KR20030079187A - Multi-functional one-component type composition for cooling water-treatment agent and method of water-treatment using the same - Google Patents

Abstract

PURPOSE: Provided is a multi functional composition for cooling water treatment agent being capable of preventing corrosion, scale deposition and the formation of microbial slime in open water circulation cooling system. CONSTITUTION: The composition comprises 0.05 to 20 wt.% of isothiazolinone represented as formula I, where R is hydrogen or chlorine; 0.5 to 30 wt.% of bronopol; 0.2 to 30 wt.% of phosphonate; 0.2 to 40 wt.% of magnesium salt; and 0.0001 to 3 wt.% of one substance selected from the group consisting of iodic acid, periodic acid and their salts.

Description

MULTI-FUNCTIONAL ONE-COMPONENT TYPE COMPOSITION FOR COOLING WATER-TREATMENT AGENT AND METHOD OF WATER-TREATMENT USING THE SAME}

The present invention relates to a multifunctional one-component cooling water treatment composition and a water treatment method using the same, and more particularly, it is possible to simultaneously suppress corrosion, scale and microbial slime formation which may occur in an open circulation cooling system using water, and its inhibitory effect. The present invention relates to an excellent multifunctional one-component cooling water treatment composition and a water treatment method using the same.

In open circulation cooling systems, a cooling tower is used to control the temperature of the cooling water. The system using the cooling tower is called an open circulation cooling system because air is introduced, and various minerals in the water are concentrated through evaporation of the water in the process of reusing the cooling water. . Summarizing these various results, three problems of open circulation cooling system are largely caused by corrosion, scale, and microbial slime.

Corrosion refers to a phenomenon in which a metal is oxidized and rust occurs. This corrosion occurs when a potential difference is formed on a metal surface when a metal, which is an electrical conductor, comes into contact with an electrolyte material that is an ion conductor.

The scale is produced by the combination of various divalent metal ions present in the sediment or water due to corrosion on the metal surface in the air or anionic chemicals, etc. This scale phenomenon is the solubility of the salts causing the scale as the temperature rises Because of the decrease, it occurs mainly in heat exchangers, for example, where the temperature is high.

Microbial slime refers to a phenomenon in which microorganisms in water or in the air enter the open circulation cooling system and adhere to the filler and the water pipe of the cooling tower.

In fact, corrosion, scale, and microbial slime can be found very easily in various industrial facilities using water pipes, including heat exchangers of cooling and air conditioning installed in industrial sites, and in this case, reduction of life, environmental pollution, and thermal efficiency of the cooling circulation system. There is a problem that causes a serious problem in the financial loss.

Therefore, various techniques for water treatment agents that can suppress such corrosion, scale, and microbial slime are known. For example, U. S. Patent No. 4,134, 959 describes a water treatment composition using an azole compound and phosphate, and U. S. Patent No. 5,227, 133 describes a cooling water treatment technique based on the composition of zinc salts, molybdates, and phosphates. Patent No. 5,156,665 describes a microbe prevention treatment technique.

However, since the conventional cooling water treatment agents are treated by adding a corrosion inhibitor, a scale inhibitor, and a microbial inhibitor separately, it is impossible to solve problems of corrosion, scale, and microbial slime by using one water treatment agent at once. Accordingly, the microbial protection function is weak in the cooling water treatment agent composition having a corrosion and scale prevention function, and the corrosion and scale prevention function is weak in the cooling water treatment agent composition having the microbial protection function.

In addition, corrosion inhibitors, scale inhibitors, and microbial inhibitors have been separately developed by conventional cooling water treatment methods. In the case of mixing them as a single product, compatibility with each other is insufficient, and precipitates are formed or the components are entangled with each other. This is because the stability of the product is lowered and the effect of each compound is not exhibited smoothly.

Therefore, there is a need for a study of a one-component cooling water treatment agent composition and a water treatment method using the same that are easy to use by preventing the occurrence of corrosion, scale, and microbial slime in an open circulation cooling system.

Disclosure of Invention It is an object of the present invention to provide a multifunctional one-component cooling water treatment composition capable of simultaneously solving corrosion, scale and microbial slime generation problems in an open circulation cooling system in view of the problems of the prior art.

Another object of the present invention is to provide a multifunctional one-component cooling water treatment composition excellent in the ability to inhibit corrosion, scale, and microbial slime.

Another object of the present invention is to provide a water treatment method using the cooling water treatment agent composition.

