Search

CN-121988056-A - Production equipment, system and method of deuterated ammonia

CN121988056ACN 121988056 ACN121988056 ACN 121988056ACN-121988056-A

Abstract

The invention discloses a production device, a system and a method of deuterated ammonia, wherein the device comprises an absorption unit, an exchange unit, a decomposition unit and a deuterated ammonia storage unit, and the production device of deuterated ammonia provided by the invention can realize the preliminary enrichment of hydrogen isotopes through natural water electrolysis, and then exchange the hydrogen isotopes in water into ammonia gas through a gas absorption-hydrogen deuterium exchange-ammonolysis process, so as to realize the efficient and continuous preparation from natural water to high-purity deuterated ammonia.

Inventors

  • GAO ZHANGHUA
  • WU TAO
  • CAO BOTAO
  • LIU KEKE
  • TANG JIANBO
  • WU YAN

Assignees

  • 宁波萃英化学技术有限公司

Dates

Publication Date
20260508
Application Date
20251222

Claims (15)

  1. 1. A production device of deuterated ammonia, which is characterized by comprising an absorption unit (500), an exchange unit (600), a decomposition unit (700) and a deuterated ammonia storage unit (800); The absorption unit (500) comprises a third condenser (520) and an absorption tower (510) which are sequentially communicated, wherein the upper part of the absorption tower (510) is provided with a heavy water stock solution inlet and a deuterated ammonia outlet, and the lower part of the absorption tower is provided with a liquid phase outlet and a deuterated ammonia gas inlet; The exchange unit (600) comprises an exchange tower (610) and an ammonia gas input assembly (620), wherein a deuterated ammonia gas outlet and a liquid phase inlet are formed in the upper portion of the exchange tower (610), a deuterated ammonia gas inlet, an ammonia gas inlet and a liquid phase outlet are formed in the lower portion of the exchange tower (610), the ammonia gas inlet in the lower portion of the exchange tower (610) is communicated with the ammonia gas input assembly (620), the deuterated ammonia gas outlet in the upper portion of the exchange tower (610) is communicated with the deuterated ammonia gas inlet in the lower portion of the absorption tower (510), the liquid phase inlet in the upper portion of the exchange tower (610) is communicated with the liquid phase outlet in the lower portion of the absorption tower (510), the absorption unit (500) comprises a feed pump (530), the feed pump (530) is communicated with the heavy water stock solution inlet in the upper portion of the absorption tower (510), and a third flow assembly is arranged between the ammonia gas inlet in the lower portion of the exchange tower (610) and the ammonia gas input assembly (620); The decomposing unit (700) comprises a second condenser (710), a decomposing tower (720) and a reboiler (730) which are sequentially communicated, wherein a liquid phase outlet is formed in the lower portion of the decomposing tower (720), a liquid phase inlet and a deuterated ammonia gas outlet are formed in the upper portion of the decomposing tower (720), the liquid phase outlet in the lower portion of the decomposing tower (720) is communicated with the reboiler (730), the liquid phase inlet in the upper portion of the decomposing tower (720) is communicated with the liquid phase outlet in the lower portion of the exchanging tower (610), the deuterated ammonia gas outlet in the upper portion of the decomposing tower (720) is communicated with the deuterated ammonia gas inlet in the lower portion of the exchanging tower (610), the reboiler (730) is provided with a heavy water treatment liquid outlet, the deuterated ammonia gas outlet in the upper portion of the decomposing tower (720) is communicated with the second condenser (710), and the deuterated ammonia gas outlet in the upper portion of the second condenser (710) is communicated with the deuterated ammonia gas inlet in the lower portion of the exchanging tower (610).
