A method of energetic material processing

Abstract

The present application relates to the technical field of energetic material processing, in particular to an energetic material processing method, which comprises: disassembling and cleaning energetic materials to obtain chemical agent decontamination water, solid energy substance and metal parts; adding first lye and organic solvent to the chemical agent decontamination water, stirring and reacting to obtain chemical hydrolysis liquid; performing first energy hydrolysis reaction on the solid energy substance to obtain pretreated energy hydrolysis liquid; performing stability analysis on the pretreated energy hydrolysis liquid; if the stability meets the requirements, adding metal precipitant, filtering and processing to obtain energy hydrolysis liquid; if the stability does not meet the requirements, performing second energy hydrolysis reaction on the pretreated energy hydrolysis liquid, adding metal precipitant, filtering and processing to obtain energy hydrolysis liquid; mixing the chemical hydrolysis liquid and the energy hydrolysis liquid, and performing supercritical water oxidation processing and salt removal processing. The method provided by the present application is safer and more reliable.

Description

Technical Field

[0001] This invention relates to the field of energetic materials processing technology, and more specifically, to an energetic materials processing method. Background Technology

[0002] With the rapid development of military technology, the reserves of energetic materials such as chemical weapons missiles, rocket propellants, and explosives are growing larger and larger. More and more energetic materials are facing scrapping, retirement, replacement, and elimination, which requires them to be demilitarized in order to achieve safe disposal.

[0003] Energetic materials mainly consist of energy substances and chemical agents. Energy substances primarily include TNT, DNT, RDX, HMX, and Tetryl, which are metastable materials with high energy density and instantaneous high power. Chemical agents mainly include isopropyl methylfluorophosphate (C4H4PO4). 10 FO2P), N,N-diethyl-2-thioethylamine (C 11 H 26 Energetic materials, such as NO2PS and dichlorobutane (C4H8Cl2), are unstable and unsafe, and some are even toxic. Therefore, the safe disposal of energetic materials has always been a major concern. Improper handling will inevitably lead to major accidents, causing significant environmental pollution and posing a serious threat to social safety and human health.

[0004] Currently, the main methods for treating energetic materials are divided into physical methods, chemical methods, and biodegradation methods. Physical methods primarily involve deep burial, dumping in the open sea, and extraction with organic solvents. Essentially, these methods transfer, store, and concentrate the energy substances without completely destroying the potential threats posed by the energy substances and chemical agents. Chemical methods use specific chemical processes to decompose energetic materials into stable products with minimal or no environmental harm, thus eliminating potential safety hazards. Examples include incineration and Fenton oxidation. However, these methods are costly, cause significant pollution, and cannot achieve safe disposal. Biodegradation methods utilize the metabolic processes of organisms to degrade energetic materials, rendering them harmless. However, biochemical methods are inefficient, and many energetic substances contain toxicity, making them unsuitable for use.

[0005] Supercritical water oxidation technology is considered an ideal method for the safe disposal of energetic materials due to its advantages such as high decomposition efficiency, short reaction time, no need for catalysts, and no secondary pollution. Numerous exploratory experiments have been conducted both domestically and internationally to demonstrate the feasibility of using supercritical water oxidation to treat energetic materials. However, most studies have focused on wastewater from ammunition manufacturing with low chemical concentrations. The application of supercritical water oxidation technology to effectively treat energetic materials containing chemical agents as a whole lacks a safe and reliable process design and is not universally applicable. Summary of the Invention

[0006] The technical problem solved by this invention is that there is still a lack of safe and reliable process design for the overall treatment of energetic materials containing chemical agents using supercritical water oxidation technology.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0008] A method for processing energetic materials, comprising:

[0009] Step S1: Disassemble and clean the energetic material to obtain chemically treated wastewater, solid energy material with a coating shell, and metal components;

[0010] Step S2: Add a first alkaline solution and an organic solvent to the wastewater containing the chemical agent to form a first hydrolysate. The first hydrolysate is stirred and reacted to obtain a chemical hydrolysate. The solid energy substance is added to a primary hydrolysis reactor to carry out a primary energy hydrolysis reaction to obtain a pretreated energy hydrolysate. A second alkaline solution is added to the primary hydrolysis reactor.

[0011] Step S3: Perform a stability analysis on the pretreated energy hydrolysate;

[0012] If the stability of the pretreated energy hydrolysate meets the requirements, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate.

