CN105861856A - Clean metallurgical system for preparing ammonium molybdate from molybdenite concentrate - Google Patents
Clean metallurgical system for preparing ammonium molybdate from molybdenite concentrate Download PDFInfo
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- CN105861856A CN105861856A CN201610341406.5A CN201610341406A CN105861856A CN 105861856 A CN105861856 A CN 105861856A CN 201610341406 A CN201610341406 A CN 201610341406A CN 105861856 A CN105861856 A CN 105861856A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The clean metallurgical system for preparing ammonium molybdate from a molybdenite concentrate comprises a raw material preparation device, a clinker generating device, a clinker pretreatment device, an ammonium salt leaching, purifying and separating device, an acid precipitation and separation device, an ammonium salt conversion and separation device and an absorption device, wherein the raw material preparation device is provided with a molybdenite inlet and a calcium carbonate inlet; the clinker generating device is provided with a roaster, an oxygen inlet, a carbon dioxide outlet and a clinker fine-grinder; the clinker pretreatment device is provided with a pretreatment solution outlet and a pretreatment slag outlet; the ammonium salt leaching, purifying and separating device is provided with a leaching agent inlet, a solution purifying and liquid-solid separating device, a coarse ammonium molybdate solution outlet and a leaching residue returning outlet; the acid precipitation and separation device is provided with a precipitator inlet, a solid-liquid separator, a multiple ammonium molybdate intermediate product outlet, an acid precipitation mother liquor outlet and a pretreatment solution inlet; the ammonium salt conversion and separation device is provided with a size solid-liquid separator, a calcium sulfate solid-phase outlet, and an NH3 and CO2 gas outlet; and the absorption device is provided with an NH3 and CO2 gas recovery inlet, a CO2 gas recovery inlet, an ammonia water supplementing inlet and a re-synthesized leaching agent outlet. The clean metallurgical system is low in production cost, high in production efficiency and free from pollution.
Description
Technical field
The present invention relates to a kind of clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate, belong to molybdenum technical field of smelting.
Background technology
Molybdenite concentrate is the topmost raw mineral materials preparing ammonium molybdate.Process molybdenite concentrate of the prior art is to prepare ammonium molybdate
The method of product mainly includes oxidizing roasting-ammonia leaching process and Whote-wet method oxidation.
Oxidizing roasting-ammonia leaching process technical maturity, invest little, easily grasp, the ammonium molybdate of more than 90% all uses this method to produce, but should
There is following subject matter in method:
1) a large amount of low concentration SO is produced during molybdenum concntrate oxidizing roasting2Flue gas, there is no the processing method of economical and efficient at present, leads
Cause environmental pollution is heavier；
2) oxidizing roasting temperature higher (about 600 DEG C), easily causes MoO in calcining3Volatilization loss, simultaneously to containing low-melting impurities
For more molybdenite concentrate, sintering process is easily lumpd, and these cause the Mo rate of recovery in concentrate relatively low the most at last；
3) the rare element rhenium contained in molybdenite concentrate is difficult to recycle, and almost all is arranged with outside flue gas；
4) higher to the quality requirements of molybdenum concntrate, unsuitable for processing complicated ore and low-grade ore.
Whote-wet method oxidation mainly includes decomposition of nitric acid, Oxygen autoclaving method, sodium hypochlorite oxidization, electroxidation method etc., with oxidation roasting
Burning ammonia leaching process is compared, and eliminates the pollution of sulfur-containing smoke gas in roasting process, is suitable for processing various low-grade complexes raw material Han molybdenum,
Improve the rate of recovery of metal molybdenum, but production cost is higher, harsh to equipment requirement, do not obtain commercial Application widely at present.
For solving SO in oxidizing roasting-ammonia leaching process roasting process2Smoke pollution and the problem of Rhenium recovery, except research Whote-wet method oxidation
Outside technique, also it has been proposed that add additive in oxidizing roasting process.
United States Patent (USP) US3,705,230 propose lime-roasting method, carry out oxidizing roasting after being i.e. mixed into lime in molybdenite concentrate,
Obtain main containing CaMoO4And CaSO4Grog；Grog enters liquid phase through sulfuric acid leaching, molybdenum, and slag is mainly CaSO mutually4；
Leaching slurry reclaims molybdenum therein through separation of solid and liquid, gained liquid phase through methods such as charcoal absorption or ion exchange, solvent extractions,
Finally prepare ammonium molybdate product.Rhenium in concentrate will convert to Ca (ReO in lime-roasting method4)2, by carrying out before acidleach
Water logging, makes rhenium preferentially enter solution and is reclaimed, and Rhenium recovery rate is up to 74%.
