Preparation method of isotope labeled ammonium energetic material

Abstract

The invention relates to a preparation method of an isotope labeled ammonium energetic material, which comprises the following steps: (1) putting 15N2 and magnesium powder into a container replaced by inert gas, and heating for reaction to obtain 15N labeled magnesium nitride powder; (2) adding heavy water into the 15N-labeled magnesium nitride powder in a dropwise manner, and collecting the 15N-labeled magnesium nitride powder through a cold trap to obtain 15ND3; and (3) reacting the 15ND3 with a precursor acid to obtain the high-abundance isotope labeled ammonium energetic material. Compared with the prior art, the method has the advantage that the isotope abundance of 15N and D in the-15ND < 4 + > group can reach 99% or above.

Description

Technical Field

[0001] The invention belongs to the technical field of isotope labeled material preparation, and relates to a method for preparing an isotope labeled ammonium energetic material. Background Art

[0002] Energetic ammonium salts are an important component in the field of energetic materials. Common ones include ammonium nitrate, ammonium perchlorate and ammonium picrate. Their structures all contain a good hydrogen bond donor group - NH4 + , -NH4 + It is an important group in energetic materials. + All are formed after isotope substitution - 15 ND4 + , its mass number increases by 5. The increase in mass will increase its density, which will greatly improve the detonation performance of the material.

[0003] Acta Cryst. (1979). B35, 1038-1041, mentions a process for preparing deuterated ammonium nitrate, dissolving ammonium nitrate in 99.6% D2O, and obtaining deuterated ammonium nitrate after recrystallization. In addition, CN111620351A discloses a method for preparing fully deuterated ammonium dinitramide, the isotope source of its deuterated ammonium group is deuterated ammonia, but does not disclose the preparation process of the key raw material deuterated ammonia. CN114506859A discloses a method for preparing high-purity deuterated ammonia, using high-purity deuterium and high-purity nitrogen, to prepare deuterated ammonia under high pressure conditions of 10MPa to 30MPa and high temperature conditions of 300℃ to 600℃. This process requires high temperature and high pressure conditions, and the reaction conditions are harsh. CN114853031B discloses a method for preparing deuterated ammonia by hydrolyzing calcium nitride. In this process, calcium nitride easily reacts with water in the air, thereby causing dilution of the isotopic abundance of the product.

[0004] It can be seen that the existing isotope labeling technology of ammonium energetic materials such as deuterated ammonium nitrate generally replaces ammonium nitrate with 15 N-labeled ammonium nitrate or ammonium perchlorate has problems such as complicated reaction steps, low isotope utilization rate, and low isotope abundance. The reasons are: (1) It is necessary to prepare 15 N-labeled ammonium nitrate or ammonium perchlorate, then prepared by heavy water exchange 15 ND4NO3 or 15 ND4ClO4, the reaction steps are complicated; (2) 15 N is introduced in the first step of the reaction. As the number of reaction steps increases, the utilization rate of isotopic atoms decreases. (3) The abundance of the prepared ammonium nitrate is low and cannot meet the requirement of high isotopic abundance. (4) The reaction usually requires high temperature, which involves 15The N atom introduction step (Atomic Energy Science and Technology, 1985, 19(003): 339-339.) is carried out in a quartz glass tube and does not meet the conditions for process amplification. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing isotope-labeled ammonium energetic materials. 15 ND4 + In the group 15 The isotopic abundances of N and D are both above 99%.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A method for preparing an isotope-labeled ammonium energetic material comprises the following steps:

[0008] (1) 15 N2 and magnesium powder are placed in a container replaced with inert gas and heated to react to obtain 15 N marks magnesium nitride powder;

[0009] (2) Add heavy water dropwise to 15 N-labeled magnesium nitride powder was collected by cold trap to obtain 15 ND3;

[0010] (3) 15 ND3 reacts with precursor acid to obtain high-abundance isotope-labeled ammonium energetic material.

[0011] Furthermore, in step (1), the container is a tubular furnace, the inert gas is argon, and the inert gas is replaced with argon for more than 3 times before the heating reaction.

