Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion

doi:10.1016/j.cjche.2025.06.007

中国化学工程学报 ›› 2025, Vol. 87 ›› Issue (11): 35-44.DOI: 10.1016/j.cjche.2025.06.007

Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion

Guoxing Wei¹, Tao Liu^1,2, Fanglin Song¹, Facun Jiao¹, Lirui Mao¹, Yuanchun Zhang¹, Shengtao Gao¹

1. School of Chemical and Blasting Engineering, Anhui University of Science and Technology, Huainan 232001, China;
2. Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology, Huainan 232001, China

收稿日期:2025-03-31 修回日期:2025-06-06 接受日期:2025-06-06 出版日期:2025-11-28 发布日期:2025-06-19
通讯作者: Tao Liu,E-mail:liutao@aust.edu.cn
基金资助:
This research program was fnancially supported by the Open Research Fund Program of Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology (MTY202201).

Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion

Guoxing Wei¹, Tao Liu^1,2, Fanglin Song¹, Facun Jiao¹, Lirui Mao¹, Yuanchun Zhang¹, Shengtao Gao¹

1. School of Chemical and Blasting Engineering, Anhui University of Science and Technology, Huainan 232001, China;
2. Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology, Huainan 232001, China

Received:2025-03-31 Revised:2025-06-06 Accepted:2025-06-06 Online:2025-11-28 Published:2025-06-19
Contact: Tao Liu,E-mail:liutao@aust.edu.cn
Supported by:
This research program was fnancially supported by the Open Research Fund Program of Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology (MTY202201).

摘要/Abstract

摘要： Coal-direct chemical looping (CDCL) is a promising CO₂ capture technology with low costs. Potassium modification can significantly enhance the reactivity of iron-based oxygen carriers and coal. However, potassium loss causes a decline in cyclic stability. To address this, we prepared a potassium hexatitanate-modified iron-based OC and conducted CDCL experiments in a fixed-bed reactor using Zhundong coal coke as fuel. The study examined the impact of potassium hexatitanate on carbon conversion, OC activity stability, and potassium maintenance. Additionally, FactSage was used to calculate potassium fugacity patterns at different temperatures, Fe₂O₃/C molar ratios, and OC reduction degrees. Results showed that potassium hexatitanate increased carbon conversion, achieving 50% conversion at 40% potassium addition. In multi-cycle tests, carbon conversion rose with increased cycle times, reaching 84%. This improvement is attributed to ion exchange between Fe³⁺ and Ti⁴⁺, which induces lattice distortion and creates oxygen vacancies, enhancing OC reactivity. Potassium content remained stable during multi-cycle tests, indicating the effective potassium retention capacity of potassium hexatitanate.

关键词: Coal-direct chemical looping combustion, Iron-based oxygen carrier, K₂Ti₆O₁₃, FactSage simulation

Abstract: Coal-direct chemical looping (CDCL) is a promising CO₂ capture technology with low costs. Potassium modification can significantly enhance the reactivity of iron-based oxygen carriers and coal. However, potassium loss causes a decline in cyclic stability. To address this, we prepared a potassium hexatitanate-modified iron-based OC and conducted CDCL experiments in a fixed-bed reactor using Zhundong coal coke as fuel. The study examined the impact of potassium hexatitanate on carbon conversion, OC activity stability, and potassium maintenance. Additionally, FactSage was used to calculate potassium fugacity patterns at different temperatures, Fe₂O₃/C molar ratios, and OC reduction degrees. Results showed that potassium hexatitanate increased carbon conversion, achieving 50% conversion at 40% potassium addition. In multi-cycle tests, carbon conversion rose with increased cycle times, reaching 84%. This improvement is attributed to ion exchange between Fe³⁺ and Ti⁴⁺, which induces lattice distortion and creates oxygen vacancies, enhancing OC reactivity. Potassium content remained stable during multi-cycle tests, indicating the effective potassium retention capacity of potassium hexatitanate.

