CN114149026B - Method for preparing vanadium pentoxide by taking ammonium vanadate as raw material - Google Patents
Method for preparing vanadium pentoxide by taking ammonium vanadate as raw material Download PDFInfo
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- CN114149026B CN114149026B CN202111346510.0A CN202111346510A CN114149026B CN 114149026 B CN114149026 B CN 114149026B CN 202111346510 A CN202111346510 A CN 202111346510A CN 114149026 B CN114149026 B CN 114149026B
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 58
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 title claims abstract description 50
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 238000002844 melting Methods 0.000 claims abstract description 48
- 230000008018 melting Effects 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 34
- 239000000498 cooling water Substances 0.000 claims description 22
- 238000010924 continuous production Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 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 claims description 9
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 9
- 230000009615 deamination Effects 0.000 claims description 7
- 238000006481 deamination reaction Methods 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 18
- 230000005587 bubbling Effects 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of vanadium metallurgy, and discloses a method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material. The method comprises the following steps: (1) Reacting ammonium vanadate at 300-600 ℃ for 40-80 min to dehydrate and deaminize; (2) Continuously heating to melt the material obtained in the step (1) at 900-1300 ℃ to form a liquid molten pool; (3) Oxidizing gas is introduced into the liquid molten pool from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa, and vapor volatilizes from the liquid molten pool and is cooled to 120-450 ℃ to obtain high-purity vanadium pentoxide. According to the invention, ammonium vanadate is used as a raw material, heating, dehydrating and deaminizing are performed first, low-valence vanadium is oxidized into vanadium pentoxide by feeding oxidizing gas, and according to the difference of the melting point and saturated vapor pressure of the vanadium pentoxide and impurity oxides, the volatilization rate of the vanadium pentoxide is accelerated by bubbling gas supplied at the bottom of a molten pool, so that the high-purity vanadium pentoxide is prepared by separation and purification.
Description
Technical Field
The invention relates to the technical field of vanadium metallurgy, in particular to a method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material.
Background
Vanadium pentoxide is widely applied to the fields of steel, chemical industry, aerospace, energy and the like. With the development of the material field, the high-end vanadium-containing materials such as vanadium electrolyte, vanadium-aluminum alloy, metal vanadium, vanadium catalyst and the like have higher and higher purity requirements on the raw material vanadium pentoxide, and the market demand of the high-purity vanadium pentoxide also has a rapid growing trend. At present, the preparation of the high-purity vanadium pentoxide comprises a chemical precipitation method, a solution extraction method, a chlorination method and the like.
CN112209441a discloses a method for preparing high-purity vanadium pentoxide by purifying ammonium metavanadate, which comprises the steps of performing alkali dissolution of ammonium metavanadate, aging of vanadium liquid, hydrolysis of precipitated vanadium, re-dissolution of precipitated vanadium to obtain ammonium metavanadate with purity of more than 99.8%, and performing calcination deamination to obtain high-purity vanadium pentoxide. The method adopts the methods of secondary dissolution, primary adsorption impurity removal, secondary precipitation and primary calcination deamination to obtain the high-purity vanadium pentoxide, and chemical agents such as sodium hydroxide, sulfuric acid, ammonia water and the like are used in the process, so that the process has the defects of long process flow, large agent dosage and high treatment difficulty of the generated wastewater.
CN111057876a discloses a method for preparing high-purity vanadium pentoxide by microemulsion extraction, which comprises the steps of adjusting the pH, preparing the microemulsion, extracting, carrying microemulsion phase washing, back extracting, precipitating vanadium from alkaline ammonium salt, calcining and deaminizing to obtain the high-purity vanadium pentoxide, wherein organic extractant, kerosene, sodium hydroxide, sodium chloride, sulfuric acid, ammonium sulfate or ammonium chloride and other chemical agents are used in the process, so that the process also has the defects of long process flow, large agent consumption and large difficulty in treating the generated wastewater.
