Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials

doi:10.11949/0438-1157.20230338

Abstract

Abstract:

Thermochemical energy storage has become an emerging research hotspot for efficient heat storage due to its high energy density and materials suitable for long-term storage and long-distance transportation. Calcium-based materials, which are low-cost, non-toxic, and non-polluting, have shown promising applications in this regard. This paper summarizes the current systems and categorization of the thermochemical thermal storage. It encompasses material modification, reactor design, and system integration applications for medium and high temperature calcium-based thermochemical storage. Then, the recent challenges and opportunities in calcium-based thermochemical energy storage technology are presented. Finally, this paper offers an outlook and provides suggestions for future research and development directions.

Key words: thermochemical energy storage, calcium-based granular material, stability, reactor design, process systems

摘要：

热化学储热由于能量密度高，材料适宜于长时储存和远距离运输，成为高效储热新兴的研究热点。钙基材料热化学储热成本低且无毒无污染，具有广阔应用前景。总结了目前热化学储热的主要体系及分类，针对中高温钙基热化学储热技术从材料改性、反应器设计及系统集成应用三个层面的研究进展进行综述。探讨钙基热化学储热技术研究中面临的挑战与机遇，并对今后的研究与发展方向提出了建议。

关键词: 热化学储热, 钙基颗粒物料, 稳定性, 反应器设计, 过程系统

CLC Number:

TK 02

Yuyuan ZHENG, Zhiwei GE, Xiangyu HAN, Liang WANG, Haisheng CHEN. Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials[J]. CIESC Journal, 2023, 74(8): 3171-3192.

郑玉圆, 葛志伟, 韩翔宇, 王亮, 陈海生. 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.

Figures/Tables 31

Fig.1 Reaction temperature and storage density of some thermochemical energy storage materials[9-10]

Table 1 The classification and reaction conditions for thermochemical energy storage

反应类型	反应式	ΔH/(kJ/mol)	T/℃
金属氢化物反应^[12-13]	$M g H_{2} (s) M g (s) + H_{2} (g)$	75	450
金属氢化物反应^[12-13]	$L i H (s) L i (s) + 1 / 2 H_{2} (g)$	88	947
氨类反应^[14]	$2 N H_{3} (g) N_{2} (g) + 3 H_{2} (g)$	66	200
氨类反应^[14]	$N H_{4} H S O_{4} (l) H_{2} O (g) + N H_{3} (g) + S O_{3} (g)$	335	467
氢氧化物反应^[15-16]	$M g {(O H)}_{2} (s) \overset{}{} M g O (s) + H_{2} O (g)$	84	330
氢氧化物反应^[15-16]	$C a {(O H)}_{2} (s) \overset{}{} C a O (s) + H_{2} O (g)$	104	515
碳酸盐反应^[9,17]	$C a C O_{3} (s) \overset{}{} C a O (s) + C O_{2} (g)$	178	900
碳酸盐反应^[9,17]	$M g C O_{3} (s) \overset{}{} M g O (s) + C O_{2} (g)$	125	400
氧化还原反应^[10,18]	$2 C o_{3} O_{4} (s) \overset{}{} 6 C o O (s) + O_{2} (g)$	205	914
氧化还原反应^[10,18]	$6 M n_{2} O_{3} (s) \overset{}{} 4 M n_{3} O_{4} (s) + O_{2} (g)$	910	948

Table 1 The classification and reaction conditions for thermochemical energy storage

反应类型	反应式	ΔH/(kJ/mol)	T/℃
金属氢化物反应^[12-13]	$M g H_{2} (s) M g (s) + H_{2} (g)$	75	450
金属氢化物反应^[12-13]	$L i H (s) L i (s) + 1 / 2 H_{2} (g)$	88	947
氨类反应^[14]	$2 N H_{3} (g) N_{2} (g) + 3 H_{2} (g)$	66	200
氨类反应^[14]	$N H_{4} H S O_{4} (l) H_{2} O (g) + N H_{3} (g) + S O_{3} (g)$	335	467
氢氧化物反应^[15-16]	$M g {(O H)}_{2} (s) \overset{}{} M g O (s) + H_{2} O (g)$	84	330
氢氧化物反应^[15-16]	$C a {(O H)}_{2} (s) \overset{}{} C a O (s) + H_{2} O (g)$	104	515
碳酸盐反应^[9,17]	$C a C O_{3} (s) \overset{}{} C a O (s) + C O_{2} (g)$	178	900
碳酸盐反应^[9,17]	$M g C O_{3} (s) \overset{}{} M g O (s) + C O_{2} (g)$	125	400
氧化还原反应^[10,18]	$2 C o_{3} O_{4} (s) \overset{}{} 6 C o O (s) + O_{2} (g)$	205	914
氧化还原反应^[10,18]	$6 M n_{2} O_{3} (s) \overset{}{} 4 M n_{3} O_{4} (s) + O_{2} (g)$	910	948

