Dopo modified dry water explosion inhibitor, and preparation method and application thereof

Abstract

The application discloses a DOPO modified dry water explosion inhibitor and a preparation method and application thereof, and belongs to the technical field of safety chemistry. A silane coupling agent is added to a DOPO solution to obtain a DOPO type silane coupling agent through stirring; the DOPO type silane coupling agent is added to fumed silica to obtain DOPO modified fumed silica through stirring or ultrasonic dispersion, and then the DOPO modified fumed silica is filtered and dried to obtain a dry water explosion inhibitor. The core material and the wall material of the dry water are modified, and the explosion inhibition performance of the dry water is significantly improved. The addition of DOPO endows the dry water with good flame retardant performance, and the dry water can effectively inhibit flame propagation under high-temperature or fire source conditions; the composite use of the explosion inhibitor enhances the explosion inhibition effect of the dry water, forms a composite material with higher explosion inhibition performance, and can adjust the types of the explosion inhibitor according to actual application environments, and can be widely applied to explosion prevention requirements in different scenes.

Description

Technical Field

[0001] This invention belongs to the field of safety chemistry technology, specifically relating to a DOPO-modified dry water explosion suppressant, its preparation method, and its application. Background Technology

[0002] Dry water is a powdery substance composed of water coated with hydrophobic silica, exhibiting strong adsorption and stability. Due to its strong isolation and flowability, dry water materials are increasingly being used in explosion-proof and explosion-suppression applications. However, existing dry water materials have limited performance in explosion-suppression applications, especially in certain high-risk environments, failing to fully realize their intended protective effect. Therefore, it is necessary to modify the core and wall materials of dry water materials to improve their explosion-suppression performance. Phosphorus-based flame retardant DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), as a highly efficient flame retardant material, possesses excellent thermal stability and flame-retardant effects. Upon heating, it decomposes to release a large amount of gas, diluting the oxygen content while simultaneously producing a porous carbon layer for thermal insulation, and is widely used in the preparation of flame-retardant materials. While DOPO is widely used in flame retardancy, its application in the explosion-suppression of dry water has not been fully utilized. In existing technologies, the compounding of DOPO and dry water faces problems of poor compatibility and uneven dispersion, which limits its explosion-suppression performance. Therefore, existing technologies have failed to achieve effective mixing of dry water and DOPO, and traditional mixing methods struggle to address their poor compatibility. Therefore, this invention proposes a method that successfully mixes dry water and DOPO through specific modification techniques and key operations, overcoming the difficulties in mixing and improving the explosion suppression performance of dry water under high temperature and extreme conditions. Summary of the Invention

[0003] To address the aforementioned problems in the prior art, this invention provides a DOPO-modified dry water explosion suppressant, its preparation method, and its application. By combining DOPO-modified dry water with the explosion suppressant, a composite material with higher explosion suppression performance is formed, which can be widely applied to explosion-proof requirements in different scenarios.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing a DOPO-modified dry water detonator, comprising the following steps:

[0006] (1) Dissolve DOPO in a solvent and stir thoroughly to disperse it evenly to form a uniform DOPO solution. Add silane coupling agent to the obtained DOPO solution and stir until transparent to obtain DOPO type silane coupling agent.

[0007] (2) Add the DOPO-type silane coupling agent prepared in step (1) to the fumed silica. Disperse the DOPO evenly on the surface of the fumed silica by stirring or ultrasonication. During this process, the DOPO is stabilized on the surface of the fumed silica through chemical bonding. Filter and dry to obtain DOPO-modified fumed silica.

[0008] (3) Add the DOPO modified fumed silica prepared in step (2) to water or a detonator solution and stir to obtain the DOPO modified dry water detonator.

[0009] The added explosion suppressant can quickly absorb heat and release gas in the early stages of an explosion, thus inhibiting the spread of the explosion.

[0010] As a preferred technical solution of the present invention, in step (1), the solvent includes ethanol and / or ethylene glycol, the mass-volume ratio of DOPO to solvent is (5-8) g:100 mL, the silane coupling agent includes HK560, the molar ratio of silane coupling agent to DOPO is (0.8-1.1):1, and the stirring is carried out at 40-60°C.

