastewater there being the open circuit flow process of discharge of wastewater to become, be not do not have technical possibility, but input even may be greater than profit, for this reason, enterprise has to select discharge, and result causes serious environmental pollution.
Summary of the invention
The object of this invention is to provide a kind of method preparing APT from tungsten mineral material, its flow process is short, solution reusable edible, environmental pollution is almost uprooted, cost is low, be easy to industrialization.
For this reason, according to an aspect of the present invention, provide a kind of method preparing APT from tungsten mineral material, the method comprises the steps:
1) by tungsten mineral material, prepare burden levigate after, mix and prepare raw material;
2) roasting is carried out to raw material, obtain grog, and grog is carried out fragmentation, levigate;
3) with volatile salt, volatile salt-bicarbonate of ammonia, volatile salt-ammonium tungstate, volatile salt-CO 2, volatile salt-ammoniacal liquor-CO 2, volatile salt-ammoniacal liquor, volatile salt-bicarbonate of ammonia-ammonium tungstate, volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2, volatile salt-ammoniacal liquor-ammonium tungstate, volatile salt-ammonium tungstate-CO 2, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2system leaches grog;
4) leaching slurry washs mutually through solid-liquid separation and slag, obtains thick ammonium tungstate solution and leached mud, and part leached mud returns step 1 as batching) carry out raw material configuration, remainder is stored up;
5) thick ammonium tungstate solution purification and impurity removal;
6) after purification, solution adopts evaporative crystallization to separate out APT, obtains ammonia and carbon dioxide simultaneously;
7) solid-liquor separation is carried out to the slurries after crystallization, obtain crystalline mother solution and solid phase, solid phase is through water and/or ammonium salt solution washing, namely APT product is obtained after oven dry, crystalline mother solution and step 6) ammonia that obtains turns back to step 3 together with carbonic acid gas), and (can by bicarbonate of ammonia or ammoniacal liquor and CO at the volatile salt of replenish loss 2some substitute) Posterior circle leaching grog.
Preferably, described tungsten mineral material comprises, sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry;
Preferably, during raw material preparation, the add-on of leached mud presses CaO/WO in raw material 3or (CaO+FeO)/WO 3or (CaO+MnO)/WO 3or (CaO+FeO+MnO)/WO 3molecular ratio is at least 1.0, is preferably 1.5-6.0, is more preferably 3.0-4.0, is more preferably 3.3-3.6; Raw material granularity is not particularly limited, and is preferably not more than 200 μm, is more preferably and is not more than 100 μm, is more preferably and is not more than 40 μm; During raw material roasting, temperature, for being not less than 500 DEG C, being preferably 800-1050 DEG C, being more preferably 850-950 DEG C;
Preferably, in raw material process for preparation, add mineralizer, be preferably Calcium Fluoride (Fluorspan), to accelerate the reaction between tungsten mineral material and batching, significantly reduce maturing temperature;
Preferably, the time of raw material roasting is 0.5-8.0h, is preferably 1.0-3.0h, is more preferably 2.0h; When tungsten mineral material is sheelite, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere;
Preferably, when tungsten mineral material is wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, calcination atmosphere is neutral or reducing atmosphere, is preferably neutral atmosphere; The granularity of grog is not particularly limited, and is preferably not more than 200 μm, is more preferably not more than 74 μm, is more preferably not more than 45 μm;
Preferably, the CO in Leaching Systems 2stove (kiln) gas that a part produces from raw material roasting process or commodity CO 2, the CO that another part produces from ammonium tungstate solution evaporation and crystal process 2;
Preferably, CO 2can pass in leaching process, also can pass into before leaching.
Preferably, leach volatile salt concentration in initial system and be greater than 20g-(NH 4) 2cO 3/ 100g-H 2o, be preferably the concentration of its saturated solution under this system, bicarbonate of ammonia then adds with the form of solution or solid, and the add-on of bicarbonate of ammonia is not particularly limited, and is preferably no less than and makes the calcium in grog be converted into CaCO 31.0 times of aequum (theoretical amount), be more preferably the 1.1-1.4 of theoretical amount doubly, ammonium tungstate concentration is not particularly limited, as long as can guarantee the tungsten ammonium tungstate concentration fully leached in rear gained solution in grog be no more than this system under equilibrium concentration, the add-on of ammoniacal liquor is also not particularly limited, NH in preferred leaching initial system 3mass percentage be 0% ~ 28%, be more preferably 5% ~ 20%, be more preferably 5% ~ 10%; The leaching process of grog carries out in enclosed system, when leaching grog with Ammonium Carbonate system, volatile salt-bicarbonate of ammonia system, volatile salt-ammonia-water systems, volatile salt-bicarbonate of ammonia-ammonium tungstate system, volatile salt-ammoniacal liquor-ammonium tungstate system and volatile salt-ammonium tungstate system, the absolute pressure of reaction system is not particularly limited, with volatile salt-CO 2system, volatile salt-bicarbonate of ammonia-CO 2system, volatile salt-ammoniacal liquor-CO 2system, volatile salt-ammonium tungstate-CO 2system, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2system and volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2when system leaches grog, the absolute pressure that need control reaction system is not less than 1atm, is preferably 2atm;
Preferably, extraction temperature is not less than 5 DEG C, is preferably 10-80 DEG C, is more preferably 20-70 DEG C, is more preferably 30-50 DEG C;
Preferably, extraction time is not particularly limited, as long as can guarantee that in grog, tungsten can fully leach, preferably extraction time is 0.5-8.0h, and more preferably extraction time is 2-5h; Purification and impurity removal process comprises at least one except molybdenum, phosphorus, tin, arsenic, silicon, iron, sodium, potassium, bismuth, antimony, calcium, magnesium process;
According to another aspect of the present invention, provide a kind of system adopting method according to claim 1 to prepare APT, comprising:
1) grinding attachment A, tungsten mineral material, prepares burden after batching metering, and adopt grinding attachment A by levigate for various raw material, mixing, preparation has the raw material of certain fineness and uniformity coefficient;
2) raw material of preparation are added roasting in roasting kiln (stove), obtain grog after cooling by roasting kiln (stove);
3) grinding attachment B, the grog burnt till adopts grinding attachment B levigate;
4) leaching plant, grog leaches in leaching plant;
5) filter plant, leaching slurry adopts filter plant to carry out filtration washing;
6) impurity removing equipment, thick ammonium tungstate solution purification and impurity removal in impurity removing equipment; And
7) crystallizer, ammonium tungstate refined liquid evaporative crystallization in crystallizer.
Preferably, described grinding attachment A is selected from: vibrating mill, ball mill, rod mill, autogenous mill, agitator mill, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc refiner, Raymond mill, micronizer mill.
Preferably, described roasting kiln (stove) comprising: static roasting kiln (stove) and dynamic roasting kiln (stove).
Preferably, described grinding attachment B is selected from: twin rollers, vibrating mill, ball mill, rod mill, autogenous mill, agitator mill, overhang roll pulverizer, tower mill, colloidal mill, centrifugal mill, high pressure disc refiner, Raymond mill, micronizer mill.
Preferably, described leaching plant can be an independent leaching plant, also can 2-4 leaching plant series connection use.
Preferably, described leaching plant can be agitation leach equipment, also can be ball milling leaching plant.
Preferably, described leaching plant can seal, and can bear 4atm pressure.
Preferably, described filter plant is pumping and filtering device, filtering equipment and/or natural filtration groove.
Preferably, described impurity removing equipment is decleaning tank, filter plant and/or subsider.
Preferably, whipping appts is provided with in described decleaning tank.
