KR100310166B1 - Descaling agent and water treating program using the same - Google Patents

Descaling agent and water treating program using the same Download PDF

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KR100310166B1
KR100310166B1 KR1019970042082A KR19970042082A KR100310166B1 KR 100310166 B1 KR100310166 B1 KR 100310166B1 KR 1019970042082 A KR1019970042082 A KR 1019970042082A KR 19970042082 A KR19970042082 A KR 19970042082A KR 100310166 B1 KR100310166 B1 KR 100310166B1
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hydrogen atom
carbon number
alkyl
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formula
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KR19990018824A (en
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한순종
유광희
최동진
신정주
박준원
하재민
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조민호
에스케이케미칼주식회사
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors
    • C23F11/188—Mixtures of inorganic inhibitors containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

PURPOSE: An antiscaling agent of preventing scale deposition on pipes has superior performance in water of which calcium hardness(CaH) is higher than 30ppm without toxicity to aqueous living creatures when discharged into water bodies. CONSTITUTION: The antiscaling agent comprises: (i) 0.5-40ppm of an orthophosphate selected from the group consisting of hydroxyethylidene diphosphonic acid, hydroxy phosphonocarboxylic acid, amino trimethylene phosphonic acid and phosphono butane tricarboxylic acid; (ii) 0.5-40ppm of a polyphosphate; (iii) 0.1-50ppm of organic phosphate; (iv) 0.1-20ppm of azole compound selected from the group consisting of tolyltriazole, benzotriazole, and mercapto benzothiazole; and (v) 0.1-100ppm of acrylate trimer represented by chemical formula I, where l, m, and n are identical or different each other, being an integer of 5 to 1000, respectively; R1 and R6 are identical or different each other, and denote hydrogen atom, alkyl or hydroxy respectively; R2 and R3 are identical or different each other, and denote hydrogen atom or alkyl with a carbon number of C1 to C2, respectively; R4 denote hydrogen atom or alkyl with a carbon number of C1 to C5; R5 denote alkyl with a carbon number of C1 to C8 or arylalkyl with a carbon number of C8 to C10; X and Y are identical or different each other, and denote hydrogen atom, alkyl with a carbon number of C1 to C5, hydroxy alkyl with a carbon number of C1 to C5; R0 is selected from chemical formula II, chemical formula III, and chemical formula IV. In the chemical formula II, III, and IV, R6 denote hydrogen atom or alkyl with a carbon number of C1 to C2; R12 denote hydrogen atom or alkyl with a carbon number of C1 to C2; R13 and R14 are identical or different each other, and denote hydrogen atom, alkyl with a carbon number of C1 to C8, cycloalkyl with a carbon number of C6 to C8, benzyl or chemical formula V; R7 denote alkyl with a carbon number of C to C7, allyl with a carbon number of C6 to C8, arylalkyl with a carbon number of C6 to C10 or chemical formula V, wherein i is an integer of 1 to 3; R9 denote hydrogen atom or alkyl with a carbon number of C1 to C2; R10 denote hydrogen atom or alkyl with a carbon number of C1 to C6.

Description

금속의 부식방지 및 수중이온의 스케일 형성을 억제하기 위한 수처리 프로그램 및 수처리 방법Water treatment program and water treatment method to prevent metal corrosion and to suppress scale formation of water ions

본 발명은 금속의 부식방지 및 수중이온의 스케일 형성을 억제하기 위한 수처리 프로그램 및 수처리 방법에 관한 것으로써, 더욱 상세하게는 칼슘 경도가 30ppm 이상인 수질에서 발생할 수 있는 부식 및 스케일의 형성을 억제하는데 유용하며, 오르토포스페이트 이온, 폴리포스페이트 이온, 오르가닉 포스페이트 이온, 아졸계화합물 및 아크릴레이트 삼중합체를 포함하고 있는 것을 특징으로 하는 새로운 수처리 프로그램에 관한 것이다.The present invention relates to a water treatment program and a water treatment method for preventing corrosion of metals and inhibiting scale formation of water ions. More particularly, the present invention is useful for inhibiting corrosion and scale formation that may occur in water quality of 30 ppm or more of calcium hardness. And a new water treatment program comprising orthophosphate ions, polyphosphate ions, organic phosphate ions, azole compounds and acrylate terpolymers.

