Insights on the effect of Si-Al interaction on Ni/Al2O3/SiC monolithic catalysts for CO2 methanation

doi:10.1016/j.cjche.2025.05.031

中国化学工程学报 ›› 2025, Vol. 87 ›› Issue (11): 171-181.DOI: 10.1016/j.cjche.2025.05.031

Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation

Xiangli Liu¹, Fei Gao¹, Jingyang Huang², Yiqing Zeng^1,3, Zhaoxiang Zhong^1,3,4, Weihong Xing^3,4,5

1. School of Environmental Science and Engineering, Nanjing Tech University, Nanjing 211816, China;
2. Department of Statistics and Operations Research, University of North Carolina, Chapel Hill, NC 27599, USA;
3. State Key Laboratory of Materials-Oriented Chemical Engineering, National Engineering Research Center for Special Separation Membrane, Nanjing Tech University, Nanjing 211816, China;
4. NJTECH University Suzhou Future Membrane Technology Innovation Center, Suzhou 215300, China;
5. Jiangsu University, Zhenjiang 212013, China

收稿日期:2025-04-01 修回日期:2025-05-21 接受日期:2025-05-21 出版日期:2025-11-28 发布日期:2025-07-18
通讯作者: Yiqing Zeng,E-mail:yiqingzeng@163.com;Zhaoxiang Zhong,E-mail:zhongzx@njtech.edu.cn
基金资助:
This work sincerely acknowledged the National Natural Science Foundation of China (22325804 and 22308148), the Natural Science Foundation of Jiangsu Province (BK20230344), the Natural Science Research Project of Jiangsu University (22KJB610001).

Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation

Xiangli Liu¹, Fei Gao¹, Jingyang Huang², Yiqing Zeng^1,3, Zhaoxiang Zhong^1,3,4, Weihong Xing^3,4,5

1. School of Environmental Science and Engineering, Nanjing Tech University, Nanjing 211816, China;
2. Department of Statistics and Operations Research, University of North Carolina, Chapel Hill, NC 27599, USA;
3. State Key Laboratory of Materials-Oriented Chemical Engineering, National Engineering Research Center for Special Separation Membrane, Nanjing Tech University, Nanjing 211816, China;
4. NJTECH University Suzhou Future Membrane Technology Innovation Center, Suzhou 215300, China;
5. Jiangsu University, Zhenjiang 212013, China

Received:2025-04-01 Revised:2025-05-21 Accepted:2025-05-21 Online:2025-11-28 Published:2025-07-18
Contact: Yiqing Zeng,E-mail:yiqingzeng@163.com;Zhaoxiang Zhong,E-mail:zhongzx@njtech.edu.cn
Supported by:
This work sincerely acknowledged the National Natural Science Foundation of China (22325804 and 22308148), the Natural Science Foundation of Jiangsu Province (BK20230344), the Natural Science Research Project of Jiangsu University (22KJB610001).

摘要/Abstract

摘要： Monolithic catalysts have been widely investigated for CO₂ methanation due to their fast mass and heat transfer rate, but the effect of the interaction between the catalyst layer and the monolithic support has been little studied. In this work, Ni/Al₂O₃/SiC monolithic catalysts, Ni/Al₂O₃ powder catalysts and Ni/Al₂O₃/SiC-M catalysts were prepared to explore the effect of Si-Al interaction between the catalyst layer and SiC ceramic for CO₂ methanation performance. Ni/Al₂O₃/SiC exhibited a CO₂ conversion of 53% and a CH₄ specific reaction rate of 0.05 mmol·g^-1·s^-1 under conditions of 0.1 MPa, 400 °C, and a WHSV of 60000 ml·g^-1·h^-1. The CO₂ conversion raised by 0.15-fold and the CH₄ specific reaction rate raised by 0.25-fold compared to Ni/Al₂O₃ with the same catalyst content. SEM, XRD, Raman, and other characterization results revealed that the formation of Si-Al interaction between the catalyst layer and SiC ceramic could weaken the interaction between Ni and Al₂O₃, thereby improving the catalytic activity of Ni/Al₂O₃/SiC catalyst. However, the Si-Al interaction was further strengthened during the high-temperature reaction process, which significantly weakened the interaction between Ni and Al₂O₃, thereby leading to a decline in the catalytic performance of Ni/Al₂O₃/SiC catalyst during an 80-h stability test. This study provides valuable insights for future research and development of monolithic catalysts.

