重质生物油理化性质及其热解特性研究

doi:10.11949/0438-1157.20190320

摘要/Abstract

摘要：

利用核磁共振波谱仪（NMR）与气相色谱/质谱联用仪（GC/MS）对重质生物油理化性质进行表征，并应用热重分析仪（ TG-DTG）与热裂解仪-气相色谱/质谱联用仪（Py-GC/MS）对重质生物油热解特性进行研究。结果表明：重质生物油主要由芳香族化合物和糖类物质组成。重质生物油在N₂氛围下热解主要分为三个阶段: 室温~300℃为蒸发段，300～520℃为热解段，520～800℃为成焦段。重质生物油经不同温度热解后，产物种类有明显差异：中温段（低于500℃）热解时，产物种类随温度的升高逐渐增加；高温段（高于500℃）热解时，随着热解温度的提高，产物种类逐渐趋于稳定。

关键词: 重质生物油, NMR, TG-DTG, Py-GC /MS, 热解

Abstract:

The physicochemical properties of heavy bio-oil were characterized by NMR and GC/MS, and thermogravimetric analyzer (TG-DTG) and pyrolysis instrument-gas chromatography/mass spectrometry (Py-GC/MS) was used to study the pyrolysis characteristics of heavy bio-oil. The results indicate that the heavy bio-oil consists of aromatic compounds and saccharides. The first stage is the volatilization of light compounds from ambient temperature to 300℃. The second stage is the pyrolysis, oxidation and polymerization of the heavy compounds at higher temperature (300—520℃). The last stage is the formation of coke (520—800℃). When the pyrolysis temperature is lower than 500℃, the species of products gradually increases with increasing temperature. When the temperature is higher than 500℃, the species of products tends to be stable with increasing temperature.

Key words: heavy bio-oil, NMR, TG-DTG, Py-GC/MS, pyrolysis

中图分类号:

TK 6

罗泽军, 胡永华, 王雨松, 朱谢飞, 朱锡锋. 重质生物油理化性质及其热解特性研究[J]. 化工学报, 2019, 70(8): 3196-3201.

Zejun LUO, Yonghua HU, Yusong WANG, Xiefei ZHU, Xifeng ZHU. Physicochemical properties and pyrolysis characteristics of heavy bio-oil[J]. CIESC Journal, 2019, 70(8): 3196-3201.

图/表 8

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物质	含量/%（质量）
苯酚	1.29
愈创木酚	1.16
4-甲基愈创木酚	1.10
4-乙基愈创木酚	1.18
紫丁香醇	1.08

物质	含量/%（质量）
苯酚	1.29
愈创木酚	1.16
4-甲基愈创木酚	1.10
4-乙基愈创木酚	1.18
紫丁香醇	1.08

停留时间	物质	分子式	分子量	相对峰面积/%
11.98	苯酚	C₆H₆O	94	4.00
14.94	邻甲酚	C₇H₈O	108	2.95
15.30	间甲酚	C₇H₈O	108	5.44
16.25	愈创木酚	C₇H₈O₂	124	5.06
17.05	2,3-二甲酚	C₈H₁₀O	122	0.53
18.93	3-甲基-1H-茚	C₁₀H₁₀	130	0.70
19.26	3,4-二甲基苯酚	C₈H₁₀O	122	4.15
20.17	萘	C₁₀H₈	128	1.26
20.31	4-乙基苯酚	C₈H₁₀O	122	0.97
20.39	3-乙基苯酚	C₈H₁₀O	122	2.04
20.66	3,4-二甲基苯酚	C₈H₁₀O	122	0.92
20.98	4-甲基愈创木酚	C₈H₁₀O₂	138	1.86
23.08	2,4,5-三甲基苯酚	C₉H₁₂O	136	0.54
23.27	2-乙基，5-甲基苯酚	C₉H₁₂O	136	2.04
23.50	2,4,5-三甲基苯酚	C₉H₁₂O	136	0.84
24.35	3-甲基-5-乙基苯酚	C₉H₁₂O	136	0.99
24.70	4-乙基愈创木酚	C₉H₁₂O₂	152	2.93
25.13	1-甲基萘	C₁₁H₁₀	97	1.56
26.56	5-异丙基-2-甲基苯酚	C₁₀H₁₄O	150	0.78
26.77	2,6-二羟基甲苯	C₇H₈O₂	124	1.18
30.31	4-烯丙基-2-甲氧基苯酚	C₁₀H₁₂O₂	164	0.81
30.46	1H-茚酚	C₉H₈O	132	0.55
30.54	3- (4-羟基-3-甲氧基)-2- 丙烯-1-醇	C₁₀H₁₂O₃	180	0.52
30.62	香兰素	C₈H₈O₃	152	0.66
31.02	2-烯丙基-4-甲基苯酚	C₁₀H₁₂O	148	0.84
31.53	亚联苯	C₁₂H₈	152	0.92
32.07	4-乙基苯邻二酚	C₈H₁₀O₂	138	3.68
32.68	5,8-二氢-1-萘酚	C₁₀H₁₀O	146	0.60
36.81	芴	C₁₃H₁₀	166	0.52

