Gel foam compositions and applications

Abstract

The present application relates to the field of emergency treatment of dangerous chemical leakage, and discloses a composition for gel foam and application, and a product and method for treating leaked dangerous chemicals. The composition comprises independently stored component A and component B, the component A comprises polyvinyl alcohol, a foaming agent and another water-soluble film-forming polymer, and the component B comprises an organic boron crosslinking agent. When the composition for gel foam is used, the gel time is controllable, the foam strength is high, the covering area is large, the covering time is long, the steam suppression effect is good, the composition is suitable for treating dangerous chemicals with different properties, and the composition does not need to be re-dispensed on site and can be used immediately, so that the treatment of dangerous chemicals is more efficient, and no secondary pollution is caused after use.

Description

Technical Field

[0001] This invention relates to the field of emergency response to hazardous chemical spills, specifically to a composition for gel foam and its application. Background Technology

[0002] In recent years, the demand for petrochemical raw materials and products has been strong, and road transportation has become increasingly common due to its high mobility and economy. However, at the same time, tanker truck accidents have occurred frequently. These accidents are complex and often result in leaks of volatile liquid hazardous chemicals, and may even trigger fires and explosions, posing a serious threat to the ecological environment.

[0003] Currently, the main response measure for liquid leaks is fire-fighting foam spraying. Spraying fire-fighting foam onto the surface of the leaking liquid can maintain the integrity of the foam layer and provide good anti-evaporation performance for a relatively short time. However, fire-fighting foam coverage has poor stability, a short effective coverage time, and its effectiveness is greatly affected by on-site environmental factors. Furthermore, different hazardous chemicals have different properties; for example, water solubility necessitates switching between different types of extinguishing agents depending on the properties of the leaking liquid. At the same time, foam extinguishing agents often contain fluorocarbon surfactants. While these components have high surface activity, they are extremely stable, toxic, bioaccumulative, and difficult to degrade, posing further harm to the ecological environment and human health.

[0004] Gel foam exhibits good fluidity and stability before gelation, and is already used as a treatment fluid in oil extraction and coal mine fire prevention and extinguishing. However, currently used gel foams still suffer from drawbacks such as excessively long or short gelation times, the presence of large amounts of solid particulate contaminants after gelation, and the need for on-site preparation of foam solution, which is time-consuming and does not meet the requirements for efficient emergency response and coverage of leaks.

[0005] Therefore, there is a need to develop a gel foam fire-fighting product that has high stability, is suitable for hazardous chemicals of different properties, has a large coverage area, long coverage time, good anti-evaporation (anti-volatilization) effect, does not cause secondary pollution, has controllable gelation time, and can be used immediately. Summary of the Invention

[0006] The purpose of this invention is to overcome the above-mentioned problems existing in the prior art and provide a composition for gel foam and its application. When using the composition for gel foam, the gelation time is controllable, the foam strength is high, the coverage area is large, the coverage time is long, and the anti-evaporation effect is good. It is suitable for the treatment of hazardous chemicals of different properties, and it can be used immediately without on-site remixing, making the treatment of hazardous chemicals more efficient, and it will not cause secondary pollution after use.

[0007] To achieve the above objectives, a first aspect of the present invention provides a composition for gel foam, the composition comprising separately stored component A and component B, wherein component A comprises polyvinyl alcohol, a foaming agent and another water-soluble film-forming polymer, and component B comprises an organoboron crosslinking agent.

[0008] The degree of alcoholysis of the polyvinyl alcohol is 88-100%; the viscosity of a 4% by weight aqueous solution of polyvinyl alcohol at 20°C is 20-35 mPa·s.

[0009] In component A, the concentration of polyvinyl alcohol is 1.8-6% by weight.

[0010] A second aspect of the invention provides the use of the gel foam composition described above in the spillage of polar and / or non-polar hazardous chemicals.

[0011] A third aspect of the present invention provides an article for handling spilled hazardous chemicals, the article comprising a static mixer, a storage tank I and a storage tank II, wherein the storage tank I and the storage tank II respectively store component A and component B of the gel foam composition as described in the first aspect, the storage tank A and the storage tank B are respectively provided with valves, the static mixer is connected to the storage tank A and the storage tank B respectively through the valves, and the static mixer is provided with an outlet.

[0012] A fourth aspect of the present invention provides a method for treating a leaked hazardous chemical, the method comprising: covering the surface of the leaked hazardous chemical with components A and B of the composition described in the first aspect;

[0013] Alternatively, using the article described in the third aspect, the valve is opened to allow materials from storage tank A and storage tank B to mix in a static mixer, and the materials in the static mixer are sprayed out and covered on the surface of the leaked hazardous chemicals.

[0014] Through the above technical solution, the present invention can achieve the following beneficial effects:

[0015] 1. The gel foam composition provided by this invention has a controllable crosslinking time. The crosslinking time (gelation time) can be adjusted by changing the mixing ratio of the two components, making it more flexible in use. When covering hazardous chemicals, the two components can be directly mixed and sprayed out, eliminating the need for on-site mixing and making the process more efficient.

[0016] 2. The gel foam composition provided by the present invention has fluidity comparable to that of aqueous film-forming foam before crosslinking. It has good fluidity and can therefore cover a larger area. The resulting gel foam has greater strength, is not easy to break, can remain stable for a longer period of time, and better suppresses volatilization.

