WO2018038196A1 - 耐硫酸露点腐食鋼 - Google Patents

耐硫酸露点腐食鋼 Download PDF

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WO2018038196A1
WO2018038196A1 PCT/JP2017/030259 JP2017030259W WO2018038196A1 WO 2018038196 A1 WO2018038196 A1 WO 2018038196A1 JP 2017030259 W JP2017030259 W JP 2017030259W WO 2018038196 A1 WO2018038196 A1 WO 2018038196A1
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sulfuric acid
steel
point corrosion
acid dew
less
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PCT/JP2017/030259
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English (en)
French (fr)
Japanese (ja)
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康人 猪原
村瀬　正次
啓泰 菊池
俊司 桐本
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Ｊｆｅスチール株式会社
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Priority to JP2017564516A priority Critical patent/JP6332576B1/ja
Priority to KR1020197008032A priority patent/KR102220619B1/ko
Priority to CN201780049872.9A priority patent/CN109563594B/zh
Priority to MYPI2019000896A priority patent/MY189754A/en
Publication of WO2018038196A1 publication Critical patent/WO2018038196A1/ja

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper

Definitions

  • the present invention relates to a sulfuric acid dew-point corrosion steel used as a constituent material for heat exchangers, tanks, plants, etc. in an environment in contact with sulfuric acid or in an environment where sulfuric acid dew point occurs, in particular, in addition to excellent sulfuric acid dew point corrosion resistance,
  • the present invention relates to a sulfuric acid dew-point corrosion resistant steel having excellent hydrochloric acid resistance and manufacturability, and having excellent bendability and fatigue resistance.
  • Patent Document 2 aims to improve hot workability by reducing the amount of S and adding Mo and B. “By weight, C: 0.01 to 0.15%, Si: 0.1 to 0.5%, Mn: 0.1 to 0.5%, P: 0.03% or less, S: 0.0.
  • JP 2003-213367 A Japanese Patent Laid-Open No. 10-110237
  • the concentration of sulfuric acid generated in the sulfuric acid dew point environment varies depending on the temperature.
  • sulfuric acid concentration about 20% by mass at low temperature: 40 ° C.
  • sulfuric acid concentration about 50% by mass at medium temperature: 70 ° C.
  • high temperature 100
  • the sulfuric acid concentration is 70 to 80% by mass at °C to 140 °C.
  • the desired sulfuric acid dew point corrosion resistance may not be obtained even when S is reduced or Mo is added.
  • the present invention has been developed in view of the above-mentioned current situation, and has excellent sulfuric acid dew point corrosion resistance, excellent hydrochloric acid resistance and manufacturability at the same time, and also has excellent bending resistance and fatigue resistance.
  • the object is to provide dew point corrosion steel.
  • each additive element that improves sulfuric acid dew point corrosion resistance has an effect on hydrochloric acid resistance and manufacturability, as well as on bendability and fatigue resistance, as well as hydrochloric acid resistance, manufacturability, bendability, and fatigue resistance.
  • the gist configuration of the present invention is as follows.
  • the sulfuric acid dew-point corrosion steel according to any one of 1 to 3, In the cathodic polarization curve showing the relationship between the current density and the potential in a sulfuric acid aqueous solution having a temperature of 70 ° C. and a concentration of 50% by mass, the potential at the current density of 0.1 A / cm 2 is shown.
  • Is Va (V) The above Va is related to the potential Vg (V) when the current density in the cathode polarization curve in the sulfuric acid aqueous solution of the reference steel of the sulfuric acid dew-point corrosion steel is 0.1 A / cm 2 , and the following (4) Sulfuric acid dew-point corrosion steel that satisfies the formula.
  • a sulfuric acid dew point corrosion steel having excellent sulfuric acid dew point corrosion resistance and hydrochloric acid resistance, excellent manufacturability, and excellent bendability and fatigue resistance can be obtained.
  • the sulfuric acid dew point corrosion steel of the present invention can be suitably used as a constituent material for tanks, plants, etc. under various sulfuric acid dew point corrosion environments. Such a tank, plant, etc. can be manufactured.
  • C 0.050 to 0.150%
  • C is an element that increases the strength of steel.
  • the C content is 0.050% or more.
  • the C content is in the range of 0.050 to 0.150%.
  • it is in the range of 0.060 to 0.100%.
