芦苇秆热解特性及动力学分析

doi:10.3969/j.issn.1673-5854.2019.04.002

摘要/Abstract

摘要：

为了充分利用芦苇秆生物质能源，以不同升温速率对芦苇秆进行热重实验，分别运用Coats-Redfern（CR）法、Flynn-Wall-Ozawa（FWO）法、Kissinger-Akahira-Sunose（KAS）法计算芦苇秆热解动力学参数，并利用主函数图法确定反应机理和动力学。结果表明：芦苇秆热解可分为4个阶段，其中190~400℃为主要热解阶段。在此阶段，将3种方法计算所得转化率（α）与实验数据进行对比，发现当温度大于250℃时，Coats-Redfern法计算值与实验数据偏差较大，而Flynn-Wall-Ozawa法与Kissinger-Akahira-Sunose法在整个阶段内吻合度较高。由主函数图法可知芦苇秆热解最佳反应机理为随机成核，反应级数为2。对比残差平方和发现，Kissinger-Akahira-Sunose法相比于Flynn-Wall-Ozawa法更适合计算芦苇秆热解动力学参数，计算的表观活化能随转化率的增大呈先增大后减小的趋势，并在转化率为50%时达到最大值286.9 kJ/mol。

关键词: 热解, 动力学, 热重分析, 生物质, 芦苇秆

Abstract:

In order to make full use of the Phragmites australis as biomass energy, pyrolysis test for Phragmites australis stalk was performed at different heating rates. The kinetic parameters of Phragmites australis pyrolysis were calculated by Coats-Redfern(CR) method, Flynn-Wall-Ozawa(FWO) method and Kissinger-Akahira-Sunose(KAS) method. The results showed that the pyrolysis of Phragmites australis stalk could be divided into four stages, of which the stage of 190-400℃ was the main pyrolysis stage. At this stage, comparing the conversion rate(α)calculated from the three methods with the experimental data, it was found that the deviation between the calculated values of the Coats-Redfern method and the experimental data was larger when the temperature was more than 250℃. The conversion rates obtained by using Flynn-Wall-Ozawa method and Kissinger-Akahira-Sunose method were in good agreement with the experimental values at the whole pyrolysis stage. According to the master-plots method, the optimal reaction mechanism of pyrolysis was random nucleation and the reaction series was 2.It was found that the Kissinger-Akahira-Sunose method was more suitable for calculating the kinetic parameters of Phragmites australis stalk pyrolysis compared with the Flynn-Wall-Ozawa method. The apparent activation energy calculated by the Kissinger-Akahira-Sunose method increased first and then decreased with the increase of conversion rate. And the activation energy reached the maximum(286.9 kJ/mol) when the conversion rate was 50%.

Key words: pyrolysis, kinetic, thermogravimetric analysis, biomass, Phragmites australis stalk

中图分类号:

TQ35
TK6

张旭,孙姣,范赢,曹永全,陈文义. 芦苇秆热解特性及动力学分析[J]. 生物质化学工程, 2019, 53(4): 9-18.

Xu ZHANG,Jiao SUN,Ying FAN,Yongquan CAO,Wenyi CHEN. Pyrolysis Characteristics and Kinetic Analysis of Phragmites australis Stalk[J]. Biomass Chemical Engineering, 2019, 53(4): 9-18.

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升温速率(β)/ (℃·min^-1) heating rate	热解初始温度(T_i)/℃ initial temperature of pyrolysis	热解最终温度(T_f)/℃ final temperature of pyrolysis	最大失重速率对应的温度(T_p)/℃ temperature of the maximum weight loss rate	最大失重速率(DTG_max)/(%·min^-1) the maximum weight loss rate	失重率/% quality loss
10	198	386	360	8.4	64.3
20	208	405	371	15.7	65.1
30	216	432	379	18.3	66.9

升温速率(β)/ (℃·min^-1) heating rate	活化能(E)/(kJ·mol^-1) activation energy	指前因子(A)/min^-1 pre-finger factor	相关系数(R²) correlation coefficient
10	80.7	9.86×10⁵	0.95387
20	81.7	2.41×10⁶	0.95254
30	85.9	4.74×10⁶	0.96275