The present invention is relative to the industrial process of existing APT, and its advantage is:
1) achieve the closed cycle being prepared solution in APT process by tungsten mineral material, thus the problem of environmental pollution caused due to a large amount of discharge of wastewater in APT production process can be eradicated in theory;
2) by tungsten mineral material roasting is made the transition, W elements is changed and is contained in the material easily leached by ammonium carbonate salt solution, achieve the low-temp extraction of tungsten, reduce the energy expenditure in leaching process and cost, meanwhile, leached mud can recycle as the batching in tungsten mineral material transformation process again;
3) adopt the ammonium carbonate salts system leaching tungsten minerals grog of low cost, easily circulation, directly obtain ammonium tungstate solution, eliminate step transition from sodium tungstate solution to ammonium tungstate solution, flow process is simple;
4) due to the recycle of multiple supplies, supplies consumption significantly reduces, and processing charges significantly reduces;
5) simple to operate, be convenient to control, be easy to industrial application.
According to the present invention, with " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" system or " volatile salt-ammoniacal liquor-ammonium tungstate " or " volatile salt-ammoniacal liquor " or " volatile salt " or " volatile salt-bicarbonate of ammonia " or " volatile salt-ammoniacal liquor-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate-CO 2" or " volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2" or " volatile salt-CO 2" or " volatile salt-ammonium tungstate " or " volatile salt-bicarbonate of ammonia-CO 2" as leach liquor non-obvious, this is because: the weakly alkaline system process raw material (or processing efficiency is extremely low) that chemical reactivities such as sheelite, wolframite, Scheelite-Wolframite Mixed Mine and tungsten slurry are not lower.Tungsten smelting industry generally adopts at present strong acid (example hydrochloric acid) or highly basic (as sodium hydroxide) gonosome system and leach tungsten mineral material under high temperature, hyperbaric environment, and " volatile salt-bicarbonate of ammonia-ammonium tungstate ", " volatile salt-ammonium tungstate-CO 2", " volatile salt-ammoniacal liquor-ammonium tungstate ", " volatile salt-ammoniacal liquor ", " volatile salt ", " volatile salt-bicarbonate of ammonia ", " volatile salt-ammoniacal liquor-CO 2", " volatile salt-ammoniacal liquor-ammonium tungstate-CO 2", " volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2", " volatile salt-CO 2", " volatile salt-ammonium tungstate " and " volatile salt-bicarbonate of ammonia-CO 2" system all belongs to weakly alkaline system, have to pass through raw material step transition and could realize leaching.
According to the present invention, select " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate " or " volatile salt-ammoniacal liquor " or " volatile salt " or " volatile salt-bicarbonate of ammonia " or " volatile salt-ammoniacal liquor-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate-CO 2" or " volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2" or " volatile salt-CO 2" or " volatile salt-ammonium tungstate " or " volatile salt-bicarbonate of ammonia-CO 2" system leaches; Leaching Systems material changes into ammonia and carbonic acid gas after crystallisation step; just can replenish Leaching Systems; thus achieve whole recycles of supplies; thoroughly abandon traditional open circuit not circulating system or open circuit half circulating system; eradicated disposal of pollutants, really achieved green metallurgical.
According to the present invention, not only leach liquid-solid higher time the tungsten leaching effect that can obtain, when leaching liquid-solid ratio and being less than 10, in grog, the leaching yield of tungsten does not also decline, WO in gained leach liquor 3concentration still enough suitability for industrialized production.
According to the present invention, adopt " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate " or " volatile salt-ammoniacal liquor " or " volatile salt " or " volatile salt-bicarbonate of ammonia " or " volatile salt-ammoniacal liquor-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate-CO 2" or " volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2" or " volatile salt-CO 2" or " volatile salt-ammonium tungstate " or " volatile salt-bicarbonate of ammonia-CO 2" system system leaching grog, when leaching liquid-solid ratio is 4, good tungsten leaching effect still can be obtained, WO in gained leach liquor 3concentration is higher, is very adapted to suitability for industrialized production.
According to the present invention, adopt close circulation technology, only arrange waste residue relief outlet, no longer need to arrange waste water discharge opening, the pollution problem of discharge of wastewater obtains thorough elimination.
According to the present invention, supplies are no longer expendable consumed products, the leaching agent of leaching process recycles, even if the excessive use of supplies, corresponding processing step also no longer direct outer row after completion of the reaction, no longer need to use corresponding acid or alkali neutralization, therefore, supplies consumption significantly reduces, and production cost significantly reduces.
According to the present invention, achieve circulation metallurgical technology, " waste water " of conventional process systems is blotted to be squeezed only, and thoroughly avoid part W elements to be emitted in vain, therefore, the W elements rate of recovery also improves.
According to the present invention, can realize integrated production, the Working environment in workshop can significantly improve, and facility investment return rate significantly improves, and technical process shortens, and productivity is largely increased, and can realize continuous print automatic production.
According to the present invention, add the pretreatment process of tungsten mineral material, adopt " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate " or " volatile salt-ammoniacal liquor " or " volatile salt " or " volatile salt-bicarbonate of ammonia " or " volatile salt-ammoniacal liquor-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate-CO 2" or " volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2" or " volatile salt-CO 2" or " volatile salt-ammonium tungstate " or " volatile salt-bicarbonate of ammonia-CO 2" system leaches tungsten minerals grog, leaching condition is gentle, and leaching agent is cheap, be easy to get, and supplies reusable edible, can eliminate the discharge of wastewater in production process in theory.
According to the present invention, depart from prior art completely, propose theory and the technique of a kind of preparation APT completely newly, save sodium tungstate solution step transition that can produce a large amount of waste water, directly obtain ammonium tungstate solution, fundamentally eliminate the discharge of waste water in APT production process, and achieve the recycle of supplies and solution.
According to the present invention, technical process is simple, and easy to operate, production cost is low, non-wastewater discharge, and environmental pollution is reduced to minimum level.
Accompanying drawing explanation
Fig. 1 is according to a kind of process flow sheet being prepared APT by tungsten mineral material of the present invention.
Fig. 2 is according to a kind of structural principle schematic diagram being prepared the system of APT by tungsten mineral material of the present invention.
Embodiment
Below in conjunction with accompanying drawing 1-2, embodiments of the invention are described further.
