Environment-friendly coal dust suppressant based on bionic adhesion technology and preparation method of environment-friendly coal dust suppressant

Abstract

The invention relates to the technical field of coal dust suppression, in particular to an environment-friendly coal dust suppressant based on a bionic adhesion technology and a preparation method of the environment-friendly coal dust suppressant. The dust suppressant comprises the following components in parts by weight: 15-35 parts of catechol group modified polyvinyl alcohol, 5-15 parts of glycerol, 5-12 parts of sodium humate, 3-8 parts of nano silicon dioxide, 1-3 parts of a surfactant, 0.5-2 parts of a defoaming agent and 40-60 parts of water. Inspired by a strong adhesion mechanism of mussel mucoprotein, the core of the invention is to introduce catechol group modified polyvinyl alcohol as a main film-forming binding material. According to the modified PVA, a layer of three-dimensional cross-linked network protection film with super-strong adhesion and good weather resistance can be formed on the surface of coal through multiple interactions of strong coordinate bonds, hydrogen bonds and the like formed by catechol groups and particles on the surface of the coal powder and inside the coal powder, the wind erosion resistance, the wear resistance and the durability of the dust suppressant are greatly improved, all the components are biodegradable, and the dust suppressant is environment-friendly and pollution-free. The method is environment-friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coal railway transportation environmental protection technology, and particularly relates to a high-efficiency and environmentally-friendly coal dust suppressant based on biomimetic adhesion technology and a preparation method thereof. BACKGROUND

[0002] In the process of coal railway open wagon transportation, the surface of the coal pile is extremely prone to serious dust raising under the combined action of high-speed airflow stripping and long-term vibration. This not only causes coal quality loss and economic loss during transportation, but also forms continuous particulate matter pollution along the railway, and the demand for governance is urgent.

[0003] Currently, one of the main technical means for preventing and controlling dust pollution and reducing coal spillage loss in the process of railway coal transportation is to apply chemical dust suppressants. Such preparations form a high-molecular solidification film layer on the surface of the coal body to block the outward diffusion of dust, thereby achieving the purpose of dust suppression. However, the existing chemical dust suppressants suitable for railway coal transportation still have several key shortcomings: the film-forming material has weak bonding strength with the surface of the coal particles, and under the action of continuous mechanical vibration during long-distance transportation and wind and rain erosion, the film layer is prone to breakage, pulverization and even peeling; at the same time, the solidification film has insufficient flexibility and is difficult to adapt to repeated vibration during train operation and the pressure generated by coal stacking; in addition, most products have poor environmental degradability, and chemical residues may pose potential risks to the ecological environment of soil and water along the railway. Therefore, there is an urgent need to develop a special dust suppressant that can adapt to the harsh conditions of railway transportation, while having the characteristics of firm adhesion, resistance to dynamic vibration and environmental friendliness throughout the life cycle.

[0004] In nature, marine mussels can secrete a kind of mucin, such as Mfp protein, which is rich in catechol groups, to produce extremely firm adhesion on the wet and turbulent seabed rocks. The chemical nature of this process lies in that the catechol group can form a strong coordination bond with the metal oxides on the rock surface, such as iron, manganese and silicon oxides, when it approaches the rock surface. At the same time, the catechol group can also form a large number of hydrogen bonds between the rock surface and the mucin molecules, and form a covalent bond network through oxidative crosslinking. The multiple synergistic effects of coordination bond, hydrogen bond and covalent bond enable the mussel mucin to achieve persistent and high-strength adhesion to various substrates in a water environment.

[0005] Inspired by this, the present application provides an environmentally-friendly coal dust suppressant based on biomimetic adhesion technology and a preparation method thereof. The dust suppressant takes catechol group-modified polyvinyl alcohol as the core and can form a strong and durable protective film on the surface of coal powder, having excellent dust suppression performance and biodegradability. SUMMARY

[0006] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The application provides an environment-friendly coal dust suppressant based on a biomimetic adhesion technology, and components of the dust suppressant include, by weight fraction, 15-35 parts of catechol group modified polyvinyl alcohol, 5-15 parts of glycerol, 5-12 parts of sodium humate, 3-8 parts of nano silicon dioxide, 1-3 parts of a surfactant, 0.5-2 parts of a defoaming agent, and 40-60 parts of water.

