活性金属不同浸渍顺序对Mo-Ni/Al<sub>2</sub>O<sub>3</sub>催化剂硫醚化反应性能的影响

申志兵; 柯明; 张君涛; 梁生荣

活性金属不同浸渍顺序对Mo-Ni/Al₂O₃催化剂硫醚化反应性能的影响

申志兵^{1, 2},
柯明^2, ,,
张君涛¹,
梁生荣¹

1.
西安石油大学化学化工学院, 陕西西安 710065
2.
中国石油大学 (北京) 国家重质油加工重点实验室, 北京 102249

基金项目:

国家自然科学基金 21276276

详细信息

通讯作者:
柯明, E-mail: keming@cup.edu.cn

中图分类号: TE624
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- 文章访问数: 125
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- PDF下载量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2016-12-12
- 修回日期: 2017-03-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-05-10

Effect of impregnation sequence of Mo and Ni on the performance of Mo-Ni/Al₂O₃ catalyst in thioetherification

1.
School of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, China
2.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China

Funds:

the National Natural Science Foundation of China 21276276

摘要

摘要: 针对硫醚化反应过程使用的Mo-Ni/Al₂O₃催化剂，考察了不同浸渍方法对其催化性能和表面结构性质的影响。结果表明，通过同步浸渍和分步浸渍方法制得Mo-Ni/Al₂O₃催化剂的活性顺序为：先浸渍Mo后浸渍Ni的催化剂（SI-mn）≈Ni和Mo共同浸渍的催化剂（MN）>先浸渍Ni后浸渍Mo的催化剂（SI-nm）。对于SI-mn催化剂，先负载Mo后减弱了二次浸渍的Ni金属与载体间的相互作用，有利于负载金属的活化，并在二次浸渍后焙烧过程显现出显著的电子效应，形成新的Mo-Ni前体物种，有利于在预硫化过程形成适宜硫醚化和二烯烃选择性加氢的活性中心相，促进硫醚化反应和二烯烃选择性加氢。对于共同浸渍的MN催化剂也有类似的性质，因而也具有较好的催化性能。
- 硫醚化反应 /
- 二烯烃选择性加氢 /
- 分步浸渍 /
- 共同浸渍 /
- Mo-Ni/Al₂O₃催化剂
Abstract: Mo-Ni/Al₂O₃ catalysts were prepared by different impregnation sequences of Mo and Ni; the effect of impregnation sequence on the performance of Mo-Ni/Al₂O₃ catalysts in thioetherification was investigated. The results showed that the activity of the catalyst obtained by first impregnating Mo and then Ni (SI-mn) is close to that prepared by co-impregnation of Mo and Ni (MN); both are much more active than the catalyst obtained by first impregnating Ni and then Mo (SI-nm). For the SI-mn catalyst, Mo loaded on Al₂O₃ at the first stage can weaken the interaction between Ni and supporter, leading to a strong electronic effect between Ni and Mo, which can promote the formation of active phase in the presulfidation process and then enhance the catalytic performance of Mo-Ni/Al₂O₃ in thioetherification and selective hydrogenation of diene. Similar phenomena are observed for the MN catalyst obtained by co-impregnation, which also exhibits high activity in thioetherification.
- thioetherification /
- selective hydrogenation of diene /
- consecutive impregnation /
- co-impregnation /
- Mo-Ni/Al₂O₃ catalyst

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图 1 不同浸渍顺序催化剂的反应性能

Figure 1 Performance of the Mo-Ni/Al₂O₃ catalysts prepared by different impregnation sequences in thioetherification reactions were conducted at 90 ℃ and 3 MPa, with a space velocity of 4 h^-1 and a H₂/oil ration of 3

: x(mercaptan); : x(diene); : x(olefin)

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图 2 不同浸渍顺序催化剂 (氧化态) XRD谱图

Figure 2 XRD patterns of the Mo-Ni/Al₂O₃ catalysts (oxidation state) prepared by different impregnation sequences

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图 3 不同浸渍顺序催化剂 (氧化态) H₂-TPR谱图

Figure 3 H₂-TPR profiles of the Mo-Ni/Al₂O₃ catalysts (oxidation state) prepared by different impregnation sequences

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图 4 不同浸渍顺序催化剂 (氧化态) XPS谱图

Figure 4 XPS spectra of the Mo-Ni/Al₂O₃ catalysts (oxidation state) prepared by different impregnation sequences

(a): Ni 2p_3/2; (b): Mo 3d

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图 5 不同浸渍顺序催化剂 (硫化态) H₂-TPR谱图

Figure 5 H₂-TPR profiles of the Mo-Ni/Al₂O₃ catalysts (sulfide state) prepared by different impregnation sequences

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图 6 不同浸渍顺序催化剂的 (硫化态) XPS谱图

Figure 6 XPS spectra of the Mo-Ni/Al₂O₃ catalysts (sulfide state) prepared by different impregnation sequences

(a): Ni 2p_3/2; (b): Mo 3d

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图 7 不同浸渍顺序硫化态催化剂的HR-TEM照片

Figure 7 HR-TEM images of the Mo-Ni/Al₂O₃ catalysts (sulfide state) prepared by different impregnation sequences

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表 1 不同浸渍顺序催化剂的孔结构性质

Table 1 Textural properties of the Mo-Ni/Al₂O₃ catalysts prepared by different impregnation sequences

Sample	Specific area A /(m²·g^-1)	Average pore diameter d/nm	Pore volume v /(cm³·g^-1)
Al₂O₃	297.5	8.54	0.49
MN	217.2	7.84	0.43
SI-mn	199.3	7.90	0.39
SI-nm	194.6	7.78	0.37

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