KR100592084B1 - Water treatment composition for cooling system - Google Patents

Abstract

The present invention relates to a water treatment agent composition for a cooling system, comprising: (a) isothiazononone represented by the following formula (1), (b) polyhexamethylene guanidine chloride represented by the following formula (2), (c) phosphate, and (d) phosphate When the water treatment agent composition for a cooling system including fonate and (e) water is applied to the cooling system, it is possible to simultaneously prevent corrosion of the metal constituting the system, microbial sterilization effect and generation of scale.

[Formula 1]

In Formula 1, R is hydrogen or chlorine.

[Formula 2]

In Formula 2, m and n are the same as or different from each other, and are integers of 1 to 14.

Water treatment composition, cooling tower, open circulation system, isothiazolone, poly hexamethylene guanidine chloride

Description

Water treating composition for a cooling system

[TECHNICAL FIELD OF THE INVENTION]

The present invention relates to a water treatment agent composition for a cooling system, and more particularly, to be applied to a cooling system to achieve corrosion prevention, microbial sterilization effect, and prevention of generation of scale constituting the system at the same time. The present invention relates to a water treatment agent composition for a cooling system comprising isothiazolone, (b) polyhexamethylene guanidine chloride represented by the following formula (2), (c) phosphate, (d) phosphonate and (e) water.

[Formula 1]

In Formula 1, R is hydrogen or chlorine.

[Formula 2]

In Formula 2, m and n are the same as or different from each other, and are integers of 1 to 14.

[Private Technology]

Corrosion refers to a phenomenon in which metal is oxidized and rust occurs. This corrosion occurs when a metal, which is an electrical conductor, comes into contact with an electrolyte material, which is an ion conductor, to form a potential difference on a metal surface. The scale is formed by the combination of various divalent metal ions present in the sediment or water quality due to corrosion on the metal surface in the air or anionic chemicals, etc. This scale phenomenon decreases the solubility of the salts causing the scale as the temperature rises. Therefore, it occurs mainly in high temperature heat exchanger. Microbial slime refers to a phenomenon in which microorganisms in the water quality or microorganisms in the atmosphere enter the open circulation cooling system and attach to the filter and the water pipe of the cooling tower.

It can be found that corrosion, scale and microbial slime occur very easily in various industrial facilities using water pipes, including heat exchangers of cooling and air conditioning installed in actual industrial sites. In this case, the life cycle, environmental pollution and thermal efficiency of the cooling circulation system are reduced. Is causing serious problems, causing huge economic losses.

Various programs widely used as conventional coolant water treatment agents were treated with corrosion inhibitors, scale inhibitors, and microbial inhibitors separately. Therefore, it was not possible to solve corrosion, scale, and microbial slime problems with one product.

As a conventional water treatment agent composition, anti-corrosion and anti-scale technologies and microbial protection technologies are introduced separately, and are widely used in practice. 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 reports cooling water treatment technology based on the composition of zinc salts, molybdates, and phosphates. Patent No. 5,156,665 reports a microbial prevention treatment technology.

However, the water treatment agent composition having a corrosion and scale prevention function has a weak microbial protection function, the microbial protection composition has a problem that its use is limited because it can not expect the corrosion and scale prevention function.

In order to solve the problems of the prior art, the present invention can treat the corrosion, scale and microbial problems of the conventional water treatment agent with a single drug, and at the same time, an object of the present invention is to provide a water treatment agent that is easier to use in an open circulation cooling system. .

Another object of the present invention is to provide a method of suppressing corrosion and scale of metal in water by administering the water treatment agent to various water pipes including a cooling tower and a heat exchanger.

In order to achieve the above object, the present invention is (a) isothiazononone represented by the following formula (1), (b) polyhexamethylene guanidine chloride represented by the following formula (2), (c) phosphate, (d) phosphonate and (e) It provides a water treatment agent composition for a cooling system comprising water.

[Formula 1]

In Formula 1, R is hydrogen or chlorine.

[Formula 2]

In Formula 2, m and n are the same as or different from each other, and are integers of 1 to 14.

