Co@C催化木质素衍生酚类化合物的加氢转化

赵云鹏; 赵薇; 司兴刚; 曹景沛; 魏贤勇

doi:10.19906/j.cnki.JFCT.2021004

Co@C催化木质素衍生酚类化合物的加氢转化

doi: 10.19906/j.cnki.JFCT.2021004

赵云鹏^{1, 2, ,},
赵薇¹,
司兴刚¹,
曹景沛^1, ,,
魏贤勇^{1, 2}

1.
中国矿业大学煤炭加工与高效利用教育部重点实验室，江苏徐州 221116
2.
新疆大学化工学院，新疆乌鲁木齐 830046

基金项目: 国家自然科学基金(21878325)，中央高校基本科研业务费(中国矿业大学，2019XKQYMS49)和江苏省高校优势学科项目资助

详细信息

通讯作者:
E-mail: zhaoyp@cumt.edu.cn,

caojingpei@cumt.edu.cn

中图分类号: TQ530
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- 被引次数: 0
出版历程
- 收稿日期: 2020-09-09
- 修回日期: 2020-10-10
- 刊出日期: 2021-01-29

Hydrogenation of lignin-derived phenolic compounds over Co@C catalysts

ZHAO Yun-peng^{1, 2
, ,},
ZHAO Wei¹,
SI Xing-gang¹,
CAO Jin-pei^{1
, ,},
WEI Xian-yong^{1, 2}

1.
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou 221116, China
2.
School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830046, China

Funds: The project was supported by the National Natural Science Foundation of China (21878325), the Fundamental Research Funds for the Central Universities (China University of Mining and Technology, 2019XKQYMS49), and the Priority Academic Program Development of Jiangsu Higher Education Institutions

摘要

摘要: 采用溶剂热法合成Co-MOF，然后通过一步热解法制备了Co@C催化剂。通过N₂物理吸附-脱附(BET)、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等分析手段对Co@C催化剂的结构进行了表征。探讨了Co-MOF热解温度、反应温度、初始氢压以及反应时间对Co@C催化愈创木酚加氢转化的影响。结果表明，Co-MOF和Co@C中均以介孔为主；片层结构的Co-MOF热解后变成不规则的球状，并且随着热解温度升高，Co@C的比表面积不断减小。以Co@C-600为催化剂，在反应温度180 ℃、初始氢压2 MPa、反应时间2 h的条件下，愈创木酚完全转化，环己醇的选择性为92.8%。Co@C催化愈创木酚加氢转化的主要反应路径为先通过脱甲氧基生成苯酚，进一步加氢生成环己醇。此外，Co@C-600对苯酚、对甲氧基苯酚和4-甲基愈创木酚等其他衍生酚单体也具有较好的催化活性。
- 木质素 /
- 愈创木酚 /
- 环己醇 /
- 加氢脱氧 /
- Co@C催化剂
Abstract: Co-MOF was firstly prepared by solvothermal method, and then Co@C catalyst was prepared by one-step pyrolysis method from Co-MOF. The structure of Co@C catalyst was characterized by N₂ physical adsorption-desorption (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Effects of Co-MOF pyrolysis temperature, reaction temperature, initial hydrogen pressure and reaction time on catalytic hydrogenation of guaiacol were investigated. The results show that both Co-MOF and Co@C are dominated by mesoporous. After pyrolysis, lamellar structure of Co-MOF changes into irregular sphericity. As raising pyrolysis temperature, specific surface area of Co@C decreases continuously. Under the conditions of reaction temperature 180 ℃, initial hydrogen pressure 2 MPa and reaction time 2 h, the guaiacol was completely transformed and selectivity of cyclohexanol was 92.8% using Co@C-600 as catalyst. The main reaction pathway of guaiacol hydrogenation catalyzed by Co@C is that guaiacol firstly forms phenol through removal of methoxyl group, and further is hydrogenated to cyclohexanol. In addition, Co@C-600 also has good catalytic activity for other phenolic monomers derived from lignin, such as phenol, p-methoxyphenol and 4-methyl guaiacol.
- lignin /
- guaiacol /
- cyclohexanol /
- hydrodeoxygenation /
- Co@C catalyst

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图 1 Co@C-X催化剂制备过程示意图

Figure 1 Preparation process of Co@C-X catalyst

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图 2 (a) N₂吸附-脱附等温线和(b) Co-MOF和Co@C-X催化剂的孔径分布

Figure 2 N₂ BET characterization of Co-MOF and Co@C-X: (a) N₂ adsorption-desorption isotherms and (b) pore size distribution of Co-MOF

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图 3 Co-MOF和Co@C-X催化剂的XRD谱图

Figure 3 XRD patterns of Co-MOF and Co@C-X

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图 4 Co@C-600的XPS谱图

Figure 4 XPS spectra of Co@C-600 catalyst

(a): survey; (b):Co 2p; (c):C 1s

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图 5 Co-MOF (a)、Co@C-600 (b)的TEM照片，Co-MOF (c)、Co@C-600 (d)的SEM照片，Co@C-600 (e)、Co (f)、C (g)和O (h)元素的SEM-EDS照片

Figure 5 TEM images of Co-MOF (a) and Co@C-600 (b); SEM images of Co-MOF (c) and Co@C-600 (d); SEM-EDS mapping images of Co@C-600 catalyst (e) with Co (f), C (g) and O (h) elements

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图 6 温度对愈创木酚催化加氢脱氧的影响

Figure 6 Effect of temperature on the guaiacol hydrodeoxygenation

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图 7 初始氢压对愈创木酚催化加氢脱氧的影响

Figure 7 Effect of initial H₂ pressure on the guaiacol hydrodeoxygenation

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图 8 反应时间对愈创木酚加氢脱氧的影响

Figure 8 Effect of time on the guaiacol hydrodeoxygenation

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图 9 Co@C催化愈创木酚的加氢脱氧反应路径

Figure 9 Proposed pathway for guaiacol hydrodeoxygenation

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图 10 Co@C-600催化剂重复使用性能

Figure 10 Co@C-600 reuse performance

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表 1 Co-MOF及Co@C-X的理化性质

Table 1 Physicochemical properties of Co-MOF and Co@C-X

Sample	Surface area/ (m²·g⁻¹)^a	Pore volume/ (cm³·g⁻¹)^b	Pore diameter/ nm^b	Cobalt content w/%^c
Co-MOF	56.30	0.03	3.41	37.3
Co@C-500	35.51	0.03	3.83	50.6
Co@C-600	31.93	0.04	3.81	56.2
Co@C-700	17.77	0.04	3.82	64.8
^acalculated by BET method; ^bcalculated by BJH method; ^cmeasured with LA-ICP-MS

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表 2 愈创木酚在不同催化剂上的转化及产物分布

Table 2 Guaiacol conversion and product distribution over different catalysts

Sample	Conversion/%	Selectivity/%
Sample	Conversion/%		(trans-, cis-)
Co@C-500	6.4	77.6	22.4
Co@C-600	92.5	90.8	9.2
Co@C-700	trace	−	−

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表 3 Co@C-600对木质素衍生酚类单体的催化

Table 3 Catalysis of Co@C-600 to lignin-derived phenolic monomers

Substrate	Conversion/%	Selectivity/%
	99.9	100
	99.9	75.1	2.8	22.1
	99.9	2.6	97.4
	99.9	100.0
	99.9	100.0
	99.9	100.0

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