CN109112404B - A kind of microbial corrosion resistant pipeline steel - Google Patents
A kind of microbial corrosion resistant pipeline steel Download PDFInfo
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- 239000010959 steel Substances 0.000 title claims abstract description 65
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- 238000005260 corrosion Methods 0.000 title claims abstract description 36
- 230000000813 microbial effect Effects 0.000 title claims abstract description 33
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- 238000009749 continuous casting Methods 0.000 claims description 2
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- 238000005242 forging Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
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- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
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Abstract
本发明的目的在于满足现有管线钢力学性能的前提下，提供一种具有耐微生物腐蚀性能的管线钢，以实现从材料自身角度降低发生微生物腐蚀的风险。按重量百分比计，该钢的化学成分如下：C：≤0.1％；Si：≤0.6％；Mn：≤2.0％；Ga：0.1‑1.2％；S≤0.02；P≤0.03％；余量为Fe及不可避免的杂质。本发明管线钢中添加了Ga元素，在改善管线钢力学性能的基础上还使得该钢具有优异的耐微生物腐蚀性能。
The purpose of the present invention is to provide a pipeline steel with microbial corrosion resistance under the premise of satisfying the mechanical properties of the existing pipeline steel, so as to reduce the risk of microbial corrosion from the perspective of the material itself. By weight percentage, the chemical composition of the steel is as follows: C: ≤ 0.1%; Si: ≤ 0.6%; Mn: ≤ 2.0%; Ga: 0.1‑1.2%; S ≤ 0.02; P ≤ 0.03%; the balance is Fe and inevitable impurities. Ga element is added to the pipeline steel of the present invention, and on the basis of improving the mechanical properties of the pipeline steel, the steel has excellent resistance to microbial corrosion.
Description
技术领域technical field
本发明属于管线钢技术领域，具体涉及一种具有耐微生物腐蚀性能的管线钢。本发明的管线钢能够降低发生微生物腐蚀的风险，可应用于石油、天然气集输和输送用管线钢的生产。The invention belongs to the technical field of pipeline steel, in particular to a pipeline steel with microbial corrosion resistance. The pipeline steel of the invention can reduce the risk of microbial corrosion, and can be applied to the production of pipeline steel for oil and natural gas gathering and transportation.
背景技术Background technique
微生物腐蚀是引起埋地管线腐蚀的一个重要原因。据统计，管线腐蚀的15-30％都与微生物腐蚀相关。随着微生物腐蚀导致的管线失效案例的增加，微生物对油气管道造成的腐蚀问题已引起国内外的高度重视。微生物腐蚀造成的经济损失巨大，而且防治困难。目前，国内对管线的微生物腐蚀防护还未引起重视，而已经服役或现有的管线钢无论是在化学成分上，还是在生产工艺上，均没有考虑到材料自身具有耐微生物腐蚀的性能。中国发明专利(申请号：201510418577.9)提供了一种具有耐微生物腐蚀性能的管线钢，该钢是通过添加适量具有广谱抗菌功能的Cu元素来起到耐微生物腐蚀性能。Microbial corrosion is an important cause of buried pipeline corrosion. According to statistics, 15-30% of pipeline corrosion is related to microbial corrosion. With the increase of pipeline failure cases caused by microbial corrosion, the corrosion of oil and gas pipelines caused by microorganisms has attracted great attention at home and abroad. The economic loss caused by microbial corrosion is huge, and the prevention and control is difficult. At present, domestic attention has not been paid to the microbial corrosion protection of pipelines, and the existing or existing pipeline steels have not taken into account the microbial corrosion resistance of the materials themselves in terms of chemical composition or production process. The Chinese invention patent (application number: 201510418577.9) provides a pipeline steel with microbial corrosion resistance, which is achieved by adding an appropriate amount of Cu element with broad-spectrum antibacterial function to achieve microbial corrosion resistance.
