KR100315438B1 - Water treatment composition for preventing scale and corrosion in enclosed circulation cooling system - Google Patents

Water treatment composition for preventing scale and corrosion in enclosed circulation cooling system Download PDF

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KR100315438B1
KR100315438B1 KR1019970042083A KR19970042083A KR100315438B1 KR 100315438 B1 KR100315438 B1 KR 100315438B1 KR 1019970042083 A KR1019970042083 A KR 1019970042083A KR 19970042083 A KR19970042083 A KR 19970042083A KR 100315438 B1 KR100315438 B1 KR 100315438B1
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corrosion
water treatment
scale
cooling system
treatment composition
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KR1019970042083A
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KR19990018825A (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
    • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
    • 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)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

PURPOSE: A water treatment composition for preventing scale deposition on pipes and corrosion of metal pipes in enclosed circulation cooling system is provided. CONSTITUTION: The water treatment composition comprises 0.1 to 50 wt.% of sodium nitrite or potassium nitrite; 0.1 to 40.0 wt.% of one or more phosphonate compounds selected from the group consisting of phosphonobutane tricarboxylic acid, hydroxyethylidine diphosphonic acid, hydroxyphosphono carboxylic acid and amino trimethylene phosphonic acid; 0.1 to 20.0 wt.% of azole compounds selected from the group consisting of tolyltriazole, mercapto benzothiazole and benzotriazole; and a balance of water.

Description

밀폐 순환 냉각시스템의 부식 및 스케일 억제 수처리제 조성물 및 그 방법Corrosion and Scale Inhibition Water Treatment Composition and Its Method in a Closed-Circulation Cooling System

본 발명은 밀폐 순환 냉각시스템의 냉각수에 의해 발생하는 부식 및 스케일의 형성을 억제하는 수처리제 및 그 방법에 관한 것으로써, 더욱 상세하게는 아질산염, 포스포네이트 및 아졸계 화합물을 함유하고 있는 것을 특징으로 하는 밀폐순환 냉각시스템용 수처리제 조성물에 관한 것이다.The present invention relates to a water treatment agent and a method for inhibiting corrosion and scale formation caused by cooling water in a closed circulation cooling system, and more particularly, containing nitrite, phosphonate and azole compounds. It relates to a water treatment agent composition for hermetic circulation cooling system.

실제 산업현장에 설치된 각종 산업용 설비의 냉각시스템에서는 부식 및 스케일이 발생하여 냉각수의 순환 시스템에 커다란 장애를 주고 있는 실정이다. 특히, 밀폐 순환식 냉각수계는 이온 전도체인 전해질과 전기전도체인 금속배관이 서로 접촉되어 있으므로 항상 부식에 대한 위험요소가 있으며, 냉각수 속에 용해되어 있는 칼슘염, 마그네슘염 등의 2가 금속염이 고온에서 탄산염이나 수산화물의 형태로 침전됨으로서 스케일을 형성하기 쉽다. 이러한 스케일이 형성되면 금속배관의 열전도도가 나빠질 뿐 만 아니라, 금속배관의 국부 부식을 유발하게 되므로, 냉각시스템의 원활한 운전을 위하여는 생성된 스케일을 물리적으로 제거하거나, 냉각수속에 염류가 함유되지 않도록 주의하여야 한다. 그러나 이러한 방법은 그 공정이 위험하고 번거로울 뿐만 아니라, 금속배관의 부식 및 스케일 형성을 본질적으로 억제하지 못한다는 단점이 있다.Actually, in the cooling systems of various industrial facilities installed in industrial sites, corrosion and scale occur, which causes a great obstacle to the circulation system of the cooling water. Especially, in the closed circulation cooling water system, there is always a risk of corrosion because the electrolyte which is the ion conductor and the metal pipe which is the electrical conductor are in contact with each other, and the divalent metal salts such as calcium salt and magnesium salt dissolved in the cooling water are kept at It is easy to form scale by precipitation in the form of carbonate or hydroxide. When such scale is formed, not only the thermal conductivity of the metal pipe is degraded, but also the local corrosion of the metal pipe is caused. Therefore, for the smooth operation of the cooling system, physically removing the scale or preventing salt from being contained in the cooling water. Care must be taken. However, this method has the disadvantage that the process is not only dangerous and cumbersome, but also inherently does not inhibit corrosion and scale formation of the metal pipe.

