CN110129552A - A method of vanadic sulfide material is prepared using containing vanadium leachate - Google Patents
A method of vanadic sulfide material is prepared using containing vanadium leachate Download PDFInfo
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- CN110129552A CN110129552A CN201910540730.3A CN201910540730A CN110129552A CN 110129552 A CN110129552 A CN 110129552A CN 201910540730 A CN201910540730 A CN 201910540730A CN 110129552 A CN110129552 A CN 110129552A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a kind of using the method for preparing vanadic sulfide material containing vanadium leachate, is that will contain vanadium mineral to obtain by pretreatments such as roasting-leachings containing vanadium leachate；, as mother liquor, sulphur source thioacetamide is added containing vanadium leachate, vanadium disulfide or four vanadic sulfides are generated by hydro-thermal reaction.The vanadium disulfide of preparation or four vanadic sulfides can be used as the use of lithium/sodium-ion battery negative electrode material.The method of the present invention eliminates the preparation process of the pure materials such as sodium vanadate, ammonium vanadate in existing vanadic sulfide material preparation process, directly from containing vanadic sulfide material is prepared in vanadium leachate, shortens material preparation flow, significantly reduces production cost.
Description
Technical field
The present invention relates to a kind of using the method for preparing vanadic sulfide material containing vanadium leachate, belongs to vanadium Chemical Engineering Technology and resource
Recycle utilization technology field.
Background technique
With the fast development of current world economy, the development and utilization of energy and material, which has become one, has decisive shadow
Ring the natural science technology of power.Exploitation new energy simultaneously applies it to the top priority that each field has become researcher.Lithium from
Oneself develops sub- each component part of battery through being furtherd investigate, but can't meet the requirement of large-scale energy consumption application.Sodium
Ion battery is and similar to lithium property and be concerned since sodium storage capacity is high.And transiting state metal sulfide is higher because of its
Theoretical specific capacity, it is considered to be a kind of potential anode material of lithium-ion battery, such as molybdenum sulfide, vanadic sulfide etc..Vanadic sulfide at present
Negative electrode material is usually synthesized by vanadium source of the pure chemistry reagent of vanadium, and the pure chemistry reagent of vanadium is usually to pass through to contain in vanadium mineral
Vanadium the pretreatments such as be fired-leach and be transferred to liquid phase, then be made through series of process such as removal of impurities, precipitating, crystallizations；Face cost
It is higher, the defects of technique is longer.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of utilize and prepares vanadic sulfide material containing vanadium leachate
Method, it can be achieved that the short route of vanadic sulfide material, low cost, efficiently preparation, the vanadic sulfide material of preparation can be further used as
Lithium/sodium-ion battery negative electrode material uses.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A method of vanadic sulfide material is prepared using containing vanadium leachate comprising following steps:
(1) containing the preparation of vanadium leachate
After S1, roasting: will contain vanadium mineral saltless roasting or will contain vanadium mineral and roasting additive is mixed to get mixed material
Roasting obtains roasting clinker；
S2, leaching: the roasting clinker that step S1 is obtained being leached in leaching medium, separates solid-liquid, obtains leaching containing vanadium
Liquid and tailings；
(2) preparation of vanadic sulfide material
S3, contain vanadium leachate and stirring and dissolving acquisition mixed liquor for what sulphur source addition step S2 was obtained；
S4, the obtained mixed liquor of step S3 is transferred to reaction kettle, is reacted after heating；Reaction is taken out after reaction
Kettle is simultaneously cooled to room temperature；
S5, by step S4 products therefrom through being separated by solid-liquid separation, after the solid repeated flushing of acquisition drying obtain vanadic sulfide material.
In a preferred embodiment, in step sl, the vanadium mineral that contains is vanadium titano-magnetite, vanadium slag, vanadium extraction
One or more of tailings, Rock coal containing alum, vanadium-containing wasting catalyst, wherein in vanadium titano-magnetite content of vanadium with V2O5It is calculated as 0.2%
~1.8%；Vanadium in Vanadium Residue content is with V2O5It is calculated as 5%~20%；Content of vanadium is in tailings in vanadium extraction with V2O5It is calculated as 0.5%~3%；
Content of vanadium is in Rock coal containing alum with V2O5It is calculated as 0.1%~1.2%；Content of vanadium is in vanadium-containing wasting catalyst with V2O5It is calculated as 5%~8%；
The roasting additive is sodium salt or calcium salt；Adding sodium salt is sodium roasting, and calcium salt is calcification baking；
When sodium roasting, the amount ratio containing vanadium mineral and sodium salt be by containing vanadium in vanadium mineral with V2O5Contain sodium in meter and sodium salt
Molar ratio be 1: 0.5~3；In this proportional region, vanadium leaching rate with higher not only can guarantee, but also can limit and contain vanadium mineral
The leaching of the impurity elements such as middle chromium.