  • Si 0.10 to 0.80% Si is a component added as a deoxidizer and has the effect of increasing the strength of steel. For this reason, the amount of Si shall be 0.10% or more. However, if the Si content exceeds 0.80%, the toughness of the steel deteriorates. Therefore, the Si amount is in the range of 0.10 to 0.80%. Note that Si contributes to the improvement of the resistance to sulfuric acid dew point corrosion by forming an anticorrosion film in a sulfuric acid aqueous solution environment. In order to obtain such an effect of improving the resistance to sulfuric acid dew point corrosion, the Si content is preferably 0.25% or more.
  • Mn 0.50 to 1.00%
  • Mn is an element that increases the strength of steel. In order to obtain a desired strength, the amount of Mn is set to 0.50% or more. On the other hand, when the amount of Mn exceeds 1.00%, the toughness and weldability of steel are reduced. Therefore, the amount of Mn is set in the range of 0.50 to 1.00%. From the viewpoint of maintaining strength and suppressing the formation of inclusions that degrade the sulfuric acid dew point corrosion resistance, the Mn content is preferably in the range of 0.50 to 0.70%.
  • P 0.050% or less
  • P is a harmful element that segregates at grain boundaries and lowers the toughness of steel.
  • the P content is 0.050% or less.
  • P is desirably reduced as much as possible, a reduction to less than 0.005% causes an increase in manufacturing cost. Therefore, the lower limit of the amount of P is preferably 0.005%.
  • S 0.0020 to 0.0200%
  • S is an element that contributes to the formation of a Cu 2 S film in the presence of Cu, suppresses the corrosion reaction on the steel surface, and improves the resistance to sulfuric acid dew point corrosion.
  • S forms MnS which is a non-metallic inclusion, and this MnS is a harmful element that lowers the local corrosion resistance due to the origin of local corrosion. Therefore, from the viewpoint of ensuring sulfuric acid dew point corrosion resistance, the S amount is set to 0.0020% or more. On the other hand, from the viewpoint of avoiding a decrease in local corrosion resistance, the amount of S is set to 0.0200% or less. In addition, from the viewpoint of further improving the sulfuric acid dew point corrosion resistance, the S amount is preferably 0.0050% or more.
  • Cu 0.20 to 0.50%
  • Cu is an essential element that improves acid resistance in a corrosive environment caused by acid.
  • the amount of Cu is less than 0.20%, the effect is small.
  • the amount of Cu exceeds 0.50%, the acid resistance improving effect is saturated and the productivity, in particular, the hot workability is deteriorated. Therefore, the Cu amount is set in the range of 0.20 to 0.50%.
  • Ni 0.10 to 0.80%
  • Ni is an element that suppresses deterioration of hot workability due to the addition of Cu or Sb. However, when the amount of Ni is less than 0.10%, the effect is small. On the other hand, if the Ni content exceeds 0.80%, the effect of suppressing deterioration of hot workability is saturated and the cost is increased. Therefore, the Ni content is in the range of 0.10 to 0.80%.
  • Cr 0.20 to 1.50%
  • Cr does not greatly contribute to the effect of improving the sulfuric acid dew point corrosion resistance in a normal temperature environment, it is an element that improves the sulfuric acid dew point corrosion resistance when the use environment becomes a high temperature of 120 ° C. or higher.
  • the Cr content is less than 0.20%, these effects are small.
  • the Cr content exceeds 1.50%, these effects are saturated and the cost is increased. Therefore, the Cr content is in the range of 0.20 to 1.50%. Preferably, it is in the range of 0.40 to 1.50%.
  • Sb 0.050 to 0.300%
  • Sb is an element that concentrates on the steel surface as a Cu compound by complex addition with Cu and improves acid resistance.
  • the Sb content is less than 0.050%, the effect is small.
  • the amount of Sb exceeds 0.300%, the effect is saturated and manufacturability, particularly hot workability is deteriorated. Therefore, the Sb amount is set in the range of 0.050 to 0.300%.
  • the Sb content is preferably in the range of 0.100 to 0.200%.
  • Co 0.002 to 0.020%
  • Co is an element that suppresses the deterioration of hot workability due to the addition of Cu or Sb.
  • Co is an element that contributes to the improvement of the resistance to sulfuric acid dew point corrosion even in a small amount.
  • the Co content is less than 0.002%, the effect is small.
