Newtonian foam superconcentrate
10071273 ยท 2018-09-11
Assignee
Inventors
Cpc classification
A62C35/023
HUMAN NECESSITIES
A62C3/00
HUMAN NECESSITIES
A62C99/0009
HUMAN NECESSITIES
A62C99/009
HUMAN NECESSITIES
A62C99/0018
HUMAN NECESSITIES
International classification
A62C3/00
HUMAN NECESSITIES
A62C35/02
HUMAN NECESSITIES
Abstract
The invention provides an aqueous foaming Newtonian concentrate, an expanded foam composition and a process of forming a foam composition concentrate. The aqueous foaming concentrate includes a carbonized saccharide mixture, a surfactant, water and optionally further agents including cross-linking agents, thickeners, solvents, stabilizers, buffers, corrosion inhibitors and preservatives. Foaming concentrates of the present invention are free of fluorine and persistent organic pollutants and particularly suited for use in fire prevention, suppression and extinguishment, vapor suppression and wetting of surfaces at concentrations less than 1.3% by weight.
Claims
1. A method of making a fire extinguishing foam solution comprising: providing a fluorine-free concentrate including a sugar that has been subjected to a carbonization step during its manufacture and one or more surfactants, wherein the concentrate is free of fluorine, and forming a foam forming solution by diluting the concentrate with water, wherein the foam forming solution contains less than 1.3% by volume of the concentrate and exhibits a viscosity of 100 cSt or less.
2. The method according to claim 1 wherein the concentrate includes a cross-linker.
3. The method according to claim 1 wherein the water is sea water.
4. The method according to claim 1 wherein the sugar is a dark brown sugar.
5. The method according to claim 1 wherein the concentrate includes less than 34% by weight of water.
6. The method according to claim 1 wherein the concentrate includes one or more polysaccharides.
7. The method according to claim 6 wherein the one or more polysaccharides are present in the concentrate at an amount equal to or less than 0.1% by weight.
8. The method according to claim 1 wherein the foam forming solution is a Newtonian solution.
9. The method according to claim 1 further comprising aerating the foam forming solution thereby forming a foam.
10. The method according to claim 9 further comprising applying the foam to a Class B fire and effectively extinguishing the fire.
11. The method according to claim 1 wherein the concentrate is free of persistent organic pollutants.
12. A fire extinguishing foam solution comprising: a concentrate including a sugar that has been subjected to a carbonization step during its manufacture, an amount of water added to the concentrate to provide a mix including 1.3% by volume or less of the concentrate, and one or more surfactants, wherein the concentrate is free of fluorine and persistent organic pollutants and the mix exhibits a viscosity of 100 cSt or less.
13. The solution according to claim 12 wherein the concentrate includes between 10% by weight and 35% by weight of the water.
14. The solution according to claim 12 wherein the concentrate includes 6% to 17% by weight of the sugar.
15. The solution according to claim 12 wherein the concentrate includes about 19% by weight of the one or more surfactants.
16. The solution according to claim 12 wherein the concentrate includes a total polysaccharide content of 0.1% by weight or less.
17. The solution according to claim 12 wherein the mix is a Newtonian solution.
18. The solution according to claim 12 wherein the mix is in the form of a foam.
19. The solution according to claim 12 further comprising 15% to 20.0% by weight of total active surfactant.
20. The solution according to claim 12 further comprising 4.5% to 7.0% by weight of amphoteric surfactant.
21. The solution according to claim 12 further comprising 7.0% to 11.0% by weight of anionic surfactant.
22. The solution according to claim 12 further comprising 1.0% to 4.0% by weight of nonionic surfactant.
23. The solution according to claim 12 further comprising 0.1% to 2.0% by weight of a stabilizer.
24. The solution according to claim 12 further comprising 6.0% to 20.0% by weight of salt.
25. The solution according to claim 12 further comprising 0.1% to 15.0% by weight of solvent.
26. A method of extinguishing a fire comprising: providing a concentrate including a sugar that has been subjected to a carbonization step during its manufacture, and one or more surfactants, wherein the concentrate is free of fluorine, mixing the concentrate with an amount of water to provide a solution including 1.3% or less by volume of the concentrate, aerating the solution to produce a foam, and applying the foam to a fire, wherein the foam is not an aqueous film forming foam or an alcohol-resistant aqueous film forming foam.