[0017] 3. The gel foam composition provided by this invention employs an additional water-soluble film-forming polymer. When this composition is used to treat leaked polar liquids, the additional water-soluble film-forming polymer tends to form a thin film, covering the surface of the leaked polar liquid and isolating the leaked liquid from the foam. This prevents the polar liquid from defoaming the foam, allowing it to function effectively. When treating leaked non-polar liquids, the polyvinyl alcohol, foaming agent, and other components in the composition are generally poorly soluble in non-polar liquids, and therefore can also function normally. Therefore, the composition provided by this invention is applicable to both polar and non-polar hazardous chemicals, eliminating the need for re-selection based on the properties of the hazardous chemicals. Polyvinyl alcohol and the additional water-soluble film-forming polymer do not interfere with each other and can even work synergistically, enabling the gel foam composition of this invention to treat both polar and non-polar hazardous chemicals. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] In a first aspect, the present invention provides a composition for gel foam, the composition comprising separately stored component A and component B, wherein component A comprises polyvinyl alcohol, a foaming agent and another water-soluble film-forming polymer, and component B comprises an organoboron crosslinking agent;

[0020] The degree of alcoholysis of the polyvinyl alcohol is 88-100%; the viscosity of the polyvinyl alcohol aqueous solution at a concentration of 4% by weight at 20°C is 20-35 mPa·s.

[0021] In component A, the concentration of polyvinyl alcohol is 1.8-6% by weight.

[0022] The degree of hydrolysis and viscosity of the polyvinyl alcohol were measured according to GB / T 12010.2-2010. It is understood that the degree of hydrolysis and the viscosity of the 4% by weight aqueous solution of polyvinyl alcohol at 20°C are inherent characteristics of polyvinyl alcohol itself, and the polyvinyl alcohol in the composition of this invention needs to meet the above parameters.

[0023] Traditional firefighting foams have short coverage times and poor stability, especially when affected by environmental factors such as wind, making them more prone to breakage. Furthermore, they contain fluorocarbon surfactants, which are difficult to degrade. Gel foams, on the other hand, have better flowability before gelation, allowing them to cover a larger area; therefore, a slightly longer gelation time can result in a larger coverage area. However, some precipitation of the foam solution occurs before gelation, leading to decreased stability due to excessively long gelation times. While gel foams are used in oil and coal mines, excessively short or long gelation times can lead to small coverage areas, clogging of spray pipes, or poor coverage stability in leak emergency response. They also require on-site preparation of foam solution, resulting in inefficient treatment. Moreover, gel foams used in coal mines often contain water glass and fluorocarbon surfactants, which can leave residual solid pollutants.

[0024] The inventors of this invention discovered during their research that when using the gel foam composition provided by this invention to treat leaked hazardous chemicals, the gel foam composition can suppress evaporation when covering the hazardous chemicals. Furthermore, the crosslinking time can be controlled by simply adjusting the mixing ratio of the two components, allowing for adjustments based on on-site conditions and making it more flexible in use. In use, the two components are sprayed directly without on-site mixing, resulting in more efficient treatment. In particular, the use of the specific polyvinyl alcohol combined with the organoboron crosslinking agent described above ensures that the formed gel foam has higher strength, better stability, longer duration, and better resistance to environmental interference. With good stability, the gel foam, with its large coverage area and a certain height, can better suppress the volatilization of hazardous chemicals. When treating leaked polar liquids, the other water-soluble film-forming polymers tend to form a thin film, thereby isolating the leaked liquid from the foam and preventing the polyvinyl alcohol and foaming agent in the foam from dissolving in the leaked liquid, allowing them to function effectively. When treating leaked non-polar liquids, polyvinyl alcohol and foaming agents are generally difficult to dissolve in non-polar liquids, thus also functioning normally. Therefore, the composition described above is applicable to both polar and non-polar hazardous chemicals, eliminating the need to reselect based on the properties of the hazardous chemicals.

[0025] Understandably, when the two components are mixed, foaming occurs immediately, while cross-linking (i.e., gel formation) is slightly delayed. However, after cross-linking, a gel foam is formed, significantly enhancing stability and strength. Furthermore, various polyvinyl alcohols with different degrees of hydrolysis and viscosity can be used, as well as polyvinyl alcohols with the same degree of hydrolysis and viscosity.

[0026] According to the present invention, in order to further improve the stability of the formed gel foam, preferably, the degree of alcoholysis of the polyvinyl alcohol is 92-96%.

[0027] According to the present invention, preferably, the additional water-soluble film-forming polymer has a weight-average molecular weight of 210-250 g / mol. Using the additional water-soluble film-forming polymer as described above provides better anti-evaporation effect on polar liquids.

[0028] According to the present invention, in order to further improve the foaming effect of the composition and the strength of the formed gel foam simultaneously, preferably, the content of the foaming agent is 50-95 parts by weight (e.g., 50, 55, 60, 65, 70, 75, 77, 80, 83, 85, 88, 90, 93, 95) relative to 100 parts by weight, and the content of the additional water-soluble film-forming polymer is 3-5 parts by weight (e.g., 3, 3.5, 4, 4.5, 5).

[0029] According to the present invention, in order to further improve the foaming effect, preferably, the foaming agent is selected from at least one of anionic surfactants and amphoteric surfactants, more preferably from at least one of cocamidopropyl betaine, sodium lauryl sulfate, alkyl glycosides, and sodium lauryl aminopropionate. It is understood that alkyl glycosides refer to products synthesized from glucose and fatty alcohols, generally abbreviated as APG, and the alkyl glycoside may be APG0810.

[0030] According to the present invention, the additional water-soluble film-forming polymer is selected from at least one of xanthan gum, sodium alginate, carboxymethyl cellulose, and nonionic polyacrylamide. Using the water-soluble polymer described above can further improve the anti-evaporation stability against polar liquids.

