NL2022567B9 - Long term fire retardant - Google Patents
Long term fire retardant Download PDFInfo
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- NL2022567B9 NL2022567B9 NL2022567A NL2022567A NL2022567B9 NL 2022567 B9 NL2022567 B9 NL 2022567B9 NL 2022567 A NL2022567 A NL 2022567A NL 2022567 A NL2022567 A NL 2022567A NL 2022567 B9 NL2022567 B9 NL 2022567B9
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- fire
- retardant
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- concentrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
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Abstract
The present invention is in the field of a biodegradable long term fire retardant concentrate, a fire retardant solu— tion comprising said fire retardant concentrate, a method of retarding a fire using said solution, a method of preparing said long term fire retardant concentrate, and a method of preparing said fire retardant solution.
Description
Long term fire retardant
FIELD OF THE INVENTION The present invention is in the field of a biodegradable long term fire retardant concentrate, a fire retardant solu- tion comprising said fire retardant concentrate, a method of retarding a fire using said solution, a method of preparing said long term fire retardant concentrate, and a method of preparing said fire retardant solution.
BACKGROUND OF THE INVENTION The present invention is in the field of a biodegradable long term fire retardant concentrate, a fire retardant solu- tion, and use thereof. Fire may be symbolized by a tetrahedron, which symbol char- acterizes itself by four (tetra) elements, namely oxygen, heat, fire source, and an uninhibited chain reaction. An opti- mized agent should preferably provide a chemical/physical ac- tion in all four of the tetrahedron domains. A burning process can be chemically symbolized in the fol- lowing reaction scheme: Colm + O2 —through ignition — CO: +H:20 wherein CpHn is a fire source. Ignition is considered to take place through heat. However in reality the reaction is much more complex and typically comprising various intermediate and often incomplete steps. These steps may form radicals. If these could be captured or bounded the fire process may be in- terrupted and the fire may be easily extinguished. A typical burning process may be divided into three phases, a growth phase, a burning phase, and an extinguishing phase, each with an accompanying temperature profile. In addition there also is a spatial gradient. A heat gradient has a typi- cal temperature profile from a peripheral temperature of about 20°C to a central temperature of some 1200° C or higher. The present invention is focused on the growth phase and intends to limit growth of the fire by providing a fire re- tardant. Various prior art fire retardants are available. How- ever these retardants are relatively toxic to life in general and to an environment to which the retardant is provided. They typically comprise large amounts of polyphosphates (typically 40 > 93%) ,and corrosion inhibitors (some 1.5%, such as sodium ferrocyanide). They are typically effective and storage sta- ble.
Hence there still is a need for a relative simple and ef- fective long term fire retardant, which overcomes one or more of the above mentioned disadvantages without jeopardizing ben- eficial characteristics.
SUMMARY OF THE INVENTION The present invention relates in a first aspect to a biode- gradable long term fire retardant concentrate comprising an aqueous concentrate. It is aimed at long term stability for storage, a high viscosity, and to be applied as a diluted so- lution with sufficient viscosity and fire retardant proper- ties. Said sclution can be applied from air and from the ground. Manufacture of the concentrate is found difficult in view of the large amounts of components (e.g. a high salt level), and to arrive at a composition that is stable over time and stable at elevated temperatures, and hence the pre- sent invention also relates to a method of preparing said fire retardant concentrate, and fire retardant solution. The con- centrate comprises 0.2-5 wt.% biopolymer comprising polysac- charide, preferably 0.5-3 wt.%, 5-25 wt.$%$ phosphate, prefera- bly 7-15 wt.%, such as 8-12 wt.%, 10-40 wt.% sulfate, prefera- bly 15-30 wt.%, such as 18-25 wt.%, 0.5-10 wt.% solvent, pref- erably 1-8 wt.%, such as 3-6 wt.%, 0.0-10 wt.% thickener, preferably 0.5-8 wt.%, such as 1-5 wt.%, 0.5-20 wt.$% nanopar- ticles, wherein the nanoparticles are selected from clay min- erals, silicate minerals, and combinations thereof, preferably 1-15 wt.%, such as 2-10 wt.%, 0.05-2 wt.% colorant, preferably
