CN102836516B - A kind of oil product extinguishment hollow glass micropearl three-phase froth and preparation method thereof - Google Patents
A kind of oil product extinguishment hollow glass micropearl three-phase froth and preparation method thereof Download PDFInfo
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- CN102836516B CN102836516B CN201110172399.8A CN201110172399A CN102836516B CN 102836516 B CN102836516 B CN 102836516B CN 201110172399 A CN201110172399 A CN 201110172399A CN 102836516 B CN102836516 B CN 102836516B
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Abstract
The present invention relates to a kind of oil product extinguishment hollow glass micropearl three-phase froth and preparation method thereof.The component of this three-phase froth is by the general proteins fire foam of following percentage by weight proportioning: 8-15% and the hollow glass micropearl of 3-10%, and surplus is water.Hollow glass micropearl used is hated oil processing through fluorine containing silane coupling agent and obtains.This three-phase froth can adopt conventional foam maker foaming obtained.Three-phase froth of the present invention can form form compact and stable solid overlayer at pasta when being subject to flame thermal radiation, and its anti-burning and anti-resume combustion performance are better than general proteins fire foam, and stability significantly improves.Have consumption little, high, the anti-resume combustion of fire-fighting efficiency, feature simple to operate, can put out oil fire rapidly.
Description
Technical field
The invention belongs to extinguish material field, relate to a kind of oil product extinguishment hollow glass micropearl three-phase froth and preparation method thereof.
Technical background
Oil product generally has inflammable and explosive characteristic, and oil tank, once accident of very easily blasting of catching fire, brings tremendous economic to lose to the people and country.Crude oil and heavy crude storage tank also can be boiled over and splash in combustion process, and the intensity of a fire and firing range are expanded instantaneously.Especially Large Size Oil Storage Tank district, because situation is complicated, putting out a fire to save life and property of fire is more difficult, often produces very serious casualties and the heavy losses of property.
At present, the main method of domestic and international To Extinguish The Fire On Oil utilizes the foam annihilator of fixing or movement to spray foam in tank, and utilize foam trap heat to liquid level transmission, reduction liquid evaporation rate is to reach fire extinguishing object.The most frequently used fire foam of current tank fire is air foam.
Air foam is also called mechanical air foam, and it is that the aqueous solution of fire foam and air are carried out mechanical mixture stirring and generates in foam producer.Different by frostproof froth n multiple, be divided into low expansion foam, medium expansion foam and high expansion foam three class.The coefficient of foaming of low expansion foam is generally below 20 times; The coefficient of foaming of medium expansion foam extinguishing agent is generally at 20 ~ 200 times; The coefficient of foaming of high-expansion foam extinguishing agent is 201 ~ 1000 times.According to type and the purposes of blowing agent, low expansion foam extinguishing chemical can be divided into again general proteins foam, fluoroprotein foam, AFFF, synthetic foam and alcohol foam five type.
The concentrated type air foam agent that general proteins fire foam is is main component with animal protein hydrolysate.Because abundant raw material source, with low cost and applicating history are permanent, but protein foam stability and mobility poor, be difficult to cover rapidly burning things which may cause a fire disaster, extinguishing effect is poor, particularly poorer to the extinguishing effect of oil fire, and resistance to resume combustion is bad.
Fluoroprotein foam extinguishing agent comes from the sixties in last century.It take protein foam extinguishing agent as base-material, makes by adding appropriate " 6201 " prefabricated solution.(" 6201 " prefabricated solution also known as FCS solution, being by the formulated aqueous solution of the mass ratio of 3: 3: 4 by " 6201 " fluorocarbon surfactant, isopropyl alcohol and water).Compared with protein foam extinguishing agent, fluorocarbon surfactant can significantly reduce surface tension and Osima jacoti, Osima excavata, and the protein foam that blow-off velocity compares not fluorocarbon surfactant improves 3 ~ 4 times, and its resistance to resume combustion is good.Fluoroprotein foam extinguishing agent surface tension low energy reaches fuel surface by hydrocarbon class A fuel A rapidly in addition, can adopt subsurface injection.In addition, fluoroprotein foam extinguishing agent can also use with dry powder (when regular-type foam extinguishing chemical and dry powder use simultaneously, foam is destroyed very soon disappears) simultaneously.But the cost of fluoroprotein foam extinguishing agent is higher.
