Method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace stabilizer

Abstract

The application discloses a method for improving the thermal stability of a hydroxylamine perchlorate solution by adding a trace amount of a stabilizer, which comprises the following steps: preparing a HAP solution containing metal impurity ions, adding a certain amount of a specific stabilizer (DTPA, ATMP, etc.) and mixing uniformly; and experiment results show that the thermal decomposition temperature of the HAP solution can be increased by 21.8 DEG C at most, and the chemical stability time can be prolonged to 146.5 h at most. The application effectively solves the decomposition risk of the HAP caused by metal etching during preparation and storage, and has important significance for the safe application of the HAP in the field of liquid propellants.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials and relates to a method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace amounts of stabilizers. Background Technology

[0002] Hydroxylamine perchlorate (HAP), as a novel high-energy liquid oxidant, has broad application prospects in the field of liquid propellants. However, HAP aqueous solutions are highly corrosive and readily undergo etching reactions with metal containers or pipes during preparation, transportation, and storage. This etching introduces metallic impurities such as iron or copper ions into the solution. Studies have found that these two metal ions have a significant catalytic effect on the decomposition of HAP, severely reducing the thermal stability and combustion performance of HAP solutions.

[0003] Existing solutions mainly rely on protective coatings on the container surface or the use of non-metallic materials, but there is a lack of effective chemical suppression methods for the trace amounts of metal ions that have already been generated. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for enhancing the thermal stability of hydroxylamine perchlorate (HAP) solutions by adding trace stabilizers. This addresses the problem that copper or iron ions present in HAP solutions can lower the thermal decomposition temperature and chemical stability of the solution. Through systematic research, the present invention has discovered that the intrinsic mechanism of metal ion-induced decomposition lies in its reduction of the activation energy of the HAP decomposition reaction. Therefore, introducing highly efficient metal chelating agents to convert free catalytic ions into stable chelates is key to improving the thermal safety of HAP solutions. By comparing various stabilizers (DTPA, ATMP, EDTMP, NTA, HEDTA), the aim is to derive a formulation that can significantly improve the stability of HAP solutions containing metal ion impurities. The present invention is a method for inhibiting the addition of trace stabilizers. In 10 mL of 82.5% HAP solution, a solution containing 100 μg / mL of copper ions, iron ions, or a mixture of both metals as impurities is prepared. By adding 5 mg of stabilizer, its chemical stability and thermal decomposition temperature are enhanced.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace amounts of stabilizers involves adding a chelating stabilizer to a HAP solution containing metal ions, thereby inhibiting the catalytic decomposition of HAP by metal ions through complexation. The HAP solution is a hydroxylamine perchlorate solution, the metal ions are one or both of copper and iron ions, and the stabilizer is selected from DTPA, ATMP, EDTMP, NTA, and HEDTA.

[0007] The present invention also includes the following technical features: Specifically, it includes the following steps: Step 1: Take an 82.5% HAP solution as the base system and set it aside. Step 2: Add ferric nitrate, copper nitrate, or ferric nitrate and copper nitrate to the solution to make the concentration of metal ions in the system reach 100 μg / mL; Step 3: Weigh out the stabilizer and add it to the above solution. Stir the mixture continuously at room temperature to ensure that the stabilizer and metal ions are in full contact and undergo a chelation reaction. Step 4: Perform thermal decomposition and chemical stability tests on the obtained solution.

[0008] Specifically, the addition ratio of 82.5% HAP solution, metal ions in the system, and stabilizer is 10 mL: 1 mg: 5 mg.

[0009] Specifically, in step 3, the stirring conditions are: continuous stirring at 200 rpm for 30 minutes.

[0010] Specifically, in step 4, the obtained solution is subjected to thermal decomposition and chemical stability tests: For HAP solutions containing copper ion impurities, the thermal decomposition temperature of HAP increased from 121.3℃ to a maximum of 143.1℃, and the chemical stability time increased from 8.8 h to a maximum of 67.8 h. For HAP solutions containing iron ion impurities, the thermal decomposition temperature of HAP increased from 132.1℃ to a maximum of 147.2℃, and the chemical stability time increased from 34 h to a maximum of 146.5 h. For HAP solutions containing copper and iron ion impurities, the thermal decomposition temperature of HAP increased from 123.8℃ to a maximum of 141.7℃, and the chemical stability time increased from 10.2 h to a maximum of 68.2 h.

