WO2013023578A1 - 一种新型灭火组合物 - Google Patents

一种新型灭火组合物 Download PDF

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WO2013023578A1
WO2013023578A1 PCT/CN2012/080104 CN2012080104W WO2013023578A1 WO 2013023578 A1 WO2013023578 A1 WO 2013023578A1 CN 2012080104 W CN2012080104 W CN 2012080104W WO 2013023578 A1 WO2013023578 A1 WO 2013023578A1
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fire extinguishing
extinguishing composition
fire
mass
composition according
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PCT/CN2012/080104
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English (en)
French (fr)
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翟腾飞
田巍
张为鹏
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陕西坚瑞消防股份有限公司
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Publication of WO2013023578A1 publication Critical patent/WO2013023578A1/zh

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    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components

Definitions

  • the invention belongs to the field of aerosol fire extinguishing technology, and in particular relates to an aerosol fire extinguishing composition. Background technique:
  • Aerosol fire extinguishing technology has attracted much attention because of its characteristics of non-toxicity, non-corrosion, high volumetric efficiency, long storage period, full flooding, and all-round fire extinguishing. From the end of the last century to the present, aerosol technology has been rapidly developed. The development of related patents has emerged one after another.
  • the existing aerosol fire extinguishing agents mainly include S-type and K-type fire extinguishing agents.
  • Aerosol fire extinguishing agents use redox reaction to release a large amount of gas and active. Particles, through the chain scission reaction of active particles, a large amount of gas covering suffocation, realizing chemical and physical aerosols, releasing a large amount of heat, in order to effectively reduce the temperature of the device and aerosol, avoid secondary fires, increase the cooling system
  • the addition of the cooling system results in a complicated and cumbersome structure, complicated process flow and high cost.
  • the present invention provides a new fire extinguishing composition with high fire extinguishing efficiency, good safety performance and high utilization rate.
  • a novel fire extinguishing composition characterized in that: the fire extinguishing composition comprises
  • the fire extinguishing composition is a pyrotechnic agent as a heat source and a power source, and the fire extinguishing composition reacts by igniting the pyrotechnic composition to generate a large amount of fire extinguishing substance, with the fireworks The medicinal agents are sprayed together to extinguish the fire.
  • the fire extinguishing composition may further comprise a binder in a mass percentage of 1% to 15%; and is mainly selected from the group consisting of water glass, shellac, starch, dextrin, rubber, epoxy resin, acetal glue, hydroxypropyl methyl group.
  • a binder in a mass percentage of 1% to 15%; and is mainly selected from the group consisting of water glass, shellac, starch, dextrin, rubber, epoxy resin, acetal glue, hydroxypropyl methyl group.
  • cellulose and phenolic resin One or more of cellulose and phenolic resin.
  • the use of an adhesive in a fire extinguishing composition is a conventional technique in the art, and its content is usually controlled to be 15% or less.
  • a performance catalyst may be added to the above fire extinguishing composition, and the mass percentage thereof is controlled in a range of more than 0% to 5% or less. It may be selected from one or more of manganese dioxide, metallic nickel, and metallic iron.
  • the gas-fired component of the present invention may be melamine or I and cesium carbonate, which are selected depending on the application ratio.
  • the fire extinguishing composition of the present invention may further add an additive, which is one or more of a stearate, talc, graphite, and a water-soluble high polymer compound solution, but the content of the additive is controlled to be 20 or less. % (quality).
  • an additive which is one or more of a stearate, talc, graphite, and a water-soluble high polymer compound solution, but the content of the additive is controlled to be 20 or less. % (quality).
  • the fire extinguishing composition of the invention uses hydroxymethyl cellulose or hydroxyethyl cellulose as its surface coating agent to improve the surface finish of the composition system, improve the strength, wear resistance and shock resistance, and prevent fire during transportation.
  • the composition pulverizes, slags and overflows the fire extinguishing device.
  • the flame suppression mechanism of the fire extinguishing composition of the present invention is as follows:
  • the fire extinguishing composition can be decomposed and released at a high temperature to release a fire extinguishing substance, which can be cut by one or more of 0, 0H, and H ⁇ radicals necessary for radical and chain combustion reactions.
  • the chain combustion reaction can also reduce the partial pressure of oxygen by physical action to suppress the flame, or simultaneously achieve physical and chemical inhibition to achieve the fire extinguishing effect, and at the same time, synergistic effect with the pyrotechnic agent, further improving the fire extinguishing agent
  • the fire extinguishing efficiency greatly shortens the effective fire extinguishing time.
  • the fire extinguishing composition of the present invention has the advantages of: the optimum ratio of the fire composition, thereby greatly improving the performance of the fire extinguishing composition, and fully utilizing the effectiveness of the components of the fire extinguishing composition, and improving the effective utilization rate of the fire extinguishing composition. .
