水合盐基中低温热化学储热材料性能测试及数值研究

doi:10.11949/0438-1157.20201484

摘要/Abstract

摘要：

以水合盐K₂CO₃·1.5H₂O和膨胀石墨（EG）分别作为化学蓄热材料和多孔基质，研制了复合储热吸附剂K₂CO₃@EG。对该复合吸附剂和未掺杂膨胀石墨的纯水合盐就脱附储热、吸附性能、循环稳定性等方面进行了对比分析。结果表明，复合吸附剂所需的脱附温度降低，对吸附质的吸附动力学性能也有明显提升且可有效避免潮解现象。经过连续15次的脱附-水合循环实验后，纯盐和复合吸附剂的储热密度分别下降27.6%和10.9%。此外，对储热单元的数值研究结果初步验证了该蓄热体系的可行性。

关键词: 水合盐, 热化学储热, 复合吸附剂, 动力学, 传热, 储热密度, 循环稳定性

Abstract:

Using hydrated salt K₂CO₃·1.5H₂O and expanded graphite (EG) as chemical heat storage materials and porous matrix respectively, a composite heat storage adsorbent K₂CO₃@EG was developed. The desorption, adsorption performance and cycle stability of the composite sorbent and pure salt without EG-doping were compared and analyzed. The results show that the desorption temperature of the composite adsorbent is reduced, and the adsorption kinetics of adsorbate is obviously improved, which can effectively avoid deliquescence. After fifteen consecutive desorption-hydration cycle experiments, the heat storage density of pure salt and composite adsorbent decreased by 27.6% and 10.9%, respectively. In addition, the numerical results of the thermal storage unit preliminarily verify the feasibility of the thermal storage system.

Key words: salt-hydrate, thermochemical heat storage, composite sorbent, kinetics, heat transfer, energy storage density, cycle stability

中图分类号:

TK 02

李威, 王秋旺, 曾敏. 水合盐基中低温热化学储热材料性能测试及数值研究[J]. 化工学报, 2021, 72(5): 2763-2772.

LI Wei, WANG Qiuwang, ZENG Min. Performance test and numerical study of salt hydrate-based thermochemical heat storage materials at middle-low temperature[J]. CIESC Journal, 2021, 72(5): 2763-2772.

图/表 11

图1 水合盐基化学蓄热系统运行示意图

Fig.1 Schematic diagram of hydrated salt-based chemical heat storage system

图2 膨胀石墨(a)，纯水合盐(b)以及 K2CO3@EG复合吸附剂(c)的SEM图

Fig.2 SEM images of expanded graphite (a), pure salt (b), and composite sorbent of K2CO3@EG (c)

图3 纯盐与复合吸附剂在30℃，(a)29% RH 和(b)不同相对湿度条件下的吸附情况

Fig.3 Adsorption of pure salt and composite sorbent at 30℃ with (a) 29% RH and (b) various vapor pressures

表1 两种吸附剂不同工况下平衡吸附量及所需时间

Table 1 Equilibrium adsorption capacities and corresponding times of sorbents

工况	纯K₂CO₃		CS15
工况	平衡吸附量/(g/g)	所需时间/min	平衡吸附量/(g/g)	所需时间/min
30℃，29% RH	0.1906	360	0.168	250
30℃，40% RH	0.1924	350	0.169	230
30℃，55% RH	0.24	400	0.2031	360

图4 纯盐与复合吸附剂的TG-DSC测量结果

Fig.4 TG-DSC results of the pure salt hydrate and the composite sorbent

图5 (a) 纯K2CO3和 (b) CS15复合吸附剂在循环过程中含水量和储热密度的变化

Fig.5 Water uptakes and energy storage densities of pure K2CO3 and CS15 sorbent in cyclability testing

图6 整体式储热管道(a)和储热单元对称结构一半及边界条件示意图(b)，网格独立性验证(c)

Fig.6 Schematic of the integral heat storage pipe (a) and a half of the symmetrical structure and boundary conditions (b), grid independence verification (c)

