CN111634945B - Device and method for producing low-valence vanadium oxide - Google Patents
Device and method for producing low-valence vanadium oxide Download PDFInfo
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Abstract
The invention relates to the technical field of vanadium oxide, in particular to a device and a method for producing low-valence vanadium oxide. The device for producing the low-valence vanadium oxide comprises a combustion device, a circulating decomposition reaction device and a cooling and collecting device. In the invention, the cyclic decomposition reaction device comprises a reaction pipeline, a recirculation pipeline and a dust removal device, and materials are decomposed and reduced for multiple times through the recirculation pipeline, so that the materials are fully reduced to obtain low-valence vanadium oxide; according to the invention, the ammonium metavanadate powder is taken as a raw material, the high-temperature airflow generated by the combustion device is utilized to drive the ammonium metavanadate powder to enter the circulating decomposition reaction device for decomposition and reduction, the ammonia gas generated by the raw material is taken as a reducing agent to complete the reduction reaction process, no reducing agent is required to be added, the advantages of rapidness and low energy consumption are achieved, and the low-cost preparation of the low-valence vanadium oxide is realized.
Description
Technical Field
The invention relates to the technical field of vanadium oxide, in particular to a device and a method for producing low-valence vanadium oxide.
Background
The industrial-grade low-valence vanadium oxide powder can be used as a high-quality raw material of vanadium-nitrogen alloy, vanadium-iron alloy, vanadium-aluminum alloy and lithium battery anode material lithium vanadium phosphate, is an upgraded substitute product of a traditional vanadium raw material vanadium pentoxide tablet, and can greatly save a reducing agent compared with the vanadium pentoxide tablet, improve the production efficiency and save the cost in the preparation of the products such as the vanadium-nitrogen alloy, the vanadium-aluminum alloy and the like.
The standard for detecting the low-valence vanadium oxide in the industry is to detect the all-vanadium content of a low-valence vanadium oxide product, and the low-valence vanadium oxide is generally considered to have the all-vanadium content in a range of more than 60% and less than 68% (all-vanadium). And the total vanadium content of the vanadium pentoxide is between 54 and 56 percent.
The traditional process for producing the low-valence vanadium oxide powder at present uses a sleeve type rotary kiln to heat ammonium polyvanadate powder, one end of an inner cylinder of the kiln is used for feeding material while slowly rotating, coke oven gas is introduced into one end of the inner cylinder, blast furnace gas is introduced between the inner cylinder and an outer cylinder and then is combusted to heat the inner cylinder, about 40-50 minutes is generally needed from raw materials to finished products, and the production method has the advantages of high equipment cost, low production efficiency and high energy consumption.
Disclosure of Invention
The device provided by the invention has a simple structure, can greatly shorten the time for producing the low-valence vanadium oxide, improves the production efficiency, reduces the cost, and is suitable for industrial scale growth.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a device for producing low-valence vanadium oxide, which comprises a combustion device 1, a circulating decomposition reaction device 2 and a cooling and collecting device 3;
the circulating decomposition reaction device 2 comprises a reaction pipeline 2-1, a recirculation pipeline 2-2 and a dust removal device 2-3; the inlet of the reaction pipeline 2-1 is communicated with the air outlet of the combustion device 1; one end of the recirculation pipeline 2-2 is communicated with the tail part of the reaction pipeline 2-1, and the other end of the recirculation pipeline 2-2 is communicated with the feeding hole of the dust removal device 2-3; the discharge hole of the dust removal device 2-3 is communicated with the head of the reaction pipeline 2-1;
and the outlet of the reaction pipeline 2-1 is communicated with the feed inlet of the cooling and collecting device 3.
Preferably, the reaction tube 2-1 is a U-shaped coil or a spiral tube.
Preferably, the length of the reaction pipeline 2-1 is 10-18 m, and the inner diameter of the reaction pipeline 2-1 is 0.2-0.8 m.
Preferably, one or more burners are arranged in the combustion device 1.
Preferably, the cooling and collecting device 3 comprises a heat exchanger 3-1, a dust remover 3-2 and a second fan 3-3 which are communicated in sequence; and a feed inlet of the heat exchanger 3-1 is communicated with an outlet of the reaction pipeline 2-1.
The invention also provides a method for producing the low-valence vanadium oxide by adopting the device in the technical scheme, which comprises the following steps:
mixing natural gas and air, and introducing the mixture into a combustion device 1 for combustion reaction to obtain high-temperature airflow;
the high-temperature airflow drives ammonium metavanadate powder to enter a reaction pipeline 2-1 for carrying out a first decomposition reduction reaction; the obtained reaction material is collected by the dust removal device 2-3 through the recycling pipeline 2-2, then returns to the reaction pipeline 2-1 again, continues to carry out the second decomposition reduction reaction, and the above steps are repeated in a circulating way until the ammonium metavanadate powder is completely converted into the low-valence vanadium oxide powder;
and conveying the obtained low-valence vanadium oxide powder to a cooling and collecting device 3 for cooling and collecting finished products to obtain low-valence vanadium oxide.
