Experimental study on cyclic heat storage performance of TiO2-doped calcium based materials under pressurized carbonation

doi:10.11949/0438-1157.20240922

Abstract

Abstract:

Pressurizing the heat release (carbonation) process in CaCO₃/CaO thermochemical energy storage cycle can significantly improve the cyclic heat storage performance of calcium-based materials. The carbonation cycle heat storage performance of TiO₂-doped calcium-based materials (CaCO₃-TiO₂) under pressurized conditions was studied. The influences of TiO₂ doping amount, carbonation pressure, temperature and cycle times on the heat storage performance of CaCO₃-TiO₂ were discussed. The results show that when doped with 5% (mass) TiO₂, CaCO₃-5TiO₂ is more alkaline than pure CaCO₃, the carbonation reaction proceeds more easily, and the cyclic heat storage performance is the best. The increase of carbonation pressure can enhance the heat storage performance of CaCO₃-5TiO₂, but the enhancement range decreases with the increase of pressure. Under the best working condition (0.8 MPa, 850℃), after 30 cycles, the heat storage density of CaCO₃-5TiO₂ is 1829 kJ/kg, which is 23% higher than that under normal pressure, and 2.9 times higher than that of pure CaCO₃ under normal pressure. SEM/TEM and BET characterization shows that CaTiO₃ produced by the reaction of TiO₂ with CaO effectively relieves the sintering and agglomeration of the material. After 30 cycles, the specific surface area and pore volume of calcined CaCO₃-5TiO₂ are 2 times and 1.4 times that of calcined pure CaCO₃. It has more stable pressurized carbonation cycle heat storage performance.

Key words: thermochemical energy storage, calcium-based materials, pressurized carbonation, carbon dioxide, adsorption, stability

摘要：

在CaCO₃/CaO热化学储能循环的释热（碳酸化）过程中，加压可显著提高钙基材料的循环储热性能。本文对TiO₂掺杂钙基材料（CaCO₃-TiO₂）在加压条件下的碳酸化循环储热性能展开研究，重点讨论了TiO₂掺杂量、碳酸化压力、循环次数等对CaCO₃-TiO₂储热性能的影响。结果表明：掺杂5%（质量分数）TiO₂时，CaCO₃-5TiO₂比纯CaCO₃碱性更强，碳酸化反应更易进行，循环储热性能最好。碳酸化压力升高可以增强CaCO₃-5TiO₂的储热性能，但增强幅度随着压力升高而减小。在最佳工况（0.8 MPa，850℃）下循环30次后，CaCO₃-5TiO₂储热密度是常压下纯CaCO₃的2.9倍。SEM/TEM和BET表征显示，TiO₂与CaO反应生成的CaTiO₃有效缓解了材料的烧结与团聚，循环30次后，煅烧CaCO₃-5TiO₂的比表面积和孔容是煅烧纯CaCO₃的2倍和1.4倍，具有更稳定的加压碳酸化循环储热性能。

关键词: 热化学储能, 钙基材料, 加压碳酸化, 二氧化碳, 吸附, 稳定性

CLC Number:

TK 02

Yao FU, Yingjuan SHAO, Wenqi ZHONG. Experimental study on cyclic heat storage performance of TiO₂-doped calcium based materials under pressurized carbonation[J]. CIESC Journal, 2025, 76(3): 1180-1190.

伏遥, 邵应娟, 钟文琪. TiO₂掺杂钙基材料加压碳酸化循环储热性能实验研究[J]. 化工学报, 2025, 76(3): 1180-1190.

Figures/Tables 17

Fig.1 Preparation process of TiO2-doped calcium based material

Fig.2 Schematic diagram of the pressurized fixed bed

Table 1 Experimental design scheme

实验组	TiO₂掺杂量/%	碳酸化温度/℃	碳酸化压力/MPa	循环次数
1	0	850	0.8	15
2	2	850	0.8	15
3	5	850	0.8	15
4	10	850	0.8	15
5	15	850	0.8	15
6	20	850	0.8	15
7	5	850	0.1	10
8	5	850	0.2	10
9	5	850	0.4	10
10	5	850	0.6	10
11	5	750	0.8	10
12	5	800	0.8	10
13	5	900	0.8	10
14	0	850	0.1	30
15	0	850	0.8	30
16	5	850	0.1	30
17	5	850	0.8	30

Fig.3 XRD patterns of calcined pure CaCO3 and calcined CaCO3-5TiO2

Fig.4 CO2-TPD spectra of calcined CaCO3 and calcined CaCO3-5TiO2

Fig.5 Effect of TiO2 doping amount on heat storage performance of doped calcium based materials