[0011] Compared with the prior art, the present invention has the following technical effects: After adding trace amounts of stabilizer, the thermal decomposition temperature of HAP in HAP solutions containing copper ion impurities increased from a maximum of 121.3℃ to 143.1℃, and the chemical stability time was extended from a maximum of 8.8 h to a maximum of 67.8 h; the thermal decomposition temperature of HAP in HAP solutions containing iron ion impurities increased from a maximum of 132.1℃ to 147.2℃, and the chemical stability time was extended from a maximum of 34 h to a maximum of 146.5 h; the thermal decomposition temperature of HAP in HAP solutions containing both copper and iron ion impurities increased from a maximum of 123.8℃ to a maximum of 141.7℃, and the chemical stability time was extended from a maximum of 10.2 h to a maximum of 68.2 h. Furthermore, the addition amount of 5 mg is extremely low and does not change the energy density or liquid rheological properties of the HAP itself. Detailed Implementation

[0012] This invention provides a method for improving the thermal stability of hydroxylamine perchlorate (HAP) solution by adding a trace amount of stabilizer. The method involves adding a chelating stabilizer to the HAP solution containing metal ions, thereby inhibiting the catalytic decomposition of HAP by metal ions through complexation. The method includes the following steps: Step 1. Take 10 mL of 82.5% HAP solution as the basic system and set aside; Step 2. Add a specific amount of ferric nitrate, copper nitrate, or ferric nitrate and copper nitrate to the solution to make the concentration of metal ions in the system reach 100 μg / mL; Step 3. Accurately weigh 5 mg of stabilizer and add it to the above solution. Place the mixture on a magnetic stirrer and stir continuously for 30 min at room temperature and 200 rpm to ensure that the stabilizer and metal ions are in full contact and undergo a chelation reaction. Step 4. Perform thermal decomposition and chemical stability tests on the obtained solution.

[0013] Furthermore, the stabilizer is selected from one of diethylenetriaminepentaacetic acid (DTPA), aminotrimethylphosphonic acid (ATMP), ethylenediaminetetramethylphosphonic acid (EDTMP), aminotriacetic acid (NTA), and hydroxyethylethylenediaminetriacetic acid (HEDTA).

[0014] The metal ions in the HAP solution are one or both of copper and iron ions.

[0015] This invention provides a method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace amounts of stabilizers.

[0016] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0017] In the following embodiments: The thermal decomposition test was conducted using the high-pressure DSC method in JY / T0589.3-2020.

[0018] Stability was determined using the vacuum stability method in GJB772B-2020.