Preferably, the volume ratio of the natural gas to the air is 1: 8-15; the temperature of the high-temperature air flow is 200-900 ℃.
Preferably, the negative pressure of the inlet of the reaction pipeline 2-1 is-1 to-8 kPa.
Preferably, the time for completely converting the ammonium metavanadate powder into the low-valence vanadium oxide powder is 1-10 min.
Preferably, the low-valence vanadium oxide comprises vanadium tetraoxide and vanadium trioxide, and the mass ratio of the vanadium tetraoxide to the vanadium trioxide is 10: 0-1: 9; the low-valence vanadium oxide contains 60-67% of all vanadium by mass.
The invention provides a device for producing low-valence vanadium oxide, which comprises a combustion device 1, a circulating decomposition reaction device 2 and a cooling and collecting device 3. In the invention, the cyclic decomposition reaction device 2 comprises a reaction pipeline 2-1, a recycling pipeline 2-2 and a dust removal device 2-3, and materials are decomposed and reduced for multiple times through the recycling pipeline 2-2, so that the materials are fully reduced to obtain low-valence vanadium oxide; according to the invention, the ammonium metavanadate powder is taken as a raw material, the high-temperature airflow generated by the combustion device 1 is utilized to drive the ammonium metavanadate powder to enter the cyclic decomposition reaction device 2 for decomposition and reduction, the ammonia gas generated by the raw material is taken as a reducing agent to complete the reduction reaction process, no reducing agent is required to be added, the advantages of rapidness and low energy consumption are achieved, and the low-cost preparation of the low-valence vanadium oxide is realized. The low-valence vanadium oxide produced by the device provided by the invention can meet the requirements of producing products such as vanadium-nitrogen alloy, vanadium-aluminum alloy and the like, and compared with the traditional low-valence vanadium oxide powder preparation process, the method does not need to introduce reductive gas to reduce ammonium metavanadate under the condition of long-time external heating, improves the production efficiency, greatly reduces the production cost, and has remarkable economic and social benefits.
Drawings
FIG. 1 is a schematic view of a combustion apparatus;
FIG. 2 is a schematic view of a cyclic decomposition reaction apparatus in which the reaction pipe is a U-shaped coil;
FIG. 3 is a schematic view of a cyclic decomposition reaction apparatus in which the reaction pipe is a spiral pipe;
FIG. 4 is a schematic view of a reduced temperature collection device;
FIG. 5 is a schematic view of an apparatus for producing a lower vanadium oxide according to example 1;
FIG. 6 is a schematic view of an apparatus for producing a low-valent vanadium oxide according to examples 2 to 3;
wherein, 1 is a combustion device, 1-1 is a first burner, 1-2 is a second burner, and 1-3 is a third burner;
2 is a circulating decomposition reaction device, 2-1 is a reaction pipeline, 2-2 is a recycling pipeline, 2-3 is a dust removal device, 2-4 is a first fan, 2-5 is a first exhaust gas cylinder, 2-6 is a first valve, 2-7 is a feeder, and 2-8 is a charging opening;
3 is a cooling and collecting device, 3-1 is a heat exchanger, 3-2 is a dust remover, 3-3 is a second fan, 3-4 is a second exhaust funnel, and 3-5 is a second valve.
Detailed Description
The invention provides a device for producing low-valence vanadium oxide, which comprises a combustion device 1, a circulating decomposition reaction device 2 and a cooling and collecting device 3; the circulating decomposition reaction device 2 comprises a reaction pipeline 2-1, a recirculation pipeline 2-2 and a dust removal device 2-3; the inlet of the reaction pipeline 2-1 is communicated with the air outlet of the combustion device 1; one end of the recirculation pipeline 2-2 is communicated with the tail part of the reaction pipeline 2-1, and the other end of the recirculation pipeline 2-2 is communicated with the feeding hole of the dust removal device 2-3; the discharge hole of the dust removal device 2-3 is communicated with the head of the reaction pipeline 2-1; and the outlet of the reaction pipeline 2-1 is communicated with the feed inlet of the cooling and collecting device 3.
In the invention, the low-valence vanadium oxide is preferably vanadium tetraoxide or a mixture of vanadium tetraoxide and vanadium trioxide, and when the low-valence vanadium oxide is the mixture of vanadium tetraoxide and vanadium trioxide, the mass ratio of vanadium tetraoxide to vanadium trioxide is preferably 9: 1-1: 9; the V content (total vanadium) of the low-valence vanadium oxide is preferably 60 to 67%, and more preferably 61 to 65%.
