Multifunctional dust suppressant suitable for coal mine as well as preparation method and application of multifunctional dust suppressant

Abstract

The invention relates to the technical field of dust suppression materials, in particular to a multifunctional dust suppressant suitable for a coal mine and a preparation method and application of the multifunctional dust suppressant. Gastrodia elata polysaccharide and solani gum are used as base materials, the gastrodia elata polysaccharide is subjected to carboxymethylation modification so as to remarkably improve the wettability of the gastrodia elata polysaccharide, sodium trimetaphosphate is used as a cross-linking agent, and stable phosphodiester bonds are formed between carboxymethylated gastrodia elata polysaccharide and solani gum molecules under the alkaline condition; sodium dodecyl benzene sulfonate is compounded, so that the wetting and infiltration capacity of the whole system is further enhanced. Through targeted adjustment of raw material selection and raw material ratio cooperation, the prepared dust suppressant can simultaneously realize high wettability, strong cohesiveness and good water retention, and can rapidly wrap coal dust to form a compact consolidation layer with high mechanical strength, actually, the coal dust settling time is less than 20 seconds, the hardness of the consolidation layer exceeds 80 HA, and the dust suppressant has good dust suppressant performance. The dust suppression efficiency on PM10 reaches 98% or above, and good wind erosion resistance and rain erosion resistance are achieved.

Description

Technical Field

[0001] This invention relates to the field of dust suppression materials technology, specifically to a multifunctional dust suppressant suitable for coal mines, its preparation method, and its application. Background Technology

[0002] The mining, transportation, and storage of coal generate large amounts of dust, seriously threatening safe production and worker health. Currently, widely used chemical dust suppressants are mainly classified into three categories based on their mechanism of action: wetting dust suppressants, binding dust suppressants, and hygroscopic and water-retaining dust suppressants. However, all of them suffer from problems such as limited functionality and difficulty in adapting to the complex and ever-changing coal mine environment. Wetting dust suppressants quickly capture dust by reducing the surface tension of water, but the resulting solidified layer has extremely low mechanical strength and is prone to cracking under wind or mechanical disturbance, triggering secondary dust generation and compromising dust suppression durability. Binding dust suppressants rely on the adhesive force of polymer materials to bind dust particles together. However, their wetting and penetration properties are generally poor, resulting in low initial capture efficiency for highly hydrophobic coal dust. Furthermore, due to insufficient water retention, the resulting binding layer is prone to embrittlement and cracking in dry environments, losing its dust-suppressing effect. Moisture-absorbing and water-retaining dust suppressants can absorb and retain moisture from the air, but they lack the ability to quickly wet dust and have insufficient binding properties, making it impossible for dust particles to effectively agglomerate and form a stable coal dust solidification layer, thus limiting their dust suppression effect.

[0003] Therefore, it is of great significance to develop a multifunctional dust suppressant that can achieve efficient wetting, strong adhesion and long-lasting water retention and consolidation. Summary of the Invention

[0004] This application addresses the problem that existing coal mine dust suppressants have limited functionality and cannot simultaneously achieve efficient wetting, strong adhesion, and long-lasting dust suppression. It provides a multifunctional dust suppressant suitable for coal mines, along with its preparation method and application. This dust suppressant can rapidly encapsulate coal dust, forming a dense, solidified layer with high mechanical strength. Actual measurements show that its coal dust settling time is less than 20 seconds, the solidified layer hardness exceeds 80 HA, and its dust suppression efficiency for PM10 reaches over 98%. Furthermore, it possesses excellent resistance to wind and rain erosion.

[0005] The first aspect of this invention provides a multifunctional dust suppressant suitable for coal mines, prepared from raw materials comprising the following parts by weight: Gastrodia elata polysaccharide 0.2-0.6 parts; 0.2-0.4 parts of sorbitol; Sodium tripolyphosphate 0.3-0.7 parts; 0.3-0.5 parts of chloroacetic acid; Sodium hydroxide 0.8-1.5 parts; Sodium dodecylbenzenesulfonate 0.2-0.4 parts; 80-120 parts water.

[0006] This invention provides a multifunctional dust suppressant suitable for coal mines. Using Gastrodia elata polysaccharide and solanate gum as base materials, the Gastrodia elata polysaccharide is first modified by carboxymethylation to significantly improve its wetting properties. Then, sodium trimetaphosphate is used as a crosslinking agent to form stable phosphodiester bonds between the carboxymethylated Gastrodia elata polysaccharide and solanate gum molecules under alkaline conditions, thereby constructing a three-dimensional network structure. Finally, sodium dodecylbenzenesulfonate is added to further enhance the overall wetting and penetration capacity of the system. Through targeted adjustments to the selection and synergistic combination of various raw materials, the prepared dust suppressant can simultaneously achieve high wettability, strong adhesion, and good water retention. The dust suppressant can quickly encapsulate coal dust, forming a dense, solidified layer with high mechanical strength. Actual measurements show that the coal dust settling time is less than 20 seconds, the solidified layer hardness exceeds 80 HA, and the dust suppression efficiency for PM10 reaches over 98%. It also possesses excellent resistance to wind and rain erosion, achieving unexpected technical results.

[0007] Furthermore, the weight ratio of the gastrodia polysaccharide to solanac gum is (1.5:1) to (3:1).

[0008] Furthermore, the amount of sodium trimetaphosphate added is 30%-70% of the total weight of the gastrodia polysaccharide and solanac gum.

