CN114314662B - Method for preparing vanadium pentoxide by taking red vanadium as raw material through negative pressure distillation - Google Patents
Method for preparing vanadium pentoxide by taking red vanadium as raw material through negative pressure distillation Download PDFInfo
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- CN114314662B CN114314662B CN202111347646.3A CN202111347646A CN114314662B CN 114314662 B CN114314662 B CN 114314662B CN 202111347646 A CN202111347646 A CN 202111347646A CN 114314662 B CN114314662 B CN 114314662B
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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 234
- 238000000034 method Methods 0.000 title claims abstract description 70
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 69
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002994 raw material Substances 0.000 title claims abstract description 9
- 238000004821 distillation Methods 0.000 title claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 75
- 230000008018 melting Effects 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 69
- 238000001816 cooling Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000011344 liquid material Substances 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000498 cooling water Substances 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000010924 continuous production Methods 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 3
- 239000013043 chemical agent Substances 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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 red vanadium as a raw material through negative pressure distillation. The method comprises the following steps: (1) Reacting red vanadium at 250-400 ℃ for 30-120 min for dehydration; (2) Melting the material obtained in the step (1) at 800-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor; (3) And (3) guiding the vanadium pentoxide vapor out of the liquid molten pool under the pressure of 15-45 kPa, and cooling the vanadium pentoxide vapor to 150-350 ℃ to obtain the vanadium pentoxide with the purity of more than 99.90%. The method has the advantages of no chemical agent consumption, no pollution, low cost, simple process and high purity of the prepared vanadium pentoxide.
Description
Technical Field
The invention relates to the technical field of vanadium metallurgy, in particular to a method for preparing vanadium pentoxide by taking red vanadium as a raw material through negative pressure distillation.
Background
The vanadium pentoxide is a main raw material for preparing aerospace-grade vanadium-aluminum alloy, an all-vanadium redox flow battery, a luminescent material, a coloring material, a catalyst and the like. In recent years, industrial grade vanadium pentoxide is in the current situation of overproduction, low sales market, continuous price reduction and the like. And the high-precision fields such as all-vanadium batteries, vanadium-aluminum intermediate alloys, electrode materials, catalysts and the like have higher requirements on the purity of vanadium pentoxide. The high-purity vanadium pentoxide has wide application field and huge market prospect. At present, the preparation method of the high-purity vanadium pentoxide mainly comprises a chemical precipitation method, a solution extraction method, a chlorination method and the like.
CN106830077B discloses a method for purifying vanadium pentoxide, which comprises the following steps: and (3) reacting the mixture of sodium chloride, anhydrous aluminum chloride and vanadium pentoxide to be purified in an inert atmosphere, wherein the reaction temperature is 150-200 ℃, so as to obtain vanadium oxychloride gas and residues. The vanadium oxychloride gas is further treated to obtain high-purity vanadium pentoxide. The method has the advantages of high vanadium extraction rate, mild conditions and less time, and the reaction product is gaseous vanadium oxychloride, so that vanadium can be conveniently separated from other solid impurities or liquid, the process flow is short, the production cost is reduced, the generation of three wastes is reduced, the environmental pollution is small, and the purity of the prepared vanadium pentoxide product is more than or equal to 99.99%, and the requirements of the fields of vanadium-aluminum alloy, all-vanadium batteries and the like for aerospace can be met.
CN108862382a discloses a method for extracting high-purity vanadium pentoxide from lead vanadium ore. The method for extracting the high-purity vanadium pentoxide comprises the steps of preparing lead concentrate through acid leaching treatment of lead vanadium ore, oxidizing acid leaching solution, removing impurities, extracting, back extracting, removing impurities again, precipitating filtrate obtained after solid-liquid separation to obtain ammonium metavanadate solid, further refining the ammonium metavanadate solid to obtain an ammonium metavanadate product with the purity of more than 99.7%, and roasting the ammonium metavanadate to obtain the high-purity vanadium pentoxide. The method for extracting high-purity vanadium pentoxide from the lead vanadium ore can realize the conversion rate of vanadium in the lead vanadium ore up to 95 percent, and can obtain the vanadium pentoxide with the purity of more than 99.7 percent.