전기전도체인 금속이 이온전도체인 전해질 내에 포함되어 있거나 서로 접촉하면, 금속표면의 상태가 불균일하게 되어 표면에 양극과 음극이 형성된다. 이때 양극에서는 전자를 방출하고 금속 이온이 전해질 내로 용해되며, 음극에서는 양극으로부터 이동해 온 전자가 전해질 속의 이온과 결합하게 되는데, 이러한 반응과정을 통하여 금속이 본연의 모습인 산화물 상태로 되돌아가려는 현상을 부식이라고 한다. 그리고, 금속 배관 내의 물 속에 녹아있는 칼슘염, 마그네슘 염 등의 양이온이 수중의 음이온과 결합하여 금속의 탄산염이나 수산화물의 형태로 침전된 것을 스케일이라고 하는데, 이러한 스케일이 형성되면 금속 배관의 열전도도가 나빠질 뿐 만 아니라, 금속배관의 국부 부식을 유발하게 된다. 냉각탑, 열교환기, 밀폐 및 개방 냉각 시스템 등의 금속 배관에서 이러한 부식 및 스케일 형성 현상이 발생하면 산업 장치에 커다란 장애를 줄 수 있다. 이러한 현상을 방지하기 위한 종래의 수처리제 조성물로서는 크롬염, 아연염, 인산염, 아크릴레이트 공중합체를 함유하는 조성물을 사용하거나(미합중국특허 제 4,324,684호 및 4,411,865호). 아연염과 무수 말레익 중합체를 함유하는 조성물을 사용하는 것(미합중국 특허 제 4,530,955 호) 등이 알려져 있다.When a metal, which is an electrical conductor, is contained in or in contact with an electrolyte, which is an ion conductor, the state of the metal surface becomes uneven to form an anode and a cathode on the surface. At this time, the anode emits electrons and the metal ions dissolve into the electrolyte, and the electrons from the anode combine with the ions in the electrolyte. This reaction process causes the metal to return to its original oxide state. It is called. In addition, the scale of cations such as calcium salts and magnesium salts dissolved in water in the metal pipes and precipitated in the form of carbonates or hydroxides of the metal by combining with anions in the water, when the scale is formed, the thermal conductivity of the metal pipes Not only will it worsen, it will also cause local corrosion of the metal piping. Such corrosion and scale formation in metal piping, such as cooling towers, heat exchangers, sealed and open cooling systems, can cause significant disruption to industrial equipment. Conventional water treatment compositions for preventing such phenomena include compositions containing chromium salts, zinc salts, phosphates, acrylate copolymers (US Pat. Nos. 4,324,684 and 4,411,865). It is known to use a composition containing zinc salt and anhydrous maleic polymer (US Pat. No. 4,530,955).

그러나 상기와 같은 종래의 수처리제 조성물들은 부식을 방지하는 효과나 스케일을 억제하는 능력에서 다소 차이는 있지만 만족할 만한 성과를 기대할 수 없을 뿐만 아니라 특히, 크롬염의 경우에는 공해유발, 인체독성, 안정성등의 여러 문제점으로 인하여 그 사용이 규제되어 있고, 아연염의 경우에는 어폐류에 치명상을 줄수 있으며, 무기 인산염의 경우에는 관리상태에 따라 열부하를 많이 받는 열교환기내에 칼슘포스페이트 스케일을 형성시키는 단점이 있다.However, the conventional water treatment composition as described above is somewhat different in the effect of preventing corrosion or the ability to suppress scale, but can not expect satisfactory performance, in particular, in the case of chromium salt, such as pollution, human toxicity, stability, etc. Due to the problem, its use is restricted, and in case of zinc salt, it can cause fatality to fish and shellfish, and in case of inorganic phosphate, calcium phosphate scale is formed in heat exchanger which receives a lot of heat load depending on the management condition.

본 발명은 상기와 같은 문제점을 해결하는 동시에, 사용이 간편하고 안전한 수처리 프로그램 및 수처리 방법을 제공하는데 그 목적이 있다.The present invention has been made in view of solving the above problems and at the same time provides an easy-to-use and safe water treatment program and water treatment method.