[0009] A second aspect of the present invention provides a method for preparing the above-mentioned multifunctional dust suppressant suitable for coal mines, comprising the following steps: Step 1: Preparation of carboxymethylated Gastrodia elata polysaccharide solution: Gastrodia elata polysaccharide was dissolved in the first portion of water and then reacted with chloroacetic acid under alkaline conditions to undergo a carboxymethylation reaction, yielding a carboxymethylated Gastrodia elata polysaccharide solution. Step 2, Preparation of solanum solution: Dissolve the solanac gum in the second part of water, heat and stir to obtain a solanac gum solution; Step 3, cross-linking reaction: The carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 was mixed with the solanac gum solution obtained in step 2, and sodium tripolyphosphate was added under alkaline conditions to carry out a cross-linking reaction to obtain a cross-linking product solution. Step 4, Post-processing: The cross-linked product solution obtained in step 3 was neutralized to neutral, and sodium dodecylbenzenesulfonate was added and mixed evenly to obtain a dust suppressant.

[0010] Furthermore, in step 1, the gastrodia polysaccharide is dissolved in the first portion of water and heated and stirred at 50-70°C to obtain a gastrodia polysaccharide solution.

[0011] Furthermore, in step 1, the carboxymethylation reaction is carried out at a temperature of 55℃-65℃ for 2-4 hours.

[0012] Furthermore, in step 2, the heating and stirring temperature is 85℃-95℃.

[0013] Furthermore, in step 3, the carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 is mixed with the solanate gum solution obtained in step 2, the pH of the mixed solution is adjusted to 9-11, and sodium tripolyphosphate is added.

[0014] Furthermore, in step 3, sodium trimetaphosphate is added to carry out a cross-linking reaction at a temperature of 45℃-55℃.

[0015] The third aspect of the present invention provides the application of the above-mentioned multifunctional dust suppressant suitable for coal mines in dust control during coal mining, transportation and storage.

[0016] Gastrodia elata polysaccharides are a class of natural high-molecular polymers that can be completely decomposed by microorganisms in the natural environment, and are non-toxic and harmless. Their chemical structure is relatively complex, typically containing multiple monosaccharide units such as glucose, galactose, and mannose. Gastrodia elata polysaccharides with well-defined structures are composed solely of glucose and have a backbone linked by α-1,4-glycosidic bonds. They are strongly hydrophilic high-molecular-weight polysaccharides, rich in hydroxyl groups, which can combine with water to form hydrogen bonds, further enhancing their water-retention properties. They can also undergo various molecular modifications such as carboxymethylation and sulfonation, thereby improving their polysaccharide properties.

[0017] Ganten gum is a translucent, gum-like substance naturally exuded from the trunk of the broadleaf elm tree, native to India. Its production process involves no added chemicals, and the raw materials are readily available, non-toxic, harmless, and biodegradable, making it a green and environmentally friendly material. It is primarily composed of arabinose, galactose, mannose, xylose, and glucuronic acid, and is a natural anionic polysaccharide. Ganten gum possesses excellent adhesion and film-forming properties, enabling it to bind dust particles and form a solidified layer of sufficient strength on the surface of coal dust, effectively inhibiting dust diffusion.

[0018] Sodium trimetaphosphate is a non-toxic and highly efficient cross-linking agent. Its molecule contains multiple phosphate groups, which can undergo esterification reactions with functional groups such as hydroxyl groups (-OH) on polymers to form "phosphate ester bonds". The cross-linking reaction can usually be carried out under alkaline and heating conditions, and the process is simple, the conditions are mild, and it is easy to industrialize.

[0019] Chloroacetic acid is a highly efficient and mature carboxymethylating agent with low raw material costs, making it very suitable for large-scale production applications. The chlorine atom in its molecule is highly reactive and can undergo nucleophilic substitution reactions with the hydroxyl groups (-OH) on natural polysaccharides, introducing carboxymethyl groups (-CH2COOH) and thus modifying them with carboxymethylation.

[0020] Sodium dodecylbenzenesulfonate exhibits excellent wetting properties; its solution can quickly encapsulate and wet hydrophobic coal dust, causing it to settle. Furthermore, sodium dodecylbenzenesulfonate is recognized as a safe chemical raw material by international safety organizations and is commonly used as a cleaning agent in laundry detergents and dishwashing liquids. It also possesses good biodegradability.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides a multifunctional dust suppressant suitable for coal mines. Using Gastrodia elata polysaccharide and solanate gum as base materials, the Gastrodia elata polysaccharide is first modified by carboxymethylation to significantly improve its wetting properties. Then, sodium trimetaphosphate is used as a crosslinking agent to form stable phosphate diester bonds between the carboxymethylated Gastrodia elata polysaccharide and solanate gum molecules under alkaline conditions, thereby constructing a three-dimensional network structure. Finally, sodium dodecylbenzenesulfonate is added to further enhance the overall wetting and penetration capacity of the system. By specifically adjusting the selection and synergistic combination of various raw materials, the prepared dust suppressant can simultaneously achieve high wettability, strong adhesion, and good water retention. The dust suppressant can quickly encapsulate coal dust, forming a dense, solidified layer with high mechanical strength. Actual measurements show that the coal dust settling time is less than 20 seconds, the solidified layer hardness exceeds 80 HA, and the dust suppression efficiency for PM10 reaches over 98%. It also possesses excellent wind and rain erosion resistance, achieving unexpected technical results.

[0022] 2. The preparation method of this invention involves carboxylating Gastrodia elata polysaccharide with chloroacetic acid under alkaline conditions, successfully introducing hydrophilic carboxymethyl groups onto its molecular chain, significantly enhancing the wetting properties of the product. Subsequently, the obtained carboxymethylated Gastrodia elata polysaccharide solution is mixed with separately prepared solanate gum solution, and stable phosphodiester bonds are formed between the two polysaccharide molecules through the cross-linking effect of sodium trimetaphosphate in an alkaline environment, constructing a three-dimensional network structure. This structure not only significantly improves the mechanical strength and toughness of the dust suppressant film, but also enhances the water retention properties of the material through intermolecular interactions. Finally, the wetting and diffusivity of the system are further optimized by neutralization treatment and compounding with sodium dodecylbenzenesulfonate. The preparation method is simple to operate and easy to control. Attached Figure Description

[0023] Figure 1 This is a comparison chart showing water retention.

