KR101138538B1 - Method for inhibiting corrosion of base material of blast furnace cooling system - Google Patents

Method for inhibiting corrosion of base material of blast furnace cooling system Download PDF

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KR101138538B1
KR101138538B1 KR1020040110155A KR20040110155A KR101138538B1 KR 101138538 B1 KR101138538 B1 KR 101138538B1 KR 1020040110155 A KR1020040110155 A KR 1020040110155A KR 20040110155 A KR20040110155 A KR 20040110155A KR 101138538 B1 KR101138538 B1 KR 101138538B1
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blast furnace
base material
corrosion
cooling plate
azole
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KR20060071539A (en
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고광섭
이상길
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재단법인 포항산업과학연구원
주식회사 포스코
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    • 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
    • C23F11/10—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 organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2105/00—Erosion prevention

Abstract

본 발명은 고로 노체 냉각반 모재(Cu)의 부식 억제방법에 관한 것으로, 특히 고로 노체 냉각반 냉각수내 아졸(azole)류 구리(Cu) 방식제를 투입하여 고로 냉각반 모재인 구리의 부식을 효과적으로 억제할 수 있으며, 이로부터 고로 냉각시스템의 설비 부식을 방지할 수 있는 고로 노체 냉각반 모재(Cu)의 부식 억제방법에 관한 것이다.The present invention relates to a method of inhibiting corrosion of a blast furnace cooling plate base material (Cu), and particularly, by injecting an azole-type copper (Cu) anticorrosive agent in the blast furnace cooling plate cooling water effectively. The present invention relates to a method of suppressing corrosion of a blast furnace body cooling plate base material (Cu), which can be suppressed, and thereby prevents equipment corrosion of the blast furnace cooling system.

노체 냉각반, 모재, 부식 억제, 아졸류 구리 방식제Furnace cooling board, base material, corrosion control, azole copper anticorrosive

Description

고로 노체 냉각반 모재의 부식 억제방법 {METHOD FOR INHIBITING CORROSION OF BASE MATERIAL OF BLAST FURNACE COOLING SYSTEM}Method of suppressing corrosion of blast furnace base plate base material {METHOD FOR INHIBITING CORROSION OF BASE MATERIAL OF BLAST FURNACE COOLING SYSTEM}

도 1은 본 발명의 일실시예에 따른 방법과 종래 방법에 따른 냉각반 시편의 부식정도를 나타낸 그래프이다.1 is a graph showing the degree of corrosion of the cooling plate specimens according to the method and the conventional method according to an embodiment of the present invention.

도 2는 본 발명의 일실시예에 따른 방법과 종래 방법에 따른 Fe 이온농도의 변화를 나타낸 그래프이다.2 is a graph showing a change in Fe ion concentration according to the method according to an embodiment of the present invention and the conventional method.

본 발명은 고로 노체 냉각반 모재(Cu)의 부식 억제방법에 관한 것으로, 더욱 상세하게는 고로 냉각반 모재인 구리의 부식을 효과적으로 억제할 수 있으며, 이로부터 고로 냉각시스템의 설비 부식을 방지할 수 있는 고로 노체 냉각반 모재(Cu)의 부식 억제방법에 관한 것이다.The present invention relates to a method for suppressing corrosion of a blast furnace cooling plate base material (Cu), and more particularly, to effectively suppress corrosion of copper, which is a blast furnace cooling plate base material, thereby preventing corrosion of equipment of the blast furnace cooling system. The present invention relates to a method of inhibiting corrosion of a blast furnace furnace cooling plate base material (Cu).

일반적으로 고로 내에 축조된 연와의 수명연장과 고로 철피를 보호하기 위하여 냉각반을 노벽에 삽입하여 냉각하고 있는데, 냉각수량은 약 10,000～11,000 Ton/hr 정도를 순환 사용하고 있다. In general, in order to extend the life of the breeze built in the blast furnace and to protect the blast furnace shell, the cooling plate is inserted into the furnace wall and cooled.

