KR101205470B1 - Water treatment composition having biocide effect and water treatment method using the same - Google Patents

Abstract

The present invention relates to a water treatment agent composition and a water treatment method for a cooling system having a bactericidal effect on various microorganisms including algae (moss), as well as a corrosion preventing ability of metals and an inhibitory effect on the scaling of aquatic ions. A) 0.1 to 40% by weight of 1-sodium oxide-2-pyridinethiol, b) 0.1 to 7% by weight based on the concentration of polyphosphate (P), c) 0.1 to 25% by weight of the acrylate copolymer, and d The present invention relates to a water treatment composition comprising a water balance, and a water treatment method using the same.

Sterilization, Corrosion, Scale, Water Treatment

Description

WATER TREATMENT COMPOSITION HAVING BIOCIDE EFFECT AND WATER TREATMENT METHOD USING THE SAME

The present invention has a bactericidal effect on various microorganisms including algae (moss) that may occur in a cooling system, and relates to a water treatment composition and a water treatment method having a corrosion preventing ability of metals and an inhibitory effect on scaling up of water ions.

The cooling system using the cooling tower is called an open circulation cooling system because air is continuously introduced into the cooling tower. In the process of reusing water, the concentration of various ions and minerals contained in the water occurs through evaporation of water. Therefore, the results vary depending on the method of treating the water used.

Major industrial facilities at the national base, such as petrochemicals, refineries, textiles, steel, electronics, and power plants, use open circulation cooling systems to cool the heat generated during the production process. The environment of such open circulation cooling system is so good that microorganisms, including algae, breed, and should always be concerned about microbial contamination.

In addition, most of the materials constituting the open circulation cooling system are metals. In general, the metals are made of a material to be used by applying energy to an oxide state. The application of energy is an artificial force, but the emission of energy is a natural force. Corrosion is an extremely normal natural phenomenon in which energy is released to return metal to its natural state of oxide. Therefore, in the open circulation cooling system, a corrosion phenomenon, which is a natural phenomenon of returning the metal material to the oxide state, occurs.

When various metal cations present in the sediment or water quality due to the metal surface corrosion are combined with anionic substances or the like, scale is generated. When the scale is attached, porous deposits are formed on the heat transfer surface of the heat exchanger, which prevents the smooth flow of water or, in the case of severe water, blocks the water pipe.In some cases, local corrosion is caused by the difference in the concentration of dissolved oxygen in the water. It is also triggered.

Microbial contamination, corrosion and scale problems can be easily found in various industrial facilities using water pipes, including heat exchangers in open-circulation cooling systems installed in actual industrial sites. It causes serious problems in environmental pollution, human toxicity and thermal efficiency, causing enormous economic losses.

In order to solve the above problems, the water treatment agent for the cooling system is inevitably used, and is now widely used in all industrial fields.

Various water treatment agents widely used as conventional cooling water treatment agents are treated separately by adding corrosion inhibitors, scale inhibitors, and microbial inhibitors separately. Therefore, the input of one product solves all problems of microbial contamination, corrosion and scale generation including algae (moss). It is impossible to do According to the prior art, there is no known water treatment composition which exhibits the above effects at the same time as there is a problem in stabilizing the product such as generation of precipitates. Existing water treatment composition is introduced only corrosion protection and anti-scale technology and microbial protection technology, respectively.

For example, U.S. Patent No. 4,134,959 describes a water treatment agent composition using an azole compound and phosphate, and U.S. Patent No. 4,149,969 discloses zinc salts, molybdates, manganese salts, nickel salts, azole compounds, and phosphonates. Compositions containing zinc salts, cellulose gums, and phosphonates are disclosed, and US Patent Nos. 4,411,865 using zinc salts, chromium salts, phosphates, and acrylate copolymers. The technology has been reported, US Pat. No. 5,227,133 for cooling water treatment by the composition of zinc salts, molybdates, phosphates: US Pat. No. 4,673,509 shows microorganisms using tetrakis hydroxyl methyl phosphonium sulphate Treatment techniques have been reported.

Therefore, existing water treatment composition and water treatment technology can not expect satisfactory performance with one composition in the ability to prevent microbial contamination, corrosion, or to suppress the scale, and corrosion and scale problems when using chromium salt It can be solved, but its use is regulated due to various problems such as pollution induction, human toxicity and stability.

In view of the problems of the prior art water treatment agent composition as described above, the present invention can be simultaneously treated with excellent effects on microorganisms and corrosion and scale problems, and more convenient and safe water treatment composition and water treatment method in an open circulation cooling system The purpose is to provide.

In order to achieve the above object, the present invention provides a) 0.1 to 40% by weight of 1-sodium oxide-2-pyridinethiol, b) 0.1 to 7% by weight based on the concentration of phosphorus (P), c) acrylate-based air It provides a water treatment composition comprising 0.1 to 25% by weight of coal, and d) water balance.

