CN110042233B - Method for leaching vanadium by anode electrolysis in strong base electrolyte solution - Google Patents
Method for leaching vanadium by anode electrolysis in strong base electrolyte solution Download PDFInfo
- Publication number
- CN110042233B CN110042233B CN201910440720.2A CN201910440720A CN110042233B CN 110042233 B CN110042233 B CN 110042233B CN 201910440720 A CN201910440720 A CN 201910440720A CN 110042233 B CN110042233 B CN 110042233B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- anode
- electrolyte solution
- leaching
- concentrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- C22B3/045—Leaching using electrochemical processes
-
- 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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of vanadium leaching from vanadium-iron spinel type minerals by an electrolytic method, and particularly relates to a method for leaching vanadium by anode electrolysis in a strong base electrolyte solution. The method comprises the steps of preparing vanadium-iron spinel type vanadium-containing concentrate into a soluble anode, and directly electrolyzing the soluble anode in strong alkaline electrolyte solution to obtain vanadium-containing leachate. In the method, iron contained in the anode is oxidized into ferrate ions which enter a solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, no polluted oxygen is separated out from the surface of the anode. In addition, ferrate ions entering the electrolyte solution are reduced by water and the hydrogen produced at the cathode to form ferric oxide or/and ferric hydroxide precipitates, and vanadium and iron can be separated from the solution. The method utilizes the conductivity of the vanadium iron spinel and ferrate ions with strong oxidizing property generated by electrolysis, thereby electrolyzing the vanadium iron spinel type vanadium concentrate at normal temperature and normal pressure on the premise of not adding any oxidant.
Description
Technical Field
The invention belongs to the field of vanadium leaching from vanadium-iron spinel type minerals by an electrolytic method, and particularly relates to a method for leaching vanadium by anode electrolysis in a strong base electrolyte solution.
Background
Vanadium is an important alloy element, and vanadium-containing steel has the excellent characteristics of high strength, high toughness, good wear resistance and the like, and is widely applied to the industries of machinery, aviation, electronic technology, national defense industry and the like. In addition to this, vanadium is also used for producing rechargeable hydrogen batteries or vanadium redox batteries. And vanadium-containing superconducting materials have also received much attention because of their excellent properties.
At present, the sources of vanadium are mainly vanadium titano-magnetite and vanadium-containing stone coal. The vanadium titano-magnetite enters molten iron after being smelted by a blast furnace, and is blown by a converter to obtain vanadium slag. The main phases in the vanadium slag comprise vanadium iron spinel, metallic iron, a small amount of ilmenite and a silicate phase, and the vanadium iron spinel phase is the main vanadium-containing phase. In order to realize the pre-enrichment and separation of vanadium in stone coal, the prior art takes stone coal as an initial raw material and ferric oxide as an additive, roasting the stone coal at 1200 ℃ in a reducing atmosphere, and performing magnetic separation to obtain the vanadium-containing spinel concentrate. In conclusion, vanadium can be converted into the vanadium-iron spinel phase by vanadium-titanium magnetite or vanadium-containing stone coal. Therefore, the efficient and green extraction of vanadium from vanadium-iron spinel type vanadium-containing minerals has extremely important significance.
At present, the traditional process for extracting vanadium from vanadium-iron spinel type vanadium-containing minerals is sodium roasting, and the roasting temperature is higher than that of the traditional processTypically about 780 ℃ to 820 ℃. Converting the low-valence vanadium into water-soluble sodium salt of pentavalent vanadium by high-temperature sodium salt roasting, and directly leaching the roasted product to obtain vanadium-containing leachate. However, sodium metavanadate which is a sodium-modified roasting product has a low melting point, so that a large amount of liquid phase is formed in the material to cause the sintering of the material, and HCl and Cl are generated in the roasting process2And harmful gases, environmental pollution, high energy consumption, low recovery rate and the like. In order to avoid harmful gas generated by sodium roasting, in the prior art, vanadium slag containing calcium oxide is roasted at 700-950 ℃, and then the roasted product is cooled to 400-600 ℃ within 20-120 min, so that the vanadium, calcium oxide and other metal oxides can be effectively promoted to form acid-soluble vanadate. But the roasting temperature of the process is high, and the energy consumption is large; the temperature of the roasted product is required to be cooled to 400-600 ℃ within 20-120 min, and the process condition is not easy to control; in addition, the vanadium slag in the process is required to contain calcium oxide, so that the method has certain limitation on the initial raw materials.
