催化酯化升级生物质油

doi:10.7503/cjcu20180404

摘要/Abstract

摘要：

以稻壳热解油为原料, 采用减压蒸馏法将生物质油轻组分和重组分分离. 由生物质油重组分通过催化酯化反应制备了乙醇生物质油, 对催化剂硫酸采用纳米碳酸钙沉淀法进行分离, 从而实现生物质油的品质升级. 以生物质油的pH值作为评价升级反应的指标, 考察了催化酯化反应条件和后处理条件的影响. 采用气相色谱-质谱联用(GC/MS)和凝胶色谱(GPC)研究了稻壳热解油和乙醇生物质油的组成和分子量的变化. 实验结果表明, 在催化酯化过程中, 当反应温度为120 ℃, 反应时间为3 h, 硫酸用量为4 g, 溶剂为无水乙醇时, 乙醇生物质油的pH值可达5.86. 在催化剂中和过程中, 中和剂对乙醇生物质油pH值的影响顺序为BaO≈BaCO₃<CaCO₃<nano-CaCO₃<CaO. 经过催化酯化升级过程, 不仅乙醇生物质油中的酯类物质增加了26.1%, 酸类物质和酚类物质分别减少了15.9%和12.8%, 而且乙醇生物质油的分子量也降低了90%.

关键词: 生物质油升级, 乙醇生物质油, 中和剂, 催化酯化

Abstract:

Bio-oil pyrolyzed from rice husk was separated into light-oil and heavy-oil by vacuum distillation. The heavy-oil was upgraded by catalytic esterification with sulfuric acid to prepare ethanol-bio-oil. Then the sulfuric acid catalyst was separated from ethanol-bio-oil using neutralizer. Effects of the catalytic esterification and neutralization on the pH value of ethanol-bio-oil were investigated. The component and molecular weight of raw bio-oil and the ethanol-bio-oil were analyzed by GC/MS and GPC. The results show that the pH value of ethanol-bio-oil can reach 5.86 under the following optimized reaction conditions, 120 ℃, 3 h, sulfuric acid as catalyst, ethanol as solvent. The influence sequence of neutralizers on the pH value of ethanol-bio-oil is as following, BaO≈BaCO₃<CaCO₃<nano-CaCO₃<CaO. In addition, after the progress of catalytic esterification, not only did esters increase by 26.1%, acids and phenols in ethanol bio-oil decrease by 15.9% and 12.8%, respectively, but also did the molecular weight of ethanol-bio-oil decrease by 90%.

Key words: Upgrading of bio-oil, Ethanol-bio-oil, Neutralizer, Catalytic esterification

中图分类号:

O643
O69

TrendMD:

程岩岩, 隋光辉, 陈志敏, 魏庆玲, 段亚军, 王晓峰, 杨晓敏, 王子忱. 催化酯化升级生物质油. 高等学校化学学报, 2018, 39(12): 2746.

CHENG Yanyan,SUI Guanghui,CHEN Zhimin,WEI Qingling,DUAN Yajun,WANG Xiaofeng,YANG Xiaomin,WANG Zichen. Upgrading of Bio-oil by Catalytic Esterification^†. Chem. J. Chinese Universities, 2018, 39(12): 2746.

图/表 7

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Raw bio-oil compound	Reaction time/min	Area percentage(%)
Acids	3.61	21.0
(E)-2-Pentenoic acid		21.0
Esters		16.3
Ethyl butyrate	3.94	0.8
4-Ethylphenyl acetate	13.70	15.5
Phenols		51.8
2-Methoxyphenol	11.67	10.9
2-Methoxy-4-methylphenol	12.35	10.6
Raw bio-oil compound	Reaction time/min	Area percentage(%)
Phenol	12.60	12.3
4-Ethyl-2-methoxyphenol	12.84	4.7
4-Methylphenol	13.12	9.0
3-Methylphenol	13.17	3.2
2-Methoxy-4-propylphenol	13.36	1.0
Others		10.9
2,5-Diethoxy-tetrahydrofuran	6.63	3.1
4-O-β-D-Galactopyranosyl-β-D-glucopyranose	10.77	1.0
β-D-Glucopyranose	11.15	1.5
2-Hydroxy-3-methyl-2-cyclopenten-1-one	11.46	5.4

