WO2017128969A1 - 一种生产3.5价高纯钒电解液的系统及方法 - Google Patents

一种生产3.5价高纯钒电解液的系统及方法 Download PDF

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Publication number
WO2017128969A1
WO2017128969A1 PCT/CN2017/071207 CN2017071207W WO2017128969A1 WO 2017128969 A1 WO2017128969 A1 WO 2017128969A1 CN 2017071207 W CN2017071207 W CN 2017071207W WO 2017128969 A1 WO2017128969 A1 WO 2017128969A1
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Prior art keywords
vanadium
pipe
gas
cyclone
inlet
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PCT/CN2017/071207
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English (en)
French (fr)
Inventor
范川林
朱庆山
杨海涛
牟文恒
刘吉斌
王存虎
班琦勋
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Institute of Process Engineering of CAS
Beijing Zhongkaihongde Technology Co Ltd
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Institute of Process Engineering of CAS
Beijing Zhongkaihongde Technology Co Ltd
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Application filed by Institute of Process Engineering of CAS, Beijing Zhongkaihongde Technology Co Ltd filed Critical Institute of Process Engineering of CAS
Priority to US16/074,075 priority Critical patent/US10673088B2/en
Priority to AU2017210930A priority patent/AU2017210930B2/en
Priority to RU2018130745A priority patent/RU2695083C1/ru
Priority to CA3012273A priority patent/CA3012273A1/en
Priority to NZ744570A priority patent/NZ744570A/en
Priority to JP2018539348A priority patent/JP6588652B2/ja
Priority to EP17743584.9A priority patent/EP3401991B1/en
Publication of WO2017128969A1 publication Critical patent/WO2017128969A1/zh
Anticipated expiration legal-status Critical
Priority to ZA201805714A priority patent/ZA201805714B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0045—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by means of a rotary device in the flow channel
    • 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
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • 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
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • 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
    • B01J8/1836—Heating and cooling the reactor
    • 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
    • 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
    • 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
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00752—Feeding
    • 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
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • 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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of energy and chemical industry, and particularly relates to a system and a method for producing a 3.5-valent high-purity vanadium electrolyte.
  • VRB all-vanadium flow battery
  • the biggest advantage of VRB is its flexibility – power and energy storage capacity are independent.
  • the power of the VRB is determined by the number of battery cells and the effective electrode area of the battery cells, and the energy storage capacity is determined by the concentration of the active material in the electrolyte and the volume of the electrolyte.
  • Each battery cell consists of two pole chambers (the positive and negative chambers) separated by a proton exchange membrane.
  • An electrolyte solution, a vanadium sulfate solution is used to store energy.
  • Vanadium electrolyte is a vital component of all vanadium redox flow batteries.
  • Vanadium battery new reactor configuration generally uses V (III) and V (IV) concentration ratio of 1:1 mixed vanadium electrolyte, that is, the average valence state of vanadium ions in the electrolyte is 3.5.
  • the electrolyte can be directly used in the positive and negative electrodes, and the operation is simple.
  • the purity of the vanadium electrolyte plays a crucial role in battery performance.
  • the impurity concentration in the electrolyte is high, the following problems are caused: (1) The impurity ions and the vanadium ions have a competitive reaction, and the battery efficiency is lowered.
  • impurity ions are deposited on the graphite felt electrode, blocking the voids of the graphite felt, reducing the specific surface area of the graphite felt, thereby affecting the charge and discharge efficiency.
  • the impurity ions will catalyze the hydrogen over-potential, and the gas will affect the pressure balance inside the battery.
  • Impurity ions reduce the lifetime of the proton exchange membrane.
  • Impurity ions affect the stability of vanadium ions, leading to premature aging of the electrolyte.
  • VOSO 4 method US Pat. No. 849,094 discloses a method for preparing V(III) and V(IV) concentrations by electrochemically adjusting the valence state by dissolving VOSO 4 in a sulfuric acid solution. A vanadium electrolyte mixed with a ratio of 1:1.
  • a vanadium electrolyte in which V(III) and V(IV) are mixed The main problem of this method is that the degree of reduction is not easy to control accurately; the V 2 O 5 prepared by the prior process is difficult to achieve high purification, and the electrolyte configured by this process contains more impurities; the addition of reducing agent introduces new impurities into the vanadium electrolysis. Liquid system, affecting the purity of the electrolyte.
  • Electrolysis method International PCT patent AKU88/000471 introduces the addition of V 2 O 5 to sulfuric acid solution, and the preparation of mixed vanadium electrolyte with V(III) and V(IV) concentration ratio of 1:1 by constant current electrolysis. .
  • V(III) vanadium ion hydrate easily forms an oxygen bridge to produce polycondensation at a temperature of 80-150 ° C, resulting in a decrease in electrolyte activity and a lack of activation step; this method can only be used for Preparation of negative electrode electrolyte, the application surface is narrow; the patented industrial high purity V 2 O 3 , the total vanadium content is 67%, equivalent to 98.5% purity, still contains many impurity ions.
  • Cid patent CN102468509A discloses a preparation method of a vanadium battery electrolyte, which uses V-ammonium vanadate and ammonium hydrogencarbonate as raw materials to prepare V 2 O 3 by section calcination at 200-300 ° C and 600-700 ° C.
  • the V 2 O 3 is dissolved in dilute sulfuric acid at 50 to 120 ° C for 5 to 20 hours to obtain a V 2 (SO 4 ) 3 solution.
  • the V 2 O 5 was dissolved in a V 2 (SO 4 ) 3 solution at 80 to 110 ° C for 1 to 3 hours to obtain a vanadium battery electrolyte having an average vanadium ion concentration of 3.5.
  • V 2 (SO 4 ) 3 solution was prepared in this patent for use in a negative electrode electrolyte.
  • the main problem of this method is that the V(III) vanadium ion hydrate easily forms an oxygen bridge bond at a higher temperature to cause polycondensation, resulting in a decrease in electrolyte activity and a lack of activation step; the electrolyte purity is not high.
  • Chinese patent CN103401010A discloses a preparation method of an all-vanadium redox flow battery electrolyte, which is prepared by reducing V 2 O 5 powder in hydrogen to prepare V 2 O 4 powder and V 2 O 3 powder.
  • V 2 O 4 and V 2 O 3 were respectively dissolved in concentrated sulfuric acid to obtain a positive electrode and a negative electrode electrolyte of the vanadium battery.
  • the main problem of this patent is that no specific reduction process is given, and V 2 O 5 powder is reduced in hydrogen to prepare V 2 O 4 powder, which is prone to over-reduction or under-reduction, which requires precise control.
  • the present invention proposes a system and method for producing a 3.5-valent high-purity vanadium electrolyte to simplify the preparation process, improve the purity of the electrolyte, and improve the simplicity of the electrolyte.
  • the present invention adopts the following technical solutions:
  • the invention provides a system for producing a 3.5-valent high-purity vanadium electrolyte, the system comprising a vanadium oxychloride storage tank, a gas phase hydrolysis fluidized bed 2, a vanadium pentoxide feeding device 3, a preheating dust removing device 4, a reducing fluidized bed 5, primary cooling device 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation device 9, exhaust gas extraction absorption tower 10, induced draft fan 11 and chimney 12;
  • the gas phase hydrolysis fluidized bed 2 comprises a vanadium oxychloride vaporizer 2-1, a clean water vaporizer 2-2, a chloride spray gun 2-3, a gas phase hydrolysis fluidized bed main body 2-4, a hydrolyzed fluidized bed discharger 2 -5, hydrochloric acid exhaust gas absorber 2-6;
  • the vanadium pentoxide feeding device 3 comprises a vanadium pentoxide silo 3-1 and a vanadium pentoxide screw feeder 3-2;
  • the preheating dust removing device 4 comprises a venturi preheater 4-1, a first cyclone separator 4-2, a cyclone preheater 4-3, a bag filter 4-4;
  • the reducing fluidized bed 5 comprises a feeder 5-1, a bed 5-2, a discharger 5-3, a gas heater 5-4, a gas purifier 5-5, a cyclone 5-6;
  • the primary cooling device 6 includes a venturi cooler 6-1, a second cyclone separator 6-2, a cyclone cooler 6-3;
  • the low-cost vanadium oxide feeding device 8 comprises a low-cost vanadium oxide silo 8-1 and a low-cost vanadium oxide screw feeder 8-2;
  • the dissolution activation device 9 comprises a stirring dissolution device 9-1 and a microwave activation device 9-2;
  • the outlet of the bottom of the vanadium oxychloride vapor storage tank 1 is connected to the inlet of the vanadium oxychloride vaporizer 2-1 through a pipeline; the inlet of the vanadium oxychloride vaporizer 2-1 is connected to the purified nitrogen manifold through a pipeline
  • the gas outlet of the vanadium oxychloride vaporizer 2-1 is connected to the inlet of the chloride spray gun 2-3 through a pipe; the inlet of the clean water vaporizer 2-2 is separately purified from the clean water main pipe through the pipeline
  • the air main pipe is connected; the air outlet of the clean water vaporizer 2-2 is connected to the air inlet of the bottom of the gas phase hydrolysis fluidized bed main body 2-4 through a pipe; the gas phase hydrolysis fluidized bed main body 2-4 is enlarged
  • the gas outlet at the top is connected to the gas inlet of the hydrochloric acid exhaust gas absorber 2-6 through a pipe; the hydrochloric acid tail gas absorber 2-6 is provided with
  • the outlet of the bottom of the vanadium pentoxide silo 3-1 is connected to the inlet of the vanadium pentoxide screw feeder 3-2; the outlet of the vanadium pentoxide screw feeder 3-2 a port and a feed port of the venturi preheater 4-1 connected by a pipe;
  • the discharge port of the venturi preheater 4-1 is connected to the feed port of the first cyclone separator 4-2 through a pipe, and the air outlet of the first cyclone separator 4-2 and the bag
  • the air inlet of the dust collector 4-4 is connected by a pipe;
  • the discharge port of the first cyclone 4-2 is connected to the air inlet of the cyclone preheater 4-3 through a pipe;
  • the air outlet of 4-4 is connected to the air inlet of the exhaust gas absorbing absorber 10 through a pipe;
  • the fine powder outlet of the bag filter 4-4 and the air inlet of the cyclone preheater 4-3 are passed through;
  • the air inlet of the heat exchanger 4-1 is connected by a pipe;
  • the discharge port of the feeder 5-1 is connected to the inlet of the bed 5-2 through a pipe; the loose air inlet of the feeder 5-1 is connected to the purified nitrogen main pipe; the bed body The air inlet of 5-2 is connected to the air outlet of the gas heater 5-4 through a pipe; the vertical baffle is arranged in the bed 5-2; the discharge port of the bed 5-2 and the row The inlet of the feeder 5-3 is connected by a pipe; the outlet of the bed 5-2 is connected to the inlet of the cyclone 5-6 through a pipe; the outlet of the cyclone 5-6 a gas port is connected to the inlet of the cyclone preheater 4-3 through a pipe; a discharge port of the cyclone 5-6 is connected to a feed port of the discharger 5-3 through a pipe; The discharge port of the discharger 5-3 is connected to the inlet of the venturi cooler 6-1 through a pipe; the loose air inlet of the discharger 5-3 is connected to the purge nitrogen main pipe; the gas heating The air outlet of
  • a feed port of the venturi cooler 6-1 is connected to a discharge port of the discharger 5-3; an intake port of the venturi cooler 6-1 and the cyclone cooler 6-3
  • the air outlets are connected by pipes; the venturi cooler 6-1
  • the air outlet is connected to the air inlet of the second cyclone separator 6-2 through a pipe; the air outlet of the second cyclone separator 6-2 and the air inlet of the gas heater 5-4 pass through the pipeline Connected;
  • the discharge port of the second cyclone separator 6-2 is connected to the air inlet of the cyclone cooler 6-3;
  • the air inlet of the cyclone cooler 6-3 is connected to the purified nitrogen manifold;
  • An air outlet of the cyclone cooler 6-3 is connected to an air inlet of the venturi cooler 6-1 through a pipe; a discharge port of the cyclone cooler 6-3 and the secondary cooling device 7
  • the material port is connected by a pipe;
  • the feed port of the secondary cooling device 7 is connected to the discharge port of the cyclone cooler 6-3 through a pipe; the discharge port of the secondary cooling device 7 and the low-cost vanadium oxide silo 8-
  • the feed port of the first cooling device 7 is connected to the process water main pipe through a pipe; the water outlet of the secondary cooling device 7 is connected to the water inlet of the water cooling system through a pipe;
  • the discharge port at the bottom of the low-priced vanadium oxide silo 8-1 is connected to the feed port of the low-cost vanadium oxide screw feeder 8-2; the low-cost vanadium oxide screw feeder 8-2 a discharge port and a feed port of the dissolution activation device 9 are connected through a pipe;
  • the clean water inlet of the stirring and dissolving device 9-1 is connected to the clean water main pipe through a pipe; the sulfuric acid solution inlet of the stirring and dissolving device 9-1 is connected to the sulfuric acid solution main pipe through a pipe; and the gas of the stirring and dissolving device 9-1 is stirred.
