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Study on the damage mechanism of high chromia refractory in the slag tapping hole of commercial entrained-flow gasifier
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Baozi PENG1, *, Zhen LIU1, Jin BAI2, Huaizhu LI2, Kaidi SUN1, Haiquan AN1, Jun LI1
Journal of Fuel Chemistry and Technology | 2026, 54(3) : 20250193-524 - 20250193-533
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Journal of Fuel Chemistry and Technology | 2026, 54(3): 20250193-524-20250193-533
• RESEARCH PAPER •
Study on the damage mechanism of high chromia refractory in the slag tapping hole of commercial entrained-flow gasifier
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Baozi PENG1, *, Zhen LIU1, Jin BAI2, Huaizhu LI2, Kaidi SUN1, Haiquan AN1, Jun LI1
Affiliations
  • 1National Institute of Clean-and-Low-Carbon Energy, Beijing 102209, China
  • 2State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
Published: 2026-03-10 doi: 10.1016/S1872-5813(25)60600-1
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The service life of refractory brick in the slag tapping hole of gasifiers is a significant concern for long-term and stable operation. This study examined the damage mechanism of high chromia refractory of four commercial coal-water slurry gasifiers with their corresponding gasification coal samples and the corroded refractory bricks in the slag tapping hole of the gasifier. The slag characteristic, including crystallization and viscosity-temperature of four gasification coal samples were analyzed. The results revealed that the low viscosity slag could lead to more severe damage to refractory bricks. Given the risk of slag crystallization, it is recommended to establish a safe slag tapping temperature range should be set as tICT (initial crystallization temperature) − t2.5 when tICT is higher than t25. Upon examining interior morphology of these corroded refractory bricks, some cracks were observed within them. The chemical composition of molten slag was analyzed using SEM-EDS. However, XRD results found no spinel containing zirconium in these cracks. This suggests that the emergence of these cracks are mainly attributed to the molten slag penetration and the subsequent reaction with the refractory material. The difference in thermal expansion between the newly formed substances and refractory material is critical in forming these cracks. Furthermore, SEM-EDS analysis was also conducted on the slag-aggregate and the slag-matrix interface. The results reveal that the reduction in Cr2O3 content is the earliest characteristic of damage in high chromia refractories. A proposed damage mechanism of refractory brick suggests that the matrix and aggregate of high chromia refractory are initially compromised because of the reduced Cr2O3 content. Subsequently, the molten slag penetrates the interior of the refractory brick, forming new substances, leading to damage caused by the difference in thermal expansion between the new substances and the refractory brick. Understanding and preventing the reduction of Cr2O3 content is vital to prolonging the service life of refractory brick in the slag tapping hole of the gasifier based on this damage mechanism.

gasification  /  high chromia refractory  /  slag  /  damage mechanism  /  corrosion
彭宝仔, 刘臻, 白进, 李怀柱, 孙凯蒂, 安海泉, 李君. 工业气流床气化炉渣口高铬砖损毁机理研究. 燃料化学学报（中英文）, 2026 , 54 (3) : 20250193-524 -20250193-533 . DOI: 10.1016/S1872-5813(25)60600-1
Baozi PENG, Zhen LIU, Jin BAI, Huaizhu LI, Kaidi SUN, Haiquan AN, Jun LI. Study on the damage mechanism of high chromia refractory in the slag tapping hole of commercial entrained-flow gasifier[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (3) : 20250193-524 -20250193-533 . DOI: 10.1016/S1872-5813(25)60600-1
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Entrained-flow gasification is considered one of the most efficient and environmentally benign processes, converting mixtures of carbon-based materials like coal, biomass, and petroleum coke into syngas[1−2]. Entrained-flow gasifiers are categorized into refractory brick walls and water-cooling membrane wall based on the lining of the gasifier chamber[3−4]. Refractory brick lining gasifier exhibits low radial heat flux and a high conversion efficiency due to its excellent thermal insulation performance[5−6]. However, the service life of refractory brick is a bottleneck for long-term and stable operation of the gasifier[3], particularly for refractory bricks located in the slag tapping hole of the gasifier. The service life of refractory bricks varies significantly across different areas within a gasifier. In commercial gasifiers, the refractory brick service life in the slag tapping hole is approximately half that of the straight section[5,7].
