CN107177742A - A kind of method that vanadium is extracted from bone coal - Google Patents
A kind of method that vanadium is extracted from bone coal Download PDFInfo
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- CN107177742A CN107177742A CN201710436020.7A CN201710436020A CN107177742A CN 107177742 A CN107177742 A CN 107177742A CN 201710436020 A CN201710436020 A CN 201710436020A CN 107177742 A CN107177742 A CN 107177742A
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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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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Abstract
The invention discloses a kind of method that vanadium is extracted from bone coal, it is characterised in that the mixed liquor comprising phosphate radical complexing agent, oxidant, acid, bone coal is carried out into oxidation complexation leaching；Through separation of solid and liquid after, obtain containing vanadium leachate and leached mud；The concentration of P elements is more than or equal to 1mol/L in mixed liquor.Vanadium in leachate is obtained alkaline rich vanadium liquid with anionic form after solvent extraction or Ion exchange process.Into rich vanadium liquid, acid adding is adjusted and soluble calcium salt is added after pH, and phosphorus reacts with calcium and generates precipitation, so as to realize phosphorus and the separation of vanadium and recycling for phosphorus.Solution after dephosphorization is by ammonium salt precipitation and calcines and obtains high-quality vanadic anhydride product.The present invention does not need roasting process, smoke-less pollution；Just the V leaching rate more than 94.5% can be obtained under conditions of extraction temperature is less than 200 DEG C.
Description
Technical field
The present invention relates to a kind of method that vanadium is extracted from bone coal；Belong to field of hydrometallurgy.
Background technology
Bone coal is a kind of important resource containing vanadium mineral, the low-grade complex mineral of the difficult smelting of the difficult choosing of category.The generation of reproducibility
Environment cause in bone coal vanadium the overwhelming majority with V (III) form exist and preservation in mica minerals such as muscovite, illites
In.At present, the technique for vanadium being extracted from bone coal is broadly divided into two types：(1) oxidizing roasting technique, mainly including direct oxidation
Roasting-acid (alkali) extract technology, addition calcium (magnesium) salt oxidizing roasting-sulfuric acid or phosphate extract technology and addition sodium salt oxidation roasting
Burning-water (acid) extract technology.Direct oxidation roasting-acid (alkali) extract technology is by V (III), the V in bone coal by oxidizing roasting
(IV) be oxidized to the vanadic anhydride for dissolving in bronsted lowry acids and bases bronsted lowry, then by sulfuric acid by vanadium with VO2 +Form leach or pass through hydrogen-oxygen
Change sodium by vanadium with VO4 3-Form leach.Plus calcium (magnesium) salt oxidizing roasting-sulfuric acid or phosphate extract technology are added in bone coal
Plus calcium (magnesium) salt, then the V (III) in bone coal, V (IV) are aoxidized by oxidizing roasting and the calcium vanadate (magnesium) of pentavalent is converted into
Or many calcium vanadates (magnesium), then using calcium sulfate, calcium phosphate or ammonium magnesium phosphate solubility product than calcium vanadate (magnesium) or many calcium vanadates
(magnesium) lower principle realizes the leaching of vanadium.Addition sodium salt oxidizing roasting-water (acid) extract technology is by stone by oxidizing roasting
V (III), V (IV) in coal are aoxidized and are converted into the sodium vanadate or many sodium vanadates of pentavalent, then realize carrying for vanadium by leaching
Take.Oxidizing roasting technique or due to seriously polluted or because V leaching rate is low or because the interval narrow industry of optimum calcination temperature should
With reasons such as difficulties, popularization and application of all having no idea.(2) the direct wet process acid extract technology of bone coal, directly soaks including sulfuric acid
Go out technique, oxygen pressure Ore Leaching technique and addition fluoride Ore Leaching technique etc..Such technology is the oxygen using V (III) and V (IV)
Compound can be with acid reaction principle, realize the leaching of vanadium in bone coal.Sulfuric acid direct leaching process is only applicable to that to adsorb
The bone coal existed based on state vanadium, 60% is below for common bone coal V leaching rate；Addition fluoride Ore Leaching technique can be obtained
90% even more high V leaching rate, but lack the fluoride waste and waste gas containing fluoride for effectively administering technique generation at present
Means, environmental pollution is big；Oxygen pressure Ore Leaching technique general principle is to use oxygen or hydrogen peroxide for oxidant, with sulfuric acid to leach
Agent, under certain temperature, pressure and reaction time, V (III) is oxidized in V (IV) and vitriolization solution.Oxygen presses Ore Leaching
Technique can apply to all types bone coal, and the leaching rate relative to sulfuric acid direct leaching process vanadium is greatly improved, but also there was only 70-
80%；Only the leaching rate of oxygen leaching vanadium can be only achieved 95% at 300 DEG C.For oxygen pressure Ore Leaching, once temperature
More than 200 DEG C, either the requirement to equipment material or operation cost can all be greatly increased.Add soluble ferrite conduct
Oxygen presses the catalyst of Ore Leaching, can also significantly improve the leaching rate of vanadium, but can contain substantial amounts of Fe in leachate3+, its is dense
1.5~3 times of the reachable V concentration of degree.
