CN109021918B - Preparation method of low-carbon mixed gas hydrate explosion suppressant - Google Patents
Preparation method of low-carbon mixed gas hydrate explosion suppressant Download PDFInfo
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Abstract
The invention relates to a preparation method of a low-carbon mixed gas hydrate explosion suppressant, which can effectively solve the production problem of a high-efficiency environment-friendly explosion suppressant material, and is characterized in that inorganic salt is added into a solvent, so that the mass content of the inorganic salt is 0.001-0.1mol/L to form a hydrate; volume ratio: 5-15% of carbon dioxide and 85-95% of mixed gas of nitrogen and argon are mixed together to form inert mixed gas; filling inert mixed gas into a hydration agent, leading the pressure to reach 4-10MPa, reacting for 300min at the temperature of minus 10-8 ℃ to generate mixed gas hydrate, and crushing the mixed gas hydrate generated by the reaction into hydrate powder with the grain diameter less than 1.0mm at the temperature of minus 10 ℃. The explosion suppression agent has the advantages of rich raw materials, simple preparation method, easy synthesis and preparation, convenient use, low cost, cleanness, environmental protection and good explosion suppression effect, is an innovation of the explosion suppression agent, can effectively weaken energy required by explosion pressure wave propagation to block the explosion wave propagation, and has great economic and social benefits.
Description
Technical Field
The invention relates to chemical engineering, in particular to a preparation method of a low-carbon mixed gas hydrate explosion suppressant with high efficiency and environmental protection.
Background
In the industrial production and transportation and use process, flammable and explosive gases and dust are involved, fire combustion and explosion accidents are easy to occur, even secondary explosion can be caused, and great property loss and casualties are caused. The explosion suppressant can effectively weaken and control explosion disasters and reduce property loss and casualties. Therefore, various countries successively research and develop explosion suppression products, and the safety problem of flammable and explosive liquid gas in the production and transportation process is improved. The common water system has strong fluidity and limited explosion suppression effect; the powder with a complex structure has the defects of complex preparation and slow cooling, and the harm of the absorbability of the powder, particularly certain nano-powder, to human bodies is yet to be researched.
The gas hydrate is a non-stoichiometric envelope cage-shaped compound generated by gas and water under the conditions of low temperature and high pressure, and gas molecules are wrapped in a cage-shaped lattice formed by water molecules. The hydrate of unit volume can store 160-180 volumes of gas under standard conditions. Considering that a large amount of heat is absorbed and moisture is released when the gas hydrate is decomposed, it is proposed that multiple explosion suppression effects are achieved by using the inert gas hydrate added with the explosion suppression agent component.
The decomposition process of the carbon dioxide/nitrogen/argon hydrate is a violent heat absorption process, and water, low-carbon inert mixed gas and inorganic salt are released simultaneously. The explosion suppression mechanism of water energy mainly lies in that water can move, compress and evaporate under the action of shock waves generated by explosion, and a large amount of explosion energy is absorbed, so that the shock waves are effectively reduced. The mechanism of explosion suppression of the low-carbon explosion suppressor is mainly that gas in the explosion suppressor can dilute air around an explosive to reduce the oxygen concentration below an explosion limit, so that the explosion reaction cannot be continuously supported; the global warming potential of the low-carbon inert gas explosion suppressant is close to 0, and the low-carbon inert gas explosion suppressant is cleaner and more environment-friendly compared with a pure carbon dioxide explosion suppressant. The inorganic salt used as the gas hydrate accelerant during the preparation of the hydrate has the capacity of explosion suppression, the mechanism of explosion suppression is mainly that the selected inorganic salt can increase the gas storage capacity of single-volume water in the gas hydrate, more low-carbon mixed gas can be released during explosion, simultaneously released halogen anions and phosphate radicals can react with free radicals generated in the explosion process so as to interrupt chain reaction, and released silicon dioxide can absorb heat generated by explosion and cover the surface of an explosive, so that the purpose of explosion suppression is achieved.
The low-carbon inert gas explosion suppressant can only achieve the purpose of explosion suppression from the aspects of dilution, oxygen concentration reduction and the like, the water system explosion suppressant has poor explosion suppression effect due to strong fluidity, and the pure carbon dioxide explosion suppressant has strong greenhouse effect. The low-carbon inert gas hydrate explosion suppressant added with the inorganic salt has a strong heat absorption and cooling effect, can release water, low-carbon inert gas and inorganic salt with an explosion suppression effect, can be used as a novel explosion suppression material, but has no published report of the explosion suppression material.
