WO2022252601A1 - 可扑灭铝渣燃烧的灭火剂及其制备方法和应用 - Google Patents

可扑灭铝渣燃烧的灭火剂及其制备方法和应用 Download PDF

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WO2022252601A1
WO2022252601A1 PCT/CN2021/142930 CN2021142930W WO2022252601A1 WO 2022252601 A1 WO2022252601 A1 WO 2022252601A1 CN 2021142930 W CN2021142930 W CN 2021142930W WO 2022252601 A1 WO2022252601 A1 WO 2022252601A1
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Prior art keywords
extinguishing agent
fire extinguishing
aluminum slag
fire
sulfate
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PCT/CN2021/142930
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English (en)
French (fr)
Inventor
余海军
钟应声
谢英豪
李长东
张学梅
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Application filed by 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司, 湖南邦普汽车循环有限公司 filed Critical 广东邦普循环科技有限公司
Priority to HU2200292A priority Critical patent/HUP2200292A2/hu
Priority to ES202390045A priority patent/ES2958090R1/es
Priority to US18/265,374 priority patent/US11931614B2/en
Priority to DE112021005101.6T priority patent/DE112021005101T5/de
Priority to GB2313051.1A priority patent/GB2618048A/en
Priority to MA60454A priority patent/MA60454A1/fr
Publication of WO2022252601A1 publication Critical patent/WO2022252601A1/zh

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007—Solid extinguishing substances
    • A62D1/0014—Powders; Granules
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007—Solid extinguishing substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention belongs to the technical field of fire extinguishing agents, and in particular relates to a fire extinguishing agent capable of extinguishing the burning of aluminum slag and its preparation method and application.
  • waste lithium batteries are widely used in lithium battery manufacturing, 3C digital and new energy vehicles, industrial energy storage and other industries, more waste lithium batteries are also produced.
  • the recycling process of waste lithium batteries includes the following steps: discharge, dismantling, separation, high temperature and hydrometallurgy, resynthesis of positive electrode materials, etc.
  • the aluminum slag and waste aluminum foil produced in the separation of waste lithium battery materials contain acid , alkali and water.
  • the piled aluminum slag reacts very violently when it encounters acid, alkali, and water. Because it is piled in the open place, a large amount of hydrogen gas is generated in a short period of time, resulting in combustion and explosion.
  • Aluminum slag has the characteristics of high combustion temperature, fast combustion spread, high explosive power and high radiant heat, and can react with air, water and carbon dioxide, so it is difficult to remove and isolate the burning aluminum slag, and the occurrence of It is extremely difficult to extinguish a fire.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of fire extinguishing agent that can put out aluminum slag burning and its preparation method and application, and the main material of this fire extinguishing agent is sulfate, chloride salt, and sulfate, chloride salt are the resynthesis process of waste lithium battery cathode material
  • the solid waste containing sulfate and chloride salt obtained from the separation of medium and high salt wastewater, and the solid waste containing sulfate and chloride salt as fire extinguishing agent materials can effectively recycle waste resources.
  • the present invention adopts the following technical solutions:
  • a fire extinguishing agent capable of extinguishing burning aluminum slag comprising the following raw materials: sulfate, chloride, mineral, silica gel, surfactant, and stearate.
  • the sulfate, chloride salt, mineral, and silica gel are prepared as powders.
  • the mass ratio of the powder, surfactant and stearate is 100:(1-5):(0.05-0.25).
  • the sulfate is sodium sulfate, calcium sulfate.
  • the chloride salt is sodium chloride, calcium chloride.
  • the mass ratio of the sodium sulfate, sodium chloride, calcium sulfate and calcium chloride is (50-80):(20-40):(2-10):(1-10).
  • the mineral is at least one of quartz sand, quartzite, sandstone, silica or opal.
  • the surfactant is polydimethylsiloxane.
  • the stearate is one of sodium stearate, magnesium stearate, calcium stearate or zinc stearate.
  • a preparation method of a fire extinguishing agent capable of extinguishing aluminum slag combustion comprising the following steps:
  • the solid waste containing sulfate and chloride salts is obtained by membrane separation and evaporation from high-salt wastewater generated during the resynthesis of spent lithium battery anode materials.
  • the main components of the solid waste containing sulfate and chloride salts are sodium sulfate and sodium chloride.
  • the calcination temperature is 400-800°C
  • the calcination time is 0.5-3h
  • the calcination heating rate is 10-30°C/min.
  • the temperature of the water is 30-95°C; the mass ratio of the solid waste containing sulfate and chloride salts to water is (20-40):100.
  • the vacuum degree of the evaporation is 0.02-0.06 MPa, and the evaporation amount is 400 kg/h.
