CN117776825A - Energy-containing material treatment method - Google Patents
Energy-containing material treatment method Download PDFInfo
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- CN117776825A CN117776825A CN202311802813.8A CN202311802813A CN117776825A CN 117776825 A CN117776825 A CN 117776825A CN 202311802813 A CN202311802813 A CN 202311802813A CN 117776825 A CN117776825 A CN 117776825A
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to the technical field of energetic material treatment, in particular to an energetic material treatment method, which comprises the following steps: dismantling and cleaning the energetic material to obtain chemical agent to remove sewage, solid energy substances and metal parts; adding a first alkali liquor and an organic solvent into the decontaminating water of the chemical agent, and stirring for reaction to obtain a chemical hydrolysate; carrying out primary energy hydrolysis reaction on the solid energy substance to obtain pretreated energy hydrolysis solution; performing stability analysis on the pretreatment energy hydrolysis solution; if the stability meets the requirement, adding a metal precipitator, and filtering to obtain energy hydrolysis liquid; if the stability of the water-soluble polymer is not in accordance with the requirement, adding a metal precipitant after the secondary energy hydrolysis reaction of the pretreated energy hydrolysis liquid, and filtering to obtain the energy hydrolysis liquid; and mixing the chemical hydrolysate and the energy hydrolysate, performing supercritical water oxidation treatment, and performing salt removal treatment. The method provided by the invention has higher safety and reliability.
Description
Technical Field
The invention relates to the technical field of energetic material treatment, in particular to an energetic material treatment method.
Background
With the rapid development of military technology, the storage amount of energetic materials such as chemical weapon missiles, rocket propellants, explosives and powders is larger and larger, and more energetic materials are scrapped, retired, updated and eliminated, so that the military technology needs to be subjected to demilitarization treatment to achieve the aim of safe destruction.
The energetic material mainly comprises an energy substance, such as TNT, DNT, RDX, HMX, tetryl, which is a metastable substance with high energy density and high instantaneous power, and a chemical agent, such as isopropyl methylphosphonate (C 4 H 10 FO 2 P), N-diethyl-2-thioethylamine (C) 11 H 26 NO 2 PS), dichlorobutane (C) 4 H 8 Cl 2 ) Etc. Energetic materials are unstable and unsafe, and some are even toxic. Therefore, the problem of safe destruction of energetic materials is always concerned, if the energetic materials cannot be properly treated, serious accidents are necessarily caused, huge pollution is caused to the environment, and serious threats are brought to social safety and human health.
At present, the treatment method of the energetic material mainly comprises the following steps: physical, chemical and biological degradation methods. The physical method mainly adopts deep soil burying, open sea dumping, organic solvent extraction and the like, and is essentially used for transferring, placing, concentrating and the like energy substances, so that the potential threat of thoroughly destroying the energy substances and chemical agents is not caused. The chemical method adopts a certain chemical method to decompose the energetic material into products with good stability and less or harmless environmental hazard, so as to eliminate unsafe hidden dangers, such as an incineration method, a Fenton oxidation method and the like, but the methods have high investment cost, serious reaction pollution and can not realize safe destruction. The biodegradation method is a method for degrading the energetic material by utilizing the metabolism of organisms to make the energetic material harmless, but the biochemical method has low efficiency, and most of energy substances contain toxicity, so the biochemical method is not suitable for use.
The supercritical water oxidation technology has the advantages of high decomposition efficiency, short reaction time, no need of adding catalyst, no secondary pollution and the like, and is considered by researchers to be an ideal method for safely disposing energetic materials. Various exploring tests have been carried out at home and abroad to prove the feasibility of treating energetic materials by using a supercritical water oxidation method, but most of the exploring tests only take ammunition production and manufacturing wastewater with low chemical concentration as a research object, and the whole energetic materials containing chemical agents are effectively treated by using a supercritical water oxidation technology, so that safe and reliable process design is not provided, and the exploring tests have no universality.
