CN107287410A - A kind of compound additive and its application method for being used to be calcined vanadium extraction - Google Patents
A kind of compound additive and its application method for being used to be calcined vanadium extraction Download PDFInfo
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- CN107287410A CN107287410A CN201710536869.1A CN201710536869A CN107287410A CN 107287410 A CN107287410 A CN 107287410A CN 201710536869 A CN201710536869 A CN 201710536869A CN 107287410 A CN107287410 A CN 107287410A
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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Abstract
It is used to being calcined the compound additive of vanadium extraction there is provided a kind of the present invention relates to metallurgical technology field, including following four material mix by mass fraction and to be ground to 80 mesh~100 mesh obtained：35~55 parts of material containing sodium, 15~25 parts of calcium-containing material, 0.5~1 part of vanadium-containing material, 1~5 part of titaniferous material；A kind of application method for being used to be calcined the compound additive of vanadium extraction is also provided, comprised the following steps：A, batch mixing：The vanadium raw materials that contain after screening are chosen, addition compound additive is well mixed to obtain batch mixing；B, roasting：Batch mixing is calcined in two times.Using the compound additive and its application method in the technical program, stone containing navajoite is not likely to produce liquid phase in roasting process, it is not in the phenomenon of stamping device, it is not likely to produce poisonous and harmful substance, and the conversion ratio and purity of vanadium are effectively improved, shorten roasting time, simplify roasting technique, production cost is reduced, process efficiency is improved.
Description
Technical field
The present invention relates to metallurgical technology field, and in particular to a kind of compound additive and its user for being used to be calcined vanadium extraction
Method.
Background technology
Vanadium is trace element widely distributed on the earth, and its content accounts for the 0.02% of earth's crust composition, obtains relatively easy.
Because vanadium has numerous excellent physical properties and chemical property, thus the purposes of vanadium is quite varied, have metal " vitamin " it
Claim, be development modern industry, modern national defense and the indispensable important materials of modern science and technology.Vanadium in nature it is main with
Stable lower valency (trivalent) form is present in ore, and the vanadium of this valence state is not readily dissolved in acid-base solution, and vanadium is had
Effect ground dissolution from ore, then need the vanadium in ore turning valency into high-valence state (tetravalence or pentavalent) from lower valency.
Current vanadium turns method of the valency generally by roasting stone containing navajoite, is then realized again with subsequent steps such as Ore Leachings
Vanadium extraction, traditional roasting process for extracting vanadium has：1. roasting direct vanadium extraction, this method is direct oxidation roasting stone containing navajoite, right
Environmental pollution is smaller, but the conversion ratio of this process vanadium is very low, is not suitable for industrial production, this method quilt substantially
Eliminate；2. direct sulfuric acid leaching vanadium extraction, this method technical process is fairly simple, but needs to spend substantial amounts of sulfuric acid, cost
Height, is not also favored by industrial production producer.
To have solved the problems, such as in traditional process for extracting vanadium, industrial production the additivated roasting vanadium extraction side of a class gradually newborn
Method, this method is compared with traditional process for extracting vanadium, and vanadium extraction rate is higher, and production cost is relatively low, and this method is according to additive
Species can be divided into following several again：
A, sodium-salt calcination
The additive that this method is used includes single sodium salt additive and compound sodium salt additive.Single sodium salt adds
Plus agent is more using NaCl as additive, the addition of this method not only additive is larger, and the conversion ratio of vanadium is relatively low, gradually
It is eliminated.
Have many researchs at present to compound sodium salt additive, such as CN103484667A disclose a kind of sodium chloride and
Na2SO4Compound additive, also disclose that in CN101497946A a kind of using sodium hydroxide, sodium chloride, Na2CO3Constitute
Compound additive, does not react yet with materials such as the vanadium in the chlorine and ore in additive, so chlorine generally all can be by
It is discharged into natural environment, huge injury is caused to environment, and because the fusing point of sodium hydroxide is relatively low, in conventional roasting
During easily produce liquid phase so that easily lumpd in the relatively low region of temperature in roasting process, influence roasting apparatus it is smooth.
