CN108630973B

CN108630973B - System and method for preparing high-purity vanadium electrolyte by efficient clean chlorination method

Info

Publication number: CN108630973B
Application number: CN201710160987.7A
Authority: CN
Inventors: 朱庆山; 杨海涛; 范川林
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2017-03-17
Filing date: 2017-03-17
Publication date: 2020-05-19
Anticipated expiration: 2037-03-17
Also published as: CN108630973A

Abstract

The invention belongs to the fields of chemical industry and energy, and provides a system and a method for preparing high-purity vanadium electrolyte by using an efficient clean chlorination method. Preparing high-purity low-valence vanadium oxide powder by adopting chlorination, dedusting leaching, purification, catalytic oxidation, fluidized reduction and fluidized bed dissolving processes, wherein the average valence state of vanadium is any value within the range of 3.0-4.0; ultrapure water and pure sulfuric acid are added into the liquid-solid fluidized bed to dissolve low-valence vanadium oxide at low temperature to obtain high-purity vanadium electrolyte which can be directly used for the all-vanadium flow battery. The invention realizes the regeneration of chlorine by introducing clean oxygen-enriched air into the catalytic oxidation fluidized bed, finally realizes the circulation of chlorine and reduces the production cost; the hydrochloric acid condensing and absorbing tower is used for recovering hydrogen chloride in the catalytic oxidation tail gas, the generation of vanadium-containing hydrochloric acid is eliminated, and the environmental protection cost is greatly reduced. The method has the advantages of strong raw material adaptability, low production energy consumption and operation cost, stable product quality and the like, and is suitable for large-scale industrial production of the high-purity vanadium electrolyte.

Description

System and method for preparing high-purity vanadium electrolyte by efficient clean chlorination method

Technical Field

The invention belongs to the fields of chemical industry and energy, and relates to a system and a method for preparing high-purity vanadium electrolyte by using an efficient clean chlorination method.

Background

All vanadium flow batteries (VRFB) are a large-scale energy storage device with good commercial application prospects. Over thirty years of development, the VRFB technique has been gradually perfected and achieved industrial demonstrations on the order of tens of megawatts. The theoretical number of cycles for an all vanadium flow battery is infinite and its life cycle is considered to be above 20 years in actual industrial use. In the long-term service process, in order to avoid the occurrence of harmful side reactions, high requirements are put on the purity of the vanadium electrolyte. Within the range acceptable for economic cost, the higher the purity, the better. The purity is directly related to the service life of the vanadium battery.

The preparation method of the high-purity vanadium electrolyte mainly comprises two preparation methods: one is an electrolytic method and the other is a dissolving method of low-valence vanadium oxide. The electrolytic method generally uses high-purity vanadium pentoxide as a raw material, and the vanadium pentoxide is activated by concentrated sulfuric acid, added with a sulfuric acid solution and electrolyzed by constant current to prepare a vanadium electrolyte. The low-valence vanadium oxide dissolving method is to directly dissolve high-purity low-valence vanadium oxide in sulfuric acid solution to obtain vanadium electrolyte. Through the analysis, the preparation of high-purity vanadium pentoxide or high-purity low-valence vanadium oxide is a key step for preparing the high-purity vanadium electrolyte.

In recent years, the oxidation technology for preparing high-purity vanadium pentoxide or high-purity low-valence vanadium by a chlorination method is greatly developed, shows remarkable technical superiority, and is considered to be one of the technologies with the greatest large-scale industrial application prospect. The main process route for preparing the high-purity vanadium oxide by the chlorination method is as follows: vanadium-containing raw materials, chlorination, purification, ammonium salt precipitation/hydrolysis/oxidation, vanadium pentoxide, reduction and low-valence vanadium oxide.

The preparation technology of high-purity vanadium pentoxide by a chlorination method is developed for a long time and is gradually improved. In the last 60 s, researchers at the Ohiowa State university of America used ammonium polyvanadate-carbochlorination-vanadium oxychloride distillation-ammonium salt precipitation-calcination to prepare high-purity vanadium pentoxide (Journal of the Less-Common Metals,1960,2: 29-35). In the document, high-purity vanadium oxychloride is directly added into ammonia water, so that the treatment difficulty is high, the recovery rate is low, and a large amount of waste water containing ammonium chloride is generated.

In 2011, CN103130279A discloses a process route for preparing high-purity vanadium pentoxide by a chlorination method. The patent adopts a process route of vanadium-containing substance-carbon preparation chlorination-dust removal-condensation-rectification-ultrapure water hydrolysis/ammonium salt precipitation-calcination to prepare high-purity vanadium pentoxide. This patent is similar to the aforementioned research at the Iowa State university of America, and only shows the principle flow of chlorination, and is practically difficult to implement; in addition, vanadium oxychloride is introduced into the ultrapure water solution/ultrapure ammonia water, so that the recovery rate is very low, and the problem of serious water pollution is caused.

In recent years, the research institute of process engineering of the Chinese academy of sciences has conducted a great deal of research on the preparation technology of the chlorination-process high-purity vanadium oxide, so that the preparation technology of the chlorination-process high-purity vanadium oxide is gradually improved, and a good large-scale industrial application prospect is presented. But the problems of system optimization and clean and efficient conversion of vanadium oxychloride still exist and need to be solved urgently.

CN105984896A proposes a system and a method for preparing high-purity vanadium pentoxide by adopting a chlorination method and taking industrial-grade vanadium pentoxide as a raw material. The high-purity vanadium pentoxide is prepared by carbon-matching chlorination, dedusting condensation, rectification purification, gas-phase ammonization and ammonium vanadate calcination. The patent has the following disadvantages: (1) the carbon-matching chlorination is a violent exothermic process and needs to transfer heat to the outside of the chlorination furnace; in the patent, air is blown into the chlorination furnace, so that the temperature of the furnace is increased, and the fluidization state is influenced; (2) the flue gas dust removal-condensation part is very simple, a large amount of unreacted dust is mixed in the chlorinated flue gas, the single cyclone separator cannot achieve an effective dust removal effect, and the dust moves backwards to block a subsequent pipeline, so that the hidden trouble of production stop is brought; meanwhile, the recovery rate can be greatly reduced and the production cost can be increased due to insufficient condensation of vanadium oxychloride; (3) the rectification purification can only separate metal chlorides which have large difference with the saturated vapor pressure of the vanadium oxychloride, however, some titanium and silicon chlorides have similar saturated vapor pressure with the vanadium oxychloride, and the high-purity vanadium oxychloride is difficult to obtain by a single rectification method; (4) the gas phase ammonization-ammonium salt calcining process can generate a large amount of ammonium chloride and ammonia-rich tail gas, and the environmental protection cost is increased.

CN105984897A discloses a system and a method for preparing high-purity vanadium pentoxide powder by a similar chlorination method. Adopts the process technologies of carbon matching chlorination, dust removal condensation, rectification purification, gas phase hydrolysis and fluidized calcination. The gas-phase hydrolysis process is adopted to replace a gas-phase ammonification process, so that the problems of ammonium chloride and ammonia-rich tail gas are solved. However, because a large amount of water is added and the oxygen concentration in the compressed air is low, a large amount of hydrochloric acid is generated by gas phase hydrolysis, and the treatment of the vanadium-containing hydrochloric acid greatly improves the environmental protection cost. Meanwhile, the technology also has the problems of overheating of the chlorination furnace, pipeline blockage, low recovery rate of vanadium oxychloride and substandard purity of the vanadium oxychloride.

CN105984899A discloses a system and a method for preparing high-purity vanadium pentoxide by a similar chlorination method. Adopts the process technologies of carbon matching chlorination, dust removal condensation, rectification purification and plasma oxidation. The plasma oxidation process is adopted to replace gas-phase ammonification and gas-phase hydrolysis processes, so that the problems of ammonia-rich tail gas and vanadium-containing hydrochloric acid are solved. However, the plasma oxidation technology is easy to have the problems that vanadium pentoxide is molten and scabs are generated due to overhigh temperature, and the oxidation recovery efficiency is low, so that the large-scale operation is difficult. The patent technology also has the problems of overheating of the chlorination furnace, blockage of pipelines, low recovery rate of vanadium oxychloride and substandard purity of the vanadium oxychloride.

CN105984900A discloses a system and a method for preparing high-purity vanadium pentoxide powder by a chlorination method. Adopts the process technologies of carbon matching chlorination, dust removal condensation, rectification purification, ammonium salt precipitation and fluidized calcination. The ammonium salt precipitation process can bring a large amount of ammonia nitrogen wastewater, and the environmental protection cost is increased. Meanwhile, the technology also has the problems of overheating of the chlorination furnace, pipeline blockage, low recovery rate of vanadium oxychloride and substandard purity of the vanadium oxychloride.

CN105986126A discloses a process technology for preparing vanadium pentoxide powder by a chlorination method by taking vanadium slag as a raw material. Adopts the processes of carbon matching chlorination, dust removal condensation, distillation purification and gas phase hydrolysis. The patent has the following disadvantages: (1) a large amount of impurities such as iron, manganese, chromium, titanium, aluminum and the like exist in the vanadium slag, and are converted into chlorides in a chlorination process, so that a large amount of chlorination tailings pollute the environment and cannot be economically and efficiently utilized; (2) the patent technology also has the problems of overheating of a chlorination furnace, blockage of pipelines, low recovery rate of vanadium oxychloride, substandard purity of vanadium oxychloride and incapability of processing a large amount of vanadium-containing hydrochloric acid.

CN105984898A discloses a system and a method for preparing high-purity vanadium tetraoxide by a chlorination method. Adopts the process technologies of carbon matching chlorination, dust removal condensation, rectification purification, gas phase hydrolysis and fluidized bed reduction. The patent technology also has the problems of overheating of a chlorination furnace, blockage of pipelines, low recovery rate of vanadium oxychloride, substandard purity of vanadium oxychloride and incapability of processing a large amount of vanadium-containing hydrochloric acid. The valence state of the vanadium tetraoxide is difficult to accurately control in the reduction process, and a cooling device is lacked after the reduction process, so that the problem of reoxidation of the high-temperature vanadium tetraoxide is caused.

In addition, CN106257724A discloses a process for precipitation of ammonium salts of vanadium oxychloride, CN106257726A discloses a process for vapor phase amination of vanadium oxychloride, CN106257727A discloses a process for liquid phase hydrolysis, and CN106257728A discloses a process for vapor phase hydrolysis. The technologies disclosed in these patents are similar to the aforementioned patents, and mainly have the problems of ammonia nitrogen wastewater and vanadium-containing hydrochloric acid.

The low-valence vanadium oxide is mainly prepared by using vanadium-containing ammonium salt/vanadium pentoxide as a raw material through a reduction method. CN104495926A discloses a vanadium trioxide and a preparation method thereof, wherein vanadium pentoxide and graphite powder are mixed for agglomeration and are reduced in a pushed slab kiln at 600-700 ℃ to obtain vanadium trioxide powder. CN104445041A discloses vanadium trioxide for vanadium alloy smelting and a preparation method thereof, wherein coal gas is introduced into a rotary kiln to deaminate and reduce ammonium polyvanadate to obtain vanadium trioxide. CN103224252B discloses a method for preparing vanadium tetraoxide, wherein nitrogen and hydrogen are introduced into a tunnel kiln to reduce vanadium pentoxide to obtain vanadium tetraoxide. The main defects of the patent technologies are that the fixed bed or rotary kiln mode is adopted for reduction, and the energy consumption is high.

CN106257724A discloses a technology for preparing high-purity low-valence vanadium oxide by reducing ammonium vanadate by a fluidized bed, and mainly has the problems that the reduction tail gas contains a large amount of ammonia gas and ammonium chloride dust, the environment is seriously polluted, the environmental protection cost is increased, and the large-scale industrial production is difficult; and the latent heat of the reduction tail gas is not utilized, which is not beneficial to reducing the production cost. CN106257725A discloses a technology for preparing high-purity low-valence vanadium oxide by reducing vanadium-containing materials by a fluidized bed, and has the defects that the latent heat of tail gas is not utilized, and the production cost is increased. CN106257726A discloses a technology for preparing high-purity low-valence vanadium oxide by reducing ammonium vanadate with a fluidized bed, which has the defects of ammonia pollution in reduction tail gas and latent heat utilization of the reduction tail gas. CN106257727A discloses a technology for preparing high-purity vanadium oxide by reducing vanadium pentoxide wet materials by a fluidized bed, which mainly has the defects that the vanadium pentoxide filter cake has high water content and is not beneficial to conveying by a screw feeder; and the problem that the vanadium pentoxide wet material is easy to sinter when directly subjected to heat exchange of high-temperature gas from a tail gas combustor, so that the particle size distribution of the vanadium pentoxide powder is too wide, and the vanadium pentoxide powder is not beneficial to the reduction operation of a reduction fluidized bed. CN106257728A also discloses a technology for preparing high-purity low-valence vanadium oxide by reducing vanadium pentoxide powder by a fluidized bed, and the problem that the latent heat of the reduced tail gas is not utilized is also existed.

