Efficient anti-freezing and anti-corrosion snow-melting agent for roads and preparation method thereof

Abstract

The invention provides an efficient anti-freezing and anti-corrosion snow-melting agent for roads and a preparation method of the snow-melting agent. The snow-melting agent comprises 10-20% of an anti-freezing agent, an anti-corrosion additive and the balance of water, the anti-corrosion additive is prepared from 0.1 to 1 percent of sodium citrate, 0.1 to 1 percent of benzotriazole, 0.1 to 1 percent of sodium tripolyphosphate, 0.1 to 1 percent of sodium gluconate, 0.1 to 1 percent of tannic acid, 0.1 to 1 percent of polyvinylpyrrolidone and 0.1 to 1 percent of 2-hydroxyphosphonoacetic acid. The preparation method comprises the following steps: preparing an anti-freezing agent solution, preparing mother liquor containing the anti-freezing and anti-corrosion additive, and finally adding the eucalyptol and the triethanolamine oleate into the mother liquor containing the anti-freezing and anti-corrosion additive to obtain the snow melting agent. According to the snow-melting agent, a precipitation film-adsorption film composite protective layer is constructed, and meanwhile, the organic corrosion inhibitor and the inorganic corrosion inhibitor are compounded, so that all the components have a synergistic effect, and the corrosion resistance of the snow-melting agent is improved.

Description

Technical Field

[0001] The present application relates to the technical field of snow-melting agents, and in particular to a highly efficient road antifreeze and anti-corrosion snow-melting agent and a preparation method thereof. Background Art

[0002] Snow melting agents are chemicals that act on the freezing point of snow and ice to lower the melting temperature of ice and snow, making the ice and snow melt faster, thereby ensuring smooth and safe traffic.

[0003] Snow melting agents are often used in winter snow and ice road maintenance. Snow melting agents include chloride salt snow melting agents, organic snow melting agents, and environmentally friendly snow melting agents. Chloride salt snow melting agents (such as sodium chloride, calcium chloride, and magnesium chloride) are widely used due to their low cost and high snow melting efficiency. However, the chloride ions (Cl - ) will significantly accelerate the corrosion of road facilities, especially for metals and alloys such as steel, aluminum, and copper, causing oxygen absorption corrosion (neutral environment) and hydrogen evolution corrosion (acidic micro-areas), leading to serious damage to infrastructure such as bridges and vehicle chassis. According to statistics, about 20% of the economic losses caused by metal corrosion are directly related to deicing agents. Therefore, the development of efficient anti-corrosion additives has become a key demand for upgrading deicing agent technology.

[0004] Traditional anti-corrosion solutions often add a single corrosion inhibitor, such as chromate, nitrite and other anodic corrosion inhibitors. However, such substances have environmental risks. 6 +) and nitrite are highly toxic and carcinogenic, and have been strictly restricted by EU RoHS (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) and other regulations. Moreover, a single corrosion inhibitor is difficult to take into account the protection needs of multiple metals. For example, chromate has a poor corrosion inhibition effect on copper, while benzotriazole is not as effective as copper in inhibiting the corrosion of steel. In addition, the use environment of de-icing agents is complex, involving harsh conditions such as alternating dry and wet, low-temperature freeze-thaw, and Cl⁻ enrichment. A single corrosion inhibition film is prone to local damage, causing accelerated corrosion of small anode-large cathode (such as pitting corrosion).

[0005] The existing compounding technology still has problems such as insufficient corrosion inhibition efficiency, unclear synergistic mechanism, and contradiction between environmental protection and cost. Therefore, in the application process of snow melting agent, it is a technical problem to develop a low-cost and highly effective anti-corrosion additive to achieve long-term protection of road facilities and ensure environmental friendliness. Summary of the invention

[0006] The present application provides a road high-efficiency antifreeze and anti-corrosion snow-melting agent and a preparation method thereof, in order to solve the above-mentioned problems mentioned in the background technology.

[0007] On the one hand, the present application provides a road high-efficiency antifreeze and anti-corrosion snow-melting agent, which comprises, by weight percentage: Antifreeze: 10 - 20%, corrosion inhibitor additive, the balance is water; The corrosion inhibitor additive includes 0.1 - 1% sodium citrate, 0.1 - 1% benzotriazole, 0.1 - 1% sodium tripolyphosphate, 0.1 - 1% sodium gluconate, 0.1 - 1% tannic acid, 0.1 - 1% polyvinylpyrrolidone, and 0.1 - 1% 2 - hydroxyphosphonoacetic acid.

[0008] Optionally, the antifreeze is composed of calcium chloride, magnesium chloride, and sodium acetate mixed in a mass ratio of 5:4:1.

[0009] Optionally, the corrosion inhibitor additive includes 0.1 - 0.8% sodium citrate, 0.1 - 0.8% benzotriazole, 0.1 - 0.8% sodium tripolyphosphate, 0.1 - 0.8% sodium gluconate, 0.1 - 0.8% tannic acid, 0.1 - 0.8% polyvinylpyrrolidone, and 0.1 - 0.8% 2 - hydroxyphosphonoacetic acid.

