CN109338103A - The method of calcification baking clinker counter current acid leaching vanadium extraction - Google Patents
The method of calcification baking clinker counter current acid leaching vanadium extraction Download PDFInfo
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- CN109338103A CN109338103A CN201811459917.2A CN201811459917A CN109338103A CN 109338103 A CN109338103 A CN 109338103A CN 201811459917 A CN201811459917 A CN 201811459917A CN 109338103 A CN109338103 A CN 109338103A
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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
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
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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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Abstract
The invention belongs to vanadium extraction technical fields, and in particular to the method for calcification baking clinker counter current acid leaching vanadium extraction.Technical problem to be solved by the invention is to provide the methods of calcification baking clinker counter current acid leaching vanadium extraction, the following steps are included: a, clinker mixed with first order filtrate or/and second level leachate, sulfuric acid is added to be leached, controlling 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；B, 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；C, 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 oxide extractive technique fields, and in particular to the method for calcification baking clinker counter current acid leaching vanadium extraction.
Background technique
Vanadium slag is after calcification baking, and slag middle or low price vanadium is (with V3+、V4+Based on) gradually calcium oxide turn to calcium vanadate (manganese) class
Close object, such as CaV2O6、Ca2V2O7、Ca3V2O8、MnCaV2O7Deng 50~60 DEG C of extraction temperature, leaching pH value 2.8 in laboratory
~3.2, the dissolution rate of vanadium can achieve 88% or so.
However vanadium dissolution leaching rate is lower during produced on-site, main cause is: firstly, live extraction temperature is difficult to reach
To technique requirement, when especially scene does not have Insulation, extraction temperature control only determines that leachate is solid with test with experience
Than and sulfuric acid concentration, actual production process influenced by roasting calcium vanadium ratio, maturing temperature, the factors such as seasonal variety, extraction temperature
Fluctuation is very big, and when in addition extraction temperature is higher than 70 DEG C, vanadium, which can hydrolyze, occurs irreversible precipitation phenomenon, so scene haves no alternative but set
Setting extraction temperature is 30~60 DEG C, and practical leaching rate is low compared with laboratory.Secondly, leaching this range of pH=2.8~3.2 is relatively narrow,
And leaching process is that intermittent single tank leaches, it is high to the required precision of pH detection device, however pH electrode is immersed in high vanadium leaching for a long time
Out in liquid, it is easy to happen vanadium liquid poisoning problem, in addition, interval leaching requires charging and discharging every time, pH electrode is in soda acid and does
Wet alternate state, service life is short, and zero drift phenomenon frequent occurrence, cause survey pH value can not accurate stable 2.8
In~3.2 ranges, the leaching dissolution rate of vanadium is further decreased.Furthermore also by factors such as leaching liquid-solid ratio, stirring, filtration washings
Influence, in fact, scene once leach vanadium dissolution leaching rate it is 3~5 percentage points generally low compared with laboratory.
After phase research shows that vanadium slag adds calcium salt oxidizing roasting, vanadium is essentially converted to the vanadate of pentavalent, and mainly assigns
There are in vanadate, iron oxide solid solution, pseudobrookite and silicate, once sufficiently leach after washing, the vanadium base in vanadate
Originally it is completely dissolved, about 2/3 vanadium dissolution in iron oxide solid solution, about 1/3 vanadium dissolution in pseudobrookite, the vanadium base in silicate
This is insoluble, and the vanadium of final residue is primarily present in iron oxide solid solution > pseudobrookite > silicate, account for 41.94% respectively,
26.87% and 25.61%, and vanadium in a manner of wrapping up and inlay there are in these object phases, within the scope of a leaching condition
It is difficult that these three objects are mutually destroyed to and leached vanadium therein.In fact it further study show that, improves and leaches acid concentration or reduction
Iron oxide solid solution and pseudobrookite phase can effectively and rapidly be destroyed by leaching pH value, and leach wherein about 2/3 vanadium respectively, this
Leaching way is known as " depth leaching ".But due to the raising of acidity, in slag with the overwhelming majority of phosphorus existing for phosphoric acid calcium form (>=
95%) it can be leached into solution, phosphorus content is caused in leachate to be greater than 0.10g/L, and vanadium only 2-6g/L, it is heavy much higher than normal
Phosphorus≤0.03g/L, the requirement of vanadium >=20g/L technique when vanadium.It joined a large amount of acid when depth leaches simultaneously, depth leachate
PH value≤1.5 cannot return to primary leach and use, because can make when initial pH≤2.0 are when returning to primary leach containing vanadium solution
Ripe material, which leaches, occurs irreversible precipitation phenomenon early period, leads to relatively conventional low 5 percentage points once leached of the leaching rate of vanadium
More than, so being unable to direct reuse.