In addition, for industrial large-scale application, the prior chlorination method for preparing high-purity electrolyte still has the following six problems: (1) the chlorination of the vanadium raw material belongs to a strong heat release process, the heat generated by chlorination reaction can meet the preheating of solid and gas reaction materials, and a large amount of heat is still remained, so that the vanadium material is locally overheated, the fluidization state and the chlorination selectivity are influenced, and an effective method needs to be found to remove the heat out of a fluidized bed; (2) the dedusting and condensing section of the chlorinated flue gas is related to the continuity of production and the recovery rate of vanadium oxychloride, and a special device is required for reinforcement; (3) the rectification/distillation purification can only separate metal chlorides which have large difference with saturated vapor pressure of vanadium oxychloride, however, some titanium and silicon chlorides have similar saturated vapor pressure with vanadium oxychloride, and high-purity vanadium oxychloride is difficult to obtain by a rectification/distillation method alone, and other effective impurity removal methods are required to be matched; (4) the preparation of vanadium pentoxide by vanadium oxychloride still has no clean, efficient and environment-friendly preparation method. If the chlorine can not realize circulation, the vanadium-containing hydrochloric acid can not be effectively treated, so that the production cost is greatly increased, the environmental protection cost is increased, and large-scale industrialization is difficult to realize. (5) The preparation of low-valence vanadium oxide by fluidized bed reduction still faces the problems of material conveying, ammonia gas treatment in tail gas, comprehensive utilization of heat in the tail gas and the like. (6) The existing preparation method of the vanadium electrolyte has the defects. The electrolysis method needs concentrated sulfuric acid to activate vanadium pentoxide, and the production environment is severe. The low-valence vanadium oxide dissolving method usually adopts a stirring reaction kettle mode, has a stirring blind area, has low dissolving efficiency, and can be fully dissolved only by stirring for a long time.

Therefore, temperature regulation and control in the chlorination process are realized through technological and technical innovation; developing a new process for purifying and converting vanadium oxychloride into vanadium pentoxide with high efficiency, and realizing the regeneration cycle of chlorine; the novel efficient and energy-saving fluidized bed reduction process is developed, and the production energy consumption is reduced; the development of an efficient low-valence vanadium oxide dissolving reactor and the improvement of the production efficiency are the key points for realizing the large-scale industrialization of the technology for preparing the high-purity vanadium electrolyte by the chlorination method.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a system and a method for preparing high-purity vanadium electrolyte by a high-efficiency clean chlorination method, so as to avoid generating a large amount of polluted wastewater and reduce the production energy consumption and the operation cost.

In order to achieve the purpose, the invention adopts the following technical scheme:

in the invention:

the high efficiency means that the system for preparing the high-purity vanadium electrolyte provided by the invention can realize the regeneration cycle of chlorine, reduce pollution and save production cost;

the low-valence vanadium oxide in the high-purity low-valence vanadium oxide refers to vanadium oxide with the average valence of vanadium of 3.0-4.0, and the high purity refers to the purity of the low-valence vanadium oxide of more than 4N (namely 99.99%);

the high-purity vanadium oxychloride liquid is vanadium oxychloride liquid with the purity of more than 4N (namely 99.99 percent);

the equivalent average valence of vanadium in the low-valence vanadium oxide is 3.0-4.0;

the high-purity vanadium electrolyte is a vanadium electrolyte with the impurity content of less than 10 ppm;

the high boiling point component refers to a material at the bottom of the rectifying tower;

the clean oxygen-enriched air is oxygen-enriched air subjected to dust removal, oil removal and water removal treatment, and the oxygen-enriched air is air with the volume fraction of oxygen being more than 23.5%;

the clean nitrogen is nitrogen subjected to dust removal treatment;

the clean water is water with the resistivity of more than 14M omega cm (25 ℃);

the clean reducing gas is reducing gas subjected to dust removal, oil removal and water removal treatment;

the ultrapure water is water with the resistivity of 18M omega cm (25 ℃);

the high-temperature reducing gas is reducing gas with the temperature of more than 300 ℃.

The industrial nitrogen main pipe is used for providing industrial nitrogen; the chlorine gas source main pipe is used for providing chlorine gas; the clean water main pipe is used for providing clean water; the clean oxygen-enriched air main pipe is used for providing clean oxygen-enriched air; the fuel manifold is used for providing fuel; the compressed air main pipe is used for providing compressed air; the clean reducing gas main pipe is used for providing clean reducing gas; the clean nitrogen main pipe is used for providing clean nitrogen; the ultrapure water main pipe is used for supplying ultrapure water; the pure sulfuric acid header pipe is used to provide pure sulfuric acid.

On one hand, the invention provides a system for preparing high-purity vanadium electrolyte by a high-efficiency clean chlorination method, which comprises a feeding working section 1, a chlorination working section 2, a dedusting and leaching working section 3, a purification working section 4, a catalytic oxidation working section 5, a catalytic oxidation product feeding working section 6, a fluidized bed preheating working section, a reduction roasting working section 8, a cooling fluidized bed working section 9, a high-purity low-valence vanadium oxide feeding working section 10 and a liquid-solid fluidized bed dissolving working section 11;

the feeding working section 1 comprises an industrial grade vanadium oxide material bin 1-1, an industrial grade vanadium oxide star-shaped feeder 1-2, a carbon source bin 1-3, a carbon source star-shaped feeder 1-4, a mixer 1-5 and a mixer star-shaped feeder 1-6;

the chlorination working section 2 comprises a boiling chlorination furnace feeder 2-1, a boiling chlorination furnace 2-2, a chlorination furnace cyclone separator 2-3, a first slurry nozzle 2-4, a second slurry nozzle 2-5 and a chlorination residue discharger 2-6;

the dedusting and leaching section 3 comprises a dedusting tower 3-1, a first-stage leaching tower 3-2, a second-stage leaching tower 3-3, a third-stage leaching tower 3-4, a centrifugal filter 3-5 and a vanadium oxychloride slurry tank 3-6;

the purification working section 4 comprises a hydrolysis impurity removal kettle 4-1, a distillation kettle 4-2, a rectifying tower 4-3, a vanadium oxychloride condenser 4-4, a vanadium oxychloride reflux tank 4-5 and a high-purity vanadium oxychloride storage tank 4-6;

the catalytic oxidation working section 5 comprises a vanadium oxychloride vaporizer 5-1, a vanadium oxychloride nozzle 5-2, a clean water atomizing nozzle 5-3, a hydrochloric acid atomizing nozzle 5-4, a clean oxygen-enriched air preheater 5-5, a catalytic oxidation fluidized bed 5-6, a catalytic oxidation fluidized bed cyclone separator 5-7, a hydrochloric acid condensation absorption tower 5-8 and a catalytic oxidation fluidized bed discharger 5-9;

the catalytic oxidation product feeding section 6 comprises a catalytic oxidation product bin 6-1 and a catalytic oxidation product star-shaped feeder 6-2;

the fluidized bed preheating section comprises a preheating fluidized bed feeder 7-1, a preheating fluidized bed 7-2, a preheating fluidized bed discharger 7-3 and a preheating fluidized bed cyclone separator 7-4;

the reduction roasting section 8 comprises a reduction bed gas heater 8-1, a reduction fluidized bed 8-2, a reduction bed cyclone separator 8-3 and a reduction bed discharger 8-4;

the cooling fluidized bed working section 9 comprises a cooling fluidized bed 9-1, a cooling fluidized bed cyclone separator 9-2 and a cooling fluidized bed discharger 9-3;

the high-purity low-valence vanadium oxide feeding working section 10 comprises a high-purity low-valence vanadium oxide material bin 10-1 and a high-purity low-valence vanadium oxide star-shaped feeder 10-2;

the liquid-solid fluidized bed dissolving section 11 comprises a liquid-solid fluidized bed feeder 11-1, a liquid-solid fluidized bed 11-2 and a high-purity vanadium electrolyte storage tank 11-3;

a discharge hole at the bottom of the industrial-grade vanadium oxide material bin 1-1 is connected with a feed hole of the industrial-grade vanadium oxide star-shaped feeder 1-2; a discharge hole at the bottom of the carbon source bin 1-3 is connected with a feed hole of the carbon source star feeder 1-4; the discharge hole of the industrial grade vanadium oxide star feeder 1-2 and the discharge hole of the carbon source star feeder 1-4 are connected with the feed inlet of the mixer 1-5 through pipelines; a discharge hole at the bottom of the mixer 1-5 is connected with a feed hole of the mixer star-shaped feeder 1-6; the discharge hole of the mixer star-shaped feeder 1-6 is connected with the feed hole of the boiling chlorination furnace feeder 2-1 through a pipeline;

the discharge hole of the boiling chlorination furnace feeder 2-1 is connected with the feed inlet at the upper part of the boiling chlorination furnace 2-2 through a pipeline; an air inlet at the bottom of the boiling chlorination furnace feeder 2-1 is connected with an industrial nitrogen main pipe; the gas inlet at the lower part of the boiling chlorination furnace 2-2 is respectively connected with a chlorine gas source main pipe and an industrial nitrogen main pipe through pipelines; the first slurry nozzle 2-4 is positioned at the upper part of the boiling chlorination furnace 2-2; the feed inlets of the first slurry nozzles 2 to 4 are connected with the slurry outlets in the middle of the vanadium oxychloride slurry tanks 3 to 6 through pipelines; the second slurry nozzle 2-5 is positioned at the lower part of the boiling chlorination furnace 2-2; the feed inlets of the second slurry nozzles 2 to 5 are connected with the slurry outlets in the middle of the vanadium oxychloride slurry tanks 3 to 6 through pipelines; the chlorination furnace cyclone separator 2-3 is arranged at the center of the top of the boiling chlorination furnace 2-2; an air outlet at the top of the chlorination furnace cyclone separator 2-3 is connected with an air inlet of the dust removal tower 3-1 through a pipeline; a slag discharge port at the lower part of the boiling chlorination furnace 2-2 is connected with a feed inlet of the chlorination residue discharger 2-6 through a pipeline; the air inlet at the bottom of the chlorination residue discharger 2-6 is connected with an industrial nitrogen header pipe;

the vanadium oxychloride slurry nozzle at the top of the dedusting tower 3-1 is connected with the outlet at the bottom of the vanadium oxychloride slurry tank 3-6 through a pipeline; the vanadium oxychloride slurry nozzle at the top of the dedusting tower 3-1 is simultaneously connected with the bottom outlet of the distillation kettle 4-2 through a pipeline; the dust removing tower 3-1 comprises a rotary dust removing cylinder provided with a scraper; the lower part of the dust removing tower 3-1 is provided with a slag discharge port with a valve; the gas outlet of the dust removing tower 3-1 is connected with the gas inlet of the first-stage leaching tower 3-2 through a pipeline; the liquid outlet of the first-stage leaching tower 3-2 is connected with the liquid inlet of the centrifugal filter 3-5 through a pipeline; the gas outlet of the first-stage leaching tower 3-2 is connected with the gas inlet of the second-stage leaching tower 3-3 through a pipeline; the liquid outlet of the second-stage leaching tower 3-3 is connected with the liquid inlet of the centrifugal filter 3-5 through a pipeline; the gas outlet of the second-stage leaching tower 3-3 is connected with the gas inlet of the third-stage leaching tower 3-4 through a pipeline; a liquid outlet of the third-stage leaching tower 3-4 is connected with a liquid inlet of the centrifugal filter 3-5 through a pipeline; the gas outlet of the third leaching tower 3-4 is connected with the gas inlet of the tail gas treatment system through a pipeline; a supernatant outlet of the centrifugal filter 3-5 is connected with a liquid inlet of the hydrolysis impurity removal kettle 4-1 through a pipeline; the slurry outlet of the centrifugal filter 3-5 is connected with the slurry inlet of the vanadium oxychloride slurry tank 3-6 through a pipeline;

an impurity removing agent feeding port is formed in the top of the hydrolysis impurity removing kettle 4-1; the liquid outlet of the hydrolysis impurity removal kettle 4-1 is connected with the liquid inlet of the distillation kettle 4-2 through a pipeline; a gas outlet of the distillation kettle 4-2 is connected with a gas inlet of the rectifying tower 4-3 through a pipeline; a reflux port of the distillation kettle 4-2 is connected with a liquid reflux outlet at the bottom of the rectifying tower 4-3 through a pipeline; a gas outlet at the top of the rectifying tower 4-3 is connected with a gas inlet of the vanadium oxytrichloride condenser 4-4 through a pipeline; the liquid outlet of the vanadium oxytrichloride condenser 4-4 is connected with the liquid inlet of the vanadium oxytrichloride reflux tank 4-5 through a pipeline; a reflux port of the vanadium oxytrichloride reflux tank 4-5 is connected with a liquid reflux port at the upper part of the rectifying tower 4-3 through a pipeline; the high-purity vanadium oxychloride liquid outlet of the vanadium oxychloride reflux tank 4-5 is connected with the liquid inlet of the high-purity vanadium oxychloride storage tank 4-6 through a pipeline; a liquid outlet at the lower part of the high-purity vanadium trichloride storage tank 4-6 is connected with a liquid inlet of the vanadium trichloride vaporizer 5-1 through a pipeline;

