葵花杆的热解特性及热解产物分析

doi:10.3969/j.issn.1673-5854.2021.04.001

摘要/Abstract

摘要：

为充分利用生物质葵花杆，采用同步热分析仪以升温速率为影响因素对葵花杆的热解特性进行研究，利用Coats-Redfern积分法计算主要阶段热解动力学参数，并采用气相色谱/质谱联用仪对热解产物进行了定量分析。研究结果表明：葵花杆的热解过程可分为预热干燥、主要热解及炭化3个阶段；随着升温速率的增大，葵花杆热解的TG曲线向高温区移动，残余质量增加；在主热解阶段（125~400℃），葵花杆的失重率约为总失重的85%，活化能（E）37.02~40.48（kJ/mol），指前因子（A）为6.10×10²~27.67×10² min^-1，线性拟合相关系数均大于0.97。快速热裂解过程中检测出106个特征峰、86种特征物质，依据化学种类不同可分为11类，主要热裂解特征产物有硬脂酸（29.991%）、棕榈酸（27.642%）、正十八烷（7.185%）、硬酯酸甲酯（2.239%）、异戊二烯（1.678%）。

关键词: 葵花杆, 热重, 热解动力学, 产物分析

Abstract:

In order to make full use of biomass sunflower stalks, the simultaneous thermal analyzer was used to study the pyrolysis characteristics of sunflower stalks with heating rate as an influencing factor. The Coats-Redfern integral method was used to calculate the main phase pyrolysis kinetic parameters. And the quantitative analysis of pyrolysis products were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The results showed that the pyrolysis process of sunflower stalk could be divided into three stages: preheating and drying, main pyrolysis and charring; as the heating rate increased, the TG curve of sunflower stalk pyrolysis moved to the high temperature zone. In the main pyrolysis stage (125-400℃), the weight loss rate of sunflower stalk was about 85% of the total weight loss, the activation energies (E) were 37.02-40.48 kJ/mol, and the pre-exponential factors (A) were 6.10×10²-27.67×10² min^-1, the linear fitting correlation coefficients were all greater than 0.97. During the rapid thermal cracking process, 106 characteristic peaks and 86 characteristic substances were detected, which could be divided into 11 categories according to different chemical types. The main characteristic products of thermal cracking were stearic acid(29.991%), palmitic acid(27.642%), n-octadecane(7.185%), methyl stearate(2.239%), isoprene(1.678%).

Key words: sunflower stem, thremogravimetric, pyrolysis kinetics, product analysis

中图分类号:

TQ35
TK6

纪东骅, 李红岩, 雷振东, 缪高健, 赵明, 王志和. 葵花杆的热解特性及热解产物分析[J]. 生物质化学工程, 2021, 55(4): 1-6.

Donghua JI, Hongyan LI, Zhendong LEI, Gaojian MIAO, Ming ZHAO, Zhihe WANG. Pyrolysis Characteristics and Pyrolysis Products of Sunflower Stem[J]. Biomass Chemical Engineering, 2021, 55(4): 1-6.

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原料 raw material	工业分析industrial analysis			组分分析component analysis			元素分析elemental analysis
原料 raw material	挥发分 volatile	灰分 ash	固定碳 fixed carbon	纤维素 cellulose	半纤维素 hemicellulose	木质素 lignin	C	H	O	N	S
葵花杆 sunflower stem	72.87	9.50	17.63	26.23	22.82	40.46	40.50	5.02	45.10	0.98	0.43

升温速率/ (℃· min^-1) heating rate	初始热解温度(T_s)/ ℃ the initial temperature	残余质量/ % residual mass	总失重率/ % total weight loss rate	最大失重速率点 the maximum weight loss rate point		主要热解阶段 main pyrolysis stage
升温速率/ (℃· min^-1) heating rate	初始热解温度(T_s)/ ℃ the initial temperature	残余质量/ % residual mass	总失重率/ % total weight loss rate	温度/℃ temperature	速率/(%· min^-1) rate	温度区间/℃ temperature range	失重/% weight loss
10	248.7	23.1	76.9	306.7	-6.98	220~380	57.85
20	273.9	25.4	74.6	324.0	-14.76	227~387	57.40
30	282.0	26.2	73.8	333.8	-23.50	235~392	55.91