本发明在传统管线钢成分的基础上，添加适量Ga元素，以起到耐微生物腐蚀性能，与含Cu耐微生物腐蚀管线钢有本质的不同。这种新型管线钢有望成为兼具高强韧性及耐微生物腐蚀性能于一体的理想的石油、天然气集输和输送用材料，具有重要的工程应用价值。On the basis of the composition of traditional pipeline steel, the present invention adds an appropriate amount of Ga element to achieve microbial corrosion resistance, which is essentially different from the Cu-containing microbial corrosion resistance pipeline steel. This new type of pipeline steel is expected to become an ideal oil and natural gas gathering and transportation material with high strength, toughness and microbial corrosion resistance, and has important engineering application value.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于满足现有管线钢力学性能的前提下，提供一种具有耐微生物腐蚀性能的管线钢，以实现从材料自身角度降低发生微生物腐蚀的风险。The purpose of the present invention is to provide a pipeline steel with microbial corrosion resistance under the premise of satisfying the mechanical properties of the existing pipeline steel, so as to reduce the risk of microbial corrosion from the perspective of the material itself.
本发明的技术方案是：The technical scheme of the present invention is:
一种耐微生物腐蚀管线钢，按重量百分比计，该钢的化学成分如下：A microbial corrosion-resistant pipeline steel, the chemical composition of the steel is as follows:
C：≤0.1％；Si：≤0.6％；Mn：≤2.0％；Ga：0.1-1.2％；S≤0.02；P≤0.03％；余量为Fe及不可避免的杂质。C: ≤ 0.1%; Si: ≤ 0.6%; Mn: ≤ 2.0%; Ga: 0.1-1.2%; S ≤ 0.02; P ≤ 0.03%; the balance is Fe and inevitable impurities.
优选的化学成分如下：The preferred chemical compositions are as follows:
C：0.03～0.06％；Si：0.1～0.5％；Mn：0.5～1.8％；Ga：0.2-0.6％；S≤0.015；P≤0.025％；余量为Fe及不可避免的杂质。C: 0.03-0.06%; Si: 0.1-0.5%; Mn: 0.5-1.8%; Ga: 0.2-0.6%; S≤0.015; P≤0.025%; the balance is Fe and inevitable impurities.
所述耐微生物腐蚀管线钢化学成分还含有至少一种或一种以上的Nb、V、Ti、Al、B、RE(稀土)，每一种的重量百分比≤0.1％。The chemical composition of the microbial corrosion-resistant pipeline steel also contains at least one or more of Nb, V, Ti, Al, B, RE (rare earth), and the weight percentage of each is ≤0.1%.
所述耐微生物腐蚀管线钢化学成分还含有至少一种或一种以上的Cr、Ni、Mo、Cu，每一种的重量百分比≤0.5％。The chemical composition of the microbial corrosion-resistant pipeline steel further contains at least one or more of Cr, Ni, Mo, and Cu, and the weight percentage of each of them is ≤0.5%.
