Article(id=1156264258183750303, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156264148657886112, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2308582, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1698854400000, receivedDateStr=2023-11-02, revisedDate=1729094400000, revisedDateStr=2024-10-17, acceptedDate=null, acceptedDateStr=null, onlineDate=1753604481501, onlineDateStr=2025-07-27, pubDate=1740672000000, pubDateStr=2025-02-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753604481501, onlineIssueDateStr=2025-07-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753604481501, creator=13701087609, updateTime=1753604481501, updator=13701087609, issue=Issue{id=1156264148657886112, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='6', pageStart='2193', pageEnd='2636', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1753604455388, creator=13701087609, updateTime=1753771257443, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1156963767234945803, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156264148657886112, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1156963767234945804, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156264148657886112, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=2301, endPage=2310, ext={EN=ArticleExt(id=1156264258615763617, articleId=1156264258183750303, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Corrosion Failure Analysis of CO2 Flooding Injection String, columnId=1156264152168518571, journalTitle=Science Technology and Engineering, columnName=Papers·Mining and Metallurgical Engineering, runingTitle=null, highlight=null, articleAbstract=

CO2 flooding is an important part of the CO2 geological utilization process in CCUS(carbon capture, utilization and storage). The CO2 flooding and storage project carried out in the Yanchang Oilfield has achieved good results in increasing production and storing CO2. But the reasons of pipe string corrosion failure are still unclear during CO2 injection. SEM(scanning electron microscopy), 3D confocal microscopy, EDS(energy dispersive spectrometer) and XRD(X-ray diffraction spectroscopy) were used to characterize the corrosion morphology of the gas injection pipe string in the CO2 flooding and storage demonstration area of Wuqi Oilfield. The pipe string corrosion products are analyzed to clarify the reasons for pipe string failure caused by CO2 corrosion. The results show that local corrosion dominated by CO2 corrosion causes corrosion failure of the pipe string. Corrosion products include FeCO3, high-priced oxides of Fe and a small amount of FeS. Continuous injection of low-temperature CO2 cannot cause corrosion. However, the increase in wellbore temperature and the return of formation water caused by stopping CO2 injection can create conditions for CO2/H2S corrosion in the pipe string. In addition, pipe string corrosion is accelerated when gas injection wells are converted into water injection wells. It is recommended to strengthen the sterilization and anti-corrosion measures for the pipe string during the period of stopping CO2 injection and switching to water injection.

, correspAuthors=Pei-yao XIAO, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Shao-jing JIANG, Pei-yao XIAO, Ke WANG, Rui-jia TANG, Chun-yan LIU, Jing-jing LIU), CN=ArticleExt(id=1156264354216534676, articleId=1156264258183750303, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=CO2驱注气管柱腐蚀失效分析, columnId=1156264152306930605, journalTitle=科学技术与工程, columnName=论文·矿冶工程, runingTitle=null, highlight=null, articleAbstract=

CO2驱油是CO2捕集、利用与封存(carbon capture,utilization and storage,CCUS)技术中CO2地质利用环节的重要组成部分,延长油田开展CO2驱油与封存项目取得了良好的增油封碳效果,但实际CO2驱注入环境下的管柱腐蚀失效原因尚不明晰。利用扫描电镜(scanning electron microscopy,SEM)、3D共聚焦显微镜、能谱分析(energy dispersive spectrometer,EDS)、X射线衍射(X-ray diffraction spectroscopy,XRD)等实验手段对取自吴起某CO2驱油与封存示范区注气管柱的腐蚀形貌进行表征,并对管柱腐蚀产物进行分析,以期明确研究区CO2驱注气管柱腐蚀失效原因。结果表明:以CO2腐蚀为主导的局部腐蚀造成注气管柱的腐蚀失效,腐蚀产物包括FeCO3、Fe的高价氧化物及少量FeS。分析认为,低温CO2的连续注入不会引起管柱腐蚀,但CO2停注期间井筒温度回升、地层水上返使得注气管柱具备了发生CO2/H2S腐蚀的条件,且注气井转注水进一步加剧了管柱腐蚀。建议在CO2停注以及转注水期间加强对注气管柱的杀菌与防腐措施。

