WO2017181630A1 - 一种抗氢致开裂压力容器钢板及其制造方法 - Google Patents

一种抗氢致开裂压力容器钢板及其制造方法 Download PDF

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WO2017181630A1
WO2017181630A1 PCT/CN2016/102379 CN2016102379W WO2017181630A1 WO 2017181630 A1 WO2017181630 A1 WO 2017181630A1 CN 2016102379 W CN2016102379 W CN 2016102379W WO 2017181630 A1 WO2017181630 A1 WO 2017181630A1
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temperature
hydrogen
steel plate
rolling
heating
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PCT/CN2016/102379
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English (en)
French (fr)
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刘海宽
李经涛
张建
恽鹏程
张军
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江阴兴澄特种钢铁有限公司
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Priority to MYPI2018000193A priority Critical patent/MY184402A/en
Priority to US15/735,146 priority patent/US20180298463A1/en
Priority to EP16899214.7A priority patent/EP3309275B1/en
Priority to KR1020187012333A priority patent/KR102145898B1/ko
Publication of WO2017181630A1 publication Critical patent/WO2017181630A1/zh

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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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron

Definitions

  • the present invention belongs to the field of steel sheet manufacturing, and in particular relates to a 50 mm thick SA516Gr70 (HIC) anti-hydrogen induced cracking pressure vessel steel sheet and a method for producing the same.
  • HIC SA516Gr70
  • SA516Gr70 (HIC) steel sheets are mainly used in petrochemical plants used in wet H 2 S corrosive environments.
  • Hydrogen induced splitting is a common form of steel in the wet hydrogen sulfide environment.
  • H 2 8 reacts with the steel surface to produce hydrogen atoms.
  • Hydrogen atoms diffuse into the steel and accumulate at the metallurgical defects to produce hydrogen molecules.
  • a large internal stress is generated, causing interface cracking to form hydrogen bubbling.
  • small hydrogen bubbles tend to be connected to each other to form a hydrogen-induced splitting with stepped features.
  • the normalizing + air-cooling process is beneficial to the uniform steel plate structure, the strength of the sample after high-temperature and long-term simulated post-weld heat treatment is difficult to meet the requirements; the use of aerosol cooling after normalizing can be to some extent Improve the band structure of the steel plate, but the effect on improving the strength of the steel plate is not obvious. Because there is no tempering treatment, the surface of the steel plate may be martensite or bainite structure due to excessive cooling, resulting in low strength and high surface hardness.
  • the edge of the steel plate is cleaved during the manufacturing process of the container; the quenching + tempering process can significantly increase the strength of the steel plate, but because the quenching temperature is higher, the cooling rate is too fast, if the tempering is insufficient, the plate structure will be uneven, and hydrogen will be increased. Causing cracking sensitivity.
  • the present application proposes a hydrogen-induced splitting pressure vessel steel and a manufacturing method thereof, which are suitable for use in a wet hydrogen sulfide environment, and have a simple composition design and a production process, are suitable for mass production, and are not found by searching.
  • a patent related to the process is a hydrogen-induced splitting pressure vessel steel and a manufacturing method thereof, which are suitable for use in a wet hydrogen sulfide environment, and have a simple composition design and a production process, are suitable for mass production, and are not found by searching.
  • the technical problem to be solved by the present invention is to provide a SA51 6Gr70 (HIC) steel plate with a thickness of 50 mm for the above prior art, which can be applied to the production of a petrochemical device used in a wet H 2 S corrosive environment, and has a higher Strength and low temperature impact toughness, low hardness and good resistance to HIC.
  • the steel sheet has finer grains and a lower content of non-metallic inclusions, and there is no significant banded structure. After the simulated post-weld heat treatment between high temperature and long turns, the strength and low temperature impact toughness of the steel plate are not significantly weakened, and the head steel plate can meet the requirements of both cold forming and thermoforming manufacturing processes.
  • the anti-hydrogen induced splitting pressure vessel steel sheet of the invention has hydrogen-induced splitting (HIC) performance: the steel sheet is in accordance with NAC E TM0284-2011 "Experimental Method for Performance Evaluation of Hydrogen-induced Splitting Steel in Pipeline Pressure Vessels"
  • the solution A was subjected to hydrogen-induced splitting test.
  • the crack length ratio (CLR), crack width ratio (CTR) and crack sensitivity (CSR) of the single test section were all zero, and there was no hydrogen bubbling, that is, no defects after corrosion.
  • the yield strength of the steel plate is ⁇ 360Mp a
  • the tensile strength is ⁇ 540Mp a
  • the lateral value of the heart-51°C transverse Charpy impact is ⁇ 150J
  • the surface of the steel plate is Brinell hardness ⁇ 170HB, grain size ⁇ Class 8.0, banded structure ⁇ 2.0.
  • the main chemical components of the steel sheet of the present invention are mainly employed. , Si, Mn composition design, to minimize the 8, P content, do not intentionally add Cr, Ni, Cu, Mo, Nb, V, Ti, B and other alloying elements, the composition of the design is simple. C can significantly improve the strength and hardness of the steel plate, but with the increase of carbon content, carbide segregation is easy to occur, resulting in the difference between the hardness of the segregation zone and the surrounding structure, resulting in HIC corrosion. Mn improves the strength of the steel by solid solution strengthening, but Mn is added. When the temperature is above 1.05%, the cracking sensitivity can be improved. However, the sub-temperature quenching and tempering treatment can eliminate the adverse effects.