在本发明所述耐微生物腐蚀管线钢的成分设计中，镓(Ga)是钢中最重要的合金化元素。Ga是铁素体形成元素，微量Ga在低碳钢中通常以置换式固溶体存在于铁素体中，它不存在于氧化物、氮化物及硫化物等夹杂中，也不形成碳氮化物。同时，微量Ga对低碳钢具有强化效应，而且它能在一定程度上细化钢的组织和阻碍磷(P)向晶界偏聚，从而明显提高钢的低温冲击韧性。另外，Ga还可增加钢中的点缺陷，起到氢陷阱作用，使得低碳钢的氢致脆性的敏感性降低。Ga原子还可在晶界区富集，减少了原子半径较Ga大的砷、锑、铋、锡等有害元素在晶界区落位，有净化晶界的作用，起到改善钢的韧性效果。总之，镓在钢中是一种有益元素。本发明中，Ga能够抑制细菌的正常增殖活动。In the composition design of the microbial corrosion-resistant pipeline steel according to the present invention, gallium (Ga) is the most important alloying element in the steel. Ga is a ferrite forming element, and a trace amount of Ga usually exists in ferrite as a substitutional solid solution in low carbon steel. It does not exist in inclusions such as oxides, nitrides and sulfides, and does not form carbonitrides. At the same time, a small amount of Ga has a strengthening effect on low-carbon steel, and it can refine the structure of the steel to a certain extent and hinder the segregation of phosphorus (P) to the grain boundary, thereby significantly improving the low-temperature impact toughness of the steel. In addition, Ga can also increase point defects in the steel and act as a hydrogen trap, which reduces the sensitivity of the hydrogen-induced embrittlement of low-carbon steels. Ga atoms can also be enriched in the grain boundary area, which reduces the placement of harmful elements such as arsenic, antimony, bismuth, and tin with a larger atomic radius than Ga in the grain boundary area, which has the effect of purifying the grain boundary and improving the toughness of the steel. . In conclusion, gallium is a beneficial element in steel. In the present invention, Ga can inhibit the normal proliferation activity of bacteria.
本发明中添加的Ga含量为0.1-1.2％，微量的Ga在管线钢中不易析出富Ga相，当与服役环境接触时，就不能析出足够浓度的三价Ga离子，抑制细菌的增殖不明显。当Ga含量相对过高时，过多的富Ga相会导致管线钢热加工性能的下降，影响其实际生产。The content of Ga added in the present invention is 0.1-1.2%, and a trace amount of Ga is not easy to precipitate a Ga-rich phase in the pipeline steel. When it is in contact with the service environment, trivalent Ga ions of sufficient concentration cannot be precipitated, and the inhibition of bacterial proliferation is not obvious. . When the Ga content is relatively too high, the excessive Ga-rich phase will lead to the decline of the hot workability of pipeline steel and affect its actual production.
本发明还提供了上述具有耐微生物腐蚀管线钢的制备方法，按照上述化学成分的管线钢，可采用真空感应冶炼+锻造+控制轧制和控制冷却的实验室方式获得，也可采用高炉+转炉+连铸+控制轧制和控制冷却的工业化生产方式获得。The present invention also provides a method for preparing the above-mentioned pipeline steel with resistance to microbial corrosion. The pipeline steel according to the above-mentioned chemical composition can be obtained by a laboratory method of vacuum induction smelting + forging + controlled rolling and controlled cooling, or a blast furnace + converter +Continuous casting+Controlled rolling and controlled cooling are obtained by industrialized production methods.
按照以上成分和方式获得的管线钢能够明显降低发生微生物腐蚀的风险。The pipeline steel obtained according to the above composition and method can significantly reduce the risk of microbial corrosion.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明所述管线钢中添加适量的Ga元素，在改善管线钢力学性能的基础上还使得该钢具有优异的耐微生物腐蚀性能。1. Adding an appropriate amount of Ga element to the pipeline steel of the present invention improves the mechanical properties of the pipeline steel and also makes the steel have excellent resistance to microbial corrosion.
2、本发明所述耐微生物腐蚀管线钢能够从材料自身角度降低管线钢发生微生物腐蚀的风险。2. The microbial corrosion-resistant pipeline steel of the present invention can reduce the risk of microbial corrosion of the pipeline steel from the perspective of the material itself.
附图说明Description of drawings
图1为实施例2中管线钢杀灭大肠杆菌的效果照片：图中，(a)对照管线钢(对比例1)；(b)发明管线钢(实施例2)。Fig. 1 is a photo of the effect of pipeline steel in killing Escherichia coli in Example 2: in the figure, (a) control pipeline steel (Comparative Example 1); (b) invented pipeline steel (Example 2).