关键词: Carbon dioxide, Hydrogenation, Monolith, Ni/Al₂O₃/SiC monolithic catalyst, Si-Al interaction

Abstract: Monolithic catalysts have been widely investigated for CO₂ methanation due to their fast mass and heat transfer rate, but the effect of the interaction between the catalyst layer and the monolithic support has been little studied. In this work, Ni/Al₂O₃/SiC monolithic catalysts, Ni/Al₂O₃ powder catalysts and Ni/Al₂O₃/SiC-M catalysts were prepared to explore the effect of Si-Al interaction between the catalyst layer and SiC ceramic for CO₂ methanation performance. Ni/Al₂O₃/SiC exhibited a CO₂ conversion of 53% and a CH₄ specific reaction rate of 0.05 mmol·g^-1·s^-1 under conditions of 0.1 MPa, 400 °C, and a WHSV of 60000 ml·g^-1·h^-1. The CO₂ conversion raised by 0.15-fold and the CH₄ specific reaction rate raised by 0.25-fold compared to Ni/Al₂O₃ with the same catalyst content. SEM, XRD, Raman, and other characterization results revealed that the formation of Si-Al interaction between the catalyst layer and SiC ceramic could weaken the interaction between Ni and Al₂O₃, thereby improving the catalytic activity of Ni/Al₂O₃/SiC catalyst. However, the Si-Al interaction was further strengthened during the high-temperature reaction process, which significantly weakened the interaction between Ni and Al₂O₃, thereby leading to a decline in the catalytic performance of Ni/Al₂O₃/SiC catalyst during an 80-h stability test. This study provides valuable insights for future research and development of monolithic catalysts.

Key words: Carbon dioxide, Hydrogenation, Monolith, Ni/Al₂O₃/SiC monolithic catalyst, Si-Al interaction

Xiangli Liu, Fei Gao, Jingyang Huang, Yiqing Zeng, Zhaoxiang Zhong, Weihong Xing. Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation[J]. 中国化学工程学报, 2025, 87(11): 171-181.

