Coal mine dust suppression material with high wetting property and high film-forming property as well as preparation method and application of coal mine dust suppression material

Abstract

The invention discloses a coal mine dust suppression material with high wetting property and high film-forming property. The coal mine dust suppression material is prepared from the following raw materials in parts by mass: 1 to 10 parts of locust bean gum, 0.5 to 5 parts of hydrogen peroxide, 0.5 to 8 parts of polyethylene glycol didehydrated glyceryl ether, 1 to 10 parts of butanetetracarboxylic acid, 0.003 to 0.17 part of first catalyst, 0.007 to 0.33 part of second catalyst, 1 to 5 parts of wetting agent, 1 to 8 parts of water-retaining agent and 1000 to 2000 parts of distilled water. The dust suppression material can quickly reduce the surface tension and permeate and capture fine dust particles; and meanwhile, a flexible or rigid shell layer with excellent mechanical strength can be formed after water evaporation, so that the unification of rapid dust suppression and long-acting dust fixation is realized.

Description

Technical Field

[0001] This invention relates to the field of dust control technology, specifically to a coal mine dust suppression material with both high wettability and high film-forming properties, its preparation method, and its application. Background Technology

[0002] Mining and coal storage processes generate large amounts of dust, causing serious environmental pollution, material loss, equipment wear, and occupational health hazards. Currently, widely used methods for effective dust control include water spraying, covering, and the use of chemical dust suppressants. Traditional water spraying is the most common and economical method, but its effect is short-lived due to rapid water evaporation. Developing highly efficient chemical dust suppressants has become the primary solution for dust control.

[0003] Traditional chemical dust suppressants fix dust through adhesion or moisture absorption. These suppressants mainly rely on the bonding effect of polymers to form a hard, continuous solidified shell on the dust surface, thus firmly binding the dust particles. These suppressants typically have high viscosity; although they can form a hard shell, they struggle to quickly penetrate the dust layer. For thicker coal seams, the lower layers of dust remain loose. In contrast, wetting dust suppressants primarily use surfactants to significantly reduce the surface tension of water, improving its wetting, spreading, and penetration capabilities. While they offer excellent wetting properties and can quickly capture and settle airborne dust, they themselves possess almost no binding ability. Once the moisture evaporates, they fail to form an effective solidified layer, resulting in poor dust suppression durability and inability to withstand strong winds or mechanical disturbances.

[0004] Therefore, there is an urgent need to develop a new type of dust suppressant with high wettability and high film-forming properties, which can solve the technical problems of existing coal mine dust suppressant materials, such as poor strength, easy failure after mechanical disturbance, or poor wettability, making it difficult to penetrate and consolidate deep dust. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention discloses a coal mine dust suppression material possessing both high wettability and high film-forming properties, along with its preparation method and applications. This dust suppression material not only rapidly reduces surface tension, penetrating and capturing fine dust particles, but also forms a flexible or rigid shell with excellent mechanical strength after moisture evaporation, thus achieving a balance between rapid dust suppression and long-term dust fixation.

[0006] The primary objective of this invention is to provide a coal mine dust suppression material that combines high wetting and high film-forming properties. The dust suppression material comprises the following raw materials in parts by weight: 1-10 parts locust bean gum, 0.5-5 parts hydrogen peroxide, 0.5-8 parts polyethylene glycol dihydroglycerol ether, 1-10 parts butanetetracarboxylic acid, 0.003-0.17 parts first catalyst, 0.007-0.33 parts second catalyst, 1-5 parts wetting agent, 1-8 parts water-retaining agent, and 1000-2000 parts distilled water.

[0007] Specifically, the first catalyst is copper sulfate and the second catalyst is sodium hypophosphite.

[0008] Specifically, the wetting agent is an alkyl glycoside; the water-retaining agent is glycerol.

[0009] Specifically, when the amount of distilled water is 100 mL, the preferred weights of the other raw materials are as follows: 0.5 g locust bean gum, 0.25 g hydrogen peroxide, 0.3 g polyethylene glycol dihydroglycerol ether, 0.5 g butanetetracarboxylic acid, 0.05 g first catalyst, 0.1 g second catalyst, 0.25 g wetting agent, and 0.3 g water-retaining agent.

