X80管线钢的气相氢扩散、氢吸收及氢捕获特性

Gaseous hydrogen diffusion, hydrogen absorption and hydrogen trapping characteristics of X80 pipeline steel

摘要

高强度、大口径、高压力输氢管道已成为发展趋势,但其潜在的氢致开裂风险严重挑战了服役安全;氢在管材中的渗透扩散特性是导致氢致开裂的前置环节,理解材料在气相氢环境下的渗透行为至关重要。基于原位气相氢渗透实验装置,研究输氢管道X80钢的氢渗透特性,采用连续充放氢方法分析氢渗透的瞬态过程,准确计算有效氢扩散系数及亚表面吸附氢浓度,明确可逆氢、不可逆氢和晶格氢在渗透过程中的占比,并探讨显微组织对氢渗透的影响。结果表明:不可逆氢陷阱显著影响初次渗透,但不影响后续渗透瞬态;X80钢在20%掺氢比下的有效氢扩散系数约为1.72×10^-6 cm²/s,其氢捕获行为与显微组织直接相关,细晶组织和高小角度晶界占比导致X80钢可扩散氢含量较高,这是X80钢高氢脆敏感性的重要原因之一。

Abstract

High-strength, large-diameter, high-pressure hydrogen pipelines have become a prevailing development trend, but the potential risk of hydrogen-induced cracking poses a significant challenge to operational safety. The permeation and diffusion characteristics of hydrogen within pipeline materials constitute the precursor to hydrogen-induced cracking, making it crucial to understand the permeation behavior of materials in gaseous hydrogen environments. This study utilized an in-situ gaseous hydrogen permeation apparatus to investigate the hydrogen permeation characteristics of X80 steel used in hydrogen pipelines. Employing a continuous hydrogen charging and discharging method, the transient process of hydrogen permeation was analyzed. The effective hydrogen diffusion coefficient and subsurface adsorbed hydrogen concentration were accurately calculated. The proportions of reversible hydrogen, irreversible hydrogen, and lattice hydrogen during the permeation process were clarified, and the influence of microstructure on hydrogen permeation was explored. Results indicate that irreversible hydrogen traps significantly influence the initial permeation, but do not affect the subsequent transient permeation. At a hydrogen content of 20%, the effective hydrogen diffusion coefficient for X80 steel is approximately 1.72×10 ^-6 cm ²/s, and the hydrogen trapping behavior is directly correlated with microstructure. The fine-grained structure and high proportion of low-angle grain boundaries result in a high content of diffusible hydrogen in X80 steel, which is one of the important reasons for the high hydrogen embrittlement sensitivity of X80 steel.

关键词

氢气管道 / X80钢 / 氢渗透 / 氢吸收 / 氢捕获

Key words

hydrogen pipelines / X80 steel / hydrogen permeation / hydrogen absorption / hydrogen trapping

参考文献

[1] 杨永飞, 尚振骁, 秦朝中, 等 . 地下大规模储氢的挑战与发展前景[J]. 中国石油大学学报(自然科学版), 2024, 48(6): 95-104.

[2] YANG Yongfei, SHANG Zhenxiao, QIN Chaozhong, et al. Challenges and development prospects of large-scale underground hydrogen storage[J]. Journal of China University of Petroleum(Edition of Natural Science), 2024, 48(6): 95-104.

[3] 杨东海, 孙雅倩, 田磊, 等 . 天然气管道掺氢装置及混合特性[J]. 中国石油大学学报(自然科学版), 2025, 49(1): 178-184.

[4] YANG Donghai, SUN Yaqian, TIAN Lei, et al. Investigation on hydrogen blending devices and mixing characteristics of natural gas pipeline[J]. Journal of China University of Petroleum (Edition of Natural Science), 2025, 49(1): 178-184.

[5] 赵云松, 付盼, 王江帅, 等 . 盐穴储氢库老井封堵水泥塞-地层界面剥离失效模拟[J]. 石油机械, 2025, 53(9): 79-85.

[6] ZHAO Yunsong, FU Pan, WANG Jiangshuai, et al. Cement plug-formation interface debonding failure modeling for plugged back old well in salt cavern hydrogen storage[J]. China Petroleum Machinery, 2025, 53(9): 79-85.

[7] 中国世界石油理事会国家委员会. 推动能源领域科技创新 引领中国新型能源体系建设[J]. 世界石油工业, 2024, 31(1): 1-5.

[8] Chinese National Committee for the World Petroleum Council. Promote energy innovation while pioneering the development of China's new energy system[J]. World Petroleum Industry, 2024, 31(1): 1-5.

[9] 孙龙德, 张鹏程, 江航, 等 . 油气安全与能源转型的新趋势[J]. 世界石油工业, 2024, 31(1): 6-15.

