KR101280589B1 - The liquid snow removal agent of ecofriendly non-chloride type using industrial byproduct and the production method thereof - Google Patents

Abstract

The present invention relates to an environment-friendly non-chloride liquid snow removal agent composition using industrial by-products and a method for manufacturing the same, and to provide a non-chloride liquid snow removal agent composition utilizing industrial by-products generated during the production of high-performance water reducing agent for sodium aluminate and concrete. It is related. The present invention is useful for preventing the recrystallization of the organic acid salt 20 to 60% by weight, which is produced by adding acetic acid and / or formic acid to the sludge powder obtained by heating and then pulverizing the sludge generated in the manufacturing process of sodium aluminate 0.1 to 3.0% by weight of microorganisms, 1 to 5% by weight of alkali compounds generated as by-products in the production of high-performance water-reducing agents for concrete, non-chloride liquid desulfurizer comprising 0.001 to 2.0% by weight of nitrite as a corrosion inhibitor and the remaining water Composition.

Description

The liquid snow removal agent of ecofriendly non-chloride type using industrial byproduct and the production method

The present invention relates to an environment-friendly non-chloride liquid snow removal agent composition using industrial by-products and a method for manufacturing the same, and to provide a non-chloride liquid snow removal agent composition utilizing industrial by-products generated during the production of high-performance water reducing agent for sodium aluminate and concrete. It is related.

In the case of Korea, the snow removal is made in large quantities for the winter traffic safety in the snowy cold regions, and the amount of spraying is increasing every year. Generally used snow removing agents are mainly based on chlorides such as calcium chloride (CaCl ₂ ) and sodium chloride (NaCl), and most of them use calcium chloride in Korea. The chloride contained in the calcium chloride snow remover penetrates into the road structures, causing corrosion of the reinforcement due to salt damage, causing structural degradation in the actual pavement or damaged bridge structures, and in combination with the winter east sea, causing surface scaling. In particular, water pollution caused by snow removal agent has caused serious side effects from the environmental point of view. In addition, the deterioration of the concrete pavement surface is further accelerated after the use of calcium chloride snow remover. On the other hand, in addition to these environmental problems, calcium chloride has a problem that is easily re-frozen due to the lack of sustainability in the process of dehumidification after snow removal.

Various non-chloride-based snow removal agents have been developed to solve the above problems of chloride snow removal agents, and urea, calcium magnesium acetate (CMA), CMO, and the like are known. The ice making effect of CMA is similar to that of salt, and it is very corrosive and dissolves in water. After that, calcium ions and magnesium ions become nutrients to soil organisms, and acetate ions are biodegraded by bacteria, which is very dangerous for environmental pollution. little. Nevertheless, mass production is not achieved, and the main reason is high production costs. In addition, Korean Patent Registration No. 0588820 discloses a non-chlorinated liquid snow preparation composition including potassium acetate, disodium succinate, dipotassium succinate, ethylene glycol, ethanol, and PVA aqueous solution, but ethanol, PVA, It is true that since it uses a large amount of hardly decomposable organic substances such as ethylene glycol, the burden on the environment is very high and it is difficult to commercialize it at a high cost.

On the other hand, sodium aluminate (NaAlO ₂ ) is currently the most widely used in Korea as a fastener is classified into a liquid type and powder type. Sodium aluminate-based liquid filler is composed of Na ₂ O and Al ₂ O ₃ in a molar ratio of about 1.3 to 1.6, the total solid content is about 30 to 45%. Sodium aluminate is made by dissolving bauxite in a high concentration of caustic soda (NaOH) solution under heating and pressurization. The sludge produced during the manufacturing process contains Al (OH) ₃ and a significant amount of sodium. Sludge may be used for the manufacture of high purity alumina, but it contains a large amount of sodium. In order to manufacture high purity alumina, special processes such as Bayer method are required. This can be urgent.

When reviewing the development status of non-chlorinated snow removers up to now, it has achieved great results in partially alleviating and solving problems such as degradation of civil engineering and building structures and destruction of ecosystems, which are side effects of conventional chloride-based snow removers. Due to the increase in cost, there is a limit to its application, and it is being used only in special sites such as airports. Therefore, the present inventors have excellent snow removal when the organic acid produced by applying acetic acid and formic acid to the industrial by-products generated during the manufacturing process of sodium aluminate and the alkali compound, which is an industrial by-product generated when the high-performance water reducing agent for concrete is used, is diluted with water. The present invention was completed by confirming that deterioration and environmental pollution of road structures were greatly reduced when the useful microorganism group (EM) and nitrite, which exhibited ice-melting performance and retention performance and had excellent antioxidant ability, were added.