[0024] Figure 2 This is a hardness comparison chart.

[0025] Figure 3 This is a comparison chart of dust suppression efficiency.

[0026] Figure 4 This is a comparison chart of wind erosion resistance rates.

[0027] Figure 5 This is a comparison chart of rain erosion resistance rates.

[0028] Figure 6 This is a schematic diagram of the reaction principle of the present invention. Detailed Implementation

[0029] The present invention will now be described in further detail with reference to specific embodiments. However, this should not be construed as limiting the scope of the present invention to the following embodiments; all technologies implemented based on the content of the present invention fall within the scope of the present invention.

[0030] Unless otherwise specified, the use of terms such as "first," "second," and "third" in the description of specific embodiments of the present invention is merely for distinguishing descriptions of identical or similar components and should not be construed as emphasizing or implying the relative importance of a particular component.

[0031] Furthermore, in the description of the embodiments of the present invention, "several", "more than", and "a number of" represent at least two. The number can be any number, such as 2, 3, 4, 5, 6, 7, 8, or 9, and can even exceed nine.

[0032] To address the problem that existing coal mine dust suppressants have limited functionality and cannot simultaneously achieve efficient wetting, strong adhesion, and long-lasting dust suppression, this embodiment provides a multifunctional dust suppressant suitable for coal mines, along with its preparation method and application.

[0033] This dust suppressant uses Gastrodia elata polysaccharide and solanate gum as base materials. First, the Gastrodia elata polysaccharide is modified by carboxylation to significantly improve its wetting properties. Then, sodium trimetaphosphate is used as a crosslinking agent to form stable phosphate diester bonds between the carboxylated Gastrodia elata polysaccharide and solanate gum molecules under alkaline conditions, thereby constructing a three-dimensional network structure. Finally, sodium dodecylbenzenesulfonate is added to further enhance the overall wetting and penetration ability of the system.

[0034] The first aspect of this embodiment provides a multifunctional dust suppressant suitable for coal mines, prepared from raw materials comprising the following parts by weight: 0.2-0.6 parts of Gastrodia elata polysaccharide; 0.2-0.4 parts of solanate gum; 0.3-0.7 parts of sodium trimetaphosphate; 0.3-0.5 parts of chloroacetic acid; 0.8-1.5 parts of sodium hydroxide; 0.2-0.4 parts of sodium dodecylbenzenesulfonate; and 80-20 parts of water.

[0035] By weight, for example, in some embodiments, the raw materials for preparing the multifunctional dust suppressant include: 0.2 parts of Gastrodia elata polysaccharide; 0.2 parts of solanate gum; 0.3 parts of sodium trimetaphosphate; 0.3 parts of chloroacetic acid; 0.8 parts of sodium hydroxide; 0.2 parts of sodium dodecylbenzenesulfonate; and 80 parts of water. For example, the raw materials for preparing the multifunctional dust suppressant include: 0.6 parts of Gastrodia elata polysaccharide; 0.4 parts of solanate gum; 0.7 parts of sodium trimetaphosphate; 0.5 parts of chloroacetic acid; 1.5 parts of sodium hydroxide; 0.4 parts of sodium dodecylbenzenesulfonate; and 120 parts of water. In some other embodiments, the raw materials for preparing the multifunctional dust suppressant include: 0.45 parts of Gastrodia elata polysaccharide; 0.35 parts of solanate gum; 0.45 parts of sodium trimetaphosphate; 0.35 parts of chloroacetic acid; 1.2 parts of sodium hydroxide; 0.34 parts of sodium dodecylbenzenesulfonate; and 110 parts of water.

[0036] The dust suppressant can quickly coat coal dust and form a dense, solidified layer with high mechanical strength. Actual measurements show that the coal dust settling time is less than 20 seconds, the hardness of the solidified layer exceeds 80HA, the dust suppression efficiency for PM10 is over 98%, and it also has excellent resistance to wind and rain erosion.

[0037] In some embodiments, the weight ratio of Gastrodia elata polysaccharide to solanate gum is (1.5:1) to (3:1). For example, the weight ratio of Gastrodia elata polysaccharide to solanate gum is 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3:1. By controlling the weight ratio of Gastrodia elata polysaccharide to solanate gum within an optimal range, the two polysaccharides achieve optimal synergistic effects in the cross-linking reaction. This ratio ensures that the system contains sufficient Gastrodia elata polysaccharide to maintain excellent wetting and penetration properties, while providing an appropriate amount of solanate gum to guarantee sufficient adhesion and film-forming effects. As a result, the final three-dimensional network structure possesses both ideal hydrophilicity to quickly capture dust and sufficient mechanical strength and toughness to resist external damage. This effectively avoids the problems of decreased wettability caused by excessive solanate gum or insufficient adhesion caused by excessive Gastrodia elata polysaccharide, achieving the best balance between wettability and adhesion.