  • the sieve used for the sieving has a pore size of 200-400 mesh.
  • the mass ratio of the crystals to liquid nitrogen is 10:1-3.
  • the mass ratio of crystals, minerals, and silica gel is 100:(1-5):(1-2).
  • the mineral is at least one of quartz sand, quartzite, sandstone, silica or opal.
  • the silica gel is micronized silica gel.
  • the purity of the silica gel is analytically pure or ⁇ 98%.
  • the mixing time is 1-5 minutes, and the mixing speed is 120-360 r/min.
  • the grinding time is 15-60 min, and the speed of the grinder used in the grinding is 200-720 r/min.
  • the particle size of the ground powder is ⁇ 100 ⁇ m.
  • the mass ratio of the powder, surfactant and stearate is 100:(1-5):(0.05-0.25).
  • the surfactant is polydimethylsiloxane.
  • the purity of the polydimethylsiloxane and the stearate are analytically pure or above.
  • the stearate is one of sodium stearate, magnesium stearate, calcium stearate or zinc stearate.
  • the mixing temperature is 40-90° C.
  • the mixing time is 30-60 minutes
  • the rotation speed is 120-360 r/min.
  • step (3) the drying is performed until the water content is ⁇ 2.5%.
  • the principle of fire extinguishing agent burning aluminum slag First, coating.
  • the main components of fire extinguishing agent are sulfate, chloride salt and burning metal (aluminum, iron, copper and their alloys) have no chemical reaction, and are physically wrapped by high temperature melting.
  • the second is endothermic, sodium sulfate at high temperature 1.
  • the vibration of sodium chloride molecules is intensified.
  • the main materials of the fire extinguishing agent in the present invention are sulfate and chloride salts, which are the main component salts of the waste water produced in the resynthesis process of the positive electrode materials of waste lithium batteries.
  • waste water as the material of the fire extinguishing agent can effectively recycle the waste resources , the selected auxiliary material quartz minerals come from nature, which can reduce the production cost of fire extinguishing agent.
  • the amount of waste water generated during the resynthesis of the positive electrode material of the waste lithium battery is large, the salt content is high, and the solid waste containing sulfate and chloride salt obtained by membrane separation and evaporation is more, so the main material of the fire extinguishing agent can be prepared in large quantities.
  • the fire extinguishing agent of the present invention has dual fire extinguishing effects of physical fire extinguishing and chemical fire extinguishing: there is no chemical reaction between the main fire extinguishing components of the fire extinguishing agent, sodium sulfate and sodium chloride, and the burning aluminum slag, and it is only melted physical covering, containing sulfuric acid
  • Other impurity salts in the solid waste of salt and chlorine salt such as magnesium chloride, calcium chloride and other chlorine salts, can also be used as active ingredients of fire extinguishing agents; there is a limited chemical reaction between other auxiliary materials of fire extinguishing agents and the burning aluminum slag, forming a non-combustible An inert compound that passivates the surface of the aluminum to be chemically covered.
  • the crystal structure of the crystal is unstable and more easily destroyed, so that after the grinding treatment, the particle size of the powder will be smaller, the surface area will increase, and the surface energy will increase, making it easier to burn the aluminum
  • the slag is physically covered and chemically covered, thus improving the fire extinguishing efficiency of the fire extinguishing agent.
  • the ground powder of the crystals is easy to absorb moisture, causing agglomeration and agglomeration.
  • the added polydimethylsiloxane has hydrophobic characteristics, which can strengthen the moisture-proof performance of the fire extinguishing agent.
  • the surfactant is polydimethylsiloxane, which has good chemical stability and is characterized by strong surface activity, inertness, non-toxicity and non-flammability. At the same time, it can stably and effectively play its role as a surfactant in systems such as residual acid and alkali in aluminum slag, and will not react or decompose with the combustion reaction system of aluminum slag.
  • the high chemical stability of polydimethylsiloxane means high chemical inertness.
  • Polydimethylsiloxane surfactants are well compatible with powders, quartz minerals, and stearates. The stability between different materials, because polydimethylsiloxane has the ability of hydrophobic, which can reduce the moisture absorption capacity of fire extinguishing agent.
  • the main function of the stearate in the present invention is to reduce the resistance of agglomeration between particles and strengthen the polydimethylsiloxane coating powder.
  • the silica gel in the present invention has a grinding aid function, and can reduce the friction force between particles to improve particle fluidity during grinding, reduce the weight difference between particles of different materials, and facilitate grinding.
  • the mineral in the present invention has excellent electrical insulation performance, and adding it to the fire extinguishing agent can ensure the electrical insulation of the fire extinguishing agent.
