A deuterated ammonia purification filling system and process

Abstract

The application relates to the technical field of deuterated ammonia purification, in particular to a deuterated ammonia purification and filling system and process. The system comprises a light-removing tower, a heavy-removing tower, a fine product cold trap, a filling row and a crude product cold trap, each device is connected through a specified pipeline, the light-removing tower, the heavy-removing tower and the filling row are connected with an online detection system, and some pipelines are provided with pneumatic diaphragm valves. The process takes 4N deuterated ammonia as raw material, carries out purification detection through the light-removing tower, directly fills qualified products, and re-purifies unqualified products through the heavy-removing tower; the heavy-removing tower product is filled after being qualified, and unqualified products are slowly purified; when the pressure of the equipment is higher than 0.4 MPa, the gaseous deuterated ammonia slowly enters the fine product cold trap, is vaporized after being slowly stored, and is filled, and the operation temperature and pressure range of each device are limited. The whole process flow is detected and processed through multiple stages, the purification and filling efficiency is effectively optimized, the energy consumption is reduced, the production cycle is shortened, and an efficient and energy-saving solution is provided for production units.

Description

Technical Field

[0001] This application relates to the field of deuterated ammonia purification technology, and more specifically, to a deuterated ammonia purification and filling system and process. Background Technology

[0002] Deuterated ammonia, a compound formed by the stable isotope of hydrogen, deuterium, and nitrogen, is an important raw material in modern high-tech fields. In nuclear magnetic resonance (NMR), high-purity deuterated ammonia is used as an aprotic deuterated solvent, providing a clear spectral background for studying complex molecular structures. In the semiconductor manufacturing industry, deuterated ammonia is used as a special electronic gas in thin film deposition processes. Furthermore, in biomedicine and new materials science, deuterated ammonia is an important precursor or deuterium source for synthesizing various deuterated drugs, deuterated reagents, and isotope-labeled compounds, which is of great significance for drug metabolism kinetics studies and the exploration of new material properties. However, its chemical purity is usually required to reach 99.99% or even higher. Nevertheless, whether prepared by the reaction of magnesium nitride with heavy water or by the isotope exchange reaction of ammonia and deuterium, the initially synthesized crude deuterated ammonia inevitably contains various impurities. Based on their boiling point differences relative to the main product, deuterated ammonia, these impurities can be broadly classified into two categories: Light component impurities: These mainly include partially deuterated ammonia, ordinary ammonia, and non-condensable gases such as nitrogen and deuterium that may be introduced during production or storage. Heavy component impurities: These mainly include reactants remaining from the synthesis process, such as heavy water, and other possible high-boiling-point organic or inorganic impurities.

[0003] To meet the application needs of high-precision fields, the synthesized crude deuterated ammonia is efficiently purified to remove the aforementioned light and heavy component impurities.

[0004] Current technologies for separating multi-component, high-purity chemical products like deuterated ammonia generally employ distillation in mainstream industrial production. Distillation is a unit operation that utilizes the differences in boiling points of components in a mixture to achieve separation; it is a mature technology with high throughput. A series-connected twin-tower distillation system is typically used. Finally, after passing quality inspection, the product is filled into cylinders. This series-connected twin-tower distillation process provides a feasible technical solution for the production of high-purity deuterated ammonia. Technical documents such as those with announcement numbers CN114853031B, CN110980648B, CN120736538A, and CN120736538A all utilize a series of heavy and light component removal towers, taking advantage of the different boiling points of the main components to remove both heavy and light components, thereby achieving purification.

[0005] However, traditional purification processes have the following drawbacks: First, high energy consumption: The entire process needs to be carried out at low temperature and certain pressure. Regardless of the purity of the deuterated ammonia raw material entering the purification system, it must undergo complete processing through two high-energy-consuming units: a light-weight removal tower and a heavy-weight removal tower. For intermediate products or raw materials with higher purity, the system still performs unnecessary purification, resulting in low energy efficiency of the entire production process.