Fig.6 Heat storage performance of various doped calcium based materials

Fig.7 Effect of carbonation pressure on heat storage performance of CaCO3-5TiO2

Fig.8 Effect of carbonation temperature on heat storage performance of CaCO3-5TiO2

Fig.9 Effect of cycle times on heat storage performance of CaCO3-5TiO2

Fig.10 XRD patterns of different cycles under pressure/atmospheric carbonation

Fig.11 Variation of CaO grain size in calcined CaCO3 and calcined CaCO3-5TiO2 under pressurized/atmospheric carbonation

Fig.12 SEM images of calcined CaCO3 and calcined CaCO3-5TiO2 at different cycles under pressurized/atmospheric carbonation(a) initial calcined CaCO3; (b) calcined CaCO3 cycled 30 times at 0.1 MPa; (c) calcined CaCO3 cycled 30 times at 0.8 MPa;(d) initial calcined CaCO3-5TiO2; (e) calcined CaCO3-5TiO2 cycled 30 times at 0.1 MPa; (f) calcined CaCO3-5TiO2 cycled 30 times at 0.8 MPa

Fig.13 TEM images of calcined CaCO3 and calcined CaCO3-5TiO2 at different cycles under pressurized/atmospheric carbonation(a) initial calcined CaCO3; (b) calcined CaCO3 cycled 30 times at 0.1 MPa; (c) calcined CaCO3 cycled 30 times at 0.8 MPa;(d) initial calcined CaCO3-5TiO2; (e) calcined CaCO3-5TiO2 cycled 30 times at 0.1 MPa; (f) calcined CaCO3-5TiO2 cycled 30 times at 0.8 MPa

Table 2 Specific surface area and pore volume of calcined CaCO3 and calcined CaCO3-5TiO2

样品	循环次数	碳酸化压力/MPa	比表面积/(m²/g)	比孔容/(cm³/g)
煅烧纯CaCO₃	0	—	19.582	0.133
	30	0.1	3.248	0.028
	30	0.8	4.401	0.052
煅烧CaCO₃-5TiO₂	0	—	11.768	0.117
	30	0.1	7.414	0.069
	30	0.8	8.918	0.075

Fig.14 N2 absorption-desorption curves of calcined CaCO3 and calcined CaCO3-5TiO2 in pressurized/atmospheric carbonated heat storage cycles

Fig.15 Pore size distribution of calcined CaCO3 and calcined CaCO3-5TiO2 in pressurized/atmospheric carbonated heat storage cycles