the air outlet of the vanadium oxytrichloride vaporizer 5-1 is connected with the air inlet of the vanadium oxytrichloride nozzle 5-2 through a pipeline; the vanadium oxytrichloride nozzle 5-2 is positioned at the middle lower part of the catalytic oxidation fluidized bed 5-6; the liquid inlet of the clean water atomizing nozzle 5-3 is connected with a clean water main pipe; the liquid inlet of the clean water atomizing nozzle 5-3 is simultaneously connected with a clean oxygen-enriched air main pipe; the clean water atomization nozzle 5-3 is positioned at the lower part of the catalytic oxidation fluidized bed 5-6; the air inlet of the clean oxygen-enriched air preheater 5-5 is connected with the clean oxygen-enriched air main pipe, and the air outlet of the clean oxygen-enriched air preheater 5-5 is connected with the fluidizing gas inlet at the bottom of the catalytic oxidation fluidized bed 5-6 through a pipeline; the hydrochloric acid atomizing nozzle 5-4 is positioned at the lower part of the catalytic oxidation fluidized bed 5-6; the liquid inlet of the hydrochloric acid atomizing nozzle 5-4 is connected with the liquid outlet of the hydrochloric acid condensation absorption tower 5-8 through a pipeline; the liquid inlets of the hydrochloric acid atomizing nozzles 5-4 are simultaneously connected with a clean oxygen-enriched air main pipe; the catalytic oxidation fluidized bed cyclone separator 5-7 is arranged at the center of the top of the catalytic oxidation fluidized bed 5-6; the gas outlet of the catalytic oxidation fluidized bed cyclone separator 5-7 is connected with the gas inlet of the hydrochloric acid condensation absorption tower 5-8 through a pipeline; the gas outlets of the hydrochloric acid condensation absorption towers 5 to 8 are connected with the gas inlet of the chlorine gas circulating system through a pipeline; the discharge hole in the middle of the catalytic oxidation fluidized bed 5-6 is connected with the feed hole of the catalytic oxidation fluidized bed discharger 5-9 through a pipeline; the loose air inlet of the catalytic oxidation fluidized bed discharger 5-9 is connected with a clean nitrogen header pipe; the discharge hole of the catalytic oxidation fluidized bed discharger 5-9 is connected with the feed hole of the catalytic oxidation product bin 6-1 through a pipeline;

the discharge hole of the catalytic oxidation product bin 6-1 is connected with the feed hole of the catalytic oxidation product star feeder 6-2; the discharge hole of the catalytic oxidation product star-shaped feeder 6-2 is connected with the feed hole of the preheating fluidized bed feeder 7-1 through a pipeline;

the discharge hole of the preheating fluidized bed feeder 7-1 is connected with the feed inlet of the preheating fluidized bed 7-2 through a pipeline; the loosening air inlet of the preheating fluidized bed feeder 7-1 is connected with a clean nitrogen header pipe; the preheating fluidized bed cyclone separator 7-4 is arranged at the top center of the preheating fluidized bed 7-2; the gas outlet of the preheating fluidized bed cyclone separator 7-4 is connected with the fuel inlet of the reducing bed gas heater 8-1 through a pipeline; the high-temperature gas inlet of the preheating fluidized bed 7-2 is connected with the gas outlet of the reduction bed cyclone separator 8-3 through a pipeline; the discharge port at the lower part of the preheating fluidized bed 7-2 is connected with the feed inlet of the preheating fluidized bed discharger 7-3 through a pipeline; the loosening air inlet of the preheating fluidized bed discharger 7-3 is connected with a clean nitrogen header pipe; the discharge hole of the preheating fluidized bed discharger 7-3 is connected with the feed hole of the reduction fluidized bed 8-2 through a pipeline;

a fluidizing gas inlet of the reducing fluidized bed 8-2 is connected with a high-temperature gas outlet of the reducing bed gas heater 8-1 through a pipeline; the fuel inlet of the reducing bed gas heater 8-1 is connected with a fuel header pipe; a combustion-supporting air inlet of the reducing bed gas heater 8-1 is connected with a compressed air main pipe; a reducing gas inlet of the reducing bed gas heater 8-1 is respectively connected with a clean reducing gas main pipe and a clean nitrogen main pipe; the reduction bed cyclone separator 8-3 is arranged at the top center of the reduction fluidized bed 8-2; a discharge hole at the upper part of the reduction fluidized bed 8-2 is connected with a feed hole of the reduction bed discharger 8-4 through a pipeline; the loosening air inlet of the reduction bed discharger 8-4 is connected with a clean nitrogen header pipe; the discharge hole of the reducing bed discharger 8-4 is connected with the feed hole of the cooling fluidized bed 9-1 through a pipeline;

a cooling gas inlet of the cooling fluidized bed 9-1 is connected with a clean nitrogen header pipe; a vertical baffle is arranged in the cooling fluidized bed 9-1; the cooling fluidized bed cyclone separator 9-2 is arranged at the top center of the cooling fluidized bed 9-1; the gas outlet of the cooling fluidized bed cyclone separator 9-2 is connected with the gas inlet of the tail gas treatment system through a pipeline; the discharge hole of the cooling fluidized bed 9-1 is connected with the feed hole of the discharger 9-3 of the cooling fluidized bed through a pipeline; a loose air inlet of the cooling fluidized bed discharger 9-3 is connected with a clean nitrogen header pipe; the discharge hole of the cooling fluidized bed discharger 9-3 is connected with the feed hole of the high-purity low-valence vanadium oxidation material bin 10-1 through a pipeline;

the discharge hole of the high-purity low-valence vanadium oxide material bin 10-1 is connected with the feed hole of the high-purity low-valence vanadium oxide star-shaped feeder 10-2; the discharge hole of the high-purity low-valence vanadium oxide star-shaped feeder 10-2 is connected with the feed hole of the liquid-solid fluidized bed feeder 11-1 through a pipeline;

the loosening air inlet of the liquid-solid fluidized bed feeder 11-1 is connected with a clean nitrogen header pipe; the discharge port of the liquid-solid fluidized bed feeder 11-1 is connected with the feed port of the liquid-solid fluidized bed 11-2 through a pipeline; an ultrapure water inlet of the liquid-solid fluidized bed 11-2 is connected with an ultrapure water main pipe; a sulfuric acid inlet of the liquid-solid fluidized bed 11-2 is connected with a pure sulfuric acid main pipe; a gas outlet at the top of the liquid-solid fluidized bed 11-2 is connected with a gas inlet of the tail gas treatment system through a pipeline; a liquid outlet of the liquid-solid fluidized bed 11-2 is connected with the high-purity vanadium electrolyte storage tank 11-3 through a pipeline; and a high-purity vanadium electrolyte outlet with a valve is arranged at the bottom of the high-purity vanadium electrolyte storage tank 11-3.

On the other hand, the invention provides a method for preparing high-purity vanadium electrolyte by using a high-efficiency clean chlorination method based on the system, which comprises the following steps:

industrial vanadium oxide in the industrial vanadium oxidation material bin 1-1 and a carbon source in the carbon source bin 1-3 simultaneously enter the mixer 1-5 to be mixed through the industrial vanadium oxide star feeder 1-2 and the carbon source star feeder 1-4 respectively; the mixed materials sequentially pass through the mixer star-shaped feeder 1-6 and the boiling chlorination furnace feeder 2-1 to enter the boiling chlorination furnace 2-2; chlorine from a chlorine gas source main pipe and nitrogen from an industrial nitrogen main pipe enter the boiling chlorination furnace 2-2 through a gas inlet at the lower part of the boiling chlorination furnace 2-2, so that industrial-grade vanadium oxide and a carbon source are kept fluidized and are subjected to chemical reaction with the industrial-grade vanadium oxide and the carbon source, and the chlorine and the carbon source jointly act to chlorinate the vanadium oxide and part of impurities, so that chlorination residues and chlorinated flue gas rich in vanadium oxychloride are obtained; vanadium oxychloride slurry from a slurry outlet in the middle of the vanadium oxychloride slurry tank 3-6 is respectively sprayed into the boiling chlorination furnace 2-2 through the first slurry nozzle 2-4 and the second slurry nozzle 2-5, and the temperature in the furnace is adjusted; the chlorination residues are discharged and treated through a residue discharge port at the lower part of the boiling chlorination furnace 2-2 and the chlorination residue discharger 2-6 in sequence; removing dust from the chlorination flue gas through the chlorination furnace cyclone separator 2-3, returning the dust to the boiling chlorination furnace 2-2, and then entering the dust removal tower 3-1;

a slurry nozzle is arranged at the top of the dust removing tower 3-1, and slurry from the vanadium oxychloride slurry tank 3-6 and the bottom of the distillation kettle 4-2 enters the dust removing tower 3-1 through the slurry nozzle to cool the chlorination flue gas; the generated dust-collecting slag is discharged through a slag discharge port at the lower part of the dust-removing tower 3-1 and is sent for treatment; the cooled chlorinated flue gas enters the first-stage leaching tower 3-2 for leaching, and leached slurry is sent to the centrifugal filter 3-5 for treatment; sending the first-stage leaching tail gas to the second-stage leaching tower 3-3 for leaching, and sending the leaching slurry to the centrifugal filter 3-5 for treatment; sending the second-stage leaching tail gas to the third-stage leaching tower for leaching 3-4, and sending the leaching slurry to the centrifugal filter for treatment 3-5; the third-stage leaching tail gas is sent to a tail gas treatment system; slurry at the bottom of the centrifugal filter 3-5 is sent to the vanadium oxychloride slurry tank 3-6, and supernatant is sent to the hydrolysis impurity removal kettle 4-1;

feeding vanadium oxychloride slurry obtained by pre-impurity removal in the hydrolysis impurity removal kettle 4-1 into the distillation kettle 4-2 for distillation, and feeding the distilled gas into the rectifying tower 4-3 for rectification treatment; spraying the concentrated solution generated by distillation into the dust removing tower 3-1 through a nozzle at the top of the dust removing tower 3-1; the high boiling point component at the bottom of the rectifying tower 4-3 enters the distillation kettle 4-2 through a reflux port; after vanadium oxychloride steam is condensed to liquid by the vanadium oxychloride condenser 4-4, part of the vanadium oxychloride steam flows back to the rectifying tower 4-3 through the vanadium oxychloride reflux tank 4-5, and the rest of the vanadium oxychloride steam enters the high-purity vanadium oxychloride storage tank 4-6;

the high-purity vanadium oxychloride in the high-purity vanadium oxychloride storage tank 4-6 is vaporized by the vanadium oxychloride vaporizer 5-1 and then enters the catalytic oxidation fluidized bed 5-6 through the vanadium oxychloride nozzle 5-2; clean water from a clean water main pipe and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter the catalytic oxidation fluidized bed 5-6 through the clean water atomization nozzle 5-3; hydrochloric acid from the hydrochloric acid condensation absorption tower 5-8 and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter the catalytic oxidation fluidized bed 5-6 through the hydrochloric acid atomization nozzle 5-4; the clean oxygen-enriched air from the clean oxygen-enriched air main pipe is preheated by the clean oxygen-enriched air preheater 5-5 and then enters the catalytic oxidation fluidized bed 5-6 through a fluidizing gas inlet at the lower part of the catalytic oxidation fluidized bed 5-6; vanadium oxychloride in the catalytic oxidation fluidized beds 5-6 obtains vanadium pentoxide powder and flue gas containing hydrogen chloride and chlorine under the catalytic oxidation action of water and oxygen-enriched air; vanadium pentoxide powder enters the catalytic oxidation product bin 6-1 through the catalytic oxidation fluidized bed discharger 5-9; flue gas containing hydrogen chloride and chlorine enters the hydrochloric acid condensation absorption tower 5-8 after being dedusted by the catalytic oxidation fluidized bed cyclone separator 5-7, the hydrochloric acid absorbed by condensation returns to the catalytic oxidation fluidized bed 5-6 through the hydrochloric acid atomizing nozzle 5-4, and the rest chlorine is sent to a chlorine circulating system;

vanadium pentoxide powder in the catalytic oxidation product bin 6-1 sequentially enters the preheating fluidized bed 7-2 through the catalytic oxidation product star feeder 6-2 and the preheating fluidized bed feeder 7-1; high-temperature reducing gas from the cyclone separator 8-3 of the reducing bed enters through a fluidizing gas inlet at the lower part of the preheating fluidized bed 7-2, so that vanadium pentoxide powder in the preheating fluidized bed 7-2 is maintained in fluidization, and preheating is completed; the preheated tail gas is dedusted by the preheating fluidized bed cyclone separator 7-4 and then is sent to the reducing bed gas heater 8-1 for combustion; vanadium pentoxide powder which is preheated in the preheating fluidized bed 7-2 enters the reduction fluidized bed 8-2 through the discharger 7-3 of the preheating fluidized bed;

after being heated by the reducing bed gas heater 8-1, clean reducing gas and clean nitrogen enter the reducing fluidized bed 8-2 to maintain fluidization of vanadium pentoxide powder and enable the vanadium pentoxide powder to carry out reduction reaction, so that reducing smoke and low-valence vanadium oxide powder are obtained; the reduction flue gas is dedusted by the reduction bed cyclone separator 8-3 and then is sent to the preheating fluidized bed 7-2 for heat exchange; the low-valence vanadium oxide enters the cooling fluidized bed 9-1 through the reduction bed discharger 8-4;

clean nitrogen enters through an air inlet at the bottom of the cooling fluidized bed 9-1 to maintain fluidization of the low-valence vanadium oxide and realize heat exchange; a vertical baffle is arranged in the cooling fluidized bed 9-1; the heat exchange tail gas is sent to a tail gas treatment system after dust is removed by the cooling fluidized bed cyclone separator 9-2; the cooled low-valence vanadium oxide enters the high-purity low-valence vanadium oxidation material bin 10-1 through the cooling fluidized bed discharger 9-3;

high-purity low-valence vanadium oxide in the high-purity low-valence vanadium oxidation material bin 10-1 sequentially enters the liquid-solid fluidized bed 11-2 through the high-purity low-valence vanadium oxide star feeder 10-2 and the liquid-solid fluidized bed feeder 11-1, and undergoes a dissolution reaction with ultrapure water from an ultrapure water main pipe and pure sulfuric acid from a pure sulfuric acid main pipe to obtain high-purity vanadium electrolyte and acid gas; and (3) sending the acid gas to a tail gas treatment system, and sending the high-purity vanadium electrolyte to the high-purity vanadium electrolyte storage tank 11-3.

