CN114149026A - 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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- CN114149026A CN114149026A CN202111346510.0A CN202111346510A CN114149026A CN 114149026 A CN114149026 A CN 114149026A CN 202111346510 A CN202111346510 A CN 202111346510A CN 114149026 A CN114149026 A CN 114149026A
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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 202
- 238000000034 method Methods 0.000 title claims abstract description 57
- 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 13
- 239000007788 liquid Substances 0.000 claims abstract description 92
- 238000002844 melting Methods 0.000 claims abstract description 49
- 230000008018 melting Effects 0.000 claims abstract description 49
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 44
- 239000000498 cooling water Substances 0.000 claims description 22
- 238000010924 continuous production Methods 0.000 claims description 11
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005192 partition Methods 0.000 claims description 7
- 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
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 19
- 230000009615 deamination Effects 0.000 abstract description 6
- 238000006481 deamination reaction Methods 0.000 abstract description 6
- 230000005587 bubbling Effects 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 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 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater 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
- 229910021529 ammonia Inorganic materials 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
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 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
- -1 organic extractant 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
- 238000005406 washing Methods 0.000 description 1
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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
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- 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 deaminate; (2) continuously heating to melt the material obtained in the step (1) at 900-1300 ℃ to form a liquid molten pool; (3) and introducing oxidizing gas from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa into the liquid molten pool, volatilizing steam from the liquid molten pool, cooling to 120-450 ℃, and obtaining the high-purity vanadium pentoxide. According to the method, ammonium vanadate is used as a raw material, heating dehydration and deamination are carried out firstly, low-valence vanadium is oxidized into vanadium pentoxide by supplying oxidizing gas, and according to the difference between the melting point and the saturated vapor pressure of the vanadium pentoxide and an impurity oxide, the vanadium pentoxide is volatilized at a high speed by supplying gas and bubbling at the bottom of a melting tank, 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 purity requirement of high-end vanadium-containing materials such as vanadium electrolyte, vanadium-aluminum alloy, metal vanadium, vanadium catalyst and the like on the raw material vanadium pentoxide is higher and higher, and the market demand of the high-purity vanadium pentoxide is in a rapid growth trend. At present, the high-purity vanadium pentoxide can be prepared by methods such as 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 dissolving ammonium metavanadate in alkali, aging vanadium liquid, hydrolyzing to precipitate vanadium, dissolving again to precipitate vanadium to obtain ammonium metavanadate with purity of more than 99.8%, and calcining to remove ammonia 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 large difficulty in treating the generated wastewater.
CN111057876A discloses a method for preparing high-purity vanadium pentoxide by microemulsion extraction, which comprises adjusting pH, preparing microemulsion, extracting, washing loaded microemulsion phase, back-extracting, precipitating vanadium with alkaline ammonium salt, calcining to remove ammonia to obtain high-purity vanadium pentoxide, and using chemical agents such as organic extractant, kerosene, sodium hydroxide, sodium chloride, sulfuric acid, ammonium sulfate or ammonium chloride, therefore, the process has the disadvantages of long process flow, large dosage of agents and large difficulty in treating 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 into a reactor, and carrying out chlorination, rectification, hydrolysis and post-treatment in sequence to obtain the high-purity vanadium pentoxide.
In conclusion, the existing preparation method of 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 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 of the high-purity vanadium pentoxide preparation process in the prior art, and provides a method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material2O5Under 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 by bubbling air supplied to 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 by condensing and collecting vanadium pentoxide vapor.
In order to achieve the purpose, the invention provides a method for preparing vanadium pentoxide by taking 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, and dehydrating and deaminating to obtain 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) and introducing oxidizing gas from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa into the liquid molten pool, volatilizing vanadium pentoxide vapor from the liquid molten pool, cooling to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9%.
Preferably, the method further comprises:
(4) when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool in the step (2), emptying the residual materials in the liquid molten pool;
(5) repeating the steps (1) to (4) to carry out continuous production.