[0010] Optionally, the corrosion inhibitor additive includes 0.2 - 0.6% sodium citrate, 0.2 - 0.6% benzotriazole, 0.2 - 0.6% sodium tripolyphosphate, 0.2 - 0.6% sodium gluconate, 0.2 - 0.6% tannic acid, 0.2 - 0.6% polyvinylpyrrolidone, and 0.2 - 0.6% 2 - hydroxyphosphonoacetic acid.

[0011] Optionally, the corrosion inhibitor additive includes 0.4 - 0.55% sodium citrate, 0.4 - 0.6% benzotriazole, 0.4 - 0.6% sodium tripolyphosphate, 0.4 - 0.5% sodium gluconate, 0.4 - 0.5% tannic acid, 0.4 - 0.6% polyvinylpyrrolidone, and 0.4 - 0.5% 2 - hydroxyphosphonoacetic acid.

[0012] Optionally, by weight percentage, 0.02 - 0.1% of an auxiliary agent is added to the snow - melting agent, and the auxiliary agent includes eudesmin and triethanolamine oleate.

[0013] Optionally, the mass ratio of eudesmin to triethanolamine oleate is 1:2 - 3.5.

[0014] On the other hand, the present application provides a preparation method for a highly efficient road anti - freeze and anti - corrosion snow - melting agent, which is used to prepare the above - mentioned snow - melting agent. The preparation method includes the following steps: (1) By weight parts, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water, and first - stage stirring and mixing are carried out to obtain an antifreeze solution; (2) By weight parts, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone, and 2 - hydroxyphosphonoacetic acid are added to the antifreeze solution, and second - stage stirring and mixing are carried out to obtain a mother liquor containing anti - freeze and anti - corrosion additives; (3) By weight, add pinoresinol and triethanolamine oleate to the mother liquor containing anti-freezing and anti-corrosion additives, and conduct the third stirring and mixing to obtain a snow melting agent.

[0015] Optionally, before the third stirring and mixing, heat the mother liquor containing anti-freezing and anti-corrosion additives to 25 - 50 °C, and then add pinoresinol and triethanolamine oleate to the heated mother liquor containing anti-freezing and anti-corrosion additives.

[0016] Optionally, the rotation speeds of the first stirring and mixing, the second stirring and mixing, and the third stirring and mixing are 200 - 600 rpm, and the time is 0.5 - 1 h.

[0017] The road highly efficient anti-freezing and anti-corrosion snow melting agent and its preparation method provided by this application achieve the preparation of the snow melting agent. Compared with the prior art, it has the following beneficial effects: (1) In this application, by adding anti-freezing agents, the freezing point of ice and snow can be reduced, enabling the ice and snow to melt at lower temperatures and avoiding road icing, thereby ensuring the traffic capacity of the road. The anti-corrosion additives can significantly reduce the corrosion of road surfaces, green plants, reinforced concrete and other infrastructure, thus extending their service life. In this application, by optimizing the component ratio, a "precipitation film - adsorption film" composite protective layer is constructed, breaking through the limitations of traditional phosphorus pollution, acidic residues and single corrosion inhibition mechanisms. The precipitation film formed by sodium tripolyphosphate / 2-hydroxyphosphonoacetic acid / benzotriazole / tannic acid covers the metal surface, physically blocking the corrosion medium; at the same time, the adsorption film formed by sodium citrate / sodium gluconate / polyvinylpyrrolidone long-term inhibits electrochemical corrosion, forming a multi-dimensional protection system. At the same time, the compounding of organic corrosion inhibitors and inorganic corrosion inhibitors exhibits characteristics such as synergistic effect, expanded application range, improved economic benefits, and reduced environmental impact. And a comprehensive performance breakthrough of low-dose anti-corrosion additives, high corrosion inhibition rate and environmental friendliness is achieved.

[0018] (2) By adding pinoresinol and triethanolamine oleate in this application, the anti-corrosion performance of the snow melting agent is improved. The nitrogen atom in triethanolamine oleate can be adsorbed on the metal surface prior to chloride ions, forming a composite film with the "precipitation film - adsorption film" formed by the anti-corrosion additives, greatly reducing the corrosion of chloride ions on the metal surface. Pinoresinol is dispersed in the snow melting agent, and the intermolecular forces (such as hydrogen bonds and electrostatic interactions) between pinoresinol and chloride ions can further prevent the electrochemical corrosion of chloride ions on the metal surface.

[0019] At the same time, pinoresinol has an inhibitory effect on bacteria and fungi. By adding pinoresinol, it can play an antibacterial role in the snow melting agent during storage and transportation, preventing the formation of biofilms in the snow melting agent and deterioration, and is conducive to the snow melting agent maintaining excellent snow melting performance.