To solve the addition pollution on the environment of sodium chloride, CN101008048A and CN101177738A disclose one
Plant and add slag or other mineral in the compound additive that NaCl and other sodium salts are constituted to fix in NaCl roasting process
Produced pernicious gas (such as Cl2, HCl) method.Solidfied material composition is mainly Fe2O3And zincblende, during solidification
Fe2O3, zincblende and chlorine form the iron chloride and zinc chloride being largely not easily decomposed, so as to reach the purpose of fixed pernicious gas.But
It is due to that iron chloride can seethe with excitement distillation more than 320 DEG C, the distillation and zinc chloride can come to life more than 740 DEG C, therefore 750
DEG C~850 DEG C of roasting condition under iron chloride and zinc chloride can generate substantial amounts of sublimation gases, substantial amounts of heat is taken away, while in temperature
The relatively low region flue gas of degree can sublimate generation solid adhesion again, bond and form tumor mass in a device, the normal fortune of influence equipment
OK.
B, calcium salt roasting
The additive that this method is used also includes single calcium salt additive and composite calcium salt additives.Single calcium salt
Additive will not produce Cl in roasting process2Or the dusty gas such as HCl, but this additive has very big to stone containing navajoite
Selectivity, it is relatively low to the conversion ratio of vanadium, be unsuitable for commercial Application.CN101215648A discloses a kind of using the compound roasting of calcium salt
The method of roasting of additive is burnt, but this method is applied to be calcined under the conditions of 870 DEG C~980 DEG C up to 7 hours, is calcined
Time is longer, and sintering temperature is too high.
C, sodium salt, calcium salt compound roasting
CN102296192A discloses a kind of cryolite (mass fraction 35%~45%), calcirm-fluoride (mass fraction
40%~50%) and alkali metal the compound additive that is made into of peroxide (mass fraction 15%~25%) mixing, but
The peroxide cost of alkali metal in this compound additive is high and is extremely easy in decomposition, and easily potential safety hazard occurs in decomposable process,
Oil repellent is too high in additive simultaneously, and too high Oil repellent is easily caused impurity more in ore deposit and be leached, and substantially reduces follow-up
The purity of vanadium product.CN101613797A also discloses that a kind of NaCl, CaF2And CaCO3The compound additive of composition, the additive
Need first to add 5%~40% water in use, the addition of water needs to add drying device before roasting, and process is relative
Complexity, adds production cycle and cost.CN101892380A and CN101492775A also disclose a kind of chemical combination of use barium
The simple substance and Na of thing or barium2CO3、CaCO3The additive of composition.Additive barium salt toxicity used in such method is stronger, workman
Easily cause acute poisoning accident after the soluble barium of a large amount of contacts.
D, biomaterial roasting
CN104561608A and CN101054634A disclose the addition of a kind of novel biomaterial maize straw and wood chip
Agent, this kind of biomaterial has stronger recyclability, and inexpensive.But maize straw and this kind of material of wood chip are in roasting
During be also easy to produce larger flue dust, it is necessary to set up the facility that gathers dust, and add biomaterial be carbonaceous material, roasting
During oxygen in easy consumption calcination atmosphere and produce the atmosphere (such as CO) of reproducibility, reducing atmosphere can translate into height again
Valence state vanadium reduction as lower valency vanadium, have a strong impact on the conversion ratio of vanadium, at the same in reducing atmosphere CO content often compared with
Many, the security incident such as easily occur being poisoned.
E, other roastings
CN101693947A discloses the compound additive that the hydroxide of a kind of nitrate and aluminium is constituted, but nitrate
Easily decompose at high temperature and produce nitrogen oxides, environmental pollution is larger, while the roasting technique of the additive is complex, production
It is less efficient.CN101693946A discloses the compound additive that a kind of tungsten oxide and titanium oxide are made into, but this is compound
Additive needs to be pre-mixed into slurry, can be calcined after drying, longer, about 4h~14h the time required to drying process, and
It is about leaching at 50 DEG C~100 DEG C that ore deposit after roasting, which is needed in temperature, and whole extraction process is less efficient.
As can be seen from the above analysis, the process for adding compound additive is the first choice being calcined in process for extracting vanadium, multiple
Close additive and also play very important effect in the technique of roasting vanadium extraction, and how to solve in the prior art, ore exists
What roasting process was present is also easy to produce liquid phase, and stamping device, roasting time is long, and complex process, cost is higher, and production efficiency is relatively low,
The conversion ratio and purity of vanadium are all relatively low, the problems such as being also easy to produce harmful and noxious substance, are the heavy difficult points in current vanadium extraction technology.