27. The method according to claim 26 wherein the concentrate includes between 10% by weight and 35% by weight of the water.
28. The method according to claim 26 wherein the concentrate includes about 17% by weight of the sugar.
29. The method according to claim 26 wherein the concentrate includes about 19% by weight of the one or more surfactants.
30. The method according to claim 26 wherein the concentrate includes a total polysaccharide content of 0.1% by weight or less.
31. The method according to claim 26 wherein the concentrate is free of persistent organic pollutants.
32. The method according to claim 26 wherein the foam forming solution is a Newtonian solution.
33. The method according to claim 26 wherein the fire is a Class B fire.
34. The method according to claim 26 wherein the solution includes 1.0% or less by weight of the concentrate.
35. The method according to claim 26 wherein the concentrate meets or exceeds European Standard EN 1568-3 for low expansion fire extinguishing foam concentrates.
36. The method according to claim 26 wherein the concentrate meets or exceeds Underwriters Laboratories standard for safety for foam equipment and liquid concentrates UL 162.
37. The method according to claim 26 comprising mixing the concentrate with an amount of water to provide a solution including between 0.9% to 1.0% by volume of the concentrate.
38. The method according to claim 26 comprising applying the foam directly to the fire using a sprinkler system.
39. A method of extinguishing a fire comprising: providing a concentrate including a sugar that has been subjected to a carbonization step during its manufacture, and one or more surfactants, wherein the concentrate is free of fluorine, mixing the concentrate with an amount of water to provide a solution including 1.3% or less by volume of the concentrate, aerating the solution to produce a foam, and applying the foam to a fire, wherein the solution exhibits a viscosity of 100 cSt or less.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The disclosure can be better understood with reference to the following drawings. The elements of the drawings are not necessarily to scale relative to each other, emphasis instead being placed upon clearly illustrating the principles of the disclosure. Furthermore, like reference numerals designate corresponding parts throughout the several views.
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DETAILED DESCRIPTION
(10) The invention provides chemical compositions that can be aerated to form an expanded foam composition (also referred to as a foam). The foam can be used in various applications including any applications understood to be useful in the art of aqueous foam materials. The foam finds particular utility in fighting Class B fires including flammable or combustible liquid or gas. The foam can also be useful to contain or suppress volatile, noxious, explosive, flammable, or otherwise dangerous chemical vapors. The vapors may evolve from a chemical such as a chemical storage tank, a liquid or solid chemical, or a chemical spill. The foam can also be used to extinguish a chemical fire or to prevent ignition or re-ignition of a chemical. These applications will be referred to collectively for purposed of the present description as application to a chemical or application to a liquid chemical. The compositions are especially useful for extinguishing and securing extremely flammable (e.g., having low boiling point and high vapor pressure) and difficult-to-secure chemicals, for example transportation fuels such as methyl t-butyl ether (MTBE) and ether/gasoline blends. Additionally, the foam can be applied to other substrates that are not necessarily hazardous, volatile, ignited, or ignitable. As an example, the foam may be applied to land, buildings, or other physical or real property in the potential path of a fire, as a fire break, e.g., to prevent or at least delay such property from catching fire.
(11) The foam is particularly useful in applications at remote or hard to reach locations, such as deep sea oil platforms or refineries. As will be discussed in greater detail below, the foam is produced in a superconcentrated form which saves space and allows for the storage of a greater amount of foam in a smaller area.
(12) As used herein, the term foam is used according to its industry-accepted sense, to mean a foam made by physically mixing a gaseous phase (e.g., air) into an aqueous liquid to form a two phase system of a discontinuous gas phase and a continuous aqueous phase.
