F改性H<i>β</i>对Mo-Ni/F-H<i>β</i>催化剂的FCC汽油硫转移反应催化性能的影响

梁生荣; 刘峰; 王倩; 武瑞瑞; 张君涛; 申志兵

F改性Hβ对Mo-Ni/F-Hβ催化剂的FCC汽油硫转移反应催化性能的影响

西安石油大学化学化工学院, 陕西西安 710065

基金项目:

中国石油科技创新基金项目 2017D-5007-0401

西安石油大学研究生创新与实践能力培养项目 YCS19113074

详细信息

中图分类号: TE624.9
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- 被引次数: 0
出版历程
- 收稿日期: 2019-11-22
- 修回日期: 2020-01-31
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-04-10

Effect of modification to Hβ with F on the performance of Mo-Ni/F-Hβ catalyst in the sulfur transfer reactions of FCC gasoline

School of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, China

Funds:

China Petroleum Science and Technology Innovation Fund Project 2017D-5007-0401

Practical Ability Training Project of Xi'an University of Petroleum YCS19113074

More Information

Corresponding author: SHEN Zhi-bing, Tel: 15388631667, E-mail: szb@xsyu.edu.cn

摘要

摘要: 通过添加不同含量的F对Hβ分子筛进行改性，制备Mo-Ni/F-Hβ催化剂，采用N₂吸附-脱附、NH₃-TPD、XRD、Py-FTIR和SEM等方法对该催化剂进行了表征，研究了F改性对该Mo-Ni/F-Hβ催化剂在FCC汽油中硫醇醚化和噻吩烷基化等硫转移反应中催化性能的影响。结果表明，以0.5%含量F修饰的β分子筛制备的催化剂对硫醚化反应和噻吩烷基化反应具有明显的促进作用，并能提高对二烯烃选择性加氢的选择性。F的引入可增强Hβ分子筛的中强酸量，降低强酸量，并提高了L/B酸中心比例，这些变化对催化性能改善起到重要作用。
- 氟改性 /
- 催化剂 /
- FCC汽油 /
- 硫转移反应
Abstract: Hβ zeolite was modified with different contents of F to prepare the Mo-Ni/F-Hβ catalysts. The Mo-Ni/F-Hβ catalysts were characterized by nitrogen physisorption, NH₃-TPD, XRD, Py-FTIR and SEM; the effect of modification to Hβ with F on the catalytic performance of Mo-Ni/F-Hβ in the sulfur transfer reactions such as etherification of mercaptan and alkylation of thiophene in FCC gasoline was then investigated. The results indicate that the Mo-Ni/F-Hβ catalyst prepared with 0.5% F-modified Hβ zeolite can promote the thioetherification and thiophene alkylation reactions and improve the selectivity of dienes hydrogenation. The introduction of F can enhance the medium strong acid content of Hβ zeolite, reduce the strong acid content, and increase the ratio of L/B acid sites, all these may contribute to improving the catalytic performance of Mo-Ni/F-Hβ in the sulfur transfer reactions of FCC gasoline.
- fluorine modification /
- catalyst /
- FCC gasoline /
- sulfur transfer reaction

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图 1 固定床管式反应器装置流程示意图

Figure 1 Flow chart of fixed bed tubular reactor

1: hydrogen source; 2: drier; 3: filter; 4: pressure reducing valve; 5: gas flowmeter; 6: one way valve; 7: gas feed vent; 8: reactor inlet pressure; 9: electronic balance; 10: liquid feed; 11: filter; 12: feed pump; 13: one way valve; 14: liquid feed vent; 15: gas liquid mixing tee; 16: temperature controller; 17: temperature displayer; 18: thermocouple for temperature controller; 19: thermocouple temperature displayer; 20: tubular reactor; 21: heating furnace; 22: condenser; 23: high separator; 24: low separator; 25: cooling water outlet; 26: cooling water inlet; 27: reactor outlet pressure; 28: dryer; 29: back pressure valve; 30: sampling valve; 31: sampling pressure indicator; 32: rotameter; 33: sampling port; 34: sampling vent; 35: tail gas vent

