WO2016119722A1 - 一种提纯制备高纯五氧化二钒粉体的系统及方法 - Google Patents

一种提纯制备高纯五氧化二钒粉体的系统及方法 Download PDF

Info

Publication number
WO2016119722A1
WO2016119722A1 PCT/CN2016/072524 CN2016072524W WO2016119722A1 WO 2016119722 A1 WO2016119722 A1 WO 2016119722A1 CN 2016072524 W CN2016072524 W CN 2016072524W WO 2016119722 A1 WO2016119722 A1 WO 2016119722A1
Authority
WO
WIPO (PCT)
Prior art keywords
bed
gas
vanadium
ammonium
pipe
Prior art date
Application number
PCT/CN2016/072524
Other languages
English (en)
French (fr)
Inventor
朱庆山
杨海涛
范川林
牟文恒
刘吉斌
王存虎
班琦勋
Original Assignee
中国科学院过程工程研究所
北京中凯宏德科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院过程工程研究所, 北京中凯宏德科技有限公司 filed Critical 中国科学院过程工程研究所
Priority to AU2016212456A priority Critical patent/AU2016212456B2/en
Priority to CA2973518A priority patent/CA2973518C/en
Priority to BR112017015812-4A priority patent/BR112017015812A2/zh
Priority to NZ733888A priority patent/NZ733888A/en
Priority to JP2017558611A priority patent/JP6383118B2/ja
Priority to RU2017130367A priority patent/RU2665520C1/ru
Priority to US15/547,068 priority patent/US10125024B2/en
Priority to EP16742784.8A priority patent/EP3252014B1/en
Publication of WO2016119722A1 publication Critical patent/WO2016119722A1/zh
Priority to ZA2017/04633A priority patent/ZA201704633B/en
Priority to PH12017550061A priority patent/PH12017550061A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71—Feed mechanisms
    • B01F35/717—Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/7173—Feed mechanisms characterised by the means for feeding the components to the mixer using gravity, e.g. from a hopper
    • B01F35/71731—Feed mechanisms characterised by the means for feeding the components to the mixer using gravity, e.g. from a hopper using a hopper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • B01J6/004—Calcining using hot gas streams in which the material is moved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L5/00—Gas handling apparatus
    • B01L5/04—Gas washing apparatus, e.g. by bubbling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/04—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention belongs to the field of chemical industry and material, and particularly relates to a system and a method for purifying and preparing high-purity vanadium pentoxide powder.
  • Vanadium pentoxide is one of the important industrial vanadium products, widely used in the production of alloy additives such as vanadium iron and vanadium nitride, as well as catalysts, colorants, and hard alloy additives. With the continuous development of new energy technologies, the battery industry is increasingly demanding high-purity vanadium pentoxide (purity of more than 3N5), including all-vanadium flow batteries (VRB) with good large-scale energy storage performance and vanadium for electric vehicles.
  • the acid salt is a lithium ion battery or the like.
  • the vanadium solution is usually obtained by leaching a vanadium solution or a vanadium-rich material (such as ammonium polyvanadate, ammonium metavanadate, industrial grade vanadium pentoxide, etc.), and is purified by chemical precipitation or (and) solvent extraction/ion.
  • a vanadium-rich material such as ammonium polyvanadate, ammonium metavanadate, industrial grade vanadium pentoxide, etc.
  • the impurity removal process parameters are closely related to the impurity content of the raw materials, so the adaptability to the raw materials is poor; the calcium salt, magnesium salt purifying agent or extractant used in the purification process, the acid-base reagent, and the ammonium salt for vanadium precipitation are also It is easy to introduce impurities.
  • it is generally required to use an expensive reagent with a high purity, so that the cost is too high, the scale cannot be produced, and the purity of the product is difficult to be stabilized at 3N5 or more.
  • the related institution also proposes to adopt the repeated precipitation method to purify and remove the vanadium solution, that is, to utilize the ammonium salt precipitation property of the vanadium-containing solution to selectively select vanadium.
  • the raw material chlorination-rectification purification-subsequent treatment is a common preparation process for high-purity materials, such as high purity. Silicon (polysilicon), high purity silica, and the like.
  • vanadium chloride vanadium oxychloride vanadium has a large difference from the boiling points of common impurities such as iron, calcium, magnesium, aluminum, sodium, potassium, etc., it is easy to obtain high purity vanadium oxychloride by rectification, and from high purity three High-purity vanadium pentoxide can be prepared by hydrolysis of vanadium oxychloride by hydrolysis and precipitation of ammonium salts, followed by calcination. Therefore, the preparation of high-purity vanadium pentoxide by the chlorination method has a great advantage in principle.
  • the patent has the following deficiencies: (1) Similar to the aforementioned Iowa State University study, the patent actually only gives the principle of chlorination, lacking specific operational solutions, such as chlorination including both boiling chlorine And include molten salt chlorination, and molten salt chlorination and boiling chlorination are completely different chlorination methods; for example, for chlorination reactors, "rotary kiln, fluidized furnace, boiling furnace, shaft furnace, Reactors such as multi-hearth furnaces actually cover almost all common mainstream reactors in the metallurgical industry, but different reactors have very different requirements for raw materials. Shaft furnaces can only handle "coarse" particles larger than 8 mm.
  • fine particles need to be treated with pellets and pre-sintering, while boiling chlorination is generally suitable for processing fine particles, so for a specific vanadium raw material, it cannot be directly applied to rotary kiln, fluidized furnace, boiling furnace, shaft furnace, and more.
  • the reactor such as a crucible furnace; and the "fluidizer” and the “boiling furnace” are essentially the same, but the name is different; thus, it can be seen that the operation modes and conditions of these reactors are very different.
  • vanadium raw material chlorination technology still has the following two problems: (1) vanadium raw material chlorination roasting is a strong exothermic process, and the heat generated by the chlorination reaction can satisfy the solid and gas. In addition to the preheating of the reaction material, it is still necessary to remove the heat through the furnace wall to stabilize the chlorination temperature. Therefore, the solid and the gas usually enter the reactor at a near room temperature, and the chlorination reaction generates heat to preheat before participating in the reaction.
  • the local reaction efficiency of the chlorination reactor is too low; (2) due to the need to remove the heat generated by the chlorination reaction by a large amount of heat dissipation to maintain the operating temperature, the operating conditions and environmental climate changes are liable to cause chlorination temperature fluctuations, resulting in chlorination selection. Reduced sex and efficiency require a reasonable heat balance supply and temperature regulation. Therefore, it is necessary to provide a reasonable heat supply and temperature control to effectively increase the chlorination efficiency and obtain a stable chlorination temperature to ensure the selectivity of chlorination to effectively suppress the chlorination of impurities.
  • the regulation of the chlorination process the improvement of the direct yield of vanadium, the avoidance of a large amount of ammonia nitrogen wastewater, and the improvement of the vanadium pentoxide purification efficiency are the techniques for improving the purity of vanadium pentoxide by chlorination.
  • the present invention provides a system and method for purifying and preparing high-purity vanadium pentoxide powder to ensure good selectivity of low-temperature chlorination, avoiding generation of a large amount of ammonia-nitrogen wastewater, and reducing production of high-purity vanadium pentoxide. Energy consumption and operating costs.
  • the present invention adopts the following technical solutions:
  • the system for purifying and preparing high-purity vanadium pentoxide powder of the invention comprises the feeding device 1, the low-temperature chlorination fluidized bed 2, the rectification and purification device 3, the gas-vaporized ammonium fluidized bed 4, the ammonium metavanadate Feeding device 5, calcining fluidized bed 6, exhaust gas leaching absorber 7, induced draft fan 8 and chimney 9;
  • the feeding device 1 comprises an industrial grade vanadium pentoxide silo 1-1, an industrial grade vanadium pentoxide screw feeder 1-2, a carbon powder silo 1-3 and a carbon powder screw feeder 1-4;
  • the low temperature chlorination fluidized bed 2 comprises a chlorination bed feeder 2-1, a chlorinated fluidized bed main body 2-2, a chlorinated bed cyclone 2-3, a flue gas heat exchanger 2-4, a smoke Gas condenser 2-5, chlorinated bed acid sealed tank 2-6 and chlorination Bed spiral slag remover 2-7;
  • the rectification and purification device 3 includes a distillation still 3-1, a rectification column 3-2, a distillate condenser 3-3, a reflux liquid collection tank 3-4, a silicon-containing vanadium oxychloride vanadium storage tank 3-5, Distillation section acid sealing tank 3-6, high purity vanadium oxychloride vanadium condenser 3-7 and high purity vanadium oxychloride vanadium storage tank 3-8;
  • the gas phase ammonium chloride fluidized bed 4 comprises an ammonium bed air purifier 4-1, an ammonium bed gas heater 4-2, a vanadium oxychloride nozzle 4-3, a gas phase ammonium chloride fluidized bed body 4-4, Ammonium bed cyclone 4-5 and ammonium bed discharger 4-6;
  • the ammonium metavanadate feeding device 5 comprises ammonium metavanadate silo 5-1 and ammonium metavanadate screw feeder 5-2;
  • the calcined fluidized bed 6 comprises a calcined bed air purifier 6-1, a calcined bed gas heater 6-2, a calcined bed feeder 6-3, a calcined fluidized bed main body 6-4, a calcined bed cyclone 6 -5 and high purity vanadium pentoxide silo 6-6;
  • the outlet of the bottom of the industrial grade vanadium pentoxide silo 1-1 is connected to the inlet of the industrial grade vanadium pentoxide screw feeder 1-2; the bottom of the carbon powder silo 1-3
  • the discharge port is connected to the feed port of the carbon powder screw feeder 1-4; the discharge port of the industrial grade vanadium pentoxide screw feeder 1-2, the carbon powder screw feeder 1-
  • the discharge ports of 4 are connected to the feed port of the chlorination bed feeder 2-1 through a pipe;
  • the discharge port of the chlorination bed feeder 2-1 is connected to the inlet of the upper portion of the chlorinated fluidized bed main body 2-2 through a pipe; the bottom of the chlorination bed feeder 2-1
  • the inlet port is connected to the nitrogen gas source manifold through a pipe;
  • the chlorination bed cyclone separator 2-3 is disposed at the top center of the enlarged section of the chlorination fluidized bed main body 2-2;
  • the chlorination bed cyclone separation The gas outlet at the top of the 2-3 is connected to the hot flue gas inlet of the flue gas heat exchanger 2-4 through a pipe; the cold flue gas outlet of the flue gas heat exchanger 2-4 passes through the pipe and the smoke a gas inlet of the gas condenser 2-5 is connected;
  • a gas outlet of the flue gas condenser 2-5 is connected to a gas inlet of the chlorinated bed acid sealing tank 2-6 through a pipe;
  • the chlorinated bed acid The gas outlet of the sealing tank 2-6 is connected
  • the liquid outlet at the bottom of the flue gas condenser 2-5 is connected to the feed port of the rectification column 3-2 through a pipe; the vapor outlet of the distillation still 3-1 passes through the pipe and the rectification column 3 a vapor inlet of -2 is connected; a reflux port of the distillation pot 3-1 is connected to a liquid reflux outlet at the bottom of the rectification column 3-2 through a pipe;
  • the gas outlet at the top of the rectification column 3-2 is connected to the gas inlet of the distillate condenser 3-3 through a conduit; the liquid outlet of the distillate condenser 3-3 is passed through the conduit and the reflux a liquid inlet of the liquid collection tank 3-4 is connected; a reflux liquid outlet of the reflux liquid collection tank 3-4 is connected to a reflux liquid inlet at the top of the rectification column 3-2 through a conduit; the reflux liquid collection tank
