CN114132962A - Method for preparing vanadium trioxide by liquid-phase hydrogen reduction - Google Patents
Method for preparing vanadium trioxide by liquid-phase hydrogen reduction Download PDFInfo
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- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 title claims abstract description 71
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000007885 magnetic separation Methods 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 239000012141 concentrate Substances 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing vanadium trioxide by liquid-phase hydrogen reduction. The technical scheme is as follows: dissolving a pentavalent vanadium compound by using a sodium hydroxide solution, adjusting the pH value to 4-6, placing the obtained vanadium-rich liquid in an autoclave, adding nickel powder as a catalyst, stirring at 250-300 ℃ under the conditions that the hydrogen partial pressure is 3-6 MPa and the hydrogen partial pressure is 300-600 r/min, cooling, and releasing pressure to obtain vanadium trioxide slurry. And then carrying out wet magnetic separation to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry. Performing solid-liquid separation on the magnetic concentrate slurry, and performing vacuum drying to obtain magnetic concentrate, and returning the obtained magnetic concentrate to the step 2 to be used as a catalyst for recycling; performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying the wet magnetic separation tailings to prepare vanadium trioxide; and (4) returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound. The invention has high safety, low energy consumption, low production cost, catalyst recycling and high purity of the prepared product.
Description
Technical Field
The invention belongs to the technical field of vanadium trioxide preparation. In particular to a method for preparing vanadium trioxide by liquid-phase hydrogen reduction.
Background
Vanadium trioxide is an important vanadium oxide and can be used for preparing sheet vanadium or powder vanadium, ferrovanadium, vanadium nitride, vanadium carbide and the like. In addition, vanadium trioxide can have phase transition due to temperature, and resistivity, magnetic susceptibility, light projection rate and reflectivity all change suddenly during phase transition, so that the vanadium trioxide has important application in aspects of thermoelectric switches, magnetic switches, optical switches, sensors, thin film materials and the like. At present, the preparation method of vanadium trioxide is roughly divided into reduction roasting and liquid phase synthesis:
at present, the most common method for preparing vanadium trioxide is reduction roasting, and reducing gases such as carbon monoxide, ammonia gas, coal gas, hydrogen or methane and the like are usually introduced for reduction roasting, wherein the roasting temperature is generally higher than 600 ℃. It can be seen that most of the reducing gases introduced in the existing reduction roasting have flammable and explosive potential safety hazards, and the high-temperature condition during roasting not only increases the production energy consumption, but also improves the danger coefficient of blasting. Therefore, researchers have proposed a liquid phase synthesis technology of vanadium trioxide.
The liquid-phase synthesis technology of vanadium trioxide generally takes high-concentration vanadium-rich liquid as a raw material, and adds a reducing agent or gas at the temperature of less than 400 ℃ to carry out liquid-phase pressurization vanadium precipitation. The patent technology of 'a method for preparing vanadium trioxide microsphere powder by tartaric acid induction' (CN 103011290B) comprises the steps of uniformly mixing vanadium pentoxide and tartaric acid in a certain proportion in water or alcohol, reacting for 20-26 h at the reaction temperature of 170-190 ℃, and calcining for 3-4 h to obtain vanadium trioxide; the patent technology of 'a preparation method of vanadium trioxide powder' (CN 105621485B) adopts a vanadium source, thioglycollic acid and water as raw materials, and the vanadium source and the thioglycollic acid have a molar ratio of 0.5-2: 1, an autoclave filling rate of 0.6-0.85 and a temperature of 240-280 ℃ to perform hydrothermal reaction for 16-32 hours to prepare pure-phase vanadium trioxide powder with a better crystal form; zhang Guobin et al (Guobin Zhang, Yimin Zhang, Shenxu Bao, lacing Huang, Liuhong Zhang. A Novel Eco-Friendly Vanadium Precipitation method hydrothermic Reduction Technology [ J ]. Minerals,2017,7(10) ], adopt a pressurized Hydrogen Reduction method to prepare Vanadium trioxide, use palladium chloride as a catalyst to enhance the reducibility of Hydrogen, and react for 2 hours under the conditions of 250 ℃ and 4MPa of Hydrogen partial pressure, thereby finally obtaining a Vanadium trioxide product with high Vanadium deposition rate and purity.
