CN106350671A - Method for purifying and enriching vanadium from stone coal pickle liquor - Google Patents

Method for purifying and enriching vanadium from stone coal pickle liquor Download PDF

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CN106350671A
CN106350671A CN201610837172.3A CN201610837172A CN106350671A CN 106350671 A CN106350671 A CN 106350671A CN 201610837172 A CN201610837172 A CN 201610837172A CN 106350671 A CN106350671 A CN 106350671A
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extraction
vanadium
pickle liquor
bone coal
organic phase
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CN106350671B (en
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张敏
张一敏
师启华
刘涛
黄晶
陈铁军
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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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
    • 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
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • 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

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  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Processing Of Solid Wastes (AREA)
  • Compounds Of Iron (AREA)

Abstract

The invention relates to a method for purifying and enriching vanadium from stone coal pickle liquor. According to the technical scheme, the method includes: adding calcium-containing substances into the stone coal pickle liquor to regulate pH, and performing solid-liquid separation to obtain neutral residues and neutral liquid; adding iron powder or sodium sulfite into the neutral liquid, and adding weak acid salt to obtain an extraction stock solution; extracting the extraction stock solution to obtain loading organic phase and raffinate, washing the loading organic phase to obtain washed loading organic phase, performing reverse extraction on the washed loading organic phase to obtain lean organic phase and rich-vanadium liquid; returning the lean organic phase to extraction after regeneration treatment. The method has the advantages that the pH of the solution during the extraction is stable, extraction stage is short, the separation effect of vanadium and various impurity ions is good, and the rich-vanadium liquid is low in impurity content.

Description

A kind of method of purification enrichment vanadium pickle liquor from bone coal
Technical field
The invention belongs to purification enrichment vanadium technical field.The side of purification enrichment vanadium more particularly, to a kind of pickle liquor from bone coal Method.
Background technology
Bone coal be China peculiar containing vanadium resource, the main preservation of the vanadium in bone coal in mica group aluminium silicate mineral lattice, While extracting vanadium from bone coal, silicate mineral is destructurized, and aluminum, ferrum, phosphorus etc. are also leached simultaneously, complicated from many impurity In solution system, purification enrichment vanadium is the committed step of extracting vanadium from stone coal.In commercial production, leachate adjusts acidity, reduction treatment Afterwards, organic faciess are obtained using acidic extractant p204 or p507 for primary raw material to be extracted, after back extraction, obtain rich vanadium liquid.Extraction During, it is primarily present problems with: (1) plurality of impurity ions can be extracted agent extraction, foreign ion common extraction impact vanadium extraction Take efficiency, contain more impurity in rich vanadium liquid simultaneously, affect vanadium product purity；(2) acidic extractant p204 or p507 extracting gold Belong to ion and belong to cation exchange mechanism, in extraction process, produce h+, so that solution ph is declined, the optimal model of ph when deviateing vanadium extraction Enclose, reduce vanadium extraction efficiency, extraction series increases.(3) in solution phosphorus with carry secretly or alternate manner enter organic faciess, through back extraction Enter rich vanadium liquid after enrichment, be unfavorable for that post precipitation reclaims vanadium.
" method of extracting vanadium from bone coal navajoite leachate " (cn 102560115 a) patented technology, this technology passes through leaching Go out the preparation of liquid, reduced iron (iii) be ferrum (ii), the step such as extraction and back extraction control ferrum to be extracted.The method is only limitted to treat The control of ferrum in treatment fluid, other impurity and ph reduce the impact that vanadium is extracted can not Effective Regulation." a kind of acidity vanadium leaches Phosphorus removing method in liquid " (cn 104480308 a) patented technology.The ph of the acid vanadium leachate that this technology phosphorus removing method is related to It is worth for 2.5 ~ 4.0, be to add composite dephosphorizing agent directly dephosphorization, mistake after again reactant liquor being aged afterwards in acid leaching liquid Filter, obtains the vanadium leachate of dephosphorization.Though the method can remove the phosphorus solution for 2.5 ~ 4.0 for the ph value, extracting vanadium from stone coal pickle liquor ph It is worth and is usually part metals ion hydrolysis when 0 ~ 2, ph value is more than 2, cause vanadium to lose, and the obstruction vanadium extraction of colloidal material can be formed Process is carried out, therefore adopting said method dephosphorization has compared with big limitation.
