Effect of Water Content on Corrosion Behavior of X65 Pipeline Steel in Supercritical CO2 Fluids

doi:10.11902/1005.4537.2023.227

Journal of Chinese Society for Corrosion and protection

2024, Vol. 44

Issue (3): 576-584 DOI: 10.11902/1005.4537.2023.227

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Effect of Water Content on Corrosion Behavior of X65 Pipeline Steel in Supercritical CO₂ Fluids

HU Lihua¹, YI Hualei¹, YANG Weijian², SUN Chong², SUN Jianbo²(

)

1. CNOOC Research Institute Co., Ltd., Beijing 100028, China
2. School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China

Cite this article:

HU Lihua, YI Hualei, YANG Weijian, SUN Chong, SUN Jianbo. Effect of Water Content on Corrosion Behavior of X65 Pipeline Steel in Supercritical CO₂ Fluids. Journal of Chinese Society for Corrosion and protection, 2024, 44(3): 576-584.

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Abstract

CO₂ induced pipeline corrosion is one of main concerns for the safe implementation and large-scale application of Carbon Capture, Utilization and Storage (CCUS) technology. Reasonably limiting the water content in supercritical CO₂ transport environments containing multiple impurities is crucial for the corrosion control of the pipeline. Herein, the effect of water content on the corrosion behavior of X65 pipeline steel in supercritical CO₂ transport environments with/without impurities of O₂, H₂S, SO₂ and NO₂ was investigated by means of simulated corrosion test with high-temperature and high-pressured autoclave, and surface analysis technology. Concurrently, the influence mechanism of impurities on the corrosion of the steel in supercritical CO₂ transport environments with different water contents was discussed. The results show that X65 steel only undergoes slight corrosion in supercritical CO₂-H₂O environment even if the water content reaches a saturated solubility of 0.4114%, and the corrosion rate is 0.0013 mm/a. However, when O₂, H₂S, SO₂and NO₂ coexist in supercritical CO₂-H₂O environment, the corrosion rate of X65 steel increases from 0.0181 mm/a to 0.2901 mm/a as the water content varies from 0.002% to 0.4114%. The impurities and their interactions significantly promote the formation of corrosive aqueous phase, therefore exacerbating the corrosion of X65 steel. The corrosion process of X65 steel in the environment with low water content is controlled by the products of impurity reactions, whereas the impurities and the products of impurity reactions jointly dominate the corrosion process of the steel in the environment with high water content.

Key words: X65 pipeline steel supercritical CO₂ water content impurity corrosion

Received: 18 July 2023 32134.14.1005.4537.2023.227

ZTFLH:

TG178

Fund: Major Scientific Research Program of CNOOC During the 14th Five-Year Plan Period(KJGG-2022-12-CCUS-0103)

Corresponding Authors: Sun Jianbo, E-mail: sunjianbo@upc.edu.cn

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https://www.jcscp.org/EN/10.11902/1005.4537.2023.227 OR https://www.jcscp.org/EN/Y2024/V44/I3/576

Fig.1 Schematic diagram of the apparatus for the corrosion test

Table 1 Test conditions

Fig.2 Variations of corrosion rates of X65 steel with water content in supercritical CO₂-H₂O environments without (a) and with (b) impurities

Fig.3 Macroscopic and microscopic surface morphologies of X65 steel exposed to supercritical CO₂-H₂O environments containing 0.05% H₂O (a), 0.2% H₂O (b) and 0.4114% H₂O (c) for 72 h

Fig.4 Macroscopic and microscopic surface morphologies of X65 steel exposed to supercritical CO₂-H₂O-impurity environments containing 0.002% H₂O (a), 0.01% H₂O (b), 0.05% H₂O (c), 0.1% H₂O (d), 0.2% H₂O (e) and 0.4114% H₂O (f) for 72 h

Table 2 EDS analysis results of corrosion products in the areas denoted by A~F in Fig.4 (atomic fraction / %)

Fig.5 Cross-sectional backscattered electron images and corresponding element mappings of X65 steel exposed to supercritical CO₂-H₂O-impurity environments containing 0.002% H₂O (a), 0.01% H₂O (b), 0.05% H₂O (c), 0.1% H₂O(d), 0.2% H₂O (e) and 0.4114% H₂O (f) for 72 h

Fig.6 XRD patterns of X65 steel exposed to supercritical CO₂-H₂O-impurity environments containing different contents of water for 72 h

Fig.7 High-resolution XPS spectra of various elements in corrosion products formed on X65 steel exposed to supercritical CO₂-H₂O-imuprity environments with impurities for 72 h (the binding energy was calibrated by 284.8 eV of C 1s peak for residual carbon): (a) 0.05% H₂O, (b) 0.1% H₂O, (c) 0.2% H₂O

Element	0.2% H₂O		0.1% H₂O		0.05% H₂O
Element	Binding energy eV	Fitted species	Binding energy eV	Fitted species	Binding energy eV	Fitted species
Fe 2p	710.8	FeSO₄^[20]	710.8	FeSO₄^[20]	711.3	FeSO₄^[20]
	712.2	FeSO₄^[21]	712.2	FeSO₄^[21]	713.6	FeSO₄^[22]
	724.5	FeOOH^[23]	724.5	FeOOH^[23]	725.3	FeOOH^[23]
O 1s	530.1	FeOOH^[24]	529.7	FeOOH^[25]	530.2	FeOOH^[23]
	531.5	FeOOH^[20]	531.7	FeOOH^[25]	531.8	FeOOH^[26]
	532.2	FeSO₄^[21]	533.7	SO $4 2 -$ ^[27]	532.3	FeSO₄^[28]
S 2p	163.7	S^[29]	164.0	S^[30]	-	-
	167.1	SO $3 2 -$ ^[21]	168.7	FeSO₄^[28]	168.7	FeSO₄^[28]
	168.6	FeSO₄^[21]	-	-	-	-

Table 3 Fitting binding energies of Fe 2p, O 1s, and S 2p and the corresponding compounds based on XPS spectra of corrosion products of X65 steel in Fig. 7

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