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CN-121988166-A - Alkaline electrolytic tank coupling on-line heavy water extraction and enrichment equipment, system and method

CN121988166ACN 121988166 ACN121988166 ACN 121988166ACN-121988166-A

Abstract

The invention discloses an alkaline electrolytic cell coupling on-line heavy water extraction and enrichment device, system and method, wherein the device comprises an alkaline electrolytic unit, a deuterium enriched water extraction unit, a gas-liquid separation and water regeneration unit; the cascade enrichment system is formed by connecting the multi-stage electrolytic enrichment equipment in series, so that the deuterium isotopes in the raw water are concentrated step by step on line, and the product water with high deuterium enrichment degree is obtained.

Inventors

  • GAO ZHANGHUA
  • WU TAO
  • TANG JIANBO
  • WU YAN
  • Bu Yalu
  • CAO BOTAO

Assignees

  • 宁波萃英化学技术有限公司

Dates

Publication Date
20260508
Application Date
20250829

Claims (15)

  1. 1. An alkaline electrolytic cell coupling on-line heavy water enrichment extraction device is characterized by comprising an alkaline electrolytic unit (100), a deuterium enriched water extraction unit (200) and a separation and circulation unit (300); The alkaline electrolysis unit (100) comprises an alkaline electrolysis cell (110); the deuterium enriched water extraction unit (200) comprises an evaporator (210), a second condenser (220) and a deuterium enriched water storage (230) which are communicated in sequence; The separation and circulation unit (300) comprises an anode gas-liquid separator (310), a cathode gas-liquid separator (320), a fuel cell (330) and a first circulation pump (360); Wherein a gas-liquid inlet of the anode gas-liquid separator (310) is communicated with an anode side (111) of the alkaline electrolytic tank (110), a gas outlet of the anode gas-liquid separator (310) is communicated with a positive electrode (332) of the fuel cell (330), and a liquid outlet of the anode gas-liquid separator (310) is communicated with the anode side (111) of the alkaline electrolytic tank (110) through a circulating pump I (360); The gas-liquid inlet of the cathode gas-liquid separator (320) is communicated with the cathode side (112) of the alkaline electrolytic tank (110), and the gas outlet of the cathode gas-liquid separator (320) is communicated with the cathode (331) of the fuel cell (330); The evaporator (210) comprises a liquid inlet (211) arranged at the upper part, a high Wen Fudao water vapor outlet (212) and a liquid outlet (213) arranged at the lower part, the liquid outlet of the cathode gas-liquid separator (320) is communicated with the liquid inlet (211) of the evaporator (210), and the condenser II (220) is communicated with the high-temperature deuterium-enriched water vapor outlet (212) of the evaporator (210).
  2. 2. The alkaline cell coupled on-line heavy water extraction plant of claim 1, wherein the liquid outlet (213) of the evaporator (210) is in communication with the cathode side (112) of the alkaline cell (110).
  3. 3. The alkaline electrolyzer coupled on-line extraction heavy water enrichment device according to claim 1 or 2, wherein the separation and recycling unit (300) further comprises a condenser one (340) and/or a condenser three (350); the condenser I (340) is arranged between the cathode gas-liquid separator (320) and the fuel cell (330), a gas outlet of the cathode gas-liquid separator (320) is communicated with a cathode (331) of the fuel cell (330) through the condenser I (340), and condensate formed by the condenser I (340) flows back to the cathode gas-liquid separator (320); The third condenser (350) is arranged at the rear side of the fuel cell (330), and the tail gas outlet of the fuel cell (330) is communicated with the inlet of the third condenser (350).
  4. 4. -Alkaline electrolyzer-coupled heavy water enrichment facility according to any of the claims 1 to 3, characterized in that the deuterium enriched water extraction unit (200) further comprises a liquid buffer (240) and a circulation pump four (260) arranged between the evaporator (210) and the cathode side (112) of the alkaline electrolyzer (110); the liquid buffer (240) is arranged between the evaporator (210) and the fourth circulating pump (260), and the liquid buffer (240) is communicated with the cathode side (112) of the alkaline electrolytic tank (110) through the fourth circulating pump (260).