(13) The foam mix of the invention comprises a concentrated mixture of a saccharide composition, a cross-linking composition or an organic salt, a surfactant and water, as taught for example in U.S. Pat. No. 7,569,155 and U.S. patent application Ser. No. 11/885,495, the disclosures of which are incorporated herein in their entireties by reference.
(14) Saccharides for use in the present invention are generally simple sugars or other such carbohydrates, preferably common sugar (sucrose) derived from sugar cane or sugar beets. Sucrose is a disaccharide composed from the basic, simple sugar molecules glucose and fructose. Sucrose is readily available given that the world production from cane and sugar beet is in the order of millions of tonnes per annum. Those skilled in the art will also be aware that other commercially available simple saccharides and sugars can be utilised in the foaming compositions of the invention.
(15) The carbonised saccharides include caramelised, charred or burnt sugars such as treacle, golden syrup and molasses. In this regard reference to the term carbonised as it refers to sugars and saccharides is taken in its broadest sense to include caramelised sugars including those that are sublimed, partially sublimed, flaked, baked, heat-treated or chemically treated to effect a morphological and/or chemical change to the sugar normally resulting in a form of polymerisation of the sugar molecules with concomitant darkening or charring of the sugar.
(16) The carbonised saccharide composition typically contains partially refined saccharide components of, for example, cane sugar present as brown or dark brown sugar, which enhances performance and consistency of performance over mixtures without caramelised, charred or burnt components.
(17) Controlled heating of a raw extract of saccharides a little above its melting point caramelises (or carbonises) the sugar molecules with a loss of water to form yellow, brown or dark brown-coloured sugar products such as molasses. As known in the art, caramelisation of sugars can be achieved by the action of steam pressure on sugar in a caramelising kettle, at a set temperature and for a controlled duration. Usually a heating interval of 60-180 minutes at a temperature of approximately 160-180.degree. C. will give satisfactory results. Typically gentler heating will produce a yellow or brown caramelised sugar, whereas stronger and/or prolonged heating will form darker brown or even black sugars more generally referred to as carbonised sugars.
(18) As used herein, the term caramelised sugar is taken to mean any darkened process sugar which includes the lighter caramelised sugars. The addition of carbonised sugar to common white sugar, with the optional addition of invert sugar, produces processed sugar commonly known as brown sugar. In a preferred embodiment, the carbonised saccharide composition for use in the foam forming compositions of the present invention is a brown sugar which has been subjected to a heating or drying step in the manufacturing process.
(19) Alternatively brown sugar is prepared by heating purified sugar syrup until it crystallises to form a soft yellow or brown sugar. The amount and duration of heating has a direct effect on the strength and darkness of the resultant brown sugar.
(20) Dark brown sugar, as supplied by CSR Australia, is particularly suitable for use in the compositions and methods of this invention. The CSR brown sugar comprises sucrose crystals painted with molasses syrup. The proportions are about >85% cane sugar (sucrose and reduced sugars such as glucose/fructose), <15% molasses, and <10% ash (carbonised sugars) and moisture, plus other organics including dextrin and other sugar cane related materials. In the production of the brown sugar, the carbonised saccharide mixture is subjected to a heating or drying step. It is thought that this processing step improves the fire resistance properties of the aqueous foaming compositions of the invention.
(21) Carbonisation of sugars is also possible by treating the sugar with a mineral acid such as sulphuric acid which chars the sugar, formic acid, carbon dioxide and sulphur dioxide being evolved, and a blackened mass of carbon resulting.
(22) A particularly preferred carbonised sugar blend is standard brown sugar obtained from CSR Australia. Best results are obtained from carbonised sugar compositions comprising 86-99.7 wt. % sucrose, 0-7 wt. % reduced sugars (eg., fructose and glucose), with molasses and charred/burnt sugars and ash 0.01-10 wt. % as balance. The quantity of water may be in the range of 5-89.9 wt. %, more preferably 45-70 wt. %; the surfactant 3-33 wt. % and the thickener 0-10 wt. %.
