CN102320903B - Method for preparing high-quality energetic crystal material fine particles - Google Patents
Method for preparing high-quality energetic crystal material fine particles Download PDFInfo
- Publication number
- CN102320903B CN102320903B CN 201110160871 CN201110160871A CN102320903B CN 102320903 B CN102320903 B CN 102320903B CN 201110160871 CN201110160871 CN 201110160871 CN 201110160871 A CN201110160871 A CN 201110160871A CN 102320903 B CN102320903 B CN 102320903B
- Authority
- CN
- China
- Prior art keywords
- crystal material
- quality
- material fine
- fine particles
- ultrasonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a method for preparing high-quality energetic crystal material fine particles. Various high-quality energetic crystal material fine particle products, such as pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), cyclotetramethylenetetranitramine (HMX), hexanitrohexaazaisowurtzitane (CL-20), DADNE (FOX-7), ammonium perchlorate (AP), and the like can be prepared by adopting an ultrasound solvating-out crystallization method in the traditional solvating-out crystallization process. The high-quality energetic crystal material fine particle product prepared by the preparation method disclosed by the invention has subglobular particle form, narrow granularity distribution, average particle diameter of 5-50 microns or so, transparent crystals, high particle density, crystal theoretical density of more than 99.9 percent and obviously reduced shock wave sensitivity and is used for pouring or pressing PBX (Plastic-bonded explosives). The method for preparing the high-quality energetic crystal material fine particles has the advantages of simple process flow and mild reaction conditions and is suitable for mass industrialized production.
Description
Technical field
The invention belongs to contain can crystalline material the field, particularly relate to contain can crystalline material the preparation method.
Background technology
Studies show that in a large number, the crystal quality of explosive (as purity, density, crystal habit, granularity and voidage etc.) is one of principal element that affects the explosive vulnerability, can improve its safety performance when keeping the original acting ability of explosive by the crystal quality of improving single chmical compound explosive, particularly reduce the shock sensitivity performance.Study by crystallization technique in recent years and improve the single chmical compound explosive crystal quality, prepare all kinds of focuses that the sense single chmical compound explosive becomes domestic and international energetic material research that fall.External successively have many units such as French Cross jakt, Australian ADI company, Norway Dyno Nobel company, German ICT etc. to develop all kinds ofly to fall sense RDX (RS-RDX) and fall and feel HMX (RS-HMX).External RS-RDX, RS-HMX technology of preparing generally adopt is non-linear process decrease temperature crystalline technology under different solvents, domestic RDX, the HMX crystallisation by cooling technology in different solvents (as dimethyl sulfoxide (DMSO), butyrolactone, cyclohexanone, N-Methyl pyrrolidone etc.) of also having studied has obtained the improved RDX of crystal quality and HMX.But the Granularity Distribution that all kinds of decrease temperature crystalline preparation methods that report both at home and abroad at present obtain is wide, in order to obtain the needed granularity of formulating of recipe, normally adopt the screening means to prepare the product that different grain size distributes, this method has not only increased technological process, the more important thing is the waste that causes large content of starting materials.The programmed cooling crystallization technique is difficult to prepare the following fine particle product of 50 μ m in addition, without satisfying the needed fine particle product requirement of formulation designs.Although adopt the dilution crystallization technology by adding fast poor solvent can prepare the fine particle product, the product crystal poor quality of this method preparation, solvent contains many, and crystalline density is low, and particle form is irregular, and can't obtain high-quality containing can crystalline material.for this problem, the present invention has studied the high-quality energetic crystal material fine particles product preparation method, adopt present method not only can effectively control product granularity, obtain the following fine particle product of 50 μ m, but also can effectively guarantee the crystal quality of product, obtain particle form regular, narrow particle size distribution, inner transparent, smooth surface, chemical purity and crystal apparent density are high, the high-quality energy crystalline material that contains that lattice defect is few, thereby greatly improved the safety performance of product, mechanical property and processing characteristics, be used for cast and press-fit PBX, can significantly reduce shock sensitivity.
Summary of the invention
The purpose of this invention is to provide the high-quality energetic crystal material fine particles preparation method.
Core content of the present invention is the power ultrasonic technology of introducing in traditional dilution crystallization process, adopts ultrasonic dilution crystallization method to prepare the high-quality energetic crystal material fine particles of median size 5 μ m to 50 μ m.Concrete steps are: (1) contains common RDX, HMX, CL-20 etc. formation saturated crystallization solution in the optimum solvent that is dissolved in respectively under energy crystalline material room temperature separately, (2) under ultrasonication, the poor solvent that adds to crystallization solution while stirring, (3) ultrasonic, stir certain hour after, filter, washing, drying, obtaining RDX, HMX, CL-20 etc. high-quality containing can crystalline material fine particle product.
