CN103550901A - Novel composite powdery fire extinguishing medium and preparation method thereof - Google Patents
Novel composite powdery fire extinguishing medium and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel composite powdery fire extinguishing medium, which is characterized by comprising the following components in percentage by mass: 60-70% of superfine powder with the particle size of 1-20 microns, 25-35% of nano-powder with the particle size of 200-500 nanometers, 2-3% of surface modifier and 3-5% of thermosensitive substance. The medium is small in particle size and good in mobility, dispersibility and floatability, can put out class A, class B and class C fire when being applied to a completely submerged fire extinguishing environment, is particularly high in fire extinguishing efficiency, inhibitive to recrudescence and non-toxic and harmless when being applied to putting out the class A fire, and can be used as a substitute of a Halon fire extinguishing agent.
Description
Technical field
The invention belongs to safety protection technique field, be specifically related to a kind of NEW TYPE OF COMPOSITE powder firing-fighting medium and preparation method thereof.
Background technology
Powder extinguishing agent is as traditional extinguishing chemical, and owing to having, blow-off velocity is fast, dry powder base-material wide material sources, cheap, to people and animals, the feature such as good, little to ambient influnence, the wide accommodation of nontoxic or low toxicity, electrical insulating property is occupied considerable status in current extinguishing chemical field.The conventional powder extinguishing agent powder particle using is at present conventionally between 10～75 μ m, this particle dispersion is relatively poor, specific area is also relatively low, thereby total specific area that quantitative powder has is less, the quality of single particle is larger, settling velocity is very fast, and the speed of particle decomposes is slower, cause it to catch the limited in one's ability of free radical or active group, its extinguishing ability is also just very limited, and then limited the scope of application of powder extinguishing agent, while putting out a fire in particular for total flooding, effect is undesirable.
China formally develops ultra-fine dry powder extinguishing agent since the nineties in last century, and came into operation in 2000, within 2006, China has issued and implemented GA578-2005 < < ultra-fine dry powder extinguishing agent > > industry standard.Ultra-fine dry powder extinguishing agent particle diameter is little, particle specific area is large, active high, after spraying, particle has longer suspension time in air, and can enter tiny space by cut-through thing, therefore ultra-fine dry powder is compared with conventional dry powder, and extinguishing ability greatly improves, and can realize in part place total flooding fire extinguishing.
And superfine powder is worked within the scope of Nano Particle, particulate will show some particularity: as quantum size effect, small-size effect, skin effect, kubo theory, make nano-powder there is larger superiority than superfine powder, show: in (1) nano-powder fire extinguishing procedure, better with the aerosol stability that air is mixed to form, aerosol stability is relevant with the particle diameter of colloidal particle.The little sinking speed of nano particle diameter is slow, therefore nanometer aerosol good stability is longer at scene of fire suspension time as extinguishing chemical, Performance Ratio sub-micron-powder is more superior.(2) nano particle suction-operated is strong.The adsorption capacity of particle is relevant with specific area, and more bulky grain adsorption capacity is stronger for specific area.Nanometer particle size is less 1000 times than micron grain size, and adsorption capacity is inevitable strong.(3) nano particle chemical reaction ability is strong.When particle size drops to nanometer scale, a particle comprises tens or tens molecules, and damaged key increases suddenly, and chemism strengthens, and this is one of performance of small-size effect.(4) nano particle fire extinguishing effectiveness is high.Dry powder particle and the collision of active transmitter, absorb its energy, makes its inactivation, reaches the effect of fire extinguishing.The cold air sol average grain diameter of succeeding in developing is 3 μ m, and its fire extinguishing effectiveness has been 4～6 times of halon fire agent.If adopt the nanoscale cold air sol that average grain diameter is 100nm, by known its fire extinguishing effectiveness of theory calculating, be 30 times of micron cold air sol.Due to the superiority of nano-powder, preparing the fire extinguishing powder that particle diameter reaches nanometer scale becomes a kind of effective way that improves powder extinguishing agent effect, is also a developing direction of powder extinguishing agent.