References 35

1	潘怡, 刘敦禹, 金晶. CaO/CaCO₃储能系统材料设计研究进展[J]. 动力工程学报, 2024, 44(5): 770-781.
	Pan Y, Liu D Y, Jin J. Research progress on material design of CaO/CaCO₃ energy storage system[J]. Journal of Chinese Society of Power Engineering, 2024, 44 (5): 770-781.
2	Han R, Xing S, Wu X Q, et al. Relevant influence of alkali carbonate doping on the thermochemical energy storage of Ca-based natural minerals during CaO/CaCO₃cycles[J]. Renewable Energy, 2022, 181: 267-277.
3	Liu Y N, Deng S, Zhao R K, et al. Energy-saving pathway exploration of CCS integrated with solar energy: a review of innovative concepts[J]. Renewable and Sustainable Energy Reviews, 2017, 77: 652-669.
4	Wang X R, Liu X L, Zheng H B, et al. Hierarchically doping calcium carbonate pellets for directly solar-driven high-temperature thermochemical energy storage[J]. Solar Energy, 2023, 251: 197-207.
5	Cheng K L, Li J H, Yu J C, et al. Novel thermoelectric generator enhanced supercritical carbon dioxide closed-brayton-cycle power generation systems: performance comparison and configuration optimization[J]. Energy, 2023, 284: 129368.
6	Ortiz C, Romano M C, Valverde J M, et al. Process integration of Calcium-looping thermochemical energy storage system in concentrating solar power plants[J]. Energy, 2018, 155: 535-551.
7	郑玉圆, 葛志伟, 韩翔宇, 等. 中高温钙基材料热化学储热的研究进展与展望[J]. 化工学报, 2023, 74(8): 3171-3192.
	Zheng Y Y, Ge Z W, Han X Y, et al. Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials[J]. CIESC Journal, 2023, 74(8): 3171-3192.
8	孙健, 柏生斌, 周子健, 等. CaCO₃/CaO复合材料热化学储能特性研究进展[J]. 华中科技大学学报(自然科学版), 2023, 51(1): 123-132.
	Sun J, Bai S B, Zhou Z J, et al. Research progress on thermochemical energy storage properties of CaCO₃/CaO compound composites[J]. Journal of Huazhong University of Science and Technology (Natural Science Edition), 2023, 51(1): 123-132.
9	Cannone S F, Stendardo S, Lanzini A. Solar-powered Rankine cycle assisted by an innovative calcium looping process as an energy storage system[J]. Industrial & Engineering Chemistry Research, 2020, 59(15): 6977-6993.
10	Edwards S E B, Materić V. Calcium looping in solar power generation plants[J]. Solar Energy, 2012, 86(9): 2494-2503.
11	Ortiz D C, Valverde M J M, Chacartegui R, et al. Carbonation of limestone derived CaO for thermochemical energy storage: from kinetics to process integration in concentrating solar plants[J]. ACS Sustainable Chemistry and Engineering, 2018, 6(5): 6404-6417.
12	Chen X Y, Jin X G, Ling X, et al. Indirect integration of thermochemical energy storage with the recompression supercritical CO₂ Brayton cycle[J]. Energy, 2020, 209: 118452.
13	Rodrigues D, Pinheiro C I C, Filipe R M, et al. Optimization of an improved calcium-looping process for thermochemical energy storage in concentrating solar power plants[J]. Journal of Energy Storage, 2023, 72:108199.
14	Nie F L, Ma T Z, Zhang Q Q, et al. Heat storage and release characteristics of a prototype CaCO₃/CaO thermochemical energy storage system based on a novel fluidized bed solar reactor[J]. Journal of Cleaner Production, 2024, 450: 142003.
15	Li C L, Li Y J, Zhang C X, et al. Ca₃B₂O₆-modified papermaking white mud for CaCO₃/CaO thermochemical energy storage[J]. Chemical Engineering Journal, 2023, 461: 142096.
16	Liu X L, Yuan C J, Zheng H B, et al. Synergy of Li₂CO₃ promoters and Al-Mn-Fe stabilizers in CaCO₃ pellets enables efficient direct solar-driven thermochemical energy storage[J]. Materials Today Energy, 2022, 30: 101174.
17	Huang X K, Ma X T, Li J, et al. Enhancement effects of hydrolysable/soluble Al-type dopants on the efficiency of CaO/CaCO₃ thermochemical energy storage[J]. Chemical Engineering Journal, 2024, 490: 151555.
18	Sun H, Li Y J, Bian Z G, et al. Thermochemical energy storage performances of Ca-based natural and waste materials under high pressure during CaO/CaCO₃ cycles[J].Energy Conversion and Management, 2019, 197: 111885.
19	Li B Y, Li Y J, Sun H, et al. Thermochemical heat storage performance of CaO pellets fabricated by extrusion-spheronization under harsh calcination conditions[J]. Energy & Fuels, 2020, 34(5): 6462-6473.
20	Xu Y F, Li Y J, Zhang C X, et al. High-temperature thermochemical heat storage performance of CaO honeycombs during CaO/CaCO₃ cycles[J]. Energy & Fuels, 2021, 35(20): 16882-16893.
21	Pang H, Xu H R, Sun A W, et al. Characteristics of MgO-based sorbents for CO₂ capture at elevated temperature and pressure[J]. Applied Surface Science, 2022, 598: 153852.
22	Khosa A A, Xu T X, Xia B Q, et al. Technological challenges and industrial applications of CaCO₃/CaO based thermal energy storage system—a review[J]. Solar Energy, 2019, 193:618-636.
23	Tian X K, Lin S C, Yan J, et al. Sintering mechanism of calcium oxide/calcium carbonate during thermochemical heat storage process[J]. Chemical Engineering Journal, 2022, 428: 131229.
24	Khosa A A, Zhao C Y. Heat storage and release performance analysis of CaCO₃/CaO thermal energy storage system after doping nano silica[J]. Solar Energy, 2019, 188: 619-630.
25	Wang K, Gu F, Clough P T, et al. Porous MgO-stabilized CaO-based powders/pellets via a citric acid-based carbon template for thermochemical energy storage in concentrated solar power plants[J]. Chemical Engineering Journal, 2020, 390: 124163.
26	Khosa A A, Yan J, Zhao C Y. Investigating the effects of ZnO dopant on the thermodynamic and kinetic properties of CaCO₃/CaO TCES system[J]. Energy, 2021, 215: 119132.
27	Han R, Gao J H, Wei S Y, et al. High-performance CaO-based composites synthesized using a space-confined chemical vapor deposition strategy for thermochemical energy storage[J]. Solar Energy Materials and Solar Cells, 2020, 206: 110346.
28	Xu T X, Tian X K, Khosa A A, et al. Reaction performance of CaCO₃/CaO thermochemical energy storage with TiO₂ dopant and experimental study in a fixed-bed reactor[J]. Energy, 2021, 236: 121451.
29	Hao Y J, Tian L G, Duan E H, et al. Low-temperature methane oxidation triggered by peroxide radicals over noble-metal-free MgO catalyst[J]. ACS Applied Materials & Interfaces, 2020, 12(19): 21761-21771.
30	Liu H, Pan F F, Wu S F. The grain growth mechanism of nano-CaO regenerated by nano-CaCO₃ in calcium looping [J]. RSC Advances, 2019, 9(46): 26949-26955.
31	Li Y J, Zhao C S, Chen H C, et al. Modified CaO-based sorbent looping cycle for CO₂ mitigation[J]. Fuel, 2009, 88(4): 697-704.
32	Hu Y, Liu W, Chen H, et al. Screening of inert solid supports for CaO-based sorbents for high temperature CO₂ capture[J]. Fuel, 2016, 181: 199-206.
33	Bai S B, Sun J, Zhou Z J, et al. Structurally improved, TiO₂-incorporated, CaO-based pellets for thermochemical energy storage in concentrated solar power plants[J]. Solar Energy Materials and Solar Cells, 2021, 226: 111076.
34	刘昊, 吴素芳. 固相反应对纳米钙基CO₂吸附剂自激活的影响[J]. 高校化学工程学报, 2021, 35(1): 57-64.
	Liu H, Wu S F. Effect of solid-phase reaction on self-reactivation of nano-calcium-based CO₂ adsorbents[J]. Journal of Chemical Engineering of Chinese Universities, 2021, 35(1): 57-64.
35	Benitez-Guerrero M, Valverde J M, Sanchez-Jimenez P E, et al. Calcium-looping performance of mechanically modified Al₂O₃-CaO composites for energy storage and CO₂ capture[J]. Chemical Engineering Journal, 2018, 334: 2343-2355.