, correspAuthors=肖沛瑶, authorNote=null, correspAuthorsNote=
* 肖沛瑶(1996—),男,汉族,陕西西安人,硕士,助理工程师。研究方向:提高采收率技术和CCUS技术。E-mail:
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江绍静(1970—),男,汉族,广东阳江人,硕士,正高级工程师。研究方向:提高采收率技术和CCUS技术。E-mail:

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江绍静(1970—),男,汉族,广东阳江人,硕士,正高级工程师。研究方向:提高采收率技术和CCUS技术。E-mail:

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江绍静(1970—),男,汉族,广东阳江人,硕士,正高级工程师。研究方向:提高采收率技术和CCUS技术。E-mail:

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Comparison of some physical & chemical performances and corresponding criteria

, figureFileSmall=null, figureFileBig=null, tableContent=
项目 化学成分检测 拉伸性能检测
P/
wt.%
S/
wt.%
抗拉强度/
MPa
屈服强度/
MPa
延伸率/
%
W38-112 3# 0.010 0.001 770 680 25
API SPEC
5CT-2018
标准要求
≤0.030 ≤0.030 ≥689 552~758 ≥15
W38-28 1# 0.011 0.002 760 655 24
API SPEC
5CT-2018
标准要求
≤0.030 ≤0.030 ≥689 552~758 ≥14
结论 符合 符合
), ArticleFig(id=1233422561237848268, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156264258183750303, language=CN, label=表1, caption=

测试试样的部分理化性能检测结果与相关标准的对比

, figureFileSmall=null, figureFileBig=null, tableContent=
项目 化学成分检测 拉伸性能检测
P/
wt.%
S/
wt.%
抗拉强度/
MPa
屈服强度/
MPa
延伸率/
%
W38-112 3# 0.010 0.001 770 680 25
API SPEC
5CT-2018
标准要求
≤0.030 ≤0.030 ≥689 552~758 ≥15
W38-28 1# 0.011 0.002 760 655 24
API SPEC
5CT-2018
标准要求
≤0.030 ≤0.030 ≥689 552~758 ≥14
结论 符合 符合
), ArticleFig(id=1233422561388843222, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156264258183750303, language=EN, label=Table 2, caption=

Element mass ratio from EDS pattern of section corrosion products

, figureFileSmall=null, figureFileBig=null, tableContent=
检测对象 质量比/%
C O Ca Cr Mn Fe
W38-112 1#测点1 7.68 27.20 0.22 0.61 0.90 63.39
1#测点2 6.27 29.94 0.07 0.17 2.08 61.48
2# 7.70 21.98 0.36 0.06 0.48 69.42
3#测点1 46.72 24.85 0.77 21.77 0.73 5.16
3#测点2 6.67 24.43 59.72 2.85
4# 9.35 35.53 0.67 54.46
W38-28 1# 2.78 21.72 0.10 0.79 74.62
2# 5.15 26.10 0.41 0.07 0.89 67.39
), ArticleFig(id=1233422561535643873, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156264258183750303, language=CN, label=表2, caption=

截面腐蚀产物EDS分析元素质量比

, figureFileSmall=null, figureFileBig=null, tableContent=
检测对象 质量比/%
C O Ca Cr Mn Fe
W38-112 1#测点1 7.68 27.20 0.22 0.61 0.90 63.39
1#测点2 6.27 29.94 0.07 0.17 2.08 61.48
2# 7.70 21.98 0.36 0.06 0.48 69.42
3#测点1 46.72 24.85 0.77 21.77 0.73 5.16
3#测点2 6.67 24.43 59.72 2.85
4# 9.35 35.53 0.67 54.46
W38-28 1# 2.78 21.72 0.10 0.79 74.62
2# 5.15 26.10 0.41 0.07 0.89 67.39
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CO2驱注气管柱腐蚀失效分析
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江绍静 1 , 肖沛瑶 1, * , 王珂 1 , 汤瑞佳 1 , 刘春燕 2 , 刘晶静 3
科学技术与工程 | 论文·矿冶工程 2025,25(6): 2301-2310
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科学技术与工程 | 论文·矿冶工程 2025, 25(6): 2301-2310
CO2驱注气管柱腐蚀失效分析
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江绍静1 , 肖沛瑶1, * , 王珂1, 汤瑞佳1, 刘春燕2, 刘晶静3
作者信息
  • 1 陕西延长石油(集团)有限责任公司研究院, 西安 710065
  • 2 陕西延长石油(集团)有限责任公司天然气研究院分公司, 西安 710065
  • 3 延长油田股份有限公司吴起采油厂, 延安 717600
  • 江绍静(1970—),男,汉族,广东阳江人,硕士,正高级工程师。研究方向:提高采收率技术和CCUS技术。E-mail:

