An explosive refinement device and method for hexanitrostyrene

Abstract

The present application relates to a kind of explosives of hexanitrostyrene and method for refining device, belong to explosive refining technical field, by reaction kettle, HNS is dissolved in solvent, by HNS solution delivery system, HNS solution is delivered to spray refining head, by cooling module, deionized water module is sent to deionized water, and by anti-solvent delivery system, the cooled deionized water is delivered from cooling module to spray refining head, spray refining head mixes the solution of deionized water and HNS solution and is sprayed to crystallization kettle, the present application can be designed by device and flow, HNS solution and deionized water flow and temperature realize automatic control, compared with single liquid refining spray, its mixed spray process turbulence is higher, product particle size is smaller, relative to mechanical ball milling refining method, product particle size is smaller and distribution is more concentrated, time-consuming is less, production efficiency is higher, improve the consistency of process, improve the automation and safety level of production process.

Description

Technical Field

[0001] This invention belongs to the field of explosive refining technology, specifically relating to an explosive refining device and method for hexanitrozimine. Background Technology

[0002] Ultrafine hexanitrostilbene-IV (HNS-IV) is an organic compound with the chemical formula C1. 14 H6N6O 12 It has excellent resistance to mechanical impact and high temperature environment adaptability. It can be reliably detonated in the range of (-193~225)℃. It has good mechanical and mechanical environment adaptability and is mainly used as the initial charge of pyrotechnics and some non-electric system detonation charge.

[0003] Regarding the preparation technology of HNS-IV, relevant domestic research institutions and some pyrotechnic product manufacturing units have conducted research, but most are still in the stage of laboratory preparation and small-batch research and production. The refinement of the explosive is mainly achieved through two methods: mechanical ball milling and spray refinement. A patent authorized by Beijing Institute of Technology (CN116903425A) discloses a device and method for preparing LLM-105 / HNS spray-blended crystals. The device forms a co-solvent, which is then atomized and sprayed into a non-solvent bottle via a high-pressure gas cylinder. After standing and filtration, the sample is obtained. A patent authorized by the Institute of Chemical Materials, China Academy of Engineering Physics (CN107814671A) discloses a method for refining hexanitrohexaazaisowulzyl host-guest explosive crystals. A small-molecule gas at a certain temperature is continuously introduced into a cavity with inlets and outlets to form a stable gas flow. Liquid is sprayed into this cavity to achieve rapid co-crystallization and form host-guest explosive crystals with ultrafine particle sizes and embedded gas molecules within the crystal cells. The patent CN106220460B authorized by North China University of Technology discloses a method for preparing graphene-based composite energetic materials. The method involves grinding explosives, solutions, and grinding balls in a spherical ink tank for 3 to 10 hours, followed by filtration, washing, and freeze-drying to obtain the product. The patent CN113694782A authorized by Nanjing University of Science and Technology discloses a micro-nano explosive preparation system and method based on a coaxial focusing micro-mixer. The system uses a high-pressure fluid to drive a non-solvent, a flow-stabilized drive unit to drive a solvent, and the mixture is sprayed after mixing in a coaxial T-type three-way connector to prepare nano-explosives. The above methods mainly have the following problems: (1) The spraying refinement method mainly uses a single liquid for production, or uses a premixed liquid to ensure the uniformity of the spraying process. At the same time, two liquids are used for spraying crystallization. The device is manually operated and controlled. Due to the instability of liquid flow control, it is difficult to ensure the consistency of products between multiple batches.

[0004] (2) Spraying refinement uses a coaxial nozzle and room temperature non-solvent to prepare nano-explosives. Its turbulence is relatively low and the precipitation rate is relatively slow, so it is impossible to obtain nano-explosives with smaller particle size.

[0005] (3) The jet refining method mainly uses high-pressure gas or airflow to drive atomization and crystallization through the jet head. This process is mostly achieved by non-automatic control equipment or manual operation, which cannot achieve continuous and automated mass production, and it is difficult to increase production capacity.