The device provided by the invention comprises a combustion device 1, and the mixed gas of natural gas and air is fully combusted to obtain high-temperature airflow. As an embodiment of the present invention, the combustion apparatus 1 is a box-type natural gas combustion apparatus, a kiln-type natural gas combustion apparatus, or a furnace-type natural gas combustion apparatus. In the invention, one or more burners are arranged in the combustion device 1; when a plurality of burners are arranged in the combustion device, preferably, a main burner is arranged in the middle of the combustion device, auxiliary burners are arranged on the periphery of the combustion device, and one or more burners are opened according to the required temperature during operation. In a specific embodiment of the present invention, a schematic view of the combustion apparatus 1 is shown in fig. 1, and the combustion apparatus includes a combustion chamber and a plurality of burners disposed in the combustion chamber, wherein a mixed gas of natural gas and air is introduced into each burner, and after the burners are ignited, a large amount of high-temperature air flow is generated.
The device provided by the invention comprises a circulating decomposition reaction device 2 which is used for decomposing and reducing materials to obtain low-valence vanadium oxide powder. In the invention, the cyclic decomposition reaction device 2 comprises a reaction pipeline 2-1, a recycling pipeline 2-2 and a dust removal device 2-3; the inlet of the reaction pipeline 2-1 is communicated with the air outlet of the combustion device 1; one end of the recirculation pipeline 2-2 is communicated with the tail part of the reaction pipeline 2-1, and the other end of the recirculation pipeline 2-2 is communicated with the feeding hole of the dust removal device 2-3; and a discharge hole of the dust removal device 2-3 is communicated with the head of the reaction pipeline 2-1.
In the present invention, the reaction tube 2-1 is preferably a U-shaped coil or a spiral tube. In a specific embodiment of the invention, the U-shaped coil is preferably obtained by connecting 3-5U-shaped pipes end to end; the number of turns of the spiral pipeline is preferably 4-6. The invention can maximize the reaction interface by limiting the adoption of the U-shaped coil pipe or the spiral pipeline, prolong the retention time of materials in the reaction pipeline 2-1, accelerate the decomposition, deamination and reduction reaction of the ammonium metavanadate powder, and ensure that the decomposition reduction reaction is more sufficient.
In the invention, the length of the reaction pipeline 2-1 is preferably 10-18 m, and more preferably 12-16 m; the inner diameter of the reaction pipeline 2-1 is preferably 0.2-0.8 m, and more preferably 0.4-0.8 m. In the invention, the material of the reaction pipeline 2-1 is preferably 304 stainless steel, and the pipe wall thickness of the reaction pipeline 2-1 is preferably 2-8 mm; the reaction pipeline 2-1 is preferably wrapped with a heat insulation layer, the heat insulation layer preferably comprises aluminum silicate heat insulation cotton, and the thickness of the heat insulation layer is preferably 50-200 mm. According to the invention, the heat-insulating layer is covered outside the reaction pipeline 2-1, so that the heat loss can be reduced, the materials in the reaction pipeline 2-1 are continuously in a high-temperature flowing state, and the decomposition reduction reaction efficiency is improved.
In the present invention, the material of the recirculation pipe 2-2 is preferably 304 stainless steel. In the specific embodiment of the invention, one end of the recirculation pipeline 2-2 communicated with the tail part of the reaction pipeline 2-1 is provided with a first valve 2-6 for controlling the materials and the gas flow to be introduced into the recirculation pipeline 2-2 from the reaction pipeline 2-1.
In the present invention, the dust removing device 2-3 is preferably a cyclone type dust collector 3-2 or a bag type dust collector 3-2 for collecting insufficiently reacted materials. In the embodiment of the invention, the device further comprises a first fan 2-4 and a first exhaust cylinder 2-5, wherein the air inlet of the first fan 2-4 is communicated with the exhaust port of the dust removing device 2-3, and the exhaust port of the first fan 2-4 is communicated with the first exhaust cylinder 2-5. In the present invention, the insufficiently reacted materials are collected by the dust removing device 2-3 and re-introduced into the reaction tube 2-1 for decomposition reduction reaction, and the gas flow passing through the dust removing device 2-3 is discharged to the atmosphere through the first fan 2-4 and the first exhaust tube 2-5.
As an embodiment of the present invention, the apparatus provided by the present invention further comprises a feeder 2-7 and a feed port 2-8 for adding the raw material ammonium metavanadate powder at the start of the cyclic decomposition reaction or during the cyclic decomposition reaction. As an embodiment of the present invention, the charging port 2-8 is disposed at the head of the reaction pipe 2-1, and more preferably, between the discharge port of the dust removing device 2-3 and the inlet of the reaction pipe 2-1. As an embodiment of the invention, the outlet of the feeder 2-7 is communicated with the feed port 2-8 to convey ammonium metavanadate powder into the reaction pipeline 2-1. In the present invention, the feeder 2-7 is preferably a jet feeder 2-7, a planetary feeder 2-7 or a screw feeder 2-7.