Content of the invention
It is contemplated that overcome prior art defect it is therefore an objective to provide the solution ph in a kind of extraction process stable, Series is short for extraction, vanadium and plurality of impurity ions good separating effect and the few purification enrichment vanadium from bone coal pickle liquor of rich vanadium liquid impurity Method.
For achieving the above object, the comprising the concrete steps that of the technical solution used in the present invention:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.0 ~ 1.4, solid-liquid separation, obtain neutralizer and neutralization slag； Add iron powder or sodium sulfite in described neutralizer again, stir 20 ~ 30min under the conditions of 15 ~ 60 DEG C；It is subsequently adding salt of weak acid Adjust ph value to 1.7 ~ 2.0, obtain extracting stock solution.
Described iron powder addition is 1.0 ~ 1.2 times that fe (iii) is reduced to the theoretical amount of iron powder needed for fe (ii), described The addition of sodium sulfite is also 1.0 ~ 1.2 times that fe (iii) is reduced to the theoretical amount of sodium sulfite needed for fe (ii).
Step 2, extraction
By extractant: tbp: the volume ratio of sulfonated kerosene is (0.1 ~ 0.3): (0.02 ~ 0.1): 1 dispensing, mixing, it is obtained organic Phase；Press described extraction stock solution again: the volume ratio of described organic faciess is (2 ~ 6): 13 ~ 5 grades of counter-current extraction, obtains load organic phases.
The temperature of described counter-current extraction is 15 ~ 40 DEG C, and the single-stage extraction time in described counter-current extraction is 5 ~ 10 min.
Step 3, washing
The preparation weak alkaline aqueous solution for 8 ~ 10 for the ph value is detergent, by described load organic phases: the volume ratio of described detergent For 1: (0.5 ~ 2) dispensing, wash and be less than 0.5 mg/l to phosphorus concentration in cleaning mixture, obtain washing back loading organic faciess.
Step 4, back extraction
Dose volume concentration is 5 ~ 12% h2so4Solution is back washing agent, by described washing back loading organic faciess: described back washing agent Volume ratio be (4 ~ 12): 13 ~ 10 grades of countercurrent reextraction, obtain rich vanadium liquid and lean organic phase；Return after lean organic phase Regeneration Treatment Extraction.
The temperature of described countercurrent reextraction is 20 ~ 50 DEG C, and the single-stage Stripping times in described countercurrent reextraction are 5 ~ 30 min.
The main chemical compositions of described bone coal pickle liquor are: v is 1.2 ~ 3.5g/l；Al is 7 ~ 25g/l；Fe is 2 ~ 9g/l；k For 2.5 ~ 6g/l；P is 0.3 ~ 1.5g/l.
Described calcareous material is caco3, cao and ca (oh)2One or more of.
Cation in described salt of weak acid is na+、k+One or more of.
Anion in described salt of weak acid is po4 3-、hpo4 2-、c2o4 2-One or more of.
Described extractant is one of p204, p507, n235.
Described weak alkaline aqueous solution is one or more of sodium hydroxide and potassium hydroxide.
Due to adopting said method, the present invention compared with prior art, has the positive effect that:
1st, the method that the present invention adopts adjusted stepwise ph value, first adjusts the ph value of bone coal leachate to 1.0 ~ 1.4, reduces solid Liquid segregational load and vanadium loss；Add salt of weak acid to adjust ph value again in neutralizer and extract optimum range 1.7 ~ 2.0 to vanadium, make molten Form weak acid root weak acid buffer system, to the h producing in extraction process in liquid+Enter row buffering, raffinate ph value stabilization exists 1.60~1.85.Compared with the raffinate ph value reduction by 0.7 ~ 1.0 of prior art, the method raffinate only reduces by 0.10 ~ 0.25, Achieve the value self-regulation of extraction system ph and ph value stabilization 1.60 ~ 1.85, promote vanadium extract and separate, extraction series shortens 1 ~ 3 Level, in the rich vanadium liquid that the present invention obtains, aluminium content is only 10 ~ 25% of aluminium content in the rich vanadium liquid that other methods obtain, the present invention In the rich vanadium liquid obtaining, iron content is only 20 ~ 35% of iron content in the rich vanadium liquid that other methods obtain.