In the system for preparing the high-purity vanadium electrolyte by the efficient clean chlorination method, the first slurry nozzle 2-4 and the second slurry nozzle 2-5 are used for spraying vanadium oxychloride slurry into the boiling chlorination furnace 2-2 to regulate and control the temperature of the boiling chlorination furnace 2-2.

The dust removal tower 3-1 comprises a rotary dust removal cylinder provided with a scraper, and can effectively prevent the collected sediment from being caked.

The catalytic oxidation section 5 comprises 5-8 of the hydrochloric acid condensation absorption tower and is used for recovering and recycling vanadium-containing hydrochloric acid.

In the method for preparing the high-purity vanadium electrolyte by the efficient clean chlorination method, the industrial-grade vanadium oxide in the industrial-grade vanadium oxide material bin 1-1 is selected from any one or a combination of at least two of industrial-grade vanadium trioxide, industrial-grade vanadium tetraoxide or industrial-grade vanadium pentoxide, and typical but non-limiting combinations such as the industrial-grade vanadium trioxide and the industrial-grade vanadium tetraoxide, the industrial-grade vanadium tetraoxide and the industrial-grade vanadium pentoxide, the industrial-grade vanadium trioxide, the industrial-grade vanadium tetraoxide and the industrial-grade vanadium pentoxide; the carbon source in the carbon source bins 1-3 is selected from any one or a combination of at least two of activated carbon, metallurgical coke, petroleum coke and coal powder, and typical but non-limiting combinations comprise the activated carbon and the metallurgical coke, the petroleum coke and the coal powder, the activated carbon, the metallurgical coke and the petroleum coke, the metallurgical coke, the petroleum coke and the coal powder; the addition amount of the carbon source is 5-30% of the mass of the industrial grade vanadium oxide, such as 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%.

In the boiling chlorination furnace 2-2, the chlorination operation temperature is 290-600 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 580 ℃, the gas velocity of the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 0.05-3.00 m/s, such as 0.08m/s, 0.10m/s, 0.15m/s, 0.18m/s, 0.20m/s, 0.25m/s or 0.28m/s, and the mole fraction of chlorine in the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 20-100%, such as 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%.

In the boiling chlorination furnace 2-2, chlorine and a carbon source act together to chlorinate vanadium oxide and part of impurities, wherein the impurities subjected to chlorination mainly comprise: the mass of the impurities subjected to chlorination accounts for 20-50% of the total mass of the impurities, such as 25%, 30%, 35%, 40% or 45%.

The preliminary impurity removal in the hydrolysis impurity removal kettle 4-1 refers to the removal of impurities titanium and silicon by a selective hydrolysis method, the used impurity removal agent is water or aqueous solution, and the dosage of the impurity removal agent is 0.00001-0.1% of the mass of the vanadium oxychloride slurry, such as 0.00005%, 0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.008%, 0.01%, 0.02%, 0.03%, 0.04%, 0.06%, or 0.08%.

In the catalytic oxidation fluidized bed 5-6, the water vapor generated by the clean water atomizing nozzle 5-3 is 0.01-9.90% of the mass of vanadium oxychloride, such as 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.7%, 0.9%, 1.0%, 1.5%, 2.5%, 3.8%, 4.9%, 5.7%, 6.6%, 7.8%, 8.5% or 9.5%, etc., the volume fraction of oxygen in the introduced clean oxygen-enriched air is 30-95%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc., the catalytic oxidation operation temperature is 130-620 ℃, such as 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 200 ℃, 250 ℃, 300 ℃, 400 ℃, 450 ℃, 550 ℃, or 600 ℃, etc.

The clean reducing gas introduced into the reducing bed gas heater 8-1 is selected from any one or a combination of at least two of hydrogen, ammonia, electric furnace gas, converter gas, blast furnace gas, coke oven gas or gas generator gas, and typical but non-limiting combinations include hydrogen and ammonia, electric furnace gas, converter gas and blast furnace gas, coke oven gas and gas generator gas, converter gas, blast furnace gas and coke oven gas.

In the reduction fluidized bed 8-2, the reduction operation temperature is 300-750 ℃, such as 350 ℃, 400 ℃, 450 ℃, 500 ℃, 520 ℃, 580 ℃, 600 ℃, 630 ℃, 680 ℃ or 720 ℃ and the like, the volume fraction of the reduction gas in the introduced mixed gas of nitrogen and the reduction gas is 9% -91%, such as 10%, 13%, 15%, 18%, 23%, 28%, 35%, 45%, 58%, 64%, 72%, 86% or 90% and the like, and the reduction reaction time is 29-95 min, such as 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min and the like.

The dissolving device is a liquid-solid fluidized bed 11-2, the equivalent valence of vanadium ions in the high-purity vanadium electrolyte is 3.0-4.0, such as 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 or 3.9, and the like, that is, the equivalent valence of vanadium ions in the high-purity vanadium electrolyte is any value of 3.0-4.0.

The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.

Compared with the prior art, the invention has the beneficial effects that:

(1) the bed temperature is regulated and controlled by returning the vanadium oxychloride slurry to the boiling chlorination furnace, so that the temperature balance problem of the reaction section is solved, the temperature distribution of the chlorination furnace is more uniform, and the chlorination selectivity is stronger;

(2) by arranging the primary dust removal and the tertiary leaching, the chlorination flue gas is effectively dedusted and condensed, the pipeline blockage is avoided, the production continuity is ensured, and the recovery rate of the vanadium oxychloride gas is greatly improved;

(3) pre-removing impurities from the vanadium oxychloride slurry before rectification operation, and removing impurities such as silicon, titanium and the like which are difficult to remove through rectification operation by using a selective hydrolysis method, thereby ensuring the successful preparation of high-purity vanadium oxychloride;

(4) tail gas containing chlorine and hydrogen chloride discharged from the catalytic oxidation fluidized bed is treated by a hydrochloric acid condensation absorption tower, hydrochloric acid absorbed by condensation returns to the catalytic oxidation fluidized bed, and the rest chlorine is sent to a chlorine circulating system to realize the recirculation of the chlorine; vanadium oxychloride generates vanadium pentoxide powder and mixed flue gas of chlorine and hydrogen chloride under the catalytic oxidation action of water and oxygen, the condensed and recovered hydrochloric acid returns to the catalytic oxidation fluidized bed, and according to the balance movement, the generation of new hydrogen chloride is inhibited, and the zero emission of hydrogen chloride is realized;

(5) in the chlorination working section of industrial grade vanadium oxide, the catalytic oxidation working section of high-purity vanadium oxychloride, the preheating dust removal working section, the fluidized reduction working section, the cooling fluidized bed working section and the liquid-solid fluidized bed dissolution working section, fluidized beds are selected as reactors, so that the method is efficient, energy-saving and high in capacity, and is convenient for realizing large-scale industrial operation;

the method has the advantages of strong adaptability of raw materials, good chlorination selectivity, no pollution to wastewater discharge, no discharge of vanadium-containing hydrogen chloride, realization of cyclic utilization of chlorine, low production energy consumption and operation cost, stable product quality and the like, is suitable for large-scale industrial preparation of high-purity vanadium electrolyte, and has good economic benefit and social benefit.

Drawings

Fig. 1 is a schematic structural diagram of a system for preparing a high-purity vanadium electrolyte by a high-efficiency clean chlorination process provided in example 1.

Wherein:

1, a feeding section;

1-1, an industrial grade vanadium oxidation material bin; 1-2, an industrial grade vanadium oxide star-shaped feeder; 1-3, a carbon source bin; 1-4, a carbon source star feeder; 1-5, a mixer; 1-6, a mixer star-shaped feeder;

2, chlorination section;

2-1, a boiling chlorination furnace feeder; 2-2, a fluidized bed chlorination furnace; 2-3, a chlorination furnace cyclone separator; 2-4, a first slurry nozzle; 2-5, a second slurry nozzle; 2-6, a chlorination residue discharger;

3, a dust removal leaching section;

3-1, a dust removal tower; 3-2, a first-stage leaching tower; 3-3, a second-stage leaching tower; 3-4, a third-stage leaching tower; 3-5, centrifugal filter; 3-6, a vanadium oxychloride slurry tank;

4, a purification section;

4-1, hydrolyzing and impurity removing kettle; 4-2, a distillation kettle; 4-3, a rectifying tower; 4-4, a vanadium oxytrichloride condenser; 4-5, a vanadium oxytrichloride reflux tank; 4-6, a high-purity vanadium oxytrichloride storage tank;

5, a catalytic oxidation section;

5-1, a vanadium oxytrichloride vaporizer; 5-2, a vanadium oxytrichloride nozzle; 5-3, a clean water atomization nozzle; 5-4, a hydrochloric acid atomizing nozzle; 5-5, a clean oxygen-enriched air preheater; 5-6, catalytic oxidation fluidized bed; 5-7, a catalytic oxidation fluidized bed cyclone separator; 5-8, a hydrochloric acid condensation absorption tower; 5-9, a catalytic oxidation fluidized bed discharger;

6, a catalytic oxidation product feeding section;

6-1, a catalytic oxidation product bin; 6-2, a catalytic oxidation product star-shaped feeder;

7-1, preheating a fluidized bed feeder; 7-2, preheating the fluidized bed; 7-3, preheating a fluidized bed discharger; 7-4, preheating a fluidized bed cyclone separator;

8, a reduction roasting section;

8-1, reducing bed gas heater; 8-2, reducing the fluidized bed; 8-3, a reduction bed cyclone separator; 8-4, a reduction bed discharger;

9, cooling the fluidized bed section;

9-1, cooling the fluidized bed; 9-2, cooling the fluidized bed cyclone separator; 9-3, cooling the fluidized bed discharger;

10, a high-purity low-valence vanadium oxide feeding section;

10-1, a high-purity low-valence vanadium oxidation material bin; 10-2, a high-purity low-valence vanadium oxide star-shaped feeder;

11, a liquid-solid fluidized bed dissolving section;

11-1, a liquid-solid fluidized bed feeder; 11-2, a liquid-solid fluidized bed; 11-3, a high-purity vanadium electrolyte storage tank.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

