WO2024067480A1 - 抗二氧化碳及微生物腐蚀的低合金钢、板材、焊管及其制造方法 - Google Patents

抗二氧化碳及微生物腐蚀的低合金钢、板材、焊管及其制造方法 Download PDF

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WO2024067480A1
WO2024067480A1 PCT/CN2023/121089 CN2023121089W WO2024067480A1 WO 2024067480 A1 WO2024067480 A1 WO 2024067480A1 CN 2023121089 W CN2023121089 W CN 2023121089W WO 2024067480 A1 WO2024067480 A1 WO 2024067480A1
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alloy steel
low alloy
corrosion
content
welded pipe
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French (fr)
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齐亚猛
张春霞
张忠铧
高展
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to US19/112,711 priority Critical patent/US20260098326A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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Definitions

  • the present disclosure relates to a low alloy steel and a plate and a welded pipe made of the same, and in particular to a corrosion-resistant (especially carbon dioxide and microbial corrosion-resistant) low alloy steel, a plate, a welded pipe and a manufacturing method thereof.
  • Microbial corrosion refers to the phenomenon that the microorganisms' own life activities and their metabolites directly and indirectly accelerate the corrosion process of metal materials. It is widely present in various natural environments, such as soil, seawater, oil field systems, etc., and is a major cause of engineering material failure. Statistics show that microbial corrosion of metal materials accounts for about 20% of the total corrosion of metal materials, causing huge economic losses.
  • Microbial corrosion is usually a synergistic corrosion process of multiple microorganisms.
  • Microorganisms such as sulfate reducing bacteria (SRB), saprophytic bacteria (TGB), and iron oxidizing bacteria (IOB) are the main microbial groups that cause local corrosion of steel materials such as pipes, pipe fittings, and sheets. Among them, SRB has the highest content and the greatest harm among the microbial groups that cause corrosion of steel materials.
  • the Chinese patent document with publication number CN 107177792A and publication date September 19, 2017, entitled "A pipeline steel with resistance to sulfate-reducing bacteria corrosion” discloses a pipeline steel, whose chemical composition includes one or more of C ⁇ 0.10%, Si ⁇ 0.50%, Mn ⁇ 2.0%, 1.5% ⁇ Cu ⁇ 4.0%, Ni ⁇ 0.60%, Mo ⁇ 0.30%, Cr ⁇ 0.30%, Nb ⁇ 0.05%, Ti ⁇ 0.05%, and the rest is Fe and unavoidable impurities.
  • the pipeline steel has excellent resistance to sulfate-reducing bacteria corrosion, it does not have resistance to CO 2 corrosion.
  • the Chinese patent document with publication number CN 107805762A and publication date March 16, 2018, entitled “A low alloy high strength steel with resistance to marine microbial corrosion” discloses a low alloy steel, whose chemical composition includes: C: 0-0.08%, Si: 0-0.40%, Mn: 0-1.8%, Cu: 0.6-4.0%, Ni: 0.6-1.0%, Mo: 0-0.6%, Cr: 0-0.60%, Nb: 0-0.05%, and the rest is Fe and unavoidable impurities.
  • the low alloy high strength steel can significantly reduce Corrosion risk caused by marine Pseudomonas aeruginosa microorganisms. Although this low alloy steel has excellent resistance to Pseudomonas aeruginosa microbial corrosion, it does not have resistance to CO 2 corrosion.
  • one of the purposes of the present disclosure is to provide a low alloy steel having good resistance to carbon dioxide and microbial corrosion, which can be suitable for a service environment where microbial and CO2 corrosion coexist.
  • the present disclosure provides a low alloy steel, wherein the low alloy steel contains the following chemical elements in addition to Fe and unavoidable impurities by mass percentage:
  • the present disclosure further provides a low alloy steel, wherein the chemical element composition of the low alloy steel is as follows, in terms of mass percentage:
  • the rare earth elements include at least La and Ce, and the mass percentages thereof satisfy 0.05% ⁇ (La+Ce) ⁇ 0.55%.