[10] SUN Longde, ZHANG Pengcheng, JIANG Hang, et al. New trends in oil and gas security and energy transition[J]. World Petroleum Industry, 2024, 31(1): 6-15.

[11] 张家轩, 王财林, 刘翠伟, 等 . 掺氢天然气环境下管道钢氢脆行为研究进展[J]. 表面技术, 2022, 51(10): 76-88.

[12] ZHANG Jiaxuan, WANG Cailin, LIU Cuiwei, et al. Research progress on hydrogen embrittlement behavior of pipeline steel in the environment of hydrogen-blended natural gas[J]. Surface Technology, 2022, 51(10): 76-88.

[13] WITKOWSKI A, RUSIN A, MAJKUT M, et al. Analysis of compression and transport of the methane/hydrogen mixture in existing natural gas pipelines[J]. International Journal of Pressure Vessels and Piping, 2018, 166: 24-34.

[14] XU Xiusai, WANG Yan, WANG Cailin, et al. FeCO₃ corrosion product films as hydrogen barrier for pipelines transporting hydrogen: Insight from hydrogen dissociative adsorption and permeation [J]. Applied Surface Science, 2026, 715: 164489.

[15] 王意东, 张建平, 王晓东, 等 . 川渝地区氢能产业发展现状及策略[J]. 世界石油工业, 2025, 32(4): 58-65.

[16] WANG Yidong, ZHANG Jianping, WANG Xiaodong, et al. Current situation and strategies of hydrogen energy industry development in Sichuan and Chongqing[J]. World Petroleum Industry, 2025, 32(4): 58-65.

[17] 程玉峰. 高压氢气管道氢脆问题明晰[J]. 油气储运, 2023, 42(1): 1-8.

[18] CHENG Yufeng. Essence and gap analysis for hydrogen embrittlement of pipelines in high-pressure hydrogen environments[J]. Oil & Gas Storage and Transportation, 2023, 42(1): 1-8.

[19] 李玉星, 宁元星, 刘翠伟, 等 . 20号钢环焊缝中夹杂物对氢扩散行为影响[J]. 中国石油大学学报(自然科学版), 2024, 48(5): 160-167.

[20] LI Yuxing, NING Yuanxing, LIU Cuiwei, et al. Effects of inclusions in steel 20 girth weld on hydrogen diffusion behaviors[J]. Journal of China University of Petroleum (Edition of Natural Science), 2024, 48(5): 160-167.

[21] 吴瑕, 滕孟君, 贾文龙, 等 . 掺氢天然气管道用钢力学性能劣化研究进展及建议[J]. 世界石油工业, 2025, 32(2): 110-119.

[22] WU Xia, TENG Mengjun, JIA Wenlong, et al. Research status and suggestions of mechanical properties degradation of hydrogen-blended natural gas pipeline steel[J]. World Petroleum Industry, 2025, 32(2): 110-119.

[23] 曹敏, 汤历平, 王锡军, 等 . 长输油气管道环向表面裂纹扩展特性研究[J]. 石油机械, 2024, 52(12): 125-133.

[24] CAO Min, TANG Liping, WANG Xijun, et al. Propagation characteristics of circumferential surface cracks in long distance oil and gas pipelines[J]. China Petroleum Machinery, 2024, 52(12): 125-133.

[25] HOU Jie, KONG Xiangshan, WU Xuebang, et al. Predictive model of hydrogen trapping and bubbling in nanovoids in bcc metals[J]. Nature Materials, 2019, 18(8): 833-839.

[26] HUANG Longchao, CHEN Dengke, XIE Degang, et al. Quantitative tests revealing hydrogen-enhanced dislocation motion in α-iron[J]. Nature Materials, 2023, 22(6): 710-716.

[27] BEHVAR A, HAGHSHENAS M, DJUKIC M B . Hydrogen embrittlement and hydrogen-induced crack initiation in additively manufactured metals: a critical review on mechanical and cyclic loading[J]. International Journal of Hydrogen Energy, 2024, 58: 1214-1239.

[28] MARTÍNEZ-PAÑEDA E, DÍAZ A, WRIGHT L, et al. Generalized boundary conditions for hydrogen transport at crack tips[J]. Corrosion Science, 2020, 173: 108698.

[29] DEVANATHAN M A V, STACHURSKI Z . The adsorption and diffusion of electrolytic hydrogen in palladium[J]. Proceedings of the Royal Society of London Series A: Mathematical and Physical Sciences, 1962, 270(1340): 90-102.