In order to avoid the defects of harmful gas generated in the roasting process, high energy consumption, high pollution and the like, metallurgical researchers actively seek a new method for cleaning and efficiently extracting vanadium. The method comprises liquid-phase oxidative decomposition of vanadium slag, electrochemical oxidative decomposition of vanadium slag and the like.
The method for electrochemically decomposing vanadium-containing minerals of vanadium-iron spinel mainly comprises the following steps: firstly, electro-catalytic oxidation leaching of converter vanadium slag, and mixing the converter vanadium slag with MnSO4、H2SO4And (4) adjusting the mixture into ore pulp to carry out non-diaphragm electrocatalytic oxidation leaching. The process is characterized in that divalent manganese ions in the manganese sulfate are oxidized at the anode to generate trivalent manganese ions with strong oxidizing property, so that low-valence vanadium in the vanadium slag can be more effectively converted into soluble high-valence vanadium. However, the method has low recovery rate of vanadium, and the additive is added into the electrolyte solution, which causes difficulty in the subsequent separation of vanadium; in addition, with sulfuric acid as an electrolyte solution, hydrogen ions therein are reduced to hydrogen gas, and as the reaction proceeds, the sulfuric acid concentration gradually decreases, so that the leaching rate of vanadium decreases.
And secondly, electrochemically decomposing vanadium slag in a low-temperature low-concentration potassium hydroxide solution to synchronously extract vanadium and chromium, mixing and heating the vanadium slag and the low-concentration potassium hydroxide solution to prepare mixed slurry, adding the mixed slurry into a normal-pressure electrolytic tank, introducing oxidizing gas into the solution, and electrolyzing to obtain reaction slurry to obtain vanadium-containing leachate. But the method still has many defects, the electrolyte solution uses potassium hydroxide as electrolyte, the production cost is improved, the mass ratio of the potassium hydroxide to the vanadium slag is 4: 1-6: 1, the concentration of the potassium hydroxide is high, and the corrosivity is strong; before the electrolytic reaction, vanadium slag and a potassium hydroxide aqueous solution are required to be mixed and heated, wherein the temperature is 100-150 ℃, so that the energy consumption is increased; in the electrolysis process, oxidizing gas needs to be continuously introduced into the reaction system, and the anode adopts a nickel plate or a nickel rod, so that the production cost is increased.
In view of the above prior art, there is a need to provide a solution that overcomes or at least alleviates at least one of the above-mentioned drawbacks of the prior art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for anode electrolysis leaching of vanadium in strong base electrolyte solution, which is a method for preparing vanadium ore concentrate with conductive ferrovanadium spinel into an anode for direct electrolysis leaching of vanadium. The vanadium-containing leaching solution is obtained under the conditions of normal temperature and normal pressure and no addition of any oxidant in the strong base electrolyte solution.
Compared with the existing roasting, liquid-phase oxidation and electrochemical oxidation vanadium extraction processes, the method directly uses the vanadium iron spinel type vanadium concentrate with electric conductivity as an electrode, directly electrolyzes the vanadium concentrate, and can extract vanadium at normal temperature and normal pressure, which is a condition that the existing vanadium extraction process does not have. In the electrolytic process, the formed ferrate ions are used as a strong oxidant, and the effect that vanadium in the vanadium concentrate is efficiently oxidized and leached can be achieved. And the iron forms a precipitate which is deposited at the bottom of the electrolytic cell, separating vanadium and iron in the solution. In addition, the process has the characteristics of low energy consumption, simple process, no pollution, low cost and the like.
