CN101844954B - Microporous smokeless firework explosive and preparation method thereof - Google Patents
Microporous smokeless firework explosive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses microporous smokeless firework explosive and a preparation method thereof. The preparation method comprises the following steps of: dissolving scrapped military smokeless explosive containing nitrated cellulose into a solvent to form macromolecular sol, emulsifying and foaming the sol to form paint emulsion, dispersing the paint emulsion into a non-solvent medium under stirring action to form balls, then driving the solvent, separating the materials, and drying the materials to obtain explosive particles with microporous structures on the inner part for emitting and dissecting fireworks. The smokeless firework explosive has high fire transfer rate and adjustable stacking density and particle size because of a large amount of microporous structures on the inner part, the appearance of the microporous smokeless firework explosive is approximately spherical or oblate, the particle size is controllable, the stacking density is 0.05 to 0.4 g/cm<3>, and the aperture of the inner part is 0.01 to 500 microns in variety.
Description
Technical field
The invention belongs to fireworks propelling charge and fireworks display and flick bud technology, particularly a kind of microporous smokeless firework explosive and preparation method thereof.
Background technology
China has not only reduced the storage and the processing costs of useless gunpowder having obtained many achievements aspect the safe handling of useless gunpowder and the recycling in recent years, can also bring remarkable social benefit and economic benefit.The part single-base gun propellant is applied to the commercial explosives aspect; Utilizing method mainly is that useless gunpowder is dosed in the explosive through after the mechanical disintegration; The over-all properties that improves explosive also can reduce cost, but this mode of utilizing is limited to the performance boost of explosive, and capacity usage ratio is also not too high.Therefore, how more effectively the recycling of Containing Waste Propellant is had great importance for aspects such as public safety, environment protection.
Up to the present, the military smokeless powder that will scrap is will scrap military smokeless powder earlier to carry out pulverization process as fireworks propelling charge main method, then through mixing with other materials or being mixed for the fireworks propelling charge with black powder.In the time of will scrapping military smokeless powder powder with black powder mixing use, can not solve the big problem of amount of smoke.Chinese patent CN1526687 discloses a kind of fireworks and has used the smokeless propellant agent; Form by Containing Waste Propellant powder, oxygenant and combustiblematerials; Wherein the mass percent of Containing Waste Propellant powder is 70-90%; Its preparation technology is fairly simple, but its apparent combustion speed ratio is lower, and combustion completion and over-all properties are not ideal enough.CN1431181 discloses a kind of fireworks with smokeless propellant and preparation method thereof; Also be to adopt the expired rifle of scrapping, shell to use single-base powder to be main raw material; The ammonium dichromate and the charcoal that add certain component; Through being ground into 120 order fine powders, use smokeless propellant thereby can be mixed and made into the microgranular fireworks of 1-1.5mm.The gunpowder that will give up is pulverized and aspect fireworks, is used, because apparent combustion speed and fire transmission rate are on the low side, result of use was not ideal enough aspect fireworks when granularity was too big; The gunpowder that will give up directly is crushed to below 100 orders and can increases the ratio of combustion surface-area, but it is bigger to pulverize difficulty, and production efficiency is lower, still has defectives such as the fast and fire transmission rate of apparent combustion is on the low side in addition, comprehensively the replace black gunpowder; In addition, contain the chromium element in the prescription and can cause certain harm environment.
USP 3824108 discloses a kind of manufacturing low density soluble cotton particulate method, and the medicine grain tap density that obtains is at 0.4-0.6g/cm
3Between; Its main process contains stablizer, water and nitrocellulosic lacquer shape material for preparation earlier; To coat with lacquer the shape material then and be distributed in the solution that contains protection glue and basic metal or alkaline earth salt and form spherical droplets, further reduce stirring velocity, make the material reunion; The solution that adds protection glue and basic metal or alkaline earth salt once more makes material be dispersed into spherical droplets, obtains final particle through processes such as solvent expelings then.This method is to carry out to containing nitrocellulosic gunpowder system, and the medicine grain tap density that obtains is at 0.4-0.6g/cm
3, its rate of combustion is lower, and to fire fast difference big with black powder, is not suitable for the luxuriant medicine of opening as fireworks propelling charge medicine and display shell.
Summary of the invention
The object of the present invention is to provide biography that a kind of inside has a large amount of micro hole constructions adjustable smoke less fire cracker medicine of rate height and tap density and particle size and preparation method thereof at top speed.