[0038] In some embodiments, the amount of sodium trimetaphosphate added is 30%-70% of the total weight of the Gastrodia elata polysaccharide and solanate gum. For example, the amount of sodium trimetaphosphate added is 30%, 35%, 40%, 45%, 50%, 60%, or 70% of the total weight of the Gastrodia elata polysaccharide and solanate gum. By controlling the amount of sodium trimetaphosphate added within the range of 30%-70% of the total weight of the Gastrodia elata polysaccharide and solanate gum, it is ensured that the crosslinking agent can fully interact with the active sites on the polysaccharide molecules, forming a moderately dense phosphodiester bond crosslinking network between the carboxymethylated Gastrodia elata polysaccharide and solanate gum. The optimized dosage ensures that the three-dimensional network structure has sufficient crosslinking density to give the solidified layer excellent mechanical strength and deformation resistance, while avoiding the problem of excessive network rigidity and increased brittleness caused by excessive crosslinking agent. At the same time, the crosslinking structure effectively locks in moisture through intermolecular forces, significantly enhancing the water retention and durability of the dust suppressant, so that the final product has excellent wind erosion and rain erosion resistance while maintaining good film-forming properties.

[0039] The second aspect of this embodiment provides a method for preparing the above-mentioned multifunctional dust suppressant suitable for coal mines, comprising the following steps: Step 1: Preparation of carboxymethylated Gastrodia elata polysaccharide solution: Gastrodia elata polysaccharide was dissolved in the first portion of water and then reacted with chloroacetic acid under alkaline conditions to undergo a carboxymethylation reaction, yielding a carboxymethylated Gastrodia elata polysaccharide solution. Step 2, Preparation of solanum solution: Dissolve the solanac gum in the second part of water, heat and stir to obtain a solanac gum solution; Step 3, cross-linking reaction: The carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 was mixed with the solanac gum solution obtained in step 2, and sodium tripolyphosphate was added under alkaline conditions to carry out a cross-linking reaction to obtain a cross-linking product solution. Step 4, Post-processing: The cross-linked product solution obtained in step 3 was neutralized to neutral, and sodium dodecylbenzenesulfonate was added and mixed evenly to obtain a dust suppressant.

[0040] In some embodiments, in step 1, the gastrodia polysaccharide is dissolved in a first portion of water and heated and stirred at 50-70°C to obtain a gastrodia polysaccharide solution. For example, the heating and stirring temperature is 50°C, 60°C, or 70°C.

[0041] In some embodiments, in step 1, the carboxymethylation reaction temperature is 55℃-65℃, and the reaction time is 2-4 hours. For example, in step 1, the carboxymethylation reaction temperature is 55℃, and the reaction time is 4 hours. In step 1, the carboxymethylation reaction temperature is 65℃, and the reaction time is 2 hours. In step 1, the carboxymethylation reaction temperature is 60℃, and the reaction time is 3 hours. By precisely controlling the carboxymethylation reaction temperature within the range of 55℃-65℃ and maintaining the reaction time for 2-4 hours, the nucleophilic substitution reaction between chloroacetic acid and the hydroxyl groups on the Gastrodia elata polysaccharide molecular chain can proceed at an ideal rate, ensuring the full introduction of carboxymethyl groups to obtain a stable wetting and enhancing effect. This also effectively avoids the degradation of the polysaccharide molecular chain that may be caused by excessively high temperature or excessively long reaction time. Thus, while significantly improving the water solubility and permeability of the product, the integrity of the Gastrodia elata polysaccharide molecular skeleton is well maintained.

[0042] In some embodiments, in step 2, the heating and stirring temperature is 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, or 95°C.

[0043] In some embodiments, in step 3, the carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 is mixed with the solanac gum solution obtained in step 2, the pH of the mixed solution is adjusted to 9-11, and sodium tripolyphosphate is added.

[0044] In some embodiments, in step 3, sodium trimetaphosphate is added to carry out a cross-linking reaction at a temperature of 45℃-55℃. By precisely controlling the pH of the cross-linking reaction system within the alkaline range of 9-11, an optimal reaction environment is created for the hydrolysis of sodium trimetaphosphate and the formation of phosphodiester bonds between it and polysaccharide molecules. Simultaneously, controlling the reaction temperature within the suitable range of 45℃-55℃ effectively promotes the full progress of the cross-linking reaction, ensuring the construction of a complete and stable three-dimensional network structure between the carboxymethylated Gastrodia elata polysaccharide and the solanacole gum molecular chains. This also avoids the possibility of polysaccharide molecular chain breakage or active site inactivation due to excessively high temperatures, thus synergistically ensuring that the final dust suppressant product possesses ideal mechanical strength, structural stability, and durable dust suppression performance.

[0045] The third aspect of this embodiment provides the application of the above-mentioned multifunctional dust suppressant suitable for coal mines in dust control during coal mining, transportation, and storage.

[0046] To better understand the technical solutions of the above embodiments, the following more detailed operating examples are provided for further explanation.

[0047] Example 1 (1) Add 50 mL of distilled water to a beaker, dissolve 0.2 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0048] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.3g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0049] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0050] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.3g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinking product aqueous solution.

[0051] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 1.

[0052] Example 2 (1) Add 50 mL of distilled water to a beaker, dissolve 0.2 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0053] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0054] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.3 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0055] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0056] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 2.

[0057] Example 3 (1) Add 50 mL of distilled water to a beaker, dissolve 0.2 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0058] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.5g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0059] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.4 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0060] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.7g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0061] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 3.

[0062] Example 4 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0063] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.3g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0064] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.3 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0065] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.7g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0066] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 4.

[0067] Example 5 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0068] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.5g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0069] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.4 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0070] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.3g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinking product aqueous solution.

[0071] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 5.

[0072] Example 6 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0073] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0074] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0075] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0076] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir at room temperature until dissolved to obtain the aqueous solution of Example 6.

[0077] Example 7 (1) Add 50 mL of distilled water to a beaker, dissolve 0.6 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0078] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.3g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0079] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.4 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0080] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0081] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 7.

[0082] Example 8 (1) Add 50 mL of distilled water to a beaker, dissolve 0.6 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0083] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0084] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0085] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.7g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0086] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 8.

