Depolymerization of the Alkali Lignin for Aromatic Compounds over Ni/SiO2-Al2O3 Solid Acid Catalysts†

doi:10.7503/cjcu20170591

Abstract

Abstract:

Optional discarded and unreasonable utilization of industrial alkali lignin leaded to water and air pollution. However, alkali lignin could be utilized as fine chemical resource for its specific phenyl propane structure. In this paper, we investigated efficient depolymerization methods on alkali lignin aiming for aromatic products over acidic SiO₂-Al₂O₃ and Ni/SiO₂-Al₂O₃ by one-step. The effects of Ni metal loading contents, reaction temperature and reaction time in this process were also discussed. Analysis of lignin depolymerized products were carried with gas chromatography(GC), gas chromatography-mass spectrometry(GC-MS), Fourier transform-infrared spectroscopy(FTIR). The results showed that Ni/SiO₂-Al₂O₃ can promote the conversion of the alkali lignin. Yield(mass fraction) of aromatic products increased and then decreased along with the rising of reaction temperature, which the yield of arenes was 9.05% and the yield of aromatic products was 22.53% over 15%Ni/SiO₂-Al₂O₃ catalyst at 300 ℃ after depolymerization. Reaction time also showed significantly influence on depolymerized products, with the reaction times increasing. The arenes yield was increased and then stabilized, aromatic products yield reached 26.54% after reacted 12 h.

Key words: Ni catalyst, Alkali Lignin, Hydrogenolysis, Aromatics

CLC Number:

O643

TrendMD:

ZHOU Lie, WU Qingyun, XU Ying, WANG Chenguang, MA Longlong, LI Wenzhi, CHEN Peili. Depolymerization of the Alkali Lignin for Aromatic Compounds over Ni/SiO₂-Al₂O₃ Solid Acid Catalysts^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 735.

Figures/Tables 9

References 33

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Catalyst	Acid content/(μmol·g^-1)	Catalyst	Acid content/(μmol·g^-1)
SiO₂-Al₂O₃	628.54	15%Ni/SiO₂-Al₂O₃	756.17
5%Ni/SiO₂-Al₂O₃	673.95	20%Ni/SiO₂-Al₂O₃	783.20
10%Ni/SiO₂-Al₂O₃	693.08

Catalyst	Acid content/(μmol·g^-1)	Catalyst	Acid content/(μmol·g^-1)
SiO₂-Al₂O₃	628.54	15%Ni/SiO₂-Al₂O₃	756.17
5%Ni/SiO₂-Al₂O₃	673.95	20%Ni/SiO₂-Al₂O₃	783.20
10%Ni/SiO₂-Al₂O₃	693.08

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm
SiO₂-Al₂O₃	459.44	0.637	4.346
5%Ni/SiO₂-Al₂O₃	432.85	0.628	4.319
10%Ni/SiO₂-Al₂O₃	402.88	0.561	3.847
15%Ni/SiO₂-Al₂O₃	390.14	0.468	3.424
20%Ni/SiO₂-Al₂O₃	353.01	0.334	3.421

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm
SiO₂-Al₂O₃	459.44	0.637	4.346
5%Ni/SiO₂-Al₂O₃	432.85	0.628	4.319
10%Ni/SiO₂-Al₂O₃	402.88	0.561	3.847
15%Ni/SiO₂-Al₂O₃	390.14	0.468	3.424
20%Ni/SiO₂-Al₂O₃	353.01	0.334	3.421

Product	Yield of product(%)
Product	SiO₂-Al₂O₃	5%Ni/SiO₂-Al₂O₃	20%Ni/SiO₂-Al₂O₃
Arenes	3.17	4.18	8.91
Toluene	-	0.04	0.03
Ethylbenzene	-	0.18	-
p-Xylene	0.01	0.01	0.08
o-Xylene	2.26	2.82	5.96
Benzene, 1-ethyl-2-methyl-	0.02	0.05	0.09
Benzene, 1,2,3-trimethyl-	0.09	0.13	0.34
Benzene, 1-ethyl-3,5-dimethyl-	0.05	0.08	0.20
Benzene, 1-methyl-3-(1-methylethyl)-	0.06	0.04	0.13
Benzene, 2-ethyl-1,4-dimethyl-	0.36	0.40	1.01
Benzene, 1,3-diethyl-5-methyl-	0.02	0.01	0.09
Benzene, 2,4-diethyl-1-methyl-	0.08	0.12	0.23
Benzene, 1-ethyl-2,4,5-trimethyl-	0.03	0.05	-
Benzene, 1,3,5-triethyl-	0.02	0.02	0.06
Benzene, 1,2-diethyl-3,4-dimethyl-	0.12	0.08	0.39
Naphthalene, 1-methyl-	0.03	0.04	0.11
Naphthalene, 2,7-dimethyl-	0.01	0.02	0.06
Naphthalene, 1,4-dimethyl-	0.01	0.01	0.04
Naphthalene, 2-(1-methylethyl)-	-	0.01	-
Phenanthrene, 9-ethyl-	0.02	0.07	0.09
Phenolic compound	7.08	9.55	14.92
6-Methyl-4-indanol	3.28	2.45	6.02
Phenol, 2-ethyl-5-methyl-	0.21	0.46	0.42
Phenol, 2-ethyl-	0.28	0.19	0.26
Phenol, 2-ethyl-4,5-dimethyl-	0.25	2.12	1.26
Propofol	0.16	0.66	0.26
Phenol, 2-ethyl-4-methyl-	0.46	0.71	0.70
Phenol, 4-ethyl-	0.76	1.70	-
Phenol, 2-methyl-5-(1-methylethyl)-	-	0.27	0.27
Product	Yield of product(%)
Product	SiO₂-Al₂O₃	5%Ni/SiO₂-Al₂O₃	20%Ni/SiO₂-Al₂O₃
Phenol, 3,5-bis(1,1-dimethylethyl)-	-	0.17	0.21
Phenol, 2-ethyl-4,5-dimethyl-	0.22	0.17	0.21
Phenol, 3,5-diethyl-	0.22	0.60	0.57
Ethanone, 1-(2-hydroxy-5-methylphenyl)-	0.47	-	0.89
Phenol, 2,4-bis(1-methylethyl)-	0.46	-	-
Benzyl alcohol compound	-	3.37	1.67
Benzenemethanol, 4-(1,1-dimethylethyl)-	-	3.37	1.67

Depolymerization of the Alkali Lignin for Aromatic Compounds over Ni/SiO₂-Al₂O₃ Solid Acid Catalysts^†

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