CN117982822A - Explosion suppressant composition and explosion suppression method for confined space containing residual oil or oil gas - Google Patents
Explosion suppressant composition and explosion suppression method for confined space containing residual oil or oil gas Download PDFInfo
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- 238000004880 explosion Methods 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 230000001629 suppression Effects 0.000 title claims abstract description 29
- 239000008263 liquid aerosol Substances 0.000 claims abstract description 60
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229960003237 betaine Drugs 0.000 claims abstract description 48
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 45
- -1 alkyl betaine Chemical compound 0.000 claims abstract description 41
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 19
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 38
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 119
- 239000007788 liquid Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 16
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- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000001294 propane Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000013022 venting Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
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- 238000004088 simulation Methods 0.000 description 5
- 230000001066 destructive effect Effects 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/06—Fire prevention, containment or extinguishing specially adapted for particular objects or places of highly inflammable material, e.g. light metals, petroleum products
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C4/00—Flame traps allowing passage of gas but not of flame or explosion wave
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- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
Abstract
The invention relates to the technical field of safety and environmental protection in petrochemical industry or chemical industry, and discloses an explosion suppression agent composition and an explosion suppression method for a limited space containing residual oil or oil gas. The explosion suppressant composition contains alkyl fluorocarbon betaine, polyoxyethylene ether and alkyl betaine. The method comprises the following steps: (1) Providing an explosion suppressant aqueous solution, wherein the explosion suppressant aqueous solution comprises the explosion suppressant composition; (2) And (3) conveying the explosion suppressant aqueous solution into a limited space containing residual oil or oil gas in a liquid aerosol form for oil-gas replacement. The liquid aerosol formed by the explosion suppressant composition can effectively reduce the risk of oil gas explosion in an oil-containing limited space.
Description
Technical Field
The invention relates to the technical field of safety and environmental protection in petrochemical or chemical industries, in particular to an explosion suppression agent composition and an explosion suppression method for a limited space containing residual oil or oil gas.
Background
The limited space containing oil gas belongs to zone 0 in the explosion danger zone, and the explosion accident easily occurs when the ignition source is encountered. The hydrocarbon which is easy to remain and volatilize in the limited space in the petrochemical industry is easy to cause accidents such as poisoning choking and fire explosion during the operation of the limited space due to incomplete purging and replacement, ineffective isolation or improper individual protection, and the like, and the accidents generally have the characteristics of rapid development, high rescue difficulty and high mortality rate.
The main measure for preventing the explosion accident of the limited space is to control the concentration of the oil gas in the space to be far lower than the explosion lower limit of the oil gas. Before the operation of the limited space containing oil and gas, the technical method for reducing the oil and gas concentration mainly comprises the steps of replacement, namely, replacement of air, replacement of nitrogen or carbon dioxide, steam filling or water filling, and the like. The conventional replacement technique has the following problems: the risk is unpredictable, time consuming and energy consuming. In addition, in the traditional replacement process, the residual oil product in the limited space still volatilizes continuously, and the volatilization speed of the residual oil product in the replacement process is increased due to the fact that the pressure in the space is lower than the saturated vapor pressure of the oil product. Therefore, the conventional replacement technology cannot thoroughly eliminate oil gas in a limited space and cannot put an end to operational dangers.
Patent application CN113856119A discloses a precise spraying method for inhibiting gas explosion in a limited variable-volume space by fine water mist, in particular relates to a precise spraying method for inhibiting gas explosion in a limited variable-volume space by fine water mist, and belongs to the technical field of explosion prevention. The device comprises a flame development stage determining module, a flame detection and installation module, a water mist spraying device and an excitation module; the flame development stage determining module is used for determining a flame development process in time and space and dividing explosion flame development stages; the flame detection installation module is used for detecting flame positions; the fine water mist spraying device and the excitation module are used for exciting and spraying fine water mist in a specific flame area. The method mainly solves the problem that spraying effect is poor by using fine water mist after gas explosion occurs in a limited variable volume space. Through the technical scheme of the patent application, the development stage of the gas explosion flame can be accurately identified, accurate stage division is performed, the stage with the best explosion suppression effect is found out, fine water mist spraying is performed, and the purpose of utilizing the fine water mist to perform high-efficiency gas explosion suppression is achieved.
