DOPO modified dry water explosion suppressant as well as preparation method and application thereof

Abstract

The invention discloses a DOPO modified dry water explosion suppressant as well as a preparation method and application thereof, and belongs to the technical field of safe chemistry. Adding a silane coupling agent into the DOPO solution, and stirring to obtain a DOPO type silane coupling agent; the preparation method comprises the following steps: adding a DOPO type silane coupling agent into fumed silica, stirring or carrying out ultrasonic dispersion, filtering and drying to obtain DOPO modified fumed silica, then adding the DOPO modified fumed silica into water or an explosion suppressant solution, and stirring to obtain the DOPO modified dry water explosion suppressant. According to the invention, the dry core material and wall material are modified, so that the explosion suppression performance is obviously improved. Due to the addition of DOPO, the dry water is endowed with good flame retardant property, and flame propagation can be effectively inhibited under the condition of high temperature or a fire source; the composite use of the explosion suppressant enhances the explosion suppression effect of the dry water, a composite material with higher explosion suppression performance is formed, the types of the explosion suppressant can be adjusted according to the actual application environment, and the explosion suppressant can be widely applied to the explosion-proof requirements in different scenes.

Description

Technical Field

[0001] The invention belongs to the technical field of safety chemistry, and specifically relates to a DOPO-modified dry water explosion suppressant and a preparation method and application thereof. Background Art

[0002] Dry water is a powdery substance in which water is coated by hydrophobic silica, which has strong adsorption and stability. Dry water materials are gradually used in the field of explosion prevention and explosion suppression due to their strong isolation and fluidity. However, the performance of existing dry water in explosion suppression applications is limited, especially in certain high-risk environments, and it fails to fully exert its due protective effect. Therefore, it is necessary to modify the core material and wall material of dry water to improve its explosion suppression performance. Phosphorus-based flame retardant DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is a highly efficient flame retardant material with excellent thermal stability and flame retardant effect. When heated, it can decompose a large amount of gas to dilute the oxygen content while producing porous carbon layer insulation, and is widely used in the preparation of flame retardant materials. DOPO has been widely used in the field of flame retardancy, but it has not been fully utilized in the explosion suppression application of dry water. In the prior art, the compounding of DOPO and dry water faces the problems of poor compatibility and uneven dispersion, which limits the performance of its explosion suppression performance. Therefore, the existing technology fails to achieve effective compounding of dry water and DOPO, and the traditional compounding method is difficult to solve the problem of poor compatibility between the two. Therefore, the present invention proposes to successfully achieve compounding of dry water and DOPO through specific modification means and key operations, overcome the difficulties in compounding, and improve the explosion suppression performance of dry water under high temperature and extreme conditions. Summary of the invention

[0003] In order to solve the above problems in the prior art, the present invention provides a DOPO-modified dry water explosion suppressant and a preparation method and application thereof. By combining DOPO-modified dry water with an explosion suppressant, a composite material with higher explosion suppression performance is formed, which can be widely used in explosion-proof needs in different scenarios.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a DOPO-modified dry water explosion suppressant, comprising the following steps:

[0006] (1) dissolving DOPO in a solvent, stirring it thoroughly to make it dispersed evenly, forming a uniform DOPO solution, adding a silane coupling agent to the obtained DOPO solution, and stirring it until transparent to obtain a DOPO-type silane coupling agent;

[0007] (2) adding the DOPO-type silane coupling agent prepared in step (1) to the fumed silica, and uniformly loading DOPO on the surface of the fumed silica by stirring or ultrasonic dispersion. During this process, DOPO is stabilized on the surface of the fumed silica by chemical bonding, and filtering and drying to obtain DOPO-modified fumed silica;

[0008] (3) Adding the DOPO-modified fumed silica prepared in step (2) into water or explosion suppressant solution and stirring to obtain the DOPO-modified dry water explosion suppressant.

[0009] The added explosion suppressant can quickly absorb heat and release gas at the initial stage of explosion, thus playing a role in suppressing the spread of 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 the solvent is (5-8) g:100 mL, the silane coupling agent includes HK560, the molar ratio of the 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 to 4 wt% of the fumed silica; the stirring speed is 150 to 300 r / min, and the time is 15 to 25 min; the power of the ultrasonic dispersion is 2000 to 2500 w, and the time is 4 to 6 min; the drying temperature is 50 to 60° C., and the time is 10 to 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 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 8-12wt%, 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 technical solution 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-mentioned preparation method of the DOPO modified dry water explosion suppressant.

[0016] The present invention also provides a use of the above-mentioned DOPO modified dry water explosion suppressant in suppressing deflagration of combustible gas.