In conclusion, although the method for synthesizing vanadium trioxide in a liquid phase can greatly reduce energy consumption, the reaction time is too long, the efficiency is low, and the industrial application is severely limited; the research of Zhang Guobin and the like shortens the reaction time to 2h, but the price of palladium chloride is as high as 1500 yuan/g, and the production cost is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a method for preparing vanadium trioxide, which has high safety, low energy consumption, low production cost and capability of recycling a catalyst, and the vanadium trioxide prepared by the method has high purity.
In order to achieve the above object, the invention adopts the technical scheme that:
Step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 40-60%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 10-40 g/L; and then stirring for 2-5 h under the conditions that the temperature is 250-300 ℃, the hydrogen partial pressure is 3-6 MPa and the rotating speed is 300-600 r/min, cooling and pressure releasing to obtain vanadium trioxide slurry.
And 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 8-13 kOe and the magnetic medium wire is 0.5-3 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry.
Step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; and (4) returning the magnetic concentrate to the step (2) to be used as a catalyst for recycling.
Step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying is carried out on the wet magnetic separation tailings to prepare vanadium trioxide; and returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
The pentavalent vanadium compound is one of vanadium pentoxide powder, sodium orthovanadate powder, sodium metavanadate powder and sodium pyrovanadate powder; the purity of the pentavalent vanadium compound is greater than 98%.
The Ni content of the nickel powder is more than 99.5 wt%; the granularity of the nickel powder is less than 0.037 mm.
Compared with the prior art, the invention has the following positive effects due to the adoption of the technical scheme:
(1) the reaction temperature of the invention is 250-300 ℃, compared with the reduction roasting (more than 500 ℃), the reaction energy consumption is obviously reduced, and the danger coefficient of explosion of the reducing gas in the reaction is also reduced, so that the safety is high.
(2) Compared with liquid-phase hydrogen reduction with palladium chloride as a catalyst, 8000 yuan can be saved in each ton of vanadium trioxide product, and the preparation cost can be obviously reduced; the reaction time of the invention is less than 5h, and compared with other liquid phase synthesis technologies, the production efficiency is high.
(3) The method adopts a cheap and efficient magnetic separation technology to recover and recycle the catalyst, avoids nickel powder from entering the product, and ensures the purity of vanadium trioxide in the product.
In the invention: the recovery rate of nickel powder is more than 99.6%, the precipitation rate of vanadium trioxide is more than 99.5%, and the purity of vanadium trioxide is more than 99.2%.
Therefore, the method has the characteristics of high safety, low energy consumption, low production cost and capability of recycling the catalyst, and the prepared vanadium trioxide has high purity.
Drawings
FIG. 1 is an XRD pattern of vanadium trioxide prepared by the invention.
Detailed Description
The invention will be further described with reference to the following drawings and detailed description, without limiting its scope:
in this embodiment:
the purity of the pentavalent vanadium compound is more than 98 percent;
the Ni content of the nickel powder is more than 99.5 wt%; the granularity of the nickel powder is less than 0.037 mm.
The detailed description is omitted in the embodiments.
Example 1
A method for preparing vanadium trioxide by liquid-phase hydrogen reduction. The method of the embodiment comprises the following specific steps:
Step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 50-60%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 10-20 g/L; and then stirring for 2-3 h under the conditions that the temperature is 250-260 ℃, the hydrogen partial pressure is 3-4 MPa and the rotating speed is 300-400 r/min, cooling and pressure releasing to obtain vanadium trioxide slurry.
And 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 8-9 kOe and the magnetic medium wire is 0.5-1 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry.
Step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; and (4) returning the magnetic concentrate to the step (2) to be used as a catalyst for recycling.
Step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying is carried out on the wet magnetic separation tailings to prepare vanadium trioxide; and returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
The pentavalent vanadium compound is vanadium pentoxide powder.
In this embodiment: the recovery rate of the nickel powder is more than 99.6 percent; the precipitation rate of vanadium trioxide is more than 99.7 percent; the purity of the vanadium trioxide is more than 99.3 percent.
