Highly efficient deicing and anticorrosive snow-melting agent for roads and preparation method thereof

Abstract

The application provides a road efficient antifreeze and corrosion inhibitor snow-melting agent and a preparation method thereof. The snow-melting agent comprises 10-20% of an antifreeze agent, a corrosion inhibitor additive, and the balance of water. The corrosion inhibitor additive comprises 0.1-1% of sodium citrate, 0.1-1% of benzotriazole, 0.1-1% of sodium tripolyphosphate, 0.1-1% of sodium gluconate, 0.1-1% of tannic acid, 0.1-1% of polyvinylpyrrolidone and 0.1-1% of 2-hydroxyphosphonoacetic acid. The preparation method comprises antifreeze solution preparation, preparation of a mother liquor containing the antifreeze and corrosion inhibitor additive, and finally adding eucalyptol and triethanolamine oleate to the mother liquor containing the antifreeze and corrosion inhibitor additive to obtain the snow-melting agent. The application constructs a "precipitation film-adsorption film" composite protective layer, and simultaneously compounding organic corrosion inhibitors and inorganic corrosion inhibitors, so that the components are synergistically enhanced, 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 agent, in particular to a road efficient anti-freezing and anti-corrosion snow-melting agent and a preparation method thereof. BACKGROUND

[0002] Snow-melting agent is a chemical substance that reduces the melting temperature of ice and snow by acting on the freezing point of snow and ice. It makes ice and snow melt faster, thereby ensuring smooth and safe traffic.

[0003] In winter ice and snow road maintenance, snow-melting agent is often used. Snow-melting agent includes chlorate snow-melting agent, organic snow-melting agent and environmentally friendly snow-melting agent and many other types. Chlorate snow-melting agent (such as sodium chloride, calcium chloride and magnesium chloride) is widely used due to its low cost and high snow-melting efficiency. However, the chloride ion (Cl⁻) in such snow-melting agent can 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 area), resulting in 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 snow-melting agent. Therefore, the development of efficient anti-corrosion additives has become a key requirement for the upgrading of snow-melting agent technology.

[0004] In the traditional anti-corrosion scheme, a single corrosion inhibitor such as chromate, nitrite and other anodic corrosion inhibitors is often added. However, a single corrosion inhibitor cannot meet the protection needs of multiple metals, for example, chromate has poor corrosion inhibition effect on copper, and benzotriazole has better corrosion inhibition effect on copper than on steel. In addition, the use environment of snow-melting agent is complex, involving dry-wet alternating, low temperature freeze-thaw, Cl⁻ enrichment and other harsh conditions. The single corrosion inhibitor 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, environmental protection and cost contradiction. Therefore, in the application process of snow-melting agent, it is an urgent technical problem to be solved to develop an additive that is both low in cost and efficient in anti-corrosion, so as to realize long-term protection of road facilities and ensure environmental friendliness. SUMMARY

[0006] The present application provides a road efficient anti-freezing and anti-corrosion snow-melting agent and a preparation method thereof, to solve the above problems mentioned in the background art.

[0007] In one aspect, the present application provides a road efficient anti-freezing and anti-corrosion snow-melting agent, which comprises, by weight percentage:

[0008] 10-20% of anti-freezing agent, anti-corrosion additive, and the balance of water;

[0009] The corrosion-preventing additive comprises 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.

[0010] Optionally, the anti-freezing agent is prepared by mixing calcium chloride, magnesium chloride and sodium acetate in a mass ratio of 5:4:1.

[0011] Optionally, the corrosion-preventing additive comprises 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.

[0012] Optionally, the corrosion-preventing additive comprises 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.

[0013] Optionally, the corrosion-preventing additive comprises 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.

[0014] Optionally, the snow-melting agent further comprises 0.02-0.1% auxiliary agent in terms of weight percentage, and the auxiliary agent comprises eucalyptol and triethanolamine oleate.

[0015] Optionally, the mass ratio of eucalyptol to triethanolamine oleate is 1:2-3.5.