[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, excellent impact resistance and thermal decomposition resistance, can effectively suppress the occurrence of explosions in dangerous environments, and is suitable for high-risk places such as chemical plants, mines, and oil and gas storage.

[0019] (2) The present invention significantly improves the explosion suppression performance of dry water by modifying the core material and wall material. The addition of DOPO gives dry water good flame retardant properties, which can effectively suppress flame propagation under high temperature or fire conditions; the composite use of explosion suppressants enhances the explosion suppression effect of dry water, forming a composite material with higher explosion suppression performance, and the type of explosion suppressant can be adjusted according to the actual application environment (for example, in a coal mine environment, sodium bicarbonate can be preferentially selected as an explosion suppressant; in a chemical plant, a P series explosion suppressant can be selected to deal with the fire hazard of phosphides), which can be widely used in explosion-proof needs in different scenarios, improving the flexibility of explosion suppressants. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 This is a flow chart of preparing DOPO modified dry water explosion suppressant according to Example 2;

[0022] Figure 2 This is an optical microscope image of the DOPO-modified dry water explosion suppressant prepared in Example 2;

[0023] Figure 3 This is a graph showing the inhibitory effect of the explosion suppressants prepared in Examples 1 to 3 and Comparative Examples 1 to 2 on the explosion intensity of 20 vol% H2;

[0024] Figure 4 This is a graph showing the inhibitory effect of the explosion suppressants prepared in Examples 1 to 3 and Comparative Examples 1 to 2 on the explosion intensity of 9.5 vol% methane. DETAILED DESCRIPTION

[0025] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0026] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range 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 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.

[0027] 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.

[0028] 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 the skilled artisan. The present invention description and examples are exemplary only.

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

[0030] In the following examples, fumed silica refers to a nanometer-sized white powder generated by high-temperature hydrolysis of silicon halides in a hydrogen-oxygen flame. The fumed silica 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 m 2 / kg; DOPO was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. The following description will not be repeated.

[0031] Example 1

[0032] The preparation method of DOPO modified dry water explosion suppressant comprises the following steps:

[0033] (1) 6.86 g of DOPO was dissolved in 100 mL of anhydrous ethanol and stirred for 10 min to disperse it evenly to form a uniform DOPO solution. Silane coupling agent HK560 was added to the DOPO solution, and the molar ratio of silane coupling agent HK560 to DOPO was 1:1. The mixture was stirred at 55° C. until transparent to obtain a DOPO-type silane coupling agent.

[0034] (2) adding the DOPO type silane coupling agent prepared in step (1) to the fumed silica, wherein the amount of the DOPO type silane coupling agent added is 3 wt % of the fumed silica, stirring at 200 r / min for 20 min to uniformly load DOPO on the surface of the fumed silica (ultrasonic dispersion at 2400 W for 5 min is also possible, with the same effect), filtering, and drying at 55° C. for 12 h to obtain DOPO-modified fumed silica;

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

[0036] Example 2

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

[0038] The flow chart of preparing DOPO modified dry water explosion suppressant in this embodiment is as follows: Figure 1 As shown, the optical microscope image of the prepared DOPO modified dry water explosion suppressant is as follows Figure 2 As shown. Figure 2 It can be seen that the prepared DOPO modified dry water has regular spheres, which means that after modification, more explosion-suppressing groups are grafted on the surface without affecting the core-shell structure, and at the same time, the spheres can be prevented from breaking and the contents can flow out.

[0039] Example 3

[0040] The same as Example 1, except that the "deionized water" added in step (3) is replaced by "explosion suppressant solution (10 wt% diammonium phosphate)", and step (3) is specifically: adding the explosion suppressant diammonium phosphate to deionized water, stirring at 55° C. until transparent, to obtain a 10 wt% diammonium phosphate solution; adding the DOPO-modified fumed silica prepared in step (2) to the 10 wt% diammonium phosphate solution at a mass ratio of 9:100, stirring at 4500 r / min for 300 s, to obtain a DOPO-modified dry water explosion suppressant.

[0041] Comparative Example 1

[0042] Same as Example 2, except that, in step (1): after adding silane coupling agent HK560 to the DOPO solution, stirring is performed at 35° C. Step (1) is specifically as follows: 6.86 g of DOPO is dissolved in 100 mL of anhydrous ethanol, stirred for 10 min to disperse it evenly to form a uniform DOPO solution, silane coupling agent HK560 is added to the DOPO solution, the molar ratio of silane coupling agent HK560 to DOPO is 1:1, and stirred at 35° C. until transparent to obtain a DOPO type silane coupling agent.