2nd, because the present invention adopts weak alkaline aqueous solution as detergent, wash and carry secretly in organic faciess and with weak chemical bond knot The phosphorus closing, in the rich vanadium liquid that the present invention obtains, phosphorus content is only 10 ~ 20% of phosphorus content in the rich vanadium liquid that other methods obtain.
Therefore, the solution ph that the present invention has in extraction process is stablized, extraction series is short, vanadium and plurality of impurity ions divide From the few feature of the good and rich vanadium liquid impurity of effect.
Specific embodiment
With reference to specific embodiment, the invention will be further described, not the restriction to its protection domain.
In this specific embodiment:
Cation in described salt of weak acid is na+、k+One or more of；
Anion in described salt of weak acid is po4 3-、hpo4 2-、c2o4 2-One or more of.
Repeat no more in embodiment.
Embodiment 1
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.0 ~ 1.2, solid-liquid separation, obtain neutralizer and neutralization slag； Add iron powder in described neutralizer again, the addition of iron powder is the theoretical amount that fe (iii) is reduced to iron powder needed for fe (ii) 1.0 ~ 1.1 times；Stir 25 ~ 30min under the conditions of 15 ~ 30 DEG C, be subsequently adding salt of weak acid and adjust ph value to 1.7 ~ 1.9, obtain Extraction stock solution.
Step 2, extraction
By extractant: tbp: the volume ratio of sulfonated kerosene is (0.1 ~ 0.2): (0.06 ~ 0.1): 1 dispensing, mixing, it is obtained organic Phase；Press described extraction stock solution again: the volume ratio of described organic faciess is (4 ~ 6): 13 ~ 4 grades of counter-current extraction, obtains load organic phases.
The temperature of described counter-current extraction is 15 ~ 25 DEG C, and the single-stage extraction time in described counter-current extraction is 5 ~ 8 min.
Step 3, washing
The preparation weak alkaline aqueous solution for 8 ~ 9 for the ph value is detergent, by described load organic phases: the volume ratio of described detergent is 1: (0.5 ~ 1) dispensing, wash and be less than 0.5mg/l to phosphorus concentration in cleaning mixture, obtain washing back loading organic faciess.
Step 4, back extraction
Dose volume concentration is 5 ~ 8% h2so4Solution is back washing agent, by described washing back loading organic faciess: described back washing agent Volume ratio is (4 ~ 8): 13 ~ 6 grades of countercurrent reextraction, obtains rich vanadium liquid and lean organic phase；Extraction is returned after lean organic phase Regeneration Treatment.
The temperature of described countercurrent reextraction is 20 ~ 30 DEG C, and the single-stage Stripping times in described countercurrent reextraction are 20 ~ 30 min.
The main chemical compositions of described bone coal pickle liquor are: v is 1.2 ~ 2.4g/l；Al is 7 ~ 14g/l；Fe is 6 ~ 9g/l；k For 2.5 ~ 4.5g/l；P is 0.3 ~ 0.7g/l.
Described calcareous material is caco3；Described extractant is p204；Described weak alkaline aqueous solution is sodium hydroxide.
Embodiment 2
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.0 ~ 1.2, solid-liquid separation, obtain neutralizer and neutralization slag； Add sodium sulfite in described neutralizer again, the addition of sodium sulfite is that fe (iii) is reduced to sulfurous needed for fe (ii) 1.0 ~ 1.1 times of the theoretical amount of sour sodium；Under the conditions of 15 ~ 30 DEG C stir 25 ~ 30min, be subsequently adding salt of weak acid adjust ph value to 1.7 ~ 1.9, obtain extracting stock solution.