In order to achieve the above object, the present invention is a) isothiazolinone represented by the following formula (1); b) bronopol; c) phosphonates; d) magnesium salts; And e) iodic acid, periodic acid, or salts thereof.

[Formula 1]

In Formula 1, R is hydrogen or chlorine.

The present invention also provides a water treatment method comprising the step of adding the multifunctional one-component cooling water treatment composition to a cooling water system.

Hereinafter, the present invention will be described in detail.

The cooling water treatment composition of the present invention is a multifunctional one-component cooling water treatment composition that can simultaneously solve the problem of corrosion, scale and microbial slime in an open circulation cooling system.

In the cooling water treatment composition of the present invention, a) isothiazolinone represented by Formula 1 is used as a microbial treatment agent. The isothiazolinone is effective in removing a wide range of microorganisms, and its sustainability is also excellent. In particular, the isothiazolinone of Formula 1 is 2-methyl-4-isothiazolone-3-one wherein R is hydrogen or 5-chloro-2-methyl-4-isothiazolone-3-one where R is chlorine Preferably, the 2-methyl-4-isothiazolone-3-one and 5-chloro-2-methyl-4-isothiazolone-3-one are mixed at a weight ratio of 1:20 to 20: 1. It is more preferred to use mixtures which are present.

The content of isothiazolinone is preferably 0.05 to 20% by weight based on the total composition. If the content of the isothiazolinone is less than 0.05% by weight, the microbial removal effect may not appear, and when the content of the isothiazolinone is more than 20% by weight, the storage stability may be lowered and it is not preferable because it is uneconomical.

B) Bronofol is 2-bromo-2-nitropropane-1,3-diol (2-bromo-2-nitropropane-1,3-diol) is excellent in sterilization fast action against microorganisms, a) iso When used with thiazolinones, a synergistic synergistic effect can be obtained.

The content of the bronopol is preferably 0.5 to 30% by weight. If the content of the bronopol is less than 0.5% by weight may not exhibit a microbial removal effect, when the content of more than 30% by weight may cause precipitation in the composition is not preferable because there is a problem that is uneconomical.

C) The phosphonate is used as a scale inhibitor, preferably hydroxy ethylidene diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphonobutane tri carboxylic acid, or ethylene diamine Tetramethylidine phosphonic acid and the like can be used.

The content of the phosphonate is preferably 0.2 to 30% by weight based on the concentration of organic phosphate ions. If the content of the phosphonate is less than 0.2% by weight may not exhibit a scale preventing effect, when it exceeds 30% by weight is not preferable because there is a problem of low economic efficiency.

It is preferable to use magnesium nitrate, magnesium oxide, or a mixture thereof as the magnesium salt.

The content of the magnesium salt is preferably 0.2 to 40% by weight, when the content of the magnesium salt is less than 0.2% by weight may precipitate the product, when the content of more than 40% by weight may precipitate the product, uneconomical There is a problem that is not preferable.

E) Iodic acid (periodic acid), periodic acid (periodic acid), or salts thereof are used as a stabilizer, preferably potassium iodate.

The content of the iodic acid, periodic acid, or salts thereof is preferably 0.0001 to 3% by weight. When the content of the iodic acid, periodic acid, or salts thereof is less than 0.0001% by weight, the effect as a stabilizer may not appear, and when it exceeds 3% by weight, the main components in the composition may be oxidized, and it is uneconomical. There is a problem, which is undesirable.

Cooling water treatment agent composition of the present invention comprises water, the content of water is adjustable.

On the other hand, the present invention provides a water treatment method comprising the step of adding a multi-functional one-component cooling water treatment composition having the composition and content as described above in the cooling water system.

The cooling water treatment agent composition of the present invention can be effectively used to suppress problems related to corrosion, scale, and microorganisms that may occur in various industrial water pipes, and can be applied to open circulation cooling systems and daily cooling systems. In particular, it is more preferable to be used as a water treatment agent in an open circulation cooling system with high scale tendency and severe microbial problems.

The cooling water treatment composition of the present invention is preferably used to maintain the concentration of 1 to 500,000 ppm in the cooling water to be treated.

Hereinafter, the present invention will be described with reference to the following Examples and Comparative Examples. However, these examples are only for illustrating the present invention, but the present invention is not limited thereto.

