CN110981658A - Safe smokeless and sulfur-free firecracker and firecracker nitrate medicament and preparation method thereof - Google Patents
Safe smokeless and sulfur-free firecracker and firecracker nitrate medicament and preparation method thereof Download PDFInfo
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- CN110981658A CN110981658A CN201911255600.1A CN201911255600A CN110981658A CN 110981658 A CN110981658 A CN 110981658A CN 201911255600 A CN201911255600 A CN 201911255600A CN 110981658 A CN110981658 A CN 110981658A
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- deuteride
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003814 drug Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 59
- -1 modified calcium deuteride Chemical class 0.000 claims abstract description 34
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 26
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 26
- 241001330002 Bambuseae Species 0.000 claims abstract description 26
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 26
- 239000011425 bamboo Substances 0.000 claims abstract description 26
- 229920002678 cellulose Polymers 0.000 claims abstract description 20
- 239000001913 cellulose Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 11
- RDJUHLUBPADHNP-UHFFFAOYSA-N 1,2,3,5-tetrahydroxybenzene Chemical compound OC1=CC(O)=C(O)C(O)=C1 RDJUHLUBPADHNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 13
- 239000000693 micelle Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 2
- 239000000920 calcium hydroxide Substances 0.000 claims 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
Abstract
The invention relates to a safe smokeless and sulfur-free firecracker and firecracker nitrate medicament and a preparation method thereof, and belongs to the field of environment-friendly pyrotechnic compositions. The components comprise: passivated hexogen, nitrated bamboo cellulose, modified calcium deuteride, trimethylolethane trinitrate, diatomite, N-benzylglycine ethyl ester and dicyandiamide. The invention adopts passivated hexogen as the main component, is safe and reliable, does not contain metal powder and sulfur element components, and can really realize the preparation of the safe smokeless and sulfur-free firecracker nitrate medicament; the self-made nitrified bamboo cellulose is adopted, and the N-benzyl glycine ethyl ester and the dicyandiamide are introduced, so that the mechanical property and the stability of the firecracker nitrate medicament can be effectively improved, and the safety of the firecracker nitrate medicament in the production, storage and use processes is ensured; the preparation method has simple process and concise steps, does not generate byproducts such as three wastes and the like in the production process, is suitable for the flow line operation of factories, is suitable for large-scale industrial production, and has remarkable economic and social benefits.
Description
Technical Field
The invention relates to a safe smokeless and sulfur-free firecracker and firecracker nitrate medicament and a preparation method thereof, and belongs to the field of environment-friendly pyrotechnic compositions.
Background
As a very common consumer product in China, fireworks and crackers are consumed in a large amount, and especially when festive holidays such as spring festival, afternoon festival and the like are festered, the setting-off amount reaches a peak value. However, the production, transportation and storage of fireworks and crackers have many unsafe factors, which threaten the safety of people's life and property, and such a large amount of fireworks and crackers cause serious environmental pollution and harm to human health.
The main components of the present firecracker nitrate agent are potassium nitrate, sulfur and charcoal, some also contain potassium chlorate, and even a large amount of metal powder and the like can be added. The burning off of the powder can generate carbon oxide, nitrogen oxide, sulfur dioxide and other toxic and harmful gases and metal oxide dust. These toxic and harmful gases and dust particles pollute the environment and damage human health. Moreover, the problem that the existing fireworks and crackers are flammable and explosive is not solved all the time, so that huge potential safety hazards exist in the processes of production, transportation, storage and setting off, and even disastrous safety accidents happen. These problems all seriously restrict the production and use of fireworks and crackers. The firework firecracker is divided into a barrel body, gunpowder and a fuse in structure, and the inner surface and the outer surface of the barrel body and a top cover are provided with a flame retardant layer and a moisture-proof layer, so that potential safety hazards (CN200520016560.2) caused by open fire or high temperature are eliminated, but the design is complex, the preparation is difficult, and the preparation process is complicated; the soup substitute improves the setting-off effect of fireworks and crackers and also improves the safety performance (CN01106953.8) by preparing the firework and cracker color light safety agent, but the agent needs to be combined with potassium chlorate for use, and the problem of environmental pollution still exists. The safety problem (CN96234064.2) of fireworks and crackers is solved through designing a circulated use's electron firecracker to the waitres, but this equipment structure is complicated, and the line connection is difficult, complex operation, and non-professional can not use, can not bring audio-visual sense organ experience for spectator moreover, can not satisfy masses' demand.
