Study on the adsorption kinetics of metal chloride-ammonia working fluid pair under non-equilibrium conditions

doi:10.11949/0438-1157.20240011

Abstract

Abstract:

Metal chloride/ammonia is a common working pair for chemical adsorption refrigeration and heat storage. Its existing kinetic model has the disadvantage of being complex or kinetic parameters change irregularly, and it cannot accurately and independently describe the adsorption process of multiple reaction stages. Taking MnCl₂/NH₃ and CaCl₂/NH₃ as representative working pairs, the sorption and desorption performances of composite sorbent of chloride and expanded natural graphite treated with sulfuric acid with mass ratio of 4∶1 were tested and investigated at the reaction pressures of 0.29, 0.42 and 0.61 MPa. The experimental results showed that the reaction rate decreased with the deepening of the reaction. Thus, a novel sorption kinetic model based on sorption capacities concerning pressure potential (μ), reaction rate constant (k), and reaction hysteresis constant (n) was built by coupling the Sigmond function and the analogy model. The robustness test results evidenced that the fitting curves of the non-equilibrium kinetic model worked satisfactorily on rebuilding the experimental data points for different chlorides, reaction stages (Ca_2-4-2 and Ca_4-8-4), and reaction directions (sorption and desorption) with the goodness of fit (R²) higher than 0.97. Moreover, the model parameters changed regularly with the various working conditions. At the same reaction pressure, k is negatively correlated with sorption temperature, but positively correlated with desorption temperature, and |n| is negatively correlated with desorption temperature.

Key words: ammonia sorption, metal chloride, kinetic model, Sigmond function, multiple reaction stages

摘要：

金属氯化物-氨是化学吸附式制冷和储热的常用工质对，其现有的动力学模型存在复杂或动力学参数变化无规律的问题，也不能准确地独立描述多反应阶段的吸附过程。以MnCl₂/NH₃和CaCl₂/NH₃为代表工作对，针对0.29、0.42和0.61 MPa的反应压力，进行吸附/解吸性能测试，在类比模型基础上耦合Sigmond函数，建立考虑压力势（μ）、反应速率常数（k）和反应滞后常数（n）的吸附量型动力学模型。鲁棒性测试结果表明：针对不同氯化物、不同反应阶段（Ca_2-4-2和Ca_4-8-4）和不同反应方向（吸附和解吸）所建立的非平衡动力学模型的拟合曲线与实验数据点吻合度较高，拟合优度R²均高于0.97；模型参数随工况呈规律变化，同一反应压力下k与吸附温度负相关，与解吸温度正相关，|n|与解吸温度负相关。

关键词: 氨吸附, 金属氯化物, 动力学模型, Sigmond函数, 多反应阶段

CLC Number:

O 647.32

Yanling CHEN, Bingzhi YUAN, Liwei WANG, Chen ZHANG, Hanyu ZHU. Study on the adsorption kinetics of metal chloride-ammonia working fluid pair under non-equilibrium conditions[J]. CIESC Journal, 2024, 75(6): 2252-2261.

陈彦伶, 袁炳志, 王丽伟, 张宸, 朱涵玉. 非平衡条件下金属氯化物-氨工质对的吸附动力学研究[J]. 化工学报, 2024, 75(6): 2252-2261.

Figures/Tables 13

Fig.1 Preparation process of chloride/ENG-TSA composite sorbents

Fig.2 Structure diagram of Rubotherm magnetic suspension thermogravimetric analyzer[21]

Fig.3 Schematic diagram of reaction equilibrium line between MnCl2/CaCl2-NH3

Fig.4 Normalized sorption capacity of MnCl2versus time at 0.42 MPa

Fig.5 Construction of sorption/desorption characteristic curve functions based on Sigmond function

Fig.6 The pressure potential of MnCl2versus time at 0.42 MPa

Fig.7 Fitting results of MnCl2-NH3 kinetic model

Table 1 Coefficients of plane equation of MnCl2-NH3 kinetic model parameters

系数	吸附工况	解吸工况
系数	k_Mn_2-6	k_Mn_6-2	n_Mn_6-2
a₁	2.44×10^-3	1.3×10^-4	-1.29×10^-2
a₂	8.42×10^-3	4.08×10^-5	-6.78×10^-3
a₃	-2.56×10^-2	-9.66×10^-5	2.49×10^-2
a₄	1.92	7.94×10^-3	-4.78
a₅	-1.43	-6.34×10^-3	2.89
a₆	62.22	7.45×10^-2	-3.22×10²