The mode of separation and concentration vanadium only has cation solvent extraction one kind to be applied to from highly acid bone coal leachate at present
Industrialization, but be due to that P204 preferentially extracts Fe3+, so needing to carry out reduction treatment before extraction, this process needs a large amount of
Reducing agent, whole process cost is high, complex process.For P204 extracting vanadiums, anion exchange resin or alkalescence extraction
Take agent separation and Extraction vanadium that there is more preferable separating effect and Geng Gao recovery rate, but anion exchange resin and basic extractant are only
V (V) in energy separation and concentration leachate, because only that V (V) can just form isopolyacid anion.In highly acid bone coal leachate
Middle V (V) is with VO2 +Form is present, and when only pH value of solution is more than 2.0 or so, V (V) could be deposited with isopolyacid anionic form
Yet with a large amount of Fe3+Presence, regulation leachate pH processes vanadium can be precipitated in the form of many ferric vandate, the loss of vanadium
Rate even can be more than more than 90%.
The content of the invention
The defect existed for the above-mentioned various handling process in the prior art to bone coal, it is an object of the invention to provide
A kind of a kind of method that vanadium is extracted from bone coal, it is desirable to provide extracting method high without roasting, mild condition, vanadium recovery.
A kind of method that vanadium is extracted from bone coal, the mixed liquor comprising phosphate radical complexing agent, oxidant, acid, bone coal is entered
Row oxidation-complexation leaching；Through separation of solid and liquid after, obtain containing vanadium leachate and leached mud；The concentration of P elements is big in mixed liquor
In or equal to 1mol/L.
The one kind of the invention that solely innovatively provides makes vanadium with vanadium phospha using phosphate radical as complexing agent, under oxidant, acid
The step of form one of polyacid is leached；The inventive method is without high-temperature roasting, mild condition, and V leaching rate is high.
In the present invention, described phosphorous acid group complexing agent be in water it is ionizable go out PO4 3-Compound, or described
Mixed liquor acid condition under can be electrolysed out PO4 3-Compound.
Preferably, described phosphate radical complexing agent is in phosphoric acid, dihydric phosphate, dibasic alkaliine, phosphoric acid normal salt
It is at least one.
Dihydric phosphate can be H2PO4 -The water soluble salt such as alkali metal salt, ammonium salt.
Dibasic alkaliine can be HPO4 2-The water soluble salt such as alkali metal salt, ammonium salt.
Phosphoric acid normal salt can be PO4 3-The water soluble salt such as alkali metal salt, ammonium salt.
Further preferably, described phosphate radical complexing agent is in phosphoric acid, sodium dihydrogen phosphate, disodium-hydrogen, sodium phosphate
It is at least one.
The inventors discovered that, the concentration of described phosphate radical has influence to leaching effect.
Preferably, the concentration of P elements is 1.0mol/L~10mol/L in leachate；More preferably 2.0mol/L
~6mol/L；Still more preferably it is 2.0mol/L~3.5mol/L.
