CN109355514A - Vanadium slag low calcium roasting-counter current acid leaching vanadium extraction method - Google Patents
Vanadium slag low calcium roasting-counter current acid leaching vanadium extraction method Download PDFInfo
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- CN109355514A CN109355514A CN201811458167.7A CN201811458167A CN109355514A CN 109355514 A CN109355514 A CN 109355514A CN 201811458167 A CN201811458167 A CN 201811458167A CN 109355514 A CN109355514 A CN 109355514A
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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Abstract
The invention belongs to vanadium extraction technical fields, are related to vanadium slag low calcium roasting-counter current acid leaching vanadium extraction method.Technical problem to be solved by the invention is to provide vanadium slag low calcium roasting-counter current acid leaching vanadium extraction methods, comprising the following steps: a, roasting；B, clinker is mixed with first order filtrate or/and second level leachate, sulfuric acid is added and is leached, control first order leaching process system pH is 2.8~3.5, is separated by solid-liquid separation to obtain first order leachate and solid；Wash to obtain first order filtrate and solid；C, solid is leached using third level leachate or/and third level filtrate, and it is 1.8~3.5 that terminal system pH is leached in the control second level, is separated by solid-liquid separation to obtain second level leachate and solid；D, solid is leached, and it is 1.4~2.2 that the control third level, which leaches terminal system pH, is separated by solid-liquid separation to obtain third level leachate and solid；Washing obtains third level filtrate and tailings in vanadium extraction.The method of the present invention has the advantages that leaching vanadium extraction rate is high, at low cost.
Description
Technical field
The invention belongs to vanadium extraction fields, and in particular to a kind of method of vanadium slag low calcium roasting-counter current acid leaching vanadium extraction.
Background technique
Lime stone is the primary raw material of vanadium slag calcification baking vanadium extraction, obtains CaO using its pyrolytic, accelerates acid vanadium slag
The decomposition of internal crystal framework, and necessary calcification agent is provided, generate the molten metavanadic acid calcium CaV of theobromine2O6, pyrovanadic acid calcium Ca2V2O7、
Positive calcium vanadate Ca3V2O8Class compound.Due in the leaching rate that pH is an acidleach in 2.5~3.5 ranges: pyrovanadic acid calcium > positive vanadium
Sour calcium > metavanadic acid calcium, and there is also the SiO of a certain amount of consumption calcium salt in vanadium slag2、TiO2Equal hydrochlorates substance, to guarantee that production connects
CaO/V is generally pressed at continuous stable operation, scene2O5Weight ratio is 0.5~0.8 and its carries out ingredient, gained calcification baking clinker above
The dissolution leaching rate of vanadium is 80~86% or so in the acidleach of pH=2.5~3.5.
In actual production, containing alkali compounds such as a large amount of vanadic acid calcium salts and other CaO, MnO in calcification clinker, leaching
Process needs to consume a large amount of sulfuric acid.And the sulfuric acid of 66~96wt% concentration in producing is added rapidly to leach in slurry, one
Aspect is diluted with water, ionizes as H+And SO4 2-, a large amount of sulfuric acid latent heat can be released, leaching slurry temperature is caused to increase suddenly；
On the other hand, due to H+H is generated with CaO, MnO class alkali substance reaction2O and Ca2+、Mn2+, can also release a large amount of reaction
Heat, in both above-mentioned resultant force, there is no under the conditions of special cooling measure, it is easy to cause the temperature for leaching slurry from 30 DEG C and
It is increased to 70 DEG C or more below, causes the leachate (V30g/L) of high vanadium concentration that hydrolysis precipitation phenomenon, the practical leaching of vanadium occurs
Extracting rate is far below 80% target.Meanwhile still remained in tailings after such calcification clinker vanadium extraction 15% or more CaSO4,
Due to the presence of dihydrate gypsum and semi-hydrated gypsum, cause moisture content in slag high, transport difficult；And S content >=3% in slag, far
It is residue further using bringing very big difficulty more than the upper limit of steel system raw material.