[0008] Preferably, components of the coal dust suppressant include, by weight fraction, 25 parts of catechol group modified polyvinyl alcohol, 10 parts of glycerol, 8 parts of sodium humate, 5 parts of nano silicon dioxide, 2 parts of a surfactant, 1 part of a defoaming agent, and 50 parts of water.

[0009] Preferably, the surfactant is one or more of sodium dodecyl sulfate, alkyl glycoside, or fatty alcohol polyoxyethylene ether.

[0010] Preferably, the defoaming agent is one or more of silicone defoaming agent or polyether modified silicone oil.

[0011] The application provides a preparation method of the catechol group modified polyvinyl alcohol, including the following steps:

[0012] Under the protection of inert gas, polyvinyl alcohol powder with an average polymerization degree of 1700 and an alcoholysis degree of 99% is dissolved in a mixed solvent of dimethyl sulfoxide and water, and the temperature is raised to 80°C; then 3,4-dihydroxybenzoic acid accounting for 10%-30% of the mass of PVA and a catalytic amount of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride are added, and the reaction is carried out at 80°C for 6-12 hours; after the reaction is completed, the solution is cooled to room temperature, precipitated in excess ethanol, and the obtained solid is washed with ethanol for three times and vacuum dried to constant weight to obtain catechol group modified polyvinyl alcohol.

[0013] The application provides a preparation method of the environment-friendly coal dust suppressant based on the biomimetic adhesion technology, including the following steps:

[0014] Step S1: water is heated to 85-95°C, and catechol group modified polyvinyl alcohol is slowly added under stirring at a speed of 800-1200 revolutions per minute, and the solution is stirred for 1-2 hours until completely dissolved to obtain transparent viscous solution A;

[0015] Step S2: the solution A is cooled to 50-60°C, and glycerol, sodium humate and nano silicon dioxide are sequentially added under stirring at a speed of 400-600 revolutions per minute, and the stirring is continuously carried out for 40-60 minutes to obtain uniform mixture B;

[0016] Step S3: Continue to cool mixture B to 35-45℃, add surfactant and defoamer, stir continuously at 200-300 rpm for 20-30 minutes, let stand and age for 1-2 hours to obtain the final dust suppressant product.

[0017] The dust suppressant of this invention meets all the requirements for dust suppressants in "TB / T 3210.1-2020 Technical Conditions for Dust Suppression in Railway Coal Transportation", and performs particularly well in terms of adhesion, durability and environmental protection.

[0018] The beneficial effects of this invention are:

[0019] Super strong adhesion and film-forming properties: The core component, catechol-modified PVA, has catechol groups on its molecular chain that can form strong coordination bonds with metal oxides and other components in coal powder. At the same time, it can tightly bind to the surface of coal powder through hydrogen bonding, π-π stacking and other effects, forming a tough and dense three-dimensional cross-linked network protective film with extremely strong wind erosion resistance.

[0020] Environmentally friendly: The main components, such as polyvinyl alcohol and sodium humate, are all biodegradable materials, avoiding secondary pollution to the environment caused by traditional polymers.

[0021] Long-lasting effect: The protective film formed is chemically stable, resistant to rain erosion and dry-wet cycle, and its dust suppression duration is significantly better than that of traditional dust suppressants.

[0022] Synergistic formulation: Glycerin acts as a plasticizer to prevent the film from becoming too brittle; sodium humate provides adhesion and water retention; and nano-silica enhances the mechanical strength and abrasion resistance of the film. The synergistic effect of these components collectively improves the overall performance of the dust suppressant. Detailed Implementation

[0023] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way.

[0024] Example 1

[0025] Dust suppressant formulation: 15 parts catechol-modified PVA, 5 parts glycerin, 5 parts sodium humate, 3 parts nano silica, 1 part sodium dodecyl sulfate, 0.5 parts organosilicon defoamer, and 40 parts water.