The invention is realized by the following technical scheme:
a method for leaching vanadium by anode electrolysis in a strong base electrolyte solution comprises the following steps:
s1, mixing the vanadium-containing concentrate with a binder according to a preset proportion, pressing and molding, and then roasting to prepare an anode with conductive performance;
s2, carrying out anode electrolysis reaction at normal temperature and normal pressure by using a strong base electrolyte solution; in the electrolysis process, iron contained in the anode is oxidized into ferrate ions which enter the solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, pollution-free oxygen is separated out from the surface of the anode; ferrate ions in the electrolyte solution are reduced by water and hydrogen generated by a cathode to form ferric oxide or/and ferric hydroxide which is deposited at the bottom of the electrolytic tank, so that the separation of vanadium and iron in the solution is realized;
and S3, after the electrolytic reaction is finished, respectively cleaning the anode and the cathode, and then carrying out solid-liquid separation on the electrolyzed electrolyte solution to finally obtain the vanadium-containing leaching solution.
Further, the roasting conditions are as follows: the temperature is 800-1000 ℃, and the atmosphere is reduced.
Further, the method comprises the steps of preparing a vanadium iron spinel type vanadium-containing concentrate into a soluble anode, and directly electrolyzing the soluble anode in a strong alkaline electrolyte solution to obtain vanadium-containing leachate; in the method, iron contained in the anode is oxidized into ferrate ions which enter a solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, no polluted oxygen is separated out from the surface of the anode. In addition, ferrate ions entering the electrolyte solution are reduced by water and the hydrogen produced at the cathode to form ferric oxide or/and ferric hydroxide precipitates, and vanadium and iron can be separated from the solution. The method utilizes the conductivity of the ferrovanadium spinel and ferrate ions with strong oxidizing property generated by electrolysis, thereby electrolyzing the ferrovanadium spinel type vanadium concentrate at normal temperature and normal pressure on the premise of not adding any oxidant.
Further, the vanadium-containing concentrate is vanadium iron spinel type vanadium concentrate.
Further, the vanadium-containing concentrate needs to be ball-milled before being mixed with the binder, and the ball-milling is carried out until the particle size is below 0.074 mm.
Further, the mass ratio of the vanadium concentrate to the binder in S1 is 5: 1-10: 1, and more preferably 8:1, the vanadium concentrate and the binder are uniformly mixed in an agate mortar, and then the mixture is pressed and molded under the pressure of 200-300 MPa.
Further, the binder is 5% polyvinyl alcohol.
Further, the specific contents of the roasting in S1 are as follows: and (3) placing the pressed round block into a high-temperature furnace, and roasting for 6-10 hours at 800-1000 ℃ under the reducing atmosphere condition to obtain the conductive electrode.
Further, the anodic electrolysis reaction process in S2 includes at least one of the following reactions:
4OH-1-4e→O2+2H2O
2H2O+2e→20H-1+H2
further, the anodic electrolysis reaction in S2 is carried out in an atmospheric pressure electrolytic cell; the cathode material of the electrolytic cell is a metal material or a carbon material, and the electrode shape is preferably rod-shaped;
the strong base electrolyte solution is one of hydroxide solutions of group IA metals, including sodium hydroxide solution, potassium hydroxide solution, sodium lithium hydroxide solution and cesium hydroxide solution.
The mass fraction of the sodium hydroxide solution is 10 to 35 percent, and more preferably 35 percent.
Further, in S2, the anodic electrolysis reaction is performed under electromagnetic stirring at normal temperature and normal pressure, and the voltage of the electrolytic cell is 5V or more, preferably 10V; the time for electrolysis is 1 hour or more, preferably 3 to 5 hours. During electrolysis, the more conductive wires connected to the vanadium concentrate cannot come into contact with the electrolyte solution to ensure that the anodic electrolysis reaction takes place on the ferrovanadium spinel.
Further, in S3, deionized water is adopted to clean the anode and the cathode respectively for 3-5 times;
further, after solid-liquid separation in S3, iron-rich tailings and vanadium-containing leachate are obtained respectively.
