WO2017128966A1 - 一种制备高纯钒电解液的系统及方法 - Google Patents

一种制备高纯钒电解液的系统及方法 Download PDF

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WO2017128966A1
WO2017128966A1 PCT/CN2017/071204 CN2017071204W WO2017128966A1 WO 2017128966 A1 WO2017128966 A1 WO 2017128966A1 CN 2017071204 W CN2017071204 W CN 2017071204W WO 2017128966 A1 WO2017128966 A1 WO 2017128966A1
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Prior art keywords
ammonium salt
vanadium
gas
pipe
cyclone
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PCT/CN2017/071204
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English (en)
French (fr)
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WO2017128966A9 (zh
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
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Priority to EP17743581.5A priority Critical patent/EP3410527A4/en
Priority to CA3012268A priority patent/CA3012268A1/en
Priority to RU2018130747A priority patent/RU2691058C1/ru
Priority to JP2018539346A priority patent/JP6704459B2/ja
Priority to AU2017210929A priority patent/AU2017210929B2/en
Priority to US16/074,080 priority patent/US10693171B2/en
Priority to NZ744576A priority patent/NZ744576A/en
Publication of WO2017128966A1 publication Critical patent/WO2017128966A1/zh
Publication of WO2017128966A9 publication Critical patent/WO2017128966A9/zh
Priority to ZA201805713A priority patent/ZA201805713B/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
    • B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/008—Feed or outlet control devices
    • 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
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/007—Separating solid material from the gas/liquid stream by sedimentation
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of energy and chemical industry, and particularly relates to a system and a method for preparing a 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 effectiveness.
  • 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.
  • the activity of the vanadium electrolyte refers to the effective vanadium ion concentration that can be used for charge and discharge in the electrolyte. Since the vanadium ions in the electrolyte are affected by temperature, impurities, etc., oxygen bridge bonds are formed, polycondensation occurs, and electrochemical activity is lowered. Increasing the activity of vanadium electrolyte can effectively improve the utilization efficiency of vanadium resources and reduce the cost of vanadium batteries.
  • 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 preparing a high-purity vanadium electrolyte to simplify the preparation process, improve the purity of the electrolyte, improve the simplicity of the electrolyte, and facilitate transportation.
  • the present invention adopts the following technical solutions:
  • the invention provides a system for preparing a high-purity vanadium electrolyte, the system comprising a vanadium oxychloride storage tank 1, an ammonium salt precipitation device 2, an ammonium salt feeding device 3, a preheating system 4, a reducing fluidized bed 5, Cooling system 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation reactor 9;
  • the ammonium salt precipitation device 2 comprises an ammonium salt precipitation reaction tank 2-1 and a washing filter 2-2;
  • the ammonium salt feeding device 3 comprises an ammonium salt silo 3-1 and an ammonium salt screw feeder 3-2;
  • the preheating system 4 includes a first-stage cyclone preheater 4-1, a venturi preheater 4-2, a secondary cyclone preheater 4-3, and a first cyclone separator 4-4;
  • the reduction fluidized bed 5 includes a feeder 5-1, a bed 5-2, a discharger 5-3, a gas heater 5-4, a gas purifier 5-5, and an ammonium chloride sedimentation tower 5-6. ;
  • the cooling system 6 includes a venturi cooler 6-1, a cyclone cooler 6-2, and a second cyclone separator 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 discharge port at the bottom of the vanadium oxychloride vana storage tank 1 is connected to the chloride feed port of the ammonium salt precipitation reaction tank 2-1 through a pipeline; the ammonium salt solution of the ammonium salt precipitation reaction tank 2-1 is inlet and The purified ammonia water main pipe and the gas outlet of the first cyclone separator 4-4 are connected by a pipeline; the flue gas outlet of the ammonium salt precipitation reaction tank 2-1 is connected to the exhaust gas treatment system through a pipeline; the ammonium salt precipitation reaction tank a slurry outlet of 2-1 is connected to a slurry inlet of the washing filter 2-2 through a pipe; a clean water inlet of the washing filter 2-2 is connected to a clean water main pipe through a pipe; the washing The washing liquid outlet of the filter 2-2 is connected to the wastewater treatment unit through a pipeline; the solid material outlet of the washing filter 2-2 is connected to the inlet of the ammonium salt silo 3-1 through a pipeline;
  • a discharge port at the bottom of the ammonium salt silo 3-1 is connected to a feed port of the ammonium salt screw feeder 3-2; a discharge port of the ammonium salt screw feeder 3-2 and the venturi
  • the feed port of the preheater 4-2 is connected by a pipe;
  • the air inlet of the venturi preheater 4-2 is connected to the air outlet of the first-stage cyclone preheater 4-1 through a pipe; the discharge port of the venturi preheater 4-2 is The air inlet of the secondary cyclone preheater 4-3 is connected through a pipeline; the air outlet of the secondary cyclone preheater 4-3 is connected to the air inlet of the first cyclone 4-4 through a pipeline
  • the discharge port of the secondary cyclone cooler 4-3 is connected to the intake port of the first-stage cyclone cooler 4-1 through a pipe;
  • the air outlet of the first cyclone separator 4-4 is The ammonia solution inlet of the ammonium salt precipitation reaction tank 2-1 is connected through a pipeline; the discharge port of the first cyclone separator 4-4 is connected to the inlet of the first-stage cyclone preheater 4-1 through a pipeline;
  • the air inlet of the first-stage cyclone preheater 4-1 is connected to the air outlet of the
  • the inlet of the venturi cooler 6-1 is connected to the purified nitrogen manifold; the venturi cooler 6-1 is out
  • the air port is connected to the air inlet of the cyclone cooler 6-2 through a pipe; the air outlet of the cyclone cooler 6-2 is connected to the air inlet of the second cyclone separator 6-3 through a pipe;
  • the discharge port of the cyclone cooler 6-2 is connected to the inlet of the secondary cooling device 7 through a pipe; the outlet of the second cyclone separator 6-3 and the inlet of the gas heater 5-4
  • the gas port is connected by a pipe; the discharge port of the second cyclone separator 6-3 is connected to the feed port of the secondary cooling device 7 through a pipe;
  • the discharge port of the secondary cooling device 7 is connected to the inlet of the low-cost vanadium oxide silo 8-1 through a pipe; the process water inlet of the secondary cooling device 7 is connected to the process water manifold; The process water outlet of the secondary cooling device 7 is connected to the water cooling system;
  • 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 reactor 9 are connected through a pipe;
  • the clean water inlet of the dissolution activation reactor 9 is connected to the clean water manifold; the sulfuric acid solution inlet of the dissolution activation reactor 9 is connected to the sulfuric acid solution manifold; the gas outlet of the dissolution activation reactor 9 is connected to the tail gas treatment system.