CN101412539A discloses the oxygen that one kind can obtain high quality vanadium product and vanadium extracting waste water is recycled
Change the clean preparation method of vanadium, vanadium slag+lime stone presses CaO/V2O5Weight ratio be 0.5~1.4 mixing carry out calcification baking, it is molten leaching,
Separation of solid and liquid, ammonium salt precipitation, calcining deamination or reduction.CN101161831A discloses a kind of method of calcification vanadium slag sintering, will
CaO and V2O5The vanadium slag that weight ratio is 0.5~0.7 is in 600 DEG C~950 DEG C roasting kiln roastings.CN102828019A discloses one
The method of the kind oxygen-enriched calcification baking of high-grade vanadium slag, by CaO and V2O5Weight ratio be 0.5~0.8 high-grade vanadium slag mixture exist
It is roasted under the atmosphere that oxygen volume content is 12-21%.The above-mentioned prior art be required to be added those high in calcium to vanadium slag into
Row roasting.
Summary of the invention
The method for needing to be added those high in calcium for existing vanadium-extracting roasting, the present invention provides a kind of vanadium slag low calcium roastings-
The method of counter current acid leaching vanadium extraction.
Technical problem to be solved by the invention is to provide a kind of methods of vanadium slag low calcium roasting-counter current acid leaching vanadium extraction.It should
Method the following steps are included:
A, it roasts: vanadium slag and lime stone is pressed into CaO/V2O5Weight ratio 0.25~0.5 is baking mixed, obtains calcification baking clinker；
B, the first order leaches: step a calcification baking clinker being mixed with first order filtrate or/and second level leachate, so
Sulfuric acid is added afterwards and carries out first order leaching, control first order leaching process system pH is 2.8~3.5, solid-liquid point after leaching
From first order leachate and solid；Then solid is washed, obtains first order filtrate and solid；
C, the second level is leached: the solid after step b washing is carried out the using third level leachate or/and third level filtrate
Second level leaches, and it is 1.8~3.5 that terminal system pH is leached in the control second level, is separated by solid-liquid separation to obtain second level leachate and solid；
D, the third level is leached: the solid after step c is leached carries out third level leaching, and the control third level leaches terminal system
PH is 1.4~2.2, is separated by solid-liquid separation to obtain third level leachate and solid；Then solid is washed, obtain third level filtrate and
Tailings in vanadium extraction.
Specifically, in the method and step a of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the maturing temperature is 840~
930℃.Calcining time is 30~120min.
Specifically, in the method and step a of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the calcification baking clinker grain
Degree≤0.125mm.
Preferably, in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the first order, which leaches, to be used
First order filtrate or/and second level leachate pH 2.2 or more.
Specifically, in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the liquid of the first order leaching
Gu mass ratio is 2~3 ﹕ 1.Content of vanadium is in 20g/L or more in gained first order leachate.
Specifically, in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the first order leachate pH
It is 2.8~4.0.
Specifically, in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the temperature of the first order leaching
Degree is room temperature~70 DEG C.Extraction time is 20~120min.
Preferably, in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the liquid of the washing use
PH is 2.8~7.0.The liquid that the washing uses is in the waste water lime and/or electrolysis treated recycle-water, pH are adjusted to
2.8~7.0.
Specifically, the liquid of the washing solid is solid in the method and step b of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction
Mass ratio is 0.5~1.0 ﹕ 1.Gained first order filtrate terminal content of vanadium < 2g/L.
Preferably, in the method and step c of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the second level, which is leached, to be used
Third level leachate or/and third level filtrate pH be 1.4~2.2.
Specifically, in the method and step c of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the liquid of the second level leaching
Gu mass ratio is 1.5~2.5 ﹕ 1.Content of vanadium < 6g/L in the leachate of the gained second level.
Specifically, in the method and step c of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the temperature of the second level leaching
Degree is room temperature~70 DEG C.Extraction time is 1~5min.
Further, in the method and step d of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the third level leaches and adopts
It is 0.7~1.5 with liquid pH.The third level leaches the liquid used in waste water lime and/or electrolysis treated reuse
Water, pH are adjusted to 0.7~1.5.
