非平衡条件下金属氯化物-氨工质对的吸附动力学研究

doi:10.11949/0438-1157.20240011

摘要/Abstract

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

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

中图分类号:

O 647.32

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.

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.

图/表 13

图1 氯化物/ENG-TSA复合吸附剂制备流程

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

图2 Rubotherm磁悬浮热重分析仪结构图[21]

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

图3 MnCl2/CaCl2-NH3反应平衡线示意图

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

图4 0.42 MPa下MnCl2归一化吸附量与反应时间的关系

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

图5 基于Sigmond函数构建吸附/解吸特性曲线函数

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

图6 0.42 MPa下MnCl2压力势与反应时间的关系

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

图7 MnCl2-NH3动力学模型拟合结果

Fig.7 Fitting results of MnCl2-NH3 kinetic model

表1 MnCl2-NH3动力学模型参数平面方程系数

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

图8 BaCl2-NH3动力学模型拟合结果

Fig.8 Fitting results of BaCl2-NH3 kinetic model

图9 0.42 MPa下CaCl2归一化吸附量与反应时间的关系

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

图10 0.42 MPa下CaCl2压力势与反应时间的关系（实心：Ca2-4、Ca8-4；空心：Ca4-8、Ca4-2）

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

图11 CaCl2-NH3动力学模型拟合结果

Fig.11 Fitting results of CaCl2-NH3 kinetic model

表2 CaCl2-NH3动力学模型参数平面方程系数

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

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