  • the method for preparing a high purity vanadium electrolyte based on the above system of the present invention comprises the following steps:
  • the vanadium oxychloride vanadium in the vanadium oxychloride vanadium 1 enters the ammonium salt precipitation reaction tank 2-1 through the pipeline and the ammonia water from the purified ammonia water main pipe and the ammonia-rich tail gas of the reduced fluidized bed 5 Hydrolyzing and precipitating to form a mixed slurry of an ammonium salt precipitate containing ammonium polyvanadate and ammonium metavanadate and an ammonium chloride solution; the generated flue gas is sent to the tail gas treatment system; the slurry enters the washing filter 2-2 Washing with clean water, filtering to obtain washing liquid and ammonium salt precipitation powder; washing liquid is sent to the wastewater treatment system; ammonium salt is precipitated into the ammonium salt silo 3-1;
  • the ammonium salt precipitate in the ammonium salt silo 3-1 sequentially enters the ammonium salt screw feeder 3-2, the venturi pre The heat exchanger 4-2, the secondary cyclone preheater 4-3, the first-stage cyclone preheater 4-1, together with the fine powder recovered by the first cyclone separator 4-4
  • Feeder 5-1 is fed into the bed 5-2; purified nitrogen from the purified nitrogen main pipe sequentially enters the venturi cooler 6-1, the cyclone cooler 6-2, the second cyclone
  • the separator 6-3 is merged with the purified reducing gas from the gas purifier 5-4, and is sent together into the bed 5-2 to maintain the fluidization of the ammonium salt precipitated powder material and reduce it.
  • the ammonia-rich reducing flue gas is settled by the ammonium chloride sedimentation tower 5-6, and then sequentially enters the first-stage cyclone preheater 4-1.
  • the sulfuric acid solution from the clean water and the sulfuric acid solution main pipe from the clean water main pipe is dissolved to obtain a high-purity vanadium electrolyte, and the generated acid mist gas is sent to the exhaust gas treatment system.
  • 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 ammonium salt precipitation reaction tank 2-1, a mass ratio of purified ammonia water to vanadium oxychloride is 0.5 to 20, and the concentration of the ammonia water is 15 mol/L.
  • the temperature is 30 to 90 °C.
  • a third feature of the present invention is that the ammonium salt in the ammonium salt silo 3-1 means one or more of ammonium metavanadate, ammonium polyvanadate and ammonium chloride.
  • a fourth feature of the present invention resides in that the reducing gas introduced into the reducing gas purifier 5-5 is hydrogen or gas.
  • the fifth feature of the present invention is that, in the bed 5-2 of the reduced fluidized bed, the operating temperature of the reduction is 400 to 700 ° C, and the reducing gas is purified by the gas purifier 5-5, and the organic substance is The content is less than 1 mg/Nm 3 , the total content of solid particles is less than 2 mg/Nm 3 , 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 min.
  • the sixth feature of the present invention is that the high-purity vanadium electrolyte is a mixture of V(III) and V(IV) vanadium ions in a molar ratio of 1:1, and the average valence of vanadium ions is 3.5, which can be directly used.
  • a seventh feature of the present invention is that the sulfuric acid solution has an electronic grade purity and a molar concentration of 4.0 to 10.0 mol/L.
  • the eighth feature of the present invention is that in the dissolution activation reactor 9, the dissolution of the low-valent vanadium oxide and the activation of vanadium ions are promoted by ultrasonic waves, and the dissolution activation time is 30 to 300 minutes, and the dissolution activation temperature is 20 to 45. °C, power density is 10 ⁇ 300W / L, frequency is 28KHz, 40KHz or 60KHz.
  • the electrolyte produced by the invention has high purity, high activity and simple electrolyte assembly, and the invention has the following outstanding advantages:
  • 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 hot-state reducing tail gas sensible heat is recovered while heating the cold vanadium-containing material;
  • 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 suitable for the new stack configuration of vanadium batteries, can be directly used in the positive and negative chambers, easy to operate.
  • the invention has the advantages of low production energy consumption, low operation cost, high product purity, stable quality, simple electrolyte configuration and simple assembly, and is suitable for large-scale industrial production of all vanadium redox flow battery electrolyte, and has good economic and social benefits. .
  • Figure 1 is a schematic view showing the configuration of a high purity vanadium electrolyte system of the present invention.
  • 8-1 low-cost vanadium oxide silo
  • 8-2 low-cost vanadium oxide screw feeder
  • FIG. 1 is a schematic view of a system and method for preparing a high purity vanadium electrolyte according to the present invention.