When calcification baking, the amount ratio containing vanadium mineral and calcium salt be by containing vanadium in vanadium mineral with V2O5Meter and calcic in calcium salt
Molar ratio be 1: 0.5~1.5；In this proportional region, vanadium leaching rate with higher not only can guarantee, but also can limit and contain navajoite
The leaching of the impurity elements such as chromium in object.
Wherein, sodium salt is at least one of sodium carbonate, sodium sulphate, sodium chloride, and calcium salt is calcium oxide, calcium carbonate, chlorination
At least one of calcium, calcium sulfate.
In a preferred embodiment, in step sl, the temperature of the saltless roasting containing vanadium mineral be 800 DEG C~
950 DEG C, the time is 30min~180min；
When the roasting additive is sodium salt, the temperature of roasting is 750 DEG C~900 DEG C, and the time is 30min~180min；
When the roasting additive is calcium salt, the temperature of roasting is 800 DEG C~950 DEG C, and the time is 30min~180min.
Above-mentioned roasting condition is obtained by many experiments, because it is found through experiment that when lower than limit temperature roasting when, vanadium
It is lower can be converted into soluble vanadate, leaching rate under current Leaching Systems for only a small amount of vanadium in slag；And it is higher than limit
When temperature calcination processed, the object of low melting point is met and is locally melted in material, and vanadium is wrapped up and is unfavorable for leaching.Roasting process
Material is put into from room temperature to assigned temperature, or after furnace temperature reaches assigned temperature by material with furnace.Calcining time is lower than
The conversion ratio of vanadium is insufficient when 30min, i.e. the amount of generation vanadate is less.And it roasts and will cause a large amount of of cost more than 300min
Loss.It material furnace cooling or is directly taken out after roasting process；It is 250~300 mesh that clinker, which is roasted, through particle size after cracking, this
Particle size range is conducive to the leaching of vanadium, and it is advantageous to above-mentioned conditions to be roasted.
In a preferred embodiment, in step s 2,
Baking modes containing vanadium mineral described in the step S1 are saltless roasting or roasting additive is that calcium salt carries out calcium salt
When roasting, the leaching medium is the carbonate such as sodium carbonate liquor, sodium bicarbonate solution, sal volatile, ammonium bicarbonate soln
At least one of；Wherein, sodium carbonate liquor concentration is 100~200g/L；Sodium bicarbonate solution concentration is 50~80g/L；Carbon
Acid ammonium solution concentration is 100~600g/L；Ammonium bicarbonate soln concentration is 100~150g/L.
It is due to the medium that carbonate solution, which why is selected, as the leaching medium of saltless roasting or calcification baking clinker
Compared with the conventional medias such as acid, alkali, resulting leachate foreign ion is less after leaching, will not influence subsequent vanadic sulfide material
Purity.
When roasting additive in the step S1 is that sodium salt carries out sodium-salt calcination, the leaching medium is water.
In a preferred embodiment, in step s 2, the leaching medium and roasting clinker press liquid-solid ratio mL/g
It is added for 3~20: 1, leaching process temperature is 60 DEG C~100 DEG C；The leaching process time is 30min~180min, separation
Solid-liquid is using filtering or centrifugation.
That is when leaching medium is carbonate solution, the liquid-solid ratio of carbonate solution and roasting clinker is by mL/g
Carry out at 3~20: 1, and leaching process temperature is 60 DEG C~100 DEG C；The leaching process time is 30min~180min；
When carrying out sodium-salt calcination, pressing mL/g as the water of leaching medium and the liquid-solid ratio of roasting clinker is 3~20: 1 progress,
Leaching process temperature is 60 DEG C~100 DEG C；The leaching process time is 30min~180min；Solid-liquid separation means were after leaching
Filter or centrifugation.
In leaching process, lesser liquid-solid ratio causes leaching process motive force insufficient, and V leaching rate is smaller, and biggish
Leaching rate will lead to leaching process increased costs；Furthermore extraction temperature is too low, extraction time is too short can all cause V leaching rate compared with
It is low；And maturing temperature is excessively high, extraction time is too long all to cause increased costs.