[0011] As a preferred technical solution of the present invention, in step (2), the amount of DOPO type silane coupling agent is 2-4 wt% of fumed silica; the stirring speed is 150-300 r / min and the time is 15-25 min; the ultrasonic dispersion power is 2000-2500 w and the time is 4-6 min; the drying temperature is 50-60℃ and the time is 10-15 h.

[0012] As a preferred technical solution of the present invention, in step (3), the mass ratio of the DOPO modified fumed silica to water or the explosion suppressant solution is (7-11):100, the stirring speed is 4000-5000 r / min, and the time is 250-350 s.

[0013] As a preferred technical solution of the present invention, in step (3), the concentration of the explosion suppressant solution is 8-12 wt%, and the explosion suppressant includes one or a combination of N-series explosion suppressants, P-series explosion suppressants, carbonate explosion suppressants and phosphate explosion suppressants.

[0014] As a preferred embodiment of the present invention, the N-series explosion suppressant includes urea and / or ammonium nitrate, the P-series explosion suppressant includes ammonium phosphate and / or calcium hydrogen phosphate, the carbonate explosion suppressant includes calcium carbonate and / or magnesium carbonate, and the phosphate explosion suppressant includes potassium phosphate and / or sodium phosphate.

[0015] The present invention also provides a DOPO modified dry water explosion suppressant prepared according to the above-described preparation method of the DOPO modified dry water explosion suppressant.

[0016] This invention also provides an application of the DOPO-modified dry water detonator described above in the suppression of combustible gas detonation.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] (1) The DOPO modified dry water explosion suppressant prepared by the present invention has a stable structure and excellent impact resistance and thermal decomposition resistance. It can effectively suppress the occurrence of explosion in dangerous environments and is suitable for high-risk places such as chemical plants, mines, and oil and gas storage.

[0019] (2) This invention significantly improves the explosion suppression performance of dry water by modifying its core and wall materials. The addition of DOPO gives dry water good flame retardant properties and can effectively suppress flame propagation under high temperature or fire source conditions. The composite use of explosion suppressants enhances the explosion suppression effect of dry water, forming a composite material with higher explosion suppression performance. The type of explosion suppressant can be adjusted according to the actual application environment (for example, sodium bicarbonate can be preferred as an explosion suppressant in coal mine environments; in chemical plants, P-series explosion suppressants can be selected to deal with the fire hazards of phosphides). It can be widely used for explosion protection needs in different scenarios, improving the flexibility of explosion suppressants. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a flowchart illustrating the preparation of the DOPO-modified dry water detonator in Example 2;

[0022] Figure 2 An optical microscope image of the DOPO-modified dry water detonator prepared in Example 2;

[0023] Figure 3 The graph shows the effect of the explosion suppressants prepared in Examples 1-3 and Comparative Examples 1-2 on the suppression of the 20 vol% H2 explosion intensity.

[0024] Figure 4 The diagram shows the effect of the explosion suppressants prepared in Examples 1-3 and Comparative Examples 1-2 on the explosion intensity of 9.5 vol% methane. Detailed Implementation

[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0026] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0027] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0028] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0029] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0030] In the following examples, fumed silica refers to a nano-sized white powder generated by the high-temperature hydrolysis of silicon halides in an oxyhydrogen flame. The fumed silica used in the following examples was purchased from Degussa, with a particle size of D[4,3] = 18.9 μm and a specific surface area of ​​522.8 m². 2 / kg; DOPO was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. This will not be repeated below.

[0031] Example 1

[0032] The preparation method of DOPO modified dry water detonator is as follows:

[0033] (1) Dissolve 6.86g DOPO in 100mL anhydrous ethanol and stir for 10min to disperse it evenly and form a uniform DOPO solution. Add silane coupling agent HK560 to the DOPO solution. The molar ratio of silane coupling agent HK560 to DOPO is 1:1. Stir at 55℃ until transparent to obtain DOPO type silane coupling agent.

[0034] (2) Add the DOPO type silane coupling agent prepared in step (1) to the fumed silica. The amount of DOPO type silane coupling agent added is 3wt% of the fumed silica. Stir at 200r / min for 20min to make DOPO uniformly loaded onto the surface of the fumed silica (or it can be ultrasonically dispersed at 2400W for 5min, with the same effect). Filter and dry at 55℃ for 12h to obtain DOPO modified fumed silica.