In the specific embodiment of the invention, the cyclic decomposition reaction device 2 is shown in fig. 2-3 and comprises a feeder 2-7, a feed inlet 2-8, a reaction pipeline 2-1, a recirculation pipeline 2-2, a dust removal device 2-3, a first fan 2-4 and a first exhaust cylinder 2-5, wherein the reaction pipeline 2-1 is a U-shaped coil (shown in fig. 2) or a spiral pipeline (shown in fig. 3); one end of the recirculation pipeline 2-2 is communicated with the tail part of the reaction pipeline 2-1, and the other end is communicated with the feeding hole of the dust removal device 2-3; the discharge hole of the dust removal device 2-3 is communicated with the head of the reaction pipeline 2-1, and the feed inlet 2-8 is arranged between the discharge hole of the dust removal device 2-3 and the inlet of the reaction pipeline 2-1; the outlet of the feeder 2-7 is communicated with the feed inlet 2-8; the exhaust port of the dust removal device 2-3 is communicated with the air inlet of the first fan 2-4; the air outlet of the first fan 2-4 is communicated with the first exhaust cylinder 2-5.
As an embodiment of the invention, a plurality of temperature sensors, wind speed sensors and wind quantity sensors are arranged on the reaction pipeline 2-1 and the recirculation pipeline 2-2. In the invention, a temperature sensor is arranged on each of the reaction pipeline 2-1 and the recycling pipeline 2-2 at intervals, and the interval is preferably 3 m; the total number of the temperature sensors is preferably 4-6; the heads of the reaction pipeline 2-1 and the recirculation pipeline 2-2 are both provided with a wind speed sensor and a wind quantity sensor; and the tail parts of the reaction pipeline 2-1 and the recirculation pipeline 2-2 are provided with a wind speed sensor and a wind quantity sensor. In the invention, parameters obtained by the temperature sensor, the wind speed sensor and the air quantity sensor are connected to a computer display end of an operator through the electric signal line control cabinet. The temperature and airflow flow of each section of the reaction pipeline 2-1 are monitored by using a temperature sensor, a wind speed sensor and an air quantity sensor, and the natural airflow flow, the temperature parameter of high-temperature airflow and the time of decomposition reduction reaction in the combustion device 1 are adjusted according to the obtained conditions of the temperature and the airflow flow.
The device provided by the invention comprises a cooling and collecting device 3 which is used for cooling the product and collecting the finished product. In the invention, the feed inlet of the cooling and collecting device 3 is communicated with the outlet of the reaction device. In the specific embodiment of the invention, the outlet of the circulating decomposition reaction device is provided with a second valve 3-5 for controlling the material after the reaction is completed to enter the cooling and collecting device 3.
As an embodiment of the invention, the cooling collection device 3 is shown in FIG. 4 and comprises a heat exchanger 3-1, a dust remover 3-2 and a second fan 3-3 which are communicated in sequence. The specific structures of the heat exchanger 3-1, the dust remover 3-2 and the second fan 3-3 are not particularly limited, and the heat exchanger 3-1, the dust remover 3-2 and the fan which are well known to those skilled in the art can be adopted. As an embodiment of the present invention, the heat exchanger 3-1 is preferably a double-pipe air cooling device; the dust collector 3-2 is preferably a bag type dust collector 3-2 or a cyclone type dust collector 3-2.
As an embodiment of the present invention, the cooling and collecting device 3 further includes a second exhaust funnel 3-4 communicated with an exhaust port of the second fan 3-3. In the invention, low-valence vanadium oxide powder obtained after the ammonium metavanadate powder passes through a circulating decomposition reaction device 2 enters a heat exchanger 3-1 for cooling, and then is collected by a dust collector 3-2 to obtain a low-valence vanadium oxide finished product; the air flow passing through the heat exchanger 3-1 and the dust removing device 2-3 is discharged to the atmosphere through a second fan 3-3 and a second exhaust funnel 3-4.
In a specific embodiment of the present invention, the first fan 2-4 and the second fan 3-3 are further configured to provide a negative pressure condition in the reaction pipeline 2-1, specifically: before the ammonium metavanadate powder is introduced, the first valve 2-6 is closed, the second valve 3-5 is opened, negative pressure is formed in the reaction pipeline 2-1 by using the second fan 3-3, and high-temperature airflow generated by the combustion device 1 rapidly passes through the reaction pipeline 2-1 under the negative pressure condition and is discharged into the atmosphere through the cooling and collecting device 3; after the ammonium metavanadate powder is introduced, the second valve 3-5 is closed, the first valve 2-6 is opened, the second fan 3-3 is closed, negative pressure is formed in the reaction pipeline 2-1 and the recirculation pipeline 2-2 by the first fan 2-4, and the materials pass through the reaction pipeline 2-1 and then enter the reaction pipeline 2-1 again through the recirculation pipeline 2-2 for circulation reaction.