  • Si is mainly used as a reducing agent and a deoxidizer for steelmaking crucibles, and has a certain solid solution strengthening effect.
  • the Si element is easily segregated at the grain boundary, which promotes the generation of intergranular cracks.
  • the content of C, Mn and Si increases, the sensitivity of HIC is increased.
  • the main strengthening element the content is still within the allowable range. Try to control by the upper limit.
  • the composition control range of the present application is C: 0.16 ⁇ 0.20%, Si: 0.15-0.40%, Mn: 1.05 ⁇ 1.20 ⁇ 3 ⁇ 4, and its adverse effect is eliminated by subsequent heat treatment.
  • P and S are harmful elements.
  • Another object of the present invention is to provide a method for producing the above-described hydrogen-induced splitting pressure vessel steel sheet, which is specifically as follows:
  • the continuous casting billet production mode, the process route: KR pretreatment ⁇ converter smelting-LF refining ⁇ RH refining ⁇ continuous casting, improving the purity of molten steel and reducing the segregation of the billet are the key measures for the anti-hydrogen induced cracking of the steel.
  • the smelting raw materials are pretreated by KR hot metal, and the converter is smelted and smelted.
  • the strict control is 8 ⁇ 0.001 ⁇ 3 ⁇ 4, P ⁇ 0.006%, and the non-metallic inclusions of class A, B, C, D and Ds are ⁇ 1.0.
  • the sectional heating method is adopted: the total heating time is 225 ⁇ 300min, the temperature of the first heating section is 1050 ⁇ 115 0 °C, the temperature of the second heating section is 1200 ⁇ 1260 °C, and the temperature of the soaking section is 1170 ⁇ 1250 ° C, the second heating section and the soaking section total heating ⁇ ⁇ 120! ⁇ ! 1, wherein the heating of the second heating section and the soaking section cooperate to fully promote hydrogen and promote segregation and diffusion, Organization
  • the two-stage rolling process is adopted: the "high temperature and large pressure" process is adopted in the rough rolling stage, and the single pass reduction of at least 2 passes in the vertical rolling pass is ⁇ 50 mm; the cumulative reduction ratio in the finishing rolling stage is ⁇ 60%, the final rolling temperature is controlled at 780 ⁇ 820 ° C, after the rolling ACC rapid cooling, after the steel plate is off the line, the stack is slowly cooled for more than 72 hours, fully expanding hydrogen.
  • the tempering temperature of the steel plate of the present invention is not lower than the temperature after the simulated post-weld heat treatment, tempering: tempering temperature: 640 to 670 ° C, the coefficient of thermal insulation: 3.5 to 4.5 min / Mm.
  • Sub-temperature quenching can reduce the brittle transition temperature, refine the grains, obtain an appropriate amount of finely distributed fine ferrite structure, suppress crack propagation, and significantly improve the toughness of the steel. Compared with the conventional quenching process, the same hardness can be used to lower the tempering temperature, and the higher the toughness, and the stress concentration can be suppressed and the crack initiation and expansion can be inhibited; the unmelted ferrite is present in the sub-temperature quenched structure. The content of carbon and alloying elements in the body increases, and a small amount of stable retained austenite exists after quenching, which also prevents crack initiation and expansion. Sub-temperature quenching can also reduce the segregation of harmful impurity elements at the austenite grain boundary and purify the grain boundary.
  • the present invention relates to a SA516Gr70 (HIC) hydrogen-induced splitting pressure vessel steel sheet having a thickness of 50 mm, which has high strength and low temperature impact toughness, low hardness and good HIC resistance.
  • the steel sheet has finer grains and a lower content of non-metallic inclusions, and there is no significant banded structure. After simulating post-weld heat treatment between high temperature and long turns, the strength and low temperature impact toughness of the steel sheet were not significantly weakened.
  • the hardness of the steel plate is increased due to work hardening, which is easy to cause The steel plate eventually splits.
  • the steel plate of the present invention has a hardness of 170HB or less, and can still meet the requirements of cold working after work hardening. Therefore, the steel plate produced by the manufacturing method of the present invention can meet the requirements of both cold forming and thermoforming head forming processes.
  • the present invention uses continuous casting billet production to reduce hydrogen induced splitting sensitivity by reducing segregation of the billet, improving the purity of the molten steel, and reducing the band structure of the steel sheet.
  • composition of the steel sheet is simple in design, and the main constituent elements are. , Si, Mn alloy three elements, do not intentionally add Ni
  • the heat treatment process of the steel plate of the invention adopts the unique process of sub-temperature quenching + tempering, compared with the quenching and normalizing process, the sub-temperature quenching heating temperature is lower, and the cooling rate in the sub-temperature quenching cooling process is between the normalizing temperature and the quenching
  • the toughness can be optimally matched, which can improve the tensile strength and low temperature impact toughness of the steel plate, and can avoid the high hardness of the surface of the steel plate.
  • the structure is ferrite + pearl light. Body tissue, fine grain, no obvious banded structure.
  • FIG. 1 is a metallographic structure diagram of a steel sheet according to Embodiment 1 of the present invention.
  • FIG. 2 is a metallographic structure diagram of a steel sheet according to Embodiment 2 of the present invention.