CN109022800B discloses an ultrasonic-assisted preparation method of high-purity V from titanium tetrachloride refined tailings 2 O 5 Is a method of (2). Mixing titanium tetrachloride refined tailings with alkali liquor, and introducing oxygen under the condition of ultrasound to carry out leaching reaction; carrying out solid-liquid separation on the leached slurry to obtain vanadium-containing leaching solution, carrying out constant-temperature impurity removal to obtain a purifying solution, and adding a vanadium precipitation agent into the purifying solution to carry out vanadium precipitation to obtain ammonium metavanadate precipitate; and drying and calcining the obtained ammonium metavanadate to obtain the high-purity vanadium pentoxide. The vanadium extraction process reduces the roasting process, reduces the energy consumption, ensures that the leaching rate of vanadium is 85% -98.5%, and ensures that the purity of the obtained vanadium pentoxide is more than 99.4%.
The method has various problems of complex flow, large reagent consumption, high cost and the like, and development of a new method for preparing high-purity V with high efficiency and low cost is needed to be urgently developed 2 O 5 Is a method of (2). Red vanadium is an important product in the process of sodium roasting, hydrolysis and vanadium precipitation, and V in the red vanadium is due to the fact that the vanadium precipitation precursor solution contains higher concentration of sodium ions 2 O 5 The purity of (2) is only 80-90%. In order to convert red vanadium into high-purity vanadium pentoxide with higher added value, the invention provides a method for preparing the vanadium pentoxide without adding chemical reagent or generating waste water, and the method has simple processVanadium.
Disclosure of Invention
The invention aims to solve the problems of complex technological process, high reagent consumption, high cost and the like in the prior art for preparing vanadium pentoxide, and provides a method for preparing vanadium pentoxide by using red vanadium as a raw material through negative pressure distillation. The method has the advantages of no chemical agent consumption, no pollution, low cost, simple process and high purity of the prepared vanadium pentoxide.
In order to achieve the above purpose, the invention provides a method for preparing vanadium pentoxide by taking red vanadium as a raw material through negative pressure distillation, which comprises the following steps:
(1) Reacting red vanadium at 250-400 ℃ for 30-120 min for dehydration;
(2) Melting the material obtained in the step (1) at 800-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
(3) And (3) guiding the vanadium pentoxide vapor out of the liquid molten pool under the pressure of 15-45 kPa, and cooling the vanadium pentoxide vapor to 150-350 ℃ to obtain the vanadium pentoxide with the purity of more than 99.90%.
Preferably, the method further comprises:
(4) When the liquid molten pool level is reduced to 0.1-0.2 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, the red vanadium contains 0.5 to 5 mass% of Na 2 O, 80 to 90 mass% of V 2 O 5 And 0.2 to 3 mass% of H 2 O。
More preferably, the Na content in the red vanadium is not less than 1 mass%.
Preferably, the red vanadium contains at least one of Fe, cr, mn, si, K, P and S impurities.
Preferably, the total content of Fe, cr, mn, si, K, P and S in the red vanadium is more than or equal to 0.5 mass percent.
Preferably, in step (2), the material obtained in step (1) is melted at 1100-1300 ℃ to form a liquid bath.
Preferably, in step (3), vanadium pentoxide vapour is led from the liquid bath at a pressure of 22 to 45 kPa.
Preferably, in step (3), the vanadium pentoxide vapour is cooled by circulating cooling water.