In a preferred embodiment, in step s3, described to be soaked containing vanadium when leaching medium is sodium carbonate liquor
Out liquid be added after soluble calcium salt will precipitating removal, the filtrate of acquisition carries out step S3 again, the soluble calcium salt be calcium chloride,
At least one of calcium nitrate.If that is containing vanadium leachate be containing vanadium mineral after saltless roasting or calcification baking sodium carbonate
Solution leaches to obtain, and soluble calcium salt should be added before sulphur source is added and remove carbonate in leachate.This is because carbonic acid
For sodium as medium is leached by use, pH of leaching solution is 12 or so, which is unfavorable for the generation of subsequent vanadic sulfide, and a large amount of
The presence of carbanion will lead to pH value and adjust without the smaller value of normal direction, therefore soluble calcium salt need to be added and be removed.
In a preferred embodiment, in step s3, the amount ratio containing vanadium leachate and sulphur source is by containing
The molar ratio of vanadium (in terms of V) and sulphur (in terms of S) in sulphur source is 1: 3~10 in vanadium leachate；The sulphur source is thioacetamide；Institute
The mode for stating stirring is magnetic agitation, mechanical stirring or ultrasonic disperse；Whipping temp is room temperature；Mixing time be 30min~
180min。
In a preferred embodiment, in step s 4, the reaction kettle is polytetrafluoroethylliner liner hydrothermal synthesis
Reaction kettle；The temperature of heating is 140 DEG C~200 DEG C；The reaction time is 12h~36h；The type of cooling is natural cooling
Or water cooling.
In a preferred embodiment, in step s 5, described be separated by solid-liquid separation is for filtering or centrifugation, the flushing
Water and ethyl alcohol elute for several times repeatedly, and the drying is 40~80 DEG C of vacuum drying 6h~36h.
In a preferred embodiment, in step s 5, when the roasting additive is sodium salt, leaching medium is
Water；Or roasting additive is calcium salt, the leaching medium is that sodium carbonate liquor is obtained containing vanadium leachate, the vanadic sulfide finally obtained
Material is four vanadic sulfides；
When roasting additive be calcium salt or saltless roasting, the leachings medium be sodium bicarbonate solution, sal volatile or
When ammonium bicarbonate soln, the vanadic sulfide material of acquisition is vanadium disulfide.
(3) beneficial effect
The beneficial effects of the present invention are:
Method provided by the invention is containing vanadium mineral such as vanadium titano-magnetite, vanadium slag, tailings in vanadium extraction, Rock coal containing alum, useless containing vanadium
One or more of catalyst etc. are raw material, are fired-leach etc. that pretreatments obtain is vanadium source, thio second containing vanadium leachate
Amide is that sulphur source prepares vanadic sulfide material, eliminates the process by the pure material containing vanadium containing vanadium mineral preparation, shortens process, save
Cost.
Method effective use of the invention contains vanadium mineral, and vanadium is carried out effective extraction and application, can be effectively treated waste residue and
The energy and material that can be used for lithium/sodium-ion battery negative electrode material is prepared, economic benefit is effectively increased.
Detailed description of the invention
Fig. 1 is the XRD spectrum of four vanadic sulfides prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD spectrum of vanadium disulfide prepared by the embodiment of the present invention 2；
Fig. 3 is the SEM photograph of four vanadic sulfides prepared by the embodiment of the present invention 3；
Fig. 4 is the EDS energy spectrum diagram of four vanadic sulfides prepared by the embodiment of the present invention 3.
Specific embodiment
The principle of the present invention is to first pass through the series of steps such as roasting-leaching to be transferred to leachate containing the vanadium in vanadium mineral
In.The barium oxide containing indissoluble in vanadium mineral is turned by saltless roasting or addition additive roasting specially in roasting process
The vanadate for dissolving in and leaching medium is turned to, then vanadate is dissolved in leachate by leaching.In vanadic sulfide preparation process
In using containing the vanadium in vanadium leachate as vanadium source, thioacetamide be sulphur source be prepared for vanadic sulfide.
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.Following percentage is not known illustrate to be mass percent.
Embodiment 1
A method of using vanadic sulfide material is prepared containing vanadium leachate, include the following steps:
(1) by content of vanadium (with V2O5Meter) be 17.5% vanadium slag carry out saltless roasting, maturing temperature is 950 DEG C, when roasting
Between be 120min, obtain roasting clinker.