In addition, the present invention provides a water treatment method to suppress the microbial and metal corrosion, and scale formation by adding to the cooling tower, heat exchanger or water pipe so that the concentration of the water treatment agent composition is maintained to 0.1 to 500,000 ppm relative to the treated water.

Hereinafter, the present invention will be described in more detail.

The present inventors found that the water treatment agent composition having the composition and content as described above is very excellent in the function of inhibiting microbial problems, corrosion and scale generation, including algae (moss), unlike the compounds which have been used as water treatment agents. I could complete it.

The water treatment composition of the present invention comprises a) 1-sodium oxide-2-pyridinethiol, b) polymerized phosphate, c) acrylate copolymer, and d) water.

In the water treatment composition according to the present invention, the concentration of a) 1-sodium oxide-2 pyridinethiol is preferably 0.1 to 40% by weight based on the concentration of 1-sodium oxide-2 pyridinethiol, and 0.5 to 35% by weight. % Is more preferred.

If the content of a) 1-sodium oxide-2 pyridinethiol in the water treatment composition is less than 0.1% by weight, the bactericidal effect against microorganisms including algae (moss) is insufficient, and if it exceeds 40% by weight, sediment may occur in the preparation of the water treatment agent. It has the disadvantage of low economic efficiency.

B) The polymeric phosphate in the water treatment composition of the present invention is preferably selected from the group consisting of tetra potassium pyro phosphate, tetra sodium pyro phosphate, sodium hexa meta polyphosphate. In this case, the content of the polymerized phosphate b) is preferably 0.1 to 7% by weight, more preferably 0.5 to 6% by weight based on the phosphorus (P) concentration. When the concentration of phosphorus (P) in the water treatment composition of the present invention is less than 0.1% by weight, corrosion and scale prevention performance is reduced, and when the concentration of phosphorus (P) exceeds 7.0% by weight, precipitates may be generated in the preparation of the water treatment agent. It is not economical.

The c) acrylate copolymer of the present invention is preferably a compound represented by the following formula (1).

[Formula 1]

Wherein each R ₁ and R ₂ are the same or different and are hydrogen, OH or alkyl, and X and Y are each independently an integer from 1 to 15.

The c) acrylate copolymer has a function of inhibiting scale formation in water, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 20% by weight, based on the concentration of the acrylate copolymer. C) Containing less than 0.1% by weight of the acrylate copolymer, the scale inhibitory effect is insignificant, and containing more than 25% by weight is not economical, and when the cooling water is discharged into the stream has a disadvantage of increasing the COD concentration of the discharged water May occur.

The water treatment composition of the present invention can be used for water treatment by adding to various industrial water pipes, such as cooling towers, heat exchangers, wherein the concentration of the water treatment agent composition is preferably maintained to 0.1 to 500,000 ppm relative to the treated water.

The water treatment composition of the present invention as described above can be used more effectively to prevent various microbial contamination including algae (moss) and to prevent corrosion and inhibit scale formation. Especially, it is more preferable to use it as a water treatment agent of an open-circulation cooling system with a severe microbial problem including algae (moss).

Hereinafter, preferred examples and comparative examples of the present invention are described. The following examples and comparative examples are described for the purpose of more clearly expressing the present invention, but the contents of the present invention are not limited to the following examples and comparative examples.

[Example]

Example  1 to 5

To prepare a water treatment composition of Examples 1 to 5 each having the composition and content as shown in Table 1.

ingredient content (% ) Example 1 Example 2 Example 3 Example 4 Example 5 1-sodium oxide-2-pyridinethiol 4.0 6.0 8.0 10.0 12.0 Polyphosphate (concentration of as P) 2.4 2.2 2.0 1.8 1.6 Acrylate copolymer 2.0 1.8 1.6 1.4 1.2 water Remainder Remainder Remainder Remainder Remainder

In Table 1, the polymerized phosphate is represented by the content of phosphorus (P) using tetra potassium pyrophosphate, and the acrylate copolymer is selected from the concentration of the acrylate copolymer using Belcrene 400 (manufactured by BIOLAB). It is represented by the content.

In addition, each of them was pre-set to a stable pH range using caustic soda in order to secure a stable pH range of 1-sodium oxide-2-pyritindiol, and water was added first to improve solubility. In order to apply Examples 1 to 5 at 100 ppm, Examples 1 to 5 were diluted to 10,000 ppm and then re-diluted.

