绝热加速量热无模型方法动力学预测

doi:10.11949/0438-1157.20221122

摘要/Abstract

摘要：

绝热加速量热主要采用基于单一实验数据的模型拟合方法进行动力学预测，难以应用于未知机理反应和复杂反应。为此，通过数值模拟方法在绝热条件下产生n级反应与Kamal自催化反应数据，采用Vyazovkin和Friedman等转化率方法进行动力学求解；然后在不同起始温度和等温条件下，采用无模型动力学参数进行绝热和等温动力学预测，并与模拟数据对比。结果表明，绝热加速量热采用Vyazovkin方法预测最大相对误差为39.9%，Friedman方法预测最大误差超100%，前者更适合进行预测；建议在预测温度±40℃范围内进行实验测量。这为未知化学物质和复杂反应热失控风险评估及化工事故模拟等提供了有效手段。

关键词: 化学反应, 稳定性, 绝热加速量热, Friedman方法, Vyazovkin方法, 动力学预测, 数值模拟

Abstract:

The adiabatic accelerating rate calorimetry (ARC) mainly adopts model-fitting method based on single experimental data for kinetic prediction, which is difficult to be applied to unknown mechanism and complex reactions. In this study, the reactions of n-order and Kamal autocatalytic model under adiabatic conditions are generated by numerical simulations, and the kinetic parameters are estimated by Vyazovkin and Friedman conversional methods. Then, under different onset temperatures and isothermal conditions, the adiabatic and isothermal reactions are predicted by using the kinetic parameters solved by the model-free methods, and compared with the simulated data. The results show that ARC can use the model-free methods to carry out adiabatic and isothermal kinetic prediction, and it has good prediction accuracy. The maximum relative error of Vyazovkin method is 39.9% and that of Friedman method is over 100%, and the Vyazovkin method is more suitable for prediction than Friedman method. It is recommended to carry out experimental measurements within the predicted temperature range of ±40℃. Kinetic predictions using the model-free methods have good accuracy and efficiency, which is of great significance for the kinetic analysis of new chemicals and complex reactions. This will effectively support the risk assessment of thermal runaway and the accident simulation.

Key words: chemical reaction, stability, adiabatic accelerating rate calorimetry, Friedman method, Vyazovkin method, kinetic prediction, numerical simulation

中图分类号:

O 643.12

杨遂军, 丁炯, 许启跃, 叶树亮, 郭子超, 陈网桦. 绝热加速量热无模型方法动力学预测[J]. 化工学报, 2022, 73(11): 4987-4997.

Suijun YANG, Jiong DING, Qiyue XU, Shuliang YE, Zichao GUO, Wanghua CHEN. Kinetic predictions from adiabatic accelerating rate calorimetric data by using the model-free methods[J]. CIESC Journal, 2022, 73(11): 4987-4997.