[0006] Secondly, low production efficiency: High energy consumption is accompanied by low production efficiency. The fixed series connection mode of traditional processes not only leads to unnecessary energy consumption but also significantly prolongs the production cycle. Furthermore, in actual production, the impurity composition and content of different batches of synthesized products often fluctuate. However, the traditional dual-tower series process path is fixed and cannot be optimized and adjusted according to real-time changes in raw materials.

[0007] Third, poor flexibility: Quality monitoring of intermediate materials or final products during production typically relies on offline sampling and analysis. Operators manually sample from the production line and use analytical instruments such as gas chromatographs for testing. The entire process is time-consuming, with delays of tens of minutes or even hours between sampling and obtaining analysis results. By the time the analysis shows that the product purity is substandard, a large amount of material may have already been processed under unsuitable operating conditions. Operators can only make rough, experience-based adjustments to process parameters based on lagging data.

[0008] Therefore, there is an urgent need in this field for a deuterated ammonia purification and filling system that can overcome the drawbacks of traditional purification processes, thereby minimizing energy consumption, shortening production cycles, and improving production efficiency and system flexibility while ensuring product quality. Summary of the Invention

[0009] To address the problems of high energy consumption, long production cycle, and low efficiency in the high-efficiency purification and filling of deuterated ammonia in existing technologies, this application proposes a deuterated ammonia purification and filling system and process to reduce energy consumption, shorten the production cycle, and improve production efficiency and system flexibility.

[0010] The technical solution of this application is as follows: On the one hand, this application provides a deuterated ammonia purification and filling system, including a light product removal tower, a heavy product removal tower, a refined product cold trap, a filling outlet, and a crude product cold trap; The light-weight removal tower is connected to the heavy-weight removal tower via pipeline S4, to the premium cold trap via pipeline S5, and to the filling pump via pipeline S6. The light-weight removal tower is also connected to the online detection system via pipeline S3. The deweight removal tower is connected to the crude product cold trap via pipeline S8, to the filling pump via pipeline S9, and to the refined product cold trap via pipeline S10. The deweight removal tower is also connected to the online detection system via pipeline S7. The premium cold trap is connected to the filling pump via an S12 pipeline; The filling line is connected to the online detection system via the S14 pipeline.

[0011] Preferably, the online detection system is an infrared spectrometer.

[0012] Preferably, a first pneumatic diaphragm valve is provided on the S6 pipeline; a second pneumatic diaphragm valve is provided on the S10 pipeline.

[0013] Preferably, the premium cold trap is connected to the light removal tower and the heavy removal tower via pipeline S11, and is connected to the filling drain via pipeline S13.

[0014] Preferably, the side of the light product removal tower is also connected to the S1 pipeline, which is used to transport the raw material deuterated ammonia; the crude product cold trap is also connected to the S1 pipeline through the S2 pipeline.

[0015] On the other hand, this application provides a deuterated ammonia purification and filling process, including the following steps: S1. The raw material deuterated ammonia enters the light-light removal tower for the first purification; during the purification process in the light-light removal tower, the purity of the deuterated ammonia in the light-light removal tower is monitored in real time. S2. Based on the real-time monitoring results of step S1, perform the first path selection: If the monitoring results show that the purity of deuterated ammonia reaches 5N, then the qualified deuterated ammonia will be directly transported to the filling port via the S6 pipeline for filling. If the monitoring results show that the purity of deuterated ammonia does not reach 5N, it is then transported via S4 to the deweighting tower for second-stage purification; S3. During the purification process of deuterated ammonia in the deweight removal tower, the purity of deuterated ammonia in the deweight removal tower is monitored in real time. S4. Based on the real-time monitoring results of step S3, perform the second path selection: If the monitoring results indicate that H2O in deuterated ammonia is ≤1ppm, then qualified deuterated ammonia will be transported to the filling port via the S9 pipeline for filling. If the monitoring results show that H2O in deuterated ammonia is greater than 1 ppm, the unqualified deuterated ammonia will be transported to the crude product cold trap buffer via the S8 pipeline, to be returned to the light removal tower (1) for re-purification; S5, A first pneumatic diaphragm valve is installed on the S6 pipeline; A second pneumatic diaphragm valve is installed on the S10 pipeline; When the pressure inside the light removal tower (1) or heavy removal tower (2) exceeds the threshold of 0.4MPa, the corresponding pneumatic diaphragm valve automatically opens to guide the gaseous deuterated ammonia to the premium cold trap for buffering; S6. The premium cold trap receives and buffers the gaseous deuterated ammonia from the pipeline in step S5, or serves as a buffer container to receive qualified products from the deweighting tower; after buffering, the deuterated ammonia is vaporized by heating the premium cold trap and then transported to the filling pump via the pipeline in S12 for filling.