[0010] The second objective of this invention is to provide a method for preparing a coal mine dust suppression material that combines high wettability and high film-forming properties. This method includes the following steps: S1. Add locust bean gum and distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath and heat and stir until completely dissolved to obtain a locust bean gum solution. S2 adds the first catalyst to the locust bean gum solution, stirs it evenly, and then adds hydrogen peroxide to carry out the oxidation reaction to obtain an oxidized locust bean gum solution. S3 added polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath to obtain pre-crosslinking product I; S4. Butanetetracarboxylic acid and a second catalyst are added sequentially to the pre-crosslinked product I to obtain a reaction solution; after adjusting the pH of the reaction solution to 3-5, the main crosslinking reaction is carried out in a constant temperature water bath to obtain crosslinked product II; S5 adjusts the pH of the crosslinking product II to neutral, then adds a wetting agent and a water-retaining agent, cools to room temperature and stirs evenly to obtain a coal mine dust suppression material with both high wetting and high film-forming properties.

[0011] Specifically, the heating and stirring process in step S1 is carried out at a temperature of 40-60°C for 1-2 hours.

[0012] Specifically, the oxidation reaction in step S2 is carried out at a temperature of 50-70°C for 1-4 hours.

[0013] Specifically, the temperature of the pre-crosslinking reaction in step S3 is 60-80℃, and the time is 1-2h.

[0014] Specifically, the temperature of the main crosslinking reaction in step S4 is 70-90℃, and the time is 1-3h.

[0015] The third objective of this invention is to provide an application of the coal mine dust suppression material described above, which combines high wettability and high film-forming properties, in coal mine dust suppression.

[0016] The reaction equations for the oxidation reactions involved in this invention are as follows:

[0017] The reaction mechanism of oxidation reaction: under the catalyst Cu 2+ Under the influence of hydrogen peroxide, highly reactive hydroxyl radicals are generated through decomposition. These radicals preferentially attack the β-1,4-glycosidic bonds in the locust bean gum backbone, causing them to break and thus cleaving the long molecular chain of locust bean gum into smaller molecular weight fragments. Simultaneously, the radicals also oxidize some secondary hydroxyl groups on the locust bean gum molecular chain to carbonyl groups. These newly introduced carbonyl groups and the reducing aldehyde groups at the ends of the broken chains provide more active sites for subsequent cross-linking reactions.

[0018] The reaction equations for the pre-crosslinking reaction involved in this invention are as follows:

[0019] The reaction mechanism of the pre-crosslinking reaction: Polyethylene glycol dihydroglycerol ether (PEGDGE) is a long-chain diepoxy compound. Under mild alkaline or neutral conditions, the epoxy groups at both ends of its molecule can undergo ring-opening etherification with the hydroxyl groups on the oxidized locust bean gum molecular chain. One PEGDGE molecule can react with the hydroxyl groups on two oxidized locust bean gum molecular chains simultaneously, thereby building "bridges" between multiple molecular chains and forming a preliminary flexible crosslinking network. This pre-crosslinking step constructs the basic framework of the dust suppressant skeleton, enhances the intermolecular cohesion, and lays the foundation for subsequent, denser main crosslinking.

[0020] The reaction equation for the main crosslinking reaction involved in this invention is as follows:

[0021] Butanetetracarboxylic acid (BTCA) is a multivalent crosslinking agent containing four carboxyl groups. Under acidic conditions and upon heating, the carboxyl groups of BTCA undergo esterification with a large number of hydroxyl groups in the pre-crosslinked oxidized locust bean gum network, removing water molecules (H2O) and forming strong covalent ester bonds. Because a BTCA molecule has four carboxyl groups, it acts as a "crosslinking hub," simultaneously connecting three to four pre-crosslinked molecular chains, thereby constructing a denser and more rigid three-dimensional crosslinked network based on the pre-crosslinked network.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects: (1) This invention uses environmentally friendly chemicals locust bean gum, polyethylene glycol dihydroglycerol ether, butanetetracarboxylic acid, and hydrogen peroxide as main raw materials. A significant synergistic effect is formed through a three-step modification strategy. First, the processability problem is solved and the reactive sites are activated by oxidative modification of locust bean gum. Then, a three-dimensional network structure with both rigidity and flexibility and a dense structure is constructed through a dual crosslinking strategy of "pre-crosslinking-main crosslinking". A flexible skeleton is constructed through pre-crosslinking, that is, the pre-crosslinking based on polyethylene glycol dihydroglycerol ether (PEGDGE) and oxidized locust bean gum provides a flexible long-chain network skeleton, and the structure of the dust suppression material is initially constructed to obtain pre-crosslinked product I, which prevents the disadvantages of low strength and easy film damage caused by excessive crosslinking in the later stage. Then, the main crosslinking finally endows the dust suppression material with excellent mechanical properties and weather resistance. That is, the main crosslinking reaction based on butanetetracarboxylic acid (BTCA) and pre-crosslinked product I introduces high-density covalent ester bonds, which greatly improves the toughness, compressive strength and shear resistance of the cured layer. The resulting dust suppression material, after being sprayed, forms a solidified layer with high film-forming properties, excellent mechanical strength, toughness and durability, and superior wettability. It can effectively resist strong ventilation airflow and mechanical disturbance in coal mines, achieving long-term dust suppression. (2) In this invention, the locust bean gum is first oxidized and modified with hydrogen peroxide, which oxidizes some of the secondary hydroxyl groups on the locust bean gum molecular chain to carbonyl groups. The newly introduced carbonyl groups and the reducing aldehyde groups at the ends of the broken chains provide more active sites for the subsequent cross-linking reaction. The long chains of the locust bean gum are also pre-cut, which reduces the viscosity of the locust bean gum solution, making it easier to pump and atomize. Then, polyethylene glycol dihydroglycerol ether (PEGDGE) reacts with the hydroxyl groups on the oxidized locust bean gum molecular chain to undergo a ring-opening etherification reaction, building "bridges" between multiple molecular chains to form a preliminary flexible cross-linking network. The basic framework of the dust suppression material was constructed, which enhanced the intermolecular cohesion, improved the initial film-forming properties and mechanical strength, and laid the foundation for subsequent denser main crosslinking. Then, hydrophilic butanetetracarboxylic acid (BTCA) was introduced. One BTCA molecule has four carboxyl groups, which can simultaneously connect to the molecular chains of 3-4 pre-crosslinked product I and undergo esterification reactions with a large number of hydroxyl groups in pre-crosslinked product I to form strong covalent ester bonds. Thus, based on pre-crosslinked product I, a three-dimensional crosslinked network with higher density and stronger rigidity was constructed to obtain crosslinked product II.