Fig.8 Fitting results of BaCl2-NH3 kinetic model

Fig.9 Normalized sorption capacity of CaCl2versus time at 0.42 MPa

Fig.10 The pressure potential of CaCl2versus time at 0.42 MPa (solid: Ca2-4, Ca8-4; hollow: Ca4-8, Ca4-2)

Fig.11 Fitting results of CaCl2-NH3 kinetic model

Table 2 Coefficients of plane equation of CaCl2-NH3 kinetic model parameters

系数	吸附工况		解吸工况
系数	k₁_Ca_2-4	k₂_Ca_4-8	k₁_Ca_8-4	n₁_Ca_8-4	k₂_Ca_4-2	n₂_Ca_4-2
a₁	1.2×10^-4	1.2×10^-4	4.51×10^-4	-1.53×10^-2	5.32×10^-5	-3.1×10^-2
a₂	1.52×10^-3	1.04×10^-3	-5.24×10^-5	-3.41×10^-3	1.92×10^-4	-1.19×10^-2
a₃	-2.71×10^-3	-1.89×10^-3	-2.77×10^-5	7.53×10^-3	-4.7×10^-4	2.81×10^-2
a₄	1.57×10^-1	1.1×10^-1	-4.05×10^-3	-1.11	4.35×10^-2	-3.86
a₅	-1.73×10^-1	-1.19×10^-1	2.52×10^-2	1.01	-3.32×10^-2	3.53
a₆	5.15	3.56	-1.7	-87.09	1.53	-2.74×10²

