KR20140046134A - Eco friendly non-chloride deicer coposig mixture of salt of organic acid - Google Patents

Abstract

The present invention relates to a deicing material, and more specifically, to an eco-friendly non-chloride deicing material formed of a mixture of organic acid salt which contains: the organic salt for improving the depression degree of a freezing point per unit weight; inorganic salt for improving the heat of dissolution and a thaw melting effect; and a base compound for preventing the corrosion of a steel material and the decrease of intensity of concrete. The eco-friendly non-chloride deicing material formed of the mixture of the organic acid is produced by comprising: 95 wt% or less of organic salt produced by a neutralization reaction after mixing one organic acid and one base compound; 20 wt% or less of base compound for improving the heat of dissolution and a thaw melting effect; and 100 g or less of alkaline compound for improving a steel material corrosion resistance function, and the amount of a mixture of the organic salt and the base compound is 100 wt%.

Description

(ECO FRIENDLY NON-CHLORIDE DEICER COPOSIG MIXTURE OF SALT OF ORGANIC ACID)

More particularly, the present invention relates to an organic acid salt for increasing the degree of freezing point drop per unit weight, an inorganic salt for enhancing the dissolution heat and a performance of the ice-melting effect, corrosion of a steel material, Based organic snow remover comprising a mixture of an organic acid salt to which a basic compound is added.

Currently, sodium chloride (NaCl) and calcium chloride (CaCl ₂ ) are used as snow removing agents and they are used to smooth traffic on highway when snowing in cold winter.

The purpose of spraying snow removers on highways and bridges is to melt snowy roads on the road, prevent re-icing of road water, and to separate snow from the road surface to facilitate snow removal. In addition, To improve the sliding friction resistance coefficient.

Generally, snow removal products are chloride based such as sodium chloride, calcium chloride and magnesium chloride, and calcium, magnesium and urea. Of these, chloride based snow removing agents are used most frequently because they are inexpensive.

Chloride-based snow removing products have a serious adverse effect on automobiles, facility structures and ecosystems due to their strong toxicity and corrosiveness, but there are few products to replace them. In addition, due to the strong corrosiveness of calcium chloride and sodium chloride, the durability of roads, bridges, vehicles, and structures are greatly affected and the ecosystem is affected by groundwater, river and soil pollution. Therefore, in developed countries, We are concentrating on the development of environmentally friendly snow removers.

In this respect, in the case of the major developed countries, in the case of the United States, sodium chloride and crushed sand are mixed at a temperature of minus 5 degrees Celsius. In the case of less than minus 5, the amount of sodium chloride is reduced or calcium chloride is mixed with crushed sand have.

In Canada, sodium chloride is mainly used, and sand is used when road surface freezing is necessary.

In Switzerland, sodium chloride and sodium chloride solution are mixed and sprayed mainly. Mountain and city sidewalks are sprayed with sand, and automatic deicing agent spraying system is installed and operated on bridges.

In the case of Japan, special legislation for securing road traffic in the winter / cold regions has been established and the designated routes have been designated. Especially, we developed new technology of slush removal equipment, snow melting facility using wind power, and snow melting snow melting facility using waste heat.

In Korea, chloride-based solid snow removers such as calcium chloride and sodium chloride are generally used for snow removal. Due to the strong toxicity of chlorides, it causes corrosive effects directly on facilities, structures and vehicles. Destruction is serious.

Since calcium chloride or sodium chloride exists in the presence of chloride ions, it reacts with iron (Fe) to form iron chloride (FeCl ₂ ) rapidly, which seriously corrode automobiles, reinforcing bars and steel structures

In addition, the damage caused by the inflow of dissolved calcium chloride or sodium chloride into the soil and the river is the main cause of environmental pollution caused by road and soil acidification, and the degree of the damage can not be calculated by the amount.

To solve these drawbacks, Patent No. 10-0977739 is disclosed.