Although nano-powder extinguishing chemical excellent performance, has fabulous application prospect in theory, in large-scale production and practical application, also there are some problems, limited the propagation and employment of nano-powder extinguishing chemical.These problems mainly contain: (1) complicated process of preparation: the I of powder diameter size that conventional physical crushing technology makes reaches micron order, but for nano particle, it is just helpless.And some other preparation method of nano material, ubiquity preparation process is too complicated, is difficult to realize the defect of large-scale production.(2) unstability of nano particle: when solid particle diminishes, while especially reaching nanometer scale, particle is no longer an inert body, but the object that can supply with electronics and trapped electrons is a chemically reactive substance.Due to the structural feature of nanoparticle, its chemism is very high; Due to the huge surface energy of nanoparticle, make very easily polymerization of nanoparticle again, form soft-agglomerated or hard aggregation.The chemism of nano powder height and surface can seriously affect stability, dispersiveness and the mobility of nanometer powder extinguishing chemical in storage, use procedure, thereby have also limited the development of nano-powder extinguishing chemical.(3) manufacturing cost is high: at present, because nano-powder preparation technology is comparatively special, complicated, the nano particle making also needs to carry out surface modification treatment.Therefore the production cost of nanometer powder extinguishing chemical is much higher than common powder extinguishing agent, and this is also a reason of restriction nanometer powder extinguishing chemical development.The present invention therefore.
Summary of the invention
The object of the invention is to propose a kind of NEW TYPE OF COMPOSITE powder firing-fighting medium, solved in prior art conventional dry powder extinguisher fire-fighting efficiency low, nano-powder high in cost of production problem.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A powder firing-fighting medium, is characterized in that described medium comprises following component:
Particle size range, at the superfine powder of 1～20 μ m, accounts for 60～70% of firing-fighting medium mass fraction;
Particle size range, at the nano-powder of 200～500nm, accounts for 25～35% of firing-fighting medium mass fraction;
Surface modifier, accounts for 2～3% of firing-fighting medium mass fraction;
Heat-sensitive substance, accounts for 3～5% of firing-fighting medium mass fraction.
In preferred technical scheme: described superfine powder is one or more any combination of ammonium phosphate salt or carbonate; Described nano-powder is one or more any combination of ammonium phosphate salt or carbonate.
In preferred technical scheme: described ammonium phosphate salt is selected from phosphoric acid dihydro amine, dibastic sodium phosphate, potassium hydrogen phosphate, phosphamide, sodium phosphate, potassium phosphate; Described carbonate is selected from carbonic hydroammonium, saleratus, ammonium carbonate, potash.
In preferred technical scheme: described heat-sensitive substance is urea; Described surface modifier is organosilan.
In preferred technical scheme: described organosilan is selected from the one or more kinds of any combination of phenyltrimethoxysila,e, phenyl triethoxysilane, n-octyl triethoxysilane, n-octyl triethoxysilane.
In preferred technical scheme: in described superfine powder, the diameter of particle of 90% weight is within the scope of 1～5 μ m; In described nano-powder, the powder one dimension particle diameter of 90% weight is within the scope of 300～500nm.
The preparation method who another object of the present invention is to provide a kind of described NEW TYPE OF COMPOSITE powder firing-fighting medium, is characterized in that said method comprising the steps of:
(1) nano-powder is distributed in liquid medium, then according to preset ratio, adds organosilan reflux heating to carry out surface modification; Finally that the nano-powder after modification is separated dry from liquid medium;
(2) prepare superfine powder and heat-sensitive substance;
(3) nano-powder after modification, superfine powder and heat-sensitive substance being carried out to ball milling mixes and obtains NEW TYPE OF COMPOSITE powder firing-fighting medium.
In preferred technical scheme: in described method step (1), liquid medium is selected from alcohol, ether or polar non-solute; Add the temperature of hot reflux between room temperature and the boiling point of liquid medium.
In preferred technical scheme: in described method step (2), superfine powder and heat-sensitive substance obtain by comminution by gas stream.
Another object of the present invention is to provide the application of a kind of described NEW TYPE OF COMPOSITE powder firing-fighting medium as extinguishing chemical aspect.
The present invention is powder fire-fighting technique field, relates to a kind of design and preparation method of Novel super-thin-composite nano-powder extinguishing chemical formula.Technical solution of the present invention is by superfine powder, nano-powder and other additive combination of different proportion, checking by experiment, obtain that a kind of fire extinguishing is efficient, cost reasonably new and effective ultra-fine-composite nano-powder extinguishing chemical fills a prescription and preparation method thereof.
NEW TYPE OF COMPOSITE powder firing-fighting medium of the present invention comprises superfine powder and nano-powder, according to powder extinguishing chemical fire extinguishing function mechanism, superfine powder, nano-powder, surface modifier, heat-sensitive substance, consists of.