In the present invention, V (III) and V (IV) compound for being oxidized to V (V) can be can be employed as oxidant in theory；Mark
Quasi- oxidation-reduction potential is more than E0 v(v)/V(IV)Compound can be employed as oxidant.
Preferably, described oxidant is chloric acid and/or chlorate.
Described chlorate is such as can the water soluble salt for the alkali metal salt of chlorate anions, ammonium salt.
Further preferably, described oxidant is sodium chlorate.
Preferably, the addition of oxidant is that V in bone coal (III) and V (IV) are oxidized to the 1~3 of V (V) theoretical amount
Times.
In the present invention, described acid can be existing conventional organic or inorganic water soluble acid.If, described phosphate radical
Complexing agent and/or oxidant introduce H+, also can be as needed, do not add described acid additionally.
Preferably, described acid is at least one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid.
Preferably, the H in mixed liquor+Concentration is 1~14mol/L.
Preferably, the particle mean size of bone coal≤120 mesh；The solid-to-liquid ratio of mixed liquor is 1: 1.1~5g/ml.Mixed liquor
Solid-to-liquid ratio is：The weight of bone coal solid in mixed liquor with comprising phosphate radical complexing agent, oxidant, acid the aqueous solution volume
Than.
In the present invention, described oxidation-complexation leaching process is carried out preferably under closed container.
Preferably, the temperature of oxidation-complexation leaching process is 70~200 DEG C；More preferably 140~180 DEG C.
Under conditions of this is preferred, V leaching rate is higher.
During oxidation-complexation leaching, it is described under confined conditions and at a temperature of, oxidation-complexation leaching process
Pressure is 0.5~7Mpa；More preferably 0.5~4Mpa.
In the present invention, it is preferred to use following methods are extracted containing the vanadium in vanadium leachate：
Adjust the pH containing vanadium leachate and be less than or equal to 2；Extracted after through extractant, alkali is stripped, or through ion exchange
Alkaline hydrolysis is analysed again after resin adsorption；Obtain alkaline rich vanadium liquid.
In the present invention there is provided two kinds it is preferred from described containing the mode that vanadium is extracted in vanadium leachate：
Mode 1：The pH containing vanadium leachate is adjusted to less than or equal to 2；Again with extractant hybrid extraction, separation
Obtain being enriched with the load organic phases of vanadium, then load organic phases are stripped using alkali, obtain being stripped phase, be that alkalescence is rich
Vanadium liquid.
Mode 2：The pH containing vanadium leachate is adjusted to less than or equal to 2；After being adsorbed again with ion exchange resin,
Then loaded resin is parsed using alkali again, desorbed solution is obtained, is the rich vanadium liquid of alkalescence.
Preferably, extractant be with primary amine groups, secondary amine, tertiary amine groups, quaternary amine base basic extractant.
For example, the extractant used is at least one of N235, N1923, N263, TOA.
Preferably, ion exchange resin be with primary amine groups, secondary amine, tertiary amine groups, quaternary amine base anion exchange resin.
For example, the ion exchange resin trade mark used is at least one of 201 × 7, D301, D290, D314.
Preferably, the alkali that alkali back extraction and alkali resolving are used is independently chosen from sodium hydroxide solution, ammonia spirit, hydrogen-oxygen
Change at least one of sodium and sodium chloride mixed solution, ammoniacal liquor and ammonium chloride mixed solution.
Preferably, the alkali added in containing vanadium leachate, regulation pH is to less than or equal to 2；Described alkali is hydroxide
In sodium, sodium carbonate, potassium hydroxide, potassium carbonate, ammoniacal liquor, ammonium carbonate, ammonium hydrogen carbonate, calcium hydroxide, calcium oxide, calcium carbonate at least
It is a kind of.
Preferably, pH of the regulation containing vanadium leachate is 0~2.