表2 控制方程及描述

Table 2 Governing equations and descriptions

控制方程		描述
反应动力学	$? α ? t = A f e x p - E a R T (1 - α) 2 / 3 p v p e q$	α为转化率；p_v, p_eq分别为蒸汽动态压力和平衡压力；A_f为指前因子；E_a为反应活化能；R为通用气体常数
克劳修斯-克拉贝隆方程	$l n p e q p r e f = - Δ H r R T e q + Δ S r R$	p_ref为参考水平压力；ΔH_r为反应焓；ΔS_r 为熵
质量守恒及质量输运	$(1 - ε) ? ρ s ? t = ρ s ? ? α ? t$ (solid) $ε ? ρ v ? t = S w - ? (ρ v u) + D g Δ ρ v$ (gas)	ε为吸附剂反应床孔隙率；D_g为蒸汽在多孔吸附剂内扩散系数
质量源项S_w	$S w = ρ s ? α ? t M v M s$	ρ_s 为储热吸附剂密度；M_v/M_s 为蒸汽摩尔质量和储热吸附剂摩尔质量比值
湿空气混合物	$? ? t ε ρ m + ? ? ρ m u = S w$	ρ_m 为湿空气密度；u 为气体速度
多孔储热材料内流体流动	$? ? t ρ m u + u ε ? ? ρ m u = ? ? [- ε p v I + μ m ? u + ? u T - 23 μ m ? ? u I] + S w u ε - ε μ v k u$	k为反应床渗透率；μ_m为水蒸气黏度
能量守恒	$(ρ C p) e f f ? ? T ? t = ? (λ e f f ? T) ? - C p v ? ρ v ? u ? ? T + q ˙$	热源 $q ˙ = ± ρ s M s ? α ? t Δ H r$ , 正负号取决于是吸附或脱附

表2 控制方程及描述

Table 2 Governing equations and descriptions

控制方程		描述
反应动力学	$? α ? t = A f e x p - E a R T (1 - α) 2 / 3 p v p e q$	α为转化率；p_v, p_eq分别为蒸汽动态压力和平衡压力；A_f为指前因子；E_a为反应活化能；R为通用气体常数
克劳修斯-克拉贝隆方程	$l n p e q p r e f = - Δ H r R T e q + Δ S r R$	p_ref为参考水平压力；ΔH_r为反应焓；ΔS_r 为熵
质量守恒及质量输运	$(1 - ε) ? ρ s ? t = ρ s ? ? α ? t$ (solid) $ε ? ρ v ? t = S w - ? (ρ v u) + D g Δ ρ v$ (gas)	ε为吸附剂反应床孔隙率；D_g为蒸汽在多孔吸附剂内扩散系数
质量源项S_w	$S w = ρ s ? α ? t M v M s$	ρ_s 为储热吸附剂密度；M_v/M_s 为蒸汽摩尔质量和储热吸附剂摩尔质量比值
湿空气混合物	$? ? t ε ρ m + ? ? ρ m u = S w$	ρ_m 为湿空气密度；u 为气体速度
多孔储热材料内流体流动	$? ? t ρ m u + u ε ? ? ρ m u = ? ? [- ε p v I + μ m ? u + ? u T - 23 μ m ? ? u I] + S w u ε - ε μ v k u$	k为反应床渗透率；μ_m为水蒸气黏度
能量守恒	$(ρ C p) e f f ? ? T ? t = ? (λ e f f ? T) ? - C p v ? ρ v ? u ? ? T + q ˙$	热源 $q ˙ = ± ρ s M s ? α ? t Δ H r$ , 正负号取决于是吸附或脱附

图7 释热过程中反应床及出口空气温度及吸附转化率变化

Fig.7 Temperature evolutions of reaction bed and outlet air and conversion degree during discharging