Preferably, the method is implemented in a vanadium pentoxide production apparatus comprising a melting furnace, a condenser and a vacuum system arranged in this order,
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;
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 30-60 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 red vanadium into the melting furnace from the charging opening, closing the charging opening, heating the melting furnace, and reacting the red vanadium for 30-120 min at 250-400 ℃ for dehydration;
s2, continuously heating the melting furnace, melting the material obtained in the step S1 at 800-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
s3, starting the vacuum system to control the pressure in the melting furnace to be 15-45 kPa, guiding the vanadium pentoxide vapor into the cooling channel from the melting furnace, cooling the vanadium pentoxide vapor to 150-350 ℃, and obtaining vanadium pentoxide with purity of more than 99.90% in the collector.
Preferably, the method further comprises:
s4, when the liquid molten pool level is reduced to 0.1-0.2 times of the initial value of the liquid molten pool level in the step S2, closing a vacuum system, stopping heating, opening the discharge port, and emptying the residual materials in the liquid molten pool in the melting furnace;
s5, closing the discharge hole, and repeating the steps S1 to S4 to perform continuous production.
According to the difference of the melting point and the saturated vapor pressure of the vanadium pentoxide in the red vanadium and the oxide of the other impurities, the method for preparing the high-purity vanadium pentoxide by adopting negative pressure volatilization separation and purification is provided, no chemical reagent is needed in the process, no waste water is generated, the process is simple, the production cost is low, the high-purity vanadium pentoxide can be obtained by only one-step heating volatilization separation, and compared with other high-purity 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 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;
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 vacuum 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 red vanadium as a raw material through negative pressure distillation, which comprises the following steps:
(1) Reacting red vanadium at 250-400 ℃ for 30-120 min for dehydration;
(2) Melting the material obtained in the step (1) at 800-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
(3) And (3) guiding the vanadium pentoxide vapor out of the liquid molten pool under the pressure of 15-45 kPa, and cooling the vanadium pentoxide vapor to 150-350 ℃ to obtain the vanadium pentoxide with the purity of more than 99.90%.
In the method, after the red vanadium is dehydrated, the red vanadium loses crystal water, the dehydrated material is melted at 800-1300 ℃ to form a liquid molten pool, vanadium pentoxide in the material is evaporated, and then the vanadium pentoxide vapor is led out and cooled under the condition of 15-45 kPa to avoid the condition that the oxygen partial pressure is too low to lead V 2 O 5 Producing O by decomposition 2 And low-valence vanadium oxide (VO 2 、V 2 O 3 Etc.), resulting in failure to obtain V 2 O 5 。
In a specific embodiment, the method further comprises:
(4) When the liquid molten pool level is reduced to 0.1-0.2 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 method, the chemical formula of the important product of the sodium roasting, hydrolysis and vanadium precipitation process of the red vanadium is xNa 2 O·yV 2 O 5 ·zH 2 O, wherein x is more than or equal to 1 and less than or equal to 3, y is more than or equal to 1 and less than or equal to 5, and z is more than or equal to 1 and less than or equal to 6. The red vanadium contains Na in an amount of 0.5 to 5 mass% 2 O, 80 to 90 mass% of V 2 O 5 0.2 to 3 mass% of H 2 O, the balance ofOther impurities.
In a specific embodiment, the content of Na in the red vanadium is more than or equal to 1 mass percent, namely the content of Na element in the red vanadium is more than or equal to 1 mass percent.
In the present invention, the other impurity is at least one of Fe, cr, mn, si, K, P and S impurities, fe, cr, mn, si, P of which exists in the form of oxide in red vanadium, and Na, K, S exist in the form of sulfate in red vanadium.
In a preferred embodiment, the total content of other impurity elements in the red vanadium is not less than 0.5 mass%, i.e., the total content of Fe, cr, mn, si, K, P and S in the red vanadium is not less than 0.5 mass%.
In the method of the invention, in order to ensure V in the material 2 O 5 Being able to melt to form a liquid bath and convert to vapor without melting the impurities to vapor requires that the melting temperature be controlled within a suitable range.
In a specific embodiment, in step (2), the material obtained in step (1) is melted at 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃ to form a liquid melt pool.
In a preferred embodiment, in step (2), the material from step (1) is melted at 1100-1300 ℃ to form a liquid bath.