  • the fire extinguishing agent of the present invention can replace conventional Class D fire extinguishing agent products for extinguishing metal combustion, and put the fire extinguishing agent into portable, cart-type, hanging-type and other fire extinguisher bottles, and can be applied to iron, copper and other simple substances or alloys. Metal fire extinguisher.
  • Fig. 1 is the flow chart that the embodiment of the present invention 1 prepares the fire extinguishing agent that can extinguish aluminum slag combustion;
  • Fig. 2 is the SEM image of the fire extinguishing agent capable of extinguishing the burning of aluminum slag according to Example 1 of the present invention.
  • the preparation method of the fire extinguishing agent that can extinguish aluminum slag combustion of the present embodiment comprises the following steps:
  • a method for extinguishing fire when aluminum slag burns comprising the following specific steps:
  • the fire extinguishing agent in the storage tank is injected into the 10kg suspended fire extinguisher.
  • the aluminum slag storage tank is stored with a 5kg aluminum slag pile.
  • the distance between the fire extinguisher and the top of the aluminum slag pile is about 0.8m . 3.5m), ignite the aluminum slag, and when the fire extinguisher senses the temperature of the aluminum slag burning fire, spray the fire extinguishing agent to extinguish the fire.
  • Fig. 1 is the flow chart of the preparation of the fire extinguishing agent that can extinguish the burning of aluminum slag in Example 1 of the present invention;
  • the solid waste containing sulfate and chloride salt is roasted, dissolved in water, and ground after adding liquid nitrogen treatment , and then add minerals, micropowder silica gel, polydimethylsiloxane, and stearate to prepare a fire extinguishing agent that can extinguish the burning of aluminum slag.
  • Fig. 2 is the SEM image of the fire extinguishing agent capable of extinguishing the burning of aluminum slag according to Example 1 of the present invention. It can be seen from the SEM image that the large particles are powders, and the powders are attached to other tiny particles.
  • the preparation method of the fire extinguishing agent that can extinguish aluminum slag combustion of the present embodiment comprises the following steps:
  • a method for extinguishing fire when aluminum slag burns comprising the following specific steps:
  • the fire extinguishing agent in the storage tank is injected into the 10kg suspended fire extinguisher.
  • the aluminum slag storage tank is stored with a 5kg aluminum slag pile. 3.5m), ignite the aluminum slag, and when the fire extinguisher senses the temperature of the aluminum slag burning fire, spray the fire extinguishing agent to extinguish the fire.
  • the preparation method of the fire extinguishing agent that can extinguish aluminum slag combustion of the present embodiment comprises the following steps:
  • a method for extinguishing fire when aluminum slag burns comprising the following specific steps:
  • the fire extinguishing agent in the storage tank is injected into the 10kg suspended fire extinguisher.
  • the aluminum slag storage tank is stored with a 4.3kg aluminum slag pile.
  • the distance from the fire extinguisher to the top of the aluminum slag pile is about 0.8m . *3.5m), ignite the aluminum slag, and when the fire extinguisher senses the temperature of the aluminum slag burning fire, spray the fire extinguishing agent to extinguish the fire.
  • a method for burning aluminum slag to extinguish a fire comprising the following specific steps:
  • step (3) is not soaked in liquid nitrogen.
  • a method for burning aluminum slag to extinguish a fire comprising the following specific steps:
  • Example 1 The difference from Example 1 is that no quartz-like minerals and micronized silica gel are added in step (3).
  • a method for burning aluminum slag to extinguish a fire comprising the following specific steps:
  • Example 1 The difference from Example 1 is that no polydimethylsiloxane is added in step (4).
  • a method for burning aluminum slag to extinguish a fire comprising the following specific steps:
  • Example 1 The difference with Example 1 is: no sodium stearate is added in the step (4).
  • the particle size of the powder is measured by a laser particle size analyzer, and the water content is measured by a conventional method.
  • the time required for the aluminum slag to be extinguished is: 30 seconds after the aluminum slag starts to burn, the fire extinguishing agent is sprayed on the burning aluminum slag to extinguish the fire. It takes time.
  • Example 1 and Comparative Example 1 the crystals of Comparative Example 1 are not treated with liquid nitrogen, and the crystal structure of the crystals is not easily destroyed, so that after the grinding process, the particle size of the powder cannot be reduced, and it is not easy to The burning aluminum slag is physically covered and chemically covered, thus reducing the fire extinguishing efficiency of the fire extinguishing agent.
