NiMoP/γ-Al2O3催化剂的煤焦油加氢性能研究

刘贞贞; 方梦祥; 马帅; 骆仲泱

NiMoP/γ-Al₂O₃催化剂的煤焦油加氢性能研究

浙江大学能源清洁利用国家重点实验室, 浙江杭州 310027

基金项目:

国家高技术研究发展计划 863 program

国家高技术研究发展计划 2013AA051203

国际合作项目 2011DFR60190

高等学校学科创新引智计划 B08026

详细信息

通讯作者:
骆仲泱, Tel: 0571-87952440, E-mail: zyluo@zju.edu.cn

中图分类号: TE624.4
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- 文章访问数: 67
- HTML全文浏览量: 29
- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2015-11-26
- 修回日期: 2016-02-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-05-10

Hydrogenation of coal tar on NiMoP/γ-Al₂O₃ catalyst

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Funds:

the National High Technology Research of China 863 program

the National High Technology Research of China 2013AA051203

International Cooperative Programme 2011DFR60190

Programme of Introducing Talents of Discipline to Universities B08026

摘要

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。
- 煤焦油 /
- 加氢 /
- 酚油
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.
- coal tar /
- hydrogenation /
- carbolic oil

HTML全文

图 1 不同Ni含量的NiMoP/γ-Al₂O₃催化剂的MoS₂平均片层长度与堆叠层数分布

Figure 1 Distribution of average slab length and stacking degree of MoS₂ in NiMoP/γ-Al₂O₃ catalyst with different Ni content

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图 2 不同Ni含量NiMoP/γ-Al₂O₃催化剂的H₂-TPR谱图

Figure 2 H₂-TPR profiles of NiMoP/γ-Al₂O₃ catalyst with different Ni contents

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图 3 DBT的HDS反应路径示意图

Figure 3 Reaction path of HDS of DBT

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图 4 DBT的转化率、产物选择性随Ni含量的变化

Figure 4 Conversion and selectivity of DBT at different Ni content

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图 5 喹啉的HDN反应路径示意图

Figure 5 Reaction path of HDN of quinoline

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图 6 喹啉的转化率、产物选择性随Ni含量的变化

Figure 6 Conversion and selectivity of quinoline at different Ni contents

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图 7 邻二甲苯的反应路径示意图

Figure 7 Reaction path of o-xylene

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图 8 1-甲基萘的反应路径示意图

Figure 8 Reaction path of 1-MN

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图 9 菲的反应路径示意图

Figure 9 Reaction path of phenanthrene

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图 10 邻二甲苯、1-甲基萘、菲的转化率随Ni含量的变化

Figure 10 Conversion of o-xylene, 1-MN and phenanthrene at different Ni contents

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图 11 菲的加氢产物选择性随Ni含量的变化

Figure 11 Selectivity of phenanthrene at different Ni contents

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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/%
Catalyst	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

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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

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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

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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

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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

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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

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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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