CN116553985A - Synchronous regulation and control method for HMX quality, granularity and distribution thereof based on additive-ultrasonic combined technology - Google Patents
Synchronous regulation and control method for HMX quality, granularity and distribution thereof based on additive-ultrasonic combined technology Download PDFInfo
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- 238000009826 distribution Methods 0.000 title claims abstract description 41
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- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000012296 anti-solvent Substances 0.000 claims abstract description 15
- 230000006698 induction Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000010413 mother solution Substances 0.000 claims abstract description 7
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- 238000001953 recrystallisation Methods 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 13
- 230000001276 controlling effect Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Chemical group Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 56
- 239000002360 explosive Substances 0.000 abstract description 18
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- 238000002425 crystallisation Methods 0.000 abstract description 7
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- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 83
- 238000002604 ultrasonography Methods 0.000 description 31
- 238000012512 characterization method Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 239000003380 propellant Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
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- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B49/00—Use of single substances as explosives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a synchronous regulation and control method for HMX quality, granularity and distribution thereof based on an additive-ultrasonic combined technology, which comprises the following steps: dissolving HMX in DMSO to prepare DMSO/H 2 Adding a certain amount of additive into the mother solution, and stirring for dissolution; then adding antisolvent H rapidly 2 And (3) after the reaction liquid system is clarified, filtering, washing and drying to obtain the high-quality HMX with different granularity. The invention combines the additive-ultrasonic induction technology, optimizes the phase transformation process in a DMSO crystal transformation system by inhibiting intermediate phase alpha of the additive and combining the ultrasonic cavitation effect to promote beta nucleation, has simple and reliable method, high process stability and high crystallization yield, and can provide a new thought for the synchronous and reliable control of the quality, granularity and distribution of explosive crystalsAnd (5) a road.
Description
Technical Field
The invention relates to a preparation technology of explosive crystals, in particular to a synchronous regulation and control method for HMX quality, granularity and distribution thereof based on an additive-ultrasonic combined technology.
Background
The explosive crystals are usually matched with other materials to form a mixed explosive for use, and the granularity and granularity distribution of the explosive crystals play an important role in the design and performance regulation of the mixed explosive. The crystal granularity and granularity distribution required by the application can be obtained through crystalline control, and the component structure, the forming property, the filling density, the mechanical property, the shock wave sensitivity, the energy output and the like of the mixed explosive can be adjusted. Therefore, the research on the technology for regulating and controlling the crystal granularity and the distribution of the explosive can provide a new theoretical basis and technical means for improving and enhancing the properties of the mixed explosive, such as the loading density, the processing performance, the mechanical performance and the like, and has important significance.
HMX is widely used in various advanced weapon charging structures as the simple substance explosive with the best comprehensive performance at present. However, the research reports at home and abroad show that the mixed explosive based on HMX has the problems of poor environmental adaptability, insufficient mechanical property safety threshold and poor forming property. If the particle size and distribution of the high-quality HMX can be regulated and controlled, the molding of the mixed explosive based on the HMX and the mechanical properties of the mixed explosive are obviously improved.
The research on quality control of HMX crystals was carried out from the beginning of the 80 s of the 20 th century abroad, and the research on recrystallization of high-quality HMX was carried out from the 2000 th China national institute of engineering and physics. At present, high-quality HMX is successfully obtained by a DMSO crystal transformation technology at home and abroad, the product has high crystal quality and few internal defects, but the particle size distribution is wide, and the production efficiency is lower. At present, the regulating and controlling methods for the particle size and distribution of HMX crystals at home and abroad mainly comprise physical methods such as sieving, ball milling and the like, but the methods have the problems of low safety, complex operation, large difficulty in controlling particle size and the like in the using process, and the quality of the HMX crystals prepared by the methods is generally poor, so that the difficulty in reliably and synchronously controlling the particle size and the crystal quality is large. There is therefore still a need to explore new techniques for preparing high quality HMX of different particle sizes and particle size distributions.