The device for producing the low-valence vanadium oxide is shown in figure 5 or 6 and comprises a combustion device 1, a circulating decomposition reaction device 2 and a cooling and collecting device 3, wherein the combustion device 1 comprises a combustion chamber and a plurality of burners; the circulating decomposition reaction device 2 consists of a reaction pipeline 2-1, a recirculation pipeline 2-2, a dust removal device 2-3, a first fan 2-4 and a first exhaust cylinder 2-5; the cooling and collecting device 3 consists of a heat exchanger 3-1, a dust remover 3-2, a second fan 3-3 and a second exhaust funnel 3-4 which are sequentially communicated; the inlet of the reaction pipeline 2-1 is communicated with the air outlet of the combustion device 1; one end of the recirculation pipeline 2-2 is communicated with the tail part of the reaction pipeline 2-1, and the other end of the recirculation pipeline 2-2 is communicated with the feeding hole of the dust removal device 2-3; the discharge hole of the dust removal device 2-3 is communicated with the head of the reaction pipeline 2-1; the exhaust port of the dust removing device 2-3 is communicated with the air inlet of the first fan 2-4, and the air outlet of the first fan 2-4 is communicated with the first exhaust barrel 2-5; an outlet of the reaction pipeline 2-1 is communicated with a feed inlet of the heat exchanger 3-1; an air outlet of the dust remover 3-2 is communicated with an air inlet of the second fan 3-3, and an air outlet of the second fan 3-3 is communicated with the second exhaust funnel 3-4.
The invention also provides a method for producing the low-valence vanadium oxide by adopting the device in the technical scheme, which comprises the following steps:
mixing natural gas and air, and introducing the mixture into a combustion device 1 for combustion reaction to obtain high-temperature airflow;
the high-temperature airflow drives ammonium metavanadate powder to enter a reaction pipeline 2-1 for carrying out a first decomposition reduction reaction; the obtained material is collected by the dust removal device 2-3 through the recycling pipeline 2-2, then returns to the reaction pipeline 2-1 again, continues to carry out the second decomposition reduction reaction, and the above steps are repeated in a circulating way until the ammonium metavanadate powder is completely converted into the low-valence vanadium oxide powder;
and conveying the obtained low-valence vanadium oxide powder to a cooling and collecting device 3 for cooling and collecting finished products to obtain low-valence vanadium oxide.
According to the invention, natural gas and air are mixed and introduced into the combustion device 1 for combustion reaction to obtain high-temperature airflow. In the present invention, the volume ratio of the natural gas to the air is preferably 1: 8 to 15, and more preferably 1:9 to 13. In the invention, the temperature of the high-temperature air flow is preferably 200-900 ℃, and more preferably 400-600 ℃. According to the invention, natural gas and air are mixed and then are introduced into the combustion device 1 for combustion, so that the natural gas is fully combusted to generate the maximum calorific value, free oxygen does not exist in the generated high-temperature airflow, and the reverse reaction of ammonium vanadate reduction can be avoided.
In the present invention, the components of the high temperature gas stream preferably include carbon dioxide and water vapor.
After high-temperature airflow is obtained, the high-temperature airflow drives ammonium metavanadate powder to enter a reaction pipeline 2-1 for carrying out a first decomposition reduction reaction; and the obtained material is collected by the dust removal device 2-3 through the recycling pipeline 2-2, then returns to the reaction pipeline 2-1 again, continues to perform the second decomposition reduction reaction, and repeats the cycle until the ammonium metavanadate powder is completely converted into the low-valence vanadium oxide powder. In the invention, the flow rate of the high-temperature air flow is preferably 400-500 m3More preferably 430 to 460m3H is used as the reference value. The invention utilizes high-temperature airflow to drive the ammonium metavanadate powder, so that the reaction interface can be maximized, the decomposition, the deammoniation and the reduction of the ammonium metavanadate are accelerated, and the ammonium metavanadate powder completes the decomposition reduction reaction in the flow.
In the invention, the particle size of the ammonium metavanadate powder is preferably 20-184 μm, and the purity is preferably 96-99.5%. In the invention, the ammonium metavanadate powder is preferably added at a constant speed or in a staged manner. In the specific embodiment of the invention, ammonium metavanadate powder is added during the first decomposition reduction reaction, and ammonium metavanadate powder is not added during the second decomposition reduction reaction to the Nth decomposition reduction reaction, so that the ammonium metavanadate powder is completely converted into low-valence vanadium oxide powder. In the specific embodiment of the invention, the adding speed of the ammonium metavanadate powder is preferably 60-90 kg/h. In the present invention, the water content of the ammonium metavanadate powder is preferably less than 0.5%.
According to the invention, before the ammonium metavanadate powder is preferably added, the interior of the reaction pipeline 2-1 is under negative pressure, the negative pressure at the inlet of the reaction pipeline 2-1 is preferably-1 to-8 kPa, and the negative pressure at the outlet is preferably-3 to-7.5 kPa. In the process of decomposition reduction reaction after the ammonium metavanadate powder is introduced, the reaction pipeline 2-1 is always in a negative pressure state, so that high-temperature air flow and materials can smoothly flow in the reaction pipeline 2-1.
In an embodiment of the present invention, the number of the cycles is preferably 2 to 4, i.e., 3 to 5 decomposition and reduction reactions in the reaction pipeline 2-1.