The content of the invention
It is an object of the invention to provide a kind of compound additive and its application method for being used to be calcined vanadium extraction so that containing vanadium
Ore is not likely to produce liquid phase in roasting process, is not in the phenomenon of stamping device, is not likely to produce poisonous and harmful substance, and have
Effect improves the conversion ratio and purity of vanadium, shortens roasting time, simplifies roasting technique, reduces production cost, improves process efficiency.
To reach above-mentioned purpose, base case of the invention is：A kind of compound additive for being used to be calcined vanadium extraction, bag are provided
Include following four material and mixed by mass fraction and be ground to the mesh of 80 mesh~100 and be made：35~55 parts of material containing sodium, calcium-containing material
15~25 parts, 0.5~1 part of vanadium-containing material, 1~5 part of titaniferous material.
The operation principle and beneficial effect of above-mentioned technical proposal are：
1st, the material containing sodium in compound additive is the mixing of the compound containing sodium or the compound containing a variety of sodium
Thing, calcium-containing material is the mixture of the compound containing calcium or the compound containing polycalcium, and vanadium-containing material is to contain vanadium
The mixture of compound or compound containing a variety of vanadium；Wherein material containing sodium and calcium-containing material, will as the transforming agent of vanadium
Vanadium is converted into the salt for being soluble in acid, and the vanadium-containing material being easy in vanadium extraction, compound additive and titaniferous material are accelerated as catalyst
The conversion rate of vanadium；
2nd, titaniferous material is as the principle of the conversion rate of catalyst quickening vanadium：There is empty d tracks on titanium atom,
Acceptable electronics or electronics pair, while the electronics on d tracks also easily loses, i.e., titanium atom can enter as acceptor with part
Row coordination, part and the Viability intermediate of titanium atom coordination type, can reduce the reaction activity of vanadium conversion, in same reaction
Under the conditions of bioactive molecule number it is more, so that the purpose for accelerating vanadium conversion reaction efficiency is reached, when there is new part attack titanium atom
When, original part departs from titanium atom, then with new ligand binding, so circulation, until completing whole reaction；And this technology
Titanium in scheme itself can not only accelerate the conversion of vanadium as catalyst, and can also increase the surface area of vanadium catalyst, so that
Improve the surface-active of vanadium catalyst, the speed of overall further lifting vanadium conversion；
3rd, compared with sodium-salt calcination method of the prior art, the conversion ratio of vanadium, and this compound addition can not only be improved
Each congruent melting point is all higher in agent, in roasting process, is difficult after distillation and sublimates to produce in the relatively low region of device temperature
Liquid phase, effectively prevents occurring bonding phenomenon in roasting apparatus；
4th, compared with calcium salt method of roasting of the prior art, sodium, calcium in this compound additive can be with vanadium combination shapes
Into vanadic salts, the efficiency that vanadium is converted into high price from low price is helped speed up, sintering temperature is reduced；
5th, compared with sodium salt in the prior art, calcium salt compound roasting system, this compound additive is difficult in roasting process
Impurity is produced, impurity more in ore will not also be leached, be favorably improved the leaching purity of vanadium, reduce the work of follow-up removal of impurities
Measure and cost；
6th, compared with biomaterial method of roasting of the prior art, this compound additive in combustion, will not be produced
Immunogenic substance of surviving reduces high price vanadium, it is ensured that vanadium is converted into high price by lower price high efficiency rate, improves the conversion ratio of vanadium；
7th, compared with sodium salt of the prior art, calcium salt compound roasting system or biomaterial method of roasting etc., this is multiple
Close each composition in additive and the materials such as poisonous and harmful substance, and calcium salt are not likely to produce in roasting process to being produced in roasting process
Waste gas have conversion solidification, environmental protection；
8th, this compound additive not only has its specific technique effect compared to various existing additives, while only passing through
This compound additive, it is possible to while reaching multinomial technique effect, solve multinomial problem present in existing vanadium extraction technology, production
Unexpected technique effect is given birth to；
9th, first each material is mixed in the technical program, then is ground to the mesh of 80 mesh~100, not only each material mixing is more equal
It is even fully, and be ground come granular size can thorough roasting, effective conversion of vanadium is can guarantee that again, contribute to save produce
Cost, improves the conversion ratio of vanadium.
