CN100348554C - Composite oxidant used for fireworks - Google Patents
Composite oxidant used for fireworks Download PDFInfo
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- CN100348554C CN100348554C CNB200610066453XA CN200610066453A CN100348554C CN 100348554 C CN100348554 C CN 100348554C CN B200610066453X A CNB200610066453X A CN B200610066453XA CN 200610066453 A CN200610066453 A CN 200610066453A CN 100348554 C CN100348554 C CN 100348554C
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- composite oxidant
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Abstract
The present invention relates to a composite oxidant used for fireworks, which belongs to the technical field of chemical materials of the firework industry. The composite oxidant uses metal oxide, potassium nitrate, potassium perchlorate and adhesive as raw materials. Firstly, the metal oxide is pulverized, the potassium nitrate and the potassium perchlorate are stirred for dissolving, and the adhesive is added; finally, the metal oxide powder is added in solution to be stirred homogeneously, and a mixture is dried and pulverized. The raw materials which are utilized to form the composite oxidant can be obtained easily, and the composite oxidant which uses the raw materials as main components not only can exert respective oxidation susceptibility but also can generate new performance because of interaction; thus, the present invention is used for replacing the existing oxidant. According to the fireworks manufactured by the traditional technology, the friction sensitivity of the composite oxidant is 0 %, the impact sensitivity of the composite oxidant is 4 %, and the combustion and the explosion of the composite oxidant can not be generated even if the composite oxidant is knocked and rubbed by various modes; thereby, the firework safety in the producing process, the loading process, the unloading process, the transportation process, the storage process, the sale process and other processes can be guaranteed.
Description
Technical field
The present invention relates to a kind of composite oxidant that is used for fireworks and firecrackers, belong to the industrial chemicals technical field that is used for the fireworks and firecrackers industry.
Background technology
The production technique that fireworks and firecrackers manufacturer generally adopts now is that oxygenant, sulphur, aluminium silver powder with outsourcing are mixed by a certain percentage of the weight and mix thoroughly, do to make making up a prescription of firecrackers; With oxygenant, sulphur, aluminium silver powder, toning material, make material etc. and be mixed by a certain percentage and mix thoroughly, do to make making up a prescription of fireworks.Wherein, oxygenant plays a part leading, for burning, blast oxygen supply, is the main component during fireworks and firecrackers makes up a prescription, and accounts for 50～75% of total amount.The power of fireworks and firecrackers explosive power, danger or safety depend mainly on wherein oxygenant kind and ratio thereof.
The oxygenant of fireworks and firecrackers manufacturer use now generally all is a Potcrate.Because the effective oxygen-supplying amount height of Potcrate (39.2%) is flammable good, be convenient to toning, the fireworks and firecrackers sound of making is clear and melodious, and the paper breaking rate height is also economic and practical.But, because Potcrate fusing point low (365 ℃) divides liberation oxygen temperature low (400 ℃), when being mixed with sulphur, metal powder or organism, impact sensitivity and friction sensitivity all very high (reaching 100%), very sensitive to mechanical vibration, have slightly to impact and rub just to set off an explosion.Therefore, with the fireworks and firecrackers of Potcrate, in links such as production, loading and unloading, transportation, storage, sale as oxygenant, explosion hazard happens occasionally, causing great serious accident, make the people's lives and property suffer very big loss, all is a kind of security threat to enterprise and workman.
The fireworks and firecrackers oxygenant of danger make to(for) Potcrate has caused the common concern of countries in the world.China State Council forbids with the medication of Potcrate preparation fireworks and firecrackers in dispatch in 2002.Australia stipulates that the oxygenant that contains Potcrate is forbidden to mix with sulphur, male sulphur, metal object.Japan stipulates that all fireworks are forbidden chloracid potassium, chlorine six generations benzene.Germany's regulation bans the use of Potcrate and metal mixed.The U.S. stipulates that all fireworks ban the use of Potcrate.