[0020] (3) While melting snow (ice) and removing snow, the present application can avoid the detachment of the composite film, prevent the corrosion of metal facilities such as road surfaces and vehicles during the snow-melting process, and during the process from snow melting to the road surface drying, the composite film can continuously protect the metal surface, avoid the corrosion of road facilities, extend the service life of the road surface, and reduce the maintenance cost of the road surface at the same time.

[0021] (4) The snow-melting agent provided by the present application has good corrosion inhibition performance and snow-melting and ice-melting ability, and can be applied not only to the de-icing and snow-removing of ordinary roads, bridges, highways, and tunnels in cold regions, but also to the snow melting and de-icing of public facilities such as airports, docks, and parking lots. Specific Embodiments

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts also belong to the scope of protection of the present application.

[0023] On the one hand, the present application provides a road efficient anti-freezing and anti-corrosion snow-melting agent, which includes by weight percentage: Anti-freezing agent 10 - 20%, anti-corrosion additive, and the balance is water; The anti-corrosion additive includes 0.1 - 1% sodium citrate, 0.1 - 1% benzotriazole, 0.1 - 1% sodium tripolyphosphate, 0.1 - 1% sodium gluconate, 0.1 - 1% tannic acid, 0.1 - 1% polyvinylpyrrolidone, and 0.1 - 1% 2-hydroxyphosphonoacetic acid.

[0024] Specifically, in the present application, by adding an anti-freezing agent, the freezing point of ice and snow can be reduced, so that the ice and snow can melt at a lower temperature, avoiding the icing of the road, and thus ensuring the traffic capacity of the road. The anti-corrosion additive can significantly reduce the corrosion of infrastructure such as road surfaces, green plants, and reinforced concrete, thereby extending their service life. Using water as a solvent enables the anti-freezing agent and anti-corrosion additive to dissolve in water, improving the fluidity of the snow-melting agent, and then facilitating the uniform spreading of the snow-melting agent on the road surface, quickly melting the snow and ice layers, improving the snow-melting efficiency of the snow-melting agent, and ensuring smooth traffic.

[0025] Sodium citrate can lower the freezing point, prevent icing, and has little corrosion, while it can form complexes with calcium, magnesium and other ions in water, thereby preventing these ions from crystallizing at low temperatures and further preventing the solution from freezing. And sodium citrate has little corrosion to the environment and will not cause corrosion damage to roads, vehicles and plants. Therefore, it is a more environmentally friendly corrosion inhibitor component. The lone pair electrons on the N atom in benzotriazole can form a coordination bond with the empty d orbital of Fe and adsorb on the reactive sites on the surface of carbon steel, forming an adsorption film on the metal surface, avoiding the intrusion of other corrosion components, and further avoiding the corrosion of the road surface metal by the snow melting agent. At the same time, sodium citrate-benzotriazole forms a chelating system, and through the π-π stacking effect of the carboxylic acid group and the azole ring, the self-repairing ability of the corrosion inhibition film is significantly improved. In the sodium citrate-benzotriazole chelating system, the mass ratio of sodium citrate to benzotriazole is 8-12:1.

[0026] The corrosion inhibition effect of sodium gluconate is mainly manifested in its complexing ability with metals and its stabilizing effect on corrosion media. It can form stable complexes with metal ions, thereby reducing the corrosion rate of metals. At the same time, sodium gluconate can also stabilize harmful ions in the corrosion medium and reduce their corrosion effect on metals. Sodium tripolyphosphate forms stable complexes with metal ions and forms a precipitation film on the metal surface to prevent the metal from reacting adversely with other chemical components, thereby protecting the road surface from corrosion. Sodium tripolyphosphate also has solubilizing and dispersing properties, which can increase the solubility of insoluble substances in water, thereby improving the dissolution efficiency of the snow melting agent, enabling the snow melting agent to melt ice and snow faster, and reducing the impact of snow accumulation on traffic. Tannic acid can combine with the water in ice and snow to form a eutectic mixture, thereby lowering the freezing point and enabling the ice and snow to melt at a lower temperature. Polyvinylpyrrolidone can absorb the water in the snow melting agent to prevent icing, further enhancing its anti-freezing effect. At the same time, it also has good film-forming and complexing properties. When attached to the metal surface, it can form a long-lasting adsorption film on the metal surface and synergistically inhibit the occurrence of electrochemical corrosion with sodium citrate-benzotriazole. In this application, by optimizing the component ratio, a "precipitation film-adsorption film" composite protective layer is constructed, breaking through the limitations of the traditional single corrosion inhibition mechanism. The precipitation film formed by sodium tripolyphosphate / 2-hydroxyphosphonoacetic acid / benzotriazole / tannic acid covers the metal surface, physically blocking the corrosion medium; at the same time, the adsorption film formed by sodium citrate / sodium gluconate / polyvinylpyrrolidone can inhibit electrochemical corrosion for a long time, forming a multi-dimensional protection system. At the same time, the compounding of organic corrosion inhibitors and inorganic corrosion inhibitors shows characteristics such as synergistic effect, expanded application range, improved economic benefits, and reduced environmental impact. Optionally, the antifreeze is composed of calcium chloride, magnesium chloride and sodium acetate mixed in a mass ratio of 5:4:1.