  • the system for preparing a high-purity vanadium electrolyte used in the present embodiment includes a vanadium oxychloride storage tank 1, an ammonium salt precipitation device 2, an ammonium salt feeding device 3, a preheating system 4, and a reducing fluidized bed 5. , cooling system 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation reactor 9;
  • the ammonium salt precipitation device 2 comprises an ammonium salt precipitation reaction tank 2-1 and a washing filter 2-2;
  • the ammonium salt feeding device 3 comprises an ammonium salt silo 3-1 and an ammonium salt screw feeder 3-2;
  • the preheating system 4 includes a first-stage cyclone preheater 4-1, a venturi preheater 4-2, a secondary cyclone preheater 4-3, and a first cyclone separator 4-4;
  • the reduction fluidized bed 5 includes a feeder 5-1, a bed 5-2, a discharger 5-3, a gas heater 5-4, a gas purifier 5-5, and an ammonium chloride sedimentation tower 5-6. ;
  • the cooling system 6 includes a venturi cooler 6-1, a cyclone cooler 6-2, and a second cyclone separator 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 discharge port at the bottom of the vanadium oxychloride vana storage tank 1 is connected to the chloride feed port of the ammonium salt precipitation reaction tank 2-1 through a pipeline; the ammonium salt solution of the ammonium salt precipitation reaction tank 2-1 is inlet and The purified ammonia water main pipe and the gas outlet of the first cyclone separator 4-4 are connected by a pipeline; the flue gas outlet of the ammonium salt precipitation reaction tank 2-1 is connected to the exhaust gas treatment system through a pipeline; the ammonium salt precipitation reaction tank
  • the slurry outlet of 2-1 is connected to the slurry inlet of the washing filter 2-2 through a pipe; the clean water inlet of the washing filter 2-2 is connected to the clean water main pipe through a pipe; the washing filter 2
  • the washing liquid outlet of 2 is connected to the waste water treatment unit through a pipe; the solid material outlet of the washing filter 2-2 is connected to the feed port of the ammonium salt silo 3-1 through a pipe;
  • a discharge port at the bottom of the ammonium salt silo 3-1 is connected to a feed port of the ammonium salt screw feeder 3-2; a discharge port of the ammonium salt screw feeder 3-2 and the venturi
  • the feed port of the preheater 4-2 is connected by a pipe;
  • the air inlet of the venturi preheater 4-2 is connected to the air outlet of the first-stage cyclone preheater 4-1 through a pipe; the discharge port of the venturi preheater 4-2 is The air inlet of the secondary cyclone preheater 4-3 is connected through a pipeline; the air outlet of the secondary cyclone preheater 4-3 and the air inlet of the first cyclone 4-4 are pipelined
  • the outlet of the secondary cyclone cooler 4-3 is connected to the inlet of the primary cyclone cooler 4-1 through a pipeline; the outlet of the first cyclone 4-4
  • the ammonia solution inlet of the ammonium salt precipitation reaction tank 2-1 is connected through a pipeline; the discharge port of the first cyclone separator 4-4 is connected to the inlet of the first-stage cyclone preheater 4-1 through a pipeline
  • the air inlet of the first-stage cyclone preheater 4-1 is connected to the air outlet of the ammonium chloride sedimentation tower 5-6 through
  • the air inlet of the venturi cooler 6-1 is connected to the purified nitrogen manifold; the air outlet of the venturi cooler 6-1 is connected to the air inlet of the cyclone cooler 6-2 through a pipe; An air outlet of the cyclone cooler 6-2 is connected to an air inlet of the second cyclone separator 6-3 through a pipe; a discharge port of the cyclone cooler 6-2 and the secondary cooling device 7
  • the inlet is connected by a pipe; the outlet of the second cyclone 6-3 is connected to the inlet of the gas heater 5-4 through a pipe; the outlet of the second cyclone 6-3 Connected to the inlet of the secondary cooling device 7 through a pipeline;
  • the discharge port of the secondary cooling device 7 is connected to the inlet of the low-cost vanadium oxide silo 8-1 through a pipe; the process water inlet of the secondary cooling device 7 is connected to the process water manifold; Process of secondary cooling device 7 The water outlet is connected to the water cooling system;
  • 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 reactor 9 are connected through a pipe;
  • the clean water inlet of the dissolution activation reactor 9 is connected to the clean water manifold; the sulfuric acid solution inlet of the dissolution activation reactor 9 is connected to the sulfuric acid solution manifold; the gas outlet of the dissolution activation reactor 9 is connected to the tail gas treatment system.
  • a method for preparing a high-purity vanadium electrolyte using the above system comprises the following steps:
  • the vanadium oxychloride vanadium in the vanadium oxychloride vanadium 1 enters the ammonium salt precipitation reaction tank 2-1 through the pipeline and the ammonia water from the purified ammonia water main pipe and the ammonia-rich tail gas of the reduced fluidized bed 5 Hydrolyzing and precipitating to form a mixed slurry of an ammonium salt precipitate containing ammonium polyvanadate and ammonium metavanadate and an ammonium chloride solution; the generated flue gas is sent to the tail gas treatment system; the slurry enters the washing filter 2-2 Washing with clean water, filtering to obtain washing liquid and ammonium salt precipitation powder; washing liquid is sent to the wastewater treatment system; ammonium salt is precipitated into the ammonium salt silo 3-1;
  • the ammonium salt precipitate in the ammonium salt silo 3-1 sequentially enters the ammonium salt auger 3-2, the venturi preheater 4-2, the secondary cyclone preheater 4-3,
  • the first-stage cyclone preheater 4-1 is sent into the bed body 5-2 via the feeder 5-1 together with the fine powder recovered by the first cyclone separator 4-4;
  • the purified nitrogen gas purifying the nitrogen gas main pipe sequentially enters the venturi cooler 6-1, the cyclone cooler 6-2, the second cyclone separator 6-3, and the purified from the gas purifier 5-4
  • the reducing gas is merged and sent to the bed 5-2 to maintain the fluidization of the ammonium salt precipitated powder material and reduce it to obtain a low-valent vanadium oxide powder and an ammonia-rich reducing flue gas; After the reduced flue gas is settled by the ammonium chloride sedimentation tower 5-6, it sequentially enters the first stage cyclone preheater 4-1.
  • the fine powder recovered by the cyclone separator 6-3 is passed through the secondary cooling device 7, the low-valent vanadium oxide silo 8-1, the low-cost vanadium oxide screw feeder 8-2, and into the dissolution.
  • the sulfuric acid solution from the clean water and the sulfuric acid solution main pipe from the clean water main pipe is dissolved to obtain a high-purity vanadium electrolyte, and the generated acid mist gas is sent to the exhaust gas treatment system. .
  • vanadium oxychloride (purity of 2N or more) is used as a raw material, and the treatment amount is 3 kg/h.
  • the mass ratio of purified ammonia water to vanadium oxychloride is 0.5, and the operation temperature is At 90 ° C, a mixed slurry of an ammonium salt precipitate containing ammonium polyvanadate and ammonium metavanadate and an ammonium chloride solution is obtained, and the slurry enters the washing filter 2-2 and is washed with clean water, and filtered to obtain a washing.
  • the liquid and the ammonium salt precipitate the powder, and the washing liquid is sent to the wastewater treatment system, and the ammonium salt precipitate is preheated by the preheating system and then enters the reducing fluidized bed; in the reducing fluidized bed 5, the reducing gas introduced is gas, and the inlet is passed.
  • the gas volume fraction of the mixed gas of nitrogen and gas in the reduced fluidized bed 5 is 10%, the average residence time of the powder is 90 min, the operating temperature is 400 ° C, and the average valence state of vanadium is 3.5, and the purity is 98.5%.
  • Valence vanadium oxide in the dissolution activation reactor is equipped with electronic grade sulfuric acid solution (4.0mol / L) and clean water (resistance 15.0M ⁇ ⁇ cm), dissolution temperature 20 ° C, ultrasonic power density 10W / L, frequency of 28KHz, After 300 minutes of activation, a vanadium electrolyte is obtained, in addition to the effective components, the total content of impurities To 0.25%.