Lime-roasting method has been done optimizing research by Chen Tingzhang, Zou Zhenqiu etc., is optimizing under operating condition, the Mo rate of recovery up to 95%,
Rhenium recovery rate is more than 86%.But, this method still suffers from following deficiency:
1) big due to lime-crushed stone pile, generate CaSO4Amount many, the quantity of slag is big；
2) grog leaches in acid condition, and equipment corrosion is more serious, and operating condition is poor；
3) sulfuric acid dosage is big, circulation is difficult, produces a large amount of difficult acid-bearing wastewater；
4) molybdic acid that calcium molybdate obtains after sulfuric acid leaching, also needs just to be converted into ammonium molybdate through ion exchange or solvent extraction and produces
Product, flow process is more complicated, relatively costly；
5) ion exchange and solvent extraction process produce a large amount of nitrogen-containing wastewaters, add processing cost.
Li little Bin et al. is for these problems, it is proposed that lime burning-sal volatile lixiviation process (CN201510223332.0),
I.e. replacing lime with lime stone in raw material preparation process, obtain after roasting is main containing CaMoO4And CaSO4Grog use instead
Sal volatile leaches, and obtains (NH4)2MoO4Solution, (NH4)2SO4Solution and CaCO3Solid；Gained leaching slurry
Through separation of solid and liquid, it is thus achieved that CaCO3Slag returns raw material arrangement step, and contains (NH4)2MoO4(NH4)2SO4Liquid phase through molten
Liquid purifies, is concentrated by evaporation, acid is heavy and evaporative crystallization etc. obtains many ammonium molybdates product and ammonium sulfate byproduct.Lime burning-carbonic acid
Ammonium salt solution lixiviation process overcomes the subject matter that lime-roasting method exists largely, but, however it remains following two aspects
Problem:
1) solution is difficult to all circulate；
2) ammonium carbonate constantly filling into system is finally converted into the ammonium sulfate byproduct that value is relatively low, and production cost certainly will be caused high.
Summary of the invention
It is an object of the invention to provide a kind of clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate, it can realize many ammonium molybdates and carry
The circulation of complete soln during taking, production cost is low, production efficiency is high and non-pollution discharge.
To this end, the invention provides a kind of clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate, it is characterised in that it includes
Raw material device for formulating, grog generating means, grog pretreatment unit, ammonium salt leach with purification and separator, acid is heavy and separates
Device, ammonium salt convert and separator, wherein:
Raw material device for formulating, it has molybdenite entrance, calcium carbonate entrance, is provided with mixing and fine grinding device；
Grog generating means, it has roasting device, oxygen intake, carbon dioxide outlet, grog fine grinding device, carbon dioxide outlet
Connect with gas absorbing device；
Grog pretreatment unit, it has pretreating agent entrance, pretreatment fluid outlet and pretreatment slag outlet；
Ammonium salt leach with purify and separator, its have pretreatment slag entrance, reclaim leaching agent entrance, supplement leaching agent entrance,
Solution purification and liquid-solid separator, thick ammonium molybdate solution export, can be used for the return outlet of raw material preparation leached mud, store up leaching
The outlet of slag, the return outlet that can be used for raw material preparation leached mud connects with raw material device for formulating；
Acid is sunk and separator, and it has in the middle of thick ammonium molybdate solution entrance, precipitant inlet, solid-liquid separator, many ammonium molybdates
Products export, acid heavy mother liquor outlet, pretreatment fluid entrance；
Ammonium salt converts and separator, and it has the heavy mother liquor entrance of acid, calcium carbonate adds entrance, slurries solid-liquid separator, calcium sulfate
Solid-phase outlet, NH3And CO2Gas vent, NH3And CO2Gas vent connects with gas absorbing device；
Absorption plant, it has NH3、CO2The CO that gas reclaims entrance, oxidizing roasting process produces2Gas recovery entrance,
Ammoniacal liquor supplements entrance, recombines the outlet of ammonium salt solution leaching agent.
Preferably, raw material device for formulating also has mineralizer entrance.
Preferably, described mineralizer entrance is calcirm-fluoride entrance, and the addition with described calcirm-fluoride is molybdenite and carbonic acid
The addition controller of the calcirm-fluoride of the 1-10% of the gross mass of calcium, preferably 2-3%.
Preferably, calcium carbonate entrance and the return outlet that can be used for raw material preparation leached mud.
Preferably, raw material device for formulating has:
The addition of calcium carbonate and the calcium carbonate magnitude of recruitment that mol ratio is 2.0-6.0, preferably 3.0-3.6 of molybdenum bisuphide in molybdenite
Controller；
D90 is less than the raw material granularity controller of 60 μm less than 110 μm, preferably D90；And/or,
Dry grinding or wet-milling, preferably wet-milling.
Preferably, grog generating means has:
Range at least includes 400-600 DEG C, the raw material sintering temperature controller of preferably 450-550 DEG C；
Range at least includes 0.4-6 hour, the raw material roasting time controller of preferably 0.5-2 hour；And/or,
Range at least includes that D90 is less than 200 μm, the preferably D90 grog Task-size Controlling device less than 70 μm.