Preferably, in step (1), the ammonium vanadate is 2NH3·3V2O5·H2O、(NH4)6-x·NaxV10O28·10H2O and 2NH3·V2O5·H2At least one of O.
More preferably, (NH)4)6-x·NaxV10O28·10H2X in O is 0 to 2.
Preferably, the content of impurities in the ammonium vanadate is more than or equal to 0.5 mass percent.
Preferably, the impurities in the ammonium vanadate are at least one of Fe, Cr, Mn, Si, Na, K, P and S.
Preferably, in the step (2), the material obtained in the step (1) is melted at 950-1200 ℃.
Preferably, in step (3), the oxidizing gas is oxygen and/or air.
Preferably, in the step (3), the vanadium pentoxide vapor is cooled by using circulating cooling water.
Preferably, the method is implemented in a vanadium pentoxide preparation device, the vanadium pentoxide preparation device comprises a melting furnace, a condenser and a tail gas treatment system which are sequentially arranged,
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 outlet and a gas supply system;
the condenser includes cooling channel, cooling channel's last inner wall and lower inner wall interval respectively are provided with a plurality of condenser baffles, cooling channel's the top outside is provided with cooling water inlet, cooling water passageway and cooling water export, cooling channel's bottom can be dismantled in succession and be provided with a plurality of collectors.
Preferably, the interval between two adjacent condenser partition plates is 20-80 cm.
Preferably, the bottom of the cooling channel is continuously detachably provided with 3-8 collectors.
Preferably, the method comprises the steps of:
s1, adding ammonium vanadate into the melting furnace from the feeding port, closing the feeding port, heating the melting furnace, and reacting at 300-600 ℃ for 40-80 min to dehydrate and deaminate the ammonium vanadate 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;
and S3, starting the gas supply system, introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling the vanadium pentoxide vapor in the cooling channel to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9% in the collector.
Preferably, the method further comprises:
s4, when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool liquid level in the step S2, closing the gas supply system, stopping heating, opening the discharge hole, and emptying the residual materials in the liquid molten pool;
s5, closing the discharge hole, repeating the steps S1-S4, and carrying out continuous production.
According to the invention, vanadium precipitation product ammonium vanadate is used as a raw material, the raw material is heated for dehydration and deamination, low-valent vanadium obtained by dehydration and deamination or the low-valent vanadium reduced by ammonia gas in the deamination process is fully oxidized to exist in the form of vanadium pentoxide after a liquid molten pool is formed, according to the difference between the melting point and the saturated vapor pressure of the vanadium pentoxide and an impurity oxide, the vanadium pentoxide volatilization rate is accelerated by gas supply bubbling at the bottom of the molten pool so as to separate and purify the high-purity vanadium pentoxide, no chemistry is used in the process, no wastewater is generated, the process is simple, the production cost is low, the high-purity vanadium pentoxide can be obtained by one-step heating, volatilization and separation, and compared with other vanadium pentoxide production processes, the method has obvious advantages in the aspects of safety, environmental protection and economic cost.
Drawings
FIG. 1 is a schematic view of a vanadium pentoxide preparation apparatus according to the present invention.
Description of the reference numerals
10 a melting furnace; 11 a feed inlet; 12 a heating element; 13, discharging a material outlet; 14, a gas supply system;
20 a condenser; 21 a cooling channel; 22 a condenser baffle; 23 cooling water inlet; 24 cooling water passages; 25 cooling water outlet; 26 a collector;
30 tail gas treatment system.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should 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, and dehydrating and deaminating to obtain 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) and introducing oxidizing gas from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa into the liquid molten pool, volatilizing vanadium pentoxide vapor from the liquid molten pool, cooling to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9%.