  • vanadium oxychloride (purity of 3N or more) is used as a raw material, and the treatment amount is 30 kg/h.
  • the mass ratio of purified ammonia water to vanadium oxychloride is 20, and the operation temperature is At 30 ° C, the polyphenolic acid is obtained.
  • the slurry enters the washing filter 2-2 and is washed with clean water, and filtered to obtain a washing liquid and an ammonium salt precipitated powder, and washed
  • the liquid is sent to the wastewater treatment system, and the ammonium salt precipitate is preheated by the preheating system and then enters the reducing fluidized bed; in the reducing fluidized bed 5, the reducing gas introduced is gas, and the nitrogen gas and the gas are introduced into the reducing fluidized bed 5.
  • the volume fraction of gas in the mixed gas is 90%, the average residence time of the powder is 30 min, and the operating temperature is 700 ° C.
  • the average valence of vanadium is 3.5, and the purity of vanadium oxide is 99.85%.
  • the kettle was equipped with an electronic grade sulfuric acid solution (10.0 mol/L) and clean water (resistance 18.0 M ⁇ cm), a dissolution temperature of 45 ° C, an ultrasonic power density of 300 W/L, a frequency of 40 KHz, and a high purity vanadium after activation for 30 minutes.
  • the electrolyte in addition to the effective components, has a total impurity content of less than 0.02%.
  • vanadium oxychloride (purity of 4N or more) is used as a raw material, and the treatment amount is 300 kg/h.
  • the mass ratio of purified ammonia water to vanadium oxychloride is 10, and the operation temperature is At 60 ° C, a mixed slurry of an ammonium salt precipitate containing ammonium polyvanadate and ammonium metavanadate and an ammonium chloride solution is obtained, and the slurry enters the washing filter 2-2 and is washed with clean water, and filtered to obtain a washing.
  • the liquid and the ammonium salt precipitate the powder, and the washing liquid is sent to the wastewater treatment system, and the ammonium salt precipitate is preheated by the preheating system and then enters the reducing fluidized bed; in the reducing fluidized bed 5, the reducing gas introduced is hydrogen, which is introduced.
  • the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen is 70%
  • the average residence time of the powder is 60 min
  • the operating temperature is 600 ° C
  • the average valence of vanadium is 3.5
  • the purity is 99.97%.
  • Valence vanadium oxide in the dissolution activation reactor is equipped with electronic grade sulfuric acid solution (8.0mol / L) and clean water (resistance 18.0M ⁇ ⁇ cm), dissolution temperature 35 ° C, ultrasonic power density 200W / L, frequency 60KHz, After 200 minutes of activation, a high purity vanadium electrolyte is obtained, in addition to the effective components, impurities Less than 0.005%.
  • vanadium oxychloride (purity of 5N or more) is used as a raw material, and the treatment amount is 3000 kg/h, and the precipitation in the ammonium salt is reversed.
  • tank 2-1 the mass ratio of purified ammonia water to vanadium oxychloride is 5, and the operating temperature is 50 ° C to obtain a mixed slurry of ammonium salt precipitation and ammonium chloride solution containing ammonium polyvanadate and ammonium metavanadate.
  • the slurry enters the washing filter 2-2 and is washed with clean water.
  • the washing liquid and the ammonium salt precipitation powder are obtained, and the washing liquid is sent to the wastewater treatment system, and the ammonium salt precipitate is preheated by the preheating system and then enters.
  • the reducing gas introduced is hydrogen
  • the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen in the reducing fluidized bed 5 is 50%
  • the average residence time of the powder is 45min
  • operating temperature is 550 ° C
  • the average valence state of vanadium is 3.5
  • in the dissolution activation reactor is equipped with electronic grade sulfuric acid solution (5.0mol / L) and clean water ( The resistance is 18.0 M ⁇ cm), the dissolution temperature is 30 ° C, the ultrasonic power density is 100 W/L, and the frequency is 60 KHz.
  • vanadium oxychloride (purity of 6N or more) is used as a raw material, and the treatment amount is 3000 kg/h.
  • the mass ratio of purified ammonia water to vanadium oxychloride is 5, and the operation temperature is At 50 ° C, a mixed slurry of an ammonium salt precipitate containing ammonium polyvanadate and ammonium metavanadate and an ammonium chloride solution is obtained, and the slurry enters the washing filter 2-2 and is washed with clean water, and filtered to obtain a washing.
  • the liquid and the ammonium salt precipitate the powder, and the washing liquid is sent to the wastewater treatment system, and the ammonium salt precipitate is preheated by the preheating system and then enters the reducing fluidized bed; in the reducing fluidized bed 5, the reducing gas introduced is hydrogen, which is introduced.
  • the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen is 50%
  • the average residence time of the powder is 45 min
  • the operating temperature is 550 ° C
  • the average valence of vanadium is 3.5
  • the purity is 5N5 (ie, purity).