The invention content is as follows:
in view of the above situation, the present invention aims to provide a preparation method of a low-carbon mixed gas hydrate explosion suppressant, which can effectively solve the production problem of high-efficiency environment-friendly explosion suppressant materials.
The technical scheme for solving the problem is that the preparation method of the low-carbon mixed gas hydrate explosion suppressant comprises the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt into a solvent to ensure that the mass content of the inorganic salt is 0.001-0.1 mol/L;
the solvent is water or dry water; the inorganic salt is silicon dioxide, potassium phosphate or metal halide ABnA is one of Na, Mg, K or Ca, B is one of F, Cl, Br or I, and n =1, 2;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 5-15% of carbon dioxide and 85-95% of mixed gas of nitrogen and argon are mixed together, and the volume ratio of nitrogen to argon is arbitrary;
(3) and (3) mixing reaction:
filling inert mixed gas into a hydration agent, leading the pressure to reach 4-10MPa, reacting for 300min at the temperature of minus 10-8 ℃ to generate mixed gas hydrate, and crushing the mixed gas hydrate generated by the reaction into hydrate powder with the grain diameter less than 1.0mm at the temperature of minus 10 ℃.
The explosion suppression agent has the advantages of rich raw materials, simple preparation method, easy synthesis and preparation, convenient use, low cost, cleanness, environmental protection and good explosion suppression effect, is an innovation of the explosion suppression agent, can effectively weaken energy required by explosion pressure wave propagation to block the explosion wave propagation, and has great economic and social benefits.
Detailed Description
The following detailed description of the embodiments of the present invention will be given with reference to the accompanying specific cases and examples.
In particular, the invention may be embodied as set forth in the following examples.
Example 1
In the specific implementation of the invention, the preparation method of the low-carbon mixed gas hydrate explosion suppressant comprises the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt silicon dioxide into water to ensure that the mass content of the silicon dioxide is 0.05 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: mixing 10% of carbon dioxide and 90% of mixed gas of nitrogen and argon, wherein the volume ratio of nitrogen to argon is 1: 1;
(3) and (3) mixing reaction:
charging inert mixed gas into the hydration agent, making the pressure reach 7MPa, reacting for 150min at 3 deg.C to generate mixed gas hydrate, and pulverizing the mixed gas hydrate generated by reaction into hydrate powder with particle size less than 1.0mm at-10 deg.C.
Example 2
In the specific implementation of the invention, the preparation method of the low-carbon mixed gas hydrate explosion suppressant comprises the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt NaCl into dry water to ensure that the mass content of the NaCl is 0.01 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 7% of carbon dioxide, and 93% of mixed gas of nitrogen and argon, wherein the volume ratio of nitrogen to argon is 1: 3;
(3) and (3) mixing reaction:
charging inert mixed gas into the hydration agent, making the pressure reach 6MPa, reacting for 160min at 1 deg.C to generate mixed gas hydrate, and pulverizing the generated mixed gas hydrate into hydrate powder with particle size less than 1.0mm at-10 deg.C.
Example 3
In the specific implementation of the invention, the preparation method of the low-carbon mixed gas hydrate explosion suppressant comprises the following steps:
(1) and preparing a hydrating agent:
adding an inorganic salt MgF into solvent dry water to ensure that the mass content of the inorganic salt is 0.03 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 14% of carbon dioxide and 86% of mixed gas of nitrogen and argon are mixed together, and the volume ratio of the nitrogen to the argon is arbitrary;
(3) and (3) mixing reaction:
filling inert mixed gas into a hydration agent, leading the pressure to reach 8MPa, reacting for 100-240min at the temperature of minus 10-5 ℃ to generate mixed gas hydrate, and crushing the mixed gas hydrate generated by the reaction into hydrate powder with the grain diameter less than 1.0mm at the temperature of minus 10 ℃.