Example 1

A system for preparing high-purity vanadium electrolyte by a high-efficiency clean chlorination method is shown in figure 1 and comprises a feeding working section 1, a chlorination working section 2, a dedusting and leaching working section 3, a purification working section 4, a catalytic oxidation working section 5, a catalytic oxidation product feeding working section 6, a fluidized bed preheating working section, a reduction roasting working section 8, a cooling fluidized bed working section 9, a high-purity low-valence vanadium oxide feeding working section 10 and a liquid-solid fluidized bed dissolving working section 11;

the dedusting and leaching section 3 comprises a dedusting tower 3-1, a first leaching tower 3-2, a second leaching tower 3-3, a third leaching tower 3-4, a centrifugal filter 3-5 and a vanadium oxychloride slurry tank 3-6;

a discharge hole at the bottom of the industrial-grade vanadium oxide material bin 1-1 is connected with a feed inlet of an industrial-grade vanadium oxide star-shaped feeder 1-2; a discharge hole at the bottom of the carbon source bin 1-3 is connected with a feed inlet of the carbon source star feeder 1-4; the discharge port of the industrial grade vanadium oxide star feeder 1-2 and the discharge port of the carbon source star feeder 1-4 are connected with the feed port of the mixer 1-5 through pipelines; a discharge hole at the bottom of the mixer 1-5 is connected with a feed inlet of the mixer star-shaped feeder 1-6; the discharge hole of the mixer star-shaped feeder 1-6 is connected with the feed hole of the boiling chlorination furnace feeder 2-1 through a pipeline;

the discharge hole of the boiling chlorination furnace feeder 2-1 is connected with the feed inlet at the upper part of the boiling chlorination furnace 2-2 through a pipeline; an air inlet at the bottom of the boiling chlorination furnace feeder 2-1 is connected with an industrial nitrogen main pipe; the gas inlet at the lower part of the boiling chlorination furnace 2-2 is respectively connected with a chlorine gas source main pipe and an industrial nitrogen main pipe through pipelines; the first slurry nozzle 2-4 is positioned at the upper part of the boiling chlorination furnace 2-2; the feed inlets of the first slurry nozzles 2 to 4 are connected with the slurry outlets in the middle of the vanadium oxychloride slurry tanks 3 to 6 through pipelines; the second slurry nozzle 2-5 is positioned at the lower part of the boiling chlorination furnace 2-2; the feed inlet of the second slurry nozzle 2-5 is connected with the slurry outlet at the middle part of the vanadium oxychloride slurry tank 3-6 through a pipeline; the chlorination furnace cyclone separator 2-3 is arranged at the top center of the boiling chlorination furnace 2-2; a gas outlet at the top of the chlorination furnace cyclone separator 2-3 is connected with a gas inlet of the dust removal tower 3-1 through a pipeline; a slag discharge port at the lower part of the boiling chlorination furnace 2-2 is connected with a feed inlet of a chlorination residue discharger 2-6 through a pipeline; the air inlet at the bottom of the chlorination residue slag discharger 2-6 is connected with an industrial nitrogen header pipe;

a vanadium oxychloride slurry nozzle at the top of the dedusting tower 3-1 is connected with a bottom outlet of the vanadium oxychloride slurry tank 3-6 through a pipeline; the vanadium oxychloride slurry nozzle at the top of the dedusting tower 3-1 is simultaneously connected with the bottom outlet of the distillation still 4-2 through a pipeline; the dust removing tower 3-1 comprises a rotary dust removing cylinder provided with a scraper; the lower part of the dedusting tower 3-1 is provided with a slag discharge port with a valve; the gas outlet of the dust removing tower 3-1 is connected with the gas inlet of the first-stage leaching tower 3-2 through a pipeline; a liquid outlet of the first-stage leaching tower 3-2 is connected with a liquid inlet of the centrifugal filter 3-5 through a pipeline; the air outlet of the first-stage leaching tower 3-2 is connected with the air inlet of the second-stage leaching tower 3-3 through a pipeline; a liquid outlet of the second-stage leaching tower 3-3 is connected with a liquid inlet of the centrifugal filter 3-5 through a pipeline; the gas outlet of the second-stage leaching tower 3-3 is connected with the gas inlet of the third-stage leaching tower 3-4 through a pipeline; a liquid outlet of the third-stage leaching tower 3-4 is connected with a liquid inlet of the centrifugal filter 3-5 through a pipeline; the gas outlet of the third leaching tower 3-4 is connected with the gas inlet of the tail gas treatment system through a pipeline; a supernatant outlet of the centrifugal filter 3-5 is connected with a liquid inlet of the hydrolysis impurity removal kettle 4-1 through a pipeline; the slurry outlet of the centrifugal filter 3-5 is connected with the slurry inlet of the vanadium oxychloride slurry tank 3-6 through a pipeline;

the top of the hydrolysis impurity removing kettle 4-1 is provided with an impurity removing agent feeding port; a liquid outlet of the hydrolysis impurity removal kettle 4-1 is connected with a liquid inlet of the distillation kettle 4-2 through a pipeline; a gas outlet of the distillation kettle 4-2 is connected with a gas inlet of the rectifying tower 4-3 through a pipeline; a reflux port of the distillation kettle 4-2 is connected with a liquid reflux outlet at the bottom of the rectifying tower 4-3 through a pipeline; a gas outlet at the top of the rectifying tower 4-3 is connected with a gas inlet of the vanadium oxytrichloride condenser 4-4 through a pipeline; a liquid outlet of the vanadium oxychloride condenser 4-4 is connected with a liquid inlet of the vanadium oxychloride reflux tank 4-5 through a pipeline; a reflux port of the vanadium oxytrichloride reflux tank 4-5 is connected with a liquid reflux port at the upper part of the rectifying tower 4-3 through a pipeline; the high-purity vanadium oxychloride liquid outlet of the vanadium oxychloride reflux tank 4-5 is connected with the liquid inlet of the high-purity vanadium oxychloride storage tank 4-6 through a pipeline; a liquid outlet at the lower part of the high-purity vanadium trichloride storage tank 4-6 is connected with a liquid inlet of a vanadium trichloride vaporizer 5-1 through a pipeline;

the air outlet of the vanadium oxytrichloride vaporizer 5-1 is connected with the air inlet of the vanadium oxytrichloride nozzle 5-2 through a pipeline; the vanadium oxytrichloride nozzle 5-2 is positioned at the middle lower part of the catalytic oxidation fluidized bed 5-6; the liquid inlet of the clean water atomizing nozzle 5-3 is connected with a clean water main pipe; the liquid inlet of the clean water atomizing nozzle 5-3 is simultaneously connected with a clean oxygen-enriched air main pipe; the clean water atomizing nozzle 5-3 is positioned at the lower part of the catalytic oxidation fluidized bed 5-6; the air inlet of the clean oxygen-enriched air preheater 5-5 is connected with a clean oxygen-enriched air main pipe, and the air outlet of the clean oxygen-enriched air preheater 5-5 is connected with a fluidizing gas inlet at the bottom of the catalytic oxidation fluidized bed 5-6 through a pipeline; the hydrochloric acid atomizing nozzle 5-4 is positioned at the lower part of the catalytic oxidation fluidized bed 5-6; a liquid inlet of the hydrochloric acid atomizing nozzle 5-4 is connected with a liquid outlet of the hydrochloric acid condensation absorption tower 5-8 through a pipeline; the liquid inlets of the hydrochloric acid atomizing nozzles 5-4 are simultaneously connected with a clean oxygen-enriched air main pipe; the catalytic oxidation fluidized bed cyclone separator 5-7 is arranged at the center of the top of the catalytic oxidation fluidized bed 5-6; the gas outlet of the catalytic oxidation fluidized bed cyclone separator 5-7 is connected with the gas inlet of the hydrochloric acid condensation absorption tower 5-8 through a pipeline; the gas outlets of the hydrochloric acid condensation absorption towers 5 to 8 are connected with the gas inlet of the chlorine gas circulating system through a pipeline; the discharge hole in the middle of the catalytic oxidation fluidized bed 5-6 is connected with the feed inlet of the catalytic oxidation fluidized bed discharger 5-9 through a pipeline; the loose air inlet of the catalytic oxidation fluidized bed discharger 5-9 is connected with a clean nitrogen header pipe; the discharge hole of the catalytic oxidation fluidized bed discharger 5-9 is connected with the feed hole of the catalytic oxidation product bin 6-1 through a pipeline;

the discharge hole of the catalytic oxidation product bin 6-1 is connected with the feed hole of the catalytic oxidation product star-shaped feeder 6-2; the discharge hole of the catalytic oxidation product star-shaped feeder 6-2 is connected with the feed inlet of the preheating fluidized bed feeder 7-1 through a pipeline;

the discharge hole of the preheating fluidized bed feeder 7-1 is connected with the feed inlet of the preheating fluidized bed 7-2 through a pipeline; a loose air inlet of the preheating fluidized bed feeder 7-1 is connected with a clean nitrogen header pipe; the preheating fluidized bed cyclone separator 7-4 is arranged at the top center of the preheating fluidized bed 7-2; the gas outlet of the preheating fluidized bed cyclone separator 7-4 is connected with the fuel inlet of the reducing bed gas heater 8-1 through a pipeline; a high-temperature gas inlet of the preheating fluidized bed 7-2 is connected with a gas outlet of the reduction bed cyclone separator 8-3 through a pipeline; the discharge hole at the lower part of the preheating fluidized bed 7-2 is connected with the feed inlet of a discharger 7-3 of the preheating fluidized bed through a pipeline; a loose air inlet of a preheating fluidized bed discharger 7-3 is connected with a clean nitrogen header pipe; the discharge hole of the preheating fluidized bed discharger 7-3 is connected with the feed hole of the reduction fluidized bed 8-2 through a pipeline;

a fluidizing gas inlet of the reduction fluidized bed 8-2 is connected with a high-temperature gas outlet of the reduction bed gas heater 8-1 through a pipeline; the fuel inlet of the reducing bed gas heater 8-1 is connected with a fuel main pipe; a combustion-supporting air inlet of the reducing bed gas heater 8-1 is connected with a compressed air main pipe; a reducing gas inlet of the reducing bed gas heater 8-1 is respectively connected with a clean reducing gas main pipe and a clean nitrogen main pipe; the reduction bed cyclone separator 8-3 is arranged at the top center of the reduction fluidized bed 8-2; a discharge hole at the upper part of the reduction fluidized bed 8-2 is connected with a feed inlet of a reduction bed discharger 8-4 through a pipeline; the loose air inlet of the reduction bed discharger 8-4 is connected with a clean nitrogen header pipe; the discharge hole of the reducing bed discharger 8-4 is connected with the feed hole of the cooling fluidized bed 9-1 through a pipeline;

a cooling gas inlet of the cooling fluidized bed 9-1 is connected with a clean nitrogen header pipe; a vertical baffle is arranged in the cooling fluidized bed 9-1; the cooling fluidized bed cyclone separator 9-2 is arranged at the top center of the cooling fluidized bed 9-1; the gas outlet of the cooling fluidized bed cyclone separator 9-2 is connected with the gas inlet of the tail gas treatment system through a pipeline; the discharge hole of the cooling fluidized bed 9-1 is connected with the feed inlet of a discharger 9-3 of the cooling fluidized bed through a pipeline; a loose air inlet of a discharger 9-3 of the cooling fluidized bed is connected with a clean nitrogen header pipe; the discharge hole of the discharger 9-3 of the cooling fluidized bed is connected with the feed hole of the high-purity low-valence vanadium oxidation material bin 10-1 through a pipeline;

a discharge hole of the high-purity low-valence vanadium oxide material bin 10-1 is connected with a feed hole of the high-purity low-valence vanadium oxide star-shaped feeder 10-2; the discharge hole of the high-purity low-valence vanadium oxide star-shaped feeder 10-2 is connected with the feed inlet of the liquid-solid fluidized bed feeder 11-1 through a pipeline;

a loosening air inlet of the liquid-solid fluidized bed feeder 11-1 is connected with a clean nitrogen header pipe; the discharge port of the liquid-solid fluidized bed feeder 11-1 is connected with the feed port of the liquid-solid fluidized bed 11-2 through a pipeline; an ultrapure water inlet of the liquid-solid fluidized bed 11-2 is connected with an ultrapure water main pipe; a sulfuric acid inlet of the liquid-solid fluidized bed 11-2 is connected with a pure sulfuric acid main pipe; a gas outlet at the top of the liquid-solid fluidized bed 11-2 is connected with a gas inlet of a tail gas treatment system through a pipeline; a liquid outlet of the liquid-solid fluidized bed 11-2 is connected with a high-purity vanadium electrolyte storage tank 11-3 through a pipeline; and a high-purity vanadium electrolyte outlet with a valve is arranged at the bottom of the high-purity vanadium electrolyte storage tank 11-3.

