钙基热化学储热反应器传热传质协同强化及储热特性研究

doi:10.19799/j.cnki.2095-4239.2025.0048

摘要/Abstract

摘要：

热化学储热技术具有储热密度高、热损失低及储热时间长等优点，已成为目前储热技术领域的研究热点。然而目前针对热化学储热过程的多物理场耦合研究相对较少，并且传统固定床反应器的传热传质性能较差，这导致反应器内热化学储热过程的反应速率较低。本研究基于能量守恒方程、质量守恒方程、动量守恒方程及化学反应动力学方程等建立了多物理场耦合的CaCO₃分解热化学储热过程模型，针对CaCO₃分解热化学储热过程进行了二维非稳态数值模拟研究，详细阐述了固定床反应器中CaCO₃分解热化学储热过程的能量转化机理。本研究分析了反应器内储热过程的温度、转化率、反应速率等指标随时间的变化过程，并讨论了孔隙率、入口气体流速和固体反应物热导率等反应条件对储热过程的影响。模拟结果表明，增大孔隙率、提高入口气体流速、提高固体反应物热导率均可以提高CaCO₃分解热化学储热过程的反应速率。通过在反应器内添加具有高渗透性的高热导率多孔通道，实现了反应器传热传质特性的协同强化，使反应器储热时间缩短45.09%，反应器的压降由87735 Pa大幅降低至10 Pa。本工作为高功率密度热化学储热反应器的设计和优化提供了重要的参数依据和指导。

关键词: 热化学储热, 数值分析, CaCO₃/CaO, 固定床反应器

Abstract:

Thermochemical heat storage technology, known for its high heat storage density, low heat loss, and long storage duration, has become a research focus in heat storage. However, limited research exists on multiphysics coupling during thermochemical heat storage, and traditional fixed-bed reactors exhibit poor heat and mass transfer performance, leading to low reaction rates. This study establishes a multiphysics coupling model for the thermochemical heat storage process of CaCO₃ decomposition based on equations such as energy conservation, mass conservation, momentum conservation, and chemical reaction kinetics. A two-dimensional unsteady-state numerical simulation was conducted to analyze the energy conversion mechanism of CaCO₃ decomposition in fixed-bed reactors. The study examined the temporal evolution of indicators such as temperature, conversion rate, and reaction rate during the heat storage process and discussed the impact of reaction conditions, including porosity, inlet gas flow rate, and solid reactant thermal conductivity, on the heat storage process. Simulation results indicated that increasing porosity, inlet gas flow rate, and solid reactant thermal conductivity enhanced the reaction rate of the CaCO₃ decomposition process. By incorporating a permeable high-thermal-conductivity porous channel into the reactor, a synergistic improvement in heat and mass transfer characteristics was achieved, reducing the reactor's heat storage time by 45.09% and pressure drop from 87735 to 10 Pa. These findings provide crucial parameters and guidance for designing and optimizing high-power-density thermochemical heat storage reactors.

Key words: thermochemical heat storage, numerical analysis, CaCO₃/CaO, fixed-bed reactors

中图分类号:

TK 02

孙霄龙, 龚海艇, 陈臻, 王振, 黄荣, 刘向雷. 钙基热化学储热反应器传热传质协同强化及储热特性研究[J]. 储能科学与技术, 2025, 14(3): 1198-1209.

Xiaolong SUN, Haiting GONG, Zhen CHEN, Zhen WANG, Rong HUANG, Xianglei LIU. Synergistic enhancement of heat and mass transfer and heat storage characteristics in calcium-based thermochemical heat storage reactors[J]. Energy Storage Science and Technology, 2025, 14(3): 1198-1209.

图/表 16

图1

表1

物性参数"

参数	符号	数值	单位
孔隙率	$ε$	0.7	—
CaO密度	$ρ C a O$	3320	kg/m³
CaCO₃密度	$ρ C a C O 3$	2650	kg/m³
反应器高度	$D$	40	mm
反应器长度	$L$	50	mm
入口通道高度	$d$	3	mm
入口通道长度	$l$	10	mm
指前因子	$A$	1×10⁶	s^-1
活化能	$E$	1.785×10⁵	J/mol
床层热导率	$λ s$	1.33	W/(m·K)
反应焓	$Δ H$	178000	J/mol
反应熵	$Δ S$	-159.7	J/(mol·K）

表1

表2

初始值和边界条件"

边界条件	方程
$t = 0$	$P = P 0 = 20265 P a, T b e d = T w a l l = 1148.2 K$
$y = 42$	$T w a l l = 1148.2 K$
$x = 0, 0 ≤ y ≤ 3$	$T i n = 1148.2 K, u = u i n = 0.2 m / s$
$x = 70, 0 ≤ y ≤ 3$	$- n ⃗ ⋅ ∇ T = 0, P o u t = 20265 P a$