[0006] (4) Mechanical ball milling is time-consuming, has low production efficiency, and its production output is limited by the size of the ball mill cavity. The particle size distribution of the ball milled products is relatively wide, and it is difficult to guarantee the consistency of the product particle size. Summary of the Invention

[0007] The purpose of this invention is to provide an apparatus and method for refining explosives containing hexanitrophos, wherein HNS solution and deionized water are mixed and sprayed out through the same nozzle. Compared with single liquid refining spray, the mixed spray process has higher turbulence and smaller product particle size. Compared with mechanical ball milling refining method, the product particle size is smaller and more concentrated, and the production efficiency is higher with less time consumption.

[0008] The above-mentioned objectives of the present invention are mainly achieved through the following technical solutions:

[0009] An explosive refining device for hexanitrozines includes a reaction vessel, an HNS solution delivery system, a crystallization vessel, an antisolvent delivery system, a deionized water module, a cooling module, and a jet refining head, wherein...

[0010] The reaction vessel is used to dissolve HNS in a solvent to obtain an HNS solution;

[0011] The HNS solution delivery system is used to deliver the HNS solution in the reactor to the jet refiner head;

[0012] The deionized water module is used to generate deionized water and deliver it to the cooling module;

[0013] The cooling module is used to cool deionized water;

[0014] The antisolvent delivery system is used to deliver deionized water from the cooling module to the jet refiner head;

[0015] The jet refiner head is used to spray a mixed solution of deionized water and HNS solution into the crystallization vessel;

[0016] The crystallization vessel is used to receive and store the mixed solution.

[0017] The HNS solution delivery system includes a first solenoid valve, a first centrifugal pump, a solution delivery pipeline, a pipeline heating and insulation layer, a first flow meter, a first thermometer, and a first flow feedback control system. The solution delivery pipeline connects the reactor and the jet refiner head. The first solenoid valve controls the flow of solution from the reactor into the solution delivery pipeline. The first centrifugal pump delivers the solution from the solution delivery pipeline to the jet refiner head. The pipeline heating and insulation layer covers the outside of the solution delivery pipeline. The first flow meter and the first thermometer detect the flow rate and temperature of the solution in the solution delivery pipeline and send the results to the first flow feedback control system. The first flow feedback control system controls the opening and closing of the first solenoid valve, the first centrifugal pump, the first flow meter, and the first thermometer.

[0018] The antisolvent delivery system includes a deionized water delivery pipeline, a pipeline insulation layer, a centrifugal pump, a solenoid valve, a second flow meter, a second thermometer, and a second flow feedback control system. The deionized water delivery pipeline connects the cooling module and the jet refiner head. The solenoid valve controls the entry of deionized water from the cooling module into the deionized water delivery pipeline. The centrifugal pump delivers the deionized water from the pipeline to the jet refiner head. The pipeline insulation layer covers the outside of the deionized water delivery pipeline. The second flow meter and the second thermometer detect the flow rate and temperature of the deionized water in the pipeline and send the results to the second flow feedback control system. The second flow feedback control system controls the opening and closing of the centrifugal pump, the solenoid valve, the second flow meter, and the second thermometer.

[0019] The spray refining head includes an explosive solution inlet and an antisolvent inlet. The spray refining head has a columnar structure, and the mixed solution outlet is located at the bottom of the spray refining head. Columnar protrusions are provided on the side wall of the columnar structure. The explosive solution inlet is located on the columnar protrusions, and the antisolvent inlet is located at the top of the spray refining head.

[0020] The reactor, crystallizer, deionized water module, and cooling module can be used simultaneously with multiple HNS solution delivery systems, antisolvent delivery systems, and jet refiners.

[0021] A method for refining explosives for hexanitrophos, using the aforementioned explosive refining apparatus, specifically includes the following steps:

[0022] (1) Add HNS and solvent to the reaction vessel and heat to dissolve;

[0023] (2) The deionized water module prepares deionized water and circulates it into the cooling module for cooling and later use.