상기 냉각반에 사용되는 냉각수는 주로 담수가 사용되며, 냉각반의 재질은 99.9 % 이상의 순동(Cu)재이다. 냉각반의 위치는 종 방향 각 단의 간격이 약 300～400 ㎜로서 어긋나게 배열하고, 횡 방향은 중심간격에서 약 1,000 ㎜로 사용범위에 따라 다르나, 냉각반의 개수는 약 1,000～1,500 개의 범위이다. 냉각수는 종 방향 3～5 단을 직렬로 연결하여 1연의 냉각수량이 3～5 Ton/hr 정도이다. Cooling water used in the cooling plate is mainly used fresh water, the material of the cooling plate is 99.9% or more pure copper (Cu) material. The positions of the cooling panels are arranged so that the intervals of each stage in the longitudinal direction are shifted about 300 to 400 mm, and the transverse direction is about 1,000 mm at the center interval depending on the use range, but the number of cooling panels is in the range of about 1,000 to 1,500 pieces. Cooling water is 3 ~ 5 Ton / hr of cooling water per stage by connecting 3 ~ 5 stages in series.

이때 고로 노체 냉각반 순환수계 냉각수의 SS 입자가 배관막힘의 주요 원인이고, 상기 입자크기는 1～150 ㎛ 정도이다.At this time, the SS particles of the blast furnace body cooling plate circulating water-based cooling water is the main cause of clogging the pipe, the particle size is about 1 ~ 150 ㎛.

고로공장에서 노체 냉각시스템 플로우(flow)는 냉각탑 후단에서 보충수와 부식억제제가 투입된 후 고로 각 냉각반을 순환하여 재사용하게 된다. In the blast furnace plant, the flow of the furnace cooling system is recycled by circulating each of the blast furnaces after supplementary water and corrosion inhibitor are introduced at the rear of the cooling tower.

상기와 같은 노체 냉각시스템 전체가 밀폐형으로 되어 있지만, 일부 노출부분설비에서 고로 내부의 강하분진 등이 냉각 순환수계에 유입되어 전체적인 냉각순환수에 유입되어 고열 냉각에 사용되는 고로 노체 냉각반내 퇴적되기 때문에 이를 제거하여 냉각의 효율을 증대할 목적으로 세정제가 일부 사용되나, 상기 세정제로 인하여 냉각반 모재인 Cu의 부식이 유발된다는 문제점이 있다.Although the whole furnace cooling system as described above is hermetically sealed, in some exposed part facilities, the falling dust inside the blast furnace flows into the cooling circulation system and enters the entire cooling circulation water and is deposited in the blast furnace cooling chamber used for high temperature cooling. Although some of the cleaners are used for the purpose of increasing the efficiency of the cooling by removing them, there is a problem that the corrosion of the cooling base substrate Cu is caused by the cleaner.

이에 따라, 종래에는 순환수중에 유입된 강하분진 등의 퇴적물의 제거를 위하여 자연침강법이나 응집침전법 등이 주로 사용되어 왔다. Accordingly, conventionally, a natural sedimentation method or a coagulation sedimentation method has been mainly used to remove deposits such as falling dust introduced into the circulating water.

상기 응집침전법은 알루미늄염이나 철염을 사용하여 폐수 중의 SS 성분을 응집, 침전시켜 제거하는 방법이다(Journal of KSEE, Vol. 18, p43～54(1996)).The flocculation sedimentation method is a method of flocculation, precipitation and removal of SS components in wastewater using aluminum salts or iron salts (Journal of KSEE, Vol. 18, p 43 to 54 (1996)).

또한 상기 자연침강법은 침전지의 소요면적의 크기에 좌우되며, 물리적인 응집침전법은 주로 음이온계 고분자 응집제를 사용함으로써 유입된 강하분진을 슬러리 형태로 응집시켜 제거가 되지만, 약품사용량 증가에 따라 폐수처리비용이 상승 하게 되고, 슬러지가 많이 발생하게 될 뿐만 아니라, 발생하는 슬러지의 처리가 어렵다는 문제점이 있다. 뿐만 아니라, 상기 침전에 소요되는 시간이 훨씬 과다하게 소요되고 있어 설비 운전이 어렵다는 문제점이 있다.In addition, the natural sedimentation method is dependent on the size of the required area of the sedimentation basin, the physical coagulation sedimentation method is mainly removed by agglomeration of the dropping dust introduced in the form of slurry by using an anionic polymer flocculant, waste water according to the increase in the amount of chemical use There is a problem that the treatment cost is increased, not only a lot of sludge is generated, but also difficult to process the sludge generated. In addition, since the time required for the precipitation is much excessively excessive, there is a problem in that facility operation is difficult.