表2

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

图13

图14

参考文献 37

1	DUAN W Q, KHURSHID A, NAZIR N, et al. From gray to green: Energy crises and the role of CPEC[J]. Renewable Energy, 2022, 190: 188-207. DOI: 10.1016/j.renene.2022.03.066.
2	YANG Q C, ZHENG M B, CHANG C P. Energy policy and green innovation: A quantile investigation into renewable energy[J]. Renewable Energy, 2022, 189: 1166-1175. DOI: 10.1016/j.renene. 2022.03.046.
3	MOULAKHNIF K, AIT OUSALEH H, SAIR S, et al. Renewable approaches to building heat: Exploring cutting-edge innovations in thermochemical energy storage for building heating[J]. Energy and Buildings, 2024, 318: 114421. DOI: 10.1016/j.enbuild. 2024.114421.
4	CHATE A, SRINIVASA MURTHY S, DUTTA P. Analysis of a coupled calcium oxide-potassium carbonate salt hydrate based thermochemical energy storage system[J]. Energy, 2024, 313: 134067. DOI: 10.1016/j.energy.2024.134067.
5	SANTAMARÍA PADILLA A, ROMERO-PAREDES RUBIO H. A thermochemical energy storage materials review based on solid-gas reactions for supercritical CO₂ solar tower power plant with a Brayton cycle[J]. Journal of Energy Storage, 2023, 73: 108906. DOI: 10.1016/j.est.2023.108906.
6	IRAM R, ANSER M K, AWAN R U, et al. Prioritization of renewable solar energy to prevent energy insecurity: An integrated role[J]. The Singapore Economic Review, 2021, 66(2): 391-412. DOI: 10.1142/s021759082043002x.
7	LAZZARIN R. Heat pumps and solar energy: A review with some insights in the future[J]. International Journal of Refrigeration, 2020, 116: 146-160. DOI: 10.1016/j.ijrefrig.2020.03.031.
8	CABEZA L. Advances in thermal energy storage systems: Methods and applications[M]. Amsterdam: Woodhead Publishing, 2021: 37-54.
9	TIAN X K, GUO S J, LV X J, et al. Progress in multiscale research on calcium-looping for thermochemical energy storage: From materials to systems[J]. Progress in Energy and Combustion Science, 2025, 106: 101194. DOI: 10.1016/j.pecs. 2024.101194.
10	ZHANG W Y, JI Y, FAN Y B, et al. Three-dimensional numerical study on finned reactor configurations for ammonia thermochemical sorption energy storage[J]. Chemical Engineering Science, 2024, 300: 120599. DOI: 10.1016/j.ces.2024.120599.
11	YADAV D, BANERJEE R. A review of solar thermochemical processes[J]. Renewable and Sustainable Energy Reviews, 2016, 54: 497-532. DOI: 10.1016/j.rser.2015.10.026.
12	PARDO P, DEYDIER A, ANXIONNAZ-MINVIELLE Z, et al. A review on high temperature thermochemical heat energy storage[J]. Renewable and Sustainable Energy Reviews, 2014, 32: 591-610. DOI: 10.1016/j.rser.2013.12.014.
13	ANDRÉ L, ABANADES S, FLAMANT G. Screening of thermochemical systems based on solid-gas reversible reactions for high temperature solar thermal energy storage[J]. Renewable and Sustainable Energy Reviews, 2016, 64: 703-715. DOI: 10.1016/j.rser.2016.06.043.
14	STRÖHLE S, HASELBACHER A, JOVANOVIC Z R, et al. The effect of the gas-solid contacting pattern in a high-temperature thermochemical energy storage on the performance of a concentrated solar power plant[J]. Energy & Environmental Science, 2016, 9(4): 1375-1389. DOI: 10.1039/C5EE03204K.
15	QIU Y N, YANG Y, YANG N, et al. Thermochemical energy storage using silica gel: Thermal storage performance and nonisothermal kinetic analysis[J]. Solar Energy Materials and Solar Cells, 2023, 251: 112153. DOI: 10.1016/j.solmat. 2022. 112153.
16	XU Q H, WANG L, LI Z S, et al. A calcium looping system powered by renewable electricity for long-term thermochemical energy storage, residential heat supply and carbon capture[J]. Energy Conversion and Management, 2023, 276: 116592. DOI: 10.1016/j.enconman.2022.116592.
17	PALACIOS A, BARRENECHE C, NAVARRO M E, et al. Thermal energy storage technologies for concentrated solar power-A review from a materials perspective[J]. Renewable Energy, 2020, 156: 1244-1265. DOI: 10.1016/j.renene.2019.10.127.
18	LI X, JIANG H C, SU Z X, et al. Integrated attrition model of mechanical-thermal-reaction for CaCO₃/CaO thermochemical energy storage[J]. Applied Thermal Engineering, 2024, 257: 124247. DOI: 10.1016/j.applthermaleng.2024.124247.