  • the fire-extinguishing composition of the present invention can rapidly undergo an endothermic decomposition reaction under heat, effectively and rapidly reducing the heat released by the pyrotechnic composition combustion, greatly reducing the temperature of the fire-extinguishing device spout and the discharge material, and being safer. Moreover, the fire extinguishing time is greatly shortened.
  • the present invention adds a component of a performance catalyst and a binder, which can further improve the fire extinguishing performance and processing property of the fire extinguishing material, and make the performance stable and easy to store for a long time.
  • the fire extinguishing composition of the present invention uses hydroxymethyl cellulose or hydroxyethyl cellulose as a surface coating agent thereof to improve the surface finish of the composition system, improve the strength, wear resistance and shock resistance, and prevent the transportation process.
  • the phenomenon occurs in which the fire extinguishing composition is pulverized, slag is discharged and the fire extinguishing device is overflowed.
  • the composition for producing a fire extinguishing substance by chemical reaction between components of the present invention comprises the components and corresponding mass percentages: ferrocene: 5 to 30 (mass)%, preferably 15% to 25% ; dicyandiamide: 10 ⁇ 60 (mass)%, preferably 15% ⁇ 30%; gas fire extinguishing component: 10 ⁇ 60 (mass)%, preferably 30% ⁇ 55%; binder: 1% ⁇ 15% Performance catalyst, greater than 0% to less than or equal to 5%; wherein, the gas-fired fire extinguishing component may be melamine or strontium carbonate, or may be a combination of melamine and strontium carbonate; adjusted according to the ratio and application Choose.
  • the binder is mainly selected from one or more of water glass, shellac, starch, dextrin, rubber, epoxy resin, acetal glue, hydroxypropyl methylcellulose, phenolic resin; One or more of manganese dioxide, metallic nickel, and metallic iron.
  • the fire extinguishing composition is used as a heat source and a power source when the pyrotechnic composition is used, and the fire extinguishing composition reacts to ignite the fire extinguishing agent to generate a large amount of fire extinguishing substance, and the fire extinguishing substance is sprayed together with the pyrotechnic agent. It can be reacted by one or more of 0, 0H, and H ⁇ radicals necessary for radical and chain combustion reactions, thereby cutting off the chain combustion reaction, and also reducing the oxygen partial pressure by physical action. Inhibition of the flame, or simultaneous physical and chemical inhibition to achieve a fire-extinguishing effect, is more efficient and safer than conventional fire-extinguishing compositions, and is primarily used to extinguish Class B fires.
  • the fire extinguishing composition of the present invention may further contain various additives as needed, and may be, for example, stearate, talc, graphite, a water-soluble high polymer compound solution or a mixture thereof, in order to facilitate its processing and performance enhancement.
  • the content can be controlled to be 20% by mass or less.
  • the fire extinguishing composition of the present invention can be formed into a spherical shape, a sheet shape, a strip shape, a block shape, a honeycomb shape by a process such as pelleting, molding, extrusion, and the like, and can be subjected to surface coating treatment.
  • a process such as pelleting, molding, extrusion, and the like
  • it is preferred to add hydroxymethylcellulose or hydroxyethylcellulose as a surface coating agent.
  • the surface coating agent can improve the surface finish of the composition system, and improve its strength, wear resistance and shock resistance, and prevent the occurrence of powdering of the fire extinguishing composition during transportation, slag discharge and overflow of the fire extinguishing device.
  • test record table 1 50 g of the prepared ferrocene, dicyandiamide, melamine, acetal and magnesium stearate composition samples were added to a fire extinguishing device equipped with 50 g of K-type hot aerosol generating agent, and the implementation area was 0. 25m 2 oil pan 93# gasoline fire extinguishing test; the experimental results are shown in test record table 1.
  • test record table 1 50 grams of the prepared ferrocene, dicyandiamide, cesium carbonate, hydroxypropyl methylcellulose and talc powder samples were added to a fire extinguishing device equipped with 50 grams of K-type hot aerosol generating agent, and the implementation area was 0. .
  • test record table 1 50 g of the prepared ferrocene, dicyandiamide, cesium carbonate, melamine, acetal and magnesium stearate composition samples were added to a fire extinguishing device equipped with 50 g of a K-type hot aerosol generating agent, and the implementation area was 0. .
  • test record table 1 50 grams of the prepared ferrocene, dicyandiamide, cesium carbonate, hydroxypropyl methylcellulose and graphite powder composition samples were added to a fire extinguishing device containing 50 grams of K-type hot aerosol generating agent, and the implementation area was 0. .
  • a fire extinguishing device sample containing only 100 g of S-type hot aerosol fire extinguishing agent was used, and a 93# gasoline fire extinguishing test with an area of 0.25 m 2 oil pan was implemented; the test test results are shown in Table 1.
  • the comparative example is also a sample of a fire extinguishing device containing 100g of S-type aerosol fire extinguishing agent or K-type aerosol fire extinguishing agent, and the fire extinguishing test is carried out under the same conditions to record the fire extinguishing effect and spray. Shoot time, the results are shown in Table 1.
  • the fire-extinguishing composition of the present invention can be used for two or three rounds, and the existing products are not extinguished.
  • the spray time of the present invention is up to 10.98 s, and the existing The product injection time can reach 36. 55 s, and the long-term injection time will affect the fire-extinguishing performance. Therefore, the fire extinguishing composition of the present invention is significantly more effective than existing products.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)

