CN101723458A - Method for cleanly extracting vanadium pentexide from vanadium containing material - Google Patents
Method for cleanly extracting vanadium pentexide from vanadium containing material Download PDFInfo
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- CN101723458A CN101723458A CN200910227422A CN200910227422A CN101723458A CN 101723458 A CN101723458 A CN 101723458A CN 200910227422 A CN200910227422 A CN 200910227422A CN 200910227422 A CN200910227422 A CN 200910227422A CN 101723458 A CN101723458 A CN 101723458A
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Abstract
The invention relates to a method for cleanly extracting vanadium pentexide from a vanadium containing material. The method is characterized in that: the vanadium containing material is milled by the wet method, and then mixed with a certain weight amount of sulfuric acid, vanadic acid, water, sulfuric acid or phosphoric acid salt having certain association; under conditions of set temperature and set time, performing three-stage reflux leaching reaction of the mixture; adding ammonia sulfate and reducing iron powder to reaction leach solution in sequence to obtain aluminum ammonium sulfate crystals and ammonium ferrous sulfate crystals respectively; adding sulfuric acid to the solution in which aluminum and iron are separated out, cooling the solution for crystallization to obtain vanadium sulfate acyl crystals, and returning the mother liquor to extract vanadium ores; performing the neutralization reaction of the vanadium sulfate acyl crystals and ammonia water to obtain a precipitate of vanadium hydroxide, and returning the solution of ammonia sulfate to precipitate the aluminum and iron; and calcining the vanadium hydroxide and oxygen gas at a high temperature of over 300 DEG C to obtain the vanadium pentexide. The method has the advantages of short process flow, less energy consumption, high vanadium yield, low production cost, environmental protection, and comprehensive utilization of valuable metallic elements in ores.
Description
Technical field
The invention belongs to technical field of wet metallurgy, be specifically related to a kind of from contain the vanadium material clean and effective extract the method for Vanadium Pentoxide in FLAKES, reclaim valuable metal elements such as the aluminium that contains in the raw material, iron simultaneously.
Background technology
Vanadium has many valuable physicochemical properties and mechanical characteristics, thereby is widely used in the The modern industry technology.80%～85% vanadium is used for ferrous metals industry and makes additive with the preparation Special Alloy Steel; Aspect chemical industry, vanadium compound has been widely used in contact acid process industry, refining of petroleum and the organic synthesis industry as catalyzer and cracking agent, is that any material cannot alternate.
Vanadium is abundant at the occurring in nature reserves, disperses but distribute, and does not have independent mineral deposit, is regarded as " rare metal ", mainly contains vanadium minerals the roscoelite of containing, roscoelite are arranged, contains vanadium kaolin, contains the vanadium iron oxide ore, contains the scherbinaite garnet, contains scherbinaite coal etc., V
2O
5Grade also contains other valuable elements such as aluminium, iron, calcium, titanium, chromium, magnesium, potassium, phosphorus, V simultaneously between 0.3%～2%
2O
5Grade is hanged down belonging to complicated difficulty below 0.8% and is soaked the ore deposit, substantially all slatterns at recovery process.In addition, also have many vanadium industrial residues that contain, as making the vitriolic vanadium containing catalysts, v-bearing steel slag contains scherbinaite cinder etc.
China generally adopts sodium-salt calcination-water logging-ammonium salt precipitation-ammonium meta-vanadate pyrolytic process flow process to extract vanadium from blast furnace vanadium slag or navajoite since the Vanadium Pentoxide in FLAKES industrial production seventies.The main drawback that this technology exposes aborning is: 1, to the type requirements height in ore deposit, only use the easily soft ore deposit of siliceous clay lithotype of leaching of higher-grade; 2, in roasting process more than 800 ℃, produce a large amount of HCl and Cl
2Deng toxic gas, leaching process produces a large amount of sodium salt waste water, and environment is caused severe contamination, and the energy consumption height; 3, the total yield of vanadium is about 50%, the navajoite serious waste of resources.
