WO2014048274A1 - 一种气溶胶发生剂 - Google Patents

一种气溶胶发生剂 Download PDF

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Publication number
WO2014048274A1
WO2014048274A1 PCT/CN2013/083844 CN2013083844W WO2014048274A1 WO 2014048274 A1 WO2014048274 A1 WO 2014048274A1 CN 2013083844 W CN2013083844 W CN 2013083844W WO 2014048274 A1 WO2014048274 A1 WO 2014048274A1
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agent
aerosol generating
phenolic resin
generating agent
acid
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PCT/CN2013/083844
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English (en)
French (fr)
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郑高锋
史军军
赵小青
高超
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西安坚瑞安全应急设备有限责任公司
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Publication of WO2014048274A1 publication Critical patent/WO2014048274A1/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 generating agent and a preparation process thereof.
  • Aerosol fire extinguishing agent is a new fire extinguishing agent with extremely high fire extinguishing efficiency, zero ozone depletion value ODN, non-toxic and harmless, no residue, low price and low equipment investment. Under the urgent background of halon elimination, it has obtained the government. The strong support also caters to the needs of the market, so aerosol fire suppression technology has become one of the most attractive halon replacement technologies in the past decade.
  • aerosol As a substitute for halon products, aerosol has the characteristics of high fire extinguishing performance and no secondary pollution. It has a wide range of applications in the domestic and international fire extinguishing industry.
  • the formulation of such generators mainly includes oxidants, reducing agents, binders, additives and processing aids.
  • the selection of a suitable material not only greatly enhances the fire extinguishing performance of the agent, but also enhances the processing, storage, and use properties of the agent. These properties are also an integral part of the aerosol generating agent.
  • the reducing agents commonly used in aerosol generating agents are all alkaline substances. If the object to be fired is too acidic, it will cause corrosion and damage to some acidic equipment while extinguishing the fire. For example, if the oil tank is on fire, the existing aerosol fire extinguishing agent can extinguish the fire, but the alkaline substance will cause some components in the crude oil to saponify and flocculate, which will affect the performance of the crude oil and affect the reuse.
  • the present invention provides an aerosol generating agent which has a simple composition, a large gas production amount, is sufficiently burned, and is more suitable for an acid fire extinguishing object, and a preparation process thereof.
  • An aerosol generating agent consisting of an oxidizing agent, a reducing agent and a binder, wherein: the oxidizing agent is cerium nitrate and potassium nitrate, the binder is a phenolic resin, and the reducing agent is tartaric acid, dihydroxytartaric acid, and B.
  • the oxidizing agent is cerium nitrate and potassium nitrate
  • the binder is a phenolic resin
  • the reducing agent is tartaric acid, dihydroxytartaric acid
  • B One or more of diaminetetraacetic acid, salicylic acid, and phthalic anhydride.
  • the reducing agent has a mass percentage of 5% to 25%.
  • the mass percentage of each component in the aerosol generating agent is:
  • the mass percentage of each component in the aerosol generating agent is
  • the mass ratio of cerium nitrate to potassium nitrate in the oxidizing agent is 2:1 to 10:1, preferably 2:1 to 4:1, more preferably 3:1.
  • Another object of the present invention is to provide a process for preparing an aerosol generating agent, which is characterized in that: 1) the phenolic resin is dissolved in ethanol to prepare a phenolic resin having a mass percentage of 50% to 65%.
  • the oxidant and reducing agent are pulverized to a fineness of 100-200 standard purpose, and mixed according to the ratio, and sieved three times with 100-200 mesh to make it evenly mixed;
  • the reducing agent is an acidic reducing substance such as tartaric acid, dihydroxytartaric acid, ethylenediaminetetraacetic acid, salicylic acid or phthalic anhydride, which is different from the basic reducing agent used in the prior art.
  • an acidic reducing substance such as tartaric acid, dihydroxytartaric acid, ethylenediaminetetraacetic acid, salicylic acid or phthalic anhydride, which is different from the basic reducing agent used in the prior art.
  • it compensates for the shortcomings of the current conventional patents in which the use of an aerosol fire extinguishing agent containing an alkaline reducing agent is less effective or has a more negative impact on the protected object after use, such as in the case of crude oil fire extinguishing, due to the crude oil itself. It is weakly acidic.
  • the alkaline aerosol will greatly increase the chance of saponification reaction between the generating agent and the crude oil component to cause flocculation, which brings about subsequent processing of the crude oil.
