Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (3): 287-294.DOI: 10.6023/A23120546 Previous Articles     Next Articles



张强, 王欢*(), 王帅, 王园园, 张梅, 宋华*()   

  1. 东北石油大学 化学化工学院 黑龙江省大庆市 163318
  • 投稿日期:2023-12-29 发布日期:2024-03-04
  • 基金资助:

Preparation of NiCe(x)/FLRC-TiO2 Catalyst and Its Performance in Hydrodeoxygenation

Qiang Zhang, Huan Wang(), Shuai Wang, Yuanyuan Wang, Mei Zhang, Hua Song()   

  1. College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang Province, China
  • Received:2023-12-29 Published:2024-03-04
  • Contact: *E-mail:;
  • Supported by:
    National Natural Science Foundation of China(22278068)

As the only renewable organic carbon source in nature, the conversion and utilization of biomass is of great significance. The bio-oil obtained from biomass pyrolysis has low calorific value, poor stability, high viscosity and high acidity due to the high content of oxygenated compounds. The hydrodeoxygenation (HDO) is considered as the most efficient technology to remove oxygen and the development of the efficient HDO catalysts remains a great challenge. In this paper, aimed to improve mass transfer rate and HDO intrinsic activity, a novel strategy of preparing a titanium dioxide (FLRC-TiO2) support with special morphology and radial pore structure was proposed. In addition, the supported metal-acid bifunctional NiCe(x)/FLRC-TiO2 catalyst (x is the atomic ratio of Ni and Ce) was prepared by introducing metal Ce to induce the acid active site on the basis of high hydrogenation activity metal Ni sites. The as-prepared catalysts were characterized by various methods. Using p-cresol as a model compound, the effects of different Ni/Ce ratios and reaction condition on the HDO performance of the catalysts were studied. The results show that the total acid amount of NiCe(1)/FLRC-TiO2 doped with the metal Ce was 148.7 μmol•g−1, which is significantly increased as compared to that of Ni/FLRC-TiO2 (45.3 μmol•g−1). The introduction of Ce can enhance the acidity of the catalyst and promote the hydrogen hydrolysis ability of the C—OH bond, thus improving the selectivity of cycloalkanes. Under the reaction conditions of 250 ℃, 3 MPa, 2 h, the selectivity to the target product methylcyclohexane (MCH) was significantly improved over the bimetallic NiCe(1)/FLRC-TiO2 (55.5%) compared to the monometallic Ni/FLRC-TiO2 (27.2%), demonstrating that introduction of Ce can greatly improve the efficiency of HDO. Increasing temperature and pressure, and extending reaction time are beneficial to HDO of p-cresol in the test range. The intersecting radial channels structure with flower-like morphology of FLRC-TiO2 was confirmed by transmission electron microscopy (TEM) characterization. Among the NiCe(x)/FLRC-TiO2, NiCe(1)/FLRC-TiO2 with atomic ratio of Ni and Ce of 1 exhibited excellent HDO performance. Under the reaction conditions of 275 ℃, 3 MPa, 2.5 h, the p-cresol was completely converted with the deoxidation products selectivity of 97.9%, and the selectivity of the target product MCH as high as 95.4%. The superior HDO performance of NiCe(1)/FLRC-TiO2 is attributed to the synergistic effect between metal site Ni and acid site Ce along with its special channel structure. The HDO reaction over NiCe(1)/FLRC-TiO2 was dominated by the hydrogenation (HYD) reaction pathway.

Key words: hydrodeoxygenation, NiCe catalyst, radial channel structure, titanium dioxide, p-cresol