  • the content of Cu is 1.5 to 4.8%, preferably 2.0 to 4.8%, by mass percentage.
  • the content of Cr is 2.0-5.5%, preferably 3.0-5.5%, by mass percentage.
  • the content of Ni is 1.0-3.0%, preferably 1.5-3.0%, by mass percentage.
  • the content of Mo is 1.0-2.5% by mass.
  • the content of V is 0.1-0.2% by mass.
  • REM includes La and Ce, and the contents of La and Ce in mass percentage satisfy the following inequality: 0.05% ⁇ (La+Ce) ⁇ 0.55%, preferably 0.24% ⁇ (La+Ce) ⁇ 0.52%.
  • the inevitable impurities include P and S, and P and S are present in an amount of 1:1 by mass percent.
  • the content in percentage meets the following requirements: P ⁇ 0.015%, S ⁇ 0.007%.
  • the microstructure of the low alloy steel is ferrite and pearlite.
  • the uniform corrosion rate of the low alloy steel is ⁇ 0.015 mm/a, and the pitting corrosion rate is ⁇ 0.033 mm/a.
  • the present disclosure further provides a plate material, which is made of the above-mentioned low alloy steel.
  • the present disclosure also provides a welded pipe, which is made of the above low alloy steel.
  • the present disclosure also provides a method for manufacturing the above-mentioned plate, which comprises the following steps:
  • step (3) the heat treatment temperature is 860-950°C and the insulation time is more than 30 minutes.
  • the heating temperature of the slab is 1150-1280°C, and the final rolling temperature is 850-980°C.
  • the present disclosure also provides a method for manufacturing the above-mentioned welded pipe, which comprises the following steps:
  • step (4) the heat treatment temperature is 860-950°C and the insulation time is more than 30 minutes.
  • the heating temperature of the slab is 1150-1280°C, and the final rolling temperature is 850-980°C.
  • the corrosion resistance test was carried out in an environment where CO 2 , SRB, TGB and IOB coexisted, at a temperature of 35° C., a CO 2 partial pressure of 1.5 MPa, an SRB concentration of 40,000 cells/ml, a TGB concentration of 25,000 cells/ml, an IOB concentration of 30,000 cells/ml, and a test time of 250 h.
  • C is beneficial to improve the strength of steel, but too high C content can easily lead to the precipitation of alloy element carbides at the grain boundaries, reducing the steel's resistance to corrosion. CO 2 and microbial corrosion performance. In addition, from the perspective of weldability, C will also strongly increase the welding crack sensitivity of steel. Therefore, the C content is controlled at 0.02-0.10%.
  • Si is an important deoxidizer in the steelmaking process.
  • Si can also improve high-temperature oxidation resistance and acid resistance.
  • the Si content must be kept above 0.1%, but too much content will reduce the toughness and plasticity of the steel. Therefore, the Si content is limited to 0.1-1.5%.
  • Mn has beneficial effects such as expanding austenite phase, increasing hardenability, and refining grains, etc. However, too much Mn has a significant adverse effect on welding performance and hot working performance, so the Mn content is controlled within 0.10% to 1.80%.
  • the Cr can significantly improve the steel's resistance to localized and uniform corrosion of CO2 .
  • the Cr content is less than 1.0%, excellent CO2 corrosion resistance cannot be guaranteed.
  • the higher the Cr content the better, because the segregation of Cr carbides at the grain boundaries can easily lead to a decrease in the corrosion resistance of the steel.
  • too high a Cr content will affect weldability. Therefore, taking all factors into consideration, the Cr content is designed to be 1.0-5.5%, preferably 2.0-5.5%, and more preferably 3.0-5.5%.
  • Ni can significantly improve the performance of the passivation film and enhance the corrosion resistance of the steel. Ni can also improve the problem of cracking of the steel billet during steelmaking. Therefore, the content of Ni is controlled at 0.3-3.0%, preferably 1.0-3.0%, and more preferably 1.5-3.0%.
  • Cu is a key alloying element in the low alloy steel disclosed herein, and is a necessary condition for ensuring resistance to microbial corrosion.
