Preparation of Ni2P/Zr-MCM-41 catalyst and its performance in the hydrodeoxygenation of Jatropha curcas oil
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摘要: 采用水热法合成MCM-41和Zr-MCM-41, 由Ni (NO3)2和(NH4)2HPO4溶液共浸渍、高温焙烧、氢气还原和钝化制备了负载型Ni2P/Zr-MCM-41催化剂。采用XRD、TEM、氮气吸附、CO吸附、吡啶吸附红外和XPS等方法对催化剂进行了表征, 并在高压反应釜中研究了其对麻风树油加氢脱氧(HDO) 的催化性能。结果表明, 氢气还原温度为650 ℃、Ni2P负载量为20%(质量分数)、Ni2P物相呈晶型时, Ni2P/Zr-MCM-41催化剂的活性最佳; 较低的Ni2P负载量有利于其在Zr-MCM-41载体表面均匀分散, 而负载量高于25%(质量分数) 时, 活性组分少量团聚, 易导致孔道堵塞。催化剂表面存在部分因钝化而形成的NiO。对于麻风树油加氢脱氧, Ni2P负载量为20%(质量分数) Ni2P/Zr-MCM-41表现出优异的催化性能; 脱氧率高达93.90%, 直链烷烃含量高达85.36%, 其中柴油组分产率较高, C15~20组分占直连烷烃组分50%以上。
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关键词:
- Ni2P/Zr-MCM-41 /
- 加氢脱氧 /
- 麻风树油 /
Abstract: With hydrothermally synthesized MCM-41 and Zr-MCM-41 as the supports, Ni2P/Zr-MCM-41 catalysts were prepared by co-impregnation with Ni (NO3)2 and (NH4)2HPO4 solution, calcination, reduction with H2 and subsequent passivation. The Ni2P/Zr-MCM-41 catalysts were characterized by XRD, Py-IR, TEM, XPS, N2 physisorption and CO chemisorption; their catalytic performance in the hydrodeoxygenation (HDO) of Jatropha curcas oil to produce the second-generation biodiesel was investigated in an autoclave. The results indicated that Ni2P can be well dispersed on Zr-MCM-41 with a loading of 20% by reduction at 650 ℃ from the phosphate precursors. The Ni2P/Zr-MCM-41 catalyst exhibit excellent performance in the HDO of Jatropha curcas oil. Over the Ni2P/Zr-MCM-41 catalyst with a Ni2P loading of 20%, the HDO conversion achieves 93.90% and the fraction of linear paraffins in the product oil reaches 85.36%, in which diesel fraction (C15~20) may exceed 61.90%; the components of oil generated through HDO are similar to those of fossil diesel.-
Key words:
- Ni2P /
- Zr-MCM-41 /
- hydrodeoxygenation /
- Jatropha curcas oil
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图 1 载体MCM-41与Zr-MCM-41的XRD谱图
Figure 1 Small-angle XRD patterns of MCM-41 (a) and Zr-MCM-41 (b)
图 2 负载还原后载体Zr-MCM-41的小角度XRD谱图
Figure 2 Small-angle XRD patterns of Ni2P/Zr-MCM-41 with different Ni2P loadings
a: 10%; b: 15%; c: 20%; d: 25%
图 3 不同还原温度下制备20%Ni2P/Zr-MCM-41的大角度XRD谱图
Figure 3 Wide-angle XRD patterns of the Ni2P/Zr-MCM-41 catalyst under different reduction temperature
▼: Ni2P; a: 450 ℃; b: 550 ℃; c: 600 ℃; d: 650 ℃
图 4 不同Ni2P负载量的Ni2P/Zr-MCM-41催化剂的大角度XRD谱图
Figure 4 Wide-angle XRD patterns of the Ni2P/Zr-MCM-41 catalysts with different Ni2P loadings
▼: Ni2P; a: 10%; b: 15%; c: 20%; d: 25%
图 5 650 ℃下制备的Ni2P/Zr-MCM-41催化剂的TEM照片
Figure 5 TEM images of the Ni2P/Zr-MCM-41 catalysts with different Ni2P loadings