Because economy and environmental stress have been done a lot of technological improvements at the extraction smelting of vanadium, number of patent application 200810058165.9 has been introduced the method that contains extracting vanadium the pickling liquor of scherbinaite coal oxygen pressure from high ferro; Number of patent application 200810302035.5 has been introduced the method that cleans vanadium extraction with hydrochloric acid and hydrofluoric acid as the leaching medicament from contain the vanadium yeath; Number of patent application 200410061233.9 has been introduced the compound calcification baking of bone coal-low acidleach and has been got-extraordinary ion-exchange system vanadium method; Number of patent application 200610031639.1 is introduced the environment-friendly type extraction vanadium method, adopts the operational path of blank roasting-diluted acid leaching-resin absorption, eliminates three-waste pollution; Number of patent application 200710303489.x has introduced a kind of from containing the scherbinaite coal or containing the method for extracting Vanadium Pentoxide in FLAKES and comprehensively extracting tschermigite and iron oxide red the vanadium lime-ash, the extraction of its vanadium is mainly by the vitriol co-precipitation, and then pyrolysis vitriol separation of iron, vanadium, again through extracting-back extraction get, ammonium salt precipitation, pyrolysis ammonium vanadate obtain Vanadium Pentoxide in FLAKES.
Few for the method research report that extracts vanadium from the industrial residue that contains vanadium also is the operational path that employing is similar to the ore vanadium extraction generally, causes the waste and the environmental pollution of secondary resource equally.The real elimination or the minimizing pollution, the processing method that reaches comprehensive utilization of resources does not also have industrialized implementation at present.
Merely traditional processing technology is undergone technological transformation or end treatment can't fundamentally be coped with various crises; therefore; the basic outlet of vanadium manufacture development is to create the new cleaning procedure of eradicating pollution from the source; can be applicable to various low-grade complex ores; improve the rate of recovery of vanadium, cut down the consumption of energy, the comprehensive utilization that realizes valuable element in the ore is to reduce production costs; being the key that refining vanadium industry is depended on for existence, also is purpose of the present invention.
Summary of the invention
The purpose of this invention is to provide a kind of from contain the vanadium material clean and effective extract the method for Vanadium Pentoxide in FLAKES, create one strong to containing the vanadium raw materials suitability, the leaching rate height, energy consumption is low, eradicate the cleaning procedure that pollutes from the source, other valuable elements are fully utilized in the vanadium raw materials to containing simultaneously, reduce production costs.
For achieving the above object, the present invention adopts following steps:
Association formula ionogen three stage countercurrents efficiently leach: will contain the vanadium material and weigh, broken, wet grinding to 60～80 orders, mix with secondary counter-current extraction liquid 2, be heated to 80～100 ℃, reacted 2～5 hours, filter, obtain filtrate 3 and filter cake 1, filter cake 1 mixes with one-level counter-current extraction liquid 1, is heated to 90～110 ℃, reacts 1～3 hour, filter, obtain leaching liquid 2 and filter cake 2, leaching liquid 2 returns the leaching raw ore, according to containing what of various valuable elements in the vanadium material, calculate acid consumption, according to 1.2～3.0 times of theoretical amount, adding has the phosphoric acid of certain association, sulfuric acid and water are at 100～120 ℃, reaction times is 0.5～2 hour, carries out third stage leaching reaction; After three grades of leachings have been reacted, filter, washing, filter residue is made cement admixture, and filtrate is returned use as one-level counter-current extraction liquid 1;