[0043] Comparative Example 2

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

[0045] Effect verification:

[0046] 1. Verify the explosion suppression effect of the products obtained by ordinary dry water (preparation method is the same as that of Example 1, the only difference is that DOPO is not added during the preparation process, and the dosage and steps of other raw materials, and each process parameter are the same as that of Example 1), Examples 1 to 3 and Comparative Examples 1 to 2 on hydrogen: 20 vol% H2 is mixed with air in a 20L standard explosion test device to form a gaseous mixture. After a delay of 90ms, the mixture is ignited and detonated (the explosion suppressant is stored in a powder tank in the 20L device. During the experiment, a certain mass of the suppressant in the powder tank is first sprayed out with compressed gas and then detonated after a delay of 90ms). The explosion 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 best explosion suppression effect is achieved by mixing 10 wt % sodium bicarbonate with DOPO modified dry water for 20 vol % H2 (the smaller the maximum explosion pressure, the better the suppression effect, where complete suppression means the maximum explosion pressure is less than 0.15 mPa). 3 Complete suppression was achieved, that is, the maximum explosion pressure was less than 0.15 mPa; and DOPO-modified dry water compounded with 10 wt% diammonium phosphate showed a good suppression effect, which could further suppress H2 explosion on the basis of the explosion suppression effect of unmodified uncompounded dry water.

[0047] 2. Verify the explosion suppression effect of the products prepared by ordinary dry water (the preparation method is the same as that of Example 1, except that DOPO is not added during the preparation process, and the amounts of other raw materials, steps, and process parameters are the same as those of Example 1), Examples 1 to 3, and Comparative Examples 1 to 2 on methane: 9.5 vol% methane and air are mixed in a 20L standard explosion test device to form a gas phase mixture. After a delay of 90s, the mixture is ignited and detonated. The explosion suppression effect of each group of explosion suppressants on 9.5 vol% methane is as follows: Figure 4 As shown. Figure 4 It can be seen that ordinary dry water has limited effect on the explosion suppression of methane at an equivalent level. 3 Increasing the inhibitor concentration does not suppress the explosion better, but DOPO modified dry water mixed with 10wt% sodium bicarbonate and 10wt% diammonium phosphate can suppress the explosion well. The DOPO molecules on the modified wall material can first be decomposed by heat to absorb the free radicals of the chain reaction in the explosion; then the dry water breaks down under the action of temperature and pressure to release the core material to continue to participate in the explosion suppression. Different core materials have different effects on the suppression of methane explosions. Among them, sodium bicarbonate is the best as the core material. At 600g / m 3 It can achieve complete explosion suppression of equivalent methane.

[0048] The above description is only a preferred specific implementation manner of the present invention, and the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, and they should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a DOPO-modified dry water explosion suppressant, characterized in that: The following steps are involved: (1) dissolving DOPO in a solvent, adding a silane coupling agent to the obtained DOPO solution, and stirring to obtain a DOPO-type silane coupling agent; (2) adding the DOPO-type silane coupling agent prepared in step (1) to the fumed silica, uniformly loading DOPO on the surface of the fumed silica by stirring or ultrasonic dispersion, filtering and drying to obtain DOPO-modified fumed silica; (3) Adding the DOPO-modified fumed silica prepared in step (2) into water or explosion suppressant solution and stirring to obtain the DOPO-modified dry water explosion suppressant.

2. The method for preparing the DOPO modified dry water explosion suppressant according to claim 1, characterized in that: In step (1), the solvent includes ethanol and / or ethylene glycol, the mass volume ratio of DOPO to the solvent is (5-8) g:100 mL, the silane coupling agent includes HK560, the molar ratio of the silane coupling agent to DOPO is (0.8-1.1):1, and the stirring is carried out at 40-60° C.

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

4. The method for preparing the DOPO modified dry water explosion suppressant according to claim 1, characterized in that: In step (3), the mass ratio of the DOPO-modified fumed silica to water or explosion suppressant solution is (7-11):100, the stirring speed is 4000-5000 r / min, and the time is 250-350 s.

5. The method for preparing the DOPO modified dry water explosion suppressant according to claim 1, characterized in that: 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.

6. The method for preparing the DOPO modified dry water explosion suppressant according to claim 5, characterized in that: The N series explosion suppressants include urea and / or ammonium nitrate, the P series explosion suppressants include ammonium phosphate and / or calcium hydrogen phosphate, the carbonate explosion suppressants include calcium carbonate and / or magnesium carbonate, and the phosphate explosion suppressants include potassium phosphate and / or sodium phosphate.

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

8. Use of the DOPO modified dry water explosion suppressant according to claim 7 in suppressing deflagration of combustible gas.

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