Disclosure of Invention
The invention solves the technical problems that: the supercritical water oxidation technology is used for effectively treating the whole energetic material containing the chemical agent, and a safe and reliable process design is not yet available.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method of energetic material processing, comprising:
s1, disassembling and cleaning an energetic material to obtain chemical agent sewage, a solid energy substance with a coating shell and a metal part;
s2, adding a first alkali liquor and an organic solvent into the chemical agent decontaminating water to form a first hydrolysate, and stirring the first hydrolysate to react to obtain a chemical hydrolysate; adding the solid energy substance into a primary hydrolysis reactor, and performing primary energy hydrolysis reaction to obtain pretreated energy hydrolysis solution; wherein, the primary hydrolysis reactor is added with a second alkali liquor;
s3, performing stability analysis on the pretreatment energy hydrolysate;
if the stability of the pretreatment energy hydrolysate meets the requirement, adding a metal precipitant, and filtering to obtain the energy hydrolysate;
if the stability of the pretreatment energy hydrolysis liquid does not meet the requirement, transferring the pretreatment energy hydrolysis liquid into a secondary hydrolysis reactor, adding a metal precipitant after secondary energy hydrolysis reaction, and filtering to obtain energy hydrolysis liquid; wherein, a third alkali liquor is added into the secondary hydrolysis reactor;
and S4, mixing the chemical hydrolysate with the energy hydrolysate, performing supercritical water oxidation treatment, and then performing salt removal treatment to obtain the fluid to be discharged.
Preferably, in the step S3, the performing stability analysis on the pretreated energy hydrolysate includes: analyzing the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate, wherein when the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate is larger than a safe concentration standard, the stability of the pretreatment energy hydrolysate does not meet the requirement; and when the concentration of the undegraded energy components in the pretreatment energy hydrolysate is not higher than the safety concentration standard, the stability of the pretreatment energy hydrolysate meets the requirement.
Preferably, in the step S2, the temperature of the first alkaline solution is 60-90 ℃, the pH value of the first hydrolysis solution is 10-13, and the stirring reaction time is 2-6h.
Preferably, in the step S2, the organic solvent includes one of methanol, isopropyl alcohol and isobutyl alcohol.
Preferably, in the step S2, the mass fraction of the second alkali liquor is 30-50%, the temperature is 100-130 ℃, and the primary energy hydrolysis reaction time is 0.5-3h; in the step S3, the mass fraction of the third alkali liquor is 30-50%, the temperature is 100-130 ℃, and the time of the secondary energy hydrolysis reaction is 0.5-3h.
Preferably, in the step S4, the supercritical water oxidation treatment is performed at a temperature of 500-700 ℃, a pressure of 22-25MPa, and a time of 10-50S.
Preferably, the method for treating energetic materials further comprises:
and S5, performing gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas.
Preferably, the method for treating energetic materials further comprises: and carrying out high-temperature decontamination treatment on the metal part to remove volatile organic matters attached to the metal part.
Preferably, the high-temperature decontamination treatment is carried out at 500-600 ℃ for 10-20min.
Compared with the prior art, in the method for processing the energetic material, firstly, the energetic material is disassembled and cleaned to obtain chemical agent sewage, solid energy substances with coating shells and metal parts; then, the chemical agent sewage is subjected to stirring reaction in the first alkali liquor and the organic solvent to obtain chemical hydrolysate with the main component of organic matters, and the safety of the chemical hydrolysate is higher because the main component of the chemical hydrolysate is the organic matters; carrying out energy hydrolysis reaction on solid energy substances so as to ensure that the stability of the finally obtained energy hydrolysate meets the requirements and ensure the safety; in order to avoid introducing excessive metal ions into the supercritical water oxidation reaction system by the energy hydrolysis liquid, the metal precipitant is added into the energy hydrolysis reaction system, so that the concentration of the metal ions in the energy hydrolysis liquid is lower, and the risks of blockage and the like caused by excessive metal precipitation in the supercritical water oxidation system can be avoided. Finally, mixing the energy hydrolysis liquid with higher safety with the chemical hydrolysis liquid, performing supercritical water oxidation treatment and salt elimination treatment to obtain fluid to be discharged, and further treating the fluid to be discharged to realize safe discharge. After the energy hydrolysis liquid and the chemical hydrolysis liquid are mixed, the heat required by the supercritical water oxidation reaction can be maintained by the heat of reaction generated in the supercritical water oxidation treatment process. Therefore, the method provided by the invention can be used for safely decomposing and destroying various chemical-based energetic materials to achieve the purpose of harmless treatment, and has the advantages of wide application range, short process flow, high efficiency, no need of adding any catalyst in the treatment process, no explosion or secondary pollution, and higher safety and reliability.
Drawings
FIG. 1 is a schematic flow chart of a method for processing energetic materials according to an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that, without conflict, features in the embodiments of the present invention may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment, reagents are commercially available unless otherwise specified.