  • the discharge opening of 3-4 is connected to the inlet of the silicon-containing vanadium oxychloride vanadium storage tank
  • the inlet of the ammonium bed air purifier 4-1 is connected to the compressed air manifold through a pipeline; the outlet of the ammonium bed air purifier 4-1 is separately connected to the ammonium bed gas heater through a pipeline
  • the inlet of 4-2, the gas inlet of vanadium oxychloride nozzle 4-3 and the inlet of the bottom of the ammonium bed discharger 4-6 are connected; the inlet of the ammonium bed gas heater 4-2
  • the gas port is connected to the ultrapure water and the purified liquid ammonia main pipe through a pipeline; the combustion air inlet and the fuel inlet of the burner of the ammonium bed gas heater 4-2 are respectively connected to the compressed air main pipe and the fuel main pipe through the pipeline;
  • the gas outlet of the ammonium bed gas heater 4-2 is connected to the gas inlet of the bottom of the gas phase ammonium chloride fluidized bed main body 4-4 through a pipe; the high purity vanadium oxychloride vanadium storage tank 3-8 The liquid outlet is connected to the
  • the discharge port at the bottom of the ammonium metavanadate silo 5-1 is connected to the feed port of the ammonium metavanadate screw feeder 5-2; the row of the ammonium metavanadate screw feeder 5-2
  • the feed port is connected to the feed port of the calcined bed feeder 6-3 through a pipe through a pipe;
  • the intake port of the calcining bed air purifier 6-1 is connected to the compressed air manifold through a pipe; the gas outlet of the calcining bed air purifier 6-1 is respectively connected to the calcined bed gas heater 6-2 through a pipe
  • the air inlet is connected to the air inlet at the bottom of the calcined bed feeder 6-3; the combustion air inlet and the fuel inlet of the calcining bed gas heater 6-2 are respectively passed through the pipeline and the compressed air main pipe and the fuel main pipe Connected; the gas outlet of the calcined bed gas heater 6-2 passes through the pipe and the bottom of the calcined fluidized bed main body 6-4
  • the gas discharge port is connected; the discharge port of the calcined bed feeder 6-3 is connected to the feed port of the lower portion of the calcined bed fluidized bed main body 6-4 through a pipe; the calcined fluidized bed main body 6-4
  • the top air outlet is connected to the inlet of the calcining bed cyclone 6-5 through
  • the gas outlet of the exhaust gas rinsing absorber 7 is connected to the gas inlet of the draft fan 8 through a pipe; the gas outlet of the draft fan 8 is connected to the gas inlet at the bottom of the chimney 9 through a pipe.
  • the method for purifying and preparing high-purity vanadium pentoxide powder based on the above system of the present invention comprises the following steps:
  • the industrial grade vanadium pentoxide powder in the industrial grade vanadium pentoxide silo 1-1 and the carbon powder of the carbon powder silo 1-3 are respectively passed through the industrial grade vanadium pentoxide spiral feeder 1 -2 and the carbon powder screw feeder 1-4 simultaneously enter the chlorination bed feeder 2-1 and then enter the chlorination fluidized bed main body 2-2; chlorine gas and nitrogen gas from the chlorine gas source main pipe
  • the nitrogen of the gas source main pipe and the air of the compressed air main pipe are preheated by heat exchange between the flue gas heat exchanger 2-4 and the chlorinated flue gas, and then enter the chlorinated fluidized bed main body 2-2 to make vanadium pentoxide.
  • the powder material such as carbon powder maintains fluidization and chemical reaction with it.
  • the air causes some of the carbon powder to burn to provide heat to maintain the fluidized bed temperature.
  • the chlorine gas and the carbon powder work together to chlorinate vanadium pentoxide and a small amount of impurities.
  • the crude vanadium oxychloride vapor formed by the flue gas condenser 2-5 enters the rectification column 3-2 and the distillation still 3-1, and is subjected to a rectification operation to obtain a vanadium-rich scrap rich in high-boiling impurities.
  • the vanadium-rich waste is used for subsequent recovery of vanadium
  • the silicon-containing vanadium oxychloride vapor is passed through the distillate condenser 3-3 After condensing to the liquid, part of the reflux liquid collection tank 3-4 is refluxed to the rectification column 3-2, and the rest is introduced into the silicon-containing vanadium oxychloride vanadium storage tank 3-5; the silicon-containing vanadium oxychloride vanadium storage
  • the spent gas generated in the tank 3-5 is sent to the exhaust gas leaching absorber 7 through the acid sealing tank 3-6 of the rectifying section, and the silicon-containing vanadium oxychloride can be used for catalysis and other chemical fields;
  • the vanadium oxychloride vapor is condensed into the liquid through the high-purity vanadium oxychloride condenser
  • the high purity vanadium oxychloride vanadium of the high purity vanadium oxychloride vanadium storage tank 3-8 is produced by the vanadium oxychloride vanadium nozzle 4-3
  • Purified air from the ammonium bed air purifier 4-1 is loaded into the gas phase ammonium chloride fluidized bed main body 4-4; ultrapure water, purified liquid ammonia and purified air are passed through the ammonium bed gas heater 4 -2 is preheated and sent to the gas phase ammonium chloride fluidized bed main body 4-4 to maintain fluidization of the powder in the bed, and hydrolyze and ammoniumlate vanadium oxychloride to form vanadium oxide containing ammonium chloride.
  • ammonium acid powder, the ammonium ammonium metaphosphate-containing ammonium metavanadate powder is discharged into the ammonium metavanadate silo 5-1 through the ammonium bed discharger 4-6, and the ammonia is produced.
  • the ammonium fluoride is removed from the dust by the ammonium bed cyclone 4-5 and sent to the tail gas treatment unit for treatment;
  • the ammonium chloride-containing ammonium metavanadate powder in the ammonium metavanadate silo 5-1 is sequentially passed through the ammonium metavanadate screw feeder 5-2 and the calcined bed feeder 6-3. Calcining the fluidized bed main body 6-4; the compressed air is sequentially preheated by the calcining bed air purifier 6-1 and the calcined bed gas heater 6-2, and then introduced into the calcined fluidized bed main body 6-4. The powder in the bed is maintained fluidized, and the ammonium meta-vanadate material containing ammonium chloride is thermally decomposed to obtain a high-purity vanadium pentoxide powder product, and the upper row of the fluidized bed main body 6-4 is calcined.
  • the feed port enters the high-purity vanadium pentoxide bin 6-6; the calcined flue gas generated by the calcination decomposition enters the calcining bed cyclone separator 6-5, and the ammonium chloride is separated and the dust is removed to be sent to the tail gas treatment unit. Processing; the ammonium chloride powder collected by the calcined bed cyclone 6-5 is sent to an ammonium chloride silo;
  • the gas discharged from the exhaust gas eluting absorber 7 after being absorbed by the alkali solution is sent to the chimney 9 through the induced draft fan 8 and then emptied.
  • One of the features of the present invention is that in the chlorinated fluidized bed main body 2-2, the chlorination process carbon powder is added in an amount of 10% to 20% by mass of the industrial grade vanadium pentoxide powder, and chlorinated.
  • the operating temperature is 300-500 ° C, and the average residence time of the powder is 30-80 min.
  • the second feature of the present invention is that in the rectification column 3-2, the number of trays in the rectification operation rectification section is 5 to 10, and the number of trays in the stripping section is 10 to 20; During the distillation operation, the reflux ratio (ie, the ratio of the reflux flow at the top of the column to the discharge amount) is maintained at 15 to 40.
  • the third feature of the present invention is that, in the gas phase ammonium chloride fluidized bed main body 4-4, ammonium metavanadate is prepared by gas phase ammonium crystallization of high-purity vanadium oxychloride, and the operating temperature of the gas phase ammonium is 130-250. °C, the molar ratio of water vapor to ammonia is 0.5 to 0.8, and the molar ratio of ammonia to vanadium oxychloride is 3.5 to 4.5.
  • the fourth feature of the present invention is that in the calcined fluidized bed main body 6-4, thermal decomposition of ammonium ammonium metaphosphate containing ammonium metavanadate is achieved by fluidized calcination, the calcination operation temperature is 400 to 650 ° C, powder The average residence time of the material is 60-180 min.
  • the purity of the high-purity vanadium pentoxide powder obtained by the invention is above 4N. Compared with the prior art, the present invention has the following outstanding advantages:
  • the chlorination gas is preheated by the heat exchange between the chlorinated gas and the chlorinated flue gas while cooling the flue gas. Heat, the temperature distribution of the chlorination reactor is more uniform, and the low-temperature chlorination efficiency of the vanadium raw material is effectively improved;
  • a part of the carbon powder is burned by appropriate amount of air to achieve heat balance supply and temperature regulation of the chlorination process, stabilize the chlorination operation temperature, improve the chlorination reaction efficiency and ensure good selectivity of chlorination, and avoid the formation of tetrachlorination.
  • side reactions such as vanadium;
  • Ammonium metavanadate containing ammonium chloride is fluidized and calcined, ammonium metavanadate is decomposed to high-purity vanadium pentoxide product, and ammonium chloride is also decomposed and discharged with flue gas. After cooling, ammonium chloride can be obtained.
  • the product effectively realizes the preparation of high-purity products and the recovery of ammonium chloride.
  • the invention has the advantages of strong adaptability of raw materials, good selectivity of low-temperature chlorination, non-polluting wastewater discharge, low production energy consumption and low operation cost, stable product quality, and the like, and is suitable for large-scale high-purity vanadium pentoxide powder of 4N or more.
  • Industrial production has good economic efficiency and social benefits.
  • Figure 1 is a schematic view showing the configuration of a high purity vanadium pentoxide powder system of the present invention.
  • FIG. 1 is a schematic view of a system for purifying and preparing high-purity vanadium pentoxide powder according to the present invention.
  • the system for purifying high-purity vanadium pentoxide powder used in the present embodiment comprises a feeding device 1, a low-temperature chlorination fluidized bed 2, a rectification purification device 3, a gas-phase ammonium chloride fluidized bed 4, Ammonium metavanadate feeding device 5, calcining fluidized bed 6, exhaust gas leaching absorber 7, induced draft fan 8 and chimney 9;
  • the feeding device 1 comprises an industrial grade vanadium pentoxide silo 1-1, an industrial grade vanadium pentoxide spiral feeder 1-2, a carbon powder silo 1-3 and a carbon powder screw feeder 1-4;
  • the low temperature chlorination fluidized bed 2 comprises a chlorination bed feeder 2-1, a chlorinated fluidized bed main body 2-2, a chlorinated bed cyclone 2-3, a flue gas heat exchanger 2-4, a flue gas condensation 2-5, chlorinated bed acid sealed tank 2-6 and chlorinated bed spiral slag remover 2-7;
  • the rectification and purification device 3 includes a distillation still 3-1, a rectification column 3-2, a distillate condenser 3-3, a reflux liquid collection tank 3-4, a silicon-containing vanadium oxychloride vanadium storage tank 3-5, and a rectification Segment acid sealing tank 3-6, high purity vanadium oxychloride vanadium condenser 3-7 and high purity vanadium oxychloride vanadium storage tank 3-8;
  • the gas phase ammonium chloride fluidized bed 4 comprises an ammonium bed air purifier 4-1, an ammonium bed gas heater 4-2, a vanadium oxychloride nozzle 4-3, a gas phase ammonium chloride fluidized bed body 4-4, and an ammonium chloride.
  • Ammonium metavanadate feeding device 5 comprises ammonium metavanadate silo 5-1 and ammonium metavanadate screw feeder 5-2;