  • the outlet is connected to the inlet of the exhaust gas absorbing absorption tower 10 through a pipe; the stirring and dissolving device 9-1 is placed inside the microwave activating device 9-2;
  • the gas outlet of the exhaust gas leaching absorption tower 10 is connected to the gas inlet of the induced draft fan 11 through a pipe; the gas outlet of the induced draft fan 11 is connected to the gas inlet at the bottom of the chimney 12 through a pipe.
  • the method for producing a 3.5-valent high-purity vanadium electrolyte based on the above system of the present invention comprises the following steps:
  • the vanadium oxychloride in the vanadium pentoxide storage tank 1 and the nitrogen from the purified nitrogen main pipe are preheated by the vaporization of the vanadium oxychloride vaporizer 2-1, and then enter the gas phase through the chloride spray gun 2-3. Hydrolyzing the fluidized bed main body 2-4; the clean water and the purified air are vaporized and preheated by the clean water vaporizer 2-2, and then sent to the gas phase hydrolysis fluidized bed main body 2-4 to cause hydrolysis of vanadium oxychloride.
  • the vanadium pentoxide powder is discharged through the hydrolyzed fluidized bed discharger 2-5 In the vanadium pentoxide silo 3-1; the hydrolyzed flue gas is removed by the enlarged section of the gas phase hydrolysis fluidized bed main body 2-4, and then enters the hydrochloric acid exhaust gas absorber 2-6 for absorption treatment to form a hydrochloric acid solution.
  • the hydrochloric acid exhaust gas absorber 2-6 for absorption treatment to form a hydrochloric acid solution.
  • the vanadium pentoxide in the vanadium pentoxide silo 3-1 sequentially enters the vanadium pentoxide screw feeder 3-2.
  • the venturi preheater 4-1, the first cyclone separator 4-2, the cyclone preheater 4-3, and the fine powder recovered from the bag filter (4-4) The particles enter the bed 5-2 together through the feeder 5-1; the purified nitrogen passes through the cyclone cooler 6-3, the venturi cooler 6-1, the second After the cyclone separator 6-2 is preheated, it is mixed with the purified reducing gas from the gas purifier 5-5, and then preheated by the gas heater 5-4 to enter the bed 5-2 to be pentridized.
  • the vanadium powder material maintains fluidization and reduces it to obtain a low-valent vanadium oxide powder and a reduced flue gas; the low-valent vanadium oxide passes through the discharge port of the bed 5-2 and the cyclone
  • the fine powder recovered by the dust remover 5-6 sequentially enters the discharger 5-3, the venturi cooler 6-1, the second cyclone separator 6-2, and the cyclone cooler 6-3.
  • the secondary cooler 7 After the secondary cooler 7 is cooled, it enters the low-cost vanadium oxide silo 8-1; the reduced flue gas in the bed 5-2 sequentially enters the cyclone 5-6, Cyclone preheater 4-3, the venturi preheater 4 -1, the first cyclone separator 4-2, after being dedusted by the bag filter 4-4, enters the exhaust gas eluting absorber 10, and the gas discharged after being absorbed by the alkali solution is passed through the induced draft fan 11 After being sent into the chimney 12, it is emptied;
  • the low-valent vanadium oxide in the low-valent vanadium oxide silo 8-1 enters the stirring and dissolving device 9-1 through the low-valent vanadium oxide screw feeder 8-2, in the microwave activating device 9 -2 provides a microwave field, and dissolves with a sulfuric acid solution from the clean water and sulfuric acid solution main pipe of the clean water main pipe to obtain a high-purity vanadium electrolyte, and the generated acid mist gas is sent to the exhaust gas elution absorber. 10 for processing.
  • the vanadium oxychloride raw material has a purity of 99% to 99.9999%, that is, 2N to 6N.
  • the second feature of the present invention is that in the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 40 to 600 ° C, and the molar ratio of nitrogen gas to vanadium oxychloride is 0.10 to 10.00.
  • the third feature of the present invention is that in the clean water vaporizer 2-2, the vaporization operation temperature is 40 to 600 ° C, and the mass ratio of air to water is 0.10 to 10.00.
  • the fourth feature of the present invention is that in the gas phase hydrolysis fluidized bed main body 2-4, the vanadium pentoxide powder is directly prepared by vapor phase hydrolysis of vanadium oxychloride, and the vapor phase hydrolysis process is carried out by introducing water vapor and vanadium oxychloride.
  • the mass ratio is 0.10 to 10.00
  • the gas phase hydrolysis operation temperature is 100 to 600 ° C
  • the average residence time of the powder is 15 to 300 min.
  • the fifth feature of the present invention is that in the reduced fluidized bed main body 5-2, the operating temperature of the reduction is 400 to 700 ° C, and the reducing gas is purified by the purifier 5-5, and the organic matter content is less than 1 mg/Nm 3 .
  • the total content of solid particles is less than 2 mg/Nm 3 , and the integral number of reducing gas in the mixed gas of nitrogen and reducing gas is 10% to 90%, and the average residence time of the powder is 30 to 90 minutes.
  • a sixth feature of the present invention resides in that the sulfuric acid solution is a sulfuric acid solution having an electronic grade purity of 4.0 to 10.0 mol/L.
  • a seventh feature of the present invention is that the high purity vanadium electrolyte is a vanadium electrolyte having a molar ratio of V(III) and V(IV) vanadium ions of 1:1, and the average valence state of the vanadium ions is 3.5.
  • the obtained 3.5-valent high-purity vanadium electrolyte can be directly used in a new stack of all-vanadium redox flow batteries.
  • the eighth feature of the present invention is that in the dissolution activation device 9, the external microwave field is used to assist the dissolution and activation of the vanadium ion of the low-valent vanadium oxide, the dissolution activation time is 30 to 300 minutes, and the dissolution activation temperature is 20 to 45 ° C, microwave power density is 10 ⁇ 300W / L, microwave frequency is 2450MHz or 916MHz,
  • the electrolyte produced by the invention has high purity, high activity, convenient electrolyte configuration and convenient use, and the invention has the following outstanding advantages over the prior art:
  • High purity vanadium oxychloride having a purity of 2N to 6N is easily obtained by using vanadium oxychloride which is easily purified.
  • the present invention can prepare a low-cost vanadium oxide having a purity of 4N5 (that is, a purity of 99.995%), thereby preparing a high-purity vanadium electrolyte, in addition to the effective component, the total impurity content is less than 5 ppm;
  • the high-temperature tail gas discharged from the reduced fluidized bed is directly contacted with the cold vanadium-containing material, and the cold-containing vanadium-containing material is heated while recovering the sensible heat of the high-temperature reducing tail gas;
  • the reduction is directly contacted with the discharged high-temperature and low-valent vanadium oxide product by the purified nitrogen gas, and the purified nitrogen product is preheated while recovering the sensible heat of the high-temperature reduction product;
  • 3.5-valent electrolyte It is suitable for the new stack configuration of vanadium battery. It can be directly used in the positive and negative chambers for easy operation.
  • the invention has low production energy consumption and operation cost, high product purity, stable quality, electrolyte configuration and assembly
  • the advantages of clean and so on are suitable for large-scale industrial production of all vanadium redox flow battery electrolyte, and have good economic and social benefits.
  • Figure 1 is a schematic view showing the configuration of a 3.5-valent high-purity electrolyte system of the present invention.