Further, the anode is in a shape of a wafer, the diameter of the anode is 9-12 mm, and the thickness of the anode is 1-3 mm; the larger the diameter of the anode electrode plate is, the larger the contact area with the electrolyte solution is, thereby accelerating the electrolytic reaction speed.
Compared with the prior art, the technical scheme adopted by the invention has the following advantages:
(1) compared with the traditional process, the method for leaching vanadium by anode electrolysis in the strong base electrolyte solution provided by the invention utilizes the conductivity of vanadium iron spinel to directly prepare vanadium iron spinel type vanadium concentrate into an electrode, does not need to add any oxidant, and directly electrolyzes to obtain vanadium-containing leachate.
(2) The method for leaching vanadium by anode electrolysis in the strong base electrolyte solution can be carried out at normal temperature and normal pressure, so that the energy consumption is reduced, and the pollution is reduced; no oxidant is added, and the components of the leaching solution are simple; in addition, the equipment is simple, the operation is convenient, the investment cost is low, and the method is suitable for industrial popularization.
(3) According to the method for leaching vanadium by anode electrolysis in the strong base electrolyte solution, from the reaction system, in the electrolysis process, ferrate ions generated by an anode accelerate the oxidation and leaching of vanadium in vanadium concentrate, and the ferrate ions entering the solution are reduced by water and hydrogen generated by a cathode to form ferric oxide or/and ferric hydroxide which is deposited at the bottom of an electrolytic tank, so that the separation of vanadium and iron in the solution is realized.
(4) According to the method for leaching vanadium by anode electrolysis in the strong base electrolyte solution, the obtained iron-rich tailings are mainly ferric oxide, and are non-toxic and pollution-free; the subsequent tailings are easy to treat.
Drawings
FIG. 1 is a schematic flow chart of a method for leaching vanadium by anodic electrolysis in a strong base electrolyte solution according to an embodiment of the invention.
Fig. 2 is a schematic diagram of a vanadium iron spinel type vanadium concentrate electrolysis device in the embodiment of the invention.
FIG. 3 is a graph showing the current versus time relationship of pure ferrovanadium spinel electrolyzed at a cell voltage of 5V in example 1 of the present invention, and illustrates the tendency of the current to decrease as the electrolysis process proceeds due to the gradual change in the anode morphology.
Fig. 4 is a schematic diagram showing the relationship between current and time when the voltage of the electrolytic cell in example 2 of the present invention is 5V, and when pure ferrovanadium spinel and vanadium concentrate are uniformly mixed at a mass ratio of 1:1, the electrode is manufactured for electrolysis, which illustrates that, compared with pure ferrovanadium spinel electrolysis, after adding vanadium concentrate, the current fluctuates sharply up and down, and as the electrolysis proceeds, the current changes continuously and tends to decrease gradually due to the dissolution of the anode.
Fig. 5 is a schematic diagram showing the relationship between current and time when the voltage of the electrolytic cell is 10V and the vanadium concentrate is electrolyzed to form an electrode in example 3 of the present invention, which illustrates that the electrolytic leaching of the vanadium concentrate can be accelerated by increasing the voltage.
FIG. 6 shows the voltage of the cell of example 4 of the present invention at 10V, and the relationship between the current and the time when the electrodes are made of vanadium concentrate, which illustrates that the concentration of vanadium in the electrolyte solution can be increased by extending the electrolysis time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The examples propose a method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution, as shown in figures 1 and 2, comprising the following steps:
s1, mixing the vanadium-containing concentrate with a binder according to a predetermined ratio, then pressing and forming, and roasting at the temperature of 800-1000 ℃ under the reducing atmosphere condition to prepare the anode with the conductive performance;
s2, carrying out anode electrolysis reaction at normal temperature and normal pressure by using a strong base electrolyte solution; in the electrolysis process, iron contained in the anode is oxidized into ferrate ions which enter the solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, pollution-free oxygen is separated out from the surface of the anode; ferrate ions in the electrolyte solution are reduced by water and hydrogen generated by a cathode to form ferric oxide or/and ferric hydroxide which is deposited at the bottom of the electrolytic tank, so that the separation of vanadium and iron in the solution is realized;
and S3, after the electrolytic reaction is finished, respectively cleaning the anode and the cathode, and then carrying out solid-liquid separation on the electrolyzed electrolyte solution to finally obtain the vanadium-containing leaching solution.