0.1-1.5 wt.%, such as 0.2-1 wt.%, and 40-60 wt.% water, such as 45-55 wt.%, with the proviso that at least one of phosphate and sulfate comprises ammonium, and with the proviso that no F is present, wherein all wt.% are relative to a total weight of the composition. Ali of the components are fully biodegrada- ble, non-toxic to human beings and to the environment. The present solution may be used as a spray, may be nebulized, or as a flow. It is found to be very effective to retard a fire in certain direction and therewith direct the fire in another direction. By doing so fire extinguishing is limited to cer- tain areas and therefore much more effective, as is supported by tests under standard conditions. In addition the present agent fully decomposes into products not being harmful to the environment and human beings within 28 days under typical con- ditions, and typically within 14 days. The present concentrate is stable for longer periods of time, typically more than 3-6 months and hence can be stored for at least said periods. Test under varying temperatures and conditions indicate a storage stability of at least 5 years. In addition it consumes rela- tively little space, and can therefore also be stored on loca- tion, such as a strategic supply, or moved to said location quickly, without any problem.
The present products have been tested by CEREN in France, and the results on performance was better than the existing products which have an dilution in water of 20 to 25% to reach the wind tunnel test. This product already reach the same per- formance level by 13,5% The results on toxicity and biodegra- dability are as follows: 1- Toxicity on Bacteria: EC 30 (30 Min) >1% ISO 11348-3; 2- Ecotoxicity Fish: EC 50 (96h) >100 mg/L OECD 203; 3- Ecotoxicity daphanids EC 50 (48h) >100 mg/L OECD 202; and 4- Ecotoxicity algae EC 50 (72h) >100 mg/L OECD
201. Biodegradability 100 % in 17 days according tc OECD 301B. The products have a density of about 1.24 g/cm? (EN ISO 12185), a pH of about 7.7, a freezing point of about -10°C, a viscos- ity of about 2000 Mpas , and being not corrosive (ASTM D 665 and ASTM D130) These are considered very satisfying results, also in view of future government regulations.
In a second aspect the present invention relates to a fire retardant solution comprising 10-15 wt.% of the present con- centrate and 85-90 wt.% water.
In a third aspect the present invention relates to a method of preparing a fire retardant concentrate according to the in- vention, comprising mixing all polysaccharide and 20-30% of the solvent thereby obtaining a first mixture, dispersing said first mixture in all the water at 500-700 rpm until a smooth gel is formed, adding all sulfate and all phosphate at 600-800 rpm until a thinner gel is formed, adding ali thickener, the remainder of the solvent, until the thickener is fully dis- persed, adding all the nanoparticles until a homogeneous mix- ture is obtained, and adding all cclorant.
In a fourth aspect the present invention relates to a method of preparing a fire retardant solution comprising providing 10-15 wt.$% of the concentrate, and mixing the con- centrate with 85-90 wt.% water.
In a fifth aspect the present invention relates to retard- ing a fire comprising providing an fire retardant solution ac- cording to the invention, limiting propagation of the fire in at least one direction by providing the fire retardant solu- tion at a side of the fire in the at least one direction, and further, in a sixth aspect, to extinguishing a fire, by re- tarding the, and extinguishing the fire in another direction.
In summary the present solution is 100% biodegradable, non- toxic for nature of all kinds, no residues are left behind, liquid starts after the fire acting as a fertilizer, it pre- vents pollution of unburned particles on big scale, it pro- vides very fast retardation of fires, typically six times faster than water, no re-ignition occurs, once the fire is ex- tinguished it will not reignite, it is 100% biodegradable, it is nontoxic to lower forms of organisms such as bacteria, fish, daphanids and algae, and it is not harmful for pecple, other animals and nature in general.
Thereby the present invention provides a solution to one or more of the above mentioned problems and drawbacks. Advantages of the present description are detailed throughout the description.