[0019] Example 1: This embodiment aims to suppress the catalytic decomposition of HAP by copper ions by introducing a trace amount of ATMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. Subsequently, 5 mg of ATMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0020] As shown in Tables 1 and 2, the thermal decomposition initiation temperature of the copper-containing HAP solution without stabilizer was only 121.3℃, and the chemical stability time at a constant temperature of 90℃ was 8.8 h. After adding 5 mg ATMP, the thermal decomposition temperature of the HAP solution shifted significantly upward to 135.6℃, and the chemical stability time at a constant temperature of 90℃ was greatly extended to 13.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0021] Example 2: This embodiment aims to suppress the catalytic decomposition of HAP by metallic iron ions by introducing a trace amount of ATMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of ferric nitrate was added to the solution to achieve an iron ion concentration of 100 μg / mL. Subsequently, 5 mg of ATMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0022] As shown in Tables 1 and 3, the thermal decomposition initiation temperature of the iron-containing HAP solution without stabilizer was only 132.1℃, and the chemical stability time at a constant temperature of 90℃ was 34 h. After adding 5 mg ATMP, the thermal decomposition temperature of the HAP solution shifted significantly upward to 136.4℃, and the chemical stability time at a constant temperature of 90℃ was greatly extended to 58.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0023] Example 3: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of ATMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. Subsequently, 5 mg of ATMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0024] As shown in Tables 1 and 4, the initial thermal decomposition temperature of the HAP solution containing copper and iron mixed ions without stabilizer was only 123.8℃, and the chemical stability time at a constant temperature of 90℃ was 10.2 h. After adding 5 mg ATMP, the thermal decomposition temperature of the HAP solution shifted significantly upward to 139.3℃, and the chemical stability time at a constant temperature of 90℃ was greatly extended to 56.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0025] Example 4: This embodiment aims to suppress the catalytic decomposition of HAP by copper ions by introducing a trace amount of DTPA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. Subsequently, 5 mg of DTPA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0026] As shown in Tables 1 and 2, the addition of 5 mg DTPA significantly increased the thermal decomposition temperature of the HAP solution to 143.1 °C, and greatly extended the chemical stability time to 67.8 h at a constant temperature of 90 °C, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0027] Example 5: This embodiment aims to suppress the catalytic decomposition of HAP by metallic iron ions by introducing a trace amount of DTPA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of ferric nitrate was added to the solution to achieve an iron ion concentration of 100 μg / mL. Subsequently, 5 mg of DTPA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0028] As shown in Tables 1 and 3, the addition of 5 mg DTPA significantly increased the thermal decomposition temperature of the HAP solution to 147.2 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 146.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0029] Example 6: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of DTPA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. Subsequently, 5 mg of DTPA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0030] As shown in Tables 1 and 4, the addition of 5 mg DTPA significantly increased the thermal decomposition temperature of the HAP solution to 141.7 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 68.2 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0031] Example 7: This embodiment aims to suppress the catalytic decomposition of HAP by copper ions by introducing a trace amount of EDTMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% (w / v) HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage of the metal material through etching, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. Subsequently, 5 mg of EDTMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0032] As shown in Tables 1 and 2, the addition of 5 mg EDTMP significantly increased the thermal decomposition temperature of the HAP solution to 126.5 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 47.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0033] Example 8: This embodiment aims to suppress the catalytic decomposition of HAP by metallic iron ions by introducing a trace amount of EDTMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of ferric nitrate was added to the solution to achieve an iron ion concentration of 100 μg / mL. Subsequently, 5 mg of EDTMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0034] As shown in Tables 1 and 3, the addition of 5 mg EDTMP significantly extended the chemical stability time to 123 h at a constant temperature of 90 °C, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0035] Example 9: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of EDTMP as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. Subsequently, 5 mg of EDTMP was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0036] As shown in Tables 1 and 4, the addition of 5 mg EDTMP significantly increased the thermal decomposition temperature of the HAP solution to 128.6 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 23.5 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0037] Example 10: This embodiment aims to suppress the catalytic decomposition of HAP by copper ions by introducing a trace amount of NTA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. Subsequently, 5 mg of NTA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0038] As shown in Tables 1 and 2, after the addition of 5 mg NTA, the thermal decomposition temperature of the HAP solution shifted significantly upward to 132.7 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 29.7 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0039] Example 11: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of NTA as a stabilizer into a system containing impurities. First, a 10 mL HAP solution with a mass fraction of 82.5% was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of ferric nitrate was added to the solution to achieve an iron ion concentration of 100 μg / mL. Subsequently, 5 mg of NTA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0040] As shown in Tables 1 and 3, the addition of 5 mg NTA significantly increased the thermal decomposition temperature of the HAP solution to 135.7 °C, and greatly extended the chemical stability time to 64.8 h at a constant temperature of 90 °C, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0041] Example 12: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of NTA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. Subsequently, 5 mg of NTA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0042] As shown in Tables 1 and 4, the addition of 5 mg NTA significantly increased the thermal decomposition temperature of the HAP solution to 137.9 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 31.3 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0043] Example 13: This embodiment aims to suppress the catalytic decomposition of HAP by copper ions by introducing a trace amount of HEDTA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% (w / v) HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage of the metal material through etching, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. Subsequently, 5 mg of HEDTA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0044] As shown in Tables 1 and 2, the addition of 5 mg HEDTA significantly increased the thermal decomposition temperature of the HAP solution to 123.6 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 20.8 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0045] Example 14: This embodiment aims to suppress the catalytic decomposition of HAP by introducing a trace amount of HEDTA as a stabilizer into a system containing impurities. First, 10 mL of an 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. Subsequently, 5 mg of HEDTA was accurately weighed and added to the solution as a stabilizer. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm to ensure sufficient contact between the stabilizer and the metal ions and a chelation reaction, thereby shielding the catalytically active sites of the metal ions through complexation.

[0046] As shown in Tables 1 and 4, the addition of 5 mg HEDTA significantly increased the thermal decomposition temperature of the HAP solution to 125.6 °C, and the chemical stability time at a constant temperature of 90 °C was greatly extended to 21.6 h, effectively improving the thermal stability of the HAP solution in a metal-contaminated environment.

[0047] Comparative Example 1: This comparative example aims to investigate the catalytic decomposition effect of copper ions on HAP aqueous solution. First, 10 mL of an 82.5% (w / v) HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage of the metal material due to etching, a specific amount of copper nitrate was added to the solution to achieve a copper ion concentration of 100 μg / mL. The mixture was placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm.

