Quan Wang*ab,
Fengqi Wanga,
Chengxiao Lia,
Zhimin Li*c and
Rui Lia
aSchool of Chemical Engineering, Anhui University of Science & Technology, Huainan 232001, China. E-mail: wqaust@163.com
bEngineering Laboratory of Explosive Materials and Technology of Anhui Province, Huainan 232001, China
cSchool of Civil Engineering and Architecture, Anhui University of Science & Technology, Huainan 232001, China
First published on 8th March 2021
In this work, four new dry water fire extinguishing agents (FEAs) were prepared by hydrophobic SiO2 and aqueous solution under certain conditions. The dry water FEAs were developed and we conducted two types of fire extinguishing experiments (i.e., class A solid fire and class B liquid fire test). Thermocouples and a color video camera were used to measure burning temperature and record the fire extinguishing process. Results indicate that the new dry water FEAs have the ability to extinguish A, B and C fires, and have a better cooling effect than dry powder FEA. It is noted, compared with traditional FEAs, that dry water FEAs have the advantages of high efficiency and high speed, and have a potential application prospect.
In the mid-20th century, a halon gas FEA was first studied and used,1 but halon halogenated hydrocarbons will decompose O3, which will damage the ozone layer structure for a long time. Currently, FEAs are divided into inert gas fire extinguishing agents, halogenated hydrocarbon fire extinguishing agents and aerosol fire extinguishing agents.2–4 Their common advantages are: no harm to people and the environment, high fire extinguishing efficiency and smaller equipment.5 However, there are also many disadvantages:6,7 inert gas extinguishing agents will expand and discharge in the storage and use process, halogenated hydrocarbon extinguishing agent emission has a long duration. The production process of aerosol extinguishing agents is complex, and the raw material cost is high. Therefore, a new type of extinguishing agent with high efficiency, environmental protection, and low cost should be developed.
Dry water material is a kind of material which takes liquid as the main component and disperses into droplet particles with extremely small size at high speed, and hydrophobic powder is uniformly coated on the outer surface of the droplets.8,9 It is found that the water content is more than 90%, and is widely used in the storage of methane, carbon dioxide, cosmetics, pharmaceuticals, and other fields.10–15 Because of the large amount of aqueous solution covered by dry water materials, it can be used in the field of fire extinguishing agent. The mechanism of dry water extinguishing agent is different from that of traditional dry powder extinguishing agent and fine water mists extinguishing agent, it combines the advantages of both, and has the combined mechanisms of physical cooling and chemical inhibition. In this paper, chemical additives such as ammonium dihydrogen phosphate are added to distilled water to modify dry water materials and investigate the fire-extinguishing effect of different components of dry water materials.
In the paper, four types of dry water extinguishing agents were developed by using hydrophobic SiO2 and an aqueous solution containing additives as raw materials utilizing the high-speed dispersion method. Fire extinguishing experiments were carried out on class A and class B fire extinguishing conditions (class A refers to the fire of solid substances, class B refers to liquid and fusible solid fire, class C refers to gas fire in GB4968-2008 in China).16 Meanwhile, ABC dry powder extinguishing agents were used as a reference to evaluate the extinguishing performance of dry water extinguishing agents, and select the dry water extinguishing agents with the best extinguishing effect. Meanwhile, ABC dry powder FEAs were taken as a reference to evaluate the extinguishing performance of dry water FEAs and select the dry water FEAs with the best extinguishing effect.
In the experiments, hydrophobic silica, distilled water, ammonium dihydrogen phosphate, sodium chloride and polyvinyl alcohol were used to prepare ammonium dihydrogen phosphate solution, sodium chloride solution and polyvinyl alcohol solution. K-type armored thermocouples are selected to detect the temperature of the class A fire. It is composed of thermocouples wire, high-temperature resistant metal tube shell, and insulating material. It can measure the temperature range from 0 to 1600 °C. It is often used with a temperature recorder and temperature conversion module. In this experiment, R-type platinum–rhodium thermocouples are selected to detect the temperature of class B fire. It is made of metal platinum wire (0.05 mm) and rhodium wire (0.05 mm). The positive electrode is the platinum–rhodium alloy, and the negative electrode is pure platinum. The temperature range is 0–1600 °C. And In this experiments, ABC dry powder FEA was used for the comparative test.
