芬顿预处理对木质素快速热解甲氧基脱除规律研究

吴晗; 吴凯; 张会岩

芬顿预处理对木质素快速热解甲氧基脱除规律研究

东南大学能源热转换及过程测控教育部重点实验室, 江苏南京 210096

基金项目:

国家重点研发项目 2019YFD1100602

国家优秀青年科学基金 51822604

江苏省杰出青年基金 BK20180014

详细信息

中图分类号: TK6
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出版历程
- 收稿日期: 2020-08-25
- 修回日期: 2020-10-04
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-10-10

Fenton pretreatment of lignin to remove methoxy in pyrolytic bio-oil

Key Laboratory of Energy Thermal Conversion and Control Ministry of Education, Southeast University, Nanjing 210096, China

Funds:

the National Key Research and Development Program of China 2019YFD1100602

The National Nature Science Fund for Excellent Young Scholar (China) 51822604

The Nature Science Fund of Jiangsu Province for Distinguished Young Scholar (China) BK20180014

More Information

Corresponding author: ZHANG Hui-yan,Tel: 13739180368, Email:hyzhang@seu.edu.cn

摘要

摘要: 采用不同H₂O₂含量的芬顿溶液对碱木质素进行预处理，并结合快速热解，探究轻质生物油中含甲氧基化合物含量的变化规律，同时研究了芬顿溶液对木质素结构的影响规律。结果表明，轻质生物油中含甲氧基团的酚类化合物峰面积从AL（未处理碱木质素）的7.3×10⁹下降至13-FML（H₂O₂含量为13 mL/g芬顿溶液预处理碱木质素）的5.2×10⁹，减少了0.29倍。而含甲基团和乙基团的酚类化合物峰面积从AL的3.9×10⁹上升到13-FML的7.2×10⁹，增加了0.85倍。同时，轻质生物油产率从22.4%提高到28.7%。通过FT-IR、¹H NMR和¹³C NMR分析发现，芬顿预处理使木质素凝缩性结构单元减少，甲氧基含量降低，为后续快速热解产生低甲氧基含量的生物油提供了有利条件。
- 木质素 /
- 芬顿预处理 /
- 快速热解 /
- 甲氧基脱除
Abstract: A Fenton solution with different H₂O₂ concentrations was used to pretreat an alkali lignin (AL), and combined with fast pyrolysis, the change in the content of phenolic compounds containing methoxy group in light bio-oil was explored, also, the influence of the Fenton solution on the structure of the alkali lignin was also studied. The results show that the peak area of phenolic compounds containing methoxy groups in light bio-oil decreases from 7.3×10⁹ with AL (untreated alkali lignin) to 5.2×10⁹ with 13-FML (pretreated alkali lignin with Fenton solution at a concentration of 13 mL/g H₂O₂), decreasing by about 29%. While the peak area of phenolic compounds containing methyl groups and ethyl groups increases from 3.9×10⁹ with AL to 7.2×10⁹ with 13-FML, increasing by about 1.85 times. At the same time, the yield of light bio-oil increases from 22.4% to 28.7%. Through FT-IR, ¹H NMR and ¹³C NMR analysis, it is found that Fenton pretreatment can destroy the condensational structural units of lignin and reduce the content of methoxy, thus providing favorable conditions for subsequent fast pyrolysis to produce bio-oil with low methoxy content.
- lignin /
- fenton pretreatment /
- fast pyrolysis /
- methoxy removal

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图 1 木质素快速热解实验装置示意图

Figure 1 Schematic diagram of experimental device for fast pyrolysis of lignin

1-nitrigon; 2-mass flowmeter; 3-temperature control system; 4-sample container; 5-quartz tube reactor; 6-tube furnace; 7-cooling system; 8-drying tube; 9-gas bag

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图 2 木质素快速热解产物产率的分布

Figure 2 Yield distribution of lignin fast pyrolysis products

(a): yield distribution of four products; (b): yield distribution of non-condensable gas

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图 3 含甲氧基团与含甲基团和乙基团酚类化合物的峰面积及选择性

Figure 3 Peak area and selectivity of phenolic compounds containing methoxy groups, methyl groups and ethyl groups

(a): peak area of phenolic compounds; (b): selectivity of phenolic compounds

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图 4 木质素的红外光谱谱图

Figure 4 FT-IR spectra analysis of four lignins

a: AL; b: 3-FML; c: 9-FML; d: 13-FML

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图 5 碱木质素(AL)和芬顿预处理碱木质素(13-FML)的¹H NMR谱图

Figure 5 ¹H NMR analysis of AL and 13-FML

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图 6 芬顿预处理碱木质素(13-FML)和碱木质素(AL)的¹³C NMR谱图

Figure 6 ¹³C NMR analysis of AL and 13-FML

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表 1 轻质生物油的GM-MS分析

Table 1 GM-MS analysis of light bio-oil

Time	Compounds	Peak area of compounds /×10⁹
Time	Compounds	AL	3-FML	5-FML	9-FML	13-FML	15-FML
Phenol methoxy groups
15.1	phenol, 2-methoxy-	1.9	1.6	1.3	1.0	0.9	0.9
16.6	phenol, 2-methoxy-3-methyl-	0.3	0.2	0.2	0.4	0.3	0.2
17.3	phenol, 2-methoxy-4-methyl-	0.6	0.8	0.8	0.7	0.7	0.7
19.2	phenol, 4-ethyl-2-methoxy-	0.8	0.8	0.8	0.7	0.7	0.6
20.4	2-methoxy-4-vinylphenol	1.5	1.1	1.0	1.0	1.0	1.0
21.5	phenol, 2, 6-dimethoxy-	1.2	0.7	0.7	0.6	0.5	0.5
21.7	3-methoxy-5-methylphenol	0.1	0.3	0.3	0.4	0.5	0.4
23.7	phenol, 4-methoxy-3-(methoxymethyl)-	0.9	0.7	0.7	0.6	0.6	0.5
Total		7.3	6.2	5.8	5.4	5.2	4.8
Phenol methyl groups and phenol ethyl groups
15.0	phenol, 2-methyl-	0.6	0.5	0.5	0.7	0.9	0.8
15.7	phenol, 4-methyl-	0.8	1.2	1.2	1.5	2.0	1.9
16.8	phenol, 2, 4-dimethyl-	0.3	0.5	0.4	0.7	0.9	0.7
17.6	phenol, 4-ethyl-	1.6	1.6	1.5	1.8	2.2	1.9
18.4	phenol, 3-ethyl-5-methyl-	0.3	0.4	0.4	0.6	0.7	0.3
20.6	2-pllylphenol	0.3	0.3	0.3	0.4	0.5	0.3
Total		3.9	4.5	4.3	5.7	7.2	5.9
Acid
6.7	acetic acid	0.2	0.3	0.3	0.4	0.5	0.6
Phenol
14.0	phenol	1.2	1.3	1.6	2.0	2.3	2.2
Others
Total		4.9	3.6	3.7	4.6	4.8	4.7

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