Present invention also offers a kind of method that vanadium is extracted in rich vanadium liquid from described alkalescence：The pH of the rich vanadium liquid of regulation and control alkalescence
It is worth for 8~14 (being preferably 9~10), then adds calcium source, stirring, precipitation obtain dephosphorization vanadium liquid and phosphorus after through separation of solid and liquid
Calcium precipitate；
Ammonium salt is added into dephosphorization vanadium liquid, the ammonium salt compound for obtaining vanadium is separated out, then calcines to obtain five oxygen for 450~650 DEG C
Change two vanadium products；
Solution recycled after phosphorus calcium precipitate is sulfuric acid-treated is to oxidation-complexation leaching process.
Described calcium source is Ca2+Water soluble compound.
Preferably, calcination time is 1~5h.
A kind of preferred method that vanadium is extracted from bone coal of the present invention, comprises the following steps：
Step (1)：Using phosphate anion as complexing agent, using sodium chlorate as oxidant, H is used+Concentration is 1~14mol/L's
Acid solution does leaching solvent, by 1: 1.1~5g/ml of solid-to-liquid ratio by the bone coal of the mesh of particle mean size≤120 with leachate in pressure
Mixed in reactor, be 0.5~7Mpa in pressure, temperature is under the conditions of 70~200 DEG C, leaches 0.5~6h, and leaching is solid after terminating
Liquid is separated, and obtains leachate containing vanadic acid and leached mud；The concentration of P elements is 1-10mol/L in leaching solvent；
Step (2)：To leachate containing vanadic acid add alkali adjust solution ph be 0~2, using solvent extraction or ion exchange come
Vanadium in separation and concentration leachate containing vanadic acid, is stripped or parsed using alkaline solution, obtains alkaline rich vanadium liquid；
Step (3)：Acid adding alkali tune richness vanadium liquid pH value is 8~14, then adds CaCl220~100 DEG C of stirring 5-
120min filters the calcium phosphate precipitation containing vanadium solution and calcium after must purifying.After purification ammonium salt deposition method is used containing the vanadium in vanadium solution
The ammonium salt compound of vanadium is obtained, then 450~650 DEG C of 1~5h of calcining obtain vanadic anhydride product；The calcium phosphate precipitation sulphur of calcium
Acid carrys out recovery phosphoric acid and returns to step (1).
Currently preferred method, it is not necessary to be calcined, vanadium recovery is high, leaching process complexing agent can be recycled, vanadium
Separation and concentration process does not need that reduction treatment, whole process be environment-friendly, production cost is low, meets industrialization production requirements.
Further preferably, in step (1), the phosphate anion is by phosphoric acid, dihydric phosphate, dibasic alkaliine, phosphoric acid
At least one of normal salt is provided, preferably at least one of phosphoric acid, sodium dihydrogen phosphate, disodium-hydrogen, sodium phosphate.
Further preferably, it is described to refer to that sodium chlorate solid or sodium chlorate are molten by oxidant of sodium chlorate in step (1)
Liquid, the addition of sodium chlorate is oxidized to 1~3 times of addition of V (V) theoretical amount according to V in bone coal (III) and V (IV).
Further preferably, in step (1), the H in the leachate+By at least one in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid
Plant and provide.
Further preferably, in step (2), described plus alkali regulation solution ph refers to adding sodium hydroxide, sodium carbonate, hydrogen
At least one of potassium oxide, potassium carbonate, ammoniacal liquor, ammonium carbonate, ammonium hydrogen carbonate, calcium hydroxide, calcium oxide, calcium carbonate.
Further preferably, in step (2), the solvent extraction, which refers to using, carries primary amine groups, secondary amine, tertiary amine groups, season
The vanadium that the basic extractant of amido comes in separation and concentration leachate containing vanadic acid.
Further preferably, in step (2), the ion exchange refers to using band primary amine groups, secondary amine, tertiary amine groups, season
The vanadium that the anion exchange resin of amido comes in separation and concentration leachate containing vanadic acid.
Further preferably, in step (2), the back extraction of use alkaline solution or parsing refer to molten using sodium hydroxide
At least one of liquid, ammonia spirit, sodium hydroxide and sodium chloride mixed solution, ammoniacal liquor and ammonium chloride mixed solution are carried out.
Preferably, in step (3), the acid refers at least one of sulfuric acid, nitric acid, hydrochloric acid.