  • Trouble, and the aerosol generated by the aerosol generator of tartaric acid, dihydroxytartaric acid, ethylenediaminetetraacetic acid, salicylic acid, phthalic anhydride and other acidic substances is weakly acidic, and does not react with crude oil during fire extinguishing. Reactions are eliminated to prevent this negative effect; on the other hand, in the use of chemical coolants, such as the use of acidic chemical coolants, acidic or neutral aerosol generators are required, otherwise the two will affect each other. Greatly reduce the storage performance and fire extinguishing performance of the generator and chemical coolant. Therefore, the aerosol generating agent of the present invention is not only a supplement to the existing aerosol fire extinguishing agent, but also an extension of its application field.
  • the aerosol generating agent of the present invention can be used alone as a fire extinguishing agent, or can be used in combination with a chemical coolant as a heat source and a power source for a chemical coolant.
  • the aerosol generating agent of the present invention has stable performance, is easy to store for a long period of time, and is excellent in environmental friendliness.
  • the aerosol generating agent of the invention adopts an acidic reducing agent, and is more suitable for the object of partial acidity, and can effectively prevent corrosion and damage of certain acidic equipments and effectively affect the re-use.
  • the present invention preferably optimizes the proportion of each component in the aerosol generating agent so that it can be sufficiently burned under the preparation conditions of the present invention, and the residual amount of the generating agent is smaller.
  • phenolic resin 7g was dissolved in 4g of industrial alcohol to prepare a uniform phenolic resin ethanol solution.
  • 42g of lanthanum nitrate, 30g of potassium nitrate, 12g of ethylenediaminetetraacetic acid, and 9g of tartaric acid were respectively sieved through a 200-mesh standard sieve and then uniformly mixed.
  • the above phenolic resin ethanol solution is forcibly stirred uniformly, granulated by a 40-mesh sieve, and dried in an environment of a temperature of 25 ° C to 55 ° C and a humidity of 30% or less until the volatile content of the composition is not more than 1%.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical placing device having ⁇ 25 ⁇ under a pressure of not less than 3 MPa for a fire extinguishing test.
  • phenolic resin 10 g was dissolved in 8 g of industrial alcohol to prepare a uniform phenolic resin ethanol solution, and 50 g of lanthanum nitrate, 24 g of potassium nitrate, and 16 g of phthalic anhydride were respectively sieved through a 200-mesh standard sieve, and then uniformly mixed, and the above phenolic resin was added.
  • the ethanol solution is forcibly stirred uniformly, granulated by a 40-mesh sieve, and dried in an environment having a temperature of 25 ° C to 55 ° C and a humidity of 30% or less until the volatile content of the composition is not more than 1%.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical placing device having ⁇ 25 ⁇ under a pressure of not less than 3 MPa for fire-extinguishing test.
  • phenolic resin 8 g was dissolved in 5 g of industrial alcohol to prepare a uniform phenolic resin ethanol solution, and 60 g of lanthanum nitrate, 20 g of potassium nitrate, 7 g of dihydroxytartaric acid, and 5 g of salicylic acid were separately sieved through a 200-mesh standard sieve, and then uniformly mixed.
  • the above phenolic resin ethanol solution is added to be uniformly stirred, granulated by a 40-mesh sieve, and dried in an environment of a temperature of 25 ° C to 55 ° C and a humidity of 30% or less until the volatile content of the composition is not more than 1%.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical insertion device having a ⁇ 25 ⁇ under a pressure of not less than 3 MPa for a fire extinguishing test.
  • 10 g of phenolic resin was dissolved in 8.5 g of industrial alcohol to prepare a uniform phenolic resin ethanol solution, and 62 g of lanthanum nitrate, 14 g of potassium nitrate, 6 g of ethylenediaminetetraacetic acid, and 8 g of salicylic acid were respectively passed through a 200-mesh standard sieve and then mixed.
  • the above phenolic resin ethanol solution is added to be uniformly stirred, granulated by a 40-mesh sieve, and dried in an environment of a temperature of 25 ° C to 55 ° C and a humidity of 30% or less until the volatile content of the composition is not more than 1%.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical insertion device having a ⁇ 25 ⁇ under a pressure of not less than 3 MPa for a fire extinguishing test.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical insertion device having a ⁇ 25 ⁇ under a pressure of not less than 3 MPa for a fire extinguishing test.
  • phenolic resin 10 g was dissolved in 6 g of industrial alcohol to prepare a uniform phenolic resin ethanol solution, and 75 g of lanthanum nitrate, 5 g of potassium nitrate, and 10 g of phthalic anhydride were respectively sieved through 200 targets, and then uniformly mixed, and the above phenolic resin was added.