  • the calcined fluidized bed 6 comprises a calcined bed air purifier 6-1, a calcined bed gas heater 6-2, a calcined bed feeder 6-3, a calcined fluidized bed main body 6-4, a calcined bed cyclone separator 6-5 And high purity vanadium pentoxide silo 6-6;
  • the outlet of the bottom of the industrial grade vanadium pentoxide silo 1-1 is connected with the inlet of the industrial grade vanadium pentoxide screw feeder 1-2; the outlet of the carbon powder silo 1-3 and the charcoal
  • the feed ports of the powder auger feeders 1-4 are connected; the discharge ports of the industrial grade vanadium pentoxide screw feeder 1-2, the discharge ports of the carbon powder screw feeders 1-4 are all fed with the chlorination bed
  • the feed ports of the 2-1 are connected by pipes;
  • the discharge port of the chlorination bed feeder 2-1 is connected to the inlet of the upper part of the chlorination fluidized bed main body 2-2 through a pipe; the inlet of the bottom of the chlorination bed feeder 2-1 is piped and The nitrogen gas source manifold is connected; the chlorination bed cyclone separator 2-3 is disposed at the top center of the enlarged section of the chlorination fluidized bed main body 2-2; the gas outlet of the chlorinated bed cyclone separator 2-3 passes through the pipeline and the smoke
  • the hot flue gas inlets of the gas heat exchangers 2-4 are connected; the cold flue gas outlets of the flue gas heat exchangers 2-4 are connected to the gas inlets of the flue gas condensers 2-5 through pipes; the flue gas condensers 2 -
  • the gas outlet of 5 is connected to the gas inlet of the chlorinated bed acid sealing tank 2-6 through a pipe; the gas outlet of the chlorinated bed acid sealing tank 2-6 is connected to the gas inlet of the exhaust gas leaching absorb
  • the liquid outlet at the bottom of the flue gas condenser 2-5 is connected to the feed port of the rectification column 3-2 through a pipe; the vapor outlet of the distillation still 3-1 is connected to the vapor inlet of the rectification column 3-2 through a pipe; The reflux port of the still 3-1 is connected to the liquid reflux outlet at the bottom of the rectification column 3-2 through a pipe; the gas outlet at the top of the rectification column 3-2 is passed through the gas inlet of the distillate condenser 3-3 through the pipe.
  • the liquid outlet of the distillate condenser 3-3 is connected to the liquid inlet of the reflux liquid collection tank 3-4 through a pipe; the reflux liquid outlet of the reflux liquid collection tank 3-4 is passed through the pipe and the top of the rectification column 3-2
  • the reflux liquid inlet is connected;
  • the discharge port of the reflux liquid collection tank 3-4 is connected to the inlet of the silicon-containing vanadium oxychloride vanadium storage tank 3-5 through the pipeline;
  • the silicon-containing vanadium oxychloride vanadium storage tank 3-5 is lacking
  • the gas outlet is connected to the gas inlet of the acid sealing tank 3-6 of the rectifying section through a pipeline;
  • the gas outlet of the rectifying acid sealing tank 3-6 is connected to the gas inlet of the exhaust gas eluting absorber 7 through a pipeline;
  • the rectification tower 3 -2 of the distillate outlet is connected to the gas inlet of the high purity vanadium oxychloride condenser 3-7 through a pipe;
  • the inlet of the ammonium bed air purifier 4-1 is connected to the compressed air manifold through a pipeline; the outlet of the ammonium bed air purifier 4-1 is separately connected to the inlet of the ammonium bed gas heater 4-2 through a pipeline. Mouth, trichloroox
  • the gas inlet of the vanadium nozzle 4-3 and the inlet of the bottom of the ammonium bed discharger 4-6 are connected; the inlet of the ammonium bed gas heater 4-2 passes through the pipeline and the ultrapure water, the purified liquid ammonia manifold
  • the gasification inlet and the fuel inlet of the burner of the ammonium bed gas heater 4-2 are respectively connected to the compressed air main pipe and the fuel main pipe through the pipeline; the gas outlet of the ammonium gasifier 4-2 passes through the pipeline and the gas phase
  • the inlet ports at the bottom of the ammonium fluidized bed main body 4-4 are connected; the liquid outlet of the high purity vanadium oxychloride vanadium storage tank 3-8 is connected through
  • the ammonium bed cyclone 4-5 is disposed at the top center of the enlarged section of the gas phase ammonium chloride fluidized bed main body 4-4; the top gas outlet of the ammonium bed cyclone 4-5 is connected to the exhaust gas treatment unit through a pipe;
  • the discharge port of the upper portion of the gas phase ammonium chloride fluidized bed main body 4-4 is connected to the feed port of the ammonium bed discharger 4-6 through a pipe;
  • the discharge port of the ammonium bed discharger 4-6 is piped and The feed ports of the ammonium metavanadate silo 5-1 are connected;
  • the discharge port at the bottom of the ammonium metavanadate silo 5-1 is connected with the feed port of the ammonium metavanadate screw feeder 5-2; the discharge port of the ammonium metavanadate screw feeder 5-2 is piped and calcined.
  • the feed ports of the bed feeder 6-3 are connected by pipes;
  • the intake port of the calcining bed air purifier 6-1 is connected to the compressed air manifold through a pipe; the gas outlet of the calcining bed air purifier 6-1 is respectively passed through the pipe to the inlet and the calcination of the calcining bed gas heater 6-2.
  • the air inlets at the bottom of the bed feeder 6-3 are connected; the combustion air inlet and the fuel inlet of the burner of the calcining bed gas heater 6-2 are respectively connected to the compressed air main pipe and the fuel main pipe through a pipe; the calcining bed gas heater
  • the gas outlet of 6-2 is connected to the inlet of the bottom of the calcined fluidized bed main body 6-4 through a pipe; the discharge port of the calcined bed feeder 6-3 passes through the pipe and the lower part of the fluidized bed main body 6-4 of the calcined bed.
  • the feed ports are connected; the gas outlet at the top of the calcined fluidized bed main body 6-4 is connected to the inlet of the calcination bed cyclone 6-5 through a pipe; the powder outlet at the bottom of the calcination bed cyclone 6-5 Connected to the inlet of the ammonium chloride silo through a pipeline; the top outlet of the calciner cyclone separator 6-5 is connected to the tail gas treatment unit through a pipe; the discharge port of the upper portion of the main body 6-4 of the calcined fluidized bed passes through the pipeline Connected to the feed port of the high purity vanadium pentoxide silo 6-6;
  • the gas outlet of the exhaust gas rinsing absorber 7 is connected to the gas inlet of the draft fan 8 through a pipe; the gas outlet of the draft fan 8 is connected to the gas inlet at the bottom of the chimney 9 through a pipe.
  • the high-purity vanadium pentoxide powder is purified by the above system, and the specific method comprises: industrial grade vanadium pentoxide powder and carbon powder silo in the industrial grade vanadium pentoxide silo 1-1
  • the carbon powder of 3 is respectively mixed into the chlorinated fluidized bed main body 2-2 by the industrial grade vanadium pentoxide screw feeder 1-2 and the carbon powder screw feeder 1-4 simultaneously entering the chlorination bed feeder 2-1.
  • the chlorine gas from the chlorine gas source main pipe, the nitrogen gas of the nitrogen gas source main pipe and the air of the compressed air main pipe are heated and preheated by the flue gas heat exchanger 2-4 and the chlorinated flue gas, and then enter the chlorinated fluidized bed main body 2-2
  • the powder materials such as vanadium pentoxide and carbon powder are maintained fluidized and chemicalized. Learning reaction, air causes some carbon powder to burn to provide heat to maintain fluidized bed temperature.
  • Chlorine gas and carbon powder work together to chlorinate vanadium pentoxide and a small amount of impurities to form chlorinated residue and chlorination of vanadium oxychloride.
  • the crude vanadium oxychloride vapor formed by the flue gas condenser 2-5 enters the rectification column 3-2 and the distillation still 3-1, and is subjected to a rectification operation to obtain a vanadium-rich scrap rich in high-boiling impurities and rich in low-boiling impurities.
  • the liquid collection tank 3-4 is refluxed to the rectification column 3-2, and the remaining portion is introduced into the silicon-containing vanadium oxychloride vanadium storage tank 3-5; the spent gas generated in the silicon-containing vanadium oxychloride vanadium storage tank 3-5 is rectified
  • the segment acid is sealed 3-6 and sent to the exhaust gas leaching absorber 7.
  • the silicon-containing vanadium oxychloride can be used in the chemical industry; the high-purity vanadium oxychloride vapor is passed through the high-purity vanadium oxychloride condenser 3-7 After condensing to liquid, enter the high purity vanadium oxychloride vanadium storage tank 3-8;
  • ammonium ammonium metavanadate powder is passed through an ammonium bed discharger 4- 6 is discharged into the ammonium metavanadate silo 5-1, and the ammonia-containing ammonium fumed flue gas is removed by the ammonium bed cyclone 4-5 and sent to the tail gas treatment unit for treatment;
  • ammonium chloride-containing ammonium metavanadate powder in the ammonium metavanadate silo 5-1 is sequentially introduced into the calcined fluidized bed main body through the ammonium metavanadate screw feeder 5-2 and the calcined bed feeder 6-3.
  • the compressed air is sequentially pre-heated by the calcining bed air purifier 6-1 and the calcined bed gas heater 6-2, and then enters the calcined fluidized bed main body 6-4 to maintain the fluidization in the bed, and
  • the ammonium metavanadate material containing ammonium chloride is thermally decomposed to obtain a high-purity vanadium pentoxide powder product, and the high-purity vanadium pentoxide silo 6 is obtained by calcining the discharge port of the upper part of the fluidized bed main body 6-4.
  • the gas discharged from the exhaust gas absorbing absorber 7 after being absorbed by the alkali solution is sent to the chimney 9 through the draft fan 8 and then emptied.
  • This embodiment uses powdered industrial grade vanadium pentoxide as raw material, and its chemical composition is listed in Table 1.
  • the treatment amount is 70kg/h, which is prepared by low temperature chlorination, vanadium oxychloride rectification, gas phase ammoniumation and calcination. A high purity vanadium pentoxide product is obtained.
  • the amount of carbon powder added in the low-temperature chlorination process is 10% of the quality of the industrial grade vanadium pentoxide powder, the chlorination operation temperature is 500 ° C, and the average residence time of the powder is 30 min;
  • the rectification column 3-2 the number of trays in the rectification section of the rectification section is 5, the number of trays in the stripping section is 10, and the reflux ratio of the rectification operation is 40;
  • the gas phase ammonium chloride fluidized bed main body 4-4 The operating temperature of the gas phase ammonium is 130 ° C, the molar ratio of water vapor to ammonia is 0.5, the molar ratio of ammonia to vanadium oxychloride is 4.5; in the calcined fluidized bed main body 6-4, the calcination operation temperature is 400 ° C Under the operating conditions of the average residence time of the powder of 180 min, the direct yield of vanadium is 80%, and the purity of the high-
  • the amount of carbon powder added in the low-temperature chlorination process is 20% of the quality of the industrial grade vanadium pentoxide powder, the chlorination operation temperature is 300 ° C, and the average residence time of the powder is 80 min;
  • the rectification column 3-2 the number of trays in the rectification section of the rectification section is 10, the number of trays in the stripping section is 20, and the reflux ratio of the rectification operation is 15;
  • in the gas phase ammonium chloride fluidized bed main body 4-4 The operating temperature of the gas phase ammonium is 250 ° C, the molar ratio of water vapor to ammonia is 0.8, the molar ratio of ammonia to vanadium oxychloride is 3.5; in the calcined fluidized bed main body 6-4, the calcination operation temperature is 650 °C, under the operating conditions of the average residence time of the powder for 60 min, the direct yield of vanadium is 81%, and the purity of the

