A kinetics model of dimensionless criterion for microwave chemical reaction:a case study of the decomposition reaction of AIBA hydrochloride

doi:10.11949/0438-1157.20200719

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 8

Fig.1 Schematic diagram of AIBA decomposition reaction

Fig.2 Experimental device diagram

Fig.3 Dimensional analysis modeling process

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

Fig.5 Variation curve of AIBA concentration under microwave heating

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

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

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

Fig.6 Comparison between experimental value and estimated value

References 36

1	魏渊, 郑成, 毛桃嫣, 等. 山嵛酸双酯基有机硅季铵盐的微波合成工艺及性能[J]. 化工进展, 2018, 37(8): 3169-3178.
	Wei Y, Zheng C, Mao T Y, et al. Microwave synthesis process and properties of behenic acid diester-based silicone quaternary ammonium salt [J]. Chemical Industry and Engineering Progress, 2018, 37(8): 3169-3178.
2	Liu S, Mei L, Liang X, et al. Anchoring Fe₃O₄ nanoparticles on carbon nanotubes for microwave-induced catalytic degradation of antibiotics[J]. ACS Applied Materials & Interfaces, 2018, 10(35): 29467-29475.
3	Chen W, Zhang A, Gu Z, et al. Enhanced degradation of refractory organics in concentrated landfill leachate by FeO/H₂O₂ coupled with microwave irradiation[J]. Chemical Engineering Journal, 2018, 354: 680-691.
4	Ao W, Fu J, Mao X, et al. Microwave assisted preparation of activated carbon from biomass: a review[J]. Renewable and Sustainable Energy Reviews, 2018, 92: 958-979.
5	Gao X, Li X, Zhang J, et al. Influence of a microwave irradiation field on vapor–liquid equilibrium[J]. Chemical Engineering Science, 2013, 90: 213-220.
6	赵振宇, 李洪, 李鑫钢, 等. 基于介电性质差异的微波诱导强化蒸馏分离[J]. 化工进展, 2020, 39(6): 2275-2283.
	Zhao Z N, Li H, Li X G, et al. Microwave-induced enhancement of distillation separation based on dielectric properties difference[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2275-2283.
7	凌慧, 郑成, 毛桃嫣, 等. 响应面法优化微波辅助合成中碳链甘油三酯工艺 [J]. 化工学报, 2016, 67: 231-244.
	Ling H, Zheng C, Mao T Y, et al. Optimization of microwave-assisted synthesis of medium-chain triacylalycerols using response surface methodology[J]. CIESC Journal, 2016, 67: 231-244.
8	Hillman F, Zimmerman J M, Paek S-M, et al. Rapid microwave-assisted synthesis of hybrid zeolitic–imidazolate frameworks with mixed metals and mixed linkers[J]. Journal of Materials Chemistry A, 2017, 5(13): 6090-6099.
9	Xin Z, Li L, Zhang X, et al. Microwave-assisted hydrothermal synthesis of chrysanthemum-like Ag/ZnO prismatic nanorods and their photocatalytic properties with multiple modes for dye degradation and hydrogen production[J]. RSC Advances, 2018, 8(11): 6027-6038.
10	Makhado E, Pandey S, Ramontja J. Microwave assisted synthesis of xanthan gum-cl-poly (acrylic acid) based-reduced graphene oxide hydrogel composite for adsorption of methylene blue and methyl violet from aqueous solution[J]. International Journal of Biological Macromolecules, 2018, 119: 255-269.
11	Le T, Ju S, Koppala S, et al. Kinetics study of microwave enhanced reactions between diasporic bauxite and alkali solution[J]. Journal of Alloys and Compounds, 2018, 749: 652-663.
12	雷向欣, 李俊, 沈瀛坪. 微波对乙酸甲酯水解的作用及反应动力学研究[J]. 化学反应工程与工艺, 2002, 18(2): 97-102.
	Lei X X, Li J, Shen Y P. Study on the hydrolysis of methyl acetate under the influence of microwave and the kinetics[J]. Chemical Reaction Engineering and Technology, 2002, 18(2): 97-102.
13	熊俊, 潘晶莹, 吕秀阳. 微波作用下苄苯醚催化转移氢解反应动力学[J]. 化工学报, 2012, 63(5): 1437-1442.
	Xiong J, Pan J Y, Lü X Y. A kinetics study on microwave-assisted catalytic hydrogenolysis of benzyl phenyl ether[J]. CIESC Journal, 2012, 63(5): 1437-1442.
14	丁志伟, 丁辉, 侯钧. 微波作用下的乙酸乙酯合成反应动力学[J]. 化学反应工程与工艺, 2012, 28(5): 458-463.
	Ding Z W, Ding H, Hou J. Kinetics of catalytic synthesis of ethyl acetate under microwave irradiation[J]. Chemical Reaction Engineering and Technology, 2012, 28(5): 458-463.
15	Sturm G S J, Verweij M D, van Gerven T, et al. On the effect of resonant microwave fields on temperature distribution in time and space[J]. International Journal of Heat and Mass Transfer, 2012, 55(13/14): 3800-3811.