The technical scheme that realizes the object of the invention is: a kind of microporous smokeless firework explosive; By following steps preparations and get: will contain and nitrocellulosicly scrap military smokeless powder and be dissolved into and form polymeric sol in the solvent; Form lacquer shape emulsion through emulsion foam again; And under stirring action, will coat with lacquer the balling-up in the non-solvent medium of shape emulsion dispersion, then through obtain after solvent expeling, feed separation, the oven dry inside have micro-pore structure as the fireworks emission and open the medicine grain of luxuriant usefulness.
The present invention compared with prior art, its remarkable advantage is: the microporous smokeless firework explosive profile of (1) the present invention preparation is similar to spherical or the oblate spheroid shape, and the globule size controlled bulk density is at 0.05g.cm
-3-0.4g.cm
-3, does not wait to 500 μ m from 0.01 μ m in inner aperture, and the particle size range of medicine grain mainly concentrates on 100 μ m-3000 μ m.With adopt mechanical disintegration to handle the smoke less fire cracker medicine that obtains to compare, normal pressure passes at top speed that rate and apparent combustion speed significantly improve, increase rate can reach 1-100 doubly not to be waited, it passes at top speed rate or apparent combustion speed more approaches black powder.(2) this smoke less fire cracker propelling charge both can be used for doing spraying decoration, ground fireworks display and display shell propelling charge; Also can be used for the luxuriant medicine of opening of display shell; Can be all for traditional black powder; Dosage is far below traditional black powder explosive load, reduces the generation of smog significantly and helps improving the safety performance of firework product.Be that microporous smokeless firework explosive directly substitutes the used black powder of ground fireworks display and display shell as propelling charge; When consumption is merely the 20%-50% of original-pack black powder amount its firing altitude just with former powder charge quite or to be higher than original-pack liquid medicine flat; The amount of smoke of emission process generation also reduces significantly in addition, and is as shown in Figure 4, and Fig. 4 is for adopting 1.5 cun ground fireworks display cartridge cases; Adorn black powder and smoke less fire cracker medicine smoke condition comparison diagram respectively in the T-time; Left figure powder charge is a black powder, and right figure powder charge is the smoke less fire cracker medicine, and the firing altitude of effect medicine inner core is identical; Smoke less fire cracker medicine explosive load is 1/3 of a black powder, can find out and adopt the smoke less fire cracker medicine to descend significantly in the amount of smoke that emission process produces.As display shell open luxuriant medicine the time, when consumption is merely the 20%-50% of black powder, open the effect that luxuriant diameter just can meet or exceed former powder charge; Amount of smoke also significantly reduces in addition, and like Fig. 5, shown in Figure 6, Fig. 6 is for adopting 2.5 cun display shells; Adorn black powder and smoke less fire cracker medicine respectively and blasting the smoke condition comparison diagram of moment; Left figure powder charge is a black powder, and right figure powder charge is the smoke less fire cracker medicine, and smoke less fire cracker medicine explosive load is 1/3 of a black powder; The blast fragment with open luxuriant diameter basically identical, can find out and adopt the smoke less fire cracker medicine to descend significantly in the amount of smoke that the process that blasts produces.(3) preparation method accomplishes under agitation condition as shaping medium at water and solvent, and whole moulding process can be accomplished in same device; Said preparation method helps obtaining higher biography rate or apparent combustion speed at top speed; And the tap density of globule size and material and apparent combustion speed are adjusted in a big way; Thereby be applicable to the fireworks medicine of various uses, comprise that spraying decoration, ground fireworks display propelling charge and the fireworks display of different size flick luxuriant medication.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is a microporous smokeless firework explosive preparation method process synoptic diagram of the present invention.
Fig. 2 is sample appearance and the internal pore structure SEM figure that embodiment 1 obtains.
Fig. 3 is sample appearance and the internal pore structure SEM figure that embodiment 2 obtains.
Fig. 4 adopts 1.5 cun ground fireworks display cartridge cases, adorns black powder and smoke less fire cracker medicine respectively at the smoke condition comparison diagram of T-time, and left figure powder charge is a black powder, and right figure powder charge is the smoke less fire cracker medicine.
Fig. 5 adorns black powder and the smoke less fire cracker medicine outward appearance comparison diagram before blasting respectively for adopting 2.5 cun display shells, and left figure powder charge is a black powder, and right figure powder charge is the smoke less fire cracker medicine.
Fig. 6 adorns black powder and smoke less fire cracker medicine respectively and is blasting the smoke condition comparison diagram of moment for adopting 2.5 cun display shells, and left figure powder charge is a black powder, and right figure powder charge is the smoke less fire cracker medicine.