Preferably, pretreating agent entrance is water inlet or sulfuric acid entrance.
Preferably, pretreatment fluid outlet connects with tungsten retracting device, it is preferable that tungsten retracting device is ion-exchange retracting device；
Or, pretreatment fluid outlet connects with raw material configuration device.
Preferably, ammonium salt leaches and has with purification and separator:
Sal volatile consistency controller more than 300g/L；The sal volatile extraction temperature controller of 30-100 DEG C；4-8 is little
Time sal volatile extraction time controller；Or,
Leaching agent consistency controller more than 200g/L, preferably greater than 280g/L；20-100 DEG C, the leaching agent of preferably 30-80 DEG C
Extraction temperature controller；The leaching agent extraction time controller of 4-8 hour.
Preferably, ammonium salt converts and has, with separator, the precipitation process terminal point control device that pH value is 1.5-3；And/or, 40-60 DEG C
Precipitation temperature controller.
According to the present invention, compared with lime burning-sal volatile lixiviation process, due in mother liquor ammonium sulfate no longer with shape
The ammonium sulfate byproduct becoming low value discharges production system, but is converted into ammonium carbonate by adding efficient calcium carbonate cheap and easy to get
Solution, it is achieved that the circulation of ammonium/ammonia in system, thus in system, complete soln can realize recycling, and molybdic acid can be greatly reduced
The production cost of ammonium；
According to the present invention, ammonium salt leaches the temperature of operation and is only 20～30 DEG C, with lime burning-sal volatile lixiviation process phase
Ratio, considerably reduces the extraction temperature of grog；
According to the present invention, product is many ammonium molybdates of the heavy gained of acid, it is simple to follow-up molybdenum product restructuring.
Accompanying drawing explanation
Fig. 1 is the clean metallurgical process chart being prepared ammonium molybdate by molybdenite concentrate according to the present invention.
Fig. 2 is the structure principle chart of the clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate according to the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is made more comprehensively, careful description, but protection scope of the present invention does not limit
In embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art is identical.
Technical term used herein is intended merely to describe specific embodiment, is not intended to limit the scope of the invention.
Except there being special instruction, the various reagent used in the present invention, raw material are can commodity commercially or permissible
The product prepared by known method.
As shown in Figure 1-2, according to the free pollution metallurgy technology of the present invention, molybdenite the metallurgical system preparing ammonium molybdate includes depending on
The raw material device for formulating 10 of secondary connection, grog generating means 20, grog pretreatment unit 30, leaching device 40, thick ammonium molybdate
Solution purification removal of impurities and evaporation concentration device 50, acid sink device 60, many ammonium molybdates ammonia are molten, evaporative crystallization and equipment for separating liquid from solid
70, wherein:
Raw material device for formulating 10, it has molybdenite entrance 11, calcium carbonate entrance 12 and mineralizer entrance 13, be provided with mixing with
Fine grinding device 14；
Grog generating means 20, it has roasting device 24, oxygen intake 21, carbon dioxide outlet 22, grog fine grinding device 23,
Carbon dioxide outlet 22 connects with gas absorbing device 70；
Grog pretreatment unit 30, it has pretreating agent entrance 31, pretreatment fluid outlet 32 and pretreatment slag outlet 33；
Ammonium salt leaches, purifies and separator 40, and it has pretreatment slag entrance 49, reclaims leaching agent entrance 41, supplementary leaching
Go out agent entrance 45, solution purification and liquid-solid separator 46, thick ammonium molybdate solution outlet 42, can be used for raw material preparation leached mud
Return outlet 43, store up the outlet 44 of leached mud, can be used for return outlet 43 and the raw material device for formulating of raw material preparation leached mud
10 connections；
Acid is heavy, separator 50, and it has thick ammonium molybdate solution entrance 51, precipitant inlet 52, solid-liquid separator 53, many
Ammonium molybdate intermediate products outlet 54, acid heavy mother liquor outlet 55, pretreatment fluid entrance 56；
Ammonium salt converts, separator 60, and it has the heavy mother liquor entrance 61 of acid, calcium carbonate adds entrance 62, slurries solid-liquid separator
63, calcium sulfate solid-phase outlet 64, NH3And CO2Gas vent 65, NH3And CO2Gas vent 65 and absorption plant 70
Connection；
Absorption plant 70, it has NH3、CO2The CO that gas reclaims entrance 71, oxidizing roasting process produces2Gas is recovered into
Mouth 72, ammoniacal liquor supplement entrance 73, recombine ammonium salt solution leaching agent outlet 74.