본 발명은 수처리 프로그램 내에서 질량 기준으로 오르토포스페이트 이온의 농도는 0.5 내지 30ppm, 폴리포스페이트 이온의 농도는 0.5 내지 40ppm, 오르가닉 포스페이트 이온의 농도는 0.1 내지 50ppm, 아졸계화합물의 농도는 0.1 내지 20ppm, 그리고 아크릴레이트 삼중합체의 농도는 0.1 내지 100ppm으로 유지되는 것을 특징으로 하는 금속의 부식방지 및 수중이온의 스케일 형성를 억제하기 위한 수처리 프로그램을 제공한다.In the present invention, the concentration of orthophosphate ions is 0.5 to 30 ppm, the concentration of polyphosphate ions is 0.5 to 40 ppm, the concentration of organic phosphate ions is 0.1 to 50 ppm, and the concentration of the azole compound is 0.1 to 20 ppm in the water treatment program. And a concentration of the acrylate terpolymer is maintained at 0.1 to 100 ppm to provide a water treatment program for preventing corrosion of metals and inhibiting scale formation of water ions.

또한 본 발명은 수처리제 조성물을 수배관에 투여하여 수처리 프로그램 내에서 질량 기준으로 오르토포스페이트 이온의 농도는 0.5 내지 30ppm, 폴리포스페이트 이온의 농도는 0.5 내지 40ppm, 오르가닉 포스페이트 이온의 농도는 0.5 내지 50ppm, 아졸계화합물의 농도는 0.1 내지 20ppm, 그리고 아크릴레이트 삼중합체의 농도는 0.1 내지 100ppm으로 유지하는 과정을 포함하는 금속의 부식방지 및 수중이온의 스케일 형성를 억제하는 방법을 제공한다.In addition, the present invention is to administer the water treatment composition to the water pipe in the water treatment program in the concentration of orthophosphate ions by mass on the basis of 0.5 to 30ppm, the concentration of polyphosphate ions is 0.5 to 40ppm, the concentration of the organic phosphate ions is 0.5 to 50ppm, It provides a method for preventing the corrosion of metals and the scale formation of water ions comprising the step of maintaining the concentration of the azole compound is 0.1 to 20ppm, and the concentration of the acrylate terpolymer is 0.1 to 100ppm.

본 발명에 따른 수처리 프로그램에 있어서, 상기 오르토포스페이트 이온의 농도를 유지하기 위한 오르토포스페이트로는 제 1인산소다, 제 2인산소다, 제 3인산소다 및 인산 등을 사용하는 것이 바람직하고, 상기 폴리포스페이트 이온의 농도를 유지하기 위한 폴리포스페이트로는 헥사메타인산소다, 피로인산소다, 피로인산칼륨 등을 사용하는 것이 바람직하며, 상기 오르가닉 포스페이트 이온의 농도를 유지하기 위한 오르가닉 포스페이트로서는 하이드록시 에틸리딘 디포스포닉산, 하이드록시 포스포노 카르복실산, 아미노 트리메틸렌포스포닉산, 포스포노 부탄 트리카르복실산 등을 사용할 수 있다. 또한, 상기 아졸계 화합물의 농도를 유지하기 위한 아졸계 화합물로서는 톨릴트리아졸, 벤조트리아졸, 머캅토 벤조씨아졸 등을 사용하는 것이 바람직하며, 상기 아크릴레이트 삼중합체의 농도를 유지하기 위한 아크릴레이트 삼중합체는 하기 화학식 1 식의 구조를 가지는 것이 바람직하다.In the water treatment program according to the present invention, as the orthophosphate for maintaining the concentration of the orthophosphate ions, it is preferable to use a first sodium phosphate, a second sodium phosphate, a third sodium phosphate and phosphoric acid. As polyphosphate for maintaining the concentration of ions, it is preferable to use sodium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, or the like, and as the organic phosphate for maintaining the concentration of the organic phosphate ion, hydroxyethylidine Diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphono butane tricarboxylic acid, etc. can be used. As the azole compound for maintaining the concentration of the azole compound, tolyl triazole, benzotriazole, mercapto benzothiazole, and the like are preferably used. The acrylate for maintaining the concentration of the acrylate terpolymer is preferable. It is preferable that a terpolymer has a structure of following General formula (1).