Reaction/separation coupling crystalline deposit: in filtrate 3, add the precipitation agent alkali metal sulfates, as ammonium sulfate, at this moment Tai-Ace S 150 in the solution and ammonium sulfate reaction forms ten less sulfate dihydrate aluminium ammonium double salt of solubleness, by stirring, cooling, crystallization, filtration, isolates ammonium aluminum sulfate crystal; The reductive agent that in filtrate, adds metering then, as sodium sulphite, iron powder etc., make the ferric iron in the solution be reduced to ferrous iron, under stirring and cooling conditions, add the precipitation agent alkali metal sulfates, as ammonium sulfate, make ferrous sulfate and ammonium sulfate reaction in the solution form ten less sulfate dihydrate ferrous ammonium double salt of solubleness; When the concentration that adds ammonium sulfate in the solution during greater than 20% (weight ratio), because salting out, the concentration of ferrous sulfate is less than 5% (weight ratio); When the concentration that adds ammonium sulfate in the solution during greater than 30% (weight ratio), the concentration of ferrous sulfate is less than 2% (weight ratio); When temperature is lower than 20 ℃, the ferrous eduction rate is more than 93%;
The vanadium sulfate acyl crystallization is separated out: separate filtrate behind aluminium, the iron and turn back to the leaching operation as the aqueous solution and recycle, when the concentration of vanadium runs up to 10% (weight ratio) when above, through evaporation concentration, add the vitriol oil then; Because vanadium sulfate acyl different solubility in the sulfuric acid of differing temps and different concns, sulfuric acid concentration is high more, and temperature is low more, the solubleness of vanadium sulfate acyl is more little, at 25 ℃, when sulfuric acid concentration is increased to 6mol/L from 0, the concentration of vanadium sulfate acyl drops to 0.7mol/L from 3.3mol/L; By in vanadium liquid, adding the vitriol oil more than 93% (weight ratio), vanadium sulfate acyl is separated out from solution with the crystalline form; Separating out sulphuric acid soln behind the vanadium sulfate acyl turns back to the dissolving of leaching operation as acid starting material and contains the vanadium raw material of substance;
In the vanadic salts and conversion: vanadium sulfate acyl crystal and ammoniacal liquor are carried out neutralization reaction, obtain that vanadium hydroxide precipitates and ammoniumsulphate soln; Reaction formula is as follows: VOSO
4+ 2NH
3H
2O+H
2O=V (OH)
4↓+(NH
4)
2SO
4By the neutralization conversion, on the one hand, the sulfate ion in the vanadium sulfate acyl enters solution, can reduce the influence of sulfate ion to the finished product purity, and on the other hand, ammonium sulfate returns use as the precipitation agent of aluminium, iron;
Oxidizing roasting: vanadium hydroxide and oxygen are calcined under 450～600 ℃ of temperature condition, obtain Vanadium Pentoxide in FLAKES.
Wherein, contain the vanadium material and comprise and contain the natural ore deposit of vanadium and contain the vanadium industrial residue, as contain the scherbinaite coal, contain vanadium shale, contain the vanadium clay, contain the vanadium mine tailing, vanadium titano-magnetite, vanadium containing catalysts, v-bearing steel slag, contain the scherbinaite putty, contain vanadium cinder etc.; The acidic substance that certain association is arranged are phosphoric acid, phosphoric acid salt, sulfuric acid and vanadic acid (Vanadium Pentoxide in FLAKES); Acidic substance phosphoric acid, sulfuric acid and the weight ratio that contains the vanadium material are 1: 2: 10～1: 10: 50.
The first step leaching temperature of reaction of three stage countercurrents leaching reaction is 80～100 ℃, and the reaction times is 2～5 hours; The second stage leaching temperature of reaction of three stage countercurrents leaching reaction is 90～110 ℃, and the reaction times is 1～3 hour; The third stage leaching temperature of reaction of three stage countercurrents leaching reaction is 100～120 ℃, and the reaction times is 0.5～2 hour.
The alkali metal sulfates that is adopted is vitriolate of tartar, sodium sulfate, ammonium sulfate, the preferably sulfuric acid ammonium; Used reductive agent is sodium sulphite, iron powder, zinc powder etc., preferred iron powder.
The weight ratio of aluminium is 10: 3～10: 6 in the weight of the alkali metal sulfates that adds and the solution for the first time, preferred 10: 4～10: 5; Cooling temperature is at 5～30 ℃, preferred 10～20 ℃; Keep the concentration of vitriol in the solution in 20%～30% (weight ratio) after adding for the second time alkali metal sulfates; The ratio of ferric amount of substance is 1: 3～1: 1 in the amount of substance that adds reductive agent and the solution.