본 발명은 밀폐 냉각시스템의 냉각수에서 발생하는 부식 및 스케일을 억제하는 동시에, 사용이 간편하고 안전한 수처리제를 제공하는데 그 목적이 있다.It is an object of the present invention to provide a water treatment agent which is easy to use and safe while suppressing corrosion and scale occurring in the cooling water of a closed cooling system.

본 발명은 아질산염 0.1 내지 50 중량%, 포스포네이트 0.1 내지 40 중량%, 아졸계 화합물 0.1 내지 20 중량% 및 잔부로서 물을 함유하고 있는 것을 특징으로 하는 밀폐순환 냉각 시스템에서의 부식 및 스케일 억제용 수처리제 조성물을 제공한다. 또한 본 발명은 상기 수처리제 조성물을 밀페 순환 냉각시스템에 투여하는 것을 포함하는 밀폐 순환 냉각 시스템의 부식 및 스케일 억제 방법을 제공한다. 본 발명의 수처리제 조성물에 있어서, 아질산염으로서는 소디움 나이트라이트, 포타슘 나이트라이트 등을 사용하는 것이 바람직하며, 포스포네이트로는 하이드록시 에틸리딘 디포스포닉산, 하이드록시 포스포노 카르복실산, 아미노 트리메틸렌포스포닉산, 포스포노부탄 트리 카르복실산을 단독으로 또는 하나이상 혼합하여 사용하는 것이 바람직하며, 아졸계 화합물로서는 톨릴트리아졸, 머캅토 벤조씨아졸, 벤조트리아졸 등이 사용될 수 있다.The present invention is for inhibiting corrosion and scale in a closed circulation cooling system, characterized in that it contains 0.1 to 50% by weight of nitrite, 0.1 to 40% by weight of phosphonate, 0.1 to 20% by weight of azole compound and the balance. It provides a water treatment composition. The present invention also provides a method of inhibiting corrosion and scale of a closed circulation cooling system comprising administering the water treatment agent composition to a closed circulation cooling system. In the water treatment composition of the present invention, it is preferable to use sodium nitrite, potassium nitrite or the like as the nitrite, and as phosphonate, hydroxy ethylidine diphosphonic acid, hydroxy phosphono carboxylic acid, amino trimethylene phosphate It is preferable to use phenic acid and phosphonobutane tricarboxylic acid alone or in mixture of one or more, and tolyltriazole, mercapto benzothiazole, benzotriazole and the like may be used as the azole compound.

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

아질산염은 수처리제 전체량 기준으로 0.1 내지 50중량%, 바람직하게는 0.2내지 45 중량%로 사용하면 적당하며, 금속배관에 산화피막을 형성하여 부식을 억제하는 역할을 한다. 이때 아질산염의 함유량이 0.1 중량% 미만이면 부식 및 스케일억제 효과가 저하되고 50 중량%를 초과하면 경제성이 떨어진다. 포스포네이트는 수처리제 조성물 전체량 기준으로 0.1 내지 40 중량%, 바람직하게는 1.0 내지 35 중량%로 사용하면 적당하며, 부식반응중 음극반응을 억제하는 기능 및 칼슘염 스케일억제 기능이 우수하다. 이때 포스포네이트의 함유량이 0.1 중량% 미만이면 부식 및 스케일 억제 효과가 저하되고 40 중량%를 초과하면 경제성이 떨어진다. 아졸계 화합물은 수처리제 조성물 전체량 기준으로 0.1 내지 20 중량%, 바람직하게는 0.2 내지 19 중량 %로 사용하면 적당하며 특히, 구리 및 구리화합물의 부식억제 능력이 탁월하다. 여기서, 아졸계 화합물의 함유량이 0.1 중량% 미만이면 부식 방지 효과가 미비하며 20 중량%을 초과하면 경제성이 떨어진다. 본 발명의 수처리제 조성물은 필요한 경우 잔부로서 물을 혼합하여 전체 100중량%로 만들수도 있다.Nitrite is suitable to use 0.1 to 50% by weight, preferably 0.2 to 45% by weight based on the total amount of the water treatment agent, and serves to suppress corrosion by forming an oxide film on the metal pipe. At this time, if the content of nitrite is less than 0.1% by weight, the corrosion and scale inhibitory effect is lowered. The phosphonate is suitably used in an amount of 0.1 to 40% by weight, preferably 1.0 to 35% by weight based on the total amount of the water treatment agent composition. At this time, if the content of the phosphonate is less than 0.1% by weight, the corrosion and scale inhibiting effect is lowered, and if it exceeds 40% by weight, the economy is inferior. The azole compound is suitably used in an amount of 0.1 to 20% by weight, preferably 0.2 to 19% by weight based on the total amount of the water treatment agent composition, and particularly, the corrosion inhibitory ability of the copper and the copper compound is excellent. Here, if the content of the azole compound is less than 0.1% by weight, the corrosion protection effect is insignificant, and if it exceeds 20% by weight, the economic efficiency is poor. The water treatment composition of the present invention may be made up to 100% by weight by mixing water as the remainder if necessary.