Specifically, in the method and step d of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the liquid of the third time leaching
Gu mass ratio is 1.2~2.0 ﹕ 1.Content of vanadium < 6g/L in gained third level leachate.
Specifically, in the method and step d of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the temperature of the third time leaching
Degree is room temperature~70 DEG C.Extraction time is 5~10min.
Preferably, in the method and step d of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the liquid of the washing use
PH is 1.4~7.The liquid that the washing uses is in the waste water lime and/or electrolysis treated recycle-water, pH are adjusted to 1.4
~7.
Specifically, the liquid of the washing solid is solid in the method and step d of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction
Mass ratio is 0.5~1.0 ﹕ 1.Gained third level filtrate terminal content of vanadium < 0.4g/L.
Further, the method for above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction further includes step e, passes through the above method
Obtained first order leachate carries out precipitation, calcining, obtains vanadic anhydride.
Specifically, in the method and step e of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the sulfuric acid of the precipitation use
Ammonium and vanadium mass ratio are 1~3.Precipitation pH is 1.5~2.0.Precipitation temperature is 90 DEG C~boiling.The precipitation time be 40~
120min。
Specifically, in the method and step e of above-mentioned vanadium slag low calcium roasting-counter current acid leaching vanadium extraction, the calcination temperature is 500~
550℃.Calcination time is 30~120min.
The method of the present invention is due to subsequent acid-leaching vanadium-extracted using multi-stage countercurrent, to reduce the calcium vanadium ratio of roasting and leach sulphur
Sour dosage avoids extraction temperature raising, and TV can reduce to 0.6% hereinafter, the rate of recovery of vanadium improves 10 in tailings in vanadium extraction
Percentage point, and the gypsum in tailings and S content are significantly reduced, be conducive to further recycle, there is significant technology
Economical and environmentally friendly advantage and wide popularization and application foreground.
Detailed description of the invention
Fig. 1 the method for the present invention process flow diagram；Wherein, liquid 1 is that the first order leaches the liquid used, and liquid 2 is
The liquid used is leached in the second level, and liquid 3 is that the third level leaches the liquid used.
Specific embodiment
Since existing vanadium slag roasting calcium vanadium ratio is 0.5~0.8, Ca when calcium additive generates pyrovanadic acid calcium is added2V2O7, this
When be the molar ratio of vanadium calcium be 1 ﹕ 1, vanadium moves be finally made in leachate, calcium reacted after leaching with sulfate radical generate calcium sulfate (with
Water combines, and is commonly called as gypsum, and residue S content is high, is not easily recycled), it is further deposited in residue, and extract a vanadium, to be added
A sulfuric acid (leaches heat releasing source, the uncontrolled main source of extraction temperature can reach 80 DEG C or more, and vanadium is caused to precipitate
Reason).Then if addition calcium content is low, the calcium of half is added, then generates metavanadic acid calcium CaV when roasting2O6, the molar ratio of vanadium calcium
It is 2 ﹕ 1, S content can all reduce in the subsequent acid consumption and tailings being related to.So the present invention devises a kind of side of low calcium roasting
Method makes up the metavanadic acid calcium defect lower than pyrovanadic acid calcium solubility by way of subsequent multi-stage countercurrent acidleach, and three stage countercurrents mention
Good effect is equally reached after taking.
The method of vanadium slag low calcium roasting-counter current acid leaching vanadium extraction of the present invention, comprising the following steps:
A, it roasts: vanadium slag and lime stone is pressed into CaO/V2O5Weight ratio 0.25~0.5 is baking mixed, obtains calcification baking clinker；
B, the first order leaches: step a calcification baking clinker being mixed with first order filtrate or/and second level leachate, so
Sulfuric acid is added afterwards and carries out first order leaching, control first order leaching process system pH is 2.8~3.5, solid-liquid point after leaching
From first order leachate and solid；Then solid is washed, obtains first order filtrate and solid；
C, the second level is leached: the solid after step b washing is carried out the using third level leachate or/and third level filtrate
Second level leaches, and it is 1.8~3.5 that terminal system pH is leached in the control second level, is separated by solid-liquid separation to obtain second level leachate and solid；
D, the third level is leached: the solid after step c is leached carries out third level leaching, and the control third level leaches terminal system
PH is 1.4~2.2, is separated by solid-liquid separation to obtain third level leachate and solid；Then solid is washed, obtain third level filtrate and
Tailings in vanadium extraction；
E, precipitation: first order leachate carries out precipitation, calcining, obtains vanadic anhydride.