Example 2
A method for preparing vanadium trioxide by liquid-phase hydrogen reduction. The method of the embodiment comprises the following specific steps:
Step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 50-60%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 20-30 g/L; and then stirring for 3-4 h under the conditions that the temperature is 260-270 ℃, the hydrogen partial pressure is 4-5 MPa and the rotating speed is 400-500 r/min, cooling and pressure releasing are carried out, so as to obtain vanadium trioxide slurry.
And 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 9-10 kOe and the magnetic medium wire is 1-1.5 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry.
Step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; and (4) returning the magnetic concentrate to the step (2) to be used as a catalyst for recycling.
Step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying is carried out on the wet magnetic separation tailings to prepare vanadium trioxide; and returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
The pentavalent vanadium compound is sodium orthovanadate powder.
In this embodiment: the recovery rate of the nickel powder is more than 99.6 percent; the precipitation rate of vanadium trioxide is more than 99.8 percent; the purity of the vanadium trioxide is more than 99.3 percent.
Example 3
A method for preparing vanadium trioxide by liquid-phase hydrogen reduction. The method of the embodiment comprises the following specific steps:
Step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 40-50%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 30-40 g/L; and then stirring for 4-5 h under the conditions that the temperature is 270-290 ℃, the hydrogen partial pressure is 5-6 MPa and the rotating speed is 500-600 r/min, cooling and pressure releasing are carried out, so as to obtain vanadium trioxide slurry.
And 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 10-11 kOe and the magnetic medium wire is 1.5-2 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry.
Step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; and (4) returning the magnetic concentrate to the step (2) to be used as a catalyst for recycling.
Step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; and carrying out vacuum drying on the wet magnetic separation tailings to prepare vanadium trioxide.
And returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
The pentavalent vanadium compound is sodium metavanadate powder.
In this embodiment: the recovery rate of the nickel powder is more than 99.7 percent; the precipitation rate of vanadium trioxide is more than 99.5 percent; the purity of the vanadium trioxide is more than 99.2 percent.
Example 4
A method for preparing vanadium trioxide by liquid-phase hydrogen reduction. The method of the embodiment comprises the following specific steps:
Step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 40-50%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 30-40 g/L; and then stirring for 4-5 h under the conditions that the temperature is 290-300 ℃, the hydrogen partial pressure is 5-6 MPa and the rotating speed is 300-400 r/min, cooling and pressure releasing are carried out, so as to obtain vanadium trioxide slurry.
And 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 11-13 kOe and the magnetic medium wires are 2-3 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry.
Step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; and (4) returning the magnetic concentrate to the step (2) to be used as a catalyst for recycling.
Step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying is carried out on the wet magnetic separation tailings to prepare vanadium trioxide; and returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
The pentavalent vanadium compound is sodium pyrovanadate powder.
In this embodiment: the recovery rate of the nickel powder is more than 99.7 percent, the precipitation rate of the vanadium trioxide is more than 99.6 percent, and the purity of the vanadium trioxide is more than 99.2 percent.
Compared with the prior art, the embodiment has the following positive effects:
(1) the reaction temperature of the specific embodiment is 250-300 ℃, compared with the reduction roasting (more than 500 ℃) technology, the reaction energy consumption is obviously reduced, the danger coefficient of explosion of reducing gas in the reaction is also reduced, and the safety is high.
(2) Compared with liquid-phase hydrogen reduction with palladium chloride as a catalyst, the vanadium trioxide per ton of the vanadium trioxide product can save more than 8000 yuan, and the preparation cost can be obviously reduced; the reaction time of the specific embodiment is less than 5h, and compared with other liquid phase synthesis technologies, the production efficiency is high.
(3) The specific embodiment adopts a cheap and efficient magnetic separation technology to recover and recycle the catalyst, thereby avoiding nickel powder from entering the product and ensuring the purity of vanadium trioxide in the product. The product prepared by the specific embodiment is shown in the attached drawing, fig. 1 is an XRD spectrum of vanadium trioxide prepared in example 1, and it can be seen from fig. 1 that the products prepared by liquid-phase hydrogen reduction are all vanadium trioxide crystals, and have no other impurities and high purity.
In this embodiment: the recovery rate of nickel powder is more than 99.6%, the precipitation rate of vanadium trioxide is more than 99.5%, and the purity of vanadium trioxide is more than 99.2%.
Therefore, the specific implementation mode has the characteristics of high safety, low energy consumption, low production cost and capability of recycling the catalyst, and the prepared vanadium trioxide is high in purity.