Figure kpo00001
Figure kpo00001

상기 식에서 l, m, n 은 서로 같거나 다른 것으로서 각각 5내지 1,000의 정수이고, R1과 R8은 서로 같거나 다른 것으로서 각각 수소원자, 알킬기 또는 하이드록시기를 나타내며, R2와 R3은 서로 같거나 다른 것으로서 각각 수소원자 또는 C1-C2알킬기를 나타내며, R4는 수소원자 또는 C1-C5의 알킬기를 나타내며, R5는 C1-C8알킬기 또는 C8-C10알알킬기를 나타내며, X, Y 는 서로 같거나 다른 것으로서 각각 수소원자, C1-C5알킬기,C1-C5하이드록시알킬기를 나타내며, R0는 하기 화학식 2, 3 및 4로 부터 선택되는 하나의 단위이다.In the above formula, l, m, n are the same as or different from each other, and are each an integer of 5 to 1,000, R 1 and R 8 are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, or a hydroxy group, and R 2 and R 3 each other. The same or different, each represent a hydrogen atom or a C 1 -C 2 alkyl group, R 4 represents a hydrogen atom or an alkyl group of C 1 -C 5 , and R 5 represents a C 1 -C 8 alkyl group or a C 8 -C 10 alalkyl group X and Y are the same as or different from each other, and each represents a hydrogen atom, a C 1 -C 5 alkyl group, a C 1 -C 5 hydroxyalkyl group, and R 0 is one selected from Formulas 2, 3, and 4, Unit.

Figure kpo00002
Figure kpo00002

Figure kpo00003
Figure kpo00003

Figure kpo00004
Figure kpo00004

여기서 R6은 서로 같거나 다른 것으로서 각각 수소원자 또는 C1-C2알킬기를 나타내며, R12는 수소원자, 또는 C1-C2알킬기이며, R13및 R14는 서로 같거나 다른 것으로서 수소원자, C1-C8알킬기, C6-C8사이클로알킬기, 벤질기 또는 하기 화학식5의 단위체를 나타내며, R7은 C1-C6알킬기 또는 C6-C10알릴기, C6-C10알알킬기 또는 화학식 5의 단위체를 나타낸다.Wherein R 6 is the same as or different from each other and represents a hydrogen atom or a C 1 -C 2 alkyl group, R 12 is a hydrogen atom or a C 1 -C 2 alkyl group, and R 13 and R 14 are the same or different and are hydrogen atoms , A C 1 -C 8 alkyl group, a C 6 -C 8 cycloalkyl group, a benzyl group or a unit of formula (5), R 7 is a C 1 -C 6 alkyl group or a C 6 -C 10 allyl group, C 6 -C 10 Alalkyl group or the unit of general formula (5) is shown.

Figure kpo00005
Figure kpo00005

상기 화학식 5에서 i는 1 내지 3의 정수이고, R9는 수소원자 또는 C1-C2알킬기, R10은 수소원자 또는 C1-C6알킬기를 나타낸다.In Formula 5, i is an integer of 1 to 3, R 9 is a hydrogen atom or a C 1 -C 2 alkyl group, R 10 is a hydrogen atom or a C 1 -C 6 alkyl group.