The purpose of the present invention is to contribute to the eco-friendly aspect by recycling the industrial by-products that are disposed of, and to solve the problems such as deterioration and environmental pollution of the structure that occurs when using the existing snow removal agent, as well as can effectively exhibit snow and ice melting performance. It is to provide a non-chloride liquid snow removal agent composition.

The present invention for achieving the above object is 20 to 60% by weight of an organic acid produced by adding acetic acid and / or formic acid to the sludge powder obtained by heating the sludge generated in the manufacturing process of sodium aluminate, and then pulverized, the organic acid A non-chloride liquid snow preparation composition comprising 0.1 to 3.0% by weight of the useful microorganism group and the remaining water to prevent recrystallization of the salt.

In addition, it is preferable that the composition further comprises 1 to 5% by weight of an alkali compound generated as a by-product in the production of a high performance water-reducing agent for concrete.

In addition, it is preferable that the composition further comprises 0.001 to 2.0% by weight of nitrite as a corrosion inhibitor.

The nitrite is preferably selected from the group consisting of sodium nitrite and calcium nitrite, and the alkali compound is preferably selected from the group consisting of Na ₂ SO ₄ (manganese) and caustic soda (NaOH).

In addition, the useful microorganism is preferably selected from the group consisting of photosynthetic bacteria, yeast, useful actinomycetes, yeast fungi, the sludge powder is preferably Al ₂ O ₃ + Na ₂ O content of 90% by weight or more.

And, the freezing point of the composition is preferably -20 ~ -60 ℃.

Preferably, 20 to 60% by weight of organic acid salt formed by adding acetic acid and / or formic acid to the sludge powder obtained by heating and then pulverizing the sludge generated in the manufacturing process of sodium aluminate, as a by-product in the production of high performance concrete for concrete 1 to 5% by weight of the alkali compound to be produced, 0.1 to 3.0% by weight of the useful microorganism group (EM), 0.001 to 2.0% by weight of nitrite, and the remaining amount are non-chlorinated liquid snow removal compositions composed of water.

In addition, the present invention comprises the steps of pulverizing the powder by heating the sludge generated in the manufacturing process of sodium aluminate; Preparing an organic acid salt by adding acetic acid and / or formic acid to the finely ground powder; Obtaining an alkali compound from by-products generated during the preparation of a high performance concrete for concrete; A non-chlorinated liquid snow removing agent comprising: 20 to 60% by weight of the organic acid salt, 1 to 5% by weight of the alkali compound, 0.1 to 3.0% by weight of the useful microorganism, and the remaining water; Provided are methods for preparing the composition. And, the nitrite-based corrosion inhibitor further comprises 0.001 to 2.0% by weight further comprising the step of making a liquid phase.

Hereinafter, the present invention will be described in detail.

Sodium aluminate is produced in a high concentration of caustic soda (NaOH) solution and always contains a significant amount of sodium as impurities, and co-precipitation of sodium oxide when precipitation of aluminum hydroxide is obtained as industrial by-products. When the industrial by-products are pulverized and reacted with acetic acid and / or formic acid, organic acid salts of aluminum acetate, sodium acetate and / or aluminum formate and sodium formate may be obtained. Since the organic acid salt has an excellent freezing point strengthening effect, the organic acid salt may lower the freezing point of water and serve as a snow removal and melting agent. In particular, the point of strengthening effect of aluminum acetate and aluminum formate is excellent. When the industrial by-product is heated at about 250 to 350 ° C. and then pulverized and added to acetic acid, mainly aluminum acetate and sodium acetate are produced. When formic acid is added, mainly aluminum formate and sodium formate are produced. It is a very environmentally friendly idea.

The organic acid salt is preferably contained 20 to 60% by weight. Since acetic acid and formate have the characteristic of freezing point drop, the aqueous solution is generated by the solubility and freezing point drop when it comes in contact with snow or ice, and continuously reacts with the surrounding snow or ice to show the overall snow removing effect. If the organic acid salt is less than 20% by weight, an effective snow removal effect may not be obtained. If the organic acid salt is more than 60% by weight, crystal precipitation may increase due to solubility, which may cause problems in snow removal. In addition, the industrial by-product sludge powder used in the present invention is preferably Al ₂ O ₃ + Na ₂ O content of 90% by weight or more. The bauxite is dissolved in a sodium hydroxide (caustic soda) solution under a heated pressurized environment to produce sodium aluminate. In addition to the aluminum component, the bauxite contains impurities such as SiO ₂ , Fe ₂ O ₃ , TiO ₂ , When the organic acid is prepared, it may be included in the crystalline state, which is not formed as a salt, and may exhibit poor solubility. These may act to reduce the snow removal effect when applied to a snow removing agent. When the Al ₂ O ₃ and Na ₂ O content is less than 90% by weight, it does not show sufficient snow removal effect by reducing the amount of organic acid salt produced, and the precipitated impurities may cause traffic accidents by reducing the frictional force of the road after thawing, Generated as dust and adversely affect the environment.