The method of the present invention step b leaching step, in first order leaching process, if the too low Leaching Vanadium that will cause of pH value sinks again
Vanadium phosphorus mass ratio is big in shallow lake, leachate, and the vanadium product of preparation is unqualified and subsequent handling yield is low；If pH value is excessively high and will cause
Leaching process dissolution is incomplete, yield is low.So the system pH that need to control first time leaching process is 2.8~3.5.Resulting
Level-one leachate pH is 2.8~4.0.
The method of the present invention step b leaching step, the first order leach the liquid used and leach for first order filtrate or the second level
Liquid is also possible to the mixed solution of the two.The liquid leached using first order filtrate or/and second level leachate as the first order
Body, in order to recycle vanadium therein, to improve the vanadium concentration in first order leachate, be received to finally improve vanadium
Rate.The first order leach liquid (i.e. first order filtrate, second level leachate or both the mixed solution) pH that uses 2.2 with
On, the liquid pH such as used is too low, can direct precipitation after leaching.When first time carrying out the method for the present invention, first order leaching is adopted
Liquid can directly select be adjusted to pH in 2.2 or more domestic water, industrial water, distilled water, recycle-water etc. or
Even if being other containing impurity but not influence that the method for the present invention carries out other use water.At second and implementation later is of the invention
When method, the first order, which leaches the liquid used, then can be used the first order filtrate or second level leachate that the method for the present invention obtains.
The method of the present invention step b leaching step, it is 2~3 ﹕ 1 that the liquid that the control first order leaches when preferably leaching, which consolidates mass ratio,.
Liquid in the liquid-solid ratio refers to first order filtrate or/and second level leachate.Content of vanadium exists in gained first order leachate
20g/L or more.The temperature that the first order leaches is room temperature~70 DEG C.Extraction time is 20~120min.
The method of the present invention step b leaching step keeps vanadium and the dissolution of minimal amount of phosphorus, vanadium most in clinker generally molten
80% or more solution, phosphorus generally dissolve 18% hereinafter, playing the role of simultaneously " checking on ", TV/P mass in control first order leachate
Than 1000 or more, and TV concentration is in 20g/L or more.In fact, being leached by the first order, most soluble vanadium in clinker
All be leached, only a small amount of soluble vanadium and by package vanadium residual in solids.
The method of the present invention step b washing step, washing purpose also for recycling solid in remaining soluble vanadium, because
To be that high vanadium solution is most stable in 2.8~4.0 ranges in pH, the too high or too low vanadium of pH can all be precipitated.In order to recycle first
Vanadium in grade filtrate, the liquid pH that washing solid uses in rate-determining steps b would not be caused in first order filtrate for 2.8~7.0
Vanadium precipitating, gained first order filtrate returns to first order leaching as the liquid used is leached and uses, to realize the recycling of vanadium.
It is described wash the liquid that uses can in waste water lime and/or the recycle-water that is electrolysed that treated, pH is adjusted to 2.8~
7.0.Gained first order filtrate pH is 2.8~4.0.
The method of the present invention step b washing step, it is 0.5~1.0 ﹕ 1 that the liquid of specific control washing solid, which consolidates mass ratio,.Gained
First order filtrate terminal content of vanadium < 2g/L.First order filtrate terminal content of vanadium < 2g/L refers to: resulting when washing terminal to wash
Content of vanadium < 2g/L in liquid is washed, the vanadium concentration < 2g/L without referring to entire first order filtrate.