  • Example 1 From Example 1 and Comparative Example 2, it can be seen that in Comparative Example 2 without adding quartz minerals and micropowdered silica gel, the particle size of the powder is large during the grinding process, and the particle size of the powder is 50-100 ⁇ m and >100 ⁇ m. ; In Example 1, the particle size of the powder in 20-50 ⁇ m accounts for the most.
  • Comparative Example 3 does not add polydimethylsiloxane, and the hydrophobic ability is poor, resulting in an increase in water content, and thus a longer time to extinguish the burning of aluminum slag.
  • Example 1 and Comparative Example 4 It can be seen from Example 1 and Comparative Example 4 that no stearate was added in Comparative Example 4, the particles were agglomerated, the particle size of the powder became larger, and the time for polydimethylsiloxane to coat the powder became longer , and then the burning time of aluminum slag becomes longer.

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Abstract

一种可扑灭铝渣燃烧的灭火剂及其制备方法和应用，包括以下原料：硫酸盐、氯盐、矿物、硅胶、表面活性剂、硬脂酸盐。其中的主要材料硫酸盐和氯盐为废旧锂电池正极材料再合成过程中产生的高盐废水分离得到的含硫酸盐、氯盐的固废，含硫酸盐、氯盐的固废作为灭火剂的材料，能有效的将废弃资源进行循环利用。废旧锂电池正极材料合成过程中产生的废水量大，盐含量较高，分离、蒸发得到含硫酸盐、氯盐的固废较多，因此可作为大量制备灭火剂的主材料。

Description

可扑灭铝渣燃烧的灭火剂及其制备方法和应用 技术领域
本发明属于灭火剂技术领域，具体涉及一种可扑灭铝渣燃烧的灭火剂及其制备方法和应用。
背景技术
锂电池材料在广泛应用于锂电池制造、3C数码及新能源汽车、工业储能等行业的同时，也产生更多的废旧锂电池。废旧锂电池回收处理过程包括以下步骤：放电、拆除、分离、高温和湿法冶金、正极材料的再合成等，但是在废旧锂电池材料的分离中产生的铝渣以及废铝箔片，残留有酸、碱以及水。堆放的铝渣遇酸、碱、水时反应非常剧烈，由于堆放在露天场所，短时间内产生大量的氢气，产生燃烧和爆炸。铝渣燃烧温度高、燃烧蔓延的速度快、爆炸威力大且产生的很高辐射热，又可与空气、水和二氧化碳反应等特点，因此难以将燃烧中的铝渣进行移除和隔离，发生火灾时极难扑救。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种可扑灭铝渣燃烧的灭火剂及其制备方法和应用，该灭火剂的主要材料为硫酸盐、氯盐，硫酸盐、氯盐为废旧锂电池正极材料再合成过程中高盐废水分离得到的含硫酸盐、氯盐的固废，将含硫酸盐、氯盐的固废作为灭火剂的材料能有效的将废弃资源进行循环利用。
为实现上述目的，本发明采用以下技术方案：
一种可扑灭铝渣燃烧的灭火剂，包括以下原料：硫酸盐、氯盐、矿物、硅胶、表面活性剂、硬脂酸盐。