Embodiment 1: by CaCO3/MoS2Mol ratio is 3.6, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 3% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 110 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 600 DEG C, roasting 2 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, ripe
Material granularity D90 is 130 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag tap and add the leaching tanks of band stirring, leach with the sal volatile that concentration is 800g/L, react 4 hours at 100 DEG C.Instead
Ore pulp should be leached after terminating and use vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is 98.12%.Leach
Liquid is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, control the heavy temperature of acid be 50 DEG C, terminal pH be 2,
Obtain the acid of ammonium tetramolybdate and liquid containing ammonium sulfate after acid is heavy and sink mother liquor.In mother liquor is sunk in acid, add calcium carbonate, at 80 DEG C, react 4 little
Time, it is thus achieved that calcium sulfate slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing,
Using as leaching agent recycle, and calcium sulfate slurries separated after obtain calcium sulphate solid and water, calcium sulfate can be former as building materials
Material, water can as during the wash water of slag.
Embodiment 2: by CaCO3/MoS2Mol ratio is 3.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 2% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 100 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 600 DEG C, roasting 0.5 hour, obtains grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 70 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds the leaching tanks of band stirring, leaches with the sal volatile that concentration is 300g/L, reacts 6 hours at 90 DEG C.Instead
Ore pulp should be leached after terminating and use vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is 75.61%.Leach
Liquid is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, and the heavy process control temp of acid is 55 DEG C, terminal pH
It is 2.2, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain that to meet national standard many after recrystallization
Ammonium molybdate product；In mother liquor is sunk in acid, add calcium carbonate, react 3 hours at 90 DEG C, it is thus achieved that CaSO4Slurries and NH3
And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and recycles as leaching agent, and CaSO4
CaSO is obtained after slurries are separated4Solid and water, CaSO4Can as building materials raw material, water can as during the wash water of slag.
Embodiment 3: by CaCO3/MoS2Mol ratio is 5.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 10% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 80 μm.Then, raw material are in roasting
In stove, being passed through air, at 400 DEG C, roasting 6 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, grog
Granularity D90 is 70 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 800g/L, at 70 DEG C
Lower reaction 8 hours.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaches
Rate is 90.05%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control temp of acid
Be 55 DEG C, terminal pH be 2.2, obtain the thick product of ammonium tetramolybdate and mother liquor sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization
Meet many ammonium molybdates product of national standard；In mother liquor is sunk in acid, add calcium carbonate, react 2 hours at 95 DEG C, it is thus achieved that CaSO4
Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and follows as leaching agent
Ring uses, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can be as building materials raw material, water can be as mistake
The wash water of slag in journey.
Embodiment 4: by CaCO3/MoS2Mol ratio is 6.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 50 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 450 DEG C, roasting 2.0 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 60 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 800g/L,
React 8 hours at 80 DEG C.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.Molybdenum in molybdenite
Leaching rate is 94.43%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control of acid
Temperature is 55 DEG C, terminal pH is 1.5, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, after recrystallization
Obtain the many ammonium molybdates product meeting national standard；In mother liquor sunk in acid, add calcium carbonate, react 8 hours at 75 DEG C, it is thus achieved that
CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile, as leaching after absorbing
Go out agent to recycle, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can as building materials raw material, water
The wash water of slag during as.
Embodiment 5: by CaCO3/MoS2Mol ratio is 3.6, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 40 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 550 DEG C, roasting 1.5 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 100 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 700g/L,
React 6 hours at 85 DEG C.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.Molybdenum in molybdenite
Leaching rate is 89.93%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control of acid
Temperature is 45 DEG C, terminal pH is 1.8, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, after recrystallization
Obtain the many ammonium molybdates product meeting national standard；In mother liquor sunk in acid, add calcium carbonate, react 2 hours at 98 DEG C, it is thus achieved that
CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile, as leaching after absorbing
Go out agent to recycle, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can as building materials raw material, water
The wash water of slag during as.
Embodiment 6: by CaCO3/MoS2Mol ratio is 4, by calcium carbonate and certain molybdenite (weight/mass percentage composition of Mo is 40.33%)
Carrying out the levigate raw material that are uniformly mixed so as to obtain with the calcirm-fluoride of 3%, raw material granularity D90 is 45 μm.Then, raw material are in roaster, logical
Entering air, at 550 DEG C, roasting 1 hour, obtains grog.Clinker cooling is to after room temperature, levigate with vibromill, grog granularity D90
It is 40 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.Leached mud after water logging is added and leaches
Equipment, leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 800g/L, reacts 6 at 90 DEG C
Hour.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is
98.13%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control temp of acid is 55 DEG C,
Terminal pH is 1.8, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization and meet country
Many ammonium molybdates product of standard；In mother liquor is sunk in acid, add calcium carbonate, react 6 hours at 85 DEG C, it is thus achieved that CaSO4Slurries,
And NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and recycles as leaching agent,
And CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can as building materials raw material, water can as during slag
Wash water.