CN103130279B discloses a method for producing high-purity vanadium pentoxide by a chlorination method, which comprises the steps of uniformly mixing a vanadium-containing substance and a carbon simple substance, drying, adding the mixture into a reactor, and sequentially carrying out chlorination, rectification, hydrolysis and post-treatment to obtain the high-purity vanadium pentoxide.
In summary, the existing preparation method of the high-purity vanadium pentoxide has the problems of long process flow, large medicament consumption, environmental pollution, incomplete impurity removal and the like, so that the development of the preparation method of the high-purity vanadium pentoxide with simple process, safety, environmental protection and low cost is necessary.
Disclosure of Invention
The invention aims to solve the problems of long process flow, large medicament consumption, environmental pollution, incomplete impurity removal and the like in the prior art for preparing high-purity vanadium pentoxide, and provides a method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material, which ensures V according to the difference of the melting point and saturated vapor pressure of the vanadium pentoxide and impurity oxide 2 O 5 Under the condition of no decomposition reaction, the vanadium pentoxide is melted to form a liquid molten pool, the saturated vapor pressure of the vanadium pentoxide is rapidly increased after the temperature is higher than the melting point, the volatilization rate of the vanadium pentoxide is accelerated through the bubbling of the gas supply at the bottom of the molten pool, and the impurity elements are difficult to volatilize, so that the high-efficiency separation of vanadium impurities is realized, and the high-purity vanadium pentoxide is obtained through the condensation and collection of the vanadium pentoxide vapor.
In order to achieve the above object, the present invention provides a method for preparing vanadium pentoxide by using ammonium vanadate as a raw material, which is characterized by comprising the following steps:
(1) Reacting ammonium vanadate at 300-600 ℃ for 40-80 min to dehydrate and deaminize, thus obtaining a material containing vanadium oxide;
(2) Continuously heating to melt the material obtained in the step (1) at 900-1300 ℃ to form a liquid molten pool;
(3) Introducing oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at the pressure of 0.15-0.2 Mpa, volatilizing vanadium pentoxide vapor from the liquid molten pool, and cooling to 120-450 ℃ to obtain vanadium pentoxide with the purity of not less than 99.9%.
Preferably, the method further comprises:
(4) When the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step (2), emptying the residual materials in the liquid molten pool;
(5) Repeating the steps (1) - (4) for continuous production.
Preferably, in step (1), the ammonium vanadate is 2NH 3 ·3V 2 O 5 ·H 2 O、(NH 4 ) 6-x ·Na x V 10 O 28 ·10H 2 O and 2NH 3 ·V 2 O 5 ·H 2 At least one of O.
More preferably, (NH) 4 ) 6-x ·Na x V 10 O 28 ·10H 2 And x in O is 0-2.
Preferably, the content of impurities in the ammonium vanadate is not less than 0.5 mass%.
Preferably, the impurity in the ammonium vanadate is at least one of Fe, cr, mn, si, na, K, P and S.
Preferably, in step (2), the material obtained in step (1) is melted at 950 to 1200 ℃.
Preferably, in step (3), the oxidizing gas is oxygen and/or air.
Preferably, in the step (3), the vanadium pentoxide vapor is cooled by adopting circulating cooling water.
Preferably, the method is implemented in a vanadium pentoxide production apparatus comprising a melting furnace, a condenser and an exhaust gas treatment system arranged in sequence,
the top of the melting furnace is provided with a feed inlet, the periphery and the bottom of the melting furnace are provided with a plurality of heating elements, and the bottom of the melting furnace is also provided with a discharge hole and an air supply system;
the condenser comprises a cooling channel, a plurality of condenser partition plates are respectively arranged on the upper inner wall and the lower inner wall of the cooling channel at intervals, a cooling water inlet, a cooling water channel and a cooling water outlet are arranged on the outer side of the top of the cooling channel, and a plurality of collectors are continuously and detachably arranged at the bottom of the cooling channel.