Preferably, in step (3), the addition CaCl2Refer to reacting according to calcium ion and phosphate anion and generate
Ca3(PO4)21~3 times of addition of theoretical amount.
The present invention principle be：
V (IV) and V (III) in bone coal is oxidized to V (V) by the present invention in an acidic solution using sodium chlorate as oxidant,
With phosphate anion complex reaction generation heteropoly acid occurs for V (V) simultaneously, so as to destroy crystal phase structure containing roscoelite in bone coal, obtains
Obtain high V leaching rate.Vanadium in leachate is adsorbed in heteropolyacid anions form by solvent extraction or ion exchange, back extraction or solution
Vanadium is main with VO in the rich vanadium liquid of alkalescence obtained after analysis4 3-And V2O7 4-Form is present, and phosphorus is mainly with PO4 3-Form is present.Acid adding is adjusted
Soluble calcium salt is added after pH, phosphorus can react generation Ca with calcium3(PO4)2Or CaHPO4Precipitation, so as to realize the separation of phosphorus and vanadium.
Solution after dephosphorization is by ammonium salt precipitation and calcines and will obtain high-quality vanadic anhydride product.The calcium phosphate precipitation of calcium with
Sulfuric acid reaction generates CaSO4Precipitation and H3PO4Solution, while a small amount of vanadium of dephosphorization process losses can also be entered with sulfuric acid reaction
H3PO4Solution.Obtained H3PO4Solution returns to leaching step cycle and used.
Beneficial effect：
The main cause that vanadium in bone coal is difficult to extract be the main preservation of vanadium in mica, illite clay mineral, this
Class mineral structure is stable, it is difficult to destroyed.And oxygen pressure complexing Ore Leaching can readily destroy this mineral structure, while vanadium meeting
With PV12O36 7-、PV14O42 9-Enter solution etc. form.The present invention does not need roasting process, smoke-less pollution；With conventional directly oxygen
Pressure leaching is compared, and being less than in extraction temperature just can obtain the leaching rate for being up to 98.7% under conditions of 200 DEG C, and cost is low, pair set
The requirement of standby material is low；Complexing agent phosphate radical can be recycled, vanadium separation and concentration process does not need reduction treatment, it is organic to extract
Iron regenerative process is removed also without progress；The rate of recovery of vanadium can be more than 93.6%.Whole process technique is simple, operation letter
Just, production cost is low, environment-friendly.
Embodiment
Following examples are intended to further illustrate present invention, rather than make further limit to protection scope of the present invention
It is fixed.
Embodiment 1
- 150 mesh bone coal 500g containing 1.2%V are taken, 600g NaH are added2PO4Make complexing agent, by V in bone coal (III) and V
(IV) 1.5 times of addition sodium chlorate of V (V) theoretical amount are oxidized to, are added by solid-to-liquid ratio 1: 3g/mL (on the basis of bone coal weight)
1.5mol/L H2SO4Solution is mixed in pressure reaction still, in confined conditions 140 DEG C of pressure leaching 4h, and liquid divides admittedly after cooling
From obtaining containing vanadium leachate, the leaching rate of vanadium is 98.1%.
To being 0.5 containing calcium oxide regulation pH value of solution is added in vanadium leachate, extract and separate, sodium hydroxide are carried out using N235
Solution is stripped, and obtains alkaline rich vanadium liquid.It is 10.0 to add sulfuric acid regulation solution pH into alkaline rich vanadium liquid, then according to calcium
Ion and phosphate anion reaction generation Ca3(PO4)21.2 times of addition CaCl of theoretical amount2It is stirred at room temperature after 1.5h, solid-liquor separation
Calcium phosphate precipitation containing vanadium solution and calcium after must purifying.After purification the inclined vanadium of basic ammonium salts precipitation method Precipitation is used containing vanadium solution
Sour ammonium, 500 DEG C of calcining 2h obtain the V that purity is 99.3%2O5.The calcium phosphate precipitation of calcium and sulfuric acid reaction generate hydrated gypsum and
Phosphoric acid, separation of solid and liquid obtains phosphoric acid solution.Whole process vanadium is recovered as 96.8%.