[0013] If the stability of the pretreated energy hydrolysate does not meet the requirements, the pretreated energy hydrolysate is transferred to a secondary hydrolysis reactor for secondary energy hydrolysis reaction. After the reaction, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate. A third alkali solution is added to the secondary hydrolysis reactor.

[0014] Step S4: After mixing the chemical hydrolysate and the energy hydrolysate, supercritical water oxidation is performed, followed by salt removal to obtain the fluid to be discharged.

[0015] Preferably, in step S3, the stability analysis of the pretreated energy hydrolysate includes: analyzing the concentration of undecomposed energy components in the pretreated energy hydrolysate; when the concentration of undecomposed energy components in the pretreated energy hydrolysate is greater than the safety concentration standard, the stability of the pretreated energy hydrolysate does not meet the requirements; when the concentration of undecomposed energy components in the pretreated energy hydrolysate is not higher than the safety concentration standard, the stability of the pretreated energy hydrolysate meets the requirements.

[0016] Preferably, in step S2, the temperature of the first alkaline solution is 60-90°C, the pH value of the first hydrolysate is 10-13, and the stirring reaction time is 2-6 hours.

[0017] Preferably, in step S2, the organic solvent includes one of methanol, isopropanol, and isobutanol.

[0018] Preferably, in step S2, the mass fraction of the second alkaline solution is 30-50%, the temperature is 100-130℃, and the time for the first-stage energy hydrolysis reaction is 0.5-3h; in step S3, the mass fraction of the third alkaline solution is 30-50%, the temperature is 100-130℃, and the time for the second-stage energy hydrolysis reaction is 0.5-3h.

[0019] Preferably, in step S4, the temperature of the supercritical water oxidation treatment is 500-700℃, the pressure is 22-25MPa, and the time is 10-50s.

[0020] Preferably, the energetic material processing method further includes:

[0021] Step S5: Perform gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas.

[0022] Preferably, the energetic material processing method further includes: subjecting the metal component to high-temperature decontamination treatment to remove volatile organic compounds adhering to the metal component.

[0023] Preferably, the high-temperature decontamination treatment is performed at a temperature of 500-600℃ for 10-20 minutes.

[0024] Compared with existing technologies, the energetic material processing method provided by this invention first involves disassembling and cleaning the energetic material to obtain chemically treated wastewater, a solid energy substance with a coated shell, and metal components. Then, the chemically treated wastewater is stirred and reacted in a first alkaline solution and an organic solvent to obtain a chemical hydrolysate whose main component is organic matter. Because the main component of this chemical hydrolysate is organic matter, it has high safety. The solid energy substance undergoes an energy hydrolysis reaction to ensure the stability of the final energy hydrolysate meets requirements, thus ensuring safety. To avoid introducing excessive metal ions into the supercritical water oxidation reaction system, a metal precipitant is added to the energy hydrolysis reaction system, resulting in a low concentration of metal ions in the energy hydrolysate. This avoids the risk of blockage caused by excessive metal precipitation in the supercritical water oxidation system. Finally, the safer energy hydrolysate and the chemical hydrolysate are mixed and subjected to supercritical water oxidation and desalination treatment to obtain a fluid to be discharged. This fluid can then be safely discharged after further treatment. The mixing of the energy hydrolysate and the chemical hydrolysate ensures that the heat generated during supercritical water oxidation can sustain the heat required for the supercritical water oxidation reaction. Therefore, the method provided by this invention can safely decompose and destroy various chemically based energetic materials, achieving harmless treatment. Furthermore, this method has a wide range of applications, a short process flow, high efficiency, requires no catalyst addition during treatment, and does not produce explosions or secondary pollution, thus offering higher safety and reliability. Attached Figure Description

[0025] Figure 1 This is a schematic flowchart of the energetic material processing method in an embodiment of the present invention. Detailed Implementation

[0026] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0027] It should be noted that, unless otherwise specified, the features in the embodiments of this invention can be combined with each other. The terms "comprising," "including," "containing," and "having" are non-limiting, meaning that other steps and other components that do not affect the results can be added. The above terms cover the terms "composed of" and "substantially composed of." Unless otherwise specified, the materials, equipment, and reagents are commercially available.