The method of the present invention step c leaching step, using third level leachate, third level filtrate or both mixture conduct
The main purpose for the liquid that the second level is leached has a following: first, recycle the vanadium in third level leachate；Second, remove the
Impurity in three-level leachate can leach Fe when pH < 1.5 in third level leachate3+, it is one of dephosphorization agent, and its leaching
Total amount can reach the dosage of complete dephosphorization, but Fe3+It must be 2.2 or more ability and PO in pH4 3-In conjunction with generation FePO4Or water
Solution generates Fe (OH)3Precipitation adsorption PO4 3-, further achieve the purpose that dephosphorization, due to remaining in the solid after step a washing
Ferric vandate manganese salt and manganese oxide class compound, after solid contact reacts after third level leachate and step b are washed pH from 1.4~
2.2 are increased to 1.8~3.5, and hydrolysis occurs for further iron ion, by a variety of methods such as chemical precipitation and adsorption precipitation,
Reach and removes the impurity purpose such as phosphorus, silicon, iron in solution；So system pH is 1.8 after need to meeting contact in order to meet removal step
~3.5, then then needing to control third level leachate, third level filtrate or both mixture pH is 1.4~2.2；Third is returned
Receive the vanadium in the vanadate after step d is washed in solid.The vanadium of recycling enters second level leachate, to return to first order leaching
It is used when out as extracted liquid, hence into first order leachate, first order leachate is the raw material of subsequent vanadium extraction.It is described
The temperature that the second level is leached is room temperature~70 DEG C.Extraction time is 1~5min.Second level leachate pH is 1.8~3.5.It is preferred that
Controlling the liquid that the second level is leached to consolidate mass ratio is 1.5~2.5 ﹕ 1.Content of vanadium < 6g/L in the leachate of the gained second level.?
When carrying out the method for the present invention for the first time, the liquid used is leached in the second level can directly select the life for being adjusted to pH 1.4~2.2
Even if containing impurity but not influence the method for the present invention implementation with water, industrial water, distilled water, recycle-water etc. are either other
Other use water.When at second and carrying out the method for the present invention later, the liquid used is leached in the second level then can be used the present invention
Third level leachate that method obtains, third level filtrate or both mixture.
The method of the present invention step d leaching step, since third level leachate of the present invention is used as the liquid when second level is leached
When, if the leaching pH that third level leaching process uses is too low, to will cause, pH is lower, leaches the liquid used when being used as the second level
When body, second level leaching will affect；If the liquid pH used in third level leaching process is excessively high, depth can not be properly arrived at
The purpose of vanadium extraction is leached, yield raising is unobvious, so need to control leaching terminal pH is 1.4~2.2, i.e. third level leachate pH
It also is 1.4~2.2.Specifically use pH for 0.7~1.5 liquid when leaching.The liquid that the leaching uses can be for from waste water
In lime and/or electrolysis treated recycle-water, pH are adjusted to 0.7~1.5.It is 1.2 that the liquid that the third time leaches, which consolidates mass ratio,
~2.0 ﹕ 1.Content of vanadium < 6g/L in gained third level leachate.The temperature that the third time leaches is room temperature~70 DEG C.It leaches
Time is 5~10min.
The method of the present invention step d leaching step is destroyed in slag by improving the liquid acidity for leaching and using and wraps up the object of vanadium
Phase structure improves and leaches motive force, further leaches more vanadium, generally leached by the step, content of vanadium in tailings in vanadium extraction
It can reduce to 0.6% or less.
The method of the present invention step d washing step cannot return to use if the liquid pH that washing solid uses is too low；If
PH is excessively high, and it will cause third level filtrate pH high, further will cause precipitation.In order to recycle the vanadium in third level filtrate,
So control washs the liquid pH that solid uses as 1.4~7.The liquid that the washing uses can be for from the neutralization of waste water lime
Or electrolysis treated recycle-water, pH are adjusted to 1.4~7.It is 0.5~1.0 ﹕ 1 that the liquid of the washing solid, which consolidates mass ratio,.Gained
Third level filtrate terminal content of vanadium < 0.4g/L.Third level filtrate terminal content of vanadium < 0.4g/L refers to: gained when washing terminal
Cleaning solution in content of vanadium < 0.4g/L, the vanadium concentration < 0.4g/L without referring to entire third level filtrate.Third level filtrate pH
It is 1.3~2.5.