Preferably, the interval between two adjacent condenser baffles is 20-80 cm.
Preferably, the bottom of the cooling channel is continuously and detachably provided with 3-8 collectors.
Preferably, the method comprises the steps of:
s1, adding ammonium vanadate from the feed inlet into the melting furnace, closing the feed inlet, heating the melting furnace, and reacting the ammonium vanadate at 300-600 ℃ for 40-80 min for dehydration and deamination to obtain a material containing vanadium oxide;
s2, continuously heating the melting furnace, and melting the material obtained in the step S1 at 900-1300 ℃ to form a liquid molten pool;
s3, starting the gas supply system, introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at the pressure of 0.15-0.2 Mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling in the cooling channel to 120-450 ℃, and obtaining vanadium pentoxide with the purity not lower than 99.9% in the collector.
Preferably, the method further comprises:
s4, when the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step S2, closing the air supply system, stopping heating, opening the discharge port, and emptying the residual materials in the liquid molten pool;
s5, closing the discharge hole, and repeating the steps S1 to S4 to perform continuous production.
According to the invention, vanadium ammonium vanadate is used as a raw material, heating, dehydrating and deaminizing are performed first to form a liquid molten pool, then oxidizing gas is supplied to enable low-valence vanadium obtained by dehydration and deaminizing or low-valence vanadium reduced by ammonia gas in the deaminizing process to fully oxidize and exist in the form of vanadium pentoxide, and according to the difference of the melting point and saturated vapor pressure of the vanadium pentoxide and the impurity oxide, the volatilization rate of the vanadium pentoxide is accelerated through gas supply bubbling at the bottom of the molten pool, so that the high-purity vanadium pentoxide is obtained by separation and purification.
Drawings
FIG. 1 is a schematic diagram of a vanadium pentoxide production apparatus according to the present invention.
Description of the reference numerals
10 a melting furnace; 11 charging ports; a heating element 12; 13, a discharge hole; 14 a gas supply system;
a 20 condenser; 21 cooling channels; 22 condenser baffles; 23 cooling water inlet; 24 cooling water channels; 25 a cooling water outlet; 26 collectors;
30 an exhaust gas treatment system.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material, which comprises the following steps:
(1) Reacting ammonium vanadate at 300-600 ℃ for 40-80 min to dehydrate and deaminize, thus obtaining a material containing vanadium oxide;
(2) Continuously heating to melt the material obtained in the step (1) at 900-1300 ℃ to form a liquid molten pool;
(3) Introducing oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at the pressure of 0.15-0.2 Mpa, volatilizing vanadium pentoxide vapor from the liquid molten pool, and cooling to 120-450 ℃ to obtain vanadium pentoxide with the purity of not less than 99.9%.
According to the method, ammonium vanadate is dehydrated and deaminated by heating to obtain low-valence and high-valence vanadium oxides, then materials containing the vanadium oxides are heated continuously to form a liquid molten pool at a higher temperature, and then oxidizing gas is introduced from the bottom of the liquid molten pool, so that on one hand, low-valence vanadium can be oxidized into vanadium pentoxide, on the other hand, the evaporation rate of the vanadium pentoxide vapor can be accelerated by supplying gas from the bottom of the molten pool, and then the vanadium pentoxide vapor volatilized from the liquid molten pool is cooled to obtain high-purity vanadium pentoxide.
In a specific embodiment, to achieve continuous production, the method further comprises:
(4) When the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step (2), emptying the residual materials in the liquid molten pool;
(5) Repeating the steps (1) - (4) for continuous production.
In the process of the present invention, the ammonium vanadate may be a conventional choice in the art.