The method comprises the steps of preparing vanadium-iron spinel type vanadium-containing concentrate into a soluble anode, and directly electrolyzing the soluble anode in strong alkaline electrolyte solution to obtain vanadium-containing leachate; in the method, iron contained in the anode is oxidized into ferrate ions which enter a solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, no polluted oxygen is separated out from the surface of the anode. In addition, ferrate ions entering the electrolyte solution are reduced by water and the hydrogen produced at the cathode to form ferric oxide or/and ferric hydroxide precipitates, and vanadium and iron can be separated from the solution. The method utilizes the conductivity of the ferrovanadium spinel and ferrate ions with strong oxidizing property generated by electrolysis, thereby electrolyzing the ferrovanadium spinel type vanadium concentrate at normal temperature and normal pressure on the premise of not adding any oxidant.
The vanadium-containing concentrate is vanadium iron spinel type vanadium concentrate.
The vanadium-containing concentrate needs to be ball-milled before being mixed with the binder until the granularity is below 0.074 mm.
S1, the mass ratio of the vanadium concentrate to the binder is 5: 1-10: 1, the further optimization is 8:1, the vanadium concentrate and the binder are uniformly mixed in an agate mortar, and then the mixture is pressed and formed under the pressure of 200-300 MPa.
The binder is 5% polyvinyl alcohol.
The roasting in S1 comprises the following specific contents: and (3) placing the pressed round block into a high-temperature furnace, and roasting for 6-10 hours at 800-1000 ℃ under the reducing atmosphere condition to obtain the conductive electrode.
The anodic electrolysis reaction process in S2 comprises at least one of the following reactions:
4OH-1-4e→O2+2H2O
2H2O+2e→2OH-1+H2
the anodic electrolysis reaction in S2 is carried out in a normal-pressure electrolytic bath; the cathode material of the electrolytic cell is a metal material or a carbon material, and the electrode shape is preferably rod-shaped;
the strong base electrolyte solution is one of hydroxide solutions of metals of group IA; the hydroxide solution of the group IA metal includes sodium hydroxide solution, potassium hydroxide solution, sodium lithium hydroxide solution, and cesium hydroxide solution.
The mass fraction of the sodium hydroxide solution is 10 to 35 percent, and more preferably 35 percent.
In S2, the anodic electrolysis reaction is carried out at normal temperature and normal pressure under the condition of electromagnetic stirring, and the voltage of the electrolytic cell is more than 5V, preferably 10V; the time for electrolysis is 1 hour or more, preferably 3 to 5 hours.
During electrolysis, the more conductive wires connected to the vanadium concentrate cannot come into contact with the electrolyte solution to ensure that the anodic electrolysis reaction takes place on the ferrovanadium spinel.
S3, respectively cleaning the anode and the cathode by deionized water for 3-5 times;
and (S3) carrying out solid-liquid separation to obtain iron-rich tailings and vanadium-containing leachate.
The anode is in a wafer shape, the diameter of the anode is 9-12 mm, and the thickness of the anode is 1-3 mm; the larger the diameter of the anode electrode plate is, the larger the contact area with the electrolyte solution is, thereby accelerating the electrolytic reaction speed.
Example 1
(1) Preparing vanadium iron spinel: vanadium trioxide and ferric oxide are used as initial raw materials, and are roasted for 48 hours at 1200 ℃ in a reducing atmosphere to obtain Fe2VO4。
(2) And (2) preparing the anode by using the pure vanadium iron spinel obtained in the step (1) as a raw material, wherein the diameter of the anode is 10mm, and the thickness of the anode is about 3 mm.
(3) The electrolytic reaction is carried out in an electrolytic cell at normal temperature and normal pressure, the cathode of the electrolytic cell is made of a graphite rod with the diameter of 6mm, the center distance between the anode and the cathode is 5cm, and the electrolyte solution is 35% of sodium hydroxide solution.