参考文献

[1] L. Jeffry, M. Y. Ong, S. Nomanbhay, M. Mofijur, M. Mubashir, P. L. Show, Greenhouse gases utilization: A review, Fuel 301 (2021) 121017.
[2] L. Sun, Q. Liu, H. Chen, H. Yu, L. Li, L. Li, Y. Li, C. D. Adenutsi, Source-sink matching and cost analysis of offshore carbon capture, utilization, and storage in China, Energy 291 (2024) 130137.
[3] C. Vogt, E. Groeneveld, G. Kamsma, M. Nachtegaal, L. Lu, C. J. Kiely, P. H. Berben, F. Meirer, B. M. Weckhuysen, Unravelling structure sensitivity in CO₂ hydrogenation over nickel, Nat. Catal. 1 (2) (2018) 127-134.
[4] P. Shafiee, S. M. Alavi, M. Rezaei, Mechanochemical synthesis method for the preparation of mesoporous Ni-Al₂O₃ catalysts for hydrogen purification via CO₂ methanation, J. Energy Inst. 96 (2021) 1-10.
[5] C. Dang, J. Zhou, H. Xia, W. Cai, A hierarchical hollow Ni/γ-Al₂O₃ catalyst derived from flower-like Ni-Al layered double hydroxide with stable catalytic performance for CO₂ methanation, J. Mater. Chem. A 12 (14) (2024) 8281-8290.
[6] D. Schmider, L. Maier, O. Deutschmann, Reaction kinetics of CO and CO₂ methanation over nickel, Ind. Eng. Chem. Res. 60 (16) (2021) 5792-5805.
[7] H. L. Huynh, Z. Yu, CO₂ methanation on hydrotalcite-derived catalysts and structured reactors: A review, Energy Technol. 8 (5) (2020) 1901475.
[8] A. Ricca, L. Truda, V. Palma, Study of the role of chemical support and structured carrier on the CO₂ methanation reaction, Chem. Eng. J. 377 (2019) 120461.
[9] A. Vita, C. Italiano, L. Pino, P. Frontera, M. Ferraro, V. Antonucci, Activity and stability of powder and monolith-coated Ni/GDC catalysts for CO₂ methanation, Appl. Catal. B-Environ. 226 (2018) 384-395.
[10] R. Zhang, H. Chen, Y. Mu, S. Chansai, X. Ou, C. Hardacre, Y. Jiao, X. Fan, Structured Ni@NaA zeolite supported on silicon carbide foam catalysts for catalytic carbon dioxide methanation, AIChE J. 66 (11) (2020) e17007.
[11] C. Italiano, G. D. Ferrante, L. Pino, M. Lagana, M. Ferraro, V. Antonucci, A. Vita, Silicon carbide and alumina open-cell foams activated by Ni/CeO₂-ZrO₂ catalyst for CO₂ methanation in a heat-exchanger reactor, Chem. Eng. J. 434 (2022) 134685.
[12] H. L. Huynh, W. M. Tucho, Z. Yu, Structured NiFe catalysts derived from in-situ grown layered double hydroxides on ceramic monolith for CO₂ methanation, Green Energy Environ. 5 (4) (2020) 423-432.
[13] Y. Wei, J. Ji, F. Liang, Y. Du, Z. Pang, H. Wang, Q. Li, G. Shi, Z. Wang, Pd/P-CeO₂-Al₂O₃ coatings supported on foam ceramic with controlled morphology for high-performance CO₂ methanation, Ceram. Int. 49 (22) (2023) 35071-35081.
[14] C. Fukuhara, K. Hayakawa, Y. Suzuki, W. Kawasaki, R. Watanabe, A novel nickel-based structured catalyst for CO₂ methanation: A honeycomb-type Ni/CeO₂ catalyst to transform greenhouse gas into useful resources, Appl. Catal. A-Gen. 532 (2017) 12-18.
[15] F. Han, Z. Zhong, Y. Yang, W. Wei, F. Zhang, W. Xing, Y. Fan, High gas permeability of SiC porous ceramics reinforced by mullite fibers, J. Eur. Ceram. Soc. 36 (16) (2016) 3909-3917.
[16] A. Aldoghachi, T.-Y. Yun Hin, M. I. Saiman, L. H. Voon, A. L. T. Zheng, S. Seenivasagam, Development of highly stable Ni-doped zeolitic imidazole framework (ZIF-67) based catalyst for CO₂ methanation reaction, Int. J. Hydrogen Energy 57 (2024) 1474-1485.
[17] L. A. Sani, H. Bai, Z. Xu, L. Fu, Y. Sun, X. Huang, H. Gao, X. Liu, D. Bai, Z. Zhang, F. Su, J. Liu, G. Xu, Optimized combustion temperature in the facile synthesis of Ni/Al₂O₃ catalyst for CO₂ methanation, J. CO₂ Util. 80 (2024) 102678.
[18] M. Taniewski, A. Lachowicz, K. Skutil, D. Czechowicz, The effect of dilution of the catalyst bed on its heat-transfer characteristics in oxidative coupling of methane Chem. Eng. Sci. 51 (18) (1996) 4271-4278.
[19] S. Pan, B. Hu, D. Liu, A. T. Kuvarega, B. B. Mamba, J. Gui, Fabrication of a highly efficient and reusable Pd/Al₂O₃/Al monolithic catalyst for the Suzuki-Miyaura reaction, Eur. J. Org. Chem. 27 (33) (2024).
[20] A. Razmjoo, H. R. Baharvandi, N. Ehsani, αSiC-βSiC graphene composites, Sci. Rep. 13 (1) (2023).
[21] Z. Xiang, Y. Wang, X. Yin, Q. He, Microwave absorption performance of porous heterogeneous SiC/SiO₂ microspheres, Chem. Eng. J. 451 (2) (2023) 138742.
[22] I. Abdullahi, N. Sakulchaicharoen, J. E. Herrera, A mechanistic study on the growth of multi-walled carbon nanotubes by methane decomposition over nickel-alumina catalyst, Diamond Relat. Mater. 23 (2012) 76-82.