In the method for the present invention, the rotatable stirring pot type of 3 Leaching ways, counterflow leaching equipment or other similar set
It is standby.It is preferred that leaching for the first time is that strong mixing perseverance pH is leached, leaches leached for band filter or low stirring to pulp for the second time, soak for the third time
It is leached out for low stirring to pulp.
Embodiment 1
Roasting: by fine powder vanadium slag (V2O5=21.52%, CaO=1.63%) with pulverized limestone (CaO=54.31%) press CaO/
V2O5It after weight ratio is 0.28 mixing, is placed in the Muffle furnace for being passed through air, is heated to 890 DEG C of heat preservation 90min, take out cooling system
Sample is to 0.12mm or less；
The first order leaches: clinker and 300mL first order filtrate after taking 100g sample preparation are controlled with sulfuric acid under agitation
After system pH=2.9-3.1, temperature are 53 DEG C of leaching 60min, solid-liquor separation obtains first time leachate, measures first order leachate
Middle TV=35.31g/L, P=0.02g/L, first order leachate pH are 3.1；Filter residue pH=7 reuse water washing, first order filter
Liquid pH is 3.5；
Leach the second level: it is after 1.8 third level leachates+third level filtrate mixed solution leaches that filter residue uses pH again after washing
The second level leachate of pH=2.5 is obtained by filtration, highest extraction temperature is 27 DEG C；
The third level is leached: filter residue is added in pH=0.75-1.1,200mL recycle-water, and liquid divides admittedly after being stirred to react 10min
From third level leachate pH is 1.8, and highest extraction temperature is 31 DEG C；It washed once again with pH=7 recycle-water, third level filtrate
PH is 1.85, obtains tailings in vanadium extraction.
Precipitation: the first leachate obtains vanadic anhydride product after precipitation-calcining, wherein V2O5=98.61%, P=
0.025%；TV=0.56% is measured after tailings in vanadium extraction drying, then dissolution leaching rate (the vanadium total amount ÷ in 1-3 grades of leachates of vanadium
Vanadium total amount in clinker) it is 91.98%.
Embodiment 2
Roasting: by fine powder vanadium slag (V2O5=17.86%, CaO=2.49%) with pulverized limestone (CaO=54.07%) press CaO/
V2O5It after weight ratio is 0.47 mixing, is placed in the Muffle furnace for being passed through air, is heated to 880 DEG C of heat preservation 90min, take out cooling system
Sample is to 0.12mm or less；
The first order leaches: clinker and 250mL first order filtrate after taking 100g sample preparation are controlled with sulfuric acid under agitation
After system pH=2.8-3.1, temperature are 60 DEG C of leaching 45min, solid-liquor separation obtains first time leachate, measures first order leachate
Middle TV=33.84g/L, P=0.02g/L, first order leachate pH are 3.05；Filter residue pH=7 reuse water washing, first order filter
Liquid pH is 3.15；
Leach the second level: it is after 1.4 third level leachates+third level filtrate mixed solution leaches that filter residue uses pH again after washing
The second level leachate of pH=2.7 is obtained by filtration, highest extraction temperature is 29 DEG C；
The third level is leached: filter residue is added in pH=0.9-1.1,150mL recycle-water, and liquid divides admittedly after being stirred to react 10min
From third level leachate pH is 1.4, and highest extraction temperature is 35 DEG C；It washed once again with pH=7 recycle-water, third level filtrate
PH is 1.5, obtains tailings in vanadium extraction.
Precipitation: the first leachate obtains vanadic anhydride product after precipitation-calcining, wherein V2O5=98.33%, P=
0.02%；TV=0.52% is measured after tailings in vanadium extraction drying, then the dissolution leaching rate of vanadium is 91.24%.
