CN109721446B

CN109721446B - Micro-pyrotechnic composition and application thereof

Info

Publication number: CN109721446B
Application number: CN201910200651.8A
Authority: CN
Inventors: 陈昊彬; 程爱宝
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-03-17
Filing date: 2019-03-17
Publication date: 2021-07-13
Anticipated expiration: 2039-03-17
Also published as: CN109721446A

Abstract

The invention discloses a micro-pyrotechnic composition and application thereof, wherein the micro-pyrotechnic composition comprises the following raw materials in percentage by mass: 1-25% of urea, 40-70% of oxidant, 20-40% of comburant, 1-10% of modified additive and 1-10% of disintegrating agent. The micro-pyrotechnic composition can be applied to pyrotechnic compositions for firecrackers, pyrotechnic compositions for firing cables, and explosive and propellant for fireworks. The ignition material has the characteristics of small usage amount, simple chemical structure of raw materials, easy complete combustion, higher ignition temperature, lower explosion temperature, large gas production and less solid residues, and can effectively reduce the pollution of atmospheric solid particles during ignition.

Description

Micro-pyrotechnic composition and application thereof

Technical Field

The invention belongs to the technical field of fireworks and crackers, relates to a compound composition and application thereof, and particularly relates to a micro-pyrotechnic composition and application thereof.

Background

In China, fireworks and crackers have a development history of more than one thousand years, are important components in various national traditional culture activities, and gradually become new business cards of Chinese traditional culture going to the world nowadays. With the increasing importance of China on the protection of traditional culture related to fireworks and crackers, a plurality of projects are now entering the national list of non-material culture heritage of China. The healthy and stable development of the firework and firecracker industry is an important support for the rapid trend of the traditional culture of China to the world.

The biggest influence on the development of the firework and firecracker industry and the inheritance of related traditional culture is the problem of atmospheric environment pollution in the process of setting off the fireworks and crackers. With the increasingly strict environmental protection requirements of China, fire-forbidden orders are issued in a plurality of cities in China, even fire-forbidden orders are completely saved in some provinces, and the development of the firework and cracker industry is directly led to great difficulty. Only by means of scientific research and customs clearance to solve the environmental protection problem and promote the upgrade of the traditional industry, the contradiction between the development of the firework and firecracker industry, the inheritance of relevant traditional culture and the environmental protection can be fundamentally solved.

The pyrotechnic composition used by the traditional fireworks and crackers has the following defects:

1. the traditional pyrotechnic composition contains a large amount of inorganic substances such as perchlorate, nitrate, permanganate, dichromate, carbon powder, sulfur, aluminum powder, aluminum magnesium alloy powder, calcium carbonate and the like. Many of them are harmful to human body when used in excess, such as dichromate, permanganate, sulfur, aluminum powder.

2. The aluminum powder in the traditional pyrotechnic composition is easy to generate oxidation-reduction reaction with air in a humid environment to generate hydrogen and heat, so that the pyrotechnic composition is easy to self-ignite.

3. In the traditional pyrotechnic composition combustion and explosion process, a large amount of fine particulate matters can be generated after generated metal salts and incompletely combusted reactants are crushed by shock waves, so that PM2.5 and PM10 are polluted.

4. The traditional pyrotechnic composition does not contain hydrogen or contains low hydrogen, and compared with substances with the same mass and high hydrogen content, the traditional pyrotechnic composition has the advantages of low heat of explosion and low gas generation amount in the combustion process, and can not effectively generate water molecules to carry out active dust fall.

5. Charcoal is commonly used in the traditional pyrotechnic composition formula, and the charcoal has the disadvantages of slow combustion speed, low explosion heat and difficult complete reaction in the combustion process, so a large amount of solid particles can be generated after combustion, and the main component of the charcoal is simple substance carbon.

