CN103550901B - NEW TYPE OF COMPOSITE powder firing-fighting medium and preparation method thereof - Google Patents
NEW TYPE OF COMPOSITE powder firing-fighting medium and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of NEW TYPE OF COMPOSITE powder firing-fighting medium, it is characterized in that described medium comprises following component: particle size range, at the superfine powder of 1 ~ 20 μm, 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.This medium granularity is little, mobility, dispersiveness, floating good, be applied to total flood fire suppression environment, A, B, C class of putting out a fire to save life and property fire, especially high to category-A fire fire-fighting efficiency, suppress resume combustion, nontoxic, can as the substitute of halon fire agent.
Description
Technical field
The invention belongs to technical field of safety protection, 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 occupies considerable status in current extinguishing chemical field.The conventional dry powder extinguishing chemical powder particle of current use is usually between 10 ~ 75 μm, this particle dispersion is relatively poor, specific area is also relatively low, thus 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, it is caused to catch the limited in one's ability of free radical or active group, its extinguishing ability is also just very limited, and then limiting the scope of application of powder extinguishing agent, when putting out a fire in particular for total flooding, effect is undesirable.
China formally develops ultra-fine dry powder extinguishing agent from the nineties in last century, and comes into operation in 2000, and within 2006, China has issued and implemented GA578-2005 " ultra-fine dry powder extinguishing agent " professional standard.Ultra-fine dry powder extinguishing agent particle diameter is little, particle specific surface area is large, active high, after spraying, particle has longer suspension time in atmosphere, and tiny space can be entered by cut-through thing, therefore ultra-fine dry powder is compared with conventional dry powder, and extinguishing ability greatly improves, and can realize total flooding fire extinguishing in part place.
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, nano-powder is made to have larger superiority than superfine powder, show: in (1) nano-powder fire extinguishing procedure, the aerosol stability be mixed to form with air is better, and 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, 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 than micron grain size 1000 times, 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 active transmitter collide, and absorb its energy, make its inactivation, reach the effect of fire extinguishing.The cold air sol average grain diameter succeeded in developing is 3 μm, and its fire extinguishing effectiveness has been 4 ~ 6 times of halon fire agent.According to the nanoscale cold air sol that average grain diameter is 100nm, be 30 times of micron cold air sol by theory calculate its fire extinguishing effectiveness known.Due to the superiority of nano-powder, preparing the fire extinguishing powder that particle diameter reaches nanometer scale becomes a kind of effective way improving powder extinguishing agent effect, is also a developing direction of powder extinguishing agent.
Although nano-powder extinguishing chemical excellent performance in theory, has fabulous application prospect, in large-scale production and practical application, also there are some problems, limit the propagation and employment of nano-powder extinguishing chemical.These problems mainly contain: (1) complicated process of preparation: the most I of the obtained powder diameter size of conventional physical crushing technology 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 the defect realizing large-scale production.(2) unstability of nano particle: when solid particle diminishes, when especially reaching nanometer scale, particle is no longer an inert body, but an object that can supply electronics and trapped electrons, be a chemically reactive substance.Due to the structural feature of nanoparticle, its chemism is very high; Again due to the surface energy that nanoparticle is huge, nanoparticle is very easily polymerized, forms soft-agglomerated or hard aggregation.The chemism of nano powder height and surface energy seriously have impact on stability, dispersiveness and the mobility of nanometer powder extinguishing chemical in storage, use procedure, thus also limit the development of nano-powder extinguishing chemical.(3) manufacturing cost is high: at present, because nano-powder preparation technology is comparatively special, complicated, and obtained nano particle 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, solve conventional dry powder fire fighting with fire extinguisher efficiency in prior art 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 kind of 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 μm, 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-octytriethoxysilane, n-octytriethoxysilane.
In preferred technical scheme: in described superfine powder, the diameter of particle of 90% weight is within the scope of 1 ~ 5 μm; In described nano-powder, the powder one dimension particle diameter of 90% weight is within the scope of 300 ~ 500nm.
