Hydrogen-doped natural gas compound powder explosion suppressant and application thereof

Abstract

The invention provides a hydrogen-doped natural gas compound powder explosion suppressant and application thereof. The hydrogen-doped natural gas compound powder explosion suppressant comprises an explosion suppression base material and an explosion suppression auxiliary material, the explosion suppression base material comprises at least two types of organic salts and / or inorganic salts with different thermal decomposition temperature intervals. The compound powder explosion suppressant provided by the invention can generate various high-activity chemical substances at the initial stage of flame development, and the generated high-activity chemical substances can quickly consume flame chain reaction free radicals and interrupt combustion chain reaction so as to quickly block the combustion explosion process of hydrogen-doped natural gas. Compared with an existing dry powder extinguishing agent as an explosion suppressant, the compound powder explosion suppressant provided by the invention can effectively block the burning and explosion process of hydrogen-doped natural gas, the explosion suppression speed and the explosion suppression performance are far higher than those of the existing dry powder extinguishing agent, and the burning and explosion power of the hydrogen-doped natural gas can be effectively reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of explosion suppression materials for hydrogen-doped natural gas, and relates to a hydrogen-doped natural gas compound powder explosion suppressant and its application. Background Art

[0002] Existing explosion suppressants are mainly composed of fire extinguishing agent materials. The main fire extinguishing principle of existing dry powder fire extinguishers is that the powder of the dry powder falls on the surface of the combustible material, undergoes a chemical reaction, and forms a glassy covering layer under the action of high temperature, thereby isolating oxygen for suffocation fire extinguishing. However, when a hydrogen-doped natural gas explodes and burns, the chemical reaction rate of the combustible material and the development rate of the flame are much greater than that of combustion. Moreover, when a gas deflagrates in a large-scale enclosed space, the dry powder product cannot fall on the combustible gas to form an isolation layer, and the effect of chemically inhibiting the free radicals generated by the fuel during the combustion process by the thermal decomposition products of the inorganic salts in the dry powder to block the deflagration of hydrogen-doped natural gas is also very weak.

[0003] In order to overcome the above-mentioned disadvantages of existing dry powder fire extinguishers as hydrogen-doped natural gas explosion suppressants, it is desired to develop a hydrogen-doped natural gas explosion suppressant with a better explosion suppression effect in this field. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a hydrogen-doped natural gas compound powder explosion suppressant and its application, and specifically provide a hydrogen-doped natural gas compound powder explosion suppressant composed of binary or multi-component effective fire extinguishing elements. Compared with the dry powder fire extinguishers commonly used at present, the compound powder explosion suppressant provided by the present invention can effectively block the deflagration process of hydrogen-doped natural gas and reduce the deflagration power of hydrogen-doped natural gas.

[0005] To achieve this purpose, the present invention adopts the following technical solutions:

[0006] In the first aspect, the present invention provides a hydrogen-doped natural gas compound powder explosion suppressant, and the hydrogen-doped natural gas compound powder explosion suppressant includes an explosion suppression base material and an explosion suppression auxiliary material;

[0007] The explosion suppression base material includes at least two types of organic salts and / or inorganic salts with different thermal decomposition temperature ranges.

[0008] In the present invention, the thermal decomposition temperature range refers to the temperature range from the start of decomposition to complete decomposition of the material during the heating process.

[0009] The compound powder explosion suppressant provided by the present invention can generate a variety of highly active chemical substances in the initial stage of flame development. These generated highly active chemical substances can rapidly consume the free radicals in the flame chain reaction, interrupt the combustion chain reaction, and thus quickly block the combustion and explosion process of hydrogen-doped natural gas. Compared with the existing dry powder fire extinguishing agent used as an explosion suppressant, the compound powder explosion suppressant provided by the present invention has an extremely strong effect of blocking the combustion and explosion of hydrogen-doped natural gas.

[0010] In the compound powder explosion suppressant provided by the present invention, there are at least two types of organic salts and / or inorganic salts with different thermal decomposition temperature ranges, including combinations of two types of inorganic salts and / or organic salts that are generally considered incompatible under normal circumstances (such as the combination of ammonium polyphosphate and sodium bicarbonate, potassium bicarbonate, etc. The reaction between the components can be effectively avoided through coating technology, physical isolation, etc., to maintain the stability of the explosion suppressant).