Report (Holston safeguard corporation. Technical report No. HDC-58-80) discloses a method for transferring HMX crystal, 1 part of alpha-HMX is dissolved in 27.6 parts of 68% acetone aqueous solution under the condition of 55 ℃ and stirring, after dissolving, cooled to 25 ℃, 0.05 part of E-grade beta-HMX seed crystal is added, 22.67 parts of water is added to the mixture at 20-30 ℃, after the temperature is increased to 99 ℃, acetone is removed after 15min, cooled to 30-40 ℃, vacuum filtration is carried out, beta-HMX is obtained, the melting point is 280 ℃, 99.4% of the product passes through 325 mesh sieve, the granularity is slightly more than E grade, and the crystal transferring rate is 99.3%. Although this method realizes the alpha-beta crystal transformation process, it has the disadvantage that colloidal impurities in the crude product are often attached to the crystal surface, making the appearance of beta-HMX darker.
The literature (Propellants Explosive Pyrotechnics,2008,33 (4): 33-36) reports that a high density HMX (near theoretical density) is obtained in different solvent systems such as DMF, NMP, acetone and the like by using a cooling recrystallization technology, the defect in the crystal is very few, the shock wave sensitivity is greatly reduced, and the detonation energy is obviously improved. Although the method can obtain high-quality HMX, the crystallization yield is low, which is not beneficial to mass production.
Document (Propellants Explosives Pyrotechnics,2011,36 (6): 505-512) compares the preparation of HMX using wet milling, solvent-antisolvent, wet sieving, wherein the solvent-antisolvent process yields HMX particles with a relatively concentrated distribution and a relatively smooth surface. Although the relative concentration of the particle size distribution of the HMX particles can be achieved by three techniques, the method is still to be improved, and all three methods can cause certain degradation of crystal quality.
The literature (Ind. Eng. Chem. Res.,2011, 50:9107-9115) reports that a supercritical carbon dioxide anti-solvent process (SAS) is based, and beta-HMX particles with the particle size of 6.3-32.1 μm are obtained under the extreme condition of 50 ℃ and 12Mpa, but the crystal quality obtained by the method is poor, the particle size distribution is wide, and the experimental condition is demanding, the cost is high, and the batch preparation is not favored.
Disclosure of Invention
The invention aims to provide a synchronous regulation and control method for HMX quality, granularity and distribution based on an additive-ultrasonic combined technology, and provides a new idea for synchronous controllable regulation and control of HMX quality, granularity and distribution.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a synchronous regulation and control method for HMX quality, granularity and distribution thereof based on additive-ultrasonic combined technology comprises the following steps:
step A: dissolving HMX in DMSO to prepare a DMSO/HMX mother solution;
and (B) step (B): adding the additive into DMSO/HMX mother solution, stirring for dissolving, and performing additive induction;
step C: antisolvent H 2 Adding O into DMSO/HMX mother liquor, and simultaneously carrying out ultrasonic-stirring treatment and ultrasonic induction;
step D: stopping ultrasonic treatment after ultrasonic treatment for different time, continuing stirring, after recrystallization is completed,
the liquid layer is clear, and the high-quality HMX with different granularity is obtained by filtering, washing and drying.
The additive is induced by adding a certain amount of crystal form inducer into DMSO/HMX mother liquor, and promoting gamma to be directly converted into beta by inhibiting the formation of intermediate stable phase alpha phase in the crystal transformation process, so as to separate out high-quality beta-HMX;
the ultrasonic induction is that under the state that the anti-solvent is viscous gamma-HMX, the viscosity is reduced through cavitation effect and mechanical effect of ultrasonic, and meanwhile, a supersaturated area is formed locally, so that generation of beta crystal nucleus is promoted, and the induction period of gamma-beta is shortened.
In the invention, in the step A, after the HMX is completely dissolved, the step B is carried out, and ultrasonic dissolution can be added. Adding antisolvent H in step B 2 After O, the mixture needs to be stirred rapidly to realize the rapid mixing of the solvent and the solvent-solvent.
The DMSO solvent adopted by the invention is industrial pure (Hubei Yixing) or chromatographic pure (Alfa Aesar).