Another object of the present invention is to the preparation method that a kind of described NEW TYPE OF COMPOSITE powder firing-fighting medium is provided, it is characterized in that said method comprising the steps of:
(1) nano-powder is distributed in liquid medium, then adds organosilan reflux heating according to preset ratio and carry out surface modification; Finally modified nano-powder is separated drying from liquid medium;
(2) superfine powder and heat-sensitive substance is prepared;
(3) modified nano-powder, superfine powder and heat-sensitive substance are carried out ball milling to mix and obtain 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 are obtained by comminution by gas stream.
Another object of the present invention is the application providing 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 design and the preparation method of a kind of Novel super-thin-composite nano-powder extinguishing chemical formula.Technical solution of the present invention, by the superfine powder of different proportion, nano-powder and other additive combination, is verified by experiment, obtain that a kind of fire extinguishing is efficient, cost rational new and effective ultra-fine-composite nano-powder extinguishing chemical formula 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, is made up of superfine powder, nano-powder, surface modifier, heat-sensitive substance.
Further, described concrete component and mass fraction as follows:
Ammonium phosphate salt/carbonate superfine powder the particle diameter of (1) 90% weight is less than 1 ~ 5 μm, accounts for 60 ~ 70% of composite granule mass fraction; In that 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 the 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 that patent, spendable organosilan comprises phenyltrimethoxysila,e, phenyl triethoxysilane, n-octytriethoxysilane, n-octytriethoxysilane etc.;
(4) heat-sensitive substance is urea, accounts for 3 ~ 5% of composite nano powder mass fraction.
Preparation process:
(1) mass ratio 25 ~ 35% ammonium phosphate salts/carbonate nano-powder prepared by solvent-nonsolvent method is chosen.Then the organosilan by adding 2 ~ 3%, carries out surface modification to it;
Process of Surface Modification: nano-powder is distributed to (such as alcohol, ether or polar non-solute) in liquid medium, then, organosilan surface modifier can be added in obtained dispersion and under reflux the mixture of gained to be heated to the temperature between room temperature and the boiling point of liquid medium, being undertaken being separated by separate modes such as optional filtrations, dry etc.
(2) choosing the mass ratio prepared by comminution by gas stream is 60-70% ammonium phosphate salt/carbonate superfine powder and heat-sensitive substance;
(3) by ball mill, mix and evenly obtain sample in 10 ~ 15 minutes.
The principle of technical solution of the present invention is:
The various raw material of NEW TYPE OF COMPOSITE powder firing-fighting medium of the present invention role in fire extinguishing is as follows:
(1) superfine powder: reacted with combustible substance by heat absorption suppression mechanism and Chemical Inhibition mechanism (homogeneous phase and out-phase reaction) in the ammonium phosphate salt bulky grain infall process of particle diameter below 20 μm, interrupt combustion chain reaction by the free radical of capturing in the scene of a fire and reach suppression, knock down the flame.The metaphosphoric acid decomposed in addition and APP are melted formation 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 fills the air in combustion space with aerosol shape at the ammonium phosphate salt granule of 300nm carrying under gas effect, play Chemical Inhibition and suppress resume combustion effect, and because particle diameter is little, easily surmount obstacles and enter into solid interior, the uniform cover layer of one deck is formed at the surface of solids of burning, 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 by the superfine powder of different proportion and nano-powder mixing, 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 increasing nano-powder significantly can not shorten attack time.This is because under the effect of air-flow, oarse-grained powder is longer for the residence time in combustion chamber, and short grained powder is easily directly taken away by air-flow, and some oarse-grained powders of therefore suitable existence are conducive to improving extinguishing effect.
(3) surface modifier: be mainly used in the table form changing composite nano powder, alleviates its hygroscopicity and reunite in surface.