In the method of the invention, in order to ensure that the vanadium pentoxide vapor can be volatilized vigorously under negative pressure and simultaneously ensure that the vanadium pentoxide is not decomposed and impurities are not volatilized, the vanadium pentoxide vapor is led out in a proper pressure range so as to realize V 2 O 5 And separating impurities.
In particular embodiments, in step (3), vanadium pentoxide vapour is withdrawn from the liquid bath at a pressure of 15kPa, 20kPa, 25kPa, 30kPa, 35kPa, 40kPa or 45 kPa.
In a preferred embodiment, in step (3), vanadium pentoxide vapour is led from the liquid bath at a pressure of 22 to 45 kPa.
In the method of the invention, the vanadium pentoxide vapor is changed from liquid stateAfter the molten pool is led out, only the molten pool is cooled to be converted into solid V 2 O 5 The high-purity vanadium pentoxide can be obtained by collecting.
In a specific embodiment, in the step (3), the vanadium pentoxide vapor is cooled by circulating cooling water.
The apparatus used to carry out the method is not limited as long as the present invention can be implemented.
In a specific embodiment, the method described above may be carried out in a vanadium pentoxide production apparatus as shown in fig. 1, which comprises a melting furnace 10, a condenser 20 and a vacuum 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;
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.
In the vanadium pentoxide production apparatus, after red vanadium is added from a charging port 11, a melting furnace 10 is heated by a heating element 12, and the red vanadium is dehydrated at a lower temperature; heating element 12 is then continued to heat melting furnace 10, the dehydrated material is melted at a higher temperature to form a liquid molten pool, the temperature of the liquid molten pool is continuously maintained to form vanadium pentoxide in the liquid material into vapor, the vapor of vanadium pentoxide is led out of melting furnace 10 into cooling channel 21 by vacuum system 30 providing negative pressure, impurities are left in melting furnace 10, and the vapor of vanadium pentoxide is cooled by circulating cooling water in cooling water channel 24 to obtain solid high-purity V 2 O 5 Falls into a collector, thereby realizing the purpose of purifying the vanadium pentoxide. The plurality of collectors 26 are arranged in succession, i.e. the plurality of collectors 26 are arranged one next to the other with no space between adjacent collectors 26, such thatSolid high-purity V capable of cooling any part in the cooling channel 21 and falling down is arranged 2 O 5 Can fall into the collector.
In the present invention, the interval between adjacent two of the condenser baffles 22 should be set within a suitable range. Too small interval, the increase of vapor flow resistance leads to the increase of residence time in the cooler, and the production efficiency is reduced; the excessive spacing, reduced vapor drag, results in reduced residence time in the cooler, failing to exchange sufficient heat to cool the vapor to the prescribed temperature and failing to enter the accumulator. The invention thus defines the spacing between adjacent two of said condenser baffles 22 in order to allow the vapor to enter the collector after sufficient heat exchange cooling to a specified temperature in the cooler while ensuring proper production efficiency.
In a preferred embodiment, the spacing between adjacent two of the condenser baffles 22 is 30 to 60cm.
In a 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 method of the invention by adopting the vanadium pentoxide preparation device of the invention, the method comprises the following steps:
s1, adding red vanadium into the melting furnace 10 from the feed inlet 11, closing the feed inlet 11, heating the melting furnace 10, and reacting the red vanadium for 30-120 min at 250-400 ℃ for dehydration;
s2, continuously heating the melting furnace 10, melting the material obtained in the step S1 at 800-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
s3, starting the vacuum system 30 to control the pressure in the melting furnace 10 to be 15-45 kPa, guiding the vanadium pentoxide vapor from the melting furnace 10 into the cooling channel 21, cooling the vanadium pentoxide vapor to 150-350 ℃, and obtaining vanadium pentoxide with purity of more than 99.90% in the collector 26.