According to the method, ammonium vanadate is heated to dehydrate and deaminate to obtain low-valence and high-valence vanadium oxides, then the ammonium vanadate is continuously heated to enable materials containing the vanadium oxides to form a liquid molten pool at a higher temperature, then oxidizing gas is introduced from the bottom of the liquid molten pool, on one hand, the low-valence vanadium can be oxidized into vanadium pentoxide, on the other hand, gas can be supplied from the bottom of the molten pool to bubble to accelerate the volatilization rate of vanadium pentoxide vapor, 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 level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool in the step (2), emptying the residual materials in the liquid molten pool;
(5) repeating the steps (1) to (4) to carry out continuous production.
In the method of the present invention, the ammonium vanadate may be selected conventionally in the art.
In a specific embodiment, in step (1), the ammonium vanadate is 2NH3·3V2O5·H2O (ammonium hexavanadate), (NH)4)6-x·NaxV10O28·10H2O (ammonium decavanadate) and 2NH3·V2O5·H2O(2NH3·V2O5·H2O). In a preferred embodiment, (NH)4)6-x·NaxV10O28·10H2X in O is any value of 0-2, and can 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 impurities in the ammonium vanadate are at least one of Fe, Cr, Mn, Si, Na, K, P and S. Further, Fe, Cr, Mn, Si, P are 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 deaminate ammonium vanadate to obtain vanadium oxide, it is necessary to dehydrate and deaminate 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 the step (2), the material obtained in the step (1) may be melted at 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃.
In a preferred embodiment, in the step (2), the material obtained in the step (1) is melted at 950-1200 ℃.
In the method of the present invention, in the step (3), the oxidizing gas is oxygen and/or air.
In order to provide sufficient oxygen to the liquid bath for the oxidation of vanadium suboxides while controlling the rate of bubbling of the gas supply at the bottom of the bath, reasonable control of the gas supply pressure is required.
In a specific embodiment, in the step (3), the oxidizing gas may be introduced into the liquid molten pool from the bottom of the liquid molten pool 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 can be cooled by a common cooling medium, preferably by circulating cooling water.
In order to better implement the invention, the method can be implemented in a vanadium pentoxide preparation device 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 arranged in sequence,
the top of the melting furnace 10 is provided with a feed inlet 11, a plurality of heating elements 12 are arranged around and at the bottom of the melting furnace 10, and the bottom of the melting furnace 10 is also provided with a discharge port 13 and a gas supply system 14;
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, 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 preparation device, ammonium vanadate is added from a feed inlet 11, and then a heating element 12 is used for heating a melting furnace 10, so that ammonium vanadate is dehydrated and deaminated; then the heating element 12 continues to heat continuously, so that the melting furnace 10 is heated, and the materials are melted at a higher temperature to form a liquid molten pool; then, the gas supply system 14 is started, oxidizing gas is introduced from the bottom of the liquid molten pool, vanadium pentoxide vapor rapidly volatilizes from the liquid molten pool and enters the cooling channel 21, the vapor is cooled by a circulating cooling medium provided in the cooling water channel 24 and then becomes vanadium pentoxide solid, and the vanadium pentoxide solid falls into the collector 26, so that high-purity vanadium pentoxide is obtained; the tail gas treatment system 30 is used for treating pollutants such as ammonia gas and dust. The plurality of collectors 26 are arranged in series, that is, the plurality of collectors 26 are arranged one after another without a space between the adjacent collectors 26, so that the solid high-purity V falling down after cooling any one portion of the cooling passage 21 is arranged2O5Can fall into the collector 26.
In a specific embodiment, the interval between two adjacent condenser partition plates 22 is 20-80 cm. In the present invention, if the interval between adjacent two of the condenser partitions 22 is too small, the vapor flow resistance increases to cause an increase in the residence time thereof in the cooler, lowering the production efficiency; if the spacing between two adjacent condenser baffles 22 is too large, the vapor drag decreases causing it to have a reduced residence time in the condenser and not be able to cool the vapor to a given temperature by sufficient heat exchange to enter the collector. Therefore, in the invention, the interval between two adjacent condenser partition plates 22 is set to be 20-80 cm, so that the steam enters the collector after being sufficiently cooled to the specified temperature in the cooler in a heat exchange manner while ensuring the proper production efficiency.