[0024] (3) Preheat the HNS solution delivery system, pass the cooled deionized water obtained in step (2) into the antisolvent delivery system and deliver it to the jet refiner head for discharge, and continue for a period of time to pre-cool it;

[0025] (4) After preheating and precooling, HNS solution and deionized water are simultaneously introduced into the jet refiner and sprayed into the crystallizer. During the process, the temperature and flow rate are continuously monitored to ensure that the temperature and flow rate are always within the preset range.

[0026] In step (1), the mass ratio of HNS to solvent is 1:10 to 1:50, and the heating temperature is 50 to 90°C.

[0027] In step (1), the solvent is N,N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.

[0028] In step (2), the temperature of the deionized water is 0 to 5°C.

[0029] In step (3), the preheating temperature of the HNS solution delivery system is 50-90°C, and the precooling time of the antisolvent delivery system is 2-5 minutes.

[0030] In step (4), the flow rate ratio of HNS solution to deionized water is 1:2 to 1:20.

[0031] Compared with the prior art, the present invention has at least the following beneficial effects:

[0032] (1) In this invention, HNS solution and deionized water are introduced into the same spray head. Compared with single liquid refining spray, the mixed spray process has higher turbulence and smaller product particle size. Compared with mechanical ball milling refining method, the product particle size is smaller and more concentrated, and the production efficiency is higher with less time consumption.

[0033] (2) In the preferred embodiment of the present invention, a centrifugal pump and a flow meter are used together, and a closed-loop feedback algorithm for automatic control is adopted to ensure accurate and adjustable flow rate and stable delivery. This avoids the problems of large fluctuations in product particle size and unintuitive flow control caused by the instability of direct flow control of pumps used manually, and improves the consistency of the process.

[0034] (3) The preferred embodiment of the present invention adopts a flow feedback control system, and the production process is carried out automatically according to the program without human intervention, which avoids long-term contact between people and pharmaceuticals and solvents, and improves the automation and safety level of the production process.

[0035] (4) In the embodiments of the present invention, multiple sets of spray heads are preferably used, and an automated closed-loop feedback flow control system is adopted to ensure accurate control and consistency of flow from multiple channels. This avoids the problem that manual production without flow control can only use a fixed spray head to ensure the particle size distribution range, which leads to the inability to increase production capacity. Attached Figure Description

[0036] Figure 1 This is a flowchart of a method for refining explosives for hexanitrozines according to the present invention;

[0037] Figure 2 This is a schematic diagram of an explosive refining device for hexanitrozines according to the present invention;

[0038] Figure 3 This is a schematic diagram of the spray refining head of an explosive refining device for hexanitrozines according to the present invention;

[0039] Figure 4 This is a schematic diagram of the control logic of an explosive refining device for hexanitrozines according to the present invention. Detailed Implementation

[0040] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments:

[0041] like Figure 2 As shown, the device of the present invention mainly includes: a reaction vessel 1, an HNS solution delivery system 2, a crystallization vessel 3, an antisolvent delivery system 4, a deionized water module 5, a cooling module 6, and a jet refining head 7. The HNS solution delivery system 2 mainly includes a first solenoid valve 21, a first centrifugal pump 22, a solution delivery pipeline 23, a pipeline heating and insulation layer 24, a first flow meter 25, a first thermometer 26, and a first flow feedback control system 27. The antisolvent delivery system 4 mainly includes a deionized water delivery pipeline 41, a pipeline insulation layer 42, a second centrifugal pump 43, a second solenoid valve 44, a second flow meter 45, a second thermometer 46, and a second flow feedback control system 47. The jet refining head 7 mainly includes an explosive solution inlet 71 and an antisolvent inlet 72.

[0042] The crystallization vessel 3 is fixed at the center of the device, and the jet refiner head 7 is connected to the reaction vessel 1 through the HNS solution delivery system 2 and to the cooling module 6 through the antisolvent delivery system 4.

