KR101895685B1 - Nonchloride solid-deicer composition - Google Patents

Abstract

The present invention relates to an organic acid salt; And an icing composition comprising an azole and an organic acid as metal corrosion inhibitors. The composition of the present invention is a solid-phase composition used for the deicing and snowing of airport airside pavement, and has an excellent corrosion preventing performance against aircraft special metals by using a mixture of triazole and an organic acid as a metal corrosion inhibiting additive. In addition, the organic acid salt is used as a raw material and shows little influence on the environment and has an effective snow removal performance even at a low temperature. It is possible to prevent the deterioration of the durability of the airport air side concrete pavement of the present invention solid-state snow removing composition, thereby enabling the safe operation of the aircraft in the airport airside.

Description

[0001] The present invention relates to a non-chloride solid-deicer composition,

The present invention relates to a non-salted environmentally friendly solid anticaking composition, and more particularly, to an environmentally friendly solid antiseptic composition for an airport airside.

In general roads and highways, inorganic salts such as calcium chloride (CaCl ₂ ) and salt (NaCl) are used mainly for cost-effective and are used for smooth road traffic in winter. However, chlorine ions contained in these inorganic salts are highly corrosive to metals and plastics of vehicles and cause durability degradation of road pavement (asphalt, concrete) and structures, thereby reducing service life, And adversely affect the environment.

<Concrete pavement damage caused by general road snow removal agent>

These problems lead to the use of chlorides such as calcium chloride (CaCl ₂ ) and magnesium chloride (MgCl ₂ ) in the FAA, as air corridors at airports and lower durability of air-side concrete pavements lead to safety accidents directly linked to personal injury. Glycol having a similar performance is strictly limited and is highly toxic to the environment and is used only for removing snow or ice on a body such as an aircraft wing surface. Urea is mainly used for snow removal on the airside in the airport air side. However, when it melts, it causes endothermal reaction, not exothermic reaction, so it does not show snow removal performance below minus 10 ℃. The element moves to the soil and the river and decomposes into ammonia and carbon dioxide. Ammonia reacts with oxygen to form nitric acid. The nitrate ions generated cause the acidity of the soil and flow into the nearby freshwater areas or rivers, thereby increasing the concentration of nitrate, which causes the fish to die.

<Process of nitrate ion generation according to urea decomposition>

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to solve the problems of the prior art described above. As a result, the present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide an organic- Antioxidants, and concrete durability deterrents, and confirmed reduced metal corrosion resistance and reduced concrete surface scaling.

Conventionally, non-saline-based snow removers containing an organic acid salt have been proposed to prevent corrosion of steel materials by using alkali compounds such as sodium hydroxide, potassium hydroxide and calcium hydroxide (Korea Patent No. 10-1426857); Nitrite (Korean Patent No. 10-1280589); Or an azole-based compound, carboxylic acid or phosphoric acid (Korean Patent No. 10-1168946) was added. However, these patents do not mention a technique to significantly reduce metal corrosion as a mixture of azole and organic acid.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors have made extensive efforts to develop a solid-state icing composition having improved metal corrosion resistance against special metals for aircraft. As a result, the inventors of the present invention have developed a non-chlorine-free environmentally-friendly deicing composition containing an organic acid salt as a raw material, a mixture of triazole and an organic acid as an aircraft special metal corrosion inhibitor, an antioxidant, and an agent for preventing durability degradation of airport air side concrete pavement. The composition of the present invention is excellent in snow removal performance and greatly reduces the impact of corrosion on aircraft special metals without affecting the durability of the airport airside concrete pavement, thereby greatly improving the long term durability of aircraft and concrete pavement.

Accordingly, an object of the present invention is to provide an environmentally-friendly solid-state freezing composition.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a process for preparing (a) an organic acid salt; And (b) an azole and an organic acid as metal corrosion inhibitors.

The inventors of the present invention have made extensive efforts to develop a solid-state anticorrosive coating composition having improved metal corrosion resistance against aircraft special metals. As a result, they have found that a mixture of triazole and organic acid as antioxidants, A non-chloride type eco-friendly icing composition containing a concrete package durability lowering agent is developed. The composition of the present invention is excellent in snow-removing performance and significantly improves the long-term durability of airplane and airside concrete pavement by preventing erosion against aircraft special metals without affecting the durability of the concrete pavement of airport air side.