In a specific embodiment, in step (1), the ammonium vanadate is 2NH 3 ·3V 2 O 5 ·H 2 O (ammonium hexapolyvanadate), (NH) 4 ) 6-x ·Na x V 10 O 28 ·10H 2 O (ammonium decavanadate) and 2NH 3 ·V 2 O 5 ·H 2 O(2NH 3 ·V 2 O 5 ·H 2 O) at least one of the following. In a preferred embodiment, (NH) 4 ) 6-x ·Na x V 10 O 28 ·10H 2 X in O is any value from 0 to 2, and may be an integer or a non-integer.
In a specific embodiment, the content of impurities in the ammonium vanadate is more than or equal to 0.5 mass%. Further, the impurity in the ammonium vanadate is at least one of Fe, cr, mn, si, na, K, P and S. Further, fe, cr, mn, si, P is present in the vanadium pentoxide in the form of oxides and Na, K, S are present in the vanadium pentoxide in the form of sulfates.
In the method of the present invention, in order to sufficiently dehydrate and deaminize the ammonium vanadate to obtain vanadium oxide, it is necessary to dehydrate and deaminize the ammonium vanadate at an appropriate temperature.
In a specific embodiment, in step (1), the ammonium vanadate may be dehydrated and deaminated by reacting at 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or 600 ℃.
In the method of the present invention, in order to melt the material obtained in step (1) to form a liquid bath while preventing volatilization of impurities, it is necessary to melt the material at an appropriate temperature.
In a specific embodiment, in step (2), the material obtained in step (1) may be melted at 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, or 1300 ℃.
In a preferred embodiment, in step (2), the material obtained in step (1) is melted at 950 to 1200 ℃.
In the method of the present invention, in step (3), the oxidizing gas is oxygen and/or air.
In order to provide sufficient oxygen to the liquid bath for oxidation of the low valence vanadium while controlling the rate of bubbling of the gas at the bottom of the bath, reasonable control of the gas supply pressure is required.
In a specific embodiment, in step (3), the oxidizing gas may be introduced into the liquid bath from the bottom of the liquid bath at a pressure of 0.15Mpa, 0.16Mpa, 0.17Mpa, 0.18Mpa, 0.19Mpa or 0.2 Mpa.
In a preferred embodiment, in step (3), the vanadium pentoxide vapor may be cooled down by a common cooling medium, preferably by circulating cooling water.
For better practice of the invention, the process may be carried out in a vanadium pentoxide production apparatus as shown in fig. 1, comprising a melting furnace 10, a condenser 20 and an exhaust gas treatment system 30 in this order,
the top of the melting furnace 10 is provided with a charging hole 11, the periphery and the bottom are provided with a plurality of heating elements 12, and the bottom of the melting furnace 10 is also provided with a discharging hole 13 and an air supply system 14;
the condenser 20 comprises a cooling channel 21, a plurality of condenser baffles 22 are respectively arranged on the upper inner wall and the lower inner wall of the cooling channel 21 at intervals, a cooling water inlet 23, a cooling water channel 24 and a cooling water outlet 25 are arranged on the outer side of the top of the cooling channel 21, and a plurality of collectors 26 are continuously arranged at the bottom of the cooling channel 21.
In the vanadium pentoxide production apparatus, after ammonium vanadate is added from a feed port 11, a melting furnace 10 is heated by a heating element 12, and ammonium vanadate is dehydrated and deaminated; the heating element 12 continues to heat, so that the melting furnace 10 is heated, and the materials are melted at a higher temperature to form a liquid molten pool; then, starting the gas supply system 14, introducing oxidizing gas from the bottom of the liquid molten pool, enabling vanadium pentoxide vapor to volatilize from the liquid molten pool rapidly and enter the cooling channel 21, cooling the vapor by a circulating cooling medium provided in the cooling water channel 24, and enabling the vapor to become vanadium pentoxide solid which falls into the collector 26 to obtain high-purity vanadium pentoxide; the exhaust gas treatment system 30 is used for treating pollutants such as ammonia and dust. The plurality of collectors 26 are arranged in series, i.e. the plurality of collectors 26 are arranged one next to the other with no space between adjacent collectors 26, such that the arrangement allows coolingSolid high-purity V falling down after any part in the cooling channel 21 is cooled 2 O 5 Can fall into the collector 26.