(4) heat-sensitive substance: can absorb heat and discharge not combustion-supporting gas simultaneously in the high temperature of the scene of a fire, reduces 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 excellent.And because granularity is little, mobility, dispersiveness, floating good, be applied to total flood fire suppression environment, A, B, C class of putting out a fire to save life and property fire, especially high to category-A fire fire-fighting efficiency, suppress resume combustion, nontoxic, can as the substitute of halon fire agent.
Relative 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 improving 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 cost; In addition, compare with nano-powder, because superfine powder has larger momentum, be conducive to improving 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, and compare with simple superfine powder, extinguishing ability greatly improves;
(3) NEW TYPE OF COMPOSITE powder firing-fighting medium is tried one's best in order to cost and is reduced nano-powder composition on guarantee extinguishing property basis, the composition used directly affects extinguishing effect, simultaneously compared with existing preparation method, the each component of the present invention can complete preparation by physical mixed, and powder is more stable, do not have particular/special requirement for the preparation of powder, transport, production aspect, cost is comparatively cheap.
Detailed description of the invention
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do 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 is prepared by following formula:
Preparation process is:
By prepared by solvent-nonsolvent method account for composite granule mass ratio be 25% ammonium dihydrogen phosphate (ADP) nano-powder add in phenyltrimethoxysila,e surfactant, be heated to 75 ~ 85 DEG C, the acetone soln of a certain proportion of fluoroacrylic resin is added dropwise under stirring, controlling fluoroacrylic resin quality is the 1-2% of powder quality, acetone soln is added dropwise to complete rear continuation stirring 5 ~ 10 minutes, and cooling is separated the dry ammonium dihydrogen phosphate (ADP) nano-powder obtaining modification.And be that 70% ammonium dihydrogen phosphate (ADP) superfine powder and urea are mixed by ball mill with the mass ratio prepared by comminution by gas stream, obtain NEW TYPE OF COMPOSITE powder firing-fighting medium (formula 1).
Embodiment 2: the preparation of NEW TYPE OF COMPOSITE powder firing-fighting medium
Various raw material components is prepared by following formula:
Preparation process is identical with example 1, prepares gained NEW TYPE OF COMPOSITE powder firing-fighting medium (formula 2).
Embodiment 3: the preparation of NEW TYPE OF COMPOSITE powder firing-fighting medium
Various raw material components is prepared by following formula:
Preparation process is identical with example 1, prepares gained NEW TYPE OF COMPOSITE powder firing-fighting medium (formula 3).
Embodiment 4 extinguishing property is investigated
Extinguishing property is analyzed:
Choose NEW TYPE OF COMPOSITE powder firing-fighting medium formula 1, formula 2, formula 3 that above-described embodiment prepares respectively, nano-powder (the ammonium dihydrogen phosphate (ADP) nano-powder through modification produced in NEW TYPE OF COMPOSITE powder firing-fighting medium formula preparation process), ultra-fine dry powder (the ammonium dihydrogen phosphate (ADP) superfine powder produced 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).
This formula extinguishing property is measured by restricted clearance and Cup-burner burner fire fighting test two kinds of modes:
(1) the restricted clearance liquid pool fire of 1.2m × 1.2m × 1.2m and Wood crib Fire fire fighting test
1) under different pressures, fire fighting test result is as follows:
Table 1 experimental result
Table 1 shows composite granule attack time and foamite amount all between nano-powder and superfine powder, and close to nano-powder, and outstanding behaviours goes out, and fire-fighting efficiency under low pressure operation is high, the few feature of powder consumption.And show composite granule and nano-powder all to suppression Wood crib Fire resume combustion successful by Wood crib Fire experiment.And for three formulas, along with nano-powder proportion increases, fire-fighting efficiency also in increase, and fills a prescription 3 substantially close to nano-powder.
2) under different distance, fire fighting test result is as follows
Table 2 experimental result
Table 2 shows, and when the distance increasing burning things which may cause a fire disaster and shower nozzle is, will be significantly less than superfine powder and common powder to the extinguishing effect impact of composite granule and nano-powder, and reason is the suspendability of these two kinds of powders and to fill the air performance good, distributes in space more even.Especially, when burning things which may cause a fire disaster is grillage, the extinguishing property of distance on composite granule and nano-powder increasing burning things which may cause a fire disaster and shower nozzle affects not quite.Same for three formulas, along with nano-powder proportion increases, fire-fighting efficiency also in increase, and fills a prescription 3 substantially close to nano-powder.