[0027] Specifically, after calcium chloride and magnesium chloride are dissolved in water, they will significantly lower the freezing point of water, enabling it to have strong snow melting ability at low temperatures. Magnesium chloride has less negative impact on the environment and is suitable for environments where vegetation needs to be protected. Sodium acetate is an organic snow melting agent with excellent snow melting effect and extremely low corrosiveness to the environment. In this application, the antifreeze agent is a compound of calcium chloride, magnesium chloride, and sodium acetate in a special ratio, ensuring the snow melting performance of the snow melting agent while significantly reducing the corrosion rate of the metal by the multi-component synergistic effect.

[0028] Optionally, the corrosion prevention additive includes 0.1 - 0.8% sodium citrate, 0.1 - 0.8% benzotriazole, 0.1 - 0.8% sodium tripolyphosphate, 0.1 - 0.8% sodium gluconate, 0.1 - 0.8% tannic acid, 0.1 - 0.8% polyvinylpyrrolidone, and 0.1 - 0.8% 2-hydroxyphosphonoacetic acid.

[0029] Optionally, the corrosion prevention additive includes 0.2 - 0.6% sodium citrate, 0.2 - 0.6% benzotriazole, 0.2 - 0.6% sodium tripolyphosphate, 0.2 - 0.6% sodium gluconate, 0.2 - 0.6% tannic acid, 0.2 - 0.6% polyvinylpyrrolidone, and 0.2 - 0.6% 2-hydroxyphosphonoacetic acid.

[0030] Optionally, the corrosion prevention additive includes 0.4 - 0.55% sodium citrate, 0.4 - 0.6% benzotriazole, 0.4 - 0.6% sodium tripolyphosphate, 0.4 - 0.5% sodium gluconate, 0.4 - 0.5% tannic acid, 0.4 - 0.6% polyvinylpyrrolidone, and 0.4 - 0.5% 2-hydroxyphosphonoacetic acid.

[0031] Optionally, by weight percentage, 0.02 - 0.1% of an auxiliary agent is also added to the snow melting agent, and the auxiliary agent includes eudesmin and triethanolamine oleate.

[0032] Optionally, the mass ratio of eudesmin to triethanolamine oleate is 1:2 - 3.5.

[0033] Specifically, the nitrogen atom in triethanolamine oleate can be adsorbed on the metal surface better than chloride ions, forming a composite film with the "precipitation film - adsorption film" formed by the corrosion inhibitor additive, greatly reducing the corrosion of chloride ions on the metal surface. At the same time, the aromatic ring with large π bonds contained in triethanolamine oleate can enhance the strength and rigidity of the composite film, avoiding the detachment of the composite film while melting snow (ice) and removing snow. It not only avoids the corrosion of metal facilities such as roads and vehicles during the snow - melting process, but also during the process from snow - melting to the road surface drying, the composite film can continuously protect the metal surface, avoid the corrosion of road facilities, extend the service life of the road surface, and reduce the maintenance cost of the road surface. Eudesmin is dispersed in the snow - melting agent, and the intermolecular forces (such as hydrogen bonds and electrostatic interactions) between eudesmin and chloride ions can further avoid the electrochemical corrosion of chloride ions on the metal surface, thereby improving the anti - corrosion performance of the snow - melting agent.

[0034] On the other hand, the present application provides a preparation method of a highly efficient anti - freezing and anti - corrosion snow - melting agent for roads. This method is used to prepare the above - mentioned snow - melting agent, and the preparation method includes the following steps: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water and subjected to the first stirring and mixing to obtain an antifreeze solution; (2) By weight, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone, and 2 - hydroxyphosphonoacetic acid are added to the antifreeze solution and subjected to the second stirring and mixing to obtain a mother liquor containing anti - freezing and anti - corrosion additives; (3) By weight, eudesmin and triethanolamine oleate are added to the mother liquor containing anti - freezing and anti - corrosion additives and subjected to the third stirring and mixing to obtain a snow - melting agent.

[0035] Specifically, through the above - mentioned scheme of the present application, the preparation of the snow - melting agent is realized. By first sequentially adding the components (calcium chloride, magnesium chloride, sodium acetate) in the antifreeze to water and performing the first stirring and mixing, calcium chloride, magnesium chloride, and sodium acetate are dissolved in water to obtain an antifreeze solution. Then, the components in the corrosion inhibitor additive are added to the antifreeze solution and subjected to the second stirring and mixing to obtain a mother liquor containing anti - freezing and anti - corrosion additives. Finally, eudesmin and triethanolamine oleate are added to the mother liquor containing anti - freezing and anti - corrosion additives and subjected to the third stirring and mixing to obtain a snow - melting agent. Stirring and dissolving in batches enables the components in the snow - melting agent to be better dissolved (or dispersed) in water, improving the dispersion uniformity of the components in the snow - melting agent, and thus improving the snow - melting effect when the snow - melting agent is spread on the road surface.