Aqueous film-forming foam extinguishing agent AFFF (Aqueous FilmForming Foaming) is coordinated by many components such as fluorine surfactant, hc-surfactant to form, and is divided into 3% and 6% two type.Its main feature can form the good polymer glued membrane of one deck closure at fuel and foam interface place, and protection foam exempts from polar liquid and destroys, and reaches fire extinguishing object by foam and diaphragm double action.Relative other types extinguishing chemical, aqueous foam-forming solution produce fire foam has strong adhesion, density is high, persistence is long, fire extinguishing is fast, the heat insulation feature effective with thermal radiation resistant.Compared with protein foam extinguishing agent, the fire-fighting efficiency of aqueous film-forming foam extinguishing agent is high more than 4 times, and sprawls rapidly on pasta, and blow-off velocity is fast, and resistance to resume combustion is good, but this foam also exists the high problem of cost.
In a word, formed serial fire-fighting foams extinguishing chemical both at home and abroad at present, in tank fire is puted out a fire to save life and property, played great role.In actual oil tank fire extinguishing process, protein foam extinguishing agent stability is in high temperature environments very poor, and anti-resume combustion ability is low.Need multi-injection, if foam supply capacity is not enough, can not form effective covering, then the foam sprayed early stage can constantly break, and makes the intensity of a fire again out of hand.
Hollow glass micropearl is a kind of novel powder material that development in recent years is got up, and be the thin-walled be made up of sodium borosilicate material through special technology, closed microspheres, granularity is between 10 ~ 250 μm, and bulk density is about 0.1 ~ 0.3g/cm
3, ball interior wraps up a certain amount of gas, has hollow, low-density, low heat conduction, high-low temperature resistant, wear-resisting, corrosion-resistant, water absorption rate is low and the advantage such as stable chemical performance.In recent years, fill agent as composite, hollow glass micropearl has been widely used in the fields such as building materials, plastics, rubber, coating, navigation and space flight.
Summary of the invention
The object of this invention is to provide a kind of oil product extinguishment three-phase froth of adding modification hollow glass micropearl and preparation method thereof, utilize cheap general proteins foam to reach the strong object of high, the anti-resume combustion ability of stability in high temperature environments to solve.
So-called three-phase froth refers to adds in fire-fighting foams by the hollow glass micropearl of powdery, the three-phase froth system comprising solid phase, liquid phase, gas phase be made up of water, air and hollow glass micropearl prepared after passing into compressed air.This hollow glass micropearl three-phase froth has the Typical physical performance of conventional foam, can utilize the heat-proof quality that hollow glass micropearl is good simultaneously, improves the anti-burning of foam and anti-resume combustion performance, contributes to improving the ability of putting out a fire to save life and property to oil fire.
The feature of hollow glass micropearl three-phase froth of the present invention is that its compositions in weight percentage contains the general proteins fire foam of 8-15% and the hollow glass micropearl of 3-10%, and surplus is water.Wherein, the preferably general proteins fire foam of 10%, the hollow glass micropearl of 8%, surplus is water.
The granularity of the hollow glass micropearl that hollow glass micropearl three-phase froth of the present invention is used is between 10-250 μm, and bulk density is about 0.1-0.3g/cm
3microspheres.Its preprocessing process is followed successively by:
(1) acid treatment: under the mixing speed of 250-500 rev/min, hollow glass micropearl is added volume ratio be 7: 3 the concentrated sulfuric acid and 30% hydrogen peroxide mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, after stirring 30min, after washing with water, filter, drying for standby.
(2) alkali treatment: by above-mentioned steps 1 under the mixing speed of 250-500 rev/min) in the hollow glass micropearl of process gained add volume ratio be 1: 1: 5 25% ammoniacal liquor, 30% hydrogen peroxide and water mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, under 60-70 DEG C of condition after ultrasonic reaction 60min, filter, drying for standby.
(3) hollow glass micropearl surface modification treatment: be that the pH of the alcoholic solution of the silane coupler of 0.1-2.0% is adjusted to 3-5 by concentration with concentrated hydrochloric acid, add the hollow glass micropearl after soda acid process, under 60-70 DEG C of condition after ultrasonic reaction 4-6h, filter, drying, both obtained required hollow glass micropearl.
Silane coupler can be 13 fluoro octyl triethoxysilanes, or the pungent sulphonyl aminopropyl triethoxysilane of perfluor etc.Be generally methyl alcohol or the ethanolic solution of above-mentioned silane coupler.
The concentrated type air foam agent that described general proteins fire foam is is main component with animal protein hydrolysate.
The preparation method of the three-phase froth of the invention described above, the steps include:
(1) premixed: in container, adds water, general proteins fire foam in order in proportion, hates the hollow glass micropearl of oil processing through surface under the mixing speed of 250-500 rev/min, stand-by after stirring 5-10min.