As shown in Figure 1, the metallurgical technology containing tungsten mineral material of the present invention comprises the following steps:
Make to become raw material 101 containing W raw mineral materials 100 and batching MN (M represents positive ion, and N represents negative ion) proportioning;
Roasting raw material 200, there is chemical reaction in short its, to make the transition as containing M and the grog containing W ion, thus makes grog obtain high chemical reactivity;
Weak base AN (A is positive ion) solution is adopted to leach (the excessive highly basic of thorough abandoning tradition leaches prejudice) grog, 300 are leached to make grog, and in circulating reaction, reclaim the solution that each link feeds back, and according to the weak base AN of actual needs replenish loss;
Solid-liquid separation 400 is carried out to leaching slurry, obtain containing A and contain the thick solution of W ion and the leached mud containing M, slag is washed mutually, washings feeds back to grog and leaches link (I closed loop), according to actual needs, be taken to small part leached mud and feed back to raw material configuration link (II closed loop) as batching, if leached mud has remainder, then store up;
At least first class purification removal of impurities 500 (last step can add extractor fan) is carried out to containing A with containing the thick solution of W ion;
Evaporative crystallization 600 is carried out, to separate out the intermediates containing W element to the solution after purification; Meanwhile, the gas discharging the gas relevant to element A and be correlated with N element is back to the step (III closed loop) leaching grog 300, and the water evaporated feeds back to the solid-liquid separation link (IV closed loop) of leaching slurry 300;
Solid-liquor separation 700 is carried out to the slurries after crystallization, to obtain crystalline mother solution and solid phase, solid phase, through water and/or ammonium salt solution washing, namely obtains the finished product (preferably again dissolving and crystallization solid phase, to obtain the higher the finished product of purity) containing W element after oven dry; And crystalline mother solution is also back to the step (V closed loop) leaching grog,
For this reason, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
As shown in Figure 2, the metallurgical system of tungsten mineral material of the present invention comprises successively:
Raw material preparation facilities 10, it has raw mineral materials entrance 11 and ingredient inlets 12 (is preferably also provided with mineralizer entrance 13; Preferably, each entrance is also provided with gauger/dosimeter), raw material fine mill (containing vortex mixer) 14, raw material outlet 15 and leached mud receiving port 16;
Roasting kiln (stove) 20, it exports 15 through feeding measurement device with raw material silo and raw material and is communicated with, and has heating unit, attemperator (preferably also comprising refrigerating unit 21), atmosphere (oxidizing atmosphere, reducing atmosphere, neutral atmosphere) control device and thick grog outlet 22;
Grog fine mill 30, it exports 22 through grog storehouse with thick grog and is communicated with, and has ore grinding device and thin grog outlet 31;
Leaching device 40, itself and thin grog outlet 31, there is leaching agent entrance 41, leaching slurry outlet 42, feedback gas recovery port 43, slurry separating, washing liquid recovery port 44, slag phase washings recovery port 45, crystal seed entrance 46 (preferably, also comprise carbonic acid gas and pass into mouth 47);
The equipment for separating liquid from solid (preferred filtration unit) of leaching slurry, itself and leaching slurry export 42 and are communicated with, have the receiving port 55 of the filtration washing device 50 of the leached mud containing batching element, thick taphole 51 containing W elements, leached mud feedback port 52, outlet 53 to residue leached mud heap warehousing, the outlet 54 of washing lotion feedback, evaporative crystallization water of condensation, this equipment for separating liquid from solid is communicated with the crystal seed entrance 46 of leaching device 40 in the way of leached mud receiving port 16 feeding back to raw material preparation facilities 10;
At least one-level purification and impurity removal device 60, the entrance 61 of the first step is communicated with the thick taphole 51 containing W elements, at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole 62 (preferably, last step adds extractor fan) containing W elements;
Crystallization apparatus 70, its entrance 71 is communicated with the thick taphole 62 containing W elements, has slurry outlet 72, feeds back to gas feedback mouth 73 and the condensation-water drain 74 (preferably having the thick solution evaporation cerium sulphate crystal device of tungsten product) of leaching device;
The liquid-solid separation device 80 of slurry, itself and slurry export 72 and are communicated with, there is the outlet 83 (preferably, dissolve with next stage, crystallization, purification subsystem be communicated with) that crystalline mother solution is back to the outlet 81 of leaching device 40, solid phase wash water entrance 82 and tungsten product.
According to the present invention, by tungsten mineral material and a certain amount of calcareous material and mineralizer after levigate, mix acquisition raw material; During raw material preparation, the add-on of calcareous material presses CaO/WO in raw material 3or (CaO+FeO)/WO 3or (CaO+MnO)/WO 3or (CaO+FeO+MnO)/WO 3molecular ratio is at least 1.0, is preferably 1.5-6.0, is more preferably 3.0-4.0, is more preferably 3.3-3.6;
During raw material preparation, the mineralizer allocated into is fluorochemical, is preferably Calcium Fluoride (Fluorspan), and the add-on of Calcium Fluoride (Fluorspan) is the 0.5-7% (mass percent) of dry tungsten mineral material amount, preferred 1-3% (mass percent); Raw material granularity is not particularly limited, and is preferably not more than 200 μm, is more preferably and is not more than 100 μm, is more preferably and is not more than 40 μm; Raw material maturing temperature is not less than 500 DEG C, and preferably raw material maturing temperature is 800 ~ 1050 DEG C, is more preferably 850 ~ 950 DEG C; Roasting time is not particularly limited, and temperature is low, needs to extend roasting time, is fully converted into Ca for making the tungsten in raw material 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6, preferably roasting time is 0.5-8.0h, is more preferably 1.0 ~ 3.0h, more preferably roasting 2.0h at 850 ~ 950 DEG C.
For sheelite raw material, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere; For wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry raw material, calcination atmosphere is neutral or reducing atmosphere, is preferably neutral atmosphere.
The present invention will containing Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6mixture join in ammonium salt solution system, leach in confined conditions, after having leached, leaching slurry, through separating, washing, obtains ammonium tungstate solution.
Preferably, described Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6can be the pure compound of synthetic, also can be tungsten mineral material obtain after treatment containing Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6mixture (grog); Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6the granularity of mixture be not more than 200 μm, be preferably less than 45 μm; Described ammonium salt solution system can be volatile salt-bicarbonate of ammonia-ammonium tungstate system, volatile salt-ammonium tungstate-CO 2system, volatile salt-ammoniacal liquor-ammonium tungstate system, volatile salt-ammonia-water systems, Ammonium Carbonate system, volatile salt-bicarbonate of ammonia system, volatile salt-ammoniacal liquor-CO 2system, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2system, volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2system, volatile salt-CO 2system, volatile salt-ammonium tungstate system, also can be volatile salt-bicarbonate of ammonia-CO 2system.
Preferably, Ca is leached by Ammonium Carbonate system, volatile salt-bicarbonate of ammonia system, volatile salt-ammonia-water systems, volatile salt-bicarbonate of ammonia-ammonium tungstate system, volatile salt-ammoniacal liquor-ammonium tungstate system and volatile salt-ammonium tungstate system 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6time, the absolute pressure of Leaching Systems is not particularly limited; With volatile salt-CO 2system, volatile salt-bicarbonate of ammonia-CO 2system, volatile salt-ammoniacal liquor-CO 2system, volatile salt-ammonium tungstate-CO 2system, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2system and volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2system leaches Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6time, in leaching process, pass into CO 2, the absolute pressure controlling Leaching Systems is not less than 1atm, is preferably 1.5-2.5atm, is more preferably 2atm.
Preferably, Leaching Systems volatile salt concentration is greater than 20g-(NH 4) 2cO 3/ 100g-H 2o, is preferably saturated sal volatile.
Preferably, described volatile salt-ammonium tungstate-bicarbonate of ammonia, volatile salt-ammonium tungstate-CO 2, volatile salt-ammoniacal liquor-ammonium tungstate, volatile salt-ammonium tungstate, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2with volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2in solution system, ammonium tungstate concentration is also not particularly limited, as long as meet Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6in tungsten fully leach after, in gained solution, ammonium tungstate concentration is no more than its solubleness in this system.
Preferably, described volatile salt-bicarbonate of ammonia, volatile salt-ammonium tungstate-bicarbonate of ammonia, volatile salt-bicarbonate of ammonia-CO 2with volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2solution system, bicarbonate of ammonia add-on is not particularly limited, and is preferably no less than 1.0 times of theoretical amount, is more preferably 1.1 ~ 1.4 times of theoretical amount.
Preferably, described volatile salt-ammoniacal liquor-ammonium tungstate, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2, volatile salt-ammoniacal liquor and volatile salt-ammoniacal liquor-CO 2in solution system, the add-on of ammoniacal liquor is also not particularly limited, NH in preferred leaching initial system 3mass percentage be 0% ~ 28%, be more preferably 5% ~ 20%, be more preferably 5% ~ 10%.
Preferably, control Leaching Systems pH and be not less than 8.0.Extraction temperature is not less than 5 DEG C, is preferably 10-80 DEG C, is more preferably 20-70 DEG C, is more preferably 30-50 DEG C; Extraction time is not particularly limited, as long as can make Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6in tungsten fully leach, be preferably 0.5-8.0h, more preferably extraction time is 2.0-5.0h.
Preferably, the initial liquid-solid ratio of Leaching Systems is not less than 1:1mL/g, is preferably 10:1-4:1mL/g.
Preferably, the mode can fed in raw material by multistage, reduces the final liquid-solid ratio of Leaching Systems, and feed in raw material preferably by two sections, the liquid-solid ratio controlling final Leaching Systems is 3:1 ~ 4:1mL/g.
Preferably, described sal volatile also can by ammonium bicarbonate soln and ammoniacal liquor or ammoniacal liquor and CO 2some substitute.
