温度对3Cr钢在CO_2-O_2环境中腐蚀的影响
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摘要
为了研究注多元热流体吞吐热力采油过程中温度对油套管钢的影响,利用高温高压电化学釜模拟注多元热流体采油工况,分别在60、100和100～60℃循环的温度条件下,对3Cr钢进行失重腐蚀挂片试验和电化学腐蚀试验,利用高温高压电化学釜得到了3Cr钢在模拟工况下的腐蚀速率和极化曲线,并利用SEM、XRD、EDS分析了腐蚀产物膜形貌和成分。结果表明,温度由60升高至100℃时,腐蚀速率由0.552增长至1.920 mm/a,在100-60℃高-低温循环时,腐蚀速率进一步升高至4.292 mm/a;60和100℃时,腐蚀产物均为单层膜结构,且存在点蚀坑;在100-60℃高-低温循环时,腐蚀产物为双层膜结构,且存在直径约为4μm的腐蚀坑。温度主要影响3Cr钢腐蚀产物膜的结构和点蚀的形态,60和100℃时,点蚀坑内的聚集的Cl~-离子使点蚀向纵深处发展,在100-60℃高-低温循环时,溶液中的O_2促进了点蚀的横向发展,而腐蚀坑底部富集的Cr将阻碍点蚀的纵向发展。注多元热流体热力采油过程应充分考虑温度变化对3Cr钢腐蚀的影响,同时也要考虑温度变化引起3Cr钢点蚀的敏感性。
To study the influence of temperature on oil casing steel in the thermal oil recovery by multiple thermal fluid injection, the weight loss and electrochemical tests of 3 Cr steel were carried out under the stable temperature of 60 and 100 ℃ as well as the temperature cycle of 100-60 ℃. HTHP electrochemical autoclave was used to simulate the oil recovery process and then the corrosion rate and electrochemical polarization curves of 3 Cr steel were obtained. The surface morphology and composition of corrosion products were investigated by scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS) and X-ray diffraction(XRD). The results showed that the corrosion rate of 3 Cr steel increased from 0.552 to 1.92 mm/a when the temperature rose from 60 to 100 ℃. The corrosion rate further increased to 4.292 mm/a with the temperature cycling between 100 and 60 ℃. The corrosion products were identified to be single-layer and tiny pitting exists on the surface at 60 or 100 ℃. While the temperature cycled between 100 and 60 ℃, the corrosion products were double-layer and a corrosion pit was found with a diameter of 4 μm. The structure of corrosion scales and the morphology of corrosion pits were mainly affected by temperature. At stable temperature of 60 and 100 ℃, Cl~- ions enriched in the pitting increase the corrosion depth. Under temperature cycle of 100-60 ℃, O_2 in the solution increased the pitting size, while Cr enriched at the bottom of corrosion pits increased the corrosion depth. In the thermal oil recovery by multiple thermal fluid injection, the influence of temperature on the corrosion of 3 Cr steel should be fully considered, as well as the pitting sensibility caused by temperature change.
To study the influence of temperature on oil casing steel in the thermal oil recovery by multiple thermal fluid injection, the weight loss and electrochemical tests of 3 Cr steel were carried out under the stable temperature of 60 and 100 ℃ as well as the temperature cycle of 100-60 ℃. HTHP electrochemical autoclave was used to simulate the oil recovery process and then the corrosion rate and electrochemical polarization curves of 3 Cr steel were obtained. The surface morphology and composition of corrosion products were investigated by scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS) and X-ray diffraction(XRD). The results showed that the corrosion rate of 3 Cr steel increased from 0.552 to 1.92 mm/a when the temperature rose from 60 to 100 ℃. The corrosion rate further increased to 4.292 mm/a with the temperature cycling between 100 and 60 ℃. The corrosion products were identified to be single-layer and tiny pitting exists on the surface at 60 or 100 ℃. While the temperature cycled between 100 and 60 ℃, the corrosion products were double-layer and a corrosion pit was found with a diameter of 4 μm. The structure of corrosion scales and the morphology of corrosion pits were mainly affected by temperature. At stable temperature of 60 and 100 ℃, Cl~- ions enriched in the pitting increase the corrosion depth. Under temperature cycle of 100-60 ℃, O_2 in the solution increased the pitting size, while Cr enriched at the bottom of corrosion pits increased the corrosion depth. In the thermal oil recovery by multiple thermal fluid injection, the influence of temperature on the corrosion of 3 Cr steel should be fully considered, as well as the pitting sensibility caused by temperature change.
引文
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[2] 黄世军,谷悦,程林松,等.多元热流体吞吐水平井热参数和加热半径计算[J].中国石油大学学报:自然科学版,2015(4):97.(Huang S J,Gu Y,Cheng L S,et al.Modeling of thermodynamic parameters and heating radius for multiple thermal fluid stimulation in horizontal wells[J].Journal of China University of Petroleum:Edition of Natural Science,2015(4):97.)
[3] 林学强,柳伟,张晶,等.含O2高温高压CO2环境中3Cr钢腐蚀产物膜特征[J].物理化学学报,2013,29(11):2405.(Lin X Q,Liu W,Zhang J,et al.Characteristics of corrosion scale of 3Cr steel at high temperature and pressure in an O2 and CO2 environment[J].Acta Physica Sinica,2013,29(11):2405.)