In order to exempt the harm of Potcrate, Chinese patent 03118049.3 discloses the technology of " a kind of safety fireworks firecrackers medicament composition ", and it is made up of by certain weight ratio oxygenant, sulphate cpd, aluminium powder, precious rock dust, wood charcoal powder.Wherein oxygenant is metallide or organic bases nitrate, or their combination.Described burning is ferric oxide, Z 250, cupric oxide, Manganse Dioxide, zinc oxide, cobalt oxide, aluminum oxide or their arbitrary combination; Described organic bases nitrate is urea nitrate, Guanidinium nitrate, nitroguanidine, or their arbitrary combination.Oxygenant in this patent, no matter be that metal oxide uses separately or organic bases nitrate uses separately, or both combine to use and have following problem:
At first, the generation heat of described metal oxide is all very high, and promptly negative value is very big, as ferric oxide is-822.16 kj/mol, Z 250 is-1121 kj/mol etc., does not enumerate one by one, and they will divide liberation oxygen to be reduced into simple substance will absorb a large amount of heats.The fusing point that adds them again is very high, as ferric oxide is 1548 ℃, Z 250 is 1540 ℃, make their fusings could divide liberation oxygen, absorb many heats again, so these oxide compounds will reduce the contribute energy of blast acting, promptly so-called " energy factors " is just little, must reduce the blast ability.Described besides metal oxide all is subgroup element except that aluminium, belongs to heavier metal, and its oxygen level of mark is not high by weight.Therefore, no matter how metal oxide makes up, and makees oxygenant separately from " energy factors " and oxygen-supplying amount, and the gunpowder explosion ability that is made into is not strong.
Secondly, described organic bases nitrate, i.e. urea nitrate, Guanidinium nitrate, nitroguanidine, they are a kind of high explosives.Nitroguanidine for example, prestige is for being the 104%TNT equivalent, brisance is 23.7mm (an aluminium post compressed value).Its decomposition reaction is as follows: NH
2-C (NH)-NHNO
2→ 2N
2+ CO+H
2O+H
2, as seen it does not provide available oxygen, is not oxygenant, and it is a kind of military high energy gun propellant that is used for.The gunpowder that it is used for civilian fireworks is infeasible.At first be complex manufacturing, make valuable product.The for example production of nitroguanidine, the first step are to make Guanidinium nitrate, then through the vitriol oil dewater nitroguanidine.Will expend a large amount of energy through 5 technological processs and produce Guanidinium nitrate, cost is very high.Next is that intermediate product in the production process has prussiates such as prussic acid calcium, cyaniding amine, Dyhard RU 100, and is extremely harmful to environment.It is used for military cannon is fine, still be used for broad masses' life in a large number, unfavorable to environment.
Summary of the invention
The objective of the invention is to propose a kind of composite oxidant that is used for fireworks and firecrackers, with fireworks and firecrackers that improve to produce set off performance and security and stability, make simultaneously that production technique is simple, production cost reduces.
The composite oxidant that is used for fireworks and firecrackers that the present invention proposes, the weight percent of each composition is:
Metal oxide 30～80
Saltpetre 20～65
Potassium perchlorate 0～2
Tackiness agent 0.5～3
Its preparation method may further comprise the steps:
(1) metal oxide is crushed to 800～1250 orders;
(2) saltpetre and potassium perchlorate are joined in proportion stirring and dissolving in 80～100 ℃ the water simultaneously, add tackiness agent then in proportion, continuously stirring 10～20 minutes stirs;
(3) metal-oxide powder is joined while stirring in proportion in the solution of step (2), continue to stir 20～40 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 600～1000 orders.
Metal oxide in the above-mentioned safe oxygenant is the mixture of ferric oxide, Z 250 and Manganse Dioxide, and its ratio is: ferric oxide: Z 250: Manganse Dioxide=100: 0～40: 0～30.
The composite oxidant that is used for fireworks and firecrackers that the present invention proposes has the following advantages:
Raw material saltpetre, ferric oxide and Manganse Dioxide that the inventive method is used, it all is oxygenant cheap and easy to get, with them is the composite oxidant that major ingredient is combined into, their oxidation susceptibilities are separately fully played, and produced the performance of many new reality owing to interact.
1, saltpetre wherein can become the initiator of reactive metal oxide.Metal oxide fusing point height (1548 ℃ of ferric oxide, 1785 ℃ of Manganse Dioxide) decomposition temperature is also high, the activation energy that reaction needed is high.Saltpetre fusing point lower (334 ℃), decomposition temperature is 400 ℃, can be at first with fireworks and firecrackers in the aluminium powder reaction cause high temperature more than 2000-2500 ℃, the carrying out that causes W-response fast.
2, effective oxygen-supplying amount of saltpetre can improve the oxygen enrichment value of composite oxidant than metal oxide height.Saltpetre is again the good pore forming agent of metal oxide, can improve the combustion speed of gunpowder significantly.After the mixed slurry drying of burning agent fine powder and potassium nitrate solution, can make oxygenant form the material of vesicular structure, the powder of this multiple oxidant mixes with combustiblematerials can significantly improve combustionvelocity.
