Mining gel-protein foam extinguishing agent and preparation method thereof

Abstract

The invention belongs to the technical field of coal mine fire prevention and extinguishing, and discloses a mining gel-protein foam extinguishing agent and a preparation method thereof.The preparation method mainly comprises the steps that kitchen waste serves as a raw material, and animal protein and plant protein in the kitchen waste are hydrolyzed through proteolytic enzyme to form hydrolyzed protein; the gel-protein foam extinguishing agent is prepared by respectively screening the concentration of the four surfactants with the optimal foaming performance, compounding the four surfactants with the prepared hydrolyzed protein and adding components such as a gelling agent, a cross-linking agent and an anti-freezing agent. According to the prepared gel-protein foam fire extinguishing agent, efficient fire extinguishing is guaranteed, meanwhile, resource utilization of domestic waste is achieved, compared with a traditional foam fire extinguishing agent, the gel-protein foam fire extinguishing agent is more stable, the used materials are all bio-based raw materials, and pollution to the environment is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of resource utilization of domestic waste and fire prevention and extinguishing in coal mines, and in particular to a gel-protein foam fire extinguishing agent for mines and a preparation method thereof. Background Art

[0002] With the acceleration of the global industrialization process, coal, as the main source of energy, has been continuously mined and utilized. However, the frequent occurrence of coal mine accidents has also become a global concern. Among them, fire is one of the common and extremely harmful accidents in coal mine production. Coal mine fires not only cause property losses, but more importantly, they threaten the lives of miners. Therefore, the study of coal mine fire prevention and extinguishing technology has become an important topic. As a major coal producer and consumer, coal mine fire prevention and control is particularly important in my country. In recent years, the Chinese government and enterprises have increased their investment in coal mine fire prevention and extinguishing technology, and actively introduced and developed various new fire prevention and extinguishing technologies to improve coal mine production safety and protect the lives of miners.

[0003] Coal mine fire prevention and extinguishing is a complex issue involving multiple disciplines. It not only involves knowledge in multiple fields such as coal mining, geological engineering, and safety engineering, but also needs to consider multiple factors such as the environment, equipment, and personnel in the mine. Therefore, the study of coal mine fire prevention and extinguishing technology requires rich theoretical knowledge and practical experience to ensure the feasibility and effectiveness of the technology. At present, my country's coal mine fire prevention and extinguishing technology has achieved certain results. For example, grouting fire prevention and extinguishing technology, inert gas fire prevention and extinguishing technology, and pressure equalization fire prevention and extinguishing technology have been widely used. The application of these technologies not only improves the safety production level of coal mines, but also provides a strong guarantee for the sustainable development of my country's coal industry. However, with the increase in the depth of coal mining and the increase in the difficulty of mining, coal mine fire prevention and extinguishing work faces more severe challenges. For example, the problem of spontaneous combustion of deep coal seams and the problem of fire prevention and control in high-gas mines need further research and resolution. Therefore, in the future, it is necessary to further strengthen the research and innovation of coal mine fire prevention and extinguishing technology to improve the safety production of coal mines in my country and protect the lives of miners.

[0004] Therefore, the study of coal mine fire prevention and extinguishing technology has important practical and economic significance. We should continue to strengthen the accumulation of technology research and development and practical experience to cope with various complex and changeable mine fire accidents.

[0005] The difficulty in solving the above problems and defects is: the environment inside the coal mine is complex, and there are a large number of flammable materials, such as coal, wood, plastic, etc. Once a fire occurs, the fire will spread rapidly. The internal space of the coal mine is small, the passages are complex, the underground ventilation is poor, and there is a lack of oxygen. Therefore, when a fire occurs, it will increase the difficulty of rescue. Fire prevention and extinguishing work requires the use of various professional equipment, such as fire extinguishing equipment, ventilation equipment, drainage equipment, etc., and the performance and reliability of the equipment are extremely high. Therefore, it is very necessary to develop a mine fire extinguishing agent with high fire extinguishing efficiency and little impact on the environment.

