Preparation method of fire extinguishing material for preventing coal spontaneous combustion in goaf
By microencapsulating and covering materials such as perfluorohexanone, microcapsule fire extinguishing materials suitable for goaf are prepared, which solves the problems of low fire extinguishing efficiency and easy loss of resistors in the prior art, and achieves an efficient and safe coal spontaneous combustion suppression effect.
Patent Information
- Application Number
- CN202510209070.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-25
- Publication Date
- 2025-06-06
AI Technical Summary
The prior art has low efficiency when extinguishing fires in goafs, and the inhibitor is easily lost in humid and heat environments, affecting the fire extinguishing effect.
Microencapsulation is used to coat materials such as perfluorohexanone, isofluorone diisocyanate and methyl novolacrobutyl ether to form microcapsules fire extinguishing materials. Microcapsules are prepared through emulsification and polymerization reactions to improve the encapsulation efficiency and storage effect of fire extinguishing materials.
It effectively suppresses coal spontaneous combustion in the goaf area, improves fire extinguishing efficiency, and is safe and non-toxic, and has a dense capsule. It is suitable for a variety of application scenarios without the need for special storage and triggering equipment.
Smart Images
Figure CN120094155A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of fire extinguishing materials, and in particular to a method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas. Background Art
[0002] Coal is currently the world's most important energy source and industrial raw material, but spontaneous combustion may occur at any time during the mining, transportation and storage processes. The spontaneous combustion of coal left in the goaf can also pose a great threat to coal mine safety production.
[0003] At present, coal mine fire extinguishing mainly relies on pressure filling fire extinguishing, inert gas fire extinguishing, inhibitor fire extinguishing and foam fire extinguishing. Among them, pressure filling and inert gas foam fire extinguishing are not suitable for fire extinguishing in coal mine goaf areas. The environment of goaf areas is complex and changeable and the environment is humid and hot. In a humid and hot environment, inhibitors are prone to loss, affecting the fire extinguishing efficiency of goaf areas. Summary of the invention
[0004] In order to overcome the deficiencies of the prior art, the object of the present invention is to provide a method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas and a preparation method thereof, so as to improve the fire extinguishing efficiency in goaf areas.
[0005] The technical solution adopted by the present invention is:
[0006] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas comprises the following steps:
[0007] S1, mixing perfluorohexanone, isophorone diisocyanate and methyl nonafluorobutyl ether in proportion at room temperature to obtain an oil phase mixture;
[0008] S2, adding the oil phase mixture to an emulsifier and stirring evenly for emulsification to obtain an O / W type emulsion;
[0009] S3, adding diethylenetriamine to the O / W type emulsion to initiate a polymerization reaction to obtain a microcapsule solution;
[0010] S4, repeatedly washing and freeze-drying the microcapsule solution to obtain a microcapsule material.
[0011] Optionally, the mass ratio of perfluorohexanone to isophorone diisocyanate is 10:1.
[0012] Optionally, the emulsifier is a compound fluorocarbon surfactant, which is composed of the following raw materials in parts by weight: 20%-70% sodium dodecyl sulfate, 10%-50% alkylphenol polyoxyethylene ether and 10%-30% perfluoroalkyl polyoxyethylene ether.
[0013] Optionally, the mass ratio of the emulsifier to the oil phase mixture is (6-8):1.
[0014] Optionally, the step S3 further comprises pentaerythritol, and the mass ratio of the diethylenetriamine to pentaerythritol is (1.2-2):1.
[0015] Optionally, in step S2: the stirring rate is 2000 rpm, and the emulsification time is 8-12 min.
[0016] Optionally, the microcapsule materials are placed evenly spaced in the coal mine goaf, and the distance between two adjacent microcapsule materials is 8-12 m.
[0017] Optionally, the amount of the microcapsule material used per unit area of the goaf is in the range of 0.3-0.5 g / m 2 .
[0018] The beneficial effects of the present invention are as follows: the present application performs microencapsulation coating on the perfluorohexanone inhibitor, and the perfluorohexanone capsule fire extinguishing material for preventing and controlling spontaneous combustion of coal in mine goafs is manufactured, which has high encapsulation efficiency, good storage effect, and a simple and controllable preparation process. Moreover, the prepared microcapsules are safe and non-toxic, the capsule shell is dense, the encapsulation effect is good, no special storage and triggering equipment is required, the application scenarios and methods are more flexible, and an endothermic reaction can occur quickly to rapidly reduce the temperature of the spontaneous combustion area of the goaf, thereby improving the fire extinguishing efficiency of the goaf.