通讯作者:

* 肖沛瑶(1996—),男,汉族,陕西西安人,硕士,助理工程师。研究方向:提高采收率技术和CCUS技术。E-mail:
Corrosion Failure Analysis of CO2 Flooding Injection String
Shao-jing JIANG1 , Pei-yao XIAO1, * , Ke WANG1, Rui-jia TANG1, Chun-yan LIU2, Jing-jing LIU3
Affiliations
  • 1 Research Institute of Shaanxi Yanchang Petroleum (Group) Co., Ltd., Xi’an 710065, China
  • 2 Natural Gas Research Institute Branch of Shaanxi Yanchang Petroleum (Group) Co., Ltd., Xi’an 710065, China
  • 3 Wuqi Oil Production Plant of Yanchang Oilfield Co., Ltd., Yan’an 717600, China
出版时间: 2025-02-28 doi: 10.12404/j.issn.1671-1815.2308582
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CO2驱油是CO2捕集、利用与封存(carbon capture,utilization and storage,CCUS)技术中CO2地质利用环节的重要组成部分,延长油田开展CO2驱油与封存项目取得了良好的增油封碳效果,但实际CO2驱注入环境下的管柱腐蚀失效原因尚不明晰。利用扫描电镜(scanning electron microscopy,SEM)、3D共聚焦显微镜、能谱分析(energy dispersive spectrometer,EDS)、X射线衍射(X-ray diffraction spectroscopy,XRD)等实验手段对取自吴起某CO2驱油与封存示范区注气管柱的腐蚀形貌进行表征,并对管柱腐蚀产物进行分析,以期明确研究区CO2驱注气管柱腐蚀失效原因。结果表明:以CO2腐蚀为主导的局部腐蚀造成注气管柱的腐蚀失效,腐蚀产物包括FeCO3、Fe的高价氧化物及少量FeS。分析认为,低温CO2的连续注入不会引起管柱腐蚀,但CO2停注期间井筒温度回升、地层水上返使得注气管柱具备了发生CO2/H2S腐蚀的条件,且注气井转注水进一步加剧了管柱腐蚀。建议在CO2停注以及转注水期间加强对注气管柱的杀菌与防腐措施。

CO2驱油  /  CO2/H2S电化学腐蚀  /  管柱腐蚀  /  腐蚀失效  /  防腐措施

CO2 flooding is an important part of the CO2 geological utilization process in CCUS(carbon capture, utilization and storage). The CO2 flooding and storage project carried out in the Yanchang Oilfield has achieved good results in increasing production and storing CO2. But the reasons of pipe string corrosion failure are still unclear during CO2 injection. SEM(scanning electron microscopy), 3D confocal microscopy, EDS(energy dispersive spectrometer) and XRD(X-ray diffraction spectroscopy) were used to characterize the corrosion morphology of the gas injection pipe string in the CO2 flooding and storage demonstration area of Wuqi Oilfield. The pipe string corrosion products are analyzed to clarify the reasons for pipe string failure caused by CO2 corrosion. The results show that local corrosion dominated by CO2 corrosion causes corrosion failure of the pipe string. Corrosion products include FeCO3, high-priced oxides of Fe and a small amount of FeS. Continuous injection of low-temperature CO2 cannot cause corrosion. However, the increase in wellbore temperature and the return of formation water caused by stopping CO2 injection can create conditions for CO2/H2S corrosion in the pipe string. In addition, pipe string corrosion is accelerated when gas injection wells are converted into water injection wells. It is recommended to strengthen the sterilization and anti-corrosion measures for the pipe string during the period of stopping CO2 injection and switching to water injection.