Have at present from pH≤1.5, vanadium 2-6g/L, phosphorus >=0.1g/L leachate recycling vanadium method very much, by Vanadium Concentrationin
Method divergence can be classified as three kinds of ion-exchange, extraction and evaporation concentration method etc., before two kinds have gained five oxidation two
The advantage of vanadium purity is high, but there is also process flow length, disadvantage at high cost, it is much like with process for extracting vanadium from stone coal；And it evaporates
Concentration method is a kind of method for preparing thick vanadic anhydride, and advantage is exactly that process is short, but disadvantage is also very prominent, i.e. vanadic anhydride
Product quality is unqualified, and evaporation and concentration water is big, at high cost.All there is at high cost ask in these three process for extracting vanadium of Comprehensive Correlation
Topic and certain environmentally friendly risk, and it is limited by vanadic anhydride turn of the market, industrialization prospect causes anxiety.
CN105219976A discloses in a kind of preceding 15min the primary interval that progress is mixed slowly after quickly stirring+15min
Property leach (pH=2.8-3.2) method.CN106987716A discloses a kind of continuous acidic leaching of vanadium slag calcification baking clinker
Current primary intermittent leach only is changed to continuous leaching by method, but minimum pH >=2.5 of leaching process.CN107475518A
A kind of method that vanadium classification is leached is disclosed, but the leachate of pH < 2.0 impurity is high, can not recycle and soak there is no solving
Water yield is big, the unbalanced problem of water.
Summary of the invention
The defects of relatively low, vanadium product quality is not high for there are vanadium extraction rates in prior art vanadium extraction field, the present invention mentions
The method for having supplied a kind of high, good product quality the calcification baking clinker counter current acid leaching vanadium extraction of vanadium extraction rate.
Technical problem to be solved by the invention is to provide a kind of methods of calcification baking clinker counter current acid leaching vanadium extraction.The party
Method the following steps are included:
A, the first order leaches: calcification baking clinker being mixed with first order filtrate or/and second level leachate, is then added
Sulfuric acid carries out first order leaching, and control first order leaching process system pH is 2.8~3.5, be separated by solid-liquid separation after leaching the
Level-one leachate and solid；Then solid is washed, obtains first order filtrate and solid；
B, the second level is leached: the solid after step a 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；
C, the third level is leached: the solid after step b 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 calcification baking clinker counter current acid leaching vanadium extraction, the calcification baking clinker granularity
≤0.125mm。
Preferably, in the method and step a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the first order leaches use
First order filtrate or/and second level leachate pH are 2.2 or more.
Specifically, the liquid that the first order leaches is solid in the method and step a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction
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 a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the first order leachate pH is
2.8~4.0.
Specifically, in the method and step a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the temperature of the first order leaching
For room temperature~70 DEG C.Extraction time is 20~120min.
Preferably, in the method and step a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the liquid pH of the washing use
It 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, in the method and step a of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the liquid stereoplasm of the washing solid
Amount is than being 0.5~1.0 ﹕ 1.Gained first order filtrate terminal content of vanadium < 2g/L.