In the present invention, the chemical reaction equations of the first decomposition reduction reaction, the second decomposition reduction reaction, and up to the nth decomposition reduction reaction are as follows:
2NH4VO3→V2O5+2NH3+H2o, formula I;
2NH3→N2+3H2formula II;
V2O5+2H2→V2O3+2H2o, formula III;
V2O5+H2→2VO2+H2o, formula IV;
wherein formula III and formula IV are carried out separately or simultaneously.
As can be seen from the above chemical reaction equation, the low-valence vanadium oxide prepared by the method is a mixture of vanadium tetraoxide and vanadium trioxide.
In the invention, the time for completely converting the ammonium metavanadate powder into the low-valence vanadium oxide powder is preferably 1-10 min, and more preferably 2-8 min. The method for preparing the low-valence vanadium oxide can greatly shorten the production time and improve the production efficiency.
After obtaining the low-valence vanadium oxide powder, the invention conveys the obtained low-valence vanadium oxide powder to a cooling and collecting device 3 for cooling and finished product collection to obtain the low-valence vanadium oxide. In the invention, the temperature of the low-valence vanadium oxide powder is preferably 300-400 ℃, and the temperature of the material obtained after cooling is preferably less than or equal to 180 ℃. In the invention, the heat exchanger 3-1 is preferably adopted to cool the low-valence vanadium oxide powder, and the airflow discharged from the reaction pipeline 2-1 is cooled at the same time. In the invention, the finished product is preferably collected by a dust collector 3-2, and the airflow passes through the dust collector 3-2 and then is discharged into the atmosphere by a second fan 3-3 and a second exhaust funnel 3-4.
According to the method, ammonium metavanadate powder commonly available in the market is used as a raw material, ammonia gas obtained by decomposing ammonium carried by the raw material and hydrogen obtained by further decomposing the ammonia gas are used as reducing agents, the ammonium metavanadate powder is prepared into low-valence vanadium oxide, and the reducing agents are not required to be added; meanwhile, high-temperature airflow with ammonium metavanadate powder rapidly passes through the device provided by the invention, a series of chemical reactions such as ammonium metavanadate decomposition, ammonium removal, reduction and the like can be completed within a few minutes, the production efficiency is high, the produced low-valence vanadium oxide finished product has stable components, compared with the traditional process, the production time is greatly shortened, and the cost is greatly reduced; the supply market after mass production can greatly reduce the production cost of manufacturers of vanadium-nitrogen alloy, vanadium-aluminum alloy and the like and improve the production efficiency, and the economic and social benefits are obvious.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The components of the ammonium metavanadate powder adopted in the embodiment of the invention are shown in Table 1;
TABLE 1 composition of ammonium metavanadate powder (mass%)
Example 1
Adopting the device shown in figure 5 to produce low-valence vanadium oxide, closing the first valve 2-6, opening the second valve 3-5, and introducing the mixed gas of natural gas and air into the first burner 1-1, the second burner 1-2 and the third burner 1-3, wherein the natural gas flow is 11m3H, air flow 111.1m3H, the flow of the high-temperature airflow generated after ignition is adjusted to be 432m3The temperature of the high-temperature airflow at the inlet of the U-shaped coil pipe (the length is 15.6m, and the inner diameter is 0.75m) is 420 ℃; adjusting the negative pressure of the U-shaped coil by adopting a second fan 3-3 to enable the negative pressure of the inlet of the U-shaped coil to be-5500 Pa; ammonium metavanadate powder pre-loaded into feeders 2-7Feeding the materials into a feeding port 2-8 of a U-shaped coil pipe from a feeder 2-7 at a speed of 80kg/h, closing a second valve 3-5, opening a first valve 2-6, closing a second fan 3-3 at the same time, opening a first fan 2-4, driving ammonium metavanadate powder to pass through the U-shaped coil pipe by high-temperature airflow, collecting the ammonium metavanadate powder by a cyclone dust collector 3-2 through a recirculation pipeline 2-2, returning the ammonium metavanadate powder to the U-shaped coil pipe again, continuously performing decomposition, deammoniation and reduction reactions, and after two cycles, converting the ammonium metavanadate powder into low-valence vanadium oxide powder, wherein the time for passing through a cyclic decomposition reaction device 2 is 2 minutes and 45 seconds; closing the first valve 2-6 and the first fan 2-4, opening the second valve 3-5 and the second fan 3-3, cooling the low-valence vanadium oxide powder in the heat exchanger 3-1 from the outlet of the U-shaped coil, collecting the finished product by using the dust remover 3-2, and discharging airflow discharged from the outlet of the U-shaped coil through the heat exchanger 3-1, the dust remover 3-2 and the fans in sequence;
the finished product collected by the dust remover 3-2 is low-valence vanadium oxide, and the product components are shown in Table 2;
TABLE 2 example 1 composition (mass%) of vanadium suboxides
Note: the percentage of vanadium tetraoxide and vanadium trioxide is mass percentage, and the total vanadium content is not in the same percentage relation with other detection items; that is, the sum of the mass percentages of vanadium tetraoxide, vanadium trioxide, ammonium content, and impurities in table 2 is 100%.