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Abstract

一种制备高纯钒电解液的系统及方法，以三氯氧钒为原料，通过铵盐沉淀、流态化还原制备低价钒氧化物，在超声波辅助溶解及活化的条件下，配加硫酸溶液和洁净水低温制备出高纯钒电解液，通过铵盐与还原尾气换热、还原产物与流化氮气换热实现热量高效利用，通过回收还原尾气中的氨气用于沉钒实现氨气循环利用，在还原流化床内设置内构件实现还原产物价态的精准调控，并利用超声波辅助溶解及活化，实现低温配制钒电解液，提高电解液活性，该系统及方法具有流程短、高效清洁、产品质量稳定等优点，适用于大规模工业化生产。

Description

一种制备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，特别涉及一种制备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。
钒电解液的活性是指电解液中能用于充放电的有效钒离子浓度，由于电解液中的钒离子受温度、杂质等影响会形成氧桥键，发生缩聚，降低电化学活性。提高钒电解液活性可以有效提高钒资源利用效率，降低钒电池成本。
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、提高电解液纯度及活性、提高电解液配置及使用的简洁性。
发明内容
针对以上问题，本发明提出了一种制备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、便于运输。为了达到这些目的，本发明采用了如下技术方案：
本发明提供了一种制备高纯钒电解液的系统，所述系统包括三氯氧钒储罐1、铵盐沉淀装置2、铵盐加料装置3、预热系统4、还原流化床5、冷却系统6、二级冷却装置7、低价钒氧化物加料装置8、溶解活化反应釜9；
所述铵盐沉淀装置2包括铵盐沉淀反应罐2-1和洗涤过滤器2-2；
所述铵盐加料装置3包括铵盐料仓3-1和铵盐螺旋加料器3-2；
所述预热系统4包括一级旋风预热器4-1、文丘里预热器4-2、二级旋风预热器4-3、第一旋风分离器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、氯化铵沉降塔5-6；
所述冷却系统6包括文丘里冷却器6-1、旋风冷却器6-2、第二旋风分离器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；
所述三氯氧钒储罐1底部的出料口与所述铵盐沉淀反应罐2-1的氯化物进料口通过管道相连；所述铵盐沉淀反应罐2-1的氨水溶液入口与纯化氨水总管及所述第一旋风分离器4-4的出气口通过管道相连；所述铵盐沉淀反应罐2-1的烟气出口与尾气处理系统通过管道相连；所述铵盐沉淀反应罐2-1的浆料出口与所述洗涤过滤器2-2的浆料入口通过管道相连；所述洗涤过滤器2-2的清水入口与洁净水总管通过管道相连；所述洗涤 过滤器2-2的洗涤液出口与废水处理单元通过管道相连；所述洗涤过滤器2-2的固体物料出口与所述铵盐料仓3-1的进料口通过管道相连；
所述铵盐料仓3-1底部的出料口与所述铵盐螺旋加料器3-2的进料口相连接；所述铵盐螺旋加料器3-2的出料口与所述文丘里预热器4-2的进料口通过管道相连；
所述文丘里预热器4-2的进气口与所述一级旋风预热器4-1的出气口通过管道相连；所述文丘里预热器4-2的出料口与所述二级旋风预热器4-3的进气口通过管道相连；所述二级旋风预热却器4-3的出气口与所述第一旋风分离器4-4的进气口通过管道相连；所述二级旋风冷却器4-3的出料口与所述一级旋风冷却器4-1的进气口通过管道相连；所述第一旋风分离器4-4的出气口与所述铵盐沉淀反应罐2-1的氨水溶液入口通过管道相连；所述第一旋风分离器4-4的出料口与所述一级旋风预热器4-1的进气口通过管道相连；所述一级旋风预热器4-1的进气口与所述氯化铵沉降塔5-6的出气口通过管道相连；所述一级旋风预热器4-1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通过管道相连；所述床体5-2的高温烟气出口与所述氯化铵沉降塔5-6的进气口通过管道相连；所述氯化铵沉降塔5-6的出气口与所述一级旋风预热器4-1的进气口通过管道相连；所述床体5-2的进气口与所述气体加热器5-4的出气口通过管道相连；所述气体加热器5-4的进气口分别与所述第二旋风分离器6-3及所述气体净化器5-5的出气口通过管道相连；所述气体加热器5-4的助燃风入口与压缩空气总管相连；所述气体加热器5-4燃料入口与燃料总管相连；所述气体净化器5-5的进气口与还原气体总管相连；
所述文丘里冷却器6-1的进气口与净化氮气总管相连；所述文丘里冷却器6-1的出 气口与所述旋风冷却器6-2的进气口通过管道相连；所述旋风冷却器6-2的出气口与所述第二旋风分离器6-3的进气口通过管道相连；所述旋风冷却器6-2的出料口与所述二级冷却装置7的进料口通过管道相连；所述第二旋风分离器6-3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6-3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的工艺水入口与工艺水总管相连；所述二级冷却装置7的工艺水出口与水冷却系统相连；
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反应釜9的进料口通过管道相连接；
所述溶解活化反应釜9的洁净水入口与洁净水总管相连；所述溶解活化反应釜9的硫酸溶液入口与硫酸溶液总管连接；所述溶解活化反应釜9的气体出口与尾气处理系统相连。
本发明的基于上述系统制备高纯钒电解液的方法，包括以下步骤：
所述三氯氧钒储罐1中的三氯氧钒液体通过管道进入所述铵盐沉淀反应罐2-1中与来自纯化氨水总管的氨水及所述还原流化床5的富氨尾气发生水解沉淀，形成含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料；产生的烟气送尾气处理系统；浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料；洗涤液送往废水处理系统；铵盐沉淀送入所述铵盐料仓3-1中；
所述铵盐料仓3-1中的铵盐沉淀依次进入所述铵盐螺旋加料器3-2、所述文丘里预 热器4-2、所述二级旋风预热器4-3、所述一级旋风预热器4-1，与所述第一旋风分离器4-4回收的细粉一同经所述进料器5-1送入所述床体5-2中；来自于净化氮气总管的净化氮气依次进入所述文丘里冷却器6-1、所述旋风冷却器6-2、所述第二旋风分离器6-3，与来自于所述气体净化器5-4净化还原气体汇合，一同送入所述床体5-2中使铵盐沉淀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富氨还原烟气；富氨还原烟气经所述氯化铵沉降塔5-6沉降后，依次进入所述一级旋风预热器4-1所述文丘里预热器4-2、所述二级旋风预热器4-3、经所述第一旋风分离器4-4除尘后，与来自于纯化氨水总管的氨水混合，一同送入所述铵盐沉淀反应罐2-1；低价钒氧化物经所述排料器5-3，依次进入所述文丘里冷却器6-1、所述旋风冷却器6-2中，与所述第二旋风分离器6-3回收的细粉一同经所述二级冷却装置7、所述低价钒氧化物料仓8-1、所述低价钒氧化物螺旋加料器8-2、进入所述溶解活化反应釜9中，在超声波场的作用下，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尾气处理系统。
本发明的特征之一在于：所述三氯氧钒原料纯度99％～99.9999％，即2N～6N。
