CN101585744B - Supercritical fluid technology coating modifying technique of ammonium nitrate - Google Patents
Supercritical fluid technology coating modifying technique of ammonium nitrate Download PDFInfo
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- CN101585744B CN101585744B CN2009100745371A CN200910074537A CN101585744B CN 101585744 B CN101585744 B CN 101585744B CN 2009100745371 A CN2009100745371 A CN 2009100745371A CN 200910074537 A CN200910074537 A CN 200910074537A CN 101585744 B CN101585744 B CN 101585744B
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- ammonium nitrate
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention relates to a supercritical fluid technology coating modifying technique of ammonium nitrate, and particularly to a supercritical fluid technology coating modifying technique of ammonium nitrate. The invention settles the problem of superfine ammonium nitrate coating existing in the prior art. The method is that the ammonium nitrate and the acetone are mixed and grinded so that the grain diameter of the ammonium nitrate is 2-10 mu m. The grinded ammonium nitrate and 10% of acetone nitrocellulose solution are prepared to a suspension and placed into a high-pressure deposition deposition kettle. Then the carbon diode is introduced as an antisolven for inter-dissolving with the acetone. The nitrocotton recrystallizes, separates out and precipitates on the surface of ammonium nitrate particle. Finally the particle with the grain diameter of 2-15 mu m is obtained. The extraction temperature of the high-pressure kettle is 30-32 DEG C. The constant-pressure extraction pressure is 9-11 Mpa. The product prepared by the technique of the invention has the advantages of no conglobation, no agglomeration, and remarkably reduced hygroscopicity.
Description
Technical field
The present invention relates to a kind of supercritical fluid technology cladding applications technology, be specially a kind of supercritical fluid technology coating modifying technique of an ammonium nitrate.
Background technology
An ammonium nitrate (AN) is one of most widely used chemical fertilizer, also is topmost main body composition in the industrial explosive, and in national defense industry, an ammonium nitrate is the good oxygenant of propelling agent, and it is widely used, and demand is huge.AN is used for propelling agent, has low signature, advantage such as cheap and safe in utilization.Because ultra-fine AN more helps the thorough mixing with other composition, the contact probability of improvement and other component, thereby can significantly improve the combustion explosion characteristic, improve stress efficacy.Ultra-fine AN will obtain widespread use future in civilian emulsion [explosive and microemulsified explosive and military propellants.
Yet no matter at national defence or civil area, an outstanding problem that perplexs people for a long time is the strong water absorbability and the anti-caking of an ammonium nitrate, has had a strong impact on its storage and use properties.For a long time, domestic and international many scientific and technical personnel are devoted to head it off, have taked several different methods and technological approaches, as adding hydrophobic material, anti-caking agent, pigment dyestuff, tensio-active agent and carrying out surface coating modification etc.As being directed against the application of AN in propelling agent; Open the outstanding person and adopt silane coupling A N-Si, surfactant A N-NH and polyvinyl butyral acetal respectively; Through spray-dired method AN is carried out micro encapsulation; Rate of moisture absorption after the modification has decline in various degree, and behind the 8h, rate of moisture absorption descends 62%, 64%, 6.1% respectively.(Zhang Jie; Yang Rongjie. the Study on Surface of micro encapsulation an ammonium nitrate (J). energetic material, 2004,12 (1): 1-5.) utilization such as Ye Zhiwen Gemini tensio-active agent, DTAB tensio-active agent; Through decompression crystallization processes modification AN; Behind the 8h than the rate of moisture absorption of common AN reduce about 50%-60% (particle diameter is 450-600 μ m) (the bright .Gemini tensio-active agent of Liu ancestral is to Modification of Ammonium Nitrate research (J) for Ye Zhiwen, Lv Chunxu. chemical circulating a notice of; 2004,67 (4): 1-6.Science and Technology).Shuichi Terada etc. is coated on AN surface (Shuichi Terada with PVA and ethyl cellulose; Makoto Kohga.Burning characteristicsof AN based composite propellant using AN coated with polymer.Science andTechnology of Energetic Material.Vol.64; No.1 (329); 2003.); YutakaHagihara sneaks into AN with 7% HTPB and urethane plastic; To reduce its water absorbability, the result produces detrimentally affect (Yutaka Hagihara.Ammonium nitrate rocket propellant.The Explosives and Weapons Forum.December, 2004.) to the combustioncharacteristics of AN compositepropellent; R.S.Damse has studied the water absorbability of material modification AN such as mineral jelly, metatitanic acid dioctyl ester, DNT, beeswax, and wherein the former effect is better relatively.Although obtained some progress in this regard; But the moisture absorption agglomeration problems of AN still is a headachy problem (R.S.Damse.Waterproofing Materials for Ammonium Nitrate.HighEnergy Materials Research Laboratory, Pune-411 021.www.drdo.com/pub/dsj/oct04/abstract.htm).For example add additive and be fit to for civilian chemical fertilizer, but for explosive and propelling agent because the blended homogeneity is wayward, and the adding of inert material certainly will influence its combustion explosion performance, obviously is inapplicable.The coating technology that some are traditional; Like spray-drying process and centrifugal coating technology and the patent No. is the 03817579.7 resin-coated technology put down in writing, is 200710070187.2 records also there is complex process in an ammonium nitrate, is prone to reunion and problem such as seriously polluted with oil film coating technology etc. with number of patent application.
