金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究

张文豪; 童乐; 冯君锋; 潘晖

doi:10.19906/j.cnki.JFCT.2023071

金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究

doi: 10.19906/j.cnki.JFCT.2023071

张文豪^1,,
童乐^1,,
冯君锋^{1, 2, ,},
潘晖^{1, 2,}

1.
南京林业大学化学工程学院, 江苏南京 210037
2.
南京林业大学江苏省林业资源高效加工利用协同创新中心江苏省高校农林生物质化学与利用国家重点实验室培育建设点, 江苏南京 210037

基金项目: 国家自然科学基金(32101469)和广西林产化学与工程重点实验室(国家民委重点实验室)开放基金课题(GXFK2204)资助

详细信息

通讯作者:
Tel: 13770663924 , E-mail: 2018149@njfu.edu.cn

中图分类号: TQ35;TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2023-05-12
- 修回日期: 2023-08-28
- 录用日期: 2023-09-12
- 网络出版日期: 2023-09-18
- 刊出日期: 2024-03-10

Study on preparation of cyclohexanol from lignin-derived phenolic compounds catalyzed by metal oxide-loaded ruthenium

ZHANG Wenhao^1
,,
TONG Le^1
,,
FENG Junfeng^{1, 2
, ,},
PAN Hui^{1, 2
,}

1.
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
2.
Jiangsu Co-Innovation Centre of Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-forest Biomass, Nanjing Forestry University, Nanjing 210037, China

Funds: The project was supported by National Natural Science Foundation of China (32101469)，Guangxi Key Laboratory of Forest Products Chemistry and Engineering (State Ethnic Affairs Commission Key Laboratory) Open Fund Project (GXFK2204)

摘要

摘要: 本研究采用初湿浸渍法，制备得到一系列钌负载于金属氧化物载体的催化剂(Ru/CeO₂、Ru/Nb₂O₅、Ru/ZrO₂、Ru/Al₂O₃和Ru/CeO_x)，用于木质素衍生酚类化合物苯酚提质加氢转化为环己醇的研究。通过采用X射线晶体衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等手段对所制备催化剂进行结构和物化特征的表征，发现Ru/CeO_x中含有的氧空位可以很好地吸附带有含氧基团的原料，从而有利于苯酚的高效加氢；同时XPS表明，Ru/CeO_x中的有效活性中心RuO₂和Ru⁰是催化加氢的活性位点，因此，氧空位和金属活性位点的共同作用使得催化剂有较好的加氢活性。探究了反应温度、压力、时间对加氢效果的影响，发现催化剂能够在140 ℃下使苯酚完全转化，得到目标产物环己醇得率为90.2%，并对催化剂的循环特性进行考察，发现循环使用四次后催化剂仍表现出优异的加氢活性。同时采用GC-MS检测加氢过程的中间产物，进而推断出苯酚加氢过程的反应路径。
- 金属氧化物 /
- 木质素 /
- 酚类化合物 /
- 催化加氢 /
- 环己醇
Abstract: Hydrodeoxygenation of lignin bio-oil to prepare liquid fuels is a very promising route. In this paper, a series of catalysts (Ru/CeO₂, Ru/Nb₂O₅, Ru/ZrO₂, Ru/Al₂O₃ and Ru/CeO_x) supported on metal oxides were prepared by incipient wetness impregnation method, which were used to study the upgrading and hydrogenation of lignin-derived phenolic compounds phenol to cyclohexanol. By means of X-ray crystal diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), the structure and physical and chemical characteristics of the prepared catalyst were characterized. It was found that the oxygen vacancies contained in Ru/CeO_x could adsorb the raw materials with oxygen groups well, which was beneficial to the efficient hydrogenation of phenol. At the same time, XPS showed that the effective active centers in Ru/CeO_x, RuO₂ and Ru⁰, were active sites for catalytic hydrogenation. Therefore, the combined action of oxygen vacancies and metal active sites made the catalyst have good hydrogenation activity. The effects of reaction temperature, pressure and time on hydrogenation were also investigated. It was found that the catalyst could completely convert phenol at a mild temperature (140 ℃) and the yield of cyclohexanol was 90.2%. The cycle characteristics of the catalyst were investigated, and it was found that the catalyst still showed excellent hydrogenation activity after being recycled for 4 times. At the same time, the intermediate products in the hydrogenation process were detected by GC-MS, and then the reaction path of phenol hydrogenation process was deduced.
- metal oxide /
- lignin /
- phenolic compounds /
- catalytic hydrogenation /
- cyclohexanol