Embodiment 3
Roasting: by fine powder vanadium slag (V2O5=18.45%, CaO=1.97%) with pulverized limestone (CaO=54.22%) press CaO/
V2O5It after weight ratio is 0.34 mixing, is placed in the Muffle furnace for being passed through air, is heated to 890 DEG C of heat preservation 90min, take out cooling system
Sample is to 0.12mm or less；
The first order leaches: clinker and 300mL first order filtrate after taking 100g sample preparation are controlled with sulfuric acid under agitation
After system pH=2.8-3.0, temperature are 55 DEG C of leaching 70min, solid-liquor separation obtains first time leachate, measures first order leachate
Middle TV=30.05g/L, P=0.02g/L, first order leachate pH are 2.9；Filter residue pH=7 reuse water washing, first order filter
Liquid pH is 3.05；
Leach the second level: it is after 1.6 third level leachates+third level filtrate mixed solution leaches that filter residue uses pH again after washing
The second level leachate of pH=2.8 is obtained by filtration, highest extraction temperature is 27 DEG C；
The third level is leached: filter residue is added in pH=1.1-1.2,150mL recycle-water, and liquid divides admittedly after being stirred to react 10min
From third level leachate pH is 1.6, and highest extraction temperature is 30 DEG C；It washed once again with pH=7 recycle-water, third level filtrate
PH is 1.7, obtains tailings in vanadium extraction.
First leachate obtains vanadic anhydride product after precipitation-calcining, wherein V2O5=98.98%, P=0.02%；It mentions
TV=0.55% is measured after vanadium tailing soil drying, then the dissolution leaching rate of vanadium is 91.26%.
Claims (10)
1. vanadium slag low calcium roasting-counter current acid leaching vanadium extraction method, it is characterised in that: the following steps are included:
A, it roasts: vanadium slag and lime stone is pressed into CaO/V2O5Weight ratio 0.25~0.5 is baking mixed, obtains calcification baking clinker；
B, the first order leach: step a calcification baking clinker is mixed with first order filtrate or/and second level leachate, then plus
Enter sulfuric acid and carry out first order leaching, control first order leaching process system pH is 2.8~3.5, is separated by solid-liquid separation after leaching
First order leachate and solid；Then solid is washed, obtains first order filtrate and solid；
C, the second level is leached: the solid after step b washing is carried out the second level using third level leachate or/and third level filtrate
It leaches, it is 1.8~3.5 that terminal system pH is leached in the control second level, is separated by solid-liquid separation to obtain second level leachate and solid；
D, the third level is leached: the solid after step c is leached carries out third level leaching, and the control third level leaches terminal system pH and is
1.4~2.2, it is separated by solid-liquid separation to obtain third level leachate and solid；Then solid is washed, obtains third level filtrate and vanadium extraction
Tailings.
2. vanadium slag low calcium according to claim 1-roasting counter current acid leaching vanadium extraction method, it is characterised in that: in step a,
At least meet following any one:
The maturing temperature is 840~930 DEG C；
The calcining time is 30~120min；
The calcification baking clinker granularity≤0.125mm.
3. the method for vanadium slag low calcium roasting-counter current acid leaching vanadium extraction according to claim 1 or 2, it is characterised in that: step b
In, the leaching at least meets following any one:
The first order leaches the first order filtrate used or/and second level leachate pH 2.2 or more；
It is 2~3 ﹕ 1 that the liquid that the first order leaches, which consolidates mass ratio,；
Content of vanadium is in 20g/L or more in the first order leachate；
The first order leachate pH is 2.8~4.0；
The temperature that the first order leaches is room temperature~70 DEG C；
The time that the first order leaches is 20~120min.
4. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions according to claim 1~3, it is characterised in that:
In step b, the washing at least meets following any one:
The liquid pH that uses of washing is 2.8~7.0；
It is 0.5~1.0 ﹕ 1 that the liquid of the washing solid, which consolidates mass ratio,；
The first order filtrate terminal content of vanadium < 2g/L.
5. the method for vanadium slag low calcium roasting-counter current acid leaching vanadium extraction according to any one of claims 1 to 4, it is characterised in that:
In step b, the liquid that the washing uses in the waste water lime and/or electrolysis treated recycle-water, pH is adjusted to 2.8~
7.0。
6. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions according to claim 1~5, it is characterised in that:
In step c, at least meet following any one:
The third level leachate used or/and third level filtrate pH are leached as 1.4~2.2 in the second level；
It is 1.5~2.5 ﹕ 1 that the liquid that the second level is leached, which consolidates mass ratio,；
Content of vanadium < 6g/L in the second level leachate；
The temperature that the second level is leached is room temperature~70 DEG C；
The time that the second level is leached is 1~5min.
7. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions according to claim 1~6, it is characterised in that:
In step d, the leaching at least meets following any one:
The third level, which is leached, uses liquid pH for 0.7~1.5；
It is 1.2~2.0 ﹕ 1 that the liquid that the third time leaches, which consolidates mass ratio,；
Content of vanadium < 6g/L in the third level leachate；
The temperature that the third time leaches is room temperature~70 DEG C；
The time that the third time leaches is 5~10min.
8. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions according to claim 1~7, it is characterised in that:
In step d, the third level leaches the liquid used in waste water lime and/or electrolysis treated recycle-water, pH are adjusted to
0.7~1.5.
9. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions according to claim 1~8, it is characterised in that:
In step d, the washing at least meets following any one:
The liquid pH that uses of washing is 1.4~7；
It is 0.5~1.0 ﹕ 1 that the liquid of the washing solid, which consolidates mass ratio,；
The third level filtrate terminal content of vanadium < 0.4g/L.
10. the method for described in any item vanadium slag low calcium roasting-counter current acid leaching vanadium extractions, feature exist according to claim 1~9
In: in step d, the liquid that the washing uses is in the waste water lime and/or electrolysis treated recycle-water, pH are adjusted to 1.4
~7.
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| CN110129576A (en) * | 2019-06-24 | 2019-08-16 | 攀钢集团钒钛资源股份有限公司 | Secondary extract technology and its belt for acid-leaching vanadium-extracted tailings elute filtration system |
| CN110387468A (en) * | 2019-08-30 | 2019-10-29 | 攀钢集团钒钛资源股份有限公司 | Control the stable method of calcification clinker second level acidleach pH |
| CN110643838A (en) * | 2019-11-12 | 2020-01-03 | 四川大学 | Method for roasting vanadium slag by adopting calcium sulfate |
| CN110951970A (en) * | 2019-11-28 | 2020-04-03 | 攀钢集团钒钛资源股份有限公司 | Method for recovering vanadium from vanadium-containing underflow slag |
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| CN110129576A (en) * | 2019-06-24 | 2019-08-16 | 攀钢集团钒钛资源股份有限公司 | Secondary extract technology and its belt for acid-leaching vanadium-extracted tailings elute filtration system |
| CN110387468A (en) * | 2019-08-30 | 2019-10-29 | 攀钢集团钒钛资源股份有限公司 | Control the stable method of calcification clinker second level acidleach pH |
| CN110643838A (en) * | 2019-11-12 | 2020-01-03 | 四川大学 | Method for roasting vanadium slag by adopting calcium sulfate |
| CN110951970A (en) * | 2019-11-28 | 2020-04-03 | 攀钢集团钒钛资源股份有限公司 | Method for recovering vanadium from vanadium-containing underflow slag |
| CN111392774A (en) * | 2020-03-13 | 2020-07-10 | 吉林吉恩镍业股份有限公司 | Method for producing ammonium polyvanadate and high-heat-energy carbon powder by using vanadium-containing carbon ash as raw material |
| CN111392774B (en) * | 2020-03-13 | 2022-09-02 | 吉林吉恩镍业股份有限公司 | Method for producing ammonium polyvanadate and high-heat-energy carbon powder by using vanadium-containing carbon ash as raw material |
| CN111719051A (en) * | 2020-06-29 | 2020-09-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from vanadium slag by low-calcium roasting and acid leaching |
| RU2793681C2 (en) * | 2020-09-24 | 2023-04-04 | Паньган Груп Паньчжихуа Айрон Энд Стил Рисёч Инститьют Ко , Лтд. | Method for extracting vanadium from vanadium slag by roasting with a composite based on calcium and manganese |
| CN112593077A (en) * | 2020-11-25 | 2021-04-02 | 四川龙蟒矿冶有限责任公司 | Method for acid countercurrent heap leaching of vanadium titano-magnetite alkaline oxidized pellets |
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