Abstract

一种提纯制备五氧化二钒粉体的系统及方法，采用流态化低温氯化将工业级五氧化二钒转化为三氯氧钒，通过流化气体与氯化烟气换热实现氯化气体预热、适量配加空气使部分炭粉燃烧实现氯化过程的热量平衡供给，提高氯化效率和保证低温氯化的良好选择性；三氯氧钒经精馏提纯后进行流态化气相铵化得到偏钒酸铵，进一步通过流态化煅烧得到高纯五氧化二钒粉体产品。该系统和方法具有原料适应性强、无污染废水排放、生产能耗和氯气消耗低、产品质量稳定等优点。

Description

一种提纯制备高纯五氧化二钒粉体的系统及方法 技术领域
本发明属于化工、材料领域，特别涉及一种提纯制备高纯五氧化二钒粉体的系统及方法。
背景技术
五氧化二钒是重要的工业钒制品之一，广泛应用于生产钒铁和氮化钒等合金添加剂以及催化剂、着色剂、硬质合金添加剂等领域。随着新能源技术的不断发展，电池行业对高纯五氧化二钒(纯度3N5以上)的需求日益强劲，包括具有良好大规模储能性能的全钒液流电池(VRB)和电动汽车用钒酸盐系锂离子电池等。然而，现有工业技术通常仅可制备纯度2N5的五氧化二钒(即HGT 3485-2003规定指标的产品)，难以满足电池行业用五氧化二钒的要求。因此，如何低成本、高效制备高纯五氧化二钒是新能源技术领域亟待解决的热点问题之一。
目前，通常以浸出钒溶液或富钒物料(如多钒酸铵、偏钒酸铵、工业级五氧化二钒等)溶解得到钒溶液为原料，采用化学沉淀净化或(和)溶剂萃取/离子树脂交换等方法进行净化，得到纯净的钒溶液然后进行铵盐沉淀得到纯净的多钒酸铵或偏钒酸铵沉淀，再经过煅烧分解得到高纯五氧化二钒粉体，如中国专利申请CN1843938A、CN102730757A、CN103145187A、CN103515642A、CN103194603A、CN103787414A、CN102181635A、CN103663557A和欧洲专利EP0713257B1等。在这些方法中，除杂工艺参数与原料的杂质含量密切相关，因而对原料的适应性差；净化过程中使用的钙盐、镁盐净化剂或萃取剂、酸碱试剂以及钒沉淀用铵盐也容易引入杂质。为了提高产品质量，通常要求使用纯度较高的昂贵试剂，因而成本过高，无法规模化生产且产品纯度难以稳定在3N5以上。
针对净化剂或萃取剂易引入杂质和试剂使用成本过高的问题，相关机构还提出采用反复沉淀法实现钒溶液的净化除杂，即利用含钒溶液的铵盐沉淀特性，选择性地将钒沉淀出来而将杂质离子部分抑制于沉淀后的溶液中，然后再次将得到的铵盐沉淀溶解后，进行多次重复操作，从而得到较为纯净的多钒酸铵或偏钒酸铵沉淀，再经过煅烧分解得到高纯五氧化二钒粉体，如中国专利申请CN103606694A和CN102923775A等。这有效降低了试剂使用量及其引入杂质的可能性，但溶解-沉淀过程仍需使用大量纯度较高的酸碱试剂和铵盐，提纯成本 仍然较高；且繁冗的多次沉淀操作既降低了生产效率又造成钒直收率的明显下降。另外，上述溶液净化方法中，萃取/反萃、沉淀、洗涤等操作步骤会产生大量的废水，主要含有少量的钒离子、铵根离子和大量的钠盐，处理难度大、污染问题突出，这也严重制约了其规模化工业应用。
因金属氯化物的沸点及饱和蒸气压相差较大，不同金属氯化物很容易通过蒸馏/精馏实现分离，原料氯化-精馏提纯-后续处理是高纯物质的常用制备工艺，如高纯硅(多晶硅)、高纯二氧化硅等。由于钒的氯化物三氯氧钒与常见杂质铁、钙、镁、铝、钠、钾等的氯化物沸点相差很大，很容易通过精馏得到高纯三氯氧钒，而从高纯三氯氧钒通过水解和铵盐沉淀，再辅以煅烧即可制备高纯五氧化二钒。因此，采用氯化法制备高纯五氧化二钒从原理上具有较大的优势。实际上，采用氯化法制备高纯五氧化二钒不仅原理上可行，而且早在上世纪60年代，就由美国爱荷华州立大学的研究人员在实验室得以实现(Journal of the Less-Common Metals,1960,2:29-35)。他们以多钒酸铵为原料，通过配碳氯化制得粗三氯氧钒，蒸馏提纯获得高纯三氯氧钒，铵盐沉淀得到高纯偏钒酸铵，最后在500～600℃下煅烧获得高纯五氧化二钒粉体，但沉淀、洗涤过程将产生大量的氨氮废水，处理难度大。然而，该项研究仅在实验室设备上、分段间歇地实现了氯化法制备高纯五氧化二钒，无法提供工业规模如何采用氯化法连续制备高纯五氧化二钒相关信息，可能也正是由于这些原因，之后的几十年里，也难觅氯化法连续制备高纯五氧化二钒的报道。
最近，中国专利申请CN103130279A提出了采用氯化法，以钒铁磁铁矿、钒渣、含钒催化剂等含钒物质为原料制备高纯五氧化二钒的方法。经配碳氯化-除尘-冷凝得到钒氯化物的混合物，经过精馏分离四氯化钒得到纯净的三氯氧钒后，将三氯氧钒通入超纯水溶液中或超纯氨水溶液中进行沉淀，经过滤、干燥、煅烧得到五氧化二钒。该项专利存在如下不足：(1)与前述美国爱荷华州立大学研究类似，该专利实际只给出了氯化的原则流程，缺乏具体可操作的方案，比如氯化方式既包括了沸腾氯化，又包括了熔盐氯化，而熔盐氯化与沸腾氯化是完全不同的氯化方法；再比如，对于氯化反应器提出采用“回转窑、流化炉、沸腾炉、竖炉、多膛炉”等反应器，实际上涵盖了冶金工业领域几乎所有的常用主流反应器，但不同的反应器对原料的要求差别非常大，竖炉只能处理大于8mm的“粗”颗粒，使用“细颗粒”时需要进行球团与烧结前处理，而沸腾氯化一般适合处理细颗粒，所以对于一种特定的钒原料，无法直接适用于回转窑、流化炉、沸腾炉、 竖炉、多膛炉等反应器；况且“流化炉”与“沸腾炉”本质上是一样的，只是叫法不同；由此可见，由于这些反应器的操作方式及条件相差很大，只给出原则流程实际上无法实施；(2)将三氯氧钒通入超纯水溶液中进行水解，由于五氧化二钒极易溶解于盐酸溶液中，钒的沉淀回收率过低；在HCl浓度大于6.0mol/L的盐酸溶液中，五氧化二钒溶解时将发生还原生成VOCl2，同时放出氯气，这将会进一步降低钒的沉淀回收率；沉淀和洗涤过程必将会产生大量的含钒盐酸溶液，难以有效实现综合处理。
另外，对于工业大规模应用而言，现有钒原料氯化技术仍存在如下两个问题：(1)钒原料氯化焙烧属于强放热过程，氯化反应产生的热量除了可满足固体和气体反应物料的预热外，仍需要通过炉壁散热等方式移出才能稳定氯化温度，故固体和气体通常均以近室温状态进入反应器内，被氯化反应产生热量预热后才能参与反应，这使得氯化反应器局部反应效率过低；(2)由于需要通过大量散热移出氯化反应产生的热量以维持操作温度，故操作条件和环境气候变化均易引起氯化温度波动，造成氯化选择性和效率降低，需要采用合理的热量平衡供给和温度调控方式。因此，必须提供合理热量供给和温度控制，才有可能有效地提高氯化效率和获得稳定氯化温度从而确保氯化的选择性以有效抑制杂质的氯化。
因此，通过工艺及技术创新，实现氯化过程的调控、提高钒的直收率、避免大量氨氮废水产生、提高五氧化二钒提纯效率，是提高氯化法提纯制备高纯五氧化二钒技术经济性的关键。
发明内容
针对上述问题，本发明提出了一种提纯制备高纯五氧化二钒粉体的系统及方法，以保证低温氯化的良好选择性、避免大量氨氮废水产生、降低高纯五氧化二钒的生产能耗和操作成本。为了达到这些目的，本发明采用了如下技术方案：
本发明的提纯制备高纯五氧化二钒粉体的系统，所述系统包括加料装置1、低温氯化流化床2、精馏提纯装置3、气相铵化流化床4、偏钒酸铵加料装置5、煅烧流化床6、尾气淋洗吸收器7、引风机8和烟囱9；
所述加料装置1包括工业级五氧化二钒料仓1-1、工业级五氧化二钒螺旋加料器1-2、炭粉料仓1-3和炭粉螺旋加料器1-4；
所述低温氯化流化床2包括氯化床进料器2-1、氯化流化床主体2-2、氯化床旋风分离器2-3、烟气换热器2-4、烟气冷凝器2-5、氯化床酸封罐2-6和氯化 床螺旋排渣器2-7；
所述精馏提纯装置3包括蒸馏釜3-1、精馏塔3-2、馏出物冷凝器3-3、回流液收集罐3-4、含硅三氯氧钒储罐3-5、精馏段酸封罐3-6、高纯三氯氧钒冷凝器3-7和高纯三氯氧钒储罐3-8；
所述气相铵化流化床4包括铵化床空气净化器4-1、铵化床气体加热器4-2、三氯氧钒喷嘴4-3、气相铵化流化床主体4-4、铵化床旋风分离器4-5和铵化床排料器4-6；
所述偏钒酸铵加料装置5包括偏钒酸铵料仓5-1和偏钒酸铵螺旋加料器5-2；
所述煅烧流化床6包括煅烧床空气净化器6-1、煅烧床气体加热器6-2、煅烧床进料器6-3、煅烧流化床主体6-4、煅烧床旋风分离器6-5和高纯五氧化二钒料仓6-6；
所述工业级五氧化二钒料仓1-1底部的出料口与所述工业级五氧化二钒螺旋加料器1-2的进料口相连接；所述炭粉料仓1-3底部的出料口与所述炭粉螺旋加料器1-4的进料口相连接；所述工业级五氧化二钒螺旋加料器1-2的出料口、所述炭粉螺旋加料器1-4的出料口均与所述氯化床进料器2-1的进料口通过管道相连接；
所述氯化床进料器2-1的排料口与所述氯化流化床主体2-2上部的进料口通过管道相连接；所述氯化床进料器2-1底部的进气口通过管道与氮气气源总管相连接；所述氯化床旋风分离器2-3设置于所述氯化流化床主体2-2的扩大段顶部中心；所述氯化床旋风分离器2-3顶部的出气口通过管道与所述烟气换热器2-4的热烟气入口相连接；所述烟气换热器2-4的冷烟气出口通过管道与所述烟气冷凝器2-5的气体入口相连接；所述烟气冷凝器2-5的气体出口通过管道与所述氯化床酸封罐2-6的气体入口相连接；所述氯化床酸封罐2-6的气体出口通过管道与所述尾气淋洗吸收器7的气体入口相连接；所述氯化流化床主体2-2下部的排渣口与所述氯化床螺旋排渣器2-7的进料口通过管道相连接；所述氯化流化床主体2-2底部的进气口通过管道与所述烟气换热器2-4的热气体出口相连接；所述烟气换热器2-4的冷气体入口通过管道分别与氯气气源总管、氮气气源总管及压缩空气总管相连接；
所述烟气冷凝器2-5底部的液体出口通过管道与所述精馏塔3-2的进料口相连接；所述蒸馏釜3-1的蒸气出口通过管道与所述精馏塔3-2的蒸气入口相连接；所述蒸馏釜3-1的回流口通过管道与所述精馏塔3-2底部的液体回流出口相连接； 所述精馏塔3-2顶部的气体出口通过管道与所述馏出物冷凝器3-3的气体入口相连接；所述馏出物冷凝器3-3的液体出口通过管道与所述回流液收集罐3-4的液体入口相连接；所述回流液收集罐3-4的回流液体出口通过管道与所述精馏塔3-2顶部的回流液体入口相连接；所述回流液收集罐3-4的排料口与所述含硅三氯氧钒储罐3-5的入口通过管道相连接；所述含硅三氯氧钒储罐3-5的乏气出口通过管道与所述精馏段酸封罐3-6的气体入口相连接；所述精馏酸封罐3-6的气体出口通过管道与所述尾气淋洗吸收器7的气体入口相连接；所述精馏塔3-2的精馏物出口通过管道与所述高纯三氯氧钒冷凝器3-7的气体入口相连接；所述高纯三氯氧钒冷凝器3-7的液体出口与所述高纯三氯氧钒储罐3-8的液体入口通过管道相连接；所述蒸馏釜3-1底部设置了底流出口；