  5. 5. The alkaline electrolyzer coupled on-line extraction heavy water enrichment device of any of claims 1-4, wherein the alkaline electrolyzer coupled on-line extraction heavy water enrichment device further comprises a deuterium enriched water supply (410); the deuterium enriched water supply (410) is in communication with the cathode side (112) of the alkaline electrolyzer (110), or The deuterium enriched water supply (410) communicates with the liquid buffer (240).
  6. 6. The alkaline electrolyzer coupling on-line heavy water extraction unit of any one of claims 1 to 5 characterized in that the deuterium enriched water extraction unit (200) further comprises a flow component one (250), said flow component one (250) being arranged between the cathode gas-liquid separator (320) and the evaporator (210), the liquid outlet of the cathode gas-liquid separator (320) being in communication with the liquid inlet (211) of the evaporator (210) through the flow component one (250), and/or, The alkaline electrolytic cell coupling on-line heavy water extraction and enrichment device further comprises a second flow component (411), wherein the second flow component (411) is arranged between the deuterium-enriched water supply device (410) and the cathode side (112) of the alkaline electrolytic cell (110), or the second flow component (411) is arranged between the deuterium-enriched water supply device (410) and the liquid buffer (240).
  7. 7. An alkaline electrolytic cell coupled on-line heavy water extraction and enrichment system, which is characterized by comprising a plurality of alkaline electrolytic cell coupled on-line heavy water extraction and enrichment devices according to any one of claims 1-6; the two adjacent alkaline electrolytic tanks are coupled with the on-line heavy water extraction and enrichment equipment and are communicated in the following manner: A deuterium enriched water storage (230) of the on-line extraction and heavy water enrichment device coupled with the alkaline electrolysis cell of the upper stage is communicated with a cathode side (112) of an alkaline electrolysis cell (110) of the on-line extraction and heavy water enrichment device coupled with the alkaline electrolysis cell of the lower stage; The fuel cell (330) of the next stage alkaline electrolyzer coupled on-line extraction heavy water enrichment facility is in communication with the cathode side (112) of the alkaline electrolyzer (110) of the previous stage alkaline electrolyzer coupled on-line extraction heavy water enrichment facility.
  8. 8. The alkaline electrolyzer coupled on-line heavy water extraction system of claim 7 characterized in that the deuterium enriched water storage (230) of the upper alkaline electrolyzer coupled on-line heavy water extraction device is in communication with the deuterium enriched water supply (410) of the lower alkaline electrolyzer coupled on-line heavy water extraction device; A fuel cell (330) of the next stage alkaline electrolyzer coupled to the on-line extraction heavy water enrichment facility communicates with a deuterium enriched water supply (410) of the previous stage alkaline electrolyzer coupled to the on-line extraction heavy water enrichment facility.
  9. 9. The system for on-line extraction of enriched heavy water by coupling an alkaline electrolyzer according to claim 7, wherein the fuel cell (330) of the on-line extraction and enrichment heavy water plant of the next alkaline electrolyzer is connected with the cathode side (112) of the alkaline electrolyzer (110) of the on-line extraction and enrichment heavy water plant of the previous alkaline electrolyzer through the condenser three (350) thereof, or The fuel cell (330) of the next stage alkaline electrolyzer coupled on-line extraction heavy water enrichment facility communicates with the deuterium enriched water supply (410) of the previous stage alkaline electrolyzer coupled on-line extraction heavy water enrichment facility through its condenser three (350).
