CN107619994B - 一种抗co2/h2s及硫酸盐还原菌腐蚀的无缝管线管及其制造方法 - Google Patents
一种抗co2/h2s及硫酸盐还原菌腐蚀的无缝管线管及其制造方法 Download PDFInfo
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Abstract
本发明提供了一种耐CO2‑H2S‑SRB腐蚀性能优异的无缝管线管。该管线管以质量分数计含有C:0.03~0.10%,Si:0.1~0.5%,Mn:0.10%~1.50%,P:0.02%以下,S:0.005%以下,Cr:1.0~4.0%,Ni:0.1~1.5%,Cu:0.15~2.0%,Mo:0.05~0.4%,Ti:0.01~0.05%,RE:0.05~0.1%,余量为Fe。该管线管经冶炼、轧制成管坯、穿孔轧制成管后,通过制成的钢管加热到920~1000℃后,根据钢管壁厚,保温0.3~1h,再进行快速冷却+回火热处理。该无缝管线管可用于油气流体输送等领域。
Description
技术领域
本发明涉及一种油气田输送油气所使用的无缝管线管。特别涉及一种适合含有二氧化碳(CO2)、硫化氢(H2S)和硫酸盐还原菌(SRB)环境下应用,具有优良的抗均匀腐蚀,特别是抗点腐蚀性能优异的无缝管线管及制造方法。
背景技术
随着油气田开采逐渐深入,开采工况条件日益苛刻,采出的油气往往伴随 CO2和H2S腐蚀性气体。集输管线管主要用来连接油气井和油气综合处理装置之间的管道,输送的都是未经过脱水、脱盐和脱硫等预处理的油气,因而集输管线管的服役工况比较苛刻。近几年国内油气田由于CO2-H2S-SRB共存环境导致的集输管线管破漏事故频发,给油气田带来很大的经济损失和环保压力。目前,单纯抗CO2/H2S腐蚀的抗腐蚀无缝管线管并不能有效解决CO2-H2S-SRB共存环境所导致的穿孔问题,因此,油气田行业迫切希望能获得一种抗CO2-H2S-SRB腐蚀的无缝管线管。
公开日为1996年10月15日,公开号为JP8269623,名称为“一种具有优良抗酸耐腐蚀性管线管”的日本专利文献公开了一种管线管,其化学元素组成为:C≤0.06%,Si0.01~0.50%,Mn 0.1~2.0%,P≤0.01%,S≤0.003%,Cr 0.25~1.0%,Al 0.01~0.10%,Ca≤0.006%,Pcm(%)≤0.18%。该管线管属于低Cr 抗CO2/H2S腐蚀管线管,然而只有0.25~1.0%Cr对抗点蚀性能贡献有限,而且不具有抗CO2-H2S-SRB共存环境均匀腐蚀和局部腐蚀的能力。
公开日为2012年6月20日,公开号为CN101921964B,名称为“具有抗HIC 性能的X70QS无缝管线管”的中国专利文献公开了一种无缝管线管,其化学成分质量百分含量为:C0.06~0.14%,Si 0.20~0.45%,Mn 1.00~1.30%,P≤ 0.015%,S≤0.003%,Cr 0.05~0.30%,Mo 0.05~0.30%,Al 0.015~0.060%, N 0.003~0.010%,Nb 0.030~0.50%,V0.05~0.09%,Ni、Cu为钢中残余元素,限制其含量Ni≤0.10%,Cu≤0.20%,余量为Fe和杂质。该管线管具有高强度、优异冲击性能和良好的抗HIC性能。然而并不具备优异的抗CO2-SRB腐蚀性能。
公开日为2016年3月30日,公开号为CN103147006B,名称为“一种抗腐蚀无缝集输管线管及其制造方法”的中国专利文献公开了一种集输管线管,其化学元素质量百分含量为:C 0.04~0.10%,Si 0.1~0.35%,Mn 0.3~0.8%,Cr 0.55~1.25%,W 0.06~0.55%,Al 0.01~0.05%,Ca 0.0005~0.006%,Cu≤0.2%, Ni≤0.2%,V≤0.05%,Ti≤0.03%,Nb≤0.05%,其余为Fe和其他不可避免的杂质。该集输管线管具备较高的强度,优良的焊接性能,良好的冲击性能等综合力学性能,且具有优质的抗CO2/H2S腐蚀性能。但不具备抗CO2-H2S-SRB共存环境腐蚀性能。
