WO2002063056A1 - Acier d"excellente resistance a la corrosion au point de rosee de l"acide sulfurique - Google Patents

Acier d"excellente resistance a la corrosion au point de rosee de l"acide sulfurique Download PDF

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Publication number
WO2002063056A1
WO2002063056A1 PCT/JP2002/000856 JP0200856W WO02063056A1 WO 2002063056 A1 WO2002063056 A1 WO 2002063056A1 JP 0200856 W JP0200856 W JP 0200856W WO 02063056 A1 WO02063056 A1 WO 02063056A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfuric acid
steel
corrosion resistance
dew point
corrosion
Prior art date
Application number
PCT/JP2002/000856
Other languages
English (en)
Japanese (ja)
Inventor
Shunji Sakamoto
Satoshi Nishimura
Akira Usami
Original Assignee
Nippon Steel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corporation filed Critical Nippon Steel Corporation
Priority to JP2002562790A priority Critical patent/JP4291573B2/ja
Publication of WO2002063056A1 publication Critical patent/WO2002063056A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • the present invention relates to a steel material excellent in sulfuric acid dew point corrosion resistance used for equipment such as a flue, a chimney, and a boiler air preheater that is exposed to exhaust gas produced by burning heavy oil, coal, refuse, and the like.
  • the present invention provides a steel material capable of ensuring excellent corrosion resistance in a sulfuric acid dew point corrosion environment in all temperature ranges from high to low temperatures, and an air preheater using the same.
  • the present inventors prepared test materials of various steel components, and as the low-temperature conditions, (a) 40% sulfuric acid, 60 ° C, (b) 50% sulfuric acid, 80 ° C (C) 80% sulfuric acid, 140 ° C,
  • the alloy elements that play a major role are three elements, i.e., Si, Cu, and Sb.
  • the maximum corrosion rates under the above four conditions are summarized for each content of Si, Cu and Sb. From this, it can be read macroscopically that the corrosion rate tends to decrease as the Si content increases, but this is limited to the case where both Sb and Cu coexist, and either Sb or Cu is contained. Otherwise, even if the amount of Si is large, satisfactory corrosion resistance cannot be obtained under all conditions of low temperature and high temperature.
  • the required amounts of Si, Cu and Sb are respectively set to 1.2 %, 0.05% or more, and 0.01% or more.
  • FIG. 3 shows the corrosion rates of steels with different C contents in the above-mentioned composite system of Si, Cu and Sb. From this, it was found that if the amount of C is inappropriate, sufficient corrosion resistance cannot be obtained no matter how the joint effect of the three elements is used.
  • the C content is suppressed to a low level of at least 0.20% or less, and the desirable content is 0.10% or less, more preferably 0.010% or less.
  • the present invention achieves, for the first time, satisfactory corrosion resistance at all temperature conditions in a sulfuric acid dew-point corrosion environment by incorporating a low C element in addition to the composite addition of Si, Cu and Sb.
  • the gist is as follows.
  • Figure 1 is a diagram schematically showing the sulfuric acid dew point corrosion behavior of steel using temperature and sulfuric acid concentration as indices.
  • Figure 2 shows the effect of Si, Cu and Sb on sulfuric acid dew point corrosion.
  • the corrosion rates on the vertical axis are (a) 40% sulfuric acid, 60 ° C, (b) 50% sulfuric acid, 80 ° C, (c) 80% sulfuric acid, 140 ° C, (d) 90% sulfuric acid, 160 ° C.
  • the maximum value of the corrosion rate under the four conditions is displayed.
  • Figure 3 shows the effect of C on sulfuric acid dew point corrosion.
  • the corrosion rates on the vertical axis are (a) 40% sulfuric acid, 60 ° (:, (b) 50% sulfuric acid, 80 ° C, (c) 80% sulfuric acid, 140 ° C, (d) 90% sulfuric acid, 160 ° C (Displays the maximum value of the corrosion rate under four conditions.
  • FIG. 4 is a diagram schematically showing the structure of the air preheater. BEST MODE FOR CARRYING OUT THE INVENTION
  • C Since C deteriorates the corrosion resistance, its content is desired to be as low as possible. Particularly, if the content exceeds 0.20%, the corrosion resistance under both low temperature and high temperature conditions will not be compatible. Was set to 0.20%.
  • the desirable content is 0.10% or less, more preferably 0.010% or less. Below.