16	Patil N G, Benaskar F, Meuldijk J, et al. Microwave assisted flow synthesis: coupling of electromagnetic and hydrodynamic phenomena[J]. AIChE Journal, 2014, 60(11): 3824-3832.
17	Zhu J, Kuznetsov A V, Sandeep K P. Mathematical modeling of continuous flow microwave heating of liquids (effects of dielectric properties and design parameters)[J]. International Journal of Thermal Sciences, 2007, 46(4): 328-341.
18	Wu Y, Hong T, Tang Z, et al. Dynamic model for a uniform microwave-assisted continuous flow process of ethyl acetate production[J]. Entropy, 2018, 20(4): 241.
19	de Bruyn M, Budarin V L, Sturm G S J, et al. Subtle microwave-induced overheating effects in an industrial demethylation reaction and their direct use in the development of an innovative microwave reactor[J]. J. Am. Chem. Soc., 2017, 139(15): 5431-5436.
20	Prosetya H, Datta A. Batch microwave heating of liquids: an experimental study[J]. Journal of Microwave Power and Electromagnetic Energy, 1991, 26(4): 215-226.
21	Gao X, Shu D, Li X, et al. Improved film evaporator for mechanistic understanding of microwave-induced separation process[J]. Frontiers of Chemical Science and Engineering, 2019, 13(4): 759-771.
22	Smith A D, Lester E H, Thurecht K J, et al. Temperature dependence of the dielectric properties of 2, 2′-azobis(2-methyl-butyronitrile) (ambn)[J]. Industrial & Engineering Chemistry Research, 2010, 49(6): 3011-3014.
23	Liu J, Jia G, Lu Z. Dielectric properties of pyridine derivative-water clusters: molecular dynamics simulation[J]. Journal of Molecular Liquids, 2017, 241: 984-991.
24	Ergan B T, Bayramoğlu M. The effects of microwave power and dielectric properties on the microwave-assisted decomposition kinetics of AIBN in n-butanol[J]. Journal of Industrial and Engineering Chemistry, 2013, 19(1): 299-304.
25	Li H, Cui J, Liu J, et al. Mechanism of the effects of microwave irradiation on the relative volatility of binary mixtures[J]. AIChE Journal, 2017, 63(4): 1328-1337.
26	汤建伟, 许秀成, 张宝林, 等. 微波作用磷矿分解反应动力学研究[J]. 化工矿物与加工, 2006, 35(4): 10-13.
	Tang J W, Xu X C, Zhang B L, et al. Study on the kinetics of dissolving reaction of phosphate ore under microwave-induced enhancement[J]. Industrial Minerals & Processing, 2006, 35(4): 10-13.
27	汤建伟, 张宝林, 范秀山, 等. 微波作用下酸解磷矿动力学模型研究[J]. 化学反应工程与工艺, 2007, 23(2): 114-119.
	Tang J W, Zhang B L, Fan X S, et al. Kinetic model of acid dissolving reaction of phosphate rock by microwave induced enhancement[J]. Chemical Reaction Engineering and Technology, 2007, 23(2): 114-119.
28	杨晓庆. 微波与化学反应体系相互作用过程中的特殊效应研究[D]. 成都: 四川大学, 2006.
	Yang X Q. Study on specific effect in the interaction between microwave and chemical reaction[D]. Chengdu: Sichuan University, 2006.
29	郑成, 毛桃嫣, 卫云路, 等. 沸腾状态下十二烷基甲基二羟乙基溴化铵微波合成的动力学研究[J]. 精细化工, 2009, 26(2): 131-135.
	Zheng C, Mao T Y, Wei Y L, et al. Study on the kinetics of the synthesis of dodecymethyldihydroxyethyl ammonium Bromide[J]. Fine Chemicals, 2009, 26(2): 131-135.
30	Dudley G B, Richert R, Stiegman A E. On the existence of and mechanism for microwave-specific reaction rate enhancement[J]. Chem. Sci., 2015, 6(4): 2144-2152.
31	Dudley G B, Stiegman A E. Changing perspectives on the strategic use of microwave heating in organic synthesis[J]. Chem. Rec., 2018, 18(3): 381-389.
32	Costa C, Santos V H S, Araujo P H H, et al. Rapid decomposition of a cationic azo-initiator under microwave irradiation[J]. Journal of Applied Polymer Science, 2010, 118(3): 1421-1429.
33	潘鹤林, 宗原, 黄婕. 《化工原理》课程中的量纲分析法[J]. 教育教学论坛, 2019, (2): 165-167.
	Pan H L, Zong Y, Huang J. Dimensional analysis means in the principles of “Chemical Engineering” [J]. Education Teaching Forum, 2019, (2): 165-167.
34	邵友元. 对量纲分析法与π定理的理解与应用[J]. 东莞理工学院学报, 2010, 17(3): 106-109.
	Shao Y Y. Comprehension and application for dimensional analysis and rule π[J]. Journal of Dongguan University of Technology, 2010, 17(3): 106-109.
35	刘宝平. 量纲分析法在物理建模与计算分析中的应用研究[J]. 太原学院学报(自然科学版), 2019, 37(1): 31-35.
	Liu B P. Application research of dimensional analysis method in physical modeling and computational analysis [J]. Journal of Taiyuan University(Natural Science Edition), 2019, 37(1): 31-35.
36	吴学勇. 量纲分析方法应用研究[J]. 甘肃高师学报, 2000, 5(2): 40-43.
	Wu X Y. Application research of dimensional analysis method [J]. Journal of Gansu Normal University, 2000, 5(2): 40-43.