本发明的特征之二在于：在所述铵盐沉淀反应罐2-1内，加入纯化氨水与三氯氧钒的质量比为0.5～20，所述氨水的浓度为15mol/L，所述操作温度30～90℃。
本发明的特征之三在于：所述铵盐料仓3-1中的铵盐是指偏钒酸铵、多钒酸铵和氯化铵中的一种或多种。
本发明的特征之四在于：所述通入还原气体净化器5-5中的还原气体为氢气或煤气。
本发明的特征之五在于：在还原流化床的床体5-2内，所述还原的操作温度为400～700℃，所述还原气体经所述气体净化器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混合电解液，钒离子的平均价态为3.5，可以直接用于全钒液流电池新电堆。
本发明的特征之七在于：所述硫酸溶液为电子级纯度、摩尔浓度为4.0～10.0mol/L。
本发明的特征之八在于：在所述溶解活化反应釜9中，采用超声波的方式促进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℃，功率密度为10～300W/L，频率为28KHz、40KHz或60KHz。
本发明生产得到的电解液高纯度，高活性，电解液装配简洁，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)直接铵盐沉淀：工艺成熟，便于工业化运用；
(3)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；
(4)实现还原流化床富氨尾气循环利用：还原流化床产生的高温富氨尾气通过管路进入铵盐沉淀反应罐中，实现氨气回收利用；
(4)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；
(5)高活性：通过超声波辅助低价钒氧化物溶解及活化钒离子，实现在低温区间20～45℃制备钒电解液，大幅度提高电解液活性；
(6)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；
(7)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为本发明的制备高纯钒电解液系统的配置示意图。
附图标记：
1、三氯氧钒储罐；
2、铵盐沉淀装置；
2-1、铵盐沉淀反应罐；2-2、洗涤过滤器；
3、铵盐加料装置；
3-1、铵盐料仓；3-2、铵盐螺旋加料器；
4、预热系统；
4-1、一级旋风预热器；4-2、文丘里预热器；
4-3、二级旋风预热器；4-4、第一旋风分离器；
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、氯化铵沉降塔；
6、冷却系统；
6-1、文丘里冷却器；6-2、旋风冷却器；6-3、第二旋风分离器；
7、二级冷却装置；
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、溶解活化反应釜。
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为本发明的一种制备高纯钒电解液的系统及方法示意图。
实施例1
结合图1，本实施例所使用的制备高纯钒电解液的系统，包括三氯氧钒储罐1、铵盐沉淀装置2、铵盐加料装置3、预热系统4、还原流化床5、冷却系统6、二级冷却装置7、低价钒氧化物加料装置8、溶解活化反应釜9；
所述铵盐沉淀装置2包括铵盐沉淀反应罐2-1和洗涤过滤器2-2；
所述铵盐加料装置3包括铵盐料仓3-1和铵盐螺旋加料器3-2；
所述预热系统4包括一级旋风预热器4-1、文丘里预热器4-2、二级旋风预热器4-3、第一旋风分离器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、氯化铵沉降塔5-6；
所述冷却系统6包括文丘里冷却器6-1、旋风冷却器6-2、第二旋风分离器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；
所述三氯氧钒储罐1底部的出料口与所述铵盐沉淀反应罐2-1的氯化物进料口通过管道相连；所述铵盐沉淀反应罐2-1的氨水溶液入口与纯化氨水总管及所述第一旋风分离器4-4的出气口通过管道相连；所述铵盐沉淀反应罐2-1的烟气出口与尾气处理系统通过管道相连；所述铵盐沉淀反应罐2-1的浆料出口与所述洗涤过滤器2-2的浆料入口通过管道相连；所述洗涤过滤器2-2的清水入口与洁净水总管通过管道相连；所述洗涤过滤器2-2的洗涤液出口与废水处理单元通过管道相连；所述洗涤过滤器2-2的固体物料出口与所述铵盐料仓3-1的进料口通过管道相连；
所述铵盐料仓3-1底部的出料口与所述铵盐螺旋加料器3-2的进料口相连接；所述铵盐螺旋加料器3-2的出料口与所述文丘里预热器4-2的进料口通过管道相连；
所述文丘里预热器4-2的进气口与所述一级旋风预热器4-1的出气口通过管道相连；所述文丘里预热器4-2的出料口与所述二级旋风预热器4-3的进气口通过管道相连；所述二级旋风预热却器4-3的出气口与所述第一旋风分离器4-4的进气口通过管道相 连；所述二级旋风冷却器4-3的出料口与所述一级旋风冷却器4-1的进气口通过管道相连；所述第一旋风分离器4-4的出气口与所述铵盐沉淀反应罐2-1的氨水溶液入口通过管道相连；所述第一旋风分离器4-4的出料口与所述一级旋风预热器4-1的进气口通过管道相连；所述一级旋风预热器4-1的进气口与所述氯化铵沉降塔5-6的出气口通过管道相连；所述一级旋风预热器4-1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通过管道相连；所述床体5-2的高温烟气出口与所述氯化铵沉降塔5-6的进气口通过管道相连；所述氯化铵沉降塔5-6的出气口与所述一级旋风预热器4-1的进气口通过管道相连；所述床体5-2的进气口与所述气体加热器5-4的出气口通过管道相连；所述气体加热器5-4的进气口分别与所述第二旋风分离器6-3及所述气体净化器5-5的出气口通过管道相连；所述气体加热器5-4的助燃风入口与压缩空气总管相连；所述气体加热器5-4燃料入口与燃料总管相连；所述气体净化器5-5的进气口与还原气体总管相连；
所述文丘里冷却器6-1的进气口与净化氮气总管相连；所述文丘里冷却器6-1的出气口与所述旋风冷却器6-2的进气口通过管道相连；所述旋风冷却器6-2的出气口与所述第二旋风分离器6-3的进气口通过管道相连；所述旋风冷却器6-2的出料口与所述二级冷却装置7的进料口通过管道相连；所述第二旋风分离器6-3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6-3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的工艺水入口与工艺水总管相连；所述二级冷却装置7的工艺 水出口与水冷却系统相连；
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反应釜9的进料口通过管道相连接；
所述溶解活化反应釜9的洁净水入口与洁净水总管相连；所述溶解活化反应釜9的硫酸溶液入口与硫酸溶液总管连接；所述溶解活化反应釜9的气体出口与尾气处理系统相连。
实施例2
本实施例利用上述系统制备高纯钒电解液的方法，具体方法包括以下步骤：
所述三氯氧钒储罐1中的三氯氧钒液体通过管道进入所述铵盐沉淀反应罐2-1中与来自纯化氨水总管的氨水及所述还原流化床5的富氨尾气发生水解沉淀，形成含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料；产生的烟气送尾气处理系统；浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料；洗涤液送往废水处理系统；铵盐沉淀送入所述铵盐料仓3-1中；