(2) after roasting chamotte crushing, taking particle size after cracking is the sodium carbonate that the roasting clinker of 250~300 mesh is placed in 160g/L
It is leached in solution, extraction temperature is 80 DEG C, extraction time 60min, and leachate and roasting clinker press liquid-solid ratio as 5:1, is leached
After be filtered, separation solid-liquid is obtained containing vanadium leachate, and the leaching rate by the way that vanadium is calculated is 93.05%.
(3) after adding calcium chloride to precipitate carbanion containing vanadium leachate, thioacetamide is added, contains vanadium leachate and sulphur
For acetamide amount ratio in containing vanadium (in terms of V) in vanadium leachate and thioacetamide the molar ratio of sulphur (in terms of S) be 1: 5,
Magnetic agitation 120min at room temperature.
(4) solution after stirring evenly is placed in the hydrothermal reaction kettle that polytetrafluoroethylene (PTFE) is liner, the hydro-thermal reaction at 160 DEG C
For 24 hours, cooled to room temperature after reaction.
(5) reaction product is separated by filtering, elutes solid for several times repeatedly with water and ethyl alcohol, and in a vacuum drying oven
In 60 DEG C of vacuum drying 6h, vanadic sulfide material is obtained.The vanadic sulfide material of acquisition is subjected to X-ray diffraction, obtains XRD spectrum,
As shown in Figure 1, the vanadic sulfide material and four vanadic sulfide standard cards that synthesize as can be seen from Figure coincide, therefore in embodiment 1
The material of the condition preparation is four vanadic sulfide materials.
Embodiment 2
A method of using vanadic sulfide material is prepared containing vanadium leachate, include the following steps:
(1) by content of vanadium (with V2O5Meter) be 0.5% vanadium titano-magnetite, add calcium oxide after roast, vanadium titano-magnetite with
The amount ratio of calcium oxide is by vanadium in vanadium titano-magnetite (with V2O5Meter) with calcium oxide in calcic molar ratio be 1: 0.5,900
DEG C carry out calcification baking 120min, obtain roasting clinker.
(2) after roasting chamotte crushing, taking particle size after cracking is the bicarbonate that the roasting clinker of 250~300 mesh is placed in 80g/L
It is leached in sodium solution, extraction temperature is 95 DEG C, extraction time 120min, and leaching liquid-solid ratio is 10, filtering point after leaching
It from solid-liquid and obtains containing vanadium leachate, the leaching rate by the way that vanadium is calculated is 92.13%.
(3) thioacetamide is added containing vanadium leachate, the amount ratio containing vanadium leachate and thioacetamide is to soak by containing vanadium
The molar ratio of vanadium (in terms of V) and sulphur (in terms of S) in thioacetamide is 1:10 in liquid out, at room temperature mechanical stirring 120min.
(4) solution after stirring evenly is placed in polytetrafluoroethylliner liner hydrothermal synthesis reaction kettle, the hydro-thermal reaction at 180 DEG C
20h, after reaction after natural cooling 1h water cooling to room temperature.
(5) reaction product is separated by filtering, filtration product water and ethyl alcohol elute for several times repeatedly, and are being dried in vacuo
In 80 DEG C of vacuum drying 12h in case, vanadic sulfide material is obtained.
By vanadic sulfide material carry out X-ray diffraction, obtain XRD spectrum as shown in Fig. 2, from figure 2 it can be seen that synthesis
Vanadic sulfide material and vanadium disulfide standard card coincide preferably, therefore with the material of the preparation of condition described in embodiment 2 for two sulphur
Change vanadium material.
Embodiment 3
A method of using vanadic sulfide material is prepared containing vanadium leachate, include the following steps:
(1) by content of vanadium (with V2O5Count) sodium roasting is carried out for 13.75% high chrome alum slag, roasting additive is carbonic acid
The amount ratio of sodium, high chrome alum slag and sodium salt is by vanadium in vanadium titano-magnetite (with V2O5Count) be with the molar ratio in sodium carbonate containing sodium
1:1, maturing temperature are 850 DEG C, calcining time 60min.
(2) after roasting chamotte crushing, taking particle size after cracking is that the roasting clinker of 250~300 mesh is placed in water leaching, leaches temperature
Degree is 70 DEG C, extraction time 180min, and leaching liquid-solid ratio is 12:1, and solid-liquid is separated by filtration after leaching and obtains soaking containing vanadium
Liquid out, the leaching rate by the way that vanadium is calculated are 94.24%, and the leaching rate of chromium is only 0.05%, realizes vanadium and impurity element
Efficiently separate.