3, ferric oxide wherein can quicken the decomposition of saltpetre, becomes the burningrate catalyst of saltpetre, and saltpetre is decomposed fully.Saltpetre decomposites NO when reacting with combustiblematerials
2, further be reduced into NO, and 2NO---N
2+ O
2Reaction very slow, the adding of ferric oxide can form activated intermediate and NO effect, quickens 2NO---N
2+ O
2The process of reaction.Saltpetre can quicken to decompose fully the deep oxidation that impels aluminium powder again.Products of combustion AlO, the Al of aluminium powder
2O further oxidation under the active oxygen effect forms Al
2O
3, produce more energy, improved explosive power.
Between the activity of the oxygenant in the inventive method and the particle diameter of metal oxide and the preparation condition direct relation is arranged.The adding of several compositions such as ferric oxide, Manganse Dioxide and saltpetre must be carried out the micritization processing, mixes and can not only make simple physics.Have only the crystallisation process that enters to saltpetre when the subparticle of oxide compound, form the crystalline particle structure, their catalytic performance just can be not fully exerted.Here require oxide particles such as ferric oxide that enough fineness must be arranged simultaneously, experimental results show that 800-1250 purpose granularity is necessary.
Add a spot of potassium perchlorate and can improve the performance of oxygenant.Under the situation that has other oxide compound and saltpetre to exist, potassium perchlorate bump and friction to external world had buffered leeway, and it is more stable that its performance becomes.But potassium perchlorate has many advantages, and is big with aluminium silver powder reaction thermal value as oxygen-supplying amount height (46.2%), when add-on is lower than 5%, has not only guaranteed safety but also the performance of oxygenant is increased.
The adding of tackiness agent forms very rare colloid, and the very big substance crystallization particulate of several difference of specific gravity is combined, and forms the micritization particle, so that subsequent drying, pulverizing, classification remain uniform system, guarantees quality product homogeneous, stable.The more important thing is to make the oxygenant particle surface that layer film is arranged, improved wear-resisting wiping and impact-resistant performance, reach the reduction mechanical sensitivity, improve the purpose of security.
Oxygenant with the inventive method preparation, substitute the oxygenant chloric acid potassium in the prior art, be equipped with sulphur, aluminium silver powder, toning agent, make agent etc. by traditional technology, make fireworks and firecrackers, its friction sensitivity is 0%, impact sensitivity is 4%, clashes into by any way, rubs can not burn, explode, and can guarantee the safety of fireworks and firecrackers in links such as production, loading and unloading, transportation, storage, sale.
Embodiment.
Embodiment 1
(1) with 55 parts of ferric oxide, 24 parts of separated pulverizing to 1250 order of Manganse Dioxide;
(2) 20 parts in saltpetre is joined stirring and dissolving in 80 ℃ the water, add 1 part of W-Gum then, continuously stirring 15 minutes stirs;
(3) the powder limit of above-mentioned ferric oxide and Manganse Dioxide is stirred the companion limit and joined in the solution of step (2), continue to stir 30 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 1000 orders.
Embodiment 2
(1) with 26 parts of ferric oxide, 24 parts of Z 250s, 12.5 parts of separated pulverizing to 1000 order of Manganse Dioxide;
(2) 0.5 part in 34 parts in saltpetre, potassium perchlorate is joined stirring and dissolving in 90 ℃ the water respectively, add 3 parts in flour then, continuously stirring 20 minutes stirs;
(3) the powder limit of step (1) is stirred the companion limit and joined in the solution of step (2), continue to stir 40 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 900 orders.
Embodiment 3
(1) with 30 parts of ferric oxide, 13 parts of Z 250s, 5 parts of separated pulverizing to 1000 order of Manganse Dioxide;
(2) 1 part of 49 parts in saltpetre and potassium perchlorate is joined simultaneously stirring and dissolving in 95 ℃ the water, add 2 parts of carboxymethyl celluloses then, continuously stirring 20 minutes stirs;
(3) the powder limit of step (1) is stirred the companion limit and joined in the solution of step (2), continue to stir 30 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 800 orders.
Embodiment 4
(1) with 26.5 parts of ferric oxide, 6 parts of separated pulverizing to 800 order of Z 250;
(2) 2 parts of saltpetre 65 and potassium perchlorates are joined simultaneously stirring and dissolving in 100 ℃ the water, add 0.5 part of carboxymethyl cellulose then, continuously stirring 20 minutes stirs;
(3) the powder limit of step (1) is stirred the companion limit and joined in the solution of step (2), continue to stir 40 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 600 orders.