6. A large amount of sulfur dioxide and nitrogen oxide are generated after the traditional pyrotechnic composition is burnt, and the generation of acid rain weather is one of the reasons. For example, the main source of nitrogen oxides is the decomposition of nitrate oxidants in pyrotechnic compositions, but not enough reductant to absorb them; the main source of sulfur dioxide is the oxidation of sulfur in the pyrotechnic composition.

It is known that micro-pyrotechnic compositions have been presented to replace traditional pyrotechnic compositions, but they also have the following drawbacks:

1. the existing micro-pyrotechnic composition still uses inorganic substances such as carbon powder or aluminum powder or perchlorate, rare earth and the like in large quantity. During combustion, the reactants are difficult to burn completely, their products still contain a large amount of solid particles, and many metal oxides are harmful to the human body. For example, the Chinese patent CN103980074A contains 10-20 parts of carbon powder and 10-30 parts of rare earth; the Chinese invention patent CN106966845A contains 10-30 parts of aluminum silver powder; the Chinese invention patent CN106397075A contains 15-25% of metal oxide and 10-20% of carbon material.

2. The existing micro-pyrotechnic composition usually uses ferrocene, cobaltocene and nickelocene as catalysts, and the aromatic ring structure is relatively stable and has higher carbon content. Upon combustion, the reaction temperature is higher than the decomposition temperature of the metallocene, and reacts with oxygen. Because the carbon content of the metallocene is high and the oxygen demand for complete reaction is large, the metallocene is difficult to completely react, and finally generates complex products, mainly comprising simple substance carbon and a plurality of compounds with aromatic ring structures, and further research needs to be carried out on whether the compounds with the aromatic ring structures have carcinogenicity; the cobalt salt generated after combustion enters human body through respiration, and has carcinogenic risk. For example, in the Chinese patent CN109206290A, 3-10% of metallocene and 10-20% of charcoal are used.

3. The existing micro-pyrotechnic composition uses a large amount of single-base powder, but the production and the sale of the single-base powder are strictly controlled, the price is high, the yield is low, and the supply and the demand are often short. Therefore, the single-base powder is only used for high-end products of fireworks and crackers at present. The use amount of the single-base powder can be effectively reduced by reducing the use amount of the single-base powder, the production cost can be greatly reduced, and the product profit is improved. For example, 10-80 parts of single-base powder is used in Chinese invention patent CN 102924193A. In the Chinese invention patent CN108774096A, 87-94% of cellulose nitrate is used. In the Chinese invention patent CN1526687, 70-90% of retired fire powder is used.

4. In the invention patent CN108586175A, the high viscosity colloidal explosive prepared from water, sodium nitrate, urea, ammonium nitrate and other materials needs an electric detonator to detonate in the using process, has high water content, cannot be ignited by the powder lead commonly used in fireworks and crackers, and has a firing effect which does not reach the existing level.

5. The use of excess ammonium nitrate as an oxidizer in the pyrotechnic charge results in the production of high concentrations of toxic gases upon combustion. According to statistics, the content of toxic gas generated by the existing ammonium nitrate explosive is far greater than 50L/Kg specified in national standard, and the generated toxic gas is mainly oxynitride.

6. The synthesis of the nickel hydrazine nitrate and other compounds as the detonator needs stronger professional chemical knowledge and synthesis equipment, and the use of a large amount of the nickel hydrazine nitrate and other compounds can greatly increase the production and safety cost of firework and cracker enterprises.

7. More leavening agents, flame suppressants and the like are additionally added in the existing micro-pyrotechnic compositions, the micro-pyrotechnic compositions do not participate in combustion and explosion reactions, most of the micro-pyrotechnic compositions are water-insoluble metal salts, and a large amount of solid particles can be formed after the micro-pyrotechnic compositions are crushed by shock waves.

8. In the existing literature reports, solid particles generated by the setting off of fireworks and crackers contain a large amount of elemental carbon, and the content of the elemental carbon can even reach 50% of the total amount of PM2.5 and PM10 generated by the setting off, so how to use reasonable materials to reduce the total amount of generated solid particles and nitrogen oxides generated after combustion and increase the total amount of generated gas and water molecules has important significance for researching novel environment-friendly micro-pyrotechnic compositions.