(2) Cup-burner burner liquid pool fire and Wood crib Fire fire fighting test
All kinds of powder fire fighting test result under the different delivery rate of table 3
Table 3 shows, and composite granule, is especially filled a prescription 3 basic close to nano-powder but closer to nano-powder based between nano-powder and superfine powder for the extinguishing effect of two class fire.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 extinguishing effect better than superfine powder.
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to Spirit Essence of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (10)
1.
a kind of composite granule firing-fighting medium, is characterized in that described medium comprises following component:
particle size range, at the superfine powder of 1 ~ 20 μm, 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. according to claim
composite granule firing-fighting medium described in 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. according to claim
composite granule firing-fighting medium described in 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. according to claim
composite granule firing-fighting medium described in 1, is characterized in that described heat-sensitive substance is urea; Described surface modifier is organosilan.
5. according to claim
composite granule firing-fighting medium described in 4, is characterized in that described organosilan is selected from the one or more kinds of any combination of phenyltrimethoxysila,e, phenyl triethoxysilane, n-octytriethoxysilane, n-octytriethoxysilane.
6. according to claim
composite granule firing-fighting medium described in 1, is characterized in that the diameter of particle of 90% weight in described superfine powder is within the scope of 1 ~ 5 μm; In described nano-powder, the powder one dimension particle diameter of 90% weight is within the scope of 300 ~ 500nm.
7. a claim
the preparation method of the composite granule firing-fighting medium described in 1 ~ 6 any one, is characterized in that said method comprising the steps of:
(1) nano-powder is distributed in liquid medium, then adds organosilan reflux heating according to preset ratio and carry out surface modification; Finally modified nano-powder is separated drying from liquid medium;
(2) superfine powder and heat-sensitive substance is prepared;
(3) modified nano-powder, superfine powder and heat-sensitive substance are carried out ball milling to mix and obtain composite granule firing-fighting medium.
8. according to claim
preparation method described in 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. according to claim
preparation method described in 7, is characterized in that in described method step (2), superfine powder and heat-sensitive substance are obtained by comminution by gas stream.
10. a claim
composite granule firing-fighting medium described in 1 ~ 6 any one is as the application of extinguishing chemical aspect.
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| CN107308584A (en) * | 2017-06-09 | 2017-11-03 | 山东环绿康新材料科技有限公司 | A kind of hydrophobic type ultra-fine dry powder extinguishing agent and preparation method thereof |
| WO2019117745A1 (en) * | 2017-12-15 | 2019-06-20 | Общество С Ограниченной Ответственностью "Лаборатория Инновационных Технологий" Квинтех" (Ооо "Лит" Квинтех) | Fire-extinguishing composition |
| CN108314063B (en) * | 2018-02-08 | 2020-08-28 | 中国科学技术大学 | Preparation method of hydrophobic and oleophobic BC superfine dry powder extinguishing agent base material carbonate |
| CN108619651A (en) * | 2018-06-12 | 2018-10-09 | 安徽科技学院 | A kind of preparation method of high effective green environmentally friendly type extinguishing chemical |
| CN110124246A (en) * | 2019-06-25 | 2019-08-16 | 安徽科技学院 | A kind of preparation method of graphite ene-type high-efficiency environment friendly extinguishing chemical |
| CN111589041B (en) * | 2020-04-30 | 2021-11-05 | 中国人民解放军92228部队 | Anti-reburning composite dry powder extinguishing agent and preparation method thereof |
| 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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| CN101239228A (en) * | 2008-03-12 | 2008-08-13 | 昆明泰康集团有限公司 | Ammonium phosphate ultra-fine dry powder extinguishing agent and preparation thereof |
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