Remaining is with embodiment 1.
Embodiment 3
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3With the mixing beyond the region of objective existence of cao, remaining is with embodiment 1.
Embodiment 4
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3With the mixing beyond the region of objective existence of cao, remaining is with embodiment 2.
Embodiment 5
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3, cao and ca (oh)2Mixing beyond the region of objective existence, remaining is with embodiment 1.
Embodiment 6
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3, cao and ca (oh)2Mixing beyond the region of objective existence, remaining is with embodiment 2.
Embodiment 7
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.1 ~ 1.3, solid-liquid separation, obtain neutralizer and neutralization slag； Add iron powder in described neutralizer again, the addition of iron powder is the theoretical amount that fe (iii) is reduced to iron powder needed for fe (ii) 1.05 ~ 1.15 times；Stir 22 ~ 28min under the conditions of 30 ~ 45 DEG C, be subsequently adding salt of weak acid and adjust ph value to 1.7 ~ 1.9, obtain To extraction stock solution.
Step 2, extraction
By extractant: tbp: the volume ratio of sulfonated kerosene is (0.15 ~ 0.25): (0.04 ~ 0.08): 1 dispensing, mixing, it is obtained Organic faciess；Press described extraction stock solution again: the volume ratio of described organic faciess is (2 ~ 4): 14 ~ 5 grades of counter-current extraction, obtain loading organic Phase.
The temperature of described counter-current extraction is 20 ~ 35 DEG C, and the single-stage extraction time in described counter-current extraction is 6 ~ 9 min.
Step 3, washing
The preparation weak alkaline aqueous solution for 9 ~ 10 for the ph value is detergent, by described load organic phases: the volume ratio of described detergent For 1: (1.5 ~ 2) dispensing, wash and be less than 0.5mg/l to phosphorus concentration in cleaning mixture, obtain washing back loading organic faciess.
Step 4, back extraction
Dose volume concentration is 7 ~ 10% h2so4Solution is back washing agent, by described washing back loading organic faciess: described back washing agent Volume ratio be (6 ~ 10): 17 ~ 10 grades of countercurrent reextraction, obtain rich vanadium liquid and lean organic phase；Return after lean organic phase Regeneration Treatment Extraction.
The temperature of described countercurrent reextraction is 30 ~ 40 DEG C, and the single-stage Stripping times in described countercurrent reextraction are 15 ~ 25 min.
The main chemical compositions of described bone coal pickle liquor are: v is 2.4 ~ 3.5g/l；Al is 17 ~ 25g/l；Fe is 4 ~ 7g/l； K is 4.5 ~ 6g/l；P is 1.0 ~ 1.5g/l.
Described calcareous material is cao；Described extractant is p507；Described weak alkaline aqueous solution is potassium hydroxide.
Embodiment 8
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.1 ~ 1.3, solid-liquid separation, obtain neutralizer and neutralization slag； Add sodium sulfite in described neutralizer again, the addition of sodium sulfite is that fe (iii) is reduced to sulfurous needed for fe (ii) 1.05 ~ 1.15 times of the theoretical amount of sour sodium；Stir 22 ~ 28min under the conditions of 30 ~ 45 DEG C, be subsequently adding salt of weak acid and adjust ph value To 1.7 ~ 1.9, obtain extracting stock solution.
Remaining is with embodiment 7.
Embodiment 9
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is cao and ca (oh) that the present embodiment removes described calcareous material2Mixing beyond the region of objective existence, remaining is with embodiment 7.
Embodiment 10
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is cao and ca (oh) that the present embodiment removes described calcareous material2Mixing beyond the region of objective existence, remaining is with embodiment 8.