Preferred scheme one：Based on scheme preferred scheme, material containing sodium is by Na2SO4And Na2CO3According to mass ratio 7
~9:1~2 mixes.The compound additive provided in the technical program, Na2SO4And Na2CO3It is main to be converted into vanadium
One of transforming agent of salt of acid is soluble in, and compared with using NaCl sodium-salt calcination method in the prior art, the technical program
In compound additive Cl will not be produced in roasting process2Deng dusty gas；Na2CO3Alkalescence it is stronger, be conducive to contain navajoite
The destruction of stone structure, makes vanadium be easier leaching, and sodium carbonate helps to reduce sintering temperature, so as to improve the conversion ratio of vanadium；And
Na in the technical program2SO4Compared to Na2CO3Ratio it is higher, can effectively reduce follow-up with sour in Ore Leaching process for extracting vanadium
Usage amount (carbonate easily and acid reaction, and sulfate radical will not be with acid reaction), reduces production cost, and Na2SO4In industrial production
In be easily obtained, advantage of lower cost further reduces cost.
Preferred scheme two：Based on scheme preferred scheme, calcium-containing material is by CaCO3Or and CaCO3With equivalent
CaO、CaF2According to mass ratio 80~95:1~5 mixes.The compound additive provided in the technical program, CaCO3(or
) and CaF CaO2It is the transforming agent for the salt that another main be converted into vanadium is soluble in acid, is made according to being matched in the technical program
The compound additive obtained；Comparatively speaking, the fluorine in the technical program proportioning contains higher additive with Oil repellent in the prior art
Amount is less, not only facilitates the conversion for promoting vanadium, and will not leach impurity more in ore, is favorably improved the pure of vanadium
Degree；Calcium can also be with reacting the SO of generation in roasting process2Solidification is combined, and generates CaSO4, prevent SO2It is discharged into environment or such as
In the prior art, the material absorbing waste gas such as other slags is further added by, the introducing and reduction that can be prevented effectively from other impurities are produced into
This；Meanwhile, the calcium in the technical program is difficult to be leached in follow-up Ore Leaching technique, effectively reduces in vanadium leachate
Impurity, improves the purity of vanadium.
Preferred scheme three：Based on scheme preferred scheme, vanadium-containing material is by V2O5With vanadic salts according to mass ratio 1~3:1
Mix, vanadic salts is Ca (VO3)2Or NaVO3Or FeVO3。V2O5The transformation efficiency of vanadium can be accelerated with vanadic salts, the conversion of vanadium is improved
Calcium and sodium in rate, and vanadic salts can also further combine to form the salt for being soluble in acid with vanadium, be favorably improved the conversion ratio of vanadium
And reaction rate；Meanwhile, the vanadium in the technical program is the high price vanadium of pentavalent, and it, can be straight not only in follow-up extract technology
Connect and the pentavalent vanadium got is converted in ore together into vanadium leachate, it is to avoid introduce impurity, and it is low with adding in the prior art
The technology of valency vanadium is compared, and the vanadium in the technical program can directly carry out catalytic-roast reaction, it is to avoid the preamble such as oxidizing lower vanadium is walked
Suddenly, calcination speed is fast, and the utilization rate of vanadium is high.
Preferred scheme four：Based on scheme preferred scheme, titaniferous material be ilmenite concentrate, rutile and high titanium slag in
It is at least one.Main component in ilmenite concentrate, rutile and high titanium slag is TiO2, TiO2As catalyst, it can effectively accelerate vanadium
Transformation efficiency；While TiO2Or a kind of material of better heat stability, effectively can stably be catalyzed vanadium conversion；And titanium is follow-up
Ore Leaching technique in, be difficult to be leached, be effectively reduced the impurity in vanadium leachate, improve the purity of vanadium, reduce follow-up place
Manage processing step and cost.
Preferred scheme five：In above-mentioned base case or preferred scheme one to four any one be used for be calcined answering for vanadium extraction
The application method of additive is closed, is comprised the following steps：
A, batch mixing：The vanadium raw materials that contain after screening are chosen, addition compound additive is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature be 400 DEG C~650 DEG C, roasting time be 0.5h~
1.5h；Second of sintering temperature is 750 DEG C~850 DEG C, and roasting time is 1h~2h.
