CN117954664A - Production process of vanadium battery electrolyte - Google Patents
Production process of vanadium battery electrolyte Download PDFInfo
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- CN117954664A CN117954664A CN202410100911.5A CN202410100911A CN117954664A CN 117954664 A CN117954664 A CN 117954664A CN 202410100911 A CN202410100911 A CN 202410100911A CN 117954664 A CN117954664 A CN 117954664A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 60
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003792 electrolyte Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 239000003513 alkali Substances 0.000 claims abstract description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229920001429 chelating resin Polymers 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000013014 purified material Substances 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/40—Purification; Separation by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a production process of vanadium battery electrolyte, which comprises the steps of dissolving ammonium metavanadate and/or ammonium polyvanadate, adding acid, adding salt, precipitating vanadium, calcining high-purity ammonium vanadate, reducing and dissolving V 2O5 to obtain vanadium battery electrolyte, concentrating and purifying mixed salt of waste water, preparing acid and alkali by a bipolar membrane, and the like.
Description
Technical Field
The invention belongs to the technical field of vanadium batteries, relates to production of vanadium battery electrolyte, and particularly relates to a production process of vanadium battery electrolyte without treatment of production associated waste brine.
Background
In recent years, all-vanadium redox flow batteries (VRB) are widely applied to energy storage processes of wind power and solar power generation as emerging energy storage batteries. The vanadium battery electrolyte is used as a key energy storage medium and is a main component of the vanadium battery.
Therefore, the low-cost and large-scale production of the vanadium battery electrolyte is beneficial to the industrial application of the vanadium battery.
However, the preparation method of the electrolyte adopted at present mainly comprises the following steps: 1. mixing V 2O5 with a certain amount of concentrated sulfuric acid, dissolving to obtain a VOSO 4 solution, assembling the solution into a battery, and charging to obtain a V (vanadium) solution. 2. Diluting concentrated sulfuric acid with distilled water according to the ratio of 1:1, adding V 2O3, gradually adding V 2O5, cooling, filtering to obtain blue VOSO4 acidic solution, and charging and discharging the battery. 3. VOSO 4 was directly dissolved in sulfuric acid (1-9 mol/L), and then charging and discharging of the battery were performed. 4. NH 4VO3 is dissolved in concentrated sulfuric acid with a certain concentration to obtain a VO 2+,V3+,NH4+,SO4 2- coexisting system, and the system can be used for directly charging and discharging a battery to obtain electrolyte required by an anode and a cathode.
For example, chinese patent publication No. CN103427103a, publication No. 2013, 12, 4, entitled a method for producing an electrolyte of an all-vanadium redox flow battery, the patent discloses that an oxide of vanadium is used as a main raw material, and the valence state of vanadium is adjusted by a proper method, so as to obtain an electrolyte of a vanadium redox flow battery with specific concentration and specific valence state. The invention has the advantages that: simple technological process, easy operation and low cost of raw materials. The method mainly comprises the following steps: 1) Diluting the acid solution, adding the concentrated acid into water, stirring uniformly, and cooling properly; 2) Adding a certain amount of vanadium oxide, and stirring until the materials are dissolved to prepare an acid solution of VO 2+; 3) Adding quantitative V 2O3, and stirring until the materials are dissolved; 4) Detecting the vanadium and acid radical concentration of the solution, and adjusting the vanadium valence state and the acid radical concentration according to the detection result. Filtering, returning filter residues to the next circulation, and enabling the filter residues to enter an adjusting tank for adjustment to obtain qualified vanadium battery electrolyte.
However, the production method causes a large amount of sodium sulfate and ammonium sulfate wastewater, and meanwhile, because vanadium resources are mostly in remote inland positions, a large amount of resources are required to be consumed for outsourcing sulfuric acid, ammonia water and sodium hydroxide and preparing pure water, so that the cost is high and the economical efficiency is low.
Disclosure of Invention
In order to solve the problems, the invention provides a production process of vanadium battery electrolyte, which comprises the steps of dissolving ammonium metavanadate and/or ammonium polyvanadate, adding acid, adding salt, precipitating vanadium, calcining high-purity ammonium vanadate, reducing and dissolving V 2O5 into vanadium battery electrolyte, concentrating and purifying mixed salt of waste water, preparing acid and alkali by a bipolar membrane, and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a production process of vanadium battery electrolyte, which comprises the following steps:
1) Dissolving and removing impurities: dissolving the solid crude product of ammonium metavanadate and/or ammonium polyvanadate by using a sodium hydroxide solution, adjusting the pH value, and adding a impurity removing agent to obtain a raw material liquid;
2) Precipitating vanadium: filtering the raw material liquid obtained in the step 1), adding sulfuric acid for acidification, adjusting the pH value, adding an ammonium sulfate solution, and separating out precipitated ammonium vanadate to obtain associated wastewater for later use;
3) Calcining: calcining the precipitated ammonium vanadate obtained in the step 2) in a reducing atmosphere to obtain a V 2O5 solid;
4) Reduction and dissolution into vanadium battery electrolyte: dissolving and reacting the V 2O5 solid obtained in the step 3) with concentrated sulfuric acid to obtain vanadium battery electrolyte;
5) Concentrating and purifying: concentrating the associated wastewater obtained in the step 2) in a homogeneous membrane system, regulating the pH value, filtering, and introducing the concentrated wastewater into a chelating resin system to remove multivalent free metal ions, thereby obtaining a purified material; the homogeneous membrane dilute brine enters a reverse osmosis system to prepare pure water for reuse;
6) Acid and alkali preparation by bipolar membrane: and 5) preparing acid and alkali again in a bipolar membrane system to obtain sulfuric acid solution and alkali mixed solution.