In a preferred embodiment, the interval between two adjacent condenser partition plates 22 is 30-60 cm.
In another preferred embodiment, the bottom of the cooling channel 21 is continuously and detachably provided with 3-8 collectors 26.
On the basis of implementing the invention by adopting the vanadium pentoxide preparation device shown in figure 1, the method comprises the following steps:
s1, adding ammonium vanadate into the melting furnace 10 from the feeding port 11, closing the feeding port 11, then heating the melting furnace 10 to raise the temperature, and reacting the ammonium vanadate at 300-600 ℃ for 40-80 min to dehydrate and deaminate to obtain a material containing vanadium oxide;
s2, continuously heating the melting furnace 10, and melting the material obtained in the step S1 at 900-1300 ℃ to form a liquid molten pool;
and S3, starting the gas supply system 14, introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling the vanadium pentoxide vapor in the cooling channel 21 to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9% in the collector 26.
According to the method, ammonium vanadate reacts at a lower temperature to be dehydrated and deaminated after being added into a melting furnace 10 from a feed inlet 11, then a heating element 12 continuously heats the melting furnace 10, materials form a liquid molten pool at a higher temperature, then an oxidizing gas is fed from the bottom of the liquid molten pool through a gas supply system 14 to promote vanadium pentoxide steam to volatilize, and the volatilized steam enters a cooling channel 21 to be cooled and converted into vanadium pentoxide solids and falls into a collector 26 to obtain high-purity vanadium pentoxide.
In a preferred embodiment, the method further comprises:
s4, when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool in the step S2, closing the gas supply system 14, stopping heating, opening the discharge hole 13, and emptying the residual materials in the liquid molten pool; s5, closing the discharge port 13, and repeating the steps S1-S4 to carry out continuous production.
In the invention, after the liquid molten pool is formed, the vanadium pentoxide is continuously volatilized from the liquid molten pool along with continuous heating and continuous introduction of oxidizing gas. And when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid level of the initial liquid molten pool, closing the gas supply system 14, stopping heating, emptying the residual materials, and closing the discharge port 13 to add ammonium vanadate again for continuous production.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The embodiments of the present invention are all implemented in the following vanadium pentoxide preparation 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 opening 11 is arranged at the top of the melting furnace 10, a plurality of heating elements 12 are arranged at the periphery and the bottom of the melting furnace 10, and a discharging opening 13 and a gas supply system 14 are also arranged at the bottom of the melting furnace 10; condenser 20 includes cooling channel 21, cooling channel 21's last inner wall and lower inner wall interval respectively are provided with a plurality of condenser baffles 22, adjacent two interval between the condenser baffle 22 is 20 ~ 80cm, cooling channel 21's the top outside is provided with cooling water inlet 23, cooling water passageway 24 and cooling water export 25, cooling channel 21's bottom can be dismantled in succession and be provided with 3 ~ 8 collectors 26.
Example 1
(1) Ammonium vanadate (2 NH) is fed from a feed port 113·3V2O5·H2O, 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 inlet 11, heating the melting furnace 10 to 450 ℃, and reacting for 50min to perform dehydration and deamination; (2) continuously heating the melting furnace 10 to 1180 ℃ to melt the materials in the furnace to form a liquid molten pool; (3) starting the gas supply system 14, introducing oxygen into the liquid molten pool from the bottom of the liquid molten pool under the pressure of 0.17Mpa, cooling the vanadium pentoxide vapor to 230 ℃ by adopting circulating cooling water after the vanadium pentoxide vapor enters the cooling channel 21, and obtaining high-purity vanadium pentoxide in the 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), closing the gas supply system 14, stopping heating, opening the discharge hole 13, and emptying the residual materials in the melting furnace 10; (5) closing the discharge port 13 and repeatingAnd (1) to (4) carrying out continuous production.