In another aspect, the present invention provides a method for inhibiting the corrosion and scale of the metal in the water, characterized in that for administering the water treatment agent composition for the cooling system to various water pipes including a cooling tower, heat exchanger.

Hereinafter, the present invention will be described in detail.

The inventors have developed a water treatment composition of the present invention as a result of studying a water treatment composition for a cooling system that can simultaneously solve problems of corrosion, scale and microbial slime in a cooling system.

 The isothiazolone of Chemical Formula 1 used in the present invention is 3-isothiazolyrone, and preferably contains 0.05 to 10% by weight of the total water treatment composition. The isothiazolone may be 2-methyl-4-isothiazolone-3-one in which R is hydrogen in Formula 1 or 5-chloro-2-methyl-4-isothiazolone-3-one in which R is chlorine. Preferably, more preferably 2-methyl-4-isothiazolone-3-one and 5-chloro-2-methyl-4-isothiazolone-3-one in a weight ratio of 1:20 to 20: 1 It is good to be mixed. The 3-isothiazolone is effective against a wide range of microorganisms and has excellent sustainability, but less than 0.05 wt% of the bactericidal effect is less than 10 wt% is good sterilization effect but not economical.

In addition, the present invention includes the polyhexamethylene guanidine chloride of the formula (2), the polyhexamethylene guanidine chloride has a synergistic effect when applied with 3-isothiazolinone, because the sterilization fastness is very excellent. In the present invention, the polyhexamethylene guanidine chloride is preferably contained 0.5 to 80% by weight of the total water treatment composition. If the polyhexamethylene guanidine chloride is less than 0.5% by weight, the sterilization effect is not good, and if it exceeds 80% by weight, the sterilization effect is good but not economical.

In addition, in the present invention, the phosphate is preferably used 0.5 to 30% by weight of the total water treatment composition based on the ortho phosphate ions. If the amount of the phosphate salt is less than 0.5% by weight based on ortho phosphate ions, the corrosion protection is insignificant, and when used in excess of 30% by weight, calcium phosphate scale may be caused. Preferably, the phosphate is preferably phosphoric acid.

In addition, the present invention includes a phosphonate, the phosphonate is preferably contained from 0.2 to 30% by weight of the total water treatment agent composition based on the organic phosphate ions. Preferably, the phosphonate is a group consisting of hydroxy ethyline diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphonobutane tri carboxylic acid, ethylene diamine tetra methylidine phosphonic acid It is preferably selected from. If the amount of the phosphonate is less than 0.2% by weight, the anticorrosive and anti-scaling effect is insignificant, and if it exceeds 30% by weight, it is not economical.

In addition, the water treatment agent composition of the present invention includes water, which serves to maintain the balance of the above-mentioned components. In the present invention, the water content may be elastically adjusted according to the form of the water treatment agent composition. That is, when storing or transporting, it may contain very little or no water at all. Preferably the content of water in the total water treatment composition is 98% by weight or less.

When the water treatment composition of the present invention is applied to a cooling system, the dilution ratio is preferably added at a concentration of 20 to 1000 ppm. When the concentration of the water treatment agent composition is less than 20 ppm, corrosion prevention and microbial slime suppression are insignificant, and when the concentration exceeds 1000 ppm, it is not economical.

As described above, the water treatment agent composition of the present invention can be used more effectively to prevent corrosion and to suppress scale that may occur in various industrial water pipes including cooling towers and heat exchangers, and thus can be used in both an open circulation cooling system and a daily cooling system. . In particular, it is more preferable to use as a water treatment agent of an open circulation cooling system having high corrosion tendency and severe microbial problems.

Hereinafter, the present invention is described in Examples. However, the following examples are intended to illustrate the invention and the present invention is not limited by the following examples.

Example 1

100% by weight of the cooling system water treatment composition was prepared by mixing 0.3% by weight of isothiazolone, 20% by weight of polyhexamethylene guanidine chloride, 2% by weight phosphate and 5% by weight of phosphonate with water. In this example, isothiazolone and polyhexamethylene guanidine chloride were used by SK Corporation, and phosphonate was used by Bayer's PBTC (2-phosphono-1,2,4-butanetricarboxylic acid).