The low chloride-based liquid snow removing agent according to the above-mentioned Patent No. 10-0977739 contains 38-45% of magnesium chloride, 3-6% of sodium acetate, 2-5% of glycerin, 1-3% of sodium citrate, As a liquid-phase removers, although the content of chlorine was reduced, it still contained chlorine, which did not solve the fundamental problem of containing chlorine.

In order to solve this problem, Patent No. 10-588820 was proposed.

The non-chloride based liquid snow removing agent according to the above-mentioned Patent No. 10-588820 has a disadvantage in that it is costly and has a lag in the quickness of the snow removing effect as compared with the chloride system.

Patent No. 10-0977739 Patent No. 10-588820

The present invention has been conceived to solve the above-mentioned problems. It is an object of the present invention to provide an organic acid salt for increasing the degree of freezing point per unit weight and an inorganic salt for enhancing the heat of dissolution and improvement of the melting effect, And a mixture of an organic acid salt to which a base compound is added to decrease the strength of the organic acid salt.

In order to accomplish the above object, the non-chloride-based eco-friendly snow removers composed of a mixture of organic acid salts according to an embodiment of the present invention include acetic acid and formic acid, which are produced through fermentation or oxidation of components obtained from plants and animals, (NaOH), potassium hydroxide (KOH) and calcium hydroxide (Ca (OH) ₂ ), which are hydroxides of an organic acid and fumaric acid and alkali metal or alkaline earth metal, Not more than 95% by weight of an organic acid salt prepared through the reaction; A basic compound which is not more than 20% by weight of any one of sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), magnesium sulfate (MgSO ₄ ) and sodium sulfate (Na ₂ SO ₄ ) And an alkali compound which is not more than 100 g of any one of sodium hydroxide (NaOH), potassium hydroxide (KOH) and calcium hydroxide (Ca (OH) ₂ ) for enhancing the corrosion resistance of the steel, Is 100% by weight.

According to the above-mentioned problem solving means, the non-chloride-based environmentally friendly snow removers composed of the mixture of organic acid salts according to the present invention are characterized in that first, chlorine is not contained and harmful to the plants around the road, Secondly, it is possible to reduce the environmental pollution caused by the acidification of the soil caused by the influx, and secondly, the inorganic salt is included to increase the heat of dissolution and the effect of the melting of the marble to improve the speed of the snow removal effect. Thirdly, .

FIG. 1 is a graph showing changes in surface temperature of ice sprayed with a non-chloride-based environmentally friendly snow remover composed of a mixture of organic acid salts according to the present invention,
FIG. 2 is a graph showing changes in the degree of melting (%) of ice sprayed with a non-chloride-based environmentally friendly snow remover composed of a mixture of organic acid salts according to the present invention with time,
FIG. 3 is a graph showing the amount of change in dissolution heat according to the blending ratio as the organic acid salt is fixed.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings.

The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Like reference numerals refer to like elements throughout the specification.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a non-chlorine-based eco-friendly snow remover comprising a mixture of an organic acid salt according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings, wherein some constructions not related to the gist of the invention are omitted or compressed, Therefore, the present invention is not necessarily required for the present invention, and can be used by a person having ordinary skill in the art to which the present invention belongs.

Soluble organic acids produced by oxidation or fermentation from organic sludge such as sewage sludge (precipitate from sewage treatment or water purification process), animal, vegetable and food waste are useful as external carbon source for the biological nitrogen removal process for wastewater And the use range thereof as a base material of a polymer material is expanding.

Organic acid can also be used as a liquid type environmentally friendly snow remover.

Organic acids such as acetic acid produced by oxidation or fermentation of wastewater are similar to sodium chloride due to the freezing point drop. They are very small in their corrosivity and are dissolved in water and decomposed by bacteria, It has advantages.