(23) Surfactants are included in the foaming compositions to facilitate foam formation upon aeration, to promote spreading of drainage from the foam composition as a vapor-sealing aqueous foam over a liquid chemical, and, where desired, to provide compatibility of the surfactant with sea water. Useful surfactants include water-soluble hydrocarbon surfactants and silicone surfactants, and may be non-ionic, anionic, cationic or amphoteric. Particularly useful surfactants include hydrocarbon surfactants which are anionic, amphoteric or cationic, e.g., anionic surfactants preferably having a carbon chain length containing from about 6 to about 12 or up to 20 carbon atoms. Salt surfactants, such as for example magnesium acetate, act as a cross linker and also offer protection against freezing. Saccharide surfactants, such as the non-ionic alkyl polyglycosides, can also be useful to the composition. Saccharide surfactants act to promote blending of the saccharides with the foam bubble.
(24) Organic solvents can be included in the foaming composition to promote solubility of a surfactant, to improve shelf life of a concentrated adaptation of the foaming composition, to stabilise the foam, and in some cases to provide freeze protection. Organic solvents useful in the foaming composition include but are not limited to glycols and glycol ethers including diethylene glycol n-butyl ether, dipropylene glycol n-propyl ether, hexylene glycol, ethylene glycol, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol, glycerol, polyethylene glycol (PEG) and sorbitol.
(25) Thickening agents are well known in the chemical and polymer arts, and include, inter alia, polyacrylamides, cellulosic resins and functionalised cellulosic resins, polyacrylic acids, polyethylene oxides and the like. One class of thickener that can be preferred for use in the foaming composition and methods of the invention is the class of water-soluble, polyhydroxy polymers, especially polysaccharides. The class of polysaccharides includes a number of water-soluble, organic polymers that can increase the thickness, viscosity or stability of a foam composition. Preferred polysaccharide thickeners include polysaccharides having at least 100 saccharide units or a number average molecular weight of at least 18,000. Specific examples of such preferred polysaccharides include xanthan gum, scleroglucan, heteropolysaccharide-7, locust bean gum, partially-hydrolyzed starch, guar gum and derivatives thereof. Examples of useful polysaccharides are described, for example, in U.S. Pat. Nos. 4,060,489 and 4,149,599. These thickening agents generally exist in the form of water-soluble solids, e.g., powders. While they are soluble in water, in their powder form they can and typically do contain a small amount of adventitious or innate water, which is absorbed or otherwise associated with the polysaccharide.
(26) In one embodiment, the foam concentrate composition of the present invention also may comprise a polysaccharide, preferably an anionic heteropolysaccharide having a high molecular weight. The polysaccharide is utilized to stabilize the foam. At rest, these long chained polysaccharide molecules are entwined and thus produce a high viscosity foam solution. During movement, such as the application of shear stress, the polysaccharide molecules elongate and the viscosity of the solution decreases. The resulting foam is thus characterized as pseudoplastic fluid, defined herein as a solution which displays lower viscosity at a higher shear rate. Pseudoplastic foam compositions present unique problems during dilution with water because of the decrease in viscosity observed with the application of shear stress during mixing. Special equipment is needed in most cases to mix the foam concentrate. As a result, creation of a more concentrated pseudoplastic foam solution is not practical.