Example 2

A method for preparing high-purity vanadium electrolyte by using an efficient clean chlorination method based on the system in the embodiment 1 comprises the following steps:

industrial vanadium oxide in the industrial vanadium oxidation material bin 1-1 and a carbon source in the carbon source bin 1-3 enter a mixer 1-5 to be mixed through an industrial vanadium oxide star feeder 1-2 and a carbon source star feeder 1-4 respectively; the mixed materials sequentially pass through a mixer star-shaped feeder 1-6 and a boiling chlorination furnace feeder 2-1 to enter a boiling chlorination furnace 2-2; chlorine from a chlorine gas source main pipe and nitrogen from an industrial nitrogen main pipe enter a boiling chlorination furnace 2-2 through a gas inlet at the lower part of the boiling chlorination furnace 2-2, so that industrial-grade vanadium oxide and a carbon source are kept fluidized and are subjected to chemical reaction with the industrial-grade vanadium oxide and the carbon source, and the chlorine and the carbon source jointly act to chlorinate the vanadium oxide and part of impurities, so that chlorination residues and chlorinated flue gas rich in vanadium oxychloride are obtained; vanadium oxychloride slurry from a slurry outlet in the middle of the vanadium oxychloride slurry tank 3-6 is respectively sprayed into the boiling chlorination furnace 2-2 through the first slurry nozzle 2-4 and the second slurry nozzle 2-5, and the temperature in the furnace is adjusted; the chlorination residues are discharged and treated through a residue discharge port at the lower part of the boiling chlorination furnace 2-2 and a chlorination residue discharger 2-6 in sequence; removing dust from the chlorination flue gas through a chlorination furnace cyclone separator 2-3, returning the dust to the boiling chlorination furnace 2-2, and then entering a dust removal tower 3-1;

a slurry nozzle is arranged at the top of the dust removing tower 3-1, and slurry from the bottom of a vanadium oxychloride slurry tank 3-6 and a distillation still 4-2 enters the dust removing tower 3-1 through the slurry nozzle to cool the chlorination flue gas; the generated dust-collecting slag is discharged through a slag discharge port at the lower part of the dust removing tower 3-1 and is sent for treatment; the cooled chlorinated flue gas enters a first-stage leaching tower 3-2 for leaching, and leached slurry is sent to a centrifugal filter 3-5 for treatment; conveying the first-stage leaching tail gas to a second-stage leaching tower 3-3 for leaching, and conveying the leaching slurry to a centrifugal filter 3-5 for treatment; conveying the second-stage leaching tail gas to a third-stage leaching tower for leaching by 3-4, and conveying the leaching slurry to a centrifugal filter for treatment by 3-5; the third-stage leaching tail gas is sent to a tail gas treatment system; feeding the slurry at the bottom of the centrifugal filter 3-5 into a vanadium oxychloride slurry tank 3-6, and feeding the supernatant into a hydrolysis impurity removal kettle 4-1;

feeding the vanadium oxychloride slurry obtained by pre-impurity removal in the hydrolysis impurity removal kettle 4-1 into a distillation kettle 4-2 for distillation, and feeding the distilled gas into a rectifying tower 4-3 for rectification treatment; spraying the concentrated solution generated by distillation into the dust removal tower 3-1 through a nozzle at the top of the dust removal tower 3-1; the high boiling point component at the bottom of the rectifying tower 4-3 enters the distillation kettle 4-2 through a reflux port; after vanadium oxychloride steam is condensed to liquid by a vanadium oxychloride condenser 4-4, part of the vanadium oxychloride steam flows back to a rectifying tower 4-3 through a vanadium oxychloride reflux tank 4-5, and the rest of the vanadium oxychloride steam enters a high-purity vanadium oxychloride storage tank 4-6;

the high-purity vanadium oxychloride in the high-purity vanadium oxychloride storage tank 4-6 is vaporized by a vanadium oxychloride vaporizer 5-1 and then enters a catalytic oxidation fluidized bed 5-6 through a vanadium oxychloride nozzle 5-2; clean water from a clean water main pipe and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter a catalytic oxidation fluidized bed 5-6 through a clean water atomization nozzle 5-3; hydrochloric acid from a hydrochloric acid condensation absorption tower 5-8 and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter a catalytic oxidation fluidized bed 5-6 through a hydrochloric acid atomization nozzle 5-4; the clean oxygen-enriched air from the clean oxygen-enriched air main pipe is preheated by a clean oxygen-enriched air preheater 5-5 and then enters the catalytic oxidation fluidized bed 5-6 through a fluidized gas inlet at the lower part of the catalytic oxidation fluidized bed 5-6; vanadium oxychloride in the catalytic oxidation fluidized beds 5-6 generates vanadium pentoxide powder and flue gas containing hydrogen chloride and chlorine under the catalytic oxidation action of water and oxygen-enriched air; vanadium pentoxide powder enters a catalytic oxidation product bin 6-1 through a catalytic oxidation fluidized bed discharger 5-9; the flue gas containing hydrogen chloride and chlorine is dedusted by a catalytic oxidation fluidized bed cyclone separator 5-7 and then enters a hydrochloric acid condensation absorption tower 5-8, the hydrochloric acid absorbed by condensation returns to a catalytic oxidation fluidized bed 5-6 through a hydrochloric acid atomizing nozzle 5-4, and the rest chlorine is sent to a chlorine circulating system;

vanadium pentoxide powder in the catalytic oxidation product bin 6-1 sequentially enters the preheating fluidized bed 7-2 through the catalytic oxidation product star feeder 6-2 and the preheating fluidized bed feeder 7-1; high-temperature reducing gas from the cyclone separator 8-3 of the reducing bed enters through a fluidizing gas inlet at the lower part of the preheating fluidized bed 7-2, so that vanadium pentoxide powder in the preheating fluidized bed 7-2 is maintained in fluidization, and preheating is completed; the preheated tail gas is dedusted by a preheating fluidized bed cyclone separator 7-4 and then is sent to a reducing bed gas heater 8-1 for combustion; the preheated vanadium pentoxide powder in the preheating fluidized bed 7-2 enters the reduction fluidized bed 8-2 through a discharger 7-3 of the preheating fluidized bed;

heating clean reducing gas and clean nitrogen by a reducing bed gas heater 8-1, and then feeding the heated clean reducing gas and clean nitrogen into a reducing fluidized bed 8-2 to maintain fluidization of vanadium pentoxide powder and enable the vanadium pentoxide powder to carry out reduction reaction to obtain reducing flue gas and low-valence vanadium oxide powder; the reduction flue gas is dedusted by a reduction bed cyclone separator 8-3 and then sent to a preheating fluidized bed 7-2 for heat exchange; the low-valence vanadium oxide enters a cooling fluidized bed 9-1 through a reduction bed discharger 8-4;

clean nitrogen enters through an air inlet at the bottom of the cooling fluidized bed 9-1 to maintain the fluidization of the low-valence vanadium oxide and realize heat exchange; a vertical baffle is arranged in the cooling fluidized bed 9-1; the heat exchange tail gas is sent to a tail gas treatment system after dust is removed by a cooling fluidized bed cyclone separator 9-2; the cooled low-valence vanadium oxide enters a high-purity low-valence vanadium oxidation material bin 10-1 through a cooling fluidized bed discharger 9-3;

high-purity low-valence vanadium oxide in the high-purity low-valence vanadium oxide material bin 10-1 sequentially enters a liquid-solid fluidized bed 11-2 through a high-purity low-valence vanadium oxide star feeder 10-2 and a liquid-solid fluidized bed feeder 11-1, and undergoes a dissolution reaction with ultrapure water from an ultrapure water main pipe and pure sulfuric acid from a pure sulfuric acid main pipe to obtain high-purity vanadium electrolyte and acid gas; and (3) sending the acid gas to a tail gas treatment system, and sending the high-purity vanadium electrolyte to a high-purity vanadium electrolyte storage tank 11-3.

Example 3

In the embodiment, powdery industrial-grade vanadium pentoxide (with a purity of 98.50%) is used as a raw material, and the method described in embodiment 2 is adopted to prepare the high-purity vanadium electrolyte. The treatment capacity of industrial grade vanadium pentoxide is 80kg/h, and the high-purity vanadium electrolyte with the average valence state of 3.0 is prepared by chlorination, dust removal and leaching, vanadium oxychloride purification, catalytic oxidation, fluidized reduction and fluidized bed dissolution.

In a boiling chlorination furnace 2-2, the addition amount of petroleum coke in the chlorination process is 30 percent of the mass of industrial-grade vanadium pentoxide powder, the chlorination operation temperature is 600 ℃, the gas velocity of the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 3.0m/s, and the mole fraction of chlorine in the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 20 percent; the impurity removing agent added in the hydrolysis impurity removing kettle 4-1 is water, and the using amount of the impurity removing agent is 0.00001 percent of the mass of the vanadium oxychloride slurry; in the catalytic oxidation fluidized bed 5-6, the mass of the introduced water vapor is 9.90 percent of that of the vanadium oxychloride in the catalytic oxidation process, the volume fraction of oxygen in the introduced clean oxygen-enriched air is 95 percent, and the catalytic oxidation operation temperature is 130 ℃; in a reduction fluidized bed 8-2, the reduction temperature is 750 ℃, the reduction reaction time is 95min, the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen is 91 percent, the direct yield of vanadium reaches 90 percent, and high-purity vanadium trioxide is obtained; and dissolving high-purity vanadium trioxide in a sulfuric acid solution in the liquid-solid fluidized bed to prepare a high-purity vanadium electrolyte with the average valence of vanadium ions of 3.0, wherein the total content of impurities except effective components is less than 10 ppm.

Example 4

In this embodiment, industrial grade vanadium trioxide (with a purity of 97.50%) is used as a raw material, and the method described in embodiment 2 is used to prepare the high-purity vanadium electrolyte. The treatment capacity of industrial grade vanadium trioxide is 2t/h, and the high-purity vanadium electrolyte with the vanadium equivalent valence state of 4.0 is prepared by chlorination, dust removal and leaching, vanadium oxychloride purification, catalytic oxidation, fluidized reduction and fluidized bed dissolution.

In a boiling chlorination furnace 2-2, the addition amount of metallurgical coke in the chlorination process is 5% of the mass of industrial-grade vanadium pentoxide powder, the chlorination operation temperature is 290 ℃, the gas velocity of the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 0.05m/s, and the mole fraction of chlorine in the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 100%; the impurity removing agent added in the hydrolysis impurity removing kettle 4-1 is aqueous hydrogen chloride solution, and the using amount of the impurity removing agent is 0.1 percent of the mass of the vanadium oxychloride slurry; in the catalytic oxidation fluidized bed 5-6, the mass of the introduced water vapor is 0.01 percent of that of the vanadium oxychloride in the catalytic oxidation process, the volume fraction of oxygen in the introduced clean oxygen-enriched air is 30 percent, and the catalytic oxidation operation temperature is 620 ℃; in a reduction fluidized bed 8-2, the reduction temperature is 300 ℃, the reduction reaction time is 29min, the volume fraction of coal gas in the mixed gas of nitrogen and coal gas is 9 percent, the direct recovery rate of vanadium reaches 90 percent, high-purity vanadium oxide with the equivalent valence of vanadium of 4.0 is obtained, and in a liquid-solid fluidized bed, high-purity vanadium electrolyte with the equivalent valence of vanadium of 4.0 is prepared, except for effective components, the total content of impurities is lower than 5 ppm.

Example 5

In the embodiment, industrial grade vanadium trioxide (with the purity of 98.00%) is used as a raw material to prepare the high-purity vanadium electrolyte. The treatment capacity of industrial grade vanadium trioxide (the purity is 98.00%) is 1t/h, and the high-purity vanadium electrolyte with the vanadium equivalent valence state of 3.5 is prepared through chlorination, dust removal leaching, vanadium oxychloride purification, catalytic oxidation, fluidized reduction and fluidized bed dissolution.

In the boiling chlorination furnace 2-2, the addition amount of the pulverized coal in the chlorination process is 10 percent of the mass of the industrial-grade vanadium pentoxide powder, the chlorination operation temperature is 400 ℃, the gas velocity of the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 0.3m/s, and the mole fraction of the chlorine in the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 50 percent; the impurity removing agent added into the hydrolysis impurity removing kettle 4-1 is a potassium hydroxide aqueous solution, and the using amount of the impurity removing agent is 0.01 percent of the mass of the vanadium oxychloride slurry; in the catalytic oxidation fluidized bed 5-6, the mass of the introduced water vapor is 1 percent of that of the vanadium oxychloride in the catalytic oxidation process, the volume fraction of the oxygen introduced into the clean oxygen-enriched air is 60 percent, and the catalytic oxidation operation temperature is 300 ℃; in a reduction fluidized bed 8-2, the reduction temperature is 500 ℃, the reduction reaction time is 60min, the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen is 50%, the direct recovery rate of vanadium reaches 90%, high-purity low-valence vanadium oxide with the equivalent valence of vanadium of 3.5 is obtained, and the high-purity vanadium electrolyte with the equivalent valence of vanadium of 3.5 is prepared by dissolving in a liquid-solid fluidized bed, wherein except effective components, the total content of impurities is lower than 1 ppm.