[0087] Example 9 (1) Add 50 mL of distilled water to a beaker, dissolve 0.6 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0088] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.5g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0089] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.3 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0090] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.3g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinking product aqueous solution.

[0091] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Example 9.

[0092] Comparative Example 1 (1) Add 100 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain the aqueous solution of Comparative Example 1.

[0093] Comparative Example 2 (1) Add 100 mL of distilled water to a beaker, dissolve 0.2 g of solanac gum in the distilled water, place it in a water bath, set the temperature to 90 °C, heat and stir for 0.5 h until the solanac gum is completely dissolved, and obtain the aqueous solution of Comparative Example 2.

[0094] Comparative Example 3 (1) Add 100mL of distilled water to a beaker, dissolve 0.4g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60℃, heat and stir for 1h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0095] (2) Add 1.2g of sodium hydroxide to the gastrodia polysaccharide aqueous solution, place it in a 45℃ water bath and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a 60℃ water bath and stir for 3h to obtain the aqueous solution of Comparative Example 3.

[0096] Comparative Example 4 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0097] (2) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0098] (3) Mix the gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly with a magnetic stirrer to obtain the aqueous solution of Comparative Example 4. Comparative Example 5 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0099] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0100] (3) Take another beaker and add 50 mL of distilled water. Dissolve 2 g of solanac gum in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the solanac gum is completely dissolved to obtain a solanac gum aqueous solution.

[0101] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0102] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 5.

[0103] Comparative Example 6 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0104] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0105] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0106] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of borax and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0107] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 6.

[0108] Comparative Example 7 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0109] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0110] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0111] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of calcium chloride and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinking product aqueous solution.

[0112] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 7.

[0113] Comparative Example 8 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of guar gum in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the guar gum is completely dissolved, and obtain a guar gum aqueous solution.

[0114] (2) Add 1.2g of sodium hydroxide to the guar gum aqueous solution and stir in a 45℃ water bath for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution and stir again in a 60℃ water bath for 3h to obtain a carboxymethylated guar gum aqueous solution.

[0115] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0116] (4) Mix carboxymethylated guar gum aqueous solution and solanate gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain crosslinking product aqueous solution.

[0117] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 8.

[0118] Comparative Example 9 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of xanthan gum in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the xanthan gum is completely dissolved, and obtain xanthan gum aqueous solution.

[0119] (2) Add 1.2g of sodium hydroxide to the xanthan gum aqueous solution and stir in a 45℃ water bath for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution and stir again in a 60℃ water bath for 3h to obtain a carboxymethylated xanthan gum aqueous solution.

[0120] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0121] (4) Mix the carboxymethylated xanthan gum aqueous solution with the solanate gum aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinking product aqueous solution.

[0122] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 9.

[0123] Comparative Example 10 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0124] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0125] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of gum arabic in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the gum arabic is completely dissolved to obtain a gum arabic aqueous solution.

[0126] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the gum arabic aqueous solution and stir evenly. Add sodium bicarbonate to the mixed solution to adjust the pH to 10, then add 0.5g of sodium trimetaphosphate and stir until dissolved. Then place the beaker in a constant temperature magnetic stirring water bath at 50℃ and react for 5h to obtain the crosslinked product aqueous solution.

[0127] (5) Add a certain amount of dilute hydrochloric acid to the aqueous solution of the crosslinking product to adjust the pH of the solution to neutral, and then add 0.3g of sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 10.

[0128] Comparative Example 11 (1) Add 50 mL of distilled water to a beaker, dissolve 0.4 g of Gastrodia elata polysaccharide in the distilled water, place it in a water bath, set the temperature to 60 °C, heat and stir for 1 h until the Gastrodia elata polysaccharide is completely dissolved, and obtain an aqueous solution of Gastrodia elata polysaccharide.

[0129] (2) Add 1.2g of sodium hydroxide to the aqueous solution of Gastrodia elata polysaccharide, place it in a water bath at 45℃ and stir for 1h to obtain an alkalized solution; then add 0.4g of chloroacetic acid to the alkalized solution, place it in a water bath at 60℃ and stir for 3h to obtain an aqueous solution of carboxymethylated Gastrodia elata polysaccharide.

[0130] (3) Take another beaker and add 50 mL of distilled water. Dissolve 0.2 g of sorbitol in the distilled water, place it in a water bath, set the temperature to 90 °C, and heat and stir for 0.5 h until the sorbitol is completely dissolved to obtain an aqueous solution of sorbitol.

[0131] (4) Mix the carboxymethylated gastrodia polysaccharide aqueous solution with the solanac gum aqueous solution and stir evenly. Adjust the pH of the solution to neutral. Then add 0.3g sodium dodecylbenzenesulfonate in a magnetic stirrer and stir until dissolved at room temperature to obtain the aqueous solution of Comparative Example 11.

[0132] The solutions prepared in Examples 1-9 and Comparative Examples 1-11 were tested for wettability, water retention, hardness of the consolidation layer, dust suppression efficiency, wind erosion resistance, and rain erosion resistance.

[0133] Experiment 1 The wettability of the solutions prepared in Examples 1-9 and Comparative Examples 1-11 was then tested.

[0134] The wettability of the solution was determined using the coal dust settling method. 40 mL of each of the prepared solutions from Examples 1-9 and Comparative Examples 1-11 was measured and placed in test tubes. Twenty portions of 0.5 g coal powder were weighed and poured into the test tubes. The time required for complete settling of the coal powder was recorded. The test results are shown in Table 1.