Key words: Coal-direct chemical looping combustion, Iron-based oxygen carrier, K₂Ti₆O₁₃, FactSage simulation

Guoxing Wei, Tao Liu, Fanglin Song, Facun Jiao, Lirui Mao, Yuanchun Zhang, Shengtao Gao. Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion[J]. 中国化学工程学报, 2025, 87(11): 35-44.

参考文献

[1] D.C. Wang, J.Z. Xiao, Z.H. Duan, Strategies to accelerate CO₂ sequestration of cement-based materials and their application prospects, Constr. Build. Mater. 314 (2022) 125646.
[2] R. Kumar, W.J. Chung, M.A. Khan, M. Son, Y.K. Park, S.S. Lee, B.H. Jeon, Breakthrough innovations in carbon dioxide mineralization for a sustainable future, Rev. Environ. Sci. Bio/Technol. 23 (3) (2024) 739-799.
[3] C.A. Horowitz, Paris agreement, Int. Leg. Mater. 55 (4) (2016) 740-755.
[4] H.T. Dang, B. Guan, J.Y. Chen, Z.R. Ma, Y.J. Chen, J.H. Zhang, Z.L. Guo, L. Chen, J.Q. Hu, C. Yi, S.Y. Yao, Z. Huang, Research on carbon dioxide capture materials used for carbon dioxide capture, utilization, and storage technology: A review, Environ. Sci. Pollut. Res. Int. 31 (23) (2024) 33259-33302.
[5] L. Miao, L.Y. Feng, Y. Ma, Comprehensive evaluation of CCUS technology: A case study of China’s first million-tonne CCUS-EOR project, Environ. Impact Assess. Rev. 110 (2025) 107684.
[6] M. Qasim, M. Ayoub, N.A. Ghazali, A. Aqsha, M. Ameen, Recent advances and development of various oxygen carriers for the chemical looping combustion process: A review, Ind. Eng. Chem. Res. 60 (24) (2021) 8621-8641.
[7] S. Alam, J.P. Kumar, K.Y. Rani, C. Sumana, Comparative assessment of performances of different oxygen carriers in a chemical looping combustion coupled intensified reforming process through simulation study, J. Clean. Prod. 262 (2020) 121146.
[8] T. Song, T.X. Shen, L.H. Shen, J. Xiao, H.M. Gu, S.W. Zhang, Evaluation of hematite oxygen carrier in chemical-looping combustion of coal, Fuel 104 (2013) 244-252.
[9] M.C. Tang, L. Xu, M.H. Fan, Progress in oxygen carrier development of methane-based chemical-looping reforming: A review, Appl. Energy 151 (2015) 143-156.
[10] J. Krzywanski, T. Czakiert, W. Nowak, T. Shimizu, W.M. Ashraf, A. Zylka, K. Grabowska, M. Sosnowski, D. Skrobek, K. Sztekler, A. Kijo-Kleczkowska, I. Iliev, Towards cleaner energy: An innovative model to minimize NOx emissions in chemical looping and CO₂ capture technologies, Energy 312 (2024) 133397.
[11] A. Abad, L.F. de Diego, F. Garcia-Labiano, M.T. Izquierdo, T. Mendiara, P. Gayan, I. Adanez-Rubio, J. Adanez, Reviewing the operational experience on chemical looping combustion of biomass at CSIC: iG-CLC vs CLOU, Energy Fuels 38 (21) (2024) 20681-20706.
[12] D.D. Miller, M. Smith, D. Shekhawat, Development of Fe-based oxygen carrier using spent FCC catalyst as support for high temperature chemical looping combustion, Fuel 259 (2020) 116239.
[13] J. Bao, W. Liu, J.P.E. Cleeton, S.A. Scott, J.S. Dennis, Z. Li, N. Cai, Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion, Proc. Combust. Inst. 34 (2) (2013) 2839-2846.
[14] Y.C. Feng, X. Cai, X. Guo, C.G. Zheng, Influence mechanism of H₂S on the reactivity of Ni-based oxygen carriers for chemical-looping combustion, Chem. Eng. J. 295 (2016) 461-467.