Comparative example  1 to 4

The water treatment agent compositions of Comparative Examples 1 to 4 were prepared in the same manner as in Examples 1 to 5, except that compositions and contents were changed as shown in Table 2 below.

ingredient content (% ) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1-sodium oxide-2-pyridinethiol 0 4.0 0 0 Polyphosphate (concentration of as P) 0 0 1.6 0 Acrylate copolymer 0 0 0 1.2 water Remainder Remainder Remainder Remainder

Table 2 is a polymer phosphate as shown in Examples 1 to 5 is represented by the content of the concentration of phosphorus (P) using tetra potassium pyro phosphate, the acrylate copolymer is used Belken 400 (manufactured by BIOLAB) It is represented by the content of the concentration of the acrylate copolymer.

In order to apply Comparative Examples 1 to 4 at 100 ppm, Comparative Examples 1 to 4 were used after diluting to 10,000 ppm.

Test water quality test

In order to perform the performance test for the water treatment agent composition of the present invention, test water quality having a water quality condition of Table 3 below was prepared in a range utilized for a conventional industrial water pipe.

Water quality 1 Water quality 2 Water quality 3 Water quality 4 pH 8.3 8.1 7.8 7.5 Calcium Hardness (ppm) 200 400 600 800 Methyl Orange-Alkalido (ppm) 100 80 60 40 Magnesium hardness (ppm) 40 80 120 160 Chlorine Ion (ppm) 150 300 450 600

In Table 3, the pH was adjusted to 0.1N aqueous sodium hydroxide solution and 0.05N sulfuric acid solution, and the calcium hardness (Ca-H) was adjusted to calcium chloride. In addition, methyl orange-alkalinity (M-Alkalinity) was adjusted to sodium bicarbonate, magnesium hardness (Mg-H) was adjusted to magnesium sulfate. Chloride was used for the concentration of chlorine ions due to the calcium chloride used to control the calcium hardness, and the deficiency was controlled using sodium chloride.

Experimental Example  1: anti-corrosion test

The corrosion rate was measured by rotating the carbon steel test piece (0.218dm ² ) at a temperature of 30 ° C. for 5 days at a rotational speed of 170 rpm. In this case, the corrosion rate [mdd, mg / (dm ² ? Day)] of the carbon steels measured after maintaining the water treatment composition of Examples 1 to 5 in the concentration of 100 ppm in the test water of Table 3, respectively, is given in Table 4 below. Indicated. In addition, in the case of Comparative Examples 1 to 5 also shows the corrosion rate results measured through the test of the same method as Examples 1 to 5 in Table 4 below.

Corrosion Rate Measurement Results (mdd) Water quality 1 Water quality 2 Water quality 3 Water quality 4 Example 1 3.6 3.9 4.8 6.2 Example 2 4.5 5.1 5.7 6.5 Example 3 4.7 5.5 5.9 6.8 Example 4 5.2 6.2 7.1 7.6 Example 5 5.5 6.5 7.3 8.4 Comparative Example 1 278.4 294.2 368.2 378.5 Comparative Example 2 282.6 292.3 360.4 395.6 Comparative Example 3 5.7 6.3 7.3 8.6 Comparative Example 4 42.5 48.6 56.8 66.4

As shown in Table 4, as a result of testing the corrosiveness of the carbon steel using the water treatment composition of Examples 1 to 5 of the present invention, compared to Comparative Examples 1 to 4, the corrosion rate of the carbon steel is significantly lowered and the corrosion prevention effect is excellent. Able to know.

Experimental Example  2: scale formation inhibition test

Using the water treatment agent composition of Examples 1 to 5 and Comparative Examples 1 to 4 was sealed the test water solution having the water conditions as shown in Table 3, and after standing for 24 hours at 70 ℃ filtered the test water solution with a 0.45 macro filter The total hardness at this time was measured and the scale inhibition was measured using the following Formula 1. At this time, each of the water treatment composition was maintained at a concentration of 100ppm was tested for the scale inhibition rate is shown in Table 5 below.

[Equation 1]

Scale Form Inhibition Rate (%) = Ce / Ct x 100

In the above formula

Ce is the total hardness in the test solution before the test,

Ct is the total hardness in the test solution after the test.

Scale Suppression Ratio (%) Water quality 1 Water quality 2 Water quality 3 Water quality 4 Example 1 100 100 98 95 Example 2 100 100 97 92 Example 3 100 98 95 88 Example 4 98 98 95 86 Example 5 98 98 92 84 Comparative Example 1 75 60 56 52 Comparative Example 2 72 64 56 50 Comparative Example 3 86 80 77 74 Comparative Example 4 88 84 81 76

As shown in Table 5, when the scale performance test using the water treatment composition of Examples 1 to 5 of the present invention, it can be seen that the scale inhibition rate is significantly improved compared to Comparative Examples 1 to 4.

