CN111004074A - Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof - Google Patents
Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof Download PDFInfo
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- CN111004074A CN111004074A CN201911255305.6A CN201911255305A CN111004074A CN 111004074 A CN111004074 A CN 111004074A CN 201911255305 A CN201911255305 A CN 201911255305A CN 111004074 A CN111004074 A CN 111004074A
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- firecracker
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- bamboo cellulose
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
- C06B31/12—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound
- C06B31/22—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound the compound being nitrocellulose
- C06B31/24—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound the compound being nitrocellulose with other explosive or thermic component
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- 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
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a 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, boron nitride, potassium nitrate, p-phenylenediamine 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 smokeless and sulfur-free firecracker nitrate medicament; by adopting the self-made nitrated bamboo cellulose and introducing potassium nitrate, p-phenylenediamine, boron nitride and dicyandiamide, the mechanical property and 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.
Description
Technical Field
The invention relates to a 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
In festivals or events of Chinese festivals, fireworks and crackers are used in large quantities, and the setting off of the fireworks and crackers is more than 1000 years old after the fireworks and crackers are used for a long time. In recent years, due to the continuous increase of consumption, the lack of environmental awareness, the proliferation of manufacturers and the like, the burning of fireworks and crackers causes very serious pollution of smoke, dust, particles and the like, and brings unprecedented burden and harm to the environment and human health.
As is known, the pyrotechnic composition is one of four inventions in China, the main components of the pyrotechnic composition are potassium nitrate, sulfur and charcoal, some pyrotechnic compositions also contain potassium chlorate, and metal powder and the like can be added into the pyrotechnic composition for the purpose of gorgeous burning effect. Carbon oxide, nitrogen oxide, sulfur dioxide and metal oxide dust are generated during the ignition of the gas, and the toxic and harmful gas and dust particles have different degrees of damage to the respiratory system, the nervous system and the like of human beings. In recent years, many professionals in the firework and firecracker industry develop novel fireworks and crackers (such as CN200420076610.1, CN201310057675.5, CN92245902.9 and the like) which take gas as a blasting substance, combustible gas needs to be pre-charged in an air bag before leaving a factory, but the gas stability is poor, the safety problem is prominent, safety accidents such as blasting and the like are easy to occur under the high-temperature environment or in the case of meeting a fire source, and potential safety hazards are really increased for transportation and storage of the fireworks and crackers; some people also develop simulated electronic acousto-optic firecrackers (such as CN93243252.2, CN200820050107.7, CN201620075248.9 and the like), although traditional fireworks and crackers can be replaced in some occasions, the acousto-optic effect displayed by the device can not meet the requirement of people on the festive atmosphere created by the fireworks and crackers due to the fact that no real object exists. Although the novel fireworks and crackers solve the problems of environmental pollution, harm to human bodies and the like of the traditional fireworks and crackers, the novel fireworks and crackers are cooled down by people due to the defects of safety problems, setting off effects and the like, and therefore the novel fireworks and crackers can not meet huge market demands.
On the premise of ensuring that the fireworks and crackers are continuously used normally by people, the pollution of setting off the fireworks and crackers to the environment and the harm to human bodies are reduced, the main contradiction to be urgently solved in the fireworks and crackers industry is also the hot point problem and the key problem on the development road of the fireworks and crackers industry, the requirement for no smoke and no sulfur of the firecracker and the firecracker and cracker industry is provided, and the direction is pointed out for the development of the fireworks and cracker industry. Therefore, the prepared smokeless and sulfur-free firecracker nitrate medicament has great social and practical significance.
Disclosure of Invention
The invention provides a smokeless and sulfur-free firecracker nitrate medicament and a preparation method thereof, aiming at solving the problem of smoke pollution after the existing firecracker nitrate medicament is set off.
The purpose of the invention is realized by the following technical scheme.
A smokeless and sulfur-free 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 smokeless and sulfur-free firecracker nitrate medicament comprises the following specific steps:
weighing passivated hexogen, nitrated bamboo cellulose, boron nitride, potassium nitrate, p-phenylenediamine and dicyandiamide according to the mass ratio of the formula;
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, the p-phenylenediamine and the boron nitride weighed in the step one under the stirring state, and uniformly stirring to obtain a mixed solution of the nitro bamboo cellulose;
step three, under the stirring and ultrasonic dispersion states, adding the passivated hexogen and potassium nitrate weighed in the step one and the B group of the nitrated bamboo cellulose obtained in the step two into the nitrated bamboo cellulose mixed sol obtained in the step two, kneading the mixture after the mixture is uniformly mixed, and adding a proper amount of ethyl acetate into the kneading process to knead the mixture to form uniform micelle with moderate hardness;
step four, granulating the uniform micelle with moderate hardness obtained in the step three 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 smokeless and sulfur-free firecracker and firecracker nitrate medicament crude product;
and step five, crushing the crude smokeless and sulfur-free firecracker and firecracker.