Further, described concrete component and mass fraction are as follows:
Ammonium phosphate salt/carbonate superfine powder particle diameter of (1) 90% weight is less than 1～5 μ m, accounts for 60～70% of composite granule mass fraction; In this patent, spendable ammonium phosphate salt and carbonate comprise phosphoric acid dihydro amine, dibastic sodium phosphate, potassium hydrogen phosphate, carbonic hydroammonium, saleratus etc.;
Ammonium phosphate salt/carbonate nano-powder one dimension particle diameter of (2) 90% weight, at 300～500nm, accounts for 25～35% of composite granule mass fraction;
(3) surface modifier is organosilan, accounts for 2～3% of composite granule mass fraction; In this patent, spendable organosilan comprises phenyltrimethoxysila,e, phenyl triethoxysilane, n-octyl triethoxysilane, n-octyl triethoxysilane etc.;
(4) heat-sensitive substance is urea, accounts for 3～5% of composite nano powder mass fraction.
Preparation process:
(1) choose by standby mass ratio 25～35% ammonium phosphate salts/carbonate nano-powder of solvent-nonsolvent legal system.Then by adding 2～3% organosilan, it is carried out to surface modification;
Process of Surface Modification: nano-powder is distributed to (for example alcohol, ether or polar non-solute) in liquid medium, then, organosilan surface modifier can be added in resulting dispersion and the mixture of gained is heated to the temperature between room temperature and the boiling point of liquid medium under refluxing, by separate modes such as optional filtrations, carrying out separation, dry etc.
(2) choosing the mass ratio of preparing by comminution by gas stream is 60-70% ammonium phosphate salt/carbonate superfine powder and heat-sensitive substance;
(3) by ball mill, mix and within 10～15 minutes, evenly obtain sample.
The principle of technical solution of the present invention is:
The various raw materials of NEW TYPE OF COMPOSITE powder firing-fighting medium of the present invention role in fire extinguishing is as follows:
(1) superfine powder: suppress mechanism and Chemical Inhibition mechanism (homogeneous phase and out-phase reaction) and combustible substance by heat absorption in the ammonium phosphate salt bulky grain infall process of particle diameter below 20 μ m and react, reach inhibition, knock down the flame by the free radical interruption combustion chain reaction of capturing in the scene of a fire.The metaphosphoric acid decomposing in addition and APP are melted and form a glassy cover layer under the high temperature on burning solid surface, and it can play insulating effect, and flame is gone out because suffocating.
(2) nano-powder: particle diameter is carrying under gas effect and filling the air in combustion space with aerosol shape at the ammonium phosphate salt granule of 300nm, play Chemical Inhibition and suppress resume combustion effect, and because particle diameter is little, easily surmount obstacles and enter into solid interior, the surface of solids in burning forms the uniform cover layer of one deck, play the effect of isolated fire extinguishing, and also easily infiltrate the depths, gap after surface of solids charing, put out the flame of deep layer.
And the superfine powder of different proportion and nano-powder are mixed, under close delivery rate, along with increasing of nano-powder proportion, corresponding attack time shortens, but when the mass percent concentration of nano-powder is increased to 40%, then the amount that increases nano-powder can not significantly shorten attack time.This is that oarse-grained powder is longer the residence time in combustion chamber because under the effect of air-flow, and short grained powder is easily directly taken away by air-flow, and therefore suitable some oarse-grained powders of existence are conducive to improve fire extinguishing effect.
(3) surface modifier: be mainly used in changing the table form of composite nano powder, alleviate its hygroscopicity and surface reunion.
(4) heat-sensitive substance: can absorb heat and discharge not combustion-supporting gas simultaneously in the high temperature of the scene of a fire, reduce oxygen content in the scene of a fire.
NEW TYPE OF COMPOSITE powder firing-fighting medium of the present invention considers fire-fighting efficiency and fire extinguishing cost.Its base-material ammonium phosphate or carbonate is easy to get, production technology is simple, low price, nontoxic, pollution-free, electrical insulation properties is good.And because granularity is little, mobility, dispersiveness, floating good, be applied to total flood fire suppression environment, can put out a fire to save life and property A, B, C class fire, especially high to category-A fire fire-fighting efficiency, suppress resume combustion, nontoxic, can be used as the substitute of halon fire agent.