Experimental Example  3: against germs MIC  exam

Minimum Inhibitory Concentration (MIC) test for bacteria was carried out by diluting the water treatment composition of Examples 1 to 5 and Comparative Examples 1 to 4 according to the 2-fold serial dilution method using 24 multiwell plates, followed by a concentration of 10 ⁴ CFU / ml. Inoculated with bacteria and incubated for 48 hours at 30 ℃ and then the MIC value was measured by visually determining the growth of bacteria based on turbidity, the measurement results are shown in Table 6 below. At this time, the turbidity was observed using Dipco's Tryptic soy broth (DIFCO Co.), the bacterium micrococcus ( Micrococcus) leteus ATCC 9341), Staphylococcus aureus ATCC 6538, and distilled water was used as the basic diluent.

Bacterial MIC (ppm) Micrococcus Letus Staphylococcus aureus Example 1 19.6 39.8 Example 2 19.6 19.6 Example 3 9.8 19.6 Example 4 9.8 9.8 Example 5 9.8 9.8 Comparative Example 1 No MIC Efficacy No MIC Efficacy Comparative Example 2 19.6 39.8 Comparative Example 3 No MIC Efficacy No MIC Efficacy Comparative Example 4 No MIC Efficacy No MIC Efficacy

As shown in Table 6, as a result of bacterial MIC test using the water treatment composition of Examples 1 to 5 of the present invention, the bactericidal effect is significantly improved since the bactericidal effect on bacteria is lower than that of Comparative Examples 1 to 4. It can be seen.

Experimental Example  4: for algae MIC  exam

Minimum Inhibitory Concentration (MIC) test for algae was performed by diluting the water treatment composition of Examples 1 to 5 and Comparative Examples 1 to 4 according to the 2-fold serial dilution using a 24 multi-well plate, followed by 0.3 mg / ch of Chlorophyll. Inoculated algae at liter concentration, incubated for 10 days at the temperature of 30 ℃ under the light condition of 16L: 8D, and MIC value was measured by visually judging whether the algae grew or not based on color (green). It is shown in Table 7 below.

At this time, C-Medium was used as the medium, and Chlorella vulgaris NIES-227 was used as the algae, and distilled water was used as the basic diluent.

Algae MIC (ppm) Chlorera Bulgari Example 1 39.8 Example 2 19.6 Example 3 4.9 Example 4 4.9 Example 5 4.9 Comparative Example 1 No MIC Efficacy Comparative Example 2 39.8 Comparative Example 3 No MIC Efficacy Comparative Example 4 No MIC Efficacy

As shown in Table 7, as a result of performing the MIC test for algae using the water treatment composition of Examples 1 to 5 of the present invention, the bactericidal effect against algae is expressed even at a very low concentration compared to Comparative Examples 1 to 4 It can be seen that the sterilization effect is significantly improved.

As can be seen in the above all experimental examples, the water treatment agent compositions of Examples 1 to 5 of the present invention exhibited an excellent bactericidal effect and at the same time exhibited an anti-corrosion and scale formation inhibitory effect, but any composition of Comparative Examples 1 to 4 In addition, as shown in the present invention, the performance required for cooling system-related water treatment was not simultaneously expressed.

As described above, the water treatment composition according to the present invention and the water treatment method using the same are easy to use, and corrosion can occur by inhibiting the bactericidal effect against various microorganisms including algae and metal surface in a wide range of water quality. It has excellent ability to control microorganisms, corrosion and scale at the same time because it has the ability to reduce the present condition as much as possible and at the same time suppress the scale of divalent metal salt.

Claims (6)

a) 0.1 to 40% by weight of 1-sodium oxide-2-pyridinethiol, b) 0.1 to 7% by weight, based on polyphosphate (P) concentration, c) 0.1 to 25% by weight of acrylate copolymer, and d) water balance Water treatment agent composition comprising a. The method of claim 1, a) 0.5-35 wt% of 1-sodium oxide-2-pyridinethiol, b) 0.5 to 6% by weight, based on the polymerized phosphate (P) concentration, c) 0.5 to 20 wt% of an acrylate copolymer, and d) water balance Water treatment agent composition comprising a. The water treatment composition of claim 1, wherein the b) polyphosphate is selected from the group consisting of tetra potassium pyro phosphate, tetra sodium pyro phosphate, sodium hexa meta polyphosphate. According to claim 1, wherein the c) acrylate polymer is a water treatment composition having the formula [Formula 1]

Where R ₁ and R ₂ are the same or different and are hydrogen, OH or alkyl, X and Y are each independently integers from 1 to 15 A water treatment method in which the concentration of the water treatment composition according to claim 1 is maintained at 0.1 to 500,000 ppm relative to the treated water. The water treatment method according to claim 5, wherein the water treatment agent composition is introduced into a cooling tower, a heat exchanger, or a water pipe.