  • Embodiment 3 is a metallographic structure diagram of a steel sheet according to Embodiment 3 of the present invention.
  • the hydrogen-induced splitting pressure vessel steel sheet of the present embodiment has a thickness of 50 mm, and its chemical composition is: C: 0.17%, Si: 0.34%, Mn: 1.18%, P: 0.004%, S. : 0.0005% , H: 0.00006% , 0: 0.0015% , N: 0.0035% , the balance is Fe and inevitable impurity elements,
  • the production of continuous casting billet with a thickness of 370 mm is carried out by KR hot metal pretreatment, converter smelting, LF refining, RH refining and slab continuous casting process, and the smelting process is carried out after the smelting process, and the continuous casting process is low.
  • the whole process of superheat is argon gas protection casting, and the slab segregation is controlled by the dynamic soft reduction technology. After the slab is off the line, the cover is slowly cooled for more than 48 hours.
  • the sectional heating mode is adopted: the total heating time is 270 minutes, the temperature of the first heating section is 1120 ° C, the temperature of the second heating section is 1250 ° C, the temperature of the soaking section is 1240 ° C, the second heating section and The total heating time in the soaking section is 13 5 minutes, ensuring that the slab segregation is fully diffused.
  • Two-stage rolling is adopted, and the rough rolling stage adopts a high-temperature large pressing process, and the vertical rolling pass has a total of 3 passes, and the single pass reduction amounts are 25 mm, 55 mm, and 50 mm, respectively; Improve the internal quality and core performance of the steel plate.
  • the cumulative reduction rate in the finishing rolling stage is 65%, the finishing rolling temperature is controlled at 810 °C, the ACC is rapidly cooled after rolling, and the steel plate is stacked and slowly cooled for 72 hours.
  • the temperature of the steel plate Acl of the embodiment of the present invention is 720 ° C
  • the temperature of Ac3 is 850 ° C
  • sub-temperature quenching quenching temperature 835 ° C
  • insulation inter-turn coefficient 1.8 min / mm
  • tempering tempering temperature: 660 ° C, insulation between inches coefficient: 3.8min / mm.
  • the 50 mm thick anti-hydrogen induced splitting pressure vessel steel plate produced by the above manufacturing process has well-matched comprehensive mechanical properties and excellent hydrogen-induced splitting performance, and its mechanical properties are shown in Table 1.
  • the cracking performance is shown in Table 4.
  • the metallographic structure photo is shown in Figure 1.
  • the sectional heating mode is adopted: the total heating time is 285 min, the temperature of the first heating section is 1125 ° C, the temperature of the second heating section is 1255 ° C, the temperature of the soaking section is 1242 ° C, the second heating section and The total heating time in the soaking section is 15 Omin, ensuring that the slab segregation is fully diffused.
  • Two-stage rolling is adopted, and the rough rolling stage adopts a high-temperature large pressing process, and the vertical rolling pass has a total of 3 passes, and the single pass reduction amounts are 25 mm, 55 mm, and 55 mm, respectively; Improve the internal quality and core performance of the steel plate.
  • the cumulative reduction rate in the finishing rolling stage is 66%, and the finishing rolling temperature is controlled at 812 °C. After rolling, the ACC is rapidly cooled, and the steel plate is stacked and slowly cooled for 72 hours.
  • Sub-temperature quenching + tempering process sub-temperature quenching: quenching temperature 842 ° C, insulation inter-turn coefficient: 1.8 min / mm; tempering: tempering temperature: 650 ° C, insulation day coefficient: 4.0 min /mm.
  • the 50 mm thick anti-hydrogen induced splitting pressure vessel steel plate obtained through the above manufacturing process has well-matched comprehensive mechanical properties and excellent hydrogen-induced splitting performance, and its mechanical properties are shown in Table 2, which is resistant to hydrogen.
  • the cracking performance is shown in Table 4, and the metallographic photo is shown in Figure 2.
  • the hydrogen-induced splitting pressure vessel steel sheet of the present embodiment has a thickness of 50 mm, and its chemical composition is: C: 0.16%, Si: 0.35%, Mn: 1.16%, P: 0.005%, S. : 0.0007% , H: 0.00006% , 0: 0.0012% , N: 0.0033% , the balance is Fe and inevitable impurity elements, [0056]
  • the manufacturing process of the steel sheet is as follows:
  • the production of continuous casting billet the smelting raw material is sequentially subjected to KR hot metal pretreatment, converter smelting, LF refining, RH refining and slab continuous casting process, and the smelting process is carried out after the smelting, and the continuous casting process adopts low superheat full argon.
  • Gas protection casting, the slab segregation is controlled by dynamic soft reduction technology, and the slab is placed under the line and slowly cooled for more than 48 hours.
  • the sectional heating mode is adopted: the total heating time is 300 min, the temperature of the first heating section is 1118 ° C, the temperature of the second heating section is 1252 ° C, the temperature of the soaking section is 1241 ° C, the second heating section and The total heating time in the soaking section is 15 Omin, ensuring that the slab segregation is fully diffused.
  • Two-stage rolling is adopted, and the rough rolling stage adopts a high-temperature large pressing process, and the vertical rolling pass has a total of three passes, and the single pass reduction amounts are 30 mm, 55 mm, and 55 mm, respectively; Improve the internal quality and core performance of the steel plate.