The mass ratio of the hydrophobic SiO2 and the above solutions were set as 1:10 respectively, the speed of the high-speed dispersing mixer was set as 4000 rpm and the stirring time was 60 s, and the pure water dry water FEA, ammonium dihydrogen phosphate dry water FEA, sodium chloride dry water extinguishing agent and polyvinyl alcohol dry water FEA were obtained. Table 1 shows the preparation parameters of dry water FEA.
Types of FEAs | Stirring speed (rpm) | Mixing time (s) | MSiO2:Maqueous solution | Additive |
---|---|---|---|---|
Pure water dry water FEA | 4000 | 60 | 1:10 | 0 |
Ammonium dihydrogen phosphate dry water FEA | 4000 | 60 | 1:10 | 10% ammonium dihydrogen phosphate |
Sodium chloride dry water FEA | 4000 | 60 | 1:10 | 10% sodium chloride |
PVA dry water FEA | 4000 | 60 | 1:10 | 0.5% polyvinyl alcohol |
The free radicals produced by the reaction can cut off the combustion reaction chain. At the same time, ammonia and water vapor can isolate the contact between oxygen and combustibles. Phosphorus pentoxide solids can cover the surface of combustibles to prevent combustion. Sodium chloride has the effect of extinguishing flames, which can destroy the center of the chain reaction during combustion and promote the interruption of the reaction chain.
Class B fire simulation system was composed of an experimental platform, oil tray, R-type platinum–rhodium thermocouples, and a temperature recorder, as shown in Fig. 4. The size of the oil tray is 400 mm × 300 mm × 40 mm. Water at a depth of 20 mm was injected first, followed by 200 ml of no. 90 gasoline. The oil tray was placed on the metal platform. According to the evaluation method of dry powder fire-FEA in GB4066-2017 (China),17 if the FEA can extinguish class B fire, it can be considered to have the fire-extinguishing ability of class C fire. Therefore, the fire-extinguishing situation of class C fire can be measured according to the fire-extinguishing result of class B fire.
(2) Build fire models of class A and B, then fix the thermocouples and temperature recorders to test the fire extinguishing temperature.
(3) Turn on the temperature measurement system, start the fire, and time it. While the fuel burns to 53–57% of the original content, use the dry water extinguisher to spray out the dry water.
(4) During the spraying process, hold the handle to maintain the maximum spraying state, the nozzle should be in front of the fire target when spraying.
(5) Timing ends when the flame goes out. When the temperature drops to room temperature, record the data and weigh the weight of the extinguisher W2.
Repeat the experiments 2 times. If two experiments continuously succeed or fail, the third experiment can be not necessary.
Type of FEAs | Fire extinguishing time (s) | Average fire extinguishing time (s) | Consumption of FEAs (g) | Average consumption of FEAs (g) | Fire situation |
---|---|---|---|---|---|
Pure water dry water FEA | 1.78, 1.76 | 1.77 | 36.03, 37.67 | 36.85 | Out, out |
PVA dry water FEA | 1.56, 1.59 | 1.58 | 34.52, 35.62 | 35.07 | Out, out |
Ammonium dihydrogen phosphate dry water FEA | 1.42, 1.48 | 1.50 | 29.32, 31.42 | 30.37 | Out, out |
Sodium chloride dry water FEA | 1.65, 1.60 | 1.63 | 33.12, 32.56 | 32.84 | Out, out |
Dry powder FEA | 1.53, 1.55 | 1.54 | 31.26, 32.54 | 31.90 | Out, out |
Through the temperature change curves, it can be found that the fire-extinguishing process of class A fire is divided into the pre-combustion stage, free burning stage, and fire-extinguishing stage. The time of the pre-combustion stage and free burning stage in several groups of simulation experiments were all around 60 s, and their maximum temperatures were around 600 °C. This indicates that the maximum burning temperature of selected wood was about 600 °C, so the fire extinguishing experiments were conducted at this time to ensure that other conditions were basically the same.