  • Venturi preheater 4-2, first cyclone separator; 4-3, cyclone preheater; 4-4, bag filter;
  • Venturi cooler 6-2, second cyclone separator; 6-3, cyclone cooler;
  • 8-1 low-cost vanadium oxide silo
  • 8-2 low-cost vanadium oxide screw feeder
  • the system for producing a 3.5-valent high-purity vanadium electrolyte used in the present embodiment includes a vanadium oxychloride vanadium 1, a gas phase hydrolyzed fluidized bed 2, a vanadium pentoxide feeding device 3, and a preheating dust removing device 4. , reducing fluidized bed 5, primary cooling device 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation device 9, exhaust gas elution absorption tower 10, induced draft fan 11 and chimney 12;
  • the gas phase hydrolysis fluidized bed 2 comprises a vanadium oxychloride vaporizer 2-1, a clean water vaporizer 2-2, a chloride spray gun 2-3, a gas phase hydrolysis fluidized bed main body 2-4, a hydrolyzed fluidized bed discharger 2 -5, hydrochloric acid exhaust gas absorber 2-6;
  • the vanadium pentoxide feeding device 3 comprises a vanadium pentoxide silo 3-1 and a vanadium pentoxide screw feeder 3-2;
  • the preheating dust removing device 4 comprises a venturi preheater 4-1, a first cyclone separator 4-2, a cyclone preheater 4-3, a bag filter 4-4;
  • the reducing fluidized bed 5 comprises a feeder 5-1, a bed 5-2, a discharger 5-3, a gas heater 5-4, a gas purifier 5-5, a cyclone 5-6;
  • the primary cooling device 6 includes a venturi cooler 6-1, a second cyclone separator 6-2, a cyclone cooler 6-3;
  • the low-cost vanadium oxide feeding device 8 comprises a low-cost vanadium oxide silo 8-1 and a low-cost vanadium oxide screw feeder 8-2;
  • the dissolution activation device 9 comprises a stirring dissolution device 9-1 and a microwave activation device 9-2;
  • the outlet of the bottom of the vanadium oxychloride vapor storage tank 1 is connected to the inlet of the vanadium oxychloride vaporizer 2-1 through a pipeline; the inlet of the vanadium oxychloride vaporizer 2-1 is connected to the purified nitrogen manifold through a pipeline
  • the gas outlet of the vanadium oxychloride vaporizer 2-1 is connected to the inlet of the chloride spray gun 2-3 through a pipe; the inlet of the clean water vaporizer 2-2 is separately purified from the clean water main pipe through the pipeline
  • the air main pipe is connected; the air outlet of the clean water vaporizer 2-2 is connected to the air inlet of the bottom of the gas phase hydrolysis fluidized bed main body 2-4 through a pipe; the gas phase hydrolysis fluidized bed main body 2-4 is enlarged
  • the gas outlet at the top is connected to the gas inlet of the hydrochloric acid exhaust gas absorber 2-6 through a pipe a hydrochloric acid solution outlet is disposed at the bottom of the
  • the outlet of the bottom of the vanadium pentoxide silo 3-1 is connected to the inlet of the vanadium pentoxide screw feeder 3-2; the outlet of the vanadium pentoxide screw feeder 3-2 a port and a feed port of the venturi preheater 4-1 connected by a pipe;
  • the discharge port of the venturi preheater 4-1 is connected to the feed port of the first cyclone separator 4-2 through a pipe, and the air outlet of the first cyclone separator 4-2 and the bag
  • the air inlet of the dust collector 4-4 is connected by a pipe;
  • the discharge port of the first cyclone 4-2 is connected to the air inlet of the cyclone preheater 4-3 through a pipe;
  • the air outlet of 4-4 is connected to the air inlet of the exhaust gas absorbing absorber 10 through a pipe;
  • the fine powder outlet of the bag filter 4-4 and the air inlet of the cyclone preheater 4-3 are passed through;
  • the air inlet of the heat exchanger 4-1 is connected by a pipe;
  • the discharge port of the feeder 5-1 is connected to the inlet of the bed 5-2 through a pipe; the loose air inlet of the feeder 5-1 is connected to the purified nitrogen main pipe; the bed body The air inlet of 5-2 is connected to the air outlet of the gas heater 5-4 through a pipe; the vertical baffle is arranged in the bed 5-2; the discharge port of the bed 5-2 and the row The inlet of the feeder 5-3 is connected by a pipe; the outlet of the bed 5-2 is connected to the inlet of the cyclone 5-6 through a pipe; the outlet of the cyclone 5-6 a gas port is connected to the inlet of the cyclone preheater 4-3 through a pipe; a discharge port of the cyclone 5-6 is connected to a feed port of the discharger 5-3 through a pipe; The discharge port of the discharger 5-3 is connected to the inlet of the venturi cooler 6-1 through a pipe; the loose air inlet of the discharger 5-3 is connected to the purge nitrogen main pipe; the gas heating The air outlet of
  • a feed port of the venturi cooler 6-1 is connected to a discharge port of the discharger 5-3; an intake port of the venturi cooler 6-1 and the cyclone cooler 6-3
  • the air outlet is connected by a pipe; the air outlet of the venturi cooler 6-1 is connected to the air inlet of the second cyclone 6-2 through a pipe; the second cyclone 6-2 is discharged a gas port is connected to the gas inlet of the gas heater 5-4 through a pipe; a discharge port of the second cyclone separator 6-2 is connected to an air inlet of the cyclone cooler 6-3; the cyclone
  • the air inlet of the cooler 6-3 is connected to the purified nitrogen manifold; the air outlet of the cyclone cooler 6-3 is connected to the air inlet of the venturi cooler 6-1 through a pipe; the cyclone cooler 6 a discharge port of -3 is connected to a feed port of the secondary cooling device 7 through a pipe;
  • the feed port of the secondary cooling device 7 is connected to the discharge port of the cyclone cooler 6-3 through a pipe; the discharge port of the secondary cooling device 7 and the low-cost vanadium oxide silo 8-
  • the feed port of the first cooling device 7 is connected to the process water main pipe through a pipe; the water outlet of the secondary cooling device 7 is connected to the water inlet of the water cooling system through a pipe;
  • the discharge port at the bottom of the low-priced vanadium oxide silo 8-1 is connected to the feed port of the low-cost vanadium oxide screw feeder 8-2; the low-cost vanadium oxide screw feeder 8-2 a discharge port and a feed port of the dissolution activation device 9 are connected through a pipe;
  • the clean water inlet of the stirring and dissolving device 9-1 is connected to the clean water main pipe through a pipe; the sulfuric acid solution inlet of the stirring and dissolving device 9-1 is connected to the sulfuric acid solution main pipe through a pipe; and the gas of the stirring and dissolving device 9-1 is stirred.
  • the outlet is connected to the inlet of the exhaust gas absorbing absorption tower 10 through a pipe; the stirring and dissolving device 9-1 is placed inside the microwave activating device 9-2;
  • the gas outlet of the exhaust gas leaching absorption tower 10 is connected to the gas inlet of the induced draft fan 11 through a pipe; the gas outlet of the induced draft fan 11 is connected to the gas inlet at the bottom of the chimney 12 through a pipe.
  • This embodiment uses the above system to produce a 3.5-valent high-purity vanadium electrolyte, and the specific method includes the following steps: vanadium oxychloride in the vanadium oxychloride tank 1 and nitrogen from the nitrogen-purifying manifold pass through the trichloroox
  • the vanadium vaporizer 2-1 is vaporized and preheated, and then enters the gas phase hydrolysis fluidized bed main body 2-4 through the chloride spray gun 2-3; the clean water and the purified air are vaporized and preheated by the clean water vaporizer 2-2.
  • the vanadium oxychloride is hydrolyzed, and the fluidization of the powder material is maintained to form vanadium pentoxide powder and hydrogen chloride-rich hydrolyzed flue gas;
  • the divana powder is discharged into the vanadium pentoxide bin 3-1 through the hydrolyzed fluidized bed discharger 2-5;
  • the hydrolyzed flue gas is expanded by the gas phase hydrolysis fluidized bed main body 2-4
  • the tail gas is sucked into the hydrochloric acid.
  • the receiver 2-6 performs an absorption treatment to form a by-product of the hydrochloric acid solution, and absorbs the exhaust gas into the exhaust gas leaching absorber 10 for treatment;
  • the vanadium pentoxide in the vanadium pentoxide silo 3-1 sequentially enters the vanadium pentoxide screw feeder 3-2, the venturi preheater 4-1, the first cyclone separator 4-2. After the cyclone preheater 4-3, together with the fine powder particles recovered from the bag filter (4-4), enter the bed body through the feeder 5-1.
  • the purified nitrogen gas is sequentially preheated by the cyclone cooler 6-3, the venturi cooler 6-1, the second cyclone separator 6-2, and from the gas purifier 5-
  • the purified reducing gas mixture of 5 is preheated by the gas heater 5-4 and then enters the bed 5-2 to maintain the fluidization of the vanadium pentoxide powder material and reduce it, resulting in low a vanadium oxide powder and a reducing flue gas; the low-valent vanadium oxide sequentially enters the discharger 5 through the discharge port of the bed 5-2 and the fine powder recovered by the cyclone 5-6.
  • the venturi cooler 6-1, the second cyclone separator 6-2, the cyclone cooler 6-3, the secondary cooler 7 are cooled, and then enter the low-valent vanadium oxidation In the material silo 8-1; in the bed 5-2
  • the reducing flue gas sequentially enters the cyclone 5-6, the cyclone preheater 4-3, the venturi preheater 4-1, the first cyclone separator 4-2, and the bag
  • the exhaust gas leaching absorber 10 is introduced, and the gas discharged after being absorbed by the alkali solution is sent to the chimney 12 through the induced draft fan 11 and then emptied;
  • the low-valent vanadium oxide in the low-valent vanadium oxide silo 8-1 enters the stirring and dissolving device 9-1 through the low-valent vanadium oxide screw feeder 8-2, in the microwave activating device 9 -2 provides a microwave field, and dissolves with a sulfuric acid solution from the clean water and sulfuric acid solution main pipe of the clean water main pipe to obtain a high-purity vanadium electrolyte, and the generated acid mist gas is sent to the exhaust gas elution absorber. 10 for processing.
  • vanadium oxychloride (purity of 2N or more) is used as a raw material, and the treatment amount is 3 kg/h.
  • the vaporization operation temperature is 40 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 10:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 40 ° C, the air to water mass ratio is 10:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and
  • the mass ratio of vanadium oxychloride to 10:1 is 100 ° C, the average residence time of the powder material is 300 min; vanadium pentoxide is obtained; in the reduction fluidized bed 5, the bed 5-2 is introduced.
  • the reducing gas is hydrogen, and the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen in the bed 5-2 is 10%, the average residence time of the powder is 90 min, and the operating temperature of the reducing fluidized bed is 400 ° C; a low-valent vanadium oxide having a valence of 3.5 and a purity of 98.5%; adding a sulfuric acid solution to the stirring and dissolving device 9-1 under microwave field conditions (4.0mol/L) and clean water (resistance 15.0M ⁇ cm), operating temperature is 20°C, microwave power density is 10W/L, microwave frequency is 916MHz, and the average valence state of vanadium ions is 3.5 after activation for 300 minutes. Pure vanadium electrolyte, in addition to the effective components, the total content of impurities is less than 0.5%.
