Effect of the component evolution of Chinese fir sawdust on wood vinegar during hydrothermal process

doi:10.11949/0438-1157.20230776

Abstract

Abstract:

Using Chinese fir sawdust as research object, wood vinegar was prepared by pyrolysis after hydrothermal pretreatment at 180—280℃. The evolution of Chinese fir sawdust components at different hydrothermal temperatures was analyzed by van Soest method, and the effects of the evolution of Chinese fir sawdust components after hydrothermal pretreatment on the yield, organic components, and physicochemical properties of wood vinegar were investigated by using gas chromatography-mass spectrometry (GC-MS), acidity meter, and other testing methods. The results showed that with the increase of hydrothermal temperature, the content of hemicellulose in hydrothermal sawdust decreased continuously. The cellulose content showed a trend of first increasing and then decreasing. The lignin content gradually increases. With the increase of hydrothermal temperature to 230℃, the contents of phenolic and aldehyde in wood vinegar increased gradually, which was consistent with the change trend of lignin and cellulose content respectively. The content of acid compounds slightly decreased, showing a positive correlation with changes in the total content of hemicellulose and cellulose, which are the main sources of acid compounds. When the hydrothermal temperature is 180—230℃, the massive decomposition of hemicellulose in hydrothermal Chinese fir sawdust leads to an increase in the content of cellulose and lignin, resulting in a higher density and lower pH of wood vinegar, but the yield increases only before 200℃. By optimizing the proportion of three components of Chinese fir sawdust through hydrothermal pretreatment, higher quality wood vinegar can be produced.

Key words: biomass, pyrolysis, wood vinegar, hydrothermal, yield, organic components

摘要：

以杉木屑为研究对象，经180~280℃水热预处理后热解制备木醋液。采用范氏法定量分析了不同水热温度下杉木屑组分的演变，并利用气相色谱-质谱联用仪（GC-MS）、酸度计等测试手段考察了水热预处理后杉木屑组分演变对木醋液产率、有机组分和理化性质的影响。结果表明：随水热温度升高，水热杉木屑中的半纤维素含量持续降低；纤维素含量呈先升高后降低趋势；木质素含量逐渐升高。随水热温度升高至230℃，木醋液中酚类和醛类化合物含量逐渐增加，分别与木质素和纤维素含量变化趋势一致；酸类化合物含量略微减少，与半纤维素和纤维素总含量变化呈正相关趋势，半纤维素和纤维素是酸类化合物的主要来源。当水热温度为180~230℃时，水热杉木屑中半纤维素的大量分解导致纤维素和木质素含量增加使得木醋液密度更高、pH更低，而产率仅在200℃前增加。通过水热预处理优化杉木屑三组分占比，可制取更高品质的木醋液。

关键词: 生物质, 热解, 木醋液, 水热, 产率, 有机组分

CLC Number:

TK 6

Xiuyuan HAN, Shouyu ZHANG, Jiaqing XU, Xuyang CHEN, Xingjia ZHANG, Zihang XU, Nan HU, Yuxin WU. Effect of the component evolution of Chinese fir sawdust on wood vinegar during hydrothermal process[J]. CIESC Journal, 2023, 74(10): 4311-4318.

韩修远, 张守玉, 徐嘉庆, 陈旭阳, 张邢佳, 徐梓航, 胡南, 吴玉新. 水热过程中杉木屑组分的演变对木醋液的影响[J]. 化工学报, 2023, 74(10): 4311-4318.

Figures/Tables 6

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样品	工业分析/%(mass， ad)				组分分析/%(mass)
样品	M	A	V	FC	抽提物	半纤维素	纤维素	木质素	灰分
FS	2.13	1.64	80.67	15.56	4.77	26.99	40.84	24.25	3.15

样品	工业分析/%(mass， ad)				组分分析/%(mass)
样品	M	A	V	FC	抽提物	半纤维素	纤维素	木质素	灰分
FS	2.13	1.64	80.67	15.56	4.77	26.99	40.84	24.25	3.15

有机化合物	相对含量/%(质量)
有机化合物	WV-FS	HTWV-180	HTWV-200	HTWV-230
酸类	24.90	13.34	11.54	10.62
甲酸	1.76	1.05		1.37
乙酸	18.05	7.77	7.73	5.96
高香草酸	2.09	2.00	1.49	0.74
酚类	25.64	34.61	37.35	42.15
4-甲基愈创木酚	6.16	10.17	13.97	12.63
邻苯二酚	2.81	4.06	2.71	8.61
2-甲氧基苯酚	7.45	7.58	10.92	11.61
4-乙基-2-甲氧基苯酚	2.46	3.69	4.16	3.85
酮类	24.71	23.53	24.81	25.11
羟基丙酮	2.35	1.91	3.45	1.79
2-羟基-2-环戊烯- 1-酮	2.28	1.60	1.92	2.37
3-甲基环戊烷- 1,2-二酮	3.94	3.18	4.5	4.93
香草乙酮	1.07	2.86	2.76	1.57
3,5-二羟基-2- 甲基-4H-吡喃- 4-酮	—	1.16	2.39	1.36
1-(4-甲基噻吩基)-2-丙酮	—	2.89	2.04	1.24
醛类	10.05	11.35	14.28	14.03
糠醛	4.67	3.29	5.05	5.44
5-羟甲基糠醛	1.02	2.96	3.18	4.43
醇类	1.36	0.84	0.15	0.38
酯类	4.01	4.62	1.26	1.01

有机化合物	相对含量/%(质量)
有机化合物	WV-FS	HTWV-180	HTWV-200	HTWV-230
酸类	24.90	13.34	11.54	10.62
甲酸	1.76	1.05		1.37
乙酸	18.05	7.77	7.73	5.96
高香草酸	2.09	2.00	1.49	0.74
酚类	25.64	34.61	37.35	42.15
4-甲基愈创木酚	6.16	10.17	13.97	12.63
邻苯二酚	2.81	4.06	2.71	8.61
2-甲氧基苯酚	7.45	7.58	10.92	11.61
4-乙基-2-甲氧基苯酚	2.46	3.69	4.16	3.85
酮类	24.71	23.53	24.81	25.11
羟基丙酮	2.35	1.91	3.45	1.79
2-羟基-2-环戊烯- 1-酮	2.28	1.60	1.92	2.37
3-甲基环戊烷- 1,2-二酮	3.94	3.18	4.5	4.93
香草乙酮	1.07	2.86	2.76	1.57
3,5-二羟基-2- 甲基-4H-吡喃- 4-酮	—	1.16	2.39	1.36
1-(4-甲基噻吩基)-2-丙酮	—	2.89	2.04	1.24
醛类	10.05	11.35	14.28	14.03
糠醛	4.67	3.29	5.05	5.44
5-羟甲基糠醛	1.02	2.96	3.18	4.43
醇类	1.36	0.84	0.15	0.38
酯类	4.01	4.62	1.26	1.01

木醋液样品	密度/（g/cm³）	pH
WV-FS	1.091	2.02
HTWV-180	1.135	1.93
HTWV-200	1.136	1.97
HTWV-230	1.124	1.98
HTWV-260	1.061	2.27
HTWV-280	1.004	3.11
日本木醋协会标准^[30]	≥1.001	1.5~3.7