CN204162768U - The system of APT is prepared by the many closed loops of tungsten mineral material - Google Patents

The system of APT is prepared by the many closed loops of tungsten mineral material Download PDF

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Publication number
CN204162768U
CN204162768U CN201420581862.3U CN201420581862U CN204162768U CN 204162768 U CN204162768 U CN 204162768U CN 201420581862 U CN201420581862 U CN 201420581862U CN 204162768 U CN204162768 U CN 204162768U
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leaching
grog
raw material
mass percentage
tungsten
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李小斌
崔源发
周秋生
李建圃
齐天贵
徐双
刘桂华
林国荣
彭志宏
李继红
徐向明
申雷霆
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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
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Abstract

Prepared a system of APT by the many closed loops of tungsten mineral material, its leaching device has the absolute pressure controller of Leaching Systems, Leaching Systems volatile salt consistency controller, leaching agent add-on controller, controls Leaching Systems pH controller, extraction temperature controller, extraction time controller, Leaching Systems initial liquid-solid ratio controller, the final liquid-solid ratio controller of Leaching Systems, leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase washings recovery port, crystal seed entrance; Equipment for separating liquid from solid has the receiving port of leached mud feedback port, the outlet of washing lotion feedback, evaporative crystallization water of condensation; Crystallization apparatus has the gas feedback mouth feeding back to leaching device; The liquid-solid separation device of slurry has the outlet that crystalline mother solution is back to the outlet of leaching device, solid phase wash water entrance and tungsten product.The utility model achieves no effuent discharge; Production cost is low, and production efficiency is high.

Description

The system of APT is prepared by the many closed loops of tungsten mineral material
Technical field
The utility model relates to a kind of system being prepared APT by the many closed loops of tungsten mineral material, belongs 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.
Term " raw material " refers to containing (AO) x(WO 3) y(BO) zmaterial, wherein A is Ca, and B is Fe or Mn, or A and B is Ca; X+z+y=4; Preferably, x=3, y=1, z=0; Or, x=2, y=1, z=1.
What term " raw material granularity controller " referred to makes the granularity of raw material be not more than 200 μm of controllers, and those skilled in the art can select its concrete structure.
Term " Seed charge controller " refers to and makes Seed charge be the controller of 0-15g/L, and those skilled in the art can select its concrete structure.
Term " leaching agent consistency controller " refers to and makes leaching agent concentration be greater than 10g-NH 4 +/ 100g-H 2the controller of O, those skilled in the art can select its concrete structure.
Term " leaching agent add-on controller " refers to that leaching agent add-on is at least makes AO and BO in raw material be converted into the controller of 1.0 times of the amount (theoretical amount) of corresponding difficulty soluble salt, and those skilled in the art can select its concrete structure.
Term " leaching pH value controller " refers to the controller making Leaching Systems pH be not less than 8, and those skilled in the art can select its concrete structure.
Term " absolute pressure controller " refers to the controller making the absolute pressure of Leaching Systems be not less than 1atm, and those skilled in the art can select its concrete structure.
Term " extraction temperature controller " refers to and makes extraction temperature be the controller of 15 ~ 100 DEG C, and those skilled in the art can select its concrete structure.
Term " extraction time controller " refers to and makes extraction time be the controller of 0.1 ~ 10.0h, and those skilled in the art can select its concrete structure.
Term " initial liquid-solid ratio controller " refers to the controller making the initial liquid-solid ratio of Leaching Systems be not less than 1:1mL/g, and those skilled in the art can select its concrete structure.
Term " final Leaching Systems liquid-solid ratio controller " refers to that the liquid-solid ratio controlling final Leaching Systems is the controller of 3:1 ~ 4:1mL/g, and those skilled in the art can select its concrete structure.
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 the circulation technology of solution and supplies.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 serious, 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.
Utility model content
The purpose of this utility model is to provide a kind of system being prepared APT by the many closed loops of tungsten mineral material, and its flow process is short, solution reusable edible, contaminated wastewater are almost uprooted, cost is low, be easy to industrialization.