Raw bio-oil compound	Reaction time/min	Area percentage(%)
Acids	3.61	21.0
(E)-2-Pentenoic acid		21.0
Esters		16.3
Ethyl butyrate	3.94	0.8
4-Ethylphenyl acetate	13.70	15.5
Phenols		51.8
2-Methoxyphenol	11.67	10.9
2-Methoxy-4-methylphenol	12.35	10.6
Raw bio-oil compound	Reaction time/min	Area percentage(%)
Phenol	12.60	12.3
4-Ethyl-2-methoxyphenol	12.84	4.7
4-Methylphenol	13.12	9.0
3-Methylphenol	13.17	3.2
2-Methoxy-4-propylphenol	13.36	1.0
Others		10.9
2,5-Diethoxy-tetrahydrofuran	6.63	3.1
4-O-β-D-Galactopyranosyl-β-D-glucopyranose	10.77	1.0
β-D-Glucopyranose	11.15	1.5
2-Hydroxy-3-methyl-2-cyclopenten-1-one	11.46	5.4

Ethanol-bio-oil compound	Reaction time/min	Area percentage(%)
Acids		5.1
(E)-2-pentenoic acid	3.62	5.1
Esters		42.4
Ethyl acetate	3.17	3.3
Ethyl butyrate	3.95	1.2
Ethyl crotonate	5.40	1.3
Ethyl palmitate	14.12	14.1
Ethyl oleate	15.46	15.1
Ethyl linoleate	15.73	7.4
Phenols		39.0
2-Methoxyphenol	11.61	5.5
4-Hydroxybenzoic acid	11.68	0.9
4-Hydroxybenzeneethanol	12.01	0.8
2-Methoxy-4-methylphenol	12.29	4.7
Phenol	12.56	5.1
4-Ethyl-2-methoxyphenol	12.78	2.7
4-Methylphenol	13.08	4.2
3-Methylphenol	13.13	0.6
2-Methoxy-4-propylphenol	13.30	1.4
4-Ethylphenol	13.66	8.8
(E)-4-[3-(Hydroxymethyl)-5-(3-hydroxyprop-1-enyl)-7-methoxy-	16.59	4.3
2,3-dihydrobenzofuran-2-yl]-2-methoxyphenol
Others		13.5
5-(Hydroxymethyl)-2-Furancarboxaldehyde	6.09	3.7
2,5-Diethoxy-tetrahydrofuran	6.50	1.3
Fructose	8.30	3.2
4-O-β-D-galactopyranosyl-β-D-glucopyranose	11.09	2.5
2-Hydroxy-3-methyl-2-cyclopenten-1-one	11.38	2.8

Ethanol-bio-oil compound	Reaction time/min	Area percentage(%)
Acids		5.1
(E)-2-pentenoic acid	3.62	5.1
Esters		42.4
Ethyl acetate	3.17	3.3
Ethyl butyrate	3.95	1.2
Ethyl crotonate	5.40	1.3
Ethyl palmitate	14.12	14.1
Ethyl oleate	15.46	15.1
Ethyl linoleate	15.73	7.4
Phenols		39.0
2-Methoxyphenol	11.61	5.5
4-Hydroxybenzoic acid	11.68	0.9
4-Hydroxybenzeneethanol	12.01	0.8
2-Methoxy-4-methylphenol	12.29	4.7
Phenol	12.56	5.1
4-Ethyl-2-methoxyphenol	12.78	2.7
4-Methylphenol	13.08	4.2
3-Methylphenol	13.13	0.6
2-Methoxy-4-propylphenol	13.30	1.4
4-Ethylphenol	13.66	8.8
(E)-4-[3-(Hydroxymethyl)-5-(3-hydroxyprop-1-enyl)-7-methoxy-	16.59	4.3
2,3-dihydrobenzofuran-2-yl]-2-methoxyphenol
Others		13.5
5-(Hydroxymethyl)-2-Furancarboxaldehyde	6.09	3.7
2,5-Diethoxy-tetrahydrofuran	6.50	1.3
Fructose	8.30	3.2
4-O-β-D-galactopyranosyl-β-D-glucopyranose	11.09	2.5
2-Hydroxy-3-methyl-2-cyclopenten-1-one	11.38	2.8

Compound	Area percentage(%)
Ethyl palmitate	14.1
Ethyl oleate	15.1
Ethyl linoleate	7.4
4-Ethylphenol	8.8
(E)-4-[3-(Hydroxymethyl)-5-(3-hydroxyprop-1-enyl)-7-methoxy-2,3-dihydrobenzofuran-2-yl]-2-methoxyphenol	4.3
5-(Hydroxymethyl)-2-Furancarboxaldehyde	3.7
Ethyl acetate	3.3