KR101929243B1 - Low-corrosive antifreeze - Google Patents

Abstract

The present invention relates to a low corrosion-resistant cryoprotectant to which an organic acid is added to calcium chloride. It is an object of the present invention to provide a low corrosive cryoprotectant, which prevents degradation of roads, pot holes, automobile body corrosion and deterioration of concrete structures, The present invention relates to a cryoprotectant.

Description

Low Corrosive Antifreeze {LOW-CORROSIVE ANTIFREEZE}

The present invention relates to a low corrosion-resistant cryoprotectant to which an organic acid is added to calcium chloride. It is an object of the present invention to provide a low corrosive cryoprotectant, which prevents degradation of roads, pot holes, automobile body corrosion and deterioration of concrete structures, The present invention relates to a cryoprotectant.

As a snow removing agent used in the winter season, a mixture of calcium chloride, calcium chloride and salt, magnesium chloride, eco-friendly low chloride, nitrate compound and the like are used. Among them, calcium chloride has the best ability of snow removal. However, since calcium chloride is highly corrosive, it has disadvantages such as deterioration of roads, occurrence of pot holes, corrosion of automobile bodies, and the like. This problem also occurs when calcium chloride is used as a concrete admixture for preventing freezing, thereby causing deterioration of the concrete structure.

In order to prevent this, an eco-friendly low chloride or nitrate compound has been developed as an alternative, but the price is 3 to 9 times higher than the price of calcium chloride.

Korean Patent Laid-Open Publication No. 2014-0046134 (published on Apr. 18, 2014) includes an organic acid salt, a basic compound and an alkaline compound, the organic acid constituting the organic acid salt has a relatively high price, The fermentation agent of No. 2006-0060406 (published on June 5, 2006) includes a bioceramic material emitting far-infrared rays. When the size of the bioceramics is small, it acts as fine dust which is harmful to human body. There is a problem that the treading force of the tire is lowered.

In consideration of the above problems, development of an antifreezing agent that is eco-friendly, less corrosive, and cost competitive is required.

Korean Patent Publication No. 2014-0046134 (published on April 18, 2014) Korean Patent Publication No. 2006-0060406 (published on June 5, 2006)

The low corrosion-preventive cryoprotectant of the present invention is contrived to solve the above-mentioned problems, and it is possible to reduce the social cost by reducing the corrosion of the road due to the corrosion, It is another object of the present invention to provide a low-corrosive cryoprotectant capable of effectively preventing deterioration of a concrete structure.

In order to accomplish the above-mentioned object, the low corrosion-

100 parts by weight of calcium chloride, and

0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.2 to 5 parts by weight, still more preferably 0.2 to 1 part by weight, Is contained in an amount of 0.2 to 0.6 parts by weight.

The low corrosion-resistant cryoprotectant of the present invention may further comprise 1 to 10 parts by weight, preferably 1.5 to 8 parts by weight, more preferably 2 to 6.5 parts by weight of the organic acid salt per 100 parts by weight of the calcium chloride.

In addition, the organic acid may be tartaric acid.

In addition, the organic acid salt may be sodium citrate.

The low corrosion-preventive cryoprotectant according to the present invention can prevent the deterioration of roads, the occurrence of pot holes, the corrosion of automobile bodies and the deterioration of concrete structures caused by road blast or concrete admixture, thereby preventing unnecessary social costs . Above all, the low-corrosive cryoprotectant of the present invention is much cheaper than the conventional environmentally-friendly snowmelt agent, which is 3 to 9 times the price of calcium chloride, and thus has an advantage of being an environment-friendly cryoprotectant having price competitiveness.

1 is a photograph showing corrosion of iron in an aqueous solution of Comparative Example 1 (calcium chloride).
2 is a photograph showing corrosion of iron in the aqueous solution of Example 1 of the present invention.
3 is a photograph showing corrosion of iron in the aqueous solution of Example 2 of the present invention.
4 is a photograph showing corrosion of iron in the aqueous solution of Example 3 of the present invention.
5 is a photograph showing corrosion of iron in the aqueous solution of Example 4 of the present invention.
6 is a photograph showing corrosion of iron in the aqueous solution of Example 5 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, numerous specific details, such as specific elements, are set forth in order to provide a thorough understanding of the present invention, and it is to be understood that the present invention may be practiced without these specific details, It will be obvious to those who have knowledge of. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In the present invention, 'organic acid' generally refers to organic compounds having acidity, and organic compounds containing a carboxy group and a sulfone group are representative. Acids such as acetic acid, butyric acid, palmitic acid, oxalic acid, tartaric acid, etc., which correspond to inorganic acids, are generally weaker than inorganic acids, but also strong acids such as sulfonic acids.

&Quot; Organic acid salt " means a salt formed by reacting the organic acid with a base.

In order to reduce the corrosion resistance of the cryoprotectant,

100 parts by weight of calcium chloride, and

0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.2 to 5 parts by weight, still more preferably 0.2 to 1 part by weight, Is contained in an amount of 0.2 to 0.6 parts by weight.

The calcium chloride is a component responsible for the snow-removing performance or the freezing-preventing performance of the cryoprotectant of the present invention.

If snow accumulates on the road during the winter season and forms ice roads, the frictional force of the vehicle can be reduced and lead to accidents. At this time, calcium chloride lowers the freezing point of the water, so that solid ice or ice turns into liquid water and flows down to the edge of the road. Also, it is added to cement concrete mixture and it plays a role to prevent the growth of ice crystals in concrete during the winter season. This is to prevent the hardening of the cement when ice crystals are grown, and consequently the strength of the concrete structure to deteriorate. The above-mentioned calcium chloride has an advantage of being excellent in the freezing prevention performance as compared with other compounds, but also being more economical than anything else, but it has been pointed out that it has a strong corrosiveness.