Comparative example 1
- 150 mesh bone coal 500g containing 1.2%V are taken, the 1.5 of V (V) theoretical amount are oxidized to by V in bone coal (III) and V (IV)
Sodium chlorate is added again, and 1.5mol/L H is added by solid-to-liquid ratio 1: 3g/mL2SO4Solution is mixed in pressure reaction still, in closed bar
The lower 140 DEG C of pressure leaching 4h of part, solid-liquor separation after cooling is obtained containing vanadium leachate, the leaching rate of vanadium is 74.3%.
Embodiment 2
- 200 mesh bone coal 500g containing 0.4%V are taken, 2 times of V (V) theoretical amount are oxidized to by V in bone coal (III) and V (IV)
Sodium chlorate is added, is added by solid-to-liquid ratio 1: 1.5g/mL (on the basis of bone coal weight) in embodiment 1 and has been diluted to 4mol/L's
Phosphoric acid solution is mixed in pressure reaction still, in confined conditions 160 DEG C of pressure leaching 3h, and solid-liquor separation after cooling is obtained containing vanadium
Leachate, the leaching rate of vanadium is 95.8%.
To being 1.0 containing sodium carbonate regulating solution pH is added in vanadium leachate, it is enriched with using ion exchange resin D314
Separation, sodium hydroxide solution is parsed, and obtains alkaline rich vanadium liquid.Adding sulfuric acid regulation solution pH into alkaline rich vanadium liquid is
9.5, then according to calcium ion and phosphate anion reaction generation Ca3(PO4)21.5 times of addition CaCl of theoretical amount260 DEG C of stirrings
Calcium phosphate precipitation containing vanadium solution and calcium after must being purified after 0.5h, solid-liquor separation.It is heavy using acid ammonium salt containing vanadium solution after purification
Vanadium method Precipitation ammonium poly-vanadate, 550 DEG C of calcining 2h obtain the V that purity is 99.1%2O5.The calcium phosphate precipitation of calcium and sulfuric acid are anti-
Hydrated gypsum and phosphoric acid should be generated, separation of solid and liquid obtains phosphoric acid solution.Whole process vanadium is recovered as 94.3%.
Embodiment 3
- 180 mesh bone coal 500g containing 0.8%V are taken, the 1.5 of V (V) theoretical amount are oxidized to by V in bone coal (III) and V (IV)
Sodium chlorate is added again, is added by solid-to-liquid ratio 1: 4g/mL (on the basis of bone coal weight) in embodiment 1 and has been diluted to 3.5mol/L
Phosphoric acid solution, then add 400g Na3PO4Mixed in pressure reaction still, in confined conditions 180 DEG C of pressure leaching 2h,
Solid-liquor separation after cooling, is obtained containing vanadium leachate, the leaching rate of vanadium is 98.7%.
To being 2.0 containing sodium hydrate regulator solution pH is added in vanadium leachate, entered using anion exchange resin 201 × 7
Row concentration and separation, sodium hydroxide and sodium chloride mixed solution are parsed, and obtain alkaline rich vanadium liquid.Added into alkaline rich vanadium liquid
Hydrochloric acid conditioning solution pH is 9.8, then according to calcium ion and phosphate anion reaction generation Ca3(PO4)2The 1.5 of theoretical amount are extraordinarily
Enter CaCl2Calcium phosphate precipitation containing vanadium solution and calcium after must being purified after 40 DEG C of stirring 1h, solid-liquor separation.Adopted after purification containing vanadium solution
With acid ammonium salt precipitation method Precipitation ammonium poly-vanadate, 550 DEG C of calcining 2h obtain the V that purity is 99.2%2O5.The phosphate of calcium
Precipitation generates hydrated gypsum and phosphoric acid with sulfuric acid reaction, and separation of solid and liquid obtains phosphoric acid solution.Whole process vanadium is recovered as
97.9%.