As a preferred embodiment of the invention, in step 1), the mass fraction of the sodium hydroxide solution is 1% -2%, and the pH is adjusted to 8.00-11.00.
As a preferable scheme of the invention, in the step 1), the impurity removing agent comprises aluminum salt impurity removing agent, and the adding amount is 100-500ppm.
In the step 2), the mass fraction of the sulfuric acid is 1% -2%, and the pH is adjusted to 1.50-2.50; the pore size of the filter membrane was 0.45. Mu.m.
As a preferred embodiment of the present invention, in the step 2), the mass fraction of the ammonium sulfate solution is 2% -4%.
In a preferred scheme of the invention, in the step 3), the reducing atmosphere is ammonia gas, the calcining temperature is 700-800 ℃, and the calcining time is 1.5-2.5h.
As a preferred scheme of the invention, in the step 5), the concentration and salt mixing content of the associated wastewater in a homogeneous membrane system are 15%, and the current density is 400A/m 2.
As a preferred embodiment of the invention, in step 5), the total amount of free multivalent metal in the purified material is less than 0.3ppm.
As a preferred scheme of the invention, in the step 6), the obtained sulfuric acid solution is recycled for acidification in the step 2) or is used for vanadium precipitation in the step 2) together with ammonia gas to generate ammonium sulfate.
In a preferred scheme of the invention, in the step 6), the ammonia gas and sodium hydroxide are obtained by heating and deaminizing the obtained mixed alkali solution, the ammonia gas is used for producing ammonium sulfate with sulfuric acid or is used for calcining in the step 3), and the sodium hydroxide is used for dissolving and removing impurities in the step 1).
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the traditional vanadium battery electrolyte production technology, the method does not need to treat and produce associated waste brine (sodium sulfate and ammonium sulfate).
2) The invention can directly prepare the waste in the original system into the required products including sodium hydroxide, sulfuric acid and ammonia water, and the waste is not required to be purchased from outside except for concentrated sulfuric acid.
3) The vast majority of the water produced in each process section can be recycled to the front-end process, so that the resource is recovered maximally.
4) The high-purity V 2O5 prepared by the method can be used for producing battery-grade vanadium electrolyte.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is a schematic diagram of a bipolar membrane of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1 and 2, the invention provides a production process of vanadium battery electrolyte, which comprises the following steps:
1) Dissolving and removing impurities of ammonium metavanadate and ammonium polyvanadate: the raw materials are directly selected from solid crude products of ammonium metavanadate and/or ammonium polyvanadate, 1% -2% sodium hydroxide solution is used for dissolving the crude products, and the pH value is adjusted to 8.00-11.00. Adding an impurity removing agent (aluminum salt impurity removing agent) to remove impurity ions in the crude product;
2) Adding acid and salt to precipitate vanadium: filtering the solution in the step 1) by a microfiltration device (0.45 mu m precision), adding 1% -2% sulfuric acid for acidification, and regulating the pH value to 1.50-2.50. Adding ammonium sulfate (2% -4%) to strengthen the precipitation of ammonium vanadate;
3) Calcining high-purity ammonium vanadate: calcining at 700-800 ℃ in the presence of reducing gas (ammonia gas) to obtain V 2O5 solid;
4) V 2O5 acidizing into vanadium battery electrolyte: v 2O5 and concentrated sulfuric acid are dissolved and reacted to generate vanadium battery electrolyte;
5) Concentrating and purifying mixed salt of waste water: and (3) concentrating the associated wastewater of ammonium vanadate in the step (2) firstly. And the mixed salt enters a homogeneous membrane system, and the concentration of the mixed salt is increased to more than 15 percent. Then adding alkali to adjust the pH to 9-10, and filtering. Finally, the mixture enters chelate resin to remove multivalent free metal ions. The homogeneous membrane dilute brine enters a reverse osmosis system to prepare pure water;
6) Acid and alkali preparation by bipolar membrane: introducing the purified material in the step 5 into a bipolar membrane system to prepare acid and alkali to obtain sulfuric acid solution (4% -5%) and mixed alkali solution (4% -5%), and evaporating ammonia water in the mixed alkali by heating and evaporating.