[0043] like Figure 3 As shown, the jet refining head 7 includes an explosive solution inlet 71 and an antisolvent inlet 72. The jet refining head 7 has a columnar structure, and the mixed solution outlet is located at the bottom of the jet refining head 7. A columnar protrusion is provided on the side wall of the columnar structure. The explosive solution inlet 71 is provided on the columnar protrusion, and the antisolvent inlet 72 is provided at the top of the jet refining head 7.

[0044] HNS solution delivery system 2 is installed on the left side of crystallizer 3. Reactor 1 is fixed above the left of HNS solution delivery system 2 and connected through solution delivery pipe 23. Antisolvent delivery system 4 is installed on the right side of crystallizer 3. Cooling module 6 is installed above the right of antisolvent delivery system 4. Deionized water module 5 is installed on the right side of cooling module 6 and connected through deionized water delivery pipe 41. Spray atomizing head 7 is fixed above crystallizer 3 and connected to HNS solution delivery system 2 and antisolvent delivery system 4 through pipes. In the HNS solution delivery system 2, the first solenoid valve 21 is installed below the outlet of the reactor 1, the first centrifugal pump 22 is located to the right of the first solenoid valve 21, the first flow meter 25 is located 10-30cm to the left of the jet refining head 7 in the pipe, the first thermometer 26 is located 10-30cm to the left of the first flow meter 25 in the pipe, the pipe heating and insulation layer 24 is wrapped around the solution delivery pipe 23, and the first flow feedback control system 27 is connected to the first solenoid valve 21, the first centrifugal pump 22, the first thermometer 26, and the first flow meter 25 through cables and is fixed on the pipe 30-50cm to the left of the first thermometer 26. In the antisolvent delivery system 4, the second solenoid valve 44 is installed below the outlet of the cooling module 6, the second centrifugal pump 43 is located to the left and below the second solenoid valve 44, the second flow meter 45 is located 10-30cm to the right of the spray refining head 7 in the pipe, the second thermometer 46 is located 10-30cm to the right of the second flow meter 45 in the pipe, the pipe insulation layer 42 is wrapped around the deionized water delivery pipe 41, and the second flow feedback control system 47 is connected to the second solenoid valve 44, the second centrifugal pump 43, the second thermometer 46, and the second flow meter 45 via cables and is fixed on the pipe 30-50cm to the right of the thermometer.

[0045] During the implementation of the equipment, a set of reaction vessel 1, crystallization vessel 3, deionized water module 5, and cooling module 6 can be combined with multiple sets of HNS solution delivery system 2, antisolvent delivery system 4, and jet refining head 7 to expand production capacity.

[0046] The implementation steps of this invention are as follows:

[0047] like Figure 1 and Figure 4 As shown, the explosive refining method of the present invention includes the following steps:

[0048] (1) Heating and dissolving. Add HNS and solvent to reaction vessel 1 at a mass ratio of 1:10 to 1:50. Heat reaction vessel 1 to 50 to 90°C and dissolve HNS in polar solvents such as N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP) for later use.

[0049] (2) Preparation and cooling of deionized water: Deionized water module 5 prepares a sufficient amount of deionized water and circulates it into cooling module 6 to cool it to about 0-5℃ for later use.

[0050] (3) Pipeline preheating. 3 to 5 minutes before spraying, turn on the pipeline heating and insulation layer 24 of the HNS solution delivery system 2 to heat and insulate the solution delivery pipeline 23 to 50 to 90°C, and check whether the temperature meets the preheating requirements by using the first thermometer 26.

[0051] (4) Pipeline pre-cooling. Five minutes before spraying, the second solenoid valve 44 and the second flow meter 45 in the antisolvent delivery system 4 are automatically opened by the second flow feedback control system 47. The cooled deionized water is poured into the second centrifugal pump 43 under gravity through the second solenoid valve 44. After the second centrifugal pump 43 is full, the second flow feedback control system 47 starts the second centrifugal pump 43 to deliver the deionized water to the spray refining head 7 through the deionized water delivery pipeline 41. After 2 to 5 minutes, the second solenoid valve 44, the second flow meter 45 and the second centrifugal pump 43 are closed. The temperature is checked by the second thermometer 46 to see if the pre-cooling requirement has been met.