The present invention relates to a solid-phase composition for the purpose of making and plowing concrete pavement of an airport airside for safe operation of an aircraft in winter, and is characterized by using a mixture of triazole and organic acid as a metal corrosion inhibitor. The icing composition of the present invention uses an organic acid salt as a raw material and has a small effect on the environment and has effective snow-removing performance even at a low temperature. It also prevents the durability of the airport airside concrete pavement from deteriorating and enables safe operation of aircraft in the winter season.

The composition of the present invention comprises (a) 92.2-97.2 wt% of an organic acid salt based on the total composition; (b) 1.8-3.8 wt% metal corrosion inhibitor based on the total composition. Or the composition of the present invention comprises (a) 92.2-97.2% by weight of an organic acid salt based on the total composition; (b) 0.3-0.8 wt.% azole and 1.5-3.0 wt.% organic acid for the total composition.

Organic acid salts that can be used in the present invention include various organic acid salts known in the art. The organic acid salt used as a raw material in the composition of the present invention may be selected from the group consisting of acetic acid, formic acid, adipic acid, citric acid, benzoic acid, succinic acid, lactic acid, malic acid, propionic acid, maleic acid, fumaric acid, Can be used. According to one embodiment of the present invention, the organic acid salt in the composition of the present invention is an acetate salt or a formate salt. According to another embodiment of the present invention, the organic acid salt in the composition of the present invention is acetal potassium, sodium acetate, potassium formate or sodium formate.

In the composition of the present invention, the organic acid salt may be contained in an amount of 92.2-97.2% by weight based on the total composition, and may be contained in an amount of 94-97% by weight or 94-96% by weight with respect to the total composition.

Azoles that can be used in the present invention include various azoles known in the art. The azoles include, for example, benzotriazole, tolythriazole, octylthiazole, decyltriazole, dodecyltriazole, aminotriazole, aminotetrazole. Methylbenzotriazole, mercaptobenzotriazole, 3-aminotriazole, 4-aminotriazole, 2,5-diaminotriazole, 4-mercaptotriazole, 3-amino- 2-aminothiazole, 2,5-dimercapto 1,3,4 thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazole, 2- 5-hydrocarbyldithio-1,3,4-thiadiazole, 2,5-bis (hydrocarbylthio) -1,3,4-thiadiazole, 2,5- (bis) Carbinol dithio-1,3,4-thiadiazole or 5-chloro-3-methylthio-l, 2,4-thiadiazole. According to one embodiment of the present invention, the azole is triazole. According to another embodiment of the present invention, the triazole is benzotriazole, tolythriazole, octylthiazole, decyltriazole, dodecyltriazole, methylbenzotriazole, or mercaptobenzotriazole. According to a particular embodiment of the invention, the triazole is benzotriazole or tolithriazole.

Organic acids that can be used in the present invention include various organic acids known in the art. The organic acids include, but are not limited to, adipic acid, citric acid, benzoic acid, succinic acid, lactic acid, malic acid, acetic acid, formic acid, propionic acid, maleic acid, fumaric acid and oxalic acid. The benzoic acid (benzoate) includes benzoate salts, including, but not limited to, sodium benzoate, potassium benzoate, calcium benzoate, and the like.

According to one embodiment of the present invention, the organic acid is a mixture of two or more organic acids. According to another embodiment of the present invention, the organic acid is a mixture of at least two organic acids selected from the group consisting of adipic acid, citric acid and benzoate. According to a particular embodiment of the present invention, the organic acid is a mixture of at least two organic acids selected from the group consisting of adipic acid, citric acid and sodium benzoate.

The composition of the present invention may further include an antioxidant or an anticorrosive agent as an additive. According to one embodiment of the present invention, the composition of the present invention may contain 1.0-4.0 wt% of additives (antioxidants and concrete durability inhibitors) relative to the total composition. According to certain embodiments of the present invention, the composition of the present invention may comprise 0.5-1.5% by weight of an antioxidant for the entire composition. According to certain embodiments of the present invention, the composition of the present invention may comprise from 0.5 to 2.5% by weight of the concrete durability reducing agent for the entire composition.