[0031] It is understood that the gel foam composition described above is sufficient to cover leaked hazardous chemicals. The gel foam composition may also contain solvents, but during storage, the gel foam composition can be stored independently, and the solvent can be added to components A and B separately before use. According to the present invention, to further improve the stability and strength of the gel foam and extend the shelf life of the composition, component A preferably includes at least one of a foam stabilizer, a preservative, and water. More preferably, relative to 100 parts by weight of polyvinyl alcohol, the foam stabilizer content is 25-40 parts by weight (e.g., 25, 26, 27, 28, 29, 30, 31, 33, 35, 37, 40), and the preservative content is 5-30 parts by weight (e.g., 5, 8, 10, 13, 15, 18, 20, 23, 25, 27, 30). Further preferably, in component A, the content of polyvinyl alcohol is 2-5.5% by weight, the content of foaming agent is 1-5% by weight, the content of water-soluble film-forming polymer is 0.1-0.2% by weight, the content of foam stabilizer is 0.5-2% by weight, and the content of preservative is 0.1-1.5% by weight. Meeting the above-mentioned content requirements further ensures a more suitable viscosity of the mixed solution, making the crosslinking time more controllable and more conducive to foaming. The content of each substance within the above range can be controlled by controlling the amount of solvent.

[0032] According to the present invention, in order to further improve the stability of the gel foam, preferably, the foam stabilizer is selected from at least one of ethylene glycol monobutyl ether, diethylene glycol butyl ether, isobutanol, and propylene glycol methyl ether. Diethylene glycol butyl ether not only improves the dispersion of the substances in component A and makes component A more uniform, but also further improves the stability of the gel foam.

[0033] According to the present invention, preferably, the preservative is selected from at least one of sodium hydroxymethylglycinate, potassium sorbate, sodium benzoate and copper sulfate pentahydrate.

[0034] According to the present invention, preferably, the organoboron crosslinking agent is a complex formed by borate and organic ligand, wherein the molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent is 2.8-5.8:1, more preferably 3-5.5:1, and even more preferably 3.5-4.2:1. The inventors of the present invention have discovered in their research that by using the organoboron crosslinking agent with a specific ratio as described above, a gel foam with higher stability can be obtained when crosslinking with component A.

[0035] According to the present invention, preferably, the borate is selected from at least one of alkali metal borates, more preferably sodium tetraborate. In practice, borax (i.e., sodium tetraborate decahydrate) can be used.

[0036] According to the present invention, preferably, the donor of the organic ligand is selected from at least one of C3-C8 alkanolamines, polyhydroxycarboxylates and sugar alcohols, more preferably from at least one of diethanolamine, triethanolamine, sodium gluconate, xylitol and sorbitol.

[0037] Using borate or organic ligand donors as described above can further improve the stability of the formed gel foam.

[0038] The preparation method of the organoboron crosslinking agent can be a conventional choice in the art. However, preferably, the preparation method of the organoboron crosslinking agent includes: mixing borate, organic ligand donor, catalyst and solvent at 40-70°C to obtain a mixture, and then reacting the mixture at 70-85°C for 3-5 hours to obtain the organoboron crosslinking agent;

[0039] The amount of borate used is 5-20% by weight, the amount of organic ligand donor is 10-35% by weight, and the amount of catalyst is 1-4% by weight, based on the total weight of the mixture.

[0040] The catalyst is selected from alkali metal hydroxides, more preferably sodium hydroxide and / or potassium hydroxide, and the solvent is a mixture of glycerol and water. The ratio of glycerol to water is not particularly limited, and can be, for example, 0.2-2:1.

[0041] It is understandable that when using borax, the amount of borax used should be such that the amount of borate contained therein meets the above-mentioned range.

[0042] According to a preferred embodiment of the present invention, the solvent is first preheated to 40-70°C, then the borate, the organic ligand donor, and the catalyst are added to the solvent, and the temperature is adjusted to 70-85°C. The reaction is carried out for 3-5 hours at a rotation speed of 500-800 rpm to obtain the organoboron crosslinking agent.

[0043] The inventors of this invention discovered in their research that preparing an organoboron crosslinking agent using the method described above can further enhance the properties of the substances in component A, especially polyvinyl alcohol, resulting in a gel foam with greater strength and better stability.

[0044] According to the present invention, preferably, component B further includes a pH adjuster and / or water. Adjusting the pH using a pH adjuster can prolong the crosslinking time and increase the coverage area.

[0045] According to the present invention, preferably, the content of the pH adjuster is 2-7.5 parts by weight (e.g., 2, 3, 4, 5, 6, 7, 7.5) relative to 100 parts by weight of the organoboron crosslinking agent.

[0046] According to the present invention, preferably, the pH adjuster is selected from at least one of alkali metal hydroxides, more preferably sodium hydroxide and / or potassium hydroxide.

[0047] According to the present invention, preferably, in component B, the content of the organoboron crosslinking agent is 30-50% by weight, and the content of the pH adjuster is 1-3% by weight.

[0048] It is understandable that polyvinyl alcohol is difficult to dissolve uniformly at low temperatures. Therefore, in preparing component A, polyvinyl alcohol is dissolved separately in water at 60-80°C, resulting in a solution concentration of 8-11% by weight. The other water-soluble film-forming polymer is dissolved separately in water at room temperature, resulting in a solution concentration of 0.3-0.7% by weight. The dissolved polyvinyl alcohol and water-soluble polymer are then mixed with other materials to obtain component A.

[0049] When preparing component B, the organoboron crosslinking agent can be prepared first according to the above method, and then mixed with other components.