19	WEI L Y, PAN Z F, SUN S C, et al. Solar-driven collaborative thermochemical energy storage and fuel production via integrating calcium looping and redox cycle[J]. Chemical Engineering Journal, 2024, 500: 157364. DOI: 10.1016/j.cej.2024.157364.
20	ZHAO J, KORBA D, MISHRA A, et al. Particle-based high-temperature thermochemical energy storage reactors[J]. Progress in Energy and Combustion Science, 2024, 102: 101143. DOI: 10.1016/j.pecs.2024.101143.
21	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. DOI: 10.1016/j.energy.2021.121451.
22	JOHN M K, VISHNU K, VISHNU C, et al. Experimental and numerical investigations on an open thermochemical energy storage system using low-temperature hydrate salt[J]. Thermal Science and Engineering Progress, 2024, 53: 102749. DOI: 10.1016/j.tsep.2024.102749.
23	MATHEW A, NADIM N, CHANDRATILLEKE T T, et al. Kinetic investigation and numerical modelling of CaCO₃/Al₂O₃ reactor for high-temperature thermal energy storage application[J]. Solar Energy, 2022, 241: 262-274. DOI: 10.1016/j.solener.2022.06.005.
24	DENG Y J, ZHU Z Y, LIU Z M, et al. Study on coupling characteristics of thermal-fluid-chemical multi-physics field in CaCO₃/CaO thermochemical exothermic reactor[J]. Chemical Engineering Science, 2024, 299: 120453. DOI: 10.1016/j.ces. 2024.120453.
25	HAN X C, XU H J, ZHAO C Y. Design and performance evaluation of multi-layered reactor for calcium-based thermochemical heat storage with multi-physics coupling[J]. Renewable Energy, 2022, 195: 1324-1340. DOI: 10.1016/j.renene.2022.06.120.
26	HAN X C, XU H J, LI Y Y. Experimental investigation on thermochemical reaction with gradient-porosity reactor for medium temperature heat storage applications[J]. Journal of Energy Storage, 2024, 78: 110021. DOI: 10.1016/j.est. 2023. 110021.
27	YAN J, JIANG L, ZHAO C Y. Numerical simulation of the Ca(OH)₂/CaO thermochemical heat storage process in an internal heating fixed-bed reactor[J]. Sustainability, 2023, 15(9): 7141. DOI: 10.3390/su15097141.
28	WANG W, SHUAI Y, YANG J Y, et al. Heat transfer and heat storage characteristics of calcium hydroxide/oxide based on shell-tube thermochemical energy storage device[J]. Renewable Energy, 2023, 218: 119364. DOI: 10.1016/j.renene.2023.119364.
29	CHEN J T, XIA B Q, ZHAO C Y. Topology optimization for heat transfer enhancement in thermochemical heat storage[J]. International Journal of Heat and Mass Transfer, 2020, 154: 119785. DOI: 10.1016/j.ijheatmasstransfer.2020.119785.
30	HUMBERT G, SCIACOVELLI A. Design of effective heat transfer structures for performance maximization of a closed thermochemical energy storage reactor through topology optimization[J]. Applied Thermal Engineering, 2024, 239: 122146. DOI: 10.1016/j.applthermaleng.2023.122146.
31	ZHU L J, CAI T F, CHEN X Y, et al. Gas-solid flow behavior and heat transfer in a spiral-based reactor for calcium-based thermochemical energy storage[J]. Journal of Energy Storage, 2024, 99: 113481. DOI: 10.1016/j.est.2024.113481.
32	SHI T, XU H J, QI C, et al. Multi-physics modeling of thermochemical heat storage with enhance heat transfer[J]. Applied Thermal Engineering, 2021, 198: 117508. DOI: 10.1016/j.applthermaleng.2021.117508.
33	YONG Z, MATA V, RODRIGUES A E. Adsorption of carbon dioxide at high temperature—A review[J]. Separation and Purification Technology, 2002, 26(2/3): 195-205. DOI: 10.1016/S1383-5866(01)00165-4.
34	SCHAUBE F, UTZ I, WÖRNER A, et al. De- and rehydration of Ca(OH)₂ in a reactor with direct heat transfer for thermo-chemical heat storage. Part B: Validation of model[J]. Chemical Engineering Research and Design, 2013, 91(5): 865-873. DOI: 10.1016/j.cherd.2013.02.019.
35	LIU X L, CHENG B, ZHU Q B, et al. Highly efficient solar-driven CO₂ reforming of methane via concave foam reactors[J]. Energy, 2022, 261: 125141. DOI: 10.1016/j.energy.2022.125141.
36	顾清之, 赵长颖. 镁-氢化镁热化学蓄热系统数值分析[J]. 化工学报, 2012, 63(12): 3776-3783. DOI: 10.3969/j.issn.0438-1157. 2012. 12.006.
	GU Q Z, ZHAO C Y. Numerical study on Mg/MgH₂ thermochemical heat storage system[J]. CIESC Journal, 2012, 63(12): 3776-3783. DOI: 10.3969/j.issn.0438-1157.2012.12.006.
37	DU PLESSIS P, MONTILLET A, COMITI J, et al. Pressure drop prediction for flow through high porosity metallic foams[J]. Chemical Engineering Science, 1994, 49(21): 3545-3553. DOI: 10.1016/0009-2509(94)00170-7.