[0036] Optionally, before the third stirring and mixing, the mother liquor containing anti - freezing and anti - corrosion additives is heated to 25 - 50 °C, and then eudesmin and triethanolamine oleate are added to the heated mother liquor containing anti - freezing and anti - corrosion additives.

[0037] Specifically, after heating the mother liquor containing the anti-freezing and anti-corrosion additives, piperonal and triethanolamine oleate are added, and the third stirring and mixing is carried out to obtain the snow melting agent, so that piperonal and triethanolamine oleate can be better dispersed in the snow melting agent. At the same time, increasing the temperature helps to form the sodium citrate-benzotriazole chelating system, thereby improving the snow melting ability of the snow melting agent.

[0038] Optionally, the rotation speeds of the first stirring and mixing, the second stirring and mixing, and the third stirring and mixing are 200-600 rpm, and the time is 0.5-1 h. In the sodium citrate-benzotriazole chelating system, the mass ratio of sodium citrate to benzotriazole is 8-12:1.

[0039] The technical solution of the present application will be described in detail below with specific examples.

[0040] Example 1 A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and the first stirring and mixing is carried out to obtain an anti-freezing agent solution; (2) Sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone, and 2-hydroxyphosphonoacetic acid are added to the anti-freezing agent solution, and the second stirring and mixing is carried out to obtain a snow melting agent.

[0041] Among them, by weight percentage, it includes: Anti-freezing agent 10%, anti-corrosion additive, and the balance is water; The anti-corrosion additive includes: 0.1% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 8:1), 0.1% sodium tripolyphosphate, 0.1% sodium gluconate, 0.1% tannic acid, 0.1% polyvinylpyrrolidone, and 0.1% 2-hydroxyphosphonoacetic acid.

[0042] Example 2 A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and the first stirring and mixing is carried out to obtain an anti-freezing agent solution; (2) By weight, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone, and 2-hydroxyphosphonoacetic acid are added to the anti-freezing agent solution, and the second stirring and mixing is carried out to obtain a snow melting agent.

[0043] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosion additive, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone and 0.45% 2-hydroxyphosphonoacetic acid.

[0044] Example 3 A preparation method of a highly efficient road anti-freezing and anti-corrosion snow melting agent includes the following steps: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water at a mass ratio of 5:4:1, and first stirring and mixing are carried out to obtain an anti-freezing agent solution; (2) By weight, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added to the anti-freezing agent solution, and second stirring and mixing are carried out to obtain a snow melting agent.

[0045] Among them, by weight percentage, it includes: 20% anti-freezing agent, anti-corrosion additive, and the balance is water; The anti-corrosion additive includes: 1% sodium citrate-benzotriazole chelating system (mass ratio of sodium citrate to benzotriazole is 12:1), 1% sodium tripolyphosphate, 1% sodium gluconate, 1% tannic acid, 1% polyvinylpyrrolidone and 1% 2-hydroxyphosphonoacetic acid.

[0046] Comparative Example 1 A preparation method of a highly efficient road anti-freezing and anti-corrosion snow melting agent includes the following steps: The difference from Example 2 is: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water at a mass ratio of 5:4:1, and first stirring and mixing are carried out to obtain an anti-freezing agent solution; Among them, by weight percentage, it includes: 10% anti-freezing agent, 0% anti-corrosion additive, and the balance is water.

[0047] Comparative Example 2 A preparation method of a highly efficient road anti-freezing and anti-corrosion snow melting agent includes the following steps: The difference from Example 2 is: (1) By weight, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water at a mass ratio of 5:4:1, and first stirring and mixing are carried out to obtain an anti-freezing agent solution; (2) By weight, sodium citrate, benzotriazole, sodium tripolyphosphate, tannic acid, and 2-hydroxyphosphonoacetic acid are added to the anti-freezing agent solution, and second stirring and mixing are carried out to obtain a snow melting agent.

[0048] Among them, by weight percentage, it includes: Antifreeze 15%, corrosion prevention additive, and the balance is water; The corrosion prevention additive includes: 0.5% sodium citrate - benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.5% tannic acid, and 0.5% 2 - hydroxyphosphonoacetic acid.

[0049] Comparative Example 3 A preparation method of a highly efficient anti - freezing, anti - corrosion and snow - melting agent for roads, comprising the following steps: The difference from Example 2 is as follows: (1) By weight parts, calcium chloride, magnesium chloride, and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and first stirred and mixed to obtain an antifreeze solution; (2) By weight parts, sodium citrate, benzotriazole, sodium gluconate, and polyvinylpyrrolidone are added to the antifreeze solution, and second stirred and mixed to obtain a snow - melting agent.

[0050] Among them, by weight percentage, it includes: Antifreeze 15%, corrosion prevention additive, and the balance is water; The corrosion prevention additive includes 0.5% sodium citrate - benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium gluconate, and 0.5% polyvinylpyrrolidone.