  • Cu is evenly dispersed in the matrix in the form of a copper-rich phase.
  • copper ions can be continuously dissolved and adsorbed on the steel surface, thereby preventing sulfate-reducing bacteria from adsorbing and growing on the steel surface, thereby playing a bactericidal role.
  • excessive Cu will cause the precipitation of coarse copper-rich phases, affecting impact toughness and hot working properties. Therefore, the Cu content is controlled at 0.3-4.8%, preferably 1.5-4.8%.
  • Mo can improve the strength of steel through carbides and solid solution strengthening, and can also effectively increase the pitting corrosion resistance of steel. Based on this, the content of Mo is controlled at 0.1-2.5%, preferably 1.0-2.5%.
  • V is a typical precipitation strengthening element that can improve the strength of steel.
  • the V content is less than 0.01%, the strengthening effect is not obvious; when the V content exceeds 0.20%, the precipitated phase is large and coarse, affecting the toughness and corrosion resistance of the steel. Based on this, the V content is controlled at 0.01-0.20%, preferably 0.1-0.2%.
  • the content of Al is controlled to be 0.01 to 0.10%.
  • REM can effectively improve the toughness and CO2 corrosion resistance of steel, among which La and Ce can effectively improve the microbial corrosion resistance of steel.
  • the total amount of REM and the content of La and Ce should not be too much, because their excessive content will produce more coarse inclusions, affecting the toughness and corrosion resistance of steel. Based on this, the content of REM is controlled at 0.10-1.0%, among which 0.05% ⁇ [La]+[Ce] ⁇ 0.55%.
  • P is a harmful element that causes a decrease in CO2 corrosion resistance and has an adverse effect on hot working properties. If the P content exceeds 0.015%, the CO2 corrosion resistance cannot meet the requirements. Therefore, the P content is limited to less than 0.015%.
  • S is a harmful element that reduces hot working properties and has an adverse effect on impact toughness. If the S content exceeds 0.007%, the welded pipe cannot be manufactured normally. Therefore, the S content is limited to 0.007% or less, preferably 0.005% or less.
  • the surface passivation film is improved by adding an appropriate amount of Cr element to form Cr(OH) 3 to increase the corrosion product protection ability, thereby improving the CO 2 corrosion resistance of the steel;
  • the microbial corrosion resistance of the steel is improved by adding an appropriate amount of Cu.
  • Cu ions and Cu-rich phases can be released continuously to ensure the long-lasting microbial corrosion resistance of the steel.
  • the pitting resistance of the steel can be effectively increased by adding an appropriate amount of Mo.
  • La and Ce have a toxic effect on SRB, TGB, and IOB microorganisms, and REM has a certain effect on improving CO 2 corrosion resistance. Therefore, the addition of REM containing La and Ce elements can simultaneously enhance CO 2 resistance and microbial corrosion resistance.
  • the low alloy steel resistant to carbon dioxide and microbial corrosion disclosed in the present invention obtains ferrite and pearlite structures through reasonable chemical composition design and specific heat treatment process.
  • the uniform corrosion rate of the low alloy steel is ⁇ 0.015 mm/a, and the pitting corrosion rate is ⁇ 0.033 mm/a, so it has excellent resistance to carbon dioxide and microbial corrosion.
  • the low alloy steel disclosed in the present invention has a simple chemical composition and a low alloy addition amount, so the economic cost is low and has good promotion prospects and application value.
  • Examples A-1 to E-1 are plates made of low alloy steel having the composition shown in Table 1, and Examples A-2 to E-2 are welded pipes made of low alloy steel having the composition shown in Table 1.
  • the heat treatment temperature is 860-950°C and the holding time is more than 30 minutes;
  • the heat treatment temperature is 860-950°C and the holding time is more than 30 minutes;
  • Table 1 lists the mass percentages of various chemical elements in the low alloy steels of Examples A-E.
  • Table 2 lists the specific process parameters of the method for manufacturing the plates of Examples A-1 to E-1.
  • Table 3 lists the specific process parameters of the method for manufacturing the welded pipes of Examples A-2 to E-2.