As (the NH in solution 4) 2wO 4when concentration is higher, especially there is a large amount of NH 4oH deposits in case, (NH 4) 2wO 4the high reactivity CaCO that can generate with leaching process 3there is secondary reaction, generate the CaWO being difficult to be leached by ammonium carbonate salt solution 4, cause tungsten loss.Principal reaction may be:
Ca(OH) 2+(NH 4) 2WO 4＝CaWO 4+2NH 4OH (2)
Reaction (2) is more easily carried out, and generally reacts (1) and be difficult to carry out, but at Ca 3wO 6leaching process in newborn CaCO 3active high, reaction (1) is then likely carried out, and carries out NH along with leaching process 4oH and (NH 4) 2wO 4concentration constantly increase, reaction (1) and react (2) strengthened, finally cause (NH 4) 2wO 4when concentration is higher, the loss of tungsten increases.Therefore, in airtight Leaching Systems, CO is passed into 2, the NH in rapid neutralization solution 4oH, makes reaction (1) be suppressed; Simultaneously by adding CaCO 3crystal seed, makes newborn CaCO 3grow up rapidly at seed surface, reduce its activity, the carrying out of further inhibited reaction (1).Thus be expected to (the NH simultaneously obtaining high density 4) 2wO 4solution and high tungsten leaching yield.
In addition, in enclosed system, CO is passed into 2, can also CO be improved 2utilization ratio.
According to embodiments of the invention, by thick ammonium tungstate solution purification and impurity removal, the method of purification and impurity removal is not particularly limited, if after purification in solution the content of the impurity such as P, As, Si, Mo, S, Sn, Sb, K, Na, Ca, Mg meet the qualified APT quality product of preparation and require.According to one embodiment of present invention, the impurity in precipitator method removing ammonium tungstate solution can be adopted, prepare ammonium tungstate refined liquid thus.
According to embodiments of the invention, can evaporative crystallization legal system be adopted to get APT ammonium tungstate refined liquid, the condition of evaporative crystallization be not particularly limited.According to one embodiment of present invention, at 95 DEG C, ammonium tungstate solution being evaporated to pH is 6.5, and after solid-liquid separation and product washing, the APT product purity of acquisition meets 0 grade of product standard in GB/T 10116-2007.
Embodiment 1: by CaO/WO 3molecular ratio is 3.3, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) (main component is CaCO with grog leached mud 3) and mineralizer Calcium Fluoride (Fluorspan) carry out levigate, mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 5.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, in stoving oven, under air atmosphere, 800 DEG C of roasting 2.0h, obtain grog.After clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm.Take 5.0g levigate after grog join band ventilation and mechanical stirring device reactor in, add 50g-(NH simultaneously 4) 2cO 3/ 100g-H 2the sal volatile 50mL of O is also airtight, then passes into CO 2gas, the absolute pressure controlling reaction system is 2atm, at 80 DEG C, react 5h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.In grog, the leaching yield of tungsten is 97.15%.
Embodiment 2: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 63.75%, Fe mass percentage is 5.90%) with 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.After clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm.Take 20.0g grog to join in the reactor of band ventilation and mechanical stirring device, add 35g-(NH simultaneously 4) 2cO 3/ 100g-H 2the sal volatile 100mL of O is also airtight, then passes into CO 2gas, the absolute pressure controlling reaction system is 2atm, at 70 DEG C, react 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.In grog, the leaching yield of tungsten is 87.17%.
Embodiment 3: by (CaO+FeO+MnO)/WO 3molecular ratio is 3.4, by certain wolframite (WO 3mass percentage is 62.40%, Fe mass percentage be 14.08%, Mn mass percentage is 2.25%) with grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate, mix after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, in pipe type calciner, under neutral atmosphere, at 800 DEG C, roasting 6.0h, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.0 times of theoretical amount; Grog is put into leaching plant, at 80 DEG C, reacts 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.The leaching yield 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, obtain ammonia and carbon dioxide simultaneously, solid-liquor separation is carried out to the slurries after crystallization, obtain crystalline mother solution and solid phase, namely solid phase obtains APT product after water washing, and APT product reaches country's 0 grade of product standard-required; The ammonia obtained turns back to leaching plant together with carbonic acid gas, and in replenish loss volatile saltposterior circle leaches grog.
Embodiment 4: by (CaO+FeO)/WO 3molecular ratio is 3.0, by certain wolframite (WO 3mass percentage is 42.17%, Fe mass percentage is 11.34%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in stoving oven, under week reduction atmosphere, 850 DEG C of roasting 5.0h, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; Leaching plant selects ball milling digester, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.1 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.78%.Then, similar embodiment 3 but supplement bicarbonate of ammonia and ammoniacal liquor.
Embodiment 5: by CaO/WO 3molecular ratio is 6.0, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%), grog leached mud and Calcium Fluoride (Fluorspan) obtains raw material after carrying out levigate mixing, the add-on of Calcium Fluoride (Fluorspan) is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at stoving oven neutral atmosphere 870 DEG C, obtain grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5%) and airtight, then pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 2atm, at 30 DEG C, react 5h.After reaction terminates, leach ore pulp pure water filter cake three times.The leaching yield of tungsten is 98.51%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2 .
Embodiment 6: by (CaO+FeO)/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 7h at stoving oven neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with centrifugal mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 35g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 9h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.99%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 7: by CaO/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤40 μm, then, roasting 5h at stoving oven neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with planet mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in unsaturated carbonate ammonium and containing 20g/LWO 3ammonium tungstate mixing solutions, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage is 9.5%) and airtight, and then, pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 3atm, at 20 DEG C, react 6h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 99.01%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 8: by CaO/WO 3molecular ratio is 8, by certain tungsten slurry (WO 3mass percentage is 16.22%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤40 μm, then, roasting 3h at stoving oven reducing atmosphere 940 DEG C, obtains grog, after clinker cooling to room temperature; The leaching vat that leaching plant select tape stirs, built-in unsaturated carbonate ammonium and containing 120g/L WO 3ammonium tungstate mixing solutions, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 10%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp, with pure water filter cake three times.The leaching yield of tungsten is 97.51%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 9: by (CaO+FeO)/WO 3molecular ratio is 1.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 1.5h at stoving oven neutral atmosphere 965 DEG C, obtains grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 67g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 18 DEG C, reacts 6.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 29.30%.Embodiment 10: by (CaO+FeO)/WO 3molecular ratio is 1.2, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then roasting 3h at stoving oven neutral atmosphere 500 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 50g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.25 times of theoretical amount; Grog is put into leaching plant, at 28 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 9.76%.
Embodiment 11: by CaO/WO 3molecular ratio is 9, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤200 μm, then, roasting 4h at stoving oven neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤40 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.1 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 10%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 89.05%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 12: by CaO/WO 3molecular ratio is 2.3, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤100 μm, then, roasting 2.5h at stoving oven neutral atmosphere 845 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5.9%) and airtight, then, pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 2.5atm, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 73.65%.Then, similar embodiment 3 but supplement ammoniacal liquor and bicarbonate of ammonia.
Embodiment 13: by CaO/WO 3molecular ratio is 3.6, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 1h at stoving oven neutral atmosphere 870 DEG C, obtains grog, after clinker cooling to room temperature, levigate with micronizer mill, grog granularity≤74 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 20%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.15%.Then, similar embodiment 3 but supplement bicarbonate of ammonia.
Embodiment 14: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤50 μm, then, roasting 2h at stoving oven neutral atmosphere 920 DEG C, obtain grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 2h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 98.22%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 15: by (CaO+FeO)/WO 3molecular ratio is 3.4, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 2h at stoving oven neutral atmosphere 960 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤200 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 98.35%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 16: by (CaO+FeO)/WO 3molecular ratio is 4.1, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤61 μm, then, roasting 2h at stoving oven oxidizing atmosphere 970 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 55 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.31%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 17: by CaO/WO 3molecular ratio is 6.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤53 μm, then, roasting 0.5h at stoving oven neutral atmosphere 990 DEG C, obtains grog, after clinker cooling to room temperature, levigate with planet mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 62 DEG C, reacts 2h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 96.78%.Then, similar embodiment 3 but supplement volatile salt and ammoniacal liquor, APT product reaches country's 0 grade of product standard-required.