[0019] When perfluorohexanone and isophorone diisocyanate are mixed into an oil phase mixture, an appropriate amount of methyl nonafluorobutyl ether is added as a solvent to improve the solubility of perfluorohexanone in isophorone diisocyanate, so that the three are miscible. Polypropylene glycol 2000 is added to form a polyurea / polyurethane composite structure to increase the density of the microcapsule. Most of the isophorone diisocyanate diffuses to the surface of the shell and reacts with diethylenetriamine to form a polyurea structure. At the same time, the polypropylene glycol 2000 inside the core material reacts with the isophorone diisocyanate inside the shell surface to form components of the polyurethane structure, and finally forms an outer shell of the polyurea polyurethane composite structure; secondly, during emulsification, the emulsifier uses a composite emulsifier of a hydrocarbon surfactant and a fluorocarbon surfactant, which improves the emulsification effect of emulsified substances with high fluorine content.
[0020] When the temperature around the device in the goaf rises to a certain level, the capsule membrane of the microcapsule is automatically degraded by heat to release the perfluorohexanone core material inside. The perfluorohexanone will undergo an endothermic reaction to reduce the surrounding temperature, inhibiting the further oxidation and spontaneous combustion of the remaining coal, and achieving the prevention and control effect of spontaneous combustion disasters in goafs with large inclination angles. No special storage and triggering equipment is required, and the application scenarios and methods are more flexible. In addition, perfluorohexanone has little harm and is quick to take effect. It can quickly undergo an endothermic reaction to rapidly reduce the temperature of the spontaneous combustion area of the goaf, thereby inhibiting the temperature rise of the coal and strangling the fire in the early stage, playing a role in preventing and controlling coal spontaneous combustion disasters. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 This is an optical electron microscope image of the perfluorohexanone microcapsule of Example 4 of the present invention.
[0022] Figure 2 This is an optical electron microscope image of comparative example 1 of the present invention.
[0023] Figure 3 This is an optical electron microscope image of Comparative Example 2 of the present invention.
[0024] Figure 4 This is an optical electron microscope image of comparative example 3 of the present invention. DETAILED DESCRIPTION
[0025] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0026] Example
[0027] Example 1
[0028] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas comprises the following steps:
[0029] At room temperature, 6.4g of perfluorohexanone, 0.64g of isophorone diisocyanate, 0.64g of polypropylene glycol 2000 and 10g of methyl nonafluorobutyl ether are uniformly mixed to form an oil phase mixture; 0.16g of sodium dodecyl sulfate, 0.096g of alkylphenol polyoxyethylene ether and 0.064g of a composite emulsifier of perfluoroalkyl polyoxyethylene ether are dissolved in 30ml of deionized water, and at 25°C, the oil phase mixture is slowly added to the emulsion solution while stirring, and the emulsification is continued at a rotation speed of 2000rpm for 10min to fully emulsify the perfluorohexanone in water to form a uniform O / W emulsion.
[0030] Add 10 ml of deionized water and 0.32 g of the compound emulsifier into the sealed tube, then transfer the prepared water-in-oil emulsion into the sealed tube, add 1.71 g of diethylenetriamine into the emulsion at a rotation speed of 200-400 rpm to initiate the polymerization reaction, react at room temperature for 1 hour, then continue to heat to 45°C and keep the reaction for 2 hours.
[0031] The solution in the sealed tube was filtered to obtain white solid small particles, which were then repeatedly washed with deionized water and anhydrous ethanol for 5 times, and finally freeze-dried for 12 hours to obtain microcapsule materials.
[0032] Example 2
[0033] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas comprises the following steps:
[0034] At room temperature, 6.4g of perfluorohexanone, 0.64g of isophorone diisocyanate and 10g of methyl nonafluorobutyl ether are uniformly mixed to form an oil phase mixture; 0.16g of sodium dodecyl sulfate, 0.096g of alkylphenol polyoxyethylene ether and 0.064g of a composite emulsifier of perfluoroalkyl polyoxyethylene ether are dissolved in 30ml of deionized water, and at 25°C, the oil phase mixture is slowly added to the emulsion solution while stirring, and the emulsification is continued at a speed of 2000rpm for 10min to fully emulsify the perfluorohexanone in water to form a uniform O / W emulsion.
[0035] Add 10 ml of deionized water and 0.32 g of the compound emulsifier into the sealed tube, then transfer the prepared water-in-oil emulsion into the sealed tube, add 1.71 g of diethylenetriamine into the emulsion at a rotation speed of 200-400 pm to initiate the polymerization reaction, react at room temperature for 1 hour, then continue to heat up to 45°C and keep the reaction for 2 hours.