[0052] (5) Spraying and refining. The first solenoid valve 21 and the first flow meter 25 of the HNS solution delivery system 2 are automatically opened by the first flow feedback control system 27. The HNS solution is poured into the first centrifugal pump 22 under the action of gravity through the first solenoid valve 21. After the first centrifugal pump 22 is full, the first flow feedback control system 27 starts the first centrifugal pump 22 to deliver the HNS solution to the spray refining head 7 through the solution delivery pipe 23 and discharge it. At the same time, the second solenoid valve 44, the second flow meter 45, and the second centrifugal pump 43 in the antisolvent delivery system 4 are automatically opened by the second flow feedback control system 47. The second centrifugal pump 43 delivers deionized water to the spray refining head 7 through the deionized water delivery pipe 41 and discharges it. The mixed solution sprayed out through the spray refining head 7 enters the crystallization tank 3.

[0053] (6) Flow and Temperature Control. When the HNS solution delivery system 2 is operating, the first flow feedback control system 27 adjusts the speed of the first centrifugal pump 22 and the opening degree of the first flow meter 25 to control the HNS solution flow rate, and the first thermometer 26 detects the solution temperature. The antisolvent delivery system 4 operates simultaneously with the HNS solution delivery system 2, adjusting the speed of the second centrifugal pump 43 and the opening degree of the second flow meter 45 to control the deionized water flow rate, and the second thermometer 46 detects the deionized water temperature. The flow feedback systems 27 and 47 detect the flow rates of the HNS solution and deionized water through the first and second flow meters 25 and 45, respectively, and compare them with the set parameters through an internal controller. If the parameters are met, the flow rate is maintained; if the flow rate exceeds or falls short of the set parameters, the PID algorithm reverses the control of the speed of the first centrifugal pump 22 and the second centrifugal pump 43 to regulate the flow rate. The first flow feedback control system 27 of the HNS solution delivery system 2 and the second flow feedback control system 47 of the antisolvent delivery system 4 communicate and negotiate to ensure that the flow ratio between the two systems is always within the set range of 1:2 to 1:20.

[0054] (7) Sequence 1 and Sequence 2 can be performed simultaneously. After they are completed, Sequence 3 and Sequence 4 can be performed simultaneously. After they are completed, Sequence 5 and Sequence 6 must be performed simultaneously.

[0055] The above description is only the best specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the protection scope of the present invention.

[0056] The contents not described in detail in this specification are common knowledge to those skilled in the art.

Claims

1. A device for refining hexanitrozines explosive, characterized in that: It includes a reaction vessel (1), an HNS solution delivery system (2), a crystallization vessel (3), an antisolvent delivery system (4), a deionized water module (5), a cooling module (6), and a jet refiner head (7), wherein, The reaction vessel (1) is used to dissolve HNS in a solvent to obtain an HNS solution; The HNS solution delivery system (2) is used to deliver the HNS solution in the reactor (1) to the jet refiner head (7); The deionized water module (5) is used to generate deionized water and deliver it to the cooling module (6); The cooling module (6) is used to cool deionized water; The antisolvent delivery system (4) is used to deliver deionized water from the cooling module (6) to the jet refiner head (7); The jet refiner head (7) is used to spray a mixed solution of deionized water and HNS solution into the crystallization vessel (3); The crystallization vessel (3) is used to receive and store the mixed solution.