[0135] Table 1 Settling Time

[0136] Table 1 shows that the settling time of coal dust in the solutions prepared in Examples 1-9 was all within 20 seconds, with the fastest being only 14.72 seconds. In contrast, the settling speed of coal dust in the solutions prepared in the comparative examples was reduced, and it could not settle completely in the solution prepared in Comparative Example 2. This indicates that the wettability of the solutions prepared in the examples is significantly better than that of the solutions prepared in the comparative examples. This is because the dust suppressant solutions prepared in Examples 1-9 underwent a carboxymethylation reaction with Gastrodia elata polysaccharide, introducing highly wettable carboxymethyl groups into the dust suppressant system, significantly enhancing the wettability of the dust suppressant solution. Furthermore, the dust suppressant prepared in this invention is compounded with sodium dodecylbenzenesulfonate, which has excellent wettability, further enhancing the wettability of the dust suppressant, enabling it to more quickly encapsulate, wet, and settle dust. Comparative Example 1 solution was a single Gastrodia elata polysaccharide solution, and Comparative Example 4 solution was a mixed solution of Gastrodia elata polysaccharide and solanac gum. Neither solution underwent carboxymethylation modification, resulting in poor wetting properties. Comparative Example 2 solution was a single solanac gum solution, which had poor wetting properties and was unable to wet dust, thus failing to settle. Comparative Example 3 solution underwent carboxymethylation modification but did not incorporate surfactants, resulting in slightly poor wetting performance. Comparative Examples 5-11 solutions underwent carboxymethylation modification and incorporated surfactants, but due to unsuitable reaction raw materials, inappropriate selection of crosslinking agents, and raw materials not being within the appropriate range, the wetting properties of all solutions could not achieve optimal results.

[0137] This invention, through a specific combination of natural polysaccharides (Gastrodia elata polysaccharide + solanate gum) and a specific cross-linking method (sodium trimetaphosphate), synergistically solves the long-standing technical problem of difficulty in simultaneously achieving wettability, adhesion and water retention, and achieves unexpected technical results.

[0138] Experiment 2 The water retention properties of the solutions prepared in Examples 1-9 and Comparative Examples 1-11 were tested below.

[0139] Weigh 5g of dried 200-mesh coal powder, and make 20 portions, placing each portion into a petri dish. Add 20mL of the solutions prepared in Examples 1-9 and Comparative Examples 1-11 to each dish. Place the samples with added solutions into a vacuum drying oven at 60℃ for drying. Record the change in coal sample mass every hour for a total of 10 hours, and calculate the water loss rate.

[0140] ; In the formula, E Water loss rate (%) m The mass of the petri dish is expressed in grams (g). m 0 represents the initial mass of the sample (g). m 1 represents the mass (g) of the sample after water loss.

[0141] like Figure 1The coal samples prepared by spraying the solutions of Examples 1-9 still retained moisture after 10 hours, with a water loss rate between 85% and 93%. The coal sample prepared by spraying the solution of Example 6 had a water loss rate of only 85.49% after 10 hours, while the coal samples prepared by spraying the solutions of Comparative Examples 1-11 all achieved a water loss rate of 100% after 10 hours. This indicates that the water retention properties of the solutions of Examples 1-9 are significantly better than those of Comparative Examples 1-11. This is because the raw material *Gastrodia elata* polysaccharide used in the dust suppressant prepared in this invention has a molecular structure rich in hydroxyl groups, which can combine with water to form hydrogen bonds, enhancing the water retention performance of the dust suppressant. Simultaneously, through a cross-linking reaction, carboxymethylated *Gastrodia elata* polysaccharide molecules form phosphodiester bonds with solanac gum molecules, enhancing the water-locking properties of the material and further improving its water retention performance. In contrast, solutions of Comparative Examples 1, 2, 3, 4, and 11 existed in monomer form without cross-linking, resulting in a lack of covalent bonds in the system and a significant reduction in water retention. Although solutions of Comparative Examples 5-10 were cross-linked, their water retention was greatly reduced due to issues such as inappropriate selection of raw materials and cross-linking agents, and improper addition of raw materials in the wrong proportions.

[0142] Experiment 3 The hardness of the consolidation layer and the dust suppression efficiency of the solutions prepared in Examples 1-9 and Comparative Examples 1-11 were tested below.

[0143] Equal amounts of coal powder were weighed and placed in petri dishes, then placed on a wind erosion simulation platform. A wind speed of 12 m / s was set to determine the hardness of the consolidation layer and the dust suppression efficiency. First, a handheld laser particle counter was used to detect the initial concentrations of PM2.5 and PM10. C 0. Subsequently, equal amounts of solutions from Examples 1-9 and Comparative Examples 1-11 were uniformly sprayed into the petri dishes, and placed in a constant temperature drying oven at 50°C until completely dry. The hardness of the coal dust consolidation layer of different samples was measured using a Shore hardness tester. The samples sprayed with different solutions and dried were then placed on a wind erosion simulation platform and blown at a wind speed of 10 m / s for 30 minutes. The PM2.5 and PM10 concentrations were then measured again using a handheld laser particle counter and recorded as follows. C 1. All data are the average of three measurements. The dust suppression rate is calculated using the following formula: ; μ Dust suppression rate (%) C 0 represents the initial concentration of PM2.5 and PM10 (μg / m³). 3 ), C 1 represents the concentrations of PM2.5 and PM10 after spraying the solution (μg / m³). 3 ).