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 smokeless and sulfur-free firecracker nitrate medicament 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 smokeless and sulfur-free firecracker nitrate medicament;
2. a smokeless and sulfur-free firecracker nitrate medicament adopts self-made nitrified bamboo cellulose, and potassium nitrate, p-phenylenediamine, boron nitride and dicyandiamide are introduced, so that the mechanical property and 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;
3. the preparation method of the smokeless and sulfur-free firecracker and firecracker nitrate medicament 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 benefit and social benefit.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A smokeless and sulfur-free firecracker nitrate medicament comprises the following components in percentage by mass:
36.57g of nitrated bamboo cellulose powder is divided into A, B groups, wherein the A group is divided into 6.57g and the B group is divided into 30g, the nitrated bamboo cellulose powder of the A group is dissolved in 65.7g of ethyl acetate, the mixture is stirred for 2 hours under the condition of ultrasonic dispersion, then 1.36g of dicyandiamide, 3.49g of p-phenylenediamine and 13.25g of boron nitride are added under the stirring state, and the mixture is stirred uniformly to prepare a nitrated bamboo cellulose mixed sol;
adding 66.71g of passivated hexogen, 5.39g of potassium nitrate and B group of nitrated bamboo cellulose into the nitrated bamboo cellulose mixed sol under the stirring and ultrasonic dispersion states, kneading after uniformly mixing, adding 2.15ml of ethyl acetate in the kneading process, and kneading to form 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 blast oven at the temperature of 80 ℃ for drying for 2 hours to prepare 119.34g of smoke-free and sulfur-free crude product of the firecracker and firecracker nitrate medicament;
119.34g of crude smokeless and sulfur-free firecracker and firecracker are made into 118.06g of smokeless and sulfur-free firecracker and firecracker, wherein.
Through tests, the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament has 31% of impact sensitivity (the drop height is 250 +/-1 mm, the drop weight is 10.0 +/-0.1 kg), 33% 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, 86dB of measured sound level value, and meets the environmental protection requirements of no smoke and sulfur; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at 73 ℃ for 48 hours, no decomposition phenomenon can be seen by naked eyes, and the burning effect of a finished product is not changed; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at the temperature of minus 30 ℃ for 48 hours, the phenomenon of frost cracking can not be seen by naked eyes, and the burning effect of a finished product is not changed.
Example 2
A smokeless and sulfur-free firecracker nitrate medicament comprises the following components in percentage by mass:
dividing 3.92kg of nitrated bamboo cellulose powder into A, B groups, wherein the A group is 1.12kg, the B group is 2.8kg, dissolving the A group of nitrated bamboo cellulose powder in 11.2kg of ethyl acetate, stirring for 2.5 hours under the ultrasonic dispersion condition, then continuously adding 0.30kg of dicyandiamide, 0.83kg of p-phenylenediamine and 1.25kg of boron nitride under the stirring state, and uniformly stirring to obtain a nitrated bamboo cellulose mixed sol;
under the stirring and ultrasonic dispersion states, adding 13.52kg of passivated hexogen, 1.55kg of potassium nitrate and B group of nitrated bamboo cellulose into the nitrated bamboo cellulose mixed sol, kneading after uniformly mixing, adding 527ml 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 uniform paste in a cool and ventilated place to be half-dry, and then transferring the uniform paste to a blast oven at the temperature of 85 ℃ for drying for 2.5 hours to prepare 20.63kg of smoke-free and sulfur-free crude firecracker and firecracker nitrate medicament;
20.63kg of the crude smokeless and sulfur-free firecracker and firecracker are manufactured, after the smokeless and sulfur-free firecracker and firecracker are crushed by light pressure, the firecracker.
Tests prove that the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament has the impact sensitivity (the drop height is 250 +/-1 mm, the drop weight is 10.0 +/-0.1 kg) of 33 percent, the friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 30mg, and the swing angle is 90 degrees) of 35 percent, excellent charging mechanical properties, normal ignition temperature, excellent finished product burning effect, 88dB of measured sound level value, and meets the environmental protection requirements of smokeless and sulfur-free; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at 77 ℃ for 48 hours, no decomposition phenomenon can be seen by naked eyes, and the burning effect of a finished product is not changed; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at the temperature of minus 25 ℃ for 48 hours, the phenomenon of frost cracking can not be seen by naked eyes, and the burning effect of a finished product is not changed.