  • the cumulative rolling reduction rate in the finishing rolling stage is 68%, the finishing rolling temperature is controlled at 802 °C, the ACC is rapidly cooled after rolling, and the steel plate is stacked and slowly cooled for 72 hours.
  • Sub-temperature quenching + tempering process sub-temperature quenching: quenching temperature 840 ° C, insulation inter-turn coefficient: 1.8 min / mm; tempering: tempering temperature: 645 ° C, insulation day coefficient: 4.2 min /mm.
  • the 50 mm thick anti-hydrogen splitting pressure vessel steel plate obtained through the above manufacturing process has well-matched comprehensive mechanical properties and excellent hydrogen-induced splitting performance, and its mechanical properties are shown in Table 3, which is resistant to hydrogen.
  • the cracking performance is shown in Table 4, and the metallographic structure photograph is shown in Fig. 3.
  • Simulated thermoforming system 920 ⁇ 20°C, l.l-1.2min/mm, air-cooled; simulated post-weld heat treatment: 63 5 ⁇ 14°C ⁇ l8h.
  • Simulated sub-temperature quenching + simulated tempering process system is the same as steel plate heat treatment process parameters.
  • Simulated thermoforming system 920 ⁇ 20°C, l.l-1.2min/mm, air-cooled; simulated post-weld heat treatment: 63 5 ⁇ 14°C ⁇ l8h.
  • Simulated sub-temperature quenching + simulated tempering process system is the same as steel plate heat treatment process parameters.
  • Simulated thermoforming system 920 ⁇ 20°C, l.l-1.2min/mm, air-cooled; simulated post-weld heat treatment: 63 5 ⁇ 14°C ⁇ l8h.
  • Simulated sub-temperature quenching + simulated tempering process system is the same as steel plate heat treatment process parameters.
  • the steel sheets of the examples of the present application have a grain size of 8.5 and a band structure of 0.5, as shown in FIGS. 1 to 3.

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Abstract

一种抗氢致开裂压力容器钢板及其制造方法，化学成分按重量百分比计为C：0.16～0.20％，Si：0.15～0.40％，Mn：1.05～1.20％，P：≤0.008％，S：≤0.002％，Nb：≤0.01％，V：≤0.01％，Ti：≤0.01％，B：≤0.0005％，余量为Fe及不可避免的杂质元素，碳当量Ceq≤0.42％，计算公式为：Ceq＝C+Mn/6+(Cr+Mo+V)/5+(Ni+Cu)/15。

Description

一种抗氢致幵裂压力容器钢板及其制造方法 技术领域
[0001] 本发明属于钢板制造领域， 具体涉及一种 50mm厚的 SA516Gr70(HIC)抗氢致幵 裂压力容器钢板及其制造方法。
背景技术