Filtrate concentration of vanadium after evaporation concentration is 15%～20% (weight ratio).
Vitriolic concentration is controlled at 3～9mol/L, preferred 4～6mol/L after adding the vitriol oil; Cooling temperature is 5～30 ℃, preferred 15～25 ℃; PH=3～8 of solution after the adding ammoniacal liquor neutralization reaction, preferred pH=4～6; The calcining temperature of vanadium hydroxide is controlled at 300～800 ℃, preferred 450～600 ℃.
The present invention adopts association formula ionogen three stage countercurrents efficiently to leach, and the leaching yield of vanadium reaches more than 95%; The precipitation process does not add other salt such as ammonium chloride, and vanadium directly settles out from mother liquor with the vanadium sulfate acyl crystalline form, does not produce brine waste, and sulfate liquor returns recycle; Vanadium Pentoxide in FLAKES is compared with the ammonium meta-vanadate pyrolysis by vanadium hydroxide oxidizing roasting preparation, and temperature of reaction is low, and product purity is up to more than 99.5%, and does not have ammonia-contaminated gas to produce; Aluminium, iron valuable element have obtained recovery, have realized the comprehensive utilization of Mineral resources.The present invention has the technical process weak point, and energy consumption is little, vanadium yield height, and production cost is low, environmental protection, the advantage of valuable metal element comprehensive utilization in the ore.
The present invention has following advantage compared with the prior art:
1, do not have selectivity to containing vanadium raw materials, variously contain the vanadium waste residue and contain navajoite stone and all be suitable for.
2, do not add sodium-salt calcination, solved the pollution problem that produces a large amount of toxic gases in the sodium roasting process.
3, adopt the hydrometallurgical processes route, containing the vanadium raw material of substance is wet grinding, does not have dust pollution.
4, leaching process adopts the acid with association as leaching agent, adds three stage countercurrents reinforcement leaching, and the leaching rate height reaches more than 98%.
5, other valuable elements in the raw material have obtained comprehensive reutilization, the resource utilization height.
6, compare with high temperature sodium sinter process, the wet method leaching process temperature is low, 80～120 ℃, has reduced energy consumption.
7, valuable elements such as aluminium, iron, vanadium mainly obtain crystalline deposit by salting out from solution, and technical process is simple, and process cost is low.
8, Vanadium Pentoxide in FLAKES is to be obtained by purified vanadium dioxide heated oxide, and the product purity height can reach more than 99%.Compare with the ammonium meta-vanadate pyrolysis, both reduced calcining temperature, do not have ammonia emission again, realized energy-saving and environmental protection.
9, total system adopts the closed cycle operation, has realized the innoxious comprehensive utilization of cleaner production and resource.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is described further below in conjunction with specific embodiment.
Embodiment 1:
Contain navajoite stone A, its composition (weight ratio) composed as follows: V
2O
51.2%, SiO
276.3%, Al
2O
36.7%, Fe
2O
33.2%, FeO 2.6%, and CaO 0.8%, and K 1.0%, and Na 0.6%, P
2O
50.1%, other are 7.5% years old.
To contain navajoite stone A fragmentation, wet grinding to 60～80 orders, and get 120 kilograms (dry weight) and add the standby filtrate 2 that next stage returns, be heated to 90～100 ℃, react 3.5 hours, filter, obtain filtrate 3 and filter cake 1; Filter cake 1 mixes with standby filtrate 1, is heated to 95～100 ℃, reacts 2 hours, filter, obtain standby filtrate 2 and filter cake 2, standby filtrate 2 is used for and raw ore reaction, filter cake 2 and 6.8 kilograms of phosphoric acid, 42 kilo sulfuric acid and double centner water mix, 100 ℃ of stirring reactions 1 hour, filter, standby filtrate 1 and filter cake 3, filter cake 3 is made cement admixture after washing, standby filtrate 1 is returned leaching filter cake 2.