In the pre-combustion stage, the gasoline was fully burned, and then the flame ignited the wood stacks above. It can be found that the initial temperature in Fig. 6 was higher because the thermocouples detected the hot air flow caused by the ignition of the gasoline under it, increasing in the initial temperature. However, since the initial temperature is relatively low and within a controllable range, it can be ignored.
When the gasoline burns out, the energy released by the gasoline combustion makes the wood stacks start to enter the free burning stage. At this time, the measured temperature is completely the flame temperature of the wood stacks burning. After 60 s, several groups of wood stacks reach the highest value of free combustion temperature, and at this time, the firefighting begins. Due to the rate and flame fluctuation of different groups of wood stacks, the maximum temperature reached will be different, but basically remain within a certain range.
During the fire extinguishing stage, the dry water FEA contacts with the flame, and the dry water structure is rapidly ruptured under the influence of high temperature, and a large number of solutions flow out to give full play to the fire extinguishing effect. The temperature of each thermocouple quickly dropped to about 200 °C, which can be found that ammonium dihydrogen phosphate dry water fire when the temperature drops fastest, the highest temperature to 200 °C almost perpendicular to the axis of the curve. The fire extinguishing image of polyvinyl alcohol is similar to that of pure water dry water FEA, and it decreases rapidly at the highest temperature of 200 °C. This is because the addition of PVA dry water only changes the coating strength, but has no effect on the extinguishing performance of the aqueous solution. Adding sodium chloride dry water FEA can extinguish the flame quickly, making the temperature in the oil tray drop rapidly, slightly steeper than the cooling curve of pure water, indicating that sodium chloride has a promoting effect on extinguishing the fire.
Compared with ABC dry powder FEA, it is found that the cooling curve of several groups of dry water FEA are roughly the same as that of ABC dry powder FEA, both of which can drop to 200 °C within 10 s, but the cooling curve of ammonium dihydrogen phosphate dry water is steeper than that of ABC dry powder, indicating that ammonium dihydrogen phosphate dry water has a better cooling effect from high temperature to low temperature. The temperature of the fire extinguisher decreases from 200 °C to 50 °C. The dry water of pure water, polyvinyl alcohol, and ammonium dihydrogen phosphate are used for about 35 s, the dry water of sodium chloride is used for about 50 s, and the dry powder of ABC is used for about 80 s. It shows that the cooling effect of the dry water extinguisher is more remarkable than that of the dry powder of ABC at about 200 °C, which is due to the large amount of water contained in the dry water extinguish. It can continuously absorb heat and evaporation, which has the effect of cooling combustible materials rapidly.
Because of the two burning conditions of type A wood stacking fire, the extinguishing process of dry water FEA can be divided into two aspects. For open fire, the dry water FEA driven by pressure first reaches the top of the flame, and the solution inside the heated cracked dry water flows out, contacting with the flame to absorb heat by evaporation. The high-temperature water vapor formed rapidly rises and drives away the air above the flame, thus reducing the oxygen content above the flame. At the same time, due to the low density of dry water FEA, part of the dry water will fly into the air during the process of ejecting, which also plays a role in reducing the oxygen content. Dry water FEA with a modifier such as ammonium dihydrogen phosphate dry water, ammonium dihydrogen phosphate when heated will quickly decompose ammonia gas and phosphoric acid, the production of free radicals can block the combustion process, these can effectively extinguish the open fire.
Type of FEA | Fire extinguishing time (s) | Mean time to extinguish (s) | Consumption of fire FEA (g) | Average FEA consumption (g) | Fire situation |
---|---|---|---|---|---|
Pure water dry water FEA | 2.94, 3.12 | 3.02 | 132.23, 135.78 | 134.01 | Out, out |
PVA dry water FEA | 2.88, 2.96 | 2.92 | 129.58, 134.42 | 132.00 | Out, out |
Ammonium dihydrogen phosphate dry water FEA | 2.62, 2.68 | 2.65 | 108.74, 115.63 | 112.19 | Out, out |
Sodium chloride dry water FEA | 2.84, 2.72 | 2.78 | 121.58, 127.93 | 124.76 | Out, out |
Dry powder dry water FEA | 2.44, 2.51 | 2.48 | 117.52, 121.69 | 119.61 | Out, out |
During the combustion fluctuation period, the flame temperature fluctuates up and down with time, this is because the gasoline volatilization accompanies the gasoline combustion process, and the instantaneous ignition of the volatile gasoline gas when it reaches the top of the flame makes the temperature rise, while the gasoline combustion range in different areas of the oil tray is not consistent, resulting in the process of competing for the oxygen above the gasoline makes the oxygen supply in some areas too little, at this time the temperature will temporarily drop. In order to ensure the consistency of the experiment, the fire extinguishing is carried out when the temperature measured by the thermocouples is above 1000 °C.