[0035] (3) The DOPO modified fumed silica prepared in step (2) is added to deionized water at a mass ratio of 9:100 and stirred at 4500 r / min for 300 s to obtain DOPO modified dry water explosion suppressant.

[0036] Example 2

[0037] Same as Example 1, except that the “deionized water” added in step (3) is replaced with “explosion suppressant solution (10wt% sodium bicarbonate)”. Step (3) is as follows: add the explosion suppressant sodium bicarbonate to deionized water and stir at 55°C until transparent to obtain a sodium bicarbonate solution with a concentration of 10wt%; add the DOPO modified fumed silica prepared in step (2) to the 10wt% sodium bicarbonate solution at a mass ratio of 9:100 and stir at 4500r / min for 300s to obtain the DOPO modified dry water explosion suppressant.

[0038] The flowchart for preparing the DOPO-modified dry water depressant in this embodiment is as follows: Figure 1 As shown in the figure, the optical microscope image of the prepared DOPO modified dry water knock suppressant is as follows. Figure 2 As shown. By Figure 2 It can be seen that the prepared DOPO modified dry water forms regular spheres, indicating that more anti-explosion groups are grafted onto the surface without affecting the core-shell structure, while also preventing the spheres from breaking and allowing the contents to flow out.

[0039] Example 3

[0040] Same as Example 1, except that the “deionized water” added in step (3) is replaced with “explosion suppressant solution (10wt% ammonium dihydrogen phosphate)”. Step (3) is as follows: add the explosion suppressant ammonium dihydrogen phosphate to deionized water and stir at 55°C until transparent to obtain a 10wt% ammonium dihydrogen phosphate solution; add the DOPO modified fumed silica prepared in step (2) to the 10wt% ammonium dihydrogen phosphate solution at a mass ratio of 9:100 and stir at 4500r / min for 300s to obtain the DOPO modified dry water explosion suppressant.

[0041] Comparative Example 1

[0042] Similar to Example 2, the difference is that in step (1): after adding silane coupling agent HK560 to the DOPO solution, the mixture is stirred at 35°C. Specifically, step (1) involves dissolving 6.86g of DOPO in 100mL of anhydrous ethanol and stirring for 10min to disperse it evenly, forming a uniform DOPO solution. Then, silane coupling agent HK560 is added to the DOPO solution, with a molar ratio of silane coupling agent HK560 to DOPO of 1:1. The mixture is stirred at 35°C until transparent to obtain the DOPO-type silane coupling agent.

[0043] Comparative Example 2

[0044] Same as Example 2, except that the stirring speed is reduced in step (3). Step (3) is as follows: Sodium bicarbonate, the detonator, is added to deionized water and stirred at 55°C until transparent to obtain a sodium bicarbonate solution with a concentration of 10 wt%; the DOPO modified fumed silica prepared in step (2) is added to the 10 wt% sodium bicarbonate solution at a mass ratio of 9:100 and stirred at 3000 r / min for 300 s to obtain DOPO modified dry water detonator.

[0045] Effect verification:

[0046] 1. Verification of the explosion suppression effect of products prepared by ordinary dry water (preparation method is the same as in Example 1, the only difference being that DOPO is not added during the preparation process, and the dosage and steps of other raw materials and process parameters are the same as in Example 1), Examples 1-3, and Comparative Examples 1-2 on hydrogen: 20 vol% H2 was mixed with air in a 20L standard explosion test apparatus to form a gaseous mixture. The mixture was ignited after a 90ms delay (the explosion suppressant was stored in a powder storage tank in the 20L apparatus; during the experiment, a certain mass of the suppressant in the powder storage tank was first sprayed out with compressed gas and then ignited after a 90ms delay). The suppression effect of each group of explosion suppressants on the explosion intensity of 20 vol% H2 is as follows: Figure 3 As shown, by Figure 3It can be seen that the combination of DOPO-modified dry water and 10wt% sodium bicarbonate has the best explosion suppression effect on 20vol% H2 (the lower the maximum explosion pressure, the better the suppression effect; complete suppression means the maximum explosion pressure is less than 0.15mPa), at 500g / m 3 Complete suppression is achieved when the maximum explosion pressure is less than 0.15 mPa; while DOPO-modified dry water combined with 10 wt% ammonium dihydrogen phosphate shows a very good suppression effect, and can further suppress H2 explosion on the basis of the explosion suppression effect of unmodified and uncombined dry water.