이하, 본 발명을 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

상기 오르토포스페이트는 부식반응중 양극 및 음극반응을 억제하는 기능을 하는 것으로서, 수처리 프로그램 내에서 질량기준으로 오르토포스페이트 이온의 농도가 0.5 내지 30ppm, 바람직하게는 1.0 내지 25.0ppm으로 유지되면 적당하다. 상기 폴리포스페이트는 부식반응중 음극반응을 억제하는 기능 및 스케일억제기능을 하는 것으로서, 수처리 프로그램 내에서 포스페이트 이온의 농도가 0.5 내지 40ppm, 바람직하게는 1.0 내지 35ppm 으로 유지되도록 하는 것이 좋다. 상기 이온의 농도가 상기 범위보다 낮으면 효과가 저하되고, 상기 범위보다 높으면 경제성이 떨어진다. 상기 포스포네이트는 부식반응중 음극반응을 억제하는 기능 및 칼슘염 스케일 형성 억제기능을 하는 것으로서, 수처리 프로그램 내에서 오르가닉 포스페이트 이온의 농도가 0.1 내지 50ppm, 바람직하게는 0.5 내지 45ppm 으로 유지되도록 하면 적당하다. 상기 오르가닉 포스페이트 이온의 농도가 0.1ppm미만이면 수처리 기능이 저하되고 40ppm을 초과하면 경제성이 떨어진다. 상기 아졸계화합물은 구리 및 구리화합물의 부식 억제 능력이 탁월하며, 수처리 프로그램 내에서 아졸계 화합물의 농도가 0.1 내지 20.0ppm, 바람직하게는 0.2 내지 19ppm으로 유지되도록 하면 적당하며, 그 사용량이 0.1ppm미만이면 방식효과가 미미하며 20ppm이상이면 경제성이 떨어진다. 또한 상기 아크릴레이트 삼중합체는 수중의 스케일 형성 억제 기능을 하는 것으로서, 수처리 프로그램 내에서 아크릴레이트 삼중합체의 농도가 0.1 내지 100ppm, 바람직하게는 0.5 내지 95ppm 으로 유지되도록 하면 적당하다. 이때, 상기 아졸계 화합물과 아크릴레이트 삼중합체의 적용 농도가 각각의 범위에 미달할 경우에는 수처리 기능이 저하되고, 그 범위를 초과할 경우에는 효과 상승에 비해 경제성이 떨어지게 된다. 여기서 수처리 프로그램이란 소정 조성의 수처리제를 수배관의 물 속에 넣은 것을 말한다.The orthophosphate serves to suppress the anodic and cathodic reactions during the corrosion reaction, and is appropriate if the concentration of orthophosphate ions is maintained at 0.5 to 30 ppm, preferably 1.0 to 25.0 ppm, on a mass basis within the water treatment program. The polyphosphate has a function of inhibiting cathodic reaction and a scale inhibitory function during the corrosion reaction, and it is preferable to maintain the concentration of phosphate ions in the water treatment program at 0.5 to 40 ppm, preferably 1.0 to 35 ppm. If the concentration of the ion is lower than the above range, the effect is lowered, and if it is higher than the above range, the economy is inferior. The phosphonate has a function of inhibiting cathodic reaction during corrosion reaction and a function of inhibiting calcium salt scale formation, so that the concentration of organic phosphate ions in the water treatment program is maintained at 0.1 to 50 ppm, preferably 0.5 to 45 ppm. It is suitable. If the concentration of the organic phosphate ion is less than 0.1 ppm, the water treatment function is lowered, and if it exceeds 40 ppm, the economy is inferior. The azole compound is excellent in the ability to inhibit the corrosion of copper and copper compounds, it is appropriate to maintain the concentration of the azole compound in the water treatment program is 0.1 to 20.0ppm, preferably 0.2 to 19ppm, the amount of use is 0.1ppm If it is less than, the anticorrosive effect is insignificant. In addition, the acrylate terpolymer has a function of inhibiting scale formation in water, and it is suitable to maintain the concentration of the acrylate terpolymer in the water treatment program at 0.1 to 100 ppm, preferably 0.5 to 95 ppm. At this time, when the application concentration of the azole compound and the acrylate terpolymer is less than the respective ranges, the water treatment function is lowered, and when it exceeds the ranges, the economy is inferior to the effect increase. Here, the water treatment program refers to a water treatment agent having a predetermined composition in water of a water pipe.

상기와 같은 본 발명의 수처리 프로그램은 냉각탑, 열교환기등 각종 산업용 수배관에서 발생할 수 있는 부식을 방지하고 스케일의 형성을 억제하는 데 보다 효과적으로 사용될 수 있으므로, 개방 순환식 냉각수계, 일과식 냉각수계가 주된 사용대상이다. 특히, 농축운전으로 염류가 농축되어 부식성향과 스케일 성향이 높은 개방 순환식 냉각수계의 수처리제로 사용하는 것이 바람직하다.The water treatment program of the present invention as described above can be used more effectively to prevent the formation of scales and to prevent corrosion that can occur in various industrial water pipes, such as cooling towers, heat exchangers, open circulation cooling water system, transient cooling water system is the main It is used. In particular, it is preferable to use the water treatment agent of an open circulation cooling water system in which salts are concentrated by a concentration operation and have high corrosion tendency and scale tendency.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같다. 단, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. However, this invention is not limited by the following Example.

[실시예 1 - 3][Examples 1-3]

온도 45℃에서 탄소강 시험편(0.218dm2)을 회전속도 170rpm으로 5일간 회전시켜서 부식속도를 측정하였다. 이때 다음 표1의 시험수질에 대하여 표2에 표시된 수처리제 성분을 표2에 표시한 각 농도로 유지시킨 후 실험하였고, 상기 시험편의 부식속도(mdd, mg/(dm2ㆍ day))를 표4에 나타내었다.The corrosion rate was measured by rotating the carbon steel test piece (0.218dm 2 ) at a temperature of 45 ° C. for 5 days at a rotational speed of 170 rpm. At this time, the test water quality of the following Table 1 was tested after maintaining the water treatment agent components shown in Table 2 at each concentration shown in Table 2, and the corrosion rate (mdd, mg / (dm 2 · day)) of the test piece Table 4 Shown in