Embodiment
Microporous smokeless firework explosive of the present invention, will contain nitrocellulosic scrap inside that military smokeless powder dissolving, emulsion foam, balling-up, solvent expeling, feed separation, oven dry obtain have micro-pore structure as the fireworks emission and open the medicine grain of luxuriant usefulness.Resulting fireworks medicine inside has a large amount of tiny holes, and its biography under normal pressure rate or apparent combustion speed at top speed more approaches black powder, can replacing whole ground fireworks display and the used black powder of display shell, also can flick luxuriant used black powder by the replacing whole fireworks display.Used raw material is for scrapping military smokeless powder; It can be the retired nitrocellulosic military smokeless powder that contains; Or the course of processing scrap contain nitrocellulosic military smokeless powder; Both can be virgin state or through break process, can also directly adopt the gunpowder of scrapping of the safe condition that contains large quantity of moisture.Describedly scrap military smokeless powder and comprise single-base powder, double-base powder and triple base propellant, the single-base powder staple is auxiliary components such as soluble cotton and a spot of tranquilizer; The double-base powder staple is soluble cotton and soup; The triple base propellant staple is compositions such as soluble cotton soup and nitroguanidine.
The present invention provides a kind of preparation method of microporous smokeless firework explosive, and this preparation method can prepare and contain nitrocellulosic biography rate height and tap density and the adjustable smoke less fire cracker medicine of particle size at top speed.
In conjunction with Fig. 1; The preparation method of microporous smokeless firework explosive of the present invention; To contain and nitrocellulosicly scrap military smokeless powder and be dissolved into and form polymeric sol in the solvent; Form lacquer shape emulsion through emulsion foam again, and under stirring action, will coat with lacquer the balling-up in the non-solvent medium of shape emulsion dispersion, pass through the smoke less fire cracker medicine that obtains having micro-pore structure after solvent expeling, feed separation, the oven dry then.
Wherein, microporous smokeless firework explosive preparation method detailed process of the present invention is following:
(1) material dissolution: at first, will contain the nitrocellulosic military smokeless powder of scrapping and join in material dissolution groove or the balling-up reactor drum, the 3-15 solvent doubly that adds the bulk drug quality carries out material dissolution.Under whipped state, bulk drug adopts solvent dispersion and dissolving to form polymeric sol in molding device.In the military smokeless powder of scrapping, add before the solvent, can add a spot of water earlier or the aqueous solution disperses, reunite and on wall, bond to prevent material, the ratio that institute adds the water or the aqueous solution is 0-2 times of useless gunpowder quality.Solvent for use can be a kind of in ETHYLE ACETATE, butylacetate, acetone, butanone, ethanol, the methyl alcohol or several mixture, preferably select for use to bulk drug have good solubility can solvent; The material dissolution time confirms that according to raw material type and particle size dissolution time is 10-180min under room temperature or heating condition, is preferably 20-90min; Solvent temperature is confirmed according to used solvent species, should not be higher than the azeotropic point of the boiling point or the mixed solvent of solvent; When adopting ETHYLE ACETATE to make solvent, solvent temperature is preferably at the 40-68 degree, and the 50-65 degree is better; The dissolution process of material also can not add the water or the aqueous solution and directly adopt dissolution with solvents.The adding of material dissolution process bulk drug and solvent can once add or repeatedly add in batches, can adopt independent dissolver batch process in addition or prepare continuously to contain the polymeric sol of scrapping military smokeless powder.
(2) emulsion foam: an amount of water or the aqueous solution evenly spread to contain carry out emulsion foam in the nitrocellulosic sol system and handle.Said emulsion foam process can be accomplished in the balling-up reactor drum; Said balling-up reactor drum is the reactor drum of general installation anchor formula, oar blade type or spiral stirring rake; Stirring rake can also adopt other patterns, and the stirring velocity in the emulsion foam process is confirmed according to the volume of balling-up reactor drum and the type of agitating vane.In the emulsion foam process; Under whipped state, in polymeric sol, add an amount of water or the aqueous solution; Can add proper amount of surfactant in the said aqueous solution as emulsification foaming agent or foam stabilizer; To guarantee that material disperses and the emulsion foam state is more even, said tensio-active agent can be a non-ionics, like TX10; Can also be aniorfic surfactant, like sodium lauryl sulphate or X 2073 etc.; Can also select cationic surfactant for use, like DTAC, cetyl trimethylammonium bromide etc.The add-on of tensio-active agent confirms that according to its kind add-on is preferably the 0.01%-0.2% of the water yield for adding the 0.01%-0.5% of the water yield usually.The adding of the said water or the aqueous solution can once add or repeatedly add, and can also add continuously.The emulsion foam process joins the aqueous solution in the system, can also be the isolated aqueous solution or mother liquor after balling-up last time.The add-on of the aqueous solution can finished product tap density as required confirm that the tap density that needs is little, and the water-soluble liquid measure that then adds should increase, but the add-on by volume of the aqueous solution is no more than the solvent total amount.Under room temperature or heating condition, carry out emulsion foam, the temperature of heating is not higher than the azeotropic point of the boiling point or the mixed solvent of solvent, and the emulsion foam time is preferably 10min-240min; The temperature of emulsion foam process system is consistent with dissolution process basically; When adopting ETHYLE ACETATE to make solvent, should keep 40 ℃-68 ℃, be preferably 50 ℃-65 ℃.