As shown in fig. 1, an embodiment of the present invention provides a method for processing an energetic material, including:
s1, disassembling and cleaning an energetic material to obtain chemical agent sewage, a solid energy substance with a coating shell and a metal part;
s2, adding a first alkali liquor and an organic solvent into the chemical agent decontaminating water to form a first hydrolysate, and stirring the first hydrolysate to react to obtain a chemical hydrolysate; adding the solid energy substance into a primary hydrolysis reactor, and performing primary energy hydrolysis reaction to obtain pretreated energy hydrolysis solution; wherein, the primary hydrolysis reactor is added with a second alkali liquor;
s3, performing stability analysis on the pretreatment energy hydrolysate;
if the stability of the pretreatment energy hydrolysate meets the requirement, adding a metal precipitant, and filtering to obtain the energy hydrolysate;
if the stability of the pretreatment energy hydrolysis liquid does not meet the requirement, transferring the pretreatment energy hydrolysis liquid into a secondary hydrolysis reactor, adding a metal precipitant after secondary energy hydrolysis reaction, and filtering to obtain energy hydrolysis liquid; wherein, a third alkali liquor is added into the secondary hydrolysis reactor;
and S4, mixing the chemical hydrolysate with the energy hydrolysate, performing supercritical water oxidation treatment, and then performing salt removal treatment to obtain the fluid to be discharged.
The supercritical water oxidation technology is characterized by high-temperature high-pressure reaction, and the waste liquid of the chemical agent with higher concentration and the solid energy substance is directly subjected to supercritical water oxidation treatment, so that higher oxidation reaction heat can be obtained to maintain the heat required by the supercritical water oxidation reaction. However, the following problems exist in the supercritical water oxidation treatment of directly preparing the chemical agent and the solid energy substance of the energetic material into the waste liquid with high concentration: on the one hand, most energetic materials have low solubility in water and are difficult to prepare into waste liquid with high concentration, and on the other hand, the concentration of chemical agents and solid energy substances in the waste liquid subjected to supercritical water oxidation is too high, so that the safety of a supercritical water oxidation system is poor.
Based on the above consideration, compared with the prior art, in the method for treating the energetic material provided by the invention, firstly, the energetic material is disassembled and cleaned to obtain chemical agent sewage, solid energy substances with a coating shell and metal parts; then, the chemical agent sewage is subjected to stirring reaction in the first alkali liquor and the organic solvent to obtain chemical hydrolysate with the main component of organic matters, and the safety of the chemical hydrolysate is higher because the main component of the chemical hydrolysate is the organic matters; carrying out energy hydrolysis reaction on solid energy substances so as to ensure that the stability of the finally obtained energy hydrolysate meets the requirements and ensure the safety; in order to avoid introducing excessive metal ions into the supercritical water oxidation reaction system by the energy hydrolysis liquid, the metal precipitant is added into the energy hydrolysis reaction system, so that the concentration of the metal ions in the energy hydrolysis liquid is lower, and the risks of blockage and the like caused by excessive metal precipitation in the supercritical water oxidation system can be avoided. Finally, mixing the energy hydrolysis liquid with higher safety with the chemical hydrolysis liquid, performing supercritical water oxidation treatment and salt elimination treatment to obtain fluid to be discharged, and further treating the fluid to be discharged to realize safe discharge. After the energy hydrolysis liquid and the chemical hydrolysis liquid are mixed, the heat required by the supercritical water oxidation reaction can be maintained by the heat of reaction generated in the supercritical water oxidation treatment process. Therefore, the method provided by the invention can be used for safely decomposing and destroying various chemical-based energetic materials to achieve the purpose of harmless treatment, and has the advantages of wide application range, short process flow, high efficiency, no need of adding any catalyst in the treatment process, no explosion or secondary pollution, and higher safety and reliability.
In some embodiments of the present invention, in step S1, the metal shell may be broken by punching, cutting, or the like, and care should be taken not to break the energy material coating shell to prevent explosion. The water is cleaned by high-pressure deionized water, the water temperature is 20-30 ℃, the pressure is 2-3MPa, and the water is used for dissolving and flushing chemical agents in the water.
In some embodiments of the present invention, in the step S3, the performing stability analysis on the pretreated energy hydrolysate includes: analyzing the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate, wherein when the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate is larger than a safe concentration standard, the stability of the pretreatment energy hydrolysate does not meet the requirement; and when the concentration of the undegraded energy components in the pretreatment energy hydrolysate is not higher than the safety concentration standard, the stability of the pretreatment energy hydrolysate meets the requirement. Stability analysis may be performed by methods such as DTA, DSC, TGA and ARC, for example.