In the present invention has the advantage of utilizing industrial by-products, and utilizes effective microorganisms (EM) in order to sufficiently maintain and exert the snow removal effect. Microbial group consisting of photosynthetic bacteria, yeast, useful actinomycetes, yeast fungus, etc. has a strong antioxidant capacity and polymer decomposition performance, and can be called a harmless and environmentally friendly material. The antimicrobial activity of the microorganisms useful in the composition of the present invention not only acts to remove the specific odor of the liquid snow removing agent composition, but also prevents the recrystallization of organic acid salts due to the polymer decomposition performance, thereby preventing the degradation of the recrystallization during the application of the snow removing agent. It works. When the amount of the useful microorganism is 0.1% or less, the specific odor removal and recrystallization prevention performance is insignificant, and when 3.0 wt% or more, the performance of the liquid snow removing agent composition is inhibited due to excessive polymer decomposition.

On the other hand, in the present invention, the alkaline compound generated during the production of a high performance water-reducing agent for concrete is utilized as a component of the liquid snow removing agent composition. High performance water reducing agents for concrete are mainly lignin-based, naphthalene-based, polycarbon-based, melamine-based. Such high-performance concrete supervisors are manufactured through complex processes such as sulfate reaction, condensation reaction and neutralization reaction. The product produced through the condensation reaction is neutralized to give the final product. In the neutralization reaction, caustic soda (NaOH) is added to maintain the pH of the intermediate product at 7.5 to 8.5. At this time, the caustic soda is combined with the sulfated reactant to precipitate as manganese (Na ₂ SO ₄ ), and the unreacted caustic soda is generated as an industrial by-product through the filtration process. In the composition of the present invention, the forget-me-not and caustic soda contained in the industrial by-products have a heat storage capacity, thereby maintaining the heat generated by the reaction of the snow removal agent and the eye for a long time, thereby improving the performance of the snow removal agent, 1 wt% When added below, the performance is insignificant, and when added in more than 5% by weight, the basicity of the snow removal agent may be excessively high, which may affect vegetation growth during use.

In the present invention, a corrosion inhibitor may be further added and used, and it is preferable to use a nitrite system. Nitrite is mainly used for oxidizing agent and organic synthesis and acts easily to prevent corrosion of rebar. The nitrite used in the composition of the present invention is preferably selected from the group consisting of sodium nitrite and calcium nitrite, if less than 0.001% by weight does not exhibit sufficient reinforcing bar corrosion protection performance, if more than 2.0% by weight, excess of nitrite Oxidative properties may also promote rebar corrosion.

In addition, the present invention introduces a process for preparing an organic acid salt which can be used as a major component of a snow removing agent by heating and pulverizing sludge generated in the manufacturing process of sodium aluminate and adding acetic acid and / or formic acid.

The present invention can provide an environmentally friendly liquid snow removal agent utilizing industrial by-products. In addition, the use of useful microorganisms and industrial by-products of alkali compounds can improve the snow removal performance, and because it is a non-chloride-based snow removal agent solves the problems of conventional chloride-based snow removal agent, and is quite economical.

Hereinafter, the present invention will be described in more detail based on the following examples. It should be noted, however, that the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The present invention is not limited to the following examples. Will be apparent to those skilled in the art to which the present invention pertains.

<Preparation of sample>

The sludge generated in the manufacturing process of sodium aluminate used as a fastener was pulverized and powdered, and then acetic acid was added to prepare acetate. In addition, the useful microorganism group used yeast. As an industrial by-product of the high-performance water reducing agent, a mixture of forget-me-not and caustic soda was used as an alkali compound, and sodium nitrite was used as a corrosion inhibitor. As a contrasting sample, calcium chloride was used as a comparative example. On the other hand, formic acid was added to the sludge powder to produce formic acid, which showed excellent snow removal performance as in the case of using acetate.

Table 1 below shows the liquid phase mixing ratios of Examples and Comparative Examples belonging to the present invention. Each unit is weight percent.