The ultrasonic frequency that the present invention adopts is 20kHz-100kHz, and ultrasonic power density is greater than 1 * 10
-3Wcm
-3
The present invention filters after 1 hour in ultrasonic, stirring, washing, drying.
The present invention is applicable to comprise the multiple high-quality energetic crystal material fine particles product preparation of PETN, RDX, HMX, CL-20, FOX-7 and AP.
Adopt containing of ultrasonic dilution crystallization method preparation of the present invention can crystalline material product crystal defective few, the crystal apparent density reaches more than 99.9% of crystal theoretical density, and particle form is good, and sphericity is high, narrow particle size distribution, and shock sensitivity significantly reduces.
Above-mentioned ultrasonic dilution crystallization technology, make other crystallization processes parameter such as starting soln concentration, solution temperature, stirring velocity and bad solution add speed etc. less on the impact of product crystal quality, more being easy to get high-quality the containing that particle form is good, crystalline density is high can crystalline material.
The ultrasonic frequency of above-mentioned ultrasonic dilution crystallization technology and power density are larger for the crystal size impact, adopt low frequency and high power density to be easier to prepare the fine particle product.
Description of drawings
The high-quality RDX fine particle refractive index matching optics microscope picture that the ultrasonic dilution crystallization legal system of Fig. 1 is standby;
The high-quality CL-20 fine particle refractive index matching optics microscope picture that the ultrasonic dilution crystallization legal system of Fig. 2 is standby.
The high-quality HMX fine particle scanning electron microscope picture that the ultrasonic dilution crystallization legal system of Fig. 3 is standby.
Embodiment
The ultrasonic dilution crystallization of embodiment 1:RDX
At room temperature, 100g DMSO is added in ultrasonic crystallizer, add while stirring the common RDX of 35g under 30 ℃ of room temperatures, until completely dissolved, start ultrasonic field, ultrasonic field frequency 40kHz, ultrasonic field power density 0.5Wcm
-3, then add fast 300g ethanol, continue ultrasonic, stirred 1 hour, filter, washing, drying obtains the high-quality RDX of 30g (seeing accompanying drawing 1), crystalline density 1.7980gcm
-3, density distribution 1.7976gcm
-3To 1.7982gcm
-3, median size 20 μ m, D10=10 μ m, D90=30 μ m, size-grade distribution is normal distribution.
The ultrasonic dilution crystallization of embodiment 2:CL-20
At room temperature, the 30g ethyl acetate is added in ultrasonic crystallizer, add while stirring the common CL-20 of 13g under 30 ℃ of room temperatures, until completely dissolved, start ultrasonic field, ultrasonic field frequency 20kHz, ultrasonic field power density 1Wcm
-3, then add fast the 60g normal heptane, continue ultrasonic, stirred 1 hour, filter, washing, drying obtains the high-quality CL-20 of 11g (seeing accompanying drawing 2), crystalline density 2.0355gcm
-3, density distribution 2.0351gcm
-3To 2.0366gcm
-3, median size 30 μ m, D10=10 μ m, D90=50 μ m, size-grade distribution is normal distribution.
The ultrasonic dilution crystallization of embodiment 3:HMX
At room temperature, the 50g dimethyl sulfoxide (DMSO) is added in ultrasonic crystallizer, add while stirring the common HMX of 15g under 20 ℃ to 50 ℃, until completely dissolved, start ultrasonic field, ultrasonic field frequency 20kHz to 120kHz, the ultrasonic field power density is greater than 1 * 10
-3Wcm
-3, then add fast 30g to 100g water, continue ultrasonic, stirred 1 hour, filter, washing, drying obtains the high-quality HMX fine particle of 14.5g product (seeing accompanying drawing 3), crystalline density 1.9018gcm
-3, density distribution 1.9010gcm
-3To 1.9021gcm
-3, median size 10 μ m to 30 μ m, size-grade distribution is normal distribution.
The ultrasonic dilution crystallization of embodiment 4:PETN
At room temperature, the 100g ethyl acetate is added in ultrasonic crystallizer, add while stirring 6g common PET N under 20 ℃, until completely dissolved, start ultrasonic field, ultrasonic field frequency 68kHz, the ultrasonic field power density is greater than 1 * 10
-3Wcm
-3, then add fast 100 trichloromethanes, continue ultrasonic, stirred 1 hour, filter, washing, drying obtains the high-quality PETN of 4.5g, crystalline density 1.7685gcm
-3, density distribution 1.7673gcm
-3To 1.7694gcm
-3, median size 25 μ m, size-grade distribution is normal distribution.