[0016] In another aspect, the application provides a preparation method of the road efficient anti-freezing and corrosion-preventing snow-melting agent, which is used for preparing the snow-melting agent and comprises the following steps:

[0017] (1) calcium chloride, magnesium chloride and sodium acetate are sequentially added into water in terms of weight parts, and first stirring and mixing is performed to obtain an anti-freezing agent solution;

[0018] (2) sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added into the anti-freezing agent solution in terms of weight parts, and second stirring and mixing is performed to obtain a mother liquor containing anti-freezing and corrosion-preventing additive;

[0019] (3) According to weight parts, eucalyptol and triethanolamine oleate are added to the mother liquor containing the anti-freezing and anti-corrosion additives to perform third stirring and mixing to obtain the snow-melting agent.

[0020] Optionally, before the third stirring and mixing, the mother liquor containing the anti-freezing and anti-corrosion additives is heated to 25-50℃, and then the eucalyptol and triethanolamine oleate are added to the heated mother liquor containing the anti-freezing and anti-corrosion additives.

[0021] Optionally, the rotating speed of the first stirring and mixing, the second stirring and mixing and the third stirring and mixing is 200-600 rpm, and the time is 0.5-1 h.

[0022] The road efficient anti-freezing and anti-corrosion snow-melting agent and the preparation method thereof provided in the application realize the preparation of the snow-melting agent, and have the following beneficial effects compared with the prior art:

[0023] (1) In the application, the freezing point of ice and snow can be reduced by adding the anti-freezing agent, so that the ice and snow can be melted at a lower temperature, the road icing is avoided, and the road traffic capacity is ensured. The anti-corrosion additives can significantly reduce the corrosion of the road surface, green plants, reinforced concrete and other infrastructure, thereby prolonging the service life thereof. In the application, the component ratio is optimized to construct a "precipitation film-adsorption film" composite protective layer, which breaks through the limitations of traditional phosphorus pollution, acid residue and single corrosion inhibition mechanism. The precipitation film formed by sodium tripolyphosphate / 2-hydroxyphosphonyl acetic acid / benzotriazole / tannic acid covers the metal surface to physically block the corrosion medium; at the same time, the adsorption film formed by sodium citrate / sodium gluconate / polyvinylpyrrolidone long-term inhibits the electrochemical corrosion to form a multi-dimensional protection system. The compounding of the organic corrosion inhibitor and the inorganic corrosion inhibitor exhibits the characteristics of synergistic effect, expanded application range, improved economic benefit, reduced environmental impact and the like. Moreover, the low-dose, high-corrosion-inhibition-rate and environmentally friendly comprehensive performance breakthrough of the anti-corrosion additives is realized.

[0024] (2) The anti-corrosion performance of the snow-melting agent is improved by adding eucalyptol and triethanolamine oleate in the application. The nitrogen atom in the triethanolamine oleate can be adsorbed on the metal surface better than the chloride ion, and a composite film is formed with the "precipitation film-adsorption film" formed by the anti-corrosion additives, which greatly reduces the corrosion of the chloride ion on the metal surface. The eucalyptol is dispersed in the snow-melting agent, and the intermolecular forces (such as hydrogen bond, electrostatic interaction) between the eucalyptol and the chloride ion can further avoid the electrochemical corrosion of the chloride ion on the metal surface.

[0025] At the same time, the eucalyptol has an inhibitory effect on bacteria and fungi, and by adding the eucalyptol, the snow-melting agent can be inhibited during storage and transportation, so that the snow-melting agent is prevented from deteriorating due to the generation of bacterial film, and the snow-melting agent is beneficial to maintain excellent snow-melting performance.

[0026] (3) The application not only melts snow (ice) and removes snow, but also avoids the separation of the composite film and the corrosion of metal facilities such as road surface and vehicle during the snow melting process. In addition, the composite film can continuously protect the metal surface during the drying process after snow melting, avoid the corrosion of road facilities, prolong the service life of the road surface, and reduce the maintenance cost of the road surface.

[0027] (4) The snow melting agent provided by the application has good corrosion inhibition performance and snow melting and ice melting capacity, and can be applied not only to ordinary roads, bridges, highways and tunnels for deicing and snow removal in cold regions, but also to public facilities such as airports, wharfs and parking lots for snow melting and deicing. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical scheme and advantages of the embodiments of the application more clear, the technical scheme in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are some embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor also belong to the protection scope of the application.