[0050] When handling leaked hazardous chemicals, the gel foam composition described above can be used alone, or it can be used in combination with existing fire extinguishing agent concentrates (such as aqueous film-forming foam fire extinguishing agent concentrates or alcohol-resistant fire extinguishing agent concentrates). For example, it can be compounded with existing 6% aqueous film-forming foam fire extinguishing agent concentrates (in which the concentrate and other substances are mixed at a volume ratio of 6:94), or 6% alcohol-resistant fire extinguishing agent concentrates, wherein the above-mentioned concentrates and the gel foam composition are mixed at a volume ratio of 6:94. The inventors of this invention have discovered in their research that using the gel foam composition described above in combination with existing fire extinguishing agent concentrates does not affect the crosslinking or evaporation inhibition effect of the gel foam composition.

[0051] According to the present invention, preferably, the gel foam composition does not contain fluorocarbon surfactants. Fluorocarbon surfactants are common components in existing foam fire extinguishing agents, but they are highly stable, toxic, bioaccumulative, and difficult to degrade. The gel foam composition of the present invention does not contain fluorocarbon surfactants, yet it can still achieve coverage of leaked hazardous chemicals without causing secondary pollution.

[0052] In a second aspect, the present invention provides the application of the gel foam composition as described above in the spillage of polar and / or non-polar hazardous chemicals.

[0053] The gel foam composition provided in the first aspect of the present invention is applicable to both polar and non-polar hazardous chemicals, and can achieve good coverage and evaporation inhibition effects.

[0054] Thirdly, the present invention provides an article for handling spilled hazardous chemicals, the article comprising a static mixer, a storage tank I and a storage tank II, wherein the storage tank I and the storage tank II respectively store component A and component B of the gel foam composition as described in the first aspect of the present invention, the storage tank A and the storage tank B are respectively provided with valves, the static mixer is connected to the storage tank A and the storage tank B respectively through the valves, and the static mixer is provided with an outlet.

[0055] The static mixer is capable of thoroughly and uniformly mixing materials from storage tanks I and II. The mixed materials are then ejected through the outlet.

[0056] In operation, opening the valves allows materials from storage tanks A and B to mix in the static mixer. The ratio of the two materials can be controlled by adjusting the valve opening, thus controlling the crosslinking time. The material from the static mixer is then discharged through the outlet and applied to the surface of the hazardous chemicals to suppress volatilization.

[0057] Fourthly, the present invention provides a method for treating a leaked hazardous chemical, the method comprising: covering the surface of the leaked hazardous chemical with components A and B of the composition described in the first aspect of the present invention;

[0058] Alternatively, using the article as described in the third aspect of the invention, the valve is opened to allow materials from storage tank A and storage tank B to be mixed in a static mixer, and the materials in the static mixer are sprayed out and covered on the surface of the leaked hazardous chemicals.

[0059] The hazardous chemicals mentioned are polar and / or non-polar hazardous chemicals.

[0060] According to the present invention, in order to adjust the crosslinking time and thus the coverage area according to the site conditions, it is preferable that the mass ratio of component A to component B is 4-9:1 during use. Using the method described above, the crosslinking time can be controlled within approximately 1-3 minutes.

[0061] According to a particularly preferred embodiment of the present invention, the following gel composition is used;

[0062] Component A contains the following components: 4.8-5.5% by mass of polyvinyl alcohol (polyvinyl alcohol 096-27 and polyvinyl alcohol 092-20, with a mass ratio of 1.1-1.3:1); 4.5-5% by mass of foaming agent (cocamidopropyl betaine, sodium lauryl sulfate, and alkyl glycoside APG0810, with a mass ratio of 2.9-3.2:1:1); 0.18-0.2% by mass of another water-soluble film-forming polymer (xanthan gum and sodium alginate, with a mass ratio of 1.4-1.6:1); 1.8-2% by mass of foam leveling agent (diethylene glycol butyl ether); and 1.3-1.5% by mass of preservative (potassium sorbate).

[0063] In component B, the contents of each substance are as follows: 48-50% by weight of organoboron crosslinking agent, 1-1.2% by weight of sodium hydroxide, and the balance is water.

[0064] The preparation method of the organoboron crosslinking agent is as follows:

[0065] Solvent is added to a glass reactor under atmospheric pressure and preheated to 48-52℃ with stirring. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide are added to the reactor, and the reaction temperature is adjusted to 81-82℃. The rotation speed is 580-600 rpm, and the reaction is carried out for 3.8-4.2 hours to obtain the organoboron crosslinking agent. The mass percentages of each component are as follows: sodium tetraborate is 18-20% by weight, the organic ligand donor is 30-35% by weight (the organic ligands are sodium gluconate, triethanolamine, and sorbitol, with a weight ratio of 3.8-4.2:2:1), sodium hydroxide is 3.8-4% by weight, and the remainder is glycerol and water, with a mass ratio of glycerol to water of 1.8-2.2:1. The molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent is approximately 3.3-3.6:1.

[0066] Components A and B are stored separately to obtain the composition for gel foam.

[0067] The present invention will be described in detail below through embodiments. In the following embodiments,

[0068] Polyvinyl alcohol 096-27 has a degree of alcoholysis of 96%, and at 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 27 mPa·s.

[0069] Polyvinyl alcohol 092-20 has a degree of alcoholysis of 92%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 20 mPa·s.

[0070] Polyvinyl alcohol 100-60 has a degree of alcoholysis of 99%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 60 mPa·s.

[0071] Polyvinyl alcohol 094-27 has a degree of alcoholysis of 94%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 27 mPa·s.

[0072] Polyvinyl alcohol 092-35 has a degree of alcoholysis of 92%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 35 mPa·s.