(Examples 1 to 5)

To prepare a cooling water treatment composition according to the components and contents shown in Table 1 below. At this time, isothiazolinone is SK Chemical's 'SKYBIO WG' (2-methyl-4-isothiazolone-3-one: 5-chloro-2-methyl-4-isothiazolone-3-one). Mixture having a weight ratio of 1: 3). In addition, a mixture of magnesium oxide and magnesium nitrate was used as the magnesium salt, and HEDP (hydroxyethylidene diphosphonic acid) manufactured by Solutia was used as the phosphonate.

(Unit: weight%) division Example 1 Example 2 Example 3 Example 4 Example 5 Isothiazolinone 4.5 4.0 3.5 3.0 1.5 Bronopol 10 20 15 5 2.5 Phosphonates 10 20 10 5 5 Magnesium ions 3 4 2.5 2 One Potassium Iodate 0.04 0.03 0.02 0.01 0.005 water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

(Comparative Examples 1 to 5)

To prepare a cooling water treatment composition according to the components and contents shown in Table 2. Isothiazolinone, magnesium salts, and phosphonates used the same products as used in Examples 1-5 above.

(Unit: weight%) division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Isothiazolinone - 0.5 - - - Bronopol - - 5 - - Phosphonates - 2 - - 4 Magnesium ions - 2 - 4 - Potassium Iodate - - - 0.02 - water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

Experimental Example

The cooling water treatment compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were tested for corrosion and microbial inhibition test, and scale performance as follows.

end. Corrosion and Microbial Suppression Test

Corrosion and microbial inhibition tests were performed using a Rotating corrosion tester. The mixture of microorganisms eight kinds (Enterobacter aerogens ATCC 13048, Escherichia coli ATCC 11229, Micrococcus luteus ATCC 9341, Pseudomonas aeruginosa ATCC 15442, Klebsiella pneumoniae ATCC 1560, Staphylococcusedidermis ATCC 155, Staphylococcus aureus ATCC 6538, Bacillus subtilis ATCC 6984) the corrosion test solution After injecting together, the carbon steel test piece was rotated at a rotational speed of 170 rpm at a temperature of 30 ° C. and 10 cc / min in air, and the corrosion rate of the carbon steel and the decrease in the concentration of microorganisms were measured after 3 days.

After applying to the test water quality of Table 3, the cooling water treatment composition of Examples 1 to 5, and Comparative Examples 1 to 5 by diluting to 100 ppm, the corrosion rate according to the weight loss of the carbon steel [mdd, mg / (dm 2 · day)] and 5 days after the residual microbial concentration was measured and the results are shown in Table 4 below.

division Water quality One 2 3 4 5 pH 7.3 7.6 7.9 8.2 8.5 Calcium Hardness (ppm) 50 100 200 300 500 Magnesium hardness (ppm) 10 20 40 60 100 Chlorine (ppm) 40 80 160 240 400 Initial Microbial Concentration (CFU / mL) 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷

The acidity (pH) of the test water quality 1 to 5 according to Table 3 was adjusted to 0.1 N sodium hydroxide solution and 0.05 N sulfuric acid solution, calcium hardness and magnesium hardness were adjusted to calcium chloride and magnesium sulfate, respectively. In addition, the initial microbial concentration was adjusted after preparing the ^eight microbial mixtures 10 ⁸ CFU (cell forming unit) / ml.

division Corrosion Result [mdd: mg / (dm ² ㆍ day)] Residual Microbial Concentration After 5 Days (CFU / mL) Water Quality 1 Water Quality 2 Water Quality 3 Water Quality 4 Water Quality 5 Water Quality 1 Water Quality 2 Water Quality 3 Water Quality 4 Water Quality 5 Example 1 11.47 10.09 9.48 9.02 8.72 0 0 0 0 0 Example 2 10.86 10.09 9.02 8.87 8.56 0 0 0 0 0 Example 3 11.31 10.55 10.24 10.09 9.17 0 0 0 0 0 Example 4 12.39 12.08 11.93 11.93 11.62 0 0 0 0 0 Example 5 12.84 12.23 12.08 11.01 10.40 0 0 0 0 10 ² Comparative Example 1 150.15 136.54 113.15 110.8 105.96 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ Comparative Example 2 118.04 104.43 98.92 92.35 83.79 10 ⁶ 10 ⁶ 10 ⁶ 10 ⁷ 10 ⁷ Comparative Example 3 165.43 133.49 120.80 110.24 101.38 10 ⁵ 10 ⁵ 10 ⁶ 10 ⁶ 10 ⁶ Comparative Example 4 153.21 131.96 118.65 107.19 107.03 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸ Comparative Example 5 72.17 61.62 52.75 46.48 37.92 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁹

As shown in Table 4, the cooling water treatment agent compositions of Examples 1 to 5 of the present invention for the test water quality 1 to 5 are better than the cooling water treatment composition of Comparative Examples 1 to 5 both anti-corrosion and microbial sterilization effect. It can be seen.