[23] A. Aminzadeh, H. Sarikhani-fard, Raman spectroscopic study of Ni/Al₂O₃ catalyst, Spectrochim. Acta, Part A 55 (7) (1999) 1421-1425.
[24] R. A. Singh, A. K. Sood, V. Jayaram, S. K. Biswas, Analysis of microresidual stresses in 6H-SiC particles within Al₂O₃-SiC-(Al,Si) CMC using raman spectroscopy, Scr. Mater. 38 (4) (1998) 617-622.
[25] B. Wang, J. Yin, D. Chen, X. Long, L. Li, H.-H. Lin, W. Hu, D. N. Talwar, R.-X. Jia, Y.-M. Zhang, I. T. Ferguson, W. Sun, Z. C. Feng, L. Wan, Optical and surface properties of 3C-SiC thin epitaxial films grown at different temperatures on 4H-SiC substrates, Superlattices Microstruct. 156 (2021) 106960.
[26] G. Busca, V. Lorenzelli, V. Sanchez Escribano, Preparation, solid-state characterization, and surface chemistry of high-surface-area nickel-aluminum (NixAl2-2xO3-2x) mixed oxides, Chem. Mater. 4 (3) (1992) 595-605.
[27] S. Ali, J. Ryl, A. S. Hakeem, K. Grochowska, N. A. Wojcik, Investigation of the structural and thermal properties of aluminum-rich Ca-Al-Si-O-N glasses, Prog. Solid State Chem. 71 (2023) 100414.
[28] P. Riani, E. Spennati, M. V. Garcia, V. S. Escribano, G. Busca, G. Garbarino, Ni/Al₂O₃ catalysts for CO₂ methanation: Effect of silica and nickel loading, Int. J. Hydrogen Energy 48 (64) (2023) 24976-24995.
[29] S. Liu, X. Cha, X. Wang, K. Xu, K. B. Tan, D. Cai, J. Huang, Q. Li, G. Zhan, Atomic layer deposition of alumina on hollow nickel phyllosilicate nanosheets for enhanced CO₂ thermal hydrogenation performance, Chem. Eng. Sci. 283 (2024) 119394.
[30] Z. Wang, Z. Li, M. Zhong, Z. Li, C. Wang, Elucidating the effect of Al₂O₃/SiO₂ mass ratio upon SiO₂-MnO-CaF2-Al₂O₃-based welding fluxes: Structural analysis and thermodynamic evaluation, J. Non-Cryst. Solids 601 (2023) 122071.
[31] J. Liao, Y. Zhang, S. Sridhar, X. Wang, Z. Zhang, Effect of Al₂O₃/SiO₂ ratio on the viscosity and structure of slags, ISIJ Int. 52 (5) (2012) 753-758.
[32] W. Yan, D. Liu, D. Tan, P. Yuan, M. Chen, FTIR spectroscopy study of the structure changes of palygorskite under heating, Spectrochim. Acta, Part A 97 (2012) 1052-1057.
[33] A. Quindimil, U. De-La-Torre, B. Pereda-Ayo, A. Davo-Quinonero, E. Bailon-Garcia, D. Lozano-Castello, J. A. Gonzalez-Marcos, A. Bueno-Lopez, J. R. Gonzalez-Velasco, Effect of metal loading on the CO₂ methanation: A comparison between alumina supported Ni and Ru catalysts, Catal. Today 356 (2020) 419-432.
[34] N. F. Sulaiman, Y. W. Leong, S. L. Lee, S. Toemen, W. A. W. A. Bakar, Enhanced transesterification reaction using chromium-doped calcium oxide-based catalyst supported on alumina and its specification of biodiesel, Energy Convers. Manage. 293 (2023) 117556.
[35] Y. Jiang, T. Huang, L. Dong, Z. Qin, H. Ji, Ni/bentonite catalysts prepared by solution combustion method for CO₂ methanation, Chinese J. Chem. Eng. 26 (11) (2018) 2361-2367.
[36] S. Musab Ahmed, J. Ren, I. Ullah, H. Lou, N. Xu, Z. Abbasi, Z. Wang, Ni-based catalysts for CO₂ methanation: Exploring the support role in structure-activity relationships, ChemSusChem 17 (9) (2024).
[37] R. Ye, L. Ma, X. Hong, T. R. Reina, W. Luo, L. Kang, G. Feng, R. Zhang, M. Fan, R. Zhang, J. Liu, Boosting low-temperature CO₂ hydrogenation over Ni-based catalysts by tuning strong metal-support interactions, Angew. Chem. Int. Ed. 63 (3) (2023).
[38] S. Kalasina, K. Kongsawatvoragul, N. Phattharasupakun, P. Phattharaphuti, M. Sawangphruk, Cobalt oxysulphide/hydroxide nanosheets with dual properties based on electrochromism and a charge storage mechanism, RSC Advances 10 (24) (2020) 14154-14160.
[39] F. Jing, S. Liu, R. Wang, X. Li, Z. Yan, S. Luo, W. Chu, Hydrogen production through glycerol steam reforming over the NiCexAl catalysts, Renew. Energy 158 (2020) 192-201.
[40] W. Xing, Y. Liu, W. Zhang, Y. Sun, X. Kai, T. Yang, Study on methanation performance of biomass gasification syngas based on a Ni/Al₂O₃ monolithic catalyst, ACS Omega 5 (44) (2020) 28597-28605.
[41] F. Meng, L. Wang, X. Li, M. Perdjon, Z. Li, Mesoporous nano Ni-Al₂O₃ catalyst for CO₂ methanation in a continuously stirred tank reactor, Catal. Commun. 164 (2022) 106437.
[42] P. Hongmanorom, J. Ashok, P. Chirawatkul, S. Kawi, Interfacial synergistic catalysis over Ni nanoparticles encapsulated in mesoporous ceria for CO₂ methanation, Appl. Catal. B-Environ. 297 (2021) 120454.

Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation

Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Hansheng Wang, Xintian Luo, Kaixuan Chen, Benduan Xiao, Xu Zhang, Qingjun Meng, Huibing He, Jing Xu, Yong Jin. Research progress on the copper-based catalyst design for dimethyl oxalate hydrogenation to ethylene glycol[J]. 中国化学工程学报, 2025, 85(9): 189-205.
[2]	Zheyuan Pang, Siying Liu, Yiting Lin, Xiangchen Fang, Honglai Liu, Chong Peng, Cheng Lian. Large language model-based multi-objective modeling framework for vacuum gas oil hydrotreating[J]. 中国化学工程学报, 2025, 84(8): 133-145.
[3]	Mengting Chen, Minjie Zhu, Tingyu Zhou, Qifeng Zhong, Meihua Zhang, Yingxin Liu, Zuojun Wei. Enhanced activity and stability of SAPO-5 zeolite supported RuMn catalyst for aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol[J]. 中国化学工程学报, 2025, 81(5): 200-207.
[4]	Zhenhui Lv, Jianan Li, Tao Yang, Yibao Li, Chong Peng. Effect of carbon modifications on the performance of hydrogenation catalysts[J]. 中国化学工程学报, 2025, 81(5): 270-276.
[5]	Haoran Yin, Lili Mu, Yifeng Chen, Licheng Li, Kang Sun, Xiaoyan Ji. Improving CO₂ solubility in a hybrid sorbent of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide/mesoporous titanium dioxide/water with confinement effect[J]. 中国化学工程学报, 2025, 80(4): 100-109.
[6]	Xiangli Liu, Yiqing Zeng, Jiahao Chen, Zhaoxiang Zhong, Weihong Xing. Research progress on the monolithic catalyst for hydrogenation of CO₂ to methane[J]. 中国化学工程学报, 2025, 80(4): 184-197.
[7]	Wenbo Li, Xinyao Fu, Weiming Zhai, Xingyang Huang, Wenbin Chen, Chen Zhang, Wei Zhang, Cuiqing Li, Yong Luo, Feng Liu, Mingfeng Li. Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts[J]. 中国化学工程学报, 2025, 79(3): 11-22.
[8]	Aleksey K. Sagidullin, Sergey S. Skiba, Tatyana P. Adamova, Andrey Y. Manakov. Investigation of the formation processes of CO₂ hydrate films on the interface of liquid carbon dioxide with humic acids solutions[J]. 中国化学工程学报, 2025, 79(3): 53-61.
[9]	Zhe Ding, Li Guo, Fang Bai, Chao Hua, Ping Lu, Jinyi Chen. Toward the rational design for low-temperature hydrogenation of silicon tetrachloride: Mechanism and data-driven interpretable descriptor[J]. 中国化学工程学报, 2025, 79(3): 172-184.
[10]	Jian Long, Mengru Zhang, Anlan Li, Cheng Huang, Dong Xue. Hybrid model of multimodal based on data enhancement and lumped reaction kinetics: Applying to industrial ebullated-bed residue hydrogenation unit[J]. 中国化学工程学报, 2025, 78(2): 284-302.
[11]	Mohammad Sohrabi, Reza Alizadeh, S. Majid Abdoli. Boron-modified ZSM-5 coated on honeycomb monolith surface for selective production of propylene from methanol[J]. 中国化学工程学报, 2025, 88(12): 21-33.
[12]	Xun Tao, Yifan Zhang, Fan Zhou, Songling Guo, Yunfei Gao, Lu Ding, Xuezhi Duan, Zhenghua Dai, Guangsuo Yu, Fuchen Wang. Acid gas combustion in the inverse diffusion flame for increasing flame temperature under low-level oxygen enrichment conditions[J]. 中国化学工程学报, 2025, 88(12): 75-84.
[13]	Ze Gong, Dexi Wang, Xueyi Ma, Lihua Fan. Thermal decomposition behavior and kinetics of magnesite under carbon dioxide atmosphere[J]. 中国化学工程学报, 2025, 87(11): 197-203.
[14]	Hong Xiao, Shilei Yu, Yuhan Yan, Junjing Zhou, Rongfei Zhou, Weihong Xing. High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid[J]. 中国化学工程学报, 2025, 87(11): 252-261.
[15]	Wei Liu, Xiaoshen Li, Shaohui Xiong, Xueyang Jiang, Jiayan Yan, Xiang Duan, Yingtian Zhang, Qingpeng Cheng, Ye Tian, Xingang Li. Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol[J]. 中国化学工程学报, 2025, 86(10): 25-33.