In the composition of the present invention, the antioxidant may be selected from the group consisting of sodium nitrate, dibutylhydroxytoluene, butylhydroxyanisole, triphenylphosphate, or a combination thereof. According to one embodiment of the present invention, the antioxidant is sodium nitrate.

In the composition of the present invention, the concrete durability reducing agent is selected from the group consisting of sodium silicate, potassium silicate, lithium silicate, acrylic acid, sodium based carbonate, potassium based carbonate, lithium based carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, , A polymer resin, or a combination thereof, but is not limited thereto. The polymer resin includes, but is not limited to, polyacrylic, polyethylene, polypropylene, ethylene propylene, polyvinyl chloride, polystyrene and the like.

According to an embodiment of the present invention, the concrete durability reducing agent is a polymer resin and sodium silicate. According to a particular embodiment of the present invention, the concrete durability reducing agent is polyacrylic and sodium metasilicate.

The composition of the present invention is characterized by comprising a mixture of two or more organic acids. The compositions of Examples 1 to 6 listed in Tables 1 and 4 of the following examples were used for metal corrosion test, evaluation of melting performance, and scaling resistance test for airport airside concrete pavement. As a corrosion test on aircraft special metals, corrosion resistance due to the chemical oxidation of special metals was measured to confirm the reduction of appearance / weight change of metal. Also, we confirmed the excellent snowing performance by the evaluation of the ice melting performance and confirmed the scaling inhibition effect by the icing and thaw cycle exposure of the concrete surface.

The upper and lower limits of each component content in the composition of the present invention were determined based on the results of the metal corrosion inhibition test (see Table 2 in Test Example 1). It was confirmed in Comparative Example 3 of Table 2 that the magnesium alloy in the aircraft special metal was the most vulnerable to the organic acid salt as the raw material. According to the results of the metal corrosion test of Comparative Example 13, the magnesium alloy is sensitive to the content of the additive Could know. Based on the above experimental results, the upper limit value / lower limit value was determined as 0.3-0.8 wt% and 1.5-3.0 wt% of the contents of triazole and organic acid, which are metal corrosion inhibitors, respectively.

The composition of the present invention has an effect of inhibiting the corrosion of special metal of an aircraft, and specifically exhibits excellent corrosion prevention performance against special metals such as aluminum, magnesium, titanium or steel.

The features and advantages of the present invention are summarized as follows:

(a) an organic acid salt; And an icing composition comprising an azole and an organic acid as metal corrosion inhibitors.

(b) The composition of the present invention is a solid-phase composition used for deicing and snowing airport airside pavement, and has excellent corrosion prevention performance against aircraft special metals by using a mixture of triazole and an organic acid as a metal corrosion inhibiting additive. In addition, the organic acid salt is used as a raw material and shows little influence on the environment and has an effective snow removal performance even at a low temperature.

(c) The composition of the present invention prevents the deterioration of the durability of airport airside concrete pavement of snow removing agent, thereby enabling safe operation of aircraft in airport airside.

Fig. 1 is a graph showing the results of the evaluation of the melting performance according to Test Example 2 of the present invention. Fig.
2 shows the results of an airport airside concrete pavement durability test for a solution of the solid composition of the present invention produced according to Tables 1 and 4. The specimens are rated 0-5 according to the surface condition. The lower the number of grades, the better the scaling resistance. The composition according to an embodiment of the present invention has a grade of 0-1. The results of Examples 1 to 6 are shown in order from the left.
3 shows the results of an airport airside concrete pavement durability test for a solution of a comparative example composition of Tables 1 and 4. The compositions according to the comparative examples showed grades 3-5. The results of Comparative Examples 1 to 3 are shown in order from the left.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Manufacturing Example 1

Components (unit: wt%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Raw materials Sodium formate 96 96 96 96 97 97 100 Metal corrosion inhibitor Benzotriazole 0.5 0.5 - - 0.5 - - Metal corrosion inhibitor Tolythriazole - - 0.5 0.5 - - - Metal corrosion inhibitor Adipic acid 1.0 1.0 1.0 1.0 Metal corrosion inhibitor Citric acid 1.0 - 1.0 1.0 - 1.0 - Metal corrosion inhibitor Sodium benzoate - 1.0 1.0 - - 1.0 - Antioxidant Sodium nitrate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Airport Airside Concrete Pavement durability inhibitor Polyacrylic acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Airport Airside Concrete Pavement durability inhibitor Sodium metasilicate 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Test Example 1