  2. 2. The deuterated ammonia production apparatus according to claim 1, comprising any one or more of the following (I) - (VI): (I) A fourth flow component (630) is arranged between the deuterated ammonia gas outlet at the upper part of the exchange tower (610) and the deuterated ammonia gas inlet at the lower part of the absorption tower (510); (II) a fifth flow assembly (540) is disposed between the third condenser (520) and the deuterated ammonia storage unit (800); (III) a fourth temperature detection component is arranged between a liquid phase inlet at the upper part of the exchange tower (610) and a liquid phase outlet at the lower part of the absorption tower (510); (IV) the ammonia gas input component (620) comprises an ammonia gas storage tank (621), wherein the ammonia gas storage tank (621) is communicated with an ammonia gas inlet at the lower part of the exchange tower (610), and the third flow component is arranged between the ammonia gas storage tank (621) and the ammonia gas inlet at the lower part of the exchange tower (610); (V) a second flow assembly is disposed between the second condenser (710) and the deuterated ammonia gas inlet of the exchange column (610); And (VI) a second temperature detection component is arranged between the liquid phase inlet at the upper part of the decomposing tower (720) and the liquid phase outlet at the lower part of the exchange tower (610).
  3. 3. The deuterated ammonia production plant according to claim 1 or 2, characterized in that it further comprises a deuterium depleted water recovery unit (900), said deuterated ammonia production plant deuterium depleted water recovery unit (900) comprising a first condenser (910); The heavy water treatment liquid outlet of the reboiler (730) is communicated with the first condenser (910); a first flow assembly is disposed between the heavy water treatment fluid outlet of the reboiler (730) and the first condenser (910); The deuterium depleted water recovery unit (900) also includes a deuterium depleted water discharge pump (920), said deuterium depleted water discharge pump (920) being in communication with the first condenser (910).
  4. 4. A method for producing deuterated ammonia, comprising the steps of: the heavy water stock solution enters an absorption tower (510) from the upper part of the absorption tower (510), deuterated ammonia gas enters the absorption tower (510) from the lower part of the absorption tower (510), and the heavy water stock solution and the deuterated ammonia gas are in countercurrent contact in the absorption tower (510) to form third deuterated ammonia water; Third deuterated ammonia water in the absorption tower (510) enters the exchange tower (610) from the upper part of the exchange tower (610), ammonia gas enters the exchange tower (610) from the lower part of the exchange tower (610), and the third deuterated ammonia water and the ammonia gas are in countercurrent contact in the exchange tower (610) to form second deuterated ammonia water and deuterated ammonia gas; the second deuterated ammonia water enters the decomposing tower (720) from the upper part of the decomposing tower (720), and is decomposed into deuterated ammonia gas and heavy water treatment liquid at high temperature in the decomposing tower (720), and the heavy water treatment liquid enters a reboiler (730) and is discharged.
  5. 5. The method for producing deuterated ammonia according to claim 4, comprising any one or more of the following conditions (I) - (X): (I) Deuterated ammonia gas generated by pyrolysis in the decomposition tower (720) is condensed and then is introduced into the exchange tower (610) from the bottom of the exchange tower (610); (II) the heavy water treatment liquid enters a reboiler (730) to be discharged, and then the heavy water treatment liquid is condensed to obtain deuterium-depleted water; (III) the inflow rate of heavy water stock solution of the absorption tower (510) is 15-2400 kg/h, and the inflow rate of ammonia gas of the exchange tower (610) is 10-1000 kg/h; (IV) the feeding mole ratio of the ammonia gas to the heavy water stock solution is 1 (1.5-2.0); (V) the intake flow rate of deuterated ammonia gas in the absorption tower (510) is 50-7100 kg/h; (VI) the inlet flow rate of deuterated ammonia gas of the exchange tower (610) is 15-2000 kg/h, and the inlet flow rate of third deuterated ammonia water of the exchange tower (610) is 30-4800 kg/h; (VII) the liquid inlet flow rate of the second deuterated ammonia water of the decomposing tower (720) is 30-4200 kg/h, and the liquid inlet flow rate of the deuterated ammonia generated by the decomposing tower (720) is 15-2000 kg/h when the deuterated ammonia water is introduced into the exchanging tower (610); (VIII) the flow rate of the heavy water treatment liquid of the decomposing tower (720) is 15-2200 kg/h; The temperature range in the absorption tower (510) is-10-30 ℃, the liquid inlet temperature of the third deuterated ammonia water into the exchange tower (610) is 10-20 ℃, and the temperature range in the exchange tower (610) is 0-80 ℃; the temperature range in the decomposing tower (720) is 95-110 ℃, and the liquid inlet temperature of the second deuterated ammonia water into the decomposing tower (720) is 50-80 ℃.