The invention converts the wastes (comprising sodium sulfate, ammonium sulfate, sodium hydroxide, sulfuric acid and ammonia water) generated in the process into the raw materials required by the production process system through the homogeneous membrane system and the bipolar membrane system, and realizes the green circulation process under the condition of low running cost.
In the present invention, "%" means mass fraction unless otherwise specified.
In the present invention, the impurity removing agent used is mainly composed of aluminum salts, including but not limited to aluminum sulfate and/or sodium metaaluminate, which are commercially available.
In the invention, the mass ratio of raw materials is 1 according to the calculation of upstream factories: 3-3:1.
Example 1
In the example, ammonium metavanadate is used as a raw material, 1% alkali liquor is used for dissolving a solid crude product at normal temperature, and the pH value of the material is about 10. Adding 100-500ppm impurity removing agent to settle impurity ion (total free multivalent metal less than 100 ppm). After filtration, 1% sulfuric acid is added for acidification (material ph=about 2) and about 3% ammonium sulfate is added for vanadium precipitation.
After filtration, the high-purity ammonium vanadate is calcined for 2 hours at 800 ℃ in an ammonia environment to form V 2O5.
Adding concentrated sulfuric acid for reduction and dissolution, and finally generating vanadium electrolyte.
Meanwhile, the associated wastewater of vanadium precipitation is introduced into a homogeneous membrane system (400A/m 2 of current density) to be concentrated until the mixed salt content is 15 percent. The homogeneous membrane fresh water enters a reverse osmosis system (2 Mpa pressure) to prepare pure water for reuse (the reuse rate is more than 90%, and the reverse osmosis concentrated water returns to the homogeneous membrane system for concentration). The pH value of the homogeneous membrane concentrated water is regulated to 9-10.5, and the solution is simply filtered and then enters a chelating resin system to remove free multivalent metal ions (the total amount of the free multivalent metal is less than 0.3 ppm).
The brine was prepared as sulfuric acid (5%) and lye (4%) using a bipolar membrane system (800A/m 2 current density). The sulfuric acid can be directly recycled to an acidification section or can be used for generating ammonium sulfate with ammonia gas for a vanadium precipitation section. The alkali liquor can be deaminated by heating (60-80 ℃), ammonia gas can be used for generating ammonium sulfate with sulfuric acid, or can be used as protective gas for a calcining working section after being purified, and sodium hydroxide is returned to an original dissolving working section.
Example 2
In the example, ammonium polyvanadate is used as a raw material, 1% alkali liquor is used for dissolving a solid crude product at normal temperature, and the pH value of the raw material is about 10. Adding 100-500ppm impurity removing agent to settle impurity ion (total free multivalent metal less than 100 ppm).
After filtration, 1% sulfuric acid is added for acidification (material ph=about 2) and about 3% ammonium sulfate is added for vanadium precipitation.
After filtration, the high-purity ammonium vanadate is calcined for 2 hours at 800 ℃ in an ammonia environment to form V 2O5.
Adding concentrated sulfuric acid for reduction and dissolution, and finally generating vanadium electrolyte.
Meanwhile, the associated wastewater of vanadium precipitation is introduced into a homogeneous membrane system (400A/m 2 of current density) to be concentrated until the mixed salt content is 15 percent. The homogeneous membrane fresh water enters a reverse osmosis system (2 Mpa pressure) to prepare pure water for reuse (the reuse rate is more than 90%, and the reverse osmosis concentrated water returns to the homogeneous membrane system for concentration). The pH value of the homogeneous membrane concentrated water is regulated to 9-10.5, and the solution is simply filtered and then enters a chelating resin system to remove free multivalent metal ions (the total amount of the free multivalent metal is less than 0.3 ppm).
The brine was prepared as sulfuric acid (5%) and lye (4%) using a bipolar membrane system (800A/m 2 current density). The sulfuric acid can be directly recycled to an acidification section or can be used for generating ammonium sulfate with ammonia gas for a vanadium precipitation section. The alkali liquor can be deaminated by heating (60-80 ℃), ammonia gas can be used for generating ammonium sulfate with sulfuric acid, or can be used as protective gas for a calcining working section after being purified, and sodium hydroxide is returned to an original dissolving working section.
Example 3
In the example, ammonium metavanadate and ammonium polyvanadate are used as raw materials, 1% alkali liquor is used for dissolving a solid crude product at normal temperature, and the pH value of the raw materials is about 10. Adding 100-500ppm impurity removing agent to settle impurity ion (total free multivalent metal less than 100 ppm).
After filtration, 1% sulfuric acid is added for acidification (material ph=about 2) and about 3% ammonium sulfate is added for vanadium precipitation.