根据本发明研究,通过合理的合金元素搭配,并辅以适当的热处理条件,可以得到具有强度高、耐CO2-H2S-SRB腐蚀性能优异的无缝管线管。
发明内容
针对上述技术问题,本发明的目的在于提供一种高强度、耐CO2-H2S-SRB腐蚀性能优异的无缝管线管及其制造方法。
经过对材料成分、组织及性能的关系研究,本发明发现CO2-H2S-SRB腐蚀中钢表面钝化膜的性能是很关键的,Cr、Ni和Cu的添加会改善钝化膜性能。本发明是基于以上发现完成的,其主要内容是包含以下内容的管线管:
该管线管以质量分数计含有C:0.03~0.10%,Si:0.1~0.5%,Mn:0.10%~1.50%,P:0.02%以下,S:0.005%以下,Cr:1.0~4.0%,Ni:0.1~1.5%,Cu: 0.15~2.0%,Mo:0.05~0.4%,Ti:0.01~0.05%,RE:0.05~0.1%,余量为Fe。
该管线管经冶炼、轧制成管坯、穿孔轧制成管后,通过淬火+回火(回火温度500-700℃)后,检验合格后即可作为合格管线管使用。
以下对各项内容进行详细说明:
1)合金构成(其中含量%均为质量分数)
C:0.03~0.10%
C有利于提高钢的强度,但C含量过高易于晶界析出合金元素碳化物,降低钢种抗腐蚀性能。另外,C会强烈提高钢的焊接裂纹敏感性。因此必须限制C在0.03~0.10%;
Si:0.1%~0.5%
Di是炼钢时有效的脱氧剂。为提高钢强度和保证脱氧效果,其含量需保持在0.1%以上;含量超过0.5%时,会显著增加钢的冷脆倾向,因此应限制Si含量在0.5%以下;
Mn:0.10%~1.50%
Mn具有扩大奥氏体相区,增加淬透性,细化晶粒等有益效果。过多Mn对焊接性能和热加工性能有明显影响,根据本发明研究,Mn含量控制在 0.10%~1.50%较为适宜;
S:0.005%以下
S是钢中的有害元素,其存在对于钢的耐腐蚀性、热加工性、韧性等都有不利影响,因此需要限制S含量在0.005%以下,以0.003%以下为更佳;
P:0.02%以下
P是钢中的有害元素,其存在对于钢的耐腐蚀性、韧性等都有不利影响,因此需要限制P含量在0.02%以下,以0.012%以下为更佳;
Cr:1.0~4.0%
Cr的添加能够大幅提高钢种抗局部腐蚀和均匀腐蚀能力,但是在本技术方案中Cr的含量并不是越高越好,Cr含量过高会导致钢种焊接性能下降,同时Cr的碳化物在晶界的偏析容易导致钢种抗硫性能下降,因此,将Cr 的含量设计为1.0~4.0%。
Ni:0.1~1.5%
Ni可以明显改善钝化膜性能,提升钢种的耐腐蚀作用,根据本发明研究, Ni含量控制在0.1%~1.5%较为适宜;
Cu:0.15~2.0%
Cu能改善钢的抗大气腐蚀及微生物腐蚀性能,但过量Cu会使得热加工时易产生裂纹,故需要限制Cu在2%以下;
Mo:0.05~0.4%
Mo会有效增加钢耐点蚀能力,同时,同时Mo有较好的固溶强化效果,有利于提升钢的性能。根据本发明研究,Ni含量控制在0.05~0.4%较为适宜;
Ti:0.01~0.05%
Ti能够有效细化晶粒,并且还可以改善焊接性能,根据本发明研究,Ni 含量控制在0.01~0.05%;
Re:0.05~0.1%
RE:稀土元素的添加能够有效提高钢种的韧性,当稀土元素含量超过0.1%时会降低钢种的焊接性能,因此将RE含量限定在0.05%~0.10%。
剩余为Fe。
2)制造工艺
本发明中所述管线管的制造工艺流程如下:
(1)将冶炼后的钢水浇铸成铸锭,并锻造(或轧制)成管坯;
(2)将管坯加热到1150~1280℃,根据管坯尺寸,保持1~4小时后,经穿孔、连轧、张力减径(定径)成荒管;
(3)制成的荒管加热到920~1000℃后,根据荒管壁厚,保温0.3~1h,再进行快速冷却(水冷或者油冷处理)+回火(回火温度500℃~700℃,以在保证强度的前提下,尽可能消除内应力,获得足够的韧性)的热处理,性能检验合格后即可作为相应的产品出厂;制得无缝管。
