基于TG-FTIR和Py-GC-MS分析的椰壳热解特性研究

doi:10.3969/j.issn.0253-2417.2020.01.007

摘要/Abstract

摘要：

采用热重-红外光谱（TG-FTIR）和裂解-气相色谱-质谱联用（Py-GC-MS）技术对椰壳粉的热失重、热裂解行为及其裂解产物进行了研究。在对N₂和空气气氛下椰壳的TG和DTG曲线进行分析的基础上，采用三维红外光谱对热解过程中气体产物进行在线检测，结果表明：N₂气氛下，椰壳的最大失重峰温度（T_m）为347.8℃，固体残余量为32.0%，主要的气体产物是CO₂；而空气气氛下椰壳的热解更完全，固体残余量仅为6.5%，且最大热失重温度为282.1℃，释放的气体除了CO₂，还有CO、H₂O和CH₄等。Py-GC-MS分析结果表明：酚类化合物是主要的裂解产物，当温度为400℃时共检测到39种裂解产物，其中酚类化合物12种（GC含量40.0%）；当温度为700℃时共检测到56种裂解产物，其中酚类化合物18种（GC含量45.8%）。

关键词: 热失重, 热重-红外光谱, 裂解-气相色谱质谱, 椰壳, 热解特性

Abstract:

The thermogravimetric, pyrolysis behavior and pyrolytic products of coconut shells meal were analyzed by thermogravimetry-Fourier transform infrared spectroscopy(TG-FTIR) and pyrolysis-gas chromatography and mass spectrometry(Py-GC-MS). Three-dimensional infrared spectroscopy was used to detect the gas products in the pyrolysis process, based on the analysis of TG and DTG curves under N₂/air atmosphere. The results showed that the maximum weight loss peak temperature(T_m) was 347.8℃, and the residual was 32.0%, CO₂ was the main gas product under the N₂ atmosphere. The solid residual was only 6.5%, and T_m was 282.1℃, and the released gas were CO₂, CO, H₂O and CH₄, under the air atmosphere.Py-GC-MS results showed that phenolic compounds were the main products. There were 39 pyrolysis products, among which 12 kinds of products were phenolic compounds (GC content 40.0%) at the temperature 400℃. There were 56 pyrolysis products, among which 18 kinds of products were phenolic compounds (GC content 45.8%) at the temperature 700℃.

Key words: thermal weight loss, TG-FTIR, Py-GC-MS, coconut, pyrolysis characteristics

中图分类号:

TQ35

陈强,王艳,翟华敏. 基于TG-FTIR和Py-GC-MS分析的椰壳热解特性研究[J]. 林产化学与工业, 2020, 40(1): 45-52.

Qiang CHEN,Yan WANG,Huamin ZHAI. Pyrolysis Characteristics of Coconut Shell Based on TG-FTIR and Py-GC-MS Analysis[J]. Chemistry and Industry of Forest Products, 2020, 40(1): 45-52.

图/表 4

图1

图2

图3

表1

椰壳的裂解产物分析结果(N2)"