After filtration, the high-purity ammonium vanadate is calcined for 2 hours at 800 ℃ in an ammonia environment to form V 2O5.
Adding concentrated sulfuric acid for reduction and dissolution, and finally generating vanadium electrolyte.
Meanwhile, the associated wastewater of vanadium precipitation is introduced into a homogeneous membrane system (400A/m 2 of current density) to be concentrated until the mixed salt content is 15 percent. The homogeneous membrane fresh water enters a reverse osmosis system (2 Mpa pressure) to prepare pure water for reuse (the reuse rate is more than 90%, and the reverse osmosis concentrated water returns to the homogeneous membrane system for concentration). The pH value of the homogeneous membrane concentrated water is regulated to 9-10.5, and the solution is simply filtered and then enters a chelating resin system to remove free multivalent metal ions (the total amount of the free multivalent metal is less than 0.3 ppm).
The brine was prepared as sulfuric acid (5%) and lye (4%) using a bipolar membrane system (800A/m 2 current density). The sulfuric acid can be directly recycled to an acidification section or can be used for generating ammonium sulfate with ammonia gas for a vanadium precipitation section. The alkali liquor can be deaminated by heating (60-80 ℃), ammonia gas can be used for generating ammonium sulfate with sulfuric acid, or can be used as protective gas for a calcining working section after being purified, and sodium hydroxide is returned to an original dissolving working section.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The production process of the vanadium battery electrolyte is characterized by comprising the following steps of:
1) Dissolving and removing impurities: dissolving the solid crude product of ammonium metavanadate and/or ammonium polyvanadate by using a sodium hydroxide solution, adjusting the pH value, and adding a impurity removing agent to obtain a raw material liquid;
2) Precipitating vanadium: filtering the raw material liquid obtained in the step 1), adding sulfuric acid for acidification, adjusting the pH value, adding an ammonium sulfate solution, and separating out precipitated ammonium vanadate to obtain associated wastewater for later use;
3) Calcining: calcining the precipitated ammonium vanadate obtained in the step 2) in a reducing atmosphere to obtain a V 2O5 solid;
4) Reduction and dissolution into vanadium battery electrolyte: dissolving and reacting the V 2O5 solid obtained in the step 3) with concentrated sulfuric acid to obtain vanadium battery electrolyte;
5) Concentrating and purifying: concentrating the associated wastewater obtained in the step 2) in a homogeneous membrane system, regulating the pH value, filtering, and introducing the concentrated wastewater into a chelating resin system to remove multivalent free metal ions, thereby obtaining a purified material; the homogeneous membrane dilute brine enters a reverse osmosis system to prepare pure water for reuse;
6) Acid and alkali preparation by bipolar membrane: and 5) preparing acid and alkali again in a bipolar membrane system to obtain sulfuric acid solution and alkali mixed solution.
2. The process for producing a vanadium redox battery electrolyte according to claim 1, wherein in step 1), the mass fraction of the sodium hydroxide solution is 1% -2%, and the pH is adjusted to 8.00-11.00.
3. The process for producing the vanadium redox battery electrolyte according to claim 1, wherein in the step 1), the impurity removing agent comprises an aluminum salt impurity removing agent, and the adding amount is 100-500ppm.
4. The process for producing the vanadium redox battery electrolyte according to claim 1, wherein in the step 2), the mass fraction of sulfuric acid is 1% -2%, and the pH is adjusted to 1.50-2.50; the pore size of the filter membrane was 0.45. Mu.m.
5. The process for producing a vanadium redox battery electrolyte according to claim 1, wherein in the step 2), the mass fraction of the ammonium sulfate solution is 2% -4%.
6. The process for producing the vanadium redox battery electrolyte according to claim 1, wherein in the step 3), the reducing atmosphere is ammonia gas, the calcining temperature is 700-800 ℃, and the calcining time is 1.5-2.5 h.
7. The process for producing the electrolyte of the vanadium battery according to claim 1, wherein in the step 5), the accompanying wastewater is concentrated and mixed with 15% of salt in a homogeneous membrane system, and the current density is 400A/m 2.
8. The process according to claim 1, wherein in step 5), the total amount of free multivalent metal in the purified material is less than 0.3ppm.
9. The process according to claim 1, wherein in step 6), the sulfuric acid solution obtained is recycled for acidification in step 2) or for use in precipitation of vanadium in step 2) with ammonia to form ammonium sulfate.
10. The process for producing the vanadium redox battery electrolyte according to claim 1, wherein in the step 6), the obtained mixed alkali solution is deaminated by heating to obtain ammonia gas and sodium hydroxide, the ammonia gas is used for producing ammonium sulfate with sulfuric acid or is used for calcining in the step 3), and the sodium hydroxide is used for dissolving and removing impurities in the step 1).
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