Especially for the coating of ultra-fine AN, also there is not a kind of effective technological approaches at present.Supercutical fluid (SCF) have good flow, transmission and dissolution characteristics, especially SC CO
2Also have unreactiveness, its technology is simple, solvent and fluid medium are reusable.It is one of operative orientation of present technician that supercutical fluid is applied to the particulate coating, and studying more process at present has anti-solvent method of gas (GAS) and using supercritical fluid quick expansion method (RESS) etc.Elvassore utilizes supercritical CO
2Polymer overmold at protein surface; Obtain micro-capsule diameter 1-5 μ m (Elvassore N; Bertucco A, CalicetiP.Production of Protein Polymer Micro-Capsules by SupercriticalAnti-Solvent Techniques.Proceedings of the 5th InternationalSymposium on Supercritical Fluids.8-12 April.Atlanta (USA), 2000.).Adopt at present this technique means that pyrotechnic composition are coated and verify should technology on coated explosive, whether to have feasibility and do not see that also report is arranged.
Summary of the invention
The present invention provides a kind of supercritical fluid technology coating modifying technique of an ammonium nitrate for the problem that solves the ultra-fine an ammonium nitrate coating that exists in the prior art.
The present invention is realized by following technical scheme; A kind of supercritical fluid technology coating modifying technique of an ammonium nitrate; Method is an ammonium nitrate to be mixed with acetone adopt mechanical milling method to grind to make an ammonium nitrate particle diameter be 2-10 μ m; The acetone nitrocellulose solution of ground an ammonium nitrate and 10% is processed suspension-s, place high pressure deposition still; Feeding carbonic acid gas then dissolves each other as anti-solvent and acetone; Cause that the solute nitro-cotton that is dissolved in wherein produces degree of supersaturation; Acetone is taken away in extraction through constant temperature and pressure, and the ammonium nitrate granule surface is separated out and be deposited in to the nitro-cotton recrystallization, obtains the particle that particle diameter is 2-15 μ m at last; 30-32 ℃ of autoclave extraction temperature, constant voltage extracting pressure 9-11Mpa.
Fig. 1 is seen in device that the coating process is used and flow process signal.Adopt supercritical CO
2Anti-solvent method can be realized the good coating of ultra-fine AN, and the product of preparation is not reunited, do not lumpd, water absorbability significantly reduces.AN sample before getting a certain amount of particle diameter 2-15 μ m modification AN respectively and coating under room temperature (20 ℃), is put into the environment of relative humidity 90%, and certain hour takes by weighing its quality at interval.The result sees table 1, and rate of moisture absorption (particle diameter 2-15 μ m) reduces about 50% (12h) than the rate of moisture absorption that does not coat, and modified effect is obvious, and free-running property significantly improves.The SEM of coating modification sample sees Fig. 2.
The water absorbability of table 1 particle diameter 2-15 μ m modified ammonium nitrate
An ammonium nitrate has 5 kinds of thermodynamically stable crystalline structure, and each structure exists in certain TR, along with each crystal formation of temperature variation changes, and this one of major reason of its caking just.This operates in temperature is to carry out under 31 ℃, guarantees the TR of coating process 32.3～16.9 ℃ of the rhombic systems of an ammonium nitrate, does not have the brilliant process of changeing.Sample free-running property after having guaranteed to coat is good, no caking phenomenon.
This invention is primarily aimed at civilian emulsion [explosive and the required ultra-fine AN of military propellants prepares and overcritical coating modification, and achievement in research also can be applicable to the modification of other commercial explosives and chemical fertilizer.
Description of drawings
Fig. 1 is implementation process using appts of the present invention and schematic flow sheet
Fig. 2 is modified ammonium nitrate sample SEM figure
Embodiment
Embodiment 1, and a kind of supercritical fluid technology coating modifying technique of an ammonium nitrate mixes (mass ratio 1: 0.8) with a certain amount of AN and carries out airtight grinding with acetone, and behind the 10min, the particle diameter of AN is 2-10 μ m.