所述铵盐料仓3-1中的铵盐沉淀依次进入所述铵盐螺旋加料器3-2、所述文丘里预热器4-2、所述二级旋风预热器4-3、所述一级旋风预热器4-1，与所述第一旋风分离器4-4回收的细粉一同经所述进料器5-1送入所述床体5-2中；来自于净化氮气总管的净化氮气依次进入所述文丘里冷却器6-1、所述旋风冷却器6-2、所述第二旋风分离器6-3，与来自于所述气体净化器5-4净化还原气体汇合，一同送入所述床体5-2中使铵盐沉淀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富氨还原烟气；富氨还原烟气经所述氯化铵沉降塔5-6沉降后，依次进入所述一级旋风预热器4-1所述文丘 里预热器4-2、所述二级旋风预热器4-3、经所述第一旋风分离器4-4除尘后，与来自于纯化氨水总管的氨水混合，一同送入所述铵盐沉淀反应罐2-1；低价钒氧化物经所述排料器5-3，依次进入所述文丘里冷却器6-1、所述旋风冷却器6-2中，与所述第二旋风分离器6-3回收的细粉一同经所述二级冷却装置7、所述低价钒氧化物料仓8-1、所述低价钒氧化物螺旋加料器8-2、进入所述溶解活化反应釜9中，在超声波场的作用下，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尾气处理系统。
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，在铵盐沉淀反应罐2-1中，加入纯化氨水与三氯氧钒的质量比为0.5，操作温度为90℃，得到含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料，浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料，洗涤液送往废水处理系统，铵盐沉淀经预热系统预热后进入还原流化床；在还原流化床5中，通入的还原气体为煤气，通入还原流化床5中氮气与煤气的混合气体中煤气体积分数为10％，粉料的平均停留时间为90min，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；在溶解活化反应釜中配加电子级硫酸溶液(4.0mol/L)和洁净水(电阻15.0MΩ·cm)，溶解温度20℃，超声功率密度10W/L，频率为28KHz，活化300分钟后，得到钒电解液，除了有效组分外，杂质总含量低于0.25％。
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，在铵盐沉淀反应罐2-1中，加入纯化氨水与三氯氧钒的质量比为20，操作温度为30℃，得到含多钒酸 铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料，浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料，洗涤液送往废水处理系统，铵盐沉淀经预热系统预热后进入还原流化床；在还原流化床5中，通入的还原气体为煤气，通入还原流化床5中氮气与煤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，操作温度为700℃，得到钒的平均价态为3.5，纯度为99.85％的低价钒氧化物；在溶解活化反应釜中配加电子级硫酸溶液(10.0mol/L)和洁净水(电阻18.0MΩ·cm)，溶解温度45℃，超声功率密度300W/L，频率为40KHz，活化30分钟后，得到高纯钒电解液，除了有效组分外，杂质总含量低于0.02％的。
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，在铵盐沉淀反应罐2-1中，加入纯化氨水与三氯氧钒的质量比为10，操作温度为60℃，得到含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料，浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料，洗涤液送往废水处理系统，铵盐沉淀经预热系统预热后进入还原流化床；在还原流化床5中，通入的还原气体为氢气，通入还原流化床5中氮气与氢气的混合气体中氢气体积分数为70％，粉料的平均停留时间为60min，操作温度为600℃，得到钒的平均价态为3.5，纯度为99.97％的低价钒氧化物；在溶解活化反应釜中配加电子级硫酸溶液(8.0mol/L)和洁净水(电阻18.0MΩ·cm)，溶解温度35℃，超声功率密度200W/L，频率为60KHz，活化200分钟后，得到高纯钒电解液，除了有效组分外，杂质总含量低于0.005％。
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，在铵盐沉淀反 应罐2-1中，加入纯化氨水与三氯氧钒的质量比为5，操作温度为50℃，得到含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料，浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料，洗涤液送往废水处理系统，铵盐沉淀经预热系统预热后进入还原流化床；在还原流化床5中，通入的还原气体为氢气，通入还原流化床5中氮气与氢气的混合气体中氢气体积分数为50％，粉料的平均停留时间为45min，操作温度为550℃，得到钒的平均价态为3.5，纯度为99.997％的低价钒氧化物；在溶解活化反应釜中配加电子级硫酸溶液(5.0mol/L)和洁净水(电阻18.0MΩ·cm)，溶解温度30℃，超声功率密度100W/L，频率为60KHz，活化100分钟后，得到高纯钒电解液，除了有效组分外，杂质总含量低于5ppm。
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，在铵盐沉淀反应罐2-1中，加入纯化氨水与三氯氧钒的质量比为5，操作温度为50℃，得到含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料，浆料进入所述洗涤过滤器2-2中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料，洗涤液送往废水处理系统，铵盐沉淀经预热系统预热后进入还原流化床；在还原流化床5中，通入的还原气体为氢气，通入还原流化床5中氮气与氢气的混合气体中氢气体积分数为50％，粉料的平均停留时间为45min，操作温度为550℃，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；在溶解活化反应釜中配加电子级硫酸溶液(5.0mol/L)和洁净水(电阻18.0MΩ·cm)，溶解温度30℃，超声功率密度100W/L，频率为60KHz，活化100分钟后，得到高纯钒电解液，除了有效组分外，杂质总含量低于1ppm。
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. 一种制备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)、铵盐沉淀装置(2)、铵盐加料装置(3)、预热系统(4)、还原流化床(5)、冷却系统(6)、二级冷却装置(7)、低价钒氧化物加料装置(8)、溶解活化反应釜(9)；
    所述铵盐沉淀装置(2)包括铵盐沉淀反应罐(2-1)和洗涤过滤器(2-2)；
    所述铵盐加料装置(3)包括铵盐料仓(3-1)和铵盐螺旋加料器(3-2)；
    所述预热系统(4)包括一级旋风预热器(4-1)、文丘里预热器(4-2)、二级旋风预热器(4-3)、第一旋风分离器(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)、氯化铵沉降塔(5-6)；