[0036] The solution in the sealed tube was filtered to obtain white solid small particles, which were then repeatedly washed with deionized water and anhydrous ethanol for 5 times, and finally freeze-dried for 12 hours to obtain microcapsule materials.
[0037] Example 3
[0038] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas comprises the following steps:
[0039] At room temperature, 6.4g of perfluorohexanone, 0.64g of isophorone diisocyanate and 10g of methyl nonafluorobutyl ether are uniformly mixed to form an oil phase mixture; 0.16g of sodium dodecyl sulfate, 0.096g of alkylphenol polyoxyethylene ether and 0.064g of a compounded emulsifier of perfluoroalkyl polyoxyethylene ether are dissolved in 30ml of deionized water, and at 25°C, the oil phase mixture is slowly added to the emulsion solution under high-speed stirring, and the emulsification is continued at a speed of 2000rpm for 10min to fully emulsify the perfluorohexanone in water to form a uniform O / W emulsion.
[0040] Add 10 ml of deionized water and 0.32 g of the compound emulsifier into the sealed tube, then transfer the prepared water-in-oil emulsion into the sealed tube, and add a mixture of 0.85 g of diethylenetriamine and 0.6 g of pentaerythritol into the emulsion at a rotation speed of 200-400 pm to initiate the polymerization reaction. After reacting at room temperature for 1 hour, continue to heat up to 45°C and keep the reaction for 2 hours.
[0041] The solution in the sealed tube was filtered to obtain white solid small particles, which were then repeatedly washed with deionized water and anhydrous ethanol for 5 times, and finally freeze-dried for 12 hours to obtain microcapsule materials.
[0042] Example 4
[0043] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas comprises the following steps:
[0044] At room temperature, 6.4g of perfluorohexanone, 0.64g of isophorone diisocyanate and 10g of methyl nonafluorobutyl ether are uniformly mixed to form an oil phase mixture; 0.16g of sodium dodecyl sulfate, 0.096g of alkylphenol polyoxyethylene ether and 0.064g of a compounded emulsifier of perfluoroalkyl polyoxyethylene ether are dissolved in 30ml of deionized water, and at 25°C, the oil phase mixture is slowly added to the emulsion solution under high-speed stirring, and the emulsification is continued at a speed of 2000rpm for 10min to fully emulsify the perfluorohexanone in water to form a uniform O / W emulsion.
[0045] Add 10 ml of deionized water and 0.32 g of a compound emulsifier into the sealed tube, then transfer the prepared oil-in-water emulsion into the sealed tube, and add a mixture of 0.76 g of propylene glycol, 0.85 g of diethylenetriamine and 0.6 g of pentaerythritol to the emulsion at a rotation speed of 200-400 pm to initiate a polymerization reaction. After reacting at room temperature for 1 hour, continue to heat up to 45°C and keep the reaction for 2 hours.
[0046] The solution in the sealed tube was filtered to obtain white solid small particles, which were then repeatedly washed with deionized water and anhydrous ethanol for 5 times, and finally freeze-dried for 12 hours to obtain microcapsule materials.
[0047] Comparative Example 1
[0048] At room temperature, 6.4g of perfluorohexanone, 0.64g of isophorone diisocyanate, 0.64g of polypropylene glycol 2000 and 10g of methyl nonafluorobutyl ether are uniformly mixed to form an oil phase mixture; 0.24g of Tween-80 and 0.08g of Span-85 compounded emulsifier is dissolved in 30ml of deionized water, and at 25°C, the oil phase mixture is slowly added to the emulsion solution under high-speed stirring, and the emulsification is continued at a speed of 2000rpm for 10min to fully emulsify the perfluorohexanone in water to form a uniform O / W emulsion.
[0049] Add 10 ml of deionized water and 0.32 of the compounded emulsifier into the sealed tube, then transfer the prepared water-in-oil emulsion into the sealed tube, add 1.71 g of diethylenetriamine into the emulsion at a rotation speed of 200-400 rpm to initiate the polymerization reaction, react at room temperature for 1 hour, then continue to heat to 45°C and keep the reaction for 2 hours.
[0050] The solution in the sealed tube was filtered to obtain white solid small particles, which were then repeatedly washed with deionized water and anhydrous ethanol for 5 times, and finally freeze-dried for 12 hours to obtain microcapsule materials.
[0051] Comparative Example 2
[0052] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf, which is different from Comparative Example 1 in that the emulsifier is SDBS.
[0053] Comparative Example 3
[0054] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf, which is different from Comparative Example 1 in that the emulsifier is Span-85.
[0055] Comparative Example 4
[0056] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf, which is different from Example 4 in that the oil phase mixture is added to the emulsion solution and the emulsification is continued for 10 minutes at a rotation speed of 1500 rpm.