  6. 6. A deuterated ammonia production system, which is characterized by comprising an alkaline electrolytic cell coupled with an on-line heavy water extraction and enrichment device and a deuterated ammonia production device; the alkaline electrolytic cell coupling online heavy water extraction and enrichment equipment comprises a deuterium enriched water extraction unit (200), an alkaline electrolytic unit (100) and a separation and circulation unit (300); The production equipment of deuterated ammonia is the production equipment of deuterated ammonia according to any one of claims 1-3; The alkaline electrolytic tank is coupled with a deuterium enriched water extraction unit (200) of an on-line heavy water enrichment device and is communicated with a heavy water stock solution inlet at the upper part of an absorption tower (510) of an absorption unit (500) of a deuterated ammonia production device.
  7. 7. The deuterated ammonia production system of claim 6 wherein the deuterium enriched water extraction unit (200) comprises an evaporator (210), a condenser two (220), and a deuterium enriched water storage (230) that are in communication in that order; the deuterium enriched water storage (230) is communicated with a heavy water stock solution inlet at the upper part of an absorption tower (510) of the absorption unit (500); The alkaline electrolysis unit (100) comprises an alkaline electrolysis cell (110); 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 circulation pump I (360).
  8. 8. The deuterated ammonia production system of claim 7, wherein an inlet of the anode gas-liquid separator (310) is in communication with an anode side of the alkaline electrolyzer (110), a gas outlet of the anode gas-liquid separator (310) is in communication with a positive electrode of the fuel cell (330), and a liquid outlet of the anode gas-liquid separator (310) is in communication with an anode side of the alkaline electrolyzer (110) via a circulation pump one (360); The inlet of the cathode gas-liquid separator (320) is communicated with the cathode side of the alkaline electrolytic tank (110), the gas outlet of the cathode gas-liquid separator (320) is communicated with the cathode of the fuel cell (330), the evaporator (210) comprises a liquid inlet arranged at the upper part, a high Wen Fudao water vapor outlet and a liquid outlet arranged at the lower part, the liquid outlet of the cathode gas-liquid separator (320) is communicated with the liquid inlet of the evaporator (210), the condenser II (220) is communicated with the high-temperature deuterium-enriched water vapor outlet of the evaporator (210), and the liquid outlet of the evaporator (210) is communicated with the cathode side of the alkaline electrolytic tank (100).
  9. 9. The deuterated ammonia production system according to claim 7, wherein the separation and circulation unit (300) further comprises a first condenser (340), wherein the first condenser (340) is disposed between a cathode gas-liquid separator (320) and a fuel cell (330), wherein a gas outlet of the cathode gas-liquid separator (320) is in communication with a negative electrode of the fuel cell (330) through the first condenser (340); condensate formed by the condenser one (340) is returned to the cathode gas-liquid separator (320), and/or The separation and circulation unit (300) further comprises a third condenser (350), the third condenser (350) is arranged at the rear side of the fuel cell (330), and a tail gas outlet of the fuel cell (330) is communicated with an inlet of the third condenser (350).
  10. 10. The deuterated ammonia production system according to any one of claims 6-9, wherein 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 of the alkaline electrolyzer (110); The liquid buffer (240) is arranged between the evaporator (210) and the fourth circulating pump (260), the liquid buffer (240) is communicated with the cathode side of the alkaline electrolytic tank (110) through the fourth circulating pump (260), and/or The alkaline electrolyzer coupled on-line extraction heavy water enrichment facility further comprises a deuterium enriched water supply (410); the deuterium enriched water supply (410) provides deuterium enriched water to the cathode side of the alkaline electrolysis cell (110).