(2) foam: the one-tenth of premixed is placed in foam maker, after applying pressure to 0.5-1Mpa, opens valve, oil product extinguishment three-phase froth can be obtained.
Described water is running water, and consumption is for supplying total amount to 100%.
The present invention uses cheap general proteins fire foam to be raw material, be subject to flame thermal radiation can form form compact and stable solid overlayer at pasta by adding the three-phase froth made through the hollow glass micropearl of oleophobic modification, its anti-burning and anti-resume combustion performance are better than general proteins fire foam, and stability significantly improves.There is consumption little, fire-fighting efficiency is high, good stability, anti-resume combustion ability are strong, simple to operate, lower-price characteristic, can put out oil fire rapidly.
In actual production process, in general proteins foam, add conventional hollow glass microballoon, the ability of anti-burning of general proteins foam, anti-resume combustion performance can be improved greatly, but interpolation hollow glass micropearl can make the foaming capacity of protein foam significantly reduce.The coefficient of foaming of protein foam can be kept constant the hollow glass micropearl of oleophobic modification obtained after soda acid and modification for conventional hollow glass microballoon, and significantly improve the stability of three-phase froth at pasta, further improve the ability of anti-burning of product.
Accompanying drawing explanation
Fig. 1 is that the modification hollow glass micropearl of pretreatment gained of the present invention and conventional hollow glass microballoon are on the impact of frostproof froth n performance.
Fig. 2 is the heat endurance of hollow glass micropearl three-phase froth of the present invention at pasta.
When Fig. 3 hollow glass micropearl content is 5%, the pattern of three-phase froth of the present invention after gasoline surface is subject to flame interaction.Wherein, state when Fig. 3 a is 1min49s; Fig. 3 b is the state of 5min23s.
Detailed description of the invention
Following examples are only for setting forth the present invention, and protection scope of the present invention is not only confined to following examples.The those of ordinary skill of described technical field, according to above disclosure of the present invention, all can realize object of the present invention.
Embodiment 1
The pretreatment of hollow glass micropearl:
(1) acid treatment: by hollow glass micropearl 100g (bulk density 0.1g/cm under the mixing speed of 250-500 rev/min
3) add volume ratio be 7: 3 the concentrated sulfuric acid and 30% hydrogen peroxide 2000ml mixed solution in, stir after 30min, after washing with water, filter, drying for standby.
(2) alkali treatment: by above-mentioned steps 1 under the mixing speed of 250-500 rev/min) in the hollow glass micropearl of process gained add volume ratio be 1: 1: 5 25% ammoniacal liquor, 30% hydrogen peroxide and water 1800ml mixed solution in, under 60-70 DEG C of condition after ultrasonic reaction 60min, filter, drying for standby.
(3) hollow glass micropearl surface modification treatment: be that the pH of the ethanolic solution of the 13 fluoro octyl triethoxysilanes of 0.1% is adjusted to 4 by concentration with concentrated hydrochloric acid, add above-mentioned hollow glass micropearl after soda acid process, solution did not have cenosphere, under 60-70 DEG C of condition after ultrasonic reaction 4h, filter, drying, both obtained required hollow glass micropearl.
The preparation of hollow glass micropearl three-phase froth:
In a kettle., under the mixing speed of 300 revs/min, add the water of 750g, 150g general proteins fire foam and 100g bulk density is successively 0.1g/cm
3through above-mentioned pretreated hollow glass micropearl, stir stand-by after 5 minutes.
Be placed in the one-tenth of above-mentioned mixing foam maker weight, after applying pressure to 0.6Mpa, opens valve, can obtain oil product extinguishment hollow glass micropearl three-phase froth of the present invention.
Embodiment 2
The pretreatment of hollow glass micropearl:
(1) acid treatment: by hollow glass micropearl 50g (bulk density 0.2g/cm under the mixing speed of 250-500 rev/min
3) add volume ratio be 7: 3 the concentrated sulfuric acid and 30% hydrogen peroxide 420ml mixed solution in, stir after 30min, after washing with water, filter, drying for standby.
(2) alkali treatment: by above-mentioned steps 1 under the mixing speed of 250-500 rev/min) in process gained hollow glass micropearl add volume ratio be 1: 1: 5 25% ammoniacal liquor, 30% hydrogen peroxide and water 450ml mixed solution in, under 60-70 DEG C of condition after ultrasonic reaction 60min, filter, drying for standby.