(27) Many prior art foam concentrates utilize a polysaccharide concentration of varying amounts. The resulting mix requires a dilution at, for example, 3% or 6% (e.g., 3% foam concentrate with 97% water). The inventors of the currently disclosed invention have unexpectedly found that a foam mix with a lowered polysaccharide concentration, for example less than 0.1%, produces a solution with improved viscosity characteristics. A mix with this concentration of polysaccharides is classified as a Newtonian solution, defined herein as a foam concentrate that displays constant viscosity at various shear rates. The decrease in polysaccharide concentration in the current invention produces a mix with lower viscosity when subjected to mixing forces, allowing the solution to be more easily diluted in water. The present foam mix requires dilution at, for example, at less than 1.3% concentrate (e.g., less 1.3% foam solution with more than 98.7% water). As a result, the current foam composition may be stored as a more concentrated solution, thus requiring less storage space and lowering operational expenses. In another embodiment, the foam concentration of the present invention contains no polysaccharides. In another embodiment, the foam mix requires dilution 0.9% to 1.3% concentrate.
(28) Commercially available polysaccharides useful in the invention include those sold under the trademarks, e.g., Kelzan and Keltrol (available from Kelco). The polymeric structure is not critical for the purposes of this invention. Only a small amount of polysaccharide is required to result in a noticeable change in properties.
(29) Optionally, other polymeric stabilizers and thickeners can be incorporated into the concentrate compositions of the invention to enhance the foam stability of the foam produced by aeration of the aqueous solution made from the concentrate. Examples of suitable polymeric stabilisers and thickeners are partially hydrolzyed protein, starches and modified starches, polyacrylic acid and its salts and complexes, polyethyleneimine and its salts and complexes, polyvinyl resins, e.g., polyvinyl alcohol, polyacrylamides, carboxyvinyl polymers and poly(oxyethylene)glycol.
(30) Other ingredients known to those skilled in the art that are usually employed in fire-fighting compositions may be employed in the concentrate compositions of this invention. Examples of such ingredients are preservatives, buffers to regulate pH (e.g., tris(2-hydroxyethyl)amine or sodium acetate), corrosion inhibitors (e.g., toluoltriazole or sodium nitrite), antimicrobial agents, divalent ion salts, foam stabilisers and humectants. In addition, flame retardant materials such as inorganic salts (ex phosphates or sulfates) and organic salts (such as salts of acetate).
(31) A foaming composition can be prepared by mixing or combining together its ingredients, e.g., water, a carbonised saccharide mixture, and surfactant, plus any additionally desired ingredients. For example, a foaming composition can be prepared by providing water, e.g., a fixed amount within a reaction vessel or other container, or preferably a flow of water travelling through a hose or pipe, most preferably a hose, and then adding non-water ingredients (e.g., surfactant, thickener, etc.) to the water. The non-water ingredients can be added to the water individually or as one or more mixtures, and in any desired order.
(32) A foaming composition can be prepared using foam production equipment known in the fire-fighting art. Such equipment can include a conventional hose to carry a flow of water, plus appurtenant equipment useful to inject, educt or otherwise add non-water ingredients to the flow of water. Water can flow under pressure through a fire hose, and surfactant, thickener, and other non-water ingredients can be injected or drawn (e.g., educed by venturi effect) into the flow of water. Other techniques such as compressed gas foaming systems can be employed as well known to those skilled in the art.
(33) The composition of the invention is employed in the usual way to combat fires of flammable liquids or to prevent evaporation of flammable vapours. The composition is particularly suitable for application in the form of a foam. Usually it is stored in the form of an aqueous concentrate only requiring dilution typically as a 1.3% or less concentrate with either fresh, brackish or sea water to form the premix, followed by aeration of the premix to produce a foam which is applied to the burning substrate or substrate to be protected as required. The use of carbonised saccharide mixtures provides better fire protective properties of the foams of the invention when sea water, or brackish water, is used as the diluent.
(34) The foam mixture of the invention is a capable Class A foam that due to the surfactant mixture is capable of wetting fuels such as wood, paper, rubber, fabric, etc., and provide higher retained moisture to prevent combustion. Without wishing to be limited to theory, it is believed that the inclusion of sugars, and charred or burnt sugars, and related molasses and partially refined components of sugar cane, will form a protective layer and char further when fire impinges on the coated material. In a fire situation, the foam mixture can extinguish the fire via cooling and smothering (oxygen removal). The related sugar compounds could again form a protective layer on the combustible fuel if applied at significant concentrations.