[1]	Zhenghao JIN, Lijie FENG, Shuhong LI. Energy and exergy analysis of a solution cross-type absorption-resorption heat pump using NH₃/H₂O as working fluid [J]. CIESC Journal, 2023, 74(S1): 53-63.
[2]	Jintong LI, Shun QIU, Wenshou SUN. Oxalic acid and UV enhanced arsenic leaching from coal in flue gas desulfurization by coal slurry [J]. CIESC Journal, 2023, 74(8): 3522-3532.
[3]	Yanhui LI, Shaoming DING, Zhouyang BAI, Yinan ZHANG, Zhihong YU, Limei XING, Pengfei GAO, Yongzhen WANG. Corrosion micro-nano scale kinetics model development and application in non-conventional supercritical boilers [J]. CIESC Journal, 2023, 74(6): 2436-2446.
[4]	Chengze WANG, Kaili GU, Jinhua ZHANG, Jianxuan SHI, Yiwei LIU, Jinxiang LI. Sulfidation couples with aging to enhance the reactivity of zerovalent iron toward Cr(Ⅵ) in water [J]. CIESC Journal, 2023, 74(5): 2197-2206.
[5]	Jieyuan ZHENG, Xianwei ZHANG, Jintao WAN, Hong FAN. Synthesis and curing kinetic analysis of eugenol-based siloxane epoxy resin [J]. CIESC Journal, 2023, 74(2): 924-932.
[6]	Yujun MA, Xiangjun LIU. Theoretical studies of water recovery from flue gas by using ceramic membrane [J]. CIESC Journal, 2022, 73(9): 4103-4112.
[7]	Huan ZHOU, Mengli ZHANG, Qing HAO, Si WU, Jie LI, Cunbing XU. Process mechanism and dynamic behaviors of magnesium sulfate type carnallite converting into kainite [J]. CIESC Journal, 2022, 73(9): 3841-3850.
[8]	Qianshi SONG, Xiaowei WANG, Wei ZHANG, Xiaohan WANG, Haowen LI, Yu QIAO. Catalytic/inhibitory effects of inorganic elements on biomass char-CO₂ gasification reactivity and model construction [J]. CIESC Journal, 2022, 73(11): 5240-5250.
[9]	ZHANG Muxing, ZHANG Xiaosong, DING Ye, SONG Yi. Molecular dynamics study on influence of interlayer spacing of nanoporous graphene oxide membrane on electrodialysis based air dehumidification [J]. CIESC Journal, 2021, 72(S1): 63-69.
[10]	ZHANG Mengfei, ZHANG Ling, LI Xiaochuang, ZU Yunqiu, HUANG Ming, SHI Xianzhang, LIU Chuntai. Simulation and experimental study on non-isothermal vulcanization process of thick-walled rubber products [J]. CIESC Journal, 2021, 72(4): 2065-2075.
[11]	LI Chaofan, WEN Yujuan, CAO Nan, SUN Dong, SONG Xiaoming, YANG Yuesuo. Biodegradation kinetics of p-nitrophenol at low-temperature [J]. CIESC Journal, 2021, 72(3): 1692-1701.
[12]	YANG Shi, CAI Yang, LI Changping, LI Xuehui. Preparation of phosphotungstic acid loaded Zr-based metal-organic framework PTA@MOF-808 and its adsorption desulfurization performance [J]. CIESC Journal, 2021, 72(3): 1722-1731.
[13]	WANG Yuejie, LI Lingling, HE Chunhong. Review on the bioleaching of spent refinery catalysts for metals removal [J]. CIESC Journal, 2021, 72(2): 901-912.
[14]	Shuangchen MA, Quan ZHOU, Jianzong CAO, Qi LIU, Wentong CHEN, Shuaijun FAN, Yakun YAO, Chenyu LIN, Caini MA. Modeling and simulation of wet desulfurization system dynamic process [J]. CIESC Journal, 2020, 71(8): 3741-3751.
[15]	Peng WANG, Jinglei LIU, Shengzhong ZHANG, Dequan FAN, Ying ZHANG, Hong XU. Effect of structured 5A molecular sieve adsorption bed structure and process parameters on N₂/H₂ adsorption performance [J]. CIESC Journal, 2020, 71(7): 3114-3122.