따라서, 고로 냉각반 내부의 Cu 부식을 효과적을 억제할 수 있는 방법에 대한 연구가 더욱 필요한 실정이다.Therefore, there is a need for further research on a method for effectively suppressing Cu corrosion in the blast furnace cooling panel.

상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 고로 냉각반 모재인 구리의 부식을 효과적으로 억제할 수 있으며, 이로부터 고로 냉각시스템의 설비 부식을 방지할 수 있는 고로 노체 냉각반 모재(Cu)의 부식 억제방법을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention can effectively suppress the corrosion of copper, the blast furnace cooling plate base material, from which the blast furnace body cooling plate base material (Cu) can prevent the equipment corrosion of the blast furnace cooling system It is an object of the present invention to provide a method of suppressing corrosion.

상기 목적을 달성하기 위하여, 본 발명은 고로 노체 냉각반 모재(Cu)의 부식 억제방법에 있어서, 상기 고로 노체 냉각반 냉각수내 아졸(azole)류 구리(Cu) 방식제를 투입하는 것을 특징으로 하는 고로 노체 냉각반 모재(Cu)의 부식 억제방법을 제공한다.In order to achieve the above object, the present invention, in the method for suppressing corrosion of the blast furnace furnace cooling plate base material (Cu), characterized in that the azole-type copper (Cu) anticorrosive agent in the blast furnace furnace cooling plate cooling water is added. Therefore, the present invention provides a method of suppressing corrosion of a furnace cooling plate base material (Cu).

이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.

본 발명의 고로 노체 냉각반 모재(Cu)의 부식 억제방법은 고체 냉각반에 사용되는 냉각수내 아졸(azole)류 구리(Cu) 방식제를 투입하는 것을 특징으로 한다.Corrosion suppression method of the blast furnace furnace cooling plate base material (Cu) of the present invention is characterized in that the azole (Cu) anticorrosive agent in the cooling water used in the solid cooling plate.

본 발명에 사용되는 상기 아졸(azole)류 구리(Cu) 방식제는 고로 냉각반 내부의 구리(Cu)의 부식을 효과적으로 억제하는 작용을 한다. The azole copper (Cu) anticorrosive agent used in the present invention serves to effectively inhibit corrosion of copper (Cu) in the blast furnace cooling panel.                     

상기 아졸류 구리 방식제는 통상의 아졸계 구리 방식제를 사용할 수 있으며, 구체적으로 벤조트리아졸(benzotriazole, BZT), 톨일트리아졸(tolyltriazole, TTA), 머캅토벤조트리아졸(mercaptobenzotriazole), 또는 HRA 등을 사용할 수 있다.The azole copper anticorrosive may be used a conventional azole copper anticorrosive, specifically benzotriazole (benzotriazole, BZT), tolyltriazole (TTA), mercaptobenzotriazole (mercaptobenzotriazole), or HRA Etc. can be used.

상기 아졸류 구리 방식제는 냉각반에 사용되는 냉각수에 대하여 1 내지 40 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 10 내지 20 중량%로 포함되는 것이다. 그 함량이 1 중량% 미만이거나, 40 중량%를 초과할 경우에는 고로 냉각반 내부의 구리 부식의 억제 효과가 미미하다는 문제점이 있다.The azole copper anticorrosive is preferably contained in an amount of 1 to 40% by weight, and more preferably 10 to 20% by weight, based on the cooling water used in the cooling plate. If the content is less than 1% by weight or more than 40% by weight, there is a problem in that the suppression effect of copper corrosion inside the blast furnace cooling plate is insignificant.