Many researchers have explored the damage mechanism of refractory bricks by the experimental method under simulated gasification conditions, focusing on the corrosion effect of different types of slag[8−14]. Kaneko et al.[15] studied the corrosion mechanism of various slags (coal slag and petroleum coke slag) on 90%Cr2O3-10%Al2O3 refractory material, which showed that the chromium spinel layers hindered the slag from penetrating the porous microstructure of the refractory, thus limiting infiltration. Kwong et al.[16] reported that iron oxide in the melting furnace slag preferentially reacts with chromium oxide to form iron chromium spinel, which the continuous growth of FeCr2O4 in a limited space resulted in the flaking of fine particles on the surface of refractory materials. Chen et al.[17] examined the corrosion characteristics of Cr2O3-Al2O3-ZrO2 refractory brick in a coal-water slurry gasifier, and the result showed the formation of an isolation layer primarily composed of (Mg, Fe2+)(Cr, Fe)2O4 complex spinel effectively inhibited the infiltration of key corrosive components in the slag (FexO, MgO). Additionally, Cai et al.[18−19] studied the corrosion properties of acidic and alkaline slag on various refractory materials, and founded that a (Mg, Fe)(Al, Cr)2O4 spinel solution formed in the reaction layer, resulting in a densification of the matrix structure. ZrO2 in the matrix dissolved directly into the molten slag and forming a ZrO2-free region that reduced the thermal shock resistance of refractory bricks.
The research mentioned above suggests that the damage mechanism of refractory bricks is highly complex, influenced by factors such as temperature fluctuation, slag characteristics, and the properties of the refractory material. However, most of the research on the damage mechanism of refractory bricks were carried out by the experimental method and focus only to the surface corrosion of refractory bricks. Therefore, the precise nature of the damage mechanism of refractory bricks remains unclear. This study selected four commercial coal-water slurry gasifiers as the focus. The four gasification coal samples and their corresponding to refractory bricks from the slag tapping hole of the gasifier were collected to investigate the damage characteristic of refractory bricks. By combining the slag characteristic and the analysis of corroded refractory brick with an understanding of slag characteristics, this study aims to gain insight into the damage mechanism and ultimately improve the service life of refractory brick of the gasifier.
1　Experimental
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1.1　Sample preparation
Gasification coal samples (No.1#−4#) from each gasifier and the corresponding corroded refractory bricks from the slag tapping hole were collected. The coal ash was prepared at 815 ℃ in a muffle furnace according to GB/T 1574—2007 standards. The chemical compositions of ash were analyzed using X-ray fluorescence (XRF) (Bruker S8 Tiger, Germany), and are presented in Table 1.
The data in Table 1 reveals that the acidic characteristic (SiO2, Al2O3 and TiO2) is more pronounced than the alkaline characteristic (Fe2O3, CaO, MgO, K2O and Na2O) across all samples, which indicate that coal with acidic/alkaline ratio greater than one is more suitable for coal water slurry gasification. Upon comparison, it is notable that the iron oxide content is relatively higher in coal samples 3# and 4#, while the 4# coal sample content of CaO is the highest.
1.2　Analysis of coal samples and corroded refractory bricks
The viscosity of coal ash was measured using a Theta high-temperature rotating viscometer (Theta Industries, Inc., USA) with molybdenum rotors and crucibles. The measurement process was detailed in the report by Cao et al.[20]. The crystallization process of molten slag was monitored by using the single hot thermocouple technique (SHTT), as reported by Lu et al.[21]. The microstructure of the corroded refractory brick in the slag tapping hole was longitudinally cut and analyzed using a Scanning Electron Microscope (SEM) with X-ray Energy Dispersive Spectroscopy (EDS). Mineralogical analysis was performed using an X-ray powder diffract meter (BRUKER D8, Germany), equipped with Cu Kα radiation (40 kV, 40 mA). The powder samples were mounted on a sample glass and scanned with a step size of 0.02° over a 2θ range of 0.2°−120°.