The further technical scheme is that the mass ratio of DMSO to HMX in the DMSO/HMX mother solution in the step A is 3:1.
According to a further technical scheme, the additive in the step B is selected from formic acid, acetic acid, oxalic acid, citric acid, HCl and H 2 SO 4 、HNO 3 、H 3 PO 4 The addition amount of any one of the components is 1 per mill to 5 percent of the mass fraction of the reaction system.
The further technical scheme is that the ultrasonic frequency in the step C is any one of 28, 35, 45 and 80MHz, and the ultrasonic time is 20 seconds to 5 minutes.
The further technical proposal is that in the step C, DMSO and an antisolvent H 2 The volume ratio of O is 5:1-1:1.
According to a further technical scheme, the step A, B, C, D is carried out at a temperature of 20-30 ℃.
The invention is further explained and illustrated below.
According to the invention, the additive and ultrasonic induction are introduced into the DMSO crystal transformation process, the inhibition of the additive to the formation of alpha phase and the cavitation effect of ultrasonic are utilized to promote beta nucleation, the original gamma-alpha-beta three-phase transformation process is changed into gamma-beta two-phase transformation, and the difficulty of process control is reduced, so that the synchronous and reliable regulation and control of the quality, granularity and distribution of HMX crystals are realized, and the crystallization time is shortened to 1/6 to 1/10 of the original crystallization time.
Antisolvent H 2 After O is added into DMSO/HMX mother liquor, the solution needs to be stirred rapidly to ensure that the solvent and the solvent are fully mixed and then ultrasonic treatment is started.
The additives of the present invention are small molecules capable of inhibiting alpha phase formation but not beta nucleation, and are exemplified herein without limitation.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method adopts an additive-ultrasonic combined induction method, inhibits the formation of alpha phase in a DMSO crystal transformation system through the additive, promotes beta nucleation through the combined ultrasonic cavitation effect, changes the original gamma-alpha-beta three-phase transformation process into gamma-beta two-phase transformation, and reduces the control difficulty of the process.
(2) The method can realize synchronous and reliable regulation and control of the quality, granularity and distribution of HMX crystals, shortens the crystallization time to 1/6 to 1/10 of the original crystallization time, is simple and reliable, has high process stability and high crystallization yield, and is suitable for industrial mass production.
(3) The HMX obtained by recrystallization has good particle morphology, is beta crystalline phase, has few internal and external defects of the crystal, has the crystal purity of more than 99.6 percent, and has the crystal density of more than 99.8 percent of the theoretical density of the beta-HMX. The invention can provide a new thought for synchronously and reliably controlling the quality, granularity and distribution of the explosive crystals, and simultaneously can provide a new theoretical basis and technical means for improving and enhancing the properties of the mixed explosive, such as the loading density, the processing performance, the mechanical performance and the like.
Drawings
FIG. 1 is a topography of an HMX feedstock;
FIG. 2 is a graph of the crystal morphology of recrystallized HMX;
FIG. 3 is a refractive matching micrograph of HMX feedstock;
FIG. 4 is a refractive matching micrograph of recrystallized HMX;
FIG. 5 is a graph of the morphology of recrystallized HMX obtained from various embodiments;
FIG. 6 is an X-ray powder diffraction pattern of recrystallized HMX;
FIG. 7 is a graph of the particle size distribution of HMX feedstock;
FIG. 8 is a graph of the particle size distribution of recrystallized HMX;
Detailed Description
The invention is further illustrated and described below in connection with the following examples of the invention.
Detection instrument:
refractive matching microscope: SK2005A refractive microscope was measured after matching with a matching fluid having a refractive index of 1.590.
Field emission scanning electron microscope: apollo 300 CSF-3A, metal spraying treatment of test sample, protective gas: argon, current: 20mA, time: 3min, working voltage: 2KV.
X-ray powder diffractometer (XRD): bruker D8 Advance, diffraction source: cuK alphaOne-dimensional array detector: vantec-1, current: the temperature of the solution was 40mA,voltage: 40kv, scan range: 5-50 DEG, scanning rate: 0.2 s/step, scan step: 0.02 °/step.