Example 2
Adopting the device shown in FIG. 6 to produce low-valence vanadium oxide, closing the first valve 2-6, opening the second valve 3-5, and introducing the mixed gas of natural gas and air into the first burner 1-1, the second burner 1-2 and the third burner 1-3, wherein the natural gas flow is 13m3H, air flow rate of 128.05m3H, the flow rate of the high-temperature airflow generated after ignition is adjusted to 468m3The temperature of the high-temperature airflow at the inlet of the spiral pipeline (the length is 14m, and the inner diameter is 0.8m) is 530 ℃; the second fan 3-3 is adopted to adjust the negative pressure of the spiral pipeline to lead the spiral to be screwedThe negative pressure at the inlet of the spiral pipeline is-6200 Pa; feeding ammonium metavanadate powder pre-loaded into a feeder 2-7 into a feed inlet 2-8 of a spiral pipeline from the feeder 2-7 at a speed of 60kg/h, closing a second valve 3-5, opening a first valve 2-6, simultaneously closing a second fan 3-3, opening a first fan 2-4, driving the ammonium metavanadate powder to pass through the spiral pipeline by high-temperature airflow, collecting the ammonium metavanadate powder by a cyclone dust collector 3-2 through a recycling pipeline 2-2, returning the ammonium metavanadate powder into the spiral pipeline again, continuously performing decomposition, deammoniation and reduction reactions, converting the ammonium metavanadate powder into low-valent vanadium oxide powder after 4 cycles, and enabling the ammonium metavanadate powder to pass through a cyclic decomposition reaction device 2 for 4 minutes and 16 seconds; closing the first valve 2-6 and the first fan 2-4, opening the second valve 3-5 and the second fan 3-3, cooling the low-valence vanadium oxide powder entering the heat exchanger 3-1 from the outlet of the spiral pipeline, then collecting a finished product by using the dust remover 3-2, and discharging airflow discharged from the outlet of the spiral pipeline through the heat exchanger 3-1, the dust remover 3-2 and the fans in sequence;
the finished product collected by the dust remover 3-2 is low-valence vanadium oxide, and the product components are shown in Table 3;
TABLE 3 example 2 composition of vanadium suboxides (mass%)
Example 3
Adopting the device shown in FIG. 6 to produce low-valence vanadium oxide, closing the first valve 2-6, opening the second valve 3-5, and introducing the mixed gas of natural gas and air into the first burner 1-1, the second burner 1-2 and the third burner 1-3, wherein the natural gas flow is 18m3H, air flow rate of 180m3H, the flow rate of the high-temperature airflow generated after ignition is adjusted to 573m3The temperature of the high-temperature airflow at the inlet of the spiral pipeline (the length is 14m, and the inner diameter is 0.8m) is 600 ℃; adjusting the negative pressure of the spiral pipeline by adopting a second fan 3-3 to ensure that the negative pressure of the inlet of the spiral pipeline is-6800 Pa; ammonium metavanadate powder pre-loaded into the feeder 2-7 is fed into the feed port 2-8 of the spiral pipeline from the feeder 2-7 at a speed of 90kg/h, the second valve 3-5 is closed, and the mixture is beatenOpening a first valve 2-6, closing a second fan 3-3 at the same time, opening the first fan 2-4, driving ammonium metavanadate powder to pass through a spiral pipeline by high-temperature airflow, collecting the ammonium metavanadate powder by a cyclone dust collector 3-2 through a recycling pipeline 2-2, returning the ammonium metavanadate powder to the spiral pipeline again, continuously performing decomposition, deammoniation and reduction reactions, converting the ammonium metavanadate powder into low-valence vanadium oxide powder after 4 cycles, and enabling the ammonium metavanadate powder to pass through a cyclic decomposition reaction device 2 for 3 minutes and 48 seconds; closing the first valve 2-6 and the first fan 2-4, opening the second valve 3-5 and the second fan 3-3, cooling the low-valence vanadium oxide powder entering the heat exchanger 3-1 from the outlet of the spiral pipeline, then collecting a finished product by using the dust remover 3-2, and discharging airflow discharged from the outlet of the spiral pipeline through the heat exchanger 3-1, the dust remover 3-2 and the fans in sequence;
the finished product collected by the dust remover 3-2 is low-valence vanadium oxide, and the product components are shown in Table 4;
table 4 example 3 composition of vanadium suboxides
Example 4