Disclosure of Invention

Aiming at the problems, the invention provides a micro-pyrotechnic composition. The compound composition has the characteristics of small using amount, less solid residue after combustion, low content of toxic and harmful gases, low explosion temperature, large generation amount of gas and water molecules, safety to environment and human bodies and the like, and also provides application of the compound composition in pyrotechnic compositions for firecrackers, pyrotechnic compositions for firing lines, explosive for fireworks and propellant.

In order to achieve the purpose, the invention adopts the following technical scheme:

a micro-pyrotechnic composition comprises urea, an oxidant, a comburent, a modified additive and a disintegrating agent. Wherein the oxidant is: potassium nitrate, sodium nitrate, ammonium nitrate, potassium perchlorate, sodium perchlorate, ammonium perchlorate, potassium chlorate and urea nitrate. The combustion products are: single base powder, nitroguanidine, hexanitrostilbene, starch, cellulose, cane sugar, sucralose, fructose, glucose, polyethylene, polypropylene, polyvinyl alcohol, ethyl cellulose, urea-formaldehyde resin, paraformaldehyde, wood powder, diammonium oxalate and ammonium hydrogen oxalate. The modified additive is as follows: iron powder, titanium powder, potassium bicarbonate, strontium oxalate, barium oxalate, magnesium oxalate, copper oxalate, ammonium iron oxalate, cobalt oxalate, sodium oxalate, potassium dihydroxydioxime, potassium phthalate, rosin, camphor, dibutyl phthalate, tricyanoamine, oxalyldiamide, potassium stearate, potassium sorbate, potassium bitartrate, diphenylamine, stearic acid, oxamide, glycoluril, paraffin, polysaccharide, gelatin, gum arabic, hydroxymethylcellulose, nickel hydrazine nitrate and nickel hydrazine azide. The disintegrating agent comprises the following components: one or more of citric acid, succinic acid, sodium bicarbonate and urea.

The micro-pyrotechnic composition comprises the following components in a mass ratio of 1:40-10: 1. preferably, the mass ratio of urea to comburent is 1: 20-10: 1.

the preferable mixture of the urea, the oxidant, the comburent, the modified additive and the disintegrant comprises the following components in percentage by mass:

1-25% of urea, 40-70% of oxidant, 20-40% of comburant, 1-10% of modified additive and 1-10% of disintegrating agent.

The invention provides a preparation method of a micro-pyrotechnic composition, which comprises the following specific preparation steps:

(1) the urea, the modified additive, the comburent and the oxidant are respectively ground for 20 minutes and sieved by a 100-130-mesh sieve for later use.

(2) And respectively heating the ground modified additive and the oxidant to 55-60 ℃, drying for 2-3 hours, and cooling for later use.

(3) The ground urea, the comburent, the modified additive after the disintegrant is dried and the oxidant are stirred and mixed for 20 minutes, so that the micro-pyrotechnic composition can be obtained and is used for producing firecrackers and firing cables.

(4) Preparing the powdery mixture in the last step into explosive particles with internal micropore structures by adopting a granulation process, and obtaining the explosive for fireworks and the propellant powder.

The invention has the beneficial effects that: 1. the compound composition has the advantages of low price of raw materials, easy acquisition and capability of being produced on the premise of not changing the existing production process to a great extent. 2. The compound composition has simple raw material structure, does not contain a large amount of ammonium nitrate and aromatic ring organic matters, does not contain simple substance carbon, is easy to completely react in the combustion process, mainly generates gas products, and has the toxic gas content lower than 50L/Kg specified in the national standard through detection; the solid residue is little, and the concentration of the generated PM2.5 and PM10 is greatly lower than the index of the conventional gunpowder. 3. The compound composition has high hydrogen and oxygen content ratio, and can generate a large amount of gas and water molecules during combustion, so that the compound composition has a good active dust settling effect. 4. The ignition temperature and the explosion temperature of the compound composition are high, and the safety risk in production, transportation and set-off can be effectively reduced. 5. The disintegrant used in the compound composition can participate in the reaction, mainly takes a gas product after the reaction, and the used flame retardant is a product generated after the reaction and is easily soluble in water, so that the problem of overhigh concentration of solid particles in the product after the combustion caused by the use of the disintegrant and the flame retardant can be greatly reduced. 6. The gas production rate of the compound composition in the combustion process is far greater than that of the traditional pyrotechnic composition and the existing micro pyrotechnic composition, and the using amount of the pyrotechnic composition can be greatly reduced on the premise of ensuring the same effect.