[30] WANG Cailin, ZHANG Jiaxuan, LIU Cuiwei, et al. Study on hydrogen embrittlement susceptibility of X80 steel through in-situ gaseous hydrogen permeation and slow strain rate tensile tests[J]. International Journal of Hydrogen Energy, 2023, 48(1): 243-256.

[31] KOREN E, HAGEN C M H, WANG D, et al. Experimental comparison of gaseous and electrochemical hydrogen charging in X65 pipeline steel using the permeation technique[J]. Corrosion Science, 2023, 215: 111025.

[32] 常庆刚, 陈业新. 氢在20 g纯净钢中的扩散研究[J]. 上海金属, 2010, 32(6): 35-38.

[33] CHANG Qinggang, CHEN Yezin. Diffusivity of hydrogen in 20 g clean steel[J]. SHANHAI METALS, 2010, 32(6): 35-38.

[34] 李勇峰, 蔡丽安, 阚文彬, 等 . 氢在低碳钢中的渗透扩散特性[J]. 华东理工大学学报(自然科学版), 2013, 39(2): 222-227.

[35] LI Yongfeng, CAI Lian, KAN Wenbin, et al. Diffusion characteristics of hydrogen in low carbon steel[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2013, 39(2): 222-227.

[36] 冯耀荣, 吉玲康, 李为卫, 等 . 中国X80管线钢和钢管研发应用进展及展望[J]. 油气储运, 2020, 39(6): 612-622.

[37] FENG Yaorong, JI Lingkang, LI Weiwei, et al. Progress and prospects of research and application of X80 pipeline steel and steel pipe in China[J]. Oil & Gas Storage and Transportation, 2020, 39(6): 612-622.

[38] ZHAO Weimin, ZHANG Timing, ZHAO Yujiao, et al. Hydrogen permeation and embrittlement susceptibility of X80 welded joint under high-pressure coal gas environment[J]. Corrosion Science, 2016, 111: 84-97.

[39] ZHENG Shi, ZHOU Guijuan, CHEN Shuhui, et al. Effect of stress and strain on hydrogen permeation process in X80 pipeline steel[J]. Corrosion Science, 2025, 251: 112934.

[40] ZHANG Lei, SHEN Hongjie, SUN Junyan, et al. Effect of calcareous deposits on hydrogen permeation in X80 steel under cathodic protection[J]. Materials Chemistry and Physics, 2018, 207: 123-129.

[41] 宁元星, 刘翠伟, 李玉星, 等 . 长周期临氢服役管材适应性评价[J]. 油气储运, 2024, 43(10): 1118-1128.

[42] NING Yuanxing, LIU Cuiwei, LI Yuxing, et al. Evaluation on pipeline steel adaptability for extended hydrogen-contacting service[J]. Oil & Gas Storage and Transportation, 2024, 43(10): 1118-1128.

[43] XU Xiusai, ZHU Mengze, WANG Cailin, et al. Effect of FeCO₃ corrosion product scale on hydrogen adsorption and permeation of pipeline steel in gaseous hydrogen-blended natural gas transportation [J]. Corrosion Science, 2024, 229: 111880.

[44] XU Xiusai, ZHANG Rui, WANG Cailin, et al. Experimental study on the temperature dependence of gaseous hydrogen permeation and hydrogen embrittlement susceptibility of X52 pipeline steel[J]. Engineering Failure Analysis, 2024, 155: 107746.

[45] ZHANG Rui, YUAN Chen, LIU Cuiwei, et al. Experimental and molecular dynamics study of the hydrogen embrittlement behavior of X52 steel: analysis of abnormal hydrogen embrittlement susceptibility[J]. International Journal of Hydrogen Energy, 2024, 83: 987-1002.

[46] MCBREEN J, NONIS L, BECK W . A method for determination of the permeation rate of hydrogen through metal membranes[J]. Journal of the Electrochemical Society, 1966, 113(11): 1218.

[47] YEN S K, HUANG I B . Critical hydrogen concentration for hydrogen-induced blistering on AISI 430 stainless steel[J]. Materials Chemistry and Physics, 2003, 80(3): 662-666.

[48] KIUCHI K, MCLELLAN R B . The solubility and diffusivity of hydrogen in well-annealed and deformed iron[J]. Acta Metallurgica, 1983, 31(7): 961-984.

[49] WU E. A mathematical treatment of the electrochemical method of hydrogen permeation and its application in hydrogen traps and embrittlement[J]. Journal of the Electrochemical Society, 1987, 134(9): 2126-2133.

[50] SEZGIN J G, BOSCH C, MONTOUCHET A, et al. Modelling of hydrogen induced pressurization of internal cavities[J]. International Journal of Hydrogen Energy, 2017, 42(22): 15403-15414.

基金资助

国家重点研发计划项目(2024YFE0211500)