CN101844954A - 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 luxuriant 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 civil explosive 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 the smokeless propellant agent of a kind of fireworks, 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 smokeless propellant and preparation method thereof, also be that the expired rifle of scrapping of employing, shell single-base powder are main raw material, the ammonium dichromate and the charcoal that add certain component, through being ground into 120 order fine powders, thereby can be mixed and made into the microgranular fireworks smokeless propellant of 1-1.5mm.The gunpowder that will give up is pulverized and is used aspect fireworks, 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.
United States Patent (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 is distributed in the solution that contains protection glue and basic metal or alkaline earth salt and forms spherical droplets; further reduce stirring velocity; material is reunited; 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 at 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 use in the luxuriant medicine of opening of 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 granular 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, consumption during only for the 20%-50% of original-pack black powder amount its firing altitude just with former powder charge quite or be higher than original-pack liquid medicine and put down, the amount of smoke of emission process generation also reduces significantly in addition, as shown in Figure 4, 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, right figure powder charge is the smoke less fire cracker medicine, the firing altitude of effect medicine inner core is identical, smoke less fire cracker medicine explosive load is 1/3 of a black powder, adopts the smoke less fire cracker medicine to descend significantly in the amount of smoke that emission process produces as can be seen.As display shell open luxuriant medicine the time, when consumption only is 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, as 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, right figure powder charge is the smoke less fire cracker medicine, smoke less fire cracker medicine explosive load is 1/3 of a black powder, and blast fragment and open luxuriant diameter basically identical adopts the smoke less fire cracker medicine to descend significantly in the amount of smoke that the process that blasts produces as can be seen.(3) preparation method finishes under agitation condition as shaping medium at water and solvent, and whole moulding process can be finished in same device; Described 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 main component is auxiliary components such as soluble cotton and a spot of tranquilizer; The double-base powder main component is soluble cotton and nitroglycerine; The triple base propellant main component is compositions such as soluble cotton nitroglycerine and nitroguanidine.
The invention provides a kind of preparation method of microporous smokeless firework explosive, this preparation method can prepare and contain nitrocellulosic biography rate height and tap density and the adjustable smoke less fire cracker medicine of granular 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, then through obtaining having the smoke less fire cracker medicine of micro-pore structure after solvent expeling, feed separation, the oven dry.
Wherein, microporous smokeless firework explosive preparation method detailed process of the present invention is as follows:
(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, 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.Add in the military smokeless powder of scrapping before the solvent, can add a spot of water earlier or the aqueous solution disperses, reunite and bond on wall 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 ethyl 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 determines that according to raw material type and granular size dissolution time is 10-180min under room temperature or heating condition, is preferably 20-90min; Solvent temperature is determined 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 ethyl 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.Described emulsion foam process can be finished in the balling-up reactor, described balling-up reactor is the reactor 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 determined according to the volume of balling-up reactor 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 described aqueous solution as emulsification foaming agent or foam stabilizer, to guarantee that material disperses and the emulsion foam state is more even, described tensio-active agent can be a nonionic surface active agent, as alkylphenol polyoxyethylene; Can also be aniorfic surfactant, as sodium lauryl sulphate or Sodium dodecylbenzene sulfonate etc.; Can also select cationic surfactant for use, as Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide etc.The add-on of tensio-active agent determines 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 described 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 determine that the tap density that needs is little, and then the water-soluble liquid measure of Jia Ruing should increase, but the add-on by volume of the aqueous solution is no more than the solvent total amount.Carry out emulsion foam under room temperature or heating condition, 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 substantially; When adopting ethyl acetate to make solvent, should keep 40 ℃-68 ℃, be preferably 50 ℃-65 ℃.
The emulsion foam process can also be finished in emulsifying device, and as 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 finished.
(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 interfacial tension and form spherical droplets; the described aqueous solution can be the aqueous solution that contains dispersion agent; can also be the mother liquor that medicine grain moulding last time preparation 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, polyacrylamide, polyvinyl alcohol, 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 substantially, keeps 40 ℃-68 ℃ when adopting ethyl acetate solvent, 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 determined 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 to carry out under higher stirring velocity, otherwise then need carry out under low stirring velocity.
(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 described 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 that surpasses the boiling point of solvent or solvent and water when temperature is more than 10 ℃ the time, keeps can stopping to drive more than the 10min molten.When adopting ethyl acetate to make solvent, molten as adopting normal pressure to steam, temperature reaches 85 ℃ and keeps can stopping to drive more than the 10min molten.
(5) feed separation: after the solvent expeling is finished, adopt the general type of cooling that the temperature of system is dropped near room temperature, or directly adopt common centrifugation or filtering mode that the aqueous solution is separated with solid particulate, the filtrate of separating is called the balling-up mother liquor, contain 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 be 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 finish under the state of vacuumizing, vacuum tightness is determined 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 by 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 substantially and produce, and do not have pollutent such as sulfurous gas.Normal pressure pass rate and apparent combustion speed at top speed far above the same particle sizes scope by scrapping military smokeless powder through pulverizing and the medicine grain that obtains is handled in simple modification.