  • Si, Cu, Sb To secure good sulfuric acid corrosion resistance under both low and high temperature conditions, it is essential to bring out the joint effect of the three elements.
  • the minimum required content of each element for this purpose is: Si: 1.2%, Cu: 0.05%, Sb: 0.01%.
  • the upper limits of practically desirable contents of these elements are as follows.
  • Upper limit of Cu Mainly effective for improving corrosion resistance under low temperature conditions, but if it exceeds 1.0%, hot workability deteriorates, so the upper limit was set to 1.0%.
  • Mn is an element effective for strengthening. When it is necessary to compensate for the decrease in strength due to low C as in the present invention, an appropriate amount is contained.
  • the desirable content is 0.2% or more, but if the content exceeds 1.0%, the corrosion resistance deteriorates. Therefore, the upper limit is set to 1.0%.
  • A1 Although it may be contained for the purpose of deoxidation in the scouring process, if it exceeds 0.10%, hot workability deteriorates, so the upper limit was set to 0.10%.
  • N Like P and S, it is an impurity, preferably as low as possible
  • the upper limit is set to 0.050%. Desirably, it is 0.002% or less, more preferably 0.01% or less.
  • the steel sheet of the present invention contains the above elements as basic components.
  • the following elements are added for the purpose of further improving corrosion resistance, adjusting mechanical properties, and improving hot workability. You may make it contain.
  • Cr, Mo Effective for improving strength, but not desirable for corrosion resistance at low temperatures.
  • the range considering the balance between the two is preferably 1.0% or less.
  • Ni Can be used to prevent the deterioration of hot workability of Cu. However, if it exceeds 0.5%, the corrosion resistance tends to deteriorate, so the upper limit is 0.5% when adding it. It is desirable to add.
  • Nb, V, Ti elements that form precipitates and are effective for toughening. However, if the content exceeds 0.1%, the corrosion resistance tends to be deteriorated. It is desirable to add as%.
  • Sn An element effective for improving corrosion resistance, but if it is less than 0.01%, no effect is exhibited, and if it exceeds 0.2%, hot workability tends to deteriorate. It is desirably set to 01 to 0.2%.
  • W the tendency to improve the high-temperature strength at 0.5% or less
  • Ca, Mg, REM total 50 ppm or less
  • other additional components such as those having an effect of improving hot workability).
  • Steel of the following composition is melted and forged in the usual way and then forged. It can be processed into the shape of a plate, tube, rod, etc. by a usual hot working method such as forming or rolling, and can be put to practical use. Further, if necessary, the hot-worked product may be subjected to a heat treatment such as annealing, or may be subjected to a pickling process followed by a cold working process. The corrosion resistance of the steel obtained through such a manufacturing process is not affected by the process conditions, and the steel can be manufactured in the same process as ordinary carbon steel.
  • the sensible heat of the exhaust gas accumulated in the heat transfer Ereme cement but has a structure for preheating the air fed to the boiler, the heat transfer Ereme cement repeatedly because sulfuric acid dew-point corrosion that is exposed to exhaust gas containing S0 X Is an important member, and is suitable for use in the present invention.
  • Sulfuric acid Dew-point corrosion conditions are representative of low and high temperature conditions, such as (a) 40% sulfuric acid, 60 ° C, (b) 50% sulfuric acid, 80 ° C, (c) 80% sulfuric acid, 140 ° C, You And (d) a 4-hour immersion test under four conditions of 90% sulfuric acid and 160 ° C to determine the corrosion rate.
  • Table 2 shows the test results. From this, the maximum corrosion rate under any of the conditions (a) to (d) is 145 to 4890 mg / m 2 / hr in Comparative Examples Nos. 11 to 18, whereas the invention example No .: in! ⁇ 10, 60 ⁇ 99g / m 2 / a is, there is the obvious advantage.
  • the difference between the maximum value and the minimum value of the corrosion rate under the four conditions is smaller in the invention steel than in the comparative example, and the change in the corrosion rate is smaller with respect to the change in temperature and sulfuric acid concentration. Steel can contribute to greater freedom in plant design.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