상기와 같은 본 발명의 아졸류 구리 방식제가 고로 노체 냉각반에 사용되는 냉각수에 투입함으로써 종래 세정제를 사용하는 방법, 자연침강법, 응집침전법 등의 방법을 사용하면서도 고로 냉각반 모재인 구리의 부식을 효과적으로 억제할 수 있으며, 이로부터 고로 냉각시스템의 설비 부식을 방지할 수 있다.By adding the azole copper anticorrosive agent of the present invention to the cooling water used in the blast furnace furnace cooling plate, the corrosion of copper as the base material of the blast furnace cooling plate while using a method using a conventional cleaning agent, a natural precipitation method, a coagulation sedimentation method, etc. Can be effectively suppressed, from which the corrosion of the installation of the blast furnace cooling system can be prevented.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[실시예][Example]

실시예 1Example 1

1 L의 비이커에 고로 냉각반 시편과 함께 세정제로 FQ701(유기인 계통의 약품과 환원제가 주성분, 폐세정 용액 중 약 2,000 ㎎/L as P의 인 함유) 10 중량%, 환원제 70 중량%, 및 아졸계 Cu 방식제로 AZ8101(톨일트리아졸, tolyltriazole) 20 중량%를 넣은 후, 5 일 동안 jar test를 실시하였다. 10 wt% of FQ701 (organic chemicals and reducing agents containing the main component, about 2,000 mg / L as P in phosphorus) in a 1 L beaker with blast furnace cooling plate specimens, 70 wt% reducing agent, and 20 weight% of AZ8101 (tolyltriazole) was added as an azole Cu anticorrosive and then jar test was performed for 5 days.

비교예 1Comparative Example 1

상기 실시예 1에서 아졸계 Cu 방식제로 AZ8101(톨일트리아졸, tolyltriazole)를 사용하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.Except that AZ8101 (tolyltriazole, tolyltriazole) was not used as the azole Cu anticorrosive agent in Example 1, it was carried out in the same manner as in Example 1.

상기 실시예 1 및 비교예 1에서 jar test한 후, 냉각반 시편의 부식정도와 Fe 이온농도의 변화를 도 1 및 도 2와 하기 표 1에 나타내었다.After jar test in Example 1 and Comparative Example 1, the change in the degree of corrosion and Fe ion concentration of the cooling plate specimens are shown in Figure 1 and 2 and Table 1 below.

구분division 실시예 1Example 1 비교예 1Comparative Example 1 냉각반 시편 부식정도 (ppm)Corrosion degree of cooling plate specimen (ppm) Fe 이온농도의 변화 (ppm)Change in Fe Ion Concentration (ppm) 냉각반 시편 부식정도 (ppm)Corrosion degree of cooling plate specimen (ppm) Fe 이온농도의 변화 (ppm)Change in Fe Ion Concentration (ppm) 00 0.0010.001 0.050.05 0.0010.001 0.050.05 1일 후1 day later 0.0020.002 0.10.1 0.0030.003 0.080.08 2일 후2 days later 0.750.75 56.856.8 0.110.11 55.455.4 3일 후3 days later 0.880.88 325325 5.35.3 322322 5일 후5 days later 0.9120.912 555555 18.318.3 525525

상기 표 1, 도 1, 및 도 2에 나타낸 바와 같이, 본 발명에 따라 아졸계 Cu 방식제를 사용한 실시예 1은 비교예 1과 비교하여 고로 노체 냉각반 모재인 냉각반 시편의 부식이 1.0 ppm 이하로 전혀 일어나지 않았음을 확인할 수 있었고, Fe 이온농도 변화 또한 아졸계 Cu 방식제의 영향을 받지 않고 세정이 잘 이루어졌음을 확인할 수 있었다.As shown in Table 1, Figure 1, and Figure 2, Example 1 using an azole-based Cu anticorrosive agent according to the present invention is 1.0 ppm corrosion of the cooling plate specimens blast furnace furnace cooling plate base material compared to Comparative Example 1 It could be confirmed that it did not occur at all below, and it was confirmed that the Fe ion concentration change was also well washed without being affected by the azole Cu anticorrosive agent.