[4] Lin X,Liu W,Wu F,et al.Effect of O2 on corrosion of 3Cr steel in high temperature and high pressure CO2-O2 environment[J].Applied Surface Science,2015,329:104.
[5] Lu S,Liu W,Zhang S,et al.Corrosion performance of carbon steel in CO2 aqueous environment containing silty sand with different sizes[J].Acta Metallurgica Sinica:English Letters,2017,30(11):1.
[6] Guo S,Xu L,Zhang L,et al.Characterization of corrosion scale formed on 3Cr steel in CO2-saturated formation water[J].Corrosion Science,2016,110:123.
[7] 曾德智,董宝军,石善志,等.高温蒸汽环境中CO2分压对3Cr钢腐蚀的影响[J].钢铁研究学报,2018,30(7):548.(Zeng D Z,Dong B J,Shi S Z,et al.Effect of CO2 partial pressure on the corrosion of 3Cr in high temperature steam environment[J].Journal of Iron and Steel Research,2018,30(7):548.)
[8] 李玉谦,杜琦铭,成慧梅.合金元素对油船用低合金钢腐蚀行为的影响[J].钢铁研究学报,2017,29(6):506.(Li Y Q,Du Q M,Cheng H M.Effect of alloy elements on corrosion behavior of low alloy steel used for oil tanker[J].Journal of Iron and Steel Research,2017,29(6):506.)
[9] Zeng D,Dong B,Shi S,et al.Effects of temperature on corrosion of N80 and 3Cr steels in the simulated CO2 auxiliary steam drive environment[J].Arabian Journal for Science and Engineering,2018:43(7):3845.
[10] 姜杉,柴锋,杨才福.流动3.5%NaCl溶液中Cr对低合金钢锈层还原行为的影响[J].钢铁研究学报,2018,30(3):251.(Jiang S,Chai F,Yang C F.Influence of Cr on reduction behavior of rust formed on low alloy steels in flowing 3.5% NaCl solution[J].Journal of Iron and Steel Research,2018,30(3):251.)
[11] Li W,Xu L,Qiao L,et al.Effect of free Cr content on corrosion behavior of 3Cr steels in a CO2 environment[J].Applied Surface Science,2017,425:32.
[12] 陈东,柳伟,路民旭,等.CO2分压对N80钢腐蚀产物膜保护性能的影响[J].北京科技大学学报,2007,29(3):288.(Chen D,Liu W,Lu M X,et al.Influence of CO2 partial pressure on the protection property of corrosion scale formed on N80 steel[J].Journal of University of Science and Technology Beijing,2007,29(3):288.)
[13] Xu L,Wang B,Zhu J,et al.Effect of Cr content on the corrosion performance of low-Cr alloy steel in a CO2 environment[J].Applied Surface Science,2016,379:39.
[14] Wei L,Pang X,Gao K.Effect of small amount of H2S on the corrosion behavior of carbon steel in the dynamic supercritical CO2 environments[J].Corrosion Science,2016,103:132.
[15] Guo S,Xu L,Zhang L,et al.Corrosion of alloy steels containing 2% chromium in CO2 environments[J].Corrosion Science,2012,63:246.
[16] 朱世东,李金灵,杨志刚,等.温度对J55油管CO2腐蚀行为的影响[J].机械工程材料,2014,38(8):6.(Zhu S D,Li J L,Yang Z G,et al.Effect of temperature on CO2 corrosion behavior of J55 tubing[J].Materials for Mechanical Engineering,2014,38(8):6.
[17] Sun C,Wang Y,Sun J,et al.Effect of impurity on the corrosion behavior of X65 steel in water-saturated supercritical CO2 system[J].Corrosion Science,2016,116:70.
[18] 林学强.碳钢和低合金钢在含O2高温高压CO2油气田环境中腐蚀行为研究[D]//北京:北京科技大学,2015.(Lin X Q.Corrosion Behavior of Carbon Steel and Low Alloy Steel in CO2 and O2 High Temperature and High Pressure Environment of Oil and Gas Fields[D]//Beijing:University of Science and Technology Beijing,2015.)
[19] Dong B,Zeng D,Yu Z,et al.Corrosion mechanism and applicability assessment of N80 and 9Cr steels in CO2 auxiliary steam drive[J].Journal of Materials Engineering and Performance,2019,28(1):1030.
[20] Zhang Y,Pang X,Qu S,et al.Discussion of the CO2 corrosion mechanism between low partial pressure and supercritical condition[J].Corrosion Science,2012,59(3):186.
[21] Tang Y,Guo X P,Zhang G A.Corrosion behaviour of X65 carbon steel in supercritical-CO2 containing H2O and O2 in carbon capture and storage(CCS)technology[J].Corrosion Science,2017,118:118.
[22] Wang B,Xu L,Zhu J,et al.Observation and analysis of pseudopassive film on 6.5%Cr steel in CO2 corrosion environment[J].Corrosion Science,2016,111:711.
[23] 李大朋,张雷,石凤仙,等.温度对13Cr不锈钢在高 CO2分压环境中腐蚀行为的影响[J].工程科学学报,2015,37(11):1463.(Li D P,Zhang L,Shi F X,et al.Effect of temperature on the corrosion behavior of 13Cr stainless steel under a high CO2 partial pressure environment[J].Journal of University of Science and Technology Beijing,2015,37(11):1463.)