[0006] The significance of solving the above problems is that fire extinguishing agent is a key factor in coal mine fire fighting. The development of efficient and environmentally friendly fire extinguishing agents can greatly improve the efficiency of fire extinguishing, quickly control the fire, and reduce the losses caused by the fire. This plays a vital role in protecting the lives of miners and reducing property losses. The development of environmentally friendly fire extinguishing agents helps to reduce the pollution of the fire extinguishing process to the environment. Traditional fire extinguishing agents may release toxic gases and damage the ecological environment during the fire extinguishing process. Environmentally friendly fire extinguishing agents have less impact on the environment with the same fire extinguishing effect, which meets the requirements of sustainable development. In the process of fire extinguishing, the rational use of fire extinguishing agents can reduce the consumption of resources such as water and human resources. By optimizing the formula and use of fire extinguishing agents, effective utilization of resources can be achieved and the cost of fire extinguishing can be reduced. Therefore, the research and development of fire extinguishing agents for coal mines is of great significance. Summary of the invention

[0007] The purpose of the present invention is to provide a preparation method and application of a gel-protein foam fire extinguishing agent to solve the problems existing in the above-mentioned prior art, so that it can effectively control coal mine fires, the product is pollution-free, and the role of recycling domestic waste is achieved.

[0008] To achieve the above-mentioned purpose, the present invention provides the following scheme: a method for preparing a gel-protein foam fire extinguishing agent, characterized in that: kitchen waste is used as a raw material, hydrolyzed protease is added, and a biohydrolysis method is adopted to prepare hydrolyzed protein as an environmentally friendly foaming agent; and surfactants of different concentrations are screened to provide a theoretical basis for compounding the foaming agent; the selected surfactants of the best concentration are added to the hydrolyzed protein aqueous solution, stirred evenly, and a multi-component composite foaming liquid is prepared; and a gelling agent is added to the composite foaming agent, and during the mechanical foaming process, a cross-linking agent is added dropwise to cause a cross-linking reaction to obtain the gel-protein foam fire extinguishing agent.

[0009] Furthermore, the kitchen waste includes one or more of meat, eggs, beans, cereals, etc.

[0010] Kitchen waste is mainly composed of protein, carbohydrates, vitamins, inorganic salts and a small amount of other substances. Under suitable temperature and pH conditions, hydrolytic proteases will cut the peptide chains and decompose the proteins into hydrolyzed proteins.

[0011] Furthermore, the hydrolyzed protein is one of papain, neutral protease, trypsin, pepsin, cathepsin and subtilisin.

[0012] Different hydrolyzed proteins cut off the peptide chains at different positions, resulting in the production of different small molecule peptides with biological activity. This can also improve the foaming properties of the protein to a certain extent, further increasing the added value of the protein.

[0013] Furthermore, the bio-based surfactant embedding agent is sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB).

[0014] Furthermore, the gelling agent is chitosan and the cross-linking agent is epichlorohydrin.

[0015] Under alkaline conditions, the carbon-chlorine bond in epichlorohydrin breaks to form a carbon cation that forms an ether with the hydroxyl group in the chitosan molecule. At the same time, the epoxy ring at the other end opens to form an ether with the hydroxyl group in another chitosan molecule, thereby generating a cross-linked product.

[0016] Further, the gel-protein foam fire extinguishing agent is prepared according to the following steps:

[0017] Step 1: Take a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of the hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45°C, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / LNaOH or 1mol / L HCl, and ultrasonically treat it for 15min. Add an appropriate amount of protease to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45°C. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After enzymolysis for 6h, boil it in 100°C boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0018] Step 2, screening of surfactants, select four different surfactants, fatty alcohol polyoxyethylene ether carboxylate sodium (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), respectively, and prepare aqueous solutions according to 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, and 0.5wt%, take 20mL of surfactant aqueous solution, 1500rpm mechanical foaming, record the volume and half-life after complete foaming. Each group of experiments was repeated at least three times, and the average value was taken.