For this reason, according to an aspect of the present utility model, provide a kind of system being prepared APT by the many closed loops of tungsten mineral material, it is characterized in that, this system comprises successively:
Raw material preparation facilities, it has the receiving port of the Task-size Controlling device of mixture and the feedback leached mud of subsequent handling generation;
Grog preparation facilities, it comprises stoving oven and grog fine mill;
Leaching device, it has the absolute pressure controller of Leaching Systems, Leaching Systems volatile salt consistency controller, leaching agent add-on controller, controls Leaching Systems pH controller, extraction temperature controller, extraction time controller, Leaching Systems initial liquid-solid ratio controller, the final liquid-solid ratio controller of Leaching Systems, leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth;
Equipment for separating liquid from solid, it has the receiving port of leached mud feedback port, the outlet of washing lotion feedback, evaporative crystallization water of condensation as filtration unit, and this equipment for separating liquid from solid is communicated with the crystal seed entrance of leaching device in the way of leached mud receiving port feeding back to raw material preparation facilities;
At least one-level purification and impurity removal device, the entrance of the first step is communicated with the thick taphole containing W elements, and at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole containing W elements;
Crystallization apparatus, it has the gas feedback mouth feeding back to leaching device and the smart solution evaporation cerium sulphate crystal device containing W elements;
The liquid-solid separation device of slurry, it has the outlet that crystalline mother solution is back to the outlet of leaching device, solid phase wash water entrance and tungsten product.
Preferably, continue to be communicated with the dissolving of next stage, crystallization, purification subsystem, and/or last step adds extractor fan.
Preferably, described leaching device is agitation leach equipment or ball milling leaching plant; And/or described leaching device is the tightness system that can bear 4atm pressure.
Preferably, described roasting kiln is static or dynamic roasting stove.
Preferably, described leaching device is an independent leaching plant, or the leaching plant that 2-4 series connection uses.
Preferably, described filtration unit is pumping and filtering device, filtering equipment and/or natural filtration groove; Described purification and impurity removal device is decleaning tank, filter plant and/or subsider, and/or, be provided with whipping appts and/or attemperator in described decleaning tank.
Preferably, the drawing-in device of sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry is also comprised.
Preferably, also comprise roasting is carried out to obtain device transition of grog to raw material.
Preferably, volatile salt, bicarbonate of ammonia, ammoniacal liquor, ammoniacal liquor+CO is also comprised 2the adding set of the weakly alkaline leaching agents such as gas.
Preferably, described raw material preparation facilities has tungsten mineral material metering entrance, batching metering entrance, mineralizer metering entrance, raw material are levigate and evenly mixing device.
Preferably, roasting kiln is through feeding measurement device and raw material silo and raw material outlet; Grog fine mill is through grog storehouse and thick grog outlet; The entrance of first step purification and impurity removal device is communicated with the thick taphole containing W elements, and at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole containing W elements; And/or the entrance of crystallization apparatus is communicated with the smart taphole containing W elements.
According to the utility model, 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 utility model, technical process is simple, and easy to operate, production cost is low, non-wastewater discharge and pollution.
Accompanying drawing explanation
Fig. 1 is according to a kind of structural principle schematic diagram being prepared the system of APT by tungsten mineral material of the present utility model.
Fig. 2 is according to a kind of process flow sheet being prepared APT by tungsten mineral material of the present utility model.
Embodiment
Below in conjunction with accompanying drawing 1-2, embodiment of the present utility model is described further.