(3) hollow glass micropearl surface modification treatment: be that the pH of the methanol solution of the pungent sulphonyl aminopropyl triethoxysilane of 2.0% perfluor is adjusted to 3 by concentration with concentrated hydrochloric acid, add the hollow glass micropearl after soda acid process, solution did not have cenosphere, under 60-70 DEG C of condition after ultrasonic reaction 6h, filter, drying, both obtained required hollow glass micropearl.
The preparation of hollow glass micropearl three-phase froth:
In a kettle., under the mixing speed of 250 revs/min, add the water of 870g, 100g general proteins fire foam and 30g bulk density is successively 0.2g/cm
3through above-mentioned pretreated hollow glass micropearl, stir stand-by after 5 minutes.
Be placed in the one-tenth of above-mentioned mixing foam maker weight, after applying pressure to 0.5Mpa, opens valve, can obtain oil product extinguishment hollow glass micropearl three-phase froth of the present invention.
Embodiment 3
In a kettle., under the mixing speed of 500 revs/min, add the water of 820g, 100g general proteins fire foam and the 80g hollow glass micropearl according to preprocessing process gained in embodiment 2 successively, stir stand-by after 10 minutes.
Be placed in the one-tenth of above-mentioned mixing foam maker weight, after applying pressure to 1Mpa, opens valve, can obtain oil product extinguishment hollow glass micropearl three-phase froth of the present invention.
Embodiment 4
In a kettle., under the mixing speed of 500 revs/min, add the water of 860g, 80g general proteins fire foam and the 60g hollow glass micropearl according to preprocessing process gained in embodiment 1 successively, stir stand-by after 8 minutes.
Be placed in the one-tenth of above-mentioned mixing foam maker weight, after applying pressure to 0.8Mpa, opens valve, can obtain oil product extinguishment hollow glass micropearl three-phase froth of the present invention.
The performance of products obtained therefrom of the present invention
Properties of product of the present invention below for being prepared by method described in embodiment 4:
(1) stability
According to fire foam current techique standard, 25% drainage time of hollow glass micropearl three-phase froth of the present invention on average can reach 20min08s, is about 6.4 times of common two-phase foam.Refer to table 1.
Table 1 the present invention and common two-phase foam 25% drainage time contrast
(2) ability of anti-burning
According to fire foam current techique standard, under flame thermal radiation condition, general proteins foam at about 3min by complete scaling loss.Three-phase froth of the present invention about 2min after being heated can form form compact and stable skeleton structure gradually, and after the 12h that is heated continuously, burn out rate is less than 25%, and ability of anti-burning significantly strengthens.
(3) anti-resume combustion performance
With reference to the standard testing of fire foam current techique, when foam coverage thickness is 5cm, general proteins two-phase foam there is resume combustion at about 3min, during 7min15s, resume combustion area reaches 50%.Three-phase froth of the present invention can form dense solid layer at about 10min, inhibits the evaporation of oil product, resume combustion does not occur.
Experiment effect
(1) before and after oleophobic modification cenosphere on the impact of foam solution foaming capacity
Ankyrin foam fire-fighting agent content is 10%, is contrasted by cenosphere after the process of modification oleophobic, the results are shown in Figure 1 to the foaming capacity of foam and conventional hollow glass microballoon.Wherein, X/% is the percentage by weight that cenosphere adds, and N is coefficient of foaming; 1 is modified hollow glass micropearl, and 2 is unmodified conventional hollow glass microballoon.
As shown in Figure 1, the process of modification oleophobic has remarkable impact to cenosphere frostproof froth n ability.Use conventional hollow glass microballoon, with the increase of its adding proportion, the coefficient of foaming of protein foam concentrate significantly reduces, and after cenosphere addition is more than 10%, protein foam concentrate can not effectively foam.And the foaming capacity of cenosphere to protein foam concentrate of gained has no significant effect after the process of modification oleophobic.
(2) hollow glass micropearl addition is on the impact of three-phase froth stability
According to the technical scheme that embodiment 1 is recorded, when hollow glass micropearl addition is different, hollow glass micropearl three-phase froth stability influence the results are shown in Table 2 (X% is the weight percentage of hollow glass micropearl)
Table 2 hollow core glass microballoon of the present invention addition is on the impact of three-phase froth 25% drainage time
(3) hollow glass micropearl addition affects three-phase froth pasta heat endurance
Fig. 2 is the technical scheme recorded according to embodiment 2, and when hollow glass micropearl addition is different, three-phase froth height over time.H is the free height of ullage foam.In figure, 1 is common two-phase protein foam; 2 for microballon content be 1%; 3 for microballon content be 3%; 4 for microballon content be 5%.
Can be found out intuitively by Fig. 2, along with increasing gradually of microballon content, foam height keeps degree also to improve gradually in time.
