Basalt three-phase foam extinguishing agent and preparation method thereofTechnical Field
The invention belongs to the field of fire-fighting and fire-extinguishing materials, and particularly relates to a foam extinguishing agent, and more particularly relates to a high-efficiency basalt three-phase foam extinguishing agent and a preparation method thereof.
Background
The traditional two-phase foam extinguishing agent plays an important role in extinguishing pool fires and oil type fires. The foam fire extinguishing agent mainly acts through three functions of cooling, shielding and heat insulation to extinguish fire. Two-phase foams are dispersions of aqueous surfactant solutions and gases, whose high surface area surface energy leads to thermodynamic instability. The primary mechanisms that lead to foam decay are drainage, coalescence and coarsening of the foam. Coalescence between small unstable bubbles occurs to form larger bubbles. Driven by gravity and laplace pressure differential, the water in the liquid film automatically flows to the Plateau boundary, causing the liquid film to thin, and in the presence of pressure differentials between bubbles of different sizes, causing the liquid film to coarsen and break. The surfactant in the foam fire suppressant may adsorb at the gas/liquid interface to form a stable foam. Since the surfactant has a function of reducing the surface tension, the drainage speed can be slowed down by reducing the pressure gradient between different bubbles. However, since the adsorption of surfactant molecules on the liquid film is reversible, low adhesion energy leads to easy desorption of the surfactant under the interference of factors such as oil and high temperature, and poor foam stability is caused as a result.
Therefore, in practical application, the foam extinguishing agent generally has the outstanding problems of poor thermal stability at high temperature, low re-ignition resistance and the like. In order to solve the problems of low interfacial film strength, fast liquid film drainage and easy defoaming of foaming agent molecules in two-phase foams, many scholars attempt to add burning-resistant powder into two-phase foams to form a foam system with air, water and solid particles coexisting in three phases of solid, liquid and gas, which is called three-phase foam.
Compared with the traditional gas-liquid two-phase foam, the solid particles are added to affect the precipitation speed of water in the liquid film and the stability of the foam, and the properties, particularly the surface characteristics, of the solid particles also have great influence on the strength of the liquid film and the stability of the liquid film. The three-phase foam stabilization mechanism has been intensively studied by many researchers. It has been shown that only particles with proper wettability have excellent foam stabilizing properties, and that the stability of a three-phase foam is also strongly dependent on the size, shape and concentration of the solid particles. Solid nanoparticles, such as silica, CaCO3, and alumina, are commonly used to stabilize three-phase foam systems. However, the use of nanoparticle-stabilized foams in large oil fields is limited due to high cost and agglomeration problems of the nanoparticles. The basalt is widely distributed in Fujian provinces, Henan provinces, Heilongjiang provinces and the like, has the advantages of low price, easy obtainment and convenient processing, and also has the advantages of good high-temperature resistance and good heat-insulating property. The basalt three-phase foam extinguishing agent is beneficial to forming an oxygen-insulating layer on the oil surface when oil gas fire is extinguished, so that the fire is extinguished quickly.
The research on the three-phase foam extinguishing agent is not much at home and abroad, and few scholars try to optimize and improve the three-phase foam extinguishing agent from different application scenes and using modes, and the three-phase foam extinguishing agent has various problems although the three-phase foam extinguishing agent has excellent performance in a specific application scene.
For example, patents CN1776195, CN210698570U, CN205042006U, CN2841966, etc. are all directed to improving the foam foaming device in the practical application environment of coal mines, but do not describe the fire extinguishing principle and the manufacturing method of three-phase foam, and the application scenario is limited.
Patents CN110448852A, CN108421196A, CN102836516A, etc. describe the preparation of three-phase foams, but all add fluorocarbon surfactants. In 4 months in 2009, 9 kinds of substances such as perfluorooctane sulfonic acid (PF0S) and salts thereof contained in AFFF were listed in the array of Persistent Organic Pollutants (POPs) by the Environmental Planning Agency (EPA) of united nations, through the stockholm convention on Persistent Organic Pollutants (POPs).
In summary, the three-phase foam extinguishing agent researched at home and abroad at present has the following defects: research contents are few, most of the research contents are based on specific application scenes to improve a foaming device, and a surfactant which is not friendly to the environment is added into a foam liquid. The three-phase foam fire extinguishing technology is not mature.
Disclosure of Invention
Aiming at the problems that the traditional two-phase fire extinguishing agent in the prior art uses fluorocarbon surfactant, chelating agent and the like, is high in price, toxic and harmful, is not friendly to the environment, and foams are easy to crack and unstable when oil fire is extinguished, the invention provides an efficient basalt three-phase foam extinguishing agent and a preparation method thereof, and aims to: improve the fire extinguishing efficiency of the foam extinguishing agent and protect the environment.