(3) thioacetamide is added containing vanadium leachate, the amount ratio containing vanadium leachate and thioacetamide is to soak by containing vanadium
The molar ratio of vanadium (in terms of V) and sulphur (in terms of S) in thioacetamide is 1:10 in liquid out, at room temperature ultrasonic disperse 120min.
(4) solution after stirring evenly is placed in hydrothermal reaction kettle, the hydro-thermal reaction 28h at 140 DEG C, water cooling is extremely after reaction
Room temperature.
(5) reaction product is separated by filtering, filtration product water and ethyl alcohol elute for several times repeatedly, and are being dried in vacuo
In case for 24 hours in 50 DEG C of vacuum drying, vanadic sulfide material is obtained.
Obtained vanadic sulfide material is scanned electron microscope analysis, obtains SEM photograph as shown in figure 3, its energy spectrum diagram such as Fig. 4
It is shown.From figure 3, it can be seen that the vanadic sulfide material of synthesis is spherical, the generation known to atomic ratio in the EDS map of Fig. 4
Material is four vanadic sulfides.
The preparation of existing vanadic sulfide material is usually pure containing vanadium with sodium metavanadate, ammonium metavanadate, sodium vanadate, positive ammonium vanadate etc.
Reagent is vanadium source, such as CN102010004A, CN105355865A, CN105810942A.And the pure reagent containing vanadium prepares raw material
Exactly contain vanadium mineral, vanadium is transferred to by leachate by roasting-leaching containing vanadium mineral, then pass through removal of impurities, precipitating, knot
The methods of brilliant, extraction, ion exchange prepare the pure reagent containing vanadium such as sodium metavanadate, ammonium metavanadate, sodium vanadate, positive ammonium vanadate out.
So if in terms of source, the starting point for preparing vanadic sulfide material is containing vanadium mineral, first from containing preparing in vanadium mineral containing the pure examination of vanadium
Agent, then vanadic sulfide material is prepared as raw material.The process flow is longer, higher cost.And the present invention proposes one kind from containing vanadium
The method that vanadic sulfide is directly prepared in leachate, substantially reduces process, reduces production cost.The above is only this hair
Bright preferred embodiment, is not the limitation that other forms are done to the present invention, and anyone skilled in the art can use
Technology contents make modifications or to change or modify the equivalent equivalent Example disclosed above.But it is all without departing from skill of the present invention
Art plan content, any simple modification to the above embodiments, equivalent variations and remodeling according to the technical essence of the invention,
Still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of utilize the method for preparing vanadic sulfide material containing vanadium leachate, which is characterized in that it includes the following steps:
S1, roasting: will contain vanadium mineral saltless roasting or will contain vanadium mineral and roasting additive be mixed to get mixed material after roast
Obtain roasting clinker；
S2, leaching: roasting clinker that step S1 is obtained being leached in leaching medium, separates solid-liquid, obtain containing vanadium leachate and
Tailings；
S3, contain vanadium leachate and stirring and dissolving acquisition mixed liquor for what sulphur source addition step S2 was obtained；
S4, the obtained mixed liquor of step S3 is transferred to reaction kettle, is reacted after heating；Take out reaction kettle simultaneously after reaction
It is cooled to room temperature；
S5, by step S4 products therefrom through being separated by solid-liquid separation, after the solid repeated flushing of acquisition drying obtain vanadic sulfide material.
2. the method as described in claim 1, which is characterized in that in step sl, the vanadium mineral that contains is vanadium titano-magnetite, vanadium
One or more of slag, tailings in vanadium extraction, Rock coal containing alum, vanadium-containing wasting catalyst；Wherein, in vanadium titano-magnetite content of vanadium with V2O5
It is calculated as 0.2%~1.8%；Vanadium in Vanadium Residue content is with V2O5It is calculated as 5%~20%；Content of vanadium is in tailings in vanadium extraction with V2O5It is calculated as
0.5%~3%；Content of vanadium is in Rock coal containing alum with V2O5It is calculated as 0.1%~1.2%；Content of vanadium is in vanadium-containing wasting catalyst with V2O5Meter
It is 5%~8%；
The roasting additive is sodium salt or calcium salt, and adding sodium salt is sodium roasting, and calcium salt is calcification baking；
When sodium roasting, the amount ratio containing vanadium mineral and sodium salt be by containing vanadium in vanadium mineral with V2O5Meter and rubbing containing sodium in sodium salt
You are than being 1: 0.5~3；
When calcification baking, the amount ratio containing vanadium mineral and calcium salt be by containing vanadium in vanadium mineral with V2O5It counts and rubs with calcic in calcium salt
You are than being 1: 0.5~1.5；
Wherein, sodium salt is at least one of sodium carbonate, sodium sulphate, sodium chloride；
Calcium salt is at least one of calcium oxide, calcium carbonate, calcium chloride, calcium sulfate.