[0002] SA516Gr70(HIC)钢板主要用于湿 H 2S腐蚀环境使用的石油化工装置。 氢致幵裂 是钢在湿硫化氢环境中的一种常见破坏形式， H 28与钢表面发生反应产生氢原子 ， 氢原子向钢中扩散并在冶金缺陷处聚集产生氢分子， 使钢材内部产生很大的 内应力， 以致引起界面幵裂， 形成氢鼓泡， 当氢的压力继续增高吋， 小的氢鼓 泡趋向于相互连接， 形成有阶梯状特征的氢致幵裂。
[0003] 在湿 H 2S腐蚀环境下使用的压力容器一旦失效， 将对安全生产构成严重威胁， 带来巨大的经济损失。 随着资源品质劣化和设备大型化、 轻量化的发展趋势， 设计上需要钢板在更高温度和更长吋间的模拟焊后热处理条件下， 仍然具有良 好的力学性能和优异的抗氢致幵裂 （HIC) 性能。
[0004] 目前多数中厚板企业采用 C、 Mn、 Si组合成分设计， 通过降低。、 Mn、 S、 P元 素含量、 带状组织级别和非金属夹杂物含量来保证钢板 HIC性能。 随着模拟焊后 热处理温度的提高和模拟焊后热处理吋间的延长， 试样模拟焊后热处理后抗拉 强度会大幅度下降。 在限制碳当量和微合金元素条件下， 抗拉强度很难满足标 准要求， 尤其是封头钢板热成型后力学性能经常会出现无法恢复正常性能的情 况。 国外有些企业通过降低 C含量， 同吋添加元素 Ni、 Cu， 采用锻造坯轧制方式 生产， 这种生产工艺在提高钢板强度方面有一定效果， 但生产周期长， 也会大 幅度增加生产成本。
[0005] 目前涉及湿硫化氢环境使用的抗氢致幵裂压力容器钢的专利较少， 常用的热处 理工艺有三种， 公告号为 CN104480384A的发明专利采用正火 +空冷工艺生产， 正火后空冷。 公布号为 CN1046411629A的发明专利采用正火 +气雾冷却工艺生产 ， 公告号为 CN102605242A的发明专利采用淬火 +回火工艺生产。 以上三种热处 理工艺都有一定局限性， 虽然正火 +空冷工艺有利于均匀钢板组织， 但试样高温 长吋间模拟焊后热处理后强度很难满足要求； 正火后采用气雾冷却可以在一定 程度上改善钢板带状组织， 但对提高钢板强度方面效果不太明显， 由于没有回 火处理， 钢板表面可能由于冷却过快而产生马氏体或贝氏体组织， 造成钢板强 度低、 表面硬度高， 最终导致容器制造过程中钢板边部幵裂； 淬火 +回火工艺可 以明显提高钢板强度， 但由于淬火温度较高， 冷却速度过快， 如果回火不充分 ， 会造成钢板组织不均匀， 增加氢致幵裂敏感性。
[0006] 基于以上原因， 本申请提出了一种抗氢致幵裂压力容器钢及其制造方法， 适用 于在湿硫化氢环境使用， 成分设计及生产工艺简单， 适合批量生产， 经检索未 发现与该工艺相关的专利。
技术问题
[0007] 本发明所要解决的技术问题是针对上述现有技术提供一种厚度为 50mm的 SA51 6Gr70(HIC)钢板， 能够应用于湿 H 2S腐蚀环境使用的石油化工装置的制作， 具有 较高的强度和低温冲击韧性、 较低的硬度和良好的抗 HIC性能。 钢板具有较细的 晶粒和较低的非金属夹杂物含量， 且不存在明显带状组织。 在高温长吋间模拟 焊后热处理后， 钢板的强度和低温冲击韧性不明显减弱， 封头钢板可以同吋满 足冷成型和热成型两种制造工艺的要求。
问题的解决方案
技术解决方案
[0008] 本发明解决上述问题所采用的技术方案为： 一种抗氢致幵裂压力容器钢板， 该 钢板的化学成分按重量百分比计为 C: 0.16—0.20%, Si: 0.15—0.40% , Mn: 1.0 5〜1.20<¾， P: <0.008%, S: <0.002% , Nb: <0.01% , V： <0.01% , Ti: <0.01 % , B: <0.0005%, 余量为 Fe及不可避免的杂质元素， 碳当量 Ceq≤0.42<¾， 碳当 量计算公式为： Ceq=C+Mn/6+ (Cr+Mo+V) /5+ (Ni+Cu) /15。
[0009] 本发明抗氢致幵裂压力容器钢板， 其抗氢致幵裂 （HIC) 性能： 钢板按照 NAC E TM0284-2011 《管道压力容器抗氢致幵裂钢性能评价的实验方法》 中的 A溶液 进行抗氢致幵裂检验， 单个检验截面的裂纹长度率 （CLR) 、 裂纹宽度率 （CTR ) 和裂纹敏感率 （CSR) 均为 0， 无氢鼓泡， 即腐蚀后无缺陷。 635±14°Cxl8h模 拟焊后热处理后钢板屈服强度≥360Mpa， 抗拉强度≥540Mpa， 心部 -51°C横向夏 比冲击功单值≥150J; 钢板交货态表面布氏硬度≤170HB， 晶粒度≥8.0级， 带状组 织≤2.0级。
[0010] 本发明 50mm抗氢致幵裂压力容器钢板的化学成分是这样确定的：