The explosion suppressant is a mixed gas hydrate generated by reacting an inert mixed gas containing carbon dioxide, nitrogen and argon and water or dry water, wherein a certain amount of inorganic salt is added, the inert mixed gas is reacted with the water or the dry water at 4-10MPa and the temperature is minus 10-8 ℃, the mixed gas hydrate is crushed into hydrate powder with the particle size of less than 1.0mm at the temperature of minus 10 ℃, the inert mixed gas contains 5-15% by volume of carbon dioxide, and the balance is mixed gas of nitrogen and argon in any proportion. When the hydrate explosion suppressant generates gas and dust explosion, hydrate powder is rapidly diffused in an explosion phase, the concentration of an explosive is diluted, oxygen is isolated from being contacted with the explosive, and the continuous progress of an explosion chemical reaction is blocked; the dissociation of the gas hydrate powder absorbs heat, so that the temperature of an explosion area and the center of explosion flame can be quickly reduced, and the propagation of explosion waves and flame waves is inhibited; the gas hydrate powder is dissociated to release a large amount of inert gas, so that the oxygen concentration in the ambient air can be diluted to inhibit the subsequent explosion reaction; fine water mist released by dissociation of the gas hydrate powder can cool the explosion wave and the flame wave; the inorganic salt released after the dissociation of the gas hydrate powder can effectively intercept and consume free radicals generated in the explosive chain reaction so as to interrupt the chain reaction and achieve the multiple explosion suppression effect. The low-carbon mixed gas hydrate explosion suppressant is a high-efficiency explosion suppressant, consists of decomposable low-carbon gas hydrate powder particles, has the advantages of convenience in synthesis, low price, cleanness, environmental friendliness and obvious explosion suppression effect, and can effectively weaken energy required by explosion pressure wave propagation to block the explosion wave propagation.
The low-carbon mixed gas hydrate explosion suppressant is solid hydrate powder generated by inert mixed gas containing carbon dioxide, nitrogen and argon and a hydrating agent added with a certain amount of inorganic salt under the conditions of low temperature and high pressure, wherein the inert mixed gas contains 5-15% by volume of carbon dioxide, the nitrogen and the argon are mixed in any proportion, and the hydrating agent can be water or dry water.
After explosion of the hydrate explosion suppressant occurs, hydrate powder enters an explosion area to dilute the concentration of an explosive, and the explosive and air are isolated to inhibit continuous chemical reaction; the gas hydrate is decomposed to absorb a great deal of heat, so that the temperature of an explosion area and a flame area can be reduced, and the propagation energy of explosion waves and flame waves can be weakened; inert mixed gas of carbon dioxide, nitrogen and argon released by decomposition of the gas hydrate dilutes air around the explosive, so that the oxygen concentration is effectively reduced; the water released by the decomposition of the gas hydrate has the functions of heat absorption and temperature reduction; in addition, the released halogen anions and phosphate radicals can be combined with free radicals generated in the explosion process so as to interrupt chain reaction, and the released silicon dioxide can absorb heat generated by explosion and cover the surface of an explosive, so that the aim of explosion suppression is fulfilled.
The novel low-carbon mixed gas hydrate explosion suppressant has the advantages of a low-carbon inert gas explosion suppressant, a water system explosion suppressant and a carbon dioxide explosion suppressant, and has the characteristics which are not possessed by the three. The low-carbon mixed gas hydrate explosion suppressant has the advantages of small required storage space, large gas storage capacity and obvious cooling effect, solves the technical problems that the pure carbon dioxide explosion suppressant has strong greenhouse effect, the water system explosion suppressant has poor adhesion, and the low-carbon inert gas explosion suppressant cannot reduce the temperature of an explosion area in the prior art, can combine released halogen anions and phosphate radicals with free radicals generated in the explosion process to interrupt a chain reaction, and can absorb heat generated by explosion and cover the surface of an explosive by released silicon dioxide to achieve the purpose of explosion suppression. The raw materials for producing the hydrate explosion suppressant are only carbon dioxide, nitrogen, argon, inorganic salt and water or dry water, so that the hydrate explosion suppressant is non-toxic and pollution-free, and the global warming potential heat value of the released gas is close to 0, so that the hydrate explosion suppressant is clean and environment-friendly.