[실시예 4 - 6]EXAMPLE 4-6

테스트 용액을 밀폐시키고 50℃ 에서 7시간 정체시킨 후 테스트 용액을 0.45 마이크로 미터 필터로 여과하여 칼슘경도를 측정하여 칼슘염 스케일 억제율을 측정하였다. 이때 다음 표1의 시험수질에 표2에 표시된 수처리제 성분을 표2에 표시한 각 농도로 유지시킨 후 실험하였고, 상기 칼슘염 스케일 억제율의 결과를 표5에 나타내었다.The test solution was sealed and allowed to stand at 7O < 0 > C for 7 hours, and then the test solution was filtered through a 0.45 micrometer filter to measure calcium hardness to determine calcium salt scale inhibition. At this time, the water treatment agent shown in Table 2 in the test water quality of the following Table 1 was tested after maintaining at each concentration shown in Table 2, the results of the calcium salt scale inhibition rate is shown in Table 5.

Figure kpo00006
Figure kpo00006

pH 는 0.5N 수산화나트륨 수용액과 0.5N 황산 수용액으로 조절하였다.pH was adjusted with 0.5N sodium hydroxide aqueous solution and 0.5N sulfuric acid aqueous solution.

Conductivity : 전기전도도Conductivity: electrical conductivity

Ca-H : 칼슘경도 (염화칼슘으로 조절하였다.)Ca-H: calcium hardness (controlled by calcium chloride)

Mg-H : 마그네슘경도 (황산마그네슘으로 조절하였다.)Mg-H: magnesium hardness (adjusted with magnesium sulfate)

Cl-: 염소이온 (염화나트륨으로 조절하였다.)Cl -: Chloride (was adjusted with sodium chloride.)

Figure kpo00007
Figure kpo00007

오르가닉 포스페이트 : 하이드록시 에틸리딘 디포스포닉산(상품명: Unihib 106, LONZA사)Organic phosphate: hydroxy ethylidine diphosphonic acid (brand name: Unihib 106, LONZA company)

아크릴레이트 삼중합체 : 상품명 Acumer 3000 (Rohm & Haas사)Acrylate terpolymer: trade name Acumer 3000 (Rohm & Haas)

[비교예 1 - 3][Comparative Example 1-3]

표1의 시험수질에 다음 표3에 표시된 수처리제 성분의 각 농도를 유지시킨 후 상기 실시예 1 - 3과 동일한 방법으로 실험하여 부식속도의 결과를 표 4에 나타내었다.After maintaining each concentration of the water treatment agent component shown in the following Table 3 in the test water quality of Table 1 and tested in the same manner as in Examples 1 to 3 shown in Table 4 the results of the corrosion rate.

[비교예 4 - 6][Comparative Example 4-6]

표1의 시험수질에 다음 표3에 표시된 수처리제 성분의 각 농도를 유지시킨 후 상기 실시예 4 - 6과 동일한 방법으로 실험하여 칼슘염 스케일 억제율의 결과를 표 5에 나타내었다.After maintaining each concentration of the water treatment agent components shown in Table 3 in the test water quality of Table 1, the experiments were performed in the same manner as in Examples 4-6, and the results of the calcium salt scale inhibition rate are shown in Table 5.

억제율 (%) = Ce/Ct × 100Inhibition Rate (%) = Ce / Ct × 100

Ct : 시험전의 시험액중의 칼슘경도Ct: Calcium hardness in test solution before test

Ce : 시험후의 시험액중의 칼슘경도Ce: calcium hardness in test solution after test

Figure kpo00008
Figure kpo00008

오르가닉 포스페이트 : 하이드록시 에틸리딘 디포스포닉산(상품명: Unihib 106, LONZA사)Organic phosphate: hydroxy ethylidine diphosphonic acid (brand name: Unihib 106, LONZA company)

아크릴레이트 삼중합체 : 상품명 Acumer 3000 (Rohm & Haas사)Acrylate terpolymer: trade name Acumer 3000 (Rohm & Haas)

Figure kpo00009
Figure kpo00009

* mdd = mg / (dm2ㆍday)* mdd = mg / (dm 2 ㆍ day)

Figure kpo00010
Figure kpo00010

상기 표 4에 의하면 표 1의 수질에 대한 본 발명에 따른 실시예 1 내지 3 의 부식속도는 비교예 1 내지 3 보다 현저히 작았으며, 또한 상기 표 5에 의하면 본 발명에 따른 실시예 4 내지 6의 수처리 프로그램의 스케일 억제율이 비교예 4 내지 6의 경우 보다 높은 수치를 나타냄을 알 수 있다.According to Table 4, the corrosion rates of Examples 1 to 3 according to the present invention for the water quality of Table 1 were significantly smaller than that of Comparative Examples 1 to 3, and also according to Table 5 of Examples 4 to 6 according to the present invention. It can be seen that the scale inhibition rate of the water treatment program is higher than that of Comparative Examples 4 to 6. FIG.