[0051] Experimental Example 1 Testing of the anti - corrosion performance of the snow - melting agent Specific experimental method: At room temperature, using a No. 20 carbon steel test piece with dimensions of 50mm×25mm×2mm, it is rinsed with anhydrous ethanol, dried to constant weight and then weighed, accurate to 0.1mg. Prepare a snow - melting agent solution with a mass percentage concentration of 10wt% of the snow - melting agents provided in Examples 1 - 3 and Comparative Examples 1 - 3. The carbon steel test pieces are respectively suspended in the solutions of Examples 1 - 3 and Comparative Examples 1 - 3 so that they are immersed at the same height (occupying 3 / 4 of the whole test piece), and continuously left standing for 7 days. After the test, the surface corrosion products are removed, and the test pieces are cleaned, dried and then weighed to obtain the mass loss of each test piece. According to the formula in Standard GB / T 18175 - 2014, its corrosion rate and corrosion inhibition rate are calculated. Each test is carried out at least three parallel tests and the average value is taken, and the results are shown in Table 1.

[0052] Table 1 <![CDATA[Corrosion rate / (mm·a -1 )]]> Corrosion inhibition rate / % Example 1 0.0187 90.71 Example 2 0.0212 89.47 Example 3 0.0244 87.88 Comparative Example 1 0.2014 - Comparative Example 2 0.0401 80.01 Comparative Example 3 0.0413 79.50 Experimental Example 2 Detection of snow - melting and ice - melting ability The snow melting and ice melting capabilities of the snow melting agents obtained in Examples 1 - 3 and Comparative Examples 1 - 3 were detected.

[0053] According to the methods and steps specified in the determination of the snow melting and ice melting capabilities of type II snow melting agents in the national standard GB / T 23851 - 2017 "Snow Melting Agents", the snow melting and ice melting capabilities of the snow melting agents provided in Examples 1 - 3 and Comparative Examples 1 - 3 were tested. Each test was carried out at least three parallel tests, and the average value was taken, and the results are shown in Table 2.

[0054] Table 2 Snow melting and ice melting ability % Example 1 150 Example 2 164 Example 3 159 Comparative Example 1 100 Comparative Example 2 112 Comparative Example 3 116 Observing Table 1 and Table 2, the corrosion inhibition performance of the snow melting agents provided in Examples 1 - 3 of the present application is significantly improved compared with that of Comparative Examples 1 - 3. Comparing Examples 1 - 3 with Comparative Example 1, no anti - corrosion additive was added in Comparative Example 1. Therefore, it shows that the addition of the anti - corrosion additive can significantly improve the anti - corrosion performance of the snow melting agent. By optimizing the component ratio of the anti - corrosion additive, a "precipitation film - adsorption film" composite protection layer was constructed, breaking through the limitations of the traditional single corrosion inhibition mechanism. The precipitation film formed by sodium tripolyphosphate / 2 - hydroxyphosphonoacetic acid / benzotriazole / tannic acid covers the metal surface, physically blocking the corrosive medium; at the same time, the adsorption film formed by sodium citrate / sodium gluconate / polyvinylpyrrolidone inhibits electrochemical corrosion for a long time, forming a multi - dimensional protection system. At the same time, the compounding of organic corrosion inhibitors and inorganic corrosion inhibitors shows characteristics such as synergistic effect, expanded application range, improved economic benefits, and reduced environmental impact.

[0055] Comparing Examples 1 - 3 with Comparative Examples 2 and 3, the main components of the anti - corrosion additive in Comparative Example 2 are sodium citrate, benzotriazole, sodium tripolyphosphate, tannic acid, and 2 - hydroxyphosphonoacetic acid that can form a precipitation film, while the main components of the anti - corrosion additive in Comparative Example 3 are sodium citrate / sodium gluconate / polyvinylpyrrolidone that can form an adsorption film. It shows that although forming a single precipitation film or adsorption film can achieve a corrosion inhibition effect, compared with the construction of the "precipitation film - adsorption film" composite protection layer, when the "precipitation film - adsorption film" exists simultaneously, the anti - corrosion performance of the snow melting agent reaches the best. At the same time, the test results of the snow melting and ice melting capabilities show that the relative snow melting and ice melting capabilities of the snow melting agent provided in the present application can meet or even far exceed the index requirement of the relative snow melting and ice melting capability ≥ 90% specified in GB / T 23851 - 2017 "Snow Melting Agents".

[0056] Example 4 The difference from Example 2 is as follows: A preparation method of a highly efficient road anti - freezing and anti - corrosion snow melting agent, comprising the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosion additives to 25°C, and then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additives, and perform the third stirring and mixing to obtain the snow melting agent.

[0057] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosion additive, auxiliary agent 0.02%, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone and 0.45% of 2-hydroxyphosphonoacetic acid.

[0058] The auxiliary agent includes eudesmin and triethanolamine oleate with a mass ratio of 1:2.