(4) The bath voltage is selected to be 5V, the electromagnetic stirring speed is 500r/min, the electrolysis temperature is room temperature, and the electrolysis reaction is selected to be 1 h.
(5) After the electrolysis reaction, the relation between the current and the time is recorded, and the result is shown in figure 3, wherein the current is stable and gradually reduced after about 250s, which indicates that the anode generates vanadate radicals and ferrate ions which enter the solution due to the electrolysis reaction, the shape of the anode is changed, so that the current is changed, after the electrolysis reaction is finished, the solid-liquid separation is carried out, and finally, the concentration of vanadium in the leachate is 579 mg/L measured by ICP-AES.
Example 2
(1) Vanadium iron spinel type vanadium concentrate is used as an initial raw material, and the particle size of the vanadium concentrate is ball-milled to be less than 0.074 mm.
(2) 0.4g of ball-milled vanadium iron spinel type vanadium concentrate and 0.4g of pure vanadium iron spinel (Fe)2VO4) Placing in agate mortar, adding 3 drops of 5% polyvinyl alcohol solution (about 0.1g), mixing, and pressing into round blocks with diameter of 10mm and thickness of about 3 mm.
(3) And (3) placing the prepared round block in a high-temperature furnace, and roasting for 6 hours at the temperature of 800 ℃ in a reducing atmosphere to prepare the anode with the conductive performance.
(4) The electrolytic reaction is carried out in an electrolytic cell at normal temperature and normal pressure, the cathode of the electrolytic cell is made of a graphite rod with the diameter of 6mm, the center distance between the anode and the cathode is 5cm, and the electrolyte solution is 35% of sodium hydroxide solution.
(5) The bath voltage is 5V, the electromagnetic stirring speed is 500r/min, and the electrolysis temperature is room temperature.
(6) After the electrolysis reaction, the relation between the current and the time is recorded, and as a result, as shown in FIG. 4, the current continuously changes and tends to decrease with the continuous progress of the electrolysis reaction, which indicates that the electrode morphology gradually changes, and after 8000s of the electrolysis reaction, the current suddenly changes to 0A because the anode is continuously dissolved, so that the electrode falls off, at the moment, the electrolysis reaction is finished, solid-liquid separation is carried out after the electrolysis reaction is finished, and finally, the concentration of vanadium in the leachate is measured to be 306 mg/L through ICP-AES.
Example 3
(1) Vanadium iron spinel type vanadium concentrate is used as an initial raw material, and the particle size of the vanadium concentrate is ball-milled to be less than 0.074 mm.
(2) 0.8g of ball-milled vanadium-iron spinel type vanadium concentrate is weighed into an agate mortar, 3 drops of polyvinyl alcohol solution (about 0.1g) with the mass fraction of 5% are added and fully and uniformly mixed, and then the mixture is pressed into round blocks with the diameter of 10mm and the thickness of about 3 mm.
(3) And (3) placing the prepared round block in a high-temperature furnace, and roasting for 6 hours at the temperature of 800 ℃ in a reducing atmosphere to prepare the anode with the conductive performance.
(4) The electrolytic reaction is carried out in an electrolytic bath at normal temperature and normal pressure; the cathode of the electrolytic cell is made of a graphite rod with the diameter of 6mm, the center distance between the anode and the cathode is 5cm, and the electrolyte solution is 35% of sodium hydroxide solution.
(5) The bath voltage is 10V, the electromagnetic stirring speed is 500r/min, and the electrolysis temperature is room temperature.
(6) After the start of the electrolytic reaction, the relationship between the current and the time was recorded, and the results are shown in FIG. 5. the electrolytic reaction was carried out for 3600s, after the completion of the reaction, solid-liquid separation was carried out, and the vanadium content in the leachate was quantitatively analyzed by ICP-AES to determine the concentration thereof as 137 mg/L.
Example 4
(1) Vanadium iron spinel type vanadium concentrate is used as an initial raw material, and the particle size of the vanadium concentrate is ball-milled to be less than 0.074 mm.