  10. 10. The method for continuously extracting the enriched heavy water on line is characterized by comprising the following steps of: s1, carrying out water electrolysis by using an alkaline electrolytic tank (110); s2, respectively carrying out gas-liquid separation on gas-liquid mixtures generated by an anode side (111) and a cathode side (112) of an alkaline electrolytic tank (110), and introducing the separated gases into a fuel cell (330) for reaction to generate deuterium-depleted water; The liquid separated from the gas-liquid mixture generated on the anode side (111) flows back to the anode side (111); The liquid separated from the gas-liquid mixture generated on the cathode side (112) is treated, deuterium enriched water and alkali-containing concentrated solution are obtained through separation, and the alkali-containing concentrated solution flows back to the cathode side (112).
  11. 11. The method for on-line continuous extraction of enriched heavy water according to claim 10, wherein the gas-liquid mixture generated at the cathode side (112) is subjected to gas-liquid separation, the separated gas is subjected to condensation treatment, the treated gas is introduced into the fuel cell (330), the treated liquid is subjected to secondary treatment, deuterium enriched water and an alkali-containing concentrated solution are separated, and the alkali-containing concentrated solution is refluxed to the cathode side (112).
  12. 12. The method for continuously extracting enriched heavy water on line according to claim 11, wherein the liquid separated from the gas and the liquid is subjected to evaporation treatment to obtain deuterium-enriched water and an alkali-containing concentrated solution, and the evaporation treatment conditions comprise any one, two or more of the following (I) to (IV): (I) The vacuum degree is 100-350KPa; (II) an evaporation temperature of 55-90 ℃; (III) performing the evaporation treatment with an evaporator (210); (IV) the liquid inlet flow rate in the evaporation treatment is 1.0-5500L/h; (V) the extraction flow rate of deuterium enriched water obtained by separation is 0.05-270Kg/h.
  13. 13. The method for continuously extracting enriched heavy water on line according to any one of claims 16 to 18, wherein the conditions for carrying out water electrolysis in the alkaline electrolytic cell (110) include any one, two or more of the following (I) to (IX): (I) The alkali concentration of the alkaline electrolyte is 20-40 wt%; (II) the alkali concentration of the alkaline electrolyte is 25-30wt%; (III) the electrolysis temperature of the alkaline electrolyte is 55-90 ℃; (IV) the electrolysis operation pressure is 0.8MPa to 1.6MPa; (V) the liquid inlet flow rate of the electrolyte at the anode side (111) of the alkaline electrolytic tank (110) is 0.05-1100L/h; (VIII) the electrolyte inlet flow rate of the cathode side (112) electrolyte of the alkaline electrolytic tank (110) is 1.0-6500L/h.
  14. 14. The method for continuously extracting and enriching heavy water with high deuteration degree on line is characterized by comprising a multi-stage treatment process, wherein any stage of the process steps is carried out according to the steps of the method for continuously extracting and enriching heavy water on line according to any one of claims 10-13; Wherein deuterium-enriched water obtained by separation in the previous step is introduced into the cathode side (112) of an alkaline electrolytic tank (110) of the next step for water electrolysis; And/or, introducing deuterium depleted water generated by the reaction of the fuel cell (330) of the next step into the cathode side (112) of the alkaline electrolytic tank (110) of the previous step for water electrolysis.
  15. 15. The comprehensive system for extracting and enriching heavy water on line is characterized by comprising a pretreatment system and a deep treatment system connected in series with the pretreatment system, wherein the deep treatment system comprises a proton exchange membrane electrolytic tank; The pretreatment system comprises the alkaline electrolytic cell coupling on-line heavy water extraction and enrichment equipment of any one of claims 1-6, Or comprises the alkaline electrolytic cell coupling on-line heavy water enrichment system as claimed in any one of claims 7-9.

