A method for wet vanadium precipitation
By adding metal salts and polymer electrets to a vanadium-containing solution and using ultrasound or stirring techniques to promote vanadium pentoxide deposition, the high energy consumption and environmental pollution problems of existing vanadium extraction technologies have been solved, realizing a green and environmentally friendly vanadium deposition process.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HOHAI UNIV
- Filing Date
- 2023-11-07
- Publication Date
- 2026-07-10
AI Technical Summary
Existing vanadium extraction technologies suffer from high energy consumption, environmental pollution, and difficulties in treating ammonia nitrogen wastewater, especially the serious environmental hazards caused by the ammonium salt precipitation process.
The reaction of metal salts containing Li+, Na+, K+, Mg2+, Cu2+, Ag+ or Zn2+ and polymer electrets in a vanadium-containing solution is promoted by ultrasound or stirring to avoid the generation of nitrogen-containing waste liquid.
It achieves an efficient and low-cost vanadium deposition process, reduces environmental pollution, and is suitable for industrial production.
Smart Images
Figure HDA0004534489500000011 
Figure HDA0004534489500000012 
Figure HDA0004534489500000021
Abstract
Description
Technical Field
[0001] This invention relates to a wet vanadium precipitation method, belonging to the field of chemical technology. Background Technology
[0002] Vanadium is a non-ferrous metal, often referred to as a "metallic vitamin," and is widely used in numerous fields including steel, metallurgy, petroleum, chemicals, ceramics, aerospace, batteries, pigments, glass, optics, coatings, electronics, pharmaceuticals, and rubber. In the steel and metallurgical industries, vanadium steel, formed by adding vanadium pentoxide, possesses excellent properties such as high strength, high toughness, and good wear resistance. Vanadium pentoxide is also a primary raw material for producing various subsequent vanadium products, such as vanadium nitride and vanadium carbide. In the glass and ceramics industries, vanadium pentoxide is used as an additive in the coatings and pigments industries; and in sulfuric acid and petrochemical production, it is used as a catalyst.
[0003] Vanadium pentoxide has extremely wide applications, making the extraction of vanadium and its compounds from vanadium ore or vanadium-containing wastewater a real problem. Currently, the world's popular vanadium extraction technologies mainly include the following methods: acid leaching and alkali dissolution vanadium extraction; sodium roasting vanadium extraction; direct roasting vanadium extraction; calcification roasting vanadium extraction; and solvent extraction vanadium extraction, which are briefly described below:
[0004] 1. Acid leaching and alkali dissolution method for vanadium extraction: This method utilizes acid to extract vanadium from vanadium-containing solid waste as VOCs. 2+ VO 2+ The vanadium is leached in its original form, neutralized with alkali, and then converted to pentavalent ions (such as VO₃) using an oxidizing agent under weakly alkaline conditions. 3- The vanadium is precipitated together with hydrated oxides of iron and other impurities. Then, crude vanadium is obtained by acid and alkali leaching. The crude vanadium is dissolved in alkali to generate sodium salt of pentavalent vanadium and remove impurities such as silicon. Then, ammonium salt is used to precipitate vanadium a second time to obtain ammonium metavanadate. After roasting, high-purity V2O5 is obtained.
[0005] 2. Sodium Roasting for Vanadium Extraction: Sodium roasting is a widely used process for extracting vanadium from vanadium-containing raw materials, and its research is relatively thorough. Professor Chen Housheng of my country made significant contributions to this technology. Its basic principle is as follows: using salt or soda as an additive, roasting converts multivalent vanadium into water-soluble pentavalent vanadium sodium salts, such as Na₂Oy·V₂O₅ and NaVO₃. The sodium roasting product is then directly leached with water to obtain a leachate containing vanadium and a small amount of aluminum impurities. Ammonium salts are then added (using the acidic ammonium salt precipitation method) to obtain ammonium metavanadate precipitate. Roasting yields crude V₂O₅, which is then dissolved in alkali, impurities removed, and vanadium precipitated a second time with ammonium salts to obtain ammonium metavanadate. After roasting, V₂O₅ with a purity greater than 98% can be obtained. Alternatively, the product can be impregnated with sulfuric acid, during which the reaction 2NaVO3 + H2SO4 = Na2SO4 + H2O + V2O5 occurs. Crude V2O5 is obtained by separation, followed by alkali dissolution, impurity removal, and secondary precipitation of vanadium with ammonium salt to obtain ammonium metavanadate. High-purity V2O5 can be obtained by roasting. This process has been used for vanadium extraction from coal shale and low-vanadium steel slag.