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 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 lacquer shape emulsion.Lacquer shape emulsion is dispersed into tiny drop in water medium or in other non-solvent media under the strong shear action that mechanical stirring produces.Because the effect of interfacial tension, 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 the easiest sphere that is shrunk to of drop.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 one deck protection glue, the gathering in the time of can having stoped spheroid to collide mutually effectively.
After the balling-up, by 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 purged in water or in other non-solvent media.Drive when molten in the temperature that is lower than solvent boiling point, solvent diffuses in the entry earlier or in the non-solvent medium, evaporates from aqueous phase or other non-solvent media then under concentration difference promotes in the particle; When driving under the temperature that is being higher than solvent boiling point when molten, 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, adopting the nitrocotton cellulose content is raw material greater than the basic useless gunpowder of 85% list, through preliminary broken, the control particle diameter is no more than 2mm, to join in the reactor through medicine grain and 1 times of water of determination of moisture band water to drug grain quality, 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 stirring 60min is continued to continue in the back 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 heat up solvent is steamed lentamente, ball hardens gradually, continues to keep to get final product discharging more than the 10min after temperature is raised to 85 ℃.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, similarly 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 be seen from Figure 2, the profile of sample approaches sphere, and a large amount of holes are contained in inside, from scale as can be seen the diameter major part of hole below 10 μ m, connect mutually between the hole.
Embodiment 2
Adopting the single base identical with embodiment 1 gunpowder that gives up is bulk drug, 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 be seen from Figure 3, the profile of sample approaches sphere, and a large amount of holes are contained in inside, hole yardstick wider distribution, from scale as can be seen the diameter major part of hole below 50 μ m, connect mutually between the hole.
Embodiment 3
Adopting the single base identical with embodiment 1 gunpowder that gives up is bulk drug, 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% nitroglycerine content is that 38% the useless gunpowder of double-basis is a bulk drug, 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 the single base useless gunpowder identical with embodiment 1 is bulk drug, and 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 the single base identical with embodiment 1 gunpowder that gives up is bulk drug, does not add water at dissolution process, and other preparation process 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 the single base identical with embodiment 1 gunpowder that gives up is bulk drug, and 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 the single base useless gunpowder identical with embodiment 1 is bulk drug, and 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 the single base identical with embodiment 1 gunpowder that gives up is bulk drug, preparation process is identical with embodiment 1, solvent adding amount is 8 times of drug grain quality, 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 the single base useless gunpowder identical with embodiment 1 is bulk drug, and preparation process is similar to Example 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 with the results are shown in Table 1.Solvent all adopts ethyl 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 preparation process, dispersant dosage is the per-cent that add-on accounts for the aqueous solution total amount of adding, the medicine grain that the contrast 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 | Polyvinyl alcohol | ??0.25 | ??400 | ??0.30 | ??28.0 |
| ??16 | ??5 | ??8 | Methylcellulose gum | ??0.5 | ??400 | ??0.25 | ??31.9 |
| The contrast sample | ??0.78 | ??7.5 |
Embodiment 17-20:
Adopting the single base identical with embodiment 1 gunpowder that gives up is bulk drug, preparation process is identical with embodiment 1, only be to adopt different material ratios, and the kinds of surfactants and the concentration of the interpolation of change emulsion foam process, dispersion agent adopts gelatine, add-on is 0.25% of the water yield, relevant parameter and the results are shown in Table 2.Solvent all adopts ethyl 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 the contrast sample obtains for the useless direct pulverization process of gunpowder of single base in 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 | Sodium dodecylbenzene sulfonate | ??0.1 | ??300 | ??0.22 |
| The contrast sample | ??0.78 |
Embodiment 21-24:
Adopt soluble cotton be 56% and nitroglycerine content be that 26% the useless gunpowder of double-basis is a bulk drug, 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 the results are shown in Table 3.Solvent all adopts ethyl 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 the contrast 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 |
| The contrast 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 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.
2. microporous smokeless firework explosive according to claim 1, it is characterized in that solvent load be scrap military smokeless powder quality 3-15 doubly, the tap density that obtains the fireworks medicine is 0.05g.cm
-3-0.4g.cm
-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 through obtaining having the smoke less fire cracker medicine of 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 load be scrap military smokeless powder quality 3-15 doubly, solvent adopts a kind of in ethyl 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 that military smokeless powder adds water or the aqueous solution disperses, and prevent to reunite, the ratio that institute adds the water or the aqueous solution 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.
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 adds in polymeric sol is a kind of in nonionic surface active agent, 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, described 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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| 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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