单宁酸的热性能及热分解动力学研究

doi:10.3969/j.issn.0253-2417.2022.03.011

摘要/Abstract

摘要：

单宁酸(TA)是一种多羟基的芳香族生物质，通过热重实验分析了TA的热性能，马弗炉加热实验观察TA的成炭过程，并采用KAS和Ozawa法计算其表观活化能，Satava法确定最概然机理函数。热失重分析表明：TA在182 ℃左右时进入快速失重状态；达到800 ℃时，TA在氮气气氛中的残炭量为15.29%，在空气气氛中由于436~538 ℃温区的第二次快速失重使得残炭量为1.97%。宏观成炭实验发现：TA受热会形成膨胀炭层，其中100~200 ℃时出现空心状炭层，300~400 ℃时形成实心炭层，且膨胀明显、完整致密、光泽度好，有成为膨胀型阻燃剂中新型碳源的潜力。热分解动力学研究结果表明：TA在氮气气氛下的热分解表观活化能为494 kJ/mol，lgA为111.32，快速失重阶段的最概然机理函数为G(α)= [-ln(1-α)]^1/n，n=0.105 3，其热分解机理符合J-M-A方程，属于随机成核和核随后增长反应。

关键词: 生物质, 成炭性能, 热解, 动力学

Abstract:

Tannic acid(TA) is a kind of multi hydroxyl aromatic biomass. The thermal properties of TA were analyzed by thermogravimetric experiment, the carbonization process of TA was observed by muffle furnace heating experiment, the apparent activation energy was observed by KAS and Ozawa method, and the most probable function was determined by Satava method. Thermogravimetric analysis showed that TA entered the state of rapid weight loss at about 182 ℃; when the temperature reached 800 ℃, the carbon residue of TA in nitrogen atmosphere was 15.29%. In air atmosphere, the carbon residue was 1.97% due to the second rapid weight loss in the temperature range of 436-538 ℃. It was found in the macro carbonization experiment that TA would form an expanded carbon layer when heated. Among them, a hollow carbon layer appeared at 100-200 ℃, and a solid carbon layer was formed at 300-400 ℃, which had obvious expansion, integrity, compactness and good gloss. It had the potential to become a new carbon source in intumescent flame retardants. The results of thermal decomposition kinetics showed that the apparent activation energy of thermal decomposition of TA in nitrogen atmosphere was 494 kJ/mol, lgA was 111.32, and the most probable mechanism function of rapid weight loss stage was G(α)=[-ln(1-α)]^1/n, n=0.105 3, and its thermal decomposition mechanism belonged to random nucleation and subsequent nucleation growth reaction.

Key words: biomass, charring performance, pyrolysis, kinetics

中图分类号:

TQ35

鲁玉鑫, 卢林刚. 单宁酸的热性能及热分解动力学研究[J]. 林产化学与工业, 2022, 42(3): 83-89.

Yuxin LU, Lingang LU. Thermal Properties and Thermal Decomposition Kinetics of Tannic Acid[J]. Chemistry and Industry of Forest Products, 2022, 42(3): 83-89.

图/表 5

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转化率(α) conversion rate	不同升温速率的对应的温度/℃ temp. at different heating rates				不同方法下的活化能(E)/(kJ·mol^-1) activation energy with different methods
转化率(α) conversion rate	10 K/min	20 K/min	30 K/min	40 K/min	KSA	Ozawa
0.20	492.81	495.68	498.77	496.55	410.74	398.43
0.25	498.07	503.05	503.81	503.93	411.84	399.55
0.30	504.36	507.92	508.62	510.15	508.27	491.35
0.35	512.17	512.47	513.64	516.22	599.34	578.06
0.40	519.94	519.29	520.42	523.71	466.71	452.06
0.45	525.55	527.92	528.59	533.14	391.33	380.51
0.50	533.81	536.08	535.95	539.42	548.11	529.70
0.55	540.27	543.56	543.40	546.03	582.12	562.14
0.60	546.29	550.77	551.34	551.96	547.42	529.24
0.65	552.81	556.26	556.41	557.86	685.70	660.83
0.70	562.48	563.25	562.17	562.94	372.00	362.65

函数号 function No.	函数名称 function name	G(α)	R²	E/(kJ·mol^-1)
9	Z-L-T	${\left[{{{(1- \alpha)}^{ - \frac{1}{3}}} - 1} \right]^2}$	0.9880	114.88
10	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{1}{4}}}$	0.9842	13.04
11	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{1}{3}}}$	0.9842	17.38
12	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{2}{5}}}$	0.9842	20.86
13	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{1}{2}}}$	0.9842	26.07
14	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{2}{3}}}$	0.9842	34.76
15	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{3}{4}}} - $	0.9842	39.11
16	Mample单行法则Mampel power law(n=1)	- ln(1-α)	0.9842	52.15
17	Avrami-Erofeev	${[- \ln (1 - \alpha)]^{\frac{3}{2}}}$	0.9842	78.22
18	Avrami-Erofeev	[-ln(1-α)]²	0.9842	104.29
19	Avrami-Erofeev	[-ln(1-α)]³	0.9842	156.44
20	Avrami-Erofeev	[-ln(1-α)]⁴	0.9842	208.59
37	反应级数reaction order	(1-α)^-1-1	0.9922	69.16
44	J-M-A(n=0.1053)	[-ln(1-α)]^1/n	0.9842	495.38

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