[0028] like Figure 1 As shown, an embodiment of the present invention provides a method for processing energetic materials, including:

[0029] Step S1: Disassemble and clean the energetic material to obtain chemically treated wastewater, solid energy material with a coating shell, and metal components;

[0030] Step S2: Add a first alkaline solution and an organic solvent to the wastewater containing the chemical agent to form a first hydrolysate. The first hydrolysate is stirred and reacted to obtain a chemical hydrolysate. The solid energy substance is added to a primary hydrolysis reactor to carry out a primary energy hydrolysis reaction to obtain a pretreated energy hydrolysate. A second alkaline solution is added to the primary hydrolysis reactor.

[0031] Step S3: Perform a stability analysis on the pretreated energy hydrolysate;

[0032] If the stability of the pretreated energy hydrolysate meets the requirements, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate.

[0033] If the stability of the pretreated energy hydrolysate does not meet the requirements, the pretreated energy hydrolysate is transferred to a secondary hydrolysis reactor for secondary energy hydrolysis reaction. After the reaction, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate. A third alkali solution is added to the secondary hydrolysis reactor.

[0034] Step S4: After mixing the chemical hydrolysate and the energy hydrolysate, supercritical water oxidation is performed, followed by salt removal to obtain the fluid to be discharged.

[0035] Supercritical water oxidation technology is characterized by high-temperature and high-pressure reactions. High-concentration chemical agents and solid energy substances in wastewater can be directly treated with supercritical water oxidation to obtain a high heat of oxidation to sustain the reaction. However, directly preparing high-concentration wastewater from energetic materials and solid energy substances for supercritical water oxidation presents several problems: First, most energetic materials have low solubility in water, making it difficult to prepare high-concentration wastewater. Second, excessively high concentrations of chemical agents and solid energy substances in the wastewater from supercritical water oxidation can lead to poor safety of the supercritical water oxidation system.

[0036] Based on the above considerations, compared with the prior art, the energetic material processing method provided by this invention firstly disassembles and cleans the energetic material to obtain chemically treated wastewater, solid energy material with a coated shell, and metal components. Then, the chemically treated wastewater is stirred and reacted in a first alkaline solution and an organic solvent to obtain a chemical hydrolysate whose main component is organic matter. Because the main component of this chemical hydrolysate is organic matter, it has high safety. The solid energy material undergoes an energy hydrolysis reaction to ensure the stability of the final energy hydrolysate meets requirements, thus ensuring safety. To avoid introducing excessive metal ions into the supercritical water oxidation reaction system, a metal precipitant is added to the energy hydrolysis reaction system, resulting in a low concentration of metal ions in the energy hydrolysate. This avoids the risk of blockage caused by excessive metal precipitation in the supercritical water oxidation system. Finally, the safer energy hydrolysate and the chemical hydrolysate are mixed and subjected to supercritical water oxidation and desalination treatment to obtain a fluid to be discharged. This fluid can then be safely discharged after further treatment. The mixing of the energy hydrolysate and the chemical hydrolysate ensures that the heat generated during supercritical water oxidation can sustain the heat required for the supercritical water oxidation reaction. Therefore, the method provided by this invention can safely decompose and destroy various chemically based energetic materials, achieving harmless treatment. Furthermore, this method has a wide range of applications, a short process flow, high efficiency, requires no catalyst addition during treatment, and does not produce explosions or secondary pollution, thus offering higher safety and reliability.

[0037] Exemplary examples, in some embodiments of the present invention, in step S1, when disassembling the energetic material, the metal outer shell can be broken by punching, cutting, or other methods. Care must be taken not to damage the outer shell covering the energetic material during this process to prevent an explosion. High-pressure deionized water is used for cleaning at a temperature of 20-30°C and a pressure of 2-3 MPa to dissolve and rinse away the chemical agents present.

[0038] In some embodiments of the present invention, step S3, which involves performing a stability analysis on the pretreated energy hydrolysate, includes: analyzing the concentration of undecomposed energy components in the pretreated energy hydrolysate; if the concentration of undecomposed energy components in the pretreated energy hydrolysate is greater than a safe concentration standard, the stability of the pretreated energy hydrolysate does not meet the requirements; if the concentration of undecomposed energy components in the pretreated energy hydrolysate is not higher than the safe concentration standard, the stability of the pretreated energy hydrolysate meets the requirements. Exemplarily, the stability analysis can be performed using methods such as DTA, DSC, TGA, and ARC.