In a specific embodiment, the interval between two adjacent condenser baffles 22 is 20-80 cm. In the present invention, if the interval between adjacent two of the condenser baffles 22 is too small, the vapor flow resistance increases to cause an increase in residence time thereof in the cooler, decreasing production efficiency; if the spacing between adjacent two of the condenser baffles 22 is too great, the reduced vapor drag results in a reduced residence time in the condenser, failing to cool the vapor to a specified temperature by sufficient heat exchange to gain access to the collector. Therefore, in the present invention, the interval between two adjacent condenser baffles 22 is set at 20 to 80cm, and vapor is sufficiently heat-exchanged cooled to a specified temperature in the cooler and then enters the collector while ensuring proper production efficiency.
In a preferred embodiment, the spacing between two adjacent ones of the condenser baffles 22 is 30 to 60cm.
In another preferred embodiment, the bottom of the cooling channel 21 is continuously detachably provided with 3 to 8 collectors 26.
On the basis of implementing the invention by adopting the vanadium pentoxide preparation device shown in fig. 1, the method comprises the following steps:
s1, adding ammonium vanadate from a charging hole 11 into a melting furnace 10, closing the charging hole 11, heating the melting furnace 10, and reacting the ammonium vanadate at 300-600 ℃ for 40-80 min for dehydration and deamination to obtain a material containing vanadium oxide;
s2, continuously heating the melting furnace 10, and melting the materials obtained in the step S1 at 900-1300 ℃ to form a liquid molten pool;
s3, starting the gas supply system 14, introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at the pressure of 0.15-0.2 Mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling in the cooling channel 21 to 120-450 ℃, and obtaining vanadium pentoxide with the purity not lower than 99.9% in the collector 26.
In the method, after ammonium vanadate is added into a melting furnace 10 from a charging port 11, the ammonium vanadate reacts at a lower temperature to be dehydrated and deaminated, then a heating element 12 continuously heats the melting furnace 10, a liquid molten pool is formed by materials at a higher temperature, oxidizing gas is supplied from the bottom of the liquid molten pool by a gas supply system 14 to promote volatilization of vanadium pentoxide vapor, the volatilized vapor enters a cooling channel 21 to be cooled down and converted into vanadium pentoxide solid, and the vanadium pentoxide solid falls into a collector 26 to obtain high-purity vanadium pentoxide.
In a preferred embodiment, the method further comprises:
s4, when the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step S2, closing the air supply system 14, stopping heating, opening the discharge port 13, and emptying the residual materials in the liquid molten pool; s5, closing the discharge hole 13, and repeating the steps S1 to S4 to perform continuous production.
In the invention, after the liquid molten pool is formed, the vanadium pentoxide is volatilized from the liquid molten pool continuously along with continuous heating and continuous ventilation of oxidizing gas. When the liquid molten pool level is reduced to 0.05-0.10 times of the initial liquid molten pool level, the air supply system 14 is closed, heating is stopped, the rest materials are emptied, and the ammonium vanadate can be added again for continuous production after the discharge hole 13 is closed.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The examples of the present invention were all carried out in the following vanadium pentoxide production apparatus.
As shown in fig. 1, the vanadium pentoxide preparation device comprises a melting furnace 10, a condenser 20 and a tail gas treatment system 30 which are sequentially arranged, wherein a charging hole 11 is formed in the top of the melting furnace 10, a plurality of heating elements 12 are arranged around and at the bottom of the melting furnace 10, and a discharging hole 13 and a gas supply system 14 are further arranged at the bottom of the melting furnace 10; the condenser 20 comprises a cooling channel 21, a plurality of condenser partition plates 22 are respectively arranged on the upper inner wall and the lower inner wall of the cooling channel 21 at intervals, the interval between every two adjacent condenser partition plates 22 is 20-80 cm, a cooling water inlet 23, a cooling water channel 24 and a cooling water outlet 25 are arranged on the outer side of the top of the cooling channel 21, and 3-8 collectors 26 are continuously and detachably arranged at the bottom of the cooling channel 21.
