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

doi:10.6023/A23120546

Abstract

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

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Qiang Zhang, Huan Wang, Shuai Wang, Yuanyuan Wang, Mei Zhang, Hua Song. Preparation of NiCe(x)/FLRC-TiO₂ Catalyst and Its Performance in Hydrodeoxygenation[J]. Acta Chimica Sinica, 2024, 82(3): 287-294.

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Fig. & Tab. 15

Figure 1. XRD spectra of NiCe(x)/FLRC-TiO2 catalysts with different Ni/Ce ratios

Figure 2. N2 adsorption-desorption isotherms (a) and pore size distributions (b) for support FLRC-TiO2 and NiCe(x)/FLRC-TiO2 catalysts

Sample	S_BET/(m²•g⁻¹)	V_p/(cm³•g⁻¹)	D_pore/nm
FLRC-TiO₂	63.1	0.390	24.7
Ce/FLRC-TiO₂	50.9	0.224	17.9
NiCe(1)/FLRC-TiO₂	51.1	0.266	20.8
NiCe(3)/FLRC-TiO₂	54.2	0.297	22.0
NiCe(5)/FLRC-TiO₂	49.1	0.279	22.7
Ni/FLRC-TiO₂	38.5	0.234	26.6

Table 1. Structural characterization of support FLRC-TiO2 and NiCe(x)/FLRC-TiO2 catalysts

Figure 3. SEM images of FLRC-TiO2 support (a), Ni/FLRC-TiO2 (b), Ce/FLRC-TiO2 (c) and NiCe(1)/FLRC-TiO2 (d)

Figure 4. TEM images of FLRC-TiO2 (a, b), Ni/FLRC-TiO2 (c, d), Ce/FLRC-TiO2 (e, f) and NiCe(1)/FLRC-TiO2 (g, h)

Figure 5. XPS spectra of samples: (a) Ni 2p, (b) Ce 3d

Figure 6. Py-FTIR spectra of Ni/FLRC-TiO2, Ce/FLRC-TiO2 and NiCe(x)/FLRC-TiO2 catalysts

Sample	Total acid/ (μmol•g⁻¹)	Acid sites distribution^a/(μmol•g⁻¹)
Sample	Total acid/ (μmol•g⁻¹)	Brønsted acid		Lewis acid		B/L
Ni/FLRC-TiO₂	45.3	—	45.3		—
Ce/FLRC-TiO₂	99.4	12.8	86.6		0.15
NiCe(1)/FLRC-TiO₂	148.7	23.2	125.5		0.18
NiCe(3)/FLRC-TiO₂	124.2	19.8	104.4		0.19
NiCe(5)/FLRC-TiO₂	115.8	18.9	96.9		0.20

Table 2. Acid analysis of Ni/FLRC-TiO2, Ce/FLRC-TiO2 and NiCe(x)/FLRC-TiO2 catalysts

Figure 7. Effect of different Ni/Ce ratios on the properties of p-cresol HDO (reaction conditions: T=250 ℃, p=3 MPa, t=2 h)

Figure 8. Effect of reaction temperature on p-cresol HDO properties over NiCe(1)/FLRC-TiO2 catalyst (reaction conditions: p=3 MPa, t=2 h)

Figure 9. Effect of reaction pressure on p-cresol HDO properties over NiCe(1)/FLRC-TiO2 catalyst (reaction conditions: T=275 ℃, t=2 h)

Figure 10. Effect of reaction time on p-cresol HDO properties over NiCe(1)/FLRC-TiO2 catalyst (reaction conditions: T=275 ℃, p=3 MPa)

Catalyst	T/℃	p_H2/MPa	t/h	Conv./%	Deoxidation products yield/%	Ref.
NiCe(1)/FLRC-TiO₂	275	3	2.5	100	97.9	This work
NiS₂-MoS₂-0.3	275	4	4	98.5	95.4	[18]
Pt/CeO₂-ZrO₂-Al₂O₃	275	4	6	95.1	100	[19]
Fe-MoS₂-0.7	250	4	3	96.3	95.7	[20]

Table 3. Comparison of p-cresol HDO performance over NiCe(1)/FLRC-TiO2 with reported metal catalysts

Figure 11. Stability of NiCe(1)/FLRC-TiO2 catalyst (a) and XRD pattern of NiCe(1)/FLRC-TiO2 catalyst before and after reaction (b)

Figure 12. Mechanism scheme of HDO reaction of p-cresol over NiCe(1)/FLRC-TiO2 catalyst

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NiCe(x)/FLRC-TiO₂催化剂的制备及其加氢脱氧性能研究

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

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NiCe(x)/FLRC-TiO2催化剂的制备及其加氢脱氧性能研究