  • vanadium oxychloride (purity of 3N or more) is used as a raw material, and the treatment amount is 30 kg/h.
  • the vaporization operation temperature is 600 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:10; in the clean water vaporizer 2-2, the vaporization operation temperature is 600 ° C, the air to water mass ratio is 1:10; in the gas phase hydrolysis fluidized bed main body 2-4, the vapor phase hydrolysis process is introduced into the water vapor and
  • the mass ratio of vanadium oxychloride to 1:10, the gas phase hydrolysis operation temperature is 600 ° C, the average residence time of the powder material is 15 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced.
  • the reducing gas is gas, the gas volume fraction of gas and nitrogen is 90%, the average residence time of the powder is 30 min, the operating temperature of the reducing fluidized bed is 700 ° C, the average valence of vanadium is 3.5, and the purity is 99.5. % of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (10.0 mol/L) and clean water (resistivity 18.0 M ⁇ cm) to the stirring and dissolving device 9-1, operating temperature is 45 ° C, microwave The power density is 300W/L, the microwave frequency is 2450MHz, and after 30 minutes of activation, the average valence state of vanadium ions is obtained. 3.5 vanadium electrolyte solution of high purity, in addition to the effective component, the total content is less than 0.05% of impurities.
  • vanadium oxychloride (purity of 4N or more) is used as a raw material, and the treatment amount is 300 kg/h.
  • the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:5; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:5; in the gas phase hydrolysis fluidized bed main body 2-4, the vapor phase hydrolysis process passes into the water vapor and
  • the reducing gas is gas, the gas volume fraction of gas and nitrogen is 80%, the average residence time of the powder is 45 min, the operating temperature of the reducing fluidized bed is 600 ° C, the average valence of vanadium is 3.5, and the purity is 99.95. % of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (8.0 mol/L) and clean water (resistance 18.0 M ⁇ cm) to the stirring and dissolving device 9-1, operating temperature is 40 ° C, microwave power The density is 200W/L, the microwave frequency is 2450MHz, and after 180 minutes of activation, the average valence state of vanadium ions is obtained.
  • High purity vanadium electrolytic solution in addition to the effective component, the total content of impurities is less than 0.005%, can be used directly in the vanadium battery new stack configuration.
  • vanadium oxychloride (purity of 5N or more) is used as a raw material, and the treatment amount is 3000 kg/h.
  • the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and
  • the mass ratio of vanadium oxychloride to 1:1, the gas phase hydrolysis operation temperature is 200 ° C, the average residence time of the powder material is 60 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced.
  • the reducing gas is hydrogen, the gas volume fraction of the mixed gas of hydrogen and nitrogen is 50%, the average residence time of the powder is 60 min, the operating temperature of the reducing fluidized bed is 500 ° C, the average valence state of vanadium is 3.5, and the purity is 4N5. (ie, purity 99.995%) of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (6.0mol/L) and clean water (resistance 18.0M ⁇ cm) to the stirring and dissolving device 9-1, the operating temperature is At 30 ° C, the microwave power density is 100 W / L, the microwave frequency is 916 MHz, after activation for 120 minutes, the vanadium ion is obtained.
  • the high-purity vanadium electrolyte with a mean valence of 3.5 in addition to the effective components, has a total impurity content of less than 5 ppm and can be directly used in the new stack configuration of the vanadium battery.
  • the vanadium oxychloride (purity of 6N or more) is used as a raw material, and the treatment amount is 3000 kg/h.
  • the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and
  • the mass ratio of vanadium oxychloride to 1:1, the gas phase hydrolysis operation temperature is 200 ° C, the average residence time of the powder material is 60 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced.
  • the reducing gas is hydrogen, the gas volume fraction of the mixed gas of hydrogen and nitrogen is 50%, the average residence time of the powder is 60 min, the operating temperature of the reducing fluidized bed is 500 ° C, the average valence of vanadium is 3.5, and the purity is 5N5. (ie purity 99.9995%) of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (6.0mol/L) and clean water (resistance 18.0M ⁇ cm) to the stirring and dissolving device 9-1, the operating temperature is At 30 ° C, the microwave power density is 100 W / L, the microwave frequency is 916 MHz, after activation for 120 minutes, vanadium ions are obtained.