On the premise of ensuring that fireworks and crackers normally meet consumption, the pollution of setting off the fireworks and crackers to the environment and the damage to human bodies are reduced, potential safety hazards are fundamentally eliminated, and safety problems are thoroughly solved. Therefore, the safe smokeless and sulfur-free firecracker and firecracker nitro-compound preparation prepared by the method has great social and practical significance.
Disclosure of Invention
The invention provides a safe smokeless and sulfur-free firecracker nitrate medicament and a preparation method thereof, aiming at solving the safety problem of the existing firecracker nitrate medicament and the smoke pollution problem existing after the firecracker nitrate medicament is set off.
The purpose of the invention is realized by the following technical scheme.
The safe smokeless and sulfur-free firecracker and firecracker nitrate medicament comprises the following components in percentage by mass:
the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent;
a preparation method of a safe smokeless and sulfur-free firecracker nitrate medicament comprises the following specific steps:
weighing passivated hexogen, nitrified bamboo cellulose, modified calcium deuteride, trimethylolethane trinitrate, diatomite, N-benzyl glycine ethyl ester and dicyandiamide according to the formula mass ratio;
step two, dividing the nitrated bamboo cellulose powder weighed in the step one into A, B groups according to the mass ratio of (1-5) to (10), dissolving the nitrated bamboo cellulose powder of the group A in ethyl acetate according to the mass ratio of 1:10, and stirring for 2-3 hours under the ultrasonic dispersion condition; then, continuously adding the dicyandiamide powder and the N-benzylglycine ethyl ester powder weighed in the step one under the stirring state, and uniformly stirring to obtain a mixed solution of the bamboo cellulose nitrate;
step three, under the stirring and ultrasonic dispersion states, adding the passivated hexogen powder weighed in the step one, trimethylolethane trinitrate and B group of nitrated bamboo cellulose obtained in the step two into the nitrated bamboo cellulose mixed sol obtained in the step two, and uniformly mixing; adding the modified calcium deuteride powder and the diatomite powder weighed in the step one, uniformly mixing, kneading, and adding a proper amount of ethyl acetate in the kneading process to obtain a uniform micelle with moderate hardness;
fourthly, granulating the uniform micelle with moderate hardness obtained in the third step by using a double-screw granulator, airing the obtained uniform micelle in a cool and ventilated place to be half-dry, and transferring the obtained uniform micelle into a blast oven at the temperature of 80-90 ℃ for drying for 2-3 hours to obtain a safety smokeless and sulfur-free firecracker nitrate medicament crude product;
and step five, crushing the crude safe smokeless and sulfur-free firecracker and.