  • the corrosion test was conducted in an environment where CO 2 , SRB, TGB, and IOB coexisted.
  • the samples taken from each example were immersed in a liquid in a container.
  • the temperature was 35°C
  • the CO 2 partial pressure was 1.5MPa
  • the SRB concentration was 40,000/ml
  • the TGB concentration was 25,000/ml
  • the IOB concentration was 30,000/ml.
  • the test time was 250 hours.
  • the weight of the samples before and after the test was compared to calculate the uniform corrosion rate.
  • the pitting pit was analyzed and the pitting rate was calculated.
  • Table 4 lists the corrosion resistance test results of the plates of Examples A-1 to E-1 and the welded pipes of Examples A-2 to E-2.

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Abstract

本申请公开了一种低合金钢，其中，该低合金钢除含有Fe和不可避免的杂质之外，还以质量百分比计含有如下化学元素：C：0.02～0.1％，Si：0.1～1.5％，Mn：0.10～1.8％，Cr：1.0～5.5％，Ni：0.3～3.0％，Cu：0.3～4.8％，Mo：0.10～2.5％，V：0.01～0.2％，Al：0.01～0.1％，REM：0.1～1.0％。本公开的低合金钢具有良好的抗二氧化碳及微生物腐蚀性能，可适用于微生物和CO2腐蚀共存的服役环境。此外，本申请还公开了由该低合金钢制成的板材和焊管，以及该板材和焊管的制造方法。

Description

抗二氧化碳及微生物腐蚀的低合金钢、板材、焊管及其制造方法 技术领域
本公开涉及一种低合金钢及由其制成的板材和焊管，尤其涉及一种耐腐蚀(特别是耐二氧化碳及微生物腐蚀)的低合金钢、板材、焊管及其制造方法。
背景技术
微生物腐蚀是指由于微生物的自身生命活动及其代谢产物直接和间接地加速金属材料腐蚀过程的现象，其普遍存在于各种自然环境中，如土壤、海水、油田系统等，是引起工程材料失效的一个主要原因。有统计表明，微生物对金属材料的腐蚀占金属材料总腐蚀的20％左右，造成的经济损失巨大。
微生物腐蚀通常是多种微生物的协同腐蚀过程。硫酸盐还原菌(Sulfate Reducing Bacteria，SRB)、腐生菌(TGB)、铁氧化细菌(Iron Oxidizing Bacteria，IOB)等微生物都是引起管道、管件、板料等钢铁材料发生局部腐蚀的主要微生物类群，其中SRB在造成钢铁材料腐蚀的微生物类群中含量最高，危害最大。
另外，很多情况下会存在微生物和CO2腐蚀共存的服役环境。然而，现有技术中的钢种产品的耐腐蚀性往往只能针对CO2腐蚀，或者只能针对微生物腐蚀，而没有同时抗CO2和微生物腐蚀的产品。
例如，针对CO2腐蚀，已有3Cr、13Cr等产品。