[0073] Polyvinyl alcohol 100-35 has a degree of alcoholysis of 99%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 35 mPa·s.

[0074] Polyvinyl alcohol 088-20 has a degree of alcoholysis of 88%. At 20°C, the viscosity of a 4% by weight aqueous solution of this polyvinyl alcohol is 20 mPa·s.

[0075] Xanthan gum, with a weight-average molecular weight of 241 g / mol;

[0076] Sodium alginate, with a weight-average molecular weight of 216 g / mol;

[0077] Carboxymethyl cellulose, with a weight-average molecular weight of 240 g / mol;

[0078] Before being mixed with other components, polyvinyl alcohol is first dissolved separately in water at 70°C, so that the concentration of the solution after dissolution is 10% by weight.

[0079] The other water-soluble film-forming polymers were first dissolved separately in water at room temperature before being mixed with other components, so that the concentration of the solution after dissolution was 0.5% by weight.

[0080] Example 1

[0081] Weigh the following substances according to the following mass percentages: 1.2 wt% polyvinyl alcohol 096-27, 0.8 wt% polyvinyl alcohol 092-20, 0.07 wt% xanthan gum, 0.03 wt% sodium alginate, 0.6 wt% cocamidopropyl betaine, 0.2 wt% sodium dodecyl sulfate, 0.2 wt% alkyl glycoside APG0810, 0.5 wt% diethylene glycol butyl ether, 0.1 wt% potassium sorbate, and the balance being water. Mix the above components and stir until fully dissolved to obtain component A.

[0082] Preparation of organoboron crosslinking agent: Solvent was added to a glass reactor under atmospheric pressure and stirred and preheated to 50°C. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide were added to the reactor, and the reaction temperature was adjusted to 80°C. The reaction speed was 600 rpm, and the reaction was allowed to proceed for 3.5 hours to obtain the organoboron crosslinking agent. The mass percentages of each component are as follows: based on the total weight of the mixture, sodium tetraborate was 5 wt%, the organic ligand donor was 10 wt% (5 wt% sodium gluconate, 3 wt% triethanolamine, 2 wt% sorbitol), sodium hydroxide was 1 wt%, glycerol was 28 wt%, and water was 56 wt%. The molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent was 4.1:1.

[0083] Component B is obtained by mixing the organoboron crosslinking agent, sodium hydroxide solution, and water in the following mass ratio: 40% by weight of organoboron crosslinking agent, 3% by weight of sodium hydroxide, and the balance being water.

[0084] Components A and B are stored separately to obtain the composition for gel foam.

[0085] Example 2

[0086] Weigh the following substances according to the following mass percentages: 3% polyvinyl alcohol 096-27, 2.5% polyvinyl alcohol 092-20, 0.12% xanthan gum, 0.08% sodium alginate, 3% cocamidopropyl betaine, 1% sodium dodecyl sulfate, 1% alkyl glycoside APG0810, 2% diethylene glycol butyl ether, 1.5% potassium sorbate, and the balance being water. Mix the above components and stir until fully dissolved to obtain component A.

[0087] Preparation of organoboron crosslinking agent: Solvent was added to a glass reactor under atmospheric pressure and stirred and preheated to 50°C. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide were added to the reactor, and the reaction temperature was adjusted to 82°C. The reaction speed was 600 rpm, and the reaction was carried out for 4 hours to obtain the organoboron crosslinking agent. The mass percentages of each component are as follows: based on the total weight of the mixture, the amount of sodium tetraborate is 20 wt%, the amount of the organic ligand donor is 35 wt% (20 wt% sodium gluconate, 10 wt% triethanolamine, 5 wt% sorbitol), the amount of sodium hydroxide is 4 wt%, the amount of glycerol is 20.5 wt%, and the amount of water is 20.5 wt%. The molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent is 3.5:1.

[0088] Component B is obtained by mixing the organoboron crosslinking agent, sodium hydroxide solution, and water in the following mass ratio: 50% by weight of organoboron crosslinking agent, 1% by weight of sodium hydroxide, and the balance being water.

[0089] Components A and B are stored separately to obtain the composition for gel foam.

[0090] Example 3

[0091] Weigh the following substances according to the following mass percentages: 4% polyvinyl alcohol 096-27, 0.07% xanthan gum, 0.08% carboxymethyl cellulose, 1% cocamidopropyl betaine, 1% sodium dodecyl sulfate, 1% alkyl glycoside APG0810, 1.2% isobutanol, 0.3% sodium hydroxymethylglycinate, 0.4% sodium benzoate, and the balance being water. Mix the above components and stir until fully dissolved to obtain component A.

[0092] Preparation of organoboron crosslinking agent: Solvent was added to a normal-pressure glass reactor and stirred and preheated to 50°C. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide were added to the reactor, and the reaction temperature was adjusted to 75°C. The reaction speed was 600 rpm, and the reaction was allowed to proceed for 4.5 hours to obtain the organoboron crosslinking agent. The mass percentages of each component are as follows: based on the total weight of the mixture, sodium tetraborate was 15 wt%, the organic ligand donor was 20 wt% (10 wt% sodium gluconate, 5 wt% triethanolamine, 5 wt% sorbitol), sodium hydroxide was 2 wt%, glycerol was 42 wt%, and water was 21 wt%. The molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent was 4:1.

[0093] Component B is obtained by mixing the organoboron crosslinking agent, sodium hydroxide solution, and water in the following mass ratio: 45% by weight of organoboron crosslinking agent, 2% by weight of sodium hydroxide, and the balance being water.

[0094] Components A and B are stored separately to obtain the composition for gel foam.