[0059] Example 5 The difference from Example 2 is that: A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosion additives to 35°C, and then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additives, and perform the third stirring and mixing to obtain the snow melting agent.

[0060] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosion additive, auxiliary agent 0.07%, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone and 0.45% of 2-hydroxyphosphonoacetic acid.

[0061] The auxiliary agent includes eudesmin and triethanolamine oleate with a mass ratio of 1:2.5.

[0062] Example 6 The difference from Example 2 is that: A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosion additives to 50°C, and then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additives, and perform the third stirring and mixing to obtain the snow melting agent.

[0063] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosion additive, auxiliary agent 0.1%, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone, and 0.45% 2-hydroxyphosphonoacetic acid.

[0064] The auxiliary agent includes eudesmin and triethanolamine oleate with a mass ratio of 1:3.5.

[0065] Comparative Example 4 The difference from Example 5 is as follows: A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosion additive to 35°C, then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additive, and conduct the third stirring and mixing to obtain the snow melting agent.

[0066] Among them, by weight percentage, it includes: 15% anti-freezing agent, anti-corrosion additive, 0.11% auxiliary agent, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone, and 0.45% 2-hydroxyphosphonoacetic acid.

[0067] The auxiliary agent includes eudesmin and triethanolamine oleate with a mass ratio of 1:2.5.

[0068] Comparative Example 5 The difference from Example 5 is as follows: A preparation method of a highly efficient anti-freezing and anti-corrosion snow melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosion additive to 35°C, then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additive, and conduct the third stirring and mixing to obtain the snow melting agent.

[0069] Among them, by weight percentage, it includes: 15% anti-freezing agent, anti-corrosion additive, 0.009% auxiliary agent, and the balance is water; The anti-corrosion additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone, and 0.45% 2-hydroxyphosphonoacetic acid.

[0070] The auxiliary agent includes eudesmin and triethanolamine oleate with a mass ratio of 1:2.5.

[0071] Comparative Example 6 The difference from Example 5 is that: A preparation method of a highly efficient anti-freezing, anti-corrosive and snow-melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosive additive to 35 °C, then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosive additive, and carry out the third stirring and mixing to obtain the snow-melting agent.

[0072] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosive additive, auxiliary agent 0.07%, and the balance is water; The anti-corrosive additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone and 0.45% 2-hydroxyphosphonoacetic acid.

[0073] The auxiliary agent is selected from eudesmin.

[0074] Comparative Example 7 The difference from Example 5 is that: A preparation method of a highly efficient anti-freezing, anti-corrosive and snow-melting agent for roads includes the following steps: (3) Heat the mother liquor containing the anti-freezing and anti-corrosive additive to 35 °C, then add eudesmin and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosive additive, and carry out the third stirring and mixing to obtain the snow-melting agent.

[0075] Among them, by weight percentage, it includes: Anti-freezing agent 15%, anti-corrosive additive, auxiliary agent 0.07%, and the balance is water; The anti-corrosive additive includes 0.5% sodium citrate-benzotriazole chelating system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% sodium tripolyphosphate, 0.4% sodium gluconate, 0.5% tannic acid, 0.5% polyvinylpyrrolidone and 0.45% 2-hydroxyphosphonoacetic acid.

[0076] The auxiliary agent is selected from triethanolamine oleate.

[0077] Experimental Example 3 Testing of the anti-corrosion performance of the snow-melting agent Using the same method as in Experimental Example 1, the corrosion rates and inhibition rates of the snow-melting agents obtained in Examples 4 - 6 and Comparative Examples 4 - 7 were detected. Each test was carried out at least three parallel tests, and the average value was taken to obtain the results shown in Table 3.

[0078] Table 3 <![CDATA[Corrosion rate / (mm·a -1 )]]> Corrosion inhibition rate / % Example 4 0.0050 97.52 Example 5 0.0046 97.72 Example 6 0.0047 97.67 Comparative Example 4 0.0244 87.88 Comparative Example 5 0.0263 86.94 Comparative Example 6 0.0169 91.61 Comparative Example 7 0.0154 92.35 Experimental Example 4 Detection of snow melting and ice melting ability Using the same method as in Experimental Example 2, the snow melting and ice melting abilities of the snow melting agents obtained in Examples 4 - 6 and Comparative Examples 4 - 7 were detected.

[0079] Each test was carried out at least three parallel tests, and the average value was taken, and the results are shown in Table 4.