CO2 flooding  /  CO2/H2S electrochemical corrosion  /  pipe string corrosion  /  corrosion failure  /  anti-corrosion measures
江绍静, 肖沛瑶, 王珂, 汤瑞佳, 刘春燕, 刘晶静. CO2驱注气管柱腐蚀失效分析. 科学技术与工程, 2025 , 25 (6) : 2301 -2310 . DOI: 10.12404/j.issn.1671-1815.2308582
Shao-jing JIANG, Pei-yao XIAO, Ke WANG, Rui-jia TANG, Chun-yan LIU, Jing-jing LIU. Corrosion Failure Analysis of CO2 Flooding Injection String[J]. Science Technology and Engineering, 2025 , 25 (6) : 2301 -2310 . DOI: 10.12404/j.issn.1671-1815.2308582
CO2驱油技术是特低渗透油藏提高石油采收率的重要技术之一[1-4],同时可实现规模化CO2地质封存。截至目前,延长油田已先后在靖边、吴起、杏子川建成4个CO2驱油与封存示范区,取得良好的驱油和封存效果[5-6]。然而,在技术大规模实施应用过程中,CO2驱注采环境下的管柱腐蚀失效问题偶有发生,导致井下作业频繁,严重影响了油田安全高效开发[7-8]
中外学者针对CO2驱油技术实施时伴随的管材腐蚀问题开展了广泛的实验室研究。杜森等[9]采用极化曲线测试、交流阻抗谱测试等方法研究了几种油田常用管材在模拟CO2驱油环境下的电化学腐蚀行为。吕雷等[10]采用类似方法研究了16Mn钢在模拟高含CO2腐蚀环境下的电化学腐蚀行为和特征,研究结果同样具有参考意义。借助高温高压反应釜,Gu等[11]以5Cr钢为例,研究了钢材表面附着的氧化膜在CO2驱油环境中的腐蚀行为及其对钢材耐腐蚀性能的影响;张星等[12]利用CO2驱实际采出液和现场原油构建高温高压CO2-油水混合环境,探究乳状液、微液滴在材料表面诱发腐蚀的动态过程及扩展机制。Zhao等[13]和李俊池等[14]将电化学测试与高温高压腐蚀模拟相结合,前者模拟CO2驱注采环境,分析了3Cr、5Cr、9Cr三种低铬钢在不同CO2分压条件下的腐蚀性能及变化规律,明确三种低铬油管材料的适用性;后者研究了X70管线钢在不同CO2压力下的腐蚀开裂规律。此外,对于CO2驱注采过程中CO2超临界状态、高Cl-浓度等因素对管材腐蚀的影响,Sun等[15]研究了H2S对N80钢在超临界CO2环境中腐蚀行为的影响;吴保玉等[16]研究了超临界CO2/H2O体系下不同碳钢在CO2驱油工况中的腐蚀行为;Song等[17]研究了CO2+蒸汽混合驱条件下不同因素对氯离子应力腐蚀开裂过程的作用。
总体而言,专家学者在当前阶段针对此问题开展研究时主要围绕“通过实验检测表征不同环境因素对不同类型管材腐蚀行为的影响程度及规律,综合各因素对CO2腐蚀过程的作用机理建立符合材料所处环境特点及腐蚀特征的CO2驱注采环境下管材腐蚀机理”这一理念展开具体工作。调研发现,这些研究的对象主要是室内模拟的腐蚀过程,即借助电化学工作站或高温高压反应釜研究管材在模拟CO2驱油环境下发生的腐蚀行为。但室内短时间模拟与现场长期腐蚀、有限考虑因素与复杂井筒环境之间的区别,无疑会导致基于模拟腐蚀过程对管材腐蚀特征、失效机理得出的认识与实际腐蚀行为的腐蚀特征、作用机理存在一定差异。若能针对发生在服役于CO2驱注采环境下的现场管材上的实际腐蚀现象进行深入研究,所取得的研究结果无疑将具有更加实际的指导作用。
并且,在室内模拟工况建立时,倾向于设置CO2驱采出环境进行模拟,对注入环境的模拟则相对较少,而注入环境下的井筒中流体理化性质较采出环境存在一定区别。此外,实际CO2注采过程中可能存在CO2与H2S共存的腐蚀环境,CO2腐蚀与H2S电化学腐蚀的相互作用机制及其对管材的影响方式仍有待研究。