[0095] Example 4

[0096] Components A and B were prepared according to the method of Example 1, except that polyvinyl alcohol 096-27 and polyvinyl alcohol 092-20 were replaced with polyvinyl alcohol 094-27.

[0097] Example 5

[0098] Components A and B were prepared according to the method of Example 1, except that polyvinyl alcohol 096-27 and polyvinyl alcohol 092-20 were replaced with polyvinyl alcohol 092-35.

[0099] Example 6

[0100] Components A and B were prepared according to the method of Example 1, except that polyvinyl alcohol 096-27 and polyvinyl alcohol 092-20 were replaced with polyvinyl alcohol 100-35.

[0101] Example 7

[0102] Components A and B were prepared according to the method of Example 1, except that polyvinyl alcohol 096-27 and polyvinyl alcohol 092-20 were replaced with polyvinyl alcohol 088-20.

[0103] Example 8

[0104] Components A and B were prepared according to the method of Example 1, except that in the preparation of component B, the organoboron crosslinking agent was prepared as follows: Solvent was added to a normal-pressure glass reactor and stirred and preheated to 40°C. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide were added to the reactor, and the reaction temperature was adjusted to 80°C. The reaction speed was 600 rpm, and the reaction was carried out for 3 hours to obtain the organoboron crosslinking agent. The mass percentages of each component were as follows: based on the total weight of the mixture, sodium tetraborate was 5% by weight, the organic ligand donor was 15% by weight (11% by weight of sodium gluconate, 2% by weight of triethanolamine, and 2% by weight of sorbitol), sodium hydroxide was 1% by weight, glycerol was 20% by weight, and water was 59% by weight. The molar ratio of hydroxyl groups to boron atoms in the prepared organoboron crosslinking agent was 5.7:1.

[0105] Example 9

[0106] Component A and component B were prepared according to the method of Example 1, except that the mass percentages of each component in component A were as follows: 2 wt% polyvinyl alcohol 096-27, 4 wt% polyvinyl alcohol 092-20, 0.07 wt% xanthan gum, 0.03 wt% sodium alginate, 0.5 wt% cocamidopropyl betaine, 0.1 wt% sodium dodecyl sulfate, 0.1 wt% APG0810, 0.5 wt% diethylene glycol butyl ether, 0.1 wt% potassium sorbate, and the balance being water. The above components were mixed and stirred until fully dissolved to obtain component A.

[0107] Preparation of organoboron crosslinking agent: Solvent was added to a normal-pressure glass reactor and stirred and preheated to 60°C. Borax, sodium gluconate, triethanolamine, sorbitol, and sodium hydroxide were added to the reactor, and the reaction temperature was adjusted to 80°C. The reaction speed was 600 rpm, and the reaction was carried out for 4 hours to obtain the organoboron crosslinking agent. The mass percentages of each component are as follows: based on the total weight of the mixture, the amount of sodium tetraborate is 20 wt%, the amount of the organic ligand donor is 20 wt% (10 wt% sodium gluconate, 5 wt% triethanolamine, 5 wt% sorbitol), the amount of sodium hydroxide is 5 wt%, the amount of glycerol is 20 wt%, and the amount of water is 35 wt%. The molar ratio of hydroxyl groups to boron atoms in the organoboron crosslinking agent is 2:1.

[0108] Component B is obtained by mixing the organoboron crosslinking agent, sodium hydroxide solution, and water in the following mass ratio: 40% by weight of organoboron crosslinking agent, 3% by weight of sodium hydroxide, and the balance being water.

[0109] Example 10.

[0110] Components A and B were prepared according to the method of Example 1, except that xanthan gum and sodium alginate were replaced with carboxymethyl cellulose at a dosage of 0.1% by weight.

[0111] Comparative Example 1

[0112] Components A and B were prepared according to the method of Example 1, except that polyvinyl alcohol 100-27 and polyvinyl alcohol 088-20 were replaced with polyvinyl alcohol 100-60.

[0113] Comparative Example 2

[0114] Component A and component B were prepared according to the method of Example 1, except that polyvinyl alcohol was replaced with hydroxypropyl guar gum in the preparation of component A.

[0115] Comparative Example 3

[0116] Component A and component B were prepared according to the method of Example 1, except that in the preparation of component A, the additional water-soluble film-forming polymer was replaced with 0.1% by weight of polyvinyl alcohol 100-27.

[0117] Comparative Example 4

[0118] Component A and component B were prepared according to the method of Example 1, with the following difference:

[0119] The mass percentages of each component in component A are as follows: 0.6 wt% polyvinyl alcohol 096-27, 0.4 wt% polyvinyl alcohol 092-20, 0.064 wt% xanthan gum, 0.016 wt% sodium alginate, 0.48 wt% cocamidopropyl betaine, 0.16 wt% sodium dodecyl sulfate, 0.16 wt% alkyl glycoside (APG0810), 0.4 wt% diethylene glycol butyl ether, 0.08 wt% potassium sorbate, and the balance being water.

[0120] Comparative Example 5

[0121] Component A and component B were prepared according to the method of Example 1, with the following difference:

[0122] The mass percentages of each component in component A are as follows: 4.2 wt% polyvinyl alcohol 096-27, 2.8 wt% polyvinyl alcohol 092-20, 0.24 wt% xanthan gum, 0.06 wt% sodium alginate, 3.2 wt% cocamidopropyl betaine, 1.6 wt% sodium dodecyl sulfate, 1.6 wt% APG0810, 2.5 wt% diethylene glycol butyl ether, 2 wt% potassium sorbate, and the balance being water.

[0123] Test Example 1

[0124] The crosslinking time, anti-evaporation time, and expansion ratio of the gel foam compositions prepared in the examples and comparative examples were tested.