The emulsion foam process can also be accomplished in emulsifying device, and like various intermittences or continuous emulsifying equipment, material changed over to and carries out the balling-up processing in the balling-up equipment after emulsion foam was accomplished.
(3) balling-up: in system, add suitable quantity of water solution; Contain nitrocellulosic organic phase material dispersion under whipped state because under the acting in conjunction of shearing force and system IT and form spherical droplets; The said aqueous solution can be the aqueous solution that contains dispersion agent; Can also be that medicine grain moulding last time prepares the mother liquor that process reclaims, add an amount of dispersion agent in the aqueous solution spherical droplets is protected.The amount that the aqueous solution or mother liquor add is 2-10 a times of bulk drug quality, and preferably 2-8 doubly can disposablely add, and also can add in batches.Dispersion agent can also directly be added in the system in the balling-up process.The kind of dispersion agent can be selected water-soluble natural polymers such as gelatin, gelatine, gum arabic for use, also can select water-soluble synthetic macromolecules such as polyoxyethylene glycol, SEPIGEL 305, Z 150PH, methylcellulose gum for use.Dispersant dosage is for adding the 0.05%-1% of total usefulness quality.Used time of balling-up process is preferably at 10min-90min; System temperature is consistent with dissolution process basically, when adopting ethyl acetate solvent, keeps 40 ℃-68 ℃, is preferably 50 ℃-65 ℃, and the balling-up process temperature can slowly promote, but should not surpass the boiling point of solvent for use.Stirring velocity is confirmed according to the volume of balling head, the shape of agitating vane and the medicine particle size of needs, needs the finished medicines grain of small particle size under higher stirring velocity, to carry out, otherwise then need under low stirring velocity, carry out.
(4) solvent is driven away: vacuumize under the state at the intensification conditioned disjunction, perhaps distill at the solvent that heats up and vacuumize under the condition progressively the system kind simultaneously.The main operating parameters that said solvent is driven away process is: the time is at 20min-240min, and temperature is along with the recovery of solvent progressively improves, and the azeotropic point of boiling point or solvent and water that surpasses solvent when temperature can stop to drive molten more than 10 ℃ the time more than the maintenance 10min.When adopting ETHYLE ACETATE to make solvent, to dissolve as adopting normal pressure to steam, temperature reaches 85 ℃ and keeps can stopping to drive more than the 10min molten.
(5) feed separation: after solvent is driven away completion; Adopt the general type of cooling that the temperature of system is dropped near room temperature; Or directly adopt common spinning or filtering mode that the aqueous solution is separated with solid particulate, the filtrating of separating is called the balling-up mother liquor, contains a spot of dispersion agent and solvent in the mother liquor; Can be saved in the fixed container when next balling-up as the dispersion medium recycle, also can pass through focusing on the back qualified discharge.
(6) oven dry: the medicine grain that feed separation obtains can adopt conventional mode to dry processing; Used drying plant preferably with warm air, hot water etc. as the heating thermal source; Top temperature is preferably lower than 100 ℃, should not adopt the direct-fired baking oven of naked light and electrothermal tube, to guarantee safety.Also can under the state of vacuumizing, accomplish, vacuum tightness is confirmed according to solvent species.When moisture content is following less than 2%, can stop oven dry.Can also adopt the continuous drying device processes.Relevant drying plant should be furnished with the good anti-static measure to guarantee safety.
(7) aftertreatment: can also carry out size classification, adopt graphite to carry out aftertreatments such as surface luster according to different needs.