본 발명에 따르면 아졸류 구리 방식제를 고로 노체 냉각반에 사용되는 냉각수에 투입함으로써 종래 세정제를 사용하는 방법, 자연침강법, 응집침전법 등의 방 법을 사용하면서도 고로 냉각반 모재인 구리의 부식을 효과적으로 억제할 수 있으며, 이로부터 고로 냉각시스템의 설비 부식을 방지할 수 있다.According to the present invention, by adding the azole copper anticorrosive to the cooling water used in the blast furnace furnace cooling plate, the corrosion of copper, which is the base material of the blast furnace cooling plate, while using a method of using a conventional cleaning agent, a natural precipitation method, a flocculation sedimentation method, etc. Can be effectively suppressed, from which the corrosion of the installation of the blast furnace cooling system can be prevented.

이상에서 본 발명의 기재된 구체예에 대해서만 상세히 설명되었지만, 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, it is natural that such variations and modifications belong to the appended claims. .

Claims (4)

고로 노체 냉각반 모재(Cu)의 부식 억제방법에 있어서, 상기 고로 노체 냉각반 냉각수내에 아졸(azole)류 구리(Cu) 방식제를 투입하되, In the method for suppressing corrosion of the blast furnace body cooling plate base material (Cu), an azole copper (Cu) anticorrosive agent is introduced into the blast furnace body cooling plate cooling water, 상기 아졸류 구리 방식제가 톨일트리아졸(tolyltriazole, TTA), 머캅토벤조트리아졸(mercaptobenzotriazole), 및 HRA로 이루어지는 군으로부터 1 종 이상 선택되는 것을 특징으로 하는 고로 노체 냉각반 모재(Cu)의 부식 억제방법.Inhibition of corrosion of the blast furnace cooling plate base material (Cu), wherein the azole copper anticorrosive is selected from the group consisting of tolyltriazole (TTA), mercaptobenzotriazole, and HRA. Way. 삭제delete 제1항에 있어서,The method of claim 1, 상기 아졸류 구리 방식제가 냉각반에 사용되는 냉각수에 대하여 1 내지 40 중량%로 포함되는 것을 특징으로 하는 고로 노체 냉각반 모재(Cu)의 부식 억제방법.The azole-type copper anticorrosive is corrosion suppression method of the blast furnace body cooling panel base material (Cu), characterized in that contained in 1 to 40% by weight relative to the cooling water used in the cooling plate. 제1항에 있어서,The method of claim 1, 상기 아졸류 구리 방식제가 냉각반에 사용되는 냉각수에 대하여 10 내지 20 중량%로 포함되는 것을 특징으로 하는 고로 노체 냉각반 모재(Cu)의 부식 억제방 법.The azole-type copper anticorrosive agent corrosion suppression method of the blast furnace body cooling plate base material (Cu), characterized in that contained in 10 to 20% by weight relative to the cooling water used in the cooling plate.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6389687A (en) 1986-10-01 1988-04-20 Japan Organo Co Ltd Method for preventing corrosion of carbon steel, copper and copper alloy in water
JPS63293179A (en) 1987-05-21 1988-11-30 インターナシヨナル・ビジネス・マシーンズ・コーポレーシヨン Protection of copper from corrosion
KR20010087263A (en) * 2000-03-03 2001-09-15 가네꼬 히사시 Anticorrosive treating concentrate
JP2002088488A (en) * 2000-09-13 2002-03-27 Kurita Water Ind Ltd Anticorrosive composition for copper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6389687A (en) 1986-10-01 1988-04-20 Japan Organo Co Ltd Method for preventing corrosion of carbon steel, copper and copper alloy in water
JPS63293179A (en) 1987-05-21 1988-11-30 インターナシヨナル・ビジネス・マシーンズ・コーポレーシヨン Protection of copper from corrosion
KR20010087263A (en) * 2000-03-03 2001-09-15 가네꼬 히사시 Anticorrosive treating concentrate
JP2002088488A (en) * 2000-09-13 2002-03-27 Kurita Water Ind Ltd Anticorrosive composition for copper

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