乙二醇对磷掺杂NiMo/Al<sub>2</sub>O<sub>3</sub>加氢催化剂性能的影响

尹海亮; 刘新亮; 周同娜; 赵健; 蔺爱国

乙二醇对磷掺杂NiMo/Al₂O₃加氢催化剂性能的影响

1.
中国石油大学(华东)科学技术研究院, 山东东营 257061
2.
东营市生态环境局, 山东东营 257091

基金项目:

国家自然科学基金 21206197

山东省自然科学基金 ZR2019MB022

中央高校基本科研业务费专项资金 19CX02063A

详细信息

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2019-07-22
- 修回日期: 2019-10-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-12-10

Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al₂O₃ catalysts

1.
Academy of Science & Technology, China University of Petroleum(East China), Dongying 257061, China
2.
Environmental Protection Agency of Dongying, Dongying 257091, China

Funds:

the National Natural Science Foundation of China 21206197

Shandong Provincial Natural Science Foundation ZR2019MB022

Fundamental Research Funds for the Central Universities 19CX02063A

More Information

Corresponding author: YIN Hai-liang, E-mail: yinhl@upc.edu.cn

摘要

摘要: 采用NiMoP浸渍液中添加乙二醇（EG）的方式制备了不同EG含量的NiMoP（x）/Al₂O₃催化剂，为研究EG及其含量对该系列催化剂催化性能和活性相结构的影响，用二苯并噻吩（DBT）和喹啉（Q）为模型化合物，考察了催化剂的加氢脱硫（HDS）和加氢脱氮（HDN）性能。结果表明，在EG添加量较低的情况下（EG/Ni物质的量比分别为0、0.5、1、2、3），EG能够明显提高催化剂对DBT和Q的HDS和HDN活性，其中，HDN活性提高幅度大于HDS，且随着EG含量提高，催化剂的HDS和HDN活性进一步提高。通过TEM分析和XPS分析可知，EG有助于增加催化剂中MoS₂颗粒的堆积层数和片层长度，且随着EG含量增加，堆积层数和片层长度都有所增加；EG有助于提高Mo表面原子浓度，对Ni表面原子浓度影响较小，但明显提高了Mo和Ni硫化程度。TG表征说明，EG在氧化铝和催化剂表面存在多种相互作用方式，并且存在与活性组分相互作用的耐高温有机物种。
- 乙二醇 /
- 催化剂 /
- 加氢脱硫 /
- 加氢脱氮
Abstract: NiMoP(x)/Al₂O₃ catalysts with different ethylene glycol (EG) contents were prepared by impregnating NiMoP solution containing EG into Al₂O₃. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performances of the catalysts were evaluated using dibenzothiophene (DBT) and quinoline (Q) as the model compounds. The results showed that the HDS and HDN performances of the catalysts could be improved by adding of EG when the amount of EG was low (n_EG/n_Ni ratio value was 0, 0.5, 1, 2, 3, respectively), and the improvement of HDN performance was more obvious than HDS performance. With the increase of EG content, the activity of HDS and HDN of the catalysts was further improved. TEM and XPS analysis showed that EG was helpful to increase the stacking layer number and lamellar length of MoS₂ particles in the catalysts, and with the increase of EG content, the stacking layer number and lamellar length of MoS₂ particles increased. EG could improve the surface atomic concentration of Mo, but practically had no influence on the surface atomic distribution of Ni. However, EG significantly increased the sulfuration degree of Mo and Ni. TG characterization showed that EG interacted with alumina and metal active components in various ways, and there were high temperature resistant organic species interacting with active components.
- ethylene glycol /
- catalyst /
- hydrodesulfurization /
- hydrodenitrogenation

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图 1 NiMoP(x)/Al₂O₃催化剂上DBT和Q的HDS和HDN活性曲线

Figure 1 HDS and HDN precentage of DBT and Q over the NiMoP(x)/Al₂O₃ catalysts

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图 2 NiMoP(x)/Al₂O₃催化剂上BP/CHB比

Figure 2 BP/CHB ratio of DBT over the NiMoP(x)/Al₂O₃ catalysts

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图 3 硫化态NiMoP(x)/Al₂O₃催化剂的XRD谱图

Figure 3 XRD patterns of the spent NiMoP(x)/Al₂O₃ catalysts

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图 4 焙烧NiMoP(x)/Al₂O₃催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of the calcined NiMoP(x)/Al₂O₃ catalysts

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图 5 未焙烧NiMoP(x)/Al₂O₃催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of the dried NiMoP(x)/Al₂O₃ catalysts

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图 6 硫化态NiMoP(x)/Al₂O₃的HRTEM照片

Figure 6 HRTEM of the spent NiMoP(x)/Al₂O₃ catalysts

(a): NiMoP(0)/Al₂O₃; (b): NiMoP(0.5)/Al₂O₃; (c): NiMoP(2)/Al₂O₃; (d): NiMoP(3)/Al₂O₃