[0125] The equipment for handling spilled hazardous chemicals includes a static mixer, storage tank I and storage tank II. Storage tank I stores component A, and storage tank II stores component B. Storage tanks A and B are each equipped with a valve. The static mixer is connected to storage tanks A and B respectively through the valves, and the static mixer is equipped with an outlet.

[0126] Perform the inhibition time test using the following method:

[0127] (1) Control the mixing mass ratio of component A to component B to be 9:1. (2) Take a stainless steel basin with an upper diameter of 600mm, a lower diameter of 500mm, and a depth of 220mm. Fix a 400mm×100mm baffle horizontally 100mm above the upper edge of the stainless steel basin, and make two holes in the baffle to fix the VOC detector probe. The two openings correspond to the center of the stainless steel basin below and the position 50mm from the edge of the basin, respectively. Place the VOC detector probe in the two openings of the baffle. (3) Pour a certain amount of water into the stainless steel basin so that the liquid level is about 20mm. Then slowly pour in a volatile polar liquid or a non-polar liquid so that the liquid level is about 30-40mm. (4) Open the above product. After the sprayed foam stabilizes, align the outlet with the wall of the stainless steel basin so that the foam liquid flows along the basin wall to the liquid surface and spreads. When the foam layer reaches a thickness of 30 mm, close the valves of storage tanks A and B and remove the stainless steel basin from below the product outlet. Connect tap water to the product and spray it out to rinse the inside of the device. (5) Start timing when the foam liquid spreads to the surface of the liquid to be covered. For non-polar liquids (using n-pentane), measure the volatile gas concentration at two detection points every 10 minutes. For polar liquids (using anhydrous ethanol), measure every 3 minutes. Stop timing when the gas concentration reaches 25% of the lower explosive limit of volatile gases. This time is recorded as the effective suppression time of the gel foam.

[0128] The gel foam compositions prepared in each of the above examples and comparative examples were tested in the manner described above to obtain their respective anti-evaporation times. The results are shown in Table 1.

[0129] Furthermore, the crosslinking time and foaming ratio of the gel foam compositions prepared in the above examples and comparative examples were tested respectively.

[0130] The method for testing the crosslinking time is as follows: Weigh 100g of component A and component B in a mass ratio of 9:1. Pour component A into a 250ml beaker and stir at a speed of 1000r / min. Add component B to component A while stirring. Simultaneously, start a stopwatch and stop the timer when the mixture exhibits the phenomenon of "climbing the rod". This time is the crosslinking time of the gel.

[0131] The expansion ratio was determined according to the method specified in GB 15308-2006 "Foam Fire Extinguishing Agents". The expansion ratio results when the mass ratio of component A to component B is 9:1 are shown in Table 1.

[0132] Table 1

[0133]

[0134]

[0135] As shown in Table 1, the gel foam compositions provided by the embodiments of the present invention exhibit a high foaming ratio and a long suppression time for both polar and non-polar liquids, indicating that the foam is more stable and stronger, making it suitable for handling hazardous chemicals of different properties. In particular, the gel foam compositions prepared in Examples 1-3 show even better results, demonstrating that the gel foam compositions provided by the present invention are sufficient to cover leaked hazardous chemicals. The product of Comparative Example 3 is ineffective when handling polar liquids. Furthermore, compared to traditional products, the gel foam compositions provided by the present invention do not require on-site mixing and can be used immediately, making the handling of hazardous chemicals more efficient and preventing secondary pollution after use.

[0136] Test Example 2

[0137] The gel foam compositions prepared in Examples 1-3 were used to test the crosslinking time, anti-evaporation time, and foaming ratio according to the method in Test Example 1, except that the mass ratio of component A to component B was 4:1. The results are shown in Table 2.

[0138] Table 2

[0139] Example 1 Example 2 Example 3 Crosslinking time 1'50” 1'08”58 1'25”33 Suppression time for n-pentane volatilization / min 220 350 320 Time to inhibit anhydrous ethanol evaporation / min 42 60 54 Foaming ratio 6 5.4 5.1

[0140] As can be seen from Table 1-2, when using the gel foam composition provided by the present invention, the crosslinking time can be adjusted by simply adjusting the ratio of component A and component B, thereby adjusting the coverage area. This allows for flexible adjustments based on the site conditions, making it more universally applicable.

[0141] Test Example 3

[0142] This is to illustrate the situation when the gel foam composition provided by the present invention is used in combination with existing fire extinguishing agent concentrates.

[0143] The gel foam composition prepared in Example 1, and conventional 6% aqueous film-forming foam extinguishing agent concentrate (purchased from Jiangsu Suolong Fire Protection Technology) and 6% alcohol-resistant extinguishing agent concentrate (purchased from Jiangsu Suolong Fire Protection Technology) were tested for crosslinking time, evaporation suppression time, and foaming time, respectively. The results are shown in Table 3.

[0144] The test for suppression time was still conducted according to Test Example 1, except that another storage tank (denoted as storage tank C) was added to the product of Test Example 1, which contained an aqueous film-forming foam extinguishing agent concentrate (or an alcohol-resistant extinguishing agent concentrate) with a concentration of 6% by weight. When using the product to spray foam, the valve of storage tank C was opened at the same time, and the valve was controlled so that the volume ratio of the aqueous film-forming foam extinguishing agent concentrate (or an alcohol-resistant extinguishing agent concentrate) to the gel foam composition was 6:94.

[0145] The crosslinking time was tested according to the method in Test Example 1, except that: component B was added to component A under stirring, and aqueous film-forming foam extinguishing agent concentrate (or anti-alcohol extinguishing agent concentrate) was added at the same time, so that the volume ratio of the concentrate to the gel foam composition prepared in Preparation Example 1 was 6:94.