Fig.2 (a) CaO conversion of natural calcium-based materials within 100 cycles at 950℃; (b) CO2 adsorption within 1000 cycles[37]

Table 2 Classification and characteristics of oxide doping modification

分类	掺杂材料	特点	文献
活性掺杂	Al₂O₃, ZrO₂	在50次煅烧/碳酸化循环中保持80%以上吸附性；允许离子在整个晶体结构中迁移，对碳酸化反应起到催化作用；有效增强循环稳定性和反应活性	[42]
	CeO₂, Mn₃O₄	分散CaO颗粒，缓解烧结；Ce和Mn之间的电子转移促进了CO₂扩散和O^2-迁移；在40次循环中保持0.61 g/g的CO₂吸附量	[43]
	Fe₂O₃, Mn₃O₄	薄片状多孔结构；促进氧空位产生并降低反应活化能；在20次循环中保持95%的转化率	[44]
	Al₂O₃, CeO₂	掺杂量为5%时表现出最高的储热能力；30次循环有效转化率和能量密度仅下降7%；具有更大的比表面积和孔隙率，促进CO₂吸附	[45]
惰性掺杂	Al₂O₃	提高反应速率，缩短反应时间（减少42%）；提高循环稳定性	[46]
	SiO₂	提高材料机械强度，在100次循环内保持28 N以上	[23]
	SiO₂	提高材料导热性能，比热容提高20%；掺杂量为5%时材料反应动力学表现最佳；循环稳定性增强28%	[47]
	TiO₂	掺杂量为2.5% 储热密度达1256.68 kJ/kg，30次循环后仍为纯CaCO₃的2.26倍；反应活化能从1117.39 kJ/mol降低到997.6 kJ/mol，脱碳温度从903.56℃降低到876.13℃；总转化率降低	[48]

Fig.3 SEM and EDS images of CaCO3-Al2O3-ZrO2 (mass fraction 13.3%) samples before and after 50 cycles (Al: blue; Zr: green; Ca: red) [42]

Fig.4 Schematic diagram of anti-sintering with doped inert components[35]

Fig.5 Mechanism of CO2 adsorption by Na2CO3-CaO adsorbent[54]

Fig.6 Effect of potassium and sodium salt doping on the cyclic stability of calcium-based materials[57]

Fig.7 Principle of hydration/ dehydration reaction of CaO/Ca(OH)2 system encapsulated in semi-permeable ceramic material (shell: brown part； core: white and gray parts)[58]

Fig.8 Formation process of the core-shell-structured CaO-based pellets using the general repeated impregnation-evaporation coating process[65]

Fig.9 Fixed bed bench and main equipment[69]

Fig.10 Indirect fixed bed reactor[70]

Fig.11 Schematic diagram of the reactor with embedded porous channels[72]

Fig.12 The schematic of multi-layer reactor structure and monitoring points[73]

Fig.13 The schematic diagram of pressurized reactor for multi-cycle energy storage[77]

Fig.14 The schematic diagram of intermittent fluidized bed experimental setup[79]

Fig.15 The schematic diagram of the fluidized bed reactor experimental setup [80]

Fig.16 A novel fluidized bed reactor based on ploughshare mixer[81]

Fig.17 The schematic diagram of a double fluidized bed device for calcium cycle CO2 capture[83]

Fig.18 The experimental setup of fluidized bed reactor with steam addition[86]

Fig.19 Intermittent fluidized bed reactor[90]

Fig.20 The flow routes of the heat transfer fluid in the shell (red arrows) and the heat storage material in the reactor tube (green arrows) (a) and 3D image of the reactor (b)[60]

Fig.21 Heat exchanger plate and material channel and cover plate and reaction gas inlet[92]

Fig.22 Spiral tube reactor[94]

Fig.23 Schematic of the carbonate looping process for CO2 capture

Fig.24 1 MWh scale double fluidized bed calcium-based carbon capture system[99]

Fig.25 Chemical heat pump operation diagram[104]

Fig.26 Conceptual diagram of CSP-Cal thermochemical thermal storage system[113]

Fig.27 Diagram of CSP-Cal closed Brayton cycle system[116]

Fig.28 The schematic diagram of double fluidized bed system[117]

Fig.29 SOCRATCES project plant flow chart (10 kW scale) [123]

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