  • the ethanol solution is forcibly stirred uniformly, granulated by a 40-mesh sieve, and dried in an environment having a temperature of 25 ° C to 55 ° C and a humidity of 30% or less until the volatile content of the composition is not more than 1%.
  • a certain amount of aerosol generating agent particles are prepared into a cylindrical placing device having ⁇ 25 ⁇ under a pressure of not less than 3 MPa for fire-extinguishing test.
  • Table 1 Comparative test table of the present invention and prior art
  • the fire extinguishing efficiency of the first to sixth embodiments of the present invention is higher than that of the control group using the alkaline reducing agent; when the existing chemical coolant is used, the storage performance reaches the service life of the product for 6 years. Above, the storage period of the comparison group and the existing chemical coolant are within 1 year.

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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

本发明公布了一种气溶胶发生剂,由氧化剂、还原剂、粘合剂组成,所述的氧化剂为硝酸锶和硝酸钾,粘合剂为酚醛树脂,所述的还原剂为酒石酸、二羟基酒石酸、乙二胺四乙酸、水杨酸、邻苯二甲酸酐中的一种或多种。其制备方法为:将酚醛树脂溶于乙醇中,制成质量百分浓度为50%〜65%的酚醛树脂溶液;将氧化剂和还原剂粉碎、混合,然后将酚醛树脂溶液加入混合好的粉体、搅拌、造粒、干燥、压制成型。本发明的气溶胶发生剂可以单独作为灭火剂使用,也可以配合化学冷却剂使用,作为化学冷却剂的热力源和动力源,可以充分燃烧,发生剂燃烧残留量更小,性能稳定、易于长期贮存,对环境友好性能优良。

Description

说 明 书 一种气溶胶发生剂
技术领域
本发明属于气溶胶灭火技术领域, 特别是涉及一种气溶胶发生剂及其制备 工艺。
背景技术
气溶胶灭火剂是一种灭火效率极高, 臭氧耗损值 ODP为零, 无毒无害, 无 残留, 价格低、 设备投资少的新型灭火剂, 在哈龙淘汰的紧迫背景下, 既得到 了政府的大力支持, 也迎合了市场的需求, 因此气溶胶灭火技术成为近十几年 来非常引人注目的哈龙替代技术之一。
气溶胶作为哈龙产品的替代产品, 具有灭火性能高, 无二次污染等特点, 在国内外灭火行业有十分广泛的应用。 现有产品中, 这类发生剂的配方主要包 括氧化剂、 还原剂、 粘合剂、 添加剂及加工助剂等。 在这些配方中, 选择合适 的材料, 不仅能大大提高发生剂的灭火效能, 也能提高发生剂的加工, 储存, 使用等性能而这些性能也是气溶胶发生剂不可或缺的组成部分。
现在气溶胶发生剂中通常使用的还原剂三聚氰胺、 双氰胺等, 均为碱性物 质。 若灭火对象为偏酸性, 则在灭火的同时会使某些酸性的设备发生腐蚀、 损 坏。 如: 油罐着火, 使用现有气溶胶灭火剂虽然可以灭火, 但是碱性的物质会 使原油中的某些成分发生皂化反应从而絮凝, 给原油的性能造成影响, 影响再 次使用。
发明内容
为了解决现有技术中存在的问题, 本发明提供了一种配方组成简单、 产气 量大、 燃烧充分、 且更适于酸性灭火对象的气溶胶发生剂及其制备工艺。 i
本发明解决技术问题的技术方案是:
一种气溶胶发生剂, 由氧化剂、 还原剂、 粘合剂组成, 其特征在于: 所述 的氧化剂为硝酸锶和硝酸钾, 粘合剂为酚醛树脂, 还原剂为酒石酸、 二羟基酒 石酸、 乙二胺四乙酸、 水杨酸、 邻苯二甲酸酐中的一种或多种。