[0023] (3) This invention uses natural biodegradable locust bean gum, which has excellent film-forming and adhesive properties. When dissolved in water, it can form a high-viscosity gel with strong adsorption and encapsulation capabilities for dust particles. After drying, it can form a continuous film, effectively consolidating dust and preventing it from flying away. The selected polyethylene glycol dihydroglycerol ether is used as a pre-crosslinking agent. The polyethylene glycol segments contained in its molecular chain are excellent flexible spacer arms, which can give the crosslinking network good toughness and elasticity, making the cured layer formed by the dust suppression material less prone to brittleness and cracking when drying shrinkage, temperature changes, or subjected to external force, and significantly improving its strength. In addition, the epoxy groups at both ends of its molecule have high reactivity and can undergo ring-opening reactions with the hydroxyl and carboxyl groups of locust bean gum to form stable ether bonds or ester bonds, efficiently constructing the primary network. Polyethylene glycol dihydroglycerol ether has good compatibility with locust bean gum and water, which facilitates on-site mixing and spraying. (3) This invention selects a polybasic organic acid, butanetetracarboxylic acid, which has four carboxyl groups on its molecular chain. Its excellent wettability ensures that the oxidized locust bean gum and its crosslinking network can achieve maximum close contact with each dust particle, which not only greatly increases the bonding sites, like coating the dust particles with a strong "structural adhesive", but also lays a solid foundation for the formation of a continuous, dense, and high-strength integral solidified layer in the subsequent drying process. Using it as a crosslinking agent can greatly improve the wettability of the dust suppressant. As the main crosslinking agent, it can crosslink with hydroxyl-containing substances with high strength to form a high-density and strong ester bond network; so that the cured layer formed after the dust suppressant is sprayed has excellent mechanical strength and resistance to rain erosion and soaking. In addition, butanetetracarboxylic acid is also formaldehyde-free and environmentally friendly. It will not release harmful aldehyde gases during use, which meets the requirements of environmental protection. (4) In this invention, glycerol is selected as a water-retaining agent and alkyl glycosides are selected as wetting agents. Each glycerol molecule can form a multi-hydrogen bond network with water molecules through three hydroxyl groups to achieve high water retention performance and has biodegradable characteristics, which meets environmental protection requirements. The nonionic surfactant alkyl glycoside is selected as a wetting agent, which has excellent wetting performance and can reduce the surface tension of the dust suppressant solution, so that it can quickly and evenly penetrate into the interior and gaps of coal dust particles to achieve deep curing. (5) The dust suppression material prepared by this invention can slowly degrade its ester bonds and polysaccharide backbone in the natural environment after its service life, avoiding ecological accumulation and secondary pollution to the surrounding environment of the mining area, which fully meets the development requirements of green mines. In addition, it is degraded by hydrogen peroxide oxidation; at the same time, the preparation method of this invention is mild and controllable, retaining enough active sites of polysaccharide molecules for subsequent cross-linking, achieving a perfect balance between processing performance and performance. Attached Figure Description

[0024] Figure 1 The process flow diagram shows the coal mine dust suppression materials with both high wettability and high film-forming properties prepared in Examples 1-9 of this invention. Figure 2 This is a comparison chart of the wettability tests of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 of the present invention; Figure 3 The graph shows a comparison of the dust suppression efficiency of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 of this invention. Detailed Implementation Plan The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing specific embodiments only and is not intended to limit the present invention.

[0025] Please see Figure 1 , Figure 1 The process flow diagram shows the coal mine dust suppression materials with both high wettability and high film-forming properties prepared in Examples 1-9 of this invention.

[0026] Example 1 S1. Add 0.5g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.15g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.2g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1h to obtain pre-crosslinking product I; S4. 0.3 g butanetetracarboxylic acid and 0.1 g sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 1.

[0027] Example 2 S1. Add 0.5g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.25g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.3g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1h to obtain pre-crosslinking product I; S4. 0.5 g of butanetetracarboxylic acid and 0.1 g of sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 2.

[0028] Example 3 S1. Add 0.5g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.4g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.3g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1h to obtain pre-crosslinking product I; S4. 0.5 g of butanetetracarboxylic acid and 0.1 g of sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 3.

[0029] Example 4 S1. Add 0.5g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.25g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.3g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1h to obtain pre-crosslinking product I; S4. 0.5 g of butanetetracarboxylic acid and 0.1 g of sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 4.

[0030] Example 5 S1. Add 0.6g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.25g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.4 g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1 h to obtain pre-crosslinking product I; S4. 0.3 g butanetetracarboxylic acid and 0.1 g sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 5.

[0031] Example 6 S1. Add 0.6g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath and heat and stir at 60℃ for 1 hour until it is completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.25g of hydrogen peroxide. The oxidation reaction is carried out at 70℃ for 1 hour to obtain an oxidized locust bean gum solution. S3 added 0.2g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 80℃ for 2h to obtain pre-crosslinking product I; S4. 0.5 g of butanetetracarboxylic acid and 0.1 g of sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 90°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 6.

[0032] Example 7 S1. Add 0.7g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 40℃ and heat and stir for 1.5h until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.15g of hydrogen peroxide. The oxidation reaction is carried out at 50°C for 4 hours to obtain an oxidized locust bean gum solution. S3 added 0.4 g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 60℃ for 2 h to obtain pre-crosslinking product I; S4. 0.7 g butanetetracarboxylic acid and 0.1 g sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 70°C for 3 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 7.