In filtrate 3, add 10～12 kilograms in ammonium sulfate, stirred 20～30 minutes, be cooled to below 20 ℃, filter, get ten sulfate dihydrate aluminium ammonium crystal; Add 1.3～1.5 kilograms of reductive agent iron powders then in filtrate, 35～45 kilograms in ammonium sulfate stirred 10～20 minutes, was cooled to below 20 ℃, filtered, and obtained the ferrous ammonium sulphate crystal, and filtrate is returned the leaching ore as water.
Circulate like this 8～10 times, the concentration of vanadium runs up to more than 10% (weight ratio) gradually in the solution, evaporation concentration is approaching saturated to vanadium, the vitriol oil of slowly adding 95%～98% (weight ratio) under agitation condition is 40 kilograms then, be cooled to 20～25 ℃, filter, get the vanadium sulfate acyl crystal, contain vitriolic filtrate and return the leaching navajoite.
The vanadium sulfate acyl crystal is slowly mixed with weak ammonia, pH=4～6 of control solution, mixing finishes, and still aging 30～90 minutes, filter, get the vanadium hydroxide solid precipitation, filtrate is ammoniumsulphate soln, returns behind the condensing crystal as aluminium, iron precipitation agent.
Vanadium hydroxide and oxygen were calcined 30 minutes under 450～600 ℃ of temperature condition, and cooling obtains Vanadium Pentoxide in FLAKES, and purity reaches 99.8%, and the vanadium yield reaches 97.8%.
Embodiment 2:
Contain navajoite stone B, its composition (weight ratio) composed as follows: V
2O
51.6%, SiO
216.3%, C 63.8%, Al
2O
37.3%, Fe
2O
31.2%, FeO 4.3%, and CaO 0.8%, and K 0.3%, and Na 0.2%, and other are 4.2% years old.
To contain navajoite stone B fragmentation, wet grinding to 60～80 orders, and get 120 kilograms (dry weight) and add the standby filtrate 2 that next stage returns, be heated to 85～95 ℃, react 4.5 hours, filter, obtain filtrate 3 and filter cake 1; Filter cake 1 mixes with standby filtrate 1, is heated to 95～100 ℃, reacts 3 hours, filter, obtain standby filtrate 2 and filter cake 2, standby filtrate 2 is used for and raw ore reaction, filter cake 2 and 8.3 kilograms of phosphoric acid, 36 kilo sulfuric acid and double centner water mix, 100 ℃ of stirring reactions 1 hour, filter, standby filtrate 1 and filter cake 2, filter cake 3 is made cement admixture after washing, standby filtrate 1 is returned leaching filter cake 2.
In filtrate 3, add 11～13 kilograms in ammonium sulfate, stirred 20～30 minutes, be cooled to below 25 ℃, filter, get ten sulfate dihydrate aluminium ammonium crystal; Add 0.5～0.7 kilogram of reductive agent iron powder then in filtrate, 30～35 kilograms in ammonium sulfate stirred 10～20 minutes, was cooled to below 20 ℃, filtered, and obtained the ferrous ammonium sulphate crystal, and filtrate is returned the leaching ore as water.
Circulate like this 8～10 times, the concentration of vanadium runs up to more than 10% (weight ratio) gradually in the solution, evaporation concentration is approaching saturated to vanadium, the vitriol oil of slowly adding 95%～98% (weight ratio) under agitation condition is 40 kilograms then, be cooled to below 20 ℃, filter, get the vanadium sulfate acyl crystal, contain vitriolic filtrate and return the leaching navajoite.
The vanadium sulfate acyl crystal is slowly mixed with weak ammonia, pH=4～6 of control solution, mixing finishes, and still aging 30～90 minutes, filter, get the vanadium hydroxide solid precipitation, filtrate is ammoniumsulphate soln, returns behind the condensing crystal as aluminium, iron precipitation agent.