Claims (2)
1. high-quality energetic crystal material fine particles preparation method is characterized in that through following steps:
(1) common containing can be dissolved in formation saturated crystallization solution in optimum solvent by crystalline material;
(2) under ultrasonication, add poor solvent to crystallization solution while stirring, the mass ratio of poor solvent and optimum solvent is greater than 1;
(3) ultrasonic, stir certain hour after, filter, washing, drying obtains the high-quality energetic crystal material fine particles product;
Described ultrasonic frequency is 20kHz to 100kHz;
Ultrasonic power density is greater than 1 * 10
-3Wcm
-3
Described ultrasonic, stir after 1 hour and filter, washing, drying.
2. high-quality energetic crystal material fine particles preparation method according to claim 1 is characterized in that: can comprise PETN, RDX, HMX, CL-20, FOX-7 and AP by crystalline material described containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110160871 CN102320903B (en) | 2011-06-16 | 2011-06-16 | Method for preparing high-quality energetic crystal material fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110160871 CN102320903B (en) | 2011-06-16 | 2011-06-16 | Method for preparing high-quality energetic crystal material fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102320903A CN102320903A (en) | 2012-01-18 |
| CN102320903B true CN102320903B (en) | 2013-11-06 |
Family
ID=45448776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110160871 Active CN102320903B (en) | 2011-06-16 | 2011-06-16 | Method for preparing high-quality energetic crystal material fine particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102320903B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2496756C1 (en) * | 2012-02-21 | 2013-10-27 | Федеральное государственное унитарное предприятие "Специальное конструкторско-технологическое бюро "Технолог" | Low-sensitive explosive compound for electric detonator charging |
| CN102924396B (en) * | 2012-10-25 | 2013-11-27 | 中国工程物理研究院化工材料研究所 | Method for crystal transformation from alpha-HMX to beta-HMX |
| CN103012299B (en) * | 2012-12-27 | 2015-01-14 | 中国工程物理研究院化工材料研究所 | HMX preparation method based on DMSO/H20 (Dimethyl Sulfoxide/H2O) binary system |
| CN103360185B (en) * | 2013-03-28 | 2016-03-09 | 北京理工大学 | A kind of round and smooth treatment unit of CL-20 particle and slip processing method |
| CN103172476A (en) * | 2013-04-08 | 2013-06-26 | 中国工程物理研究院化工材料研究所 | Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive |
| CN103588719B (en) * | 2013-11-25 | 2016-03-23 | 中国工程物理研究院化工材料研究所 | A kind of octogen and dimethyl sulfoxide (DMSO) complex compound and preparation method thereof |
| CN103936534B (en) * | 2014-05-09 | 2016-07-06 | 北京理工大学 | A kind of speciality Superfine HMX crystal and preparation method |
| CN104294366B (en) * | 2014-10-11 | 2017-01-18 | 中北大学 | Cultivation method of centimeter-level HMX monocrystals |
| CN105253857B (en) * | 2015-09-29 | 2017-10-24 | 南京工业大学 | A kind of method for preparing fine ammonium perchlorate |
| CN106518883B (en) * | 2016-10-12 | 2018-12-25 | 中国工程物理研究院化工材料研究所 | Six azepine isoamyl of nanometer ε crystal form hexanitro hereby alkane explosive and its batch preparation |
| CN107602311A (en) * | 2017-10-09 | 2018-01-19 | 西安近代化学研究所 | A kind of insensitive mixed crystal composite of high energy |
| CN109053620B (en) * | 2018-09-05 | 2022-03-15 | 西安近代化学研究所 | DNTF with low shock wave sensitivity and preparation method thereof |
| CN110698350A (en) * | 2019-11-18 | 2020-01-17 | 中北大学 | Method for preparing spherical 1,1-diamino-2,2-dinitroethylene crystal by ultrasonic wave assistance |
| RU2768622C1 (en) * | 2021-07-05 | 2022-03-24 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of increasing detonation ability of secondary explosive materials |
| CN114230534B (en) * | 2021-11-23 | 2023-11-24 | 中北大学 | Method for preparing black soxhlet spherulites by acoustic resonance auxiliary solvent erosion technology |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3222231A (en) * | 1962-09-18 | 1965-12-07 | Atlantic Res Corp | Process for producing finely divided rounded particles |
| CN1125215A (en) * | 1995-05-30 | 1996-06-26 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| CA2299891A1 (en) * | 1999-03-02 | 2000-09-02 | Aerospace Propulsion Products B.V. | Process for the production of crystalline energetic materials |