The smoke less fire cracker medical instrument that comes out through method for preparing has inner many air hole structures, and does not wait to 500 μ m from 0.01 μ m in the aperture, mainly concentrates on 0.05 μ m-100 mu m range.Profile with the sphere of being similar to or oblate spheroid type can also be flat of circle, nearly oval flat, rectangular flat or other shapes.After normal temperature and atmospheric pressure state are lighted, can't see smog basically and produce, and do not have pollutent such as sulfurous gas.Normal pressure passes rate and apparent combustion speed at top speed and handles the medicine grain that obtain by scrapping military smokeless powder through pulverizing with simple modification far above the same particle sizes scope.
The forming principle of microporous smokeless firework explosive of the present invention is compared with the general spherical shape medicine; Moulding process is broadly divided into material dissolution dispersion, balling-up, drives several steps such as molten; And the emulsion foam process that in the balling-up process, increased by; Make a large amount of small pore of the interior generation of matrix of gunpowder, thereby promoted its combustioncharacteristics significantly; In addition, the moulding process of microporous smokeless firework explosive does not need the link of processed.
The present invention will contain nitrocellulosic material and use organic solvent dissolution; Or in the medium of big water gaging and solvent coexistence, disperse and dissolving and form polymeric sol, with whipping agent and with contain non-solvent medium that nitrocellulosic material not exclusively dissolves each other and utilize stirring means or other modes to carry out emulsion foam to form and coat with lacquer the shape emulsion.Lacquer shape emulsion is dispersed into tiny drop in water medium or in other non-solvent media under the intense shear power effect that mechanical stirring produces.Because the effect of IT, the drip gauge area has the trend of as far as possible dwindling, to reduce surface energy.The material of equal volume, surface-area are minimum with the sphere, so drop is shrunk to sphere the most easily.This system is a thermodynamic instability, and drop was in the dynamic balance state of gathering and redispersion always before typing.Drop has and is gathered into oarse-grained trend automatically, when the drop surface adsorption after the layer of protecting glue, the gathering in the time of can having stoped spheroid to collide each other effectively.
After the balling-up; Through means such as improve temperature, bubbling air or vacuumize, progressively the solvent in the drop to be driven away out, the viscosity of macromolecule material drop also progressively improves; Viscosity increases to and to a certain degree will no longer take place to assemble and redispersion, is promptly changed to elastomeric state by viscous state.Solvent in the particle is driven away in water or in other non-solvent media.Drive when dissolving in the temperature that is lower than solvent boiling point, solvent diffuses in the entry earlier or in the non-solvent medium, from aqueous phase or other non-solvent media, evaporates then under concentration difference promotes in the particle; When driving under the temperature that is being higher than solvent boiling point when dissolving, solvent vapo(u)r directly steams from pellet surface, passes the aqueous solution or non-solvent medium then and discharges.The foaming medium is retained in the medicine body in the process that solvent is driven away after moulding, and the medium that will foam is again at last separated from the medicine body, obtains having the medicine grain of internal microcellular structure.
For implementation process of the present invention is described better, the elaboration of giving an example below, these processes and processing condition are not represented the whole of invention, only otherwise violate other conditions of the present invention and can adopt yet.
Embodiment 1:
Selecting volume for use is that 2 liters glass there-necked flask is as the balling-up reactor drum; Adopting the nitrocotton cellulose content is raw material greater than the basic useless gunpowder of 85% list, through preliminary fragmentation, controls particle diameter and is no more than 2mm; Medicine grain and 1 times of water to drug grain quality that will pass through determination of moisture band water join in the reactor drum; Under whipped state, add 10 times to the ethyl acetate solvent of drug grain quality, stirring and dissolving 50-60min under 45 ℃ of-50 ℃ of temperature, mixing speed remains on 300-350rpm; Under whipped state, carry out emulsion foam operation, the tap water that in 30min, adds in the system continuously, the water yield of adding is 6 times of drug grain quality, after water injection continued continues stirring 60min under 50-60 ℃ of temperature; When then temperature being adjusted to 65 ℃-68 ℃, 8 times of aqueous dispersants that contain to the bulk drug quality are joined balling-up in the system, gelatin is as dispersion agent, and the dispersion agent add-on is 0.5% of a water total amount.Continue to keep 65 ℃-68 ℃ of temperature; And under the mixing speed of 300-350rpm, disperse 30min; Contain nitrocellulosic micelle and progressively be dispersed into spherical drop uniformly; Progressively heating up steams solvent to come lentamente, and ball hardens gradually, keeps and gets final product discharging more than the 10min when temperature is raised to 85 ℃ of continued.Adopt filtering means that ball is separated, at room temperature dry and in the safety baking oven 50 ℃ the oven dry 24 hours, the sample tap density that obtains is 0.15g.cm
-3, profile is spherical, and particle diameter mainly concentrates on 300-1500 μ m, and the outside drawing of sample and internal pore structure situation are as shown in Figure 2.Adopting internal diameter is the paper web of 16mm height 200mm one end sealing; The sample segment of filling 20-40 order size range; Light the biography that obtains of test at top speed rate be 38mm/s; Likewise adopt the single-base powder particle of the same particle size scope after directly pulverizing to compare test, record it and pass at top speed that rate is 7.5mm/s.As can beappreciated from fig. 2, the profile of sample approaches sphere, and a large amount of holes are contained in inside, and the diameter major part that can find out hole from scale connects between the hole below 10 μ m each other.
Embodiment 2
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug; The preparation process is identical with embodiment 1; Only be 6 times that solvent adding amount reduces to drug grain quality, the water yield that the emulsion foam operating process adds reduces to 4 times of drug grain quality, and the sample tap density that obtains is 0.28g.cm
-3, profile is a spheroid, and particle diameter mainly concentrates on 300-2000 μ m, and the outside drawing of sample and internal pore structure situation are as shown in Figure 3.Adopt embodiment 1 used testing method to record it and pass at top speed that rate is 31.4mm/s.As can beappreciated from fig. 3, the profile of sample approaches sphere, and a large amount of holes are contained in inside, and hole yardstick wider distribution, the diameter major part that can find out hole from scale connect between the hole below 50 μ m each other.
Embodiment 3
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug; The preparation process is identical with embodiment 1; Only be 15 times that solvent adding amount reduces to drug grain quality, the water yield that the emulsion foam operating process adds is 12 times of drug grain quality, and the sample tap density that obtains is 0.05g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 300-2000 μ m.Adopt embodiment 1 used testing method to record it and pass at top speed that rate is 58.0mm/s.
Embodiment 4
Adopting the nitrocotton cellulose content is that 58% soup content is that 38% the useless gunpowder of double-basis is a bulk drug; The preparation process is identical with embodiment 1; It only is 3 times that solvent adding amount reduces to drug grain quality; The water yield that the emulsion foam operating process adds is 2 times of drug grain quality, and the sample tap density that obtains is 0.4g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 500-2000 μ m.
Embodiment 5
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug, and the preparation process is identical with embodiment 1, only is 2 times that the water yield of dissolution process adding is increased to drug grain quality, and the sample tap density that obtains is 0.16g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 300-2000 μ m.
Embodiment 6
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug, does not add water at dissolution process, and other preparation processes and condition are identical with embodiment 1, and the sample tap density that obtains is 0.18g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 300-2000 μ m.
Embodiment 7
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug, and the preparation process is identical with embodiment 1, only is the emulsion foam time is shortened to 10min, and the sample tap density that obtains is 0.18g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 300-2000 μ m.
Embodiment 8
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug, and the preparation process is identical with embodiment 1, only is the emulsion foam time lengthening is arrived 240min, and the sample tap density that obtains is 0.16g.cm
-3, profile is a spheroid, particle diameter mainly concentrates on 300-2000 μ m.
Embodiment 9
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug; The preparation process is identical with embodiment 1, and solvent adding amount is 8 times of drug grain quality, and the emulsion foam operating process adds the aqueous solution that contains 0.2% nonionogenic tenside OP-10; Add-on is 5 times of drug grain quality; Dispersion agent adopts gelatine, and adding concentration is 1% of Total Water, and the sample tap density that obtains is 0.16g.cm
-3, profile is oval flat, and particle diameter mainly concentrates on 300-1500 μ m, and thickness concentrates on the 0.1-0.2mm scope.Adopt the testing method described in the embodiment 1 to record it and pass at top speed that rate is 36.5mm/s.
Embodiment 10-16:
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug, and preparation process and embodiment 1 are similar, only are to adopt different material ratios, and change dispersion agent kind and the concentration that the balling-up process is added, and relevant parameter and result see table 1.Solvent all adopts ETHYLE ACETATE; Wherein solvent ratio is the quantity of solvent of adding and the ratio of drug grain quality; The water multiple is for adding the ratio of whole aqueous solution and drug grain quality in the preparation process; Dispersant dosage is the per-cent that add-on accounts for the aqueous solution total amount of adding, the medicine grain that comparison sample obtains for the useless direct pulverization process of gunpowder of single base.