Patent application CN113090956B discloses a zoned active explosion-proof and explosion-suppression device and a control method thereof, which utilizes fine water mist and inert gas to form an air-mist explosion-proof curtain to separate a large space into relatively independent explosion-proof zones, and the rapid response explosion suppressor in the center of each zone is matched to ensure safe production of the large space. The active explosion-proof explosion suppression device of each partition mainly comprises a detector, an explosion-proof device, an explosion suppression device and a controller; the explosion-proof device of each subarea at least comprises four groups of spraying devices, and the explosion-suppression device at least comprises an explosion suppressor. The explosion suppression device is designed with an explosion suppression device based on a double-film explosion principle, so that the response speed of the explosion suppression device is improved, and the stability and reliability of the explosion suppression effect are ensured; the explosion-proof device innovatively utilizes the high-pressure rotational flow wind-water spraying device and the single water nozzle to form an integrated explosion-suppression, explosion-proof and explosion-proof system; the zoned active explosion-proof and explosion-suppression device judges and analyzes through the external environment change condition fed back by the detector, and ensures the reliability and stability of explosion-proof and explosion-suppression in the large-scale chemical production space.
Patent application CN109173114a discloses a fine water mist automatic explosion suppression device for explosion venting premixed flame to induce vapor cloud explosion and an explosion suppression method thereof, which comprises a gas explosion venting device, a hemispherical vapor cloud cluster device and an explosion suppression device; the gas explosion venting device consists of a gas pipeline, a reducing joint and an explosion venting port channel; a sensor is arranged in the middle inner cavity of the gas pipeline; the tail end of the explosion venting port channel is provided with an explosion venting port; the hemispherical vapor cloud cluster device is formed by sealing premixed gas by a hemispherical film; the explosion suppression device consists of a sensor, a controller and an explosion suppression device, wherein the explosion suppression device consists of a high-pressure water pipe, a high-pressure pump, an electromagnetic valve and a water mist nozzle device. When the pipeline is overpressured to a certain set value of the rupture disk, the rupture disk is broken; the sensor receives the pipeline flame signal and then sends out a command through the controller, so that the water spraying device works as a premixed flame for the explosion venting port and the hemispherical vapor cloud cluster to cool and extinguish the fire. Reasonable structure, high practicability, easy disassembly, convenient inspection and replacement, and scientific and effective explosion suppression considering various explosion suppression details.
However, the solutions of the above patent applications are only applicable to special sites where fixed flame detectors and water mist facilities are required.
Disclosure of Invention
The invention aims to solve the problem that explosion risks exist in limited spaces containing residual oil products or oil gas, and provides an explosion suppressant composition and an explosion suppression method for the limited spaces containing the residual oil products or the oil gas.
The inventor of the present invention has found through intensive studies that one of the effective means for preventing continuous volatilization of hydrocarbon gas is to provide a barrier film on the surface of hydrocarbon liquid. The isolating film can be permanently present on the surface of hydrocarbon liquid to block the diffusion of hydrocarbon molecules into gas-phase environment. Because the hydrocarbon liquid surface in a truly confined space is not regular in shape and may be present on all around the walls of the storage vessel, solid films cannot be used to isolate the oil from the environment, but only liquid films can be used for sealing. Because the surface energy of the oil is low, the surface energy of the liquid forming the liquid film on the oil surface needs to be lower so as to spread on the oil surface to form the isolating film. The fluorocarbon surfactant or some special nonionic surfactant molecules in the solution can be stably adsorbed on the gas-liquid interface, so that the surface tension of the solution is reduced to below 20 mN/m. On the oil-water interface, the surfactant molecules with hydrophobic and oleophobic chain ends can be stably adsorbed on the oil-water interface and are arranged into layers to maintain the stability of the oil-water interface. When the solution forms a liquid film on the surface of the oil product, the surfactant molecular layers of the gas-liquid interface and the oil-water interface are both helpful for blocking the diffusion of oil gas molecules into the gas phase space, thereby inhibiting the volatilization of oil gas. Therefore, the inventor of the invention strives to develop an explosion suppressant solution containing a special surfactant, the explosion suppressant solution can be atomized to form liquid aerosol, and liquid drops of the liquid aerosol are deposited on the surface of residual oil products in a limited space to form a layer of liquid phase seal so as to inhibit continuous volatilization of oil gas, thereby ensuring that the concentration of the oil gas in the space can be effectively reduced and the risk of oil gas explosion in the process of oil gas replacement in the limited space.