In this method, the red vanadium is added through the feed inlet 11Putting the red vanadium into the melting furnace 10, heating the melting furnace 10 by a heating element 12, and dehydrating the red vanadium at the temperature of 250-400 ℃; then the melting furnace 10 is continuously heated by the heating element 12 to raise the temperature, so that the dehydrated material is melted to form a liquid molten pool at 800-1300 ℃, and the temperature of the liquid molten pool is continuously maintained, so that vanadium pentoxide in the liquid material forms vapor; then the vacuum system 30 provides negative pressure to control the pressure in the melting furnace 10 to be 15-45 kPa, vanadium pentoxide vapor is led out of the melting furnace 10 into the cooling channel 21 through the negative pressure, impurities remain in the melting furnace 10, and then the circulating cooling water in the cooling water channel 24 cools the vanadium pentoxide vapor to reduce the temperature, thereby realizing solid high-purity V 2 O 5 Falls into a collector.
In order to achieve continuous production with the process, in a preferred embodiment, the process further comprises:
s4, when the liquid molten pool level is reduced to 0.1-0.2 times of the initial value of the liquid molten pool level in the step S2, closing the vacuum system 30, stopping heating, opening the discharge port 13, and emptying the residual materials in the liquid molten pool in the melting furnace 10;
s5, closing the discharge hole 13, and repeating the steps S1 to S4 to perform continuous production.
The method has the advantages of no consumption of chemical agents, no pollution, low cost, simple process and the like, creatively utilizes the difference of the melting point and the saturated vapor pressure of the vanadium pentoxide in the red vanadium and the oxide of the rest impurities, and obtains the high-purity vanadium pentoxide by only one-step heating, volatilizing and separating.
The present invention will be described in detail by way of examples, but the protection of the present invention is not limited thereto.
The examples of the present invention were all carried out using the following vanadium pentoxide production apparatus.
As shown in fig. 1, the vanadium pentoxide preparing apparatus includes a melting furnace 10, a condenser 20 and a vacuum system 30 sequentially arranged, wherein a charging port 11 is arranged at 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 port 13 is also 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 30-60 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 arranged at the bottom of the cooling channel 21.
Example 1
(1) Red vanadium (V) was introduced from the inlet 11 2 O 5 The content was 83.2 mass%, impurity: na content of 1.78 mass%, fe content of 0.33 mass%, cr content of 0.12 mass%, si content of 0.42 mass%, K content of 0.15 mass% and P content of 0.02 mass%) is added into a melting furnace 10, a charging port 11 is closed, then the melting furnace 10 is heated to raise the temperature, and red vanadium reacts for 40min at 280 ℃ to dehydrate;
(2) Continuously heating the melting furnace 10 to 1050 ℃ to enable the dehydrated material in the step (1) to be completely melted to form a liquid molten pool, and maintaining the temperature of the liquid molten pool to enable vanadium pentoxide in the liquid material to be converted into vanadium pentoxide vapor;
(3) Starting a vacuum system 30 to control the pressure in the melting furnace 10 to be 22kPa, introducing vanadium pentoxide vapor from the melting furnace 10 into the cooling channel 21, cooling to 350 ℃ by adopting circulating cooling water, and obtaining high-purity vanadium pentoxide in the collector 26;
(4) When the liquid molten pool level is reduced to 0.15 times of the initial value of the liquid molten pool in the step (2), the vacuum system 30 is closed, heating is stopped, the discharge hole 13 is opened, and the residual materials in the liquid molten pool 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 high-purity vanadium pentoxide is 99.94%, the Na content is 0.012% by mass, the Fe content is 0.003% by mass, the Cr content is 0.002% by mass, the Si content is 0.006% by mass, the K content is 0.002% by mass, and the P content is 0.001% by mass.