Corrosion tests on aircraft specialty metals were evaluated according to the ASTM F 483 test method and each solid composition of the preparation example according to Table 1 was dissolved in a specific concentration and the metal specimen was immersed in the solution at 38 占 폚 for 168 hours And the degree of corrosion is checked by measuring the weight change rate of the test piece. Each metal specimen shall not exceed the weight change rate specified in the SAE AMS 1431D standard (except that magnesium is immersed for 24 hours in accordance with the test method specified).

The evaluation of the solutions of solid phase compositions prepared according to Table 1 is shown in Table 2 below.

Aircraft special metal corrosion test result Item standard Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Metal corrosion test Aluminum 1 ± 0.3 -0.020 -0.026 -0.031 -0.017 -0.273 -0.296 -0.351 Aluminum 2 ± 0.3 -0.021 -0.028 -0.029 -0.101 -0.302 -0.308 -0.347 Aluminum 3 ± 0.3 -0.019 -0.032 -0.033 -0.078 -0.291 -0.328 -0.333 Magnesium (24 hr) ± 0.2 -0.167 -0.142 -0.155 -0.121 -2.374 -2.034 -2.515 titanium ± 0.1 -0.003 -0.002 -0.005 -0.012 -0.086 -0.062 -0.010 steal ± 0.8 -0.056 -0.060 -0.055 -0.074 -0.152 -0.194 -0.276

As shown in Table 2, when the solid phase composition containing triazole and organic acid and the metal corrosion inhibiting additive (mixture of triazole and organic acid) were not included, the weight change rate Only comply with the reference values stated in the SAE AMS 1431D standard. It is considered that the mixing of triazole with an organic acid improves the metal corrosion prevention performance of the ice-making composition for the aircraft special metal.

Test Example 2

The factor used as a solid snow remover for the existing airport air sludge has a disadvantage that the melting performance is significantly lowered at a low temperature of minus 10 ° C. The following test was carried out to confirm the melting performance of the metal corrosion-preventive example based on Comparative Example 3 which is 100 wt% of the organic acid salt.

For the ice-melting performance test, 130 ml of distilled water was placed in an acrylic test dish having a diameter of 23 cm and a depth of 2 cm according to the SHRP H-205.1 test method, and ice ice for 12 hours or more was prepared at the temperature to be tested. 4.2 g of each solid composition of the preparation example was prepared, sprayed with a similar distribution on ice and allowed to stand at the test temperature for 1 hour. After 1 hour, the salt solution dissolved by the snow remover was rapidly collected using a syringe and the weight of the brine was measured.

Table 3 below shows the results of the evaluation of the melting performance of the solid composition prepared in accordance with Table 1.

Results of evaluation of melting performance Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Temperature -3 ℃ 266% 269% 258% 268% 251% 249% 267% -5 ℃ 296% 314% 302% 306% 287% 288% 304% -7 ° C 413% 415% 410% 417% 408% 407% 416% -10 ° C 1135% 1161% 1145% 1142% 1124% 1128% 1160% -12 ° C The amount of urea meltblowing is 0 and the melting performance can not be calculated

1 is a graph showing the results of the evaluation of the ice-making performance according to the embodiment. As shown, it was confirmed that as the test temperature was lowered, the salt composition due to the solid-phase composition of the Example and the element as a conventional snow remediation agent was reduced.

As shown in Table 3 and FIG. 1, as a result of the evaluation of the melting performance, the solid composition of the present invention was confirmed to have a salt concentration of at least twice as much as that of the elements used in the existing airport. It was confirmed that the snow removal performance was about 10 times.

In addition, both the examples using the organic acid salt and the comparative examples showed similar results, and it was judged that the additives such as the metal corrosion inhibitor and the antioxidant contained in the icing composition of the present invention did not affect the dropping performance .