Embodiment 18: by (CaO+FeO)/WO 3molecular ratio is 4.7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤74 μm, then, roasting 2h at stoving oven neutral atmosphere 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with high pressure disc refiner, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.6 times of theoretical amount; Grog is put into leaching plant, at 75 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.01%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 19: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 8.2%) and airtight, then pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 3atm, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 20: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 1h at stoving oven neutral atmosphere 860 DEG C, obtain grog, after clinker cooling to room temperature, levigate with tower mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in unsaturated carbonate ammonium and containing 60g/L WO 3ammonium tungstate mixing solutions; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 15%) and airtight, then pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 1.2atm, at 35 DEG C, react 6h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.03%.Then, similar embodiment 3 but supplement ammoniacal liquor, CO 2and volatile salt.
Embodiment 21: by CaO/WO 3molecular ratio is 2.0, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤36 μm, then, roasting 1h at stoving oven reducing atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 10.0%) and airtight, then pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 1.5atm, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 42.75%.Then, similar embodiment 3 but supplement bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 22: by CaO/WO 3molecular ratio is 1.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor (making the mass percentage of NH3 in infusion solution be 7.4%) and airtight simultaneously, then, pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 1.9atm, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 38.35%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 23: by (CaO+FeO)/WO 3molecular ratio is 1.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤33 μm, then, roasting 5h at stoving oven neutral atmosphere 965 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 80g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 20 DEG C, reacts 6.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 22.96%.Then, similar embodiment 3.
Embodiment 24: by (CaO+FeO)/WO 3molecular ratio is 2.9, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 3h at stoving oven neutral atmosphere 850 DEG C, obtain grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤74 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 80g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.25 times of theoretical amount; Grog is put into leaching plant, at 28 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 95.71%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia and ammoniacal liquor.
Embodiment 25: by CaO/WO 3molecular ratio is 4, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤28 μm, then, roasting 4h at stoving oven oxidizing atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 20%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.35%.Then, similar embodiment 3 but supplement ammoniacal liquor.
Embodiment 26: by CaO/WO 3molecular ratio is 2.3, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤41 μm, then, roasting 2.5h at stoving oven neutral atmosphere 845 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤83 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor (making the mass percentage of NH3 in infusion solution be 9.8%) and airtight simultaneously, at 37 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 68.65%.Then, similar embodiment 3 but supplement volatile salt, ammoniacal liquor and CO 2.
Embodiment 27: by (CaO+FeO)/WO 3molecular ratio is 4.8, by certain sheelite (WO 3mass percentage is 52.27%, Fe mass percentage is 5.86%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤61 μm, then, roasting 1h at stoving oven neutral atmosphere 870 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 32 DEG C, reacts 8.0h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.10%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 28: by (CaO+FeO+MnO)/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with rhodochrosite and Wingdale after obtain raw material, raw material granularity≤14 μm, then, roasting 2h at stoving oven neutral atmosphere 920 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 43 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 98.42%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 29: by (CaO+FeO)/WO 3molecular ratio is 4.9, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤42 μm, then, roasting 2h at stoving oven neutral atmosphere 960 DEG C, obtains grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.35%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 30: by (CaO+MnO)/WO 3molecular ratio is 4.6, by certain sheelite (WO 3mass percentage is 60.94%) carry out levigate mixing with rhodochrosite and grog leached mud after obtain raw material, raw material granularity≤44 μm, then, roasting 1.5h at stoving oven neutral atmosphere 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 4 times.The leaching yield of tungsten is 97.99%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 31: by CaO/WO 3molecular ratio is 4.3, by certain sheelite (WO 3mass percentage is 60.94%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤48 μm, then, roasting 2h at stoving oven neutral atmosphere 970 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 55 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, use pure water filter cake.The leaching yield of tungsten is 97.74%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 32: by (CaO+FeO)/WO 3molecular ratio is 4.9, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤38 μm, then, roasting 1h at stoving oven oxidizing atmosphere 990 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 62 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 97.78%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 33: by CaO/WO 3molecular ratio is 5.1, by certain sheelite (WO 3mass percentage is 60.94%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤63 μm, then, roasting 2h at stoving oven neutral atmosphere 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 75 DEG C, reacts 0.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.51%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 34: by (CaO+MnO)/WO 3molecular ratio is 5.1, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with rhodochrosite and grog leached mud after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 6.0% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5.0%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.15%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 35: by (CaO+MnO)/WO 3molecular ratio is 5.1, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with rhodochrosite and grog leached mud after obtain raw material, raw material granularity≤36 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtains grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5.0%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 86.23%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 36: by CaO/WO 3molecular ratio is 2.5, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤37 μm, then, roasting 1h at stoving oven reducing atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤53 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.15 times of theoretical amount; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 4.1%) and airtight, then, pass into carbon dioxide, the absolute pressure controlling Leaching Systems is 1.3atm, at 32 DEG C, react 9h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 74.75%.Then, similar embodiment 3 but supplement bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 37: by CaO/WO 3molecular ratio is 2.2, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with Wingdale carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤24 μm, then, roasting 3h at stoving oven reducing atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, at 32 DEG C, reacts 8.0h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 55.45%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 38: by (CaO+FeO)/WO 3molecular ratio is 10, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with spathic iron ore and grog leached mud after obtain raw material, raw material granularity≤38 μm, then, roasting 1h at stoving oven neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 58g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 9h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.93%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 39: by CaO/WO 3molecular ratio is 5.1, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.0% (mass percent) of dry tungsten mineral material amount, raw material granularity≤33 μm, then, roasting 8h at stoving oven neutral atmosphere 895 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.9 times of theoretical amount; Grog is put into leaching plant, at 20 DEG C, reacts 6h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 95.01%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 40: by CaO/WO 3molecular ratio is 3.9, by certain tungsten slurry (WO 3mass percentage is 16.22%) with Wingdale carry out levigate mixing after obtain raw material, raw material granularity≤40 μm, then, roasting 3h at stoving oven reducing atmosphere 940 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 12%) and airtight, at 50 DEG C, react 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 92.31%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 41: by (CaO+FeO)/WO 3molecular ratio is 6.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with Wingdale carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 1.5h at stoving oven neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 67g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 10 DEG C, reacts 20.0h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 91.96%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 42: by (CaO+FeO)/WO 3molecular ratio is 3.6, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤25 μm, then, roasting 3h at stoving oven neutral atmosphere 850 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 70g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.76%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 43: by CaO/WO 3molecular ratio is 10, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤28 μm, then, roasting 4h at stoving oven neutral atmosphere 845 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤74 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 28%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.01%.Then, similar embodiment 3 but supplement volatile salt, ammoniacal liquor and CO 2.