[0033] Example 8 S1. Add 0.7g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.4g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.2g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1h to obtain pre-crosslinking product I; S4. 0.7 g butanetetracarboxylic acid and 0.1 g sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 7.

[0034] Example 9 S1. Add 0.7g of locust bean gum and 100mL of distilled water to a beaker in sequence. Place the beaker in a constant temperature water bath at 50℃ and heat and stir for 2 hours until completely dissolved to obtain a locust bean gum solution. S2 Add 0.05g of copper sulfate to the locust bean gum solution, stir evenly, and then add 0.4g of hydrogen peroxide. The oxidation reaction is carried out at 60℃ for 2 hours to obtain an oxidized locust bean gum solution. S3 added 0.4 g of polyethylene glycol dihydroglycerol ether to the oxidized locust bean gum solution, stirred evenly, and carried out a pre-crosslinking reaction in a constant temperature water bath at 70℃ for 1 h to obtain pre-crosslinking product I; S4. 0.3 g butanetetracarboxylic acid and 0.1 g sodium hypophosphite were added sequentially to the pre-crosslinked product I to obtain the reaction solution; the pH of the reaction solution was adjusted to 4 with dilute hydrochloric acid and then the main crosslinking reaction was carried out in a constant temperature water bath at 80°C for 2 h to obtain crosslinked product II. S5 uses sodium hydroxide to adjust the pH of the crosslinking product II to 7, then adds 0.25g of alkyl glycoside and 0.3g of glycerol, cools to room temperature and stirs evenly to obtain the coal mine dust suppression material with high wettability and high film-forming properties prepared in Example 7.

[0035] Comparative Example 1 S1 Add 100mL of distilled water to a beaker, dissolve 0.7g of locust bean gum in the distilled water, place it in a water bath, set the temperature to 45℃, heat and stir for 2 hours until the locust bean gum is completely dissolved, and obtain a locust bean gum aqueous solution. S2 added 0.05g of copper sulfate to the locust bean gum aqueous solution, stirred and dissolved, then added 0.25g of hydrogen peroxide, and reacted in a water bath at 60℃ for 2h to obtain the dust suppression material prepared in Comparative Example 1.

[0036] Comparative Example 2 Dissolve 0.3g of polyethylene glycol dihydroglycerol ether in 100mL of distilled water and stir in an 80℃ water bath for 1h until completely dissolved to obtain the dust suppression material prepared in Comparative Example 2.

[0037] Performance testing The wettability, dust suppression effect and mechanical properties of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 are tested below.

[0038] Wettability Test: The wettability of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 to coal dust was evaluated using a contact angle measurement method. Coal powder was sieved through a 200-mesh sieve and then pressed into uniformly sized, smooth, flat discs under a specific pressure (10 MPa). Approximately 3-5 μL of the test solution was aspirated using a microsyringe. The syringe needle was placed vertically about 1-2 mm above the solid substrate. A droplet was ejected at a constant speed, allowing it to settle smoothly on the substrate surface. The contact angle value was measured using a contact angle meter. At least five different locations were measured for each sample on the same substrate, and the average value after 2 seconds was taken as the measured value.

[0039] Please refer to the test results. Figure 2 , Figure 2 This is a comparison chart showing the wettability test results of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 of this invention. Figure 2It can be seen that the contact angles of Examples 1-9 of the present invention are significantly lower than those of Comparative Examples 1 and 2, proving their superior wetting performance. Compared with Comparative Examples 1-2, neither locust bean gum nor polyethylene glycol dihydroglycerol ether alone showed good wetting properties; however, in Examples 1-9, because butanetetracarboxylic acid contains a large number of carboxyl groups, which are hydrophilic groups, the cross-linking reaction results in the molecular chains of the dust suppressant having a large number of carboxyl groups, thereby increasing the hydrophilicity of the dust suppressant. This allows it to quickly encapsulate and wet each dust particle, overcoming its hydrophobicity, and greatly improving the wetting properties of the dust suppressant. It also provides a uniform and sufficient prerequisite for the subsequent formation of a high-strength solidified shell layer through water evaporation. Among them, Example 4 performed best, with a contact angle as low as 5.4°, close to a fully spread state, indicating that its formulation can greatly reduce the surface tension of the liquid and spread rapidly on the solid surface.