  • Median state of high purity vanadium electrolytic solution in addition to the effective component is less than 1 ppm or the total content of impurities, can be used directly in the vanadium battery new stack configuration.

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Abstract

一种生产3.5价高纯钒电解液的系统及方法。采用流化床（2）气相水解将高纯度的三氯氧钒水解为五氧化二钒，在还原流化床（5）中将五氧化二钒精确控制还原为钒平均价态为3.5的低价钒氧化物，在外加微波场下配加水和硫酸溶液低温溶解得到3.5价高纯钒电解液，可直接用于全钒液流电池新电堆。通过流化床（2）气相水解制备五氧化二钒流程短、效率高，在还原流化床（5）内设置内构件实现还原产物价态的精准调控，通过微波场的特殊化学效应促进钒氧化物的溶解并活化钒离子，在低温区间溶解制备电解液，大幅度提高电解液活性。该方法具有流程短、高效清洁、产品质量稳定等优点，适用于大规模工业化生产，具有良好的经济效益和社会效益。

Description

一种生产3.5价高纯钒电解液的系统及方法 技术领域
本发明属于能源、化工领域，特别涉及一种生产3.5价高纯钒电解液的系统及方法。
背景技术
传统化石燃料一直是主要的能源来源，由于长期开采和大量使用，面临资源枯竭的问题，同时也带来严重的环境污染。风能、水能、太阳能、潮汐能等清洁的可再生能源的开发与利用逐渐引起人类社会重视。但是可再生能源存在固有的间歇性，现有的能源管理系统难以有效利用。
能量储存技术是解决这类问题的方法之一。在各式各样的能量储存系统中，全钒液流电池(VRB)是一种引人注目的能量储存装置。VRB最大的优势是它的灵活性——功率和储能容量是独立的。VRB的功率决定于电池单元的数量和电池单元有效电极面积，而储能容量决定于电解液中的活性物质的浓度及电解液体积。每个电池单元由两个极室(正极室和负极室)组成，中间被质子交换膜分开。电解液即钒的硫酸盐溶液用于存储能量。当电解液流经电池单元时，在正负极室分别发生V(IV)/V(V)和V(II)/V(III)氧化还原反应。钒电解液是全钒液流电池至关重要的组成部分。
钒电池新电堆配置时一般采用V(III)和V(IV)浓度比1:1混合的钒电解液，即电解液中钒离子的平均价态为3.5。该种电解液可以直接加入正负极室使用，操作简单。钒电解液纯度对电池性能起着至关重要的作用。当电解液中杂质浓度较高时，会带来以下问题：(1)杂质离子与钒离子存在竞争反应，降低电池效率。(2)在正极室，杂质离子在石墨毡电极上沉积，阻塞石墨毡空隙，降低石墨毡比表面积，进而影响充放电效率。(3)在负极室，杂质离子会响析氢过电位，气体产生影响电池内部的压力平衡。(4)杂质离子降低质子交换膜的寿命。(5)杂质离子影响钒离子的稳定，导致电解液过早老化。
VRB电解液的制备方法有以下几种：(1)VOSO4方法：美国专利US849094公开一种由VOSO4溶于硫酸溶液，再通过电化学调整价态制备V(III)和V(IV)浓度比1:1的混合的钒电解液。该种方法存在的主要问题是VOSO4制作工艺比较复杂，且价格高，不利于在VRB中大规模推广使用；VOSO4难以实现高度纯化，以这种工艺配置的电解液含杂质较多；需要电化学处理以调整V(III)和V(IV)浓度比1:1，使电解液中钒离子平均价态为3.5。(2)化学还原法：中国专利CN101562256公开了一种在V2O5和硫酸溶 液混合体系中加入乙二酸、丁醛等还原剂，在50-100℃保温0.5-10小时，化学还原制备出V(III)和V(IV)混合的钒电解液。该种方法主要问题是还原程度不易精确控制；现有工艺制备的V2O5难以实现高度纯化，以这种工艺配置的电解液含杂质较多；添加还原剂会引入新的杂质进入钒电解液体系，影响电解液纯度。(3)电解法：国际PCT专利AKU88/000471介绍了将V2O5活化后加入硫酸溶液，通过恒电流电解制备V(III)和V(IV)浓度比1:1的混合的钒电解液。电解法制备钒电解液适合大规模电解液生产，但是需要进行前期的活化处理，需要额外的电解装置及消耗电能；同样存在电解液杂质较多的问题(4)溶解低价钒氧化物的方法：中国专利CN101728560A公布了以高纯V2O3为原料，在80～150℃温度下，溶于1:1的稀硫酸中，制备V2(SO4)3溶液用于负极电解液。该种工艺主要的问题是在80～150℃温度下操作，V(III)钒离子水合物易形成氧桥键而产生缩聚，导致电解液活性降低，缺少活化步骤；该种方法只能用于制备负极电解液，适用面较窄；专利采用的工业高纯V2O3，全钒含量为67％，相当于98.5％的纯度，仍然含有很多杂质离子。中国专利CN102468509A公开了一种钒电池电解液的制备方法，以偏钒酸铵和碳酸氢铵为原料，经过200～300℃和600～700℃分段煅烧制备出V2O3。在50～120℃，将V2O3溶于稀硫酸中，反应5～20小时，得到V2(SO4)3溶液。在80～110℃，将V2O5溶于V2(SO4)3溶液中，反应1～3小时，得到平均钒离子浓度为3.5价的钒电池电解液。该专利中制备V2(SO4)3溶液用于负极电解液。该种方法主要问题是在较高温度下长时间溶解操作，V(III)钒离子水合物易形成氧桥键而产生缩聚，导致电解液活性降低，缺少活化步骤；电解液纯度不高。中国专利CN103401010A公开了一种全钒液流电池电解液制备方法，将V2O5粉末在氢气中还原制备V2O4粉末和V2O3粉末。将V2O4和V2O3分别溶于浓硫酸中，得到钒电池的正极和负极电解液。该专利存在的主要问题是：没有给出具体的还原工艺，在氢气中还原V2O5制备V2O4粉末，很容易出现过还原或欠还原的情况，需要精确控制才能实现，该专利中没有列出精确控制还原的措施；纯度较低；中国专利CN101880059A和CN102557134A公开了一生产高纯三氧化钒的流态化还原炉及还原方法，通过流化床中加入换热内构件，实现强化换热；采用旋风预热提高能源利用率，实现V2O3的高效制备。这两件专利所述方法只适用于V2O3的制备，不适于其他价态的低价钒氧化物的制备，因为该系统不具备精确控制还原的功能。
综上所述，本领域亟需一种能够解决全钒液流电池电解液制备工艺和技术上的不 足，以实现简化制备流程、提高电解液纯度、提高电解液配置及使用的简洁性。
发明内容
针对以上问题，本发明提出了一种生产3.5价高纯钒电解液的系统及方法，以实现简化制备流程、提高电解液纯度、提高配置电解液的简洁性。为了达到这些目的，本发明采用了如下技术方案：
本发明生产3.5价高纯钒电解液的系统，所述系统包括三氯氧钒储罐1、气相水解流化床2、五氧化二钒加料装置3、预热除尘装置4、还原流化床5、一级冷却装置6、二级冷却装置7、低价钒氧化物加料装置8、溶解活化装置9、尾气淋洗吸收塔10、引风机11和烟囱12；
所述气相水解流化床2包括三氯氧钒汽化器2-1、洁净水汽化器2-2、氯化物喷枪2-3、气相水解流化床主体2-4、水解流化床排料器2-5、盐酸尾气吸收器2-6；
所述五氧化二钒加料装置3包括五氧化二钒料仓3-1和五氧化二钒螺旋加料器3-2；
所述预热除尘装置4包括文丘里预热器4-1、第一旋风分离器4-2、旋风预热器4-3、布袋除尘器4-4；
所述还原流化床5包括进料器5-1、床体5-2、排料器5-3、气体加热器5-4、气体净化器5-5、旋风除尘器5-6；
所述一级冷却装置6包括文丘里冷却器6-1、第二旋风分离器6-2、旋风冷却器6-3；
所述低价钒氧化物加料装置8包括低价钒氧化物料仓8-1和低价钒氧化物螺旋加料器8-2；
所述溶解活化装置9包括搅拌溶解装置9-1和微波活化装置9-2；
所述三氯氧钒储罐1底部的出料口与所述三氯氧钒汽化器2-1的入口通过管道相连；所述三氯氧钒汽化器2-1的入口通过管道与净化氮气总管相连；所述三氯氧钒汽化器2-1的出气口通过管道与所述氯化物喷枪2-3的进气口相连；所述洁净水汽化器2-2的入口通过管道分别与洁净水总管及净化空气总管相连；所述洁净水汽化器2-2的出气口通过管道与所述气相水解流化床主体2-4底部的进气口相连接；所述气相水解流化床主体2-4扩大段顶部的气体出口通过管道与所述盐酸尾气吸收器2-6的气体入口相连接；所述盐酸尾气吸收器2-6底部设置了盐酸溶液出口；所述盐酸尾气吸收器2-6的气体出口通过管道与所述尾气淋洗吸收器10的气体入口相连接；所述气相水解流化床主 体2-4上部的出料口通过管道与所述水解流化床排料器2-5的进料口相连接；所述水解流化床排料器2-5的松动风入气口通过管道与净化氮气总管相连；所述水解流化床排料器2-5的排料口通过管道与所述五氧化二钒料仓3-1进料口相连接；
所述五氧化二钒料仓3-1底部的出料口与所述五氧化二钒螺旋加料器3-2的进料口相连接；所述五氧化二钒螺旋加料器3-2的出料口和与所述文丘里预热器4-1的进料口通过管道相连；
所述文丘里预热器4-1的出料口与所述第一旋风分离器4-2的进料口通过管道相连，所述第一旋风分离器4-2的出气口与所述布袋除尘器4-4的进气口通过管道相连；所述第一旋风分离器4-2的出料口与所述旋风预热器4-3的进气口通过管道相连；所述布袋除尘器4-4的出气口与所述尾气淋洗吸收器10的进气口通过管道相连；所述布袋除尘器4-4的细粉出口与所述旋风预热器4-3的进气口通过管道连接；所述旋风预热器4-3的进气口与所述旋风除尘器5-6的出气口通过管道相连；所述旋风预热器4-3的出气口与所述文丘里预热器4-1的进气口通过管道相连；所述旋风预热器4-3的出料口与所述进料器5-1的进料口通过管道相连；
所述进料器5-1的出料口与所述床体5-2的进料口通过管道相连；所述进料器5-1的松动风入口与净化氮气总管相连；所述床体5-2的进气口与气体加热器5-4的出气口通过管道相连；所述床体5-2中设置竖直挡板；所述床体5-2的出料口与所述排料器5-3的进料口通过管道相连；所述床体5-2的出气口与所述旋风除尘器5-6的进气口通过管道相连；所述旋风除尘器5-6的出气口与所述旋风预热器4-3的进气口通过管道相连；所述旋风除尘器5-6的出料口与所述排料器5-3的进料口通过管道相连；所述排料器5-3的出料口与所述文丘里冷却器6-1的进料口通过管道相连；所述排料器5-3的松动风入口与净化氮气总管相连；所述气体加热器5-4的出气口与所述床体5-2的进气口通过管道相连；所述气体加热器5-4的进气口分别与所述气体净化器5-5的出气口及所述第二旋风分离器6-2的出气口通过管道相连；所述气体加热器5-4的燃料入口与燃料总管通过管道相连；所述气体加热器5-4的助燃风入口与压缩空气总管通过管道相连；所述气体净化器5-5的进气口与还原气体总管通过管道相连；
