钨合金镀层在油田井下环境中的腐蚀行为
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摘要
目的研究钨合金在塔河油田井下(高温、高酸性及注氮气环境)的腐蚀行为规律。方法在高温高压釜中模拟塔河注气井下工况,结合腐蚀失重、镀层厚度测试、显微硬度测试以及扫描电镜、EDS、SRD等分析手段,对钨合金镀层的腐蚀行为进行研究。结果未腐蚀镀层的维氏硬度为825HV,但经过腐蚀后,镀层的显微硬度值因压痕边角塌陷而无法读取。在H_2S主控环境中,镀层试样明显增重,当温度为130℃时,镀层未观察到分层现象,但镀层表面有腐蚀产物;200℃时镀层出现明显分层和鼓泡,并且鼓泡有破裂现象,微观观察镀层表面有局部腐蚀,局部腐蚀处检测到硫元素,说明硫元素渗入镀层内部,生成硫化物。在160℃的H_2S/CO_2共存和CO_2主控环境中,试样增重不明显,也未发生失重,镀层有轻微的分层现象。在注氮气环境中,试样发生明显失重,镀层厚度减薄,镀层的腐蚀以均匀腐蚀为主,同时镀层出现分层现象。镀层在注气井井下环境中腐蚀后变脆。结论钨合金镀层在高含H_2S环境中及注氮气环境中会发生明显分层,并会出现局部腐蚀,耐蚀性较差,而在其他环境中出现轻微分层现象。
The work aims to study the corrosion behavior of Tungsten alloy coating in the underground environment of Tahe oilfield(high temperature, peracidity and N2 injection). The underground environment of Tahe oilfield was simulated in high temperature and high pressure autoclave and the corrosion behavior of Tungsten alloy coating under simulated conditions was studied by weight loss measurement, coating thickness test, mircohardness test, SEM, EDS and XRD. Hardness of sample before corrosion was 825 HV, while the hardness of all samples after corrosion could not be measured because of the collapse of indentation corners. In H_2S dominated environment, the weight of samples increased obviously. When temperature reached130 ℃, there was no stratified phenomenon on the coating, but the surface had corrosion products. Stratified phenomenon and bubbling obviously appeared on the coating at 200 ℃ and the bubbles broke out. Local corrosion was also observed on the surface and element S was detected in the local corrosion position by EDS test, indicating that S reacted with Fe to form iron sulfides. The weight of samples did not change significantly after corrosion at 160 ℃ in the H_2S/CO_2 and CO_2 dominated environment and there was no weight loss, either, but light stratified phenomenon appeared on the surface. The weight and thickness of samples decreased significantly in the environment of N_2 injection. The coating corrosion was mostly uniform and stratified phenomenon appeared in the coating as well. The coating became brittle after corrosion in all simulated environments. In the environment with high H_2S and N_2, Tungsten alloy coating has obvious stratified phenomenon, local corrosion and poor corrosion resistance, but shows slight stratified phenomenon in other environment.
The work aims to study the corrosion behavior of Tungsten alloy coating in the underground environment of Tahe oilfield(high temperature, peracidity and N2 injection). The underground environment of Tahe oilfield was simulated in high temperature and high pressure autoclave and the corrosion behavior of Tungsten alloy coating under simulated conditions was studied by weight loss measurement, coating thickness test, mircohardness test, SEM, EDS and XRD. Hardness of sample before corrosion was 825 HV, while the hardness of all samples after corrosion could not be measured because of the collapse of indentation corners. In H_2S dominated environment, the weight of samples increased obviously. When temperature reached130 ℃, there was no stratified phenomenon on the coating, but the surface had corrosion products. Stratified phenomenon and bubbling obviously appeared on the coating at 200 ℃ and the bubbles broke out. Local corrosion was also observed on the surface and element S was detected in the local corrosion position by EDS test, indicating that S reacted with Fe to form iron sulfides. The weight of samples did not change significantly after corrosion at 160 ℃ in the H_2S/CO_2 and CO_2 dominated environment and there was no weight loss, either, but light stratified phenomenon appeared on the surface. The weight and thickness of samples decreased significantly in the environment of N_2 injection. The coating corrosion was mostly uniform and stratified phenomenon appeared in the coating as well. The coating became brittle after corrosion in all simulated environments. In the environment with high H_2S and N_2, Tungsten alloy coating has obvious stratified phenomenon, local corrosion and poor corrosion resistance, but shows slight stratified phenomenon in other environment.
引文
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[18]钱进森,燕铸,刘建彬,等.微量H2S对油管钢CO2腐蚀行为的影响[J].焊管,2014,35(12):39-45.QIAN Jin-sen,YAN Zhu,LIU Jian-bin,et al.Effect of small amount H2S on CO2 corrosion behavior of oil tube steel[J].Welded pipe and tube,2014,35(12):39-45.
[2]林涛.碳酸盐岩缝洞型油藏开发工程工艺技术[M].青岛:中国石油大学出版社,2017.LIN Tao.Development engineering technology of carbonate fractured vuggy reservoir[M].Qingdao:China University of Petroleum Press,2017.
[3]陈国鑫.缝洞型碳酸盐岩油藏典型缝洞组合注采规律研究[D].青岛:中国石油大学(华东),2014.CHEN Guo-xin.Injection-production laws research on typical fracture-vugcombination in fractured-vuggy carbonate reservoir[D].Qingdao:China University of Petroleum(East China),2014.