L"invention concerne un acier présentant une excellente résistance à la corrosion au point de rosée de l"acide sulfurique, dont la composition chimique en pourcentage massique est la suivante : C :≤ 0,20 %, Si : entre 1,2 et 3,5 %, Cu : entre 0,05 et 1,0 %, Sb : entre 0,03 et 0,30 %, Mn : ≤ 1,0 %, P : ≤ 0,05 %, S : ≤ 0,05 %, Al : ≤ 0,10 %, moyenne : Fe et les composants suivants et/ou les impuretés inévitables ; l"acier comprenant l"un ou l"autre des composants suivants : Cr : ≤ 1,0 %, Mo : 1,0 %, Ni : ≤ 0,5 %, Nb : ≤ 0,1 %, V : ≤ 0,1 %, Ti : ≤ 0,1 %, Sn : entre 0,01 et 0,2 %, B : entre 0,0005 et 0,010 %. L"invention concerne d"autre part un réchauffeur d"air utilisant l"acier dans son élément de transfert thermique. Cet acier présente une excellente résistance à la corrosion au point de rosée de l"acier sulfurique dans toute la plage de température, des plus élevées aux plus faibles.
PCT/JP2002/000856 2001-02-02 2002-02-01 Acier d"excellente resistance a la corrosion au point de rosee de l"acide sulfurique WO2002063056A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002562790A JP4291573B2 (ja) 2001-02-02 2002-02-01 耐硫酸露点腐食性に優れた鋼および空気予熱器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-27455 2001-02-02
JP2001027455 2001-02-02

Publications (1)

Publication Number Publication Date
WO2002063056A1 true WO2002063056A1 (fr) 2002-08-15

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Country Status (5)

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JP (1) JP4291573B2 (fr)
KR (1) KR100511653B1 (fr)
CN (1) CN1195883C (fr)
TW (1) TW554051B (fr)
WO (1) WO2002063056A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1460145A1 (fr) * 2001-11-19 2004-09-22 Nippon Steel Corporation Acier faiblement allie tres resistant a la corrosion engendree par l'acide chlorique et l'acide sulfurique et joint soude renfermant celui-ci
JP2007239094A (ja) * 2006-02-13 2007-09-20 Nippon Steel Corp 耐酸腐食鋼
JP2007239095A (ja) * 2006-02-10 2007-09-20 Nippon Steel Corp 耐酸腐食鋼
WO2008062984A1 (fr) * 2006-11-21 2008-05-29 Posco Acier présentant une excellente résistance à la corrosion par l'acide sulfurique et son procédé de fabrication
CN112575269A (zh) * 2019-09-27 2021-03-30 宝山钢铁股份有限公司 一种耐低温酸露点腐蚀冷轧钢及其制造方法

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CN100419115C (zh) * 2006-11-23 2008-09-17 武汉钢铁(集团)公司 一种特高强度耐大气腐蚀钢
CN101775544B (zh) * 2010-03-03 2011-09-14 武钢集团昆明钢铁股份有限公司 耐硫酸露点腐蚀钢kns轧制方法
CN101892433A (zh) * 2010-06-25 2010-11-24 南京钢铁股份有限公司 一种耐低温硫酸露点腐蚀的低合金钢
CN101921966B (zh) * 2010-08-19 2011-12-21 攀钢集团钢铁钒钛股份有限公司 一种耐硫酸露点腐蚀热轧钢板的生产方法
US20150299829A1 (en) * 2012-03-19 2015-10-22 Nisshin Steel Co., Ltd. Acid dew point corrosion-resistant steel and exhaust gas flow path constituent member
CN103589972B (zh) * 2013-10-10 2015-04-29 中天钢铁集团有限公司 一种低成本耐硫酸露点腐蚀用低合金钢及其生产工艺与用途
CN104357754B (zh) * 2014-10-17 2016-06-22 江阴兴澄特种钢铁有限公司 一种耐硫酸露点腐蚀钢板及其制造方法
CN104831172A (zh) * 2015-04-23 2015-08-12 苏州劲元油压机械有限公司 一种液压站用固定板的制造工艺
CN106568094A (zh) * 2016-10-25 2017-04-19 安徽沃木采暖科技有限公司 天然气壁炉用烟囱
CN106556018A (zh) * 2016-10-25 2017-04-05 安徽沃木采暖科技有限公司 适用于木柴燃料的壁炉烟囱
CN106500119A (zh) * 2016-10-25 2017-03-15 安徽沃木采暖科技有限公司 煤炭壁炉专用烟囱
CN106568096A (zh) * 2016-10-25 2017-04-19 安徽沃木采暖科技有限公司 防腐蚀壁炉烟囱
CN108660384A (zh) * 2017-03-30 2018-10-16 宝山钢铁股份有限公司 一种耐硫酸腐蚀的低合金钢、钢管、钢板及其制造方法
KR101977471B1 (ko) 2017-07-17 2019-05-10 한국동서발전(주) 공기예열기의 냉단부 온도 조절 장치 및 방법
CN109652745A (zh) * 2019-03-01 2019-04-19 江苏建中新材料科技有限公司 一种耐酸换热管钢及其加工工艺
CN109916809A (zh) * 2019-03-28 2019-06-21 长沙理工大学 一种应用于燃机电站余热锅炉的露点腐蚀模拟装置
CN109916807A (zh) * 2019-03-28 2019-06-21 长沙理工大学 一种研究硫酸露点腐蚀的模拟气体产生方法
CN110904384B (zh) * 2019-12-02 2021-04-06 中国石油天然气集团有限公司 一种耐硫酸露点腐蚀用q345ns螺旋埋弧焊管及其制造工艺