Example 2
(1) Red vanadium (V) was introduced from the inlet 11 2 O 5 The content was 83.5 mass%, and impurity Na was contained1.88 mass percent of Fe content, 0.54 mass percent of Cr content, 0.22 mass percent of Si content, 0.33 mass percent of K content, 0.14 mass percent of P content and 0.02 mass percent of P content) are added into a melting furnace 10, a charging port 11 is closed, then the melting furnace 10 is heated to raise the temperature, and red vanadium reacts for 50 minutes at 300 ℃ to dehydrate;
(2) Continuously heating the melting furnace 10 to 1250 ℃ to enable the dehydrated material in the step (1) to be completely melted to form a liquid molten pool, and maintaining the temperature of the liquid molten pool to enable vanadium pentoxide in the liquid material to be converted into vanadium pentoxide steam;
(3) Starting a vacuum system 30 to control the pressure in the melting furnace 10 to be 36kPa, introducing vanadium pentoxide vapor from the melting furnace 10 into the cooling channel 21, cooling to 270 ℃ by adopting circulating cooling water, and obtaining high-purity vanadium pentoxide in the collector 26;
(4) When the liquid molten pool level is reduced to 0.17 times of the initial value of the liquid molten pool in the step (2), the vacuum system 30 is closed, heating is stopped, the discharge hole 13 is opened, and the residual materials in the liquid molten pool 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 high-purity vanadium pentoxide was detected to be 99.93%, the Na content was 0.010% by mass, the Fe content was 0.003% by mass, the Cr content was 0.003% by mass, the Si content was 0.005% by mass, the K content was 0.002% by mass, and the P content was 0.001% by mass.
Example 3
(1) Red vanadium (V) was introduced from the inlet 11 2 O 5 The content was 82.9 mass%, impurity: na content of 1.75 mass percent, fe content of 0.45 mass percent, cr content of 0.32 mass percent, si content of 0.41 mass percent, K content of 0.12 mass percent and P content of 0.03 mass percent are added into a melting furnace 10, a charging port 11 is closed, then the melting furnace 10 is heated to raise the temperature, and red vanadium reacts for 60 minutes at 320 ℃ to dehydrate;
(2) Continuously heating the melting furnace 10 to 1200 ℃ to enable the dehydrated material in the step (1) to be completely melted to form a liquid molten pool, and maintaining the temperature of the liquid molten pool to enable vanadium pentoxide in the liquid material to be converted into vanadium pentoxide steam;
(3) Starting a vacuum system 30 to control the pressure in the melting furnace 10 to be 35kPa, introducing vanadium pentoxide vapor into the cooling channel 21 from the melting furnace 10, cooling to 300 ℃ by adopting circulating cooling water, and obtaining high-purity vanadium pentoxide in the collector 26;
(4) When the liquid molten pool level is reduced to 0.14 times of the initial value of the liquid molten pool in the step (2), the vacuum system 30 is closed, heating is stopped, the discharge hole 13 is opened, and the residual materials in the liquid molten pool 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 high-purity vanadium pentoxide is 99.91%, the Na content is 0.011 mass%, the Fe content is 0.003 mass%, the Cr content is 0.002 mass%, the Si content is 0.004 mass%, the K content is 0.002 mass% and the P content is 0.001 mass%.
Comparative example 1
The procedure of example 3 was followed, except that in step (2), the melting furnace 10 was continuously heated to 720℃to melt the dehydrated material of step (1) to form a liquid bath.
The purity of the vanadium pentoxide obtained by the detection was 98.69%, the Na content was 0.025% by mass, the Fe content was 0.011% by mass, the Cr content was 0.013% by mass, the Si content was 0.008% by mass, the K content was 0.008% by mass, and the P content was 0.003% by mass.
Comparative example 2
The process of example 3 was carried out, except that in step (3), the vacuum system 30 was turned on to control the pressure in the melting furnace 10 to 10kPa.
The purity of the vanadium pentoxide obtained by the detection was 98.72%, the Na content was 0.021 mass%, the Fe content was 0.012 mass%, the Cr content was 0.015 mass%, the Si content was 0.007 mass%, the K content was 0.007 mass%, and the P content was 0.003 mass%.
Comparative example 3
The process of example 3 was carried out, except that in step (3), the vacuum system 30 was turned on to control the pressure in the melting furnace 10 to 50kPa.