[0006] 3. Direct Roasting Vanadium Extraction Method: This method generally includes several steps: roasting, leaching, vanadium precipitation, preparation of ammonium metavanadate, and calcination. During roasting, no additives are added; oxygen in the air directly converts low-valent vanadium into acid-soluble V₂O₅ at high temperatures. Then, sulfuric acid is used to leach the V₂O₅ from the roasting product as pentavalent vanadium ions. The leachate is then purified to remove impurities such as Fe, and red vanadium is precipitated using hydrolysis precipitation or ammonium salt precipitation. The red vanadium is then dissolved in a hot aqueous solution of caustic soda, with appropriate concentration and pH controlled so that the vanadium in the solution is mainly in the form of VO₃(OH)₂. 2- The vanadium exists in its original form. After clarification, the supernatant is used to prepare ammonium metavanadate by ammonium salt precipitation, followed by calcination to obtain high-purity V₂O₅. This method has been used for vanadium extraction from vanadium-containing coal shale.
[0007] 4. Vanadium extraction by calcination roasting: Lime or calcium-containing compounds are added as solvents to vanadium-containing solid waste to form pellets and roast, oxidizing vanadium into water-insoluble calcium vanadium salts such as Ca(VO3)2, Ca3(VO4)4, and Ca2V2O7. These are then leached with acid, with the pH carefully controlled to generate VO3. 2+ Plasma is used to purify the leachate, removing impurities such as Fe. Then, vanadium is precipitated using the ammonium salt method, and ammonium metavanadate is prepared and calcined to obtain high-purity V₂O₅. The calcination roasting method has been applied to vanadium extraction from coal shale.
[0008] 5. Solvent extraction for vanadium extraction: Vanadium in vanadium-containing solid waste is converted into water-soluble or acid-soluble vanadium-containing ion clusters, such as HV, through methods such as roasting, acid leaching, and alkaline leaching. 10 O 28 5- VO3(OH) 2- V2O7 4- V4O 12 2- VO 3- VO2+ (Different solution pH values result in different ion clusters), and then extraction is performed using an extractant (such as N-263, 7402), resulting in anion or cation exchange. For example, N-263 is used to extract [HV] at pH=5. 10 O 28 ] 5- The reaction occurs: [HV] 10 O 28 ] 5- +5R3N+CH3C1 - (O)--(R3N+CH3)5[HV 10 O 28 ] 5- (O) + 5Cl- ((O) represents the organic phase). Since most other metal ions cannot enter the organic phase, vanadium is separated from the metal impurity ions. The extracted organic solution is then back-extracted with a back-extraction agent (such as NH4Cl or ammonia) to transfer vanadium back from the organic phase to the aqueous phase. The pH value is then adjusted to precipitate vanadium in the form of ammonium polyvanadate or ammonium metavanadate. The precipitate is then calcined to obtain high-purity V2O5.
[0009] Although various vanadium extraction technologies have been developed, their process routes are similar, generally involving: preparation of a vanadium ion-containing solution – removal of impurity ions – ammonium precipitation of vanadium – deammoniation to obtain V₂O₅. However, current vanadium extraction processes face significant challenges and pressures due to severe environmental pollution problems, such as high energy consumption, harmful roasting exhaust gases, and difficult-to-treat tailings. Furthermore, the subsequent ammonium salt precipitation process for vanadium from vanadium-rich solutions generates large amounts of ammonia nitrogen wastewater, which also causes significant environmental harm. Summary of the Invention
[0010] Purpose of the invention: The purpose of this invention is to provide a highly efficient and environmentally friendly wet vanadium precipitation method.
[0011] Technical solution: The present invention provides a wet vanadium precipitation method, comprising the following steps:
[0012] (1) Take a certain amount of vanadium-containing solution; add Li to the solution. + Na + K + Mg 2+ Ca 2+ Cu 2+ Ag + , or Zn 2 + Metal salts;
[0013] (2) Add polymer electret to the solution in step (1) and stir the solution at 20-100°C;
[0014] (3) After the reaction is complete, filter the solution to obtain the final product.
[0015] Furthermore, the vanadium-containing solution mentioned in step (1) is a solution containing vanadate, metavanadate, or pyrovanadate.
[0016] Further, the metal salt mentioned in step (1) includes one or more of the following: metal chloride / hypochlorite, metal sulfate, metal nitrate, metal carbonate, or metal acetate.
[0017] Specifically, taking sodium compounds as an example, available sodium salts include one or more of sodium nitrate, sodium chloride, sodium sulfate, sodium carbonate, sodium hypochlorite, sodium bicarbonate, sodium bisulfate, and sodium acetate.