Organic acid salt alkali
compound utility
Microbial group Sodium nitrite Calcium chloride water Example 1 60.0 3.0 1.0 0.1 - 35.9 Example 2 40.0 2.0 0.5 0.1 - 57.4 Example 3 20.0 1.0 0.2 0.1 - 78.7 Example 4 60.0 1.0 0.1 - 38.9 Example 5 50.0 3.0 0.1 - 46.9 Example 6 60.0 1.0 - 39.0 Example 7 60.0 1.0 1.0 0.1 - 37.9 Comparative Example 1 - - - - 40.0 60.0 Comparative Example 2 - - - - 20.0 80.0 Comparative Example 3 60.0 40.0

<Crystalization Control Performance Comparison>

The recrystallization was evaluated according to the addition of useful microorganisms and the absence of useful microorganisms. Recrystallization was induced by slowly volatilizing the solvent of the liquid snow removing agent in room temperature air, and after 10 days, the presence or absence of recrystallization was visually evaluated. In Examples 1 to 4, an organic acid salt, an alkali compound, a useful microorganism group, and sodium nitrite were prepared in a form containing all, and Example 5 was prepared in a form not including the useful microorganism group. In order to clarify the action between the organic acid salt and the useful microorganism group, Comparative Example 3 and Example 6 prepared the organic acid salt of the organic acid salt and the useful microorganism group added.

In Comparative Example 3, as the solvent was evaporated, recrystallization was performed, whereas Example 6 did not show recrystallization. In other words, it was found that the useful microorganisms affect the degree of recrystallization of the organic acid salt used in the present invention. Recrystallization did not occur even when other components were included as in Examples 1 to 4, and in Example 5, recrystallization was observed. Recrystallization of organic acid salts is greatly controlled due to the excellent polymer resolution of the useful microorganisms, and it is expected that the deterioration factors that can be caused by precipitation of crystallized snow during snow spraying can be greatly improved. Even when other components such as alkali compounds are included as in the preferred embodiment of the present invention, the useful microorganism group has a significant effect on preventing recrystallization of the liquid snow removing agent of the present invention. On the other hand, in Comparative Examples 1 and 2, as the evaporation of the solvent occurs, crystal precipitation occurs and still has a conventional problem.

<Special Odor Removal Effect>

Deodorization characteristics were evaluated by 10 subjects for each sample. In general, the snow removal agent containing the useful microbial group did not smell, but if it does not include a lot of evaluation that feels a little smell. Deodorization evaluation results show that the odor peculiar to the snow removal agent is significantly removed due to the ability to remove the specific odor of the useful microorganism group.

<Comparison Result of Exothermic Temperature Maintenance Performance>

In order to evaluate the temperature retention performance of the non-chlorinated liquid snow removal agent of the present invention, after preparing ice specimens having a width of 30 cm and a thickness of 4 cm, the snow removal agents of the examples and the comparative examples were sprayed, respectively, and the ice making effect was compared and tested. The results are shown in Table 2. In the case of the addition of the alkali compound generated in the production of high-performance water-reducing agent for concrete, Example 4 without the addition of alkali compound while showing a high temperature retention performance up to 30 minutes of spraying due to the heat storage capacity of the forget-me-not and caustic soda , Comparative Example 1, Comparative Example 3 shows a large temperature drop due to heat exchange with ice after 30 minutes of spraying. In particular, in the case of Comparative Example 1, after the high temperature rise by the decomposition of calcium chloride immediately after the spraying, a sudden temperature drop result was shown. In Examples 1, 2, and 3, the content of the alkali compound was adjusted according to the content ratio of the organic acid salt, and the content ratio of the organic acid salt and the alkali compound was the same. According to the organic acid content ratio, the difference in temperature immediately after spraying appears, and the difference in temperature change 30 minutes after spraying seems to be due to the difference in initial temperature. In the case of Example 4 and Comparative Example 3, the heat storage capacity seems to be low because the alkali compound is not included, and the calcium chloride of Comparative Example 1 is considered to be inferior in the overall heat storage capacity, and thus, as in the present invention, the organic acid salt and the alkali When used together, it may be helpful to improve heat storage capacity.