鉴于此,现选取吴起采油厂某CO2驱油与封存示范区内的W38-28、W38-112两口CO2驱注气井长期服役注气油管作为研究对象,利用扫描电镜、3D共聚焦显微镜、EDS、XRD等实验手段对注气油管的腐蚀形貌进行表征,并对管柱腐蚀产物进行分析,以研究区域内注气井油管在CO2注入形成的CO2/H2S共存井筒环境中的腐蚀失效原因。
截取W38-112、W38-28两口注气井不同井深典型腐蚀严重的油管段,W38-112井截取4段:1#(214.42 m)、2#(662 m)、3#(1 024 m)、4#(2 010 m);W38-28井截取2段:1#(1 341.88 m)、2#(1 913.85 m)。
W38-112井和W38-28井的油藏原始地层压力13.3 MPa;温度约60 ℃,部分井段处在高腐蚀速率敏感区[18]。2021年11月进行的水质分析结果显示,两口井中地层水pH=5.5,属CaCl2水型,Cl-离子含量均为38.85 g/L;Ca2+/HC${\mathrm{O}}_{3}^{-}$比值较低,分别为0.011和0.013。两口井使用同一种N80油管作为注气管柱,其最大碳元素含量0.35%,最大铬元素含量0.2%。检测用W38-112井注气油管共服役6年,服役期间只用于注气(4年);W38-28井注气油管共服役6年10个月,服役期间前期注气(4年9个月),后期转注水(5个月)。
SC-D2磁粉探伤仪、ARL直读光谱仪、KH-3000型三维视频显微镜、HXD-2000型显微硬度计、UTM/CTM6000系列电子万能试验机、半自动冲击试验机、数码相机、NOVANANO450型场发射扫描电镜、LSM800型激光共聚焦显微镜、Empyrean型X-射线衍射仪。部分检测仪器的实物图如图1所示。
(1)无损检测及理化性能检测。利用SC-D2磁粉探伤仪对6个管段进行无损检测。选取W38-112井的3#管段和W38-28井的1#管段进行理化性能检测:利用ARL直读光谱仪对试样进行化学成分分析,利用HXD-2000型显微硬度计检测试样硬度,利用KH-3000型三维视频显微镜对试样金相组织进行分析,利用UTM/CTM6000系列电子万能试验机和半自动冲击试验机检测试样拉伸性能和冲击性能。
(2)形貌表征。使用数码相机对6个管段进行全貌、外表面和内表面宏观照相。利用NOVANANO450型场发射扫描电镜对6个管段进行腐蚀产物清洗前、后的内/外表面扫描电镜(scanning electron microscopy,SEM)形貌观测以及腐蚀产物清洗前的截面内/外侧SEM形貌观测;利用LSM800型激光共聚焦显微镜对截取自6个管段的试样进行外表面形貌测试和深度测量。
(3)成分分析。利用NOVANANO450型场发射扫描电镜配备的能谱仪、Empyrean型X-射线衍射仪对截取自6个管段的试样进行内/外表面、截面腐蚀产物元素EDS分析和内表面腐蚀产物物相组成XRD分析。
无损检测结果表明,6个管段试样的磁粉探伤合格级别均符合NB/T 47013.4—2015标准Ⅰ级要求。W38-112井3#管段试样和W38-28井1#管段试样的化学成分、拉伸性能均符合API SPEC 5CT—2018标准对N80油管的要求,检测结果如表1所示。拉伸性能中屈服强度指总延伸率为0.5%时的强度。
硬度检测时在两试样上分别随机选取的5个测点的维氏硬度范围和平均值分别为220.2~229.0、223.9和220.7~231.5、224.5。在两个管段上分别选取三块试样进行夏比V形缺口冲击性能检测,冲击功平均值分为别37 J和39 J,剪切比平均值均为100%。两管段试样的金相组织均以晶粒细小的铁素体+索氏体为主,金相组织正常。
综合各项检测结果,认为两口井使用的N80油管的材料性能整体满足标准要求,注气管柱所处的井下环境是导致其腐蚀严重甚至失效的主要原因。
