System and method for producing high-purity and high-activity vanadium electrolyte

Patent metadata

Field	Value
Publication number	US-10707515-B2
Application number	US-201716073908-A
Country	US
Kind code	B2
Filing date	Jan 16, 2017
Priority date	Jan 28, 2016
Publication date	Jul 7, 2020
Grant date	Jul 7, 2020

Abstract

A system and method for producing a high-purity and high-activity vanadium electrolyte, comprising converting high-purity vanadium oxytrichloride into an ammonium salt in a fluidized bed by gas phase ammoniation, then in another fluidized bed, reducing the ammonium salt into a low-valence vanadium oxide having an average vanadium valence of 3.5, adding clean water and sulfuric acid for dissolution, and further performing activation by ultrasound to obtain a 3.5-valence vanadium electrolyte which can be directly used in a new all-vanadium redox flow battery stack. The method of producing an ammonium salt containing vanadium in the fluidized bed by gas phase ammoniation is of short process and high efficiency. Precise regulation of the valence state of the reduction product is implemented by arranging an internal member in the reduction fluidized bed, and ultrasonication is used to activate the vanadium ion, thereby greatly improving the activity of the electrolyte.

First claim

What is claimed is:

1. A system for producing a high-purity and high-activity vanadium electrolyte, comprising a vanadium oxytrichloride storage tank a gas phase ammoniation fluidized bed, a reduction fluidized bed, a pre-cooling device, a secondary cooling device, a low-valence vanadium oxide feeding device, a dissolution reactor, and an activation device;
wherein the gas phase ammoniation fluidized bed comprises a vanadium oxytrichloride vaporizer, a purified ammonia liquor vaporizer, a chloride spray gun, a gas phase ammoniation fluidized bed body, a first cyclone separator, and an ammonium chloride settling tower;
the reduction fluidized bed comprises a material valve, a bed body, a discharger, a gas heater, a gas purifier, and a second cyclone separator;
the pre-cooling device comprises a cyclone cooler and a third cyclone separator;
the low-valence vanadium oxide feeding device comprises a low-valence vanadium oxide hopper and a low-valence vanadium oxide screw feeder;
wherein a feed outlet at the bottom of the vanadium oxytrichloride storage tank is connected with a feed inlet of the vanadium oxytrichloride vaporizer through a pipeline; the feed inlet of the vanadium oxytrichloride vaporizer is connected with a purified nitrogen gas main pipe through a pipeline; a gas outlet of the vanadium oxytrichloride vaporizer is connected with a gas inlet of the chloride spray gun through a pipeline; a feed inlet of the purified ammonia liquor vaporizer is connected with a purified ammonia liquor main pipe and the purified nitrogen gas main pipe through pipelines; respectively; a gas outlet of the purified ammonia liquor vaporizer is connected with a gas inlet at the bottom of the gas phase ammoniation fluidized bed body through a pipeline; a feed outlet at the upper part of the gas phase ammoniation fluidized bed body is connected with a feed inlet of the material valve through a pipeline; the first cyclone separator is provided at the center of the top of the expansion section of the gas phase ammoniation fluidized bed body; a gas outlet of the first cyclone separator is connected with a gas inlet of the ammonium chloride settling tower through a pipeline; and a gas outlet of the ammonium chloride settling tower is connected with a gas inlet of a tail gas absorption system through a pipeline;
a feed outlet of the material valve is connected with a feed inlet of the bed body through a pipeline; an aeration air inlet of the material valve is connected with the nitrogen gas main pipe through a pipeline; a feed outlet of the bed body is connected with a feed inlet of the discharger through a pipeline; a feed outlet of the discharger is connected with a feed inlet of the third cyclone separator through a pipeline; a gas inlet of the bed body is connected with a gas outlet of the gas heater through a pipeline; a gas inlet of the gas heater is connected with a gas outlet of the gas purifier and a gas outlet of the third cyclone separator through pipelines, respectively; a combustion air inlet of the gas heater connected with a compressed air main pipe through a pipeline; a fuel inlet of the gas heater is connected with a fuel main pipe through a pipeline; a gas inlet of the gas purifier is connected with a reducing gas main pipe through a pipeline; the second cyclone separator is provided at the center of the top of the expansion section of the bed body; and a gas outlet of the second cyclone separator is connected with the gas inlet at the bottom of the gas phase ammoniation fluidized bed body through a pipeline;
a gas inlet of the cyclone cooler is connected with the purified nitrogen gas main pipe through a pipeline; a feed outlet of the cyclone cooler is connected with a feed inlet of the secondary cooling device; a gas outlet of the cyclone cooler is connected with a gas inlet of the third cyclone separator through a pipeline; and a feed outlet of the third cyclone separator is connected with the gas inlet of the cyclone cooler through a pipeline;
a feed outlet of the secondary cooling device is connected with a feed inlet of the low-valence vanadium oxide hopper through a pipeline; a process water inlet of the secondary cooling device is connected with a process water main pipe through a pipeline; and a process water outlet of the secondary cooling device is connected with a water cooling system through a pipeline;
a feed outlet at the bottom of the low-valence vanadium oxide hopper is connected with a feed inlet of the low-valence vanadium oxide screw feeder; and a feed outlet of the low-valence vanadium oxide screw feeder is connected with a feed inlet of the dissolution reactor through a pipeline;
a clean water inlet of the dissolution reactor is connected with a clean water main pipe through a pipeline; a sulfuric acid inlet of the dissolution reactor is connected with a sulfuric acid main pipe through a pipeline; a gas outlet of the dissolution reactor is connected with a gas inlet of the tail gas absorption system through a pipeline; and a primary electrolyte outlet of the dissolution reactor is connected with an electrolyte inlet of the activation device through a pipeline.