进一步地, 所述的还原剂的质量百分含量为 5%~25%。
进一步地, 所述气溶胶发生剂中各组分其质量百分含量为:
:化剂
粘合剂
Figure imgf000003_0001
进一步地, 所述气溶胶发生剂中各组分其质量百分含量为
:化剂
粘合剂
Figure imgf000003_0002
进一步地, 所述氧化剂中硝酸锶和硝酸钾的质量比为 2: 1~10: 1, 优选为 2: 1-4: 1 , 更优选为 3: 1。
本发明的另一目的在于提出一种气溶胶发生剂的制备工艺, 其特征在于: 1 )将酚醛树脂溶于乙醇中, 制成质量百分浓度为 50%〜65%的酚醛树脂溶
2 ) 将氧化剂和还原剂粉碎至 100-200标准目的细度, 并按比例要求混合, 并用 100~200目筛过三遍, 使其混合均匀;
3 )然后将酚醛树脂溶液加入混合好的粉体之中, 强制拌合搅拌均匀后使用 40 目标准筛网造粒, 并将造好的粒子, 在温度 25 °C~55°C, 湿度 30%以下的环 境中干燥至组合物中挥发份含量不大于 1%< 4) 将干燥好的药剂在在 3MPa的压力下压制成型。
本发明的灭火组合物中, 还原剂采用酒石酸、 二羟基酒石酸、 乙二胺四乙 酸、 水杨酸、 邻苯二甲酸酐等酸性物质有别于现有技术中采用的碱性还原剂。 一方面弥补了目前常规专利在某些领域使用含有碱性还原剂的气溶胶灭火剂效 果较差或使用后对被保护对象的产生较多负面影响的缺陷, 如在原油灭火时, 由于原油本身呈弱酸性, 如果采用含有碱性还原剂的气溶胶发生剂, 则碱性的 气溶胶会造成发生剂与原油成分相互发生皂化反应而产生絮凝的机会大大增 加, 这给原油的后续处理带来麻烦, 而酒石酸、 二羟基酒石酸、 乙二胺四乙酸、 水杨酸、 邻苯二甲酸酐等酸性物质组合的气溶胶发生剂产生的气溶胶呈弱酸性, 在灭火的同时不会与原油成分发生反应而杜绝了这种负面影响; 另一方面, 在 配合化学冷却剂的使用上, 如采用酸性的化学冷却剂, 就需要酸性或者中性的 气溶胶发生剂配合, 否则二者相互影响会大大降低发生剂和化学冷却剂的储存 性能和灭火效能。 因此本发明的气溶胶发生剂既是对已有气溶胶灭火剂的补充, 也是对其应用领域的拓展。
相对于现有技术, 本发明的优点在于:
1 ) 本发明的气溶胶发生剂可以单独作为灭火剂使用, 也可以配合化学冷却 剂使用, 作为化学冷却剂的热力源和动力源。
2)本发明的气溶胶发生剂性能稳定、易于长期贮存,对环境友好性能优良。
3 ) 本发明的气溶胶发生剂采用酸性还原剂, 更适于偏酸性的灭火对象, 在 有效灭火的同时可有效避免使某些酸性的设备发生腐蚀、 损坏, 影响再次使用。
4) 本发明对气溶胶发生剂中各组分的比例进行优选, 使其在本发明所述制 备工艺条件下, 可以充分燃烧, 发生剂燃烧残留量更小。
具体实施方式 现结合具体的实施例对本发明的灭火组合物进行进一步描述:
实施例 1
将酚醛树脂 7g溶解于 4g工业酒精中, 配制成均匀的酚醛树脂乙醇溶液, 取 42g硝酸锶、 30g硝酸钾、 12g乙二胺四乙酸、 9g酒石酸分别经 200目标准筛 后再混合均匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造粒, 在温度 25°C~55°C, 湿度 30%以下的环境中干燥至组合物中挥发份含量不大于 1%。 使用时, 按照灭火条件, 将一定量气溶胶发生剂颗粒, 在不小于 3MPa的 压力下, 制备成具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。
实施例 2
将酚醛树脂 10g溶解于 8g工业酒精中, 配制成均匀的酚醛树脂乙醇溶液, 取 50g硝酸锶、 24g硝酸钾、 16g邻苯二甲酸酐分别经 200目标准筛后再混合均 匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造粒, 在温度 25°C ~55°C, 湿度 30%以下的环境中干燥至组合物中挥发份含量不大于 1%。使用时, 按照灭火条件, 将一定量气溶胶发生剂颗粒, 在不小于 3MPa的压力下, 制备成 具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。
实施例 3