 Therefore, when organic acids are produced from organic sludge such as wastewater by oxidization or fermentation, it is possible to achieve two effects at the same time: low-cost wastewater treatment and production of a liquid type environmentally friendly snow remover

The main organic acids used in the present invention are chlorine-free compounds that can be easily obtained by fermentation or oxidation of animal or plant organisms. Examples of the organic acids include acetic acid, formic acid, fumaric acid, succinic acid succinic acid, and oxalic acid.

A salt of organic acid is formed by an acid / base neutralization reaction between the organic acid and the base.

The base is an alkali metal such as sodium, potassium, calcium or magnesium or a hydroxide of an alkaline earth metal. Examples of the base used for neutralizing the organic acid include sodium hydroxide (NaOH), potassium hydroxide (KOH) OH) ₂ ) and the like.

In order to increase the degree of freezing point per unit weight as a snow removing agent, a neutralization reaction is performed mainly on organic acids and bases for neutralization and with low atomic weight and low molecular weight, and sodium acetate (Ace- N), potassium acetate (Ace-K), sodium formate (For-N), and sodium fumarate (Fum-N).

In order to increase the heat of dissolution of the organic acid salt and improve the effect of the cooling effect of the organic acid salt, inorganic salt 20 (inorganic salt) which generates 95% by weight or less of the organic acid salt and Na ⁺ , K ⁺ , or Ca ^{2 +} By weight or less.

Representative inorganic salts to be added include sodium carbonate (Na ₂ CO ₃ ), sodium hydrogencarbonate (NaHCO ₃ ), magnesium sulfate (MgSO ₄ ), and sodium sulfate (Na ₂ SO ₄ ).

The mixture of the organic acid salt and the base compound is 100% by weight.

(NaOH), potassium hydroxide (NaOH), and the like, so that the pH of the road surface is in a range of 8 to 11 when the snow remover dissolves in order to suppress the corrosion of the steel material by the spraying of the snow remover mixture and the decrease in the strength of the concrete KOH) and calcium hydroxide (Ca (OH) ₂ ) are added in an amount of not more than 100 g per 100 kg of the mixture of the organic acid salt and the inorganic salt.

Unlike sodium chloride and calcium chloride, the mixture snow removing agent does not contain chlorine, thereby reducing the saltiness of plants around roads and reducing environmental pollution.

Hereinafter, a preparation example of a non-saline type environmentally friendly snow remover comprising a mixture of an organic acid salt according to the present invention will be described.

[Manufacturing Example 1]

The concentration of the road surface on the road surface is 2%, the acidity of the road surface is maintained at pH 9, and the mixture weight of the organic acid salt and the inorganic salt is 100 kg.

Organic acid salt and weight (kg) Inorganic salt and weight (kg) Base and amount added (g) One Sodium acetate 95 Sodium sulfate 5 NaOH 2 2 Sodium acetate 90 Sodium sulfate 10 KOH 2 3 Sodium acetate 85 Sodium carbonate 15 Ca (OH) ₂ 2 4 Sodium acetate 40 Sodium hydrogencarbonate 20 NaOH 2 Potassium acetate 40

[Manufacturing Example 2]

It is the case that the road surface concentration of the snow remover is 4% by spraying the snow remover, the acidity of the road surface is maintained at pH 11, and the mixed weight of the organic acid salt and the inorganic salt is 100 kg.

Organic acid salt and weight (kg) Inorganic salt and weight (kg) Base and amount added (g) One Sodium acetate 95 Sodium sulfate 5 NaOH 100

A test example of a non-saline type eco-friendly snow remover comprising a mixture of an organic acid salt according to the present invention will be described.

[Test Example 1]

This is a test example comparing the temperature change and the dissolution rate with time for the existing snow remover when the organic acid salt is sprayed on ice.

Place ice granules in a Petri dish, sprinkle each prepared organic acid salt evenly, place each Petri dish in the refrigerator, measure the surface temperature using a surface thermometer every 5 minutes, and visually observe the degree of melting.