图/表 16

参考文献 35

1	Townsend D I, Tou J C. Thermal hazard evaluation by an accelerating rate calorimeter[J]. Thermochimica Acta, 1980, 37(1): 1-30.
2	丁炯, 陈琪, 许启跃, 等. 融合C80数据的绝热加速量热法热惯量因子修正[J]. 化工学报, 2019, 70(1): 417-424.
	Ding J, Chen Q, Xu Q Y, et al. ARC thermal inertia correction method based on C80 data merging[J]. CIESC Journal, 2019, 70(1): 417-424.
3	魏彤彤, 钱新明, 袁梦琦. 酸、碱污染物对过氧化苯甲酸叔丁酯热危险性影响[J]. 化工学报, 2015, 66(10): 3931-3939.
	Wei T T, Qian X M, Yuan M Q. Thermal hazard analysis for tert-butyl peroxybenzoate contaminated by acid or alkali[J]. CIESC Journal, 2015, 66(10): 3931-3939.
4	蒋慧灵, 闫松, 魏彤彤. 水分对过氧化苯甲酸叔丁酯热稳定性的影响[J]. 化工学报, 2011, 62(5): 1290-1295.
	Jiang H L, Yan S, Wei T T. Effect of water on thermal stability of tert-butyl peroxy benzoate[J]. CIESC Journal, 2011, 62(5): 1290-1295.
5	Samael V K J, Smitha V S, Sivanesh N E, et al. Reactive thermal hazards of irradiated tributyl phosphate with nitric acid[J]. Thermochimica Acta, 2018, 666: 18-26.
6	Roduit B, Hartmann M, Folly P, et al. New kinetic approach for evaluation of hazard indicators based on merging DSC and ARC or large scale tests[J]. Chemical Engineering Transactions, 2016, 48: 37-42.
7	Jeraal M I, Roberts K J, McRobbie I, et al. Assessment of the thermal degradation of sodium lauroyl isethionate using predictive isoconversional kinetics and a temperature-resolved analysis of evolved gases[J]. Industrial & Engineering Chemistry Research, 2019, 58(19): 8112-8122.
8	郭子超, 郝琳, 卫宏远. 一种计算最大反应速率到达时间的新方法[J]. 化工学报, 2016, 67(S1): 22-27.
	Guo Z C, Hao L, Wei H Y. A new method for calculating time to maximum rate under adiabatic condition[J]. CIESC Journal, 2016, 67(S1): 22-27.
9	朱益, 王浩, 陈利平, 等. 基于数值计算方法计算最大反应速率到达时间[J]. 化工学报, 2019, 70(1): 379-387.
	Zhu Y, Wang H, Chen L P, et al. Calculate time to maximum rate under adiabatic condition by numerical calculation method[J]. CIESC Journal, 2019, 70(1): 379-387.
10	de Jesus Silva A J, Contreras M M, Nascimento C R, et al. Kinetics of thermal degradation and lifetime study of poly(vinylidene fluoride) (PVDF) subjected to bioethanol fuel accelerated aging[J]. Heliyon, 2020, 6(7): e04573.
11	Käser F, Roduit B. Prediction of the ageing of rubber using the chemiluminescence approach and isoconversional kinetics[J]. Journal of Thermal Analysis and Calorimetry, 2008, 93(1): 231-237.
12	余成明, 彭旭东, 江锦波, 等. 宽温域下氟醚橡胶的加速老化行为和机理研究[J]. 化工学报, 2021, 72(6): 3399-3410.
	Yu C M, Peng X D, Jiang J B, et al. Investigation on accelerated aging behavior and mechanism of fluoroether rubber under wide temperature range[J]. CIESC Journal, 2021, 72(6): 3399-3410.
13	韩露, 马芳武, 陈实现, 等. 玄武岩纤维增强聚乳酸力学性能及耐老化性能[J]. 化工学报, 2019, 70(3): 1171-1178.
	Han L, Ma F W, Chen S X, et al. Mechanical properties of basalt fiber-reinforced polylactide matrix and aging resistance properties[J]. CIESC Journal, 2019, 70(3): 1171-1178.
14	Stanko M, Stommel M. Kinetic prediction of fast curing polyurethane resins by model-free isoconversional methods[J]. Polymers, 2018, 10(7): 698.
15	Vyazovkin S, Burnham A K, Criado J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1/2): 1-19.
16	Friedman H L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic[J]. Journal of Polymer Science Part C: Polymer Symposia, 1964, 6(1): 183-195.
17	Flynn J H, Wall L A. General treatment of the thermogravimetry of polymers[J]. Journal of Research of the National Bureau of Standards. Section A, Physics and Chemistry, 1966, 70A(6): 487-523.
18	Kissinger H E. Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706.
19	Vyazovkin S, Dollimore D. Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids[J]. Journal of Chemical Information and Computer Sciences, 1996, 36(1): 42-45.
20	Vyazovkin S. Evaluation of activation energy of thermally stimulated solid-state reactions under arbitrary variation of temperature[J]. Journal of Computational Chemistry, 1997, 18(3): 393-402.
21	Vyazovkin S. Modification of the integral isoconversional method to account for variation in the activation energy[J]. Journal of Computational Chemistry, 2001, 22(2): 178-183.
22	Ding J, Chen L X, Xu Q Y, et al. Differential isoconversional kinetic approach for accelerating rate calorimetry[J]. Thermochimica Acta, 2020, 689: 178607.
23	Ding J, Zhang X C, Hu D F, et al. Model-free kinetic determination of pre-exponential factor and reaction mechanism in accelerating rate calorimetry[J]. Thermochimica Acta, 2021, 702: 178983.
24	Yang S J, Ding J, Zhang X C, et al. Thermal inertias and confidence intervals in the determination of activation energy by isoconversional methods applied for accelerating rate calorimetry[J]. Thermochimica Acta, 2022, 716: 179290.
25	Yang S J, Ding J, Zhang X C, et al. Fusion method of model-free and model-fitting for complex reactions in accelerating rate calorimetry[J]. Thermochimica Acta, 2022, 712: 179212.
26	Burnham A K, Dinh L N. A comparison of isoconversional and model-fitting approaches to kinetic parameter estimation and application predictions[J]. Journal of Thermal Analysis and Calorimetry, 2007, 89(2): 479-490.
27	Cai J M, Chen Y, Liu R R. Isothermal kinetic predictions from nonisothermal data by using the iterative linear integral isoconversional method[J]. Journal of the Energy Institute, 2014, 87(3): 183-187.
28	Granado L, Sbirrazzuoli N. Isoconversional computations for nonisothermal kinetic predictions[J]. Thermochimica Acta, 2021, 697: 178859.
29	Sbirrazzuoli N. Model-free isothermal and nonisothermal predictions using advanced isoconversional methods[J]. Thermochimica Acta, 2021, 697: 178855.
30	Vyazovkin S. Isoconversional Kinetics of Thermally Stimulated Processes[M]. Cham: Springer International Publishing, 2015.
31	Roduit B, Folly P, Berger B, et al. Evaluating sadt by advanced kinetics-based simulation approach[J]. Journal of Thermal Analysis and Calorimetry, 2008, 93(1): 153-161.
32	杨庭, 陈利平, 陈网桦, 等. 分解反应自催化性质快速鉴别的实验方法[J]. 物理化学学报, 2014, 30(7): 1215-1222.
	Yang T, Chen L P, Chen W H, et al. Experimental method on rapid identification of autocatalysis in decomposition reactions[J]. Acta Physico-Chimica Sinica, 2014, 30(7): 1215-1222.
33	Kamal M R. Thermoset characterization for moldability analysis[J]. Polymer Engineering & Science, 1974, 14(3): 231-239.
34	Sbirrazzuoli N. Is the Friedman method applicable to transformations with temperature dependent reaction heat?[J]. Macromolecular Chemistry and Physics, 2007, 208(14): 1592-1597.
35	Vyazovkin S, Burnham A K, Favergeon L, et al. ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics[J]. Thermochimica Acta, 2020, 689: 178597.