[0080] Table 4 Snow melting and ice melting ability % Example 4 286 Example 5 279 Example 6 278 Comparative Example 4 136 Comparative Example 5 147 Comparative Example 6 146 Comparative Example 7 142 Observing Table 3 and Table 4, it is found that the snow melting agents provided in Examples 4 - 6 of the present application have excellent corrosion inhibition performance and snow melting and ice melting ability. Comparing Examples 4 - 6 and Comparative Examples 4 and 5, it is found that after adding 0.02 - 0.1% of the additives, the additives include eudesmin and triethanolamine oleate, the anti - corrosion performance and snow melting and ice melting ability of the snow melting agent are significantly improved. Comparing Comparative Examples 6 and 7, it is found that when adding eudesmin or triethanolamine oleate alone, the improvement amplitude of the corrosion inhibition performance and snow melting and ice melting ability of the snow melting agent is small, indicating that the nitrogen atom in triethanolamine oleate can be adsorbed on the metal surface better than chloride ions, and forms a composite film with the "precipitation film - adsorption film" formed by the anti - corrosion additive, which can greatly reduce the corrosion of chloride ions on the metal surface. The intermolecular force (such as hydrogen bond, electrostatic interaction) between eudesmin and chloride ions can further avoid the electrochemical corrosion of chloride ions on the metal surface, extend the service life of the road surface, and at the same time reduce the maintenance cost of the road surface.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An efficient road anti-freezing and anti-corrosion snow melter, characterized in that, Comprising by weight percentage: Antifreeze 10 - 20%, corrosion - prevention additive, and the balance is water; The corrosion - prevention additive includes 0.1 - 1% sodium citrate, 0.1 - 1% benzotriazole, 0.1 - 1% sodium tripolyphosphate, 0.1 - 1% sodium gluconate, 0.1 - 1% tannic acid, 0.1 - 1% polyvinylpyrrolidone, and 0.1 - 1% 2 - hydroxyphosphonoacetic acid.

2. The high-efficiency anti-freezing and anti-corrosive snow melting agent for roads according to claim 1, wherein The antifreeze is composed of calcium chloride, magnesium chloride, and sodium acetate mixed in a mass ratio of 5:4:

1.

3. The high-efficiency anti-freezing and anti-corrosion snow melting agent for roads according to claim 1, wherein The corrosion - prevention additive includes 0.1 - 0.8% sodium citrate, 0.1 - 0.8% benzotriazole, 0.1 - 0.8% sodium tripolyphosphate, 0.1 - 0.8% sodium gluconate, 0.1 - 0.8% tannic acid, 0.1 - 0.8% polyvinylpyrrolidone, and 0.1 - 0.8% 2 - hydroxyphosphonoacetic acid.

4. The high-efficiency anti-freezing and anti-corrosion snow melting agent for roads according to claim 1, characterized in that, The corrosion - prevention additive includes 0.2 - 0.6% sodium citrate, 0.2 - 0.6% benzotriazole, 0.2 - 0.6% sodium tripolyphosphate, 0.2 - 0.6% sodium gluconate, 0.2 - 0.6% tannic acid, 0.2 - 0.6% polyvinylpyrrolidone, and 0.2 - 0.6% 2 - hydroxyphosphonoacetic acid.

5. The high-efficiency anti-freezing and anti-corrosion snow-melting agent for roads according to claim 1, wherein The corrosion - prevention additive includes 0.4 - 0.55% sodium citrate, 0.4 - 0.6% benzotriazole, 0.4 - 0.6% sodium tripolyphosphate, 0.4 - 0.5% sodium gluconate, 0.4 - 0.5% tannic acid, 0.4 - 0.6% polyvinylpyrrolidone, and 0.4 - 0.5% 2 - hydroxyphosphonoacetic acid.

6. The highly efficient anti-freezing and anti-corrosive road snow melting agent according to claim 5, characterized in that, By weight percentage, 0.02 - 0.1% of an auxiliary agent is also added to the snow - melting agent, and the auxiliary agent includes eudesmin and triethanolamine oleate.

7. The high-efficiency road anti-freezing and anti-corrosion snow-melting agent according to claim 6, characterized in that The mass ratio of eudesmin to triethanolamine oleate is 1:2 - 3.

5.

8. A preparation method of an efficient anti-freezing and anti-corrosive snow melting agent for roads, the method being used to prepare the snow melting agent according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: (1) By weight parts, add calcium chloride, magnesium chloride, and sodium acetate to water in sequence, and conduct the first stirring and mixing to obtain an antifreeze solution; (2) By weight parts, add sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone, and 2 - hydroxyphosphonoacetic acid to the antifreeze solution, and conduct the second stirring and mixing to obtain a mother liquor containing antifreeze and corrosion - prevention additives; (3) By weight parts, add eudesmin and triethanolamine oleate to the mother liquor containing antifreeze and corrosion - prevention additives, and conduct the third stirring and mixing to obtain the snow - melting agent.

9. The preparation method of the high-efficiency anti-freezing and anti-corrosive snow melting agent for roads according to claim 8, characterized in that, Before the third stirring and mixing, heat the mother liquor containing antifreeze and corrosion - prevention additives to 25 - 50 °C, and then add eudesmin and triethanolamine oleate to the heated mother liquor containing antifreeze and corrosion - prevention additives.

10. The preparation method of the highly efficient anti-freezing and anti-corrosive snow melting agent for roads according to claim 9, characterized in that, The rotation speeds of the first stirring and mixing, the second stirring and mixing, and the third stirring and mixing are 200 - 600 rpm, and the time is 0.5 - 1 h.