升温速率/(℃· min^-1) heating rate	(dw/dt)_max/ (%· min^-1)	(dw/dt)_mean/ (%· min^-1)	V_∞/%	T_max/℃	T_s/℃	ΔT_1/2/℃	P
10	-6.98	-0.99	76.9	306.7	248.7	49.2	1.42×10^-4
20	-14.76	-1.92	74.6	324.0	273.9	51.4	4.63×10^-4
30	-23.50	-2.85	73.8	333.8	282.0	54.1	9.60×10^-4

升温速率/(℃· min^-1) heating rate	温度区间/℃ temperature range	拟合方程 correlation equation	R	E/(kJ·mol^-1)	A/min^-1
10	220~380	Y=-8.0511-1188.2752x	0.98191	37.02	6.10×10²
20	227~387	Y=-7.9230-1277.2881x	0.97942	39.68	19.28×10²
30	235~392	Y=-7.8845-1 320.7931x	0.97671	40.48	27.67×10²

序号 number	化合物compound	时间/min time	分子式 molecular formula	相对分子质量 molecular weight	相对峰面积/% relative area
1	异戊二烯isoprene	1.515	C₅H₈	68.06	1.678
2	甲苯toluene	3.124	C₇H₈	92.06	1.529
3	呋喃甲醛2-furaldehyde	4.046	C₅H₄O₂	96.08	0.356
4	苯酚phenol	6.506	C₆H₆O	94.04	1.103
5	3-甲基-1, 2-环戊二酮1, 2-cyclopentanedione, 3-methyl-	7.331	C₆H₈O₂	112.12	1.357
6	1, 2-甲氧基苯酚1, 2-methoxyphenol	8.353	C₇H₈O₂	124.05	0.919
7	3-甲氧基-4-甲基苯甲醛benzaldehyde, 3-methoxy-4-methy-	11.757	C₉H₁₀O₂	150.07	1.276
8	2, 6-二甲氧基苯酚2, 6-dimethoxyphenol	12.260	C₈H₁₀O₃	154.06	1.278
9	丁香酚eugenol	13.547	C₁₀H₁₂O₂	164.08	0.743
10	十四醇tetradecanol	13.941	C₁₄H₃₀O	214.39	1.307
11	月桂酸lauric acid	14.621	C₁₂H₂₄O₂	200.18	0.790
12	3, 5-二甲氧基苯乙酮ethanone, 1-(3, 5-dimethoxyphenyl)-	14.715	C₁₀H₁₂O₃	180.08	1.681
13	十六烯1-hexadecene	14.886	C₁₆H₃₂	224.25	0.568
14	十七烯1-heptadecene	15.669	C₁₇H₃₄	238.27	0.635
15	4 -烯丙基-2, 6-二甲氧基苯酚 phenol, 2, 6-dimethoxy-4-(2-propen-1-yl)-	15.799	C₁₁H₁₄O₃	194.09	0.671
16	棕榈酸甲酯hexadecanoic acid, methyl ester	17.138	C₁₇H₃₄O₂	270.26	0.977
17	棕榈酸palmitic acid	17.397	C₁₆H₃₂O₂	256.24	27.642
18	十八烯1-octadecene	17.501	C₁₈H₃₆	252.28	0.528
19	1-十九碳烯1-nonadecene	18.009	C₁₉H₃₈	266.3	0.614
20	十七腈heptadecanenitrile	18.103	C₁₇H₃₃N	251.26	0.717
21	硬酯酸甲酯methyl stearate	18.175	C₁₉H₃₈O₂	298.29	2.239
22	正十八烷n-octadecane	18.264	C₁₈H₃₈	254.3	7.185
23	硬脂酸stearic acid	18.404	C₁₈H₃₆O₂	284.27	29.991
24	1-二十二烯1-docosene	18.494	C₂₂H₄₆O	326.6	2.869
25	诱虫烯9-tricosene, (9Z)-	18.938	C₂₃H₄₆	322.36	0.873