图8 吸附床在不同时刻吸附转化程度

Fig.8 Distributions of conversion degrees of sorption bed at different times

图9 不同相对湿度对吸附床温度的影响

Fig.9 Effects of different relative humidity on adsorption bed temperature

参考文献 30

1	Wang F, Gu J, Wu J. Perspective taking, energy policy involvement, and public acceptance of nuclear energy: evidence from China [J]. Energy Policy, 2020, 145: 111716.
2	Allen-Dumas M R, Rose A N, New J R, et al. Impacts of the morphology of new neighborhoods on microclimate and building energy [J]. Renewable and Sustainable Energy Reviews, 2020, 133: 110030.
3	马坤茹, 李雪峰, 李思琦, 等. 新型太阳能/空气能直膨式热泵与空气源热泵供热性能对比[J]. 化工学报, 2020, 71: 375-381.
	Ma K R, Li X F, Li S Q. Contrastive research of heating performance of direct expansion solar/air assisted heat pump system and air-source heat pump [J]. CIESC Journal, 2020, 71: 375-381.
4	Gaeini M, Rouws A L, Salari J W O, et al. Characterization of microencapsulated and impregnated porous host materials based on calcium chloride for thermochemical energy storage [J]. Applied Energy, 2018, 212(15): 1165-1177.
5	Xu M, Zhao P, Huo Y, et al. Thermodynamic analysis of a novel liquid carbon dioxide energy storage system and comparison to a liquid air energy storage system[J]. Journal of Cleaner Production, 2020, 242: 118437.
6	刘华, 彭佳杰, 余凯, 等. 活性氧化铝基质新型复合吸附剂的制备和储热性能[J].化工学报, 2020, 71(7): 3354-3361.
	Liu H, Peng J J, Yu K, et al. Preparation and thermal storage performance of novel composite sorbent with activated alumina matrix [J]. CIESC Journal, 2020, 71(7): 3354-3361.
7	Bennici S, Polimann T, Ondarts M, et al. Long-term impact of air pollutants on thermochemical heat storage materials [J]. Renewable and Sustainable Energy Reviews, 2020, 117: 109473.
8	徐凯迪, 谢涛, 王升, 等. 太阳能甲烷干重整复杂反应体系的热化学储能特性[J]. 化工进展, 2019, 38(11): 4921-4929.
	Xu K D, Xie T, Wang S, et al. Thermochemical energy storage characteristics of complex reaction system for solar methane dry reforming system [J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4921-4929.
9	Zhang Y, Wang R. Sorption thermal energy storage: concept, process, applications and perspectives[J]. Energy Storage Materials, 2020, 27: 352-369.
10	Clark R J, Mehrabadi A, Farid M. State of the art on salt hydrate thermochemical energy storage systems for use in building applications [J]. Journal of Energy Storage, 2020, 27: 101145.
11	李威, 陈威, 王丹丹. 基于水合盐热化学储能的技术研究与进展[J]. 制冷与空调, 2017, 17(8): 14-21.
	Li W, Chen W, Wang D D. Research and development of thermochemical energy storage based on hydrated salt [J]. Refrigeration and Air-Conditioning, 2017, 17(8): 14-21.
12	郝茂森, 刘洪芝, 王婉桐, 等. 水合盐热化学储热材料的研究进展[J]. 储能科学与技术, 2020, 9(3): 791-796.
	Hao M S, Liu H Z, Wang W T, et al. Research progress of thermochemical heat storage materials of hydrated salts [J]. Energy Storage Science and Technology, 2020, 9(3): 791-796.
13	翁立奎, 张叶龙, 姜琳, 等. 基于水合盐的热化学吸附储热技术研究进展[J]. 储能科学与技术, 2020, 9(6): 1729-1736.
	Weng L K, Zhang Y L, Jiang L, et al. Research progress on thermochemical adsorption heat storage technology based on hydrate [J]. Energy Starage Science and Technology, 2020, 9(6): 1729-1736.
14	李琳, 黄宏宇, 邓立生, 等. 低品位能源化学储热材料研究进展[J]. 化工进展, 2020, 39(9): 3608-3616.
	Li L, Huang H Y, Deng L S, et al. Research progress of low-grade energy chemical heat storage materials [J] Chemical Industry and Engineering Progress, 2020, 39(9): 3608-3616.
15	Fumey B, Weber R, Baldini L. Sorption based long-term thermal energy storage - process classification and analysis of performance limitations: a review [J]. Renewable and Sustainable Energy Reviews, 2019, 111: 57-74.
