Multiscale thermogravimetric kinetics of waste polyvinyl chloride plastics

doi:10.19491/j.issn.1001-9278.2022.05.015

Abstract

Abstract:

Waste poly（vinyl chloride）（PVC） plastic was pyrolyzed to investigate its multi?steps thermal degradation reaction kinetic properties. The kinetic parameters were characterized in three different?scale methods， including the integrated method， weight?loss stage method， and overlapping complex reaction?deconvolution method. The overlapped reactions were separated by peak?fitting of the differential thermogravimetric curves using Fraser?Suzuki deconvolution function. Three model?free methods， including the Friedman’s differential method， Kissinger?Akahira?Sunose’s integral method， and Ozawa?Flynn?Wall’s integral method， were adopted to simplify the kinetics model and estimate the kinetic triplets. The master plots theory was used to obtain the most suitable mechanism model. The results indicated that the integrated method or weight?loss stage method was not appropriate to the determination of the kinetic characteristics of PVC pyrolysis due to the complex overlapping multi?step reactions. The results from the deconvolution method showed that the apparent activation energy of the separated three pseudo reactions based on the KAS method were 128.01， 182.34， and 246.49 kJ/mol， associated with the corresponding pre?exponential factors of 19.84， 26.99， and 33.26 s^-1， respectively. The pseudo reactions 1 and 3 accorded with Avrami?Erofeev^{mechanism model， whereas the pseudo reaction 2 complied with the Prout?Trompkins mechanism model. The results obtained from this work could be used as a theoretical basis for the development and application of clean and efficient waste plastics pyrolysis technology.}

Key words: poly（vinyl chloride）, pyrolysis, reaction kinetics, waste treatment, Frazer?Suzuki deconvolution

CLC Number:

TQ320.9

TANG Yuanjun, LI Xuan, DONG Jun, LI Guoneng, LUO Guanqun, WANG Weimin, XU Yousheng. Multiscale thermogravimetric kinetics of waste polyvinyl chloride plastics[J]. China Plastics, 2022, 36(5): 89-98.

Figures/Tables 12

反应机理类型	反应机理模型名称	$ƒ (α)$
成核与生长模型	A1 Avrami⁃Erofeev	$0.5 1 - α - l n 1 - α 1 / 3$
	A2 Avrami⁃Erofeev	$2 1 - α - l n 1 - α 1 / 2$
	A3 Avrami⁃Erofeev	$3 1 - α - l n 1 - α 2 / 3$
	A4 Avrami⁃Erofeev	$4 1 - α - l n 1 - α 3 / 4$
	B1 Prout⁃Trompkins	$α 1 - α$
几何模型	R2 收缩面模型	$2 1 - α 1 / 2$
	D1 一维模型	$1 / 2 α$
	D2 二维模型	$- l n 1 - α - 1$
反应阶数模型	Or1 一阶模型	1⁃ $α$
	Or2 二阶模型	$1 - α 2$
	Or3 三阶模型	$1 - α 3$
	Or4 四阶模型	$1 - α 4$
随机断裂模型	L2	$2 α 1 / 2 - α$

反应机理类型	反应机理模型名称	$ƒ (α)$
成核与生长模型	A1 Avrami⁃Erofeev	$0.5 1 - α - l n 1 - α 1 / 3$
	A2 Avrami⁃Erofeev	$2 1 - α - l n 1 - α 1 / 2$
	A3 Avrami⁃Erofeev	$3 1 - α - l n 1 - α 2 / 3$
	A4 Avrami⁃Erofeev	$4 1 - α - l n 1 - α 3 / 4$
	B1 Prout⁃Trompkins	$α 1 - α$
几何模型	R2 收缩面模型	$2 1 - α 1 / 2$
	D1 一维模型	$1 / 2 α$
	D2 二维模型	$- l n 1 - α - 1$
反应阶数模型	Or1 一阶模型	1⁃ $α$
	Or2 二阶模型	$1 - α 2$
	Or3 三阶模型	$1 - α 3$
	Or4 四阶模型	$1 - α 4$
随机断裂模型	L2	$2 α 1 / 2 - α$

Tab.1. Commonly used reaction mechanism function ??(α)

Fig.1. TG and DTG curves of PVC at different heating rates

升温速率/ ℃·min^-1	第一阶段				第二阶段
升温速率/ ℃·min^-1	温度/℃	T_pk1/℃	D_pk1/%·min^-1	W₁/%	温度/℃	T_pk2/℃	D_pk2/%·min^-1	W₂/%
5	243.75~384.17	277.75	2.65	70.27	384.17~528.67	452.58	0.39	30.12
10	250.33~386.50	290.33	2.17	70.12	386.50~558.50	464.67	0.37	30.05
15	253.00~384.25	298.00	2.19	69.88	384.25~581.00	473.25	0.35	29.95
20	250.33~383.00	303.33	1.93	69.82	383.00~592.00	474.33	0.34	29.92

Tab.2. Pyrolysis of PVC

Fig.2. Determination of Eα values of PVC using different methods

Fig.3. Relationship between Eα and α （integrated method）

Fig.4. Experimental master?plots and mechanism function curves （integrated method）

Fig.5. Relationship between Eα and α （weight loss stage method）

Fig.6. Experimental master?plots and mechanism function curves （weight loss stage method）

Fig.7. Deconvoluted DTG curves of PVC at heating rate of 5，10，15 and 20 ℃/min

Fig.8. Relationship between Eα and α （Fraser?Suzuki deconvolution method）

Fig.9. Experimental master?plots and mechanism function curves （Fraser?Suzuki deconvolution method）

方法	拟反应	E_α /kJ·mol^-1	lnA/s^-1	ƒ（ $α$ ）
KAS法	FS₁	128.01	19.85	A4
	FS₂	182.34	26.99	B1
	FS₃	246.49	33.27	A4
FWO法	FS₁	130.57	39.94	A4
	FS₂	182.91	47.16	B1
	FS₃	245.87	50.93	A4
Friedman法	FS₁	108.51	22.62	A4
	FS₂	222.22	46.63	B1
	FS₃	233.06	39.34	A4

方法	拟反应	E_α /kJ·mol^-1	lnA/s^-1	ƒ（ $α$ ）
KAS法	FS₁	128.01	19.85	A4
	FS₂	182.34	26.99	B1
	FS₃	246.49	33.27	A4
FWO法	FS₁	130.57	39.94	A4
	FS₂	182.91	47.16	B1
	FS₃	245.87	50.93	A4
Friedman法	FS₁	108.51	22.62	A4
	FS₂	222.22	46.63	B1
	FS₃	233.06	39.34	A4

Tab.3. Kinetic parameters of proposed reactions under Fraser?Suzuki function deconvolution

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