In some embodiments of the present invention, in the step S3, the metal precipitant includes at least one of hydroxyquinoline, urea, xanthates or dithiocarbamates.
In some embodiments of the present invention, in the step S2, the temperature of the first alkaline solution is 60-90 ℃, the pH value of the first hydrolysis solution is 10-13, and the stirring reaction time is 2-6 hours. And the reaction process is fully stirred, so that the chemical agent components in the chemical agent wastewater can be effectively promoted to be fully hydrolyzed, and solid particles are prevented from being deposited.
In some embodiments of the invention, in the step S2, the organic solvent includes one of methanol, isopropyl alcohol and isobutyl alcohol.
In some embodiments of the present invention, in the step S2, the mass fraction of the second alkaline solution is 30-50%, the temperature is 100-130 ℃, and the time of the primary energy hydrolysis reaction is 0.5-3 hours; in the step S3, the mass fraction of the third alkali liquor is 30-50%, the temperature is 100-130 ℃, and the time of the secondary energy hydrolysis reaction is 0.5-3h.
In some embodiments of the present invention, in the step S4, the supercritical water oxidation treatment is performed at a temperature of 500-700 ℃, a pressure of 22-25MPa, and a time of 10-50S. The chemical hydrolysate and the energy hydrolysate are contacted with high-pressure air in a high-temperature high-pressure reactor to perform supercritical water oxidation reaction. Inorganic salt generated by oxidizing chemical hydrolysate and energy hydrolysate with supercritical water is insoluble in supercritical water, and is easy to precipitate, and the salt is discharged by arranging a salt discharging device at the outlet of the reactor, so that the discharged salt can be collected for reuse or directly disposed.
In some embodiments of the invention, the energetic material processing method further comprises:
and S5, performing gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas. The main component of the waste gas is CO 2 、H 2 O、N 2 And O 2 Can be directly discharged to the atmosphere; the waste liquid can be used for conductivity detection, can be directly recycled as cleaning water if the conductivity is low, and can be used for general production wastewater treatment if the conductivity is high.
In some embodiments of the invention, the energetic material processing method further comprises: performing high-temperature decontamination treatment on the metal part to remove volatile organic matters attached to the metal part; wherein the high-temperature decontamination treatment is carried out at 500-600 ℃ for 10-20min. The high temperature may volatilize volatile organic compounds attached to the metal parts into organic gases which may be collected for further exhaust treatment.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
Taking a certain energetic material as an example, the chemical agent component of the energetic material is C 4 H 10 FO 2 P, solid energy consists of 60% rdx, 39% tnt and 1% paraffin.
Firstly, punching a metal shell of an energetic material, then flushing an internal chemical agent by using deionized water at 25 ℃ and 3MPa, cutting and damaging the metal shell by using a cutting machine after flushing, taking care of avoiding coating the shell by an energy substance, and flushing by using high-pressure deionized water to obtain chemical agent sewage, solid energy substance coated with the metal shell and a metal part;
1.2, adding a first alkali liquor and an organic solvent into the chemical agent decontaminating water to form a first hydrolysate, and stirring the first hydrolysate to react to obtain a chemical hydrolysate, wherein the main components of the chemical hydrolysate are isopropyl methyl sodium phosphate, sodium fluoride, sodium hydroxide, isopropanol, butylamine and the like; wherein the first alkali liquor is a NaOH solution with the temperature of 60 ℃, the pH value of the first hydrolysis liquor is about 10.5, the organic solvent is isopropanol, and the stirring reaction time is 3 hours;
1.3, adding the solid energy substance into a primary hydrolysis reactor, and performing primary energy hydrolysis reaction to obtain pretreated energy hydrolysis liquid; wherein, a second alkali liquor is added in the primary hydrolysis reactor, the second alkali liquor is a NaOH solution (mass fraction 40%) with the temperature of 120 ℃, and the time of the primary hydrolysis reaction is 3 hours;
1.4, performing stability analysis on the pretreatment energy hydrolysate; through analysis, the stability of the pretreated energy hydrolysate meets the requirement, a metal precipitator is added into the pretreated energy hydrolysate, and the energy hydrolysate is obtained through filtration treatment, wherein the main components of the energy hydrolysate are nitrate, nitrite, formate, acetate, glycerin and aromatic organic matters; wherein the metal precipitant is hydroxyquinoline;
1.5, mixing the chemical hydrolysate and the energy hydrolysate according to a mass ratio of 2:3, after mixing, carrying out supercritical water oxidation treatment, and then carrying out salt removal treatment to obtain fluid to be discharged; wherein the temperature of the supercritical water oxidation treatment is 600 ℃, the pressure is 25MPa, the peroxide amount is 150%, and the time is 30s;
and 1.6, carrying out gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas. The main component of the waste gas is CO 2 、H 2 O、N 2 And O 2 Directly discharging to the atmosphere; the waste liquid is subjected to conductivity detection, and the conductivity is higher, so that the waste liquid is used for treating general production waste water.