FIG. 1 is a graph showing changes in surface temperature of ice sprayed with a non-saline-based environmentally friendly snow remover composed of a mixture of organic acid salts according to the present invention. (%) Of ice sprayed over time.

As shown in FIGS. 1 and 2, the surface temperature of ice after the organic acid salt spraying drops sharply and then gradually rises.

Fum-N has the lowest temperature and CaCl ₂ has the lowest temperature at the beginning.

CaCl ₂ The temperature rises relatively quickly after 5 minutes and melts first.

In the case of Fum-N, the temperature is slightly lower at the beginning and is not the most soluble.

In case of Ace-K, the temperature is lowest at -28 after 10 minutes, and the temperature rises steadily.

As the salt melts in the ice granules, the freezing point is lowered, and the surface temperature drops sharply.

After 60 minutes, the sample showed a similar surface temperature when compared to the control, but all of the samples sprayed with the salt were found to be melted.

[Test Example 2]

The steel corrosivity test is a test in which a nail is put into a solution of an organic acid salt and a mixture thereof to visually observe it.

For comparative tests, the same concentrations of calcium chloride and sodium chloride are used for comparison.

Table 3 shows the results of the nail steel corrosion test of the organic acid salts contained in the non-chlorine-based environmentally friendly snow removers composed of the mixture of organic acid salts according to the present invention.

NaCl CaCl ₂ Tap water Ace-N Ace-K For-N Fum-N One week

Three weeks

5 weeks later

As shown in Table 3, For-N, Ace-K, and Ace-N are similar to or more severe than conventional snow removers.

It can be seen that Fum-N is very low in corrosiveness, and that additives for preventing corrosion are required when For-N, Ace-K and Ace-N are used as snow removing agents.

In order to investigate the effect of mixing with organic acid salt only on the corrosion of steel, Ace-N, which exhibits high corrosion resistance, and Fum-N, which exhibits the lowest corrosion resistance, were mixed at a ratio of 95%: 5% same.

Ace-N (95%) + Fum-N (5%) After 3 weeks

Ace-N three weeks later

As shown in Table 4, when a small amount of Fum-N was added, it was confirmed that the corrosion resistance of the nail was remarkably decreased, and that the organic acid salt Fum-N had a corrosion inhibiting effect.

Table 5 shows the results of the nail steel corrosion test of the inorganic salts contained in the non-chlorine-based environmentally friendly snow removers composed of the mixture of organic acid salts according to the present invention.

NaCl MgSO ₄ (pH 7) Na ₂ SO ₄ (pH 7) Na ₂ CO ₃ (pH 11.68) NaHCO ₃ (pH 8.36) After 1 week

After 3 weeks

After 5 weeks

As shown in Table 5, MgSO ₄ , Na ₂ SO ₄ are comparable or slightly less corrosive as compared to NaCl, and Na ₂ CO ₃ and NaHCO ₃ show less corrosivity.

Tests were conducted to determine whether the low corrosivity of basic Na ₂ CO ₃ , NaHCO ₃ is associated with pH.

The results of forced corrosion under acidic and basic conditions are shown in Table 6.

Cacl ₂ (pH 10.77) Cacl ₂ (pH 3.02) Distilled water + HCL (pH 3) Distilled water + NAOH (pH 10.05) After 1 week

After 3 weeks

After 5 weeks

As shown in Table 6, when the pH is high, the basicity is low, and when it is acidic and neutral, it is highly corrosive.

[Test Example 3]

This is a dissolution heat test in which the heat of dissolution generated when an aqueous solution of an organic acid salt compound is prepared is measured using a calorimeter.

Because ice absorbs heat when it melts, it is necessary to investigate the heat of dissolution that is related to the melting characteristics of each material through literature and actual measurements, since the material that exothermally dissolves is the snow melting material.