따라서, 본 발명의 수처리제는 금속의 부식 및 스케일 생성을 방지하는 효과가 매우 우수하며, 또한 본 발명의 수처리제는 금속표면에서 발생할 수 있는 부식 반응을 억제하여 부식이 일어날 수 있는 조건을 최대한 축소시킴으로써 탄소강과 구리재질에 대해 뛰어난 방식효과를 기대할 수 있고, 아크릴레이트 공중합체와 포스포네이트가 2가 금속 염의 스케일을 억제하는 능력이 우수하므로 적은 양으로 부식 및 스케일을 동시에 조절하는 기능이 뛰어나다.Therefore, the water treatment agent of the present invention is very effective in preventing corrosion and scale generation of the metal, and also the water treatment agent of the present invention inhibits the corrosion reaction that may occur on the metal surface to reduce the conditions that can cause corrosion as possible carbon steel Excellent anticorrosive effect can be expected for the copper and copper materials, and the acrylate copolymer and phosphonate have excellent ability to suppress the scale of the divalent metal salt.

Claims (4)

(a) 수처리 프로그램 내에서 질량 기준으로 오르토포스페이트 이온의 농도가 0.5 내지 30 ppm;(a) a concentration of orthophosphate ions from 0.5 to 30 ppm on a mass basis within the water treatment program; (b) 폴리포스페이트 이온의 농도가 0.5 내지 40 ppm;(b) the concentration of polyphosphate ions is from 0.5 to 40 ppm; (c) 오르가닉 포스페이트 이온의 농도가 0.1 내지 50 ppm;(c) the concentration of organic phosphate ions is from 0.1 to 50 ppm; (d) 아졸계 화합물의 농도가 0.1 내지 20 ppm; 및(d) the concentration of azole compound is 0.1-20 ppm; And (e) 하기 화학식 1로 표시되는 아크릴레이트 삼중합체의 농도가 0.1 내지 100 ppm으로 유지되는 것을 특징으로 하는 금속의 부식방지 및 수중이온의 스케일 형성을 억제하기 위한 수처리 프로그램:(e) a water treatment program for preventing corrosion of metals and inhibiting scale formation of water ions, wherein the concentration of the acrylate terpolymer represented by Formula 1 is maintained at 0.1 to 100 ppm: [화학식 1][Formula 1]
Figure kpo00011
Figure kpo00011
 상기 화학식 1에서,In Chemical Formula 1, l, m, n 은 서로 같거나 다른 것으로서 각각 5내지 1,000의 정수이고; R1과 R8은 서로 같거나 다른 것으로서 각각 수소원자, 알킬기 또는 하이드록시기를 나타내며; R2와 R3은 서로 같거나 다른 것으로서 각각 수소원자 또는 C1-C2알킬기를 나타내며; R4는 수소원자 또는 C1-C5의 알킬기를 나타내며; R5는 C1-C8알킬기 또는 C8-C10알알킬기를 나타내며; X, Y 는 서로 같거나 다른 것으로서 각각 수소원자; C1-C5알킬기,C1-C5하이드록시알킬기를 나타내며; R0는 하기 화학식 2, 화학식 3 및 화학식 4로 이루어진 군으로부터 선택되는 화합물을 나타낸다.l, m, n are the same or different from each other and are an integer of 5 to 1,000; R 1 and R 8 are the same as or different from each other, and each represent a hydrogen atom, an alkyl group, or a hydroxy group; R 2 and R 3 , which are the same as or different from each other, represent a hydrogen atom or a C 1 -C 2 alkyl group; R 4 represents a hydrogen atom or an alkyl group of C 1 -C 5 ; R 5 represents a C 1 -C 8 alkyl group or a C 8 -C 10 alalkyl group; X and Y are the same as or different from each other, and each hydrogen atom; A C 1 -C 5 alkyl group, a C 1 -C 5 hydroxyalkyl group; R 0 represents a compound selected from the group consisting of the following general formulas (2), (3) and (4). [화학식 2][Formula 2]
Figure kpo00012
Figure kpo00012
 [화학식 3][Formula 3]
Figure kpo00013
Figure kpo00013
 [화학식 4][Formula 4]
Figure kpo00014
Figure kpo00014