Embodiment 4
- 160 mesh bone coal 1000g containing 0.35%V are taken, 1704g Na are added2HPO4Make complexing agent, by V in bone coal (III)
1.2 times of addition sodium chlorate of V (V) theoretical amount are oxidized to V (IV), are added by solid-to-liquid ratio 1: 2g/mL (on the basis of bone coal weight)
The HCl solution for entering 2.5mol/L is mixed in pressure reaction still, in confined conditions 170 DEG C of pressure leaching 5h, and liquid is consolidated after cooling
Separation, is obtained containing vanadium leachate, the leaching rate of vanadium is 94.5%.
To being 0 containing ammonium carbonate regulation pH value of solution is added in vanadium leachate, extract and separate, sodium hydroxide are carried out using N1923
Solution is stripped, and obtains alkaline rich vanadium liquid.It is 9.5 to add hydrochloric acid conditioning solution pH into alkaline rich vanadium liquid, then according to calcium
Ion and phosphate anion reaction generation Ca3(PO4)21.2 times of addition CaCl of theoretical amount2It is stirred at room temperature after 1.5h, solid-liquor separation
Calcium phosphate precipitation containing vanadium solution and calcium after must purifying.After purification the inclined vanadium of basic ammonium salts precipitation method Precipitation is used containing vanadium solution
Sour ammonium, 500 DEG C of calcining 2h obtain the V that purity is 99.1%2O5.The calcium phosphate precipitation of calcium and sulfuric acid reaction generate hydrated gypsum and
Phosphoric acid, separation of solid and liquid obtains phosphoric acid solution.Whole process vanadium is recovered as 93.6%.
Embodiment 5
- 150 mesh bone coal 1000g containing 1.4%V are taken, 750gNaH is added2PO4Make complexing agent, by V in bone coal (III) and V
(IV) 1.1 times of addition sodium chlorate of V (V) theoretical amount are oxidized to, 1.5mol/L salpeter solution is added by solid-to-liquid ratio 1: 2.5g/mL
Mixed in pressure reaction still, 180 DEG C of pressure leaching 3h, solid-liquor separation after cooling, are obtained containing vanadium leachate, vanadium in confined conditions
Leaching rate be 98.3%.
To being 0.5 containing sodium hydrate regulator solution pH is added in vanadium leachate, extracted using basic extractant N235
Separation, sodium hydroxide solution is stripped, and obtains alkaline rich vanadium liquid.Nitric acid regulation pH value of solution is added into alkaline rich vanadium liquid is
10.0, then according to calcium ion and phosphate anion reaction generation Ca3(PO4)21.4 times of addition CaCl of theoretical amount2It is stirred at room temperature
Calcium phosphate precipitation containing vanadium solution and calcium after must being purified after 2.0h, solid-liquor separation.It is heavy using basic ammonium salts containing vanadium solution after purification
Vanadium method Precipitation ammonium metavanadate, 500 DEG C of calcining 2h obtain the V that purity is 99.2%2O5.The calcium phosphate precipitation of calcium and sulfuric acid are anti-
Hydrated gypsum and phosphoric acid should be generated, separation of solid and liquid obtains phosphoric acid solution.Whole process vanadium is recovered as 97.2%.
Claims (10)
1. a kind of method that vanadium is extracted from bone coal, it is characterised in that phosphate radical complexing agent, oxidant, acid, bone coal will be included
Mixed liquor carries out aoxidizing-complexation leaching；Through separation of solid and liquid after, obtain containing vanadium leachate and leached mud；P elements in mixed liquor
Concentration be more than or equal to 1mol/L.
2. the method for vanadium is extracted from bone coal as claimed in claim 1, it is characterised in that described phosphate radical complexing agent is phosphorus
At least one of acid, dihydric phosphate, dibasic alkaliine, phosphoric acid normal salt.
3. as claimed in claim 1 from bone coal extract vanadium method, it is characterised in that described oxidant be chloric acid and/
Or chlorate；The addition of oxidant is oxidized to 1~3 times of V (V) theoretical amount for V (III) and V (IV) in bone coal.
4. the method for vanadium is extracted from bone coal as claimed in claim 1, it is characterised in that the concentration of P elements is in mixed liquor
1~10mol/L.
5. the method for vanadium is extracted from bone coal as claimed in claim 1, it is characterised in that oxidation-complexation leaching process is close
Close in container and carry out, the temperature of oxidation-complexation leaching process is 70~200 DEG C.