  • the amount of Co exceeds 0.020%, the cost increases. Therefore, the Co amount is set to a range of 0.002 to 0.020%. Preferably it is 0.002 to 0.010% of range.
  • W 0.005-0.200%
  • W is an element that improves acid resistance, particularly hydrochloric acid resistance. That is, WO 4 2 ⁇ ions formed in a corrosive environment exhibit a barrier effect against anions such as chloride ions, and form insoluble FeWO 4 to suppress the progress of corrosion. Moreover, the rust layer (corrosion product) formed on the steel sheet surface in a sulfuric acid environment is densified by the presence of W. Furthermore, W has a function of repairing such a rust layer while suppressing the inhibition of the stabilization of such a rust layer by chloride ions.
  • W suppresses corrosion in an acid environment, particularly an environment in which hydrochloric acid is added to sulfuric acid, by chemical and physical action, and greatly improves hydrochloric acid resistance.
  • the amount of W is less than 0.005%, the above effect cannot be obtained sufficiently.
  • the amount of W exceeds 0.200%, the above effect is saturated and the cost is increased. Therefore, the W amount is in the range of 0.005 to 0.200%. Preferably it is 0.020 to 0.100% of range.
  • the improvement effect is acquired by adding Cu and Sb similarly to sulfuric acid dew point corrosion resistance.
  • W has the effect of stabilizing the above corrosion products, and in order to improve the hydrochloric acid resistance in an environment in which hydrochloric acid is added to such sulfuric acid, together with an anticorrosive element such as Cu or Sb. It is very effective to add W in combination.
  • Ti 0.005 to 0.050%
  • Ti is an element added for the purpose of improving the strength and toughness of steel.
  • the amount of Ti is less than 0.005%, a desired effect cannot be obtained.
  • the amount of Ti exceeds 0.050%, the effect of improving the strength and toughness of the steel is saturated. Therefore, the Ti amount is set to a range of 0.005 to 0.050%.
  • Al 0.001 to 0.050%
  • Al is an element added as a deoxidizer. From the viewpoint of obtaining such an effect, the Al amount needs to be 0.001% or more. On the other hand, if the Al content exceeds 0.050%, the toughness of the steel decreases. Therefore, the Al content is set in the range of 0.001 to 0.050%. Preferably, it is in the range of 0.010 to 0.050%.
  • N 0.0005 to 0.0050% N is an element that degrades the toughness of steel in a solid solution state, and is preferably reduced as much as possible, but is acceptable if the N content is 0.0050% or less. On the other hand, it is technically difficult to completely remove N, and reduction more than necessary causes an increase in manufacturing cost. Therefore, the lower limit of the N amount is 0.0005%.
  • each component satisfies the above range.
  • the contents of S, Cu, Sb and W are the following formula (1), and the contents of Cu, Ni, Sb and Co are the following formula (2). It is important to satisfy each of these relationships. 0.50 ⁇ [% Cu] / (10 ⁇ [% S] + [% Sb] + [% W]) ⁇ 5.00 (1) 0.50 ⁇ ([% Ni] + 5 ⁇ [% Co]) / ([% Cu] + [% Sb]) ⁇ 2.50 (2)
  • [% S], [% Cu], [% Ni], [% Sb], [% Co] and [% W] are respectively S, Cu, Ni, Sb, Co and W in the component composition. Content (mass%).
  • the rolling reduction 97.75%
  • the finishing temperature 850 ° C.
  • the winding temperature 560 ° C.
  • the average cooling rate from 800 ° C. to 650 ° C. is 3.0 to 8.0 ° C./s. It was made to be within the range.
  • a corrosion test piece having a width of 20 mm ⁇ length of 30 mm ⁇ thickness of 3 mm was cut out, and the cut out corrosion test piece was subjected to a sulfuric acid aqueous solution ( (Corrosion weight loss was measured in a sulfuric acid immersion corrosion test immersed in a temperature of 70 ° C. and a concentration of 50 mass%) for 6 hours, and the corrosion rate of each specimen was calculated from the corrosion weight loss.
  • the sulfuric acid dew point corrosion resistance was evaluated according to the following criteria.
  • the contents of C, Ti and N satisfy the relationship of the following formula (3). 0.30 ⁇ [% Ti] / (0.2 ⁇ [% C] + [% N]) ⁇ 2.50 (3)
  • [% C], [% Ti] and [% N] are the contents (mass%) of C, Ti and N in the component composition, respectively.
