Influence of Cu and Mo components of γ-Al2O3 supported nickel catalysts on hydrodeoxygenation of fatty acid methyl esters to fuel-like hydrocarbons
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摘要: 制备一系列包含或不包含铜、钼组分的Ni/γ-Al2O3催化剂，并对其进行表征和性能测试。考察了铜、钼负载量，浸渍顺序（包括连续浸渍和共浸渍），反应条件对脂肪酸甲酯加氢脱氧反应性能的影响。根据TG数据，使用过的20Ni-6Cu/γ-Al2O3催化剂其热失重小于20Ni/γ-Al2O3催化剂，这表明，铜的引入能够有效抑制反应过程中催化剂表面的积炭行为。对于20Ni-6Cu/γ-Al2O3和20Ni-6Cu-nMo/γ-Al2O3（n=2、5、8和12）催化剂，NH3-TPD分析结果显示，钼物相的引入对载体γ-Al2O3的酸性位有着显著影响，当钼负载量达到5%时，可以观察到一个新的酸位对应于中强酸位。铜和钼修饰过的催化剂其催化性能要高于Ni/γ-Al2O3催化剂。从XPS的分析可以看出，催化剂中的铜主要以正二价形式存在，钼主要以正四价和正六价形式存在，而且不同的浸渍顺序会影响催化剂表面活性组分的实际含量。此外，脂肪酸甲酯的转化率和烷烃产品的收率也和所制备出来的催化剂的浸渍顺序有关。在所有的催化剂中，使用连续浸渍（先浸渍镍铜组分、浸渍钼组分）所制备的三金属20Ni-6Cu-5Mo/γ-Al2O3催化剂展现了优异的催化性能。在适宜的反应条件下（350 ℃，2.5 MPa，WSHV=2.0 h-1，H2/oil ratio=1250 mL/mL），脂肪酸甲酯的转化率和烷烃产品的收率分别达到98.4%和94.2%。Abstract: In this work, series of Ni/γ-Al2O3 catalysts with or without Cu and Mo components were prepared, characterized and tested for the hydrodeoxygenation of fatty acid methyl esters (FAME) to hydrocarbons. The effects of Cu and Mo loading, impregnation sequence with sequential impregnation and co-impregnation involved and reaction conditions on catalytic performance were investigated. According to the TG data, the spent 20Ni-6Cu/γ-Al2O3 catalyst gives less weight loss than the spent 20Ni/γ-Al2O3 catalyst, which indicates that the addition of copper inhibits the carbon deposits behavior on catalyst surface during reaction. For 20Ni-6Cu/γ-Al2O3 and 20Ni-6Cu-nMo/γ-Al2O3(n=2, 5, 8 and 12) catalysts, NH3-TPD analysis shows that the addition of molybdenum phase has significant impact on the acid sites of γ-Al2O3. When the loading of molybdenum is 5%, a new acid site is observed corresponding to the medium strength acid site. The Cu and Mo modified catalysts demonstrate better catalytic performance than Ni/γ-Al2O3 catalysts. Based on XPS results, Cu in the catalysts exists in the Cu2+ and Mo in the catalysts has two states:Mo4+ and Mo6+, and different impregnation sequences may influence the actual element composition of active phase on the surface of catalysts. In addition, the conversion of FAME and yield of alkane are related to the catalysts prepared with different impregnation sequence. Among all the catalysts, the trimetallic 20Ni-6Cu-5Mo/γ-Al2O3 prepared by sequential impregnation (the former Ni and Cu impregnation, the latter Mo impregnation) exhibits optimal catalytic performance. Under appropriate reaction conditions 350℃, 2.5 MPa, WSHV=2.0 h-1, H2/oil ratio=1250 mL/mL, the conversion of FAME and yield of alkane are 98.4% and 94.2%.
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Key words:
- hydrodeoxygenation /
- fatty acid methyl esters /
- Ni-based catalysts /
- γ-Al2O3
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Figure 1 XRD patterns of γ-Al2O3 and catalysts
(a): a: γ-Al2O3; b: 20Ni/γ-Al2O3; c: 20Ni-1Cu/γ-Al2O3; d: 20Ni-3Cu/γ-Al2O3; e: 20Ni-6Cu/γ-Al2O3; f: 20Ni-10Cu/γ-Al2O3
(b): a: 20Ni-6Cu/γ-Al2O3; b: 20Ni-6Cu-2Mo/γ-Al2O3; c: 20Ni-6Cu-5Mo/γ-Al2O3; d: 20Ni-6Cu-8Mo/γ-Al2O3; e: 20Ni-6Cu-12Mo/γ-Al2O3
(c): a: 20Ni-6Cu/γ-Al2O3; b: Ni-Cu-Mo(s)/γ-Al2O3; c: Ni-Cu-Mo/γ-Al2O3; d: Mo-Ni-Cu/γ-Al2O3
(a): ◆: NiO; ●: Al2O3; (b): ▲: MoO3
Figure 2 adsorption-desorption isotherm of catalysts