[0019] Step three, the best compounding ratio is selected, and the concentrations of the four surfactants with the best foaming effects are taken respectively, and aqueous solutions are prepared, and compounded according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0, and the foaming multiples and half-lives are recorded, and the comprehensive foam index is calculated, and the compounding ratios with the highest comprehensive foam index among sodium polyoxyethylene alcohol ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB) are selected as composite foaming agents.

[0020] Step 4: In order to determine the optimal ratio of the gelling agent and the cross-linking agent and the mass fraction of the polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, the composite foaming agent and the antifreeze agent were uniformly stirred, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0021] Step 5: Conduct fire extinguishing experiments on the group with a comprehensive foam index greater than 200 and select the ratio with the best fire extinguishing agent performance.

[0022] The temperature, stirring speed, time and dosage set in the present invention are optimized according to single factor test and are all optimal parameters, so that the prepared gel-protein foam fire extinguishing agent has the best foaming property, the best morphology, the best stability and the best fire extinguishing performance.

[0023] Combining all the above technical solutions, the advantages and positive effects of the present invention are as follows:

[0024] (1) Selecting kitchen waste as the raw material for extracting hydrolyzed protein not only realizes the resource utilization of domestic waste, but also reduces product costs.

[0025] (2) The hydrolyzed protein was prepared by protease hydrolysis method, which has good foaming performance, high stability, can effectively prolong the cooling time and isolate oxygen.

[0026] (3) The optimal foaming concentration was screened by the surfactant concentration gradient method, which greatly improved the foaming performance and stability of the composite foaming agent.

[0027] (4) The product generated by the cross-linking reaction of chitosan and epichlorohydrin is used as a foam stabilizing material, which greatly improves the stability and cooling properties of the foam fire extinguishing agent while extending the foam half-life.

[0028] The invention of gel-protein foam fire extinguishing agent has achieved efficient utilization of kitchen waste, solved problems such as poor cooling performance and obvious re-ignition phenomenon of traditional fire extinguishing agents, effectively suppressed coal mine fires and protected the ecological environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments of the present application. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0030] Figure 1 It is a surfactant screening diagram provided by an embodiment of the present invention.

[0031] Figure 2 is a foam expansion rate diagram provided by an embodiment of the present invention.

[0032] Figure 3 It is a macroscopic picture of the gel-protein foam fire extinguishing agent provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0033] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0034] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0035] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0036] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0037] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0038] Example 1

[0039] ① Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a raw material for hydrolyzed protein. Take 80g of hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45°C, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of papain to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45°C. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0040] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0041] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0042] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0043] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0044] Example 2

[0045] ② Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45℃, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of neutral protease to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45℃. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0046] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0047] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0048] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0049] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0050] Example 3

[0051] ③ Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45℃, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of trypsin to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymatic hydrolysis under ultrasonic conditions at 45℃. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymatic hydrolysis reaction. During the enzymatic hydrolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymatic hydrolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymatic hydrolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0052] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0053] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0054] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0055] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0056] Example 4

[0057] ④ Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45℃, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of pepsin to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45℃. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0058] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0059] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0060] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0061] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0062] Example 5

[0063] ① Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of the hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45°C, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of cathepsin to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45°C. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0064] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0065] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0066] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0067] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0068] Example 6

[0069] ① Weigh a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material. Take 80g of the hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45°C, adjust the pH value to the optimal pH value of the protease (pH=7 in this paper) with 1mol / L NaOH or 1mol / L HCl, and treat it ultrasonically for 15min. Add an appropriate amount of cathepsin to the hydrolyzed protein raw material after ultrasonic treatment, and perform enzymolysis under ultrasonic conditions at 45°C. The cavitation effect of ultrasonic waves is used to increase the reaction rate of the enzymolysis reaction. During the enzymolysis process, adjust the pH to the optimal value every 15min. After 6h of enzymolysis, boil it in 100℃ boiling water for 5min to inactivate the enzyme, and then quickly cool it to room temperature. The liquid after enzymolysis is centrifuged for 20min using a centrifuge (8000r / min), and the supernatant is taken for use. During the reaction, the pH of the system was maintained with 0.1 mol / L NaOH solution (variable range ± 0.05).