[0026] Preparation method:

[0027] Step S1: Heat water to 85°C, slowly add catechol-modified polyvinyl alcohol while stirring at 800 rpm, keep warm and stir for 1-2 hours until completely dissolved to obtain transparent viscous liquid A;

[0028] Step S2: Cool solution A to 50°C, add glycerol, sodium humate and nano silica sequentially while stirring at 400 rpm, and continue stirring for 40 minutes to obtain a homogeneous mixture B;

[0029] Step S3: Continue to cool mixture B to 35°C, add sodium dodecyl sulfate and silicone defoamer, stir continuously at 200 rpm for 20 minutes, and let stand for 1 hour to obtain the final dust suppressant product.

[0030] The performance of the dust suppressant solution from Example 1 was measured according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0031]

[0032] All indicators in Example 1 meet the requirements of TB / T 3210 standard, with a low wind erosion rate, indicating that its dust suppression layer has good wind erosion resistance. The system viscosity is moderate, and the spraying performance is good; the pH value is slightly alkaline but still within the safe range, and it does not corrode metals. Overall, this formulation can still form an effective adhesive film layer with a low amount of modified PVA, possessing good basic dust suppression performance and environmental friendliness.

[0033] Example 2

[0034] Dust suppressant formulation: 35 parts catechol-modified PVA, 15 parts glycerin, 12 parts sodium humate, 8 parts nano silica, 3 parts alkyl glycoside, 2 parts polyether-modified silicone oil, and 60 parts water.

[0035] Preparation method:

[0036] Step S1: Heat water to 95°C, slowly add catechol-modified polyvinyl alcohol while stirring at 1200 rpm, keep warm and stir for 2 hours until completely dissolved to obtain transparent viscous liquid A;

[0037] Step S2: Cool solution A to 60°C, add glycerol, sodium humate and nano silica sequentially while stirring at 600 rpm, and continue stirring for 60 minutes to obtain a homogeneous mixture B;

[0038] Step S3: Continue to cool mixture B to 45°C, add alkyl glycoside and polyether modified silicone oil, stir continuously at 300 rpm for 30 minutes, let stand and age for 2 hours to obtain the final dust suppressant product.

[0039] The performance of the dust suppressant solution from Example 2 was measured according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0040]

[0041] Example 2 demonstrates system stability even at higher solids content, with a further reduction in wind erosion rate, indicating a denser and more robust dust suppression layer. Significantly increased viscosity makes it suitable for applications requiring higher film thickness. All safety and environmental indicators meet standards, demonstrating that the system maintains good environmental performance and safety even at high dosages.

[0042] Example 3 (Preferred)

[0043] Dust suppressant formula: 25 parts catechol-modified PVA, 10 parts glycerin, 8 parts sodium humate, 5 parts nano silica, 2 parts fatty alcohol polyoxyethylene ether, 1 part organosilicon defoamer, and 50 parts water.

[0044] Preparation method:

[0045] Step S1: Heat water to 90°C, slowly add catechol-modified PVA while stirring at 1000 rpm, keep warm and stir for 1.5 hours until completely dissolved to obtain solution A.

[0046] Step S2: Cool solution A to 55°C, add glycerol, sodium humate and nano silica in sequence, and stir at 500 rpm for 50 minutes to obtain mixture B.

[0047] Step S3: Cool mixture B to 40°C, add fatty alcohol polyoxyethylene ether and silicone defoamer, stir at 250 rpm for 25 minutes, let stand and age for 1.5 hours, and then discharge.

[0048] The performance of the dust suppressant solution from Example 3 was measured according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0049]

[0050] Example 3, under balanced formulation and optimized process, exhibited the best overall performance: the lowest wind erosion rate and the thickest cured layer, indicating the strongest and densest biomimetic adhesion network. Viscosity and pH were within ideal ranges, balancing workability and material compatibility. This optimized formulation fully demonstrates the core advantages of catechol-modified PVA, achieving an optimal balance between dust suppression, durability, and environmental friendliness.