The operation principle of the technical program is：Material containing sodium is Na using in compound additive2SO4And Na2CO3, calcic thing
Expect for CaCO3And CaF2, vanadium-containing material is V2O5With Ca (VO3)2, titaniferous material be ilmenite concentrate exemplified by, the master in the technical program
Chemically reacting is：
V2O3+Na2SO4+1/2O2=2NaVO3+SO2↑；
V2O3+O2+CaCO3=Ca (VO3)2+CO2↑；
V2O3+O2+Na2CO3=2NaVO3+CO2↑；
V2O3+O2=V2O5；
V2O5+CaCO3=Ca (VO3)2+CO2↑；
V2O5+Na2CO3=2NaVO3+CO2↑；
SO2+CaCO3+1/2O2=CaSO4+CO2↑；
The beneficial effect of the technical program is：
1st, wherein material containing sodium and calcium-containing material are used as catalyst as main transforming agent, calcium-containing material and vanadium-containing material
Accelerate reaction rate, the metavanadate (predominantly sodium metavanadate and metavanadic acid calcium) that vanadium is converted into is soluble in acid, is conducive to vanadium
Leaching and follow-up vanadium extraction；
2nd, will contain vanadium raw materials and compound additive it is well mixed after be calcined again, can allow and enter containing vanadium raw materials and compound additive
The sufficiently effective contact of row, reaction improves the conversion efficiency of calcination speed and vanadium；
3rd, by this compound additive and containing after vanadium raw materials mixing can roasting direct, technique is simple, and sintering temperature is relative
Relatively low, roasting time also obtains certain shortening, and process efficiency is high, without adding other additional steps, can effectively reduce production
Cost.
Preferred scheme six：Preferably five preferred scheme containing vanadium raw materials is vanadium titano-magnetite, v-bearing steel slag, contained
At least one of scherbinaite colliery, vanadium-containing shale and vanadium-containing wasting catalyst.This compound additive has general applicability, can be suitably used for
The stone containing navajoite of diversified forms in nature, it is adaptable to vanadium titano-magnetite, v-bearing steel slag, Rock coal containing alum in the technical program
When ore deposit, vanadium-containing shale and vanadium-containing wasting catalyst, the conversion ratio of vanadium is especially high.
Preferred scheme seven：Preferably five preferred scheme, the addition of compound additive is containing V in vanadium raw materials2O5
0.8~1.4 times of weight.Compound additive is added according to the ratio in the technical program, can not only to greatest extent allow and contain
Vanadium in vanadium raw materials is extracted, and compound additive also can fully be reacted, it is to avoid compound additive is wasted, and is saved
Production cost.
Preferred scheme eight：Preferably six or seven preferred scheme, the granular size containing vanadium raw materials is 80 mesh~100
Mesh.Using in the technical program granular size contain vanadium raw materials, mixing contain vanadium raw materials and compound additive when, more quickly have
Effect, meanwhile, in roasting process, because both sizes are almost suitable, so calcination also can be carried out uniformly, the extraction effect of vanadium
Rate and conversion ratio are all higher.
Preferred scheme nine：The content of free oxygen is 10% in preferably eight preferred scheme, step B calcination atmospheres
~30%.Free oxygen will be oxidized into high price vanadium containing the Low Valent Vanadium in vanadium raw materials, be carried out according to the oxygen content in the technical program
Roasting, can not only improve the high conversion rate that the oxygenation efficiency of vanadium, i.e. Low Valent Vanadium are converted into high price vanadium, improve having for this compound additive
Utilization rate is imitated, and for industrialization, free oxygen, without too high, is that can reduce the economical selection of production cost.
Embodiment
Embodiment 1
A kind of compound additive for being used to be calcined vanadium extraction that the present embodiment is provided, including following four material are mixed and ground
It is made to 80 mesh：Material containing sodium, calcium-containing material, vanadium-containing material and titaniferous material, wherein material containing sodium is by Na2SO4And Na2CO3Press
It is 9 according to mass ratio:2 mix, and calcium-containing material is by CaO and CaF2It is 95 according to mass ratio:1 mixes, vanadium-containing material by
V2O5With Ca (VO3)2It is 1 according to mass ratio:1 is constituted, and titaniferous material is made up of ilmenite concentrate.Material containing sodium, calcium-containing material, containing vanadium
The mixing match method of material and titaniferous material is：By Na2SO4And Na2CO3Mass conversion into same equivalent Na2O, by CaO
And CaF2Mass conversion into same equivalent CaO, by V2O5With Ca (VO3)2Mass conversion into same equivalent V2O5, by titanium
TiO of the mass conversion of concentrate into same equivalent2, then by four kinds of materials respectively according to Na2O、CaO、V2O5、TiO2On an equal basis work as
The mass ratio of amount is 55:25:0.5:1 carries out dispensing.