Preferably, in the method and step b of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, use is leached in the second level
Third level leachate or/and third level filtrate pH are 1.4~2.2.
Specifically, the liquid that the second level is leached is solid in the method and step b of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction
Mass ratio is 1.0~2.5 ﹕ 1.Content of vanadium < 6g/L in the leachate of the gained second level.
Specifically, in the method and step b of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the temperature of the second level leaching
For room temperature~70 DEG C.Extraction time is 1~5min.
Preferably, in the method and step c of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the third level, which is leached, uses liquid
Body pH is 0.7~1.5.The third level leaches the liquid used in waste water lime and/or electrolysis treated recycle-water,
PH is adjusted to 0.7~1.5.
Specifically, the liquid that the third time leaches is solid in the method and step c of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction
Mass ratio is 0.7~1.5 ﹕ 1.Content of vanadium < 6g/L in gained third level leachate.
Specifically, in the method and step c of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the temperature of the third time leaching
For room temperature~70 DEG C.Extraction time is 5~10min.
Preferably, in the method and step c of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the liquid pH of the washing use
It is 1.4~7.The liquid that the washing uses in the waste water lime and/or electrolysis treated recycle-water, pH is adjusted to 1.4~
7。
Specifically, in the method and step c of above-mentioned calcification baking clinker counter current acid leaching vanadium extraction, the liquid stereoplasm of the washing solid
Amount is than being 0.5~1.0 ﹕ 1.Gained third level filtrate terminal content of vanadium < 0.4g/L.
The method of the present invention is by counterflow leaching, and compared with traditional primary interval extract technology, TV can be steady in tailings in vanadium extraction
Surely 0.9% is reduced to hereinafter, the dissolution leaching rate of vanadium improves 8 percentage points.Since 2-3 grades of leaching acidity are high, reaction is pushed
Power is big, leaches rapidly and efficiently, can relax the 1st leaching production control and require, the 1st vanadium not leached of actual production passes through
2-3 grades of leachings can still recycle, and improve production efficiency and stability.The full vanadium concentration of the method for the present invention first order leachate is high,
Impurity is low, and the resulting vanadium product quality of Direct precipitation is high.The method of the present invention leaching equipment is simply easily implemented, and there is no water balances
Problem is easy to industrialization.
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
The method of calcification baking clinker counter current acid leaching vanadium extraction of the present invention, comprising the following steps:
A, the first order leaches: calcification baking clinker being mixed with first order filtrate or/and second level leachate, is then added
Sulfuric acid carries out first order leaching, and control first order leaching process system pH is 2.8~3.5, be separated by solid-liquid separation after leaching the
Level-one leachate and solid；Then solid is washed, obtains first order filtrate and solid；
B, the second level is leached: the solid after step a 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；
C, the third level is leached: the solid after step b 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.
The method of the present invention step a 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 a 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 leaches liquid (i.e. first order filtrate, second level leachate or both the mixed solution) pH used 2.2 or more,
Liquid pH such as use is too low, can direct precipitation after leaching.When first time carrying out the method for the present invention, the first order leaches use
Liquid can directly select be adjusted to pH 2.2 or more domestic water, industrial water, distilled water, recycle-water etc. either its
Even if it is containing impurity but not the other of influence the method for the present invention implementation use water.The method of the present invention is being carried out for the second time and later
When, 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 a 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 a leaching step, most vanadium and the dissolution of minimal amount of phosphorus, vanadium generally dissolve in clinker
80% or more, phosphorus generally dissolves 18% hereinafter, playing the role of simultaneously " checking on ", TV/P mass ratio in control first order leachate
1000 or more, and TV concentration is in 20g/L or more.In fact, leached by the first order, in clinker, most soluble vanadium is all
Be leached, only a small amount of soluble vanadium and by package vanadium residual in solids.
The method of the present invention step a 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 a 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 a 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 b 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 a 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 c 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 1.0~2.5 ﹕ 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 c 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 0.7 that the liquid that the third time leaches, which consolidates mass ratio,
~1.5 ﹕ 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 c 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 0.9% or less.