In order to achieve the above object, the present invention provides in one aspect an explosion suppressant composition comprising an alkyl fluorocarbon betaine, a polyoxyethylene ether, and an alkyl betaine.
Preferably, the weight ratio of the alkyl fluorocarbon betaine, the polyoxyethylene ether and the alkyl betaine is 1:0.1-0.7:2-8, more preferably 1:0.2-0.5:4-6.
Preferably, the alkyl group in the alkyl fluorocarbon betaine is a C12-C16 alkyl group. More preferably, the alkyl fluorocarbon betaine has the formula C 21H19F23N2O6.
Preferably, the polyoxyethylene ether has a molecular weight of 300 to 500, more preferably 350 to 450.
Preferably, the alkyl group in the alkyl betaine is a C12-C16 alkyl group. More preferably, the alkyl betaine has the formula C 20H40N2O3.
Preferably, the explosion suppressant composition further comprises triethanolamine phosphate and/or sodium alkyl sulfate.
Preferably, the weight ratio of the alkyl fluorocarbon betaine to the triethanolamine phosphate is 1:0.01-0.5, preferably 1:0.03-0.07.
Preferably, the weight ratio of the alkyl fluorocarbon betaine to the sodium alkyl sulfate is 1:0.05-0.3, preferably 1:0.05-0.15.
Preferably, the alkyl in the sodium alkyl sulfate is a C12-C16 alkyl.
The second aspect of the invention provides an explosion suppression method for a confined space containing residual oil or oil gas, comprising the following steps:
(1) Providing an aqueous explosion suppressant solution comprising an explosion suppressant composition as described above;
(2) And (3) conveying the explosion suppressant aqueous solution into a limited space containing residual oil or oil gas in a liquid aerosol form for oil-gas replacement.
Preferably, the concentration of the aqueous explosion suppressant solution is 0.1-2wt%, more preferably 0.2-1wt%, and still more preferably 0.26-0.5wt%.
Preferably, the liquid aerosol has a particle size of 2-50 μm.
Preferably, the content of the liquid aerosol in the confined space is made to be 0.5 to 5wt%, more preferably 2 to 3wt%.
The technical scheme of the invention can solve the problem of explosion risk of the limited space containing residual oil or oil gas. The explosion suppressant composition can be prepared into an environment-friendly explosion suppressant solution with low surface tension, can be subjected to superfine atomization to form liquid aerosol, and is pneumatically conveyed into a limited space to replace oil gas in the limited space. In the limited space oil gas replacement process, the oil gas concentration in the limited space is maintained below 10% LEL (lower explosion limit) for more than 24 hours. In the oil gas replacement process, explosion suppressant liquid drops in liquid aerosol are deposited on the surface of an oil product to form an isolating film, so that the volatilization of oil gas is blocked; meanwhile, the gas-liquid interface of the liquid drop and the liquid film can adsorb oil gas molecules, so that the oil gas concentration is reduced. In addition, the explosion suppressant liquid aerosol is suspended in a limited space, and the energy or the destructive power of oil gas explosion in the space can be obviously reduced. Therefore, the liquid aerosol formed by the explosion suppressant composition provided by the invention can effectively reduce the oil gas explosion risk in an oil-containing limited space.
Specifically, the mechanism for reducing the explosion risk of the limited space or inhibiting the explosion of the limited space in the technical scheme of the invention mainly has three aspects: a) The liquid drops are deposited on the surface of the residual oil product to form liquid film sealing, so that volatilization of oil gas is inhibited; b) The liquid drops in the liquid aerosol can absorb oil gas molecules in the space, so that the oil gas concentration is reduced; c) The explosion suppressant liquid aerosol is suspended in a limited space, so that the energy or destructive power of oil gas explosion in the space can be reduced.
The technical scheme of the invention can be applied to the limited space containing residual oil or oil gas in the petrochemical or chemical field, and can effectively reduce the oil gas concentration and the oil gas explosion risk in the limited space, thereby guaranteeing the operation safety of the subsequent limited space, and having larger application prospect and market space in the petrochemical safety and environmental protection field.
The technical scheme of the invention is suitable for all limited places containing residual oil products or oil gas, and the explosion suppressant liquid aerosol can reach all places in the limited space along with the replacement air flow, so that liquid seal is formed for the residual oil products to suppress the volatilization of the oil gas.
Drawings
FIG. 1 is a graph of the spreading of an aqueous explosion suppressant solution and an aqueous ordinary surfactant solution on the surface of xylene according to the present invention, wherein the left is a graph of the spreading of an aqueous explosion suppressant solution according to the present invention on the surface of xylene, and the right is a graph of the spreading of an aqueous ordinary surfactant solution on the surface of xylene;
FIG. 2 is a graph showing the particle size distribution of droplets of an aerosol solution of an aqueous explosion suppressant solution of the present invention using an ultrasonic atomizer;
FIG. 3 is a schematic view of 5 hydrocarbon concentration detection ports provided in a simulated confined space in example 1 and comparative example 1;
FIG. 4 shows concentration detection data for displacement of oil and gas in a confined space using an explosion suppressant liquid aerosol in example 1;
FIG. 5 shows concentration detection data for air alone used to displace hydrocarbon in a confined space in comparative example 1;
FIG. 6 shows oil and gas concentration measurements in a confined space for explosion suppressant liquid aerosol reduction in example 5;
FIG. 7 is a process diagram of an experiment for suppressing the oil and gas explosion energy in a confined space with the explosion suppressant liquid aerosol of example 6;
Fig. 8 shows graphs of the explosion phenomenon of the plastic bags in the experiments of example 6 and comparative example 2, in which fig. 8a is the explosion phenomenon of comparative example 2 (i.e., the inside of the plastic bag is a mixture of propane and air), and fig. 8b is the explosion phenomenon of example 6 (i.e., the propane and explosion suppressant liquid aerosol mixture, in which the propane content is 4.2% by volume and the explosion suppressant liquid aerosol content is 2.5% by weight).
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The explosion suppressant composition disclosed by the invention contains alkyl fluorocarbon betaine, polyoxyethylene ether and alkyl betaine.
In the present invention, the weight ratio of the alkyl fluorocarbon betaine, the polyoxyethylene ether, and the alkyl betaine may be 1:0.1-0.7:2-8, preferably 1:0.2-0.5:4-6.
In the present invention, the alkyl group in the alkyl fluorocarbon betaine may be a C12-C16 alkyl group. In a most preferred embodiment, the alkyl fluorocarbon betaine has a formula of C 21H19F23N2O6.
In the present invention, the molecular weight of the polyoxyethylene ether is preferably 300 to 500, more preferably 350 to 450.
In the present invention, the alkyl group in the alkyl betaine may be a C12-C16 alkyl group. In a most preferred embodiment, the alkyl betaine has the formula C 20H40N2O3.
In a preferred embodiment of the present invention, the explosion suppressant composition further comprises triethanolamine phosphate and/or sodium alkyl sulfate.
Wherein the weight ratio of the alkyl fluorocarbon betaine to the triethanolamine phosphate can be 1:0-0.5, preferably 1:0.01 to 0.5, more preferably 1:0.03-0.07.
Wherein the weight ratio of the alkyl fluorocarbon betaine to the sodium alkyl sulfate may be 1:0-0.3, preferably 1:0.05-0.3, more preferably 1:0.05-0.15.
In the present invention, the alkyl group in the sodium alkyl sulfate may be a C12-C16 alkyl group. In a specific embodiment, the sodium alkyl sulfate is sodium dodecyl sulfate.
According to a preferred embodiment of the present invention, the explosion suppressant composition contains alkyl fluorocarbon betaine, polyoxyethylene ether, alkyl betaine, triethanolamine phosphate and sodium alkyl sulfate, wherein the weight ratio of alkyl fluorocarbon betaine, polyoxyethylene ether, alkyl betaine, triethanolamine phosphate and sodium alkyl sulfate is 1:0.1-0.7:2-8:0.01-0.5:0.05-0.3, preferably 1:0.2-0.5:4-6:0.03-0.07:0.05-0.15.
The explosion suppression method for the limited space containing residual oil or oil gas comprises the following steps:
(1) Providing an aqueous explosion suppressant solution comprising an explosion suppressant composition as described above;
(2) And (3) conveying the explosion suppressant aqueous solution into a limited space containing residual oil or oil gas in a liquid aerosol form for oil-gas replacement.
In the existing limited space oil gas replacement process, residual oil products are volatilized continuously, so that the oil gas concentration in the space cannot be reduced thoroughly and effectively, and the oil gas explosion risk is eliminated. However, according to the method disclosed by the invention, the environment-friendly explosion suppressant aqueous solution with low surface tension is used, so that the surface of residual oil spread in a limited space can be deposited to form a layer of liquid-phase sealing film, thus continuous oil gas volatilization of the residual oil can be inhibited, and oil gas molecules in the space can be absorbed, thus the oil gas concentration in the space can be effectively reduced and the risk of oil gas explosion in the space can be reduced in the process of oil gas replacement in the limited space. In a displacement test experiment, the method disclosed by the invention can maintain the oil gas concentration in a limited space below 10% LEL for more than 24 hours. In a more preferred embodiment, the energy or destructive power of the hydrocarbon explosion can be significantly reduced when 2-3wt% (most preferably 2.5 wt%) of the explosion suppressant liquid aerosol is contained in the confined space.
In the step (1), the process of providing the explosion suppressant aqueous solution specifically comprises the following steps: the main components of the explosion suppressant composition (such as alkyl fluorocarbon betaine, polyoxyethylene ether, alkyl betaine, optional polyoxyethylene propylene ether, optional triethanolamine phosphate and optional sodium alkyl sulfate) are added into deionized water, the temperature is raised to 40-60 ℃, and the mixture is stirred for 4-6 hours at the rotating speed of 40-60rpm, so that the explosion suppressant aqueous solution is prepared.
In the method of the present invention, the concentration of the explosion suppressant aqueous solution may be 0.1 to 2wt%, preferably 0.2 to 1wt%, and more preferably 0.26 to 0.5wt%.
In step (2), the process of forming the liquid aerosol from the aqueous explosion suppressant solution may be performed using an ultra-fine atomization device (e.g., an ultrasonic atomization device or a high velocity air stream impingement atomization device).
In the method of the present invention, the particle size of the liquid aerosol may be 1 to 100. Mu.m, preferably 2 to 50. Mu.m.
In the method of the present invention, the content of the liquid aerosol in the confined space is preferably 0.5 to 5wt%, more preferably 2 to 3wt%, most preferably 2.5wt%.
In the specific implementation process, an inlet and an outlet are arranged in a limited space, oil products in the limited space are volatilized continuously, a compressed gas atomizer is adopted to form a liquid aerosol from an explosion suppressant solution, and the liquid aerosol enters from the inlet of the limited space through pneumatic conveying; in the limited space, liquid drops of liquid aerosol can be deposited on the surface of an oil product and spread to form a thin liquid film, so as to play a role in liquid sealing and block volatilization of oil gas; the explosion suppressant liquid film on the surface of the oil product is formed by liquid drop deposition, so that the liquid film is very thin, and the liquid film is in a dynamic balance process on the surface of the oil product, so that the explosion suppressant liquid film is required to be continuously supplied to the liquid seal of the explosion suppressant liquid film on the surface of the oil product for a long time; liquid aerosols enter from the inlet of the confined space and displacement gas exits from the outlet of the confined space.
The explosion suppressant composition of the present invention and the method of suppressing an explosion in a confined space containing residual oil or gas are further described by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
In the following examples and comparative examples, some reagent sources were as follows:
Alkyl fluorocarbon betaine, molecular formula C 21H19F23N2O6, available from fire fighting agent limited in Yangzhou Jiang Ya;
polyoxyethylene ether with molecular weight of 400 is purchased from national drug reagent;
alkyl betaine, molecular formula C 20H40N2O3, available from Yangzhou Jiang Ya fire fighting agent Co., ltd;
Triethanolamine phosphate, purchased from chinese medicine reagent;
sodium dodecyl sulfate, purchased from chinese medicinal agents.
Experimental example 1
0.403G of alkyl fluorocarbon betaine, 0.121g of polyoxyethylene ether, 2.016g of alkyl betaine, 0.020g of triethanolamine phosphate and 0.040g of sodium alkyl sulfate are added into 1000mL of deionized water, the temperature is raised to 50 ℃, and stirring is carried out for 5 hours at the rotating speed of 50rpm, so as to prepare the explosion suppressant aqueous solution.
The explosion suppressant aqueous solution was slowly dropped onto the xylene surface with a syringe at room temperature. As a result, the explosion suppressant aqueous solution rapidly spreads to form a thin liquid film on the surface of xylene, as shown in FIG. 1 (left).
0.7G of polyoxyethylene ether, 0.15g of triethanolamine phosphate, 0.05g of methylbenzotriazole and 0.1g of tetrahydrofurfuryl alcohol are added to 99mL of deionized water, the temperature is raised to 50℃and stirred at 50rpm for 5 hours, and an aqueous surfactant solution is prepared.
The aqueous surfactant solution was slowly dropped onto the xylene surface using a syringe. As a result, droplets of the aqueous surfactant solution could not spread out to form a film on the surface of xylene, as shown in fig. 1 (right).
As can be seen from FIG. 1, the explosion suppressant aqueous solution of the present invention has lower surface energy and lower surface tension than the conventional surfactant solution, and can be spread on the oil surface to form a liquid film and cover the oil surface.
Experimental example 2
An aqueous solution of explosion suppressant was prepared as in experimental example 1.
And forming the explosion suppressant aqueous solution into liquid aerosol by adopting an ultrasonic atomization device, measuring the droplet size of the liquid aerosol by a laser particle sizer, wherein the measured droplet size range is 2-50 mu m, and the particle size distribution diagram is shown in figure 2.
Example 1
(1) Preparation of an aqueous explosion suppressant solution
0.403G of alkyl fluorocarbon betaine, 0.121g of polyoxyethylene ether, 2.016g of alkyl betaine, 0.020g of triethanolamine phosphate and 0.040g of sodium alkyl sulfate are added into 1000mL of deionized water, the temperature is raised to 50 ℃, and stirring is carried out for 5 hours at the rotating speed of 50rpm, so as to prepare an explosion suppressant aqueous solution A1.
(2) Constructing oil tank simulation experiments
A simulated oil tank (volume about 30m 3) is enclosed by a plastic film and a steel bar support frame and is used as a limited space, and an inlet and an outlet for replacement gas are arranged, as shown in figure 3. And the oil product is placed in the limited space, and the oil product is volatilized continuously in the limited space.
(3) Oil and gas displacement
And atomizing the explosion suppressant aqueous solution A1 by adopting a compressed gas atomizer to form liquid aerosol, enabling pneumatic transmission to enter from an inlet of the restricted space, and enabling replacement gas to flow out from an outlet of the restricted space. Wherein, the equipment parameters of the compressed gas atomizer are: the gas flow rate range is 30m 3·min-1, and the particle size range of the generated liquid drops is 2-50 mu m; the air supply adopts a screw compressor, and the air supply parameters are as follows: 30m 3·min-1, and the air supply pressure is 1.0MPa.
At different heights and depths of the main area in the simulated confined space, 5 oil and gas concentration detection ports are provided, as shown in fig. 3. The oil gas concentration measurement adopts a flammable gas detector, the flammable gas measurement range is 0-100% LEL, and the measurement accuracy is 1% LEL.
The explosion suppressant liquid aerosol is adopted to replace oil gas in the limited space, and oil gas concentration detection data in the limited space are simulated as shown in fig. 4.
As can be seen from fig. 4, after 5 hours of aerosol displacement of the explosion suppressant liquid, the oil gas concentration in the main area of the space is reduced to below 10% LEL; moreover, no oil gas is volatilized for the second time in the replacement process, and the oil gas can be maintained for a long time, and the reason is that: tiny liquid drops in the explosion suppressant liquid aerosol are deposited on the surface of the oil product and spread into a film, so that a liquid seal is formed for the oil product.
Therefore, by adopting the explosion suppressant liquid aerosol replacement method, the oil gas concentration in a limited space can be effectively reduced, and the oil gas explosion risk in the space is eliminated.
Comparative example 1
The hydrocarbon displacement was performed as in example 1, except that air alone was used to displace hydrocarbon in the confined space, and the hydrocarbon concentration detection data in the confined space was as shown in fig. 5.
Because the oil gas in the simulated limited space is volatilized continuously in the replacement process, after 15 hours of air replacement, the concentration of the oil gas in the main area in the space is still above 25% LEL, so that the oil gas explosion risk in the limited space cannot be effectively eliminated by adopting an air replacement mode alone.
Example 2
(1) Preparation of an aqueous explosion suppressant solution
Unlike example 1, an aqueous explosion suppressant solution A2 was prepared without adding triethanolamine phosphate and sodium alkyl sulfate.
(2) Constructing oil tank simulation experiments
The same as in example 1.
(3) Oil and gas displacement
Unlike example 1, oil and gas displacement was performed with an aqueous explosion suppressant solution A2.
As a result, after 5 hours of the explosion suppressant liquid aerosol displacement, the oil and gas concentration in the main area of the space was reduced to 20% LEL.
Example 3
(1) Preparation of an aqueous explosion suppressant solution
Unlike example 1, an aqueous explosion suppressant solution A3 was prepared without adding triethanolamine phosphate.