[Examples 2 to 5 and Comparative Examples 1 to 5]

A water treatment composition was prepared in the same manner as in Example 1, except that the content of the constituents as compared to Example 1 was changed as in Table 1 below. However, the comparative example 1 shall not contain a component at all.

Content (ppm) Isothiazolone Polyhexamethylene guanidine chloride Phosphate Phosphonates water Example 1 0.3 20 2 5 Add remaining amount up to 100% by weight Example 2 0.4 18 4 5 Example 3 0.5 16 6 4 Example 4 1.3 2.7 8 4 Example 5 1.4 1.4 10 3 Comparative Example 1 - - - - Comparative Example 2 0.4 - - 2 Comparative Example 3 - - 4 2 Comparative Example 4 - 3 6 - Comparative Example 5 - 1.4 8 One

[Experiment 1] Corrosion and Microbial Suppression Test

In order to determine the efficacy of the water treatment agent composition of the present invention, the corrosion and microbial inhibition tests were performed on Examples 1 to 5 and Comparative Examples 1 to 5. The test method was prepared in advance the test water quality of # 1 to # 5 as shown in Table 2, using a rotating corrosion tester (Rotating corrosion tester) at 30 ℃, 170 rpm, 10 cc / min air injection state, and also microorganisms Eight types of mixed Bacillus subtilis solution for Enterobacter aerogens ATCC 13048, Escherichia coli ATCC 11229, Micrococcus luteus ATCC 9341, Pseudomonas aeruginosa ATCC 15442, Klebsiella pneumoniae ATCC 1560, Staphylococcus edidermis ATCC 155 It was injected together to measure the corrosion rate and the concentration of microorganisms of carbon steel after 5 days. The results of the experiment are shown in Table 3.

Water quality #One #2 # 3 #4 # 5 pH 8.5 7.1 7.4 7.7 8.0 Ca-H (ppm) 0 50 100 200 300 M-Alkalinity 100 25 40 60 80 Mg-H (ppm) 0 10 20 40 60 Chloride (ppm) 1000 40 80 160 240 Initial Microbial Concentration (CFU / ml) 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷

In Table 2, the pH was adjusted to 0.1 N aqueous sodium hydroxide solution and 0.05 N sulfuric acid solution. Ca-H shows calcium hardness and was adjusted with calcium chloride. M-Alkalinity was adjusted to sodium bicarbonate as M-alkalinity. Mg-H was adjusted to magnesium sulfate as magnesium hardness. In addition, the initial microbial concentration was adjusted to the initial microbial concentration after preparing a mixture of ⁸ microorganisms at 10 ⁸ CFU / ml. (CFU: Cell Forming Unit)

Corrosion Result (mdd) Residual Microbial Concentration After 5 Days (CFU / ml) Water quality #One #2 # 3 #4 # 5 #One #2 # 3 #4 # 5 Example 1 17.86 8.26 9.53 12.34 15.87 0 0 0 0 0 Example 2 15.27 7.87 6.68 10.86 14.89 0 0 0 0 0 Example 3 12.18 5.67 6.51 7.56 9.52 0 0 0 0 0 Example 4 13.55 5.76 6.12 7.23 8.65 0 10 ¹ 10 ¹ 10 ¹ 10 ¹ Example 5 12.00 6.90 5.55 6.87 7.84 0 10 ¹ 10 ¹ 10 ¹ 10 ¹ Comparative Example 1 346.33 205.60 213.30 229.36 341.01 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ 10 ⁷ Comparative Example 2 110.09 84.40 84.86 91.74 105.50 10 ⁷ 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸ Comparative Example 3 29.36 13.03 13.94 13.51 25.68 10 ⁷ 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸ Comparative Example 4 25.23 12.93 14.04 15.96 23.85 10 ⁶ 10 ⁷ 10 ⁸ 10 ⁸ 10 ⁸ Comparative Example 5 23.21 10.00 11.19 13.47 22.57 10 ⁷ 10 ⁸ 10 ⁸ 10 ⁸ 10 ⁸

In Table 3, mdd is mg / (dm ² · day) and CFU / ml is cell forming unit / ml.