Example 3
A smokeless and sulfur-free firecracker nitrate medicament comprises the following components in percentage by mass:
dividing 7.83kg of nitrated bamboo cellulose powder into A, B groups, wherein the A group is 2.61kg, the B group is 5.22kg, dissolving the A group of nitrated bamboo cellulose powder in 26.1kg of ethyl acetate, stirring for 3 hours under the ultrasonic dispersion condition, then continuously adding 1.02kg of dicyandiamide, 1.43kg of p-phenylenediamine and 4.08kg of boron nitride under the stirring state, and uniformly stirring to obtain a nitrated bamboo cellulose mixed sol;
under the stirring and ultrasonic dispersion states, adding 47.55kg of passivated hexogen, 5.49kg of potassium nitrate and B group of nitrated bamboo cellulose into the nitrated bamboo cellulose mixed sol, kneading after uniformly mixing, adding 1187ml 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 transferring the dried paste to a 90 ℃ blast oven for drying for 3 hours to prepare 66.37kg of a smokeless and sulfur-free firecracker and nitre crude product;
66.37kg of crude smokeless and sulfur-free firecracker and firecracker are manufactured, wherein the firecracker and firecracker are manufactured, 66.37kg of crude smokeless and sulfur-free firecracker and firecracker.
Tests prove that the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament has the impact sensitivity (the drop height is 250 +/-1 mm, the drop weight is 10.0 +/-0.1 kg) of 30 percent, the friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 30mg, and the swing angle is 90 degrees) of 33 percent, has excellent explosive-charging mechanical property, normal ignition temperature and excellent finished product burning effect, has the measured sound level value of 84dB, and meets the environmental protection requirement of no smoke and sulfur; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at 75 ℃ for 48 hours, no decomposition phenomenon can be seen by naked eyes, and the burning effect of a finished product is not changed; the obtained smokeless and sulfur-free firecracker and firecracker nitrate medicament is placed in a constant-temperature safety box at the temperature of-35 ℃ for 48 hours, the phenomenon of frost cracking can not be seen by naked eyes, and the burning effect of a finished product is not changed.
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 (3)
1. The smokeless and sulfur-free firecracker nitrate medicament is characterized in that: the components and the occupied mass percentage are as follows:
2. the medicament of claim 1, wherein: the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent.
3. A process for preparing the medicament of claim 1, wherein: the method comprises the following specific steps:
weighing passivated hexogen, nitrated bamboo cellulose, boron nitride, potassium nitrate, p-phenylenediamine and dicyandiamide according to the mass ratio of the formula;
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, the p-phenylenediamine and the boron nitride weighed in the step one under the stirring state, and uniformly stirring to obtain a mixed solution of the nitro bamboo cellulose;
step three, under the stirring and ultrasonic dispersion states, adding the passivated hexogen and potassium nitrate weighed in the step one and the B group of the nitrated bamboo cellulose obtained in the step two into the nitrated bamboo cellulose mixed sol obtained in the step two, kneading the mixture after the mixture is uniformly mixed, and adding a proper amount of ethyl acetate into the kneading process to knead the mixture to form uniform micelle with moderate hardness;
step four, granulating the uniform micelle with moderate hardness obtained in the step three 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 smokeless and sulfur-free firecracker and firecracker nitrate medicament crude product;
step five, crushing the crude 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.
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| CN201911255305.6A CN111004074B (en) | 2019-12-10 | 2019-12-10 | Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof |
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| CN201911255305.6A CN111004074B (en) | 2019-12-10 | 2019-12-10 | Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747803A (en) * | 2020-07-14 | 2020-10-09 | 北京理工大学 | Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof |
| CN111912300A (en) * | 2020-08-04 | 2020-11-10 | 北京理工大学 | Stability treatment method of nitrated bamboo cellulose paper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2472648A (en) * | 2009-08-14 | 2011-02-16 | John Douglas Michael Wraige | Pyrotechnic composition and device |
| CN109180395A (en) * | 2018-10-18 | 2019-01-11 | 浏阳市梦幻烟花制造有限公司 | A kind of application of flame retardant dicyandiamide in fireworks medicament |
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2019
- 2019-12-10 CN CN201911255305.6A patent/CN111004074B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2472648A (en) * | 2009-08-14 | 2011-02-16 | John Douglas Michael Wraige | Pyrotechnic composition and device |
| CN109180395A (en) * | 2018-10-18 | 2019-01-11 | 浏阳市梦幻烟花制造有限公司 | A kind of application of flame retardant dicyandiamide in fireworks medicament |
Non-Patent Citations (2)
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| 张先福: "《公安机关民用爆炸物品安全管理工作规范化指南》", 31 May 2012, 中国人民公安大学出版社 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747803A (en) * | 2020-07-14 | 2020-10-09 | 北京理工大学 | Smokeless and sulfur-free firecracker nitrate medicament and preparation method thereof |
| CN111912300A (en) * | 2020-08-04 | 2020-11-10 | 北京理工大学 | Stability treatment method of nitrated bamboo cellulose paper |
| CN111912300B (en) * | 2020-08-04 | 2021-07-20 | 北京理工大学 | Stability treatment method of nitrated bamboo cellulose paper |
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