Efficient catalytic hydrodeoxygenation of lignin derived phenolics on Ni-VO x interface

doi:10.11949/0438-1157.20250519

Abstract

Abstract:

Hydrodeoxygenation of phenolics is a key reaction for the conversion of lignin into renewable liquid fuels and aromatic chemicals. In this study, non-precious Ni and VO _x species were loaded onto an inert SiO₂ support to produce a series of NiV/ SiO₂ catalysts. Raman, X-ray diffraction (XRD), H₂-temperature programed reduction (H₂-TPR), and ammonia-temperature programed desorption (NH₃-TPD) were used to characterize the structure and physicochemical properties of these catalysts, and m-cresol was used as a lignin model compound to investigate the catalytic performance of different active sites in hydrodeoxygenation of phenolic compounds. Research has found that Ni metal mainly catalyzes the hydrogenation and C—C bond cleavage of m-cresol, with low selectivity for the target product toluene. There is a strong interaction between VO _x species and Ni metal, and the introduction of an appropriate amount of VO _x can reduce the particle size of Ni metal, enrich the Ni-VO _x interface sites, and significantly improve the selective hydrodeoxygenation of m-cresol to toluene. Based on the investigation of process conditions and the probe reaction of methyl cyclohexanol, it was revealed that the main mechanism of m-cresol hydrodeoxygenation at the Ni-VO _x interface is direct deoxygenation, providing a certain theoretical basis for the development of efficient phenolic deoxygenation catalysts.

Key words: Ni, hydrodeoxygenation, lignin, phenolics, heterogeneous catalysis, catalyst, biomass, interface

摘要：

酚类加氢脱氧是木质素转化为可再生液体燃料和芳烃化工原料的关键反应。本研究在惰性SiO₂载体上负载非贵金属Ni和VO _x 物种，得到系列NiV/SiO₂催化剂。采用Raman、XRD、H₂-TPR和NH₃-TPD对催化剂结构和物化性质进行表征，并以间甲酚为木质素模型化合物，考察不同活性位对酚类加氢脱氧反应的催化性能。研究发现，Ni金属主要催化间甲酚加氢和C—C断键反应，对目标产物甲苯的选择性较低。而VO _x 物种和Ni金属之间存在强相互作用，适量VO _x 的引入能减小Ni金属的粒径，丰富Ni-VO _x 界面位点，进而显著促进间甲酚选择性加氢脱氧为甲苯。结合工艺条件的考察和甲基环己醇探针反应，揭示了Ni-VO _x 界面上酚类加氢脱氧主要为直接脱氧机理，为高效酚类脱氧催化剂的研制提供一定理论基础。

关键词: 镍, 加氢脱氧, 木质素, 酚类, 多相催化, 催化剂, 生物质, 界面

CLC Number:

O 643.36

Wei ZHOU, Zhiqian WU, Yapeng QIAO, Xinyu XIE, Feifei YANG. Efficient catalytic hydrodeoxygenation of lignin derived phenolics on Ni-VO _x interface[J]. CIESC Journal, 2025, 76(12): 6366-6375.

周维, 吴之倩, 乔亚鹏, 谢欣雨, 杨菲菲. Ni-VO _x 界面高效催化木质素衍生酚类加氢脱氧[J]. 化工学报, 2025, 76(12): 6366-6375.

Figures/Tables 15

Fig.1 Raman spectra of calcined catalysts

Fig.2 XRD patterns of reduced catalysts with different Ni and V loading amount

Table 1 Crystalline size and acid properties of catalysts

催化剂	晶相粒径^①/nm		酸密度^②/ (μmol·g^-1)
催化剂	Ni	V₂O₃	酸密度^②/ (μmol·g^-1)
Ni/SiO₂	18.0	—	15.3
Ni4.3V/SiO₂	6.3	—	181.8
Ni8.6V/SiO₂	6.5	20.4	295.4
4.3V/SiO₂	—	—	362.7

Fig.3 H2-TPR profiles of various catalysts

Fig.4 NH3-TPD prefiles of various catalysts

Fig.5 Influence of VO x species introduction on catalyst structure

Fig.6 Effect of reduction temperature of Ni4.3V/SiO2 on its catalytic performance[Ben: benzene; CH4: methane; Ph: phenol; Tol: toluene. Reaction conditions: 350℃, 1 atm(1 atm=101325 Pa), W/F = 0.05 h, H2/m = 146, TOS = 20 min]

Fig.7 Catalytic performance of various catalysts in m-cresol hydrodeoxygenation under 350℃(Reaction conditions: 1 atm, W/F = 0.09 h, H2/m = 146, TOS = 20 min)

Fig.8 Catalytic performance of various catalysts in m-cresol hydrodeoxygenation under 250℃(DMB: dimethylbiphenyl compounds; MCHene: methylcyclohexene; MCHane: methylcyclohexane; MCHol: methylcyclohexanol; MCHone: methylcyclohexanone. Reaction conditions: 1 atm, W/F = 0.09 h, H2/m = 146, TOS = 20 min)

Fig.9 Difference of conversion and product distribution between Ni/SiO2 and Ni4.3V/SiO2 under distinct reaction temperature （Reaction conditions: 1 atm, W/F = 0.09 h, H2/m = 146, TOS = 20 min）

Fig.10 Trend of product yield with different m-cresol conversion on Ni4.3V/SiO2 catalyst under 350℃(Reaction conditions: 1 atm, H2/m = 146, TOS = 20 min, W/F is changed to obtain different m-cresol conversion)

Fig.11 Trend of product yield with different m-cresol conversion on Ni4.3V/SiO2 catalyst under 250℃(Reaction conditions: 1 atm, H2/m = 146, TOS = 20 min, W/F is changed to obtain different m-cresol conversion)

Fig.12 Product distribution of methylcyclohexane reaction on different catalysts(Reaction conditions: 250℃, 1 atm, H2/m = 146, TOS = 20 min, W/F = 0.065 h)

Fig.13 Main reaction routes and structure-activity relationships of m-cresol hydrodeoxygenation on NiV/SiO2 catalysts

Fig.14 The stability of m-cresol hydrodeoxygenation on Ni4.3V/SiO2 catalyst(Reaction conditions: 350℃, 1 atm, W/F = 0.51 h, H2/m = 146)

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