[0011] The explosion suppression base material provided by the present invention includes at least two types of organic salts and / or inorganic salts with different thermal decomposition temperature ranges. After the different types of organic salts and / or inorganic salts are thermally decomposed, they should be able to generate different active chemical substances to better capture and neutralize the generation of free radicals, achieving the effect of blocking the reaction.

[0012] Preferably, the thermal decomposition temperature ranges of the organic salts and / or inorganic salts are each independently 30 - 500 °C, such as 30 °C, 40 °C, 60 °C, 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, 300 °C, 320 °C, 340 °C, 360 °C, 380 °C, 400 °C, 420 °C, 440 °C, 460 °C, 480 °C, 500 °C, etc., as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list all the specific point values included in the range.

[0013] Preferably, the explosion suppression base material includes at least two types of organic salts and / or inorganic salts with different thermal decomposition temperature ranges, and the thermal decomposition temperature ranges of the different types of organic salts and / or inorganic salts overlap.

[0014] Preferably, the organic salts include metal salts of organic oxygen-containing acid radicals and / or non-metal salts of organic oxygen-containing acid radicals.

[0015] Preferably, the metal salts of organic oxygen-containing acid radicals include any one or at least two combinations of metal salts formed by citrate radicals and metals, and metal salts formed by oxalate radicals and metals.

[0016] Preferably, the metal salts formed by the citrate radical and metals (such as alkali metals, alkaline earth metals, transition metals, etc.) include any one or a combination of at least two of metal salts such as sodium citrate, potassium citrate, magnesium citrate, zinc citrate, copper citrate, etc.

[0017] Preferably, the metal salts formed by the oxalate radical and metals include any one or a combination of at least two of metal salts such as sodium oxalate, potassium oxalate, zinc oxalate, etc.

[0018] Preferably, the non-metal salts of the organic oxygen-containing acid radical include the non-metal salts formed by the citrate radical and ammonium.

[0019] Preferably, the non-metal salts formed by the citrate radical and ammonium include any one or a combination of at least two of ammonium salts such as ammonium citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate, etc.

[0020] The metal salts of the organic oxygen-containing acid radical and / or the non-metal salts of the organic oxygen-containing acid radical can rapidly dissociate into highly active free radicals under the action of a certain temperature, and can also produce inerting gases such as ammonia and carbon dioxide, and high-density water vapor.

[0021] Preferably, the inorganic salts include the metal salts of the inorganic oxygen-containing acid radical and / or the non-metal salts of the inorganic oxygen-containing acid radical.

[0022] Preferably, the metal salts of the inorganic oxygen-containing acid radical include the metal salts formed by the bicarbonate radical and metals.

[0023] Preferably, the metal salts formed by the bicarbonate radical and metals (such as alkali metals or alkaline earth metals, etc.) include any one or a combination of at least two of metal salts such as sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate or barium bicarbonate, etc.

[0024] Preferably, the non-metal salts of the inorganic oxygen-containing acid radical include the non-metal salts formed by the phosphorus-based oxygen-containing acid radical and ammonium, the salts formed by the carbonate radical and non-metal compounds, and the salts formed by the bicarbonate radical and non-metal compounds.

[0025] Preferably, the non-metal salts formed by the phosphorus-based oxygen-containing acid radical and ammonium include any one or a combination of at least two of ammonium salts such as ammonium phosphate, ammonium polyphosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium polyphosphate, etc.

[0026] Preferably, the salt formed by the carbonate radical and non-metal compounds includes ammonium carbonate.

[0027] Preferably, the salt formed by the bicarbonate radical and non-metal compounds includes ammonium bicarbonate.

[0028] Metal salts of inorganic oxoacids and / or non-metal salts of inorganic oxoacids can also rapidly dissociate into highly reactive free radicals under the action of a certain temperature, and can generate inerting gases such as ammonia and high-density water vapor to rapidly block the development of the flame.

[0029] The organic salts and inorganic salts of the composite powder explosion suppressant applicable to the present invention can be purchased, or can be prepared according to the synthesis methods known to those skilled in the art, such as the methods recorded in the literature.

[0030] Preferably, the hydrogen-doped natural gas composite powder explosion suppressant, by weight percentage, comprises 73%-90% of an explosion suppression base material (such as 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, etc., and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the scope), and 10%-27% of explosion suppression auxiliary materials (such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, etc., and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the scope).

[0031] Preferably, the explosion suppression auxiliary materials include any one or a combination of at least two of a flame retardant, a lubricant, and a moisture-proof agent.