  11. 11. The deuterated ammonia production system of claim 10, wherein the alkaline electrolyzer is coupled to a number of on-line extraction and enrichment heavy water facilities; The two adjacent alkaline electrolytic tanks are coupled with on-line heavy water extraction and enrichment equipment which is connected in the following manner: A deuterium enriched water storage (230) of the on-line extraction and heavy water enrichment equipment coupled with the alkaline electrolysis cell of the upper stage is communicated with the cathode side of an alkaline electrolysis cell (110) of the on-line extraction and heavy water enrichment equipment coupled with the alkaline electrolysis cell of the lower stage; a fuel cell (330) of the on-line extraction and enrichment heavy water device coupled with the alkaline electrolytic tank of the next stage is communicated with the cathode side of an alkaline electrolytic tank (110) of the on-line extraction and enrichment heavy water device coupled with the alkaline electrolytic tank of the previous stage; the upper alkaline electrolyzer is coupled to a deuterium enriched water storage (230) of an on-line extraction heavy water enrichment device and is in communication with a deuterium enriched water supply (410) of an on-line extraction heavy water enrichment device of a lower alkaline electrolyzer.
  12. 12. The deuterated ammonia production system of claim 11 wherein a fuel cell (330) of the next stage alkaline electrolyzer coupled to the on-line extraction heavy water enrichment facility is in communication with a deuterium enriched water supply (410) of the previous stage alkaline electrolyzer coupled to the on-line extraction heavy water enrichment facility; The fuel cell (330) of the on-line extraction and enrichment heavy water device coupled with the next alkaline electrolytic cell is communicated with the cathode side of the alkaline electrolytic cell (110) of the on-line extraction and enrichment heavy water device coupled with the previous alkaline electrolytic cell through the condenser III (350); 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).
  13. 13. The deuterated ammonia production system according to any one of claims 6-9 and 11-12 further comprising a proton exchange membrane electrolyzer, wherein the proton exchange membrane electrolyzer is coupled with an alkaline electrolyzer in series with an on-line heavy water extraction and enrichment device; And/or the production system of deuterated ammonia further comprises liquid ammonia rectifying equipment, wherein the liquid ammonia rectifying equipment comprises a rectifying tower unit, and deuterated ammonia prepared by the production equipment of deuterated ammonia is used as a raw material of the liquid ammonia rectifying equipment.
  14. 14. A continuous process for the production of deuterated ammonia comprising: Production of heavy water stock solution; Production of deuterated ammonia as described in claim 6 or 7; the production of the heavy water stock solution comprises the following steps: s1, carrying out water electrolysis by using an alkaline electrolytic tank (110); s2, respectively carrying out gas-liquid separation on gas-liquid mixtures generated on the anode side and the cathode side of the 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 flows back to the anode side; and (3) treating liquid separated from the gas-liquid mixture generated on the cathode side, and separating to obtain deuterium-enriched water and alkali-containing concentrated solution, wherein the alkali-containing concentrated solution flows back to the cathode side.
  15. 15. The continuous production method of deuterated ammonia according to claim 14 comprising a multi-stage treatment process wherein any one of said process steps is performed according to an on-line continuous extraction process for enriching heavy water; wherein deuterium-enriched water obtained by separation in the previous step is introduced into the cathode side of an alkaline electrolytic tank (110) in the next step for water electrolysis; And/or, introducing deuterium depleted water generated by the reaction of the fuel cell (330) of the next stage process into the cathode side of the alkaline electrolytic tank (110) of the previous stage process for water electrolysis.