Claims (1)
1, a kind of composite oxidant that is used for fireworks and firecrackers is characterized in that the weight percent of each composition in this oxygenant is:
Metal oxide 30～80
Saltpetre 20～65
Potassium perchlorate 0～2
Tackiness agent 0.5～3
Described metal oxide is the mixture of ferric oxide, Z 250 and Manganse Dioxide, its weight ratio is: ferric oxide: Z 250: Manganse Dioxide=100: 0～40: 0～30, described tackiness agent are any in W-Gum, flour, the carboxymethyl cellulose;
Its preparation method may further comprise the steps:
(1) metal oxide is crushed to 800～1250 orders;
(2) saltpetre and potassium perchlorate are joined in proportion stirring and dissolving in 80～100 ℃ the water simultaneously, add tackiness agent then in proportion, continuously stirring 10～20 minutes stirs;
(3) metal-oxide powder is joined while stirring in proportion in the solution of step (2), continue to stir 20～40 minutes, stir;
(4) said mixture is dried to water content less than 0.2%, be crushed to 600～1000 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610066453XA CN100348554C (en) | 2006-03-31 | 2006-03-31 | Composite oxidant used for fireworks |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610066453XA CN100348554C (en) | 2006-03-31 | 2006-03-31 | Composite oxidant used for fireworks |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1830923A CN1830923A (en) | 2006-09-13 |
| CN100348554C true CN100348554C (en) | 2007-11-14 |
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ID=36993449
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610066453XA Expired - Fee Related CN100348554C (en) | 2006-03-31 | 2006-03-31 | Composite oxidant used for fireworks |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475422B (en) * | 2009-01-16 | 2012-06-20 | 王平安 | Composite oxidizing compound for firework |
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|---|---|---|---|---|
| CN103497079A (en) * | 2013-09-30 | 2014-01-08 | 昆山市巴城镇顺拓工程机械配件厂 | Safe firecracker |
| CN105152824B (en) * | 2015-06-10 | 2017-09-12 | 北京理工大学 | A kind of point of safes gunpowder and preparation method |
| CN106631640B (en) * | 2016-11-24 | 2018-10-02 | 茹友顺 | A kind of electric arc nailing gun of nail shooting pill and preparation method and application the nail shooting pill |
| CN108840783A (en) * | 2018-09-17 | 2018-11-20 | 浏阳市鼎腾烟花有限公司 | A kind of preparation method of firework high energy composite oxidant composition |
| CN110981671A (en) * | 2019-12-03 | 2020-04-10 | 江西吉润花炮新材料科技有限公司 | Smokeless and sulfur-free firework bursting charge and preparation method thereof |
| CN115557820A (en) * | 2021-07-20 | 2023-01-03 | 北京理工大学 | Low-cost environment-friendly explosive containing alloy reducing agent |
| CN115583861A (en) * | 2021-07-21 | 2023-01-10 | 北京理工大学 | Preparation method of metal-based enhanced safe and environment-friendly firework blasting powder |
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| US6749702B1 (en) * | 1996-05-14 | 2004-06-15 | Talley Defense Systems, Inc. | Low temperature autoignition composition |
| EP1498403A2 (en) * | 2003-07-17 | 2005-01-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Additives containing ammonium nitrate particles and process for their preparation |
| WO2005028401A1 (en) * | 2003-09-19 | 2005-03-31 | Britanite S/A - Indústrias Químicas | Process for production of thermal shock tube, and product thereof |
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2006
- 2006-03-31 CN CNB200610066453XA patent/CN100348554C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6749702B1 (en) * | 1996-05-14 | 2004-06-15 | Talley Defense Systems, Inc. | Low temperature autoignition composition |
| US6544363B1 (en) * | 2000-10-30 | 2003-04-08 | Federal Cartridge Company | Non-toxic, heavy-metal-free shotshell primer mix |
| CN1454881A (en) * | 2003-04-17 | 2003-11-12 | 浏阳市化工厂有限公司 | Firecrackers oxidant |
| CN1450030A (en) * | 2003-05-19 | 2003-10-22 | 汪石成 | Safety type compound oxidant |
| EP1498403A2 (en) * | 2003-07-17 | 2005-01-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Additives containing ammonium nitrate particles and process for their preparation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475422B (en) * | 2009-01-16 | 2012-06-20 | 王平安 | Composite oxidizing compound for firework |
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| Publication number | Publication date |
|---|---|
| CN1830923A (en) | 2006-09-13 |
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Granted publication date: 20071114 Termination date: 20120331 |