The purpose of the invention is realized by the following technical scheme:
a low-carbon mixed gas hydrate explosion suppressant is prepared by reacting inert gas containing carbon dioxide gas with water or dry water added with inorganic salt at the temperature of-10 to-8 ℃ under the pressure of 4 MPa to 10MPa to generate mixed gas hydrate, wherein the inert mixed gas contains 5 to 15 volume percent of carbon dioxide, and the balance of gas mixed by nitrogen and argon in any proportion, the inorganic salt is metal halide, silicon dioxide or potassium phosphate, the concentration of the inorganic salt is 0 to 0.1mol/L, and the inorganic salt is ground at the temperature of-10 ℃ and sieved to form hydrate powder with the particle size of less than 1.0 mm.
Preferably, the low-carbon hydrate explosion suppressant is a mixed gas hydrate generated by reacting inert gas containing carbon dioxide gas and water or dry water added with inorganic salt at the temperature of-5-4 ℃ under the pressure of 6-9 MPa, wherein the inert mixed gas contains 7-11% by volume of carbon dioxide, and the balance is gas mixed by nitrogen and argon in any proportion, the concentration of the inorganic salt is 0.01-0.07 mol/L, and the mixture is ground and sieved at the temperature of-10 ℃ to form hydrate powder with the particle size of less than 0.5 mm.
The explosion suppressant is applied when an explosion occurs, and once an explosion pressure wave signal is received, hydrate powder is sprayed into a space containing explosives, so that the concentration of the explosives is reduced, and the contact between the explosives and air is reduced; meanwhile, the gas hydrate is heated and decomposed, and a large number of water molecules are released to absorb heat efficiently so as to reduce the temperature of an explosion area and a flame area, and the released carbon dioxide, nitrogen and argon dilute the air around the explosive so as to reduce the oxygen concentration of the explosion area and the flame area; the released halogen anions and phosphate radicals can be combined with free radicals generated in the explosion process so as to interrupt chain reaction, and the released silicon dioxide can absorb heat generated by explosion and cover the surface of an explosive, so that the aim of explosion suppression is fulfilled. The explosion suppressant has the advantages of a water system explosion suppressant, a low-carbon inert gas explosion suppressant and a carbon dioxide explosion suppressant.
Compared with the prior art, the invention has the advantages and beneficial effects that:
during the explosion suppression process, hydrate powder enters an explosion area or a flame area to reduce the concentration of explosives, reduce the contact of the explosives and air, decompose and absorb heat to reduce the temperature of the explosion area and the flame area, released carbon dioxide, nitrogen and argon can dilute the oxygen concentration around the explosives, released water can form a water film on the surface of the explosives and reduce the temperature, released halogen anions and phosphate radicals can be combined with free radicals generated in the explosion process to interrupt a chain reaction, and released silicon dioxide can absorb heat generated by explosion and cover the surface of the explosives, so that the purpose of explosion suppression is achieved.
The explosion suppressant has the advantages of a carbon dioxide inhibitor, a water system explosion suppressant and a low-carbon inert gas explosion suppressant, and has the characteristics which are not possessed by the three. Compared with a water-based explosion suppressant, the hydrate explosion suppressant powder is contacted with an explosive and then is melted and decomposed into water, a water layer is formed on the surface of the explosive, and the contact of the explosive and air is isolated to a certain extent; compared with the carbon dioxide explosion suppressant, the global warming potential heat value of the gas released by the hydrate explosion suppressant is close to 0, and the greenhouse effect cannot be deepened; compared with the low-carbon inert gas explosion suppressant, the hydrate explosion suppressant can decompose and absorb heat by itself to reduce the temperature of an explosion area; compared with a carbon dioxide explosion suppressant, a water system explosion suppressant and a low-carbon inert gas explosion suppressant, halogen anions and phosphate radicals in the explosion suppressant can be combined with free radicals generated in the explosion process, and silicon dioxide can absorb heat generated by explosion and cover the surface of an explosive, so that the purpose of explosion suppression is achieved. The hydrate explosion suppressant decomposes to release water to isolate contact of explosives and oxygen, absorbs a large amount of heat, reduces the temperature of an explosion area and a flame area, absorbs shock waves generated by explosion, combines oxygen concentration, halogen anions and phosphate radicals in inert gas diluted air with free radicals generated in the explosion process to interrupt a chain reaction, and can absorb heat generated by explosion and cover the surface of the explosives, so that the hydrate explosion suppressant is a high-efficiency explosion suppressant.