Vanadium hydroxide and oxygen were calcined 30 minutes under 500～550 ℃ of temperature condition, and cooling obtains Vanadium Pentoxide in FLAKES, and purity reaches 99.6%, vanadium recovery 98.2%.
Embodiment 3:
Industrial residue C, its composition (weight ratio) composed as follows: V
2O
54.2%, SiO
22 6.3%, Al
2O
311.7%, Fe
2O
30.2%, FeO 35.6%, and CaO 10.8%, and other are 3.7% years old.
With industrial residue C fragmentation, wet grinding to 60～80 orders, get 120 kilograms (dry weight) and add the standby filtrate 2 that next stage returns, be heated to 80～90 ℃, reacted 2.5 hours, filter, obtain filtrate 3 and filter cake 1; Filter cake 1 mixes with standby filtrate 1, is heated to 90～95 ℃, reacts 1 hour, filter, obtain standby filtrate 2 and filter cake 2, standby filtrate 2 is used for and industrial residue reaction, filter cake 2 and 36 kilograms of phosphoric acid, 96 kilo sulfuric acid and 180 kg water are mixed, 100 ℃ of stirring reactions 0.5 hour, filter, standby filtrate 1 and filter cake 3, filter cake 3 is made cement admixture after washing, standby filtrate 1 is returned leaching filter cake 2.
In filtrate 3, add 18～21 kilograms in ammonium sulfate, stirred 20～30 minutes, be cooled to below 20 ℃, filter, get ten sulfate dihydrate aluminium ammonium crystal; Add 0.1～0.2 kilogram of reductive agent iron powder then in filtrate, 100～135 kilograms in ammonium sulfate stirred 40～60 minutes, was cooled to below 25 ℃, filtered, and obtained the ferrous ammonium sulphate crystal, and filtrate is returned the leaching ore as water.
Circulate like this 3～4 times, the concentration of vanadium runs up to more than 10% (weight ratio) gradually in the solution, evaporation concentration is approaching saturated to vanadium, the vitriol oil of slowly adding 95%～98% (weight ratio) under agitation condition is 42 kilograms then, be cooled to below 20 ℃, filter, get the vanadium sulfate acyl crystal, contain vitriolic filtrate and return the leaching navajoite.
The vanadium sulfate acyl crystal is slowly mixed with weak ammonia, pH=4～6 of control solution, mixing finishes, and still aging 30～90 minutes, filter, get the vanadium hydroxide solid precipitation, filtrate is ammoniumsulphate soln, returns behind the condensing crystal as aluminium, iron precipitation agent.
Vanadium hydroxide and oxygen were calcined 40 minutes under 550～600 ℃ of temperature condition, and cooling obtains Vanadium Pentoxide in FLAKES, and purity reaches 99.7%, vanadium recovery 98.7%.
Claims (8)
1. one kind is cleaned the method for extracting Vanadium Pentoxide in FLAKES from contain the vanadium material, it is characterized in that taking following steps:
(1), association formula ionogen three stage countercurrents efficiently leach: mix according to certain weight ratio with water and the acidic substance with certain association after will containing the wet grinding of vanadium material, under the temperature of setting, time conditions, carry out three stage countercurrents leaching reaction, leaching slag as cement mixture material material;
(2), reaction/separation coupling crystalline deposit: in the reaction leach liquor of step (1), add the alkali metal sulfates of manipulated variable, stir, cool off, filter, obtain the double salt crystal of Tai-Ace S 150; And then in filtrate, adding alkali metal sulfates and reductive agent, stirring reaction obtains the double salt crystal of ferrous sulfate, filtering separation; When the concentration of vanadium in the filtrate is lower than 10%, turns back to step (1) leaching navajoite and recycle; When the concentration of vanadium in the filtrate is higher than 10%, enter into step (3);
(3), the vanadium sulfate acyl crystallization is separated out: the filtrate behind step (2) separation aluminium, the iron adds the vitriol oil to finite concentration then through evaporation concentration, and crystallisation by cooling filters, and obtains the vanadium sulfate acyl crystal, and filtrate is returned step (1) leaching and contained the vanadium material;
(4), in the vanadic salts and conversion: vanadium sulfate acyl crystal and ammoniacal liquor that step (3) is obtained carry out neutralization reaction, obtain the vanadium hydroxide precipitation, and sulfate ion transfers to that formation ammonium sulfate turns back to step (2) in the solution;
(5), oxidizing roasting: vanadium hydroxide and oxygen are calcined under the design temperature condition, obtain Vanadium Pentoxide in FLAKES.
