微波化学反应的无量纲准数动力学模型研究：以偶氮二异丁脒盐酸盐（AIBA）分解反应为例

doi:10.11949/0438-1157.20200719

摘要/Abstract

摘要：

微波辅助化学已成为备受关注的研究课题，但微波反应动力学模型缺乏系统的研究严重阻碍了微波在化学工业化上的应用，微波化学反应在化学工程化的放大设计及应用缺乏基础依据。以偶氮二异丁脒盐酸盐（AIBA）分解反应为例，通过选择合适的溶剂调整其复配比例，得到一系列具有不同沸点的混合溶剂作为反应介质，使反应在混合溶剂沸点下进行，以保证反应过程中微波的持续作用来研究微波反应动力学。从微波作用下动量传递、热量传递和质量传递的影响因素进行考虑，选择了对微波化学反应必须和充分的因素，包括微波功率密度 p、黏度 μ、密度ρ、反应物的浓度 C_A、温度 T、热导率 λ、损耗角正切δ 和微波辐射频率f。采用量纲分析方法，通过模型分析建立了微波分解反应动力学模型。通过大量的实验数据进行拟合，回归出特定反应的模型参数。该模型估算值与实验值的误差较小，相关性较高，具有一定的预测能力可解决微波反应过程放大的基础性问题，有望用于指导微波工业化生产。

关键词: 微波辐射, 动力学模型, 分解反应, 量纲分析法

Abstract:

Microwave-assisted chemistry has become a hot research topic, but the lack of systematic research on microwave reaction kinetics model has seriously hindered the application of microwave in chemical industrialization. And the amplification design and application of microwave chemical reactions in chemical engineering is lack of foundation. In this paper, the decomposition reaction of AIBA is taken as an example. A series of mixed solvents with different boiling points were obtained by adjusting the mixture ratio of solvents. And the reaction was carried out under the boiling point of mixed solvents, so as to ensure the consistency of temperature and the continuous action of microwave in the reaction process. The influence factors of momentum transfer, heat transfer and mass transfer under microwave irradiation were considered comprehensively. The necessary and sufficient factors for microwave chemical reaction were selected, including microwave power density p, viscosity μ,density ρ, reactant concentration C_A, temperature T, thermal conductivity λ, loss angle tangent tan δ, and microwave radiation frequency f. A kinetic model of microwave decomposition reaction of AIBA is established by dimensionless dimensional analysis. The model parameters of the specific reaction are regressed by fitting a large number of experimental data. The error between the estimated value and the experimental value is small and the correlation is high, which indicates that the model has certain predictive ability. So the model can solve the basic problem of microwave reaction amplification, and is expected to be used to guide the industrial production of microwave reaction.

Key words: microwave irradiation, kinetic model, decomposition reaction, dimensional analysis

中图分类号:

毛桃嫣, 邹敏婷, 郑成, 曾昭文, 伍旭贤, 肖润辉, 彭思玉. 微波化学反应的无量纲准数动力学模型研究：以偶氮二异丁脒盐酸盐（AIBA）分解反应为例[J]. 化工学报, 2021, 72(3): 1364-1371.

MAO Taoyan, ZOU Minting, ZHENG Cheng, ZENG Zhaowen, WU Xuxian, XIAO Runhui, PENG Siyu. A kinetics model of dimensionless criterion for microwave chemical reaction:a case study of the decomposition reaction of AIBA hydrochloride[J]. CIESC Journal, 2021, 72(3): 1364-1371.

图/表 8

图1 AIBA分解反应过程示意图

Fig.1 Schematic diagram of AIBA decomposition reaction

图2 实验装置流程图

Fig.2 Experimental device diagram

图3 量纲分析建模流程

Fig.3 Dimensional analysis modeling process

图4 AIBA分解反应在微波辐射下的加热曲线和功率曲线

Fig.4 Heating and power curve of AIBA decomposition reaction under different microwave irradiation

图5 AIBA在微波加热的浓度变化曲线

Fig.5 Variation curve of AIBA concentration under microwave heating

表1 物理参数的量纲

Table 1 Dimension of various parameters

物理参数	符号	单位	量纲
反应速率	$(- r A)$	mol·m^-3·s^-1	NT^-1L^-1
功率密度	p	W·m^-3	ML^-1T^-3
黏度	μ	Pa·s	ML^-1T^-1
密度	ρ	kg·m^-3	ML^-3
反应物浓度	C_A	mol·m^-3	NL^-3
温度	T	K	Θ
损耗角正切	$t a n δ$		1
微波频率	f	Hz	T^-1
热导率	λ	W·m^-1·K^-1	MLT^-3Θ^-1

表1 物理参数的量纲

Table 1 Dimension of various parameters

物理参数	符号	单位	量纲
反应速率	$(- r A)$	mol·m^-3·s^-1	NT^-1L^-1
功率密度	p	W·m^-3	ML^-1T^-3
黏度	μ	Pa·s	ML^-1T^-1
密度	ρ	kg·m^-3	ML^-3
反应物浓度	C_A	mol·m^-3	NL^-3
温度	T	K	Θ
损耗角正切	$t a n δ$		1
微波频率	f	Hz	T^-1
热导率	λ	W·m^-1·K^-1	MLT^-3Θ^-1

表2 不同复配比例下溶液的理化性质

Table 2 Physical and chemical properties of solutions with different compound proportions

水-乙醇体积比	沸点/K	密度/ (kg·m^-3)	黏度/ (Pa·s)	热导率/ (W·m^-1·K^-1)
1.5∶8.5（500 W）	366	950.4	0.310×10^-3	0.603
2∶8（500 W）	363.8	947.8	0.319×10^-3	0.594
2.5∶7.5（500 W）	362.1	944.3	0.327×10^-3	0.583
3∶7（500 W）	360.7	940.1	0.343×10^-3	0.572
3.5∶6.5（500 W）	358.4	936.2	0.345×10^-3	0.560
1.5∶8.5（400 W）	366.2	950.2	0.309×10^-3	0.603
2∶8（400 W）	362.7	948.9	0.323×10^-3	0.594
2.5∶7.5（400 W）	361.1	945.3	0.331×10^-3	0.584
3∶7（400 W）	359.3	941.5	0.349×10^-3	0.572
3.5∶6.5（400 W）	357	937.6	0.351×10^-3	0.560
1.5∶8.5（300 W）	366	950.4	0.310×10^-3	0.603
2∶8（300 W）	362.1	949.5	0.325×10^-3	0.594
2.5∶7.5（300 W）	360.7	945.7	0.332×10^-3	0.584
3∶7（300 W）	358.4	942.4	0.348×10^-3	0.572
3.5∶6.5（300 W）	357.3	937.3	0.350×10^-3	0.560
1.5∶8.5（200 W）	366.2	950.2	0.309×10^-3	0.603
2∶8（200 W）	362.5	949.1	0.324×10^-3	0.594
2.5∶7.5（200 W）	360.4	946.0	0.333×10^-3	0.584
3∶7（200 W）	358.2	942.6	0.355×10^-3	0.572
3.5∶6.5（200 W）	355.5	939.1	0.357×10^-3	0.560

图6 实验值与估算值的比较

Fig.6 Comparison between experimental value and estimated value

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