[0040] Mechanical Performance Testing: The compressive strength test was used to evaluate the strength performance of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 on the surface of pulverized coal. First, dust suppression materials of different concentrations were prepared according to Examples 1-9 and Comparative Examples 1-2 and thoroughly mixed with coal samples to form samples, ensuring uniform distribution of the dust suppression material within the coal samples and thus guaranteeing the reliability of subsequent test results. After mixing, 40g of the treated samples were taken. These samples underwent pretreatment steps such as natural drying, grinding, and sieving to eliminate differences between samples. Then, the treated samples were evenly spread in petri dishes, ensuring a smooth surface and uniform thickness to facilitate uniform penetration of the subsequent spraying solution. Each group of samples was sprayed with solutions from Examples 1-9 and Comparative Examples 1-2, respectively. After spraying, the samples were allowed to stand for 24 hours to fully solidify, ensuring the dust suppressant forms a stable solidified layer in the coal samples. Next, the compressive strength test was performed, placing the samples on a compression testing machine to ensure good contact between the samples and the pressure sensor. At the start of the test, pressure was gradually applied, and the maximum applied force was recorded, representing the highest pressure the sample could withstand before failure. By measuring the maximum pressure and the cross-sectional area of ​​the sample, its compressive strength could be calculated and data analysis performed to evaluate the performance of dust suppressants at different concentrations. The test results are shown in Table 1 below: Table 1

[0041] Table 1 shows that the dust suppression materials prepared in Examples 1-9 and Examples 1-2 exhibit significantly different compressive strengths. Example 4 shows the highest compressive strength, at 13.5 MPa. The compressive strengths of the comparative examples are 5 MPa and 3 MPa, respectively. This indicates that the cross-linked dust suppressant, after solidification with coal dust, has a higher compressive strength. This is because oxidized locust bean gum pre-crosslinks with polyethylene glycol dihydroglycerol ether to form a flexible bridge structure, laying the foundation for the basic structure of the dust suppressant. Then, it undergoes primary crosslinking with butanetetracarboxylic acid, forming a complex three-dimensional network structure between the coal seams, resulting in a dense, continuous, and high-strength solidified layer.

[0042] Dust suppression effect test: This test plan aims to study the surface solidification effect of coal dust suppressants. First, the experiment will use different dust suppressant samples prepared according to Examples 1-9 and Comparative Examples 1-2. Coal powder of 100-200 mesh was selected and dried in an oven at 50°C for 300 minutes to remove moisture. 100g of coal powder was weighed and placed on a surface level with the graduation mark, then leveled with a scraper. The dust suppressant was applied at the required concentration of 2.5mL / m³. 2 Spray evenly onto the surface of the coal powder. Bake in an oven at 50°C for 120 minutes. Measure the thickness of the cured layer at four random locations and take the average value.

[0043] Test results are as follows Figure 3 As shown, please refer to Figure 3 , Figure 3 This is a comparison chart showing the dust suppression effects of the dust suppression materials prepared in Examples 1-9 and Comparative Examples 1-2 of the present invention. Figure 3 It can be seen that in Comparative Examples 1-2, the solidification layer thicknesses of 0.5cm and 0.2cm resulted in a small solidification effect and the highest coal dust release, directly impacting environmental safety and reflecting the stubbornness of coal dust without dust suppression measures. The examples show significant improvement, with Example 4 exhibiting the best dust suppression effect among all groups, achieving a solidification layer thickness of 2.1cm. Under this formulation, the dust suppressant effectively penetrates and adheres to the coal powder surface, forming a strong solidification layer that significantly reduces dust release while maintaining good physical properties.