[15] Q. Imtiaz, A.M. Kierzkowska, C.R. Muller, Coprecipitated, copper-based, alumina-stabilized materials for carbon dioxide capture by chemical looping combustion, ChemSusChem 5 (8) (2012) 1610-1618.
[16] H.B. Zhao, L. Guo, X.X. Zou, Chemical-looping auto-thermal reforming of biomass using Cu-based oxygen carrier, Appl. Energy 157 (2015) 408-415.
[17] A. Zylka, J. Krzywanski, T. Czakiert, K. Idziak, M. Sosnowski, K. Grabowska, T. Prauzner, W. Nowak, The 4th generation of CeSFaMB in numerical simulations for CuO-based oxygen carrier in CLC system, Fuel 255 (2019) 115776.
[18] H. Zhou, G.Q. Wei, Q. Yi, Z.M. Zhang, Y.J. Zhao, Y.K. Zhang, Z. Huang, A.Q. Zheng, K. Zhao, Z.L. Zhao, Reactivity investigation on chemical looping gasification of coal with iron-manganese based oxygen carrier, Fuel 307 (2022) 121772.
[19] M. Matzen, J. Pinkerton, X.M. Wang, Y. Demirel, Use of natural ores as oxygen carriers in chemical looping combustion: A review, Int. J. Greenh. Gas Contr. 65 (2017) 1-14.
[20] N. Berguerand, A. Lyngfelt, Design and operation of a 10kWth chemical-looping combustor for solid fuels-Testing with South African coal, Fuel 87 (12) (2008) 2713-2726.
[21] A. Zylka, J. Krzywanski, T. Czakiert, K. Idziak, M. Sosnowski, M.L. de Souza-Santos, K. Sztekler, W. Nowak, Modeling of the chemical looping combustion of hard coal and biomass using ilmenite as the oxygen carrier, Energies 13 (20) (2020) 5394.
[22] S. Liang, Y.F. Liao, T.Y. Zhang, H.L. Yang, T.W. Wang, Mechanism of lattice oxygen migration in decarburized Fe-based oxygen carriers to chemical looping gasification, Renew. Energy 236 (2024) 121456.
[23] P.L. Wang, C.H. Zheng, Y. Li, Z.W. Xu, H.B. Zhao, Exploring the regulation mechanism of Ca/Fe-based oxygen carrier in biomass chemical looping gasification, Chem. Eng. J. 498 (2024) 155488.
[24] R.Z. He, J. Deng, X.L. Deng, X.G. Xie, Y. Li, S.F. Yuan, Effects of alkali and alkaline earth metals of inherent minerals on Fe-catalyzed coal pyrolysis, Energy 238 (2022) 121985.
[25] Y. Zhang, Q. Shang, D.D. Feng, H.L. Sun, F.H. Wang, Z.C. Hu, Z.Y. Cheng, Z.J. Zhou, Y.J. Zhao, S.Z. Sun, Interaction mechanism of in situ catalytic coal H₂O-gasification over biochar catalysts for H₂O-H₂-tar reforming and active sites conversion, Fuel Process. Technol. 233 (2022) 107307.
[26] T. Liu, Z.L. Yu, F.C. jiao, H.X. Li, Y.T. Fang, Effect of preparation conditions on the performance of K-decorated Fe2O3/Al₂O₃ oxygen carrier (OC) in chemical looping conversion of coal process with deep OC reduction, J. Energy Inst. 98 (2021) 179-187.
[27] T. Liu, L.R. Mao, F.C. Jiao, C.L. Wu, M.D. Zheng, H.X. Li, Catalytic performance of Na/Ca-based fluxes for coal char gasification, Green Process. Synth. 11 (1) (2022) 204-217.
[28] K. Mitsuoka, S. Hayashi, H. Amano, K. Kayahara, E. Sasaoaka, M.A. Uddin, Gasification of woody biomass char with CO₂: The catalytic effects of K and Ca species on char gasification reactivity, Fuel Process. Technol. 92 (1) (2011) 26-31.