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JPH11350081A (ja) * 1998-06-11 1999-12-21 Nippon Steel Corp 耐食鋼
JP2000073138A (ja) * 1998-08-26 2000-03-07 Nkk Corp 耐硫酸腐食性に優れたボルト用鋼
JP2000073139A (ja) * 1998-08-26 2000-03-07 Nkk Corp 耐硫酸腐食性に優れたボルト用鋼

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JPS4937172B1 (fr) * 1969-06-25 1974-10-07
JP2000017382A (ja) * 1998-07-03 2000-01-18 Nippon Steel Corp 耐硫酸腐食性に優れた鋼
JP2002047538A (ja) * 2000-07-27 2002-02-15 Nkk Corp 耐震性及び耐硫酸性に優れた圧延形鋼及びその製造方法

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH11350081A (ja) * 1998-06-11 1999-12-21 Nippon Steel Corp 耐食鋼
JP2000073138A (ja) * 1998-08-26 2000-03-07 Nkk Corp 耐硫酸腐食性に優れたボルト用鋼
JP2000073139A (ja) * 1998-08-26 2000-03-07 Nkk Corp 耐硫酸腐食性に優れたボルト用鋼

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1460145A1 (fr) * 2001-11-19 2004-09-22 Nippon Steel Corporation Acier faiblement allie tres resistant a la corrosion engendree par l'acide chlorique et l'acide sulfurique et joint soude renfermant celui-ci
EP1460145A4 (fr) * 2001-11-19 2005-03-09 Nippon Steel Corp Acier faiblement allie tres resistant a la corrosion engendree par l'acide chlorique et l'acide sulfurique et joint soude renfermant celui-ci
US7718014B2 (en) 2001-11-19 2010-05-18 Nippon Steel Corporation Low alloy steel and weld joint thereof excellent in corrosion resistance to hydrochloric acid and sulfuric acid
US7731896B2 (en) 2001-11-19 2010-06-08 Nippon Steel Corporation Low alloy steel and weld joint thereof excellent in corrosion resistance to hydrochloric acid and sulfuric acid
JP2007239095A (ja) * 2006-02-10 2007-09-20 Nippon Steel Corp 耐酸腐食鋼
JP2007239094A (ja) * 2006-02-13 2007-09-20 Nippon Steel Corp 耐酸腐食鋼
WO2008062984A1 (fr) * 2006-11-21 2008-05-29 Posco Acier présentant une excellente résistance à la corrosion par l'acide sulfurique et son procédé de fabrication
KR100946148B1 (ko) 2006-11-21 2010-03-10 주식회사 포스코 황산 내식성이 우수한 내황산 부식강과 그 제조방법
CN112575269A (zh) * 2019-09-27 2021-03-30 宝山钢铁股份有限公司 一种耐低温酸露点腐蚀冷轧钢及其制造方法

Also Published As

Publication number Publication date
JPWO2002063056A1 (ja) 2004-06-10
TW554051B (en) 2003-09-21
CN1455822A (zh) 2003-11-12
KR20020093882A (ko) 2002-12-16
JP4291573B2 (ja) 2009-07-08
KR100511653B1 (ko) 2005-09-01
CN1195883C (zh) 2005-04-06

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