[0051] Comparative Example 1 (Blank Control)

[0052] Dust suppressant formula: No film-forming binder added, namely 10 parts glycerin, 8 parts sodium humate, 5 parts nano silica, 2 parts fatty alcohol polyoxyethylene ether, 1 part silicone defoamer, and 50 parts water.

[0053] Preparation method:

[0054] Step S1: Heat water to 90°C and stir at 1000 rpm for 1.5 hours to obtain solution A.

[0055] Step S2: Cool solution A to 55°C, add glycerol, sodium humate and nano silica in sequence, and stir at 500 rpm for 50 minutes to obtain mixture B.

[0056] Step S3: Cool mixture B to 40°C, add fatty alcohol polyoxyethylene ether and silicone defoamer, stir at 250 rpm for 25 minutes, let stand and age for 1.5 hours, and then discharge.

[0057] The dust suppressant solution used in Comparative Example 1 was tested for performance according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0058]

[0059] Comparative Example 1, without the addition of film-forming adhesive material, exhibited a severely excessive wind erosion rate and failed to form an effective cured layer, demonstrating that the system lacks dust suppression functionality when the core adhesive component is absent. Although its basic physicochemical and safety indicators were satisfactory, it failed to meet the basic requirements for dust suppressant use, highlighting the indispensability of catechol-modified PVA as the main body for film formation and adhesion.

[0060] Comparative Example 2 (Standard PVA Control)

[0061] Dust suppressant formula: 25 parts ordinary PVA (average degree of polymerization 1700, degree of alcoholysis 99%), 10 parts glycerin, 8 parts sodium humate, 5 parts nano silica, 2 parts fatty alcohol polyoxyethylene ether, 1 part silicone defoamer, and 50 parts water.

[0062] Preparation method:

[0063] Step S1: Heat water to 90°C, slowly add ordinary PVA while stirring at 1000 rpm, keep warm and stir for 1.5 hours until completely dissolved to obtain solution A.

[0064] Step S2: Cool solution A to 55°C, add glycerol, sodium humate and nano silica in sequence, and stir at 500 rpm for 50 minutes to obtain mixture B.

[0065] Step S3: Cool mixture B to 40°C, add fatty alcohol polyoxyethylene ether and silicone defoamer, stir at 250 rpm for 25 minutes, let stand and age for 1.5 hours, and then discharge.

[0066] The performance of the dust suppressant solution in Comparative Example 2 was tested according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0067]

[0068] Comparative Example 2 used ordinary PVA instead of modified PVA. Although its wind erosion rate was improved compared to Comparative Example 1, it was still significantly higher than that of the embodiments of the present invention, and the thickness of the cured layer was insufficient. This indicates that although ordinary PVA has certain film-forming and adhesion capabilities, it lacks the multiple bonding effect provided by catechol groups, resulting in its bonding strength with the coal powder surface, film toughness, and resistance to dynamic peeling being far inferior to the modified system.

[0069] Comparative Example 3 (Control without Nano SiO2)

[0070] Dust suppressant formulation: 25 parts catechol-modified PVA, 10 parts glycerin, 8 parts sodium humate, 2 parts surfactant, 1 part defoamer, and 50 parts water.

[0071] Preparation method:

[0072] Step S1: Heat water to 90°C, slowly add catechol-modified PVA while stirring at 1000 rpm, keep warm and stir for 1.5 hours until completely dissolved to obtain solution A.

[0073] Step S2: Cool solution A to 55°C, add glycerol and sodium humate in sequence, and stir at 500 rpm for 50 minutes to obtain mixture B.

[0074] Step S3: Cool mixture B to 40°C, add fatty alcohol polyoxyethylene ether and silicone defoamer, stir at 250 rpm for 25 minutes, let stand and age for 1.5 hours, and then discharge.

[0075] The performance of the dust suppressant solution in Comparative Example 3 was tested according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0076]

[0077] Comparative Example 3, even without the reinforcement of nano-silica, still exhibited a wind erosion rate below the standard limit, but significantly higher than that of the preferred embodiment. This indicates that the addition of nano-silica effectively improved the mechanical strength, density, and wear resistance of the film. The absence of this component resulted in a slightly weaker performance of the film in resisting continuous wind erosion and mechanical stress, confirming the synergistic enhancement effect of nanofillers on performance in the composite system.