Abstract

本发明涉及一种新型灭火组合物,该灭火组合物包括:二茂铁:5~30(质量)%;双氰胺:10~60(质量)%;产气灭火组分:10~60(质量)%;其以烟火类药剂为热力源和动力源,通过点燃烟火类药剂燃烧放出热量使该灭火组合物发生反应产出大量灭火物质,随烟火类药剂一起喷出而灭火。通过优选组分以及优化组分含量,确定了灭火组合物的最佳配比,从而大大提高灭火组合物的效能,而且充分利用了灭火组合物的各组分的效能,提高灭火组合物的有效利用率。

Description

一种新型灭火组合物 本申请依赖并要求 2011 年 08 月 16 日提交的中国专利申请 201110235063.1的优先权, 在此通过参考将其全部内容并入本文。
技术领域:
本发明属于气溶胶灭火技术领域, 特别涉及一种气溶胶灭 火组合物。 背景技术:
气溶胶灭火技术, 因为具有无毒、 无腐蚀、 容积效率高、 贮存周期 长、 全淹没、 全方位灭火等特点而备受瞩目, 从上世纪末到目前的十多 年间, 气溶胶技术得到了迅猛的发展, 相关专利层出不穷。
现有的气溶胶灭火剂主要有 S 型和 K 型灭火剂, 通过综 合分析其性能特点, 其不足之处主要有: 气溶胶灭火剂均是利 用灭火剂发生氧化还原反应释放出大量气体、 活性粒子, 通过 活性粒子的断链反应, 大量气体的覆盖窒息, 实现化学与物理 气溶胶的同时, 释放出大量的热, 为了有效降低装置和气溶胶 的温度, 避免发生二次火灾, 需增加冷却系统, 增加了冷却系 统导致装置结构复杂笨重, 工艺流程复杂, 成本高, 由于冷却 系统的存在, 使大量活性粒子经过冷却层过滤后失去活性, 导 致灭火性能大大降低; 另外现有的灭火剂也没有充分利用各灭 火组分的灭火效能, 其灭火效能有限, 造成药剂成本在一定程 度上的浪费。 发明内容:
基于现有技术中的灭火药剂存在的灭火性能不高, 有效利用率低的 问题, 本发明提供了一种灭火效能高、 安全性能好而且利用率较高的新 型灭火组合物。
本发明所采用的技术方案是:
一种新型灭火组合物, 其特征在于: 该灭火组合物包含
二茂铁: 5 ~ 30 (质量)%, 优选 15 ~ 25 (质量)%; 双氰胺: 10 - 60 (质量)%,优选 15% ~ 30%;产气灭火组分: 10 ~ 60 (质量)%,优选 30% ~ 55%; 该灭火组合物是以烟火类药剂为热力源和动力源, 通过点燃烟火类 药剂燃烧放出热量使该灭火组合物发生反应产出大量灭火物质, 随烟火 类药剂一起喷出而灭火。
上述灭火组合物还可以包括粘合剂,质量百分比为 1% ~ 15%; 其主要 选自水玻璃、 虫胶、 淀粉、 糊精、 橡胶、 环氧树脂、 缩醛胶、 羟丙基甲 基纤维素以及酚醛树脂中的一种或多种。 但是对于粘合剂在灭火组合物 中的应用属于本领域的常规技术手段, 通常其含量控制在 15%以下。
为了加强其药剂的性能, 在上述灭火组合物中还可以添加性能催化 剂, 将其质量百分比控制在大于 0%至小于等于 5%的范围内。 其可以选自 二氧化锰、 金属镍、 金属铁中的一种或多种。
本发明的产气灭火组分可以是三聚氰胺或 I和碳酸胍, 根据应用配比 进行选择。
本发明的灭火组合物还可以添加添加剂, 所述添加剂为硬脂酸盐、 滑石粉、 石墨、 水溶性高聚物复配溶液中的一种或多种, 但是添加剂的 含量控制要小于等于 20 % (质量)。