[4]赵文娜,王宇宾,张烨.高温地面交联酸体系研究及其现场应用[J].科学技术与工程,2013,13(8):2191-2193.ZHAO Wen-na,WANG Yu-bin,ZHANG Ye.Study and application of the ground cross-linked acid with hightemperature resistance[J].Science technology and engineering,2013,13(8):2191-2193.
[5]唐世春,张志宏,张江江.塔河油田点蚀测试及评价技术应用[J].科技导报,2013,31(32):42-48.TANG Shi-chun,ZHANG Zhi-hong,ZHANG Jiang-jiang.Application of test and evaluation technology of pitting corrosion in Tahe oilfield[J].Science&technology review,2013,31(32):42-48.
[6]詹俊阳,马旭杰,何长江.塔河油田缝洞型油藏开发模式及提高采收率[J].石油与天然气地质,2012,33(4):655-660.ZHAN Jun-yang,MA Xu-jie,HE Chang-jiang.Development scheme and EOR technique of fracture-vugreservoirs in Tahe oilfield[J].Oil&gas geology,2012,33(4):655-660.
[7]张江江.气液环境下注氮气井管道腐蚀因素和机理研究[J].科学技术与工程,2014,14(29):9-14.ZHANG Jiang-jiang.Study on nitrogen gas pipeline and mechanism of corrosionfactors on gas-liquid environment[J].Science technology and engineering,2014,14(29):9-14.
[8]任增泉.塔河油田注气开发地面配套技术研究[D].青岛:中国石油大学(华东),2016.REN Zeng-quan.The studies on ground supporting technology for gas flooding of Tahe oil field[D].Qingdao:China University of Petroleum(East China),2016.
[9]张江江.塔河油田注气井管道腐蚀特征及规律[J].科技导报,2014,32(31):65-70.ZHANG Jiang-jiang.Tahe oilfield gas pipeline corrosion characteristics and rules[J].Science&technology review,2014,32(31):65-70.
[10]祁丽莎,陈明贵,王小玮,等.塔河油田注气井井筒氧腐蚀机理研究[J].石油工程建设,2016,42(6):70-72.QI Li-sha,CHEN Ming-gui,WANG Xiao-wei,et al.Study of oxygen corrosion mechanism in wellbore tube for gas injection in Tahe oilfield[J].Petroleum engineering construction,2016,42(6):70-72.
[11]胡松阳,毕琳琳,张艳敏,等.电镀钨基合金抽油杆耐腐蚀性能试验研究[J].石油机械,2011,39(10):12-15.HU Song-yang,BI Lin-lin,ZHANG Yan-min,et al.Experimental study on corrosion resistance of electroplated tungsten alloy sucker rod[J].China petroleum machinery,2011,39(10):12-15.
[12]李春茂,郭庆荣,韩民强.镀钨合金防腐抽油杆[J].石油科技论坛,2017(S1):128-131.LI Chun-mao,GUO Qing-rong,HAN Min-qiang.Tungsten alloy plated sucker rod[J].Petroleum technology forum,2017(S1):128-131.
[13]侯铎,施太和,曾德智,等.电镀钨合金镀层组织及其耐腐蚀性能研究[J].材料导报,2012,26(5):12-15.HOU Duo,SHI Tai-he,ZENG De-zhi,et al.Coating microsturcture characteristics and corrosion resistance of electroplating W alloy[J].Material review,2012,26(5):12-15.
[14]孙福洋,赵国仙,郭清超,等.镍钨合金镀层对QT-900油管耐CO2腐蚀的影响[J].表面技术,2014,43(6):6-15.SUN Fu-yang,ZHAO Guo-xian,GUO Qing-chao,et al.Effect of Ni-W alloy coating on the corrosion resistance of QT-900 coiled tubing[J].Surface technology,2014,43(6):6-15.
[15]裘智超,熊春明,叶正荣,等.镍钨合金镀层在高含CO2及低含H2S环境下腐蚀行为[J].石油矿场机械,2017,46(4):47-51.QIU Zhi-chao,XIONG Chun-ming,YE Zheng-rong,et al.Corrosion behavior of nickel and tungsten alloy plating in high CO2 and low H2S corrosive environment[J].Oil field equipment,2017,46(4):47-51.
[16]宋中华,张士诚,周理志,等.钨镍合金镀层油管适用性[J].腐蚀与防护,2014,35(12):1256-1259.SONG Zhong-hua,ZHANG Shi-Cheng,ZHOU Li-zhi,et al.Applicability of tungsten nickel alloy coated tubing[J].Corrosion&protection,2014,35(12):1256-1259.
[17]雷丹.钨合金镀层油管在高含H2S环境下的腐蚀行为研究[D].西安:西安石油大学,2013.LEI Dan.Research on corrosion behavior of tungstenbased alloy coating under high H2S environment[D].Xian:Xi'an Shiyou University,2013.
[18]钱进森,燕铸,刘建彬,等.微量H2S对油管钢CO2腐蚀行为的影响[J].焊管,2014,35(12):39-45.QIAN Jin-sen,YAN Zhu,LIU Jian-bin,et al.Effect of small amount H2S on CO2 corrosion behavior of oil tube steel[J].Welded pipe and tube,2014,35(12):39-45.
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