Description

Production equipment, system and method of deuterated ammonia Technical Field The invention belongs to the technical field of hydrogen isotope enrichment, and particularly relates to production equipment, system and method of deuterated ammonia. Background Deuterated ammonia is used as a key isotope labeling reagent and has irreplaceable application value in two fields of chemical synthesis and electronic industry. In the field of chemical synthesis, deuterated ammonia is a core precursor substance for introducing amino, has been widely applied to the synthesis process of various deuterated medicaments and intermediates thereof, provides important technical support for medicament development and production, plays an indispensable role in the manufacturing link of memory chips in the field of electronic industry, and has the core application of depositing silicon nitride (SiN) and silicon oxynitride (SiON) films, wherein the film materials have excellent insulating property and protective property, and are key basic materials for guaranteeing the stable operation of microelectronic devices. Currently, the mainstream preparation method of deuterated ammonia takes magnesium nitride (Mg 3N2) as a raw material, and the synthesis of a target product is realized through the chemical reaction of the magnesium nitride and heavy water (D 2 O). However, this production process has significant limitations, particularly in four aspects, one of which is raw material supply and cost constraints. Magnesium nitride (Mg 3N2) is taken as a core raw material, so that the market price is high, the supply stability is insufficient, the final production cost of deuterated ammonia is directly high, and the large-scale application of the deuterated ammonia is limited. Secondly, the technical difficulty in the reaction process. Magnesium nitride (Mg 3N2) reacts with heavy water (D 2 O) to form heavy magnesium hydroxide (Mg (OD) 2), a water-insoluble byproduct. The existence of the byproducts can increase the uniformity difficulty of material mixing in a reaction system, and simultaneously, the stirring process is required to be higher, so that the reaction efficiency and the product yield are affected, and the large-scale amplification of the process is hindered. Thirdly, the resource utilization efficiency is low. In the reaction process, part of heavy hydrogen (D) element can be fixed in the byproduct heavy magnesium hydroxide (Mg (OD) 2) and cannot be effectively converted into a target product, so that the waste of heavy hydrogen resources is caused, and the atomic utilization rate of raw materials is reduced. Fourth, the technical challenges of product purification. Because trace moisture is inevitably introduced into a reaction system, and the separation difficulty of deuterated ammonia and water is high, the separation and purification of high-purity deuterated ammonia from a reaction product becomes extremely difficult, and the expansion of the product quality and the application scene is directly influenced. Based on this, patent application CN114506818a discloses a recovery process adopting reactive distillation in combination with multi-tower serial connection, which promotes the forward progress of hydrogen-deuterium exchange by adjusting the molar ratio of heavy water to ammonia gas and the feeding position, and simultaneously sets an ammonia recovery tower, a heavy water recovery tower and a purification tower to realize the cyclic utilization of intermediate products and unreacted substances, thereby improving the utilization rate of deuterium atoms and reducing the impurity content. However, the ammonia recovery tower and the heavy water recovery tower are required to meet the design of 'high theoretical plate number plus high reflux ratio', a high-power circulating pump and a condenser are required to be relied on to further increase energy consumption, on one hand, a high-power compressor and a pressure control system are required to be matched for high-pressure operation, the energy consumption for maintaining the system pressure accounts for 25-35% of total energy consumption, on the other hand, the temperature of the reaction rectifying tower kettle is required to be controlled at 145-212 ℃, the temperature of the deuterated ammonia purifying tower kettle is required to be 130-200 ℃, high-temperature heat sources (such as steam and electric heating) are required to be continuously supplied, and the long-term operation cost is extremely high. In addition, the intermediate product is recycled by means of multi-tower circulation, cross contamination is easy to cause by the intermediate product circulation, the purity control risk is high, four parameters including pressure, temperature, reflux ratio and raw material proportion are required to be synchronously controlled, the difficulty of multi-parameter coupling regulation and control of strong coupling relation exists among the parameters, and the process interfe