优选地，所述硫酸盐、氯盐、矿物、硅胶制备得到粉体。
进一步优选地，所述粉体、表面活性剂和硬脂酸盐的质量比为100：(1～5)：(0.05～0.25)。
优选地，所述硫酸盐为硫酸钠、硫酸钙。
优选地，所述氯盐为氯化钠、氯化钙。
更优选地，所述硫酸钠、氯化钠、硫酸钙和氯化钙的质量比为(50～80)：(20～40)：(2～10)：(1～10)。
优选地，所述矿物为石英砂、石英岩、砂岩、硅石或蛋白石中的至少一种。
优选地，所述表面活性剂为聚二甲基硅氧烷。
优选地，所述硬脂酸盐为硬脂酸钠、硬脂酸镁、硬脂酸钙或硬脂酸锌中的一种。
一种可扑灭铝渣燃烧的灭火剂的制备方法，包括以下步骤：
(1)将含硫酸盐、氯盐的固废进行焙烧，加水溶解，过滤取滤液，进行蒸发、结晶，得结晶体；
(2)将所述结晶体加入液氮中浸泡，浸泡后的结晶体与矿物、硅胶混合，制成粉体；
(3)将所述粉体、表面活性剂、硬脂酸盐混合，干燥，即得所述的可扑灭铝渣燃烧的灭火剂。
优选地，步骤(1)中，所述含硫酸盐、氯盐的固废是由废旧锂电池正极材料再合成过程中产生的高盐废水，经膜分离、蒸发得到。
更优选地，所述含硫酸盐、氯盐的固废的主要成分为硫酸钠、氯化钠。
优选地，步骤(1)中，所述焙烧的温度在400～800℃，焙烧的时间在0.5～3h，焙烧的升温速度为10～30℃/min。
优选地，步骤(1)中，所述水的温度为30～95℃；所述含硫酸盐、氯盐的固废和水的质量比为(20～40):100。
优选地，步骤(1)中，所述蒸发的真空度为0.02～0.06MPa，蒸发的量为400kg/h。
优选地，步骤(1)中，所述过筛使用的筛网的孔径为200～400目。
优选地，步骤(2)中，所述结晶体与液氮的质量比为10:1～3。
优选地，步骤(2)中，所述结晶体、矿物、硅胶的质量比为100：(1～5)：(1～2)。
优选地，步骤(2)中，所述矿物为石英砂、石英岩、砂岩、硅石或蛋白石中的至少一种。
优选地，步骤(2)中，所述硅胶为微粉硅胶。
优选地，步骤(2)中，所述硅胶纯度为分析纯或≥98％。
优选地，步骤(2)中，所述混合的时间为1～5min，混合的转速为120～360r/min。
优选地，步骤(2)中，所述研磨的时间为15～60min，所述研磨使用的研磨机的转速为200～720r/min。
优选地，步骤(2)中，所述研磨的粉体粒度＜100μm。
优选地，步骤(3)中，所述粉体、表面活性剂、硬脂酸盐的质量比为100：(1～5)：(0.05～0.25)。
优选地，步骤(3)中，所述表面活性剂为聚二甲基硅氧烷。
更优选地，所述聚二甲基硅氧烷纯度和硬脂酸盐纯度为分析纯及以上。
优选地，步骤(3)中，所述硬脂酸盐为硬脂酸钠、硬脂酸镁、硬脂酸钙或硬脂酸锌中的一种。
优选地，步骤(3)中，所述混合的温度为40～90℃，混合的时间为30～60min，转速为120～360r/min。
优选地，步骤(3)中，所述干燥至含水量≤2.5％。
灭火剂灭铝渣燃烧的原理：一是包覆，灭火剂主要组分为硫酸盐、氯盐与燃烧的金属(铝、铁、铜及其合金)没有化学反应，是以高温融熔物理包覆，灭火剂添加的辅料(矿物：石英)与燃烧的铝渣存在有限的化学反应，形成不燃烧的惰性化合物，钝化铝渣表面，产生化学包覆；二是吸热，高温下硫酸钠、氯化钠分子的振动加剧，为了减少分子间束缚，熔融过程中会不断吸收金属燃烧产生的热量。因此通过物理和化学包覆、来隔绝、窒息铝渣的燃烧，伴有吸热，来达到对铝渣燃烧的灭火。
相对于现有技术，本发明的有益效果如下：
1、本发明中灭火剂的主要材料为硫酸盐、氯盐，为废旧锂电池正极材料再合成过程中产生的废水主要成分盐，将废水作为灭火剂的材料能有效的将废弃资源进行循环利用，所选的辅助材料石英类矿物来自于自然界，能降低灭火剂生产成本。废旧锂电池正极材料再合成过程中产生的废水量大，盐含量较高，膜分离、蒸发得到含硫酸盐、氯盐的固废较多，因此可大量制备灭火剂主材料。
2、本发明的灭火剂有物理灭火、化学灭火双重的灭火作用：灭火剂主要灭火组分硫酸钠、氯化钠与燃烧的铝渣之间没有化学反应，仅仅是融熔物理覆盖，含硫酸盐、氯盐的固废中的其他杂质盐如氯化镁、氯化钙等氯盐也可以当做灭火剂的有效成分；灭火 剂其他辅助材料与燃烧的铝渣间存在有限的化学反应，形成不燃烧的惰性化合物，钝化铝的表面，予以化学覆盖。