本发明的灭火组合物采用羟甲基纤维素或羟乙基纤维素作为其表面 包覆剂, 改善组合物体系的表面光洁度, 并提高其强度、 耐磨性和抗震 性, 防止运输过程中灭火组合物发生粉化, 掉渣并溢出灭火装置现象的 出现。
本发明的灭火组合物的火焰抑制机理如下: 灭火组合物在高温下可分解释放出灭火物质, 该灭火物质可通过自 由基与链式燃烧反应所必需的 0 ·、 0H ·、 H · 自由基中的一种或几种进行 反应, 从而切断了链式燃烧反应, 也可通过物理作用减少氧气分压而抑 制火焰, 或同时发生物理及化学抑制作用共同实现灭火效果, 与此同时, 与烟火药剂产生协同增效作用, 进一步提高了灭火剂的灭火效能, 大大 缩短了有效灭火时间。
本发明的灭火组合物的优点是: 火组合物的最佳配比, 从而大大提高灭火组合物的效能, 而且充分利用 了灭火组合物的各组分的效能, 提高灭火组合物的有效利用率。
2、本发明的灭火组合物在受热情况下,即可迅速发生吸热分解反应, 有效快速的降低了烟火药剂燃烧释放的热量, 大大降低了灭火装置喷口 及喷放物质的温度, 更安全, 而且灭火时间大大缩短。
3、 本发明添加了性能催化剂和粘合剂的成分, 能够进一步提高了灭 火材料的灭火性能和加工性能, 使其性能稳定并易于长期贮存。
4、 本发明的灭火组合物采用羟甲基纤维素或羟乙基纤维素作为其表 面包覆剂, 改善组合物体系的表面光洁度, 并提高其强度、 耐磨性和抗 震性, 防止运输过程中灭火组合物发生粉化, 掉渣并溢出灭火装置现象 的出现。
Figure imgf000004_0001
本发明的通过组分间发生化学反应产生灭火物质的组合物 , 其包含 的各组分及对应的质量百分含量为:二茂铁: 5 ~ 30 (质量)%,优选 15% ~ 25%; 双氰胺: 10 ~ 60 (质量)%, 优选 15% ~ 30%; 产气灭火组分: 10 ~ 60 (质量)%, 优选 30% ~ 55%; 粘合剂: 1% ~ 15%; 性能催化剂, 大于 0% 至小于等于 5%; 其中, 产气灭火组分可以是三聚氰胺, 也可以是碳酸胍, 或者还可以是三聚氰胺和碳酸胍的组合; 根据配比与应用来进行调整选 择。 粘合剂主要选自水玻璃、 虫胶、 淀粉、 糊精、 橡胶、 环氧树脂、 缩 醛胶、 羟丙基甲基纤维素、 酚醛树脂中的一种或多种; 性能催化剂可选 自二氧化锰、 金属镍、 金属铁中的一种或多种。
本灭火组合物在使用时是以烟火类药剂为热力源和动力源, 通过点 燃烟火类药剂燃烧放出热量使灭火组合物发生反应产出大量灭火物质, 该灭火物质随烟火类药剂一起喷出, 可通过自由基与链式燃烧反应所必 需的 0 ·、 0H ·、 H · 自由基中的一种或几种进行反应, 从而切断了链式燃 烧反应, 也可通过物理作用减少氧气分压而抑制火焰, 或同时发生物理 及化学抑制作用共同实现灭火效果, 与传统的灭火组合物相比, 其更高 效、 更安全, 而且其主要是用于朴灭 B类火。
本发明的灭火组合物还可以根据需要加入各种添加剂, 例如可以为 硬脂酸盐、 滑石粉、 石墨、 水溶性高聚物复配溶液或其混合物, 以便于 其加工成型且性能加强, 其含量可以控制在 20 质量%以下。
本发明的灭火组合物可以采用制丸、 模压、 挤压等工艺成型为球状, 片状, 条状, 块状, 蜂窝状, 并且可经过表面包覆处理。 进行表面包覆 处理时优选加入羟甲基纤维素或羟乙基纤维素作为表面包覆剂。 该表面 包覆剂可以改善组合物体系的表面光洁度, 并提高其强度、 耐磨性和抗 震性, 防止运输过程中灭火组合物发生粉化, 掉渣并溢出灭火装置现象 的出现。