温度/ ℃	方法	t_α_=10%/ min	t_α_=50%/ min	t_α_=90%/ min	TMR_ad/ min
50	SIM	3432415	4258816	4262877	4262893
	VYA	3380655 (-1.5%)	4198628 (-1.4%)	4202742 (-1.4%)	4202758 (-1.4%)
	FR	830242 (-75.8%)	1433763 (-66.3%)	1437120 (-66.3%)	1437133 (-66.3%)
80	SIM	26793	36108	36226	36225
	VYA	26755 (-0.1%)	36029 (-0.2%)	36149 (-0.2%)	36148 (-0.2%)
	FR	12346 (-53.9%)	20377 (-43.6%)	20480 (-43.5%)	20480 (-43.5%)
110	SIM	445.80	656.40	662.00	662.00
	VYA	450.50 (1.1%)	661.10 (0.7%)	666.90 (0.7%)	666.80 (0.7%)
	FR	453.30 (1.7%)	661.30 (0.7%)	666.40 (0.7%)	666.30 (0.6%)
150	SIM	4.65	7.74	7.91	7.91
	VYA	4.76 (2.4%)	7.85 (1.4%)	8.04 (1.6%)	8.03 (1.5%)
	FR	17.00 (265.6%)	20.44 (164.1%)	20.61 (160.6%)	20.61 (160.6%)
180	SIM	0.26	0.47	0.49	0.49
	VYA	0.26 (0)	0.48 (2.1%)	0.50 (2.0%)	0.50 (2.0%)
	FR	3.02 (1061.5%)	3.27 (595.7%)	3.29 (571.4%)	3.29 (571.4%)

温度/ ℃	方法	t_α_=10%/ min	t_α_=50%/ min	t_α_=90%/ min	TMR_ad/ min
50	SIM	3432415	4258816	4262877	4262893
	VYA	3380655 (-1.5%)	4198628 (-1.4%)	4202742 (-1.4%)	4202758 (-1.4%)
	FR	830242 (-75.8%)	1433763 (-66.3%)	1437120 (-66.3%)	1437133 (-66.3%)
80	SIM	26793	36108	36226	36225
	VYA	26755 (-0.1%)	36029 (-0.2%)	36149 (-0.2%)	36148 (-0.2%)
	FR	12346 (-53.9%)	20377 (-43.6%)	20480 (-43.5%)	20480 (-43.5%)
110	SIM	445.80	656.40	662.00	662.00
	VYA	450.50 (1.1%)	661.10 (0.7%)	666.90 (0.7%)	666.80 (0.7%)
	FR	453.30 (1.7%)	661.30 (0.7%)	666.40 (0.7%)	666.30 (0.6%)
150	SIM	4.65	7.74	7.91	7.91
	VYA	4.76 (2.4%)	7.85 (1.4%)	8.04 (1.6%)	8.03 (1.5%)
	FR	17.00 (265.6%)	20.44 (164.1%)	20.61 (160.6%)	20.61 (160.6%)
180	SIM	0.26	0.47	0.49	0.49
	VYA	0.26 (0)	0.48 (2.1%)	0.50 (2.0%)	0.50 (2.0%)
	FR	3.02 (1061.5%)	3.27 (595.7%)	3.29 (571.4%)	3.29 (571.4%)