[0070] ② Select four different surfactants, namely, sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), and prepare aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, respectively. Take 20mL of the surfactant aqueous solution, and mechanically foam at 1500rpm. Record the volume and half-life after complete foaming. Repeat each group of experiments at least three times and take the average value.

[0071] ③ Selection of the optimal compound ratio: take the concentrations with the best foaming effects of the four surfactants respectively, prepare aqueous solutions, and compound them according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. Record the foaming multiples and half-life, and calculate the comprehensive foam index. Select the compound ratio with the highest comprehensive foam index among sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S), and cocamidopropyl hydroxysulfobetaine (CHSB) as the composite foaming agent.

[0072] ④ In order to determine the optimal ratio of gelling agent and cross-linking agent and the mass fraction of polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used. After the gelling agent, composite foaming agent and antifreeze agent were stirred evenly, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to cause a cross-linking reaction in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200.

[0073] ⑤ Carry out fire extinguishing test on the group with comprehensive foam index greater than 200, and select the ratio with the best fire extinguishing agent performance.

[0074] Analysis items and methods

[0075] Protein extraction rate determination: Kjeldahl method

[0076] Calculation formula:

[0077] Protein extraction rate = (supernatant protein content / raw material total protein content) * 100%

[0078] Calculation of the Foam Composite Index (FCI):

[0079] The following formula is used for calculation:

[0080]

[0081] Where E is the maximum volume of the foam, V; T 1 / 2 is the half-life, s.

[0082] The test results are shown in Table 1.

[0083] Table 1 Protein extraction rate

[0084]

[0085] Note: The sample mass of each sample is 2±0.01g, and the protein content in the protein extraction raw material is 0.3397g.

[0086] From the data in Table 1, it can be seen that the hydrolysis protein extraction rate of trypsin is the highest, so the hydrolysis protein extraction of this patent is mainly based on trypsin. The optimal temperature range of trypsin hydrolysis is 10℃~60℃, and the optimal pH range is 6.0~11.0, at which time the protein extraction rate is about 60.02%.

[0087] When the concentration is 0.2wt%, the foaming performance and stability of the four surfactants are the best, so the concentration of the surfactants is 0.2wt% during compounding. When the compounding ratio is 2:8 (surfactant: hydrolyzed protein), the obtained FCI is the highest, indicating that the comprehensive foam performance is the best at this time.

[0088] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with the technical field within the technical scope disclosed by the present invention and within the spirit and principle of the present invention should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a gel-protein foam fire extinguishing agent for mining, characterized in that: Kitchen waste is used as raw material, hydrolyzed protein is added, and a biohydrolysis method is adopted to prepare hydrolyzed protein as an environmentally friendly foaming agent; surfactants of different concentrations are screened to provide a theoretical basis for the compound foaming agent; the selected surfactant with the best concentration is added to the hydrolyzed protein aqueous solution, stirred evenly, to prepare a multi-component composite foaming liquid; and a gelling agent is added to the composite foaming agent, and a cross-linking agent is added dropwise during the mechanical foaming process to cause a cross-linking reaction to obtain a gel-protein foam fire extinguishing agent.

2. The method for preparing the hydrolyzed protein according to claim 1, wherein The kitchen waste includes one or more of meat, eggs, beans, cereals and the like.

3. The method for preparing the hydrolyzed protein according to claim 1, wherein The hydrolytic protease is one of papain, neutral protease, trypsin, pepsin, cathepsin and subtilisin.