Laser particle size analyzer: the great Britain Markersizer 2000 type, high capacity Hydro 2000MU, hydro 2000SU type wet dispersion system, helium-neon gas laser source (633 nm) and blue light auxiliary source (466 nm), the particle size measuring range is 0.02-2 000 μm.
High Performance Liquid Chromatograph (HPLC): HP1100 high performance liquid chromatograph, configuration G1311A quaternary gradient pump, G1316A thermostated column incubator, G1315A diode array detector, 7725i hand sampler, HPA.07.01 edition chemical workstation. Chromatographic column: zorbax phenyl, inner diameter 4.6mm, length 250mm, filler particle size 5 μm, reagent: acetonitrile (chromatographic purity), dimethyl sulfoxide (analytical purity), pure water (resistivity. Gtoreq.16mΩ).
Density gradiometer: the density measuring device developed by the research institute of chemical materials is adopted, zinc bromide is used as density gradient solution, and explosive crystal density characterization is carried out.
Example 1:
(1) Weighing 18mL of DMSO, placing in a 50mL beaker, weighing 6g of HMX raw material, adding, dissolving with the aid of ultrasound until crystals are completely dissolved, adding a certain amount of HCl (6%o), and mixing uniformly to obtain DMSO/HMX mother liquor;
(2) Antisolvent H 2 Adding O6 mL into DMSO/HMX mother liquor rapidly and stirring uniformly to obtain a mixed solution;
(3) After being stirred uniformly, the mixed solution is subjected to ultrasonic treatment, the ultrasonic frequency is 80MHz, and the ultrasonic time is 2 minutes;
(4) After ultrasonic treatment for 2 minutes, stopping ultrasonic treatment, continuing stirring, filtering, washing and drying after the liquid layer is clear, taking a small amount of samples, carrying out characterization by a refraction matching microscope to confirm that crystal transformation is completed, confirming that the crystal form meets the requirement by XRD, and confirming that the granularity and granularity distribution of HMX obtained by recrystallization meet the requirement by laser granularity meter characterization.
Example 2:
(1) Weighing 24mL of DMSO, placing in a 50mL beaker, weighing 8g of HMX raw material, adding, dissolving with the aid of ultrasound until the crystal is completely dissolved, adding a certain amount of citric acid (1%), and mixing uniformly to obtain DMSO/HMX mother liquor;
(2) Antisolvent H 2 Adding O8 mL into DMSO/HMX mother liquor rapidly and stirring uniformly to obtain a mixed solution;
(3) After being stirred uniformly, the mixed solution is subjected to ultrasonic treatment, the ultrasonic frequency is 45MHz, and the ultrasonic time is 30s;
(4) After ultrasonic treatment for 30 seconds, stopping ultrasonic treatment, continuing stirring, filtering, washing and drying after the liquid layer is clear, taking a small amount of samples, carrying out refraction matching microscope characterization to confirm that crystal transformation is completed, confirming that the crystal form meets the requirements through XRD, and confirming that the HMX granularity and granularity distribution obtained through recrystallization meet the requirements through laser granularity meter characterization.
Example 3:
(1) Weighing 24mL of DMSO, placing in a 50mL beaker, weighing 8g of HMX raw material, adding, dissolving with the aid of ultrasound until the crystal is completely dissolved, adding a certain amount of acetic acid (5%o), and mixing uniformly to obtain DMSO/HMX mother liquor;
(2) Antisolvent H 2 Adding O8 mL into DMSO/HMX mother liquor rapidly and stirring uniformly to obtain a mixed solution;
(3) After being stirred uniformly, the mixed solution is subjected to ultrasonic treatment, the ultrasonic frequency is 80MHz, and the ultrasonic time is 2 minutes;
(4) After ultrasonic treatment for 2 minutes, stopping ultrasonic treatment, continuing stirring, filtering, washing and drying after the liquid layer is clear, taking a small amount of samples, carrying out characterization by a refraction matching microscope to confirm that crystal transformation is completed, confirming that the crystal form meets the requirement by XRD, and confirming that the granularity and granularity distribution of HMX obtained by recrystallization meet the requirement by laser granularity meter characterization.