[0012] Furthermore, in step (1), the heating reaction temperature is 700-830° C. and the time is 2-4 hours.

[0013] Further, in step (1), the 15 The ratio of N2 to magnesium powder added is 20L: (20~25)g.

[0014] Further, in step (2), the heavy water and 15 The molar ratio of the N-labeled magnesium nitride powder is 6:1 to 12:1.

[0015] Furthermore, in step (2), the temperature of the cold trap is -35°C to -90°C.

[0016] Furthermore, in step (3), the precursor acid is 15 ND3 (or NH3) reacts to generate an acid corresponding to the ammonium energetic material, illustratively, nitric acid or perchloric acid.

[0017] Furthermore, in step (3), 15 The molar ratio of ND3 to the precursor acid is 1:1 to 3:1.

[0018] Furthermore, in step (3), the reaction temperature is room temperature and the reaction time is 2 to 4 hours.

[0019] The present invention optimizes the process parameters such as the material molar ratio, adopts a tubular furnace and argon protection, so that the reaction is carried out under relatively mild conditions, while avoiding the risk of deuterium isotope abundance dilution, so that the deuterium isotope abundance of the product reaches more than 99.6%. In addition, under the premise of ensuring that the isotope abundance is not diluted, the reaction process is combined and optimized, and a one-step preparation method is adopted. 15 The method of simultaneously labeling ammonia with N and deuterium simplifies the reaction process and improves the utilization rate of isotope atoms.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] 1) The present invention designs a preparation process of isotope labeled ammonium energetic materials, the key point is 15 ND 4+ The preparation process of the radical adopts a tubular reactor, so that the materials are fully mixed in the tubular furnace, the reaction temperature is lower, and the reaction conditions are relatively mild.

[0022] 2) The present invention can make the deuterium isotope abundance greater than 99.6% by controlling the number of argon replacements and strictly collecting the cold trap temperature, and the product isotope abundance is high;

[0023] 3) The present invention can complete the reaction within 4 hours, and the reaction time is shorter. DETAILED DESCRIPTION

[0024] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0025] In the following examples, unless otherwise specified, raw materials or processing techniques are conventional commercially available raw materials or conventional processing techniques in the art.

[0026] Embodiment 1:

[0027] A preparation process of an isotope-labeled ammonium energetic material comprises the following steps:

[0028] 20L 15 N2 was mixed with 21.43 g magnesium powder in a tube furnace, replaced with argon three times, heated to 830 ° C, reacted for 4 h, and prepared by reduction reaction.15 N-labeled magnesium nitride (Mg3 15 N2) powder 88.34g (0.87mol), yield 97%;

[0029] 103.93 g (5.2 mol) of heavy water was added dropwise to the Mg3 15 N2 powder was collected in a -90℃ cold trap to obtain 15.46g 15 ND3, the reaction yield of this step is 85%;

[0030] Then 15 ND3 reacts with 46.38 g of the corresponding nitric acid to prepare 56.32 g of ammonium labeled ammonium nitrate ( 15 ND4NO3, abundance is 99.2atom% 15 N, 99.6 atom % D).

[0031] Embodiment 2:

[0032] Compared with Example 1, most of the contents were the same, except that 155.89 g (7.79 mol) of heavy water was added, and 16.55 g of 15 ND3, the reaction yield of this step is 91%; 60.29g of ammonium labeled ammonium nitrate ( 15 ND4NO3, abundance is 99.19atom% 15 N, 99.7 atom % D).

[0033] Embodiment 3:

[0034] Compared with Example 2, most of the contents are the same, except that 207.86 g (10.39 mol) of heavy water was added, and 17.82 g of 15 ND3, the reaction yield of this step is 98%; 64.93g of ammonium labeled ammonium nitrate ( 15 ND4NO3, abundance is 99.24atom% 15 N, 99.8 atom % D).