4. The method for screening different surfactants according to claim 1, characterized in that: The concentration gradient of the surfactant is set to 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, and 0.5wt%.

5. The method for preparing the gel-protein foam fire extinguishing agent according to claim 1, characterized in that: The gelling agent is chitosan aqueous solution, and the cross-linking agent is epichlorohydrin.

6. The method for preparing the gel-protein foam fire extinguishing agent according to claim 1, characterized in that: Prepare according to the following steps: Step 1: Take a certain amount of kitchen waste (try to select materials with high content of plant protein and animal protein), wash, dry and grind the kitchen waste through a 120-mesh sieve as a hydrolyzed protein raw material; take 80g of the hydrolyzed protein raw material, add it to 300mL of deionized water, place it in a water bath and heat it to 45°C, and use 1mol / LNaOH or 1mol / L HCl was used to adjust the pH value to the optimum pH value of the protease (pH=7 in this paper), and ultrasonic treatment was performed for 15 minutes; an appropriate amount of protease was added to the hydrolyzed protein raw material after ultrasonic treatment, and enzymatic hydrolysis was performed under ultrasonic conditions at 45°C, and the cavitation effect of ultrasonic waves was used to increase the reaction rate of the enzymatic hydrolysis reaction. During the enzymatic hydrolysis process, the pH was adjusted to the optimum value every 15 minutes. After 6 hours of enzymatic hydrolysis, the enzyme was inactivated by boiling water bath at 100°C for 5 minutes, and then quickly cooled to room temperature; the liquid after enzymatic hydrolysis was centrifuged for 20 minutes using a centrifuge (8000r / min), and the supernatant was taken for use; during the reaction process, a 0.1mol / L NaOH solution was used to maintain the pH of the system (variation range ±0.05); Step 2, screening of surfactants, selecting four different surfactants, including sodium alcohol polyoxyethylene ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB), respectively preparing aqueous solutions at 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, and 0.5wt%, taking 20mL of the surfactant aqueous solution, mechanically foaming at 1500rpm, and recording the volume and half-life after complete foaming; each group of experiments was repeated at least three times, and the average value was taken; Step 3, the best compounding ratio is selected, and the concentrations with the best foaming effects of four surfactants are taken respectively, and aqueous solutions are prepared, and compounded according to the ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0, and the foaming multiple and half-life are recorded, and the foam comprehensive index is calculated, and the compounding ratio with the highest foam comprehensive index among sodium polyoxyethylene alcohol ether carboxylate (AEC), coconut oil glucoside (EG), sodium lauroyl glutamate (LG-S) and cocamidopropyl hydroxysulfobetaine (CHSB) is selected respectively as the composite foaming agent; Step 4: In order to determine the optimal ratio of the gelling agent and the cross-linking agent and the mass fraction of the polymer, different ratios of chitosan to epichlorohydrin (λ, from 1:4 to 9:1) and mass fractions (from 0.1 to 0.6wt%) were used; after the gelling agent, the composite foaming agent and the antifreeze agent were uniformly stirred, mechanical foaming was performed at 1500rpm, and the cross-linking agent was added dropwise to allow a cross-linking reaction to occur in the solution to form a dense three-dimensional network gel structure, thereby improving the stability of the foam, recording its foaming multiple and half-life, and calculating the comprehensive foam index, and selecting the ratio with a comprehensive foam index greater than 200; Step 5: Conduct fire extinguishing experiments on the group with a comprehensive foam index greater than 200 and select the ratio with the best fire extinguishing agent performance.

7. The method for preparing the gel-protein foam fire extinguishing agent according to claim 6, characterized in that: In the process of preparing gel protein foam, the following are included according to the mass percentage requirements: 75% to 80% composite foaming agent, 1% to 5% gelling agent, 1% to 5% crosslinking agent, 1% antifreeze agent, and the balance is deionized water.

8. A gel-protein foam fire extinguishing agent according to any one of claims 1 to 7 and a preparation method thereof.

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