According to claim 1 described from contain the vanadium material cleaning extract the method for Vanadium Pentoxide in FLAKES, it is characterized in that: contain the vanadium material and comprise and contain the natural ore deposit of vanadium and contain the vanadium industrial residue; The acidic substance that certain association is arranged are phosphoric acid, phosphoric acid salt, sulfuric acid and vanadic acid.
According to claim 2 described from contain the vanadium material cleaning extract the method for Vanadium Pentoxide in FLAKES, it is characterized in that: acidic substance phosphoric acid, sulfuric acid and the weight ratio that contains the vanadium material are 1: 2: 10～1: 10: 50.
4. according to the described method of extracting Vanadium Pentoxide in FLAKES that cleans from contain the vanadium material of claim 3, it is characterized in that: the first step leaching temperature of reaction of three stage countercurrents leaching reaction is 80～100 ℃, and the reaction times is 2～5 hours; The second stage leaching temperature of reaction of three stage countercurrents leaching reaction is 90～110 ℃, and the reaction times is 1～3 hour; The third stage leaching temperature of reaction of three stage countercurrents leaching reaction is 100～120 ℃, and the reaction times is 0.5～2 hour.
5. according to claim 1 or the 4 described methods of extracting Vanadium Pentoxide in FLAKES that clean from contain the vanadium material, it is characterized in that: the alkali metal sulfates that is adopted is vitriolate of tartar, sodium sulfate, ammonium sulfate, the preferably sulfuric acid ammonium; Used reductive agent is sodium sulphite, iron powder, zinc powder, preferred iron powder; The weight ratio of aluminium is 10: 3～10: 6 in the weight of the alkali metal sulfates that adds and the solution for the first time, preferred 10: 4～10: 5; Cooling temperature is at 5～30 ℃, preferred 10～20 ℃; Keep the concentration of vitriol in the solution 20%～30% after adding for the second time alkali metal sulfates; The ratio of ferric amount of substance is 1: 3～1: 1 in the amount of substance that adds reductive agent and the solution.
6. according to the described method of extracting Vanadium Pentoxide in FLAKES that cleans from contain the vanadium material of claim 5, it is characterized in that: filtrate concentration of vanadium after evaporation concentration is 15%～20%; Vitriolic concentration is to be controlled at 3～9mol/L, preferred 4～6mol/L behind the adding vitriol oil; Cooling temperature is 5～30 ℃, preferred 15～25 ℃.
7. according to the described method of extracting Vanadium Pentoxide in FLAKES that from contain the vanadium material, cleans of claim 6, it is characterized in that: pH=3～8 of solution after the adding ammoniacal liquor neutralization reaction, preferred pH=4～6.
8. according to the described method of extracting Vanadium Pentoxide in FLAKES that cleans from contain the vanadium material of claim 7, it is characterized in that: the calcining temperature of vanadium hydroxide is controlled at 300～800 ℃, preferred 450～600 ℃.
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| CN115557535A (en) * | 2022-11-14 | 2023-01-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium oxide by reducing sodium vanadate zinc powder and recycling water |
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| CN115557535B (en) * | 2022-11-14 | 2023-12-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium oxide by reducing sodium vanadate zinc powder and recycling water |
| CN115807172B (en) * | 2022-11-29 | 2024-01-26 | 武汉科技大学 | Method for extracting valuable elements from vanadium shale |
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