[0146] The expansion ratio was determined according to the method in GB 15308-2006 "Foam Extinguishing Agents". The mass ratio of component A to component B was 9:1, and the volume ratio of aqueous film-forming foam extinguishing agent concentrate (or alcohol-resistant extinguishing agent concentrate) to the gel foam composition prepared in Example 1 was 6:94.

[0147] Table 3

[0148] Combined with aqueous film-forming foam extinguishing agent concentrate Combined with solvent-resistant fire extinguishing agent concentrate Crosslinking time 2'37”24 2'44”87 Suppression time for n-pentane volatilization / min 280 310 Time to inhibit anhydrous ethanol evaporation / min 54 72 Foaming ratio 6.8 6.3

[0149] As can be seen from Tables 1 and 3, the effectiveness of the gel foam composition provided by this invention is not significantly affected when used in combination with conventional fire extinguishing agent concentrates. That is, when using the gel foam composition provided by this invention alone, or in combination with conventional fire extinguishing agent concentrates, to treat leaked hazardous chemicals, good coverage can be achieved, meeting emergency response requirements.

[0150] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for use in gel foams, characterized in that, The composition comprises separately stored component A and component B, wherein component A includes polyvinyl alcohol, a foaming agent and additional water-soluble film-forming polymer, and component B includes an organoboron crosslinking agent; The degree of hydrolysis of the polyvinyl alcohol is 88-100%; the viscosity of a 4% by weight aqueous solution of polyvinyl alcohol at 20°C is 20-35 mPa·s. In component A, the concentration of polyvinyl alcohol is 1.8-6% by weight. The foaming agent is selected from at least one of anionic surfactants, amphoteric surfactants, and nonionic surfactants; The additional water-soluble film-forming polymer is selected from at least one of xanthan gum, sodium alginate, and carboxymethyl cellulose; The foaming agent content is 50-95 parts by weight relative to 100 parts by weight of polyvinyl alcohol, and the content of the additional water-soluble film-forming polymer is 3-5 parts by weight. The preparation method of the organoboron crosslinking agent includes: mixing borate, organic ligand donor, catalyst and solvent at 40-70℃ to obtain a mixture, and then reacting the mixture at 70-85℃ for 3-5 hours to obtain the organoboron crosslinking agent; The amount of borate used, based on the total weight of the mixture, is 5-20% by weight, the amount of organic ligand donor is 10-35% by weight, and the amount of catalyst is 1-4% by weight. The catalyst is selected from alkali metal hydroxides; The borate is selected from at least one of alkali metal borates; The donor of the organic ligand is selected from at least one of C3-C8 alkanolamines, polyhydroxycarboxylate salts, and sugar alcohols; In component B, the content of organoboron crosslinking agent is 30-50% by weight. When using, the mass ratio of component A to component B is 4-9:

1.

2. The composition according to claim 1, wherein, The degree of alcoholysis of the polyvinyl alcohol is 92-96%; And / or, other water-soluble film-forming polymers have a weight-average molecular weight of 210-250 g / mol.

3. The composition according to claim 1, wherein, The foaming agent is selected from at least one of cocamidopropyl betaine, sodium lauryl sulfate, alkyl glycosides, and sodium lauryl aminopropionate.

4. The composition according to claim 1 or 3, wherein, Component A also includes at least one of a foaming agent, a preservative, and water.

5. The composition according to claim 4, wherein, The content of the foaming agent is 25-40 parts by weight relative to 100 parts by weight of polyvinyl alcohol, and the content of the preservative is 5-30 parts by weight.

6. The composition according to claim 4, wherein, In component A, the content of polyvinyl alcohol is 2-5.5% by weight, the content of foaming agent is 1-5% by weight, the content of other water-soluble film-forming polymer is 0.1-0.2% by weight, the content of foam stabilizer is 0.5-2% by weight, and the content of preservative is 0.1-1.5% by weight.

7. The composition according to claim 4, wherein, The foaming agent is selected from at least one of ethylene glycol monobutyl ether, diethylene glycol butyl ether, isobutanol, and propylene glycol methyl ether.

8. The composition according to claim 4, wherein, The preservative is selected from at least one of sodium hydroxymethylglycinate, potassium sorbate, sodium benzoate, and copper sulfate pentahydrate.

9. The composition according to claim 1, wherein, The borate is sodium tetraborate; And / or, the donor of the organic ligand is selected from at least one of diethanolamine, triethanolamine, sodium gluconate, xylitol and sorbitol.

10. The composition according to claim 9, wherein, The catalyst is sodium hydroxide and / or potassium hydroxide, and the solvent is a mixture of glycerol and water.

11. The composition according to claim 1 or 9, wherein, Component B also includes a pH adjuster and / or water.

12. The composition according to claim 11, wherein, The pH adjuster content is 2-7.5 parts by weight relative to 100 parts by weight of the organoboron crosslinking agent.

13. The composition according to claim 12, wherein, The pH adjuster is selected from at least one of alkali metal hydroxides.

14. The composition according to claim 13, wherein, The pH adjuster is sodium hydroxide and / or potassium hydroxide.

15. The composition according to claim 11, wherein, In component B, the content of pH adjuster is 1-3% by weight.

16. The use of the gel foam composition according to any one of claims 1-15 in the spill of polar and / or non-polar hazardous chemicals.

17. A method for handling spilled hazardous chemicals, characterized in that, The method includes: covering the surface of the leaked hazardous chemical with components A and B of the composition according to any one of claims 1-15.

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