| US6841016B1 (en) * | 2000-03-02 | 2005-01-11 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process for the production of crystalline energetic materials |
| NO20071891L (en) * | 2006-04-13 | 2007-10-15 | Saint Louis Inst | Device for painting the volume of particles for buoyancy |
| CN101863725A (en) * | 2010-06-10 | 2010-10-20 | 南京师范大学 | Method for preparing nano catalytic composite materials by utilizing integrating process of ultrasonic-film-anti-solvent method |
| CN101955469A (en) * | 2010-09-17 | 2011-01-26 | 北京理工大学 | Separation method of mixture of HMX and RDX |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040216822A1 (en) * | 2001-07-03 | 2004-11-04 | Heinz Hofmann | Process for the production of a pressed insensitive explosive mixture |
-
2011
- 2011-06-16 CN CN 201110160871 patent/CN102320903B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3222231A (en) * | 1962-09-18 | 1965-12-07 | Atlantic Res Corp | Process for producing finely divided rounded particles |
| CN1125215A (en) * | 1995-05-30 | 1996-06-26 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| CA2299891A1 (en) * | 1999-03-02 | 2000-09-02 | Aerospace Propulsion Products B.V. | Process for the production of crystalline energetic materials |
| US6841016B1 (en) * | 2000-03-02 | 2005-01-11 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process for the production of crystalline energetic materials |
| NO20071891L (en) * | 2006-04-13 | 2007-10-15 | Saint Louis Inst | Device for painting the volume of particles for buoyancy |
| CN101863725A (en) * | 2010-06-10 | 2010-10-20 | 南京师范大学 | Method for preparing nano catalytic composite materials by utilizing integrating process of ultrasonic-film-anti-solvent method |
| CN101955469A (en) * | 2010-09-17 | 2011-01-26 | 北京理工大学 | Separation method of mixture of HMX and RDX |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102320903A (en) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102320903B (en) | Method for preparing high-quality energetic crystal material fine particles | |
| CN102230227B (en) | Method for preparing high-quality fine granules of energy-containing crystal material | |
| CN103012299B (en) | HMX preparation method based on DMSO/H20 (Dimethyl Sulfoxide/H2O) binary system | |
| CN110590565B (en) | Preparation method of highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal | |
| EP3476840B1 (en) | Method for purifying crude 2,5-furandicarboxylic acid by crystallization | |
| Xu et al. | Phase stability of ammonium nitrate with organic potassium salts | |
| CN114149295A (en) | Coated molecular perovskite energetic material and preparation method thereof | |
| Vijayalakshmi et al. | Particle Size Management Studies on Spherical 3‐Nitro‐1, 2, 4‐triazol‐5‐one | |
| CN111689821A (en) | Activated boron powder and preparation method thereof | |
| CN103641669B (en) | Prepared by a kind of phase stable ammonium nitrate organic additive and phase stable ammonium nitrate thereof | |
| EP1799655A1 (en) | Melamine cyanurate in crystalline form | |
| CN105418619A (en) | Special hexanitrohexaazaisowurtzitane preparation method | |
| CN108623499B (en) | Crystallization method for preparing triaminoguanidine nitrate crystal with narrow particle size distribution and triaminoguanidine nitrate crystal | |
| CN101979384B (en) | Method for preparing sphericized hexogen by nitric acid corrosion | |
| JPS62258343A (en) | Independent particulate beta-crystal tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)-methane and production thereof | |
| JP5993241B2 (en) | Manufacturing method of RDX | |
| CN102010379B (en) | Method for producing hexogen | |
| CN103497070A (en) | Method for spheroidizing hexanitrohexaazaisowurtzitane (HNIW) explosive | |
| JP2009051692A (en) | Polyhedral rdx, method for making rdx polyhedral and method for producing spherical rdx | |
| RU2281931C1 (en) | High-dispersed octanite preparation method | |
| CN102807408A (en) | Earing fertilizer special for rice and production method thereof | |
| CN116041352A (en) | Preparation method of dinitroglycoluril | |
| CN111138236A (en) | 1,2, 4-triazole nitrate coated boron-magnesium composite metal powder fuel and preparation method thereof | |
| CN103694183A (en) | Multi-nitrogen compounds and synthesis methods thereof | |
| CN105440037A (en) | Preparation method for 1,4,5,8-tetranitro-1,4,5,8-tetraazabicyclo[4.4.0]decane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |