CN115814325B - Fluorine-containing fire extinguishing agent composition - Google Patents
Fluorine-containing fire extinguishing agent composition Download PDFInfo
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- CN115814325B CN115814325B CN202211477107.6A CN202211477107A CN115814325B CN 115814325 B CN115814325 B CN 115814325B CN 202211477107 A CN202211477107 A CN 202211477107A CN 115814325 B CN115814325 B CN 115814325B
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 72
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 25
- 239000011737 fluorine Substances 0.000 title claims abstract description 25
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 claims abstract description 24
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 28
- 229950008618 perfluamine Drugs 0.000 claims description 13
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229920004449 Halon® Polymers 0.000 description 8
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- -1 halocarbon radicals Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- Fire-Extinguishing Compositions (AREA)
Abstract
The invention relates to a fluorine-containing fire extinguishing agent composition, which consists of the following components in parts by mass: 40-60 parts of heptafluoropropane, 30-40 parts of fire extinguishing auxiliary agent and 10-20 parts of stabilizer; the extinguishing auxiliary agent in the extinguishing agent composition adopts perfluoro triethylamine or 2-BTP, so that a stable azeotropic mixture can be formed with heptafluoropropane, the stable azeotropic mixture has good stability and strong chemical extinguishing effect, the azeotropic mixture is in a liquid state, the extinguishing concentration of the heptafluoropropane extinguishing agent is greatly reduced, the transportation is more convenient, a stabilizer with good compatibility and stable properties is added into the azeotropic mixture formed by the heptafluoropropane and the extinguishing auxiliary agent for further stabilizing the azeotropic mixture, and the fluorine-containing extinguishing agent composition obtained by uniformly mixing the components has the advantages of difficult volatilization, stable properties, convenience in transportation, low extinguishing concentration, high extinguishing efficiency and the like, and has good application prospect.
Description
Field of the art
The invention relates to a safe and efficient fluorine-containing fire extinguishing agent composition.
(II) background art
Halon extinguishing agents are a generic term for halogenated hydrocarbons. The 'Haron' fire extinguishing medium is widely applied to civil aviation, precision and precious fire scenes due to the advantages of high fire extinguishing efficiency, stable chemical property and the like. Serious environmental problems are caused by the reaction of halocarbon radicals with ozone during decomposition. Therefore, finding a new generation of highly efficient, environmentally friendly "halon" alternative products to extinguish fires has become a hotspot problem. Thus a series of halon substitutes appear in succession.
Heptafluoropropane is taken as a typical halon substitute fire extinguishing agent, and does not damage an atmospheric ozone layer and leave residues or oil stains after release because of no chlorine or bromine, so that the heptafluoropropane is widely applied to fire extinguishing scenes of precision electronic equipment and valuables; however, the fire extinguishing agent still needs to be packaged in a pressure container for transportation at normal temperature and normal pressure, which is inconvenient and has certain potential safety hazard.
The fire extinguishing efficiency of the contrast halon fire extinguishing agent heptafluoropropane fire extinguishing agent can only reach one half of that of the halon fire extinguishing agent, the fire extinguishing effect is not ideal, HF gas with irritation and corrosiveness is easy to generate in the fire extinguishing process, and the life safety of personnel on the fire extinguishing site is endangered.
In summary, the heptafluoropropane is gas at normal temperature and normal pressure, potential safety hazards exist in the transportation process, the fire extinguishing effect of the heptafluoropropane fire extinguishing agent is not superior to that of the traditional halon fire extinguishing agent, and harmful gas generated in the fire extinguishing process also causes harm to life safety of field personnel, so that the defects are very unfavorable for popularization and use of the halon fire extinguishing agent.
(III) summary of the invention
Aiming at the prior art problems, the invention provides the fluorine-containing fire extinguishing agent composition, which can further reduce the fire extinguishing concentration and improve the fire extinguishing efficiency while enhancing the stability of the heptafluoropropane fire extinguishing agent so as to facilitate transportation, thereby achieving the optimization effect on the prior heptafluoropropane fire extinguishing agent.
The technical scheme adopted by the invention is as follows:
a fluorine-containing fire extinguishing agent composition comprises the following components in parts by mass:
40 to 60 parts of heptafluoropropane
30-40 Parts of fire extinguishing auxiliary agent
10-20 Parts of stabilizer;
The fire extinguishing auxiliary agent is one or a mixture of more than two of the following components: 2-BTP, perfluorotriethylamine, trifluoromethane, pentafluoroethane, hexafluoropropane.
The stabilizer is one or a mixture of more than two of the following: perfluorotripropylamine, perfluorotributylamine, hexafluoropropylene dimer, hexafluoropropylene trimer.
Preferably, the fire extinguishing auxiliary agent is 2-BTP or perfluoro triethylamine; the preferred fire extinguishing auxiliary agent is liquid at normal temperature and normal pressure, has better compatibility with heptafluoropropane to form a stable azeotropic mixture, has excellent chemical fire extinguishing effect, and can generate a large amount of F-containing active free radicals to consume H.OH and O.free radicals necessary for flame combustion in the fire extinguishing process so as to improve the fire extinguishing effect of the heptafluoropropane fire extinguishing agent.
More preferably, the fire extinguishing auxiliary agent is perfluoro triethylamine.
Preferably, the stabilizer is perfluorotripropylamine or perfluorotributylamine; the optimized stabilizer of the invention has excellent solubility and stable property with the azeotropic mixture according to the similar compatible principle, can provide a certain active free radical to participate in the fire extinguishing reaction in the high-temperature environment of fire extinguishment, and has an improvement effect on the overall stability and the fire extinguishing effect of the fluorine-containing fire extinguishing agent composition.
More preferably, the stabilizer is perfluorotributylamine.
Preferably, the fire extinguishing agent composition consists of the following components in parts by mass:
45 to 55 percent of heptafluoropropane
35 To 39 percent of perfluoro triethylamine
10 To 16 percent of perfluoro tributylamine.
Or the fire extinguishing agent composition consists of the following components in parts by mass:
45 to 55 percent of heptafluoropropane
2-BTP 35％～39％
10 To 16 percent of perfluoro tributylamine.
Or the fire extinguishing agent composition consists of the following components in parts by mass:
45 to 55 percent of heptafluoropropane
35 To 39 percent of perfluoro triethylamine
10 To 16 percent of perfluoro tripropylamine.
Or the fire extinguishing agent composition consists of the following components in parts by mass:
45 to 55 percent of heptafluoropropane
2-BTP 35％～39％
10 To 16 percent of perfluoro tripropylamine.
The preparation method of the fire extinguishing agent composition comprises the following steps: the heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent under the condition of normal temperature being slightly higher than normal pressure (126-151 kpa) to form azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer to obtain the required fire extinguishing agent composition, and the fire extinguishing agent composition is stored under the condition of pressurizing by a pressure container.
The beneficial effects of the invention are mainly as follows: according to the fire extinguishing agent composition, the characteristic that a relatively stable azeotropic mixture can be formed under normal temperature and slightly pressurized pressure of the heptafluoropropane and the perfluorotriethylamine has excellent chemical fire extinguishing effect is utilized, and in order to further stabilize the obtained azeotropic mixture, the perfluorotributylamine with stable property and good compatibility is added as a stabilizer, and after the three are mixed according to the proportion, the original gaseous heptafluoropropane is converted into the liquid fluorine-containing fire extinguishing agent composition which is more stable and convenient to transport, and the fire extinguishing concentration of the heptafluoropropane fire extinguishing agent is greatly reduced, so that the fire extinguishing efficiency is improved, and the fire extinguishing agent composition has a good application prospect.
(IV) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
Example 1:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 45% perfluorotriethylamine: 39% perfluorotributylamine: 16%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained (the fire extinguishing agent composition is stored under the condition that a pressure vessel is needed for pressurization and sealing, and the steps are the same).
Example 2:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 50% perfluorotriethylamine: 36% perfluorotributylamine: 14%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained.
Example 3:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 55% perfluorotriethylamine: 33% perfluorotributylamine: 12%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained.
Example 4:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 45%2-BTP:39% perfluorotributylamine: 16%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Example 5:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 50%2-BTP:36% perfluorotributylamine: 14%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Example 6:
Heptafluoropropane: 55%2-BTP:33% perfluorotributylamine: 12%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Example 7:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 45% perfluorotriethylamine: 39% perfluorotripropylamine: 16%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained.
Example 8:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
heptafluoropropane: 50% perfluorotriethylamine: 36% perfluorotripropylamine: 14%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained.
Example 9:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 55% perfluorotriethylamine: 33% perfluorotripropylamine: 12%
The heptafluoropropane is fully contacted and mixed with the perfluorotriethylamine serving as a fire extinguishing auxiliary agent under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa), so as to form an azeotropic mixture, and then the azeotropic mixture and the perfluorotributylamine serving as a stabilizer are uniformly mixed, so that the required fire extinguishing agent composition is obtained.