  • Fe and inevitable impurities are elements that are inevitably mixed from steel raw material ore and scrap, etc., and are not added consciously and do not affect the effects of the present invention. It refers to an impurity component. Examples of such inevitable impurities include O (oxygen), and the upper limit is about 0.0050%.
  • the area ratio of the ferrite phase occupying the entire steel structure is 75% or more, the area ratio of the pearlite phase is less than 25%, and the remainder other than the ferrite phase and the pearlite phase.
  • Examples include steel structures having a total area ratio of less than 5%.
  • the hot rolling conditions described later are appropriately controlled.
  • the average cooling rate in the temperature range of 800 ° C. to 650 ° C. is 1.0 ° C./s to 20.0 ° C. It is important to keep it below / s.
  • Area ratio of ferrite phase 75% or more
  • the sulfuric acid dew-point corrosion steel may be used after being bent depending on the shape of the final product.
  • the area ratio of the ferrite phase in the entire steel structure is preferably 75% or more. More preferably, it is 80% or more.
  • the area ratio of the ferrite phase may be 100%.
  • Perlite phase area ratio less than 25%
  • the sulfuric acid dew-point corrosion steel may be used after being bent depending on the shape of the final product.
  • the area ratio of the pearlite phase is 25% or more, there is a possibility that cracking may occur during bending. Therefore, the area ratio of the pearlite phase in the entire steel structure is preferably less than 25%. More preferably, it is 20% or less.
  • the area ratio of the pearlite phase may be 0%.
  • the remaining structure other than the ferrite phase and the pearlite phase includes a bainite phase and the like, and when a bainite phase or a martensite phase is mixed, there is a concern about cracking during bending. Therefore, the total area ratio of the remaining structure other than the ferrite phase and the pearlite phase is preferably less than 5%.
  • the maximum Vickers hardness exceeds 200, cracks tend to occur during bending, and fatigue resistance tends to deteriorate.
  • the average Vickers hardness is less than 80, it is difficult to ensure a predetermined strength. For this reason, it is preferable that the maximum Vickers hardness is 200 or less and the average Vickers hardness is 80 or more.
  • the current density 0.1 A / cm in the cathodic polarization curve showing the relationship between the current density and the potential in a sulfuric acid aqueous solution having a temperature of 70 ° C. and a concentration of 50% by mass.
  • Va is the current density in the cathodic polarization curve in the sulfuric acid aqueous solution of the reference steel of the sulfuric acid dew-point corrosion steel: 0.1 A / cm 2
  • FIG. 4 shows the relationship between the cathodic polarization curve representing the relationship between the current density and potential of the reduction reaction of hydrogen ions in a sulfuric acid aqueous solution at a temperature of 70 ° C. and a concentration of 50% by mass, and the relationship between the current density and potential of the iron dissolution reaction.
  • An example of the anodic polarization curve to represent is shown. In FIG. 4, the point where the cathodic polarization curve and the anodic polarization curve intersect is the point where corrosion actually proceeds.
  • the inventors obtained the cathode polarization curves of various steels under various conditions, and further investigated the relationship between the cathode polarization curves and sulfuric acid dew point corrosion resistance. As a result, it is effective to suppress the cathodic reaction to improve the sulfuric acid dew point corrosion resistance.
  • the sulfuric acid dew point corrosion resistance is cathodic polarization in a sulfuric acid aqueous solution having a temperature of 70 ° C. and a concentration of 50% by mass. The current density in the curve was found to be closely related to the potential at 0.1 A / cm 2 .
  • Va is a standard that is so-called general steel.
  • Current density: Vg (V) which is the potential at 0.1 A / cm 2 , as described above (4 It has been found that it is preferable to satisfy the formula (1), and by satisfying such a relationship, the resistance to sulfuric acid dew point corrosion is further enhanced. Therefore, it is preferable to satisfy the relationship of Vg ⁇ Va> 0.03. More preferably, Vg ⁇ Va> 0.05.
  • Vg ⁇ Va is not particularly limited, but is usually about 0.15. Note that when potential measurement is performed using the Hg / Hg (SO 4 ) reference electrode, both Va and Vg show negative values. Even in this case, Va is made relatively smaller than Vg. This is very important. In addition, the current density in the cathode polarization curve: 0.1 A / cm 2 potential was selected. If the current density is smaller than this, noise may occur depending on the measurement conditions. This is because the cathode reaction itself is rate-limiting and it may be difficult to accurately measure the potential.