Embodiment 44: by CaO/WO 3molecular ratio is 3.5, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 5.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 10h at stoving oven neutral atmosphere 845 DEG C, obtain grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤150 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 7.5%) and airtight, at 27 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.49%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 45: by CaO/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 6h at stoving oven neutral atmosphere 1050 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 9.1%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.15%.Then, similar embodiment 3 but supplement bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 46: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at stoving oven neutral atmosphere 995 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.22%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 47: by (CaO+FeO)/WO 3molecular ratio is 5.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at stoving oven reducing atmosphere 960 DEG C, obtain grog, after clinker cooling to room temperature, levigate with micronizer mill, grog granularity≤20 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 98.16%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 48: by (CaO+FeO)/WO 3molecular ratio is 4.2, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 3.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at stoving oven neutral atmosphere 850 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake 4 times.The leaching yield of tungsten is 98.33%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 49: by (CaO+FeO)/WO 3molecular ratio is 4.1, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤53 μm, then, roasting 8h at stoving oven neutral atmosphere 930 DEG C, obtains grog, after clinker cooling to room temperature, levigate with overhang roll pulverizer, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.1 times of theoretical amount; Grog is put into leaching plant, at 25 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 94.22%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 50: by CaO/WO 3molecular ratio is 5.6, by certain sheelite (WO 3mass percentage is 60.94%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤53 μm, then, roasting 1h at stoving oven neutral atmosphere 910 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 62 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 98.78%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 51: by (CaO+FeO)/WO 3molecular ratio is 4.7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤74 μm, then, roasting 2h at stoving oven neutral atmosphere 900 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.6 times of theoretical amount; Grog is put into leaching plant, at 75 DEG C, reacts 1.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 95.01%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 52: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 3.3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 8.0%) and airtight, at 50 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 53: by CaO/WO 3molecular ratio is 4.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤40 μm, then, roasting 1h at stoving oven neutral atmosphere 810 DEG C, obtain grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5.5%) and airtight, at 45 DEG C, react 6h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.63%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 54: by CaO/WO 3molecular ratio is 3.0, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤96 μm, then, roasting 1h at stoving oven reducing atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor (making the mass percentage of NH3 in infusion solution be 3.5%) and airtight simultaneously, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.75%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 55: by CaO/WO 3molecular ratio is 12, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 5h at stoving oven neutral atmosphere 750 DEG C, obtain grog, after clinker cooling to room temperature, levigate with twin rollers, grog granularity≤100 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 32 DEG C, reacts 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 86.35%.
Embodiment 56: by (CaO+FeO)/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with Wingdale carry out levigate mixing after obtain raw material, raw material granularity≤106 μm, then, roasting 7h at stoving oven neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 35g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 9h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 95.99%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 57: by CaO/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 5h at stoving oven neutral atmosphere 1200 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 20 DEG C, reacts 6h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 78.01%.
Embodiment 58: by CaO/WO 3molecular ratio is 8, by certain tungsten slurry (WO 3mass percentage is 16.22%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤96 μm, then, roasting 3h at stoving oven reducing atmosphere 1400 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 6%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 81.51%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 59: by (CaO+FeO)/WO 3molecular ratio is 3.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 8h at stoving oven neutral atmosphere 965 DEG C, obtains grog, after clinker cooling to room temperature, levigate with centrifugal mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 20g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 18 DEG C, reacts 6.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 92.96%.Then, similar embodiment 3.
Embodiment 60: by (CaO+FeO)/WO 3molecular ratio is 3.2, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 3h at stoving oven neutral atmosphere 850 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.25 times of theoretical amount; Grog is put into leaching plant, at 28 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.76%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 61: by CaO/WO 3molecular ratio is 9, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at stoving oven neutral atmosphere 950 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤96 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 5.9%) and airtight, at 47 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.15%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 62: by CaO/WO 3molecular ratio is 3.2, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 5h at stoving oven neutral atmosphere 845 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in sal volatile, volatile salt concentration is 40g-(NH 4) 2cO 3/ 100g-H 2o; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 4%) and airtight, at 45 DEG C, react 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.65%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 63: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤120 μm, then, roasting 3h at stoving oven neutral atmosphere 870 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in sal volatile, volatile salt concentration is 45g-(NH 4) 2cO 3/ 100g-H 2o; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 7.9%) and airtight, at 5 DEG C, react 15h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 93.15%.Then similar embodiment 3 but supplement volatile salt, ammoniacal liquor and CO 2.
Embodiment 64: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 5.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 4h at stoving oven neutral atmosphere 750 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.22%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 65: by (CaO+FeO)/WO 3molecular ratio is 3.4, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 3% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 15h at stoving oven neutral atmosphere 760 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.35%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 66: by (CaO+FeO)/WO 3molecular ratio is 4.2, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 8h at stoving oven neutral atmosphere 980 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 4 times of theoretical amount; Grog is put into leaching plant, at 50 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 4 times.The leaching yield of tungsten is 96.33%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 67: by (CaO+FeO)/WO 3molecular ratio is 4.1, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with Wingdale and fluorite after obtain raw material, the add-on of fluorite is 6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤48 μm, then, roasting 2h at stoving oven neutral atmosphere 970 DEG C, obtain grog, after clinker cooling to room temperature, levigate with agitator mill, grog granularity≤40 μm; Leaching plant selects agitation leach device, and built-in sal volatile, volatile salt concentration is 25g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.4 times of theoretical amount; Grog is put into leaching plant, at 80 DEG C, reacts 0.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 96.36%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 68: by (CaO+FeO)/WO 3molecular ratio is 6.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤53 μm, then, roasting 8h at stoving oven neutral atmosphere 990 DEG C, obtains grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 3 times of theoretical amount; Grog is put into leaching plant, at 62 DEG C, reacts 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 97.70%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 69: by (CaO+FeO)/WO 3molecular ratio is 4.7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with grog leached mud and fluorite after obtain raw material, the add-on of fluorite is 4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at stoving oven neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤40 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.6 times of theoretical amount; Grog is put into leaching plant, at 75 DEG C, reacts 3.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 97.01%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 70: by CaO/WO 3molecular ratio is 3.2, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤36 μm, then, roasting 1h at stoving oven neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 6.7%) and airtight, at 90 DEG C, react 0.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 93.15%.Then similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 71: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 3.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤90 μm, then, roasting 1h at stoving oven neutral atmosphere 860 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.1 times of theoretical amount; Grog is put into leaching plant, at 45 DEG C, reacts 6h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.09%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 72: by CaO/WO 3molecular ratio is 3.1, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.8% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at stoving oven reducing atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 7.5%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.75%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 73: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.7% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 9h at stoving oven neutral atmosphere 880 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 8.6%) and airtight, at 32 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.65%.Then similar embodiment 3 but supplement volatile salt, ammoniacal liquor and CO 2.
Embodiment 74: by CaO/WO 3molecular ratio is 3.7, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, in stoving oven, under air atmosphere, 800 DEG C of roasting 2.0h, obtain grog.After clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm.Take 25.0g levigate after grog join band ventilation and mechanical stirring device reactor in, add 60g-(NH simultaneously 4) 2cO 3/ 100g-H 2the sal volatile 100mL of O is also airtight, then, passes into CO 2gas, the absolute pressure controlling reaction system is 2atm, at 80 DEG C, react 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.In grog, the leaching yield of tungsten is 97.25%.
Embodiment 75: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 63.75%, Fe mass percentage is 5.90%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) 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.After clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm.Take 30.0g levigate after grog join band ventilation and mechanical stirring device reactor in, add 45g-(NH simultaneously 4) 2cO 3/ 100g-H 2the sal volatile 100mL of O is also airtight, then passes into CO 2gas, the absolute pressure controlling reaction system is 2atm, at 70 DEG C, react 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.In grog, the leaching yield of tungsten is 95.17%.
Embodiment 76: by (CaO+FeO)/WO 3molecular ratio is 3.8, by certain wolframite (WO 3mass percentage is 60.40%, Fe mass percentage is 15.08%) with grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate, mix after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) 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, levigate with rod mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 80 DEG C, reacts 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.13%.Then, the volatile salt of similar embodiment 3 replenish loss.
Embodiment 77: by (CaO+FeO)/WO 3molecular ratio is 3.5, by certain wolframite (WO 3mass percentage is 42.17%, Fe mass percentage is 11.34%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.9% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm.Then, in stoving oven, under week reduction atmosphere, 950 DEG C of roasting 5.0h, obtain grog, after clinker cooling to room temperature, levigate with Ball-stirring mill, grog granularity≤40 μm; Leaching plant selects ball milling digester, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.1 times of theoretical amount; Grog is put into leaching plant, at 75 DEG C, reacts 4h.After reaction terminates, leach ore pulp and adopt vacuum filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.78%.Then, similar embodiment 3 but supplement bicarbonate of ammonia.