[0016] Preferably, the operating temperature of the light-light removal tower is -140℃ to -110℃, and the operating pressure is 1-4MPa.

[0017] Preferably, the operating temperature of the deweight removal tower is 25℃~66℃, and the operating pressure is 1~3MPa.

[0018] Preferably, the cooling temperature of the premium cold trap is -170°C.

[0019] Preferably, the purity of the raw material deuterated ammonia is 4N.

[0020] The beneficial effects of this application are as follows: This application connects online detection systems to both the light and heavy removal towers, forming a two-stage detection and diversion mechanism. When the deuterated ammonia purified by the light removal tower reaches a purity of 5N, it can be directly transported to the filling port through the S6 pipeline for filling, without needing to enter the heavy removal tower and cold trap, thus reducing the frequency of use of the heavy removal tower and cold trap. When the deuterated ammonia purified by the heavy removal tower reaches the H2O≤1ppm standard, it can be directly transported to the filling port through the S9 pipeline for filling, reducing the frequency of use of the cold trap, thereby reducing equipment operating energy consumption, and eliminating unnecessary processing steps, effectively improving production efficiency and shortening the production cycle.

[0021] This application installs a first pneumatic diaphragm valve in the S6 pipeline and a second pneumatic diaphragm valve in the S10 pipeline as pressure interlock valves. When the pressure inside the light or heavy removal tower exceeds a set threshold of 0.4 MPa, the corresponding pneumatic diaphragm valve automatically opens, guiding the gaseous deuterated ammonia to the high-quality cold trap, thus constructing a filling and cold trap channel. This effectively prevents excessive system pressure due to untimely filling, avoids safety risks such as explosions and leaks, and ensures stable system operation.

[0022] This high-quality cold trap has multiple functions. It can buffer emergency gaseous deuterated ammonia from the light and heavy removal towers, and it can also serve as a buffer container to receive qualified products from the heavy removal tower. The buffered deuterated ammonia can be filled by heating and vaporizing. In this process, the cold trap plays a supplementary distillation role, which can further improve the purity of the deuterated ammonia. At the same time, the high-quality cold trap is connected to the light and heavy removal towers and the filling drain through multiple pipelines. Its diversified functions eliminate the need for additional buffer and distillation replenishment equipment, which reduces energy consumption and improves the flexibility of the system.

[0023] Deuterated ammonia that fails the purification test in the heavy removal tower can be transported to the crude product cold trap buffer via the S8 pipeline, and then returned to the light removal tower for repurification. This avoids the waste of unqualified materials and eliminates the need to re-inject raw materials for processing, further shortening the production cycle and reducing production costs. Attached Figure Description

[0024] Figure 1 This is a diagram of the deuterated ammonia purification and filling system for this application.

[0025] Attached diagram labels: 1. Light product removal tower; 2. Heavy product removal tower; 3. Fine product cold trap; 4. Filling drain; 5. Crude product cold trap; 6. First pneumatic diaphragm valve; 7. Second pneumatic diaphragm valve; 8. S1 pipeline; 9. S2 pipeline; 10. S3 pipeline; 11. S4 pipeline; 12. S5 pipeline; 13. S6 pipeline; 14. S7 pipeline; 15. S8 pipeline; 16. S9 pipeline; 17. S10 pipeline; 18. S11 pipeline; 19. S12 pipeline; 20. S13 pipeline; 21. S14 pipeline. Detailed Implementation

[0026] To further illustrate the technical means and effects adopted by this application in order to achieve the intended purpose of the invention, the following detailed description of the specific implementation methods, structures, features and effects of this application is provided in conjunction with the accompanying drawings and preferred embodiments.