[0032] Preferably, based on the total weight of the hydrogen-doped natural gas composite powder explosion suppressant being 100%, the dosage of the flame retardant is 10%-15%, such as 10%, 11%, 12%, 13%, 14%, 15%, etc., and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the scope, and the total dosage of the lubricant and the moisture-proof agent is 0-15%, such as 0, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the scope.

[0033] The flame retardants for the compound powder explosion suppressant applicable to the present invention include organic flame retardants, such as halogen-based flame retardants, for example, tetrabromobisphenol A (TBBA), decabromodiphenylethane (DBDPO), tris(2,3-dibromopropyl) isocyanurate (TBC), etc.; phosphorus-based flame retardants, such as phosphates, phosphites, organic phosphonium salts, phosphorus oxides, and phosphorus-nitrogen compounds, etc.; and inorganic phosphorus-based flame retardants such as red phosphorus, ammonium polyphosphate (APP), etc.; nitrogen-based flame retardants, such as melamine and its derivatives (such as melamine cyanurate MCA), etc.; silicon-based flame retardants, such as organosilicon-based flame retardant SFR-100, etc.; inorganic flame retardants, such as hydroxide flame retardants, antimony trioxide, and zinc borate, etc.

[0034] To ensure that the compound powder explosion suppressant remains in a loose state during storage, avoid caking, and can be smoothly ejected from the nozzles of various fire extinguishing equipment and devices during actual application, similar to the dry powder fire extinguishing agent on the current market, specific proportions of lubricants and moisture-proof agents are deliberately added to the explosion suppressant. These components include but are not limited to mica powder, activated clay, magnesium stearate, talc powder, and silica white, etc., and their addition amounts follow the generally recognized conventional ranges in the industry, preferably 0 - 15% by weight. To further improve the fluidity of the explosion suppressant, surface coating treatment of the compound powder explosion suppressant with silicone oil can also be carried out to achieve a silicification effect.

[0035] Through the above measures, the compound powder explosion suppressant can not only effectively prevent moisture absorption and caking problems, but also ensure its efficient spraying during actual application, meeting the explosion suppression requirements of hydrogen-doped natural gas in various scenarios.

[0036] It should be noted that the present invention does not specifically limit the preparation method of the hydrogen-doped natural gas compound powder explosion suppressant, and it can be prepared according to the same or similar preparation methods as the existing dry powder fire extinguishing agent (for example, it can be obtained by direct mixing).

[0037] Preferably, the D90 particle size of the hydrogen-doped natural gas compound powder explosion suppressant is 0.1 - 100 microns, for example, 0.1 micron, 0.3 micron, 0.5 micron, 0.8 micron, 1 micron, 3 micron, 5 micron, 8 micron, 10 micron, 20 micron, 30 micron, 40 micron, 50 micron, 60 micron, 70 micron, 80 micron, 90 micron, 100 micron, etc., as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range, and preferably 0.1 - 20 microns. When the D90 particle size of the explosion suppressant is within the range of 0.1 - 20 microns, it belongs to ultrafine powder, and compared with the conventional dry powder fire extinguishing agent, its explosion suppression efficiency will be further improved.

[0038] In a second aspect, the present invention provides an application of the hydrogen-doped natural gas compound powder explosion suppressant as described in the first aspect in hydrogen-doped natural gas explosion suppression materials.

[0039] The compound powder explosion suppressant provided by the present invention can be used to block the combustion and explosion process of hydrogen - doped natural gas and reduce the combustion and explosion power of hydrogen - doped natural gas, including but not limited to scenarios where hydrogen - doped natural gas combustion and explosion may occur in production and transportation links such as closed / semi - closed spaces, pipelines, pipe networks, etc. The compound powder explosion suppressant provided by the present invention can be loaded into various fire - fighting equipment such as portable fire extinguishers and fire bombs for use, and can also be used in fixed fire - fighting equipment in closed spaces.