具体实施方式Detailed ways
将如表1所述的通过真空感应冶炼炉冶炼而得到的具有不同成分的管线钢经过锻造、热机械控制轧制和控制冷却工艺(TMCP)得到管线钢板材，然后进行抗菌实验和力学性能测试。Pipeline steels with different compositions obtained by smelting in a vacuum induction smelting furnace as described in Table 1 were forged, thermomechanically controlled rolling and controlled cooling process (TMCP) to obtain pipeline steel sheets, and then antibacterial experiments and mechanical property tests were carried out. .
抗菌实验按照“JIS Z2801-2000《抗菌加工制品－抗菌性试验方法和抗菌效果》、GB/T2591-2003《抗菌塑料抗菌性能实验方法和抗菌效果》”等标准规定，进行了常见的大肠杆菌和金黄色葡萄球菌两种细菌的抗菌性能检测。Antibacterial experiments were carried out in accordance with the provisions of "JIS Z2801-2000 "Antibacterial Processed Products - Antibacterial Test Methods and Antibacterial Effects", GB/T2591-2003 "Antibacterial Plastic Antibacterial Performance Test Methods and Antibacterial Effects" and other standards, common Escherichia coli and antibacterial effects were carried out. Detection of antibacterial properties of two bacteria Staphylococcus aureus.
对实施例和对比例按照下述公式计算管线钢(含Ga)和对照样品(不含Ga管线钢)对细菌作用后的杀菌率：Calculate the sterilization rate of pipeline steel (containing Ga) and control sample (without Ga pipeline steel) to bacteria according to the following formula for Examples and Comparative Examples:
杀菌率(％)＝[(对照样品活菌数-管线钢活菌数)/对照样品活菌数]×100％。Sterilization rate (%)=[(the number of viable bacteria in the control sample-the number of viable bacteria in the pipeline steel)/the number of viable bacteria in the control sample]×100%.
其中，对照样品活菌数是指在对照样品(不含Ga管线钢)上进行细菌培养后的活菌数，管线钢活菌数是指在本发明管线钢(含Ga)上进行细菌培养后的活菌数。Wherein, the number of viable bacteria in the control sample refers to the number of viable bacteria after culturing bacteria on the control sample (without Ga), and the number of viable bacteria in the pipeline steel refers to the number of bacteria after culturing on the pipeline steel (containing Ga) of the present invention. of viable bacteria.
表1实施例和对比例管线钢成分表(重量百分比，％)Table 1 Example and comparative example pipeline steel composition table (weight percentage, %)
表2实施例和对比例的杀菌率及力学性能The sterilization rate and mechanical properties of table 2 embodiment and comparative example
*冲击试样为全尺寸：10mm×10mm×55mm，测试温度为-20℃*The impact sample is full size: 10mm×10mm×55mm, the test temperature is -20℃
从表2中数据可以看出，与对比例1管线钢相比，本发明所述管线钢具有优异的抗菌作用，当钢中的Ga含量低于0.1％时(对比例2)，抗菌性能不佳，当Ga含量达到0.6％时，抗菌性能便达到99％以上，而且强韧性较好；当Ga含量超过0.6％时，抗菌性能仍然在99％以上，但韧性有小幅下降。从表中数据可以看到，相似化学成分钢中，添加Ga的钢甚至具有更加优良的力学性能。As can be seen from the data in Table 2, compared with the pipeline steel of Comparative Example 1, the pipeline steel of the present invention has excellent antibacterial effect. When the Ga content in the steel is lower than 0.1% (Comparative Example 2), the antibacterial performance is not good. When the Ga content reaches 0.6%, the antibacterial performance reaches more than 99%, and the toughness is good; when the Ga content exceeds 0.6%, the antibacterial performance is still above 99%, but the toughness decreases slightly. As can be seen from the data in the table, among steels with similar chemical composition, the steels with Ga addition even have better mechanical properties.
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with the art to understand the content of the present invention and implement accordingly, and cannot limit the protection scope of the present invention by this. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.
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