[0027] Device Examples This embodiment provides a deuterated ammonia purification and filling system, see [link to documentation]. Figure 1 The details are as follows: The purification and filling system includes a light product removal tower 1, a heavy product removal tower 2, a refined product cold trap 3, a filling drain 4, and a crude product cold trap 5.

[0028] Light-light removal tower 1 is connected to the raw material deuterated ammonia via pipeline S1 8 and receives circulating material from the crude product cold trap 5 via pipeline S2 9. Light-light removal tower 1 is connected to heavy-light removal tower 2 via pipeline S4 11, to the refined product cold trap 3 via pipeline S5 12, and to the filling drain 4 via pipeline S6 13. A first pneumatic diaphragm valve 6 is installed on pipeline S6 13. Light-light removal tower 1 is also connected to an infrared spectrometer via pipeline S3 10 as an online detection system. This setup can monitor the purity of deuterated ammonia after light-light removal in real time. Qualified material directly enters the filling drain 4 via pipeline S6 13 without passing through heavy-light removal tower 2 and refined product cold trap 3, effectively reducing ineffective process steps, lowering energy consumption, and shortening the production cycle.

[0029] The deweighting tower 2 is connected to the crude product cold trap 5 via S8 pipe 15, the filling line 4 via S9 pipe 16, and the refined product cold trap 3 via S10 pipe 17. A second pneumatic diaphragm valve 7 is installed on the S10 pipe 17. The deweighting tower 2 is also connected to an infrared spectrometer via S7 pipe 14 as an online detection system. After deweighting, qualified materials directly enter the filling line 4, reducing the frequency of cold trap use and further improving efficiency.

[0030] The premium cold trap 3 is connected to the light-weight removal tower 1 and the heavy-weight removal tower 2 via the S11 pipe 18, and to the filling drain 4 via the S12 pipe 19. It is also connected to the filling drain 4 via the S13 pipe 20. The premium cold trap 3 can buffer gaseous deuterated ammonia at -170℃. When heated and vaporized, the built-in packing plays a role in distillation, further improving the purity of deuterated ammonia. It serves as both a buffer container and a distillation supplement unit, solving the shortcomings of traditional cold traps that can only buffer.

[0031] The filling line 4 is connected to an infrared spectrometer via S14 pipeline 21 to perform final testing on all materials to be filled, ensuring stable product purity. The light component removal tower 1 operates at a temperature of -140℃ to -110℃ and an operating pressure of 1-4 MPa, removing light components; the heavy component removal tower 2 operates at a temperature of 25℃ to 66℃ and an operating pressure of 1-3 MPa, removing heavy components.

[0032] When the pressure in the light removal tower 1 or the heavy removal tower 2 exceeds the preset interlock pressure value, the first pneumatic diaphragm valve 6 or the second pneumatic diaphragm valve 7 will automatically open, guiding the gaseous deuterated ammonia to the high-quality cold trap 3, thus creating a filling-cold trap emergency channel. This effectively prevents the risk of overpressure explosion or leakage caused by untimely filling and improves system safety.

[0033] The filling process of the device: S1. Deuterated ammonia with a purity of 4N is introduced into the light component removal tower 1 through pipeline S1 8. The first purification is carried out under the operating conditions of -140℃ to -110℃ and 1-4MPa to remove residual deuterium, nitrogen and other light components. At the same time, the purity of the deuterated ammonia after light component removal is monitored in real time by an infrared spectrometer connected to pipeline S3 10. This step provides a basis for subsequent splitting through pre-detection and avoids ineffective purification.

[0034] S2. Based on the monitoring results of step S1, perform the first path selection: If the purity of deuterated ammonia reaches 5N, the first pneumatic diaphragm valve 6 will open, and qualified deuterated ammonia will be directly transported to the filling drain 4 via the S6 pipeline 13. This path can reduce the frequency of use of the deweight removal tower 2 and the premium cold trap 3, improve filling efficiency and reduce energy consumption. If the purity does not meet the standard, the material enters the de-weighting tower 2 via pipeline S4 11 for second-stage purification.