The method of the present invention step c 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
The first order leaches: being added into pH=2.6, first order filtrate 150mL and second level leachate 350mL mixed solution
200g calcification baking clinker (TV=8.66%) uses sulfuric acid control system pH=2.8-3.0 under agitation, controlled at
50 DEG C of leaching 45min, filter to obtain first order leachate and filter residue, measure TV=33.87g/L, P=in first order leachate
0.02g/L, first order leachate pH are 3.1；Filter residue pH=7 reuse water washing, first order filtrate pH are 3.5；
Leach the second level: it is that 1.42 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；
The third level is leached: filter residue is added to pH=0.7,200mL recycle-water and leaches third level leaching, is stirred to react 10min
After filter, third level leachate pH be 1.40；PH=7 reuse water washing is used again, and third level filtrate pH is 1.45, obtains vanadium extraction tail
Slag.
Tailings in vanadium extraction drying measures TV=0.74%, then (the vanadium total amount ÷ in 1-3 grades of leachates is ripe for the dissolution leaching rate of vanadium
Vanadium total amount in material) it is 91%.
Embodiment 2
The first order leaches: to pH=2.8, first order filtrate 12m3With second level leachate 6m36t calcium is added in mixed solution
Salt roasting clinker (TV=8.66%) uses sulfuric acid control system pH=2.8-3.0 under agitation, soaks controlled at 41 DEG C
60min out filters to obtain first order leachate and filter residue, measures TV=32.67g/L, P=0.02g/L in first order leachate, the
Level-one leachate pH is 3.05；Filter residue pH=6.78 reuse water washing, first order filtrate pH are 3.41；
Leach the second level: it is that 1.6 third level leachates leach that filter residue uses pH again after washing, and the of pH=2.7 is obtained by filtration
Second level leachate；
The third level is leached: filter residue is added to pH=1.4,7m3Recycle-water carries out third level leaching, after being stirred to react 10min
Filtering, third level leachate pH are 1.6；PH=7 reuse water washing is used again, and third level filtrate pH is 1.65, obtains tailings in vanadium extraction.
Tailings in vanadium extraction drying measures TV=0.81%, then the dissolution leaching rate of vanadium is 90.64%.
Embodiment 3
The first order leaches: to pH=2.7, first order filtrate 12m3With second level leachate 6m36.5t is added in mixed solution
Calcification baking clinker (TV=8.12%) uses sulfuric acid control system pH=2.8-3.0, under agitation controlled at 56 DEG C
60min is leached, first order leachate and filter residue is filtered to obtain, measures TV=34.35g/L, P=0.02g/L in first order leachate,
First order leachate pH is 2.94；Filter residue pH=7 reuse water washing, first order filtrate pH are 2.98；
Leach the second level: it is that 1.45 third level leachates leach that filter residue uses pH again after washing, and the of pH=2.5 is obtained by filtration
Second level leachate；
The third level is leached: filter residue is added to pH=1.0,7m3Recycle-water carries out third level leaching, is stirred to react mistake after 7min
Filter, third level leachate pH are 1.45；PH=1.5 reuse water washing is used again, and third level filtrate pH is 1.50, obtains tailings in vanadium extraction.
Tailings in vanadium extraction drying measures TV=0.74%, then the dissolution leaching rate of vanadium is 90.89%.
Comparative example 1
To 17m36.5t calcification baking clinker (TV=8.12%) is added in tap water, controls pH with sulfuric acid under agitation
After=2.8-3.0, temperature are 56 DEG C of leaching 60min, solid-liquor separation obtains leachate, measures TV=25.76g/L, P=0.02g/L,
After filter residue is sufficiently washed with tap water, tailings in vanadium extraction is obtained, drying measures to obtain TV=1.38%, and the dissolution leaching rate of vanadium is 83%.