1.3　Thermodynamic equilibrium calculations
Equilib-module in FactSage (version 8.3) was used for calculating phase distribution under a reducing atmosphere (CO/CO2 = 60∶40, volume fraction) from 1300 to 1000 ℃ via 20 ℃. The FactPS and FToxid databases were used for these calculations.
2　Results and discussion
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2.1　Slag characteristic analysis
The crystallization behavior of slag is vital for efficient operation of gasifier and for preventing refractory brick corrosion. Typically, the operation temperature of the gasifier should exceed the slag crystallization temperature to ensure smooth slag tapping. To analyze the slag crystallization characteristics of four coal samples used in gasification, the SHTT method was used to measure their crystallization behavior, and the results are illustrated in Figure 1.
Figure 1 reveals that both 1# and 2# coal samples did not exhibit crystallization behavior even at 1000 ℃. However, crystallization behavior was observed for 3# and 4# coal samples (as shown by the blue circle in the (c-3), (c-4) and (d-3) of Figure 1). In the crystallization process of 4# coal sample, crystallization accelerated as the temperature decreased, and quickly spread over the molten slag surface. The tICT (initial crystallization temperature) of 3# and 4# coal samples observed by the SHTT were 1044 and 1174 ℃, respectively. Additionally, the phase distribution of four gasification coal samples at thermodynamic equilibrium conditions under a weak reducing atmosphere was calculated by using the FactSage software packages 8.3 and is presented in Figure 2.
Figure 2 reveals that the thermodynamic liquid phase temperature of the 1#−4# coal samples are 1245.6, 1267.0, 1196.8 and 1198.8 ℃, respectively. As the temperature decreases, crystalline formations appear in the molten slag. The initial crystallization phase for 1#−3# coal samples are anorthite and gehlenite for 4# coal sample. The difference in the crystallization phases for the 4# coal sample compared to the others may be because of the high calcium content and the low crystallization activation energy of gehlenite[22]. As the temperature decreases further, different types crystallization are formed in each coal sample. However, according to Figure 1, the crystallization process of the 1# and 2# coal samples was not observed. It can be observed from Figure 2 that the slope of the liquidus line for 1# and 2# coal samples is smaller than that of 3# and 4# coal samples, indicating the need for a larger thermodynamic driving force for crystallization. This may explain why the crystallization process of the 1# and 2# coal samples was not observed. The viscosity-temperature curves of different slags were also measured and depicted in Figure 3.
Figure 3 reveals that the 1# and 2# coal samples exhibited the behavior of a glassy slag, whereas 3# and 4# coal samples have behavior typical of crystalline slag.
Furthermore, the range of slag tapping temperature range is a vital parameter for selecting gasification feedstock to ensure smooth tapping, and the ideal viscosity range of slag is 2.5−25 Pa·s[21]. Table 2 displays the corresponding temperature range of 2.5−25 Pa·s and tICT for 1#−4# coal samples.
Table 2 reveals that the tICT of 4# coal sample surpasses that of t25, whereas the tICT of 3# coal sample is lower than that of t25. In the context of a commercial gasifier, even if the slag is in a flowable, the slag crystallization poses a significant risk to the operation of a gasifier state. Therefore, it is recommended to establish the safe slag tapping temperature range should be set as tICT−t2.5 when tICT exceeds t25. Furthermore, the temperatures of 3# and 4# coal samples at which the slag viscosity was 2.5 Pa·s are excessively low, this may intensify the corrosion of high chromia refractory more serious because of the temperature fluctuation in the gasifier. Figure 4 presents the slag distribution of 2# and 4# coal samples in the inner wall of the gasifier. It is clear that the slag distribution for the 2# coal sample is uniform, while there is almost no slag for 4# coal sample in the inner wall of the gasifier, with the chrome green being prominently visible. This phenomenon is primarily attributed to the low viscosity of the molten slag.