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FIG. 3013. FIG. 3013.

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图 1 (a) 载体CeO_x的X射线衍射谱图及(b) 催化剂RuNi/CeO_x和Ru/CeO_x的X射线衍射谱图

Figure 1 (a) X-ray diffraction pattern of CeO_x support and (b) X-ray diffraction patterns of catalysts RuNi/CeO_x and Ru/CeO_x

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图 2 CeO_x载体和Ru/CeO_x催化剂的扫描电镜照片

Figure 2 SEM of CeO_x support and Ru/CeO_x catalyst ((a) (10 μm) CeO_x, (b) (5 μm) CeO_x, (c) (1 μm) CeO_x, (d) (10 μm) Ru/CeO_x, (e) (5 μm) Ru/CeO_x, (f) (1 μm) Ru/CeO_x)

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图 3 Ru/CeO_x催化剂的HRTEM照片

Figure 3 HRTEM image of Ru/CeO_x catalyst ((a) Ru/CeO_x image, (b) Ru particle size distribution diagram, (c) Ru and CeO₂ lattice, (d) local enlargement of Ru particles)

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图 4 Ru/CeO₂和Ru/CeO_x催化剂的XPS谱图

Figure 4 XPS spectra of Ru/CeO₂ catalyst ((a) Ce 3d, (c) Ru 3p, (f) O 1s) and Ru/CeO_x catalyst ((b) Ce 3d, (d) Ru 3p, (e) O 1s)

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图 5 催化剂Ru/CeO_x和Ru/CeO₂的激光拉曼光谱谱图

Figure 5 Raman spectra of catalysts Ru/CeO_x and Ru/CeO₂

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图 6 反应时间对催化剂性能的影响

Figure 6 Effect of reaction time on catalyst performance

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图 7 反应温度对催化剂性能的影响

Figure 7 Effect of reaction temperature on catalyst performance

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图 8 反应氢气压力对催化剂性能的影响

Figure 8 Effect of reaction hydrogen pressure on catalyst performance

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图 9 反应后液体产物的GC-MS谱图

Figure 9 GC-MS spectrum of liquid product after reaction

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图 10 苯酚催化转化的可能反应途径

Figure 10 Possible reaction pathway of catalytic conversion of phenol

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图 11 Ru/CeO_x循环性能

Figure 11 Ru/CeO_x Cyclic experiment

Reaction conditions: 0.05 g Ru/CeO_x, 3 MPa H₂, 140 ℃, 3 h.

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图 12 Ru/CeO_x催化剂的XPS谱图

Figure 12 XPS spectra of Ru/CeO_x catalyst ((a) not used Ce 3d, (b) used Ce 3d, (c) not used Ru 3p, (d) used Ru 3p)

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表 1 不同催化剂的性能研究

Table 1 Performance study of different catalysts

Catalyst	Conversion/%	Cyclohexanol yield/%
Ni/Nb₂O₅	31.00	0.00
Ni/CeO₂	73.50	62.70
Ru/Nb₂O₅	41.70	37.50
Ru/CeO₂	100.00	82.50
Ru-Ni/CeO₂	90.00	80.00
Ru/ZrO₂	10.00	0.40
Ru/Al₂O₃	12.50	0.76
Ru/CeO_x	100.00	90.20
Reaction conditions: catalyst 0.05 g, reaction time 3 h, reaction temperature 140 ℃, hydrogen pressure 3 MPa.

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