公开号为CN 107177792A，公开日为2017年9月19日，名称为“一种具有耐硫酸盐还原菌腐蚀性能的管线钢”的中国专利文献公开了一种管线钢，其化学成分包括：C≤0.10％，Si≤0.50％，Mn≤2.0％，1.5％≤Cu≤4.0％，Ni≤0.60％，Mo＜0.30％，Cr＜0.30％，Nb＜0.05％，Ti＜0.05％中的一种或多种，其余为Fe和不可避免的杂质。虽然该管线钢具备优异耐硫酸盐还原菌腐蚀性能，但不具备抗CO2腐蚀性能。
公开号为CN 107805762A，公开日为2018年3月16日，名称为“一种具有耐海洋微生物腐蚀性能的低合金高强度钢”的中国专利文献公开了一种低合金钢，其化学成分包括：C：0～0.08％，Si：0～0.40％，Mn：0～1.8％，Cu：0.6～4.0％，Ni：0.6～1.0％，Mo：0～0.6％，Cr：0～0.60％，Nb：0～0.05％，其余为Fe和不可避免的杂质。该低合金高强钢可明显降低 海洋铜绿假单胞微生物的腐蚀风险。虽然该低合金钢具备优异耐铜绿假单胞微生物腐蚀性能，但不具备抗CO2腐蚀性能。
发明内容
鉴于本领域的上述不足，期望获得一种钢种，其兼具良好的抗CO2和抗微生物腐蚀性能。
因此，本公开的目的之一在于提供一种低合金钢，其具有良好的抗二氧化碳及微生物腐蚀性能，可适用于微生物和CO2腐蚀共存的服役环境。
为了实现上述目的，本公开提供了一种低合金钢，其中，所述低合金钢除含有Fe和不可避免的杂质之外，还以质量百分比计含有如下化学元素：
C：0.02～0.1％，Si：0.1～1.5％，Mn：0.10～1.8％，Cr：1.0～5.5％，Ni：0.3～3.0％，Cu：0.3～4.8％，Mo：0.10～2.5％，V：0.01～0.2％，Al：0.01～0.1％，REM：0.1～1.0％。
另一方面，本公开还提供了一种低合金钢，其中，以质量百分比计，所述低合金钢的化学元素组成如下：
C：0.02～0.10％，Si：0.1～1.5％，Mn：0.10～1.8％，Cr：1.0～5.5％，Ni：0.3～3.0％，Cu：0.3～4.8％，Mo：0.10～2.5％，V：0.01～0.2％，Al：0.01～0.1％，REM：0.1～1.0％，余量为Fe和不可避免的杂质。
优选地，在本公开的低合金钢中，稀土元素(REM元素)至少包括La和Ce，并且其质量百分含量满足0.05％≤(La+Ce)≤0.55％。
优选地，在本公开的低合金钢中，以质量百分比计，Cu的含量为1.5～4.8％，优选为2.0～4.8％。
优选地，在本公开的低合金钢中，以质量百分比计，Cr的含量为2.0-5.5％，优选为3.0-5.5％。
优选地，在本公开的低合金钢中，以质量百分比计，Ni的含量为1.0-3.0％，优选为1.5-3.0％。
优选地，在本公开的低合金钢中，以质量百分比计，Mo的含量为1.0-2.5％。
优选地，在本公开的低合金钢中，以质量百分比计，V的含量为0.1-0.2％。
优选地，在本公开的低合金钢中，REM包括La和Ce，并且，La和Ce以质量百分比计的含量满足如下不等式：0.05％≤(La+Ce)≤0.55％，优选0.24％≤(La+Ce)≤0.52％。
优选地，在本公开的低合金钢中，不可避免的杂质包括P和S，并且，P和S以质量百 分比计的含量满足如下：P≤0.015％，S≤0.007％。
优选地，低合金钢的微观组织为铁素体和珠光体。
优选地，在存在CO2、SRB、TGB和IOB的环境中，低合金钢的均匀腐蚀速率≤0.015mm/a，点腐蚀速率≤0.033mm/a。
另一方面，本公开还提供了一种板材，其由上述低合金钢制得。
另一方面，本公开还提供了一种焊管，其由上述低合金钢制得。
另一方面，本公开还提供了一种制造上述板材的方法，其包括以下步骤：
(1)冶炼和铸造，制得板坯；