With respect to scheme of the prior art, advantage of the present invention is:
Compare with ultra-fine extinguishing chemical with existing powder extinguishing agent, NEW TYPE OF COMPOSITE powder firing-fighting medium of the present invention has carried out integrating improvement to existing extinguishing chemical composition, embodies the advantage of composite powder fire extinguishing agent in the following aspects:
(1) superfine powder in NEW TYPE OF COMPOSITE powder firing-fighting medium can reduce nano-powder consumption, significantly reduces production costs; In addition, compare with nano-powder, because superfine powder has larger momentum, be conducive to improve the ability that composite nano powder penetrates fire plume, arrive flame surface and realize effective fire attack, therefore compare with simple nano-powder, the extinguishing ability of composite nano powder is stronger;
(2) nano-powder in NEW TYPE OF COMPOSITE powder firing-fighting medium, has larger specific area, compares with simple superfine powder, and extinguishing ability greatly improves;
(3) NEW TYPE OF COMPOSITE powder firing-fighting medium is guaranteeing on extinguishing property basis for cost reduces nano-powder composition as far as possible, the composition using directly affects fire extinguishing effect, compare with existing preparation method simultaneously, each component of the present invention can complete preparation by physical mixed, and powder is more stable, preparation, transportation, production aspect for powder do not have specific (special) requirements, and cost is comparatively cheap.
The specific embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
The preparation of embodiment 1 NEW TYPE OF COMPOSITE powder firing-fighting medium
Various raw material components are prepared by following formula:
Preparation process is:
To be that 25% ammonium dihydrogen phosphate (ADP) nano-powder adds in phenyltrimethoxysila,e surfactant by the standby composite granule mass ratio that accounts for of solvent-nonsolvent legal system, be heated to 75～85 ℃, under stirring, be added dropwise to the acetone soln of a certain proportion of fluoroacrylic resin, control the 1-2% that fluoroacrylic resin quality is powder quality, acetone soln is added dropwise to complete rear continuation and stirs 5～10 minutes, the separated dry ammonium dihydrogen phosphate (ADP) nano-powder that obtains modification of cooling.And be that 70% ammonium dihydrogen phosphate (ADP) superfine powder and urea mix by ball mill with the mass ratio of preparing by comminution by gas stream, obtain NEW TYPE OF COMPOSITE powder firing-fighting medium (filling a prescription 1).
Embodiment 2: the preparation of NEW TYPE OF COMPOSITE powder firing-fighting medium
Various raw material components are prepared by following formula:
Preparation process is identical with example 1, prepares gained NEW TYPE OF COMPOSITE powder firing-fighting medium (filling a prescription 2).
Embodiment 3: the preparation of NEW TYPE OF COMPOSITE powder firing-fighting medium
Various raw material components are prepared by following formula:
Preparation process is identical with example 1, prepares gained NEW TYPE OF COMPOSITE powder firing-fighting medium (filling a prescription 3).
Embodiment 4 extinguishing properties are investigated
Extinguishing property is analyzed:
Choose respectively NEW TYPE OF COMPOSITE powder firing-fighting medium formula 1 that above-described embodiment prepares, fill a prescription 2, fill a prescription 3, nano-powder (the ammonium dihydrogen phosphate (ADP) nano-powder through modification of producing in NEW TYPE OF COMPOSITE powder firing-fighting medium formula preparation process), ultra-fine dry powder (the ammonium dihydrogen phosphate (ADP) superfine powder of producing by comminution by gas stream that NEW TYPE OF COMPOSITE powder firing-fighting medium formula is chosen) and the common powder extinguishing agent of ammonium dihydrogen phosphate (ADP).
By restricted clearance and two kinds of modes of Cup-burner burner fire extinguishing experiment, measure this formula extinguishing property:
(1) the restricted clearance oil sump of 1.2m * 1.2m * 1.2m fire and grillage fire fire extinguishing experiment
1) experimental result of putting out a fire under different pressures is as follows:
Table 1 experimental result
Table 1 has shown that composite granule attack time and foamite amount are all between nano-powder and superfine powder, and close to nano-powder, and outstanding behaviours goes out under low pressure operation, and fire-fighting efficiency is high, the few feature of powder consumption.And show that by the experiment of grillage fire composite granule and nano-powder are all to suppressing grillage fire resume combustion successful.And for three formulas, along with nano-powder proportion increases, fire-fighting efficiency is also increasing, and fill a prescription, 3 substantially approached nano-powder.
2) experimental result of putting out a fire under different distance is as follows
Table 2 experimental result
Table 2 shows, when increasing burning things which may cause a fire disaster, with the distance of shower nozzle is, to the fire extinguishing influential effect of composite granule and nano-powder, will be significantly less than superfine powder and common powder, and it is good that reason is the suspendability of these two kinds of powders and fills the air performance, and in space, distribution is more even.Especially when burning things which may cause a fire disaster is grillage, the distance that increases burning things which may cause a fire disaster and shower nozzle is little on the extinguishing property impact of composite granule and nano-powder.Equally for three formulas, along with nano-powder proportion increases, fire-fighting efficiency is also increasing, and fill a prescription, 3 has substantially approached nano-powder.