Embodiment 7: by CaCO3/MoS2Mol ratio is 3.6, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 4% carries out the levigate raw material that are uniformly mixed so as to obtain, raw material granularity D90=60 μm.Then, raw material are at roaster
In, under oxygen-enriched atmosphere, at 500 DEG C, roasting 2 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, grog
Granularity D90 is 45 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 800g/L, at 90 DEG C
Lower reaction 7 hours.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaches
Rate is 94.58%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control temp of acid
Be 55 DEG C, terminal pH be 2.8, obtain the thick product of ammonium tetramolybdate and mother liquor sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization
Meet many ammonium molybdates product of national standard；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 80 DEG C, it is thus achieved that CaSO4
Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and follows as leaching agent
Ring uses, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can be as building materials raw material, water can be as mistake
The wash water of slag in journey.
Embodiment 8: by CaCO3/MoS2Mol ratio is 3.3, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, raw material granularity D90=100 μm.Then, raw material are at roaster
In, under oxygen-enriched atmosphere, at 500 DEG C, roasting 2 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, grog
Granularity D90 is 200 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 700g/L, at 30 DEG C
Lower reaction 6 hours.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaches
Rate is 65.33%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control temp of acid
Be 40 DEG C, terminal pH be 1.8, obtain the thick product of ammonium tetramolybdate and mother liquor sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization
Meet many ammonium molybdates product of national standard；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 90 DEG C, it is thus achieved that CaSO4
Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and follows as leaching agent
Ring uses, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can be as building materials raw material, water can be as mistake
The wash water of slag in journey.
Embodiment 9: by CaCO3/MoS2Mol ratio is 3.3, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 7% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 50 μm.Then, raw material are in roasting
In stove, being passed through air, at 450 DEG C, roasting 2 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, grog
Granularity D90 is 45 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 700g/L, at 60 DEG C
Lower reaction 7 hours.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaches
Rate is 84.53%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control temp of acid
Be 60 DEG C, terminal pH be 3.0, obtain the thick product of ammonium tetramolybdate and mother liquor sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization
Meet many ammonium molybdates product of national standard；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 90 DEG C, it is thus achieved that CaSO4
Slurries and NH3And CO2Gas, NH3And CO2Gas recombines sal volatile after absorbing, and follows as leaching agent
Ring uses, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can be as building materials raw material, water can be as mistake
The wash water of slag in journey.
Embodiment 10: by CaCO3/MoS2Mol ratio is 3.6, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 40 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 550 DEG C, roasting 1.5 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 45 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 500g/L,
React 2 hours at 80 DEG C.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.Molybdenum in molybdenite
Leaching rate is 86.73%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control of acid
Temperature is 55 DEG C, terminal pH is 1.8, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, after recrystallization
Obtain the many ammonium molybdates product meeting national standard；Calcium carbonate is added in mother liquor is sunk in acid, reaction 4 hours at 80 DEG C, then
1 hour it is incubated again, it is thus achieved that CaSO after temperature is brought up to 98 DEG C4Slurries and NH3And CO2Gas, NH3And CO2
Gas recombines sal volatile after absorbing, and recycles as leaching agent, and CaSO4CaSO is obtained after slurries are separated4
Solid and water, CaSO4Can as building materials raw material, water can as during the wash water of slag.
Embodiment 11: by CaCO3/MoS2Mol ratio is 3.6, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 40 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 550 DEG C, roasting 1.5 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 45 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 500g/L,
React 0.5 hour at 90 DEG C.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite
Molybdenum leaching rate is 54.73%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, and acid was sunk program control
Temperature processed is 55 DEG C, terminal pH is 1.8, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, recrystallization
Rear acquisition meets many ammonium molybdates product of national standard；Calcium carbonate is added in mother liquor is sunk in acid, reaction 4 hours at 75 DEG C, so
After be warmed up to 95 DEG C and be incubated 2 hours, it is thus achieved that CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas warp
Recombine sal volatile after absorption, recycle as leaching agent, and CaSO4CaSO is obtained after slurries are separated4Solid
And water, CaSO4Can as building materials raw material, water can as during the wash water of slag.
Embodiment 12: by CaCO3/MoS2Mol ratio is 2.5, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 3% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 110 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 450 DEG C, roasting 3 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, ripe
Material granularity D90 is 120 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slag tap and add the leaching tanks of band stirring, leach with the sal volatile that concentration is 300g/L, react 4 hours at 60 DEG C.Reaction
Leach ore pulp after end and use vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is 97.21%.Leachate
Through purifying, concentrating, it is heavy that the ammonium molybdate solution after concentrating carries out acid, control the heavy temperature of acid be 50 DEG C, terminal pH be 2,
Obtain the acid of ammonium tetramolybdate and liquid containing ammonium sulfate after acid is heavy and sink mother liquor.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization and meet national standard
Many ammonium molybdates product；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 75 DEG C, be then warmed up to 95 DEG C and be incubated
2 hours, it is thus achieved that CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas recombines ammonium carbonate after absorbing
Solution, recycles as leaching agent, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can be as building
Material raw material, water can as during the wash water of slag.