16	Okhrimenko L, Favergeon L, Johannes K, et al. New kinetic model of the dehydration reaction of magnesium sulfate hexahydrate: application for heat storage [J]. Thermochimica Acta, 2020, 687: 178569.
17	Li W, Zeng M, Wang Q W. Development and performance investigation of MgSO₄/SrCl₂ composite salt hydrate for mid-low temperature thermochemical heat storage [J]. Solar Energy Materials and Solar Cells, 2020, 210: 110509.
18	Zhang Y N, Wang R Z, Li T X. Thermochemical characterizations of high-stable activated alumina/LiCl composites with multistage sorption process for thermal storage [J]. Energy, 2018, 156: 240-249.
19	Xu J X, Li T X, Chao J W, et al. High energy-density multi-form thermochemical energy storage based on multi-step sorption processes [J]. Energy, 2019, 185: 1131-1142.
20	Wei S, Han R, Su Y, et al. Development of pomegranate-type CaCl₂@C composites via a scalable one-pot pyrolysis strategy for solar-driven thermochemical heat storage [J]. Energy Conversion and Management, 2020, 212: 112694.
21	Nonnen T, Preißler H, Kött S, et al. Salt inclusion and deliquescence in salt/zeolite X composites for thermochemical heat storage [J]. Microporous and Mesoporous Materials, 2020, 303: 110239.
22	Togawa J, Kurokawa A, Nagano K. Water sorption property and cooling performance using natural mesoporous siliceous shale impregnated with LiCl for adsorption heat pump [J]. Applied Thermal Engineering, 2020, 173: 115241.
23	Calabrese L, Brancato V, Palomba V, et al. Magnesium sulphate-silicone foam composites for thermochemical energy storage: assessment of dehydration behaviour and mechanical stability [J]. Solar Energy Materials and Solar Cells, 2019, 200: 109992.
24	Ait Ousaleh H, Said S, Zaki A, et al. Silica gel/inorganic salts composites for thermochemical heat storage: Improvement of energy storage density and assessment of cycling stability [J]. Materials Today: Proceedings, 2020, 30: 937-941.
25	Li W, Klemeš J J, Wang Q W, et al. Development and characteristics analysis of salt-hydrate based composite sorbent for low-grade thermochemical energy storage [J]. Renewable Energy, 2020, 157: 920-940.
26	Cammarata A, Verda V, Sciacovelli A, et al. Hybrid strontium bromide-natural graphite composites for low to medium temperature thermochemical energy storage: formulation, fabrication and performance investigation [J]. Energy Conversion and Management, 2018, 166: 233-240.
27	Ait Ousaleh H, Sair S, Mansouri S, et al. New hybrid graphene/inorganic salt composites for thermochemical energy storage: synthesis, cyclability investigation and heat exchanger metal corrosion protection performance [J]. Solar Energy Materials and Solar Cells, 2020, 215: 110601.
28	Zhou H, Zhang D. Effect of graphene oxide aerogel on dehydration temperature of graphene oxide aerogel stabilized MgCl₂⋅6H₂O composites [J]. Solar Energy, 2019, 184: 202-208.
29	Li W, Klemeš J J, Wang Q W, et al. Performance analysis of consolidated sorbent based closed thermochemical energy storage reactor for environmental sustainability[J]. Journal of Cleaner Production, 2020, 265: 121821.
30	Li W, Guo H, Zeng M, et al. Performance of SrBr₂·6H₂O based seasonal thermochemical heat storage in a novel multilayered sieve reactor [J]. Energy Conversion and Management, 2019, 198: 111843.

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