The application method for the compound additive for being calcined vanadium extraction that the present embodiment is provided, comprises the following steps：
A, batch mixing：V will be contained2O5It is ground for 0.5wt%-1.0wt% vanadium-containing shale, is broken into the mesh of granular size 80
Contain vanadium raw materials, addition vanadium-containing shale in V2O50.8 times of compound additive of weight, is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature is 400 DEG C, and roasting time is 0.5h；Second of roasting
It is 750 DEG C to burn temperature, and roasting time is that control the content of free oxygen in calcination atmosphere in 1h, roasting process be 10%, after roasting
Mineral leached with 2mol/L dilute sulfuric acids, leaching rate reaches 91%, and leachate is used for follow-up vanadium extraction.
Embodiment 2
A kind of compound additive for being used to be calcined vanadium extraction that the present embodiment is provided, including following four material are mixed and ground
It is made to 85 mesh：Material containing sodium, calcium-containing material, vanadium-containing material and titaniferous material, wherein material containing sodium is by Na2SO4And Na2CO3Press
It is 7 according to mass ratio:2 mix, and calcium-containing material is by CaO and CaF2It is 80 according to mass ratio:1 mixes, vanadium-containing material by
V2O5And NaVO3It is 2 according to mass ratio:1 is constituted, and titaniferous material is made up of rutile.Material containing sodium, calcium-containing material, vanadium-containing material
Mixing match method with titaniferous material is：By Na2SO4And Na2CO3Mass conversion into same equivalent Na2O, by CaO and
CaF2Mass conversion into same equivalent CaO, by V2O5And NaVO3Mass conversion into same equivalent V2O5, by rutile
Mass conversion into same equivalent TiO2, then by four kinds of materials respectively according to Na2O、CaO、V2O5、TiO2Same equivalent
Mass ratio is 45:20:1:5 carry out dispensing.
The application method for the compound additive for being calcined vanadium extraction that the present embodiment is provided, comprises the following steps：
A, batch mixing：V will be contained2O5It is ground for 0.5wt%-1.0wt% vanadium titano-magnetite, is broken into granular size 85
Purpose contains V in vanadium raw materials, addition vanadium titano-magnetite2O51 times of compound additive of weight, is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature is 500 DEG C, and roasting time is 0.5h；Second of roasting
It is 800 DEG C to burn temperature, and roasting time is that control the content of free oxygen in calcination atmosphere in 1h, roasting process be 15%, after roasting
Mineral leached with 2mol/L dilute sulfuric acids, leaching rate reaches 93%, and leachate is used for follow-up vanadium extraction.
Embodiment 3
A kind of compound additive for being used to be calcined vanadium extraction that the present embodiment is provided, including following four material are mixed and ground
It is made to 90 mesh：Material containing sodium, calcium-containing material, vanadium-containing material and titaniferous material, wherein material containing sodium is by Na2SO4Pressed with Na2CO3
It is 7 according to mass ratio:1 mixes, and calcium-containing material is by CaO and CaF2It is 95 according to mass ratio:5 mix, vanadium-containing material by
V2O5And FeVO3It is 3 according to mass ratio:1 is constituted, and titaniferous material is made up of high titanium slag.Material containing sodium, calcium-containing material, vanadium-containing material
Mixing match method with titaniferous material is：By Na2SO4And Na2CO3Mass conversion into same equivalent Na2O, by CaO and
CaF2Mass conversion into same equivalent CaO, by V2O5And FeVO3Mass conversion into same equivalent V2O5, by high titanium slag
Mass conversion into same equivalent TiO2, then by four kinds of materials respectively according to Na2O、CaO、V2O5、TiO2Same equivalent
Mass ratio is 40:20:0.7:3 carry out dispensing.
The application method for the compound additive for being calcined vanadium extraction that the present embodiment is provided, comprises the following steps：
A, batch mixing：V will be contained2O5It is ground for 0.4wt%-1.5wt% Rock coal containing alum ore deposit, is broken into granular size 90
Purpose contains V in vanadium raw materials, addition Rock coal containing alum ore deposit2O51.2 times of compound additive of weight, is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature is 550 DEG C, and roasting time is 1h；Second of roasting
Temperature is 800 DEG C, and roasting time is that control the content of free oxygen in calcination atmosphere in 1.5h, roasting process be 20%, after roasting
Mineral leached with 2mol/L dilute sulfuric acids, leaching rate reaches 96%, and leachate is used for follow-up vanadium extraction.