(2) Constructing oil tank simulation experiments
The same as in example 1.
(3) Oil and gas displacement
Unlike example 1, oil and gas displacement was performed with an aqueous explosion suppressant solution A3.
As a result, after 5 hours of the explosion suppressant liquid aerosol displacement, the oil and gas concentration in the main area of the space was reduced to 16% LEL.
Example 4
(1) Preparation of an aqueous explosion suppressant solution
Unlike example 1, an aqueous explosion suppressant solution A4 was prepared without adding sodium alkyl sulfate.
(2) Constructing oil tank simulation experiments
The same as in example 1.
(3) Oil and gas displacement
Unlike example 1, oil and gas displacement was performed with an aqueous explosion suppressant solution A4.
As a result, after 5 hours of the explosion suppressant liquid aerosol displacement, the oil and gas concentration in the main area of the space was reduced to 15% LEL.
Example 5
(1) Preparation of an aqueous explosion suppressant solution
0.403G of alkyl fluorocarbon betaine, 0.081g of polyoxyethylene ether, 2.418g of alkyl betaine, 0.012g of triethanolamine phosphate and 0.020g of sodium alkyl sulfate are added into 1000mL of deionized water, the temperature is raised to 50 ℃, and stirring is carried out for 5 hours at the rotating speed of 50rpm, so as to prepare an explosion suppressant aqueous solution A5.
(2) Oil gas experiment and concentration monitoring in explosion suppressant liquid aerosol absorption limited space
A plastic bag (4 m 3) is used for enclosing a simulated limited space. First, gasoline was placed in an open container (volume 5L) and placed in a confined space. As the gasoline volatilizes, the concentration of oil and gas in the simulated confined space increases from 0 to 45% LEL (lower explosion limit), and then the gasoline container is removed from the simulated confined space. Secondly, atomizing the explosion suppressant water solution A5 by utilizing an ultrasonic atomizer to form liquid aerosol, and entering a simulated restricted space along with water vapor. As the liquid aerosol and water vapor enter the simulated confined space, the volume of the plastic bag (simulated confined space) expands. When the volume of the plastic bag is expanded to the limit, the supply of the liquid aerosol is stopped, and after the volume of the plastic bag is contracted, the liquid aerosol is supplied. In the simulated confined space, liquid aerosol liquid drops are deposited on the wall surface to form a liquid film, and the gas-liquid interface of the liquid drops and the liquid film absorbs oil gas molecules, so that the oil gas concentration in the simulated confined space is continuously reduced.
Experimental testing found that it took about 40 minutes to simulate the drop in oil and gas concentration in the confined space from 45% LEL to below 20% LEL, as shown in fig. 6. The particle size distribution of the explosion suppressant liquid aerosol is in the range of 2-50 mu m, and the micro-droplet group has larger specific surface area; under the action of electrostatic force and Van der Waals force, the gas-liquid interface of the liquid aerosol can effectively absorb oil gas molecules in the space, so that the oil gas concentration in the space is reduced.
Example 6
(1) Preparation of an aqueous explosion suppressant solution
0.403G of alkyl fluorocarbon betaine, 0.202g of polyoxyethylene ether, 1.612g of alkyl betaine, 0.028g of triethanolamine phosphate and 0.060g of sodium alkyl sulfate are added into 1000mL of deionized water, the temperature is raised to 50 ℃, and stirring is carried out for 5 hours at the rotating speed of 50rpm, so as to prepare the explosion suppressant aqueous solution A6.
(2) Experiment for inhibiting oil gas explosion energy in limited space by explosion suppressant liquid aerosol
An experiment for suppressing oil-gas explosion characteristics by designing explosion suppressant liquid aerosol is shown in fig. 7. The confined space was simulated with a closed plastic bag having a volume of 3.0m 3. First, a propane air mixture having a concentration of 30% of 1.5Nm 3 was injected into the plastic bag through a propane gas cylinder, with propane as an oil and gas component in a confined space. Then, the ultra-fine atomizer was turned on, and an explosion suppressant liquid aerosol (particle size distribution was in the range of 2 to 50 μm) was produced using the explosion suppressant aqueous solution A6, and a certain amount (0.2 kg, 0.4kg, 0.6kg, 0.8 kg) of the explosion suppressant liquid aerosol was injected into the bag. The liquid aerosol mainly consists of tiny liquid drops and water vapor, and the mass of the liquid aerosol added into the space can be measured by weighing the liquid aerosol back and forth through the superfine atomizer. Finally, compressed air is added into the bag through an air compressor until the plastic bag is full, so that the content of the explosion suppressant aerosol in the plastic bag is 2.5wt%.