Example 1 Example 2 Example 3 Example 4 Example 7 Comparative Example 1 Comparative Example 3 Temperature immediately after spraying (℃) 25 22 20 23 25 36 25 Temperature after 30 minutes of spraying (℃) 16 13 11 5 12 3 3

<Freezing point drop and ice making performance comparison result>

In order to measure the freezing point of each sample, 50 g of the sample was added to an ultra-cold freezer, and the freezing point was measured while falling to 90 ° C. In addition, in order to evaluate the melting performance of the liquid snow-drier composition, after spraying 200g of the snow-driver sample to 1000g of ice prepared at -20 ℃ each, the amount of melted for 10 minutes was measured, the results are shown in Table 3. Overall, as the dilution ratio of water decreases, the freezing point drops and the amount of ice melt increases. It was confirmed that the non-chlorinated liquid snow removing agent exhibits an excellent freezing point drop performance compared to Comparative Example 1 and Comparative Example 2, which is a chloride snow removing agent, and the amount of melted ice also has an excellent performance equal to or higher than that of the chloride snow removing agent. This shows that even when a small amount of non-chloride snow removal agent is sprayed compared to the chloride snow removal agent, effective snow melting and thawing are possible, and the re-freezing prevention performance after snow melting and thawing is excellent. In comparison with Examples 1 to 3, the higher the content of the organic acid salt, the lower the freezing point and the higher the amount of melting. The same is true for the fourth to seventh embodiments. However, the ones containing alkali compounds are expected to have a higher sustained melt amount than the other ones as described above.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Point (℃) -59.1 -41.5 -29.8 -54.0 -47.3 -54.1 -56.5 -30.6 -18.6 Melting amount (g) 59 51 45 56 54 55 57 49 37

<Corrosion test of metal>

After immersing the iron plate in the liquid snow removing agent composition prepared in Examples and Comparative Examples for 4 days, the weight change of the sample was measured and the discoloration result was confirmed. Table 4 shows the results.

Example 1 Example 2 Example 3 Example 4 Example 6 Comparative Example 1 Comparative Example 2 Weight change none none none none Slight differences has exist has exist Discoloration or not none none none none Slight differences has exist has exist

In the case of the addition of the preservative, there was no change in weight as well as discoloration. In the case of Example 6, there was a very slight weight change and discoloration due to the addition of a corrosion inhibitor, but this was not a significant level. In total, the non-chloride snow removal agent of the present invention seems to have solved the corrosion problem of the metal. However, if a longer time is expected to have some significant difference, it may be more advantageous to use a corrosion inhibitor together. In the case of Comparative Example 1 and Comparative Example 2, the weight change and discoloration are considered to have a serious influence on the corrosion problem of the metal, and the present invention solves this problem.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention, and are not intended to limit the scope of the invention. .

Claims (9)

20 to 60% by weight of organic acid salt formed by adding acetic acid and / or formic acid to the sludge powder obtained by heating and pulverizing the sludge generated in the manufacturing process of sodium aluminate, consisting of photosynthetic bacteria, yeast, useful actinomycetes and yeast fungus Non-chlorinated liquid snow preparation composition comprising 0.1 to 3.0% by weight of the microorganism selected from the group and the remaining water.
The method of claim 1,
Non-chlorinated liquid snow preparation composition, characterized in that it further comprises 1 to 5% by weight of an alkali compound generated as a by-product in the production of a high performance water-reducing agent for concrete.
The method of claim 2,
Non-chlorinated liquid snow preparation composition characterized in that it further comprises 0.001 to 2.0% by weight of nitrite as a corrosion inhibitor.
The method of claim 3,
The nitrite is sodium chloride, calcium nitrite non-chloride liquid snow removal agent composition, characterized in that selected from the group consisting of.
The method of claim 2,
The alkali compound is a non-chloride liquid snow removal agent composition, characterized in that selected from the group consisting of Na ₂ SO ₄ (forget-me-not), caustic soda (NaOH).
delete 6. The method according to any one of claims 1 to 5,
The sludge powder is a non-chloride liquid snow removal agent composition, characterized in that the Al ₂ O ₃ + Na ₂ O content of more than 90% by weight.
Powdered by heating and then pulverizing the sludge generated in the production process of sodium aluminate;
Preparing an organic acid salt by adding acetic acid and / or formic acid to the finely ground powder;
Obtaining an alkali compound from by-products generated during the preparation of a high performance concrete for concrete;
20 to 60% by weight of the organic acid salt, 1 to 5% by weight of the alkali compound, photosynthetic bacteria, yeast, useful actinomycetes and yeast fungi microorganism selected from the group consisting of fungi and water to make a liquid containing Method of producing a non-chloride-based liquid snow removal composition comprising the step.
The method of claim 8,
Method for producing a non-chloride-based liquid snow removing agent composition, characterized in that it further comprises the step of making a liquid phase containing 0.001 to 2.0% by weight of a nitrite-based corrosion inhibitor.