The technical scheme adopted by the invention is as follows:
a preparation method of a basalt three-phase foam extinguishing agent comprises the following steps:
s1: grinding basalt particles to a particle size of micron order;
s2: dispersing the ground basalt particles in deionized water, and then adding ammonium polyphosphate to perform ultrasonic treatment until the basalt particles are completely dispersed to obtain a basalt dispersion liquid;
s3: adding a tris buffer solution into the basalt dispersion liquid, adjusting the pH value to 8.5, adding dopamine, stirring for reaction, washing, filtering and drying after the reaction is finished to obtain the basalt coated with dopamine;
s4: weighing 1-5 parts by weight of sulfamic acid, dissolving in 40-60 parts by weight of ethanol, weighing 1-5 parts by weight of KH560, stirring to react with the ethanol solution of sulfamic acid, adding 2-3 parts by weight of dopamine-coated basalt into the solution, continuing to react, adding 0.2-1 part by weight of octyl trimethylsilane, continuing to react until the reaction is finished, washing, filtering and drying to obtain modified basalt powder;
s5: adding 1-3 parts by weight of sodium dodecyl sulfate, 2-5 parts by weight of an organic silicon surfactant, 21-42 parts by weight of alkyl glycoside and 4-8 parts by weight of dodecyl betaine into 40 parts by weight of deionized water, fully stirring to obtain a component A, adding 10-31 parts by weight of propylene glycol and 0.8-2.5 parts by weight of dodecanol into 20 parts by weight of deionized water to obtain a component B, adding the component A into the component B, fully mixing, adding 1.5-5 parts by weight of polyacrylamide, and adding deionized water to prepare a 100% foam concentrated solution;
s6: mixing the foam concentrated solution with deionized water according to the volume ratio of 6: 94 to obtain foam liquid;
s7: weighing 0.2-0.5 part of modified basalt powder into 100 parts of foam liquid by weight, and carrying out ultrasonic treatment until the modified basalt powder is completely dispersed to obtain the basalt three-phase foam extinguishing agent.
Preferably, the particle size of the basalt ground in step S1 is 0.8 to 2.0 μm.
Preferably, in the step S2, the basalt particles are 5-10 parts, the deionized water is 100-200 parts, and the ammonium polyphosphate is 0.5-1 part by weight.
Preferably, in the step S3, 0.2-0.5 parts of dopamine and 0.2-0.4 parts of tris buffer are calculated according to parts by weight.
Preferably, the reaction time of step S3 is 13 to 17 hours.
Preferably, in step S3, the pH is adjusted with a saturated sodium hydroxide solution, and the reaction temperature is room temperature.
Preferably, the washing treatment in steps S3 and S4 is centrifuge centrifugation 3-5 times.
Preferably, the reaction temperature of step S4 is 60 ℃ to 80 ℃ and the reaction time is 7h to 13 h.
A basalt three-phase foam extinguishing agent is prepared by any one of the preparation methods.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) the surfactant material adopted by the technical scheme of the invention does not contain harmful substances to the environment such as fluoride and the like, and is an environment-friendly foam extinguishing agent.
(2) The technical scheme of the invention adopts the basalt three-phase foam, has the advantages of simple material taking, convenience and easy obtaining, low price, convenient processing and no secondary pollution, and the basalt has good heat insulation and high temperature resistance, not only can play a good heat insulation and reduction role in extinguishing high-temperature oil fire, but also can enhance the stability of the foam, isolate the contact of an oil surface and air, and achieve the effect of extinguishing fire by isolating oxygen.