As shown in Figure 1, the metallurgical technology containing tungsten mineral material of the present utility model 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 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 supplement the weak base AN of consumption according to actual needs;
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 leaching ore deposit agent (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, leached mud remainder is stored up;
At least first class purification removal of impurities 500 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;
Carry out solid-liquor separation 700 to the slurries after crystallization, to obtain crystalline mother solution and solid phase, namely solid phase 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 water washing; 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 utility model comprises successively:
Raw material preparation facilities 10, it has raw mineral materials metering entrance 11 and batching metering entrance 12 (being preferably also provided with mineralizer metering entrance 13), 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) 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, and at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole 62 containing W elements;
Crystallization apparatus 70, its entrance 71 is communicated with the smart 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 smart solution evaporation cerium sulphate crystal device containing W elements) 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 utility model, 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 is at least and makes the tungsten in tungsten mineral material by generating Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 61.0 times of theoretical amount, preferred 1.1-1.5 doubly, more preferably 1.2 times;
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 less than 200 μm, is preferably less than 45 μm; Raw material maturing temperature is not less than 500 DEG C, is preferably 800 ~ 1050 DEG C, is preferably 850 ~ 950 DEG C; Roasting time is not particularly limited, and is fully converted into Ca for making the tungsten in raw material 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 6, temperature is low, needs to extend roasting time, is preferably roasting 2h at 800 DEG C; Roasting time is 0.5-8.0h, is 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 utility model is by 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; Ca 3wO 6and/or Ca 2feWO 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-ammonium bicarbonate soln system, volatile salt-ammonium tungstate-ammonium bicarbonate soln system, also can be volatile salt-CO 2solution system, volatile salt-ammonium tungstate-CO 2solution system can also be volatile salt-ammonia soln system, volatile salt-ammoniacal liquor-ammonium tungstate solution system.
Preferably, Ca is leached by volatile salt-bicarbonate of ammonia, volatile salt-ammonium tungstate-bicarbonate of ammonia and volatile salt-ammoniacal liquor-ammonium tungstate solution 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 2with volatile salt-ammonium tungstate-CO 2solution system 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.Volatile salt-ammonium tungstate-bicarbonate of ammonia and volatile salt-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-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, and preferably leaches NH in initial system 3mass percentage be 0% ~ 28%, be more preferably 5% ~ 20%, be more preferably 5% ~ 10%.
Preferably, described volatile salt-bicarbonate of ammonia and volatile salt-ammonium tungstate-ammonium bicarbonate soln system, bicarbonate of ammonia add-on is at least 1.0 times of theoretical amount, is preferably 1.1 ~ 1.4 times.
Preferably, control Leaching Systems pH and be not less than 8.Extraction temperature 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 10 ~ 80 DEG C, be 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 at 0.5 ~ 8.0h, be more preferably 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:
CaCO 3+2NH 4OH Ca(OH) 2+(NH 4) 2CO 3(1)
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 embodiment of the present utility model, 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, Ca, Mg, K, Na meet the qualified APT quality product of preparation and require.According to an embodiment of the present utility model, the impurity in precipitator method removing ammonium tungstate solution can be adopted, prepare ammonium tungstate refined liquid thus.
According to embodiment of the present utility model, 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 an embodiment of the present utility model, 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.1 times of theoretical amount, allocate into after grog leached mud (main component is calcium carbonate) and mineralizer (Calcium Fluoride (Fluorspan)) carry out levigate, mixing and 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 63.75%, Fe mass percentage is 5.90%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate, mixing and obtain raw material, raw material granularity≤45 μm, then, in shaft furnace, under weak reducing atmosphere, 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 certain wolframite (WO 3mass percentage is 62.40%, Fe mass percentage be 14.08%, Mn mass percentage is 2.25%) by generating Ca 3wO 6and Ca 2feWO 6and Ca 2mnO 61.13 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate, mixing and 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, roasting 6.0h at 800 DEG C, obtain 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 certain wolframite (WO 3mass percentage is 42.17%, Fe mass percentage is 11.34%) by generating Ca 3wO 6and Ca 2feWO 61.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 carbon acid hydrogen ammonium and ammoniacal liquor.