本发明较其他管线管而言,具有以下优点:
1)本发明中所述管线管根据热处理工艺可获得300MPa~500MPa的屈服强度,同时优良的韧性(0℃全尺寸冲击功≥50J);
2)本发明中所述管线管具备优异的抗CO2-H2S-SRB腐蚀性能。在38℃, CO2分压为0.1MPa,H2S分压为0.1MPa,CO2、H2S、SRB共存环境下进行腐蚀试验,试验时间为168h,均匀腐蚀速率小于0.13mm/a,点腐蚀速率小于0.9mm/a。
综上所述,本发明能提供一种耐CO2-H2S-SRB腐蚀性能优异的无缝管线管,可用于油气流体输送等领域。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例成分列表见表1所示
表1实施例成分(wt/%)
利用具有表1中成分的合金制成了规格为219*14.5的管线管,具体流程如下:
1.将具有以上成分的合金浇铸成锭,并将铸锭锻造成φ300mm的圆管坯;
2.将管坯加热到1250℃保持了3小时后,经穿孔、热轧、定径等一般热轧管线管生产工序,制成荒管;
3.将制成的荒管加热到920~1000℃并保持40分钟后,采用不同冷却工艺进行淬火,随后对各钢种进行了温度500~ 700℃,保持一个小时的回火。各管线管的热处理工艺、性能及耐腐蚀性能情况如表2所示。
表2实施例组织、力学性能、腐蚀性能情况
表2中的各项数据具体测定情况:
屈服强度数据是将制成的管线管加工成API弧形试样,按API标准检验后取平均数得出;
全尺寸夏比V型冲击吸收功数据是在制成的钢管上取截面积为10*10*55全尺寸V型冲击试样,按GB/T229标准检验后取平均数得出;
腐蚀试验在CO2、H2S、SRB共存环境进行,将试样浸入容器中液体,温度为38℃,CO2分压为0.1MPa,H2S分压为0.1MPa,试验时间为168h,对比试验前后的试样重量,计算得出均匀腐蚀速率。对点蚀坑进行了截面分析计算得到点蚀速率。
Claims (10)
1.一种抗CO2、H2S及硫酸盐还原菌腐蚀的无缝管,其特征在于:该无缝管以质量分数计含有C:0.03~0.10%,Si:0.1~0.5%,Mn:0.10%~1.50%,P:0.02%以下,S:0.005%以下,Cr:1.0~4.0%,Ni:0.6~1.5%,Cu:0.8~2.0%,Mo:0.05~0.4%,Ti:0.01~0.05%,Re:0.05~0.1%,余量为Fe。
2.根据权利要求1所述的无缝管,其特征在于:S含量为0.003%以下。
3.根据权利要求1所述的无缝管,其特征在于:P含量为0.012%以下。
4.一种制备无缝管方法,所述的方法包括如下步骤:
1)将冶炼后的具有权利要求1-3任一项所述的无缝管成份的钢水浇铸成铸锭,并锻造或轧制成管坯;
2)将管坯加热到1150~1280℃,根据管坯尺寸,保持1~4小时后,经穿孔、连轧、张力减径或定径成荒管;
3)制成的钢管加热到920~1000℃后,根据钢管壁厚,保温0.3~1h,再进行快速冷却和回火热处理,得到无缝管。
5.根据权利要求4所述的方法,其特征在于:所述的快速冷却为水冷或者油冷处理。
6.根据权利要求4所述的方法,其特征在于:回火温度为500℃~700℃。
7.根据权利要求4所述的方法,其特征在于:无缝管的屈服强度300MPa~500MPa。
8.根据权利要求4所述的方法,其特征在于:韧性为0℃全尺寸冲击功≥50J。
9.根据权利要求4所述的方法,其特征在于:在38℃,CO2分压为0.1MPa,H2S分压为0.1MPa,CO2、H2S、SRB共存环境下进行腐蚀试验,试验时间为168h,均匀腐蚀速率小于0.13mm/a,点腐蚀速率小于0.9mm/a。
10.权利要求1-3任一项所述的无缝管的用途,用于油气流体输送领域。
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