Embodiment 13: by CaCO3/MoS2Mol ratio is 3.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 2% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 100 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 600 DEG C, roasting 0.5 hour, obtains grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 70 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds the leaching tanks of band stirring, leaches with the sal volatile that concentration is 300g/L, reacts 12 hours at 90 DEG C.
Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is 92.11%.Leaching
Going out liquid through purifying, concentrating, it is heavy that the ammonium molybdate solution after concentrating carries out acid, wherein the heavy process control temp of acid be 55 DEG C, eventually
Point pH is 1.7, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization and meet country's mark
Accurate many ammonium molybdates product；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 75 DEG C, be then warmed up to 95 DEG C and protect
Temperature 2 hours, it is thus achieved that CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas recombines carbonic acid after absorbing
Ammonium salt solution, recycles as leaching agent, and CaSO4CaSO is obtained after slurries are separated4Solid and water, CaSO4Can conduct
Building materials raw material, water can as during the wash water of slag.
Embodiment 14: by CaCO3/MoS2Mol ratio is 5.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 10% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 50 μm.Then, raw material are in roasting
In stove, being passed through air, at 400 DEG C, roasting 10 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill, ripe
Material granularity D90 is 70 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.By the leaching after water logging
Slagging tap addition leaching equipment, leaching equipment is the leaching tanks of band stirring, leaches with unsaturated carbonate ammonium salt solution, reacts 8 at 70 DEG C
Hour.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.In molybdenite, molybdenum leaching rate is
94.23%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, wherein the heavy process control temp of acid
Be 55 DEG C, terminal pH be 2.2, obtain the thick product of ammonium tetramolybdate and mother liquor sunk in acid.Ammonium tetramolybdate is molten through ammonia, obtain after recrystallization
Meet many ammonium molybdates product of national standard；In mother liquor is sunk in acid, add calcium carbonate, react 4 hours at 75 DEG C, then heat up
To 95 DEG C and be incubated 2 hours, it is thus achieved that CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas is after absorbing
Recombine sal volatile, recycle as leaching agent, and CaSO4CaSO is obtained after slurries are separated4Solid and water,
CaSO4Can as building materials raw material, water can as during the wash water of slag.
Embodiment 15: by CaCO3/MoS2Mol ratio is 6.0, and by calcium carbonate, (weight/mass percentage composition of Mo is with certain molybdenite
40.33%) calcirm-fluoride of and 5% carries out the levigate raw material that are uniformly mixed so as to obtain, and raw material granularity D90 is 30 μm.Then, raw material are in roasting
In stove, under oxygen-enriched atmosphere, at 450 DEG C, roasting 2.0 hours, obtain grog.Clinker cooling is to after room temperature, levigate with vibromill,
Grog granularity D90 is 60 μm.Carry out separation of solid and liquid after grog water logging being gone out, from leachate, reclaim rhenium.After water logging
Leached mud adds leaching equipment, and leaching equipment is the leaching tanks of band stirring, leaches with the sal volatile that concentration is 800g/L,
React 5 hours at 80 DEG C.Reaction is leached ore pulp after terminating and is used vacuum filtration, with pure water filter cake three times.Molybdenum in molybdenite
Leaching rate is 93.91%.Leachate is through purifying, concentrating, and it is heavy that the ammonium molybdate solution after concentrating carries out acid, the heavy process control of acid
Temperature is 55 DEG C, terminal pH is 1.5, obtains the thick product of ammonium tetramolybdate and mother liquor is sunk in acid.Ammonium tetramolybdate is molten through ammonia, after recrystallization
Obtain the many ammonium molybdates product meeting national standard；Calcium carbonate is added in mother liquor is sunk in acid, reaction 4 hours at 75 DEG C, then
It is warmed up to 95 DEG C and is incubated 2 hours, it is thus achieved that CaSO4Slurries and NH3And CO2Gas, NH3And CO2Gas is through inhaling
Recombine sal volatile after receipts, recycle as leaching agent, and CaSO4CaSO is obtained after slurries are separated4Solid and
Water, CaSO4Can as building materials raw material, water can as during the wash water of slag.