[1]	姚亮, 贺楠, 陈奇成. 氧化钙基多级孔隙结构储热模块的制备及其储热性能[J]. 储能科学与技术, 2024, 13(12): 4282-4289.
[2]	马鸿坤, 纪明希, 丁玉龙. 中低温吸附式热化学储热研究现状与进展[J]. 储能科学与技术, 2024, 13(12): 4436-4451.
[3]	王乐霄, 罗伊默, 王利明, 杨格桑. 水合盐热化学反应器多因素耦合作用下的性能研究[J]. 储能科学与技术, 2024, 13(12): 4396-4405.
[4]	葛继翔, 纪明希, 丁玉龙, 罗伊默, 王利明. 水合盐热化学反应器参数优化与供暖应用案例分析[J]. 储能科学与技术, 2023, 12(12): 3799-3807.
[5]	张叶龙, 苗琪, 宋鹏飞, 谈玲华, 金翼, 丁玉龙. 矿物基硫酸镁热化学吸附材料的制备与性能评价[J]. 储能科学与技术, 2023, 12(1): 42-50.
[6]	姜竹, 邹博杨, 丛琳, 谢春萍, 李传, 谯耕, 赵彦琦, 聂彬剑, 张童童, 葛志伟, 马鸿坤, 金翼, 李永亮, 丁玉龙. 储热技术研究进展与展望[J]. 储能科学与技术, 2022, 11(9): 2746-2771.
[7]	李明飞, 饶睦敏, 孙婉妹, 崔树鑫, 陈伟. 基于多孔介质模化的大容量电池储能热管理系统性能分析方法[J]. 储能科学与技术, 2022, 11(8): 2526-2536.
[8]	李仲博, 汉京晓, 王成成, 杨慧, 杨娜, 尹少武, 王立, 童莉葛, 唐志伟, 丁玉龙. 热化学反应器放热过程模拟及参数影响规律[J]. 储能科学与技术, 2022, 11(7): 2133-2140.
[9]	杨娜, 王成成, 杨慧, 胡志昊, 童莉葛, 李仲博, 王立, 丁玉龙, 李娜. 基于热化学反应的硅胶非等温动力学计算及储热性能分析[J]. 储能科学与技术, 2022, 11(5): 1331-1338.
[10]	王为术, 张向薪, 姚紫琨, 甄娟. MgH₂ 反应器储氢反应速度特性[J]. 储能科学与技术, 2022, 11(5): 1543-1550.
[11]	莫雅超, 闫君, 赵长颖. CaO/Ca（OH） ₂ 核壳结构颗粒的制备及其储热性能[J]. 储能科学与技术, 2022, 11(12): 3828-3835.
[12]	徐钿昕, 田希坤, 闫君, 叶强, 赵长颖. TiO₂改性的CaCO₃热化学储热的反应性能[J]. 储能科学与技术, 2022, 11(1): 1-8.
[13]	杨博文, 闫君, 赵长颖. 氢氧化镁热化学储热系统流化床反应器性能分析[J]. 储能科学与技术, 2021, 10(5): 1735-1744.
[14]	韩翔宇, 王亮, 葛志伟, 凌浩恕, 林曦鹏, 陈海生, 彭珑. Co₃O₄/CoO氧化还原反应储/释热动力学特性[J]. 储能科学与技术, 2021, 10(5): 1701-1708.
[15]	罗伊默, 芮金金, 徐薇, 彭晋卿, 折晓会, 李念平, 丁玉龙. 热化学储热反应器内水合盐物性调控及传热传质优化研究进展[J]. 储能科学与技术, 2021, 10(4): 1273-1284.