2.2　Morphology of corroded refractory bricks
The corroded high chromia refractory bricks in the slag tapping hole of four commercial coal-water slurry gasifiers were obtained, each corresponding to a different coal sample used as gasification feedstock (1#−4#). These corroded high chromia refractory bricks were cut longitudinally and marked as 1#−4# brick. The morphology of these corroded bricks were shown in Figure 5.
Figure 5 reveals that some cracks occurred in the interior of all corroded refractory bricks, particularly for bricks 1# and 4#, where the width of the crack is larger. The poor flow characteristic of crystallization slag causes severe penetration and corrosion due to prolonged residence time of molten slag on the surface of refractory brick. To further investigate the cause of the crack formation, these cracks in the 3# and 4# refractory bricks were examined, and their microstructures were analyzed by SEM-EDS. Figure 6(a) and (b) depict the microstructure of the crack internal surface of the 3# refractory brick, Figure 6(c) and (d) are the microstructure of the crack internal surface of 4# refractory brick.
In Figure 6(a), (b), the surface of refractory material appeared muddy and some trip-shaped crystals were found in the cracks. An analysis of the trip-shaped crystal and the area in Figure 6(a) using EDS. The results are shown in Table 3. It is evident from Table 3 that the chemical composition of slag was found in the cracks, and the trip-shaped crystal mainly comprise Fe and P elements. In the case of the crack in the 4# refractory brick, significant fragments and dendritic substances were observed in Figure 6(c) and (d), respectively. These were also analyzed using EDS and the results are presented in Table 3. Similarly, the chemical composition of slag was also found in the crack of 4# refractory brick. According to the EDS analysis, the dendritic substance mainly comprised Ca and P elements. This may be related to the high calcium content in the 4# coal sample. Additionally, the XRD analysis was conducted to determine the substance in the crack, and the results are illustrated in Figure 7 and Figure 8.
Figure 7 and Figure 8 revealed that the substances in the crack of 3# refractory brick were similar to that in the crack of 4# refractory brick and both containing (Al,Cr)2O3, Ba(PO3)2, Cr2O3, (Cr,Fe)2O4, Fe, KAlSi3O8, ZrO2. The presence of Ca3Si2O7 in the crack of the 4# refractory brick indicated the high calcium content in the coal sample.
Based on the identified substances, it can be concluded that a reaction occurred between chromium oxides in refractory brick and Fe oxides and Al oxides in molten slag. However, the absence of zirconium-containing spinel in these cracks, as confirmed by XRD, indicates that the thermal shock resistance of the cracks remains unchanged[23]. The results suggest that the formation of these cracks is mainly attributable to molten slag penetration and the ensuing reaction with the refractory material. The new substance formed by reaction, such as Fe, has a higher linear expansion coefficient (1.22×10−5 ℃−1) than Cr2O3 (9.6×10−6 ℃−1). The difference in thermal expansion between the newly formed substances resulting from the reaction and the refractory material is a vital factor in forming these cracks.
2.3　Analysis of the interface between molten slag and refractory brick
Refractories typically comprise multiple phases, including aggregate and matrix[24]. In the case of high chromia refractory bricks, the aggregate consists of Cr2O3, while the matrix composition comprises ZrO2, Al2O3 and Cr2O3. Since the interface between molten slag and refractory brick is the primary reaction region, the microstructure of the slag-aggregate interface and the slag-matrix interface were analyzed using SEM-EDS. Figure 9 presents the micrographs of the slag-aggregate interface for corroded 1#−4# refractory bricks.
Figure 9 reveals that the slag layer and the aggregate are separated by the slag-aggregate interface (see red dashed line in the figure). The chemical composition of slag near the slag-aggregate interface was analyzed using EDS and the results are presented in Table 4.