The coating process adopts the supercritical fluid anti-solvent process, utilizes supercritical extraction unit.Process is divided into: the expansion of coating solution, the extraction of solvent, coating are at AN surperficial deposition, solvent and CO
2Separation, specifically be to be that 10% acetone nitrocellulose solution is processed suspension-s (mass ratio of an ammonium nitrate and nitro-cotton is 99: 1) with ground an ammonium nitrate and massfraction, place high pressure deposition still; Feed carbonic acid gas then as anti-solvent; Rapid and acetone dissolves each other, and causes that the solute nitro-cotton that is dissolved in wherein produces certain degree of supersaturation, and acetone is taken away in extraction through constant temperature and pressure; The ammonium nitrate granule surface is separated out and be deposited in to the nitro-cotton recrystallization; Obtain the particle that particle diameter is 2-15 μ m at last, 31 ℃ of autoclave extraction temperature, constant voltage extracting pressure 10Mpa.
Meaning as shown in Figure 1, the fine porosity sintered sheets all is equipped with in the top and the bottom of high pressure deposition still 2, and material was pulled away when the top sintered sheets prevented to discharge, and the bottom sintered sheets plays CO
2Spreader plate and the effect of carrying material; CO by pressure liquid pump 1 pressurization
2Add acetone nitro-cotton suspension-s 3 from the bottom, not only can play stirring, accelerate the effect of system's heat and mass efficient, and make the abundant suspended dispersed of material.Pressure in the autoclave is measured with precision pressure gauge, and temperature is controlled by an automatic temp control unit.The upper valve rate of release is kept watch on by spinner-type flowmeter, ensures that flow velocity is moderate, stable.
The supercritical fluid technology coating modifying technique of embodiment 3, a kind of an ammonium nitrate; An ammonium nitrate mixed with acetone adopt mechanical milling method to grind to make an ammonium nitrate particle diameter be 2-10 μ m; The acetone nitrocellulose solution of ground an ammonium nitrate and 10% is processed suspension-s (mass ratio of an ammonium nitrate and nitro-cotton is 100: 1), place high pressure deposition still; Feed carbonic acid gas then as anti-solvent; Rapid and acetone dissolves each other, and causes that the solute nitro-cotton that is dissolved in wherein produces certain degree of supersaturation, and acetone is taken away in extraction through constant temperature and pressure; The ammonium nitrate granule surface is separated out and be deposited in to the nitro-cotton recrystallization; Obtain the particle that particle diameter is 2-15 μ m at last, 30 ℃ of autoclave extraction temperature, constant voltage extracting pressure 11Mpa.
Claims (2)
1. the supercritical fluid technology coating modifying technique of an an ammonium nitrate; It is characterized in that: an ammonium nitrate is mixed with acetone adopt mechanical milling method to grind to make an ammonium nitrate particle diameter be 2-10 μ m; With ground an ammonium nitrate and massfraction is that 10% acetone nitrocellulose solution is processed suspension-s, places high pressure deposition still; Feeding carbonic acid gas then dissolves each other as anti-solvent and acetone; Cause that the solute nitro-cotton that is dissolved in wherein produces degree of supersaturation; Acetone is taken away in extraction through constant temperature and pressure, and the ammonium nitrate granule surface is separated out and be deposited in to the nitro-cotton recrystallization, obtains the particle that particle diameter is 2-15 μ m at last; 30-32 ℃ of autoclave extraction temperature, constant voltage extracting pressure 9-11MPa.
2. the supercritical fluid technology coating modifying technique of an ammonium nitrate according to claim 1 is characterized in that: 31 ℃ of autoclave extraction temperature, constant voltage extracting pressure 10MPa.
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| CN104829856B (en) * | 2015-05-14 | 2018-03-27 | 贵州省材料产业技术研究院 | The method that critical carbon dioxide wraps epoxy resin layer in microsphere surface |
| CN106431798A (en) * | 2016-09-19 | 2017-02-22 | 南京理工大学 | Gas expanding agent and application thereof |
| CN106519265B (en) * | 2016-11-28 | 2019-03-05 | 中北大学 | A kind of preparation method of micron order nitrocotton ball |
| CN110283012A (en) * | 2019-06-13 | 2019-09-27 | 徐悦阳 | A kind of Pesticidal and sterilizing organic fertilizer and preparation method thereof |
| CN110357703A (en) * | 2019-06-13 | 2019-10-22 | 徐悦阳 | A kind of Slow-release organic fertilizer and preparation method thereof |
| CN113816814B (en) * | 2021-10-13 | 2023-05-09 | 西南科技大学 | Preparation method of high-energy insensitive aluminum-containing explosive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036194C (en) * | 1995-05-30 | 1997-10-22 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| CN2736356Y (en) * | 2004-08-30 | 2005-10-26 | 龙文革 | Novel oxidizing agent particles for fireworks and firecrackers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036194C (en) * | 1995-05-30 | 1997-10-22 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| CN2736356Y (en) * | 2004-08-30 | 2005-10-26 | 龙文革 | Novel oxidizing agent particles for fireworks and firecrackers |
Non-Patent Citations (1)
| Title |
|---|
| 张树海等.硝胺炸药的超临界溶液快速膨胀包覆技术研究.《火工品》.2004,(第2期),20-23，26. * |
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