[1]	Sanlong WANG, Yuelin WANG, Yu CAO. Research on the performance of inorganic perovskite solar cells based on phase heterojunction [J]. CIESC Journal, 2025, 76(3): 1346-1352.
[2]	Jiayi YAO, Donghui ZHANG, Zhongli TANG, Wenbin LI. Research on carbon capture by pressure swing adsorption based on two-stage dual reflux [J]. CIESC Journal, 2025, 76(2): 744-754.
[3]	Zheng GONG, Xiulu GAO, Ling ZHAO, Dongdong HU. Preparation and shape memory properties of PBAT/PLA foams by supercritical CO₂ [J]. CIESC Journal, 2025, 76(2): 888-896.
[4]	Jingyu JIA, Deqi KONG, Yuanhui SHEN, Donghui ZHANG, Wenbin LI, Zhongli TANG. Simulation and analysis of ammonia separation process by pressure swing adsorption from synthetic ammonia reactor-off gas [J]. CIESC Journal, 2025, 76(2): 718-730.
[5]	Jiaxin WANG, Yanhong WEI, Shunyang NONG, Yanshu XIONG, Mei LI, Wen LI. Molecular mechanism analysis of melanoidin adsorption by polyamine-modified chitosan aerogel based on multiple quantum chemical theory calculations [J]. CIESC Journal, 2025, 76(1): 107-119.
[6]	Xinyu DONG, Longfei BIAN, Yiyi YANG, Yuxuan ZHANG, Lu LIU, Teng WANG. Study on flow and heat transfer mechanism of supercritical CO₂ in inclined upward tube under cooling conditions [J]. CIESC Journal, 2024, 75(S1): 195-205.
[7]	Yanlin CHEN, Aiguo ZHOU, Jiale ZHENG, Chuanruo YANG, Tianshu GE. Effects of support materials on amine-impregnated DAC adsorbents [J]. CIESC Journal, 2024, 75(S1): 217-222.
[8]	Xinyue WANG, Xiaohu XU, Haiyang ZHANG, Chunhua YIN. Study on encapsulation and properties vitamin A acetate/cyclodextrin [J]. CIESC Journal, 2024, 75(S1): 321-328.
[9]	Huanjuan ZHAO, Yingxin BAO, Kang YU, Jing LIU, Xinming QIAN. Quantitative experimental study on detonation instability of multi-component [J]. CIESC Journal, 2024, 75(S1): 339-348.
[10]	Guanyu REN, Yifei ZHANG, Xinze LI, Wenjing DU. Numerical study on flow and heat transfer characteristics of airfoil printed circuit heat exchangers [J]. CIESC Journal, 2024, 75(S1): 108-117.
[11]	Bei PEI, Zhibin HAO, Tianxiang XU, Ziqi ZHONG, Rui LI, Chong JIA, Yulong DUAN. Effect of surfactants on fire extinguishing efficiency of salted double fluid fine water mist [J]. CIESC Journal, 2024, 75(9): 3369-3378.
[12]	Xinyue LU, Ruiying CHEN, Xiaxue JIANG, Hairui LIANG, Ge GAO, Zhengfang YE. Comparative study on liquid air energy storage system and liquid carbon dioxide energy storage system coupled with liquefied natural gas cold energy [J]. CIESC Journal, 2024, 75(9): 3297-3309.
[13]	Haoyu WANG, Yang YANG, Wenjie JING, Bin YANG, Yu TANG, Yi LIU. Study on characteristics of gas-liquid spiral annular flow under action by different swirlers [J]. CIESC Journal, 2024, 75(8): 2744-2755.
[14]	Gang ZENG, Lin CHEN, Dong YANG, Haizhuan YUAN, Yanping HUANG. Visualization of local boundary thermal flow field of supercritical CO₂ inside a rectangular channel [J]. CIESC Journal, 2024, 75(8): 2831-2839.
[15]	Mingjun YANG, Wei SONG, Lei ZHANG, Zheng LING, Bingbing CHEN, Yongchen SONG. Research on the enhanced method of CO₂-seawater hydrate generation [J]. CIESC Journal, 2024, 75(8): 2939-2948.