Example 1
(1) Ammonium vanadate (2 NH) was fed from the feed inlet 11 3 ·3V 2 O 5 ·H 2 O, impurities include: adding 0.32% of Fe, 0.17% of Cr, 0.15% of Si, 0.77% of Na, 0.13% of K and 0.07% of P into a melting furnace 10, closing a feed port 11, heating the melting furnace 10 to 450 ℃, and reacting for 50min to dehydrate and deaminize; (2) Continuously heating to raise the temperature of the melting furnace 10 to 1180 ℃ to melt the materials in the furnace to form a liquid molten pool; (3) Starting an air supply system 14, introducing oxygen into the liquid molten pool from the bottom of the liquid molten pool at a pressure of 0.17Mpa, allowing vanadium pentoxide vapor to enter a cooling channel 21, cooling to 230 ℃ by adopting circulating cooling water, and obtaining high-purity vanadium pentoxide in a collector 26; (4) When the liquid level of the molten pool is reduced to 0.08 times of the initial value of the liquid level of the molten pool in the step (2), the air supply system 14 is closed, heating is stopped, the discharge port 13 is opened, and the residual materials in the melting furnace 10 are emptied; (5) And (5) closing the discharge hole 13, and repeating the steps (1) - (4) to perform continuous production.
The purity of the vanadium pentoxide obtained by the detection was 99.92%, the content of Fe was 0.002%, the content of Cr was 0.004%, the content of Si was 0.02%, the content of Na was 0.04%, the content of K was 0.002%, and the content of P was 0.001% by mass.
Example 2
(1) Ammonium vanadate (2 NH) was fed from the feed inlet 11 3 ·V 2 O 5 ·H 2 O, impurities include: adding 0.16 mass% of Fe, 0.20 mass% of Mn, 0.07 mass% of Si, 0.31 mass% of Na and 0.11 mass% of P into the melting furnace 10, closing the feed port 11, heating the melting furnace 10 to 340 ℃, and reacting for 75min for dehydration and deamination; (2) Continuously heating to raise the temperature of the melting furnace 10 to 1000 ℃ to melt the materials in the furnace to form a liquid molten pool; (3) The gas supply system 14 was started and the pressure from the bottom of the liquid bath was 0.19MPaIntroducing air into the liquid molten pool, allowing the vanadium pentoxide vapor to enter a cooling channel 21, adopting circulating cooling water to cool to 300 ℃, and obtaining high-purity vanadium pentoxide in a collector 26; (4) When the liquid level of the molten pool is reduced to 0.07 times of the initial value of the liquid level of the molten pool in the step (2), closing the air supply system 14, stopping heating, opening the discharge port 13, and emptying the residual materials in the melting furnace; (5) And (5) closing the discharge hole 13, and repeating the steps (1) - (4) to perform continuous production.
The purity of the vanadium pentoxide obtained by the detection was 99.90%, the content of Fe was 0.022 mass%, the content of Mn was 0.018 mass%, the content of Si was 0.009 mass%, the content of Na was 0.039 mass%, and the content of P was 0.002 mass%.