In a word, the low-carbon mixed gas hydrate explosion suppressant is generated by adding inorganic salt-containing inert mixed gas containing carbon dioxide and water or dry water under the conditions of high pressure and low temperature, and is ground and sieved into crystalline hydrate powder with a certain particle size in a liquid nitrogen environment. The hydrate only needs a small amount of carbon dioxide, inert gas, water and cheap inorganic salt, the production raw materials are low in price, low-carbon emission is realized, cleanness and environmental protection are realized, the preparation is convenient, the explosion suppression agent inhibits explosion propagation from multiple aspects such as physical explosion suppression, chemical explosion suppression and the like, multiple explosion suppression effects are realized, the explosion suppression is rapid, the explosion suppression effect is obvious, the explosion suppression effect is at least improved by 50 percent compared with the explosion suppression effect of the carbon dioxide explosion suppression agent, the explosion suppression agent is a high-efficiency explosion suppression agent, great innovation is realized on the explosion suppression agent, and the economic and social benefits are huge.
Claims (4)
1. A preparation method of a low-carbon mixed gas hydrate explosion suppressant is characterized by comprising the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt into a solvent to ensure that the mass content of the inorganic salt is 0.001-0.1 mol/L;
the solvent is water or dry water; the inorganic salt is silicon dioxide, potassium phosphate or metal halide ABnA is one of Na, Mg, K or Ca, B is one of F, Cl, Br or I, and n =1, 2;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 5-15% of carbon dioxide and 85-95% of mixed gas of nitrogen and argon are mixed together, and the volume ratio of nitrogen to argon is arbitrary;
(3) and (3) mixing reaction:
filling inert mixed gas into a hydration agent, leading the pressure to reach 6-10MPa, reacting for 300min at the temperature of minus 10-8 ℃ to generate mixed gas hydrate, and crushing the mixed gas hydrate generated by the reaction into hydrate powder with the grain diameter less than 1.0mm at the temperature of minus 10 ℃.
2. The preparation method of the low-carbon mixed gas hydrate explosion suppressant according to claim 1, characterized by comprising the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt silicon dioxide into water to ensure that the mass content of the silicon dioxide is 0.05 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: mixing 10% of carbon dioxide and 90% of mixed gas of nitrogen and argon, wherein the volume ratio of nitrogen to argon is 1: 1;
(3) and (3) mixing reaction:
charging inert mixed gas into the hydration agent, making the pressure reach 7MPa, reacting for 150min at 3 deg.C to generate mixed gas hydrate, and pulverizing the mixed gas hydrate generated by reaction into hydrate powder with particle size less than 1.0mm at-10 deg.C.
3. The preparation method of the low-carbon mixed gas hydrate explosion suppressant according to claim 1, characterized by comprising the following steps:
(1) and preparing a hydrating agent:
adding inorganic salt NaCl into dry water to ensure that the mass content of the NaCl is 0.01 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 7% of carbon dioxide, and 93% of mixed gas of nitrogen and argon, wherein the volume ratio of nitrogen to argon is 1: 3;
(3) and (3) mixing reaction:
charging inert mixed gas into the hydration agent, making the pressure reach 6MPa, reacting for 160min at 1 deg.C to generate mixed gas hydrate, and pulverizing the generated mixed gas hydrate into hydrate powder with particle size less than 1.0mm at-10 deg.C.
4. The preparation method of the low-carbon mixed gas hydrate explosion suppressant according to claim 1, characterized by comprising the following steps:
(1) and preparing a hydrating agent:
adding an inorganic salt MgF into solvent dry water to ensure that the mass content of the inorganic salt is 0.03 mol/L;
(2) preparing inert mixed gas:
the inert mixed gas is prepared from the following components in percentage by volume: 14% of carbon dioxide and 86% of mixed gas of nitrogen and argon are mixed together, and the volume ratio of the nitrogen to the argon is arbitrary;
(3) and (3) mixing reaction:
filling inert mixed gas into a hydration agent, leading the pressure to reach 8MPa, reacting for 100-240min at the temperature of minus 10-5 ℃ to generate mixed gas hydrate, and crushing the mixed gas hydrate generated by the reaction into hydrate powder with the grain diameter less than 1.0mm at the temperature of minus 10 ℃.
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| GB2018561A (en) * | 1978-04-05 | 1979-10-24 | Pennwalt Corp | Potassium bromate composition |
| CN101514300A (en) * | 2009-03-23 | 2009-08-26 | 江苏工业学院 | Method for preparing gas hydrate accelerant |
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