图2腐蚀产物清洗前整体宏观形貌图上看,随着井深的增大,W38-112井油管外表面腐蚀特征愈加突出,尤其是1 024 m、2 016 m处形成的腐蚀产物层大块脱落。在大致相同的井深附近,W38-28井油管外表面和内表面的腐蚀更加严重。井深1 314.88 m处丝扣基本保持完好,但丝扣端附近发生了严重腐蚀处于失效状态[图2(b)中W38-28井1#管段外表面],这可能是由于螺纹连接部位存在一定的间隙,更容易积聚腐蚀介质,延长了其与管壁基体的接触时间,加剧了此部位的腐蚀。在井深1 913.85 m处,油管因严重腐蚀发生变形,管体出现大量穿孔特征,处于完全失效状态。局部宏观形貌特征方面,清除腐蚀产物后可在W38-112井的3#和4#管段表面略见局部腐蚀特征;W38-28井的腐蚀环境则导致其油管发生了严重的局部腐蚀,清除腐蚀产物后可在1#和2#管段表面看到大量连片的坑状腐蚀形态。
图3图4所示为管段试样清洗腐蚀产物后的内、外表面SEM微观形貌。从观测结果来看,W38-112井1#、2#、3#管段的内表面以及1#、2#管段的外表面腐蚀较均匀;4#管段的内表面以及3#、4#管段的外表面出现较明显的局部腐蚀特征,有大片的腐蚀产物层脱落。W38-28井试样清洗后可以观察到裸露的油管基体表面不平整,形成大量蚀坑或腐蚀台阶,符合CO2腐蚀的典型特征[19-20]
图5图6所示为管段试样清洗腐蚀产物前的内、外侧截面SEM微观形貌。可见“膜下腐蚀”现象大量存在,这表明不断有腐蚀介质穿透产物膜侵蚀基体表面,若继续处于井下腐蚀环境中,部分蚀坑将很大可能进一步发展,形成微裂纹并逐步扩展成为裂缝,作为腐蚀介质接触材料基体的新路径加速管柱腐蚀。
管段试样腐蚀产物清洗后的外表面共聚焦轮廓显微特征及深度变化测试情况如图7所示,结果显示:W38-112井管段试样外表面存在一定的局部腐蚀区域,W38-28井管段试样外表面整体都处于十分显著的局部腐蚀区域。W38-112井选取较典型区域进行表面深度测试,1#~4#管段试样外表面最大深度分别为200、250、410、600 μm;W38-28井随机选取区域进行表面深度测试,1#、2#管段试样外表面最大深度分别为370、520 μm,均表现出随着井深加大,注气油管外表面局部腐蚀逐渐加重的特征。
EDS能谱分析结果显示,两注气井油管表面、截面腐蚀产物均以C、O、Fe元素为主。截面腐蚀产物EDS分析的元素质量比情况如表2所示。从表2可知:①试样截面腐蚀产物的主要元素为C、O、Fe以及极少量Cr、Mn、Ca,其中Ca可能由CaCO3垢引起;②W38-112井1#试样和3#试样有两个不同测试点,分别位于整体腐蚀区(测点1)与蚀坑区(测点2),可以看出3#试样C元素含量差异较大,可能是因为蚀坑区的腐蚀产物大量脱落,X射线探测较接近基体。
根据元素质量比、原子个数比数据绘制W38-112井、W38-28井注气油管内/外表面的C、O、Fe元素含量随井深变化曲线图,如图8图9所示。
综合分析元素质量比曲线(实线)和原子个数比曲线(虚线)的形态特征,可以看到,Fe元素对应的内外表面元素含量随井深变化曲线均在封隔器坐封位置附近存在交点,交点上下的Fe元素含量大小关系相反,而Fe元素又是形成管壁腐蚀产物的必要组分,表明封隔器坐封位置上下的油管表面主要腐蚀形式发生转变,封隔器上部的油管以内壁腐蚀为主,下部油管则以外壁腐蚀为主。
以W38-112井油管样品的检测结果为例,从内表面腐蚀产物XRD分析结果(图10)来看,W38-112井上部和下部油管的腐蚀产物差异很大,上部油管的腐蚀产物的主要是Fe3O4和FeS,而下部油管的腐蚀产物主要是FeCO3;W38-28井中部油管的腐蚀产物主要是FeCO3,下部油管的腐蚀产物主要是FeO(OH)和Fe2O3
内表面腐蚀产物中,FeCO3是CO2腐蚀的典型产物;Fe3O4、Fe2O3和FeO(OH)可能是金属在空气中氧化产物,也可能是FeCO3在空气中的分解或氧化产物[21]。由于W38-112井在钻井过程中无H2S显示,注入气成分检测结果也显示气源纯净,CO2浓度大于99%、未检出H2S,但持续注气较长一段时间后监测到井筒内有H2S气体出现,认为W38-112井腐蚀产物中的FeS可能来源于随其他地面注入物进入井筒并附着于管壁的硫酸盐还原菌生成的H2S形成的高浓度CO2/低浓度H2S共存的井筒环境中发生的H2S腐蚀。
综合以上两项腐蚀产物检测的结果,认为注气油管内表面在CO2注入环境中发生的腐蚀主要为CO2腐蚀,局部区域发生H2S腐蚀,Cl-的存在加速了局部腐蚀。