[0144] Depend on Figure 2It can be seen that the hardness of the consolidated layer of the coal samples treated with solutions from Examples 1-9 is above 80 HA, while the hardness of the consolidated layer of the coal samples treated with solutions from Comparative Examples 1-11 ranges from a maximum of 75.19 HA to a minimum of only 35.69 HA. Figure 3 It can be seen that the dust suppression efficiency of the coal samples treated with the solutions of Examples 1-9 is significantly higher than that of the coal samples treated with the solutions of Comparative Examples 1-11. Specifically, Example 6 achieved dust suppression efficiencies of 98.56% and 95.41% for PM10 and PM2.5, respectively, while Comparative Example 1 achieved only 36.18% and 21.19% for PM10 and PM2.5, respectively. This is because the dust suppressant prepared in this invention crosslinks carboxymethylated Gastrodia elata polysaccharide with solanate gum via phosphate diester bonds, constructing a stable three-dimensional network structure between molecules and enhancing the mechanical strength of the coal dust consolidation layer. Simultaneously, solanate gum possesses excellent adhesion and film-forming properties. Through the synergistic effect of sodium trimetaphosphate and carboxymethylated Gastrodia elata polysaccharide, the dust suppressant can effectively bind dust particles, forming a high-hardness, anti-interference consolidation layer, thereby achieving effective dust suppression.

[0145] Experiment 4 The solutions prepared in Examples 1-9 and Comparative Examples 1-11 were tested for resistance to wind erosion and rain erosion.

[0146] Coal samples of equal initial mass were placed in petri dishes. Equal amounts of solutions from Examples 1-9 and Comparative Examples 1-11 were sprayed evenly into the petri dishes. The dishes were then placed in a constant-temperature drying oven at 50°C until completely dry. The weight of the samples at this point was measured using a balance and recorded as _____. M 0. Then, place it on a wind erosion simulation platform, set the wind speed to 12 m / s, and conduct a wind erosion resistance experiment. After 30 minutes, weigh the sample again using a balance, and record the weight as . M 1. All data are the average of three measurements.

[0147] The wind erosion resistance rate is calculated using the following formula: ; α The wind erosion resistance rate (%) M 0 represents the initial mass of the sample (g). M 1 represents the mass (g) of the sample after wind erosion. M The mass (g) of the petri dish.

[0148] Coal samples of equal initial mass were placed in petri dishes and uniformly sprayed with solutions of equal mass from Examples 1-9 and Comparative Examples 1-11. The dishes were then placed in a vacuum drying oven at 50°C until completely dry, and the mass at this point was recorded. N 0. A 10-minute spray test was conducted on the materials sprayed with the materials from Examples 1-9 and Comparative Examples 1-11. After the test, the coal samples were again dried in a vacuum drying oven at 50°C until completely dry, and the mass at this point was recorded. N1. Calculate the rain erosion resistance rate according to the following formula: ; η The percentage of rain erosion resistance. N 0 represents the initial mass (g). N 1 represents the mass (g) after spraying. N The mass (g) of the petri dish.

[0149] Depend on Figure 4 , 5 It can be seen that the coal samples treated with the solutions in Examples 1-9 have a wind erosion resistance rate of over 95% and a rain erosion resistance rate of over 90%, both significantly higher than those in Comparative Examples 1-11. This indicates that the dust suppressant prepared in this invention crosslinks solanate gum and carboxymethylated Gastrodia elata polysaccharide through sodium trimetaphosphate, forming a three-dimensional network structure. After spraying, it can form a dust suppressant film with excellent weather resistance, effectively resisting wind erosion and rainwater erosion. The materials prepared in Comparative Examples 1, 2, 3, 4, and 11 did not form an effective covalent crosslinked network, and therefore had poor resistance. Although the materials prepared in Comparative Examples 5-10 formed a covalent crosslinked network, the strength and toughness of the formed dust suppressant film were insufficient, and the dust suppressant film was prone to cracking, thus making it difficult to withstand wind and rainwater erosion.

[0150] In summary, the novel multifunctional dust suppressant prepared by this invention is suitable for coal mines. It is a multifunctional dust suppressant with high wettability, strong adhesion, excellent water retention, good mechanical properties and excellent weather resistance. It is suitable for coal mine dust control under different working conditions and effectively overcomes the shortcomings of traditional dust suppressants, such as single function and limited scope of application. It has good social benefits and considerable economic benefits.

[0151] (1) Gastrodia elata polysaccharide is a highly hydrophilic polymeric polysaccharide with a large number of hydroxyl groups in its molecular structure, which can combine with water to form hydrogen bonds to enhance its water retention performance. At the same time, this invention introduces carboxymethyl groups into the molecular chain of Gastrodia elata polysaccharide through carboxymethylation reaction, which significantly enhances its wetting performance. The introduction of carboxymethyl groups not only improves the wetting performance of Gastrodia elata polysaccharide, enabling it to quickly reduce the surface tension of water and rapidly penetrate and encapsulate coal dust particles, but also enhances the spreading and adsorption capacity of dust suppressants on complex coal dust surfaces, thereby effectively improving the wetting and capture efficiency of hydrophobic coal dust.

[0152] (2) A stable three-dimensional network structure was constructed between carboxymethylated Gastrodia elata polysaccharide and solanate gum through the cross-linking effect of sodium trimetaphosphate. This structure not only enhances the mechanical strength of the coal dust consolidation layer, enabling it to maintain its integrity under the influence of complex environmental factors such as wind erosion and rain scouring, thus preventing secondary dust generation, but also improves the water retention performance of the material through the phosphate diester bonds formed between molecules, delaying water evaporation and preventing the consolidation layer from cracking due to dryness, thereby achieving long-term dust suppression. Solanate gum has excellent adhesion and good film-forming properties. Through the synergistic effect of sodium trimetaphosphate and carboxymethylated Gastrodia elata polysaccharide, the adhesion and film-forming properties of the dust suppressant are further enhanced, improving the toughness and strength of the dust suppressant film. This allows the dust suppressant to effectively bind dust particles, forming a high-strength, interference-resistant consolidation layer that effectively resists environmental disturbances such as wind erosion and rain scouring, solving the problems of poor adhesion, brittle film formation, and easy cracking of the dust suppressant.