所述铵化床空气净化器4-1的进气口与压缩空气总管通过管道相连接；所述铵化床空气净化器4-1的出气口通过管道分别与所述铵化床气体加热器4-2的进气口、三氯氧钒喷嘴4-3的气体入口及铵化床排料器4-6底部的进气口相连接；所述铵化床气体加热器4-2的进气口通过管道与超纯水、纯化液氨总管相连接；所述铵化床气体加热器4-2燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；所述铵化床气体加热器4-2的出气口通过管道与所述气相铵化流化床主体4-4底部的进气口相连接；所述高纯三氯氧钒储罐3-8的液体出口通过管道与所述三氯氧钒喷嘴4-3的三氯氧钒入口相连接；所述铵化床旋风分离器4-5设置于所述气相铵化流化床主体4-4扩大段顶部中心处；所述铵化床旋风分离器4-5的顶部出气口通过管道与尾气处理单元相连接；所述气相铵化流化床主体4-4上部的排料口通过管道与所述铵化床排料器4-6的进料口相连接；所述铵化床排料器4-6的排料口通过管道与所述偏钒酸铵料仓5-1的进料口相连接；
所述偏钒酸铵料仓5-1底部的出料口与所述偏钒酸铵螺旋加料器5-2的进料口相连接；所述偏钒酸铵螺旋加料器5-2的排料口通过管道与所述煅烧床进料器6-3的进料口通过管道相连接；
所述煅烧床空气净化器6-1的进气口与压缩空气总管通过管道相连接；所述煅烧床空气净化器6-1的出气口通过管道分别与所述煅烧床气体加热器6-2的进气口和煅烧床进料器6-3底部的进气口相连接；所述煅烧床气体加热器6-2燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；所述煅烧床气体加热器6-2的出气口通过管道与所述煅烧流化床主体6-4底部的进 气口相连接；所述煅烧床进料器6-3的排料口通过管道与所述煅烧床流化床主体6-4下部的进料口相连接；所述煅烧流化床主体6-4顶部的出气口通过管道与所述煅烧床旋风分离器6-5的进气口相连接；所述煅烧床旋风分离器6-5底部的粉料出口通过管道与氯化铵料仓进料口相连接；所述煅烧床旋风分离器6-5的顶部出气口通过管道与尾气处理单元相连接；所述煅烧流化床主体6-4上部的排料口通过管道与所述高纯五氧化二钒料仓6-6的进料口相连接；
所述尾气淋洗吸收器7的气体出口通过管道与所述引风机8的气体入口相连接；所述引风机8的气体出口通过管道与所述烟囱9底部的气体入口相连接。
本发明的基于上述系统的提纯制备高纯五氧化二钒粉体的方法，包括以下步骤：
所述工业级五氧化二钒料仓1-1中的工业级五氧化二钒粉料和所述炭粉料仓1-3的炭粉分别经所述工业级五氧化二钒螺旋加料器1-2和所述炭粉螺旋加料器1-4同时进入所述氯化床进料器2-1混合后进入所述氯化流化床主体2-2；来自氯气气源总管的氯气、氮气气源总管的氮气及压缩空气总管的空气经所述烟气换热器2-4与氯化烟气换热预热后进入所述氯化流化床主体2-2中使五氧化二钒、炭粉等粉体物料维持流态化并与之发生化学反应，空气使部分炭粉发生燃烧提供热量维持流化床温度，氯气与炭粉共同作用使五氧化二钒和少量杂质发生氯化，形成氯化残渣和富含三氯氧钒的氯化烟气；氯化残渣经所述氯化流化床主体2-2下部的排渣口、所述氯化床螺旋排渣器2-7排出；氯化烟气经所述氯化床旋风分离器2-3将粉尘脱除并落回氯化流化床主体2-2后，再经所述烟气换热器2-4预冷却并进入烟气冷凝器2-5中使其中的三氯氧钒冷凝形成粗三氯氧钒液体，剩余尾气经所述氯化床酸封罐2-6后进入所述尾气淋洗吸收器7中；
所述烟气冷凝器2-5形成的粗三氯氧钒液体进入所述精馏塔3-2和所述蒸馏釜3-1后进行精馏操作，得到富含高沸点杂质的富钒废料、富含低沸点杂质的含硅三氯氧钒蒸气和高纯三氯氧钒蒸气；富钒废料用于后续回收钒，含硅三氯氧钒蒸气经所述馏出物冷凝器3-3冷凝至液体后，部分经回流液收集罐3-4回流至所述精馏塔3-2，其余部分进入所述含硅三氯氧钒储罐3-5中；含硅三氯氧钒储罐3-5中产生的乏气经所述精馏段酸封罐3-6后送往所述尾气淋洗吸收器7中，含硅三氯氧钒可用于催化等化工领域；高纯三氯氧钒蒸气经所述高纯三氯氧钒冷凝器3-7冷凝至液体后进入所述高纯三氯氧钒储罐3-8中；
所述高纯三氯氧钒储罐3-8的高纯三氯氧钒经所述三氯氧钒喷嘴4-3，由来 自铵化床空气净化器4-1的净化空气气载进入所述气相铵化流化床主体4-4中；超纯水、纯化液氨和净化空气经所述铵化床气体加热器4-2预热后送入所述气相铵化流化床主体4-4中使床内粉料维持流态化，并使三氯氧钒发生水解和铵化，生成含氯化铵的偏钒酸铵粉体，所述含氯化铵的偏钒酸铵粉体经所述铵化床排料器4-6排出后进入所述偏钒酸铵料仓5-1中，产生的含氨的铵化烟气经铵化床旋风分离器4-5脱除粉尘后送尾气处理单元处理；
所述偏钒酸铵料仓5-1中的含氯化铵的偏钒酸铵粉料依次经所述偏钒酸铵螺旋加料器5-2和煅烧床进料器6-3进入所述煅烧流化床主体6-4中；压缩空气依次经所述煅烧床空气净化器6-1净化和煅烧床气体加热器6-2预热后进入所述煅烧流化床主体6-4中使床内粉料维持流态化，并使含氯化铵的偏钒酸铵物料发生热分解，得到高纯五氧化二钒粉体产品，经所述煅烧流化床主体6-4上部的排料口进入所述高纯五氧化二钒料仓6-6中；煅烧分解产生的煅烧烟气进入所述煅烧床旋风分离器6-5降温析出氯化铵并脱除粉尘后送尾气处理单元处理；所述煅烧床旋风分离器6-5收集到的氯化铵粉料送往氯化铵料仓中；
所述尾气淋洗吸收器7经碱溶液吸收处理后排出的气体经所述引风机8送入所述烟囱9后排空。
本发明的特征之一在于：在所述氯化流化床主体2-2内，所述氯化过程炭粉添加量为工业级五氧化二钒粉料质量的10％～20％，氯化操作温度为300～500℃，粉料的平均停留时间为30～80min。
本发明的特征之二在于：在精馏塔3-2内，所述精馏操作精馏段的塔板数为5～10块，提馏段的塔板数为10～20块；在精馏操作过程中，保持回流比(即塔顶回流量与排料量之比)为15～40。
本发明的特征之三在于：在气相铵化流化床主体4-4内，通过高纯三氯氧钒气相铵化制备得到偏钒酸铵，所述气相铵化的操作温度为130～250℃，水蒸气与氨气的摩尔比为0.5～0.8，氨气与三氯氧钒的摩尔比为3.5～4.5。
本发明的特征之四在于：在煅烧流化床主体6-4内，通过流态化煅烧实现含氯化铵的偏钒酸铵的热分解，所述煅烧操作温度为400～650℃，粉料的平均停留时间为60～180min。
本发明制得的高纯五氧化二钒粉体纯度均在4N以上。相对于现有技术，本发明具有如下突出的优点：
(1)通过氯化气体与氯化烟气换热，在冷却烟气的同时，实现氯化气体预 热，使氯化反应器温度分布更为均匀，有效提高钒原料低温氯化效率；
(2)通过适量配加空气使部分炭粉燃烧实现氯化过程的热量平衡供给和温度调控，稳定氯化操作温度，提高氯化反应效率和保证氯化的良好选择性，避免生成四氯化钒等副反应的发生；
(3)精馏纯化后的三氯氧钒经喷嘴送入气相铵化流化床进行水解铵化得到含氯化铵的偏钒酸铵粉体，相对于传统水解/铵盐沉淀，可有效避免氯化铵废盐水的产生；
(4)含氯化铵的偏钒酸铵进行流态化煅烧，偏钒酸铵分解至高纯五氧化二钒产品，氯化铵也发生分解随烟气排出，冷却后即可得到氯化铵产品，有效地实现高纯产品的制备和氯化铵的回收。
本发明具有原料适应性强、低温氯化的选择性良好、无污染废水排放、生产能耗和操作成本低、产品质量稳定等优点，适用于4N以上高纯五氧化二钒粉体的大规模工业化生产，具有良好经济效率和社会效益。
附图说明
附图用来提供对本发明的进一步阐释，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。
图1为本发明的生产高纯四氧化二钒粉体系统的配置示意图。
附图标记
1 加料装置
1-1 工业级五氧化二钒料仓        1-2 工业级五氧化二钒螺旋加料器
1-3 炭粉料仓                    1-4 炭粉螺旋加料器
2 低温氯化流化床
2-1 氯化床进料器      2-2 氯化流化床主体      2-3 氯化床旋风分离器
2-4 烟气换热器        2-5 烟气冷凝器          2-6 氯化床酸封罐
2-7 氯化床螺旋排渣器
3 精馏提纯装置
3-1 蒸馏釜            3-2 精馏塔              3-3 馏出物冷凝器
3-4 回流液收集罐      3-5 含硅三氯氧钒储罐    3-6 精馏段酸封罐
3-7 高纯三氯氧钒冷凝器                       3-8 高纯三氯氧钒储罐
4 气相铵化流化床
4-1 铵化床空气净化器  4-2 铵化床气体加热器    4-3 三氯氧钒喷嘴
4-4 气相铵化流化床主体 4-5 铵化床旋风分离器   4-6 铵化床排料器
5 偏钒酸铵加料装置
5-1 偏钒酸铵料仓       5-2 偏钒酸铵螺旋加料器
6 煅烧流化床
6-1 煅烧床空气净化器   6-2 煅烧床气体加热器   6-3 煅烧床进料器
6-4 煅烧流化床主体   6-5 煅烧床旋风分离器  6-6 高纯五氧化二钒料仓
7 尾气淋洗吸收器       8 引风机               9 烟囱
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。值得说明的是，实施例仅用以说明本发明的技术方案，而非对其限制。图1为本发明的一种提纯制备高纯五氧化二钒粉体的系统示意图。
结合图1，本实施例所使用的提纯制备高纯五氧化二钒粉体的系统，包括加料装置1、低温氯化流化床2、精馏提纯装置3、气相铵化流化床4、偏钒酸铵加料装置5、煅烧流化床6、尾气淋洗吸收器7、引风机8和烟囱9；
加料装置1包括工业级五氧化二钒料仓1-1、工业级五氧化二钒螺旋加料器1-2、炭粉料仓1-3和炭粉螺旋加料器1-4；