The analyses in Table 4 show the presence of Cr2O3 and ZrO2 in the chemical composition of slag near the slag-aggregate interface. However, EDS analysis indicates that the chemical composition of aggregate near the slag-aggregate interface remains unchanged. This suggests that the corrosion of slag on refractory bricks is mainly due to the chemical reaction and/or dissolution of slag on refractory material. Furthermore, other phenomenon like slag permeation and residual carbon, were observed in the 1# brick and 3# brick as shown in Figure 9. These phenomena may be related to the operation temperature of the gasifier, with higher temperature corresponding to higher probability of slag permeation and lower residual carbon. The average gasification operation temperature is 1350 ℃ for 1# brick and 1250 ℃ for 3# brick. The observed slag permeation in the aggregate indicates a significant chemical reaction and/or dissolution between slag and Cr2O3. Figure 10 presents the micrographs of the slag-matrix interface for the 1#−4# refractory bricks.
Figure 10 reveals that the interface between slag and matrix appears relatively clear and residual carbon was observed in the 3# brick. The EDS analysis revealed that the white particles in the matrix consist of 100% ZrO2. Furthermore, the chemical composition in the slag layer and matrix near the slag-matrix interface was analyzed using EDS and results are presented in Table 5.
Table 5 reveals that the presence of Cr2O3 and ZrO2 in the slag layer was observed, and their chemical composition was also found in the matrix. These findings indicate a chemical reaction between slag and matrix. Furthermore, the relatively high content of Fe2O3 in the matrix suggests that iron oxide from slag has permeated into the matrix and reacted with Cr2O3 in a reducing atmosphere to form a spinel solution[18]. Typically, the Cr2O3 content in the matrix of the initial high chromia refractory brick is around 76%.
However, in Table 5, a noticeable decrease in the Cr2O3 content in the matrix compared to the initial high chromia brick is evident. After analyzing the slag-aggregate interface and the slag-matrix interface, it became evident that the reduction of Cr2O3 content is the initial sign of high chromia refractory damage. Figure 11 shows the schematic of high chromia refractory damage mechanism.
As shown in Figure 11, the damage mechanism of refractory brick in the slag tapping hole of the gasifier suggests that the matrix and aggregate of high chromia refractory are primarily affected due to the reduction of Cr2O3 content. This allows the slag penetrates the interior of the refractory brick and form new substances, ultimately resulting in damage caused by difference in thermal expansion between the new substances and the refractory brick. It is imperative to focus on preventing the reduction of Cr2O3 content to improve the service life of refractory brick in the slag tapping hole of the gasifier. It is crucial to dedicate more effort to this area in the future.
3　Conclusion
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This study examined the damage mechanism of high chromia refractory in four commercial coal-water slurry gasifiers. Coal samples used for gasification and the corroded refractory bricks in the slag tapping hole of the gasifier were analyzed to understand the damage mechanism. The slag characteristic of coal samples, including crystallization and viscosity-temperature of four gasification coal samples were investigated. The interior morphology of the corroded refractory bricks and the interface between slag and refractory brick were analyzed. The main conclusions were as follows:
The low-viscosity slag causes more severe damage to refractory bricks, suggesting that the safe slag tapping temperature range should be set as tICT−t2.5 when tICT is higher than t25.
Cracks were observed in the interior of all corroded refractory bricks, primarily due to the molten slag penetration and the reaction between molten slag and refractory material. The difference in thermal expansion between the new substances formed by the reaction and refractory material plays a vital role in these crack formations.
The reduction of Cr2O3 content is the earliest characteristic of high chromia refractory damage, as shown by the slag-aggregate and slag-matrix interface analysis results. Early detection or prevention of this reduction is vital to further damage.
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Appendix
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Year 2026 volume 54 Issue 3
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doi: 10.1016/S1872-5813(25)60600-1
  • Receive Date：2025-08-04
  • Online Date：2026-09-23
  • Published：2026-03-10
Article Data
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History
  • Received：2025-08-04
  • Revised：2025-09-01
  • Accepted：2025-09-08
Affiliations
    1National Institute of Clean-and-Low-Carbon Energy, Beijing 102209, China
    2State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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