Test Example 3

The durability test for concrete pavement is evaluated according to ASTM C 672 test method. The cured concrete specimen is exposed to the icing and thawing cycle for 50 times by immersing the solution of the solid composition in the prescribed concentration to the surface of the test piece, . The specimens are rated 0-5 according to the surface condition. The lower the number of grades, the better the scaling resistance.

The results of the durability test on airport airside concrete pavement for the solid composition solution of Examples 1 to 6 described in Tables 1 and 4 are as shown in Fig. 2, and from the left, Examples 1 to 6 .

The results of the airport airside concrete durability test for the solutions of the fancy compositions of Comparative Examples 1 to 3 in Table 1 and Table 4 are as shown in Fig. 3, and are the results of Comparative Examples 1 to 3 in order from the left.

As can be seen from Fig. 3, the evaluation results of Comparative Examples 1 and 2, which contain antioxidants and concrete durability inhibitors, are superior to those of Comparative Example 3, which does not include any additives, , And a metal corrosion inhibitor (a mixture of triazole and an organic acid), the concrete scaling prevention performance was further improved in the example of the present invention (FIG. 2). It is believed that the mixing of triazole with organic acid not only improves the metal corrosion resistance of aircraft special metals but also has the function of preventing durability degradation of airport airside concrete pavement.

Manufacturing Example 2

Components (unit: wt%) Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Raw materials Sodium formate 95 94.8 97 97 100 Metal corrosion inhibitor Benzotriazole 0.5 - 0.5 - - Tolythriazole - 0.5 - - - Adipic acid 1.0 1.0 1.0 Citric acid 1.0 1.0 - 1.0 - Sodium benzoate 1.0 1.0 - 1.0 - Antioxidant Sodium nitrate 0.5 0.5 0.5 0.5 0.5 Airport Airside Concrete Pavement durability inhibitor Polyacrylic acid 0.5 0.5 0.5 0.5 0.5 Sodium meta
Silicate 0.5 0.5 0.5 0.5 0.5

Test Example 4

Using the composition shown in Table 4, the metal corrosion test, the evaluation of the melting performance, and the durability test of the airport airside concrete pavement shown in the following Table 5 were carried out, and the same tests as those in Examples 1-3 were carried out. Even when all three kinds of organic acids were used, excellent corrosion resistance of special metals and excellent scaling resistance to airport airside concrete pavement were shown, and the effect was also excellent in the evaluation of the melting performance.

Item standard Example 5 Example 6 metal
corrosion
exam Aluminum 1 ± 0.3 -0.035 -0.021 Aluminum 2 ± 0.3 -0.040 -0.027 Aluminum 3 ± 0.3 -0.038 -0.026 Magnesium (24 hr) ± 0.2 -0.176 -0.131 titanium ± 0.1 -0.004 -0.010 steal ± 0.8 -0.056 -0.066 Melting performance evaluation No degradation No degradation

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

(a) sodium formate; And (b) an azole and an organic acid as metal corrosion inhibitors.
The organic acid is a mixture of at least two organic acids selected from the group consisting of adipic acid, citric acid and benzoate.
The composition of claim 1, wherein the composition comprises: (a) 92.2-97.2 wt% sodium formate, based on the total composition; (b) 1.8 to 3.8% by weight, based on the total composition, of a metal corrosion inhibitor.
The composition of claim 1, wherein the composition comprises: (a) 92.2-97.2 wt% sodium formate, based on the total composition; (b) 0.3-0.8 wt.% azole and 1.5-3.0 wt.% organic acid relative to the total composition.
delete The icemaker composition of claim 1, wherein the azole is triazole.
delete The icemaker composition of claim 1, wherein the composition further comprises an antioxidant or a concrete durability inhibitor as an additive.
The icemaker composition of claim 1, wherein the metal is aluminum, magnesium, titanium, or steel.
8. The icemaker composition of claim 7, wherein the antioxidant is selected from the group consisting of sodium nitrate, dibutylhydroxytoluene, butylhydroxyanisole, triphenyl phosphate or combinations thereof.
The method of claim 7, wherein the concrete durability reducing agent is selected from the group consisting of sodium silicate, potassium silicate, lithium silicate, acrylic acid, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, A flame retardant, a polymeric resin, or a combination thereof.

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