[0153] (3) The raw materials selected in this invention are all derived from natural or environmentally friendly materials, including biodegradable Gastrodia elata polysaccharide, solanate gum, and non-toxic crosslinking agent sodium trimetaphosphate, etc., which will not cause secondary pollution to the soil and water bodies in the mining area, and meet the requirements of environmental protection and sustainable development. At the same time, the materials prepared by this invention have been successfully modified by carboxymethylation synergistic crosslinking to prepare a multifunctional dust suppressant that combines high wettability, strong adhesion, excellent water retention, good mechanical properties and excellent weather resistance. It realizes the whole process control from rapid dust suppression to long-term dust fixation, and is suitable for coal mine dust control under different working conditions. It has good application and promotion value.

[0154] The preparation and reaction principle of the dust suppressant of the present invention are further explained as follows: Figure 6 As shown: (1) Sodium hydroxide deprotonates the hydroxyl groups (-OH) on the gastrodia polysaccharide molecular chain, forming a more nucleophilic alkoxide anion (-O). - This activates the polysaccharide chain. The activated polysaccharide alkoxide anion undergoes a nucleophilic substitution reaction with the chlorine atom in the chloroacetic acid (ClCH2COOH) molecule. The chlorine atom is replaced as a leaving group, and the alkoxide anion combines with the carbon atom of chloroacetic acid to form a carboxymethyl ether bond (-O-CH2-COO). - ), while releasing chloride ions (Cl ions) - Since a single gastrodia polysaccharide molecule contains multiple hydroxyl groups, these hydroxyl groups can react with chloroacetic acid, thereby introducing multiple carboxymethyl groups onto the gastrodia polysaccharide molecule chain, resulting in carboxymethylated gastrodia polysaccharide.

[0155] (2) Sodium trimetaphosphate hydrolyzes and rearranges under alkaline conditions to generate a cross-linking intermediate with higher reactivity. The positively charged phosphorus atom in this intermediate can be nucleophilically attacked by the hydroxyl groups (-OH) on the carboxymethylated Gastrodia elata polysaccharide molecular chain and the solanate gum molecular chain, respectively, resulting in two nucleophilic substitution reactions. In each reaction, the oxygen atom of the polysaccharide attacks the phosphorus center and forms a PO covalent bond with the phosphorus atom, ultimately forming a stable phosphodiester bond (-OP(=O)(O-)) between the hydroxyl groups of the two polysaccharide molecular chains. Since a sodium trimetaphosphate molecule has three phosphate groups, and one phosphate group can react with two different polysaccharide molecules, and each polysaccharide molecular chain contains multiple hydroxyl groups, the carboxymethylated Gastrodia elata polysaccharide and solanate gum can be cross-linked through multiple phosphodiester bonds to form a three-dimensional network structure.

[0156] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A multifunctional dust suppressant suitable for coal mines, characterized in that, It is prepared from the following raw materials in parts by weight: Gastrodia elata polysaccharide 0.2-0.6 parts; 0.2-0.4 parts of sorbitol; Sodium tripolyphosphate 0.3-0.7 parts; 0.3-0.5 parts of chloroacetic acid; Sodium hydroxide 0.8-1.5 parts; Sodium dodecylbenzenesulfonate 0.2-0.4 parts; 80-120 parts water.

2. The multifunctional dust suppressant suitable for coal mines according to claim 1, characterized in that, The weight ratio of Gastrodia elata polysaccharide to solanate gum is (1.5:1) to (3:1).

3. The multifunctional dust suppressant suitable for coal mines according to claim 1, characterized in that, The amount of sodium trimetaphosphate added is 30%-70% of the total weight of the gastrodia polysaccharide and solanate gum.

4. The method for preparing the multifunctional dust suppressant suitable for coal mines as described in any one of claims 1-3, characterized in that, Includes the following steps: Step 1: Preparation of carboxymethylated Gastrodia elata polysaccharide solution: Gastrodia elata polysaccharide was dissolved in the first portion of water and then reacted with chloroacetic acid under alkaline conditions to undergo a carboxymethylation reaction, yielding a carboxymethylated Gastrodia elata polysaccharide solution. Step 2, Preparation of solanum solution: Dissolve the solanac gum in the second part of water, heat and stir to obtain a solanac gum solution; Step 3, cross-linking reaction: The carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 was mixed with the solanac gum solution obtained in step 2, and sodium tripolyphosphate was added under alkaline conditions to carry out a cross-linking reaction to obtain a cross-linking product solution. Step 4, Post-processing: The cross-linked product solution obtained in step 3 was neutralized to neutral, and sodium dodecylbenzenesulfonate was added and mixed evenly to obtain a dust suppressant.

5. The preparation method according to claim 4, characterized in that, In step 1, the gastrodia polysaccharide is dissolved in the first portion of water and heated and stirred at 50-70°C to obtain a gastrodia polysaccharide solution.

6. The preparation method according to claim 4, characterized in that, In step 1, the carboxymethylation reaction is carried out at a temperature of 55℃-65℃ for 2-4 hours.

7. The preparation method according to claim 4, characterized in that, In step 2, the heating and stirring temperature is 85℃-95℃.

8. The preparation method according to claim 4, characterized in that, In step 3, the carboxymethylated Gastrodia elata polysaccharide solution obtained in step 1 is mixed with the solanac gum solution obtained in step 2, the pH of the mixed solution is adjusted to 9-11, and sodium tripolyphosphate is added.

9. The preparation method according to any one of claims 4-8, characterized in that, In step 3, sodium trimetaphosphate is added to carry out a cross-linking reaction at a temperature of 45℃-55℃.

10. The application of the multifunctional dust suppressant for coal mines as described in any one of claims 1-3 in dust control during coal mining, transportation, and storage.

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