[0057] Comparative Example 5
[0058] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf, which is different from Example 4 in that the oil phase mixture is added to the emulsion solution and the emulsification is continued for 10 minutes at a rotation speed of 3000 rpm.
[0059] Comparative Example 6
[0060] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas, which is different from Example 4 in that the prepared water-in-oil emulsion is transferred to a sealed tube, 0.85 g of diethylenetriamine is added to the emulsion at a rotation speed of 200-400 pm to initiate a polymerization reaction, and after reacting at room temperature for 1 hour, the temperature is continuously raised to 45°C and kept for reaction for 2 hours.
[0061] Comparative Example 7
[0062] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas, which is different from Example 4 in that the prepared water-in-oil emulsion is transferred to a sealed tube, 0.76 g of propylene glycol is added to the emulsion at a rotation speed of 200-400 pm to initiate a polymerization reaction, and after reacting at room temperature for 1 hour, the temperature is continuously raised to 45°C and kept for reaction for 2 hours.
[0063] Comparative Example 8
[0064] A method for preparing a fire extinguishing material for preventing and controlling spontaneous combustion of coal in goaf areas, which is different from Example 4 in that the prepared water-in-oil emulsion is transferred to a sealed tube, 0.6 g of pentaerythritol is added to the emulsion at a rotation speed of 200-400 pm to initiate a polymerization reaction, and after reacting at room temperature for 1 hour, the temperature is continuously raised to 45° C. and kept for reaction for 2 hours.
[0065] Performance Testing
[0066] The following performance tests were performed on the microcapsule materials provided in Examples 1-4 and Comparative Examples 1-8 of the present invention:
[0067] Embedding rate: embedding rate = (actually embedded perfluorohexanone mass / initial perfluorohexanone mass) × 100%.
[0068] Particle size distribution: The average particle size and distribution range of the microcapsule material were determined by a laser particle size analyzer.
[0069] Fire extinguishing effect: 0.5 g of the microcapsule materials of Examples 1-4 and Comparative Examples 1-8 were placed in an area of 1 m2, and the fire extinguishing time was tested at 60°C, and the time from when the materials came into contact with the flame to when the flame was completely extinguished was recorded.
[0070] Storage stability: The state of the microcapsule material stored in a room temperature and light-proof environment for 30 days is manually observed.
[0071] The performance results of the fire extinguishing materials prepared in Examples 1-4 of the present invention and Comparative Examples 1-8 are shown in Table 1.
[0072] Table 1 Performance results
[0073]
[0074]
[0075]
[0076] Finally, it should be noted that the above description is only a preferred example of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf, characterized in that: The steps include: S1, mixing perfluorohexanone, isophorone diisocyanate and methyl nonafluorobutyl ether in proportion at room temperature to obtain an oil phase mixture; S2, adding the oil phase mixture to an emulsifier and stirring evenly for emulsification to obtain an O / W type emulsion; S3, adding diethylenetriamine to the O / W type emulsion to initiate a polymerization reaction to obtain a microcapsule solution; S4, repeatedly washing and freeze-drying the microcapsule solution to obtain a microcapsule material.
2. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The mass ratio of the perfluorohexanone to isophorone diisocyanate is 10:
1.
3. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The emulsifier is a compound fluorocarbon surfactant, which is composed of the following raw materials in parts by weight: 20%-70% of sodium lauryl sulfate, 10%-50% of alkylphenol polyoxyethylene ether and 10%-30% of perfluoroalkyl polyoxyethylene ether.
4. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The mass ratio of the emulsifier to the oil phase mixture is (6-8):
1.
5. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The oil phase mixture also includes polypropylene glycol 2000, and the mass ratio of isophorone diisocyanate to polypropylene glycol is 1:
1.
6. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The step S3 also includes pentaerythritol, and the mass ratio of diethylenetriamine to pentaerythritol is (1.2-2):
1.
7. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: In the step S2: the stirring rate is 2000 rpm, and the emulsification time is 8-12 min.
8. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: In the step S3, the stirring speed of the polymerization reaction solution is 200-400 rpm, and the temperature is raised to 45° C. after the reaction is kept at room temperature for 1 hour, and the microcapsule solution is obtained after the reaction is kept at room temperature for 2 hours.
9. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 1, characterized in that: The microcapsule materials are evenly spaced and placed in the coal mine goaf, and the distance between two adjacent microcapsule materials is 8-12m.
10. The method for preparing a fire extinguishing material for preventing spontaneous combustion of coal in goaf according to claim 9, characterized in that: The dosage of the microcapsule material per unit area of the goaf is in the range of 0.3-0.5 g / m 2 .