[0029] In one aspect, the application provides a road efficient anti-freezing and anti-corrosion snow melting agent, which comprises, by weight percentage:

[0030] 10-20% of anti-freezing agent, anti-corrosion additive, and the balance of water;

[0031] The anti-corrosion additive comprises 0.1-1% of sodium citrate, 0.1-1% of benzotriazole, 0.1-1% of sodium tripolyphosphate, 0.1-1% of sodium gluconate, 0.1-1% of tannic acid, 0.1-1% of polyvinylpyrrolidone, and 0.1-1% of 2-hydroxyphosphonoacetic acid.

[0032] Specifically, by adding the anti-freezing agent, the freezing point of ice and snow can be reduced, so that the ice and snow can be melted at a lower temperature, and the icing of the road can be avoided, thereby ensuring the traffic capacity of the road. The anti-corrosion additive can significantly reduce the corrosion of the road surface, green plants, reinforced concrete and other infrastructure, thereby prolonging the service life thereof. Water is used as the solvent, so that the anti-freezing agent and the anti-corrosion additive are dissolved in water, the flowability of the snow melting agent is improved, and then the snow melting agent can be easily and uniformly spread on the road surface, the accumulated snow and ice layer can be quickly melted, the snow melting efficiency of the snow melting agent is improved, and the traffic is ensured to be smooth.

[0033] Sodium citrate can lower the freezing point, prevent freezing and corrosion is small, while the formation of complex with calcium, magnesium and other ions in water, so as to prevent the crystallization of these ions at low temperature, and then prevent the solution freezing. And sodium citrate on the environment corrosion is small, will not cause corrosion damage to the road, vehicles and plants, so it is a more environmentally friendly corrosion inhibitor ingredients. Benzotriazole in the N atom on the lone pair of electrons can and Fe empty d orbital form coordination bond adsorbed on the surface of carbon steel reactive sites, on the metal surface to form adsorption film, avoid the immersion of other corrosion inhibitor, and thus avoid the corrosion of deicing salt on the road metal. At the same time, sodium citrate-benzotriazole formation chelate system, through the carboxylic acid group and azole ring π-π stacking effect, significantly improve the self repair ability of corrosion inhibitor film. Sodium citrate-benzotriazole chelate system, the mass ratio of sodium citrate and benzotriazole is 8-12:1.

[0034] The corrosion inhibition effect of sodium gluconate mainly reflects its complexing ability to metal and its stabilizing effect on corrosive medium. It can form stable complexes with metal ions, thereby reducing the corrosion rate of metal. At the same time, sodium gluconate can also stabilize harmful ions in corrosive medium, reducing their corrosion effect on metal. Sodium tripolyphosphate forms stable complexes with metal ions, forming a precipitate film on the metal surface, preventing the metal from reacting 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 deicing agent, allowing the deicing agent to melt ice and snow more quickly and reduce the impact of snow accumulation on traffic. Tannic acid can combine with water in ice and snow to form a eutectic mixture, thereby lowering the freezing point and allowing ice and snow to melt at a lower temperature. Polyvinylpyrrolidone can absorb water in the deicing agent to prevent freezing, further enhancing its anti-freezing effect, and also has good film-forming and complexing properties. When attached to the metal surface, it can form a long-acting adsorption film on the metal surface, which, in combination with sodium citrate-benzotriazole, inhibits the occurrence of electrochemical corrosion.

[0035] In this application, by optimizing the component ratio, a "precipitate film-adsorption film" composite protective layer is constructed, breaking through the limitations of traditional single corrosion inhibition mechanism. The precipitate 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 long-term inhibits electrochemical corrosion, forming a multi-dimensional protection system. The combination of organic and inorganic corrosion inhibitors exhibits synergistic effects, expands the application range, improves economic efficiency, and reduces environmental impact.

[0036] Optionally, the anti-freezing agent is composed of calcium chloride, magnesium chloride, and sodium acetate in a mass ratio of 5:4:1.

[0037] Specifically, calcium chloride and magnesium chloride can significantly reduce the freezing point of water after dissolving in water, so that the snow-melting agent has strong snow-melting ability at low temperature. Magnesium chloride has less negative impact on the environment and is suitable for environments that need to protect vegetation. Sodium acetate is an organic snow-melting agent that has excellent snow-melting effect and little corrosiveness to the environment. In the present application, the antifreeze agent is compounded with calcium chloride, magnesium chloride and sodium acetate in a special proportion to ensure the snow-melting performance of the snow-melting agent, and through the synergistic effect of multiple components, the corrosion rate of the chlorosalt snow-melting agent on metal is significantly reduced.

