模式拟合法和无模式函数法对月桂酸热解行为及机理的研究

doi:10.3969/j.issn.1001-1803.2021.04.001

Abstract

Abstract:

The pyrolysis kinetics of lauric acid powder in nitrogen and air was studied by comprehensive thermal analysis. The experimental results showed that 30 µm lauric acid powder was rapidly pyrolyzed and gasified in nitrogen atmosphere without exothermic combustion reaction. At different heating rates, the pyrolysis of lauric acid powder in air included two stages: fast pyrolysis and slow pyrolysis. The kinetic parameters of lauric acid pyrolysis in nitrogen and air atmosphere were solved by means of Coats-Redfern method, and the pyrolysis mechanism was described. The results showed that, the rapid pyrolysis of lauric acid in nitrogen and air atmosphere followed the one-dimensional reaction model at phase interface （R1 model）; the apparent activation energy （9.1 kJ/mol） and pre-exponential factor （8.606 1） of lauric acid pyrolysis in nitrogen atmosphere were relatively low, indicating that the oxidation and exothermic behavior of lauric acid inhibited the pyrolysis reaction, but had no obvious effect on its pyrolysis mechanism; when the heating rate was 15 ℃/min, at the same temperature, the conversion of lauric acid pyrolysis in nitrogen atmosphere was higher than that in air atmosphere. The apparent activation energy of lauric acid for different conversion α in air atmosphere was also calculated by using the methods of model-free functions （Flynn-Wall-Ozawa method and Kissinger-Akahira-Sunose method）. The results obtained by the two methods were close to those by the model-fitting method. The average apparent activation energy of lauric acid in air atmosphere was 14.82 kJ/mol; in the range of 10%~80% conversion, the apparent activation energy in the oxidation stage of rapid pyrolysis showed a gentle change with the conversion, which verified that the pyrolysis of lauric acid followed the one-dimensional phase-interface reaction mechanism.

Key words: lauric acid, pyrolysis, model-fitting method, model-free method, kinetics

CLC Number:

TQ645.6

ZHANG Gong-yan,ZHANG Yan-song,CHEN Kun,ZHANG Xin-yan,HUANG Xing-wang. Study on the behavior and mechanism of pyrolysis of lauric acid bymodel-fitting and model-free methods[J].China Surfactant Detergent & Cosmetics, 2021, 51(4): 265-271.

Figures/Tables 10

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References 24

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	机理函数	符号	f（α）	G（α）
化学反应机理	1级	F1	1-α	-ln （1-α）
	1.5级	F1.5	（1-α）^3/2	2[（1-α） ^-1/2-1]
	2级	F2	（1-α）²	（1-α） ^-1-1
	3级	F3	（1-α）³	1/2[（1-α） ^-2-1]
	4级	F4	（1-α）⁴	1/3[（1-α） ^-3-1]
相界面反应机理	一维	R1	1	α
	二维	R2	2 （1-α）^1/2	1- （1-α）^1/2
	三维	R3	3 （1-α）^2/3	1- （1-α）^1/3
随机成核与生长反应机理	Arrami-Erofeev, n=2	A2	2 （1-α）[-ln （1-α）] ^1/2	[-ln （1-α）] ^1/2
	Arrami-Erofeev, n=3	A3	3 （1-α）[-ln （1-α）] ^2/3	[-ln （1-α）] ^1/3
	Arrami-Erofeev, n=4	A4	4 （1-α）[-ln （1-α）] ^3/4	[-ln （1-α）] ^1/4

氮气气氛快速热解气化阶段			空气气氛快速热解氧化阶段
活化能 E/（kJ·mol^-1）	指前因子A/min^-1	相关系数R²	活化能 E/（kJ·mol^-1）	指前因子A/min^-1	相关系数R²
9.1	8.606 1	0.988 9	14.2	49.734 9	0.991 2

转化率/%	Flynn-Wall-Ozawa		Kissinger-Akahira-Sunose
转化率/%	E/（kJ·mol^-1）	R²	E/（kJ·mol^-1）	R²
10	14.01	0.996 3	11.39	0.994 4
20	15.26	0.991 2	12.44	0.986 0
30	16.08	0.988 9	13.14	0.982 7
40	16.57	0.987 4	13.54	0.980 2
50	17.01	0.988 3	13.92	0.981 7
60	17.52	0.987 4	14.38	0.980 5
70	18.16	0.992 0	14.97	0.987 8
80	18.43	0.994 8	15.19	0.992 2
平均值	16.63	—	13.62	—

Study on the behavior and mechanism of pyrolysis of lauric acid bymodel-fitting and model-free methods

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