(2)轧制；
(3)热处理；
(4)空冷，
其中，在步骤(3)中，热处理温度为860～950℃，保温时间为30min以上。
优选地，在步骤(2)中，板坯的加热温度为1150～1280℃，终轧温度为850～980℃。
另一方面，本公开还提供了一种制造上述焊管的方法，其包括以下步骤：
(1)冶炼和铸造，制得板坯；
(2)轧制；
(3)焊接成型，制得焊管；
(4)热处理；
(5)空冷，
其中，在步骤(4)中，热处理温度为860～950℃，保温时间为30min以上。
优选地，在步骤(2)中，板坯的加热温度为1150～1280℃，终轧温度为850～980℃。
具体实施方式
下面将结合具体的实施方案对本公开的低合金钢、板材、焊管及其制造方法做进一步的解释和说明，然而该解释和说明并不对本公开的技术方案构成不当限定。
如实施例部分所述地，耐腐蚀试验在CO2、SRB、TGB、IOB共存的环境中进行，温度为35℃，CO2分压为1.5MPa，SRB浓度为40000个/ml，TGB浓度为25000个/ml，IOB浓度为30000个/ml，试验时间为250h。
在本公开的低合金钢中，各化学元素的设计原理如下所述：
C有利于提高钢的强度，但C含量过高容易导致晶界析出合金元素碳化物，降低钢种抗 CO2和微生物腐蚀性能。另外，从可焊性角度考虑，C还会强烈提高钢的焊接裂纹敏感性。因此，将C的含量控制在0.02-0.10％。
Si是炼钢过程中重要的脱氧剂。此外，Si还可以提高高温抗氧化和耐酸性能。为保证钢的脱氧效果，Si含量需保持在0.1％以上，但含量过多会降低钢的韧性和塑性。因此，将Si的含量限定在0.1～1.5％。
Mn具有扩大奥氏体相区、增加淬透性、细化晶粒等有益效果。然而，过多Mn对焊接性能和热加工性能有明显不利影响，因此，将Mn的含量控制在0.10％～1.80％。
Cr能够明显提高钢种抗CO2局部腐蚀和均匀腐蚀能力。当Cr含量小于1.0％时，不能保证优异的耐CO2腐蚀性能。然而，Cr不是越高越好，因为Cr的碳化物在晶界的偏析容易导致钢种抗腐蚀性能下降。另一方面，Cr过高会使可焊性受到影响。因此，综合考虑，将Cr的含量设计为1.0～5.5％，优选为2.0-5.5％，更优选为3.0-5.5％。
Ni可以明显改善钝化膜性能，提升钢种的耐腐蚀作用。Ni还可以改善炼钢时钢坯开裂的问题。因此，将Ni的含量控制在0.3～3.0％，优选为1.0-3.0％，更优选为1.5-3.0％。
Cu是本公开的低合金钢中的关键性合金元素，是保证耐微生物腐蚀性能的必要条件。Cu以富铜相均匀弥散分布在基体中。服役工况环境下，铜离子可以持续溶出并吸附在钢表面，从而阻止硫酸盐还原菌在钢表面的吸附生长，由此起到杀菌作用。但是，过量的Cu会导致粗大的富铜相析出，影响冲击韧性和热加工性能。因此，将Cu含量控制在0.3～4.8％，优选1.5～4.8％。
Mo可通过碳化物及固溶强化来提高钢强度，并且还可有效增加钢的耐点蚀能力。基于此，将Mo的含量控制在0.1～2.5％，优选为1.0-2.5％。
V是典型析出强化元素，可提高钢的强度。当V含量小于0.01％时，强化效果不明显；当V含量超过0.20％时，析出相较多且粗大，影响钢的韧性和耐腐蚀性能。基于此，将V的含量控制在0.01～0.20％，优选为0.1-0.2％。
作为本公开低合金钢的脱氧元素，Al的含量被控制在0.01～0.10％。
REM可以有效提高钢的韧性和耐CO2腐蚀性能，其中La和Ce可有效提升钢的耐微生物腐蚀性能。但REM的总量以及La和Ce的含量不宜过多，因为它们的含量过多会产生较多粗大夹杂物，影响钢的韧性和耐腐蚀性能。基于此，将REM的含量控制在0.10～1.0％，其中0.05％≤[La]+[Ce]≤0.55％。