The implementation of the clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate of the present invention comprises the steps:
1) raw material configuration: molybdenite concentrate, the circulation slag that is mainly composed of calcium carbonate are mixed and finely ground, are configured to raw material；
2) raw material are carried out oxidizing roasting, it is thus achieved that grog by oxidizing roasting: in an oxidizing atmosphere；Produce during oxidizing roasting
Carbon dioxide absorbed, preparation process 4) in ammonium salt solution leaching agent, and grog is carried out fine grinding；
3) pretreatment: using pretreating agent to pre-process in the grog after fine grinding, gained slurries, through solid-liquor separation, obtain solid phase
And liquid phase；
4) ammonium salt leaches, purifies and separate: step 3) in gained solid phase be placed in leaching agent leaching, and through solution purification and liquid-solid
Obtaining thick ammonium molybdate solution and slag phase after separation, wherein overwhelming majority slags return steps 1 as circulation slags mutually) in carry out raw material configuration,
Arrange outside few part slag；
5) acid is heavy, separate: in step 4) in the thick ammonium molybdate solution that obtains adds precipitating reagent, the heavy gained slurries of acid are through liquid-solid point
From, it is thus achieved that mother liquor is sunk in many ammonium molybdates intermediate products and acid；
6) ammonium salt converts, separates: in step 5) in the acid that obtains sink and mother liquor adds calcium carbonate carry out ammonium salt conversion, institute after conversion
Obtain slurries through solid-liquor separation, it is thus achieved that calcium sulfate solid phase, the NH produced during conversion reaction3And CO2Gas is through absorbing, again
Carbonate synthesis ammonium salt solution, as circulating leaching agent；
7) absorb: step 6) in the NH that obtains3、CO2Gas and step 2) in the CO that produces of oxidizing roasting process2Gas is through inhaling
Obtain sal volatile after receipts and supplement appropriate ammoniacal liquor, with preparation process 4) in required ammonium salt solution leaching agent.
Particularly, the heavy mother liquor of acid be mainly composed of ammonium sulfate, in mother liquor is sunk in acid, add CaCO3, make (NH4)2SO4
It is completely converted into (NH4)2CO3, gained sal volatile is absorbing NH3And CO2Recycle as leaching agent afterwards.
Preferably, described step 1) in, calcium carbonate is made up of two parts, the part leached mud i.e. returned and the calcium carbonate supplemented,
Its addition is 2.0-6.0, preferably 3.0-3.6 with the mol ratio of molybdenum bisuphide in molybdenite；
Preferably, described step 1) in, mineralizer is calcirm-fluoride, and the addition of described calcirm-fluoride is the total of molybdenite and calcium carbonate
The 1-10% of quality, more preferably 2-3%.
Preferably, described step 1) in, raw material granularity D90 is less than 60 μm less than 110 μm, more preferably D90.
Preferably, described step 1) in, the process of being mixed and finely ground can be dry grinding can also be wet-milling, preferably wet-milling.
Preferably, described step 2) in, raw material sintering temperature is 400-600 DEG C, more preferably 450-550 DEG C；Roasting time is
0.4-6 hour, more preferably 0.5-2 hour；Grog granularity D90 is less than 70 μm less than 200 μm, more preferably D90.
Preferably, described step 2) in, oxidizing atmosphere is air or oxygen-enriched air.
Preferably, described step 2) in, described carbon dioxide enters step 5 after collecting) and the reaction of ammonia.
Preferably, described step 3) in, described pretreating agent is water or sulfuric acid.
Preferably, described step 3) in, reclaim the tungsten in described pretreatment fluid, preferably ion-exchange and reclaim tungsten or return step
Rapid 1) the raw material configuration process in.
Preferably, described step 4) in, leaching agent is containing NH4 +Solution, preferably sal volatile, ammonium bicarbonate soln, ammonia
Water, ammoniacal liquor+CO2, their any mixture and/or their any mixture with ammonium molybdate.Wherein, use ammonium carbonate molten
During liquid, ammonium carbonate concentration is more than 300g/L, and extraction temperature is 30-100 DEG C, and extraction time is 4-8 hour.
Preferably, described step 4) in, leaching agent concentration is more than 200g/L, preferably greater than 280g/L；Extraction temperature is
20-100 DEG C, preferably 30-80 DEG C；Extraction time is 4-8 hour.
Preferably, described step 6) in, described precipitating reagent is sulfuric acid or step 3) in pretreatment fluid, described byproduct is sulfuric acid
Ammonium, the terminal pH of precipitation process controls at 1.5-3, and precipitation temperature is 40-60 DEG C.Ammonium sulfate and step 4) in leached mud mix
After closing stirring reaction, return leaching process.
Preferably, described step 3) in, from described leachate, reclaim rhenium metal.