The preparation method of the modified calcium deuteride comprises the following steps: in the glove box, setting the argon pressure of the glove box to be 0.4-0.6 MPa, the water content to be 0.3-0.5 ppm and the oxygen content to be 0.3-0.8 ppm; soaking the calcium deuteride powder in anhydrous ethyl acetate according to the mass ratio of 1:5, and performing ultrasonic dispersion for 30-50 minutes; filtering, and drying in a vacuum oven at 90-100 ℃ for 20-30 minutes; after cooling, placing the calcium deuteride powder in a glove box, adding the calcium deuteride powder, zirconium n-propoxide and dibutyl tin oxide powder into a tetrahydrofuran solution according to the ratio of 1:0.5 (0.01-0.03): 10, stirring for 30-50 minutes under an ultrasonic state, and then adding graphene powder, wherein the mass ratio of the calcium deuteride powder to the graphene powder is 1 (0.02-0.03), and then obtaining a mixed solution D; placing the mixed solution D in an oil bath pan, setting the temperature to be 150-170 ℃, and stirring for 5-7 hours; filtering, washing for 3-5 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3-5 times by using anhydrous ethyl acetate; drying in a vacuum oven at 100-120 ℃ for 2-5 hours, taking out and crushing to obtain modified calcium deuteride;
the method for judging the moderate hardness comprises the following steps: after the micelle-shaped objects are extruded to pass through a 20-mesh copper sieve, the micelle-shaped objects are in a continuous thin strip shape, are not adhered with each other and have certain plasticity and tensile strength;
advantageous effects
1. The safe smokeless and sulfur-free firecracker and firecracker nitro agent adopts passivated hexogen as a main component, is safe and reliable, does not contain metal powder and sulfur elements, and can really realize the preparation of the safe smokeless and sulfur-free firecracker and nitre agent;
2. a safe smokeless and sulfur-free firecracker nitro-chemical adopts self-made nitrified bamboo cellulose, and introduces N-benzyl glycine ethyl ester and dicyandiamide, so that the mechanical property and stability of the firecracker nitro-chemical can be effectively improved, and the safety of the firecracker nitro-chemical in the production, storage and use processes is ensured;
3. the preparation method of the safe smokeless and sulfur-free firecracker and firecracker nitro agent has the advantages of simple process and concise steps, does not generate byproducts such as three wastes and the like in the production process, is suitable for the flow line operation of factories, is suitable for large-scale industrial production, and has remarkable economic and social benefits.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The safe smokeless and sulfur-free firecracker and firecracker nitrate medicament comprises the following components in percentage by mass:
134.72g of nitrobamboo cellulose powder is divided into A, B groups, wherein the A group is 34.72g, the B group is 100g, the A group of nitrobamboo cellulose powder is dissolved in 347.2g of ethyl acetate, the mixture is stirred for 2 hours under the ultrasonic dispersion condition, then 8.75g of dicyandiamide and 18.18g of N-benzyl glycine ethyl ester are added under the stirring state, and the mixture is stirred uniformly to prepare a nitrobamboo cellulose mixed sol;
in the glove box, the argon pressure of the glove box is set to be 0.4MPa, the water content is 0.3ppm, and the oxygen content is 0.3 ppm; 70g of calcium deuteride powder is soaked in 350g of anhydrous ethyl acetate, and ultrasonic dispersion is carried out for 30 minutes; filtering, and drying in a vacuum oven at 90 deg.C for 30 min; after cooling, in a glove box, adding 60g of calcium deuteride powder, 30g of zirconium n-propoxide and 0.8g of dibutyltin oxide powder into 600g of tetrahydrofuran solution, stirring for 35 minutes under an ultrasonic state, and then adding 1.5g of graphene powder to obtain a mixed solution D; placing the mixed solution D in an oil bath kettle, setting the temperature to be 150 ℃, and stirring for 5.5 hours; filtering, washing for 3 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3 times by using anhydrous ethyl acetate; drying in a vacuum oven at 120 deg.C for 2 hr, taking out, and crushing to obtain 87.86g modified calcium deuteride powder;
adding 419.73g of passivated hexogen powder, 65.52g of trimethylolethane trinitrate and B-group nitrated bamboo cellulose into the nitrated bamboo cellulose mixed sol under the stirring and ultrasonic dispersion states, and uniformly mixing; then 83.09g of modified calcium deuteride powder and 37.21g of diatomite powder are added and mixed evenly; then kneading, adding 18ml of ethyl acetate in the kneading process, and kneading until the mixture is a uniform micelle with moderate hardness;
granulating the uniform paste by using a double-screw granulator, airing the paste to be half-dry in a cool and ventilated place, and then transferring the dried paste to a blast oven at the temperature of 85 ℃ for drying for 2 hours to prepare 765.39g of a safe smokeless and sulfur-free firecracker and;
765.39g of the crude product of the safe smokeless sulfur-free firecracker nitrate medicament is crushed by light pressure, sieved by a 60-mesh copper sieve, and sieved residues with too small particles are removed, then sieved by a 30-mesh copper sieve, and sieved residues of the 30-mesh copper sieve are taken to prepare 762.17g of the safe smokeless sulfur-free firecracker nitrate medicament with uniform particles, wherein the yield reaches 99.58%.