停留时间	物质	分子式	分子量	相对峰面积/%
11.98	苯酚	C₆H₆O	94	4.00
14.94	邻甲酚	C₇H₈O	108	2.95
15.30	间甲酚	C₇H₈O	108	5.44
16.25	愈创木酚	C₇H₈O₂	124	5.06
17.05	2,3-二甲酚	C₈H₁₀O	122	0.53
18.93	3-甲基-1H-茚	C₁₀H₁₀	130	0.70
19.26	3,4-二甲基苯酚	C₈H₁₀O	122	4.15
20.17	萘	C₁₀H₈	128	1.26
20.31	4-乙基苯酚	C₈H₁₀O	122	0.97
20.39	3-乙基苯酚	C₈H₁₀O	122	2.04
20.66	3,4-二甲基苯酚	C₈H₁₀O	122	0.92
20.98	4-甲基愈创木酚	C₈H₁₀O₂	138	1.86
23.08	2,4,5-三甲基苯酚	C₉H₁₂O	136	0.54
23.27	2-乙基，5-甲基苯酚	C₉H₁₂O	136	2.04
23.50	2,4,5-三甲基苯酚	C₉H₁₂O	136	0.84
24.35	3-甲基-5-乙基苯酚	C₉H₁₂O	136	0.99
24.70	4-乙基愈创木酚	C₉H₁₂O₂	152	2.93
25.13	1-甲基萘	C₁₁H₁₀	97	1.56
26.56	5-异丙基-2-甲基苯酚	C₁₀H₁₄O	150	0.78
26.77	2,6-二羟基甲苯	C₇H₈O₂	124	1.18
30.31	4-烯丙基-2-甲氧基苯酚	C₁₀H₁₂O₂	164	0.81
30.46	1H-茚酚	C₉H₈O	132	0.55
30.54	3- (4-羟基-3-甲氧基)-2- 丙烯-1-醇	C₁₀H₁₂O₃	180	0.52
30.62	香兰素	C₈H₈O₃	152	0.66
31.02	2-烯丙基-4-甲基苯酚	C₁₀H₁₂O	148	0.84
31.53	亚联苯	C₁₂H₈	152	0.92
32.07	4-乙基苯邻二酚	C₈H₁₀O₂	138	3.68
32.68	5,8-二氢-1-萘酚	C₁₀H₁₀O	146	0.60
36.81	芴	C₁₃H₁₀	166	0.52

序号	化学位移	官能团	质子数^①/ （mol/100g）
a	7.8～6.0	芳香氢或双键氢	1.26
b	4.1～3.0	与苯环相连甲氧基氢	0.72
c	3.0～1.8	与苯环连接甲基、亚甲基氢	1.86
d	1.8～0.5	与烷基相连甲基或亚甲基氢	1.26
总计			5.10