(3) The technical scheme of the invention adopts the methods of dopamine coating and silane coupling agent in-situ grafting modification to change the physical and chemical properties of the basalt, so that the lipophilicity of the basalt is increased, and the basalt is more beneficial to being in close contact with foam, thereby achieving the effect of enhancing the stability of the foam.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the attached tables in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
Examples 1
Taking the basalt particles after the rough grinding treatment, putting the basalt particles into a planetary ball mill of 0.8L for ball milling treatment, performing ball milling for multiple times to enable the particle diameter of the basalt particles to reach 2 mu m, and then sealing and storing the basalt particles. Weighing 5 parts by weight of ground basalt, dispersing in 100 parts by weight of deionized water, adding 0.5 part by weight of ammonium polyphosphate, and carrying out ultrasonic treatment for 10min by using a probe until the basalt is completely dispersed; and adding 0.3 part of tris buffer solution into the basalt dispersion liquid subjected to ultrasonic treatment, adjusting the pH value to 8.5 by using a saturated sodium hydroxide solution, adding 0.2 part of dopamine, and stirring and reacting at normal temperature for 13 hours. And after the reaction is finished, centrifuging the dispersion liquid, washing the dispersion liquid for 3 times by using deionized water, then carrying out suction filtration and drying a filter cake, grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing the sample bottle to obtain the dopamine-coated basalt. Weighing 1 part of sulfamic acid according to parts by weight, dissolving in 50 parts of ethanol, weighing 1 part of KH560, adding the solution and sulfamic acid ethanol solution into a 250ml three-neck flask, stirring and reacting at 60 ℃ for 7 hours, adding 2 parts of dopamine-coated basalt, continuing to react for 11 hours, adding 0.2 part of octyl trimethylsilane, continuing to react for 13 hours until the reaction is finished, washing the dispersion liquid with deionized water for 3 times, centrifuging, carrying out suction filtration, and drying a filter cake. And grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing to obtain the in-situ graft modified basalt powder. 1 part of Sodium Dodecyl Sulfate (SDS), 2 parts of organosilicon surfactant (Silok-8008), 20 parts of alkyl glycoside (APG 0810) and 4 parts of dodecyl betaine (BS-12) are weighed into 40 parts of deionized water and sufficiently stirred to obtain component A. Then 10 parts of propylene glycol and 1 part of dodecanol are weighed and added into 20 parts of deionized water to obtain the component B. Adding the component A into the component B, fully mixing, adding 1.5 parts of polyacrylamide, and adding the rest deionized water to prepare a foam concentrated solution. Mixing the prepared foam concentrated solution with deionized water according to the weight ratio of 6: 94 to obtain foam liquid. Weighing 0.2 part by weight of modified basalt powder into 100 parts of foam liquid, and carrying out ultrasonic treatment until the modified basalt powder is completely dispersed to obtain the basalt three-phase foam extinguishing agent.
EXAMPLES example 2
Taking the basalt particles after the rough grinding treatment, putting the basalt particles into a 2L planetary ball mill for ball milling treatment, performing ball milling for multiple times to enable the particle diameter to reach 1.2 mu m, and then sealing and storing. Weighing 5 parts by weight of ground basalt, dispersing in 100 parts by weight of deionized water, adding 0.8 part by weight of ammonium polyphosphate, and carrying out ultrasonic treatment for 10min by using a probe until the basalt is completely dispersed; 0.3 part of tris buffer solution is added into the basalt dispersion liquid after ultrasonic treatment, the pH value is adjusted to 8.5 by using saturated sodium hydroxide solution, then 0.4 Part of Dopamine (PDA) is added, and stirring reaction is carried out for 15 hours at normal temperature. And after the reaction is finished, washing the dispersion liquid for 3 times by using deionized water, centrifuging, then carrying out suction filtration and drying a filter cake, grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing to obtain the dopamine-coated basalt. Weighing 2 parts of sulfamic acid according to parts by weight, dissolving in 50 parts of ethanol, weighing 2 parts of KH560, adding the mixture into a 250ml three-neck flask together with an ethanol solution of sulfamic acid, stirring and reacting at 60 ℃ for 8 hours, adding 3 parts of dopamine-coated basalt, continuing to react for 12 hours, adding 0.3 part of octyl trimethylsilane, continuing to react for 14 hours until the reaction is finished, washing the dispersion liquid with deionized water for 3 times, centrifuging, carrying out suction filtration, and drying a filter cake. And grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing to obtain the in-situ graft modified basalt powder. 2 parts of Sodium Dodecyl Sulfate (SDS), 4 parts of silicone surfactant (Silok-8008), 30 parts of alkyl glycoside (APG 0810) and 6 parts of dodecyl betaine (BS-12) were weighed into 40ml of deionized water, and thoroughly stirred to give component A. Then 20 parts of propylene glycol and 2 parts of dodecanol are weighed and added into 20 parts of deionized water to obtain the component B. And adding the component A into the component B, fully mixing, adding 3 parts of polyacrylamide, and adding the rest deionized water to prepare a foam concentrated solution. Mixing the prepared foam concentrated solution with deionized water according to the weight ratio of 6: 94 to obtain foam liquid. Weighing 0.3 part by weight of modified basalt powder into 100 parts by weight of foam liquid, and carrying out ultrasonic treatment until the powder is completely dispersed to obtain the basalt three-phase foam extinguishing agent.