编号 No.	时间/min time	化合物名称 compound name	分子式 formula	GC含量GC content/%
编号 No.	时间/min time	化合物名称 compound name	分子式 formula	400 ℃	700 ℃
1	1.328	1-甲基环丙烷甲醇(1-methylcyclopropyl)methanol	C₅H₁₀O	—	0.62
2	1.660	1-戊烯-3-醇1-penten-3-ol	C₅H₁₀O	2.97	1.59
3	2.002	1, 2-二甲基肼dimethyl hydrazine	C₂H₈N₂	3.07	1.74
4	2.118	丙酸propionic acid	C₃H₆O₂	—	0.16
5	2.563	碳酸亚乙烯酯vinylene carbonate	C₃H₂O₃	0.78	0.34
6	3.178	3-甲基丁醛3-methyl butanal	C₅H₁₀O	0.92	0.57
7	3.439	1-羟基-2-丁酮1-hydroxybutan-2-one	C₄H₈O₂	—	0.65
8	3.710	丙醛propanal	C₃H₆O	—	0.51
9	4.816	糠醛furfural	C₅H₄O₂	2.55	1.56
10	5.466	糠醇2-furanmethanol	C₅H₆O₂	—	0.41
11	6.350	2-吡咯烷酮2-pyrrolidinone	C₄H₇NO	0.92	—
12	7.359	α-当归内酯α-angelic lactone	C₅H₆O₂	0.67	1.05
13	8.481	2-乙烯基-2-丁烯醛2-ethenyl-2-butenal	C₆H₈O	—	0.83
14	9.375	苯酚phenol	C₆H₆O	9.95	7.02
15	9.588	2-丁基-2-乙基-3-甲基-噁唑烷2-butyl-2-ethyl-3-methyl-oxazolidine	C₁₁H₂₃NO	5.47	—
16	10.588	甲基环戊烯醇酮methyl cyclopentenolone	C₆H₈O₂	—	0.48
17	11.578	2-甲基苯酚2-methyl-phenol	C₇H₈O	0.77	1.16
18	12.275	3-甲基苯酚3-methyl-phenol	C₇H₈O	—	0.85
19	12.428	愈创木酚guaiacol	C₇H₈O₂	2.13	2.54
20	12.612	1-己烯-3-醇1-hexen-3-ol	C₆H₁₂O	0.78	—
21	14.442	2, 4-二甲基苯酚2, 4-dimethylphenol	C₈H₁₀O	—	0.56
22	14.789	2, 3-二羟基苯甲醛2, 3-dihydroxybenzaldehyde	C₇H₆O₃	—	0.32
23	15.161	2-甲氧基-3-甲基苯酚2-methoxy-3-methyl-phenol	C₈H₁₀O₂	—	0.45
24	15.620	2-甲氧基-4-甲基苯酚2-methoxy-4-methyl-phenol	C₈H₁₀O₂	0.47	1.39
25	16.394	对苯二酚1, 2-benzenediol	C₆H₆O₂	—	2.29
26	16.714	2, 3-二氢苯并呋喃2, 3-dihydrobenzofuran	C₈H₈O	—	0.92
27	17.802	3-甲氧基儿茶酚3-methoxycatechol	C₇H₈O₃	—	2.67
28	18.158	4-乙基愈创木酚4-ethyl-2-methoxyphenol	C₉H₁₂O₂	1.70	1.50
29	18.677	3, 4-二氢-1H-苯并吡喃chromane	C₉H₁₀O	—	0.68
30	18.927	4-甲基儿茶酚4-methylcatechol	C₇H₈O₂	—	1.73
31	19.117	对乙烯基愈创木酚2-methoxy-4-vinylphenol	C₉H₁₀O₂	5.14	4.55
32	20.016	2, 6-二甲氧基苯酚2, 6-dimethoxy-phenol	C₈H₁₀O₃	3.91	4.99
33	20.089	丁香油酚eugenol	C₁₀H₁₂O₂	0.91	—
34	20.237	3, 4-二甲氧基苯酚3, 4-dimethoxy-phenol	C₈H₁₀O₃	—	1.97
35	21.028	异香草醛vanillin	C₈H₈O₃	0.98	3.15
36	21.122	异丁香酚trans-isoeugenol	C₁₀H₁₂O₂	0.42	—
37	21.670	对甲氧基苯甲酸4-methoxybenzoic acid	C₈H₈O₃	—	1.13
38	21.894	顺式异丁香酚cis-isoeugenol	C₁₀H₁₂O₂	5.40	4.76
39	22.116	2-甲氧基-4-丙基苯酚2-methoxy-4-propylphenol	C₁₀H₁₄O₂	—	1.23
40	22.249	尼泊金甲酯methyl 4-hydroxybenzoate	C₈H₈O₃	0.69	1.96
41	22.367	4-(3-甲基-2-丁烯基)苯酚4-(3-methyl-2-butenyl)phenol	C₁₁H₁₄O	1.08	—
42	22.581	香草乙酮apocynin	C₉H₁₀O₃	0.68	1.16
43	22.723	特丁基对苯二酚tert-butylhydroquinone	C₁₀H₁₄O₂	—	1.06
44	23.143	3, 4, 5-三甲氧基甲苯3, 4, 5-trimethoxytoluene	C₁₀H₁₄O₃	2.22	1.73
45	23.285	高香草醇homovanillyl alcohol	C₉H₁₂O₃	1.39	1.81
46	23.650	对羟基苯甲酸4-hydroxybenzoic acid	C₇H₆O₃	—	2.16
47	23.751	2, 5-二甲氧基-4-甲苯甲醛2, 5-dimethoxy-4-methylbenzaldehyde	C₁₀H₁₂O₃	5.76	4.19
48	23.937	香草酸4-hydroxy-3-methoxybenzoic acid	C₈H₈O₄	0.79	1.18
49	24.054	4-乙氧基-3-甲氧基苯甲醛4-ethoxy-3-methoxybenzaldehyde	C₁₀H₁₂O₃	0.30	2.17
50	24.289	(E)-阿魏酸(E)-ferulic acid	C₁₀H₁₀O₄	1.25	1.81
51	24.751	4-乙烯基联苯4-vinylbiphenyl	C₁₄H₁₂	—	1.30
52	24.958	阿魏酸ferulic acid	C₁₀H₁₀O₄	1.12	1.49
53	25.121	丁香醛syringaldehyde	C₉H₁₀O₄	1.75	1.95
54	25.320	5, 6-二甲氧基-1-茚酮5, 6-dimethoxy-1-indanone	C₁₁H₁₂O₃	0.87	0.81
55	25.603	4-烯丙基-2, 6-二甲氧基苯酚2, 6-dimethoxy-4-allylphenol	C₁₁H₁₄O₃	8.12	5.04
56	26.093	4-羟基-3-甲氧基肉桂醛4-hydroxy-3-methoxy cinnamaldehyde	C₁₀H₁₀O₃	9.98	5.31
57	26.488	1-(2, 4, 6-三羟基-3-甲苯基)丁酮1-(2, 4, 6-trihydroxy-3-methylphenyl)butan-1-one	C₁₁H₁₄O₄	4.78	1.89
58	27.130	二苯基-2, 2′-二甲醛biphenyl-2, 2′-dicarboxaldehyde	C₁₄H₁₀O₂	0.87	1.15
59	27.530	邻苯二甲酸单丁酯monobutyl phthalate	C₁₂H₁₄O₄	0.46	0.30
60	28.508	棕榈酸palmitic acid	C₁₆H₃₂O₂	0.33	0.54
61	28.916	3, 5-二甲氧基-4-羟基肉桂醛3, 5-dimethoxy-4-hydroxycinnamaldehyde	C₁₁H₁₂O₅	—	0.98
62	39.383	苯二甲酸(2-乙基己基)辛酯phthalic acid, (2-ethylhexyl) octyl ester	C₂₄H₃₈O₄	6.19	3.19

表1

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