Hydrogenation of coal tar on NiMoP/γ-Al2O3 catalyst
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摘要: 采用分步浸渍法制备了一系列NiMoP/γ-Al2O3催化剂, 并用电感耦合等离子体光谱、N2吸附脱附、透射电镜、H2程序升温还原等技术对NiMoP/γ-Al2O3催化剂进行了表征。在固定床反应器中, 进行了模型化合物的加氢实验, 确定了催化剂活性组分Ni的最佳含量(4%, 质量分数), 将最佳Ni含量的催化剂用于实际的煤焦油加氢研究, 并对比分析了酚油的切除对加氢效果的影响, 结果表明, 酚油的切除可以促进S、N原子的脱除以及芳烃的饱和。Abstract: The NiMoP/γ-Al2O3 catalyst was prepared through a multi-step impregnation method and characterized by inductively coupled plasma mass spectrometry (ICP-MS), N2 adsorption-desorption, transmission electron microscope (TEM) and H2 temperature programmed reduction (H2-TPR). The catalyst with 4%Ni is determined to be the best one with optimum component proportion by the tests with model compounds in a fixed-bed reactor. The coal tar hydrogenation was conducted over the optimum catalyst. The results reveal that the removal of carbolic oil can promote the removal of S and N and the saturation of aromatics.
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Key words:
- coal tar /
- hydrogenation /
- carbolic oil
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表 1 NiMoP/γ-Al2O3催化剂的活性组分含量
Table 1 Content of active component in NiMoP/γ-Al2O3 catalysts
Catalyst Theoretical results w/% Test results w/% Ni Mo P Ni Mo P HT1 1 10 1.5 1.01 9.71 1.65 HT2 2 10 1.5 1.95 9.56 1.46 HT3 4 10 1.5 3.99 9.65 1.54 HT4 6 10 1.5 5.87 9.92 1.63 表 2 不同Ni含量的NiMoP/γ-Al2O3催化剂的物理特性
Table 2 Physical properties of NiMoP/γ-Al2O3 catalyst with different Ni content
Catalyst BET surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Average pore diameter d/nm γ-Al2O3 283.30 0.49 19.15 HT1 145.07 0.24 3.83 HT2 146.31 0.25 3.84 HT3 147.48 0.27 3.82 HT4 143.54 0.21 3.84 表 3 不同Ni含量的NiMoP/γ-Al2O3催化剂中MoS2平均片层长度与堆叠层数
Table 3 Average slab length and stacking degree of MoS2 in NiMoP/γ-Al2O3 catalyst with different Ni content
Catalyst Average slab length d/nm Average stacking degree HT1 4.02 2.11 HT2 3.61 2.28 HT3 3.45 2.28 HT4 4.00 2.27 表 4 煤焦油馏分油模型化合物的组成
Table 4 Model compound of distillate oil
Model compound Content w/% Type Dibenzothiophene 1 S-containing compound Quinoline 5 N-containing compound o-xylene 10 mononuclear aromatic 1-methylnaphthalene 25 diaromatics Phenanthrene 10 triaromatics Hexadecane 10 long chain hydrocarbon Hexane 39 chain hydrocarbon 表 5 1-甲基萘的加氢产物物质的量比
Table 5 Molar ratio of hydrogenated products of 1-methylnaphthalene
Catalyst Methyl tetralin/methyl decalin HT1 8.05 HT2 1.50 HT3 1.67 HT4 2.30 表 6 馏分油加氢前后物质类别分布
Type Distillate oil
(phenol oil excision)Distillate oil Hydrogenation products
(phenol oil excision)Hydrogenation product Alkene 1.02 0.87 0.00 0.00 Alkane 4.79 4.09 13.98 11.46 Cycloalkane 0.00 0.00 10.66 9.40 Bicyclic alkane 3.91 3.33 2.76 2.30 Cycloolefine 0.00 0.00 0.11 0.23 Alkylbenzene 3.91 3.33 13.00 13.25 Hydrogenated aromatic 8.33 7.11 43.54 43.52 Other di-aromatics 9.65 8.23 1.38 1.96 Alkylnaphthalene 45.09 38.49 4.57 6.98 Biphenyl 6.05 5.17 2.89 4.92 Triaromatic 1.85 1.58 1.56 1.50 Oxygen containing compound 8.48 7.24 5.57 4.48 Phenol 6.97 20.59 0.00 0.00 表 7 馏分油以及加氢产物的S、N含量
Table 7 Content of S and N in distillate oil and hydrogenation products
Distillate oil
(phenol oil excision)Distillate oil Hydrogenation products
(phenol oil excision)Hydrogenation product S/10-6 12 150.00 12 000.00 76.18 220.41 N/10-6 4 300.00 4 900.00 5.00 21.13 -
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