高溫高壓環境下不同濃度KBr溶液對13Cr不銹鋼的腐蝕行為影響

朱金陽; 鄭子易; 許立寧; 路民旭

doi:10.13374/j.issn2095-9389.2019.05.009

高溫高壓環境下不同濃度KBr溶液對13Cr不銹鋼的腐蝕行為影響

doi: 10.13374/j.issn2095-9389.2019.05.009

1.
北京科技大學國家材料服役安全科學中心, 北京 100083
2.
北京科技大學新材料技術研究院, 北京 100083

基金項目:

國家自然科學基金資助項目 51871025

詳細信息

通訊作者:
朱金陽, E-mail: zhujinyang@ustb.edu.cn

中圖分類號: TG174.2
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出版歷程
- 收稿日期: 2018-12-24
- 刊出日期: 2019-05-01

Influence of KBr concentration on corrosion behaviors of 13Cr stainless steels under high temperature and high pressure

1.
National Center for Materials Service Safety, University of Science and Technology Beijing, Beijing 100083, China
2.
Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: ZHU Jin-yang, E-mail: zhujinyang@ustb.edu.cn

摘要

摘要: 油氣工業中溴鹽完井液的使用極易導致油套管腐蝕失效的發生, 尤其是局部腐蝕風險.針對這一問題, 采用高溫高壓腐蝕模擬試驗、掃描電鏡觀察與分析、電化學測試等試驗研究方法, 研究了高溫高壓環境下不同濃度溴鹽溶液對普通13Cr和超級13Cr兩種典型油套管材腐蝕行為的影響.結果表明: 從平均腐蝕速率來看, 兩種13Cr管材在三種濃度溴鹽溶液中均表現出較好的耐蝕性能, 屬于輕度或中度腐蝕, 但從局部腐蝕速率來看, 兩種材料均達到嚴重或極嚴重腐蝕; 隨著溴鹽濃度的提高, 普通13Cr的自腐蝕電位和點蝕電位均明顯負移, 對應材料的平均腐蝕速率和局部腐蝕速率均明顯上升, 而超級13Cr僅點蝕電位明顯負移, 自腐蝕電位則相對穩定, 對應其平均腐蝕速率變化幅度較小, 局部腐蝕速率則明顯上升, 這說明相比普通13Cr, 超級13Cr對溴鹽溶液具有更強的整體耐受能力, 但局部腐蝕敏感性仍然較高; 激光共聚焦(LSCM)三維表征結果表明, 在高質量濃度溴鹽溶液(1.40 g·cm^-3)中, 不論是普通13Cr還是超級13Cr都有明顯的點蝕傾向, 這主要與溶液中高濃度的侵蝕性陰離子Br^-有關, 相比于普通13Cr, 超級13Cr的點蝕敏感性相對較低, 但其點蝕風險仍不可忽視.
- 13Cr油套管 /
- 溴鹽完井液 /
- 高溫高壓 /
- 點蝕 /
- 動電位極化
Abstract: Recently, the use of bromine completion fluids in the oil and gas industry has caused numerous severe corrosion problems of the oil well casing and tubing, particularly the localized corrosion failure. Bromine completion fluids, such as KBr solution, are highly corrosive to steels. Even if the stainless steel is subjected to a high concentration of bromate under high temperature and pressure, it can still experience severe corrosion failure risks. In this study, the influence of KBr concentrations on corrosion behaviors of plain and super 13Cr steels under high temperature and pressure was investigated by corrosion simulation, scanning electron microscopy (SEM) observation, and electrochemical measurements. The results show that both plain and super 13Cr steels exhibit good corrosion resistance in KBr solutions with various concentrations regarding average corrosion rate, which is either mild or moderate. However, the local corrosion rates of plain and super 13Cr steels are serious or extremely serious. With the increase of bromide concentration, the free corrosion and pitting potentials of plain 13Cr steel significantly decrease. Both the average and local corrosion rates increase significantly. For super 13Cr steel, the pitting potential decreases, whereas the free potential remains relatively stable. The average corrosion rate of super 13Cr steel shows a lower scope of change than the local corrosion rate, which increases significantly and indicates that super 13Cr steel is much more corrosion resistant than plain 13Cr steel, but its local corrosion sensitivity is still high. Laser scanning confocal microscopy (LSCM) results show that both plain and super 13Cr steels exhibit serious pitting corrosion in a KBr solution with a concentration of 1.40 g·cm^-3, and this is related to the aggressiveness of Br^-. Compared with plain 13Cr steel, super 13Cr steel shows a lower pitting sensitivity; however, its pitting corrosion risk cannot be ignored.
- 13Cr oil casing /
- bromine completion fluid /
- high temperature and pressure /
- pitting corrosion /
- potentiodynamic polarization

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圖 1 高溫高壓腐蝕模擬試驗裝置

Figure 1. Autoclave used in corrosion simulation tests under high temperature and pressure

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圖 2 試驗所用的條形掛片試樣

Figure 2. Experimental sample used in corrosion simulation tests

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圖 3 普通13Cr和超級13Cr在不同濃度溴鹽溶液下腐蝕7 d后的腐蝕速率對比. (a) 平均腐蝕速率; (b) 最大局部腐蝕速率