3、结晶体经液氮处理后，结晶体的晶体结构不稳定，更容易被破坏，使得在研磨处理后，粉体的粒度将更小，表面积增大，表面能增大，更易于将燃烧的铝渣进行物理覆盖、化学覆盖，因此提升灭火剂的灭火效率。结晶体经研磨后的粉体容易吸潮，引起团聚结块，加入的聚二甲基硅氧烷有疏水特性，对灭火剂有加强防潮的性能。
4、表面活性剂为聚二甲基硅氧烷化学稳定性好，特点为：表面活性强，惰性，无毒，不易燃。同时可在铝渣中残酸、残碱等体系中稳定有效地发挥其表面活性剂作用，不会与铝渣燃烧反应体系发生反应或分解。聚二甲基硅氧烷高的化学稳定性就意味着高的化学惰性，聚二甲基硅氧烷表面活性剂能与粉体、石英类矿物、硬脂酸盐很好地相容，保持不同材料之间的稳定性，因为聚二甲基硅氧烷具有疏水的能力，可降低灭火剂吸湿能力。
5、本发明中硬脂酸盐主要作用为降低颗粒之间团聚的阻力，加强聚二甲基硅氧烷包覆粉体。本发明中的硅胶有助磨作用，在研磨时，能降低颗粒间的摩擦力而能改善颗粒流动性，减少不同材质颗粒之间的重量差异，利于研磨。本发明中的矿物拥有优异的电绝缘性能，将其加入到灭火剂中可保证灭火剂的电绝缘性。
6、利用本发明的灭火剂可以代替常规灭金属燃烧的D类灭火剂产品，将灭火剂装入手提式、推车式、挂式等灭火器瓶，能应用于铁、铜等单质或合金的金属火灾灭火。
附图说明
图1为本发明实施例1制备可扑灭铝渣燃烧的灭火剂的流程图；
图2为本发明实施例1的可扑灭铝渣燃烧的灭火剂的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例的可扑灭铝渣燃烧的灭火剂的制备方法，包括以下步骤：
(1)收集：由废旧锂电池正极材料再合成过程中产生的高盐废水，经膜分离、蒸 发得到56kg的含硫酸盐、氯盐的固废(含盐固废)；
(2)提纯：通风环境下，将含硫酸盐、氯盐的固废在升温速度为10℃/min下升温至400℃下焙烧3h，焙烧后加入至65℃的去离子水中进行溶解，溶解的质量比为35:100，利用筛网孔径大小为200目的筛网过滤得滤液，滤渣，将滤液在真空度为0.04MPa下进行蒸发12min、降温、结晶，在室外环境下干燥5d，得结晶体(硫酸钠占比57.10％、氯化钠占比22.56％、水占比15.43％、硫酸钙占比3.25％、氯化钙1.66％)；
(3)研磨：将结晶体加入液氮中浸泡，结晶体与液氮的质量比为10:1，浸泡至液氮蒸发，并使结晶体升至室温，将质量比为100：2：1的结晶体、矿物(石英砂、石英岩、砂岩)、微粉硅胶加入至转速为150r/min的洁净混合机进行混合2min，混合完毕的混合料加至转速为480r/min的洁净球磨机进行研磨45min，出料时间为3min(出料量为0.5t/h，研磨的质量为27.6kg)，研磨后得到粒度＜100μm的粉体；
(4)改性：将质量比为100：1：0.05的粉体、聚二甲基硅氧烷、硬脂酸钠加入至转速为150r/min的洁净干燥混合机中，设置混合时的温度为70℃，进行混合35min、干燥后既得灭火剂产品，干燥完毕测得灭火剂产品的含水量为1.87％，得到可扑灭铝渣燃烧的灭火剂。
一种铝渣燃烧时灭火的方法，包括以下具体步骤：
(1)将保存好的灭火剂注入到干燥的储存罐中，同时储存罐中充入干燥的氩气保存，灭火剂：惰性气体体积比为8:1，储存罐压力为2.5MPa；
(2)储存罐的灭火剂注入到10kg规格的悬挂式灭火器中，铝渣储存槽存放有5kg铝渣堆，灭火器距离铝渣堆顶约0.8m，铝渣储存槽大小为14m 2(4m*3.5m)，点燃铝渣，当灭火器感温到铝渣燃烧的火情时，喷射灭火剂，进行灭火。
图1为本发明实施例1制备可扑灭铝渣燃烧的灭火剂的流程图；从图1中可以看出将含硫酸盐、氯盐的固废进行焙烧、加水溶解、加入液氮处理后研磨、再加入矿物、微粉硅胶、聚二甲基硅氧烷、硬脂酸盐，制备得到可扑灭铝渣燃烧的灭火剂。图2为本发明实施例1的可扑灭铝渣燃烧的灭火剂的SEM图，可从SEM图中看出大颗粒即为粉体，粉体附着其他微小颗粒。
实施例2
本实施例的可扑灭铝渣燃烧的灭火剂的制备方法，包括以下步骤：