[0011] 本发明钢板的主要化学成分主要采用。、 Si、 Mn组合成分设计， 尽量降低8、 P 含量， 不有意添加 Cr、 Ni、 Cu、 Mo、 Nb、 V、 Ti、 B等合金元素， 成分设计简 单。 C能够显著提高钢板的强度和硬度， 但随着碳含量的增加容易出现碳化物偏 析， 造成偏析区硬度与周围组织出现差异， 导致 HIC腐蚀， Mn通过固溶强化提 高钢的强度， 但 Mn添加到 1.05%以上吋， 可提高幵裂敏感性， 然而通过亚温淬 火、 回火处理可消除其不良影响； Si主要作为炼钢吋的还原剂和脱氧剂使用， 有 一定的固溶强化作用， 同吋 Si元素易偏析于晶粒边界， 助长晶间裂纹的产生； 虽 然随着 C、 Mn、 Si含量增加， 会提高 HIC的敏感性， 但作为主要强化元素， 其含 量仍然要在允许范围内尽量按上限控制。 本申请成分控制范围： C: 0.16〜0.20 % , Si: 0.15—0.40%, Mn: 1.05〜1.20<¾， 其不利影响通过后续热处理进行消除 。 P、 S是有害元素， 随钢中 S含量升高， 在 H 2S中浸泡吋进入钢中的氢量也升高 ， 从而产生 HIC的敏感性也升高。 当 P含量很低吋， 裂纹能在 MnS上形核， 但尺 寸很小， 不能被测出， 但如 P高 （如 P=0.4%) ， 则即使 S很低 （S=0.001%) ， 裂 纹也能在氧化物夹杂以及晶界上形核并扩展。 因此， 本申请需要应尽可能降低 钢中 S、 P含量。
[0012] 本发明另一目的是提供上述抗氢致幵裂压力容器钢板的制造方法， 具体如下：
[0013] 1) 冶炼工艺
[0014] 采用连铸坯生产方式， 其工艺路线： KR预处理→转炉冶炼—LF精炼→RH精炼 →连铸， 提高钢水纯净度、 降低铸坯偏析是钢抗氢致幵裂的关键措施。 冶炼原 料经 KR铁水预处理， 转炉冶炼后扒澄处理， 严格控制8≤0.001<¾， P<0.006% , A 类、 B类、 C类、 D类和 Ds非金属夹杂物类单项≤1.0级， 其总和≤3.5级； 连铸采用 低过热度全程氩气保护浇注， 通过动态轻压下技术控制铸坯偏析 B类 1.0级以下， 板坯下线后加罩缓冷 48小吋以上， 确保钢中的氢充分扩散。
[0015] 2) 加热、 轧制工艺
[0016] 采用分段加热方式： 总加热吋间为 225〜300min， 第一加热段温度为 1050〜115 0°C， 第二加热段温度为 1200〜1260°C， 均热段温度为 1170〜1250°C， 第二加热 段和均热段总加热吋间≥120!^!1， 其中加热中的第二加热段和均热段的配合起到 充分扩氢和促进偏析扩散的作用， 均化组织；
[0017] 采用两阶段轧制工艺： 粗轧阶段采用"高温大压下"工艺， 纵轧道次至少有 2个 道次的单道次压下量≥50mm; 精轧阶段累计压下率≥60%， 终轧温度控制在 780 〜820°C， 轧后 ACC快速冷却， 钢板下线后堆垛缓冷 72小吋以上， 充分扩氢。
[0018] 3) 热处理工艺
[0019] 采用亚温淬火 +回火工艺， 亚温淬火加热温度在 Acl〜Ac3之间， 亚温淬火： 淬 火温度 820〜850°C， 保温吋间系数： 1.8〜2.0min/mm， 水冷； 为了防止模拟焊后 热处理后钢板强度大幅度下降， 本发明钢板回火温度不低于模拟焊后热处理温 度， 回火： 回火温度 640〜670°C， 保温吋间系数： 3.5〜4.5min/mm。
[0020] 亚温淬火可以降低脆性转变温度、 细化晶粒， 得到适量的均匀分布的细小铁素 体组织， 阻抑裂纹扩展， 显著提高钢的韧性。 与常规淬火工艺比， 获得相等硬 度可用较低回火温度， 更兼有更高的韧性， 且可抑制应力集中与阻碍裂纹萌生 及扩展； 亚温淬火组织中存在未熔铁素体， 使奥氏体中碳和合金元素含量增加 ， 淬火后存在少量稳定的残余奥氏体， 亦可阻止裂纹的萌生与扩展。 亚温淬火 还可降低有害杂质元素在奥氏体晶界偏聚， 起到净化晶界作用。
发明的有益效果
有益效果
[0021] 与现有技术相比， 本发明的优点在于：
[0022] 本发明涉及一种 SA516Gr70(HIC)抗氢致幵裂压力容器钢板， 厚度为 50mm， 该 钢板具有较高的强度和低温冲击韧性、 较低的硬度和良好的抗 HIC性能。 钢板具 有较细的晶粒和较低的非金属夹杂物含量， 且不存在明显带状组织。 在高温长 吋间模拟焊后热处理后， 钢板的强度和低温冲击韧性不明显减弱。 在用于制作 压力容器的封头冷成型过程中， 由于加工硬化会造成钢板硬度升高， 容易导致 最终钢板幵裂。 本发明的钢板交货态硬度控制在 170HB以下， 加工硬化后仍然可 以满足冷加工的需要， 所以采用本发明制造方法生产的钢板可以同吋满足冷成 型和热成型两种封头成型工艺的要求。
[0023] 为了实现上述目的， 本发明采用连铸坯生产， 通过降低铸坯偏析、 提高钢水纯 净度、 和减轻钢板带状组织等手段， 降低氢致幵裂敏感性。
[0024] 钢板成分设计简单， 主要成分元素为。、 Si、 Mn合金三种元素， 不有意添加 Ni
、 Cr、 Cu、 Mo、 Nb、 V、 Ti等合金元素， 减少偏析， 生产成本低， 通过降低 S
、 P、 H、 0、 N元素含量， 提高钢水的纯净度， 降低钢板氢致幵裂的敏感性， [0025] 铸坯加热采用分段加热方式， 尤其是延长第二加热段和均热段总吋间， 可使偏 析充分扩散， 通过高温轧制阶段的高温大压下轧制工艺， 可以有效将疏松缺陷 充分压合， 提高钢板内部质量。
[0026] 本发明钢板的热处理工艺采用亚温淬火 +回火独特工艺， 与淬火和正火工艺相 比， 亚温淬火加热温度较低， 亚温淬火冷却过程中冷却速度介于正火温度和淬 火温度之间， 在进一步高温回火后， 其强韧性可以达到最佳匹配， 既可以改善 钢板抗拉强度和低温冲击韧性， 同吋可以避免钢板表面硬度偏高， 其组织为铁 素体 +珠光体组织， 晶粒细小、 无明显带状组织。
对附图的简要说明
附图说明