[0038] Optionally, the corrosion-resistant 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.

[0039] Optionally, the corrosion-resistant 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.

[0040] Optionally, the corrosion-resistant 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.

[0041] Optionally, 0.02-0.1% of an auxiliary agent including eucalyptol and triethanolamine oleate is added to the snow-melting agent by weight percentage.

[0042] Optionally, the mass ratio of eucalyptol to triethanolamine oleate is 1:2-3.5.

[0043] Specifically, the nitrogen atom in the oleic acid triethanolamine can be adsorbed on the metal surface better than the chloride ion, and form a composite film with the "precipitation film-adsorption film" formed by the corrosion inhibitor additive, greatly reducing the corrosion of the chloride ion on the metal surface, while the aromatic ring with a large pi bond contained in the oleic acid triethanolamine can enhance the strength and rigidity of the composite film, avoiding the separation of the composite film while snow melting (ice), snow removal, not only avoiding the corrosion of the metal facilities such as road surface and vehicle during snow melting, but also continuously protecting the metal surface after snow melting to dry the road surface, avoiding the corrosion of the road facilities, prolonging the service life of the road surface, and reducing the maintenance cost of the road surface. Eucalyptol is dispersed in the snow melting agent, and the intermolecular force (such as hydrogen bond, electrostatic interaction) between eucalyptol and chloride ion can further avoid the electrochemical corrosion of chloride ion on the metal surface, thereby improving the corrosion resistance of the snow melting agent.

[0044] In another aspect, the application provides a preparation method of a road efficient anti-freezing and anti-corrosion snow melting agent, which is used for preparing the snow melting agent described above, and the preparation method comprises the following steps:

[0045] (1) According to the weight parts, calcium chloride, magnesium chloride and sodium acetate are sequentially added into water, and first stirring and mixing is carried out to obtain an anti-freezing agent solution;

[0046] (2) According to the weight parts, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added into the anti-freezing agent solution, and second stirring and mixing is carried out to obtain a mother liquor containing anti-freezing and anti-corrosion additives;

[0047] (3) According to the weight parts, eucalyptol and oleic acid triethanolamine are added into the mother liquor containing anti-freezing and anti-corrosion additives, and third stirring and mixing is carried out to obtain the snow melting agent.

[0048] Specifically, the application realizes the preparation of the snow melting agent through the above scheme. By sequentially adding the components (calcium chloride, magnesium chloride and sodium acetate) in the anti-freezing agent into water, the calcium chloride, magnesium chloride and sodium acetate are dissolved in water through first stirring and mixing to obtain an anti-freezing agent solution, then the components in the anti-corrosion additive are added into the anti-freezing agent solution, and second stirring and mixing is carried out to obtain a mother liquor containing anti-freezing and anti-corrosion additives, and finally eucalyptol and oleic acid triethanolamine are added into the mother liquor containing anti-freezing and anti-corrosion additives, and third stirring and mixing is carried out to obtain the snow melting agent. Batch stirring and dissolution make the components in the snow melting agent better dissolved (or dispersed) in water, improve the dispersion uniformity of the components in the snow melting agent, and further improve the snow melting effect when the snow melting agent is spread on the road surface.

[0049] Optionally, before the third stirring and mixing, the mother liquor containing anti-freezing and anti-corrosion additives is heated to 25-50℃, and then eucalyptol and oleic acid triethanolamine are added into the heated mother liquor containing anti-freezing and anti-corrosion additives.

[0050] Specifically, the mother liquor containing the anti-freezing and anti-corrosion additives is heated, and then eudesmin and triethanolamine oleate are added, and a third stirring and mixing is performed to obtain the snow melting agent, so that the eudesmin and triethanolamine oleate can be better dispersed in the snow melting agent. Meanwhile, the temperature is increased, which is helpful to the formation of the sodium citrate-benzotriazole chelate system, and further improves the snow melting capacity of the snow melting agent.

[0051] Optionally, the rotating speed of the first, second and third stirring and mixing is 200-600 rpm, and the time is 0.5-1 h. In the sodium citrate-benzotriazole chelate system, the mass ratio of sodium citrate to benzotriazole is 8-12:1.