  • the reference steel referred to here is mass%, C: 0.050 to 0.150%, Si: 0.10 to 0.80%, Mn: 0.50 to 1.00%, P: 0. .050% or less, S: 0.0020 to 0.0200%, Al: 0.001 to 0.050% and N: 0.0005 to 0.0050%, with the balance being Fe and inevitable impurities Steel having a component composition (in particular, Cu: less than 0.02%, Ni: less than 0.02%, Cr: less than 0.02%, Sb: less than 0.010%, Co: less than 0.002%, W : Less than 0.005% and Ti: less than 0.005%).
  • the cathodic polarization curves in a sulfuric acid aqueous solution having a temperature of 70 ° C. and a concentration of 50% by mass are substantially the same.
  • the sulfuric acid dew-point corrosion steel of the present invention is obtained by finishing a steel material adjusted to the above component composition into various shapes such as a thin steel plate, a thick steel plate, and a shaped steel. After melting by a generally known method such as a furnace, electric furnace, vacuum degassing apparatus, etc., a steel slab is formed by a continuous casting method, etc., and this steel slab is hot-rolled by reheating immediately or after cooling. A method is mentioned. Moreover, when making it a cold-rolled steel sheet, pickling, cold rolling, and annealing are further performed to obtain a product.
  • the hot rolling conditions include the required mechanical properties, ie, strength (hardness), bendability, and fatigue resistance, from the viewpoint of ensuring the reduction rate of 50 to 99% and the finishing temperature of 650 to 950 ° C.
  • the winding temperature is preferably 400 to 650 ° C.
  • the average cooling rate from 800 ° C. to 650 ° C. is preferably 1.0 to 20.0 ° C./s.
  • the average cooling rate from 800 ° C. to 650 ° C. is preferably set to 1.0 to 10.0 ° C./s.
  • Vickers hardness is an arbitrary value in the surface layer (position 0.5 mm from the surface) of the hot-rolled steel sheet obtained as described above under the condition of load: 9.8 N according to JIS Z 2244. These 20 points were measured, and the average value and the maximum value were obtained.
  • a corrosion test piece having a width of 20 mm, a length of 30 mm, and a thickness of 3 mm was cut out from the hot-rolled steel sheet obtained as described above, and the cut out corrosion test piece was converted into a sulfuric acid aqueous solution (temperature: 140 ° C., concentration: 80
  • the sample was subjected to a sulfuric acid immersion corrosion test that was immersed in (mass%) for 3 hours, the corrosion weight loss was measured, and the corrosion rate of each specimen was calculated from the corrosion weight loss.
  • the sulfuric acid dew point corrosion resistance at high temperatures was evaluated according to the following criteria.
  • test material having a size of 10 mm ⁇ 10 mm was cut out from the hot-rolled steel sheet obtained as described above, and the end surface and the back surface of the cut-out test piece were covered with a protective coating to be protected.
  • This test material was immersed in a sulfuric acid aqueous solution (temperature: 70 ° C., concentration: 50 mass%) for 10 minutes, and then the potential was swept to the cathode side at a rate of 1 mV / sec to about 0.4 V to obtain a cathode polarization curve. Collected. Using the obtained cathode polarization curve, the potential Va (V) at a current density of 0.1 A / cm 2 was obtained by drawing, and the reference steel No. 1 was obtained.
  • the current difference in the cathode polarization curve of 18 was determined as a potential difference from the potential Vg (V) at 0.1 A / cm 2 .
  • a Hg / Hg (SO 4 ) reference electrode was used. The results are also shown in Table 2.

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PCT/JP2017/030259 2016-08-25 2017-08-24 耐硫酸露点腐食鋼 WO2018038196A1 (ja)

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Application Number Priority Date Filing Date Title
JP2017564516A JP6332576B1 (ja) 2016-08-25 2017-08-24 耐硫酸露点腐食鋼
KR1020197008032A KR102220619B1 (ko) 2016-08-25 2017-08-24 내황산 이슬점 부식강
CN201780049872.9A CN109563594B (zh) 2016-08-25 2017-08-24 耐硫酸露点腐蚀钢
MYPI2019000896A MY189754A (en) 2016-08-25 2017-08-24 Sulfuric acid dew point corrosion-resistant steel

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