Table 1 embodiment 10-16 significant parameter and result
| Embodiment | Solvent ratio | The water multiple | The dispersion agent kind | Dispersant dosage/% | Mixing speed/rpm | Tap density/(g.cm -3) | Normal pressure fire transmission rate/(mm.s -1) |
| 10 | 8 | 9 | Gelatin | 0.25 | 300 | 0.25 | 32.6 |
| 11 | 8 | 10 | Gum arabic | 0.50 | 300 | 0.23 | 33.8 |
| 12 | 8 | 11 | Polyoxyethylene glycol | 0.50 | 300 | 0.28 | 30.4 |
| 13 | 5 | 5 | Gelatin | 0.25 | 300 | 0.32 | 25.5 |
| 14 | 5 | 6 | Gelatin | 0.50 | 400 | 0.28 | 30.8 |
| 15 | 5 | 6 | Z 150PH | 0.25 | 400 | 0.30 | 28.0 |
| 16 | 5 | 8 | Methylcellulose gum | 0.5 | 400 | 0.25 | 31.9 |
| Comparison sample | 0.78 | 7.5 |
Embodiment 17-20:
Adopting with the embodiment 1 identical useless gunpowder of single base is bulk drug; The preparation process is identical with embodiment 1; Only be to adopt different material ratios, and change kinds of surfactants and the concentration that the emulsion foam process is added, dispersion agent adopts gelatine; Add-on is 0.25% of the water yield, and relevant parameter and result see table 2.Solvent all adopts ETHYLE ACETATE, and wherein solvent ratio is the quantity of solvent that adds and the ratio of drug grain quality, and the water multiple is for adding the ratio of whole aqueous solution and drug grain quality, the medicine grain that comparison sample obtains for the useless direct pulverization process of gunpowder of single base in the preparation process.
Table 2 embodiment 16-19 significant parameter and result
| Embodiment | Solvent ratio | The water multiple | The emulsification foaming agent kind | Emulsification foaming agent consumption/% | Mixing speed/rpm | Tap density/(g.cm -3) |
| 17 | 8 | 10 | OP-10 | 0.1 | 300 | 0.18 |
| 18 | 8 | 10 | Cetyl trimethylammonium bromide | 0.1 | 300 | 0.20 |
| 19 | 8 | 10 | Sodium lauryl sulphate | 0.1 | 300 | 0.22 |
| 20 | 8 | 10 | X 2073 | 0.1 | 300 | 0.22 |
| Comparison sample | 0.78 |
Embodiment 21-24:
Adopt soluble cotton be 56% with soup content be that 26% the useless gunpowder of double-basis is a bulk drug; The preparation process is identical with embodiment 1; Only be to adopt different material ratios, and change dispersion agent kind and the concentration that the balling-up process is added, relevant parameter and result see table 3.Solvent all adopts ETHYLE ACETATE; Wherein solvent ratio is the quantity of solvent of adding and the ratio of drug grain quality; The water multiple is at the aqueous solution total amount of preparation process adding and the ratio of drug grain quality; Dispersant dosage is the per-cent that add-on accounts for the aqueous solution total amount of adding, the medicine grain that comparison sample obtains for the useless direct pulverization process of gunpowder of single base.
Table 3 embodiment 21-24 significant parameter and result
| Embodiment | Solvent ratio | The water multiple | The dispersion agent kind | Dispersant dosage/% | Mixing speed/rpm | Tap density/(g.cm -3) |
| 21 | 5 | 5 | Gelatin | 0.25 | 300 | 0.28 |
| 22 | 5 | 6 | Gelatin | 0.25 | 300 | 0.28 |
| 23 | 8 | 10 | Gum arabic | 0.50 | 300 | 0.15 |
| 24 | 8 | 10 | Polyoxyethylene glycol | 0.50 | 300 | 0.18 |
| Comparison sample | 0.78 |
Claims (10)
1. microporous smokeless firework explosive; It is characterized in that by following steps preparations and get: will contain and nitrocellulosicly scrap military smokeless powder and be dissolved into and form polymeric sol in the solvent; Form lacquer shape emulsion through emulsion foam again; And under stirring action, will coat with lacquer the balling-up in the non-solvent medium of shape emulsion dispersion, then with obtain after solvent expeling, feed separation, the oven dry inside have micro-pore structure as the fireworks emission and open the medicine grain of luxuriant usefulness.