所述文丘里冷却器6-1的进料口与所述排料器5-3的出料口相连；所述文丘里冷却器6-1的进气口与所述旋风冷却器6-3的出气口通过管道相连；所述文丘里冷却器6-1 的出气口与所述第二旋风分离器6-2的进气口通过管道相连；所述第二旋风分离器6-2的出气口与所述气体加热器5-4的进气口通过管道相连；所述第二旋风分离器6-2的出料口与所述旋风冷却器6-3的进气口相连；所述旋风冷却器6-3的进气口与净化氮气总管相连；所述旋风冷却器6-3的出气口与所述文丘里冷却器6-1的进气口通过管道相连；所述旋风冷却器6-3的出料口与所述二级冷却装置7的进料口通过管道相连；
所述二级冷却装置7的进料口与所述旋风冷却器6-3的出料口通过管道相连；所述二级冷却装置7的出料口与所述低价钒氧化物料仓8-1的进料口通过管道相连；所述二级冷却装置7的进水口与工艺水总管通过管道相连；所述二级冷却装置7的出水口与水冷却系统的进水口通过管道相连；
所述低价钒氧化物料仓8-1底部的出料口与所述低价钒氧化物螺旋加料器8-2的进料口相连接；所述低价钒氧化物螺旋加料器8-2的出料口和与所述溶解活化装置9的进料口通过管道相连；
所述搅拌溶解装置9-1的洁净水入口与洁净水总管通过管道相连；所述搅拌溶解装置9-1的硫酸溶液入口通过管道与硫酸溶液总管连接；所述搅拌溶解装置9-1的气体出口通过管道与所述尾气淋洗吸收塔10的进气口连接；所述搅拌溶解装置9-1置于所述微波活化装置9-2内部；
所述尾气淋洗吸收塔10的气体出口通过管道与所述引风机11的气体入口相连接；所述引风机11的气体出口通过管道与所述烟囱12底部的气体入口相连接。
本发明的基于上述系统的生产3.5价高纯钒电解液的方法，包括以下步骤：
所述三氯氧钒储罐1中的三氯氧钒和来自净化氮气总管的氮气经所述三氯氧钒汽化器2-1汽化预热后通过所述氯化物喷枪2-3进入所述气相水解流化床主体2-4；洁净水和净化空气经所述洁净水汽化器2-2汽化预热后送入所述气相水解流化床主体2-4中，使三氯氧钒发生水解、并维持粉体物料的流态化，形成五氧化二钒粉体和富含氯化氢的水解烟气；五氧化二钒粉体经所述水解流化床床排料器2-5排出送入所述五氧化二钒料仓3-1中；水解烟气经所述气相水解流化床主体2-4扩大段脱除粉尘后，进入所述盐酸尾气吸收器2-6进行吸收处理形成盐酸溶液副产品，吸收尾气进入所述尾气淋洗吸收器10进行处理；
所述五氧化二钒料仓3-1中的五氧化二钒依次进入所述五氧化二钒螺旋加料器3-2、 所述文丘里预热器4-1、所述第一旋风分离器4-2、所述旋风预热器4-3之后，与来自于所述布袋除尘器(4-4)回收的细粉颗粒一同经所述进料器5-1进入所述床体5-2中；所述净化氮气依次经所述旋风冷却器6-3、所述文丘里冷却器6-1、所述第二旋风分离器6-2预热后与来自所述气体净化器5-5的净化还原气体混合经所述气体加热器5-4二次预热后进入所述床体5-2中使五氧化二钒粉体物料维持流态化，并使之发生还原，得到低价钒氧化物粉体和还原烟气；低价钒氧化物经所述床体5-2的排料口与所述旋风除尘器5-6回收的细粉一同依次进入所述排料器5-3、所述文丘里冷却器6-1、所述第二旋风分离器6-2、所述旋风冷却器6-3、所述二级冷却器7冷却后，进入所述低价钒氧化物料仓8-1中；所述床体5-2中的还原烟气依次进入所述旋风除尘器5-6、所述旋风预热器4-3、所述文丘里预热器4-1、所述第一旋风分离器4-2、经所述布袋除尘器4-4除尘后进入所述尾气淋洗吸收器10，经碱溶液吸收处理后排出的气体经所述引风机11送入所述烟囱12后排空；
所述低价钒氧化物料仓8-1中的低价钒氧化物通过所述低价钒氧化物螺旋加料器8-2进入所述搅拌溶解装置9-1中，在所述微波活化装置9-2提供微波场的作用下，与来自于洁净水总管的洁净水、硫酸溶液总管的硫酸溶液发生溶解反应，得到高纯钒电解液，产生的酸雾气体送入所述尾气淋洗吸收器10进行处理。
本发明的特征之一在于：所述三氯氧钒原料纯度为99％～99.9999％，即2N～6N。
本发明的特征之二在于：在所述三氯氧钒汽化器2-1内，汽化操作温度为40～600℃，氮气与三氯氧钒摩尔比为0.10～10.00。
本发明的特征之三在于：在所述洁净水汽化器2-2内，汽化操作温度为40～600℃，空气与水的质量比为0.10～10.00。
本发明的特征之四在于：在所述气相水解流化床主体2-4内，通过三氯氧钒气相水解直接制备五氧化二钒粉体，气相水解过程通入水蒸气与三氯氧钒的质量比为0.10～10.00，气相水解操作温度为100～600℃，粉料的平均停留时间为15～300min。
本发明的特征之五在于：在还原流化床主体5-2中，还原的操作温度为400～700℃，还原气体经所述净化器5-5净化后，有机物含量小于1mg/Nm3，固体颗粒总含量小于2mg/Nm3，通入氮气与还原气体的混合气体中还原气体积分数为10％～90％，粉料的平均停留时间为30～90min。
本发明的特征之六在于：所述硫酸溶液是电子级纯度、摩尔浓度为4.0～10.0mol/L的硫酸溶液。
本发明的特征之七在于：所述高纯钒电解液是V(III)和V(IV)钒离子摩尔浓度比为1:1混合的钒电解液，钒离子的平均价态为3.5。所得3.5价高纯钒电解液可以直接用于全钒液流电池新电堆。
本发明的特征之八在于：在所述溶解活化装置9中，采用外加微波场的方式辅助低价钒氧化物溶解及活化钒离子，溶解活化时间为30～300分钟，溶解活化温度为20～45℃，微波功率密度为10～300W/L，微波频率为2450MHz或916MHz，
本发明生产得到的电解液高纯度，高活性，电解液配置及使用便捷，相对于现有技术，本发明具有如下突出的优点：
(1)高纯度：选用易于高度提纯的三氯氧钒为原料，纯度为2N～6N的高纯度的三氯氧钒易于获得。以5N三氯氧钒为例，通过本发明可以制备纯度4N5(即纯度99.995％)的低价钒氧化物，进而配制出高纯钒电解液，除了有效组分，杂质总含量低于5ppm；
(2)流态化气相水解：流程短，产量大，便于工业化运用；
(3)精准控制还原：采用矩形多仓流化床的形式，实现价态精确控制还原；
(4)实现流化床高温尾气与高温还原产物的显热利用：还原流化床排出的高温尾气与冷的含钒物料直接接触，回收高温还原尾气显热的同时加热冷的含钒物料；还原用净化氮气与排出的高温低价钒氧化物产物直接接触，冷却还原产物的同时，净化氮气被预热，回收高温还原产物的显热；
(5)实现超细粉开路：还原流化床尾气经过外置旋风分离器，回收的粉体进入还原流化床排料器，实现了细粉颗粒的开路，避免了细粉颗粒的密闭循环；
(6)高活性：通过微波场的特殊化学效应促进钒氧化物的溶解并活化钒离子，在低温区间(20～45℃)溶解制备电解液，大幅度提高电解液活性；
(7)运输方便：本工艺生产电解液流程短，适用于钒电池现场配置，可以运输低价钒氧化物，大大降低运输成本；
(8)3.5价电解液：适用于钒电池新电堆配置，可以直接加入正负极室使用，操作简单。
本发明具有生产能耗和操作成本低、产品纯度高、质量稳定、电解液配置及装配简 洁等优点，适用于全钒液流电池电解液的大规模工业化生产，具有良好的经济效益和社会效益。
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3.5价高纯电解液系统的配置示意图。
附图标记：
1、三氯氧钒储罐；
2、气相水解流化床；
2-1、三氯氧钒汽化器；2-2、洁净水汽化器；2-3、氯化物喷枪；
2-4、气相水解流化床主体；2-5、水解流化床排料器；2-6、盐酸尾气吸收器；
3、五氧化二钒加料装置；
3-1、五氧化二钒料仓；3-2、五氧化二钒螺旋加料器；
4、预热除尘装置；
4-1、文丘里预热器；4-2、第一旋风分离器；4-3、旋风预热器；4-4、布袋除尘器；
5、还原流化床；
5-1、进料器；5-2、床体；5-3、排料器；
5-4、气体加热器；5-5、气体净化器；5-6、旋风除尘器；
6、一级冷却装置；
6-1、文丘里冷却器；6-2、第二旋风分离器；6-3、旋风冷却器；
8、低价钒氧化物加料装置；
8-1、低价钒氧化物料仓；8-2、低价钒氧化物螺旋加料器；
9、溶解活化装置；
9-1、搅拌溶解装置；9-2、微波活化装置；
10、尾气淋洗吸收塔；
11、引风机；
12、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。
实施例1
结合图1，本实施例所使用的生产3.5价高纯钒电解液的系统，包括三氯氧钒储罐1、气相水解流化床2、五氧化二钒加料装置3、预热除尘装置4、还原流化床5、一级冷却装置6、二级冷却装置7、低价钒氧化物加料装置8、溶解活化装置9、尾气淋洗吸收塔10、引风机11和烟囱12；
所述气相水解流化床2包括三氯氧钒汽化器2-1、洁净水汽化器2-2、氯化物喷枪2-3、气相水解流化床主体2-4、水解流化床排料器2-5、盐酸尾气吸收器2-6；
所述五氧化二钒加料装置3包括五氧化二钒料仓3-1和五氧化二钒螺旋加料器3-2；
所述预热除尘装置4包括文丘里预热器4-1、第一旋风分离器4-2、旋风预热器4-3、布袋除尘器4-4；
所述还原流化床5包括进料器5-1、床体5-2、排料器5-3、气体加热器5-4、气体净化器5-5、旋风除尘器5-6；
所述一级冷却装置6包括文丘里冷却器6-1、第二旋风分离器6-2、旋风冷却器6-3；
所述低价钒氧化物加料装置8包括低价钒氧化物料仓8-1和低价钒氧化物螺旋加料器8-2；
所述溶解活化装置9包括搅拌溶解装置9-1和微波活化装置9-2；
所述三氯氧钒储罐1底部的出料口与所述三氯氧钒汽化器2-1的入口通过管道相连；所述三氯氧钒汽化器2-1的入口通过管道与净化氮气总管相连；所述三氯氧钒汽化器2-1的出气口通过管道与所述氯化物喷枪2-3的进气口相连；所述洁净水汽化器2-2的入口通过管道分别与洁净水总管及净化空气总管相连；所述洁净水汽化器2-2的出气口通过管道与所述气相水解流化床主体2-4底部的进气口相连接；所述气相水解流化床主体2-4扩大段顶部的气体出口通过管道与所述盐酸尾气吸收器2-6的气体入口相连 接；所述盐酸尾气吸收器2-6底部设置了盐酸溶液出口；所述盐酸尾气吸收器2-6的气体出口通过管道与所述尾气淋洗吸收器10的气体入口相连接；所述气相水解流化床主体2-4上部的出料口通过管道与所述水解流化床排料器2-5的进料口相连接；所述水解流化床排料器2-5的松动风入气口通过管道与净化氮气总管相连；所述水解流化床排料器2-5的排料口通过管道与所述五氧化二钒料仓3-1进料口相连接；
所述五氧化二钒料仓3-1底部的出料口与所述五氧化二钒螺旋加料器3-2的进料口相连接；所述五氧化二钒螺旋加料器3-2的出料口和与所述文丘里预热器4-1的进料口通过管道相连；
所述文丘里预热器4-1的出料口与所述第一旋风分离器4-2的进料口通过管道相连，所述第一旋风分离器4-2的出气口与所述布袋除尘器4-4的进气口通过管道相连；所述第一旋风分离器4-2的出料口与所述旋风预热器4-3的进气口通过管道相连；所述布袋除尘器4-4的出气口与所述尾气淋洗吸收器10的进气口通过管道相连；所述布袋除尘器4-4的细粉出口与所述旋风预热器4-3的进气口通过管道连接；所述旋风预热器4-3的进气口与所述旋风除尘器5-6的出气口通过管道相连；所述旋风预热器4-3的出气口与所述文丘里预热器4-1的进气口通过管道相连；所述旋风预热器4-3的出料口与所述进料器5-1的进料口通过管道相连；