Claims (3)
1. A method for preparing vanadium trioxide by liquid-phase hydrogen reduction is characterized in that the method for preparing vanadium trioxide is as follows:
step 1, completely dissolving a pentavalent vanadium compound by using a sodium hydroxide solution, and then adjusting the pH value to 4-6 to obtain a vanadium-rich solution; the vanadium concentration of the vanadium-rich liquid is 0.1-1.0 mol/L;
step 2, placing the vanadium-rich liquid into an autoclave according to the filling rate of the vanadium-rich liquid in the autoclave being 40-60%; adding nickel powder into the vanadium-rich liquid in the high-pressure kettle as a catalyst according to the solid-to-liquid ratio of 10-40 g/L; then stirring for 2-5 h under the conditions that the temperature is 250-300 ℃, the hydrogen partial pressure is 3-6 MPa and the rotating speed is 300-600 r/min, cooling and pressure releasing to obtain vanadium trioxide slurry;
step 3, carrying out wet magnetic separation on the vanadium trioxide slurry under the conditions that the magnetic field intensity is 8-13 kOe and the magnetic medium wire is 0.5-3 mm to obtain magnetic separation concentrate slurry and magnetic separation tailing slurry;
step 3.1, performing solid-liquid separation on the magnetic concentrate slurry to obtain wet magnetic concentrate; then carrying out vacuum drying on the wet magnetic concentrate to obtain a magnetic concentrate; returning the magnetic concentrate to the step 2 to be used as a catalyst for recycling;
step 3.2, performing solid-liquid separation on the magnetic separation tailing slurry to obtain wet magnetic separation tailings and alkali liquor; vacuum drying is carried out on the wet magnetic separation tailings to prepare vanadium trioxide; and returning the alkali liquor to the step 1 for recycling so as to dissolve the pentavalent vanadium compound.
2. The method for preparing vanadium trioxide by liquid-phase hydrogen reduction according to claim 1, wherein the pentavalent vanadium compound is one of vanadium pentoxide powder, sodium orthovanadate powder, sodium metavanadate powder and sodium pyrovanadate powder; the purity of the pentavalent vanadium compound is greater than 98%.
3. The method for preparing vanadium trioxide by liquid-phase hydrogen reduction according to claim 1, characterized in that the Ni content of the nickel powder is > 99.5 wt%; the granularity of the nickel powder is less than 0.037 mm.
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Citations (6)
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| US2665970A (en) * | 1952-12-26 | 1954-01-12 | Ca Nat Research Council | Precipitation of vanadium oxides |
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| CN107117654A (en) * | 2017-06-26 | 2017-09-01 | 武汉科技大学 | It is a kind of from the method that vanadium dioxide is prepared containing vanadium solution |
| CN112047390A (en) * | 2020-09-02 | 2020-12-08 | 北京石油化工学院 | Nickel-doped lithium vanadate nanorod with large specific surface area as well as preparation method and application thereof |
| CN113336267A (en) * | 2021-05-11 | 2021-09-03 | 武汉科技大学 | Method for preparing vanadium trioxide by utilizing catalytic reduction of metal coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2665970A (en) * | 1952-12-26 | 1954-01-12 | Ca Nat Research Council | Precipitation of vanadium oxides |
| CN1105178A (en) * | 1993-03-16 | 1995-07-12 | 埃尔夫·阿奎坦生产公司 | Method for removing hydrogen sulphide from a gas and recovering in the form of sulphur |
| US20040005270A1 (en) * | 2002-07-02 | 2004-01-08 | Conoco Inc. | Stabilized nickel-containing catalysts and process for production of syngas |
| CN107117654A (en) * | 2017-06-26 | 2017-09-01 | 武汉科技大学 | It is a kind of from the method that vanadium dioxide is prepared containing vanadium solution |
| CN112047390A (en) * | 2020-09-02 | 2020-12-08 | 北京石油化工学院 | Nickel-doped lithium vanadate nanorod with large specific surface area as well as preparation method and application thereof |
| CN113336267A (en) * | 2021-05-11 | 2021-09-03 | 武汉科技大学 | Method for preparing vanadium trioxide by utilizing catalytic reduction of metal coating |
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Application publication date: 20220304 |