三种木质素水热液化制备生物油实验研究

杨天华; 刘正; 李秉硕; 张海军; 王鹤逸

doi:10.1016/S1872-5813(23)60345-7

三种木质素水热液化制备生物油实验研究

doi: 10.1016/S1872-5813(23)60345-7

沈阳航空航天大学能源与环境学院辽宁省清洁能源重点实验室, 辽宁沈阳 110136

基金项目: 国家自然科学基金（52176195）和辽宁省兴辽英才计划（XLYC200512）资助

详细信息

通讯作者:
E-mail: thyang@sau.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2022-12-20
- 修回日期: 2023-01-25
- 录用日期: 2023-02-09
- 网络出版日期: 2023-03-08
- 刊出日期: 2023-08-01

Experimental study on preparation of bio-oil by hydrothermal liquefaction of three kinds of lignin

Shenyang Aerospace University, College of Energy and Environment, Key Laboratory of Clean Energy of Liaoning, Shenyang 110136, China

Funds: The project was supported by the National Natural Science Foundation of China (52176195), and Liaoning Revitalization Talents Program (XLYC200512)

摘要

摘要: 木质素是具有芳香族结构的天然可再生资源，可以通过水热液化技术将其转化为生物油。不同种类的木质素结构特点和反应活性存在差异，故本研究选取三种木质素（工业碱木质素（KL）、酶解木质素（EHL）和乙醇木质素（OL））为原料，首先对三种原料理化特性进行分析；其次考察反应条件对三种木质素水热液化生物油特性的影响。在三种木质素中，EHL、OL为愈创木基型结构。OL的C、H元素含量最高，其高位热值为23.54 MJ/kg，芳香特征更加明显，酚羟基含量相对较高。KL为紫丁香基型结构，甲氧基与酚羟基含量较少。液化实验结果显示，反应温度为300 ℃时，木质素生物油产率及能量回收率最高，该温度下产率OL>KL>EHL，生物油的H/C比值为1.0–1.4。三种生物油化学成分不同，OL生物油中含有9.14%的芳香烃，EHL生物油酚类物质含量达到41.34%，KL生物油中酸类含量较高。
- 木质素 /
- 水热液化 /
- 生物油 /
- 芳香族化合物
Abstract: Lignin is a natural and renewable resource with aromatic structure. It can be converted into bio-oil by hydrothermal liquefaction. Due to the complex structure of wood fiber, the structural characteristics and reactivity of different kinds of lignin are different. Therefore, three typical lignin (kraft lignin (KL), enzymatic hydrolysis lignin (EHL) and ethanol lignin (OL)) were selected as raw materials. Firstly, physical and chemical properties of the raw materials were analyzed. Secondly, effects of reaction conditions on characteristics of their hydrothermal liquefaction bio-oil were investigated. Among them, EHL and OL are guaiacyl units. OL has the highest content of carbon and hydrogen elements, and its higher heating value reaches 23.54 MJ/kg. The aromatic characteristics are more obvious, and the phenolic hydroxyl content is relatively high. KL is mainly syringyl unit with less methoxy and phenolic hydroxyl groups. The results of liquefaction experiment show that when the reaction temperature was 300 ℃, yield and energy recovery rate of lignin bio-oil were the highest. The bio-oil yield ranked in the order of OL>KL>EHL. H/C ratio of bio-oil was concentrated within 1.0-1.4. Chemical composition of the three bio-oils was different. OL bio-oil contains 9.14% aromatic hydrocarbons, EHL bio-oil contains 41.34% phenolic species, and KL bio-oil has a higher acid content.
- lignin /
- hydrothermal liquefaction /
- bio-oil /
- aromatic compound

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FIG. 2574. FIG. 2574.

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图 1 木质素液化实验流程图

Figure 1 Flow chart of lignin liquefaction experiment

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图 2 木质素的红外光谱谱图

Figure 2 FT-IR spectra of three types of lignin

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图 3 木质素的 TG 和 DTG 曲线

Figure 3 TG and DTG curves of three types of lignin

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图 4 热解特性指标确定示意图

Figure 4 Schematic diagram of pyrolysis characteristic index determination

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图 5 反应温度对木质素液化生物油产率及热值的影响

Figure 5 Effect of reaction temperature on yield and calorific value of lignin liquefied bio-oil

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图 6 木质素及液化生物油的H/C和O/C比的变化

Figure 6 H/C and O/C variations of lignin and liquefied bio-oil

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图 7 木质素液化生物油的红外光谱谱图

Figure 7 FT-IR spectra of lignin liquefied bio-oils

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图 8 木质素液化生物油组成分布

Figure 8 Composition distribution of liquefied of lignin liquefied bio-oils

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表 1 木质素的元素分析及高位热值

Table 1 Ultimate analysis and higher heating value of lignin

Sample	Ultimate analysis w/%					Q_HHV /(MJ·kg⁻¹)
Sample	C	H	O*	N	S	Q_HHV /(MJ·kg⁻¹)
EHL	47.26	5.74	44.49	0.53	0	18.87
KL	39.02	4.42	21.75	0.38	2.03	17.08
OL	58.04	5.78	34.48	1.09	0	23.60
*: by difference

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表 2 木质素热解特性

Table 2 Pyrolysis characteristics of lignin

Sample	Start temperature t/℃	End temperature t/℃	Maximum pyrolysis rate V_p/(%·min⁻¹)	Maximum pyrolysis rate temperature t_p/℃	Average pyrolysis rate V_a/(%·min⁻¹)
KL	230.7	389.2	4.57	269.8	3.82
EHL	322.4	382.5	24.27	364.3	24.99
OL	305.5	400.3	13.29	360.7	12.45

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表 3 液化反应的质量衡算

Table 3 Mass balance of liquefaction reaction

Sample	Bio-oil yield /%	Solid residue yield /%	Gas + aqueous yield /%
KL (280 ℃)	22.5	9.34	68.16
KL (300 ℃)	26.84	7.28	65.88
KL (320 ℃)	19.32	6.46	74.22
KL (340 ℃)	17.1	6.04	76.86
EHL (280 ℃)	20.44	35.3	44.26
EHL (300 ℃)	24.08	33.4	42.52
EHL (320 ℃)	22.28	29.8	47.92
EHL (340 ℃)	16.4	28.42	55.18
OL (280 ℃)	25.7	42.86	31.44
OL (300 ℃)	35.8	37.64	26.56
OL (320 ℃)	25.28	35.1	39.62
OL (340 ℃)	20.18	32.44	47.38

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表 4 不同反应条件下液化生物油的元素分析

Table 4 Elemental analysis of liquefied bio-oil under different reaction conditions

Sample	Elemental analysis w/%					H/C	O/C	Q_HHV /(MJ·kg⁻¹)
Sample	C	H	O	N	S	H/C	O/C	Q_HHV /(MJ·kg⁻¹)
KL (280 ℃)	49.33	5.39	44.18	0.44	0.67	1.31	0.67	19.3
KL (300 ℃)	60.37	6.07	32.42	0.65	0.49	1.21	0.4	25.03
KL (320 ℃)	68.56	6.23	24.3	0.81	0.11	1.09	0.27	28.75
KL (340 ℃)	70.8	6.51	21.68	0.78	0.23	1.1	0.23	30.13
EHL (280 ℃)	66.64	5.95	27.06	0.36	0	1.07	0.3	27.42
EHL (300 ℃)	66.75	5.91	26.95	0.39	0	1.06	0.3	27.42
EHL (320 ℃)	69.27	6.11	24.21	0.42	0	1.06	0.26	28.79
EHL (340 ℃)	71.26	6.32	22.01	0.42	0	1.06	0.23	29.95
OL (280 ℃)	66.37	6.56	26.07	1.01	0	1.19	0.29	28.22
OL (300 ℃)	68.34	7.09	27.15	0.39	0	1.24	0.3	29.7
OL (320 ℃)	70.48	7.04	21.25	1.23	0	1.2	0.23	30.71
OL (340 ℃)	72.05	6.97	20.56	0.43	0	1.16	0.21	31.17

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表 5 木质素液化生物油的化学成分分析（反应温度300 ℃）

Table 5 GC-MS analysis of lignin liquefaction bio-oil (reaction temperature 300 ℃)

No.	RT	Compound	Formula	KL-oil	EHL-oil	OL-oil
1	5.87	acetic acid, methyl ester	C₃H₆O₂	4.37		2.38
2	6.67	acetic acid	C₂H₄O₂	2.29
3	6.74	pentane, 3-methyl-	C₆H₁₄	2.65		1.93
4	6.79	ethane, 1,1-dimethoxy-	C₄H₁₀O₂	3.22	12.72
5	6.86	2-butanone	C₄H₈O		6.38	1.40
6	7.48	cyclopentane, methyl-	C₆H₁₂	0.58
7	9.31	propane, 1,1-dimethoxy-	C₅H₁₂O₂	1.27
8	9.38	2-butanone, 3-methyl-	C₅H₁₀O		1.33
9	9.39	2-pentanone	C₅H₁₀O	0.48
10	9.54	1,3-dioxolane, 2,2-dimethyl-	C₅H₁₀O₂	1.81
11	10.65	butanoic acid, methyl ester	C₅H₁₀O₂	0.39	2.62
12	12.39	toluene	C₇H₈	1.23	5.59
13	12.85	butanoic acid, 2-methyl-, methyl ester	C₆H₁₂O₂	0.47
14	13.67	furan, 2-methoxy-	C₅H₆O₂			24.01
15	14.37	acetic acid, butyl ester	C₆H₁₂O₂	0.57	3.06
16	15.15	cyclohexane, ethyl-	C₈H₁₆	0.57	1.88	0.52
17	15.28	1,1,4-trimethylcyclohexane	C₉H₁₈	0.53
18	15.48	2-pentanone, 4-hydroxy-4-methyl-	C₆H₁₂O₂	8.43		5.55
19	16.34	ethylbenzene	C₈H₁₀	3.57		7.53
20	17.06	acetamide, N-(cyanomethyl)-	C₄H₆N₂O		2.64
21	17.07	3-penten-2-one, 4-methyl-	C₆H₁₀O			0.97
22	17.07	2-hexanone, 6-(acetyloxy)-	C₈H₁₄O₃		2.55
23	17.63	ethylbenzene	C₈H₁₀			2.96
24	18.30	2-pentanone, 4-methoxy-4-methyl-	C₇H₁₄O₂	3.88	13.89	6.89
25	19.91	alpha-hydroxyisobutyric acid, acetate	C₆H₁₀O₄	2.99
26	20.88	phenol	C₆H₆O	6.74		2.22
27	21.501	benzene, 1,2,4-trimethyl-	C₉H₁₂	1.83		1.20
28	23.51	dl-erythro-1-phenyl-1,2-propanediol	C₉H₁₂O₂	1.00
29	24.19	p-cresol	C₇H₈O	0.82
30	24.69	benzene, 1-methyl-3-(1-methylethyl)-	C₁₀H₁₄	0.57	1.78
31	24.7	o-cymene	C₁₀H₁₄	1.26
32	24.85	phenol, 2-methoxy-	C₇H₈O₂	7.75		2.55
33	25.75	benzene, 1-ethyl-2,4-dimethyl-	C₁₀H₁₄	0.57
34	25.89	benzene, 1,2,4,5-tetramethyl-	C₁₀H₁₄	1.64
35	26.54	benzene, 1,2-dimethoxy-	C₈H₁₀O₂	2.98
36	27.93	phenol, 4-methoxy-3-methyl-	C₈H₁₀O₂	1.48
37	27.13	phenol, 4-ethyl-	C₈H₁₀O		13.36	14.55
38	28.13	2-methoxy-5-methylphenol	C₈H₁₀O₂	5.54		0.98
39	29.37	2,3-dimethoxytoluene	C₉H₁₂O₂	2.49
40	30.70	phenol, 4-ethyl-2-methoxy-	C₉H₁₂O₂	5.83	5.63	4.74
41	30.78	ethanone, 1-(2,4-dihydroxyphenyl)-	C₈H₈O₃	1.75
42	31.52	1,2,3-trimethoxybenzene	C₉H₁₂O₃	1.46
43	31.99	1-methylindan-2-one	C₁₀H₁₀O	0.83
44	32.68	2,3-dimethoxyphenol	C₈H₁₀O₃	2.61		7.27
45	32.69	phenol, 2,6-dimethoxy-, acetate	C₁₀H₁₂O₄		12.87
46	33.18	phenol, 2-methoxy-4-propyl-	C₁₀H₁₄O₂	1.12
47	33.97	benzene, 1,2,3-trimethoxy-5-methyl-	C₁₀H₁₄O₃	1.28
48	35.21	3,5-dimethoxy-4-hydroxytoluene	C₉H₁₂O₃	2.01		1.54
49	35.48	dimethyl phthalate	C₁₀H₁₀O₄	3.87		1.49
50	35.94	ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)-	C₁₀H₁₂O₄	0.91	6.54
51	36.37	ethanone, 1-(3-hydroxy-4-methoxyphenyl)-	C₉H₁₀O₃	0.71
52	37.21	2,5-dihydroxy-4-methoxyacetophenone	C₉H₁₀O₄	1.58
53	37.22	4-ethyl-2,6-dimethoxyphenol	C₁₀H₁₄O₃		2.94	1.62
54	38.78	7-methylnaphthalen-2-ol, me derivative	C₁₂H₁₂O	0.49
55	39.25	2,6-dimethoxy-4-propylphenol	C₁₁H₁₆O₃			2.30
56	42.15	4,5-dimethoxy-2-hydroxyacetophenone	C₁₀H₁₂O₄			1.65
57	42.57	1-naphthol, 6,7-dimethyl-	C₁₂H₁₂O	0.77
58	45.86	hexadecanoic acid, methyl ester	C₁₇H₃₄O₂		2.93	3.01
59	49.71	methyl stearate	C₁₉H₃₈O₂			0.76

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