P是导致抗CO2腐蚀性能下降的有害元素，且会对热加工性能产生不利影响。若P的含量超过0.015％，则CO2抗腐蚀性能无法满足要求。因此，将P的含量限定在0.015％以下。
S是使得热加工性能降低同时对冲击韧性产生不良影响的有害元素。若S的含量超过0.007％，则不能正常制造焊管。因此，将S的含量限定在0.007％以下，优选0.005％以下。
从成分的角度来说，在本公开的低合金钢中，通过添加适量的Cr元素来改善表面钝化膜，以形成Cr(OH)3增加腐蚀产物保护能力，进而提高钢种的耐CO2腐蚀性能；通过添加适量的Cu来提升钢的耐微生物腐蚀性能。在微生物环境中，Cu离子和富Cu相可以源源不断地释放，保证钢材持久的耐微生物腐蚀性能。另外，通过添加适量的Mo可以有效增加钢的耐点蚀能力。此外，La和Ce对SRB、TGB、IOB微生物具有毒杀作用，REM对提升耐CO2腐蚀性能具有一定作用。因此，添加含有La和Ce元素的REM可同时增强耐CO2和微生物腐蚀性能。
从工艺的角度来说，在本公开的板材和焊管的制造方法中，通过使热处理温度在860～950℃之间，可以保证完全奥氏体化。热处理过程中在材料表面会形成Cr(OH)3，提升耐CO2腐蚀性能；同时Cu会以富铜相方式析出，有利于提升耐微生物腐蚀性能。
综上所述，本公开的抗二氧化碳及微生物腐蚀的低合金钢通过合理的化学成分设计，配合特定的热处理工艺，获得铁素体和珠光体组织，同时，该低合金钢在CO2、SRB、TGB、IOB共存的环境中，均匀腐蚀速率≤0.015mm/a，点腐蚀速率≤0.033mm/a，因而具有优异的抗二氧化碳及微生物腐蚀性能。
此外，本公开的低合金钢的化学成分简单，合金添加量低，因此经济成本低廉，具有良好的推广前景和应用价值。
下面结合实施例对本公开作进一步详细的说明。以下实施例仅用于说明本公开而不用于限制本公开的范围。实施例中未注明具体条件的实验方法，系按照本领域已知的常规条件，或按照制造厂商所建议的条件进行操作。
实施例A-E
实施例A-1至E-1是采用表1所示成分的低合金钢制得的板材，实施例A-2至E-2是采用表1所示成分的低合金钢制得的焊管。
实施例A-1至E-1的板材采用以下步骤制得(具体工艺参数参见表2)：
(1)按照表1所示成分配料，进行冶炼和铸造，获得板坯；
(2)轧制：板坯的加热温度为1150～1280℃，终轧温度为850～980℃；
(3)热处理：热处理温度为860～950℃，保温时间为30min以上；
(4)空冷。
实施例A-2至E-2的焊管采用以下步骤制得(具体工艺参数参见表3)：
(1)按照表1所示的成分配料，进行冶炼和铸造，获得板坯；
(2)对板坯进行轧制，获得热轧板，其中板坯的加热温度为1150～1280℃，终轧温度为850～980℃；
(3)将热轧板焊接成型，制得焊管；
(4)热处理：热处理温度为860～950℃，保温时间为30min以上；
(5)空冷。
表1列出了实施例A-E的低合金钢的各化学元素质量百分比。
表1.实施例A-E(wt％，余量为Fe和P、S以外的不可避免的杂质)
表2列出了实施例A-1至E-1的板材的制造方法的具体工艺参数。
表2.
表3列出了实施例A-2至E-2的焊管的制造方法的具体工艺参数。
表3.

对上述各实施例的板材和焊管进行耐腐蚀测试，所得的测试结果列于表4中，具体测试方式如下：
腐蚀试验在CO2、SRB、TGB、IOB共存的环境中进行，将取自各实施例的试样浸入容器中的液体中，温度为35℃，CO2分压为1.5MPa，SRB浓度为40000个/ml，TGB浓度为25000个/ml，IOB浓度为30000个/ml，试验时间为250h，对比试验前后的试样重量，计算得出均匀腐蚀速率。对点蚀坑进行截面分析计算得到点蚀速率。
表4列出了实施例A-1至E-1的板材以及实施例A-2至E-2的焊管的耐腐蚀性能测试结果。
表4.