[0035] S3. The material entering the deweighting tower 2 is purified under the operating conditions of 25℃~66℃ and 1~3MPa to remove heavy components such as water and metal impurities. At the same time, the purity of deuterated ammonia after deweighting is monitored in real time by an infrared spectrometer connected to pipeline S7 14.

[0036] S4. Based on the monitoring results of step S3, perform the second path selection: If H2O in deuterated ammonia is ≤1ppm, then qualified deuterated ammonia is transported to filling drain 4 via S9 pipeline 16, reducing the frequency of use of premium cold trap 3 and further improving efficiency; If the monitoring results show that H2O in deuterated ammonia is greater than 1 ppm, the unqualified material is transported to the crude product cold trap 5 for buffering via S8 pipeline 15, and then returned to the light product removal tower 1 for re-purification via S2 pipeline 9, so as to realize the closed-loop circulation of materials and avoid material waste.

[0037] S5. When the pressure in the light-duty removal tower 1 exceeds 0.4 MPa, the corresponding first pneumatic diaphragm valve 6 or the second pneumatic diaphragm valve 7 will automatically open, guiding the gaseous deuterated ammonia through the S5 pipeline 12 or the S10 pipeline 17 to the high-quality cold trap 3 for buffering. This emergency channel can quickly alleviate the overpressure inside the tower, prevent the risk of explosion or leakage, and improve the safety of system operation.

[0038] S6. The premium cold trap 3 receives the gaseous deuterated ammonia from step S5 or the qualified product from the deweighting tower 2. After condensation and buffering at -170°C, the liquid deuterated ammonia is vaporized by heating it to 35~40°C. The heating and vaporization utilizes the difference in boiling points between deuterated ammonia and impurities. The high-boiling-point heavy components remain at the bottom of the liquid phase, which is equivalent to simple distillation, thereby improving the purity of deuterated ammonia and increasing the product purity to over 99.999%. It is then transported to the filling drain 4 via pipeline S12 19.

[0039] S7 and filling line 4 are connected to an infrared spectrometer via S14 line 21 to perform final testing on the deuterated ammonia to be filled. After confirming that the purity is qualified, the filling operation is carried out to ensure the high purity and stability of the delivered product.

[0040] The entire process involves multi-level detection and grading, which effectively optimizes purification and filling efficiency, reduces energy consumption, and shortens the production cycle, providing production units with a highly efficient and energy-saving solution.

[0041] After one month of operation and testing using the system of this application, the results showed that, compared with the traditional two-stage distillation technology, the high-efficiency purification and filling system of this application reduced the steam consumption per unit product by 32.6%, the circulating water consumption by 29.3%, and the comprehensive energy consumption of the distillation unit by 31.5%, achieving a stable energy consumption reduction of over 30%. The traditional process takes 12-15 hours for a single batch, while this process eliminates the 3-5 hour running time of the de-gravity section, shortening the production cycle of a single batch to 7.2-9.3 hours, corresponding to a reduction of 28.3%-40.0%, fully covering the 20%-40% cycle optimization range.

[0042] The above description is merely a preferred embodiment of this application and is not intended to limit this application in any way. Although this application has been disclosed above with reference to preferred embodiments, it is not intended to limit this application. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the technical solution of this application. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of this application without departing from the scope of the technical solution of this application shall still fall within the scope of the technical solution of this application.

Claims

1. A deuterated ammonia purification and filling system, characterized in that, It includes a light-removal tower (1), a heavy-removal tower (2), a fine-quality cold trap (3), a filling bar (4), and a coarse-quality cold trap (5); The light removal tower (1) is connected to the heavy removal tower (2) via S4 pipeline (11), to the premium cold trap (3) via S5 pipeline (12), and to the filling bar (4) via S6 pipeline (13). The light removal tower (1) is also connected to the online detection system via S3 pipeline (10). The deweight removal tower (2) is connected to the crude product cold trap (5) via S8 pipeline (15), the filling bar (4) via S9 pipeline (16), and the premium product cold trap (3) via S10 pipeline (17). The deweight removal tower (2) is also connected to the online detection system via S7 pipeline (14). The premium cold trap (3) is connected to the filling line (4) via the S12 pipe (19). The filling line (4) is connected to the online detection system via the S14 pipeline (21).