2. The explosive refining device for hexanitrozines according to claim 1, characterized in that: The HNS solution delivery system (2) includes a first solenoid valve (21), a first centrifugal pump (22), a solution delivery pipeline (23), a pipeline heating and insulation layer (24), a first flow meter (25), a first thermometer (26), and a first flow feedback control system (27). The solution delivery pipeline (23) connects the reactor (1) and the jet refiner head (7). The first solenoid valve (21) controls the flow of solution from the reactor (1) into the solution delivery pipeline (23). The first centrifugal pump (22) is used to pump the solution... The solution in the liquid delivery pipe (23) is delivered to the jet refining head (7). The pipe heating and insulation layer (24) covers the outside of the solution delivery pipe (23). The first flow meter (25) and the first thermometer (26) are used to detect the flow rate and temperature of the solution in the solution delivery pipe (23) and send the results to the first flow feedback control system (27). The first flow feedback control system (27) is used to control the opening and closing of the first solenoid valve (21), the first centrifugal pump (22), the first flow meter (25) and the first thermometer (26).

3. The explosive refining device for hexanitrozines according to claim 1, characterized in that: The antisolvent delivery system (4) includes a deionized water delivery pipe (41), a pipe insulation layer (42), a centrifugal pump (43), a solenoid valve (44), a second flow meter (45), a second thermometer (46), and a second flow feedback control system (47). The deionized water delivery pipe (41) connects the cooling module (6) and the jet refiner head (7). The solenoid valve (44) controls the entry of deionized water from the cooling module (6) into the deionized water delivery pipe (41). The centrifugal pump (43) delivers the deionized water... Deionized water is transported from the pipeline (41) to the jet refiner head (7). The pipeline insulation layer (42) covers the outside of the deionized water transport pipeline (41). The second flow meter (45) and the second thermometer (46) are used to detect the flow rate and temperature of the deionized water in the deionized water transport pipeline (41) and send the results to the second flow feedback control system (47). The second flow feedback control system (47) is used to control the opening and closing of the centrifugal pump (43), the solenoid valve (44), the second flow meter (45), and the second thermometer (46).

4. The explosive refining device for hexanitrozines according to claim 1, characterized in that: The jet refining head (7) includes an explosive solution inlet (71) and an antisolvent inlet (72). The jet refining head (7) has a columnar structure. The mixed solution outlet is located at the bottom of the jet refining head (7). A columnar protrusion is provided on the side wall of the columnar structure. The explosive solution inlet (71) is located on the columnar protrusion, and the antisolvent inlet (72) is located at the top of the jet refining head (7).

5. The explosive refining device for hexanitrozines according to claim 1, characterized in that: The reactor (1), crystallizer (3), deionized water module (5) and cooling module (6) are simultaneously equipped with multiple HNS solution delivery systems (2), antisolvent delivery systems (4) and jet refiners (7).

6. A method for refining explosives for hexanitrophos, characterized in that: The explosive refining apparatus according to any one of claims 1 to 5 specifically includes the following steps: (1) Add HNS and solvent to reaction vessel (1) and heat to dissolve; (2) The deionized water module (5) prepares deionized water and introduces it into the cooling module (6) for circulating cooling and ready for use; (3) Preheat the HNS solution delivery system (2), and pass the cooled deionized water obtained in step (2) into the antisolvent delivery system (4) and deliver it to the jet refiner head (7) for discharge. Continue for a period of time to pre-cool. (4) After preheating and precooling, HNS solution and deionized water are simultaneously introduced into the jet refiner head (7) and sprayed into the crystallizer (3). During the process, the temperature and flow rate are continuously monitored to ensure that the temperature and flow rate are always within the preset range.

7. A method for refining explosives for hexanitrozines according to claim 6, characterized in that: In step (1), the mass ratio of HNS to solvent is 1:10 to 1:50, and the heating temperature is 50 to 90°C.

8. A method for refining explosives for hexanitrozines according to claim 6, characterized in that: In step (1), the solvent is N,N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.

9. A method for refining explosives for hexanitrozines according to claim 6, characterized in that: In step (2), the temperature of the deionized water is 0-5℃; In step (3), the preheating temperature of the HNS solution delivery system (2) is 50-90°C, and the precooling time of the antisolvent delivery system (4) is 2-5 minutes.

10. A method for refining explosives for hexanitrozines according to claim 6, characterized in that: In step (4), the flow rate ratio of HNS solution to deionized water is 1:2 to 1:20.

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