2. A method for producing a high-purity and high-activity vanadium electrolyte according to the system of claim 1 , comprising the following steps:
introducing vanadium oxytrichloride into the vanadium oxytrichloride storage tank and the nitrogen gas from the purified nitrogen gas main pipe to be vaporized and preheated by the vanadium oxytrichloride vaporizer, and then enter the gas phase ammoniation fluidized bed body through the chloride spray gun; passing the purified ammonia liquor and purified nitrogen gas to be vaporized and preheated by the purified ammonia liquor vaporizer and then be merged with high-temperature tail gas from the second cyclone separator of the reduction fluidized bed, and be transmitted together into the gas phase ammoniation fluidized bed body, such that vanadium oxytrichloride is ammoniated and the powder material is kept at a fluidized state, to form ammonium salt powder and flue gas rich in ammonium chloride; discharging the ammonium salt powder into the bed body through the material valve; and moving the flue gas to be subjected to dust removing by the first cyclone separator, and then entering the ammonium chloride settling tower, and transmitting the tail gas after settlement to the tail gas absorption system;
moving the purified nitrogen gas from the purified nitrogen gas main pipe into the cyclone cooler and the third cyclone separator and then merged with the reducing gas purified by the gas purifier; and preheating the gas mixture by the gas heater and then transmitted into the bed body, such that the ammonium salt is subjected to a reduction reaction wherein the powder material is kept at a fluidized state, and the formed flue gas is subjected to dust removing by the second cyclone separator and then merged with the gas from the purified ammonia liquor vaporizer, and transmitted together into the gas phase ammoniation fluidized bed body; wherein the formed low-valence vanadium oxide is transmitted to the discharger, the third cyclone separator, the cyclone cooler, the secondary cooling device, the low-valence vanadium oxide hopper, and transmitted to the dissolution reactor through the low-valence vanadium oxide screw feeder to undergo dissolution reaction together with clean water from the clean water main pipe and sulfuric acid from the sulfuric acid main pipe to obtain a primary vanadium electrolyte; and transmitting the produced acid mist gas to the tail gas treatment system; and activating the primary electrolyte by the activation device to obtain the vanadium electrolyte.

3. The method for producing a high-purity and high-activity vanadium electrolyte according to claim 2 , wherein the raw material of vanadium oxytrichloride has a purity of 99%-99.9

Assignees

• Inst Process Eng Cas
• Beijing Zhongkaihongde Tech Co Ltd

Inventors

• Yang Haitao
• Zhu Qingshan
• Fan Chuanlin
• Ban Qixun

Classifications

• Y02E60/50

  Fuel cells · CPC title

• C01G31/02

  Oxides · CPC title

• H01M2300/0011

  Sulfuric acid-based · CPC title

• H01M8/188 Primary

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• B01J2219/00002

  Chemical plants · CPC title