Example 10:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 45%2-BTP:39% perfluorotripropylamine: 16%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Example 11:
a fluorine-containing fire extinguishing agent composition comprises the following components in percentage by weight:
Heptafluoropropane: 50%2-BTP:36% perfluorotripropylamine: 14%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Example 12:
Heptafluoropropane: 55%2-BTP:33% perfluorotripropylamine: 12%
The heptafluoropropane is fully contacted and mixed with the fire extinguishing auxiliary agent 2-BTP under the condition that the normal temperature is slightly higher than the normal pressure (130 kpa) to form an azeotropic mixture, and then the azeotropic mixture is uniformly mixed with the stabilizer perfluorotributylamine to obtain the required fire extinguishing agent composition.
Comparative example 1:
heptafluoropropane: 100%.
The lowest fire extinguishing concentration of the above-described fire extinguishing agent composition was tested by the cup combustion method.
Pouring n-heptane into a drying tower, connecting the drying tower with a combustion cup, guiding the n-heptane into the cup, and adjusting the liquid level and the cup top to 5-10 mm. Opening an air steel cylinder, and regulating the air flow to be stable at 30L/min; igniting the fuel and pre-burning for 60s, during which the fuel level in the cup is adjusted to within 1mm from the cup top; starting to feed the fire extinguishing agent compositions of examples 1 to 12 into the oil bath tube respectively by peristaltic pumps (in comparative example 1, heptafluoropropane gas cylinders are used instead of peristaltic pumps), setting the temperature of the oil bath to 130 ℃ to enable the fire extinguishing agent to be fully gasified, gradually increasing the flow rate of the fire extinguishing agent until the flame is extinguished within 1min at the flow rate, recording the flow rate of the fire extinguishing agent and the fire extinguishing time, increasing the rotation speed of the peristaltic pumps to increase the concentration of the fire extinguishing agent, and paying attention to the increase in operation not to exceed 2% of the previous concentration; before the next experiment, the fuel in the cup, residues attached to the cup and soot should be removed in time. The above operations were repeated 2 times, and the fire extinguishing concentrations in examples 1 to 12 and comparative example 1 were calculated, respectively, based on the average value of three experiments:
The formula for calculating the fire extinguishing concentration is as follows:
Wherein: c is the volume fraction of the fluorine-containing extinguishing agent composition during extinguishment, namely the extinguishing concentration;
v is the volume flow rate after gasification of the fluorine-containing fire extinguishing agent composition, L/min;
v air is the volume flow of air, L/min.
The experimental results are shown in table 1:
TABLE 1
As can be seen from the data in table 1, the comparative example 1 and examples 1 to 12 show that the fire extinguishing concentration of the fluorine-containing fire extinguishing agent composition obtained by pressure mixing is reduced from 7.59% to 4.23% by more than 40%, which indicates that the fire extinguishing effect of the heptafluoropropane fire extinguishing agent is greatly improved with the addition of the fire extinguishing auxiliary agent and the stabilizer; compared with examples 4-6, examples 1-3 can find that the effect of reducing the fire-extinguishing concentration by adding the fire-extinguishing auxiliary agent and selecting perfluoro-triethylamine is better than that of 2-BTP, and the mixed fire-extinguishing agent composition has better synergistic effect because the perfluoro-triethylamine and the heptafluoropropane have better compatibility; comparison of examples 1-3 with examples 7-9 shows that the stabilizer selected from perfluorotributylamine has better fire extinguishing effect than perfluorotripropylamine, because perfluorotributylamine is more susceptible to cracking at high temperature and generates more active free radicals to participate in the fire extinguishing reaction.
Claims (3)
1. A fluorine-containing fire extinguishing agent composition comprises the following components in parts by mass:
40-60 parts of heptafluoropropane
30-40 Parts of fire extinguishing auxiliary agent
10-20 Parts of a stabilizer;
The fire extinguishing auxiliary agent is perfluoro triethylamine;
The stabilizer is one of the following: perfluoro tripropylamine and perfluoro tributylamine.
2. The fluorine-containing fire extinguishing agent composition according to claim 1, characterized in that the fire extinguishing agent composition consists of the following components by mass:
45% -55% of heptafluoropropane
35-39% Of perfluoro triethylamine
10% -16% Of perfluoro tributylamine.
3. The fluorine-containing fire extinguishing agent composition according to claim 1, characterized in that the fire extinguishing agent composition consists of the following components by mass:
45% -55% of heptafluoropropane
35-39% Of perfluoro triethylamine
10% -16% Of perfluoro tripropylamine.
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| CN115814325A (en) | 2023-03-21 |
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