[0052] The technical solution of the present application will be illustrated in detail by specific examples as follows.

[0053] Example 1

[0054] A preparation method of a road efficient anti-freezing and anti-corrosion snow melting agent, comprising the following steps:

[0055] (1) According to the weight parts, calcium chloride, magnesium chloride and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and a first stirring and mixing is performed to obtain an anti-freezing solution;

[0056] (2) Sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added to the anti-freezing solution, and a second stirring and mixing is performed to obtain a snow melting agent.

[0057] Among them, the percentage by weight includes:

[0058] The anti-freezing agent is 10%, the anti-corrosion additives, and the balance is water;

[0059] The anti-corrosion additives include: 0.1% sodium citrate-benzotriazole chelate 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. Example 2

[0060] A preparation method of a road efficient anti-freezing and anti-corrosion snow melting agent, comprising the following steps:

[0061] (1) According to the weight parts, calcium chloride, magnesium chloride and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and a first stirring and mixing is performed to obtain an anti-freezing solution;

[0062] (2) According to weight parts, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added to the antifreeze solution, and second stirring mixing is carried out to obtain the snow melting agent.

[0063] Among them, according to the weight percentage includes:

[0064] Antifreeze 15%, corrosion inhibitor, the balance is water;

[0065] The corrosion inhibitor includes 0.5% sodium citrate-benzotriazole chelate 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. Example 3

[0066] A preparation method of a road efficient antifreeze and corrosion inhibitor snow melting agent, comprising the following steps:

[0067] (1) According to weight parts, calcium chloride, magnesium chloride and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and first stirring mixing is carried out to obtain an antifreeze solution;

[0068] (2) According to weight parts, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxyphosphonoacetic acid are added to the antifreeze solution, and second stirring mixing is carried out to obtain the snow melting agent.

[0069] Among them, according to the weight percentage includes:

[0070] Antifreeze 20%, corrosion inhibitor, the balance is water;

[0071] The corrosion inhibitor includes: 1% sodium citrate-benzotriazole chelate system (the 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.

[0072] Comparative Example 1

[0073] A preparation method of a road efficient antifreeze and corrosion inhibitor snow melting agent, comprising the following steps:

[0074] The difference from Example 2 is:

[0075] (1) According to weight parts, calcium chloride, magnesium chloride and sodium acetate are sequentially added to water in a mass ratio of 5:4:1, and first stirring mixing is carried out to obtain an antifreeze solution;

[0076] Among them, according to the weight percentage includes:

[0077] Antifreeze 10%, corrosion inhibitor 0%, the rest is water.

[0078] Comparative Example 2

[0079] A preparation method of a road efficient antifreeze corrosion inhibitor snow melting agent, comprising the following steps:

[0080] The difference from Example 2 is that:

[0081] (1) According to the weight part, calcium chloride, magnesium chloride, sodium acetate are added into water in the mass ratio of 5:4:1 in turn, and first stirring and mixing is carried out to obtain an antifreeze solution;

[0082] (2) According to the weight part, sodium citrate, benzotriazole, sodium tripolyphosphate, tannic acid, and 2-hydroxyphosphonoacetic acid are added to the antifreeze solution, and second stirring and mixing is carried out to obtain a snow melting agent.

[0083] Among them, the percentage by weight includes:

[0084] Antifreeze 15%, corrosion inhibitor, the rest is water;

[0085] The corrosion inhibitor includes 0.5% sodium citrate-benzotriazole chelate 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.

[0086] Comparative Example 3

[0087] A preparation method of a road efficient antifreeze corrosion inhibitor snow melting agent, comprising the following steps:

[0088] The difference from Example 2 is that:

[0089] (1) According to the weight part, calcium chloride, magnesium chloride, sodium acetate are added into water in the mass ratio of 5:4:1 in turn, and first stirring and mixing is carried out to obtain an antifreeze solution;

[0090] (2) According to the weight part, sodium citrate, benzotriazole, sodium tripolyphosphate, tannic acid, and 2-hydroxyphosphonoacetic acid are added to the antifreeze solution, and second stirring and mixing is carried out to obtain a snow melting agent.