Embodiment 78: by CaO/WO 3molecular ratio is 6.0, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 2.4% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then roasting 4h at stoving oven neutral atmosphere 870 DEG C, obtains grog, after clinker cooling to room temperature, levigate by planetary mills, grog granularity≤74 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 6.5%) and airtight, at 30 DEG C, react 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.09%.Then similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 79: by (CaO+FeO)/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤25 μm, then, roasting 7h at stoving oven neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibrating mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 60g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 9h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.03%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 80: by CaO/WO 3molecular ratio is 3.0, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 3.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 5h at stoving oven neutral atmosphere 950 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 10.0%) and airtight, the absolute pressure controlling Leaching Systems is 1.0atm, at 20 DEG C, react 12h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 96.20%.Then, similar embodiment 3 but supplement bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 81: by CaO/WO 3molecular ratio is 8, by certain tungsten slurry (WO 3mass percentage is 16.22%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 3h at stoving oven reducing atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 6.3%) and airtight, at 35 DEG C, react 15h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 91.51%.Then, ammoniacal liquor and CO is supplemented 2.
Embodiment 82: by (CaO+FeO)/WO 3molecular ratio is 3.6, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1.5h at stoving oven neutral atmosphere 965 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤60 μm; Leaching plant selects ball milling leacher, and built-in volatile salt-ammonium tungstate mixing solutions, volatile salt concentration is 45g-(NH 4) 2cO 3/ 100g-H 2o, WO in solution 3concentration is 40g/L, and adds bicarbonate of ammonia according to 2 times of theoretical amount; Grog is put into leaching plant, at 18 DEG C, reacts 6.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 97.96%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 83: by (CaO+FeO)/WO 3molecular ratio is 3.3, by certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%), raw material are obtained after carrying out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan), the add-on of Calcium Fluoride (Fluorspan) is 2.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then roasting 3h at stoving oven neutral atmosphere 850 DEG C, obtain grog, after clinker cooling to room temperature, levigate with rod mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, and built-in sal volatile, volatile salt concentration is 40g-(NH 4) 2cO 3/ 100g-H 2o, and add bicarbonate of ammonia according to 1.25 times of theoretical amount; Grog is put into leaching plant, at 42 DEG C, reacts 20h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.76%.Then, similar embodiment 3 but supplement volatile salt and bicarbonate of ammonia, APT product reaches country's 0 grade of product standard-required.
Embodiment 84: by CaO/WO 3molecular ratio is 9, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.55% (mass percent) of dry tungsten mineral material amount, raw material granularity≤30 μm, then, roasting 4h at stoving oven neutral atmosphere 950 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in unsaturated carbonate ammonium and containing 60g/L WO 3ammonium tungstate mixing solutions; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 9.1%) and airtight, at 37 DEG C, react 4.5h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.72%.Then similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 85: by CaO/WO 3molecular ratio is 2.7, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤45 μm, then, roasting 2.5h at stoving oven neutral atmosphere 845 DEG C, obtains grog, after clinker cooling to room temperature, levigate with overhang roll pulverizer, grog granularity≤74 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution, and add bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 45 DEG C, reacts 4.5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 81.65%.Then similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 86: by CaO/WO 3molecular ratio is 3.8, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 1.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 1h at stoving oven neutral atmosphere 870 DEG C, obtain grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat of leaching plant select tape ball milling, built-in supersaturation volatile salt slurries, volatile salt concentration is 100g (NH 4) 2cO 3/ 100g H 2o; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 6.5%) and airtight, at 52 DEG C, react 3.8h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.25%.Then similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
Embodiment 87: by (CaO+FeO)/WO 3molecular ratio is 4.5, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) carry out levigate mixing with Wingdale and fluorite after obtain raw material, the add-on of fluorite is 2.6% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 2h at stoving oven reducing atmosphere 920 DEG C, obtain grog, after clinker cooling to room temperature, levigate with Raymond mill, grog granularity≤8 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 38 DEG C, reacts 5h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 2 times.The leaching yield of tungsten is 98.12%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 88: by (CaO+FeO)/WO 3molecular ratio is 3.4, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with embodiment 86 in grog leach after slag (main component is CaCO 3) and Calcium Fluoride (Fluorspan) carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 4.1% (mass percent) of dry tungsten mineral material amount, raw material granularity≤100 μm, then, roasting 2h at stoving oven neutral atmosphere 960 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects agitation leach device, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.2 times of theoretical amount; Grog is put into leaching plant, at 50 DEG C, reacts 3h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake 5 times.The leaching yield of tungsten is 98.39%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 89: by (CaO+FeO)/WO 3molecular ratio is 4.2, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with embodiment 88 in grog leach after slag and Calcium Fluoride (Fluorspan) carry out levigate mixing after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 0.2% (mass percent) of dry tungsten mineral material amount, raw material granularity≤74 μm, then, roasting 1.5h at stoving oven neutral atmosphere 980 DEG C, obtain grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤85 μm; Leaching plant selects ball milling leacher, and built-in supersaturation volatile salt slurries, volatile salt concentration is 120g (NH 4) 2cO 3/ 100g H 2o, and add bicarbonate of ammonia according to 1.5 times of theoretical amount; Grog is put into leaching plant, at 70 DEG C, reacts 6h.After reaction terminates, leach ore pulp press filtration, with pure water filter cake 4 times.The leaching yield of tungsten is 97.23%.Then, similar embodiment 3 but supplement volatile salt and bicarbonate of ammonia, APT product reaches country's 0 grade of product standard-required.
Embodiment 90: by (CaO+FeO)/WO 3molecular ratio is 7, by certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤80 μm, then, roasting 7h at stoving oven neutral atmosphere 1000 DEG C, obtains grog, after clinker cooling to room temperature, levigate with vibration mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution, and adds bicarbonate of ammonia according to 1.3 times of theoretical amount; Grog is put into leaching plant, at 40 DEG C, reacts 24h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 98.66%.Then, similar embodiment 3, APT product reaches country's 0 grade of product standard-required.
Embodiment 91: by CaO/WO 3molecular ratio is 4, by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) with grog leached mud carry out levigate mixing after obtain raw material, raw material granularity≤53 μm, then, roasting 10h at stoving oven neutral atmosphere 950 DEG C, obtains grog, after clinker cooling to room temperature, levigate with ball mill, grog granularity≤45 μm; The leaching vat that leaching plant select tape stirs, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 13.0%) and airtight, at 40 DEG C, react 20h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 99.01%.Then, similar embodiment 3 but supplement ammoniacal liquor and CO 2.
Embodiment 92: by CaO/WO 3molecular ratio is 8, by certain tungsten slurry (WO 3mass percentage is 16.22%) carry out levigate mixing with grog leached mud and Calcium Fluoride (Fluorspan) after obtain raw material, the add-on of Calcium Fluoride (Fluorspan) is 6.5% (mass percent) of dry tungsten mineral material amount, raw material granularity≤45 μm, then, roasting 0.5h at stoving oven reducing atmosphere 750 DEG C, obtains grog, after clinker cooling to room temperature, levigate with centrifugal mill, grog granularity≤45 μm; Leaching plant selects ball milling leacher, built-in volatile salt saturated solution; Grog is put into leaching plant, adds ammoniacal liquor simultaneously and (make NH in infusion solution 3mass percentage be 8.5%) and airtight, at 45 DEG C, react 4h.After reaction terminates, leach ore pulp suction filtration, with pure water filter cake three times.The leaching yield of tungsten is 94.51%.Then, similar embodiment 3 but supplement volatile salt, bicarbonate of ammonia, ammoniacal liquor and CO 2.
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 technical conceive of the present invention, there is not the problem of employing " common practise " or " customary means ".Even so, even if there has been design, the multiple factors related to are all often restrictions mutually, interactional, be not separate, even if adopt the modernization scientific methods such as orthogonal design, still infinite may combining is had, and enough excellent technical scheme can not be doped, " experiment of limited number of time " can not obtain the suitable value of each factor, and enough excellent technical scheme is not " obviously ".