Adopting the device shown in figure 5 to produce low-valence vanadium oxide, closing the first valve 2-6, opening the second valve 3-5, and introducing the mixed gas of natural gas and air into the first burner 1-1, the second burner 1-2 and the third burner 1-3, wherein the natural gas flow is 16m3Flow rate of air 160m3H, the flow of the high-temperature airflow generated after ignition is regulated to 491m3The temperature of the high-temperature airflow at the inlet of the U-shaped coil pipe (the length is 15.6m, and the inner diameter is 0.75m) is 580 ℃; adjusting the negative pressure of the U-shaped coil by adopting a second fan 3-3 to enable the negative pressure of the inlet of the U-shaped coil to be-5800 Pa; ammonium metavanadate powder pre-loaded into a feeder 2-7 is fed into a feed inlet 2-8 of a spiral pipeline from the feeder 2-7 at a speed of 70kg/h, a second valve 3-5 is closed, a first valve 2-6 is opened, a second fan 3-3 is closed at the same time, a first fan 2-4 is opened, the ammonium metavanadate powder is driven by high-temperature air flow to pass through a U-shaped coil pipe, is collected by a cyclone dust collector 3-2 through a recirculation pipeline 2-2, and returns to the U-shaped coil pipe againIn the process, decomposition, deammoniation and reduction reaction are continuously carried out, after 3 cycles, ammonium metavanadate powder is converted into low-valence vanadium oxide powder, and the time of passing through a cyclic decomposition reaction device 2 is 3 minutes and 06 seconds; closing the first valve 2-6 and the first fan 2-4, opening the second valve 3-5 and the second fan 3-3, cooling the low-valence vanadium oxide powder in the heat exchanger 3-1 from the outlet of the U-shaped coil, collecting the finished product by using the dust remover 3-2, and discharging airflow discharged from the outlet of the U-shaped coil through the heat exchanger 3-1, the dust remover 3-2 and the fans in sequence;
the finished product collected by the dust remover 3-2 is low-valence vanadium oxide, and the product components are shown in Table 5;
TABLE 5 example 4 composition of vanadium suboxides
It can be seen from the above embodiment that, the device provided by the application is adopted to produce low-valence vanadium oxide, so that the production efficiency can be obviously improved while the low-valence vanadium oxide is ensured to be obtained, no additional reducing gas is required to be added, the production cost is reduced, and the device has the advantages of high speed, high efficiency and low energy consumption, and is suitable for popularization and application.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for producing vanadium suboxides using an apparatus for producing vanadium suboxides, comprising the steps of:
mixing natural gas and air, and introducing the mixture into a combustion device (1) for combustion reaction to obtain high-temperature gas flow;
the high-temperature airflow drives ammonium metavanadate powder to enter a reaction pipeline (2-1) for carrying out a first decomposition reduction reaction; the obtained reaction material is collected by the dust removal device (2-3) through the recirculation pipeline (2-2), then returns to the reaction pipeline (2-1) again, continues to carry out the second decomposition reduction reaction, and the above steps are repeated in a circulating manner until the ammonium metavanadate powder is completely converted into the low-valence vanadium oxide powder;
conveying the obtained low-valence vanadium oxide powder to a cooling and collecting device (3) for cooling and collecting finished products to obtain low-valence vanadium oxide;
the device for producing the low-valence vanadium oxide comprises a combustion device (1), a circulating decomposition reaction device (2) and a cooling and collecting device (3);
the circulating decomposition reaction device (2) comprises a reaction pipeline (2-1), a recycling pipeline (2-2) and a dust removal device (2-3); the inlet of the reaction pipeline (2-1) is communicated with the air outlet of the combustion device (1); one end of the recirculation pipeline (2-2) is communicated with the tail part of the reaction pipeline (2-1), and the other end of the recirculation pipeline (2-2) is communicated with the feeding hole of the dust removal device (2-3); the discharge hole of the dust removal device (2-3) is communicated with the head of the reaction pipeline (2-1);
an outlet of the reaction pipeline (2-1) is communicated with a feed inlet of the cooling and collecting device (3);
the reaction pipeline (2-1) is a U-shaped coil pipe or a spiral pipeline, and the U-shaped coil pipe is obtained by connecting 3-5U-shaped pipes end to end; the number of turns of the spiral pipeline is 4-6;
the length of the reaction pipeline (2-1) is 10-18 m, the inner diameter of the reaction pipeline (2-1) is 0.2-0.8 m, and the outside of the reaction pipeline (2-1) is wrapped with a heat insulation layer.
2. The method of claim 1, wherein the volume ratio of natural gas to air is 1: 8-15; the temperature of the high-temperature air flow is 400-600 ℃.
3. The method according to claim 1, wherein the negative pressure at the inlet of the reaction pipeline (2-1) is-1 to-8 kPa.
4. The method of claim 1, wherein the time for completely converting the ammonium metavanadate powder into the low-valence vanadium oxide powder is 1-10 min.
5. The method according to claim 1, wherein the low-valence vanadium oxide comprises vanadium tetraoxide and vanadium trioxide, and the mass ratio of the vanadium tetraoxide to the vanadium trioxide is 10: 0-1: 9; the low-valence vanadium oxide contains 60-67% of all vanadium by mass.
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