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图 7 空气气氛中NiMoP(x)/Al₂O₃催化剂的失重曲线和DTG曲线

Figure 7 TG curves (a) and DTG curves (b) of the NiMoP(x)/Al₂O₃ catalysts in air atmosphere

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图 8 空气气氛中EG(x)/Al₂O₃样品的失重曲线(a)和DTG曲线(b)

Figure 8 TG curves (a) and DTG curves (b) of EG(x)/Al₂O₃ samples under air atmosphere

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表 1 DBT在NiMoP(x)/Al₂O₃催化剂上HDS产物分布

Table 1 Product distribution of DBT HDS over the NiMoP(x)/Al₂O₃ catalysts

Catalyst	w_mol/%
Catalyst	NiMoP(0)/Al₂O₃	NiMoP(0.5)/Al₂O₃	NiMoP(1)/Al₂O₃	NiMoP(2)/Al₂O₃	NiMoP(3)/Al₂O₃
	0.14	0.33	0.14	0.15	0.13
	0.64	0.77	0.68	0.69	0.66
	0.00	0.00	0.00	0.00	0.00
	19.91	22.76	24.61	26.61	27.52
	44.87	51.28	51.76	52.83	56.38
	0.21	0.66	0.14	0.15	0.10
	0.43	0.63	0.59	0.35	0.27
	33.8	23.57	22.07	19.21	14.88

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表 2 Q在NiMoP(x)/Al₂O₃催化剂HDN产物分布

Table 2 Product distribution of quinoline HDN over the NiMoP(x)/Al₂O₃ catalysts

Catalyst	w_mol/%
Catalyst	NiMoP(0)/Al₂O₃	NiMoP(0.5)/Al₂O₃	NiMoP(1)/Al₂O₃	NiMoP(2)/Al₂O₃	NiMoP(3)/Al₂O₃
	54.21	74.63	84.31	86.87	88.88
	7.68	5.86	5.52	5.23	5.07
	0.79	0	0	0	0
	1.13	0	0	0	0
	0	0	0	0	0
	1.45	0.18	0.15	0.17	0.13
	29.31	18.64	9.72	7.48	5.72
	0	0	0	0	0
	5.42	1.06	0.30	0.81	0.20

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表 3 MoS₂颗粒的平均堆垛层数(N_A)、平均片长(L_A)以及可暴露Mo原子比(f_Mo)

Table 3 Average stacking number (N_A), average slab length (L_A) and fraction of available Mo (f_Mo) of MoS₂

Catalyst	N_A	L_A /nm	f_Mo
NiMoP(0)/Al₂O₃	1.6	3.95	0.267
NiMoP(0.5)/Al₂O₃	1.7	4.30	0.247
NiMoP(2)/Al₂O₃	2.0	4.32	0.252
NiMoP(3)/Al₂O₃	2.5	4.60	0.222

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表 4 反应后催化剂Mo 3d和Ni 2p的结合能

Table 4 Mo 3d and Ni 2p binding energy of the spent catalysts

Catalyst	Binding energy E_B/eV
Catalyst	Mo 3d_5/2	Mo 3d_3/2	Ni 2p_3/2
NiMoP(0)/Al₂O₃	229.3, 231.5, 233.5	232.5, 234.7, 236.5	852.9, 854.2, 856.3
NiMoP(0.5)/Al₂O₃	229.1, 231.4, 232.9	232.3, 234.6, 236.1	853.3, 853.9, 856.1
NiMoP(2)/Al₂O₃	229.1, 231.6, 233.1	232.3, 234.8, 236.3	853.3, 854.1, 855.9
NiMoP(3)/Al₂O₃	229.2, 231.6, 233.2	232.4, 234.8, 236.4	853.3, 854.2, 856.3

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表 5 反应后催化剂表面Ni、Mo物质的量比

Table 5 Atomic ratios of Ni, Mo of the spent catalysts

Parameter		NiMoP(0)/Al₂O₃	NiMoP(0.5)/Al₂O₃	NiMoP(2)/Al₂O₃	NiMoP(3)/Al₂O₃
Mo(3d)	MoS₂/Al	0.115	0.128	0.135	0.139
	Mo⁵⁺/Al	0.015	0.016	0.017	0.018
	Mo⁶⁺/Al	0.021	0.021	0.020	0.021
	Mo⁴⁺/Mo_total	0.762	0.776	0.785	0.781
	Mo_total/Al	0.151	0.165	0.172	0.178
Ni (2p)	Ni-sulf/Al	0.017	0.019	0.023	0.022
	NiMoS/Al	0.030	0.031	0.028	0.038
	Ni²⁺/Al	0.024	0.012	0.009	0.008
	Ni(总)/Al	0.064	0.062	0.060	0.068

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