[0018] Furthermore, in step (1), the final concentration of metal ions in the solution after adding the metal salt is 10 mM to 1 M.
[0019] Furthermore, the polymer electret mentioned in step (2) includes one or more of polymethyl methacrylate, polycarbonate, polypropylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoropropylene copolymer, paraffin wax, hard rubber, and hydrocarbons. These polymer electrets are catalysts in the vanadium precipitation process and can be removed from the solution and reused after the reaction is complete.
[0020] Furthermore, the above solution can be injected into a container made of polymer electret.
[0021] Furthermore, an external excitation source can be added when stirring the solution in step (2).
[0022] Furthermore, the excitation source includes one of light, ultrasound, microwave, or magnetic field.
[0023] Furthermore, when the excitation source is ultrasound, the ultrasound frequency is 40–80 kHz.
[0024] Beneficial effects: Compared with the prior art, the present invention has the following outstanding advantages: The wet vanadium precipitation method of the present invention is simple and low in cost. The addition of polymer electret improves the precipitation efficiency. No nitrogen-containing waste liquid, ammonia and other waste substances are generated during the precipitation process, thus avoiding environmental pollution and making it more suitable for industrial production. Attached Figure Description
[0025] Figure 1 Vanadium pentoxide deposition induced by polytetrafluoroethylene film in lithium chloride solution.
[0026] Figure 2 Vanadium pentoxide deposition induced by polytetrafluoroethylene film in sodium chloride solution.
[0027] Figure 3 Vanadium pentoxide deposition induced by polytetrafluoroethylene film in potassium chloride solution.
[0028] Figure 4 Vanadium pentoxide deposition induced by polytetrafluoroethylene film in magnesium chloride solution.
[0029] Figure 5 Vanadium pentoxide deposition induced by polymethyl methacrylate film in zinc chloride solution.
[0030] Figure 6 Vanadium pentoxide deposition induced by polycarbonate film in zinc chloride solution.
[0031] Figure 7 Vanadium pentoxide deposition induced by polypropylene film in zinc chloride solution.
[0032] Figure 8 Images of the polymer electrets added in the examples.
[0033] Figure 9 The deposition process induced by polyethylene terephthalate in zinc chloride solution. Detailed implementation method:
[0034] The technical solution of the present invention will be further described below with reference to the accompanying drawings.
[0035] Example 1
[0036] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0037] 2. Add a certain amount of lithium chloride to the above solution to make the lithium ion concentration 0.2 mol / L.
[0038] 3. Add a 5*20cm cube to the prepared solution. 2 Polytetrafluoroethylene film ( Figure 8 ).
[0039] 4. Place this solution in an ultrasonic instrument, maintain the water temperature in the ultrasonic instrument at 70℃, and allow it to vibrate ultrasonically at a frequency of 80KHz for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the generated vanadium pentoxide colloid.
[0040] 5. Filter the ultrasonically treated brick-red gelatinous liquid to obtain the brick-red sample. Dry the sample to obtain vanadium pentoxide powder.
[0041] The results are as follows Figure 1As shown, a is the solution of vanadium pentoxide that has just been dissolved; b is the solution after ultrasonic vibration for 5 hours (the white film floating in the bottle is the polytetrafluoroethylene film); c is the V2O5 after filtration; d is the V2O5 after drying and grinding into powder.
[0042] Example 2
[0043] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0044] 2. Add a certain amount of sodium chloride to the above solution so that the concentration of sodium ions is 0.1 mol / L.
[0045] 3. Place a 5*20cm container into the prepared solution. 2 Polytetrafluoroethylene film ( Figure 8 ).
[0046] 4. Place this solution in an ultrasonic instrument, maintain the water temperature in the ultrasonic instrument at 60℃, and allow it to vibrate ultrasonically at a frequency of 40KHz for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the generated vanadium pentoxide colloid.
[0047] 5. The ultrasonically treated brick-red colloidal liquid was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 2 As shown.
[0048] Example 3:
[0049] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0050] 2. Add a certain amount of potassium chloride to the above solution so that the concentration of potassium ions is 0.5 mol / L.
[0051] 3. Place a 5*20cm container into the prepared solution. 2 Polytetrafluoroethylene film ( Figure 8 ).
[0052] 4. Place this solution in an ultrasonic instrument, maintain the water temperature in the ultrasonic instrument at 80℃, and allow it to vibrate ultrasonically at a frequency of 80KHz for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the generated vanadium pentoxide colloid.