Embodiment 5: by certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 62.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 7h at 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain tungsten slurry (WO 3mass percentage is 16.22%) by generating Ca 3wO 62.67 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤40 μm, then, 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 60.5 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, raw material granularity≤45 μm, then, roasting 1.5h at 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) by generating Ca 3wO 6and Ca 2feWO 60.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then roasting 3h at stoving oven neutral atmosphere 500 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 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 63.0 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.77 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.2 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.13 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 2h at 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.37 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤61 μm, then, roasting 2h at 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤53 μm, then, roasting 0.5h at 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.57 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤74 μm, then, roasting 2h at 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.67 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 60.5 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, raw material granularity≤33 μm, then, roasting 5h at 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) by generating Ca 3wO 6and Ca 2feWO 60.97 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.77 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.27%, Fe mass percentage is 5.86%) by generating Ca 3wO 6and Ca 2feWO 61.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 6and Ca 2mnO 61.5 times of theoretical amount, allocate into after rhodochrosite and Wingdale carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.63 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤42 μm, then, roasting 2h at 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 certain sheelite (WO 3mass percentage is 60.94%) by generating Ca 3wO 6and Ca 2mnWO 61.53 times of theoretical amount, allocate into after rhodochrosite and grog leached mud carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 60.94%) by generating Ca 3wO 61.43 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤48 μm, then, 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.63 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤38 μm, then, roasting 1h at 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 certain sheelite (WO 3mass percentage is 60.94%) by generating Ca 3wO 61.7 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤63 μm, then, 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 6and Ca 2mnWO 61.7 times of theoretical amount, allocate into after rhodochrosite and grog leached mud carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 6and Ca 2mnWO 61.7 times of theoretical amount, allocate into after rhodochrosite and grog leached mud carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.83 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.73 times of theoretical amount, allocate into after Wingdale carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 63.33 times of theoretical amount, allocate into after spathic iron ore and grog leached mud carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.7 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain tungsten slurry (WO 3mass percentage is 16.22%) by generating Ca 3wO 61.3 times of theoretical amount, allocate into after Wingdale carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.17 times of theoretical amount, allocate into after Wingdale carries out levigate mixing and 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) by generating Ca 3wO 6and Ca 2feWO 61.2 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 63.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.83 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.37 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤53 μm, then, roasting 8h at 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 certain sheelite (WO 3mass percentage is 60.94%) by generating Ca 3wO 61.87 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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, 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 1.5 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.57 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.6 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.0 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 64.0 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.33 times of theoretical amount, allocate into after Wingdale carries out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 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 certain tungsten slurry (WO 3mass percentage is 16.22%) by generating Ca 3wO 62.67 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤96 μm, then, 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 8h at 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) by generating Ca 3wO 6and Ca 2feWO 61.07 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 63.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.07 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.13 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.4 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, roasting 8h at 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.37 times of theoretical amount, allocate into after Wingdale and fluorite carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.17 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤53 μm, then, roasting 8h at 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.57 times of theoretical amount, allocate into after grog leached mud and fluorite carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.07 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.03 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.23 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 63.75%, Fe mass percentage is 5.90%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain wolframite (WO 3mass percentage is 60.40%, Fe mass percentage is 15.08%) by generating Ca 3wO 6and Ca 2feWO 61.27 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate, mixing and 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 certain wolframite (WO 3mass percentage is 42.17%, Fe mass percentage is 11.34%) by generating Ca 3wO 6and Ca 2feWO 61.17 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 62.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤25 μm, then, roasting 7h at 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain tungsten slurry (WO 3mass percentage is 16.22%) by generating Ca 3wO 62.67 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤45 μm, then, 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.2 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain Scheelite-Wolframite Mixed Mine (WO 3mass percentage is 43.20%, Fe mass percentage is 7.18%) by generating Ca 3wO 6and Ca 2feWO 61.1 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and obtain raw material, 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, obtains 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 63.0 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 60.9 times of theoretical amount, allocates into after grog leached mud carries out levigate mixing and obtains raw material, raw material granularity≤45 μm, then, roasting 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.27 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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/ 100gH 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.5 times of theoretical amount, allocate into after Wingdale and fluorite carry out levigate mixing and 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.13 times of theoretical amount, allocate into grog in embodiment 86 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 61.4 times of theoretical amount, allocate into grog in embodiment 88 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 certain sheelite (WO 3mass percentage is 52.33%, Fe mass percentage is 2.04%) by generating Ca 3wO 6and Ca 2feWO 62.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤80 μm, then, roasting 7h at 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 certain sheelite (WO 3mass percentage is 49.53%, Fe mass percentage is 0.43%) by generating Ca 3wO 61.33 times of theoretical amount, allocate into after grog leached mud carries out levigate mixing and obtain raw material, raw material granularity≤53 μm, then, roasting 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 certain tungsten slurry (WO 3mass percentage is 16.22%) by generating Ca 3wO 62.67 times of theoretical amount, allocate into after grog leached mud and Calcium Fluoride (Fluorspan) carry out levigate mixing and 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, obtain 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.