상기와 같은 본 발명의 수처리제 조성물을 밀폐 냉각 시스템의 냉각수에, 바람직하게는 50ppm이상이 되도록 투여하며, 각종 산업용 수배관에서 발생할 수 있는 부식을 방지하고 스케일을 억제하는 데 보다 효과적이고, 특히, 미생물에 의한 영향을 적게 받고, 칼슘염 스케일 생성의 위험이 있는 밀폐 순환 냉각 공정에 적용하면 효과적이다.The water treatment agent composition of the present invention as described above is administered to the cooling water of the hermetic cooling system, preferably 50 ppm or more, and is more effective in preventing scale and inhibiting scale that may occur in various industrial water pipes, in particular, microorganisms. It is effective when applied to a closed circulation cooling process that is less affected by the risk and has a risk of generating calcium salt scale.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.

실시예 1 - 3Examples 1-3

온도 45 ℃에서 탄소강 시험편(0.218dm2)을 회전속도 170rpm으로 5일간 회전시켜서 부식속도를 측정하였다. 이때 다음 표1의 시험수질에 표2에 표시된 수처리제를 2000ppm의 농도로 유지시킨 후 시험하였고, 시험편의 부식속도(mdd, mg/(dm2·day))의 결과를 표4에 나타내었다.The corrosion rate was measured by rotating a 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 water treatment agent shown in Table 2 was tested after maintaining the concentration of 2000ppm in the test water quality of Table 1, and the results of the corrosion rate (mdd, mg / (dm 2 · day)) of the test piece is shown in Table 4.

실시예 4 - 6Examples 4-6

테스트 용액을 밀폐시키고 50℃ 에서 7시간 정체시킨 후 테스트 용액을 0.45 마크로미터 필터로 여과하여 칼슘경도를 측정하여 칼슘염 스케일 억제율을 측정하였다. 이때 다음 표1의 시험수질에 표2에 표시된 수처리제를 2000ppm의 농도로 유지시킨 후 시험하였고, 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 macrometer filter to measure calcium hardness to determine calcium salt scale inhibition. At this time, the water treatment agent shown in Table 2 was tested after maintaining the concentration of 2000 ppm in the test water quality of Table 1, and the results of calcium salt scale inhibition rate are shown in Table 5.

Figure pat00001
Figure pat00001

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

Conductivity : 전기전도도Conductivity: electrical conductivity

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

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

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

Figure pat00002
Figure pat00002

포스포네이트 1 : 하이드록시 에틸리딘 디포스포닉산(상품명: Unihib 106, LONZA사 제품)Phosphonate 1: hydroxy ethylidine diphosphonic acid (brand name: Unihib 106, product of LONZA company)

포스포네이트 2 : 하이드록시 포스포노 카르복실산(상품명: Belcor 575, FMC사 제품)Phosphonate 2: hydroxy phosphono carboxylic acid (brand name: Belcor 575, product of FMC company)

비교예 1 - 3Comparative Example 1-3

표1의 시험수질에 다음 표3에 표시된 수처리제를 2000ppm의 농도로 유지시킨 후 상기 실시예 1 - 3과 동일한 방법으로 실험하여 부식속도의 결과를 표 4에 나타내었다.In the test water quality of Table 1, the water treatment agent shown in Table 3 was maintained at a concentration of 2000 ppm, and then experimented in the same manner as in Examples 1 to 3, and the results of the corrosion rates are shown in Table 4.

비교예 4 - 6Comparative Example 4-6

표1의 시험수질에 다음 표3에 표시된 수처리제를 2000ppm의 농도로 유지시킨 후 상기 실시예 4 - 6과 동일한 방법으로 실험하여 스케일 억제율의 결과를 표 5에나타내었으며 스케일 억제율은 다음 식에 의하여 계산하였다.In the test water quality of Table 1, the water treatment agent shown in Table 3 was maintained at a concentration of 2000 ppm, and the experiment was carried out in the same manner as in Examples 4 to 6, and the results of scale inhibition were shown in Table 5, and the scale inhibition was calculated by the following equation. It was.