2. microporous smokeless firework explosive according to claim 1, it is characterized in that solvent be scrap military smokeless powder quality 3-15 doubly, the tap density that obtains the fireworks medicine is 0.05gcm
-3-0.4gcm
-3
3. the preparation method of a microporous smokeless firework explosive; It is characterized in that: will contain and nitrocellulosicly scrap military smokeless powder and be dissolved into and form polymeric sol in the solvent; Form lacquer shape emulsion through emulsion foam again; And under stirring action, will coat with lacquer the balling-up in the non-solvent medium of shape emulsion dispersion, then with the smoke less fire cracker medicine that obtains having micro-pore structure after solvent expeling, feed separation, the oven dry.
4. the preparation method of microporous smokeless firework explosive according to claim 3; It is characterized in that: in the dissolution process; Solvent be scrap military smokeless powder quality 3-15 doubly, solvent adopts a kind of in ETHYLE ACETATE, butylacetate, acetone, butanone, ethanol, the methyl alcohol or several mixture.
5. according to the preparation method of claim 3 or 4 described microporous smokeless firework explosives, it is characterized in that: dissolution time is 10-180min under room temperature or heating condition, and the temperature of heating is not higher than the azeotropic point of the boiling point or the mixed solvent of solvent.
6. the preparation method of microporous smokeless firework explosive according to claim 4; It is characterized in that: scrap military smokeless powder and add before the solvent; To scrap military smokeless powder and add water and disperse, and prevent to reunite, the ratio that institute adds water is 0-2 times of useless gunpowder quality.
7. the preparation method of microporous smokeless firework explosive according to claim 3; It is characterized in that: under room temperature or heating condition, carry out emulsion foam; The temperature of heating is not higher than the azeotropic point of the boiling point or the mixed solvent of solvent, and the emulsion foam time is 10-240min; In the emulsion foam process, once add in the polymeric sol, repeatedly add, or add the entry or the aqueous solution continuously, the add-on of the water or the aqueous solution is no more than the solvent total amount; The said aqueous solution is the aqueous solution of tensio-active agent.
8. the preparation method of microporous smokeless firework explosive according to claim 7 is characterized in that: the tensio-active agent that contains in the aqueous solution that in polymeric sol, adds is a kind of in non-ionics, aniorfic surfactant or the cationic surfactant or several mixture.
9. the preparation method of microporous smokeless firework explosive according to claim 3, it is characterized in that: in the balling-up process, the non-solvent medium is the aqueous solution that contains dispersion agent, said dispersion agent is water-soluble natural polymer or water-soluble synthetic macromolecule.
10. the preparation method of microporous smokeless firework explosive according to claim 3 is characterized in that: in the drying course, as thermal source, temperature is no more than 100 degrees centigrade with water vapor or hot water.
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| CN102219621B (en) * | 2011-03-25 | 2013-03-13 | 南京理工大学 | Modularized smokeless firework propellant and preparation method thereof |
| CN102219620B (en) * | 2011-03-25 | 2013-03-27 | 南京理工大学 | Modularized bud-opening powder for display shell and preparation method thereof |
| CN102898259A (en) * | 2012-09-25 | 2013-01-30 | 北京理工大学 | White snowflake tail combined firework and method for preparing same |
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| CN103554524B (en) * | 2013-11-01 | 2015-05-13 | 南京理工大学 | Ultrafine dispersion method for single-compound explosive in energetic composite material |
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| CN103787799B (en) * | 2014-01-22 | 2016-07-06 | 南京理工大学 | Continuous preparation system and method containing energy polymer microsphere |
| CN105085127A (en) * | 2014-05-06 | 2015-11-25 | 南京理工大学 | Continuous preparation system and method for smokeless fireworks |
| CN104710252A (en) * | 2015-02-10 | 2015-06-17 | 张光辉 | Firework initiating explosive and preparation method thereof |
| CN106938455B (en) * | 2016-11-02 | 2020-03-27 | 柏才富 | Nail shooting bullet for nail shooting fastener and manufacturing method thereof |
| CN112028722A (en) * | 2019-06-04 | 2020-12-04 | 南京理工大学 | Preparation method of high-burning-speed solid propellant |
| CN113307708B (en) * | 2021-06-17 | 2022-06-03 | 张宏善 | Preparation method of single-base powder and single-base powder obtained by method |
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| CN1526687A (en) * | 2003-09-22 | 2004-09-08 | 中国北方化学工业总公司 | Smokeless gun propellant for fireworks and its prepn |
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| CN1526687A (en) * | 2003-09-22 | 2004-09-08 | 中国北方化学工业总公司 | Smokeless gun propellant for fireworks and its prepn |
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