(1)收集：由废旧锂电池正极材料再合成过程中产生的高盐废水，经膜分离、蒸 发得到91kg的含硫酸盐、氯盐的固废；
(2)提纯：通风环境下，将含硫酸盐、氯盐的固废在升温速度为18℃/min下升温至550℃下焙烧2h，焙烧后加入至65℃的去离子水中进行溶解，溶解的质量比为35:100，利用筛网孔径大小为200目的筛网过滤得滤液，滤渣，将滤液在真空度为0.04MPa下进行蒸发12min、降温、结晶，在室外环境下干燥5d，得结晶体(硫酸钠占比53.58％、氯化钠占比27.24％、水占比11.69％、硫酸钙占比5.98％、氯化钙1.51％)；
(3)研磨：将结晶体加入液氮中浸泡，结晶体与液氮的质量比为10:2.5，浸泡至液氮蒸发，并使结晶体升至室温，将质量比为100:2.5:2的结晶体、矿物(石英砂、石英岩、砂岩)、微粉硅胶加入至转速为150r/min的洁净混合机进行混合2min，混合完毕的混合料加至转速为480r/min的洁净球磨机进行研磨45min，出料时间为4min(出料量为0.5t/h，研磨的质量为35.7kg)，研磨后得到粒度＜100μm的粉体；
(4)改性：将质量比为100：2：0.17的粉体、聚二甲基硅氧烷、硬脂酸钠加入至转速为150r/min的洁净干燥混合机中，设置混合时的温度为70℃，进行混合35min、干燥后既得灭火剂产品，干燥完毕测得灭火剂产品的含水量为1.41％，得到可扑灭铝渣燃烧的灭火剂。
一种铝渣燃烧时灭火的方法，包括以下具体步骤：
(1)将保存好的灭火剂注入到干燥的储存罐中，同时储存罐中充入干燥的氩气保存，灭火剂：惰性气体体积比为9:1，储存罐压力为2.5MPa；
(2)储存罐的灭火剂注入到10kg规格的悬挂式灭火器中，铝渣储存槽存放有5kg铝渣堆，灭火器距离铝渣堆顶约0.7m，铝渣储存槽大小为14m 2(4m*3.5m)，点燃铝渣，当灭火器感温到铝渣燃烧的火情时，喷射灭火剂，进行灭火。
实施例3
本实施例的可扑灭铝渣燃烧的灭火剂的制备方法，包括以下步骤：
(1)收集：由废旧锂电池正极材料再合成过程中产生的高盐废水，经膜分离、蒸发得到56kg的含硫酸盐、氯盐的固废；
(2)提纯：通风环境下，将含硫酸盐、氯盐的固废在升温速度为30℃/min下升温至750℃下焙烧0.5h，焙烧后加入至65℃的去离子水中进行溶解，溶解的质量比为35:100，利用筛网孔径大小为400目的筛网过滤得滤液，滤渣，将滤液在真空度为0.04MPa下进行蒸发12min、降温、结晶，在室外环境下干燥5d，得结晶体(硫酸钠占比52.46％、 氯化钠占比23.08％、水占比15.97％、硫酸钙占比4.75％、氯化钙3.74％)；
(3)研磨：将结晶体加入液氮中浸泡，结晶体与液氮的质量比为10:3，浸泡至液氮蒸发，并使结晶体升至室温，将质量比为100：3：2的结晶体、矿物(石英砂、石英岩、砂岩)、微粉硅胶加入至转速为150r/min的洁净混合机进行混合2min，混合完毕的混合料加至转速为480r/min的洁净球磨机进行研磨45min，出料时间为6min(出料量为0.5t/h，研磨的质量为47.3kg)，研磨后得到粒度＜100μm的粉体；
(4)改性：将质量比为100：5：0.25的粉体、聚二甲基硅氧烷、硬脂酸钠加入至转速为150r/min的洁净干燥混合机中，设置混合时的温度为70℃，进行混合35min、干燥后既得灭火剂产品，干燥完毕测得灭火剂产品的含水量为1.87％，得到可扑灭铝渣燃烧的灭火剂。
一种铝渣燃烧时灭火的方法，包括以下具体步骤：
(1)将保存好的灭火剂注入到干燥的储存罐中，同时储存罐中充入干燥的氩气保存，灭火剂：惰性气体体积比为7.5:1，储存罐压力为2.5MPa；
(2)储存罐的灭火剂注入到10kg规格的悬挂式灭火器中，铝渣储存槽存放有4.3kg铝渣堆，灭火器距离铝渣堆顶约0.8m，铝渣储存槽大小为14m 2(4m*3.5m)，点燃铝渣，当灭火器感温到铝渣燃烧的火情时，喷射灭火剂，进行灭火。
对比例1
一种铝渣燃烧灭火的方法，包括以下具体步骤：
与实施例1的区别在于：步骤(3)中未经液氮浸泡。
对比例2
一种铝渣燃烧灭火的方法，包括以下具体步骤：
与实施例1的区别在于：步骤(3)中未加石英类矿物和微粉硅胶。
对比例3