[0047] 2. Verification of the explosion suppression effect of ordinary dry water (preparation method is the same as in Example 1, the only difference being that DOPO is not added during the preparation process, and the dosage, steps, and process parameters of other raw materials are the same as in Example 1), the products prepared in Examples 1-3, and Comparative Examples 1-2 on methane: 9.5 vol% methane was mixed with air in a 20L standard explosion test apparatus to form a gaseous mixture. After a 90s delay, the mixture was ignited and detonated. The suppression effect of each group of explosion suppressants on the explosion intensity of 9.5 vol% methane was as follows: Figure 4 As shown. By Figure 4 It can be seen that ordinary dry water has a limited effect on suppressing the explosion of methane at an equivalent concentration, at 400 g / m³. 3 Increasing the inhibitor concentration did not further suppress the explosion, but a DOPO-modified dry water mixture with 10wt% sodium bicarbonate and 10wt% ammonium dihydrogen phosphate effectively suppressed the explosion. The DOPO molecules on the modified wall material first decompose upon heating, absorbing free radicals from the chain reaction during the explosion; then, the dry water breaks down under temperature and pressure, releasing the core material to continue suppressing the explosion. Different core materials showed varying effects in suppressing methane explosions. Sodium bicarbonate was the most effective core material at 600 g / m³. 3 It can achieve complete suppression of explosion of an equivalent amount of methane.

[0048] The above description is merely a preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a DOPO-modified dry water detonator, characterized in that, Includes the following steps: (1) Dissolve DOPO in a solvent, add a silane coupling agent to the obtained DOPO solution, and stir to obtain a DOPO-type silane coupling agent; the solvent is ethanol and / or ethylene glycol; the stirring is carried out at 40-60°C; (2) Add the DOPO-type silane coupling agent prepared in step (1) to the fumed silica, and uniformly load the DOPO onto the surface of the fumed silica by stirring or ultrasonic dispersion, and filter and dry to obtain DOPO-modified fumed silica. (3) Add the DOPO modified fumed silica prepared in step (2) to water or a detonator solution and stir to obtain the DOPO modified dry water detonator. In step (3), the stirring speed is 4000-5000 r / min and the time is 250-350 s.

2. The preparation method of the DOPO-modified dry water detonator according to claim 1, characterized in that, In step (1), the mass-volume ratio of DOPO to solvent is (5-8) g: 100 mL, the silane coupling agent includes HK560, and the molar ratio of silane coupling agent to DOPO is (0.8-1.1):

1.

3. The preparation method of the DOPO-modified dry water detonator according to claim 1, characterized in that, In step (2), the amount of DOPO-type silane coupling agent is 2-4 wt% of fumed silica; the stirring speed is 150-300 r / min and the time is 15-25 min; the ultrasonic dispersion power is 2000-2500 W and the time is 4-6 min; the drying temperature is 50-60℃ and the time is 10-15 h.

4. The preparation method of the DOPO-modified dry water detonator according to claim 1, characterized in that, In step (3), the mass ratio of the DOPO modified fumed silica to water or the explosion suppressant solution is (7-11):

100.

5. The preparation method of the DOPO-modified dry water detonator according to claim 1, characterized in that, In step (3), the concentration of the anti-explosion agent solution is 8-12 wt%.

6. The preparation method of the DOPO-modified dry water detonator according to claim 1, characterized in that, The explosion suppressant includes one or more combinations of urea, ammonium nitrate, ammonium phosphate, dicalcium phosphate, calcium carbonate, magnesium carbonate, potassium phosphate, and sodium phosphate.

7. A DOPO-modified dry water explosion suppressant prepared by the preparation method of the DOPO-modified dry water explosion suppressant according to any one of claims 1 to 6.

8. The application of the DOPO-modified dry water detonator according to claim 7 in the suppression of combustible gas detonation.

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