Embodiment 4
A kind of compound additive for being used to be calcined vanadium extraction that the present embodiment is provided, including following four material are mixed and ground
It is made to 100 mesh：Material containing sodium, calcium-containing material, vanadium-containing material and titaniferous material, wherein material containing sodium is by Na2SO4And Na2CO3
It is 9 according to mass ratio:1 mixes, and calcium-containing material is by CaO and CaF2It is 80 according to mass ratio:5 mix, vanadium-containing material
By V2O5With Ca (VO3)2It is 3 according to mass ratio:1 is constituted, and titaniferous material is made up of high titanium slag.Material containing sodium, calcium-containing material, contain
The mixing match method of vanadium material and titaniferous material is：By Na2SO4And Na2CO3Mass conversion into same equivalent Na2O, will
CaO and CaF2 mass conversion into same equivalent CaO, by V2O5With Ca (VO3)2Mass conversion into same equivalent V2O5,
By the mass conversion of high titanium slag into same equivalent TiO2, then by four kinds of materials respectively according to Na2O、CaO、V2O5、TiO2It is same
The mass ratio of equivalent is 35:15:1:5 carry out dispensing.
The application method for the compound additive for being calcined vanadium extraction that the present embodiment is provided, comprises the following steps：
A, batch mixing：V will be contained2O5It is ground for 4.2wt%-14.7wt% v-bearing steel slag, is broken into granular size 100
Purpose contains V in vanadium raw materials, addition v-bearing steel slag2O51.4 times of compound additive of weight, is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature is 600 DEG C, and roasting time is 1h；Second of roasting
Temperature is 850 DEG C, and roasting time is that control the content of free oxygen in calcination atmosphere in 2h, roasting process be 30%, after roasting
Mineral are leached with 2mol/L dilute sulfuric acids, and leaching rate reaches 98%, and leachate is used for follow-up vanadium extraction.
Embodiment 5
A kind of compound additive for being used to be calcined vanadium extraction that the present embodiment is provided, including following four material are mixed and ground
It is made to 95 mesh：Material containing sodium, calcium-containing material, vanadium-containing material and titaniferous material, wherein material containing sodium is by Na2SO4And Na2CO3Press
It is 8 according to mass ratio:1.5 mix, and calcium-containing material is by CaCO3And CaF2It is 90 according to mass ratio:3 mix, vanadium-containing material
By V2O5With Ca (VO3)2It is 2.5 according to mass ratio:1 is constituted, and titaniferous material is made up of high titanium slag and rutile.Material containing sodium, contain
The mixing match method of calcium material, vanadium-containing material and titaniferous material is：By Na2SO4And Na2CO3Mass conversion into same equivalent
Na2O, by CaCO3And CaF2Mass conversion into same equivalent CaO, by V2O5With Ca (VO3)2Mass conversion into equal
The V of equivalent2O5, by the mass conversion of high titanium slag and rutile into same equivalent TiO2, then by four kinds of materials respectively according to
Na2O、CaO、V2O5、TiO2Same equivalent mass ratio be 50:18:1:1 carries out dispensing.
The application method for the compound additive for being calcined vanadium extraction that the present embodiment is provided, comprises the following steps：
A, batch mixing：V will be contained2O5It is ground, crushes for 0.8wt%-1.4wt% vanadium-containing shale and vanadium-containing wasting catalyst
Contain V in vanadium raw materials, addition vanadium-containing shale and vanadium-containing wasting catalyst into the purpose of granular size 952O51.4 times of compound addition of weight
Agent, is well mixed to obtain batch mixing；
B, roasting：Batch mixing is calcined in two times, first time sintering temperature is 650 DEG C, and roasting time is 1.5h；Second of roasting
It is 850 DEG C to burn temperature, and roasting time is that control the content of free oxygen in calcination atmosphere in 2h, roasting process be 30%, after roasting
Mineral leached with 2mol/L dilute sulfuric acids, leaching rate reaches 98%, and leachate is used for follow-up vanadium extraction.
Using the compound additive in embodiment 1 to 5 during roasting, liquid phase is not likely to produce, is not in condense
The phenomenon of equipment；In roasting process, it is difficult to leach the impurity in stone containing navajoite, is favorably improved the purity of vanadium；It is difficult production
Raw poisonous and harmful substance, environmental protection effectively reduces the discharge to environment " three wastes ", active response Sustainable development policies；Will
The technique that this compound additive is used to be calcined is also simple, it is only necessary to which carrying out batch mixing can be calcined, and production efficiency is higher, is not required to
Add other processes or equipment, it is possible to decrease production cost；Meanwhile, compound additive to the conversion ratio of the stone containing navajoite also compared with
Height, the utilization rate of compound additive itself is also higher, can make full use of the raw material of process for extracting vanadium, saves the cost of raw material.