Example 3
(1) Ammonium vanadate ((NH) was fed from the feed port 11 4 ) 6-x ·Na x V 10 O 28 ·10H 2 O (x is 0.01), and impurities include: adding 0.21 mass percent of Fe, 0.13 mass percent of Cr, 0.34 mass percent of Si and 0.76 mass percent of Na into the melting furnace 10, closing a charging port 11, heating the melting furnace 10 to 520 ℃, and reacting for 40min for dehydration and deamination; (2) Continuously heating to raise the temperature of the melting furnace 10 to 970 ℃ to melt the materials in the furnace to form a liquid molten pool; (3) Starting an air supply system 14, introducing air into the liquid molten pool from the bottom of the liquid molten pool at a pressure of 0.20Mpa, allowing vanadium pentoxide vapor to enter a cooling channel 21, cooling to 380 ℃ by adopting circulating cooling water, and obtaining high-purity vanadium pentoxide in a collector 26; (4) When the liquid level of the molten pool is reduced to 0.05 times of the initial value of the liquid level of the molten pool in the step (2), the air supply system 14 is closed, heating is stopped, the discharge port 13 is opened, and the residual materials in the melting furnace 10 are emptied; (5) And (5) closing the discharge hole 13, and repeating the steps (1) - (4) to perform continuous production.
The purity of the vanadium pentoxide obtained by the detection was 99.97%, the content of Fe was 0.002 mass%, the content of Cr was 0.003 mass%, the content of Si was 0.007 mass%, and the content of Na was 0.010 mass%.
Comparative example 1
The process of example 2 was carried out, except that in step (2), the melting furnace 10 was heated to 800 ℃ continuously to melt the material in the furnace to form a liquid bath.
The purity of the vanadium pentoxide obtained by the detection was 99.67%, the content of Fe was 0.076% by mass, the content of Mn was 0.051% by mass, the content of Si was 0.026% by mass, the content of Na was 0.12% by mass, and the content of P was 0.03% by mass.
Comparative example 2
The procedure of example 2 was followed, except that in step (3), air was introduced into the liquid bath from the bottom of the liquid bath at a pressure of 0.13 MPa.
The purity of the vanadium pentoxide obtained by the detection was 99.70%, the content of Fe was 0.040 mass%, the content of Mn was 0.029 mass%, the content of Si was 0.041 mass%, the content of Na was 0.15 mass%, and the content of P was 0.02 mass%.
Comparative example 3
The high-purity vanadium pentoxide is prepared by adopting the raw materials described in the example 2 according to the method of multiple re-dissolution-precipitation of the existing production process, the ammonium vanadate is dissolved by adopting sodium hydroxide, then sulfuric acid solution is added to adjust the pH value to 1.85, vanadium is precipitated at 95 ℃, the ammonium vanadate is obtained by filtering after the precipitation is finished, and the ammonium vanadate is deaminated under the condition of 520 ℃ after the above operation is repeated for 5 times.
The purity of the vanadium pentoxide obtained by the detection was 99.54%, the content of Fe was 0.09% by mass, the content of Mn was 0.04% by mass, the content of Si was 0.05% by mass, the content of Na was 0.17% by mass, and the content of P was 0.06% by mass.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. The method for preparing the vanadium pentoxide by taking the ammonium vanadate as the raw material is characterized by comprising the following steps of:
(1) Reacting ammonium vanadate at 300-600 ℃ for 40-80 min to dehydrate and deaminize, so as to obtain a material containing vanadium oxide;
(2) Continuously heating to melt the material obtained in the step (1) at 950-1200 ℃ to form a liquid molten pool;
(3) Introducing oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at the pressure of 0.15-0.2 mpa, volatilizing vanadium pentoxide vapor from the liquid molten pool, and cooling to 120-450 ℃ to obtain vanadium pentoxide with the purity of not less than 99.9%.
2. The method according to claim 1, wherein the method further comprises:
(4) When the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step (2), emptying the residual materials in the liquid molten pool;
(5) Repeating the steps (1) - (4), and carrying out continuous production.
3. The method of claim 1, wherein in step (1), the ammonium vanadate is 2NH 3 ·3V 2 O 5 ·H 2 O、(NH 4 ) 6-x ·Na x V 10 O 28 ·10H 2 O and 2NH 3 ·V 2 O 5 ·H 2 At least one of O.
4. A method according to claim 3, characterized in that (NH) 4 ) 6-x ·Na x V 10 O 28 ·10H 2 And x in O is 0-2.
5. The method according to claim 3, wherein the content of impurities in the ammonium vanadate is not less than 0.5 mass%.