(2) 0.8g of ball-milled vanadium-iron spinel type vanadium concentrate is weighed into an agate mortar, 3 drops of polyvinyl alcohol solution (about 0.1g) with the mass fraction of 5% are added and fully and uniformly mixed, and then the mixture is pressed into round blocks with the diameter of 10mm and the thickness of about 3 mm.
(3) And (3) placing the prepared round block in a high-temperature furnace, and roasting for 6 hours at the temperature of 800 ℃ in a reducing atmosphere to prepare the anode with the conductive performance.
(4) The electrolytic reaction is carried out in an electrolytic bath at normal temperature and normal pressure; the cathode of the electrolytic cell is made of a graphite rod with the diameter of 6mm, the center distance between the anode and the cathode is 5cm, and the electrolyte solution is 35% of sodium hydroxide solution by mass fraction.
(5) The bath voltage is 10V, the electromagnetic stirring speed is 500r/min, and the electrolysis temperature is room temperature.
(6) After the start of the electrolytic reaction, the current was recorded as a function of time, and the results are shown in FIG. 6, which shows that the current gradually decreased due to the dissolution of the anode as the electrolysis proceeded, and after 7600s, the electrolytic reaction was completed due to the falling off of the anode, after the completion of the electrolytic reaction, solid-liquid separation was performed, the leachate was qualitatively analyzed by ICP-AES, and the results are shown in the following Table I, and finally, vanadium in the leachate was quantitatively analyzed by ICP-AES, and the concentration thereof was measured as 385 mg/L.
TABLE-semi-quantitative analysis of all elements in the leachate of the electroanalysis of vanadium concentrates
Claims (7)
1. A method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution, characterised in that it comprises the following steps:
s1, mixing the vanadium-containing concentrate with a binder according to a preset proportion, pressing and molding, and roasting to prepare the anode with the conductive performance;
s2, carrying out anode electrolysis reaction at normal temperature and normal pressure by using a strong base electrolyte solution;
s3, after the electrolytic reaction is finished, respectively cleaning the anode and the cathode, and then carrying out solid-liquid separation on the electrolyzed electrolyte solution to finally obtain vanadium-containing leachate;
iron contained in the anode is oxidized into ferrate ions which enter the solution, the ferrate ions further promote the oxidation and leaching of vanadium in the vanadium concentrate, and meanwhile, pollution-free oxygen is separated out from the surface of the anode; ferrate ions entering the electrolyte solution are reduced by water and hydrogen generated by a cathode to form ferric oxide or/and ferric hydroxide precipitates, and vanadium and iron can be separated from the solution;
the strong base electrolyte solution is a sodium hydroxide solution, and the mass fraction of the sodium hydroxide solution is 10-35%;
the roasting in S1 comprises the following specific contents: placing the pressed round block in a high-temperature furnace, and roasting for 6-10 hours at 800-1000 ℃ under the reducing atmosphere condition to obtain an electrode with conductive performance;
the vanadium-containing concentrate is vanadium iron spinel type vanadium concentrate.
2. The method for leaching vanadium by anode electrolysis in strong base electrolyte solution as claimed in claim 1, wherein the vanadium containing concentrate is ball milled to a particle size below 0.074mm before being mixed with the binder.
3. The method for leaching vanadium by anode electrolysis in strong base electrolyte solution according to claim 1, wherein the mass ratio of the vanadium concentrate to the binder in S1 is 5: 1-10: 1.
4. The method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution as claimed in claim 1, wherein the binder is polyvinyl alcohol with a mass fraction of 5%.
5. The method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution according to claim 1, characterized in that the anodic electrolytic reaction in S2 is carried out in an atmospheric electrolytic cell; the cathode material of the electrolytic cell is a metal material or a carbon material.
6. The method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution according to claim 1, wherein the solid-liquid separation in S3 is performed to obtain an iron-rich tailings and a vanadium-containing leachate.