Claims (10)
1. the clean metallurgical system being prepared ammonium molybdate by molybdenite concentrate, it is characterised in that it includes raw material device for formulating, ripe
Material generating means, grog pretreatment unit, ammonium salt leach with purify and separator, acid heavy convert with separator, ammonium salt with
Separator, wherein:
Raw material device for formulating, it has molybdenite entrance, calcium carbonate entrance, is provided with mixing and fine grinding device；
Grog generating means, it has roasting device, oxygen intake, carbon dioxide outlet, grog fine grinding device, carbon dioxide outlet
Connect with gas absorbing device；
Grog pretreatment unit, it has pretreating agent entrance, pretreatment fluid outlet and pretreatment slag outlet；
Ammonium salt leach with purify and separator, its have pretreatment slag entrance, reclaim leaching agent entrance, supplement leaching agent entrance,
Solution purification and liquid-solid separator, thick ammonium molybdate solution export, can be used for the return outlet of raw material preparation leached mud, store up leaching
The outlet of slag, the return outlet that can be used for raw material preparation leached mud connects with raw material device for formulating；
Acid is sunk and separator, and it has in the middle of thick ammonium molybdate solution entrance, precipitant inlet, solid-liquid separator, many ammonium molybdates
Products export, acid heavy mother liquor outlet, pretreatment fluid entrance；
Ammonium salt converts and separator, and it has the heavy mother liquor entrance of acid, calcium carbonate adds entrance, slurries solid-liquid separator, calcium sulfate
Solid-phase outlet, NH3And CO2Gas vent, NH3And CO2Gas vent connects with gas absorbing device；
Absorption plant, it has NH3、CO2The CO that gas reclaims entrance, oxidizing roasting process produces2Gas recovery entrance,
Ammoniacal liquor supplements entrance, recombines the outlet of ammonium salt solution leaching agent.
2. the system as claimed in claim 1, it is characterised in that raw material device for formulating also has mineralizer entrance.
3. system as claimed in claim 2, it is characterised in that described mineralizer entrance is calcirm-fluoride entrance, and has institute
State the 1-10% of the gross mass that addition is molybdenite and calcium carbonate of calcirm-fluoride, the addition controller of the calcirm-fluoride of preferably 2-3%.
4. the system as claimed in claim 1, it is characterised in that calcium carbonate entrance and the return that can be used for raw material preparation leached mud
Outlet.
5. the system as claimed in claim 1, it is characterised in that raw material device for formulating has
The addition of calcium carbonate and the calcium carbonate magnitude of recruitment that mol ratio is 2.0-6.0, preferably 3.0-3.6 of molybdenum bisuphide in molybdenite
Controller；
D90 is less than the raw material granularity controller of 60 μm less than 110 μm, preferably D90；And/or,
Dry grinding or wet-milling, preferably wet-milling.
6. the system as claimed in claim 1, it is characterised in that grog generating means has:
Range at least includes 400-600 DEG C, the raw material sintering temperature controller of preferably 450-550 DEG C；
Range at least includes 0.4-6 hour, the raw material roasting time controller of preferably 0.5-2 hour；And/or,
Range at least includes that D90 is less than 200 μm, the preferably D90 grog Task-size Controlling device less than 70 μm.
7. the system as claimed in claim 1, it is characterised in that pretreating agent entrance is water inlet or sulfuric acid entrance.
8. the system as claimed in claim 1, it is characterised in that pretreatment fluid outlet connects with tungsten retracting device, it is preferable that
Tungsten retracting device is ion-exchange retracting device；Or, pretreatment fluid outlet connects with raw material configuration device.
9. the system as claimed in claim 1, it is characterised in that ammonium salt leaches to be had with purification and separator:
Sal volatile consistency controller more than 300g/L；The sal volatile extraction temperature controller of 30-100 DEG C；4-8 is little
Time sal volatile extraction time controller；Or,
Leaching agent consistency controller more than 200g/L, preferably greater than 280g/L；20-100 DEG C, the leaching agent of preferably 30-80 DEG C
Extraction temperature controller；The leaching agent extraction time controller of 4-8 hour.
10. the system as claimed in claim 1, it is characterised in that it is 1.5-3's that ammonium salt conversion has pH value with separator
Precipitation process terminal point control device；And/or, the precipitation temperature controller of 40-60 DEG C.
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| CN108504858A (en) * | 2018-01-23 | 2018-09-07 | 胡小多 | A kind of association Determination of Rare-Expensive Elements enrichment extraction separated structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204162765U (en) * | 2014-10-09 | 2015-02-18 | 江西稀有金属钨业控股集团有限公司 | The metallurgical system of the tungsten mineral material of omnidistance non-pollution discharge |
| CN104762474A (en) * | 2015-05-06 | 2015-07-08 | 中南大学 | Method for preparing ammonium molybdate through molybdenite |
| CN205576251U (en) * | 2016-05-20 | 2016-09-14 | 中南大学 | Clean metallurgical system by brightness molybdenum concntrate preparation ammonium molybdate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204162765U (en) * | 2014-10-09 | 2015-02-18 | 江西稀有金属钨业控股集团有限公司 | The metallurgical system of the tungsten mineral material of omnidistance non-pollution discharge |
| CN104762474A (en) * | 2015-05-06 | 2015-07-08 | 中南大学 | Method for preparing ammonium molybdate through molybdenite |
| CN205576251U (en) * | 2016-05-20 | 2016-09-14 | 中南大学 | Clean metallurgical system by brightness molybdenum concntrate preparation ammonium molybdate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108504858A (en) * | 2018-01-23 | 2018-09-07 | 胡小多 | A kind of association Determination of Rare-Expensive Elements enrichment extraction separated structure |
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