(a): 20Ni-mCu/γ-Al2O3; (b): 20Ni-6Cu-nMo/γ-Al2O3; (c): catalysts from different impregnation sequence
Figure 3 Pore diameter distributions of catalysts
(a): 20Ni-mCu/γ-Al2O3; (b): 20Ni-6Cu-nMo/γ-Al2O3; (c): catalysts from different impregnation sequence
Figure 4 H2-TPR profiles of catalysts
(a): a: 20Ni/γ-Al2O3; b: 20Ni-1Cu/γ-Al2O3; c: 20Ni-3Cu/γ-Al2O3; d: 20Ni-6Cu/γ-Al2O3; e: 20Ni-10Cu/γ-Al2O3; f: 6Ni-20Cu/γ-Al2O3
(b): a: 20Ni-6Cu/γ-Al2O3; b: 20Ni-6Cu-2Mo/γ-Al2O3; c: 20Ni-6Cu-5Mo/γ-Al2O3; d: 20Ni-6Cu-8Mo/γ-Al2O3; e: 20Ni-6Cu-12Mo/γ-Al2O3
(c): a: 20Ni-6Cu/γ-Al2O3; b: Ni-Cu-Mo(s)/γ-Al2O3; c: Mo-Ni-Cu/γ-Al2O3; d: Ni-Cu-Mo/γ-Al2O3
Figure 5 NH3-TPD profiles of γ-Al2O3 and catalysts
(a): a: γ-Al2O3; b: 20Ni/γ-Al2O3; c: 20Ni-1Cu/γ-Al2O3; d: 20Ni-3Cu/γ-Al2O3; e: 20Ni-6Cu/γ-Al2O3; f: 20Ni-10Cu/γ-Al2O3
(b): a: 20Ni-6Cu/γ-Al2O3; b: 20Ni-6Cu-2Mo/γ-Al2O3; c: 20Ni-6Cu-5Mo/γ-Al2O3; d: 20Ni-6Cu-8Mo/γ-Al2O3; e: 20Ni-6Cu-12Mo/γ-Al2O3
(c): a: 20Ni-6Cu/γ-Al2O3; b: Ni-Cu-Mo(s)/γ-Al2O3; c: Mo-Ni-Cu/γ-Al2O3; d: Ni-Cu-Mo/γ-Al2O3
Figure 8 SEM and EDS spectra of γ-Al2O3 and catalyst
(a): γ-Al2O3; (b): 20Ni-6Cu/γ-Al2O3; (c): 20Ni-6Cu-5Mo/γ-Al2O3
Figure 9 Catalytic performance and products distributions over the catalysts with different Cu loadings
Figure 10 Catalytic performance and products distributions over the catalysts with different Mo loading
Figure 11 Catalytic performance and products distributions over the catalysts from different impregnation sequences
Figure 12 Catalytic performance of 20Ni-6Cu-5Mo/γ-Al2O3 catalyst with different temperature
Figure 13 Catalytic performance of 20Ni-6Cu-5Mo/γ-Al2O3 catalyst with different pressure
Figure 15 Catalytic performance of 20Ni-6Cu-5Mo/γ-Al2O3 catalyst with different H2/oil ratio
Table 1 Textural properties of the catalysts
Catalyst BET surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Avg. pore diameter d/nm 20Ni/γ-Al2O3 278 0.68 4.88 20Ni-1Cu/γ-Al2O3 271 0.64 4.89 20Ni-3Cu/γ-Al2O3 242 0.62 4.88 20Ni-6Cu/γ-Al2O3 222 0.47 4.90 20Ni-10Cu/γ-Al2O3 203 0.44 4.90 20Ni-6Cu-2Mo/γ-Al2O3 212 0.45 4.89 20Ni-6Cu-5Mo/γ-Al2O3 207 0.43 4.89 20Ni-6Cu-8Mo/γ-Al2O3 204 0.41 4.31 20Ni-6Cu-12Mo/γ-Al2O3 188 0.31 3.82 Ni-Cu-Mo(s)/γ-Al2O3 214 0.45 4.89 Mo-Ni-Cu/γ-Al2O3 213 0.43 4.31 
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Table 2 Relative atomic ratios of elements in the near-surface layer of catalysts with different Mo contents
Catalyst [Ni]/[Al] [Cu]/[Al] [Mo]/[Al] [O]/[Al] 20Ni-6Cu/γ-Al2O3 0.05 0.006 － 1.04 20Ni-6Cu-2Mo/γ-Al2O3 0.05 0.006 0.01 1.17 20Ni-6Cu-5Mo/γ-Al2O3 0.05 0.006 0.03 1.14 20Ni-6Cu-8Mo/γ-Al2O3 0.04 0.007 0.04 1.20 20Ni-6Cu-12Mo/γ-Al2O3 0.06 0.008 0.07 1.47
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Table 3 Relative atomic ratios of elements in the near-surface layer of catalysts from different impregnation sequence
Catalyst [Ni]/[Al] [Cu]/[Al] [Mo]/[Al] [O]/[Al] Ni-Cu-Mo/γ-Al2O3 0.05 0.006 0.03 1.14 Mo-Ni-Cu/γ-Al2O3 0.04 0.006 0.02 1.16 Ni-Cu-Mo(s)/γ-Al2O3 0.04 0.005 0.02 1.12
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Table 4 Contents of various elements of γ-Al2O3, 20Ni-6Cu/γ-Al2O3 and 20Ni-6Cu-5Mo/γ-Al2O3catalysts
Sample Elemental composition w/% O Al Ni Cu Mo γ-Al2O3 56.17 43.83 20Ni-6Cu/γ-Al2O3 48.89 27.53 17.99 5.59 20Ni-6Cu-5Mo/γ-Al2O3 46.30 26.72 17.44 4.67 4.87
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