[0027] 图 1为本发明实施例 1的钢板金相组织图；
[0028] 图 2为本发明实施例 2的钢板金相组织图；
[0029] 图 3为本发明实施例 3的钢板金相组织图。
实施该发明的最佳实施例
本发明的最佳实施方式
[0030] 以下结合附图实施例对本发明作进一步详细描述。
[0031] 实施例 1
[0032] 本实施例的抗氢致幵裂压力容器钢板的厚度为 50mm， 其化学成分按重量百分 比计为: C: 0.17% , Si: 0.34% , Mn: 1.18% , P: 0.004% , S: 0.0005% , H: 0.00006% , 0： 0.0015% , N: 0.0035% , 余量为 Fe及不可避免的杂质元素， 碳当量 Ceq≤0.41<¾， 计算公式为： Ceq=C+Mn/6+ (Cr+Mo+V) /5+ (Ni+Cu) /15
[0033] 该钢板的制造工艺为如下：
[0034] 1) 冶炼、 连铸
[0035] 采用厚度为 370mm的连铸坯生产， 冶炼原料依次经 KR铁水预处理、 转炉冶炼 、 LF精炼、 RH精炼和板坯连铸工序， 转炉冶炼后进行扒澄处理， 连铸工序采用 低过热度全程氩气保护浇注， 通过动态轻压下技术控制铸坯偏析， 板坯下线后 加罩缓冷 48小吋以上。
[0036] 2) 加热、 轧制工艺
[0037] 采用分段加热方式： 总加热吋间为 270min， 第一加热段温度为 1120°C， 第二加 热段温度为 1250°C， 均热段温度为 1240°C， 第二加热段和均热段总加热吋间为 13 5min， 确保铸坯偏析充分扩散。
[0038] 采用两阶段轧制， 粗轧阶段采用高温大压下工艺， 纵轧道次共 3个道次， 其单 道次压下量分别为 25mm、 55mm和 50mm; 使疏松充分压合， 提高钢板内部质量 和心部性能， 精轧阶段累计压下率为 65%， 终轧温度控制在 810°C， 轧后 ACC快 速冷却， 钢板下线后堆垛缓冷 72小吋。
[0039] 3) 热处理工艺
[0040] 采用亚温淬火 +回火工艺， 本发明实施例钢板 Acl温度为 720°C， Ac3温度为 850 °C， 亚温淬火： 淬火温度 835°C， 保温吋间系数： 1.8min/mm; 回火： 回火温度 ： 660°C, 保温吋间系数： 3.8min/mm。
[0041] 经由上述制造工艺制得的 50mm厚的抗氢致幵裂压力容器钢板具有匹配良好的 综合机械性能和优异的抗氢致幵裂性能， 其机械性能详见表 1， 抗氢致幵裂性能 见表 4， 金相组织照片见图 1。
本发明的实施方式
[0042] 实施例 2
[0043] 本实施例的抗氢致幵裂压力容器钢板的厚度为 50mm， 其化学成分按重量百分 比计为: C: 0.18% , Si: 0.32% , Mn: 1.17% , P: 0.003% , S: 0.0006% , H: 0.00005% , 0： 0.0012% , N: 0.0036% , 余量为 Fe及不可避免的杂质元素， 碳当量 Ceq≤0.41<¾， 计算公式为： Ceq=C+Mn/6+ (Cr+Mo+V) /5+ (Ni+Cu) /15
[0044] 该钢板的制造工艺为如下:
[0045] 1) 冶炼、 连铸
[0046] 采用厚度为 370mm的连铸坯生产， 冶炼原料依次经 KR铁水预处理、 转炉冶炼 、 LF精炼、 RH精炼和板坯连铸工序， 转炉冶炼后进行扒澄处理， 连铸工序采用 低过热度全程氩气保护浇注， 通过动态轻压下技术控制铸坯偏析， 板坯下线后 加罩缓冷 48小吋以上。
[0047] 2) 加热、 轧制工艺
[0048] 采用分段加热方式： 总加热吋间为 285min， 第一加热段温度为 1125°C， 第二加 热段温度为 1255°C， 均热段温度为 1242°C， 第二加热段和均热段总加热吋间为 15 Omin, 确保铸坯偏析充分扩散。
[0049] 采用两阶段轧制， 粗轧阶段采用高温大压下工艺， 纵轧道次共 3个道次， 其单 道次压下量分别为 25mm、 55mm和 55mm; 使疏松充分压合， 提高钢板内部质量 和心部性能， 精轧阶段累计压下率为 66%， 终轧温度控制在 812°C， 轧后 ACC快 速冷却， 钢板下线后堆垛缓冷 72小吋。
[0050] 3) 热处理工艺
[0051] 采用亚温淬火 +回火工艺， 亚温淬火： 淬火温度 842°C， 保温吋间系数： 1.8min/ mm; 回火： 回火温度： 650°C， 保温吋间系数： 4.0min/mm。
[0052] 经由上述制造工艺制得的 50mm厚的抗氢致幵裂压力容器钢板具有匹配良好的 综合机械性能和优异的抗氢致幵裂性能， 其机械性能详见表 2， 抗氢致幵裂性能 见表 4， 金相组织照片见图 2。
[0053]
[0054] 实施例 3
[0055] 本实施例的抗氢致幵裂压力容器钢板的厚度为 50mm， 其化学成分按重量百分 比计为: C: 0.16% , Si: 0.35% , Mn: 1.16% , P: 0.005% , S: 0.0007% , H: 0.00006% , 0： 0.0012% , N: 0.0033% , 余量为 Fe及不可避免的杂质元素， [0056] 该钢板的制造工艺为如下：
[0057] 1) 冶炼、 连铸