[0039] In some embodiments of the present invention, in step S3, the metal precipitant includes at least one of hydroxyquinoline, urea, xanthate esters or dithiocarbamate.

[0040] In some embodiments of the present invention, in step S2, the temperature of the first alkaline solution is 60-90°C, the pH value of the first hydrolysate is 10-13, and the stirring reaction time is 2-6 hours. Thorough stirring during the reaction effectively promotes the complete hydrolysis of chemical components in the wastewater and prevents the deposition of solid particles.

[0041] In some embodiments of the present invention, in step S2, the organic solvent includes one of methanol, isopropanol, and isobutanol.

[0042] In some embodiments of the present invention, in step S2, the mass fraction of the second alkaline solution is 30-50%, the temperature is 100-130°C, and the time of the first-stage energy hydrolysis reaction is 0.5-3h; in step S3, the mass fraction of the third alkaline solution is 30-50%, the temperature is 100-130°C, and the time of the second-stage energy hydrolysis reaction is 0.5-3h.

[0043] In some embodiments of the present invention, in step S4, the supercritical water oxidation treatment is carried out at a temperature of 500-700℃, a pressure of 22-25MPa, and a time of 10-50s. The chemical hydrolysate and the energy hydrolysate come into contact with high-pressure air in a high-temperature, high-pressure reactor, undergoing a supercritical water oxidation reaction. The inorganic salts generated after supercritical water oxidation of the chemical hydrolysate and the energy hydrolysate are insoluble in supercritical water and easily precipitate. Therefore, a salt discharge device needs to be installed at the reactor outlet to discharge the salts. The discharged salts can be collected for reuse or directly disposed of.

[0044] In some embodiments of the present invention, the energetic material processing method further includes:

[0045] Step S5: Separate the fluid to be discharged into gas and liquid to obtain waste liquid and waste gas. The main components of the waste gas are CO2, H2O, N2 and O2, which can be directly discharged into the atmosphere; the waste liquid can be tested for conductivity. If the conductivity is low, it can be directly reused as cleaning water; if the conductivity is high, it can be treated as general production wastewater.

[0046] In some embodiments of the present invention, the energetic material treatment method further includes: subjecting the metal component to a high-temperature decontamination treatment to remove volatile organic compounds adhering to the metal component; wherein the high-temperature decontamination treatment is performed at a temperature of 500-600°C for a time of 10-20 minutes. The high temperature causes the volatile organic compounds adhering to the metal component to volatilize into organic gases, which can be collected for further waste gas treatment.

[0047] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0048] Example 1

[0049] Taking a certain energetic material as an example, the chemical composition of this energetic material is C4H. 10 FO2P, a solid energy source, consists of 60% RDX, 39% TNT, and 1% paraffin.

[0050] 1.1 First, punch holes in the metal shell containing the energy material, then rinse the internal chemical agent with 25℃, 3MPa deionized water. After rinsing, use a cutting machine to cut and destroy the metal shell, taking care to avoid the energy material covering the shell. Then rinse with high-pressure deionized water to obtain the chemical agent-free wastewater, solid energy material covered with the metal shell, and metal parts.

[0051] 1.2. A first alkaline solution and an organic solvent are added to the wastewater containing the chemical agent to form a first hydrolysate. The first hydrolysate is stirred to obtain a chemical hydrolysate. The main components of the chemical hydrolysate are sodium isopropyl methyl phosphate, sodium fluoride, sodium hydroxide, isopropanol, and butylamine, etc. The first alkaline solution is a NaOH solution at 60°C, the pH value of the first hydrolysate is about 10.5, the organic solvent is isopropanol, and the stirring reaction time is 3 hours.

[0052] 1.3. The solid energy substance is added to a primary hydrolysis reactor to carry out a primary energy hydrolysis reaction to obtain a pretreated energy hydrolysate; wherein, a second alkaline solution is added to the primary hydrolysis reactor, the second alkaline solution being a 120°C NaOH solution (40% by mass), and the time for the first-stage hydrolysis reaction is 3 hours;

[0053] 1.4. The stability of the pretreated energy hydrolysate was analyzed. The analysis showed that the stability of the pretreated energy hydrolysate met the requirements. A metal precipitant was added to the pretreated energy hydrolysate, and the mixture was filtered to obtain the energy hydrolysate. The main components of this energy hydrolysate were nitrates, nitrites, formates, acetates, glycerol, and aromatic organic compounds. The metal precipitant was hydroxyquinoline.