The purity of vanadium pentoxide obtained by the detection was 98.75%, the Na content was 0.023 mass%, the Fe content was 0.014 mass%, the Cr content was 0.014 mass%, the Si content was 0.007 mass%, the K content was 0.008 mass%, and the P content was 0.004 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 (10)
1. The method for preparing vanadium pentoxide by using red vanadium as a raw material through negative pressure distillation is characterized by comprising the following steps of:
(1) Reacting red vanadium at 250-400 ℃ for 30-120 min for dehydration;
(2) Melting the material obtained in the step (1) at 1050-1300 ℃ to form a liquid molten pool, maintaining the temperature of the liquid molten pool, and converting vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
(3) Guiding out vanadium pentoxide vapor from a liquid molten pool under the pressure of 15-45 kPa, and cooling the vanadium pentoxide vapor to 150-350 ℃ to obtain vanadium pentoxide with purity of more than 99.90%;
the Na content in the red vanadium is more than or equal to 1 mass percent; the red vanadium contains at least one of Fe, cr, mn, si, K, P and S impurities; the total content of Fe, cr, mn, si, K, P and S in the red vanadium is more than or equal to 0.5 mass percent.
2. The method according to claim 1, characterized in that the method further comprises:
(4) When the liquid molten pool level is reduced to 0.1-0.2 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 according to claim 1, wherein the red vanadium contains 0.5 to 5 mass% of Na 2 O, 80-90 mass% of V 2 O 5 And 0.2 to 3 mass% of H 2 O。
4. The method according to claim 1, characterized in that in step (3) vanadium pentoxide vapour is led out of the liquid bath at a pressure of 22 to 45 kpa.
5. The method according to claim 1, wherein in step (3), the vanadium pentoxide vapor is cooled down by circulating cooling water.
6. The method according to any one of claims 1 to 5, characterized in that the method is carried out in a vanadium pentoxide production apparatus comprising a melting furnace (10), a condenser (20) and a vacuum 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);
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).
7. The method according to claim 6, wherein a spacing between two adjacent condenser baffles (22) is 30-60 cm.
8. Method according to claim 6, characterized in that the bottom of the cooling channel (21) is continuously detachably provided with 3-8 collectors (26).
9. The method according to claim 6, characterized in that the method comprises the steps of:
s1, adding red vanadium into the melting furnace (10) from the charging opening (11), closing the charging opening (11), heating the melting furnace (10), and reacting the red vanadium for 30-120 min at 250-400 ℃ for dehydration;
s2, continuously heating the melting furnace (10), melting the material obtained in the step S1 at 800-1300 ℃ to form a liquid molten pool, and maintaining the temperature of the liquid molten pool to convert vanadium pentoxide in the liquid material into vanadium pentoxide vapor;
s3, starting the vacuum system (30) to control the pressure in the melting furnace (10) to be 15-45 kPa, guiding vanadium pentoxide vapor from the melting furnace (10) into the cooling channel (21), cooling the vanadium pentoxide vapor to 150-350 ℃, and obtaining vanadium pentoxide with purity of more than 99.90% in the collector (26).
10. The method of claim 9, wherein the method further comprises:
s4, when the liquid molten pool level is reduced to 0.1-0.2 times of the initial value of the liquid molten pool level in the step S2, closing a vacuum system (30), stopping heating, opening a discharge port (13), and emptying residual materials in the liquid molten pool in the melting furnace (10);
s5, closing the discharge hole (13), and repeating the steps S1-S4 to perform continuous production.
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| 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 |
| KR102248361B1 (en) * | 2020-11-17 | 2021-05-06 | 한국지질자원연구원 | Pyrometallurgical purification method of vanadium pentoxide and vanadium pentoxide prepared from the same |
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| 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 |
| KR102248361B1 (en) * | 2020-11-17 | 2021-05-06 | 한국지질자원연구원 | Pyrometallurgical purification method of vanadium pentoxide and vanadium pentoxide prepared from the same |
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