[0091] Among them, the percentage by weight includes:

[0092] Antifreeze 15%, corrosion inhibitor, the rest is water;

[0093] The corrosion inhibitor includes 0.5% sodium citrate-benzotriazole chelate system (the mass ratio of sodium citrate to benzotriazole is 10:1), 0.5% tannic acid, and 0.5% 2-hydroxyphosphonoacetic acid.

[0094] Experimental Example 1

[0095] Corrosion resistance test of snow-melting agent

[0096] Specific experimental method: under room temperature environment, 20# carbon steel test pieces with size of 50mm x 25mm x 2mm were washed with anhydrous ethanol, dried to constant weight, and weighed to 0.1mg. The mass percentage concentration of 10wt% of the snow-melting agent solution provided by Examples 1-3 and Comparative Examples 1-3 was configured, and the carbon steel test pieces were respectively hung in the solutions of Examples 1-3 and Comparative Examples 1-3, so that they were immersed to the same height (3 / 4 of the whole test piece), and continuously placed for 7 days. After the test, the surface corrosion was removed, and the test pieces were cleaned and dried, then weighed to obtain the mass loss of each test piece. According to the formula in standard GB / T 18175-2014, the corrosion rate and corrosion inhibition rate were calculated. Each test was carried out at least three times in parallel, and the average value was taken to obtain the results as shown in Table 1.

[0097] Table 1

[0098]

[0099] Experimental Example 2

[0100] Snow-melting and ice-melting ability test

[0101] The snow-melting and ice-melting ability of the snow-melting agent obtained from Examples 1-3 and Comparative Examples 1-3 was tested.

[0102] According to the method and steps specified in national standard GB / T 23851-2017 "Snow-melting agent" 6.5.3.2.2Ⅱ type snow-melting agent snow-melting and ice-melting ability test, the snow-melting and ice-melting ability of the snow-melting agent provided by Examples 1-3 and Comparative Examples 1-3 was tested. Each test was carried out at least three times in parallel, and the average value was taken to obtain the results as shown in Table 2.

[0103] Table 2

[0104]

[0105] From the observation of Table 1 and Table 2, the corrosion inhibition performance of the snow-melting agent provided by the embodiments 1-3 of the present application is obviously improved compared with the comparative examples 1-3. Comparing the embodiments 1-3 with the comparative example 1, the corrosion inhibitor is not added in the comparative example 1, so it is illustrated that the addition of the corrosion inhibitor can obviously improve the corrosion inhibition performance of the snow-melting agent. By optimizing the component ratio of the corrosion inhibitor, the “precipitation film-adsorption film” composite protective layer is constructed, which breaks through the limitation of the traditional single corrosion inhibition mechanism. The precipitation film formed by sodium tripolyphosphate / 2-hydroxyphosphonoacetic acid / benzotriazole / tannic acid covers the metal surface, and physically blocks the corrosion medium; at the same time, the adsorption film formed by sodium citrate / sodium gluconate / polyvinylpyrrolidone long-term inhibits the electrochemical corrosion, and forms a multi-dimensional protection system. The compounding of the organic corrosion inhibitor and the inorganic corrosion inhibitor exhibits the characteristics of synergistic effect, expansion of application range, improvement of economic benefit, and reduction of environmental impact.

[0106] Comparing the comparative examples 1-3 with the comparative examples 2 and 3, the main components of the corrosion inhibitor in the comparative example 2 are sodium citrate, benzotriazole, sodium tripolyphosphate, tannic acid, and 2-hydroxyphosphonoacetic acid, which can form a precipitation film, while the main components of the corrosion inhibitor in the comparative example 3 are sodium citrate / sodium gluconate / polyvinylpyrrolidone, which can form an adsorption film. It is illustrated that although the formation of a single precipitation film or adsorption film can achieve the corrosion inhibition effect, compared with the construction of the “precipitation film-adsorption film” composite protective layer, the corrosion inhibition performance of the snow-melting agent reaches the best under the coexistence of the “precipitation film-adsorption film”. At the same time, the snow-melting and ice-melting capacity test results show that the relative snow-melting and ice-melting capacity of the snow-melting agent provided by the present application can meet or even far exceed the index requirement of the relative snow-melting and ice-melting capacity ≥90% in GB / T 23851-2017 “Snow-melting agent”.