The direct yield of vanadium in the above examples refers to the atomic percentage of vanadium in the raw material converted to high purity vanadium suboxides.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A system for preparing high-purity vanadium electrolyte by a high-efficiency clean chlorination method is characterized by comprising a feeding working section (1), a chlorination working section (2), a dedusting and leaching working section (3), a purification working section (4), a catalytic oxidation working section (5), a catalytic oxidation product feeding working section (6), a fluidized bed preheating working section, a reduction roasting working section (8), a cooling fluidized bed working section (9), a high-purity low-valence vanadium oxide feeding working section (10) and a liquid-solid fluidized bed dissolving working section (11);

the feeding working section (1) comprises an industrial-grade vanadium oxide material bin (1-1), an industrial-grade vanadium oxide star-shaped feeder (1-2), a carbon source bin (1-3), a carbon source star-shaped feeder (1-4), a mixer (1-5) and a mixer star-shaped feeder (1-6);

the chlorination working section (2) comprises a boiling chlorination furnace feeder (2-1), a boiling chlorination furnace (2-2), a chlorination furnace cyclone separator (2-3), a first slurry nozzle (2-4), a second slurry nozzle (2-5) and a chlorination residue discharger (2-6);

the dust removal leaching section (3) comprises a dust removal tower (3-1), a first-stage leaching tower (3-2), a second-stage leaching tower (3-3), a third-stage leaching tower (3-4), a centrifugal filter (3-5) and a vanadium oxychloride slurry tank (3-6);

the purification working section (4) comprises a hydrolysis impurity removal kettle (4-1), a distillation kettle (4-2), a rectifying tower (4-3), a vanadium oxytrichloride condenser (4-4), a vanadium oxytrichloride reflux tank (4-5) and a high-purity vanadium oxytrichloride storage tank (4-6);

the catalytic oxidation working section (5) comprises a vanadium oxychloride vaporizer (5-1), a vanadium oxychloride nozzle (5-2), a clean water atomization nozzle (5-3), a hydrochloric acid atomization nozzle (5-4), a clean oxygen-enriched air preheater (5-5), a catalytic oxidation fluidized bed (5-6), a catalytic oxidation fluidized bed cyclone separator (5-7), a hydrochloric acid condensation absorption tower (5-8) and a catalytic oxidation fluidized bed discharger (5-9);

the catalytic oxidation product feeding section (6) comprises a catalytic oxidation product bin (6-1) and a catalytic oxidation product star-shaped feeder (6-2);

the fluidized bed preheating section comprises a preheating fluidized bed feeder (7-1), a preheating fluidized bed (7-2), a preheating fluidized bed discharger (7-3) and a preheating fluidized bed cyclone separator (7-4);

the reduction roasting section (8) comprises a reduction bed gas heater (8-1), a reduction fluidized bed (8-2), a reduction bed cyclone separator (8-3) and a reduction bed discharger (8-4);

the cooling fluidized bed working section (9) comprises a cooling fluidized bed (9-1), a cooling fluidized bed cyclone separator (9-2) and a cooling fluidized bed discharger (9-3);

the high-purity low-valence vanadium oxide feeding working section (10) comprises a high-purity low-valence vanadium oxide material bin (10-1) and a high-purity low-valence vanadium oxide star-shaped feeder (10-2);

the liquid-solid fluidized bed dissolving section (11) comprises a liquid-solid fluidized bed feeder (11-1), a liquid-solid fluidized bed (11-2) and a high-purity vanadium electrolyte storage tank (11-3);

a discharge hole at the bottom of the industrial vanadium oxide material bin (1-1) is connected with a feed hole of the industrial vanadium oxide star-shaped feeder (1-2); a discharge hole at the bottom of the carbon source bin (1-3) is connected with a feed inlet of the carbon source star feeder (1-4); the discharge hole of the industrial grade vanadium oxide star feeder (1-2) and the discharge hole of the carbon source star feeder (1-4) are connected with the feed inlet of the mixer (1-5) through pipelines; a discharge hole at the bottom of the mixer (1-5) is connected with a feed inlet of the mixer star-shaped feeder (1-6); the discharge hole of the mixer star-shaped feeder (1-6) is connected with the feed hole of the boiling chlorination furnace feeder (2-1) through a pipeline;

the discharge hole of the boiling chlorination furnace feeder (2-1) is connected with the feed inlet at the upper part of the boiling chlorination furnace (2-2) through a pipeline; an air inlet at the bottom of the boiling chlorination furnace feeder (2-1) is connected with an industrial nitrogen header pipe; the air inlet at the lower part of the boiling chlorination furnace (2-2) is respectively connected with a chlorine gas source main pipe and an industrial nitrogen main pipe through pipelines; the first slurry nozzle (2-4) is positioned at the upper part of the boiling chlorination furnace (2-2); the feed inlet of the first slurry nozzle (2-4) is connected with the slurry outlet in the middle of the vanadium oxychloride slurry tank (3-6) through a pipeline; the second slurry nozzle (2-5) is positioned at the lower part of the boiling chlorination furnace (2-2); the feed inlet of the second slurry nozzle (2-5) is connected with the slurry outlet in the middle of the vanadium oxychloride slurry tank (3-6) through a pipeline; the chlorination furnace cyclone separator (2-3) is arranged at the center of the top of the boiling chlorination furnace (2-2); an air outlet at the top of the chlorination furnace cyclone separator (2-3) is connected with an air inlet of the dust removal tower (3-1) through a pipeline; a slag discharge port at the lower part of the boiling chlorination furnace (2-2) is connected with a feed inlet of the chlorination residue slag discharger (2-6) through a pipeline; the air inlet at the bottom of the chlorination residue discharger (2-6) is connected with an industrial nitrogen header pipe;

the vanadium oxychloride slurry nozzle at the top of the dust removal tower (3-1) is connected with the outlet at the bottom of the vanadium oxychloride slurry tank (3-6) through a pipeline; the vanadium oxychloride slurry nozzle at the top of the dust removal tower (3-1) is simultaneously connected with the bottom outlet of the distillation kettle (4-2) through a pipeline; the dust removal tower (3-1) comprises a rotary dust removal cylinder provided with a scraper; a slag discharge port with a valve is arranged at the lower part of the dust removing tower (3-1); the gas outlet of the dust removal tower (3-1) is connected with the gas inlet of the first-stage leaching tower (3-2) through a pipeline; the liquid outlet of the first-stage leaching tower (3-2) is connected with the liquid inlet of the centrifugal filter (3-5) through a pipeline; the gas outlet of the first-stage leaching tower (3-2) is connected with the gas inlet of the second-stage leaching tower (3-3) through a pipeline; the liquid outlet of the secondary leaching tower (3-3) is connected with the liquid inlet of the centrifugal filter (3-5) through a pipeline; the air outlet of the second-stage leaching tower (3-3) is connected with the air inlet of the third-stage leaching tower (3-4) through a pipeline; the liquid outlet of the third leaching tower (3-4) is connected with the liquid inlet of the centrifugal filter (3-5) through a pipeline; the gas outlet of the third leaching tower (3-4) is connected with the gas inlet of the tail gas treatment system through a pipeline; the supernatant outlet of the centrifugal filter (3-5) is connected with the liquid inlet of the hydrolysis impurity removal kettle (4-1) through a pipeline; the slurry outlet of the centrifugal filter (3-5) is connected with the slurry inlet of the vanadium oxychloride slurry tank (3-6) through a pipeline;

the top of the hydrolysis impurity removal kettle (4-1) is provided with an impurity removal agent feeding port; the liquid outlet of the hydrolysis impurity removal kettle (4-1) is connected with the liquid inlet of the distillation kettle (4-2) through a pipeline; the gas outlet of the distillation kettle (4-2) is connected with the gas inlet of the rectifying tower (4-3) through a pipeline; a reflux port of the distillation kettle (4-2) is connected with a liquid reflux outlet at the bottom of the rectifying tower (4-3) through a pipeline; a gas outlet at the top of the rectifying tower (4-3) is connected with a gas inlet of the vanadium oxytrichloride condenser (4-4) through a pipeline; the liquid outlet of the vanadium oxychloride condenser (4-4) is connected with the liquid inlet of the vanadium oxychloride reflux tank (4-5) through a pipeline; a reflux port of the vanadium oxytrichloride reflux tank (4-5) is connected with a liquid reflux port at the upper part of the rectifying tower (4-3) through a pipeline; a high-purity vanadium oxychloride liquid outlet of the vanadium oxychloride reflux tank (4-5) is connected with a liquid inlet of the high-purity vanadium oxychloride storage tank (4-6) through a pipeline; a liquid outlet at the lower part of the high-purity vanadium trichloride storage tank (4-6) is connected with a liquid inlet of the vanadium trichloride vaporizer (5-1) through a pipeline;

the air outlet of the vanadium oxytrichloride vaporizer (5-1) is connected with the air inlet of the vanadium oxytrichloride nozzle (5-2) through a pipeline; the vanadium oxytrichloride nozzle (5-2) is positioned at the middle lower part of the catalytic oxidation fluidized bed (5-6); the liquid inlet of the clean water atomizing nozzle (5-3) is connected with a clean water main pipe; the liquid inlet of the clean water atomizing nozzle (5-3) is simultaneously connected with the clean oxygen-enriched air main pipe; the clean water atomization nozzle (5-3) is positioned at the lower part of the catalytic oxidation fluidized bed (5-6); the air inlet of the clean oxygen-enriched air preheater (5-5) is connected with the clean oxygen-enriched air main pipe, and the air outlet of the clean oxygen-enriched air preheater (5-5) is connected with the fluidizing gas inlet at the bottom of the catalytic oxidation fluidized bed (5-6) through a pipeline; the hydrochloric acid atomizing nozzle (5-4) is positioned at the lower part of the catalytic oxidation fluidized bed (5-6); a liquid inlet of the hydrochloric acid atomizing nozzle (5-4) is connected with a liquid outlet of the hydrochloric acid condensing absorption tower (5-8) through a pipeline; the liquid inlet of the hydrochloric acid atomizing nozzle (5-4) is simultaneously connected with the clean oxygen-enriched air main pipe; the catalytic oxidation fluidized bed cyclone separator (5-7) is arranged at the center of the top of the catalytic oxidation fluidized bed (5-6); the gas outlet of the catalytic oxidation fluidized bed cyclone separator (5-7) is connected with the gas inlet of the hydrochloric acid condensation absorption tower (5-8) through a pipeline; the gas outlet of the hydrochloric acid condensation absorption tower (5-8) is connected with the gas inlet of the chlorine gas circulating system through a pipeline; the discharge hole in the middle of the catalytic oxidation fluidized bed (5-6) is connected with the feed inlet of the catalytic oxidation fluidized bed discharger (5-9) through a pipeline; the loose air inlet of the catalytic oxidation fluidized bed discharger (5-9) is connected with a clean nitrogen header pipe; the discharge hole of the catalytic oxidation fluidized bed discharger (5-9) is connected with the feed hole of the catalytic oxidation product bin (6-1) through a pipeline;

the discharge hole of the catalytic oxidation product bin (6-1) is connected with the feed hole of the catalytic oxidation product star feeder (6-2); the discharge hole of the catalytic oxidation product star-shaped feeder (6-2) is connected with the feed inlet of the preheating fluidized bed feeder (7-1) through a pipeline;

the discharge hole of the preheating fluidized bed feeder (7-1) is connected with the feed hole of the preheating fluidized bed (7-2) through a pipeline; the loosening air inlet of the preheating fluidized bed feeder (7-1) is connected with a clean nitrogen header pipe; the preheating fluidized bed cyclone separator (7-4) is arranged at the top center of the preheating fluidized bed (7-2); the gas outlet of the preheating fluidized bed cyclone separator (7-4) is connected with the fuel inlet of the reducing bed gas heater (8-1) through a pipeline; a high-temperature gas inlet of the preheating fluidized bed (7-2) is connected with a gas outlet of the reduction bed cyclone separator (8-3) through a pipeline; the discharge port at the lower part of the preheating fluidized bed (7-2) is connected with the feed inlet of the preheating fluidized bed discharger (7-3) through a pipeline; the loose air inlet of the preheating fluidized bed discharger (7-3) is connected with a clean nitrogen header pipe; the discharge hole of the preheating fluidized bed discharger (7-3) is connected with the feed hole of the reduction fluidized bed (8-2) through a pipeline;

a fluidizing gas inlet of the reduction fluidized bed (8-2) is connected with a high-temperature gas outlet of the reduction bed gas heater (8-1) through a pipeline; the fuel inlet of the reducing bed gas heater (8-1) is connected with a fuel header pipe; a combustion-supporting air inlet of the reducing bed gas heater (8-1) is connected with a compressed air main pipe; a reducing gas inlet of the reducing bed gas heater (8-1) is respectively connected with a clean reducing gas main pipe and a clean nitrogen main pipe; the reduction bed cyclone separator (8-3) is arranged at the top center of the reduction fluidized bed (8-2); a discharge hole at the upper part of the reduction fluidized bed (8-2) is connected with a feed hole of the reduction bed discharger (8-4) through a pipeline; the loosening air inlet of the reduction bed discharger (8-4) is connected with a clean nitrogen header pipe; the discharge hole of the reduction bed discharger (8-4) is connected with the feed hole of the cooling fluidized bed (9-1) through a pipeline;