Experimental study on cyclic heat storage performance of TiO₂-doped calcium based materials under pressurized carbonation

TiO₂掺杂钙基材料加压碳酸化循环储热性能实验研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 17

References 35

Related Articles 15

Recommended Articles

Metrics

Comments

实验组	TiO₂掺杂量/%	碳酸化温度/℃	碳酸化压力/MPa	循环次数
1	0	850	0.8	15
2	2	850	0.8	15
3	5	850	0.8	15
4	10	850	0.8	15
5	15	850	0.8	15
6	20	850	0.8	15
7	5	850	0.1	10
8	5	850	0.2	10
9	5	850	0.4	10
10	5	850	0.6	10
11	5	750	0.8	10
12	5	800	0.8	10
13	5	900	0.8	10
14	0	850	0.1	30
15	0	850	0.8	30
16	5	850	0.1	30
17	5	850	0.8	30

实验组	TiO₂掺杂量/%	碳酸化温度/℃	碳酸化压力/MPa	循环次数
1	0	850	0.8	15
2	2	850	0.8	15
3	5	850	0.8	15
4	10	850	0.8	15
5	15	850	0.8	15
6	20	850	0.8	15
7	5	850	0.1	10
8	5	850	0.2	10
9	5	850	0.4	10
10	5	850	0.6	10
11	5	750	0.8	10
12	5	800	0.8	10
13	5	900	0.8	10
14	0	850	0.1	30
15	0	850	0.8	30
16	5	850	0.1	30
17	5	850	0.8	30

实验组	TiO₂掺杂量/%	碳酸化温度/℃	碳酸化压力/MPa	循环次数
1	0	850	0.8	15
2	2	850	0.8	15
3	5	850	0.8	15
4	10	850	0.8	15
5	15	850	0.8	15
6	20	850	0.8	15
7	5	850	0.1	10
8	5	850	0.2	10
9	5	850	0.4	10
10	5	850	0.6	10
11	5	750	0.8	10
12	5	800	0.8	10
13	5	900	0.8	10
14	0	850	0.1	30
15	0	850	0.8	30
16	5	850	0.1	30
17	5	850	0.8	30

实验组	TiO₂掺杂量/%	碳酸化温度/℃	碳酸化压力/MPa	循环次数
1	0	850	0.8	15
2	2	850	0.8	15
3	5	850	0.8	15
4	10	850	0.8	15
5	15	850	0.8	15
6	20	850	0.8	15
7	5	850	0.1	10
8	5	850	0.2	10
9	5	850	0.4	10
10	5	850	0.6	10
11	5	750	0.8	10
12	5	800	0.8	10
13	5	900	0.8	10
14	0	850	0.1	30
15	0	850	0.8	30
16	5	850	0.1	30
17	5	850	0.8	30