低温氯化流化床2包括氯化床进料器2-1、氯化流化床主体2-2、氯化床旋风分离器2-3、烟气换热器2-4、烟气冷凝器2-5、氯化床酸封罐2-6和氯化床螺旋排渣器2-7；
精馏提纯装置3包括蒸馏釜3-1、精馏塔3-2、馏出物冷凝器3-3、回流液收集罐3-4、含硅三氯氧钒储罐3-5、精馏段酸封罐3-6、高纯三氯氧钒冷凝器3-7和高纯三氯氧钒储罐3-8；
气相铵化流化床4包括铵化床空气净化器4-1、铵化床气体加热器4-2、三氯氧钒喷嘴4-3、气相铵化流化床主体4-4、铵化床旋风分离器4-5和铵化床排料器4-6；
偏钒酸铵加料装置5包括偏钒酸铵料仓5-1和偏钒酸铵螺旋加料器5-2； 煅烧流化床6包括煅烧床空气净化器6-1、煅烧床气体加热器6-2、煅烧床进料器6-3、煅烧流化床主体6-4、煅烧床旋风分离器6-5和高纯五氧化二钒料仓6-6；
工业级五氧化二钒料仓1-1底部的出料口与工业级五氧化二钒螺旋加料器1-2的进料口相连接；炭粉料仓1-3底部的出料口与炭粉螺旋加料器1-4的进料口相连接；工业级五氧化二钒螺旋加料器1-2的出料口、炭粉螺旋加料器1-4的出料口均与氯化床进料器2-1的进料口通过管道相连接；
氯化床进料器2-1的排料口与氯化流化床主体2-2上部的进料口通过管道相连接；氯化床进料器2-1底部的进气口通过管道与氮气气源总管相连接；氯化床旋风分离器2-3设置于氯化流化床主体2-2的扩大段顶部中心；氯化床旋风分离器2-3顶部的出气口通过管道与烟气换热器2-4的热烟气入口相连接；烟气换热器2-4的冷烟气出口通过管道与烟气冷凝器2-5的气体入口相连接；烟气冷凝器2-5的气体出口通过管道与氯化床酸封罐2-6的气体入口相连接；氯化床酸封罐2-6的气体出口通过管道与尾气淋洗吸收器7的气体入口相连接；氯化流化床主体2-2下部的排渣口与氯化床螺旋排渣器2-7的进料口通过管道相连接；氯化流化床主体2-2底部的进气口通过管道与烟气换热器2-4的热气体出口相连接；烟气换热器2-4的冷气体入口通过管道分别与氯气气源总管、氮气气源总管及压缩空气总管相连接；
烟气冷凝器2-5底部的液体出口通过管道与精馏塔3-2的进料口相连接；蒸馏釜3-1的蒸气出口通过管道与精馏塔3-2的蒸气入口相连接；蒸馏釜3-1的回流口通过管道与精馏塔3-2底部的液体回流出口相连接；精馏塔3-2顶部的气体出口通过管道与馏出物冷凝器3-3的气体入口相连接；馏出物冷凝器3-3的液体出口通过管道与回流液收集罐3-4的液体入口相连接；回流液收集罐3-4的回流液体出口通过管道与精馏塔3-2顶部的回流液体入口相连接；回流液收集罐3-4的排料口与含硅三氯氧钒储罐3-5的入口通过管道相连接；含硅三氯氧钒储罐3-5的乏气出口通过管道与精馏段酸封罐3-6的气体入口相连接；精馏酸封罐3-6的气体出口通过管道与尾气淋洗吸收器7的气体入口相连接；精馏塔3-2的精馏物出口通过管道与高纯三氯氧钒冷凝器3-7的气体入口相连接；高纯三氯氧钒冷凝器3-7的液体出口与高纯三氯氧钒储罐3-8的液体入口通过管道相连接；蒸馏釜3-1底部设置了底流出口；
铵化床空气净化器4-1的进气口与压缩空气总管通过管道相连接；铵化床空气净化器4-1的出气口通过管道分别与铵化床气体加热器4-2的进气口、三氯氧 钒喷嘴4-3的气体入口及铵化床排料器4-6底部的进气口相连接；铵化床气体加热器4-2的进气口通过管道与超纯水、纯化液氨总管相连接；铵化床气体加热器4-2燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；铵化床气体加热器4-2的出气口通过管道与气相铵化流化床主体4-4底部的进气口相连接；高纯三氯氧钒储罐3-8的液体出口通过管道与三氯氧钒喷嘴4-3的三氯氧钒入口相连接；铵化床旋风分离器4-5设置于气相铵化流化床主体4-4扩大段顶部中心处；铵化床旋风分离器4-5的顶部出气口通过管道与尾气处理单元相连接；气相铵化流化床主体4-4上部的排料口通过管道与铵化床排料器4-6的进料口相连接；铵化床排料器4-6的排料口通过管道与偏钒酸铵料仓5-1的进料口相连接；
偏钒酸铵料仓5-1底部的出料口与偏钒酸铵螺旋加料器5-2的进料口相连接；偏钒酸铵螺旋加料器5-2的排料口通过管道与煅烧床进料器6-3的进料口通过管道相连接；
煅烧床空气净化器6-1的进气口与压缩空气总管通过管道相连接；煅烧床空气净化器6-1的出气口通过管道分别与煅烧床气体加热器6-2的进气口和煅烧床进料器6-3底部的进气口相连接；煅烧床气体加热器6-2燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；煅烧床气体加热器6-2的出气口通过管道与煅烧流化床主体6-4底部的进气口相连接；煅烧床进料器6-3的排料口通过管道与煅烧床流化床主体6-4下部的进料口相连接；煅烧流化床主体6-4顶部的出气口通过管道与煅烧床旋风分离器6-5的进气口相连接；煅烧床旋风分离器6-5底部的粉料出口通过管道与氯化铵料仓进料口相连接；煅烧床旋风分离器6-5的顶部出气口通过管道与尾气处理单元相连接；煅烧流化床主体6-4上部的排料口通过管道与高纯五氧化二钒料仓6-6的进料口相连接；
尾气淋洗吸收器7的气体出口通过管道与引风机8的气体入口相连接；引风机8的气体出口通过管道与烟囱9底部的气体入口相连接。
本实施例利用上述系统进行提纯制备高纯五氧化二钒粉体，具体方法包括：工业级五氧化二钒料仓1-1中的工业级五氧化二钒粉料和炭粉料仓1-3的炭粉分别经工业级五氧化二钒螺旋加料器1-2和炭粉螺旋加料器1-4同时进入氯化床进料器2-1混合后进入氯化流化床主体2-2；来自氯气气源总管的氯气、氮气气源总管的氮气及压缩空气总管的空气经烟气换热器2-4与氯化烟气换热预热后进入氯化流化床主体2-2中使五氧化二钒、炭粉等粉体物料维持流态化并与之发生化 学反应，空气使部分炭粉发生燃烧提供热量维持流化床温度，氯气与炭粉共同作用使五氧化二钒和少量杂质发生氯化，形成氯化残渣和富含三氯氧钒的氯化烟气；氯化残渣经氯化流化床主体2-2下部的排渣口、氯化床螺旋排渣器2-7排出；氯化烟气经氯化床旋风分离器2-3将粉尘脱除并落回氯化流化床主体2-2后，再经烟气换热器2-4预冷却并进入烟气冷凝器2-5中使其中的三氯氧钒冷凝形成粗三氯氧钒液体，剩余尾气经氯化床酸封罐2-6后进入尾气淋洗吸收器7中；
烟气冷凝器2-5形成的粗三氯氧钒液体进入精馏塔3-2和蒸馏釜3-1后进行精馏操作，得到富含高沸点杂质的富钒废料、富含低沸点杂质的含硅三氯氧钒蒸气和高纯三氯氧钒蒸气；富钒废料用于后续回收钒，含硅三氯氧钒蒸气经馏出物冷凝器3-3冷凝至液体后，部分经回流液收集罐3-4回流至精馏塔3-2，其余部分进入含硅三氯氧钒储罐3-5中；含硅三氯氧钒储罐3-5中产生的乏气经精馏段酸封罐3-6后送往尾气淋洗吸收器7中，含硅三氯氧钒可用于催化等化工领域；高纯三氯氧钒蒸气经高纯三氯氧钒冷凝器3-7冷凝至液体后进入高纯三氯氧钒储罐3-8中；
高纯三氯氧钒储罐3-8的高纯三氯氧钒经三氯氧钒喷嘴4-3，由来自铵化床空气净化器4-1的净化空气气载进入气相铵化流化床主体4-4中；超纯水、纯化液氨和净化空气经铵化床气体加热器4-2预热后送入气相铵化流化床主体4-4中使床内粉料维持流态化，并使三氯氧钒发生水解和铵化，生成含氯化铵的偏钒酸铵粉体，所述含氯化铵的偏钒酸铵粉体经铵化床排料器4-6排出后进入偏钒酸铵料仓5-1中，产生的含氨的铵化烟气经铵化床旋风分离器4-5脱除粉尘后送尾气处理单元处理；
偏钒酸铵料仓5-1中的含氯化铵的偏钒酸铵粉料依次经偏钒酸铵螺旋加料器5-2和煅烧床进料器6-3进入煅烧流化床主体6-4中；压缩空气依次经煅烧床空气净化器6-1净化和煅烧床气体加热器6-2预热后进入煅烧流化床主体6-4中使床内粉料维持流态化，并使含氯化铵的偏钒酸铵物料发生热分解，得到高纯五氧化二钒粉体产品，经煅烧流化床主体6-4上部的排料口进入高纯五氧化二钒料仓6-6中；煅烧分解产生的煅烧烟气进入煅烧床旋风分离器6-5降温析出氯化铵并脱除粉尘后送尾气处理单元处理；煅烧床旋风分离器6-5收集到的氯化铵粉料送往氯化铵料仓中。
尾气淋洗吸收器7经碱溶液吸收处理后排出的气体经引风机8送入烟囱9后排空。
本实施例以粉状的工业级五氧化二钒为原料，其化学组成见表1所列，处理量为70kg/h，经低温氯化、三氯氧钒精馏、气相铵化、煅烧制备得到高纯五氧化二钒产品。
表1实施例使用工业级五氧化二钒原料的化学组成(wt％)
V2O5 Si Ca Al Ti Fe Mn Na K S
98.8 0.0150 0.0275 0.0099 0.0260 0.0971 0.0293 0.1385 0.0714 0.1274
在氯化流化床主体2-2内，低温氯化过程炭粉添加量为工业级五氧化二钒粉料质量的10％，氯化操作温度500℃，粉料的平均停留时间30min；在精馏塔3-2内，精馏操作精馏段的塔板数5块，提馏段的塔板数10块，精馏操作的回流比40；在气相铵化流化床主体4-4内，气相铵化的操作温度为130℃，水蒸气与氨气的摩尔比0.5，氨气与三氯氧钒的摩尔比4.5；在煅烧流化床主体6-4内，煅烧操作温度400℃，粉料的平均停留时间180min的操作条件下，钒的直收率达80％，高纯五氧化二钒产品的纯度达99.995wt％(4N5)。
在氯化流化床主体2-2内，低温氯化过程炭粉添加量为工业级五氧化二钒粉料质量的20％，氯化操作温度300℃，粉料的平均停留时间80min；在精馏塔3-2内，精馏操作精馏段的塔板数10块，提馏段的塔板数20块，精馏操作的回流比15；在气相铵化流化床主体4-4内，气相铵化的操作温度为250℃，水蒸气与氨气的摩尔比0.8，氨气与三氯氧钒的摩尔比3.5；在煅烧流化床主体6-4内，煅烧操作温度为650℃，粉料的平均停留时间60min的操作条件下，钒的直收率达81％，高纯五氧化二钒产品的纯度达99.999wt％(5N)。
本发明未详细阐述部分属于本领域公知技术。
当然，本发明还可以有多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明的公开做出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明的权利要求的保护范围。