DETAILED DESCRIPTION OF THE INVENTION The present invention relates in a first aspect to a biode- gradable long term fire retardant concentrate according to claim 1.
In an exemplary embodiment the present long term fire re- tardant concentrate may comprise 1-7 wt.% ammonium, preferably 2-5 wt.%, such as 3.5-4.5 wt.%.
In an exemplary embodiment of the present long term fire retardant concentrate no polyphosphate is present, such as am- monium polyphosphate.
In an exemplary embodiment the present long term fire re- tardant concentrate the phosphate and/or sulfate may comprise a cation selected from Ht, Nat, K+, NHa*, and Ca?2*, and combina- tions thereof, preferably NH.
In an exemplary embodiment of the present long term fire retardant concentrate the soivent is selected from aliphatic, branched, and partly saturated Ci-Cs alcohols, aliphatic, branched, and partly saturated Ci-Cs diols, and combinations 5 thereof, preferably isopropyl alcohol (CAS 67-63-0), propylene glycol (CAS 57-55-6)}), and propanol.
In an exemplary embodiment of the present long term fire retardant concentrate the biopolymer is selected from biopoly- mers, oligomers of said biopolymers, copolymers of said bi- opolymers, and combinations thereof.
In an exemplary embodiment of the present long term fire retardant concentrate the biopolymer has a molecular weight of > 2 kDa, preferably 10-300 kDa, more preferably 30-150 kDa, such as 50-100 kDa.
In an exemplary embodiment of the present long term fire retardant concentrate the biopolymer is selected from alginate or bacterial alginate (KYMERA), preferably extracellular poly- meric substances obtainable from granular sludge, wherein the granular sludge preferably is one or more of aerobic granular sludge and anammox granular sludge.
In an exemplary embodiment of the present long term fire retardant concentrate the thickener is selected from natural gums, such as guar gum, xanthan gum, lccust bean gum, chicie gum, dammar gum, and polypeptides, such as proteins.
In an exemplary embodiment of the present long term fire retardant concentrate the thickener has a molecular weight of > 50 kDa, preferably 100-1500 kDa, more preferably 200-1000 kDa, such as 300-800 kDa.
In an exemplary embodiment of the present long term fire retardant concentrate the concentrate has a dynamic viscosity (@ 20 °C; ASTM D445) of 1500-2500 mPa*s, preferably 1800-2200 mPa*s, such as 1900-2100 mPa*s, and/cr a kinematic viscosity (@ 20 °C; ASTM D445) of 1070-1925 mm2/s, and/or a density of
1.25-1.5 g/cm?, such as 1.3-1.4 g/cm?, such as 1.33-1.38 g/cm3, and/or wherein the pH is from 6.5-7.5.
In an exemplary embodiment of the present concentrate the nanoparticles are selected from montmorillonite (MMT). It is preferred to use 0.1-10 wt.% clay mineral. It has been found that fires are extinguished more efficiently, using less wa- ter, and the alginate and clay are considered to form a coat- ing, which coating does not set fire. It is preferred to use
0.2-5 wt.% alginate, such as 1-2.5 wt.%. It is preferred to use 0.2-5 wt.% clay mineral, such as 1-2.5 wt.%. In an example the pre-sent clay minerals are one or more of a natural or ar- tificial clay, the clay preferably being a monovalent cation clay. The clay preferably has a cationic exchange capacity of 2-200 meg/100 grams clay at a pH of 7, more preferably 5-150 meg/100 grams, even more preferably 10-120 meg/100 grams. It has been found that clays having a relatively higher CEC per- form better in terms of relevant characteristics for the pre- sent invention. The clay may comprise one or more of H+, Na+, K+, Li+. The clay may be a tetrahedral-octahedral-tetrahedral (TOT) -clay (or 2:1 clay), such as a kaolin clay, such as kao- linite, dickite, halloysite and nacrite, a smectite clay, such as bentonite, montmorillonite, nontronite and saponite, an il- lite clay, a chlorite clay. Also a silicate mineral, such as mica, such as biotite, lepidolite, muscovite, phlogopite, zinnwaldite, clintonite, and allophane, are applicable as well as platelet like particles. The one or mere of the above examples and embodiments may be combined, falling within the scope of the invention.