When the oil gas explosion characteristics in the limited space are tested, propane in the plastic bag is ignited remotely through the igniter, and the mixed gas in the bag is exploded. The explosion pressure of the gas mixture in the bag is measured by a pressure measuring system (high-sensitivity pressure sensor).
Comparative example 2
An experiment was performed in the same manner as in the step (2) in example 6, specifically, 1.0Nm 3 propane was first added to the plastic bag as the oil and gas component in the bag. Compressed air is then added to the bag until the plastic bag is full.
When the oil gas explosion characteristics in the limited space are tested, propane in the plastic bag is ignited remotely through the igniter, and the mixed gas in the bag is exploded. The explosion pressure of the gas mixture in the bag is measured by a pressure measuring system (high-sensitivity pressure sensor).
The experiment in which the bag contained an explosion suppressant liquid aerosol (i.e., example 6) was compared to comparative example 2 to characterize the ability of the explosion suppressant liquid aerosol to suppress oil and gas explosions in confined spaces.
The explosion of comparative example 2 (i.e., the mixture of propane and air in the plastic bag) is shown in fig. 8a, and there is a remarkable explosion, and the flame after the explosion is spread over the entire simulation limited space. Example 6 (i.e., a propane and explosion suppressant liquid aerosol mixture having a propane content of 4.2% by volume and an explosion suppressant liquid aerosol content of 2.5% by weight) shows the phenomenon of explosion as shown in fig. 8b, with regional explosion occurring only in the lower portion of the simulated confined space and no significant explosion occurring in the upper confined space.
Therefore, the explosion suppressant liquid aerosol with the content of 2.5 weight percent in the limited space can effectively suppress oil gas explosion in the space, and reduce the probability and explosion destructive power of the oil gas explosion in the space.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. An explosion suppressant composition is characterized by comprising alkyl fluorocarbon betaine, polyoxyethylene ether and alkyl betaine.
2. The explosion suppressant composition of claim 1, wherein the weight ratio of said alkyl fluorocarbon betaine, said polyoxyethylene ether, and said alkyl betaine is 1:0.1-0.7:2-8, preferably 1:0.2-0.5:4-6.
3. The explosion suppression composition according to claim 1 or 2, wherein the alkyl group in the alkyl fluorocarbon betaine is a C12-C16 alkyl group;
Preferably, the alkyl fluorocarbon betaine has a formula of C 21H19F23N2O6.
4. The explosion suppressant composition according to claim 1 or 2, wherein the polyoxyethylene ether has a molecular weight of 300-500, more preferably 350-450.
5. The explosion suppression composition according to claim 1 or 2, wherein the alkyl group in the alkyl betaine is a C12-C16 alkyl group;
preferably, the alkyl betaine has a formula of C 20H40N2O3.
6. The explosion suppressant composition of any one of claims 1-5, further comprising triethanolamine phosphate and/or sodium alkyl sulfate;
Preferably, the weight ratio of the alkyl fluorocarbon betaine to the triethanolamine phosphate is 1:0.01-0.5, preferably 1:0.03-0.07;
preferably, the weight ratio of the alkyl fluorocarbon betaine to the sodium alkyl sulfate is 1:0.05-0.3, preferably 1:0.05-0.15;
preferably, the alkyl in the sodium alkyl sulfate is a C12-C16 alkyl.
7. A method of suppressing explosion in a confined space containing residual oil or gas, the method comprising:
(1) Providing an aqueous explosion suppression agent solution comprising the explosion suppression agent composition of any one of claims 1-6;
(2) And (3) conveying the explosion suppressant aqueous solution into a limited space containing residual oil or oil gas in a liquid aerosol form for oil-gas replacement.
8. The method of claim 7, wherein the concentration of the aqueous explosion suppressant solution is 0.1-2wt%, preferably 0.2-1wt%, more preferably 0.26-0.5wt%.
9. The method according to claim 7 or 8, wherein the liquid aerosol has a particle size of 2-50 μm.
10. A method according to any one of claims 7-9, characterized in that the content of the liquid aerosol in the confined space is made to be 0.5-5wt%, preferably 2-3wt%.
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