6. The method of claim 5, wherein the impurity in the ammonium vanadate is at least one of Fe, cr, mn, si, na, K, P and S.
7. The method according to claim 1, wherein in step (3), the oxidizing gas is oxygen and/or air.
8. The method of claim 1, wherein in step (3), the vanadium pentoxide vapor is cooled using circulating cooling water.
9. The method according to any one of claims 1 to 8, characterized in that the method is carried out in a vanadium pentoxide production plant comprising a melting furnace (10), a condenser (20) and an exhaust gas treatment system (30) arranged in this order,
the top of the melting furnace (10) is provided with a charging hole (11), the periphery and the bottom are provided with a plurality of heating elements (12), and the bottom of the melting furnace (10) is also provided with a discharging hole (13) and an air supply system (14);
the condenser (20) comprises a cooling channel (21), a plurality of condenser baffles (22) are respectively arranged on the upper inner wall and the lower inner wall of the cooling channel (21) at intervals, a cooling water inlet (23), a cooling water channel (24) and a cooling water outlet (25) are arranged on the outer side of the top of the cooling channel (21), and a plurality of collectors (26) are continuously and detachably arranged at the bottom of the cooling channel (21).
10. The method according to claim 9, wherein the spacing between two adjacent condenser baffles (22) is 20-80 cm.
11. Method according to claim 9, characterized in that the bottom of the cooling channel (21) is continuously detachably provided with 3-8 collectors (26).
12. The method according to claim 9, characterized in that it comprises the steps of:
s1, adding ammonium vanadate from the feed inlet (11) into the melting furnace (10), closing the feed inlet (11), heating the melting furnace (10), and reacting the ammonium vanadate at 300-600 ℃ for 40-80 min for dehydration and deamination to obtain a vanadium oxide-containing material;
s2, continuously heating the melting furnace (10), and melting the materials obtained in the step S1 at 900-1300 ℃ to form a liquid molten pool;
s3, starting the gas supply system (14), introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool at a pressure of 0.15-0.2 mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling in the cooling channel (21) to 120-450 ℃, and obtaining vanadium pentoxide with purity not lower than 99.9% in the collector (26).
13. The method according to claim 12, wherein the method further comprises:
s4, when the liquid molten pool level is reduced to 0.05-0.10 times of the initial value of the liquid molten pool level in the step S2, closing the air supply system (14), stopping heating, opening the discharge port (13), and emptying the residual materials in the liquid molten pool;
s5, closing the discharge hole (13), and repeating the steps S1-S4 to perform continuous production.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039582A (en) * | 1975-12-29 | 1977-08-02 | Gakif Zakirovich Nasyrov | Method of preparing vanadium pentoxide |
| CN111592041A (en) * | 2020-06-05 | 2020-08-28 | 攀钢集团钒钛资源股份有限公司 | Melting furnace and method for smelting vanadium pentoxide by using same |
| CN111994952A (en) * | 2020-10-10 | 2020-11-27 | 攀钢集团研究院有限公司 | Method for preparing high-purity vanadium pentoxide by vacuum sublimation of metallurgical-grade vanadium pentoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039582A (en) * | 1975-12-29 | 1977-08-02 | Gakif Zakirovich Nasyrov | Method of preparing vanadium pentoxide |
| CN111592041A (en) * | 2020-06-05 | 2020-08-28 | 攀钢集团钒钛资源股份有限公司 | Melting furnace and method for smelting vanadium pentoxide by using same |
| CN111994952A (en) * | 2020-10-10 | 2020-11-27 | 攀钢集团研究院有限公司 | Method for preparing high-purity vanadium pentoxide by vacuum sublimation of metallurgical-grade vanadium pentoxide |
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| 电热法制取五氧化二钒熔片;黄国辉;《湖南有色金属》;第第5卷卷(第第5期期);44-46页 * |
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