(a): 25%; (b): 20%; (c): 15%; (d): 10%
图 6 650 ℃下制备的Ni2P/Zr-MCM-41催化剂的XPS谱图
Figure 6 XPS spectra of the Ni2P/Zr-MCM-41 catalyst reduced at 650 ℃
(a): Ni 2p; (b): P 2p
表 1 载体Zr-MCM-41与MCM-41在150和350 ℃下的L酸和B酸值
Table 1 Contents of Lewis and Brönsted acid sites of MCM-41 and Zr-MCM-41 measured by Py-IR at 150 and 350 ℃
Support Acid density at 150 ℃ /(μmol·g-1) Acid density at 350 ℃ /(μmol·g-1) Lewis Brönsted Lewis Brönsted MCM-41 0.012 0 0.004 0 Zr-MCM-41 0.022 0.066 0.005 0.002 
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表 2 载体与催化剂的孔结构参数
Table 2 Specific surface area, pore diameter, pore volume and CO uptake of various supports and catalysts
Sample ABET /(m2·g-1) vBJH /(cm3·g-1) Pore diameter d/nm CO uptakes v/(cm3·g-1) MCM-41 843.625 0.982 3.892 - Zr-MCM-41 828.091 0.922 3.387 - 10%Ni2P/Zr-MCM-41 647.810 0.607 3.349 0.086 15%Ni2P/Zr-MCM-41 576.164 0.555 3.393 0.116 20%Ni2P/Zr-MCM-41 500.438 0.798 2.843 0.170 25%Ni2P/Zr-MCM-41 379.940 0.573 2.902 0.165
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表 3 麻风树油的脂肪酸组成
Table 3 Fatty acid composition of Jatropha curcas oil
Fatty acid component Content w/% C 14：0 myristic acid 0.1 C 16：0 palmitic acid 13.3 C 16：1 hypogaeic acid 1.1 C 18：0 octadecanoic acid 6.7 C 18：1 oleic acid 40.7 C 18：2 linoleic acid 37.6 C 18：3 linolenic acid 0.2 C 20：0 arachic acid 0.2 C 20：1 eicosenoic acid 0.1
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表 4 不同负载量催化剂所得生成油组分含量
Table 4 Yields of various oil components obtained over the Ni2P/Zr-MCM-41 catalysts with different Ni2P loadings
Ni2P loading w/% Yield of components w/% linear paraffin oxy-compound isoparaffin cycloparaffin olefin aromatic 10 76.09 14.61 0 4.79 3.35 1.16 15 81.45 8.68 2.30 3.57 2.23 1.77 20 85.36 6.10 0.89 2.36 1.88 3.41 25 82.17 7.10 1.06 5.09 0.29 4.18
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表 5 生物柴油中直链烷烃的组分含量
Table 5 Components of linear paraffins in the oil generated from HDO of Jatropha curcas oil over the Ni2P/Zr-MCM-41 catalysts with different Ni2P loadings
Sample Content w% 10% 15% 20% 25% Nonane 2.21 2.48 4.11 6.35 Decane 2.55 0 5.26 7.29 Undecane 3.29 4.00 6.14 8.38 Dodecane 3.60 4.41 7.03 8.62 Tridecane 3.96 4.74 6.89 8.78 Tetradecane 4.13 5.16 6.84 8.41 Pentadecane 11.84 13.67 15.41 16.32 Hexadecane 4.32 5.58 6.62 2.62 Heptadecane 29.45 31.14 32.67 6.43 Octadecane 4.76 2.08 2.44 0 Nonadecane 2.81 2.29 3.06 2.53 Eicosane 1.83 1.40 1.70 1.74 Heneicosane 0.49 3.27 1.02 1.06 Tetracosane 0 0.49 0 0.67 Pentacosane 0.86 0.76 0.81 2.97
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