将酚醛树脂 8g溶解于 5g工业酒精中, 配制成均匀的酚醛树脂乙醇溶液, 分别取 60g硝酸锶、 20g硝酸钾、 7g二羟基酒石酸、 5g水杨酸分别经 200目标 准筛后再混合均匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造 粒,在温度 25°C~55°C,湿度 30%以下的环境中干燥至组合物中挥发份含量不大 于 1%。 使用时, 按照灭火条件, 将一定量气溶胶发生剂颗粒, 在不小于 3MPa 的压力下, 制备成具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。 将酚醛树脂 10g溶解于 8.5g工业酒精中,配制成均匀的酚醛树脂乙醇溶液, 取 62g硝酸锶、 14g硝酸钾、 6g乙二胺四乙酸、 8g水杨酸分别经 200目标准筛 后再混合均匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造粒, 在温度 25°C~55°C, 湿度 30%以下的环境中干燥至组合物中挥发份含量不大于 1%。 使用时, 按照灭火条件, 将一定量气溶胶发生剂颗粒, 在不小于 3MPa的 压力下, 制备成具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。
实施例 5
将酚醛树脂 12g溶解于 8g工业酒精中, 配制成均匀的酚醛树脂乙醇溶液, 取 68g硝酸锶、 8g硝酸钾、 8g邻苯二甲酸酐、 4g酒石酸分别经 200目标准筛后 再混合均匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造粒, 在 温度 25°C~55°C,湿度 30%以下的环境中干燥至组合物中挥发份含量不大于 1%。 使用时,按照灭火条件,将一定量气溶胶发生剂颗粒,在不小于 3MPa的压力下, 制备成具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。
实施例 6
将酚醛树脂 10g溶解于 6g工业酒精中, 配制成均匀的酚醛树脂乙醇溶液, 取 75g硝酸锶、 5g硝酸钾、 10g邻苯二甲酸酐分别经 200 目标准筛后再混合均 匀, 加入上述酚醛树脂乙醇溶液强制搅拌均匀, 经 40目筛网造粒, 在温度 25°C ~55°C, 湿度 30%以下的环境中干燥至组合物中挥发份含量不大于 1%。使用时, 按照灭火条件, 将一定量气溶胶发生剂颗粒, 在不小于 3MPa的压力下, 制备成 具有 Φ25ηιηι的圆柱形放入装置进行灭火试验。
实施例 7
本发明的气溶胶发生剂与现有技术的对比试验, 见表 1。 表 1 : 本发明与现有技术的对比试验表
Figure imgf000007_0001
[1]测试方法参考 GA499.1— 2010
[2]为市售 PFE-1型灭火器所用化学冷却剂, 经分析其主要成分为二茂铁和草 酸。
从上表的比较可以看出, 本发明实施例 1~6与采用碱性还原剂的对照组相 比灭火效能更高; 配合现有化学冷却剂时, 其贮存性能均达到产品使用寿命 6 年以上, 对比组与现有化学冷却剂配合时贮存期都在 1年以内。
上述具体实施例仅仅是示例性的, 在本发明的上述教导下, 本领域技术人 员可以在上述实施例的基础上进行各种改进和变形, 而这些改进或者变形落在 本发明的保护范围内。 本领域技术人员应该明白, 上面的具体描述只是为了解 释本发明的目的, 并非用于限制发明

Claims

权 利 要 求 书
1、 一种气溶胶发生剂, 由氧化剂、 还原剂、 粘合剂组成, 其特征在于: 所 述的氧化剂为硝酸锶和硝酸钾, 粘合剂为酚醛树脂, 还原剂为酒石酸、 二羟基 酒石酸、 乙二胺四乙酸、 水杨酸、 邻苯二甲酸酐中的一种或多种。
2、 根据权利要求 1所述的一种气溶胶发生剂, 其特征在于: 所述的还原剂 的质量百分含量为 5%~25%。
3、 根据权利要求 2所述的一种气溶胶发生剂, 其特征在于: 所述气溶胶发 生剂中各组分其质量百分含量为:
Figure imgf000009_0001
4、 根据权利要求 3所述的一种气溶胶发生剂, 其特征在于: 所述气溶胶发 生剂中各组分其质量百分含量为:
Figure imgf000009_0002
5、 根据权利要求 1~4中任一项所述的一种气溶胶发生剂, 其特征在于: 所 述氧化剂中硝酸锶和硝酸钾的质量比为 2: 1~10: 1。
6、 根据权利要求 5所述的一种气溶胶发生剂, 其特征在于: 所述氧化剂中 硝酸锶和硝酸钾的质量比为 2: 1~4: 1。
7、 如权利要求 1所述的 2 ) 将氧化剂和还原剂粉碎至 100-200标准目的细度, 并按比例要求混合, 并用 100~200目筛过三遍, 使其混合均匀;
3 ) 然后将酚醛树脂溶液加入混合好的粉体之中, 强制拌合搅拌均匀后使用 40 目标准筛网造粒, 并将造好的粒子, 在温度 25 °C~55°C, 湿度 30%以下的环 境中干燥至组合物中挥发份含量不大于 1%。
4) 将干燥好的药剂在在 3MPa的压力下压制成型。
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