Ni/SiO2-Al2O3固体酸催化剂催化氢解碱木质素制备芳香类化合物

doi:10.7503/cjcu20170591

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (4): 735.doi: 10.7503/cjcu20170591

Ni/SiO₂-Al₂O₃固体酸催化剂催化氢解碱木质素制备芳香类化合物

周列^1,², 吴青云², 徐莹²(), 王晨光², 马隆龙², 李文志¹, 陈佩丽²

1. 中国科学技术大学纳米科学与技术学院, 苏州 215123
2. 中国科学院广州能源研究所,中国科学院可再生能源重点实验室, 广东省新能源和可再生能源研究开发与应用重点实验, 广州 510640

收稿日期:2017-08-31 出版日期:2018-04-10 发布日期:2018-03-27
作者简介:联系人简介: 徐莹, 女, 博士, 研究员, 主要从事木质素定向解聚、催化剂开发和生物油提制方面的研究. E-mail:xuying@ms.giec.ac.cn
基金资助:
国家自然科学基金(批准号: 51676191)、广东省特支计划青年拔尖人才计划(批准号: 2015TQ01W652)、广东省科技计划项目(批准号: 2014A010106019)和中国科学院青年创新促进会项目(批准号: 2016313)资助

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

ZHOU Lie^1,², WU Qingyun², XU Ying^2,^*(), WANG Chenguang², MA Longlong², LI Wenzhi¹, CHEN Peili²

1. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China
2. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, CAS Key Laboratory of Renewable Energy,Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development,Guangzhou 510640, China

Received:2017-08-31 Online:2018-04-10 Published:2018-03-27
Contact: XU Ying E-mail:xuying@ms.giec.ac.cn
Supported by:
† Supported by the National Natural Science Foundationof China(No.51676191), the Youth Science and Technology Innovation Talents Plan of Guangdong Province, China(No.2015TQ01W652), the Science and Technology Plan Project of Guangdong Province, China(No.2014A010106019), the Program of Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2016313)

摘要/Abstract

摘要：

以具有弱酸中心和中强酸中心的无定形硅铝为载体, 负载Ni基催化剂, 对碱木质素进行解聚制备了芳香类化合物. 考察了Ni负载量、反应温度和反应时间对碱木质素氢解产物生成及分布的影响. 对解聚产物进行气相色谱(GC)、气相色谱-质谱(GC-MS)及傅里叶变换红外光谱(FTIR)等分析, 探讨了氢解反应过程. 研究结果表明, 催化剂的酸性是促进木质素解聚生成芳烃类产物的主要因素, 且随着催化剂酸量的增加, 芳烃类产物的收率呈上升趋势. 以15%Ni/SiO₂-Al₂O₃为催化剂氢解木质素时, 随着反应温度升高, 芳香类化合物收率先增加后降低, 在反应温度为300 ℃时最优, 芳烃类产物收率为9.05%, 芳香类化合物总收率为22.53%. 随着反应时间的延长, 芳香烃类产物收率先增加, 后趋于稳定, 酚类化合物收率逐渐提高, 反应12 h时, 芳香类化合物收率最高为26.54%.

关键词: 镍催化剂, 碱木质素, 氢解, 芳香化合物

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

中图分类号:

O643

TrendMD:

周列, 吴青云, 徐莹, 王晨光, 马隆龙, 李文志, 陈佩丽. Ni/SiO₂-Al₂O₃固体酸催化剂催化氢解碱木质素制备芳香类化合物. 高等学校化学学报, 2018, 39(4): 735.

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^†. Chem. J. Chinese Universities, 2018, 39(4): 735.

图/表 9

参考文献 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

Ni/SiO₂-Al₂O₃固体酸催化剂催化氢解碱木质素制备芳香类化合物

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

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