[0040] Compared with the prior art, the present invention has at least the following beneficial effects:

[0041] The compound powder explosion suppressant provided by the present invention can generate a variety of highly active chemical substances in the initial stage of flame development. These generated highly active chemical substances can rapidly consume free radicals in the flame chain reaction, interrupt the combustion chain reaction, and thus quickly block the combustion and explosion process of hydrogen - doped natural gas. Compared with the existing dry powder fire extinguishing agent used as an explosion suppressant, the compound powder explosion suppressant provided by the present invention can effectively block the combustion and explosion process of hydrogen - doped natural gas. The explosion suppression speed and performance are much higher than those of the existing dry powder fire extinguishing agent, and can effectively reduce the combustion and explosion power of hydrogen - doped natural gas. Specific embodiments

[0042] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0043] Unless otherwise specified, the D90 particle size of the solid raw materials used in the following examples and comparative examples of the present invention is in the range of 0.1 - 20 microns.

[0044] Example 1

[0045] In this example, a hydrogen - doped natural gas compound powder explosion suppressant is provided, and its specific components and the content of each component (weight percentage) are shown in Table 1 below:

[0046] Table 1

[0047]

[0048] The preparation method includes the following steps: Mix the formulated amounts of organic salts, inorganic salts, flame retardants, lubricants, and moisture - proof agents to obtain the hydrogen - doped natural gas compound powder explosion suppressant.

[0049] Example 2

[0050] In this example, a hydrogen - doped natural gas compound powder explosion suppressant is provided, and its specific components and the content of each component (weight percentage) are shown in Table 2 below:

[0051] Table 2

[0052]

[0053] The preparation method refers to Example 1.

[0054] Example 3

[0055] In this example, a hydrogen-doped natural gas compound powder explosion suppressant is provided, and its specific components and the content of each component (weight percentage) are shown in Table 3 below:

[0056] Table 3

[0057]

[0058] The preparation method refers to Example 1.

[0059] Comparative Example 1

[0060] In this comparative example, a hydrogen-doped natural gas compound powder explosion suppressant is provided, and its specific components and the content of each component (weight percentage) are shown in Table 4 below:

[0061] Table 4

[0062]

[0063] The preparation method includes the following steps: Mix the organic salts, flame retardants, lubricants, and moisture-proof agents in the formula amounts to obtain the hydrogen-doped natural gas compound powder explosion suppressant.

[0064] Comparative Example 2

[0065] In this comparative example, a hydrogen-doped natural gas compound powder explosion suppressant is provided, and its specific components and the content of each component (weight percentage) are shown in Table 5 below:

[0066] Table 5

[0067]

[0068]

[0069] The preparation method includes the following steps: Mix the inorganic salts, flame retardants, lubricants, and moisture-proof agents in the formula amounts to obtain the hydrogen-doped natural gas compound powder explosion suppressant.

[0070] Perform performance tests on the explosion suppressants provided in the examples and comparative examples. The test method is as follows:

[0071] The experimental device is an elliptical tank with a volume of 2 cubic meters. First, 5% hydrogen-doped natural gas with an equivalence ratio of 0.8 is injected at a rate of 50 L / min. After standing for 3 minutes, a compound powder explosion suppressant is sprayed in. After spraying the powder, it stands for 15 - 20 s. After waiting for the powder to be evenly distributed, a chemical igniter is used to detonate the hydrogen-doped natural gas. Through the explosion suppression test of hydrogen-doped natural gas in a closed space, explosion pressure of hydrogen-doped natural gas in the closed space, flame temperature data at the time of explosion, and combustion explosion characteristic parameters such as the flame development process are obtained to comprehensively test the explosion suppression performance of the mixed powder.

[0072] The performance test results are shown in Table 6.

[0073] Table 6

[0074] Peak explosion pressure Flame temperature during explosion Example 1 20 kPa 350℃ Example 2 35 kPa 375℃ Example 3 32 kPa 382℃ Comparative example 1 253 kPa 621℃ Comparative example 2 320 kPa 653℃

[0075] As can be seen from Table 6, the compound powder explosion suppressant provided in the embodiments of the present invention has good explosion suppression effects on hydrogen-doped natural gas (peak explosion pressure: 20 - 35 kPa, flame temperature at the time of explosion: 350 - 382 °C).

[0076] Compared with the explosion suppressant provided in Comparative Example 1, the peak explosion pressure of Example 1 is reduced by 92.09%, and the flame temperature at the time of explosion is reduced by 271 °C; compared with the explosion suppressant provided in Comparative Example 2, the peak explosion pressure of Example 1 is reduced by 93.75%, and the flame temperature at the time of explosion is reduced by 303 °C. Generally speaking, Example 1 can greatly reduce the peak explosion pressure and the flame temperature at the time of explosion, achieving the effect of effective explosion suppression.