温度/ ℃	方法	t_α_=10%/ min	t_α_=50%/ min	t_α_=90%/ min
50	SIM	7636348	50239458	166899493
	VYA	7554461 (-1.1%)	50680113 (0.9%)	173364554 (3.9%)
	FR	2683485 (-64.9%)	40428782 (-19.5%)	155819398 (-6.6%)
80	SIM	53330	350856	1165572
	VYA	53340 (0)	354912 (1.2%)	1211859 (4.0%)
	FR	29833 (-44.1%)	315057 (-10.2%)	1139930 (-2.2%)
110	SIM	810	5331	17711
	VYA	818 (1.0%)	5406 (1.4%)	18429 (4.1%)
	FR	807 (-0.4%)	5464 (2.5%)	18263 (3.1%)
150	SIM	7.70	50.50	167.80
	VYA	7.80 (1.3%)	51.40 (1.8%)	174.80 (4.2%)
	FR	21.50 (179.2%)	69.00 (36.6%)	192.80 (14.9%)
180	SIM	0.40	2.63	8.75
	VYA	0.41 (2.5%)	2.68 (1.9%)	9.11 (4.1%)
	FR	3.31 (727.5%)	5.91 (124.7%)	12.45 (42.3%)

温度/ ℃	方法	t_α_=10%/ min	t_α_=50%/ min	t_α_=90%/ min
50	SIM	7636348	50239458	166899493
	VYA	7554461 (-1.1%)	50680113 (0.9%)	173364554 (3.9%)
	FR	2683485 (-64.9%)	40428782 (-19.5%)	155819398 (-6.6%)
80	SIM	53330	350856	1165572
	VYA	53340 (0)	354912 (1.2%)	1211859 (4.0%)
	FR	29833 (-44.1%)	315057 (-10.2%)	1139930 (-2.2%)
110	SIM	810	5331	17711
	VYA	818 (1.0%)	5406 (1.4%)	18429 (4.1%)
	FR	807 (-0.4%)	5464 (2.5%)	18263 (3.1%)
150	SIM	7.70	50.50	167.80
	VYA	7.80 (1.3%)	51.40 (1.8%)	174.80 (4.2%)
	FR	21.50 (179.2%)	69.00 (36.6%)	192.80 (14.9%)
180	SIM	0.40	2.63	8.75
	VYA	0.41 (2.5%)	2.68 (1.9%)	9.11 (4.1%)
	FR	3.31 (727.5%)	5.91 (124.7%)	12.45 (42.3%)

温度/ ℃	方法	t_α_=10%/ h	t_α_=50%/ h	t_α_=90%/ h	TMR_ad/ h
80	SIM	21425	23652	23656	23656
	VYA	22145 (3.4%)	24972 (5.6%)	24977 (5.6%)	24977 (5.6%)
	FR	9913 (-53.7%)	12851 (-45.7%)	12855 (-45.7%)	12855 (-45.7%)
100	SIM	918	1113	1114	1114
	VYA	926 (0.9%)	1116 (0.3%)	1117 (0.3%)	1117 (0.3%)
	FR	685 (-25.4%)	893 (-19.8%)	894 (-19.7%)	894 (-19.7%)
110	SIM	211.50	268.90	269.30	269.30
	VYA	214.60 (1.5%)	270.20 (0.5%)	270.70 (0.5%)	270.60 (0.5%)
	FR	210.00 (-0.7%)	272.20 (1.2%)	272.60 (1.2%)	272.60 (1.2%)
120	SIM	52.20	69.40	69.60	69.60
	VYA	53.60 (2.7%)	71.10 (2.4%)	71.30 (2.4%)	71.30 (2.4%)
	FR	71.40 (36.8%)	91.30 (31.6%)	91.50 (31.5%)	91.50 (31.5%)
150	SIM	1.16	1.73	1.75	1.75
	VYA	1.24 (6.9%)	2.04 (17.9%)	2.08 (18.9%)	2.07 (18.3%)
	FR	5.06 (336.2%)	6.00 (246.8%)	6.03 (244.6%)	6.03 (244.6%)