一种铝渣燃烧灭火的方法，包括以下具体步骤：
与实施例1的区别在于：步骤(4)中未加聚二甲基硅氧烷。
对比例4
一种铝渣燃烧灭火的方法，包括以下具体步骤：
与实施例1的区别在于：步骤(4)中未加硬脂酸钠。
对比例、实施例分析：
表1中，粉体粒度采用激光粒度仪测定，含水量常规测定方法测得，铝渣被灭所需时间为：铝渣开始燃烧30s后，灭火剂喷射到燃烧的铝渣，灭掉火所需时间。
表1中，可见与对比例1、2相比，实施例1、2、3的粒度均＜100μm，粉体的粒度更小，表面积增大，表面能增大，易于将燃烧的铝渣进行物理覆盖、化学覆盖，因此灭火剂的灭火效率高。与对比例3相比，实施例1、2、3含水量均＜2.5％，。实施例1、2、3的灭火时间均短于对比例1、2、3的灭火时间，效果较好。
表1 实施例与对比例参数表
Figure PCTCN2021142930-appb-000001
从实施例1和对比例1可以看出，对比例1的结晶体未经液氮处理，结晶体的晶体结构不容易被破坏，使得在研磨处理后，粉体的粒度没法减小，不易于将燃烧的铝渣进行物理覆盖、化学覆盖，因此降低了灭火剂的灭火效率。
从实施例1和对比例2可以看出，对比例2的未加石英类矿物和微粉硅胶，在研磨处理时，粉体的粒度大，粉体的粒度在50～100μm、>100μm占比较多；实施例1粉体粒度在20～50μm占比最多。
从实施例1和对比例3可以看出，对比例3未加聚二甲基硅氧烷，疏水能力差，导致含水量增加，进而扑灭铝渣燃烧的时间变长。
从实施例1和对比例4可以看出，对比例4未加硬脂酸盐，颗粒之间团聚，粉体的粒径变大，聚二甲基硅氧烷包覆粉体的时间变长，进而灭铝渣燃烧的时间变长。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种可扑灭铝渣燃烧的灭火剂，其特征在于，包括以下原料：硫酸盐、氯盐、矿物、硅胶、表面活性剂、硬脂酸盐。
  2. 根据权利要求1所述的可扑灭铝渣燃烧的灭火剂，其特征在于，所述硫酸盐为硫酸钠、硫酸钙；所述氯盐为氯化钠、氯化钙。
  3. 根据权利要求1所述的可扑灭铝渣燃烧的灭火剂，其特征在于，所述表面活性剂为聚二甲基硅氧烷。
  4. 根据权利要求1所述的可扑灭铝渣燃烧的灭火剂，其特征在于，所述硬脂酸盐为硬脂酸钠、硬脂酸镁、硬脂酸钙或硬脂酸锌中的一种。
  5. 根据权利要求1所述的可扑灭铝渣燃烧的灭火剂，其特征在于，所述矿物为石英砂、石英岩、硅石或蛋白石中的至少一种。
  6. 权利要求1-5任一项所述的可扑灭铝渣燃烧的灭火剂的制备方法，其特征在于，包括以下步骤：
    (1)将含硫酸盐、氯盐的固废进行焙烧，加水溶解，过滤取滤液，进行蒸发、结晶，得结晶体；
    (2)将所述结晶体加入液氮中浸泡，浸泡后的结晶体与矿物、硅胶混合，制成粉体；
    (3)将所述粉体、表面活性剂、硬脂酸盐混合，干燥，即得所述的可扑灭铝渣燃烧的灭火剂。
  7. 根据权利要求6所述的制备方法，其特征在于，步骤(1)中，所述含硫酸盐、氯盐的固废是由废旧锂电池正极材料再合成过程中产生的含盐废水，经膜分离、蒸发得到。
  8. 根据权利要求6所述的制备方法，其特征在于，步骤(1)中，所述焙烧的温度为400～800℃，焙烧的时间为0.5～3h，焙烧的升温速度为10～30℃/min。
  9. 根据权利要求6所述的制备方法，其特征在于，步骤(2)中，所述结晶体与液氮的质量比为10:(1～3)；步骤(2)中，所述结晶体、矿物、硅胶的质量比为100：(1～5)：(1～2)。
  10. 一种灭火器，其特征在于，包括权利要求1-5任一项所述的可扑灭铝渣燃烧的灭 火剂。
PCT/CN2021/142930 2021-05-31 2021-12-30 可扑灭铝渣燃烧的灭火剂及其制备方法和应用 WO2022252601A1 (zh)

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ES2958090R1 (es) 2024-04-09
CN113413569A (zh) 2021-09-21
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