CO2注气阶段,油管在连续注低温CO2期间是基本不会发生CO2/H2S腐蚀的。但CO2停注后,井筒温度逐渐恢复,井筒、环空压力随着CO2向地层扩散而逐渐降低导致地层水进入井筒和油套环空,综合作用使得注气管柱具备了发生CO2/H2S腐蚀的环境条件。
对于不含H2S的CO2驱注气井,停注期间形成温度适宜的酸性环境;恢复注气后CO2率先在油管内潮湿的环境下引起CO2腐蚀,腐蚀产物FeCO3在内壁形成、附着,且随着注气时间的增加,FeCO3产物膜趋于完整、致密,对金属基体的保护性逐渐增强。
由于入井流体质量控制不严,硫酸盐还原菌进入井筒并生成H2S,使得注气油管内原本的单一CO2腐蚀体系逐步转变为高浓度CO2/低浓度H2S共存体系;在此环境下,受高CO2分压的抑制作用[22]、致密FeCO3膜的阻碍作用[23]、过酸性环境的溶解作用[24]等不利影响(影响方式见图11),H2S电化学腐蚀只能在部分管段区间发生,生成的腐蚀产物FeS只能在部分管段区间留存,因而只能在以上两个区间相交的部分检测到少量FeS的存在,整个油管内壁的腐蚀产物以FeCO3为主,腐蚀形态以符合CO2腐蚀典型特征的点蚀、台阶状腐蚀为主;管壁金属长期被CO2、H2S、溶解氧等腐蚀介质侵蚀,造成注气油管内壁的腐蚀程度逐渐加重,甚至腐蚀穿孔、腐蚀失效。此外,不同膜类产物间的电偶腐蚀效应也会加速油管内壁的局部腐蚀[25]
此外,由此次腐蚀检测可以看出,W38-28井注气油管的腐蚀程度比W38-112井严重得多。生产资料显示,W38-112井自2019年8月停注气后未注水,而W38-28井自2019年9月停注气后在2020年7—9月间转注水,这表明注气井转注水对油管腐蚀影响极大,原因可能是注入水中含有溶解氧等杂质加剧了管壁的腐蚀。
(1)注气管柱在低温CO2连续注入过程中不易受到腐蚀侵害,但CO2停注及注气转注水期间井筒温度回升、地层水上返,造成油管内壁在高CO2/低H2S井筒环境中发生严重的电化学腐蚀,腐蚀形式以CO2腐蚀为主。
(2)封隔器坐封位置以上的油管以内壁腐蚀为主,以下以外壁腐蚀为主。注气井转注水井进一步加剧了管柱的腐蚀,尤其是局部腐蚀。
(3)对于CO2驱注气井的管柱防腐,需从减少气源含杂(尤其是H2S的含量)、转注工艺(停注与转注前加注防腐保护液或缓蚀杀菌剂)以及耐蚀材质(抗硫钢或耐蚀钢)三方面入手加以改善。
  • 陕西省秦创原碳中和背景下油藏CO2地质封存关键技术“科学家+工程师”项目(2022KXJ-050)
  • 延长石油集团“揭榜挂帅”项目(ycsy2021jbgs-A-04)
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2025年第25卷第6期
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doi: 10.12404/j.issn.1671-1815.2308582
  • 接收时间:2023-11-02
  • 首发时间:2025-07-27
  • 出版时间:2025-02-28
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  • 收稿日期:2023-11-02
  • 修回日期:2024-10-17
基金
陕西省秦创原碳中和背景下油藏CO2地质封存关键技术“科学家+工程师”项目(2022KXJ-050)
延长石油集团“揭榜挂帅”项目(ycsy2021jbgs-A-04)
作者信息
    1 陕西延长石油(集团)有限责任公司研究院, 西安 710065
    2 陕西延长石油(集团)有限责任公司天然气研究院分公司, 西安 710065
    3 延长油田股份有限公司吴起采油厂, 延安 717600

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* 肖沛瑶(1996—),男,汉族,陕西西安人,硕士,助理工程师。研究方向:提高采收率技术和CCUS技术。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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