NiCe(x)/FLRC-TiO2催化剂的制备及其加氢脱氧性能研究

doi:10.6023/A23120546

摘要/Abstract

生物质作为自然界唯一可再生的有机碳源, 其转化利用具有重要意义. 本工作制备了具有特殊形貌和孔道结构的放射状二氧化钛(FLRC-TiO₂)载体, 并在高加氢活性Ni基础上, 引入Ce赋予催化剂酸活性位, 制备了负载型金属-酸双功能NiCe(x)/FLRC-TiO₂催化剂(x为Ni和Ce的原子比), 并以对甲酚为模型化合物, 研究了Ni/Ce比对催化剂加氢脱氧(HDO)性能的影响. 结果表明, Ce的引入能够增强催化剂的酸性, 增强催化剂C—OH键氢解能力, 从而提高甲基环己烷(MCH)选择性. 与单金属Ni/FLRC-TiO₂相比, 双金属NiCe(1)/FLRC-TiO₂的目标产物MCH的选择性显著提高. 在275 ℃、3 MPa、2.5 h的反应条件下, NiCe(1)/FLRC-TiO₂催化剂对对甲酚转化率为100%, 脱氧产物选择性为97.9%, 且MCH的选择性高达95.4%. NiCe(1)/FLRC-TiO₂催化剂上的HDO以hydrogenation (HYD)反应路径为主.

关键词: 加氢脱氧, NiCe催化剂, 放射状孔道结构, 二氧化钛, 对甲酚

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

引用此文

张强, 王欢, 王帅, 王园园, 张梅, 宋华. NiCe(x)/FLRC-TiO₂催化剂的制备及其加氢脱氧性能研究[J]. 化学学报, 2024, 82(3): 287-294.

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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图/表 15

图1. 不同Ni/Ce比的NiCe(x)/FLRC-TiO2催化剂的XRD谱图

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

图2. 载体FLRC-TiO2和NiCe(x)/FLRC-TiO2催化剂的N2吸附-脱附等温线(a)和孔径分布(b)

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

表1. 载体FLRC-TiO2和NiCe(x)/FLRC-TiO2催化剂的结构表征

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

图3. FLRC-TiO2载体(a), Ni/FLRC-TiO2 (b), Ce/FLRC-TiO2 (c)和NiCe(1)/FLRC-TiO2 (d)的SEM图

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

图4. FLRC-TiO2 (a, b), Ni/FLRC-TiO2 (c, d), Ce/FLRC-TiO2 (e, f)和NiCe(1)/FLRC-TiO2 (g, h)的TEM图

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)

图5. 样品的XPS谱图: (a) Ni 2p, (b) Ce 3d

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

图6. Ni/FLRC-TiO2, Ce/FLRC-TiO2和NiCe(x)/FLRC-TiO2催化剂的Py-FTIR谱图

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

表2. Ni/FLRC-TiO2, Ce/FLRC-TiO2和NiCe(x)/FLRC-TiO2催化剂的酸性分析

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

图7. 不同Ni/Ce比对对甲酚HDO性能的影响(反应条件: T=250 ℃, p=3 MPa, t=2 h)

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)

图8. NiCe(1)/FLRC-TiO2催化剂上反应温度对对甲酚HDO性能的影响(反应条件: 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)

图9. NiCe(1)/FLRC-TiO2催化剂上初始反应压力对对甲酚HDO性能的影响(反应条件: T=275 ℃, 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)

图10. NiCe(1)/FLRC-TiO2催化剂上反应时间对对甲酚HDO性能的影响(反应条件: T=275 ℃, p=3 MPa)

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]

表3. NiCe(1)/FLRC-TiO2与已报道金属催化剂上对甲酚HDO性能比较

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

图11. NiCe(1)/FLRC-TiO2催化剂的稳定性(a)和反应前后NiCe(1)/FLRC-TiO2催化剂的XRD谱图(b)

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

图12. 对甲酚在NiCe(1)/FLRC-TiO2催化剂上的HDO反应机理图

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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