Claims (8)

  1. 一种提纯制备高纯五氧化二钒粉体的系统，其特征在于，所述系统包括加料装置(1)、低温氯化流化床(2)、精馏提纯装置(3)、气相铵化流化床(4)、偏钒酸铵加料装置(5)、煅烧流化床(6)、尾气淋洗吸收器(7)、引风机(8)和烟囱(9)；
    所述加料装置(1)包括工业级五氧化二钒料仓(1-1)、工业级五氧化二钒螺旋加料器(1-2)、炭粉料仓(1-3)和炭粉螺旋加料器(1-4)；
    所述低温氯化流化床(2)包括氯化床进料器(2-1)、氯化流化床主体(2-2)、氯化床旋风分离器(2-3)、烟气换热器(2-4)、烟气冷凝器(2-5)、氯化床酸封罐(2-6)和氯化床螺旋排渣器(2-7)；
    所述精馏提纯装置(3)包括蒸馏釜(3-1)、精馏塔(3-2)、馏出物冷凝器(3-3)、回流液收集罐(3-4)、含硅三氯氧钒储罐(3-5)、精馏段酸封罐(3-6)、高纯三氯氧钒冷凝器(3-7)和高纯三氯氧钒储罐(3-8)；
    所述气相铵化流化床(4)包括铵化床空气净化器(4-1)、铵化床气体加热器(4-2)、三氯氧钒喷嘴(4-3)、气相铵化流化床主体(4-4)、铵化床旋风分离器(4-5)和铵化床排料器(4-6)；
    所述偏钒酸铵加料装置(5)包括偏钒酸铵料仓(5-1)和偏钒酸铵螺旋加料器(5-2)；
    所述煅烧流化床(6)包括煅烧床空气净化器(6-1)、煅烧床气体加热器(6-2)、煅烧床进料器(6-3)、煅烧流化床主体(6-4)、煅烧床旋风分离器(6-5)和高纯五氧化二钒料仓(6-6)；
    所述工业级五氧化二钒料仓(1-1)底部的出料口与所述工业级五氧化二钒螺旋加料器(1-2)的进料口相连接；所述炭粉料仓(1-3)底部的出料口与所述炭粉螺旋加料器(1-4)的进料口相连接；所述工业级五氧化二钒螺旋加料器(1-2)的出料口、所述炭粉螺旋加料器(1-4)的出料口均与所述氯化床进料器(2-1)的进料口通过管道相连接；
    所述氯化床进料器(2-1)的排料口与所述氯化流化床主体(2-2)上部的进料口通过管道相连接；所述氯化床进料器(2-1)底部的进气口通过管道与氮气气源总管相连接；所述氯化床旋风分离器(2-3)设置于所述氯化流化床主体(2-2)的扩大段顶部中心；所述氯化床旋风分离器(2-3)顶部的出气口通过管道与所述烟气换热器(2-4)的热烟气入口相连接；所述烟气换热器(2-4)的冷烟气出 口通过管道与所述烟气冷凝器(2-5)的气体入口相连接；所述烟气冷凝器(2-5)的气体出口通过管道与所述氯化床酸封罐(2-6)的气体入口相连接；所述氯化床酸封罐(2-6)的气体出口通过管道与所述尾气淋洗吸收器(7)的气体入口相连接；所述氯化流化床主体(2-2)下部的排渣口与所述氯化床螺旋排渣器(2-7)的进料口通过管道相连接；所述氯化流化床主体(2-2)底部的进气口通过管道与所述烟气换热器(2-4)的热气体出口相连接；所述烟气换热器(2-4)的冷气体入口通过管道分别与氯气气源总管、氮气气源总管及压缩空气总管相连接；
    所述烟气冷凝器(2-5)底部的液体出口通过管道与所述精馏塔(3-2)的进料口相连接；所述蒸馏釜(3-1)的蒸气出口通过管道与所述精馏塔(3-2)的蒸气入口相连接；所述蒸馏釜(3-1)的回流口通过管道与所述精馏塔(3-2)底部的液体回流出口相连接；所述精馏塔(3-2)顶部的气体出口通过管道与所述馏出物冷凝器(3-3)的气体入口相连接；所述馏出物冷凝器(3-3)的液体出口通过管道与所述回流液收集罐(3-4)的液体入口相连接；所述回流液收集罐(3-4)的回流液体出口通过管道与所述精馏塔(3-2)顶部的回流液体入口相连接；所述回流液收集罐(3-4)的排料口与所述含硅三氯氧钒储罐(3-5)的入口通过管道相连接；所述含硅三氯氧钒储罐(3-5)的乏气出口通过管道与所述精馏段酸封罐(3-6)的气体入口相连接；所述精馏酸封罐(3-6)的气体出口通过管道与所述尾气淋洗吸收器(7)的气体入口相连接；所述精馏塔(3-2)的精馏物出口通过管道与所述高纯三氯氧钒冷凝器(3-7)的气体入口相连接；所述高纯三氯氧钒冷凝器(3-7)的液体出口与所述高纯三氯氧钒储罐(3-8)的液体入口通过管道相连接；所述蒸馏釜(3-1)底部设置了底流出口；
    所述铵化床空气净化器(4-1)的进气口与压缩空气总管通过管道相连接；所述铵化床空气净化器(4-1)的出气口通过管道分别与所述铵化床气体加热器(4-2)的进气口、三氯氧钒喷嘴(4-3)的气体入口及铵化床排料器(4-6)底部的进气口相连接；所述铵化床气体加热器(4-2)的进气口通过管道与超纯水、纯化液氨总管相连接；所述铵化床气体加热器(4-2)燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；所述铵化床气体加热器(4-2)的出气口通过管道与所述气相铵化流化床主体(4-4)底部的进气口相连接；所述高纯三氯氧钒储罐(3-8)的液体出口通过管道与所述三氯氧钒喷嘴(4-3)的三氯氧钒入口相连接；所述铵化床旋风分离器(4-5)设置于所述气相铵化流化床主体(4-4)扩大段顶部中心处；所述铵化床旋风分离器(4-5)的顶部出气 口通过管道与尾气处理单元相连接；所述气相铵化流化床主体(4-4)上部的排料口通过管道与所述铵化床排料器(4-6)的进料口相连接；所述铵化床排料器(4-6)的排料口通过管道与所述偏钒酸铵料仓(5-1)的进料口相连接；
    所述偏钒酸铵料仓(5-1)底部的出料口与所述偏钒酸铵螺旋加料器(5-2)的进料口相连接；所述偏钒酸铵螺旋加料器(5-2)的排料口通过管道与所述煅烧床进料器(6-3)的进料口通过管道相连接；
    所述煅烧床空气净化器(6-1)的进气口与压缩空气总管通过管道相连接；所述煅烧床空气净化器(6-1)的出气口通过管道分别与所述煅烧床气体加热器(6-2)的进气口和煅烧床进料器(6-3)底部的进气口相连接；所述煅烧床气体加热器(6-2)燃烧嘴的助燃风入口和燃料入口分别通过管道与压缩空气总管和燃料总管相连接；所述煅烧床气体加热器(6-2)的出气口通过管道与所述煅烧流化床主体(6-4)底部的进气口相连接；所述煅烧床进料器(6-3)的排料口通过管道与所述煅烧床流化床主体(6-4)下部的进料口相连接；所述煅烧流化床主体(6-4)顶部的出气口通过管道与所述煅烧床旋风分离器(6-5)的进气口相连接；所述煅烧床旋风分离器(6-5)底部的粉料出口通过管道与氯化铵料仓进料口相连接；所述煅烧床旋风分离器(6-5)的顶部出气口通过管道与尾气处理单元相连接；所述煅烧流化床主体(6-4)上部的排料口通过管道与所述高纯五氧化二钒料仓(6-6)的进料口相连接；
    所述尾气淋洗吸收器(7)的气体出口通过管道与所述引风机(8)的气体入口相连接；所述引风机(8)的气体出口通过管道与所述烟囱(9)底部的气体入口相连接。
  2. 一种基于权利要求1所述系统的提纯制备高纯五氧化二钒粉体的方法，包括以下步骤：
    所述工业级五氧化二钒料仓(1-1)中的工业级五氧化二钒粉料和所述炭粉料仓(1-3)的炭粉分别经所述工业级五氧化二钒螺旋加料器(1-2)和所述炭粉螺旋加料器(1-4)同时进入所述氯化床进料器(2-1)混合后进入所述氯化流化床主体(2-2)；来自氯气气源总管的氯气、氮气气源总管的氮气及压缩空气总管的空气经所述烟气换热器(2-4)与氯化烟气换热预热后进入所述氯化流化床主体(2-2)中使五氧化二钒和炭粉维持流态化并与之发生化学反应，空气使部分炭粉发生燃烧提供热量维持流化床温度，氯气与炭粉共同作用使五氧化二钒和少量杂质发生氯化，形成氯化残渣和富含三氯氧钒的氯化烟气；氯化残渣依次经所 述氯化流化床主体(2-2)下部的排渣口和所述氯化床螺旋排渣器(2-7)排出；氯化烟气经所述氯化床旋风分离器(2-3)将粉尘脱除并落回氯化流化床主体(2-2)后，再经所述烟气换热器(2-4)预冷却并进入烟气冷凝器(2-5)中使其中的三氯氧钒冷凝形成粗三氯氧钒液体，剩余尾气经所述氯化床酸封罐(2-6)后进入所述尾气淋洗吸收器(7)中；
    所述烟气冷凝器(2-5)形成的粗三氯氧钒液体进入所述精馏塔(3-2)和所述蒸馏釜(3-1)后进行精馏操作，得到富含高沸点杂质的富钒废料、富含低沸点杂质的含硅三氯氧钒蒸气和高纯三氯氧钒蒸气；含硅三氯氧钒蒸气经所述馏出物冷凝器(3-3)冷凝至液体后，部分经回流液收集罐(3-4)回流至所述精馏塔(3-2)，其余部分进入所述含硅三氯氧钒储罐(3-5)中；含硅三氯氧钒储罐(3-5)中产生的乏气经所述精馏段酸封罐(3-6)后送往所述尾气淋洗吸收器(7)中；高纯三氯氧钒蒸气经所述高纯三氯氧钒冷凝器(3-7)冷凝至液体后进入所述高纯三氯氧钒储罐(3-8)中；
    所述高纯三氯氧钒储罐(3-8)的高纯三氯氧钒经所述三氯氧钒喷嘴(4-3)，由来自铵化床空气净化器(4-1)的净化空气气载进入所述气相铵化流化床主体(4-4)中；超纯水、纯化液氨和净化空气经所述铵化床气体加热器(4-2)预热后送入所述气相铵化流化床主体(4-4)中使床内粉料维持流态化，并使三氯氧钒发生水解和铵化，生成含氯化铵的偏钒酸铵粉体，所述含氯化铵的偏钒酸铵粉体经铵化床排料器(4-6)排出后进入所述偏钒酸铵料仓(5-1)中，产生的含氨的铵化烟气经铵化床旋风分离器(4-5)脱除粉尘后送尾气处理单元处理；
    所述偏钒酸铵料仓(5-1)中的含氯化铵的偏钒酸铵粉料依次经所述偏钒酸铵螺旋加料器(5-2)和煅烧床进料器(6-3)进入所述煅烧流化床主体(6-4)中；压缩空气依次经煅烧床空气净化器(6-1)净化和煅烧床气体加热器(6-2)预热后进入所述煅烧流化床主体(6-4)中使床内粉料维持流态化，并使含氯化铵的偏钒酸铵物料发生热分解，得到高纯五氧化二钒粉体产品，经所述煅烧流化床主体(6-4)上部的排料口进入所述高纯五氧化二钒料仓(6-6)中；煅烧分解产生的煅烧烟气进入所述煅烧床旋风分离器(6-5)降温析出氯化铵并脱除粉尘后送尾气处理单元处理；所述煅烧床旋风分离器(6-5)收集到的氯化铵粉料送往氯化铵料仓中；
    所述尾气淋洗吸收器(7)经碱溶液吸收处理后排出的气体经所述引风机(8)送入所述烟囱(9)后排空。
  3. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，在所述氯化流化床主体(2-2)内，所述氯化过程炭粉添加量为工业级五氧化二钒粉料质量的10％～20％。
  4. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，在所述氯化流化床主体(2-2)内，氯化操作温度为300～500℃，粉料的平均停留时间为30～80min。
  5. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，在所述精馏塔(3-2)内，所述精馏操作精馏段的塔板数为5～10块，提馏段的塔板数为10～20块。
  6. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，所述精馏操作的回流比为15～40。
  7. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，在所述气相铵化流化床主体(4-4)内，通过高纯三氯氧钒气相铵化制备得到偏钒酸铵，所述气相铵化的操作温度为130～250℃，水蒸气与氨气的摩尔比为0.5～0.8，氨气与三氯氧钒的摩尔比为3.5～4.5。
  8. 根据权利要求2所述的提纯制备高纯五氧化二钒粉体的方法，其特征在于，在所述煅烧流化床主体(6-4)内，通过流态化煅烧实现含氯化铵的偏钒酸铵的热分解，所述煅烧操作温度为400～650℃，粉料的平均停留时间为60～180min。
PCT/CN2016/072524 2015-01-30 2016-01-28 一种提纯制备高纯五氧化二钒粉体的系统及方法 WO2016119722A1 (zh)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AU2016212456A AU2016212456B2 (en) 2015-01-30 2016-01-28 System and method for purifying and preparing high-purity vanadium pentoxide powder
CA2973518A CA2973518C (en) 2015-01-30 2016-01-28 System and method for purifying and preparing high-purity vanadium pentoxide powder
BR112017015812-4A BR112017015812A2 (zh) 2015-01-30 2016-01-28 A system and method for production of high purity vanadium pentoxide powder purification
NZ733888A NZ733888A (en) 2015-01-30 2016-01-28 System and method for purifying and preparing high-purity vanadium pentoxide powder
JP2017558611A JP6383118B2 (ja) 2015-01-30 2016-01-28 五酸化二バナジウム粉末の精製システム及び精製方法
RU2017130367A RU2665520C1 (ru) 2015-01-30 2016-01-28 Система и способ очистки и получения порошка высокочистого пентоксида ванадия
US15/547,068 US10125024B2 (en) 2015-01-30 2016-01-28 System and method for purifying and preparing high-purity vanadium pentoxide powder
EP16742784.8A EP3252014B1 (en) 2015-01-30 2016-01-28 System and method for purifying and preparing high-purity vanadium pentoxide powder
ZA2017/04633A ZA201704633B (en) 2015-01-30 2017-07-10 System and method for purifying and preparing high-purity vanadium pentoxide powder
PH12017550061A PH12017550061A1 (en) 2015-01-30 2017-07-28 System and method for purifying and preparing high-purity vanadium pentoxide powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510051577.XA CN105984896B (zh) 2015-01-30 2015-01-30 一种提纯制备高纯五氧化二钒粉体的系统及方法
CN201510051577.X 2015-01-30