Above numerous embodiment of the present invention is not limitation of the invention.Those skilled in the art will appreciate that under the prerequisite not departing from spirit of the present invention and design, any details to technical solution of the present invention and form carry out amendment, supplement, improve and replace, all in the protection domain of appended claims.

Claims (10)

1. containing a metallurgical technology for tungsten mineral material, comprising: make raw mineral materials become raw material with batching proportioning; Roasting raw material, to make the transition as grog; Adopt weak caustic solution to leach grog, reclaim the solution that each link feeds back; Carry out solid-liquid separation to leaching slurry, wash mutually slag, washings feeds back to grog and leaches link (I closed loop), and at least part of leached mud feeds back to raw material configuration link (II closed loop) as batching; Purification and impurity removal is carried out to thick solution; Evaporative crystallization is carried out to the solution after purification; The gas discharged is back to the step (III closed loop) leaching grog, and the water evaporated feeds back to the solid-liquid separation link (IV closed loop) of leaching slurry; Carry out solid-liquor separation to the slurries after crystallization, solid phase, through water and/or ammonium salt solution washing, namely obtains the finished product containing W element after oven dry; And crystalline mother solution is also back to the step (V closed loop) leaching grog, for this reason, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
2., containing a metallurgical technology for tungsten mineral material, it is characterized in that, this technique comprises the following steps:
Make to become raw material containing W raw mineral materials and batching MN (M represents positive ion, and N represents negative ion) proportioning;
Roasting raw material, there is chemical reaction in short its, to make the transition as containing M and the grog containing W ion, thus makes grog obtain high chemical reactivity;
Weak base AN (A is positive ion) solution is adopted to leach (the excessive highly basic of thorough abandoning tradition leaches prejudice) grog, leach to make grog, and in circulating reaction, reclaim the solution that each link feeds back, and supplement the weak base AN of consumption according to actual needs;
Solid-liquid separation is carried out to leaching slurry, obtain containing A and contain the thick solution of W ion and the leached mud containing M, slag is washed mutually, washings feeds back to grog and leaches link (I closed loop), according to actual needs, be taken to small part leached mud and feed back to raw material configuration link (II closed loop) as batching, if leached mud has remainder, then store up;
At least first class purification removal of impurities is carried out to containing A with containing the thick solution of W ion;
Evaporative crystallization is carried out, to separate out the intermediates containing W element to the solution after purification; Meanwhile, the gas discharging the gas relevant to element A and be correlated with N element is back to the step (III closed loop) leaching grog, and the water evaporated feeds back to the solid-liquid separation link (IV closed loop) of leaching slurry;
Solid-liquor separation is carried out to the slurries after crystallization, to obtain crystalline mother solution and solid phase, solid phase, through water and/or ammonium salt solution washing, namely obtains the finished product (preferably solid phase again being dissolved and crystallization, to obtain the higher the finished product of purity) containing W element after oven dry; And crystalline mother solution is also back to the step (V closed loop) leaching grog,
For this reason, this technique comprises multiple closed cycle, omnidistance non-wastewater discharge.
3. metallurgical technology according to claim 1 and 2, is characterized in that, described tungsten mineral material comprises sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry; And/or described transition comprise by tungsten mineral material, prepare burden levigate, mix, to prepare raw material; Roasting is carried out to raw material, to obtain grog (preferably carried out by grog fragmentation, levigate).
4. metallurgical technology according to claim 1 and 2, is characterized in that, described weak base is volatile salt, bicarbonate of ammonia, ammoniacal liquor, ammoniacal liquor+CO 2gas, and any mixture of their any mixture and/or they and ammonium tungstate.
5. metallurgical technology according to claim 1 and 2, is characterized in that, comprise following additional technical feature at least one of them:
Slurry is after solid-liquor separation and/or washing, after the ammonia of crystalline mother solution and washing lotion and collection and carbon dioxide mix (or respectively), feed back to the leaching device of grog, solid then or after washing and drying obtains product A PT, or enters next stage dissolving, crystallization, purification subsystem;
Described batching is for containing CaCO 3material, its add-on presses CaO/WO in raw material 3or (CaO+FeO)/WO 3or (CaO+MnO)/WO 3or (CaO+FeO+MnO)/WO 3molecular ratio is at least 1.0, is preferably 1.5-6.0, is more preferably 3.0-4.0, is more preferably 3.3-3.6;
Described raw material granularity is not particularly limited, and is preferably not more than 200 μm, is more preferably and is not more than 100 μm, is more preferably and is not more than 40 μm;
The temperature of raw material roasting, for being not less than 500 DEG C, being preferably 800-1050 DEG C, being more preferably 850-950 DEG C; And
The time of raw material roasting is 0.5-8.0h, is preferably 1.0-3.0h, is more preferably 2.0h.
6. metallurgical technology according to claim 1 and 2, is characterized in that, when described tungsten mineral material is sheelite, calcination atmosphere is not particularly limited, and is preferably neutral or oxidizing atmosphere; And when described tungsten mineral material wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry, calcination atmosphere is neutral or reducing atmosphere, be preferably neutral atmosphere.
7. metallurgical technology according to claim 1 and 2, is characterized in that, comprise following additional technical feature at least one of them:
The granularity of grog is not particularly limited, and is preferably not more than 200 μm, is more preferably not more than 74 μm, is more preferably not more than 45 μm;
CO in Leaching Systems 2stove (kiln) gas that a part produces from raw material roasting process or commodity CO 2, the CO that another part produces from ammonium tungstate solution evaporation and crystal process 2, CO 2can pass in leaching process, also can pass into before leaching;
Leach volatile salt concentration in initial system and be greater than 20g-(NH 4) 2cO 3/ 100g-H 2o, is preferably the concentration of its saturated solution under this system; And
Bicarbonate of ammonia then adds with the form of solution or solid, and the add-on of bicarbonate of ammonia is not particularly limited, and is preferably no less than and makes the calcium in grog be converted into CaCO 31.0 times of aequum (theoretical amount), are more preferably the 1.1-1.4 of theoretical amount doubly;
The add-on of ammoniacal liquor is also not particularly limited, NH in preferred leaching initial system 3mass percentage be 0% ~ 28%, be more preferably 5% ~ 20%, be more preferably 5% ~ 10%;
Ammonium tungstate concentration is not particularly limited, if can guarantee the tungsten ammonium tungstate concentration fully leached in rear gained solution in grog be no more than this system under equilibrium concentration.
8. metallurgical technology according to claim 1 and 2, it is characterized in that, the leaching process of grog carries out in enclosed system, when leaching grog with Ammonium Carbonate system, volatile salt-bicarbonate of ammonia system, volatile salt-ammonia-water systems, volatile salt-bicarbonate of ammonia-ammonium tungstate system, volatile salt-ammoniacal liquor-ammonium tungstate system and volatile salt-ammonium tungstate system, the absolute pressure of reaction system is not particularly limited; With volatile salt-CO 2system, volatile salt-bicarbonate of ammonia-CO 2system, volatile salt-ammoniacal liquor-CO 2system, volatile salt-ammonium tungstate-CO 2system, volatile salt-ammoniacal liquor-ammonium tungstate-CO 2system and volatile salt-bicarbonate of ammonia-ammonium tungstate-CO 2when system leaches grog, the absolute pressure that need control reaction system is not less than 1atm, is preferably 2atm.
9. metallurgical technology according to claim 1 and 2, is characterized in that, extraction temperature is not less than 5 DEG C, is preferably 10-80 DEG C, is more preferably 20-70 DEG C, is more preferably 30-50 DEG C; And/or extraction time is preferably 0.5-8.0h, more preferably extraction time is 2-5h (extraction time is not particularly limited, as long as can guarantee that in grog, tungsten can fully leach).
10. metallurgical technology according to claim 1 and 2, is characterized in that, purification and impurity removal process comprise except in molybdenum, phosphorus, tin, arsenic, silicon, iron, sodium, potassium, bismuth, antimony, calcium, magnesium at least one of them.
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