EXAMPLES The invention is further detailed by the accompanying exam- ple, which is exemplary and explanatory of nature and are not limiting the scope of the invention. To the person skilled in the art it may be clear that many variants, being obvious or not, may be conceivable falling within the scope of protec- tion, defined by the present claims. Example Preparation of fire retardant concentrate. 20 gr IPA and 18 gr alginate (Satialgine S1100 of Algaia) were thoroughly mixed and dispersed in 1000 gr of water under mixing with a rotary mixer at 500-700 rpm. When a homogeneous gel is formed, with- out clods, 400 gr of NHa4S04 and 212 gr H(NH4)2PCs are added. The speed of the rotary mixer is increase with 100 rpm, and the gel becomes somewhat thinner. Thereafter 60 gr guar gum and 60 gr IPA are mixed, and then dispersed in the gel under thorough mixing. Then 140 gr kaolin clay is slowly added under constant mixing until a homogenous mixture is formed. Finally 12 gr red vegetable pigment is added. The formed concentrate has a pH of about 7, and a viscosity of 2000 mPa*s (£10%). The concentrate may then be mixed with water in a ratic of 13.5% concentrate and 86.5% water, therewith forming a solution. The viscosity of the solution is from 50-500 mPa*s, and typically 320 mPa*s (+10%). It has a density of 1.05-1.15 gr/cm3, typically about
1.08 gr/cm3.
For the purpose of searching prior art the following sec- tion is added, representing a translation of the last section in English:
1. Biodegradable long term fire retardant concentrate comprising
0.2-5 wt.% biopolymer comprising polysaccharide, preferably
0.5-3 wt.$%, 5-25 wt.% phosphate, preferably 7-15 wt.%, 10-40 wt.3 sulfate, preferably 15-30 wt.$%,
0.5-10 wt.% solvent, preferably 1-8 wt.%,
0.0-10 wt.% thickener, preferably 0.5-8 wt.$%,
0.5-20 wt.% nanoparticles, wherein the nanoparticles are selected from clay minerals, silicate minerals, and combina- tions thereof, preferably 1-15 wt.%,
0.05-2 wt.% colorant, preferably 0.1-1.5 wt.%, and 40-60 wt.% water, with the proviso that at least one of phosphate and sulfate comprises ammonium, and with the proviso that no F is present, wherein all wt.$% are relative to a total weight of the composition.
2. Fire retardant concentrate according to embodiment 1, com- prising 1-7 wt.% ammonium, preferably 2-5 wt.%, preferably with the proviso that no polyphosphate is present, such as am- monium polyphosphate.
3. Fire retardant according to any of embodiments 1-2, wherein the phosphate and/or sulfate comprise a cation selected from H*, Na*, K, NHat, and Ca?", and combinations thereof, preferably NH".
4. Fire retardant concentrate according to any of embodiments 1-2, wherein the sclvent is selected from aliphatic, branched, and partly saturated C;-Cs alcohols, aliphatic, branched, and partly saturated C:i-Cs diols, and combinations thereof, prefer- ably isopropyl alcohol (CAS 67-63-0), propylene glycol (CAS 57-55-6}, and propanol.
5. Fire retardant concentrate according to any of embodiments 1-4, wherein the biopolymer is selected from biopolymers, oli- gomers of said biopolymers, copolymers of said biopolymers, and combinations thereof, and/or wherein the biopolymer has a molecular weight of > 2 kDa, preferably 10-300 kDa, more pref- erably 30-150 kDa, such as 50-100 kDa.
6. Fire retardant concentrate according to embodiment 3, wherein the biopolymer is selected from alginate or bacterial alginate (KYMERA), preferably extracellular polymeric sub- stances obtainable from granular sludge, wherein the granular sludge preferably is one or more of aerobic granular sludge and anammox granular sludge.