[0048] As shown in Tables 1 and 2, the thermal decomposition initiation temperature of the copper-containing HAP solution without added stabilizer is only 121.3℃, and the chemical stability time at a constant temperature of 90℃ is 8.8 h.

[0049] Comparative Example 2: This comparative example aims to investigate the catalytic decomposition effect of iron ions on HAP aqueous solution. First, 10 mL of an 82.5% (w / v) HAP solution was used as the base system. To simulate the environment of impurities introduced during the preparation and storage process due to etching of the metal material, a specific amount of copper nitrate was added to the solution to achieve an iron ion concentration of 100 μg / mL. The mixture was placed on a magnetic stirrer and stirred continuously at room temperature and 200 rpm for 30 min.

[0050] As shown in Tables 1 and 3, the thermal decomposition initiation temperature of the iron-containing HAP solution without added stabilizer is only 132.1℃, and the chemical stability time at a constant temperature of 90℃ is 34 h.

[0051] Comparative Example 3: This comparative example aims to investigate the catalytic decomposition effect of copper-iron mixed ions on HAP aqueous solution. First, 10 mL of 82.5% HAP solution was used as the base system. To simulate the environment of impurities introduced by etching of the metal material during preparation and storage, specific amounts of ferric nitrate and copper nitrate (mass ratio 1:1) were added to the solution to achieve a copper-iron mixed ion concentration of 100 μg / mL. The mixture was then placed on a magnetic stirrer and stirred continuously for 30 min at room temperature and 200 rpm.

[0052] As shown in Tables 1 and 4, the thermal decomposition initiation temperature of the HAP solution containing copper and iron mixed ions without the addition of stabilizer is only 123.8℃, and the chemical stability time at a constant temperature of 90℃ is 10.2 h.

[0053] Table 1. Effect of stabilizers on the decomposition performance of HAP contaminated with copper and iron ions (90℃ isothermal thermal monitoring method)

[0054] Table 2. Effect of stabilizers on the thermal decomposition of HAP solutions containing copper ions

[0055] Table 3. Effect of stabilizers on the thermal decomposition of HAP solutions containing iron ions

[0056] Table 4. Effect of stabilizers on the thermal decomposition of HAP solutions containing mixed iron and copper ions

Claims

1. A method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace amounts of stabilizer, characterized in that, A chelating stabilizer is added to a HAP solution containing metal ions to inhibit the catalytic decomposition of HAP by metal ions through complexation. The HAP solution is a hydroxylamine perchlorate solution, the metal ions are one or both of copper and iron ions, and the stabilizer is selected from DTPA, ATMP, EDTMP, NTA, and HEDTA.

2. The method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace stabilizers as described in claim 1, characterized in that, Includes the following steps: Step 1: Take an 82.5% HAP solution as the base system and set it aside. Step 2: Add ferric nitrate, copper nitrate, or ferric nitrate and copper nitrate to the solution to make the concentration of metal ions in the system reach 100 μg / mL; Step 3: Weigh out the stabilizer and add it to the above solution. Stir the mixture continuously at room temperature to ensure that the stabilizer and metal ions are in full contact and undergo a chelation reaction. Step 4: Perform thermal decomposition and chemical stability tests on the obtained solution.

3. The method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace stabilizers as described in claim 2, characterized in that, The addition ratio of 82.5% HAP solution, metal ions in the system, and stabilizer is 10 mL: 1 mg: 5 mg.

4. The method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace stabilizers as described in claim 2, characterized in that, In step 3, the stirring conditions are: continuous stirring at 200 rpm for 30 minutes.

5. The method for improving the thermal stability of hydroxylamine perchlorate solution by adding trace stabilizers as described in claim 2, characterized in that, In step 4, the obtained solution is subjected to thermal decomposition and chemical stability tests: For HAP solutions containing copper ion impurities, the thermal decomposition temperature of HAP increased from 121.3℃ to a maximum of 143.1℃, and the chemical stability time increased from 8.8 h to a maximum of 67.8 h. For HAP solutions containing iron ion impurities, the thermal decomposition temperature of HAP increased from 132.1℃ to a maximum of 147.2℃, and the chemical stability time increased from 34 h to a maximum of 146.5 h. For HAP solutions containing copper and iron ion impurities, the thermal decomposition temperature of HAP increased from 123.8℃ to a maximum of 141.7℃, and the chemical stability time increased from 10.2 h to a maximum of 68.2 h.

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