Tests prove that the obtained safe smokeless and sulfur-free firecracker and firecracker nitrate medicament has 17% of impact sensitivity (the drop height is 250 +/-1 mm, and the drop weight is 10.0 +/-0.1 kg), 21% of friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 30mg, and the swing angle is 90 degrees), excellent explosive-charging mechanical properties, normal ignition temperature, excellent finished product burning effect, no smoke generation and no sulfur-containing substance emission in the burning process, and meets the environmental protection requirements of smokeless and sulfur-free.
Example 2
The safe smokeless and sulfur-free firecracker and firecracker nitrate medicament comprises the following components in percentage by mass:
dividing 28.63kg of nitrated bamboo cellulose powder into A, B groups, wherein the A group is 8.63kg, the B group is 20kg, dissolving the A group of nitrated bamboo cellulose powder in 86.3kg of ethyl acetate, stirring for 2 hours under the ultrasonic dispersion condition, then continuously adding 4.90kg of dicyandiamide and 8.46kg of N-benzyl glycine ethyl ester under the stirring state, and uniformly stirring to obtain a nitrated bamboo cellulose mixed sol;
in the glove box, the argon pressure of the glove box is set to be 0.5MPa, the water content is 0.4ppm, and the oxygen content is 0.5 ppm; 30.2kg of calcium deuteride powder is soaked in 151kg of anhydrous ethyl acetate, and ultrasonic dispersion is carried out for 40 minutes; filtering, and drying in a vacuum oven at 100 deg.C for 20 min; after cooling, adding 30kg of calcium deuteride powder, 15kg of zirconium n-propoxide and 0.3kg of dibutyltin oxide powder into 300kg of tetrahydrofuran solution in a glove box, stirring for 40 minutes under an ultrasonic state, and then adding 0.7kg of graphene powder to obtain a mixed solution D; placing the mixed solution D in an oil bath kettle, setting the temperature to be 150 ℃, and stirring for 5.5 hours; filtering, washing for 3 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3 times by using anhydrous ethyl acetate; drying in a vacuum oven at 120 deg.C for 2 hr, taking out, and crushing to obtain 43.94kg modified deuterated calcium powder;
under the stirring and ultrasonic dispersion state, 116.40kg of passivated hexogen powder, 21.14kg of trimethylolethane trinitrate and B group of nitrated bamboo cellulose are added into the nitrated bamboo cellulose mixed sol and mixed uniformly; then adding 39.56kg of modified calcium deuteride powder and 7.76kg of diatomite powder, and uniformly mixing; kneading, adding 2350ml ethyl acetate during kneading, and kneading until the mixture is a uniform micelle with moderate hardness;
granulating the uniform paste by using a double-screw granulator, airing the paste to be half-dry in a cool and ventilated place, and then transferring the paste to a 90 ℃ blast oven for drying for 2.5 hours to prepare 225.73kg of safe smokeless and sulfur-free firecracker and;
225.73kg of crude safe smokeless sulfur-free firecracker nitrate medicament is crushed by light pressure, sieved by a 60-mesh copper sieve, and sieved residues with too small particles are removed, then sieved by a 30-mesh copper sieve, and the sieved residues with the 30-mesh copper sieve are taken to prepare 224.41kg of safe smokeless sulfur-free firecracker nitrate medicament with uniform particles, wherein the yield reaches 99.42%.
Tests prove that the obtained safe smokeless and sulfur-free firecracker and firecracker nitrate medicament has 18% of impact sensitivity (the drop height is 250 +/-1 mm, and the drop weight is 10.0 +/-0.1 kg), 23% of friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 30mg, and the swing angle is 90 degrees), excellent explosive-charging mechanical property, normal ignition temperature, excellent finished product burning effect, no smoke generation and no sulfur-containing substance emission in the burning process, and meets the smokeless and sulfur-free environmental protection requirements.