[0044] This invention tests the freeze resistance and dust suppression efficiency of the dust suppression materials prepared in Examples 1-9 by designing different formulations. Notably, in the performance test, the cured layer formed in Example 4 had the largest thickness, reaching 2.1 cm; the compressive strength was the highest, reaching 13.5 MPa, forming a strong cured layer. In the dust suppression efficiency and mechanical tests, the dust suppression material prepared in Example 4 had the best dust suppression effect and the best mechanical properties of the cured layer. Therefore, under the condition of 100 mL distilled water, the preferred addition amounts of other raw materials are 0.5 g locust bean gum, 0.25 g hydrogen peroxide, 0.3 g polyethylene glycol dihydroglycerol ether, 0.5 g butanetetracarboxylic acid, 0.05 g first catalyst, 0.1 g second catalyst, 0.25 g wetting agent, and 0.3 g water-retaining agent. The dust suppression material prepared under this preferred formulation has superior mechanical strength, higher wettability, and high dust suppression performance.

[0045] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A coal mine dust suppression material with high wetting and high film forming property, characterized in that, The dust suppression material comprises the following raw materials in mass fraction: 1-10 parts of locust bean gum, 0.5-5 parts of hydrogen peroxide, 0.5-8 parts of polyethylene glycol diglyceryl ether, 1-10 parts of butane tetracarboxylic acid, 0.003-0.17 parts of a first catalyst, 0.007-0.33 parts of a second catalyst, 1-5 parts of a wetting agent, 1-8 parts of a water-retaining agent, and 1000-2000 parts of distilled water.

2. The dust suppressing material of claim 1, wherein, The first catalyst is copper sulfate, and the second catalyst is sodium hypophosphite.

3. The dust suppressing material of claim 1, wherein, The wetting agent is alkyl polyglycoside, and the water-retaining agent is glycerol.

4. The dust suppressing material of claim 1, wherein, When the distilled water is 100 mL, the weights of the other raw materials are preferably 0.5 g of locust bean gum, 0.25 g of hydrogen peroxide, 0.3 g of polyethylene glycol diglyceryl ether, 0.5 g of butane tetracarboxylic acid, 0.05 g of the first catalyst, 0.1 g of the second catalyst, 0.25 g of the wetting agent, and 0.3 g of the water-retaining agent.

5. The method for preparing the coal mine dust suppression material with high wetting and high film forming property according to any one of claims 1-4, characterized in that, The preparation method comprises the following steps: S1 adding locust bean gum and distilled water into a beaker in sequence, heating and stirring the beaker in a constant-temperature water bath until the locust bean gum is completely dissolved to obtain a locust bean gum solution; S2 adding a first catalyst to the locust bean gum solution, stirring uniformly, and then adding hydrogen peroxide to perform an oxidation reaction to obtain an oxidized locust bean gum solution; S3 adding polyethylene glycol diglyceryl ether to the oxidized locust bean gum solution, stirring uniformly, and then performing a pre-crosslinking reaction in a constant-temperature water bath to obtain a pre-crosslinking product I; S4 adding butane tetracarboxylic acid and a second catalyst to the pre-crosslinking product I to obtain a reaction solution; adjusting the pH of the reaction solution to 3-5, and then performing a main crosslinking reaction in a constant-temperature water bath to obtain a crosslinking product II; S5 adjusting the pH of the crosslinking product II to neutral, and then adding a wetting agent and a water-retaining agent, stirring uniformly after cooling to room temperature, to obtain a coal mine dust suppression material with high wetting and high film-forming properties.

6. The production method according to claim 5, wherein In step S1, the heating and stirring treatment is performed at a temperature of 40-60°C for 1-2 h.

7. The preparation method according to claim 5, characterized in that, In step S2, the oxidation reaction is performed at a temperature of 50-70°C for 1-4 h.

8. The preparation method according to claim 5, characterized in that, In step S3, the pre-crosslinking reaction is performed at a temperature of 60-80°C for 1-2 h.

9. The preparation method according to claim 5, characterized in that, In step S4, the main crosslinking reaction is performed at a temperature of 70-90°C for 1-3 h.

10. Application of the coal mine dust suppression material with high wetting and high film-forming properties in coal mining dust suppression according to any one of claims 1-4.

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