所述进料器5-1的出料口与所述床体5-2的进料口通过管道相连；所述进料器5-1的松动风入口与净化氮气总管相连；所述床体5-2的进气口与气体加热器5-4的出气口通过管道相连；所述床体5-2中设置竖直挡板；所述床体5-2的出料口与所述排料器5-3的进料口通过管道相连；所述床体5-2的出气口与所述旋风除尘器5-6的进气口通过管道相连；所述旋风除尘器5-6的出气口与所述旋风预热器4-3的进气口通过管道相连；所述旋风除尘器5-6的出料口与所述排料器5-3的进料口通过管道相连；所述排料器5-3的出料口与所述文丘里冷却器6-1的进料口通过管道相连；所述排料器5-3的松动风入口与净化氮气总管相连；所述气体加热器5-4的出气口与所述床体5-2的进气口通过管道相连；所述气体加热器5-4的进气口分别与所述气体净化器5-5的出气口及所述第二旋风分离器6-2的出气口通过管道相连；所述气体加热器5-4的燃料入口与燃料总管通过管道相连；所述气体加热器5-4的助燃风入口与压缩空气总管通过管道相连；所述气体净化器5-5的进气口与还原气体总管通过管道相连；
所述文丘里冷却器6-1的进料口与所述排料器5-3的出料口相连；所述文丘里冷却器6-1的进气口与所述旋风冷却器6-3的出气口通过管道相连；所述文丘里冷却器6-1的出气口与所述第二旋风分离器6-2的进气口通过管道相连；所述第二旋风分离器6-2的出气口与所述气体加热器5-4的进气口通过管道相连；所述第二旋风分离器6-2的出料口与所述旋风冷却器6-3的进气口相连；所述旋风冷却器6-3的进气口与净化氮气总管相连；所述旋风冷却器6-3的出气口与所述文丘里冷却器6-1的进气口通过管道相连；所述旋风冷却器6-3的出料口与所述二级冷却装置7的进料口通过管道相连；
所述二级冷却装置7的进料口与所述旋风冷却器6-3的出料口通过管道相连；所述二级冷却装置7的出料口与所述低价钒氧化物料仓8-1的进料口通过管道相连；所述二级冷却装置7的进水口与工艺水总管通过管道相连；所述二级冷却装置7的出水口与水冷却系统的进水口通过管道相连；
所述低价钒氧化物料仓8-1底部的出料口与所述低价钒氧化物螺旋加料器8-2的进料口相连接；所述低价钒氧化物螺旋加料器8-2的出料口和与所述溶解活化装置9的进料口通过管道相连；
所述搅拌溶解装置9-1的洁净水入口与洁净水总管通过管道相连；所述搅拌溶解装置9-1的硫酸溶液入口通过管道与硫酸溶液总管连接；所述搅拌溶解装置9-1的气体出口通过管道与所述尾气淋洗吸收塔10的进气口连接；所述搅拌溶解装置9-1置于所述微波活化装置9-2内部；
所述尾气淋洗吸收塔10的气体出口通过管道与所述引风机11的气体入口相连接；所述引风机11的气体出口通过管道与所述烟囱12底部的气体入口相连接。
实施例2
本实施例利用上述系统进行生产3.5价高纯钒电解液，具体方法包括以下步骤：所述三氯氧钒储罐1中的三氯氧钒和来自净化氮气总管的氮气经所述三氯氧钒汽化器2-1汽化预热后通过所述氯化物喷枪2-3进入所述气相水解流化床主体2-4；洁净水和净化空气经所述洁净水汽化器2-2汽化预热后送入所述气相水解流化床主体2-4中，使三氯氧钒发生水解、并维持粉体物料的流态化，形成五氧化二钒粉体和富含氯化氢的水解烟气；五氧化二钒粉体经所述水解流化床床排料器2-5排出送入所述五氧化二钒料仓3-1中；水解烟气经所述气相水解流化床主体2-4扩大段脱除粉尘后，进入所述盐酸尾气吸 收器2-6进行吸收处理形成盐酸溶液副产品，吸收尾气进入所述尾气淋洗吸收器10进行处理；
所述五氧化二钒料仓3-1中的五氧化二钒依次进入所述五氧化二钒螺旋加料器3-2、所述文丘里预热器4-1、所述第一旋风分离器4-2、所述旋风预热器4-3之后，与来自于所述布袋除尘器(4-4)回收的细粉颗粒一同经所述进料器5-1进入所述床体5-2中；所述净化氮气依次经所述旋风冷却器6-3、所述文丘里冷却器6-1、所述第二旋风分离器6-2预热后与来自所述气体净化器5-5的净化还原气体混合经所述气体加热器5-4二次预热后进入所述床体5-2中使五氧化二钒粉体物料维持流态化，并使之发生还原，得到低价钒氧化物粉体和还原烟气；低价钒氧化物经所述床体5-2的排料口与所述旋风除尘器5-6回收的细粉一同依次进入所述排料器5-3、所述文丘里冷却器6-1、所述第二旋风分离器6-2、所述旋风冷却器6-3、所述二级冷却器7冷却后，进入所述低价钒氧化物料仓8-1中；所述床体5-2中的还原烟气依次进入所述旋风除尘器5-6、所述旋风预热器4-3、所述文丘里预热器4-1、所述第一旋风分离器4-2、经所述布袋除尘器4-4除尘后进入所述尾气淋洗吸收器10，经碱溶液吸收处理后排出的气体经所述引风机11送入所述烟囱12后排空；
所述低价钒氧化物料仓8-1中的低价钒氧化物通过所述低价钒氧化物螺旋加料器8-2进入所述搅拌溶解装置9-1中，在所述微波活化装置9-2提供微波场的作用下，与来自于洁净水总管的洁净水、硫酸溶液总管的硫酸溶液发生溶解反应，得到高纯钒电解液，产生的酸雾气体送入所述尾气淋洗吸收器10进行处理。
实施例3
本实施例以三氯氧钒(纯度2N以上)为原料，处理量为3kg/h，在三氯氧钒汽化器2-1内，汽化操作温度为40℃，氮气与三氯氧钒摩尔比为10:1；在洁净水汽化器2-2内，汽化操作温度为40℃，空气与水的质量比为10:1；在气相水解流化床主体2-4内，气相水解过程通入水蒸气与三氯氧钒的质量比10:1，气相水解操作温度为100℃，粉料的平均停留时间为300min；得到五氧化二钒；在还原流化床5中，通入床体5-2的还原气体为氢气，通入床体5-2中氮气与氢气的混合气体中氢气体积分数为10％，粉料的平均停留时间为90min，还原流化床操作温度为400℃；得到钒的平均价态为3.5，纯度为98.5％的低价钒氧化物；在微波场条件下，向搅拌溶解装置9-1中加入硫酸溶液 (4.0mol/L)和洁净水(电阻15.0MΩ·cm)，操作温度为20℃，微波功率密度为10W/L，微波频率为916MHz，活化300分钟后得到钒离子平均价态为3.5的高纯钒电解液，除了有效组分，杂质总含量低于0.5％。
实施例4
本实施例以三氯氧钒(纯度3N以上)为原料，处理量为30kg/h，在三氯氧钒汽化器2-1内，汽化操作温度为600℃，氮气与三氯氧钒摩尔比为1:10；在洁净水汽化器2-2内，汽化操作温度为600℃，空气与水的质量比为1:10；在气相水解流化床主体2-4内，气相水解过程通入水蒸气与三氯氧钒的质量比1:10，气相水解操作温度为600℃，粉料的平均停留时间为15min，得到五氧化二钒；在还原流化床5中，通入床体5-2的还原气体为煤气，煤气与氮气的混合气体中煤气体积分数为90％，粉料的平均停留时间为30min，还原流化床操作温度为700℃，得到钒的平均价态为3.5，纯度为99.5％的低价钒氧化物；在微波场条件下，向搅拌溶解装置9-1中加入硫酸溶液(10.0mol/L)和洁净水(电阻率18.0MΩ·cm)，操作温度为45℃，微波功率密度为300W/L，微波频率为2450MHz，活化30分钟后，得到钒离子平均价态为3.5的高纯钒电解液，除了有效组分，杂质总含量低于0.05％。
实施例5
本实施例以三氯氧钒(纯度4N以上)为原料，处理量为300kg/h，在三氯氧钒汽化器2-1内，汽化操作温度为200℃，氮气与三氯氧钒摩尔比为1:5；在洁净水汽化器2-2内，汽化操作温度为200℃，空气与水的质量比为1:5；在气相水解流化床主体2-4内，气相水解过程通入水蒸气与三氯氧钒的质量比1:5，气相水解操作温度为200℃，粉料的平均停留时间为120min，得到五氧化二钒；在还原流化床5中，通入床体5-2的还原气体为煤气，煤气与氮气的混合气体中煤气体积分数为80％，粉料的平均停留时间为45min，还原流化床操作温度为600℃，得到钒的平均价态为3.5，纯度为99.95％的低价钒氧化物；在微波场条件下，向搅拌溶解装置9-1中加入硫酸溶液(8.0mol/L)和洁净水(电阻18.0MΩ·cm)，操作温度为40℃，微波功率密度为200W/L，微波频率为2450MHz，活化180分钟后，得到钒离子平均价态3.5的高纯钒电解液，除了有效组分，杂质总含量低于0.005％，可以直接用于钒电池新电堆配置。
实施例6
本实施例以三氯氧钒(纯度5N以上)为原料，处理量为3000kg/h，在三氯氧钒汽化器2-1内，汽化操作温度为200℃，氮气与三氯氧钒摩尔比为1:1；在洁净水汽化器2-2内，汽化操作温度为200℃，空气与水的质量比为1:1；在气相水解流化床主体2-4内，气相水解过程通入水蒸气与三氯氧钒的质量比1:1，气相水解操作温度为200℃，粉料的平均停留时间为60min，得到五氧化二钒；在还原流化床5中，通入床体5-2的还原气体为氢气，氢气与氮气的混合气体中煤气体积分数为50％，粉料的平均停留时间为60min，还原流化床操作温度为500℃，得到钒的平均价态为3.5，纯度为4N5(即纯度99.995％)的低价钒氧化物；在微波场条件下，向搅拌溶解装置9-1中加入硫酸溶液(6.0mol/L)和洁净水(电阻18.0MΩ·cm)，操作温度为30℃，微波功率密度为100W/L，微波频率为916MHz，活化120分钟后，得到钒离子平均价态3.5的高纯钒电解液，除了有效组分，杂质总含量低于5ppm，可以直接用于钒电池新电堆配置。
实施例7
本实施例以三氯氧钒(纯度6N以上)为原料，处理量为3000kg/h，在三氯氧钒汽化器2-1内，汽化操作温度为200℃，氮气与三氯氧钒摩尔比为1:1；在洁净水汽化器2-2内，汽化操作温度为200℃，空气与水的质量比为1:1；在气相水解流化床主体2-4内，气相水解过程通入水蒸气与三氯氧钒的质量比1:1，气相水解操作温度为200℃，粉料的平均停留时间为60min，得到五氧化二钒；在还原流化床5中，通入床体5-2的还原气体为氢气，氢气与氮气的混合气体中煤气体积分数为50％，粉料的平均停留时间为60min，还原流化床操作温度为500℃，得到钒的平均价态为3.5，纯度为5N5(即纯度99.9995％)的低价钒氧化物；在微波场条件下，向搅拌溶解装置9-1中加入硫酸溶液(6.0mol/L)和洁净水(电阻18.0MΩ·cm)，操作温度为30℃，微波功率密度为100W/L，微波频率为916MHz，活化120分钟后，得到钒离子平均价态3.5的高纯钒电解液，除了有效组分，杂质总含量低于1ppm，可以直接用于钒电池新电堆配置。
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 (10)

  1. 一种生产3.5价高纯钒电解液的系统，其特征在于，所述系统包括三氯氧钒储罐(1)、气相水解流化床(2)、五氧化二钒加料装置(3)、预热除尘装置(4)、还原流化床(5)、一级冷却装置(6)、二级冷却装置(7)、低价钒氧化物加料装置(8)、溶解活化装置(9)、尾气淋洗吸收塔(10)、引风机(11)和烟囱(12)；