Figure pat00003
Figure pat00003

Ct : 시험전의 시험액중의 칼슘 경도Ct: calcium hardness in test solution before test

Ce : 시험후의 시험액중의 칼슘 경도Ce: calcium hardness in test solution after test

Figure pat00004
Figure pat00004

포스포네이트 1 : 하이드록시 에틸리딘 디포스포닉산(상품명: Unihib 106, LONZA사 제품)Phosphonate 1: hydroxy ethylidine diphosphonic acid (brand name: Unihib 106, product of LONZA company)

포스포네이트 2 : 하이드록시 포스포노 카르복실산(상품명: Belcor 575, FMC사 제품)Phosphonate 2: hydroxy phosphono carboxylic acid (brand name: Belcor 575, product of FMC company)

Figure pat00005
Figure pat00005

Figure pat00006
Figure pat00006

상기 표 4에 의하면 표 1 의 수질에 대한 본 발명에 따른 실시예 1 내지 3의 부식속도는 비교예 1 내지 3 보다 부식속도가 훨씬 작음을 알수있으며, 또한 상기표 5에 의하면 본 발명에 따른 실시예 4 내지 6의 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 can be seen that the corrosion rate is much smaller than Comparative Examples 1 to 3, and also according to the table 5 according to the present invention It can be seen that the scale inhibition rate of Examples 4 to 6 is higher than that of Comparative Examples 4 to 6.

따라서 본 발명의 수처리제는 금속의 부식 및 스케일 생성을 방지하는 효과가 매우 우수하며, 또한 본 발명은 금속표면에서 발생할 수 있는 부식반응을 억제하여 부식이 일어날 수 있는 조건을 최대한 축소시키므로써 탄소강과 구리재질에 대해 뛰어난 방식효과를 기대할 수 있고, 스케일을 억제하는 능력이 우수하므로 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 the present invention also suppresses the corrosion reaction that may occur on the metal surface to minimize the conditions that can occur corrosion by carbon steel and copper Excellent anticorrosive effect can be expected on the material, and the ability to control scale is excellent, so it is excellent in controlling corrosion and scale at the same time.

Claims (2)

(a) 소디움 나이트라이트 또는 포타슘 나이트라이트인 몰리브덴산염 0.1 ∼ 50 중량%;(a) 0.1 to 50% by weight molybdate, which is sodium nitrite or potassium nitrite; (b) 포스포노부탄 트리카르복실산, 하이드록시에틸리딘 디포스포닉산, 하이드록시포스포노 카르복실산, 및 아미노 트리메틸렌 포스포닉산으로 이루어진 군으로부터 선택되는 1 종 이상의 포스포네이트 화합물 0.1 ∼ 40.0 중량%;(b) 0.1 to 1 or more phosphonate compounds selected from the group consisting of phosphonobutane tricarboxylic acid, hydroxyethylidine diphosphonic acid, hydroxyphosphono carboxylic acid, and amino trimethylene phosphonic acid 40.0 wt%; (c) 톨릴트리아졸, 머캅토 벤조티아졸 및 벤조트리아졸로 이루어진 군으로부터 선택되는 아졸계 화합물 0.1 ∼ 20.0 중량%; 및(c) 0.1 to 20.0% by weight of an azole compound selected from the group consisting of tolyltriazole, mercapto benzothiazole and benzotriazole; And (d) 잔부로서 물(d) water as balance 을 포함하는 것을 특징으로 하는 부식 및 스케일 억제 수처리제 조성물.Corrosion and scale inhibitory water treatment composition comprising a. 제 1 항 기재의 수처리제 조성물을 밀폐 및 순환 냉각시스템에 투어하는 것을 특징으로 하는 부식 및 스케일 억제방법.A method for suppressing corrosion and scale, characterized in that the water treatment agent composition according to claim 1 is toured in a closed and circulating cooling system.
KR1019970042083A 1997-08-28 1997-08-28 Water treatment composition for preventing scale and corrosion in enclosed circulation cooling system KR100315438B1 (en)

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KR101003064B1 (en) 2004-06-25 2010-12-21 에스케이케미칼주식회사 Multifunctional cooling water treating composition not including divalent metal salt, and water-treating method using the same
CN103663745A (en) * 2013-12-11 2014-03-26 山东华亚环保科技有限公司 Scale and corrosion inhibitor
CN103663746A (en) * 2013-12-11 2014-03-26 山东华亚环保科技有限公司 Scale and corrosion inhibitor
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