Example one

According to the above preparation method, the urea content was 0.0140g, the sodium perchlorate content was 0.4154g, and the cellulose content was 0.1705 g.

Example two

According to the preparation method, the content of urea is 0.0265g, the content of potassium perchlorate is 0.4269g, and the content of cellulose is 0.1436 g.

EXAMPLE III

According to the preparation method, the urea content is 0.0412g, the potassium perchlorate content is 0.4268g, and the cellulose content is 0.1300 g.

Example four

According to the preparation method, the urea content is 0.080g, the potassium nitrate content is 0.1347g, the potassium perchlorate content is 0.2771g, and the starch content is 0.1080 g.

EXAMPLE five

According to the preparation method, the content of urea is 0.0161g, the content of potassium nitrate is 0.1363g, the content of ammonium chloride is 0.0577g, the content of potassium perchlorate is 0.2803g, and the content of sucralose is 0.1093 g.

EXAMPLE six

According to the preparation method, the content of the single base powder is 0.2518g, the content of the urea is 0.0578g, the content of the potassium nitrate is 0.0974g, and the content of the ammonium nitrate is 0.1928 g.

EXAMPLE seven

According to the preparation method, the iron powder content is 0.0410g, the urea content is 0.0879g, the potassium nitrate content is 0.1776g, and the ammonium nitrate content is 0.2932 g.

Example eight

According to the preparation method, the titanium powder content is 0.0355g, the urea content is 0.0888g, the potassium nitrate content is 0.1794g, and the ammonium nitrate content is 02961 g.

Example nine

According to the preparation method, 0.0594g of polyvinyl alcohol, 0.2388g of potassium nitrate, 0.0912g of urea and 0.2105g of potassium perchlorate are contained.

Example ten

According to the preparation method, 0.0987g of diammonium oxalate, 0.1083g of urea, 0.3603g of potassium perchlorate and 0.0324g of sodium stearate are adopted.

Comparative example

According to the preparation method, 75g of potassium nitrate, 15g of charcoal and 10g of sulfur are adopted.

The embodiment can be directly applied to pyrotechnic compositions of firecrackers and pyrotechnic compositions of firing cables, and can be used for explosive bursting and propellant of fireworks after a granulation process.

According to GB10631-2013 and GJB5384.6-2005 standards, part of the test results are as follows:

the principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.

Claims

1. The micro-pyrotechnic composition comprises effective components, and is characterized in that the effective components are urea, an oxidant, a comburant, a modification additive and a disintegrant, the oxidant is potassium perchlorate and/or sodium perchlorate, the comburant is starch and/or cellulose and/or sucrose and/or sucralose and/or wood flour, the modification additive is potassium stearate and/or potassium sorbate and/or potassium hydrogen tartrate and/or stearic acid and/or iron powder and/or titanium powder and/or strontium oxalate and/or barium oxalate and/or cobalt oxalate and/or sodium oxalate and/or potassium oxalate and/or magnesium oxalate, the disintegrant is citric acid and/or succinic acid and/or sodium bicarbonate, the mass ratio of the urea to the comburant is 1:40-10:1, the compound composition comprises the following components in percentage by mass: 1-25% of urea; 40-70% of an oxidant; 20-40% of a comburent; 1-10% of modified additive; 1-10% of disintegrating agent.