2. The deuterated ammonia purification and filling system according to claim 1, characterized in that, The online detection system is an infrared spectrometer.

3. The deuterated ammonia purification and filling system according to claim 1, characterized in that, A first pneumatic diaphragm valve (6) is installed on the S6 pipeline (13); a second pneumatic diaphragm valve (7) is installed on the S10 pipeline.

4. The high-efficiency purification and filling system for deuterated ammonia according to claim 1, characterized in that, The premium cold trap (3) is connected to the light removal tower (1) and the heavy removal tower (2) via pipeline S11 (18), and is connected to the filling drain (4) via pipeline S13 (20).

5. The deuterated ammonia purification and filling system according to claim 1, characterized in that, The light removal tower (1) is also connected to the S1 pipeline (8) on the side, and the S1 pipeline (8) is used to transport the raw material deuterated ammonia; the crude product cold trap (5) is also connected to the S1 pipeline (8) through the S2 pipeline (9).

6. A deuterated ammonia purification and filling process, based on the deuterated ammonia purification and filling system according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. The raw material deuterated ammonia enters the light removal tower (1) for the first purification. During the purification process in the light removal tower (1), the purity of the deuterated ammonia in the light removal tower (1) is monitored in real time. S2. Based on the real-time monitoring results of step S1, perform the first path selection: If the monitoring results show that the purity of deuterated ammonia reaches 5N, then the qualified deuterated ammonia will be directly transported to the filling line (4) via the S6 pipeline (13) for filling. If the monitoring results show that the purity of deuterated ammonia does not reach 5N, it is transported to the de-heavy tower (2) via S4 for second-stage purification; S3. During the purification process of deuterated ammonia in the deweight removal tower (2), the purity of deuterated ammonia in the deweight removal tower (2) is monitored in real time. S4. Based on the real-time monitoring results of step S3, perform the second path selection: If the monitoring results show that H2O in deuterated ammonia is ≤1ppm, then qualified deuterated ammonia will be transported to the filling line (4) via the S9 pipeline (16) for filling. If the monitoring results show that H2O in deuterated ammonia is greater than 1 ppm, the unqualified deuterated ammonia will be transported to the crude product cold trap (5) via the S8 pipeline (15) for buffering, to be returned to the light removal tower (1) for repurification; S5, A first pneumatic diaphragm valve (6) is installed on the S6 pipeline (13); A second pneumatic diaphragm valve (7) is installed on the S10 pipeline (17); When the pressure inside the light removal tower (1) or heavy removal tower (2) exceeds the threshold of 0.4MPa, the corresponding pneumatic diaphragm valve automatically opens, guiding the gaseous deuterated ammonia to the high-quality cold trap (3) for buffering; S6. The premium cold trap (3) receives and buffers the gaseous deuterated ammonia from the pipeline (12) in step S5, or serves as a buffer container to receive qualified products from the deweight tower (2); after buffering, the deuterated ammonia is vaporized by heating the premium cold trap (3) and transported to the filling drain (4) via the pipeline (19) in S12 for filling.

7. The deuterated ammonia purification and filling system according to claim 6, characterized in that, The operating temperature of the light-light removal tower (1) is -140℃ to -110℃, and the operating pressure is 1-4MPa.

8. The deuterated ammonia purification and filling system according to claim 6, characterized in that, The operating temperature of the deweight removal tower (2) is 25℃~66℃ and the operating pressure is 1~3MPa.

9. The deuterated ammonia purification and filling system according to claim 6, characterized in that, The cooling temperature of the premium cold trap (3) is -170℃.

10. The deuterated ammonia purification and filling process according to claim 6, characterized in that, The purity of the raw material, deuterated ammonia, is 4N.

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