6. the method for vanadium is extracted from bone coal as claimed in claim 1, it is characterised in that the H in mixed liquor+Concentration be 1~
14mol/L。
7. the method that vanadium is extracted from bone coal as described in any one of claim 1~6, it is characterised in that regulation is leached containing vanadium
The pH of liquid is less than or equal to 2；Extracted after through extractant, alkali back extraction, or alkaline hydrolysis is analysed again after being adsorbed through ion exchange resin；
To alkaline rich vanadium liquid.
8. the method for vanadium is extracted from bone coal as claimed in claim 7, it is characterised in that extractant is with primary amine groups, secondary
Amido, tertiary amine groups, the basic extractant of quaternary amine base；
Ion exchange resin be with primary amine groups, secondary amine, tertiary amine groups, quaternary amine base anion exchange resin.
9. the method for vanadium is extracted from bone coal as claimed in claim 7, it is characterised in that alkali is stripped and alkali resolving is used
Alkali be independently chosen from sodium hydroxide solution；Ammonia spirit；Sodium hydroxide and sodium chloride mixed solution；Ammoniacal liquor mixes molten with ammonium chloride
At least one of liquid.
10. the method for vanadium is extracted from bone coal as claimed in claim 7, it is characterised in that the pH value of the rich vanadium liquid of regulation and control alkalescence
For 8~14, calcium source is then added, stirring, precipitation obtain dephosphorization vanadium liquid and phosphorus calcium precipitate after through separation of solid and liquid；
Ammonium salt is added into dephosphorization vanadium liquid, the ammonium salt compound for obtaining vanadium is separated out, then five oxidations two are calcined to obtain for 450~650 DEG C
Vanadium product；
Solution recycled after phosphorus calcium precipitate is sulfuric acid-treated is to oxidation-complexation leaching process.
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| CN108707748A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of purification bone coal pickle liquor simultaneously recycles aluminium, potassium and iron |
| CN109207720A (en) * | 2018-11-14 | 2019-01-15 | 南华大学 | A kind of leaching method of extracting vanadium from stone coal |
| CN109943734A (en) * | 2019-03-22 | 2019-06-28 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for improving pentavalent vanadium leachate stability |
| CN110423890A (en) * | 2019-08-28 | 2019-11-08 | 重庆大学 | A method of the deep phosphorous removal in acid vanadium extraction solution |
| CN111378836A (en) * | 2018-12-29 | 2020-07-07 | 陕西华地矿业有限公司 | Method for generating vanadium pentoxide by pentavalent vanadium extraction method |
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| CN108707748A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of purification bone coal pickle liquor simultaneously recycles aluminium, potassium and iron |
| CN109207720A (en) * | 2018-11-14 | 2019-01-15 | 南华大学 | A kind of leaching method of extracting vanadium from stone coal |
| CN111378836A (en) * | 2018-12-29 | 2020-07-07 | 陕西华地矿业有限公司 | Method for generating vanadium pentoxide by pentavalent vanadium extraction method |
| CN109943734A (en) * | 2019-03-22 | 2019-06-28 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for improving pentavalent vanadium leachate stability |
| CN110423890A (en) * | 2019-08-28 | 2019-11-08 | 重庆大学 | A method of the deep phosphorous removal in acid vanadium extraction solution |
| CN110423890B (en) * | 2019-08-28 | 2021-06-18 | 重庆大学 | Method for deeply removing phosphorus in acidic vanadium extraction solution |
| CN112320847A (en) * | 2020-10-29 | 2021-02-05 | 攀枝花市山青钒业有限公司 | Method for extracting vanadium from high-phosphate vanadium solution and recycling wastewater |
| CN114243042A (en) * | 2021-12-09 | 2022-03-25 | 大连博融新材料有限公司 | Method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid and vanadium electrolyte |
| CN115449649A (en) * | 2022-10-13 | 2022-12-09 | 神华准能资源综合开发有限公司 | Method for precipitating vanadium from acidic aluminum chloride leaching solution |
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