3. method according to claim 1 or 2, which is characterized in that in step sl, the temperature of the saltless roasting containing vanadium mineral
Degree is 800 DEG C~950 DEG C, and the time is 30min~180min；
When the roasting additive is sodium salt, the temperature of roasting is 750 DEG C~900 DEG C, and the time is 30min~180min；
When the roasting additive is calcium salt, the temperature of roasting is 800 DEG C~950 DEG C, and the time is 30min~180min.
4. the method as described in claim 1, which is characterized in that in step s 2,
Baking modes containing vanadium mineral described in the step S1 are saltless roasting or roasting additive is that calcium salt carries out calcium salt roasting
When, the leaching medium is at least one of sodium carbonate liquor, sodium bicarbonate solution, sal volatile, ammonium bicarbonate soln；
Wherein, sodium carbonate liquor concentration is 100~200g/L；Sodium bicarbonate solution concentration is 50~80g/L；Sal volatile concentration is
100~600g/L；Ammonium bicarbonate soln concentration is 100~150g/L；
When roasting additive in the step S1 is that sodium salt carries out sodium-salt calcination, the leaching medium is water.
5. the method as described in claim 1, which is characterized in that in step s 2, the leaching medium and roasting clinker press liquid
Gu being added than mL/g for 3~20: 1, leaching process temperature is 60 DEG C~100 DEG C；The leaching process time be 30min~
180min, separation solid-liquid is using filtering or centrifugation.
6. the method as described in claim 1, which is characterized in that in step s3, when leaching medium is sodium carbonate liquor, institute
It states to be added after soluble calcium salt containing vanadium leachate and removes precipitating, the filtrate of acquisition carries out step S3, the soluble calcium salt again
For at least one of calcium chloride, calcium nitrate.
7. the method as described in claim 1, which is characterized in that in step s3, the dosage containing vanadium leachate and sulphur source
Than to be 1: 3~10 by the molar ratio containing sulphur in vanadium in vanadium leachate and sulphur source；The sulphur source is thioacetamide；The stirring
Mode be magnetic agitation, mechanical stirring or ultrasonic disperse；Whipping temp is room temperature；Mixing time is 30min~180min.
8. the method as described in claim 1, which is characterized in that in step s 4, the reaction kettle is polytetrafluoroethylliner liner
Hydrothermal synthesis reaction kettle；The temperature of heating is 140 DEG C~200 DEG C；The reaction time is 12h~36h；The type of cooling is
Natural cooling or water cooling.
9. the method as described in claim 1, which is characterized in that in step s 5, described to be separated by solid-liquid separation as filtering or centrifugation, institute
Stating flushing is that water and ethyl alcohol elute for several times repeatedly, and the drying is 40~80 DEG C of vacuum drying 6h~36h.
10. method as claimed in any one of claims 1-9 wherein, which is characterized in that in step s 5, when the roasting additive
For sodium salt, leaching medium is water；Or roasting additive is calcium salt, the leaching medium is that sodium carbonate liquor obtains leaching containing vanadium
Liquid, the vanadic sulfide material finally obtained are four vanadic sulfides；
When roasting additive is calcium salt or saltless roasting, the leaching medium is sodium bicarbonate solution, sal volatile or carbonic acid
When hydrogen ammonium salt solution, the vanadic sulfide material of acquisition is vanadium disulfide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910540730.3A CN110129552A (en) | 2019-06-21 | 2019-06-21 | A method of vanadic sulfide material is prepared using containing vanadium leachate |
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| CN201910540730.3A CN110129552A (en) | 2019-06-21 | 2019-06-21 | A method of vanadic sulfide material is prepared using containing vanadium leachate |
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| CN110453065A (en) * | 2019-09-12 | 2019-11-15 | 内蒙古工业大学 | The method of vanadium extraction in vanadium titano-magnetite, the leachate containing sodium vanadate extracted using this method and its application |
| CN112018339A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Method for preparing sodium ion battery vanadium fluorophosphate/carbon composite positive electrode material from vanadium-containing mineral aggregate and prepared positive electrode material |
| CN113976137A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN113976136A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN114057404A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Aluminum silicate fiber and preparation method and application thereof |
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| CN114057404A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Aluminum silicate fiber and preparation method and application thereof |
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