Example 3
The safe smokeless and sulfur-free firecracker and firecracker nitrate medicament comprises the following components in percentage by mass:
38.24kg of nitrobamboo cellulose powder is divided into A, B groups, wherein the A group is 8.24kg, the B group is 30kg, the A group of nitrobamboo cellulose powder is dissolved in 82.4kg of ethyl acetate, the mixture is stirred for 2 hours under the ultrasonic dispersion condition, then under the stirring state, 3.13kg of dicyandiamide and 4.09kg of N-benzyl glycine ethyl ester are added, and the mixture is uniformly stirred to prepare a nitrobamboo cellulose mixed sol;
in the glove box, the argon pressure of the glove box is set to be 0.6MPa, the water content is 0.3ppm, and the oxygen content is 0.6 ppm; soaking 22.2kg of calcium deuteride powder in 111kg of anhydrous ethyl acetate, and performing ultrasonic dispersion for 40 minutes; filtering, and drying in a vacuum oven at 95 ℃ for 25 minutes; after cooling, in a glove box, adding 22kg of calcium deuteride powder, 11kg of zirconium n-propoxide and 0.24kg of dibutyltin oxide powder into 300kg of tetrahydrofuran solution, stirring for 50 minutes under an ultrasonic state, and then adding 0.5kg of graphene powder to obtain a mixed solution D; placing the mixed solution D in an oil bath kettle, setting the temperature to be 150 ℃, and stirring for 7 hours; filtering, washing for 3 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3 times by using anhydrous ethyl acetate; drying in a vacuum oven at 110 deg.C for 4 hr, taking out, and crushing to obtain 32.62kg modified calcium deuteride powder;
under the stirring and ultrasonic dispersion state, 89.75kg of passivated hexogen powder, 15.33kg of trimethylolethane trinitrate and B group of nitrated bamboo cellulose are added into the nitrated bamboo cellulose mixed sol and mixed uniformly; then adding 29.76kg of modified calcium deuteride powder and 7.34kg of diatomite powder, and uniformly mixing; kneading, adding 2810ml of ethyl acetate during kneading, and kneading until the mixture is a uniform micelle with moderate hardness;
granulating the uniform paste by using a double-screw granulator, airing the paste to be half-dry in a cool and ventilated place, and then transferring the dried paste to a blast oven at the temperature of 85 ℃ for drying for 3 hours to prepare 186.41kg of safe smokeless and sulfur-free crude firecracker and nitre medicament products;
186.41kg of crude safe smokeless sulfur-free firecracker nitrate medicament is crushed by light pressure, sieved by a 60-mesh copper sieve, and sieved residues with too small particles are removed, then sieved by a 30-mesh copper sieve, and the sieved residues with the 30-mesh copper sieve are taken to prepare 185.87kg of safe smokeless sulfur-free firecracker nitrate medicament with uniform particles, wherein the yield reaches 99.71%.
Tests prove that the obtained safe smokeless and sulfur-free firecracker and firecracker nitrate medicament has the impact sensitivity (the drop height is 250 +/-1 mm, and the drop weight mass is 10.0 +/-0.1 kg) of 19 percent, the friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 30mg, and the swing angle is 90 degrees) of 21 percent, excellent explosive-charging mechanical properties, normal ignition temperature, excellent finished product burning effect, no smoke generation and no sulfur-containing substance emission in the burning process, and meets the smokeless and sulfur-free environmental protection requirements.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. The safe smokeless and sulfur-free firecracker and firecracker nitrate medicament is characterized in that: the components and the occupied mass percentage are as follows:
the preparation method of the modified calcium deuteride comprises the following steps: in the glove box, setting the argon pressure of the glove box to be 0.4-0.6 MPa, the water content to be 0.3-0.5 ppm and the oxygen content to be 0.3-0.8 ppm; soaking the calcium deuteride powder in anhydrous ethyl acetate according to the mass ratio of 1:5, and performing ultrasonic dispersion for 30-50 minutes; filtering, and drying in a vacuum oven at 90-100 ℃ for 20-30 minutes; after cooling, placing the calcium deuteride powder in a glove box, adding the calcium deuteride powder, zirconium n-propoxide and dibutyl tin oxide powder into a tetrahydrofuran solution according to the ratio of 1:0.5 (0.01-0.03): 10, stirring for 30-50 minutes under an ultrasonic state, and then adding graphene powder, wherein the mass ratio of the calcium deuteride powder to the graphene powder is 1 (0.02-0.03), and then obtaining a mixed solution D; placing the mixed solution D in an oil bath pan, setting the temperature to be 150-170 ℃, and stirring for 5-7 hours; filtering, washing for 3-5 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3-5 times by using anhydrous ethyl acetate; and (3) drying the calcium hydroxide in a vacuum oven at 100-120 ℃ for 2-5 hours, taking out and crushing to obtain the modified calcium deuteride.
