Upgrading of Bio-oil by Catalytic Esterification†

doi:10.7503/cjcu20180404

Abstract

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

CLC Number:

O643
O69

TrendMD:

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

Figures/Tables 7

References 26

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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