[0107] Embodiment 4

[0108] The difference between the embodiment 2 and the embodiment 4 is that:

[0109] A preparation method of a road efficient anti-freezing and anti-corrosion snow-melting agent, comprising the following steps:

[0110] (3) heating the mother liquor containing the anti-freezing and anti-corrosion additive to 25℃, then adding eucalyptol and triethanolamine oleate to the heated mother liquor containing the anti-freezing and anti-corrosion additive, and performing third stirring and mixing to obtain the snow-melting agent.

[0111] Among them, the percentage by weight includes:

[0112] The anti-freezing agent is 15%, the anti-corrosion additive and the auxiliary agent are 0.02%, and the balance is water.

[0113] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0114] The auxiliary agent includes eucalyptol and triethanolamine oleate at a mass ratio of 1:2.

[0115] Example 5

[0116] The difference from Example 2 is that:

[0117] A preparation method of a road efficient anti-freezing and anti-corrosion snow-melting agent, comprising the following steps:

[0118] (3) The mother liquor containing the anti-freezing and anti-corrosion additives is heated to 35℃, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and anti-corrosion additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0119] Among them, by weight percentage includes:

[0120] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.07%, and the balance is water;

[0121] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0122] The auxiliary agent includes eucalyptol and triethanolamine oleate at a mass ratio of 1:2.5.

[0123] Example 6

[0124] The difference from Example 2 is that:

[0125] A preparation method of a road efficient anti-freezing and anti-corrosion snow-melting agent, comprising the following steps:

[0126] (3) The mother liquor containing the anti-freezing and anti-corrosion additives is heated to 50℃, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and anti-corrosion additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0127] Among them, by weight percentage includes:

[0128] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.1%, and the balance is water;

[0129] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0130] The auxiliary agent includes eucalyptol and triethanolamine oleate at a mass ratio of 1:3.5.

[0131] Comparative Example 4

[0132] The difference from Example 5 is that:

[0133] A preparation method of a road efficient anti-freezing and anti-corrosion snow-melting agent, comprising the following steps:

[0134] (3) The mother liquor containing the anti-freezing and anti-corrosion additives is heated to 35°C, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and anti-corrosion additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0135] Among them, by weight percentage includes:

[0136] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.11%, and the balance is water;

[0137] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0138] The auxiliary agent includes eucalyptol and triethanolamine oleate at a mass ratio of 1:2.5.

[0139] Comparative Example 5

[0140] The difference from Example 5 is that:

[0141] A preparation method of a road efficient anti-freezing and anti-corrosion snow-melting agent, comprising the following steps:

[0142] (3) The mother liquor containing the anti-freezing and anti-corrosion additives is heated to 35°C, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and anti-corrosion additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0143] Among them, by weight percentage includes:

[0144] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.009%, and the balance is water;

[0145] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0146] The auxiliary agent includes eucalyptol and triethanolamine oleate with a mass ratio of 1:2.5.

[0147] Comparative Example 6

[0148] The difference from Example 5 is that:

[0149] A preparation method of a road efficient anti-freezing and corrosion preventing snow-melting agent, comprising the following steps:

[0150] (3) The mother liquor containing the anti-freezing and corrosion preventing additives is heated to 35°C, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and corrosion preventing additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0151] Among them, by weight percentage includes:

[0152] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.07%, and the balance is water.

[0153] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0154] The auxiliary agent is selected from eucalyptol.

[0155] Comparative Example 7

[0156] The difference from Example 5 is that:

[0157] A preparation method of a road efficient anti-freezing and corrosion preventing snow-melting agent, comprising the following steps:

[0158] (3) The mother liquor containing the anti-freezing and corrosion preventing additives is heated to 35°C, and then eucalyptol and triethanolamine oleate are added into the heated mother liquor containing the anti-freezing and corrosion preventing additives, and a third stirring and mixing is performed to obtain the snow-melting agent.

[0159] Among them, by weight percentage includes:

[0160] The anti-freezing agent is 15%, the corrosion inhibitor additives and the auxiliary agent are 0.07%, and the balance is water.

[0161] The corrosion inhibitor additives include 0.5% sodium citrate-benzotriazole chelate 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.

[0162] The auxiliary agent is selected from triethanolamine oleate.