In the dissolution heat test method, 250 ml of distilled water is filled in the calorimeter, the calorimeter is closed, the temperature is stabilized, the initial temperature is measured, and 10 g of the sample to be measured for dissolution heat is measured.

The heat of dissolution of the organic acid salt and the inorganic salt is shown in Table 9.

matter T0 (占 폚) T1 (° C) ΔT (° C) Sample dissolution heat (kj / mol) NaOH 24.8 32.2 7.4 30.96 KOH 25.3 31.8 6.5 38.15 CaCl ₂ 25.4 30 4.6 53.41 NaCl 24.9 24.5 -0.4 -2.45 Ace-N 24.8 26.2 1.4 12.01 Ace-K 24.7 25.6 0.9 9.24 For-N 24.9 24.8 -0.1 -0.71 Fum-N 25.8 25.6 -0.2 -3.35 Sodium nitrate 25.1 23.3 -1.8 -16.00 Calcium nitrate 24.4 23.5 -0.9 -22.23 Magnesium acetate 24.8 25.3 0.5 11.22 Na ₂ CO ₃ 25.5 27.3 1.8 19.95 NaHCO ₃ 24.8 23.2 -1.6 -14.06 MgSO ₄ 24.5 29.1 4.6 57.91 Na ₂ SO ₄ 24.6 24.9 0.3 4.46

As shown in Table 9, the organic acid salt has a lower heat of dissolution than that of CaCl ₂ , and Ace-K and Ace-N exothermic, and For-N and Fum-N exothermic.

In inorganic salts MgSO ₄ , Na ₂ CO _{3 ,} Na ₂ SO ₄ exothermic and NaHCO ₃ exothermic.

FIG. 3 is a graph showing the amount of change in the dissolution heat of the inorganic salt depending on the weight% of each organic acid salt, and FIG. 4 is a graph showing the amount of change in dissolution heat of the organic acid salt according to the weight% of each inorganic salt.

FIG. 3 shows that the calorific value of the inorganic salt according to the weight% of each organic acid salt is in the order of MgSO ₄ > Na ₂ CO ₃ > Na ₂ SO ₄ > NaHCO ₃ .

The present invention is not limited to the above-described embodiment, but may be modified in various ways within the scope of the following claims. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

Sodium hydroxide (NaOH), hydroxide, which is a hydroxide of an organic acid of any of acetic acid, formic acid, and fumaric acid, which is produced through fermentation or oxidation of components obtained from animals and plants, and alkali or alkaline earth metals. 95% by weight or less of an organic acid salt prepared by mixing a base compound of any one of potassium (KOH) and calcium hydroxide (Ca (OH) ₂ ) through a neutralization reaction;
A basic compound which is not more than 20% by weight of any one of sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), magnesium sulfate (MgSO ₄ ) and sodium sulfate (Na ₂ SO ₄ ) And
Alkali compound which is 100 g or less of any one of sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca (OH) ₂ ) to increase steel corrosion resistance performance;
A non-chloride-based eco-friendly snow removing agent prepared by comprising a mixture of the organic acid salt is a mixture of the organic acid salt and the base compound 100% by weight.
The method of claim 1,
Wherein the organic acid is produced by fermentation or oxidation of waste water sludge or food waste, wherein the organic acid salt is a mixture of organic acid salts.
The method of claim 1,
The organic acid is a mixture of organic acid salts, characterized in that succinic acid (lucci acid), lactic acid (lactic acid), citric acid (citric acid), malic acid (malic acid), propionic acid (maleic acid), etc. Non-chloride eco-friendly snow removal agent.
The method of claim 1,
The organic acid salt is a sodium chloride (sodium acetate), potassium acetate (potassium acetate), sodium formate (sodium formate), sodium fumarate (sodium fumarate) and the like non-chloride eco-friendly snow removal agent consisting of a mixture of salts.
The method of claim 1,
wherein the pH of the mixture is between 8 and 11.

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