上述的灭火组合物, 其通过以下的方式以及实验结果可以毫无疑义 地得出本发明的灭火组合物的效能明显优于现有的灭火药剂, 而且灭火 时间也大大缩短。 具体可参见如下实验:
实施例 1
将制成的二茂铁、 双氰胺、 三聚氰胺、 缩醛胶及硬脂酸镁组合物样 品 50 克加入装有 50 克 K型热气溶胶发生剂的灭火装置中, 实施面积为 0. 25m2 油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
实施例 2
将制成的二茂铁、 双氰胺、 三聚氰胺、 缩醛胶及硬脂酸镁组合物样 品 50 克加入装有 50 克 K型热气溶胶发生剂的灭火装置中, 实施面积为 0. 25m2油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
实施例 3
将制成的二茂铁、 双氰胺、 碳酸胍、 缩醛胶及硬脂酸镁组合物样品 50克加入装有 50克 K型热气溶胶发生剂的灭火装置中,实施面积为 0. 25m2 油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
实施例 4
将制成的二茂铁、 双氰胺、 碳酸胍、 羟丙基甲基纤维素及滑石粉组 合物样品 50克加入装有 50克 K型热气溶胶发生剂的灭火装置中, 实施面 积为 0. 25m2 油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
实施例 5
将制成的二茂铁、 双氰胺、 碳酸胍、 三聚氰胺、 缩醛胶及硬脂酸镁 组合物样品 50克加入装有 50克 K型热气溶胶发生剂的灭火装置中, 实施 面积为 0. 25m2 油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
实施例 6
将制成的二茂铁、 双氰胺、 碳酸胍、 羟丙基甲基纤维素及石墨粉组 合物样品 50克加入装有 50克 K型热气溶胶发生剂的灭火装置中, 实施面 积为 0. 25m2 油盘的 93#汽油灭火试验; 实验结果见试验记录表 1。
对比例 1
将只装有 100g K 型热气溶胶灭火剂的灭火装置样品, 实施面积为 0. 25m2油盘的 93#汽油灭火试验; 试验测试结果见表 1。
对比例 2
将只装有 100g S 型热气溶胶灭火剂的灭火装置样品, 实施面积为 0. 25m2油盘的 93#汽油灭火试验; 试验测试结果见表 1。
将下表中的灭火材料、粘合剂及添加剂制成的灭火组合物 50g, 制备 成型后, 分别加入装有 5 OgK型气溶胶发生剂的灭火装置中, 分别进行 8B 灭火试验, 具体试验模型见 GA86-2009 中 6. 3. 2. 1。 每组进行三发, 记 录灭火效果及灭火时间, 试验结果见表 1。
对比例也是分别装有 100gS型气溶胶灭火剂或者 K型气溶胶灭火剂 的灭火装置的样品, 在相同的条件下进行灭火试验, 记录灭火效果及喷 射时间, 结果见表 1。
表 1 各种组分成分比较和试验结果对比
Figure imgf000007_0001
由上述表 1可以得出: 本发明的灭火组合物可以灭掉两发或 者三发, 而现有的产品均未灭掉, 另外, 本发明的喷射时间最 长为 10. 98s , 而现有的产品喷射时间可达 36. 55 s , 喷射时间长 即灭火效能就会受到影响。 因此, 本发明的灭火组合物效果明 显优于现有的产品。