Implement the method preparing APT from tungsten mineral material of the present utility model to comprise 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-bicarbonate of ammonia-ammonium tungstate or volatile salt-ammonium tungstate-CO 2or volatile salt-ammoniacal liquor-ammonium tungstate solution system 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, namely solid phase obtains APT product after water washing, 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, tungsten slurry;
Preferably, during raw material preparation, the add-on of calcareous material is at least tungsten by generation Ca 3wO 6and/or Ca 2feWO 6and/or Ca 2mnWO 61.0 times of theoretical amount, preferred 1.1-1.5 doubly, more preferably 1.2 times; Raw material granularity is not more than 200 μm, is preferably not more than 100 μm, is more preferably and is not more than 45 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, 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, 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, the add-on of bicarbonate of ammonia is at least 1.0 times of theoretical amount, be preferably the 1.1-1.4 of theoretical amount doubly, 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; The add-on of ammoniacal liquor is also not particularly limited, and preferably leaches NH in 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, and when leaching grog with volatile salt-bicarbonate of ammonia-ammonium tungstate, volatile salt-ammoniacal liquor-ammonium tungstate solution system, the absolute pressure of reaction system is not particularly limited, with volatile salt-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 comprise except the processes such as molybdenum, phosphorus, tin, arsenic, silicon, iron, sodium, potassium, bismuth, antimony, calcium, magnesium at least one of them.
According to another one aspect of the present utility model, provide a kind of system preparing 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: vibrating mill, twin rollers, 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, natural filtration groove.
Preferably, described impurity removing equipment is decleaning tank, filter plant, subsider.
Preferably, whipping appts, attemperator is provided with in described decleaning tank.
The utility model 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) tungsten minerals grog directly obtains ammonium tungstate solution after leaching, and eliminates step transition from sodium tungstate solution to ammonium tungstate solution;
3) low-temp extraction of tungsten mineral material is achieved;
4) supplies consumption significantly reduces, and flow process is simple, and easy to operate, cost is low, is easy to industrial application.
According to the utility model, with " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate " system 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" and " volatile salt-ammoniacal liquor-ammonium tungstate " all belong to weakly alkaline system, have to pass through raw material transition step could realize leaching.
According to the utility model, select " volatile salt-bicarbonate of ammonia-ammonium tungstate " or " volatile salt-ammonium tungstate-CO 2" or " volatile salt-ammoniacal liquor-ammonium tungstate " system leach; 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 abandoned traditional open circuit not circulating system or open circuit half circulating system; eradicated discharge of wastewater, really achieved green metallurgical.
According to the utility model, 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 utility model, adopt volatile salt-bicarbonate of ammonia-ammonium tungstate or volatile salt-ammonium tungstate-CO 2or " volatile salt-ammoniacal liquor-ammonium tungstate " system leaches 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 utility model, 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 utility model, 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 utility model, achieve circulation metallurgical technology, system non-wastewater discharge, thoroughly avoid part W elements to be emitted in vain, therefore, the W elements rate of recovery also improves.
According to the utility model, 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 utility model, add the pretreatment process of tungsten mineral material, adopt volatile salt-bicarbonate of ammonia-ammonium tungstate or volatile salt-ammonium tungstate-CO 2or volatile salt-ammoniacal liquor-ammonium tungstate 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.