[0053] 5. The ultrasonically treated brick-red colloidal liquid was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 3 As shown.
[0054] Example 4
[0055] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0056] 2. Add a certain amount of magnesium chloride to the above solution so that the concentration of magnesium ions is 1 mol / L.
[0057] 3. Add a 5*20cm cube to the prepared solution. 2 Polytetrafluoroethylene film ( Figure 8 ).
[0058] 4. Place this solution in a warm water bath at 80°C and stir for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the vanadium pentoxide colloid that has been formed.
[0059] 5. The brick-red colloidal liquid after the reaction was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 4 As shown.
[0060] Example 5
[0061] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0062] 2. Add a certain amount of zinc chloride to the above solution so that the concentration of zinc ions is 0.5 mol / L.
[0063] 3. Place a 10*10cm [material] into the prepared solution. 2 Polymethyl methacrylate film ( Figure 8 ).
[0064] 4. Place this solution in a warm water bath at 80°C and stir for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the vanadium pentoxide colloid that has been formed.
[0065] 5. The brick-red colloidal liquid after the reaction was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 5 As shown.
[0066] Example 6
[0067] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0068] 2. Add a certain amount of zinc chloride to the above solution so that the concentration of zinc ions is 0.5 mol / L.
[0069] 3. Place a 5*5cm [piece of material] into the prepared solution. 2 polycarbonate film ( Figure 8 ).
[0070] 4. Place this solution in a warm water bath at 80°C and stir for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the vanadium pentoxide colloid that has been formed.
[0071] 5. The brick-red colloidal liquid after the reaction was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 6 As shown.
[0072] Example 7
[0073] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0074] 2. Add a certain amount of zinc chloride to the above solution so that the concentration of zinc ions is 0.5 mol / L.
[0075] 3. Place a 5*5cm [piece of material] into the prepared solution. 2 Polypropylene film ( Figure 8 ).
[0076] 4. Place this solution in a warm water bath at 80°C and stir for 5 hours. The solution will turn into a brick-red gel. This brick-red substance is the vanadium pentoxide colloid that has been formed.
[0077] 5. The brick-red colloidal liquid after the reaction was filtered to obtain the brick-red sample. The sample was then dried to obtain vanadium pentoxide powder. The results are as follows: Figure 7 As shown.
[0078] Comparative Example
[0079] 1. Weigh 1.5g of vanadium pentoxide, add 10ml of 7% hydrogen peroxide to dissolve the vanadium pentoxide in the aqueous solution, and then add a certain amount of deionized water to make the solution 300ml.
[0080] 2. Add a certain amount of zinc chloride to the above solution so that the concentration of zinc ions is 0.5 mol / L.
[0081] 3. Add 5*10cm to the prepared solution. 2 Polyethylene terephthalate (PET).
[0082] 4. Place this solution in an ultrasonic instrument, maintain the water temperature in the instrument at 80℃, and allow it to vibrate ultrasonically at a frequency of 80kHz for 5 hours. Figure 9 As shown, no brick-red precipitate appeared in the solution, proving that non-electrode is ineffective for the deposition of vanadium by wet chemical methods.
Claims
1. A wet vanadium precipitation method, characterized in that, Includes the following steps: (1) Take a certain amount of vanadium-containing solution; add Li to the solution. + Na + K + Mg 2+ Cu 2+ Ag + , or Zn 2+ Metal salts; Vanadium-containing solutions are solutions containing vanadate, metavanadate, or pyrovanadate. (2) Add polymer electret to the solution in step (1) and stir the solution at 20~100℃; The polymer electret includes one or more of polymethyl methacrylate, polycarbonate, polypropylene, and tetrafluoroethylene-perfluoropropylene copolymer; (3) After the reaction is complete, filter the solution to obtain the final product.
2. The vanadium precipitation method according to claim 1, characterized in that, The metal salt mentioned in step (1) includes one or more of the following: metal chloride / hypochlorite, metal sulfate compound, metal nitrate compound or metal acetate compound.
3. The vanadium precipitation method according to claim 1, characterized in that, The final concentration of metal ions in the solution after adding metal salt in step (1) is 10 mM ~ 1 M.
4. The vanadium precipitation method according to claim 1, characterized in that, An external excitation source is added when stirring the solution in step (2).
5. The vanadium precipitation method according to claim 4, characterized in that, The excitation source includes one of light, ultrasound, microwave, or magnetic field.
6. The vanadium precipitation method according to claim 5, characterized in that, When the excitation source is ultrasound, the ultrasound frequency is 40~80KHz.