[0054] 1.5 The chemical hydrolysate and the energy hydrolysate are mixed at a mass ratio of 2:3 and then subjected to supercritical water oxidation treatment, followed by salt removal treatment to obtain the fluid to be discharged; wherein the temperature of the supercritical water oxidation treatment is 600℃, the pressure is 25MPa, the oxygen content is 150%, and the time is 30s.

[0055] 1.6 The fluid to be discharged is subjected to gas-liquid separation to obtain waste liquid and waste gas. The main components of the waste gas are CO2, H2O, N2 and O2, which are directly discharged into the atmosphere; the waste liquid is tested for conductivity, and the conductivity is high, so it is treated as general production wastewater.

[0056] 1.7. The metal parts are subjected to high-temperature decontamination treatment to remove volatile organic compounds adhering to the metal parts; wherein the high-temperature decontamination treatment is performed at a temperature of 550°C for 15 minutes, and the high temperature causes the volatile organic compounds adhering to the metal parts to volatilize into organic gases, which are then collected and treated and purified using an RTO system.

[0057] Furthermore, it should be noted that although the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and all such changes and modifications will fall within the scope of protection of the present invention.

Claims

1. A method for processing energetic materials, characterized in that, include: Step S1: Disassemble and clean the energetic material to obtain chemically treated wastewater, solid energy material with a coating shell, and metal components; Step S2: Add a first alkaline solution and an organic solvent to the wastewater containing the chemical agent to form a first hydrolysate. The first hydrolysate is stirred and reacted to obtain a chemical hydrolysate. The solid energy substance is added to a primary hydrolysis reactor to carry out a primary energy hydrolysis reaction to obtain a pretreated energy hydrolysate. A second alkaline solution is added to the primary hydrolysis reactor. Step S3: Perform a stability analysis on the pretreated energy hydrolysate; the stability analysis includes: analyzing the concentration of undecomposed energy components in the pretreated energy hydrolysate; when the concentration of undecomposed energy components in the pretreated energy hydrolysate is greater than the safety concentration standard, the stability of the pretreated energy hydrolysate does not meet the requirements; when the concentration of undecomposed energy components in the pretreated energy hydrolysate is not higher than the safety concentration standard, the stability of the pretreated energy hydrolysate meets the requirements. If the stability of the pretreated energy hydrolysate meets the requirements, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate. If the stability of the pretreated energy hydrolysate does not meet the requirements, the pretreated energy hydrolysate is transferred to a secondary hydrolysis reactor for secondary energy hydrolysis reaction. After the reaction, a metal precipitant is added, and the mixture is filtered to obtain the energy hydrolysate. A third alkali solution is added to the secondary hydrolysis reactor. Step S4: After mixing the chemical hydrolysate and the energy hydrolysate, supercritical water oxidation is performed, followed by salt removal to obtain the fluid to be discharged.

2. The method for processing energetic materials according to claim 1, characterized in that, In step S2, the temperature of the first alkaline solution is 60-90℃, the pH value of the first hydrolysate is 10-13, and the stirring reaction time is 2-6 hours.

3. The method for processing energetic materials according to claim 1, characterized in that, In step S2, the organic solvent includes one of methanol, isopropanol, and isobutanol.

4. The method for processing energetic materials according to claim 1, characterized in that, In step S2, the mass fraction of the second alkaline solution is 30-50%, the temperature is 100-130℃, and the time for the first-stage energy hydrolysis reaction is 0.5-3h; in step S3, the mass fraction of the third alkaline solution is 30-50%, the temperature is 100-130℃, and the time for the second-stage energy hydrolysis reaction is 0.5-3h.

5. The method for processing energetic materials according to claim 1, characterized in that, In step S4, the temperature of the supercritical water oxidation treatment is 500-700℃, the pressure is 22-25MPa, and the time is 10-50s.

6. The method for processing energetic materials according to claim 1, characterized in that, Also includes: Step S5: Perform gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas.

7. The method for processing energetic materials according to claim 1, characterized in that, Also includes: The metal parts are subjected to high-temperature decontamination treatment to remove volatile organic compounds adhering to the metal parts.

8. The method for processing energetic materials according to claim 7, characterized in that, The high-temperature decontamination treatment is performed at a temperature of 500-600℃ for 10-20 minutes.

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