The purity of the obtained vanadium pentoxide 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%.
Example 2
(1) Ammonium vanadate (2 NH) is fed from a feed port 113·V2O5·H2O, impurities include: 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 a melting furnace 10, closing a charging port 11, heating the melting furnace 10 to 340 ℃, and reacting for 75min to dehydrate and deaminate; (2) continuously heating the melting furnace 10 to 1000 ℃ to melt the materials in the furnace to form a liquid molten pool; (3) starting the gas supply system 14, introducing air from the bottom of the liquid molten pool into the liquid molten pool at the pressure of 0.19Mpa, cooling the vanadium pentoxide vapor to 300 ℃ by adopting circulating cooling water after the vanadium pentoxide vapor enters the cooling channel 21, and obtaining high-purity vanadium pentoxide in the collector 26; (4) when the liquid level of the molten pool is reduced to 0.07 time of the initial value of the liquid level of the liquid molten pool in the step (2), closing the gas supply system 14, stopping heating, opening the discharge hole 13, and emptying the residual materials in the melting furnace; (5) and (5) closing the discharge hole 13, and repeating the steps (1) to (4) to carry out continuous production.
The purity of the obtained vanadium pentoxide 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) is fed from a feed port 114)6-x·NaxV10O28·10H2O (x is 0.01), and impurities include: 0.21 mass% of Fe, 0.13 mass% of Cr, 0.34 mass% of Si, and 0.76 mass% of Na) into a melting furnace 10, closing a feed port 11, heating the melting furnace 10 to 520 ℃, and reacting for 40min to dehydrate and deaminate; (2) continuously heating the melting furnace 10 to 970 ℃ so that the materials in the furnace are melted to form a liquid molten pool; (3) opening deviceStarting the gas supply system 14, introducing air from the bottom of the liquid molten pool into the liquid molten pool at the pressure of 0.20Mpa, cooling the vanadium pentoxide vapor to 380 ℃ by adopting circulating cooling water after the vanadium pentoxide vapor enters the cooling channel 21, and obtaining high-purity vanadium pentoxide in the 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), closing the gas supply system 14, stopping heating, opening the discharge hole 13, and emptying the residual materials in the melting furnace 10; (5) and (5) closing the discharge hole 13, and repeating the steps (1) to (4) to carry out continuous production.
The purity of the vanadium pentoxide obtained by 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 is followed except that in step (2), the furnace 10 is heated to 800 ℃ by continuous heating to melt the contents of the furnace to form a liquid bath.
The purity of the vanadium pentoxide obtained by detection was 99.67%, the content of Fe was 0.076 mass%, the content of Mn was 0.051 mass%, the content of Si was 0.026 mass%, the content of Na was 0.12 mass%, and the content of P was 0.03 mass%.
Comparative example 2
The procedure is as in example 2, except that in step (3), air is introduced into the liquid bath from the bottom thereof at a pressure of 0.13 MPa.
The purity of the vanadium pentoxide obtained by 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 raw materials described in embodiment 2 are adopted to prepare high-purity vanadium pentoxide by a multiple dissolution-precipitation method according to the existing production process, ammonium vanadate is dissolved by sodium hydroxide, then a sulfuric acid solution is added to adjust the pH value to 1.85, vanadium is precipitated at 95 ℃, ammonium vanadate is obtained by filtering after precipitation is completed, and after the operations are repeated for 5 times, the ammonium vanadate is deaminated at 520 ℃.