Comparing several groups of temperature change images in the cooling intervals, it is found that the FEA prepared by dry water can make the temperature drop within 2 s. Among them, ammonium dihydrogen phosphate dry water FEA has the best cooling effect, sodium chloride is second, and pure water and polyvinyl alcohol are slower. Ammonium dihydrogen phosphate can break down the ammonia and phosphoric acid, produce free radicals that can cut off the combustion reaction chains, sodium chloride has the effect of restraining flame. The decrease of PVA is slower than that of pure water, which is due to the large particle size dry water FEA formed by PVA, which makes the content of FEAs scattered to various areas in the process of extinguishing not dense enough. As a result, the oil fire that is cooled is quickly heated by the oil fire that is not cooled, making the cooling process floating.
Compared with dry powder FEA, dry powder FEA time is the shortest, but the slowest cooling process, it is because the dry powder FEA contains a lot of ammonium salt compounds, these substances can have the effect of effective extinguishing, but when the flame was extinguished, the oil temperature is still high. However, the cooling effect of dry powder FEA is not as good as that of water solution in dry water FEAs, and the temperature dropping process of dry powder FEA appears to rise again and again. It takes about 5 seconds to drop from the highest temperature to 50 °C, but the cooling after 50 °C is slower, and it is not recorded by the temperature recorder.
The biggest difference between class B fire and class A fire is that the combustible liquids in class B fires are volatile. During the combustion process, they continuously volatilize into the air to form very small droplets, which can burn more fully after contacting with the air. In the initial stage of fire extinguisher spraying, the airflow carried by fire extinguisher will reach the ignition area before the extinguisher, so that part of the combustible liquid will be blown into the air, at the same time, it will accelerate the airflow above, speed up the fresh air supply, and make the starting flame bigger. The principle of extinguishing the fire lies in the balance of the cooling of dry water FEA and the rate of combustion and heat release. If the cooling rate is fast, the flame is extinguished, it can be seen that polyvinyl alcohol and sodium chloride dry water cooling process curve jitter, indicating that the process of dry water FEA cooling effect and gasoline combustion heating at the same time, so that the temperature rise and fall. Ammonium phosphate dry water can also be faster to extinguish the flame, and the cooling effect is obvious, indicating that in the destruction of B-type fires, the chemicals produced by the decomposition of ammonium dihydro phosphate in the chemical effect (such as ammonium, phosphoric acid, etc.), while water plays a role in rapid heat absorption cooling flammable liquid. However, pure dry water has no additives in it, but it can also extinguish class B fires, indicating that the hydrophobic SiO2 coated on the outside after the structure is broken plays a good role in isolating oxygen. This also shows that the modifier of dry water FEA has a great influence on the extinguishing effect, and in the process of extinguishing class B fire, both physical and chemical extinguishing principles are used.
(1) All four groups of dry water FEAs can effectively extinguish class A fire and class B fire, and the extinguishing effect is similar to that of ABC dry powder FEA, so it is considered that dry water FEA has the ability to extinguish class A fire, class B fire, and class C fire.
(2) Dry water FEA with ammonium dihydrogen phosphate added in four groups of dry water FEA has the best extinguishing effect, and the cooling effect of dry water FEA is better than that of dry powder in the extinguishing process of category B fire.
(3) The extinguishing mechanism of dry water FEA combines physical cooling and chemical inhibition, which can not only use the free radicals generated to cut off the combustion reaction chain but also use aqueous solution heat absorption to cool down.
This journal is © The Royal Society of Chemistry 2021 |