Embodiment 11
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.2 ~ 1.4, solid-liquid separation, obtain neutralizer and neutralization slag； Add iron powder in described neutralizer again, the addition of iron powder is the theoretical amount that fe (iii) is reduced to iron powder needed for fe (ii) 1.1 ~ 1.2 times；Stir 20 ~ 25min under the conditions of 45 ~ 60 DEG C, be subsequently adding salt of weak acid and adjust ph value to 1.8 ~ 2.0, obtain Extraction stock solution.
Step 2, extraction
By extractant: tbp: the volume ratio of sulfonated kerosene is (0.25 ~ 0.3): (0.02 ~ 0.06): 1 dispensing, mixing, being obtained has Machine phase；Press described extraction stock solution again: the volume ratio of described organic faciess is (3 ~ 5): 14 ~ 5 grades of counter-current extraction, obtains load organic phases.
The temperature of described counter-current extraction is 25 ~ 40 DEG C, and the single-stage extraction time in described counter-current extraction is 7 ~ 10 min.
Step 3, washing
The preparation weak alkaline aqueous solution for 9 ~ 10 for the ph value is detergent, by described load organic phases: the volume ratio of described detergent For 1: (1 ~ 1.5) dispensing, wash and be less than 0.5mg/l to phosphorus concentration in cleaning mixture, obtain washing back loading organic faciess.
Step 4, back extraction
Dose volume concentration is 9 ~ 12% h2so4Solution is back washing agent, by described washing back loading organic faciess: described back washing agent Volume ratio be (8 ~ 12): 15 ~ 8 grades of countercurrent reextraction, obtain rich vanadium liquid and lean organic phase；Extraction is returned after lean organic phase Regeneration Treatment Take.
The temperature of described countercurrent reextraction is 40 ~ 50 DEG C, and the single-stage Stripping times in described countercurrent reextraction are 5 ~ 15 min.
The main chemical compositions of described bone coal pickle liquor are: v is 1.8 ~ 3.0g/l；Al is 10 ~ 18g/l；Fe is 2 ~ 5g/l； K is 3.5 ~ 5g/l；P is 0.6 ~ 1.1g/l.
Described calcareous material is ca (oh)2；Described extractant is n235；Described weak alkaline aqueous solution is sodium hydroxide Mixture with potassium hydroxide.
Embodiment 12
A kind of method of purification enrichment vanadium pickle liquor from bone coal.The comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.2 ~ 1.4, solid-liquid separation, obtain neutralizer and neutralization slag； Add sodium sulfite in described neutralizer again, the addition of sodium sulfite is that fe (iii) is reduced to sulfurous needed for fe (ii) 1.1 ~ 1.2 times of the theoretical amount of sour sodium；Under the conditions of 45 ~ 60 DEG C stir 20 ~ 25min, be subsequently adding salt of weak acid adjust ph value to 1.8 ~ 2.0, obtain extracting stock solution.
Remaining is with embodiment 11.
Embodiment 13
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3With ca (oh)2Mixing beyond the region of objective existence, remaining is with embodiment 11.
Embodiment 14
A kind of method of purification enrichment vanadium pickle liquor from bone coal.
It is caco that the present embodiment removes described calcareous material3With ca (oh)2Mixing beyond the region of objective existence, remaining is with embodiment 12.
This specific embodiment compared with prior art, has the positive effect that:
1st, the method that this specific embodiment adopts adjusted stepwise ph value, first by the ph value regulation of bone coal leachate to 1.0 ~ 1.4, Reduce solid-liquid separation load and vanadium loss；Add in neutralizer again salt of weak acid adjust ph value to vanadium extraction optimum range 1.7 ~ 2.0, make to be formed weak acid root weak acid buffer system in solution, to the h producing in extraction process+Enter row buffering, raffinate ph value Stablize 1.60 ~ 1.85.Compared with the raffinate ph value reduction by 0.7 ~ 1.0 of prior art, the method raffinate only reduces by 0.10 ~ 0.25 it is achieved that the value self-regulation of extraction system ph and ph value stabilization 1.60 ~ 1.85, promote vanadium extract and separate, extraction series contracting Short 1 ~ 3 grade, in the rich vanadium liquid that this specific embodiment obtains, aluminium content is only aluminium content in the rich vanadium liquid that other methods obtain 10 ~ 25%, in the rich vanadium liquid that this specific embodiment obtains, iron content is only 20 of iron content in the rich vanadium liquid that other methods obtain ~35%.