The purity of the vanadium pentoxide obtained by the detection was 99.54%, the content of Fe was 0.09 mass%, the content of Mn was 0.04 mass%, the content of Si was 0.05 mass%, the content of Na was 0.17 mass%, and the content of P was 0.06 mass%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing vanadium pentoxide by taking ammonium vanadate as a raw material is characterized by comprising the following steps:
(1) reacting ammonium vanadate at 300-600 ℃ for 40-80 min, and dehydrating and deaminating to obtain 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) and introducing oxidizing gas from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa into the liquid molten pool, volatilizing vanadium pentoxide vapor from the liquid molten pool, cooling to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9%.
2. The method of claim 1, further comprising:
(4) when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool in the step (2), emptying the residual materials in the liquid molten pool;
(5) repeating the steps (1) to (4) to carry out continuous production.
3. The method according to claim 1, wherein in step (1), the ammonium vanadate is 2NH3·3V2O5·H2O、(NH4)6-x·NaxV10O28·10H2O and 2NH3·V2O5·H2At least one of O;
preferably, (NH)4)6-x·NaxV10O28·10H2X in O is 0 to 2.
4. The method according to claim 3, wherein the content of impurities in the ammonium vanadate is not less than 0.5 mass%;
preferably, the impurities in the ammonium vanadate are at least one of Fe, Cr, Mn, Si, Na, K, P and S.
5. The method according to claim 1, wherein in the step (2), the material obtained in the step (1) is melted at 950 to 1200 ℃.
6. The method according to claim 1, wherein in step (3), the oxidizing gas is oxygen and/or air;
preferably, in the step (3), the vanadium pentoxide vapor is cooled by using circulating cooling water.
7. The method according to any one of claims 1 to 6, wherein the method is implemented in a vanadium pentoxide production plant comprising, in succession, a melting furnace (10), a condenser (20) and a tail gas treatment system (30),
the top of the melting furnace (10) is provided with a feed inlet (11), the periphery and the bottom of the melting furnace are provided with a plurality of heating elements (12), and the bottom of the melting furnace (10) is also provided with a discharge outlet (13) and a gas supply system (14);
condenser (20) include cooling channel (21), the last inner wall of cooling channel (21) is provided with a plurality of condenser baffles (22) with lower inner wall interval respectively, the top outside of cooling channel (21) is provided with cooling water inlet (23), cooling water passageway (24) and cooling water export (25), the bottom of cooling channel (21) can be dismantled in succession and be provided with a plurality of collectors (26).
8. The method according to claim 7, wherein the interval between two adjacent condenser partitions (22) is 20-80 cm;
preferably, the bottom of the cooling channel (21) is continuously and detachably provided with 3-8 collectors (26).
9. The method according to claim 7, characterized in that it comprises the steps of:
s1, adding ammonium vanadate into the melting furnace (10) from the feeding port (11), closing the feeding port (11), heating the melting furnace (10), and reacting at 300-600 ℃ for 40-80 min to dehydrate and deaminate the ammonium vanadate to obtain a material containing vanadium oxide;
s2, continuously heating the melting furnace (10), and melting the material obtained in the step S1 at 900-1300 ℃ to form a liquid molten pool;
and S3, starting the gas supply system (14), introducing the oxidizing gas into the liquid molten pool from the bottom of the liquid molten pool under the pressure of 0.15-0.2 Mpa, volatilizing the vanadium pentoxide vapor from the liquid molten pool, cooling the vanadium pentoxide vapor in the cooling channel (21) to 120-450 ℃, and obtaining vanadium pentoxide with the purity of not less than 99.9% in the collector (26).
10. The method of claim 9, further comprising:
s4, when the liquid level of the liquid molten pool is reduced to 0.05-0.10 times of the initial value of the liquid molten pool in the step S2, closing the gas supply system (14), stopping heating, opening the discharge hole (13), and emptying the residual materials in the liquid molten pool;
s5, closing the discharge hole (13), and repeating the steps S1-S4 to carry out continuous production.
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| CN115849445A (en) * | 2022-12-12 | 2023-03-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium oxynitride and preparation method thereof |
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| 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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| 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 |
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