Example 4:
(1) Weighing 24mL of DMSO, placing in a 50mL beaker, weighing 8g of HMX raw material, adding, dissolving with the aid of ultrasound until crystals are completely dissolved, adding a certain amount of oxalic acid (2%o), and mixing uniformly to obtain DMSO/HMX mother liquor;
(2) Antisolvent H 2 Adding 24mL of O into the DMSO/HMX mother solution rapidly and stirring uniformly to obtain a mixed solution;
(3) After being stirred uniformly, the mixed solution is subjected to ultrasonic treatment, the ultrasonic frequency is 80MHz, and the ultrasonic time is 2 minutes;
(4) After ultrasonic treatment for 2 minutes, stopping ultrasonic treatment, continuing stirring, filtering, washing and drying after the liquid layer is clear, taking a small amount of samples, carrying out characterization by a refraction matching microscope to confirm that crystal transformation is completed, confirming that the crystal form meets the requirement by XRD, and confirming that the granularity and granularity distribution of HMX obtained by recrystallization meet the requirement by laser granularity meter characterization.
Example 5:
the process is the same as in example 1 except that in step one the additive is H 2 SO 4 (2.5%) ultrasonic time in step three was 1 minute.
Example 6:
the procedure is as in example 1 except that the additive is formic acid (5%) in step one and the sonication time in step three is 1 minute.
Example 7:
the process is the same as in example 1 except that in step one the additive is H 3 PO 4 (1.5%) ultrasonic time in step three was 1 minute.
Example 8:
the procedure is as in example 1, except that the additive in step one is HNO 3 (5%) ultrasonic time in step three was 1 minute.
Example 9:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 45Mhz and the ultrasound time is 1 minute.
Example 10:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 45Mhz and the ultrasound time is 30 seconds.
Example 11:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 45Mhz and the ultrasound time is 1.5 minutes.
Example 12:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 45Mhz and the ultrasound time is 3 minutes.
Example 13:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 35Mhz and the ultrasound time is 30 seconds.
Example 14:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 35Mhz and the ultrasound time is 1 minute.
Example 15:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 35Mhz and the ultrasound time is 1.5 minutes.
Example 16:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 28Mhz and the ultrasound time is 30 seconds.
Example 17:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 28Mhz and the ultrasound time is 1 minute.
Example 18:
the procedure is as in example 1, except that in step three, the ultrasound frequency is 28Mhz and the ultrasound time is 1.5 minutes.
Example 19:
the procedure is as in example 1, except that the ultrasound time in step three is 20 seconds.
Example 20:
the procedure is as in example 1, except that the ultrasound time in step three is 30 seconds.
Example 21:
the procedure is as in example 1, except that the ultrasound time in step three is 45 seconds.
Example 22:
the procedure is as in example 1, except that the ultrasound time in step three is 1 minute.
Example 23:
the procedure is as in example 1, except that the ultrasound time in step three is 1.5 minutes.
Example 24:
the procedure is as in example 1, except that the ultrasound time in step three is 3 minutes.
Example 25:
the procedure is as in example 1, except that the amount of additive in step one is 3% per mill.
Example 26:
the procedure is as in example 1 except that the amount of additive in step one is 3% and the ultrasound time in step three is 3 minutes.
The morphology diagram of the recrystallized HMX crystal particles prepared by the method of the embodiment 1 is shown in fig. 2, and compared with the HMX raw material (see fig. 1), the recrystallized HMX crystals have regular morphology, improved crystal quality and narrow crystal particle size distribution.
Fig. 3 and 4 show refraction matching microscopic diagrams of raw material HMX and recrystallized HMX, and it can be seen from the diagrams that the HMX before recrystallization has poor internal quality and has the phenomena of mother liquor occlusion, twinning, and the like, and the HMX recrystallized by the method in example 1 has good crystal quality and few internal defects.