(4) the anti-resume combustion performance of hollow glass micropearl three-phase froth
Hollow glass micropearl three-phase froth and general proteins two-phase foam test the results are shown in Table 3, table 4 and Fig. 3.
Fig. 3 for being 8% (embodiment 3 products obtained therefrom) when hollow glass micropearl addition, during anti-resume combustion performance test, not hollow glass micropearl three-phase froth pattern in the same time.Wherein, state when Fig. 3 a is 1min49s; Fig. 3 b is the state of 5min23s.
Table 3 common two-phase protein foam anti-resume combustion performance test result
Table 4 hollow glass micropearl three-phase froth anti-resume combustion performance test result
Claims (5)
1. an oil product extinguishment hollow glass micropearl three-phase froth, it is characterized in that, comprise following component, following component components by weight percentage is: the general proteins fire foam of 8-15%, with the hollow glass micropearl of the surface modification treatment of 3-10%, surplus is water;
The hollow glass micropearl of surface modification treatment prepares by the following method:
(1) acid treatment: under the mixing speed of 250-500 rev/min by volume ratio be the hollow glass micropearl of 50%-75% add volume ratio be 7: 3 the concentrated sulfuric acid and 30% hydrogen peroxide mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, after stirring 30min, after washing with water, filter, drying for standby;
(2) alkali treatment: by above-mentioned steps 1 under the mixing speed of 250-500 rev/min) in the volume ratio of process gained be the hollow glass micropearl of 50%-75% add volume ratio be 1: 1: 5 25% ammoniacal liquor, 30% hydrogen peroxide and water mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, under 60-70 DEG C of condition after ultrasonic reaction 60min, filter, drying for standby;
(3) hollow glass micropearl surface modification treatment: be that the pH of the alcoholic solution of the silane coupler of 0.1-2.0% is adjusted to 3-5 by concentration with concentrated hydrochloric acid, add the hollow glass micropearl after soda acid process, under 60-70 DEG C of condition after ultrasonic reaction 4-6h, filter, drying, obtains the hollow glass micropearl of surface modification treatment.
2. a kind of oil product extinguishment hollow glass micropearl three-phase froth as claimed in claim 1, it is characterized in that, comprise following component, following component components by weight percentage is: the general proteins fire foam of 10%, with the hollow glass micropearl of the surface modification treatment of 8%, surplus is water.
3. a kind of oil product extinguishment hollow glass micropearl three-phase froth as claimed in claim 1 or 2, is characterized in that, the granularity of the hollow glass micropearl of described surface modification treatment is between 10-250 μm, and bulk density is 0.1-0.3g/cm
3.
4. the preparation method for hollow glass micropearl three-phase froth of the oil product extinguishment described in claim 1 or 2, is characterized in that, the steps include:
1) premixed: in container, adds water, general proteins fire foam, hollow glass micropearl in proportion in order under the mixing speed of 250-500 rev/min, stand-by after stirring 5-10min;
2) foam: the one-tenth of premixed is placed in foam maker, after applying pressure to 0.5-1Mpa, opens valve, described oil product extinguishment hollow glass micropearl three-phase froth can be obtained;
Described hollow glass micropearl carries out following process successively before described pre-blend step:
1) acid treatment: under the mixing speed of 250-500 rev/min, hollow glass micropearl is added volume ratio be 7: 3 the concentrated sulfuric acid and 30% hydrogen peroxide mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, after stirring 30min, after washing with water, filter, dry;
2) alkali treatment: under the mixing speed of 250-500 rev/min by acid treatment step, hollow glass micropearl add volume ratio be 1: 1: 5 25% ammoniacal liquor, 30% hydrogen peroxide and water mixed solution in, wherein, the volume ratio of hollow glass micropearl and above-mentioned mixed solution is 1: 1.5-1: 2, under 60-70 DEG C of condition after ultrasonic reaction 60min, filter, dry;
3) hollow glass micropearl surface modification treatment: be that the pH of the alcoholic solution of 0.1-2.0% silane coupler is adjusted to 3-5 by concentration with concentrated hydrochloric acid, add the hollow glass micropearl after soda acid process, under 60-70 DEG C of condition after ultrasonic reaction 4-6h, filter, drying, both obtained required hollow glass micropearl.
5. the preparation method of a kind of oil product extinguishment hollow glass micropearl three-phase froth as claimed in claim 4, it is characterized in that, described silane coupler is: 13 fluoro octyl triethoxysilanes, or the pungent sulphonyl aminopropyl triethoxysilane of perfluor.
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