Publications (1)

Publication Number Publication Date
WO2016119722A1 true WO2016119722A1 (zh) 2016-08-04

Family

ID=56542449

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/072524 WO2016119722A1 (zh) 2015-01-30 2016-01-28 一种提纯制备高纯五氧化二钒粉体的系统及方法

Country Status (12)

Country Link
US (1) US10125024B2 (zh)
EP (1) EP3252014B1 (zh)
JP (1) JP6383118B2 (zh)
CN (1) CN105984896B (zh)
AU (1) AU2016212456B2 (zh)
BR (1) BR112017015812A2 (zh)
CA (1) CA2973518C (zh)
NZ (1) NZ733888A (zh)
PH (1) PH12017550061A1 (zh)
RU (1) RU2665520C1 (zh)
WO (1) WO2016119722A1 (zh)
ZA (1) ZA201704633B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109292817A (zh) * 2018-12-07 2019-02-01 攀钢集团攀枝花钢铁研究院有限公司 制备偏钒酸铵的方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105984898B (zh) * 2015-01-30 2017-06-13 中国科学院过程工程研究所 一种生产高纯四氧化二钒粉体的系统及方法
CN105984897B (zh) * 2015-01-30 2017-05-17 中国科学院过程工程研究所 一种生产高纯五氧化二钒粉体的系统及方法
CN105984900B (zh) * 2015-01-30 2017-06-13 中国科学院过程工程研究所 一种制备高纯五氧化二钒粉体的系统及方法
CN106257726B (zh) * 2016-01-28 2018-03-23 中国科学院过程工程研究所 一种生产高纯度高活性钒电解液的系统及方法
CN109837395B (zh) * 2017-11-24 2020-09-18 中国科学院过程工程研究所 一种高值化综合利用高铬型钒渣的系统及方法
CN109835948B (zh) * 2017-11-24 2020-04-24 中国科学院过程工程研究所 一种高铬型钒渣生产液流电池用高纯储能材料的系统及方法
CN112090106B (zh) * 2020-09-15 2021-07-27 中国地质大学（武汉） 一种试剂提纯装置以及利用该装置提纯氟化氢铵或氟化铵的方法
CN114249306A (zh) * 2021-12-06 2022-03-29 武汉科技大学 一种基于富钒液的氮化钒及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845552A (zh) * 2010-04-23 2010-09-29 河北钢铁股份有限公司承德分公司 一种钒渣梯度氯化回收有价元素的方法
CN102234117A (zh) * 2010-05-05 2011-11-09 刘基扬 一种含可水解卤原子的物质的水解方法
CN103130279A (zh) * 2011-11-29 2013-06-05 刘艳梅 一种氯化生产高纯五氧化二钒的方法
CN103922403A (zh) * 2014-03-24 2014-07-16 攀钢集团攀枝花钢铁研究院有限公司 一种多钒酸铵流态化生产粉状五氧化二钒的方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3085634B2 (ja) 1994-11-17 2000-09-11 鹿島北共同発電株式会社 高純度バナジウム電解液の製造法
JPH10114525A (ja) * 1997-08-29 1998-05-06 Kashima Kita Kyodo Hatsuden Kk 高純度五酸化バナジウムの製造法
RU2175990C1 (ru) * 2000-04-05 2001-11-20 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения пентаоксида ванадия
RU23292U1 (ru) * 2001-11-16 2002-06-10 ООО Научно-производственная экологическая фирма "ЭКО-технология" Поточная линия для получения пентаоксида ванадия
JP5014565B2 (ja) * 2004-04-08 2012-08-29 Ｊｘ日鉱日石金属株式会社 高純度ｖ２ｏ５及びその製造方法
RU41719U1 (ru) * 2004-06-01 2004-11-10 Общество с ограниченной ответственностью Научно-производственная экологическая фирма "ЭКО-технология" Технологическая линия для получения пентаоксида ванадия
CN1843938A (zh) 2006-04-30 2006-10-11 宿素满 一种五氧化二钒的生产方法
CN100510127C (zh) * 2006-07-27 2009-07-08 张荣禄 从高钛型钒铁精矿中提取铁钛钒的方法
NL2004740C2 (en) * 2010-05-18 2011-11-22 Greenshores Patent B V Process for preparing vanadium pentoxide.
JP5742130B2 (ja) * 2010-08-04 2015-07-01 住友金属鉱山株式会社 五酸化バナジウムの製造方法
CN102730757A (zh) 2011-04-03 2012-10-17 崇阳县恒通工贸有限公司 一种用偏钒酸铵制备高纯五氧化二钒的方法
CN102181635A (zh) 2011-04-08 2011-09-14 北京矿冶研究总院 一种石煤钒矿硫酸浸出液制备五氧化二钒的方法
CN102557134B (zh) * 2011-12-23 2014-07-02 中国科学院过程工程研究所 一种生产高纯三氧化二钒的流态化还原炉及生产方法
CN103515642A (zh) 2012-06-25 2014-01-15 中国人民解放军63971部队 一种高纯度高浓度钒电池电解液的制备方法
CN102923775A (zh) 2012-11-27 2013-02-13 攀钢集团攀枝花钢铁研究院有限公司 一种高纯度五氧化二钒的制备方法
CN103145187B (zh) 2013-03-22 2014-11-05 中南大学 一种无害化高纯五氧化二钒的生产工艺
CN103194603B (zh) 2013-04-01 2015-06-10 攀枝花学院 高纯五氧化二钒的制备方法
CN103606694B (zh) 2013-11-15 2015-07-08 河北钢铁股份有限公司承德分公司 一种商用钒电池电解液的制备方法
CN103663557B (zh) 2014-01-07 2015-06-17 湖南有色金属研究院 一种粗钒制备高纯五氧化二钒的方法
CN103787414B (zh) 2014-01-26 2016-04-13 贵州义信矿业有限公司 焙烧法钒溶液制取高纯五氧化二钒的方法
CN105984898B (zh) * 2015-01-30 2017-06-13 中国科学院过程工程研究所 一种生产高纯四氧化二钒粉体的系统及方法
CN105984900B (zh) * 2015-01-30 2017-06-13 中国科学院过程工程研究所 一种制备高纯五氧化二钒粉体的系统及方法
CN105984897B (zh) * 2015-01-30 2017-05-17 中国科学院过程工程研究所 一种生产高纯五氧化二钒粉体的系统及方法
CN105984899B (zh) * 2015-01-30 2017-05-17 中国科学院过程工程研究所 一种提纯五氧化二钒的系统及方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845552A (zh) * 2010-04-23 2010-09-29 河北钢铁股份有限公司承德分公司 一种钒渣梯度氯化回收有价元素的方法
CN102234117A (zh) * 2010-05-05 2011-11-09 刘基扬 一种含可水解卤原子的物质的水解方法
CN103130279A (zh) * 2011-11-29 2013-06-05 刘艳梅 一种氯化生产高纯五氧化二钒的方法
CN103922403A (zh) * 2014-03-24 2014-07-16 攀钢集团攀枝花钢铁研究院有限公司 一种多钒酸铵流态化生产粉状五氧化二钒的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MCCARLEY, R.E. ET AL.: "Preparation of High Purity Vanadium Pentoxide by A Chlorination Procedure", THE LESS-COMMON METALS, 30 April 1960 (1960-04-30), pages 29 - 35, XP022782006 *
See also references of EP3252014A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109292817A (zh) * 2018-12-07 2019-02-01 攀钢集团攀枝花钢铁研究院有限公司 制备偏钒酸铵的方法

Also Published As

Publication number Publication date
RU2665520C1 (ru) 2018-08-30
CN105984896B (zh) 2017-06-13
NZ733888A (en) 2018-08-31
US10125024B2 (en) 2018-11-13
ZA201704633B (en) 2019-06-26
AU2016212456A1 (en) 2017-08-31
CA2973518C (en) 2019-11-26
BR112017015812A2 (zh) 2018-06-19
JP6383118B2 (ja) 2018-08-29
EP3252014A4 (en) 2018-01-03
JP2018511552A (ja) 2018-04-26
US20180009673A1 (en) 2018-01-11
CA2973518A1 (en) 2016-08-04
AU2016212456B2 (en) 2018-01-18
EP3252014A1 (en) 2017-12-06
EP3252014B1 (en) 2018-10-03
CN105984896A (zh) 2016-10-05
PH12017550061A1 (en) 2018-02-05

Similar Documents

Publication Publication Date Title
WO2016119722A1 (zh) 一种提纯制备高纯五氧化二钒粉体的系统及方法
WO2016119719A1 (zh) 一种生产高纯四氧化二钒粉体的系统及方法
WO2016119717A1 (zh) 一种生产高纯五氧化二钒粉体的系统及方法
WO2016119716A1 (zh) 一种制备高纯五氧化二钒粉体的系统及方法
WO2016119718A1 (zh) 一种提纯五氧化二钒的系统及方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16742784

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2973518

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2017558611

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15547068

Country of ref document: US

Ref document number: 12017550061

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2016742784

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112017015812

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2017130367

Country of ref document: RU

ENP Entry into the national phase

Ref document number: 2016212456

Country of ref document: AU

Date of ref document: 20160128

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01E

Ref document number: 112017015812

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112017015812

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20170724