[0077] The applicant declares that the present invention uses the above embodiments to illustrate the hydrogen-doped natural gas compound powder explosion suppressant and its application of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A hydrogen-doped natural gas composite powder explosion suppressant, characterized in that: The hydrogen-doped natural gas composite powder explosion suppressant comprises an explosion suppressing base material and an explosion suppressing auxiliary material; The explosion suppression base material comprises at least two types of organic salts and / or inorganic salts having different thermal decomposition temperature ranges.

2. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 1, characterized in that: The thermal decomposition temperature range of the organic salt and / or inorganic salt is independently 30-500°C; Preferably, the explosion suppression base material comprises at least two types of organic salts and / or inorganic salts having different thermal decomposition temperature ranges, and the thermal decomposition temperature ranges of different types of organic salts and / or inorganic salts overlap.

3. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 1 or 2, characterized in that: The organic salt includes a metal salt of an organic oxygen-containing acid radical and / or a non-metal salt of an organic oxygen-containing acid radical.

4. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 3, characterized in that: The metal salt of the organic oxygen-containing acid radical includes any one or a combination of at least two of a metal salt formed by a citrate radical and a metal, and a metal salt formed by an oxalate radical and a metal; Preferably, the metal salt formed by the citrate and the metal includes any one of sodium citrate, potassium citrate, magnesium citrate, zinc citrate, copper citrate, or a combination of at least two thereof; Preferably, the metal salt formed by the oxalate and the metal includes any one of sodium oxalate, potassium oxalate and zinc oxalate, or a combination of at least two of them.

5. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 3 or 4, characterized in that: The non-metallic salt of the organic oxygen-containing acid radical comprises a non-metallic salt formed by citrate and ammonium; Preferably, the non-metallic salt formed by the citrate and ammonium includes any one of ammonium citrate, diammonium hydrogen citrate, and diammonium hydrogen citrate, or a combination of at least two of them.

6. The hydrogen-doped natural gas composite powder explosion suppressant according to any one of claims 1 to 5, characterized in that: The inorganic salt includes a metal salt of an inorganic oxygen-containing acid radical and / or a non-metallic salt of an inorganic oxygen-containing acid radical.

7. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 6, characterized in that: The metal salt of the inorganic oxygen-containing acid radical includes a metal salt formed by bicarbonate and a metal; Preferably, the metal salt formed by the bicarbonate and the metal includes any one of sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate or barium bicarbonate, or a combination of at least two thereof.

8. The hydrogen-doped natural gas composite powder explosion suppressant according to claim 6 or 7, characterized in that: The inorganic oxygen-containing acid radical non-metallic salts include non-metallic salts formed by phosphorus-containing oxygen-containing acid radicals and ammonium, salts formed by carbonate radicals and non-metallic compounds, and salts formed by bicarbonate radicals and non-metallic compounds; Preferably, the non-metallic salt formed by the phosphorus-based oxygen-containing acid radical and ammonium includes any one of ammonium phosphate, ammonium polyphosphate, ammonium polyphosphate, ammonium pyrophosphate, and ammonium metaphosphate, or a combination of at least two thereof; Preferably, the salt formed by the carbonate ion and the non-metallic compound comprises ammonium carbonate; Preferably, the salt formed by the bicarbonate and the non-metal compound comprises ammonium bicarbonate.

9. The hydrogen-doped natural gas composite powder explosion suppressant according to any one of claims 1 to 8, characterized in that: The hydrogen-doped natural gas composite powder explosion suppressant comprises, by weight percentage, 73%-90% of an explosion suppressant base material and 10%-27% of an explosion suppressant auxiliary material; Preferably, the explosion suppression auxiliary material includes any one or a combination of at least two of a flame retardant, a lubricant, and a moisture proof agent; Preferably, based on the total weight of the hydrogen-doped natural gas composite powder explosion suppressant being 100%, the amount of the flame retardant is 10%-15%, and the total amount of the lubricant and moisture-proofing agent is 0-15%; Preferably, the flame retardant comprises an organic flame retardant and / or an inorganic flame retardant; Preferably, the D90 particle size of the hydrogen-doped natural gas composite powder explosion suppressant is 0.1 to 100 microns, preferably 0.1 to 20 microns.

10. Use of the hydrogen-doped natural gas composite powder explosion suppressant according to any one of claims 1 to 9 in hydrogen-doped natural gas explosion suppressant materials.

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