[0078] Comparative Example 4 (Process Comparison)

[0079] Dust suppressant formula: 25 parts catechol-modified PVA, 10 parts glycerin, 8 parts sodium humate, 5 parts nano silica, 2 parts fatty alcohol polyoxyethylene ether, 1 part organosilicon defoamer, and 50 parts water.

[0080] Preparation method:

[0081] All components were stirred at room temperature of approximately 25°C and at a stirring speed of 1000 rpm for 2 hours and 45 minutes, aged for 1.5 hours, and then discharged.

[0082] The performance of the dust suppressant solution in Comparative Example 4 was tested according to the provisions of TB / T 3210 "Technical Conditions for Dust Suppression in Railway Coal Transportation" as follows:

[0083]

[0084] Comparative Example 4 employed a simplified one-step mixing process, resulting in decreased solution stability and a tendency towards flocculation and stratification. The increased wind erosion rate and thinner cured layer indicate that the non-temperature-controlled, non-step mixing method affected the full dissolution, dispersion, and interaction of the components (especially the modified PVA), leading to inferior homogeneity, stability, and film-forming properties of the final product compared to the optimized process. This demonstrates the importance of the proposed preparation method in ensuring product performance.

[0085] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. An environmentally friendly coal dust suppressant based on biomimetic adhesion technology, characterized in that, The coal dust suppressant comprises, by weight, 15-35 parts of catechol-modified polyvinyl alcohol, 5-15 parts of glycerin, 5-12 parts of sodium humate, 3-8 parts of nano silica, 1-3 parts of surfactant, 0.5-2 parts of defoamer, and 40-60 parts of water.

2. The environmentally friendly coal dust suppressant based on biomimetic adhesion technology according to claim 1, characterized in that, The preparation method of the catechol-modified polyvinyl alcohol is as follows: under inert gas protection, polyvinyl alcohol powder with an average degree of polymerization of 1700 and a degree of alcoholysis of 99% is dissolved in a mixed solvent of dimethyl sulfoxide and water, and the temperature is raised to 80°C; then 10%-30% of 3,4-dihydroxybenzoic acid by mass of PVA and a catalytic amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added, and the reaction is carried out at 80°C for 6-12 hours; after the reaction is completed, the solution is cooled to room temperature, precipitated in excess ethanol, the obtained solid is washed three times with ethanol, and dried under vacuum to constant weight to obtain catechol-modified polyvinyl alcohol.

3. The environmentally friendly coal dust suppressant based on biomimetic adhesion technology according to claim 1, characterized in that, The surfactant is one or more of sodium dodecyl sulfate, alkyl glycoside, or fatty alcohol polyoxyethylene ether.

4. The environmentally friendly coal dust suppressant based on biomimetic adhesion technology according to claim 1, characterized in that, The defoamer is one or more of organosilicon defoamers or polyether-modified silicone oils.

5. A method for preparing an environmentally friendly coal dust suppressant based on biomimetic adhesion technology as described in any one of claims 1-4, characterized in that, Includes the following steps: Step S1: Heat deionized water to 85-95℃, slowly add catechol-modified polyvinyl alcohol under high-speed stirring, keep warm and stir for 1-2 hours until completely dissolved, to obtain transparent viscous liquid A; Step S2: Cool solution A to 50-60℃, add glycerol, sodium humate and nano silica in sequence, and keep stirring for 40-60 minutes to obtain a homogeneous mixture B; Step S3: Continue to cool mixture B to 35-45℃, add surfactant and defoamer, stir at low speed for 20-30 minutes, and let stand for aging for 1-2 hours to obtain the final dust suppressant product.

6. The preparation method according to claim 5, characterized in that, The high-speed stirring speed in step S1 is 800-1200 rpm.

7. The preparation method according to claim 5, characterized in that, The stirring speed in step S2 is 400-600 rpm.

8. The preparation method according to claim 5, characterized in that, The low-speed stirring speed in step S3 is 200-300 rpm.

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