    所述气相水解流化床(2)包括三氯氧钒汽化器(2-1)、洁净水汽化器(2-2)、氯化物喷枪(2-3)、气相水解流化床主体(2-4)、水解流化床排料器(2-5)、盐酸尾气吸收器(2-6)；
    所述五氧化二钒加料装置(3)包括五氧化二钒料仓(3-1)和五氧化二钒螺旋加料器(3-2)；
    所述预热除尘装置(4)包括文丘里预热器(4-1)、第一旋风分离器(4-2)、旋风预热器(4-3)、布袋除尘器(4-4)；
    所述还原流化床(5)包括进料器(5-1)、床体(5-2)、排料器(5-3)、气体加热器(5-4)、气体净化器(5-5)、旋风除尘器(5-6)；
    所述一级冷却装置(6)包括文丘里冷却器(6-1)、第二旋风分离器(6-2)、旋风冷却器(6-3)；
    所述低价钒氧化物加料装置(8)包括低价钒氧化物料仓(8-1)和低价钒氧化物螺旋加料器(8-2)；
    所述溶解活化装置(9)包括搅拌溶解装置(9-1)和微波活化装置(9-2)；
    所述三氯氧钒储罐(1)底部的出料口与所述三氯氧钒汽化器(2-1)的入口通过管道相连；所述三氯氧钒汽化器(2-1)的入口通过管道与净化氮气总管相连；所述三氯氧钒汽化器(2-1)的出气口通过管道与所述氯化物喷枪(2-3)的进气口相连；所述洁净水汽化器(2-2)的入口通过管道分别与洁净水总管及净化空气总管相连；所述洁净水汽化器(2-2)的出气口通过管道与所述气相水解流化床主体(2-4)底部的进气口相连接；所述气相水解流化床主体(2-4)扩大段顶部的气体出口通过管道与所述盐酸尾气吸收器(2-6)的气体入口相连接；所述盐酸尾气吸收器(2-6)底部设置了盐酸溶液出口；所述盐酸尾气吸收器(2-6)的气体出口通过管道与所述尾气淋洗吸收器(10)的气体入口相连接；所述气相水解流化床主体(2-4)上部的出料口通过管道与所述水 解流化床排料器(2-5)的进料口相连接；所述水解流化床排料器(2-5)的松动风入气口通过管道与净化氮气总管相连；所述水解流化床排料器(2-5)的排料口通过管道与所述五氧化二钒料仓(3-1)进料口相连接；
    所述五氧化二钒料仓(3-1)底部的出料口与所述五氧化二钒螺旋加料器(3-2)的进料口相连接；所述五氧化二钒螺旋加料器(3-2)的出料口和与所述文丘里预热器(4-1)的进料口通过管道相连；
    所述文丘里预热器(4-1)的出料口与所述第一旋风分离器(4-2)的进料口通过管道相连，所述第一旋风分离器(4-2)的出气口与所述布袋除尘器(4-4)的进气口通过管道相连；所述第一旋风分离器(4-2)的出料口与所述旋风预热器(4-3)的进气口通过管道相连；所述布袋除尘器(4-4)的出气口与所述尾气淋洗吸收器(10)的进气口通过管道相连；所述布袋除尘器(4-4)的细粉出口与所述旋风预热器(4-3)的进气口通过管道连接；所述旋风预热器(4-3)的进气口与所述旋风除尘器(5-6)的出气口通过管道相连；所述旋风预热器(4-3)的出气口与所述文丘里预热器(4-1)的进气口通过管道相连；所述旋风预热器(4-3)的出料口与所述进料器(5-1)的进料口通过管道相连；
    所述进料器(5-1)的出料口与所述床体(5-2)的进料口通过管道相连；所述进料器(5-1)的松动风入口与净化氮气总管相连；所述床体(5-2)的进气口与气体加热器(5-4)的出气口通过管道相连；所述床体(5-2)中设置竖直挡板；所述床体(5-2)的出料口与所述排料器(5-3)的进料口通过管道相连；所述床体(5-2)的出气口与所述旋风除尘器(5-6)的进气口通过管道相连；所述旋风除尘器(5-6)的出气口与所述旋风预热器(4-3)的进气口通过管道相连；所述旋风除尘器(5-6)的出料口与所述排料器(5-3)的进料口通过管道相连；所述排料器(5-3)的出料口与所述文丘里冷却器(6-1)的进料口通过管道相连；所述排料器(5-3)的松动风入口与净化氮气总管相连；所述气体加热器(5-4)的出气口与所述床体(5-2)的进气口通过管道相连；所述气体加热器(5-4)的进气口分别与所述气体净化器(5-5)的出气口及所述第二旋风分离器(6-2)的出气口通过管道相连；所述气体加热器(5-4)的燃料入口与燃料总管通过管道相连；所述气体加热器(5-4)的助燃风入口与压缩空气总管通过管道相连；所述气体净化器(5-5)的进气口与还原气体总管通过管道相连；
    所述文丘里冷却器(6-1)的进料口与所述排料器(5-3)的出料口相连；所述文丘里冷却器(6-1)的进气口与所述旋风冷却器(6-3)的出气口通过管道相连；所述文丘里冷却器(6-1)的出气口与所述第二旋风分离器(6-2)的进气口通过管道相连；所述第二旋风分离器(6-2)的出气口与所述气体加热器(5-4)的进气口通过管道相连；所述第二旋风分离器(6-2)的出料口与所述旋风冷却器(6-3)的进气口相连；所述旋风冷却器(6-3)的进气口与净化氮气总管相连；所述旋风冷却器(6-3)的出气口与所述文丘里冷却器(6-1)的进气口通过管道相连；所述旋风冷却器(6-3)的出料口与所述二级冷却装置(7)的进料口通过管道相连；
    所述二级冷却装置(7)的进料口与所述旋风冷却器(6-3)的出料口通过管道相连；所述二级冷却装置(7)的出料口与所述低价钒氧化物料仓(8-1)的进料口通过管道相连；所述二级冷却装置(7)的进水口与工艺水总管通过管道相连；所述二级冷却装置(7)的出水口与水冷却系统的进水口通过管道相连；
    所述低价钒氧化物料仓(8-1)底部的出料口与所述低价钒氧化物螺旋加料器(8-2)的进料口相连接；所述低价钒氧化物螺旋加料器(8-2)的出料口和与所述溶解活化装置(9)的进料口通过管道相连；
    所述搅拌溶解装置(9-1)的洁净水入口与洁净水总管通过管道相连；所述搅拌溶解装置(9-1)的硫酸溶液入口通过管道与硫酸溶液总管连接；所述搅拌溶解装置(9-1)的气体出口通过管道与所述尾气吸收淋洗塔(10)的进气口连接；所述搅拌溶解装置(9-1)置于所述微波活化装置(9-2)内部；
    所述尾气淋洗吸收塔(10)的气体出口通过管道与所述引风机(11)的气体入口相连接；所述引风机(11)的气体出口通过管道与所述烟囱(12)底部的气体入口相连接。
  2. 一种基于权利要求1所述系统生产3.5价高纯钒电解液的方法，所述方法包括以下步骤：
    所述三氯氧钒储罐(1)中的三氯氧钒和来自净化氮气总管的氮气经所述三氯氧钒汽化器(2-1)汽化预热后通过所述氯化物喷枪(2-3)进入所述气相水解流化床主体(2-4)；洁净水和净化空气经所述洁净水汽化器(2-2)汽化预热后送入所述气相水解流化床主体(2-4)中，使三氯氧钒发生水解、并维持粉体物料的流态化，形成五氧化二钒粉体和富含氯化氢的水解烟气；五氧化二钒粉体经所述水解流化床床排料器(2-5)排出送 入所述五氧化二钒料仓(3-1)中；水解烟气经所述气相水解流化床主体(2-4)扩大段脱除粉尘后，进入所述盐酸尾气吸收器(2-6)进行吸收处理形成盐酸溶液副产品，吸收尾气进入所述尾气淋洗吸收器(10)进行处理；
    所述五氧化二钒料仓(3-1)中的五氧化二钒依次进入所述五氧化二钒螺旋加料器(3-2)、所述文丘里预热器(4-1)、所述第一旋风分离器(4-2)、所述旋风预热器(4-3)之后，与来自于所述布袋除尘器(4-4)回收的细粉颗粒一同经所述进料器(5-1)进入所述床体(5-2)中；所述净化氮气依次经所述旋风冷却器(6-3)、所述文丘里冷却器(6-1)、所述第二旋风分离器(6-2)预热后与来自所述气体净化器(5-5)的净化还原气体混合经所述气体加热器(5-4)二次预热后进入所述床体(5-2)中使五氧化二钒粉体物料维持流态化，并使之发生还原，得到低价钒氧化物粉体和还原烟气；低价钒氧化物经所述床体(5-2)的排料口与所述旋风除尘器(5-6)回收的细粉一同依次进入所述排料器(5-3)、所述文丘里冷却器(6-1)、所述第二旋风分离器(6-2)、所述旋风冷却器(6-3)、所述二级冷却器(7)冷却后，进入所述低价钒氧化物料仓(8-1)中；所述床体(5-2)中的还原烟气依次进入所述旋风除尘器(5-6)、所述旋风预热器(4-3)、所述文丘里预热器(4-1)、所述第一旋风分离器(4-2)、经所述布袋除尘器(4-4)除尘后进入所述尾气淋洗吸收器(10)，经碱溶液吸收处理后排出的气体经所述引风机(11)送入所述烟囱(12)后排空；
    所述低价钒氧化物料仓(8-1)中的低价钒氧化物通过所述低价钒氧化物螺旋加料器(8-2)进入所述搅拌溶解装置(9-1)中，在所述微波活化装置(9-2)提供微波场的作用下，与来自于洁净水总管的洁净水、硫酸溶液总管的硫酸溶液发生溶解反应，得到高纯钒电解液，产生的酸雾气体送入所述尾气淋洗吸收器(10)进行处理。
  3. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，所述三氯氧钒原料纯度为99％～99.9999％。
  4. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，在所述三氯氧钒汽化器(2-1)内，汽化操作温度为40～600℃，氮气与三氯氧钒摩尔比为0.10～10.00。
  5. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，在所述洁净水汽化器(2-2)内，汽化操作温度为40～600℃，空气与水的质量比为0.10～10.00。
  6. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，在所述气相水解流化床主体(2-4)内，通过三氯氧钒气相水解直接制备五氧化二钒粉体，气相水解过程通入水蒸气与三氯氧钒的质量比为0.10～10.00，气相水解操作温度为100～600℃，粉料的平均停留时间为15～300min。
  7. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，在还原流化床主体(5-2)内，还原的操作温度为400～700℃，还原气体经所述净化器(5-5)净化后，有机物含量小于1mg/Nm3，固体颗粒总含量小于2mg/Nm3，通入氮气与还原气体的混合气体中还原气体积分数为10％～90％，粉料的平均停留时间为30～90min。
  8. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，所述硫酸溶液是电子级纯度、摩尔浓度为4.0～10.0mol/L的硫酸溶液。
  9. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，所述高纯钒电解液是V(III)和V(IV)钒离子摩尔浓度比为1:1混合的钒电解液，钒离子的平均价态为3.5。
  10. 根据权利要求2所述的生产3.5价高纯钒电解液的方法，其特征在于，在所述溶解活化装置(9)中，采用外加微波场的方式辅助低价钒氧化物溶解及活化钒离子，溶解活化时间为30～300分钟，溶解活化温度为20～45℃，微波功率密度为10～300W/L，微波频率为2450MHz或916MHz。。
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