(35) The foam of the invention has rapid flow characteristics on flammable liquids, like an aqueous film forming foam (AFFF), yet does not necessarily fulfill the mathematical parameters of the spreading coefficient calculation, nor does it necessarily have a positive spreading coefficient. However the mixtures do have measurable and well-defined surface tensions and interfacial tensions.
(36) Other uses, embodiments and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof cited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
EXAMPLES
Example 1
(37) For comparison purposes,
Example 2
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(39) TABLE-US-00001 TABLE 1 Amount Ranges (% by (% by Class Chemical Name Weight) Weight) Foam Stabilizer Polycarboxylic acid 2.0 0.1 to 2.00 Nonionic Alkyl Polyglucoside 1.5 1.2 to 6.0 Surfactant Anionic/Biocide Monolaurin 0.5 0.5 to 2.0 Nonionic Sodium 1.5 0.2 to 2.0 Surfactant Decylgmcosides Hydroxypropyl Phosphate Nonionic Sodium 1.5 0.1 to 5.0 Surfactant Laurylglucosides Hydroxypropylsulfonate Nonionic Polmeric Alkyl 1.5 0.1 to 2.0 Surfactant Polyglucoside anionic surfactant Anionic Triethanolamine Alkyl 7.0 0.0 to 10.0 Surfactant Sulphate Anionic Sodium-n-Octylsulfate 9.0 0.0 to 15.0 Surfactant Anionic Sodium-n-Decylsulfate 2.0 0.0 to 5.0 Surfactant Anionic Sodium Alkyl Ethoxy 6.0 0.0 to 10.0 Surfactant Sulphate Amphoteric Cocamidopropyl 7.14 2.0 to 8.0 Surfactant Hydroxysutaine Amphoteric Cocoamido Propyl 5.63 1.5 to 7.0 Surfactant Betaine Amphoteric Cocamidopropylamine 0.75 0.2 to 0.8 Surfactant Oxide Silicone Coco Glucosides 1.5 0.0 to 2.0 Surfactant Hydroxylpropyl Dimethicone Copolymer Sucrose/Molasses Dark Brown Sugar 8.0 5.0 to 15.0 Sucrose Short Chain Sugar 7.0 0.0 to 10.0 Dextrose White Sugar 2.0 1.0 to 10.0 Salt Magnesium Acetate 7.0 6.0 to 20.0 Solvent Butyl Carbitol 5.0 0.0 to 15.0 Buffer Triethanolamine 0.5 0.0 to 5.0 Water 22.98 Total 100 Total Active Surfactant 18.75 Amphoteric Surfactant 5.48 Anionic Surfactant 9.62 Nonionic Surfactant 2.8 Sugar 17.0
Nonionic surfactants may be selected from Agnique series surfactants from BASF, ALKADET series and ECOTERIC series surfactants from Hunstman Surfactant Technology, and SugaFax, Poly SugaPhos and Suganate series surfactants from Colonial Chemical, Inc. Anionic surfactants may be selected from Texapon series surfactants from BASF and Tensagex series surfactants from TensaChem, SA. Amphoteric surfactants may be selected from GARDIQUAT series surfactants from Albright & Wilson and Dehyton series surfactant from BASF.
(40) The results illustrated in
(41) Performance testing of the foam mixture showed that the mixture is effective for fire control, fire extinguishment, and burn back resistance capabilities similar to AFFF technology when used on flammable liquids. This has been observed on a number of flammable liquid fuels and a variety of flammable liquid test pools (of surface area 0.28 m2, 3.0 m2, 4.5 M2, and 90 m2). Tests were conducted on flammable liquids such as AVGAS, AVTUR, and naphthalated blends. The 90 m2 surface area test does not represent a standard test, but represents an application density of between 2.5-5.0 ltm/m2 on larger fires as per the recommendations of Underwriters Laboratories.
Example 3
(42)