The main feature of the present invention is that an organic acid is introduced in order to reduce the corrosiveness of such calcium chloride. The organic acid which can be used in the present invention is not limited as long as it can reduce the corrosiveness of calcium chloride. Examples thereof include tartaric acid, acetic acid, butyric acid, palmitic acid and oxalic acid. Among them, tartaric acid is preferable in terms of economy and high environmental friendliness. As described above, the present invention is advantageous in that a relatively small amount of organic acid is used, but a high corrosion resistance is exhibited.

The low corrosion-resistant cryoprotectant of the present invention may further comprise 1 to 10 parts by weight, preferably 1.5 to 8 parts by weight, more preferably 2 to 6.5 parts by weight, of the organic acid salt per 100 parts by weight of the calcium chloride.

In the present invention, the organic acid salt assists the corrosion-preventing function of the organic acid, and by using a salt of an organic acid similar to the organic acid, the corrosion-preventing function of the organic acid can be stably and efficiently exhibited. Specifically, if the concentration of the organic acid exhibiting freezing-preventing performance is reduced in the system where the snow removal is performed, the organic acid of the organic acid salt is dissociated by the common ion effect to be supplied to the system where the snow removal is performed. As the organic acid is converted into a salt form, the freezing point depressing effect is lowered and the freezing prevention function is stably expressed.

The organic acid salt which can be used in the present invention is not limited as long as it can stably assure the freezing-preventing function of the organic acid, and sodium citrate is particularly preferable.

Hereinafter, embodiments of the present invention will be described.

Example

Example  1 to Example 6: Preparation of Low Corrosion Freezing Agent

Calcium chloride, tartaric acid and sodium citrate were mixed with the composition shown in Table 1 below to prepare a low corrosion-resistant cryoprotectant of the present invention.

Calcium chloride (g) Tartaric acid (g) Sodium citrate (g) Example 1 97.8 0.2 2 Example 2 96.7 0.3 3 Example 3 95.6 0.4 4 Example 4 94.5 0.5 5 Example 5 93.4 0.6 6 Example 6 84.0 10.0 6

Comparative Example 1 and Comparative Example 2: Preparation of a cryoprotectant

Calcium chloride, tartaric acid and sodium citrate were mixed with the composition shown in Table 2 below to prepare a cryoprotectant.

Calcium chloride (g) Tartaric acid (g) Sodium citrate (g) Comparative Example 1 100 0 0 Comparative Example 2 93.95 0.05 6

Test Example 1: Steel corrosion evaluation

The cutter blade was immersed for 168 hours in an aqueous solution prepared by diluting sodium chloride in the concentration of 3% by weight in the above Examples 1 to 6, Comparative Examples 1 and 2 and as a control, and the corrosion state was evaluated. 1 to 6. FIG. 1 shows the result of Comparative Example 1, FIG. 2 shows Example 1, FIG. 3 shows Example 2, FIG. 4 shows Example 3, FIG. 5 shows Example 4 and FIG.

Weight loss per unit area (mg / cm2) Corrosivity (%) Example 1 0.0111 30.32 Example 2 0.0074 20.23 Example 3 0.0062 18.92 Example 4 0.0056 15.33 Example 5 0.0083 10.61 Example 6 0.0037 10.13 Comparative Example 1 0.0184 50.27 Comparative Example 2 0.0147 40.33 Control Example 0.0366

The weight loss per unit area is a value obtained by dividing the difference between the weight of the cutter blade before the test and the weight after the test by the surface area of the cutter blade, and the corrosion resistance is a value obtained by dividing the weight difference by the weight before the test. From Table 3 and FIG. 1 to FIG. 6, it can be seen that the cryoprotectant of the present invention shows much lower corrosivity than the comparative examples.

Test Example 2: Evaluation of melting performance

The anti-freezing performance of Examples 1 to 5 was evaluated by the melting performance against sodium chloride as a control. Table 4 shows the percentage of how much rusty debris is generated at 15, 30 and 60 minutes compared to the control at 5 ° C, 5 ° C and 15 ° C, respectively.

Melting performance test (-5 ℃) 15 minutes 30 minutes 60 minutes Example 1 114 131 145 Example 2 113 129 141 Example 3 113 128 138 Example 4 110 126 135 Example 5 109 122 134

Melting performance test (-10 ℃) 15 minutes 30 minutes 60 minutes Example 1 110  137 146 Example 2 112  135 143 Example 3 109  134 139 Example 4 108  133 138 Example 5 105  133 135

Melting performance test (-15 ℃) 15 minutes 30 minutes 60 minutes Example 1 111 129 141 Example 2 109 128 140 Example 3 109 125 139 Example 4 103 123 139 Example 5 103 121 138

As a result of the above-mentioned melting test, it was confirmed that the cryoprotectant of the present invention had an excellent frost resistance as compared with sodium chloride

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course it is possible. Accordingly, the scope of the present invention should not be construed as being limited to the above-described embodiments, but should be determined by equivalents to the appended claims, as well as the following claims.

Claims (4)

100 parts by weight of calcium chloride,
0.1 to 10 parts by weight of tartaric acid, and
2 to 6.5 parts by weight of sodium citrate.
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