7. Fire retardant concentrate according to any of embodiments 1-6, wherein the thickener is selected from natural gums, such as guar gum, xanthan gum, locust bean gum, chicle gum, dammar gum, and polypeptides, such as proteins, and/or wherein the thickener has a molecular weight of > 50 kDa, preferably 100- 1500 kDa, more preferably 200-1000 kDa, such as 300-800 kDa.
8. Pire retardant concentrate according to any of embodiments 1-7, wherein the concentrate has a dynamic viscosity (@ 20 °C; ASTM D445) of 1500-2500 mPa*s, preferably 1800-2200 mPa*s, and/or a kinematic viscosity (@ 20 °C; ASTM D445) of 1070-1925 mm?/s, and/or a density of 1.25-1.5 g/cm?®, such as 1.3-1.4 g/cm, and/or wherein the pH is from 6.5-7.5.
9. Fire retardant concentrate according to any of embodiments 1-8, wherein the colorant is selected from natural pigments, such as vegetable pigments, and metal oxides, such as iron ox- ide, preferably natural pigments.
10. Fire retardant solution comprising 10-15 wt.% of a concentrate according to any of embodiments 1-9, and 85-90 wt.$% water.
11. Fire retardant solution according to embodiment 10, wherein the concentrate has a dynamic viscosity (@ 20 °C; ASTM D445) of 50-500 mPa*s, preferably 100-400 mPa*s, and/or a kin- ematic viscosity {(@ 20 °C; ASTM D445) of 43-475 mm?/s, and/or a density of 1.05-1.15 g/cm?, such as 1.06-1.09 g/cm3, and/or wherein the pH is from 6.5-7.5.
12. Method of preparing a fire retardant concentrate according to any of embodiments 1-9, comprising mixing all polysaccharide and 20-30% of the solvent thereby obtaining a first mixture, dispersing said first mixture in all the water at 500-700 rpm until a smooth gel is formed, adding all sulfate and all phosphate at 600-800 rpm until a thinner gel is formed, adding all thickener, the remainder of the solvent, until the thickener is fully dispersed, adding all the nanoparticles until a homogeneous mixture is obtained, and adding all colorant.
13. Method of preparing a fire retardant solution comprising providing 10-15 wt.% of the concentrate according to any of embodiments 1-9, and mixing the concentrate with 85-90 wt.% water.
14. Method of retarding a fire comprising providing an fire retardant solution according to embodi- ment 13, and limiting propagation of the fire in at least one direc- tion by providing the fire retardant solution at a side of the fire in the at least one direction.
15. Method of extinguishing a fire, comprising retarding the fire according to embodiment 14, and extinguishing the fire in another direction.
16. Method according tc embodiment 14 or 15, wherein the solu- tion is provided from air, from ground, or a combination thereof.
Claims (16)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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NL2022567A NL2022567B9 (en) | 2019-02-13 | 2019-02-13 | Long term fire retardant |
PCT/NL2020/050074 WO2020167116A1 (en) | 2019-02-13 | 2020-02-12 | Long term fire retardant |
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NL2022567A NL2022567B9 (en) | 2019-02-13 | 2019-02-13 | Long term fire retardant |
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NL2022567B1 NL2022567B1 (en) | 2020-08-27 |
NL2022567B9 true NL2022567B9 (en) | 2020-12-15 |
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NL2022567A NL2022567B9 (en) | 2019-02-13 | 2019-02-13 | Long term fire retardant |
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WO (1) | WO2020167116A1 (en) |
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US6162375A (en) * | 1994-07-21 | 2000-12-19 | Fire-Trol Holdings, L.L.C. | Fugitive color fire retardant composition for aerial application |
US6322726B1 (en) * | 1998-02-27 | 2001-11-27 | Astaris, Llc | Fire retardant concentrates and methods for preparation thereof and use |
CN109260644B (en) * | 2018-11-06 | 2021-07-06 | 陈金城 | Water-based extinguishing agent and preparation method thereof |
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