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图 2 不同F处理量对H β分子筛处理前后的XRD谱图

Figure 2 XRD patterns of H β zeolites before and after F modification

a: H β; b: H β (0.3%F); c: H β (0.5%F); d: H β (0.7%F)

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图 3 H β载体改性前后N₂吸附-脱附等温线

Figure 3 Adsorption-desorption isotherms of H β zeolites before and after F modification

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图 4 H β载体改性前后的孔径分布

Figure 4 Pore size distributions of H β zeolites before and after F modification

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图 5 F处理前后H β分子筛的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of H β zeolites before and after F modification

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图 6 F处理前后H β分子筛的Py-FTIR谱图

Figure 6 Py-FTIR spectra of H β zeolites before and after F modification

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图 7 H β、H β (0.3%F)、H β (0.5%F)和H β (0.7%F)的SEM照片

Figure 7 SEM images of H β, H β (0.3%F), H β (0.5%F) and H β (0.7%F)

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图 8 F处理H β分子筛对硫转移过程噻吩烷基化转化率的影响

Figure 8 Conversion of thiophene over H β zeolites before and after F modification

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图 9 F处理H β分子筛对硫转移过程正丁硫醇醚化反应的转化率

Figure 9 Conversion of n-butyl mercaptan over H β zeolites before and after F modification

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图 10 F处理前后H β分子筛对硫转移过程烯烃类化合物加氢性能测试

Figure 10 Hydrogenation of olefins (di-olefins) over H β zeolites before and after F modification

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表 1 催化剂中F、Ni、Mo元素检测结果

Table 1 Contents of F, Ni and Mo elements in various F-modified Mo-Ni/F-H β catalysts

Catalyst	Element content w/(μg·g^-1)
Catalyst	F	Ni	Mo
Mo-Ni/F-Hβ(0 F)	0	3.64	11.56
Mo-Ni/F-Hβ(0.3%F)	0.29	3.77	11.83
Mo-Ni/F-Hβ(0.5%F)	0.49	3.64	11.56
Mo-Ni/F-Hβ(0.7%F)	0.68	3.59	11.88
note: the contents of Ni and Mo in the Mo-Ni/F-H β catalyst (5.78% MoO₃ and 15% NiO) are 11.79 and 3.85 μ g/g, respectively

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表 2 不同F处理量对H β分子筛相对结晶度分析

Table 2 Relative crystallinity of F-modified H β zeolites determined by XRD

Zeolite	Peak at 7.88°		Peak at 22.55°		Relative crystallinity η/%
Zeolite	area	retention value	area	retention value	Relative crystallinity η/%
Hβ(0)	998.22	100%	398.64	100%	100
Hβ(0.3%F)	905.38	90.70%	359.47	90.17%	90.55
Hβ(0.5%F)	878.61	88.02%	351.42	88.14%	88.06
Hβ(0.7%F)	852.12	85.36%	339.36	85.13%	85.30

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表 3 F处理前后H β分子筛孔结构参数

Table 3 Textural properties of H β zeolites before and after F modification

Zeolite	Specific surface area A/(m²·g^-1)			Pore volume v/(cm³·g^-1)
Zeolite	A_BET	A_micro	A_meso	v_total	v_micro	v_meso
Hβ(0)	475	351	124	0.43	0.20	0.23
Hβ(0.3%F)	465	334	131	0.43	0.19	0.24
Hβ(0.5%F)	464	327	137	0.43	0.18	0.25
Hβ(0.7%F)	463	290	173	0.54	0.17	0.37

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表 4 F处理前后H β分子筛酸量变化

Table 4 Acidity of H β zeolites before and after F modification

Zeolite	Lewis / (μmol·g^-1)	Brønsted/ (μmol·g^-1)	Total acid/ (μmol·g^-1)	L/B
Hβ(0)	117.96	634.88	752.84	0.19
Hβ(0.3%F)	426.51	459.92	886.43	0.93
Hβ(0.5%F)	678.12	297.37	975.49	2.28
Hβ(0.7%F)	520.56	250.73	771.29	2.08

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