a cooling gas inlet of the cooling fluidized bed (9-1) is connected with a clean nitrogen header pipe; a vertical baffle is arranged in the cooling fluidized bed (9-1); the cooling fluidized bed cyclone separator (9-2) is arranged at the top center of the cooling fluidized bed (9-1); the gas outlet of the cooling fluidized bed cyclone separator (9-2) is connected with the gas inlet of the tail gas treatment system through a pipeline; the discharge hole of the cooling fluidized bed (9-1) is connected with the feed hole of the discharger (9-3) of the cooling fluidized bed through a pipeline; a loose air inlet of the cooling fluidized bed discharger (9-3) is connected with a clean nitrogen header pipe; the discharge hole of the cooling fluidized bed discharger (9-3) is connected with the feed hole of the high-purity low-valence vanadium oxidation material bin (10-1) through a pipeline;

the discharge hole of the high-purity low-valence vanadium oxide material bin (10-1) is connected with the feed hole of the high-purity low-valence vanadium oxide star-shaped feeder (10-2); the discharge hole of the high-purity low-valence vanadium oxide star-shaped feeder (10-2) is connected with the feed hole of the liquid-solid fluidized bed feeder (11-1) through a pipeline;

a loosening air inlet of the liquid-solid fluidized bed feeder (11-1) is connected with a clean nitrogen header pipe; the discharge port of the liquid-solid fluidized bed feeder (11-1) is connected with the feed port of the liquid-solid fluidized bed (11-2) through a pipeline; an ultrapure water inlet of the liquid-solid fluidized bed (11-2) is connected with an ultrapure water main pipe; the sulfuric acid inlet of the liquid-solid fluidized bed (11-2) is connected with a pure sulfuric acid main pipe; a gas outlet at the top of the liquid-solid fluidized bed (11-2) is connected with a gas inlet of the tail gas treatment system through a pipeline; the liquid outlet of the liquid-solid fluidized bed (11-2) is connected with the high-purity vanadium electrolyte storage tank (11-3) through a pipeline; a high-purity vanadium electrolyte outlet with a valve is arranged at the bottom of the high-purity vanadium electrolyte storage tank (11-3);

the low-valence vanadium oxide in the high-purity low-valence vanadium oxide refers to vanadium oxide with the average valence of vanadium of 3.0-4.0, and the high purity refers to the purity of the low-valence vanadium oxide of more than 4N;

the high-temperature gas is gas with the temperature of more than 300 ℃.

2. The method for preparing the high-purity vanadium electrolyte by using the system for preparing the high-purity vanadium electrolyte by using the high-efficiency clean chlorination method as claimed in claim 1 comprises the following steps:

industrial vanadium oxide in the industrial vanadium oxidation material bin (1-1) and a carbon source in the carbon source bin (1-3) simultaneously enter the mixer (1-5) to be mixed through the industrial vanadium oxide star feeder (1-2) and the carbon source star feeder (1-4) respectively; the mixed materials sequentially pass through the mixer star-shaped feeder (1-6) and the boiling chlorination furnace feeder (2-1) to enter the boiling chlorination furnace (2-2); chlorine from a chlorine gas source main pipe and nitrogen from an industrial nitrogen main pipe enter the boiling chlorination furnace (2-2) through a gas inlet at the lower part of the boiling chlorination furnace (2-2), so that industrial-grade vanadium oxide and a carbon source are kept fluidized and are subjected to chemical reaction with the industrial-grade vanadium oxide and the carbon source, and the chlorine and the carbon source jointly act to chlorinate the vanadium oxide and part of impurities, so that chlorination residues and chlorination flue gas containing vanadium oxychloride are obtained; vanadium oxychloride slurry from a slurry outlet in the middle of the vanadium oxychloride slurry tank (3-6) is respectively sprayed into the boiling chlorination furnace (2-2) through the first slurry nozzle (2-4) and the second slurry nozzle (2-5), and the temperature in the furnace is adjusted; the chlorination residues are discharged and treated through a residue discharge port at the lower part of the boiling chlorination furnace (2-2) and the chlorination residue discharger (2-6) in sequence; the chlorination flue gas is subjected to dust removal through the chlorination furnace cyclone separator (2-3) and falls back to the boiling chlorination furnace (2-2), and then enters the dust removal tower (3-1);

a slurry nozzle is arranged at the top of the dust removing tower (3-1), and slurry from the vanadium oxychloride slurry tank (3-6) and the bottom of the distillation kettle (4-2) enters the dust removing tower (3-1) through the slurry nozzle to cool the chlorination flue gas; the generated dust-collecting slag is discharged through a slag discharge port at the lower part of the dust-removing tower (3-1) and is sent for treatment; the cooled chlorinated flue gas enters the first-stage leaching tower (3-2) for leaching, and leaching slurry is sent to the centrifugal filter (3-5) for treatment; sending the first-stage leaching tail gas to the second-stage leaching tower (3-3) for leaching, and sending leaching slurry to the centrifugal filter (3-5) for treatment; conveying the second-stage leaching tail gas to the third-stage leaching tower (3-4) for leaching, and conveying the leaching slurry to the centrifugal filter (3-5) for treatment; the third-stage leaching tail gas is sent to a tail gas treatment system; slurry at the bottom of the centrifugal filter (3-5) is sent to the vanadium oxychloride slurry tank (3-6), and supernatant is sent to the hydrolysis impurity removal kettle (4-1);

feeding vanadium oxychloride slurry obtained by pre-impurity removal in the hydrolysis impurity removal kettle (4-1) into the distillation kettle (4-2) for distillation, and feeding the distilled gas into the rectifying tower (4-3) for rectification treatment; spraying the concentrated solution generated by distillation into the dust removing tower (3-1) through a nozzle at the top of the dust removing tower (3-1); the high boiling point component at the bottom of the rectifying tower (4-3) enters the distillation kettle (4-2) through a reflux port; after the vanadium oxychloride steam is condensed to liquid by the vanadium oxychloride condenser (4-4), part of the vanadium oxychloride steam reflows to the rectifying tower (4-3) by the vanadium oxychloride reflowing tank (4-5), and the rest of the vanadium oxychloride steam enters the high-purity vanadium oxychloride storage tank (4-6);

the high-purity vanadium oxychloride in the high-purity vanadium oxychloride storage tank (4-6) is vaporized by the vanadium oxychloride vaporizer (5-1) and then enters the catalytic oxidation fluidized bed (5-6) through the vanadium oxychloride nozzle (5-2); clean water from a clean water main pipe and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter the catalytic oxidation fluidized bed (5-6) through the clean water atomization nozzle (5-3); hydrochloric acid from the hydrochloric acid condensation absorption tower (5-8) and clean oxygen-enriched air from a clean oxygen-enriched air main pipe enter the catalytic oxidation fluidized bed (5-6) through the hydrochloric acid atomization nozzle (5-4); the clean oxygen-enriched air from the clean oxygen-enriched air main pipe is preheated by the clean oxygen-enriched air preheater (5-5) and then enters the catalytic oxidation fluidized bed (5-6) through a fluidizing gas inlet at the lower part of the catalytic oxidation fluidized bed (5-6); vanadium oxychloride in the catalytic oxidation fluidized bed (5-6) is subjected to catalytic oxidation by water and oxygen-enriched air to obtain vanadium pentoxide powder and flue gas containing hydrogen chloride and chlorine; vanadium pentoxide powder enters the catalytic oxidation product bin (6-1) through the catalytic oxidation fluidized bed discharger (5-9); flue gas containing hydrogen chloride and chlorine is dedusted by the catalytic oxidation fluidized bed cyclone separator (5-7) and then enters the hydrochloric acid condensation absorption tower (5-8), the hydrochloric acid absorbed by condensation returns to the catalytic oxidation fluidized bed (5-6) through the hydrochloric acid atomizing nozzle (5-4), and the rest chlorine is sent to a chlorine circulating system;

vanadium pentoxide powder in the catalytic oxidation product bin (6-1) sequentially passes through the catalytic oxidation product star feeder (6-2) and the preheating fluidized bed feeder (7-1) and enters the preheating fluidized bed (7-2); high-temperature reducing gas from the cyclone separator (8-3) of the reducing bed enters through a fluidizing gas inlet at the lower part of the preheating fluidized bed (7-2), so that vanadium pentoxide powder in the preheating fluidized bed (7-2) is maintained in fluidization, and preheating is completed; the preheated tail gas is delivered to the gas heater (8-1) of the reducing bed for combustion after dust is removed from the preheated tail gas through the preheated fluidized bed cyclone separator (7-4); vanadium pentoxide powder preheated in the preheating fluidized bed (7-2) enters the reduction fluidized bed (8-2) through a discharger (7-3) of the preheating fluidized bed;

clean reducing gas and clean nitrogen enter the reduction fluidized bed (8-2) after being heated by the reduction bed gas heater (8-1) to maintain fluidization of vanadium pentoxide powder and enable the vanadium pentoxide powder to carry out reduction reaction, and reduction flue gas and low-valence vanadium oxide are obtained; the reduction flue gas is subjected to dust removal through the reduction bed cyclone separator (8-3) and then is sent into the preheating fluidized bed (7-2) for heat exchange; the low-valence vanadium oxide enters the cooling fluidized bed (9-1) through the reduction bed discharger (8-4);

clean nitrogen enters through an air inlet at the bottom of the cooling fluidized bed (9-1) to maintain fluidization of the low-valence vanadium oxide and realize heat exchange; a vertical baffle is arranged in the cooling fluidized bed (9-1); the heat exchange tail gas is sent to a tail gas treatment system after dust is removed by the cooling fluidized bed cyclone separator (9-2); the cooled low-valence vanadium oxide enters the high-purity low-valence vanadium oxidation material bin (10-1) through the cooling fluidized bed discharger (9-3);

high-purity low-valence vanadium oxide in the high-purity low-valence vanadium oxide material bin (10-1) sequentially enters the liquid-solid fluidized bed (11-2) through the high-purity low-valence vanadium oxide star feeder (10-2) and the liquid-solid fluidized bed feeder (11-1) and is subjected to dissolution reaction with ultrapure water from an ultrapure water main pipe and pure sulfuric acid from a pure sulfuric acid main pipe to obtain high-purity vanadium electrolyte and acid gas; the acid gas is sent to a tail gas treatment system, and the high-purity vanadium electrolyte is sent to a high-purity vanadium electrolyte storage tank (11-3);

3. The method for preparing the high-purity vanadium electrolyte by the efficient clean chlorination process according to claim 2, wherein the industrial-grade vanadium oxide in the industrial-grade vanadium oxidation material bin (1-1) is any one or a combination of at least two of industrial-grade vanadium trioxide, industrial-grade vanadium tetraoxide and industrial-grade vanadium pentoxide; the carbon source in the carbon source bin (1-3) is any one or a combination of at least two of activated carbon, metallurgical coke, petroleum coke or coal powder; the addition amount of the carbon source is 5-30% of the mass of the industrial-grade vanadium oxide.

4. The method for preparing the high-purity vanadium electrolyte by the efficient clean chlorination process according to claim 2, wherein the chlorination operation temperature in the boiling chlorination furnace (2-2) is 290-600 ℃, the gas velocity of the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 0.05-3.00 m/s, and the mole fraction of chlorine in the mixed gas of chlorine and nitrogen entering the boiling chlorination furnace 2-2 is 20-100%.

5. The method for preparing high-purity vanadium electrolyte according to the high-efficiency clean chlorination process of claim 2, characterized in that, in the boiling chlorination furnace (2-2), the impurities undergoing chlorination are mainly: the mass of the impurities subjected to chlorination accounts for 20-50% of the total mass of the impurities.

6. The method for preparing the high-purity vanadium electrolyte by the high-efficiency clean chlorination method according to claim 2, wherein the pre-impurity removal in the hydrolysis impurity removal kettle (4-1) is to remove impurities titanium and silicon by a selective hydrolysis method, the impurity removal agent is water or an aqueous solution, and the amount of the impurity removal agent is 0.00001-0.1% of the mass of the vanadium oxychloride slurry.

7. The method for preparing the high-purity vanadium electrolyte by the high-efficiency clean chlorination method according to claim 2, wherein in the catalytic oxidation fluidized bed (5-6), the water vapor generated by a clean water atomization nozzle (5-3) is 0.01-9.90% of the mass of vanadium oxychloride, the volume fraction of oxygen in the introduced clean oxygen-enriched air is 30-95%, and the catalytic oxidation operation temperature is 130-620 ℃.

8. The method for preparing the high-purity vanadium electrolyte by the high-efficiency clean chlorination method according to claim 2, wherein the clean reducing gas introduced into the reducing bed gas heater (8-1) is selected from any one or a combination of at least two of hydrogen, ammonia, electric furnace gas, converter gas, blast furnace gas, coke oven gas and gas generator gas.

9. The method for preparing the high-purity vanadium electrolyte by the efficient clean chlorination method according to claim 2, wherein in a reduction fluidized bed (8-2), the reduction operation temperature is 300-750 ℃, the volume fraction of the reduction gas in the introduced mixed gas of nitrogen and the reduction gas is 9-91%, and the reduction reaction time is 29-95 min.

10. The method for preparing the high-purity vanadium electrolyte according to claim 2, wherein the equivalent valence of vanadium ions in the high-purity vanadium electrolyte is 3.0-4.0.