转化率(α)/% conversion rate	活化能(E)/(kJ·mol^-1) reaction activation energy	指前因子(A)/min^-1 pre-finger factor	相关系数(R²) correlation coefficient
10	221.8	8.66×10¹²	0.97552
20	225.8	5.90×10¹²	0.96367
30	263.9	4.40×10¹⁵	0.97563
40	283.8	5.42×10¹⁶	0.96367
50	286.2	1.79×10¹⁶	0.99264
60	275.5	1.12×10¹⁵	0.99573
70	250.5	5.87×10¹²	0.99913
80	223.1	5.74×10⁹	0.99049

反应机理 reaction mechanism	符号 symbol	f(α)	G(α)	δ²
反应机理 reaction mechanism	符号 symbol	f(α)	G(α)	FWO	KAS
随机成核 Avrami-Erofeev	A_3/2	${ \frac{{3}}{{2}}}$(1-α)[-ln(1-α)]$^{ \frac{{1}}{{3}}}$	[-ln(1-α)]$^{ \frac{{2}}{{3}}}$	21.84	22.17
随机成核 Avrami-Erofeev	A₂	2(1-α)[-ln(1-α)]$^{ \frac{{1}}{{2}}}$	[-ln(1-α)]$^{ \frac{{1}}{{2}}}$	2.17	2.08
随机成核 Avrami-Erofeev	A₃	3(1-α)[-ln(1-α)]$^{ \frac{{2}}{{3}}}$	[-ln(1-α)]$^{ \frac{{1}}{{3}}}$	2.28	2.16
随机成核 Avrami-Erofeev	A₄	4(1-α)[-ln(1-α)]$^{ \frac{{3}}{{4}}}$	[-ln(1-α)]$^{ \frac{{1}}{{4}}}$	2.39	2.26
一维扩散 one-dimensional diffusion	D₁	${ \frac{{1}}{{ 2α}}}$	α²	5.80	5.86
二维扩散 two-dimensional diffusion	D₂	[-ln(1-α)]^-1	α+(1-α)ln(1-α)	10.83	11.01
三维扩散 three-dimensional diffusion(Jander)	D₃	${ \frac{{3}}{{2}}}$(1-α)$^{ \frac{{2}}{{3}}}$[1-(1-α)$^{ \frac{{1}}{{3}}}$]^-1	1-${ \frac{{2}}{{3α}}}$-(1-α)$^{ \frac{{2}}{{3}}}$	15.08	15.33
四维扩散 four-dimensional diffusion (Ginstring-Brounshtein)	D₄	${ \frac{{2}}{{3}}}$[(1-α)$^{ \frac{{1}}{{3}}}$-1]^-1	[1-(1-α)$^{ \frac{{1}}{{3}}}$]²	30.58	30.99
0级反应zero-order	F₀	1	α	2.98	2.88
一级反应first-order	F₁	1-α	-ln(1-α)	4.51	4.56
二级反应second-order	F₂	(1-α)²	(1-α)^-1-1	54.17	54.75
三级反应third-order	F₃	(1-α)³	${ \frac{{1}}{{2}}}$[(1-α)^-2-1]	989.39	991.98
幂定律power law	P₂	2α$^{ \frac{{1}}{{2}}}$	α$^{ \frac{{1}}{{2}}}$	2.87	2.72
幂定律power law	P₃	3α$^{ \frac{{2}}{{3}}}$	α$^{ \frac{{1}}{{3}}}$	2.85	2.70
幂定律power law	P₄	4α$^{ \frac{{3}}{{4}}}$	α$^{ \frac{{1}}{{4}}}$	2.84	2.68
相界反应 contracting cylinder	R₂	2(1-α)$^{ \frac{{1}}{{2}}}$	1-(1-α)$^{ \frac{{1}}{{2}}}$	2.91	2.86
相界反应 contracting cylinder	R₃	3(1-α)$^{ \frac{{2}}{{3}}}$	1-(1-α)$^{ \frac{{1}}{{3}}}$	3.12	3.11

转化率(α)/% conversion rate	活化能(E)/(kJ·mol^-1) reaction activation energy	指前因子(A)/min^-1 pre-finger factor	相关系数(R²) correlation coefficient
10	220.1	8.04×10¹¹	0.96681
20	223.7	5.88×10¹¹	0.96068
30	260.2	4.41×10¹⁴	0.97387
40	282.7	5.38×10¹⁵	0.97613
50	286.9	1.76×10¹⁵	0.98423
60	274.8	1.11×10¹⁴	0.97652
70	251.5	5.77×10¹¹	0.98601
80	222.4	5.60×10⁹	0.98960