In addition, it can be seen that the corrosion prevention and microbial sterilization effect is excellent at the same time.

I. Scale Suppression Test

After the test solution was sealed and allowed to stand at 75 ° C. for 24 hours, the test solution was filtered through a 0.22 micron filter and the total hardness at this time was measured to determine scale inhibition. Test water quality of the test solution was used in the same water quality as described in Table 3 above, after controlling the microorganisms in the test water quality, each concentration of the cooling water treatment composition composition of Examples 1 to 5 and Comparative Examples 1 to 5 Tested while maintaining. Scale inhibition was calculated by the following equation 1 and the results are shown in Table 5.

[Equation 1]

In Equation 1, Ct represents the total hardness of the test solution before the test, Ce represents the total hardness of the test solution after the test.

division Scale inhibition rate (%) Test water quality 1 Test water quality 2 Test Quality 3 Test water quality 4 Test water quality 5 Example 1 100 100 99 97 96 Example 2 100 100 97 97 96 Example 3 100 100 99 97 96 Example 4 100 98 97 97 94 Example 5 100 98 97 97 90 Comparative Example 1 60 54 44 33 25 Comparative Example 2 75 60 54 48 42 Comparative Example 3 64 50 42 33 25 Comparative Example 4 56 50 40 33 20 Comparative Example 5 80 75 68 66 58

As shown in Table 5, it can be seen that the scale inhibition rate of the cooling water treatment composition according to Examples 1 to 5 of the present invention is significantly superior to the cooling water treatment composition of Comparative Examples 1 to 5.

Taken together, these test results show that the cooling water treatment composition for the open-circulation cooling system according to the present invention has synergistically improved corrosion protection, scale generation, and microbial sterilization effects of metals. there was.

As described above, the cooling water treatment agent composition of the present invention has a sterilization sustainability, has excellent sterilization effect against all microorganisms in the open circulation cooling system, and has a function of preventing both the anode reaction and the cathode reaction during the corrosion reaction. Therefore, it is possible to expect the excellent anticorrosive effect by reducing the corrosion conditions that can occur on the metal surface as much as possible. In addition, since the phosphonate converts the crystal structure of the divalent metal salt scale and has an excellent ability to suppress the scale, it is possible to simultaneously solve the problems of corrosion, scale and microbial slime in an open circulation cooling system.

Claims (7)

a) isothiazolinone represented by the following formula (1); b) bronopol; c) phosphonates; d) magnesium salts; And e) iodic acid, periodic acid, or salts thereof Multifunctional one-component coolant treatment composition comprising: [Formula 1] In Formula 1, R is hydrogen or chlorine. According to claim 1, wherein the content of isothiazolinone is 0.05 to 20% by weight, the content of the bronopol is 0.5 to 30% by weight, the content of the phosphonate is 0.2 to 30% by weight, The content is 0.2 to 40% by weight, the content of the iodic acid, periodic acid, or salts thereof is 0.0001 to 3% by weight of the multifunctional one-component cooling water treatment composition. The method of claim 1, wherein the isothiazolinone has 5-chloro-2-methyl-4-isothiazolone-3-one and 2-methyl-4-isothiazolone-3-one in a 1:20 to 20: A multifunctional one-component cooling water treatment composition which is a mixture mixed in a weight ratio of 1. The phosphonate of claim 1, wherein the phosphonate is hydroxy ethylidene diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphonobutane tri carboxylic acid, and ethylene diamine tetra methylidine phospho. Multifunctional one-component chilled water treatment composition which is one kind of compound selected from the group consisting of nic acids. The multifunctional one-component cooling water treatment composition of claim 1, wherein the magnesium salt is magnesium nitrate, magnesium oxide, or a mixture thereof. A water treatment method, wherein the multifunctional one-component cooling water treatment composition according to any one of claims 1 to 5 is introduced into a cooling water system. The water treatment method according to claim 6, wherein the concentration of the coolant treatment composition is 1 to 500,000 ppm with respect to the coolant.