7. The method for the anodic electrolytic leaching of vanadium in a strong base electrolyte solution as claimed in claim 1, wherein the anode is in the shape of a wafer with a diameter of 9-12 mm and a thickness of 1-3 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910440720.2A CN110042233B (en) | 2019-05-24 | 2019-05-24 | Method for leaching vanadium by anode electrolysis in strong base electrolyte solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910440720.2A CN110042233B (en) | 2019-05-24 | 2019-05-24 | Method for leaching vanadium by anode electrolysis in strong base electrolyte solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110042233A CN110042233A (en) | 2019-07-23 |
| CN110042233B true CN110042233B (en) | 2020-07-31 |
Family
ID=67283593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910440720.2A Expired - Fee Related CN110042233B (en) | 2019-05-24 | 2019-05-24 | Method for leaching vanadium by anode electrolysis in strong base electrolyte solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110042233B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5012369Y2 (en) * | 1971-01-30 | 1975-04-16 | ||
| CN103060843A (en) * | 2012-12-29 | 2013-04-24 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution |
| CN104294040A (en) * | 2013-07-15 | 2015-01-21 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5012369B1 (en) * | 1964-09-30 | 1975-05-12 |
-
2019
- 2019-05-24 CN CN201910440720.2A patent/CN110042233B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5012369Y2 (en) * | 1971-01-30 | 1975-04-16 | ||
| CN103060843A (en) * | 2012-12-29 | 2013-04-24 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution |
| CN104294040A (en) * | 2013-07-15 | 2015-01-21 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110042233A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102758091B (en) | Treatment method for electroplating sludge | |
| CN111254294B (en) | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation | |
| CN111154980B (en) | Neodymium iron boron waste solution electrolytic regeneration method | |
| CN106048251A (en) | Technological method for cleaning and efficiently treating arsenic matte | |
| CN114318417A (en) | Method for producing electrolytic manganese by using low-grade manganese oxide three-ore method | |
| CN103498051B (en) | Method for recovering copper and nickel from nickel-iron-copper alloy waste | |
| CN110331284A (en) | A method of electrolytic manganese is prepared using pyrolusite | |
| CN106756008A (en) | The method that two sections of adverse current atmospheric pressure oxidations of sulfonic acid solutions leach lead in concentrate of lead sulfide ore | |
| CN112941321B (en) | Method for strengthening leaching reaction of neodymium iron boron magnet by combining electrochemical anodic oxidation with ionic flocculant | |
| CN103468947B (en) | The Wet-process metallurgy method of a kind of separation and Extraction Mn, Fe, Pb and Ag from silver-colored manganese ore | |
| CN114853016B (en) | Method for preparing niobium titanium carbide from niobium-containing mineral | |
| CN110042233B (en) | Method for leaching vanadium by anode electrolysis in strong base electrolyte solution | |
| CN110117714B (en) | Method for leaching vanadium by anode electrolysis in normal-temperature saturated oxalic acid solution | |
| CN103668323A (en) | Method for treating copper and nickel containing material by electrolysis-segmented electrodeposition method | |
| CN106834679A (en) | The method that lead in concentrate of lead sulfide ore is leached in two sections of adverse current pressure oxidations of sulfonic acid solutions | |
| CN105861822A (en) | Reduction leaching method for cobalt-copper mixed oxidized ores | |
| CN102899689B (en) | Environment protection type metal refining method | |
| JP6201905B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries | |
| CN114702017B (en) | Method for preparing ferric phosphate from lithium extraction slag | |
| CN110306043B (en) | Method for leaching vanadium in magnetic vanadium iron spinel type powder vanadium concentrate through normal-temperature electrooxidation | |
| CN111286615B (en) | Method for separating PGMs from Fe-PGMs alloy | |
| JPH0733442A (en) | Production of mn-zn ferrite | |
| CN109652645B (en) | Method for separating and extracting tellurium and bismuth in low-grade tellurium-bismuth ore | |
| CN113818047B (en) | Method for recovering copper from reclaimed copper smelting fly ash | |
| Zubryckyj et al. | Extra‐High‐Purity Nickel Powder from Nickel Sulfate Solution by Hydrogen Reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200731 |