The above are combination exemplary embodiments to elaborate to of the invention, however, the present invention is not limited thereto.
Claims (10)
1. the method for calcification baking clinker counter current acid leaching vanadium extraction, it is characterised in that: the following steps are included:
A, the first order leaches: calcification baking clinker being mixed with first order filtrate or/and second level leachate, sulfuric acid is then added
First order leaching is carried out, control first order leaching process system pH is 2.8~3.5, and the first order is separated by solid-liquid separation to obtain after leaching
Leachate and solid；Then solid is washed, obtains first order filtrate and solid；
B, the second level is leached: the solid after step a 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；
C, the third level is leached: the solid after step b 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. the method for calcification baking clinker counter current acid leaching vanadium extraction according to claim 1, it is characterised in that: in step a, institute
It states first order leaching and 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.
3. the method for calcification baking clinker counter current acid leaching vanadium extraction according to claim 1 or 2, it is characterised in that: step a
In, 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.
4. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~3, it is characterised in that:
In step a, 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。
5. the method for calcification baking clinker counter current acid leaching vanadium extraction according to any one of claims 1 to 4, it is characterised in that:
In step b, 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 1.0~2.5 ﹕ 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.
6. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~5, it is characterised in that:
In step c, the third time leaching at least meets following any one:
The third level, which is leached, uses liquid pH for 0.7~1.5；
It is 0.7~1.5 ﹕ 1 that the liquid that the third time leaches, which consolidates mass ratio,；
Content of vanadium < 6g/L in gained 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.
7. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~6, it is characterised in that:
In step c, 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.
8. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~7, it is characterised in that:
In step c, 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.
9. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~8, it is characterised in that:
In step c, the liquid that the washing uses in the waste water lime and/or electrolysis treated recycle-water, pH is adjusted to 1.4~
7。
10. the method for described in any item calcification baking clinker counter current acid leaching vanadium extractions according to claim 1~9, it is characterised in that:
In step a, the calcification baking clinker granularity≤0.125mm.
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| 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 |
| CN112593097A (en) * | 2020-12-02 | 2021-04-02 | 攀钢集团研究院有限公司 | Continuous leaching vanadium extraction method for vanadium slag calcified clinker |
| CN114350982A (en) * | 2021-11-30 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for extracting vanadium by using calcified roasting clinker and recycling leaching washing liquid |
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| CN115232961B (en) * | 2022-08-02 | 2023-07-25 | 四川省冶金地质勘查局六0一大队 | Method for extracting vanadium by decalcification of calcified vanadium extraction tailings |
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| CN105331832A (en) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid-leaching washing method for vanadium-containing roasting clinker |
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| CN100582257C (en) * | 2007-11-26 | 2010-01-20 | 攀枝花钢铁(集团)公司 | Method for roasting high-calcium vanadium slag by using fluidizing equipment |
| CN103993161B (en) * | 2014-05-21 | 2016-11-16 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of the two-part calcification baking of vanadium-containing material |
| CN104388679B (en) * | 2014-09-30 | 2016-09-28 | 边悟 | Method containing vanadium raw materials vanadium extraction |
| CN104894370B (en) * | 2015-05-29 | 2017-07-07 | 河北钢铁股份有限公司承德分公司 | The method for leaching solvable vanadium from roasted vanadic slag with low-concentration sulfuric acid |
| RU2651842C2 (en) * | 2016-05-24 | 2018-04-24 | Акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method for processing black shale ores |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112593097A (en) * | 2020-12-02 | 2021-04-02 | 攀钢集团研究院有限公司 | Continuous leaching vanadium extraction method for vanadium slag calcified clinker |
| CN114350982A (en) * | 2021-11-30 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for extracting vanadium by using calcified roasting clinker and recycling leaching washing liquid |
| CN114350982B (en) * | 2021-11-30 | 2023-09-15 | 攀钢集团研究院有限公司 | Method for extracting vanadium and recycling leaching washing liquid by calcified roasting clinker |
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