1.7, carrying out high-temperature decontamination treatment on the metal part to remove volatile organic matters attached to the metal part; the high-temperature decontamination treatment is carried out at 550 ℃ for 15min, so that volatile organic matters attached to the metal part can be volatilized into organic gases, and the organic gases are collected and purified by adopting an RTO system.
In addition, although the present invention is disclosed above, the scope of the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications will fall within the scope of the invention.
Claims (9)
1. A method of treating an energetic material, comprising:
s1, disassembling and cleaning an energetic material to obtain chemical agent sewage, a solid energy substance with a coating shell and a metal part;
s2, adding a first alkali liquor and an organic solvent into the chemical agent decontaminating water to form a first hydrolysate, and stirring the first hydrolysate to react to obtain a chemical hydrolysate; adding the solid energy substance into a primary hydrolysis reactor, and performing primary energy hydrolysis reaction to obtain pretreated energy hydrolysis solution; wherein, the primary hydrolysis reactor is added with a second alkali liquor;
s3, performing stability analysis on the pretreatment energy hydrolysate;
if the stability of the pretreatment energy hydrolysate meets the requirement, adding a metal precipitant, and filtering to obtain the energy hydrolysate;
if the stability of the pretreatment energy hydrolysis liquid does not meet the requirement, transferring the pretreatment energy hydrolysis liquid into a secondary hydrolysis reactor, adding a metal precipitant after secondary energy hydrolysis reaction, and filtering to obtain energy hydrolysis liquid; wherein, a third alkali liquor is added into the secondary hydrolysis reactor;
and S4, mixing the chemical hydrolysate with the energy hydrolysate, performing supercritical water oxidation treatment, and then performing salt removal treatment to obtain the fluid to be discharged.
2. The method according to claim 1, wherein in the step S3, the stability analysis of the pretreated energy hydrolysate comprises: analyzing the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate, wherein when the concentration of the energy components which are not decomposed in the pretreatment energy hydrolysate is larger than a safe concentration standard, the stability of the pretreatment energy hydrolysate does not meet the requirement; and when the concentration of the undegraded energy components in the pretreatment energy hydrolysate is not higher than the safety concentration standard, the stability of the pretreatment energy hydrolysate meets the requirement.
3. The method according to claim 1, wherein in the step S2, the temperature of the first alkaline solution is 60-90 ℃, the pH of the first hydrolysate is 10-13, and the stirring reaction time is 2-6 hours.
4. The method of claim 1, wherein in step S2, the organic solvent comprises one of methanol, isopropyl alcohol, and isobutyl alcohol.
5. The method according to claim 1, wherein in the step S2, the mass fraction of the second alkaline solution is 30-50%, the temperature is 100-130 ℃, and the primary energy hydrolysis reaction time is 0.5-3 hours; in the step S3, the mass fraction of the third alkali liquor is 30-50%, the temperature is 100-130 ℃, and the time of the secondary energy hydrolysis reaction is 0.5-3h.
6. The method according to claim 1, wherein in the step S4, the supercritical water oxidation treatment is performed at a temperature of 500-700 ℃, a pressure of 22-25MPa, and a time of 10-50S.
7. The energetic material processing method as recited in claim 1, further comprising:
and S5, performing gas-liquid separation on the fluid to be discharged to obtain waste liquid and waste gas.
8. The energetic material processing method as recited in claim 1, further comprising: and carrying out high-temperature decontamination treatment on the metal part to remove volatile organic matters attached to the metal part.
9. The method of claim 1, wherein the high temperature decontamination process is performed at a temperature of 500-600 ℃ for a period of 10-20 minutes.
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