Fig. 5 shows morphology graphs of recrystallized HMX obtained according to different examples, from which it can be seen that narrow distribution DHMX with different particle size distribution can be obtained by simply adjusting the addition ratio of the additive and the time of the ultrasonic treatment. In fig. 5, morphology diagrams of example 19, example 20, example 21, example 22, example 23, example 1, example 24, example 2, and example 26 are sequentially from left to right from top to bottom.
As can be seen from XRD characterization, the recrystallization method in example 1 is adopted to completely convert the raw materials into high-quality beta-HMX (see figure 6), and the purity of the crystalline phase is high.
The particle size distributions of the raw material HMX and the HMX crystals after refinement are shown in fig. 7 and 8, respectively, and it can be seen from the figure that the particle size distribution of HMX before recrystallization is wide, and the dispersibility of the particle size distribution of the raw material of different batches is large, whereas the particle size distribution of the crystals obtained after HMX recrystallization by the method of example 1 is extremely narrow.
The chemical purity of HMX crystals before and after recrystallization is analyzed by adopting a high performance liquid chromatography method, the purity range is 99.6-99.9%, which indicates that the chemical purity of HMX recrystallized by adopting the method is high (more than 99.6 percent) and can meet the use requirement.
The density of HMX before and after recrystallization was characterized by a density gradient method, resulting in 1.9006-1.9018g.cm -3 The HMX crystal density after recrystallization is improved to reach the theoretical density of the beta-HMX crystal of 1.905g.cm -3 99.8% or more of (2) can satisfyThe use requirement. It is summarized that the method can realize synchronous and reliable regulation and control of the crystal quality, granularity and distribution of HMX.
Although the invention has been described herein with reference to the above-described illustrative embodiments thereof, the above-described embodiments are merely preferred embodiments of the present invention, and the embodiments of the present invention are not limited by the above-described embodiments, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.
Claims (6)
1. The method for synchronously regulating and controlling the quality, granularity and distribution of HMX based on the additive-ultrasonic combined technology is characterized by comprising the following steps of: .
Step A: dissolving HMX in DMSO to prepare a DMSO/HMX mother solution;
and (B) step (B): adding the additive into DMSO/HMX mother solution, stirring for dissolving, and performing additive induction;
step C: antisolvent H 2 Adding O into DMSO/HMX mother liquor, and simultaneously carrying out ultrasonic-stirring treatment and ultrasonic induction;
step D: stopping ultrasonic treatment after ultrasonic treatment for different times, continuing stirring, and after recrystallization is finished, clearly obtaining a liquid layer, and filtering, washing and drying to obtain high-quality HMX with different granularity.
2. The method for synchronously regulating and controlling the quality, the granularity and the distribution of the HMX based on the additive-ultrasonic combined technology according to claim 1, wherein the mass ratio of DMSO to HMX in the DMSO/HMX mother liquor in the step A is 3:1.
3. The method for simultaneous control of HMX quality, particle size and distribution thereof based on additive-ultrasonic combined technology according to claim 1, wherein the additive in step B is selected from formic acid, acetic acid, oxalic acid, citric acid, HCl, H 2 SO 4 、HNO 3 、H 3 PO 4 Any one of the components is added in the reverse wayThe mass fraction of the reaction system is 1 per mill to 5 percent.
4. The method for synchronously regulating and controlling the quality, the granularity and the distribution of the HMX based on the additive-ultrasonic combined technology according to claim 1, wherein the ultrasonic frequency in the step C is any one of 28, 35, 45 and 80MHz, and the ultrasonic time is 20 seconds to 5 minutes.
5. The method for synchronously regulating and controlling the quality, the granularity and the distribution of HMX based on the additive-ultrasonic combined technology according to claim 1, wherein DMSO and an antisolvent H in the step C 2 The volume ratio of O is 5:1-1:1.
6. The method for synchronously regulating and controlling the quality, the granularity and the distribution of the HMX based on the additive-ultrasonic combined technology according to claim 1, wherein the step A, B, C, D is carried out at the temperature of 20-30 ℃.
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