Corrosion Behavior of 12Cr1MoVG Steel in a Simulated Flue Gas for High-chlorine Coal while Containing Different Forms of Chlorine

doi:10.11901/1005.3093.2025.354

Chinese Journal of Materials Research

2026, Vol. 40

Issue (9): 697-709 DOI: 10.11901/1005.3093.2025.354

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Corrosion Behavior of 12Cr1MoVG Steel in a Simulated Flue Gas for High-chlorine Coal while Containing Different Forms of Chlorine

GUO Feifan¹, MA Jigang¹, CHEN Lijuan¹^,²(

), XIE Weizhi¹, WEI Bo¹^,²(

), MA Rui³, AN Tiantian¹, LI Yihua¹, LI Xinyue¹

^1.School of Chemical Engineering, Xinjiang University, Urumqi 830017, China
^2.Xinjiang Key Laboratory of Clean Coal Conversion and Chemical Processes, Urumqi 830017, China
^3.School of Electrical Engineering, Xinjiang University, Urumqi 830017, China

Cite this article:

GUO Feifan, MA Jigang, CHEN Lijuan, XIE Weizhi, WEI Bo, MA Rui, AN Tiantian, LI Yihua, LI Xinyue. Corrosion Behavior of 12Cr1MoVG Steel in a Simulated Flue Gas for High-chlorine Coal while Containing Different Forms of Chlorine. Chinese Journal of Materials Research, 2026, 40(9): 697-709.

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Abstract

The flue gas generated from combustion of high-chlorine containing coals may induce severe corrosion on boiler heat exchanger tubes due to chlorine-containing species, significantly compromising the operational safety. Herein the high-temperature corrosion behavior of boiler steel 12Cr1MoVG was investigated in flue gas containing different chlorine species. For this purpose, a high-temperature corrosion test rig was established to simulate the flue gas environment (Cl₂/HCl + CO₂ + H₂O + N₂, 550 ^oC/650 ^oC) in boilers firing high-chlorine coal while containing different forms of chlorine. The corrosion behavior of the steel was characterized by means of mass loss measurement, SEM-EDS, XRD, and thermodynamic calculations. The results revealed that temperature significantly influences material corrosion. When temperature increased from 550 ^oC to 650 ^oC, oxide scale thickness increased by 232.4 µm with a corresponding mass loss increase of 21.26 mg/cm². Microcracks developed in the surface oxide scale due to thermal stress. Under identical conditions, Cl₂ induced more severe corrosion than HCl. When the corrosion of steel in artificial flue gas containing HCl may generate volatile FeCl₂, whose sublimation created porous pathways allowing HCl penetration through the oxide scale to react with the steel substrate, simultaneously inducing transverse and longitudinal cracks. In contrast, when exposure to ones containing Cl₂ the steel corrosion could induce the formation of FeCl₃, which volatilizes at lower temperatures, producing dense porosity that facilitated inward chlorine diffusion and subsequent reaction with the steel substrate, ultimately causing severe oxide scale delamination and spallation. Chlorine-induced high-temperature corrosion of the steel follows an autocatalytic cycle: HCl/Cl₂ reacts with the steel to form volatile iron chlorides (FeCl₂/FeCl₃). These compounds volatilize and undergo oxidation with H₂O, regenerating HCl to sustain the corrosive cycle. This process ultimately leads to metallic oxide scale degradation through delamination and spallation. The stronger oxidizing capability of Cl₂ and higher volatility of its corrosion products result in more severe material degradation compared to HCl.

Key words: metallic materials high-temperature corrosion chlorine corrosion high-chlorine coal combustion 12Cr1MoVG

Received: 27 November 2025

ZTFLH:

TG172

Fund: Program for Research Innovation Capabilities of Young Faculty Members in Higher Education Institutions(SRICSPYF-BS2025042);National Natural Science Foundation of China(52261022);2025 National Undergraduate Innovation Training Program(202510755044)

Corresponding Authors: CHEN Lijuan, Tel: 18016827217, E-mail: ljchenxju@163.com;
WEI Bo, Tel: 18703028892, E-mail: weiboxju@163.com

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	Articles by authors
	GUO Feifan
	MA Jigang
	CHEN Lijuan
	XIE Weizhi
	WEI Bo
	MA Rui
	AN Tiantian
	LI Yihua
	LI Xinyue

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https://www.cjmr.org/EN/10.11901/1005.3093.2025.354 OR https://www.cjmr.org/EN/Y2026/V40/I9/697

Table 1 Chemical composition and content of 12Cr1MoVG steel (mass fraction, %)

Fig.1 Schematic diagram of a controlled atmosphere high-temperature corrosion test bench

Table 2 Experimental conditions and composition (volume fraction, %)

Fig.2 Mass loss of 12Cr1MoVG steel after corrosion in N₂, HCl, and Cl₂ atmospheres at 550 ^oC and 650 ^oC for 100 h

Fig.3 Macroscopic morphologies of 12Cr1MoVG steel after corrosion in N₂ (a1, a4, b1, b4), HCl (a2, a5, b2, b5), and Cl₂ (a3, a6, b3, b6) atmospheres at 550 ^oC (a1-a6) and 650 ^oC (b1-b6) for 20 h (a1-a3, b1-b3) and 100 h (a4-a6, b4-b6)

Fig.4 Microstructural morphologies of 12Cr1MoVG steel after corrosion in N₂ (a, b), HCl (c, d), and Cl₂ (e, f) atmospheres at 550 ^oC (a, c, e) and 650 ^oC (b, d, f) for 100 h

Fig.5 XRD patterns of 12Cr1MoVG steel after corrosion in N₂, HCl, and Cl₂ atmospheres at 550 ^oC (a) and 650 ^oC (b) for 100 h

Fig.6 Micro-element distribution in cross-sections of 12Cr1MoVG steel after corrosion in N₂ (a), HCl (b), and Cl₂ (c) atmospheres at 550 ^oC for 100 h

Fig.7 Micro-element distribution in cross-sections of 12Cr1MoVG steel after corrosion in N₂ (a), HCl (b), and Cl₂ (c) atmospheres at 650 ^oC for 100 h

Fig.8 Line scan of the cross-section of 12Cr1MoVG steel after corrosion in N₂ (a), HCl (b), and Cl₂ (c) atmospheres at 550 ^oC for 100 h

Fig.9 Line scan of the cross-section of 12Cr1MoVG steel after corrosion in N₂ (a), HCl (b), and Cl₂ (c) atmospheres at 650 ^oC for 100 h

Fig.10 Thermodynamic parameters of reactions of Fe Cr, Mn, and V with H₂O (a), HCl (b),Cl₂ (c) and MCl _x with H₂O (d) in the temperature range of 450 ^oC to 750 ^oC

Table 3 Melting points and saturated vapor pressures of iron, chromium, and manganese chlorides

Fig.11 High-Temperature Corrosion Mechanism of 12Cr1MoVG steel in HCl (a) and Cl₂ (b) environments

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