Description

Alkaline electrolytic tank coupling on-line heavy water extraction and enrichment equipment, system and method Technical Field The application belongs to the technical field of electrolyzed water, and particularly relates to equipment, a system and a method for on-line extraction and enrichment of heavy water by coupling an alkaline electrolytic tank. Background Currently there are three main technologies for electrolytic enhancement of deuterium content in water, including laboratory and industrial scale, which differ primarily in the type of electrolyte used in the cell. Three major types of water electrolysis cells that are currently commercially available are alkaline electrolysis cells, proton exchange membrane cells and solid oxide electrolysis cells. The alkaline electrolytic tank (ALKALINE WATER Electrolyzer, ALK) is one of the most mature and widely applied water electrolysis hydrogen production equipment in the prior art, and water is electrolyzed into hydrogen (H 2) and oxygen (O 2) mainly through alkaline electrolyte solution (such as KOH and NaOH), so that the alkaline electrolytic tank has the characteristics of low cost and high reliability, is particularly suitable for large-scale fixed scene hydrogen production, and is one of the core technologies of the current hydrogen energy industry. The proton exchange membrane battery (Proton Exchange Membrane Battery, PEM) is usually a proton exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell, PEMFC), is a high-efficiency power generation device taking a Proton Exchange Membrane (PEM) as electrolyte, has the advantages of quick low-temperature starting, high power density, zero emission and the like, and is widely applied to the fields of transportation, portable power sources, distributed energy sources and the like. Solid oxide electrolyzer (Solid Oxide Electrolysis Ce, SOEC) is a high-efficiency electrolytic hydrogen production technology based on solid oxide electrolytes, mainly used for converting water (H 2 O) or carbon dioxide (CO 2) into hydrogen (H 2), carbon monoxide (CO) or synthesis gas (H 2 +co). The method has the core advantages of high-temperature working characteristics (600-1000 ℃) and fuel flexibility, and is particularly suitable for large-scale green hydrogen production and industrial decarburization scenes. The first two types of water baths operate at near ambient temperature (typically from ambient to 90 ℃) whereas SOEC water baths typically operate at temperatures between 700-950 ℃. Hydrogen production by ALK water electrolysis cells is now a well established technology and electrolytic devices up to the Megawatt (MW) scale have been commercially used. ALK water baths use aqueous KOH as the liquid electrolyte. Compared with a PEM water electrolyzer, the ALK water electrolyzer has the advantages of low cost of hydrogen production capacity, large treatment capacity and the like, and is suitable for electrolysis of the first several stages of serial deuterium extraction devices. However, deuterium enrichment and concentration of base are carried out with electrolysis, which is disadvantageous for continuous operation control. There is therefore a need for an efficient evaporation apparatus for treating lye. Based on this, CN105408234B discloses an electrolytic enrichment method for heavy water comprising enriching heavy water by electrolysis with an alkaline electrolysis cell comprising an anode chamber containing an anode, a cathode chamber containing a cathode and a membrane. In this method, an electrolyte prepared by adding high-concentration alkaline water to raw water containing heavy water is circulated and supplied from a circulation tank to an anode chamber and a cathode chamber, an anode-side gas-liquid separator and an anode-side water seal device are connected to the anode chamber and a cathode-side gas-liquid separator and a cathode-side water seal device are connected to the cathode chamber, and continuous electrolysis is performed while maintaining the concentration of alkali in the electrolyte supplied to both electrolysis chambers at a constant concentration by circulating the electrolyte to the circulation tank and separating gas generated from the electrolyte from the anode-side gas-liquid separator and the cathode-side gas-liquid separator, but the separation of hydrogen isotopes in the electrolyte is limited by the gas separation efficiency at the time of electrolysis in an alkaline electrolytic tank, the deuteration degree of heavy water cannot be continuously improved on line, and/or the concentration of heavy water enrichment is limited, and the deuteration degree of commercially available heavy water cannot be satisfied. Disclosure of Invention Problems to be solved Aiming at the problems that the existing heavy water electrolytic enrichment can not continuously improve the deuteration degree of the heavy water on line and/or the concentration of the heavy water enrichment is limited and can