EXAMPLE 3
Taking the basalt particles after the rough grinding treatment, putting the basalt particles into a 2L planetary ball mill for ball milling treatment, performing ball milling for multiple times to enable the particle diameter to reach 0.8 mu m, and then sealing and storing. Weighing 10 parts by weight of ground basalt, dispersing in 200 parts by weight of deionized water, adding 1 part by weight of ammonium polyphosphate, and carrying out ultrasonic treatment for 10min by using a probe until the basalt is completely dispersed; 0.6 part of tris buffer solution is added into the basalt dispersion liquid after ultrasonic treatment, the pH value is adjusted to 8.5 by using saturated sodium hydroxide solution, then 0.5 Part of Dopamine (PDA) is added, and the mixture is stirred and reacted for 17 hours at normal temperature. And after the reaction is finished, washing the dispersion liquid for 3 times by using deionized water, centrifuging, then carrying out suction filtration and drying a filter cake, grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing to obtain the dopamine-coated basalt. Weighing 5 parts of sulfamic acid according to parts by weight, dissolving in 100 parts of ethanol, weighing 5 parts of KH560, adding the mixture into a 250ml three-neck flask together with an ethanol solution of sulfamic acid, stirring and reacting at 60 ℃ for 9 hours, adding 3 parts of dopamine-coated basalt, continuing to react for 13 hours, adding 0.8 part of octyl trimethylsilane, continuing to react for 15 hours until the reaction is finished, washing the dispersion liquid with deionized water for 3 times, centrifuging, carrying out suction filtration, and drying a filter cake. And grinding the dried filter cake by using a mortar, filling the ground filter cake into a sample bottle, and sealing and storing to obtain the in-situ graft modified basalt powder. 3 parts of Sodium Dodecyl Sulfate (SDS), 5 parts of silicone surfactant (Silok-8008), 40 parts of alkyl glycoside (APG 0810) and 8 parts of dodecyl betaine (BS-12) were weighed into 40ml of deionized water, and thoroughly stirred to give component A. Then 30 parts of propylene glycol and 3 parts of dodecanol are weighed and added into 20 parts of deionized water to obtain the component B. And adding the component A into the component B, fully mixing, adding 5 parts of polyacrylamide, and adding the rest deionized water to prepare a foam concentrated solution. Mixing the prepared foam concentrated solution with deionized water according to the weight ratio of 6: 94 to obtain foam liquid. Weighing 0.5 part by weight of modified basalt powder into 100 parts by weight of foam liquid, and carrying out ultrasonic treatment until the powder is completely dispersed to obtain the basalt three-phase foam extinguishing agent.
The foam performances of the basalt three-phase foam extinguishing agent material prepared by the invention and the two-phase foam extinguishing agent sold in the market are tested, and the specific test results are shown in the following table 1:
table 1: the foam performance of the product of the invention is compared with that of a two-phase foam extinguishing agent sold on the market
| Name of test sample | Expansion ratio of foam | Half life of liquid separation/min | Height of foam/ml |
| Basalt three-phase foam extinguishing agent | 5.1 times of | 28.08 | 510 |
| 3% water-based extinguishing agent | 5.9 times of | 11.27 | 590 |
| 6% anti-soluble foam extinguishing agent | 6 times of | 9 | 600 |
| 6% environment-friendly water-based extinguishing agent | 5.9 times of | 9 | 590 |
From the above embodiments and the experimental results of table 1, it can be seen that the beneficial effects of the present invention are embodied in:
1. is friendly to the environment: the invention does not add reagents and medicines harmful to the environment in the production and preparation process, has simple and easily obtained raw materials, saves resources, has no secondary pollution in the production process, and belongs to an environment-friendly foam extinguishing agent.
2. The foam stability is high: from the table 1, it can be seen that the half-life of the liquid separating of the basalt three-phase foam extinguishing agent is far higher than that of the common commercial two-phase foam extinguishing agent. Therefore, when aiming at fire disasters such as oil and the like, the basalt three-phase foam extinguishing agent can effectively improve the fire extinguishing efficiency, increase the fire extinguishing efficiency and reduce the fire extinguishing time.
3. The cost is low: the cost of the fluorocarbon surfactant which must be added is high, so that the aqueous film-forming foam extinguishing agent which is widely used in the market is mostly imported abroad, and the use cost is high. In comparison, the surfactants used in the invention are all common surfactants, belong to domestic self-production and use, and are superior to fluorocarbon surfactants in terms of convenience and easiness in use and cost. The basalt added in the invention has rich resources in China, simple processing and treatment and lower overall production cost.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.