[0035] Embodiment 4:

[0036] Compared with Example 1, most of the conditions were the same, except that the number of argon replacements was reduced from 3 to 2, and 56.3 g of ammonium-labeled ammonium nitrate ( 15 ND4NO3, abundance is 92.19atom% 15 N, 99.7atom%D), it can be seen that the number of argon replacements has an effect on 15 N abundance has a greater impact.

[0037] Embodiment 5:

[0038] A preparation process of an isotope-labeled ammonium energetic material comprises the following steps:

[0039] 20L 15 N2 was mixed with 21.43 g magnesium powder in a tube furnace, replaced with argon three times, heated to 830 ° C, reacted for 4 h, and prepared by reduction reaction. 15 N-labeled magnesium nitride (Mg3 15 N2) powder 88.79g (0.87mol), the yield is 97.5%; 208.93g (10.45mol) of heavy water is added dropwise to the Mg3 15 N2 powder was collected in a -90℃ cold trap to obtain 17.92g 15 ND3, the reaction yield of this step is 98%; 15 ND3 reacts with 85.74 g of perchloric acid to prepare 99.28 g of ammonium labeled ammonium nitrate ( 15 ND4ClO4, abundance 99.3atom% 15 N, 99.8 atom % D).

[0040] Embodiment 6:

[0041] Compared with Example 5, most of the above are the same, except that the heating temperature is 700°C and the reduction reaction is performed to obtain 15 N-labeled magnesium nitride (Mg3 15 N2) powder 69.21g (0.68mol), the yield is 76%; and 66.83g perchloric acid to prepare 77.39g ammonium labeled ammonium nitrate ( 15 ND4ClO4, abundance 99.2atom% 15 N, 99.6 atom % D).

[0042] Embodiment 7:

[0043] Compared with Example 5, most of the conditions are the same, except that the reaction time is 2 h and the reduction reaction is performed to obtain 15 N-labeled magnesium nitride (Mg3 15 N2) powder 61.93g (0.61mol), the yield is 68%; and 59.8g perchloric acid to prepare 69.24g ammonium labeled ammonium nitrate ( 15 ND4ClO4, abundance 99.3atom% 15 N, 99.7 atom % D).

[0044] Embodiment 8:

[0045] Compared with Example 5, most of the above are the same, except that the cold trap temperature is -35°C and the reduction reaction is performed to prepare15 N-labeled magnesium nitride (Mg3 15 N2) powder 88.79g (0.87mol), the yield is 97.5%; after collecting in a cold trap, 16.82g 15 ND3, the reaction yield of this step is 92%; react with 80.49g perchloric acid to prepare 93.2g of ammonium labeled ammonium nitrate ( 15 ND4ClO4, abundance is 99.25atom% 15 N, 99.66 atom % D).

[0046] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing an isotope-labeled ammonium energetic material, characterized in that: The following steps are involved: (1) 15 N2 and magnesium powder are placed in a container replaced with inert gas and heated to react to obtain 15 N marks magnesium nitride powder; (2) Add heavy water dropwise to 15 N-labeled magnesium nitride powder was collected by cold trap to obtain 15 ND3; (3) 15 ND3 reacts with precursor acid to obtain high-abundance isotope-labeled ammonium energetic material.

2. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (1), the container is a tubular furnace, which is replaced with inert gas more than 3 times before the heating reaction.

3. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (1), the inert gas is argon.

4. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (1), the heating reaction temperature is 700-830° C. and the time is 2-4 hours.

5. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (1), the 15 The ratio of N2 to magnesium powder added is 20L: (20~25)g.

6. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (2), the heavy water and 15 The molar ratio of the N-labeled magnesium nitride powder is 6:1 to 12:

1.

7. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (2), the temperature of the cold trap is -35°C to -90°C.

8. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (3), the precursor acid is nitric acid or perchloric acid.

9. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (3), 15 The molar ratio of ND3 to the precursor acid is 1:1 to 3:

1.

10. The method for preparing an isotope-labeled ammonium energetic material according to claim 1, characterized in that: In step (3), the reaction temperature is room temperature and the reaction time is 2 to 4 hours.