Figure 3. Corrosion rates of plain and super 13Cr steels after seven days exposure in KBr solutions with different concentrations: (a) general corrosion rate; (b) maximum local corrosion rate

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圖 4 普通13Cr在不同質量濃度溴鹽溶液下腐蝕7 d后酸洗前(左)和酸洗后(右)的宏觀腐蝕形貌照片. (a, b) 1.01 g·cm^-3; (c, d) 1.10 g·cm^-3; (e, f) 1.40 g·cm^-3

Figure 4. Macro-photographs of plain 13Cr steel before (left) and after (right) cleaning after seven days exposure in KBr solutions with different concentrations: (a, b) 1.01 g·cm^-3; (c, d) 1.10 g·cm^-3; (e, f) 1.40 g·cm^-3

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圖 5 超級13Cr在不同質量濃度溴鹽溶液下腐蝕7 d后酸洗前(左)和酸洗后(右)的宏觀腐蝕形貌照片. (a, b) 1.01 g·cm^-3; (c, d) 1.10 g·cm^-3; (e, f) 1.40 g·cm^-3

Figure 5. Macro-photographs of super 13Cr steel before (left) and after (right) cleaning after seven days exposure in KBr solutions with different concentrations: (a, b) 1.01 g·cm^-3; (c, d) 1.10 g·cm^-3; (e, f) 1.40 g·cm^-3

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圖 6 普通13Cr在1.40 g·cm^-3溴鹽溶液下腐蝕7 d后的表面微觀形貌及三維形貌照片. (a) 表面形貌; (b) 三維形貌; (c) 蝕坑截面尺寸

Figure 6. D and 3D images of plain 13Cr steel after seven days exposure in a KBr solution with a concentration of 1.40 g·cm^-3: (a) surface morphology; (b) 3D topographic image; (c) depth profile of corrosion pit

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圖 7 普通13Cr在1.40 g·cm^-3溴鹽溶液下腐蝕7 d后蝕坑能譜測試結果

Figure 7. EDS result of the corrosion product in the corrosion pit on plain 13Cr steel after seven days exposure in a KBr solution with concentration of 1.40 g·cm^-3

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圖 8 超級13Cr在1.40 g·cm^-3溴鹽溶液下腐蝕7 d后的表面微觀形貌及三維形貌照片. (a) 表面形貌; (b) 三維形貌; (c) 蝕坑截面尺寸

Figure 8. 2D and 3D images of super 13Cr steel after seven days exposure in a KBr solution with concentration of 1.40 g·cm^-3: (a) surface morphology; (b) 3D topographic image; (c) depth profile of corrosion pit

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圖 9 超級13Cr在1.40 g·cm^-3溴鹽溶液下腐蝕7 d后蝕坑能譜測試結果

Figure 9. EDS result of the corrosion product in the corrosion pit on super 13Cr steel after seven days exposure in KBr solution with concentration of 1.40 g·cm^-3

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圖 10 普通13Cr在不同濃度溴鹽溶液下腐蝕7 d后的截面微觀形貌照片. (a) 1.01 g·cm^-3; (b) 1.10 g·cm^-3; (c) 1.40 g·cm^-3

Figure 10. Cross-sectional morphologies of plain 13Cr steel after seven days exposure in KBr solutions with different concentrations: (a) 1.01 g·cm^-3; (b) 1.10 g·cm^-3; (c) 1.40 g·cm^-3

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圖 11 超級13Cr在不同濃度溴鹽溶液下腐蝕7 d后的截面微觀形貌照片. (a) 1.01 g·cm^-3; (b) 1.10 g·cm^-3; (c) 1.40 g·cm^-3

Figure 11. Cross-sectional morphologies of super 13Cr steel after seven days exposure in KBr solutions with different concentrations: (a) 1.01 g·cm^-3; (b) 1.10 g·cm^-3; (c) 1.40 g·cm^-3

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圖 12 材料在不同質量濃度溴鹽溶液下的動電位極化曲線對比. (a) 普通13Cr; (b) 超級13Cr

Figure 12. Potentiodynamic polarization curves in KBr solutions with different concentrations: (a) plain 13Cr; (b) super 13Cr

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圖 13 普通13Cr和超級13Cr在不同濃度溴鹽溶液下的點蝕電位對比

Figure 13. Pitting potential plots of plain and super 13Cr steels in KBr solutions with different concentrations

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表 1 實驗所用的兩種13Cr不銹鋼材質成分(質量分數)

Table 1. Main chemical composition of the two kinds of 13Cr steels

材料	C	Cr	Ni	Mo	Si	Mn	P	S	V	Fe
普通13Cr	0.19	12.1			0.30	0.23	0.015	0.004	0.042	余量
超級13Cr	0.03	13.2	5.12	2.11	0.35	0.39	0.016			余量

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表 2 三種不同濃度的溴鹽溶液成分

Table 2. Chemical compositions of three test solutions with different concentrations

溶液密度/(g·cm^-3)	配置1 L溴鹽溶液
溶液密度/(g·cm^-3)	KBr質量/g	去離子水體積/L
1.01	10	1
1.10	100	1
1.40	400	1

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