 상기 화학식 2, 화학식 3 및 화학식 4의 식에서,In Formula 2, Formula 3 and Formula 4, R6은 서로 같거나 다른 것으로서 각각 수소원자 또는 C1-C2알킬기를 나타내며; R12는 수소원자, 또는 C1-C2알킬기이며; R13및 R14는 서로 같거나 다른 것으로서 수소원자, C1-C8알킬기, C6-C8사이클로알킬기, 벤질기 또는 하기 화학식 5의 단위체를 나타내며; R7은 C1-C6알킬기 또는 C6-C10알릴기, C6-C10알알킬기 또는 하기 화학식 5로 표시되는 화합물을 나타낸다.R 6 is the same or different from each other and represents a hydrogen atom or a C 1 -C 2 alkyl group; R 12 is a hydrogen atom or a C 1 -C 2 alkyl group; R 13 and R 14 , which are the same as or different from each other, represent a hydrogen atom, a C 1 -C 8 alkyl group, a C 6 -C 8 cycloalkyl group, a benzyl group, or a unit of formula 5; R 7 represents a C 1 -C 6 alkyl group or a C 6 -C 10 allyl group, a C 6 -C 10 alalkyl group, or a compound represented by the following formula (5). [화학식 5][Formula 5]
Figure kpo00015
Figure kpo00015
 상기 화학식 5에서,In Chemical Formula 5, i는 1 내지 3의 정수이고; R9는 수소원자 또는 C1-C2알킬기이고; R10은 수소원자 또는 C1-C6알킬기를 나타낸다.i is an integer from 1 to 3; R 9 is a hydrogen atom or a C 1 -C 2 alkyl group; R 10 represents a hydrogen atom or a C 1 -C 6 alkyl group. 제1항에 있어서, 상기 오르가닉 포스페이트 이온의 농도를 유지하기 위한 포스포네이트는 하이드록시 에틸리딘 디포스포닉산, 하이드록시 포스포노 카르복실산, 아미노 트리메틸렌포스포닉산, 포스포노 부탄 트리 카르복실산으로 이루어진 군으로 부터 선택되는 것인 금속의 부식방지 및 수중이온의 스케일 형성를 억제하기 위한 수처리 프로그램.The method of claim 1, wherein the phosphonate for maintaining the concentration of the organic phosphate ions is hydroxy ethylidine diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphonic acid, phosphono butane tricarboxyl Water treatment program to prevent corrosion of metals and scale formation of water ions selected from the group consisting of acids. 제1항에 있어서, 상기 아졸계 화합물의 농도를 유지하기 위한 아졸계 화합물은 톨릴트리아졸, 벤조트리아졸, 머캅토 벤조씨아졸으로 이루어진 군으로부터 선택되는 것인 금속의 부식방지 및 수중이온의 스케일 형성를 억제하기 위한 수처리 프로그램.According to claim 1, wherein the azole compound for maintaining the concentration of the azole-based compound is selected from the group consisting of tolyltriazole, benzotriazole, mercapto benzothiazol anti-corrosion and scale of the water ion Water treatment program to suppress formation. 제1항 기재의 수처리 프로그램으로 실시되는 금속의 부식방지 및 수중 이온의 스케일 형성을 억제하는 방법.A method for preventing corrosion of metals and scale formation of ions in water carried out by the water treatment program according to claim 1.
KR1019970042082A 1997-08-28 1997-08-28 Descaling agent and water treating program using the same KR100310166B1 (en)

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CN103508570A (en) * 2012-06-25 2014-01-15 上海思曼泰化工科技有限公司 Environmental protection and high efficiency corrosion inhibitor for inhibiting salt water corrosion on carbon steel, preparation method and use method thereof

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JP2002250845A (en) * 2001-02-23 2002-09-06 Hosiden Corp Optical connector with shutter
KR20040012135A (en) * 2002-08-01 2004-02-11 에스케이케미칼주식회사 Water treatmrnt composition, preparation method of the same and water treatment method using the same

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KR970026953A (en) * 1995-11-29 1997-06-24 김준웅 Corrosion prevention water treatment composition of metal

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KR970026953A (en) * 1995-11-29 1997-06-24 김준웅 Corrosion prevention water treatment composition of metal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103508570A (en) * 2012-06-25 2014-01-15 上海思曼泰化工科技有限公司 Environmental protection and high efficiency corrosion inhibitor for inhibiting salt water corrosion on carbon steel, preparation method and use method thereof

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