[0163] Experimental Example 3

[0164] Corrosion inhibition performance test of the snow-melting agent

[0165] The corrosion rate and corrosion inhibition rate of the snow-melting agents obtained in Examples 4-6 and Comparative Examples 4-7 are detected by using the same method as in Experimental Example 1. Each test is carried out at least three times in parallel, and the average value is taken to obtain the results shown in Table 3.

[0166] Table 3

[0167]

[0168] Experimental Example 4

[0169] Snow-melting and ice-melting ability detection

[0170] The snow-melting and ice-melting ability of the snow-melting agents obtained in Examples 4-6 and Comparative Examples 4-7 is detected by using the same method as in Experimental Example 2.

[0171] Each test is carried out at least three times in parallel, and the average value is taken to obtain the results shown in Table 4.

[0172] Table 4

[0173]

[0174] It is found from Tables 3 and 4 that the snow-melting agents provided in Examples 4-6 have excellent corrosion inhibition performance and snow-melting and ice-melting ability. It is found from the comparison of Examples 4-6 and Comparative Examples 4, 5 that after adding 0.02-0.1% auxiliary agent, the corrosion inhibition performance and snow-melting and ice-melting ability of the snow-melting agent are obviously improved, and the auxiliary agent includes eucalyptol and triethanolamine oleate. It is found from the comparison of Comparative Examples 6 and 7 that the corrosion inhibition performance and snow-melting and ice-melting ability of the snow-melting agent are less improved when eucalyptol or triethanolamine oleate is added alone, which indicates that the nitrogen atom in triethanolamine oleate can be better adsorbed on the metal surface than the chloride ion, and a composite film formed by the “precipitation film-adsorption film” formed by the corrosion inhibitor additives can greatly reduce the corrosion of the chloride ion on the metal surface. The intermolecular forces (such as hydrogen bond and electrostatic interaction) between eucalyptol and the chloride ion can further avoid the electrochemical corrosion of the chloride ion on the metal surface, prolong the service life of the road surface and reduce the maintenance cost of the road surface.

[0175] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that; it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement to part 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. A road efficient de-icing and anti-corrosion snow-melting agent, characterized in that, By weight percentage comprising: Antifreeze 10-20%, corrosion inhibitor additive, the balance is water; 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-hydroxy phosphono acetic acid; The snow melting agent also adds 0.02-0.1% auxiliary agent, the auxiliary agent includes eucalyptol and oleic acid triethanolamine with mass ratio of 1:2-3.

5.

2. The road efficient deicing anticorrosive snowmelt of claim 1, wherein, The antifreeze is mixed by calcium chloride, magnesium chloride, sodium acetate with mass ratio of 5:4:

1.

3. A process for the preparation of a road efficient deicing anticorrosive snowmelt agent, said process for the preparation of a snowmelt agent as claimed in claim 2, characterized in that, The preparation method includes the following steps: (1) by weight parts, calcium chloride, magnesium chloride, sodium acetate are added into water in turn, first stirring and mixing, obtaining antifreeze solution; (2) by weight parts, sodium citrate, benzotriazole, sodium tripolyphosphate, sodium gluconate, tannic acid, polyvinylpyrrolidone and 2-hydroxy phosphono acetic acid are added to the antifreeze solution, second stirring and mixing, obtaining mother liquor containing antifreeze corrosion inhibitor additive; (3) by weight parts, eucalyptol and oleic acid triethanolamine are added to the mother liquor containing antifreeze corrosion inhibitor additive, third stirring and mixing, obtaining the snow melting agent.

4. The method of claim 3, wherein the road deicing and anticorrosive snow melting agent is prepared by adding 0.1 to 0.3 parts by weight of the sodium salt of the carboxylic acid to 100 parts by weight of the sodium salt of the sulfonic acid. Before the third stirring and mixing, the mother liquor containing antifreeze corrosion inhibitor additive is heated to 25-50℃, then the eucalyptol and the oleic acid triethanolamine are added to the heated mother liquor containing antifreeze corrosion inhibitor additive.

5. The method of preparing a road efficient deicing anticorrosive snowmelt of claim 4, wherein, The rotation speed of the first stirring and mixing, the second stirring and mixing and the third stirring and mixing is 200-600rpm, and the time is 0.5-1h.

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