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 utility model, 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 utility model is not to restriction of the present utility model.It will be appreciated by those skilled in the art that; under the prerequisite not departing from spirit of the present utility model and design; any details to technical solutions of the utility model and form carry out amendment, supplement, improve and replace, all in the protection domain of appended claims.

Claims (11)

1. prepared a system of APT by the many closed loops of tungsten mineral material, it is characterized in that, this system comprises successively:
Raw material preparation facilities, it has the receiving port of the Task-size Controlling device of mixture and the feedback leached mud of subsequent handling generation;
Grog preparation facilities, it comprises stoving oven and grog fine mill;
Leaching device, it has the absolute pressure controller of Leaching Systems, Leaching Systems volatile salt consistency controller, leaching agent add-on controller, Leaching Systems pH controller, extraction temperature controller, extraction time controller, Leaching Systems initial liquid-solid ratio controller, the final liquid-solid ratio controller of Leaching Systems, leaching agent entrance, leaching slurry outlet, feedback gas recovery port, slurry separating, washing liquid recovery port, slag phase washings recovery port, crystal seed entrance, carbonic acid gas pass into mouth;
The equipment for separating liquid from solid of leaching slurry, it has the receiving port of leached mud feedback port, the outlet of washing lotion feedback, evaporative crystallization water of condensation as filtration unit, and this equipment for separating liquid from solid is communicated with the crystal seed entrance of leaching device in the way of leached mud receiving port feeding back to raw material preparation facilities;
At least one-level purification and impurity removal device, the entrance of the first step is communicated with the thick taphole containing W elements, and at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole containing W elements;
Crystallization apparatus, it has the gas feedback mouth feeding back to leaching device and the smart solution evaporation cerium sulphate crystal device containing W elements;
The equipment for separating liquid from solid of slurry, it has the outlet that crystalline mother solution is back to the outlet of leaching device, solid phase wash water entrance and tungsten product.
2. the system as claimed in claim 1, is characterized in that, continues to be communicated with the dissolving of next stage, crystallization, purification subsystem, and/or last step purification and impurity removal device adds extractor fan.
3. the system as claimed in claim 1, is characterized in that, described leaching device is agitation leach equipment or ball milling leaching plant; And/or described leaching device is the tightness system that can bear 4atm pressure.
4. the system as claimed in claim 1, is characterized in that, described roasting kiln is static or dynamic roasting stove.
5. the system as claimed in claim 1, is characterized in that, described leaching device is an independent leaching plant, or the leaching plant that 2-4 series connection uses.
6. the system as claimed in claim 1, is characterized in that, described filtration unit is pumping and filtering device, filtering equipment and/or natural filtration groove; Described purification and impurity removal device is decleaning tank, filter plant and/or subsider, and/or, be provided with whipping appts and/or attemperator in described decleaning tank.
7. the system as claimed in claim 1, is characterized in that, also comprises the drawing-in device of sheelite, wolframite, Scheelite-Wolframite Mixed Mine and/or tungsten slurry.
8. the system as claimed in claim 1, is characterized in that, also comprises and carries out roasting to obtain device transition of grog to raw material.
9. the system as claimed in claim 1, is characterized in that, also comprises volatile salt, bicarbonate of ammonia, ammoniacal liquor, ammoniacal liquor+CO 2the adding set of the weak base leaching agent of gas.
10. system according to claim 1, is characterized in that, described raw material preparation facilities has raw mineral materials metering entrance, batching metering entrance, mineralizer metering entrance, raw material are levigate and evenly mixing device.
11. the system as claimed in claim 1, is characterized in that, roasting kiln is through feeding measurement device and raw material silo and raw material outlet; Grog fine mill is through grog storehouse and thick grog outlet; The entrance of first step purification and impurity removal device is communicated with the thick taphole containing W elements, and at different levels have purification and impurity removal agent entrance and impurity collector, and last step has the smart taphole containing W elements; And/or the entrance of crystallization apparatus is communicated with the smart taphole containing W elements.
CN201420581862.3U 2014-10-09 2014-10-09 The system of APT is prepared by the many closed loops of tungsten mineral material Expired - Fee Related CN204162768U (en)

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