Compound additive in embodiment 1 to 5 and additive of the prior art are carried with carrying out roasting containing vanadium raw materials
Vanadium, contrasts the parameter in the leaching rate and roasting technique of vanadium, the results are shown in Table 1, wherein under additive of the prior art selection
Row are several：Prior art 1：Lime adds fluorite to be mixed with to form；Prior art 2：Tungsten oxide and titanium oxide are mixed with
Form；Prior art 3：Sodium chloride, calcirm-fluoride and calcium carbonate, which are mixed with, to be formed.
Table 1
As it can be seen from table 1 compared with additive of the prior art and roasting technique, being carried out using this compound additive
Roasting, not only shortens roasting time, and the leaching rate of vanadium is also improved much to a certain extent, i.e., vanadium from ore by low
The conversion ratio that valency vanadium is converted into high price vanadium is improved a lot, and for actual industrial production, and leaching rate is higher, be more difficult into
One step obtains higher leaching rate, it is seen that this compound additive breaches existing vanadium extraction technical bottleneck, significantly improves vanadium
Conversion ratio, and be calcined using compound additive, sintering temperature can be effectively reduced, process efficiency is improved.
Above-described is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without departing from the inventive concept of the premise, several modifications and improvements can also be made, these should also be considered as the guarantor of the present invention
Scope is protected, these effects and practical applicability for implementing all without the influence present invention.The present invention omits the technology of description, shape
Shape, construction part are known technology.
Claims (10)
1. a kind of compound additive for being used to be calcined vanadium extraction, it is characterised in that mixed including following four material by mass fraction
And it is obtained to be ground to 80 mesh~100 mesh：35~55 parts of material containing sodium, 15~25 parts of calcium-containing material, 0.5~1 part of vanadium-containing material contains
1~5 part of titanium material.
2. a kind of compound additive for being used to be calcined vanadium extraction according to claim 1, it is characterised in that the material containing sodium
By Na2SO4And Na2CO3According to mass ratio 7~9:1~2 mixes.
3. a kind of compound additive for being used to be calcined vanadium extraction according to claim 1, it is characterised in that the calcium-containing material
By CaCO3Or and CaCO3With CaO, CaF of equivalent2According to mass ratio 80~95:1~5 mixes.
4. a kind of compound additive for being used to be calcined vanadium extraction according to claim 1, it is characterised in that the vanadium-containing material
By V2O5With vanadic salts according to mass ratio 1~3:1 mixes, and the vanadic salts is Ca (VO3)2Or NaVO3Or FeVO3。
5. a kind of compound additive for being used to be calcined vanadium extraction according to claim 1, it is characterised in that the titaniferous material
For at least one of ilmenite concentrate, rutile and high titanium slag.
6. being used for described in any one is calcined the application method of the compound additive of vanadium extraction in claim 1 to 5, its feature exists
In comprising the following steps：
A, batch mixing：The vanadium raw materials that contain after screening are chosen, addition compound additive is well mixed to obtain batch mixing；
B, roasting：The batch mixing is calcined in two times, first time sintering temperature be 400 DEG C~650 DEG C, roasting time be 0.5h~
1.5h；Second of sintering temperature is 750 DEG C~850 DEG C, and roasting time is 1h~2h.
7. the application method according to claim 6 for being used to be calcined the compound additive of vanadium extraction, it is characterised in that described to contain
Vanadium raw materials are at least one of vanadium titano-magnetite, v-bearing steel slag, Rock coal containing alum ore deposit, vanadium-containing shale and vanadium-containing wasting catalyst.
8. the application method according to claim 6 for being used to be calcined the compound additive of vanadium extraction, it is characterised in that described multiple
Close the addition of additive and contain V in vanadium raw materials to be described2O50.8~1.4 times of weight.
9. being used for according to claim 7 or 8 is calcined the application method of the compound additive of vanadium extraction, it is characterised in that institute
It is the mesh of 80 mesh~100 to state the granular size containing vanadium raw materials.
10. the application method according to claim 9 for being used to be calcined the compound additive of vanadium extraction, it is characterised in that step B
The content of free oxygen is 10%~30% in calcination atmosphere.
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