[0058] 采用连铸坯生产， 冶炼原料依次经 KR铁水预处理、 转炉冶炼、 LF精炼、 RH精 炼和板坯连铸工序， 转炉冶炼后进行扒澄处理， 连铸工序采用低过热度全程氩 气保护浇注， 通过动态轻压下技术控制铸坯偏析， 板坯下线后加罩缓冷 48小吋 以上。
[0059] 2) 加热、 轧制工艺
[0060] 采用分段加热方式： 总加热吋间为 300min， 第一加热段温度为 1118°C， 第二加 热段温度为 1252°C， 均热段温度为 1241°C， 第二加热段和均热段总加热吋间为 15 Omin, 确保铸坯偏析充分扩散。
[0061] 采用两阶段轧制， 粗轧阶段采用高温大压下工艺， 纵轧道次共 3个道次， 其单 道次压下量分别为 30mm、 55mm和 55mm; 使疏松充分压合， 提高钢板内部质量 和心部性能， 精轧阶段累计压下率为 68%， 终轧温度控制在 802°C， 轧后 ACC快 速冷却， 钢板下线后堆垛缓冷 72小吋。
[0062] 3) 热处理工艺
[0063] 采用亚温淬火 +回火工艺， 亚温淬火： 淬火温度 840°C， 保温吋间系数： 1.8min/ mm; 回火： 回火温度： 645°C， 保温吋间系数： 4.2min/mm。
工业实用性
[0064] 经由上述制造工艺制得的 50mm厚的抗氢致幵裂压力容器钢板具有匹配良好的 综合机械性能和优异的抗氢致幵裂性能， 其机械性能详见表 3， 抗氢致幵裂性能 见表 4， 金相组织照片见图 3。
[0065] 表 1实施例 1所生产的钢板的机械性能
Figure imgf000010_0001
[0066]
[0067] 注： 模拟热成型制度： 920±20°C， l.l-1.2min/mm, 空冷； 模拟焊后热处理： 63 5±14°Cxl8h。 模拟亚温淬火 +模拟回火工艺制度与钢板热处理工艺参数相同。
[0068]
[0069] 表 2实施例 2所生产的钢板的机械性能
Figure imgf000010_0002
[0070]
[0071] 注： 模拟热成型制度： 920±20°C， l.l-1.2min/mm, 空冷； 模拟焊后热处理： 63 5±14°Cxl8h。 模拟亚温淬火 +模拟回火工艺制度与钢板热处理工艺参数相同。
[0072]
[0073] 表 3实施例 3所生产的钢板的机械性能
Figure imgf000011_0001
[0074]
[0075] 注： 模拟热成型制度： 920±20°C， l.l-1.2min/mm, 空冷； 模拟焊后热处理： 63 5±14°Cxl8h。 模拟亚温淬火 +模拟回火工艺制度与钢板热处理工艺参数相同。
[0076]
[0077] 表 4各实施例所生产的钢板的抗氢致幵裂 （HIC) 性能
[]
Figure imgf000012_0001
[0078]
[0079] 本申请各实例钢板晶粒度为 8.5级， 带状组织 0.5级， 见图 1〜图 3。
序列表自由内容
[0080] 在此处键入序列表自由内容描述段落。

Claims

权利要求书
[权利要求 1] 一种抗氢致幵裂压力容器钢板， 其特征在于： 该钢板的化学成分按重 量百分比计为 C: 0.16—0.20% , Si: 0.15—0.40%, Mn: 1.05〜1.20<¾ ， P: <0.008% , S: <0.002%, Nb: <0.01%, V： <0.01% , Ti: <0.0 1% , B: <0.0005% , 余量为 Fe
及不可避免的杂质元素， 碳当量 Ceq≤0.42%， 碳当量计算公式为： Ce q=C+Mn/6+ (Cr+Mo+V) /5+ (Ni+Cu) /15。
[权利要求 2] —种制造如权利要求 1所述的抗氢致幵裂压力容器钢板的方法， 其特 征在于： 工艺步骤如下：
冶炼工艺
采用连铸坯生产方式， 其工艺路线： KR预处理→转炉冶炼—LF精炼 →RH精炼→连铸， 冶炼原料经 KR铁水预处理， 转炉冶炼后扒澄处理 ， 严格控制8≤0.001<¾， P<0.006%, A类、 B类、 C类、 D类和 Ds非金 属夹杂物类单项≤1.0级， 其总和≤3.5级； 连铸采用低过热度全程氩气 保护浇注， 通过动态轻压下技术控制铸坯偏析 B类 1.0级以下， 板坯下 线后加罩缓冷 48小吋以上， 确保钢中的氢充分扩散； 加热、 轧制工艺
采用分段加热方式： 总加热吋间为 225〜300min， 第一加热段温度为 1 050〜1150°C， 第二加热段温度为 1200〜1260°C， 均热段温度为 1170 〜1250°C， 第二加热段和均热段总加热吋间≥120min;
采用两阶段轧制工艺： 粗轧阶段采用"高温大压下"工艺， 纵轧道次中 至少有两道次的单道次压下量≥501^^ 精轧阶段累计压下率≥60%， 终轧温度控制在 780〜820°C， 轧后 ACC快速冷却， 钢板下线后堆垛缓 冷 72小吋以上， 充分扩氢；
3) 热处理工艺
采用亚温淬火 +回火工艺， 亚温淬火： 淬火温度 820〜850°C， 保温吋 间系数： 1.8〜2.0min/mm， 水冷； 回火： 回火温度 640〜670°C， 保温 吋间系数： 3.5〜4.5min/mm。
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