The results of Table 3 show that the water treatment composition of Examples 1 to 5 has a very excellent corrosion inhibitory effect and microbial inhibitory effect regardless of the type of water quality.

[Experiment 2] Scale performance test method

After removing the microorganisms in the water quality # 2 to # 4 of Table 2, the water treatment agent of Examples 1 to 5 and Comparative Examples 1 to 5 was added, the test water solution was sealed and the test water solution was suspended for 24 hours at 75 ℃ Was filtered with a 0.22 macro filter to measure the total hardness at this time to determine the scale inhibition. Inhibition rate in this experiment was calculated through the following formula 1, the results are shown in Table 4.

[Calculation 1]

% Inhibition = (Ct / Ce) × 100

Ct: total hardness in test solution before test

Ce: total hardness in test solution after test

TABLE 4

Scale Suppression Ratio (%) Water quality #2 # 3 #4 # 5 Example 1 100 98 99 96.7 Example 2 98 96 97 95.3 Example 3 98 96 97 95.3 Example 4 96 96 96 95.3 Example 5 94 96 94 90.0 Comparative Example 1 72 76 73 68 Comparative Example 2 92 92 92 88 Comparative Example 3 84 82 79 76.7 Comparative Example 4 68 70 68 66.7 Comparative Example 5 72 74 70 68

According to Table 4, the scale inhibition rate of Examples 1 to 5 according to the present invention was much higher than that of Comparative Examples 1 to 5.

As described above, the water treatment agent composition for the cooling system according to the present invention was found to have a very excellent effect of preventing corrosion, microbial sterilization and scale generation of metals. The present invention has instant sterilization and continuous sterilizing power, and has excellent sterilizing effect on all microorganisms, and has both anodized and precipitated film type, so that corrosion is suppressed by suppressing the anode and cathode reactions, which are electrochemical reactions that may occur on metal surfaces. Excellent anticorrosive effect can be expected by minimizing the conditions that can occur. Since phosphonate has excellent ability to suppress the scale by converting the crystal structure of the divalent metal salt scale, the ability to simultaneously control corrosion, scale and microbial slime is provided. outstanding.                     

Claims (7)

(a) isothiazolone represented by the following formula (1); (b) polyhexamethylene guanidine chloride represented by Formula 2 below; (c) regular phosphate; (d) phosphonates; And (e) water Water treatment agent composition for a cooling system comprising: [Formula 1]

In Formula 1, R is hydrogen or chlorine, [Formula 2]

In Formula 2, m and n are the same as or different from each other, and are integers of 1 to 14. The method of claim 1, The water treatment agent composition for the cooling system with respect to the total water treatment agent composition 0.05 to 10 wt% of (a) isothiazolone; 0.5 to 80% by weight of (b) polyhexamethylene guanidine chloride; (C) 0.5-30% by weight of an orthophosphate based on orthophosphate ions; (D) 0.2 to 30% by weight of phosphonate, based on organic phosphate ions; And (E) water balance Water treatment agent composition for a cooling system comprising a. The method of claim 1, wherein the isothiazolone of formula 1 is 2-methyl-4-isothiazolone-3-one, 5-chloro-2methyl-4-isothiazoron-3-one and 2-methyl- 4-isothiazolone-3-one and 5-chloro-2methyl-4-isothiazoron-3-one being selected from the group consisting of mixtures mixed in a weight ratio of 1:20 to 20: 1 A water treatment composition for a cooling system, characterized in that. The water treatment composition for a cooling system of claim 1, wherein the phosphate is phosphoric acid. The method of claim 1, wherein the phosphonate is selected from the group consisting of hydroxy ethyline diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphonobutane tri carboxylic acid and ethylene diamine tetra methylidine phosphonic acid. Water treatment agent composition for a cooling system, characterized in that selected from the group consisting of. The water treatment composition of claim 1, wherein the cooling system is an open circulation cooling system. The water treatment agent composition of claim 1 is administered to various water pipes including a cooling tower and a heat exchanger.