2nd, because this specific embodiment adopts weak alkaline aqueous solution as detergent, wash in organic faciess and carry secretly and with weak The phosphorus of chemical bonds, in the rich vanadium liquid that this specific embodiment obtains, phosphorus content is only phosphorus in the rich vanadium liquid that other methods obtain The 10 ~ 20% of content.
Therefore, the solution ph that this specific embodiment has in extraction process is stablized, extraction series is short, vanadium is miscellaneous with multiple The few feature of the good and rich vanadium liquid impurity of matter ion isolation effect.

Claims (7)

1. a kind of pickle liquor from bone coal the method for purification enrichment vanadium it is characterised in that comprising the concrete steps that of methods described:
Step one, extraction stock solution preparation
Calcareous material is added in bone coal pickle liquor, regulation ph value to 1.0 ~ 1.4, solid-liquid separation, obtain neutralizer and neutralization slag； Add iron powder or sodium sulfite in described neutralizer again, stir 20 ~ 30min under the conditions of 15 ~ 60 DEG C；It is subsequently adding salt of weak acid Adjust ph value to 1.7 ~ 2.0, obtain extracting stock solution；
Described iron powder addition is 1.0 ~ 1.2 times that fe (iii) is reduced to the theoretical amount of iron powder needed for fe (ii), described sulfurous The addition of sour sodium is also 1.0 ~ 1.2 times that fe (iii) is reduced to the theoretical amount of sodium sulfite needed for fe (ii)；
Step 2, extraction
By extractant: tbp: the volume ratio of sulfonated kerosene is (0.1 ~ 0.3): (0.02 ~ 0.1): 1 dispensing, mixing is obtained organic Phase；Press described extraction stock solution again: the volume ratio of described organic faciess is (2 ~ 6): 13 ~ 5 grades of counter-current extraction, obtains load organic phases；
The temperature of described counter-current extraction is 15 ~ 40 DEG C, and the single-stage extraction time in described counter-current extraction is 5 ~ 10 min；
Step 3, washing
The preparation weak alkaline aqueous solution for 8 ~ 10 for the ph value is detergent, by described load organic phases: the volume ratio of described detergent For 1: (0.5 ~ 2) dispensing, wash and be less than 0.5 mg/l to phosphorus concentration in cleaning mixture, obtain washing back loading organic faciess；
Step 4, back extraction
Dose volume concentration is 5 ~ 12% h2so4Solution is back washing agent, by described washing back loading organic faciess: described back washing agent Volume ratio is (4 ~ 12): 13 ~ 10 grades of countercurrent reextraction, obtains rich vanadium liquid and lean organic phase；Extraction is returned after lean organic phase Regeneration Treatment Take；
The temperature of described countercurrent reextraction is 20 ~ 50 DEG C, and the single-stage Stripping times in described countercurrent reextraction are 5 ~ 30 min.
2. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described bone coal is sour The main chemical compositions of immersion are: v is 1.2 ~ 3.5g/l；Al is 7 ~ 25g/l；Fe is 2 ~ 9g/l；K is 2.5 ~ 6g/l；P is 0.3 ~1.5g/l.
3. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described calcic thing Matter is caco3, cao and ca (oh)2One or more of.
4. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described salt of weak acid In cation be na+、k+One or more of.
5. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described salt of weak acid In anion be po4 3-、hpo4 2-、c2o4 2-One or more of.
6. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described extractant For one of p204, p507 and n235.
7. the pickle liquor from bone coal according to claim 1 the method for purification enrichment vanadium it is characterised in that described alkalescence Aqueous solution is one or more of sodium hydroxide and potassium hydroxide.
CN201610837172.3A 2016-09-21 2016-09-21 A kind of method of purification enrichment vanadium in pickle liquor from bone coal Active CN106350671B (en)

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