2. The safe smokeless and sulfur-free firecracker nitro agent as claimed in claim 1, wherein: the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent.
3. The preparation method for preparing the safe smokeless and sulfur-free firecracker nitrate medicament according to claim 1 is characterized by comprising the following steps: the method comprises the following specific steps:
weighing passivated hexogen, nitrified bamboo cellulose, modified calcium deuteride, trimethylolethane trinitrate, diatomite, N-benzyl glycine ethyl ester and dicyandiamide according to the formula mass ratio;
step two, dividing the nitrated bamboo cellulose powder weighed in the step one into A, B groups according to the mass ratio of (1-5) to (10), dissolving the nitrated bamboo cellulose powder of the group A in ethyl acetate according to the mass ratio of 1:10, and stirring for 2-3 hours under the ultrasonic dispersion condition; then, continuously adding the dicyandiamide powder and the N-benzylglycine ethyl ester powder weighed in the step one under the stirring state, and uniformly stirring to obtain a mixed solution of the bamboo cellulose nitrate;
step three, under the stirring and ultrasonic dispersion states, adding the passivated hexogen powder weighed in the step one, trimethylolethane trinitrate and B group of nitrated bamboo cellulose obtained in the step two into the nitrated bamboo cellulose mixed sol obtained in the step two, and uniformly mixing; adding the modified calcium deuteride powder and the diatomite powder weighed in the step one, uniformly mixing, kneading, and adding a proper amount of ethyl acetate in the kneading process to obtain a uniform micelle with moderate hardness;
fourthly, granulating the uniform micelle with moderate hardness obtained in the third step by using a double-screw granulator, airing the obtained uniform micelle in a cool and ventilated place to be half-dry, and transferring the obtained uniform micelle into a blast oven at the temperature of 80-90 ℃ for drying for 2-3 hours to obtain a safety smokeless and sulfur-free firecracker nitrate medicament crude product;
step five, crushing the crude product of the safe smokeless and sulfur-free firecracker and;
the method for judging the moderate hardness comprises the following steps: after the micelle is extruded to pass through a 20-mesh copper sieve, the micelle is in a continuous thin strip shape, is not adhered with each other, and has certain plasticity and tensile strength.
4. The method of claim 3, wherein: the preparation method of the modified calcium deuteride comprises the following steps: in the glove box, setting the argon pressure of the glove box to be 0.4-0.6 MPa, the water content to be 0.3-0.5 ppm and the oxygen content to be 0.3-0.8 ppm; soaking the calcium deuteride powder in anhydrous ethyl acetate according to the mass ratio of 1:5, and performing ultrasonic dispersion for 30-50 minutes; filtering, and drying in a vacuum oven at 90-100 ℃ for 20-30 minutes; after cooling, placing the calcium deuteride powder in a glove box, adding the calcium deuteride powder, zirconium n-propoxide and dibutyl tin oxide powder into a tetrahydrofuran solution according to the ratio of 1:0.5 (0.01-0.03): 10, stirring for 30-50 minutes under an ultrasonic state, and then adding graphene powder, wherein the mass ratio of the calcium deuteride powder to the graphene powder is 1 (0.02-0.03), and then obtaining a mixed solution D; placing the mixed solution D in an oil bath pan, setting the temperature to be 150-170 ℃, and stirring for 5-7 hours; filtering, washing for 3-5 times by using a dilute hydrochloric acid solution with the mass fraction of 1%, and then washing for 3-5 times by using anhydrous ethyl acetate; and (3) drying the calcium hydroxide in a vacuum oven at 100-120 ℃ for 2-5 hours, taking out and crushing to obtain the modified calcium deuteride.
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