(2) Cup-burner burner oil sump fire and grillage fire fire extinguishing experiment
All kinds of powder fire extinguishing experimental results under the different delivery rates of table 3
Table 3 shows, composite granule is for the fire extinguishing effect of two class fire based between nano-powder and superfine powder, but closer to nano-powder, especially filling a prescription 3 approaches nano-powder substantially.And the flame power of normal heptane fire is greater than ethanol fire, just can there is thermal decomposition before leaving combustion chamber in composite granule and nano-powder, therefore easily shows than the better fire extinguishing effect of superfine powder.
Above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that Spirit Essence is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a NEW TYPE OF COMPOSITE powder firing-fighting medium, is characterized in that described medium comprises following component:
Particle size range, at the superfine powder of 1～20 μ m, accounts for 60～70% of firing-fighting medium mass fraction;
Particle size range, at the nano-powder of 200～500nm, accounts for 25～35% of firing-fighting medium mass fraction;
Surface modifier, accounts for 2～3% of firing-fighting medium mass fraction;
Heat-sensitive substance, accounts for 3～5% of firing-fighting medium mass fraction.
2. NEW TYPE OF COMPOSITE powder firing-fighting medium according to claim 1, is characterized in that described superfine powder is one or more any combination of ammonium phosphate salt or carbonate; Described nano-powder is one or more any combination of ammonium phosphate salt or carbonate.
3. NEW TYPE OF COMPOSITE powder firing-fighting medium according to claim 2, is characterized in that described ammonium phosphate salt is selected from phosphoric acid dihydro amine, dibastic sodium phosphate, potassium hydrogen phosphate, phosphamide, sodium phosphate, potassium phosphate; Described carbonate is selected from carbonic hydroammonium, saleratus, ammonium carbonate, potash.
4. NEW TYPE OF COMPOSITE powder firing-fighting medium according to claim 1, is characterized in that described heat-sensitive substance is urea; Described surface modifier is organosilan.
5. NEW TYPE OF COMPOSITE powder firing-fighting medium according to claim 4, is characterized in that described organosilan is selected from the one or more kinds of any combination of phenyltrimethoxysila,e, phenyl triethoxysilane, n-octyl triethoxysilane, n-octyl triethoxysilane.
6. NEW TYPE OF COMPOSITE powder firing-fighting medium according to claim 1, is characterized in that the diameter of particle of 90% weight in described superfine powder is within the scope of 1～5 μ m; In described nano-powder, the powder one dimension particle diameter of 90% weight is within the scope of 300～500nm.
7. a preparation method for the NEW TYPE OF COMPOSITE powder firing-fighting medium described in claim 1～6 any one, is characterized in that said method comprising the steps of:
(1) nano-powder is distributed in liquid medium, then according to preset ratio, adds organosilan reflux heating to carry out surface modification; Finally that the nano-powder after modification is separated dry from liquid medium;
(2) prepare superfine powder and heat-sensitive substance;
(3) nano-powder after modification, superfine powder and heat-sensitive substance being carried out to ball milling mixes and obtains NEW TYPE OF COMPOSITE powder firing-fighting medium.
8. preparation method according to claim 7, is characterized in that in described method step (1), liquid medium is selected from alcohol, ether or polar non-solute; Add the temperature of hot reflux between room temperature and the boiling point of liquid medium.
9. preparation method according to claim 7, is characterized in that the middle superfine powder of described method step (2) and heat-sensitive substance obtain by comminution by gas stream.
10. the NEW TYPE OF COMPOSITE powder firing-fighting medium described in claim 1～6 any one is as the application of extinguishing chemical aspect.
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| CN111589041A (en) * | 2020-04-30 | 2020-08-28 | 中国人民解放军92228部队 | Anti-reburning composite dry powder extinguishing agent and preparation method thereof |
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| CN115738159A (en) * | 2022-11-22 | 2023-03-07 | 晋西铁路车辆有限责任公司 | Water-based extinguishing agent and preparation method thereof |
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| CN113546361B (en) * | 2021-08-17 | 2022-09-02 | 湖南神州防务科技有限公司 | Ammonium oligomeric phosphate-based composite forest dry powder extinguishing agent and preparation method and application thereof |
| CN115738159A (en) * | 2022-11-22 | 2023-03-07 | 晋西铁路车辆有限责任公司 | Water-based extinguishing agent and preparation method thereof |
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