References 31

1	Chauhan P R, Kaushik S C, Tyagi S K. Current status and technological advancements in adsorption refrigeration systems: a review[J]. Renewable and Sustainable Energy Reviews, 2022, 154: 111808.
2	Souissi M, Guidara Z, Maalej A. Numerical simulation and experimental investigation on a solar refrigerator with intermittent adsorption cycle[J]. Solar Energy, 2019, 180: 277-292.
3	Zhang L Z. Design and testing of an automobile waste heat adsorption cooling system[J]. Applied Thermal Engineering, 2000, 20(1): 103-114.
4	Islam M P, Morimoto T. A new zero energy cool chamber with a solar-driven adsorption refrigerator[J]. Renewable Energy, 2014, 72: 367-376.
5	Metcalf S J, Tamainot-Telto Z, Critoph R E. Application of a compact sorption generator to solar refrigeration: case study of Dakar (Senegal)[J]. Applied Thermal Engineering, 2011, 31(14/15): 2197-2204.
6	Kubota M, Matsuo K, Yamanouchi R, et al. Absorption and desorption characteristics of NH₃ with metal chlorides for ammonia storage[J]. Journal of Chemical Engineering of Japan, 2014, 47(7): 542-548.
7	Shen C, Wang P, Shen L H, et al. NH₃ adsorption performance of silicon-supported metal chlorides[J]. Industrial & Engineering Chemistry Research, 2022, 61(25): 8616-8623.
8	Wang L W, Wang R Z, Oliveira R G. A review on adsorption working pairs for refrigeration[J]. Renewable and Sustainable Energy Reviews, 2009, 13(3): 518-534.
9	Berdiyeva P, Karabanova A, Blanchard D, et al. Sr(NH₃)₈Cl₂-expanded natural graphite composite for thermochemical heat storage applications studied by in situ neutron imaging[J]. Journal of Energy Storage, 2021, 34: 102176.
10	Yeo T H C, Tan I A W, Abdullah M O. Development of adsorption air-conditioning technology using modified activated carbon—a review[J]. Renewable and Sustainable Energy Reviews, 2012, 16(5): 3355-3363.
11	Attan D, Alghoul M A, Saha B B, et al. The role of activated carbon fiber in adsorption cooling cycles[J]. Renewable and Sustainable Energy Reviews, 2011, 15(3): 1708-1721.
12	Cabeza L F, Solé A, Barreneche C. Review on sorption materials and technologies for heat pumps and thermal energy storage[J]. Renewable Energy, 2017, 110: 3-39.
13	林肯, 许肖永, 李强, 等. 石蜡-膨胀石墨复合相变材料热导率研究[J]. 化工学报, 2021, 72(8): 4425-4432.
	Lin K, Xu X Y, Li Q, et al. Study on thermal conductivity of paraffin-expanded graphite composite phase change materials[J]. CIESC Journal, 2021, 72(8): 4425-4432.
14	Yuan Y, Bao H S, Ma Z W, et al. Investigation of equilibrium and dynamic performance of SrCl₂-expanded graphite composite in chemisorption refrigeration system[J]. Applied Thermal Engineering, 2019, 147: 52-60.
15	Lebrun M, Spinner B. Models of heat and mass transfers in solid-gas reactors used as chemical heat pumps[J]. Chemical Engineering Science, 1990, 45(7): 1743-1753.
16	Goetz V, Marty A. A model for reversible solid-gas reactions submitted to temperature and pressure constraints: simulation of the rate of reaction in solid-gas reactor used as chemical heat pump[J]. Chemical Engineering Science, 1992, 47(17/18): 4445-4454.
17	Lu H B, Mazet N, Coudevylle O, et al. Comparison of a general model with a simplified approach for the transformation of solid-gas media used in chemical heat transformers[J]. Chemical Engineering Science, 1997, 52(2): 311-327.
18	Mazet N, Amouroux M, Spinner B. Analysis and experimental study of the transformation of a non-isothermal solid/gas reacting medium[J]. Chemical Engineering Communications, 1991, 99(1): 155-174.
19	Atkinson G H, Hinmers S, Critoph R E, et al. Ammonium chloride (NH₄Cl)-ammonia (NH₃): sorption characteristics for heat pump applications[J]. Energies, 2021, 14(18): 6002.
20	Hinmers S, Atkinson G H, Critoph R E, et al. Modelling and analysis of ammonia sorption reactions in halide salts[J]. International Journal of Refrigeration, 2022, 137: 188-211.
21	An G L, Li Y F, Wang L W, et al. Wide applicability of analogical models coupled with hysteresis effect for halide/ammonia working pairs[J]. Chemical Engineering Journal, 2020, 394: 125020.
22	Yan T, Zhang H, Yu N, et al. Performance of thermochemical adsorption heat storage system based on MnCl₂-NH₃ working pair[J]. Energy, 2022, 239: 122327.
23	Zisopoulos G, Nesiadis A, Atsonios K, et al. Conceptual design and dynamic simulation of an integrated solar driven thermal system with thermochemical energy storage for heating and cooling[J]. Journal of Energy Storage, 2021, 41: 102870.
24	王丽伟, 王如竹, 吴静怡, 等. 氯化钙-氨的吸附特性研究及在制冷中的应用[J]. 中国科学: 技术科学, 2004, 34(3): 268-279.
	Wang L W, Wang R Z, Wu J Y, et al. Study on adsorption characteristics of calcium chloride-ammonia and its application in refrigeration[J]. Scientia Sinica Technologica, 2004, 34(3): 268-279.
25	Jiang L, Wang L W, Wang R Z. Investigation on thermal conductive consolidated composite CaCl₂ for adsorption refrigeration[J]. International Journal of Thermal Sciences, 2014, 81: 68-75.
26	Cai S S, Hua Z P, Dai M, et al. Performance analysis of adsorption refrigeration using a composite adsorbent with improved heat and mass transfer[J]. International Journal of Heat and Mass Transfer, 2023, 216: 124523.
27	高娇, 王丽伟, 周志松, 等. 多盐复合吸附剂的非平衡吸附/解吸特性[J]. 化工学报, 2016, 67(S2): 184-190.
	Gao J, Wang L W, Zhou Z S, et al. Non-equilibrium adsorption/desorption characteristics of multi-salt composite adsorbent[J]. CIESC Journal, 2016, 67(S2): 184-190.
28	Neveu P, Castaing J. Solid-gas chemical heat pumps: field of application and performance of the internal heat of reaction recovery process[J]. Heat Recovery Systems and CHP, 1993, 13(3): 233-251.
29	李白雅, 封志鹏, 王锦涛, 等. 基于改进Sigmoid函数的PMSM调速系统自抗扰控制[J]. 传感器与微系统, 2023, 42(6): 90-93.
	Li B Y, Feng Z P, Wang J T, et al. Active disturbance rejection control of speed governing system for PMSM based on improved Sigmoid function[J]. Transducer and Microsystem Technologies, 2023, 42(6): 90-93.
30	Han J, Moraga C. The influence of the sigmoid function parameters on the speed of backpropagation learning[M]//Lecture Notes in Computer Science. Berlin, Heidelberg: Springer Berlin Heidelberg, 1995: 195-201.
31	Veselovskaya J V, Tokarev M M. Novel ammonia sorbents “porous matrix modified by active salt” for adsorptive heat transformation(4): Dynamics of quasi-isobaric ammonia sorption and desorption on BaCl₂/vermiculite[J]. Applied Thermal Engineering, 2011, 31(4): 566-572.

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