[29] Z. Ma, J.F. Wang, G.F. Liu, H. Zhang, Y.G. Lu, J.H. Xiong, C.Y. Xie, C. Zou, Regeneration of deactivated Fe2O3/Al₂O₃ oxygen carrier via alkali metal doping in chemical looping combustion, Fuel Process. Technol. 220 (2021) 106902.
[30] L.L. Wang, L.H. Shen, W.D. Liu, S.X. Jiang, Chemical looping hydrogen generation using synthesized hematite-based oxygen carrier comodified by potassium and copper, Energy Fuels 31 (8) (2017) 8423-8433.
[31] T. Liu, S.X. Hu, Z.L. Yu, J.J. Huang, J.Z. Li, Z.Q. Wang, Y.T. Fang, Research of coal-direct chemical looping hydrogen generation with iron-based oxygen carrier modified by potassium, Int. J. Hydrog. Energy 42 (16) (2017) 11038-11046.
[32] F. Hildor, M. Zevenhoven, A. Brink, L. Hupa, H. Leion, Understanding the interaction of potassium salts with an ilmenite oxygen carrier under dry and wet conditions, ACS Omega 5 (36) (2020) 22966-22977.
[33] V. Andersson, X.R. Kong, H. Leion, T. Mattisson, J.B.C. Pettersson, Gaseous alkali interactions with ilmenite, manganese oxide and calcium manganite under chemical looping combustion conditions, Fuel Process. Technol. 254 (2024) 108029.
[34] Z. Xu, C. Zhu, Y.Q. Zhang, L. Li, Z.K. Sun, H.J. Tang, L.B. Duan, High-temperature potassium capture by ilmenite ore residue, Proc. Combust. Inst. 40 (1-4) (2024) 105531.
[35] P. Ponce-Pena, M. Poisot, A. Rodriguez-Pulido, M.A. Gonzalez-Lozano, Crystalline structure, synthesis, properties and applications of potassium hexatitanate: A review, Materials 12 (24) (2019) 4132.
[36] T. Ishii, R. Takioka, H. Yasumura, A. Yamamoto, H. Yoshida, Fine crystals of potassium hexatitanate prepared by a sol-gel method for photocatalytic reduction of carbon dioxide with water, Catal. Today 429 (2024) 114476.
[37] W. Sarwana, A. Yamamoto, H. Yoshida, Granule of potassium hexatitanate fine crystals for photocatalytic steam reforming of methane, Catal. Today 411 (2023) 113858.
[38] Y.F. Du, B.L. Wen, R.L. Shu, L.P. Cao, W. Wang, Potassium titanate whiskers on the walls of cordierite honeycomb ceramics for soot catalytic combustion, Ceram. Int. 47 (24) (2021) 34828-34835.
[39] Q.U. Hassan, D. Yang, J.P. Zhou, Y.X. Lei, J.Z. Wang, S.U. Awan, Novel single-crystal hollandite K1.46Fe0.8Ti7.2O16 microrods: Synthesis, double absorption, and magnetism, Inorg. Chem. 57 (24) (2018) 15187-15197.
[40] X.J. Wang, Q. Chen, B. Wei, G.S. Yu, H.X. Li, X.L. Chen, H.F. Liu, F.C. Wang, Volatile potassium transfer behavior in carbon matrix and its effect on char gasification, Fuel 333 (2023) 126302.
[41] T. Liu, Z.L. Yu, F.C. jiao, L.R. Mao, M.D. Zheng, H.X. Li, Potassium occurrence form in the deep reduction of potassium-modified iron-based oxygen carrier by coal char, Int. J. Hydrog. Energy 48 (1) (2023) 67-77.
[42] J.C. Huang, Y. Fu, S.G. Li, W.B. Kong, J. Zhang, Y.H. Sun, Enhanced activity of MgFeO ferrites for two-step thermochemical CO₂ splitting, J. CO₂ Util. 27 (2018) 450-458.

Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion

Effect of potassium hexatitanate addition on the performance of iron-based oxygen carriers in coal-direct chemical looping combustion

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics

本文评价