Claims

权利要求
1、 一种新型灭火组合物, 其特征在于: 所述灭火组合物的组分及其 含量为:
二茂铁: 5 ~ 30 (质量)%
双氰胺: 1 0 - 60 (质量)%
产气灭火组分: 1 Q ~ 6 Q (质量)%
所述灭火组合物是以烟火类药剂为热力源和动力源,通过点燃烟火类 药剂燃烧放出热量使该灭火组合物发生反应产出大量灭火物质, 随烟火 类药剂一起喷出而灭火。
2、 根据权利要求 1所述的新型灭火组合物, 其特征在于: 所述灭火 组合物还包括粘合剂, 质量百分比为 1% ~ 15%。
3、 根据权利要求 2所述的新型灭火组合物, 其特征在于: 所述粘合 剂为水玻璃、 虫胶、 淀粉、 糊精、 橡胶、 环氧树脂、 缩醛胶、 羟丙基甲 基纤维素以及酚酸树脂中的一种或多种。
4、 根据权利要求 1所述的新型灭火组合物, 其特征在于: 所述灭火 组合物还包括性能催化剂, 质量百分比为大于 0%至小于等于 5%。
5、 根据权利要求 4所述的新型灭火组合物, 其特征在于: 所述性能 催化剂为二氧化锰、 金属镍、 金属铁中的一种或多种。
6、 根据权利要求 1至 5任一所述的新型灭火组合物, 其特征在于: 所述的二茂铁质量百分比优选为 15% ~ 25%。
7、 根据权利要求 1至 5任一所述的新型灭火组合物, 其特征在于: 所述的双氰胺质量百分比优选为 15% ~ 30%。
8、 根据权利要求 1至 5任一所述的新型灭火组合物, 其特征在于: 所述的产气灭火组分为三聚氰胺或 /和碳酸胍, 其质量百分比为 30% ~ 55%。
9、 根据权利要求 1至 5任一所述的新型灭火组合物, 其特征在于: 所述灭火组合物还包括添加剂; 所述添加剂的含量为大于 0至小于等于 20质量%。
10、 根据权利要求 9所述的新型灭火组合物, 其特征在于: 所述添 加剂为硬脂酸盐、 滑石粉、 石墨、 水溶性高聚物复配溶液中的一种或其 混合物。
11、 根据上述任一权利要求所述的新型灭火组合物, 其特征在于: 所述灭火组合物采用羟甲基纤维素或羟乙基纤维素作为其表面包覆剂。
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