由表4可看出，各实施例在CO2、SRB、TGB、IOB共存环境中的均匀腐蚀速率均≤0.015mm/a，点腐蚀速率≤0.033mm/a。由此可见，本公开的低合金钢具有优异的抗二氧化碳及微生物腐蚀性能。
虽然通过参照本公开的某些优选实施方式，已经对本公开进行了描述，但本领域的普通技术人员应该明白，以上内容是结合具体的实施方式对本公开所作的进一步详细说明，不能认定本公开的具体实施只局限于这些说明。本领域技术人员可以在形式上和细节上对其作各种改变，包括做出若干简单推演或替换，而不偏离本公开的精神和范围。

Claims (13)

  1. 一种低合金钢，其中，所述低合金钢除含有Fe和不可避免的杂质之外，还以质量百分比计含有如下化学元素：
    C：0.02～0.1％，Si：0.1～1.5％，Mn：0.10～1.8％，Cr：1.0～5.5％，Ni：0.3～3.0％，Cu：0.3～4.8％，Mo：0.10～2.5％，V：0.01～0.2％，Al：0.01～0.1％，REM：0.1～1.0％。
  2. 如权利要求1所述的低合金钢，其中，以质量百分比计，所述低合金钢的化学元素组成如下：
    C：0.02～0.1％，Si：0.1～1.5％，Mn：0.10～1.8％，Cr：1.0～5.5％，Ni：0.3～3.0％，Cu：0.3～4.8％，Mo：0.10～2.5％，V：0.01～0.2％，Al：0.01～0.1％，REM：0.1～1.0％，余量为Fe和不可避免的杂质。
  3. 如权利要求1或2所述的低合金钢，其中，以质量百分比计，所述低合金钢满足如下条件中的至少一个：Cu的含量为1.5～4.8％，优选为2.0～4.8％；Cr的含量为2.0-5.5％，优选为3.0-5.5％；Ni的含量为1.0-3.0％，优选为1.5-3.0％；Mo的含量为1.0-2.5％；和/或V的含量为0.1-0.2％。
  4. 如权利要求1或2所述的低合金钢，其中，REM包括La和Ce，并且，La和Ce以质量百分比计的含量满足如下不等式：0.05％≤(La+Ce)≤0.55％，优选0.24％≤(La+Ce)≤0.52％。
  5. 如权利要求1或2所述的低合金钢，其中，所述不可避免的杂质包括P和S，并且，P和S以质量百分比计的含量满足如下：P≤0.015％，S≤0.007％。
  6. 如权利要求1或2所述的低合金钢，其中，所述低合金钢的微观组织为铁素体和珠光体。
  7. 如权利要求1或2所述的低合金钢，其中，在存在CO2、SRB、TGB和IOB的环境中，所述低合金钢的均匀腐蚀速率≤0.015mm/a，点腐蚀速率≤0.033mm/a。
  8. 一种板材，其由权利要求1至6中任一项所述的低合金钢制得。
  9. 一种焊管，其由权利要求1至6中任一项所述的低合金钢制得。
  10. 一种制造权利要求8所述的板材的方法，其中，所述方法包括以下步骤：
    (1)冶炼和铸造，制得板坯；
    (2)轧制；
    (3)热处理；
    (4)空冷，
    其中，在步骤(3)中，热处理温度为860～950℃，保温时间为30min以上。
  11. 如权利要求10所述的方法，其中，在步骤(2)中，所述板坯的加热温度为1150～1280℃，终轧温度为850～980℃。
  12. 一种制造权利要求9所述的焊管的方法，其中，所述方法包括以下步骤：
    (1)冶炼和铸造，制得板坯；
    (2)轧制；
    (3)焊接成型，制得焊管；
    (4)热处理；
    (5)空冷，
    其中，在步骤(4)中，热处理温度为860～950℃，保温时间为30min以上。
  13. 如权利要求12所述的方法，其中，在步骤(2)中，所述板坯的加热温度为1150～1280℃，终轧温度为850～980℃。
PCT/CN2023/121089 2022-09-28 2023-09-25 抗二氧化碳及微生物腐蚀的低合金钢、板材、焊管及其制造方法 Ceased WO2024067480A1 (zh)

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