    所述冷却系统(6)包括文丘里冷却器(6-1)、旋风冷却器(6-2)、第二旋风分离器(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)；
    所述三氯氧钒储罐(1)底部的出料口与所述铵盐沉淀反应罐(2-1)的氯化物进料口通过管道相连；所述铵盐沉淀反应罐(2-1)的氨水溶液入口与纯化氨水总管及所述第一旋风分离器(4-4)的出气口通过管道相连；所述铵盐沉淀反应罐(2-1)的烟气出口与尾气处理系统通过管道相连；所述铵盐沉淀反应罐(2-1)的浆料出口与所述洗涤过滤器(2-2)的浆料入口通过管道相连；所述洗涤过滤器(2-2)的清水入口与洁净水总管通过管道相连；所述洗涤过滤器(2-2)的洗涤液出口与废水处理单元通过管道相连；所述洗涤过滤器(2-2)的固体物料出口与所述铵盐料仓(3-1)的进料口通过管道相连；
    所述铵盐料仓(3-1)底部的出料口与所述铵盐螺旋加料器(3-2)的进料口相连接；所述铵盐螺旋加料器(3-2)的出料口与所述文丘里预热器(4-2)的进料口通过管道相连；
    所述文丘里预热器(4-2)的进气口与所述一级旋风预热器(4-1)的出气口通过管道相连；所述文丘里预热器(4-2)的出料口与所述二级旋风预热器(4-3)的进气口通过管道相连；所述二级旋风预热却器(4-3)的出气口与所述第一旋风分离器(4-4)的进气口通过管道相连；所述二级旋风冷却器(4-3)的出料口与所述一级旋风冷却器(4-1)的进气口通过管道相连；所述第一旋风分离器(4-4)的出气口与所述铵盐沉淀反应罐(2-1)的氨水溶液入口通过管道相连；所述第一旋风分离器(4-4)的出料口与所述一级旋风预热器(4-1)的进气口通过管道相连；所述一级旋风预热器(4-1)的进气口与所述氯化铵沉降塔(5-6)的出气口通过管道相连；所述一级旋风预热器(4-1)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通过管道相连；所述床体(5-2)的高温烟气出口与所述氯化铵沉降塔(5-6)的进气口通过管道相连；所述氯化铵沉降塔(5-6)的出气口与所述一级旋风预热器(4-1)的进气口通过管道相连；所述床体(5-2)的进气口与所述气体加热器(5-4)的出气口通过管道相连；所述气体加热器(5-4)的进气口分别与所述第二旋风分离器(6-3)及所述气体净化器(5-5)的出气口通过管道相连；所述气体加热器(5-4)的助燃风入口与压缩空气总管相连；所述气体加热器(5-4)燃料入口与燃料总管相连；所述气体净化器(5-5)的进气口与还原气体总管相连；
    所述文丘里冷却器(6-1)的进气口与净化氮气总管相连；所述文丘里冷却器(6-1) 的出气口与所述旋风冷却器(6-2)的进气口通过管道相连；所述旋风冷却器(6-2)的出气口与所述第二旋风分离器(6-3)的进气口通过管道相连；所述旋风冷却器(6-2)的出料口与所述二级冷却装置(7)的进料口通过管道相连；所述第二旋风分离器(6-3)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(6-3)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)的工艺水入口与工艺水总管相连；所述二级冷却装置(7)的工艺水出口与水冷却系统相连；
    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反应釜(9)的进料口通过管道相连接；
    所述溶解活化反应釜(9)的洁净水入口与洁净水总管相连；所述溶解活化反应釜(9)的硫酸溶液入口与硫酸溶液总管连接；所述溶解活化反应釜(9)的气体出口与尾气处理系统相连。
  2. 一种基于权利要求1所述系统制备高纯钒电解液的方法，包括以下步骤：
    所述三氯氧钒储罐(1)中的三氯氧钒液体通过管道进入所述铵盐沉淀反应罐(2-1)中与来自纯化氨水总管的氨水及所述还原流化床(5)的富氨尾气发生水解沉淀，形成含多钒酸铵、偏钒酸铵的铵盐沉淀与氯化铵溶液的混合浆料；产生的烟气送尾气处理系统；浆料进入所述洗涤过滤器(2-2)中经洁净水洗涤，过滤后得到洗涤液和铵盐沉淀粉料；洗涤液送往废水处理系统；铵盐沉淀送入所述铵盐料仓(3-1)中；
    所述铵盐料仓(3-1)中的铵盐沉淀依次进入所述铵盐螺旋加料器(3-2)、所述文 丘里预热器(4-2)、所述二级旋风预热器(4-3)、所述一级旋风预热器(4-1)，与所述第一旋风分离器(4-4)回收的细粉一同经所述进料器(5-1)送入所述床体(5-2)中；来自于净化氮气总管的净化氮气依次进入所述文丘里冷却器(6-1)、所述旋风冷却器(6-2)、所述第二旋风分离器(6-3)，与来自于所述气体净化器(5-5)净化还原气体汇合，一同送入所述床体(5-2)中使铵盐沉淀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富氨还原烟气；富氨还原烟气经所述氯化铵沉降塔(5-6)沉降后，依次进入所述一级旋风预热器(4-1)、所述文丘里预热器(4-2)、所述二级旋风预热器(4-3)、经所述第一旋风分离器(4-4)除尘后，与来自于纯化氨水总管的氨水混合，一同送入所述铵盐沉淀反应罐(2-1)；低价钒氧化物经所述排料器(5-3)，依次进入所述文丘里冷却器(6-1)、所述旋风冷却器(6-2)中，与所述第二旋风分离器(6-3)回收的细粉一同经所述二级冷却装置(7)、所述低价钒氧化物料仓(8-1)、所述低价钒氧化物螺旋加料器(8-2)、进入所述溶解活化反应釜(9)中，在超声波场的作用下，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尾气处理系统。
  3. 根据权利要求2所述的制备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所述的制备高纯钒电解液的方法，其特征在于，在所述铵盐沉淀反应罐(2-1)内，加入纯化氨水与三氯氧钒的质量比为0.5～20，所述氨水的浓度为15mol/L，所述操作温度30～90℃。
  5. 根据权利要求2所述的制备高纯钒电解液的方法，其特征在于，所述铵盐料仓(3-1)中的铵盐是指偏钒酸铵、多钒酸铵和氯化铵中的一种或多种。
  6. 根据权利要求2所述的制备高纯钒电解液的方法，其特征在于，所述通入还原气体净化器(5-5)中的还原气体为氢气或煤气。
  7. 根据权利要求2所述的制备高纯钒电解液的方法，其特征在于，在还原流化床的床体(5-2)内，还原的操作温度为400～700℃，所述还原气体经所述气体净化器(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所述的制备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混合电解液，钒离子的平均价态为3.5。
  9. 根据权利要求2所述的制备高纯钒电解液的方法，其特征在于，所述硫酸溶液为电子级纯度、摩尔浓度为4.0～10.0mol/L。
  10. 根据权利要求2所述的制备高纯钒电解液的方法，其特征在于，在所述溶解活化反应釜(9)中，采用超声波的方式促进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℃，功率密度为10～300W/L，频率为28KHz、40KHz或60KHz。
PCT/CN2017/071204 2016-01-28 2017-01-16 一种制备高纯钒电解液的系统及方法 WO2017128966A1 (zh)

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